JP2014123750A - Coating composition for solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition and the like for a solar cell excellent in base material adhesion, antifouling properties, and base material protective properties.SOLUTION: A coating composition for a solar cell comprises a component A and a component B. The component A is metal compound particles with a particle diameter of 1 to 400 nm. The component B is polymer emulsion particles with a particle diameter of 10 to 800 nm. The polymer emulsion particles as the component B are obtained by polymerizing polymer stock solution containing the following respective components (b1) to (b4): the component (b1) is a hydrolyzable silicon compound; the component (b2) is a vinyl monomer containing at least one kind of functional group selected from a group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an ether group; the component (b3) is an emulsifying agent; and the component (b4) is water.

Description

  The present invention relates to a solar cell coating composition, a laminate, a solar cell cover material, and a solar cell.

  Solar cells can directly convert sunlight into electrical energy. Unlike fossil fuels, solar cells use semi-permanent sunlight as a resource, so they can be used semipermanently and are very clean energy.

  The light receiving surface of the solar cell is usually protected by a protective cover made of glass, a weather resistant resin film, or the like. Here, since the protective cover is soiled with dust during long-term use, the light transmittance is lowered, and the energy conversion efficiency of the solar cell is lowered. In particular, with recent environmental pollution, the cover is quickly soiled, and the conversion efficiency of the solar cell tends to decrease early. Although it is desirable to clean a solar cell cover regularly or as needed, since a solar cell cover is generally installed in the outer wall of a roof or a building, cleaning of a cover is not easy.

  Under such circumstances, Patent Document 1 (Japanese Patent Application Laid-Open No. 10-107303) discloses a surface layer portion including photocatalyst particles and silicone and water repellent fluororesin, or photocatalyst particles, amorphous silica and water repellent fluororesin. A solar cell cover provided with is proposed.

In Patent Document 2 (Japanese Patent Laid-Open No. 10-270732), a protective cover film layer, a fluorine-based resin film layer, and a photocatalyst-containing surface layer portion are sequentially provided on the battery surface, and contaminants attached to the surface are removed. A solar battery cover characterized by being disassembled has been proposed.
JP-A-10-107303 JP-A-10-270732

However, in the method described in Patent Document 1, the base material layer of the protective cover film may be deteriorated by the organic substance decomposition action of the photocatalyst in the surface layer portion, and the appearance of the solar cell cover may be deteriorated.
In the method described in Patent Document 2, a fluororesin film layer is provided to prevent the protective cover film layer from deteriorating due to the organic substance decomposition action of the photocatalyst in the surface layer portion, and the manufacturing process tends to be complicated. . Moreover, since an interface exists between the layers, there is a concern about problems such as peeling of the photocatalyst layer. Therefore, a solar cell cover having a simpler layer structure has been demanded.
Furthermore, recent solar cells have a strong demand for low cost and long-term durability, so they have excellent long-term adhesion to glass substrates and resin substrates used for solar cell covers, and have a low environmental impact. An agent was desired.
The subject of this invention is providing the coating composition for solar cells etc. with favorable base-material adhesiveness, antifouling property, and base-material protection.

（式中、Ｒは式（１）で定義した通りである。）

[１４] （Ａ’）成分が、光触媒活性を有する上記［１３］に記載の太陽電池用コーティング組成物。
[１５] （Ａ’）成分の粒子長（ｌ）と粒子直径（ｄ）の比（ｌ／ｄ）が、１／１から２０／１である上記［１３］又は［１４］に記載の太陽電池用コーティング組成物。
[１６] 上記［１］〜［１５］のいずれかに記載の太陽電池用コーティング組成物を用いて形成される塗膜と、樹脂基材とを含む積層体。
[１７] 塗膜のヘイズが２０以下である上記［１６］に記載の積層体。
[１８] 上記［１６］〜［１７］のいずれかに記載の積層体を用いてなる太陽電池用カバー材。
[１９] 上記［１］〜［１５］のいずれかに記載の太陽電池用コーティング組成物を含んでなる太陽電池。 As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention is as follows.
[1] Each component of the following (A) and (B),
(A) component: metal compound particles having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle size of 10 nm to 800 nm,
Including
The component (B) is the following components (b1) to (b4):
(B1) component: hydrolyzable silicon compound,
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: emulsifier,
(B4) component: water,
A coating composition for solar cells, which is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing
[2] The solar cell coating composition according to [1], wherein the component (b2) is a vinyl monomer having a secondary and / or tertiary amide group.
[3] The above [1] or [2], wherein the ratio (b2) / (B) (mass ratio) between the component (b2) and the component (B) is 0.1 / 1 to 0.8 / 1. The coating composition for solar cells described in 1.
[4] In any one of the above [1] to [3], the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer. The coating composition for solar cells described.
[5] In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer, The coating composition for solar cells according to the above [4], wherein the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.1 / 1 to 5/1.
[6] The above [1] to [3], wherein the component (B) has a three-layer structure including a core layer, a shell first layer that covers the core layer, and a shell second layer that covers the outer side of the core layer. ] The coating composition for solar cells in any one of.
[7] In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and in the shell first layer (b2 ) / (B1) (mass ratio) is 0.1 / 1 to 1/1, and (b2) / (b1) (mass ratio) is 1/1 to 9/1 in the shell second layer [6] The coating composition for solar cells described in 1.
[8] The component (B) is obtained by polymerizing the polymerization stock solution in the presence of the seed particles forming the core layer, and the seed particles include the component (b1), the component (b2), and the following (b5) component,
Component (b5): other vinyl monomer copolymerizable with component (b2),
The coating composition for solar cells according to any one of the above [4] to [7], obtained by polymerizing at least one selected from the group consisting of:
[9] The component (b1) is the following component (b1-1):
(B1-1) component: a hydrolyzable silicon compound having a vinyl polymerizable group,
Including
Of the above [1] to [8], the ratio (b1-1) / (B) (mass ratio) of the component (b1-1) to the component (B) is 0.01 / 100 to 20/100. The coating composition for solar cells in any one.
[10] The above [9], wherein the ratio (b1-1) / (b2) (mass ratio) of the component (b1-1) to the component (b2) is 0.1 / 100 to 100/100. The coating composition for solar cells.
[11] The component according to any one of [1] to [10], wherein the component (A) is formed using any one of silicon dioxide, a metal oxide having photocatalytic activity, or a metal oxide having conductivity. The coating composition for solar cells.
[12] The ratio (l / d) of the particle length (l) and the particle diameter (d) of the component (A) is any one of the above [1] to [11], which is 1/1 to 20/1. The coating composition for solar cells described.
[13] The component (A) is the following component (A ′):
(A ′) component: triorganosilane unit represented by formula (1), monooxydiorganosilane unit represented by formula (2), dioxyorganosilane unit represented by formula (3), formula ( 4) Using a modifier compound having at least one structural unit selected from the group consisting of a trioxysilane unit represented by 4) and a difluoromethylene unit, the metal compound particles of component (A) are modified. Modified metal compound particles formed,
The solar cell coating composition according to any one of the above [1] to [12].
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)

[14] The solar cell coating composition according to [13], wherein the component (A ′) has photocatalytic activity.
[15] The sun as described in [13] or [14] above, wherein the ratio (l / d) of the particle length (l) to the particle diameter (d) of the component (A ′) is from 1/1 to 20/1. Battery coating composition.
[16] A laminate comprising a coating film formed using the solar cell coating composition according to any one of [1] to [15], and a resin base material.
[17] The laminate according to [16], wherein the coating film has a haze of 20 or less.
[18] A solar cell cover material comprising the laminate according to any one of [16] to [17].
[19] A solar cell comprising the solar cell coating composition according to any one of [1] to [15].

  The coating composition for solar cells of the present invention can provide a coating composition for solar cells with good substrate adhesion, antifouling properties, and substrate protection properties.

Hereinafter, the best mode for carrying out the present invention (hereinafter, sometimes abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The solar cell coating composition of the present embodiment includes the following components (A) and (B):
(A) component: metal compound particles having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle size of 10 nm to 800 nm,
Including
The component (B) is the following components (b1) to (b4):
(B1) component: hydrolyzable silicon compound,
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: emulsifier,
(B4) component: water,
It is the polymer emulsion particle | grains obtained by superposing | polymerizing the polymerization stock solution containing this.
The component (A) is considered to act as a curing agent for the component (B) by interacting with the component (B). Examples of the interaction include a hydrogen bond between the hydroxyl group that the component (A) generally has and the hydroxyl group, carboxyl group, amide group, amino group, and ether group that the component (B) has, or the component (A). Can be exemplified by the condensation (chemical bond) of the hydroxyl group generally possessed by the polymerization product of the component (b1) constituting the component (B).
Moreover, it is preferable that the component (A) exists while forming a continuous layer between the particles of the component (B) while interacting with the component (B). In this case, the transparency of the resulting solar cell coating composition can be further improved.

Examples of the metal compound used for the component (A) include silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, and oxide from the viewpoint of interaction with the component (B). Examples thereof include lead, iron oxide, calcium silicate, magnesium oxide, niobium oxide, and cerium oxide.
Among these, from the viewpoint of the strength of interaction, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, and complex oxides thereof having a large surface hydroxyl group are preferable, and these two or more are used in combination. Is fine.

The metal compound used for the component (A) is a compound that expresses photocatalytic activity and / or hydrophilicity upon irradiation with light (hereinafter, simply referred to as “photocatalyst”) from the viewpoint of imparting antifouling properties. ) Is preferred. When a compound that expresses photocatalytic activity by light irradiation is used as the component (A), the surface of the resulting solar cell coating composition can exhibit excellent decomposition activity and contamination resistance of contaminating organic substances. Further, when a compound that exhibits hydrophilicity by light irradiation is used as the component (A), the surface of the resulting solar cell coating composition can exhibit self-cleaning ability (self-cleaning) by water such as rain. , Can exhibit stain resistance. In the present embodiment, “hydrophilic” means that the contact angle of water (20 ° C.) with respect to the surface of the measurement object is preferably 60 ° or less, more preferably 30 ° or less, and still more preferably 20 ° or less. Means that.
In addition, when a photocatalyst that exhibits photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 nm to 800 nm) (a visible light responsive photocatalyst) is selected, the surface of the resulting coating composition for solar cells is This is preferable because the environmental purification effect and antifouling effect in a place (such as indoors) where ultraviolet rays are not sufficiently irradiated become very large.

More specifically, examples of the photocatalyst include TiO ₂ , ZnO, SrTiO ₃ , BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe ₂ O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO _2, etc., and at least selected from Ti, Nb, Ta, V Layered oxides having one element (for example, JP-A-62-274452, JP-A-2-172535, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800) JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10-2 It can be cited reference No. Publication 4165). Among these photocatalysts, TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. As the titanium oxide, any of anatase type, rutile type and brookite type can be used, but a rutile type having relatively mild photocatalytic activity is preferable from the viewpoint of ultraviolet absorption.
Examples of the visible light responsive photocatalyst include oxynitride compounds such as TaON, LaTiO ₂ N, CaNbO ₂ N, LaTaON ₂ , and CaTaO ₂ N (see, for example, JP-A-2002-66333), Sm ₂ Ti ₂ S. oxysulfide compounds such as ₂ O ₇ (see, for example JP 2002-233770 _{JP), CaIn 2 O 4, SrIn} 2 O 4, ZnGa 2 O 4, Na 2 Sb 2 O 6 , etc. ^{d 10} of electronic state metal ion Oxides (see, for example, JP-A-2002-59008), titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxy titanium, etc.) and high surface titanium oxide in the presence of nitrogen-containing compounds such as ammonia and urea. Nitrogen-doped titanium oxide obtained by firing (for example, JP 2002-29750 A, 2002-87818, JP-A-2002-154823, JP-A-2001-207082), titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of sulfur compounds such as thiourea. Sulfur-doped titanium oxide obtained by calcining titanium, oxygen-deficient titanium oxide obtained by subjecting titanium oxide to hydrogen plasma treatment or heat treatment under vacuum (for example, see JP-A-2001-98219), and Is a surface-treated photocatalyst obtained by treating a photocatalyst particle with a platinum halide compound (see, for example, JP-A-2002-239353) or tungsten alkoxide (see, for example, JP-A-2001-286755), etc. Can be preferably mentioned.

Among the visible light responsive photocatalysts, oxynitride compounds and oxysulfide compounds have a large photocatalytic activity by visible light, and can be particularly preferably used.
Moreover, as a metal compound used for said (A) component, the metal oxide which has electroconductivity is used suitably from a viewpoint of expressing the antistatic performance etc. of the coating composition for solar cells obtained.
Examples of such conductive metal oxides include indium oxide (ITO) doped with tin, tin oxide (ATO) doped with antimony, tin oxide, and zinc oxide.
In addition, the said (A) component can be formed using the various metal compounds mentioned above (preferably using as a main component). Here, in the present embodiment, the “main component” means that the proportion of the specific component (the total amount thereof when two or more specific components are used in combination) in the matrix component is preferably 50% by mass or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, and it means that 100 mass% may be sufficient.
Examples of forms when the component (A) is used include powders, dispersions, and sols.
The dispersion or sol as used herein refers to primary particles in which the component (A) is in a concentration of 0.01 to 80% by mass, preferably 0.1 to 50% by mass in water and / or a hydrophilic organic solvent. And / or a state of being dispersed as secondary particles.

Examples of the hydrophilic organic solvent include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran and dioxane, and the like. Examples include ethers, amides such as dimethylacetamide, dimethylformamide, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof.
The number average particle size of the component (A) observed in the dispersion or sol (may be a mixture of primary particles and secondary particles, or only primary particles or secondary particles). May be 1 nm to 400 nm, more preferably 1 nm to 100 nm, still more preferably 3 nm to 80 nm, and particularly preferably 5 nm to 50 nm. The number average particle diameter of the component (A) can contribute to the optical characteristics and the like of a laminate (such as a solar cell cover material) formed using the resulting solar cell coating composition. In particular, setting the thickness to 100 nm or less can greatly improve the transparency of the obtained solar cell cover material.
In addition, the number average particle diameter (simply abbreviated as “particle diameter”) in the present embodiment is a value measured according to the method of Examples described later.

As the component (A), from the viewpoint of improving dispersion stability, chemical stability and durability with respect to a solvent, the following component (A ′):
(A ′) component: triorganosilane unit represented by formula (1), monooxydiorganosilane unit represented by formula (2), dioxyorganosilane unit represented by formula (3), formula ( Using the modifier compound having at least one structural unit selected from the group consisting of a trioxysilane unit represented by 4) and a difluoromethylene unit, the metal compound particles of the component (A) are modified. It is preferable that the modified | denatured metal compound particle formed in this is included. “Modification” means immobilizing the modifier compound on the surface of the metal compound particles. The immobilization of the modifier compound on the surface of the metal compound particles is considered to be caused by van der Waals force (physical adsorption) or chemical bonding.
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

（式中、Ｒは式（１）で定義した通りである。）

(In the formula, R is as defined in formula (1).)

Examples of the modifier compound include Si—H group, hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, It preferably has a thiol group, an acid anhydride group or the like. In addition, the modifier compound is preferably a silicon compound, a fluoroalkyl compound, or a fluoroolefin polymer. Such a modifier compound can be firmly bonded to the metal compound particles.
When the specific example of a fluoroalkyl compound is shown in the said modifier compound, the compound shown by Formula (5) can be mentioned.
_{CF 3 (CF 2) g-} Y- (V) w (5)
{In the formula, g represents an integer of 0 to 29. Y represents a w-valent organic group having a molecular weight of 14 to 50,000. w is an integer of 1-20. V is composed of an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group, a phosphoric acid group, and a group represented by the following formula (6). It represents at least one functional group selected from the group.
-SiWxRy (6)
(In the formula, W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. Represents at least one selected group, wherein R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more. Is an integer of 3 or less, and y is an integer of 0 or more and 2 or less, and x + y = 3.)}

  Moreover, as said modifier compound, from a viewpoint of making the surface energy of the (A ') component obtained small and expressing a self-inclination function (for example, in said formula (1)-(4)), a small surface energy is used. The substituent R is a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, a linear or branched carbon number 2 to 2. It is preferable to select a compound which is at least one selected from 30 alkenyl groups and / or a compound having a difluoromethylene unit.

Here, “express self-grading function” means that a solar cell cover material is formed by laminating a solar cell coating composition containing the component (A ′) and the component (B) on a substrate. When this is done, the concentration gradient of the component (A ′) (the concentration deviation in the layer formed by the coating composition for solar cells) is self-supporting corresponding to the properties of the substrate surface (particularly hydrophilic / hydrophobic). It means that it is formed.
When the photocatalyst modified with a compound having a small surface energy is used as the component (A ′) and a solar cell cover material is formed using a substrate having a large surface hydrophilicity, the component (A ′) It tends to be unevenly distributed on the side in contact with the surface of the base material and decrease in the abundance. In such a case, high photocatalytic activity can be expected, and the substrate is hardly decomposed (durability of the substrate is improved), which is preferable.

In addition, as a method for the above modification treatment, for example, the metal compound particles and the modifier compound are mixed in the presence or absence of water and / or an organic solvent, preferably 0 to 200 ° C. Preferably, a method of heating at 10 to 80 ° C., a method of mixing the metal compound particles and the modifier compound in the presence of a mixed solvent, and changing the solvent composition of the mixed solvent by (vacuum) distillation or the like, Etc.
The proportion of the component (A ′) in the component (A) is preferably 0.01 to 100% by mass, more preferably 0.01 to 99.99% by mass, and still more preferably 0.1 to 100% by mass. It is 95 mass%, Most preferably, it is 1-90 mass%. Setting the ratio to 0.01% by mass or more is preferable from the viewpoint of imparting self-tilting property. In addition, it is suitable that the said ratio shall be 99.99 mass% or less from a viewpoint of making photocatalytic performance express in a comparatively short time.

In addition, regarding the component (A) or the component (A ′), the ratio (l / d) of the particle length (l) to the particle diameter (d) is a viewpoint of securing a specific surface area and the orientation of the particles. From the viewpoint of the effect, it is preferably 1/1 to 20/1, more preferably 1/1 to 15/1, and further preferably 1/1 to 10/1.
As a method for measuring the particle length and particle diameter, a method of observation with a transmission electron microscope can be used.

The component (B) includes the following components (b1) to (b4):
(B1) component: hydrolyzable silicon compound,
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: emulsifier,
(B4) component: water,
Polymer emulsion particles obtained by polymerizing a polymerization stock solution containing As the component (B) thus obtained, it is preferable to use a compound in which the hydroxyl group derived from the component (b1) and the polymerization product of the component (b2) are combined by hydrogen bonding or the like. It is.

As said (b1) component, the compound represented by following formula (7), its condensation product, and a silane coupling agent can be illustrated.
SiWxRy (7)
(In the formula, W represents an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. Represents at least one selected group, wherein R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or carbon atom. It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more and 4; And y is an integer of 0 or more and 3 or less, and x + y = 4.)
In addition, a silane coupling agent means the compound in which the functional group which has reactivity with organic substances, such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, an isocyanate group, exists in a molecule | numerator.

  Specific examples of the compound represented by the formula (7) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltri Toxisilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-tri Fluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) Atacyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysila , Trialkoxysilanes such as 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane , Diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxy Silane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyl The Dialkoxysilanes such as toxisilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane And the like. Moreover, these can be used individually or in mixture of 2 or more types.

As the component (b1), a silicon alkoxide having a phenyl group (for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc.) can be used. When a silicon alkoxide having a phenyl group is used, the polymerization stability in the presence of water and an emulsifier is good, which is preferable.
Furthermore, as said (b1) component, the silane coupling agent which has a thiol group, the following (b1-1) component,
(B1-1) Component: A hydrolyzable silicon compound having a vinyl polymerizable group may be included. When these are used, the weather resistance and antifouling properties of the obtained solar cell cover material are favorable, which is preferable.

Examples of the silane coupling agent having a thiol group include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
Examples of the component (b1-1) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acryloyloxypropylmethyldimethoxysilane. 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether Examples thereof include silane coupling agents having a vinyl polymerizable group.
These silane coupling agents can generate chemical bonds by copolymerization or chain transfer reaction with the component (b2) described later. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used by mixing or combining with the above-described component (b1), the polymerization product of (b1) and the component (b2) described later These polymerization products can be combined by chemical bonding.
Examples of the “vinyl polymerizable group” referred to as the component (b1-1) include a vinyl group and an allyl group. Among them, a 3- (meth) acryloxypropyl group is preferable.

Moreover, as said (b1) component, the following (b1-2) components,
Component (b1-2): A cyclic siloxane oligomer may be included. When the said (b1-2) component is used, the softness | flexibility of the solar cell cover material obtained becomes more favorable, and is suitable.

As said cyclic siloxane oligomer, the compound represented by following formula (8) can be illustrated.
(R ′ ₂ SiO) m (8)
(In the formula, R ′ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted carbon atom having 1 to 30 carbon atoms. It represents at least one selected from an alkyl group having 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, m is an integer, and 2 ≦ m ≦ 20 is there.)
Of these, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferred from the viewpoint of reactivity.

  In addition, when the said (b1) component is used as a condensation product, the polystyrene conversion weight average molecular weight (by GPC method) of the said condensation product becomes like this. Preferably it is 200-5000, More preferably, it is 300-1000.

The ratio (b1) / (B) (mass ratio) between the component (b1) and the component (B) described later is preferably 0.01 / 100 to 80/100, from the viewpoint of polymerization stability. Preferably it is 0.1 / 100-70 / 100.
On the other hand, the ratio (b1-1) / (B) (mass ratio) between the component (b1-1) and the component (B) is preferably 0.01 / 100 to from the viewpoint of polymerization stability. 20/100, more preferably 0.5 / 100 to 10/100.
The ratio (b1-1) / (b2) (mass ratio) between the component (b1-1) and the component (b2) is preferably 0.1 / 100 to from the viewpoint of polymerization stability. 100/100, more preferably 0.5 / 100 to 50/100.
On the other hand, the ratio (b1-2) / (B) (mass ratio) between the component (b1-2) and the component (B) is preferably 0.01 / 100 to 20 from the viewpoint of hydrophilicity. / 100, more preferably 0.5 / 100 to 5/100.
The ratio (b1-2) / (b2) (mass ratio) between the component (b1-2) and the component (b2) is preferably 0.5 / 100 to from the viewpoint of polymerization stability. 50/100, more preferably 1.0 / 100 to 20/100.

Examples of the component (b2) include various hydroxyl groups-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates; various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether; various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; polyethylene glycol, etc. Monoesters of polyoxyalkylene glycols obtained from various polyether polyols as typified and various unsaturated carboxylic acids as typified by (meth) acrylic acid and the like; Adducts of various hydroxyl group-containing monomers and lactones such as ε-caprolactone; or various epoxy groups such as glycidyl (meth) acrylate Adducts of the unsaturated monomer containing and various acids such as represented by acetic acid; and various unsaturated carboxylic acids such as represented by (meth) acrylic acid; Various hydroxyl group-containing vinyl monomers such as adducts with various monoepoxy compounds other than epoxides of α-olefins as represented by “Cardura E” (trade name of Shell, Netherlands) Etc.
As the carboxyl group-containing vinyl monomer, various unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid; monomethyl itaconate, Monoesters of unsaturated dicarboxylic acids with saturated monohydric alcohols such as mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate (Half esters); monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate or monovinyl succinate; various saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride Acid anhydrides and various hydroxyl-containing vinyl monomers listed above Addition reaction products of; further, and the like monomers, such as obtained allowed the addition reaction of various carboxyl group-containing monomers and lactones, such as supra.

  Examples of amino group-containing vinyl monomers include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) ) Various tertiary amino group-containing (meth) acrylic esters such as acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine; vinylpyridine, N-vinyl Various tertiary amino group-containing aromatic vinyl monomers such as carbazole N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide N- (2-di-n-propylamino) ethyl (meth) acrylate Various tertiary amino acids such as luamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide] ethylmorpholine Group-containing (meth) acrylamides; N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, N- (2-di-n-propylamino) ethylcrotonamide, Various tertiary amino group-containing crotonic acid amides such as N- (3-dimethylamino) propyl crotonic acid amide or N- (4-dimethylamino) butyl crotonic acid amide; 2-dimethylaminoethyl vinyl ether, 2-diethylamino Ethyl vinyl ether, 3-dimethylaminopropyl vinyl ether Or 4, such as dimethylamino-butyl vinyl ether, tertiary amino group-containing vinyl ethers of various or the like.

  Examples of ether group-containing vinyl monomers include various polyether chains such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, and polyoxyethylene-polyoxypropylene block copolymer. Examples thereof include vinyl ethers, allyl ethers or vinyl monomers such as (meth) acrylic acid esters having a side chain. As specific examples, Bremer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 [above, manufactured by NOF Corporation], MA-30, MA- 50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA [above, manufactured by Nippon Emulsifier Co., Ltd.]. Here, as for the oxyethylene unit of a polyoxyethylene chain, 2-30 are preferable. If it is less than 2, the flexibility of the coating film becomes insufficient, and if it exceeds 30, the coating film becomes soft and the blocking resistance is poor.

Examples of the amide group-containing vinyl monomer include N-alkyl or N-alkylene-substituted (meth) acrylamide.
More specifically, for example, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl- Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acrylo Ruhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N-vinylacetamide, dye Acetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, etc. can be mentioned.

  As said (b2) component, it is preferable to use the vinyl monomer which has a secondary and / or tertiary amide group from a viewpoint of improving a hydrogen bond property with another component more.

The ratio (b2) / (B) (mass ratio) between the component (b2) and the component (B) is preferably 0.1 / 1 to 0.5 / 1 from the viewpoint of polymerization stability. is there.
The ratio (b2) / (A) (mass ratio) between the component (b2) and the component (A) is preferably from the viewpoint of hydrogen bondability with the component (A) and blending stability. 0.1 / 1 to 1.0 / 1.
Examples of the component (b3) include acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid, Anionic surfactants such as alkali metal (Li, Na, K, etc.) salts of emulsifiers, ammonium salts of acidic emulsifiers, fatty acid soaps; quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate , Pyridinium salt, imidazolinium salt type cationic surfactants; polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethyleneoxypropylene bromide Kukoporima, nonionic surfactants such as polyoxyethylene distyryl phenyl ether; and the like. These can be used alone or in combination of two or more.

As the component (b3), from the viewpoint of improving the water dispersion stability of the component (B) to be obtained, and from the viewpoint of improving the weather resistance and antifouling properties of the resulting solar cell cover material, radical polymerization is possible. It is preferable to use a reactive emulsifier having a double bond.
More specifically, the reactive emulsifier includes, for example, a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, an alkali metal salt thereof, an ammonium salt, a polyoxyethylene, etc. Examples thereof include a vinyl monomer having a nonionic group and a vinyl monomer having a quaternary ammonium salt.
Examples of the vinyl monomer having a sulfonic acid group or a sulfonate group include, for example, a radically polymerizable double bond, and partly by a substituent such as an ammonium salt, a sodium salt, or a potassium salt of the sulfonic acid group. Selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, a phenyl group, a naphthyl group, and a succinic acid group. A compound having a substituent, a vinyl sulfonate compound having a vinyl group to which a substituent is bonded, such as an ammonium salt, a sodium salt, or a potassium salt of a sulfonic acid group;
As the vinyl monomer having a sulfate ester group, for example, it has a radical polymerizable double bond and is partially substituted by a substituent such as an ammonium salt, sodium salt or potassium salt of the sulfate ester group. , A compound having a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, a phenyl group, and a naphthyl group. It is done.
Specific examples of the compound having a succinic acid group partially substituted with a substituent such as ammonium salt, sodium salt or potassium salt of the sulfonic acid group include allylsulfosuccinate. More specifically, for example, Eleminol JS-2 (trade name) (manufactured by Sanyo Chemical Co., Ltd.), Latemuru S-120, S-180A or S-180 (trade name) (manufactured by Kao Corporation), etc. Can do.

Further, a compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group. Specific examples include, for example, Aqualon HS-10 or KH-1025 (trade name) (Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE-1025N or SR-1025 (trade name) (Asahi Denka Kogyo Co., Ltd.) Manufactured).
Specific examples of the vinyl monomer having a nonionic group include, for example, α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: ADEKA Rear soap NE-20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN- 50, manufactured by Dai-ichi Pharmaceutical Co., Ltd.).
The amount of the component (b3) used is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (B) from the viewpoint of polymerization stability.
The component (B) is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing the components (b1) to (b3) described above and the component (b4) (that is, “water”). The amount of the component (b4) used is preferably 30 to 99.9% by mass as the content in the polymerization stock solution from the viewpoint of polymerization stability.
In addition to the components (b1) to (b4), various components can be further mixed in the polymerization stock solution.

First, the polymerization stock solution contains the following component (b5):
Component (b5): other vinyl monomer copolymerizable with component (b2),
Can be mixed.
The use of such component (b5) means that the properties of the polymerization product to be produced (glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, polymerization of hydrolyzable silicon compound (b1)) From the viewpoint of controlling compatibility with the product.
Examples of the component (b5) include acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds, vinyl cyanides, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, anionic vinyl monomers. Examples thereof include a monomer containing a functional group such as a monomer.
The proportion of the component (b5) in the total vinyl monomer is preferably 0.001 to 30% by mass, and more preferably 0.05 to 10% by mass. The use amount is such that the glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, compatibility with the polymerization product of the hydrolyzable silicon compound (b1), and the like are controlled. To preferred.
Further, a chain transfer agent can be mixed in the polymerization stock solution.
Examples of such chain transfer agents include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thiomalic acid and the like. Thiocarboxylic acids or their salts or their alkyl esters, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and allyl compounds such as dimers of α-methylstyrene be able to.
The amount of these chain transfer agents to be used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of all vinyl monomers. Setting the amount to be used is suitable from the viewpoint of polymerization stability.
Furthermore, a dispersion stabilizer can be mixed in the polymerization stock solution.
Examples of such a dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resins, poly Synthetic or natural water-soluble or water-dispersible various water-soluble polymer substances such as acrylic acid (salt), polyacrylamide, water-soluble or water-dispersible acrylic resin, and the like, one or more of these Mixtures can be used.
The amount of these dispersion stabilizers used is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymer emulsion particles (B).
The polymerization of the polymerization stock solution described above is preferably carried out in the presence of a polymerization catalyst.
Examples of the polymerization catalyst for the component (b1) include hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid, and sulfonic acids such as sulfuric acid and p-toluenesulfonic acid. Acid emulsifiers such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, acidic or weakly acidic inorganic salts, phthalates Acid compounds such as acid, phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylene Basic compounds such as amines, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; tin compounds such as dibutyltin octylate and dibutyltin dilaurate Etc.

Among them, as the polymerization catalyst for the hydrolyzable silicon compound (b1), not only the polymerization catalyst but also an acidic emulsifier having an action as an emulsifier, particularly an alkylbenzene sulfonic acid having 5 to 30 carbon atoms (such as dodecylbenzene sulfonic acid). Highly preferred.
The polymerization catalyst for the component (b2) is preferably a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of a vinyl monomer. Water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are preferably used. More specifically, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2, Examples include 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), and the like.

In addition, as a usage-amount of a polymerization catalyst, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of all the vinyl monomers. When acceleration of the polymerization rate and polymerization at a low temperature of 70 ° C. or lower are desired, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or longalite in combination with the radical polymerization catalyst. is there.
In the present embodiment, the polymerization of the component (b1) and the polymerization of the component (b2) can be carried out separately. This is preferable because it can be achieved.
As a method for obtaining the component (B), so-called emulsion polymerization in which the emulsifier polymerizes the component (b1) and the component (b2) in the presence of a sufficient amount of water to form micelles is suitable. Yes.
As a method of emulsion polymerization, for example, the component (b1) and the component (b2), and further, the component (b3) as necessary, as they are or in an emulsified state, are collectively or divided, or continuously. And a method of polymerizing at a reaction temperature of about 30 to 150 ° C. in the presence of the polymerization catalyst, preferably from atmospheric pressure to a pressure of 10 MPa if necessary. In some cases, the polymerization may be carried out at a higher pressure or lower temperature.
In addition, as a mixing | blending of superposition | polymerization stock solution, from a viewpoint of superposition | polymerization stability, the amount of final solid content is 0.1-70 mass%, Preferably it is 1-55 mass% of said (b1)-(b4). Each component is preferably blended.
Furthermore, when performing the emulsion polymerization, it is preferable to use a seed polymerization method from the viewpoint of appropriately growing or controlling the particle diameter. The seed polymerization method is a method in which emulsion particles (seed particles) are previously present in an aqueous phase for polymerization. The pH in the polymerization system when performing the seed polymerization method is preferably 1.0 to 10.0, more preferably 1.0 to 6.0. The pH can be adjusted using a pH buffer such as disodium phosphate, borax, sodium hydrogen carbonate, or ammonia.
In addition, as a method of obtaining the component (B), the component (b1) and the component (b2) in the presence of the component (b3) and the component (b4) necessary for polymerizing the component (b1). A method in which water is added until the polymerization product becomes an emulsion after the components are polymerized in the presence of a solvent, if necessary, can also be applied.

As said (B) component, from a viewpoint of improving the base-material adhesiveness of the coating film formed using the coating composition for solar cells obtained, 1 layer or 2 layers which coat | cover the said core layer It is preferable to have a core / shell structure provided with the above shell layer. As a method for forming the core / shell structure, multistage emulsion polymerization in which the emulsion polymerization is performed in multiple stages is very useful.
More specifically as an example of multi-stage emulsion polymerization, for example, as the first stage, in the presence of the component (b3) and the component (b4), a group consisting of the components (b1), (b2), and (b5) At least one selected from the above is polymerized to form seed particles, and in the second stage, in the presence of the seed particles, the component (b1) and the component (b2), and further, if necessary (b5) ) Polymerization is conducted by adding a polymerization stock solution containing the component (two-stage polymerization method). When carrying out multi-stage emulsion polymerization of three or more stages, for example, as a third stage, polymerization is carried out by adding a polymerization stock solution further containing the component (b1) and the component (b2) and, if necessary, the component (b5). be able to. Such a method is also suitable from the viewpoint of polymerization stability.

In the two-stage polymerization method, as a mass ratio of the solid content mass (M1) in the polymerization stock solution used in the first stage and the solid content mass (M2) in the polymerization stock solution added in the second stage, From the viewpoint of polymerization stability, (M1) / (M2) = 9/1 to 1/9, more preferably 8/2 to 2/8.
In the three-stage polymerization method, the solid content mass (M1) in the polymerization stock solution used in the first stage, the solid content mass (M2) in the polymerization stock solution added in the second stage, and the third stage The mass ratio of the solid content mass (M3) in the added polymerization stock solution is preferably (M2 + M3) / (M1) = 9/1 to 1/9, M3 / M2 = 1 / from the viewpoint of polymerization stability. 1 to 0.1 / 1 is preferable.

Further, the ratio (b2) / (b1) (mass ratio) between the component (b1) and the component (b2) is (in the core part formed in the first stage of polymerization from the viewpoint of substrate adhesion) b2) / (b1) = 1/1 or less, (b2) / (b1) = 0.1 / 1 to 1/1 in the shell layer formed in the second stage, shell layer formed in the third stage Is more preferably (b2) / (b1) = 1/1 to 9/1.
Further, as the core / shell structure, from the viewpoint of polymerization stability, the particle size distribution (volume average particle size / number average particle size) of the seed particles does not change greatly, and the particles are obtained by the second stage polymerization. It is preferable to have a structure with an increased diameter. The volume average particle diameter can be measured in the same manner as the number average particle diameter.
The core / shell structure can be observed, for example, by morphological observation using a transmission electron microscope or the like, analysis by viscoelasticity measurement, or the like.
The glass transition temperature (Tg) of the core layer having the core / shell structure is preferably 0 ° C. or lower. In this case, as a physical property of the obtained coating composition for solar cells, it becomes possible to form a solar cell cover material that is excellent in flexibility at room temperature and is less likely to be cracked.
In addition, Tg in this Embodiment can be measured with a differential scanning calorimeter (DSC).
The particle size of the component (B) is 10 nm to 800 nm. By adjusting to such a particle diameter range and forming the composition in combination with the component (A) having a particle diameter of 1 nm to 400 nm, the weather resistance and antifouling properties are good, and the resin base material A coating composition for solar cells with good protection can be realized. Moreover, it is suitable from a viewpoint of the transparency improvement of the coating film obtained that the particle diameter of the said (B) component shall be 50 nm-300 nm.
The ratio (A) / (B) (mass ratio) of the component (A) to the component (B) is preferably 1/99 to 99/1, more preferably 5/95 to 90/10, and even more preferably. Is 9/91 to 83/17. From the coating composition for solar cells blended in this range, a solar cell cover material excellent in weather resistance and antifouling property can be realized, which is preferable.

The ratio (SA) / (SB) of the surface area (SA) of the component (A) and the surface area (SB) of the component (B) is preferably in the range of 0.001 to 1000. The surface area can be calculated from the particle diameter of each of the component (A) and the component (B) and the blending mass number.
In the solar cell coating composition of the present embodiment, depending on its use and usage, etc., additive components that are usually added and blended into paints and molding resins, such as light stabilizers, ultraviolet absorbers, Thickener, leveling agent, thixotropic agent, antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skinning agent, dispersing agent, wetting agent, oxidation Inhibitors, UV absorbers, rheology control agents, film forming aids, rust inhibitors, dyes, plasticizers, lubricants, reducing agents, antiseptics, antifungal agents, deodorants, anti-yellowing agents, antistatic An agent, a charge control agent, or the like can be selected or combined depending on the purpose.
As the light stabilizer, for example, a hindered amine light stabilizer is preferably used. Among these, a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule is preferable.
Moreover, as said ultraviolet absorber, an organic type ultraviolet absorber can be mentioned, for example. Examples of such organic ultraviolet absorbers include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. Among these, it is preferable to use a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule. Moreover, a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber having high ultraviolet absorbing ability are preferable.
The light stabilizer is preferably used in combination with the organic ultraviolet absorber. Using both together can contribute to improving the weather resistance of the resulting solar cell coating composition.

Moreover, these organic ultraviolet absorbers, light stabilizers, and various additive components can be simply blended with the component (A) and the component (B), or the component (B) is synthesized. It is also possible to coexist when doing so.
The laminated body of this Embodiment is a laminated body containing the resin base material and the coating film formed with the coating composition for solar cells mentioned above, Preferably, the resin base material for solar cells mentioned above is preferable. A laminate comprising a coating film made of a coating composition.
Further, the solar cell cover material of the present embodiment is formed using the laminate, and is preferably formed as a laminate comprising a resin base material and a coating film comprising the above-described solar cell coating composition. The

Furthermore, the solar cell of the present embodiment includes the solar cell cover material.
Here, as said base material, organic base materials, such as a synthetic resin and a natural resin, inorganic base materials, such as glass, those combinations, etc. can be mentioned, for example.
The solar cell coating composition described above is not particularly limited, but can be prepared in a state dissolved or dispersed in a solvent such as water.
The coating film is, for example, coated on the substrate with the solar cell coating composition dispersed in a solvent such as water (sometimes abbreviated as “water dispersion”) and dried. Formed. Here, as solid content concentration of an aqueous dispersion, Preferably it is 0.01-60 mass%, More preferably, it is 1-40 mass%. The viscosity of the aqueous dispersion is preferably 0.1 to 100,000 mPa · s, preferably 1 to 10,000 mPa · s at 20 ° C. Furthermore, as the coating method, for example, spraying method, flow solar cell coating method, roll coating method, brush coating method, dip solar cell coating method, spin solar cell coating method, screen printing method, casting method, Examples include gravure printing and flexographic printing. The laminate is, for example, after drying the coating film on the base material, preferably subjected to heat treatment or ultraviolet irradiation at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C., if desired. It is also possible to form.
The thickness of the coating film is preferably 0.05 to 100 μm, more preferably 0.1 to 10 μm. From the viewpoint of transparency, the thickness is preferably 100 μm or less, and in order to exhibit functions such as weather resistance and antifouling properties, the thickness is preferably 0.05 μm or more.
The “coating film” referred to in the present embodiment is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
The haze of the coating film may be selected comprehensively from the viewpoint of the strength and durability of the coating film and the conversion efficiency of the solar cell, but is preferably 20 or less, more preferably 10 from the viewpoint of the conversion efficiency of the solar cell. Hereinafter, it is more preferably 5 or less.

  In addition, "haze" here can be measured according to the Example mentioned later, and can be adjusted with the magnitude | size of the particle diameter of the said (A) and (B) component.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. Various physical properties were evaluated by the following methods.
1. Number average particle size The sample was diluted with a suitable solvent so that the solid content in the sample was 0.01 to 20% by mass, and measured using a wet particle size analyzer (Microtrac UPA-9230, manufactured by Nihon Kikkiso). .
2. Contact angle (CA)
A surface of the solar cell cover material (coating surface of the solar cell coating composition) was placed on a deionized water drop and allowed to stand at 20 ° C. for 1 minute, and then contact angle measuring device (CA-X150, manufactured by Kyowa Interface Science, Japan). Type contact angle meter).
3. Using a haze turbidimeter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., Japan), the haze value of the coating film of the solar cell coating composition was measured according to JIS-K7105 (initial haze value).
4). Contamination resistance After applying the solar cell coating composition to a commercially available solar cell module, it is attached to an exposure table facing the general road (south surface, exposure angle 30 degrees) for 1 month, and the conversion efficiency is converted to an IV curve tracer. (Measured by Eihiro Seiki Co., Ltd., model MP-160) and compared with the conversion efficiency before exposure, the degree of decrease was evaluated according to the following criteria.
○: Efficiency decrease 5% or less Δ: Efficiency decrease 5 to 10%
X: Efficiency reduction 20% or less Adhesion of base material After the exposure test (black panel temperature 63 ° C, rainfall 18 minutes / 2 hours) using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), cover the solar cell cover material with cellophane (registered) Trademark) (1 cm × 5 cm) was applied, and the cellotape (registered trademark) was peeled off at an angle of 180 ° C., and the adhesion state of the coating film of the solar cell coating composition on the cellotape (registered trademark) was visually determined.
○: No adhesion Δ: Slight adhesion ×: Adhesion Substrate protection The cover material for solar cells was irradiated with ultraviolet light at an illuminance of 10 mW for 6 hours using a UV irradiator (UV300 manufactured by Oak Manufacturing Co., Ltd.). Then, the yellowing degree of the base material (PET film) was evaluated using a color difference meter (color guide 45/0 manufactured by BYK Gardner). The Δb value for the PET film before UV light irradiation was measured and evaluated according to the following criteria.
○: Less than 1 △: 1 or more and less than 5 ×: 5 or more

[Production Example 1]
[Emulsion particles B-1]
Into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 3 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR-1025” Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution with the temperature in the reaction vessel kept at 80 ° C. for about 2 hours It was dripped at the same time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., and then cooled to room temperature. After filtration through a 100 mesh wire mesh, the solid content is adjusted to 10% by mass with ion-exchanged water to obtain a 10% by mass aqueous dispersion (number average particle size 160 nm) of emulsion particles B-1 (component (B)). It was.

[Production Example 2]
[Emulsion particles B-2]
Into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 3 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR-1025” Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution with the temperature in the reaction vessel kept at 80 ° C. for about 2 hours It was dripped at the same time. Further, a mixed solution of 5 g of butyl acrylate, 5 g of phenyltrimethoxysilane, 0.1 g of 3-methacryloxypropyltrimethoxysilane, 30 g of diethylacrylamide, 0.1 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap SR- 1025 ", manufactured by Asahi Denka Co., Ltd., 25 g solid content aqueous solution) 0.1 g, ammonium persulfate 2 g% aqueous solution 4 g, ion-exchanged water 190 g mixed solution and about 2 at a temperature of 80 ° C in the reaction vessel Stirring was continued for an hour, and then cooled to room temperature. After filtration through a 100 mesh wire mesh, the solid content is adjusted to 10% by mass with ion-exchanged water to obtain a 10% by mass aqueous dispersion (number average particle size 180 nm) of emulsion particles B-2 (component (B)). It was.

[Production Example 3]
[Emulsion particles B-3]
Into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 3 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane and polyoxymethylene methacrylate (trade name “Blenmer PE-200”, manufactured by NOF Corporation) 137 g , 3 g of acrylic acid, 13 g of reactive emulsifier (trade name “Adekaria Soap SR-1025”, manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), 40 g of 2 mass% aqueous solution of ammonium persulfate, and 1900 g of ion-exchanged water The liquid was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., and then cooled to room temperature. After filtration through a 100 mesh wire mesh, the solid content is adjusted to 10% by mass with ion-exchanged water to obtain a 10% by mass aqueous dispersion (number average particle size 250 nm) of emulsion particles B-3 (component (B)). It was.

[Production Example 4]
[Emulsion particles B-4]
Into a reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 3 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring. To this, a mixture of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while maintaining the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. And stirring was continued for about 1 hour. Next, a mixed solution of 86 g of butyl acrylate, 133 g of phenyltrimethoxysilane, 1.3 g of 3-methacryloxypropyltrimethoxysilane, 137 g of dimethyldimethoxysilane and 3 g of acrylic acid and a reactive emulsifier (trade name “ADEKA rear soap SR-1025” "Asahi Denka Co., Ltd., 25% solid content aqueous solution) 13 g, ammonium persulfate 2 mass% aqueous solution 40 g, and ion-exchanged water 1900 g mixed solution of about 4 with the temperature in the reaction vessel maintained at 80 ℃. It was dripped simultaneously over time. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., and then cooled to room temperature. After filtration through a 100 mesh wire mesh, the solid content is adjusted to 10% by mass with ion-exchanged water to obtain a 10% by mass aqueous dispersion (number average particle size 160 nm) of emulsion particles B-4 (component (B)). It was.

[Examples 1 to 3, Comparative Example 1]
The coating composition for solar cells was obtained with the formulation shown in Table 1.

  The obtained solar cell coating composition is bar-coated on a 10 cm × 10 cm PET film so that the film thickness becomes 0.5 μm, and then dried at 70 ° C. for 10 minutes to obtain a solar cell cover material. It was. These evaluation results are shown in Table 1.

［コロイダルシリカの１０質量％水分散体］
日産化学工業（株）製商品名「スノーテックスＯ」（（Ａ）成分）を水中に分散させたもの（固形分１０質量％、数平均粒子径１０ｎｍ）。

[10 mass% aqueous dispersion of colloidal silica]
A product name “Snowtex O” (component (A)) manufactured by Nissan Chemical Industries, Ltd. dispersed in water (solid content 10% by mass, number average particle size 10 nm).

[10 mass% aqueous dispersion of silica-coated titanium oxide]
A product name “TSK-5” (component (A)) manufactured by Ishihara Sangyo Co., Ltd. dispersed in water (solid content 10 mass%, number average particle size 73 nm).

（式中、Ｒは式（１）で定義した通りである。）

［１４] （Ａ’）成分が、光触媒活性を有する上記［１３］に記載の太陽電池用コーティング組成物。
［１５] （Ａ’）成分の粒子長（ｌ）と粒子直径（ｄ）の比（ｌ／ｄ）が、１／１から２０／１である上記［１３］又は［１４］に記載の太陽電池用コーティング組成物。
［１６] 上記［１］〜［１５］のいずれかに記載の太陽電池用コーティング組成物を用いて形成される塗膜と、樹脂基材とを含む積層体。
［１７] 塗膜のヘイズが２０以下である上記［１６］に記載の積層体。
［１８] 上記［１６］〜［１７］のいずれかに記載の積層体を用いてなる太陽電池用カバー材。
［１９] 上記［１］〜［１５］のいずれかに記載の太陽電池用コーティング組成物を含んでなる太陽電池。 As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention is as follows.
[1] Each component of the following (A) and (B),
(A) component: metal compound particles having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle size of 10 nm to 800 nm,
Including
The component (B) is the following components (b1) to (b4):
(B1) component: hydrolyzable silicon compound,
(B2) component: polyoxymethylene methacrylate ,
(B3) component: emulsifier,
(B4) component: water,
A coating composition for solar cells, which is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing
[ 2 ] The sun according to [ 1 ] above, wherein the ratio (b2) / (B) (mass ratio) of the component (b2) to the component (B) is 0.1 / 1 to 0.8 / 1. Battery coating composition.
[ 3 ] The sun according to [1] or [ 2 ], wherein the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer. Battery coating composition.
[ 4 ] In the outermost layer of the shell layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.1 / 1 to 5/1. 3] The coating composition for solar cells according to [3].
[ 5 ] In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer The coating composition for solar cells according to [ 3 ] above, wherein the ratio (b2) / (b1) (mass ratio) between the component (b2) and the component (b1) is 0.1 / 1 to 5/1. object.
[6] The above [1] or [2] , wherein the component (B) has a three-layer structure including a core layer, a shell first layer that covers the core layer, and a shell second layer that covers the outer side of the core layer. ] The coating composition for solar cells as described in above.
[7] In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and in the shell first layer (b2 ) / (B1) (mass ratio) is 0.1 / 1 to 1/1, and (b2) / (b1) (mass ratio) is 1/1 to 9/1 in the shell second layer [6] The coating composition for solar cells described in 1.
[8] The component (B) is obtained by polymerizing a polymerization stock solution in the presence of seed particles forming the core layer, and the seed particles are the component (b1), the component (b2), and the following (b5) component,
Component (b5): other vinyl monomer copolymerizable with component (b2),
The coating composition for solar cells according to any one of the above [ 3 ] to [7], which is obtained by polymerizing at least one selected from the group consisting of:
[9] The component (b1) is the following component (b1-1):
(B1-1) component: a hydrolyzable silicon compound having a vinyl polymerizable group,
Including
Of the above [1] to [8], the ratio (b1-1) / (B) (mass ratio) of the component (b1-1) to the component (B) is 0.01 / 100 to 20/100. The coating composition for solar cells in any one.
[10] The above [9], wherein the ratio (b1-1) / (b2) (mass ratio) of the component (b1-1) to the component (b2) is 0.1 / 100 to 100/100. The coating composition for solar cells.
[11] The component according to any one of [1] to [10], wherein the component (A) is formed using any one of silicon dioxide, a metal oxide having photocatalytic activity, or a metal oxide having conductivity. The coating composition for solar cells.
[12] The ratio (l / d) of the particle length (l) and the particle diameter (d) of the component (A) is any one of the above [1] to [11], which is 1/1 to 20/1. The coating composition for solar cells described.
[13] The component (A) is the following component (A ′):
(A ′) component: triorganosilane unit represented by formula (1), monooxydiorganosilane unit represented by formula (2), dioxyorganosilane unit represented by formula (3), formula ( 4) Using a modifier compound having at least one structural unit selected from the group consisting of a trioxysilane unit represented by 4) and a difluoromethylene unit, the metal compound particles of component (A) are modified. Modified metal compound particles formed,
The solar cell coating composition according to any one of the above [1] to [12].
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)

[14] The solar cell coating composition according to [13], wherein the component (A ′) has photocatalytic activity.
[15] The sun according to [13] or [14], wherein the ratio (l / d) of the particle length (l) to the particle diameter (d) of the component (A ′) is from 1/1 to 20/1. Battery coating composition.
[16] A laminate comprising a coating film formed using the coating composition for solar cells according to any one of [1] to [15], and a resin base material.
[17] The laminate according to [16], wherein the coating film has a haze of 20 or less.
[18] A solar cell cover material using the laminate according to any one of [16] to [17].
[19] A solar cell comprising the solar cell coating composition according to any one of [1] to [15].

Claims (19)

The following components (A) and (B)
(A) component: metal compound particles having a particle diameter of 1 nm to 400 nm,
(B) component: polymer emulsion particles having a particle size of 10 nm to 800 nm,
Including
The component (B) is the following components (b1) to (b4):
(B1) component: hydrolyzable silicon compound,
(B2) component: a vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group;
(B3) component: emulsifier,
(B4) component: water,
A coating composition for solar cells, which is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing   The solar cell coating composition according to claim 1, wherein the component (b2) is a vinyl monomer having a secondary and / or tertiary amide group.   The ratio (b2) / (B) (mass ratio) between the component (b2) and the component (B) is 0.1 / 1 to 0.8 / 1, for a solar cell according to claim 1 or 2. Coating composition.   The solar cell according to any one of claims 1 to 3, wherein the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer. Coating composition.   In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer, The coating composition for solar cells according to claim 4, wherein the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.1 / 1 to 5/1.   The component (B) has a three-layer structure including a core layer, a shell first layer that covers the core layer, and a shell second layer that covers the outer side thereof. The coating composition for solar cells described in 1.   In the core layer, the ratio (b2) / (b1) (mass ratio) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1, and (b2) / ( The sun according to claim 6, wherein (b1) (mass ratio) is 0.1 / 1 to 1/1 and (b2) / (b1) (mass ratio) is 1/1 to 9/1 in the second shell layer. Battery coating composition. Component (B) is obtained by polymerizing a polymerization stock solution in the presence of seed particles forming a core layer, and the seed particles are (b1) component, (b2) component, and the following (b5) component:
Component (b5): other vinyl monomer copolymerizable with component (b2),
The coating composition for solar cells according to claim 4, obtained by polymerizing at least one selected from the group consisting of: (B1) component is the following (b1-1) component,
(B1-1) component: a hydrolyzable silicon compound having a vinyl polymerizable group,
Including
The ratio (b1-1) / (B) (mass ratio) between the component (b1-1) and the component (B) is 0.01 / 100 to 20/100. The coating composition for solar cells according to item.   The ratio (b1-1) / (b2) (mass ratio) between the (b1-1) component and the (b2) component is 0.1 / 100 to 100/100. Coating composition.   The component (A) is formed using any one of silicon dioxide, a metal oxide having a photocatalytic activity, or a metal oxide having conductivity, for the solar cell according to any one of claims 1 to 10. Coating composition.   The solar cell according to any one of claims 1 to 11, wherein the ratio (l / d) of the particle length (l) of the component (A) to the particle diameter (d) is 1/1 to 20/1. Coating composition. (A) component is the following (A ') component,
(A ′) component: triorganosilane unit represented by formula (1), monooxydiorganosilane unit represented by formula (2), dioxyorganosilane unit represented by formula (3), formula ( 4) Using a modifier compound having at least one structural unit selected from the group consisting of a trioxysilane unit represented by 4) and a difluoromethylene unit, the metal compound particles of component (A) are modified. Modified metal compound particles formed,
The coating composition for solar cells as described in any one of Claims 1-12 containing these.
R ₃ Si- (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon group having 1 to 30 carbon atoms. (A fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group.)
_{- (R 2 SiO) - (} 2)
(In the formula, R is as defined in formula (1).)

(In the formula, R is as defined in formula (1).)

  The coating composition for solar cells according to claim 13, wherein the component (A ') has photocatalytic activity.   The coating composition for solar cells according to claim 13 or 14, wherein the ratio (l / d) of the particle length (l) and particle diameter (d) of the component (A ') is from 1/1 to 20/1.   The laminated body containing the coating film formed using the coating composition for solar cells as described in any one of Claims 1-15, and a resin base material.   The laminate according to claim 16, wherein the coating film has a haze of 20 or less.   The solar cell cover material which uses the laminated body as described in any one of Claims 16-17.   The solar cell which comprises the coating composition for solar cells of Claims 1-15.