JPH0465407A - Composition for plastic lenses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composition useful for manufacturing plastic lenses having excellent heat resistance, impact resistance, low water absorption, and moldability.

[Prior Art] Plastic lenses have come to be widely used in optical products due to their ease of molding and light weight. Among these, eyeglass lenses are desired to be lightweight, and in recent years, resins made of polydiethylene glycol bisallyl carbonate (CR-39) have become the mainstream for plastic eyeglass lenses.

However, in recent years, there has been a demand for higher refractive index and higher productivity for plastic lenses, and plastic lenses manufactured from various types of polymers and oligomers have been proposed in place of CR-39.

Important performance requirements for plastic lenses include heat resistance, impact resistance, low water absorption, surface precision of molded products,
It has stainability, etc. Conventionally, monomers and oligomers that impart structures rich in elasticity, such as ether bonds, urethane bonds, ester bonds, and carbonate bonds, have been used as components to improve impact resistance and dyeability. Among these, a low-viscosity di(meth)acrylate having an ether bond in its molecule and capable of improving casting workability has been proposed (Japanese Patent Application Laid-open No. 16813/1983).

Typical di(meth)acrylate monomers that provide this polyether structure include polyethylene glycol di(meth)acrylate, polybrobylene glycol di(
There are meta)acrylates. The impact resistance and dyeability of the lens improve in proportion to the increase in the number of repeating units of ethylene oxide or propylene oxide.

[Problem to be solved by the invention] However, this method, on the contrary,
Problems arose in terms of heat resistance, low water absorption, and maintaining surface precision. In order to improve heat resistance and low water absorption, the polymer should be made to have low water absorption. In order to improve the low water absorption of polymers, hydrocarbon chains, aromatic rings, halogen atoms, etc. have been introduced into the molecules (Japanese Patent Laid-Open No. 57-66401). However, although this method achieved heat resistance and low water absorption, impact resistance and dyeability decreased.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have discovered that polybutylene glycol dimethacrylate and impact-resistant polybutylene glycol dimethacrylate containing the same are used as monomers that provide a polymer having a well-balanced impact resistance and low water absorption. When a low water absorption composition was discovered and this composition was applied to plastic lenses, it was found that plastic lenses with excellent impact resistance, dyeability, good heat resistance, and low water absorption could be obtained. However, in this composition,
The surface precision (the curvature of the lens must be the same as the designed curvature), which is the performance required for lenses, was not perfect.

As a result of further investigation, we found that urethane poly(meth)acrylate is a component that imparts heat resistance, and polybutylene glycol di(meth)acrylate is a component that imparts impact resistance, low water absorption, and dyeability. , and a composition containing a mono(meth)acrylate of a monoalcohol having an aromatic hydrocarbon or a halogen-substituted aromatic hydrocarbon group as a component for improving surface precision has been found to provide an excellent cured lens product. , we have completed the present invention.

[Means for Solving the Problems] That is, the present invention provides: (A) an epoxy poly(meth)acrylate having two or more (meth)acryloyloxy groups in one molecule;
20-80 parts by weight (B) General formula (
I) 10 to 60 parts by weight of polybutylene glycol cyclo(meth)acrylate (C) General formula (n), (m ) or (rV) (wherein R2 is hydrogen or a methyl group, R3 is CH3 -CH2--Ct(zCH2-0-1-CH-CI(2
-0-1H -CHz-CH-CHz-0- or -CH2CH2C
H2CH, -0-1X is C1, Br or I, m is 0-
3, p is an integer of 0 to 5, q is an integer of 0 to 4, and r is an integer of 0 to 3) 5 to 60 parts by weight of a mono(meth)acrylate compound and (D) in the molecule 0 to 60 parts by weight of a compound having at least one polymerizable double bond (however,
This is a composition for a plastic lens containing as a main component (the total of components (A) to (D) is 100 parts by weight).

[Function] The epoxy poly(meth)acrylate (A) having two or more (meth)acryloyloxy groups in one molecule, which is the first component of the present invention, is an epoxy poly(meth)acrylate (A) having two or more glycidyl groups in the molecule. Examples include glycidyl group ring-opening reaction products between a compound and (meth)acrylic acid or a compound having a (meth)acryloyloxy group and a carboxyl group in the molecule.

This first component (A) is a component that imparts heat resistance that is insufficient only with the second component, polybutylene glycol di(meth)acrylate.

The epoxy compounds (epoxy compounds having at least two glycidyl groups in the molecule) used in the above-mentioned ring-opening reaction to obtain the first component (A) include 1,6-hexanesiol diglycidyl ether, ethylene Glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxypivalic acid ester, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether Glycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, sorbitol tetraglycidyl ether, Tris(2- Aliphatic epoxy compounds such as the diglycidyl ether of hydroxyethyl)in cyanurate, the triglycidyl ether of tris(2-hydroxyethyl)isocyanurate, the diglycidyl ether of isophorone diol, and the diglycidyl ether of 1,4-bis(hydroxymethyl)cyclohexane. glycidyl ether, bis-2
, alicyclic epoxy compounds such as diglycidyl ether of 2-hydroxycyclohexylpropane, resorcin diglycidyl ether, bisphenol A, bisphenol F, bisphenol A diglycidyl ether obtained by condensation of bisphenol S and epichlorohydrin, bisphenol F diglycidyl ether. , bisphenol S
diglycidyl ether, tetrabromobisphenol A
Zig IJ cidyl ether, bis(3,5-dimethyl-4
-Hydroxyphenyl)sulfone, bis(3-methyl-
4-hydroxyphenyl) sulfone, condensate of bis(3-phenyl-4-hydroxyphenyl) sulfone and epichlorohydrin, condensate of 2,6-xylenol dimer and engineered dichlorohydrin, orthophthalic acid diglycidyl ester, phenol novolak polyglycidyl Examples include aromatic epoxy compounds such as ether and cresol novolak polyglycidyl ether.

Compounds to be reacted with these epoxy compounds include acrylic acid, methacrylic acid, carboxyl group-containing (meth)acrylate obtained by reacting hydroxyethyl (meth)acrylate with an acid anhydride such as 〇-phthalic anhydride, Examples include carboxyl group-containing (meth)acrylates obtained by reacting glycidyl (meth)acrylate with a compound having two or more carboxyl groups in the molecule, such as adipic acid.

The reaction between an epoxy compound and a carboxyl group-containing (meth)acrylate can be carried out, for example, by mixing the two, adding a tertiary amine compound such as dimethylaminonithyl methacrylate or a quaternary amine salt such as benzyltrimethylammonium chloride as a catalyst, and It is carried out by heating to 110°C.

In the present invention, epoxy poly(meth)acrylate (A) can be used alone or in combination of two or more, but the colorless transparency and heat resistance of the plastic lens obtained by curing are From, 1,6-hexanesiol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl of tris(2-hydroxyethyl)isocyanurate Epoxy poly( Particular preference is given to using meth)acrylates.

Polybutylene glycol di(meth)acrylate, which is the second component of the composition of the present invention, is obtained by sealing both ends of polybutylene glycol having a degree of polymerization of 5 to 16 with two acrylic acids or methacrylic acids. Here, the degree of polymerization is the number n of repeating units represented by the formula: (CH2CHzCHzCH20h), and is from 5 to 16. As the water absorption increases, the crosslinking density decreases, the polymer hardness decreases, and the heat resistance also decreases.Moreover, the viscosity of the monomer also increases, resulting in a decrease in casting workability.The preferred degree of polymerization is 7 to 12. However, since polybutylene glycol dimethacrylate is a mixture of polymers having different degrees of polymerization in a normal distribution, the degree of polymerization n here means the median value.

The polybutylene glycol di(meth)acrylate used in the present invention can be produced by, for example, a condensation reaction between polybutylene glycol obtained by ring-opening polymerization of tetrahydrofuran and acrylic acid or methacrylic acid, or polybutylene glycol and methyl acrylate or methyl methacrylate. Although it can be easily produced by a transesterification reaction, a method using a transesterification reaction is preferable because it yields a colorless and transparent crystal.

The third component of the composition of the present invention is general formula (II), (I
II) or (rV) (wherein R2 is hydrogen or a methyl group, R3 is CH3-Ct(2--CI(2CH2-0-1-CH-C)1
2-0-1 leaf CH2-CH-C11, -0- or -C112C1 (
2C) 12C) 12-0-1X is C1, Br or I,
m is an integer of 0 to 3, p is an integer of 0 to 5, q is an integer of O to 4, and r is an integer of D to 3).
This component exhibits the effect of improving surface accuracy during lens molding, which cannot be obtained by using only the first and second components.

These mono(meth)acrylate compounds (meth)acrylate compounds (C) of monoalcohols having an aromatic hydrocarbon group or a halogen-substituted aromatic hydrocarbon group are ring-opening additions of ethylene oxide, propylene oxide, or tetrahydrofuran to the above-mentioned monoalcohol or to the same monoalcohol. It can be prepared by reacting a monoalcohol with (meth)acrylic acid.

Specific examples of the mono(meth)acrylate compound (C) include phenyl(meth)acrylate, benzyl(meth)acrylate,
Acrylate, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, phenyludi(oxyethyl)-(meth)
Acrylate, Phenyl-tri(oxyethyl)-(meth)acrylate, Phenyludi(2-methyloxyethyl)-(meth)acrylate, Phenyl-tri(2-
Methyloxyethyl)-(meth)acrylate, phenoxybutyl(meth)acrylate, phenyludi(oxybutyl)-(meth)acrylate, phenyl-tri(
(oxybutyl)-(meth)acrylate, 2-phenylphenyl (meth)acrylate, 4-phenylphenyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 2-phenylphenyl -2-Methyloxyethyl (meth)acrylate, 4-phenylphenyl-2-methyloxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, 3-(4-phenyl) phenyl)-2-hydroxypropyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (
meth)acrylate, 1-naphthyloxyethyl(meth)acrylate, 2-naphthyloxyethyl(meth)acrylate, l-naphthyludi(oxyethyl)-(meth)acrylate, 2-naphthyloxyethyl(oxyethyl)
-(meth)acrylate, 1-naphthyl-2-methyloxyethyl-(meth)acrylate, 2-naphthyl-2
-Methyloxyethyl-(methacrylate), 3-(
1-Naphthyl)-2-hydroxypropyl (meth)acrylate, 3-(2-naphthyl)-2-hydroxypropyl (meth)acrylate, 2-bromophenyl (meth)acrylate, 4-bromophenyl (meth)acrylate, 2 .4-dibromophenyl (meth)acrylate, 2,4.6-4ribromophenyl (meth)acrylate, 2,3.4,5.6-pentabromophenyl (meth)acrylate, 2,4-dibromophenoxyethyl (
meth)acrylate, 2,4.6-dribromophenyludi(oxyethyl)-(meth)acrylate, 2,4
．． 6-dribromophenyl-2-methyloxyethyl (
meth)acrylate, 2-bromobenzyl(meth)acrylate, 4-bromobenzyl(meth)acrylate,
2.4-dibromobenzyl (meth)acrylate, 2,
4.6-Tribromobenzyl (meth)acrylate, 2
, 3,4.5,6-pentabromobenzyl (meth)acrylate, 2-chlorophenyl (meth)acrylate,
4-chlorophenyl (meth)acrylate, 2゜4-dichlorophenyl (meth)acrylate, 2゜4.6-trichlorophenyl (meth)acrylate, 2,3,4,
5.6-pentachlorophenyl (meth)acrylate,
2.4-dichlorophenyloxyethyl (meth)acrylate, 2,4゜6-trichlorophenyloxyethyl (meth)acrylate, 2,4.6-dichlorophenyl-di(oxyethyl)-(meth)acrylate, 2.
4.6-Trichlorophenoxy-2methyloxyethyl (meth)acrylate, 3- (2゜4.6-tribromophenyl)-2-hydroxypropyl (meth)acrylate, 3- (2,3゜4.5. 6-pentabromophenyl)-2-hydroxypropyl (meth)acrylate, 2-phenyl-4-bromophenyl °C meth)acrylate, 2-(4-bromophenyl)-4,6-dibromophenyl (meth)acrylate, 2 - (4-chlorophenyl)-4,6-dichlorophenyl (meth)acrylate, 2-phenyl-4-promophenyolxyethyl (meth)acrylate, 2-(4-bromophenyl)
-4,6-dibromophenyloxyethyl (meth)acrylate, 2-(2,4,6-tribromophenyl)
-4,6-dibromophenyl (meth)acrylate, 2
-(2,4-dibromophenyl)-4,6-dibromophenyloxyethyl (meth)acrylate, 1-(4-
Chloronaphthyl)-oxyethyl (meth)acrylate, 2-(4-chloronaphthyl)-oxyethyl-(meth)acrylate, 1-(4-bromonaphthyl)-oxydiethyl (meth)acrylate, 2-(4-bromonaphthyl) -oxyethyl-(meth)acrylate, 3-[
Examples include 1-(2-bromonaphthyl)-2-hydroxypropyl (meth)acrylate, 3-[2-(2-bromonaphthyl)]-]2-hydroxypropyl meth)acrylate, and the like.

In the present invention, the mono(meth)acrylate compound as the third component can be used alone or in combination of two or more, but from the viewpoint of surface precision and colorless transparency of the molded lens, phenyl ( meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)
Acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenyl (meth)acrylate, 4-phenylphenyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate , 1-(4-phenylphenyl)-2-hydroxypropyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate, 2
．． 4.6-to1nobromophenyl (meth)acrylate, 2,4.6-tribromophenoxyethyl (meth)acrylate, 2,4.6-tribromophenyl di(oxyethyl)-(meth)acrylate and 2 ,4.6
-4 ribromobenzyl (meth)acrylate is preferred.

The fourth component of the composition of the present invention (FD), a compound having at least one polymerizable double bond in the molecule, has heat resistance,
A component that provides surface hardness and low viscosity. In particular, since a highly viscous epoxy poly(meth)acrylate is used in the present invention, it is preferable that the viscosity of the resin composition be as low as possible in order to improve casting workability. Therefore, as component (D), a low-viscosity ester monomer is particularly preferred.

Specific examples of component (D) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, 1-butyl (meth)acrylate, t-Butyl (meth)acrylate, Pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate, Lauryl (meth)acrylate, Stearyl (meth)acrylate, (Meth) ) butoxyethyl acrylate, allyl (meth)acrylate, methallyl (meth)acrylate, (
Glycidyl meth)acrylate, (meth)acrylic acid N,
N-dimethylamine ethyl, (meth)acrylic acid N, N
-diethylaminoethyl, 2-cyanethyl (meth)acrylate, dibromopropyl (meth)acrylate, N-vinyl-2-pyrrolidone (meth)acnolate, (meth)
Acrylic acid polyethylene glycol monoalkyl ether, (meth)acrylic acid polypropylene glycol monoalkyl ether, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl,
Mono (meth)acrylate compounds such as 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and phosphonityl (meth)acrylate: Ethylene glycol di(meth) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bentaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, etc. Methacrylate: Brobylene glycol di(meth)acrylate, dibrobylene glycol di(meth)acrylate, tribrobylene glycol di(meth)acrylate, tetrabrobylene glycol di(meth)acrylate, nonabrobylene glycol di(meth)acrylate Di(meth)acrylate of polypropylene glycol such as acrylate; 1.3-butylene glycol di(meth)acrylate, 1.4-butylene glycol di(meth)acrylate, 1,6-hexamethylene glycol di(meth)acrylate, 1.14-Tetrade-force methylene glycol di(meth)acrylate, neobentyl glycol di(meth)acrylate, neobentyl hydroxypivalate di(meth)acrylate, di(meth)acrylate of caprolactone adduct of neopentyl glycol hydroxypivalate meth)acrylate, neopentyl glycol adivate di(meth)acrylate, dicyclopentenyl di(meth)acrylate, dicyclopentanyl di(meth)
Acrylate, 2-(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-5-ethyl-1,
3-Dioxane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, di(meth)acryloyloxyethyl isocyanurate, tris(meth)acryloyloxyethyl isocyanurate, 2,2-bis(4-(meth)acryloyloxyphenyl)-propane, 2 , 2-bis(4-(meth)acryloyloxyethoxyphenyl)-propane, 2.2-bis(4-(
meth)acryloyloxyjetoxyphenyl)-propane, 2゜2-bis(4-(meth)acryloyloxypentaethoxyphenyl)-propane, 2.2-bis(
4-(meth)acryloyloxyethoxy-3,5-dibromophenyl)-propane, 2,2-bis(4-(meth)acryloyloxyethoxy-3,5-dibromophenyl)-propane, 2.2-bis (4-(meth)acryloyloxypentaethoxy-3,5-dibromophenyl)-propane, 2,2-bis(4-(meth)acryloyloxyethoxy-3,5-dimethylphenyl)
-propane, 2,2-bis(4-(meth)acryloyloxyethoxy-3-phenylphenyl)-propane,
Bis(4-(meth)acryloyloxyphenyl)-sulfone, bis(4-(meth)acryloyloxyethoxyphenyl)-sulfone, bis(4-(meth)acryloyloxyjetoxyphenyl)-sulfone, bis(4-( meth)acryloyloxypentaethoxyphenyl)-sulfone, bis(4-(meth)acryloyloxyethoxy-3-phenylphenyl)-sulfone, bis(4-(meth)acryloyloxyethoxy-
3,5-dimethylphenyl-sulfone, bis(4-
(meth)acryloyloxyphenyl)-sulfide,
Bis(4-(meth)acryloyloxyethoxyphenyl)-sulfide, bis(4-(meth)acryloyloxypentaethoxyphenyl)-sulfide, bis(4
-(meth)acryloyloxyethoxy-3-phenylphenyl)-sulfide, bis(4-(meth)acryloyloxyethoxy-3,5-dimethylphenyl)-sulfide, di((meth)acryloyloxyethoxy)
Polyfunctional (meth)acrylic compounds such as phosphate and tri((meth)acryloyloxyethoxy)phosphate: styrene, vinyltoluene, chlorostyrene, bromostyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, N- Vinyl compounds such as vinylpyrrolidone; allyl compounds such as diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, diallyl phthalate, dimethallyl phthalate =
Examples include (meth)acrylic acid and metal salts of barium, lead, antimony, titanium, tin, zinc, and the like. These may be used alone or in a mixed system of two or more.

(A) in the composition for plastic lenses of the present invention
(When the total amount of components (A) to ([1)] is 100 parts by weight, the mixing ratio of the DJ acid component is (A) 20 to 80 parts by weight, (B) 10 to 60 parts by weight, (C) 5 parts by weight. ~60 parts by weight, (C) 0 to 60 parts by weight.If component (A) is less than 20 parts by weight, sufficient heat resistance cannot be imparted to the lens, and if it exceeds 80 parts by weight, the viscosity of the composition will decrease. becomes high, and the workability of cast polymerization decreases.The preferred blending amount is 30 to 6
It is 0 parts by weight. Furthermore, if the amount of component (B) is less than 10 parts by weight, sufficient impact resistance cannot be imparted to the lens, and the amount of water absorption cannot be suppressed.

On the other hand, if it exceeds 60 parts by weight, the heat resistance and surface hardness of the lens will deteriorate, which is not desirable. The preferred amount is 20~
It is 50 parts by weight. Furthermore, if component (C) is less than 5 parts by weight, the surface precision of the molded lens will deteriorate, and if it exceeds 60 parts by weight, the heat resistance and toughness of the lens will deteriorate, which is not desirable.

The preferred amount is 10 to 40 parts by weight. Component (D) is not an essential component, but is a component used to further improve the heat resistance and surface hardness of the lens, and to lower the viscosity of the composition and improve casting workability. The preferred amount is 5 to 30 parts by weight.

The composition for plastic lenses of the present invention may contain various additives such as antioxidants, anti-yellowing agents, ultraviolet absorbers, bluing agents, pigments, etc., as necessary, to the extent that they do not impair the effects of the present invention. may be done.

The composition for plastic lenses of the present invention includes (A) to (D
) The components can be mixed and stirred in a conventional manner, and further various additives may be added as necessary.

Examples of the polymerization initiator used in curing the composition for plastic lenses of the present invention include organic compounds such as benzoyl peroxide, t-butylperoxyisobutyrate, and t-butylperoxy-2-ethylhexanoate. Peroxide: 2,2'-azobisisobutyronitrile, 2,2'
-Azo compounds such as azobis(2,4-dimethylvaleronitrile): 2-hydroxy-2-methyl-1-phenylpropan-1-one, methylphenylglyoxylate, 2,4.6-trimethylbenzoyldiphenylphosph Examples include photopolymerization initiators such as inoxide. These may be used alone or in a mixed system of two or more. The blending ratio of this polymerization initiator is a total of 100% of components (A) to (D).
It is usually 0.005 to 5 parts by weight.

In the polymerization curing method, for example, the composition of the present invention containing a polymerization initiator is injected into a mold made of two mirror-polished glass plates through a gasket made of ethylene-vinyl acetate copolymer, and one side of the mold is injected into the mold. Alternatively, it is carried out by irradiating active energy rays from both sides or by heat treatment. Alternatively, a combination of irradiation and heating may be used. Here, the molds include glass and glass, glass and plastic plates,
There are molds made of glass, metal plates, or a combination of these. Further, as the gasket, in addition to the above-mentioned thermoplastic resin, an adhesive tape made of polyester may be used.

[Example J] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, the abbreviations of monomers are as follows.

EDMI: Epoxy dimethacrylate made by reacting bisphenol A diglycidyl ether with methacrylic acid EDA2: Epoxy diacrylate made by reacting tetrabromobisphenol A diglycidyl ether with acrylic acid EDM3: Made by reacting bisphenol S diglycidyl ether with methacrylic acid Reacted epoxy dimethacrylate 1.9BGDM Nonabutylene glycol dimethacrylate 12BGDM: Dodecabutylene glycol dimethacrylate 9EGDM: Nonaethylene glycol dimethacrylate PhM: Phenyl methacrylate BPhM: 2-phenyl phenyl methacrylate 3Br
PM: 2,4.6-tribromophenoxyethyl acrylate HPM: 3-phenoxy-2-hydroxypropyl methacrylate BzM: Benzyl methacrylate POM + phenoxyethyl methacrylate HDDM:
1,6-hexamethylene glycol dimethacrylate HDDA: 1 6-hexamethylene glycol diacrylate DGBC diethylene glycol bisallyl carbonate Synthesis Example 1 (Synthesis of 9BGDM by transesterification method) Nonabutyl glycol (
Average molecular weight: 680, manufactured by Osugaya Chemical, product name: P
TG-650SN) 2.0 kg, MMA2, 0k
g and 0.5 g of hydroquinone monomethyl ether, and titanium tetra-n-butoxide 5 g was added as a catalyst.
While stirring at 100 to 120° C., generated methanol was azeotropically removed with MMA, and the mixture was reacted for 3 hours. After the reaction, excess MMA was distilled off under reduced pressure, 1 kg of toluene was added to the residue, and after washing with alkaline water, toluene was distilled off under reduced pressure to obtain 9BGDM.

The obtained 9BGDM was colorless and transparent, and purity analysis by bromine addition showed it to be 100%.

Synthesis Example 2 (Synthesis of epoxy dimethacrylate) In a three-necked flask at 5°C, 3 bisphenol A diglycidyl ether (manufactured by Tobu Kasei Co., Ltd., trade name "YD-8125J") was added.
．． 015g, methacrylic acid (provided by Mitsubishi Rayon) 14
85 g of benzyltrimethylammonium chloride as a catalyst and 1 g of hydroquinone monomethyl ether as an inhibitor were added and reacted at 70°C for 3 hours, at 80°C for 3 hours, and at 110°C for 8 hours, and the acid value of the reaction mixture was 0. 15, the reaction was terminated and epoxy dimethacrylate (EDMl) was obtained.

Example I EDMI 40 g, 9BGDM35g, TCDM2
0g, HDDM 5g, 2,4.6-1-limethylbenzoyldiphenylphosphine oxide, 0,. 03
g, t-butyl peroxyisobutyrate 0.1 g, 2
-Hydroxy-4-methoxybenzophenone 0.05g
, tridodecyl phosphate (0.2 g) were mixed, and after stirring well at room temperature, the pressure was reduced to 50 mmftg and degassed for 10 minutes.

This composition was polished to a mirror finish with an outer diameter of 80 mm and a curvature of 38 mm.
A 6 mm glass and a glass having an outer diameter of 80 mm and a curvature of 65 mm were combined to form a concave lens with a center thickness of 1.5 mm, and the lens was poured into a mold surrounded by a polyvinyl chloride gasket.

Next, a 2KW high-pressure mercury lamp was used to heat the mold from both sides.
After irradiating with ultraviolet rays of 000mJ/cm2, 130
Heated at ℃ for 2 hours. After that, remove the lens from the mold,
Annealing treatment was performed by heating at 120° C. for 1 hour.

The lenses manufactured in this way were evaluated using the following evaluation method,
The results are shown in Table 1. In addition, evaluation items other than surface area and falling ball test were: thickness 2mm or 5mm, outer diameter 75m
Measurements were made using a disc-shaped flat plate of rn.

Visible light transmittance (%): ASTM 01003-
61.

Refractive index: Measured at 589.3 nm D line using an Atsube refractometer.

Saturated water absorption rate (weight %): Using a disk-shaped flat plate with a thickness of 5 mm, it was left in a 100% saturated steam bath at 70° C. for 3 days, and the increase in weight was measured.

Falling Ball Test Lenses with a thickness of 1.5 mm were tested according to FDA standards. However, the maximum weight of a steel ball when dropped from a height of 127 mm is shown.

Rockwell hardness: Measured according to JIS K7202.

Heat resistance: Tg was measured at a load of 10 g using a TMA measuring machine.

Surface accuracy: Observe the curved state of the center of the lens with the naked eye,
Classified into the following ranks.

A: There is no curvature at all. (The difference between the curvature at the time of design and the curvature of the molded lens is 0 to 1%) B: Slightly curved. (Difference is 1 to 3%) C: Slightly curved. (Difference is 3-5%) D: Curved. (Difference is 5-10%) E: Significantly curved. (Difference is 10-20%) F: Unusable, (
Difference of 20% or more) Casting workability: The difficulty level of pouring the monomer mixture into the mold was determined.

○: Easy to inject oil. X: Difficult to inject.

Dyeing property Koseiko Blacks Diamond Coat dyeing agent Amber D (trade name, manufactured by Seiko Seiko) 2g was dispersed in 1j2 water and dyed at 90℃ for 3 minutes, and the visible light transmittance value was determined. It was measured.

Examples 2 to 8 Lenses were manufactured and evaluated in the same manner as in Example 1, except that monomers were used in the proportions shown in Table 1. Results first
It is also shown in the table.

Comparative Example I 100 g of CR-39 (diethylene glycol bisallyl carbonate) and 3 g of diisopropyl peroxy percarbonate were mixed and stirred well, and then Example 1
Pour into the same mold used in , and heat at 45°C for 10 hours.
Molding was carried out by holding at 60°C for 3 hours, at 80°C for 3 hours, and at 95°C for 6 hours. The lens was removed from the mold and annealed by heating at 120°C for 1 hour. The lenses and flat plates thus manufactured were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Examples 2 to 8 Lenses were manufactured and evaluated in the same manner as in Example 1, except that 1,000 yen was used in the proportions shown in Table 1. Results first
They are also shown in the table.

〔Effect of the invention〕

The plastic lens composition of the present invention can be polymerized in a short period of time using active energy rays. Furthermore, it is possible to produce a cured plastic lens that has excellent heat resistance, impact resistance, dyeability, and low water absorption. Furthermore, the surface precision when molding a concave lens is particularly excellent.

Patent applicant: Mitsubishi Rayon Co., Ltd. Seiko Epson Corporation

Claims (1)

[Claims] 1) (A) Epoxy poly(meth)acrylate 20 having two or more (meth)acryloyloxy groups in one molecule
~80 parts by weight (B) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R^1 represents hydrogen or a methyl group, and n represents an integer from 5 to 16) 10 to 60 parts by weight of polybutylene glycol di(meth)acrylate (C) General formula (II), (III) or (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲Mathematical formulas, chemical formulas, tables, etc. ▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R^2 is hydrogen or a methyl group, R^3 is -CH
_2-, -CH_2CH_2-O-, ▲numerical formula, chemical formula,
There are tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or -CH_2CH_2CH_2CH_2-O-, X is Cl, Br or I, m is an integer from 0 to 3, p is an integer from 0 to 5, q is from 0 to 4 and r represents an integer of 0 to 3) 5 to 60 parts by weight of a mono(meth)acrylate compound represented by (D) 0 to 60 parts by weight of a compound having at least one polymerizable double bond in the molecule (provided that the total of components (A) to (D) is 100 parts by weight) as a main component.