WO2019167414A1 - Aqueous coating material, film and production method therefor, layered product and production method therefor, and aqueous coating material kit - Google Patents

Abstract

Provided are: an aqueous coating material comprising water, at least one compound selected from the group consisting of siloxane compounds represented by formula 1, hydrolysates of the siloxane compounds represented by formula 1, and hydrolysis-condensation products of the siloxane compounds represented by formula 1, a surfactant, and core-shell particles containing an organic solvent as a core material, wherein 20 mass% or more of the organic solvent is a nonpolar solvent having a boiling point of 90-350°C; a film using the aqueous coating material and a production method for the film; a layered product and a production method for the layered product; and an aqueous coating material kit capable of producing the aqueous coating material.

Description

Water-based coating material, film and method for producing the same, laminate and method for producing the same, and water-based coating material kit

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.
Generally, 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 JP-T-2017-500384 or JP-A-2014-203006.
JP-T-2017-500384 discloses that 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. And forming an oil-in-water emulsion by forming 1 to 50% by weight of emulsified droplets having a particle size of 30 to 300 nm, wherein the particle size is measured by DLS. Providing an inorganic oxide shell layer to the emulsified droplets by adding at least one inorganic oxide precursor to the emulsion obtained in step 2) and in step 1). Forming organic-inorganic core / shell nanoparticles having a core / shell mass ratio of 0.2 to 25, wherein the core is the sum of compound A and emulsion stabilizer C, and the shell is And a step which is an inorganic oxide precursor equal metal oxide, and a process for producing an antireflective coating composition, Compound A, non-polar organic compound having a water solubility of 5 kg / m ³ at most And the emulsion stabilizer C comprises at least one monomer unit having a cationic charge and at least one monomer unit that is neutral or non-ionic and has an overall positive zeta potential. A process is described which is a sex addition copolymer.

Japanese Patent Application Laid-Open No. 2014-203006 discloses an optical coating film formed of a coating film formed on a base material, wherein the coating film includes a maximum value of a major axis (L) and a minor axis perpendicular thereto. Average value of (D): ((L + D) / 2) has voids (X) of 20 nm or more, and the major axis (L) and minor axis (D) of the voids (X) are 1 <L / D An optical coating film in which the gap (X) is not in contact with the substrate at the interface with the substrate is described.

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. An aqueous solution containing at least one compound, a surfactant, and core-shell particles containing an organic solvent as a core material, wherein 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower. Coat material.

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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m 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 at least 50% by mass in the organic solvent is the nonpolar solvent.
<3> The aqueous coating material according to <1> or <2>, wherein the nonpolar solvent is a hydrocarbon compound having 7 or more carbon atoms.
<4> The aqueous coating material according to <3>, wherein the hydrocarbon compound is an alkane.
<5> The aqueous coating material according to any one of <1> to <4>, wherein a coefficient of variation of the particle diameter of the core-shell particles is 100% or less.
<6> The coating layer is dried, and the coating layer includes water, a hydrolysis-condensation product of the siloxane compound represented by Formula 1, a surfactant, and core-shell particles containing an organic solvent as a core material, 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower, and a film having voids in at least some of the core-shell particles in the coated layer after drying.

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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m 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 comprising a step of applying the aqueous coating material according to any one of <1> to <5> on a base material to form a coating layer, 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 comprising a step of applying the aqueous coating material according to any one of <1> to <5> on a substrate to form a coating layer, 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 an organic solvent, and 20% by mass of the organic solvent in the composition B The above is an aqueous coating material kit which is a nonpolar solvent having a boiling point of 90 ° C or higher and 350 ° C or lower.

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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m 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 the present specification, “to” indicating a numerical range is used in a sense including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
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 an organic solvent as a core material, wherein 20% by mass or more of the organic solvent has a boiling point of 90 ° C or higher and 350 ° C or lower. It is a 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 ( Vinylphenyl group), (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Represents an organic 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.
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 core-shell particles containing an organic solvent as a core material, and 20% by mass or more of the organic solvent has a boiling point of 90 ° C. or higher and 350 ° C. or lower. By being a polar solvent, at the time of drying at the time of forming a film, at least a part of the organic solvent volatilizes, and voids can be easily formed in the resulting film. It is presumed that the organic solvent has little influence at the time of volatilization and is excellent in volatility of the organic solvent even at a low temperature below the boiling point, and the refractive index of the film obtained by the voids can be reduced. Therefore, it is estimated that the obtained film is excellent in light transmittance.
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 obtained because 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or more and 350 ° C. or less, so that components remaining in the film after drying are reduced. Excellent film haze.

<Core shell particles containing organic solvent as core material>
The aqueous coating material according to the present disclosure includes core-shell particles containing an organic solvent as a core material, and 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
The “boiling point” in the present disclosure is a boiling point at 1 atm (101,325 Pa). In addition, 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 having a boiling point of 90 ° C. or higher and 350 ° C. or lower include hydrocarbon compounds, fluorinated hydrocarbon compounds, and silicone compounds. From the viewpoint of light transmittance and haze of the resulting film, hydrocarbon compounds It is preferable that
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 100 ° C. or higher and 340 ° C. or lower, more preferably 120 ° C. or higher and 320 ° C. or lower, and 200 ° C. or higher, from the viewpoint of light transmittance and haze of the obtained film. It is particularly preferable that the temperature is 310 ° C or lower.

Specific examples of nonpolar solvents having a boiling point of 90 ° C. or higher and 350 ° C. or lower include, for example, 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), cyclo Preferred examples include octane (boiling point: 149 ° C), toluene (boiling point: 111 ° C), p-xylene (boiling point: 138 ° C), m-xylene (boiling point: 139 ° C), o-xylene (boiling point: 144 ° C). .

The organic solvent may be only one kind of organic solvent or a mixed solvent of two or more kinds of organic solvents.
Moreover, the nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower may be used alone or in combination of two or more.
The content of the nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower in the organic solvent contained as the core agent of the core-shell particles may be 20% by mass or more with respect to the total mass of the organic solvent. From the viewpoint of light transmittance and haze of the film, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 99% by mass or more and 100% by mass. It is particularly preferred that

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 1.0 μm, from the viewpoint of the strength, light transmittance, and haze of the obtained film. It is preferably 0.1 μm to 0.6 μm, more preferably 0.1 μm to 0.4 μm.
In addition, 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 from 08 μm to 1.0 μm, further preferably from 0.1 μm to 0.6 μm, and particularly preferably from 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 90% or less from the viewpoint of light transmittance and haze of the obtained film. More preferably, it is 70% or less, more preferably 0% or more and 50% 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 obtained film, light transmittance and haze, and 5:95 to 5 : 95 is more preferable, and 10:90 to 90:10 is particularly preferable.

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

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. More preferably, the content is 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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m 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, branched, 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, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, and cyclohexyl groups. 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 resulting 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, and preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoints of strength, light transmittance and haze of the resulting 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 selected from the group consisting of acryloxy group, (meth) acrylamide group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group An alkyl group having a group is preferable, an alkyl group is more preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable.
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 KBE-04, KBE-13, KBE-22, KBE-1003, KBM-303, KBE-403, KBM-1403, KBE-503, KBM- manufactured by Shin-Etsu Chemical Co., Ltd. 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, Dynasylan 4150 manufactured by Evonik Japan Co., Ltd., MKC silicate MS-51, MS-56, MS-57, MS-56S manufactured by Mitsubishi Chemical Co., Ltd., ethyl silicate 28 manufactured by Colcoat Co., Ltd. N-propyl silicate, N-butyl silicate, SS-101, etc. It is.

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, light transmittance and haze of the resulting film. It is more preferably 99% by mass, and particularly preferably 70% by mass to 95% by 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.

<Surfactant>
The aqueous coating material according to the present disclosure includes a surfactant.
Examples of the surfactant include nonionic surfactants, anionic surfactants that are ionic surfactants, cationic surfactants, and amphoteric surfactants, and any of them can be suitably used in the present disclosure.
Among these, from the viewpoint of efficient formation of core-shell particles by the attractive force interactive with the above-mentioned specific siloxane compound, storage stability, and light transmittance and haze of the obtained film, a nonionic surfactant, and At least one surfactant selected from the group consisting of cationic surfactants is preferred, and cationic surfactants are more preferred.
The molecular weight of the surfactant is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoints of storage stability and light transmittance and haze of the resulting film. Is more preferably 000 or less, and particularly preferably 300 or more and 800 or less.

Examples of the cationic surfactant include a quaternary ammonium salt type, a pyridinium salt type, an amine salt type, and a polyamine type surfactant. Specific examples include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylpyridinium salts, benzalkonium salts, and alkylamine salts. More specifically, hexadecyltrimethylammonium bromide, hexadecylpyridinium chloride, benzalkonium chloride, monomethylamine hydrochloride, polyethyleneimine and the like can be mentioned.
From the viewpoint of emulsion particle stability of the nonpolar solvent, quaternary ammonium salt type, pyridinium salt type and polyamine type surfactants are preferable, and quaternary ammonium salt type and pyridinium salt type surfactants are more preferable.

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.

Examples of other ionic surfactants include anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates; amphoteric surfactants such as 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 F-444 and other MegaCure series manufactured by DIC, Surflon S-221 and other AGC Seimi Chemical Co. Surflon series, and Footage 100 and other Neos Corporation footers. Examples include the Gent series. Examples of the silicone surfactant include leveling material 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 viewpoint of storage stability and light transmittance and haze of the obtained film. The content 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.
In addition, the content of the surfactant is 0.5% by mass with respect to the total mass of the organic solvent that is the core material in the core-shell particles, from the viewpoints of storage stability and light transmittance and haze of the obtained film. It is preferably 70% by mass or less, more preferably 1% by mass or more and 35% by mass or less, and particularly preferably 5% by mass or more and 25% by mass or less.

<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 relative 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 is 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, more preferably 40% by mass to 99.9% by mass with respect to the total mass of the aqueous coating material. The content is more preferably 50% by mass to 99.8% by mass, and particularly preferably 70% by mass to 99.5% by mass.

[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 water-based coating material-
The method for producing an aqueous coating material according to the present disclosure is not particularly limited, and an organic solvent, a surfactant, and water are mixed, the organic solvent is dispersed in water, and a specific siloxane compound is added to partially add water. Forming a shell layer on the surface of the organic solvent dispersed by decomposing and dispersing to produce core-shell particles, a method for producing an aqueous coating material, core-shell particles containing an organic solvent as a core material, a specific siloxane compound, a surfactant, And the method of mixing and manufacturing water is mentioned.
Above all, organic solvent, surfactant and water are mixed, organic solvent is dispersed in water, specific siloxane compound is added and partially hydrolyzed and condensed to form a shell layer on the surface of the dispersed organic solvent. A method of producing core-shell particles and producing an aqueous coating material is preferred. The specific siloxane compound may be added together with an organic solvent, a surfactant, and water, or may be added after the organic 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 or 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 type 20 manufactured by PRIMIX Co., Ltd., an ultrasonic homogenizer SONIFIER SFX250 manufactured by Nippon Emerson Co., Ltd., OMEGA LAB manufactured by Ashizawa Finetech Co., Ltd., and SUGINO CO., LTD. Examples include machine starburst 10 and SPG Techno Co., Ltd. KH-125.

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.
Surfactant and organic solvent may be added to the resulting hydrolyzate solution of the specific siloxane compound, or organic solvent, surfactant and water are mixed to disperse the organic solvent in water. The solution obtained may be mixed with the hydrolyzate solution of the specific siloxane compound. Alternatively, hydrolysis and shell formation may be carried out simultaneously by mixing a liquid obtained by mixing an organic solvent, a surfactant and water and dispersing the organic solvent in water with the specific siloxane compound.

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)
1st Embodiment in the film | membrane which concerns on this indication is formed by drying a coating layer, and the said coating layer is water, the hydrolysis-condensation product of the siloxane compound represented by the said Formula 1, surfactant, and organic Including core-shell particles containing a solvent in a core material, wherein 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower, and at least a part of the core-shell particles in the coated layer after drying. Have voids inside.
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 an organic solvent in the core material in the coating layer is described above in the aqueous coating material according to the present disclosure. This is the same as the preferred embodiment.
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.
Moreover, it is preferable to have the said coating layer on a base material.

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, and further preferably 40 nm to 150 nm from the viewpoint of strength, light transmittance, and haze. It is particularly preferred that
Further, the coefficient of variation of the internal 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 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 variation coefficient 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), thereby 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, the thickness 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, a device 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 The measurement is performed by an apparatus in which a large-sized large sample chamber (MPC-3100, manufactured by Shimadzu Corporation) is connected to an ultraviolet-visible infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation).

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. 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 ultraviolet irradiation (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 suppressing coloring, it is preferable to carry out the heating to 40 to 700 ° C. When using a resin base material, it is necessary to heat at a temperature not higher than the decomposition temperature of the base material. Specifically, it is preferably performed by heating to 40 ° C. to 200 ° C. Further, from the viewpoint of suppressing thermal deformation of the substrate, it is more preferable to carry out the heating to 40 ° C. to 120 ° C.
When heating is performed, the heating time is not particularly limited, but is preferably 1 minute to 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 resin, polycarbonate resin, polyolefin resin, polyacrylic resin, cellulose, polyvinyl chloride, polyimide resin, polyamide resin, and fluorine-based polymer. Among these, polyester resin, polyolefin resin, acrylic resin, or cellulose is preferable from the viewpoint of cost, mechanical strength, transmittance, and transparency.
Examples of the polyester resin include polyethylene terephthalate and polyethylene naphthalate.
Examples of the polyolefin resin 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, particularly 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 and 450 micrometers or less are 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.
It does not specifically limit as a crosslinking agent, An oxazoline type crosslinking agent, an epoxy-type crosslinking agent, a carbodiimide type crosslinking agent, a block isocyanate type crosslinking agent etc. are mentioned, An oxazoline type 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, 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, 2009-269881, JP 2009-263567, JP 2009-75248, JP 2007-164206, JP 2006-96811, JP 2004-75970, JP 2002-156505, JP 2001. -272503 gazette, International Publication No. 12/018087 WO 12/098967, WO 12/086659, it may be made of a hard coat layer as described in WO 11/105594.

Further, the pencil hardness of the surface of the hard coat layer is preferably B or more, more preferably HB or more, and further preferably F or more, from the viewpoint of scratch resistance of the laminate.
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 workability of the laminate. It is.
The pencil hardness on the surface of the hard coat layer means a value measured based on JIS K5600-5-4: 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 particle selected from the group consisting of a metal oxide filler and an inorganic nitride filler 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.

The hard coat layer preferably contains a silica filler from the viewpoint of crosslinking with the siloxane resin in the 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 Seahoster series such as Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.) and the 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 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, the alumina sol series such as alumina sol AS-200 (manufactured by Nissan Chemical Industries), the aluminum sol series such as aluminum sol 10C and aluminum sol F-1000 (Kawaken Fine Chemical Co., Ltd.) Product), Heidilite 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 polyhedron shape, a flat plate shape, and a scale shape, a bead shape, a needle shape, and a fiber shape.
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.
When the inorganic filler is a bead shape, needle shape, or fiber shape, the aspect ratio is preferably 4 or more, more preferably 9 or more, still more preferably 100 or more, and particularly preferably 500 or more. By using particles having a high aspect ratio, both the hardness and flexibility of the hard coat layer can be achieved.
The aspect ratio means a value obtained by dividing the secondary particle diameter (bonding length of primary particles) by the primary particle diameter in the case of a bead shape, and the major axis is divided by the minor diameter in the case of a needle shape or a fiber shape. Mean value.

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. 0.1% by mass to 1% by 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 phosphoric acid, 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, acrylic resin, polyester, and polyurethane.
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.
The back layer functions as, for example, a layer for adhesion to a sealing material (for example, a sealing material containing an ethylene-vinyl acetate copolymer (EVA)) in a solar cell module.
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 Arrowbase (registered trademark) SE-1013N, SD-1010, TC-4010, TD-4010, DA-1010 (both manufactured by Unitika 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. Examples of acrylic resins include 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, a preservative, inorganic particles, 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 agent, a surfactant, an antistatic agent, a preservative, inorganic particles, 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, a preservative, inorganic particles, 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 50% by mass or more of the binder polymer is an acrylic resin, 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. The laminate and the polyester film can be constituted by being sealed with a sealing agent typified by a resin such as an ethylene-vinyl acetate copolymer.

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.

The solar cell element used in the solar cell module according to the present disclosure is not particularly limited, and silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, copper-indium-gallium-selenium, copper-indium-selenium. Various known solar cell elements such as III-V and II-VI compound semiconductors 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 a composition A containing the siloxane compound represented by the formula 1 and a composition B containing water, a surfactant, and an organic solvent, 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
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 hydrolysis condensate of the siloxane compound represented by formula 1 on the surface of the dispersed organic solvent. Thus, 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, water, surfactant, and organic solvent represented by Formula 1 in the aqueous coating material kit according to the present disclosure are the same as the preferred embodiments of the aqueous coating material described above, except for the embodiments described below. is there.
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>
The composition B contains water, a surfactant, and an organic solvent, and 20% by mass or more of the organic solvent in the composition B is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
In composition B, the organic solvent is preferably in a state 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 organic 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 content of the organic 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 particularly preferably 0.2% by mass to 30% by mass.
The content of the surfactant in the composition B is preferably 0.01% by mass to 30% by mass with respect to the content of the organic solvent.
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.

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.): 0.83 parts Hexane (n-hexane, manufactured by Wako Pure Chemical Industries, Ltd.): 1.94 parts Ca-1 (hexadecylpyridinium) Chloride 10% distilled water dilution, cationic surfactant, manufactured by Wako Pure Chemical Industries, Ltd.): 4.42 parts, distilled water: 42.81 parts For the preparation of the emulsion particle dispersion, the following procedure is used. went.
Hexadecane, hexane, Ca-1 and ion-exchanged water are mixed, and by using an ultrasonic homogenizer Sonifier 450 manufactured by Nippon Emerson Co., Ltd., cooling with ice water and treating with stirring for 30 minutes, an emulsion of hexadecane is formed in water. An existing dispersion 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) MS-51 is a compound in which R ¹ , R ² and R ³ in the above formula 1 are methyl groups, m is 2 and n is 5 on average.

Next, MS-51, acetic acid, and distilled water are added to the emulsion particle dispersion, and the mixture is further stirred at 25 ° C. for 16 hours, whereby core-shell particles containing a nonpolar solvent as a core material, represented by Formula 1. A core-shell particle dispersion containing a compound, 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-exchanged water and F-444 were added to the core-shell particle dispersion, and the mixture was stirred at 25 ° C. for 2 days to obtain an aqueous coating material 1.

<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. The transmittance of the laminate is measured with an ultraviolet-visible infrared spectrophotometer (model number: UV-3100PC, manufactured by Shimadzu Corporation), and 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 battery 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 31)
As shown in Tables 1 to 3, Examples 2 to 3 were performed in the same manner as in Example 1 except that the base material, organic solvent, surfactant, W / O ratio, bar number, and drying conditions were changed. 31 emulsion particle dispersions, core-shell particle dispersions, aqueous coating materials 2 to 31 and laminates 2 to 31 were prepared.

(Example 32)
An emulsion particle dispersion 32, a core-shell particle dispersion 32, an aqueous coating material 32, and a laminate 32 were produced in the same manner as in Example 4 except that the composition of the core-shell particle dispersion was changed.

-Composition of core shell particle dispersion 32-
Emulsion particle dispersion: 9.74 parts Distilled water: 29.04 parts Acetic acid (diluted with 5% distilled water): 1.26 parts MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) 9.96 parts

(Example 33)
An emulsion particle dispersion 33, a core-shell particle dispersion 33, an aqueous coating material 33, and a laminate 33 were produced in the same manner as in Example 4 except that the composition of the core-shell particle dispersion was changed.

-Composition of core shell particle dispersion 32-
Emulsion particle dispersion: 21.06 parts Distilled water: 17.72 parts Acetic acid (diluted with 5% distilled water): 1.26 parts MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) 9.96 parts

(Example 34)
An emulsion particle dispersion 34, a core-shell particle dispersion 34, an aqueous coating material 34, and a laminate 34 were produced in the same manner as in Example 4 except that the composition of the emulsion particle dispersion and the core-shell particle dispersion was changed.

-Composition of emulsion particle dispersion 34-
Hexadecane (n-hexadecane, manufactured by Wako Pure Chemical Industries, Ltd.): 5.53 partsCa-1 (hexadecylpyridinium chloride 10% distilled water diluted, cationic surfactant, manufactured by Wako Pure Chemical Industries, Ltd.) : 8.85 parts ・ Distilled water: 35.62 parts

-Composition of core-shell particle dispersion 34-
Emulsion particle dispersion: 18.66 parts Distilled water: 24.08 parts Acetic acid (diluted with 5% distilled water): 1.26 parts MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) (Made) 6.00 parts

(Example 35)
An emulsion particle dispersion 35, a core-shell particle dispersion 35, an aqueous coating material 35, and a laminate 35 were produced in the same manner as in Example 34 except that the composition of the core-shell particle dispersion was changed.

-Composition of core shell particle dispersion 35-
Emulsion particle dispersion: 38.05 parts Distilled water: 4.69 parts Acetic acid (diluted in 5% distilled water): 1.26 parts MS-51 (compound represented by formula 1, Mitsubishi Chemical Corporation) (Made) 6.00 parts

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Tables 1 to 3.

(Example 36)
[Preparation of solar cell front sheet]
-Production of adhesive layer-
An adhesive layer forming coating solution 36 was obtained by mixing an adhesive layer forming composition having the following composition.

-Composition of Adhesive Layer Forming Composition 36-
Polyolefin resin (Arrowbase 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 Chemicals 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 composition 36 was applied by a bar coater using a bar number # 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 liquid 36 was obtained by mixing a hard coat layer-forming composition having the following composition.

-Composition of hard coat layer forming composition 36-
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, manufactured by Kawaken Fine Chemical Co., Ltd., 100% solid content): 2.13 parts ・ UV absorber (cerium oxide sol, Niedral U-15, 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, manufactured by Sanyo Chemical Industries, 1% water dilution): 2.43 parts, acetic acid (manufactured by 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, the hard coat forming coating solution 36 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 4 prepared in Example 4 was subjected to a 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 layer A-
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 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 layer B-
-Composition of backside B layer forming composition 36-
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, manufactured by FUJIFILM Fine Chemicals, 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 / m ² . Then, the back surface B layer forming coating solution 36 was applied by a bar coater using a 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 backside C layer-
-Composition of backside C layer forming composition 36-
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, manufactured by FUJIFILM Fine Chemicals Co., Ltd., 2% water dilution): 2.84 parts, distilled water: 63.63 parts

Corona discharge treatment was performed on the back surface B layer of the laminate with the back surface B layer under the condition of 730 J / m ² . Then, the back surface B layer forming coating solution 36 was applied by a bar coater using a bar number # 8 and dried at 80 ° C. for 2 minutes to produce a solar cell front sheet having an average thickness of 1 μm.

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 37)
A solar cell front sheet was produced in the same manner as in Example 36 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 37-
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, manufactured by Kawaken Fine Chemical Co., Ltd., solid content 76% isopropyl alcohol solution): 1.29 parts ・ UV absorber (cerium oxide sol, Niedral B-) 10, manufactured by Taki Chemical Co., Ltd., solid content 10%): 45.56 parts Surfactant (Naroacty CL-95, manufactured by 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

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 38)
A solar cell front sheet was produced in the same manner as in Example 36 except that the hard coat layer-forming composition was changed to the following composition.

-Composition of hard coat layer forming composition 38-
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, manufactured by Kawaken Fine Chemical Co., Ltd., 100% solid content): 2.13 parts ・ UV absorber (cerium oxide sol, Niedral U-15, Taki Chemical) Co., Ltd., solid content 15%): 12.53 parts, inorganic filler (alumina sol, F1000, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 5%): 38.95 parts, surfactant (Naroacty CL- 95, manufactured by Sanyo Chemical Industries, 1% water dilution): 2.43 parts, acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.): 0.77 parts, distilled water: 30.64 parts

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 39)
[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 resulting polymer in the polycondensation reaction tank to which the esterification reaction product had been transferred. 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, as the titanium alkoxide compound, the titanium alkoxide compound (Ti content = 4.44 mass%) synthesized in Example 1 described in paragraph 0083 of JP-A-2005-340616 was used.

-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 parts Oxazoline-based crosslinking agent (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 Chemicals ( Co., Ltd., 2% water dilution): 0.1 part / distilled water: remaining amount of 100 parts in total

-Production of adhesive layer-
An adhesive layer forming coating solution 38 was obtained by mixing an adhesive layer forming composition having the following composition.

-Composition of the adhesive layer forming composition 39-
Acrylic resin (Ceranate WSA-1070, manufactured by DIC Corporation, solid content 40%): 60.87 parts Oxazoline-based crosslinking agent (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 Fluorine surfactant (sodium bis (3,3,4,4,5) , 5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, manufactured by 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 39 was applied by a bar coater using a bar count # 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 39 was obtained by mixing a hard coat layer forming composition having the following composition in the following procedure.
The hard coat layer forming coating solution 39 was adjusted by the following procedure.
After adding KBE-403 to an acetic acid aqueous solution and sufficiently hydrolyzing it, it is sufficiently hydrolyzed by adding KBE-04, and a mixed solution containing hydrolysates of these alkoxysilanes (KBE-403 and KBE-04) Got. Next, a hard coat forming coating solution 39 was obtained by adding aluminum chelate D, Snowtex OZL-35, Lapisol A-90, Naroacty CL-95, and water to this mixed solution.

-Composition of hard coat layer forming composition 39-
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, NOF Corporation, 1% water dilution): 3.30 parts Surfactant (NAROACTY CL-95, Sanyo Chemical Industries, 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, a hard coat forming coating solution 39 was applied by a bar coater using bar number # 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 4 prepared in Example 4 was subjected to a 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 layer A-
By mixing a back surface A layer forming composition having the following composition, a back surface A layer forming coating liquid 39 was obtained.

-Composition of backside A layer forming composition 39-
Acrylic resin (AS-563A, manufactured by Daicel Finechem, Inc., solid content 28%): 52.08 parts Polyolefin resin (Arrow Base SE-1013N, manufactured by Unitika Ltd., solid content 20%): 8.02 Parts / oxazoline-based crosslinking agent (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 Crosslinking catalyst (dibasic ammonium phosphate aqueous solution, manufactured by 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, manufactured by FUJIFILM Fine Chemicals Co., Ltd., 2% water Interpretation): 0.47 parts 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 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 layer B-
-Composition of backside B layer forming composition 39-
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 liquid 39 was applied by a bar coater using 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.

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

-Fabrication of solar cell module-
Solar cell front sheet described in Examples 36 to 39, 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 manufactured by hot pressing the solar cell front sheet described in 36 to 39 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 40)
-Composition A-
The composition A was obtained by mixing the following composition in the following procedures.

-Composition of hydrolyzed liquid for forming composition A-
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 solution for forming composition A: 14.99 parts-Distilled water: 79.01 parts-F-444 (Fluorine-based surfactant 1% distilled water diluted, manufactured by DIC Corporation): 6.00 parts Above 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 4 obtained in Example 4, and the mixture was stirred at 25 ° C. for 16 hours. A core-shell particle dispersion was obtained.
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 40 was obtained by mixing the composition A and the composition B in the following ratio.

-Composition of aqueous coating material 40-
-Composition A: 50.00 parts-Composition B: 50.00 parts

Next, a corona discharge treatment was performed on a polypropylene substrate (PP, Trefan BO 60-2500, manufactured by Toray Industries, Inc., substrate thickness 60 μm) under the condition of 730 J / m ² . Thereafter, the aqueous coating material 40 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.

In addition, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.

(Comparative Examples 1 and 2)
As shown in Table 5, the aqueous coating material C1 of Comparative Examples 1 and 2 was the same as Example 1 except that the base material, organic solvent, surfactant, W / O ratio, and drying conditions were changed. And C2, and laminates C1 and C2 were produced, respectively.
Further, performance evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

“W / O ratio” in Tables 1 to 5 represents the content of the surfactant at the time of emulsion particle formation relative to the total mass of the organic solvent in the aqueous coating material used.
Details of the abbreviations described in Tables 1 to 5 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, Mw 1,200, cationic surfactant, Wako Pure Yaku Kogyo Co., Ltd. Ca-4: Polyethyleneimine, Mw 10,000, Cationic surfactant, Wako Pure Chemical Industries, Ltd. No-1: Polyoxye Ren lauryl ether, nonionic surfactant, Nippon Emulsion Co., Ltd. EMALEX 710
Glass: Glass base material, OA-10G manufactured by Nippon Electric Glass Co., Ltd., thickness 700μm
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, Sumitomo Chemical Co., Ltd. Technoloy S001G, thickness 75 μm

As shown in Tables 1 to 5, the aqueous coating materials of Examples 1 to 40 are excellent in the light transmittance of the obtained films (coat layers).
On the other hand, the aqueous coating material of Comparative Example 1 or 2 was inferior in light transmittance of the resulting film (coating layer) as compared with the aqueous coating materials of Examples 1 to 40.

The disclosure of Japanese Patent Application No. 2018-035216 filed on February 28, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

Claims (15)

1. 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 an organic solvent as a core material,
   An aqueous coating material, wherein 20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
   

   

   
   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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.
2. The aqueous coating material according to claim 1, wherein at least 50 mass% of the organic solvent is the nonpolar solvent.
3. The aqueous coating material according to claim 1 or 2, wherein the nonpolar solvent is a hydrocarbon compound having 7 or more carbon atoms.
4. The aqueous coating material according to claim 3, wherein the hydrocarbon compound is an alkane.
5. The water-based coating material according to any one of claims 1 to 4, wherein a variation coefficient of a particle diameter of the core-shell particles is 100% or less.
6. The coat layer 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 an organic solvent as a core material,
   20% by mass or more of the organic solvent is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower,
   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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.
7. 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.
8. The film according to claim 6 or 7, which is an antireflection film.
9. A laminate having the film according to any one of claims 6 to 8.
10. The laminate according to claim 9, which has the film on a substrate.
11. The laminate according to claim 10, wherein the substrate is a resin substrate.
12. The laminate according to any one of claims 9 to 11, which is a solar cell front sheet.
13. Applying a water-based coating material according to any one of claims 1 to 5 on a substrate to form 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.
14. Applying a water-based coating material according to any one of claims 1 to 5 on a substrate to form 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.
15. A composition A containing a siloxane compound represented by the following formula 1,
    Comprising water, a surfactant, and a composition B containing an organic solvent,
    An aqueous coating material kit, wherein 20% by mass or more of the organic solvent in the composition B is a nonpolar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
    

    

    
    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, Represents an organic group having a group selected from the group consisting of (meth) acryl group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group, Each m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.