JPH04239539A - Plastic lens - Google Patents

Abstract

PURPOSE:To obtain plastic lens having high refractive index and good adhesion of coating film and reduced in discoloration by weather. CONSTITUTION:The objective plastic lens obtained by mixing a composition obtained by reacting 4,4'-bis(methacryloylthio)diphenyl sulfide with ethylene glycol dithioglycolate with styrene and azobisisobutyronitrile to afford a solution and pouring the solution into a mold for lens forming and heating the solution to give a plastic lens and providing an acrylic primer layer, silicone hard coat layer and refraction preventing layer of inorganic compound on the surface of the resultant plastic lens.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to optical materials and lenses that have a high refractive index and low water absorption, and more particularly to plastic lenses that have excellent scratch resistance and antireflection effects.

0002

[Prior Art] Conventionally, polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate polymers, etc. have been used as organic optical materials. The demand for it has been increasing in recent years due to its excellent properties.

However, conventional organic optical materials, such as polymethyl methacrylate resins, have a high hygroscopic property, which causes their shape and refractive index to change, making them unstable as optical materials. In addition, polystyrene resin,
In the case of polycarbonate resin, it has drawbacks such as optical birefringence, generation of scattered light, and decrease in transparency due to changes over time. Furthermore, the polymer of diethylene glycol diallyl carbonate has a low refractive index (refractive index = 1.499).
Therefore, the range of its application as an optical material was naturally limited.

Various resins for optical materials have been proposed to improve these drawbacks. Examples of these include, for example, JP-A-57-28115 and JP-A-57-2811.
Publication No. 6, Publication No. 59-184210, Publication No. 60-73
Publication No. 14, Publication No. 60-179406, Publication No. 60-2
No. 17301, No. 60-186514, No. 6
No. 0-166307, No. 60-103301, No. 60-124607, No. 62-232414
No. 62-235901, No. 62-267
Publication No. 316, Publication No. 63-15811, Publication No. 63-4
No. 6213, No. 63-72707, No. 63-
Publication No. 75022, Publication No. 63-113012, Publication No. 6
No. 3-130614, No. 63-130615, No. 63-170401, No. 63-170404
No. 63-191813, No. 63-248
No. 811, No. 63-251408, No. 63-
Publication No. 268707, Publication No. 64-54021, etc. can be mentioned. However, the cured products obtained by these prior art techniques were not necessarily satisfactory as optical materials, as they were optically non-uniform, had significant weather-resistant coloring, and lacked dimensional stability.

A method for solving these drawbacks is disclosed in Japanese Patent Application Laid-Open No. 2-113027, and improvements have been made in the physical properties of lenses as well. However, the scratch resistance and light transmittance are insufficient to make a practical plastic lens, and there are problems with the storage stability of intermediate products during the manufacturing process.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to overcome the drawbacks of the conventional resins for optical materials, and to provide a plastic that has a high refractive index, low water absorption, and excellent scratch resistance and antireflection effect. Our goal is to provide lenses.

[0007]

[Means for solving the problem] As a result of studies to solve the above problem, (A) formula (I)

[0008]

4,4'-bis(methacryloylthio)diphenyl sulfide represented by [Chemical formula 3] and (B) formula (II) R-(SH)n

(II) (wherein R represents an organic group consisting of a polyvalent aliphatic or aromatic hydrocarbon, and n represents an integer of 2 or more). ■ On the surface of a plastic lens using a material obtained by polymerizing a curable composition consisting of a prepolymer having a thioether skeleton and other polymerizable monomers, ■ in the solid content with a film thickness of 0.1 to 3.0 μm. Titania 5
Acrylic primer layer containing ~40% by weight Formula (III)
) consisting of one or more hydrolysates of organosilicon compounds and/or partial condensates thereof.
Silicone hard coat layer with a thickness of 5 to 6.0 μm

[0009]

[Image Omitted] (In the formula, R1 and R2 are hydrocarbon groups and are not particularly limited, including amino groups, epoxy groups, aryl groups, halogens,
It may have a substituent selected from epoxy groups. R
3 is a hydrolyzable group selected from alkoxy, halogen, acyloxy, and phenoxy groups, and a and b are 0 or 1) ■ Excellent plastic lenses can be obtained by sequentially providing antireflection layers of inorganic compounds. I understand.

[0010] The curable composition used in the plastic lens according to the present invention is prepared by reacting components (A) and (B) in a solvent in the presence of a base catalyst, removing the solvent, and then adding other polymerizable components. It can be obtained by mixing with monomers or by addition reaction in other polymerizable monomers in the presence of a base catalyst.

4,4'-bis(methacryloylthio)diphenyl sulfide represented by formula (I) used in the present invention is easy to mix with other organic compounds and has extremely low affinity for water. , and its cured product has a high refractive index (refractive index=1.689). The formula (II) used as component (B) in the present invention
), n is 2 or more,
Preferably, aliphatic polythiols or aromatic polythiols in which n is an integer of 2 to 5 are used. Representative examples of such polythiols include, for example, 9,10
-anthracene dimethanethiol, 1,11-undecanedithiol, 4-ethylbenzene-1,3-dithiol, 1,2-ethanedithiol, 1,8-octanedithiol, 1,18-octadecanedithiol, 2,5-
Dichlorobenzene-1,3-dithiol, 1,3-(4
-chlorophenyl)propane-2,2-dithiol, 1
, 1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 1,4-cyclohexanedithiol,
1,1-cycloheptanedithiol, 1,1-cyclopentanedithiol, 4,8-dithiaundecane-1,1
1-dithiol, dithiopentaerythritol, dithiothreitol, 1,3-diphenylpropane-2,2-
Dithiol, 1,3-dihydroxy-2-propyl-2
',3'-dimercaptopropyl ether, 2,3-dihydroxypropyl-2',3'-dimercaptopropyl ether, 2,6-dimethyloctane-2,6-dithiol, 2,6-dimethyloctane-3, 7-dithiol, 2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol, 3,
3-dimethylbutane-2,2-dithiol, 2,2-dimethylpropane-1,3-dithiol, 1,3-di(4
-methoxyphenyl)propane-2,2-dithiol,
3,4-dimethoxybutane-1,2-dithiol, 10
, 11-dimercaptoundecanoic acid, 6,8-dimercaptooctanoic acid, 2,5-dimercapto-1,3,4-
Thiadiazole, 2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 3,4-dimercaptobutanol,
3,4-dimercaptobutyl acetate, 2,3-dimercapto-1-propanol, 1,2-dimercapto-
1,3-butanediol, 2,3-dimercaptopropionic acid, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl-2',3'-dimethoxypropyl ether, 3,4-thiophenedithiol , 1,10-decanedithiol, 1,12-dodecanedithiol, 3,5,5-trimethylhexane-1,1-
Dithiol, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1
, 5-naphthalenedithiol, 2,6-naphthalenedithiol, 1,9-nonanedithiol, norbornene-2
, 3-dithiol, bis(2-mercaptoisopropyl) ether, bis(11-mercaptoundecyl) sulfide, bis(2-mercaptoethyl) ether, bis(2-mercaptoethyl) sulfide, bis(18-mercaptooctadecyl) sulfide , bis(8-mercaptooctyl) sulfide, bis(12-mercaptodecyl) sulfide, bis(9-mercaptononyl) sulfide, bis(4-mercaptobutyl) sulfide, bis(3-mercaptopropyl) ether, bis(3- mercaptopropyl) sulfide, bis(6-mercaptohexyl) sulfide, bis(7-mercaptoheptyl) sulfide, bis(5-mercaptopentyl) sulfide, 2,2'-bis(mercaptomethyl)acetic acid, 1,
1'-bis(mercaptomethyl)cyclohexane, bis(mercaptomethyl)dyrene, phenylmethane-1,
1-dithiol, 1,2-butanedithiol, 1,4-
Butanedithiol, 2,3-butanedithiol, 2,2
-butanedithiol, 1,2-propanedithiol, 1
, 3-propanedithiol, 2,2-propanedithiol, 1,2-hexanedithiol, 1,6-hexanedithiol, 2,5-hexanedithiol, 1,7-heptanedithiol, 2,6-heptanedithiol, 1, 5
-pentanedithiol, 2,4-pentanedithiol,
3,3-pentanedithiol, 7,8-heptanedecanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 2-
In addition to dithiols such as methylcyclohexane-1,1-dithiol, 2-methylbutane-2,3-dithiol, ethylene glycol dithioglycolate, and ethylene glycol bis(3-mercaptopropionate), 1,2
, 3-propane trithiol, 1,2,4-butane trithiol, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), pentaerythritol tris(3-mercapto) propionate), 1,3,5-benzene trithiol, 2,4,6-mesitylene trithiol, neopentanetetrathiol, 2,2'-bis(mercaptomethyl)-1,3- Propanedithiol, pentaerythritol tetrakis (3-mercaptopropionate), 1,3,5-benzene trithiol,
Examples include 2,4,6-toluentrithiol and 2,4,6-mesitylenetrithiol. The polythiols as component (B) exemplified above can be used alone or as a mixture of two or more.

The above formula (I) used as component (A)
When carrying out an addition reaction between 4,4'-bis(methacryloylthio)diphenyl sulfide represented by the formula (B) and the polythiol represented by the formula (II) used as the component (B), The functional group equivalent ratio of the mercapto group of component (B) is 0.0
It is preferably within the range of 2 to 1.01, particularly 0.
The range is preferably from 0.05 to 0.60. When the functional group equivalent ratio of the mercapto group of component (B) to the methacryloyl group of component (A) is less than 0.02, the cured product is generally brittle and sufficient impact resistance cannot be obtained. In addition, if the functional equivalent ratio of the mercapto group of component (B) to the methacryloyl group of component (A) is greater than 1.01, unreacted mercapto groups may reduce the stability of the composition and increase the viscosity of the composition. There are problems such as a rise in temperature and non-uniformity of the cured product due to non-uniformity of the polymerization reaction.

[0013] There are no particular limitations on the use of a solvent in the addition reaction of components (A) and (B), but it is desirable that the solvent can dissolve components (A) and (B) well. Examples of such solvents include ether solvents such as diethyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran, aromatic hydrocarbon solvents such as benzene and toluene, and chlorine solvents such as dichloromethane and carbon tetrachloride, which have relatively low boiling points. Examples include solvents.

When a high boiling point solvent is used in the addition reaction of components (A) and (B), if a method involving heating is used to remove the solvent, if component (A) remains,
This is not preferred because it tends to cause gelation due to homopolymerization of component (A).

For gelation, it is possible to add a phenolic or amine inhibitor to the extent that it does not inhibit the next step of polymerization between other polymerizable monomers. Further, when it is necessary to remove the base catalyst for addition reaction, known methods such as adsorption, extraction, vacuum suction, etc. can be applied as long as they do not affect the next step of polymerization. In particular, for the removal of amine compounds, adsorption removal methods using neutral, acidic alumina, and acidic ion exchange resins can be applied, and in the case of low boiling point amine compounds, removal methods using vacuum suction can also be used. be able to.

The temperature at which the addition reaction is carried out cannot be unconditionally defined as it varies depending on the type and amount of component (B), or the type and amount of the basic catalyst used, but it is generally 0 to 100°C, preferably 20°C. ~60°C. Even if the addition reaction temperature exceeds 100° C., depending on the type and amount of the basic catalyst used, homopolymerization of component (A) may be prevented in some cases, but gelation often occurs, which is not preferable. On the other hand, although the addition reaction proceeds below 0°C, the reaction rate is extremely slow, which is unfavorable in terms of production.

As the base catalyst for the addition reaction, basic ion exchange resins, potassium t-butoxide, phosphine compounds, and amine compounds can be used, but in particular, phosphine compounds or amine compounds can be used. is preferred.

Examples of phosphine compounds include triphenylphosphine, tri-n-butylphosphine,
Examples include triethylphosphine. Examples of amine compounds include pyridine, N,N-dimethylaniline, N,N-diethylaniline, trimethylamine, triethylamine, tri(n-propyl)amine, tri(iso-propyl)amine, tri(n- butyl)amine, tri(iso-butyl)amine, tri(sec-
butyl) amine, dimethylethylamine, diethylmethylamine, diethylamine, triethanolamine, dimethylethanolamine, monomethyldiethanolamine, and the like.

These base catalysts may be used alone or in combination, and the amount used varies depending on the type and amount of component (B) used, so it cannot be unconditionally specified, but generally (A 0.01 to 3% by weight, preferably 0.03 to 1% by weight based on the total amount of component ) and component (B)
Weight%. When the amount of the base catalyst used is less than 0.01% by weight, it does not substantially function as a catalyst, and often (A)
Homopolymerization of the methacryloyl groups of the components occurs. On the other hand, when the amount of the base catalyst used exceeds 3% by weight, not only the effect of using a large amount is not observed, but also coloration occurs during polymerization, which is not preferable. Furthermore, even if the base catalyst is removed after the reaction, a large amount of removal agent is required, which is rather undesirable.

In the addition reaction, it is preferable to carry out the addition reaction in an inert gas atmosphere in order to prevent the formation of disulfide due to autooxidation of component (B).

After the addition reaction is completed, a prepolymer having a polythioether skeleton can be obtained by removing the solvent.

The prepolymer having a polythioether skeleton thus obtained has a structure in which the molecular ends are capped with polymerizable vinyl groups, and has excellent storage stability.

The prepolymer having a polythioether skeleton obtained as described above is mixed with other polymerizable monomers.

The other polymerizable monomers may be any ones that can be copolymerized with the prepolymer having a polythioether skeleton, such as unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, Examples include unsaturated dibasic acids and their derivatives, vinyl cyanide compounds such as (meth)acrylonitrile, and the like. Examples of unsaturated fatty acid esters include methyl (meth)acrylate (in this specification, refers to both methyl acrylate and methyl methacrylate; the same applies in other cases), ethyl (meth)acrylate, butyl (meth)acrylate, 2- ethylhexyl (meth)acrylate,
Alkyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, (iso)bornyl (meth)acrylate, adamantyl (meth)acrylate, etc. ) acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 1-naphthyl (
meth)acrylate, fluorophenyl(meth)acrylate, chlorophenyl(meth)acrylate, bromophenyl(meth)acrylate, tribromophenyl(
Aromatic acrylic esters such as meth)acrylate, methoxyphenyl(meth)acrylate, cyanophenyl(meth)acrylate, biphenyl(meth)acrylate, bromobenzyl(meth)acrylate, fluoromethyl(meth)acrylate, chloromethyl(meth)acrylate Acrylate, haloalkyl (meth)acrylates such as bromoethyl (meth)acrylate, trichloromethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, etc., as well as glycidyl (meth)acrylate, alkyl Examples include (meth)acrylic acid esters such as amino (meth)acrylate. In addition, α-fluoroacrylic acid ester, α-cyanoacrylic acid ester, etc.
Examples include substituted acrylic esters.

[0025] Examples of the aromatic vinyl compound include styrene,
or α-methylstyrene, α-ethylstyrene, α-
Examples include α-substituted styrenes such as chlorostyrene, and nuclear-substituted styrenes such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene.

[0026] Unsaturated fatty acids and their derivatives include:
Examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylamide, and (meth)acrylic acid.

Examples of unsaturated dibasic acids and derivatives thereof include N-methylmaleimide, N-ethylmaleimide, N-
Butylmaleimide, N-cyclohexylmaleimide, N
- N-substituted maleimides such as phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, maleic acid,
Examples include maleic anhydride and fumaric acid.

In addition to the above-mentioned monofunctional polymerizable monomers, other polymerizable monomers used in the present invention include crosslinkable polyfunctional monomers. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate,
meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate
Acrylate, tripropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentadiol di(meth)acrylate, 1,6 -Hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, oligoester di(meth)acrylate, polybutadiene di(meth)acrylate, 2
, 2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(ω-(meth)acryloyloxypolyethoxy)phenyl)propane, 2,
2-bis(4-(ω-(meth)acryloyloxypolyethoxy)dibromophenyl)propane, 2,2-bis(4-(ω-(meth)acryloyloxypolypropoxy)phenyl)propane, bis(4-( Di(meth)acrylates such as ω-(meth)acryloyloxypolyethoxy)phenyl)methane, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, divinylbiphenyl, N,
Bifunctional crosslinking monomers such as N'-m-phenylenebismaleimide, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)allylisocyanate Examples include trifunctional crosslinking monomers such as nurate, triallyl trimellitate, and diallyl chlorendate, and tetrafunctional crosslinking monomers such as pentaerythritol tetra(meth)acrylate. Two or more of the above other polymerizable monomers may be used in combination.

The blending ratio of the prepolymer having a polythioether skeleton and other polymerizable monomers is 30 to 90% by weight of the prepolymer having a polythioether skeleton and 70 to 10% by weight of the other polymerizable monomer, preferably polythioether. It is desirable that the composition be composed of 50 to 85% by weight of a prepolymer having a skeleton and 50 to 15% by weight of other polymerizable monomers. If the amount of the prepolymer having a polythioether skeleton is less than 30% by weight, it is not preferable because the physical property of high refractive index, which is the most distinctive feature, will not be utilized.

If the amount of the prepolymer having a polythioether skeleton is more than 90% by weight, the composition will have a high viscosity and will be difficult to handle, which is unfavorable in terms of industrial production.

The case where the addition reaction is carried out in a solvent has been explained above, but when the addition reaction is carried out between component (A) and component (B) in another polymerizable monomer, the above-mentioned 4,4'-bis(methacryloylthio)diphenyl sulfide represented by the formula (I) and the polythiol represented by the formula (II) used as the component (B), among other polymerizable monomers, in the presence of a base catalyst. The addition reaction may be carried out in the presence of.

Component (A) used in the above method,
The amounts of component (B) and the base catalyst used are the same as in the case where the addition reaction is carried out in advance in a solvent to synthesize a prepolymer having a polythioether skeleton.

When carrying out an addition reaction between component (A) and component (B), as in the case where the addition reaction is carried out in advance in a solvent to synthesize a prepolymer having a polythioether skeleton, (B for methacryloyl group)
) component has a functional group equivalent ratio of mercapto groups of 0.02 to 1.
．． It is preferably within the range of 0.01, particularly 0.05 to
A range of 0.60 is desirable. When the functional group equivalent ratio of the mercapto group of component (B) to the methacryloyl group of component (A) is less than 0.02, the cured product is generally brittle and sufficient impact resistance cannot be obtained. Also, (A
If the functional equivalent ratio of the mercapto group in component (B) to the methacryloyl group in component (B) is greater than 1.01, unreacted mercapto groups may reduce the stability of the composition, excessively increase the viscosity of the composition, or cause polymerization. There are problems such as non-uniformity of the cured product due to non-uniform reaction.

Other polymerizable monomers used in the addition reaction of component (A) and component (B) are not particularly limited as long as they polymerize in the presence of a normal radical polymerization initiator. , from the viewpoint of reaction control, is liquid at room temperature,
Preferably, those that do not react or are difficult to react with component (B) in the presence of a base catalyst, that is, have substantially no reactivity with component (B), and are curable with common radical polymerization initiators. Specific examples include styrene, α-methylstyrene, α-ethylstyrene, methylstyrene, ethylstyrene, chlorostyrene, bromostyrene, 2,4-
dichlorostyrene, 2-chloro-4-methylstyrene,
Examples include aromatic vinyl monomers such as divinylbenzene and divinylbiphenyl. Two or more of these aromatic vinyl monomers may be used in combination.

The amount of other polymerizable monomers to be used is determined when component (A) and component (B) are subjected to an addition reaction.
B) In the total amount of component and other polymerizable monomers, 10 to 7
Preferably it is 0% by weight, preferably 15-50% by weight. If the amount of other polymerizable monomers used is less than 10% by weight, the composition will have a high viscosity, which is unfavorable for handling and production during industrialization, and if it is more than 70% by weight, the component (A) will have a high refractive index. I don't like it because it doesn't make the most of my sexuality.

In the case of preparation by addition reaction in other polymerizable monomers, addition reaction conditions such as addition reaction temperature and conditions when removal of the base catalyst for addition reaction is required are as follows:
This is carried out in the same manner as in the case where a prepolymer having a polythioether skeleton is synthesized by carrying out an addition reaction in advance in a solvent.

The curable composition containing the prepolymer having a polythioether skeleton thus obtained has a structure in which the molecular terminal of the prepolymer in the composition is capped with a polymerizable vinyl group, and has excellent storage stability. There is.

This curable composition may further contain other polymerizable monomers that can be copolymerized with the prepolymer having a polythioether skeleton. This method is particularly useful when a polymerizable monomer having higher reactivity than the polymerizable monomer used in the addition reaction in other polymerizable monomers is also used.

It is said that a composition obtained by simply mixing 4,4'-bis(methacryloylthio)diphenyl sulfide, polythiols, and other polymerizable monomers does not have sufficient stability, and the cured product obtained therefrom has poor homogeneity. In contrast, the curable composition according to the present invention has a
It does not gel even after being left for a long time and is extremely stable with almost no increase in viscosity, and the cured product obtained by curing the curable composition has excellent optical uniformity.

The curable composition according to the present invention can be cured by radical polymerization. As the radical polymerization initiator used in radical polymerization, any radical polymerization initiator that can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays can be used, and the use of the curable composition, It can be selected as appropriate depending on the purpose.

Examples of radical initiators that can be used in polymerization using heat, microwaves, and infrared rays include 2,2'
-Azo compounds such as azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, Ketone peroxides such as cyclohexanone peroxide and acetylacetone peroxide, diacyl peroxides such as isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide, and p-chlorobenzoyl peroxide. hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide , G-t-
Butyl peroxide, tris (t-butyl peroxy)
Dialkyl peroxides such as triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di(
Peroxyketals such as t-butylperoxy)butane, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxy Oxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate,
Alkyl peresters such as t-butyl peroxybenzoate and di-t-butyl peroxytrimethyl adipate, diisopropyl peroxydicarbonate, di-
Examples include percarbonates such as sec-butylperoxydicarbonate and t-butylperoxyisopropyl carbonate.

Examples of radical polymerization initiators that can be used in polymerization using ultraviolet light include acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis(diethylamino)benzophenone, benzophenone,
Methyl (o-benzoyl)benzoate, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, benzoin , benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl,
Carbonyl compounds such as benzyl dimethyl ketal, benzyl diethyl ketal, diacetyl, methyl anthraquinone, chloroanthraquinone, chlorothioxanthone,
Examples include anthraquinone or thioxanthone derivatives such as 2-methylthioxanthone and 2-isopropylthioxanthone, and sulfur compounds such as diphenyl disulfide and dithiocarbamate.

The amount of the radical polymerization initiator to be used cannot be determined unconditionally because it varies depending on the type of radical polymerization initiator, the type of monomer charged, and the composition ratio, but it is usually used for curing containing a prepolymer having a polythioether skeleton. The amount is in the range of 0.001 to 20 mol%, preferably 0.01 to 10 mol%, based on the total amount of the sexual composition. If the amount of the radical polymerization initiator used is less than 0.001 mol%, polymerization will not substantially proceed, and if the amount used exceeds 20 mol%, it will not only be uneconomical but may also cause foaming during polymerization or polymerization. This is not preferable because the molecular weight of the cured product obtained by this method becomes significantly small.

[0044] The curable composition used in the plastic lens according to the present invention may also contain polymerization inhibitors, ultraviolet absorbers, antioxidants, mold release agents, antistatic agents, and other additives as necessary. can be added.

[0045] The polymerization temperature and polymerization time for curing the curable composition cannot be unconditionally specified because they vary depending on the type and amount of radical polymerization initiator used, but the polymerization temperature is usually 0 to 200°C. The polymerization time is preferably in the range of 0.5 to 50 hours.

Next, a method for manufacturing a plastic lens will be explained. Plastic lenses are made by dissolving and mixing additives such as radical initiators and ultraviolet initiators in a cavity made by combining two glass molds with different radii of curvature separated by a flexible annular synthetic resin gasket. The prepared prepolymer is injected and cured in an oven. The polymerization temperature varies depending on the thickness of the lens to be manufactured and the radical initiator used, but is usually 30°C to 150°C.
C., and the polymerization time is preferably in the range of 0.5 to 20 hours from the viewpoint of productivity. After heating and curing, the annular gasket is removed and the glass mold is then removed by thermal shock or by driving a wedge between the molds to obtain a lens.

Next, regarding the coated lens,
In particular, the primer layer, hard coat layer, and antireflection layer provided on the lens surface will be explained below. The acrylic primer layer is provided to improve the adhesion between the lens base material and the hard coat layer. The (meth)acrylic polymer that is the main component of the primer layer is one or more esters of acrylic acid and methacrylic acid with lower alcohols such as methanol, ethanol, n-propyl alcohol, and n-butyl alcohol. It is made of a copolymer and may contain other vinyl monomers as necessary. Other vinyl monomers are not particularly limited as long as they can be polymerized with (meth)acryloyl groups, but copolymers with aromatic vinyl compounds are preferred because they improve affinity with lens base materials. be.

Methods for preparing the copolymer include radical polymerization in an organic solvent or radical polymerization in water using a nonionic or anionic surfactant to form an emulsion. Whether the radical polymerization is carried out in an organic solvent or in water to form an emulsion can be selected depending on the wettability of the base lens used, the adhesiveness with the base lens, etc. When carrying out radical polymerization in an organic solvent, the solvent is not particularly limited as long as it dissolves the polymer. Representative examples of such solvents include aromatic hydrocarbon solvents such as toluene and benzene, ether solvents such as ethylene glycol diethyl ether and tetrahydrofuran, and chlorine solvents such as dichloromethane and carbon tetrachloride. The polymer solution thus obtained is preferably further diluted with the above-mentioned solvent in order to adjust the evaporation rate and viscosity. It is also useful to improve the coating properties by adding a silicone-based or fluorine-based surfactant, if necessary. Furthermore, it is also useful to add an ultraviolet absorber to the solution for the purpose of improving the weather resistance of the base material.

However, the primer coating solution generally contains a large amount of polar solvent such as methanol or diethylene glycol monoethyl ether acetate, and the amount of organic ultraviolet absorber dissolved therein is often severely restricted. Furthermore, the addition of an ultraviolet absorber to the hard coat liquid also causes a decrease in the adhesion of the hard coat to the base material and a decrease in scratch resistance, so the amount added is similarly severely restricted. Therefore, by introducing titania into the primer layer structure in which a relatively large amount of ultraviolet absorber can be added, a film that can efficiently cut ultraviolet rays can be easily obtained.

[0050] The titania used in the present invention is usually used in a sol state. The average particle size of the sol used is 1
-100 nm, more preferably 10-100 nm. If the average particle size is less than 1 nm, the effect of improving scratch resistance will be small, and if it exceeds 100 nm, transparency will decrease, making it unsuitable for use. The amount used is 5 to 40% by weight based on the solid content in the primer. If it is less than 5% by weight, the effect in terms of adhesion with the antireflection layer is small, and if it is more than 40% by weight, cracks are likely to occur. As the dispersion medium for the sol, alcohols such as methanol, ethanol, and i-propyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, or water are preferable.

When radical polymerization is carried out in water to form an emulsion, alcohols such as methanol, ethanol, i-propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve, etc. are used to adjust the evaporation rate and viscosity after polymerization. It can be used after being diluted with a water-soluble solvent such as dioxane or tetrahydrofuran. Further, when radical polymerization is carried out in an organic solvent, a silicone-based or fluorine-based surfactant may be added to improve paintability, or an ultraviolet absorber may be added to improve weather resistance. As a method for applying the primer, any method can be selected from dipping, spin coating, and spraying. The thickness of the primer layer is 0.1-3.0μ
can be used arbitrarily between m. More preferably, the thickness is 0.2 to 3.0 μm; if it is less than 0.1 μm, adhesion is insufficient, and if it exceeds 3.0 μm, it is difficult to apply uniformly. In order to thicken the primer layer, the concentration of the primer liquid may be increased or the pulling speed may be increased. Although drying varies depending on the solvent of the primer liquid, a uniform film can be obtained by heating at a temperature of 60 to 150°C for 2 to 60 minutes. If the drying temperature is 60° C. or lower, it will take a long time to perform sufficient drying, and if the drying temperature is 150° C. or higher, the base lens will turn yellow. Regarding the drying time, if the drying time is less than 2 minutes, the drying will be insufficient and whitening will easily occur when applying the hard coat, and if the drying time is more than 60 minutes, it will not be efficient from the viewpoint of productivity.

Next, the silicon-based hard coat layer will be explained. The component is a hydrolyzate of one or more organosilicon compounds represented by the above formula (III). Specific examples of organosilicon compounds include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetra-n-butoxysilane, trialkoxysilanes such as methyltrimethoxysilane and methyltriethoxysilane, methyltriacetoxysilane, and ethyl. Examples include triacetoxysilanes such as triethoxysilane, and dialkoxysilanes such as dimethyldimethoxysilane and diphenyldimethoxysilane. In particular, for the purpose of improving scratch resistance, it is desirable to use tetraalkoxysilanes, trialkoxysilanes, etc. that have many hydrolyzable groups, and for the purpose of improving impact resistance, it is desirable to use organosilicon compounds that have few hydrolyzable groups. , the use of organosilicon compounds containing epoxy groups is preferred. The hydrolyzable group is usually cured by dehydration condensation after hydrolysis. Therefore, it is used after being hydrolyzed in a solvent such as water, alcohol, or cellosolve using a mineral acid or an organic acid as a catalyst. Colloidal silica may be added to the hard coat solution prepared in this manner for the purpose of improving scratch resistance and adhesion to the antireflection layer. The particle size of the colloidal silica used is preferably 1 to 100 nm, more preferably 10 to 100 nm. Particle size is 1
If it is less than 100 nm, the effect of improving scratch resistance will be small, and if it is more than 100 nm, the transparency will decrease, making it unsuitable for use. The amount used is 10 to 80% by weight, more preferably 30 to 60% by weight, based on the solid content of the hard coat liquid. If it is less than 30% by weight, the effect in terms of adhesion with the antireflection layer will be small, and if it exceeds 60% by weight, cracks will easily occur.

[0053] As the dispersion medium, methanol, ethanol,
Alcohols such as i-propyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, or water are preferable. Application methods include dipping, spin coating,
Spray method etc. are possible. After application, drying at 60°C to 80°C or not, and drying at a temperature of 80°C to 150°C for 2 hours.
It can be cured by heating for 0 to 120 minutes. If the curing temperature is below 80°C, it will take a long time for sufficient curing, and if it is above 150°C, the base lens will be colored yellow. If the curing time is less than 20 minutes, curing will not be sufficient, and if it is more than 120 minutes, it will not be effective in terms of productivity. Similarly to the primer layer, an ultraviolet absorber can be used in the hard coat liquid for the purpose of improving the weather resistance of the base material.

Next, the antireflection layer will be explained. The inorganic antireflection layer is formed by vacuum evaporation method or ion sputtering method, and is made of SrO, BaO, VO, V2 O3, V
O2, V2 O5, NbO, NbO2, Nb2
O5, TaO2, Ta2 O5, CrO, Cr2
O3, CrO3, MoO, Mo2 O3, Mo
O3, WO, W2 O3, WO3, MnO, Mn
2 O3 , MnO2 , Mn3 O4 , Mn2 O
7, FeO, Fe2 O3, Fe3 O4, Co
O, Co2 O3, Co3 O4, NiO, Cu2
O, CuO, ZnO, ZnO2, Ga2 O, Ga
2 O3 , In2 O, InO, In2 O3 , G
eO, GeO2, SnO, SnO2, PbO, Pb
3 O4 , Pb2 O3 , PbO2 , SiO, S
iO2, ZnO2, Al2O3, TiO2,
Inorganic compounds such as Ti2 O3 and MgO, especially SiO, S
iO2, ZrO2, Al2O3, TiO2,
It is used as a single layer or multilayer film of Ti2O3, MgO, etc. λ/4- with different refractive index from the viewpoint of anti-reflection effect
A three-layer film with a thickness of λ/4-λ/4 or a multilayer film of three or more layers is effective.

The high refractive index lens thus obtained is a practical lens with low water absorption, excellent scratch resistance, and high antireflection effect.

[0056]

[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples. The high refractive index lenses obtained in the following examples were evaluated by the following method.

(1) Adhesion using Sunshine Weatherometer (manufactured by Suga Test Instruments) 2
After 40 hours, a cross-hatch test (100 squares were made at 1 mm intervals on the lens surface with a knife, adhered with cellophane tape, and then peeled off) was performed, and the number of squares that were in close contact was calculated.

(2) Weather resistance and discoloration Using a Sunshine Weather-Ometer (manufactured by Suga Test Instruments) 2
Yellow index of -2D lens after 40 hours (
JIS K7103) values are shown.

Example 1 (1) Preparation of lens base material A stirrer and dropping funnel were set in a 2-liter separable flask, and 4,4'-bis(methacryloylthio) was added at room temperature.
500 g of diphenyl sulfide was charged and dissolved in 600 ml of distilled dichloromethane. Add 0.8 g of diethylamine at room temperature while continuing to stir under a nitrogen stream,
Next, 50 g of ethylene glycol dithioglycolate was added dropwise. The reaction temperature was controlled at 25°C to 35°C. Thereafter, stirring was continued for an additional 3 hours to complete the reaction. The completion of the reaction was determined by confirming the disappearance of the mercapto group in mercapto group analysis using the Volhard method. After the reaction was completed, 50 g of an inorganic adsorbent for strong base adsorption (Kyoward 700SL, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to remove diethylamine. After the adsorbent was filtered off, the mixture was concentrated under reduced pressure to obtain a highly viscous syrup-like liquid. 400 g of this liquid was diluted with 182 g of styrene to obtain a low viscosity composition.

0.3 parts by weight of azobisisobutyronitrile was mixed and dissolved in 100 parts by weight of the obtained curable composition, and a mixture was prepared between two flat glasses with an interval of 3 mm and 0.1 m.
Mold set to m and center thickness 1.2 m after curing
m, and the power was injected into a glass mold for forming a lens designed to have a power of -2.00D. These castings were held in a hot air oven at 35°C for 6 hours, then heated to 80°C over 5 hours, and then held at 80°C for 2 hours to harden. After demolding, annealing treatment was performed at 100° C. for 2 hours.

(2) Preparation and application of primer liquid Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content: 40%) was used as an acrylic aqueous emulsion. Add polyvinyl alcohol (molecular weight approximately 2) to 100 g of the aqueous emulsion.
After thoroughly mixing 1.5 g of 2000), 178 g of a titania sol methanol solution with a solid content of 15% and 767 g of diethylene glycol monoethyl ether acetate were added under stirring to prepare a primer liquid (the titania content ratio in the solid content of the primer liquid was 40%).

After filtering this primer solution through a glass filter with 3.0 μm pores, dipping was performed on the base lens prepared in (1) at a lifting speed of 30 cm/min. Immediately after dipping, drying was performed at 100° C. for 5 minutes to obtain a uniform film. The film thickness was measured using a contact type surface roughness meter and was found to be 0.4 μm.

(3) Preparation and application of hard coating liquid In a 1-liter separable flask equipped with a stirrer, 300 g of isopropyl alcohol-dispersed colloidal silica (manufactured by Nissan Chemical Industries, Ltd., solid content 30%) and 4-ethoxy silicon 66
．． 7 g, 33.4 g of methyltriethoxysilicon, and further 70 g of isopropyl alcohol, 30 g of 0.05N hydrochloric acid.
g was added, stirred at room temperature to perform hydrolysis, and then aged for 24 hours or more. Furthermore, 80 g of n-butanol is added to 100 g of this liquid.
g, 40 g of acetic acid, and 0.4 g of sodium acetate were added to prepare a hard coat liquid. The lens obtained in step (2) was dipped into a solution obtained by filtering this hard coat solution through a glass filter with 3.0 μm holes at a lifting speed of 30 cm/min. Immediately after pulling up, the film was cured by heating at 120° C. for 2 hours to obtain a uniform hard coat film. When the film thickness was measured using a contact type surface roughness meter, it was found to be 3.0 μm including the thickness of the previous primer layer.

(4) Preparation of antireflection layer The lens obtained in (3) was coated with SiO2 (first layer) and ZrO2 from the lens side in a vacuum of 1.0 x 10-5 torr.
A total of five vapor deposited films were provided: SiO2 (second layer), SiO2 (third layer), ZrO2 (fourth layer), and SiO2 (fifth layer). The respective film thicknesses are 1/4λ (first layer) and 1/4λ (
Total film thickness of 2nd layer and 3rd layer), 1/4λ (4th layer), 1
/4λ (fifth layer). The design wavelength λ is 520 nm.
I went there.

The evaluation results of Example 1 are shown in Table 2. Table 2
As shown in Figure 2, the lenses obtained with this prescription had good film adhesion and weather resistance.

Example 2 2, 2',
6.8 g of 4,4'-tetrahydroxybenzophenone (
The preparation of the lens substrate, the preparation and coating of the hard coat liquid, and the preparation of the antireflection layer were carried out under the same conditions as in Example 1, except that 10% by weight of the solid content in the primer liquid was added and dissolved. The evaluation results are shown in Table 2.

Example 3 Regarding the preparation of a lens base material, bis(2) was used as the component (B).
-Mercaptoethyl) sulfide was used, but the primer, hard coat, and antireflection layer were carried out according to the same conditions as in Example 2. The types and amounts of component (B) are shown in Table 1. The evaluation results are shown in Table 2.

Example 4 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40%) was used as the primer liquid, and 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) was added to 100 g of the aqueous emulsion. After mixing, 5.2 g of 2,2',4,4'-tetrahydroxybenzophenone (10% by weight of solids in the primer solution), 66.7 g of titania sol methanol solution with 15% solids, and 575 g of diethylene glycol monoethyl ether acetate. The preparation of the lens base material, hard coat, and antireflection layer was the same as in Example 2, except that the titania content in the solid content of the primer solution was 20% by weight by adding the following under stirring to obtain a primer solution. It was carried out according to the conditions. The evaluation results are shown in Table 2.

Example 5 The same material as in Example 3 was used as the lens base material.
The primer, hard coat, and antireflection layer were prepared according to the same conditions as in Example 4. The evaluation results are shown in Table 2.

Example 6 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40%) was used as a primer liquid, and 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) was thoroughly mixed with 100 g of the aqueous emulsion. After that,
4.6 g of 2,2',4,4'-tetrahydroxybenzophenone (10% by weight of solid content in the primer liquid), 29.6 g of titania sol methanol solution with a solid content of 15%, and diethylene glycol monoethyl ether acetate 5
The lens base material, hard coat, and antireflection layer were prepared as in Example 2, except that 11 g of the primer solution was added under stirring (the titania content ratio in the solid content of the primer solution was 10% by weight). Performed according to the same conditions. The evaluation results are shown in Table 2.

Example 7 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40%) was used as a primer liquid, and 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) was thoroughly mixed with 100 g of the aqueous emulsion. After that,
4.4 g of 2,2',4,4'-tetrahydroxybenzophenone (solid content in the primer liquid: 10% by weight), 14.0 g of a titania sol methanol solution with a solid content of 15%, and diethylene glycol monoethyl ether acetate 4
The preparation of the lens base material, hard coat, and antireflection layer was the same as in Example 2, except that 84 g was added under stirring to make a primer solution (the titania content ratio in the solid content of the primer solution was 5%). It was carried out according to the conditions. Table 2 shows the evaluation results.
Shown below.

Example 8 The preparation of the lens base material was performed in accordance with Example 1 except that the types of other polymerizable monomers and the type of component (B) were changed.
subject to the terms of. The conditions for preparing the primer, hard coat, and antireflection layer were all the same as in Example 7. The evaluation results are shown in Table 2.

Comparative Example 1 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40% by weight) was used as the primer liquid.
), 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) was thoroughly mixed with 100 g of the aqueous emulsion, and 4.3 g of 2,2',4,4'-tetrahydroxybenzophenone (10% by weight of solid content in the primer liquid) was thoroughly mixed with 100 g of the aqueous emulsion. ),
8.2 g of a titania sol methanol solution with a solid content of 15% and 474 g of diethylene glycol monoethyl ether acetate were added under stirring to prepare a primer liquid (the titania content ratio in the solid content of the primer liquid was 3% by weight). The lens base material, hard coat, and antireflection layer were prepared according to the same conditions as in Example 2. The evaluation results are shown in Table 2.

Comparative Example 2 2, 2', 4 was used as an ultraviolet absorber when preparing the primer solution.
, 4'-tetrahydroxybenzophenone (20% by weight of the solid content in the primer liquid) was added and dissolved, but the same conditions as in Comparative Example 1 were followed. The evaluation results are shown in Table 2.

Comparative Example 3 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40%) was used as a primer liquid, and 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) was thoroughly mixed with 100 g of the aqueous emulsion. After that,
2,2',4,4'-tetrahydroxybenzophenone 7.4g (10% solid content in primer liquid), solid content 1
218 g of 5% by weight titania sol methanol solution and 83 g of diethylene glycol monoethyl ether acetate
The lens base material, hard coat, and antireflection layer were prepared as in Comparative Example 1, except that 6 g was added under stirring to make a primer solution (the titania content ratio in the solid content of the primer solution was 45% by weight). Performed according to the same conditions. The evaluation results are shown in Table 2.

Comparative Example 4 Acrylic aqueous emulsion Polysol F341 (manufactured by Showa Kobunshi Co., Ltd., solid content 40%) was used as the primer liquid.
After thoroughly mixing 1.5 g of polyvinyl alcohol (molecular weight approximately 22,000) with 100 g of the aqueous emulsion using a )
, titania sol methanol solution with solid content of 15% by weight 40
0 g and 1150 g of diethylene glycol monoethyl ether acetate were added under stirring to prepare a primer liquid (the titania content ratio in the solid content in the primer liquid was 60
The lens base material, hard coat, and antireflection film were subjected to the same conditions as in Comparative Example 1, except for (expressed as % by weight). The evaluation results are shown in Table 2.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

According to the present invention, it is possible to provide a practical plastic lens which has a high refractive index, good adhesion of a coating film, and little discoloration due to weathering. In particular, the plastic lens according to the present invention is useful for eyeglasses.

Claims (1)

[Claims] Claim 1: (A) 4,4'-bis(methacryloylthio)diphenyl sulfide represented by formula (I) and (B) R-(SH)n of formula (II)

(II) (wherein R represents an organic group consisting of a polyvalent aliphatic or aromatic hydrocarbon, and n represents an integer of 2 or more). ■0.1-3 on the surface of a plastic lens obtained by polymerizing a curable composition consisting of a prepolymer having a thioether skeleton and another polymerizable monomer
．． 5-40% by weight of titania in solid content with a film thickness of 0 μm
Acrylic primer layer containing: 0.5 to 6.0μ consisting of one or more hydrolysates of organosilicon compounds represented by formula (III) and/or partial condensates thereof;
A silicon-based hard coat layer with a film thickness of m:
It may have a substituent selected from epoxy groups. R
3 is a hydrolyzable group selected from alkoxy, halogen, acyloxy, and phenoxy groups, and a and b are 0 or 1) ① A plastic lens sequentially provided with an antireflection layer of an inorganic compound.