CN110337456A - Resin combination and preparation method thereof for refractive optical lenses in propylene oxide acids - Google Patents
Resin combination and preparation method thereof for refractive optical lenses in propylene oxide acids Download PDFInfo
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- CN110337456A CN110337456A CN201880013795.6A CN201880013795A CN110337456A CN 110337456 A CN110337456 A CN 110337456A CN 201880013795 A CN201880013795 A CN 201880013795A CN 110337456 A CN110337456 A CN 110337456A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00355—Production of simple or compound lenses with a refractive index gradient
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0006—Arrays
- G02B3/0012—Arrays characterised by the manufacturing method
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- Ophthalmology & Optometry (AREA)
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- Epoxy Resins (AREA)
Abstract
The present invention relates to propylene oxide acids optical lenses, in particular, being related to the resin combination and preparation method thereof that the transparency, Abbe number, thermal stability, light resistance and compression strength that solid phase refractive index is 1.53~1.58 are effectively used for refractive optical lenses in propylene oxide acids.In the present invention, a kind of resin combination for refractive optical lenses in propylene oxide acids of solid phase refractive index 1.53~1.58 is provided, comprising by make to be indicated by following chemical formula 1 and the bisphenol A diglycidyl ether of 100~1700ppm of chlorinity and acrylic acid are reacted come the bisphenol A epoxy acrylate of 50~70 weight percent obtained, the methyl methacrylate of 21~45 weight percent, 1~17 weight percent reactive diluent.In the present invention, chlorinity by controlling bisphenol A diglycidyl ether makes composition (MMA) containing a large amount of methyl methacrylates, the compression strength for the middle refractor that refractive index is 1.53~1.58 is improved, and can provide the transparency, Abbe number, thermal stability, the light resistance also very outstanding resin combination for being used for refractive optical lenses in propylene oxide acids.Refractive optical lenses can be widely used in various fields in refractive optical lenses replacement in propylene oxide acids of the invention.
Description
Technical field
The present invention relates to a kind of propylene oxide acids optical lens more particularly to refractive index be 1.53~1.58 it is transparent
Property, Abbe number, thermal stability, light resistance and the outstanding resin for refractive optical lenses in propylene oxide acids of compression strength
Composition and preparation method thereof.
Background technique
A kind of polymethyl methacrylate (polymethyl- used as acrylic resin released in 1936
Methacrylate, PMMA) lens be also referred to as acrylic lenses, Abbe number is 57 to have a high grade of transparency, but refractive index
It is lower for 1.49, compared with the CR-39 with similar refractive index, have the shortcomings that heat resistance and surface strength are low.
Japanese DISO company is in 1992 in tetrabromobisphenol A diacrylate (diacrylate of
Tetrabromobisphenol A) in mix styrene isoreactivity diluent, develop acrylic compounds high refractive index tree for the first time
Rouge, but utilize the thermal stability of its lens and light resistance insufficient, therefore not yet use.
Then, it proposes in Japanese Laid-Open Patent Japanese Laid-Open Patent Publication 6-49133 and Japanese Laid-Open Patent Publication 7-206974 in tetrabromobisphenol A two
The method for mixing divinylbenzene, styrene, benzyl methacrylate, isocyanates etc. in acrylate to prepare lens.This
The light resistance and heat resistance of a little optical lenses are improved, but since its thermal stability is low, there are color occurs when hard conating
The problem of variation.
In order to solve these problems, it is 1.58 that a kind of refractive index is proposed in KR published patent 10-2004-0083942
~1.61 lens mix styrene, methyl styrene isoreactivity diluent, Xiang Qi in tetrabromobisphenol A diacrylate
It is middle to add acid phosphoric acid ester to greatly improve the thermal stability and light resistance of eyeglass.This epoxy acrylic is lens-like excellent
Point is there is high refractive index and high Abbe number, and the optical characteristics such as the transparency, light weight, heat resistance are outstanding, material is cheap.
But when preparing Epoxy Acrylates lens, exist cause because of unknown cause thermal stability, the transparency,
The case where light resistance declines.Furthermore, it is desirable to which the reactive diluent of Adjustable viscosity and reaction speed, in the past, anti-as these
Answering property diluent is used alone or mixes two or more styrene, divinylbenzene, α-methylstyrene, α-methylstyrene
Dimer, benzyl methacrylate, chlorostyrene, smelly styrene, methoxy styrene, malic acid dibenzyl ester etc. use.This
The selection of a little diluents will affect the productivity and optical characteristics of lens, and have an effect on producing cost.For example, often depositing at present
And in resin the styrene containing high-content be the reason of leading to strength reduction.
On the other hand, the previous optical lens of ranges of indices of refraction as in used polyethylene glycol diene propyl carbonate,
The various kinds of resin such as polymethyl methacrylate, diallyl phthalate, polystyrene, polycarbonate.
A kind of mixing acrylic acid and 5~40 in the styrene of 15~50 parts by weight is provided in European patent 06905A2
The bisphenol A type epoxy resin reactant of parts by weight, the acrylic acid of 5~40 parts by weight and the reaction of double tetrabromobisphenol A based epoxy resins
Object, and divinylbenzene, diallyl diphenyl ester (phenate), vinyltoluene and the chlorine of 5~20 parts by weight are mixed thereto
The optical resin composition of styrene, but there is a problem of its thermal stability deficiency.
The diallyl isophthalate and 15 weights of 85 weight percent of polymerization are provided in Japanese Laid-Open Patent Showa 53-7787
The optical lens for measuring the diethylene glycol (DEG) diallylcarbonate of percentage, in the case where this lens, although successfully reducing lens
Thickness, but the problem low there are still impact resistance.
Also provided in Japanese Laid-Open Patent Showa 62-235901, Showa 64-45412 and Japan Patent Heisei 1-60494 by
It is modified the plastic lens of the copolymer preparation of diallyl phthalate and dibenzyl fumarate composition and by phthalic acid
The plastic lens of the copolymer preparation of diallyl and methyl acrylate composition, these problems low there is also impact resistance.
It is disclosed in Korean Patent Publication 10-0431434 by diallyl oligomer, apple acid dialkyl ester, two
The middle refractor of 1.53~1.55 ranges of glycol diene propyl carbonate and two acrylic ester of adipic acid composition is combined with monomer
Object.Compared with existing middle refractor, there is the photostability and impact resistance being improved, but there are Abbe number and thoroughly
The problem that bright property declines and heat resistance is low.
In the lens-like situation of epoxy acrylic, the optical characteristics such as the transparency, Abbe number are outstanding, if therefore heat-resisting
Property, improve quality in terms of light resistance, compression strength and reduce production cost, then relative to other materials, refractive index is 1.53~
1.58 or so middle refractor can have competitiveness.
Existing technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication Showa 53-7787
Patent document 2: Japanese Laid-Open Patent Publication Showa 62-235901
Patent document 3: Japanese Laid-Open Patent Publication Showa 64-45412
Patent document 4: Japanese Laid-Open Patent No. is at 1-60494
Patent document 5: European patent 06905
Patent document 6: Korean Patent Publication 10-0431434
Patent document 7: Korean Patent Publication 10-0496911
Patent document 8: Korean Patent Publication 10-0498896
Patent document 9: Korean Patent Publication 10-2015-0071170
Summary of the invention
Problems to be solved by the invention
It is an object of the present invention to unknown saturating of the reason of illustrating when preparing Epoxy Acrylates lens frequent occurrence
The problem of bright property, thermal stability and light resistance decline with occur in the preparation process of bisphenol A diglycidyl ether (BPDE)
Chlorinity is related, and solves the problems, such as this.
Methyl methacrylate and existing styrene or divinylbenzene, α-methylstyrene, α-methylstyrene two
Aggressiveness etc. together be used as reactive diluent, but the usage amount in resin be 20 weight percent more than when, physical property albefaction,
Polymerizeing many aspects such as imbalance, there are problems, most of to be used only on a small quantity.However, using a large amount of methyl methacrylates
In the case of, relative to styrene is used, compression strength improves, even if therefore can also be improved intensity with production cost is not increased
The advantages of.Include a large amount of methyl more than 20 weight percent in the object of the present invention is to provide lenticular resins composition
Methyl acrylate, the transparency, Abbe number, thermal stability, light resistance are outstanding, and compression strength is excellent and economical to be used for
The resin combination of refractive optical lenses in propylene oxide acids.
The solution to the problem
In order to realize that purpose as described above, the present invention provide a kind of epoxy for being 1.53~1.58 for solid phase refractive index
The resin combination of refractive optical lenses in acrylic compounds, comprising by make to be indicated by following chemical formula 1 and chlorinity 100~
50~70 weight percent that the bisphenol A diglycidyl ether and acrylic acid of 1700ppm is reacted to obtain by followingization
The methyl methacrylate and 1~17 weight percent of bisphenol A epoxy acrylate, 21~45 weight percent that formula 2 indicates
The reactive diluent of ratio.
Chemical formula 1:
In the chemical formula 1, n=0~15.
Chemical formula 2:
In the chemical formula 2, n=0~15.
The resin combination for refractive optical lenses in propylene oxide acids also may include internal release agent.
Also, in the resin combination for refractive optical lenses in propylene oxide acids, composition can also be wrapped
Heat stabilizer containing 0.01~5 weight percent.
It provides and a kind of is consolidated by polymerizeing the resin combination for optical lens in a mold come what is obtained in the present invention
Refractive optical lenses in the propylene oxide acids that phase refractive index is 1.53~1.58, the resin combination for optical lens
Comprising by making to be indicated by following chemical formula 1 and the bisphenol A diglycidyl ether and acrylic acid of 100~1700ppm of chlorinity
The bisphenol A epoxy acrylate of 50~70 weight percent for being reacted to obtain indicated by following chemical formula 2,21~45
The reactive diluent of the methyl methacrylate of weight percent and 1~17 weight percent.
Chemical formula 1:
In the chemical formula 1, n=0~15.
Chemical formula 2:
In the chemical formula 2, n=0~15.
Also, the present invention provides a kind of preparation method of refractive optical lenses in acrylic compounds, including will be used for epoxy third
The step of resin combination of refractive optical lenses is added in mold and is polymerize in olefin(e) acid class.
Invention effect
According to the present invention, a kind of propylene oxide acids optical lens resin combination is provided, comprising passing through control bisphenol-A
The chlorinity of diglycidyl ether opens the bisphenol A epoxy acrylate of acquisition, and contains a large amount of methyl methacrylates (MMA),
Thus mentioned significantly in refractive optical lenses with low production cost in the propylene oxide acids that solid phase refractive index is 1.53~1.58
High compressive strength, and the transparency, Abbe number, thermal stability, light resistance are also very outstanding.
Specific embodiment
Resin combination for refractive optical lenses in propylene oxide acids of the invention includes by 2 table of following chemical formula
Bisphenol A epoxy acrylate (BPDA), methyl methacrylate and the reactive diluent shown.
Chemical formula 2:
In the chemical formula 2, n=0~15.
The bisphenol A epoxy acrylate passes through the bisphenol A diglycidyl ether and propylene for making to be indicated by following chemical formula 1
Acid is reacted to obtain.
Chemical formula 1:
In the chemical formula 1, n=0~15.
The inventors discovered that when preparing Epoxy Acrylates lens frequent occurrence the reason of the unknown transparency, heat
The problem of stability and light resistance decline is related with the content of chlorine produced during the preparation process in bisphenol A diglycidyl ether.
In the present invention, it is preferred to the chlorinity of the bisphenol A diglycidyl ether be 100~1700ppm, more preferably 200~
1500ppm.Chlorinity can be removed or reduced by the process cleaned with water and ammonium hydroxide in bisphenol A diglycidyl ether.It is preferred that
Ground, the chlorinity in bisphenol A diglycidyl ether are less than 100ppm, still, relative to being not easy to drop below chlorinity
100ppm, can through the invention following embodiments confirmation, almost do not have on lens quality less than 100ppm and 100~200ppm
It is variant.Therefore, when considering lens quality and production cost, it is preferable that the chlorinity of bisphenol A diglycidyl ether is 100
~1700ppm, more preferably 200~1500ppm.
In the present invention, total chlorine that the chlorinity of bisphenol A diglycidyl ether is defined as bisphenol A diglycidyl ether contains
It measures (Total Cl (ppm)), measures by the following method.
The measuring method of chloride content
The bisphenol-A diethylene glycol (DEG) etherificate of 1g and 2g is separately added into the conical flask cleaned up using deionized-distilled water
Object is closed, and adds the dioxane of 30mL.The KOH 2-methyl cellosolve solution of the 1N of 5mL is added into the solution of dissolution and returns
Stream 20 minutes.Then, the solution of acquisition is transferred in the new flask of 200mL.Using this solution of acetone solution and by total amount tune
After the acetic acid of 3mL is added into the solution of 100mL, with the AgNO of 0.01N3Aqueous solution carries out point titration.
Formula 1:
A1, a2: the AgNO of the 0.01N corresponding to b1, b23Ml
B1, b2: the amount of weighing (g) of bisphenol-A diethylene glycol ethers compound
The AgNO of F:0.01N3Multiple (factor)
It include 50~70 weight hundred in resin combination for refractive optical lenses in propylene oxide acids of the invention
The bisphenol A epoxy acrylate (BPDA) for dividing ratio, preferably includes 55~65 weight percent.
It include the methyl methacrylate and styrene or divinylbenzene, Alpha-Methyl in resin combination of the invention
Styrene, α-methylstyrene dimer etc. are used as reactive diluent in existing propylene oxide acids optical resin together.
But it is different from styrene or divinylbenzene, do not include a large amount of methyl methacrylates, generally using a small amount of 3% or so, most
Mostly less than 20%.Since when methyl methacrylate contains 20 weight percent or more in optical lens resin, lens
Physical property in albefaction, there are problems for many aspects of polymerization imbalance etc..But in the present invention, 20 weight hundred are contained in resin
Divide than above a large amount of methyl methacrylates, and will be used in the preparation for the bisphenol A epoxy acrylate that be used together
The chlorinity of bisphenol A diglycidyl ether controls in 100~1700ppm, while bisphenol A epoxy acrylate in resin being contained
Amount is adjusted to 50~70 weight percent, thus can improve the transparency, Abbe number, thermal stability, light resistance.At the same time, make
Styrene is replaced with a large amount of methyl methacrylates, even if not increasing production cost, compression strength can also be greatly improved.It is excellent
Selection of land, resin combination of the invention include the methyl methacrylate of 21~45 weight percent, more preferably may include 25
The methyl methacrylate of~40 weight percent.
Included in the reactive diluent of resin combination of the invention play appropriate regulation composition viscosity and
The effect of polymerization speed, in propylene oxide acids optical lens resin, reactive diluent is not particularly limited, as long as
As reactive diluent.
Preferably, the reactive diluent can be used alone or using two or more selected from by styrene, divinyl
Benzene, α-methylstyrene, α-methylstyrene dimer, benzyl methacrylate, chlorostyrene, smelly styrene, methoxybenzene
Ethylene, malic acid list benzyl ester, mono-benzyl fumarate, malic acid dibenzyl ester, dibenzyl fumarate, malic acid methylbenzyl ester, malic acid
Dimethyl ester, diethyl malate, dibutyl malate, dibutyl fumarate, butyl maleate, maleic acid list pentyl ester, Malaysia
The compound in group that sour diamyl ester, fumarate monopentyl ester, diamyl fumarate and diethylene glycol diaryl carbonate form.More
Preferably, the reactive diluent is selected from by styrene, divinylbenzene, α-methylstyrene, α-methylstyrene two
Compound in the group of aggressiveness composition.
The methyl methacrylate that resin combination of the invention must be included in plays the role of reactive diluent, therefore
Preferably, other a small amount of reactive diluents comprising 1~17 weight percent.Anti- with other comprising methyl methacrylate
In the case that the content of the global reactivity diluent of answering property diluent is greater than 60 weight percent, due to the viscosity of composition is too low
It is likely to result in binder tape fusing, in the case, albinism and solidification after the implantation may occur for adhesive tape
Leakage may occur in journey, thus albefaction may occur in lens and haze.
Resin combination of the invention comprising methyl methacrylate and reactive diluent is being suitable for cast polymerization
25 DEG C at a temperature of liquid phase viscosity be 20~200cps, the liquid phase refractive index (nD, 20 DEG C) of resin combination is 1.48~
1.55, solid phase refractive index (nE, 20 DEG C) is 1.53~1.58.If being sealed when liquid phase viscosity is less than 20cps to by synthetic resin
It encloses in the glass mold of assembling and injects liquid resin composition when forming, there are problems that composition flows out mold, if liquid phase
Viscosity be greater than 200cps, then there are problems that being difficult to by composition injection mold.It is highly preferred that viscosity is 30~100cps.
Resin combination of the invention also may include internal release agent.Before cast polymerization, add into resin combination
Add internal release agent, to be greatly improved release after polymerization.It preferably, may include 0.001~10 in polymerizable composition, polymerizable composition
The internal release agent of weight percent.
Two or more phosphate compounds, silicon class surface can be used individually or used simultaneously as internal release agent
Activating agent, fluorine class surfactant, alkyl quaternary ammonium salts etc..
Fluorine class nonionic surfactant is the compound in molecule with perfluoroalkyl, there is You Nien (UNIDYNE) DS-
401TM(Japan, Daikin Ind Ltd), You Nien DS-403TM(Japan, Daikin Ind Ltd), F top EF
122ATM(Japan, new nurse Kasei Co., Ltd.), F top EF 126TM(Japan, Kasei plants of formula meetings of new nurse
Society), F top EF 301TM(Japan, new nurse Kasei Co., Ltd.) etc..
Silicon class nonionic surfactant is the compound in molecule with dimethylpolysiloxane--based, there is U.S. Dow ' s
The Q2-120A of companyTMDeng.
Alkyl quaternary ammonium salts is generally known as cationic surfactant, there is halogen, phosphate, sulfate etc., wherein as
The example of villaumite has trimethyl cetyl chloride ammonium, trimethyl stearyl ammonium chloride, dimethyl ethyl cetyl chloride ammonium, three
Ethyl decyl hydroxylammonium chloride, tri-n-octyl methyl ammonium chloride, decyl ammonium chloride etc..
Phosphate compound can be used preferably as internal release agent.Phosphate compound is phosphate-based chemical combination
Object, for example, p isopropylbenzoic acid ester, diisopropyl phosphate, butylphosphoric acid ester, dibutylphosphoric acid ester, octyl phosphate, dioctylphosphoric acid ester, phosphoric acid
Isodecyl ester, phosphoric acid diisodecyl ester, phosphoric acid tridecane ester, phosphoric acid bis- (tridecane esters) and their two or more mixtures etc..
It can be used preferably as phosphate compound selected from by polyoxyethylene nonylphenol ether phosphate, (ethylene oxide adds 5 moles
5 weight percent, 80 weight percent for adding 4 moles, 10 weight percent for adding 3 moles, 5 weight for adding 1 mole
Percentage), (ethylene oxide adds 9 moles of 5 weight percent to polyoxyethylene nonylphenyl phosphate, ethylene oxide addition 8 rubs
Your 80 weight percent, ethylene oxide add 7 moles of 10 weight percent, ethylene oxide adds 6 moles of 5 weight below
Percentage), polyoxyethylene nonylphenol ether phosphate (ethylene oxide add 11 moles 3 weight percent, add 10 moles 80
Weight percent, 5 weight percent for adding 9 moles, 6 weight percent for adding 7 moles, 6 weight percents for adding 6 moles
Than), (ethylene oxide adds 13 moles of 3 weight percent, adds 12 moles of 80 weight polyoxyethylene nonylphenol ether phosphate
Percentage, 8 weight percent for adding 11 moles, 3 weight percent for adding 9 moles, 6 weight percents for adding 4 moles
Than), (ethylene oxide adds 17 moles of 3 weight percent, adds 16 moles of 79 weight polyoxyethylene nonylphenol ether phosphate
Percentage, 10 weight percent for adding 15 moles, 4 weight percent for adding 14 moles, 4 weight percents for adding 13 moles
Than), (ethylene oxide adds 21 moles of 5 weight percent, adds 20 moles of 78 weight polyoxyethylene nonylphenol ether phosphate
Percentage, 7 weight percent for adding 19 moles, 6 weight percent for adding 18 moles, 4 weight percents for adding 17 moles
Than), dioctyl acid phosphoric acid salt and Zelec UNTMThe compound of one or more of the group of composition.
Resin combination of the invention also may include heat stabilizer.Preferably, may include 0.01 in resin combination~
The heat stabilizer of 5.00 weight percent.When using the heat stabilizer less than 0.01 weight percent, thermostable effect is weak, when
When using being greater than 5.00 weight percent, solidification polymerization fraction defective is high, and the thermal stability of solidfied material declines instead.
For example, can be used as heat stabilizer selected from the calcium stearate, barium stearate, tristearin as fatty acid metal salt
One of compounds such as sour zinc, cadmium stearate, lead stearate, magnesium stearate, aluminum stearate, potassium stearate, zinc octoate or two
Kind or more compound.
Preferably, Phosphorus can be used is selected from triphenyl phosphite, diphenyl decyl phosphite ester, phenyl didecyl phosphorous
Acid esters, diphenyl dodecyl phosphite ester, diphenyl-isodecyl base phosphate, tritylphenyl phosphite ester, diphenyl are different
Octyl phosphite ester, tributyl phosphite ester, tripropyl phosphite ester, triethyl phosphorite, trimethyl phosphite, three
One or more of (single decyl phosphite ester), three (single phenyl) phosphite esters compound.Especially, it is preferable that can make
With diphenyl-isodecyl base phosphate.
Also, lead class is yet using selected from 3PbOPbSO4·4H2O、2PbO·Pb(C8H4O4)、3PbO·Pb
(C4H2O4)·H2One or more of compounds such as O.
Also, it can be used double selected from the dibutyl tin dilaurate, dibutyitin maleate, dibutyl tin as organotin
(the different monooctyl ester of maleic acid), malic acid dioctyl tin, dibutyl tin bis- (monomethyl maleates), the bis- (lauryl mercaptans of dibutyl tin
Ester), dibutyl bis- (thioacetic acid isodecyl esters), Monobutyltin three (iso-octyl mercaptoacetate), bis- (the iso-octyl mercaptos of stannous methide
Yl acetate), three (isooctyl thioglycolates), dioctyl tin bis- (iso-octyl mercaptoacetates), bis- (the 2- sulfydryl second of dibutyl tin
Acid esters), Monobutyltin three (2 mercapto ethanol ester), stannous methide bis- (2- thioglycolate salts), (the 2- thioacetic acid of monomethyl tin three
Salt) etc. one or more of compounds.
Also, it can also be used in mixed way the heat stabilizer illustrated to different series two or more in heat stabilizer.It is optimal
Selection of land is greatly improved the heat of the initial color and optical lens of molding lens by using Phosphorus heat stabilizer
Stability, without reducing the optical characteristics such as the transparency, impact strength, heat resistance, polymerization yield.
According to the routine techniques in plastic optical lens field, in addition to this resin combination of the invention may be used also as needed
Include ultraviolet absorbing agent, organic dyestuff, inorganic pigment, stainblocker, antioxidant, light stabilizer, catalyst etc..
It can be prepared in propylene oxide acids of the invention by the way that mold is added in the resin combination of the invention
Refractive optical lenses.According to preferred embodiment, after the resin combination is injected mold, and mold is put into forced circulation
Baking oven, by from 30 DEG C be heated to 120 DEG C of slow heat cures after be cooled to 70 ± 10 DEG C, remove mold obtain lens.At this point, excellent
Choosing, the high-purity compound that all raw material is 70~99.99% using purity.Preferably, by confirming all raw material
Purity purify the compound of low-purity, and without purification using the compound of high-purity.
Refractive optical lenses are that solid phase is refracted as 1.53~1.58 in the acrylic compounds obtained by the preparation method
Middle refractor can replace existing middle refractor to be widely used in various fields.Specifically, it can be used as Plastic eyeglasses mirror
Piece is equipped with lens, camera lens of 3D light polarizing film etc. in eyeglass, in addition, can be applicable in a variety of optical articles, such as uses
The recording medium substrate or colour filter of prism, optical fiber, CD etc. and ultraviolet absorbing filter etc..
Hereinafter, by specific embodiment, present invention be described in more detail.But these embodiments are only used for illustrating
The present invention, the scope of the present invention are not limited to these embodiments.
The measuring method of chloride content (Total Cl (ppm))
The bisphenol-A diethylene glycol (DEG) etherificate of 1g and 2g is separately added into the conical flask cleaned up using deionized-distilled water
Object is closed, and adds the dioxane of 30mL.The KOH 2-methyl cellosolve solution of the 1N of 5mL is added into the solution of dissolution and returns
Stream 20 minutes.Then, the solution of acquisition is transferred in the new flask of 200mL.Using this solution of acetone solution and by total amount tune
The acetic acid of 3mL is added after to 100mL, with the AgNO of 0.01N3Aqueous solution carries out point titration.
Formula 1:
A1, a2: the AgNO of the 0.01N corresponding to b1, b23Ml
B1, b2: the amount of weighing (g) of bisphenol-A diethylene glycol ethers compound
The AgNO of F:0.01N3Multiple (factor)
The synthesis of bisphenol A diglycidyl ether compound
Synthesis example 1
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, filtrate is used
5% salt water (50g) cleaning is primary, is cleaned three times with water (50g), is cleaned twice with 0.01% ammonium hydroxide (50g) and use water
(50g) is cleaned five times, by the way that the bisphenol A diglycidyl ether compound (BPDE1) for obtaining and having viscosity is concentrated under reduced pressure.BPDE1
Chloride content be 100ppm.
Reaction equation 1:
Synthesis example 2
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, filtrate is used
5% salt water (50g) cleaning is primary, washes with water twice, cleans primary with 0.01% ammonium hydroxide and wash with water three times, pass through
The bisphenol A diglycidyl ether compound (BPDE2) for obtaining and there is viscosity is concentrated under reduced pressure.The chloride content of BPDE2 is 200ppm.
Synthesis example 3
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, filtrate is used
5% salt water (50g) cleaning is primary, is cleaned twice with water (50g), is cleaned once with 0.01% ammonium hydroxide (50g), use water
(50g) cleaning is primary, by the way that the bisphenol A diglycidyl ether compound (BPDE3) for obtaining and having viscosity is concentrated under reduced pressure.BPDE3
Chloride content be 500ppm.
Synthesis example 4
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, filtrate is used
5% salt water (50g) cleaning is primary, washes with water five times, by the way that the bisphenol-A 2-glycidyl for obtaining and having viscosity is concentrated under reduced pressure
Ether compound (BPDE4).The chloride content of BPDE4 is 1000ppm.
Synthesis example 5
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, by filtrate water
(50g) is cleaned three times, after going water removal, by the way that the bisphenol A diglycidyl ether compound for obtaining and having viscosity is concentrated under reduced pressure
(BPDE5).The chloride content of BPDE5 is 1700ppm.
Synthesize comparative example 1
In method identical with reaction equation 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 1500g is extracted once, by being filtered under diminished pressure the NaCl (aq) removed as sediment, by filtrate water
(50g) cleaning is primary, by the way that the bisphenol A diglycidyl ether compound (BPDE6) for obtaining and having viscosity is concentrated under reduced pressure.BPDE6
Chloride content be 1900ppm.
Synthesize comparative example 2
In method identical with synthesis example 1, bisphenol-A (228g, 1mol), epoxychloropropane are added into there-necked flask
(925.3g, 10mol) and water (50g), slow heating stop heating when epoxychloropropane boils and comes to life, stirring
It is slowly added to a small amount of caustic soda (80g, 2mol) simultaneously.After all caustic soda are added, by reaction mixture heat intensive about 50 minutes,
Stop heating when the viscosity of reactant increases, the epoxy chloropropionate hydride compounds being then excessively added by being evaporated under reduced pressure removal.
The residue toluene of 2000g is extracted once, it is dense by depressurizing by being filtered under diminished pressure the NaCl (aq) removed as sediment
Contracting obtains the bisphenol A diglycidyl ether compound (BPDE7) with viscosity.The chloride content of BPDE7 is 2500ppm.
Epoxy acrylic ester compounds
Synthesis example 8
Acrylic acid (147g, 2mol), benzhydrylamine (5g) and 2, bis- uncle of 6- are added in the compound of BPDE1 (187 equivalent)
Reaction temperature is gradually increased to 105 DEG C from 60 DEG C and carries out reaction 20 hours by butyl -4- methylphenol (4g), is obtained 259 and is worked as
The compound (BPDA1) of the reaction equation 2 of the acroleic acid esterification of amount.
Reaction equation 2:
Synthesis example 9
Other than the compound and acrylic acid that make BPDE2 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA2) of the acroleic acid esterification of equivalent.
Synthesis example 10
Other than the compound and acrylic acid that make BPDE3 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA3) of the acroleic acid esterification of equivalent.
Synthesis example 11
Other than the compound and acrylic acid that make BPDE4 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA4) of the acroleic acid esterification of equivalent.
Synthesis example 12
Other than the compound and acrylic acid that make BPDE5 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA5) of the acroleic acid esterification of equivalent.
Compare synthesis example 3
Other than the compound and acrylic acid that make BPDE6 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA6) of the acroleic acid esterification of equivalent.
Compare synthesis example 4
Other than the compound and acrylic acid that make BPDE7 are reacted, 259 are obtained in method identical with synthesis example 8
The compound (BPDA7) of the acroleic acid esterification of equivalent.
The preparation of propylene oxide acids optical lens
Embodiment 1
Alpha-Methyl benzene of the addition as the 0.5g of polymerization regulator into the epoxy acrylic ester compounds (BPDA1) of 60g
Ethylene dimerization body, after addition is as the styrene of 5g and the methyl methacrylate of 35g of reaction diluent, stir about 30 divides
Clock.Then, it is filtered with 0.45 μm of filter paper below, the 3-M of the V65 and 0.12g of the 0.05g as catalyst is added thereto,
And the 8-PENPP for adding the 4-PENPP and 0.2g of 0.05g as internal release agent is mixed to prepare optical lens resin group
After closing object, it is prepared via a method which optical lens and measures the physical property of optical lens.
(1) after stirring optical lens produced above 1 hour with resin combination, deaerate 10 minutes and mistake under reduced pressure
After filter, inject in the glass mold assembled by polyester tape.
(2) injection is used for the resin combination glass mold of eyeglass from 35 DEG C to 110 in forced circulation baking oven
It DEG C is heating and curing after 20 hours, is cooled to 70 DEG C and removes glass mold to obtain lens.The lens of acquisition are processed into diameter
To carry out ultrasonic cleaning with alkaline aqueous cleaning solution after 72 ㎜, and anneal 2 hours at 120 DEG C.It measures by the following method
Simultaneously its result is shown in table 1 for physical property.
Physical property experiment method
The physical property for the optical lens that method measurement is prepared in embodiment through the following experiment, and by its result in table 1
It shows.
1) it refractive index and Abbe number: is measured using the Abbe refractometer of the model DR-M4 of Atago company.
2) it specific gravity: is measured using assay balance and by displacement method in water.
3) compression strength: the diameter for eyeglass is 75mm, center thickness 1.2mm, degree 8.00, utilization
The LR5K-Plus universal testing machine of LLOYD Instruments is measured according to the method for ISO14889 and JIS T57331
Until eyeglass is broken, and its measured value is indicated with N.
4) thermal stability: by cured optical lens 100 DEG C at a temperature of keep 10 hours, in the measurement of color change
In, it is indicated, is indicated when APHA value becomes 3~5 with "○", APHA value becomes using when 6~8 with " ◎ " when APHA value becomes 2 or more
" △ " is indicated, is indicated when APHA value becomes 9 or more with "×".
5) transparent: to detect by an unaided eye 100 under the mercury arc lamp (Mercury Arc Lamp) of USHIO USH-10D
Lens indicated when discovery 2~3 with "○" when muddiness for finding optical lens is 1 or less with " ◎ " expression,
It is indicated when finding 4 or more with "×".
6) light resistance: used Q-Lab. company to QUV/SE model accelerated ageing tester (Accelerated
Weathering Tester).QUV test is in UVA-340 (340nm), the light of 0.76W/m2, Black panel temperature
(Black Panel Temperature, BPT) (60 DEG C) 4 hours, condensation (condensation) (50 DEG C) 4 hours condition
Under to a thickness of 1.2mm planar lens irradiate 48 hours after, used when APHA value becomes 0~2 in the measurement of color change
" ◎ " is indicated, is indicated when APHA value becomes 3~5 with "○", and APHA value, which becomes "×" when 5 or more, to be indicated.
2~embodiment of embodiment 5
Other than with the forming and prepare optical lens resin combination of table 1, prepare in the same manner as in Example 1
Optical lens, and its physical property is measured, the results are shown in Table 1.
Comparative example 1
The Alpha-Methyl of the 0.5g as polymerization regulator is added into the epoxy acrylate (BPDA6) of 60g
Styrene dimer, and the styrene of 5g as reactive diluent and the methyl methacrylate of 35g, stir about 30 is added
Minute.With 0.45 μm of filter paper filtering below, the 3-M of the V65 and 0.12g of the 0.05g as catalyst are added thereto, and add
The 8-PENPP of the 4-PENPP and 0.2g of the 0.05g as internal release agent is added to mix to prepare optical lens resin combination
Afterwards, it is prepared via a method which optical lens and measures the physical property of optical lens.
2~comparative example of comparative example 3
Other than with the forming and prepare optical lens resin combination of table 1, prepare in the same manner as in Example 1
Optical lens, and its physical property is measured, the results are shown in Table 1.
Table 1
Abbreviation
MMA: methyl methacrylate
4-PENPP: (ethylene oxide adds 5 moles of 5 weight percent, ethylene oxide to ethylene oxide nonyl phenyl phosphate ester
80 weight percent of 4 moles of addition, 10 weight percent of 3 moles of ethylene oxide addition, ethylene oxide add the 5 of 1 mole
Weight percent)
8-PENPP: (ethylene oxide adds 9 moles of 5 weight percent, epoxy second to polyoxyethylene nonylphenyl phosphate
Alkane add 8 moles 80 weight percent, ethylene oxide add 7 moles 10 weight percent, ethylene oxide add 6 moles with
Under 5 weight percent)
(2,4- methyl pentane nitrile (the 2,2'-azobis (2,4-dimethylvaleronitrile) of V65:2,2'- azo two
Bis- (the t-butyl peroxy) -3,3,5- trimethyl-cyclohexanes of 3-M:1,1- (1,1-bis (t-butylperoxy) -3,3,
5-trimethyl cyclohexane)
Industrial availability
In accordance with the invention it is possible to be provided with low production ingredient, the transparency, thermal stability, light resistance be outstanding and compression strength
Refractive optical lenses in the propylene oxide acids that high solid phase refractive index is 1.53~1.58.Optical lens generation according to the present invention
It can be widely used in related field for existing middle refractor.In particular, can be used in plastic eyeglass lens, matching in eyeglass
In the lens of standby 3D light polarizing film, camera lens field, in addition, can be applicable in a variety of optical articles, such as using prism, optical fiber,
The recording medium substrate or colour filter of CD etc. and ultraviolet absorbing filter etc..
Claims (12)
1. a kind of resin combination is refractive optical lenses in 1.53~1.58 propylene oxide acids for solid phase refractive index,
It is characterized in that, comprising by making to be indicated by following chemical formula 1 and the bisphenol-A 2-glycidyl of 100~1700ppm of chlorinity
The bisphenol-A epoxy propylene of 50~70 weight percent that ether and acrylic acid are reacted to obtain indicated by following chemical formula 2
Acid esters, the methyl methacrylate of 21~45 weight percent, 1~17 weight percent reactive diluent:
Chemical formula 1:
In the chemical formula 1, n=0~15,
Chemical formula 2:
In the chemical formula 2, n=0~15.
2. resin combination according to claim 1, which is characterized in that the chlorinity is 200~1500ppm.
3. resin combination according to claim 1, which is characterized in that the reactive diluent is selected from by benzene second
Alkene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, benzyl methacrylate, chlorostyrene, smelly benzene second
Alkene, methoxy styrene, malic acid list benzyl ester, mono-benzyl fumarate, malic acid dibenzyl ester, dibenzyl fumarate, malic acid first
Benzyl ester, apple dimethyl phthalate, diethyl malate, dibutyl malate, dibutyl fumarate, butyl maleate, maleic acid
In the group that single pentyl ester, dipentyl maleate, fumarate monopentyl ester, diamyl fumarate and diethylene glycol diaryl carbonate form
One or more kinds of compounds.
4. resin combination according to claim 1, which is characterized in that the reactive diluent is selected from by benzene second
The chemical combination of one or more of alkene, divinylbenzene, α-methylstyrene, the group of α-methylstyrene dimer composition
Object.
5. resin combination according to claim 1, which is characterized in that also include internal release agent.
6. resin combination according to any one of claim 1 to 5, which is characterized in that the composition also includes
The heat stabilizer of 0.01~5 weight percent.
7. resin combination according to claim 6, which is characterized in that the heat stabilizer is selected from by triphenyl phosphorous
Acid esters, diphenyl decyl phosphite ester, phenyl didecyl phosphite, diphenyl dodecyl phosphite ester, diphenyl-isodecyl
Base phosphate, tritylphenyl phosphite ester, diphenyl iso-octyl phosphite ester, tributyl phosphite ester, tripropyl phosphorous
Acid esters, triethyl phosphorite, trimethyl phosphite, three (single decyl phosphite esters), three (single phenyl) phosphite esters composition
One or more of group compound.
8. refractive optical lenses in a kind of propylene oxide acids, solid phase refractive index is 1.53~1.58, which is characterized in that by
Polymerization is obtained for the resin combination of optical lens in mold, and the resin combination for optical lens includes to pass through
Make to be indicated by following chemical formula 1 and the bisphenol A diglycidyl ether of 100~1700ppm of chlorinity and acrylic acid are reacted
Come the bisphenol A epoxy acrylate of 50~70 weight percent obtained indicated by following chemical formula 2,21~45 weight percents
The reactive diluent of the methyl methacrylate of ratio, 1~17 weight percent:
Chemical formula 1:
In the chemical formula 1, n=0~15,
Chemical formula 2:
In the chemical formula 2, n=0~15.
9. refractive optical lenses in propylene oxide acids according to claim 8, which is characterized in that the reactivity dilution
Agent be selected from one of group being made of styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer or
Two or more compounds.
10. refractive optical lenses in propylene oxide acids according to claim 8 or claim 9, which is characterized in that the composition
It also include the heat stabilizer of 0.01~5 weight percent.
11. refractive optical lenses in propylene oxide acids according to claim 10, which is characterized in that the heat stabilizer
For selected from sub- by triphenyl phosphite, diphenyl decyl phosphite ester, phenyl didecyl phosphite, diphenyl dodecyl
Phosphate, diphenyl-isodecyl base phosphate, tritylphenyl phosphite ester, diphenyl iso-octyl phosphite ester, tributyl are sub-
Phosphate, tripropyl phosphite ester, triethyl phosphorite, trimethyl phosphite, three (single decyl phosphite esters), three (lists
Phenyl) phosphite ester composition one or more of group compound.
12. the preparation method of refractive optical lenses in a kind of acrylic compounds, which is characterized in that including by the resin of claim 1
The step of composition is added in mold and is polymerize.
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| KR1020170051781A KR101816722B1 (en) | 2017-04-21 | 2017-04-21 | A method of preparing epoxy acryl based optical material |
| KR10-2017-0051781 | 2017-04-21 | ||
| PCT/KR2018/003956 WO2018194298A2 (en) | 2017-04-21 | 2018-04-04 | Resin composition for epoxy acryl-based medium-refractive optical lens and preparation method therefor |
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| KR20180128296A (en) * | 2017-05-23 | 2018-12-03 | 주식회사 케이오씨솔루션 | A method of preparing epoxy acryl based optical material |
| CN112430435B (en) * | 2020-11-12 | 2022-05-24 | 江苏鹿山新材料有限公司 | Composite packaging adhesive film, preparation method thereof and photovoltaic module |
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| JPH07247331A (en) * | 1994-03-11 | 1995-09-26 | Nippon Kayaku Co Ltd | Resin composition, resin composition for optical resin material, and cured product thereof |
| CN104045808A (en) * | 2013-03-12 | 2014-09-17 | 陶氏环球技术有限公司 | Epoxy resin compositions, methods of making same, and articles thereof |
| KR101816722B1 (en) * | 2017-04-21 | 2018-01-11 | 주식회사 케이오씨솔루션 | A method of preparing epoxy acryl based optical material |
| CN108699222A (en) * | 2016-02-16 | 2018-10-23 | 欧司朗光电半导体有限公司 | Epoxy-resin systems, the application of epoxy-resin systems, opto-electronic device and the method for being used to prepare epoxy-resin systems |
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| JP2004333902A (en) * | 2003-05-08 | 2004-11-25 | Jsr Corp | Radiation-curing resin composition for optical member, and optical member |
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| JP5487976B2 (en) * | 2008-02-13 | 2014-05-14 | 三菱瓦斯化学株式会社 | Resin composition and optical lens containing the same |
| WO2013187539A1 (en) * | 2012-06-13 | 2013-12-19 | 주식회사 케이오씨솔루션 | 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 |
| KR102105717B1 (en) * | 2013-08-08 | 2020-04-28 | 주식회사 케이오씨솔루션 | Polymerizable composition for high refractive optical material and method of preparing the optical material |
| KR102117129B1 (en) * | 2013-12-18 | 2020-06-02 | 주식회사 케이오씨솔루션 | A method of preparing epoxy acryl based optical material |
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| US3758448A (en) * | 1971-10-05 | 1973-09-11 | Union Optics Corp | Copolymers and hydrogels of unsaturated esters |
| JPH07247331A (en) * | 1994-03-11 | 1995-09-26 | Nippon Kayaku Co Ltd | Resin composition, resin composition for optical resin material, and cured product thereof |
| CN104045808A (en) * | 2013-03-12 | 2014-09-17 | 陶氏环球技术有限公司 | Epoxy resin compositions, methods of making same, and articles thereof |
| CN108699222A (en) * | 2016-02-16 | 2018-10-23 | 欧司朗光电半导体有限公司 | Epoxy-resin systems, the application of epoxy-resin systems, opto-electronic device and the method for being used to prepare epoxy-resin systems |
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| CN113831441A (en) * | 2021-09-26 | 2021-12-24 | 湖北巴乐福化工科技有限公司 | Preparation method and reaction system of optical resin monomer |
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