JP2000009902A - Plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic lens for glasses having enough optical characteristics as a lens for correction of eyesight and excellent impact resistance by forming a primer layer of an org. resin on the surface of a lens base body consisting of a specified polycarbonate resin and further forming a hardened layer of a silicone resin thereon. SOLUTION: As for the plastic lens base body, an aromatic-aliphatic copolymerized polycarbonate having units expressed by the formula I and formula II is used. A primer layer of 0.1 to 20 μm thickness consisting of an org. resin is formed on the surface of the lens base body, and further a silicone-based hardened layer is formed thereon. In the formulae, X is expressed by the formula III, R3 and R4 are hydrogen atoms or 1-10C alkyl groups or phenyl groups. R1 and R2 are hydrogen atoms, 1-10C alkyl groups or halogens, (m) and (n) represent the numbers of substituents and are integers 0 to 4, and R5 to R8 are hydrogen atoms or 1-10C univalent alkyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens having characteristics such as abrasion resistance, hot water resistance, chemical resistance, and adhesion between a lens substrate and a cured layer, and particularly excellent in impact resistance.

[0002]

2. Description of the Related Art Plastic lenses, which have excellent properties such as lightness, fashionability, and impact resistance, are rapidly becoming popular in optical materials, especially in the field of spectacle lenses. Problems such as low surface hardness and surface reflection, which have been considered to be the drawbacks of plastic materials, are due to surface modification such as the provision of a silicone-based hard coat film or the provision of an anti-reflection film in which an inorganic substance is deposited on the lens surface. The quality of plastic lenses has been greatly improved by the development of quality technology, and the market for plastic lenses has been expanding with the added value of lenses. However, it has been pointed out that when a silicone-based hard coat or an inorganic antireflection film is provided, the impact resistance inherent in a plastic lens is greatly reduced.
For example, when allyl diglycol carbonate, which is a general-purpose thermosetting plastic lens material, is used as a material, the impact resistance of the base material itself (the center of the lens having a center thickness of 2 mm, the height of 1
In a falling ball impact test in which a steel ball having a predetermined weight is dropped from 27 cm) is about 200 g, but when a hard coat is applied, the drop is reduced to about 60 g, and when an antireflection film is further provided thereon, the impact resistance is remarkably reduced to 10 g. It is known that the property is reduced. For the purpose of avoiding this problem, in the case of a thermosetting plastic lens, a method of improving the impact resistance by providing a primer layer between a plastic lens substrate and a silicone-based hard coat is disclosed. . For example, by a method of providing a layer made of a urethane resin as a primer layer (Japanese Patent Application Laid-Open No. 8-54501), spectacles having impact resistance that clears US FDA standards (falling ball impact value of 16.4 g) even after an inorganic antireflection coating. It is disclosed that a lens is obtained. However, it cannot be said that sufficient impact resistance is obtained for use in a field where more safety is required.

[0003] On the other hand, thermoplastic transparent plastic materials are:
Since it can be injection-molded, it has excellent features such as improved productivity, precision moldability, and no coloring with time, as compared with thermosetting resins. Above all, the property of polycarbonate having extremely excellent impact resistance is utilized, and the demand is expanding as a spectacle lens for sports and children in which safety is emphasized. The excellent impact resistance is hardly reduced by surface modification as seen in the thermosetting material. However, polycarbonate has a relatively high refractive index, but a low Abbe number (νD = 30), and cannot be said to have sufficient performance as a corrective spectacle lens. Bad, not widely used. Acrylic resin, which is another typical transparent thermoplastic resin, cannot be said to have sufficient properties as a material for eyeglass lenses in terms of heat resistance and impact resistance.

[0004]

SUMMARY OF THE INVENTION The present invention aims to solve the problems associated with the prior art described above, and in particular, has sufficient optical characteristics as a corrective spectacle lens, and An object of the present invention is to provide a thermoplastic spectacle lens excellent in impact resistance that can meet safety requirements for spectacle lenses.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to overcome the drawbacks of the conventional plastic lens, and as a result, as a constitutional unit, a polycarbonate resin having the above structural formulas (1) and (2). By providing a primer layer made of an organic resin on the surface of a plastic lens substrate, and further providing a cured layer made of a silicone resin on the primer layer, it has sufficient abrasion resistance and has a lens made of a polycarbonate resin. The present invention has been found to solve the drawback of a low Abbe number and to maintain excellent impact resistance, which is a characteristic of a lens made of a polycarbonate resin.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a plastic lens according to the present invention will be specifically described.

As the plastic lens substrate used in the present invention, an aromatic-aliphatic copolymer polycarbonate having the above structural formulas (1) and (2) is used. The copolymer includes a random, block or alternating copolymer, or a blend of an aromatic-aliphatic copolymer having the structural formulas (1) and (2) with a polycarbonate having the structural formula (1). And a structural unit represented by the above structural formula (1) (hereinafter referred to as I)
) And the structural unit represented by the above structural formula (2) (hereinafter referred to as II) have a molar ratio (I / II) of 90/10
Preferably, it is in the range of 70/30 to 30/70. When the molar ratio (I / II) of the structural formulas (1) and (2) is higher than 90/10, the effect of improving the Abbe number is small, and when the molar ratio (I / II) is lower than 10/90, heat resistance, impact resistance and the like are reduced. Inferior. Also,
The weight average molecular weight of the aliphatic-aromatic copolymerized polycarbonate resin is preferably from 50,000 to 200,000, more preferably from 70,000 to 150,000.
0. If the weight average molecular weight is lower than 50,000, the impact resistance becomes low, and if it is higher than 200,000, the melt viscosity becomes too high and injection molding becomes extremely difficult, which is not preferable.

The above-mentioned aromatic-aliphatic copolymerized polycarbonate can be produced by a known method for producing a general polycarbonate, and is particularly preferably produced by a transesterification method. In the transesterification using a carbonic acid diester, polymerization can be carried out by a known melt polycondensation method. That is, by-products are produced under heating at normal pressure or reduced pressure using an aromatic dihydroxy compound represented by the following formula (3), an aliphatic dihydroxy compound represented by the following formula (4), a carbonic acid diester and a catalyst. Melt polycondensation is performed while removing. The reaction is generally carried out in two or more stages.

Embedded image (X in the above formula (3) is

Embedded image , And the here, R ₃ and R ₄ is a hydrogen atom or an alkyl group or a phenyl group having 1 to 10 carbon atoms, R ₃
And R ₄ may combine to form a ring. R ₁ and R ₂
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen, and R ₁ and R ₂ may be the same or different. Further, m and n represent the number of substituents and are integers of 0 to 4. )

Embedded image (In the above formula (4), R ₅ , R ₆ , R ₇ , and R ₈ are a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.)

Specifically, the first-stage reaction is carried out at 120 to 2
The reaction is carried out at a temperature of 60 ° C, preferably 180 to 240 ° C, for 0 to 5 hours, preferably 0.5 to 3 hours. Next, the degree of reaction was increased while increasing the degree of vacuum of the reaction system.
The polycondensation reaction is performed at a temperature of 200 to 300 ° C. under a reduced pressure of not more than mmHg. Further, the reaction device used for performing the above reaction may be a tank type or an extruder type.

As a polymerization catalyst, a basic compound is used. Examples of such a basic compound include an alkali metal compound, an alkaline earth metal compound, a nitrogen-containing compound and the like, and these compounds can be used alone or in combination.

As such an alkali metal compound,
Organic acid salts of inorganic metals, inorganic acid salts, oxides, hydroxides, hydrides, alcoholates and the like are used, and specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, hydrogen carbonate Sodium, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate,
Potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, benzoic acid Cesium, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, disodium salt of bisphenol A, 2 Potassium salts, dicesium salts, dilithium salts, sodium salts of phenol, potassium salts, cesium salts, lithium salts and the like are used.

Further, as the alkaline earth metal compound,
Alkaline earth metal organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides, alcoholates and the like are used, specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, Calcium bicarbonate,
Barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate,
Calcium stearate, barium stearate, magnesium stearate, strontium stearate,
Are used.

As the nitrogen-containing compound, quaternary ammonium hydroxide, quaternary ammonium salts, amines and the like are used. Specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutyl Ammonium hydroxides having alkyl, aryl, araryl groups such as ammonium hydroxide, trimethylbenzyl ammonium hydroxide, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylamine, diethylamine, etc. Secondary amine, methylamine, primary amines such as ethylamine, 2-methylimidazole, 2-phenylimidazole, imidazoles such as,
Alternatively, basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetramethylammonium tetraphenylborate and the like are used.

These catalysts are used in an amount of 10 ^-9 to 1 mol of the aromatic dihydroxy compound represented by the above formula (3) and the aliphatic dihydroxy compound represented by the above formula (4) in total.
An amount of from 10 to 10 ^-3 mol, preferably from 10 ^-7 to 10 ^-5 mol, is used.

As the aromatic dihydroxy compound used in the above formula (3), specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl)
Octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-
t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
4,4′-dihydroxydiphenyl ether, 4,4 ′
-Dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,
4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4'-dihydroxy-3,3'-
Dimethyldiphenyl sulfone and the like. Among these, 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A or 1,1-bis (4-hydroxyphenyl) cyclohexane is particularly preferred.

As the aliphatic dihydroxy compound represented by the above formula (4), specifically, (3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro ( Five.
5) Undecane), (3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane), (3,9-bis (2- (Hydroxy-1,1-diethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane), (3,9-bis (2-hydroxy-1,1-dipropylethyl) -2,4 , 8,10-tetraoxaspiro (5.5) undecane) and the like. Preferably, (3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane) is used. Preferably, (3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane) is used.

Further, as the carbonic acid diester, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate Are used. Of these, diphenyl carbonate is particularly preferred. Diphenyl carbonate is
1.01 to 1.0 mol per 1 mol of the aromatic dihydroxy compound (3) and the aliphatic dihydroxy compound (4) in total.
It is preferably used in an amount of 1.30 mol.

It is preferable to remove or deactivate the catalyst in the polycarbonate resin of the present invention in order to maintain heat stability and hydrolysis stability. In general, a method of deactivating a transesterification catalyst such as an alkali metal or an alkaline earth metal by adding a known acidic substance is suitably performed. As these substances, specifically,
Aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl paratoluenesulfonic acid, organic halides such as stearic acid chloride, butyric acid chloride, benzoyl chloride, and toluenesulfonic acid chloride; Organic halides such as alkyl sulfates and benzyl chloride are preferably used.

After deactivation of the catalyst, a step of devolatilizing and removing low boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and at a temperature of 200 to 300 ° C. may be provided. A horizontal or thin-film evaporator having eyeglasses or the like is preferably used.

In the present invention, the above-mentioned heat stabilizer,
In addition to the hydrolysis stabilizer, antioxidants, pigments, dyes, reinforcing agents and fillers, ultraviolet absorbers, lubricants, release agents, crystal nucleating agents, plasticizers, flow improvers, antistatic agents, etc. Can be added. Further, for the purpose of further improving the properties of the resin, another polycarbonate resin or a thermoplastic resin may be blended and used.

Each of these additives can be mixed with the polycarbonate resin by a conventionally known method. For example, a method in which each component is dispersed and mixed by a high-speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, or a super mixer, and then melt-kneaded by an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

It is preferable that the primer resin used in the present invention has excellent adhesion to the resin substrate and the silicone-based cured film, and has some flexibility to relieve stress. Specific examples include a polyacrylic and / or polymethacrylic resin composition, an epoxy resin composition, and a polyurethane resin composition.

The polyacrylic and / or polymethacrylic resin composition includes a thermoplastic resin obtained by polymerizing one or more acrylate and / or methacrylate monomers. Examples of specific monomers include esters of acrylic acid and methacrylic acid such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, and hexyl. . Specific examples of the acrylate monomer include methyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, and 2-ethylhexyl acrylate. Specific examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, isobutyl methacrylate, and propyl methacrylate. Homopolymers derived from these single monomers or copolymers derived from two or more monomers are suitably used as primer resins.

Examples of the polyacrylic and / or polymethacrylic thermosetting resin composition include a resin composition obtained by reacting a polyacrylic and / or polymethacrylic resin having active hydrogen with an isocyanate. Such a resin composition can be obtained by a curing reaction of a primer composition comprising a (meth) acryl polyol and a polyfunctional organic isocyanate compound.

Specific examples of (meth) acrylic polyols include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
It is a copolymer of (meth) acrylates having a hydroxyl group such as hydroxypropyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, glycerol monomethacrylate and other unsaturated compounds. Where, as the other unsaturated compound monomer,
Examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-butyl acrylate, and n-butyl methacrylate.
The production of the (meth) acryl polyol can be easily carried out by a known method, and is carried out using an azo compound such as azobisisobutyronitrile or a peroxide compound such as benzoyl peroxide as a polymerization initiator.

Specific examples of the polyfunctional organic isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and bis (isocyanatomethyl) cyclohexane. , Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, biuret conjugate of hexamethylene diisocyanate or isocyanurate conjugate, reaction adduct of hexamethylene diisocyanate with trimethylolpropane, 2-isocyanatoethyl-2,6-diisocyanate Hexanoate, 1,
There are 6,1,1-undecane triisocyanate, a reaction adduct of isophorone diisocyanate with trimethylolpropane, and a reaction adduct of bis (isocyanatomethyl) cyclohexane with trimethylolpropane.

Examples of the epoxy resin composition include diglycidyl ethers such as glycerin, sorbitol, trimethylolpropane, and trimethylolmelamine, polyethylene glycol, polypropylene glycol, neopentyl glycol, catechol, resorcinol, alkylene glycol, hexanediol, and hexanediol. ,
Examples include diglycidyl ethers of bifunctional alcohols such as butanediol, virphenol A, and hydrogenated bisphenol A. Perchlorates are preferably used as the epoxy curing catalyst. Specifically, zinc perchlorate,
Examples include ammonium perchlorate, oxazine perchlorate, potassium perchlorate, ferric perchlorate, tetraethylammonium perchlorate, sodium perchlorate, barium perchlorate, and lithium perchlorate.

Examples of the polyurethane resin composition include a resin formed by a reaction between a compound having active hydrogen and polyisocyanate. Examples of the active hydrogen compound include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, diethylene glycol,
Polyalkylene glycols such as alkylene glycol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, etc., poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly (neopenthylene adipate), etc. Poly (alkylene adipates), poly-ε-caprolactone, poly (1,4-
Polybutadiene glycols such as butanediene) glycol and poly (1,2-butanediene) glycol; poly (alkylene carbonates) such as poly (hexamethylene carbonate); and polyol compounds having two or more hydroxyl groups such as silicone polyol. be able to. Examples of polyisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate,
4,4'-diphenylmethane diisocyanate, 1,5
-Naphthalenediisocyanate, 3,3-dimethyl-
Aromatic diisocyanates such as 4,4'-diphenyl diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate And the like aliphatic diisocyanates.

The polyurethane resin can be manufactured by a known method, and various amines and metal compounds such as dibutyltin dilaurate are used as a catalyst.

The various resin compositions described above are dissolved in a solvent and used as a primer composition. Examples of the solvent include hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers and the like. Particularly preferred solvents that do not dissolve the resin of the base material, do not cause whitening, swelling, and the like include methanol, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, and diacetone alcohol. These may be used alone or as a mixed solvent. Various leveling agents are added to the solution for the purpose of improving applicability, or UV absorbers and antioxidants for the purpose of improving the weather resistance, as well as dyes and pigments, and various other additives for improving the film performance are added. be able to.
The method for applying the primer composition is appropriately selected from spin coating, dipping, and other known methods. After applying the primer composition, 30 to 200 ° C,
Preferably, by heating at an arbitrary temperature in the range of 60 to 120 ° C., a desolvation or curing reaction can be performed to form a primer film. The upper limit of the heating temperature is preferably selected according to the glass transition temperature of the resin substrate. The heating time varies depending on the primer composition used, but a heating time of 1 to 120 minutes is preferred.

The primer layer has a thickness of 0.1 to 20 μm, which is effective for improving impact resistance, and particularly preferably 1 to 10 μm.
μm. If the thickness is 0.1 μm or less, the effect of improving the impact resistance is not so large. If the thickness exceeds 20 μm, the effect is not so much improved, and there is an adverse effect such as a decrease in surface accuracy of the lens.

In the present invention, a silicone-based cured layer is provided by curing a coating composition containing an organosilicon compound and / or a hydrolyzate thereof on the cured primer layer. The silicone resin used in the present invention is obtained by drying and / or heating and curing an organosilicon coating composition comprising the general formula R ₁ aR ₂ bSi (OR ₃ ) 4-ab and / or a hydrolyzate thereof. It is a cured resin layer. (Where R ₁ and R ₂ each represent an alkyl group, an alkenyl group, an allyl group, a hydrocarbon group having a halogen, an epoxy group, a glycidoxy group, an amino group, a mercapto group, a methacryloxy group or a cyano group, R ₃ Is an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group, an acyl group, or a phenyl group;
And b is 0 or 1)

Examples of these organosilicon compounds include tetraalkoxysilanes such as methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate and tert-butyl silicate, and hydrolysis thereof. Product, further, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane,
Methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , Phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloro Methyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α
-Glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α -Glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ -Glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-
Glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3 , 4-Epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl)
Methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3
4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4
-Epoxycyclohexyl) propyltriethoxysilane, trialkoxysilanes such as δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, triacylsilanes, triphenoxysilanes or hydrolysates thereof, dimethyldimethoxysilane, phenylmethyldimethoxy Silane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, glycidoxymethylmethyldimethoxysilane, α
-Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropyldimethoxysilane, etc. Or a diacyloxysilane or a hydrolyzate thereof.

These organosilicon compounds may be used alone or in combination of two or more. In particular, the use of an organosilicon compound containing an epoxy group is suitable for imparting dyeability.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and promote the curing. The hydrolysis is performed by adding pure water or an acidic aqueous solution of hydrochloric acid, acetic acid, sulfuric acid or the like to the organosilicon compound and stirring. The degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution. Upon hydrolysis,
The addition of pure water or an acidic aqueous solution in an amount equal to or more than 3 moles of the alkoxy group is preferable from the viewpoint of promoting the curing.

The hydrolysis may be performed without a solvent, or a solvent may be used for the purpose of performing the hydrolysis more uniformly.
When a solvent is used, it is preferable to carry out hydrolysis after mixing the organosilicon compound with the solvent. Depending on the purpose, the alcohol or the like after the hydrolysis may be removed by heating and / or an appropriate amount under reduced pressure before use, or another solvent may be added after removal. These solvents include alcohols, ethers, ketones, esters, and aromatic hydrocarbons. Further, these solvents may be used as a mixed solvent of two or more kinds as necessary.

If necessary, the hydrolysis may be carried out under heating at room temperature or higher in order to promote the hydrolysis reaction and advance the reaction such as precondensation. It may be performed under cooling.

In the formation of the cured silicone resin layer in the present invention, that is, the curing of the organosilicon coating composition, the coating composition is applied to a plastic lens substrate, and then dried and / or heated, irradiated with ultraviolet rays or irradiated with an electron beam. For example, various curing agents can be used in combination for the purpose of accelerating curing and enabling low-temperature curing. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are suitably used. Specific examples include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, metal alkoxides, organic carboxylate salts of alkali metals, carbonate salts of alkali metals, and the like. These curing agents may be used alone or as a mixture of two or more as needed. Among these curing agents, aluminum chelate compounds are preferably used from the viewpoint of the stability of the coating composition and the coloring of the cured layer.

In the present invention, in order to improve the flow when applying the coating composition to the plastic lens substrate, and to improve the smoothness of the coating to reduce the coefficient of friction of the coating surface, the coating composition is used. It is preferable to use a surfactant after adding a surfactant. Specifically, a block or graft copolymer of dimethylsiloxane and alkylene oxide, or a fluorine-based surfactant is effective.

It is also possible to disperse dyes and pigments or fillers, dissolve the organic polymer to color the coating film, and improve the coating properties, the adhesion between the cured film and the substrate, and the physical properties of the cured film. It is. Further, addition of an ultraviolet absorber for improving the weather resistance of the cured film and addition of an antioxidant for improving the heat deterioration are also preferably performed.

Further, for the purpose of further improving the surface hardness of the cured layer made of a silicone resin, and improving the antistatic property, the refractive index of the cured layer, and the weather resistance, various inorganic substances can be added to the coating composition. The addition is preferably carried out.
In particular, colloidal silica which is a colloidal dispersion of a high molecular weight inorganic silicic acid in an organic solvent such as water and / or alcohol is preferably used for improving the surface hardness. Colloidal silica is silica fine particles having a particle size of 1 to 100 mμ,
More preferably, a dispersion of silica fine particles having a particle size of 5 to 40 μm is suitably used. Colloidal silica is preferably used in the range of 5 to 70% for improving the adhesion to the antireflection film.

The method for applying the silicone cured layer is appropriately selected from the same methods as the above-mentioned primer composition, that is, spin coating, dipping, spraying, and the like. Since this curing reaction proceeds by heating, 6
0 to 150 ° C, more preferably 80 to 120 ° C in hot air 3
It is performed by heating for 0 to 240 minutes.

In the present invention, after the silicone-based cured layer is cured, a single-layer or multilayer anti-reflection film may be further provided. Examples of the substance used for the antireflection film include metal, metal or metal oxides, fluorides, silicides, borides, carbides, nitrides, and sulfides. Specifically, SiO ₂ , SiO, ZrO ₂ ,
Metal oxides such as Al ₂ O ₃ , TiO ₂ , Sb ₂ O ₃ , Sb ₂ O ₅ , tantalum oxide, and fluorides such as MgF ₂ .

As a method for forming a single-layer or multi-layer antireflection film made of these substances, there are a vacuum deposition method, a sputtering method, an ion plating method, an ion beam assist method and the like.

[0045]

According to the present invention, a lens having sufficient optical properties as a spectacle lens and excellent in hardness, adhesion and impact resistance can be manufactured, which is very useful.

[0046]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 (Production of lens substrate) 771,6.9 g (33.80 mol) of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 3,9-bis (2-
Hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane (hereinafter referred to as spiroglycol) 9498.2 g (31.20 mol), diphenyl carbonate
15129.5 g (70.63 mol), sodium bicarbonate 0.0161 g
(1.921 × 10 −4 mol) was prepared with a stirrer and a distilling device.
The reactor was charged to a 0-liter reactor equipped with a stirrer and a distilling apparatus, heated to 180 ° C. under a nitrogen atmosphere and maintained for 2 hours.
Adjusted to 0 Torr. After 1 hour in this state, the pressure was reduced to 0.2 Torr over 2 hours, the temperature was raised to 260 ° C. over 1 hour while maintaining the reduced pressure, and the resulting phenol was distilled off for a total of 9 hours while distilling off. The reaction was performed. After completion of the reaction, nitrogen was blown into the reactor to normal pressure, and polycarbonate was extracted from the bottom of the reactor with a gear pump. This resin is fed into a twin-screw extruder (barrel temperature 260 ° C.), 0.12 g of n-butyl p-toluenesulfonate is used as a catalyst deactivator, and ADK STAB AO-50 (manufactured by Asahi Denka Co., Ltd.) is used as an antioxidant. ) And ADK STAB 2112 (made by Asahi Denka Co., Ltd.) for 3.
70 g, and 55.8 g of SH556 (manufactured by Toray Dow Corning Co., Ltd.) as a release agent were kneaded to obtain a uniform polymer. The polymer was formed into a strand through a die, and then cut into pellets by a pelletizer. This copolymerized polycarbonate has a bisphenol A: spiroglycol molar ratio = 5.
2:48, weight average molecular weight Mw = 85,000.
Physical properties of this resin are as follows: refractive index nD = 1.525, Abbe number ΔD = 40, glass transition temperature Tg = 123 ° C.
In a falling ball impact test in which a steel ball was dropped from a height of 27 cm, the ball was extremely high in impact resistance, not cracking even with a 535 g ball. After the obtained resin composition was sufficiently dried at 100 ° C., it was molded into a disk having a diameter of 50 mm and a thickness of 2 mm using an injection molding machine, and subjected to the following tests.

Example 2 (Preparation of Composition for Silicone Coating) γ-glycidoxypropylmethyldiethoxysilane 10
6.8 g was cooled to 10 ° C., and 15.5 g of a 0.05 N hydrochloric acid aqueous solution was gradually added dropwise with stirring. After completion of the addition, methanol-dispersed colloidal silica (average particle size: 12 ± 1 m) was used.
490 g) were added dropwise with stirring.
After completion of the dropwise addition, stirring was continued at 10 ° C. for further 12 hours.
To this liquid, 73 g of methyl cellosolve, 292 g of isopropyl alcohol, 146 g of n-butanol, and a silicone surfactant (L-7002 manufactured by Nippon Unicar Co., Ltd.)
After adding 2.8 g and stirring sufficiently, a silicone-based coating composition was obtained.

Example 3 As a commercially available acrylic-styrene-based aqueous emulsion, F430 (manufactured by Showa Polymer Co., Ltd., solid content: 45%) was used.
%) 200 g of pure water, methanol 2
Then, 800 g of ethyl cellosolve and 100 g of propylene glycol monomethyl ether were added. Subsequently, pt-butylphenyl salicylate 25
g and polymer stabilizers (SANOL LS manufactured by Sankyo Co., Ltd.)
-770) 5 g was added to prepare a primer solution. The primer solution obtained above was applied to the resin disk sample obtained in Example 1 by a dipping method. This sample was heated and cured in a hot air dryer at 100 ° C. for 1 hour. The thickness of this primer layer was 3.0 μm. On top of this, the silicone-based coating solution obtained in Example 2 was applied by a dipping method.
Heat cured for hours. Table 1 shows the physical properties of the hard-coated disk thus obtained.

Example 4 To a mixed solution of 100 g of glycerin diglycidyl ether (Denacol EX313 manufactured by Nagase Sangyo Co., Ltd.) and 8.1 g of magnesium perchlorate, 216 g of methyl cellosolve was added to obtain a homogeneous solution. To this, several drops of a leveling agent (Y-7002 manufactured by Nippon Unicar Co., Ltd.) was added to prepare a primer solution. The primer solution obtained above was applied to the resin disk sample obtained in Example 1 by a dipping method. This sample was placed in a hot air drier at 100 ° C.
For 1 hour to cure by heating. The thickness of this primer layer was 2.0 μm. The silicone-based coating liquid obtained in Example 2 was applied thereon by a dipping method, and was cured by heating at 110 ° C. for 1 hour. Table 1 shows the physical properties of the hard-coated disk thus obtained.

Example 5 Commercially available polyurethane E380 (Nippon Elastollan Co., Ltd.)
(Polyalkylene carbonate), and adjusted to a primer concentration of 3% by adding tetrahydrofuran. A resin disk with a primer layer and a silicone cured layer was obtained in the same manner as in Example 3 except that this solution was used as a primer solution. Table 1 shows the physical properties of the obtained disk.

Comparative Example 1 The silicone coating liquid prepared in Example 2 was directly applied to the resin disk obtained in Example 1 without applying a primer layer by a dipping method.
Heat cured for hours. The results are shown in Table 1. The adhesion of the film was not sufficient and the falling ball impact value was very low.

Measurement of coating film hardness: The coating film was rubbed 10 times under a load of 1 kg with # 0000 steel wool under a load of 1 kg, and evaluated according to the degree of scratching in four steps. a: There is no damage even with strong friction. b: Slightly scratched when strongly rubbed. c: Scratches even with weak friction. d: easily scratched with nails. -Adhesion: 100 squares of 1 mm are formed on the application surface of the base material using a steel knife. Next, a cellophane pressure-sensitive adhesive tape was pressed firmly on the tape, and then rapidly peeled off in the direction of 90 °, and the presence or absence of peeling of the coating film was examined. -Falling ball impact test: steel balls of various weights from a height of 127 cm
The molded article was dropped naturally toward the center of the molded article, and the maximum weight at which the molded article did not crack was defined as the falling ball impact value.

[0054]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09D 183/04 G02B 1/04 G02B 1/04 // C09D 133/00 C09D 133/00 G02C 7/02 G02C 7/02 B29K 69:00 (72) Takashi Konishi 22nd Wadai, Tsukuba-shi, Ibaraki Pref. AA28 AA33 AG03 AH74 WA14 WA54 WA58 WA87 4J002 CD001 CG011 CG021 CK021 CP051 CP081 CP091 CP101 GF00 GP01 4J038 CG142 DB002 DG002 DL031 PA07 PC08

Claims (4)

[Claims] 1. A primer layer made of an organic resin and having a thickness of 0.1 to 20 μm on a surface of a plastic lens substrate made of a polycarbonate resin having the following structural formulas (1) and (2) as constituent units. And a coating composition containing an organosilicon compound and / or a hydrolyzate thereof is cured to form a silicone-based cured layer. Embedded image (In the above structural formula (1), X is , And the here, R ₃ and R ₄ is a hydrogen atom or an alkyl group or a phenyl group having 1 to 10 carbon atoms, R ₃
And R ₄ may combine to form a ring. R ₁ and R ₂
Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen, and R ₁ and R ₂ may be the same or different. Further, m and n represent the number of substituents and are integers of 0 to 4. ) (In the above structural formula (2), R ₅ , R ₆ , R ₇ , R ₈
Is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms. ) 2. The method according to claim 1, wherein the primer layer comprises polyacryl and / or
2. The plastic lens according to claim 1, which comprises a polymethacrylic resin as a main component. 3. The plastic lens according to claim 1, wherein the primer layer contains an epoxy resin as a main component. 4. The plastic lens according to claim 1, wherein the primer layer contains a polyurethane resin as a main component.