JPH085803A - Method for manufacturing laminated body - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a method capable of easily producing a laminate having a transparent coating film having a high antireflection effect and an antistatic effect formed on a substrate. [Method] A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. The high refractive index layer is composed of (a) a specific aminosilane compound, (b) a heteropolyacid compound, (c) an organic solvent, and (d) water containing an acid in a specific ratio, and (a) and ( The molar ratio of b), (c) and (d) is 1: 0.001-0.2.
It is characterized by comprising a layer obtained by applying an antistatic coating composition of 5:10 to 100: 1 to 30.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a laminate. In particular, the present invention relates to a method for producing a laminate in which a transparent coating film having a high antireflection effect and a high antistatic effect is formed on a substrate.

[0002]

2. Description of the Related Art The reason why glass and transparent plastics materials reflect external light rays is that when light enters a different substance from the medium, it is reflected at the interface due to the difference in its refractive index. In the above case, since the refractive index of air as a medium and the refractive index of the glass or transparent plastics material as the base material are different, reflection and loss of light occur at the interface.

In order to reduce the above-mentioned light reflection and loss, there has been a method of applying a fluororesin-based material to a base material to form a coating having a low refractive index on the base material (Japanese Patent Laid-Open No. Hei 2).
-123771). There is also a method of laminating thin films having different refractive indexes in multiple layers using a vacuum vapor deposition method, an ion plating method, a sputtering method, or the like. Although this method has advantages such as film thickness control and antireflection effect in a wide wavelength range, it is not suitable for a large-area substrate because it produces a thin film in a limited space, and it is costly. There is a problem that it is not industrially suitable and cannot be applied to a base material having a complicated shape.

The conditions for laminating thin films for reducing the reflectance of a certain substrate to 0 are expressed by equations (1) and (2). n ₁ = (n _o n _s ) ^0.5 ... (1) n ₁ t ₁ = (λ / 4), (3λ / 4), (5λ / 4) ... (2) n _o : Refraction of air Index (n _o = 1), n _s : refractive index of base material, n ₁ : refractive index of thin film, t ₁ : thin film thickness, λ:
Incident light wavelength As described above, it is necessary to control the refractive index and the film thickness of the thin films to be laminated according to the refractive index of the base material.

As a conventional technique for controlling the refractive index of a thin film, a composition comprising a silane coupling agent, various oxide sols and an epoxy resin is applied to a substrate,
After curing, a method of making the thin film porous by immersing it in an aqueous acid or alkaline solution to selectively elute the oxide sol (Japanese Patent Laid-Open No. 1-312501), a method in which fine particles of MgF2 are dispersed in a silicon alkoxide is used. What is applied to a substrate to form a thin film (JP-A-2-256001), a composition comprising a silicon alkoxide, a polyether and an organic solvent is applied to the substrate, and then the polyether in the film is treated with an organic solvent. There is a method of making the thin film porous by elution (Japanese Patent Laid-Open No. 3-199043).

In the above method, the solubility of the oxide sol is low, so that elution takes time, the strength of the thin film decreases as the concentration of the composition increases, and the refractive index distribution easily occurs in the film thickness direction. There was a problem. The above method is
The step of dispersing fine particles of gF2 is required, a high-performance device is required for improving the dispersion, and the controllable refractive index range is narrow within the range of 1.34 to 1.46 and its accuracy is small. There were problems such as bad things. In the above method, since the solubility of polyether in an organic solvent is low, it takes time to elute, the thin film swells with an organic solvent to reduce the thin film strength, and the refractive index distribution easily occurs in the film thickness direction. There was a problem.

On the other hand, many studies have been made on the provision of an antistatic layer, and a conductive film is formed on the surface of a base material to prevent electrification. In many cases, this coating is required to be transparent so that the texture and color of the glass and plastics as the base materials are not lost.

A coating having such conductivity and transparency
Then, the following is known. (1) Interface
Activator-based paint applied. (2) Lithium chloride
And inorganic salts such as magnesium chloride, carboxylic acid groups,
Ionic conductivity like polyelectrolytes containing sulfonic acid groups
The substance is dispersed in a film-forming substance such as synthetic resin or silicate.
A film formed from the resulting composition. For example, Japanese Patent Publication Sho 58-
Japanese Patent No. 35867 discloses that an acrylic resin is used as a film-forming substance.
Lithium nitrate is used as an ion conductive material
It is a blended antistatic coating composition containing polyester fiber
The one coated with rum is disclosed. Also, Journal
of the American Ceramic Society, 484〜486, Vol.72, N
O.3, (1989), phosphomolybdic acid (H₃PMo₁₂O
_4o・ 29H ₂O) is a hydrolyzate of tetraethoxysilane
Glass plate or stainless steel plate dissolved in the solution
A film formed on the above is disclosed. (3) Silver and nickel
Conductors such as powders of metals such as copper, copper, tin or oxides thereof.
Acrylic resin, polyester resin
Disperse in a film-forming substance such as fat or tetraethoxysilane
A film formed from the composition. For example, Japanese Patent Publication No. 63-33
Japanese Patent No. 778 discloses that it is made of tin oxide containing antimony and has a particle size of
Of conductive fine powder with a particle size of 0.2 micron or less
The coating composition containing 50 to 70% by weight of
It is disclosed that an antistatic coating for plastic products is obtained.
Have been.

However, in the above film (1),
Surface resistance not only as high as ¹⁰ 10 Ω / □ or more, over time there is a disadvantage that the surface resistance value becomes high.
The above-mentioned coating (2) has a drawback in that conventionally used ion conductive substances have low conductivity when humidity is low, and sufficient antistatic properties cannot be obtained. For example, in the above-mentioned Japanese Patent Publication No. 58-35867, the surface resistance is about 10 ¹⁰ Ω / □ at a relative humidity of 50%.
That is, the antistatic performance is insufficient. In addition, phosphomolybdic acid (H ₃ PMo ₁₂ O _4o・ 29H ₂ O)
However, when a solution of tetraethoxysilane in a solution of a hydrolyzate of tetraethoxysilane is applied onto a plastic plate to form a film, cracks occur in the film, which is not applicable to plastic products. In the coating film of (3), in order to obtain sufficient antistatic property, it is necessary to increase the concentration of conductive fine particles in the film. Therefore, there is a drawback that haze occurs due to the scattering of light by the fine particles and the transparency is impaired.

[0010]

The present invention is intended to solve these problems, and its object is to provide a laminate having a transparent coating film having a high antireflection effect and an antistatic effect formed on a substrate. It is an object of the present invention to provide a method capable of easily manufacturing.

[0011]

The method for producing a laminate of the present invention comprises a transparent base material, a conductive high refractive index layer, a low refractive index layer, and a low refractive index layer being the outermost layer. So that
A method for producing a laminate having a multilayer structure, wherein the high refractive index layer is a layer obtained by applying an antistatic coating composition having a specific composition.

The aminosilane compound A (a) used in the present invention (the invention of claim 1 is referred to as the present invention) is represented by the following general formula [I].

[Chemical 3]

In the formula, Y represents an organic group having an amino group, and examples thereof include an amino group itself and a substituted amino group in which a hydrogen atom of the amino group is substituted with an aminoalkyl group. Y ¹ represents a hydrocarbon group, and examples thereof include an alkyl group and a substituted alkyl group. R has 1 to 1 carbon atoms
The number of carbon atoms is limited to 1 to 5 because the stability of the antistatic coating composition decreases and the long-term storage stability deteriorates when the number of carbon atoms increases. As an example of R,
Examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. m is an integer of 1 to 5, n is 0
It is an integer of 2.

As the compound represented by the general formula [I],
For example, γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl)
-Γ-aminopropyltrimethoxysilane, N- (β-
Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine and the like can be mentioned. Of these, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane is particularly preferable. The aminosilane compound A (a) may be used alone or in combination of two or more kinds.

Further, in the present invention, the aminosilane compound A
A silane compound represented by the following general formula [II] or general formula [III] may be used in combination with (a). Si (OR ¹ ) ₄ ... [II] In the formula, R ¹ represents an alkyl group having 1 to 5 carbon atoms. Y ² _p Si (OR ²⁾ in _4-p ··· [III] formula, p is is an integer of 1-3. R ² has 1 carbon
The number of carbon atoms is limited to 1 to 5, since the stability of the antistatic coating composition decreases and the long-term storage stability deteriorates when the number of carbon atoms increases. Examples of R ² are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert.
A butyl group and the like. Y ² represents an organic group other than OR ² , and examples thereof include a hydrocarbon group, a glycidoxyalkyl group, an epoxycyclohexylalkyl group, an aminoalkyl group, a (meth) acryloyloxyalkyl group, and a mercaptoalkyl group. Examples of the hydrocarbon group include an alkyl group, a substituted alkyl group, an allyl group, a vinyl group, a phenyl group and a naphthyl group. When p is 2 or 3, Y ² may be the same or different.

As the compound represented by the general formula [II],
For example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-
Propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane and the like can be mentioned.

As the compound represented by the general formula [III],
When p is 1, for example, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyltri-iso-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-sec-butoxy is used. Silane, monomethyltri-tert-butoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4epoxycyclohexyl) ethyltrimethoxysilane, γ -Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, acryloxypropyltrimethoxysilane and the like can be mentioned.

When p is 2, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, Dimethyl di-tert
-Butoxysilane, diethyldiethoxysilane, ethylvinyldiethoxysilane, ethylphenyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, acryloxypropylmethyldiethoxysilane, etc. Can be mentioned.

When p is 3, for example, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane, trimethylmono- Examples thereof include sec-butoxysilane, trimethylmono-tert-butoxysilane, triethylethoxysilane, diethylvinylethoxysilane, diethylphenylethoxysilane and γ-glycidoxypropylethylmethylethoxysilane.

The heteropolyacid compound (b) used in the present invention includes boron, aluminum, gallium, silicon, germanium, cesium, titanium, zirconium,
Antimony, bismuth, rhodium, copper, platinum, phosphorus,
Consists of at least one element selected from the group consisting of iron, cobalt, nickel, arsenic, chromium, sulfur, selenium, tellurium, and thorium, and molybdenum, tungsten, vanadium, niobium, and tantalum as adjacent metal atoms forming a heteropolyacid. It is a heteropoly acid or a salt thereof which is a complex oxygen acid composed of at least one element selected from the group. Examples of the salt include sodium salt and ammonium salt.

Examples of the heteropolyacid include lintan
Gustonic acid (H₃PW₁₂O₄₀・ NH ₂O), phosphorus morib
Denic acid (H₃PMo₁₂O₄₀・ NH₂O), Katangs
Tenic acid (H₃SiW₁₂O40 / nH₂O) etc.
It Heteropolyacid salts include, for example, phosphorus molybdate.
Sodium vanadate acid (Na_3-XPMo_12-XV_XO
₄₀・ NH₂O). These heteropoly oxidation
The compounds may be used alone or in combination of two or more kinds.
Good.

The amount of the heteropolyacid compound (b) used in the present invention is the above-mentioned aminosilane compound A (a) (and a mixture of the compound of the general formula [II] or [III] which is optionally added). Hereinafter, the aminosilane compound A (a)
In that case, when the compound of the general formula [II] or [III] is added if necessary, it means a mixture of the aminosilane compound A and the compound of the general formula [II] or [III]. The ratio is limited to 0.001 to 0.25 mol with respect to 1 mol. When the amount of the heteropolyacid compound (b) is small, the film does not have sufficient conductivity to prevent electrification, and when it is large, the film becomes cloudy and opaque.

The organic solvent (c) used in the present invention is compatible with the aminosilane compound A (a) and water (d) containing an acid, and dissolves the heteropolyacid compound (b). It is not particularly limited, and examples thereof include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, ketones such as acetone and methyl ethyl ketone, and tetrahydrofuran. Particularly, methyl alcohol, ethyl alcohol and isopropyl alcohol. Is preferred. These may be used alone or in combination of two or more.

The amount of the organic solvent (c) is limited to 10 to 100 mol per 1 mol of the aminosilane compound A (a). When the organic solvent (c) decreases,
When the coating composition is difficult to mix uniformly and becomes a non-homogeneous composition, and when the coating composition increases, the solid content concentration of the coating composition becomes too low, and a sufficient antistatic ability cannot be obtained when formed into a film. The preferred addition amount is aminosilane compound A
(A) It is in the range of 20 to 50 mol per mol.

Water (d) containing the acid used in the present invention
In the above, since the acid is added as a catalyst for the hydrolysis of the aminosilane compound A (a), it may be contained in the water to be added in a proportion of 0.01 to 5% by weight. When the amount of acid is small, the effect as a catalyst cannot be expected, and when it is large, the coating becomes inhomogeneous. The acid is not particularly limited, and either an inorganic acid or an organic acid can be used, and examples thereof include hydrochloric acid, sulfuric acid, and nitric acid. Water (d) is also added for the above hydrolysis. The amount of water (d) is limited to a ratio of 1 to 30 mol with respect to 1 mol of the aminosilane compound A (a). When the amount of water (d) is small, sufficient hydrolysis is unlikely to occur, and when it is large, the compatibility with the coating composition is poor. The preferable addition amount is 3 to 10 mol per 1 mol of the aminosilane compound A (a).

The composition of the antistatic coating composition used in the present invention is as described above, but a hydrophilic polymer such as polyethylene glycol may be added to further improve the conductivity. Further, in order to improve the film forming property, a cellulose derivative such as methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose may be contained. For the same purpose,
An oxide colloid such as silica sol, alumina sol, zirconia sol may be contained. Further, an alkoxide of a metal other than silicon may be added in order to improve the hardness of the film. In addition, the above aminosilane compound A
A known curing catalyst may be added for curing (a).

Further, in order to obtain a layer having a high refractive index, ultrafine tantalum oxide (Ta) having an average particle diameter of 1000 Å or less is used.
₂ O ₅ ), ultrafine particles of zirconium oxide (ZrO ₂ ), ultrafine particles of zinc oxide (ZnO), ultrafine particles of titanium oxide (TiO ₂ ), and the like, or a mixture thereof in an antistatic coating composition. May be dispersed and mixed.

The method for preparing the antistatic coating composition used in the present invention is not particularly limited. For example, a method of mixing the above-mentioned constituent materials at once, or dividing a specific constituent material After mixing, there may be mentioned a method of adding the remaining constituent materials and mixing. As a method of dividing and mixing, for example, an organic solvent is added to the aminosilane compound A (a), mixed and stirred, and water containing an acid as a catalyst for hydrolysis is added to the aminosilane compound A (a). A hydrolyzate is obtained. To this solution, a mixture of one or more heteropolyacid compounds is added, and the mixture is stirred and mixed to obtain the composition.

In the method for producing a laminate of the present invention, the low refractive index layers are further laminated on the base material alternately with the high refractive index layers. The low refractive index layer is not particularly limited as long as it is a transparent layer having a lower refractive index than the high refractive index layer.
For example, a coating layer made of fluororesin, a porous silica layer,
Examples thereof include a coating layer made of a fluorine-containing inorganic compound, and a layer in which fine particles of the fluorine-containing inorganic compound are dispersed and mixed in a binder. Incidentally, as specific representative examples of this fluorine-containing inorganic compound, MgF ₂ , AlF ₃ , BaF ₂ ,
LaF _2, etc. CaF _2, Na ₃ AlF ₆ and the like.

In the present invention, the base material forming the laminate is not particularly limited as long as it is a transparent base material, and silicate glass, alkali silicate glass, soda lime glass, Potassium lime glass, lead lime glass, barium glass, silicate glass such as borosilicate glass, aluminosilicate glass, lithium aluminosilicate glass, glass such as quartz glass, short crystals such as corundum, magnesia, sialon, etc. Plastics such as organic ceramics, polycarbonate, acrylic resin, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyester, polyurethane and cellulose triacetate can be used. In particular, silicate glass, alkali silicate glass and soda lime glass are preferable. Further, the shape of the base material is not particularly limited.

In the method for producing a laminate of the present invention, the high refractive index layer and the low refractive index layer are alternately laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Laminate. The method for producing a laminate having the smallest number of layers is as follows.First, a high refractive index layer is laminated on the surface of a transparent substrate, dried, and then a low refractive index layer is laminated thereon, dried, and cured. Is the way to do it.

The layers are preferably laminated by painting. Various methods such as a spin coating method, a dipping method, a spraying method, a roll coater method, and a meniscus coater method can be used as the method of coating the substrate.

In the second aspect of the present invention (the invention of claim 2 is referred to as the second aspect of the present invention), a heteropolyacid compound ( Instead of b), the perchloric acid compound (b ₁ ) is used.

Perchloric acid compound (b) used in the present invention 2
₁ ) is a compound represented by the general formula XClO ₄ . In the formula, X is a hydrogen atom, a monovalent metal atom, NH4 or quaternary ammonium represented by the following general formula [IV].

[Chemical 4] Examples of the monovalent metal atom include lithium, sodium and potassium. Quaternary ammonium substituent, M
¹ , M ² , M ³ and M ⁴ are alkyl groups having 1 to 20 carbon atoms. Examples of the perchloric acid compound (b ₁ ) include perchloric acid, lithium perchlorate, ammonium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate and the like. These perchloric acid compounds may be used alone or in combination of two or more kinds.

Perchloric acid compound (b) used in the present invention 2
The amount of ₁ ) is limited to a ratio of 0.001 to 0.65 mol with respect to 1 mol of the aminosilane compound A (a). When the amount of the perchloric acid compound (b ₁ ) is small, the film does not have sufficient conductivity to prevent static electricity, and when it is large, the film becomes cloudy and opaque.

The organic solvent (c) used in the present invention 2 is
There is no particular limitation as long as it is compatible with the aminosilane compound A (a) and water (d) containing an acid and can dissolve the perchloric acid compound (b ₁ ). It is the same as that used in the antistatic coating composition for obtaining the refractive index layer. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention.

The method of preparing the antistatic coating composition for obtaining the high refractive index layer of the present invention 2 is that the perchloric acid compound (b ₁ ) is used in place of the heteropolyacid compound (b). Is similar to the manufacturing method of the present invention.

In the method for producing a laminate of the present invention 2, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. The method for producing a laminate of the present invention is the same as the method for producing a laminate of the present invention, except that the antistatic coating composition containing the perchloric acid compound (b ₁ ) is used.

In the present invention 3 (the invention of claim 3 is referred to as the present invention 3), in the antistatic coating composition for obtaining the high refractive index layer of the method for producing a laminate of the present invention, the heteropolyacid compound ( Instead of b), a trifluoromethanesulfonic acid compound (b ₂ ) represented by the general formula CF ₃ SO ₃ X ¹ is used. In the formula, X ¹ represents a hydrogen atom or a monovalent metal atom. Examples of the monovalent metal atom include lithium, sodium and potassium. Examples of the trifluoromethanesulfonic acid compound (b ₂ ) include trifluoromethanesulfonic acid, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, and the like. These may be used alone or in combination of two or more.

Trifluoromethanesulfonic acid compound (b
The amount of ₂ ) is limited to 0.001 to 0.3 mol per 1 mol of the aminosilane compound A (a). When the amount of the trifluoromethanesulfonic acid compound (b ₂ ) is small, the film does not have sufficient conductivity for antistatic, and when it is large, the film becomes cloudy and opaque. The preferable addition amount is 0. 1 with respect to 1 mol of the aminosilane compound A (a).
It is in the range of 05 to 0.2 mol.

The organic solvent (c) used in the present invention 3 is
It is not particularly limited as long as it is compatible with the aminosilane compound A (a) and water (d) and dissolves the trifluoromethanesulfonic acid compound (b ₂ ). For example, the high refractive index layer of the present invention Are similar to those used in the antistatic coating composition to obtain The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention.

The water (d) used in the present invention 3 is added for the hydrolysis of the aminosilane compound A (a).
Water (d) is added in a ratio of 1 to 30 mol with respect to 1 mol of the aminosilane compound A (a). When the amount of water (d) is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the antistatic coating composition is poor. The preferred addition amount is 3 to 10 mol per 1 mol of the mixture (a).

In the antistatic coating composition used in the present invention 3, the aminosilane compound A may be further added, if necessary.
An acid may be added as a catalyst for the hydrolysis of (a). The acid may be added in an amount of 0.01 to 5% by weight in the water added to the composition in the above ratio.
If it is less than this ratio, the effect as a catalyst cannot be expected,
The higher the amount, the more inhomogeneous the coating. The acid is not particularly limited, and either an inorganic acid or an organic acid can be used, and examples thereof include hydrochloric acid, sulfuric acid, and nitric acid.

The method of preparing the antistatic coating composition used in the present invention 3 is not particularly limited, and examples thereof include a method of mixing the above-mentioned constituent materials at once and a method of dividing a specific constituent material. And the like, and then the remaining constituent materials are added and mixed. As a method of dividing and mixing, for example, an aminosilane compound A (a) is used.
An organic solvent is added to and mixed and stirred, and water containing an acid if necessary is added to obtain a hydrolyzate of the aminosilane compound A (a). To this solution, a mixture of one or more trifluoromethanesulfonic acid compounds is added and mixed by stirring to obtain the composition.

In the method for producing a laminate of the present invention 3, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. The method for producing a laminate of the present invention is the same as the method for producing a laminate of the present invention, except that an antistatic coating composition containing a trifluoromethanesulfonic acid compound (b ₂ ) is used.

In the present invention 4 (the invention of claim 4 is referred to as the present invention 4), in the composition for antistatic coating for obtaining the high refractive index layer of the method for producing a laminate of the present invention, the heteropolyacid compound ( Instead of b), sulfuric acid (b ₃ ) is used.

The amount of sulfuric acid (b ₃ ) is limited to the ratio of 0.01 to 1 mol with respect to 1 mol of the aminosilane compound A (a). When the amount of sulfuric acid (b ₃ ) is small, the film does not have sufficient conductivity to prevent static electricity, and when it is large, the film becomes cloudy and opaque. The preferred addition amount is in the range of 0.05 to 0.5 mol with respect to 1 mol of the aminosilane compound A (a).

The organic solvent (c) used in the present invention 4 is
There is no particular limitation as long as it is compatible with the aminosilane compound A (a) and water (d) and dissolves sulfuric acid (b ₃ ). For example, for obtaining the high refractive index layer of the present invention, It is similar to that used in the antistatic coating composition. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention.

Regarding the water (d) used in the present invention 4,
The purpose of use, the amount used, and the fact that an acid may be added as a catalyst, if necessary, are the same as in the third embodiment.

Regarding the method for producing the antistatic coating composition used in the present invention 4, the method for producing the antistatic coating composition in the present invention 3 is different from the trifluoromethanesulfonic acid compound (b ₂ ) in sulfuric acid. It is the same as the present invention 3 except that (b ₃ ) is used.

In the method for producing a laminate of the present invention 4, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. The method for producing the laminate of the present invention is the same as the method for producing the laminate of the present invention, except that the antistatic coating composition containing sulfuric acid (b ₃ ) is used.

In the present invention 5 (the invention of claim 5 is referred to as the present invention 5), in the composition for antistatic coating for obtaining the high refractive index layer of the method for producing a laminate of the present invention, the heteropolyacid compound ( Fluorosulfonic acid (b ₄ ) instead of b)
(FSO ₃ H) is used.

Fluorosulfonic acid (b_Four) Is
0.0001 relative to 1 mol of the nosilane compound A (a)
It is limited to a ratio of 0.1 mol. Fluorosulfonic acid
(B _Four) Is less, there is sufficient conductivity to prevent electrification.
If it is not applied to the film and increases, the film becomes cloudy and opaque.
Become. The preferred addition amount is aminosilane compound A (a)
It is in the range of 0.008 to 0.05 mol with respect to 1 mol.
It

The organic solvent (c) used in the present invention 5 is
There is no particular limitation as long as it is compatible with the aminosilane compound A (a) and water (d) and dissolves the fluorosulfonic acid (b ₄ ). For example, the high refractive index layer of the present invention is obtained. Are similar to those used in antistatic coating compositions for. The amount of the organic solvent (c) used is also
It is similar to the amount used in the antistatic coating composition of the present invention.

Regarding the water (d) used in the present invention 5,
The purpose of use, the amount used, and the fact that an acid may be added as a catalyst, if necessary, are the same as in the third embodiment.

Regarding the method for producing the antistatic coating composition used in the present invention 5, the fluorocarbon compound (b ₂ ) is used in place of the trifluoromethanesulfonic acid compound (b ₂ ) in the method for producing the antistatic coating composition in the present invention 3. It is the same as the third aspect of the invention except that a sulfonic acid (b ₄ ) is used.

In the method for producing a laminate of the present invention 5, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. Except that the antistatic coating composition containing fluorosulfonic acid (b ₄ ) is used,
This is the same as the method for producing a laminate of the present invention.

In the present invention 6 (the invention of claim 6 is referred to as the present invention 6), as an antistatic coating composition for obtaining a high refractive index layer, the charging used in the method for producing a laminate of the present invention. Aminosilane compound A in a composition for preventing coating
Instead of (a), the aminosilane compound A according to the present invention
A silane compound (a ₁ ) containing 50 to 100 mol% of is added, and the antistatic coating composition of the present invention further added with a metal alkoxide (e) is used.

The silane compound (a ₁ ) used in the present invention 6 is the aminosilane compound A described in the present invention.
A silane compound containing ˜100 mol% is used. In the silane compound (a ₁ ) used in the present invention 6, the silane compound other than the aminosilane compound A is a silane represented by the general formula [II] or the general formula [III] described in the description of the present invention. A compound is used. In the silane compound (a ₁ ) used in the present invention 6, when the amount of the silane compound other than the aminosilane compound A is large, white precipitation occurs or gelation occurs during preparation of the antistatic coating composition, It cannot be used as a coating solution.

The metal alkoxide (e) used in the present invention 6 is a zirconium tetraalkoxide represented by the general formula Zr (OR ³ ) ₄ , a titanium tetraalkoxide represented by the general formula Ti (OR ⁴ ) ₄ , and a general tetraalkoxide. Formula Al
It is at least one metal alkoxide selected from the group consisting of aluminum trialkoxides represented by (OR ⁵ ) ₃ .

Zr (OR ³ ) ₄ zirconium tetraalkoxides, Ti (OR ⁴ ) ₄ titanium tetraalkoxides and Al (OR ⁵ ) ₃ aluminum trialkoxides R ³ and R ⁴ And R ⁵ represents an alkyl group having 1 to 5 carbon atoms. However, when the carbon number increases, the stability of the antistatic coating composition decreases and the long-term storage stability deteriorates. Limited. Examples of R ³ , R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group and a tert-butyl group.

Examples of the zirconium tetraalkoxide include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-iso-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide. , Zirconium tetra-
tert-butoxide and the like, particularly zirconium tetra-n-butoxide, zirconium tetra-is.
O-propoxide is preferred.

As the titanium tetraalkoxide,
For example, titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide,
Titanium tetra-iso-propoxide, titanium tetra-n-butoxide, titanium tetra-sec-
Examples thereof include butoxide and titanium tetra-tert-butoxide, and titanium tetra-n-butoxide and titanium tetra-iso-propoxide are particularly preferable.

As aluminum trialkoxide,
For example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide,
Aluminum tri-iso-propoxide, aluminum tri-n-butoxide, aluminum tri-sec-
Examples thereof include butoxide and aluminum tri-tert-butoxide, and aluminum tri-sec-butoxide and aluminum tri-iso-propoxide are particularly preferable.

Composition for Antistatic Coating Used in Present Invention 6
In the product, the silane compound (a ₁) And metal alkoki
The molar ratio of side (e) is 70:30 to 99: 1.
If the amount of metal alkoxide (e) decreases, the effect of addition will increase.
However, if the amount is large, the film-forming property of the composition may be deteriorated.
The film is likely to be cracked. Metal alkoxide
In the case of zirconium tetraalkoxide,
The ratio is preferably 80:20 to 99: 1, 8
0:20 to 95: 5 is particularly preferable. Titanium tetra
In the case of alkoxide, this molar ratio is 80: 20-9.
5: 5 is particularly preferred. Aluminum trialkoxide
, The molar ratio should be 85:15 to 99: 1.
Is preferred, and 85:15 to 95: 5 is particularly preferred.

The amount of the heteropolyacid compound (b) used in the present invention 6 is limited to 0.001 to 0.15 mol with respect to 1 mol of the silane compound (a ₁ ). When the amount of the heteropolyacid compound (b) is small, the film does not have sufficient conductivity to prevent electrification, and when it is large, the film becomes cloudy and opaque. The preferable addition amount is in the range of 0.01 to 0.15 mol with respect to 1 mol of the silane compound (a ₁ ).

The organic solvent (c) used in the present invention 6 is
There is no particular limitation as long as it is compatible with the silane compound (a ₁ ), water (d) containing an acid and metal alkoxide (e) and can dissolve the heteropolyacid compound (b), and examples thereof include , Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran and the like, and methyl alcohol, ethyl alcohol and isopropyl alcohol are particularly preferable. These may be used alone or 2
You may use together 1 or more types.

The amount of the organic solvent (c) is limited to a ratio of 10 to 100 mol with respect to 1 mol of the silane compound (a ₁ ). When the amount of the organic solvent (c) is small, the coating solution is difficult to mix uniformly, resulting in an inhomogeneous composition. When the amount is large, the solid content concentration of the composition becomes too low, and a sufficient antistatic ability is obtained when formed into a film. Can't get The preferable addition amount is 20 to 50 with respect to 1 mol of the silane compound (a ₁ ).
It is in the molar range.

In the acid-containing water (d) used in the present invention 6, the acid is added as a catalyst for the hydrolysis of the silane compound (a ₁ ) and the metal alkoxide (e). The addition amount may be 0.001 to 5% by weight in the water (d) used for producing the coating composition. When the amount of acid is small, the effect as a catalyst cannot be expected, and when it is large, the coating becomes inhomogeneous. The acid is not particularly limited, and either an inorganic acid or an organic acid can be used, and examples thereof include hydrochloric acid, sulfuric acid, and nitric acid. Water is added for the hydrolysis of the silane compound (a ₁ ) and the metal alkoxide (e).
The amount of water (d) is limited to a ratio of 0.1 to 5 mol with respect to 1 mol of the silane compound (a ₁ ). When the amount of water (d) is small, sufficient hydrolysis is unlikely to occur, and when it is large, the compatibility with the coating composition is poor. The preferable addition amount is 0.5 to 3 mol per 1 mol of the silane compound (a ₁ ).

The composition of the coating composition used in the present invention 6 is as described above, but a hydrophilic polymer such as polyethylene glycol may be added to further improve the conductivity. In addition, in order to improve the film forming property, methyl cellulose, hydroxypropyl methyl cellulose,
A cellulose derivative such as hydroxyethyl cellulose or hydroxypropyl cellulose may be contained. Further, for the same purpose, an oxide colloid such as silica sol, alumina sol, zirconia sol may be contained. Further, a known curing catalyst may be added for curing the above silane compound (a ₁ ) and metal alkoxide (e).

Further, in order to obtain a layer having a high refractive index, ultrafine tantalum oxide (Ta) having an average particle diameter of 1000 Å or less is used.
₂ O ₅ ), ultrafine particles of zirconium oxide (ZrO ₂ ), ultrafine particles of zinc oxide (ZnO), ultrafine particles of titanium oxide (TiO ₂ ), and the like, or a mixture thereof in an antistatic coating composition. May be dispersed and mixed.

The method for preparing the antistatic coating composition used in the present invention 6 is not particularly limited, and examples thereof include a method of mixing the above-mentioned constituent materials at once and a method of dividing a specific constituent material. And the like, and then the remaining constituent materials are added and mixed. As a method of dividing and mixing, for example, the aminosilane compound A and another silane compound are mixed, an organic solvent is added to this mixture, and water containing an acid is added to the mixture and stirred, and the silane compound (a ₁ ) Is obtained. To this solution, a metal alkoxide was added and mixed with stirring to obtain a silane compound (a
₁ ) and a solution of the hydrolyzate of metal alkoxide are obtained. To this solution, one kind or a mixture of two or more kinds of heteropolyacid compounds is added and mixed by stirring to obtain the coating composition.

In the method for producing a laminated body of the present invention 6, further,
Low refractive index layers are laminated on the base material alternately with the high refractive index layers. The low refractive index layer is not particularly limited as long as it is a transparent layer having a lower refractive index than the high refractive index layer. Examples thereof include a coating layer made of a fluororesin, a porous silica layer, a coating layer made of a fluorine-containing inorganic compound, and a layer in which fine particles of the fluorine-containing inorganic compound are dispersed and mixed in a binder. Incidentally, as specific representative examples of this fluorine-containing inorganic compound, MgF ₂ , AlF ₃ , BaF
₂ , LaF ₂ , CaF ₂ , Na ₃ AlF _{6 and the} like can be mentioned.

In the present invention 6, the base material forming the laminate is not particularly limited as long as it is a transparent base material, and silicate glass, alkali silicate glass, soda lime glass are used according to the purpose. , Potassium lime glass, lead lime glass, barium glass, borosilicate glass, and other silicate glasses, aluminosilicate glass, lithium aluminosilicate glass, quartz glass, and other short crystals, magnesia, sialon, and other transparent materials. Plastics such as photo-ceramics, polycarbonate, acrylic resin, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyester, polyurethane and cellulose triacetate can be used. In particular, silicate glass, alkali silicate glass and soda lime glass are preferable. Further, the shape of the base material is not particularly limited.

In the method for producing a laminate of the present invention 6, the high refractive index layer and the low refractive index layer are alternately laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Laminate the layers. The method for producing a laminate having the smallest number of layers is as follows.First, a high refractive index layer is laminated on the surface of a transparent substrate, dried, and then a low refractive index layer is laminated thereon, dried, and cured. Is the way to do it.

The layers are laminated preferably by painting. Various methods such as a spin coating method, a dipping method, a spraying method, a roll coater method, and a meniscus coater method can be used as the method of coating the substrate.

In the present invention 7 (the invention of claim 7 is referred to as the invention 7), the heteropolyacid compound is used in the antistatic coating composition for obtaining the high refractive index layer of the method for producing a laminate of the invention 6. Instead of (b), the perchloric acid compound (b ₁ ) is used.

The perchloric acid compound (b) used in the present invention 7
₁) Is the amount of the silane compound (a ₁) For 1 mol
Therefore, the amount is limited to 0.005 to 0.32 mol. Excessive
Chloric acid compound (b₁) Is low enough to prevent static
If the conductivity is not imparted to the film and the amount increases, the film becomes cloudy.
And becomes opaque.

The organic solvent (c) used in the present invention 7 is
There is no particular limitation as long as it is compatible with the silane compound (a ₁ ), water (d) and the metal alkoxide (e) and can dissolve the perchloric acid compound (b ₁ ). The same as that used in the antistatic coating composition for obtaining the high refractive index layer of No. 6. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention 6.

The water (d) used in the present invention 7 is added for the hydrolysis of the above-mentioned silane compound (a ₁ ) and metal alkoxide (e). The amount of water (d) is limited to a ratio of 0.1 to 5 mol with respect to 1 mol of the silane compound (a ₁ ). When the amount of water (d) is small, sufficient hydrolysis is unlikely to occur, and when it is large, the compatibility with the coating composition is poor. The preferred addition amount is silane compound (a ₁ ) 1
It is 1 to 3 moles per mole. Particularly, in the case of aluminum trialkoxide as the metal alkoxide, the amount is 0.5 to 3 mol per 1 mol of the total of the mixture (a ₁ ) and the metal alkoxide (e).

If necessary, an acid may be added to the antistatic coating composition used in the present invention 7 as a catalyst for the hydrolysis of the silane compound (a ₁ ) and the metal alkoxide (e). . The amount of the acid added may be 0.001 to 5% by weight in the water added to the composition in the above ratio. If it is less than this ratio, the effect as a catalyst cannot be expected, and if it is more than this ratio, the coating becomes inhomogeneous. The acid is not particularly limited, and either an inorganic acid or an organic acid can be used, and examples thereof include hydrochloric acid, sulfuric acid, and nitric acid.

The method for preparing the antistatic coating composition used in the present invention 7 is not particularly limited, and examples thereof include a method of mixing the above-mentioned constituent materials at once, and a method of dividing a specific constituent material. And the like, and then the remaining constituent materials are added and mixed. As a method of dividing and mixing, for example, the aminosilane compound A and another silane compound are mixed, an organic solvent is added to this mixture, and water containing an acid is added to the mixture after stirring, if necessary. A hydrolyzate of the compound (a ₁ ) is obtained. A metal alkoxide is added to this solution and mixed with stirring to obtain a solution of a hydrolyzate of the silane compound (a ₁ ) and the metal alkoxide. To this solution, one kind or a mixture of two or more kinds of perchloric acid compound (b ₁ ) is added, and mixed by stirring to obtain the coating composition.

The method for producing a laminate of the present invention 7 is the same as the method for forming an antistatic coating for forming a high refractive index layer, in which an antistatic coating composition containing a heteropolyacid compound (b) is used. The method for producing a laminate of the present invention 6 is the same as that of the present invention 6 except that the antistatic coating composition containing the perchloric acid compound (b ₁ ) is used.

In the present invention 8 (the invention of claim 8 is referred to as the present invention 8), the heteropolyacid compound is used in the antistatic coating composition for obtaining the high refractive index layer of the method for producing a laminate of the present invention 6. Instead of (b), a trifluoromethanesulfonic acid compound (b ₂ ) is used.

The amount of the trifluoromethanesulfonic acid compound (b ₂ ) used in the present invention 8 is limited to 0.001 to 0.3 mol per 1 mol of the silane compound (a ₁ ). . When the amount of the trifluoromethanesulfonic acid compound (b ₂ ) is small, the film does not have sufficient conductivity for antistatic, and when it is large, the film becomes cloudy and opaque. The preferable addition amount is in the range of 0.05 to 0.2 mol with respect to 1 mol of the silane compound (a ₁ ).

The organic solvent (c) used in the present invention 8 is
It is not particularly limited as long as it is compatible with the silane compound (a ₁ ), water (d) and metal alkoxide (e) and dissolves the trifluoromethanesulfonic acid compound (b ₂ ). It is the same as that used in the antistatic coating composition for obtaining the high refractive index layer of Invention 6. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention 6.

Regarding the water (d) used in the present invention 8,
The purpose of use, the amount used, and the addition of an acid as a catalyst, if necessary, are the same as in the present invention 7.

The method for producing the antistatic coating composition used in the present invention 8 is the same as in the method for producing the antistatic coating composition in the present invention 7, except that trifluoromethane is used instead of the perchloric acid compound (b ₁ ). It is the same as the present invention 7 except that the sulfonic acid compound (b ₂ ) is used.

In the method for producing a laminate of the present invention 8, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. The method for producing the laminate of the present invention 6 is the same as that of the present invention 6 except that the antistatic coating composition containing the trifluoromethanesulfonic acid compound (b ₂ ) is used.

In the present invention 9 (the invention of claim 9 is referred to as invention 9), the heteropolyacid compound is used in the antistatic coating composition for obtaining the high refractive index layer of the method for producing a laminate of the invention 6. Sulfuric acid (b ₃ ) is used instead of (b).

The amount of sulfuric acid (b ₃ ) used in the present invention 9 is 0.001 with respect to 1 mol of the silane compound (a ₁ ).
Limited to a proportion of ~ 0.4 mol. When the amount of sulfuric acid (b ₃ ) is small, the film does not have sufficient conductivity to prevent static electricity, and when it is large, the film becomes cloudy and opaque.

The organic solvent (c) used in the present invention 9 is
There is no particular limitation as long as it is compatible with the silane compound (a ₁ ), water (d) and metal alkoxide (e) and can dissolve sulfuric acid (b ₃ ). It is the same as that used in the antistatic coating composition for obtaining the refractive index layer. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention 6.

Regarding the water (d) used in the present invention 9,
The purpose of use, the amount used, and the addition of an acid as a catalyst, if necessary, are the same as in the present invention 7.

The method for producing the antistatic coating composition used in the present invention 9 is the same as in the method for producing the antistatic coating composition in the present invention 7, except that the perchloric acid compound (b ₁ ) is replaced by sulfuric acid ( It is the same as the present invention 7 except that b ₃ ) is used.

The method for producing a laminate of the present invention 9 is the same as the method for preparing an antistatic coating composition for forming a high refractive index layer, in which an antistatic coating composition containing a heteropolyacid compound (b) is used. The method for producing a laminate of the present invention 6 is the same as that of the present invention, except that the antistatic coating composition containing sulfuric acid (b ₃ ) is used.

In the tenth aspect of the present invention (the tenth aspect of the invention is referred to as the tenth aspect of the present invention), a heteropolyacid compound is used in the antistatic coating composition for obtaining the high refractive index layer of the method for producing a laminate of the sixth aspect of the present invention. Instead of (b), fluorosulfonic acid (b ₄ ) is used.

The amount of the fluorosulfonic acid (b ₄ ) used in the present invention 10 is limited to a ratio of 0.0001 to 0.1 mol based on 1 mol of the silane compound (a ₁ ). When the amount of fluorosulfonic acid (b ₄ ) is small, the film does not have sufficient conductivity to prevent electrification, and when it is large, the film becomes cloudy and opaque.

Organic solvent (c) used in the present invention 10
Is compatible with the silane compound (a ₁ ), water (d) and the metal alkoxide (e), and the fluorosulfonic acid (b
There is no particular limitation as long as it dissolves ₄ ), and for example, it is the same as that used in the antistatic coating composition for obtaining the high refractive index layer of the present invention 6. The amount of the organic solvent (c) used is the same as the amount used in the antistatic coating composition of the present invention 6.

With respect to the water (d) used in the present invention 10, the purpose of use, the amount used, and, if necessary, an acid may be added as a catalyst are the same as in the present invention 7.

Regarding the method for preparing the antistatic coating composition used in the present invention 10, the present invention is applied except that fluorosulfonic acid (b ₄ ) is used in place of the perchloric acid compound (b ₁ ). Similar to 7.

In the method for producing a laminate of the present invention 10, the antistatic coating composition containing the heteropolyacid compound (b) is used as the antistatic coating composition for forming the high refractive index layer. The method for producing the laminate of the present invention 6 is the same as that of the present invention 6, except that the antistatic coating composition containing fluorosulfonic acid (b ₄ ) is used.

The present invention 11 (the invention of claim 11 is referred to as the present invention 11) is characterized in that a high refractive index layer having conductivity, a low refractive index layer and a low refractive index layer are provided on the surface of a transparent substrate. A method for producing a laminate in which a plurality of layers are laminated so as to be an outermost layer, wherein the high refractive index layer is the high refractive index layer according to claims 1 to 10, and the low refractive index layer is generally Formula Si (OR ⁶ ) ₄
(In the formula, R ⁶ is an alkyl group having 1 to 5 carbon atoms) 1 mol of an alkoxysilane, 2 to 8 mol of a basic aqueous solution having a pH of 10.0 to 12.0, and 10 to 30 mol of an organic solvent. The condensation composition (B) obtained by mixing and the general formula (R ⁸ ) _s Si (OR ⁷ ) _4-s (in the formula, R ⁷ and R ⁸
Is an alkyl group having 1 to 5 carbon atoms, s is an integer of 0 to 3), and 1 mole of an alkoxysilane, 3 to 8 moles of an acidic aqueous solution having a pH of 0 to 2.6, and 10 to 30 moles of an organic solvent are mixed. The condensation composition (C) thus obtained is mixed with the weight ratio B / C =
It is a method for producing a laminate, which comprises a layer obtained by applying a composition obtained by mixing at 0.4 to 2.4.

Used in the method for producing a laminate according to the present invention 11
The condensation composition (B) is ⁶)_Four(In the formula, R⁶
Is an alkoxy group represented by an alkyl group having 1 to 5 carbon atoms.
Orchid, basic aqueous solution and organic solvent are mixed and alkoxy
It is obtained by partially hydrolyzing and polycondensing silane.

In the above-mentioned alkoxysilane represented by Si (OR ⁶ ) ₄ , when the carbon number of R ⁶ is large, the stability of the composition is deteriorated and the long-term storage stability is deteriorated. 5 alkyl group, for example, methyl group, ethyl group, n-propyl group, iso-propyl group,
Examples thereof include n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkoxysilane represented by Si (OR ⁶ ) ₄ include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane and tetra. -Sec-butoxysilane, tetra-t
ert-butoxysilane and the like, tetramethoxysilane, from the viewpoint of reactivity in hydrolysis, polycondensation,
Tetraethoxysilane is preferred, and tetraethoxysilane is particularly preferred.

The above-mentioned basic aqueous solution is a solution having a pH of 10.0 to 12.0 in which a basic species is dissolved in water. The base species is not particularly limited as long as it can adjust the pH of the basic aqueous solution to 10.0 to 12.0, and examples thereof include ammonia, ammonium hydroxide, potassium hydroxide, etc. Ammonia is preferred because it is easy.

When the pH of the basic aqueous solution is low, the molecular weight of the colloidal silica obtained is low, making it difficult to form an antireflection coating, and when it is high, the stability of the condensation composition (B) obtained is low. It is limited to 10.0 to 12.0, preferably 10.3 to 11.5, and 10.8 to
11.4 is particularly preferred.

When the amount of the basic aqueous solution is small, the molecular weight of the obtained colloidal silica is low, and it becomes difficult to form the antireflection layer. When the basic aqueous solution is large, the stability of the condensation composition (B) is low. 2 to 8 moles and preferably 3 to 4 moles are added to 1 mole of silane.

The organic solvent is not particularly limited as long as it is compatible with the above-mentioned alkoxysilane and basic aqueous solution, and examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethoxyethyl alcohol and allyl alcohol. However, isopropyl alcohol is particularly preferable.

When the amount of the organic solvent added is small, the stability of the condensation composition (B) is low, and when it is large, the molecular weight of the obtained colloidal silica is low and it becomes difficult to form an antireflection coating. It is limited to 10 to 30 mol per 1 mol of the above-mentioned alkoxysilane, and from the viewpoint of stability of the composition, 13 to 18 mol per 1 mol of alkoxysilane is preferable.

The method for preparing the condensation composition (B) is not particularly limited, and examples thereof include a method in which the above-mentioned alkoxysilane, basic aqueous solution and organic solvent are supplied to a stirrer and mixed to produce them. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature for preparing the condensation composition (B) is
When it becomes lower, the polycondensation reaction becomes insufficient, and when it becomes higher,
Since the stability of the condensation composition (B) decreases, it is 10 to 30.
It is preferably carried out at a temperature of 20 ° C., particularly preferably 20 to 25 ° C.

The time for preparing the condensation composition (B) is
When it is shortened, the reaction rate of the polycondensation reaction is lowered, and when it is lengthened, the stability of the condensation composition (B) is lowered.
0 hours are preferred, and 2-4 hours are particularly preferred. Therefore, the condensation composition (B) is prepared at 10 to 30 ° C.
It is preferably carried out for 10 hours, particularly preferably at 20 to 25 ° C. for 2 to 4 hours.

Used in the method for producing a laminate of the present invention 11.
The condensation composition (C) having the general formula (R ⁸)_sSi (O
R⁷)_4-s(In the formula, R⁷And R⁸Is a C1-C5
Alkyl group, s is an integer of 0 to 3)
Mix the orchid, acidic aqueous solution and organic solvent, and
It is obtained by partially hydrolyzing and polycondensing orchid.

The above general formula (R ⁸ ) _s Si (OR ⁷ )
_{In the} alkoxysilane represented by _4-s , R ⁷ and R ⁸ are alkyl groups having 1 to 5 carbon atoms because the stability of the condensation composition decreases and the long-term stability deteriorates when the number of carbon atoms increases. And a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, se
Examples thereof include c-butyl group and tert-butyl group.
In addition, s shows the integer of 0-3.

The alkoxysilane represented by (R ⁸ ) _s Si (OR ⁷ ) _4-s is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane and tetra-n-.
Propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyl. Tri-iso-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-sec-butoxysilane, monomethyltri-tert-butoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-.
Propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-
sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, trimethylmono-n-butoxysilane , Trimethylmono-sec-butoxysilane, trimethylmono-tert-butoxysilane, triethylethoxysilane, and the like, and from the viewpoint of reactivity, tetramethoxysilane, tetraethoxysilane, and monomethyltriethoxysilane are preferable, and tetraethoxysilane is particularly preferable. Is preferred.

The above acidic aqueous solution has a pH of 0 to 2.6 in which an acidic species is dissolved in water. The acidic species is not particularly limited as long as it can adjust the pH of the acidic aqueous solution to 0 to 2.6, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid and the like, hydrochloric acid and nitric acid are preferable, and hydrochloric acid is particularly preferable. .

When the pH of the acidic aqueous solution becomes high, the hydrolysis of the alkoxysilane becomes insufficient, so that the pH is 0 to 2.6.
If it is too low, the stability of the condensation composition (C) may decrease, and if it is too high, the hydrolysis of the alkoxysilane may be insufficient.
0 to 1.7 is preferable, and 1.1 to 1.2 is particularly preferable.

If the amount of the acidic aqueous solution added is small, the hydrolysis of the alkoxysilane will be insufficient, and furthermore, it will be difficult to apply the resulting composition to the substrate, and if it is large,
Since the stability of the condensation composition (C) decreases, (R ⁸ ) _s
It is limited to 3 to 8 mol, preferably 4 to 7 mol, per 1 mol of the alkoxysilane represented by Si (OR ⁷ ) _4-s .

The above organic solvent is (R ⁸ ) _s Si (O
R ⁷ ) _4-s is not particularly limited as long as it is compatible with the alkoxysilane represented by _4-s and the acidic aqueous solution, and for example, the same one as used in the production of the condensation composition (B) can be used. When the addition amount of the organic solvent is small, the stability of the condensation composition (C) is lowered, and when the addition amount is large, the alkoxysilane is not sufficiently hydrolyzed, so that (R ⁸ ) _s Si
It is limited to 10 to 30 mol, and preferably 13 to 18 mol, based on 1 mol of the alkoxysilane represented by (OR ⁷ ) _4-s .

The method for preparing the condensation composition (C) is not particularly limited, and for example, an alkoxysilane represented by (R ⁸ ) _s Si (OR ⁷ ) _4-s , an acidic aqueous solution and an organic solvent may be added to a stirrer. The method of supplying, mixing and preparing is mentioned. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

The temperature for preparing the condensation composition (C) is
When it becomes lower, the polycondensation reaction becomes insufficient, and when it becomes higher,
Since the stability of the condensation composition (C) decreases, it is 10 to 30.
It is preferably carried out at a temperature of 20 ° C., particularly preferably 20 to 25 ° C.

The time for producing the condensation composition (C) is
When the length is short, a sufficient molecular weight cannot be obtained, and when the length is long, the stability of the condensation composition (C) is lowered.
0 hours are preferred, and 2-4 hours are particularly preferred. Therefore, the condensation composition (C) is produced at 10 to 30 ° C.
It is preferably carried out for 10 hours, particularly preferably at 20 to 25 ° C. for 2 to 4 hours.

In the method for producing the composition used in the present invention 11, the condensation composition (B) and the condensation composition (C) are mixed in a weight ratio B / C = 0.4 to 2.4.

When the amount of the condensation composition (B) decreases, the porosity of the obtained coating decreases, and the antireflection effect of the obtained laminate decreases, and when the amount of the condensation composition (B) increases, the adhesion between the obtained coating and the base material decreases. Therefore, the weight ratio of the condensation composition (B) to the condensation composition (C) is limited to 0.4 to 2.4, for improving the stability of the composition and the adhesion between the coating and the substrate. , 1.5
~ 2.3 is preferred.

When the temperature at which the condensation composition (B) and the condensation composition (C) are mixed is lowered, polycondensation of the colloidal silica and silica sol becomes difficult, and the antireflection effect of the obtained coating is lowered, and the temperature is high. If so, the stability of the obtained composition is lowered, so it is preferable to carry out at -10 to 30 ° C,
-8-25 degreeC is especially preferable.

If the time for mixing the condensation composition (B) and the condensation composition (C) is shortened, the polycondensation of the colloidal silica and the silica sol becomes insufficient, and the antireflection effect of the obtained coating decreases, and the time increases. , The stability of the sol decreases, so that 0.5 to 4 hours are preferable, and 2 to 3 hours are particularly preferable. Therefore, the condensation composition (B) and the condensation composition (C) are preferably mixed at -10 to 30 ° C for 0.5 to 4 hours, and at -8 to 25 ° C for 2 to 3 hours. Is particularly preferable.

The method of mixing the condensation composition (B) and the condensation composition (C) is not particularly limited. For example, the condensation composition (B) and the condensation composition (C) are supplied to a stirrer and mixed by stirring. And a method of manufacturing the same. The stirrer is not particularly limited, and a simple stirrer such as a magnetic stirrer is sufficient.

In the method for producing a laminate of the present invention 11, a conductive high refractive index layer and a low refractive index layer are provided on the surface of a transparent substrate, and the low refractive index layer is the outermost layer. A method for producing a laminate having a plurality of laminated layers, wherein the high refractive index layer is the high refractive index layer according to claim 1 and the low refractive index layer is a layer obtained from the composition. Consists of. The method for laminating the low refractive index layer is performed by applying the composition and curing the composition.

The substrate and coating method used for the above-mentioned lamination are not particularly limited, and are the same as the substrate and coating method described in the present invention. It should be noted that the coating is preferably performed at a relative humidity of 50% or less in the atmosphere because the obtained coating becomes cloudy when the humidity in the atmosphere is high.

When the composition is applied, the film thickness is not particularly limited, but it is necessary to apply the composition so as to obtain a film having the following relationship with the wavelength for which the antireflection effect is desired. This is preferable because it can be improved.

[0132]

[Equation 1]

D: film thickness λ: wavelength at which antireflection effect is desired to be obtained n: refractive index of film m: 0 or natural number

When the above composition is applied, it is preferable to dilute it with a solvent to adjust the viscosity of the composition, if necessary, because the coating efficiency of the composition on the substrate is improved. .

In such a case, the solvent used is not particularly limited as long as it is compatible with the above composition,
For example, isopropyl alcohol, ethoxy ethanol, allyl alcohol and the like can be mentioned, and from the viewpoint of improving the porosity of the obtained coating, isopropyl alcohol and ethoxy ethanol are preferable.

The above-mentioned curing method is not particularly limited and may be naturally dried at room temperature to be cured, or may be dried by heating to be cured. For example, a silicate glass is used as a substrate, and the composition for coating a low refractive index layer is formed on the surface of a material having the high refractive index layer described in the present invention 1 to 10 laminated on the surface thereof. When laminated by the method, naturally dried at room temperature, and then cured at a temperature of 60 to 300 ° C., the silica sol in the composition became porous due to the difference in shrinkage between the cured silicon matrix and colloidal silica. A laminate having an antireflection coating is obtained. Further, for example, a plastics product is used as a substrate, and the composition for coating a low refractive index layer described above is provided on the surface of a material on which the high refractive index layer described in the present invention 1 to 10 is laminated. After laminating by the above method and natural drying at room temperature, the temperature is 60 to 150 ° C., preferably 80 to 10 ° C.
When cured at a temperature of 0 ° C., a laminate having an antireflection coating, which is also made porous, is obtained.

In the present invention 12 (the invention of claim 12 is referred to as the invention 12), the high refractive index layer and the low refractive index of the invention and the inventions 2 to 11 are formed on the surface of a transparent substrate. A method of manufacturing a laminated body in which layers are alternately laminated so that the low refractive index layer becomes the outermost layer, characterized in that when laminating each layer, the already laminated layers are cured. . According to the method for producing a laminate of the present invention 12, there is an advantage that the elution phenomenon from the underlying layer does not occur even when the coating liquid is applied to form the high refractive index layer and the low refractive index layer.

[0138]

The high refractive index layer prepared as described above from the antistatic coating composition used in the present invention and the present inventions 2 to 5 is a heteropolyacid compound, a perchloric acid compound, a trifluoromethanesulfonic acid compound. , Sulfuric acid or fluorosulfonic acid uniformly exists in an ionic state, so that it has high transparency and high conductivity. Therefore, according to the present invention and the production methods of the present inventions 2 to 5, a high refractive index layer having sufficient antistatic performance can be obtained while maintaining the optical characteristics of the base material before the film formation. Present Invention and Present Inventions 2-5
Further, according to the method for producing a laminate, since the low refractive index layer is laminated on the surface of the high refractive index layer, a transparent coating having a high antireflection effect and an antistatic effect is formed on the substrate. The laminated body can be easily manufactured.

The high refractive index layer produced as described above from the antistatic coating compositions used in the present inventions 6 to 10 is a heteropolyacid compound, a perchloric acid compound, a trifluoromethanesulfonic acid compound, sulfuric acid or Since the fluorosulfonic acid is present in a uniform ionic state, it has high transparency and high conductivity. Also, since the obtained coating contains oxides of zirconium, titanium or aluminum, scratches are less likely to occur even when strongly rubbed with a hard material,
The appearance is not easily deteriorated by scratches, and the performance can be maintained for a long time. Therefore, according to the production methods of the present inventions 6 to 10, it is possible to obtain a high refractive index layer having sufficient antistatic performance while maintaining the optical characteristics of the substrate before the film formation. According to the method for producing a laminate of the present inventions 6 to 10, since the low refractive index layer is laminated on the surface of the high refractive index layer, the antireflection effect and the antistatic effect are high on the substrate. A laminate having a transparent coating can be easily manufactured.

In the composition for coating a low refractive index layer used in the present invention 11, in the condensation composition (B), polycondensation of alkoxysilane is considerably advanced and colloidal silica is formed,
In the condensation composition (C), the polycondensation of the alkoxysilane does not proceed relatively and is suppressed at the stage of silica sol, and the above composition, which is a mixture of both, is a mixture of colloidal silica and silica sol. This composition is applied on a substrate on which the high refractive index layers of the present inventions 1 to 10 are laminated,
By curing, the polycondensation reaction of silica sol and colloidal silica proceeds, and a porous coating film can be obtained due to the difference in contraction rate between silica sol and colloidal silica. Further, since this coating is an inorganic substance, it is less likely to be scratched even when it is rubbed with a hard material such as steel wool, and the appearance is not easily deteriorated due to scratches. Therefore, according to the eleventh aspect of the present invention, it is possible to easily manufacture a laminate having a transparent film having a high antireflection effect and an antistatic effect on a base material and having excellent scratch resistance.

According to the method for producing a laminate of the present invention 12,
Even if a coating liquid is applied to form the high-refractive index layer and the low-refractive index layer, the phenomenon of elution from the underlying layer does not occur, so a transparent coating with high antireflection and antistatic effects can be formed on the substrate. The formed laminate can be manufactured easily and constantly.

[0142]

EXAMPLES Examples of the present invention and the present inventions 2 to 12 will be described below. In addition, the evaluation method of each physical property regarding the laminated body shown in the result was as follows.

(1) Electrostatic potential measurement The evaluation sample was rubbed with a cloth, and the electrostatic potential after that was measured.
The measurement was performed with a meter KSD-0102 (manufactured by Kasuga Denki). (2) Reflectance Spectrophotometer (Shimadzu Corporation, trade name "UV-3101
PC ”), using only the substrate without the coating laminated
The light transmittance is measured in the range of 400 to 800 nm, and
Maximum transmittance (T_B) And both sides calculated from the refractive index of the substrate
Minimum reflectance (R _E) And the absorption rate of the substrate
Calculate (α). α = 100- (T_B+ R_E) Next, a laminated body in which a low refractive index layer and a high refractive index layer are laminated
The light transmittance is measured in the range of 400 to 800 nm, and
Maximum transmittance (T_S) And the absorption rate of the substrate obtained by the above formula
Calculate the one-sided minimum reflectance (R) from (α) using the following formula
To do. R = [100- (T_S+ Α)] / 2

(3) Pencil hardness The coating layer of the obtained laminate was measured and evaluated according to JIS K5400.

Examples 1 to 17 and Comparative Examples 1 to 12 (1) Preparation of High Refractive Index Layer Coating Composition (Antistatic Coating Composition) In the following Examples 1 to 12 and Comparative Examples 1 to 12,
The coating composition for obtaining the high refractive index layer having conductivity is N- (β- as the aminosilane compound A (a).
Aminoethyl) -γ-aminopropyltrimethoxysilane was used. Methyl alcohol is used as the organic solvent (c), and the compounding amount is aminosilane compound A (a) 1.
It was 25 molar equivalents relative to the molar equivalents. The blending amount of water (d) was 5 molar equivalents with respect to 1 molar equivalent of the aminosilane compound A (a). In water (d), Examples 1-4,
In 11 and Comparative Examples 1 to 6, 0.36% by weight of hydrochloric acid was contained. Through Examples 1 to 12 and Comparative Examples 1 to 12, the above compounding amounts were fixed, and the heteropoly acid compound (b), the perchloric acid compound (b ₁ ) to be compounded therein were fixed,
Tables 2 and 4 show the types of trifluoromethanesulfonic acid compound (b ₂ ), sulfuric acid (b ₃ ) or fluorofluorosulfonic acid (b ₄ ), and the compounding amount with respect to 1 molar equivalent of aminosilane compound A (a). Changed to. Since the heteropolyacid compound (b) contains water of hydration, the amount of water including this water of hydration was adjusted to a predetermined amount.

Further, in Examples 13 to 17, the aminosilane compound A (a) was used as the above Examples 1 to 12.
In place of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and methyltrimethoxysilane 9: 1 (molar ratio) Was used. The amount of the organic solvent (c) and water (d) compounded is N
It was 25 molar equivalents and 5 molar equivalents, respectively, with respect to 1 molar equivalent of the mixture of-(β-aminoethyl) -γ-aminopropyltrimethoxysilane and methyltrimethoxysilane. The water (d) contained 0.36% by weight of hydrochloric acid in Examples 13 and 14. Throughout Examples 13 to 17, the above blending amount was fixed, and the heteropolyacid compound (b), the perchloric acid compound (b ₁ ), the trifluoromethanesulfonic acid compound (b ₂ ) and the sulfuric acid (b) to be blended therein were fixed. ₃ ) or fluorofluorosulfonic acid (b ₄ ) and the compounding amount with respect to 1 molar equivalent of the silane compound mixture (a) were changed as shown in Table 3. Since the heteropolyacid compound (b) contains water of hydration, the amount of water including this water of hydration was adjusted to a predetermined amount.

Specific operating procedures of Examples 1 to 17 and Comparative Examples 1 to 12 were carried out as follows. The above-mentioned predetermined amount of ethyl alcohol is supplied to a glass beaker, the above-mentioned predetermined amount of aminosilane compound A (Examples 13 to 17 is further methyltrimethoxysilane) is added, and water containing 0.36% by weight of hydrochloric acid is further added. (However, Examples 5-10, 1
2, 15 to 17 and Comparative Examples 7 to 12 use pure water containing no hydrochloric acid), and after stirring at room temperature for 3 hours at a stirring speed of 800 rpm, an alcohol solution of a silane compound is obtained. It was The obtained alcohol solution is shown in Table 2
The predetermined amount of heteropolyacid compound, perchloric acid compound, trifluoromethanesulfonic acid compound, sulfuric acid or fluorosulfonic acid shown in 4 was added, and the mixture was further stirred at room temperature for 3 hours at a stirring speed of 800 rpm to coat the high refractive index layer. To obtain a composition (antistatic coating composition).

(2) Preparation of Composition for Coating Low Refractive Index Layer Next, a predetermined amount of tetraethoxysilane shown in Table 1, a basic aqueous solution whose pH was adjusted with ammonia, and isopropyl alcohol were applied to a magnetic stirrer. Supplying and mixing at 800 rpm for 2 hours at 20 ° C., a condensation composition (B) was obtained. Further, each of predetermined amounts of tetraethoxysilane, methyltriethoxysilane, an acidic aqueous solution whose pH was adjusted with hydrochloric acid and isopropyl alcohol shown in Table 1 were supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C., A condensation composition (C) was obtained.

Furthermore, the condensation composition (B) obtained above
And the condensation composition (C) at a weight ratio (condensation composition (B) / condensation composition (C)) shown in Table 1 to a magnetic stirrer, mixed at 800 rpm for 2 hours at 20 ° C. A composition for coating the refractive index layer was prepared. The obtained low-refractive-index-layer coating compositions are (b), (c), (d), (e), and (f), respectively, as shown in Table 1. Further, as a commercially available composition for coating a low refractive index layer, a fluororesin (manufactured by Asahi Glass Co., Ltd., trade name “CYTOP CTL-102” is used.
A ") was also used. This "Cytop CTL-102
"A" is the composition (a) for coating the low refractive index layer.

(3) Manufacture of Laminates (Manufacture of Laminates of Examples 1 to 10, 13 to 17 and Comparative Examples 1 to 12) A polycarbonate plate was added to the composition for coating a high refractive index layer prepared as described above. (Made by Teijin Ltd., trade name “Panlite”, 40 × 10 × 1 mm)
After pulling up at a speed of a minute, it was dried at room temperature for 10 minutes to obtain a polycarbonate plate on which a high refractive index layer was laminated. next,
The obtained high-refractive-index-layer-coated laminate was formed into a composition (a), (b), (c) for coating a low-refractive-index layer shown in Tables 2 to 4.
It is dipped in (d), (e) or (f), pulled up at a speed of 100 mm / min, dried at room temperature for 10 minutes, and the obtained laminate is cured at 110 ° C. for 60 minutes to obtain the objective. A laminated body was obtained. The physical properties of the laminate obtained as described above were evaluated based on the above-mentioned measurement methods, and the results are shown in Tables 2 to 4. In Comparative Examples 1, 4, 7, 9, and 11, the film was clouded and a transparent laminate could not be obtained. In Comparative Example 3, the low refractive index layer could not be laminated. Further, in Comparative Example 6, the composition for coating the low refractive index layer was gelated and the intended laminate could not be obtained.

(Production of Laminates of Examples 11 and 12) Table 2
In the same manner as above, a polycarbonate plate (manufactured by Teijin Ltd., trade name “Panlite”, 4
(0 × 10 × 1 mm), dried, and cured at 110 ° C. for 60 minutes, and then the composition for coating a low refractive index layer (b) (Example 11) or (d) (Example 12) described above. After coating in the same manner as above, drying and then curing at 110 ° C. for 60 minutes to obtain a target laminate. The physical properties of the obtained laminate were evaluated based on the above-mentioned measurement methods, and the results are shown in Table 2.

[0152]

[Table 1]

[0153]

[Table 2]

[0154]

[Table 3]

[0155]

[Table 4]

Examples 18 to 29, Comparative Examples 13 to 22 (1) Preparation of high refractive index layer coating composition (antistatic coating composition) In Examples 18 to 29 and Comparative Examples 13 to 22 below, The composition of the coating composition for obtaining the high refractive index layer having conductivity is N-as the aminosilane compound A (a).
A mixture of (β-aminoethyl) -γ-aminopropyltrimethoxysilane and tetraethoxysilane was used, and the metal alkoxide (e) shown in Table 5 and Table 6 was used. The compounding amount is a molar ratio of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane: tetraethoxysilane: metal alkoxide (e) = 8: 1:
It was set to 1. Methyl alcohol was used as the organic solvent (c), and the compounding amount was 25 molar equivalents with respect to 1 molar equivalent of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and tetraethoxysilane in total. did.

The blending amount of water (d) was 3 molar equivalents relative to the total 1 molar equivalent of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and tetraethoxysilane. Water (d) contains 0.036% by weight of hydrochloric acid in Examples 18 to 21 and 28 and Comparative Examples 13 to 16.
Included. Examples 18-29 and Comparative Examples 13-22
Through the above, the above-mentioned compounding amount is fixed, and the heteropoly acid compound (b), perchloric acid compound (b ₁ ), trifluoromethanesulfonic acid compound (b ₂ ), sulfuric acid (b ₃ ) or fluoro Sulfonic acid (b
₄ ) and the compounding amount per 1 molar equivalent of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and tetraethoxysilane in total were changed as shown in Tables 5 and 6. The heteropolyacid compound (b)
As for the above, since the water of hydration is included, the amount of water including this water of hydration was set to a predetermined amount. Table 5
In Table 6, Ti represents titanium tetra-n-butoxide, Zr represents zirconium tetra-n-butoxide, and Al represents aluminum tri-iso-propoxide.

The specific operation procedure was performed as follows.
The above-mentioned predetermined amount of methyl alcohol is supplied to a glass beaker, and the above-mentioned predetermined amount of N- (β-aminoethyl) -γ-
Aminopropyltrimethoxysilane and tetraethoxysilane were added, and water containing 0.036% by weight of hydrochloric acid was added (however, Examples 22 to 27 and 29 and Comparative Examples 17 to 2).
2 was added pure water containing no hydrochloric acid), and the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm to obtain an alcohol solution of a silane compound. In the obtained alcohol solution, a predetermined amount of the metal alkoxide (e) and the heteropolyacid compound (b), the perchloric acid compound (b ₁ ), the trifluoromethanesulfonic acid compound (b ₂ ), the sulfuric acid ( b ₃ ) or fluorosulphonic acid (b
₄ ) is added and the stirring speed is 800r for 3 hours at room temperature.
The mixture was stirred at pm to obtain a high refractive index layer coating composition (antistatic coating composition).

(2) Manufacture of Laminates (Manufacture of Laminates of Examples 18 to 27 and Comparative Examples 13 to 22) The composition for coating a high refractive index layer prepared as described above,
A polycarbonate plate (Teijin Ltd., trade name “Panlite”, 40 × 10 × 1 mm) is dipped, pulled up at a speed of 100 mm / min, and then dried at room temperature for 10 minutes to laminate a high refractive index layer. Got Next, the obtained high-refractive-index-layer-coated laminate was treated with the above-mentioned low-refractive-index-coating compositions (a), (b) shown in Tables 5 and 6.
Immerse in (c), (d), (e) or (f) and
After pulling up at a speed of mm / min, it was dried at room temperature for 10 minutes, and the obtained laminated body was cured at 110 ° C. for 60 minutes to obtain a desired laminated body. The physical properties of the laminate obtained as described above were evaluated based on the above-mentioned measurement methods, and the results are shown in Tables 5 and 6. Incidentally, Comparative Examples 13, 15, 17,
In Nos. 19 and 21, the film was clouded and a transparent laminate could not be obtained.

(Production of Laminates of Examples 28 and 29) Table 5
In the same manner as above, a polycarbonate plate (manufactured by Teijin Ltd., trade name “Panlite”, 4
(0 × 10 × 1 mm), dried, and cured at 110 ° C. for 60 minutes, and then the composition (b) (Example 28) or (d) (Example 29) for coating the low refractive index layer described above. After coating in the same manner as above, drying and then curing at 110 ° C. for 60 minutes to obtain a target laminate. The physical properties of the obtained laminate were evaluated based on the above-mentioned measurement methods, and the results are shown in Table 5.

[0161]

[Table 5]

[0162]

[Table 6]

[0163]

The method for producing the laminate of the present invention and the inventions 2 to 5 is as described above. According to this production method, sufficient charging is performed while maintaining the optical characteristics of the base material before film formation. It is possible to obtain a high refractive index layer having prevention performance. Further, since the low refractive index layer is laminated on the surface of the high refractive index layer, it is possible to easily manufacture a laminate in which a transparent coating having a high antireflection effect and an antistatic effect is formed on the substrate. . Furthermore, since the antistatic coating composition used in the present invention and the present inventions 2 to 5 can be prepared by an ordinary simple method and can be used in the same manner as a conventional silicon-based coating solution, Invention and Invention 2
According to Nos. 5 to 5, it is possible to easily manufacture a laminate in which a transparent coating film having a high antireflection effect and an antistatic effect is formed on a base material.

The method for producing a laminate of the present inventions 6 to 10 is as described above. According to this production method, the laminate has sufficient antistatic performance while maintaining the optical characteristics of the base material before film formation. Since the obtained coating contains oxides of zirconium, titanium or aluminum, it is difficult to scratch even if it is hardly rubbed with a hard material, and it is hard to cause deterioration in appearance due to scratches, and it is possible to maintain performance for a long period of time. A high refractive index layer can be obtained. Further, since the low refractive index layer is laminated on the surface of the high refractive index layer,
It is possible to easily manufacture a laminate in which a transparent coating having a high antireflection effect and an antistatic effect is formed on a base material. further,
The antistatic coating composition used in the present invention 6 to 10 is
Since it can be produced by an ordinary simple method and can be used in the same manner as a conventional silicon-based coating solution, according to the present invention 6 to 10, a transparent material having a high antireflection effect and an antistatic effect on a substrate. It is possible to easily manufacture a laminate having a different coating.

The method for producing a laminate of the eleventh aspect of the present invention is as described above, and a mixture of colloidal silica and silica sol is formed on the substrate on which the high refractive index layer having conductivity of the first to tenth aspects of the present invention is laminated. Since the composition for coating a low refractive index layer consisting of is applied and cured, the surface is made porous, and even if it is rubbed with a hard material such as steel wool, it is hard to be scratched, and the appearance is deteriorated due to scratches. Especially difficult to wake up.
Therefore, according to the eleventh aspect of the present invention, it is possible to easily manufacture a laminate having a transparent film having a high antireflection effect and an antistatic effect on a base material and having excellent scratch resistance.

The method for producing a laminate of the invention 12 is as described above, and according to the invention 12, even if a coating liquid is applied to form the high refractive index layer and the low refractive index layer, Since the phenomenon of elution from the layers does not occur, it is possible to easily and always stably manufacture a laminate having a transparent coating film having a high antireflection effect and an antistatic effect formed on a substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuaki Miyamoto 2-2 Kamitobaue Tonkocho Minami-ku, Kyoto City Sekisui Kagaku Kogyo Co., Ltd.

Claims (12)

[Claims] 1. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a) an aminosilane compound A represented by the following general formula [I]: (In the formula, Y is an organic group having an amino group, Y ¹ is a hydrocarbon group, R is an alkyl group having 1 to 5 carbon atoms, m is an integer of 1 to 5, and n is an integer of 0 to 2) (b) Heteropoly acid compound,
(C) organic solvent and (d) water containing acid in a proportion of 0.01 to 5% by weight, wherein the molar ratio of (a), (b), (c) and (d) is 1: 0. 0.001-0.25: 10
A method for producing a laminate, comprising a layer obtained by applying an antistatic coating composition of 100: 1 to 30. 2. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a) an aminosilane compound A according to claim 1, (b ₁ ) a perchloric acid compound represented by the general formula XClO ₄ (wherein X is a hydrogen atom, a monovalent compound). Metal atom, NH ₄ or quaternary ammonium represented by the following general formula [IV]): (In the formula, M ¹ , M ² , M ³ and M ⁴ have 1 to 20 carbon atoms.
Alkyl group), (c) organic solvent, and (d) 0.01-
It is composed of water containing 5% by weight of acid, and the molar ratio of (a) to (b ₁ ), (c) to (d) is 1: 0.001.
A method for producing a laminate, which comprises a layer obtained by applying an antistatic coating composition having a proportion of from about 0.65: 10 to 100: 1 to 30. 3. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a) the aminosilane compound A according to claim 1, (b ₂ ) a trifluoromethanesulfonic acid compound represented by the general formula CF ₃ SO ₃ X ¹ (wherein X ¹ Is a hydrogen atom or a monovalent metal atom), (c) an organic solvent and (d) water, and (a), (b ₂ ), (c) and (d)
Molar ratio of 1: 0.001 to 0.3: 10 to 100:
A method for producing a laminate, comprising a layer obtained by applying the antistatic coating composition of 1 to 30. 4. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer comprises (a) the aminosilane compound A according to claim 1, (b ₃ ) sulfuric acid, (c) an organic solvent and (d) water, and (a) and (b ₃ ) And a layer obtained by applying an antistatic coating composition having a molar ratio of (c) and (d) of 1: 0.01 to 1:10 to 100: 1 to 30. A method for manufacturing a laminated body. 5. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. The high refractive index layer comprises (a) the aminosilane compound A according to claim 1, (b ₄ ) fluorosulfonic acid, (c) an organic solvent and (d) water, and (a) and (b) ₄ ) The molar ratio of (c) and (d) is 1: 0.0001 to 0.1: 10.
A method for producing a laminate, which is a layer obtained by applying an antistatic coating composition of 100: 1 to 30. 6. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a ₁ ) a silane compound containing 50 to 100 mol% of the aminosilane compound A according to claim 1.
(B) heteropolyacid compound, (c) organic solvent, (d)
Water containing an acid in a proportion of 0.001 to 5% by weight, and (e) a zirconium tetraalkoxide represented by the general formula Zr (OR ³ ) ₄ and a titanium tetraalkoxide represented by the general formula Ti (OR ⁴ ) _4. And the general formula Al (O
An aluminum trialkoxide represented by R ⁵ ) ₃ (in the formula, R ³ , R ⁴ and R ⁵ are alkyl groups having 1 to ⁵ carbon atoms), and at least one metal alkoxide selected from the group consisting of silane compounds The molar ratio of (a ₁ ) to the metal alkoxide (e) is 70:30 to 99: 1,
The molar ratio of the silane compounds (a ₁ ), (b), (c) and (d) is 1: 0.001 to 0.15: 10 to 10: 0.
A method for producing a laminate, comprising a layer obtained by applying the antistatic coating composition of 1 to 5. 7. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a ₁ ) the silane compound according to claim 6,
(B ₁ ) a perchloric acid compound, (c) an organic solvent, (d) water and (e) a metal alkoxide according to claim 6,
The silane compound (a ₁ ) and the metal alkoxide (e) have a molar ratio of 70:30 to 99: 1, and the silane compounds (a ₁ ), (b ₁ ), (c) and (d) have a molar ratio of 1:
A method for producing a laminate, comprising a layer obtained by applying an antistatic coating composition of 0.005 to 0.32: 10 to 100: 0.1 to 5. 8. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a ₁ ) the silane compound according to claim 6,
(B ₂ ) trifluoromethanesulfonic acid compound, (c)
An organic solvent, (d) water, and (e) a metal alkoxide according to claim 6, wherein the silane compound (a ₁ ) and the metal alkoxide (e) have a molar ratio of 70:30 to 99: 1, and the silane compound ( a ₁ ), (b ₂ ), (c) and (d)
Molar ratio of 1: 0.001 to 0.3: 10 to 100:
A method for producing a laminate, comprising a layer obtained by applying an antistatic coating composition having a thickness of 0.1 to 5. 9. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a ₁ ) the silane compound according to claim 6,
(B ₃ ) sulfuric acid, (c) organic solvent, (d) water and (e)
The metal alkoxide according to claim 6, wherein the silane compound (a ₁ ) and the metal alkoxide (e) have a molar ratio of 70:
30 to 99: 1, and the molar ratio of the silane compounds (a ₁ ), (b ₃ ), (c) and (d) is 1: 0.001.
A method for producing a laminate, which comprises a layer obtained by applying an antistatic coating composition of 0.4 to 10 to 100: 0.1 to 5. 10. A method for producing a laminate in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. Wherein the high refractive index layer is (a ₁ ) the silane compound according to claim 6, (b ₄ ) fluorosulfonic acid (c) organic solvent,
(D) water and (e) consisting of the metal alkoxide according to claim 6, wherein the silane compound (a ₁ ) and the metal alkoxide (e) have a molar ratio of 70:30 to 99: 1, and the silane compound (a ₁ ) And (b ₄ ), (c) and (d) have a molar ratio of 1: 0.0001 to 0.1: 10 to 100: 0.1.
A method for producing a laminate, comprising a layer obtained by applying the antistatic coating composition of Nos. 5 to 5 above. 11. A method for producing a laminate, in which a high refractive index layer having conductivity and a low refractive index layer are laminated on the surface of a transparent substrate so that the low refractive index layer is the outermost layer. a is, the high refractive index layer, a high refractive index layer according to claim 10, further the low refractive index layer, in the general formula Si (OR ⁶⁾ ₄ (wherein, R ⁶ is the number of carbon atoms 1 mol of an alkoxysilane represented by 1 to 5 alkyl groups), pH
And a condensation composition (B) obtained by mixing 2 to 8 mol of a basic aqueous solution of 10.0 to 12.0 and 10 to 30 mol of an organic solvent, and a general formula (R ⁸ ) _s Si (OR ⁷ ) _{4 -s} (in the formula, R ⁷ and R ⁸ are alkyl groups having 1 to 5 carbon atoms, s is an integer of 0 to 3), 1 mol of alkoxysilane, and pH is 0 to 0.
2.6 to 8 mol of acidic aqueous solution and 10 to 3 of organic solvent
Condensation composition (C) obtained by mixing 0 moles thereof is mixed in a weight ratio B / C = 0.4 to 2.4, and the obtained composition is applied to form a layer. A method for manufacturing a laminate, comprising: 12. The method according to claims 1 to 1 on the surface of a transparent substrate.
1. A method for producing a laminate, wherein the high refractive index layer and the low refractive index layer are alternately laminated so that the low refractive index layer is the outermost layer, which is already laminated at the time of laminating each layer. A method for producing a laminated body, characterized in that the layer is cured.