JPH03255118A - Composition for plastic lens - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a plastic lens excellent not only in heat resistance, impact resistance and low hygroscopicity but also in surface precision by mixing urethane poly(meth)acrylate with a di(meth) acrylate compound, a mono(meth)acrylate compound and a copolymerizable double bond-containing compound as the principal components. CONSTITUTION:The title composition mainly consists of 20-80 pts.wt. urethane poly(meth)acrylate having at least two (meth)acryloyloxy groups in the molecule, 10-60 pts.wt. di(meth)acrylate compound of formula I (wherein R<1> is hydrogen or methyl; and (m) and (n) are each an integer of 1-4), 5-60 pts.wt. mono(meth) acrylate compound of formula II, III or IV (wherein R<2> is hydrogen or methyl; R<3> is CH2, CH2CH2-O, CH2CH2CH2CH2-O or the like; X is Cl, Br or I; (m) is an integer of 0-3; (p) is an integer of 0-5; (q) is an integer of 0-4; and (r) is an integer of 0-3) and 0-60 pts.wt. compound having at least one polymerizable double bond in the molecule (the total of these components being 100 pts.wt.).

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.

[Conventional technology]

Plastic lenses have become 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 (: Various monomers to replace R-39,
Plastic lenses made from oligomers have been proposed.

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 provide highly elastic structures 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 which has an ether bond in its molecule and can improve casting workability has been proposed (Japanese Patent Application Laid-Open No. 168-1989, No. 3).

Typical di(meth)acrylate monomers providing this polyether structure include polyethylene glycol di(meth)acrylate and polybrobylene glycol di(meth)acrylate. 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 in the monomer.

[Problem to be solved by the invention]

However, this method, on the contrary, requires the lens to
Problems arose in terms of heat resistance, low water absorption, and maintaining surface precision. In order to improve heat resistance and low water absorption, it is sufficient to make the polymer numerically low in 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 heat resistance and low water absorption were achieved with this method, aIH resistance and dyeability were reduced.

As a result of intensive studies to solve the above problems, the present inventors found that a di(meth)acrylate compound with a specific structure is used as a monomer to provide a polymer having a well-balanced impact resistance and low water absorption. find the composition,
When this composition was applied to plastic lenses, it was found that plastic lenses with excellent impact resistance and 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 the lens, was not perfect.

As a result of further investigation, we found urethane poly(meth)acrylate as a component to impart heat resistance, and di(meth)acrylate with a specific structure as a component to impart impact resistance, low water absorption, and dyeability. A composition containing a compound and a mono(meth)acrylate compound of a monoalcohol having an aromatic hydrocarbon or a halogen-substituted aromatic hydrocarbon group as a component for improving surface precision provides an excellent cured lens product. They discovered this and completed the present invention.

[Means to solve the problem]

That is, the present invention provides (A) a urethane poly(meth)acrylate in which two (meth)acryloyloxy groups are arranged upwind in one molecule;
20 to 80 parts by weight (B) - Formula (I) (I) (wherein, R1 is hydrogen or a methyl group, m and n are 1 to
(representing an integer of 4) 10 to 60 parts by weight of a di(meth)acrylate compound (C) - formula (II), (m) or (IV) (in the formula,
R2 is hydrogen or a methyl group, R3 is CH3 -CH2-, -CHzCH2-0-1-co-ct+2
-o--Ctb-CH-CL-0- or -C1hCH
2CH2CH2-0-5X is CI, Br or 1%+n
is an integer of 0 to 3, p is an integer of 0 to 5, q is an integer of 0 to 4, and 5 to 60 parts by weight of a mono(meth)acrylate compound represented by ) 0 to 60 parts by weight of a compound having at least one polymerizable double bond in the molecule (however, (A
) to (D) (the total of components is ioo parts by weight)) is a composition for a plastic lens, the main component of which is:

[Function] As the urethane poly(meth)acrylate (A) having two or more (meth)acryloyloxy groups in one molecule, which is the first component of the present invention, the urethane poly(meth)acrylate (A) containing a hydroxyl group (
Examples include urethane reaction products of meth)acrylate and isocyanate compounds having two or more isocyanate groups in the molecule. This first component (A) is a component that imparts heat resistance that is insufficient only with the second component, the di(meth)acrylate compound (B).

Specific examples of polyisocyanate compounds having at least two isocyanate groups in the molecule include aliphatic, aromatic or alicyclic incyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl xamethylene diisocyanate, dimer acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, ], 3-bis(α,α-dimethylisocyanate methyl)benzene, diphenylmethane diisocyanate, m
-phenylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, biphenyl diisocyanate, and the like. A compound having at least two isocyanate groups in the molecule obtained by the reaction of these incyanates with a compound having at least two active hydrogen atoms such as an amino group, a hydroxyl group, a carboxyl group, or water, or three of the above diisocyanate compounds. mer to pentamer can also be used.

Hydroxyl group-containing (
As the meth)acrylate, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Hydroxyl group-containing (meth)acrylates such as acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc. Addition reaction products of monoepoxy compounds and (meth)acrylic acid; mono(meth)acrylic acid esters such as polyethylene glycol and polypropylene glycol;
Examples include mono(meth)acrylic acid ester of polycaprolactone diol (n=1 to 5).

The addition reaction between a polyisocyanate and a hydroxyl group-containing (meth)acrylate can be carried out using a known method, for example, a reaction between a hydroxyl group-containing (meth)acrylate and a catalyst such as di-n-butyltin laurate in the presence of an isocyanate compound. It can be produced by reacting the mixture dropwise under conditions of 50 to 90°C.

In the present invention, urethane poly(meth)acrylates can be used alone or in a mixture of two or more, but from the viewpoint of colorless transparency and heat resistance of the plastic lens obtained by curing, isophorone diisocyanate is used. , 2,2.4-trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, 1,3-bis(α,α-dimethylisocyanatomethyl)benzene, tolylene diisocyanate or naphthalene diisocyanate, and 2
It is particularly preferred to use urethane poly(meth)acrylate which is an adduct with -hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

The second component of the composition of the present invention has the general formula (1) (1) (wherein R' is hydrogen or a methyl group, m and n are 1 to
The di(meth)acrylate compound (B) represented by (representing an integer of 4) is a di(meth)acrylate of a caprolactone adduct of hydroxypivalic acid neopentyl glycol ester. In this di(meth)acrylate compound (B), 1 to 4 moles (i.e., 2 to 8 moles in total) of caprolactone are ring-opened to each of the hydroxyl groups at both ends of the esterified product of hydroxypivalic acid and neopentyl glycol. It can be easily produced by synthesizing an added diol and performing a condensation reaction between this diol and acrylic acid or methacrylic acid, or a transesterification reaction between this diol and methyl acrylate or methyl methacrylate. The method for producing the di(meth)acrylate compound (B) may be arbitrarily selected depending on the intended use of the lens, but a transesterification method is preferred since it yields a colorless and transparent monomer.

Note that when di(meth)acrylate of neopentyl glycol hydroxypivalate to which caprolactone is not added is used as component (B), it is possible to achieve low water absorption of the lens, but the invention is not effective in terms of impact resistance. It is not possible to obtain excellent results as in .

The amount of caprolactone added, that is, m and n in general formula (I) are each within the range of 1 to 4. The total amount (m+n) of addition may be any of 2 to 8, but from the viewpoint of balance between low water absorption, impact resistance, and heat resistance,
m+n=2-5 is preferable, and m+n=2-4 is more preferable. When the total amount of m and n exceeds 8, heat resistance is poor. However, the above-mentioned addition of caprolactone is a mixture of substances with different addition amounts according to a normal distribution, so
n and m here mean the median value.

The third component of the composition of the present invention is general formula (II), (I
II) or (IV) (wherein R2 is hydrogen or a methyl group, R3 is (:l+3 (:R2-, -(1:R2CH2-0-1-11;H-
fa2-0-5H CH2-C1(-(:R2-0- or -CHzCH2
CH2CH2-0-1x is C1, Br or I, m is 0
The mono(meth)acrylate compound (C) is represented by:
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 (C) of monoalcohols having an aromatic hydrocarbon or 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, Fesoroutri(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, 2-phenylphenyl-2-hydroxypropyl (
meth)acrylate 4-phenylphenyl-2-hydroxyoxypropyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl ( meta) acrylate,
1-naphthyl di(oxyethyl)-(meth)acrylate, 2-naphthyl di(oxyethyl)-(meth)acrylate, 1-naphthyl-2-methyloxyethyl=
(meth)acrylate, 2-naphthyl-2-methyloxyethyl-(methacrylate), 1-naphthyl-2-
Hydroxyoxypropyl (meth)acrylate, 2-
Naphthyl-2=hydroxyoxypropyl (meth)acrylate, 2-bromophenyl (meth)acrylate 4
-bromophenyl (meth)acrylate, 2゜4-dibromophenyl (meth)acrylate 2.4.6-tribromophenyl (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)4 acrylate, 2,4.6-tribromobenzyl (meth)acrylate, 2,3,4, 5.6-
Pentabromohenzyl (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-dichlorophenyl Oxyethyl (meth)acryle-h, 2.4.6-
Trichlorophenyloxyethyl (meth)acrylate, 2,4.6-drichlorophenyl-di(oxyethyl)-(meth)acrylate, 2゜4.6-trichlorophenoxy-2methyloxyethyl (meth)acrylate, 2,4 .6-dribromophenyl-2-hydroxyoxypropyl (meth)acrylate, 2.3,4,5.
6-bentapromophenyl-2-hydroxyoxypropyl (meth)acrylate, 2-phenyl-4-bromophenyl (meth)acrylate 2-(4-bromophenyl)-4,6-dibromophenyl (meth)acrylenide, 2- (4-chlorophenyl)-4,6-cyclophenyl (meth)acrylate 2-phenyl-4-bromopheniolkoxyethyl (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)-oxyethyl (meth)acrylate, 2
-(4-bromonaphthyl>-oxyethyl-(meth)acrylate 1- [3-(2-bromonaphthyl)]-]
2-Hydroxyoxypropyl meth)acrylate, 2
- [3-(2-bromonaphthyl)]-2 part 2 part droxyoxypropyl) acrylate.

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, phenoxy(meth)acrylate, 3-phenoxy-2-hydroxypropyl(meth)acrylate, 2-phenylphenyl(meth)acrylate, 4-phenylphenyl(meth)acrylate, 2-phenyl Phenyl-2- and 10xoxypropyl (meth)acrylate, 4-phenylphenyl-2-
Hydroxyoxyprobyl (meth)acrylate, 1-
Naphthyloxyethyl (meth)acrylate, 2-naphthyloxyethyl (meth)acrylate 2,4.6-
Tribromophenyl (meth)acrylate, 2.4゜6
-tribromophenoxyethyl (meth)acrylate and 2,4.6-tribromobenzyl (meth)acrylate are preferred.

The compound (D) having at least one polymerizable double bond in the molecule, which is the fourth component of the composition of the present invention, supplements the heat resistance and surface hardness, and also reduces the viscosity of the composition. It is also the ingredient that makes it possible. In particular, since a highly viscous urethane poly(meth)acrylate is used in the present invention, the lower the viscosity of the resin composition, the better 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, <meth>butyl 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)acrynoate,
(meth)glycidyl acrylate, (meth)acrylic acid N
, N-dimethylaminoethyl, (meth)acrylic acid N,
N-diethylaminoethyl, 2-cyanoethyl (meth)acrylate, dibromopropyl (meth)acrylate, (
N-vinyl-2-pyrrolidone meth)acrylate, polyethylene glycol monoalkyl ether (meth)acrylate, polypropylene glycol monoalkyl ether (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate - Mono(meth)acrylate compounds such as hydroxypropyl, 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 Dimethacrylate of polyethylene glycol such as: Brobylene glycol di(meth)
1 .3-Butylene glycol di(meth)acrylate 1.4-butylene glycol di(meth)acrylate, 1,6-hexamethylene di(meth)acrylate, 1.14-tetradecamethylene di(meth)acrylate, neobentyl Glycol di(meth)acrylate,
Neobentyl glycol hydroxypivalate di(meth)acrylate, neobentyl glycol hydroxypivalate di(meth)acrylate with caprolactone adduct, neobentyl glycol acyl di(meth)acrylate, cyclobentenyl di(meth)acrylate , dicyclobentanyl di(meth)acrylate, 2-
(2-hydroxy-1,1-dimethylethyl)-5-hydroxymethyl-5-ethyl-1,3-dioxazine (
meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolbronopentetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol 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)acryloyloxyjethoxy-3,5-dibromophenyl)-propane, 2,2-bis(4-(meth)acryloyloxypentaethoxy-3,5-dibromo phenyl)-propane, 2.2-bis(4-(meth)acryloyloxyethoxy-3,5-dimethylphenyl)-propane, 2.
2-bis(4-(meth)acryloyloxyethoxy-
3-phenylphenyl)-propane, 2,2-bis(4
-(meth)acryloyloxyethoxyphenyl)-sulfone, 2.2-bis(4-(meth)acryloyloxyjetoxyphenyl)-sulfone, 2.2-bis(4-(meth)acryloyloxypentaethoxyphenyl)- Sulfone, 2.2-bis(4-(meth)acryloyloxyethoxy-3-phenylphenyl)-sulfone, 2.2-bis(4-meth)acryloyloxyethoxy-3,5 dimethylphenyl)-sulfone, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)-sulfide, 2,2-bis(4-(meth)acryloyloxyjetoxyphenyl>-sulfite, 2,2-bis(4-(meth) Acryloyloxypentaethoxyphenyl)-sulfite, di((meth)
acryloyloxyethoxy) phosphate, tri(
Polyfunctional (meth)acrylic compounds such as (meth)acryloyloxyethoxy)phosphate: Vinyl compounds such as styrene, vinyltoluene, chlorostyrene, bromostyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylnaphthalene, N-vinylpyrrolidone, etc. Compounds; Allyl compounds such as diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, diallyl phthalate, and 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
The blending ratio of component (D) is (A) 20 to 80 parts by weight, (B) 10 to 60 parts by weight, and (C) 5 parts by weight when the total lid of components (A) to (D) is 100 parts by weight. ~60 parts by weight,
(D) 0 to 60 groin parts. 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 increases and the workability of cast polymerization decreases. The preferred amount is 30 to 60
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 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. Although component (D) is not an essential component, it is a component used to reduce 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 blended.

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 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, methylphenylcrioxylate, 2,4.6-trimethylhenzoyldif Examples include photopolymerization initiators such as enylphosphine oxide. These may be used alone or in a mixed system of two or more. The blending ratio of this polymerization initiator is (total of components A3 to (D) 10
It is usually 0.005 to 5 parts by weight relative to 0 parts by weight.

In the joint 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. 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 of crow and metal plates, or a combination of these. In addition to the above-mentioned thermoplastic resin, an adhesive tape made of polyester may be used as the gasket.

As the gasket, in addition to using the above-mentioned soft thermoplastic resin, the two molds may be fixed with polyester adhesive tape or the like.

〔Example〕

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.

UDMI: Urethane dimethacrylate obtained by reacting isophorone cyisocyanate and 2-hydroxypropyl methacrylate UDM2: 1.3-Bis(α,α-dimethylisocyanate methyl) Hensen and 2-hydroxypropyl methacrylate Obtained urethane dimethacrylate UDA3 Urethane diacrylate obtained by reacting nitolylene diisocyanate and 2-hydroxyethyl acrylate DAI: Diacrylate of 2 mole adduct of hydroxypivalic acid neopentyl glycol ester/caprolactone ('m+n=2 ) DM2: Dimethacrylate of 4-mole adduct of hydroxypivalic acid neopentyl glycol ester/caprolactone (m+n=4) DA3: Diacrylate of hydroxypivalic acid neopentyl glycol ester (m+no) 9EGDM: Nonaethylene glycol dimethacrylate PhM :Phenyl methacrylate BPhM: 2-phenyl phenyl methacrylate 3B
rPM: 2,4,6-tribromophenoxyethyl acrylate HPM: 3-phenoxy-2-hydroxypropyl methacrylate HDDM: 1,6-hexamethylene dimethacrylate HDDA: 1,6-hexamethylene diacrylate DGBC: diethylene glycol bis Allyl carbonate BzM: Penzyl methacrylate POM: Phenoxyethyl methacrylate Synthesis Example 1 (
Synthesis of DM2 by transesterification) 2.2 kg of diol prepared by adding a total of 4 moles of caprolactone to hydroxypivalic acid neopentyl glycol ester, 2.0 kg of MMA, and 0.5 g of hydroquinone monomethyl ether were placed in a 5Il fourth flask. and using 50 g of titanium tetra-n-butoxide as a catalyst, 10
The methanol produced while stirring at 0 to 120°C is
It was azeotropically removed with MA and 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 DM2.

The obtained DM2 was colorless and transparent, and its purity was 100% when analyzed by bromine addition.

Synthesis Example 2 (Synthesis of urethane dimethacrylate) 222 parts of 5-isophorone diisocyanate and 0.3 part of hydroquinone monomethyl ether were placed in a three-necked flask.
A mixture of 302 parts of 2-hydroxypropyl methacrylate and 0.3 parts of di-n-butyltin laurate was added dropwise to the mixture over 3 hours while stirring at a temperature of .degree. After the dropwise addition was completed, the reaction was further continued at 70° C. for 8 hours to obtain urethane dimethacrylate (UDML).

Example I UDMI 40 g, DM235 g, PhM20 g,
HDDM 5g, 2,4.6-1-limethylbenzoyldiphenylphosphine oxide 0.03g.

Mix 0.1 g of t-butylperoxyisobutyrate, 0.05 g of 2-hydroxy-4-methoxybenzophenone, and 0.2 g of tridotesyl phosphate, stir well at room temperature, and then reduce the pressure to 50 mmHg for 10 minutes. I deflated.

This composition was mirror-finished with an outer diameter of 80IIIll+,
Glass with a curvature of 386mm, outer diameter of 80mm, and curvature of 65mm
glass to form a concave lens with a center thickness of 5 mm and 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, 13
Heated at 0°C for 2 hours. Thereafter, the lens was removed from the mold and annealed by heating at 120° C. for 1 hour. The lenses manufactured in this manner were evaluated using the following evaluation method, and the results are shown in Table 1. In addition, evaluation items other than surface accuracy and falling ball test were thickness 2[Ilm or 5mm, outer diameter 75Io]
The measurement was carried out using a disk-shaped plate of lIl.

0 light transmittance (%): ASTM DI003
-6].

Refractive index: Measured on the D line at 589.3 parts m 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 center thickness of 1.5 mm were tested according to FDA standards. However, the maximum weight of the steel ball is shown when the steel ball is dropped from a height of 127 mm.

Rockwell hardness: Measured according to JIS K7202.

Heat resistance: Tg at log load was measured using a TMA measuring device.

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: 5 to 10%) E: Significantly curved. (Difference is 10-20%) F: Unusable. (
Difference of 20% or more) Injection workability: The difficulty level of injecting the monomer mixture into the mold was determined.

O: Easy to inject. ×: Difficult to inject.

Dyeability: Seiko Blacks Diamond Coat Staining Agent Amber D (Seiko Hanbanbu Seiko) 2g was dispersed in 1 fl of water and colored for 5 minutes at 90°C, and the visible light transmittance was measured. .

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
It is also shown in the table.

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

Comparative Examples 2 to 9 Lenses were manufactured and evaluated in the same manner as in Example 1, except that the monomers were used in the proportions shown in Table 1. Results first
It is also shown in the table.

〔Effect of the invention〕

The plastic lens composition of the present invention can be polymerized in a short 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 concave lenses and the like is particularly excellent.

Claims (1)

[Claims] 1) (A) Urethane poly(meth)acrylate 20 having two or more (meth)acryloyloxy groups in one molecule
~80 parts by weight (B) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R^1 is hydrogen or a methyl group, m and n are 1
10 to 60 parts by weight of a di(meth)acrylate compound (representing an integer of ~4) (C) General formula (II), (III) or (IV) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) ▲There are 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-, ▲ There are mathematical formulas, chemical formulas, 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 from 0 to 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) at least A composition for a plastic lens, the main component of which is 0 to 60 parts by weight of a compound having one polymerizable double bond (the total of components (A) to (D) being 100 parts by weight).