CN116997624A - Inorganic particle dispersion liquid - Google Patents

Abstract

The present invention provides an inorganic fine particle dispersion capable of forming a coating film with high light transmittance and high coating film strength (high adhesion of the coating film to a substrate) and having good storage stability. An inorganic particle dispersion liquid, the inorganic particle dispersion liquid includes: inorganic particles, a liquid dispersion medium A with a boiling point greater than or equal to 100°C and less than 190°C (excluding water), and a liquid dispersion medium B with a boiling point less than 100°C , where, when the total amount of the inorganic fine particle dispersion liquid is 100 mass%, the content rate of the liquid dispersion medium A is 0.5 mass% or more and less than 15 mass%.

Description

Inorganic particle dispersion

Technical Field

The present invention relates to an inorganic particle dispersion.

Background Art

Conventionally, an anti-reflection film is formed on the surface of a display in order to prevent display glare, etc. As a material of the anti-reflection film, for example, Patent Document 1 describes an inorganic particle dispersion containing inorganic particle chains, inorganic particles, and a liquid dispersion medium.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Publication No. 2006-327187

Summary of the invention

Problems to be solved by the invention

In recent years, an anti-reflection film is formed on the surface of the protective glass of the solar cell in order to improve the power generation efficiency. However, it is required to further improve the light transmittance of the protective glass of the solar cell.

An object of the present invention is to provide an inorganic fine particle dispersion capable of forming a layer having a higher light transmittance.

Means used to solve problems

The present inventors have conducted intensive studies in view of such background and have completed the present invention as a result.

That is, the present invention relates to the following contents, but is not limited thereto.

[1]

An inorganic particle dispersion, comprising:

Inorganic particles,

a liquid dispersion medium A (excluding water) having a boiling point of 100° C. or more and less than 190° C., and

Liquid dispersion medium B with a boiling point less than 100°C,

in,

When the total amount of the inorganic fine particle dispersion is 100 mass %, the content of the liquid dispersion medium A is 0.5 mass % or more and less than 15 mass %.

Hereinafter, [2] to [14] are each a preferred aspect or embodiment of the present invention.

[2]

The inorganic fine particle dispersion according to [1], wherein the content of the liquid dispersion medium B is 20 mass % or more and 85 mass % or less, when the total amount of the inorganic fine particle dispersion is 100 mass %.

[3]

The inorganic fine particle dispersion according to [1] or [2], wherein the liquid dispersion medium B is alcohol.

[4]

The inorganic fine particle dispersion according to any one of [1] to [3], wherein the inorganic fine particle dispersion further contains water.

[5]

The inorganic fine particle dispersion according to [4], wherein the content of water is 5 mass % or more and 55 mass % or less, when the total amount of the inorganic fine particle dispersion is 100 mass %.

[6]

The inorganic fine particle dispersion according to any one of [1] to [5], wherein the inorganic fine particle dispersion further contains alkoxysilane and/or a condensate thereof.

[7]

The inorganic fine particle dispersion as described in any one of [1] to [5], wherein the inorganic fine particle dispersion further comprises one or more selected from the group consisting of alkoxysilane, alkoxysilane condensates in which a plurality of Si-O-Si bonds are linearly linked, and alkoxysilane condensates in which a plurality of Si-O-Si bonds are three-dimensionally linked.

[8]

The inorganic fine particle dispersion according to any one of claims 1 to 7, wherein the liquid dispersion medium A is an alcohol.

[9]

The inorganic fine particle dispersion according to any one of [1] to [8], further comprising a surfactant.

[10]

The inorganic fine particle dispersion according to any one of [1] to [8], wherein the inorganic fine particle dispersion further comprises a surfactant, and the surfactant comprises a polyether-modified siloxane.

[11]

The inorganic fine particle dispersion according to any one of [1] to [10], wherein the inorganic fine particles are colloidal silica.

[12]

The inorganic fine particle dispersion according to any one of [1] to [11], wherein the content of the inorganic fine particles is 0.1% by mass or more and 10% by mass or less, based on 100% by mass of the total amount of the inorganic fine particle dispersion.

[13]

A method for manufacturing a laminate, wherein the method for manufacturing the laminate comprises the following steps:

A step of coating the inorganic fine particle dispersion according to any one of [1] to [12] on a substrate (coating step); and

A step of removing the liquid dispersion medium A and the liquid dispersion medium B from the inorganic fine particle dispersion applied on the substrate to form an inorganic fine particle layer on the substrate (dispersion medium removal step).

[14]

The method for producing a laminate according to [13], further comprising a heat treatment step after the dispersion medium removal step.

[15]

A laminated body obtained by the method described in [13] or [14], wherein the laminated body comprises a substrate and an inorganic fine particle layer.

Effects of the Invention

According to the present invention, it is possible to provide an inorganic fine particle dispersion which can form a coating film having high light transmittance and high coating film strength (high adhesion of the coating film to a substrate) and has good storage stability.

According to the present invention, it is also possible to provide a laminate having high light transmittance and high coating film strength (high adhesion of the coating film to the substrate).

DETAILED DESCRIPTION

Hereinafter, one embodiment of the present invention will be described in detail.

＜Inorganic fine particle dispersion＞

The inorganic microparticle dispersion of the present invention comprises:

Inorganic particles,

a liquid dispersion medium A (excluding water) having a boiling point of 100° C. or more and less than 190° C., and

Liquid dispersion medium B with a boiling point less than 100°C,

in,

When the total amount of the inorganic fine particle dispersion is 100 mass %, the content of the liquid dispersion medium A is 0.5 mass % or more and less than 15 mass %.

[Inorganic particles]

In the present invention, the inorganic particles may be inorganic particles X having a primary particle size of 1 nm or more and 60 nm or less, or inorganic particles Y formed by connecting a plurality of inorganic particles having a primary particle size of 1 nm or more and 60 nm or less. Here, the expression "plural connected" includes not only a state connected in a straight line, but also a state connected in a bent manner, a state connected in a ring shape, and a branched state.

The primary particle size of the inorganic fine particles is evaluated as the number average of particle sizes of 50 or more particles observed with a transmission microscope. The state of "a plurality of inorganic fine particles connected" in the inorganic fine particles Y can also be determined by observation with a transmission microscope.

As the material of the inorganic particles, for example, silicon oxide (silicon dioxide), titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, etc., one or more of which can be used. From the viewpoint of dispersibility in the inorganic particle dispersion, silicon dioxide is preferred, and colloidal silicon dioxide and fumed silicon dioxide are further preferred among silicon dioxides, and colloidal silicon dioxide is particularly preferred. Colloidal silicon dioxide can be an inorganic particle dispersion containing colloidal silicon dioxide particles at a solid content concentration of 5% to 50% by weight, for example, 5% to 40% by weight, and preferably 10% to 30% by weight. Colloidal silicon dioxide can be used as colloidal silicon dioxide dispersed in various solvents, and as the solvent, the following can be mentioned:

Alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, and ethylene glycol mono-n-propyl ether;

Amide solvents such as dimethylacetamide and N-methylpyrrolidone;

Aromatic solvents such as toluene;

Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;

Ester solvents such as ethyl acetate;

Water, etc., and a plurality of these solvents may be used in mixture.

Preferred are alcohol solvents such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol mono-n-propyl ether and water, more preferred are methanol, ethanol, isopropanol and water, more preferred are ethanol, isopropanol and water, and more preferred is water.

The inorganic fine particles may be inorganic fine particles X having a primary particle diameter of 1 nm to 60 nm, or inorganic fine particles Y in which a plurality of inorganic fine particles having a primary particle diameter of 1 nm to 60 nm are connected.

From the viewpoint of achieving both transmittance and coating strength, the primary particle size of the inorganic fine particles X is preferably 1 nm to 50 nm, more preferably 1 nm to 30 nm, further preferably 1 nm to 20 nm, particularly preferably 3 nm to 10 nm.

From the perspective of both transmittance and coating strength, the primary particle size of the inorganic particle Y formed by connecting multiple inorganic particles with a primary particle size of 1 nm or more and 60 nm or less is preferably 1 nm or more and 50 nm or less, more preferably 1 nm or more and 45 nm or less, further preferably 1 nm or more and 30 nm or less, and particularly preferably 5 nm or more and 20 nm or less.

The average particle size of the inorganic particles Y is preferably 1 nm to 500 nm, more preferably 1 nm to 400 nm, and is obtained by a dynamic light scattering method or a Sears method. The determination of the average particle size by the dynamic light scattering method can be carried out using a commercially available particle size distribution measuring device. The Sears method is a method as follows: It is described in Analytical Chemistry, Vol. 28, pp. 1981-1983, 1956, and is an analytical method for the determination of the average particle size of silica particles, wherein the surface area is obtained by adjusting the amount of NaOH consumed by the colloidal silica dispersion having a pH of 3 to a pH of 9, and the equivalent spherical diameter is calculated from the obtained surface area. The equivalent spherical diameter obtained in this way is taken as the average particle size.

In addition, the mixing ratio of the inorganic particles Y formed by the inorganic particles X that is more than 1nm and less than 60nm and multiple primary particle diameters are connected to each other with more than 1nm and less than 60nm is not particularly limited to primary particle diameter, from the viewpoint of transmittance and coating strength, it is preferred to use the two, (the quality of inorganic particles Y)/[(the quality of inorganic particles X)+(the quality of inorganic particles Y)] is preferably more than 0.01 and less than 0.99, more preferably more than 0.10 and less than 0.95, more preferably more than 0.20 and less than 0.95, more preferably more than 0.40 and less than 0.95, more preferably more than 0.50 and less than 0.90, more preferably more than 0.60 and less than 0.80. In addition, as inorganic particles X, one or more inorganic particles can be used, as inorganic particles Y, one or more inorganic particles can be used.

There is no particular restriction on the content of inorganic particles. Consider from the viewpoint of the transparency of the obtained coating and the dispersibility in the inorganic particle dispersion liquid, when the gross weight of the inorganic particle dispersion liquid is set to 100 weight %, the content of inorganic particles is preferably more than 0.1 mass % and less than 10 weight %, more preferably more than 0.1 mass % and less than 7.5 weight %, further preferably more than 0.2 mass % and less than 5.0 weight %, particularly preferably more than 1 mass % and less than 5.0 weight %. Below, sometimes the content of inorganic particles in the case where the inorganic particle dispersion liquid is set to 100 mass % as a whole is recorded as "the solid component concentration of inorganic particles in the inorganic particle dispersion liquid". In addition, "the content of inorganic particles" refers to the total value of the content of inorganic particles X and the content of inorganic particles Y.

From the viewpoint of dispersibility, coating and film formation in the dispersion, the inorganic particles in the inorganic particle dispersion can be surface treated. As the surface treated method, known methods can be used, and suitable additives can be cited for processing. The surface treatment of inorganic particles can be carried out by mixing the liquid containing inorganic particles, additives and solvents.

Specific examples of the inorganic fine particles X include: commercially available Snowtex (registered trademark) ST-XS, ST-OXS, ST-NXS, ST-CXS, ST-S, ST-OS, ST-NS, ST-3O, ST-O, ST-N, ST-C, ST-AK, ST-5O-T, ST-O-4O, ST-N-4O, ST-CM, ST-3OL, ST-OL, ST-AK-L, ST-YL, ST-OYL, ST-AK-YL in the form of a methanol dispersion; commercially available methanol silica sol (registered trademark), MA-ST-M, MA-ST-L in the form of an isopropyl alcohol dispersion; commercially available IPA-ST, IPA-ST-L in the form of an ethylene glycol monopropyl ether dispersion. NPC-ST-30, a commercial product, in the form of a toluene dispersion; TOL-ST, a commercial product, in the form of a toluene dispersion; MEK-ST-40, MEK-ST-L, MEK-EC-2130Y, MEK-EC-2430Z, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, a commercial product, in the form of a 2-butanone dispersion; MIBK-ST, MIBK-ST-L, MIBK-AC-2140Z, MIBK-SD-L, in the form of a 4-methyl-2-pentanone dispersion; CHO-ST-M, in the form of a cyclohexanone dispersion; EAC-ST, a commercial product, in the form of an ethyl acetate dispersion; and PMA-ST, in the form of a propylene glycol 1-monomethyl ether 2-acetate dispersion. Among them, inorganic fine particles in the form of aqueous dispersion are preferred, with ST-OXS, ST-NXS, ST-CXS, ST-OS, ST-NS, ST-O, ST-N, ST-C, ST-O-4O, ST-N-4O, ST-CM, ST-OL and ST-OYL being particularly preferred, and ST-OXS, ST-OS, ST-O, ST-O-4O, ST-OL and ST-OYL being more preferred.

Specifically, inorganic fine particles Y include, for example, commercially available Snowtex (registered trademark) ST-UP, ST-OUP, ST-PS-S, ST-PS-SO, ST-PS-M, and ST-PS-MO in the form of aqueous dispersions; commercially available MA-ST-UP in the form of methanol dispersions; commercially available IPA-ST-UP in the form of isopropyl alcohol dispersions; and commercially available MEK-ST-UP in the form of 2-butanone dispersions. Among them, inorganic fine particles in the form of aqueous dispersions are preferred, with ST-OUP, ST-PS-SO, and ST-PS-MO being particularly preferred, and ST-OUP being more preferred.

There is no particular limitation on the method for synthesizing the inorganic particles X and Y. Examples thereof include hydrolysis and/or condensation of metal alkoxides, thermal decomposition of metal salts, pulverization and/or crushing of metal oxides, precipitation of metal salt aqueous solutions, and hydrothermal treatment of metal salt aqueous solutions.

From the viewpoint of dispersibility, the preferred silica is synthesized by a method in which an aqueous sodium silicate solution is subjected to ion exchange using an ion exchange resin or the like, followed by particle growth and concentration (sometimes also referred to as a water glass method), a method in which an aqueous sulfuric acid solution is added to an aqueous sodium silicate solution to neutralize the solution, followed by particle growth and concentration (sometimes also referred to as a sedimentation method), a method in which silicon tetrachloride is thermally decomposed, a method in which an alkoxysilane is hydrolyzed and condensed, and other well-known methods (sometimes also referred to as a sol-gel method).

In the case of the synthesis method by ion exchange of sodium silicate, the sodium ion content in the silica sol is preferably 0.5 wt% or less, more preferably 0.05 wt% or less, and further preferably 0.03 wt% or less in terms of _Na2O amount, from the viewpoint of forming an inorganic fine particle layer with high light transmittance.

[Liquid dispersion medium A]

In the present invention, the liquid dispersion medium A is a liquid (excluding water) having a boiling point of 100° C. or more and less than 190° C. at atmospheric pressure (1013.25 hPa). When the entire inorganic fine particle dispersion is 100% by mass, the content of the liquid dispersion medium A is 0.5% by mass or more and less than 15% by mass.

The boiling point range of the liquid dispersion medium A is preferably 115° C. or higher and lower than 190° C., preferably 125° C. or higher and lower than 190° C., further preferably 135° C. or higher and lower than 190° C., further preferably 150° C. or higher and lower than 190° C., further preferably 155° C. or higher and lower than 190° C., further preferably 155° C. or higher and lower than 180° C., further preferably 160° C. or higher and lower than 180° C., further preferably 170° C. or higher and lower than 180° C.

As the lower limit of the content of the liquid dispersion medium A, from the viewpoint of suppressing the aggregation of inorganic particles when the coating film is dried and improving the transmittance and coating film strength by using the liquid dispersion medium A, when the entire inorganic particle dispersion is 100 mass %, it is preferably contained 0.7 mass % or more of the liquid dispersion medium A, and more preferably contains 0.8 mass % or more of the liquid dispersion medium A. In addition, as the upper limit of the content of the liquid dispersion medium A, from the viewpoint of deterioration of the storage stability due to gelation of the inorganic particle dispersion when an excessive amount of the liquid dispersion medium A is contained, when the entire inorganic particle dispersion is 100 mass %, it is preferably contained 13 mass % or less of the liquid dispersion medium A, more preferably contains 12 mass % or less of the liquid dispersion medium A, more preferably contains 8 mass % or less of the liquid dispersion medium A, more preferably contains 5 mass % or less of the liquid dispersion medium A, and more preferably contains 3 mass % or less of the liquid dispersion medium A.

As the liquid dispersion medium A, a liquid dispersion medium having a δtA defined by the following formula of 20 MPa ^0.5 or more and 40 MPa ^0.5 or less can be exemplified as a preferable example.

δtA＝{4(δDA-15.6) ² +(δPA-16.0) ² +(δHA-42.0) ² } ^0.5 (1)

(In formula (1), δDA, δPA, and δHA represent the dispersion term (Mpa ^0.5 ), polar term (Mpa ^0.5 ), and hydrogen bonding term (Mpa ^0.5 ) in the Hansen solubility parameters of the liquid dispersion medium A, respectively.)

The above-mentioned δDA, δPA, and δHA were calculated using "HSPiP 5th 5.2.06" which is a generally available commercial software, and applying a method called Y-MB in the software.

As a preferred range of δtA, the upper limit is preferably 39Mpa ^0.5 or less, more preferably 35.5Mpa ^0.5 or less, and further preferably 34Mpa ^0.5 or less. The lower limit is preferably 25Mpa ^0.5 or more, more preferably 29Mpa ^0.5 or more, and further preferably 30Mpa ^0.5 or more. The liquid dispersion medium A having δtA within such a range can obtain a high affinity with the silica particles, and the coating property becomes good.

From the viewpoint of coating properties, the lower limit of the molecular weight of the liquid dispersion medium A is preferably 60 or more, more preferably 70 or more, further preferably 90 or more, and particularly preferably 100 or more. The upper limit is preferably 300 or less, more preferably 200 or less, further preferably 170 or less, and particularly preferably 140 or less.

Examples of the type of liquid dispersion medium A include, but are not limited to, ethers, esters, alcohols, ketones, amines, amides, and sulfoxides. Specific examples of the liquid dispersion medium A include, but are not limited to, the following substances:

2-Methoxyethyl acetate, 4-methyl-2-pentanone, 1-methoxy-2-propanol, 4-ethylmorpholine, isoamyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 1-propoxy-2-propanol, N,N-dimethylformamide, 2-ethoxyethyl acetate, dimethyl sulfoxide, dipropylene glycol dimethyl ether,

n-Amyl acetate, n-propyl acetate, ethyl acetoacetate, 2-pentanone, 3-pentanone, acetylacetone (2,4-pentanedione), n-butanol, isobutanol, 1-hexanol, furfuryl alcohol, 2-methyl-2-butanol, 1-pentanol, 3-pentanol, dibutyl ether, 1,4-dioxane, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), 2-ethylhexanol, N,N-dimethylacetamide, ethyl lactate, diethylene glycol Ethyl methyl ether, 3-methoxybutyl acetate, 2-(butylamino)ethanol, 2-(methylamino)ethanol, N-cyclohexylamine, 1,2-propylene glycol, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-tert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, tetrahydrofurfuryl alcohol, 2-hydroxyethyl acetate, 1-butanol,

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 1,2-diethoxyethane,

1,2-diacetoxypropane, 3-methoxy-3-methylbutyl acetate.

Preferred liquid dispersion medium A includes a liquid dispersion medium corresponding to any one of an alcohol liquid dispersion medium, a liquid dispersion medium having an ether bond, and a liquid dispersion medium having an ester bond. More preferably, a liquid dispersion medium corresponding to any one of an alcohol liquid dispersion medium, a liquid dispersion medium having an ether bond, and a liquid dispersion medium having an ester bond and containing no nitrogen atom can be included. When such a liquid dispersion medium A is used, coating properties become better.

As one embodiment of the inorganic particle dispersion, the liquid dispersion medium A is preferably an alcohol. When the liquid dispersion medium A is an alcohol, the compatibility of the inorganic particle component during coating with the alkoxysilane and/or its condensate (C) described later is improved, the coating property becomes good, and a laminate having a high coating film strength (high adhesion of the coating film to the substrate) can be obtained.

When the liquid dispersion medium A is an alcohol, monohydric alcohols can be cited as good examples. In addition, it is preferred to have an alcohol having any one or more of an ether bond and an ester bond. When the liquid dispersion medium A is such an alcohol, the dispersion and coating properties of the inorganic particles become good. As such specific examples, 1-methoxy-2-propanol, 1-propoxy-2-propanol, furfuryl alcohol, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-methoxyethanol (ethylene glycol monomethyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), ethyl lactate, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol mono-tert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, 2-allyloxyethanol, tetrahydrofurfuryl alcohol, 2-hydroxyethyl acetate,

More preferably, the following can be cited:

1-propoxy-2-propanol, 2-butoxyethanol (ethylene glycol monobutyl ether), 2-ethoxyethanol (ethylene glycol monoethyl ether), ethyl lactate, 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 1-ethoxy-2-propanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol monotert-butyl ether, 2-isopropoxyethanol, 2-propoxyethanol, 2-isobutoxyethanol, tetrahydrofurfuryl alcohol,

Further preferred examples include:

2-Butoxyethanol (ethylene glycol monobutyl ether), 3-methoxy-3-methylbutanol, propylene glycol 1-monobutyl ether, 3-methoxy-1-propanol, 3-methoxy-1-butanol, ethylene glycol monotert-butyl ether, 2-propoxyethanol, 2-isobutoxyethanol, tetrahydrofurfuryl alcohol.

[Liquid dispersion medium B]

In the present invention, the liquid dispersion medium B is a liquid having a boiling point of less than 100° C. at atmospheric pressure (1013.25 hPa).

As the liquid dispersion medium B, a liquid dispersion medium having a δtB defined by the following formula of 15 MPa ^0.5 or more and 39 MPa ^0.5 or less can be exemplified as a preferable example.

δtB＝{4(δDB-15.6) ² +(δPB-16.0) ² +(δHB-42.0) ² } ^0.5 (2)

(Wherein, δDB, δPB, and δHB represent the dispersion term (Mpa ^0.5 ), polar term (Mpa ^0.5 ), and hydrogen bond term (Mpa ^0.5 ) in the Hansen solubility parameters of the liquid dispersion medium B, respectively.)

The above-mentioned δDB, δPB, and δHB are calculated using "HSPiP 5th 5.2.06" which is a generally available commercial software, and applying a method called Y-MB in the software.

As a preferred range of δtB, the upper limit is preferably 32Mpa ^0.5 or less, preferably 31Mpa ^0.5 or less, and more preferably 27Mpa ^0.5 or less. The lower limit is preferably 18Mpa ^0.5 or more, more preferably 23Mpa ^0.5 or more, and more preferably 25Mpa ^0.5 or more. The liquid dispersion medium B with δtB within such a range can obtain a high affinity with the silica particles, and the coating property becomes good.

As the type of liquid dispersion medium B, for example, ethers, esters, alcohols, etc. can be listed, as ethers, for example, diethyl ether can be listed, as esters, for example, methyl acetate and ethyl acetate can be listed, as alcohols, for example, methanol, ethanol, tert-butyl alcohol, sec-butyl alcohol, isopropyl alcohol and n-propyl alcohol can be listed. From the viewpoint of dispersibility of inorganic particles in the inorganic particle dispersion, alcohols are preferred, methanol, ethanol and isopropyl alcohol are more preferred, ethanol and isopropyl alcohol are particularly preferred, and from the viewpoint of safety, ethanol is more preferred.

The content of the liquid dispersion medium B is not particularly limited. From the viewpoint of coating properties and storage stability, when the entire inorganic fine particle dispersion is 100% by mass, it is preferred that the content of the liquid dispersion medium B is 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 95% by mass or less of the liquid dispersion medium B, more preferably 90% by mass or less of the liquid dispersion medium B, more preferably 85% by mass or less of the liquid dispersion medium B, and more preferably 80% by mass or less of the liquid dispersion medium B.

[water]

In the present invention, as a mode, the inorganic particle dispersion preferably includes water. As the lower limit of the content of water, from the viewpoint of coating property and storage stability, when the inorganic particle dispersion is set to 100% by mass as a whole, it is preferred to include more than 1% by mass of water, further preferably include more than 3% by mass of water, further preferably include more than 5% by mass of water, further preferably include more than 8% by mass of water, further preferably include more than 10% by mass of water. In addition, as the upper limit of the content of water, from the viewpoint of transmittance, it is preferred to include less than 55% by mass of water, further preferably include less than 50% by mass of water, further preferably include less than 45% by mass of water, further preferably include less than 35% by mass of water, further preferably include less than 25% by mass of water, further preferably include less than 20% by mass of water.

[Alkoxysilane and/or its condensate (C)]

In one embodiment of the present invention, the inorganic fine particle dispersion preferably contains alkoxysilane and/or its condensate (component C). Component C is alkoxysilane and/or its condensate. Examples of the alkoxysilane include tetraalkoxysilane.

As one embodiment, tetraalkoxysilane is represented by the following formula: Si(OR) ₄ (wherein, four Rs independently represent an alkyl group having 1 to 6 carbon atoms). As one embodiment, the condensate of tetraalkoxysilane is represented by the following formula: Si _n O _n-1 (OR) _2n+2 (wherein, each R independently represents an alkyl group having 1 to 6 carbon atoms. n is 2 to 1000, and as one embodiment, n is 2 to 100). Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc., preferably tetramethoxysilane and tetraethoxysilane. Hereinafter, alkoxysilane is sometimes described as "component C1". Commercially available alkoxysilanes can be used.

The OR site of these alkoxysilanes may be partially hydrolyzed, and the hydrolyzed portion may be further condensed.

As one embodiment of the alkoxysilane, a silicon compound represented by the following formula (1) can be mentioned.

Si(R ^a ) _q (R ^b ) _4-q (1)

In the formula (1), ^Ra represents a hydrogen atom or a non-hydrolyzable organic group, ^Rb represents a hydrolyzable group, and q represents an integer of 0-2.

In this specification, "hydrolyzable" means a property of generating a silanol group by reaction with water.

Examples of the non-hydrolyzable organic group of ^Ra include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, tert-pentyl (1,1-dimethylpropyl), 1,1-dimethyl-3,3-dimethylbutyl, heptyl, octyl, nonyl and decyl; cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl; alkenyl groups having 2 to 10 carbon atoms, such as vinyl and allyl; alkylidene groups having 2 to 10 carbon atoms, such as ethylidene and propylidene; aromatic groups having 6 to 15 carbon atoms, such as phenyl, naphthyl and anthracenyl; and the like.

The hydrogen atoms contained in these organic groups may be substituted by (meth)acryloyloxy, epoxy, amino, mercapto, hydroxyl, halogen, alkoxy, fluoroalkyl, glycidoxy, etc. One hydrogen atom in the organic group may be substituted, or two or more hydrogen atoms in the organic group may be substituted.

Examples of the hydrolyzable group of R ^b include alkoxy groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, and propoxy.

q represents an integer of 0 to 2, and is preferably 0 or 1. In one embodiment, q is 0. In one embodiment, q is 1.

The hydrolyzable group of the silicon compound represented by the formula (1) may be hydrolyzed, and further condensed at the hydrolyzed portion.

Examples of the silicon compound represented by formula (1) include silicon compounds wherein q is 0, such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-isobutoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyl ...methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyl Silicon compounds wherein q is 1, such as butyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane; silicon compounds wherein q is 2, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylphenyldimethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane; etc.

The inorganic particle dispersion may contain only one silicon compound represented by formula (1), or may contain two or more silicon compounds represented by formula (1). In addition, the inorganic particle dispersion may contain a silicon compound represented by formula (1) and a silicon compound wherein q is 3 such as trimethylmethoxysilane, triethylmethoxysilane, triethylmethoxysilane, triethylethoxysilane, trivinylmethoxysilane, or trivinylethoxysilane.

The condensate of alkoxysilane (hereinafter, sometimes described as "component C2") can be obtained by subjecting these alkoxysilane monomers to hydrolysis and condensation reaction. There is no particular limitation on the degree of polymerization of the condensate of alkoxysilane. As one embodiment, the degree of polymerization of the condensate of alkoxysilane is 2 to 1000, and as one embodiment, the degree of polymerization of the condensate of alkoxysilane is 2 to 100. Hereinafter, the condensate of alkoxysilane having a degree of polymerization of 2 to 1000 is sometimes described as "component C2-1". As one embodiment, the condensate of alkoxysilane may be an oligomer of a dimer to a decamer. As one embodiment of the condensate of alkoxysilane, an alkoxysilane condensate in which a plurality of Si-O-Si bonds are linearly connected (hereinafter, sometimes described as "component C2-2") can be listed. As one embodiment of component C2-2, an alkoxysilane condensate in which more than half of the ends of the alkoxysilane condensate are alkoxy groups can be listed. As one form of the condensate of alkoxysilane, an alkoxysilane condensate (hereinafter, sometimes described as "component C2-3") in which a plurality of Si-O-Si bonds are three-dimensionally connected can be cited. As one form of component C2-3, an alkoxysilane condensate in which more than half of the ends of the alkoxysilane condensate are hydroxyl groups can be cited. The average particle size of the condensate of alkoxysilane is preferably less than 1 μm. The condensate of alkoxysilane can use a commercial product. The above-mentioned OR portion of the condensate of alkoxysilane can be partially hydrolyzed, and the hydrolyzed portion can be further condensed.

Examples of commercially available products of condensates of alkoxysilanes include: Methyl Silicate 51, which is an average tetramer oligomer of tetramethoxysilane; Methyl Silicate 53A, which is an average heptamer oligomer of tetramethoxysilane; Ethyl Silicate 40, which is an average pentamer oligomer of tetraethoxysilane; Ethyl Silicate 48, which is an average decamer oligomer of tetraethoxysilane; and EMS-485, which is a mixture of tetramethoxysilane oligomers and tetraethoxysilane oligomers and is an average decamer oligomer (all manufactured by Colcoat Co., Ltd.).

In addition, as commercially available products of the hydrolysis condensate of methyl silicate among the alkoxysilane condensates, for example, MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation) can be cited, and these substances are condensates in which a plurality of Si-O-Si bonds are linearly connected and more than half of the terminals of the condensate are alkoxy groups.

In addition, commercially available products of the hydrolysis condensate of ethyl silicate among the alkoxysilane condensates include, for example, HAS-1, HAS-6, and HAS-10 (all manufactured by Colcoat Co., Ltd.), which are condensates in which multiple Si-O-Si bonds are linearly connected and more than half of the ends of the condensate are alkoxy groups.

The peak top molecular weight of the condensate of alkoxysilane is preferably 100 to 10000, more preferably 500 to 5000. In one embodiment, the peak top molecular weight of the condensate of alkoxysilane is 500 to 2000. In one embodiment, the peak top molecular weight of the condensate of alkoxysilane is 500 to 1000.

As the peak top molecular weight of the condensate of alkoxysilane, a value measured by gel permeation chromatography can generally be used.

The inorganic fine particle dispersion may contain alkoxysilane alone or a condensate thereof alone, or both. The inorganic fine particle dispersion may contain only one component C, or two or more components C.

The amount of component C in the inorganic fine particle dispersion is not particularly limited. When the total weight of the inorganic fine particle dispersion is set to 100 weight %, the amount of component C is preferably 0.001 weight % to 2 weight %, more preferably 0.005 weight % to 1 weight %, and further preferably 0.01 weight % to 0.5 weight %. Hereinafter, the content of component C may be described as "solid content concentration of component C in the dispersion".

The inorganic particle dispersion may contain only alkoxysilane as component (C), may contain only condensates of alkoxysilane as component (C), or may contain condensates of alkoxysilane and alkoxysilane as component (C). When the inorganic particle dispersion contains condensates of alkoxysilane and alkoxysilane, the combinations thereof include: a combination of a silicon compound in which q is 0 in formula (1) and a dimer to a decamer of alkoxysilane; a combination of a silicon compound in which q is 0 in formula (1) and a condensate in which a plurality of Si-O-Si bonds are linearly connected, and more than half of the ends of the condensate are alkoxy groups; a combination of a silicon compound in which q is 0 in formula (1) and a condensate in which a plurality of Si-O-Si bonds are three-dimensionally connected, and more than half of the ends of the condensate are alkoxy groups; A combination of condensates in which more than half of the terminals are hydroxyl groups; a combination of a silicon compound in which q is 1 in formula (1) and a dimer to a decamer of alkoxysilane; a combination of a silicon compound in which q is 1 in formula (1) and a condensate in which a plurality of Si-O-Si bonds are linearly connected, and more than half of the terminals of the condensate are alkoxy groups; a combination of a silicon compound in which q is 1 in formula (1) and a condensate in which a plurality of Si-O-Si bonds are three-dimensionally connected, and more than half of the terminals of the condensate are hydroxyl groups.

The inorganic fine particle dispersion may contain only one kind of alkoxysilane as the component (C), or may contain two or more kinds of alkoxysilanes as the component (C).

The inorganic fine particle dispersion may contain only one condensate of alkoxysilane as component (C), or may contain condensates of two or more alkoxysilanes as component (C). When the inorganic fine particle dispersion contains condensates of two or more alkoxysilanes, the combination thereof may include: a combination of a dimer to a decamer of alkoxysilane and a condensate linearly connected to a plurality of Si-O-Si bonds, wherein more than half of the terminals of the condensate are alkoxy groups; a combination of a dimer to a decamer of alkoxysilane and a condensate three-dimensionally connected to a plurality of Si-O-Si bonds, wherein more than half of the terminals of the condensate are hydroxy groups; a combination of a condensate linearly connected to a plurality of Si-O-Si bonds, wherein more than half of the terminals of the condensate are alkoxy groups, and a condensate three-dimensionally connected to a plurality of Si-O-Si bonds, wherein more than half of the terminals of the condensate are hydroxy groups.

The inorganic particle dispersion preferably contains one or more alkoxysilane condensates as component (C). As one embodiment, as an alkoxysilane condensate, a condensate of an alkoxysilane in which multiple Si-O-Si bonds are linearly connected is preferred. As such an alkoxysilane condensate, an alkoxysilane condensate represented by the following formula can be cited: Si _n O _n-1 (OR) _2n+2 (wherein, each R independently represents an alkyl group having 1 to 6 carbon atoms. N represents 2 to 1000). The coating strength of such an inorganic particle dispersion is more excellent. In the above formula, as an alkyl group having 1 to 6 carbon atoms, methyl, ethyl, propyl, butyl, pentyl, and hexyl can be cited, preferably methyl, ethyl, and butyl can be cited, and more preferably methyl and ethyl can be cited. In the above formula, n represents 2 to 1000, n is preferably 3 to 100, n is more preferably 4 to 50, n is more preferably 6 to 30, and n is more preferably 8 to 30.

Specific examples of commercially available products of the alkoxysilane condensate include, but are not limited to, MS51, MS56, MS57, MS56S (all manufactured by Mitsubishi Chemical Corporation), HAS-1, HAS-6, HAS-10 (all manufactured by Colcoat Corporation).

<Weight ratio of _SiO2 in component C>

The ratio of the weight of SiO ₂ in component C to the total weight of the inorganic fine particles X and the inorganic fine particles Y is preferably 0.005 to 0.6, more preferably 0.005 to 0.2, further preferably 0.007 to 0.15, and particularly preferably 0.01 to 0.12.

As the raw material liquid when preparing the inorganic fine particle dispersion, a liquid containing component C and a solvent can be used. The raw material liquid containing component C may contain additives that promote hydrolysis and dehydration condensation, inhibit aggregation of condensates, or control adhesion to the substrate. As an example of the additive, an acrylic-urethane resin can be cited.

[Surfactant]

As a mode, from the viewpoints of the smoothness of the coating film, the inorganic particle dispersion preferably includes a surfactant. In the case where the inorganic particle dispersion includes a surfactant, relative to 100 parts by weight of a liquid dispersion medium, the content of the surfactant is preferably 0.01 parts by mass or more and 0.5 parts by mass or less, as a further preferred mode, the content of the surfactant is 0.1 parts by mass or more and 0.45 parts by mass or less, as a further preferred mode, the content of the surfactant is greater than 0.3 parts by mass and less than or equal to 0.45 parts by mass. There is no particular restriction on the surfactant used, for example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be cited. As a preferred surfactant, a nonionic surfactant can be cited.

Examples of the anionic surfactant include alkali metal salts of carboxylic acids, specifically sodium octanoate, potassium octanoate, sodium caprate, sodium caproate, sodium myristate, potassium oleate, tetramethylammonium stearate, sodium stearate, etc. Alkali metal salts of carboxylic acids having an alkyl chain having 6 to 10 carbon atoms are particularly preferred.

Examples of the cationic surfactant include hexadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, N-octadecylpyridinium bromide, Hexadecyltriethyl bromide wait.

Examples of nonionic surfactants include polyether-modified siloxanes. The siloxane chain of the main chain of the polyether-modified siloxane may be a linear or branched structure, the ether chain of the side chain of the polyether-modified siloxane may be a linear or branched structure, and a portion of the side chain of the polyether-modified siloxane may be modified with an alkyl group or the like. Commercially available products may be used as polyether-modified siloxanes, examples of which include: KF-6015, KF-6017, KF-6017P, KF-6028, KF-6028P, KF-6038, KF-6043, KF-6048 (all manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-306, BYK-307, BYK-310, BYK-333, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-378 (all manufactured by BYK Chemical Japan Co., Ltd.); DOWSIL (trademark) 501W Additive, DOWSIL (trademark) FZ-2104 Fluid, DOWSIL (trademark) FZ-2110, DOWSIL (trademark) FZ-2123, DOWSIL (trademark) FZ-2164 , DOWSIL (trademark) FZ-2191, DOWSIL (trademark) FZ-5609 Fluid, DOWSIL (trademark) L-7001, DOWSIL (trademark) L-7002, DOWSIL (trademark) L-7604, DOWSIL (trademark) SH3746 Fluid, DOWSIL (trademark) SH3771 Fluid, DOWSIL (trademark) SH8400 Fluid, DOWSIL (trademark) SF8410 Fluid, DOWSIL (trademark) SF8700 Fluid, SYLGARD (trademark) OFX-0309 Fluid, XIAMETER (trademark) OFX-0193 Fluid, XIAMETER (trademark) OFX-5211 Fluid, DOWSIL (trademark) Y-7006 (all manufactured by Dow Toray Industries, Ltd.), etc.

Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline Betaine, lauroyl propyl betaine, etc.

[Other ingredients]

The inorganic particle dispersion may contain silicon dioxide in addition to the inorganic particles X and the inorganic particles Y. The inorganic particle dispersion may contain an organic electrolyte and an additive. In addition, depending on the purpose and the method of use, it may contain a thickener, a thixotropic agent, a defoaming agent, a light stabilizer, a pigment, a mildewproof agent, a dustproof agent, an antifreeze performance improver, a weathering agent, an ultraviolet stabilizer, etc.

In the case where the inorganic particle dispersion contains an organic electrolyte, the content of the organic electrolyte is usually less than 0.01 parts by weight relative to 100 parts by weight of the liquid dispersion medium. The organic electrolyte in the present invention refers to an organic compound having an ionizable ionic group (excluding surfactants). For example, sodium p-toluenesulfonate, sodium benzenesulfonate, potassium butylsulfonate, sodium phenylphosphinate, sodium diethyl phosphate, etc. The organic electrolyte is preferably a benzenesulfonic acid derivative.

In the case where the inorganic particle dispersion liquid contains additives, for example, the surface treatment of the inorganic particles can be performed using appropriate additives. As additives, for example, additives having polar groups such as hydroxyl, oxy, carbonyl, carboxyl, and epoxy groups can be listed, which can be hydrogen-bonded or covalently bonded to the inorganic particles via these polar groups. As additives, for example, polycarboxylic acids and their salts, polymer unsaturated acid esters, modified or unmodified polyurethanes, modified or unmodified polyesters, modified or unmodified poly (methacrylates), (meth) acrylic copolymers, polyoxyethylene alkyl phosphates, and alkoxysilanes and alkoxysilane condensates listed as component (C), acrylic-urethane resins can be exemplified. The polymer additives are adsorbed on the surface of the inorganic particles to prevent re-agglomeration, so it is preferred to have an additive with an anchoring site anchored to the particle surface, and terminal modified polymers, grafted polymers, and block polymers can be listed as preferred structures. The surface treatment of the inorganic particles can be performed, for example, by mixing a liquid containing inorganic particles, additives, and a solvent.

<Method for producing inorganic fine particle dispersion>

The inorganic fine particle dispersion can be prepared by combining part or all of the steps of [Step 1] to [Step 10] described below in any order, but the method is not limited to these methods.

[Step 1] A step of obtaining a dispersion of inorganic particles X. The dispersion of inorganic particles X is obtained, for example, by hydrolysis and/or condensation of metal alkoxides, hydrolysis of metal salts, pulverization and/or crushing of metal oxides, precipitation of metal salt aqueous solutions, hydrothermal treatment of metal salt aqueous solutions, and mixing the inorganic particles X in a liquid dispersion medium and stirring to disperse them. In addition, as the dispersion of inorganic particles X, commercially available products can also be used.

[Process 2] is a process for obtaining a dispersion of inorganic particles Y. The dispersion of inorganic particles Y is obtained by, for example, hydrolysis of metal alkoxides and/or condensation thereof, hydrolysis of metal salts, crushing and/or crushing of metal oxides, precipitation of metal salt aqueous solutions, hydrothermal treatment of metal salt aqueous solutions, and mixing of inorganic particles Y into a liquid dispersion medium and stirring to disperse the inorganic particles Y. In addition, as the dispersion of inorganic particles Y, commercially available products may also be used.

[Process 3] A process for obtaining a first dispersion liquid. The first dispersion liquid comprises inorganic particles X and a first liquid dispersion medium. The first dispersion liquid may contain inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C, surfactant or other components contained in the inorganic particle dispersion liquid as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion of the amount. The first dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Process 4] A process for obtaining a second dispersion liquid. The second dispersion liquid comprises inorganic particles Y and a second liquid dispersion medium. The second dispersion liquid may contain inorganic particles X, liquid dispersion medium A, liquid dispersion medium B, water, component C, surfactant or other components contained in the inorganic particle dispersion liquid as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion of the amount. The second dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 5] A step of obtaining a third dispersion. The third dispersion comprises component C and a third liquid dispersion medium. The third dispersion may contain inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, a surfactant or other components contained in the inorganic particle dispersion as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion or a portion of the amount. The third dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 6] A step of obtaining a fourth dispersion. The fourth dispersion comprises a surfactant and a fourth liquid dispersion medium. The fourth dispersion may contain inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C or other components contained in the inorganic particle dispersion as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion or a portion of the amount. The fourth dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 7] A step of obtaining a fifth dispersion. The fifth dispersion comprises a liquid dispersion medium A and a fifth liquid dispersion medium. The fifth dispersion may contain inorganic particles X, inorganic particles Y, a liquid dispersion medium B, water, component C, a surfactant or other components contained in the inorganic particle dispersion as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion or a portion of the amount. The fifth dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 8] A step of obtaining a sixth dispersion. The sixth dispersion comprises a liquid dispersion medium B and a sixth liquid dispersion medium. The sixth dispersion may contain inorganic particles X, inorganic particles Y, a liquid dispersion medium A, water, component C, a surfactant or other components contained in the inorganic particle dispersion as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion or a portion of the amount. The sixth dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 9] A step of obtaining a seventh dispersion liquid. The seventh dispersion liquid comprises water and a seventh liquid dispersion medium. The seventh dispersion liquid may contain inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, component C, surfactants or other components contained in the inorganic particle dispersion liquid as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion liquid or a portion of the amount. The seventh dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

[Step 10] A step of obtaining an eighth dispersion. The eighth dispersion comprises other components contained in the inorganic particle dispersion and an eighth liquid dispersion medium. The eighth dispersion may contain inorganic particles X, inorganic particles Y, liquid dispersion medium A, liquid dispersion medium B, water, component C or a surfactant as required. In this case, the content of these components may be the total amount contained in the inorganic particle dispersion or a portion of the amount. The eighth dispersion medium may comprise a single liquid dispersion medium or a mixture of multiple liquid dispersion media.

In the above steps [Step 1] to [Step 10] and any other steps for preparing the inorganic fine particle dispersion, the inorganic fine particles can be dispersed particularly uniformly in the inorganic fine particle dispersion by applying a strong dispersion method such as ultrasonic dispersion or ultrahigh pressure dispersion.

In order to achieve more uniform dispersion, the inorganic particles in the dispersion of inorganic particles X and inorganic particles Y used in the preparation of the inorganic particle dispersion and the inorganic particle dispersion finally obtained are preferably in a colloidal state. As the dispersion medium, water or a volatile organic solvent can be used.

In addition, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing the inorganic fine particle dispersion, when the dispersion of inorganic fine particles X, the dispersion of inorganic fine particles Y, or both the dispersion of inorganic fine particles X and the dispersion of inorganic fine particles Y are colloidal alumina, in order to stabilize the positively charged alumina particles, it is preferred to add anions such as chloride ions, sulfate ions, acetate ions, etc. to the colloidal alumina as counter anions. The pH of the colloidal alumina is not particularly limited, but from the viewpoint of the stability of the inorganic fine particle dispersion, the pH is preferably 2 to 6.

In addition, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing the inorganic particle dispersion, when at least one of the inorganic particles X and the inorganic particles Y is aluminum oxide and the dispersion of the inorganic particles X or the inorganic particles Y or the inorganic particle dispersion is in a colloidal state, it is preferred to add anions such as chloride ions, sulfate ions, acetate ions, etc. to the dispersion.

In addition, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing the inorganic fine particle dispersion, when the dispersion of inorganic fine particles X, the dispersion of inorganic fine particles Y, or both the dispersion of inorganic fine particles X and the dispersion of inorganic fine particles Y are dispersions of colloidal silica, in order to stabilize the negatively charged silica particles, cations such as ammonium ions, alkali metal ions, and alkaline earth metal ions are preferably added to the colloidal silica as counter cations. The pH of the colloidal silica is not particularly limited.

In addition, in the above-mentioned steps [Step 1] to [Step 10] and any other steps for preparing the inorganic particle dispersion, when at least one of the inorganic particles X and the inorganic particles Y is silicon dioxide and the dispersion of the inorganic particles X or the inorganic particles Y or the inorganic particle dispersion is in a colloidal state, it is preferred to add cations such as ammonium ions, alkali metal ions, and alkaline earth metal ions to the dispersion.

As a preferred method when the inorganic particle dispersion contains component C, from the perspective of long-term stable storage and management of the coating agent, the following method can be listed: the inorganic particle dispersion is prepared in advance by dividing the inorganic particle dispersion into the following agent A and agent B, and the agent A and agent B are mixed immediately before coating to prepare the inorganic particle dispersion.

[Agent A]: contains inorganic fine particles and water, and may appropriately contain liquid dispersion medium A, liquid dispersion medium B, a surfactant, and other components.

[Agent B]: contains component C, and may appropriately contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components.

The agent A contains inorganic fine particles and water, and may contain a liquid dispersion medium A, a liquid dispersion medium B, a surfactant, and other components as appropriate.

When the total weight of Agent A is 100 mass %, the content of inorganic fine particles contained in Agent A is preferably 0.2 mass % to 30 mass %, more preferably 0.3 mass % to 20 mass %, and further preferably 0.5 mass % to 15 mass %.

When the total weight of Agent A is set to 100% by mass, as the lower limit of the water content contained in Agent A, it is preferably that it contains more than 1% by mass of water, more preferably that it contains more than 5% by mass of water, more preferably that it contains more than 10% by mass of water, and more preferably that it contains more than 15% by mass of water.

In addition, as the upper limit of the water content contained in Agent A, it is preferably 90% by mass or less of water, more preferably 80% by mass or less of water, more preferably 60% by mass or less of water, more preferably 50% by mass or less of water, more preferably 40% by mass or less of water, and more preferably 30% by mass or less of water.

The above-mentioned agent B contains component C and may contain liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components as appropriate. Regarding agent B, only component C may be used as agent B. In addition, agent B may be a composition containing component C and, as appropriate, further containing liquid dispersion medium A, liquid dispersion medium B, water, a surfactant, and other components.

The water content in Agent B is preferably small. When the total weight of Agent B is set to 100% by weight, the water content in Agent B is preferably 5% by weight or less, more preferably 3% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less.

When agent B is a composition as described above, when the total weight of agent B is set to 100 mass%, the content of component C is 0.002 mass% to 99.9 mass%, more preferably 0.5 mass% to 95 mass%, more preferably 1 mass% to 60 mass%, more preferably 3 mass% to 40 mass%, more preferably 3 mass% to 20 mass%, and more preferably 3 mass% to 15 mass%.

[Method for producing laminated body]

A laminate comprising a substrate and an inorganic particle layer can be obtained by a method comprising the steps of coating an inorganic particle dispersion on a substrate (coating step) and then removing a liquid dispersion medium from the inorganic particle dispersion coated on the substrate by an appropriate method to form an inorganic particle layer (hereinafter sometimes described as a "coating film") on the substrate (dispersion medium removal step).

＜Method of coating on substrate＞

There is no particular limitation on the method for coating the inorganic fine particle dispersion on the substrate, and examples thereof include gravure coating, reverse coating, brush roller coating, spray coating, lick roller coating, die coating, dipping, and bar coating.

As the substrate, plastic films or sheets, glass plates can be cited. As specific examples of plastic films or sheets, films or sheets of polyethylene terephthalate, polyethylene, polypropylene, cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate, polymethyl methacrylate, polycarbonate, polystyrene, MS resin, SAN resin, silicone resin, etc. can be cited. From the viewpoint of excellent transparency and no optical anisotropy, it is preferred to include films or sheets of triacetyl cellulose and polyethylene terephthalate, and glass plates. In addition, optical components such as polarizing plates, diffusion plates, light guide plates, brightness enhancement films, and reflective polarizing plates can also be used as substrates. The substrate can have a hard coating layer including ultraviolet curable resins, etc., and an antistatic layer containing conductive particles, etc. as a surface layer.

When glass is used as the substrate, there are no particular restrictions on the composition and manufacturing method of the glass that can be used. Soda glass, crystal glass, borosilicate glass, quartz glass, aluminosilicate glass, borate glass, phosphate glass, alkali-free glass, composite glass with ceramics, etc. can be used.

Before applying the inorganic fine particle dispersion onto the substrate, the surface of the substrate may be subjected to pretreatment such as corona treatment, ozone treatment, plasma treatment, flame treatment, electron beam treatment, anchor coating treatment, cleaning treatment, etc.

<Method for removing liquid dispersion medium>

The inorganic particle layer can be formed on the surface of the substrate by removing the liquid dispersion medium from the inorganic particle dispersion applied on the surface of the substrate (dispersion medium removal step). The removal of the liquid dispersion medium can be performed, for example, by natural drying at room temperature and then heating under normal pressure or reduced pressure.

The pressure and heating temperature when removing the liquid dispersion medium can be appropriately selected according to the materials used (i.e., inorganic particles X, inorganic particles Y and liquid dispersion medium). For example, it can be dried usually at a temperature of 50°C or more and 120°C or less, preferably at a temperature of about 60°C or more and about 110°C or less. In one embodiment, it can be dried at a temperature of 50°C or more and 80°C or less, and in one embodiment, it can be dried at a temperature of 20°C or more and 50°C or less.

After the liquid dispersion medium is removed by the above-mentioned drying, the substrate having the inorganic particle layer formed on the surface may be further subjected to heat treatment to improve the adhesion between the substrate and the inorganic particle layer (heat treatment step). There is no particular limitation on the heat treatment method. Examples include heating in an oven, local heating of the inorganic particle layer by electromagnetic wave irradiation, etc.

When heat treatment is further performed after the drying (heat treatment step), the heating temperature, atmosphere and heating time are not particularly limited. The heat treatment temperature is preferably 500° C. or higher and 800° C. or lower.

The atmosphere during heating is preferably air, and the heating time is preferably 10 minutes or less.

In one embodiment of the inorganic fine particle dispersion of the present invention, the inorganic fine particle dispersion may be applied to the glass substrate before the quenching step in the manufacture of the glass substrate, and the glass substrate coated with the inorganic fine particle dispersion may be directly quenched.

[Laminated body]

In one embodiment, the inorganic particle layer of the laminated body including the substrate and the inorganic particle layer obtained by the above method has an anti-reflection function. The thickness of the inorganic particle layer is not particularly limited. In one embodiment, the thickness of the inorganic particle layer is more than 40nm and less than 300nm, in another embodiment, the thickness of the inorganic particle layer is more than 50nm and less than 240nm, in another embodiment, the thickness of the inorganic particle layer is more than 50nm and less than 220nm, in another embodiment, the thickness of the inorganic particle layer is more than 80nm and less than 200nm, in another embodiment, the thickness of the inorganic particle layer is more than 50nm and less than 150nm, in another embodiment, the thickness of the inorganic particle layer is more than 80nm and less than 130nm.

The thickness of the inorganic particle layer is preferably 50 nm or more and 240 nm or less, more preferably 50 nm or more and 220 nm or less, and further preferably 80 nm or more and 200 nm or less. The thickness of the inorganic particle layer can be adjusted by changing the amount of the inorganic particle X and the inorganic particle Y in the inorganic particle dispersion and the coating amount of the inorganic particle dispersion.

On the inorganic fine particle layer formed by coating the inorganic fine particle dispersion, an antifouling layer containing a fluorine-containing compound or the like may be further formed. As a method for forming the antifouling layer, a dip coating method may be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.

The main materials used are described below.

[Base material]

Slide glass (manufactured by Azowan Co., Ltd.; soda-lime glass; transmittance: 89%; width 26 mm, length 76 mm, thickness 1.3 mm) The slide glass having a transmittance of 89% is referred to as substrate-1.

Slide glass (transmittance: 88.6%; width 26 mm, length 76 mm, thickness 1.3 mm) The slide glass having a transmittance of 88.6% is referred to as substrate-2.

The transmittance value of the slide glass used as the substrate is measured by the method described in the section [Transmittance] of the following Examples.

[Inorganic particles]

The following dispersion liquid was used as the inorganic fine particles.

Particle-1 (inorganic fine particles Y): Snowtex (registered trademark) ST-OUP (manufactured by Nissan Chemical Industries, Ltd.; an aqueous dispersion of colloidal silica fine particle chains formed by three or more particles having a particle size of 5 nm or more and 20 nm or less connected in a chain; an average particle size of 40 nm or more and 300 nm or less as determined by a dynamic light scattering method; a solid content concentration of 15% by weight)

Particle-2 (inorganic fine particles X): Snowtex (registered trademark) ST-OXS (manufactured by Nissan Chemical Industries, Ltd.; aqueous dispersion of colloidal silica; average particle size of 4 nm to 6 nm; solid content concentration of 10 wt%)

The numerical values of the addition amounts of the inorganic fine particles in Table 1-1, Table 1-2, and Table 1-3 are the addition amounts at the solid content concentration when the total amount of the composition (total amount of the dispersion) is 100% by mass.

[Liquid dispersion medium A]

As the liquid dispersion medium A, the following was used.

Liquid A-1: 2-methoxyethyl acetate (boiling point 143°C)

Liquid A-2: 4-methyl-2-pentanone (boiling point 116°C)

Liquid A-3: 1-methoxy-2-propanol (boiling point 120°C)

Liquid A-4: 4-ethylmorpholine (boiling point 139°C)

Liquid A-5: Isoamyl acetate (boiling point 141°C)

Liquid A-6: Propylene glycol 1-monomethyl ether 2-acetate (boiling point 146°C)

Liquid A-7: 1-propoxy-2-propanol (boiling point 149°C)

Liquid A-8: N,N-dimethylformamide (boiling point 153°C)

Liquid A-9: 2-ethoxyethyl acetate (boiling point 156°C)

Liquid A-10: dimethyl sulfoxide (boiling point 189°C)

Liquid A-11: γ-butyrolactone (boiling point 204°C) (Comparative Example)

Liquid A-12: Ethylene carbonate (boiling point 244°C) (Comparative Example)

Liquid A-13: 1,6-diacetoxyhexane (boiling point 260°C) (Comparative Example)

Liquid A-14: dipropylene glycol dimethyl ether (boiling point 175°C)

Liquid A-15: Tetrahydrofurfuryl alcohol (boiling point 176°C)

Liquid A-16: 3-methoxy-3-methylbutanol (boiling point 174°C)

Liquid A-17: 3-methoxy-1-butanol (boiling point 158°C)

Liquid A-18: 1-butanol (boiling point 118°C)

[Liquid dispersion medium B]

Liquid B-1: Ethanol (boiling point 78°C)

Liquid B-2: Isopropyl alcohol (boiling point 82°C)

[Ingredient C, surfactant and other ingredients, etc.]

Component-1: BYK (registered trademark)-349 (manufactured by BYK Chemical Japan Co., Ltd.; polyether-modified siloxane)

Component-2: a dispersion of an alkoxysilane condensate in which a plurality of Si-O-Si bonds are three-dimensionally connected (the peak molecular weight of the alkoxysilane condensate is 700; the content of the alkoxysilane condensate in the dispersion is 2% by weight; more than half of the terminals of the alkoxysilane condensate are hydroxyl groups; an acrylic-urethane resin is contained as an additive). Hereinafter, the alkoxysilane condensate in Component-2 may be referred to as "Component C-3".

Ingredient-3: Silquest (registered trademark) A-187J (manufactured by Momentive Advanced Materials Japan Co., Ltd.; γ-glycidoxypropyltrimethoxysilane)

Ingredient-4: MKC Silicate (registered trademark) MS56S (manufactured by Mitsubishi Chemical Corporation; polymethoxysiloxane)

The laminated bodies including the glass substrate and the inorganic fine particle layer in the examples and comparative examples were produced by the following method.

Examples 1 to 29 and Comparative Examples 1 to 8

The inorganic particle dispersion liquid was prepared by stirring a mixture of inorganic particles, liquid dispersion medium A, liquid dispersion medium B, water, component C, surfactant, and other components in a manner that the component ratios described in Table 1-1, Table 1-2, and Table 1-3 were obtained. Next, a substrate was prepared in which one side of the substrate was masked using a masking tape. Here, substrate-1 was used as the substrate.

Using a micro-speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), for the above-mentioned substrate subjected to masking treatment, the prepared inorganic particle dispersion is applied to the side of the substrate that is not subjected to masking treatment. After coating, the masking tape is removed from the substrate and dried naturally at room temperature. For the obtained substrate, an oven is used to perform a heat treatment at 100°C/3 minutes in air, and then a muffle furnace is used to perform a heat treatment at 700°C/2 minutes in air, thereby forming an inorganic particle layer on the substrate, thereby obtaining a laminate comprising a substrate and an inorganic particle layer.

Embodiments 30 to 32

The mixture containing inorganic particles, liquid dispersion medium A, liquid dispersion medium B and component-1 was stirred in a manner to form the component ratios described in Tables 1-4, and then component-4 was added and stirred, thereby preparing an inorganic particle dispersion liquid. In addition, a substrate having a single-sided side of the substrate masked by a masking tape was prepared. Here, substrate-2 was used as the substrate.

Using a slow dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), for the above-mentioned substrate subjected to masking treatment, the prepared inorganic particle dispersion is immediately applied to the side of the substrate that is not subjected to masking treatment. After coating, the masking tape is removed from the substrate and dried naturally at room temperature. For the obtained substrate, an oven is used to heat the substrate at 100°C for 3 minutes in air, and then a muffle furnace is used to heat the substrate at 700°C for 2 minutes in air, thereby forming an inorganic particle layer on the substrate, thereby obtaining a laminate comprising a substrate and an inorganic particle layer. The results are summarized and shown in Table 1-4.

Embodiment 33

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. A mixture comprising grain-1 and grain-2 was prepared in a manner where the value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silica solid content was 2.59 mass %. The obtained mixture comprising grain-1 and grain-2, liquid dispersion medium A (1.30 mass %), liquid dispersion medium B (71.19 mass %) and component-1 (0.25 mass %) were stirred. Then, a mixture of component-4 (0.39 mass %) and liquid dispersion medium B (7.48 mass %) was added to the obtained agitator and stirred, thereby preparing an inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, a laminate comprising a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized and shown in Table 1-4.

Embodiment 34

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. A mixture comprising grain-1 and grain-2 was prepared in a manner where the value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silica solid content was 2.59 mass %. The obtained mixture comprising grain-1 and grain-2 was mixed with liquid dispersion medium A (5.18 mass %), liquid dispersion medium B (67.31 mass %) and component-1 (0.25 mass %) and stirred. Then, a mixture of component-4 (0.39 mass %) and liquid dispersion medium B (7.48 mass %) was added to the obtained agitator and stirred, thereby preparing an inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, a laminate comprising a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized and shown in Table 1-4.

Embodiment 35

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. The value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silica solid content was 2.59 mass % when the obtained inorganic particle dispersion was set to 100.0 mass %, and the particle-1 and particle-2 were weighed, and their mixture was prepared. The obtained mixture comprising particle-1 and particle-2, liquid dispersion medium A (10.35 mass %), liquid dispersion medium B (62.14 mass %) and component-1 (0.25 mass %) were stirred. Then, the mixture comprising liquid dispersion medium B (7.48 mass %) and component-4 (0.39 mass %) was added to the obtained agitator and stirred, thus preparing inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, the laminated body comprising substrate and inorganic particle layer was obtained by the same method as Example 30. The results are summarized in Tables 1-4.

Embodiment 36

The mixture containing inorganic particles, liquid dispersion medium A, liquid dispersion medium B and component-1 was stirred in a manner to become the component ratio recorded in Table 1-4, and then component-4 was added and stirred, thereby preparing an inorganic particle dispersion liquid. Using the obtained inorganic particle dispersion liquid, a laminate containing a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized and shown in Table 1-4.

Embodiment 37

The mixture containing inorganic particles, liquid dispersion medium A, liquid dispersion medium B and component-1 was stirred in a manner to form the component ratios described in Tables 1-4, and then component-4 was added and stirred to prepare an inorganic particle dispersion liquid. In addition, a substrate having a single-sided side of the substrate masked by a masking tape was prepared. Here, substrate-2 was used as the substrate.

Using a micro-speed dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), for the above-mentioned substrate subjected to masking treatment, the prepared inorganic particle dispersion is immediately applied to the side of the substrate that is not subjected to masking treatment. After coating, the masking tape is removed from the substrate and dried naturally at room temperature. For the obtained substrate, an oven is used to heat the substrate at 100°C for 3 minutes in air, and then a muffle furnace is used to heat the substrate at 700°C for 2 minutes in air, thereby forming an inorganic particle layer on the substrate, thereby obtaining a laminate comprising a substrate and an inorganic particle layer. The results are summarized and shown in Table 1-4.

Embodiment 38

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. Grain-1 and grain-2 were weighed in a manner where the value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silicon dioxide solid content was 2.59 mass %, and their mixture was prepared. The obtained mixture comprising grain-1 and grain-2 was mixed with liquid dispersion medium A (5.18 mass %), liquid dispersion medium B (67.31 mass %) and component-1 (0.25 mass %) and stirred. A mixture comprising liquid dispersion medium B (7.48 mass %) and component-4 (0.39 mass %) was added to the obtained agitator and stirred, thereby preparing inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, a laminate comprising a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized and shown in Table 1-4.

Embodiment 39

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. Grain-1 and grain-2 were weighed in a manner where the value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silicon dioxide solid content was 2.59 parts by weight, and their mixture was prepared. The obtained mixture comprising grain-1 and grain-2 was mixed with liquid dispersion medium A (5.18 mass %) and liquid dispersion medium B (67.55 mass %) and stirred. A mixture comprising liquid dispersion medium B (7.24 mass %), component-1 (0.25 mass %) and component-4 (0.39 mass %) was added to the obtained agitator and stirred, thereby preparing an inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, a laminate comprising a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized and shown in Table 1-4.

Embodiment 40

The preparation of inorganic particle dispersion (100.0 mass %) was implemented as follows. Grain-1 and grain-2 were weighed in a manner such that the value of (mass of inorganic particle Y)/[(mass of inorganic particle X)+(mass of inorganic particle Y)] was 0.75 and the silicon dioxide solid content was 2.59 mass %, and their mixture was prepared. The obtained mixture comprising grain-1 and grain-2 was mixed with liquid dispersion medium A (1.43 mass %) and liquid dispersion medium B (29.20 mass %) and stirred. A mixture comprising liquid dispersion medium A (3.75 mass %), liquid dispersion medium B (45.59 mass %), component-1 (0.25 mass %) and component-4 (0.39 mass %) was added to the obtained agitator and stirred, thereby preparing inorganic particle dispersion (100.0 mass %). Using the obtained inorganic particle dispersion, a laminate comprising a substrate and an inorganic particle layer was obtained by the same method as Example 30. The results are summarized in Tables 1-4.

Embodiments 41 to 48

The mixture containing inorganic particles, liquid dispersion medium A, liquid dispersion medium B and component-1 was stirred in a manner to form the component ratios described in Tables 1-4 and 1-5, and then component-4 was added and stirred to prepare an inorganic particle dispersion liquid. In addition, a substrate having a single-sided side of the substrate masked by a masking tape was prepared. Here, substrate-2 was used as the substrate.

Using a slow dip coater MD-0408-01 (manufactured by SDI Co., Ltd.), for the above-mentioned substrate subjected to masking treatment, the prepared inorganic particle dispersion is immediately applied to the side of the substrate that is not subjected to masking treatment. After coating, the masking tape is removed from the substrate and dried naturally at room temperature. For the obtained substrate, an oven is used to heat the substrate at 100°C for 3 minutes in air, and then a muffle furnace is used to heat the substrate at 700°C for 2 minutes in air, thereby forming an inorganic particle layer on the substrate, thereby obtaining a laminate comprising a substrate and an inorganic particle layer. The results are summarized and shown in Tables 1-4 and 1-5.

Evaluations of Examples and Comparative Examples were performed by the following methods.

[Spectral transmittance]

The total light transmittance of the laminate including the substrate and the inorganic fine particle layer was measured using an ultraviolet-visible-near-infrared spectrophotometer UV-3150 (manufactured by Shimadzu Corporation). Then, the total light transmittance value in the region of wavelengths of 380 nm or more and 1100 nm or less was read from the obtained total light transmittance spectrum, and the average value was calculated.

The spectral transmittance of the resulting laminate was observed to increase relative to the uncoated substrate. The increase in spectral transmittance is defined as shown below.

[Increase in spectral transmittance (%)]

=[spectral transmittance of the laminate (%)] - [spectral transmittance of the uncoated substrate (%)]

[Coating strength] (Adhesion of the coating to the substrate)

Cellotape (registered trademark) LP-24 (manufactured by Michibon Co., Ltd.) is pasted on the surface of the laminated body including the substrate and the inorganic particle layer where the inorganic particle layer exists, and it is peeled off. At this time, if the adhesive component of Cellotape is transferred to the surface where the inorganic particle layer exists, it can be said that the inorganic particle layer adheres to the substrate very strongly, and the evaluation in this case is recorded as "◎". In addition, in the case where the adhesive component of Cellotape is not transferred to the surface where the inorganic particle layer exists and the substrate is irradiated with light without generating reflection peculiar to the inorganic particle layer, the inorganic particles are transferred to Cellotape, and it can be said that the inorganic particle layer adheres to the substrate weakly, and the evaluation in this case is recorded as "×". In addition, in the case where the adhesive component of Cellotape is not transferred to the surface where the inorganic particle layer exists and generates reflection peculiar to the inorganic particle layer, the inorganic particle layer adheres to the substrate, but it can be said that the adhesion is not as strong as the case of "◎", and the evaluation in this case is recorded as "○".

[Storage stability of inorganic fine particle dispersion]

The inorganic particle dispersions in the embodiments and comparative examples were stored in an oven at 40°C in air for 28 days to confirm the storage stability of the inorganic particle dispersions. As a result, if the liquid state is maintained, it can be said that the storage stability is good, and the evaluation in this case is recorded as "0". In addition, if gelation occurs, it can be said that the storage stability is poor, and the evaluation in this case is recorded as "×". In the embodiments 1 to 48 (and comparative examples 1 to 7) described in Tables 1-1, 1-2, 1-3, 1-4, and 1-5, the storage stability is all "0".

[Table 1-5]

Industrial Applicability

According to the present invention, it is possible to provide an inorganic fine particle dispersion which can form a coating film having high light transmittance and high coating film strength (high adhesion of the coating film to a substrate) and has good storage stability.

According to the present invention, it is also possible to provide a laminate with high light transmittance and high film strength (film to substrate high adhesion). In addition, the film of the present invention is by the silanol group on the silicon dioxide contained in the film, and the hydrophilicity of the film surface is high, and it also has the antifouling performance of washing away dirt with water and rainwater. These films can be used as anti-reflection film, anti-fouling film, anti-fouling film, etc., and can be appropriately used for various films such as anti-reflection film and anti-fouling film, anti-reflection film for display, anti-fog film of agricultural film (plastic greenhouse) on the surface of the protective glass of solar cells, various housing equipment machine parts, various agricultural parts, various industrial parts, various building materials parts, various parts of household appliances, various automotive interior parts and exterior parts, etc., in the fields of industries such as building construction industry, transportation machinery industry, electrical and electronic industry, household goods, there is high industrial practicality.

Claims (15)

1. An inorganic fine particle dispersion liquid, comprising:

inorganic particles,

A liquid dispersion medium A having a boiling point of 100 ℃ or higher and 190 ℃ or lower (excluding water), and

a liquid dispersion medium B having a boiling point of less than 100 ℃,

wherein,,

when the total amount of the inorganic fine particle dispersion liquid is 100% by mass, the content of the liquid dispersion medium a is 0.5% by mass or more and less than 15% by mass.

2. The inorganic fine particle dispersion according to claim 1, wherein the content of the liquid dispersion medium B is 20 mass% or more and 85 mass% or less, based on 100 mass% of the total amount of the inorganic fine particle dispersion.

3. The inorganic fine particle dispersion liquid according to claim 1 or 2, wherein the liquid dispersion medium B is an alcohol.

4. The inorganic fine particle dispersion liquid according to any one of claims 1 to 3, wherein the inorganic fine particle dispersion liquid further comprises water.

5. The inorganic fine particle dispersion according to claim 4, wherein the water content is 5 mass% or more and 55 mass% or less, based on 100 mass% of the total inorganic fine particle dispersion.

6. The inorganic fine particle dispersion liquid according to any one of claims 1 to 5, wherein the inorganic fine particle dispersion liquid further comprises an alkoxysilane and/or a condensate thereof.

7. The inorganic fine particle dispersion according to any one of claims 1 to 5, wherein the inorganic fine particle dispersion further comprises at least one selected from the group consisting of an alkoxysilane, an alkoxysilane condensate in which a plurality of Si-O-Si bonds are linearly linked, and an alkoxysilane condensate in which a plurality of Si-O-Si bonds are three-dimensionally linked.

8. The inorganic fine particle dispersion liquid according to any one of claims 1 to 7, wherein the liquid dispersion medium a is an alcohol.

9. The inorganic fine particle dispersion liquid according to any one of claims 1 to 8, wherein the inorganic fine particle dispersion liquid further comprises a surfactant.

10. The inorganic fine particle dispersion liquid according to any one of claims 1 to 8, wherein the inorganic fine particle dispersion liquid further comprises a surfactant comprising a polyether-modified siloxane.

11. The inorganic fine particle dispersion liquid according to any one of claims 1 to 10, wherein the inorganic fine particles are colloidal silica.

12. The inorganic fine particle dispersion according to any one of claims 1 to 11, wherein the content of the inorganic fine particles is 0.1 mass% or more and 10 mass% or less, based on 100 mass% of the total amount of the inorganic fine particle dispersion.

13. A method for producing a laminate, comprising the steps of:

A step of applying the inorganic fine particle dispersion liquid according to any one of claims 1 to 12 to a substrate (coating step); and

and a step (dispersion medium removal step) of removing the liquid dispersion medium a and the liquid dispersion medium B from the inorganic fine particle dispersion liquid applied to the substrate to form an inorganic fine particle layer on the substrate.

14. The method for producing a laminate according to claim 13, further comprising a heat treatment step after the dispersion medium removal step.

15. A laminate, wherein the laminate is obtained by the method of claim 13 or 14, and the laminate comprises a substrate and an inorganic particulate layer.