JPH0760855A - Anti-reflection article - Google Patents

Abstract

(57) [Summary] [Construction] In an antireflection article having four layers of antireflection layers, the refractive index n _i and the optical film thickness d _i of each layer are 0.2λ ₀ ≦ n _i · d. I met _i ≦ _{0.3λ 0,} and anti-reflection article, characterized in _{that n i} is in the range of below. 1.8 ≤ n ₁ ≤ 2.0 2.3 ≤ n ₂ ≤ 2.5 2.05 ≤ n ₃ ≤ 2.25 1.3 ≤ n ₄ ≤ 1.50 (where i is 1 to 4) , Which indicates the number of layers from the substrate side, and λ ₀ represents the set wavelength.) [Effect] The antireflection article of the present invention has excellent antireflection performance.

Description

Detailed Description of the Invention

[0001]

[Field of Industrial Application] On the surface of a plastic or glass substrate, about several to 10% of the amount of incident light is reflected. This not only reduces the amount of transmitted light, but also causes ghost and flare in the use of optical members such as lenses. In addition, when used as a display for LCDs or their filters, the reflected light not only makes the operator uncomfortable, but also causes eye fatigue and various other adverse health effects. In order to solve these problems, the surface of the base material is subjected to antireflection processing.

At present, as a method for forming an antireflection layer on a plastic or glass substrate, a chemical method in which a coating agent composed of an organic silane compound, inorganic fine particles or the like is multi-layered, or an inorganic oxide or an inorganic fluoride is used. A general method is to apply a multilayer coating by vacuum deposition or sputtering. However, under the present circumstances, chemical methods have not yet obtained sufficient antireflection properties. It is known that the physical method is superior in antireflection property to the chemical method. For example, Japanese Patent Application Laid-Open No. 5-2101 discloses a technique of providing an antireflection film composed of five layers. However, in the technique disclosed in Japanese Patent Laid-Open No. 5-2101, not only the cost is increased because five antireflection layers are required, but also the antireflection characteristics are not sufficient.

[0003]

SUMMARY OF THE INVENTION The present invention is intended to solve the above problems of the prior art, and provides an antireflection article having excellent antireflection properties in the entire visible light range.

[0004]

That is, the present invention is
“In an antireflection article having an antireflection layer consisting of four layers on a substrate, the refractive index _ni and the optical film thickness d of each layer are
_i satisfies _{0.2λ 0 ≦ n i · d i} ≦ 0.3λ 0,
Further, the antireflection article is characterized in that _ni is in the following range.

1.8 ≤ n ₁ ≤ 2.0 2.3 ≤ n ₂ ≤ 2.5 2.05 ≤ n ₃ ≤ 2.25 1.3 ≤ n ₄ ≤ 1.50 (where i = 1 4 shows the layer number from the substrate side, and λ ₀ represents the set wavelength.) ”.

The constituent material of the antireflection layer in the present invention is not particularly limited. Examples of the constituent substance include silicon monoxide, silicon dioxide, zirconium oxide, aluminum oxide, yttrium oxide, ytterbium oxide,
Cerium oxide, hafnium oxide, tin oxide, ITO (I
Abbreviation for ndium tin oxide, which means a mixture of tin oxide and indium oxide. ) And the like, inorganic oxides such as silicon nitride, lithium fluoride,
Aluminum fluoride, magnesium fluoride, cryolite, thiolite, neodymium fluoride, sodium fluoride,
Examples thereof include fluorine-containing inorganic compounds such as lead fluoride, samarium fluoride and strontium fluoride, fluororesins and silicone resins.

From the viewpoint of improving antireflection performance, it is preferable to provide a film made of a fluorine-containing inorganic compound on the outermost surface layer of the inorganic film. Among the fluorine-containing inorganic compounds, magnesium fluoride is preferably used from the viewpoints of easy availability, improvement of surface hardness, improvement of antireflection performance, and improvement of durability.

To prevent static electricity, ITO may be provided between the antireflection layer and the substrate. The film thickness of ITO is not particularly limited, but is 30 from the viewpoint of antireflection property.
nm or less is preferably used.

In the present invention, the method of coating the antireflection layer is not particularly limited. For example, a dipping method, a vacuum vapor deposition method, a sputtering method and the like can be mentioned. Adhesive strength with the coated surface, the formation means under vacuum atmosphere is preferably used from the viewpoint of improving the film density, vacuum deposition method, ion beam assisted deposition method, ion plating method, sputtering method is preferred, especially hardness improvement,
Ion beam assisted vapor deposition is effective for improving the film density. Here, the ion beam assisted vapor deposition method means irradiating some ions at the same time during vapor deposition.

It is also possible to pretreat the coated surface before coating in order to improve the adhesion of the film. The pretreatment method is not particularly limited, but chemical treatment, plasma treatment, ion beam treatment (hereinafter, pretreatment using an ion beam is referred to as ion beam cleaning) and the like are preferably used and particularly effective. A high ion beam cleaning process is more preferably used.

The temperature during the film formation of the antireflection layer made of an inorganic coating is not particularly limited. From the viewpoint of improving the film characteristics, the film forming temperature is preferably high, specifically 80 ° C. or higher, and particularly 130 from the viewpoint of improving durability.
It is preferably at least ° C. If the temperature is lower than 80 ° C., the antireflection layer made of an inorganic coating tends to be peeled off by immersion in warm water or the like.

Further, the film formation temperature of the antireflection layer 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 if it is 5 ° C. or more lower than the glass transition temperature, the deformation is more difficult to occur. It is preferably used.

In the present invention, the substrate is not particularly limited. From the viewpoint of the film forming temperature of the antireflection layer, a glass transition temperature of 150 ° C. or higher is preferably used, and 170 ° C.
A substance having the above glass transition temperature has further improved heat resistance and is more preferably used. Here, the glass transition temperature means the physics and chemistry dictionary third edition (Iwanami Shoten, 197).
In the transition region, various characteristics such as elastic modulus, expansion coefficient, heat capacity, refractive index, and dielectric constant change. It is possible to measure the glass transition temperature from changes in these characteristics, and specifically, differential scanning calorimetry (DS
It can be evaluated by a known method such as C) (eg J
IS K7121). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be determined by evaluating the substrate itself or the one obtained by subjecting it to heat treatment.

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

The components of the substrate include, for example, polyolefin resins such as polymethacrylic acid resins such as polymethacrylic acid and polycarboxyphenylmethacrylamide, polystyrene resins such as poly (biphenyl) styrene, and poly (2,2). Polyether resin represented by 6-dimethyl-1,4-phenylene oxide), polycarbonate resin represented by poly (oxycarbonyloxy-1,4-phenylene isopropylidene-1,4-phenylene), poly ( Oxy-2,2,4,4-tetramethyl-1,3-cyclobutyleneoxyterephthaloyl), a polyester resin represented by poly (oxy-1,4-phenylenesulfonyl-1,4-phenylene), Poly (oxy-1,4-phenylene isopropylidene-1,4-phen Polysulfone-based resin typified by renoxy-1,4-phenylenesulfonyl-1,4-phenylene), polyamide-based resin typified by poly (iminoisophthaloyluimino-4,4'-biphenylene), poly (thio) -1,4-phenylenesulfonyl-
1,4-phenylene) represented by polysulfide resin, unsaturated polyester resin, epoxy resin, melamine resin, phenol resin, diallyl phthalate resin, polyimide resin, polyphosphazene resin, etc. It is possible to obtain a three-dimensional crosslinked resin exhibiting the above thermal characteristics by introducing a three-dimensional crosslinked structure in these polymer groups. In particular, a polyolefin resin is preferable from the viewpoint of moldability, and a polyolefin copolymer obtained by polymerizing a composition containing a polyfunctional monomer having two or more unsaturated groups is more preferably used.
Further, glass, silicon, or the like is preferably used as the inorganic substrate.

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

[0017]

[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.) General formula R contained in the maleimide derivative compound represented by (A)
¹ and R ² 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 halogeno group such as fluorine, chlorine and bromine, cyano group, carboxyl group, sulfonic acid group, nitro group, hydroxy group and alkoxy group. It may have been done.

Specific examples of the compound represented by the general formula (A) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide and N-methylmaleimide. −
p-Methylphenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimide, N
-O-chlorophenyl maleimide, Nm-chlorophenyl maleimide, Np-chlorophenyl maleimide,
Examples include N-o-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like.

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 viewpoint 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 characteristics, N-alkylmaleimides such as N-isopropylmaleimide and N-cyclohexylmaleimide and N-alicyclic alkylmaleimides can be used. The combination is most preferable. The ratio of N-alkylmaleimide and N-alicyclic alkylmaleimide at the time of combined use 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, it is preferable to use 10 parts by weight to 500 parts by weight of N-alicyclic maleimide with respect to 100 parts by weight of N-alkylmaleimide.

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.

Preferred specific 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, esters such as (meth) acrylic acid vinyl ester and (meth) acrylic acid allyl ester, dienes such as butadiene, hexadiene and pentadiene, and dichlorophosphazene. Examples of the raw material include a monomer having a phosphazene skeleton having a polymerized polyfunctional group introduced therein, and a polyfunctional monomer having a heteroatom cyclic skeleton such as triallyl diisocyanurate.

The above polyolefin-based copolymer preferably contains 20 to 98% by weight of the above-mentioned monomer represented by the general formula (A), but when it is less than 20% by weight, it is sufficient. Such properties as heat resistance, mechanical strength and optical isotropy cannot be satisfied. On the other hand, when it exceeds 98% by weight, the degree of cross-linking decreases, and solvent resistance and low water absorption cannot be satisfied. Furthermore, 30-80
It is preferably in the range of 40% by weight, more preferably 40 to
It is 60% by weight.

On the other hand, the polyfunctional monomer having two or more unsaturated groups is preferably contained in the three-dimensional crosslinked polymer in a proportion of 2 to 80% by weight, but in the case of less than 2% by weight. The three-dimensional crosslinking does not proceed sufficiently and the heat resistance and solvent resistance are deteriorated. Moreover, if it exceeds 80% by weight,
There arises a problem that impact resistance and the like are deteriorated and the characteristics of the plastic are significantly deteriorated.

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. Examples of other vinyl-based monomers include vinyl cyanide-based monomers such as acrylonitrile and methacrylonitrile, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate, benzyl methacrylate, and acrylic. Preferable specific examples include (meth) acrylic acid (ester) -based monomers such as 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 in the above polyolefin-based copolymer is 30% by weight in the three-dimensional crosslinked resin. % Or more, and more preferably 40% by weight or more. That is, if it is less than 30% by weight, transparency, heat resistance, chemical resistance, impact resistance and the like may be insufficient.

It is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the substrate in the present invention for the purpose of improving light resistance, oxidation deterioration resistance 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. As a preferable example of such a monomer,
Examples thereof 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. These copolymerization monomers are preferably used in the range of 0.5 to 20% by weight. 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 substrate of 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.

The method for polymerizing the substrate of the present invention is not particularly limited, and it can be polymerized by a generally known method.
When the substrate 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 substrate 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 substrate of the present invention is not particularly limited, but an effective molding method is a cast polymerization method.

Further, in the present invention, it is preferable to provide a cured coating on the substrate from the viewpoint of resistance to moist heat, resistance to dry heat, resistance to hot water, improvement of surface hardness and the like. A material having a refractive index difference of 0.5 or less between the cured film and the substrate is preferably used, and a material having a refractive index difference of 0.1 or less with the substrate is more preferably used in order to further reduce the influence of interference fringes. . In order to obtain a high-quality antireflection property with very few interference fringes, it is preferable to set the refractive index difference with the substrate to be 0.05 or less. Further, particularly in applications where it is necessary to suppress the generation of interference fringes, it is preferable to use one having a refractive index difference of 0.02 or less. Further, in order to prevent ripples from occurring in the spectral reflection characteristics of the prepared antireflection article, it is preferable that the difference in refractive index between the cured film and the substrate is 0.1 or less, and high quality antireflection characteristics with minimal ripples. In order to obtain the above, it is preferable to set the difference in refractive index from the substrate to be 0.05 or less.
In addition, it is preferable to use one having a difference in refractive index of 0.02 or less particularly in applications where it is necessary to prevent ripples from occurring in the spectral reflection characteristics.

As the cured film, one having an organic polymer as a main component is preferably used. Here, the organic polymer is not particularly limited. Specific examples of organic polymers include acrylic resins, silicone resins, polyurethane resins, epoxy resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins, etc. Is mentioned. 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. 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 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 (B) 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- (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-
Trialkoxysilanes such as epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilane, or triphenoxy. Silanes 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, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyl Dimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycid Xypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxy Dialkoxysilanes such as silane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or their hydrolysates. Degradation products are an example.

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.

It is preferable to add a fine particle inorganic oxide to the cured coating for the purpose of improving scratch resistance, heat resistance, wet heat resistance and dry 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, antimony oxide sol, alumina sol and the like. The shape and particle size of the fine particle inorganic oxide are not particularly limited.

The method of pretreating the substrate when the cured coating is formed on the substrate is not particularly limited, but solution treatment, plasma treatment, ultraviolet treatment, ion beam cleaning treatment and the like are used. In particular, plasma treatment, solution treatment and the like are preferably used from the viewpoints of treatment effect, economical efficiency, workability, etc. Among them, alkali treatment and the like are preferably used. Here, in addition to the alkali, a surfactant and / or an organic solvent and / or a catalyst may be added to the alkaline treatment liquid. Here, the catalyst is one that enhances the treatment effect and is not particularly limited.

The method for providing the cured coating is not particularly limited, but a dipping method, a spin method, a shower method and the like are preferably used. In particular, the dipping method is preferably used in terms of workability and economy.

The processed article having antireflection property formed as described above has high surface hardness, excellent antireflection property and durability, and thus is suitable for optical lenses, display element filters and the like. Particularly preferably used.

[0041]

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 in 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 antireflection layer 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 The surface of the base material having a diameter of 1 mm is 100 mm with a steel knife.
Cellophane adhesive tape (manufactured by Nichiban Co., Ltd., trade name “Cellotape”) was strongly adhered to each other and rapidly peeled off in the direction of 90 ° to examine the presence or absence of peeling.

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

(E) Hot water resistance The antireflection layer was treated with hot water at 60 ° C. for 2 hours to examine the adhesiveness.

Example 1 (1) Preparation of cross-linked resin 26.5 g of isopropylmaleimide, 18.5 of styrene
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 × 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.

(2) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 160.0 g of γ-glycidoxypropyltrimethoxysilane was placed in a reactor equipped with a rotor. 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 coating material 105.8 g of methanol, 52.9 g of dimethylformamide and 0.5 g of a silicone-based surfactant were added to and mixed with the silane hydrolyzate, 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 (trade name: cation BB, dodecyltrimethylammonium chloride, manufactured by NOF CORPORATION) 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 treated plate (I) obtained in the above (4) is subjected to the above (2).
20 cm / withdrawing speed of the coating composition prepared in
The coating was applied by dipping under the condition of minutes, followed by pre-curing at 100 ° C. for 10 minutes, and further heating at 150 ° C. for 30 minutes to form a cured coating on the treated plate (I).

(6) Formation of Antireflection Layer Made of Inorganic Film The crosslinked resin having the cured film obtained in (5) above is set at 160 ° C. and ZrO ₂ / T which is an inorganic compound is set.
iO ₂ / Ta ₂ O ₅ / MgF ₂ was formed by vacuum vapor deposition in the order of optical thicknesses λ / 4, λ / 4, λ / 4, λ / 4.
(Λ = 510 nm) was set for multi-layer coating.

The cured film / ZrO ₂ interface and T
The interface of a ₂ O ₅ / MgF ₂ was subjected to Ar ion beam cleaning treatment, and the ion beam assisted vapor deposition method was applied to each layer.

The reflection interference color of the obtained antireflection article was slightly reddish gray.

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

[0062]

[Table 1] Example 2 The same procedure as in Example 1 was carried out except that SiO ₂ was used instead of MgF ₂ in Example 1. In addition, Ta ₂
The interface of O ₅ / SiO ₂ was similarly subjected to Ar ion beam cleaning treatment.

The reflection interference color of the obtained antireflection article was reddish gray. The evaluation results are shown in Table 1 and the reflection characteristics are shown in FIG.

Example 3 In Example 1, glass was used instead of the casting plate (I), an antireflection layer was directly formed on the glass, and ZrO 2 was used.
Except for using Y ₂ O ₃ in the _second place, in Example 1
I went the same way. The interface between the cured film and Y ₂ O ₃ was similarly subjected to Ar ion beam cleaning treatment.

The reflection interference color of the obtained antireflection article was slightly reddish gray. The evaluation results are shown in Table 1 and the reflection characteristics are shown in FIG.

Example 4 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 160 ° 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 reddish gray. The evaluation results are shown in Table 1, and the reflection characteristics are shown in FIG.
It was shown to.

Example 5 All steps were performed in the same manner as in Example 1 except that an ITO layer was formed between ZrO ₂ / TiO ₂ with an optical film thickness of λ / 40 (λ = 510 nm). In addition, even when ITO is vapor-deposited
The r ion beam assisted vapor deposition method was applied.

The reflection interference color of the obtained antireflection article was reddish gray. The evaluation results are shown in Table 1 and the reflection characteristics are shown in FIG.

Comparative Example 1 ZrO ₂ / TiO ₂ / Ta ₂ O ₅ / M in Example 1
Instead of gF ₂ , Y ₂ O ₃ / TiO ₂ / MgF ₂ was formed by a vacuum vapor deposition method, and the optical film thickness was λ / 4 and λ /
The same procedure as in Example 1 was carried out except that the number of layers was set to 2, λ / 4 (λ = 510 nm) for multi-layer coating. The interface of the cured film / Y ₂ O _{3 and} the interface of TiO ₂ / MgF ₂ were subjected to Ar ion beam cleaning treatment. Moreover, the Ar ion beam assisted vapor deposition method was applied to each layer.

The reflection interference color of the obtained antireflection article was dull reddish purple. The evaluation results are shown in Table 1 and the reflection characteristics are shown in FIG.

[0071]

The antireflection article of the present invention has excellent antireflection performance.

[Brief description of drawings]

FIG. 1 shows the reflection characteristics of the antireflection article obtained according to Example 1 of the present invention.

FIG. 2 shows the reflection characteristics of the antireflection article obtained according to Example 2 of the present invention.

FIG. 3 shows the reflection characteristics of the antireflection article obtained according to Example 3 of the present invention.

FIG. 4 shows the reflection characteristics of the antireflection article obtained according to Example 4 of the present invention.

FIG. 5 shows the reflection characteristics of the antireflection article obtained according to Example 5 of the present invention.

FIG. 6 shows the reflection characteristics of the antireflection article obtained in Comparative Example 1 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G02B 1/11

Claims (5)

[Claims] 1. An antireflection article having a four-layer antireflection layer on a substrate, wherein each layer has a refractive index n _i and an optical film thickness d _i of 0.2λ ₀ ≦ n _i · d _i ≦ 0. An antireflection article satisfying 3λ ₀ and having n _i in the following range. 1.8 ≤ n ₁ ≤ 2.0 2.3 ≤ n ₂ ≤ 2.5 2.05 ≤ n ₃ ≤ 2.25 1.3 ≤ n ₄ ≤ 1.50 (where i is 1 to 4) , Shows the number of layers from the substrate side, and λ ₀ represents the set wavelength.) 2. The antireflection article according to claim 1, wherein the outermost layer of the antireflection layer contains a fluorine-containing inorganic compound as a main component. 3. The antireflection article according to claim 1, wherein an ITO layer is included in any of the four layers of the antireflection layer and each layer of the substrate. 4. The antireflection article according to claim 1, wherein the glass transition temperature of the substrate is 150 ° C. or higher. 5. A substrate 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. The antireflection article according to claim 1, which is a copolymer. [Chemical 1] (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group.)