JP3362987B2 - Composition for plastic lens - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition useful for producing a plastic lens having excellent heat resistance, impact resistance, dyeability, low water absorption, moldability, surface accuracy, and high elastic modulus.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their features such as easy molding and light weight. Above all, since transparent plastics used as spectacle lenses are required to have heat resistance and chemical resistance, they are not thermoplastics such as polymethylmethacrylate and polystyrene, but heat such as polydiethylene glycol bisallyl carbonate (trademark CR-39 of PPG). Curable plastics have been used.

However, in recent years, due to the demands for high refractive index, low specific gravity and high productivity of plastic lenses, plastic lenses manufactured from various monomers and oligomers replacing CR-39 have been proposed.

Important properties required of the plastic lens are heat resistance, impact resistance, dyeability, low water absorption, surface accuracy of the molded product and the like. Heretofore, as a component for improving impact resistance and dyeability, a monomer or oligomer having a structure having a high elasticity such as an ether bond, a urethane bond, an ester bond or a carbonate bond has been used.
Among these, low-viscosity di (meth) acrylate compounds having an ether bond in the molecule have been proposed (JP-A-64-16813).

Di (meth) which gives this polyether structure
Typical examples of the acrylate monomer include polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate. The impact resistance and the dyeability of the plastic lens obtained by curing are improved in proportion to the increase in the number of repeating units of ethylene oxide or propylene oxide of these monomers and in proportion to the added amount of these monomers. However, with this method, on the contrary, problems arise in that the lens requires heat resistance, low water absorption (water resistance), and maintaining surface accuracy.

As a result of intensive studies to solve the above problems, the present inventors have found that polybutylene glycol di (meth) is a monomer that gives a polymer having a good balance of impact resistance, dyeability and low water absorption. When we found an acrylate and applied it to a plastic lens in combination with an epoxy poly (meth) acrylate that gives heat resistance, elastic modulus, and refractive index to the plastic lens, the impact resistance,
It was found that a plastic lens having excellent dyeability, good heat resistance and low water absorption can be obtained. However, in this composition, the surface accuracy (the curvature of the lens and the designed curvature are the same) required for the lens was not perfect. Therefore, as a result of further study, a lens composition comprising the above-mentioned epoxy poly (meth) acrylate and polybutylene glycol di (meth) acrylate was added to a monoalcohol having an aromatic hydrocarbon group or a halogen-substituted aromatic hydrocarbon group. It has been found that the surface accuracy can be improved by blending a (meth) acrylate (JP-A-4-65407).

[0007]

However, as the amount of polybutylene glycol di (meth) acrylate used as the impact resistance component and the dyeability component is increased, the impact resistance of the lens obtained by curing is increased, Although the dyeability can be increased, there is a problem that the elastic modulus is lowered.

In recent years, spectacle lens materials have been required to have a higher elastic modulus because of the necessity of designing the lens thickness to be thin. In addition to various performances such as impact resistance, heat resistance, dyeability, surface accuracy, etc. Need to achieve rate.

Generally, the elastic modulus can be increased by increasing the crosslink density, but in order to increase the crosslink density, the addition amount of polybutylene glycol di (meth) acrylate is reduced and other polyfunctional monomer is substituted. , Impact resistance and dyeability are deteriorated.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that epoxy poly (meth) acrylate, polybutylene glycol di (meth) acrylate, and monofunctional (meth) acrylate having an aromatic hydrocarbon group are used. Addition of urethane poly (meth) acrylate having a specific structure to the composition which gives a plastic lens excellent in impact resistance, heat resistance, dyeability, low water absorption, and surface accuracy impairs the above-mentioned various performances. The inventors have found that a high elastic modulus can be imparted to the present invention, and completed the present invention.

That is, the present invention provides (A) an epoxy poly (meth) acrylate having two or more (meth) acryloyloxy groups in one molecule.
20 to 80 parts by weight (B) General formula (I)

[0012]

[Chemical 4] (In the formula, R ¹ is hydrogen or a methyl group, and n is an integer of 5 to 16.) Polybutylene glycol di (meth) acrylate 5 to 40 parts by weight (C) General formula (II), (III) ) Or (IV)

[0013]

[Chemical 5] (In the formula, R² Is hydrogen or a methyl group, R³ Is -CH₂ 
-, -CH₂ CH₂ O-, -CH (CH₃ ) CH₂ O
-, -CH₂ CH (OH) CH₂ O- or -CH ₂ C
H₂ CH₂ CH₂ O-, X is Cl, Br or I, m is
An integer of 0 to 3, p is an integer of 0 to 5, q is an integer of 0 to 4
And r represent an integer of 0 to 3. )
) Acrylate 5-40 weight
Department (D) Two or more (meth) acryloyloxy groups in the molecule
Urethane poly (meth) acrylate having
                          5-60 parts by weight and (E) at least one polymerizable double bond in the molecule
Compound having 0 to 60 parts by weight (However, the total of components (A) to (E) is 100 parts by weight.
To do. ) Composition for plastic lenses
It is a thing.

In the present specification, (meth) acryloyl represents (meth) acryloyloxy and / or acryloyloxy, (meth) acryl represents methacryl and / or acryl, and (meth) acrylate is methacrylate and / Or acrylate.

Hereinafter, each component of the plastic lens composition of the present invention will be described in detail.

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, has two or more glycidyl groups in the molecule. Examples thereof include a glycidyl group ring-opening reaction product of an epoxy compound and (meth) acrylic acid or a (meth) acrylate compound containing a carboxyl group in the molecule.

The first component (A) imparts to the lens obtained by curing the elastic modulus, heat resistance and refractive index which are insufficient by the second component polybutylene glycol di (meth) acrylate (B) alone. It is an ingredient.

The epoxy compound used in the above-mentioned ring-opening reaction for obtaining the first component (A) has at least two glycidyl groups in the molecule, and is a condensation reaction between various polyol compounds and epichlorohydrin. Is obtained by It is also possible to use a compound having at least two glycidyl groups in the molecule having a repeating structure obtained by the addition reaction of the obtained epoxy compound and the raw material polyol.

Specifically, 1,6-hexanediol 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, neopentyl glycol hydroxypivalate diester Glycidyl ether, trimethylolpropane diglycidyl ether Tell, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, sorbitol tetraglycidyl ether, Aliphatic epoxy compounds such as diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, diglycidyl ether of isophoronediol, 1,4-bis (hydroxymethyl)
Diglycidyl ether of cyclohexane, bis-2,2
Alicyclic epoxy compounds such as diglycidyl ether of hydroxycyclohexyl propane, resorging glycidyl ether, bisphenol A diglycidyl ether,
Bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bis (3,5-dimethyl-
4-Hydroxyphenyl) sulfone diglycidyl ether, bis (3-methyl-4-hydroxyphenyl) sulfone diglycidyl ether, bis (3-phenyl-
Examples thereof include a diglycidyl ether of 4-hydroxyphenyl) sulfone, a condensate of 2,6-xylenol dimer and epichlorohydrin, an aromatic epoxy compound such as orthophthalic acid diglycidyl ether and cresol novolac polyglycidyl ether.

As the compound to be reacted with these epoxy compounds, in addition to (meth) acrylic acid, a hydroxy group (meth) acrylate and a carboxyl group-containing (meth) acrylate obtained by reacting an acid anhydride such as o-phthalic anhydride are used. ) An acrylate compound, a glycidyl (meth) acrylate, and a carboxyl group-containing (meth) acrylate compound obtained by reacting a compound having two or more carboxyl groups in the molecule such as adipic acid.

The reaction of the epoxy compound with the (meth) acrylic acid or the carboxyl group-containing (meth) acrylate compound is carried out, for example, by mixing the two and using as a catalyst a tertiary amine such as trimethylamine or a quaternary ammonium salt such as benzyltrimethylammonium chloride. 60 to 1
It is carried out by heating to 10 ° C.

In the present invention, epoxy poly (meth)
The acrylate (A) may be used alone or in combination of two or more kinds.

From the viewpoint of colorless transparency and heat resistance of the plastic lens obtained by curing, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, glycerol triglycidyl ether, Tris ( 2-Hydroxyethyl) isocyanurate triglycidyl ether, 2,2-bis (4-glycidyloxycyclohexyl) propane, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S Epoxy poly (meth) acrylate, which is a reaction product of diglycidyl ether and (meth) acrylic acid, is preferably used. Further, at least 2 in the molecule having a repeating structure obtained by the addition reaction of these epoxy compounds and the raw material diol.
It is also possible to use an epoxy compound having one or more glycidyl groups.

Further, it is particularly preferable to use an epoxy poly (meth) acrylate represented by the following general formula (V) from the viewpoint of the elastic modulus and refractive index of the lens. S in the general formula (V) represents the number of repeating units and is an integer of 1 to 5. Also, as the number of repeating units increases, the viscosity increases, so 1
It is preferably an integer of ˜3.

[0025]

[Chemical 6] (In the formula, R ⁴ and R ⁵ are hydrogen or a methyl group, Y is hydrogen or Cl, Br, or I. s is an integer of 1 to 5.) Poly which is the second component of the composition of the present invention Butylene glycol di (meth) acrylate (B) is a compound obtained by converting polybutylene glycol having a degree of polymerization of 5 to 16 into (meth) acrylate, and has impact resistance on a lens obtained by curing,
It is a component that imparts dyeability. In general, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate are often used for this purpose. In this case, although the above-mentioned object is achieved, these monomers are hydrophilic. Due to its high property, there is a problem that the water absorption of the lens obtained by curing is increased. Second component, polybutylene glycol di (meth)
The acrylate (B) is represented by the general formula (I). Here, the degree of polymerization formula _{:-( CH 2 CH 2 CH 2 CH} 2 O) n
It means the number n of repeating units represented by-and is 5 to 16. If the degree of polymerization is less than 5, sufficient flexibility cannot be obtained, and if it exceeds 16, the crosslinking density is lowered, and the surface hardness, elastic modulus and heat resistance of the polymer are lowered. Further, since the viscosity of the monomer also increases, casting workability also decreases. The preferred degree of polymerization is 7-12. However, since polybutylene glycol di (meth) acrylate is generally a mixture having a different degree of polymerization in a normal distribution, the degree of polymerization n here means the central value.

The polybutylene glycol di (meth) acrylate used in the present invention is, for example, a condensation reaction of polybutylene glycol and (meth) acrylic acid obtained by ring-opening polymerization of tetrahydrofuran or polybutylene glycol and (meth) acrylic acid. It can be easily produced by a transesterification reaction with, but a method by a transesterification reaction is preferable because it gives a colorless and transparent monomer.

The mono (meth) acrylate compound (C) represented by the general formula (II), (III) or (IV), which is the third component of the composition of the present invention, contains only the first and second components. It is a component that exerts the effect of improving the surface accuracy during lens molding, which cannot be obtained by use.

The mono (meth) acrylate compound (C) of a monoalcohol having an aromatic hydrocarbon or a halogen-substituted aromatic hydrocarbon group is obtained by opening ethylene oxide, propylene oxide or tetrahydrofuran in the above monoalcohol or monoalcohol. It can be synthesized by subjecting a monoalcohol obtained by cycloaddition and (meth) acrylic acid to a condensation reaction. Also (meta)
It can also be synthesized by a transesterification reaction with methyl acrylate.

Specific examples of the mono (meth) acrylate compound (C) include phenyl (meth) acrylate, benzyl (meth) acrylate and phenoxyethyl (meth).
Acrylate, phenoxy-2-methylethyl (meth)
Acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, phenyl-di (oxyethyl)-(meth) acrylate, phenyl-di (2-methyloxyethyl)-(meth) acrylate, phenyl-
Tri (2-methyloxyethyl)-(meth) acrylate, phenoxybutyl (meth) acrylate, phenyl-di (oxybutyl)-(meth) acrylate, phenyl-tri (oxybutyl)-(meth) acrylate, 2
-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-phenylphenoxy) -2-hydroxypropyl (meth) acrylate,
3- (4-phenylphenoxy) -2-hydroxypropyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthyloxyethyl (meth) acrylate, 2-naphthyloxyethyl ( (Meth) acrylate, 1-naphthyl-
Di (oxyethyl)-(meth) acrylate, 2-naphthyl-di (oxyethyl)-(meth) acrylate, 1
-Naphthyl-2-methyloxyethyl- (meth) acrylate, 2-naphthyl-2-methyloxyethyl- (meth) acrylate, 3- (1-naphthyloxy) -2-
Hydroxypropyl (meth) acrylate, 3- (2-
Naphthyloxy) -2-hydroxypropyl (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-tribromophenyl-di (oxyethyl)-(meth) acrylate, 2,4,4. 6-tribromophenyl-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-penta Chlorophenyl (meth) acrylate, 2,4-dichlorophenoxyethyl (meth) acrylate, 2,
4,6-trichlorophenoxyethyl (meth) acrylate, 2,4,6-trichlorophenyl-di (oxyethyl)-(meth) acrylate, 2,4,6-trichlorophenoxy-2-methyloxyethyl (meth) acrylate, 3- (2,4,6-tribromophenoxy)-
2-hydroxypropyl (meth) acrylate, 3-
(2,3,4,5,6-pentabromophenoxy) -2
-Hydroxypropyl (meth) acrylate, 2-phenyl-4-bromophenyl (meth) acrylate, 2-
(4-Bromophenyl) -4,6-dibromophenyl (meth) acrylate, 2- (4-chlorophenyl)-
4,6-dichlorophenyl (meth) acrylate, 2-
Phenyl-4-bromophenyloxyethyl (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, 3- [1- (2
-Bromonaphthyl)]-2-hydroxypropyl (meth) acrylate, 3- [2- (2-bromonaphthyl)]-2-hydroxypropyl (meth) acrylate and the like.

In the present invention, the third component, the mono (meth) acrylate compound (C), may be used alone or in combination of two or more kinds. 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, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenoxy) -2-hydroxypropyl (meth) Acrylate,
1- (4-phenylphenoxy) -2-hydroxypropyl (meth) acrylate, 1-naphthyloxyethyl (meth) acrylate, 2-naphthyloxyethyl (meth) acrylate, 2,4,6-tribromophenyl (meth) Acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenyl-di (oxyethyl)-(meth) acrylate and 2,4,6-tribromobenzyl (meth) acrylate Is preferred.

The urethane poly (meth) acrylate (D) having at least two (meth) acryloyloxy groups in the molecule, which is the fourth component of the present invention, includes a hydroxy group-containing (meth) acrylate compound and a molecule. Examples thereof include urethanization reaction products with an aromatic, alicyclic or aliphatic polyisocyanate compound having two or more isocyanate groups. The fourth component (D) is a component that imparts a high elastic modulus to the lens obtained by curing without lowering impact resistance.

Specific examples of the aromatic, alicyclic or aliphatic polyisocyanate compound having two or more isocyanate groups in the molecule include cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate and 1,3. -Bis (α, α-dimethyldiisocyanate methyl) benzene, 4,4-diphenylmethane diisocyanate, m-
Examples thereof include phenylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), naphthalene diisocyanate, biphenyl diisocyanate and trimethylhexamethylene diisocyanate. Compounds having at least two isocyanate groups in the molecule obtained by reacting these isocyanates with compounds having at least two active hydrogens such as amino groups, hydroxy groups, carboxyl groups and water, or 3 to 3 of the above diisocyanate compounds A pentamer or the like can also be used.

From the viewpoint of heat resistance and elastic modulus, aromatic compounds,
Polyisocyanates having an alicyclic skeleton are preferred. Further, from the viewpoint of weather resistance, polyisocyanates having an alicyclic skeleton such as isophorone diisocyanate and methylenebis (4-cyclohexyl isocyanate) are particularly preferable.

Specific examples of the hydroxy group-containing (meth) acrylate compound to be reacted with the polyisocyanate compound include 2-hydroxyethyl (meth) acrylate,
Hydroxy group-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, Addition reaction product of a monoepoxy compound such as glycidyl (meth) acrylate and (meth) acrylic acid; mono (meth) acrylic acid ester of a diol compound such as polyethylene glycol and polypropylene glycol; polycaprolactone diol (n = 1 to 5) And mono (meth) acrylic acid ester of

A preferred hydroxy group-containing (meth) acrylate compound is a compound represented by the general formula (VI).

[0036]

[Chemical 7] (In the formula, R ⁶ is hydrogen or a methyl group, and R ⁷ is —CH ₂ C.
_{H 2 O -, - CH (} CH) 3 CH 2 O- or -CH _{2
CH 2 CH 2 CH 2 0-,} t is an integer of 1-3. ) Polyisocyanate compound and hydroxy group-containing (meth)
The addition reaction with an acrylate compound is carried out by a known method, for example, a mixture of a hydroxy group-containing (meth) acrylate compound and a catalyst, for example, di-n-butyltin dilaurate in the presence of a polyisocyanate compound, under the condition of 50 to 90 ° C. It can be produced by dropping and reacting.

In the present invention, the urethane poly (meth) acrylate (D) may be used alone or in combination of two or more kinds.

The compound (E) having at least one polymerizable double bond in the molecule, which is the fifth component of the composition of the present invention, is used for the cured lens product obtained by curing, such as heat resistance and surface hardness. It is a component that imparts various physical properties or low viscosity to the composition to improve workability.

Particularly in the present invention, since highly viscous epoxy poly (meth) acrylate and urethane poly (meth) acrylate are used, the composition viscosity is lowered and casting workability is improved. Is preferably a low-viscosity (meth) acrylate monomer.

Specific examples of the compound (E) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. i-butyl, (meth)
T-butyl acrylate, pentyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate,
Stearyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, methallyl (meth) acrylate, glycidyl (meth) acrylate,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
2-Cyanoethyl (meth) acrylate, dibromopropyl (meth) acrylate, N-vinyl-2-pyrrolidone (meth) acrylate, polyethylene glycol monoalkyl ether (meth) acrylate, polypropylene glycol monoalkyl (meth) acrylate Ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (meth) acrylic acid
Hydroxybutyl, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Mono (meth) such as phosphoethyl acrylate (meth)
Acrylate compound; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di ( Di (meth) acrylate of poly (or mono) ethylene glycol such as (meth) acrylate; propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di ( Di (meth) acrylate of poly (or mono) propylene glycol such as (meth) acrylate and nonapropylene glycol di (meth) acrylate; Lene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,14-tetradecamethylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, di (meth) acrylate of a caprolactone adduct of neopentyl glycol hydroxypivalate, neopentyl glycol adipate 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, dipenta Erythritol penta (meth) 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) acryloyloxydiethoxyphenyl] -propa , 2,2-bis [4-
(Meth) acryloyloxypentaethoxyphenyl]
-Propane, 2,2-bis [4- (meth) acryloyloxyethoxy-3,5-dibromophenyl] -propane, 2,2-bis [4- (meth) acryloyloxydiethoxy-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,
5-phenylphenyl] -propane, bis [4- (meth) acryloyloxylphenyl] -sulfone, bis [4- (meth) acryloyloxyethoxyphenyl]
-Sulfone, bis [4- (meth) acryloyloxydiethoxyphenyl] -sulfone, bis [4- (meth) acryloyloxypentaethoxyphenyl] -sulfone, bis [4- (meth) acryloyloxyethoxy-3-phenylphenyl ] -Sulphone, 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,
Polyfunctional (meth) acrylate compounds such as di ((meth) acryloyloxyethoxy) phosphate and tri [(meth) acryloyloxyethoxy] phosphate;
Styrene, vinyltoluene, chlorostyrene, bromostyrene, divinylbenzene, 1-vinylnaphthalene, 2
Vinyl compounds such as vinylnaphthalene and N-vinylpyrrolidone; allyl compounds such as diethylene glycol bisallyl carbonate, trimethylolpropane diallyl, diallyl phthalate and dimethallyl phthalate; (meth) acrylic acid and barium, lead, antimony, titanium,
Examples thereof include metal salts such as tin and zinc. These can be used alone or in a mixture of two or more.

Regarding the blending ratio of the components (A) to (E) in the composition of the present invention, when the total amount of the components (A) to (E) is 100 parts by weight, (A) 20 to 80 parts by weight. ,
(B) 5 to 40 parts by weight, (C) 5 to 40 parts by weight, (D)
5 to 60 parts by weight, (E) 0 to 60 parts by weight.

When the amount of the component (A) is less than 20 parts by weight, it is impossible to impart sufficient elastic modulus, heat resistance and surface hardness to the lens obtained by curing, and when it exceeds 80 parts by weight, the viscosity of the composition is high. Therefore, the workability of cast polymerization is reduced. A preferred blending amount is 30 to 60 parts by weight. If the amount of component (B) is less than 5 parts by weight, sufficient impact resistance cannot be imparted to the lens and dyeability cannot be imparted. On the other hand, if it exceeds 40 parts by weight, the elastic modulus, heat resistance and surface hardness of the lens are lowered, which is not preferable. The preferred amount is 10 to 3
5 parts by weight. Further, if the amount of the component (C) is less than 5 parts by weight, the surface accuracy of the molded lens is deteriorated, and if it exceeds 40 parts by weight, the impact resistance and heat resistance of the lens are deteriorated, which is not preferable.
A preferred blending amount is 10 to 35 parts by weight. The component (D) is a component that imparts a high elastic modulus without reducing the impact resistance of the lens. If it is 5 parts by weight or less, high elastic modulus and impact resistance cannot be imparted at the same time, and if it exceeds 60 parts by weight, the viscosity of the composition becomes high and the workability at the time of casting decreases. The preferred blending amount is 10 to 50 parts by weight.
The component (E) is not an essential component, but is a component used for further improving the heat resistance and surface hardness of the lens, and for lowering the viscosity of the composition and improving the workability of casting. The preferred blending amount is 0 to 30 parts by weight. Further, the composition of the present invention, if necessary, an antioxidant,
You may mix | blend various additives, such as an anti-yellowing agent, a ultraviolet absorber, a bluing agent, and a pigment, within the range which does not impair the effect of this invention.

The composition for plastic lenses of the present invention comprises
The components (A) to (E) may be mixed and stirred by a conventional method, and further various additives may be added, if necessary, to produce the composition.

Examples of the polymerization initiator used for curing the plastic lens composition of the present invention include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate and t-butyl peroxy-2. -Organic peroxides such as ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2 '
-Azo compounds such as azobis (2,4-dimethylvaleronitrile); 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxycyclohexylphenylketone, methylphenylglyoxylate, acetophenone, benzophenone, diethoxy Acetophenone,
2,2-dimethoxy-2-phenylacetophenone, 1
-Phenyl-1,2-propane-dione-2- (o-ethoxycarbonyl) oxime, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, benzoin methyl ether, benzoin ethyl ether , Benzoin propyl ether, benzoin isobutyl ether, 2-chlorothioxanthone,
Examples include photopolymerization initiators such as isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, and benzoyldimethoxyphosphine oxide. These are used alone or in a mixture of two or more. The mixing ratio of this polymerization initiator is
It is usually 0.005 to 5 parts by weight based on 100 parts by weight of the total of the components (A) to (E).

The polymerization and curing method is carried out, for example, by placing two glass molds, which have been mirror-polished, facing each other, and surrounding a polymerization initiator in a mold surrounded by a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer or the like. It is carried out by injecting the composition of the present invention containing the composition and irradiating with active energy rays from one side or both sides of the template, or by heat treatment. Further, it may be a combination of irradiation and heating. Here, as the molding mold, there are glass and glass, glass and plastic plate, glass and metal plate, or a combination thereof. Further, as the gasket, in addition to the thermoplastic resin as described above, an adhesive tape made of polyester or the like may be used.

[0046]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The abbreviations and synthesis examples of each monomer are as follows.

EDM1: Epoxy dimethacrylate obtained by reacting bisphenol A diglycidyl ether with methacrylic acid EDA2: Epoxy diacrylate obtained by reacting tetrabromobisphenol A diglycidyl ether with acrylic acid UM1: Isophorone Urethane dimethacrylate UM2 obtained by reacting diisocyanate and 2-hydroxypropyl methacrylate: Urethane dimethacrylate UM3 obtained by reacting 2-hydroxyethyl methacrylate with methylenebis (4-cyclohexyl isocyanate): Xylylene diisocyanate and 2- Urethane dimethacrylate 9BGDM obtained by reacting hydroxyethyl methacrylate: nonabutylene glycol dimethacrylate 12BGDM: dode Butylene glycol dimethacrylate PHM: phenyl methacrylate BZM: benzyl methacrylate BPHM: o-biphenyl methacrylate HDDM: 1,6-hexamethylene glycol dimethacrylate 9 EGDM: nonaethylene glycol dimethacrylate Synthesis example 1 [Nonabutylene glycol dimethacrylate by transesterification method ( 9BGDM)] In a 5-liter four-necked flask, 2000 g of nonabutylene glycol (PTG-650SN manufactured by Hodogaya Chemical Co., Ltd., average molecular weight 680), 2000 g of methyl methacrylate (molecular weight 100, hereinafter abbreviated as MMA) and hydroquinone. 0.5 g of monomethyl ether was added, and 50 g of titanium tetra-n-butoxide was used as a catalyst.
The methanol produced was azeotropically removed with MMA while stirring at 00 to 120 ° C., and the mixture was reacted for 3 hours. After the reaction, excess MMA was distilled off under reduced pressure, 1000 g of toluene was added to the residue, and the residue was washed with alkaline water, and toluene was distilled off under reduced pressure to give 9B.
GDM was obtained. The obtained 9BGDM is colorless and transparent,
It was 100% in the purity analysis by bromine addition. Synthesis Example 2 Synthesis of [epoxy dimethacrylate (EDM1)] In a 5 liter glass reaction vessel, bisphenol A diglycidyl ether (Epototo Y manufactured by Tohto Kasei Co., Ltd.)
D-8125, epoxy equivalent 173g / eq) 1730
g, 860 g of methacrylic acid (molecular weight 86), 13 g of benzyltrimethylammonium chloride as a catalyst, and 0.78 g of 2-hydroxy-4-methoxybenzophenone as a polymerization inhibitor were added, and the mixture was uniformly stirred while heating at 60 ° C. After that, 3 hours at 70 ℃, 3 hours at 80 ℃, 90 ℃
And heated for 12 hours to obtain EDM1. EDM1 is
It was a colorless and transparent high-viscosity liquid. The end point of the reaction was determined by measuring the acid value of the reaction solution. Synthesis Example 3 Synthesis of [epoxy diacrylate (EDA2)] Tetrabromobisphenol A diglycidyl ether (manufactured by Tohto Kasei Co., Ltd.) was placed in a 5-liter glass reaction container.
Epotote YDB-340, epoxy equivalent 340g / e
q) 3400 g, acrylic acid (molecular weight 72) 720 g,
Benzyltrimethylammonium chloride 13 as a catalyst
g and 0.78 g of 2-hydroxy-4-methoxybenzophenone as a polymerization inhibitor were added, and the mixture was stirred uniformly while heating at 60 ° C. Then, heating was performed at 70 ° C. for 3 hours, 80 ° C. for 3 hours, and 90 ° C. for 12 hours to obtain EDA2. E
DA2 was a colorless and transparent high-viscosity liquid. The end point of the reaction was determined by measuring the acid value of the reaction solution. Synthesis Example 4 Synthesis of [Urethane Dimethacrylate (UM1)] 2183 g of isophorone diisocyanate (IPDI manufactured by Daicel Huls KK, molecular weight 218.3) in a 5 liter glass reaction vessel, and dilauric acid di-
6.4 g of n-butyltin, 2,6-di-te as an inhibitor
6.4 g of rt-butyl-4-methylphenol was added,
While heating to 70 ° C., the mixture was stirred to make a uniform solution. While keeping the temperature of this system at 70 ° C., 2884 g of 2-humanroxypropyl methacrylate (Acryester HP manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 144.2) was gradually added dropwise over 5 hours. Further, the temperature of this system was kept at 70 ° C. and the reaction was continued for 8 hours to obtain UM1. The termination of the reaction was carried out by measuring the IR spectrum and the isocyanate equivalent. Synthesis Example 5 Synthesis of [urethane dimethacrylate (UM2)] Methylenebis (4-cyclohexylisocyanate) (manufactured by Sumitomo Bayer Urethane Co., Desmodur W, molecular weight 262.4) 26 in a 5 liter glass reaction vessel 26
24 g, di-n-butyltin dilaurate as a catalyst 2.
6 g and 1.6 g of 2,6-di-tert-butyl-4-methylphenol as a polymerization inhibitor were added, and the mixture was stirred while heating to 60 ° C to form a uniform solution. The temperature of this system is 70
2604 g of 2-hydroxyethylmethacrylate (Acryester HO, manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 130.2) was gradually added dropwise to the mixture while maintaining the temperature at 0 ° C. over 5 hours. Further, the temperature of this system was kept at 70 ° C. and the reaction was continued for 8 hours to obtain UM1. The termination of the reaction was carried out by measuring the IR spectrum and the isocyanate equivalent. Synthesis Example 6 Synthesis of [urethane dimethacrylate (UM3)] 1952 g of xylylene diisocyanate (Takenate 500 manufactured by Takeda Pharmaceutical Co., Ltd., molecular weight 194.2) in a 5 liter glass reaction vessel, and dilauric acid di-n- as a catalyst 2.0 g of butyltin and 1.3 g of 2,6-di-tert-butyl-4-methylphenol were added, and the mixture was stirred while heating to 60 ° C to form a uniform solution. 2-Hydroxyethyl methacrylate (Acryester H manufactured by Mitsubishi Rayon Co., Ltd.) while maintaining the temperature of this system at 70 ° C. with stirring.
2604 g of O and molecular weight 130.2) were gradually added dropwise over 5 hours. Further, the temperature of this system was kept at 70 ° C. and the reaction was continued for 8 hours to obtain UM3. The termination of the reaction was carried out by measuring the IR spectrum and the isocyanate equivalent.

The method of evaluating the plastic lens and the plastic plate obtained by curing is as follows. Refractive index: A plastic plate having a thickness of 2 mm was measured with an Abbe refractometer at a D line of 589.3 nm. Visible light transmittance (%): 2 mm thick flat plate, ASTM
It was measured according to D1003. Saturated water absorption (% by weight): A disk-shaped flat plate having a thickness of 4 mm and a diameter of 80 mm was used and allowed to stand in a 100% saturated steam tank at 70 ° C. for 3 days to measure the increased weight. Drop ball test: A lens with a thickness of 1.5 mm was tested according to the FDA standard. However, when the steel ball was dropped from a height of 127 cm, the maximum weight of the steel ball which the plastic lens did not break was shown. Elastic modulus: A plastic lens flat plate having a thickness of 4 mm, a width of 10 mm, and a length of 85 mm was measured according to JIS K7203 (3-point bending test). Rockwell hardness: Measured according to JIS K7202 using a plastic plate having a thickness of 4 mm. Heat resistance: TMA using a 2 mm thick plastic plate
The Tg (° C) under a load of 10 g was measured with a measuring instrument. Surface accuracy: observe the curved state of the center of the lens with the naked eye,
It was classified into the following ranks. A: No curve 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 (the difference is 1 to 3%) C: Slightly curved (the difference is 3) ~ 5%) D: Curved (difference 5-10%) E: Remarkably curved (difference 10-20%) F: Unreliable (difference 20% or more) Casting workability: mold The difficulty of injecting the monomer mixture into was determined. ○: Easy to inject. X: It is difficult to inject due to high viscosity and poor fluidity. Dyeability: A plastic plate having a thickness of 2 mm was dyed for 10 minutes at 90 ° C. for 10 minutes using a liquid prepared by dispersing a Seiko Plax diamond coat dye in 1 liter of distilled water, and the numerical value of% visible light transmittance was measured. Example 1 40 g of EDM1, 20 g of 9BGDM, PHM 25
g, UM1 15 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.03 g, t-butylperoxyisobutyrate 0.1 g, 2-hydroxy-4-methoxybenzophenone 0.05 g, tridodecyl phosphate 0. After mixing 2 g and stirring well at room temperature, the pressure was reduced to 50 mmHg and degassing was performed for 10 minutes.

Then, two types of plastic flat plate molding molds having an inner thickness of 2 mm and 4 mm sandwiched between two glass molds having a diameter of 80 mm and having a polyvinyl chloride gasket and mirror-finished with this composition, and a plastic lens molding. The composition was injected into a casting mold (having a center inner thickness of 1.5 mm sandwiched between two polyvinyl chloride glass molds having a diameter of 70 mm and a polyvinyl chloride gasket and having a frequency of −2.0 D).

Next, each molding mold in which the composition was injected was irradiated with ultraviolet rays of 30 J / cm ² from both sides by a high-pressure mercury lamp having a lamp length of 10 inches and 2 kW, and then the plastic lens and the flat plate were released from each mold. , 130 ° C. for 2 hours to perform annealing treatment.

The plastic lens thus obtained was subjected to a falling ball test and evaluation of surface accuracy, and other performances were evaluated with the obtained plastic flat plate. The evaluation results are shown in Table 1. Examples 2 to 12 Evaluations were performed in the same manner as in Example 1 except that each component was used in the ratio shown in Table 1. The results are also shown in Table 1.

[0052]

[Table 1]

[0053]

[Table 2] Comparative Examples 1 to 9 Evaluations were performed in the same manner as in Example 1 except that each component was used in the ratio shown in Table 2. The results are also shown in Table 2. Comparative Example 10 100 g of CR-39 (diethylene glycol bisallyl carbonate) and 3 g of diisopropyl peroxypercarbonate were mixed and stirred well, and then poured into the same mold as that used in Example 1, and then at 45 ° C. for 10 hours. 60
After molding by holding at 3 ° C. for 3 hours, at 80 ° C. for 3 hours, and at 95 ° C. for 6 hours, the plastic lens and the flat plate were removed from the mold and heat-annealed at 120 ° C. for 1 hour. The plastic lenses and flat plates produced in this manner were evaluated in the same manner as in Examples, and the results are shown in Table 2.

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

By using the plastic lens composition of the present invention, a lens having excellent heat resistance, impact resistance, dyeability, low water absorption, excellent surface accuracy and a high elastic modulus can be easily produced. it can.

Front page continued (72) Inventor Mitsuaki Yoshizawa 3-5 Yamato, Suwa, Nagano Seiko Epson Corporation (72) Inventor Hiroshi Fukushima 4-chome, Sunadabashi, Higashi-ku, Aichi Prefecture Mitsubishi Rayon Product Development Laboratory, Inc. (72) Inventor Akira Motonaga 4-60, Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Prefecture 4-chome 1-60 Mitsubishi Rayon Co., Ltd. Product Development Research Laboratory (56) Reference JP-A-4-65407 (JP, A) JP-A-3-239711 (JP, A) JP-A-5-310871 (JP , A) JP 5-287040 (JP, A) JP 4-164910 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 290/00-290/14 G02B 1/04

Claims (3)

(57) [Claims] 1. (A) (Meth) acryloyl in one molecule
Epoxy poly (meth) acryl having two or more oxy groups
Rate 20-80 parts by weight (B) General formula (I) [Chemical 1] (In the formula, R¹ Is hydrogen or a methyl group, n is an integer of 5 to 16
Represents a number. ) Polybutylene glycol di (
) Acrylate 5-40 parts by weight (C) General formula (II), (III) or (IV) [Chemical 2] (In the formula, R² Is hydrogen or a methyl group, R³ Is -CH₂ 
-, -CH₂ CH₂ O-, -CH (CH₃ ) CH₂ O
-, -CH₂ CH (OH) CH₂ O- or -CH ₂ C
H₂ CH₂ CH₂ O-, X is Cl, Br or I, m is
An integer of 0 to 3, p is an integer of 0 to 5, q is an integer of 0 to 4
And r represent an integer of 0 to 3. )
) Acrylate 5-40 weight
Department (D) Two or more (meth) acryloyloxy groups in the molecule
Urethane poly (meth) acrylate having
                          5-60 parts by weight and (E) at least one polymerizable double bond in the molecule
Compound having 0 to 60 parts by weight (However, the total of components (A) to (E) is 100 parts by weight.
To do. ) Composition for plastic lenses
Stuff. 2. The composition for a plastic lens according to claim 1, wherein the component (D) is a urethane poly (meth) acrylate having an alicyclic skeleton. 3. The composition for a plastic lens according to claim 1, wherein the epoxy poly (meth) acrylate represented by the component (A) is represented by the general formula (V). [Chemical 3] (In the formula, R ⁴ and R ⁵ are hydrogen or a methyl group, Y is hydrogen or Cl, Br, or I. s is an integer of 1 to 5.)