JPH0675104A - Antireflective article and its production - Google Patents

Abstract

PURPOSE:To provide the antireflective article which has excellent heat resistance, surface hardness, durability and antireflectiveness and is free from microcracks by providing an antireflection film consisting of inorg. films on a hardening film provided on a crosslinked resin having a glass transition temp. of a specific value or above. CONSTITUTION:This antireflective article has the hardening film on the crosslinked resin having >=130 deg.C glass transition temp. and is further provided with the antireflection film consisting of >=1 layers of the inorg. film on this hardening film. A copolymer prepd. by polymerizing a compsn. contg. 20 to 98wt.% monomer expressed by formula and 2 to 80wt.% multifunctional monomer having >=2 pieces of unsatd. groups and having >=30wt.% total weight ratio of the monomer expressed by the formula and the multifunctional monomer having >=2 pieces of unsatd. groups is preferably used as the crosslinked resin. In the formula, R<3> denotes the substituent selected from hydrogen and 1 to 20C hydrocarbon groups; R<1>, R<2> denote the substituent selected from hydrogen, methyl group and ethyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflective article and a method for producing the same, and particularly to the excellent antireflective article,
Since it has heat resistance, it can be used for optical lenses, CRTs, LCDs,
It is preferably used for a front plate of a plasma display or a filter.

[0002]

2. Description of the Related Art At present, as a method for forming an antireflection coating on a plastic substrate, a chemical method in which a coating agent composed of an organic silane compound, inorganic fine particles or the like is multilayer-coated, or an inorganic oxide or an inorganic fluoride is vacuumed is used. A physical method in which multilayer coating is performed by vapor deposition or sputtering is common. However, it is the current situation that sufficient antireflection properties have not yet been obtained by chemical methods. It is known that the physical method is superior in antireflection property to the chemical method, and as a concrete proposal, it is disclosed in JP-A-61-61.
-117503 and JP-A-3-242602 can be cited. Japanese Unexamined Patent Publication (Kokai) No. 61-117503 discloses a technique of vacuum-depositing an inorganic fluoride while irradiating an Ar ion beam on a substrate made of a diethylene glycol bisallyl carbonate polymer in a fluorine compound gas. On the other hand, Japanese Patent Application Laid-Open No. 3-242602 discloses a technique of providing an antireflection film on a substrate having heat resistance.

[0003]

Problems to be Solved by the Invention JP-A-61-1175
In the technique disclosed in Japanese Patent Publication No. 03, No. 03, the plastic substrate does not have sufficient heat resistance, so high temperature conditions cannot be taken during film formation, and the resulting antireflection film has low surface hardness and durability. However, there is a big problem that the coating film is peeled off by immersion in warm water. On the other hand, the technique disclosed in Japanese Patent Application Laid-Open No. 3-242602 is capable of forming a film under high temperature conditions, and an antireflection film having excellent antireflection performance and high surface hardness is obtained. However, there is a problem that micro-cracks are likely to occur in the antireflection film when the above procedure is repeated.

The present invention is intended to solve the above problems of the prior art, and provides an antireflection article excellent in heat resistance, surface hardness, durability and antireflection property, and free from microcracks. The purpose is to

[0005]

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

"(1) A cured film is provided on a crosslinked resin having a glass transition temperature of 130 ° C or higher, and an antireflection film composed of one or more inorganic coatings is further provided on the cured film. Anti-reflective article.

(2) A cured film is provided on a crosslinked resin having a glass transition temperature of 130 ° C. or higher, and 1 is further formed on the cured film.
A method for producing an antireflection article, which comprises providing an antireflection film comprising an inorganic coating film having at least one layer. The crosslinked resin in the present invention has a glass transition temperature of 13
Any cross-linked resin having a temperature of 0 ° C. or higher can be used without particular limitation, but a resin having a glass transition temperature of 150 ° C. or higher is more preferable because it has better heat resistance. Here, the glass transition temperature refers to the temperature at which a polymer changes from an amorphous glass state to a rubber state, but in the transition region, various characteristics such as elastic modulus, expansion coefficient, heat capacity, refractive index, and dielectric constant are Change. The glass transition temperature can be measured from these changes in characteristics, and specifically, it can be evaluated by a known method such as differential scanning calorimetry (DSC) (for example, JIS K7121). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be determined by evaluating the crosslinked resin itself or a product obtained by heat treating it.

The mechanical properties of the crosslinked resin are preferably 200 kg / mm ² or more, and more preferably 330 kg / mm ² or more when the flexural modulus is used as an index.

The components of the crosslinked resin having a glass transition temperature of 130 ° C. or higher are represented by polymethacrylic acid resins such as polymethacrylic acid and polycarboxyphenylmethacrylamide, polystyrene resins such as poly (biphenyl) styrene, and the like. Polyolefin resin represented by poly (2,6-dimethyl-1,4-phenylene oxide), poly (oxycarbonyloxy)
-1,4-phenylene isopropylidene-1,4-phenylene)
Polycarbonate resin typified by
Polyester resin represented by 2,2,4,4-tetramethyl-1,3-cyclobutyleneoxyterephthaloyl), poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene), poly ( Oxy-1,4-phenylene isopropylidene
-1,4-phenyleneoxy-1,4-phenylenesulfonyl-
Polysulfone-based resins such as 1,4-phenylene), polyamide-based resins such as poly (iminoisophthaloyluimino-4,4'-biphenylene), poly (thio-1,4)
-Phenylenesulfonyl-1,4-phenylene), polysulfide resin represented by unsaturated polyester resin,
Epoxy resin, melamine resin, phenol resin,
Examples thereof include diallyl phthalate resin, polyimide resin, polyphosphazene resin, and the like, and it is possible to obtain a crosslinked resin exhibiting the above-mentioned thermal characteristics by introducing a crosslinked structure into these polymer groups. In particular, a polyolefin resin is preferable from the viewpoint of moldability, and the unsaturated group is 2
A polyolefin-based copolymer obtained by polymerizing a composition containing at least one polyfunctional monomer is more preferably used.

As the above polyolefin-based copolymer,
20 to 98% by weight of the monomer represented by the general formula (A), and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups.
Polymerization of a composition containing a total amount of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups of 30% by weight or more. A copolymer obtained by the above is preferably used.

[0011]

[Chemical 3] (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group.) General formula R ¹ and R ² contained in the maleimide derivative compound represented by (A) may be the same or different.

When R ³ is a hydrocarbon group, specific examples include a methyl group, an ethyl group, a propyl group, an octyl group,
Linear alkyl group such as octadecyl group, isopropyl group, sec-butyl group, tert-butyl group, branched alkyl group such as isopentyl group, cyclohexyl group, alicyclic hydrocarbon group such as methylcyclohexyl group, phenyl group Examples include various groups such as an aryl group such as a methylphenyl group, an aralkyl group such as a benzyl group, and a phenethyl group.

Further, R ¹ , R ² and R ³ are substituted with various substituents such as a halogen group such as fluorine, chlorine and bromine, a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxy group and an alkoxy group. It may have been done.

Specific examples of the compound represented by the general formula (A) include N-methylmaleimide, N-butylmaleimide and N-
Phenylmaleimide, No-methylphenylmaleimide,
Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, No- Chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-
Examples thereof include carboxyphenyl maleimide, Np-carboxyphenyl maleimide, Np-nitrophenyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide and N-isopropyl maleimide.

These monomers may be used alone or in combination.
You may use it as a mixture of 2 or more types. Among these maleimide compounds, alkylmaleimide and cycloalkylmaleimide are particularly preferable, and N-isopropylmaleimide and N-cyclohexylmaleimide are particularly preferable, from the viewpoints of yellowing after weathering test and weather resistance. Furthermore, from the viewpoint of ease of preparation of a monomer solution at the time of cast polymerization and satisfying the above-mentioned properties, N-isopropylmaleimide and N-alkylmaleimide such as N-cyclohexylmaleimide and N-alicyclic alkylmaleimide The combination is most preferable. The ratio of N-alkylmaleimide and N-alicyclic alkylmaleimide when used in combination should be appropriately determined experimentally depending on the type and amount of the polyfunctional monomer having two or more unsaturated groups. However, in order to bring out the effect of the combined use, usually, from 100 parts by weight of N-alkylmaleimide, 10 to 50 parts by weight of N-alicyclic maleimide is used.
It is preferably used in the range of 0 parts by weight.

Next, the polyfunctional monomer having two or more unsaturated groups will be described. That is, the polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide, and as the copolymerizable functional group, a vinyl group, Methyl vinyl group,
Examples thereof include an acrylic group and a methacrylic group. Further, a monomer having two or more different copolymerizable functional groups in one molecule is also included in the polyfunctional monomer in the present invention.

Specific preferred examples of the polyfunctional monomer having two or more unsaturated groups as described above include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate. , Glycerol (di / tri) (meta)
Acrylate, trimethylolpropane (di / tri)
Di-, tri-, tetra- (meth) acrylates of polyhydric alcohols such as (meth) acrylate, pentaerythritol (di / tri / tetra) (meth) acrylate,
Aromatic polyfunctional monomers such as p-divinylbenzene and o-divinylbenzene, (meth) acrylic acid vinyl ester,
Esters such as (meth) acrylic acid allyl ester,
Examples thereof include dienes such as butadiene, hexadiene, and pentadiene, monomers having a phosphazene skeleton in which a polymerization polyfunctional group is introduced from dichlorophosphazene as a raw material, and polyfunctional monomers having a heteroatom cyclic skeleton such as triallyl diisocyanurate.

In the above polyolefin-based copolymer, the monomer represented by the general formula (A) is 20 to 98% by weight.
It is preferably contained, but if it is less than 20% by weight, sufficient heat resistance, mechanical strength, optical isotropy and the like properties may not be satisfied. Also, 98
If the content is more than wt%, the degree of crosslinking will decrease, solvent resistance,
In some cases, lowering the water absorption is insufficient. Further, the content of the monomer represented by the general formula (A) is 30 to
It is preferably 80% by weight, more preferably 4
It is 0 to 60% by weight.

On the other hand, the polyfunctional monomer having two or more unsaturated groups is preferably contained in the crosslinked polymer in a proportion of 2 to 80% by weight. If it is less than 2% by weight, crosslinking may not proceed sufficiently, and heat resistance, solvent resistance, etc. tend to be lowered. Moreover, if it exceeds 80% by weight,
The impact resistance and the like may be reduced, and the characteristics of the plastic may be reduced.

Further, in the above polyolefin-based copolymer, the mechanical strength is improved, the optical isotropy is improved, the refractive index is increased, the water absorption is decreased, the dyeability is improved, the heat resistance is improved, and the impact resistance is improved. For this purpose, various copolymerizable monomers are preferably used in combination. Examples of such monomers that can be used in combination include aromatic vinyl-based monomers, olefin-based vinyl monomers, (meth) acrylic acid and its ester-based monomers, and polyvalent carboxylic acid anhydrides. Specific examples of such an aromatic vinyl-based monomer include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene, chlorostyrene and bromostyrene. Usually, styrene, α-methylstyrene, p-methylstyrene, and the like are used from the viewpoint of performance and industrial availability. Further, as other vinyl-based monomers, acrylonitrile, methacrylonitrile and other vinyl cyanide monomers, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate,
Specific preferred examples include (meth) acrylic acid (ester) -based monomers such as t-butyl methacrylate, benzyl methacrylate, acrylic acid, and methacrylic acid, and maleic anhydride.

The total content of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups is preferably 30% by weight or more in the crosslinked resin. It is preferably 40% by weight or more. That is, 30
If it is less than 10% by weight, the obtained polymer is insufficient in transparency, heat resistance, chemical resistance, impact resistance and the like.

It is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the crosslinked resin in the present invention for the purpose of improving light resistance, resistance to oxidative deterioration and antistatic property. In particular, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property because these properties can be improved without lowering the chemical resistance and heat resistance. Preferred examples of such a monomer include a benzophenone-based UV absorber having an unsaturated double bond, a phenylbenzoate-based UV absorber having an unsaturated double bond, and a (meth) acrylic monomer having a hindered amino group as a substituent. Is mentioned. These copolymerized monomers are preferably used in the range of 0.5 to 20% by weight based on the total monomers. If it is less than 0.5% by weight, the effect of addition is not observed, and if it exceeds 20% by weight, heat resistance, mechanical strength and the like tend to be lowered.

It is also useful to add a dye to the crosslinked resin in the present invention for adjusting the light transmittance and absorbing light of a specific wavelength. The dye is not particularly limited, and two or more kinds may be mixed and used.

Regarding the method for polymerizing the crosslinked resin of the present invention,
There is no particular limitation, and the polymerization can be performed by a generally known method. When the cross-linking resin is a polyolefin-based copolymer, it can be polymerized by keeping the above-mentioned monomer mixture under a predetermined temperature condition in the presence or absence of a radical-generating initiator. Various methods such as bulk polymerization, solution polymerization, suspension polymerization and cast polymerization can be used. The degree of polymerization of the crosslinked resin of the present invention is not particularly limited, but a higher polymerization rate is preferable, and 90% or more is preferable in consideration of solution coating such as a cured film and post-processing such as vacuum deposition.

The method for molding the crosslinked resin of the present invention is not particularly limited, but an effective molding method is a cast polymerization method.

As the cured coating in the present invention, a coating containing an organic polymer as a main component is preferably used. Here, the organic polymer is not particularly limited, and specific examples include acrylic resins, silicone resins, polyurethane resins, epoxy resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins. , Urea resin, nylon resin, polycarbonate resin 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. Especially 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. Further, in consideration of various characteristics such as surface hardness, heat resistance, chemical resistance, and transparency, it is preferable to use a silicone resin, more preferably an organosilicon compound represented by the following general formula (B) or Mention may be made of polymers obtained from the hydrolysates.

R ⁴ _a R ⁵ _b SiX _4-ab (B) (wherein R ⁴ is an organic group having 1 to 10 carbon atoms, and R ⁵
Is selected from a hydrocarbon group having 1 to 6 carbon atoms and a halogenated hydrocarbon group, X is a hydrolyzable group, and a and b are 0 or 1. ) Examples of the organosilicon compound represented by the general formula (B) include methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate. Tetraalkoxysilanes and hydrolysates thereof, and further methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetate Shishiran, .gamma.-chloropropyl trimethoxy silane, .gamma.-chloropropyl triethoxysilane, .gamma.-chloropropyl triacetoxy silane,
γ-methacryloxypropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β- Cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 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, δ-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltrimethoxysilane and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes, or triphenoxysilanes or hydrolysates thereof and dimethyldimethoxy. Silane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ
-Methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane,
γ-mercaptopropylmethyldiethoxysilane, γ-
Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyl Dimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxy Propylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethane Tyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ -Glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxy Examples are silanes, dialkoxysilanes such as γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or their hydrolysates.

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 flexibility and dyeability to the cured film, it is preferable to use an epoxy group, an organosilicon compound containing a glycidoxy group,
It will have higher 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. Upon hydrolysis, it is preferable to add pure water or an acidic aqueous solution in an amount of equimolar or more and 3 times or less the molar amount of the hydrolyzable group contained in the compound represented by the general formula (B) from the viewpoint of accelerating the curing.

During the hydrolysis, it is possible to perform the hydrolysis without a solvent since alcohol or the like is produced. However, for the purpose of making the hydrolysis even more uniform, after mixing the organosilicon compound and the solvent, the hydrolysis is performed. It is also possible to disassemble. It is also possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use depending on the purpose, and to add an appropriate solvent after that.

It is preferable that the above composition is usually diluted with a volatile solvent and applied as a liquid composition, but the solvent applied is not particularly limited. It is required to be determined in consideration of stability of the composition, wettability with respect to an object to be coated, volatility, and the like. Further, the solvent can be used not only as one kind but also as a mixture of two or more kinds. Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and aprotic polar solvents.

The cured coating in the present invention has improved adhesion to an antireflection film made of an inorganic coating, improved surface hardness, refractive index adjustment, mechanical strength improvement, thermal characteristics improvement, conductivity improvement, etc. For the purpose, a fine particle inorganic substance or the like can be added as a constituent component preferably used. The particulate inorganic substance is not particularly limited as long as it achieves its purpose in a film state, and as a particularly preferable example from the viewpoint of improving workability and imparting transparency, a colloidally dispersed sol can be mentioned. To be More specific examples include silica sol, titania sol, zirconia sol, ceria sol, antimony oxide sol, magnesium fluoride sol, ITO (indium-tin oxide) sol, tin oxide sol, and the like.

The refractive index of the cured coating in the present invention is not particularly limited, but in order to obtain a high quality antireflection property with less interference fringes, and to prevent ripples from occurring in the spectral reflection characteristics. For that purpose, it is preferable to set the difference in refractive index between the crosslinked resin and the cured film to ± 0.5 or less. To obtain high-quality antireflection characteristics with less influence of interference fringes and ripples, ± 0.1 or less, and further ±
It is preferably 0.05 or less and ± 0.02 or less.
In particular, it is preferably set within ± 0.02 in an application where it is necessary to suppress the generation of interference fringes and ripples as much as possible.

In the present invention, the above-mentioned cured film is provided on the crosslinked resin, but the method for providing the cured film is not particularly limited, and an immersion method, a spin method, a shower method or the like may be used.

In the present invention, an antireflection film composed of one or more inorganic coatings is provided on the cured coating.
As the antireflection film constituent material, for example, SiO, SiO
₂ , ZrO ₂ , Al ₂ O ₃ , TiO, TiO ₂ , Ti ₂
O ₃ , Y ₂ O ₃ , Yb ₂ O ₃ , MgO, Ta ₂ O ₅ , C
eO ₂ , HfO ₂ , SnO ₂ , inorganic oxides such as ITO, inorganic nitrides such as Si ₃ N ₄ , MgF ₂ , Al
F ₃ , BaF ₂ , LiF, CaF ₂ , Na ₃ AlF ₆ ,
Examples thereof include fluorine-containing inorganic compounds such as Na ₅ Al ₃ F ₁₄ . Further, from the viewpoint of improving antireflection performance, it is preferable to provide a coating film made of a fluorine-containing inorganic compound on the outermost surface layer of the inorganic coating film.

Further, among the fluorine-containing inorganic compounds, MgF ₂ is preferably used from the viewpoints of improving surface hardness, antireflection performance and durability.

In the present invention, the method for coating the antireflection film comprising the inorganic coating on the cured coating is preferably a forming means in a vacuum atmosphere from the viewpoint of improving the adhesive strength with the cured coating and the film density. The vacuum vapor deposition method, the ion beam assisted vapor deposition method, the ion plating method, and the sputtering method are preferable, and the ion beam assisted vapor deposition is particularly effective for improving hardness and film density.

Further, the temperature during the formation of the antireflection film made of an inorganic coating is preferably higher, specifically, 80 ° C. or higher, particularly 150 ° C. from the viewpoint of improving durability.
The above is preferable. If the temperature is lower than 80 ° C., the antireflection film made of an inorganic coating tends to be peeled off by immersion in warm water.

The film formation temperature of the antireflection film is preferably lower than the glass transition temperature of the substrate from the viewpoint of deformation of the substrate such as warp and strain, and particularly 5 ° C. above the glass transition temperature.
When it is lower than the above, deformation is less likely to occur and it is more preferably used.

Further, the antireflection film comprising the inorganic coating of the present invention may be a single layer film or a multilayer film from the viewpoint of antireflection performance, and in particular, from the viewpoint of antireflection performance, the outermost layer film is It is preferably a coating film containing a fluorine-containing inorganic compound as a main component.

Further, in order to improve the antireflection performance, a multilayer film having two or more layers is preferably applied. When using a multilayer film,
Regarding the combination of the film structure in the multilayer film, the setting of the film thickness, etc., the optimum combination varies depending on the refractive index of the crosslinked resin, the refractive index of the cured film, etc.
Many combinations have already been proposed (Optical Technology Contact Vol 9, No. 8.17 ~ 23. (1971), 'OPTICS OF THIN
FILMS '159 ~ 283.A.VASICEK (NORTHHOLLAND PUBLISHIN
G COMPANY) AMSTERDAM (1960)), and these combinations can also be used in the present invention.

Further, chemical treatment, high frequency discharge treatment, ion beam treatment and the like are effective as means for improving the adhesion between the layers.

Since the antireflection article formed as described above has high surface hardness, excellent antireflection property and durability, it can be used for optical lenses, CRTs, LCDs,
It is particularly preferably used for a front plate of a display device such as a plasma display and a filter.

[0044]

EXAMPLES The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

Various characteristics of the substrate were measured as follows.

The total light transmittance was measured according to ASTM D-648, and the solvent resistance was evaluated by visually observing the change of the surface condition at the time of rubbing the surface with gauze impregnated with acetone. The bending test is JIS K-720.
Based on 3. The glass transition temperature is Mettle
r TA3000 (measured at 2nd run).

The antireflection article provided with the coating and the inorganic coating was measured as follows.

(A) Transparency The transparency of the film was visually examined under a fluorescent lamp.

(B) Scratch resistance The surface was rubbed with # 0000 steel wool and judged from the degree of scratches.

(C) Adhesiveness 100 pieces of crevices reaching the base material of 1 mm are put on the surface of the coating with a steel knife from the top of the coating, and cellophane adhesive tape (product name "Cellotape" manufactured by Nichiban Co., Ltd.) is strongly adhered. , 9
It was rapidly peeled in the direction of 0 degree, and the presence or absence of peeling of the coating film was examined.

(D) Minimal surface reflectance U-3410 self-recording spectrophotometer (manufactured by Hitachi, Ltd.)
Was used to measure the minimum surface reflectance on one side.

(E) Refractive Index The refractive index of the substrate and the cured film was measured using a fully automatic ellipsometer L1116A (manufactured by Gartner).

Example 1 (1) Preparation of crosslinked resin Isopropylmaleimide 26.5 g, styrene 18.5
g, 5.0 g of divinylbenzene and 0.05 g of azobisisobutyronitrile were mixed and dissolved, and cast molding was performed by cast polymerization. Cast polymerization was performed as follows.

Size 150 mm x 150 mm, thickness 5 mm 2
The outer peripheral portions of the two glass plates were bonded with a gasket made of soft vinyl chloride and assembled so that the distance between the two glass plates was 2 mm. The above-mentioned monomer mixture was poured into the assembled glass plate, and the temperature was 70 ° C. for 8 hours and 100 ° C. for 1 hour.
Polymerization was further performed at 160 ° C. for 1 hour to obtain a transparent casting plate (hereinafter referred to as casting plate (I)).

The glass transition temperature of this casting plate (I) is 19
The temperature was 0 ° C., the total light transmittance was 90%, and the solvent resistance was also good. Table 1 shows the refractive index of the casting plate (I).

(2) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate In a reactor equipped with a rotor, 160.0 g of γ-glycidoxypropyltrimethoxysilane was added. Preparation, liquid temperature 10 ℃
Keep it at 0.0 while stirring with a magnetic stirrer.
36.6 g of 1N hydrochloric acid aqueous solution was gradually added dropwise. After completion of dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of paint To the silane hydrolyzate, 105.8 g of methanol, 52.9 g of dimethylformamide and 0.5 g of a silicone-based surfactant were added and mixed, and a colloidal antimony pentoxide sol (Nissan Chemical Co., Ltd.) was added. Product name: Antimonzol A-2
550, average particle diameter 50 mμ) 83.3 g, and aluminum acetylacetonate 5.0 g were added and sufficiently stirred to obtain a coating composition.

(3) Preparation of Alkali Treatment Liquid 100 g of sodium hydroxide was dissolved in 300 g of water, and 2 g of an alkylammonium type cationic surfactant (manufactured by NOF CORPORATION, trade name: cation BB, dodecyltrimethylammonium chloride) was added. , An alkaline treatment liquid was prepared.

(4) Surface treatment of resin The alkaline treatment liquid prepared in (3) above was heated to 80 ° C. The casting plate (I) obtained in (1) was dipped in this heated alkaline treatment liquid for 10 minutes, washed with hot water at 50 ° C. for 10 minutes, and dried to obtain a treated plate (hereinafter, treated plate (I )) Was created.

(5) Application of coating composition The coating composition prepared in (2) above was applied by dip coating to the crosslinked resin obtained in (1) above at a pulling rate of 20 cm / min, and then at 100 ° C./10. After pre-curing for 15 minutes, heating was further performed at 150 ° C. for 30 minutes to provide a cured coating on the crosslinked resin (1).

The refractive index of the obtained cured coating is shown in Table 1.

(6) Formation of Antireflection Film Consisting of Inorganic Film The crosslinked resin having the cured film obtained in (2) above is set at 180 ° C. and Y ₂ O ₃ / T which is an inorganic compound is formed.
The iO ₂ / MgF ₂ was vacuum-deposited, and the optical film thickness was set to λ / 4, λ / 2, λ / 4 (λ = 521 nm) in this order to form a multilayer coating.

The interface between the cured film and Y ₂ O ₃ was subjected to Ar ion beam cleaning treatment, and TiO ₂ was subjected to ion beam assisted vapor deposition.

The reflection interference color of the obtained antireflection article is
It had a dull magenta color.

The evaluation results of the antireflection article obtained as described above are shown in Table 1.

Example 2 The crosslinked resin having a cured coating in Example 1 was heated to 100 ° C.
To ZrO ₂ / TiO ₂ / S which is an inorganic compound
The optical film thickness of io ₂ was λ
The same procedure as in Example 1 was carried out except that the multi-layer coating was performed by setting / 4, λ / 4, λ / 4 (λ = 521 nm). The reflection interference color of the obtained antireflection article was dull reddish purple, and the evaluation results are shown in Table 1.

Example 3 In the preparation of the coating composition (b) of the coating composition of Example 1, an epoxy resin (“EP-82” manufactured by NOF CORPORATION) was used.
7 ") A cured coating was provided in the same manner as in Example 1 except that 20.0 g was added. The refractive index of the obtained cured coating is shown in Table 1. Also, as in Example 1, the multilayer structure The resulting antireflection article had a dull reddish purple color as a reflection interference color, and the evaluation results are shown in Table 1.

Example 4 Multilayer coating was carried out in the same manner as in Example 1 except that the temperature of the crosslinked resin in the formation of the antireflection film of Example 1 was 180 ° C. The reflection interference color of the obtained antireflection article was dull reddish purple, and the evaluation results are shown in Table 1.

Comparative Example 1 Multilayer coating was carried out in the same manner as in Example 1 except that the alkali treatment was not carried out and the cured coating was not provided. The reflection interference color of the obtained antireflection article was dull reddish purple, and the evaluation results are shown in Table 1.

Comparative Example 2 All of the examples except that the cross-linking resin was a polymethylmethacrylate resin plate (Tg 100 ° C.) in Example 1 and the resin temperature was 180 ° C. in the film formation of the antireflection film was 85 ° C. Multilayer coating was performed in the same manner as in 1. The reflection interference color of the obtained antireflection article was dull reddish purple, and the evaluation results are shown in Table 1.

[Table 1]

[0071]

The antireflection article of the present invention has the following effects.

(1) It has excellent antireflection performance.

(2) It has a high surface hardness.

(3) An antireflection article having few microcracks can be obtained.

(4) An antireflection article having excellent durability can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadayoshi Matsunaga 1-1-1, Sonoyama, Otsu City, Shiga Toray Co., Ltd. Shiga Plant

Claims (11)

[Claims] 1. An antireflection coating comprising a cured coating on a crosslinked resin having a glass transition temperature of 130 ° C. or higher, and an antireflection coating comprising one or more inorganic coatings on the cured coating. Sex goods. 2. The antireflection article according to claim 1, which has a glass transition temperature of 150 ° C. or higher. 3. The difference in refractive index between the crosslinked resin and the cured coating is
It is 0.5 or less, The antireflection article of Claim 1 or 2 characterized by the above-mentioned. 4. The antireflection article according to claim 1, wherein the outermost layer film of the antireflection film is a film containing a fluorine-containing inorganic compound as a main component. 5. A crosslinked resin contains 20 to 98% by weight of a monomer represented by the general formula (A) and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups, Further, the composition is obtained by polymerizing a composition in which the total weight ratio of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. It is a copolymer, The antireflection article in any one of Claims 1-4 characterized by the above-mentioned. [Chemical 1] (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group.) 6. An antireflection property, characterized in that a cured coating film is provided on a crosslinked resin having a glass transition temperature of 130 ° C. or higher, and an antireflection film composed of one or more inorganic coating films is further provided on the cured coating film. Article manufacturing method. 7. The method for producing an antireflection article according to claim 6, wherein the film formation temperature of the antireflection film is 5 ° C. or more lower than the glass transition temperature of the crosslinked resin. 8. The method for producing an antireflection article according to claim 6, wherein the glass transition temperature is 150 ° C. or higher. 9. The refractive index difference between the crosslinked resin and the cured coating is
It is 0.5 or less, The manufacturing method of the antireflection article in any one of Claims 6-8. 10. The method for producing an antireflection article according to claim 6, wherein the outermost surface film of the antireflection film is a film containing a fluorine-containing inorganic compound as a main component. 11. A crosslinked resin contains 20 to 98% by weight of a monomer represented by the general formula (A) and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups, Further, the composition is obtained by polymerizing a composition in which the total weight ratio of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. It is a copolymer, The manufacturing method of the antireflection article in any one of Claims 6-10. [Chemical 2] (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group.)