CN104583249B - The preparation method of propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material - Google Patents
The preparation method of propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material Download PDFInfo
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- CN104583249B CN104583249B CN201380045137.2A CN201380045137A CN104583249B CN 104583249 B CN104583249 B CN 104583249B CN 201380045137 A CN201380045137 A CN 201380045137A CN 104583249 B CN104583249 B CN 104583249B
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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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- G02B1/041—Lenses
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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
- C08F12/00—Homopolymers and 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 an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
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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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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Abstract
The present invention relates to the preparation method of propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material, especially, it is related to maintain appropriate polymerization speed such that it is able to obtain the propylene oxide acids polymerizable composition for optical material and the preparation method of optical material of the optical material of the high-quality for not having arteries and veins reason or albinism in high yield.The present invention provides propylene oxide acids polymerizable composition for optical material, which includes Epoxy Acrylates compound, the α-methylstyrene dimer of 0.1～2 percentage by weight of the above-mentioned propylene oxide acids polymerizable composition for optical material comprising total polymerization compositionss.In the present invention, by stably maintaining appropriate polymerization speed, the propylene oxide acids optical material of fine qualities for not having arteries and veins reason, albinism etc. can easily be prepared with low preparation expense.
Description
Technical field
The present invention relates to propylene oxide acids polymerizable composition for optical material and propylene oxide acids optical material
Preparation method, especially, is related to maintain appropriate polymerization speed such that it is able to obtain no arteries and veins reason or albinism in high yield
The propylene oxide acids polymerizable composition for optical material and the preparation method of optical material of the optical material of high-quality.
Background technology
Plastic optical lenses are described as the substitute for solving the problems, such as high specific gravity and low impact as glass lens.Represent
Property has Polyethylene Glycol diene propyl carbonate (polyethylene glycol bis (allyl carbonate)), poly- methyl
Acrylic acid methyl ester. (polymethyl methacrylate), diallyl phthalate (diallyl phthalate) etc..
But, by the optical lenses of the polymer preparation in them in things such as template, dyeability, hard coat film compactness, resistances to impact
Property in terms of it is outstanding, but there is a problem of because refractive index drop to 1.50 (nD) and 1.55 (nD) left and right make lens thickening.Therefore,
In order to reduce the thickness of lens, it is intended to develop the high optical material of various refractive indexs.
Korea log in special permission 10-0136698,10-0051275,10-0051939,10-0056025,10-0040546,
By by polyisocyanate (polyisocyanate) compound and mercaptan compound heat cure obtaining in 10-0113627 etc.
Thioxanthamide (thiourethane) class optical lenses.The dyeability of thioxanthamide class optical lenses,
The optical characteristics such as resistance to impact, the transparency are outstanding, but exist and uprise with refractive index, the problem of Abbe number step-down, also, material
It is expensive, it is sensitive to dampness reaction, thus the preparation section of lens is difficult to, there is also because in air when lens are preserved
Moisture and make the problem that the center of lens deforms.
Disclose and this thioxanthamide class in Korea logs in special permission 10-0496911,10-0498896 etc.
Lens are different, and with high refractive index, the optical characteristics such as Abbe number height, the transparency, light weight, thermostability are outstanding, and material
Cheap propylene oxide acids composition for optical material.For this propylene oxide acids optical material, in high temperature
In more wet area, without additional management moisture in air, and lens can be produced, and also will not be because in air during preservation lens
Moisture and make the center of lens deform.When polymeric epoxy acrylate class compound is to prepare lens, need adjustable
The reactive diluent of section viscosity and response speed, and as this reactive diluent, in the past, used styrene
(styrene), divinylbenzene (divinylbenzene), α-methyl styrene (α-methyl styrene), Alpha-Methyl benzene
Ethylene dimerization thing (α-methyl styrene dimer), benzyl methacrylate (benzyl methacrylate), chlorobenzene second
Alkene (chlorostyrene), bromstyrol (bromostyrene), methoxy styrene (methoxy styrene), maleic acid
One kind or the two or more mixture in them in dibenzyl ester (dibenzyl maleate) etc..But, using reaction
In the case of property diluent, it is also difficult to stably constant maintenance polymerization speed.The situation of appropriate polymerization speed can not maintained
Under, i.e. response speed is slow at the beginning, in the case of but being accelerated as temperature rises suddenly, it is possible to produce arteries and veins reason, albefaction are existing
As etc., conversely, when mixing post polymerization carry out it is too fast in the case of, imperfect due to being polymerized, refractive index, intensity, transparency etc. are each
Planting optical characteristics reduces, and the quality of final acquired lens is reduced, as a result, the reduction of lens yield.Thus be polymerized
When, the response speed for remaining appropriate becomes the important factor for affecting that produce on lens quality, and produces impact to yield, because
And also become the key factor of production cost.
Prior art literature
Patent documentation
Patent documentation 1：Korea logs in Application Publication 10-0496911
Patent documentation 2：Korea logs in Application Publication 10-0498896
The content of the invention
Technical problem
The present inventor learns that in the various reactive diluents for being used in the past α-methylstyrenedimer is to reaction
Speed has a direct impact, also, when unexpectedly learning using less than the α-methylstyrenedimer of amount in the past, i.e.
When the α-methylstyrenedimer that the past is used with the scope of 4～10 percentage by weights, with less in its 0.1～2 weight
When the scope of amount percentage ratio is used, the polymerization speed of epoxy acrylic Type of Collective compositionss is stably maintained with appropriate scope
Degree such that it is able to obtain the lens of the high-quality for not having arteries and veins reason or albinism in high yield.
The present invention confirms this case and completes, it is an object of the present invention to provide maintaining compositionss by appropriate
Polymerization speed, propylene oxide that can be to obtain in high yield not having arteries and veins reason, albinism etc. and the outstanding lens of optical characteristics
Acids polymerizable composition for optical material." arteries and veins reason " is referred to because of difference of constituent etc. and the normal refraction rate office with surrounding
The different phenomenon in portion, arteries and veins reason or albinism are possible to the quality to optical material or performance produces bad impact.The present invention's
Purpose is, when the polymerization speed of appropriate regulation composition is to prepare lens, does not produce this arteries and veins reason or albinism, but
Prepare the propylene oxide acids optical material of water white high-quality.
Technical scheme
The present invention provides propylene oxide acids polymerizable composition for optical material, it is characterised in that comprising by chemical formula 1
The compound of expression, above-mentioned propylene oxide acids polymerizable composition for optical material comprising total polymerization compositionss 0.1～2
The α-methylstyrenedimer of percentage by weight.The propylene oxide acids polymerizable composition for optical material of the present invention may be used also
Comprising the compound represented by formula 2 below.
Chemical formula 1：
(wherein, n=0～15, R1For H or CH3, R2For H or Br.)
Chemical formula 2：
(wherein, R is H or CH3, m=0～5, n=0～5 are 0, m+n=1～10) when m is different with n.
Also, the present invention provides the preparation method of propylene oxide acids optical material, above-mentioned propylene oxide acids optics material
The preparation method of material comprises the steps：When by the propylene oxide acids optics comprising the compound represented by above-mentioned chemical formula 1
When material carries out matrix polymerization with polymerizable composition, polymerizable composition, add above-mentioned propylene oxide acids polymerizable composition for optical material
Matrix polymerization is carried out after the α-methylstyrenedimer of 0.1～2 percentage by weight of gross weight mixing, for remaining appropriate
Polymerization speed.Now, it is preferable that propylene oxide acids polymerizable composition for optical material can also be comprising by above-mentioned chemical formula
2 compounds for representing.
Also, above-mentioned propylene oxide acids polymerizable composition for optical material is carried out matrix polymerization and is obtained by present invention offer
To optical material and the optical lenses formed by above-mentioned optical material.Above-mentioned optical lenses especially include lenses or polariscope
Piece.
Beneficial effect
The present invention provides through stably maintaining appropriate polymerization speed, can be managed or albefaction with preparing no arteries and veins in high yield
The propylene oxide acids polymerizable composition for optical material of the lens of the high-quality of phenomenon.Can be managed with pulsus deletuss according to the present invention
Or the high-quality of albinism is prepared with high index of refraction, high Abbe number, and the optical characteristics such as the transparency, light weight, thermostability
Outstanding propylene oxide acids optical material, and by improving yield reducing producing cost.
Specific embodiment
The propylene oxide acids polymerizable composition for optical material of the present invention is comprising the chemical combination represented by formula 1 below
One or more of thing are used as monomer component, and the α-methyl styrene of 0.1～2 percentage by weight comprising total composition
Dimer.Preferably, propylene oxide acids polymerizable composition for optical material of the invention can also be comprising by formula 2 below
The compound of expression.
Chemical formula 1：
Wherein, n is 0～15, R1For H or CH3、R2For H or Br.N is preferably 0～10, more preferably 0～5.
Chemical formula 2：
(wherein, R is H or CH3, m=0～5, n=0～5 are 0, m+n=1～10 when m is different with n.)
In the propylene oxide acids polymerizable composition for optical material of the present invention, for stably constant maintenance compositionss
Polymerization speed, the α-methylstyrenedimer of 0.1～2 percentage by weight comprising a small amount of total composition.When epoxy third
Olefin(e) acid class polymerizable composition for optical material is when polyreaction is carried out, it is impossible to maintain appropriate polymerization speed, and with temperature
Degree rises, in the case that response speed is accelerated suddenly, it is possible to produce arteries and veins reason etc., conversely, working as blend compositions post-polymerization
When carrying out too fast, as polyreaction carries out imperfect, the various optical characteristics reductions such as refractive index, intensity, transparency.Therefore,
The polymerization speed of compositionss produces important impact to the quality of final acquired lens, and determines the yield of lens.In the past,
α-methylstyrenedimer also serves as the reactive diluent of the viscosity and response speed of regulation composition, but mainly with benzene second
Other reactive diluents such as alkene are used together, when being used together with styrene etc., also using compositionss gross weight 4 weights
It is more than amount percentage ratio, substantially 4～10 percentage by weights.That is, thought in the past using Alpha-Methyl benzene more than at least 4 percentage by weights
Ethylene dimerization thing just can be effective as reactive diluent.But, in the present invention, learn α-first in various reactive diluents
Base styrene dimer thing is produced on response speed most directly to be affected, and learns using less in 0.1～2 weight hundred of conventional amount
During the α-methylstyrenedimer of the scope of point ratio, being capable of the more effectively constant polymerization speed for maintaining compositionss.The present invention
Epoxy acrylic Type of Collective compositionss in, the α-methyl styrene dimerization of 0.1～2 percentage by weight comprising total composition
Thing, it is highly preferred that the α-methylstyrenedimer comprising 0.2～1 percentage by weight.In the composition, α-methyl styrene
The content of dimer is nearly free from impact to the polymerization speed of compositionss, thus has less than in the case of 0.1 percentage by weight
Arteries and veins reason may be produced because being polymerized bad, in the case where the content of α-methylstyrenedimer is more than 2 percentage by weights, one
Start response speed slow, but as temperature flies up, response speed accelerates, cause to be possible to produce by uneven the causing that be polymerized
Arteries and veins reason or albinism.Conversely, the α-methylstyrenedimer of the low content of 0.2～1 weight percentage ranges can be by
The response speed of compositionss is constant to maintain to obtain less fast also less slow appropriate scope, especially, can suppress to rise with temperature
Response speed situation about rapidly rising, it is thus possible to prepare the lens of pulsus deletuss reason or albinism.
The propylene oxide acids polymerizable composition for optical material of the present invention is except above-mentioned α-methylstyrenedimer
Outside, can also include other reactive diluents.Preferably, combined with polymerism to adjust propylene oxide acids optical material
The appropriate viscosity of thing, also comprising other reactive diluents.Other reactive diluents are selected from styrene, divinyl
Benzene, α-methyl styrene, benzyl methacrylate, chlorostyrene, bromstyrol, methoxy styrene, maleic acid list benzyl ester, richness
Horse acid list benzyl ester, dibenzyl maleate, dibenzyl fumarate, methyl-benzyl maleate, dimethyl maleate, maleic acid diethyl
Ester, dibutyl maleate, dibutyl fumarate, butyl maleate, maleic acid list pentyl ester, dipentyl maleate, fumaric acid list
One or more compound in the group of the double aryl carbonates compositions of pentyl ester, fumaric acid diamyl ester and diethylene glycol.Phase
Also it is mixed with for the compound represented by above-mentioned chemical formula 1 of 100 weight portions or in the compound represented by above-mentioned chemical formula 1
The total monomer composition of the compound represented by chemical formula 2, it is preferable that comprising 30～300 weight portions containing with Alpha-Methyl benzene second
The global reactivity diluent of other different reactive diluents of alkene dimer.Using the reactivity dilution less than 30 weight portions
In the case of agent, it is difficult to the viscosity of regulation composition so that treatability is likely to decrease, conversely, using more than 300 weight portions
Reactive diluent in the case of, the viscosity of compositionss is too low, so as to refractive index produce bad influence, and produce arteries and veins reason etc. it is right
Polyreaction has a negative impact.
Preferably, in epoxy acrylic Type of Collective compositionss of the invention, liquid phase viscosity at a temperature of 25 DEG C for 20～
1000cps, liquid phase refractive index (nE, 20 DEG C) are 1.50～1.58, and solid phase refractive index (nE, 20 DEG C) is 1.54～1.63.If liquid
Phase viscosity is less than 20cps, then inject liquid-phase resin compositionss to the glass mold assembled by synthetic resin gasket and carry out molding
When, there is a problem of that compositionss are flowed out to outside mould, if liquid phase viscosity is more than 1000cps, presence is difficult to inject compositionss
In the problem of mould.Viscosity is more preferably 30～500cps.
In addition, propylene oxide acids polymerizable composition for optical material of the invention may be used also according to usual way
Comprising internal mould release, heat stabilizer, UV absorbent, organic dyestuff, inorganic pigment, coloring preventing agent, antioxidant, light
Stabilizer, catalyst etc..
As internal mould release, can be using in phosphate compound, silicon class surfactant, fluorine class surfactant etc.
One or more, it is preferable that 0.001～10 weight in propylene oxide acids polymerizable composition for optical material can be included
Amount percentage ratio.Preferably, phosphate compound can be used as internal mould release.For the phosphate compound of internal mould release
Polyoxyethylene nonylphenol ether phosphate (polyoxy ethylenenonylphenolether are selected from for example,
Phosphate) (5 percentage by weights of the oxirane of 5 moles of addition, 80 weight percents of the oxirane of 4 moles of addition
Than, addition 3 moles oxirane 10 percentage by weights, addition 1 mole oxirane 5 percentage by weights), polyoxy second
Alkene nonyl phenol ether phosphate (5 percentage by weights of the oxirane of 9 moles of addition, 80 weights of the oxirane of 8 moles of addition
Amount percentage ratio, 10 percentage by weights of the oxirane of 7 moles of addition, 5 weight percents of the oxirane of less than 6 moles of addition
Than), (3 percentage by weights of the oxirane of 11 moles of addition are, 10 moles of ring of addition for polyoxyethylene nonylphenol ether phosphate
80 percentage by weights of oxidative ethane, 5 percentage by weights of the oxirane of 9 moles of addition, the 6 of the oxirane of 7 moles of addition
Percentage by weight, addition 6 moles oxirane 6 percentage by weights), polyoxyethylene nonylphenol ether phosphate (addition 13
Mole 3 percentage by weights of oxirane, 80 percentage by weights of the oxirane of 12 moles of addition, 11 moles of ring of addition
8 percentage by weights of oxidative ethane, 3 percentage by weights of the oxirane of 9 moles of addition, 6 weights of the oxirane of 4 moles of addition
Amount percentage ratio), (3 percentage by weights of the oxirane of 17 moles of addition, addition 16 rub polyoxyethylene nonylphenol ether phosphate
79 percentage by weights of your oxirane, 10 percentage by weights of the oxirane of 15 moles of addition, the ring of 14 moles of addition
4 percentage by weights of 4 percentage by weights of oxidative ethane, the oxirane of 13 moles of addition), polyoxyethylene nonylphenol ether phosphoric acid
Ester (5 percentage by weights of the oxirane of 21 moles of addition, 78 percentage by weights of the oxirane of 20 moles of addition, addition
7 percentage by weights of 19 moles of oxirane, 6 percentage by weights of the oxirane of 18 moles of addition, 17 moles of addition
4 percentage by weights of oxirane), two sad phosphate esters (dioctylacid phosphate) and Zelec UNTMThe group of composition
In one or more compound.
Preferably, the heat stabilizer of 0.01～5 percentage by weight can in compositionss, be included.When using less than 0.01 weight
During the heat stabilizer of percentage ratio, thermal stability result is low, during using being more than the heat stabilizer of 5 percentage by weights, when there is solidification
Polymerization fraction defective is high, and the heat stability of solidfied material problem low on the contrary.As heat stabilizer, for example, can use selected from as gold
The category calcium stearate of fatty acid salt, barium stearate, zinc stearate, cadmium stearate, lead stearate, magnesium stearate, aluminium stearate,
One or more compound in the compound of potassium stearate, zinc octoate etc..Preferably, can be using selected from as Phosphorus
Triphenyl phosphite (triphenyl phosphite), diphenyl decyl phosphite ester (diphenyldecyl
Phosphite), phenyl didecyl phosphite (phenyldidecyl phosphite), diphenyl dodecyl phosphite ester
(diphenyldodecyl phosphite), trinonylphengl phosphite (trinonylphenyl phosphite), diphenyl
Iso-octyl phosphite ester (diphenylisooctyl phosphite), tributyl phosphite (tributyl phosphate),
Tripropyl phosphite (tripropyl phosphite), NSC 5284 (triethylphosphite), phosphorous acid front three
Ester (trimethylphosphite), three (single decyl phosphite ester) (tris (monodecylphosphite)), three (single phenyl
Phosphite ester) one or more compound in (tris (monophenylphosphite)).And, it is possible to use
Selected from the 3PbO.PbSO4.4H as lead class2O、2PbO.Pb(C8H4O4)、3PbO.Pb(C4H2O4).H2In the compound of O etc.
One or more.And, it is possible to use selected from the dibutyl tin laurate as organic tin
(dibutyltindilaurate), double (maleic acid is different for dibutyitin maleate (dibutyltin maleate), dibutyl tin
Monooctyl ester) (dibutyltinbis (isooctyl maleate)), di-2-ethylhexyl maleate (dioctyl maleate), dibutyl tin
Double (monomethyl maleates) (dibutyltinbis (monomethyl maleate)), dibutyl tin are double (lauryl mercaptan)
Double (different epoxide the mercaptoacetate) (dibutylbis of (dibutyltinbis (laurylmercaptan)), dibutyl
(isooxylmercaptoacetate)), Monobutyltin three (isooctyl thioglycolate) (monobutyltintris
(isooctylmercaptoacetate)), double (isooctyl thioglycolate) (dimethyltinbis (isooctyl of stannous methide
Mercapto acetate)), three (isooctyl thioglycolates) (tris (isooctyl mercapto acetate)), dioctyl
Double (the 2- of stannum double (isooctyl thioglycolate) (dioctyltinbis (isooctyl mercapto acetate)), dibutyl tin
Mercaptoethanol salt) (dibutyltinbis (2-mercapto ethylate)), Monobutyltin three (2 mercapto ethanol salt)
(monobutyltintris (2-mercapto ethylate)), stannous methide are double (2 mercapto ethanol salt)
(dimethyltinbis (2-mercapto ethylate)), monomethyl stannum three (2 mercapto ethanol salt)
One or more in the compound of (monomethyltintris (2-mercapto ethylate)) etc..Also,
The two or more heat stabilizer of different series in foregoing illustrative heat stabilizer can be mixed and used.Most preferably, using phosphorus
The heat stabilizer of class, is not only the priming color of the lens being molded with, and is not also reducing the transparency, impact strength, thermostability
In the case of etc. optical characteristics and polymerization yield, the heat stability of optical lenses is greatly improved.
The preparation method of propylene oxide acids optical material of the present invention comprises the steps, i.e. when will be with by above-mentionedization
The compound or epoxy acrylic ester compounds that formula 1 is represented carries out matrix polymerization as the polymerizable composition, polymerizable composition of monomer component
When, add the α-first of 0.1～2 percentage by weight of the gross weight of above-mentioned propylene oxide acids polymerizable composition for optical material
Matrix polymerization is carried out after base styrene dimer thing mixing, for maintaining appropriate polymerization speed, above-mentioned epoxy acrylic esterification
Compound is also to be mixed with the compound that represented by chemical formula 2 in the compound represented by above-mentioned chemical formula 1.According to preferred
Embodiment, before matrix polymerization is carried out, confirms the purity of all raw material, and the compound low to purity carries out purification, and makes
With the high compound of unpurified purity.Preferably, the high-purity compound till the use of purity being 70～99.99%.According to
After preferred embodiment, hybrid epoxidized acrylate compounds and α-methylstyrenedimer and other reactive diluents, add
Plus catalysts are stirred, then through vacuum deaerator, polymerizable composition, polymerizable composition is flow into into mould.Polymerism group will be injected with
The mould of compound is put into forced cyclic type baking oven, is slowly heating and curing to after 100 DEG C from 30 DEG C, is cooled to 70 ± 10 DEG C, so as to
Assemble and disassemble mould to obtain lens.
Embodiment
Hereinafter, the present invention is illustrated in greater detail by specific embodiment.But, these embodiments are only used for more specifically
The bright present invention, the scope of the present invention should not be limited to these embodiments.
Epoxy Acrylates compound
1) synthesis of composition (I) compound
Composition (I) compound is represented in chemical formula 3, in the YD-128 epoxy resin of the national capital chemistry that equivalent is 187
Addition acrylic acid simultaneously carries out acroleic acid esterification (at a temperature of 105 DEG C react 20 hours to prepare) to be prepared for equivalent be 259
Compound, is mixture that mean molecule quantity is 518.
Chemical formula 3：
(n=0～15.)
2) composition (II) compound
Composition (II) compound is represented in chemical formula 4, in the epoxy resin for equivalent being 187, adds methacrylic acid simultaneously
Carry out acroleic acid esterification (reacting 20 hours to prepare at a temperature of 105 DEG C) to be prepared for the compound that equivalent is 273, be average
Molecular weight is 546 mixture.
Chemical formula 4：
(n=0～15.)
3) composition (III) compound
Composition (III) compound is represented in chemical formula 5, to the YDB-400 epoxy resin of the national capital chemistry that equivalent is 400
Middle addition acrylic acid simultaneously carries out acroleic acid esterification (reacting 20 hours to prepare at a temperature of 105 DEG C) to be prepared for equivalent for 472
Compound, be mixture that mean molecule quantity is 944.
Chemical formula 5：
(n=0～15.)
4) composition (IV) compound
Composition (IV) compound is represented in chemical formula 6, in the epoxy resin for equivalent being 400, adds methacrylic acid simultaneously
Carry out acroleic acid esterification (reacting 20 hours to prepare at a temperature of 105 DEG C) to be prepared for the compound that equivalent is 486, be average
Molecular weight is 972 mixture.
Chemical formula 6：
(n=0～15.)
5) composition (V) compound
Add acrylic acid during the ethanol of oxirane is added with the bisphenol-A for equivalent being 175 and carry out acroleic acid esterification
(at a temperature of 105 DEG C react 20 hours to prepare) are being prepared for the compound that equivalent is 229.Be mean molecule quantity be 458
Mixture, structural formula such as formula 7 below.
Chemical formula 7：
(m=0～5, n=0～5 are 0, m+n=1～10 when m is different with n.)
6) composition (VI) compound
Add methacrylic acid during the ethanol of oxirane is added with the bisphenol-A for equivalent being 175 and carry out acrylic acid
It is esterified (20 hours are reacted at a temperature of 105 DEG C to prepare) to be prepared for the compound that equivalent is 243.It is that mean molecule quantity is
486 mixture, structural formula such as formula 8 below.
Chemical formula 8：
(m=0～5, n=0～5 are 0, m+n=1～10 when m is different with n.)
Embodiment 1
The composition (III) of composition (I), 30g to the 15g in the Epoxy Acrylates compound for obtaining in the above-described manner
And the α-methylstyrenedimer as polymerization regulator of addition 0.5g, the conduct of 40g react dilute in the composition (V) of 10g
The α-methyl styrene of the styrene and 5g of agent is released, and adds the diphenyl 1-isobutyl-3,5-dimethylhexylphosphoric acid as heat stabilizer of 2g
The sad phosphate ester (DOP, dioctylacid phosphate) of the two of (DPDP, diphenyl dodecyl phosphate), 1g
And the triphenyl phosphite (TPP, triphenyl phosphite) stir about 30 minutes of 1g.Afterwards, using less than 0.45 μm
Filter paper being filtered, and be added to 0.05g V65,0.12g 3-M as catalyst, addition as it is internal from
The 8-PENPP of the 4-PENPP and 0.2g of the 0.05g of type agent is simultaneously mixed, so as to be prepared for polymerizable composition, polymerizable composition.So will make
Standby optical lenses with polymerizable composition, polymerizable composition stir 1 hour after, vacuum deaerator 10 minutes is simultaneously filtered, afterwards, flow into by
The glass mold of polyester adhesive tape assembling.The glass mold for being injected with polymerizable composition, polymerizable composition is put in forced cyclic type baking oven,
It was heating and curing to after 110 DEG C Jing 20 hours from 35 DEG C, is cooled to 70 DEG C, and assembles and disassembles glass mold to have obtained lens.Obtain
After lens are processed to a diameter of 72mm, ultrasound wave cleaning is carried out in alkali aqueous rinsing liquid, afterwards, moved back at a temperature of 120 DEG C
Fire is processed 2 hours.Physical property is determined in the following manner, and be the results are shown in table 1.
Physical property experiment method
The physical property of the optical lenses prepared by following physical property experiment method is determined, and its result is recorded in following table 1
In.
1) refractive index and Abbe number：Carried out using the Abbe refractometer of the DR-M4 models that (Atago) company is opened up as love
Determine.
2) proportion：It is determined using analytical balance and by method of substitution in water.
3) release：When optical lenses are prepared, heat curing epoxy acrylic resin composition, and at a temperature of 70 DEG C
The demoulding is carried out, now, the extent of damage of lens or mould when separating with mould according to optical lenses is expressed as "○" and "×".
"○" represents that during 100 optical lenses and mould are detached lens or mould are not damaged or 1 impaired feelings completely
Condition, "×" represented during 100 optical lenses and mould are detached, the impaired situation of the lens of more than 4 or mould.
4) heat stability：The optical lenses of solidification are maintained 10 hours at a temperature of 100 DEG C, if determining color change
During, APHA values are less than 2, then it represents that for "○", if during color change is determined, APHA values are more than 2, then it represents that
For "×".
5) arteries and veins reason：By the mercury-arc lamp (Mercury Arc Lamp) as USH10USH-102D and observe by the naked eye
100 lens, and judge that confirming as the lens in arcuation has arteries and veins reason phenomenon, and calculate arteries and veins reason generation rate.
6) albefaction：The demoulding is carried out after polymerization, afterwards, in the state of the processing of the face of not carrying out, is entered with more than 1800LUX illumination
Row irradiation, so as to the part or some that are calculated in lens in percentage observe by the naked eye it is grey boundless and indistinct and muddy existing
The quantity of elephant.
2～embodiment of embodiment 6
Constituent according to described in table 1 in the same manner as in Example 1 prepares compositionss and optical lenses respectively,
Physical property is tested, and be the results are shown in table 1.
Comparative example 1
The composition (III) of composition (I), 30g to the 15g in the Epoxy Acrylates compound for obtaining in the above-described manner
And the α-methylstyrenedimer as polymerization regulator of addition 0.05g, the conduct of 40g are reacted in the composition (V) of 10g
The α-methyl styrene of the styrene and 5g of diluent, and add the diphenyl dodecylphosphoric acid as heat stabilizer of 2g
Ester, the tributyl phosphate (TBP, tributyl phosphate) of 1g and triphenyl phosphite (TPP, the triphenyl of 1g
) and stir about 30 minutes phosphite.Afterwards, using less than 0.45 μm of filter paper being filtered, and it is added to
The 3-M of V65,0.13g of 0.05g is used as catalyst, 12- of the addition as the 8-PENPP and 0.1g of the 0.1g of internal mould release
PENPP is simultaneously mixed, and so as to prepare after optical lenses resin combination, prepares optical lenses as follows, determines saturating
The physical property of mirror, and the results are shown in table 1.
Comparative example 2
Compositionss and optical lens are respectively prepared according to constituent described in table 1 with 1 identical method of comparative example
Mirror, is tested to physical property, and the results are shown in table 1.
Table 1
Referred to as
Internal mould release
4-PENPP：Ethylene nonyl phenyl phosphate ester (polyoxyethylene nonyl phenyl
Phosphate) (5 percentage by weights of the oxirane of 5 moles of addition, 80 weight percents of the oxirane of 4 moles of addition
Than, addition 3 moles oxirane 10 percentage by weights, addition 1 mole oxirane 5 percentage by weights)
8-PENPP：Ethylene nonyl phenyl phosphate ester (5 percentage by weights of the oxirane of 9 moles of addition, addition 8
Mole oxirane 80 percentage by weights, addition 7 moles oxirane 10 percentage by weights, addition less than 6 moles
Oxirane 5 percentage by weights)
12-PENPP：Polyoxyethylene nonylphenol ether phosphate (polyoxyethylene nonyl phenol ether
Phosphate) (3 percentage by weights of the oxirane of 13 moles of addition, 80 weight percents of the oxirane of 12 moles of addition
Than, 8 percentage by weights of the oxirane of 11 moles of addition, 3 percentage by weights of the oxirane of 9 moles of addition, addition 4 rub
6 percentage by weights of your oxirane)
16-PENPP：Polyoxyethylene nonylphenol ether phosphate (3 percentage by weights of the oxirane of 17 moles of addition,
79 percentage by weights of the oxirane of 16 moles of addition, 10 percentage by weights of the oxirane of 15 moles of addition, addition 14
Mole oxirane 4 percentage by weights, addition 13 moles oxirane 4 percentage by weights)
Heat stabilizer
DPDP：Diphenyl 1-isobutyl-3,5-dimethylhexylphosphoric acid (diphenyl dodecyl phosphate)
DOP：Two sad phosphate esters (dioctylacid phosphate)
TBP：Tributyl phosphate (tributyl phosphate)
DBTM：Dibutyitin maleate (dibutyltin maleate)
TPP：Triphenyl phosphite (triphenyl phosphite)
DPP：Diphenyl isodecyl phosphite (diphenylisodecyl phosphite)
Polymerization initiator
V65：2, double (2,4- methyl pentane nitrile) (2, the 2 '-azobis (2,4- of 2 '-azo
dimethylvaleronitrile)
3-M：1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes (1,1-bis (t-butylperoxy) -3,
3,5-trimethyl cyclohexane)
Industrial applicability
According to the present invention, by stably maintaining appropriate polymerization speed, nothing can easily be prepared with low preparation expense
The propylene oxide acids optical material of fine qualities of arteries and veins reason, albinism etc..Propylene oxide acids prepared in accordance with the present invention
Optical material has an outstanding optical characteristics such as high index of refraction, high Abbe number, the transparency, light weight, thermostability, no arteries and veins reason,
Albinism etc., and it is of fine qualities, it is thus possible to replace conventional optical material to be widely used in various fields.Especially,
Lenses or camera lens etc. can be widely utilized as, specifically, plastic spectacle lens can be utilized as, be installed in lenses
Have 3D polarized lenses of light polarizing film etc., furthermore it is possible to use in the recording medium substrate used in prism, fiber optics, CD etc. or
Various optical articles of coloring filter and ultra-violet absorption filter.
Claims (15)
1. a kind of propylene oxide acids polymerizable composition for optical material, it is characterised in that comprising being represented by formula 1 below
Compound, above-mentioned propylene oxide acids polymerizable composition for optical material comprising total polymerization compositionss 0.1～0.95
The α-methylstyrenedimer of percentage by weight,
Chemical formula 1：
Wherein, n=0～15, R1For H or CH3, R2For H or Br.
2. propylene oxide acids polymerizable composition for optical material according to claim 1, it is characterised in that also include
The compound represented by formula 2 below,
Chemical formula 2：
Wherein, R is H or CH3, m=0～5, n=0～5 are 0, m+n=1～10 when m is different with n.
3. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterised in that on
State in propylene oxide acids polymerizable composition for optical material, liquid phase viscosity is 20～1000cps at a temperature of 25 DEG C, liquid phase
Refractive index nE is 1.50～1.58 at 20 DEG C, and solid phase refractive index nE is 1.54～1.63 at 20 DEG C.
4. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterised in that remove
Outside above-mentioned α-methylstyrenedimer, as reactive diluent also comprising selected from styrene, divinylbenzene, α-
Methyl styrene, benzyl methacrylate, chlorostyrene, bromstyrol, methoxy styrene, maleic acid list benzyl ester, fumaric acid
Single benzyl ester, dibenzyl maleate, dibenzyl fumarate, methyl-benzyl maleate, dimethyl maleate, ethyl maleate.,
Dibutyl maleate, dibutyl fumarate, butyl maleate, maleic acid list pentyl ester, dipentyl maleate, fumaric acid list penta
One or more compound in the group of the double aryl carbonates compositions of ester, fumaric acid diamyl ester and diethylene glycol.
5. propylene oxide acids polymerizable composition for optical material according to claim 4, it is characterised in that relative to
The compound represented by above-mentioned chemical formula 1 of 100 weight portions is also mixed with by changing in the compound represented by above-mentioned chemical formula 1
The monomer component of the compound that formula 2 is represented, the global reactivity diluent comprising 30～300 weight portions.
6. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterised in that also
Comprising phosphate compound as internal mould release.
7. propylene oxide acids polymerizable composition for optical material according to claim 6, it is characterised in that above-mentioned phosphorus
Ester compound is the oxirane selected from 5 percentage by weights comprising the oxirane for adding 5 moles, 4 moles of addition
80 percentage by weights, 10 percentage by weights of the oxirane of 3 moles of addition, 5 weight percents of the oxirane of 1 mole of addition
The polyoxyethylene nonylphenol ether phosphate of ratio, 5 percentage by weights of the oxirane comprising 9 moles of addition, 8 moles of addition
80 percentage by weights of oxirane, 10 percentage by weights of the oxirane of 7 moles of addition, the epoxy of less than 6 moles of addition
The polyoxyethylene nonylphenol ether phosphate of 5 percentage by weights of ethane, 3 weight hundred comprising the oxirane for adding 11 moles
Divide ratio, 80 percentage by weights of the oxirane of 10 moles of addition, 5 percentage by weights of the oxirane of 9 moles of addition, addition
6 percentage by weights of 7 moles of oxirane, the ethylene nonyl benzene of 6 percentage by weights of the oxirane of 6 moles of addition
2, 2-Oxydiphenol phosphate ester, 3 percentage by weights comprising the oxirane for adding 13 moles, 80 weight of the oxirane of 12 moles of addition
Percentage ratio, addition 11 moles oxirane 8 percentage by weights, addition 9 moles oxirane 3 percentage by weights, add
Plus polyoxyethylene nonylphenol ether phosphate, the epoxy comprising 17 moles of addition of 6 percentage by weights of 4 moles of oxirane
3 percentage by weights of ethane, 79 percentage by weights of the oxirane of 16 moles of addition, the 10 of the oxirane of 15 moles of addition
Percentage by weight, 4 percentage by weights of the oxirane of 14 moles of addition, 4 weight percents of the oxirane of 13 moles of addition
The polyoxyethylene nonylphenol ether phosphate of ratio, 5 percentage by weights comprising the oxirane for adding 21 moles, 20 moles of addition
78 percentage by weights of oxirane, 7 percentage by weights of the oxirane of 19 moles of addition, 18 moles of epoxy second of addition
6 percentage by weights of alkane, the polyoxyethylene nonylphenol ether phosphate of 4 percentage by weights of the oxirane of 17 moles of addition,
Two sad phosphate esters and Zelec UNTMOne or more compound in the group of composition.
8. propylene oxide acids polymerizable composition for optical material according to claim 1 and 2, it is characterised in that
Heat stabilizer in total composition, also comprising 0.01～5 percentage by weight.
9. a kind of preparation method of propylene oxide acids optical material, it is characterised in that comprise the steps：When will comprising by with
When the propylene oxide acids polymerizable composition for optical material of the compound that lower chemical formula 1 is represented carries out matrix polymerization, addition
The Alpha-Methyl benzene of 0.1～0.95 percentage by weight of the gross weight of above-mentioned propylene oxide acids polymerizable composition for optical material
Matrix polymerization is carried out after ethylene dimerization thing mixing, for maintaining appropriate polymerization speed,
Chemical formula 1：
Wherein, n=0～15, R1For H or CH3, R2For H or Br.
10. the preparation method of propylene oxide acids optical material according to claim 9, it is characterised in that above-mentioned epoxy
Acrylic compounds polymerizable composition for optical material also comprising the compound represented by formula 2 below,
Chemical formula 2：
Wherein, R is H or CH3, m=0～5, n=0～5 are 0, m+n=1～10 when m is different with n.
The preparation method of the 11. propylene oxide acids optical materials according to claim 9 or 10, it is characterised in that include
Following steps：In addition to above-mentioned α-methylstyrenedimer, as reactive diluent, also addition selected from styrene,
Divinylbenzene, α-methyl styrene, benzyl methacrylate, chlorostyrene, bromstyrol, methoxy styrene, maleic acid
Single benzyl ester, mono-benzyl fumarate, dibenzyl maleate, dibenzyl fumarate, methyl-benzyl maleate, dimethyl maleate,
Ethyl maleate., dibutyl maleate, dibutyl fumarate, butyl maleate, maleic acid list pentyl ester, maleic acid diamyl
In the group of the double aryl carbonates composition of ester, fumaric acid list pentyl ester, fumaric acid diamyl ester, diethylene glycol one or more
Matrix polymerization is carried out after compound mixing.
The preparation method of 12. propylene oxide acids optical materials according to claim 11, it is characterised in that relative to
The compound represented by above-mentioned chemical formula 1 of 100 weight portions is also mixed with by changing in the compound represented by above-mentioned chemical formula 1
The monomer component of the compound that formula 2 is represented, is mixed after the global reactivity diluent for adding 30～300 weight portions.
13. a kind of optical materials, it is characterised in that the propylene oxide acids optical material described in claim 1 or 2 is polymerized
Property compositionss carry out matrix polymerization and obtain.
14. a kind of optical lenses, it is characterised in that formed by the optical material described in claim 13.
15. optical lenses according to claim 14, it is characterised in that above-mentioned optical lenses are lenses or polariscope
Piece.
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| PCT/KR2013/007684 WO2014035121A1 (en) | 2012-08-27 | 2013-08-27 | Polymerization composition for epoxy acrylic optical material and method for manufacturing epoxy acrylic optical material |
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| CN1418318A (en) * | 2000-11-20 | 2003-05-14 | 日本油脂株式会社 | Composition for optical materical, optical material and lenses |
| CN103635497A (en) * | 2012-06-13 | 2014-03-12 | 可奥熙搜路司有限公司 | 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 |
| CN104520376A (en) * | 2012-08-14 | 2015-04-15 | 可奥熙搜路司有限公司 | Polymerizable composition for epoxy acrylic optical material, and method for preparing epoxy acrylic optical material |
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| JP3362987B2 (en) * | 1994-12-22 | 2003-01-07 | 三菱レイヨン株式会社 | Composition for plastic lens |
| JP2001122926A (en) * | 1999-10-29 | 2001-05-08 | Nof Corp | Monomer composition for optical material, method of producing synthetic resin lens and lens |
| KR100496911B1 (en) | 2000-11-07 | 2005-06-23 | 장동규 | A Material for Plastic Lense |
| KR100474586B1 (en) * | 2002-06-12 | 2005-03-08 | 주식회사 두산 | Resin compositions, and optical lens prepared by them |
| KR100498896B1 (en) * | 2003-03-25 | 2005-07-04 | 장동규 | Epoxy acrylate resin composition for optical lens |
| JP4228780B2 (en) * | 2003-05-23 | 2009-02-25 | Ｄｉｃ株式会社 | Active energy ray-curable resin composition for casting polymerization |
| KR100529369B1 (en) * | 2004-03-02 | 2005-11-21 | 주식회사 니드필 | Resin composition for producing optical lens having low density and medium refraction index, and optical lens produced with the same |
| KR101347611B1 (en) * | 2007-12-13 | 2014-01-06 | 가부시끼가이샤 도꾸야마 | Photochromic curable composition |
| 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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| CN1418318A (en) * | 2000-11-20 | 2003-05-14 | 日本油脂株式会社 | Composition for optical materical, optical material and lenses |
| CN103635497A (en) * | 2012-06-13 | 2014-03-12 | 可奥熙搜路司有限公司 | 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 |
| CN104520376A (en) * | 2012-08-14 | 2015-04-15 | 可奥熙搜路司有限公司 | Polymerizable composition for epoxy acrylic optical material, and method for preparing epoxy acrylic optical material |
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