JPH06208001A - Plastic lens - Google Patents

Abstract

PURPOSE:To provide the lens constituted by laminating a plastic lens base material having a small sp. gr., a primer having sufficient adhesive power thereto and a hardened silicone film. CONSTITUTION:This plastic lens is constituted by laminating a resin film consisting essentially of a copolymer having alkyl ester (meth)acrylate and arom. vinyl compd. as essential components and having further a hydroxyl group, carboxyl group, epoxy group or alkoxysilyl group as the primer layer on the plastic lens base material contg. a polymer consisting of (meth)acrylate (e.g. tricyclodecyl methacrylate having 5 to 22C alicyclic hydrocarbon group in an ester part as an essential component and further laminating the cured matter layer of a silicone resin thereon. This lens has the low sp. gr., low dispersibility (high Abbe number), high refractiveness, excellent heat resistance and good transparency, scratching resistance, dyeability and machinability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to eyeglass plastic lenses and other plastic lenses that can be used as optical lenses.

[0002]

2. Description of the Related Art Conventionally, as materials for optical lenses, highly transparent acrylic resin, diethylene glycol bisallyl carbonate resin (for example, CR-39), polystyrene,
Polycarbonate and the like are used. Among them, a lens that is widely used as a spectacle lens is a lens using diethylene glycol bisallyl carbonate, which is a thermosetting resin. The reason is that it is excellent in transparency, low dispersibility (high Abbe number), heat resistance and impact resistance.

However, the lens using diethylene glycol bisallyl carbonate has a refractive index of 1.50 and has a problem that the thickness of the lens is larger than that of a glass lens (particularly, it is remarkable when the lens power is large). .

Recently, there has been a strong demand for thinner and lighter spectacle lenses, and development of spectacle lens materials having a high refractive index, which makes it possible, has been actively pursued. For example, JP-A-5
No. 6,166,214 proposes a copolymer of dimethacrylate having a nuclear halogen-substituted aromatic ring and a monofunctional monomer having an aromatic ring. This material has high refraction, but has a problem that the specific gravity becomes large because it contains a halogen group in the resin skeleton. In addition, JP-A-6
A copolymer of polyisocyanate and polythiol is proposed in JP-A 3-46213. This material has high refraction, but has a problem of low heat resistance.

On the other hand, examples of high-refraction thermoplastic resins include polystyrene (refractive index 1.58, Abbe number 31) and polycarbonate (refractive index 1.58, Abbe number 30). Although they have a high refractive index, they have a problem that the chromatic aberration is large due to the low Abbe number, the former has low heat resistance, and the latter has low surface hardness and is easily scratched.

Also, these materials are inferior in scratch resistance like general plastics. Therefore, a method of coating the lens surface with an organic silane-based cured film has been proposed,
Since this organosilane-based cured film has insufficient uniform adhesion to the surface of the plastic lens, it has a thermoplastic acrylic primer (Japanese Patent Laid-Open No. 52-138565) and an acrylic resin having a functional group such as an amino group. System primer
(JP-A-53-138476), a silicon-based primer comprising a reaction product of an alkoxysilane having a functional group such as an amino group or a hydroxy group and a cyclic acid anhydride.
(JP-A-53-81533), a silicon-based primer comprising a mixture of an epoxysilane hydrolyzate and aminosilane (JP-A-54-63176), a functional group-containing thermoplastic acrylic resin and an ultraviolet absorber. Acrylic primer consisting of (Japanese Patent Application Laid-Open No. 55-500809), an acrylic primer consisting of a thermosetting acrylic emulsion and an ultraviolet shielding compound (Japanese Patent Application Laid-Open No. 55-16).
No. 0033), a silicon-based primer comprising a reaction product of an aminosilane, an epoxysilane and an acid anhydride (JP-A-56-16573), and a method of applying a melamine-modified acrylic emulsion to improve the adhesive strength (JP-A-No. 5
6-88469), a thermoplastic acrylic primer comprising a reaction product of an acrylic monomer with an epoxy methacrylate and a hydroxybenzophenone ultraviolet absorber (JP-A-57-23661), self-crosslinking property. A primer consisting of an acrylic copolymer (JP-A-57-
No. 76035), a primer composed of a polyfunctional vinyl polymer (JP-A-57-140162), a primer composed of an acrylic polymer and an alkyltrialkoxysilane (JP-A-57-162729), and methacryl. A method is disclosed in which the surface of a plastic base material is modified with a primer composed of a copolymer of methyl acrylate and methyl acrylate (Japanese Patent Laid-Open No. 58-179237) and the like to improve the adhesion to a silicone cured film. . However, these have been developed for each purpose material. The plastic lens substrate of the present invention shown below did not have a sufficient effect.

[0007]

As is apparent from the above, plastic lens substrates having a low specific gravity have hitherto been used,
Also, there was no primer or silicone-based cured film having sufficient adhesion on this plastic lens substrate. Therefore, the present invention is a plastic lens substrate having a small specific gravity,
The present invention provides a plastic lens in which a primer having a sufficient adhesion and a silicon-based cured film are sequentially laminated.

[0008]

The plastic lens of the present invention comprises a polymer containing, as an essential component, a methacrylic acid ester or an acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion. The surface of the plastic lens substrate contains an acrylic acid alkyl ester or a methacrylic acid alkyl ester and an aromatic vinyl compound as essential components, and further has at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group and an alkoxysilyl group. A resin film containing a copolymer as a main component is provided as a primer layer, and a cured product layer of a silicone resin is provided thereon.

The above ester portion has 5 to 2 carbon atoms.
Specific examples of the methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group of 2 include cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, norbornyl methacrylate, norbornyl methacrylate. Methyl, isobornyl methacrylate,
Bornyl methacrylate, menthyl methacrylate, fentyl methacrylate, adamantyl methacrylate, dimethyl adamantyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl methacrylate, tricyclo methacrylate [5.2. 1.0 ^2,6 ] deca-4-methyl,
Methacrylic acid esters such as cyclodecyl methacrylate,
Cyclopentyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, trimethyl cyclohexyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, isobornyl acrylate,
Bornyl acrylate, menthyl acrylate, fentyl acrylate, adamantyl acrylate, dimethyl adamantyl acrylate, tricyclo acrylate [5.2.
1.0 ^2,6] dec-8-yl, acrylic acid tricyclo [5.2.1.0 ^2,6] dec-4-methyl, acrylic acid esters such as cyclodecyl acrylate. These are used alone or in combination of two or more. Among these, from the viewpoint of Abbe number, specific gravity and heat resistance, cyclohexyl methacrylate, norbornyl methacrylate, norbornyl methyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl methacrylate , Tricyclo [5.2.1.0 ^2,6 ] deca-4-methyl and the like are particularly preferable.

The ester portion in the above has 5 to 2 carbon atoms.
The polymer containing methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group of 2 as an essential component is
Styrene, methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion, radically polymerizable polyfunctional monomer having two or more functional groups, and other copolymerizable It is preferable that the polymer is composed of a vinyl monomer, and particularly styrene 30-
60 parts by weight, 10 to 70 parts by weight of a methacrylic acid ester or an acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion, a radically polymerizable polyfunctional monomer having two or more functional groups 1 to 30 parts by weight and 0 to 40 parts by weight of other copolymerizable vinyl monomer as a whole
It was blended so that it would be 00 parts by weight, and was added to all monomers in an amount of 0.
It is preferably a transparent resin obtained by copolymerization in the presence of 1 to 5% by weight of a molecular weight modifier.

In the above, the amount of styrene used is preferably 30 to 60 parts by weight based on 100 parts by weight of all the monomers. If it is less than 30 parts by weight, it tends to be difficult to increase the refractive index, particularly to make the refractive index 1.54 or more. If it exceeds 60 parts by weight, it is difficult for the dispersion to be optically low, and it is particularly difficult for the Abbe number to be 35 or more, and the heat resistance tends to be low.

The above ester portion has 5 to 2 carbon atoms.
The amount of the methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group of 2 is preferably 10 to 70 parts by weight with respect to 100 parts by weight of all the monomers. If it is less than 10 parts by weight, the effect of improving heat resistance tends to be low, and if it exceeds 70 parts by weight, unreacted monomers of methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group tend to increase, and impact resistance is high. Tends to be inferior.

Specific examples of the radical-polymerizable polyfunctional monomer having two or more functional groups described above include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate,
Tetraethylene glycol diacrylate, glycerin diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,
6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, 1-acryloyl-2-hydroxy-3-acryloylpropane, pentaerythritol tetraacrylate, 1,1,1-trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, hexamethylolmelamine hexaacrylate,
N, N ′, N ″ -tris (2-acryloyloxyethyl) isocyanurate, 2,2′-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2′-bis [4
-(Acryloxy-diethoxy) phenyl] methane, bis (acryloxymethyl) tricyclo [5.2.1.0]
^2,6] decane, bis (acryloxymethyl) pentacyclo [6.5.1 ^3,6. 0 ^2,7 . 0 ^9,13] pentadecane, bis (acryloxymethyl) heptacyclo [10.5.
1.1 ^3,10 . 1 ^5,8 . 0 ^2,11 . 0 ^4,9 . 0 ^13,17 ] Eicosane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, glycerin dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,
10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, 1-methacryloyl-2-hydroxy-3-methacryloylpropane, pentaerythritol tetramethacrylate. , 1,1,1-trimethylolpropane trimethacrylate, dipentaerythritol hexamethacrylate, hexamethylolmelamine hexamethacrylate, N, N ′, N ″ -tris (2-methacryloyloxyethyl) isocyanurate, 2,2′-bis [4- (methacryloxy-diethoxy) phenyl] propane, 2,2'-
Bis [4- (methacryloxydiethoxy) phenyl]
Methane, bis (methacryloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, bis (methacryloxymethyl) pentacyclo [6.5.1, ^3,6 . 0 ^2,7 .
0 ^9,13 ] Pentadecane, bis (methacryloxymethyl)
Heptacyclo [10.5.1.1 ^3,10. 1 ^5,8 .
0 ^2,11 . 0 ^4,9 . 0 ^13,17 ] Eicosane, acrylic acid esters such as polyethylene glycol diacrylate, ethylene glycol bisallyl carbonate, diethylene glycol bisallyl carbonate, triethylene glycol bisallyl carbonate, tetraethylene glycol bisallyl carbonate, pentaethylene glycol bisallyl carbonate, Polypropylene glycol bisallyl carbonate, trimethylene glycol bisallyl carbonate, 3-hydroxypropoxy propanol bisallyl carbonate, glycerin bisallyl carbonate, triglycerin bisallyl carbonate, diallyl carbonate, diarylidene pentaerythritol, triarylidene sorbitol, diarylidene-2 , 2,6,6-Tetramethylol Cyclohexanone, triallylidene hexamethylol melamine, diarylidene-D-glucose, bisphenol A diallyl ether, bisphenol S diallyl ether, ethylene glycol diallyl ether, diethylene glycol diallyl ether, triethylene glycol diallyl ether, 1,1,1-trimethylol Propane triallyl ether, neopentyl glycol triallyl ether,
Allyl acrylate, methallyl acrylate, vinyl acrylate, diallyl phthalate (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate and mixtures of two or more thereof), allyl methacrylate, methallyl methacrylate, vinyl methacrylate, diallyl phthalate (diallyl orthophthalate,
Examples thereof include diallyl isophthalate, diallyl terephthalate and mixtures of two or more thereof, allyl compounds such as triallyl isocyanurate and allylidene compounds, and divinylbenzene. These are used alone or in combination of two or more.

Specific examples of the radical-polymerizable polyfunctional monomer having two or more functional groups described above include divinyl from the viewpoints of specific gravity, transparency, heat resistance and impact resistance. Benzene, diallyl phthalate, allyl acrylate, methallyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,1
Alkylene glycol diacrylate in which the alkylene group such as 2-dodecanediol diacrylate has 2 to 12 carbon atoms, allyl methacrylate, methallyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimeacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,9
-Nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate having an alkylene group having 2 to 2 carbon atoms.
An alkylene glycol dimethacrylate of 12 is preferred.

In the above, the range of use of the radical-polymerizable polyfunctional monomer having two or more functional groups is preferably 1 to 30 parts by weight with respect to 100 parts by weight of all monomers. It is particularly preferable that the amount is ˜15 parts by weight. Three
If it exceeds 0 parts by weight, the specific gravity tends to be 1.15 or more,
If it is less than 1 part by weight, problems such as heat resistance and machinability tend to occur.

The above-mentioned other copolymerizable vinyl-based monomer is not particularly limited as long as it does not impair the transparency of the polymer, and specific examples thereof include methyl acrylate and acrylic acid. Ethyl, propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-acrylate
Butyl, pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate, octadecyl acrylate, butoxyethyl acrylate, phenyl acrylate,
Acrylic esters such as benzyl acrylate, naphthyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, methacrylic acid T-Butyl acid, pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n methacrylate
-Octyl, dodecyl methacrylate, octadecyl methacrylate, butoxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, glycidyl methacrylate, methacrylic acid esters such as 2-hydroxyethyl methacrylate, α-methylstyrene, α-ethylstyrene, α-fluorostyrene,
Aromatic vinyl compounds such as α-chlorostyrene, α-bromostyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene and methoxystyrene, N-
Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide,
N-substituted maleimides such as N-methoxyphenylmaleimide and N-carboxyphenylmaleimide, acrylamide, methacrylamide, N-dimethylacrylamide,
(Meth) acrylamides such as N-diethylacrylamide, N-dimethylmethacrylamide, N-diethylmethacrylamide, calcium acrylate, barium acrylate, lead acrylate, tin acrylate acrylate, zinc acrylate, calcium methacrylate, Examples include (meth) acrylic acid metal salts such as barium methacrylate, lead methacrylate, tin methacrylate and zinc methacrylate, unsaturated fatty acids such as acrylic acid and methacrylic acid, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. . These are used alone or in combination of two or more.

Among the above examples, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-methacrylic acid are preferable in terms of transparency, heat resistance, and impact resistance.
Butyl, i-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n methacrylate
Methacrylic acid esters such as octyl, butoxyethyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, glycidyl methacrylate are preferred.

When the amount of the other copolymerizable vinyl-based monomer exceeds 40 parts by weight, the refractive index tends to be small, particularly the refractive index tends to be less than 1.54, and the specific gravity tends to be large. The specific gravity tends to be 1.15 or more.

As the molecular weight modifier used in the plastic lens substrate described above, general chain transfer agents, mercaptans, dialkyldisulfides, chloroform, carbon tetrachloride and the like can be used. Considering transparency, color, heat resistance, etc.,
The dimer of α-methylstyrene is preferred. The molecular weight modifier is preferably used in an amount of 0.1 to 5% by weight based on 100 parts by weight of the total monomers. If it is less than 0.1% by weight, the haze value tends to be high, and if it exceeds 5% by weight, various physical properties such as heat resistance may be deteriorated.

In the above-mentioned method for producing a plastic lens, as the polymerization initiator, those used in ordinary radical polymerization can be used as they are. For example,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4′-bis (t-butylperoxy) (Oxy) valerate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dinormalpropyl peroxydicarbonate, dimethoxyisopropyl Peroxydicarbonate, cumylperoxy neodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, di-t-butyldiperoxy Isophthalate, t-butyl Organic peroxides such as peroxyisopropyl carbonate, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,
4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,
2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile), 2-phenylazo-2,4-dimethyl-4- Examples thereof include azo-based polymerization initiators such as methoxyvaleronitrile and 2,2′-azobis (2-methylpropane). Two or more of these polymerization initiators may be used in combination.

The above-mentioned polymerization initiator is preferably used in the range of 0.001 to 10% by weight based on 100 parts by weight of all the monomers, and the surface condition of the obtained polymer and the polymerization time are taken into consideration. Then, it is 0.01 with respect to 100 parts by weight of all the monomers.
It is particularly preferable to use ˜5% by weight.

In the production of the polymer used for the plastic lens substrate described above, the above-mentioned molecular weight regulator and polymerization initiator are used by being dissolved in a monomer, and the resin obtained by the polymerization is a cross-linked polymer. Because there is usually
Curing and molding by a cast polymerization method is preferable. The curing temperature varies depending on the polymerization initiator used, but is 30 to 12
0 ° C is suitable. However, in order to obtain a molded product with less distortion, it is preferable to cure slowly at a relatively low temperature.

In the use of the plastic lens substrate described above, antioxidants such as phosphite-based compounds, phenol-based compounds, thioether-based compounds, aliphatic alcohols and fatty acids are used from the viewpoints of prevention of deterioration, thermal stability and processability. Ester, phthalate ester, triglycerides, fluorine-based surfactants, release agents such as higher fatty acid metal salts, other lubricants, plasticizers, antistatic agents, UV absorbers, flame retardants, heavy metal deactivators, etc. are added. You may use it. These are preferably used by dissolving in a monomer during polymerization.

The surface of the plastic lens substrate described above is coated with an inorganic compound such as MgF2 or SiO2 by a vacuum deposition method, a sputtering method, an ion plating method, or the like, and the surface of the molded product is an organic silicon such as a silane coupling agent. By hard coating a compound, vinyl monomer, melamine resin, epoxy resin, fluorine resin, silicone resin, etc., it is possible to improve moisture resistance, optical characteristics, chemical resistance, abrasion resistance, antifog, etc. .

In the present invention, the plastic lens substrate preferably has a specific gravity of 1.15 or less, a refractive index of 1.54 or more and an Abbe number of 35 or more.

The surface of the plastic lens base material contains an alkyl acrylate or alkyl methacrylate and an aromatic vinyl compound as essential components,
Furthermore, a resin film containing as a main component a copolymer having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group and an alkoxysilyl group is provided as a primer layer, and a cured product layer of a silicone resin is provided thereon. The plastic lens thus obtained has preferable characteristics.

Examples of the alkyl acrylate used as a component of the above-mentioned primer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, etc. Examples of the methacrylic acid alkyl ester Examples thereof include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate and the like. Further, examples of the aromatic vinyl compound include styrene and α-methylstyrene. The copolymer used as the primer also has a reactive residue such as a hydroxyl group, a carboxyl group, an epoxy group and an alkoxysilyl group. These reactive residues are glycidyl acrylate, glycidyl methacrylate and acrylic acid 2
-Hydroxyethyl, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) triethoxysilane, γ- (methacryloxypropyl) tributoxysilane, etc. It can be introduced by copolymerizing a polymerizable monomer having a reactive residue of the above with the above-mentioned monomer.

The mixing ratio of these monomers is 10 to 60% by weight of alkyl acrylate or alkyl methacrylate, and 30 to 70 for aromatic vinyl compounds.
%, And the polymerizable monomer having a reactive residue is preferably in the range of 1 to 20% by weight.

When the acrylic acid alkyl ester or methacrylic acid alkyl ester is less than 10% by weight, the flexibility of the primer film tends to decrease, and when it exceeds 60% by weight, the adhesion to the substrate tends to decrease. . If the amount of the aromatic vinyl compound is less than 30% by weight, the adhesion to the base material tends to decrease, and if it exceeds 70% by weight, the solubility in the organic solvent decreases, so that the film forming property tends to decrease. Further, if the amount of the polymerizable monomer having a reactive residue is less than 1% by weight or more than 20% by weight, the adhesion of the silicone-based cured film tends to decrease.

All the above-mentioned monomers which are the constituents of the polymer used for the primer layer are polymerized in the presence of a polymerization initiator to give a polymer. As the polymerization initiator, those used in ordinary radical polymerization can be used. For example, the same polymerization initiator as that used for the plastic lens substrate described above can be used.
The polymerization initiator is 0.00 based on 100 parts by weight of all the monomers.
It is preferably used in the range of 1 to 10 parts by weight, and is 0.01 in view of the molecular weight of the obtained polymer and the polymerization time.
-5 parts by weight are particularly preferred.

The layer composed of the above-mentioned primer is applied to the substrate by applying a solution of the above-mentioned polymer (primer solution) to the substrate by a dipping method, a spin coat method, a flow coat method, a spray method or the like. It is formed by air drying or drying and curing at 50 to 130 ° C. for 3 to 60 minutes. The thickness of the primer layer is 1 to
The thickness is preferably 10 μm, and particularly preferably 2 to 5 μm. Further, if necessary, a silicone-based or fluorine-based surfactant, an ultraviolet absorber, a dyeing agent or the like can be added.

As the solvent used in the above primer solution, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, cyclopentanol and hexanol, acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone, acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate, ethers such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, carbitols such as methyl carbitol, ethyl carbitol and butyl carbitol, dioxane, Tetrahydrofuran, polar aprotic solvent such as dimethylformamide, pentane, hexane, heptane, octane, cyctopentane, cyctohexane, benzene, toluene,
There are hydrocarbons such as xylene.

The silicone resin is, for example, a compound represented by the chemical formula 1 [general formula (1)]:

Embedded image R ¹ R ² _a Si (OR ³ ) _3-a (I) (wherein R ¹ is an organic group containing an epoxy group having 2 to 8 carbon atoms, and R ² is an organic group having 1 to 6 carbon atoms). An alkyl group, an alkenyl group, a halogenated alkyl group or an allyl group, R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a is an integer of 0 to 2). There are organic silicon compounds or partial hydrolysates thereof. More specific examples are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltris (methoxyethoxy) silane, γ-glycidoxypropylmethyldimethoxysilane, γ There are organosilicon compounds such as glycidoxypropylmethyldiethoxysilane or partial hydrolysates thereof.

A solution prepared by dissolving (and dispersing) the above silicone resin in water or a solvent such as alcohol such as methanol, ethanol, isobutanol, diacetone alcohol or the like, together with inorganic fine particles, is preferably used. A cured product layer can be obtained by applying the composition on the primer layer and heating and curing at 50 to 140 ° C.

The above-mentioned inorganic fine particles impart a preferable hardness to the cured film of the silicone resin. The inorganic fine particles include antimony oxide sol, silica sol, titania sol, alumina sol and the like, and those having a particle size of 1 to 200 mμ, particularly 5 to 100 mμ are preferable. If the particle size of the inorganic fine particles is smaller than 1 mμ, there is no effect of improving the hardness of the cured film of the silicone resin, and if it exceeds 200 mμ, the transparency decreases. The inorganic fine particles are 5 to 2 with respect to 100 parts by weight of the silicone resin.
It is preferably used in an amount of 00 parts by weight, particularly 20 to 100 parts by weight. If the amount of the inorganic fine particles used is too small, there is no effect of improving the hardness of the cured film of the silicone resin, and if it is too large, the cured film of the silicone resin becomes brittle. As the inorganic fine particles, a commercially available colloidal solution dispersed in water or an organic solvent can be used. Examples of such inorganic fine particles include Snowtex O, methanol silica gel, alumina sol 520, titanium oxide sol NTS-1.
0R (both manufactured by Nissan Chemical Co., Ltd.) and alumina clear sol (manufactured by Kawaken Fine Chemical Co., Ltd.).

If desired, the silicone resin of the present invention may contain perchlorates such as aluminum chelate, perchloric acid, ammonium perchlorate and aluminum perchlorate.
A curing catalyst such as an alkali metal salt such as sodium acetate or potassium propionate or a quaternary ammonium salt such as tetramethylammonium hydroxide can also be used.

[0037]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

Production Examples 1-1 to 1-12 [Production of Plastic Lens Substrate] In a mixed solution having the composition shown in Table 1, as a radical polymerization initiator,
After adding 0.5 part of lauroyl peroxide and 0.2% by weight of 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and stirring sufficiently, a mold consisting of two pieces of glass and a gasket was formed. It was poured and heated from 30 ° C to 90 ° C over 20 hours. The cured lens was removed from the mold and heat-treated at 120 ° C. for 1 hour.

The refractive index, Abbe number, specific gravity, heat resistance, haze value (transparency), impact resistance, chemical resistance, machinability, etc. of the products obtained in Production Examples 1-1 to 1-12 were examined. , Shown in Table 2.

The characteristic evaluation was based on the following methods. -Refractive index, Abbe number: It measured at 20 degreeC using the Abbe refractometer (made by Atago Co., Ltd.). D line (589.3n
The value in m) is shown. -Specific gravity: Measured by the water substitution method. -Heat resistance: TMA (made by Seiko Instruments Inc.) was used to measure Tg (softening temperature). Haze value (transparency): according to ASTM D 1003
The haze value of a lens having a center thickness of 5 mm was measured. The smaller the haze value, the better the transparency. -Impact resistance: A lens having a center thickness of 2 mm was evaluated according to the FDA standard. (Evaluation) ◯: No cracking, ×: Cracking-Chemical resistance: Dipped in acetone or toluene at room temperature for 24 hours, and those having no cloudiness on the surface in any solvent were passed. (Evaluation) ○: No change in appearance, △: Slightly cloudy, ×:
Cloudy or Melting-Machinability: Judgment was made based on whether or not the lens can be cut by a scoring machine for eyeglass lenses. (Evaluation) ○: Can be cut, ×: Shavings are sticky

In the following, ST is styrene, TCDM
A is tricyclo [5.2.1.02,6] dec-8-yl methacrylate, NBMA is norbornyl methacrylate,
MMA is methyl methacrylate, AMA is allyl methacrylate, EGDM is ethylene glycol dimethacrylate, α-MSD is a dimer of α-methylstyrene, and NOM.
Is n-octyl mercaptan, and TDM is t-dodecyl mercaptan. The amounts of α-MSD, NOM, and TDM used are shown in weight% based on the total monomers.

[0042]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Mixed liquid composition ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Monomer composition (weight part) α-MSD manufacturing example ST TCDMA NBMA MMA AMA EGDM (wt%) ──────────────────────────────────── 1-1 50 30-10 10-1.0 1-230 50-10 10-1.0 1-350 30-10-10-10 1.0 1-430 50-10-10 1.0 1-5 50 30-10-10 NOM 1.0 1-6 50 30- 10-10 TDM 1.0 1-7 50-30 10 10-1.0 1-8 30-50 10 10-1.0 1-9 50-30 10-10 1.0 1-10 30-50 10-10 1.0 1-11 50- 30 10-10 NOM 1.0 1-12 50-30 30-10 TDM 1.0 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━ ━

[0043]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Evaluation results ━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Refractive index Abbe number Specific gravity Heat resistance Cloudiness ratio Impact resistance Chemical resistance Cutting Manufacturing example (- ) (-) (G / cm3) (℃) (%) Hammerability Product quality Processability ────────────────────────────── ─────── 1-1 1.55 40 1.08 117 0.6 ○ ○ ○ 1-2 1.54 43 1.08 130 0.5 ○ ○ ○ 1-3 1.55 41 1.08 115 0.5 ○ ○ ○ 1-4 1.54 43 1.09 128 0.6 ○ ○ ○ 1-5 1.55 41 1.08 108 0.9 * ○ ○ ○ 1-6 1.55 41 1.09 109 0.8 ○ ○ ○ 1-7 1.55 40 1.08 116 0.6 ○ ○ ○ 1-8 1.54 43 1.08 129 0.6 ○ ○ ○ 1-9 1.55 41 1.08 115 0.6 ○ ○ ○ 1-10 1.54 43 1.09 127 0.6 ○ ○ ○ 1-11 1.55 41 1.08 110 0.9 * ○ ○ ○ 1 -12 1.55 41 1.08 107 0.9 ○ ○ ○ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Colored yellow.

Production Examples 2-1 to 2-7 [Preparation of Primer Coating Liquid] In a flask equipped with a stirrer, 100 parts by weight of a mixed solution having the composition shown in Table 3, 200 parts by weight of ethyl cellosolve, t-as a radical polymerization initiator were used. 0.2 part by weight of butylperoxy-2-ethylhexanoate and 0.05 part by weight of a dimer of α-methylstyrene as a chain transfer agent were added, and the mixture was heated under a nitrogen atmosphere to 80
After heating and stirring at 4 ° C for 4 hours, the mixture was further heated and stirred at 90 ° C for 2 hours to complete the reaction. This solution was mixed with diacetone alcohol, ethyl cellosolve, methyl isobutyl ketone, isobutyl acetate, isopropanol, etc. to give a solid content of 10% by weight.
Adjusted to.

Production Example 3 [Preparation of silicone resin coating solution] In a flask equipped with a stirrer, 100 g of γ-glycidoxypropyltrimethoxysilane, 100 g of γ-glycidoxypropylmethyldiethoxysilane, and 8 of isobutyl alcohol.
Add 0 g and keep the inside of the flask at 0 to 10 ° C.
35 g of 5N dilute hydrochloric acid was added dropwise over 30 minutes, and colloidal silica SNO-TEX O (manufactured by Nissan Kagaku Co., Ltd.,
300 g (containing 20% SiO2) was added and the mixture was stirred at room temperature for 20 hours, then 50 g of ethanol and 70 of ethyl cellosolve were added.
After adding 2 g of 10% potassium propionate aqueous solution, the pH was adjusted to 6 to 7 with acetic acid.

Examples 1 to 15 and Comparative Examples 1 to 3 The lens base materials obtained in Production Examples 1-1 to 1-12 were dipped with the primer solutions obtained in Production Examples 2-1 to 2-7. After applying at a pulling speed of 20 cm / min,
Drying was performed with a hot air dryer at 90 ° C. for 1 hour. Subsequently, the silicone resin coating solution obtained in Production Example 3 was applied to this primer-treated lens by a dipping method (pulling rate: 30 cm / min), and then heat-cured at 110 ° C. for 2 hours with a hot air dryer. . The thickness of the primer and the silicone resin cured film thus obtained are each 3 μm.
Met. Further, the adhesion of the primer to the obtained lens substrate, the adhesion of the cured silicone resin film to the lens subjected to the primer treatment, and the scratch resistance were examined, and the results are shown in Table 4.

The adhesion and scratch resistance were examined by the following methods.・ Adhesion: The number of squares that were not peeled off after putting 11 pieces of cross-cuts 1 mm apart in the length and width with a knife on the cured film and adhering serothepes (made by Nichiban) I checked. (Evaluation) ○: 100/100, ×: 0/100 ・ Scratch resistance: using a steel wool (# 0000), 5
The cured film was reciprocated 10 times with a load of 00 g, and the scratches on the surface were visually evaluated. (Evaluation) ○: no scratch, ×: scratch

In the following, MMA is methyl methacrylate, ST is styrene, HEMA is 2-hydroxyethyl methacrylate, MA is methacrylic acid, GMA is glycidyl methacrylate, and SiMA is γ- (methacryloxypropyl) trimethoxysilane. .

[0049]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 3 Mixed liquid composition (parts by weight) ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Manufacturing example MMA ST HEMA MA GMA SiMA ───── ─────────────────────────────── 2-1 47.5 47.5 5.0 − − − 2-2 47 .5 47.5 -5.0 --- 2-3 47.5 47.5 --- 5.0 -2-4 47.5 47.5 --- 5.0 2-5 100 --- --- 2-6 -100----2-7 50.0 50.0----━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━

[0050]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 4 Trial results ━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Lens base material Primer Adhesion Scratch resistance (Production example) (Production example) ( -) (-) ──────────────────────────────────── Example 1 1-1 2-4 ○ ○ 〃 2 1-2 2-4 ○ ○ 〃 3 1-3 2-4 ○ ○ 〃 4 1-4 4-4 ○ ○ 〃 5 1-5 2-4 ○ ○ 〃 6 1-6 2-4 ○ ○ 〃 7 1-7 2-4 ○ ○ 〃 8 1-8 2-4 ○ ○ 〃 9 1-9 2-4 ○ ○ 〃 10 1-10 2-4 ○ ○ 〃 11 1-11 2-4 ○ ○ 〃 12 1-12 2-4 ○ ○ 〃 13 1-3 2-1 ○ ○ 〃 14 1-3 2-3 2 ○ ○ 〃 15 1-3 2-3 ○ ○ Comparative Example 1 1-3 2-5 × × 〃 2 1-3 2-6 × × 〃 3 1-3-3 2-7 × × ━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━

[0051]

The plastic lens according to claim 1 or 2 can have a low specific gravity, low dispersibility (high Abbe number), excellent heat resistance, and excellent adhesion and resistance to a cured silicone resin film. Good scratch resistance. The plastic lens according to claim 3 has a low specific gravity, excellent transparency and machinability, low dispersibility (high Abbe number), high refractive index, and high heat resistance, in addition to the effects of the first aspect. Excellent in. The plastic lens in claim 4,
In addition to the effect exhibited by the first aspect, it has a low specific gravity, excellent transparency, machinability, low dispersibility (high Abbe number), high refraction and high heat resistance, but specific gravity and transparency. It is particularly preferable in terms of heat resistance and impact resistance. The plastic lens according to claim 5 has a low specific gravity, excellent transparency and machinability, low dispersibility (high Abbe number), high refractivity and high heat resistance, in addition to the effects of the first aspect. However, it is particularly preferable in terms of specific gravity and low dispersibility.
The plastic lens of claim 6 has a low specific gravity, transparency, in addition to the effect of the one of claim 1.
It excels in machinability, low dispersibility (high Abbe number), high refractivity and high heat resistance, but transparency and heat resistance are particularly preferable. The plastic lens according to claim 7 has the best balance of low specific gravity, low dispersibility (high Abbe number), and high refractive index, in addition to the effect of the first aspect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Fumiaki Kanaga No. 14 Goi South Coast, Ichihara City, Chiba Hitachi Chemical Co., Ltd. Goi Factory

Claims (7)

[Claims] 1. An alkyl acrylate ester is provided on the surface of a plastic lens substrate containing a polymer containing a methacrylic acid ester or an acrylate ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion as an essential component. Alternatively, a resin film containing, as an essential component, a methacrylic acid alkyl ester and an aromatic vinyl compound as a main component and a copolymer having at least one functional group selected from a hydroxyl group, a carboxyl group, an epoxy group and an alkoxysilyl group is used as a primer. -A plastic lens having a layer and a cured layer of a silicone resin on the layer. 2. A polymer containing methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion as an essential component is styrene, and an alicyclic ring having 5 to 22 carbon atoms in the ester portion. A polymer comprising a methacrylic acid ester or an acrylic acid ester having a hydrocarbon group, a radically polymerizable polyfunctional monomer having two or more functional groups, and another copolymerizable vinyl monomer. 1. The plastic lens according to 1. 3. A polymer containing a methacrylic acid ester or an acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion as an essential component, the plastic lens substrate is 30 to 60 parts by weight of styrene, 10 to 70 parts by weight of methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion, and radically polymerizable polyfunctional monomer 1 to 30 having 2 or more functional groups Parts by weight and 0 to 40 parts by weight of another copolymerizable vinyl monomer so that the total amount is 100 parts by weight. The plastic lens according to claim 2, which is a transparent resin obtained by copolymerization in the presence. 4. A methacrylic acid ester or acrylic acid ester having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester moiety is cyclohexyl methacrylate, norbornyl methacrylate, norbornyl methyl methacrylate,
Tricyclomethacrylate [5.2.1.0 ^2,6 ] deca
8-yl and tricyclomethacrylate [5.2.1.0
The plastic lens according to any one of claims 1 to 3, which is one or more compounds selected from the group consisting of ^2,6 ] deca-4-methyl. 5. The polyfunctional monomer is divinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate, methallyl acrylate, methallyl methacrylate, alkylene glycol diacrylate in which the alkylene group has 2 to 12 carbon atoms, alkylene group. 4. The plastic lens according to claim 2 or 3, wherein the plastic lens is one or more monomers selected from the group consisting of alkylene glycol dimethacrylates having 2 to 12 carbon atoms. 6. The molecular weight modifier is α-methylstyrene 2
The plastic lens according to claim 2 or 3, which is a monomer. 7. The plastic lens substrate has a specific gravity of 1.1.
The plastic lens according to claim 1, which has a refractive index of 5 or less, a refractive index of 1.54 or more, and an Abbe number of 35 or more.