JP2019147928A - Aqueous coating material, film and production method thereof, laminate and production method thereof, and aqueous coating material kit - Google Patents

Abstract

To provide an aqueous coating material excellent in light permeability of the resulting film.SOLUTION: The aqueous coating material includes: water; at least one kind of compound selected from the group consisting of a siloxane compound represented by formula 1, a hydrolysate of the siloxane compound represented by formula 1 and a hydrolysis condensate of the siloxane compound represented by formula 1; a surfactant; and a core-shell particle including a nonpolar solvent as a core material in which the surfactant includes at least one kind of surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less; and the total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5 mass% to 70 mass% based on the total mass of the nonpolar solvent. A film using the aqueous coating material and a production method thereof are provided. A laminate and a production method thereof are provided. An aqueous coating material kit capable of producing the aqueous coating material is provided.SELECTED DRAWING: None

Description

  The present disclosure relates to an aqueous coating material, a film and a manufacturing method thereof, a laminate and a manufacturing method thereof, and an aqueous coating material kit.

An aqueous coating material containing a siloxane compound uses a solvent containing water, and is used for various applications because the formed film has low surface energy and excellent transparency.
As its application, it is suitably used for optical lenses, optical filters, flat films for thin film transistors (TFT) of various displays, antireflection films, anticondensation films, antifouling films, surface protective films, and the like.

In recent years, solar cell modules, which are power generation methods with a low environmental load during power generation, have attracted attention. A solar cell module generally includes a solar cell in which a solar cell element is sealed with a surface protective material, a sealing material, and a back surface side base material in order from a light receiving surface side (front surface side) on which sunlight is incident. Yes.
In general, glass, a weather-resistant resin film, or the like is used as a surface protective material provided on the light receiving surface of the solar cell module.

Examples of conventional surface protective materials or methods for producing surface protective materials include those described in Patent Document 1 or 2.
In Patent Document 1, 1) an organic compound A; an emulsion stabilizer C; and an aqueous medium having a pH of 2-6 are mixed at a C / A mass ratio of 0.1-2. A step of preparing an oil-in-water emulsion by forming 1 to 50% by mass of emulsified droplets of 30 to 300 nm, wherein the particle size is a Z-average hydrodynamic diameter measured by DLS And 2) adding an inorganic oxide shell layer to the emulsified droplets by adding at least one inorganic oxide precursor to the emulsion obtained in step 1), resulting in a core / shell mass. Forming organic-inorganic core / shell nanoparticles having a ratio of 0.2 to 25, wherein the core is the sum of compound A and emulsion stabilizer C, and the shell is an inorganic oxide precursor; Shii and a step which is a metal oxide, a process for producing an antireflective coating composition, Compound A is a non-polar organic compound having a water solubility of 5 kg / m ³ at most, and the emulsion Stabilizer C is a cationic addition copolymer comprising at least one monomer unit having a cationic charge and at least one monomer unit that is neutral or nonionic and has an overall positive zeta potential. There is a process described.

  Patent Document 2 discloses an optical coating film formed of a coating film formed on a substrate, wherein the coating film has a major axis (L) and a maximum value (D) of a minor axis perpendicular to the major axis (L). Average value: ((L + D) / 2) has voids (X) of 20 nm or more, the major axis (L) and minor axis (D) of the voids (X) are 1 <L / D, An optical coating is described in which the gap (X) is non-contact with the substrate at the interface with the substrate.

  Examples of the conventional method for producing hollow particles or hollow particle dispersions include those described in Patent Document 3 or 4.

  Patent Document 3 discloses a step of synthesizing core / shell type particles in which the main component of the core is an organic compound and the main component of the shell is an inorganic compound in an aqueous medium, and the synthesized core / shell type particles are organic. A method for producing hollow particles, comprising: a step of dispersing in a solvent; and a step of heating the core / shell particles dispersed in the organic solvent to remove the core to produce hollow particles. Have been described.

  Patent Document 4 discloses that the main component of the core is an organic compound, the main component of the shell is an inorganic compound, and a shell having an average thickness of 2 nm or more and 10 nm or less is generated and the core / shell type particles are dispersed in an aqueous medium. And a step of hydrophobizing the core / shell type particles and extracting them with an aromatic organic solvent to obtain a dispersion of hollow particles formed of shells. A method for producing a dispersion of hollow particles is described.

Special table 2017-500384 gazette JP 2014-203006 A JP 2013-226539 A JP 2014-34488 A

The problem to be solved by the embodiments of the present invention is to provide an aqueous coating material that is excellent in light transmittance of the obtained film.
The problem to be solved by another embodiment of the present invention is to provide a film using the above aqueous coating material and a method for producing the same, and a laminate and a method for producing the same.
The problem to be solved by still another embodiment of the present invention is to provide an aqueous coating material kit capable of producing the above aqueous coating material.

Means for solving the above problems include the following aspects.
<1> Selected from the group consisting of water, a siloxane compound represented by the following formula 1, a hydrolyzate of the siloxane compound represented by the following formula 1, and a hydrolysis condensate of the siloxane compound represented by the following formula 1. At least one compound, a surfactant, and a core-shell particle containing a nonpolar solvent as a core material, and the surfactant is a cationic surfactant having a molecular weight of 10,000 or less and a nonionic interface having a molecular weight of 10,000 or less The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less, which contains at least one surfactant selected from the group consisting of surfactants, is that of the nonpolar solvent. An aqueous coating material that is 0.5% by mass or more and 70% by mass or less with respect to the total mass.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

<2> The aqueous coating material according to <1>, wherein the surfactant includes a cationic surfactant having a molecular weight of 10,000 or less.
<3> The aqueous coating material according to <1> or <2>, wherein the nonpolar solvent is a hydrocarbon having 7 or more carbon atoms.
<4> The aqueous coating material according to any one of <1> to <3>, wherein a coefficient of variation of the particle diameter of the core-shell particles is 100% or less.
<5> The aqueous coating material according to any one of <1> to <4>, wherein the surface of the core-shell particles is hydrophilic.
<6> A coating layer formed on a base material is dried, and the coating layer is composed of water, a hydrolysis condensate of a siloxane compound represented by Formula 1, a surfactant, and a nonpolar solvent as a core material. Including the core-shell particles, and the surfactant includes at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less, The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass or less with respect to the total mass of the nonpolar solvent. A film having voids in at least some of the core-shell particles in the coating layer.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

<7> The film according to <6>, wherein the average internal void diameter of the film is 30 nm or more, and the variation coefficient of the void diameter is 60% or less.
<8> The film according to <6> or <7>, which is an antireflection film.
<9> A laminate having the film according to any one of <6> to <8>.
<10> The laminate according to <9>, having the film on a substrate.
<11> The laminate according to <10>, wherein the substrate is a resin substrate.
<12> The laminate according to any one of <9> to <11>, which is a solar cell front sheet.
<13> The core-shell particle including a step of forming a coating layer by applying the aqueous coating material according to any one of <1> to <5> on a substrate, and a step of drying the coating layer A method for producing a film in which at least a part of the film becomes hollow particles that form voids inside the coat layer after the drying step.
<14> The core-shell particle including a step of forming a coating layer by applying the aqueous coating material according to any one of <1> to <5> on a substrate, and a step of drying the coating layer The manufacturing method of the laminated body from which at least one part becomes a hollow particle which forms a space | gap inside the said coat layer after the said drying process.
<15> A composition A containing a siloxane compound represented by the following formula 1 and a composition B containing water, a surfactant, and a nonpolar solvent, wherein the surfactant has a molecular weight of 10,000 or less. The composition B contains at least one surfactant selected from the group consisting of a cationic surfactant and a nonionic surfactant having a molecular weight of 10,000 or less, and the cationic surfactant having a molecular weight of 10,000 or less and a molecular weight of 10,000 in the composition B The aqueous coating material kit whose total content of the following nonionic surfactant is 0.5 mass% or more and 70 mass% or less with respect to the total mass of the said nonpolar solvent.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

According to the embodiment of the present invention, it is possible to provide an aqueous coating material that is excellent in light transmittance of the obtained film.
According to other embodiment of this invention, the film | membrane using the said aqueous | water-based coating material, its manufacturing method, a laminated body, and its manufacturing method can be provided.
According to still another embodiment of the present invention, an aqueous coating material kit capable of producing the above aqueous coating material can be provided.

Hereinafter, the contents of the present disclosure will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In addition, in this specification, "-" which shows a numerical range is used by the meaning containing the numerical value described before and behind that as a lower limit and an upper limit.
In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
Moreover, in the description of groups (atomic groups) in this specification, the description that does not indicate substitution and non-substitution includes those that have a substituent as well as those that do not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the term “process” in this specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term is used as long as the intended purpose of the process is achieved. included. In the present disclosure, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer and converted using polystyrene as a standard substance.
Hereinafter, the present disclosure will be described in detail.

(Water-based coating material)
An aqueous coating material according to the present disclosure includes water, a siloxane compound represented by the following formula 1, a hydrolyzate of the siloxane compound represented by the following formula 1, and a hydrolytic condensation of the siloxane compound represented by the following formula 1. At least one compound selected from the group consisting of a product, a surfactant, and core-shell particles containing a nonpolar solvent as a core material, the surfactant having a molecular weight of 10,000 or less and a cationic surfactant and a molecular weight A total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less, comprising at least one surfactant selected from the group consisting of 10,000 or less nonionic surfactants And 0.5 mass% or more and 70 mass% or less with respect to the total mass of the nonpolar solvent.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, or a styryl group ( (Vinylphenyl group), (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide, polyoxyalkylene group, carboxy group and organic having a group selected from the group consisting of quaternary ammonium groups Represents a group, each m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

As a result of intensive studies by the present inventors, it has been found that by adopting the above-described configuration, an aqueous coating material having excellent light transmittance of a film obtained and a laminate using the obtained film can be provided.
Although the mechanism of the excellent effect by the above configuration is not clear, it is estimated as follows.
The present inventors have found that the conventional water-based coating material does not yet have sufficient light transmittance of the obtained film.
At least one selected from the group consisting of the siloxane compound represented by the above formula 1, the hydrolyzate of the siloxane compound represented by the above formula 1, and the hydrolysis condensate of the siloxane compound represented by the above formula 1. (Hereinafter also referred to as “specific siloxane compound”), a surfactant, and a core-shell particle containing a non-polar solvent as a core material, the surfactant having a molecular weight of 10,000 or less and a molecular weight of 1 The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less, comprising at least one surfactant selected from the group consisting of 10,000 or less nonionic surfactants, The surfactant is present at the time of drying when forming a film by being 0.5% by mass or more and 70% by mass or less with respect to the total mass of the nonpolar solvent. Further, at least a part of the nonpolar solvent is volatilized, and voids can be easily formed in the obtained film, and the presence of the surfactant makes the nonpolar solvent into film properties. It is presumed that the nonpolar solvent is excellent in volatility even at a low temperature below the boiling point, and the light transmittance of the film obtained by the voids is excellent. In addition, by reducing the refractive index of the obtained film, the antireflection effect for the substrate provided with the obtained film is also improved, and it is presumed that the laminate having the obtained film on the substrate is also excellent in light transmittance. Is done.
Further, the aqueous coating material according to the present disclosure is such that the surfactant is at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less. The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass or less with respect to the total mass of the nonpolar solvent. By being, it is excellent also in the haze (degree of cloudiness) of the film | membrane obtained.

<Surfactant>
The aqueous coating material according to the present disclosure includes a surfactant, and the surfactant is at least one selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less. The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass with respect to the total mass of the nonpolar solvent. It is below mass%.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant that is an ionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like, but the aqueous coating material according to the present disclosure has at least a molecular weight. Including a cationic surfactant having a molecular weight of 10,000 or less, a nonionic surfactant having a molecular weight of 10,000 or less, or both.
Among these, it is preferable to contain a cationic surfactant having a molecular weight of 10,000 or less from the viewpoints of storage stability and light transmittance and haze of the resulting film.

The molecular weight of the cationic surfactant or nonionic surfactant is preferably 5,000 or less, preferably 2,000 or less, from the viewpoints of storage stability and light transmittance and haze of the resulting film. Is more preferably 1,000 or less, and particularly preferably 300 or more and 800 or less.
The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass or less, based on the total mass of the nonpolar solvent, and stored. From the viewpoints of stability and light transmittance and haze of the resulting film, it is preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 35% by mass or less.

The cationic surfactant represents a compound having a cationic site in the molecule and having surface activity. Examples of the cationic site include an aminic nitrogen atom, an aromatic heterocyclic nitrogen atom, a boron atom having four bonds with carbon, and a phosphorus atom. Of these, an amine nitrogen atom or an aromatic heterocyclic nitrogen atom is preferred. Among these, a quaternary nitrogen atom is particularly preferable.
Examples of the cationic surfactant include quaternary ammonium salt compounds, alkylpyridinium salt compounds, alkylamine salt compounds, benzalkonium salt compounds, benzethonium salt compounds, imidazolium salt compounds, and polyethyleneimine.
Among them, at least one cationic interface selected from the group consisting of a quaternary ammonium salt compound, an alkylpyridinium salt compound, and polyethyleneimine from the viewpoint of storage stability and light transmittance and haze of the resulting film. Activators are preferred, and at least one cationic surfactant selected from the group consisting of quaternary ammonium salt compounds and alkylpyridinium salt compounds is more preferred.
Further, the cationic surfactant is preferably a compound having an alkyl group having 8 to 24 carbon atoms from the viewpoint of storage stability and light transmittance and haze of the resulting film, and has 12 to 22 carbon atoms. The compound having an alkyl group is more preferable, and the compound having an alkyl group having 14 to 20 carbon atoms is particularly preferable.

  Specific examples of the cationic surfactant include hexadecylpyridinium chloride, hexadecylpyridinium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyldodecyldimethylammonium bromide, benzyldimethyltetradecylammonium chloride, benzyloctadecyldimethyl. Ammonium chloride, stearyltrimethylammonium bromide, benzyldimethylhexadecylammonium chloride, dimethyldipalmitylammonium bromide, dimethyldioctadecylammonium bromide, trimethylamine hydrochloride, benzalkonium chloride, dodecyldimethylbenzylammonium chloride, benzethonium chloride, polyethyleneimine, etc. Preferred It is.

Examples of nonionic surfactants include polyalkylene glycol monoalkyl ether, polyalkylene glycol monoalkyl ester, polyalkylene glycol monoalkyl ester / monoalkyl ether, and the like. More specifically, polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, polyethylene glycol monostearyl ester and the like can be mentioned.
Among these, polyalkylene glycol monoalkyl ether is preferable from the viewpoints of storage stability and light transmittance and haze of the obtained film.

Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates.
Examples of amphoteric surfactants include alkyl carboxybetaines.

The aqueous coating material according to the present disclosure may contain only one type of surfactant or may contain two or more types of fluorine from the viewpoint of improving the wettability and coating properties of the aqueous coating material to the substrate. A surfactant, a silicone surfactant, an acetylene surfactant, and the like.
Fluorosurfactants include Megafac series manufactured by DIC Corporation, such as Megafac F-444, Surflon series manufactured by AGC Seimi Chemical Co., Ltd., such as Surflon S-221, and Neos Corporation, such as Footgent 100. For example, the company's Footage series.
Examples of the silicone-based surfactant include leveling materials KP series manufactured by Shin-Etsu Chemical Co., Ltd. such as KP-124. Examples of acetylene surfactants include Surfinol series and Olphine series manufactured by Nissin Chemical Industry Co., Ltd. such as Surfinol 420 and Olphine E1004.
The content of the surfactant in the aqueous coating material according to the present disclosure is 0.01% by mass to the total mass of the aqueous coating material from the viewpoints of storage stability and light transmittance and haze of the obtained film. It is preferably 10% by mass, more preferably 0.02% by mass to 5% by mass, and particularly preferably 0.03% by mass to 1% by mass.

<Core shell particles containing nonpolar solvent as core material>
The aqueous coating material according to the present disclosure includes core-shell particles including a nonpolar solvent as a core material.
The “nonpolar solvent” in the present disclosure refers to a solvent having a solubility in water of 0.1% by mass or less at 20 ° C. and a relative dielectric constant of 10 or less.
Examples of the nonpolar solvent include a hydrocarbon compound, a fluorinated hydrocarbon compound, a silicone compound, and the like. From the viewpoint of light transmittance and haze of the obtained film, a hydrocarbon compound is preferable.
The hydrocarbon compound may be an aliphatic hydrocarbon compound or an aromatic hydrocarbon compound, but from the viewpoint of light transmittance and haze of the resulting film, it should be an aliphatic hydrocarbon compound. Are preferred, and alkanes are more preferred.
The hydrocarbon compound may be linear, branched, ring structure, or unsaturated bond, but the obtained film has light transmittance and From the viewpoint of haze, a linear hydrocarbon compound or a branched hydrocarbon compound is preferable, and a linear hydrocarbon compound is more preferable.
Moreover, it is preferable that the said hydrocarbon compound is a compound which does not have an unsaturated bond.
Furthermore, it is preferable that the said hydrocarbon compound is a compound which consists only of a carbon atom and a hydrogen atom from a viewpoint of the light transmittance and haze of the film | membrane obtained.
The number of carbon atoms of the hydrocarbon compound is preferably 7 or more, more preferably 8 or more and 20 or less, and further preferably 10 or more and 19 or less, from the viewpoint of light transmittance and haze of the resulting film. Preferably, it is 12 or more and 17 or less.

  The boiling point of the nonpolar solvent is preferably 90 ° C. or higher and 350 ° C. or lower, more preferably 100 ° C. or higher and 340 ° C. or lower, and 120 ° C. or higher, from the viewpoint of light transmittance and haze of the resulting film. The temperature is more preferably 320 ° C. or lower, and particularly preferably 200 ° C. or higher and 310 ° C. or lower. The “boiling point” in the present disclosure is a boiling point at 1 atm (101,325 Pa).

  Specific examples of the nonpolar solvent include n-heptane (boiling point: 98 ° C.), n-octane (boiling point: 125 ° C.), n-dodecane (boiling point: 216 ° C.), n-tetradecane (boiling point: 254 ° C.). N-hexadecane (boiling point: 287 ° C.), n-heptadecane (boiling point: 302 ° C.), n-octadecane (boiling point: 317 ° C.), n-icosane (boiling point: 343 ° C.), cyclooctane (boiling point: 149 ° C.), Preferable examples include toluene (boiling point: 111 ° C.), p-xylene (boiling point: 138 ° C.), m-xylene (boiling point: 139 ° C.), o-xylene (boiling point: 144 ° C.) and the like.

The said nonpolar solvent in the said core material may be included individually by 1 type, or may contain 2 or more types.
The core material may contain a polar solvent such as water, an alcohol compound, and tetrahydrofuran, but the content of the polar solvent is less than 50% by mass with respect to the total mass of the organic solvent contained in the core material. It is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 1% by mass or less.

The material of the shell of the core-shell particles is not particularly limited, but the shell preferably contains a polysiloxane compound from the viewpoint of the strength, light transmittance, and haze of the obtained film, and is represented by the above formula 1. It is more preferable to include a hydrolysis condensate of a siloxane compound, and it is further preferable to include 50% by mass or more of the hydrolysis condensate of the siloxane compound represented by the formula 1 with respect to the total mass of the shell. It is particularly preferable that it consists of a hydrolysis condensate of the siloxane compound represented by 1.
The surface of the core-shell particles may be hydrophobic or hydrophilic, but is preferably hydrophilic from the viewpoint of storage stability and haze of the resulting film.

The volume average particle diameter of the core-shell particles is preferably 0.05 μm to 1.5 μm, more preferably 0.08 μm to 1 μm, from the viewpoint of the strength of the film obtained, light transmittance, and haze. More preferably, it is 0.1 micrometer-0.6 micrometer, and it is especially preferable that it is 0.1 micrometer-0.4 micrometer.
Further, the volume average particle diameter of the particles contained in the aqueous coating material according to the present disclosure is preferably 0.05 μm to 1.5 μm from the viewpoint of the strength, light transmittance, and haze of the obtained film. The thickness is more preferably 08 μm to 1 μm, further preferably 0.1 μm to 0.6 μm, and particularly preferably 0.1 μm to 0.4 μm.
Further, the coefficient of variation of the particle diameter of the core-shell particles is preferably 100% or less, more preferably 90% or less, and more preferably 70% or less from the viewpoint of light transmittance and haze of the obtained film. More preferably, it is particularly preferably 0% or more and 50% or less.
Further, the coefficient of variation of the particle diameter of the particles contained in the aqueous coating material according to the present disclosure is preferably 100% or less, and preferably 95% or less from the viewpoint of light transmittance and haze of the obtained film. More preferably, it is 90% or less, more preferably 0% or more and 87% or less.
The volume average particle size of the particles in the present disclosure is measured using a laser diffraction / scattering particle size distribution measuring device (model number: Microtrack MT3300EXII, manufactured by Microtrack Bell Co., Ltd.). In the present disclosure, the average particle diameter means a median diameter.
Further, the coefficient of variation of the particle diameter of the core-shell particles in the present disclosure is calculated by dividing the standard deviation in the volume distribution of the particle diameter measured in the above measurement by the median diameter.

  The mass ratio of the core to the shell in the core-shell particles is preferably core: shell = 1: 99 to 99: 1 from the viewpoint of the strength of the film obtained, light transmittance, and haze, and 5:95 to 5-5. : 95 is more preferable, and 10:90 to 90:10 is particularly preferable.

The core size (maximum diameter) in the core-shell particles is preferably 40 nm or more, more preferably 40 nm to 1,000 nm, more preferably 60 nm, from the viewpoint of the strength, light transmittance, and haze of the obtained film. It is particularly preferable that the thickness is ˜600 nm.
The measuring method of the core size (maximum diameter) in the core-shell particles can be measured by the same method as the measuring method of the internal void diameter of the membrane described above.

The core-shell particles may be used alone or in combination of two or more.
The content of the core-shell particles is preferably 0.05% by mass to 40% by mass with respect to the total mass of the aqueous coating material from the viewpoint of the strength, light transmittance, and haze of the obtained film. It is more preferably from 20% by mass to 20% by mass, and particularly preferably from 0.5% by mass to 10% by mass.

<Specific siloxane compound>
The aqueous coating material according to the present disclosure includes a siloxane compound represented by the following formula 1, a hydrolyzate of the siloxane compound represented by the following formula 1, and a hydrolysis condensate of the siloxane compound represented by the following formula 1. At least one compound (specific siloxane compound) selected from the group consisting of:

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

  The hydrolyzate of the siloxane compound represented by Formula 1 refers to a compound in which at least a part of the substituents on the silicon atom in the siloxane compound represented by Formula 1 is hydrolyzed to form a silanol group. The hydrolytic condensate of the siloxane compound represented by Formula 1 is two or more compounds selected from the group consisting of the siloxane compound represented by Formula 1 and the hydrolyzate of the siloxane compound represented by Formula 1. Refers to a condensed compound.

The organic group having 1 to 6 carbon atoms in R ¹ and R ² in Formula 1 may be linear, have a branch, or have a ring structure. Examples of the organic group having 1 to 6 carbon atoms include an alkyl group and an alkenyl group, and an alkyl group is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, and cyclohexyl group. It is done.
R ¹ and R ² in Formula 1 are each independently preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 4 carbon atoms from the viewpoint of the strength, light transmittance, and haze of the obtained film. Is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ³ in Formula 1 is preferably an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoint of the strength, light transmittance, and haze of the obtained film. Is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ⁴ in Formula 1 is independently an alkyl group, a vinyl group, or a vinyl group, an epoxy group, a styryl group (vinylphenyl group), (meth) from the viewpoint of the strength, light transmittance, and haze of the obtained film. At least one group selected from the group consisting of acryloxy group, (meth) acrylamide group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group. Is preferably an alkyl group, more preferably an alkyl group, and particularly preferably an alkyl group having 1 to 8 carbon atoms.
M in Formula 1 is preferably 1 or 2 and more preferably 2 from the viewpoint of the strength, light transmittance, and haze of the obtained film.
N in Formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength, light transmittance, and haze of the obtained film.
Examples of such specific siloxane compounds include Shin-Etsu Chemical Co., Ltd. KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM-5103, KBE-903, KBE-9103P, KBE-585, KBE-803, KBE-846, KR-500, KR-515, KR-516, KR-517, KR-518, X-12-1135, X-12-1126, X-12-1131, Evonik Japan Co., Ltd. Dynasylan 4150, Mitsubishi Chemical Co., Ltd. MKC silicate MS-51, MS-56, MS-57, MS-56S, Colcoat (Co., Ltd.) ) Ethyl silicate 28, N-propyl silicate, N-butyl silicate, SS-101, etc. And the like.

The aqueous coating material which concerns on this indication may contain only 1 type of specific siloxane compounds, and may contain 2 or more types.
The content of the specific siloxane compound is preferably 30% by mass to 99% by mass with respect to the total solid content of the aqueous coating material, and is preferably 50% by mass to 50% by mass, from the viewpoint of the strength of the film obtained, light transmittance, and haze. More preferably, it is 99 mass%, and it is especially preferable that it is 70 mass%-95 mass%. The “solid content” of the aqueous coating material in the present disclosure means a component excluding water and a hydrophilic organic solvent described later.

<Water>
The aqueous coating material according to the present disclosure contains water.
The aqueous coating material according to the present disclosure contains water, but may further contain a hydrophilic organic solvent or the like that is excellent in affinity with water.
The water content in the aqueous coating material is preferably 30% by mass or more based on the total content of water and the hydrophilic organic solvent (not including the organic solvent of the core material in the core-shell particles), and 50 More preferably, it is at least 80% by mass, and particularly preferably at least 80% by mass and not more than 100% by mass.
Examples of the hydrophilic organic solvent that can be included in the aqueous coating material according to the present disclosure include hydrophilic compounds such as alcohol compounds, glycol compounds, ether compounds, and ketone compounds.
The hydrophilic organic solvent that can be used in the present disclosure is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, butanol, acetone, ethylene glycol, and ethyl cellosolve. From the viewpoint of availability and reduction of environmental burden, an alcohol compound is preferable, and at least one compound selected from the group consisting of ethanol and isopropanol is more preferable.

The content of the solid content with respect to the total mass of the aqueous coating material according to the present disclosure is preferably 0.1% by mass to 50% by mass from the viewpoint of light transmittance and haze of the obtained film, and 0.2% by mass. % To 40% by mass is more preferable, and 0.5% to 30% by mass is particularly preferable.
Further, the water content in the aqueous coating material according to the present disclosure is preferably 30% by mass or more, and more preferably 40% by mass to 99.9% by mass with respect to the total mass of the aqueous coating material. 50 mass% to 99.8 mass% is more preferable, and 70 mass% to 99.5 mass% is particularly preferable.

<Other ingredients>
The aqueous coating material according to the present disclosure can contain other components depending on the purpose as long as the effects according to the present disclosure are not impaired in addition to the essential components described above.
As other components, known additives can be used, and examples thereof include a charge control agent, a condensation catalyst for a siloxane compound, and a preservative.
As described above, the aqueous coating material according to the present disclosure forms a film by condensation and curing of the specific siloxane compound due to a decrease in water, which is a solvent, as described above. Further, at the time of drying, at least a part of the organic solvent that is the core material of the core-shell particles is volatilized to form voids. Therefore, formation of a cured film does not require light irradiation or high-temperature heat treatment required for a polymerization reaction, a crosslinking reaction, or the like. Moreover, it is not necessary to contain the photoinitiator required for a polymerization reaction, a crosslinking reaction, etc., a thermal polymerization initiator, etc.
For this reason, the aqueous | water-based coating material which concerns on this indication which does not contain the photoinitiator which influences storage stability, a thermal-polymerization initiator, etc. has favorable storage stability.
According to the aqueous coating material according to the present disclosure, a film having excellent light transmittance can be formed by a simple method.

-Antistatic agent-
The aqueous coating material according to the present disclosure may contain an antistatic agent.
Antistatic agents are used for the purpose of suppressing the adhesion of contaminants by imparting antistatic properties to a film formed of an aqueous coating material.
There are no particular restrictions on the antistatic agent for imparting antistatic properties.
As the antistatic agent used in the present disclosure, at least one selected from the group consisting of metal oxide particles, metal nanoparticles, conductive polymers, and ionic liquids can be preferably used. Two or more antistatic agents may be used in combination.
The metal oxide particles need to be added in a relatively large amount in order to impart antistatic properties. Dirty can be further increased.

Although there is no restriction | limiting in particular in a metal oxide particle, A tin oxide particle, an antimony dope tin oxide particle, a tin dope indium oxide particle, a zinc oxide particle, a silica particle, etc. are mentioned.
The metal oxide particles have a large refractive index, and if the particle size is large, there is concern about a decrease in light transmittance due to scattering of transmitted light. Therefore, the average primary particle size of the metal oxide particles is preferably 100 nm or less, and 50 nm. More preferably, it is more preferably 30 nm or less. Moreover, it is preferable that a lower limit is 2 nm or more.
The shape of the particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
The average primary particle diameter of the metal oxide particles can be obtained from a photograph obtained by observing the dispersed particles with a transmission electron microscope. From the image of the photograph, the projected area of the particle is obtained, and the equivalent circle diameter is obtained therefrom, which is taken as the average particle size (average primary particle size). As the average primary particle diameter in the present specification, a value calculated by measuring a projected area of 300 or more particles and obtaining an equivalent circle diameter is used.
In addition, when the shape of the metal oxide particles is not spherical, it may be obtained using other methods, for example, a dynamic light scattering method.

One kind of antistatic agent may be contained in the aqueous coating material, or two or more kinds thereof may be contained. When two or more types of metal oxide particles are contained, two or more types having different average primary particle diameters, shapes, and materials may be used.
In the aqueous coating material according to the present disclosure, the content of the antistatic agent is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass with respect to the total solid content of the aqueous coating material. % Or less is particularly preferable.
By making content of an antistatic agent into the said range, antistatic property can be effectively provided to the formed film | membrane, without reducing the film forming property of an aqueous coating material.
The content when metal oxide particles are used as the antistatic agent is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass with respect to the total mass of the aqueous coating material. % Or less is particularly preferable.
By making the content of the metal oxide particles in the above range, the dispersibility of the metal oxide particles in the aqueous coating material is improved, the occurrence of aggregation is suppressed, and the necessary antistatic property is formed by the aqueous coating material. It can be applied to the membrane.

-Condensation catalyst-
The aqueous coating material according to the present disclosure preferably contains a condensation catalyst that promotes the condensation of the siloxane compound.
When the aqueous coating material contains a condensation catalyst, a film having higher durability can be formed. In the present disclosure, at least a part of the hydroxy groups of the hydrolyzate of the siloxane compound represented by Formula 1 are condensed with each other as the aqueous coating material is dried after coating to reduce the moisture in the film. By forming a condensate, a stable film is formed. When the film is formed, the aqueous coating material contains the siloxane compound represented by Formula 1 and a hydrolyzate thereof, and a catalyst that promotes the condensation of the hydrolyzed condensate so that the film can be formed more quickly. Can proceed.

Although the condensation catalyst which can be used for this indication is not specifically limited, An acid catalyst, an alkali catalyst, an organometallic catalyst, etc. are mentioned.
Examples of the acid catalyst include phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
Examples of organometallic catalysts include aluminum bis (ethyl acetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate) Zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate), titanium chelate compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), and dibutyltin diacetate, dibutyltin dilaurate, And organotin compounds such as dibutyltin dioctiate.
Although the kind of condensation catalyst is not particularly limited, an organometallic catalyst is preferable, and an aluminum chelate compound or a zirconium chelate compound is more preferable.

  The content of the condensation catalyst is preferably 0.001% by mass to 20% by mass with respect to the total solid content of the aqueous coating material from the viewpoint of the strength, light transmittance, and haze of the film obtained, More preferably, the content is from 15% by mass to 15% by mass, and particularly preferably from 0.01% by mass to 10% by mass.

In addition, the condensation catalyst which accelerates | stimulates the condensation of a siloxane compound is useful also for acceleration | stimulation of the hydrolysis reaction of the siloxane compound represented by Formula 1 mentioned above.
The hydrolysis reaction and condensation reaction of the silicon-bonded alkoxy group of the siloxane compound represented by Formula 1 are in an equilibrium relationship, and if the water content in the aqueous coating material is large, If the content of is small, it proceeds in the direction of condensation. Since the condensation catalyst that promotes the condensation reaction of the alkoxy group has an effect of promoting the reaction in both directions, the hydrolysis reaction can be promoted in a state where the water content in the aqueous coating material is large. Due to the presence of the condensation catalyst, the siloxane compound represented by Formula 1 can be hydrolyzed under milder conditions.

-Manufacturing method of aqueous coating material-
The method for producing an aqueous coating material according to the present disclosure is not particularly limited, and a nonpolar solvent, a surfactant, and water are mixed, the nonpolar solvent is dispersed in water, and a specific siloxane compound is added. A shell layer is formed on the surface of a nonpolar solvent dispersed by partial hydrolysis-condensation to produce core-shell particles, a method for producing an aqueous coating material, a core-shell particle containing a nonpolar solvent as a core material, a specific siloxane compound, The method of mixing and manufacturing surfactant and water is mentioned.
Among them, a nonpolar solvent, a surfactant, and water are mixed, the nonpolar solvent is dispersed in water, a specific siloxane compound is added, and a shell is formed on the surface of the nonpolar solvent dispersed by hydrolytic condensation. A method of producing a water-based coating material by forming core-shell particles by forming a layer is preferred. The specific siloxane compound may be added together with a nonpolar solvent, a surfactant, and water, or may be added after the nonpolar solvent is dispersed in water.

The core-shell particles are preferably produced by emulsifying the core material in water and forming a shell layer on the surface of the core material. By emulsifying the core material before forming the shell layer, an interactive attractive force is generated between the material forming the shell layer and the core material, and the core-shell formation proceeds efficiently.
The method of emulsifying the core material includes a method using a rotor (rotating blade) and a stator (fixed blade), a method using ultrasonic cavitation, a method using a grinding medium such as balls / beads, and high-speed collision between raw materials. And a method in which a dispersion solvent is passed through a solvent through a porous membrane. In any case, the core material can be emulsified by applying a shearing force.
As an apparatus used for the method of emulsifying the core material, an automixer 20 type manufactured by Primix Co., Ltd., an ultrasonic homogenizer Sonifier SFX250 manufactured by Nippon Emerson Co., Ltd., OMEGA LAB manufactured by Ashizawa Finetech Co., Ltd. There are Starburst 10 manufactured by Sugino Machine, KH-125 manufactured by SPG Techno Co., Ltd.

The specific siloxane compound is preferably first mixed with a solvent containing water to form a hydrolyzate of the specific siloxane compound to prepare a hydrolyzate solution of the specific siloxane compound. At this time, a condensation catalyst for promoting the condensation of the specific siloxane compound can be added.
To the obtained hydrolyzate solution of the specific siloxane compound, a surfactant and a nonpolar solvent may be added, or a nonpolar solvent, a surfactant and water are mixed to add a nonpolar solvent. You may mix the liquid disperse | distributed in water and the hydrolyzate solution of the said specific siloxane compound. Alternatively, a mixture of a nonpolar solvent, a surfactant, and water mixed with a nonpolar solvent dispersed in water and the specific siloxane compound may be mixed to perform hydrolysis and shell formation simultaneously.

By using the aqueous coating material according to the present disclosure, a film having good light transmittance is formed.
For this reason, the aqueous | water-based coating material which concerns on this indication is suitable for formation of the film | membrane which protects the surface of the apparatus used outdoors, such as a solar cell module. The formed film is excellent in light transmittance, excellent in power generation efficiency, and excellent in durability of the film by using a specific siloxane compound.
Therefore, the aqueous coating material according to the present disclosure is useful for the surface material of various base materials, optical devices, in particular, the formation of antireflection films, and the formation of solar cell module front sheets (solar cell front sheets).

(film)
The first embodiment of the film according to the present disclosure is obtained by drying a coat layer formed on a substrate, and the coat layer is water, a hydrolytic condensate of a siloxane compound represented by Formula 1, a surface activity. And at least a surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less. The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass with respect to the total mass of the nonpolar solvent. It is 40 mass% or less, and in the coat layer after drying, there are voids in at least some of the core-shell particles.
The second embodiment of the membrane according to the present disclosure is a membrane obtained by drying the aqueous coating material according to the present disclosure, and is a membrane having voids therein, preferably hollow particles.
The coating layer is preferably a coating film of an aqueous coating material, and a preferable aspect of the core-shell particles containing a surfactant and a nonpolar solvent in the coating material in the coating material is the aqueous coating material according to the present disclosure. This is the same as the preferred embodiment described above.
Moreover, the preferable aspect of the hydrolysis-condensation product of the siloxane compound represented by Formula 1 in the said coating layer is the preferable aspect of the hydrolysis-condensation product of the siloxane compound represented by Formula 1 mentioned above in the aqueous coating material which concerns on this indication. It is the same.

The membrane according to the present disclosure has voids in at least some of the core-shell particles in the coat layer after drying.
The average internal void diameter of the film is preferably 20 nm or more, more preferably 30 nm or more, still more preferably 30 nm to 200 nm, further preferably 40 nm to 150 nm, from the viewpoint of strength, light transmittance, and haze. It is particularly preferred that
Further, the variation coefficient of the void diameter of the film is preferably 100% or less, more preferably 90% or less, and particularly preferably 60% or less from the viewpoint of light transmittance and haze.
The measurement method of the average internal void diameter of the film was performed by the method described below.
The laminate with an antireflection film was cut in a direction perpendicular to the substrate, and the cut surface was observed with a scanning electron microscope to evaluate the diameter of the closed void, the coefficient of variation of the void diameter, and the porosity.
The equivalent circle diameter was calculated for 200 arbitrarily selected voids, and the average value was taken as the diameter of the closed void.
The void ratio was calculated by dividing the internal void portion and the resin binder portion by performing image processing (binarization) using image processing software (ImageJ), and calculating the ratio of the internal void portion.
The variation coefficient of the void diameter of the film is calculated by dividing the standard deviation in the distribution of the void diameter measured in the above measurement by the average internal void diameter.

The average thickness of the film according to the present disclosure is not particularly limited and can be formed to a desired thickness. However, from the viewpoint of light transmittance and haze, it is preferably 10 nm to 1 μm, and 50 nm to 350 nm. More preferably, it is more preferably 80 nm to 200 nm, and particularly preferably 100 nm to 180 nm.
Moreover, the average thickness of the said film | membrane shall measure thickness at 10 or more places in the said film | membrane, and shall take an average.

The integrating sphere transmittance (average of the transmittance of light having a wavelength λ = 300 nm to 1,100 nm) of the film according to the present disclosure is preferably 90% or more, and more preferably 93% or more.
The integral sphere transmittance of the membrane in the present disclosure is determined by measuring the integral sphere transmittance of a base material provided with a membrane formed of an aqueous coating material, using a barium sulfate white plate as a reference.
The measurement of the integrating sphere transmittance of the membrane in the present disclosure can be measured by using a transmission spectrophotometer with an integrating sphere. Specifically, for example, an apparatus in which an integrating sphere attachment device (ISR-2200, manufactured by Shimadzu Corporation) is connected to an ultraviolet-visible infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), or It measures with the apparatus which connected the versatile large sample chamber (MPC-3100, Shimadzu Corporation Corp.) to the ultraviolet visible infrared spectrophotometer (UV-3600, Shimadzu Corp. make).

  The film according to the present disclosure is suitably used for optical lenses, optical filters, flattening films for thin film transistors (TFTs) of various displays, antireflection films, anticondensation films, antifouling films, surface protective films, etc. It is preferably used for an antireflection film. Further, since the surface protective film of the solar cell module is also required to have antireflection performance from the viewpoint of power generation efficiency, the film according to the present disclosure is more preferably used as the surface protective film of the solar cell module. The front sheet (solar cell front sheet) is particularly preferably used.

<Method for producing membrane>
The method for producing a film according to the present disclosure is not particularly limited, and includes a step of forming a coat layer by applying the aqueous coating material according to the present disclosure on a substrate, and a step of drying the coat layer, It is preferable that at least a part of the core-shell particles become a hollow particle that forms voids in the coat layer after the drying step.
There is no restriction | limiting in particular in the base material used for this indication, For example, desired base materials, such as a base material or composite base material of the material mentioned later, a board | substrate which has wiring etc., a solar cell module, can be used.
Moreover, you may use a temporary support body as a base material.
As the material of the base material, for example, any of glass, resin, metal, ceramics and the like can be suitably used.
The method for applying the aqueous coating material according to the present disclosure to the substrate is not particularly limited, and for example, any known application method such as spray application, brush application, roller application, bar application, dip application, etc., may be applied. Can do. Further, it is also preferable to subject the base material to a surface treatment such as corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, or UV treatment before applying the aqueous coating material.

The coating layer may be dried at room temperature (25 ° C.) or may be heated. However, the organic solvent is sufficiently volatilized to form voids, and the light transmittance of the obtained film and From the viewpoint of suppression of coloring, it is preferable to carry out heating to 40 ° C to 700 ° C. When using a resin base material, it is necessary to heat at a temperature equal to or lower than the decomposition temperature of the base material. Specifically, it is preferably performed by heating to 40 ° C. to 200 ° C., and a viewpoint of suppressing thermal deformation of the base material. It is more preferable to carry out by heating to 40 to 120 ° C.
Moreover, when performing a heating, although heating time does not have a restriction | limiting in particular, It is preferable that it is 1 minute-30 minutes.

(Laminate)
1st Embodiment in the laminated body which concerns on this indication has a film | membrane which concerns on this indication.
Further, the second embodiment of the laminate according to the present disclosure is a laminate having a film formed by drying the aqueous coating material according to the present disclosure, and voids, preferably hollow particles are provided inside the film. Have.
Moreover, it is preferable that the laminated body which concerns on this indication has the said film | membrane on a base material.
There is no restriction | limiting in particular as a base material of the laminated body which concerns on this indication, Although the base material mentioned above can be used, A resin base material is mentioned preferably from a viewpoint of versatility and weight reduction.
Examples of the resin base material include polyester, polycarbonate, polyolefin, acrylic resin, cellulose, polyvinyl chloride, polyimide, polyamide, and fluorine-based polymer. Among these, polyester, polyolefin, poly (meth) acryl, and cellulose are preferable from the viewpoints of cost, mechanical strength, transmittance, and transparency.
Examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.
Examples of the polyolefin include polypropylene, polyethylene, and cycloolefin.
Examples of the acrylic resin include polymethyl methacrylate.
Examples of cellulose include triacetyl cellulose.
In the case of using a resin base material for the base material, the thickness of the resin base material is preferably 1 μm or more, more preferably 10 μm or more, further preferably 45 μm or more, and more preferably 145 μm or more from the viewpoints of handleability and withstand voltage. Preferably, it is 200 μm or more. As an upper limit, 500 micrometers or less are preferable, 450 micrometers or less are more preferable, and 500 micrometers or less are further more preferable.
When a glass substrate is used as the substrate, the thickness of the glass substrate is preferably 500 μm or more. As an upper limit, 4,000 micrometers or less are preferable and 3,500 micrometers or less are more preferable.

The laminate according to the present disclosure may further include other layers.
As another layer, it can have a well-known various layer. Specific examples include an adhesive layer, a hard coat layer, an ultraviolet absorption layer, and an undercoat layer.
Moreover, when using the laminated body which concerns on this indication for the solar cell module mentioned later, it is preferable that the laminated body which concerns on this indication has these layers.

<Adhesive layer>
The laminate according to the present disclosure may include an adhesive layer between the base material and the film according to the present disclosure.
By providing the adhesive layer, the adhesion between the substrate and the film according to the present disclosure is improved, and a laminate having excellent durability can be obtained.

Examples of the adhesive layer include a known pressure-sensitive adhesive, a layer containing a known adhesive, or a layer containing a cured product thereof.
The adhesive layer is preferably a layer obtained by applying a coating solution for forming an adhesive layer containing a resin and a crosslinking agent and then drying or curing.
Although it does not specifically limit as resin, A polyolefin resin, a urethane resin, a polyester resin, an acrylic resin, polyvinyl alcohol, a polyamide resin, a silicone resin etc. are mentioned, A polyolefin resin is preferable from an adhesive viewpoint.
The crosslinking agent is not particularly limited, and examples thereof include a carbodiimide-based crosslinking material, an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, a block isocyanate-based crosslinking agent, and the like, and an oxazoline-based crosslinking agent is preferable.
The coating liquid for forming the adhesive layer may further contain known components such as a surfactant and a solvent.

  The thickness of the adhesive layer is not particularly limited, but is preferably 0.2 μm to 10 μm and more preferably 0.4 μm to 5 μm from the viewpoint of light transmittance.

  The adhesive layer is formed, for example, by applying an adhesive layer-forming coating solution to a substrate or a film according to the present disclosure and drying it.

<Hard coat layer>
The laminate according to the present disclosure preferably further includes a hard coat layer, and more preferably further includes a hard coat layer on the side of the substrate on which the film according to the present disclosure is provided. It is particularly preferable to further have a hard coat layer between such films.
By providing the hard coat layer, a laminate having further excellent heat resistance can be obtained. This is presumably because the hard coat layer suppresses the permeation of oxygen into the laminate, thereby suppressing the deterioration of the base material due to oxygen.

  The hard coat layer is not particularly limited, and examples thereof include hard coat layers known in the field of solar cells. For example, JP 2013-45045 A, JP 2013-43352 A, and JP 2012-232459 A. JP, 2012-128157, JP, 2011-131409, JP, 2011-131404, JP, 2011-126162, JP, 2011-75705, JP, 2009-286981, special JP 2009-263567, JP 2009-75248, JP 2007-164206, JP 2006-96811, JP 2004-75970, JP 2002-156505, JP 2001. -272503, International Publication No. 12/018087, When Publication No. 12/098967, WO 12/086659, may be made of a hard coat layer as described in WO 11/105594.

The pencil hardness on the surface of the hard coat layer is preferably B or higher from the viewpoint of scratch resistance of the laminate, and the pencil hardness on the surface of the hard coat layer is more preferably HB or higher, and F or higher. More preferably.
The upper limit of the pencil hardness on the surface of the hard coat layer is not particularly limited, but the upper limit of the pencil hardness on the surface of the hard coat layer is preferably 6H or less, more preferably 3H or less from the viewpoint of processability of the laminate. is there.
In addition, the pencil hardness of the surface of a hard-coat layer means the value measured based on JISK5600-5-4: 1999. A high uni from Mitsubishi Pencil Co., Ltd. is used as the pencil.

As a material of the hard coat layer, known materials can be included, but the hard coat layer preferably contains a siloxane resin from the viewpoint of durability.
Moreover, when producing the said siloxane resin by a sol-gel method, it is preferable that a hard-coat layer contains a metal complex as a hardening | curing agent.
As the metal complex, a metal complex containing at least one metal element selected from the group consisting of aluminum, magnesium, manganese, titanium, copper, cobalt, zinc, hafnium, and zirconium is preferable.
The content of the siloxane resin contained in the hard coat layer is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more based on the solid content of the hard coat layer. An upper limit is not specifically limited, 100 mass% may be sufficient.

-Inorganic filler-
The hard coat layer preferably contains at least one inorganic filler from the viewpoint of further improving the hardness of the hard coat layer.
The inorganic filler is preferably at least one inorganic filler selected from the group consisting of metal oxide fillers and inorganic nitride fillers from the viewpoint of further improving the hardness of the hard coat layer.

Examples of the metal oxide filler include silica filler, alumina filler, zirconia filler, and titania filler.
Examples of the inorganic nitride filler include boron nitride filler.

  It is preferable that a hard-coat layer contains a silica filler from a viewpoint of bridge | crosslinking with the siloxane resin in a hard-coat layer.

Examples of the silica filler include dry powdered silica produced by combustion of silicon tetrachloride; colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water; and the like.
When using dry powdery silica, it can be used by dispersing in water using an ultrasonic disperser or the like.
The silica filler is not particularly limited. Specifically, the Sea Hoster series such as Sea Hoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), Snowtex (registered trademark) series such as Snowtex (registered trademark) OZL-35 ( Nissan Chemical Industries, Ltd.).
Examples of the alumina filler include aluminum oxide, which is an amphoteric oxide of aluminum, and alumina hydrate (aluminum hydroxide) containing crystal water.
Examples of the aluminum oxide include α-alumina, γ-alumina, δ-alumina, and θ-alumina depending on the crystal structure. Alumina hydrates include dibsite, bayerite, boehmite, diaspore, pseudoboehmite, and amorphous states depending on the crystal structure.
The alumina filler is not particularly limited. Specifically, an alumina sol series such as alumina sol AS-200 (manufactured by Nissan Chemical Industries), an aluminum sol series such as aluminum sol 10C, and aluminum sol F-1000 (Kawaken Fine Chemical Co., Ltd.) Product), Hijilite series such as Heidilite H-43, Alumina AS series such as Alumina AS10 (manufactured by Showa Denko KK) and the like.
In the case of colloidal form, it may be used directly, and in the case of powder form, it can be used by dispersing in a solvent such as water using an ultrasonic disperser or the like.

Examples of the shape of the inorganic filler include a particle shape such as a spherical shape, a rod shape, a polyhedral shape, a flat plate shape, and a scale shape, a bead shape, a needle shape, and the like.
When the inorganic filler has a particle shape (inorganic particles), the number average primary particle size is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less.
When the number average primary particle size of the inorganic particles is 300 nm or less, a hard coat layer having a smooth surface can be obtained.
On the other hand, the number average primary particle size of the inorganic particles is preferably 2 nm or more, and more preferably 10 nm or more.
When the number average primary particle size of the inorganic particles is 2 nm or more, the hardness of the hard coat layer can be further improved.

The number average primary particle size of the inorganic particles is determined by observing a cross section of the hard coat layer with a scanning electron microscope (SEM), selecting 100 particles included in a range corresponding to an actual area of 1 mm ^2, and determining the particle size of each particle. Is a value obtained by simply averaging the measured values (particle size of each particle).

The content of the inorganic filler is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and more preferably 20% by mass to 50% by mass with respect to the solid content of the hard coat layer. It is particularly preferred that
The total amount of the siloxane resin and the inorganic filler is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass with respect to the solid content of the hard coat layer.

-Other ingredients-
The hard coat layer may contain other components other than the components described above.
For example, the hard coat layer may contain at least one surfactant.
Thereby, the slip property of the surface of a hard-coat layer improves, and the friction of the hard-coat layer surface is reduced.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

Only one type of surfactant may be used, or two or more types may be combined.
The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass, and still more preferably based on the solid content of the hard coat layer. It is 0.1 mass%-1 mass%.

The hard coat layer (or hard coat layer forming coating solution) may contain a pH adjuster.
Examples of the pH adjuster include acids such as nitric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid, and alkalis such as ammonia, triethylamine, ethylenediamine, sodium hydroxide, and potassium hydroxide.

The hard coat layer may contain an ultraviolet absorber.
As an ultraviolet absorber, the compound similar to the ultraviolet absorber contained in the ultraviolet absorption layer mentioned later is mentioned, A metal oxide particle is mentioned preferably.

The thickness of the hard coat layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm, and still more preferably 0.3 μm to 6 μm.
When the thickness of the hard coat is 0.1 μm or more, it is advantageous in terms of the hardness of the hard coat layer surface.
When the thickness of the hard coat layer is 10 μm or less, the transparency and handleability of the laminate are further improved.

<Ultraviolet absorbing layer>
The laminate according to the present disclosure is provided between the base material and the hard coat layer (if the hard coat layer is omitted, the surface of the base material opposite to the side on which the film according to the present disclosure is provided) ) May have an ultraviolet absorbing layer.
The ultraviolet absorbing layer is preferably a layer containing an ultraviolet absorber, and is preferably a layer containing an ultraviolet absorber and a sol-gel cured product, or a layer containing an ultraviolet absorber and a binder polymer.
As the ultraviolet absorber, a known ultraviolet absorber can be used without particular limitation, and it may be an organic compound or an inorganic compound.
Examples of the ultraviolet absorber include triazine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid compounds, metal oxide particles, and the like. Further, the ultraviolet absorber may be a polymer having an ultraviolet absorbing structure, and the polymer having an ultraviolet absorbing structure includes at least a part of a structure such as a triazine compound, a benzotriazole compound, a benzophenone compound, and a salicylic acid compound. An acrylic resin containing a monomer unit derived from an acrylate compound is exemplified.
Examples of the metal oxide particles include titanium oxide particles, zinc oxide particles, and cerium oxide particles.
Examples of the sol-gel cured product include a cured product obtained by hydrolysis and polycondensation of an alkoxide compound of at least one element selected from the group consisting of Si, Ti, Zr and Al.
Examples of the binder polymer include polyolefin resin, acrylic resin, polyester resin, and polyurethane resin.
The ultraviolet absorbing layer is formed by applying each component contained in the ultraviolet absorbing layer and, if necessary, a coating solution for forming an ultraviolet absorbing layer containing a solvent on a surface substrate and drying as necessary. The

<Back layer>
The laminated body which concerns on this indication may be provided with the back layer on the opposite side to the side in which the film | membrane which concerns on this indication of the base material was provided.
A back surface layer functions as a layer for adhesion | attachment with the sealing material (for example, sealing material containing ethylene-vinyl acetate copolymer (EVA)) in a solar cell module, for example.
The back layer preferably contains a binder polymer.
The back layer may be a single layer or two or more layers.

For example, the laminate can include a layer A, a layer B, and a layer C in this order as the back layer on the side opposite to the side on which the film according to the present disclosure is provided.
Hereinafter, the A-layer, the B-layer, and the C-layer that are provided in the laminated body as necessary will be described.

-Layer A-
The layer A preferably contains a binder polymer.
Although it does not specifically limit as a binder polymer which can be contained in A layer, For example, from the viewpoint of adhesiveness with the sealing material when applied to a solar cell module, polyolefin resin, urethane resin, polyester resin, acrylic resin, silicone Examples of the resin include polyolefin resins, polyurethane resins, and acrylic resins from the viewpoint of adhesion.
Examples of the polyolefin resin include Arrow Base (registered trademark) SE-1013N, SD-1010, TC-4010, TD-4010, DA-1010 (both manufactured by Unitika Co., Ltd.), Hitech S3148, S3121 and S8512 (both Toho). Chemical Co., Ltd.), Chemipearl (registered trademark) S-120, S-75N, V100, EV210H (both manufactured by Mitsui Chemicals, Inc.) and the like. As the acrylic resin, Jurimer AS-563A (manufactured by Daicel Finechem Co., Ltd.), Bonlon PS-001, PS-002 (Mitsui Chemicals Co., Ltd.), SIFCLEARS-101, F-101, F102 (manufactured by JSR Corporation), Ceranate WSA1070 (DIC Corporation) etc. are mentioned. Examples of the polyurethane resin include Takelac WS-6021, WS-5000, WS-5100, WS-4000, and the like.
The crosslinking agent is not particularly limited, and examples thereof include an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, a carbodiimide-based crosslinking material, and a block isocyanate-based crosslinking agent, and an oxazoline-based crosslinking agent is preferable.
The coating solution for forming the A layer may further contain known components such as a crosslinking agent, a surfactant, an antistatic agent, an antiseptic, an inorganic filler, and a solvent.

The A layer may contain a known ultraviolet absorber.
Examples of the ultraviolet absorbing compound that can be contained in the layer A include the same compounds as the ultraviolet absorbing compound of the ultraviolet absorbing layer.

  Further, the thickness of the A layer is preferably 0.2 μm or more, and more preferably 0.4 μm or more. Further, the thickness of the A layer is preferably 7.0 μm or less.

The method for forming the A layer is not particularly limited.
As a method for forming the A layer, for example, a method of applying a coating solution for forming the A layer containing the solvent and the above-described component (solid content) of the A layer on the back surface of the composite substrate and drying it. Is mentioned.

-B layer-
The laminate of the present disclosure may include a B layer on the A layer.

The B layer preferably contains a binder polymer.
The binder polymer in the B layer is preferably at least one polymer selected from the group consisting of polyolefins, acrylic resins, polyesters, and polyurethanes from the viewpoint of adhesion to the sealing material.
The binder polymer in the B layer is preferably a polyolefin resin or an acrylic resin from the viewpoints of adhesion to the sealing material and cohesive strength of the coating film.

  The B layer may contain a crosslinking material, a surfactant, an antistatic agent, an antiseptic, an inorganic filler, and the like.

The method for forming the B layer is not particularly limited.
Examples of the method for forming the B layer include a method in which a coating solution for forming a B layer containing a solvent and the above-described component (solid content) of the B layer is applied on the A layer and dried. .

-Layer C-
The laminate according to the present disclosure may include a C layer on the B layer.
The C layer is a layer that is in direct contact with the sealing material of the solar cell module, that is, a layer that functions as an easy adhesion layer for the sealing material of the solar cell module.
The C layer preferably contains a binder polymer.
The binder polymer that can be contained in the C layer is not particularly limited. For example, from the viewpoint of adhesion with a sealing material when applied to a solar cell module, polyolefin resin, urethane resin, polyester resin, acrylic resin, silicone Examples of the resin include polyolefin resins, polyurethane resins, and acrylic resins from the viewpoint of adhesion.
The crosslinking agent is not particularly limited, and examples thereof include an oxazoline-based crosslinking agent, an epoxy-based crosslinking agent, a carbodiimide-based crosslinking material, and a block isocyanate-based crosslinking agent, and an oxazoline-based crosslinking agent is preferable.
The coating solution for forming the C layer may further contain known components such as a surfactant, an antistatic agent, an antiseptic, an inorganic filler, and a solvent.

<Undercoat layer>
The laminate according to the present disclosure may have an undercoat layer on at least one surface of the base material or the film according to the present disclosure.

The undercoat layer preferably contains a binder polymer.
The binder polymer that can be contained in the undercoat layer is not particularly limited.
Examples of the binder polymer that can be contained in the undercoat layer include acrylic resin, polyester, polyolefin, polyurethane resin, and silicone resin.
The undercoat layer preferably contains an acrylic resin.
As an acrylic resin, the thing similar to the acrylic resin which may be contained in the A layer mentioned above is mentioned.
The acrylic resin content ratio in the binder polymer contained in the undercoat layer is more preferably 50% by mass or more.
When the acrylic resin is 50% by mass or more of the binder polymer, it is easy to adjust the elastic modulus of the undercoat layer to 0.7 GPa or more, and the cohesive failure resistance in the case of a solar cell front sheet is further improved.

  The undercoat layer may contain a surfactant, an antioxidant, a preservative, and the like.

The thickness of the undercoat layer is preferably 0.01 μm or more, more preferably 0.03 μm or more, and further preferably 0.05 μm or more.
Further, the thickness of the undercoat layer is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.7 μm or less.

The undercoat layer can be formed by applying a coating solution for forming an undercoat layer containing a solvent and a solid content of the undercoat layer on a surface base material or a composite base material and drying it.
The undercoat layer may be formed by an in-line coating method using the above undercoat layer forming coating solution.
The in-line coating method is a method in which a coating liquid for forming an undercoat layer is applied at a stage before winding up the manufactured base material. Differentiated.
As an aspect of forming an undercoat layer by an in-line coating method, a film in which an undercoat layer-forming coating solution is applied to one surface of a film stretched in the first direction, A mode in which a substrate with an undercoat layer is produced by stretching in a second direction perpendicular to the first direction along the surface is preferable.

The laminated body which concerns on this indication may be provided with other layers other than the layer mentioned above.
Further, in the laminate according to the present disclosure, the light transmittance at 25 ° C. and a wavelength of 550 nm is preferably 80% or more, more preferably 83% or more, and further preferably 85% or more. . The transmittance is measured using a spectrophotometer V670 (manufactured by JASCO Corporation).

The laminate according to the present disclosure can be suitably used for a surface protection member, an antireflection member, an optical device, an antifouling material for building materials such as a window glass and a guide mirror, and the like.
Especially, it can use especially suitably as a solar cell front sheet.

<Method for producing laminate>
The method for producing a laminate according to the present disclosure is not particularly limited, and includes a step of forming a coat layer by applying the aqueous coating material according to the present disclosure on a substrate, and a step of drying the coat layer. It is preferable that at least a part of the core-shell particles become a hollow particle that forms voids in the coat layer after the drying step.
The application of the aqueous coating material to the substrate and the drying of the coating layer can be performed in the same manner as the above-described film manufacturing method.

(Solar cell module)
The solar cell module according to the present disclosure preferably includes the film according to the present disclosure and includes the laminate according to the present disclosure.
The solar cell module according to the present disclosure is represented by a laminate and a polyester film according to the present disclosure, which are excellent in transparency and are provided on the side where sunlight is incident, with solar cell elements that convert light energy of sunlight into electrical energy. More preferably, it is arranged between the back sheet for a solar cell. Between a laminated body and a polyester film, it can seal and comprise with sealing agents represented by resin, such as ethylene-vinyl acetate copolymer, for example.

About members other than a laminated body and a back sheet, such as a solar battery module and a solar battery cell, for example, it describes in detail in "Solar power generation system constituent material" (Eiichi Sugimoto supervision, Kogyo Kenkyukai, 2008 issue). Has been. The solar cell module according to the present disclosure may take any configuration except that the solar cell module according to the present disclosure includes a film according to the present disclosure, preferably a laminate according to the present disclosure, on a side where sunlight enters.
As a base material provided in the side which sunlight injects, resin base materials, such as a glass base material and an acrylic resin, etc. can be mentioned, for example, From a viewpoint of weight reduction, a resin base material can be mentioned preferably.

  There is no restriction | limiting in particular as a solar cell element used for the solar cell module which concerns on this indication, Silicon-type, such as a single crystal silicon, a polycrystalline silicon, an amorphous silicon, copper-indium-gallium-selenium, copper-indium-selenium Any of various known solar cell elements such as III-V and II-VI compound semiconductor systems such as cadmium-tellurium and gallium-arsenic can be applied.

(Water-based coating material kit)
An aqueous coating material kit according to the present disclosure includes the composition A containing the siloxane compound represented by the formula 1 and the composition B containing water, a surfactant, and a nonpolar solvent, and the surfactant. Comprising at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less, and a cation having a molecular weight of 10,000 or less in the composition B The total content of the surfactant and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 40% by mass or less with respect to the total mass of the nonpolar solvent.
By mixing the composition A and the composition B in the aqueous coating material kit according to the present disclosure, a shell is formed by the hydrolytic condensate of the siloxane compound represented by Formula 1 on the surface of the dispersed nonpolar solvent. As a result, core-shell particles are produced, and the aqueous coating material according to the present disclosure can be easily produced.
The preferred embodiments of the siloxane compound represented by Formula 1 in the aqueous coating material kit according to the present disclosure, water, a surfactant, and a nonpolar solvent are the same as the preferred embodiments of the aqueous coating material described above, except for the embodiments described below. It is.
In addition, the above-described hydrophilic organic solvent, charge control agent, preservative and the like may be contained in either or both of the composition A and the composition B.

<Composition A>
The composition A contains a siloxane compound represented by the above formula 1.
In the composition A, the siloxane compound represented by the above formula 1 partially reacts, the hydrolyzate of the siloxane compound represented by the above formula 1, and the hydrolysis condensate of the siloxane compound represented by the above formula 1. May be included.
Moreover, it is preferable that the composition A contains water as a solvent. By containing water, mixing with the composition B can be performed more easily, and the production of the aqueous coating material is facilitated. The composition A may contain a water-soluble organic solvent as a solvent.
When the composition A contains water, the siloxane compound represented by the above formula 1, the hydrolyzate of the siloxane compound represented by the above formula 1, and the hydrolysis condensate of the siloxane compound represented by the above formula 1 The total content is preferably 1% by mass to 50% by mass with respect to the total mass of the composition A.
Furthermore, the composition A preferably contains a surfactant. By containing the surfactant, mixing with the composition B can be performed more easily, and the production of the aqueous coating material is facilitated.

<Composition B>
Composition B was selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less, which contains water, a surfactant, and a nonpolar solvent. The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less in the composition B, which contains at least one surfactant, is based on the total mass of the nonpolar solvent. 0.5 mass% or more and 40 mass% or less.
In the composition B, it is preferable that the nonpolar solvent is dispersed in water.
Moreover, it is preferable that the composition B contains the said condensation catalyst. By including the condensation catalyst, the formation of the core-shell particles becomes easier.
Composition B may contain a water-soluble organic solvent in addition to water.
The composition B may contain core-shell particles, and may contain the nonpolar solvent as a core material of the core-shell particles. Moreover, the remainder of the siloxane compound represented by the said Formula 1 which was not used for shell formation in the case of core-shell formation may be included.

The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less in the composition B is 0.5% by mass or more and 70% by mass or less based on the total mass of the nonpolar solvent. From the viewpoints of storage stability and light transmittance and haze of the resulting film, it is preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 35% by mass. .
The content of the nonpolar solvent in the composition B is preferably 0.05% by mass to 50% by mass and more preferably 0.1% by mass to 40% by mass with respect to the total mass of the composition B. The content is preferably 0.2% by mass to 30% by mass.
Moreover, the content of water in the composition B is preferably 50% by mass to 99.9% by mass and more preferably 70% by mass to 99.5% by mass with respect to the total mass of the composition B. preferable.

  Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. In this example, “%” and “part” mean “% by mass” and “part by mass”, respectively, unless otherwise specified.

Example 1
<Preparation of aqueous coating material 1>
-Composition of emulsion particle dispersion 1-
Hexadecane (n-hexadecane, manufactured by Wako Pure Chemical Industries, Ltd.): 2.77 partsCa-1 (hexadecylpyridinium chloride 10% distilled water diluted, cationic surfactant, manufactured by Wako Pure Chemical Industries, Ltd.) : 4.42 parts-distilled water: 42.81 parts In MS-51, R ¹ , R ² and R ³ in the above formula 1 are methyl groups, m is 2, and n is 5 on average A compound.

In detail, the emulsion particle dispersion was prepared by the following procedure.
Hexadecane, Ca-1 and distilled water are mixed, and by using an ultrasonic homogenizer Sonifier 450 manufactured by Nippon Emerson Co., Ltd., the mixture is cooled with ice water and treated for 30 minutes with stirring, whereby a dispersion of hexadecane in water is present. A liquid was obtained.

-Composition of core-shell particle dispersion 1-
Emulsion particle dispersion: 35.94 parts Distilled water: 2.84 parts Acetic acid (diluted with 5% distilled water): 1.26 parts MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) 9.96 parts

  Next, MS-51, acetic acid, and distilled water are added to this dispersion, and the mixture is further stirred for 16 hours at 25 ° C., whereby core-shell particles containing a nonpolar solvent as a core material, a compound represented by Formula 1 A core-shell particle dispersion containing a surfactant and water was obtained.

-Composition of aqueous coating material 1-
-Core shell particle dispersion: 15.04 parts-Ion exchange water: 79.46 parts-F-444 (Fluorine-based surfactant diluted with 1% distilled water, manufactured by DIC Corporation): 5.50 parts

  Subsequently, ion-exchange water and F-444 were added to this dispersion, and the aqueous coating material 1 was obtained by stirring at 25 degreeC for 2 days.

<Formation of laminated body 1>
A polypropylene substrate (PP, Trefan BO 60-2500, manufactured by Toray Industries, Inc., substrate thickness 60 μm) was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the aqueous | water-based coating material 1 was apply | coated with the bar coater using bar number # 4, and the coating layer with an average thickness of 130 nm was formed by drying at 80 degreeC for 2 minutes, and the laminated body 1 was obtained.

[Evaluation]
The following performance evaluation was performed using the aqueous coating material prepared above and the prepared laminate. The evaluation results are shown in Table 1.

1. Particle diameter of core-shell particles in aqueous coating material Using a laser diffraction / scattering particle size distribution measuring device (model number: Microtrack MT3300EXII, manufactured by Microtrack Bell Co., Ltd.), the volume average particle diameter of core-shell particles in aqueous coating material ( The median diameter was measured.
In addition, the coefficient of variation of the particle diameter of the core-shell particles was calculated by dividing the standard deviation in the volume distribution of the particle diameter by the median diameter.

2. Transmittance of the laminate Using an ultraviolet-visible infrared spectrophotometer (model number: UV-3100PC, manufactured by Shimadzu Corporation), an index for measuring the transmittance of the laminate and evaluating the light transmittance of the laminate did. The transmittance was measured with the surface on which the film (coat layer) of the obtained laminate was formed facing the light source.
It means that it is a coat layer which is excellent in light transmittance, so that the measured value of effective transmittance is high.
The transmittance was evaluated using an average transmittance obtained by calculating an average value of transmittances at wavelengths of 300 nm to 1,100 nm and an effective transmittance. The effective transmittance is based on the following formula T, using the transmittance of the laminate at a wavelength of 300 nm to 1,100 nm, the spectral distribution of sunlight (AM1.5), and the spectral sensitivity of the crystalline silicon solar cell. Calculated. The spectral sensitivity was defined as the spectral irradiance of the crystalline silicon type reference solar cell.

  In formula T, E (λ) represents the spectral distribution of sunlight at wavelength λ, S (λ) represents the spectral sensitivity of the crystalline silicon solar cell at wavelength λ, and T (λ) is at wavelength λ. It represents the transmittance of the laminate.

3. Using a haze haze meter (model number: NDH 5000, manufactured by Nippon Denshoku Industries Co., Ltd.), the haze (Haze) of the obtained laminate was measured, and the obtained measured value was measured for light transmittance. The index to be evaluated. Haze was measured with the surface of the laminate film (coat layer) formed facing the light source.
It means that the lower the measured value of haze, the better the laminate and the coat layer are, and it is preferably 5% or less.

(Examples 2 to 28)
As shown in Table 1 or 2, the same procedure as in Example 1 was performed except that the base material, organic solvent, surfactant, W / O ratio, and drying conditions, film thickness, and nonpolar solvent ratio were changed. The emulsion particle dispersions 2-28, the core-shell particle dispersions 2-28, the aqueous coating materials 2-28, and the laminates 2-28 of Examples 2-28 were prepared.
Further, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 29)
[Preparation of solar cell front sheet]
-Production of adhesive layer-
An adhesive layer forming coating solution 29 was obtained by mixing an adhesive layer forming composition having the following composition.

-Composition of the adhesive layer forming composition 29-
Polyolefin resin (Arrow Base DA-1010, manufactured by Unitika Ltd., solid content 25%): 27.25 parts Polyurethane resin (Takelac WS-5100, manufactured by Mitsui Chemicals, Inc., solid content 30%): 22. 71 parts-Fluorosurfactant (sodium bis (3,3,4,4,5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, FUJIFILM Fine Chemical Co., Ltd. ) 2% water dilution): 1.34 parts, distilled water: 48.71 parts

A polypropylene substrate (PP, Trefan BO 60-2500, manufactured by Toray Industries, Inc., substrate thickness 60 μm) was subjected to corona discharge treatment under the condition of 730 J / m ² . Thereafter, the adhesive layer forming coating solution 29 was applied by a bar coater using a bar count # 4 and dried at 80 ° C. for 2 minutes to form a laminate with an adhesive layer having an average thickness of 1 μm.

-Preparation of hard coat layer-
A hard coat layer forming coating solution 25 was obtained by mixing a hard coat layer forming composition having the following composition.

-Composition of hard coat layer forming composition 29-
Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%): 2.93 parts Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) ): 9.62 parts ・ Condensation aid (metal chelate, ALCH, Kawaken Fine Chemical, solid content 100%): 2.13 parts ・ UV absorber (cerium oxide sol, Niedral U-15, manufactured by Taki Chemical Co., Ltd.) , Solid content 15%): 12.53 parts · Inorganic filler (alumina sol, F3000, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 5%): 38.95 parts · Surfactant (Naroacty CL-95, Sanyo Chemical) Industrial Co., Ltd., 1% water dilution): 2.43 parts Acetic acid (Wako Pure Chemical Industries, Ltd.): 0.77 parts Distilled water: 30.64 parts

Next, a corona discharge treatment was performed on the adhesive layer of the laminate with the adhesive layer under the condition of 730 J / m ² . Thereafter, a hard coat forming coating solution 29 was applied by a bar coater using bar number # 22 and dried at 80 ° C. for 2 minutes to obtain a laminate with a hard coat film having an average thickness of 3 μm.

-Formation of antireflection film-
The aqueous coating material 1 prepared in Example 1 was subjected to corona discharge treatment on the hard coat layer of the laminate with a hard coat film under the condition of 730 J / m ² . Then, it apply | coated with the bar coater using bar number # 4, and was dried at 80 degreeC for 2 minutes, and the laminated body with an antireflection film with an average thickness of 130 nm was obtained.

-Formation of back surface A layer-
The surface opposite to the surface on which the antireflection film of the laminate with antireflection film was formed was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the said coating liquid 29 for contact bonding layer formation was apply | coated with the bar coater using bar number # 4, and the laminated body with a back surface A layer with an average thickness of 1 micrometer was obtained by making it dry at 80 degreeC for 2 minutes.

-Formation of back surface B layer-
-Composition of back surface B layer forming composition 29-
Acrylic resin (Ceranate WSA-1070, manufactured by DIC Corporation, solid content 40%): 68.23 parts Fluorosurfactant (sodium bis (3, 3, 4, 4, 5, 5, 6, 6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, FUJIFILM Fine Chemical Co., Ltd., 2% water dilution): 1.13 parts, distilled water: 30.64 parts

  Corona discharge treatment was performed on the back surface A layer of the laminate with the back surface A layer under the condition of 730 J / m2. Then, the back surface B layer forming coating solution 29 was applied by a bar coater using bar number # 20, and dried at 80 ° C. for 2 minutes to form a laminate with a back surface B layer having an average thickness of 10 μm. .

-Formation of back surface C layer-
-Composition of backside C layer forming composition 29-
Polyolefin resin (Arrow Base SE-1013N, manufactured by Unitika Ltd., solid content 20%): 33.52 parts Fluorosurfactant (sodium bis (3,3,4,4,5,5,6) , 6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, Fujifilm Fine Chemical Co., Ltd., 2% water dilution): 2.84 parts, distilled water: 63.63 parts Laminate with back B layer A corona discharge treatment was performed on the rear surface B layer of 730 under the condition of 730 J / m2. Then, the coating liquid 29 for back surface C layer formation was apply | coated with the bar coater using bar number # 8, and it dried at 80 degreeC for 2 minutes, and produced the solar cell front sheet of average thickness 1 micrometer.

(Example 30)
A solar cell front sheet was produced in the same manner as in Example 29 except that the hard coat layer forming composition was changed to the following composition and the bar number was changed to # 10.

-Composition of hard coat layer forming composition 30-
Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%): 16.56 parts Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) ): 26.91 parts ・ Condensation aid (metal chelate, aluminum chelate D, Kawaken Fine Chemical, solid content 76% isopropyl alcohol solution): 1.29 parts ・ UV absorber (cerium oxide sol, Niedral B-10, Taki Chemical Co., Ltd., solid content 10%): 45.56 parts, surfactant (Naroacty CL-95, Sanyo Chemical Industries, 1% water dilution): 2.38 parts, surfactant ( Lapisol A-90, manufactured by NOF Corporation, 1% water dilution): 3.40 parts, distilled water: 3.90 parts

(Example 31)
A solar cell front sheet was produced in the same manner as in Example 29 except that the hard coat layer-forming composition was changed to the following composition.

-Composition of hard coat layer forming composition 31-
Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%): 2.93 parts Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) ): 9.62 parts ・ Condensation aid (metal chelate, ALCH, Kawaken Fine Chemical, solid content 100%): 2.13 parts ・ UV absorber (cerium oxide sol, Niedral U-15, manufactured by Taki Chemical Co., Ltd.) , Solid content 15%): 12.53 parts · Inorganic filler (alumina sol, F1000, manufactured by Kawaken Fine Chemical Co., Ltd., solid content 5%): 38.95 parts · Surfactant (Naroacty CL-95, Sanyo Kasei) Industrial Co., Ltd., 1% water dilution): 2.43 parts Acetic acid (Wako Pure Chemical Industries, Ltd.): 0.77 parts Distilled water: 30.64 parts

(Example 32)
[Production of base film with undercoat layer]
A base film with an undercoat layer having a structure in which an undercoat layer was provided on the back surface of the base film was produced as follows.

-Synthesis of polyester-
About 123 kg of bis (hydroxyethyl) terephthalate was previously charged in a slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.). The esterification reaction tank maintained at 2 × 10 ⁵ Pa was sequentially supplied over 4 hours, and the esterification reaction was further performed over 1 hour after the completion of the supply. Thereafter, 123 kg of the obtained esterification reaction product was transferred to a polycondensation reaction tank.

  Subsequently, 0.3% by mass of ethylene glycol was added to the polycondensation reaction tank to which the esterification reaction product had been transferred, based on the resulting polymer. After stirring for 5 minutes, an ethylene glycol solution of cobalt acetate and manganese acetate was added to 30 ppm and 15 ppm, respectively, with respect to the resulting polymer. After further stirring for 5 minutes, a 2% by mass ethylene glycol solution of a titanium alkoxide compound was added to 5 ppm with respect to the resulting polymer. Five minutes later, a 10% by mass ethylene glycol solution of ethyl diethylphosphonoacetate was added so as to be 5 ppm with respect to the resulting polymer. Thereafter, while stirring the low polymer at 30 rpm, the reaction system was gradually heated from 250 ° C. to 285 ° C. and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, and the polycondensation reaction was stopped. Then, the polymer obtained by the polycondensation reaction was discharged into cold water in a strand shape and immediately cut to produce polymer pellets (diameter: about 3 mm, length: about 7 mm). The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.

  Here, the titanium alkoxide compound used was the titanium alkoxide compound synthesized in Example 1 described in paragraph 0083 of JP-A-2005-340616 (Ti content = 4.44 mass%).

-Solid state polymerization-
The pellets obtained above were held in a vacuum vessel maintained at 40 Pa at a temperature of 220 ° C. for 30 hours for solid phase polymerization.

-Production of polyester film-
The pellets after undergoing solid-phase polymerization as described above were melted at 280 ° C. and cast on a metal drum to produce an unstretched polyethylene terephthalate (PET) film having a thickness of about 3 mm.
Thereafter, the unstretched PET film was stretched 3.4 times in the machine direction (MD) at 90 ° C. Next, on one side of the uniaxially stretched PET film stretched in the MD, a coating liquid for forming an undercoat layer having the following composition is stretched in the transverse direction (TD: TD :) so that the coating amount is 5.1 mL / m 2. Transverse Direction) Coating was performed by in-line coating method before stretching.
The PET film coated with the undercoat layer forming coating solution was TD-stretched to form an undercoat layer having a thickness of 0.1 μm and an elastic modulus of 1.5 GPa. The TD stretching was performed under the conditions of a temperature of 105 ° C. and a stretching ratio of 4.5 times.
The PET film on which the undercoat layer is formed is heat-set at a film surface of 190 ° C. for 15 seconds, and then at 190 ° C. with an MD relaxation rate of 5% and a TD relaxation rate of 11%, MD direction and TD direction. Was subjected to a thermal relaxation treatment to obtain a 250 μm thick biaxially stretched PET film (PET film with an undercoat layer) with an undercoat layer.

-Composition of undercoat layer forming composition-
Acrylic resin (AS-563A, manufactured by Daicel FineChem, Inc., solid content 28%): 21.9 partsOxazoline-based cross-linking material (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content 25%): 4 .9 parts Fluorosurfactant (sodium bis (3,3,4,4,5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, Fuji Film Fine Chemical ( Co., Ltd.) 2% water dilution): 0.1 part ・ Distilled water: Remaining amount of 100 parts

-Production of adhesive layer-
An adhesive layer forming coating liquid 32 was obtained by mixing an adhesive layer forming composition having the following composition.

-Composition of the adhesive layer forming composition 32-
Acrylic resin (Ceranate WSA-1070, manufactured by DIC Corporation, solid content 40%): 60.87 parts Oxazoline-based cross-linking material (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content 25%): 5 .13 parts UV absorber (triazine UV absorber, TINUVIN479DW, manufactured by BASF, solid content 40%): 22.75 parts Fluorosurfactant (sodium bis (3,3,4,4,5) , 5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, FUJIFILM Fine Chemicals Co., Ltd., 2% water dilution): 1.01 parts, distilled water: 10.24 parts

Corona discharge treatment was performed on the surface side where the undercoat layer of the PET film with the undercoat layer was not formed under the condition of 730 J / m ² . Thereafter, the adhesive layer-forming coating solution 32 was applied by a bar coater using a bar number # 18 and dried at 170 ° C. for 2 minutes to form a laminate with an adhesive layer having an average thickness of 9 μm.

-Preparation of hard coat layer-
A hard coat layer forming coating liquid 32 was obtained by mixing the hard coat layer forming composition having the following composition in the following procedure.
The hard coat layer forming coating solution 32 was adjusted by the following procedure.
After adding KBE-403 to an acetic acid aqueous solution and fully hydrolyzing it, KBE-04 is added and fully hydrolyzed, and a mixed solution containing hydrolysates of these alkoxysilanes (KBE-403 and KBE-04) Got. Subsequently, the coating liquid 32 for hard-coat formation was obtained by adding aluminum chelate D, Snowtex OZL-35, Lapisol A-90, Naroacty CL-95, and water to this liquid mixture.

-Composition of hard coat layer forming composition 32-
Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%): 0.91 part Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%) ): 2.98 parts, acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.): 0.06 parts, condensation aid (metal chelate, aluminum chelate D, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 76% isopropyl alcohol solution) ): 0.89 parts · Inorganic filler (silica, average particle size 100 nm, Snowtex OZL-35, manufactured by Nissan Chemical Industries, Ltd., solid content 35.5%): 8.59 parts · Surfactant (Lapisol A) -90, manufactured by NOF Corporation, 1% water dilution): 3.30 parts Surfactant (NAROACTY CL-95, manufactured by Sanyo Chemical Industries, Ltd., 1% water dilution): 2.30 parts Distilled water: 80.98 parts

Next, a corona discharge treatment was performed on the adhesive layer of the laminate with the adhesive layer under the condition of 730 J / m ² . Thereafter, the hard coat forming coating solution 32 was applied by a bar coater using a bar count # 4 and dried at 170 ° C. for 2 minutes to obtain a laminate with a hard coat film having an average thickness of 0.2 μm. .

-Formation of antireflection film-
The aqueous coating material 1 prepared in Example 1 was subjected to corona discharge treatment on the hard coat layer of the laminate with a hard coat film under the condition of 730 J / m ² . Then, it apply | coated with the bar coater using bar number # 4, and was dried at 170 degreeC for 2 minutes, and the laminated body with an antireflection film with an average thickness of 130 nm was obtained.

-Formation of back surface A layer-
The back surface A layer forming coating liquid 32 was obtained by mixing the back surface A layer forming composition having the following composition.

-Composition of back surface A layer forming composition 32-
-Acrylic resin (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 28%): 52.08 parts-Polyolefin resin (Arrow Base SE-1013N, manufactured by Unitika Co., Ltd., solid content 20%): 8.02 Parts / oxazoline-based cross-linking material (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content 25%): 16.20 parts / UV absorber (triazine-based UV absorber, TINUVIN479DW, manufactured by BASF, solid content 40%) ): 3.50 parts Cross-linking catalyst (dibasic ammonium phosphate aqueous solution, Nippon Chemical Industry Co., Ltd., 35% solids diluted with water): 1.26 parts Fluorosurfactant (sodium bis (3,3 , 4,4,5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, Fuji Film Fine Chemicals Co., Ltd., 2% water dilution): 0 47 parts of distilled water: 18.47 parts

The surface opposite to the surface on which the antireflection film of the laminate with antireflection film was formed was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the said coating liquid 32 for contact bonding layer formation was apply | coated with the bar coater using bar number # 12, and the laminated body with a back surface A layer with an average thickness of 5 micrometers was obtained by making it dry at 170 degreeC for 2 minutes.

-Formation of back surface B layer-
-Composition of back surface B layer forming composition 32-
Polyolefin resin (Arrow Base SE-1013N, manufactured by Unitika Ltd., solid content 20%): 17.45 parts Oxazoline-based cross-linking material (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content 25%): 3.59 parts-Surfactant (EMALEX 110, manufactured by Nippon Emulsion Co., Ltd., 10% solid content diluted with water): 4.27 parts-Distilled water: 74.69 parts

Corona discharge treatment was performed on the back surface A layer of the laminate with the back surface A layer under the condition of 730 J / m ² . Thereafter, the back surface B layer forming coating solution 32 is applied by a bar coater using a bar number # 5.6, and dried at 170 ° C. for 2 minutes to obtain a solar cell front sheet having an average thickness of 0.5 μm. Produced.

-Fabrication of solar cell module-
Solar cell front sheet described in Examples 29 to 32, EVA sheet (F806P: manufactured by Hangzhou first PV material), crystalline solar cell, EVA sheet (F806P: manufactured by Hangzhou first PV material), Examples A solar cell module was produced by hot pressing the solar cell front sheet described in 29-32 as a back sheet.
Moreover, the adhesion conditions for the EVA sheet were as follows.
Using a vacuum laminator, vacuuming was performed at 145 ° C. for 5 minutes, followed by pressure heating at 0.1 MPa for 10 minutes for adhesion.
When the power generation operation was performed using the produced solar cell module, it showed good power generation performance as a solar cell.

(Example 33)
-Composition A-
The composition A was obtained by mixing the following composition in the following procedures.

-Composition of hydrolyzate for composition A formation-
MS-51 (compound represented by Formula 1, manufactured by Mitsubishi Chemical Corporation): 1.50 parts Acetic acid (diluted with 5% distilled water): 0.38 parts Distilled water: 13.11 parts The above composition Were mixed and stirred at room temperature for 16 hours to obtain a hydrolyzate for forming composition A.

-Composition of Composition A-
-Hydrolysis liquid for forming composition A: 14.99 parts-Distilled water: 79.01 parts-F-444 (Fluorine-based surfactant diluted with 1% distilled water, manufactured by DIC Corporation): 6.00 parts After mixing the composition, the composition A was obtained by filtering with a # 380 nylon mesh filter.

-Composition B-
Composition B was obtained by mixing the following composition according to the following procedure.

-Composition of core-shell particle dispersion for forming composition B-
Emulsion particle dispersion 4: 10.81 parts Distilled water: 2.35 parts Acetic acid (diluted with 5% distilled water): 0.38 parts MS-51 (compound represented by Formula 1, Mitsubishi Chemical Corporation )): 1.50 parts

Distilled water, acetic acid and MS-51 were added to the emulsion particle dispersion 1 obtained in Example 1 and stirred at 25 ° C. for 16 hours to obtain a core-shell particle dispersion for composition B formation. Next, 84.96 parts of distilled water was mixed, and then filtered through a # 380 nylon mesh filter to obtain a composition B containing core-shell particles containing a nonpolar solvent as a core material, a surfactant and water.
The aqueous coating material 33 was obtained by mixing the composition A and the composition B in the following ratio.

-Composition of aqueous coating material 33-
-Composition A: 50.00 parts-Composition B: 50.00 parts

Next, a corona discharge treatment was performed on a polypropylene base material (PP, Trefan BO 60-2500, manufactured by Toray Industries, Inc., base material thickness 60 μm) under the condition of 730 J / m ² . Thereafter, the aqueous coating material 33 was applied by a bar coater using a bar number # 8, and dried at 80 ° C. for 2 minutes to form a coating layer having an average thickness of 130 nm, thereby obtaining a laminate.

(Comparative Example 1)
As shown in Table 3, the water-based coating material C1 of Comparative Example 1 was used in the same manner as in Example 1, except that the base material, organic solvent, surfactant, W / O ratio, and drying conditions were changed. Each of the laminates C1 was produced.
Further, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

“W / O ratio” in Tables 1 to 3 represents the total content of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less with respect to the total mass of the nonpolar solvent.
Details of the abbreviations described in Tables 1 to 3 other than those described above are shown below.
Heptane: n-heptane, manufactured by Wako Pure Chemical Industries, Ltd. Octane: n-octane, manufactured by Wako Pure Chemical Industries, Ltd. Cyclooctane: manufactured by Wako Pure Chemical Industries, Ltd. xylene: p-xylene, Wako Pure Chemical Industries ( Dodecane: n-dodecane, manufactured by Wako Pure Chemical Industries, Ltd. Tetradecane: n-tetradecane, manufactured by Wako Pure Chemical Industries, Ltd. Heptadecane: n-heptadecane, manufactured by Wako Pure Chemical Industries, Ltd. Octadecane: n-octadecane , Manufactured by Wako Pure Chemical Industries, Ltd. Ca-2: hexadecyltrimethylammonium bromide, cationic surfactant, manufactured by Wako Pure Chemical Industries, Ltd. Ca-3: polyethyleneimine, molecular weight Mw1,200, cationic surfactant, Japanese Kojun Pharmaceutical Co., Ltd. Ca-4: Polyethyleneimine, molecular weight Mw 10,000, cationic surfactant, Wako Pure Chemical Industries, Ltd. Ca-5: Li ethyleneimine, molecular weight Mw70,000, cationic surfactant, manufactured by Nippon Shokubai Co., Ltd. No-1: polyoxyethylene lauryl ether, nonionic surfactant, Nippon Emulsion Co., Ltd. EMALEX 710
Glass: Glass base material, manufactured by Nippon Electric Glass Co., Ltd., OA-10G, thickness 700 μm
PET: Polyethylene terephthalate base material PC: Polycarbonate base material, Carbo Glass C110 manufactured by Asahi Glass Co., Ltd., thickness 500 μm
Acrylic resin: Acrylic resin base material, manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G, thickness 75 μm

As shown in Tables 1 to 3, the aqueous coating materials of Examples 1 to 33 are excellent in the light transmittance of the obtained films.
On the other hand, the water-based coating material of Comparative Example 1 was inferior in light transmittance of the obtained film as compared with the water-based coating materials of Examples 1 to 33.

Claims (15)

water,
At least one selected from the group consisting of a siloxane compound represented by the following formula 1, a hydrolyzate of the siloxane compound represented by the following formula 1, and a hydrolysis condensate of the siloxane compound represented by the following formula 1. A compound of
Surfactants, and
Including core-shell particles containing a nonpolar solvent as a core material,
The surfactant includes at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less,
The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass or less based on the total mass of the nonpolar solvent. Wood.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.   The aqueous coating material according to claim 1, wherein the surfactant contains a cationic surfactant having a molecular weight of 10,000 or less.   The aqueous coating material according to claim 1, wherein the nonpolar solvent is a hydrocarbon having 7 or more carbon atoms.   The water-based coating material according to any one of claims 1 to 3, wherein a variation coefficient of a particle diameter of the core-shell particles is 100% or less.   The aqueous coating material according to any one of claims 1 to 4, wherein a surface of the core-shell particle is hydrophilic. The coating layer formed on the substrate is dried,
The coating layer includes core-shell particles containing water, a hydrolytic condensate of a siloxane compound represented by Formula 1, a surfactant, and a nonpolar solvent as a core material,
The surfactant includes at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less,
The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less is 0.5% by mass or more and 70% by mass or less based on the total mass of the nonpolar solvent,
A film having voids in at least some of the core-shell particles in the dried coating layer.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.   The film according to claim 6, wherein the average internal void diameter of the film is 30 nm or more, and the variation coefficient of the void diameter is 60% or less.   The film according to claim 6 or 7, which is an antireflection film.   The laminated body which has a film | membrane of any one of Claims 6-8.   The laminated body of Claim 9 which has the said film | membrane on a base material.   The laminate according to claim 10, wherein the substrate is a resin substrate.   It is a solar cell front sheet, The laminated body of any one of Claims 9-11. The process of providing the aqueous | water-based coating material of any one of Claims 1-5 on a base material, and forming a coating layer, and
Including a step of drying the coating layer,
A method for producing a membrane, wherein at least a part of the core-shell particles becomes hollow particles that form voids inside the coat layer after the drying step. The process of providing the aqueous | water-based coating material of any one of Claims 1-5 on a base material, and forming a coating layer, and
Including a step of drying the coating layer,
A method for producing a laminate, wherein at least a part of the core-shell particles become hollow particles that form voids inside the coat layer after the drying step. A composition A containing a siloxane compound represented by the following formula 1,
Comprising water, a surfactant, and a non-polar solvent composition B,
The surfactant includes at least one surfactant selected from the group consisting of a cationic surfactant having a molecular weight of 10,000 or less and a nonionic surfactant having a molecular weight of 10,000 or less,
The total content of the cationic surfactant having a molecular weight of 10,000 or less and the nonionic surfactant having a molecular weight of 10,000 or less in the composition B is 0.5% by mass or more and 70% by mass with respect to the total mass of the nonpolar solvent. A water-based coating material kit.

In Formula 1, R ¹ and R ² each independently represent a monovalent organic group having 1 to 6 carbon atoms, and R ³ and R ⁴ each independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, An organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyoxyalkylene group, carboxy group and quaternary ammonium group; Each independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.