WO2003064526A1 - Light-diffusing resin composition - Google Patents

Light-diffusing resin composition Download PDF

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Publication number
WO2003064526A1
WO2003064526A1 PCT/JP2003/000799 JP0300799W WO03064526A1 WO 2003064526 A1 WO2003064526 A1 WO 2003064526A1 JP 0300799 W JP0300799 W JP 0300799W WO 03064526 A1 WO03064526 A1 WO 03064526A1
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WIPO (PCT)
Prior art keywords
light
resin composition
block copolymer
weight
diffusing
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PCT/JP2003/000799
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French (fr)
Japanese (ja)
Inventor
Teiji Kohara
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Zeon Corporation
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Publication of WO2003064526A1 publication Critical patent/WO2003064526A1/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a light-diffusing resin composition having excellent light-transmitting, light-diffusing properties and moldability, and a light-diffusing molded article made of the light-diffusing resin composition.
  • the light diffusion molded body is a molded body that diffuses incident light and emits the light.
  • This light-diffusing molded article is used when it is desired to uniformly irradiate the whole, but it is difficult to irradiate the whole due to the positional relationship with the light source.
  • the plate-shaped molded body is installed between the light source and the back of the display, so that light from the pack-light source in the immediate vicinity of the liquid crystal is uniformly emitted from the display surface, and Light and dark are not generated on the spray.
  • Such a light-diffusing molded article has a high ratio of outgoing light to incident light, that is, the total light transmittance, which is the sum of parallel light transmittance and diffuse light transmittance, in order to effectively use the light of the light source.
  • the total light transmittance which is the sum of parallel light transmittance and diffuse light transmittance, in order to effectively use the light of the light source.
  • a molded article in which particles are dispersed in a transparent resin matrix is known (for example, Japanese Patent Application Laid-Open No. Hei 5-218408 / Japanese Patent Application Laid-Open No. Hei 6-178781). Gazettes).
  • this molded article when the number of particles to be dispersed is increased, the light diffusion property is improved, but the light transmittance is reduced. Conversely, when the number of particles is reduced, the light transmittance improves, but the light diffusivity decreases. Light transmission and light diffusion have an inverse correlation. Therefore, depending on the application, either light transmittance or light diffusivity may be insufficient, and there has been a demand for a light diffusing molded body having both high light transmittance and high light diffusion ⁇ fe.
  • the light diffusing plate made of this composition has practically sufficient characteristics, the light stability and dimensional accuracy may be slightly insufficient depending on the selection of molding conditions. is there.
  • a transparent resin a resin in which an aromatic ring portion of polystyrene is added to hydrogen, or a light diffusing resin using a resin containing an alicyclic structure-containing ethylenically unsaturated monomer unit Compositions have been proposed (for example, Japanese Patent Application Laid-Open No. 2001-131419, Japanese Patent Application Laid-Open No. 2001-210613).
  • An object of the present invention is to provide a water-soluble resin composition and a light-diffusing molded article formed by using the resin composition.
  • a block copolymer having a specific structure obtained by hydrogenating a block copolymer of an aromatic vinyl compound having a specific block composition and a conjugated gen to an aromatic ring is obtained.
  • the gate is formed by injection molding a light diffusing plate using a light diffusing resin composition having a specific modulus of elasticity equal to or higher than a specific value, in which a transparent organic filler 7 and an inorganic filler are dispersed.
  • the inventors have found that even when the thickness is reduced, no crack is generated even when the mold is released, and the mechanical strength is improved so that no crack or the like is generated even during the cutting process, and the present invention has been completed.
  • a light-diffusing resin composition comprising an alicyclic structure-containing block copolymer and a filler
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • R 2 — R 12 represent R 2 , R 3 , R 4 , R 5 , R s , R 7 , R 7 8 , R 9 , R xo , R 11 and R 12 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group the expressed. even R 2 one R 12 is each the same or different.
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • two polymer blocks [A] are bonded to both ends of one polymer block [B] ([A]-[B]).
  • — [A]) is a type of triplock copolymer.
  • the block copolymer having an alicyclic structure has a weight-average molecular weight (Mw) of 20,000 to 400,000, and the weight-average molecular weight (Mw) is a gel permeate using tetrahydrofuran as a solvent. Chillon. Chromatography (GP)
  • the block copolymer having an alicyclic structure has a weight average molecular weight (Mw) and a number average molecular weight ( ⁇ ) ratio (Mw / Mn) of 3 or less, and the weight average molecular weight (Mw / Mn).
  • Mw) and number average molecular weight (Mn) are the values in terms of polystyrene measured by gel 'permeation' chromatography (GPC) using tetrahydrofuran as a solvent.
  • the alicyclic structure-containing block copolymer is obtained by living anion polymerization.
  • the filler has an average particle size of 1 ⁇ m or more and 30 ⁇ m or less.
  • the filler is an organic filler composed of a polymer or a crosslinked product of the polymer.
  • the organic filler has a total light transmittance of 70% or more, and the total light transmittance is a value when a plate-like molded body having a thickness of 1 mm is formed.
  • the refractive index of the alicyclic structure-containing block copolymer is ⁇ 1 and the refractive index of the organic filler is ⁇ 2
  • the organic filler is a fine particle made of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof.
  • the filler is at least one inorganic filler selected from the group consisting of talc, silicon oxide, alumina and silica alumina.
  • a light diffusing molded article obtained by molding any of the light diffusing resin compositions described above.
  • the light diffusing molded article according to the present invention is a light diffusing plate.
  • the light diffusing resin composition according to the present invention has an alicyclic structure-containing block copolymer and a filler.
  • the alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A] containing 90% by weight or more of a repeating unit [1] represented by the following formula (1), and a polymer block [A] represented by the following formula (2). And a polymer block [B] containing a total of 30% by weight or more of the repeating unit [2] and Z represented by the formula (3) or the repeating unit [3] represented by the following formula (3).
  • the repeating unit [1] contained in the polymer block [A] is represented by the following formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 2 — R 12 represents R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , each of which is independently a hydrogen atom Represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group.
  • R 2 —R 12 may be the same or different.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 to R 12 are all hydrogen atoms.
  • the repeating unit [2] contained in the polymer block [B] is represented by the following formula (2).
  • R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 120 carbon atoms, a halogen group or an aryl group.
  • a preferred structure of the repeating unit [2] represented by the formula (2) is that in which R 13 and R 14 are a hydrogen atom or a methyl group.
  • the repeating unit [3] contained in the polymer block [B] is represented by the following formula (3).
  • R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
  • R 15 is a hydrogen atom and R 16 is an ethyl group or an isopropyl group.
  • Polymer block [A] repeat units in [1], the weight fraction of total alicyclic structure-containing Proc co polymer (weight%) is taken as w 1AT, the ⁇ is better good It is preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 70% by weight. w When 1AT is in the above range, the heat resistance of the molded body is improved.
  • the remainder other than the repeating unit [1] in the polymer block [A] may be the one obtained by hydrogenating a carbon-carbon unsaturated bond of a repeating unit derived from a chain conjugated gen or a chain bull compound. preferable.
  • the weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire polymer block [B] is w 2BB
  • the repeating unit [3] in the polymer block [B] is the weight fraction of total polymer block [B] (weight 0/0)
  • the total amount (W2BB + W3BB) with W2BB C W3BB is 3
  • the weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire alicyclic structure-containing block copolymer is defined as w 2BT, and the repeating unit in the polymer block [B] is [ 2 ].
  • the weight fraction (weight 0 / ⁇ ) of the alicyclic structure-containing block copolymer in [3] is W3BT
  • the total amount (w 2B T + W 3B ⁇ ) of W 2BT and W 3BT is It is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. If the total amount (W2BT + W3BT) is too small, the flexibility of the resin molded article may be low and brittle, and if too large, the heat resistance may be reduced.
  • the polymer block [B] may contain the above-mentioned repeating unit [1].
  • 1 BT is preferably 30 weight. / 0 or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less.
  • the higher the w1BT the higher the transparency of the resin molded body. However, if the w1BT exceeds the above range, the resin may become brittle and have poor mechanical strength.
  • the polymer block [A] and the polymer block [B] may further contain a repeating unit [X] represented by the following formula (4).
  • R 17 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 18 represents a nitrile group, an alkoxycarbyl group, a hydrocarbyl group, a hydroxycarbyl group, or a halogen group.
  • R 19 is a hydrogen atom. R 18 and R 19 may form an acid anhydride group or an imido group.
  • the weight fraction of the repeating unit [X] in the total block copolymer containing an alicyclic structure is preferred.
  • the w XT preferably 2 0 wt% or less, preferably Ri yo 1 0 wt. / 0 or less.
  • the alicyclic structure-containing block copolymer used in the present invention has a weight fraction of WA of all the repeating units constituting the polymer block [A], and a weight fraction of all the repeating units constituting the polymer block [B].
  • the ratio (WA: WB) is preferably 10:90 to 95: 5.
  • the ratio (WA: WB) is more preferably 50:50 to 90:10, and particularly preferably. 60: 40 to 85: 15.
  • T, WXT, WA, and WB are values calculated as follows.
  • the amount of each monomer in the reaction solution is quantified by gas chromatography analysis.
  • W 1 AT, W XAA, ( 2BT + W 3BT),, W 2BB + W 3BB), W 1BT, WXT N WA, WB is calculated.
  • W 2BT and W SBT are calculated from the ratio of vinyl groups to vinylene groups by iH-NMR analysis of the block copolymer before hydrogenation.
  • the alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A]
  • [A]-[B]) type triblock copolymer a block copolymer in which a total of four or more polymer blocks [A] and polymer blocks [B] are alternately connected may be used.
  • ([A]-[B]-[A]) type triplock copolymers are preferred from the viewpoints of flexibility, mechanical strength, and productivity.
  • Each polymer block may have the same or different molecular length. However, in order to increase the elastic modulus of the molded article of the light-diffusing resin composition of the present invention, at least two A blocks (A 1 block, It is preferable that the ratio of the molecular length be different between the A2 blocks).
  • the ratio A 1 / A 2 of the molecular length of the block is preferably 1.5 to 8, more preferably 1.7 to 7, and particularly preferably 2 to 6.
  • the molecular length of each polymer block is a value calculated by measuring the molecular weight before and after polymerizing each polymer block by gel permeation 'chromatography analysis and calculating the molecular weight increase.
  • the molecular weight of the block copolymer containing an alicyclic structure used in the present invention is determined by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by (GPC) is preferably 20,000 to 400,000, more preferably 30,000 to 300,000, and particularly preferably 40,000 to 200,000. 000 range. If the Mw of the block copolymer containing an alicyclic structure is excessively small, the mechanical strength and heat resistance of the molded article may decrease.On the other hand, if the copolymer is excessively large, the productivity in the resin production stage and the resin addition may be reduced. There is a possibility that the moldability and the like may be reduced.
  • the molecular weight distribution of the block copolymer having an alicyclic structure can be appropriately selected depending on the purpose of use.
  • the ratio Mw between the polystyrene-converted Mw and the number average molecular weight ( ⁇ ) measured by genole permeation 'chromatography is described.
  • / Mn is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. preferable.
  • Mw / Mn is in the above range, the molded article is excellent in mechanical strength, heat resistance, and the like.
  • the block copolymer having an alicyclic structure used in the present invention can be produced, for example, as follows.
  • the unsaturated bond is hydrogenated step (3) And characterized in that:
  • Step (1) is a step of polymerizing the monomer mixture (a) to obtain a polymer block [A].
  • step (2) the monomer mixture (b) is polymerized to form a polymer block.
  • the monomer mixture (b) may contain at least one of an aromatic butyl compound, a bulcycloalkene, and a butylcycloalkene at a total amount of 70% by weight or less.
  • the production method of the present invention will be described more specifically by taking, as an example, a method for obtaining the most preferred triplock copolymer of the present invention. Since there are two steps of polymerizing the monomer mixture (a), the monomer mixture (a) used in each step is referred to as a monomer mixture ( ai ) and a monomer mixture (a 2 ).
  • the monomer mixture ( ai ) is polymerized to obtain a polymer block [A].
  • the monomer mixture (b) is polymerized in an organic solvent solution of the polymer.
  • a diblock copolymer composed of the polymer block [Ai] and the polymer block [B] is obtained.
  • a monomer mixture (a 2 ) is polymerized at the terminal on the polymer block [B] side, and a polymer block is attached to both terminals of the polymer block [B].
  • [A] is obtained one by one to obtain a triploc copolymer.
  • the block copolymer obtained as described above has an unsaturated bond (including one in an aromatic ring)
  • the unsaturated portion is saturated by a hydrogenation reaction, so that the present invention is the most preferable.
  • An alicyclic structure-containing block copolymer is obtained.
  • aromatic vinyl compound examples include styrene, ct-methinolestyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methynolestyrene, 2,4-diisopropynolestyrene, and 2,4-dimethino Examples thereof include styrene, 4-t-butynolestyrene, 5-t-butynole-2-methynolestyrene, 4-monochlorostyrene, dichlorostyrene, 4-monophenololerostyrene, and 4-phenylstyrene.
  • Examples of the bulcycloaken include 4-bulcyclohexene, 4-isopropininolecyclohexene, 1-methinole 4-vinylinolecyclohexene, 2-methinole 4-bienoresic mouth hexene, and 1-methinole 4-isopropeninolecin hexene.
  • 2-methinolay 4-isopropininolecyclohexene, 3-vinylinolecyclopentene, 4-bi-cyclopentene, 5-vinylinolecyclo [2.2.1] hept-2-ene, and the like.
  • bulcycloalkane examples include biercyclobutane, bursik pentane, vininolesik hexane, 2-vininolevisic mouth [2.2.1] heptane, isopropininolecyclohexane, 3-methinolebininolecyclohexane, Examples thereof include 4-methylvinylcyclohexane, 3-methylisopropenylcyclohexane, and 4-methylisopropenylvinylsiloxane.
  • These compounds may have a substituent such as a halogen group, an alkoxy group and a hydroxy group. These compounds may be used alone or in combination of two or more.
  • the use of the aromatic vinyl conjugate increases the polymerization yield. Furthermore, among these, styrene, high-methyl styrene, 2-methynolestyrene, 3- More preferably, one or more aromatic butyl compounds of methylstyrene and 4-methylstyrene are used.
  • linear biel compound examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1_heptene, 1-otaten, 1-nonene, 1_decene, 1-dodecene, 1- Examples include chain-like olefins such as eicosene, 4-methylino-11-pentene, and 4,6-dimethyl-11-heptene. Among them, ethylene and propylene are preferred.
  • chain conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among them, 1,3-butadiene and isoprene are preferred.
  • the monomer mixture (a) and the monomer mixture (b) may contain a butyl compound other than the above.
  • vinyl compounds include, for example, nitrile monomers such as acrylonitrile, methacrylonitrile, 1-cyano-1-chloroethylene; 2-methoxycarbyl-1-propene, 2-ethoxycarboloop-loop pen, 2-Propoxy lipoloop loop pen, 2-butoxycarboloop loop pen, 1-methoxycarbonylethylene, 1-ethoxycarboninoleethylene, 1-propoxycanolepounethylene, 1-butoxycanoleponinoleethylene (Meth) acrylate monomers such as 1-carboxyethylene, 1-carboxy-1-methylethylene, unsaturated fatty acid-based monomers such as maleic anhydride; 1-hydrocanoleponinoleethylene, 2-hydrocanolepo 2-propene, 1-methylcarbonylethylene, 2-methylca Boyuru one propene, N- Fueniruma Ray Mi de
  • any of radical polymerization, ion polymerization, cationic polymerization, coordination anion polymerization, coordination cation polymerization and the like may be used.
  • a method in which radical polymerization, anion polymerization, force polymerization, or the like is performed by living polymerization is preferable, and living polymerization is more preferably used.
  • living anion polymerization the hydrogenation reaction in the polymerization operation and the subsequent steps is facilitated, and the transparency of the obtained alicyclic structure-containing block copolymer is improved.
  • the polymerization temperature is usually 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C, particularly preferably 20 ° C to 80 ° C in the presence of a polymerization initiator.
  • a polymerization initiator for example, monoorganic lithium such as n-butylinolelithium, sec-butyllithium, t_butyllithium, hexyllithium, phenyllithium; dilithiomethane, 1,4-dilithiobutane, Polyfunctional organic lithium compounds such as 1,4-diethyl-2-ethylsilyl hexane can be used.
  • the type of polymerization reaction may be any of solution polymerization, slurry polymerization and the like, but the use of solution polymerization makes it easy to remove the heat of reaction. In this case, an inert solvent in which the polymer obtained in each step is dissolved is used.
  • inert solvent examples include aliphatic hydrocarbons such as n_butane, n-pentane, isopentane, n-hexane, ⁇ -heptane, and isootatan; cyclopentane, cyclohexane, methylcyclopentane, hexane Mechirushiku port, decalin, bicyclo [4 3 0..] nonane, preparative Rishikuro [4 3 0 I 2 '5...] alicyclic hydrocarbons such as decane, benzene, aromatic such torr E down Hydrocarbons and the like.
  • aliphatic hydrocarbons such as n_butane, n-pentane, isopentane, n-hexane, ⁇ -heptane, and isootatan
  • cyclopentane, cyclohexane, methylcyclopentane, hexane Mechirushiku port decalin
  • alicyclic hydrocarbons are preferable because it can be used as it is as an inert solvent also in the hydrogenation reaction described below and the solubility of the block copolymer is good.
  • Each of these solvents may be used alone, or two or more of them may be used in combination.
  • the amount of these solvents to be used is usually 200 to 2000 parts by weight based on 100 parts by weight of the total monomers used.
  • a randomizer or the like can be used to prevent a chain of one component from becoming long.
  • a Lewis base compound or the like it is preferable to use a Lewis base compound or the like as a randomizer.
  • Lewis base compounds include, for example, dimethinooleatenole, getinoleatenole, diisopropinoleatel, dibutinoleatel, tetrahydrofuran, dipheninoleatenole, ethyleneglycoreleetenole, ethyleneglycoreleatenole, ethyleneglycorelemethino Ethenolay conjugates, such as refenoleatenole; tertiary amine compounds such as tetramethinoleethylenediamine, trimethy ⁇ amine, triethylamine, pyridine, etc .; tertiary amine compounds, tertiary amine compounds; Alkali metal alkoxide compounds such as luoxide; phosphine compounds such as triphenylphosphine; and the like.
  • the molecular weight of the block copolymer obtained by the polymerization reaction according to the above method is preferably 20,000 to 400,000, more preferably 30,000, as Mw in terms of polystyrene measured by GPC using THF as a solvent. To 300,000, particularly preferably in the range of 40,000 to 200,000. Further, the molecular weight distribution MwZ ⁇ is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
  • the block copolymer obtained by the above polymerization method when an unsaturated bond (including an aromatic ring portion) is present therein, is obtained by hydrogenating the unsaturated bond.
  • the alicyclic structure-containing block copolymer of the present invention can be obtained.
  • the method of hydrogenating the unsaturated bond, the reaction form, and the like are not particularly limited, and may be performed according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and causes less polymer chain scission reaction is preferable. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, any of a heterogeneous catalyst and a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.
  • the heterogeneous catalyst can be used as it is, as a metal or a metal compound, or supported on a suitable carrier.
  • the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like.
  • the amount of the supported catalyst is usually in the range of 0.1 to 60% by weight, preferably 1 to 50% by weight, based on the total amount of the catalyst and the carrier.
  • Examples of the supported catalyst include a specific surface area of 100 to 500 m 2 Zg and an average pore diameter of 100. Those having ⁇ 100 A, preferably 200-500 OA are preferred.
  • the value of the specific surface area is a value calculated by measuring the amount of adsorbed nitrogen and using the BET equation, and the value of the average pore diameter is a value measured by a mercury intrusion method.
  • the homogeneous catalyst examples include a catalyst obtained by combining a nickel, cobalt, titanium or iron compound with an organometallic compound (eg, an organoaluminum compound, an organolithium compound); transition metals such as rhodium, palladium, platinum, ruthenium, and rhenium; A complex catalyst or the like can be used.
  • an organometallic compound eg, an organoaluminum compound, an organolithium compound
  • transition metals such as rhodium, palladium, platinum, ruthenium, and rhenium
  • a complex catalyst or the like can be used.
  • the nickel, cobalt, titanium or iron compound for example, acetyl acetonato compounds of various metals, carboxylate salts, cyclopentagenenyl compounds and the like are used.
  • organic aluminum compound examples include alkyl phenols such as triethylaluminum and triisobutylaluminum; aluminum halides such as getylaluminum chloride and ethylaluminum dichloride; and hydrogenation such as disobutylaluminum hydride. Alkyl aluminum and the like.
  • organometallic complex catalyst examples include dihydrido-tetrakis (triphenyl norephosphine) norethenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentagenenyl) And transition metal complexes such as Huckel.
  • Each of these hydrogenation catalysts may be used alone, or two or more of them may be used in combination.
  • the amount of the hydrogenation catalyst to be used is usually from 0.01 to: L00 parts by weight, preferably from 0.05 to 50 parts by weight, more preferably from 0 to 100 parts by weight of the polymer. : 30 to 30 parts by weight.
  • the hydrogenation reaction temperature is usually from 10 ° C to 250 ° C, preferably from 50 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C. Conversion increases and molecular cleavage decreases.
  • the hydrogen pressure is usually 0.1 MPa to 30 MPa, preferably 1 MPa to 20 MPa, more preferably 2 MPa to 1 OMPa, the hydrogenation rate increases and the molecular chain breaks. And the operability is excellent.
  • the hydrogenation rate of the block copolymer containing an alicyclic structure can be measured by iH-NMR using carbon-carbon unsaturated bonds in the main chain and side chains, and carbon-carbon unsaturated carbon in the aromatic ring and cycloalkene ring. All of the bonds are preferably 90% or more, more preferably 97% More preferably, it is set to 99% or more.
  • the hydrogenation rate is high, the obtained biblock copolymer having an aliphatic structure has improved low birefringence and thermal stability.
  • the hydrogenation reaction solution or polymerization reaction solution of the block copolymer contains a hydrogenation catalyst and / or a polymerization catalyst, it is removed by a method such as filtration or centrifugation, and then the reaction solution is removed from the reaction solution. An alicyclic structure-containing block copolymer is recovered.
  • the method for recovering the alicyclic structure-containing block copolymer from the reaction solution is not particularly limited.
  • a steam coagulation method in which the solvent is removed from the alicyclic structure-containing block polymer solution by steam stripping
  • a direct desolvent method in which the solvent is removed by heating under reduced pressure
  • a solution in which the alicyclic structure-containing block is used.
  • the polymer can be collected by a known method such as a solvent coagulation method in which the polymer is poured into a poor solvent and solidified.
  • the form of the recovered alicyclic structure-containing block copolymer is usually pelletized so as to be advantageous for the subsequent melt molding, but is not limited thereto.
  • a molten alicyclic structure-containing block copolymer may be extruded from a die into a strand, cooled, and then forced into a pellet by a pelletizer to form a pellet.
  • the obtained coagulate can be dried and then melt-extruded with an extruder to form pellets in the same manner as described above.
  • the filler used in the present invention may be an organic filler or an inorganic filler.
  • the organic filler examples include a polymer capable of forming transparent fine particles in an alicyclic structure-containing block copolymer or a crosslinked product thereof.
  • the total light transmittance is preferably 70% or more, more preferably 80% or more. Preferably, those with 90% or more are particularly preferred. If the total light transmittance is too low, the light transmittance of the obtained light diffusing molded article is reduced due to light loss inside the polymer.
  • the total light transmittance here is generally 400 to
  • the refractive index of the organic filler is nlZn2 or n2Zn1 when the refractive index of the alicyclic structure-containing block copolymer is nl and the refractive index of the organic filler is n2.
  • the lower limit is preferably 1.01, more preferably 1.015, particularly preferably 1.025, and the upper limit is preferably 1.2, more preferably 1.1.
  • n2 is preferably from 1.4 to 1.8, more preferably from 1.45 to 1.72. If this refractive index ratio is too low, the light diffusibility of the obtained molded article will be low. If the refractive index ratio is too high, the light transmittance of the obtained molded article decreases.
  • the refractive index is a value at a wavelength according to the purpose of use.
  • the refractive index varies depending on the type of the polymer used, but the value can be adjusted by, for example, the amount of a monomer containing a ferul group. As the amount of the monomer containing a phenyl group increases, the refractive index of the polymer tends to increase.
  • organic fillers examples include (1) butyl monomers such as styrenes and acrylonitriles; methyl (meth) acrylate, ethyl (meth) acrylate,
  • (Meth) acrylate monomers such as butyl (meth) acrylate; homopolymers or copolymers such as (2) the above monomers and diethylene glycol di (meth) acrylate which can be copolymerized with them; , 1,3—butylene glycol di
  • Copolymers with polyfunctional monomers such as (meth) atalilate, dibielbenzene,
  • the organic filler needs to maintain the shape as fine particles in the molded body. If the shape cannot be maintained during molding, a uniform light-diffusing molded body cannot be obtained as described later. Therefore, it is preferably a crosslinked product.
  • Those which can be crosslinked at the time of polymerization such as a copolymer obtained by adding a polyfunctional monomer and copolymerizing, are preferably crosslinked to obtain particles.
  • Fine particles which are crosslinked by a method such as irradiation with ultraviolet light after being formed into particles after polymerization or after being polymerized into particles can also be used.
  • cross-linked polymethyl methacrylate cross-linked polystyrene, cross-linked sodium polyacrylate, cross-linked silicone, cross-linked acryl-styrene copolymer, cross-linked polydimethylsiloxane, and the like.
  • fine particles composed of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof are preferred.
  • the method of converting the above polymer used in the present invention into fine particles is not particularly limited, but the particles can be formed by suspension polymerization or the like.
  • suspension polymerization or the like For example, styrene and dibulbene If suspension-polymerization of a monomer containing a polyfunctional monomer, such as copolymerization of zen, is performed, crosslinked polymer fine particles can be obtained.After polymerization, washing, drying, and classification using a wind micron separator, etc. Thus, crosslinked fine particles having a desired particle size distribution can be obtained.
  • the inorganic filler examples include inorganic fine particles capable of forming transparent fine particles in an alicyclic structure-containing block copolymer. Specific examples include silica, silica alumina, alumina, aluminum hydroxide, magnesium hydroxide, tanolek, glass flakes, glass beads, sodium silicate, and the like. Among these inorganic fillers, silica and talc are preferable because of their excellent transparency. These inorganic fillers can be used alone or in combination of two or more, or can be used in combination with a transparent organic filler.
  • the inorganic filler in the case of blending the inorganic filler by melt-kneading the block copolymer having an alicyclic structure with a twin-screw kneader or the like, avoid deterioration of the color tone of the resin composition due to abrasion of the cylinder screw. For this reason, among the above-mentioned inorganic fillers, it is preferable to use one having a low hardness, such as talc.
  • the particle size of the organic filler and / or the inorganic filler is not particularly limited, but the lower limit of the average particle size is preferably 1 m, more preferably 3 / ⁇ , and particularly preferably 5 ⁇ m.
  • the upper limit is preferably 30 m, more preferably 20 ⁇ m, particularly preferably 15 m. If it is too small, the light diffusivity of the composition of the present invention increases, but the light transmittance decreases.If it is too large, the light transmissivity increases but the light diffusivity decreases, and the surface smoothness of the molded article further decreases. It may be reduced or unevenness may occur.
  • the organic filler and the Z or inorganic filler include a large number of spherical fillers.
  • spherical refers to fine particles having a minor axis and a major axis of preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 0.9 or more, and have no corner.
  • the minor diameter refers to the smallest diameter of one fine particle.
  • the longest diameter is the largest diameter of the same fine particles.
  • the ratio of the spherical fine particles in the fine particles to be used is preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%.
  • the minor axis, major axis, average particle diameter, and the presence or absence of a corner may be measured based on a micrograph image. If there are many non-spherical ones, dispersion tends to be non-uniform at the time of molding, or it becomes difficult to obtain a molded article having uniform orientation and light diffusion.
  • the organic filler and / or the inorganic filler need not be a single kind.For example, a plurality of kinds of organic fillers may be used for the purpose of adjusting the light transmittance and light diffusivity and for the purpose of adjusting to the use environment. Agent and Z or an inorganic filler may be used in combination.
  • the amount of the organic filler and / or the inorganic filler in the resin composition varies depending on the desired optical path length of the light diffusion molded article.
  • the amount in the case of a light diffusion plate having a thickness of 100, the amount is usually from 10 to 30% by weight, and in the case of a light diffusion plate having a thickness of 1 mm, it is usually from 1 to 15% by weight.
  • the content is usually 0.1 to 2% by weight, and for a light diffusing plate having a thickness of 10 mm, usually 0.1 to 0.1% by weight. 2% by weight.
  • the light diffusing resin composition according to the present invention may contain various compounding agents in addition to the alicyclic structure-containing block copolymer and the filler.
  • compounding agents there are no particular limitations on the compounding agents, but stabilizers such as antioxidants, heat stabilizers, light stabilizers, weather stabilizers, ultraviolet absorbers, near infrared absorbers, etc .; esters of aliphatic alcohols, polyhydric alcohols Lubricants such as partial esters and partial ethers; plasticizers; coloring agents such as dyes and pigments; antistatic agents and the like.
  • a blue colorant blueing agent
  • compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.
  • the antioxidant examples include a phenol-based antioxidant, a phosphorus-based antioxidant, and a zeolite-based antioxidant.
  • a phenol-based antioxidant particularly an alkyl-substituted phenol-based antioxidant is preferable.
  • antioxidants may be used alone or in combination of two or more.
  • the blending amount is appropriately selected within a range not to impair the object of the present invention, but is usually 0.001 to 5 parts by weight based on 100 parts by weight of the alicyclic structure-containing block copolymer. , Preferably 0.01-:! Parts by weight.
  • the light-diffusing resin composition according to the present invention has a flexural modulus at 25 ° C. of 10,000 to 27, measured at a temperature of 25 ° C., measured by molding into a plate having a thickness of 2 mm based on the ASTM-D790 method. 000 kgf / cm 2 , preferably 14,000 to 24,000 kgf / cm 2 , and more preferably 17,000 to 21,000 kgf / cm 2 .
  • the flexural modulus is in the above range, there is no cracking of the gate at the time of molding release, and the occurrence of cracks at the time of cutting can be prevented.
  • the light-diffusing resin composition according to the present invention uses a compounding agent blended as required in addition to the alicyclic structure-containing block copolymer and the filler described above, and uses a usual melt-kneading method, such as 1 It can be prepared (manufactured) by a method using a shaft kneader or a twin-screw kneader.
  • the melt-kneading temperature is usually from 200 to 280 ° C, preferably from 220 to 270 ° C, particularly preferably from 240 to 260 ° C, in order to suppress the thermal decomposition of the alicyclic structure-containing block copolymer and the filler. It is desirable to do.
  • the organic filler and the Z or inorganic filler are uniformly dispersed in the block copolymer having an alicyclic structure. If the organic filler and the Z or inorganic filler are not uniformly dispersed due to agglomeration or the like, unevenness in light diffusion and light transmittance occurs, which is undesirable.
  • the light-diffusing resin composition according to the present invention can be molded into various molded articles and used for various applications.
  • a method of molding a general thermoplastic resin can be used. Specifically, extrusion molding, injection molding, compression molding, compressed air molding, vacuum molding and the like are used.
  • the obtained compact is used as a light diffusing plate, etc., and when a product of different size is to be produced in a large variety and small quantity, the extruded plate-like compact is cut, punched, etc. Whatever shape you want, you can produce a lot of the same size In this case, a method by injection molding is advantageous.
  • the light diffusing resin composition is extruded with a T-die or the like, and then sandwiched and pressed by a roll having a mat pattern, so that the mat pattern is formed on the surface. Any method may be used, such as a method of transferring.
  • the molding conditions are appropriately selected depending on the molding method.
  • the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 200 to 280 ° C, more preferably 220 to 250 ° C.
  • the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 180 to 270 ° C, more preferably 200 to 240 ° C. If the resin temperature is excessively low, the fluidity will deteriorate, and the molded product may have sink marks, distortion, and rough surfaces. Conversely, if the resin temperature is excessively high, silver streaks and die lines are generated due to thermal decomposition of the resin. There is a risk of molding defects such as rubbing and yellowing of the molded product.
  • the light diffusing molded article according to the present invention has various shapes such as a spherical shape, a rod shape, a plate shape, a column shape, a cylindrical shape, a lens shape, a film or sheet shape, and has an arbitrary shape depending on the application. be able to.
  • Examples of the light diffusing molded body include a light diffusing plate used for a pack-light type liquid crystal display and the like.
  • the light diffusing plate is disposed between the light source and the irradiation target, so that the light from the pack light source is uniformly emitted, and the light and dark on the emission surface are uniform.
  • Other applications include anti-reflection films, light-diffusing films, lighting covers, reflective screens, transmissive screens, and bulletin board backlights.
  • Mn was measured by GPC at 30 ° C. using THF as a solvent, Mn in terms of standard polystyrene was determined, and the ratio of Mw to Mn (MwZMn) determined in the above (1) was calculated.
  • the hydrogenation rates of the main chain and the aromatic ring of the hydrogenated block copolymer were calculated by measuring the ⁇ H-NMR spectrum.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and the antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate] (ilganox 1010, Ciba Specialty Chemicals) 0.1
  • the antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate] (ilganox 1010, Ciba Specialty Chemicals) 0.1
  • Add 1 part dissolve, and remove solvent using a thin film dryer (Conto Kokuchi, Hitachi, Ltd.) at 260 ° C and 1 OTorr. went.
  • the desolventized block copolymer was extruded as a strand from a die in a molten state by an extruder, cooled with water, and then cut to obtain pellets.
  • the pellet obtained here is a.
  • the obtained hydrogenated block copolymer is a ternary block copolymer composed of a block (St) containing a repeating unit derived from styrene, a block (Ip) containing a repeating unit derived from isoprene, and St. It was a polymer.
  • the block copolymer had Mw of 130,000, MwZMn of 1.20, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%.
  • the pellet was compression molded at 220 ° C to produce a 0.1 mm thick sheet, and the refractive index measured by Abbe refractometer was 1.51.
  • the same reactor as in Production Example 1 was charged with 300 parts of dehydrated cyclohexane, 30 parts of styrene and 0.20 parts of dibutyl ether, and stirred at 60 ° C. while stirring at a temperature of 60 ° C. to a content of 15%. (Xan solution) 0.25 parts was added to initiate the polymerization reaction. After performing the polymerization reaction for 1 hour, 10 parts of styrene was added to the reaction solution, and the polymerization reaction was further performed for 1 hour. Thereafter, 20 parts of isoprene was further added, and the polymerization reaction was further performed for 1 hour. Thereafter, 40 parts of styrene was further added, and the polymerization reaction was continued for another hour. Then, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
  • the pellet obtained here is referred to as resin b.
  • the obtained hydrogenated block copolymer was a ternary block copolymer composed of St, Ip, and St.
  • the block copolymer had an Mw of 134,000, an Mw / M of 1.21, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%.
  • the refractive index measured in the same manner as in Production Example 1 was 1.51.
  • the pellet obtained here is referred to as resin c.
  • the obtained hydrogenated block copolymer was a random copolymer composed of St and Ip.
  • the Mw of the random copolymer was 138,000, MwZMn was 1.22, and the hydrogenation ratio of the main chain and the aromatic ring was 99.9%.
  • the refractive index measured in the same manner as in Production Example 1 was 1.51.
  • Resin a obtained in Production Example 1 100 parts by weight, and spherical crosslinked polystyrene beads (Techpolymer SB X-8, manufactured by Sekisui Plastics Co., Ltd., average particle size 8111, refractive index 1.59) 5 parts by weight
  • a twin-screw kneader TEM-35B, manufactured by Toshiba Machine Co., Ltd.
  • the light diffusing resin composition was extruded from a twin-screw kneader into a strand, cooled with water, and pelletized by a pelletizer.
  • injection molding is performed using an injection molding machine (IS 450, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 260 ° C and a mold temperature of 90 ° C. Length 295 mm, width 225 mm, thickness A 2 mm light diffusion plate was made.
  • the haze which is an index of the total light transmittance and light diffusivity of this light diffusion plate, was measured by a turbidity meter (NDH-300 mm, manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method of JIS K7105.
  • a turbidity meter NDH-300 mm, manufactured by Nippon Denshoku Industries Co., Ltd.
  • JIS K7105 JIS K7105
  • the mechanical strength of the light diffusing plate is determined by cutting out the light diffusing plate into test pieces 100 mm long and 15 mm wide, and using a strograph (manufactured by Toyo Seiki Seisakusho; V10-B) in accordance with ASTM D790 The bending strength at 25 ° C was measured. The bending test showed a yield point and was flexible.
  • the outer shape of the longitudinal end of the light diffuser plate is cut by 2 mm width from the both ends by 100 mm from the both ends with a NC machine, leaving a 25 mm long positioning projection at the center of the end, cracking, cracking, etc. It was confirmed that there was no occurrence of poor appearance. Table 1 shows the results of the evaluation, in which there was no noticeable defect and the appearance was good.
  • spherically crosslinked silicone resin beads (Tospearl 145, manufactured by Toshiba Silicone Co., average particle size 4.5 Mm, refractive index 1.43): 5 parts by weight Except for use, a light diffusing resin composition was obtained in the same manner as in Example 1, and this light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. It was evaluated similarly. The results are shown in Table 1.
  • Example 4 Light diffusing property was obtained in the same manner as in Example 1 except that talc (Microace, manufactured by Nippon Talc Co., average particle size: 4111): 5 parts by weight was used instead of the spherical crosslinked polystyrene beads of Example 1. A resin composition was obtained, and this light-diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light-diffusing plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Example 4
  • a light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin b obtained in Production Example 2 was used instead of the resin a of Example 1.
  • the hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • resin b obtained in Production Example 2 100 parts by weight, spherical spherical crosslinked polystyrene beads used in Example 2 in place of spherical crosslinked polystyrene beads
  • Resin beads A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • a light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin c obtained in Production Example 3 was used instead of the resin a of Example 1.
  • the hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 parts by weight, and in place of the spherical crosslinked polystyrene beads, the same spherical crosslinked silicone as used in Example 2 was used.
  • Resin beads A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 3 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 weight parts, and in place of the spherical crosslinked polystyrene beads, the same talc used in Example 3 was used: 5 parts by weight.
  • a light diffusing resin composition was obtained in the same manner as in Example 1 except that the light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. Was evaluated. The results are shown in Table 1.
  • Compounding amount (parts by weight) Compounding amount (parts by weight) 'Thickness of the ancestral material ⁇ Heinos, like 3 ⁇ 4lA "o fam ⁇ " ft' gfsCr
  • Example 1 100 5-19,000 Good appearance 62 94 Good appearance
  • Example 4 100 5 14,000 Good appearance 61 93 Good appearance
  • Example 5 100 5 14,000 Good appearance 68 92 Good appearance
  • a St-Ip-St hydrogenated ternary block copolymer obtained in Production Example 1 and Production Example 2 and a filler had a flexural modulus of 10, 000 ⁇ 27, OOO kg fZcm 2 It was confirmed that the light diffusing molded product (Examples 1-6) comprising the light diffusing resin composition of the present invention was excellent in both light transmittance and light diffusivity. did it.
  • the light-diffusing molded articles of Examples 1 to 6 consist of the conventional hydrogenated styrene-based random copolymer obtained in Production Example 3 and a filler, and have a flexural modulus of 27, OOO kgf Xcm Mechanical flexibility is imparted as compared to the light-diffusing molded article made of the light-diffusing resin composition of 2 or more (Comparative Examples 1 to 3), and the gate portion cracks at the time of release from the injection molding, It was confirmed that chipping and cracking hardly occurred on the cut surface during cutting of the light diffusion plate.
  • the improved mechanical flexibility has a great industrial advantage because small and large variety of molded products can be easily prepared from extruded plates or plates of a certain size by cutting or the like. Industrial applicability
  • a light-diffusing resin suitable for light-diffusing molded articles such as a light-diffusing plate, which has both excellent light-transmitting properties and light-diffusing properties, and has mechanical strength that is hard to be broken during molding and actual use.
  • a composition is provided.

Abstract

A light-diffusing composition having an alicyclic structure-containing block copolymer and a filler, in which the alicyclic structure-containing block copolymer has a polymer block [A] containing a specific repeating unit [1] in an amount of 90% by weight or more and another polymer block [B] containing a specific repeating unit [2] and/or another specific repeating unit [3] in a total amount of 30% by weight or more and which has a flexural modulus determined by molding the composition into a plate of 2 mm in thickness and measuring at 25 ° C in accordance with ASTM-D790 of from 10,000 to 27,000 kgf/cm2. Thus, a light-diffusing composition appropriate for molded light-diffusing articles (a light-diffusing plate, etc.) which has a high light permeability, excellent light-diffusing properties and such a high mechanical strength as being hardly broken at molding or practically using is provided.

Description

明糸田書 光拡散性樹脂組成物 発明の属する技術分野  Akira Itoda Light-diffusing resin composition TECHNICAL FIELD
本発明は、 光透過性、 光拡散性及び成形加工性に優れた光拡散性樹脂組成物と、 該光拡散性樹脂組成物から成る光拡散性成形体とに、 関する。 背景技術  The present invention relates to a light-diffusing resin composition having excellent light-transmitting, light-diffusing properties and moldability, and a light-diffusing molded article made of the light-diffusing resin composition. Background art
光拡散性成形体は、 入射した光を拡散させて出射する成形体である。 この光拡 散性成形体は、 全体を均一に照射したいが、 光源との位置関係などによりそれが 困難である場合などに用いられる。 例えば、 パックライ ト型の液晶ディスプレイ では、 光源とディスプレイ裏面との間に板状の該成形体を設置して、 液晶のすぐ 近くのパックライ ト光源からの光がディスプレイ表面から均一に出射され、 ディ スプレイ上で明暗が生じないようにしている。  The light diffusion molded body is a molded body that diffuses incident light and emits the light. This light-diffusing molded article is used when it is desired to uniformly irradiate the whole, but it is difficult to irradiate the whole due to the positional relationship with the light source. For example, in a pack-light type liquid crystal display, the plate-shaped molded body is installed between the light source and the back of the display, so that light from the pack-light source in the immediate vicinity of the liquid crystal is uniformly emitted from the display surface, and Light and dark are not generated on the spray.
このような光拡散性成形体は、 光源の光を有効に利用するために、 入射光に対 する出射光の割合、 すなわち平行光線透過率と拡散光線透過率を合わせた全光線 透過率が高くなくてはならない。 そのため、 入射面で光を反射しにくく、 かつ、 光を吸収しにくいことが要求される。 また、 光を拡散させるという目的から拡散 光線透過率が十分大きくなくては機能しない。  Such a light-diffusing molded article has a high ratio of outgoing light to incident light, that is, the total light transmittance, which is the sum of parallel light transmittance and diffuse light transmittance, in order to effectively use the light of the light source. Must-have. Therefore, it is required that the light is hardly reflected on the incident surface and the light is hardly absorbed. Also, it does not work if the diffused light transmittance is sufficiently large for the purpose of diffusing light.
光拡散性成形体として、 透明樹脂マトリックス中に粒子を分散させたものが知 られている (例えば、 特開平 5— 2 8 1 4 0 8号公報ゃ特開平 6— 1 0 7 8 8 1 号公報など) 。 この成形体では、 分散させる粒子数を多くすると、 光拡散性が向 上するが光透過性が低下する。 逆に粒子数を少なくすると、 光透過性は向上する が光拡散性が低下する。 光透過性と光拡散性とは逆相関の関係にある。 そのため、 用途によっては、 光透過性あるいは光拡散性のどちらかが不足することがあり、 光透過性と光拡散 ^feが共に高い光拡散性成形体が求められていた。  As a light diffusing molded article, a molded article in which particles are dispersed in a transparent resin matrix is known (for example, Japanese Patent Application Laid-Open No. Hei 5-218408 / Japanese Patent Application Laid-Open No. Hei 6-178781). Gazettes). In this molded article, when the number of particles to be dispersed is increased, the light diffusion property is improved, but the light transmittance is reduced. Conversely, when the number of particles is reduced, the light transmittance improves, but the light diffusivity decreases. Light transmission and light diffusion have an inverse correlation. Therefore, depending on the application, either light transmittance or light diffusivity may be insufficient, and there has been a demand for a light diffusing molded body having both high light transmittance and high light diffusion ^ fe.
そこで、 熱可塑性ノルボルネン系樹脂のマトリックスに透明な高分子微粒子を 分散させてなる光拡散性樹脂組成物及びそれによつて成形された光拡散板が提案 されている (特開平 8— 3 2 7 8 0 6号広報) 。 Therefore, a light-diffusing resin composition in which transparent polymer fine particles are dispersed in a matrix of a thermoplastic norbornene-based resin and a light-diffusing plate molded therefrom have been proposed. (Publication of Japanese Patent Application Laid-Open No. Hei 8-32 7806).
しかし、 この組成物からなる光拡散板は、 実用上、 十二分の特性を有している が、 成形条件などの選択の仕方で、 耐光安定性や寸法精度などが若干不足するこ とがある。  However, although the light diffusing plate made of this composition has practically sufficient characteristics, the light stability and dimensional accuracy may be slightly insufficient depending on the selection of molding conditions. is there.
上記問題点を解決するために、 透明樹脂としてポリスチレンの芳香環部分を水 素添加した樹脂、 あるいは、 脂環式構造含有エチレン性不飽和単量体単位を含有 する樹脂を使用した光拡散性樹脂組成物が提案されている (例えば、 特開 2 0 0 1 - 1 3 1 4 1 9号公報、 特開 2 0 0 1— 2 0 1 6 1 3号公報) 。  In order to solve the above problems, as a transparent resin, a resin in which an aromatic ring portion of polystyrene is added to hydrogen, or a light diffusing resin using a resin containing an alicyclic structure-containing ethylenically unsaturated monomer unit Compositions have been proposed (for example, Japanese Patent Application Laid-Open No. 2001-131419, Japanese Patent Application Laid-Open No. 2001-210613).
しかし、 液晶ディスプレイが従来以上に大型 ·薄型化されていく状況にあって は、 射出成形等により大型且つ薄型の光拡散板を成形する際、 ゲートが細くなつ てくると離型時にゲート部が割れたり、 成形後の切削加工時にクラック等が発生 する可能性があった。 発明の開示  However, in a situation where the liquid crystal display is becoming larger and thinner than before, when molding a large and thin light diffusion plate by injection molding, etc. There was a possibility of cracking and cracking during cutting after molding. Disclosure of the invention
本発明の目的は、 光透過性及び光拡散性に優れ、 さらに、 大型且つ薄型の成形 体を成形しても成形時や加工時に割れゃクラック等が発生しない程に機械的強度 に優れる光拡散性樹脂組成物及ぴ該樹脂組成物を用いて成形した光拡散性成形体 を提供することである。  It is an object of the present invention to provide a light diffusion material which has excellent light transmittance and light diffusion property, and has excellent mechanical strength so that cracks and cracks do not occur during molding or processing even when a large and thin molded article is molded. An object of the present invention is to provide a water-soluble resin composition and a light-diffusing molded article formed by using the resin composition.
本発明者は、 前記課題を解決すべく鋭意研究を重ねた結果、 特定ブロック組成 の芳香族ビュル化合物と共役ジェンとのブロック共重合体を芳香環まで水素化し てなる特定構造のブロック共重合体中に、 透明な有機充填剤及ぴ 7又は無機充填 剤を分散させてなる、 弾性率が特定値以上である光拡散性樹脂組成物を用いて光 拡散板を射出成形することにより、 ゲートが細くなっても金型離型時にも割れが 発生せず、 切削加工時にもクラック等が発生しない程に機械的強度が向上するこ とを見出し、 本発明を完成するに至った。  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a block copolymer having a specific structure obtained by hydrogenating a block copolymer of an aromatic vinyl compound having a specific block composition and a conjugated gen to an aromatic ring is obtained. The gate is formed by injection molding a light diffusing plate using a light diffusing resin composition having a specific modulus of elasticity equal to or higher than a specific value, in which a transparent organic filler 7 and an inorganic filler are dispersed. The inventors have found that even when the thickness is reduced, no crack is generated even when the mold is released, and the mechanical strength is improved so that no crack or the like is generated even during the cutting process, and the present invention has been completed.
すなわち、 本発明によれば、  That is, according to the present invention,
脂環式構造含有プロック共重合体と、 充填剤とを、 有する光拡散性樹脂組成物 であって、  A light-diffusing resin composition comprising an alicyclic structure-containing block copolymer and a filler,
前記脂環式構造含有プロック共重合体が、 下記式 (1) で表される繰り返し単位 [1] を 90重量%以上含有する重合体 プロック [A] と、 The alicyclic structure-containing block copolymer, A polymer block [A] containing 90% by weight or more of the repeating unit [1] represented by the following formula (1);
下記式 (2) で表.される繰り返し単位 [2] 及ぴ Z又は下記式 (3) で表され る'繰り返し単位 [3] を合計で 30重量%以上含有する重合体ブロック [B] と を、 有し、  A polymer block [B] containing a total of 30% by weight or more of repeating units [2] and Z represented by the following formula (2) and Z or 'repeating units [3] represented by the following formula (3): Having,
ASTM-D 790法に基づいて厚さ 2 mmの板に成形して測定された、 25 °Cにおける曲げ弾性率が、 10, 000〜 27, 000 k g f/cm2 である 光拡散性樹脂組成物 A light diffusing resin composition having a flexural modulus at 25 ° C of 10,000 to 27,000 kgf / cm 2 measured on a plate having a thickness of 2 mm based on the ASTM-D 790 method
が提供される。 Is provided.
(式 (1) 中、 R1 は水素原子、 又は炭素数 1〜20のアルキル基を表し、 R2 — R12は R2 、 R3 、 R4 、 R5 、 Rs 、 R7 、 R8 、 R9 、 Rxo, R11及ぴ R 12を意味し、 これらはそれぞれ独立に水素原子、 炭素数 1〜20のアルキル基、 ヒドロキシル基、 炭素数 1〜20のアルコキシ基、 又はハロゲン基を表す。 R2 一 R12は各々同一であっても、 異なっていてもよい。 ) (In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 2 — R 12 represent R 2 , R 3 , R 4 , R 5 , R s , R 7 , R 7 8 , R 9 , R xo , R 11 and R 12 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group the expressed. even R 2 one R 12 is each the same or different.)
CHゲ (2) (式 (2) 中、 R13及び R14は、 それぞれ独立に水素原子、 炭素数 1〜20のァ ルキル基、 ハロゲン基又はァリール基を表す。 ) CH Ge (2) (In the formula (2), R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.)
(式 (3) 中、 R15及び R16は、 それぞれ独立に水素原子、 炭素数 1〜20のァ ルキル基、 ハロゲン基又はァリール基を表す。 ) (In the formula (3), R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.)
好ましくは、 前記脂環式構造含有プロック共重合体が、 1個の前記重合体プロッ ク [B] の両端に 2個の前記重合体プロック [A] が結合した ([A]— [B]— [A]) 型のトリプロック共重合体である。  Preferably, in the block copolymer having an alicyclic structure, two polymer blocks [A] are bonded to both ends of one polymer block [B] ([A]-[B]). — [A]) is a type of triplock copolymer.
好ましくは、 前記脂環式構造含有プロック共重合体が、 20, 000〜 400, 000の重量平均分子量 (Mw) を持ち、 該重量平均分子量 (Mw) がテトラヒ ドロフランを溶媒とするゲル ·パーミエーシヨン。クロマトグラフィー (GP Preferably, the block copolymer having an alicyclic structure has a weight-average molecular weight (Mw) of 20,000 to 400,000, and the weight-average molecular weight (Mw) is a gel permeate using tetrahydrofuran as a solvent. Chillon. Chromatography (GP
C) により測定されるポリスチレン換算の値である。 It is a value in terms of polystyrene measured by C).
好ましくは、 前記脂環式構造含有プロック共重合体が、 3以下の、 重量平均分 子量 (Mw) と数平均分子量 (Μη) との比 (Mw/Mn) を持ち、 該重量平均 分子量 (Mw) と数平均分子量 (Mn) とがテトラヒドロフランを溶媒とするゲ ル 'パーミエーシヨン 'クロマトグラフィー (GPC) により測定されるポリス チレン換算の値である。  Preferably, the block copolymer having an alicyclic structure has a weight average molecular weight (Mw) and a number average molecular weight (Μη) ratio (Mw / Mn) of 3 or less, and the weight average molecular weight (Mw / Mn). Mw) and number average molecular weight (Mn) are the values in terms of polystyrene measured by gel 'permeation' chromatography (GPC) using tetrahydrofuran as a solvent.
好ましくは、 前記脂環式構造含有ブロック共重合体が、 リビングァニオン重合 により得られたものである。  Preferably, the alicyclic structure-containing block copolymer is obtained by living anion polymerization.
好ましくは、 前記充填剤が、 1 μ m以上 30 μ m以下の平均粒径を持つ。  Preferably, the filler has an average particle size of 1 μm or more and 30 μm or less.
好ましくは、 前記充填剤が、 重合体又は該重合体の架橋物からなる有機充填剤 である。 好ましくは、 前記有機充填剤が、 70%以上の全光線透過率を持ち、 該全光線 透過率が厚さ 1 mmの板状成形体にしたときの値である。 Preferably, the filler is an organic filler composed of a polymer or a crosslinked product of the polymer. Preferably, the organic filler has a total light transmittance of 70% or more, and the total light transmittance is a value when a plate-like molded body having a thickness of 1 mm is formed.
好ましくは、 前記脂環式構造含有プロック共重合体の屈折率を η 1とし、 前記 有機充填剤の屈折率を η 2としたとき、 該 n lと η 2との比 (n l/n 2) 又は (112/n l) 力 1. 01以上1. 2以下である。  Preferably, when the refractive index of the alicyclic structure-containing block copolymer is η 1 and the refractive index of the organic filler is η 2, the ratio (nl / n 2) between nl and η 2 or (112 / nl) Force 1. More than 01 and less than 1.2.
好ましくは、 前記有機充填剤が、 ポリスチレン系重合体、 ポリシロキサン系重 合体又はそれらの架橋物からなる微粒子である。  Preferably, the organic filler is a fine particle made of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof.
好ましくは、 前記充填剤が、 タルク、 酸化ケィ素、 アルミナ及ぴシリカアルミ ナからなる群から選ばれる少なくとも 1種の無機充填剤である。  Preferably, the filler is at least one inorganic filler selected from the group consisting of talc, silicon oxide, alumina and silica alumina.
本発明によれば、 上記いずれかの光拡散性樹脂組成物を成形してなる光拡散性 成形体が提供される。  According to the present invention, there is provided a light diffusing molded article obtained by molding any of the light diffusing resin compositions described above.
好ましくは、 本発明に係る光拡散性成形体は、 光拡散板である。 発明を実施するための最良の形態  Preferably, the light diffusing molded article according to the present invention is a light diffusing plate. BEST MODE FOR CARRYING OUT THE INVENTION
光拡散性樹脂組成物  Light diffusing resin composition
本発明に係る光拡散性樹脂組成物は、 脂環式構造含有プロック共重合体と、 充 填剤とを、 有する。  The light diffusing resin composition according to the present invention has an alicyclic structure-containing block copolymer and a filler.
脂環式構造含有プロック共重合体  Block copolymer containing alicyclic structure
本発明に用いる脂環式構造含有ブロック共重合体は、 下記式 (1) で表される 繰り返し単位 [1] を 90重量%以上含有する重合体ブロック [A] と、 下記式 (2) で表される繰り返し単位 [2] 及び Z又は下記式 (3) で表される繰り返 し単位 [3] を合計で 30重量%以上含有する重合体ブロック [B] とを、 有す る。 重合体プロック [A] に含有される繰り返し単位 [1] は、 下記式 (1) で表 される。 The alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A] containing 90% by weight or more of a repeating unit [1] represented by the following formula (1), and a polymer block [A] represented by the following formula (2). And a polymer block [B] containing a total of 30% by weight or more of the repeating unit [2] and Z represented by the formula (3) or the repeating unit [3] represented by the following formula (3). The repeating unit [1] contained in the polymer block [A] is represented by the following formula (1).
ここで、 式 (1) 中、 R1 は水素原子、 又は炭素数 1〜20のアルキル基を表 す。 R2 — R12は R2 、 : R3 、 R4 、 R5 、 R6 、 R7 、 R8 、 R9 、 R10、 R 11及び R12を意味し、 これらはそれぞれ独立に水素原子、 炭素数 1〜20のアル キル基、 ヒ ドロキシル基、 炭素数 1〜20のアルコキシ基、 又はハロゲン基を表 す。 R2 —R12は各々同一であっても、 異なっていてもよい。 Here, in the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R 2 — R 12 represents R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , each of which is independently a hydrogen atom Represents an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group. R 2 —R 12 may be the same or different.
式 (1) で表される繰り返し単位 [1] の好ましい構造は、 R1 が水素原子ま たはメチル基で、 R2 〜R12がすべて水素原子のものである。 In the preferred structure of the repeating unit [1] represented by the formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 to R 12 are all hydrogen atoms.
重合体プロック [B] に含有される繰り返し単位 [2] は、 下記式 (2) で表 される。  The repeating unit [2] contained in the polymer block [B] is represented by the following formula (2).
CHクー CH——CH—— CH 2 CH cool CH——CH—— CH 2
R 13 R 13
R 14  R 14
(2)  (2)
ここで、 式 (2) 中、 R13及び R14は、 それぞれ独立に水素原子、 炭素数 1 20のアルキル基、 ハ口ゲン基又はァリ一ル基を表す。 式 (2) で表される繰り返し単位 [2] の好ましい構造は R13及ぴ R14が水素 原午又はメチル基のものである。 Here, in the formula (2), R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 120 carbon atoms, a halogen group or an aryl group. A preferred structure of the repeating unit [2] represented by the formula (2) is that in which R 13 and R 14 are a hydrogen atom or a methyl group.
重合体ブロック [B] に含有される繰り返し単位 [3] は、 下記式 (3) で表 される。  The repeating unit [3] contained in the polymer block [B] is represented by the following formula (3).
ここで、 式 (3) 中、 R15及び R16は、 それぞれ独立に水素原子、 炭素数 1〜 20のアルキル基、 ハロゲン基又はァリ一ル基を表す。 Here, in the formula (3), R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.
式 (3) で表される繰り返し単位 [3] の好ましい構造は R15が水素原子で、 R16がェチル基又はィソプロピル基のものである。 In the preferred structure of the repeating unit [3] represented by the formula (3), R 15 is a hydrogen atom and R 16 is an ethyl group or an isopropyl group.
重合体ブロック [A] 中の繰り返し単位 [1] の、 重合体ブロック [B] 全体 に占める重量分率 (重量%) を w1AA としたときに、 該 w1AA は、 本発明では 9 0重量%以上であり、 好ましくは 95重量%以上である。 The polymer block [A] the repeating unit [1] in the polymer block [B] weight fraction of total (% by weight) when the w 1AA, the w 1AA is 9 0 weight in the present invention %, Preferably 95% by weight or more.
重合体ブロック [A] 中の繰り返し単位 [1] の、 脂環式構造含有プロック共 重合体全体に占める重量分率 (重量%) を w1AT としたときに、 該^^^ は、 好 ましくは 50重量%以上、 より好ましくは 60重量%、 特に好ましくは 70重量 %以上である。 w1AT が上記範囲にあるときに、 成形体の耐熱性が高められる。 重合体ブロック [A] 中の繰り返し単位 [1] 以外の残部は、 鎖状共役ジェン 又は鎖状ビュル化合物に由来する繰り返し単位の炭素一炭素不飽和結合が水素化 ' されたものであることが好ましい。 Polymer block [A] repeat units in [1], the weight fraction of total alicyclic structure-containing Proc co polymer (weight%) is taken as w 1AT, the ^^^ is better good It is preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 70% by weight. w When 1AT is in the above range, the heat resistance of the molded body is improved. The remainder other than the repeating unit [1] in the polymer block [A] may be the one obtained by hydrogenating a carbon-carbon unsaturated bond of a repeating unit derived from a chain conjugated gen or a chain bull compound. preferable.
重合体ブロック [B] 中の繰り返し単位 [2] の、 重合体ブロック [B] 全体 に占める重量分率 (重量%) を w2BB とし、 重合体ブロック [B] 中の繰り返し 単位 [3] の、 重合体ブロック [B] 全体に占める重量分率 (重量0 /0) を としたとき、 該 W2BB C W3BB との合計量 (W2BB + W3BB ) は、 本発明では 3The weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire polymer block [B] is w 2BB, and the repeating unit [3] in the polymer block [B] is the weight fraction of total polymer block [B] (weight 0/0) In the present invention, the total amount (W2BB + W3BB) with W2BB C W3BB is 3
0重量%以上であり、 好ましくは 50重量%以上、 特に好ましくは 70重量%以 上である。 It is at least 0% by weight, preferably at least 50% by weight, particularly preferably at least 70% by weight.
重合体ブロック [B] 中の繰り返し単位 [2] の、 脂環式構造含有プロック共 重合体全体に占める重量分率 (重量%) を w2BT とし、 重合体ブロック [B] 中 の繰り返し単位 [3] の、 脂環式構造含有ブロック共重合体全体に占める重量分 率 (重量0 /θ) を W3BT としたとき、 該 W2BT と W3BT との合計量 (w2BT + W 3B τ ) は、 好ましくは 5〜50重量%、 より好ましくは 10〜40重量%、 特に好 ましくは 15〜30重量%である。 合計量 (W2BT + W3BT ) が少なすぎると樹 脂成形体の柔軟性が低く脆くなるおそれがあり、 多過ぎると耐熱性が低くなる可 能性がある。 The weight fraction (% by weight) of the repeating unit [2] in the polymer block [B] with respect to the entire alicyclic structure-containing block copolymer is defined as w 2BT, and the repeating unit in the polymer block [B] is [ 2 ]. When the weight fraction (weight 0 / θ) of the alicyclic structure-containing block copolymer in [3] is W3BT, the total amount (w 2B T + W 3B τ) of W 2BT and W 3BT is It is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. If the total amount (W2BT + W3BT) is too small, the flexibility of the resin molded article may be low and brittle, and if too large, the heat resistance may be reduced.
なお、 重合体プロック [B] は、 上述した繰り返し単位 [1] を含有してもよ い。 この場合において、 重合体プロック [B] 中の繰り返し単位 [1] の、 脂環 式構造含有プロック共重合体全体に占める重量分率 (重'量%) を w1BT としたと き、 該 w1BT は、 好ましくは 30重量。 /0以下、 より好ましくは 20重量%以下、 特に好ましくは 10重量%以下である。 w1BT が高い方が樹脂成形体の透明性が 高くなるが、 w1BT が上記範囲を超えると脆くなつて機械的強度が劣るおそれが ある。 The polymer block [B] may contain the above-mentioned repeating unit [1]. In this case, when the weight fraction (weight% amount) of the repeating unit [1] in the polymer block [B] with respect to the entire alicyclic structure-containing block copolymer is defined as w 1BT , 1 BT is preferably 30 weight. / 0 or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less. The higher the w1BT , the higher the transparency of the resin molded body. However, if the w1BT exceeds the above range, the resin may become brittle and have poor mechanical strength.
重合体ブロック [A] 及び重合体プロック [B] は、 さらに、 下記式 (4) で 表される繰り返し単位 [X] を含有していてもよい。  The polymer block [A] and the polymer block [B] may further contain a repeating unit [X] represented by the following formula (4).
こで、 式 (4) 中、 R17は水素原子、 又は炭素数 1〜20のアルキル基を表 す。 R 18は二トリル基、 アルコキシカルボ-ル基、 ヒドロカルボ-ル基、 ヒドロ キシカルボ二ル基、 又はハロゲン基を表す。 R 19は水素原子である。 R 18と R 19 は、 酸無水物基、 又はイミ ド基を形成してもよい。 Here, in the formula (4), R 17 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. You. R 18 represents a nitrile group, an alkoxycarbyl group, a hydrocarbyl group, a hydroxycarbyl group, or a halogen group. R 19 is a hydrogen atom. R 18 and R 19 may form an acid anhydride group or an imido group.
脂環式構造含有ブロック共重合体中に繰り返し単位 [X] が存在すると、 成形 体の表面に塗膜等を形成する場合の密着性は向上するが、 成形体の吸湿性が高く なり高温高湿条件下において反りなどの不具合が発生し易くなる。 従って、 成形 体の吸湿性を低くし、 高温高湿条件下においても反りなどの不具合を抑制するた めに、 繰り返し単位 [X] の脂環式構造含有プロック共重合体全体に占める重量 分率 (重量%) を WXT としたとき、 該 wXT を、 好ましくは 2 0重量%以下、 よ り好ましくは 1 0重量。 /0以下とする。 When the repeating unit [X] is present in the alicyclic structure-containing block copolymer, the adhesion when a coating film or the like is formed on the surface of the molded body is improved, but the hygroscopicity of the molded body is increased and the temperature is increased. Problems such as warpage are likely to occur under wet conditions. Therefore, in order to reduce the hygroscopicity of the molded article and to suppress problems such as warping even under high-temperature and high-humidity conditions, the weight fraction of the repeating unit [X] in the total block copolymer containing an alicyclic structure is preferred. when the (% by weight) WXT, the w XT, preferably 2 0 wt% or less, preferably Ri yo 1 0 wt. / 0 or less.
さらに、 本発明で使用する脂環式構造含有プロック共重合体は、 重合体プロッ ク [A] を構成する全繰り返し単位の重量分率を WA 、 重合体プロック [ B ] を 構成する全繰り返し単位の重量分率を WB とした場合に、 その比 (WA : WB ) が 1 0 : 9 0〜9 5 : 5であることが好ましい。 また、 光拡散板に必要な耐熱性、 強度、 及び弾性率の観点からは、 前記比 (WA : WB ) が 5 0 : 5 0〜9 0 : 1 0であることがより好ましく、 特に好ましくは 6 0 : 4 0〜8 5 : 1 5である。  Further, the alicyclic structure-containing block copolymer used in the present invention has a weight fraction of WA of all the repeating units constituting the polymer block [A], and a weight fraction of all the repeating units constituting the polymer block [B]. When the weight fraction of WB is WB, the ratio (WA: WB) is preferably 10:90 to 95: 5. In addition, from the viewpoint of heat resistance, strength, and elastic modulus required for the light diffusion plate, the ratio (WA: WB) is more preferably 50:50 to 90:10, and particularly preferably. 60: 40 to 85: 15.
( WA : WB ) が上記範囲にあると、 成形体は機械的強度、 成形性などに優れる。 尚、 ここで G載し 7こ 、 、 、 、 、 、 When (WA: WB) is in the above range, the molded product has excellent mechanical strength, moldability, and the like. In addition, G is placed here, and this is 7,,,,,
T 、 WXT, WA 、 及ぴ W B は、 以下のようにして計算される値である。 T, WXT, WA, and WB are values calculated as follows.
まず、 重合体ブロック [A] 及ぴ重合体ブロック [ B ] をそれぞれ重合するェ 程の前後において、 反応溶液中の各モノマー量をガスクロマトグラフィー分析に より定量する。 次に、 それぞれの重合工程で、 (重合体ブロックに取り込まれた モノマー量) == (仕込みモノマ一量 +重合工程前のモノマー量) 一 (重合工程後 の残留モノマー量) として測定する。 これにより W 1 AT 、 W XAA 、 ( 2BT + W 3BT ) 、 、W 2BB + W 3BB ) 、 W 1BT 、 WXTN WA 、 WB は計算される。 First, before and after the step of polymerizing the polymer block [A] and the polymer block [B], the amount of each monomer in the reaction solution is quantified by gas chromatography analysis. Next, in each polymerization step, the amount is measured as (amount of monomer incorporated in the polymer block) == (amount of charged monomer + amount of monomer before the polymerization step) / (amount of residual monomer after the polymerization step). Thus W 1 AT, W XAA, ( 2BT + W 3BT),, W 2BB + W 3BB), W 1BT, WXT N WA, WB is calculated.
W 2BT 、 W SBT は、 水素化前のブロック共重合体の iH— NMR分析によりビ ニル基とビニレン基の比率から計算される。  W 2BT and W SBT are calculated from the ratio of vinyl groups to vinylene groups by iH-NMR analysis of the block copolymer before hydrogenation.
、 は、 ェ11一 NMR分析により計算してそれぞれ求めた当該重合 体プロック [ B ] を重合する前後のビュル基とビニレン基の比率の差、 及ぴ当該 重合体ブロック [B] を重合する前後において、 前述した方法で計算して求めた プロック共重合体の重量比率を基に計算される。 The difference between the ratio of the butyl group to the vinylene group before and after the polymerization of the polymer block [B] calculated by NMR analysis, respectively, and Before and after the polymer block [B] is polymerized, it is calculated based on the weight ratio of the block copolymer obtained by the calculation described above.
本発明で使用する脂環式構造含有プロック共重合体は、 重合体ブロック [A] The alicyclic structure-containing block copolymer used in the present invention comprises a polymer block [A]
(以降 [A] と略記することがある) 及び重合体プロック [B] (以降 [B] と 略記することがある) の各 1個が結合した ( [A] — [B] ) 型のジブロック共 重合体であってもよい。 また、 ( [A] ― [B] 一 [A] ) 型や ( [B] ― (Hereinafter sometimes abbreviated as [A]) and polymer block [B] (hereinafter sometimes abbreviated as [B]), each of which is bound ([A]-[B]) type It may be a block copolymer. In addition, ([A]-[B]-[A]) type and ([B]-
[A] - [B] ) 型のトリブロック共重合体であってもよい。 さらに重合体プロ ック [A] と重合体ブロック [B] とが、 交互に合計 4個以上つながったブロッ ク共重合体であってもよい。 中でも ( [A] - [B] ― [A] ) 型のトリプロッ ク共重合体が、 柔軟性、 機械的強度、 及び生産性などの観点から好ましい。 また、 各重合体ブロックは、 分子長が同じでも異なってもよいが、 本発明の光拡散性樹 脂組成物の成形体の弾性率を高めるために、 少なくとも 2つの Aプロック (A 1 ブロック、 A 2ブロック) 間で、 分子長の比が異なることが好ましい。 この場合、 プロックの分子長の比 A 1 /A 2は、 好ましくは 1. 5〜 8、 より好ましくは 1. 7〜7、 特に好ましくは 2〜 6である。 尚、 各重合体のブロックの分子長は、 各 重合体プロックを重合する前後の分子量をゲル ·パーミエーション 'クロマトグ ラフィー分析により測定し、 その分子量増加分から計算される値である。  [A]-[B]) type triblock copolymer. Further, a block copolymer in which a total of four or more polymer blocks [A] and polymer blocks [B] are alternately connected may be used. Among them, ([A]-[B]-[A]) type triplock copolymers are preferred from the viewpoints of flexibility, mechanical strength, and productivity. Each polymer block may have the same or different molecular length. However, in order to increase the elastic modulus of the molded article of the light-diffusing resin composition of the present invention, at least two A blocks (A 1 block, It is preferable that the ratio of the molecular length be different between the A2 blocks). In this case, the ratio A 1 / A 2 of the molecular length of the block is preferably 1.5 to 8, more preferably 1.7 to 7, and particularly preferably 2 to 6. The molecular length of each polymer block is a value calculated by measuring the molecular weight before and after polymerizing each polymer block by gel permeation 'chromatography analysis and calculating the molecular weight increase.
本発明で使用する脂環式構造含有プロック共重合体の分子量は、 テトラヒ ドロ フラン (THF) を溶媒とするゲル ·パーミェ一シヨン 'クロマトグラフィー The molecular weight of the block copolymer containing an alicyclic structure used in the present invention is determined by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
(GPC) により測定されるポリスチレン換算の重量平均分子量 (Mw) が、 好 ましくは 20, 000〜 400, 000、 より好ましくは 30, 000〜 300, 000、 特に好ましくは 40, 000〜200, 000の範囲である。 脂環式構 造含有プロック共重合体の Mwが過度に小さいと成形体の機械的強度や耐熱性が 低下するおそれがあり、 逆に、 過度に大きいと樹脂製造段階での生産性や樹脂加 ェでの成形性などが低下する可能性がある。 The weight average molecular weight (Mw) in terms of polystyrene measured by (GPC) is preferably 20,000 to 400,000, more preferably 30,000 to 300,000, and particularly preferably 40,000 to 200,000. 000 range. If the Mw of the block copolymer containing an alicyclic structure is excessively small, the mechanical strength and heat resistance of the molded article may decrease.On the other hand, if the copolymer is excessively large, the productivity in the resin production stage and the resin addition may be reduced. There is a possibility that the moldability and the like may be reduced.
脂環式構造含有プロック共重合体の分子量分布は、 使用目的に応じて適宜選択 できるが、 ゲノレ ·パーミエーション 'クロマトグラフィにより測定されるポリス チレン換算の Mwと数平均分子量 (Μη) との比 Mw/Mnが、 3以下であるこ とが好ましく、 2以下であることがより好ましく、 1. 5以下であることが特に 好ましい。 Mw/Mnが上記範囲にあると、 成形体は機械的強度や耐熱性などに 優れる。 The molecular weight distribution of the block copolymer having an alicyclic structure can be appropriately selected depending on the purpose of use. The ratio Mw between the polystyrene-converted Mw and the number average molecular weight (Μη) measured by genole permeation 'chromatography is described. / Mn is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. preferable. When Mw / Mn is in the above range, the molded article is excellent in mechanical strength, heat resistance, and the like.
本発明に用いる脂環式構造含有プロック共重合体は、 たとえば以下のようにし て製造できる。  The block copolymer having an alicyclic structure used in the present invention can be produced, for example, as follows.
本発明に係る脂環式構造含有プロック共重合体の製造方法は、  The method for producing an alicyclic structure-containing block copolymer according to the present invention,
芳香族ビニル化合物、 環内に不飽和結合を有する不飽和脂環族ビュル化合物 (以後、 ビュルシクロアルケンと記す) 、 及び飽和脂環族ビュル化合物 (以降、 ビュルシクロアルカンと記す。 ) よりなる群から選ばれる少なくとも 1種以上を 合計 90重量%以上含有するモノマー混合物 (a) を重合させる工程 (1) と、 鎖状ビュル系化合物及び鎖状共役ジェン系化合物よりなる群から選ばれる少な くとも 1種以上を合計 30重量%以上含有するモノマー混合物 (b) を重合させ る工程 (2) と、  A group consisting of an aromatic vinyl compound, an unsaturated alicyclic bur compound having an unsaturated bond in a ring (hereinafter, referred to as bulcycloalkene), and a saturated alicyclic bur compound (hereinafter, referred to as bulcycloalkane); (A) polymerizing a monomer mixture (a) containing at least one member selected from the group consisting of at least 90% by weight, and at least one selected from the group consisting of a chain-like compound and a chain-like conjugated diene compound. A step (2) of polymerizing a monomer mixture (b) containing at least 30% by weight of at least one kind,
少なくとも工程 (1) 及び (2) を経て得られたブロック共重合体が不飽和結 合 (芳香環内の不飽和結合を含む) を有する場合、 その不飽和結合を水素化する 工程 (3) とを、 含むことを特徴とする。  When at least the block copolymer obtained through steps (1) and (2) has an unsaturated bond (including an unsaturated bond in an aromatic ring), the unsaturated bond is hydrogenated step (3) And characterized in that:
工程 (1) は、 モノマー混合物 (a) を重合して重合体プロック [A] を得る 工程である。 工程 (2) は、 モノマー混合物 (b) を重合して重合体ブロック Step (1) is a step of polymerizing the monomer mixture (a) to obtain a polymer block [A]. In step (2), the monomer mixture (b) is polymerized to form a polymer block.
[B] を得る工程である。 したがって、 重合反応の全工程中には、 工程 (1) 及 ぴ工程 (2) f 本発明に使用するプロック共重合体中の重合体ブロック [Α] 及ぴ重合体ブロック [Β] の数だけそれぞれ存在する。 This is the step of obtaining [B]. Therefore, during the entire process of the polymerization reaction, the number of the polymer blocks [Α] and the number of the polymer blocks [Β] in the block copolymer used in the present invention are equal to the number of the steps (1) and (2). Each exists.
尚、 モノマー混合物 (b) は、 芳香族ビュル化合物、 ビュルシクロアルケン、 及ぴビュルシク口アル力ンのいずれか 1種以上を合計量 70重量%以下の割合で 含んでいてもよい。  Incidentally, the monomer mixture (b) may contain at least one of an aromatic butyl compound, a bulcycloalkene, and a butylcycloalkene at a total amount of 70% by weight or less.
本発明の最も好ましいトリプロック共重合体を得る方法を例にして、 本発明の 製法をより具体的に説明する。 尚、 モノマー混合物 (a) を重合する工程が 2回 存在するため、 それぞれの工程で使用するモノマー混合物 (a) を、 モノマー混 合物 (a i ) 及ぴモノマー混合物 (a2 ) とする。 The production method of the present invention will be described more specifically by taking, as an example, a method for obtaining the most preferred triplock copolymer of the present invention. Since there are two steps of polymerizing the monomer mixture (a), the monomer mixture (a) used in each step is referred to as a monomer mixture ( ai ) and a monomer mixture (a 2 ).
まず、 モノマー混合物 (a i ) を重合して重合体プロック [A ] を得る。 次 いで、 前記重合体の有機溶媒溶液中でモノマー混合物 (b) を重合させることに より、 重合体ブロック [Ai ] 及ぴ重合体ブロック [ B ] からなるジブロック共 重合体を得る。 First, the monomer mixture ( ai ) is polymerized to obtain a polymer block [A]. Next, the monomer mixture (b) is polymerized in an organic solvent solution of the polymer. Thus, a diblock copolymer composed of the polymer block [Ai] and the polymer block [B] is obtained.
次いで、 前記ジブロック共重合体の溶液中で、 前記重合体ブロック [ B ] 側の 末端に、 モノマー混合物 (a 2 ) を重合させて、 重合体ブロック [ B ] の両末端 に重合体プロック [A] が 1つずつ結合したトリプロック共重合体を得る。 Next, in the solution of the diblock copolymer, a monomer mixture (a 2 ) is polymerized at the terminal on the polymer block [B] side, and a polymer block is attached to both terminals of the polymer block [B]. [A] is obtained one by one to obtain a triploc copolymer.
以上のようにして得られたブロック共重合体が、 不飽和結合 (芳香環中のもの を含む) を有する場合、 その不飽和部分を水素化反応によって飽和させることに より、 本発明の最も好ましい脂環式構造含有プロック共重合体を得る。  In the case where the block copolymer obtained as described above has an unsaturated bond (including one in an aromatic ring), the unsaturated portion is saturated by a hydrogenation reaction, so that the present invention is the most preferable. An alicyclic structure-containing block copolymer is obtained.
芳香族ビュル化合物としては、 たとえば、 スチレン、 ct—メチノレスチレン、 2 ーメチノレスチレン、 3—メチノレスチレン、 4—メチノレスチレン、 2 , 4—ジイソ プロピノレスチレン、 2, 4—ジメチノレスチレン、 4— t—プチノレスチレン、 5— tーブチノレ一 2—メチノレスチレン、 4—モノク口ロスチレン、 ジク口ロスチレン、 4一モノフノレオロスチレン、 4—フエエルスチレン等が挙げられる。  Examples of the aromatic vinyl compound include styrene, ct-methinolestyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methynolestyrene, 2,4-diisopropynolestyrene, and 2,4-dimethino Examples thereof include styrene, 4-t-butynolestyrene, 5-t-butynole-2-methynolestyrene, 4-monochlorostyrene, dichlorostyrene, 4-monophenololerostyrene, and 4-phenylstyrene.
ビュルシクロア ケンとしては、 たとえば、 4—ビュルシクロへキセン、 4— イソプロぺニノレシクロへキセン、 1—メチノレー 4—ビニノレシクロへキセン、 2— メチノレー 4―ビエノレシク口へキセン、 1—メチノレー 4ーィソプロぺニノレシク口へ キセン、 2—メチノレー 4一イソプロぺニノレシクロへキセン、 3—ビニノレシクロぺ ンテン、 4—ビ -Λ^ンクロペンテン、 5—ビニノレビシクロ [ 2 . 2 . 1 ] ヘプタ - 2—ェン等が挙げられる。  Examples of the bulcycloaken include 4-bulcyclohexene, 4-isopropininolecyclohexene, 1-methinole 4-vinylinolecyclohexene, 2-methinole 4-bienoresic mouth hexene, and 1-methinole 4-isopropeninolecin hexene. , 2-methinolay 4-isopropininolecyclohexene, 3-vinylinolecyclopentene, 4-bi-cyclopentene, 5-vinylinolecyclo [2.2.1] hept-2-ene, and the like.
ビュルシクロアルカンとしては、 たとえば、 ビエルシクロブタン、 ビュルシク 口ペンタン、 ビニノレシク口へキサン、 2 -ビニノレビシク口 [ 2 . 2 . 1 ] ヘプタ ン、 イソプロぺニノレシクロへキサン、 3—メチノレビニノレシクロへキサン、 4ーメ チルビニルシクロへキサン、 3—メチルイソプロぺニルシクロへキサン、 4—メ チルイソプロぺニルビ二ルシク口へキサン等が挙げられる。  Examples of the bulcycloalkane include biercyclobutane, bursik pentane, vininolesik hexane, 2-vininolevisic mouth [2.2.1] heptane, isopropininolecyclohexane, 3-methinolebininolecyclohexane, Examples thereof include 4-methylvinylcyclohexane, 3-methylisopropenylcyclohexane, and 4-methylisopropenylvinylsiloxane.
これらの化合物は、 ハロゲン基、 アルコキシ基、 ヒ ドロキシル基等の置換基を 有していてもよい。 また、 これらの化合物は、 それぞれ単独で用いてもよいし、 2種以上を組み合わせて用いることもできる。  These compounds may have a substituent such as a halogen group, an alkoxy group and a hydroxy group. These compounds may be used alone or in combination of two or more.
これらの中でも、 芳香族ビニルイ匕合物を用いると、 重合収率が高くなる。 さら にこれらの中でも、 スチレン、 ひーメチルスチレン、 2—メチノレスチレン、 3— メチルスチレン、 及び 4—メチルスチレンのいずれか 1種以上の芳香族ビュル化 合物を用いるのがより好ましい。 Among them, the use of the aromatic vinyl conjugate increases the polymerization yield. Furthermore, among these, styrene, high-methyl styrene, 2-methynolestyrene, 3- More preferably, one or more aromatic butyl compounds of methylstyrene and 4-methylstyrene are used.
鎖状ビエル系化合物としては、 たとえば、 エチレン、'プロピレン、 1—ブテン、 1一ペンテン、 1一へキセン、 1 _ヘプテン、 1—オタテン、 1—ノネン、 1 _ デセン、 1—ドデセン、 1—エイコセン、 4ーメチノレ _ 1一ペンテン、 4 , 6— ジメチル一 1—ヘプテン等の鎖状ォレフィン等が挙げられる。 中でも、 エチレン、 プロピレンが好ましい。  Examples of the linear biel compound include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1_heptene, 1-otaten, 1-nonene, 1_decene, 1-dodecene, 1- Examples include chain-like olefins such as eicosene, 4-methylino-11-pentene, and 4,6-dimethyl-11-heptene. Among them, ethylene and propylene are preferred.
鎖状共役ジェン系化合物としては、 たとえば、 1 , 3—ブタジエン、 イソプレ ン、 2, 3—ジメチル一 1 , 3—ブタジエン、 1 , 3 _ペンタジェン等が挙げら れる。 中でも 1 , 3—ブタジエン、 イソプレンが好ましい。  Examples of the chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Among them, 1,3-butadiene and isoprene are preferred.
上記方法において、 モノマー混合物 (a ) 及ぴモノマー混合物 (b ) は、 上記 以外のビュル系化合物を含んでいてもよい。 このようなビニル系化合物としては、 たとえば、 アクリロニトリル、 メタクリロニトリル、 1—シァノ一 1—クロロェ チレン等の二トリル系モノマー; 2—メ トキシカルボエル一プロペン、 2—エト キシカルボ二ループ口ペン、 2—プロポキシ力ルポ二ループ口ペン、 2—ブトキ シカルボ二ループ口ペン、 1—メ トキシカルボニルエチレン、 1—エトキシカル ボニノレエチレン、 1—プロポキシカノレポュノレエチレン、 1 _ブトキシカノレポ二ノレ エチレン等の (メタ) ァクリル酸エステル系モノマー; 1—カルポキシエチレン、 1—カルボキシー 1一メチルエチレン、 無水マレイン酸等の不飽和脂肪酸系モノ マー; 1—ヒ ドロカノレポニノレエチレン、 2—ヒ ドロカノレポ二ノレ一プロペン、 1— メチルカルボニルエチレン、 2—メチルカルボュル一プロペン、 N—フエニルマ レイ ミ ド等が挙げられる。  In the above method, the monomer mixture (a) and the monomer mixture (b) may contain a butyl compound other than the above. Such vinyl compounds include, for example, nitrile monomers such as acrylonitrile, methacrylonitrile, 1-cyano-1-chloroethylene; 2-methoxycarbyl-1-propene, 2-ethoxycarboloop-loop pen, 2-Propoxy lipoloop loop pen, 2-butoxycarboloop loop pen, 1-methoxycarbonylethylene, 1-ethoxycarboninoleethylene, 1-propoxycanolepounethylene, 1-butoxycanoleponinoleethylene (Meth) acrylate monomers such as 1-carboxyethylene, 1-carboxy-1-methylethylene, unsaturated fatty acid-based monomers such as maleic anhydride; 1-hydrocanoleponinoleethylene, 2-hydrocanolepo 2-propene, 1-methylcarbonylethylene, 2-methylca Boyuru one propene, N- Fueniruma Ray Mi de like.
上記モノマー混合物を用いてそれぞれの重合体プロックを重合する方法として は、 ラジカル重合、 ァ-オン重合、 カチオン重合、 配位ァニオン重合、 配位カチ オン重合等のいずれを用いてもよい。 中でも、 ラジカル重合、 ァニオン重合、 力 チオン重合等を、 リビング重合により行う方法が好ましく、 より好ましくはリビ ングァ二オン重合を用いる。 リビングァニオン重合により行う方法を用いた場合 に、 重合操作及ぴ後工程での水素化反応が容易になり、 得られる脂環式構造含有 プロック共重合体の透明性が向上する。 重合温度は、 重合開始剤の存在下、 通常 0 °C〜1 5 0 °C、 好ましくは 1 0 °C〜 1 0 0 °C、 特に好ましくは 2 0 °C〜8 0 °Cの範囲において行う。 リビングァニォ ン重合の場合は、 開始剤として、 たとえば、 n—プチノレリチウム、 s e c—プチ ルリチウム、 t _ブチルリチウム、 へキシルリチウム、 フエニルリチウム等のモ ノ有機リチウム;ジリチオメタン、 1 , 4ージリチォブタン、 1 , 4ージリチォ 一 2—ェチルシク口へキサン等の多官能性有機リチウム化合物等が使用可能であ る。 As a method of polymerizing each polymer block using the above monomer mixture, any of radical polymerization, ion polymerization, cationic polymerization, coordination anion polymerization, coordination cation polymerization and the like may be used. Above all, a method in which radical polymerization, anion polymerization, force polymerization, or the like is performed by living polymerization is preferable, and living polymerization is more preferably used. In the case of using the method of living anion polymerization, the hydrogenation reaction in the polymerization operation and the subsequent steps is facilitated, and the transparency of the obtained alicyclic structure-containing block copolymer is improved. The polymerization temperature is usually 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C, particularly preferably 20 ° C to 80 ° C in the presence of a polymerization initiator. Do. In the case of living anion polymerization, as an initiator, for example, monoorganic lithium such as n-butylinolelithium, sec-butyllithium, t_butyllithium, hexyllithium, phenyllithium; dilithiomethane, 1,4-dilithiobutane, Polyfunctional organic lithium compounds such as 1,4-diethyl-2-ethylsilyl hexane can be used.
重合反応形態は、 溶液重合、 スラリー重合等のいずれでも構わないが、 溶液重 合を用いると、 反応熱の除去が容易である。 この場合、 各工程で得られる重合体 が溶解する不活性溶媒を用いる。 使用する不活性溶媒としては、 たとえば、 n _ ブタン、 n—ペンタン、 ィソペンタン、 n—へキサン、 η—ヘプタン、 イソオタ タン等の脂肪族炭化水素類;シクロペンタン、 シクロへキサン、 メチルシクロべ ンタン、 メチルシク口へキサン、 デカリン、 ビシクロ [ 4 . 3 . 0 ] ノナン、 ト リシクロ [ 4 . 3 . 0 . I 2' 5 ] デカン等の脂環式炭化水素類;ベンゼン、 トル ェン等の芳香族炭化水素類等が挙げられる。 中でも脂環式炭化水素類を用いると、 後述する水素化反応にも不活性な溶媒としてそのまま使用でき、 プロック共重合 体の溶解性も良好であるため好ましい。 これらの溶媒は、 それぞれ単独で用いて もよいし、 あるいは 2種類以上を組み合わせて使用することもできる。 これらの 溶媒使用量は、 全使用モノマー 1 0 0重量部に対して、 通常 2 0 0〜 2 0 0 0重 量部である。 The type of polymerization reaction may be any of solution polymerization, slurry polymerization and the like, but the use of solution polymerization makes it easy to remove the heat of reaction. In this case, an inert solvent in which the polymer obtained in each step is dissolved is used. Examples of the inert solvent used include aliphatic hydrocarbons such as n_butane, n-pentane, isopentane, n-hexane, η-heptane, and isootatan; cyclopentane, cyclohexane, methylcyclopentane, hexane Mechirushiku port, decalin, bicyclo [4 3 0..] nonane, preparative Rishikuro [4 3 0 I 2 '5...] alicyclic hydrocarbons such as decane, benzene, aromatic such torr E down Hydrocarbons and the like. Among them, the use of alicyclic hydrocarbons is preferable because it can be used as it is as an inert solvent also in the hydrogenation reaction described below and the solubility of the block copolymer is good. Each of these solvents may be used alone, or two or more of them may be used in combination. The amount of these solvents to be used is usually 200 to 2000 parts by weight based on 100 parts by weight of the total monomers used.
それぞれのモノマー混合物が 2種以上の成分からなる場合、 或る 1成分の連鎖 だけが長くなるのを防止するために、 ランダマイザ一等を使用することができる。 特に重合反応をァニオン重合により行う場合には、 ルイス塩基化合物等をランダ マイザ一として使用するのが好ましい。 ルイス塩基化合物としては、 たとえば、 ジメチノレエーテノレ、 ジェチノレエーテノレ、 ジイソプロピノレエ一テル、 ジブチノレエ一 テル、 テトラヒ ドロフラン、 ジフエニノレエ一テノレ、 エチレングリコーノレジェチノレ エーテノレ、 エチレングリコーノレメチノレフェュノレエーテノレ等のエーテノレイ匕合物; テ トラメチノレエチレンジァミン、 トリメチ^^ァミン、 トリェチルァミン、 ピリジン 等の第 3級ァミン化合物;力リゥムー tーァミルォキシド、 力リゥムー t—ブチ ルォキシド等のアルカリ金属アルコキシド化合物; トリフエニルホスフィン等の ホスフィン化合物;等が挙げられる。 これらのルイス塩基化合物は、 それぞれ単 独で用いてもよいし、 あるいは 2種類以上を組み合わせて使用することもできる。 上記方法で重合反応して得られるプロック共重合体の分子量は、 THFを溶媒 とする GPCにより測定されるポリスチレン換算の Mwで、 好ましくは 20, 0 00〜 400, 000、 より好ましくは 30, 000〜 300, 000、 特に好 ましくは 40, 000〜200, 000の範囲にする。 また、 分子量分布 MwZ Μηは、 3以下であることが好ましく、 2以下であることがより好ましく、 1. 5以下であることが特に好ましい。 Mw及ぴ MwZMriが上記範囲となるように すると、 脂環式構造含有ブロック共重合体 (後述する水素化反応を行う場合は水 素化後の脂環式構造含有ブロック共重合体) の機械強度や耐熱性が向上する。 さ らに水素化反応を行った場合には水素化率が高くなり、 得られる脂環式構造含有 ブロック共重合体の透明性や熱安定性等も向上する。 When each monomer mixture is composed of two or more components, a randomizer or the like can be used to prevent a chain of one component from becoming long. In particular, when the polymerization reaction is carried out by anion polymerization, it is preferable to use a Lewis base compound or the like as a randomizer. Lewis base compounds include, for example, dimethinooleatenole, getinoleatenole, diisopropinoleatel, dibutinoleatel, tetrahydrofuran, dipheninoleatenole, ethyleneglycoreleetenole, ethyleneglycoreleatenole, ethyleneglycorelemethino Ethenolay conjugates, such as refenoleatenole; tertiary amine compounds such as tetramethinoleethylenediamine, trimethy ^ amine, triethylamine, pyridine, etc .; tertiary amine compounds, tertiary amine compounds; Alkali metal alkoxide compounds such as luoxide; phosphine compounds such as triphenylphosphine; and the like. Each of these Lewis base compounds may be used alone, or two or more of them may be used in combination. The molecular weight of the block copolymer obtained by the polymerization reaction according to the above method is preferably 20,000 to 400,000, more preferably 30,000, as Mw in terms of polystyrene measured by GPC using THF as a solvent. To 300,000, particularly preferably in the range of 40,000 to 200,000. Further, the molecular weight distribution MwZΜη is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and MwZMri are within the above range, the mechanical strength of the alicyclic structure-containing block copolymer (or the alicyclic structure-containing block copolymer after hydrogenation when a hydrogenation reaction described below is performed). And heat resistance is improved. Further, when a hydrogenation reaction is performed, the hydrogenation rate increases, and the transparency, thermal stability, and the like of the obtained alicyclic structure-containing block copolymer also improve.
上記の重合方法を用いて得られたプロック共重合体は、 その中に不飽和結合 (芳香環部分のものも含む) が存在する場合には、 該不飽和結合を水素化するこ とにより本発明の脂環式構造含有ブロック共重合体とすることができる。  The block copolymer obtained by the above polymerization method, when an unsaturated bond (including an aromatic ring portion) is present therein, is obtained by hydrogenating the unsaturated bond. The alicyclic structure-containing block copolymer of the present invention can be obtained.
不飽和結合の水素化方法、 反応形態等は特に限定されず、 公知の方法にしたが つて行えばよいが、 水素化率を高くでき、 重合体鎖切断反応の少ない水素化方法 が好ましい。 このような好ましい水素化方法としては、 ニッケル、 コバルト、 鉄、 チタン、 ロジウム、 パラジウム、 白金、 ルテニウム、 レニウム等から選ばれる少 なくとも 1種の金属を含む触媒を用いて行う方法が挙げられる。 水素化触媒は、 不均一系触媒、 均一系触媒のいずれも使用可能であり、 水素化反応は有機溶媒中 で行うのが好ましい。  The method of hydrogenating the unsaturated bond, the reaction form, and the like are not particularly limited, and may be performed according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and causes less polymer chain scission reaction is preferable. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, any of a heterogeneous catalyst and a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.
不均一系触媒は、 金属又は金属化合物のままで、 又は適当な担体に担持して用 いることができる。 担体としては、 たとえば、 活性炭、 シリカ、 アルミナ、 炭酸 カルシウム、 チタニア、 マグネシア、 ジルコニァ、 ケイソゥ土、 炭化珪素、 フッ 化カルシウム等が挙げられる。 触媒の担持量は、 触媒と担体との合計量に対して、 通常、 0. 1 ~60重量%、 好ましくは 1〜50重量%の範囲である。 担持型触 媒としては、 たとえば、 比表面積が 100〜 500 m2 Zg、 平均細孔径 100 〜1 0 0 0 A、 好ましくは 2 0 0〜5 0 O Aを有するものが好ましい。 上記の比 表面積の値は窒素吸着量を測定し、 B E T式を用いて算出した値であり、 平均細 孔径の値は水銀圧入法により測定した値である。 The heterogeneous catalyst can be used as it is, as a metal or a metal compound, or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like. The amount of the supported catalyst is usually in the range of 0.1 to 60% by weight, preferably 1 to 50% by weight, based on the total amount of the catalyst and the carrier. Examples of the supported catalyst include a specific surface area of 100 to 500 m 2 Zg and an average pore diameter of 100. Those having を 100 A, preferably 200-500 OA are preferred. The value of the specific surface area is a value calculated by measuring the amount of adsorbed nitrogen and using the BET equation, and the value of the average pore diameter is a value measured by a mercury intrusion method.
均一系触媒としては、 たとえば、 ニッケル、 コバルト、 チタン又は鉄化合物と 有機金属化合物 (たとえば、 有機アルミニウム化合物、 有機リチウム化合物) と を組み合わせた触媒; ロジウム、 パラジウム、 白金、 ルテニウム、 レニウム等の 遷移金属錯体触媒等を用いることができる。 ニッケル、 コバルト、 チタン又は鉄 化合物としては、 たとえば、 各種金属のァセチルァセトナト化合物、 カルボン酸 塩、 シクロペンタジェニル化合物等が用いられる。 有機アルミユウム化合物とし ては、 トリェチルアルミニウム、 トリイソプチルアルミニウム等のアルキルァノレ ミニゥム ; ジェチルアルミニウムクロリ ド、 ェチルアルミニウムジクロリ ド等の ハロゲン化アルミニウム ;ジィソブチルアルミ二ゥムハイ ドライ ド等の水素化ァ ルキルアルミニウム等が挙げられる。  Examples of the homogeneous catalyst include a catalyst obtained by combining a nickel, cobalt, titanium or iron compound with an organometallic compound (eg, an organoaluminum compound, an organolithium compound); transition metals such as rhodium, palladium, platinum, ruthenium, and rhenium; A complex catalyst or the like can be used. As the nickel, cobalt, titanium or iron compound, for example, acetyl acetonato compounds of various metals, carboxylate salts, cyclopentagenenyl compounds and the like are used. Examples of the organic aluminum compound include alkyl phenols such as triethylaluminum and triisobutylaluminum; aluminum halides such as getylaluminum chloride and ethylaluminum dichloride; and hydrogenation such as disobutylaluminum hydride. Alkyl aluminum and the like.
有機金属錯体触媒としては、 たとえば、 ジヒドリ ド一テトラキス (トリフエ二 ノレホスフィン) ノレテニゥム、 ジヒ ドリ ド一テトラキス (トリフエニルホスフィ ン) 鉄、 ビス (シクロォクタジェン) ニッケル、 ビス (シク口ペンタジェニル) ュッケル等の遷移金属錯体が挙げられる。  Examples of the organometallic complex catalyst include dihydrido-tetrakis (triphenyl norephosphine) norethenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentagenenyl) And transition metal complexes such as Huckel.
これらの水素化触媒は、 それぞれ単独で用いてもよいし、 2種以上を組み合わ せて使用してもよい。 水素化触媒の使用量は、 重合体 1 0 0重量部に対して、 通 常、 0. 0 1〜: L 0 0重量部、 好ましくは 0. 0 5〜5 0重量部、 より好ましく は 0. :!〜 3 0重量部である。  Each of these hydrogenation catalysts may be used alone, or two or more of them may be used in combination. The amount of the hydrogenation catalyst to be used is usually from 0.01 to: L00 parts by weight, preferably from 0.05 to 50 parts by weight, more preferably from 0 to 100 parts by weight of the polymer. : 30 to 30 parts by weight.
水素化反応温度は、 通常、 1 0 °C〜 2 5 0 °C、 好ましくは 5 0 °C〜 2 0 0 °C、 より好ましくは 8 0°C〜1 8 0°Cであるときに水素化率が高くなり、 分子切断も 減少する。 また水素圧力は、 通常、 0. l MP a〜3 0MP a、 好ましくは 1 M P a〜2 0MP a、 より好ましくは 2MP a〜l OMP aであると水素化率が高 くなり、 分子鎖切断も減少し、 操作性にも優れる。  The hydrogenation reaction temperature is usually from 10 ° C to 250 ° C, preferably from 50 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C. Conversion increases and molecular cleavage decreases. When the hydrogen pressure is usually 0.1 MPa to 30 MPa, preferably 1 MPa to 20 MPa, more preferably 2 MPa to 1 OMPa, the hydrogenation rate increases and the molecular chain breaks. And the operability is excellent.
脂環式構造含有プロック共重合体の水素化率は、 iH— NMRによる測定にお いて、 主鎖及ぴ側鎖の炭素一炭素不飽和結合、 芳香環ゃシクロアルケン環の炭素 —炭素不飽和結合のいずれもが、 好ましくは 9 0 %以上、 より好ましくは 9 7 % 以上、 さらに好ましくは 9 9 %以上となるようにする。 水素化率が高いと、 得ら れる脂璟式構造含有プロック共重合体の低複屈折性、 熱安定性等が向上する。 プロック共重合体の水素化反応溶液又は重合反応溶液には、 水素化触媒及ぴノ 又は重合触媒が含まれているので、 これを濾過、 遠心分離等の方法により除去し た後、 反応溶液から脂環式構造含有プロック共重合体を回収する。 The hydrogenation rate of the block copolymer containing an alicyclic structure can be measured by iH-NMR using carbon-carbon unsaturated bonds in the main chain and side chains, and carbon-carbon unsaturated carbon in the aromatic ring and cycloalkene ring. All of the bonds are preferably 90% or more, more preferably 97% More preferably, it is set to 99% or more. When the hydrogenation rate is high, the obtained biblock copolymer having an aliphatic structure has improved low birefringence and thermal stability. Since the hydrogenation reaction solution or polymerization reaction solution of the block copolymer contains a hydrogenation catalyst and / or a polymerization catalyst, it is removed by a method such as filtration or centrifugation, and then the reaction solution is removed from the reaction solution. An alicyclic structure-containing block copolymer is recovered.
脂環式構造含有プロック共重合体の反応溶液からの回収方法は特に限定されな レ、。 例えば、 脂環式構造含有プロック重合体溶液から溶媒をスチームストリッピ ングにより除去するスチーム凝固法、 溶媒を減圧下で加熱して除去する直接脱溶 媒法、 溶液を脂環式構造含有プロック共重合体の貧溶媒中に注いで凝固させる溶 媒凝固法等の公知の方法で回収することができる。  The method for recovering the alicyclic structure-containing block copolymer from the reaction solution is not particularly limited. For example, a steam coagulation method in which the solvent is removed from the alicyclic structure-containing block polymer solution by steam stripping, a direct desolvent method in which the solvent is removed by heating under reduced pressure, and a solution in which the alicyclic structure-containing block is used. The polymer can be collected by a known method such as a solvent coagulation method in which the polymer is poured into a poor solvent and solidified.
回収する脂環式構造含有プロック共重合体の形態は、 その後の溶融成形加工に 有利なように、 通常、 ペレツトにされるが、 これに限定されない。 直接脱溶媒法 を用いる場合は、 例えば、 溶融状態の脂環式構造含有ブロック共重合体をダイか らストランド状に押出し、 冷却後、 ペレタイザ一で力ッティングしてペレツトに することができる。 凝固法を用いる場合は、 例えば、 得られた凝固物を乾燥した 後、 押出し機により溶融押出しし、 上記と同様にペレットにすることができる。  The form of the recovered alicyclic structure-containing block copolymer is usually pelletized so as to be advantageous for the subsequent melt molding, but is not limited thereto. In the case of using the direct desolvation method, for example, a molten alicyclic structure-containing block copolymer may be extruded from a die into a strand, cooled, and then forced into a pellet by a pelletizer to form a pellet. When the coagulation method is used, for example, the obtained coagulate can be dried and then melt-extruded with an extruder to form pellets in the same manner as described above.
充填剤  filler
本発明に用いる充填剤は、 有機充填剤でも無機充填剤でもよい。  The filler used in the present invention may be an organic filler or an inorganic filler.
有機充填剤としては、 脂環式構造含有プロック共重合体中で透明微粒子を形成 し得る、 重合体又はその架橋物が挙げられる。 具体的には、 該重合体又はその架 橋物を厚さ 1 mmの板状成形体にしたときの全光線透過率が、 7 0 %以上のもの が好ましく、 8 0 %以上のものがより好ましく、 9 0 %以上のものが特に好まし レ、。 全光線透過率が低過ぎると、 重合体内部での光損失により、 得られる光拡散 性成形体の光透過率が低下する。 ここでいう全光線透過率は、 一般には 4 0 0〜 Examples of the organic filler include a polymer capable of forming transparent fine particles in an alicyclic structure-containing block copolymer or a crosslinked product thereof. Specifically, when the polymer or its bridge is formed into a plate-like molded product having a thickness of 1 mm, the total light transmittance is preferably 70% or more, more preferably 80% or more. Preferably, those with 90% or more are particularly preferred. If the total light transmittance is too low, the light transmittance of the obtained light diffusing molded article is reduced due to light loss inside the polymer. The total light transmittance here is generally 400 to
7 0 0 n mの可視光であるが、 例えば、 透過、 拡散させたい光線がこれ以外の波 長の場合は、 その目的とする波長において上記の光線透過率を有していることが 好ましい。 Although it is a visible light of 700 nm, for example, when a light beam to be transmitted or diffused has any other wavelength, it is preferable to have the above-mentioned light transmittance at a target wavelength.
また、 上記有機充填剤の屈折率は、 脂環式構造含有プロック共重合体の屈折率 を n l、 有機充填剤の屈折率を n 2としたときに、 n l Z n 2又は n 2 Z n 1の 下限が、 好ましくは 1 . 0 1、 より好ましくは 1 . 0 1 5、 特に好ましくは 1 . 0 2 5、 また上限が、 好ましくは 1 . 2、 より好ましくは 1 . 1である。 また、 n 2は、 好ましくは 1 . 4〜1 . 8、 より好ましくは 1 . 4 5〜1 . 7 2である。 この屈折率比が低すぎると得られる成形体の光拡散性が低くなる。 屈折率比が高 過ぎると得られる成形体の光透過率が低下する。 なお、 この屈折率は、 使用目的 に応じた波長における値である。 屈折率は用いる重合体の種類によって異なるが、 例えば、 フエュル基を含有するモノマーの使用量などによりその値を調節できる。 フエ二ル基を含有するモノマーの使用量が多いほど重合体の屈折率は高くなり易 レ、。 The refractive index of the organic filler is nlZn2 or n2Zn1 when the refractive index of the alicyclic structure-containing block copolymer is nl and the refractive index of the organic filler is n2. of The lower limit is preferably 1.01, more preferably 1.015, particularly preferably 1.025, and the upper limit is preferably 1.2, more preferably 1.1. Also, n2 is preferably from 1.4 to 1.8, more preferably from 1.45 to 1.72. If this refractive index ratio is too low, the light diffusibility of the obtained molded article will be low. If the refractive index ratio is too high, the light transmittance of the obtained molded article decreases. The refractive index is a value at a wavelength according to the purpose of use. The refractive index varies depending on the type of the polymer used, but the value can be adjusted by, for example, the amount of a monomer containing a ferul group. As the amount of the monomer containing a phenyl group increases, the refractive index of the polymer tends to increase.
このような有機充填剤としては、 (1 ) スチレン類、 アクリロニトリル類など のビュル系モノマー; (メタ) アクリル酸メチル、 (メタ) アクリル酸ェチル、 Examples of such organic fillers include (1) butyl monomers such as styrenes and acrylonitriles; methyl (meth) acrylate, ethyl (meth) acrylate,
(メタ) アクリル酸ブチル、 などの (メタ) アクリル酸エステル類モノマー;な どの単独重合体又は共重合体、 (2 ) 上記モノマーと、 それらと共重合可能なジ エチレングリコールジ (メタ) アタリレート、 1 , 3—プチレングリコールジ(Meth) acrylate monomers such as butyl (meth) acrylate; homopolymers or copolymers such as (2) the above monomers and diethylene glycol di (meth) acrylate which can be copolymerized with them; , 1,3—butylene glycol di
(メタ) アタリ レート、 ジビエルベンゼン、 などの多官能モノマーとの共重合体、Copolymers with polyfunctional monomers such as (meth) atalilate, dibielbenzene,
( 3 ) ポリシロキサン系重合体、 などが挙げられる。 (3) Polysiloxane-based polymers, and the like.
上記有機充填剤は、 成形体中で微粒子としての形状を維持していることが必要 である。 成形時に形状が維持できなければ、 後述のように、 均一な光拡散性の成 形体が得られない。 そのため、 架橋物であることが好ましい。 多官能モノマーを 加えて共重合した共重合体などのように、 重合時に架橋可能のものは、 架橋して 粒子形状のものを得ることが好ましい。 重合後に粒子の形状にした後、 または粒 子形状に重合した後に、 紫外線照射などの方法で架橋した微粒子も使用できる。 具体的には、 架橋ポリメタクリル酸メチル、 架橋ポリスチレン、 架橋ポリアタリ ル酸ナトリウム、 架橋シリコーン、 架橋アクリル一スチレン共重合体、 架橋ポリ ジメチルシロキサン、 などが例示される。  The organic filler needs to maintain the shape as fine particles in the molded body. If the shape cannot be maintained during molding, a uniform light-diffusing molded body cannot be obtained as described later. Therefore, it is preferably a crosslinked product. Those which can be crosslinked at the time of polymerization, such as a copolymer obtained by adding a polyfunctional monomer and copolymerizing, are preferably crosslinked to obtain particles. Fine particles which are crosslinked by a method such as irradiation with ultraviolet light after being formed into particles after polymerization or after being polymerized into particles can also be used. Specific examples thereof include cross-linked polymethyl methacrylate, cross-linked polystyrene, cross-linked sodium polyacrylate, cross-linked silicone, cross-linked acryl-styrene copolymer, cross-linked polydimethylsiloxane, and the like.
上記の有機充填剤の中でも、 ポリスチレン系重合体、 ポリシロキサン系重合体 又はそれらの架橋物からなる微粒子が好適である。  Among the organic fillers described above, fine particles composed of a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof are preferred.
本発明に用いられる上記重合体を微粒子にする方法は、 特に限定されないが、 懸濁重合などにより粒子とすることができる。 例えば、 スチレンとジビュルベン ゼンの共重合のように多官能モノマーを含有するモノマーを懸濁重合すれば、 架 橋重合体微粒子が得られ、 重合後、 洗浄、 乾燥し、 風力ミクロンセパレーターな どをもちレヽて分級すれば、 所望の粒径分布の架橋微粒子が得られる。 The method of converting the above polymer used in the present invention into fine particles is not particularly limited, but the particles can be formed by suspension polymerization or the like. For example, styrene and dibulbene If suspension-polymerization of a monomer containing a polyfunctional monomer, such as copolymerization of zen, is performed, crosslinked polymer fine particles can be obtained.After polymerization, washing, drying, and classification using a wind micron separator, etc. Thus, crosslinked fine particles having a desired particle size distribution can be obtained.
無機充填剤としては、 脂環式構造含有プロック共重合体中で透明微粒子を形成 し得る無機微粒子を例示することができる。 具体的には、 シリカ、 シリカアルミ ナ、 アルミナ、 水酸化アルミニウム、 水酸化マグネシウム、 タノレク、 ガラスフレ ーク、 ガラスビーズ、 ケィ酸ナトリウム、 などを挙げることができる。 これらの 無機充填剤の中では、 シリカ、 タルクが透明性に優れ好ましい。 これらの無機充 填剤は、 1種または 2種以上組み合わせて用いることも、 透明有機充填剤と組み 合わせて用いることもできる。  Examples of the inorganic filler include inorganic fine particles capable of forming transparent fine particles in an alicyclic structure-containing block copolymer. Specific examples include silica, silica alumina, alumina, aluminum hydroxide, magnesium hydroxide, tanolek, glass flakes, glass beads, sodium silicate, and the like. Among these inorganic fillers, silica and talc are preferable because of their excellent transparency. These inorganic fillers can be used alone or in combination of two or more, or can be used in combination with a transparent organic filler.
また、 例えば二軸混練機などにより、 脂環式構造含有プロック共重合体を溶融 混練して上記無機充填剤を配合する場合には、 シリンダーゃスクリユーの磨耗に よる樹脂組成物の色調悪化を避けるために、 上記無機充填剤の中でも硬度の低い もの、 例えばタルクなどを用いることが好ましい。  In addition, in the case of blending the inorganic filler by melt-kneading the block copolymer having an alicyclic structure with a twin-screw kneader or the like, avoid deterioration of the color tone of the resin composition due to abrasion of the cylinder screw. For this reason, among the above-mentioned inorganic fillers, it is preferable to use one having a low hardness, such as talc.
有機充填剤及び/又は無機充填剤の粒子径は、 特に限定されないが、 平均粒径 の下限は好ましくは 1 m、 より好ましくは 3 /ζ ηι、 特に好ましくは 5 μ mであ る。 上限は好ましくは 3 0 m、 より好ましくは 2 0 μ m、 特に好ましくは 1 5 mである。 小さ過ぎると本発明の組成物の光拡散性は増大するが光透過率が低 下し、 大き過ぎると光透過率は増大するが光拡散性が低下し、 さらに成形体の表 面平滑性が低下したり、 ムラが発生したりすることがある。  The particle size of the organic filler and / or the inorganic filler is not particularly limited, but the lower limit of the average particle size is preferably 1 m, more preferably 3 / ζηι, and particularly preferably 5 μm. The upper limit is preferably 30 m, more preferably 20 μm, particularly preferably 15 m. If it is too small, the light diffusivity of the composition of the present invention increases, but the light transmittance decreases.If it is too large, the light transmissivity increases but the light diffusivity decreases, and the surface smoothness of the molded article further decreases. It may be reduced or unevenness may occur.
有機充填剤及び Z又は無機充填剤は、 球状のものを多く含むほど好ましい。 球 状とは微粒子の短径ノ長径が、 好ましくは 0 . 6以上、 より好ましくは 0 . 8以 上、 特に好ましくは 0 . 9以上であり、 角を有していないものをいう。 短径とは、 ひとつの微粒子の最も小さい径をいう。 長径とは同じ微粒子の最も大きな径をい う。 本発明においては、 用いる微粒子中の球状微粒子の割合が 8 0 %以上である ことが好ましく、 9 0 %以上であることがより好ましく、 9 5 %以上であること が特に好ましい。 短径、 長径、 平均粒径、 角の有無については、 顕微鏡写真の映 像を基に測定すればよい。 球状でないものが多いと、 成形時に分散が不均一にな つたり、 配向性を有して均一な光拡散性の成形体を得ることが困難となり易い。 なお、 有機充填剤及び/又は無機充填剤は、' 1種類である必要はなく、 例えば、 光透過性と光拡散性を調節する目的や、 使用環境に合わせる目的で、 複数種の有 機充填剤及び Z又は無機充填剤を併用してもよレ、。 It is preferable that the organic filler and the Z or inorganic filler include a large number of spherical fillers. The term “spherical” refers to fine particles having a minor axis and a major axis of preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 0.9 or more, and have no corner. The minor diameter refers to the smallest diameter of one fine particle. The longest diameter is the largest diameter of the same fine particles. In the present invention, the ratio of the spherical fine particles in the fine particles to be used is preferably at least 80%, more preferably at least 90%, particularly preferably at least 95%. The minor axis, major axis, average particle diameter, and the presence or absence of a corner may be measured based on a micrograph image. If there are many non-spherical ones, dispersion tends to be non-uniform at the time of molding, or it becomes difficult to obtain a molded article having uniform orientation and light diffusion. The organic filler and / or the inorganic filler need not be a single kind.For example, a plurality of kinds of organic fillers may be used for the purpose of adjusting the light transmittance and light diffusivity and for the purpose of adjusting to the use environment. Agent and Z or an inorganic filler may be used in combination.
有機充填剤及び/又は無機充填剤の樹脂組成物中の量は、 目的とする光拡散成 形体の光路長により異なる。 例えば、 1 0 0 の厚さの光拡散板においては、 通常、 1 0〜3 0重量%でぁり、 1 mmの厚さの光拡散板においては、 通常、 1 〜1 5重量%でぁり、 1 O mmの厚さの光拡散板においては、 通常、 0 . 1〜2 重量%であり、 1 0 O mmの厚さの光拡散板においては、 通常、 0 . 0 1〜0 . 2重量%である。 これは、 光路長が短い (厚さが薄い) 場合は、 多量に有機充填 剤及び 又は無機充填剤を配合しないと十分に光拡散性が得られないためである。 一方、 光路長が長い (厚さが厚い) 場合には、 少量の有機充填剤おょぴ /または 無機充填剤を配合しただけでも、 光透過性が低下してしまうので、 透明微粒子の 量を少なくしなければならないからである。  The amount of the organic filler and / or the inorganic filler in the resin composition varies depending on the desired optical path length of the light diffusion molded article. For example, in the case of a light diffusion plate having a thickness of 100, the amount is usually from 10 to 30% by weight, and in the case of a light diffusion plate having a thickness of 1 mm, it is usually from 1 to 15% by weight. For a light diffusing plate having a thickness of 10 mm, the content is usually 0.1 to 2% by weight, and for a light diffusing plate having a thickness of 10 mm, usually 0.1 to 0.1% by weight. 2% by weight. This is because if the optical path length is short (thin thickness), sufficient light diffusivity cannot be obtained unless a large amount of the organic filler and / or the inorganic filler is blended. On the other hand, when the optical path length is long (thick), even if a small amount of the organic filler and / or the inorganic filler is blended, the light transmittance is reduced. This is because it must be reduced.
任意成分  Optional ingredients
本発明に係る光拡散性樹脂組成物は、 上記脂環式構造含有プロック共重合体と 充填剤の他に、 各種配合剤が配合してあっても良い。  The light diffusing resin composition according to the present invention may contain various compounding agents in addition to the alicyclic structure-containing block copolymer and the filler.
配合剤としては、 格別限定はないが、 酸化防止剤、 熱安定剤、 光安定剤、 耐候 安定剤、 紫外線吸収剤、 近赤外線吸収剤等の安定剤;脂肪族アルコールのエステ ル、 多価アルコールの部分エステルおよび部分エーテル等の滑剤;可塑剤;染料 や顔料等の着色剤;帯電防止剤等が挙げられる。 さらに、 樹脂の劣化による黄変 性がもたらす外観不良を防ぐために、 青色着色剤 (ブルーイング剤) を添加して もよレ、。 これらの配合剤は、 単独で、 あるいは 2種以上を組み合せて用いること ができ、 その配合量は本発明の目的を損ねない範囲で適宜選択される。  There are no particular limitations on the compounding agents, but stabilizers such as antioxidants, heat stabilizers, light stabilizers, weather stabilizers, ultraviolet absorbers, near infrared absorbers, etc .; esters of aliphatic alcohols, polyhydric alcohols Lubricants such as partial esters and partial ethers; plasticizers; coloring agents such as dyes and pigments; antistatic agents and the like. In addition, a blue colorant (blueing agent) may be added to prevent poor appearance caused by yellowing due to deterioration of the resin. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.
酸化防止剤としては、 フエノール系酸化防止剤、 リン系酸化防止剤、 ィォゥ系 酸化防止剤などが挙げられ、 これらの中でもフエノール系酸化防止剤、 特にアル キル置換フエノール系酸化防止剤が好ましい。 これらの酸ィヒ防止剤を配合するこ とにより、 透明性、 低吸水性等を低下させることなく、 成形時の酸化劣化等によ る成形物の着色や強度低下を防止できる。  Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a zeolite-based antioxidant. Among these, a phenol-based antioxidant, particularly an alkyl-substituted phenol-based antioxidant is preferable. By blending these acid proofing agents, it is possible to prevent coloring and strength reduction of the molded article due to oxidative deterioration during molding without reducing transparency, low water absorption and the like.
これらの酸化防止剤は、 それぞれ単独で、 あるいは 2種以上を組み合わせて用 いることができ、 その配合量は、 本発明の目的を損なわれない範囲で適宜選択さ れるが、 脂環式構造含有プロック共重合体 1 00重量部に対して通常 0. 001 〜5重量部、 好ましくは 0. 01〜:!重量部である。 These antioxidants may be used alone or in combination of two or more. The blending amount is appropriately selected within a range not to impair the object of the present invention, but is usually 0.001 to 5 parts by weight based on 100 parts by weight of the alicyclic structure-containing block copolymer. , Preferably 0.01-:! Parts by weight.
曲げ弾性率  Flexural modulus
本発明に係る光拡散性樹脂組成物は、 AS TM— D 790法に基づいて厚さ 2 mmの板に成形して測定された、 25 °Cにおける曲げ弾性率が 10, 000〜 2 7, 000 k g f /cm2 、 好ましくは 14, 000〜 24, 000 k g f / c m2 、 より好ましくは 1 7, 000〜 21, 000 k g f/cm2 である。 曲げ 弾性率が上記範囲にあると、 成形離型時のゲートの割れ等がなく、 切削加工時の クラック等の発生も防止できる。 The light-diffusing resin composition according to the present invention has a flexural modulus at 25 ° C. of 10,000 to 27, measured at a temperature of 25 ° C., measured by molding into a plate having a thickness of 2 mm based on the ASTM-D790 method. 000 kgf / cm 2 , preferably 14,000 to 24,000 kgf / cm 2 , and more preferably 17,000 to 21,000 kgf / cm 2 . When the flexural modulus is in the above range, there is no cracking of the gate at the time of molding release, and the occurrence of cracks at the time of cutting can be prevented.
光拡散性樹脂組成物の調製方法 (製造方法)  Preparation method of light diffusing resin composition (production method)
本発明に係る光拡散性樹脂組成物は、 上述した脂環式構造含有プロック共重合 体や充填剤の他に、 必要に応じて配合される配合剤を用い、 通常の溶融混練方法、 例えば 1軸混練機や 2軸混練機による方法、 などにより調製 (製造) することが できる。 溶融混練温度は、 脂環式構造含有ブロック共重合体や充填剤の熱分解を 抑制するため、 通常 200〜280°C、 好ましくは 220〜270°C、 特に好ま しくは 240〜 260 °Cで行なうことが望ましい。 光拡散性樹脂組成物は、 脂環 式構造含有プロック共重合体中に有機充填剤及び Z又は無機充填剤が均一に分散 していることが好ましい。 有機充填剤及び Z又は無機充填剤が凝集などして均一 に分散していない場合には、 光拡散性や光透過率にムラを生じるため好ましくな レ、。  The light-diffusing resin composition according to the present invention uses a compounding agent blended as required in addition to the alicyclic structure-containing block copolymer and the filler described above, and uses a usual melt-kneading method, such as 1 It can be prepared (manufactured) by a method using a shaft kneader or a twin-screw kneader. The melt-kneading temperature is usually from 200 to 280 ° C, preferably from 220 to 270 ° C, particularly preferably from 240 to 260 ° C, in order to suppress the thermal decomposition of the alicyclic structure-containing block copolymer and the filler. It is desirable to do. In the light diffusing resin composition, it is preferable that the organic filler and the Z or inorganic filler are uniformly dispersed in the block copolymer having an alicyclic structure. If the organic filler and the Z or inorganic filler are not uniformly dispersed due to agglomeration or the like, unevenness in light diffusion and light transmittance occurs, which is undesirable.
成形おょぴ成形体  Molding molding
本発明に係る光拡散性樹脂組成物は、 各種成形体に成形して各種用途に使用す ることができる。  The light-diffusing resin composition according to the present invention can be molded into various molded articles and used for various applications.
成形方法としては、 一般の熱可塑性樹脂を成形する方法を用いることができる。 具体的には、 押出成形、 射出成形、 圧縮成形、 圧空成形、 真空成形等が用いられ る。 得られた成形体を光拡散板として使用する場合等において、 異なるサイズの ものを多品種少量生産する場合は、 押出成形した板状成形体を、 切削加工、 打抜 き加工、 等の方法で所望の形状にすればよく、 同サイズのものを多量に生産する 場合には射出成形による方法が有利である。 また、 マット模様を有する光拡散板 を製造するには、 たとえば、 光拡散性樹脂組成物を、 Tダイ等により押出し、 次 いでマツト模様を有するロールで挟持加圧して、 マツト模様をその表面に転写さ せる方法等によればよい。 As a molding method, a method of molding a general thermoplastic resin can be used. Specifically, extrusion molding, injection molding, compression molding, compressed air molding, vacuum molding and the like are used. When the obtained compact is used as a light diffusing plate, etc., and when a product of different size is to be produced in a large variety and small quantity, the extruded plate-like compact is cut, punched, etc. Whatever shape you want, you can produce a lot of the same size In this case, a method by injection molding is advantageous. In order to manufacture a light diffusing plate having a mat pattern, for example, the light diffusing resin composition is extruded with a T-die or the like, and then sandwiched and pressed by a roll having a mat pattern, so that the mat pattern is formed on the surface. Any method may be used, such as a method of transferring.
成形条件は、 成形方法により適宜選択される。 射出成形法の場合、 樹脂温度は、 通常 150~300°C、 好ましくは 200〜280°C、 より好ましくは 220〜 250°Cの範囲で適宜選択される。 押出し成形の場合、 樹脂温度は、 通常 150 〜 300 °C、 好ましくは 180〜270°C、 より好ましくは 200〜 240での 範囲で適宜選択される。 樹脂温度が過度に低いと流動性が悪化し、 成形体にヒケ、 ひずみ、 表目荒れを生じるおそれがあり、 逆に、 樹脂温度が過度に高いと樹脂の 熱分解によりシルバーストリークゃダイラインが発生したり、 成形物が黄変する などの成形不良が発生する危険性がある。  The molding conditions are appropriately selected depending on the molding method. In the case of the injection molding method, the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 200 to 280 ° C, more preferably 220 to 250 ° C. In the case of extrusion molding, the resin temperature is appropriately selected in the range of usually 150 to 300 ° C, preferably 180 to 270 ° C, more preferably 200 to 240 ° C. If the resin temperature is excessively low, the fluidity will deteriorate, and the molded product may have sink marks, distortion, and rough surfaces. Conversely, if the resin temperature is excessively high, silver streaks and die lines are generated due to thermal decomposition of the resin. There is a risk of molding defects such as rubbing and yellowing of the molded product.
本発明に係る光拡散性成形体は、 球状、 棒状、 板状、 円柱状、 筒状、 レンズ状、 フィルムまたはシート形状など種々の形状のものであり、 用途に応じて任意の形 状にすることができる。  The light diffusing molded article according to the present invention has various shapes such as a spherical shape, a rod shape, a plate shape, a column shape, a cylindrical shape, a lens shape, a film or sheet shape, and has an arbitrary shape depending on the application. be able to.
光拡散性成形体としては、 パックライ ト型の液晶ディスプレイ等に用いる光拡 散板が挙げられる。 この光拡散板は光源と照射対象の間に配置され、 パックライ ト光源からの光が均一に出射され、 出射面での明暗が均一になるようにするもの である。 その他の用途として、 反射防止フィルム、 光拡散フィルム、 照明カバー、 反射型スクリーン、 透過型スクリーン、 掲示板のバックライト等が挙げられる。 実施例  Examples of the light diffusing molded body include a light diffusing plate used for a pack-light type liquid crystal display and the like. The light diffusing plate is disposed between the light source and the irradiation target, so that the light from the pack light source is uniformly emitted, and the light and dark on the emission surface are uniform. Other applications include anti-reflection films, light-diffusing films, lighting covers, reflective screens, transmissive screens, and bulletin board backlights. Example
以下に、 製造例、 実施例及び比較例を挙げて、 本発明についてより具体的に説 明する。 ただし、 本発明は、 これらの製造例、 実施例のみに限定されるものでは ない。 これらの例中の 「部」 は、 特記のない限り重量基準である。  Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples, and Comparative Examples. However, the present invention is not limited only to these production examples and examples. “Parts” in these examples are on a weight basis unless otherwise specified.
各種の試料作成及ぴ試験は、 下記の方法に従って行つた。  Various sample preparation and tests were performed according to the following methods.
(1) (水素化) ブロック共重合体の重量平均分子量  (1) (Hydrogenated) Weight average molecular weight of block copolymer
THFを溶媒にして 30でで0?じにょり測定し、 標準ポリスチレン換算の M w 求めた。 (2) 分子量分布 Using THF as a solvent, the measurement was carried out at 0 to 30 to determine the Mw in terms of standard polystyrene. (2) Molecular weight distribution
THFを溶媒にして、 30°Cで GPCにより測定し、 標準ポリスチレン換算の Mnを求め、 上記 (1) で求めた Mwの Mnに対する比 (MwZMn) を算出し た。  Gn was measured by GPC at 30 ° C. using THF as a solvent, Mn in terms of standard polystyrene was determined, and the ratio of Mw to Mn (MwZMn) determined in the above (1) was calculated.
(3) 水素化率  (3) Hydrogenation rate
水素化ブロック共重合体の、 主鎖及び芳香環の水素化率は、 ^H— NMRスぺ クトルを測定し算出した。  The hydrogenation rates of the main chain and the aromatic ring of the hydrogenated block copolymer were calculated by measuring the ^ H-NMR spectrum.
製造例 1  Production Example 1
十分に乾燥した、 攪拌装置を備えたステンレス鋼製反応器を窒素置換した後、 脱水シクロへキサン 300部、 スチレン 30部及びジブチルエーテル 0. 20部 を仕込み、 60°Cで攪拌しながら n—プチルリチウム溶液 (15%含有へキサン 溶液) 0. 25部を添加して重合反応を開始した。 重合反応を 1時間行つた後、 反応溶液中に、 スチレン 30部を添加し、 重合反応をさらに 1時間行った。 スチ レンの転化率は 100%であった。 その後、 イソプレン 20部をさらに添加して、 重合反応をさらに 1時間行った。 その後、 さらにスチレン 20部をさらに添加し て、 重合反応をさらに 1時間継続した後、 反応溶液にィソプロピルアルコール 0. 2部を添加して反応を停止させた。  After replacing a sufficiently dried stainless steel reactor equipped with a stirrer with nitrogen, 300 parts of dehydrated cyclohexane, 30 parts of styrene and 0.20 part of dibutyl ether are charged, and the mixture is stirred at 60 ° C while n- 0.25 parts of a butyllithium solution (15% hexane solution) was added to initiate the polymerization reaction. After performing the polymerization reaction for 1 hour, 30 parts of styrene was added to the reaction solution, and the polymerization reaction was further performed for 1 hour. The conversion of styrene was 100%. Thereafter, 20 parts of isoprene was further added, and the polymerization reaction was further performed for 1 hour. Thereafter, 20 parts of styrene was further added, and the polymerization reaction was further continued for 1 hour. Then, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
次いで、 上記重合反応溶液 400部を、 攪拌装置を備えた耐圧反応器に移送し、 水素化触媒として、 ケイソゥ土担持型ニッケル触媒 (E 22U、 日揮化学社製) 3部を添加して混合した。 反応器内の気相部を水素ガスで置換した後、 溶液を攪 拌しながら水素を供給し、 温度 1 70°C、 圧力 4. 5MP aにて 6時間水素化反 応を行った。  Next, 400 parts of the above polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 3 parts of a diatomaceous earth-supported nickel catalyst (E22U, manufactured by JGC Chemicals) was added and mixed as a hydrogenation catalyst. . After replacing the gas phase in the reactor with hydrogen gas, hydrogen was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 170 ° C and a pressure of 4.5 MPa for 6 hours.
水素化反応終了後、 反応溶液をろ過して水素化触媒を除去し、 酸化防止剤ペン タエリスリ トールテトラキス [3— (3, 5—ジ一 t—プチル一 4—ヒ ドロキシ フエニル) プロピオネート] (ィルガノックス 1010、 チバスぺシャリティ · ケミカルズ社製) 0. 1部を添加、 溶解させ、 薄膜乾燥機 (コント口、 日立製作 所製) を使用して、 260°C、 1 OTo r rの条件で脱溶剤を行った。 脱溶剤さ れたブ口ック共重合体を、 押出機で溶融状態でダイからストランドとして押出し、 水冷した後、 カッティングしてペレットを得た。 ここで得られたペレットを樹脂 aとする。 After the completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and the antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate] (ilganox 1010, Ciba Specialty Chemicals) 0.1 Add 1 part, dissolve, and remove solvent using a thin film dryer (Conto Kokuchi, Hitachi, Ltd.) at 260 ° C and 1 OTorr. went. The desolventized block copolymer was extruded as a strand from a die in a molten state by an extruder, cooled with water, and then cut to obtain pellets. The pellet obtained here is a.
得られた水素化ブロック共重合体は、 スチレン由来の繰り返し単位を含有する ブロック (S t) 、 イソプレン由来の繰り返し単位を含有するブロック (I p) 、 及ぴ S tとからなる 3元プロック共重合体であった。 該プロック共重合体の Mw は 130 , 000、 MwZMnは 1. 20、 主鎖及ぴ芳香環の水素化率は 99. 9%であった。 ペレッ トを 220°Cで圧縮成形して 0. 1mm厚みのシートを作 成し、 アッベ屈折計により測定した屈折率は 1. 51であった。  The obtained hydrogenated block copolymer is a ternary block copolymer composed of a block (St) containing a repeating unit derived from styrene, a block (Ip) containing a repeating unit derived from isoprene, and St. It was a polymer. The block copolymer had Mw of 130,000, MwZMn of 1.20, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%. The pellet was compression molded at 220 ° C to produce a 0.1 mm thick sheet, and the refractive index measured by Abbe refractometer was 1.51.
製造例 2  Production Example 2
製造例 1と同様の反応器に、 脱水シクロへキサン 300部、 スチレン 30部及 ぴジプチルエーテル 0. 20部を仕込み、 60°Cで攪拌しながら n—プチルリチ ゥム溶液 (1 5%含有へキサン溶液) 0. 25部を添加して重合反応を開始した。 重合反応を 1時間行った後、 反応溶液中に、 スチレン 10部を添加し、 重合反応 をさらに 1時間行った。 その後、 イソプレン 20部をさらに添加して、 重合反応 をさらに 1時間行った。 その後、 さらにスチレン 40部をさらに添加して、 重合 反応をさらに 1時間継続した後、 反応溶液にイソプロピルアルコール 0. 2部を 添加して反応を停止させた。  The same reactor as in Production Example 1 was charged with 300 parts of dehydrated cyclohexane, 30 parts of styrene and 0.20 parts of dibutyl ether, and stirred at 60 ° C. while stirring at a temperature of 60 ° C. to a content of 15%. (Xan solution) 0.25 parts was added to initiate the polymerization reaction. After performing the polymerization reaction for 1 hour, 10 parts of styrene was added to the reaction solution, and the polymerization reaction was further performed for 1 hour. Thereafter, 20 parts of isoprene was further added, and the polymerization reaction was further performed for 1 hour. Thereafter, 40 parts of styrene was further added, and the polymerization reaction was continued for another hour. Then, 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
次いで、 上記重合反応溶液 400部を、 攪拌装置を備えた耐圧反応器に移送し、 製造例 1と同様にして水素化反応を行った。  Next, 400 parts of the above polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and a hydrogenation reaction was carried out in the same manner as in Production Example 1.
水素化反応終了後、 製造例 1と同様にして、 脱溶剤して、 ペレッ トを得た。 こ こで得られたペレツトを樹脂 bとする。  After completion of the hydrogenation reaction, the solvent was removed in the same manner as in Production Example 1 to obtain a pellet. The pellet obtained here is referred to as resin b.
得られた水素化ブロック共重合体は、 S t、 I p及ぴ S tからなる 3元ブロッ ク共重合体であった。 該プロック共重合体の Mwは 134, 000、 Mw/M は 1. 21、 主鎖及び芳香環の水素化率は 99. 9 %であった。 製造例 1と同様 にして測定した屈折率は 1. 51であった。  The obtained hydrogenated block copolymer was a ternary block copolymer composed of St, Ip, and St. The block copolymer had an Mw of 134,000, an Mw / M of 1.21, and a hydrogenation ratio of the main chain and the aromatic ring of 99.9%. The refractive index measured in the same manner as in Production Example 1 was 1.51.
製造例 3  Production Example 3
製造例 1と同様の反応器に、 脱水シクロへキサン 300部、 スチレン 28. 5 部とイソプレン 1. 5部の混合物及ぴジブチルエーテル 0. 20部を仕込み、 6 0°Cで攪拌しながら n—ブチルリチウム溶液 (15%含有へキサン溶液) 0. 2 5部を添加して重合反応を開始した。 重合反応を 1時間行った後、 反応溶液中に、 スチレン 66. 5部とイソプレン 3. 5部の混合物を、 2時間に渡って連続的に 添加し、 重合反応を継続した。 その後、 さらに 1時間重合反応を行った後、 反応 溶液にィソプロピルアルコール 0. 2部を添加して反応を停止させた。 The same reactor as in Production Example 1 was charged with 300 parts of dehydrated cyclohexane, a mixture of 28.5 parts of styrene and 1.5 parts of isoprene and 0.20 part of dibutyl ether, and stirred at 60 ° C. while stirring n —Butyllithium solution (15% hexane solution) 0.25 parts was added to initiate the polymerization reaction. After conducting the polymerization reaction for 1 hour, A mixture of 66.5 parts of styrene and 3.5 parts of isoprene was added continuously over 2 hours to continue the polymerization reaction. Thereafter, the polymerization reaction was further performed for 1 hour, and then 0.2 parts of isopropyl alcohol was added to the reaction solution to stop the reaction.
次いで、 上記重合反応溶液 400部を、 攪拌装置を備えた耐圧反応器に移送し、 製造例 1と同様にして水素化反応を行った。  Next, 400 parts of the above polymerization reaction solution was transferred to a pressure-resistant reactor equipped with a stirrer, and a hydrogenation reaction was carried out in the same manner as in Production Example 1.
水素化反応終了後、 製造例 1と同様にして、 脱溶剤して、 ペレッ トを得た。 こ こで得られたペレツトを樹脂 cとする。  After completion of the hydrogenation reaction, the solvent was removed in the same manner as in Production Example 1 to obtain a pellet. The pellet obtained here is referred to as resin c.
得られた水素化プロック共重合体は、 S t、 I pからなるランダム共重合体で あった。 該ランダム共重合体の Mwは 138 , 000、 MwZMnは 1. 22、 主鎖及び芳香環の水素化率は 99. 9 %であった。 製造例 1と同様にして測定し た屈折率は 1. 51であった。  The obtained hydrogenated block copolymer was a random copolymer composed of St and Ip. The Mw of the random copolymer was 138,000, MwZMn was 1.22, and the hydrogenation ratio of the main chain and the aromatic ring was 99.9%. The refractive index measured in the same manner as in Production Example 1 was 1.51.
実施例 1  Example 1
製造例 1で得られた樹脂 a : 100重量部と、 真球状架橋ポリスチレンビーズ (テクポリマー SB X— 8、 積水化成品工業社製、 平均粒径 8 111、 屈折率 1. 59) 5重量部とを、 樹脂温度 240°Cで二軸混練機 (TEM— 35B、 東芝機 械社製) を用いて混練し、 光拡散性樹脂組成物を得た。 この光拡散性樹脂組成物 は二軸混練機からストランドに押出し、 水冷して、 ペレタイザ一によりペレット にした。  Resin a obtained in Production Example 1: 100 parts by weight, and spherical crosslinked polystyrene beads (Techpolymer SB X-8, manufactured by Sekisui Plastics Co., Ltd., average particle size 8111, refractive index 1.59) 5 parts by weight Were kneaded with a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 240 ° C. to obtain a light diffusing resin composition. The light diffusing resin composition was extruded from a twin-screw kneader into a strand, cooled with water, and pelletized by a pelletizer.
(光拡散性樹脂組成物の曲げ弾性率)  (Flexural modulus of light diffusing resin composition)
このペレッ トを 80°Cで 3時間乾燥した後、 射出成形機 (AUTOSHOT MODE L 3 OA :ファナック社製) により樹脂温度 260 °C、 金型温度 90 °Cで射出成形し、 長さ 127 mm, 幅 12. 7 mm, 厚み 2 mmの試験片を作成 し、 曲げ弾性率を AS TM D 790法に準じて測定した。 結果を表 1に記載し た。  After drying this pellet at 80 ° C for 3 hours, it was injection-molded with an injection molding machine (AUTOSHOT MODEL 3OA: FANUC) at a resin temperature of 260 ° C and a mold temperature of 90 ° C, and the length was 127 mm. A specimen having a width of 12.7 mm and a thickness of 2 mm was prepared, and the flexural modulus was measured according to the ASTM D790 method. The results are shown in Table 1.
(光拡散板の成形)  (Formation of light diffusion plate)
上記ペレツトを同様に乾燥した後、 射出成形機 ( I S 450、 東芝機械社製) により樹脂温度 260°C、 金型温度 90°Cで射出成形し、 長さ 295 mm, 幅 2 25 mm, 厚み 2 mmの光拡散板を作成した。  After drying the above pellets in the same manner, injection molding is performed using an injection molding machine (IS 450, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 260 ° C and a mold temperature of 90 ° C. Length 295 mm, width 225 mm, thickness A 2 mm light diffusion plate was made.
(光学特性の評価) この光拡散板の全光線透過率と光拡散性の指標であるヘイズを J I S K71 05の方法に従って、 濁度計 (NDH— 300Α、 日本電色工業社製) で測定し た。 これらの光学的指標は、 例えば、 光拡散板では、 全光線透過率が高く、 ヘイ ズが大きいことが望ましい。 結果を表 1に示す。 (Evaluation of optical characteristics) The haze, which is an index of the total light transmittance and light diffusivity of this light diffusion plate, was measured by a turbidity meter (NDH-300 mm, manufactured by Nippon Denshoku Industries Co., Ltd.) according to the method of JIS K7105. For these optical indices, for example, it is desirable that a light diffusion plate has a high total light transmittance and a large haze. Table 1 shows the results.
(成形性の評価)  (Evaluation of moldability)
成形性は、 前記の光拡散板の射出成形時のシルバー、 ヒケ、 割れ、 等の外観不 良の発生有無の確認を行なった。 目立った不良は無く、 外観は良好であった。 評 価結果を表 1に合わせて記載した。  Regarding the moldability, it was confirmed whether or not appearance defects such as silver, sink marks, cracks, etc. occurred during the injection molding of the light diffusion plate. There were no noticeable defects and the appearance was good. The evaluation results are shown in Table 1.
(機械的強度の評価)  (Evaluation of mechanical strength)
光拡散板の機械的強度は、 光拡散板を長さ 100mm、 幅 15 mmの試験片に 切り出し、 ASTM D 790法に準じて、 ストログラフ (東洋精機製作所社製 ; V 10-B) にて、 25 °Cにおける曲げ強度を測定した。 曲げ試験では、 降伏 点を示し、 柔軟性を有していた。 また、 光拡散板の長手側端部の外形を NC加工 機により、 両端から 100mmづっ 2mm幅で削り取り、 端部中央に長さ 25m mの位置決め用凸部を残す加工を行ない、 割れやクラック等の外観不良の発生有 無を確認した。 目立った不良は無く、 外観は良好であった評価結果を表 1に合わ せて記載した。  The mechanical strength of the light diffusing plate is determined by cutting out the light diffusing plate into test pieces 100 mm long and 15 mm wide, and using a strograph (manufactured by Toyo Seiki Seisakusho; V10-B) in accordance with ASTM D790 The bending strength at 25 ° C was measured. The bending test showed a yield point and was flexible. In addition, the outer shape of the longitudinal end of the light diffuser plate is cut by 2 mm width from the both ends by 100 mm from the both ends with a NC machine, leaving a 25 mm long positioning projection at the center of the end, cracking, cracking, etc. It was confirmed that there was no occurrence of poor appearance. Table 1 shows the results of the evaluation, in which there was no noticeable defect and the appearance was good.
実施例 2  Example 2
実施例 1の真球状架橋ポリスチレンビーズに代えて、 真球状架橋シリコ一ン樹 脂ビーズ (トスパール 145、 東芝シリコーン社製、 平均粒径 4. 5 Mm, 屈折 率 1. 43) : 5重量部を使用する以外は、 実施例 1と同様にして光拡散性樹脂 組成物を得、 この光拡散性樹脂組成物を実施例 1と同様にして射出成形し光拡散 板を作成して実施例 1と同様に評価した。 結果を表 1に合わせて記載した。  Instead of the spherically crosslinked polystyrene beads of Example 1, spherically crosslinked silicone resin beads (Tospearl 145, manufactured by Toshiba Silicone Co., average particle size 4.5 Mm, refractive index 1.43): 5 parts by weight Except for use, a light diffusing resin composition was obtained in the same manner as in Example 1, and this light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. It was evaluated similarly. The results are shown in Table 1.
実施例 3  Example 3
実施例 1の真球状架橋ポリスチレンビーズに代えて、 タルク (ミクロエース、 日本タルク社製、 平均粒径 4 111) : 5重量部を使用する以外は、 実施例 1と同 様にして光拡散性樹脂組成物を得、 この光拡散性樹脂組成物を実施例 1と同様に して射出成形し光拡散板を作成して実施例 1と同様に評価した。 結果を表 1に合 わせて記載した。 実施例 4 Light diffusing property was obtained in the same manner as in Example 1 except that talc (Microace, manufactured by Nippon Talc Co., average particle size: 4111): 5 parts by weight was used instead of the spherical crosslinked polystyrene beads of Example 1. A resin composition was obtained, and this light-diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light-diffusing plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1. Example 4
実施例 1の樹脂 aに代えて、 製造例 2で得られた樹脂 b : 1 0 0重量部を使用 する以外は、 実施例 1と同様にして光拡散性樹脂組成物を得、 この光拡散性樹脂 組成物を実施例 1と同様にして射出成形し光拡散板を作成して実施例 1と同様に 評価した。 結果を表 1に合わせて記載した。  A light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin b obtained in Production Example 2 was used instead of the resin a of Example 1. The hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
実施例 5  Example 5
実施例 1の樹脂 aに代えて、 製造例 2で得られた樹脂 b : 1 0 0重量部、 真球 状架橋ポリスチレンビーズに代えて、 実施例 2で使用したのと同じ真球状架橋シ リコーン樹脂ビーズ: 5重量部を使用する以外は、 実施例 1と同様にして光拡散 性樹脂組成物を得、 この光拡散性樹脂組成物を実施例 1と同様にして射出成形し 光拡散板を作成して実施例 1と同様に評価した。 結果を表 1に合わせて記載した。  In place of resin a in Example 1, resin b obtained in Production Example 2: 100 parts by weight, spherical spherical crosslinked polystyrene beads used in Example 2 in place of spherical crosslinked polystyrene beads Resin beads: A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
実施例 6  Example 6
実施例 1の樹脂 aに代えて、 製造例 2で得られた樹脂 b : 1 0 0重量部、 真球 状架橋ポリスチレンビーズに代えて、 実施例 3で使用したのと同じタルク : 5重 量部を使用する以外は、 実施例 1と同様にして光拡散性樹脂組成物を得、 この光 拡散性樹脂組成物を実施例 1と同様にして射出成形し光拡散板を作成して実施例 1と同様に評価した。 結果を表 1に合わせて記載した。  In place of resin a in Example 1, resin b obtained in Production Example 2: 100 parts by weight, in place of spherical cross-linked polystyrene beads, the same talc as used in Example 3: 5 weight A light diffusing resin composition was obtained in the same manner as in Example 1 except that the parts were used, and the light diffusing resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusing plate. Evaluation was made in the same manner as in 1. The results are shown in Table 1.
比較例 1  Comparative Example 1
実施例 1の樹脂 aに代えて、 製造例 3で得られた樹脂 c : 1 0 0重量部を使用 する以外は、 実施例 1と同様にして光拡散性樹脂組成物を得、 この光拡散性樹脂 組成物を実施例 1と同様にして射出成形し光拡散板を作成して実施例 1と同様に 評価した。 結果を表 1に合わせて記載した。  A light-diffusing resin composition was obtained in the same manner as in Example 1, except that 100 parts by weight of the resin c obtained in Production Example 3 was used instead of the resin a of Example 1. The hydrophilic resin composition was injection molded in the same manner as in Example 1 to prepare a light diffusion plate, and evaluated in the same manner as in Example 1. The results are shown in Table 1.
比較例 2  Comparative Example 2
実施例 1の樹脂 aに代えて、 製造例 3で得られた樹脂 c : 1 0 0重量部、 真球 状架橋ポリスチレンビーズに代えて、 実施例 2で使用したのと同じ真球状架橋シ リコーン樹脂ビーズ: 5重量部を使用する以外は、 実施例 1と同様にして光拡散 性樹脂組成物を得、 この光拡散性樹脂組成物を実施例 1と同様にして射出成形し 光拡散板を作成して実施例 1と同様に評価した。 結果を表 1に合わせて記載した。 比較例 3 実施例 1の樹脂 aに代えて、 製造例 3で得られた樹脂 c : 1 0 0重量、 真球状 架橋ポリスチレンビーズに代えて、 実施例 3で使用したのと同じタルク : 5重量 部を使用する以外は、 実施例 1と同様にして光拡散性樹脂組成物を得、 この光拡 散性樹脂組成物を実施例 1と同様にして射出成形し光拡散板を作成して実施例 1 同様に評価した。 結果を表 1に合わせて記載した。 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 parts by weight, and in place of the spherical crosslinked polystyrene beads, the same spherical crosslinked silicone as used in Example 2 was used. Resin beads: A light diffusing resin composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used, and the light diffusing resin composition was injection-molded in the same manner as in Example 1 to obtain a light diffusing plate. It was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 3 In place of the resin a in Example 1, the resin c obtained in Production Example 3 was 100 weight parts, and in place of the spherical crosslinked polystyrene beads, the same talc used in Example 3 was used: 5 parts by weight. A light diffusing resin composition was obtained in the same manner as in Example 1 except that the light diffusing resin composition was injection-molded in the same manner as in Example 1 to prepare a light diffusing plate. Was evaluated. The results are shown in Table 1.
樹脂 充填剤 Resin filler
光拡散性樹脂  Light diffusing resin
光拡散性 全光線  Light diffusing property All rays
配合量 (重量部) 配合量 (重量部) '祖成物の厚^ へイノス、 尤 ¾lA"ォfaム÷"ft' gfsCr取士 の J^nSlHin丁  Compounding amount (parts by weight) Compounding amount (parts by weight) 'Thickness of the ancestral material ^ Heinos, like ¾lA "o fam ÷" ft' gfsCr
Τλ)削刀 U ,トル -L 3i 樹脂組成物の  Τλ) Sharp U, Tor -L 3i resin composition
2mmの試験片の 透過率  2mm specimen transmittance
架橋ホ °リ 架橋シリ 曲げ弾性率 の曲げ強度  Crosslinked resin Crosslinked silicon Flexural modulus Flexural strength
樹脂 a 樹脂 b 樹脂 C スチレン コーン樹 タルク 射出成形性 % %  Resin a Resin b Resin C Styrene Corn tree Talc Injection moldability%%
ビーズ kgf/ mm2 kgf/ mm2 Beads kgf / mm 2 kgf / mm 2
脂ビ-ズ  Fat beads
- - - 590  ---590
実施例 1 100 5 - 19,000 外観は良好 62 94 外観は良好 Example 1 100 5-19,000 Good appearance 62 94 Good appearance
(降伏点)  (Yield point)
一 - - 590  One--590
実施例 2 100 5 一 19,000 外観は良好 68 91 外観は良好 Example 2 100 5 1 19,000 Appearance is good 68 91 Appearance is good
(降伏点)  (Yield point)
580  580
実施例 3 100 5 19,500 外観は良好 55 87 外観は良好 Example 3 100 5 19,500 Appearance is good 55 87 Appearance is good
(降伏点)  (Yield point)
470  470
実施例 4 100 5 14,000 外観は良好 61 93 外観は良好 Example 4 100 5 14,000 Good appearance 61 93 Good appearance
(降伏点)  (Yield point)
470  470
実施例 5 100 5 14,000 外観は良好 68 92 外観は良好 Example 5 100 5 14,000 Good appearance 68 92 Good appearance
(降伏点)  (Yield point)
460  460
実施例 6 100 5 14,500 外観は良好 55 87 外観は良好 Example 6 100 5 14,500 Appearance is good 55 87 Appearance is good
(降伏点)  (Yield point)
離型時にグー 400 切削面からクラック、及ぴ、 比較例 1 100 5 30,500 61 91  Goo 400 cracks from the cut surface when releasing, and Comparative Example 1 100 5 30,500 61 91
ト部で割れ (破断点) 欠けが発生し、外観不良 比較例 2 100 ぴ、 Crack (break point) chipped at the part, resulting in poor appearance Comparative Example 2 100 mm
5 離型時にグー 420 切削面からクラック、及 5 When releasing the goo 420
30,500 68 89  30,500 68 89
ト部で割れ (破断点) 欠けが発生し、外観不良 離型時にゲー 390  Crack (break point) chipped at the part, resulting in poor appearance.
比較例 3 切削面力 クラック、及ぴ、Comparative Example 3 Cutting Surface Force Crack,
100 5 31,000 55 84 100 5 31,000 55 84
ト部で割れ (破断点) 欠けが発生し、外観不良 Crack (break point)
表 1に示すように、 製造例 1及び製造例 2で得られた S t— I p— S tの水素 ィ匕 3元ブロック共重合体と、 充填剤とからなり、 曲げ弾性率が 10, 000〜2 7, O O O k g fZcm2 である本発明の光拡散性樹脂組成物からなる光拡散性 成形体 (実施例 1〜6) は、 光透過性、 光拡散性共に優れていることが確認でき た。 また、 これら実施例 1〜6の光拡散性成形体は、 製造例 3で得られた従来の 水素化スチレン系ランダム共重合体と、 充填剤とからなり、 曲げ弾性率が 27, O O O k g f Xcm2 以上である光拡散性樹脂組成物からなる光拡散性成形体 (比較例 1〜3) に比べ、 機械的柔軟性が付与され、 射出成形での離型時のゲ一 ト部割れや、 光拡散板の切削加工時の切削面での欠けゃクラックが発生し難いこ とが確認された。 このように機械的柔軟性が改善されていることにより、 少量多 品種の成形品を、 押出し板や一定サイズの板から切削加工等により容易に作成で きるため、 工業上の利点が大きい。 産業上の利用可能性 As shown in Table 1, a St-Ip-St hydrogenated ternary block copolymer obtained in Production Example 1 and Production Example 2 and a filler had a flexural modulus of 10, 000 ~ 27, OOO kg fZcm 2 It was confirmed that the light diffusing molded product (Examples 1-6) comprising the light diffusing resin composition of the present invention was excellent in both light transmittance and light diffusivity. did it. The light-diffusing molded articles of Examples 1 to 6 consist of the conventional hydrogenated styrene-based random copolymer obtained in Production Example 3 and a filler, and have a flexural modulus of 27, OOO kgf Xcm Mechanical flexibility is imparted as compared to the light-diffusing molded article made of the light-diffusing resin composition of 2 or more (Comparative Examples 1 to 3), and the gate portion cracks at the time of release from the injection molding, It was confirmed that chipping and cracking hardly occurred on the cut surface during cutting of the light diffusion plate. The improved mechanical flexibility has a great industrial advantage because small and large variety of molded products can be easily prepared from extruded plates or plates of a certain size by cutting or the like. Industrial applicability
本発明によれば、 光透過性と光拡散性が共に優れ、 さらに成形加工時や実使用 時にも割れ難い機械強度を有する、 光拡散板等の光拡散性成形体に好適な光拡散 性樹脂組成物が提供される。  According to the present invention, a light-diffusing resin suitable for light-diffusing molded articles such as a light-diffusing plate, which has both excellent light-transmitting properties and light-diffusing properties, and has mechanical strength that is hard to be broken during molding and actual use. A composition is provided.

Claims

言青求の範囲 Scope of Word
1. 脂環式構造含有ブロック共重合体と、 充填剤とを、 有する光拡散 性樹脂組成物であって、 1. A light-diffusing resin composition having an alicyclic structure-containing block copolymer and a filler,
前記脂環式構造含有プロック共重合体が、  The alicyclic structure-containing block copolymer,
下記式 (1) で表される繰り返し単位 [1] を 90重量%以上含有する重合体 プロック [A] と、  A polymer block [A] containing 90% by weight or more of the repeating unit [1] represented by the following formula (1);
下記式 (2) で表される繰り返し単位 [2] 及び Z又は下記式 (3) で表され る繰り返し単位 [3] を合計で 30重量%以上含有する重合体ブロック [B] と を、 有し、  And a polymer block [B] containing a total of 30% by weight or more of the repeating unit [2] and Z represented by the following formula (2) or the repeating unit [3] represented by the following formula (3). And
ASTM-D 790法に基づいて厚さ 2mmの板に成形して測定された、 25 °Cにおける曲げ弾性率が、 10, 000〜 27, 000 k g i/cm2 である 光拡散性樹脂組成物。 A light-diffusing resin composition having a flexural modulus at 25 ° C of 10,000 to 27,000 kgi / cm 2, which is measured by molding a plate having a thickness of 2 mm based on the ASTM-D 790 method.
(式 (1) 中、 R1 は水素原子、 又は炭素数 1〜20のアルキル基を表し、 R2 一 R12は R2 、 R3 、 R4 、 R5 、 Re 、 R7 、 Rs 、 R9 、 R10、 Κ 1及ぴ R 12を意味し、 これらはそれぞれ独立に水素原子、 炭素数 1〜20のアルキル基、 ヒドロキシル基、 炭素数 1~20のアルコキシ基、 又はハロゲン基を表す。 R2 — R12は各々同一であっても、 異なっていてもよい。 ) (In the formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 2 and R 12 represent R 2 , R 3 , R 4 , R 5 , R e , R 7 , R s , R 9 , R 10 , Κ 1 and R 12 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a halogen group R 2 — R 12 may be the same or different.)
(式 (2) 中、 R13及び R14は、 それぞれ独立に水素原子、 炭素数 1〜20のァ ルキル'基、 ハロゲン基又はァリール基を表す。 ) (In the formula (2), R 13 and R 14 each independently represent a hydrogen atom, an alkyl ′ group having 1 to 20 carbon atoms, a halogen group or an aryl group.)
(式 (3) 中、 R15及ぴ R16は、 それぞれ独立に水素原子、 炭素数 1〜20のァ ルキル基、 ハロゲン基又はァリール基を表す。 ) (In the formula (3), R 15 and R 16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen group or an aryl group.)
2. 前記脂環式構造含有プロック共重合体が、 1個の前記重合体プロッ ク [B] の両端に 2個の前記重合体ブロック [A] が結合した ([A]— [B]— [A]) 型のトリプロック共重合体である請求項 1に記載の光拡散性樹脂組成物。 2. In the block copolymer having an alicyclic structure, two polymer blocks [A] are bonded to both ends of one polymer block [B] ([A] — [B] — 2. The light-diffusing resin composition according to claim 1, which is a [A])-type triploc copolymer.
3. 前記脂環式構造含有ブロック共重合体が、 20, 000〜 400, 000の重量平均分子量 (Mw) を持ち、 該重量平均分子量 (Mw) がテトラヒ ドロフランを溶媒とするゲル ·パ一ミエーシヨン ' クロマトグラフィー (GP C) により測定されるポリスチレン換算の値である請求項 1に記載の光拡散性樹 脂組成物。 3. The alicyclic structure-containing block copolymer has a weight average molecular weight (Mw) of 20,000 to 400,000, and the weight average molecular weight (Mw) is a gel permeation using tetrahydrofuran as a solvent.光 The light-diffusing tree according to claim 1, which is a value in terms of polystyrene measured by chromatography (GPC). Fat composition.
4. 前記脂環式構造含有ブロック共重合体が、 3以下の、 重量平均分 子量 (Mw) と数平均分子量 (Mn) との比 (MwZMn) を持ち、 該重量平均 分子量 (Mw) と数平均分子量 (Mn) とがテトラヒ ドロブランを溶媒とするゲ ノレ'パーミエーシヨン 'クロマトグラフィー (GPC) により測定されるポリス チレン換算の値である請求項 1に記載の光拡散性樹脂組成物。 4. The alicyclic structure-containing block copolymer has a weight average molecular weight (Mw) and a number average molecular weight (Mn) ratio (MwZMn) of 3 or less, and the weight average molecular weight (Mw) 2. The light-diffusing resin composition according to claim 1, wherein the number average molecular weight (Mn) is a value in terms of polystyrene measured by genole'permeation 'chromatography (GPC) using tetrahydrobran as a solvent.
5. 前記脂環式構造含有プロック共重合体が、 リビングァニオン重合 により得られたものである請求項 1に記載の光拡散性樹脂組成物。 5. The light-diffusing resin composition according to claim 1, wherein the block copolymer having an alicyclic structure is obtained by living anion polymerization.
6. 前記充填剤が、 1 μ m以上 30 μ m以下の平均粒径を持つ請求項 1に記載の光拡散性樹脂組成物。 6. The light diffusing resin composition according to claim 1, wherein the filler has an average particle size of 1 μm or more and 30 μm or less.
7. 前記充填剤が、 重合体又は該重合体の架橋物からなる有機充填剤 である請求項 1に記載の光拡散性樹脂組成物。 7. The light diffusing resin composition according to claim 1, wherein the filler is an organic filler composed of a polymer or a crosslinked product of the polymer.
8. 前記有機充填剤が、 70%以上の全光線透過率を持ち、 該全光線 透過率が厚さ 1 mmの板状成形体にしたときの値である請求項 7に記載の光拡散 性樹脂組成物。 8. The light diffusing property according to claim 7, wherein the organic filler has a total light transmittance of 70% or more, and the total light transmittance is a value when a plate-like molded body having a thickness of 1 mm is formed. Resin composition.
9. 前記脂環式構造含有プロック共重合体の屈折率を n 1とし、 前記 有機充填剤の屈折率を n 2としたとき、 該 η 1と n 2との比 (n 1/n 2) 又は (n 2/n 1) 力 1. 01以上 1. 2以下である請求項 7に記載の光拡散性樹 脂組成物。 9. When the refractive index of the block copolymer having an alicyclic structure is n 1 and the refractive index of the organic filler is n 2, the ratio of η 1 to n 2 (n 1 / n 2) 8. The light-diffusing resin composition according to claim 7, which has a (n 2 / n 1) force of not less than 1.01 and not more than 1.2.
10. 前記有機充填剤が、 ポリスチレン系重合体、 ポリシロキサン系 重合体又はそれらの架橋物からなる微粒子である請求項 7に記載の光拡散性樹脂 組成物。 10. The light-diffusing resin composition according to claim 7, wherein the organic filler is a fine particle comprising a polystyrene-based polymer, a polysiloxane-based polymer, or a crosslinked product thereof.
1 1 . 前記充填剤が、 タルク、 酸化ケィ素、 アルミナ及びシリカアル ミナからなる群から選ばれる少なくとも 1種の無機充填剤である請求項 1に記載 の光拡散性樹脂組成物。 11. The light diffusing resin composition according to claim 1, wherein the filler is at least one inorganic filler selected from the group consisting of talc, silicon oxide, alumina, and silica alumina.
1 2 . 請求項 1〜 1 1のいずれかに記載の光拡散性樹脂組成物を成形 してなる光拡散性成形体。 12. A light diffusing molded article obtained by molding the light diffusing resin composition according to any one of claims 1 to 11.
1 3 . 光拡散板である請求項 1 2に記載の光拡散性成形体。 13. The light diffusing molded article according to claim 12, which is a light diffusing plate.
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