JPWO2019167414A1 - Water-based coating material, film and its manufacturing method, laminate and its manufacturing method, and water-based coating material kit - Google Patents

Abstract

At least selected from the group consisting of water, a siloxane compound represented by the following formula 1, a hydrolyzate of a siloxane compound represented by the following formula 1, and a hydrolyzed condensate of a siloxane compound represented by the following formula 1. An aqueous coating material containing 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 non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower. In addition, a film using the water-based coating material and a method for producing the same, a laminate and a method for producing the same, and a water-based coating material kit capable of producing the water-based coating material.

Description

The present disclosure relates to a water-based coating material, a film and a method for producing the same, a laminate and a method for producing the same, and a water-based coating material kit.

The water-based coating material containing a siloxane compound uses a solvent containing water, has a low surface energy of the formed film, and is excellent in transparency, and is therefore used for various purposes.
It is preferably used for optical lenses, optical filters, flattening films for thin film transistors (TFTs) of various displays, antireflection films, dew condensation prevention films, antifouling films, surface protective films, and the like.

Further, in recent years, a solar cell module, which is a power generation method having a small environmental load during power generation, has attracted attention. Generally, a solar cell module is provided with a surface protective material, a solar cell in which a solar cell element is sealed with a sealing material, and a back surface side base material in order from the light receiving surface side (front surface side) where sunlight is incident. There is.
As a surface protective material provided on the light receiving surface of the solar cell module, glass, a weather resistant resin film, or the like is generally used.

Examples of the conventional surface protective material or a method for producing the surface protective material include those described in Japanese Patent Application Laid-Open No. 2017-520384 or Japanese Patent Application Laid-Open No. 2014-203006.
In Japanese Patent Application Laid-Open No. 2017-500244, 1) organic compound A; emulsion stabilizer C; and an aqueous medium having a pH of 2 to 6 are mixed at a C / A mass ratio of 0.1 to 2, and as a result, the emulsion is mixed. In the step of preparing an oil-in-water emulsion by forming 1 to 50% by mass of emulsified droplets having a particle size of 30 to 300 nm, the above particle size is measured by DLS in Z average hydrodynamics. By adding at least one kind of inorganic oxide precursor to the steps having a diameter and 2) the emulsion obtained in step 1), an inorganic oxide shell layer is provided to the emulsified droplets, and as a result, A step of 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 inorganic oxidation. A process of producing an antireflection coating composition comprising a step of being a metal oxide equal to a precursor, wherein compound A is a non-polar organic compound having a water solubility of up to 5 kg / m ³ . And the emulsion stabilizer C contains at least one monomer unit having a cationic charge and at least one monomer unit which is neutral or nonionic and has an overall positive zeta potential. The process, which is a copolymer, is described.

Further, Japanese Patent Application Laid-Open No. 2014-203006 describes an optical coating film composed of a coating film formed on a substrate, and the maximum value of the major axis (L) and the minor axis orthogonal to the major axis (L) in the coating film. Mean value of (D): ((L + D) / 2) has a void (X) of 20 nm or more, and the major axis (L) and the minor axis (D) of the void (X) are 1 <L / D. An optical coating film is described in which the void (X) is in non-contact with the base material at the interface with the base material.

An object to be solved by the embodiment of the present invention is to provide a water-based coating material having excellent light transmittance of the obtained film.
An object to be solved by another embodiment of the present invention is to provide a film using the water-based coating material and a method for producing the same, and a laminate and a method for producing the same.
An object to be solved by yet another embodiment of the present invention is to provide a water-based coating material kit capable of producing the above-mentioned water-based coating material.

The means for solving the above problems include the following aspects.
<1> Select from the group consisting of water, a siloxane compound represented by the following formula 1, a hydrolyzate of a siloxane compound represented by the following formula 1, and a hydrolysis condensate of a siloxane compound represented by the following formula 1. Aqueous solution containing at least one 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 is a non-polar 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

<2> The water-based coating material according to <1>, wherein at least 50% by mass in the organic solvent is the non-polar solvent.
<3> The aqueous coating material according to <1> or <2>, wherein the non-polar 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 water-based coating material according to any one of <1> to <4>, wherein the coefficient of variation of the particle size of the core-shell particles is 100% or less.
<6> The coat layer is dried, and the coat layer contains water, a hydrolyzed condensate of a siloxane compound represented by the formula 1, a surfactant, and core-shell particles containing an organic solvent in the core material. A film in which 20% by mass or more of the organic solvent is a non-polar 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 has voids inside 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of 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 coefficient of variation 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>, which has the above film on a base material.
<11> The laminate according to <10>, wherein the base material is a resin base material.
<12> The laminate according to any one of <9> to <11>, which is a solar cell front sheet.
<13> The core-shell particles include a step of applying the water-based 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. A method for producing a film in which at least a part of the above is hollow particles that form voids inside the coat layer after the drying step.
<14> The core-shell particles include a step of applying the water-based 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. A method for producing a laminate in which at least a part of the above is 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 and a composition B containing water, a surfactant, and an organic solvent are provided, and 20% by mass of the organic solvent in the composition B is provided. The above is a water-based coating material kit which is a non-polar 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of 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 having excellent light transmission of the obtained film.
According to another embodiment of the present invention, it is possible to provide a film and a method for producing the same, and a laminate and a method for producing the same, using the above-mentioned water-based coating material.
Further, according to still another embodiment of the present invention, it is possible to provide a water-based coating material kit capable of producing the above-mentioned water-based coating material.

The contents of the present disclosure will be described in detail below. The description of the constituents described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In addition, in this specification, "~" indicating a numerical range is used in the meaning of including numerical values described before and after it as a lower limit value and an upper limit value.
In the numerical range described stepwise in the present 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 described stepwise. Good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
Further, in the notation of a group (atomic group) in the present specification, the notation that does not describe substitution and non-substitution includes those having no substituent as well as those having 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 the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term "process" will be used as long as the intended purpose of the process is achieved. included. Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by THF Co., Ltd.). It is a molecular weight converted by using a solvent THF (tetrahydrofuran) and a differential refraction meter and using polystyrene as a standard substance by the gel permeation chromatography (GPC) analyzer.
Hereinafter, the present disclosure will be described in detail.

(Aqueous coating material)
The aqueous coating material according to the present disclosure includes water, a hydrolyzate of a siloxane compound represented by the following formula 1, a hydrolyzate of a siloxane compound represented by the following formula 1, and a hydrolysis condensation of a siloxane compound represented by the following formula 1. It contains at least one compound selected from the group consisting of substances, 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. It is a non-polar 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 independently represent an alkyl group, a vinyl group, an epoxy group, and a styryl group ( It has a group selected from the group consisting of (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, m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.

As a result of diligent studies by the present inventors, it has been found that by adopting the above structure, it is possible to provide a water-based coating material having excellent light transmittance of the obtained film and the laminate using the obtained film.
The mechanism of action of the excellent effect of the above configuration is not clear, but 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 a core-shell particle 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 least a part of the organic solvent is volatilized at the time of drying when forming a film, and voids can be easily formed in the obtained film, and the physical properties of the film can be improved. It is presumed that the effect of the organic solvent during volatilization is small, the volatility of the organic solvent is excellent even at a low temperature lower than the boiling point, and the refractive index of the film obtained by the voids can be reduced. Therefore, it is presumed that the obtained film has excellent light transmittance.
In addition, it is presumed that by reducing the refractive index of the obtained film, the antireflection effect on the base material provided with the obtained film is also improved, and the light transmittance of the laminate having the obtained film on the base material is also excellent. Will be 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 non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower, so that the amount of components remaining on the film after drying is reduced. It also has excellent film haze (degree of cloudiness).

<Core shell particles containing an organic solvent as a core material>
The aqueous coating material according to the present disclosure contains core-shell particles containing an organic solvent as a core material, and 20% by mass or more of the organic solvent is a non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
The "boiling point" in the present disclosure is the boiling point at 1 atm (101,325 Pa). Further, the "non-polar solvent" in the present disclosure means a solvent having a solubility in water of 0.1% by mass or less at 20 ° C. and a relative permittivity value of 10 or less.
Examples of the non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower include hydrocarbon compounds, fluorinated hydrocarbon compounds, silicone compounds and the like. From the viewpoint of light transmission and haze of the obtained film, hydrocarbon compounds Is preferable.
The hydrocarbon compound may be an aliphatic hydrocarbon compound or an aromatic hydrocarbon compound, but is an aliphatic hydrocarbon compound from the viewpoint of light transmission and haze of the obtained film. Is preferable, and an alkylan is more preferable.
The above-mentioned hydrocarbon compound may be linear, has a branch, has a ring structure, or has an unsaturated bond, but the light transmittance of the obtained film 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.
Further, the hydrocarbon compound is preferably a compound having no unsaturated bond.
Further, the hydrocarbon compound is preferably a compound consisting of only carbon atoms and hydrogen atoms from the viewpoint of light transmission and haze of the obtained film.
The carbon number 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 transmission and haze of the obtained film. It is preferably 12 or more and 17 or less, and particularly preferably.

The boiling point of the non-polar 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 transmission and haze of the obtained film. It is particularly preferable that the temperature is 310 ° C. or lower.

Specific examples of non-polar solvents having a boiling point of 90 ° C. or higher and 350 ° C. or lower include n-heptane (boiling point: 98 ° C.), n-octane (boiling point: 125 ° C.), n-dodecane (boiling point: 216 ° C.), n. -Tetradecane (boiling point: 254 ° C), n-hexadecane (boiling point: 287 ° C), n-heptadecane (boiling point: 302 ° C), n-octadecane (boiling point: 317 ° C), n-icosan (boiling point: 343 ° C), cyclo 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.) and the like are preferable. ..

The organic solvent may be only one kind of organic solvent or a mixed solvent of two or more kinds of organic solvents.
Further, the non-polar 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 non-polar 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 based on the total mass of the organic solvent, but can be obtained. 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, further preferably 90% by mass or more, and 99% by mass or more and 100% by mass. The following is particularly preferable.

The material of the shell of the core-shell particles is not particularly limited, but from the viewpoint of the strength of the obtained film, light transmission, and haze, the shell preferably contains a polysiloxane compound, and is represented by the above formula 1. It is more preferable to contain a hydrolyzed condensate of a siloxane compound, and it is further preferable to contain a hydrolyzed condensate of a siloxane compound represented by the above formula 1 in an amount of 50% by mass or more based on the total mass of the shell. It is particularly preferably composed of a hydrolyzed 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 obtained 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 transmission and haze of the obtained film. It is more preferably 0.1 μm to 0.6 μm, and particularly preferably 0.1 μm to 0.4 μm.
Further, the volume average particle diameter of the particles contained in the aqueous coating material according to the present disclosure is preferably 0.05 μm to 1.5 μm from the viewpoint of the strength, light transmission and haze of the obtained film. It is more preferably 08 μm to 1.0 μm, further preferably 0.1 μm to 0.6 μm, and particularly preferably 0.1 μm to 0.4 μm.
The coefficient of variation of the particle size 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. It is more preferable, and it is particularly preferable that it is 0% or more and 50% or less.
Further, the coefficient of variation of the particle size of the particles contained in the aqueous coating material according to the present disclosure is preferably 100% or less, preferably 90% or less, from the viewpoint of light transmission and haze of the obtained film. More preferably, it is more preferably 70% or less, and particularly preferably 0% or more and 50% or less.
The volume average particle size of the particles in the present disclosure shall be measured using a laser diffraction / scattering type particle size distribution measuring device (model number: Microtrack MT3300EXII, manufactured by Microtrack Bell Co., Ltd.). In the present disclosure, the average particle size means the median diameter.
The coefficient of variation of the particle size of the core-shell particles in the present disclosure is calculated by dividing the standard deviation in the volume distribution of the particle size 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 transmission, and haze, and is preferably 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 60 nm from the viewpoint of the strength, light transmission, and haze of the obtained film. It is particularly preferably ~ 600 nm.
The core size (maximum diameter) of the core-shell particles can be measured by the same method as the method for measuring 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, preferably 0.1% by mass, based on the total mass of the aqueous coating material from the viewpoint of the strength, light transmission and haze of the obtained film. It is more preferably from 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 is composed of a siloxane compound represented by the following formula 1, a hydrolyzate of a siloxane compound represented by the following formula 1, and a hydrolyzate of a siloxane compound represented by the following formula 1. Contains at least one compound (specific siloxane compound) selected from the group.

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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of 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 the formula 1 refers to a compound in which at least a part of the substituents on the silicon atom of the siloxane compound represented by the formula 1 is hydrolyzed to become a silanol group. The hydrolyzed condensate of the siloxane compound represented by the formula 1 is two or more compounds selected from the group consisting of the siloxane compound represented by the formula 1 and the hydrolyzate of the siloxane compound represented by the formula 1. Refers to a compound condensed with.

The organic groups having 1 to 6 carbon atoms in R ¹ and R ² in the formula 1 may be linear, have a branch, or have a ring structure. Examples of the organic group having 1 to 6 carbon atoms include an alkyl group and an alkenyl group, and an alkyl group is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group. Be done.
R ¹ and R ² in the 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 transmission and haze of the obtained film. It is more preferable that it is a methyl group or an ethyl group, and it is particularly preferable that it is a methyl group.
Each of R ³ in the formula 1 is preferably an alkyl group having 1 to 6 carbon atoms, and is an alkyl group having 1 to 4 carbon atoms, independently from the viewpoint of the strength, light transmission and haze of the obtained film. Is more preferable, a methyl group or an ethyl group is further preferable, and a methyl group is particularly preferable.
R ⁴ in Formula 1 is an alkyl group, a vinyl group, or a vinyl group, an epoxy group, a styryl group (vinylphenyl group), (meth) independently from the viewpoint of the strength, light transmission and haze of the obtained film. At least one selected from the group consisting of an acryloxy group, a (meth) acrylamide group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, a polyalkyleneoxyalkyl group, a carboxy group and a quaternary ammonium group. It is preferably an alkyl group having a group, more preferably an alkyl group, and particularly preferably an alkyl group having 1 to 8 carbon atoms.
From the viewpoint of the strength, light transmission and haze of the obtained film, m in the formula 1 is preferably 1 or 2, and more preferably 2.
N in Formula 1 is preferably an integer of 2 to 20 from the viewpoint of the strength, light transmission 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 Industry 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 Ebonic Japan Co., Ltd., MKC Siloxane MS-51, MS-56, MS-57, MS-56S manufactured by Mitsubishi Chemical Co., Ltd. Examples thereof include N-propyl silicate, N-butyl silicate, SS-101 and the like.

The water-based coating material according to the present disclosure may contain only one type of the specific siloxane compound, or may contain two or more types.
The content of the specific siloxane compound is preferably 30% by mass to 99% by mass, preferably 50% by mass to 99% by mass, based on the total solid content of the aqueous coating material, from the viewpoint of the strength, light transmission and haze of the obtained 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 water-based coating material according to the present disclosure contains a surfactant.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant which is an ionic surfactant, a cationic surfactant, an amphoteric surfactant and the like, and all of them can be suitably used in the present disclosure.
Among them, nonionic surfactants and haze from the viewpoints of efficient formation of core-shell particles by attractive force interacting with the above-mentioned specific siloxane compound, storage stability, and light transmission and haze of the obtained film. , At least one surfactant selected from the group consisting of cationic surfactants is preferable, and cationic surfactants are more preferable.
The molecular weight of the surfactant is preferably 10,000 or less, more preferably 5,000 or less, from the viewpoint of storage stability, light transmission of the obtained film, and haze. It 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, a polyamine type surfactant and the like. Specific examples thereof include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylpyridinium salt, benzalkonium salt, and alkylamine salt. 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 non-polar 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 ethers, polyalkylene glycol monoalkyl esters, polyalkylene glycol monoalkyl esters and monoalkyl ethers. 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, alkylbenzene sulfonates and alkyl phosphates; and amphoteric surfactants such as alkyl carboxybetaines.

The water-based coating material according to the present disclosure may contain only one type of surfactant or two or more types, and fluorine may be contained from the viewpoint of improving the wettability and coatability of the water-based coating material on the substrate. It may have a based surfactant, a silicone based surfactant, an acetylene based surfactant and the like.
Fluorine-based surfactants include Megafuck series manufactured by DIC Corporation such as Megafuck F-444, Surfron series manufactured by AGC Seimi Chemical Co., Ltd. such as Surflon S-221, and Footer manufactured by Neos Co., Ltd. such as Futergent 100. Gent series etc. can be mentioned. Examples of the silicone-based surfactant include the KP series of leveling materials manufactured by Shin-Etsu Chemical Co., Ltd. such as KP-124. Examples of the acetylene-based surfactant include the surfinol series and the olphin series manufactured by Nisshin Kagaku Kogyo Co., Ltd., such as Surfinol 420 and Orfin E1004.

The content of the surfactant in the water-based coating material according to the present disclosure is 0.01% by mass or more with respect to the total mass of the water-based coating material from the viewpoint of storage stability, light transmittance and haze of the obtained film. It is preferably 10% by mass, more preferably 0.02% by mass to 5% by mass, and particularly preferably 0.03% by mass to 1% by mass.
The content of the surfactant is 0.5% by mass with respect to the total mass of the organic solvent as the core material in the core-shell particles from the viewpoint of storage stability, light transmission of the obtained film and haze. 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 water-based coating material according to the present disclosure contains water.
The water-based coating material according to the present disclosure contains water, but may further contain a hydrophilic organic solvent or the like having an excellent affinity with water.
The content of water in the water-based coating material is preferably 30% by mass or more, preferably 50% by mass or more, based on the total content of water and the hydrophilic organic solvent (excluding the organic solvent of the core material in the core shell particles). It is more preferably mass% or more, and particularly preferably 80 mass% or more and 100 mass% or less.
Examples of the hydrophilic organic solvent that can be contained 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 load, an alcohol compound is preferable, and at least one compound selected from the group consisting of ethanol and isopropanol is more preferable.

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

[Other ingredients]
In addition to the essential components described above, the water-based coating material according to the present disclosure may contain other components depending on the purpose as long as the effects according to the present disclosure are not impaired.
As other components, known additives can be used, and examples thereof include charge control agents, condensation catalysts of siloxane compounds, and preservatives.
In the water-based coating material according to the present disclosure, when a film is formed after coating, as described above, the specific siloxane compound is condensed and cured by reducing the amount of water or the like as a solvent to form a film. Further, at the time of drying, at least a part of the organic solvent which is the core material of the core-shell particles volatilizes to form voids. Therefore, the formation of the cured film does not require light irradiation or high-temperature heat treatment required for polymerization reaction, cross-linking reaction, or the like. Further, it is not necessary to contain a photopolymerization initiator, a thermal polymerization initiator and the like required for a polymerization reaction, a cross-linking reaction and the like.
Therefore, the aqueous coating material according to the present disclosure, which does not contain a photopolymerization initiator, a thermal polymerization initiator, or the like that affects the storage stability, has good storage stability.
According to the water-based coating material according to the present disclosure, a film having excellent light transmission can be formed by a simple method.

-Antistatic agent-
The water-based coating material according to the present disclosure may contain an antistatic agent.
The antistatic agent is used for the purpose of suppressing the adhesion of contaminants by imparting antistatic properties to the film formed of the water-based coating material.
The antistatic agent for imparting antistatic properties is not particularly limited.
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 provide antistatic properties, but since they are inorganic particles, the inclusion of the metal oxide particles prevents the film formed by the water-based coating material. It can be more dirty.

The metal oxide particles are not particularly limited, and examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles, and silica particles.
The metal oxide particles have a large refractive index, and if the particle size is large, there is a concern that the light transmittance may decrease due to scattering of transmitted light. Therefore, the average primary particle size of the metal oxide particles is preferably 100 nm or less, preferably 50 nm. It is more preferably less than or equal to, and particularly preferably 30 nm or less. The lower limit is preferably 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 size of the metal oxide particles can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. From the image of the photograph, the projected area of the particles is obtained, and the equivalent circle diameter is obtained from the projected area, which is used as the average particle diameter (average primary particle diameter). As the average primary particle diameter in the present specification, a value calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter is used.
When the shape of the metal oxide particles is not spherical, it may be obtained by another method, for example, a dynamic light scattering method.

Only one type of antistatic agent may be contained in the water-based coating material, or two or more types may be contained. When two or more kinds of metal oxide particles are contained, two or more kinds having different average primary particle diameters, shapes, and materials may be used.
In the water-based 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 20% by mass, based on the total solid content of the water-based coating material. It is particularly preferable that it is% or less.
By setting the content of the antistatic agent in the above range, it is possible to effectively impart antistatic properties to the formed film without deteriorating the film-forming property of the water-based coating material.
When the metal oxide particles are used as the antistatic agent, the content is preferably 30% by mass or less, more preferably 20% by mass or less, and 10% by mass with respect to the total mass of the aqueous coating material. It is particularly preferable that it is% or less.
By setting the content of the metal oxide particles in the above range, the dispersibility of the metal oxide particles in the water-based coating material is improved, the occurrence of aggregation is suppressed, and the necessary antistatic property is formed by the water-based 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 condensation of the siloxane compound.
Since the aqueous coating material contains a condensation catalyst, a film having more excellent durability can be formed. In the present disclosure, as the aqueous coating material is applied and then dried to reduce the water content in the film, at least a part of the hydroxy groups of the hydrolyzate of the siloxane compound represented by the formula 1 is condensed with each other. By forming a condensate, a stable film is formed. When the film is formed, the aqueous coating material contains a siloxane compound represented by the formula 1 and its hydrolyzate, and a catalyst that promotes condensation of the hydrolyzate condensate thereof, so that the film can be formed more quickly. You can proceed.

The condensation catalyst that can be used in the present disclosure is not particularly limited, and examples thereof include an acid catalyst, an alkali catalyst, and an organometallic catalyst.
Examples of acid catalysts 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 alkaline catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
Examples of organometallic catalysts include aluminum chelate compounds such as aluminum bis (ethylacetate acetate) mono (acetylacetone), aluminum tris (acetylacetone), aluminum ethylacetacetate diisopropirate, and zirconium tetrakis (acetylacetonate). , Zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetone), titanium chelate compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetone) and dibutyltin diacetate, dibutyltin dilaurate, Examples thereof include organotin compounds such as dibutyltin dioctate.
The type of the condensation catalyst is not particularly limited, but 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, preferably 0.005% by mass, based on the total solid content of the aqueous coating material from the viewpoint of the strength, light transmission and haze of the obtained film. It is more preferably from mass% to 15% by mass, and particularly preferably 0.01% by mass to 10% by mass.

The condensation catalyst that promotes the condensation of the siloxane compound is also useful for promoting the hydrolysis reaction of the siloxane compound represented by the above formula 1.
The hydrolysis reaction and the condensation reaction of the alkoxy group bonded to silicon of the siloxane compound represented by the formula 1 are in an equilibrium relationship, and when the content of water contained in the aqueous coating material is large, water tends to be hydrolyzed. If the content of is low, it proceeds in the direction of condensation. Since the condensation catalyst that promotes the condensation reaction of the alkoxy group has the effect of promoting the reaction in both directions, the hydrolysis reaction can be promoted when the water content in the aqueous coating material is high. The presence of the condensation catalyst makes it possible to hydrolyze the siloxane compound represented by the formula 1 under milder conditions.

-Manufacturing method of water-based coating material-
The method for producing the 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. A method of producing a core-shell particle by forming a shell layer on the surface of an organic solvent decomposed and condensed and dispersed to produce a water-based coating material, a core-shell particle containing an organic solvent as a core material, a specific siloxane compound, a surfactant, In addition, a method of mixing and producing water can be mentioned.
Above all, an organic solvent, a surfactant, and water are mixed to disperse the organic solvent in water, and a specific siloxane compound is added to partially hydrolyze and condense to form a shell layer on the surface of the dispersed organic solvent. A method of producing core-shell particles to produce an aqueous coating material is preferable. Further, the specific siloxane compound may be added together with the organic solvent, the surfactant and water, or may be added after the organic solvent is dispersed in water.

The core-shell particles are preferably prepared 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 core shelling is efficiently promoted.
As a method of emulsifying the core material, a method using a rotor (rotary blade) or a stator (fixed blade), a method using ultrasonic cavitation, a method using a crushing medium such as a ball or a bead, and high-speed collision between raw materials. There are a method of allowing the dispersion solvent to pass through the solvent through the porous membrane, and the like, and the core material can be emulsified by applying a shearing force.
The devices used for the method of emulsifying the core material include Primix Corporation Automixer Type 20, Emerson Japan, Ltd. Ultrasonic Homogenizer SonifierSFX250, Ashizawa Finetech Co., Ltd. OMEGA LAB, and Sugino Co., Ltd. Examples include Starburst 10 manufactured by Machine, KH-125 manufactured by SPG Techno Co., Ltd., and the like.

It is preferable that the specific siloxane compound is 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 that promotes the condensation of the specific siloxane compound can be added.
A surfactant and an organic solvent may be added to the obtained hydrolyzate solution of the specific siloxane compound, or the organic solvent, the surfactant and water are mixed to disperse the organic solvent in water. The solution and the hydrolyzate solution of the specific siloxane compound may be mixed. Further, the solution obtained by mixing an organic solvent, a surfactant and water and dispersing the organic solvent in water may be mixed with the above-mentioned specific siloxane compound to simultaneously perform hydrolysis and shell formation.

By using the water-based coating material according to the present disclosure, a film having good light transmission is formed.
Therefore, the water-based coating material according to the present disclosure is suitable for forming a film that protects the surface of a device used outdoors such as a solar cell module. The formed film has excellent light transmission, excellent power generation efficiency, and excellent durability of the film by using a specific siloxane compound.
Therefore, the water-based coating material according to the present disclosure is useful for forming surface materials of various base materials, optical devices, particularly antireflection films, and front sheets of solar cell modules (solar cell front sheets).

(film)
In the first embodiment of the film according to the present disclosure, the coat layer is dried, and the coat layer is composed of water, a hydrolyzed condensate of a siloxane compound represented by the above formula 1, a surfactant, and an organic substance. The core material contains core-shell particles containing a solvent, and 20% by mass or more of the organic solvent is a non-polar 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. Has a void inside the solvent.
The second embodiment of the film according to the present disclosure is a film obtained by drying the aqueous coating material according to the present disclosure, and is a film having voids, preferably hollow particles, inside.
The coating layer is preferably a coating film of a water-based coating material, and a preferred embodiment 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 water-based coating material according to the present disclosure. This is the same as the preferred embodiment.
A preferred embodiment of the hydrolyzed condensate of the siloxane compound represented by the formula 1 in the coat layer is a preferred embodiment of the hydrolyzed condensate of the siloxane compound represented by the formula 1 in the aqueous coating material according to the present disclosure. Is similar to.
Further, it is preferable that the coat layer is provided on the base material.

The film according to the present disclosure has voids inside at least a part of the core-shell particles in the coated layer after drying.
From the viewpoint of strength, light transmission and haze, the average internal void diameter of the film is preferably 20 nm or more, more preferably 30 nm or more, further preferably 30 nm to 200 nm, and 40 nm to 150 nm. Is particularly preferable.
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 transmission and haze. ..
The method for measuring the average internal void diameter of the film was as described below.
The laminate with the antireflection film was cut in a direction orthogonal to the substrate, and the cut surface was observed with a scanning electron microscope to evaluate the diameter of the closed void, the coefficient of variation of the void diameter, and the porosity.
The equivalent circle diameter was calculated for each of the 200 arbitrarily selected voids, and the average value was taken as the diameter of the closed void.
The porosity was determined by calculating the ratio of the internal void portion by performing image processing (binarization) on the internal void portion and the resin binder portion using image processing software (ImageJ) to separate them.
The coefficient of variation of the void diameter of the film is calculated by dividing the standard deviation in the void diameter distribution 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, but from the viewpoint of light transmission and haze, it is preferably 10 nm to 1 μm, preferably 50 nm to 350 nm. It is more preferably 80 nm to 200 nm, and particularly preferably 100 nm to 180 nm.
Further, the average thickness of the film shall be averaged by measuring the thickness at 10 or more points in the film.

The integrating sphere transmittance of the film according to the present disclosure (average of the transmittance of light having a wavelength λ = 300 nm to 1,100 nm) is preferably 90% or more, and more preferably 93% or more.
The integrating sphere transmittance of the film in the present disclosure is obtained by measuring the integrating sphere transmittance of a base material provided with a film formed of an aqueous coating material using a barium sulfate white plate as a reference.
The measurement of the integrating sphere transmittance of the film 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 accessory device (ISR-2200, manufactured by Shimadzu Corporation) is connected to an ultraviolet visible infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), or Measurement is performed by an apparatus in which a multipurpose 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 an optical lens, an optical filter, a flattening film for a thin film transistor (TFT) of various displays, an antireflection film, a dew condensation prevention film, an antifouling film, a surface protective film, and the like. It is preferably used by an antireflection film. Further, since the surface protective film of the solar cell module is also required to have antireflection ability 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, and the solar cell module. It is particularly preferably used as a front seat (solar cell front seat).

<Membrane manufacturing method>
The method for producing the film according to the present disclosure is not particularly limited, but includes a step of applying the aqueous coating material according to the present disclosure on a substrate to form a coat layer, and a step of drying the coat layer. It is preferable that at least a part of the core-shell particles becomes hollow particles that form voids inside the coat layer after the drying step.
The base material used in the present disclosure is not particularly limited, and for example, a desired base material such as a base material or composite base material of a material described later, a substrate having wiring or the like, a solar cell module, or the like can be used.
Moreover, you may use a temporary support as a base material.
As the material of the base material, for example, glass, resin, metal, ceramics and the like can be preferably used.
The method of applying the water-based coating material according to the present disclosure to the base material is not particularly limited, and for example, any known coating method such as spray coating, brush coating, roller coating, bar coating, and dip coating shall be applied. Can be done. It is also preferable to perform surface treatment such as corona discharge treatment, glow treatment, atmospheric pressure plasma treatment, flame treatment, and ultraviolet irradiation (UV) treatment on the base material before applying the water-based coating material.

The coating layer may be dried at room temperature (25 ° C.) or heated, but the organic solvent is sufficiently volatilized to form voids, and the light transmittance of the obtained film and From the viewpoint of suppressing coloration, it is preferable to heat the mixture to 40 ° C. to 700 ° C. When a resin base material is used, it is necessary to heat it at a temperature equal to or lower than the decomposition temperature of the base material, and specifically, it is preferable to heat it to 40 ° C. to 200 ° C. Further, from the viewpoint of suppressing thermal deformation of the base material, it is more preferable to heat the base material 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)
The first embodiment of the laminate according to the present disclosure has a film according to the present disclosure.
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 formed inside the film. Have.
Further, the laminate according to the present disclosure preferably has the above-mentioned film on the base material.
The base material of the laminate according to the present disclosure is not particularly limited, and the above-mentioned base material can be used, but a resin base material is preferably mentioned from the 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 fluoropolymer. Among them, 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, cycloolefin and the like.
Examples of the acrylic resin include polymethyl methacrylate and the like.
Examples of cellulose include triacetyl cellulose and the like.
When a resin base material is used as the base material, the thickness of the resin base material is preferably 1 μm or more, more preferably 10 μm or more, further preferably 45 μm or more, and particularly preferably 145 μm or more, from the viewpoint of handleability and withstand voltage. It is preferably 200 μm or more, and most preferably 200 μm or more. The upper limit is preferably 500 μm or less, more preferably 450 μm or less.
When a glass base material is used as the base material, the thickness of the glass base material is preferably 500 μm or more. The upper limit is preferably 4,000 μm or less, more preferably 3,500 μm or less.

The laminate according to the present disclosure may further have other layers.
As the other layer, various known layers can be provided. Specific examples thereof include an adhesive layer, a hard coat layer, an ultraviolet absorbing layer, and an undercoat layer.
Further, when the laminate according to the present disclosure is used for a solar cell module described later, it is preferable that the laminate according to the present disclosure 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 base material and the film according to the present disclosure is improved, and a laminated body having excellent durability can be obtained.

Examples of the adhesive layer include a known pressure-sensitive adhesive, a layer containing a known adhesive, and a layer containing a cured product thereof.
The adhesive layer is preferably a layer to which a coating liquid for forming an adhesive layer containing a resin and a cross-linking agent is applied and dried or cured.
The resin is not particularly limited, and examples thereof include polyolefin resin, urethane resin, polyester resin, acrylic resin, polyvinyl alcohol, polyamide resin, and silicone resin, and polyolefin resin is preferable from the viewpoint of adhesion.
The cross-linking agent is not particularly limited, and examples thereof include an oxazoline-based cross-linking agent, an epoxy-based cross-linking agent, a carbodiimide-based cross-linking agent, and a blocked isocyanate-based cross-linking agent, and an oxazoline-based cross-linking agent is preferable.
The coating liquid for forming an adhesive layer may further contain known components such as a surfactant and a solvent.

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

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

<Hard coat layer>
The laminate according to the present disclosure preferably further has a hard coat layer, and more preferably further has a hard coat layer on the side of the base material provided with the film according to the present disclosure. It is particularly preferable to further have a hard coat layer between the film and the film.
By providing the hard coat layer, a laminate having further excellent heat resistance can be obtained. It is considered that this is because the hard coat layer suppresses the permeation of oxygen into the inside of the laminate, so that the deterioration of the base material and the like due to oxygen is suppressed.

The hard coat layer is not particularly limited, and examples thereof include hard coat layers known in the field of solar cells. For example, JP2013-45045A, JP2013-43352A, and JP2012-232459A. , Japanese Patent Application Laid-Open No. 2012-128157, Japanese Patent Application Laid-Open No. 2011-131409, Japanese Patent Application Laid-Open No. 2011-131404, Japanese Patent Application Laid-Open No. 2011-126162, Japanese Patent Application Laid-Open No. 2011-75705, Japanese Patent Application Laid-Open No. 2009-286981 Open 2009-263567, 2009-75248, 2007-164206, 2006-96811, 2004-75970, 2002-156505, 2001 The hard coat layer described in -272503, International Publication No. 12/01887, International Publication No. 12/098967, International Publication No. 12/086659, International Publication No. 11/105594 can be used.

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 laminated body.
The upper limit of the pencil hardness on the surface of the hard coat layer is not particularly limited, but the upper limit of the pencil hardness on the surface of the hard coat layer is preferably 6H or less, more preferably 3H or less, from the viewpoint of processability of the laminate. Is.
The pencil hardness on the surface of the hard coat layer means a value measured based on JIS K5600-5-4: 1999. As the pencil, Hi-Uni manufactured by Mitsubishi Pencil Co., Ltd. is used.

As the 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.
When the siloxane resin is produced by the sol-gel method, the hard coat layer preferably contains a metal complex as a 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. The upper limit is not particularly limited and may be 100% by mass.

-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.
As the inorganic filler, at least one kind of inorganic particles selected from the group consisting of a metal oxide filler and an inorganic nitride filler is preferable 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 and the like.

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 burning silicon tetrachloride; colloidal silica in which silicon dioxide or its hydrate is dispersed in water; and the like.
When dry powdered silica is used, it can be used by dispersing it in water using an ultrasonic disperser or the like.
The silica filler is not particularly limited, but 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 (registered trademark). Nissan Chemical Industries, Ltd.), etc.
Examples of the alumina filler include aluminum oxide, which is an amphoteric oxide of aluminum, and alumina hydrate (aluminum hydroxide) containing water of crystallization.
Aluminum oxide includes α-alumina, γ-alumina, δ-alumina, θ-alumina and the like depending on the crystal structure. Alumina hydrates include dibsite, bayarite, boehmite, diaspore, pseudoboehmite, and amorphous state depending on the crystal structure.
Alumina filler is not particularly limited, but specifically, alumina sol series such as alumina sol AS-200 (manufactured by Nissan Chemical Industry Co., Ltd.), aluminum sol series such as aluminum sol 10C and aluminum sol F-1000 (Kawaken Fine Chemicals Co., Ltd.) , 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 powdery form, it can be used by dispersing it in a solvent such as water using an ultrasonic disperser or the like.

Examples of the shape of the inorganic filler include particle shapes such as spherical, rod-shaped, polyhedral, flat plate-shaped or scaly-shaped, beads-shaped, needle-shaped or fibrous-shaped.
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 has a bead shape, a needle shape, or a fiber shape, the aspect ratio is preferably 4 or more, more preferably 9 or more, further preferably 100 or more, and particularly preferably 500 or more. By using particles having a high aspect ratio, it is possible to achieve both hardness and flexibility of the hard coat layer.
The aspect ratio means the value obtained by dividing the secondary particle diameter (bond length of the primary particles) by the primary particle diameter in the case of the bead shape, and the major axis divided by the minor axis in the case of the needle shape and the fiber shape. Means a value.

For the number average primary particle size of the inorganic particles, the cross section of the hard coat layer was observed with a scanning electron microscope (SEM), 100 particles included in the range corresponding to the actual area of 1 mm ² were selected, and the particle size of each particle was selected. Refers to the 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 20% by mass to 50% by mass with respect to the solid content of the hard coat layer. Is particularly preferable.
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, based on the solid content of the hard coat layer.

-Other ingredients-
The hard coat layer may contain other components other than those described above.
For example, the hard coat layer may contain at least one type of surfactant.
As a result, the slipperiness of the surface of the hard coat layer is improved, and the friction of the surface of the hard coat layer 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, still more preferably, with respect to the solid content of the hard coat layer. It is 0.1% by mass to 1% by mass.

The hard coat layer (or the coating liquid for forming the hard coat layer) 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.
Examples of the ultraviolet absorber include compounds similar to the ultraviolet absorber contained in the ultraviolet absorbing layer described later, and metal oxide particles are preferably mentioned.

The thickness of the hard coat layer is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 8 μm, and even 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 surface of the hard coat layer.
When the thickness of the hard coat layer is 10 μm or less, the transparency and handleability of the laminated body are further improved.

<UV absorption layer>
The laminate according to the present disclosure is between the base material and the hard coat layer (when the hard coat layer is omitted, the surface of the base material on the side 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 preferably a layer containing an ultraviolet absorber and a cured solgel, 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 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 containing an ultraviolet absorbing structure includes at least a part of the structure such as a triazine compound, a benzotriazole compound, a benzophenone compound and a salicylic acid compound. Examples thereof include an acrylic resin containing a monomer unit derived from an acrylic acid ester compound.
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 hydrolyzing and polycondensing 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, polyurethane and the like.
The ultraviolet absorbing layer is formed by applying each component contained in the ultraviolet absorbing layer and, if necessary, a coating liquid for forming an ultraviolet absorbing layer containing a solvent on a surface base material and drying it if necessary. To.

<Back layer>
The laminate according to the present disclosure may be provided with a back surface layer on the side of the base material opposite to the side on which the film according to the present disclosure is provided.
The back surface 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 surface layer preferably contains a binder polymer.
The back surface layer may be only one layer or two or more layers.

For example, the laminate may be provided with a first layer, a Bth layer, and a Cth layer as backside layers in this order on the side of the base material opposite to the side on which the film according to the present disclosure is provided.
Hereinafter, the Ath layer, the Bth layer, and the Cth layer provided in the laminated body as needed will be described.

-Layer A-
The layer A preferably contains a binder polymer.
The binder polymer that can be contained in the layer A is not particularly limited, but is, for example, a polyolefin resin, a urethane resin, a polyester resin, an acrylic resin, or a silicone from the viewpoint of adhesion to a sealing material when applied to a solar cell module. Examples thereof include resins, and polyolefin resins, polyurethane resins, and acrylic resins are preferable from the viewpoint of adhesion.
Examples of the polyolefin resin include Arrow Base (registered trademark) SE-1013N, SD-1010, TC-4010, TD-4010, DA-1010 (both manufactured by Unitika Ltd.), Hi-Tech S3148, S3121, and S8512 (both Toho). Chemicals (manufactured by Chemical Industries, Ltd.), Chemipal (registered trademark) S-120, S-75N, V100, EV210H (all manufactured by Mitsui Chemicals, Inc.) and the like. As the acrylic resin, Julimer AS-563A (manufactured by Dicelle Finechem Co., Ltd.), Bonron PS-001, PS-002 (Mitsui Chemicals Co., Ltd.), SIFCLEARS-101, F-101, F102 (manufactured by JSR Corporation), Examples thereof include Ceranate WSA1070 (DIC Corporation). Examples of the polyurethane resin include Takelac WS-6021, WS-5000, WS-5100, WS-4000 and the like.
The cross-linking agent is not particularly limited, and examples thereof include an oxazoline-based cross-linking agent, an epoxy-based cross-linking agent, a carbodiimide-based cross-linking material, and a blocked isocyanate-based cross-linking agent, and an oxazoline-based cross-linking agent is preferable.
The coating liquid for forming the first layer A may further contain known components such as a cross-linking agent, a surfactant, an antistatic agent, a preservative, inorganic particles, and a solvent.

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

The thickness of the A layer is preferably 0.2 μm or more, more preferably 0.4 μm or more. 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 coating liquid for forming the A layer containing a solvent and the above-mentioned component (solid content) of the A layer is applied onto the back surface of the composite base material and dried. Can be mentioned.

-Layer B-
The laminate of the present disclosure may include a third layer on the first layer A.
The B layer preferably contains a binder polymer.
As the binder polymer in the B layer, at least one polymer selected from the group consisting of polyolefin, acrylic resin, polyester and polyurethane is preferable from the viewpoint of adhesion to the encapsulant.
The binder polymer in the B-layer is preferably a polyolefin resin or an acrylic resin from the viewpoint of adhesion to the sealing material and cohesive force of the coating film.

The B-layer may contain a cross-linking 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 liquid for forming the B-layer containing a solvent and the above-mentioned component (solid content) of the B-layer is applied onto the A-layer and dried. ..

-Layer C-
The laminate of the present disclosure may include a C-th layer on the B-layer.
The C-th 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 to 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-th layer is not particularly limited, but is, for example, a polyolefin resin, a urethane resin, a polyester resin, an acrylic resin, or a silicone from the viewpoint of adhesion to a sealing material when applied to a solar cell module. Examples thereof include resins, and polyolefin resins, polyurethane resins, and acrylic resins are preferable from the viewpoint of adhesion.
The cross-linking agent is not particularly limited, and examples thereof include an oxazoline-based cross-linking agent, an epoxy-based cross-linking agent, a carbodiimide-based cross-linking material, and a blocked isocyanate-based cross-linking agent, and an oxazoline-based cross-linking agent is preferable.
The coating liquid 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.
Examples of the acrylic resin include the same acrylic resins that can be contained in the above-mentioned layer A.
It is more preferable that the acrylic resin content ratio in the binder polymer contained in the undercoat layer is 50% by mass or more.
When 50% by mass or more of the binder polymer is an acrylic resin, the elastic modulus of the undercoat layer can be easily adjusted to 0.7 GPa or more, and the cohesive fracture resistance when used as 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.
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 liquid 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 the undercoat layer.
Further, the undercoat layer may be formed by an in-line coating method using the above-mentioned coating liquid for forming an undercoat layer.
The in-line coating method is a method of applying a coating liquid for forming an undercoat layer before winding up the manufactured base material, and is different from the offline coating method in which the manufactured base material is wound up and then separately applied. Distinguished.
As an embodiment of forming the undercoat layer by the in-line coating method, the undercoat layer forming coating liquid is applied to one surface of the film stretched in the first direction, and the film coated with the undercoat layer forming coating liquid is applied to the film. It is preferable to manufacture a base material with an undercoat layer by stretching along the surface in a second direction orthogonal to the first direction.

The laminate according to the present disclosure may include other layers other than the above-mentioned layers.
Further, the laminate according to the present disclosure has a light transmittance of 80% or more, more preferably 83% or more, still more preferably 85% or more at 25 ° C. and a wavelength of 550 nm. .. The transmittance is measured using a spectrophotometer V670 (manufactured by JASCO Corporation).

The laminate according to the present disclosure can be suitably used as a surface protective member, an antireflection member, an optical device, an antifouling material for building materials such as window glass and a guide mirror, and the like.
Above all, it can be particularly preferably used as a solar cell front seat.

<Manufacturing method of laminated body>
The method for producing the laminate according to the present disclosure is not particularly limited, but includes a step of applying the aqueous coating material according to the present disclosure on a substrate to form a coat layer, and a step of drying the coat layer. It is preferable that at least a part of the core-shell particles becomes hollow particles that form voids inside the coat layer after the drying step.
The water-based coating material can be applied to the substrate and the coating layer can be dried in the same manner as in the film production method described above.

(Solar cell module)
It is preferable that the solar cell module according to the present disclosure has 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 highly transparent laminate and a polyester film provided on the side where sunlight is incident, in which a solar cell element that converts light energy of sunlight into electric energy is provided. It is more preferable that the solar cell is arranged between the back sheet and the back sheet. The laminate and the polyester film can be sealed with a sealing agent typified by a resin such as an ethylene-vinyl acetate copolymer.

Members other than laminates and backsheets, such as solar cell modules and solar cells, are described in detail in, for example, "Solar Power System Components" (supervised by Eiichi Sugimoto, Kogyo Chosakai Co., Ltd., published in 2008). Has been done. The solar cell module according to the present disclosure may have any configuration except that the film according to the present disclosure, preferably the laminate according to the present disclosure, is provided on the side where sunlight is incident.
Examples of the base material provided on the side where sunlight is incident include a glass base material, a resin base material such as an acrylic resin, and the resin base material is preferably mentioned from the viewpoint of weight reduction.

The solar cell element used in the solar cell module according to the present disclosure is not particularly limited, and is silicon-based such as single crystal silicon, polycrystalline silicon, and amorphous silicon, copper-indium-gallium-selenium, and copper-indium-selenium. , Cadmium-tellu, gallium-arsenide and other III-V group and II-VI group compound semiconductor systems, and various known solar cell elements can be applied.

(Aqueous coating material kit)
The aqueous coating material kit according to the present disclosure comprises a composition A containing a siloxane compound represented by the above formula 1 and a composition B containing water, a surfactant, and an organic solvent, and the above composition B includes the composition B. 20% by mass or more of the organic solvent is a non-polar 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 on the surface of the dispersed organic solvent by the hydrolyzed condensate of the siloxane compound represented by the formula 1. , Core-shell particles are generated, and the water-based 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 the above formula 1 in the aqueous coating material kit according to the present disclosure are the same as those of the aqueous coating material described above, except for the embodiments described below. is there.
Further, the above-mentioned 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, and the hydrolyzate of the siloxane compound represented by the above formula 1 and the hydrolyzed condensate of the siloxane compound represented by the above formula 1 May include.
Further, the composition A preferably contains water as a solvent. By containing water, mixing with the composition B can be performed more easily, and the production of an aqueous coating material becomes easy. Further, the composition A may contain a water-soluble organic solvent as the 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 hydrolyzed 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.
Further, the composition A preferably contains a surfactant. By including the surfactant, mixing with the composition B can be carried out more easily, and the production of an aqueous coating material becomes easy.

<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 non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
In the composition B, it is preferable that the organic solvent is dispersed in water.
Further, the composition B preferably contains the above-mentioned condensation catalyst. The inclusion of a condensation catalyst facilitates the formation of core-shell particles.
The composition B may contain a water-soluble organic solvent in addition to water.
Further, the composition B may contain core-shell particles, and may contain the above-mentioned organic solvent as the core material of the core-shell particles. Further, the residue of the siloxane compound represented by the above formula 1 which was not used for shell formation at the time of core shell formation may be contained.

The content of the organic solvent in the composition B is preferably 0.05% by mass to 50% by mass, more preferably 0.1% by mass to 40% by mass, based on the total mass of the composition B. , 0.2% by mass to 30% by mass is particularly preferable.
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, more preferably 70% by mass to 99.5% by mass, based on 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 addition, in this Example, "%" and "part" mean "mass%" and "part by mass", respectively, unless otherwise specified.

(Example 1)
<Preparation of water-based coating material 1>
-Composition of emulsion particle dispersion 1-
-Hexadecan (n-hexadecan, 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% diluted distilled water, cationic surfactant, manufactured by Wako Pure Chemical Industries, Ltd.): 4.42 parts, distilled water: 42.81 parts To prepare the emulsion particle dispersion, follow the procedure below. went.
Hexadecane, hexane, Ca-1 and ion-exchanged water are mixed, cooled with ice water using an ultrasonic homogenizer Sonifier450 manufactured by Emerson Japan, Ltd., and treated for 30 minutes with stirring to obtain an emulsion of hexadecane in water. The 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 Co., Ltd.) 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 after the addition, the mixture is further stirred at 25 ° C. for 16 hours to form core-shell particles containing a non-polar solvent as a core material, represented by the formula 1. A core-shell particle dispersion containing a compound, a surfactant and water was obtained.

-Composition of water-based coating material 1-
-Core-shell particle dispersion: 15.04 parts-Ion-exchanged water: 79.46 parts-F-444 (fluorine-based surfactant 1% distilled water dilution, manufactured by DIC Corporation): 5.50 parts

Next, 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 base material (PP, Trefan BO60-2500, manufactured by Toray Industries, Inc., base material thickness 60 μm) was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the aqueous coating material 1 was applied by a bar coater using a bar count # 4, and dried at 80 ° C. for 2 minutes to form a coating layer having an average thickness of 130 nm to obtain a laminate 1.

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

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

2. 2. Transmittance of the laminate Using an ultraviolet-visible infrared spectrophotometer (model number: UV-3100PC, manufactured by Shimadzu Corporation), the transmittance of the laminate is measured and used as an index to evaluate 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.
The higher the measured value of the effective transmittance, the more the coat layer has excellent light transmittance.
The transmittance was evaluated using the calculated average transmittance and the effective transmittance obtained by calculating the average value of the transmittances having a wavelength of 300 nm to 1,100 nm. The effective transmittance is based on the following formula T, using the transmittance of the laminate at a wavelength of 300 nm to 1,100 nm, the spectral distribution of sunlight (AM1.5), and the spectral sensitivity of the crystalline silicon solar cell. Calculated. As the spectral sensitivity, the spectral irradiance of the crystalline silicon type reference solar cell was taken as the spectral sensitivity.

In equation 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) represents the spectral sensitivity of the crystalline silicon solar cell at wavelength λ. Represents the transmittance of the laminate.

3. 3. The haze of the obtained laminate was measured using a haze meter (model number: NDH 5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the obtained measured value was used to measure the light transmission. It was used as an index to evaluate. Haze measured the surface on which the film (coat layer) of the laminated body was formed toward the light source.
The lower the measured value of the haze, the more the laminated body and the coat layer have excellent light transmission, and the value is preferably 5% or less.

(Examples 2-31)
As shown in Tables 1 to 3, Examples 2 and 2 are the same as in Example 1 except that the substrate, organic solvent, surfactant, W / O ratio, bar count, and drying conditions are changed. 31 emulsion particle dispersion liquid, core shell particle dispersion liquid, aqueous coating material 2-31, and laminate 2-31 were prepared, respectively.

(Example 32)
An emulsion particle dispersion 32, a core-shell particle dispersion 32, an aqueous coating material 32, and a laminate 32 were prepared 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) Made) 9.96 copies

(Example 33)
An emulsion particle dispersion 33, a core-shell particle dispersion 33, an aqueous coating material 33, and a laminate 33 were prepared 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) Made) 9.96 copies

(Example 34)
The emulsion particle dispersion liquid 34, the core shell particle dispersion liquid 34, the aqueous coating material 34, and the laminate 34 were prepared in the same manner as in Example 4 except that the compositions of the emulsion particle dispersion liquid and the core shell particle dispersion liquid were changed.

-Composition of emulsion particle dispersion 34-
-Hexadecane (n-hexadecane, manufactured by Wako Pure Chemical Industries, Ltd.): 5.53 parts-Ca-1 (hexadecylpyridinium chloride 10% diluted with distilled water, 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 copies

(Example 35)
An emulsion particle dispersion 35, a core-shell particle dispersion 35, an aqueous coating material 35, and a laminate 35 were prepared 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 with 5% distilled water): 1.26 parts-MS-51 (Compound represented by formula 1, Mitsubishi Chemical Corporation) Made) 6.00 copies

Further, the performance was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 to 3.

(Example 36)
[Manufacturing of solar cell front sheet]
-Preparation of adhesive layer-
By mixing the adhesive layer forming composition having the following composition, a coating liquid 36 for forming an adhesive layer was obtained.

-Composition of Adhesive Layer Forming Composition 36-
-Polyurethane resin (Arrow base DA-1010, manufactured by Unitika Ltd., solid content 25%): 27.25 parts-Polyurethane resin (Takelac WS-5100, manufactured by Mitsui Chemicals Co., Ltd., solid content 30%): 22. 71 parts ・ Fluorine-based surfactant (sodium = bis (3,3,4,5,5,5,6,6,6-nonafluorohexyl) = 2-sulfonitoxysuccinate, FUJIFILM Fine Chemicals, Inc. ), 2% water dilution): 1.34 parts, distilled water: 48.71 parts

A polypropylene base material (PP, Trefan BO60-2500, manufactured by Toray Industries, Inc., base material thickness 60 μm) was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the adhesive layer forming composition 36 was applied by a bar coater using a bar count # 4, and dried at 80 ° C. for 2 minutes to form a laminated body with an adhesive layer having an average thickness of 1 μm.

-Preparation of hard coat layer-
By mixing the hard coat layer forming composition having the following composition, a coating liquid 36 for forming a hard coat layer was obtained.

-Composition of hard coat layer forming composition 36-
-Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Industries, Ltd., solid content 100%): 2.93 parts-Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Industries, Ltd., solid content 100%) ): 9.62 parts-Condensing aid (metal chelate, ALCH, manufactured by Kawaken Fine Chemical Industries, Ltd., solid content 100%): 2.13 parts-UV absorber (cerium oxide sol, Niedral U-15, Taki Chemical) Made by Co., Ltd., solid content 15%): 12.53 parts ・ Inorganic filler (alumina sol, F3000, manufactured by Kawaken Fine Chemical Industries, Ltd., solid content 5%): 38.95 parts ・ Surfactant (Naroacty CL- 95, manufactured by Sanyo Kasei Kogyo Co., Ltd., diluted with 1% water): 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 laminated body with the adhesive layer under the condition of 730 J / m ² . Then, the coating liquid 36 for forming a hard coat was applied by a bar coater using a bar count # 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 water-based coating material 4 prepared in Example 4 was subjected to corona discharge treatment under the condition of 730 J / m ² on the hard coat layer of the laminate with the hard coat film. Then, it was applied by a bar coater using bar count # 4, and dried at 80 ° C. for 2 minutes to obtain a laminate with an antireflection film having an average thickness of 130 nm.

-Formation of back surface A layer-
A corona discharge treatment was performed on the surface of the laminated body with the antireflection film on the opposite side of the surface on which the antireflection film was formed under the condition of 730 J / m ² . Then, the coating liquid for forming the adhesive layer was applied by a bar coater using a bar count # 4, and dried at 80 ° C. for 2 minutes to obtain a laminate with a back surface A layer having an average thickness of 1 μm.

-Formation of back surface B layer-
-Composition of back surface 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-Sulphonite oxysuccinate, manufactured by FUJIFILM Fine Chemicals Co., Ltd., diluted with 2% water): 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 coating liquid 36 for forming the back surface B layer was applied by a bar coater using a bar count # 20, and dried at 80 ° C. for 2 minutes to form a laminate with a back surface B layer having an average thickness of 10 μm. ..

-Formation of back surface C layer-
-Composition of back surface 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-Sulphonite oxysuccinate, manufactured by FUJIFILM Fine Chemicals Co., Ltd., diluted with 2% water): 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 coating liquid 36 for forming the back surface B layer was applied by a bar coater using a bar count # 8 and dried at 80 ° C. for 2 minutes to prepare a solar cell front sheet having an average thickness of 1 μm.

Further, the performance was evaluated 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 by the same method as in Example 36 except that the hard coat layer forming composition was changed to the following composition and the bar count was changed to # 10.

-Composition of hard coat layer forming composition 37-
-Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Industry Co., Ltd., solid content 100%): 16.56 parts-Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd., solid content 100%) ): 26.91 parts-Condensing aid (metal chelate, aluminum chelate D, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 76% isopropyl alcohol solution): 1.29 parts-ultraviolet absorber (cerium oxide sol, nidraal B- 10. Made by Taki Chemical Co., Ltd., solid content 10%): 45.56 parts ・ Surfactant (Naro Acty CL-95, manufactured by Sanyo Kasei Kogyo Co., Ltd., 1% water dilution): 2.38 parts ・Surfactant (Lapisol A-90, manufactured by Nichiyu Co., Ltd., diluted with 1% water): 3.40 parts, distilled water: 3.90 parts

Further, the performance was evaluated 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 by the same method 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 Industries, Ltd., solid content 100%): 2.93 parts-Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Industries, Ltd., solid content 100%) ): 9.62 parts-Condensing aid (metal chelate, ALCH, manufactured by Kawaken Fine Chemical Industries, Ltd., solid content 100%): 2.13 parts-UV absorber (cerium oxide sol, Niedral U-15, Taki Chemical) Made by Co., Ltd., solid content 15%): 12.53 parts ・ Inorganic filler (alumina sol, F1000, manufactured by Kawaken Fine Chemical Industries, Ltd., solid content 5%): 38.95 parts ・ Surfactant (Naroacty CL- 95, manufactured by Sanyo Kasei Kogyo Co., Ltd., diluted with 1% water): 2.43 parts, acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.): 0.77 parts, distilled water: 30.64 parts

Further, the performance was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

(Example 39)
[Preparation of base film with undercoat layer]
As described below, 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.

-Polyester synthesis-
A slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Kagaku Co., Ltd.) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) was charged with about 123 kg of bis (hydroxyethyl) terephthalate in advance, and the temperature was 250 ° C. and the pressure was 1. The esterification reaction tank held at 2 × 105 Pa was sequentially supplied over 4 hours, and the esterification reaction was further carried out over 1 hour after the end of supply. Then, 123 kg of the obtained esterification reaction product was transferred to a polycondensation reaction tank.

Subsequently, ethylene glycol was added in an amount of 0.3% by mass based on the obtained polymer to the polycondensation reaction tank to which the esterification reaction product was transferred. After stirring for 5 minutes, ethylene glycol solutions of cobalt acetate and manganese acetate were added to the resulting polymer at 30 ppm and 15 ppm, respectively. After further stirring for 5 minutes, a 2% by mass ethylene glycol solution of the titanium alkoxide compound was added to the resulting polymer at 5 ppm. Five minutes later, a 10 mass% ethylene glycol solution of ethyl diethylphosphonoacetate was added to the resulting polymer at 5 ppm. Then, while stirring the low polymer at 30 rpm, the reaction system was gradually heated from 250 ° C. to 285 ° C., and the pressure was lowered to 40 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reached a predetermined value, the reaction system was purged with nitrogen, returned to normal pressure, and the polycondensation reaction was stopped. Then, the polymer obtained by the above-mentioned polycondensation reaction was discharged into cold water in a strand shape, and immediately cut to prepare polymer pellets (diameter: about 3 mm, length: about 7 mm). The time from the start of depressurization 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% by mass) synthesized in Example 1 described in paragraph 0083 of JP-A-2005-340616 was used.

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

-Making polyester film-
The pellets after undergoing solid-phase polymerization as described above were melted at 280 ° C. and cast on a metal drum to prepare an unstretched polyethylene terephthalate (PET) film having a thickness of about 3 mm.
Then, the unstretched PET film was stretched 3.4 times in the longitudinal direction (MD: Machine Direction) at 90 ° C. Next, a coating liquid for forming an undercoat layer having the following composition was applied to one surface of the uniaxially stretched PET film stretched to the MD so that the coating amount was 5.1 mL / m2, and after the MD stretching, the coating solution was laterally (TD:: Transverse Direction) Application was performed by the in-line coating method before stretching.
The PET film coated with the coating liquid for forming an undercoat layer 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 carried out 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 was formed was heat-fixed at 190 ° C. for 15 seconds, and then at 190 ° C., the MD relaxation rate was 5% and the TD relaxation rate was 11% in the MD direction and the TD direction. Was subjected to heat 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 Co., Ltd., solid content 28%): 21.9 parts-Oxazoline-based cross-linking agent (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content 25%): 4 .9 parts ・ Fluorine-based surfactant (sodium = bis (3,3,4,5,5,5,6,6,6-nonafluorohexyl) = 2-sulfonitoxysuccinate, FUJIFILM Fine Chemicals ( Manufactured by Co., Ltd., diluted with 2% water): 0.1 parts ・ Distilled water: 100 parts in total

-Preparation of adhesive layer-
By mixing the adhesive layer forming composition having the following composition, a coating liquid 38 for forming an adhesive layer was obtained.

-Composition of Adhesive Layer Forming Composition 39-
-Acrylic resin (Ceranate WSA-1070, manufactured by DIC Corporation, solid content 40%): 60.87 parts-Oxazoline-based cross-linking 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 (3,3,4,5,5) , 5,6,6,6-nonafluorohexyl) = 2-sulfonitoxysuccinate, manufactured by Fujifilm Fine Chemicals Co., Ltd., diluted with 2% water): 1.01 part, distilled water: 10.24 part

Corona discharge treatment was performed under the condition of 730 J / m ^{2 on} the surface side of the PET film with an undercoat layer on which the undercoat layer was not formed. Then, the coating liquid 39 for forming an adhesive layer 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 coating liquid 39 for forming a hard coat layer was obtained by mixing the hard coat layer forming composition having the following composition in the following procedure.
The coating liquid 39 for forming the hard coat layer was adjusted by the following procedure.
After adding KBE-403 to the acetic acid aqueous solution and sufficiently hydrolyzing it, KBE-04 is added and sufficiently hydrolyzed, and a mixed solution containing hydrolyzates of these alkoxysilanes (KBE-403 and KBE-04). Got Next, aluminum chelate D, Snowtex OZL-35, Lapisol A-90, Naroacty CL-95, and water were added to this mixed solution to obtain a coating liquid 39 for forming a hard coat.

-Composition of hard coat layer forming composition 39-
-Silane coupling agent (KBE-04, manufactured by Shin-Etsu Chemical Industry Co., Ltd., solid content 100%): 0.91 parts-Silane coupling agent (KBE-403, manufactured by Shin-Etsu Chemical Industry 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 Chemical Co., Ltd., solid content 76% isopropyl alcohol solution) ): 0.89 parts-Inorganic filler (Silane, average particle size 100 nm, Snowtex OZL-35, manufactured by Nissan Chemical Industries, Ltd., solid content 35.5%): 8.59 parts-Surfactant (Lapisol A) -90, manufactured by Nichiyu Co., Ltd., diluted with 1% water): 3.30 parts, surfactant (Naroacty CL-95, manufactured by Sanyo Kasei Kogyo Co., Ltd., diluted with 1% water): 2.30 parts, Diluted water: 80.98 parts

Next, a corona discharge treatment was performed on the adhesive layer of the laminated body with the adhesive layer under the condition of 730 J / m ² . Then, the coating liquid 39 for forming a hard coat was applied by a bar coater using a bar count # 4, and dried at 170 ° C. for 2 minutes to obtain a laminate with a hard coat film having an average thickness of 0.2 μm. ..

-Formation of antireflection film-
The water-based coating material 4 prepared in Example 4 was subjected to corona discharge treatment under the condition of 730 J / m ² on the hard coat layer of the laminate with the hard coat film. Then, it was applied by a bar coater using bar count # 4, and dried at 170 ° C. for 2 minutes to obtain a laminate with an antireflection film having an average thickness of 130 nm.

-Formation of back surface A layer-
By mixing the back surface A layer forming composition having the following composition, a coating liquid 39 for forming the back surface A layer was obtained.

-Composition of back surface A layer forming composition 39-
-Acrylic resin (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 28%): 52.08 parts-Crosslink resin (Arrow base SE-1013N, manufactured by Unitica Co., Ltd., solid content 20%): 8.02 Part-Oxazoline-based cross-linking agent (Epocross WS-700, manufactured by Nippon Catalyst Co., Ltd., solid content 25%): 16.20 parts-UV absorber (Triazine-based UV absorber, TINUVIN479DW, manufactured by BASF, solid content 40%) ): 3.50 parts, cross-linking catalyst (second ammonium phosphate aqueous solution, manufactured by Nippon Chemical Industry Co., Ltd., solid content 35% water dilution): 1.26 parts, fluorine-based surfactant (sodium = bis (3, 3) 3,4,4,5,5,6,6,6-nonafluorohexyl) = 2-sulfonite oxysuccinate, manufactured by Fujifilm Fine Chemicals Co., Ltd., diluted with 2% water): 0.47 parts, distilled Water: 18.47 copies

A corona discharge treatment was performed on the surface of the laminated body with the antireflection film on the opposite side of the surface on which the antireflection film was formed under the condition of 730 J / m ² . Then, the coating liquid for forming the adhesive layer was applied by a bar coater using a bar count # 12, and dried at 170 ° C. for 2 minutes to obtain a laminate with a back surface A layer having an average thickness of 5 μm.

-Formation of back surface B layer-
-Composition of back surface 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 (EMALEX110, manufactured by Nippon Emulsion Co., Ltd., diluted with 10% solid 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 . Then, the back surface B layer forming coating liquid 39 is applied by a bar coater using a bar count # 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. Made.

Further, the performance was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

-Manufacturing of solar cell module-
Examples of the solar cell front sheet according to Examples 36 to 39, an EVA sheet (F806P: manufactured by Hangzhou first PV material), a crystalline solar cell, and an EVA sheet (F806P: manufactured by Hangzhou first PV material). A solar cell module was produced by hot-pressing the solar cell front sheets described in 36 to 39 as a back sheet.
The bonding conditions for the EVA sheet were as follows.
After vacuuming at 145 ° C. for 5 minutes using a vacuum laminator, the mixture was pressurized and heated at a pressure of 0.1 MPa for 10 minutes for adhesion.
When power generation was performed using the manufactured solar cell module, it showed good power generation performance as a solar cell.

(Example 40)
-Composition A-
Composition A was obtained by mixing the following compositions in the following procedure.

-Composition of hydrolyzed solution 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 Was mixed and stirred at room temperature for 16 hours to obtain a hydrolyzed solution for forming Composition A.

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

-Composition B-
Composition B was obtained by mixing the following compositions in 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 Co., Ltd. ): 1.50 parts For forming composition B by adding distilled water, acetic acid, and MS-51 to the emulsion particle dispersion 4 obtained in Example 4 and stirring at 25 ° C. for 16 hours. A core-shell particle dispersion was obtained.
Then, 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 non-polar 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 ratios.

-Composition of water-based coating material 40-
-Composition A: 50.00 parts-Composition B: 50.00 parts

Next, a polypropylene base material (PP, Trefan BO60-2500, manufactured by Toray Industries, Inc., base material thickness 60 μm) was subjected to corona discharge treatment under the condition of 730 J / m ² . Then, the water-based coating material 40 was applied by a bar coater using a bar count # 8 and dried at 80 ° C. for 2 minutes to form a coating layer having an average thickness of 130 nm to obtain a laminate.

Further, the performance was evaluated 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 materials C1 of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that the substrate, the organic solvent, the surfactant, the W / O ratio, and the drying conditions were changed. And C2, and laminates C1 and C2, respectively.
Further, the performance was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

The “W / O ratio” in Tables 1 to 5 represents the content of the surfactant at the time of forming the emulsion particles with respect to the total mass of the organic solvent in the aqueous coating material used.
Details of the abbreviations shown in Tables 1 to 5 other than those described above are shown below.
Heptan: n-Heptan, 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. Xylen: p-xylene, manufactured by Wako Pure Chemical Industries, Ltd. Dodecan manufactured by Wako Pure Chemical Industries, Ltd .: n-dodecane, Tetradecane manufactured by Wako Pure Chemical Industries, Ltd .: n-tetradecane, Heptadecan manufactured by Wako Pure Chemical Industries, Ltd .: n-Heptadecan, Octadecan manufactured by Wako Pure Chemical Industries, Ltd .: n-octadecan , Wako Pure Chemical Industries, Ltd. Ca-2: Hexadecyltrimethylammonium bromide, cation surfactant, Wako Pure Chemical Industries, Ltd. Ca-3: Polyethylene Imine, Mw1,200, cation surfactant, Wako Pure Chemical Industries, Ltd. Made by Yaku Kogyo Co., Ltd. Ca-4: Polyethylene Imine, Mw 10,000, Cationic Surface Active Agent, Wako Pure Chemical Industries, Ltd. No-1: Polyoxyethylene Lauryl Ether, Nonion Surfing Agent, Nippon Emulsion Co., Ltd. Made by Emarex 710
Glass: Glass base material, OA-10G manufactured by Nippon Electric Glass Co., Ltd., thickness 700 μm
PET: Polyethylene terephthalate base material PC: Polycarbonate base material, Carboglass C110 manufactured by Asahi Glass Co., Ltd., thickness 500 μm
Acrylic resin: Acrylic resin base material, Technoroy S001G manufactured by Sumitomo Chemical Co., Ltd., thickness 75 μm

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

The disclosure of Japanese Patent Application No. 2018-035216, filed February 28, 2018, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (15)

water,
At least one selected from the group consisting of a siloxane compound represented by the following formula 1, a hydrolyzate of a siloxane compound represented by the following formula 1, and a hydrolyzate of a siloxane compound represented by the following formula 1. Compound,
Surfactants, as well as
Contains core-shell particles containing an organic solvent as a core material,
A water-based coating material in which 20% by mass or more of the organic solvent is a non-polar 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20. The water-based coating material according to claim 1, wherein at least 50% by mass in the organic solvent is the non-polar solvent. The aqueous coating material according to claim 1 or 2, wherein the non-polar solvent is a hydrocarbon compound having 7 or more carbon atoms. The aqueous coating material according to claim 3, wherein the hydrocarbon compound is an alkane. The water-based coating material according to any one of claims 1 to 4, wherein the coefficient of variation of the particle size of the core-shell particles is 100% or less. After the coat layer has dried,
The coat layer contains water, a hydrolyzed condensate of a siloxane compound represented by the formula 1, a surfactant, and core-shell particles containing an organic solvent in the core material.
20% by mass or more of the organic solvent is a non-polar solvent having a boiling point of 90 ° C. or higher and 350 ° C. or lower.
A film having voids inside at least a part 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20. The film according to claim 6, wherein the average internal void diameter of the film is 30 nm or more, and the coefficient of variation of the void diameter is 60% or less. The film according to claim 6 or 7, which is an antireflection film. A laminate having the film according to any one of claims 6 to 8. The laminate according to claim 9, which has the film on a base material. The laminate according to claim 10, wherein the base material is a resin base material. The laminate according to any one of claims 9 to 11, which is a solar cell front sheet. A step of applying the water-based coating material according to any one of claims 1 to 5 on a base material to form a coating layer, and
Including the step of drying the coat layer
A method for producing a film in which at least a part of the core-shell particles becomes hollow particles that form voids inside the coat layer after the drying step. A step of applying the water-based coating material according to any one of claims 1 to 5 on a base material to form a coating layer, and
Including the step of drying the coat layer
A method for producing a laminate in which at least a part of the core-shell particles becomes hollow particles that form voids inside the coat layer after the drying step. Composition A containing a siloxane compound represented by the following formula 1 and
The composition B containing water, a surfactant, and an organic solvent is provided.
A water-based coating material kit in which 20% by mass or more of the organic solvent in the composition B is a non-polar 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 independently represent an alkyl group, a vinyl group, an epoxy group, a styryl group, respectively. Represents an organic group having a group selected from the group consisting of (meth) acrylic group, amino group, isocyanurate group, ureido group, mercapto group, sulfide group, polyalkyleneoxyalkyl group, carboxy group and quaternary ammonium group. Each of m independently represents an integer of 0 to 2, and n represents an integer of 1 to 20.