CN103635497A - Method for polymerizing resin casting for use as epoxy acrylic optical lens and resin composition containing internal releasing agent for use in epoxy acrylic optical lens - Google Patents
Method for polymerizing resin casting for use as epoxy acrylic optical lens and resin composition containing internal releasing agent for use in epoxy acrylic optical lens Download PDFInfo
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- CN103635497A CN103635497A CN201280003139.0A CN201280003139A CN103635497A CN 103635497 A CN103635497 A CN 103635497A CN 201280003139 A CN201280003139 A CN 201280003139A CN 103635497 A CN103635497 A CN 103635497A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
Abstract
The present invention relates to a method for polymerizing a resin casting for use as an epoxy acrylic optical lens which facilitates the separation of same from a mold, and to a resin composition containing an internal releasing agent for use in epoxy acrylic optical lenses. According to the present invention, a compound having a polar group or a phosphate ester compound is added as an internal releasing agent to the resin composition used for epoxy acrylate lenses for eyeglasses so that the resin for the optical lens can be manufactured to have little polymerization imbalance and excellent release performance.
Description
Technical field
The present invention relates to the serial optical mirror slip of epoxy acrylic (Epoxy Acrylate) resin die casting (mold) polymerization (polymerization) method, relate in particular to a kind of serial optical mirror slip resin composition of epoxy acrylic (Epoxy Acrylate) that is easy to epoxy acrylic (Epoxy Acrylate) resin die casting for serial optical mirror slip (mold) polymerization (polymerization) method from mould separation and comprises internal mold release (release agent).
Background technology
Plastic optics eyeglass is the substitute products that can make up the low shock-resistance of optical mirror slip high specific gravity.That as plastic optics eyeglass, uses has polyethylene glycol diene propyl carbonate (polyethyl glycol bis allyl carbonate), polymethylmethacrylate (Polymethylmethacrylate), a polyethylene glycol diene propyl carbonate (polyethyl glycol bis allyl carbonate) and diallyl phthalate (Diallyl phthalate).Although the optical mirror slip die casting of manufacturing with the polymer of these materials; dyeability; combining closely property of hard protecting film (hard protective coating); the physical propertiess such as shock-resistance are outstanding; but refractive index is 1.50 (nD) and 1.55 (nD), lower, cause the problem of eyeglass thickening.In order to reduce the thickness of eyeglass, a lot of attainments have been done in the research of the high refractive index optical material of exploitation.
In Korea S patent of invention 10-1987-0001768,10-1987-014268,10-1989-001686,10-1989-001865,10-1989-001913,10-1993-015515, introduced polymeric polyisocyanate (Polyisocyanate) compound and polythiol (polythiol) compound have been carried out to the method that heat embrittlement obtains the serial optical mirror slip of urethanum (Urethane).Urethanum (Urethane) is although the optical characteristics such as serial optical mirror slip tint permanence, shock-resistance, Abbe number (Abbe ' s number) and the transparency are outstanding, but exist material price expensive, the problem that eyeglass manufacturing process technical difficulty is high.Be urethanum (Urethane) resin composition owing to being subject to the impact of moisture, therefore from allotment resin composition till to inject mould complete, completely cut off moisture.Therefore be necessary the atmospheric moisture in workshop to control.If mould medial surface and resin composition and airborne contact with moisture, lens surface there will be muddiness (cloudiness) phenomenon, reduces the transparency of eyeglass.And, if for a long time in warehouse or shop keeping, be not only blank, the problem that the product that the complete eyeglass that hardening treatment (hard multy coating) finishes also can partly deform because absorbing moisture, the thinnest center of lens of appearance.
In Korea S patent of invention 10-2003-0018653, even if introduced, a kind of not only optical characteristics is outstanding, but also cheap epoxy acrylic for optical mirror slip (Epoxy Acrylate) the series plastics synthetics that also need not manage atmospheric moisture, can not deform because of airborne moisture eyeglass while taking care of for a long time of producing in high temperature humid area of material price.But compare when manufacturing eyeglasses with other resin compositions, while manufacturing eyeglass with epoxy acrylic (Epoxy Acrylate) series plastics, more difficult from mould Separator lens.
Internal mold release (release agent) is to sneak into resin composition, reduces the bonding force between mould and finished product, is easy to the product of the demoulding, can improve the production efficiency of eyeglass.The internal mold release (release agent) using now has fluorine series non-ionic surfactants (nonionicsurfactant), silica gel series non-ionic surfactants (nonionicsurfactant), alkyl quaternary ammonium salts (Alkyl quaternary ammonium salt), phosphoric acid ester (phosphate ester) compound, whiteruss (liquid paraffin), wax (wax), higher fatty acid (higher aliphatic acid) and metal-salt thereof, high-grade aliphatic ester (Senior fatty acid ester), high fatty alcohol (higher aliphatic alcohol), bisamide (Bis amide) class, polysiloxane (Polysiloxane) class, fatty amine ethylene oxide adduct (Aliphatic amide ethylene oxide adduct) etc.This internal mold release (release agent) is mainly for the manufacture of the serial optical mirror slip of urethanum (Urethane).
The internal mold release that the serial optical mirror slip of urethanum (Urethane) is relevant (release agent) is although very many, but epoxy acrylic (Epoxy Acrylate) resin is different from the characteristic of urethanum (Urethane) resin, simply copy the internal mold release (release agent) that the serial optical mirror slip manufacture of urethanum (Urethane) is used mechanically, be difficult to obtain satisfied stripping result.
Summary of the invention
The problem of invention
The object of the present invention is to provide and the release property of epoxy acrylic (Epoxy Acrylate) resin can be brought up to satisfactory level, be i.e. during die casting (mold) polymerization (polymerization), be easy to bring up to from mould Separator lens, release property die casting (mold) polymerization (polymerization) method that damaged degree occurs hardly.The spendable known internal mold release of manufacture (release agent) of the serial optical mirror slip of epoxy acrylic (Epoxy Acrylate) has phosphoric acid ester (phosphate ester) compound, and it contributes to the optical mirror slip having hardened from glass mold separation.But, as internal mold release (release agent) even if use known general with phosphoric acid ester (phosphate ester) compound, release property can not reach satisfied degree (in the present invention, when " satisfied degree " refers to from mould Separator lens, there is damaged degree hardly), therefore need to improve.Particularly, for the thin eyeglass in edge (low powered posterior chamber of negative eyeglass, positive eyeglass), even if use phosphoric acid ester (phosphate ester) compound, harden rear or be difficult to from mould Separator lens.This not only reduces production efficiency, also can reduce production yield.
The present invention is the invention proposing in order to address the above problem, its object is to provide a kind of die casting (mold) polymerization (polymerization) method, and the release property after epoxy acrylic (Epoxy Acrylate) resin optical lens die casting (mold) polymerization (polymerization) is brought up to satisfied degree.Especially, even if the object of the present invention is to provide the thin eyeglass in a kind of production edge (low powered posterior chamber of negative eyeglass, positive eyeglass), also can be after sclerosis from die casting (mold) polymerization (polymerization) method of the easy Separator lens of mould.In addition, the present invention also aims to provide a kind of production that allows the serial optical mirror slip of epoxy acrylic (Epoxy Acrylate) become and be easy to the serial optical mirror slip resin composition of epoxy acrylic (Epoxy Acrylate) containing releasing agent (release agent).
Embodiment
The present invention is based on and chance on a compound for band polar group (polar group) (hydroxyl (hydroxy) and/or carboxyl (carboxylic acid)) while using as internal mold release (release agent), can with resin composition release property, bring up to satisfied degree take the optical mirror slip that epoxy acrylic (Epoxy Acrylate) resin is principal constituent.The compound of band polar group (polar group) (hydroxyl (hydroxy) and/or carboxyl (carboxylic acid)) is used as internal mold release (release agent) separately, or with known general with together with phosphoric acid ester (phosphate ester) compound as internal mold release (release agent) use the release property of epoxy acrylic (Epoxy Acrylate) resin can be brought up to satisfied degree.
In addition, the present invention is based on and chance on when phosphoric acid ester (phosphate ester) compound shown in following chemical formula 3 is used as internal mold release (release agent), can with resin composition release property, bring up to satisfied degree take the optical mirror slip that epoxy acrylic (Epoxy Acrylate) resin is principal constituent.
Accordingly, the invention provides the serial optical mirror slip of a kind of epoxy acrylic (Epoxy Acrylate) resin die casting (mold) polymerization (polymerization) method, it is characterized in that: by die casting (mold) polymerization (polymerization) mode manufacture, comprise while using synthetics containing epoxy acrylic (Epoxy Acrylate) resin compound 20～80wt% of compound shown in one or both following Chemical formula 1s and the optical mirror slip of reactive diluent 15～75wt%, as internal mold release (release agent), add in advance shown in following Chemical formula 2 with phosphoric acid ester (phosphate ester) compound 0.001～10wt% shown in the compound of polar group (polar group) or following chemical formula 3.
Chemical formula 1
(here, n=0～15, R1 is H or CH3, R2 is H or Br.)
Chemical formula 2
R—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
Chemical formula 3
(here, R is hydrocarbon 3～20 alkyl (Alkyl), and n is that 0～10, m is 1～2.)
In addition, the invention provides the serial optical mirror slip resin composition of a kind of epoxy acrylic (Epoxy Acrylate), it comprises containing one or both the as above epoxy acrylic of compound shown in Chemical formula 1 (Epoxy Acrylate) resin compound 20～80wt% reactive diluent 15～75wt%, as internal mold release (release agent), as above shown in Chemical formula 2 with the compound of polar group (polar group) or as above phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound 0.001～10wt%.
The invention provides a kind of optical material, it adds catalyzer to the serial optical mirror slip of described epoxy acrylic (Epoxy Acrylate) with resin composition, carries out heat embrittlement acquisition.Described optical material can be for the manufacture of plastic eyeglass lens or polarized lenses.
Invention effect
The present invention is to the as above mixture of epoxy acrylic shown in Chemical formula 1 (Epoxy Acrylate) compound, reactive diluent, additive etc., as internal mold release (release agent), add as above shown in Chemical formula 2 with the compound of polar group (polar group) or as above phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound, carry out die casting (mold) polymerization (polymerization), can prevent polymerization non-uniform phenomenon, and solve the problem of demoulding separation.Particularly, for the thin eyeglass in edge, the damage that the present invention likely produces in the time of can avoiding equally from mould Separator lens, can improve production yield.Optical mirror slip resin composition of the present invention, compare with the serial high ametropia lens of urethanum (Urethane), cost is low, faint with reacting of moisture, be not subject to the environmental restraint of high temperature humidity, while producing eyeglass, need not separately establish dehumidification equipment, even if eyeglass, center of lens position can not deform because of airborne moisture yet certainly for a long time, solved the poor problem points of original epoxy acrylic (Epoxy Acrylate) resin lens release property simultaneously, can replace the serial optical mirror slip of urethanum (Urethane) etc., widespread use.The optical material that the resin composition of the present invention that hardens obtains, can be widely used in glasses lens or pick up camera eyeglass.Particularly, epoxy acrylic of the present invention (Epoxy Acrylate) resin can be applicable to plastic eyeglass lens, the 3D polarized lenses of light polarizing film is installed at glasses lens, can also be applied in multiple optical articles fields such as prism (prism), fiber optics, the recording medium substrate that is used in CD etc. or painted strainer and ultraviolet radiation absorption strainers.
Embodiment
Die casting of the present invention (mold) polymerization (polymerization) method, it is characterized in that: by die casting (mold) polymerization (polymerization) mode manufacture, comprise while using synthetics containing epoxy acrylic (Epoxy Acrylate) resin compound 20～80wt% of compound shown in one or both Chemical formula 1s and the optical mirror slip of reactive diluent 15～75wt%, as internal mold release (release agent), add in advance shown in Chemical formula 2 with phosphoric acid ester (phosphate ester) compound shown in the compound of polar group (polar group) or chemical formula 3.
In addition, optical mirror slip resin composition of the present invention is the resin compound 20～80wt% containing compound shown in one or both Chemical formula 1s, reactive diluent 15～75wt%, the optical mirror slip resin composition mixing with phosphoric acid ester (phosphate ester) compound 0.001～10wt% shown in the compound of polar group (polar group) or more than one chemical formulas 3 shown in more than one Chemical formula 2s.
Described synthetics can also comprise UV light absorber, phosphoric acid ester (phosphate ester) compound, speed of response conditioning agent, thermo-stabilizer, pigment, catalyzer etc.The liquid phase viscosity of synthetics in the time of 25 ℃ 20～1,000cps, liquid phase refractive index (nE, 20 ℃) is 1.50～1.58, solid phase refractive index (nE, 20 ℃) is 1.57～1.63 to be advisable.
Chemical formula 1
(here, n=0～15, R1 is H or CH3, R2 is H or Br.)
Chemical formula 2
R—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
Chemical formula 3
(here, R is hydrocarbon 3～20 alkyl (Alkyl), and n is that 0～10, m is 1～2.)
Take the serial optical mirror slip of epoxy acrylic (Epoxy Acrylate) that compound shown in Chemical formula 1 is principal constituent with after synthetics implantation glass mould, while carrying out heat embrittlement, due in molecule-OH base and glass mold produce bonding force, and the eyeglass of sclerosis is very difficult during from mould separation.The present invention is in order to address this problem, as internal mold release (release agent), to optical resin synthetics, add shown in Chemical formula 2 with phosphoric acid ester (phosphate ester) compound shown in the compound of polar group (polar group) or chemical formula 3, the serial optical mirror slip of epoxy acrylic (Epoxy Acrylate) can be brought up to satisfied degree with the release property of resin, while especially manufacturing the thin eyeglass in edge, also can prevent edge distortion or damaged.Here, known general also passable with the serial internal mold release of phosphoric acid ester (phosphate ester) (release agent) use to the compound of band polar group (polar group) as internal mold release (release agent), to the compound use with polar group (polar group) shown in phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound Chemical formula 2, also can.
Shown in described Chemical formula 2, with the compound of polar group (polar group), be from by acetic acid (acetic acid), formic acid (formic acid), oxalic acid (oxalic acid), propionic acid (propionic acid), vinylformic acid (acrylic acid), methacrylic acid (methacrylic acid), water, methyl alcohol (methanol), ethanol (ethanol), propyl alcohol (propanol), butanols (Butanol), isopropylcarbinol (isobutanol), amylalcohol (pentanol), hexanol (hexanol), vinyl carbinol (allyl alcohol), 2 hydroxy propanoic acid (2-hydroxy propionic acid), 3-hydroxy-propionic acid (3-hydroxy propionic acid), 2,2-dimethylol propionic acid (2,2-Di methylol propionic acid), 3-(aromatic poly amide-hydroxyphenyl) propionic acid (3-(para-hydroxyphenyl) propionic acid), β-lactic acid (β-lactic acid), sulfuric acid (sulfuric acid), tartrate (tartaric acid), oxysuccinic acid (malic acid), Whitfield's ointment (salicylic acid), one or more compounds of selecting in the group that phenolic acid (phenolic acid) forms.
Phosphoric acid ester shown in described chemical formula 3 (phosphate ester) compound is from (adding the 5wt% of 5 moles, oxyethane (ethylene oxide) by polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate), the 80wt% of 4 moles, the 10wt% of 3 moles, the 5wt% of 1 mole), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 8wt% of 9 moles, oxyethane (ethylene oxide), the 80wt% of 8 moles, the 6wt% of 7 moles, the 6wt% of 6 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 3wt% of 13 moles, oxyethane (ethylene oxide), the 80wt% of 12 moles, the 8wt% of 11 moles, the 3wt% of 9 moles, the 6wt% of 4 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 3wt% of 17 moles, oxyethane (ethylene oxide), the 79wt% of 16 moles, the 10wt% of 15 moles, the 4wt% of 14 moles, the 4wt% of 13 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 5wt% of 21 moles, oxyethane (ethylene oxide), the 76wt% of 20 moles, the 7wt% of 19 moles, the 6wt% of 18 moles, the 4wt% of 17 moles), Zelec UN
tMone or more compounds of selecting in the group who forms.
Shown in the Chemical formula 2 using as internal mold release (release agent), with phosphoric acid ester (phosphate ester) compound shown in the compound of polar group (polar group) or chemical formula 3, with 0.001～10wt%, add in synthetics and be advisable.The compound of band polar group (polar group) preferably adds 0.01～5wt%, if be less than 0.01wt%, release property can be poor, if more than 5wt%, likely there is the problem of eyeglass muddy (cloudiness) or in polymerization process eyeglass shift to an earlier date separated problem with mould.Phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound preferably adds 0.03～1.0wt%, especially adds 0.05～0.5% best.Experimental result, while using 0.08wt%, the release property of eyeglass is fine, and comprehensive yield is also very high.
In order to improve the optical characteristics of resin composition for optical mirror slip, synthetics of the present invention can also comprise thermo-stabilizer.Thermo-stabilizer preferably adds in synthetics and is advisable with 0.01～5.00wt%.If thermo-stabilizer is less than 0.01wt%, can reduce thermal stability result, if more than 5.00wt%, the problem that the polymerization fraction defective in the time of can bringing increase sclerosis, the thermostability of hardening thing decline on the contrary.As thermo-stabilizer, can use metal fatty acid salt (Metal fatty acid salt) series compound, from calcium stearate (calcium stearate), barium stearate (barium stearate), Zinic stearas (zinc stearate), cadmium stearate (cadmium stearate), lead stearate (lead stearate), Magnesium Stearate (magnesium stearate), aluminum stearate (aluminum stearate), potassium stearate (Kalium stearate), one or more compounds of selecting in the compounds such as zinc octanoate (zinc octoate).Preferably use phosphorus series compound, from triphenyl phosphite (Triphenyl phosphite), phosphorous acid hexichol in the last of the ten Heavenly stems (diphenyl decyl phosphite), didecyl phenyl sub-(Phenyl didecyl phosphite), phosphorous acid hexichol dodecane ester (diphenyl dodecyl phosphite), triphenyl Noryl (trinoryl phenyl phosphite), isooctyl diphenyl phosphite (diphenyl isooctyl phosphite), tributyl phosphate (tributyl phosphite), tripropyl phosphite (tripropyl phosphite), triethyl-phosphite (triethyl phosphite), trimethyl phosphite (trimethyl phosphite), Tutofusin tris (list phosphorous acid ester in the last of the ten Heavenly stems) (tris (monodecyl phosphite)), one or more compounds of selecting in Tutofusin tris (single benzene) phosphorous acid ester (tris (mono phenyl) phosphite).In addition, also can use plumbous series compound, from 3PbO.PbSO4.4H
2o, 2PbO.Pb (C
8h
4o
4), 3PbO.Ph (C
4h
2o
4) .H
2one or more compounds that the compounds such as O are selected, also can use organotin (organotin) series compound, from dibutyl auric acid tin (dibutyltin di aurate), dibutyl toxilic acid tin (dibutyltin maleate), dibutyl two (toxilic acid is different pungent) (dibutyltin bis (isooctyl maleate)), dioctyl maleate (dioctyl maleate), dibutyl two (monomethyl maleate) (dibutyltin bis (mono methyl maleate)), dibutyl two (lauryl mercaptan salt) (dibutyltin bis (Lauryl mercaptide)), dibutyl two (Thiovanic acid is different pungent) (dibutyltin bis (isooctyl mercapto acetate)), Monobutyltin three (Thiovanic acid is different pungent) (mono butyltin tris (isooctyl mercapto acetate)), dimethyl two (Thiovanic acid is different pungent) (dimethyltin bis (isooctyl mercapto acetate)), three (Thiovanic acid is different pungent) tris (isooctyl mercapto acetate)), finish pyridine (Thiovanic acid is different pungent) (bioctyltin bis (isooctyl mercapto acetate)), dibutyl tin two (2-sulfydryl ethyl laurate) (dibutyltin bis (2-mercapto ethyllaurate)), Monobutyltin three (2-sulfydryl ethyl laurate) (monobutyltin tris (2-mercapto ethyllaurate)), dimethyl two (2-sulfydryl ethyl laurate) (dimethyltin bis (2-mercapto ethyllaurate)), monomethyl three (2-sulfydryl ethyl laurate) (monomethyltin tris (2-mercapto ethyllaurate)), Deng one or more compounds of selecting in compound.In addition, also can mix the two or more thermo-stabilizers that use different series.Preferably use phosphorus series of heat stablizer.Use phosphorus series of heat stablizer, can, in the situation that not reducing the optical characteristics such as transparency, shock strength, thermotolerance and polymerization yield, significantly improve the thermostability of optical mirror slip.
Of the present invention is 15～75wt% for regulating optical mirror slip with the reactive diluent content of resin composition viscosity.While adding reactive diluent in synthetics, can obtain the liquid phase viscosity that is easy to implantation glass mould is the serial high dioptric optical mirror slip resin composition of epoxy acrylic (Epoxy Acrylate) of 20～1000cps at 25 ℃ of temperature.Here, glass mold is by adhesive tape or the assembling of synthetic resins sealing-ring.If liquid phase viscosity is lower than 20cps, to the glass mold with synthetic resins sealing-ring assembling, when injecting liquid resin composition and carrying out moulding, there will be the problem of synthetic overflow outside, if liquid phase viscosity is greater than 1000cps, there will be the problem that is difficult to synthetics to inject mould.Best range of viscosities is 30～500cps.For regulating optical mirror slip with the reactive diluent of resin composition viscosity can be but be not limited to from by vinylbenzene (styrene), Vinylstyrene (divinylbenzene), α-methylstyrene (α methyl styrene), α-methylstyrene dimer (α methyl styrene dimer), phenyl methacrylate (benzyl methacrylate), chloro-styrene (Chloro styrene), bromstyrol (Bromo styrene), methoxy styrene (methoxy styrene), monobenzyl malate (Monobenzyl malate), dibenzyl malate (dibenzyl malate), monobenzyl fumaric acid esters (Monobenzyl fumarate), dibenzyl fumaric acid esters (dibenzyl fumarate), methyl-benzyl malate (Methyl benzyl malate), oxysuccinic acid dimethyl ester (dimethyl malate), diethyl malate (diethyl malate), oxysuccinic acid fourth diester (dibutyl malate), dibutyl fumarate (dibutyl fumarate), oxysuccinic acid only son (monobutyl malate), oxysuccinic acid list pentyl ester (monopentyl malate), oxysuccinic acid diamyl ester (dipentyl malate), fumaric acid list pentyl ester (monopentyl fumarate), fumaric acid diamyl ester (dipentyl fumarate), one or more compounds of selecting in the group that Diethylene Glycol diene propyl carbonate (diethylene glycol bis allyl carbonate) forms.After preferably purifying, obtain high purity substance for the synthesis of all reactive diluents of thing, be used in synthetics.
In the present invention, manufacturing for optical mirror slip with before epoxy acrylic (Epoxy Acrylate) resin compound and reactive diluent compound of resin composition, first confirm the purity of all raw material, the compound that purity is low is purified, and the compound that purity is high is not purified and is directly used and be advisable.In the present invention, preferably using purity is 70～99.99% high-purity compound.
In order to improve optical characteristics, optical mirror slip of the present invention can also comprise the known UV light absorber of adding with usual method, organic dye, mineral dye, anti-coloring agent, thermo-stabilizer, oxidation inhibitor, photostabilizer, catalyzer etc. with resin composition.
In polymerization process of the present invention or synthetics, if use shown in Chemical formula 2 the compound with polar group (polar group) as internal mold release (release agent), as auxiliary internal releasing agent (release agent), can use general by phosphoric acid ester (phosphate ester) compound, silica gel series of surfactants (surfactant) and fluorine series of surfactants (surfactant) simultaneously.As auxiliary internal releasing agent (release agent), preferably use phosphoric acid ester (phosphate ester) compound.Here, spendable generally have with phosphate (phosphate ester) compound, such as, from (single, two) methyl acid phosphate ((mono, di) methyl phosphoric), (single, two) ethyl phosphonic acid ((mono, di) ethyl phosphoric), (single, two) (n-propyl group) phosphoric acid ((mono, di) (n-propyl) phosphoric), (single, two) isopropyl phosphoric acid ((mono, di) isopropyl phosphoric), (single, two) (n-butyl) phosphoric acid ((mono, di) (n-butyl) phosphoric), (single, two) (n-amyl group) phosphoric acid ((mono, di) (n-pentyl) phosphoric), (single, two) (n-hexyl) phosphoric acid ((mono, di) (n-hexyl) phosphoric), (single, two) (n-heptyl) phosphoric acid ((mono, di) (n-Heptyl) phosphoric), (single, two) (n-octyl group) phosphoric acid ((mono, di) (n-octyl) phosphoric), (single, two) (2-ethylhexyl) phosphoric acid ((mono, di) (2-ethyl hexyl) phosphoric), (single, two) (n-nonyl) phosphoric acid ((mono, di) (n-nonyl) phosphoric), (single, two) (n-decyl) phosphoric acid ((mono, di) (n-decyl) phosphoric), (single, two) (isodecyl) phosphoric acid ((mono, di) (isodecyl) phosphoric), (single, two) (n-undecyl) phosphoric acid ((mono, di) (n-undecyl) phosphoric), (single, two) (n-dodecyl) phosphoric acid ((mono, di) (n-dodecyl) phosphoric), (single, two) (tridecyl) phosphoric acid ((mono, di) (tridecyl) phosphoric), (single, two) (n-myristyl) phosphoric acid ((mono, di) (n-tetradecyl) phosphoric), (single, two) (n-pentadecyl) phosphoric acid ((mono, di) (n-pentadecyl) phosphoric), (single, two) (n-cetyl) phosphoric acid ((mono, di) (n-hexadecyl) phosphoric), (single, two) (n-octadecyl) phosphoric acid ((mono, di) (n-octadecyl) phosphoric), (single, two) (o-methyl decyl) phosphoric acid ((mono, di) (o-methyl decyl) phosphoric),(single, two) (p-aminomethyl phenyl) phosphoric acid ((mono, di) (p-methyl phenyl) phosphoric), (single, two) (p-ethylphenyl) phosphoric acid ((mono, di) (p-ethyl phenyl) phosphoric), (single, two) (p-propyl group phenyl) phosphoric acid ((mono, di) (p-propyl phenyl) phosphoric), (single, two) (p-butyl phenyl) phosphoric acid ((mono, di) (p-butyl phenyl) phosphoric), (single, two) (p-nonyl phenyl) phosphoric acid ((mono, di) (p-nonyl phenyl) phosphoric), (single, two) (p-methyl) phosphoric acid ((mono, di) (p-methyl methyl) phosphoric), (single, two) (2-phenethyl) phosphoric acid ((mono, di) (2-phenylethyl) phosphoric), (single, two) (4-benzene butyl) phosphoric acid ((mono, di) (4-phenyl butyl) phosphoric), (single, two) (3-oxa-butyl) phosphoric acid ((mono, di) (3-oxa butyl) phosphoric), (single, two) (3-oxa-amyl group) phosphoric acid ((mono, di) (3-oxa pentyl) phosphoric), (single, two) (3-oxa-hexyl) phosphoric acid ((mono, di) (3-oxa hexyl) phosphoric), (single, two) (3-oxa-heptyl) phosphoric acid ((mono, di) (3-oxa Heptyl) phosphoric), (single, two) (3-oxa-octyl group) phosphoric acid ((mono, di) (3-oxa octyl) phosphoric), (single, two) (3-oxa-nonyl) phosphoric acid ((mono, di) (3-oxa nonyl) phosphoric), (single, two) (3-oxa-undecyl) phosphoric acid ((mono, di) (3-oxa undecyl) phosphoric), (single, two) (3-oxa-tridecyl) phosphoric acid ((mono, di) (3-oxa tridecyl) phosphoric), (single, two) (3-oxa-pentadecyl) phosphoric acid ((mono, di) (3-oxa pentadecyl) phosphoric), (single, two) (3-oxa-heptadecyl) phosphoric acid ((mono, di) (3-oxa heptadecyl) phosphoric), (single, two) (3-oxa-nonadecyl) phosphoric acid ((mono,Di) (3-oxa nonadecyl) phosphoric), (single, two) (3-oxa-heneicosyl) phosphoric acid ((mono, di) (3-oxa heneicosyl) phosphoric), (single, two) (1-methyl-3-oxa-butyl) phosphoric acid ((mono, di) (1-methyl-3-oxa butyl) phosphoric), (single, two) (1-methyl-3-oxa-amyl group) phosphoric acid ((mono, di) (1-methyl-3-oxa pentyl) phosphoric), (single, two) (1-methyl-3-oxa-heptyl) phosphoric acid ((mono, di) (1-methyl-3-oxa Heptyl) phosphoric), (single, two) (1,2-dimethyl-3-oxa-heptyl) phosphoric acid ((mono, di) (1,2-dimethyl-3-oxa Heptyl) phosphoric), (single, two) (1-methyl-3-oxa-tridecyl) phosphoric acid ((mono, di) (1-methyl-3-oxa tridecyl) phosphoric), (single, two) (1-methyl-2-(o-methylphenoxy) ethyl) phosphoric acid ((mono, di) (1-methyl-2-(o-methyl phenoxy) ethyl) phosphoric), (single, two) (1-methyl 2-(p-Nonylphenoxy ethyl) phosphoric acid ((mono, di) (1-methyl2-(p-nonyl phenoxy ethyl) phosphoric), (single, two) (1-methyl 4-phenyl-3-oxa-butyl) phosphoric acid ((mono, di) (1-methyl-4-phenyl-3-oxa butyl) phosphoric), (single, two) (3,6-dioxaheptyl) phosphoric acid ((mono, di) (3,6-dioxa Heptyl) phosphoric), (single, two) (3,6-dioxa octyl group) phosphoric acid ((mono, di) (3,6-dioxa octyl) phosphoric), (single, two) (3,6-dioxa decyl) phosphoric acid ((mono, di) (3,6-dioxa decyl) phosphoric), (single, two) (3,6-dioxa myristyl) phosphoric acid ((mono, di) (3,6-dioxa tetradecyl) phosphoric), (single, two) (3,6-dioxa cetyl) phosphoric acid ((mono, di) (3,6-dioxa hexadecyl) phosphoric), (single, two) (3,6-dioxa octadecyl) phosphoric acid ((mono, di) (3,6-dioxa octadecyl) phosphoric), (3,6-dioxa eicosyl) phosphoric acid ((3,6-dioxa eicosyl) phosphoric), (3,6-dioxa docosyl) phosphoric acid ((3,6-dioxa docosyl) phosphoric), (single, two) (3,6-dioxa tetracosyl) phosphoric acid ((mono, di) (3,6-dioxa tetracosyl) phosphoric), (single, two) (Isosorbide-5-Nitrae-dimethyl 3,6-dioxa decyl) phosphoric acid ((mono, di) (Isosorbide-5-Nitrae-dimethyl3,6-dioxa decyl) phosphoric), (single, two) (3,6,9-trioxa decyl) phosphoric acid ((mono, di) (3,6,9-trioxa decyl) phosphoric), (single, two) (3,6,9-trioxa undecyl) phosphoric acid ((mono, di) (3,6,9-trioxa undecyl) phosphoric), (single, two) (3,6,9-trioxa tridecyl) phosphoric acid ((mono, di) (3,6,9-trioxa tridecyl) phosphoric), (single, two) (3,6,9-trioxa heptadecyl) phosphoric acid ((mono, di) (3,6,9-trioxa heptadecyl) phosphoric), (single, two) (3,6,9-trioxa heneicosyl) phosphoric acid ((mono, di) (3,6,9-trioxa heneicosyl) phosphoric), (single, two) (3,6,9-trioxa heptacosane base) phosphoric acid ((mono, di) (3,6,9-trioxa heptacosyl) phosphoric), (single, two) (Isosorbide-5-Nitrae, 7-trimethyl-3,6,9-trioxa tridecyl) phosphoric acid ((mono, di) (Isosorbide-5-Nitrae, 7-trimethyl-3,6,9-trioxa tridecyl) phosphoric), (single, two) (3,6,9,12-tetraalkyl oxa-cetyl) phosphoric acid ((mono, di) (3,6,9,12-tetraoxahexadecyl) phosphoric), (single, two) (3,6,9,12-tetraalkyl oxa-octadecyl) phosphoric acid ((mono, di) (3,6,9,12-tetra oxa octadecyl) phosphoric), (single, two) (3,6,9,12-tetraalkyl oxa-eicosyl) phosphoric acid ((mono, di) (3,6,9,12-tetra oxa eicosyl) phosphoric), (single,Two) (3,6,9,12-tetraalkyl oxa-docosyl) phosphoric acid ((mono, di) (3,6,9,12-tetra oxa docosyl) phosphoric), (single, two) (3,6,9,12-tetraalkyl oxa-tetracosyl) phosphoric acid ((mono, di) (3,6,9,12-tetra oxa tetra cosyl) phosphoric), (single, two) (Isosorbide-5-Nitrae, 7,10-tetraalkyl methyl-3,6,9,12-tetraalkyl oxa-cetyl) phosphoric acid ((mono, di) (Isosorbide-5-Nitrae, 7,10-tetra methyl3,6,9,12-tetra oxa hexadecyl) phosphoric), three isothioate acid esters (triisopropyl phosphate), tributyl phosphate (tributyl phosphate), trioctyl phosphate (trioctyl phosphate), tricresyl phosphate isodecyl (triisodecyl phosphate), tridecanol phosphate (tridecanol phosphate), two (decyl alcohol) phosphate (bis (decanol) phosphate), trimethyl phosphate (trimethyl phosphate), triethyl phosphate (triethyl phosphate), tripropyl ester (tripropyl ester), benzyl phosphate (benzyl phosphate), dibenzyl phosphate (dibenzyl phosphate), tribenzyl phosphate (tribenzyl phosphate), two (tridecanol) phosphate (bis (tridecanol phosphate)) ethylene glycol list ethyl phosphonic acid ester (ethylene glycol mono ethyl phosphate), diethylene glycol list ethyl phosphonic acid ester (diethylene glycol mono ethyl phosphate), triethylene glycol list ethyl phosphonic acid ester (triethylene glycol mono ethyl phosphate), diethylene glycol monophosphate dibutyl ester (diethylene glycol mono butyl diphosphate), diethylene glycol monophosphate butyl ester (diethylene glycol mono butyl phosphate), Isopropanediol list ethyl phosphonic acid ester (isopropylene glycol mono ethyl phosphate), di-isopropylene glycol list ethyl phosphonic acid ester (diisopropylene glycol mono ethyl phosphate),Three Isopropanediol list ethyl phosphonic acid esters (triisopropylene glycol mono ethyl phosphate), Zelec UN
TMSelect one or more uses.Spendable phosphoric acid ester (phosphate ester) compound is not limited to above-claimed cpd, is not limited to the compound that uses single proportioning.
In addition, in polymerization process of the present invention or synthetics, if use phosphoric acid ester (phosphate ester) compound shown in chemical formula 3 as internal mold release (release agent), in order more to improve release property, as complementary internal mold release (release agent), can use shown in Chemical formula 2 the compound with polar group (polar group).
[embodiment]
For making object, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is carried out to clear, complete description, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
epoxy acrylic (Epoxy Acrylate) compound
1) composition (I) compound is synthetic
Composition (I) compound is as shown in chemical formula 4, (the KUKDO CHEMICAL CO. of the state Dow Chemical Company that is 187 to equivalent, LTD.) YD-128 epoxy resin (epoxy resin) adds vinylformic acid (acrylic acid) and carries out acrylated (acrylate) (reacting manufacture in 20 hours at 105 ℃), the compound that to have manufactured equivalent be 259 is molecular-weight average is 518 mixture.
Chemical formula 4
2) composition (II) compound
Compound Phase shown in composition (II) compound and chemical formula 3 is same, it is a kind of mixture, after acrylated (acrylate) finishes, add 0.1wt% oxalic acid (oxalic acid), 100 ℃ of condition bottom fermentations 30 minutes, other are identical with composition (I).
3) composition (III) compound
Composition (III) compound is as shown in chemical formula 5, the epoxy resin that is 201 to equivalent (epoxy resin) adds vinylformic acid (acrylic acid) and carries out acrylated (acrylate) (reacting manufacture in 20 hours at 105 ℃), the compound that to have manufactured equivalent be 273 is molecular-weight average is 546 mixture.
Chemical formula 5
4) composition (IV) compound
Composition (IV) compound is as shown in chemical formula 6, (the KUKDO CHEMICAL CO. of the state Dow Chemical Company that is 400 to equivalent, LTD.) YDB-400 epoxy resin (epoxy resin) adds vinylformic acid (acrylic acid) and carries out acrylated (acrylate) (reacting manufacture in 20 hours at 105 ℃), the compound that to have manufactured equivalent be 472 is molecular-weight average is 944 mixture.
Chemical formula 6
5) composition (V) compound
Composition (V) compound is as shown in chemical formula 7, the epoxy resin that is 414 to equivalent (epoxy resin) adds vinylformic acid (acrylic acid) and carries out acrylated (acrylate) (reacting manufacture in 20 hours at 105 ℃), the compound that to have manufactured equivalent be 486 is molecular-weight average is 972 mixture.
Chemical formula 7
Embodiment 1
In epoxy acrylic (Epoxy Acrylate) compound obtaining in the above-described manner, to composition (I) 21g and composition (IV) 35g, add after vinylbenzene (styrene) 40g, styrene dimer (styrene dimer) 2g, DBTM2g, oxalic acid (oxalic acid) 0.05g, approximately stir 30 minutes.With the following filter paper of 0.45 μ m, filter afterwards, to it, as catalyzer, add V650.05g, 3-M0.12g, mixes Zelec UN as internal mold release (release agent)
tM0.2g, manufactures optical mirror slip with after resin composition, with following method, manufactures optical mirror slip, the physical property of the eyeglass of detection.
(1) optical mirror slip of as above manufacturing is stirred after 1 hour with resin composition, decompression dehydration 10 minutes, filters, and injects the glass mold with the assembling of polyester (polyester) adhesive tape.
(2) being injected with glasses lens, with the glass mold of resin composition, put into forced cyclic type stove, from 35 ℃ to 110 ℃, heat hardening is after 20 hours, cooling with 70 ℃ after, unload glass mold, obtained eyeglass.The machining eyeglass obtaining is become after diameter 72mm size, by buck (alkaline aqueous) washings, undertaken after ultrasonic washing, under 120 ℃ of conditions, heat-treat (annealing) 2 hours.Detect by the following method physical property, result is as shown in table 1.
physical property measurement method
By following physical property measurement method, the optical mirror slip of manufacturing is carried out to physical property measurement, outcome record in table 1.
1) refractive index and Abbe number (Abbe ' s number): use and like to open up the Abbe dioptrometer that (Atago) company model is DR-M4, detect.
2) proportion: utilize analytical balance, measure by substitution method in water.
2) release property: allow epoxy acrylic (Epoxy Acrylate) resin composition heat embrittlement, when 70 ℃ of demouldings, according to the damaged degree of glass lens and mould, fill in zero, △, X.Here, as eyeglass, manufacture respectively dioptry (diopter) for-1.00 100, dioptry (diopter) be 0.00 100, dioptry (diopter) are 1.00 100, detect.To each dioptry group eyeglass,
Zero: mean that eyeglass or mould do not have breakage or occur 1 breakage;
△: have 2～3 that mean eyeglass or mould breakage.
X: mean having more than 4 of eyeglass or mould breakage.
3) polymerization is inhomogeneous: to obtain by operation 100 eyeglasses, the mercury arc lamp (Mercury Arc Lamp) that naked eyes and model be USH10USH-102D of take is observed, as occurred there are 3 above, marks " X " in optical distortion, as optical distortion occurs that 3 with next mark " zero ".
Embodiment 2～20
With the method for embodiment 1, by table 1, to proportioning shown in 3, manufacture respectively each synthetics and optical mirror slip, done physical property detection, result is if table 1 is to as shown in the of 3.
Comparative example 1
To composition (I) 21g and composition (IV) 35g in epoxy acrylic (Epoxy Acrylate) compound, add after vinylbenzene (styrene) 40g, methyl styrene dimer body (methyl styrene dimer) 2g, DBTM2g, approximately stir 30 minutes.With the following filter paper of 0.45 μ m, filter afterwards, to it, as catalyzer, add V650.05g, 3-M0.12g, mixes Zelec UN as internal mold release (release agent)
tM0.2g, manufactures optical mirror slip resin composition with the method as embodiment 1.By this synthetics, manufacture after optical mirror slip, the physical property of the eyeglass of detection, outcome record is as table 3.
Comparative example 2～4
With the method for comparative example 1, the proportioning of recording by table 3, manufactures respectively each synthetics and optical mirror slip, detects physical property, and outcome record is as table 3.
[table 1]
[table 2]
[table 3]
If table 1 is to as shown in the of 3, to epoxy acrylic (Epoxy Acrylate) resin and reactive diluent add internal mold release of the present invention (release agent) and resin composition (embodiment), compare with comparative example, polymerization non-uniform phenomenon is few, and release property is good.In addition, while manufacturing epoxy acrylic (Epoxy Acrylate) series compound, add in advance after internal mold release of the present invention (release agent), hybrid reaction thinner, manufacture optical mirror slip resin composition, also can reduce polymerization non-uniform phenomenon, and improve release property.Thereby known, while using internal mold release of the present invention (release agent), can prevent polymerization non-uniform phenomenon, obtain outstanding release property, can improve the efficiency that optical mirror slip is manufactured, and eyeglass damage can prevent the demoulding time, can improve yield, the optical characteristics such as the transparency and thermostability are also outstanding.
Be called for short
internal mold release (release agent)
Zelec UN
tM: be phosphoric acid ester (phosphate ester) compound that Si Taipan (Stapan) company manufactures, trade name is Zelec UN
DOP: dioctylphosphoric acid ester (dioctyl acid pho sphate)
4-PENPP: polyoxyethylene nonylphenol ether phosphoric acid ester (polyoxyethylene nonyl phenyl ether phosphate) (add 5 moles, oxyethane (ethylene oxide) 5wt%, add 4 moles, oxyethane (ethylene oxide) 80wt%, add 3 moles, oxyethane (ethylene oxide) 10wt%, add the 5wt% of 1 mole, oxyethane (ethylene oxide))
8-PENPP: polyoxyethylene nonylphenol ether phosphoric acid ester (polyoxyethylene nonyl phenyl ether phosphate) (adding 5wt%, the 80wt% that adds 8 moles, oxyethane (ethylene oxide), the 10wt% that adds 7 moles, oxyethane (ethylene oxide), 6 moles of following 5wt% of interpolation oxyethane (ethylene oxide) of 9 moles, oxyethane (ethylene oxide))
12-PENPP: polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adding 3wt%, the 80wt% of 12 moles, 8wt%, the 3wt% of 9 moles, the 6wt% of 4 moles of 11 moles of 13 moles, oxyethane (ethylene oxide))
16-PENPP: polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adding 3wt%, the 79wt% of 16 moles, 10wt%, the 4wt% of 14 moles, the 4wt% of 13 moles of 15 moles of 17 moles, oxyethane (ethylene oxide))
20-PENPP: polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adding 5wt%, the 76wt% of 12 moles, 7wt%, the 6wt% of 10 moles, the 4wt% of 9 moles of 11 moles of 13 moles, oxyethane (ethylene oxide))
KF96: the silica gel series releasing agent that company of SHIN-ETSU HANTOTAI (shin-etsu) produces, trade name is KF96.
thermo-stabilizer
DBTM: dibutyl toxilic acid tin (dibutyltin maleate)
DOTM: maleic acid ester tin octylate (dioctyltinmaleate)
ZnST: Zinic stearas (zinc stearate)
TPP: triphenyl phosphite (triphenyl phosphite)
TBP: tributyl phosphate (tributyl phosphite)
DPP: phosphorous acid hexichol isodecyl (diphenyl isodecyl phosphite)
polymerization starter
V65:2,2 '-azo two (2,4-diformazan valeronitrile) (2,2 '-azobis (2,4-dimethyl valeronitrile)
3-M:1,1-bis-(t-butyl peroxy)-3,3-5-trimethyl-cyclohexane (1,1-bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane)
Industry is utilized feasibility
The serial optical mirror slip of epoxy acrylic of the present invention (Epoxy Acrylate) can overcome the problem points of original technology with resin---the poor problem of release property after polymerization, can bring into play the excellent optical properties of the aspects such as self light weight, formability, dyeability, the transparency, be to be subject to the resin that moisture effects is low, thermostability is high, can be widely used in optical field.Press the resin of method manufacture of the present invention applicable to optical mirror slip, particularly glasses lens and pick up camera eyeglass.This resin also can be used in the 3D polarized lenses that light polarizing film is installed at glasses lens, can also be applied in multiple optical articles fields such as prism (prism), fiber optics, the recording medium substrate that is used in CD, disk etc. or painted strainer and ultraviolet radiation absorption strainers.
Claims (17)
1. resin die casting (mold) polymerization (polymerization) method for the serial optical mirror slip of an epoxy acrylic (Epoxy Acrylate), it is characterized in that: by die casting (mold) polymerization (polymerization), manufacture and to comprise while using synthetics containing epoxy acrylic (Epoxy Acrylate) resin compound 20～80wt% of compound shown in one or both Chemical formula 1s and the optical mirror slip of reactive diluent 15～75wt%, as internal mold release (release agent), add in advance shown in Chemical formula 2 with phosphoric acid ester (phosphate ester) compound 0.001～10wt% shown in the compound of polar group (polar group) or chemical formula 3.
Chemical formula 1
(here, n=0～15, R1 is H or CH3, R2 is H or Br.)
Chemical formula 2
R1—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
Chemical formula 3
(here, R is hydrocarbon 3～20 alkyl (Alkyl), and n is that 0～10, m is 1～2.)
2. resin die casting (mold) polymerization (polymerization) method for the serial optical mirror slip of epoxy acrylic according to claim 1 (Epoxy Acrylate), is characterized in that:
The compound of described band polar group (polar group) is from by acetic acid (acetic acid), formic acid (formic acid), oxalic acid (oxalic acid), propionic acid (propionic acid), vinylformic acid (acrylic acid), methacrylic acid (methacrylic acid), water, methyl alcohol (methanol), ethanol (ethanol), propyl alcohol (propanol), butanols (Butanol), isopropylcarbinol (isobutanol), amylalcohol (pentanol), hexanol (hexanol), vinyl carbinol (allyl alcohol), 2 hydroxy propanoic acid (2-hydroxy propionic acid), 3-hydroxy-propionic acid (3-hydroxy propionic acid), 2,2-dimethylol propionic acid (2,2-Di methylol propionic acid), 3-(aromatic poly amide-hydroxyphenyl) propionic acid (3-(para-hydroxyphenyl) propionic acid), β-lactic acid (β-lactic acid), sulfuric acid (sulfuric acid), tartrate (tartaric acid), oxysuccinic acid (malic acid), Whitfield's ointment (salicylic acid), one or more compounds of selecting in the group that phenolic acid (phenolic acid) forms.
3. resin die casting (mold) polymerization (polymerization) method for the serial optical mirror slip of epoxy acrylic according to claim 1 (Epoxy Acrylate), is characterized in that:
Described phosphoric acid ester (phosphate ester) compound is from (adding the 5wt% of 5 moles, oxyethane (ethylene oxide) by polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate), the 80wt% of 4 moles, the 10wt% of 3 moles, the 5wt% of 1 mole), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 8wt% of 9 moles, oxyethane (ethylene oxide), the 80wt% of 8 moles, the 6wt% of 7 moles, the 6wt% of 6 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 3wt% of 13 moles, oxyethane (ethylene oxide), the 80wt% of 12 moles, the 8wt% of 11 moles, the 3wt% of 9 moles, the 6wt% of 4 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether pho sphate) (adds the 3wt% of 17 moles, oxyethane (ethylene oxide), the 79wt% of 16 moles, the 10wt% of 15 moles, the 4wt% of 14 moles, the 4wt% of 13 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 5wt% of 21 moles, oxyethane (ethylene oxide), the 76wt% of 20 moles, the 7wt% of 19 moles, the 6wt% of 18 moles, the 4wt% of 17 moles), Zelec UN
tMone or more compounds of selecting in the group who forms.
4. resin die casting (mold) polymerization (polymerization) method for the serial optical mirror slip of epoxy acrylic according to claim 1 (Epoxy Acrylate), is characterized in that:
Described reactive diluent is from by vinylbenzene (styrene), Vinylstyrene (divinylbenzene), α-methylstyrene (α methyl styrene), α-methylstyrene dimer (α methyl styrene dimer), phenyl methacrylate (benzyl methacrylate), chloro-styrene (Chloro styrene), bromstyrol (Bromo styrene), methoxy styrene (methoxy styrene), monobenzyl malate (Monobenzyl malate), dibenzyl malate (dibenzyl malate), monobenzyl fumaric acid esters (Monobenzyl fumarate), dibenzyl fumaric acid esters (dibenzyl fumarate), methyl-benzyl malate (Methyl benzyl malate), oxysuccinic acid dimethyl ester (dimethyl malate), diethyl malate (diethyl malate), oxysuccinic acid fourth diester (dibutyl malate), dibutyl fumarate (dibutyl fumarate), oxysuccinic acid only son (monobutyl malate), oxysuccinic acid list pentyl ester (monopentyl malate), oxysuccinic acid diamyl ester (dipentyl malate), fumaric acid list pentyl ester (monopentyl fumarate), fumaric acid diamyl ester (dipentyl fumarate), one or more compounds of selecting in the group that Diethylene Glycol diene propyl carbonate (diethylene glycol bis allyl carbonate) forms.
5. resin die casting (mold) polymerization (polymerization) method for the serial optical mirror slip of epoxy acrylic according to claim 1 (Epoxy Acrylate), is characterized in that:
Described optical mirror slip also comprises thermo-stabilizer with synthetics.
6. according to the serial optical mirror slip of the epoxy acrylic described in any one in claim 1,2,4,5 (Epoxy Acrylate) resin die casting (mold) polymerization (polymerization) method, it is characterized in that:
Described internal mold release (release agent) is the compound of polar group (polar group) shown in band Chemical formula 2, and described optical mirror slip also comprises phosphoric acid ester (phosphate ester) compound with synthetics as internal mold release (release agent).
7. according to the serial optical mirror slip of the epoxy acrylic described in any one in claim 1,3 to 5 (Epoxy Acrylate) resin die casting (mold) polymerization (polymerization) method, it is characterized in that:
Described internal mold release (release agent) is phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound, and described optical mirror slip also comprises shown in following Chemical formula 2 the compound with polar group (polar group) with synthetics as internal mold release (release agent).
Chemical formula 2
R—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
8. the serial optical mirror slip resin composition of epoxy acrylic (Epoxy Acrylate), is characterized in that:
Comprise epoxy acrylic (Epoxy Acrylate) resin compound 20～80wt% containing compound shown in one or both Chemical formula 1s, reactive diluent 15～75wt%, as shown in internal mold release (release agent), Chemical formula 2 with phosphoric acid ester (phosphate ester) compound 0.001～10wt% shown in the compound of polar group (polar group) or chemical formula 3.
Chemical formula 1
(here, n=0～15, R1 is H or CH3, R2 is H or Br.)
Chemical formula 2
R—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
Chemical formula 3
(here, R is hydrocarbon 3～20 alkyl (Alkyl), and n is that 0～10, m is 1～2.)
9. the serial optical mirror slip resin composition of epoxy acrylic according to claim 8 (Epoxy Acrylate), is characterized in that:
Liquid phase viscosity in the time of 25 ℃ 20～1,000cps, liquid phase refractive index (nE, 20 ℃) is 1.50～1.58, solid phase refractive index (nE, 20 ℃) is 1.54～1.63.
10. the serial optical mirror slip resin composition of epoxy acrylic according to claim 8 (Epoxy Acrylate), is characterized in that:
The compound of described band polar group (polar group) is from by acetic acid (acetic acid), formic acid (formic acid), oxalic acid (oxalic acid), propionic acid (propionic acid), vinylformic acid (acrylic acid), methacrylic acid (methacrylic acid), water, methyl alcohol (methanol), ethanol (ethanol), propyl alcohol (propanol), butanols (Butanol), isopropylcarbinol (isobutanol), amylalcohol (pentanol), hexanol (hexanol), vinyl carbinol (allyl alcohol), 2 hydroxy propanoic acid (2-hydroxy propionic acid), 3-hydroxy-propionic acid (3-hydroxy propionic acid), 2,2-dimethylol propionic acid (2,2-Di methylol propionic acid), 3-(aromatic poly amide-hydroxyphenyl) propionic acid (3-(para-hydroxyphenyl) propionic acid), β-lactic acid (β-lactic acid), sulfuric acid (sulfuric acid), tartrate (tartaric acid), oxysuccinic acid (malic acid), Whitfield's ointment (salicylic acid), one or more compounds of selecting in the group that phenolic acid (phenolic acid) forms.
The serial optical mirror slip resin composition of 11. epoxy acrylics according to claim 8 (Epoxy Acrylate), is characterized in that:
Described phosphoric acid ester (phosphate ester) compound is from (adding the 5wt% of 5 moles, oxyethane (ethylene oxide) by polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate), the 80wt% of 4 moles, the 10wt% of 3 moles, the 5wt% of 1 mole), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 8wt% of 9 moles, oxyethane (ethylene oxide), the 80wt% of 8 moles, the 6wt% of 7 moles, the 6wt% of 6 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 3wt% of 13 moles, oxyethane (ethylene oxide), the 80wt% of 12 moles, the 8wt% of 11 moles, the 3wt% of 9 moles, the 6wt% of 4 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 3wt% of 17 moles, oxyethane (ethylene oxide), the 79wt% of 16 moles, the 10wt% of 15 moles, the 4wt% of 14 moles, the 4wt% of 13 moles), polyoxyethylene nonyl phenol ether phosphate (polyoxyethylene nonyl phenol ether phosphate) (adds the 5wt% of 21 moles, oxyethane (ethylene oxide), the 76wt% of 20 moles, the 7wt% of 19 moles, the 6wt% of 18 moles, the 4wt% of 17 moles), Zelec UN
tMone or more compounds of selecting in the group who forms.
The serial optical mirror slip resin composition of 12. epoxy acrylics according to claim 8 (Epoxy Acrylate), is characterized in that:
Described reactive diluent is from by vinylbenzene (styrene), Vinylstyrene (divinylbenzene), α-methylstyrene (α methyl styrene), α-methylstyrene dimer (α methyl styrene dimer), phenyl methacrylate (benzyl methacrylate), chloro-styrene (Chloro styrene), bromstyrol (Bromo styrene), methoxy styrene (methoxy styrene), monobenzyl malate (Monobenzyl malate), dibenzyl malate (dibenzyl malate), monobenzyl fumaric acid esters (Monobenzyl fumarate), dibenzyl fumaric acid esters (dibenzyl fumarate), methyl-benzyl malate (Methyl benzyl malate), oxysuccinic acid dimethyl ester (dimethyl malate), diethyl malate (diethyl malate), oxysuccinic acid fourth diester (dibutyl malate), dibutyl fumarate (dibutyl fumarate), oxysuccinic acid only son (monobutyl malate), oxysuccinic acid list pentyl ester (monopentyl malate), oxysuccinic acid diamyl ester (dipentyl malate), fumaric acid list pentyl ester (monopentyl fumarate), fumaric acid diamyl ester (dipentyl fumarate), one or more compounds of selecting in the group that Diethylene Glycol diene propyl carbonate (diethylene glycol bis allyl carbonate) forms.
The serial optical mirror slip resin composition of 13. epoxy acrylics according to claim 8 (Epoxy Acrylate), is characterized in that:
Also comprise thermo-stabilizer.
The serial optical mirror slip resin composition of epoxy acrylic in 14. according to Claim 8 to 10,12 to 13 described in any one (Epoxy Acrylate), is characterized in that:
Described internal mold release (release agent) is the compound of polar group (polar group) shown in band Chemical formula 2, as internal mold release (release agent), also comprises phosphoric acid ester (phosphate ester) compound.
The serial optical mirror slip resin composition of epoxy acrylic (Epoxy Acrylate) 15. according to Claim 8, in 9,11 to 13 described in any one, is characterized in that:
Described internal mold release (release agent) is phosphoric acid ester shown in chemical formula 3 (phosphate ester) compound, as internal mold release (release agent), also comprises shown in following Chemical formula 2 the compound with polar group (polar group).
[Chemical formula 2]
R—X
n
(here, R is the residue (residue) of hydrogen, carbon, alkyl (Alkyl), the alkyl (Alkyl) that comprises unsaturated (unsaturated) base, aromatic base, alkyl phenyl (Alkylphenyl), phenylalkyl (phenylalkyl), alicyclic (Cycloaliphatic).X is hydroxyl (hydroxy) or carboxyl (carboxylic acid) or both double fingers.N is 1～6 integer.)
16. 1 kinds of optical materials, is characterized in that:
Synthetics to claim 8 adds enzyme, carries out heat embrittlement acquisition.
17. 1 kinds of plastic eyeglass lenses or polarized lenses, is characterized in that:
Optical material by claim 16 forms.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| PCT/KR2012/004673 WO2013187539A1 (en) | 2012-06-13 | 2012-06-13 | Method for polymerizing resin casting for use as epoxy acrylic optical lens and resin composition containing internal releasing agent for use in epoxy acrylic optical lens |
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| CN103635497A true CN103635497A (en) | 2014-03-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104583249A (en) * | 2012-08-27 | 2015-04-29 | 可奥熙搜路司有限公司 | Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material |
| CN107107403A (en) * | 2014-12-26 | 2017-08-29 | 三井化学株式会社 | The manufacture method of internal mold release, the composition comprising the internal mold release and the plastic lens using said composition |
| CN109575239A (en) * | 2018-12-13 | 2019-04-05 | 山东鲁源化工科技有限公司 | A kind of high refractive index epoxy acrylic optical resin and preparation method thereof |
| CN110637060A (en) * | 2017-05-23 | 2019-12-31 | 可奥熙搜路司有限公司 | Epoxy acrylate resin composition for medium refractive optical lens and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101816722B1 (en) * | 2017-04-21 | 2018-01-11 | 주식회사 케이오씨솔루션 | A method of preparing epoxy acryl based optical material |
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| US5880171A (en) * | 1989-05-01 | 1999-03-09 | 2C Optics, Inc. | Fast curing polymeric compositions for ophthalmic lenses and apparatus for preparing lenses |
| CN1646589A (en) * | 2002-02-20 | 2005-07-27 | 大日本印刷株式会社 | Resin composition and optical elements |
| KR20120004673A (en) * | 2010-07-07 | 2012-01-13 | 엘지전자 주식회사 | Operating method of display system outputting 3 dimensional contents and display system enabling of the method |
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| KR20120058655A (en) * | 2010-09-25 | 2012-06-08 | 주식회사 케이오씨솔루션 | Resin Composition for Optical Lens and Optical Lens Using It |
| KR101802480B1 (en) * | 2010-12-13 | 2017-12-28 | 주식회사 케이오씨솔루션 | Epoxy Acryl Optical Resin Composition Comprising Internal Mold Release Agent |
| KR101227436B1 (en) * | 2011-03-22 | 2013-01-29 | 주식회사 케이오씨솔루션 | Mold polymerization method for epoxy acryl optical lens and the resin composition containing internal mold release agents |
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2012
- 2012-06-13 WO PCT/KR2012/004673 patent/WO2013187539A1/en active Application Filing
- 2012-06-13 CN CN201280003139.0A patent/CN103635497A/en active Pending
Patent Citations (3)
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| US5880171A (en) * | 1989-05-01 | 1999-03-09 | 2C Optics, Inc. | Fast curing polymeric compositions for ophthalmic lenses and apparatus for preparing lenses |
| CN1646589A (en) * | 2002-02-20 | 2005-07-27 | 大日本印刷株式会社 | Resin composition and optical elements |
| KR20120004673A (en) * | 2010-07-07 | 2012-01-13 | 엘지전자 주식회사 | Operating method of display system outputting 3 dimensional contents and display system enabling of the method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104583249A (en) * | 2012-08-27 | 2015-04-29 | 可奥熙搜路司有限公司 | Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material |
| CN104583249B (en) * | 2012-08-27 | 2017-03-29 | 可奥熙搜路司有限公司 | The preparation method of propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material |
| CN107107403A (en) * | 2014-12-26 | 2017-08-29 | 三井化学株式会社 | The manufacture method of internal mold release, the composition comprising the internal mold release and the plastic lens using said composition |
| CN107107403B (en) * | 2014-12-26 | 2019-04-02 | 三井化学株式会社 | The manufacturing method of internal mold release, the composition comprising the internal mold release and the plastic lens using the composition |
| CN110637060A (en) * | 2017-05-23 | 2019-12-31 | 可奥熙搜路司有限公司 | Epoxy acrylate resin composition for medium refractive optical lens and preparation method thereof |
| CN109575239A (en) * | 2018-12-13 | 2019-04-05 | 山东鲁源化工科技有限公司 | A kind of high refractive index epoxy acrylic optical resin and preparation method thereof |
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| WO2013187539A1 (en) | 2013-12-19 |
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