JPH06337303A - Antireflection plastic optical parts - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] Obtained by vinyl polymerization of a urethanated (meth) acrylic monomer obtained by reacting a (meth) acrylic monomer represented by the following general formula (I) with a polyfunctional isocyanate. An antireflection plastic optical component comprising a transparent plastic substrate made of a polymer and the following coatings A and B laminated in this order. (Here, R ¹ and R ² are hydrogen or a methyl group, m and n are integers whose sum is 0 to 4, and X is chlorine, iodine, or bromine.) A. A coating composed mainly of an organopolysiloxane and a fine-particle inorganic oxide. B. A multilayer antireflection film made of an inorganic oxide, at least one of which is a layer containing titanium oxide. [Effect] It has light resistance and weather resistance that does not change yellow due to sunlight, ultraviolet rays, etc., has excellent abrasion resistance, adhesion, and dyeability, and does not have yellowing or transparency deterioration due to haze. It is possible to provide an optical component which is excellent in appearance without being visible.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical component, and more particularly to an antireflection plastic optical component excellent in light resistance, weather resistance and the like, whose transparency is important. In particular, it is preferably used for eyeglass lenses, camera lenses, CRT filters, optical recording substrates and the like. Further, it is also suitable for an optical body (transparent resin building article) used for architectural purposes.

[0002]

2. Description of the Related Art In recent years, plastic molded products, especially those used for optical applications, have excellent impact resistance and transparency, and are easily dyed, so that the demand for them has increased significantly in recent years. . In addition, various plastic moldings have been developed as represented by higher functionality, for example, higher refractive index of plastic lenses. However, even though the transparency is important, there is a problem that it turns yellow when exposed to sunlight or an illumination lamp.

As a technique for cutting off ultraviolet rays which is one of the causes of yellowing, there is a method of mixing an ultraviolet absorber with a plastic transparent substrate or paint. As transparent ultraviolet absorbers, for example, benzophenone-based and benzotriazole-based ones are known as organic ones, and titanium oxide, cerium oxide, etc. are known as inorganic ones. As a method of using this inorganic oxide as a hard coating agent, JP-A-58-46301, JP-A-59-49501, and JP-A-63-22563.
No. 5, for example, discloses a composition comprising titanium alcoholate and colloidal silica, or colloidal titanium oxide and a silane coupling agent.

[0004]

However, the organic UV absorber absorbs UV rays and deteriorates itself to turn yellow or brown, and finally becomes saturated and absorbs UV rays. In addition to disappearing, there is a problem of toxicity because it is an organic substance.

On the other hand, although inorganic oxides are less likely to deteriorate, they are not disclosed in JP-A-58-46301 and JP-A-59-49.
In the method described in Japanese Patent Publication No. 501, etc., there is a problem that the coating film is easily yellowed by irradiation with ultraviolet rays and has poor weather resistance, and particularly, there is a fatal defect that the adhesion of the coating film after a weather resistance test becomes poor. Met.

Therefore, the present invention is intended to solve these problems, and has excellent light resistance, weather resistance and water resistance, and has no yellowing or transparency deterioration due to haze, and has an appearance. It is an object of the present invention to provide an excellent antireflection plastic optical component.

[0007]

In order to solve the above object, the present invention has the following constitution.

"On a plastic transparent substrate made of a polymer obtained by vinyl-polymerizing a urethanized (meth) acrylic monomer obtained by reacting a (meth) acrylic monomer represented by the following general formula (I) with a polyfunctional isocyanate. , An antireflection plastic optical component, characterized in that the following A and B coatings are laminated in this order.

[0009]

[Chemical 2] (Here, R ¹ and R ² are hydrogen or a methyl group, m and n are integers whose sum is 0 to 4, and X is chlorine, iodine, or bromine.) A. A coating composed mainly of an organopolysiloxane and a fine-particle inorganic oxide. B. A multilayer antireflection film made of an inorganic oxide, at least one of which is a layer containing titanium oxide. The following can be mentioned as the (meth) acrylic monomer (hereinafter referred to as the component (a)) used in the present invention.

2- (4-hydroxyethoxy-3,5-
Dibromophenyl) -2- (4-acryloxyethoxy-3,5-dibromophenyl) propane, 2- (4-hydroxyethoxy-3,5-dibromophenyl) -2-
(4-methacryloxyethoxy-3,5-dibromophenyl) propane, 2- (4-hydroxyethoxy-3,
5-dibromophenyl) -2- (4-acryloxy-
3,5-dibromophenyl) propane, 2- (4-hydroxyethoxy-3,5-dibromophenyl) -2-
(4-methacryloxy-3,5-dibromophenyl) propane, 2- (4-hydroxy-3,5-dibromophenyl) -2- (4-acryloxy-3,5-dibromophenyl) propane, 2- (4-Hydroxy-3,5-dibromophenyl) -2- (4-methacryloxy-3,5
-Dibromophenyl) propane, 2- (4-hydroxydiethoxy-3,5-dibromophenyl) -2- (4-
Acryloxydiethoxy-3,5-dibromophenyl)
Propane, 2- (4-hydroxydiethoxy-3,5-
Dibromophenyl) -2- (4-methacryloxydiethoxy-3,5-dibromophenyl) propane and the like.

Particularly preferred among the above compounds are 2
-(4-Hydroxyethoxy-3,5-dibromophenyl) -2- (4-acryloxyethoxy-3,5-dibromophenyl) propane, 2- (4-hydroxyethoxy-3,5-dibromophenyl) ) -2- (4-Acryloxy-3,5-dibromophenyl) propane, 2- (4
-Hydroxydiethoxy-3,5-dibromophenyl)
2- (4-methacryloxydiethoxy-3,5-dibromophenyl) propane and mixtures thereof.

The polyfunctional isocyanate (hereinafter referred to as the component (a)) includes the following.

As the diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
There are 2,2,4-trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate methyl ester, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and trifunctional or higher functional compounds. Examples of the polyfunctional isocyanate include a product of hexamethylene diisocyanate that is piuretized, a reaction adduct of hexamethylene diisocyanate and trimethylolpropane, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and 1,6,11-undecane. Reaction adduct of triisocyanate, isophorone diisocyanate and trimethylolpropane, xylylene diisocyanate and The reaction adduct of trimethylolpropane, is reactive adduct of bis (isocyanatomethyl) cyclohexane and trimethylolpropane.

Among the above-mentioned isocyanate compounds, particularly preferable ones are xylylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane and the like.

In the present invention, the OH group of the (meth) acrylic monomer (a) represented by the above general formula is reacted with the NCO group of the polyfunctional isocyanate (a) to synthesize the urethanized (meth) acrylic monomer. .

By vinyl polymerizing this urethanized (meth) acrylic monomer, a resin for plastics having a high refractive index can be obtained. 1 vinyl monomer), other vinyl monomer having an aromatic ring in the molecule (hereinafter referred to as the second vinyl monomer)
Is preferably copolymerized.

The second vinyl monomer is intended to improve various performances required for the lens by copolymerizing with the first vinyl monomer. The second vinyl monomer preferably has a homopolymer having a refractive index of 1.55 or more, and particularly preferably has a nuclear halogen-substituted aromatic ring. Specific examples are as follows.

Styrene, divinylbenzene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, iodostyrene, phenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, mono Bromphenyl (meth) acrylate, dibromophenyl (meth) acrylate,
Tribromophenyl (meth) acrylate, bendabromophenyl (meth) acrylate, monochlorophenoxyethyl (meth) acrylate, dichlorophenoxyethyl (meth) acrylate, trichlorophenoxyethyl (meth) acrylate, monobromophenoxyethyl (meth) acrylate, Dibromophenoxyethyl (meth) acrylate, tribromophenoxyethyl (meth) acrylate, pentabromphenoxyethyl (meth) acrylate, N-vinylcarbazole, 2,2-
Bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, 2-
(4-methacryloxy-3,5-dibromophenyl)-
2- (4-hydroxy-3,5-dibromophenyl) propane, diallyl phthalate, diallyl isophthalate, triallyl trimellitate, benzyl acrylate and the like.

Among the above vinyl monomers, styrene, chlorostyrene, bromostyrene, dibromostyrene, tribromophenyl methacrylate, tribromophenoxyethyl methacrylate, divinylbenzene and mixtures thereof are particularly preferable. The amount of component (a) and component (b) used depends on the NCO group in component (a) and the amount in component (a).
It is preferable that the molar ratio of OH groups is selected in the range of 0.5 to 2.0, more preferably NCO / OH = 0.5.
It is 1.5. Outside this range, the mechanical and thermal properties of the lens tend to deteriorate, and the machinability and polishability tend to become poor. The second vinyl monomer having an aromatic ring in the molecule is preferably used in an amount of 0 to 70% by weight based on the total weight, but it is preferable to use an appropriate amount depending on reactivity and physical properties. If it exceeds 70% by weight, mechanical properties and machinability tend to be poor.

In the present invention, other than the first vinyl monomer and the second vinyl monomer, another polymerizable monomer or a compound containing a hydroxyl group containing no vinyl group is used.
Copolymerization can be carried out in a proportion of 0% by weight or less, or another polymer can be mixed in a proportion of 20% by weight or less.

As a method for producing a plastic lens using the resin for optical parts of the present invention, a known cast polymerization method is preferably used. In one embodiment, for example, the components (a) and (a) of the present invention are mixed, a usual polymerization initiator is added, and the reaction is preliminarily advanced to some extent (preliminary polymerization),
After the dissolved gas such as air is degassed in vacuum, it is injected into a mold and heated to polymerize.

The heating temperature is initially relatively low (eg 40
It is preferable that the reaction is carried out at a temperature of up to 50 ° C.), the temperature is raised to about 110 ° C. as the reaction progresses, and the addition polymerization is slowly carried out in order to reduce distortion of the lens.

As the polymerization initiator, various known ones can be used, but they should be selected according to the desired reaction temperature. For example, 1,1-azobiscyclohexane carbonate, diisopropyl peroxycarbonate, 1,
1'-azobiscyclohexane nitrate, di-tert
-Butyl peroxide and the like are good.

The plastic lens containing the resin of the present invention as a resin component has a higher refractive index and a tougher plastic lens than conventional plastic lenses, and has excellent impact resistance and shrinkage during molding polymerization. The rate is relatively small. Further, each of the (meth) acrylic monomer, the isocyanate compound and the aromatic vinyl monomer can be appropriately selected, whereby the optical properties can be freely adjusted and the bending elasticity is also excellent.

When producing these resins, known additives such as ultraviolet absorbers, antioxidants, colorants and the like may be appropriately contained.

Next, a coating film containing an organopolysiloxane and a fine-particle inorganic oxide as main components is used. Examples of the organopolysiloxane include, for example, an organosilicon compound represented by the following general formula (II) and / or The hydrolyzate can be mentioned.

R ³ _a R ⁴ _b SiX _4-ab (II) (wherein R ³ is an organic group having 1 to 10 carbon atoms, R ⁴ 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. ) As specific representative examples, tetraalkoxysilanes such as methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate, and their hydrates. Decomposition products and further methyltrimethoxysilane, methyltriethoxysilane,
Methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltri Ethoxysilane, 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) methyltri Methoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) Ethyltributoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-
Epoxycyclohexyl) butyltrimethoxysilane,
Trialkoxysilanes such as δ- (3,4-epoxycyclohexyl) butyl trimexisilane, triacyloxysilanes or triphenoxysilanes or their hydrolysates 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-glycidoxypropylmethyldibutoxyethoxysilane, γ- Glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxy Silane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. Alkoxysilanes, diphenoxylate 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 organosilicon compound containing an epoxy group or a glycidoxy group, which gives a high added value.

The above composition is usually diluted with a volatile solvent and applied as a liquid composition. The solvent used is not particularly limited, but the surface property of the object to be coated should not be impaired in use. Is required and should be determined in consideration of stability of the composition, wettability to a substrate, volatility, and the like. Also, the number of solvents is not limited to 1 and 2
It is also possible to use it as a mixture of two or more species.

Further, in order to improve the hardness, improve the adhesion to the inorganic oxide layer, and make the refractive index of the hard coat layer and the substrate coincide with each other, 5% by weight or more and 80% or less of the fine particle inorganic oxide is contained. preferable. That is, if it is less than 5% by weight, B
It is difficult to firmly and sufficiently adhere to the multi-layered coating, and when it exceeds 80% by weight, problems such as poor adhesion to the transparent plastic substrate, cracking in the coating itself, and reduction in impact resistance tend to occur.

The fine particle inorganic oxide is not particularly limited as long as it has good transparency in a coating film state, but workability,
A particularly preferable example from the viewpoint of imparting transparency is a sol dispersed in a colloidal form. As a more specific example, one or more selected from sol of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, tin oxide, beryllium oxide, and antimony oxide. The selection of the particulate inorganic oxide is important as one means for matching the refractive indexes of the plastic transparent substrate and the hard coat layer. For example, when polycarbonate is selected as the heat resistant plastic, it is preferable to select antimony pentoxide or a complex of titanium oxide and cerium oxide as the particulate inorganic oxide.
By suppressing the difference in refractive index between the plastic transparent substrate and the hard coat layer within 0.05, it is possible to suppress the occurrence of reflection interference fringe patterns caused by the minute difference in the thickness of the hard coat layer, and obtain an optical component with a clean appearance. it can.

Furthermore, it is possible to use various surfactants in these coating compositions for the purpose of improving the flow at the time of application, in particular, a block of dimethylpolysiloxane and alkylene oxide or Graft 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 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 (III), chelate compounds and / or hydrolysates thereof.

M (OR ⁴ ) m (III) (wherein R ⁴ is an alkyl group, an acyl group or an alkoxyalkyl group, and m is the same as the charge number of the metal M. M
Examples thereof include silicon, titanium, zircon, antimony, tantalum, germanium, aluminum and the like. ) In the case of forming the B multi-layer coating in the present invention, various curing agents can be used for the purpose of promoting curing, curing at low temperature and the like. 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 alkali metal organic carboxylates and carbonates. 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 each is a lower alkyl group) -derived ligand, and a general 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 AlX _n Y _3-n , aluminum acetylacetonate and aluminum bisethylacetate are preferred from the viewpoints of solubility in the composition, stability, effect as a curing catalyst and the like. Acetate monoacetylacetonate, aluminum di-n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like are preferable. 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, a dip coating, a flow coating method, a 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 liquid coating composition of the present invention, it is preferable that the surface to be applied is cleaned. During cleaning, dirt is removed with a surfactant, degreasing with an organic solvent, and freon. Steam cleaning is applied. Further, various pretreatments are also effective means for the purpose of improving adhesion and durability. Particularly preferably used methods are activation gas treatment, which will be described later, and treatment with a chemical such as acid or alkali, depending on the concentration.

The thickness of the coating film containing the organopolysiloxane and the fine-particle inorganic oxide as the main components in the present invention 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.

The present invention provides an antireflection film which is a multi-layered film made of an inorganic oxide, at least one of which is a layer containing titanium oxide, on these A films. Here, titanium oxide means TiO, TiO ₂ , Ti ₂ O ₃ , and Ti ₃ O.
₅ and so on. At least one layer of this antireflection film may be a layer containing titanium oxide. The layer containing titanium oxide may be a mixture of titanium oxide and other inorganic oxides, or may be a composite film containing titanium oxide. Here, the inorganic oxide other than titanium oxide in the mixture means SiO ₂ , SiO, ZrO ₂ , Al ₂ O ₃ , Y
₂ O ₃ , Yb ₂ O ₃ , MgO, Sb ₂ O ₃ , SnO ₂ ,
I. T. O. , Ta ₂ O ₅ , CeO ₂ , HfO ₂ , Pr
₆ O ₁₁ , MgF ₂ , Bi ₂ O ₃ , Cr ₂ O ₃ , Eu ₂ O
₃ , Fe ₂ O ₃ , In ₂ O ₃ , La ₂ O ₃ , MoO ₃ ,
Nd ₂ O ₃ , PbO, Sm ₂ O ₃ , Sc ₂ O ₃ , W
O ₃ , ZnO, AlF ₃ , BaF ₂ , CeF ₃ , CaF
₂ , LaF ₃ , LiF, Na ₃ AlF ₆ , Na ₅ Al ₃
F ₁₄ , NdF ₃ , NaF, PbF ₂ , SmF ₃ , SrF
₂ , ZnS, Ge, Si and the like are preferably used. It is possible to use not only one kind of these substances but also a mixture of two or more kinds. A composite film is an equivalent film and is a film that produces an equivalent single layer by combining titanium oxide and other layers. For example, this is the case where titanium oxide and silicon oxide are formed in this order at a certain ratio. .

In the case of a multilayer film, the optimum combination is determined by the refractive index of the plastic substrate or the hard coat film in determining the combination of film structures in the multilayer film, the film thickness, and the refractive index. Although the optimum combination varies depending on the required antireflection characteristics, other physical characteristics, and durability characteristics, many combinations have already been proposed for antireflection characteristics (Optical Technology Contact Vol. , No8.17〜23. (1971), 'OPTICS OF
THIN FILMS '159-283.A.VASICEK (NORTH-HOLLAND PUBL
ISHING COMPANY) AMSTERDAM (1960)), and there is no problem in using the combination of these in the present invention.

In forming the film, it is preferable that a surface treatment is performed to improve the adhesion between the hard coat film and the antireflection film on the surface thereof. Here, surface treatment means
Chemical treatment, alkali treatment, plasma treatment by high frequency discharge in oxygen atmosphere, treatment by ion beam irradiation of argon or oxygen in vacuum, treatment by ultraviolet irradiation, etc., but preferably activated gas treatment, in vacuum Ion beam irradiation is good.

The activated gas treatment is a generated ion, electron or excited gas under normal pressure or reduced pressure. As a method of generating these activated gases, for example, corona discharge, high-voltage discharge by direct current under low pressure, low frequency, high frequency, or microwave, or the like is used. In particular, the treatment with low temperature plasma obtained by high frequency discharge under reduced pressure is preferably used from the viewpoints of reproducibility and productivity. 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 type but also as a mixture of two or more types. Among the above, preferred gas is oxygen, and it may be one that exists in the natural world such as air. Particularly preferably, pure oxygen gas is effective for improving adhesion.

Next, the ion beam irradiation in vacuum is to treat the surface of the A coating by ionizing a gas of argon, oxygen, nitrogen or a mixture thereof.

Furthermore, for the same purpose, it is possible to raise the temperature of the treated substrate during the above-mentioned use. Above all, it is particularly effective when the treatment with an activated gas or the ion beam irradiation in vacuum is used.

The determination of the conditions for such treatment should be optimized depending on the composition for forming the organopolysiloxane, the type of the particulate inorganic oxide, the curing conditions, the film thickness thereof, the presence or absence of dyeing, and the like. Should be specified in.

In the present invention, the low-temperature high-frequency plasma condition is 1 × 10 ^-5 by reducing the pressure and introducing oxygen.
It is preferable to provide a high frequency output of 1-1000 W under a pressure of -1 Torr. Furthermore, 1 × 10 ⁻⁵ to 1 × 10
^It is particularly preferable to provide a high frequency output of 10 to 300 W under a pressure of ^-2 Torr.

In the present invention, the conditions for irradiating the ion gun in a vacuum include an acceleration voltage of 10 to 1000 V and an acceleration current of 1 to 500 m when a Kauffman type ion gun is used.
A is preferably used. An acceleration voltage of 100 to 900 V and an acceleration current of 10 to 200 mA are preferable for stable extraction of the ion current density.

In the present invention, as a method for providing an antireflection film which is a multi-layered film made of an inorganic oxide, at least one layer of which is a layer containing titanium oxide, there is liquid coating or dry coating such as vacuum deposition or sputtering. However, dry coating such as vacuum deposition and sputtering is preferably used from the viewpoints of denseness and productivity of the multilayer coating. At that time, under high frequency plasma generation, ion-assisted deposition with an ion gun,
Alternatively, ion plating using the voltage effect may be used.

In the present invention, the physical film thickness of at least one layer containing titanium oxide is preferably 10 nm or more. In addition, the degree of light yellowing resistance depends on the film thickness of the titanium oxide, and the thicker the film thickness, the less the degree of yellowing.

The plastic transparent substrate in the present invention may be colored gray, blue, red, yellow, green or the like for the purpose of improving contrast when used as an optical component. Examples of the method include methods such as dyeing and dyeing.

The antireflection plastic optical component obtained by the present invention is excellent in light resistance and weather resistance, and is also excellent in abrasion resistance, abrasion resistance, adhesion and dyeing property, and further is yellowed and has transparency due to haze. Of the correction lens, the CRT filter, because the transparency can be maintained even with a material that easily turns yellow due to sunlight, etc. It is especially useful as other precision equipment.

[0056]

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

Example 1 (1) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate γ-glycidoxypropyltrimethoxysilane 60.g was added to a reactor equipped with a rotor. 0 g 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 The silane hydrolyzate was mixed with 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. 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., average particle diameter 60 μ)
m) 177.1 g and aluminum acetylacetonate 8.5 g were added and sufficiently stirred to obtain a coating composition.

(2) Preparation of transparent plastic substrate 2-isocyanatoethyl-2,6-diisocyanate hexanoate 11.5 parts by weight, and 2- (4-acryloxyethoxy-3,5-dibromophenyl) -2-
To 88.5 parts by weight of (4-hydroxyethoxy-3,5-dibromophenyl) propane, 0.001 part of dibutyltin dilaurate as an NCO-OH reaction catalyst and 0.1 part by weight of ditertiary butyl peroxide as an initiator of the polymerization part are added. % Was added and mixed well. Since this mixed solution has a high viscosity and is difficult to uniformly mix, it was diluted with a solvent of dimethylformamide and uniformly mixed, and then the solvent was completely removed.

This mixed solution was heated to 50 ° C. to reduce the viscosity, poured into a mold composed of a glass plate having a diameter of 100 mm and a gasket made of polyethylene, and cast polymerization was carried out.

First, the NCO / OH reaction was completed by heating at 60 ° C. for 5 hours, then the temperature was raised to 80 ° C., and the polymerization was carried out for 30 hours while gradually increasing the temperature from 80 ° C. to 120 ° C. After the completion of the polymerization, the polymer was gradually cooled, and the polymer was released from the mold. The obtained resin was tough, colorless and transparent, had a high refractive index nD of 1.61, and had an Abbe number of 34.

(3) Coating and curing The plastic transparent substrate obtained in (2) above
The coating composition prepared in (1) is pulled up at a speed of 10
It was dip-coated on a plastic transparent substrate under the condition of cm / min, and then precured at 93 ° C. for 12 minutes. Then 110
It was heated at 0 ° C. for 4 hours to obtain a practic molding having the A coating.

(4) Formation of B multi-layer coating (formation of antireflection film) Vacuum deposition apparatus (BMC-800 manufactured by Syncron Corporation)
Was used to form an antireflection film corresponding to the B multi-layer coating by vacuum vapor deposition in the configuration shown in Table 1.

(A) Exhaust The transparent plastic substrate obtained in (3) was put into the vacuum vapor deposition apparatus and evacuated for 30 minutes, and the degree of vacuum was about 1 × 10 ^−5.
Torr (1.33 × 10 ⁻³ Pa) was used.

(B) Pretreatment Using a Kaufman type ion gun, an argon ion beam was irradiated for 1 minute under the above-mentioned atmosphere under the conditions of an acceleration voltage of 600 V and an acceleration current of 120 mA.

(C) The vapor deposition temperature was set to 60 ° C. for both the micro heater and the halogen heater. Deposition was performed while monitoring the film thickness using an optical film thickness meter. The first layer is introduced with oxygen and the degree of vacuum is about 6 × 10 ^-5 Torr.
Under the condition of (7.98 × 10 ^-3 Pa), oxygen is introduced into the second layer to obtain a vacuum degree of about 8 × 10 ^-5 Torr (1.064 × 10 ^-2 P
Under the condition of a), the third layer has a vacuum degree of about 1 × 10 ^-5 Torr.
It was vapor-deposited under the condition of (1.33 × 10 ⁻³ Pa).

[0067]

[Table 1] Example 2 In the same manner as in (1) to (3) of Example 1, a practic molded article having an A coating film was obtained.

The B multi-layer coating is formed by using a Kauffman type ion gun at the time of forming the third layer and accelerating voltage of 600 V and 12
All were prepared by the same method except that the vapor deposition (ion-assisted vapor deposition) was performed under the condition of 0 mA while irradiating the ion beam of argon.

Example 3 A practic molded article having an A coating was obtained in the same manner as in (1) to (3) of Example 1. (1) to (3) are in accordance with the first embodiment.

(4) Formation of B multi-layer coating (formation of antireflection film) Vacuum deposition apparatus (BMC-800 manufactured by Syncron Corporation)
Was used to form an antireflection film corresponding to the B multi-layer coating by vacuum vapor deposition in the configuration shown in Table 2.

(A) Evacuation: The plastic transparent substrate obtained in (3) was put into the vacuum vapor deposition apparatus and evacuated for 30 minutes, and the degree of vacuum was about 1 × 10 ^-5.
Torr (1.33 × 10 ⁻³ Pa) was used.

(B) Pretreatment Under the above conditions, oxygen is introduced and the degree of vacuum is set to about 1.0 × 10 ^−4.
It was set to Torr (1.33 × 10 ^-2 Pa). Under the conditions, the surface of the base material obtained in (2) was treated with plasma generated by applying high frequency (13.56 MHz) 300 W for 1 minute.

(C) The vapor deposition temperature was set to 60 ° C. for both the micro heater and the halogen heater. Deposition was performed while monitoring the film thickness using an optical film thickness meter. The first layer is introduced with oxygen and the degree of vacuum is about 3 × 10 ^-5 Torr
Under the condition of (3.99 × 10 ^-3 Pa), oxygen is introduced into the second layer to obtain a vacuum degree of about 8 × 10 ^-5 Torr (1.064 × 10 ^-2 P
Under the condition of a), the third layer has a vacuum degree of about 1 × 10 ^-5 Torr.
It was vapor-deposited under the condition of (1.33 × 10 ⁻³ Pa).

[0074]

[Table 2] Examples 4 to 6 Practical moldings having an A coating were obtained in the same manner as in (1) to (3) of Example 1. (1) to (3) are in accordance with the first embodiment.

(4) Formation of B Multilayered Film (Formation of Antireflection Film) Vacuum evaporation system (BMC-800 manufactured by Syncron Co., Ltd.)
Was used to form an antireflection film corresponding to the B multi-layer coating by vacuum vapor deposition in the configurations shown in Tables 3 to 5 (corresponding to Examples 3 to 5).

(A) Exhaust The transparent plastic substrate obtained in (3) was put into the vacuum vapor deposition apparatus and evacuated for 30 minutes, and the degree of vacuum was about 1 × 10 ^-5.
Torr (1.33 × 10 ⁻³ Pa) was used.

(B) Pretreatment A Kaufman type ion gun was used to irradiate an argon ion beam for 1 minute under the conditions of an acceleration voltage of 600 V and an acceleration current of 120 mA.

(C) The vapor deposition temperature was set to 60 ° C. for both the micro heater and the halogen heater. Deposition was performed while monitoring the film thickness using an optical film thickness meter. The first layer is introduced with oxygen and the degree of vacuum is about 3 × 10 ^-5 Torr.
Under the condition of (3.99 × 10 ^-3 Pa), oxygen is introduced into the second layer to obtain a vacuum degree of about 8 × 10 ^-5 Torr (1.064 × 10 ^-2 P
Under the condition of a), the third layer has a vacuum degree of about 1 × 10 ^-5 Torr.
It was vapor-deposited under the condition of (1.33 × 10 ⁻³ Pa).

[0079]

[Table 3] Comparative Example 1 In the same manner as in (1) to (3) of Example 1, a practic molded article having an A coating film was obtained. (1) to (3) are in accordance with the first embodiment.

(4) Formation of antireflection film Vacuum deposition apparatus (BMC-800 manufactured by Syncron Corporation)
Was used to form an antireflection film by vacuum vapor deposition in the configuration shown in Table 6.

(A) Evacuation: The transparent plastic substrate obtained in (3) was put into the vacuum vapor deposition apparatus and evacuated for 30 minutes, and the degree of vacuum was about 1 × 10 ^-5.
Torr (1.33 × 10 ⁻³ Pa) was used.

(B) Pretreatment Using a Kauffman type ion gun, an oxygen ion beam was irradiated for 1 minute under the conditions of an acceleration voltage of 600 V and an acceleration current of 120 mA.

(C) The vapor deposition temperature was set to 60 ° C. for both the micro heater and the halogen heater. Deposition was performed while monitoring the film thickness using an optical film thickness meter. The first layer is introduced with oxygen and the degree of vacuum is about 3 × 10 ^-5 Torr.
Under the condition of (3.99 × 10 ⁻³ Pa), the second layer has a vacuum degree of about 1 × 10 ⁻⁵ Torr (1.33 × 10 ⁻³ Pa),
The vacuum level is about 1 × 10 ^-5 Torr (1.33 × 10 ^-3 Pa)
It vapor-deposited on condition of.

Performance Evaluation (a) Appearance A black cloth is placed on the back, and the transparency, occurrence of microcracks, etc. are observed by the transmitted light of a fluorescent lamp. Good transparency,
The sample with no occurrence of microcracks was rated as ◯.

(B) Surface Hardness Steel wool of # 0000 was rubbed on the surface 5 times while applying a load of about 1 kg / cm ² to evaluate the degree of scratches. The criteria are as follows: A: No damage.

B: Slightly scratched.

C: There are many scratches.

(C) Adhesiveness With a feather single-edged razor, insert 100 cross hatches in a grid pattern at intervals of about 1 mm. Then, a cellophane tape (made by Nichiban) is attached to the cross-shaped surface, and the tape is peeled off in a direction of 90 degrees from the surface. Repeat this 3 times. The number of crosshatch that did not peel off at this time is evaluated.

(D) Abrasion resistance A non-woven fabric is moistened with a 5 times concentrated solution of artificial sweat (JIS B), and the surface is rubbed while a load of 2 kg is applied. The peeled state of the film is observed using transmitted light.

(E) Total light transmittance and yellowness The total light transmittance and yellowness (YI) were measured with a digital SM color computer (manufactured by Suga Test Instruments Co., Ltd.).

(F) Weather resistance The coated surface of the present invention was exposed to the south side at 45 ° for 3 months and the change in yellowness was traced. The difference from the initial yellowness (ΔYI) was evaluated.

(G) Light resistance Using a UV long life fade meter FA-3 type (manufactured by Suga Test Instruments Co., Ltd.), the irradiation time was changed to trace the change in yellowness. The difference from the initial yellowness (ΔYI) was evaluated. Examples 1 to 6 and Comparative Example 1 according to the above performance evaluation
Table 7 shows the results of comparative evaluation of the above. As is clear from the results in Table 7, by forming the B multi-layered film made of an inorganic oxide containing titanium oxide, a clear difference was observed in the light yellowing resistance and the weathering yellowing resistance. Comparative Examples 1 to 6 are optical parts Examples 1 to 6 which are oxide films.
It turns out that the result is very good compared to.
Further, as is clear from the comparison of Examples 1 to 6, it is understood that the larger the thickness of the film made of the inorganic oxide containing the titanium oxide layer, the greater the effect. Further, at this time, since the physical properties which are problematic when used as an optical component, particularly as a lens for spectacles, are sufficiently satisfied, it can be said that the optical component is also excellent in physical properties.

[0093]

[Table 4]

[Table 5]

[0094]

EFFECTS OF THE INVENTION According to the present invention, even a plastic transparent substrate which tends to change in yellow color has light resistance and weather resistance that does not change in yellow color due to sunlight, ultraviolet rays, etc., and has scratch resistance, abrasion resistance, adhesiveness, It is possible to provide an optical component which is excellent in dyeability, has no yellowing, does not deteriorate transparency due to haze, has no visible interference fringes, and has an excellent appearance. Therefore, light can be efficiently transmitted without lowering the transmittance of the transparent plastic substrate, and it is excellent in fashionability when used as a lens for spectacles.

Claims (8)

[Claims] 1. A plastic transparent substrate comprising a polymer obtained by vinyl polymerization of a urethanized (meth) acrylic monomer obtained by reacting a (meth) acrylic monomer represented by the following general formula (I) with a polyfunctional isocyanate. An antireflection plastic optical component, characterized in that the following A and B coatings are laminated in this order. [Chemical 1] (Here, R ¹ and R ² are hydrogen or a methyl group, m and n are integers whose sum is 0 to 4, and X is chlorine, iodine, or bromine.) A. A coating composed mainly of an organopolysiloxane and a fine-particle inorganic oxide. B. A multilayer antireflection film made of an inorganic oxide, at least one of which is a layer containing titanium oxide. 2. The organopolysiloxane is a polymer of a composition comprising an organosilicon compound represented by the following general formula (II) and / or a hydrolyzate thereof as a main component. Anti-reflection plastic optical parts. R ³ _a R ⁴ _b SiX _4-ab (II) (wherein R is an organic group having 1 to 10 carbon atoms, R ¹ is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms, and X is a hydrolyzed group. It is a decomposable group, and a and b are 0 or 1.) 3. The antireflection plastic optical component according to claim 1, wherein the fine particle inorganic oxide is contained in the film A in an amount of 5% by weight or more and 80% by weight or less. 4. The fine particle inorganic oxide contains at least one selected from silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, tin oxide, beryllium oxide and antimony oxide. The antireflection plastic optical component according to claim 1. 5. The antireflection plastic optical component according to claim 1, wherein the multilayer antireflection film is produced by a method selected from a vacuum deposition method, a sputtering method and an ion plating method. 6. The physical thickness of the layer containing titanium oxide is 10.
The antireflection plastic optical component according to claim 1, having a thickness of at least nm. 7. The transparent plastic substrate and / or A
The coating is colored, wherein the coating is colored.
The antireflection plastic optical component described. 8. The antireflection plastic optical component according to claim 1, wherein the difference between the refractive index of the A coating and the refractive index of the plastic transparent substrate is within 0.05.