JP2011207170A - Functional laminate, and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional laminate excelling in antifouling property and having high light transmittance.SOLUTION: The functional laminate includes an organic-inorganic composite coating film containing components in the following (A)-(C) in at least one principal plane of a base material. The organic-inorganic composite coating film is formed by applying, to the base material, a coating composition containing each of (A) component: a metal oxide whose particle size is 1-400 nm, (B) component: polymer emulsion particles whose particle size is 10-800 nm, and (C) component: a light-sensitive acid generator, and carrying out drying processing and ultraviolet irradiation.

Description

  The present invention relates to a functional laminate and a method for producing the functional laminate.

In recent years, the global warming phenomenon has heightened awareness of the environment, and a new energy system that does not generate greenhouse gases such as carbon dioxide is attracting attention.
So-called environmentally friendly renewable energy, such as solar power generation and wind power generation, does not emit carbon dioxide and other gases that are said to induce global warming, so research and development are actively conducted as clean energy. Because of its excellent safety and ease of handling, solar cell power generation technology is rapidly spreading.
Protective covers such as glass used on the surface of the solar cell are contaminated with dust or sand accumulation, so that the light transmittance of sunlight is reduced and the energy output of the solar cell is reduced. It has become. Therefore, there is a demand for a practical antifouling technique that can suppress a decrease in energy output of the solar cell for a long period of time.

In Patent Document 1 below, a coating solution in which tungstic acid dissolved in ammonia water and distilled water are added is applied onto an anatase-type titanium oxide-containing layer, and a layer made of tungsten oxide is applied by baking at 700 ° C. A technique for forming and forming a surface layer is disclosed.
In the laminate of the anatase-type titanium oxide-containing layer and the surface layer disclosed in Patent Document 1, organic substances attached to the surface layer are decomposed by the anatase-type titanium oxide-containing layer having a photocatalytic function, so that the surface is hydrophilic. And the hydrophilicity of the surface is maintained by the layer made of tungsten oxide.
Thereby, the condensed water and water droplets adhering to the surface can easily spread over the entire surface, and the dirt adhering to the surface can be washed away with rainwater or the like.

  However, in recent years, high energy efficiency is required even in a few percent in large-scale power generation plants. Under such circumstances, not only the antifouling technology described above, but also a technology that can efficiently use sunlight. In view of such requirements, Patent Document 2 below discloses an active energy ray-curable composition using an alkyl silicate, and Patent Document 3 discloses an organic-inorganic composite composition.

JP-A-10-114545 JP 2007-16191 A International Publication No. 2007/069596

However, the active energy ray-curing composition using the alkyl silicate disclosed in Patent Document 2 cannot exhibit sufficient antifouling properties, and the organic-inorganic composite composition disclosed in Patent Document 3 above. Even with things, it cannot be said that sufficient solar light utilization efficiency has been improved, and there is still room for improvement.
Then, in this invention, it aims at providing the functional laminated body excellent in antifouling property and light transmittance.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that at least one main surface of the base material has a metal oxide having a predetermined particle diameter, polymer emulsion particles, and a photosensitive acid generator. It has been found that a functional laminate having an organic-inorganic composite film formed by applying a coating composition containing, applying a drying treatment and irradiating with ultraviolet rays can solve the above problems.
That is, the present invention is as follows.

[1]
It is a functional laminate having an organic-inorganic composite coating film containing each of the following components (A) to (C) on at least one main surface of the substrate,
The organic-inorganic composite coating film is formed by applying a coating composition containing the following components (A) to (C) to the substrate, performing a drying treatment, and irradiating with ultraviolet rays. Laminate.
Component (A): Metal oxide having a particle size of 1 nm to 400 nm (B) Component: Polymer emulsion particle having a particle size of 10 nm to 800 nm (C) Component: Photosensitive acid generator

[2]
The functional laminate according to [1] above, wherein the refractive index of the organic-inorganic composite coating film after the ultraviolet irradiation is 1.10 to 1.45.

[3]
The component (B) is
(B1) component: a 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;
The functional laminate according to [1] or [2], wherein the functional emulsion is a polymer emulsion particle obtained by polymerizing a polymerization stock solution.

[4]
The functional laminate according to any one of [1] to [3], wherein the refractive index of the component (A) is 1.40 to 3.00.

[5]
The functional laminate according to any one of [1] to [4], which is used as a protective cover for a solar cell.

[6]
Applying a coating composition containing the following components (A) to (C) to at least one principal surface of the substrate;
Applying a drying process;
Ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, a step of irradiating with ultraviolet rays using at least one selected from the group consisting of a carbon arc lamp,
A method for producing a functional laminate having:
Component (A): Metal oxide having a particle size of 1 nm to 400 nm (B) Component: Polymer emulsion particle having a particle size of 10 nm to 800 nm (C) Component: Photosensitive acid generator

  According to the present invention, a functional laminate having excellent antifouling properties and high light transmittance can be obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

[Functional laminate]
The functional laminate of this embodiment has an organic-inorganic composite coating film obtained by applying a coating composition to at least one principal surface of a substrate and then irradiating with ultraviolet rays.

Hereinafter, the coating composition and the substrate will be described in order.
(Coating composition)
The coating composition contains the following components (A) to (C).
(A) Component: Metal oxide having a number average particle diameter of 1 nm to 400 nm (B) Component: Polymer emulsion particle having a number average particle diameter of 10 nm to 800 nm (C) Component: Photosensitive acid generator

By irradiating the coating composition containing the components (A) to (C) with ultraviolet rays, a coating film having excellent antifouling property and high light transmittance can be obtained.
In the coating composition, the component (A) acts as a curing agent for the component (B) by interacting with the component (B) (however, the function of this embodiment is not limited to this function). .)
Examples of the interaction include, for example, a hydrogen bond between a hydroxyl group that the component (A) generally has and a functional group that the component (B) has, such as a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group, Examples thereof include condensation (chemical bond) between a hydroxyl group generally contained in the component (A) and a polymerization product of the component (b1) constituting the component (B).
From the above viewpoint, in the coating film, the component (A) is preferably a continuous phase, and the component (A) forms a continuous layer between the particles of the component (B) while interacting with the component (B). More preferably it exists. In the present embodiment, the dispersion form in the coating film is not limited, but by taking such a dispersion form, the resulting coating film and laminate are more resistant to contamination, light transmittance, and weather resistance. Further improvement.

((A) component: metal oxide)
As the metal oxide used in the component (A), from the viewpoint of interaction with the component (B), for example, silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, indium oxide, tin oxide, zirconium oxide, Examples thereof include lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, and cerium oxide.
Of these, silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, and complex oxides thereof having a large number of surface hydroxyl groups are preferred because of their strong interaction with the component (B).
Further, the component (A) having a large number of surface hydroxyl groups is preferable because it forms a continuous layer between the particles of the component (B), thereby increasing the hydroxyl group density on the coating film surface and increasing its own hydrophilicity. .
Here, the component (A) may be used alone or in combination of two or more.

As the metal oxide used for the component (A), from the viewpoint of imparting organic matter decomposability to the functional laminate of the present embodiment, a compound that expresses photocatalytic activity and / or hydrophilicity by light irradiation (hereinafter, referred to as “a”). It is preferable to use a simple abbreviated “photocatalyst”.
When a compound that exhibits photocatalytic activity when irradiated with light is used as the component (A), the surface of the coating film made of the resulting coating composition can exhibit excellent decomposition activity and contamination resistance of contaminating organic substances. .
The “hydrophilicity” expressed in the functional laminate of the present embodiment is preferably 50 ° or less, more preferably 30 ° or less, as a contact angle of water (23 ° C.) with respect to the surface of the measurement object. Preferably, it means 20 ° or less.

Examples of the photocatalyst as the component (A) 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 further selected from Ti, Nb, Ta, V Layered oxides having at least 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-10-244165, etc.) It is.
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.

Moreover, as a metal oxide used for the said (A) component, it is preferable to use the metal oxide which has electroconductivity from a viewpoint which expresses antistatic performance etc. in the said coating composition.
Examples of such conductive metal oxides include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, and zinc oxide.

Examples of the form when the metal oxide of the component (A) is used for the coating composition include powders, dispersions, and sols.
The dispersion or sol as used herein means that the component (A) is a primary particle having 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, dioxane and the like. Examples include ethers, amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide, and nitrobenzene. These may be used alone or in a mixture of two or more.

The number average particle diameter of the component (A) (hereinafter sometimes simply referred to as “particle diameter”) is 1 nm to 400 nm, preferably 1 nm to 100 nm, more preferably 3 nm to 80 nm, and still more preferably. 5 nm to 50 nm.
The number average particle diameter of the component (A) can contribute to the optical properties and the like of the functional laminate formed using the resulting coating composition.
Particularly, when the thickness is 100 nm or less, the light transmittance of the obtained functional laminate can be greatly improved.
The number average particle diameter (simply abbreviated as “particle diameter”) can be measured according to the method of Examples described later.
The measurement target of the number average particle diameter of the metal oxide of the component (A) may be a mixture of primary particles and secondary particles, or only primary particles or secondary particles.
When the number average particle diameter of the component (A) exceeds 400 nm, the optical properties such as transparency of the obtained coating film and laminate are not sufficient. When the number average particle diameter of the component (A) is less than 1 nm, the storage stability of the coating composition is deteriorated and handling properties are deteriorated.

The metal oxide (A) is preferably colloidal silica from the viewpoint of handleability.
Colloidal silica can be prepared and used by a sol-gel method, and a commercially available product can also be used.
For preparation by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D .; Badley et al; Lang muir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like.

Colloidal silica is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit, and the particle diameter thereof is 1 to 400 nm, preferably 1 to 100 nm, more preferably 5 to 50 nm.
If the particle diameter of colloidal silica is 1 nm or more, the storage stability of the coating composition is good, and by setting it to 400 nm or less, the transparency of the coating film is good.
Colloidal silica having a number average particle size in the above range can be used in the state of an aqueous dispersion, whether acidic or basic, and is appropriately selected according to the stable region of the component (B) to be mixed. be able to. Examples of acidic colloidal silica using water as a dispersion medium include, for example, commercially available products from Nissan Chemical Industries, Snowtex (trademark) -O, Snowtex-OS, Snowtex-OL, Asahi Denka Kogyo Co., Ltd., and Adelite (trademark). ) AT-20Q, Clariant Japan, Clevozole (trademark) 20H12, Clevozole 30CAL25, etc. can be used.
The stable region basically means the stability of latex, that is, a region where particles are not aggregated and the particle diameter becomes extremely large or does not settle.

  Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, and amines. For example, SNOWTEX-20, SNOWTEX-30, SNOWTEX-C, and SNOWTEX-C manufactured by Nissan Chemical Industries, Ltd. Tex-C30, Snotex-CM40, Snotex-N, Snotex-N30, Snotex-K, Snotex-XL, Snotex-YL, Snotex-ZL, Snotex PS-M, Snotex PS-L Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50, etc. manufactured by Asahi Denka Kogyo Co., Ltd. Clariant Japan Co., Ltd. Kurebozoru 30R9, Kurebozoru 30R50, such Kurebozoru 50R50, DuPont Ludox (TM) HS-40, Ludox HS-30, Ludox LS, include Ludox SM-30 and the like.

  Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm), IPA-ST (particle size of 10) manufactured by Nissan Chemical Industries, Ltd. ˜15 nm isopropyl alcohol dispersion type), EG-ST (ethylene glycol dispersion type with particle diameter of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70 to 100 nm), NPC-ST (particles) And ethylene glycol monopropyl ether dispersion type) having a diameter of 10 to 15 nm.

The colloidal silica mentioned above may be used alone or in combination of two or more.
Moreover, alumina, sodium aluminate, etc. may be included as a minor component.
Furthermore, colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

((B) component: polymer emulsion particles)
The component (B) is a polymer emulsion particle having a number average particle size of 10 nm to 800 nm. By using such emulsion particles, interaction with the above-mentioned component (A) can be expressed.
By being polymer emulsion particles, it becomes possible to easily form a sea-island structure with the component (A) and the component (B) when a coating film described later is formed, and a metal oxide is formed on the outermost surface of the coating film. Localization and good hydrophilicity can be expressed by a hydrophilic group such as a hydroxyl group of the metal oxide (however, the operation of the present embodiment is not limited to this).
The polymer emulsion particles are not particularly limited as long as the monomer component having an unsaturated bond is polymerized by the intervention of radicals, cations, anions, etc. The type of emulsion particles is not particularly limited. An emulsion, a styrene emulsion, an acrylic styrene emulsion, an acrylic silicon emulsion, a silicon emulsion, a fluororesin emulsion, etc. are mentioned.
(B) The number average particle diameter of a component is 10 nm-800 nm. By adjusting to such a particle diameter range and combining with the component (A), it is possible to obtain a functional laminate having excellent antifouling property and high light transmittance. The number average particle diameter of the component (B) is preferably 10 nm to 100 nm from the viewpoint of improving light transmittance.

The component (B) is preferably polymer emulsion particles obtained by polymerizing a polymerization stock solution containing the following components (b1) and (b2), and a polymerization stock solution containing the following components (b1) to (b4): More preferred are polymer emulsion particles obtained by polymerization.
(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,
In the polymer emulsion particles (B) obtained from the polymerization stock solution containing at least the component (b1) and the component (b2), the hydroxyl group derived from the component (b1) and the polymerization product of the component (b2) are bonded by hydrogen bonding or the like. Can be combined. By using such a component (B), the interaction with the component (A) described above can be further enhanced.

<(B1) component: hydrolyzable silicon compound>
Examples of the component (b1) include compounds represented by the following formula (1), condensation products thereof, and silane coupling agents.
SiWxRy (1)

In formula (1), 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, an amide. Represents at least one group selected from the group;
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 alkyl group having 1 to 20 carbon atoms or 1 carbon atom. Represents at least one hydrocarbon group selected from an alkoxy group having 20 carbon atoms or an aryl group having 6-20 carbon atoms substituted with a halogen atom.
x is an integer from 1 to 4, and y is an integer from 0 to 3. Also, x + y = 4.

  In addition, the said 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, and an isocyanate group exists in a molecule | numerator.

Examples of the compound represented by the formula (1) 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, vinyltriethoxysilane, allyltrimethoxysilane Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-c Ropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyl Trimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltri Trialkoxysilanes such as methoxysilane and 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxy Silane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethyl Kishishiran, diphenyldiethoxysilane, 3- (meth) acryloyl dialkoxysilane such as propyl methyl dimethoxy silane;
Monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane;
Etc.
These may be used alone or in combination of two or more.

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, the (b1) component may contain a silane coupling agent having a thiol group and the following (b1-1) component.
(B1-1) Component: A hydrolyzable silicon compound having a vinyl polymerizable group.
When these are used, the long-term antifouling property of the obtained functional laminate is good, 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.
In addition, 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.

The component (b1) may include the following component (b1-2).
(B1-2) component: Cyclic siloxane oligomer When the said (b1-2) component is used, the softness | flexibility of the functional laminated body obtained becomes more favorable, and is suitable.

As said cyclic siloxane oligomer, the compound represented by following formula (2) can be illustrated.
(R ′ ₂ SiO) m (2)

In the formula (2), 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 group. It represents at least one 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.
m is an integer, and 2 ≦ m ≦ 20.

  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 the gel permeation chromatography (GPC) method) of the said condensation product becomes like this. Preferably it is 200-5000, More preferably 300-1000.

  The ratio (b1) / (B) (mass ratio) between the component (b1) and the component (B) is preferably 0.01 / 100 to 80/100, more preferably 0, from the viewpoint of polymerization stability. 1/100 to 70/100, and further 0.2 / 100 to 40/100.

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 20 from the viewpoint of polymerization stability. / 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 100 from the viewpoint of polymerization stability. / 100, more preferably 0.5 / 100 to 50/100.

The ratio (b1-2) / (B) (mass ratio) between the component (b1-2) and the component (B) is preferably 0.01 / 100 to 20/100, from the viewpoint of hydrophilicity. More preferably, it is 0.5 / 100-5 / 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.

<(B2) component: vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amide group, amino group, and ether group>
Of the component (b2), examples of the hydroxyl group-containing vinyl monomer include various types 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 Monoesters of polyoxyalkylene glycols obtained from various polyether polyols such as glycol and the like and various unsaturated carboxylic acids such as (meth) acrylic acid; Each like Adducts of various hydroxyl group-containing monomers and various lactones such as ε-caprolactone; various epoxy group-containing unsaturations such as glycidyl (meth) acrylate Adducts of monomers and various acids as represented by acetic acid and the like; Furthermore, various unsaturated carboxylic acids as represented by (meth) acrylic acid and the like, and “Cardura E” There are various hydroxyl group-containing vinyl monomers such as adducts with various monoepoxy compounds other than the α-olefin epoxide as represented by Can be mentioned.

Among the components (b2), as the carboxyl group-containing vinyl monomer, there are various types such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid. Unsaturated carboxylic acids;
Unsaturated dicarboxylic acids and saturated monohydric alcohols such as monomethyl itaconate, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate, mono-n-butyl fumarate Monoesters (half-esters); monovinyl esters of various saturated dicarboxylic acids, such as monovinyl adipate or monovinyl succinate; such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride Addition reaction products of various saturated polycarboxylic acid anhydrides with the above-mentioned various hydroxyl group-containing vinyl monomers; and further, various carboxyl group-containing monomers and lactones as described above. And the like that can be obtained by addition reaction.

  Among the components (b2), examples of the amino group-containing vinyl monomer include 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meta). ) Various tertiary amino group-containing (meth) such as acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, or N- [2- (meth) acryloyloxy] ethylmorpholine Acrylic esters; various tertiary amino group-containing aromatic vinyl monomers such as vinyl pyridine and N-vinyl carbazole N-vinyl quinoline; N- (2-dimethylamino) ethyl (meth) acrylamide; N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n Of propylamino) ethyl (meth) acrylamide, N- (3-dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide] ethylmorpholine Various tertiary amino group-containing (meth) acrylamides such as N- (2-dimethylamino) ethylcrotonamide, N- (2-diethylamino) ethylcrotonamide, N- (2-di-n-propyl) Various tertiary amino group-containing crotonic acid amides such as amino) ethyl crotonic acid amide, N- (3-dimethylamino) propyl crotonic acid amide or N- (4-dimethylamino) butyl crotonic acid amide; 2-dimethyl Aminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3 Such as dimethyl amino propyl vinyl ether or 4-dimethylamino-butyl vinyl ether, tertiary amino group-containing vinyl ethers of various like.

Among the components (b2), ether group-containing vinyl monomers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer. Examples include vinyl ethers having such various polyether chains in the side chain, allyl ethers, or vinyl monomers such as (meth) acrylic acid esters.
Commercially available products can also be used. Specific examples include Bremer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 [above, Nippon Oil & Fat Co., Ltd. )], MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA [above, Nippon Emulsifier Co., Ltd. ) Made].
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.

Among the components (b2), examples of the amide group-containing vinyl monomer include N-alkyl or N-alkylene-substituted (meth) acrylamide.
More specifically, 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-N -N-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloyl Sahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N-vinylacetamide, diacetone Examples include acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.

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 hydrogen bonding property with another component more.
In particular, a vinyl monomer having a tertiary amide group is preferable from the viewpoint of hydrogen bonding strength.

The ratio (b2) / (B) (mass ratio) of component (b2) to component (B) is preferably 0.05 / 1 to 1/1, more preferably 0.1 /, from the viewpoint of polymerization stability. It is 1-0.8 / 1, Furthermore, it is 0.2 / 1-0.5 / 1.
In addition, the ratio (b2) / (A) (mass ratio) of the component (b2) to the component (A) is preferably 0.05 / from the viewpoint of hydrogen bonding with the component (A) and blending stability. It is 1-1 / 1, More preferably, it is 0.1 / 1-0.8 / 1, More preferably, it is 0.2 / 1-0.5 / 1.
It is.

<(B3) component: emulsifier>
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 salts, imidazolinium salt type cationic surfactants;
Nonionic surfactants such as polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene block copolymer, polyoxyethylene distyryl phenyl ether;
Etc.
These may 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 obtained component (B) and improving the long-term antifouling property of the resulting functional laminate, a radical polymerizable double It is preferable to use a reactive emulsifier having a bond.
Examples of the reactive emulsifier include a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, and a nonionic group such as an alkali metal salt, ammonium salt or polyoxyethylene thereof. Examples include vinyl monomers and vinyl monomers having a quaternary ammonium salt.

  As the reactive emulsifier, the vinyl monomer having a sulfonic acid group or a sulfonate group has, for example, a radical polymerizable double bond, and an ammonium salt, a sodium salt, or a potassium salt of a sulfonic acid group. Alkyl group having 1 to 20 carbon atoms, alkyl ether group having 2 to 4 carbon atoms, polyalkyl ether group having 2 to 4 carbon atoms, phenyl group, naphthyl group, and succinic acid partially substituted by various substituents A compound having a substituent selected from the group consisting of a group; a vinyl sulfonate compound having a vinyl group to which a substituent is bonded, such as an ammonium salt, sodium salt or potassium salt of a sulfonic acid group;

  Examples of the vinyl monomer having a sulfate group that is the reactive emulsifier include a radical polymerizable double bond and a substituent such as an ammonium salt, a sodium salt, or a potassium salt of the sulfate 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, and a naphthyl group. The compound which has a substituent is mentioned.

Examples of the reactive emulsifier include compounds having a succinic acid group partially substituted with a substituent such as an ammonium salt, sodium salt or potassium salt of the sulfonic acid group, for example, allylsulfosuccinate. It is done.
Commercially available products can also be used. For example, Eleminol JS-2 (trade name) (manufactured by Sanyo Chemical Co., Ltd.), Latemuru S-120, S-180A or S-180 (trade name) (Kao Corporation) Manufactured) and the like.

  Moreover, the C2-C4 alkyl ether group or C2-C4 partly substituted by the group which is the ammonium salt of the said sulfonic acid group which is an example of the said reactive emulsifier, a sodium salt, or potassium salt Examples of the compound having a polyalkyl ether group include 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.).

  Examples of the vinyl monomer having a nonionic group as an example of the reactive emulsifier include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxy. Ethylene (trade names: Adeka 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, etc., 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. .
When the component (B) includes the component (b4) (that is, “water”), the amount of the component (b4) used is preferably 30 to 99 as the content in the polymerization stock solution from the viewpoint of polymerization stability. .9% by mass.

<(B5) component>
In addition to the components (b1) to (b4), various components can be further mixed into the polymerization stock solution for polymerizing the component (B).
The following component (b5) may be mixed in the polymerization stock solution.
Component (b5): Other vinyl monomer copolymerizable with component (b2) Using such a component (b5) means that the properties of the resulting polymerization product (glass transition temperature, molecular weight, hydrogen bond strength, From the viewpoint of controlling polarity, dispersion stability, weather resistance, compatibility with the polymerization product of the hydrolyzable silicon compound (b1), and the like.
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 monomers containing a functional group such as a monomer.

The proportion of the component (b5) in the total vinyl monomer, that is, (b2) + (b5) is preferably 0.001 to 30% by mass, more preferably 0.05 to 10% by mass. Range.
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.

<Chain transfer agent>
A chain transfer agent can be mixed in the polymerization stock solution for polymerizing the component (B) described above.
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. It is done.

  The amount of the chain transfer agent 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.

<Dispersion stabilizer>
A dispersion stabilizer can be mixed in the polymerization stock solution for polymerizing the component (B).
Examples of the 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 resin, polyacrylic acid ( Salt), polyacrylamide, water-soluble or water-dispersible acrylic resins, and other synthetic or natural water-soluble or water-dispersible water-soluble polymer substances.
These may be used alone or in combination of two or more.

  The amount of these dispersion stabilizers to be 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).

<Polymerization catalyst>
The polymerization of the polymerization stock solution for polymerizing the component (B) 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). More 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. In particular, water-soluble or oil-soluble persulfates, peroxides, azobis compounds and the like are preferably used. For example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2- Diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.

In addition, as the usage-amount of the polymerization catalyst of (b2) component, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of all vinyl monomers ((b2) + (b5)).
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.
The polymerization of the component (b1) and the polymerization of the component (b2) can be performed separately. However, it is preferable to perform the polymerization at the same time because a micro organic / inorganic composite by hydrogen bonding or the like can be achieved. .

(Production method of component (B))
The polymerization method for obtaining the component (B) is not particularly limited, and the component (b1) and the component (b2) are polymerized in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization is preferred.
As a method of emulsion polymerization, for example, the (b1) component and the (b2) component, and further, if necessary, the (b3) component and the (b4) component as they are or in an emulsified state, A method of polymerizing at a reaction temperature of about 30 to 150 ° C. by dropping dropwise into a predetermined reaction vessel in a divided manner or continuously and in the presence of the above-described polymerization catalyst, preferably from atmospheric pressure to a pressure of 10 MPa as necessary. Is mentioned. In some cases, the polymerization may be carried out at a higher pressure or lower temperature.

  In addition, as a mixing | blending of the polymerization undiluted solution for obtaining (B) component, from a viewpoint of superposition | polymerization stability, final solid content will be 0.1-70 mass%, Preferably it will be the range of 1-55 mass%, It is preferable to blend the components (b1) to (b4).

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 for obtaining the component (B), for example, when the component (b3) or the component (b4) is used, the component (b1) and the component (b2) are changed in the presence of the component (b3) and the component (b4). If necessary, after polymerization in the presence of a solvent, a method of further adding water as component (b4) until the polymerization product becomes an emulsion can also be applied.

The component (B) (polymer emulsion particles) includes a core layer and the core from the viewpoint of improving the substrate adhesion of the coating film formed using the coating composition obtained and the adhesion between the coating films. It is preferable to have a core / shell structure including one layer or two or more shell layers covering the layer.
By having such a core / shell structure, it is possible to improve the substrate adhesion of the obtained coating film, the adhesion between the coating films, and the like. The method for forming the core / shell structure is not particularly limited, but multistage emulsion polymerization in which emulsion polymerization is performed in multiple stages is very useful.

For example, as a specific example of multistage emulsion polymerization in the case of using the components (b1) to (b5), as the first step, in the presence of the component (b3) and the component (b4), (b1), (b2 ) And (b5) at least one selected from the group consisting of components is polymerized to form seed particles, and in the second stage, in the presence of the seed particles, the components (b1) and (b2) A polymerization method (two-stage polymerization method) can be applied by adding a polymerization stock solution containing the component and, if necessary, the component (b5).
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, the mass ratio between 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 is as follows. From the viewpoint of polymerization stability, (M1) / (M2) = 9/1 to 1/9, more preferably 8/2 to 2/8.

  In addition, the core / shell structure has a particle diameter obtained by the second-stage polymerization without significantly changing the particle size distribution (volume average particle diameter / number average particle diameter) of the seed particles from the viewpoint of polymerization stability. Those having an increased structure are preferred. 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 and confirmed by, for example, morphological observation with a transmission electron microscope or the like, or analysis by viscoelasticity measurement.
The glass transition temperature (Tg) of the core layer having the core / shell structure is preferably 0 ° C. or lower.
In this case, the functional laminate of the present embodiment is preferable because it has excellent flexibility at room temperature, and cracks and the like hardly occur when the film is thickened.
Tg 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 light transmittance and the antifouling property of the functional laminate of the present embodiment. Will be good.
Moreover, it is suitable from a viewpoint of the light transmittance improvement of the functional laminated body of this embodiment that the particle diameter of the said (B) component shall be 10 nm-100 nm.

(Ratio of (A) component and (B) component)
The ratio (A) / (B) (mass ratio) of the component (A) to the component (B) is preferably 10/100 to 500/100, more preferably 50/100 to 300/100, and further Preferably it is 100/100-250/100.
This is preferable because a functional laminate excellent in light transmittance and antifouling property can be realized. Moreover, since such antifouling property tends to last for a long time, it is preferable.

  The ratio (SA) / (SB) of the surface area (SA) of the component (A) to 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 number average particle diameter of each of the component (A) and the component (B) and the blending mass number.

(Additive)
In the coating composition for forming the functional laminate of the present embodiment, an additive component that is usually added and blended with a coating material or a molding resin, for example, a light stabilizer, depending on its use and usage method. , UV absorber, thickener, leveling agent, thixotropic agent, antifoaming agent, freezing stabilizer, matting agent, crosslinking reaction catalyst, pigment, curing catalyst, crosslinking agent, filler, anti-skinning agent, dispersant , Wetting agents, antioxidants, UV absorbers, rheology control agents, film forming aids, rust inhibitors, dyes, plasticizers, lubricants, reducing agents, preservatives, antifungal agents, deodorants, yellowing prevention An agent, an antistatic agent, a charge control agent, or the like can be selected and combined depending on the purpose.

As the light stabilizer, for example, a hindered amine light stabilizer is preferably used.
In particular, 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 in combination can contribute to improving the weather resistance of the resulting 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.

(Component (C): Photosensitive acid generator)
Component (C) contained in the organic-inorganic composite coating film constituting the functional laminate of the present embodiment: a photosensitive acid generator is an acid generated by visible light, ultraviolet rays, heat rays, electron beams, etc. This acid is a compound that can promote condensation of siloxane.
These can also be used in combination with a heat-sensitive acid generator that generates an acid by heat rays.
Examples of the photosensitive acid generator (C) include diphenyliodonium compounds, triphenylsulfonium compounds, diazodisulfone compounds, and the like.
For example, Irgacure 250 (manufactured by Ciba Specialty Chemicals), Adekaoptomer SP-150, SP-170 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990 Syracure UVI-6950 (manufactured by Union Carbide, USA), DAICAT II (manufactured by Daicel Chemical Industries, Ltd.), UVAC1591 (manufactured by Daicel UCB), CI-2734, CI-2855, CI-2823, CI Commercial products such as -2758 (manufactured by Nippon Soda Co., Ltd.) and Syracure UVI-6992 (manufactured by Dow Chemical Japan Co., Ltd.) can be used.
The content of the photosensitive acid generator (C) in the coating composition forming the organic-inorganic composite coating film is C / B = 0.000 / 100 with respect to the solid content of the polymer emulsion particles (B). The range of 10 to 100 parts by mass is preferable.
Furthermore, C / B = 0.01 / 100 to 5/100, more preferably C / B = 0.1 / 100 to 3/100.
When the blending amount of the photosensitive acid generator (C) is 0.001 part by mass or more, the condensation of silanol groups can be efficiently promoted by irradiation with ultraviolet light or the like. The stability of the particles may decrease, and the transparency of the coating film may decrease.

((D) component: hydrolyzable silicon-containing compound)
From the viewpoint of improving the strength and antifouling properties of the resulting coating film, the coating composition preferably further contains a hydrolyzable silicon compound as component (D).
As the hydrolyzable silicon-containing compound used for the component (D), a hydrolyzable silicon-containing compound (d1) represented by the following formula (3), a hydrolyzable silicon-containing compound represented by the following formula (4) ( d2) and a hydrolyzable silicon-containing compound (d3) represented by the following formula (5) can be used.

R ¹ _n SiX _4-n (3)

In the above formula (3), R ¹ represents any one selected from the group consisting of hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, and an aryl group.
Moreover, you may have functional groups, such as a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, an epoxy group, on these substituents.
X represents a hydrolyzable group, and n is an integer of 0 to 3.
The hydrolyzable group may be a group that generates a hydroxyl group by hydrolysis, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, and an oxime group.

X ₃ Si—R ² _n —SiX ₃ (4)

In said formula (4), X represents a hydrolyzable group and R < ² > represents a C1-C6 alkylene group or a phenylene group. n is 0 or 1.

R ³ — (O—Si (OR ³ ) ₂ ) _n —OR ³ (5)

In the above formula (5), R ³ represents an alkyl group having 1 to 6 carbon atoms. n is an integer of 2-8.

  Examples of the hydrolyzable silicon compounds (d1) and (d2) as the component (D) include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (n -Butoxy) silane, tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyl Dimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (triphenoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (Triethoxysilyl) ethane, bis (triphenoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,3-bis (triphenoxysilyl) propane 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3 -Hydroxypropyl Liethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -Acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, tetraacetoxysilane, tetrakis (trichloroacetoxy) silane, tetrakis (trifluoroacetoxy) silane, triacetoxysilane, tris (Trichloroacetoxy) silane, tris (trifluoroacetoxy) silane, methyltriacetoxysilane, methyltris (trichloroacetoxy) silane, tetrachlorosilane Lan, tetrabromosilane, tetrafluorosilane, trichlorosilane, tribromosilane, trifluorosilane, methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, tetrakis (methylethylketoxime) silane, tris (methylethylketoxime) silane, methyltris (Methylethylketoxime) silane, phenyltris (methylethylketoxime) silane, bis (methylethylketoxime) silane, methylbis (methylethylketoxime) silane, hexamethyldisilazane, hexamethylcyclotrisilazane, bis (dimethylamino) dimethylsilane, bis (diethylamino) ) Dimethylsilane, bis (dimethylamino) methylsilane, bis (diethylamino) methylsilane and the like.

Moreover, as a hydrolysable silicon containing compound (d3) represented by following formula (5), a commercial item can also be used.
Specific examples include a partial hydrolysis condensate of tetramethoxysilane (trade name “M silicate 51” manufactured by Tama Chemical Industry Co., Ltd., trade name “MSI51” manufactured by Colcoat Co., Ltd.), trade names “MS51”, “MS56”. “Mitsubishi Chemical Co., Ltd.”, partially hydrolyzed condensate of tetoethoxysilane (trade names “Silicate 35”, “Silicate 45”, manufactured by Tama Chemical Industry Co., Ltd., trade names “ESI 40”, “ESI 48” Colcoat Co., Ltd. )), And a co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name “FR-3” manufactured by Tama Chemical Industry Co., Ltd., product name “EMSi48” manufactured by Colcoat Co., Ltd.). .

The said hydrolysable silicon compound (D) can be used individually or in mixture of 2 or more types.
Further, the hydrolyzable silicon compound (D) can be blended after advance hydrolysis and condensation in advance, but may be blended with the metal oxide (A) and / or the emulsion particles (B). Good.

The mass ratio of the component (D) to the component (A) is preferably D / A = 0.01 / 100 to 300/100, preferably D / A = 1/100 to 200/100, Is D / A = 10/100 to 120/100.
When D / A is smaller than 0.01 / 100, it cannot be said that the coating film strength is sufficient, and when D / A exceeds 300/100, the coating film tends to be brittle.

(Base material)
As the base material constituting the functional laminate of the present embodiment, glass or resin is preferably used, but glass is preferable from the viewpoint of transparency and weather resistance.
The substrate preferably has a visible light transmittance of 30% to 99%, more preferably 80% to 99%, and still more preferably 92% to 99%.
A texture may be formed for the purpose of improving the light transmittance.
The texture here is glass having a regular concavo-convex structure on one side or both sides of the glass.
Further, tempered glass, laminated glass, multilayer glass, and the like can be used depending on the purpose.

  Examples of the resin constituting the base material include acrylic resin, polycarbonate resin, cyclic polyolefin resin, polyethylene terephthalate resin, ethylene-fluoroethylene copolymer, and the like. In addition, weathering agents such as ultraviolet absorbers may be further kneaded.

[Method for producing functional laminate]
The functional laminate of the present embodiment is a coating composition containing the components (A) to (C) described above, more preferably the component (D), on at least one main surface of the substrate described above. UV light using at least one selected from the group consisting of a step of applying an object, a step of applying a drying process, and a super high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, and a carbon arc lamp as a light source It can manufacture by the process to irradiate.
Component (A): Metal oxide (B) having a particle size of 1 nm to 400 nm Component: Polymer emulsion particle (C) having a particle size of 10 nm to 800 nm Component: Photosensitive acid generator (A) Component to (C) The components are as described above.

(Preparation of coating composition)
The method for preparing the coating composition is not particularly limited, and the coating composition can be prepared by dissolving or dispersing a material for forming the coating composition in a predetermined solvent such as water.
Here, as solid content concentration of an aqueous dispersion, Preferably it is 0.01-60 mass%, More preferably, it is 1-40 mass%.
Moreover, it is preferable that the viscosity of an aqueous dispersion is 0.1-100,000 mPa * s in 20 degreeC, More preferably, it is 1-10000 mPa * s.

(Application of coating composition)
Examples of a method for coating a coating composition (sometimes abbreviated as “aqueous dispersion”) on the substrate include spray spraying, flow coating, roll coating, brush coating, and dip coating. Method, spin coating method, screen printing method, casting method, gravure printing method, flexographic printing method and the like.
For the purpose of repair, it is preferable to spray coat the functional laminate.
In this case, it is possible to perform coating at an installed site, which is preferable.
Moreover, when laminating again on a large functional laminate having a length exceeding 1 m, a method of obtaining a functional laminate by flow coating or dip coating is preferred from the viewpoint of handling and cost.

(Drying process)
The functional laminate of this embodiment is subjected to a drying treatment after the coating composition is coated. In this case, heat treatment at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C. may be performed as desired.

It is preferable that it is 10 nm-4000 nm by the film thickness at the time of drying, More preferably, it is 50 nm-1000 nm, More preferably, it is 80 nm-500 nm.
When the film thickness is smaller than 10 nm, it is difficult to control the film thickness.
When the film thickness exceeds 4000 nm, cracks are likely to occur in the coating film.
The organic / inorganic composite coating film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.

(UV irradiation)
After the drying treatment, irradiation with ultraviolet rays is performed to form an organic-inorganic composite coating film constituting the functional laminate of the present embodiment.
The ultraviolet light used for the ultraviolet irradiation can be an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a metal halide lamp, or a carbon arc lamp.
The term “ultraviolet light” used herein means a wavelength of 400 nm or less, and preferably has a strong wavelength intensity of 300 nm or less. From such a viewpoint, it is preferable to use a high pressure mercury lamp or a low pressure mercury lamp.
Preferably illuminance of ultraviolet is 1 to 100 mW / cm ^2, more preferably 5~60mW / cm ^2, more preferably 10~40mW / cm ^2. If it is 1 mW / cm ² or less, the time required to obtain the desired refractive index becomes long, and if it exceeds 100 mW / cm ² , the coating film may be deteriorated.
In addition, vacuum ultraviolet rays, visible rays, near infrared rays, infrared rays, far infrared rays, microwaves, electron beams, β rays, γ rays, and the like can be used. Specifically, the light source may be an incandescent bulb, a halogen lamp, a fluorescent lamp, a tungsten lamp, an excimer laser, the sun, or the like.
One of these light sources may be used alone, or a plurality of these light sources may be used simultaneously or sequentially. The irradiation intensity and irradiation time can be appropriately selected.
The refractive index of the organic-inorganic composite coating film can be reduced by irradiation with ultraviolet rays.
With respect to the mechanism of action in which the refractive index decreases due to irradiation with ultraviolet rays, it is presumed that voids are formed inside the coating film due to decomposition and shrinkage of the polymer emulsion particles.

[Characteristics of functional laminate]
As described above, the refractive index can be lowered after irradiation by applying the coating composition on a substrate, drying, and then performing ultraviolet irradiation, as compared with before ultraviolet irradiation.
The refractive index of the functional laminate after irradiation with ultraviolet rays is preferably 1.10 to 1.45, more preferably 1.20 to 1.35 from the viewpoint of light transmittance, More preferably, it is 1.32. When the refractive index is lower than 1.10, the coating film needs to have voids and the strength may be lowered. On the other hand, if the refractive index is greater than 1.45, sufficient light transmittance may not be ensured.
In particular, when the functional laminate of this embodiment is used as a protective cover for a solar cell, the output of the solar cell can be improved.

[Use]
The functional laminate of the present embodiment is suitable as a protective cover for solar cells that are required to be transparent as a laminate having excellent antifouling properties and high light transmittance.
The protective cover of the solar cell protects the power generation element of the solar cell and the like, but in order to achieve high energy conversion efficiency, it is necessary to allow more sunlight to reach the power generation element.
Since the functional laminate of the present embodiment has a high light transmittance, a large amount of sunlight can be sent to the power generation element.
Moreover, since it is excellent also in antifouling property, even if it is a case where a solar cell is installed outdoors, adhesion of dust etc. can be prevented.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

The evaluation methods for various physical properties are shown below.
[1. Total light transmittance (%)]
Using the turbidimeter (Nippon Denshoku Industries NDH2000), the total light transmittance of the functional laminated body was measured according to JIS-K7105.
[2. (Refractive index)
Using a film thickness meter (FE-3000 manufactured by Otsuka Electronics Co., Ltd.), the refractive index with respect to light having a wavelength of 633 nm was measured.
The glass of the base material to be described later has a refractive index of 1.5. If it is lower than this value, the reflectance is lowered and the total light transmittance is increased.
[3. Initial contact angle (°)
After putting water droplets of deionized water on the outermost surface of the functional laminates of Examples and Comparative Examples described later and leaving them at 23 ° C. for 10 seconds, a contact angle meter (CA-X150 type contact angle meter manufactured by Kyowa Interface Science) Was used to measure the initial contact angle.

[Production Example 1]
(Synthesis of polymer emulsion particles (B-1) aqueous dispersion)
In a reaction vessel having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 6 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring.
To this, a mixed solution of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. In this state, 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 ", manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), a mixed solution of ammonium persulfate 2% by mass aqueous solution 40 g, and ion-exchanged water 1900 g, with the temperature in the reaction vessel maintained at 80 ° C. It was dripped simultaneously over about 2 hours.
Further, stirring was continued for about 8 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100 mesh wire net, and then solid content was adjusted to 10.0% by mass with ion-exchanged water. The polymer emulsion particles (B-1) aqueous dispersion having a number average particle diameter of 70 nm were prepared. The aqueous phase component was 5% by mass.
Content of water phase component (%) = (Dry mass of filtrate obtained by filtering component (B) with a molecular weight cut off of 50,000) × (100−total solid mass) / (mass of the filtrate−dryness of the filtrate) Mass) × 100 / total solid content mass.

[Production Example 2]
(Synthesis of polymer emulsion particles (B-2) aqueous dispersion)
In a reaction vessel having a reflux condenser, a dropping tank, a thermometer, and a stirrer, 1600 g of ion-exchanged water and 4 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring.
To this, a mixed solution of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. In this state, 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 ", manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), a mixed solution of ammonium persulfate 2% by mass aqueous solution 40 g, and ion-exchanged water 1900 g, with the temperature in the reaction vessel maintained at 80 ° C. It was dripped simultaneously over about 2 hours.
Further, stirring was continued for about 8 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100 mesh wire net, and then solid content was adjusted to 10.0% by mass with ion-exchanged water. The polymer emulsion particles (B-2) aqueous dispersion having a number average particle diameter of 130 nm were prepared. The aqueous phase component was 5% by mass.
Content of water phase component (%) = (Dry mass of filtrate obtained by filtering component (B) with a molecular weight cut off of 50,000) × (100−total solid mass) / (mass of the filtrate−dryness of the filtrate) Mass) × 100 / total solid content mass.

[Production Example 3]
(Synthesis of polymer emulsion particles (B-3) aqueous dispersion)
In a reaction vessel having a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1600 g of ion-exchanged water and 10 g of dodecylbenzenesulfonic acid were added, and then the temperature was heated to 80 ° C. with stirring.
To this, a mixed solution of 185 g of dimethyldimethoxysilane and 117 g of phenyltrimethoxysilane was dropped over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. In this state, 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 ", manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), a mixed solution of ammonium persulfate 2% by mass aqueous solution 40 g, and ion-exchanged water 1900 g, with the temperature in the reaction vessel maintained at 80 ° C. It was dripped simultaneously over about 2 hours.
Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100 mesh wire net, and then solid content was adjusted to 10.0% by mass with ion-exchanged water. The polymer emulsion particles (B-3) aqueous dispersion having a number average particle size of 40 nm were prepared. The aqueous phase component was 18% by mass.
Content of water phase component (%) = (Dry mass of filtrate obtained by filtering component (B) with a molecular weight cut off of 50,000) × (100−total solid mass) / (mass of the filtrate−dryness of the filtrate) Mass) × 100 / total solid content mass.

[Example 1]
As the photosensitive acid generator (C), thiobis (4,1-phenylene) -S, S, S ′, S′-tetraphenyldisulfonium bishexafluorophosphate and diphenyl (4-phenylthiophenyl) Propylene glycol monomethyl ether and ethanol were added to a propylene carbonate solution of sulfonium hexafluorophosphate (Syracure UVI-6992: manufactured by Dow Chemical Japan Co., Ltd.) to adjust the solid content to 0.1% by mass. The weight ratio of solid particles was added to the polymer emulsion (B-1) synthesized in Production Example 1] so that C / (B-1) = 0.01 / 100.
Next, a product name “Snow Tech O” (component (A)) manufactured by Nissan Chemical Industries, Ltd. is diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 10 nm). / (B-1) = 100/100.
Next, as a tetraethoxysilane (D1), a trade name “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. is blended so that D1 / A = 10/100 as a component ratio not including a diluent solvent and water, A coating composition was obtained.
The obtained coating composition was dip-coated on white plate glass (2 mm thick, 6 × 6 cm square, manufactured by SCHOTT) so as to have a film thickness of 500 nm. Then, it was dried at 70 ° C. for 30 minutes, and further irradiated with handy UV1200, QRU-2161 (manufactured by Oak Co., Ltd., illuminance 18 mW / cm ² ) for 30 minutes to obtain a functional laminate.
In the obtained functional laminate, the total light transmittance was 93.7%, the refractive index was 1.32 and the initial contact angle was 9 °.

[Example 2]
The polymer emulsion (B-2) synthesized in [Production Example 2] was changed.
Other conditions were the same as in the above [Example 1] to obtain a functional laminate.
In the obtained functional laminate, the total light transmittance was 93.8%, the refractive index was 1.30, and the initial contact angle was 6 °.

Example 3
As the photosensitive acid generator (C), thiobis (4,1-phenylene) -S, S, S ′, S′-tetraphenyldisulfonium bishexafluorophosphate and diphenyl (4-phenylthiophenyl) Propylene glycol monomethyl ether and ethanol were added to a propylene carbonate solution of sulfonium hexafluorophosphate (Syracure UVI-6992: manufactured by Dow Chemical Japan Co., Ltd.) to adjust the solid content to 0.1% by mass. The weight ratio of solid particles was added to the polymer emulsion (B-3) synthesized in Production Example 3] so that C / (B-3) = 0.01 / 100.
Next, a product name “Snow Tech O” (component (A)) manufactured by Nissan Chemical Industries, Ltd. is diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 10 nm). / (B-3) = 100/100.
Next, as a tetraethoxysilane (D1), a trade name “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. is blended so that D1 / A = 10/100 as a component ratio not including a diluent solvent and water, A coating composition was obtained.
The obtained coating composition was dip-coated on white plate glass (2 mm thick, 6 × 6 cm square, manufactured by SCHOTT) so as to have a film thickness of 500 nm. Then, it was dried at 70 ° C. for 30 minutes, and further irradiated with handy UV1200, QRU-2161 (manufactured by Oak Co., Ltd., illuminance 18 mW / cm ² ) for 30 minutes to obtain a functional laminate.
In the obtained functional laminate, the total light transmittance was 93.2%, the refractive index was 1.39, and the initial contact angle was 15 °.

[Comparative Example 1]
As the photosensitive acid generator (C), thiobis (4,1-phenylene) -S, S, S ′, S′-tetraphenyldisulfonium bishexafluorophosphate and diphenyl (4-phenylthiophenyl) Isopropanol was added to a propylene carbonate solution of sulfonium hexafluorophosphate (Syracure UVI-6992: manufactured by Dow Chemical Japan Co., Ltd.) to adjust the solid content to 0.1% by mass.
The product name “IPA-ST” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with isopropanol to obtain a dispersion having a solid content of 10% by mass (number average particle diameter 16 nm, refractive index 1.46). It was prepared and blended with the component (C) so that the weight ratio of solid content was C / A = 0.1 / 100.
Next, tetraethoxysilane (D1) and methyltriethoxysilane (D2) were blended so as to have a ratio of D1 / D2 / A = 50/10/100 to obtain a coating composition.
The obtained coating composition was dip-coated on a white plate glass (2 mm thick, 6 × 6 cm square, manufactured by SCHOTT) to a film thickness of 200 nm, then dried at 70 ° C. for 30 minutes, and further, handy UV1200 Then, irradiation with QRU-2161 (manufactured by Oak Co., Ltd., illuminance of 18 mW / cm ² ) for 30 minutes gave a functional laminate.
In the obtained functional laminate, the total light transmittance was 92.6%, the refractive index was 1.48, and the initial contact angle was 58 °.

[Comparative Example 2]
To the polymer emulsion (B-3) synthesized in [Production Example 3], a product name “Snow Tech O” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with water to obtain a solid content of 10 mass. % Dispersion (number average particle diameter 10 nm), and blended so that A / (B-3) = 100/100.
Next, as a tetraethoxysilane (D1), a trade name “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. is blended so that D1 / A = 10/100 as a component ratio not including a diluent solvent and water, A coating composition was obtained.
The obtained coating composition was dip-coated on white plate glass (2 mm thick, 6 × 6 cm square, manufactured by SCHOTT) so as to have a film thickness of 500 nm. Then, it dried at 70 degreeC for 30 minutes, and also irradiated with handy UV1200, QRU-2161 (made by Oak Co., Ltd., illumination intensity 18mW / cm < ² >) for 30 minutes, and obtained the functional laminated body.
In the obtained functional laminate, the total light transmittance was 92.8%, the refractive index was 1.46, and the initial contact angle was 28 °.

  As described above, the functional laminates of Examples 1 to 3 all have high light transmittance, a small water contact angle, excellent antifouling property, and excellent characteristics as a protective cover for solar cells. It turns out that it is possible.

  The functional laminate of the present invention has industrial applicability as a protective cover for solar cells.

Claims (6)

It is a functional laminate having an organic-inorganic composite coating film containing each of the following components (A) to (C) on at least one main surface of the substrate,
The organic-inorganic composite coating film is formed by applying a coating composition containing the following components (A) to (C) to the substrate, performing a drying treatment, and irradiating with ultraviolet rays. Laminate.
Component (A): Metal oxide having a particle size of 1 nm to 400 nm (B) Component: Polymer emulsion particle having a particle size of 10 nm to 800 nm (C) Component: Photosensitive acid generator   The functional laminate according to claim 1, wherein a refractive index of the organic-inorganic composite coating film after the ultraviolet irradiation is 1.10 to 1.45. The component (B) is
(B1) component: a 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;
The functional laminate according to claim 1, which is a polymer emulsion particle obtained by polymerizing a polymerization stock solution comprising   The functional laminate according to any one of claims 1 to 3, wherein the refractive index of the component (A) is 1.40 to 3.00.   The functional laminated body as described in any one of Claims 1 thru | or 4 used as a protective cover of a solar cell. Applying a coating composition containing the following components (A) to (C) to at least one principal surface of the substrate;
Applying a drying process;
Ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, a step of irradiating with ultraviolet rays using at least one selected from the group consisting of a carbon arc lamp,
A method for producing a functional laminate having:
Component (A): Metal oxide having a particle size of 1 nm to 400 nm (B) Component: Polymer emulsion particle having a particle size of 10 nm to 800 nm (C) Component: Photosensitive acid generator