JPH0796555A - Plastic optical articles - Google Patents

Abstract

(57) [Summary] [Structure] A plastic optical article characterized by having a hard coat layer on a transparent substrate whose main component is a resin containing sulfur, in which at least a part of the surface is treated with an alkaline solution. . The transparent plastic optical article having the hard coat obtained by the present invention has the following effects. (1) By treating the surface of the base material, the film has excellent film adhesion and excellent light resistance and weather resistance. (2) It has excellent surface hardness and scratch resistance, and good transparency. (3) A prescription lens having a thin edge thickness can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic optical article having excellent durability such as impact resistance and abrasion resistance.
In particular, it is suitable for eyeglass lenses, camera lenses, and the like.

[0002]

2. Description of the Related Art Generally, a plastic material is lightweight and excellent in impact resistance, workability and mass productivity,
It is used for many purposes. Among the plastics having such characteristics, a resin containing sulfur has been attracting attention as a resin having a high refractive index (for example, Japanese Patent Laid-Open No. 6-58242).
4-26613). Further, a technique of providing a hard coat film on such a plastic substrate for the purpose of improving impact resistance, scratch resistance and the like of these surfaces has been disclosed (for example, JP-A-1-29724).

[0003]

However, in such a conventional technique, in addition to the fact that the adhesion between the hard coat film and the substrate is poor and the durability is insufficient,
It had a big problem that the heat resistance was extremely poor. .

Therefore, the present invention is intended to solve these problems, and has excellent adhesion to the hard coat film, plastic optics excellent in durability such as impact resistance and scratch resistance, and heat resistance. The purpose is to provide an article.

[0005]

The present invention has the following constitution in order to achieve the above object.

"A plastic optical article characterized by having a hard coat layer on a transparent substrate whose main component is a resin containing sulfur, which has at least a part of its surface treated with an alkaline solution." The alkaline solution is one obtained by mixing one or more alkali metal hydroxides, alkaline earth metal hydroxides, organic alkali metal compounds and organic bases and dissolving them in water, and preferably having a pH of 10 or more. , And more preferably an aqueous solution having a pH of 12 or more. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and the like. Specific examples of the alkaline earth metal hydroxide include calcium hydroxide, beryllium hydroxide, magnesium hydroxide and the like. Specific examples of the organic alkali metal compound include sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium methoxide, lithium ethoxide and the like. Specific examples of the organic base include aliphatic amines such as diethylamine and triethylamine, and aromatic amines such as aniline. Among these compounds, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like are preferably applied from the viewpoints of easy availability and economy.

The concentration of the alkaline solution is not particularly limited, but 1 to 50% by weight is preferably applied, and more preferably 5 to 30% by weight, from the viewpoint of shortening the processing time, stability of the processing solution and the like. Used in a range.

It is also preferable to add a surfactant or an organic solvent to the alkaline solution of the present invention for the purpose of improving the adhesiveness of the cured film or shortening the alkaline treatment time.

As the surface active agent, a cationic surface active agent, an anionic surface active agent and a nonionic surface active agent may be used alone or in combination of two or more. Specific examples of the cationic surfactant, octadecylamine acetate, tetradecylamine acetate, and stearyl amine acetate, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, Examples thereof include amine salts such as distearyldimethylammonium chloride and tetradecyldimethylbenzylammonium chloride, amines such as oxyethylenedodecylamine, and the like. Specific examples of the anionic surfactant, sodium dodecylbenzene sulfonate, sodium lauroylmethyl taurate, and sulfonates such as sodium dioctylsulfosuccinate, sodium lauryl sulfate, ammonium lauryl sulfate, sulfates such as triethanolamine lauryl sulfate, And so on. Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and other polyoxyethylene derivatives, polyoxyethylene derivatives. Oxyethylene monolaurate, polyoxyethylene monostearate,
Esters such as polyoxyethylene monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan monolaurate Is mentioned.

The surfactant is the composition of the resin containing sulfur,
A cationic surfactant is preferably used in view of stability in an alkaline solution and treatment effect, though it is appropriately selected depending on the characteristics and the like. The content of the surfactant in the alkaline solution should be appropriately determined, but usually 0.01% by weight to 20% by weight is applied, and particularly 0.1% by weight from the viewpoint of treatment effect and stability. -10 wt% is preferably applied.

Examples of the organic solvent include alcohols, ketones and esters. The present invention is a method of providing a cured film after contacting a resin containing sulfur with an alkaline solution, but the contact method is not particularly limited, but a dipping method, a shower method or the like is appropriately selected and used.

The treatment time is empirically determined, but is usually 1 minute to 100 hours, preferably 1 minute to 5 hours.
Processed in a time range. The treatment temperature is determined experimentally in consideration of the composition and characteristics of the three-dimensional crosslinked resin, but is usually 5 ° C to 100 ° C, preferably 50 ° C to
95 ° C is applied. The alkali treatment can be performed in combination with ultrasonic treatment in order to enhance the treatment effect.

Before and after the alkali treatment, an activating gas treatment may be performed as a cleaning process or a physical treatment for the purpose of improving the stability of the treatment and the treatment effect. The activated gas treatment means placing a gas in the presence of generated ions, electrons or excited gas under normal pressure or reduced pressure. As a method of generating these activated gases, for example, a method using low-temperature plasma obtained by corona discharge, direct current under reduced pressure, low frequency, high frequency discharge is preferably used from the viewpoint of reproducibility, productivity, etc. It The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, water vapor, ammonia, carbon monoxide, chlorine. , Nitric oxide, nitrogen dioxide and the like. These can be used not only as one kind but also as a mixture of two or more kinds.

Oxygen is mentioned as a preferable gas among the above, and it may be one existing in nature such as air. Particularly preferably, pure oxygen gas is effective for improving adhesion. When such an activated gas is applied, it should be optimized depending on the composition of the transparent substrate containing a resin containing sulfur as a main component, curing conditions, physical properties such as heat resistance, and is determined experimentally. It should be.

On the surface of the transparent substrate formed by these treatments and containing a resin containing sulfur as a main component, there is a large difference in the existing amount of sulfur before and after the treatment, and the sulfur is remarkably reduced after the treatment. Was confirmed. It was also confirmed that the surface of the substrate was in a state where the number of active functional groups was increased. For example, X-ray photoelectron spectroscopy (ESC
A), or Fourier transform infrared spectroscopy (FT-IR-
The amount of sulfur atoms on the surface in ATR) was 3/4 or less of the amount of sulfur atoms before treatment.

Further, by observing the surface with an atomic force microscope (AFM), it was confirmed that the degree of unevenness of the surface of the substrate was significantly changed before and after the above-mentioned surface treatment.
For example, the degree of unevenness on the surface of the substrate before the treatment, that is, the average height (depth) is 1 nm or less, whereas the average height after the treatment increases to 5 nm, and the average particle size varies depending on before and after the surface treatment. , 8 nm to 35 nm. Thus, it is considered that the decrease of S or the change of the surface shape greatly contributes to the adhesion of the hard coat film.

The average height (depth) obtained by AFM observation here is 1/2 of the distance between the peaks and valleys in the concavo-convex state, and is the average of all images observed in the 400 nm square field of view. It is a thing.

The average particle size is 40 in the AFM observation image.
This is the average of all particle sizes in the 0 nm field.

The resin containing sulfur in the present invention can be used without limitation as long as it is a resin containing sulfur, and a resin having sulfur in the main chain and / or side chain is preferably used. Among them, a resin obtained by polymerizing a monomer composition containing 10% by weight or more of at least one selected from monomers having one or more thiol (meth) acrylate groups in the molecule is particularly preferably used. . Particularly, the refractive index is 1.54 or more, and further 1.5
It is preferably 4 to 1.70.

Here, examples of the thiol (meth) acrylate include compounds represented by the following general formulas (II), (III) and (IV).

[0021]

[Chemical 1] (In the formula, R ⁴ represents hydrogen or a methyl group. M is 1 to 4
Indicates an integer. )

[Chemical 2] (In the formula, R ⁵ represents hydrogen or a methyl group, and n represents 0 or 1.)

[Chemical 3] (In the formula, R ⁶ represents hydrogen or a methyl group.) Here, as a dehydrochlorinating agent for obtaining a thiol (meth) acrylate-based monomer, 3-95 molar equivalents of a tertiary amine and 5 with respect to —SH group are used. By using the metal hydroxide in an amount of up to 120 molar equivalents, the purity and yield of the monomer can be increased.

The thiol (meth) acrylate is
For example, a peroxide-based or azo-based initiator generally used for radical polymerization is added in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the monomer, and then polymerization is performed by heating or irradiating light. Therefore, a resin having excellent transparency can be manufactured. At this time, other monomers can be added to the above thiol (meth) acrylate as a monomer and copolymerized. In this case, due to the characteristics of the obtained resin, the above general formulas (II), (III) and (IV)
It is preferable to add 10% by weight or more of at least one kind of monomer selected from the monomers shown in.

The monomer to be added is not particularly limited as long as it is an olefin compound, and (meth) acryl compound, styrene compound, acrylonitrile, N-phenylmaleimide and the like are preferable.

A resin having excellent processability can be obtained by adding a polyfunctional thiol compound in addition to the olefin compound as a copolymerization component. Examples of polyfunctional thiol compounds include pentaerythritol tetrakisthioglycolate and trismercaptopropyl isocyanurate. In order to obtain resins having excellent mechanical properties using various thiol (meth) acrylate-based monomers, thiol (meth) acrylate is 15 to 90% by weight, styrene is 10 to 85% by weight, and halogen atom-containing or non-containing. It is preferable to copolymerize the di (meth) acrylate containing bisphenol A in the structure at a ratio of 75% by weight or less. At this time, the above-mentioned olefin compound may be copolymerized at a ratio of 45% by weight or less.

As the di (meth) acrylate containing bisphenol A in the structure, for example, the following general formula (V)
The compound shown by is mentioned.

[0026]

[Chemical 4] (In the formula, R ⁷ represents hydrogen or a methyl group.) The various thiol (meth) acrylate-based monomers used in this copolymer can be used without particular limitation, and particularly, the above general formula (I
When the compounds represented by I), (III) and (IV) are used, it is possible to obtain a resin excellent in optical properties such as a high refractive index and a high Abbe number in addition to mechanical properties. Further, in order to obtain a resin having excellent wear characteristics by using various thiol (meth) acrylate-based monomers,
15 to 90% by weight of at least one selected from thiol (meth) acrylate-based monomers, and 10 monomers having both urethane bond and (meth) acrylic group in the molecule are used.
It is preferable to copolymerize at a ratio of about 85% by weight. At this time, the above-mentioned olefinic compound may be copolymerized at a ratio of less than 45% by weight.

Examples of the monomer having both a urethane bond and a (meth) acryl group in the molecule include a monomer having a substituent represented by the following general formula (VI).

[0028]

[Chemical 5] (Here, R ⁸ is hydrogen or a methyl group, X is a carbon number of 1 to
10 represents an alkylene group, and 1 represents an integer of 0 to 3. ) The thiol (meth) acrylate-based monomer can be used without any limitation. In particular, when the compounds of the general formulas (II) to (IV) are used, in addition to abrasion resistance, high refractive index is obtained. It is possible to obtain a resin having excellent optical characteristics such as a high rate and a high Abbe number.

A cast polymerization method is suitable as a method for producing the resin containing sulfur of the present invention. As a preferable example of the molding method in this case, the above-mentioned thiol (meth)
A liquid obtained by mixing at least one of acrylates or copolymerization components and the thiol (meth) acrylate of the present invention is poured together with a polymerization initiator into a mold made of a glass or metal mold and an adhesive tape or a plastic gasket, and 30 A method of molding by heating at ˜150 ° C. for 0.1 to 40 hours or by irradiating with ultraviolet rays can be mentioned.

When a resin is produced from thiol (meth) acrylate, peroxide initiators such as benzoyl peroxide, t-butyl peroxyisobutyrate, diisopropyl peroxydicarbonate and t-butyl are particularly preferable. Polymerization using peroxypivalate makes it possible to produce a resin having excellent appearance quality.

When producing the sulfur-containing resin of the present invention, known additives such as an ultraviolet absorber, an antioxidant and a colorant may be appropriately contained.

By using the above-mentioned thiol (meth) acrylate, a resin having a high refractive index and a high Abbe number and excellent transparency can be produced, and the obtained resin is a sulfur-containing resin. No, there was no odor during processing. Further, since it is a thiol ester-based compound, it has a lower water absorption rate than the ester-based compound and is also excellent in chemical resistance.

In the present invention, a hard coat film is provided on the upper layer of a transparent substrate having a high refractive index and containing sulfur in the main chain and / or side chain. The hard coat film has an organic polymer as a main component, but the organic polymer is not particularly limited here. Specific examples of the organic polymer include acrylic resin, silicone resin,
Polyurethane resin, epoxy resin, melamine resin,
Examples thereof include polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins and the like. These resins can be used alone or in combination of two or more kinds, and can be three-dimensionally crosslinked by using various curing agents, crosslinking agents and the like. Particularly for applications where surface hardness is important, a curable resin is preferable, and for example, an acrylic resin, a silicone resin, an epoxy resin, a polyurethane resin, a melamine resin is preferably used alone or in combination. To be done. When considering various characteristics such as surface hardness, heat resistance, chemical resistance, and transparency, it is preferable to use a silicone resin.
More preferably, a polymer obtained from an organosilicon compound represented by the following general formula (A) or a hydrolyzate thereof can be mentioned.

R ¹ _a R ² _b SiX _4-ab (A) (wherein R ¹ is an organic group having 1 to 10 carbon atoms, and R ²
Is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, X is a hydrolyzable group, and a and b are 0 or 1.
And (a + b) is 0, 1 or 2. ) Examples of the organosilicon compound represented by the general formula (A) include methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate.
Tetraalkoxysilanes such as butyl silicate, and their hydrolysates, further methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxy. Silane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ
-Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (amonoethyl) -γ
-Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane,
Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane α-glycidoxyethyltriethoxysilane, β-glyce Sidoxyethyltrimethoxysilane, 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- (3,3 4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ-
(3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl)
Propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltriemethoxysilane, triacyloxysilanes, or triphenoxysilanes or hydrolysates thereof and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane,
Phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-
Methacryloxypropylmethyldiethoxysilane, γ
-Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane Silane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethylsilane Ethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyl Ludiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glyce Sidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane , Γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. Shishiran, diphenoxy silane or diacyl-oxy silane or hydrolyzate thereof are examples.

These organosilicon compounds may be used alone or in combination.
It is also possible to add more than one species. In particular, for the purpose of imparting dyeability, it is preferable to use an organic silicon compound containing an epoxy group or a glycidoxy group, which gives a high added value.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and accelerate the curing. Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid, or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added.

Since alcohol and the like are produced during the hydrolysis, it is possible to carry out the hydrolysis without a solvent. However, for the purpose of making the hydrolysis even more uniform, after mixing the organic silicon compound and the solvent, the hydrolysis is carried out. It is also possible to disassemble. Further, depending on the purpose, it is possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use, and to add an appropriate solvent after that. Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as N, N-dimethylformamide. Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary.

It is preferable to add a fine particle inorganic oxide to the hard coat film for the purpose of improving scratch resistance and heat resistance. The fine particle inorganic oxide may be used alone or in combination of two or more, and is not particularly limited, but a colloidally dispersed sol is preferably used from the viewpoint of workability. Specific examples thereof include silica sol, titania sol, zirconia sol, antimony oxide sol, ceria sol, alumina sol and the like.

Further, various surfactants can be used in these coating compositions for the purpose of improving the flow at the time of coating, and in particular, a block or graft of dimethylpolysiloxane and alkylene oxide can be used. Copolymers and further fluorochemical surfactants are effective.

Further, for the purpose of improving the weather resistance, it is possible to add an ultraviolet absorber or an antioxidant as a method for improving heat resistance deterioration.

Further, an inorganic compound other than the particulate inorganic oxide may be added to these coating compositions as long as the film performance and transparency are not significantly reduced. By using these additives together, various properties such as adhesion to the substrate, chemical resistance, surface hardness, durability, dyeability can be improved. Examples of the inorganic material that can be added include metal alkoxides represented by the following general formula (VII), chelate compounds and / or hydrolysates thereof.

M (OR) m (VII) (wherein R is an alkyl group, an acyl group or an alkoxyalkyl group, and m is the same value as the charge number of the metal M. M is silicon, titanium, zircon, Antimony, tantalum, germanium, aluminum, etc.) When forming the hard coat film in the present invention, various curing agents can be used for the purpose of accelerating curing and low temperature curing. As the curing agent, various epoxy resin curing agents, various organic silicon resin curing agents, etc. are applied.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds or metal alkoxides, and organic carboxylates of alkali metals, carbonic acid. Examples include various salts such as salts, and radical polymerization initiators such as peroxides and azobisisobutyronitrile. These curing agents can be used as a mixture of two or more kinds. Among these curing agents, the following aluminum chelate compounds are particularly useful for the purpose of the present invention from the viewpoints of stability of coating materials and prevention of coloration of coating films after coating.

The aluminum chelate compound as used herein is an aluminum chelate compound represented by the general formula AlX _n Y _3-n (where X is OL (L is a lower alkyl group) and Y is the general formula M ¹ COCH). ₂ COM ² (M ¹ , M
² is a lower alkyl group), a ligand derived from a compound represented by the formula: M ³ COCH ₂ COOM
⁴ (at least M ³ and M ⁴ are lower alkyl groups) is at least one selected from ligands derived from compounds, and n is 0, 1 or 2. ).

Among the aluminum chelate compounds represented by Al _n Y _3-n , aluminum acetylacetonate and aluminum bisethylacetonate are preferred from the viewpoints of solubility in the composition, stability, effect as a curing catalyst, and the like. Acetate monoacetylacetonate, aluminum di-
Preferred are n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like. It is also possible to use a mixture of two or more of these.

As a coating method, a method used in a usual coating operation can be applied, but for example, dip coating, flow coating method, spin coating method and the like are preferable. The coating composition thus applied is dried by heating,
Or cured.

As a heating method, hot air or infrared rays can be used. The heating temperature should be determined depending on the substrate to be applied and the coating composition to be used, but usually room temperature to 250 ° C, more preferably 35 to 200 ° C is used. If the temperature is lower than this, curing or drying tends to be insufficient, and if the temperature is higher than this, thermal decomposition, cracking and the like occur, and further problems such as yellowing are likely to occur.

In applying the hard coat in the present invention, it is preferable that the surface to be applied is cleaned, and in the case of cleaning, dirt is removed by a surfactant, degreasing by an organic solvent, and steam cleaning by Freon. Etc. are applied.

The film thickness of the coating film containing the organopolysiloxane and the fine particle inorganic oxide as the main components is not particularly limited. However, it is preferably used in the range of 0.1 to 20 microns from the viewpoints of maintaining adhesion strength and hardness. Particularly preferably, it is 0.4 to 10 microns.

Further, it is generally known that an antireflection effect is obtained by laminating a plurality of coating films having different refractive indexes, and it is preferably used when a plastic substrate having a high refractive index is used.

In order to impart antireflection properties, there is also a method of forming a single-layer or multilayer antireflection film on the hard coat film by a dry method. The substance to be formed is an inorganic substance having essentially high hardness, and metal, metal or metalloid oxides, fluorides, silicides, borides, carbides, nitrides, sulfides and the like are selected.

As the metal oxide, SiO ₂ , SiO,
ZrO ₂ , Al ₂ O ₃ , TiO ₂ , Sb ₂ O ₃ , Sb ₂
O ₂ , Y ₂ O ₃ , thallium oxide, ytterbium oxide,
Examples thereof include tantalum oxide. As the fluoride, Mg
F _{2 and the} like can be mentioned. As the metal nitride, Si ₃ N ₄
Etc.

Examples of the method for forming a single-layer or multi-layer antireflection film of the above-mentioned substance include a vacuum deposition method, a sputtering method, an ion plating method, and an ion beam assist method. Furthermore, a coating of a water-repellent organic substance on the surface of the antireflection film for the purpose of preventing stains and imparting water repellency is also preferably used as long as the antireflection effect is not impaired. The transparent plastic optical article having a hard coat obtained by the present invention has excellent weather resistance, and has good surface hardness, scratch resistance, transparency, excellent appearance, and a high refractive index substrate, and thus has a thickness of edge. A thin lens can be obtained, which is useful for various lenses. Furthermore, it is particularly useful for optical lenses such as corrective lenses and sunglass lenses by the high value-added processing that is usually performed on the hard coat surface.

The following examples are given to clarify the gist of the present invention, but the present invention is not limited to these examples.

[0055]

【Example】

Examples 1-3, Comparative Examples 1-2 (1) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate γ-glycidoxypropyl was added to a reactor equipped with a rotor. 60.0 g of trimethoxysilane was charged, the liquid temperature was maintained at 10 ° C., and 13.7 g of 0.01N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. After completion of dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of coating composition 102.0 g of methanol, 59.5 g of benzyl alcohol, 131.7 g of N, N-dimethylformamide, 0.9 g of a fluorinated surfactant and bisphenol A were added to the silane hydrolyzate. 42.5 g of epoxy resin (trade name: Epicoat 827, manufactured by Shell Chemical Co., Ltd.) was added and mixed, and colloidal antimony pentoxide sol (trade name: Antimonsol A-2550, manufactured by Nissan Chemical Co., Ltd. average particle diameter 60
(mμ) 177.1 g and aluminum acetylacetonate 8.5 g were added and sufficiently stirred to obtain a coating composition.

(2) Preparation of plastic base material A 1000 cc three-necked flask was charged with 30 g of the compound represented by the following formula (VIII), 300 g of toluene, 500 g of 1N sodium hydroxide, 1 g of sodium pororohydride, and 100 mg of hydroquinone monomethyl ether. , 0
Methacrylic acid chloride 33 under stirring at ℃ under nitrogen
After slowly adding g, the mixture was stirred at 0 ° C. for 2 hours. afterwards,
The toluene layer was washed, filtered, and the solvent was distilled off to obtain a compound of the following formula (IX).

[0058]

[Chemical 6] Further, a solvent prepared by adding 1 part by weight of benzoyl peroxide to 99 parts by weight of the obtained compound was poured into a mold composed of a glass mold and an adhesive tape, and the mixture was heated at 50 ° C to 120 ° C.
The temperature was raised to 15 ° C over 15 hours to obtain a resin. The refractive index of the obtained resin was 1.64.

(3) Substrate treatment Table 1 shows the plastic substrate obtained in (2) above.
It processed by the method shown in.

(4) Coating and curing The coating composition prepared in (1) above was pulled up to the plastic substrate obtained in (3) above at a speed of 1
It was applied by dipping onto a plastic substrate under the condition of 0 cm / min, and then precured at 100 ° C. for 12 minutes. Then 11
It was heated at 0 ° C. for 4 hours to obtain a transparent plastic molding having a hard coat.

(5) On the transparent plastic molding having the hard coat obtained in (4) above, inorganic oxides ZrO ₂ , SiO ₂ , which are antireflection coatings,
The optical film thicknesses of TiO ₂ and SiO ₂ are 0.5λ / 4, 0.5λ / 4, λ / 2, λ /
4 (λ = 521 nm) was set to form a multilayer coating.

Various properties of this coating film were measured. The evaluation method is shown below, and the results are shown in Table 1.

(6) Performance Evaluation (a) Appearance The sample having good transparency and no cracks with the naked eye was evaluated as ◯.

(B) Total light transmittance Digital SM color computer (Suga Test Instruments Co., Ltd.)
The total light transmittance (Tt%) was measured.

(C) Adhesion 100 pieces of cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) were put on the surface of the coating film with a steel knife to insert 100 scorings reaching the base material of 1 mm. Crucifixion 9
The sample which was peeled off rapidly in the direction of 0 degree and had no coating film isolation was rated as ◯.

(D) Weather resistance Adhesion was evaluated after exposure to the outdoors, and the period during which no film peeling occurred was shown.

(E) Light resistance Adhesion after irradiation was evaluated by using an ultraviolet regular life fade meter FA-3 type (manufactured by Suga Test Instruments Co., Ltd.), and those having no peeling of the coating film were evaluated as ◯.

(F) Steel Wool Hardness The coated surface is rubbed with # 0000 steel wool to determine the degree of scratching. The criteria are as follows: A ... No scratches even with strong friction.

B ... Strong rubbing causes a slight scratch.

C ... Scratch occurs even with weak friction.

However, the number of times of friction was 5 reciprocations.

[0072]

[Table 1]

[0073]

The transparent plastic optical article having a hard coat obtained by the present invention has the following effects.

(1) By subjecting the surface of the base material to excellent film adhesion, light resistance and weather resistance are excellent.

(2) The surface hardness and the scratch resistance are excellent, and the transparency is good.

(3) A prescription lens having a thin edge thickness can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area // B29K 81:00

Claims (6)

[Claims] 1. A plastic optical article having a hard coat layer on a transparent substrate whose main component is a resin containing sulfur, at least a part of the surface of which is treated with an alkaline solution. 2. The sulfur-containing resin contains one monomer having at least one thiol (meth) acrylate group in the molecule.
The plastic optical article according to claim 1, which is a resin obtained by polymerizing a monomer composition containing 0% by weight or more. 3. The resin containing sulfur has a refractive index of 1.54.
The plastic optical article according to claim 1, which is ˜1.70. 4. The hard coat layer comprises an organopolysiloxane and a particulate inorganic oxide as main components.
A plastic optical article as described above. 5. The plastic optical article according to claim 4, wherein the organopolysiloxane is an organosilicon compound represented by the following general formula (I) and / or a hydrolyzate thereof. R _a R ¹ _b SiX _4-ab (I) (wherein R is an organic group having 1 to 10 carbon atoms, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, and a and b is 0 or 1.) 6. The particulate inorganic oxide is 5% by weight or more,
The plastic optical article according to claim 4, which is contained in an amount of 80% by weight or less.