CN104203526B - The manufacture method of plastic lens - Google Patents
The manufacture method of plastic lens Download PDFInfo
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- CN104203526B CN104203526B CN201380016414.7A CN201380016414A CN104203526B CN 104203526 B CN104203526 B CN 104203526B CN 201380016414 A CN201380016414 A CN 201380016414A CN 104203526 B CN104203526 B CN 104203526B
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- polymeric compositions
- plastic lens
- manufacture method
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0016—Lenses
Abstract
The present invention provides the manufacture method of a kind of polyurethanes plastic lens, even if it was polymerized under the short time, to be not easy to thus produce texture bad.The method makes containing having the compound of multiple sulfydryl or hydroxyl and (C) polymerization catalyst in (A) polyisocyanate compound, (B) molecule and meet the polymeric compositions of following condition (1) and (2) initial temperature 20 DEG C below, be polymerized under the polymerizing condition below polymerization time 12 hours.(1) the described polymeric compositions after just allocating is below 200mPa s the viscosity of 10 DEG C, and (2) viscosity of the described polymeric compositions after 8 hours under 10 DEG C of controlled conditions is more than 400mPa s and 100Pa below s.
Description
Technical field
The present invention relates to the manufacture method of a kind of plastic lens, particularly relate to a kind of polyurethane or sulphur for ammonia
The manufacture method of carbamate class glasses plastic lens.
Background technology
Compared with inorganic lenses, plastic lens is lightweight and not broken, can dye, and is therefore used as eye
The optical elements such as mirror eyeglass, camera lens.As the material of plastic lens, due to polyurethane based resin
Refractive index is high and lightweight, excellent impact resistance, therefore generally uses by polyisocyanates and polythiol
The polyurethane based resin (patent document 1) that the polymer of compound is formed.Before these plastic lens for example will be polymerized
Composition be injected in the shaping mould with glass mold and pad, heat up at leisure, little to amount to 24
Being polymerized for a long time when about.
In the manufacture method of plastic lens, volume according to lens to be manufactured and want the lens obtaining
Intensity, character, produce texture become problem sometimes, in polyurethanes plastic lens, it is proposed that
Carry out pre-reaction, carry out heating up after the viscosity of monomer composition is viscosified and improve the productivity ratio of plastic lens
Technology, thus can realize preventing the purpose (patent document 2) of such texture.
In addition, in patent document 3, as the productivity ratio with practicality and available without optical distortion
Manufacture method with the thicker plastic lens of texture etc., it is proposed that a kind of manufacture method, the method possesses
Polymerizable composition, polymerizable composition is maintained at and fills out by following operation: after being filled in polymerizable composition, polymerizable composition in mould
Holding operation more than initial temperature when filling;And the cooling that above-mentioned polymerizable composition, polymerizable composition cooled down
Operation.In the course of the polymerization process, although slow at starting stage polymerization speed, but drastically accelerate in certain stage,
Therefore, the purpose of the method is to prevent from rising the unfavorable conditions such as the distortion causing because of this speed.
Prior art literature
Patent document
Patent document 1: Japanese Patent No. 3279784
Patent document 2: Japanese Unexamined Patent Publication 2007-90574 publication
Patent document 3: Japanese Unexamined Patent Publication 2009-226742 publication
Content of the invention
Problems to be solved by the invention
In the manufacture method of plastic lens, need the plenty of time for being polymerized polymeric compositions, example
As, in the method for patent document 2, for specific embodiment, arranged about 20~40 hours left sides
Right heating schedule is polymerized.In addition, in the method for patent document 3, with regard to specific embodiment
For, utilize the heating schedule of about about 17~30 hours to be polymerized.From the productivity ratio of plastic lens,
Reduce the viewpoints such as furnace equipment expense to consider, preferably manufacture plastic lens with shorter polymerization time, but deposit
In following problem: be easy for producing the unfavorable conditions such as texture if shortening polymerization time.
Therefore, the problem of the present invention is, provides the manufacture method of a kind of polyurethanes plastic lens, its
Even if with short time polymerization, being not easy to thus produce texture bad.
The method of solution problem
Initial viscosity and its polymerization property to composition for the present inventor has carried out concentrated research, it was found that
By using the polymeric compositions meeting specified conditions, even if being not easy to thus produce line with short time polymerization
Reason, thus complete the present invention.
That is, the present invention provides following [1]~[5].
[1] manufacture method of a kind of plastic lens, comprising:
Make polymeric compositions below initial temperature 20 DEG C, under the polymerizing condition below polymerization time 12 hours
It is polymerized, wherein,
Described polymeric compositions contains: have multiple sulfydryl in (A) polyisocyanate compound, (B) molecule
Or the compound of hydroxyl and (C) polymerization catalyst,
And described polymeric compositions meets following condition (1) and (2):
(1) the described polymeric compositions after just allocating is below 200mPa s the viscosity of 10 DEG C,
(2) under 10 DEG C of controlled conditions, the viscosity of the described polymeric compositions after 8 hours is 400mPa s
Above and below 100Pa s.
The manufacture method of the plastic lens described in [2] above-mentioned [1], wherein, described polymerization catalyst is following logical
Organo-metallic compound shown in formula (I),
(R)n-Sn-(X)4-n (I)
[in formula (I), R represents the alkyl of carbon number 1 to 12, and X represents fluorine atom, chlorine atom or bromine
Atom, n is the integer of 1 to 3].
[3] above-mentioned [1] or [2] described in the manufacture method of plastic lens, wherein, in described polymerizing condition,
Final temperature is 100~150 DEG C, and makes the ratio of its time being polymerized below 60 DEG C be 60~90%.
[4] manufacture method of the plastic lens any one of above-mentioned [1]~[3], wherein, polymerization time is 10 little
When below.
[5] manufacture method of the plastic lens any one of above-mentioned [1]~[4], wherein, polymerization time is 5 little
When below.
The effect of invention
The manufacture method of the plastic lens according to the present invention, even if providing a kind of with short time polymerization, texture
The manufacture method of bad also less plastic lens.
Detailed description of the invention
The manufacture method of the plastic lens of the present invention includes making polymeric compositions below initial temperature 20 DEG C,
Polymerization under polymerizing condition below polymerization time 12 hours, described polymeric compositions contains: (A) many isocyanides
Ester compound, (B) molecule have compound and (C) polymerization catalyst of multiple sulfydryl or hydroxyl, and
And, described polymeric compositions meets following condition (1) and (2),
(1) the described polymeric compositions after just allocating is below 200mPa s the viscosity of 10 DEG C,
(2) under 10 DEG C of controlled conditions, the viscosity of the described polymeric compositions after 8 hours is 400mPa s
Above and below 100Pa s.
By using the polymeric compositions meeting above-mentioned condition, even if polymerization is to complete with the short time, produce
The bad plastic lens of texture also can tail off.
The reason that can obtain such effect uncertain, but it has been generally acknowledged that its reason is as follows.
Think and as the polymeric compositions using in the present invention, show particular viscosity performance by use
Polymeric compositions, be possible to prevent polymeric compositions based on the convection current (thermal convection current) of the Temperature Distribution in die cavity,
Even if being therefore polymerized by the short time, its texture is bad also can tail off.
Think manufacture plastic lens when texture bad due to when polymeric compositions is polymerized at mould
The heat producing in die cavity, especially because polymerization time is shorter, the heat that time per unit produces increases
Greatly, therefore the Temperature Distribution in die cavity expands, and it is bad that result will produce texture in a large number.
With regard to such thermal convection current, have shown in following mathematical expression (a) be referred to as Rayleigh number as fluid thermal
The dimensionless number of transmission index.
Ra=[g β △ Td3]/[νX]
Ra: Rayleigh number
G: acceleration of gravity
β: the coefficient of cubical expansion
△ T: temperature difference
d3: 3 powers of distance between the upper and lower
ν: dynamic viscosity coefficient
X: thermal diffusion coefficient
That is, according to above-mentioned formula, in the case that temperature difference is bigger, between the upper and lower apart from big when Rayleigh number become
Greatly, display easily causes convection current, and when viscosity is big, Rayleigh number diminishes, and display is difficult to cause convection current.
If considering the polymerization of the lens of definite shape herein, then acceleration of gravity is constant, is equivalent to
The distance between the upper and lower of mirror wall thickness is also constant.In addition, it is believed that the coefficient of cubical expansion, thermal diffusion coefficient according to
The degree of polymerization of monomer and be intrinsic value, in addition, the contribution to Rayleigh number is less.Therefore, at lens
In polymerization, dynamic viscosity coefficient ν and temperature difference △ T is bigger on Rayleigh number impact.
With regard to condition (1), at the polymerization initial stage, few because being polymerized the heat release causing in low-temperature region, there is △ T
The tendency that value diminishes.Therefore, as shown in condition (1), even if viscosity is low, dynamic viscosity coefficient ν value is little,
Rayleigh number is also suppressed relatively low, is therefore difficult to cause thermal convection current.
With regard to condition (2), the phase is many because being polymerized the heat release causing after polymerisation, there is the tendency that △ T value becomes big.
Therefore, as shown in condition (2), rise fast polymeric compositions by using viscosity, become big gathering at △ T
Closing the sufficiently high dynamic viscosity coefficient ν of later stage acquisition, Rayleigh number can be suppressed relatively low, therefore be difficult to by result
Cause thermal convection current.
It is understood that can be with the polymeric compositions of the application of the invention, even providing the short time
Polymerization, the manufacture method of the bad also less plastic lens of texture.
Below the composition of the present invention is described in detail.
[polymeric compositions]
For the polymeric compositions of the present invention, after (1) its just allotment, the viscosity at 10 DEG C is 200mPa s
Below.By the polymeric compositions that the viscosity after the described allotment of use is below 200mPa s, simultaneously will be poly-
Close initial temperature and be set as below uniform temperature, be possible to prevent initial thermal convection current, therefore can significantly subtract
The texture of few plastic lens is bad.
In addition, the viscosity in condition (1) is preferably below 150mPa s, more preferably below 100mPa s.
The lower limit of the viscosity in condition (1) is not particularly limited, for example, 10mPa s.
Viscosity after just allocating refers to mix composition, and the viscosity being measured within 10 minutes.
In addition, in the present invention, viscosity is to use SEKONIC company vibrating type viscometer
VISCOMATE VM-10A, the value being measured according to JIS Z8803 standard at 10 DEG C.
(2) under 10 DEG C of controlled conditions, the viscosity of the described polymeric compositions after 8 hours is 400mPa s
Above and below 100Pa s.
By using the polymeric compositions of the range of viscosities meeting condition (1) and condition (2), can substantially reduce
Texture is bad.
Viscosity in condition (2) is preferably more than 500mPa s and 50Pa below s, more preferably 700mPa s
Above and below 3Pa s.
It should be noted that the viscosity in condition (2) is also according to the method identical with condition (1), at 10 DEG C
The value of lower mensuration.
For polymeric compositions used in the present invention, based on the general knowledge of this area, can be by regulation
The polymerization catalyst that the monomer component character that used and the polymerization property with monomer component adapt
Addition obtains the polymeric compositions meeting above-mentioned condition (1) and (2).Particularly gathering in polymeric compositions
The content closing catalyst easily produces impact to the physical property of condition (2).Below to polymerization used in the present invention
Each composition of composition and content illustrate.
Polymeric compositions used in the present invention contains (A) polyisocyanate compound (hereinafter referred to as
" (A) composition "), (B) molecule has the compound (hereinafter referred to as " (B) composition ") of multiple sulfydryl or hydroxyl
(C) polymerization catalyst (hereinafter referred to as " (C) composition ").
<(A) polyisocyanate compound>
It as polyisocyanate compound, is not particularly limited, can enumerate for example: xyxylene two isocyanide
Acid esters (1,3-bis-(isocyanatomethyl) benzene), tetramethyl xylylene diisocyanate, 3,3 '-dichloro two
Phenyl-4,4 '-diisocyanate, 4,4 '-methyl diphenylene diisocyanate, hexamethylene diisocyanate,
2,2 ', 5,5 '-Tetrachlorodiphenyl-4,4 '-diisocyanate, toluene di-isocyanate(TDI), two (isocyanatomethyl)
Hexamethylene, two (4-isocyanates butylcyclohexyl) methane, two (4-isocyanatomethyl cyclohexyl) methane,
Cyclohexane diisocyanate, IPDI, two (isocyanatomethyl) bicyclic [2.2.2] are pungent
Alkane, two (isocyanatomethyl) bicyclic [2.2.1] heptane, 2-isocyanatomethyl-3-(3-NCO
Propyl group)-5-isocyanatomethyl bicyclic [2.2.1] heptane, 2-isocyanatomethyl-3-(3-isocyanates third
Base)-6-isocyanatomethyl bicyclic [2.2.1] heptane, 2-isocyanatomethyl-2-[3-NCO third
Base]-5-isocyanatomethyl bicyclic [2.2.1] heptane, 2-isocyanatomethyl-2-(3-NCO third
Base)-6-isocyanatomethyl bicyclic [2.2.1] heptane, 2-isocyanatomethyl-3-(3-NCO third
Base)-6-(2-isocyanatoethyl) bicyclic [2.2.1] heptane, 2-isocyanatomethyl-3-(3-isocyanates
Base propyl group)-6-(2-isocyanatoethyl) bicyclic [2.2.1] heptane, 2-isocyanatomethyl-2-(3-isocyanide
Perester radical propyl group)-5-(2-isocyanatoethyl) bicyclic [2.2.1] heptane, 2-isocyanatomethyl-2-(3-
NCO propyl group)-6-(2-isocyanatoethyl) bicyclic [2.2.1] heptane etc..Particularly preferred xyxylene
Diisocyanate, tetramethyl xylylene diisocyanate, two (isocyanatomethyl) bicyclic [2.2.1] heptan
Alkane and two (isocyanatomethyl) hexamethylene.Above-claimed cpd can be used alone or combine two or more
Use.
It is excellent that the content of polyisocyanate compound presses equivalent ratio relative to (B) composition in polymeric compositions
Elect 0.6~1.4 as, more preferably 0.8~1.2, more preferably 0.9~1.1.Equivalent proportion mentioned here
Refer to the molal quantity of NCO of (A) composition and the ratio of the sulfydryl of (B) composition and the total mole number of hydroxyl
[(A)/(B)]。
The content of polyisocyanate compound is not particularly limited, and is preferably relative to polymeric compositions total amount
30~60 mass %, more preferably 35~55 mass %, more preferably 40~50 mass %.
<(B) molecule has the compound of multiple sulfydryl or hydroxyl>
As the compound in (B) molecule with multiple sulfydryl or hydroxyl, following polythiol chemical combination can be enumerated
Thing, polyol compound, the mercaptan compound containing hydroxyl.It should be noted that in a so-called molecule
There is the compound that the compound of multiple sulfydryl or hydroxyl comprises to have multiple sulfydryl and hydroxyl in a molecule.
As multi-thioalcohol compound, can enumerate for example: dimercapto methane, 1,1-dimercaptoethane, 1,2-bis-
Ethane thiol, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercapto third
Alkane, 1,1-dimercapto butane, 1,2-dimercapto butane, 1,3-dimercapto butane, 1,4-dimercapto butane, 2,2-
Dimercapto butane, 2,3-dimercapto butane, 1,2-thioresorcin, 1,3-thioresorcin, 1,4-thioresorcin,
Double mercapto methyl-the 1,4-of 1,2-dimercapto dimethylbenzene, 1,3-dimercapto dimethylbenzene, 1,4-dimercapto dimethylbenzene, 2,5-
Dithiane and polymer, the double mercapto methyl-1,3-dithiane of 4,5-and polymer, 2,5-dimercapto-1,4-
Dithiane, 4,5-dimercapto-1,3-dithiane, 4,5-double mercapto methyl-1,3-dithiolane, 4,5-bis-mercapto
Two mercaptan compounds such as base-1,3-dithiolane, 2,3-bis-(2-sulfydryl ethylmercapto group)-1-propane mercaptan, double
Mercapto methyl-3,6,9-trithio generation-1,11-hendecane two mercaptan, four mercapto methyl methane, pentaerythrite four mercapto
Base propionic ester, pentaerythrite four mercaptoacetate etc. or its mixture.
As polyol compound, can enumerate for example: ethylene glycol, diethylene glycol, propane diols, dipropyl two
Alcohol, butanediol, neopentyl glycol, glycerine, trimethylolethane, trimethylolpropane, butane triol,
1,2-methyl glucoside, pentaerythrite, dipentaerythritol, tripentaerythritol, D-sorbite, erythrite,
Threitol, ribitol, arabite, xylitol, allitol, mannitol, cholesterine (dorcitol),
Iditol, glycol, inositol, hexanetriol, triglycerin, two glycerine, triethylene glycol, polyethylene glycol,
Three (2-hydroxyethyl) chlorinated isocyanurates, cyclobutanediol, pentamethylene glycol, cyclohexane diol, cycloheptane
Glycol, cyclooctane glycol, cyclohexanedimethanol, hydroxypropyl cyclohexanol, three rings [5,2,1,0,2,6] decane
Dimethanol, two rings [4,3,0] nonane glycol, bicyclohexane glycol, three rings [5,3,1,1] dodecanediol, two
Ring [4,3,0] nonane dimethanol, three rings [5,3,1,1] dodecane diethanol, hydroxypropyl three ring [5,3,1,1] 12
Alkanol, spiral shell [3,4] octane glycol, butyl cyclohexane glycol, 1,1 '-two cyclohexylidene glycol, phloroglucitol,
The aliphatic polyol such as maltitol, lactitol, dihydroxy naphthlene, trihydroxynaphthalene, tetrahydroxy naphthalene, dihydroxy
Base benzene, benzene triol, biphenyl tetrol, pyrogaelol, (hydroxynaphenyl) pyrogaelol, trihydroxy phenanthrene, bisphenol-A,
Aromatic polyol, two (2-hydroxyethyl) thioether, the 1,2-such as Bisphenol F, benzene dimethanol, tetrabromobisphenol A
Double (2-hydroxyethyl sulfydryl) ethane, double (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-glycol, double (2,3-
Dihydroxypropyl) thioether, four (4-hydroxyl-2-sulphur butyl) methane, double (4-hydroxy phenyl) sulfone (trade name bis-phenol
S), tetrabromo-bisphenol s, tetramethyl bisphenol S, 4,4 '-thiobis (the 6-tert-butyl group-3-methylphenol), the double (2-of 1,3-
Hydroxyethyl sulphur ethyl) polyalcohol etc. containing sulphur atom such as hexamethylene.
In addition, as the mercaptan compound containing hydroxyl, can enumerate for example: 2 mercapto ethanol, 2,3-bis-mercapto
Base-1-propyl alcohol, 3-hydroxyl-2-butane thiol, 3-sulfydryl hexanol, 3-sulfydryl-2-methyl butanol, 3-sulfydryl-3-
Methyl butanol, 3-sulfydryl-2-methyl anyl alcohol etc..
Above-claimed cpd can be used alone or be applied in combination two or more.
<(C) polymerization catalyst>
It as polymerization catalyst, is not particularly limited, amines, organo-metallic compound etc. can be enumerated.
As amines, can enumerate for example: triethylenediamine, hexa, N, N-diformazan
Base octylame, N, N, N ', N '-tetramethyl-1,6-diamino hexane, 4,4 '-trimethylene double (1-methyl piperidine),
1,8-diazabicylo (5,4,0)-7-endecatylene.
As organo-metallic compound, organotin, copper oleate, acetylacetone copper, acetylacetone,2,4-pentanedione can be enumerated
Iron, iron naphthenate, ferric lactate, ironic citrate, iron gluconate, metatitanic acid 2-Octyl Nitrite etc..
As polymerization catalyst, wherein preferred organotin, the organometallic shown in preferably following formula (1)
Compound.
(R)n-Sn-(X)4-n (1)
[in formula (1), R represents the alkyl of carbon number 1 to 12 (preferably 4 to 8), X represent fluorine atom,
Chlorine atom or bromine atoms (preferably chlorine atom), n are the integer (preferably 2) of 1 to 3.]
As above-mentioned concrete example, dimethyltin chloride, dibutyl tin dichloride, dioctyl can be enumerated
Stannous chloride, dimethyl tin bibromide, dibutyl tin bibromide, dioctyl tin bibromide, dioctyl two
Tin fluoride etc..These catalyst may be used singly or in combination of two or more.
In these polymer, preferably dimethyltin chloride, dibutyl tin dichloride.
The content of polymer can be according to the polymerization property of polymeric compositions with the technology general knowledge of this area as base
Plinth suitably sets, relative to polymeric compositions total amount, and preferably 0.001~2.0 mass %, more preferably
0.005~1.5 mass %, more preferably 0.01~1.0 mass %.
Additionally, the polymeric compositions of the present invention also can contain episulfide compounds.As episulfide compounds,
Can enumerate for example: the double (β-epithio third of double (β-epithiopropyl) thioether, double (β-epithiopropyl sulphur generation) methane, 1,2-
Base sulphur generation) ethane, double (β-epithiopropyl sulphur generation) propane of 1,3-, double (β-epithiopropyl sulphur generation) propane of 1,2-, 1-(β-
Epithiopropyl sulphur generation)-2-(β-epithiopropyl sulphomethyl) propane, double (β-epithiopropyl sulphur generation) butane of 1,4-,
1,3-double (β-epithiopropyl sulphur generation) butane, 1-(β-epithiopropyl sulphur generation)-3-(β-epithiopropyl sulphomethyl) fourth
Alkane, 1,5-double (β-epithiopropyl sulphur generation) pentane, 1-(β-epithiopropyl sulphur generation)-4-(β-epithiopropyl sulphomethyl)
Double (β-epithiopropyl sulphur generation) hexane of pentane, 1,6-, (β-epithiopropyl sulphur is for first for-5-for 1-(β-epithiopropyl sulphur generation)
Base) hexane, 1-(β-epithiopropyl sulphur generation)-2-[(2-β-epithiopropyl thio-ethyl) sulphur generation] ethane, 1-(β-ring
Thiopropyl sulphur generation)-2-{ [2-(2-β-epithiopropyl thio-ethyl) thio-ethyl] sulphur generation } the chain chemical combination such as ethane
Thing;Four-(β-epithiopropyl sulphomethyl) methane, 1,1,1-tri-(β-epithiopropyl sulphomethyl) propane, 1,5-
Double (β-the epithiopropyl of double (β-epithiopropyl sulphur generation)-2-(β-epithiopropyl sulphomethyl)-3-thia pentane, 1,5-
Sulphur generation) double (β-epithiopropyl sulphomethyl)-3-thia pentane of-2,4-, 1-(β-epithiopropyl sulphur generation)-2,2-double (β-
Epithiopropyl sulphomethyl)-4-thia hexane, 1,5,6-tri-(β-epithiopropyl sulphur generation)-4-(β-epithiopropyl sulphur generation
Methyl)-3-thia hexane, double (β-epithiopropyl sulphur generation)-4-(β-epithiopropyl sulphomethyl)-3,6-two sulphur of 1,8-
Double (β-epithiopropyl sulphomethyl)-3,6-dithia of double (β-epithiopropyl sulphur generation)-4,5-of miscellaneous octane, 1,8-is pungent
Double (β-epithiopropyl sulphur generation)-4,4-of alkane, 1,8-double (β-epithiopropyl sulphomethyl)-3,6-dithia octane, 1,8-
Double (β-epithiopropyl sulphur generation)-2,4,5-three (β-epithiopropyl sulphomethyl)-3,6-dithia octane, 1,8-pair (β-
Epithiopropyl sulphur generation)-2,5-pair of (β-epithiopropyl sulphomethyl)-3,6-dithia octane, the double (β-epithio third of 1,9-
Base sulphur generation)-5-(β-epithiopropyl sulphomethyl)-5-[(2-β-epithiopropyl thio-ethyl) sulphomethyl]-3,7-two
Double [(2-β-epithiopropyl thio-ethyl) sulphur of double (β-epithiopropyl sulphur generation)-5,6-of thia nonane, 1,10-
Generation] double (β-epithiopropyl sulphur is for first for-3,6,9-three thia decane, double (β-epithiopropyl sulphur generation)-4,8-of 1,11-
Base) double (β-epithiopropyl sulphur is for first for-3,6,9-three thia hendecane, double (β-epithiopropyl sulphur generation)-5,7-of 1,11-
Base)-3,6,9-three thia hendecane, [(2-β-epithiopropyl sulphur is for second for-5,7-for 1,11-double (β-epithiopropyl sulphur generation)
Base) sulphomethyl]-3,6,9-three thia hendecane, the double (β-epithio third of double (β-epithiopropyl sulphur generation)-4,7-of 1,11-
Base sulphomethyl) the branched compound such as-3,6,9-three thia hendecane;Double (β-epithiopropyl the sulphur of 1,3-and 1,4-
Generation) hexamethylene, 1,3-and 1,4-double (β-epithiopropyl sulphomethyl) hexamethylene, double [4-(β-epithiopropyl sulphur generation)
Cyclohexyl] methane, 2,2-double [4-(β-epithiopropyl sulphur generation) cyclohexyl] propane, double [4-(β-epithiopropyl sulphur generation)
Cyclohexyl] sulfide, double (β-epithiopropyl sulphomethyl)-1,4-dithiane of 2,5-, the double (β-epithiopropyl of 2,5-
Sulphur is for Ethylsulfanylmethyl) the ester ring type compound such as-1,4-dithiane;Double (β-epithiopropyl sulphur generation) benzene of 1,3-and
Double (β-epithiopropyl sulphur generation) benzene of 1,4-, double (β-epithiopropyl sulphomethyl) benzene of 1,3-and the double (β-epithio third of 1,4-
Base sulphomethyl) benzene, double [4-(β-epithiopropyl sulphur generation) phenyl] methane, the double [4-(β-epithiopropyl sulphur generation) of 2,2-
Phenyl] propane, double [4-(β-epithiopropyl sulphur generation) phenyl] thioether, double [4-(β-epithiopropyl sulphur generation) phenyl] sulfone,
The aromatic compounds such as 4,4 '-bis-(β-epithiopropyl sulphur generation) biphenyl;And the epithio base of these compounds is at least
The compound etc. that 1 hydrogen is replaced by methyl.Particularly preferably double (β-epithiopropyl) thioethers.These chemical combination
Thing can be used alone or in combination of two or more kinds.
Peeling off from lens shaping mold in order to easy after polymerisation, the polymeric compositions of the present invention is also permissible
Containing releasing agent.
As releasing agent, phosphate is preferably used, specifically, acidic isopropyl phosphate, acid can be enumerated
Formula butylphosphoric acid ester, acid phosphate monooctyl ester, acid phosphate nonyl ester, acid phosphate ester in the last of the ten Heavenly stems, acid phosphate isodecyl
Ester, acid phosphate 13 ester, acid phosphate stearyl ester, acid phosphate propyl group phenylester, acid phosphate fourth
The phosphate monoesters such as base phenylester, acid phosphate butoxy ethyl ester;Acid phosphate diisopropyl ester, acid phosphorus
Dibutyl phthalate, acid phosphate dioctyl ester, acid phosphate two isodecyl ester, double (acid phosphate 13 esters), acid
Di(2-ethylhexyl)phosphate stearyl ester, acid phosphate dipropyl phenylester, acid phosphate dibutylphenyl ester, acid phosphate
The di-phosphate esters etc. such as dibutoxyethyl ester.These releasing agents can be used alone or be applied in combination 2 kinds with
On.
The content of releasing agent is preferably 0.001~0.5 weight % relative to polymeric compositions total amount.
Other any compositions as polymeric compositions, it is also possible to contain such as blueing agent, ultraviolet radiation absorption
Agent etc..
As blueing agent, can enumerate indigo plant is the dyestuff with red system or pigment.The content of blueing agent is not especially
Limit, be 0.00002~0.0002 mass % preferably with respect to polymeric compositions total amount.
As ultra-violet absorber, can enumerate for example: 2,4-DihydroxyBenzophenone, 2-hydroxyl-4-methoxyl group
Benzophenone, BP-4, UV-531,
2-hydroxyl-4-positive 12-alkoxy benzophenone, 2-hydroxyl-4-behzyloxybenzophenone, 2,2 '-dihydroxy-4-
The benzophenone compounds such as methoxy benzophenone;2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA,
2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-methyl
Phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tertiary pentyl phenyl) BTA, 2-(2 '-hydroxyl
-3 ', 5 '-di-t-butyl phenyl) BTA, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) BTA, 2-(2 '-
Hydroxyl-5 '-t-octyl phenyl) benzo three such as BTA, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) BTA
Azole compounds;Dibenzoyl methane, Eusolex 9020 etc..These ultraviolets
Light absorbers can be used alone or be applied in combination two or more.The content of ultra-violet absorber additionally depends on
Ultraviolet radiation absorption energy and maximum absorption wavelength, but relative to the total amount of polymeric compositions, preferably 0.03~3
Quality %.
[manufacture method]
The manufacture method of the plastic lens of the present invention is below initial temperature 20 DEG C, polymerization time 12 hours
The polymerization of above-mentioned polymeric compositions is made to obtain plastic lens under following polymerizing condition.
Polymerization is that above-mentioned polymeric compositions injects lens shaping mold, and heating is polymerized.
Lens shaping mold is preferably used the existing known mold being made up of pad and mould.As pad
The material of piece, can enumerate the fluororesin such as tetrafluoroethene.As the material of mould, generally use glass.
The temperature conditions of polymerization is preferably carried out the scope of 0~150 DEG C.In addition, as the temperature strip of polymerization
Part, initial temperature is less than 20 DEG C, more preferably 0~15 DEG C, more preferably 0~10 DEG C.Finally
Temperature is not particularly limited, but for example preferably 100~150 DEG C, more preferably 110~140 DEG C, further preferably
120~130 DEG C.These temperature conditionss consider art technology general knowledge, according to polymeric compositions viscosity through when
Change, sets heating schedule under conditions of not producing thermal convection current and is warming up to final temperature.
The ratio making its time being polymerized below 60 DEG C is not particularly limited, but is being in polymeric compositions
In the case of viscosity low state, from the viewpoint of keeping temperature lower, preventing thermal convection current, relatively
It is preferably 60~90% in the total polymerization time, more preferably 65~85%, more preferably 70~80%.
Particularly in the manufacture method of the plastic lens of the present invention, owing to using the aggregate combinations meeting condition (2)
Thing, though be therefore polymerized under above-mentioned cryogenic conditions also can high viscosity, therefore in the heating schedule later stage,
Even if heating up with the short time, plastic lens is not easy to produce texture.
Polymerization time is less than 12 hours, from the viewpoint of productivity ratio, and preferably less than 10 hours,
More preferably less than 5 hours.The lower limit of polymerization time is not particularly limited, but is more than 3 hours.
Above-mentioned heating schedule can be set according to these polymerization times.
By the manufacture method of the present invention, pellicle mirror and finishing lenses can be manufactured.Wherein, to system
Make the lens weight before the processing such as cutting is eyeglass frame shape to be the lens of more than 20g and there is certain thickness
Lens, then due to the substantial amounts of polymeric compositions of needs, based on easily causing the reasons such as thermal convection current and easy
Generation texture, but the polymeric compositions using in the application of the invention, it is possible to reduce the generation of texture.
Embodiment
Below, the present invention is described in further detail by embodiment, but the present invention is not limited to these in fact
Execute example.It should be noted that the physical property of the glasses plastic lens obtaining in embodiment and comparative example is commented
Valency is carried out as follows.
(1) viscosity (mPa s (10 DEG C))
Use SEKONIC company vibrating type viscometer VISCOMATE VM-10A, enter at 10 DEG C
Row measures.It should be noted that assay method is according to JIS Z8803 standard.
(2) there is texture-free
USHIO motor (strain) appearance inspection device processed Optical Modulex SX-UI251HQ is used to carry out
Projection check.
The high pressure UV lamp of light source uses USH-102D, and the distance at 1m arranges white screen, by tested
Lens are inserted between light source and screen, and whether qualified determine according to the perspective view picture on screen.
The lens of irregular wire will not had on perspective view picture to be defined as certified products, will have irregular wire
Lens are defined as defective products.
(embodiment 1~10, comparative example 1~4)
Polymeric compositions shown in table 1 below is poured into a mould, then in lens shaping mold, in
Carry out polymerizing curable under the Elevated Temperature Conditions of the polymerization procedure described in table, manufacture plastic lens.
* 1 finishing lenses: diameter 70mm, the lens number of degrees-6.00 diopter, center wall thickness 1.0mm,
The thick 9.0mm in edge
* 2 pellicle mirrors: diameter 70mm, lens base curve 136mm (radius of curvature R), center wall thickness
4.0mm, the thick 8.0mm in edge
(polymerization procedure)
P1: initial temperature 10 DEG C, was warming up to 40 DEG C through 3.5 hours, was then warming up to 125 DEG C with 0.5 hour,
And then keep 1 hour (totally 5 hours, less than 60 DEG C about 4 hours) at 125 DEG C.
P2: keep 5.0 hours initial temperature 7.5 DEG C, be then warming up to 55 DEG C through 3.0 hours, thereafter,
It was warming up to 125 DEG C with 1.0 hours, and then within 1 hour, (totally 10 hours, less than 60 DEG C about 125 DEG C of holdings
8 hours).
P3: keep 5.0 hours initial temperature 15 DEG C, be warming up to 55 DEG C through 3.0 hours after it, thereafter,
It was warming up to 125 DEG C with 1.0 hours, and then within 1 hour, (totally 10 hours, less than 60 DEG C about 125 DEG C of holdings
8 hours).
P4: keep 5.0 hours initial temperature 25 DEG C, be warming up to 55 DEG C through 3.0 hours after it, thereafter,
It was warming up to 125 DEG C with 1.0 hours, and then within 1 hour, (totally 10 hours, less than 60 DEG C about 125 DEG C of holdings
8 hours).
P5: keep 4.0 hours initial temperature 13 DEG C, be warming up to 80 DEG C through 4.0 hours after it, thereafter,
It was warming up to 125 DEG C with 0.5 hour, and then within 1 hour, (totally 9.5 hours, less than 60 DEG C about 125 DEG C of holdings
7 hours).
From result above, in the case that use meets the polymeric compositions of condition (1) and (2), even if
In the case of being the polymerization procedure manufacture plastic lens within utilizing 12 hours, by initial temperature 20 DEG C
Make it be polymerized under conditions of following, be not likely to produce texture bad.
Industrial applicibility
According to the present invention, owing to the bad less plastic lens of texture can be manufactured with short polymerization time,
Therefore can improve plastic lens productivity ratio, and then furnace equipment expense can be reduced.
Claims (6)
1. a manufacture method for plastic lens, comprising:
Make polymeric compositions below initial temperature 20 DEG C, under the polymerization time polymerizing condition of 3~12 hours
It is polymerized, wherein,
Described polymeric compositions contains: have multiple mercapto in (A) polyisocyanate compound, (B) molecule
The compound of base or hydroxyl and (C) polymerization catalyst,
And described polymeric compositions meets following condition (1) and (2):
(1) the described polymeric compositions after just allocating is below 200mPa s the viscosity of 10 DEG C, described just
Within referring to after allotment mix described polymeric compositions latter 10 minutes,
(2) under 10 DEG C of controlled conditions, the viscosity of the described polymeric compositions after 8 hours is
More than 400mPa s and 100Pa below s,
Described viscosity uses vibrating type viscometer, is measured according to JIS Z8803 standard at 10 DEG C
Value.
2. the manufacture method of plastic lens as claimed in claim 1, wherein, described polymerization catalyst is
Organo-metallic compound shown in following logical formula (I),
(R)n-Sn-(X)4-n (I)
In formula (I), R represents the alkyl of carbon number 1 to 12, and X represents fluorine atom, chlorine atom or bromine atoms,
N is the integer of 1 to 3.
3. the manufacture method of plastic lens as claimed in claim 1, wherein, in described polymerizing condition,
Final temperature is 100~150 DEG C, and the time making described polymeric compositions be polymerized below 60 DEG C accounts for total poly-
The ratio of conjunction time is 60~90%.
4. the manufacture method of plastic lens as claimed in claim 2, wherein, in described polymerizing condition,
Final temperature is 100~150 DEG C, and when the time making described composition be polymerized below 60 DEG C accounts for total polymerization
Between ratio be 60~90%.
5. the manufacture method of the plastic lens as according to any one of Claims 1 to 4, wherein, described
In polymerizing condition, polymerization time is 3~10 hours.
6. the manufacture method of the plastic lens as according to any one of Claims 1 to 4, wherein, described
In polymerizing condition, polymerization time is 3~5 hours.
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PCT/JP2013/057869 WO2013146481A1 (en) | 2012-03-27 | 2013-03-19 | Method for producing plastic lens |
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KR101996981B1 (en) * | 2017-10-18 | 2019-07-05 | 에스케이씨 주식회사 | Polymerizable composition for plastic lens |
KR20190079956A (en) | 2017-12-28 | 2019-07-08 | 에스케이씨 주식회사 | Polymerizable composition for optical material |
KR102003056B1 (en) * | 2018-01-12 | 2019-07-23 | 에스케이씨 주식회사 | Plastic tinted lenses and manufacturing method thereof |
JP7332251B2 (en) * | 2018-06-28 | 2023-08-23 | ホヤ レンズ タイランド リミテッド | Polymerizable composition for optical members |
JP7296754B2 (en) * | 2019-03-28 | 2023-06-23 | ホヤ レンズ タイランド リミテッド | Polymerizable composition for optical member, optical member, and spectacle lens |
KR102150592B1 (en) * | 2019-09-11 | 2020-09-01 | 에스케이씨 주식회사 | Polymerizable composition for optical material |
EP3916470B1 (en) | 2020-01-27 | 2023-12-27 | Mitsui Chemicals, Inc. | Polymerizable composition for optical material, polymerizable prepolymer composition for optical material, cured product, and method of producing optical material |
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CN1035520A (en) * | 1988-02-17 | 1989-09-13 | 三井东圧化学株式会社 | Based on the resin for making lens of urethane, contain the manufacture method of plastic lens and this kind lens of this kind resin |
CN1119195A (en) * | 1994-04-08 | 1996-03-27 | 三井东压化学株式会社 | Composition for urethane-base plastic lens, urethane-base plastic lens obtained from the composition and process for the production of the plastic lens |
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JPH09254267A (en) * | 1996-03-21 | 1997-09-30 | Nasu Nikon:Kk | Production of plastic lens |
JP3390307B2 (en) * | 1996-09-09 | 2003-03-24 | 三井化学株式会社 | Urethane-based plastic lens composition, plastic lens comprising the same, and method for producing the same |
JP3642973B2 (en) * | 1999-03-10 | 2005-04-27 | 三井化学株式会社 | New optical resin |
JP4214870B2 (en) * | 2003-09-10 | 2009-01-28 | セイコーエプソン株式会社 | Method for manufacturing optical article |
JP2009226742A (en) * | 2008-03-24 | 2009-10-08 | Seiko Epson Corp | Manufacturing method of plastic lens |
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- 2013-03-19 CN CN201380016414.7A patent/CN104203526B/en active Active
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CN1035520A (en) * | 1988-02-17 | 1989-09-13 | 三井东圧化学株式会社 | Based on the resin for making lens of urethane, contain the manufacture method of plastic lens and this kind lens of this kind resin |
US5744568A (en) * | 1993-09-29 | 1998-04-28 | Hoya Corporation | Process for the production of polyurethane lens |
CN1119195A (en) * | 1994-04-08 | 1996-03-27 | 三井东压化学株式会社 | Composition for urethane-base plastic lens, urethane-base plastic lens obtained from the composition and process for the production of the plastic lens |
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JP6095646B2 (en) | 2017-03-15 |
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