JPH08304604A - Production of laminated body - Google Patents

Abstract

PURPOSE: To easily produce a laminated body comprising a coating film having a high antireflection effect and antistatic effect formed on a base body by applying a compsn. for an antistatic coating film having a specified compsn. to form a layer as a high refractive index layer. CONSTITUTION: The high refractive index layer consists of an aminoalkyl alkoxy silane compd. (A) expressed by formula I, an expoxyalkyl alkoxy silane compd. (B) expressed by formula II, zirconium tetra alkoxide expressed by Zr(OR<2> )4 , wherein R<2> is 1-5C alkyl group, nitric acid, org. solvent and water. This layer is formed by applying a compsn. for an antistatic coating film containing the compd. (A), compd. (B) and zirconium tetra alkoxide by (93 to 53):(35 to 5):(12 to 2) molar ratio. In formula I, Y is an org. group having an amino group, Y<1> is a hydrocarbon group, R is 1-5C alkyl group, m is an integer 1 to 5, and n is an integer 0 to 2. In formula II, Z is a glycidoxy group or epoxy cyclohexyl group, Y<2> is a hydrocarbon group, R<1> is 1-5C alkyl group, p is an integer 1 to 5 and t is an integer 0 to 2.

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 coating having a high antireflection effect and an antistatic effect is formed on a substrate and which has a light transmittance of 40% or more.

[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 an object thereof is to form a coating film having a high antireflection effect and an antistatic effect on a substrate.
An object of the present invention is to provide a method capable of easily producing a laminate having a light transmittance of 40% or more.

[0011]

In the method for producing a laminate of the present invention, a high refractive index layer having conductivity and a low refractive index layer are formed on the surface of a substrate, and the low refractive index layer is the outermost layer. As described above, in the method for manufacturing a laminate having a multilayer structure, the high refractive index layer comprises:
It is a layer obtained by applying an antistatic coating composition having a specific composition.

The aminoalkylalkoxysilane 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].

Embedded image

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,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-
Examples include a pentyl group. m is an integer of 1 to 5, and n is an integer of 0 to 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.

The epoxyalkylalkoxysilane compound B (b) used in the present invention is represented by the following general formula [II].

[Chemical 4]

In the formula, Z represents a glycidoxy group or an epoxycyclohexyl group, Y ² represents a hydrocarbon group, and examples thereof include an alkyl group and a substituted alkyl group.
R ¹ 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, so the carbon number is limited to 1 to 5. It
Examples of R ¹ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-
Examples thereof include a pentyl group and a neo-pentyl group. p is an integer of 1 to 5 and t is an integer of 0 to 2.

As the compound represented by the general formula [II],
For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxy. Examples include silane. Of these, γ-glycidoxypropyltrimethoxysilane is particularly preferable. As the epoxyalkylalkoxysilane compound B (b), compounds within the range defined above may be used alone or in combination of two or more kinds.

The zirconium tetraalkoxide (c) used in the present invention is represented by the general formula Zr (OR ² ) ₄ , and R ² represents an alkyl group having 1 to 5 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. Examples of R ² are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec.
-Butyl group, tert-butyl group, n-pentyl group, i
Examples thereof include so-pentyl group and neo-pentyl group.

Examples of the zirconium tetraalkoxide (c) include zirconium tetramethoxide, zirconium tetraethoxide and zirconium tetra-n-.
Propoxide, zirconium tetra-iso-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetra-tert-butoxide, zirconium tetra-n-pentoxide, zirconium tetra-iso-pentoxide and the like, and the like. Zirconium tetra-n-butoxide and zirconium tetra-iso-propoxide are particularly preferable. As the zirconium tetraalkoxide (c) used in the present invention, a compound within the range defined above may be used alone or in combination of two or more kinds.

In the antistatic coating composition used in the present invention, the aminoalkylalkoxysilane compound A is used.
(A) and epoxyalkylalkoxysilane compound B
The molar ratio of (b) and zirconium tetraalkoxide (c) is limited to 93-53: 35-5: 12-2.
If it deviates from this range, gelation of the composition may occur or water resistance may not be obtained.

The nitric acid (d) used in the present invention is
It may be added as it is or as nitric acid water. The addition amount of nitric acid is appropriately determined, but is preferably 0.01 to 0.5 mol with respect to 1 mol of the aminoalkylalkoxysilane compound A (a). When the nitric acid (d) is small, the film does not have sufficient conductivity for antistatic, and when it is large, it is difficult to obtain a uniform film.

The organic solvent (e) used in the present invention is compatible with the aminoalkylalkoxysilane compound A (a), the epoxyalkylalkoxysilane compound B (b), the zirconium tetraalkoxide (c) and the water (f). It is not particularly limited as long as it is soluble and can dissolve nitric acid (d), 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. And so on,
Particularly, methyl alcohol, ethyl alcohol and isopropyl alcohol are preferable. These may be used alone or in combination of two or more.

The amount of the organic solvent (e) is preferably 15 to 100 mol per 1 mol of the aminoalkylalkoxysilane compound A (a). When the amount of the organic solvent (e) is small, the coating composition is difficult to be mixed uniformly, resulting in a heterogeneous composition, and when the amount is large, the solid content concentration of the coating composition becomes too low, which is sufficient when a film is formed. Antistatic ability cannot be obtained. A more preferable amount of addition is in the range of 18 to 50 mol per 1 mol of the aminoalkylalkoxysilane compound A (a).

The water (f) used in the present invention is added for the hydrolysis of the aminoalkylalkoxysilane compound A (a), the epoxyalkylalkoxysilane compound B (b) and the zirconium tetraalkoxide (c). . The amount of water (f) is preferably 0.1 to 5 mol per 1 mol of the aminoalkylalkoxysilane compound A (a). When the amount of water (f) is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the coating composition is poor.

An acid such as an inorganic acid or an organic acid may be added to the water (f) used in the present invention as a catalyst for hydrolysis.

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, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or the like 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. Further, a known curing catalyst may be added for curing the aminoalkylalkoxysilane compound A (a), the epoxyalkylalkoxysilane compound B (b) and the zirconium tetraalkoxide (c).

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, the aminoalkylalkoxysilane compound A (a) is mixed with a part of the organic solvent (e), and nitric acid (d) and a part of water (f) are added thereto. Add and stir-mix to obtain a hydrolyzed solution of the aminoalkylalkoxysilane compound A (a). On the other hand, the epoxyalkylalkoxysilane compound B (b), the zirconium tetraalkoxide (c), and the rest of the organic solvent (e) are mixed, the rest of the water (f) is added thereto, and the mixture is stirred and mixed to form an epoxy resin. Alkylalkoxysilane compound B (b)
And a hydrolyzed solution of zirconium tetraalkoxide (c) is obtained. This solution is added to the above-mentioned hydrolysis solution of the aminoalkylalkoxysilane compound A (a) to prepare a hydrolyzate of the mixture, which is used as an antistatic coating composition.

In the method for producing a laminate of the present invention, a high refractive index layer is obtained by applying this antistatic coating composition onto a substrate and drying. The drying method is not particularly limited, and may be natural drying at room temperature or heat drying. In addition, after drying, high temperature heat treatment may be performed, if necessary. For example, when the surface of a plastic product is coated with the coating composition, naturally dried at room temperature, and then cured at a temperature of 60 to 150 ° C.,
A plastic product having a high refractive index layer having an antistatic ability is obtained.

In the method for producing a laminated body of the present invention, the low refractive index layer and the high refractive index layer are alternately laminated on the base material. The low refractive index layer is not particularly limited as long as it has 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. In addition, specific representative examples of the fluorine-containing inorganic compound include MgF ₂ , AlF ₃ , BaF ₂ , and La.
F ₂ , CaF ₂ , Na ₃ AlF _{6 and the} like can be mentioned.

In the present invention, the base material forming the laminated body is not particularly limited as long as it is a base material which makes the light transmittance of the laminated body 40% or more, and depending on the purpose. Acid 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 balls, translucent ceramics such as magnesia and sialon, polycarbonate, acrylic resin, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyester, polyurethane, cellulose triacetate and other plastics are used. it can. 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 the base material so that the low refractive index layer is the outermost layer. . The method for producing the laminate having the smallest number of layers is a method in which a high refractive index layer is first laminated on the surface of the substrate, dried, and then a low refractive index layer is laminated on the dried layer, followed by drying and curing. Is.

In the method for producing a laminated body of the present invention, the light transmittance of the finally obtained laminated body is limited to 40% or more.

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.

The aminoalkylalkoxysilane compound A (a) and the epoxyalkylalkoxysilane compound B (b) used in the present invention 2 (the invention of claim 2 is referred to as the present invention 2) are the same as those of the present invention. It is the same.

The titanium tetraalkoxide (c ₁ ) used in the present invention 2 is represented by the general formula Ti (OR ³ ) ₄ , and R ³ represents an alkyl group having 1 to 5 carbon atoms, When the amount is large, the stability of the antistatic coating composition is lowered and the long-term storage property is deteriorated. Therefore, the carbon number is limited to 1 to 5. Examples of R ³ are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec.
-Butyl group, tert-butyl group, n-pentyl group, i
Examples thereof include so-pentyl group and neo-pentyl group.

Examples of the titanium tetraalkoxide (c ₁ ) include titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-iso-propoxide, titanium tetra-n-butoxide, titanium tetra. −
sec-butoxide, titanium tetra-tert-butoxide, titanium tetra-n-pentoxide, titanium tetra-iso-pentoxide and the like,
Particularly, titanium tetra-n-butoxide and titanium tetra-iso-propoxide are preferable. As the titanium tetraalkoxide (c ₁ ) used in the present invention, compounds within the range defined above may be used alone or in combination of two or more kinds.

In the antistatic coating composition used in the present invention 2, the aminoalkylalkoxysilane compound A is used.
(A) and epoxyalkylalkoxysilane compound B
The molar ratio of (b) and titanium tetraalkoxide (c ₁ ) is limited to 93 to 55:35 to 5:10 to 2.
If it deviates from this range, gelation of the composition may occur or water resistance may not be obtained.

The nitric acid (d) used in the present invention 2 may be added as it is or as nitric acid water. The addition amount of nitric acid is appropriately determined, but is preferably 0.01 to 0.5 mol with respect to 1 mol of the aminoalkylalkoxysilane compound A (a). When the nitric acid (d) is small, the film does not have sufficient conductivity for antistatic, and when it is large, it is difficult to obtain a uniform film.

The organic solvent (e) used in the present invention 2 is
The aminoalkylalkoxysilane compound A (a),
There is no particular limitation as long as it is compatible with the epoxyalkylalkoxysilane compound B (b), the titanium tetraalkoxide (c ₁ ) and water (f) and dissolves the nitric acid (d). alcohol,
Examples thereof include alcohols such as ethyl alcohol, isopropyl alcohol, and butyl alcohol, ketones such as acetone and methyl ethyl ketone, and tetrahydrofuran. Methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly preferable. These may be used alone or in combination of two or more.

The amount of the organic solvent (e) is preferably 15 to 100 mol per 1 mol of the aminoalkylalkoxysilane compound A (a). When the amount of the organic solvent (e) is small, the coating composition is difficult to be mixed uniformly, resulting in a heterogeneous composition, and when the amount is large, the solid content concentration of the coating composition becomes too low, which is sufficient when a film is formed. Antistatic ability cannot be obtained. A more preferable amount of addition is in the range of 18 to 50 mol per 1 mol of the aminoalkylalkoxysilane compound A (a).

The water (f) used in the present invention 2 is used for the hydrolysis of the aminoalkylalkoxysilane compound A (a), the epoxyalkylalkoxysilane compound B (b) and the titanium tetraalkoxide (c ₁ ). Added. The amount of water (f) is preferably 0.1 to 5 mol per 1 mol of the aminoalkylalkoxysilane compound A (a). When the amount of water (f) is small, sufficient hydrolysis is unlikely to occur, and when the amount is large, the compatibility with the coating composition is poor.

An acid such as an inorganic acid or an organic acid may be added to the water (f) used in the present invention 2 as a catalyst for hydrolysis.

The composition of the antistatic coating composition used in the present invention 2 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, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose or the like 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. Further, a known curing catalyst may be added for curing the aminoalkylalkoxysilane compound A (a), the epoxyalkylalkoxysilane compound B (b) and the titanium tetraalkoxide (c ₁ ).

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 2 is not particularly limited. For example, a method of mixing the above-mentioned constituent materials at once or dividing a specific constituent material is divided. And the like, and then the remaining constituent materials are added and mixed. As a method of dividing and mixing, for example, the aminoalkylalkoxysilane compound A (a) is mixed with a part of the organic solvent (e), and nitric acid (d) and a part of water (f) are added thereto. Add and stir-mix to obtain a hydrolyzed solution of the aminoalkylalkoxysilane compound A (a). On the other hand, the epoxyalkylalkoxysilane compound B (b), the titanium tetraalkoxide (c ₁ ) and the rest of the organic solvent (e) are mixed, the rest of the water (f) is added thereto, and the mixture is stirred and mixed, Epoxyalkylalkoxysilane compound B (b)
To obtain a hydrolysis solution of titanium tetraalkoxide (c ₁ ). This solution is added to the above-mentioned hydrolysis solution of the aminoalkylalkoxysilane compound A (a) to prepare a hydrolyzate of the mixture, which is used as an antistatic coating composition.

In the method for producing a laminate of the present invention 2, a high refractive index layer is obtained by applying this antistatic coating composition onto a substrate and drying. As the drying method,
It is not particularly limited and may be naturally dried at room temperature or may be dried by heating. In addition, after drying, high temperature heat treatment may be performed, if necessary. For example, when the surface of a plastic product was coated with the coating composition, naturally dried at room temperature and then cured at a temperature of 60 to 150 ° C., a high refractive index layer having an antistatic ability was formed. Plastics products are obtained.

In the method for producing a laminated body of the present invention 2, 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 has 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. In addition, specific representative examples of the fluorine-containing inorganic compound include MgF ₂ , AlF ₃ , BaF ₂ , and La.
F ₂ , CaF ₂ , Na ₃ AlF _{6 and the} like can be mentioned.

In the present invention 2, the substrate forming the laminate is the same as the substrate described in the present invention 1.

In the method for producing a laminate of the present invention 2, the high refractive index layer and the low refractive index layer are alternately laminated on the surface of the base material so that the low refractive index layer is the outermost layer. Let The manufacturing method of the laminated body with the smallest number of laminated layers is as follows.
In this method, a high refractive index layer is laminated, dried, and then a low refractive index layer is laminated thereon, dried, and cured.

In the method for producing a laminate of the present invention 2, the light transmittance of the finally obtained laminate is limited to 40% or more.

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.

The present invention 3 (the invention of claim 3 is referred to as the present invention 3) is a high refractive index layer having conductivity and a low refractive index layer on the surface of a substrate, and the low refractive index layer is the outermost layer. So that
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 or 2, and the low refractive index layer is the general formula Si (OR ⁴ ) ₄ (In the formula,
R ⁴ is a mixture of 1 mol of a tetraalkoxysilane represented by an alkyl group having 1 to 5 carbon atoms, 2 to 8 mol of basic water having a pH of 10.0 to 12.0, and 10 to 30 mol of an organic solvent. The resulting condensation composition (C) and the general formula (R ⁶ ) _s S
i (OR ⁵ ) _4-s (In the formula, R ⁵ and R ⁶ are each a carbon number of 1 to
Alkyl group of 5; s is an integer of 0 to 3) 1 mole of alkoxysilane represented by pH of 0 to 2.6;
8 mol and a condensation composition (D) obtained by mixing 10 to 30 mol of an organic solvent were used in a weight ratio (C) / (D) = 0.
A light transmittance of 40, which comprises a layer obtained by coating the composition obtained by mixing at 4 to 2.4.
% Of the laminated body.

The condensation composition (C) used in the method for producing a laminate according to the third aspect of the present invention is a tetrahedral compound represented by Si (OR ⁴ ) ₄ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms). It is obtained by mixing alkoxysilane, basic water and an organic solvent, and partially hydrolyzing and polycondensing the alkoxysilane.

In the above tetraalkoxysilane represented by Si (OR ⁴ ) ₄ , when R ⁴ has a large number of carbons, the stability of the composition decreases and the long-term storage stability deteriorates. To 5 alkyl groups, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group. Group, neo-pentyl group and the like.

Examples of the tetraalkoxysilane represented by Si (OR ⁴ ) ₄ include tetramethoxysilane and
Tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-
Butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra-n-pentoxysilane, tetra-iso-pentoxysilane, tetraneopentoxysilane and the like are mentioned, and the reaction in hydrolysis and polycondensation. From the point of sex, tetramethoxysilane,
Tetraethoxysilane is preferred, and tetraethoxysilane is particularly preferred.

The above basic water has a pH of 1 depending on the type of base.
It means water adjusted to 0.0 to 12.0. The base species is not particularly limited as long as it can adjust the pH of water to 10.0 to 12.0, and examples thereof include ammonia, sodium hydroxide, potassium hydroxide and the like. Ammonia is particularly preferable because it is less likely to contain impurities.

When the pH of the basic water 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 (C) 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 basic water is small, the molecular weight of the colloidal silica obtained is low, making it difficult to form an antireflection layer, and when it is high, the stability of the condensation composition (C) is low. 2 to 8 moles, preferably 3 to 4 moles, are added to 1 mole of alkoxysilane.

The organic solvent is not particularly limited as long as it is compatible with the above tetraalkoxysilane and basic water, and examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, ethoxyethyl alcohol and allyl alcohol. Etc., but isopropyl alcohol is particularly preferable.

When the amount of the organic solvent added is small, the stability of the condensation composition (C) 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. The above tetraalkoxysilane 1
The amount is limited to 10 to 30 mol per mol, and from the viewpoint of stability of the composition, 1 mol per tetraalkoxysilane
3-18 mol is preferable.

The method for preparing the condensation composition (C) is not particularly limited, and examples thereof include a method in which the above-mentioned tetraalkoxysilane, basic water and an 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 (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 preparing the condensation composition (C) 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 (C) is lowered.
0 hours are preferred, and 2-4 hours are particularly preferred. Therefore, the condensation composition (C) 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.

The condensation composition (D) used in the method for producing a laminate of the present invention 3 has the general formula (R ⁶ ) _s Si (OR ⁵ ).
An alkoxysilane represented by _4-s (in the formula, R ⁵ and R ⁶ are alkyl groups having 1 to 5 carbon atoms, s is an integer of 0 to 3),
It is obtained by mixing acidic water and an organic solvent and partially hydrolyzing and polycondensing an alkoxysilane.

The above general formula (R ⁶ ) _s Si (OR ⁵ )
_{In the} alkoxysilane represented by _4-s , when R ⁵ and R ⁶ have a large number of carbon atoms, the stability of the condensation composition decreases and the long-term stability deteriorates. And a methyl group, an ethyl group, n-
Propyl group, iso-propyl group, n-butyl group, se
c-butyl group, tert-butyl group, n-pentyl group,
Examples thereof include an iso-pentyl group and a neo-pentyl group. In addition, s shows the integer of 0-3.

The alkoxysilane represented by (R ⁶ ) _s Si (OR ⁵ ) _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, tetra-n-pentoxysilane, tetra-iso-pentoxysilane, tetra-neo. Pentoxysilane, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyltri-iso-propoxysilane, monomethyltri-
n-Butoxysilane, monomethyltri-sec-butoxysilane, monomethyltri-tert-butoxysilane, monomethyltri-n-pentoxysilane, monomethyltri-iso-pentoxysilane, monomethyltri-
Neopentoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Dimethyldi-n-propoxysilane, dimethyldi-is
o-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldi-n-pentoxysilane, dimethyldi-iso-pentoxysilane,
Dimethyldi-neopentoxysilane, diethyldiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane,
Trimethylmono-n-butoxysilane, trimethylmono-sec-butoxysilane, trimethylmono-tert
-Butoxysilane, trimethylmono-n-pentoxysilane, trimethylmono-iso-pentoxysilane, trimethylmono-neopentoxysilane, triethylethoxysilane, etc., and tetramethoxysilane, tetraethoxysilane from the viewpoint of reactivity. , Monomethyltriethoxysilane is preferable, and tetraethoxysilane is particularly preferable.

The acidic water has a pH of 0 to 0 depending on the acidic species.
It means water adjusted to 2.6. Acidic species increase the pH of water
It is not particularly limited as long as it can be adjusted 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 water is high, the hydrolysis of the alkoxysilane is insufficient, so the pH is limited to 0 to 2.6, and when it is too low, the stability of the condensation composition (D) is lowered. If it is too high, hydrolysis of the alkoxysilane may be insufficient, so 1.0-
1.7 is preferable, and 1.1 to 1.2 is particularly preferable.

If the amount of the acidic water added is small, the hydrolysis of the alkoxysilane will be insufficient, and it will be difficult to apply the resulting composition to the substrate. If the amount is large, the stability of the condensation composition (D) will be improved. Properties are reduced, (R ⁶ ) _s Si
It is limited to 3 to 8 mol, preferably 4 to 7 mol, per 1 mol of alkoxysilane represented by (OR ⁵ ) _4-s .

The above organic solvent is (R ⁶ ) _s Si (O
There is no particular limitation as long as it is compatible with the alkoxysilane represented by R ⁵ ) _4-s and acidic water, and for example, the same one as used in the production of the condensation composition (C) can be used. When the addition amount of the organic solvent is small, the stability of the condensation composition (D) is lowered, and when the addition amount is large, the alkoxysilane is not sufficiently hydrolyzed, so that (R ⁶ ) _s Si (O
It is limited to 10 to 30 mol, preferably 13 to 18 mol, per 1 mol of alkoxysilane represented by R ⁵ ) _4-s .

The method for preparing the condensation composition (D) is not particularly limited, and for example, an alkoxysilane represented by (R ⁶ ) _s Si (OR ⁵ ) _4-s , acidic water and an organic solvent are 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 (D) is
When it becomes lower, the polycondensation reaction becomes insufficient, and when it becomes higher,
Since the stability of the condensation composition (D) 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 (D) 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 (D) decreases, so that 1 to 1
0 hours are preferred, and 2-4 hours are particularly preferred. Therefore, the condensation composition (D) 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 third aspect of the present invention, the condensation composition (C) and the condensation composition (D) are mixed in a weight ratio (C) / (D) = 0.4 to 2.4. Mix with.

When the amount of the condensation composition (C) is small, the porosity of the obtained coating film is low, and the antireflection effect of the obtained laminate is low, and when it is large, the adhesion between the obtained coating film and the substrate is low. Therefore, the weight ratio of the condensation composition (C) and the condensation composition (D) 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 (C) and the condensation composition (D) are mixed becomes low, 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.

When the time for mixing the condensation composition (C) and the condensation composition (D) is shortened, the polycondensation of the colloidal silica and silica sol becomes insufficient, and the antireflection effect of the obtained coating is lowered, and the time is prolonged. , 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 mixing of the condensation composition (C) and the condensation composition (D) is preferably performed 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 (C) and the condensation composition (D) is not particularly limited, and for example, the condensation composition (C) and the condensation composition (D) are fed 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.

The method for producing a laminate of the present invention 3 is a multilayer structure in which a conductive high refractive index layer and a low refractive index layer are provided on the surface of a base material, and the low refractive index layer is the outermost layer. A method for producing a laminated body, wherein the high refractive index layer is a layered product.
The high refractive index layer described above, and the low refractive index layer further comprises a layer obtained from the composition. 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 that a coating having the following relationship with the wavelength for which the antireflection effect is desired is obtained. This is preferable because it can be improved.

D = (1/4 + m / 2) × λ / n d: film thickness of coating λ: wavelength at which antireflection effect is desired n: refractive index of coating 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, silicate glass is used as a substrate, and the surface thereof is defined by claim 1.
On the surface of the material having the high refractive index layer described in 1 above, the above low refractive index layer coating composition is laminated by the above method,
After air-drying at room temperature and then curing at a temperature of 60 to 300 ° C., the silica sol in the composition is made porous due to the difference in shrinkage ratio between the cured silicon matrix and colloidal silica, and an antireflection coating. A laminated body in which is formed is obtained. Further, for example, a plastic product is used as a substrate, and the composition for coating a low refractive index layer is provided on the surface of a material having the high refractive index layer according to claim 1 or 2 laminated thereon. After laminating by the above-mentioned method and naturally drying at room temperature, the temperature is 60 to 150 ° C., preferably 80 to
When it is cured at a temperature of 100 ° C., a laminate having an antireflection coating, which is also made porous, is obtained.

The light transmittance of the laminates of the present inventions 1 to 3 is measured by the total light transmittance according to ASTM D-1003.

In the method for producing a laminate of the present invention, the present invention 2 and the present invention 3, when the respective layers of the high refractive index layer and the low refractive index layer are laminated, the layers already laminated are cured. Even if a coating liquid is applied to form the next layer, there is an advantage that the elution phenomenon from the underlying layer does not occur.

In the method for producing a laminate of the present invention, the present invention 2 and the present invention 3, a high refractive index layer and a low refractive index layer are alternately laminated to form a multi-layer laminate, thereby providing a wide wavelength range. An antireflection effect can be exhibited with respect to light.

[0090]

The high refractive index layer produced as described above from the antistatic coating composition used in the present invention and the present invention 2 has high conductivity because protons from nitric acid are uniformly present. Moreover, since there is no haze due to the addition of the conductive fine particles, the transparency is high. Further, since the zirconium tetraalkoxide or the titanium tetraalkoxide is a coating film obtained from a composition in which a specific amount of the zirconium tetraalkoxide or titanium tetraalkoxide is mixed, the water resistance is particularly improved because the coating film is dense. Further, since the metal oxide film is formed, it is hard to be scratched by a hard material even if it is strongly rubbed, the appearance is less likely to be deteriorated due to scratches, and the performance can be maintained for a long time. Therefore,
According to the present invention and the production method of the present invention 2, it is possible to obtain a water resistant high refractive index layer having sufficient antistatic performance while maintaining the optical characteristics of the substrate before film formation. According to the method for producing a laminate of the present invention and the present invention 2, further,
Since the low refractive index layer is laminated on the surface of the high refractive index layer, a laminate having a light transmittance of 40% or more in which a coating having a high antireflection effect and an antistatic effect is formed on a substrate can be easily formed. Can be manufactured.

In the composition for coating a low refractive index layer used in the present invention 3, in the condensation composition (C), polycondensation of alkoxysilane is considerably advanced to form colloidal silica,
In the condensation composition (D), 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. By coating this composition on a substrate on which the high refractive index layer according to claim 1 or 2 is laminated and curing the composition, the polycondensation reaction of silica sol and colloidal silica is promoted, and the shrinkage ratio of silica sol and colloidal silica is increased. Due to the difference, it is possible to obtain a porous film. 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 present invention 3, a laminate having a high antireflection effect and an antistatic effect on a substrate, being transparent, and having a coating film excellent in scratch resistance and having a light transmittance of 40% or more can be easily produced. You can

[0092]

EXAMPLES Examples of the present invention, the present invention 2 and the present invention 3 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 of is measured in the range of 400 to 800 nm.
Maximum transmittance of (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
I 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. (4) Water resistance test The obtained laminated body was immersed in distilled water for 30 minutes, dried, and then subjected to electrostatic potential measurement in the same manner as in (1) above. (5) Light Transmittance The obtained laminate was measured by ASTM D-1003.
The light transmittance was measured and judged as follows. The light transmittance was 40% or more. × The light transmittance was less than 40%.

Examples 1 to 4 and Comparative Examples 1 to 20 (1) Preparation of high refractive index layer coating composition (antistatic coating composition) (1) to (11) The following Examples 1 to 4 and In Comparative Examples 1 to 20, the composition of the coating composition for obtaining the conductive high refractive index layer was prepared by aminoaminoalkoxysilane compound A (a).
As N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane as the epoxyalkylalkoxysilane compound B (b), and zirconium tetraalkoxide (c) as Zirconium tetra-n-butoxide was used. The compounding amount is N- (β-aminoethyl)
-Γ-Aminopropyltrimethoxysilane: γ-glycidoxypropyltrimethoxysilane: zirconium tetra-n-butoxide were mixed so that the molar ratio was as shown in Table 1. Methyl alcohol was used as the organic solvent (e), and distilled water was used as the water (f). The compounding amount is the aminoalkylalkoxysilane compound A (a) 1.
The amount of methyl alcohol was 20 mol and the amount of water was 3 mol with respect to the mol. The nitric acid (d) was added in Table 1 to 1 mol of the aminoalkylalkoxysilane compound A (a).
Compounded in the number of moles shown in.

The specific operation procedure for obtaining the above composition for coating a high refractive index layer was carried out as follows. Half of the above-mentioned predetermined amount of methyl alcohol is supplied to a glass beaker, the above-mentioned predetermined amount of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane is added, and N- (β-aminoethyl) -γ is added. Obtaining an alcoholic solution of aminopropyltrimethoxysilane. To this alcohol solution, the above-mentioned predetermined amount of nitric acid and the above-mentioned predetermined amount of water 3/4 amount were added, and the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm,
An alcohol aqueous solution of a hydrolyzate of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane was obtained.

On the other hand, half of the above-mentioned predetermined amount of methyl alcohol was supplied to a glass beaker, and the above-mentioned predetermined amounts of γ-glycidoxypropyltrimethoxysilane and zirconium tetra-n-butoxide were added to the γ-glycid. Xypropyltrimethoxysilane and zirconium tetra-n-
An alcoholic solution of butoxide was obtained.

To the obtained alcohol solution, 1/4 amount of the above-mentioned predetermined amount of water was added, and the stirring rate was 80 at room temperature for 3 hours.
By stirring at 0 rpm, an aqueous alcohol solution of a hydrolyzate of γ-glycidoxypropyltrimethoxysilane and zirconium tetra-n-butoxide was obtained.

A hydrolyzate of the above N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and γ-
Glycidoxypropyl trimethoxysilane and zirconium tetra-n-butoxide hydrolyzate were mixed with alcohol aqueous solutions, and the mixture was stirred at room temperature for 3 hours at a stirring rate of 80.
The mixture was stirred at 0 rpm to obtain a composition for coating a high refractive index layer.
The obtained high refractive index layer coating composition is shown in Table 1,
(1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (11)
And

(2) Composition for coating low refractive index layer (a)
Preparation of (q) Next, a predetermined amount of each of tetraethoxysilane, basic water whose pH was adjusted by ammonia, and isopropyl alcohol shown in molar ratios in Tables 2 and 3 were supplied to a magnetic stirrer at 800 rpm. 2 hours, 2
The mixture was mixed at 0 ° C to obtain a condensation composition (C). Furthermore, Table 2
And a predetermined amount of each of tetraethoxysilane shown in Table 3 by molar ratio, acidic water whose pH is adjusted by hydrochloric acid and isopropyl alcohol are supplied to a magnetic stirrer and mixed at 800 rpm for 2 hours at 20 ° C. to form a condensation composition. The product (D) was obtained.

Further, the condensation composition (C) obtained above
And the condensation composition (D) at a weight ratio (condensation composition (C) / condensation composition (D)) shown in Tables 2 and 3 to a magnetic stirrer, and 2 hours at 800 rpm.
The mixture was mixed at 0 ° C. to prepare a composition for coating a low refractive index layer. The obtained low-refractive-index-layer coating composition was prepared as shown in Tables 2 and 3, respectively, with a low-refractive-index-layer coating composition (b),
(C), (d), (e), (f), (g), (h),
(I), (j), (k), (l), (m), (n),
Let (o), (p), and (q). 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-102A”) was also used.
This "CYTOP CTL-102A" is used as a composition (a) for coating a low refractive index layer.

(3) Manufacture of Laminates (Manufacture of Laminates of Examples 1 to 4 and Comparative Examples 1 to 20) High refractive index layer coating compositions (1) to () shown in Tables 4 and 5, respectively. 11), a polycarbonate plate (made by Teijin Limited,
Product name "Panlite", 40 x 10 x 1 mm) is dipped and pulled up at a speed of 100 mm / min, then at room temperature for 10
After drying for 1 minute, it was cured at 110 ° C. for 60 minutes to obtain a polycarbonate plate on which a high refractive index layer was laminated. Next, the obtained high refractive index layer-covered laminate was dipped in the low refractive index layer-coating compositions (a) to (q) shown in Tables 4 and 5, respectively, and pulled up at a speed of 100 mm / min. Then at room temperature for 10
It was dried for 1 minute and then cured at 110 ° C. for 60 minutes to obtain the target laminate. 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 4 and 5. In Comparative Examples 1 to 6, the composition for coating the high refractive index layer was gelated and could not be used as the composition for coating the high refractive index layer. In addition, Comparative Examples 7 and 1
Nos. 1, 14 and 15 could not be used as a composition for coating a low refractive index layer because the composition for coating a low refractive index layer was gelled. In Comparative Examples 12 and 18, the low refractive index layers could not be laminated. Further, in Comparative Example 13, the film was clouded when the low refractive index layer was coated, and a transparent laminate could not be obtained.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

Examples 5 to 8 and Comparative Examples 21 to 34 (1) Preparation of high refractive index layer coating composition (antistatic coating composition) (12) to (22) The following Examples 5 to 8 and In Comparative Examples 21 to 34,
Aminoalkylalkoxysilane compound A is used for blending the coating composition to obtain a conductive high refractive index layer.
N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane is used as (a), γ-glycidoxypropyltrimethoxysilane is used as the epoxyalkylalkoxysilane compound B (b), and titanium tetraalkoxide (c) is used. ₁ ) as titanium tetra-n-
Butoxide was used. The compounding amount is such that the molar ratio of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane: γ-glycidoxypropyltrimethoxysilane: titanium tetra-n-butoxide is as shown in Table 6. Blended into. Methyl alcohol was used as the organic solvent (e), and distilled water was used as the water (f). The compounding amount is an aminoalkylalkoxysilane compound A (a)
20 mol of methyl alcohol and 3 mol of water per 1 mol
It was blended so that it would be a mole. The nitric acid (d) was blended in the number of moles shown in Table 6 with respect to 1 mole of the aminoalkylalkoxysilane compound A (a).

The specific operation procedure for obtaining the above composition for coating a high refractive index layer was performed as follows. Half of the above-mentioned predetermined amount of methyl alcohol is supplied to a glass beaker, the above-mentioned predetermined amount of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane is added, and N- (β-aminoethyl) -γ is added. Obtaining an alcoholic solution of aminopropyltrimethoxysilane. To this alcohol solution, the above-mentioned predetermined amount of nitric acid and the above-mentioned predetermined amount of water 3/4 amount were added, and the mixture was stirred at room temperature for 3 hours at a stirring speed of 800 rpm,
An alcohol aqueous solution of a hydrolyzate of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane was obtained.

On the other hand, half of the above-mentioned predetermined amount of methyl alcohol was supplied to a glass beaker, and the above-mentioned predetermined amount of γ-glycidoxypropyltrimethoxysilane and titanium tetra-n-butoxide were added to give γ-glycide. An alcohol solution of xypropyltrimethoxysilane and titanium tetra-n-butoxide was obtained.

To the obtained alcohol solution, 1/4 amount of the above-mentioned predetermined amount of water was added, and the stirring rate was 80 at room temperature for 3 hours.
The mixture was stirred at 0 rpm to obtain an aqueous alcohol solution of a hydrolysis product of γ-glycidoxypropyltrimethoxysilane and titanium tetra-n-butoxide.

The above-mentioned hydrolyzate of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and γ-
Glycidoxypropyltrimethoxysilane and titanium tetra-n-butoxide hydrolyzate were mixed with aqueous alcohol solutions and stirred at room temperature for 3 hours at a stirring speed of 800.
By stirring at rpm, a composition for coating a high refractive index layer was obtained. The obtained composition for coating a high refractive index layer is, as shown in Table 6, (12), (13), (14), (15) and (1
6), (17), (18), (19), (20), (2
1) and (22).

(2) Preparation of Composition for Coating Low Refractive Index Layer The same compositions as those for coating low refractive index layer (a) to (q) shown in Tables 2 and 3 were used.

(3) Manufacture of Laminates (Manufacture of Laminates of Examples 5 to 8 and Comparative Examples 21 to 34) High refractive index layer coating compositions (12) to
A polycarbonate plate (manufactured by Teijin Ltd., trade name “Panlite”, 40 × 10 × 1 mm) is dipped in (22), and 10
After pulling up at a speed of 0 mm / min, it was dried at room temperature for 10 minutes and then cured at 110 ° C. for 60 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 dipped in each of the low refractive index layer coating compositions (a) to (q) shown in Table 7, and pulled up at a speed of 100 mm / min. It was dried at room temperature for 10 minutes and then cured at 110 ° C. for 60 minutes to obtain a target laminate. 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 Table 7. In Comparative Examples 21 to 26, the composition for coating the high refractive index layer was gelated and could not be used as the composition for coating the high refractive index layer. In Comparative Example 30, the film was clouded when the low refractive index layer was covered, and a transparent laminate could not be obtained.

[0115]

[Table 6]

[0116]

[Table 7]

[0117]

The method for producing a laminate of the present invention and the present invention 2 is as described above, and it is produced from the antistatic coating composition used in the present invention and the present invention 2 as described above. The high refractive index layer has high conductivity because protons from nitric acid are uniformly present, and has high transparency because there is no haze and the like due to addition of conductive fine particles. Further, since the zirconium tetraalkoxide or the titanium tetraalkoxide is a coating film obtained from a composition in which a specific amount of the zirconium tetraalkoxide or titanium tetraalkoxide is mixed, the water resistance is particularly improved because the coating film is dense. Further, since the metal oxide film is formed,
It is a hard material that is hard to be scratched even when strongly rubbed, and is unlikely to cause a deterioration in appearance due to scratches, and its performance can be maintained for a long period of time. Therefore, according to the present invention and the production method of the present invention 2, while maintaining the optical characteristics of the substrate before the film formation,
A water resistant high refractive index layer having sufficient antistatic performance can be obtained. According to the present invention and the method for producing a laminate of the present invention 2, since the low refractive index layer is further laminated on the surface of the high refractive index layer, the antireflection effect and the antistatic effect can be achieved on the substrate. It is possible to easily manufacture a laminate having a high coating and a light transmittance of 40% or more.

The method for producing a laminate of the present invention 3 is as described above, and the composition for coating a low refractive index layer used in the present invention 3 is the condensation composition (C), which is polycondensation of alkoxysilane. Has progressed considerably and colloidal silica has been formed,
In the condensation composition (D), 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. By coating this composition on a substrate on which the high refractive index layer according to claim 1 or 2 is laminated and curing the composition, the polycondensation reaction of silica sol and colloidal silica is promoted, and the shrinkage ratio of silica sol and colloidal silica is increased. Due to the difference, it is possible to obtain a porous film. 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 present invention 3, a laminate having a high antireflection effect and an antistatic effect on a substrate, being transparent, and having a coating film excellent in scratch resistance and having a light transmittance of 40% or more can be easily produced. You can

Claims (3)

[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 base material so that the low refractive index layer is the outermost layer. Thus, the high refractive index layer comprises (a) an aminoalkylalkoxysilane 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) An epoxyalkylalkoxysilane compound B represented by the following general formula [II]: (In the formula, Z is a glycidoxy group or an epoxycyclohexyl group, Y ² is a hydrocarbon group, R ¹ is an alkyl group having 1 to 5 carbon atoms, p is an integer of 1 to 5, and t is an integer of 0 to 2) (c ) General formula Zr (OR ² ) ₄ (In the formula, R ² has 1 carbon atom.
~ 5 alkyl group), zirconium tetraalkoxide, (d) nitric acid, (e) organic solvent and (f)
Aminoalkylalkoxysilane compound A consisting of water
(A) and epoxyalkylalkoxysilane compound B
Light transmission comprising a layer obtained by applying an antistatic coating composition having a molar ratio of (b) and zirconium tetraalkoxide (c) of 93 to 53:35 to 5:12 to 2 A method for producing a laminate having a rate of 40% or more. 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 base material so that the low refractive index layer is the outermost layer. The high refractive index layer comprises (a) the aminoalkylalkoxysilane compound A according to claim 1, (b) the epoxyalkylalkoxysilane compound B according to claim 1, and (c ₁ ) the general formula Ti.
Titanium tetraalkoxide represented by (OR ³ ) ₄ (wherein R ³ is an alkyl group having 1 to 5 carbon atoms), (d)
Consisting of nitric acid, (e) organic solvent and (f) water, and the molar ratio of aminoalkylalkoxysilane compound A (a), epoxyalkylalkoxysilane compound B (b) and titanium tetraalkoxide (c ₁ ) is 93 to 55: 35
A method for producing a laminate having a light transmittance of 40% or more, which comprises a layer obtained by applying an antistatic coating composition of 5: 10-2. 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 base material so that the low refractive index layer is the outermost layer. And the high refractive index layer is the high refractive index layer according to claim 1 or 2,
Further, the low refractive index layer has 1 mol of tetraalkoxysilane represented by the general formula Si (OR ⁴ ) ₄ (wherein R ⁴ is an alkyl group having 1 to 5 carbon atoms), and the pH is 10.0 to 12. 0 of the basic water 2-8 mole and a condensation composition obtained by mixing the organic solvent 10 to 30 mole (C), and the general formula _{^{(R 6) s Si (oR}} 5) 4-s ( wherein, R ⁵ and R ⁶ are alkyl groups having 1 to 5 carbon atoms, s is an alkoxysilane represented by 0 to 3), and the pH is 0 to
The condensation composition (D) obtained by mixing 3 to 8 mol of the acidic water of 2.6 and 10 to 30 mol of the organic solvent in a weight ratio (C) / (D) = 0.4 to 2.4. A method for producing a laminate having a light transmittance of 40% or more, which comprises a layer obtained by mixing and applying the obtained composition.