JP6179649B2 - Laminate - Google Patents

Description

The present invention relates to a laminate including a coating layer and a hydrophilic layer.

Since the coating film formed from the fluororesin paint has excellent weather resistance, the surface of an article used outdoors can be covered with the coating film formed from the fluororesin paint to impart weather resistance to the article. Has been done.

However, although the coating film formed from the fluororesin coating material has excellent weather resistance, it has a defect that the surface is easily contaminated with dirt, so in order to solve this defect, A method for forming a hydrophilic coating film on the coating film has been proposed.

For example, Patent Document 1 proposes an outdoor article having a coating film surface having an octane contact angle of 102 degrees or more in water as an outdoor article having a coating film surface particularly for preventing the occurrence of rain streak stains. And a surface treatment comprising a silicon compound (A) and a synthetic resin film-forming component (B) such as a fluororesin for paints on the surface of the coating film of an outdoor article having a hydrophobic synthetic resin coating film surface. It has been proposed to form by applying an agent.

Patent Document 2 has a primer layer and a polyvinylidene fluoride-based fluorocoating intermediate coating film on a metal plate as a pre-coated metal plate that is difficult to be contaminated with carbon-based pollutants in the atmosphere. It has a top coat film formed from a paint obtained by adding 0.5 to 100 parts by weight of alkoxysilane or a partially hydrolyzed condensate of alkoxysilane to 100 parts by weight of a vinylidene-based fluororesin paint. Precoated metal plates have been proposed.

In Patent Document 3, a protective layer formed of an inorganic paint containing no photocatalyst and a photocatalyst layer formed of an inorganic paint containing a photocatalyst and fluororesin wax are laminated on at least one surface of a metal plate. A painted metal plate characterized by the above has been proposed.

JP-A-7-109435 Japanese Patent Laid-Open No. 10-128232 JP 2007-181951 A

However, since the methods proposed in Patent Documents 1 and 2 are not sufficiently hydrophilized, a method capable of further hydrophilization is required.
In patent document 3, since the binder which forms a protective layer with a photocatalyst decomposes | disassembles and a weather resistance is not enough, the improvement of a weather resistance is calculated | required.

The objective of this invention is providing the laminated body excellent in the weather resistance and hydrophilicity in view of the said present condition.

The present inventors will solve the above-mentioned problems by forming a fluorine-containing polymer layer or an acrylic polymer layer having excellent weather resistance on the surface of the substrate as a coating layer, and further providing a hydrophilic layer on the layer. I tried. However, it was not easy to form a hydrophilic layer on the fluorine-containing polymer layer or the acrylic polymer layer, and even if it could be formed, it was found that the hydrophilicity of the laminate disappeared after the weather resistance test.

Therefore, as a result of intensive studies on the structure of the laminate, the present inventors can form a hydrophilic layer on the coating layer only when the coating layer has a specific surface free energy, even after the weather resistance test. The inventors found that the hydrophilicity of the laminate was maintained, and completed the present invention.

That is, this invention is a laminated body characterized by including the coating layer whose surface free energy is 30-40 mJ / m < ² >, and a hydrophilization layer.

The coating layer is preferably made of a dry coating film of a paint blended with a resin.

The coating layer includes a resin, and the resin is preferably a fluorine-containing polymer or an acrylic polymer having a curable functional group.

The coating layer includes a resin, and the resin is a composite polymer particle. The composite polymer particle includes the fluoropolymer (A) and the acrylic polymer (B) in the same particle, and the fluoropolymer (A ) And the acrylic polymer (B), the mass ratio (A / B) is preferably 90/10 to 10/90.

The fluoropolymer (A) preferably contains vinylidene fluoride units.

The fluoropolymer (A) preferably contains a vinylidene fluoride unit and at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene.

The acrylic polymer (B) preferably contains at least one acrylic monomer unit selected from the group consisting of acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester.

The acrylic polymer (B) preferably contains a methacrylic acid ester unit and a methacrylic acid unit.

The hydrophilic layer is formed of a paint containing water and at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorocarbon sulfonic acid resins, transition metal polyvalent ions and metal oxides. It is preferable.

It is preferable that the laminated body further includes a base material, and the base material, the coating layer, and the hydrophilic layer are laminated in this order.

Since the laminated body of this invention has the said structure, it is excellent in a weather resistance and hydrophilicity, and shows the hydrophilic property which was excellent even after the weather resistance test.

Hereinafter, the present invention will be specifically described.

The laminate of the present invention includes a coating layer and a hydrophilic layer.

The hydrophilic layer preferably has a contact angle with water of 70 ° or less. The contact angle is more preferably 60 ° or less, and the lower limit is not particularly limited, but may be 0 ° or 13 °.

The contact angle is measured with a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as a device and water as a solvent.

The coating layer has a surface free energy of 30 to 40 mJ / m ² . The surface free energy is preferably 32 mJ / m ² or more, and more preferably 38 mJ / m ² or less.

The surface free energy is measured with a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as an apparatus and n-hexadecane and water as solvents.

In the laminate of the present invention, since the coating layer has a specific surface free energy, the hydrophilic layer and the coating layer are firmly bonded, and both layers do not peel even after the weather resistance test. Excellent hydrophilicity even after the weather resistance test.

The coating layer preferably contains a resin. The resin is preferably a fluorine-containing polymer or an acrylic polymer having a curable functional group.

Examples of the fluorine-containing polymer having a curable functional group include polymers obtained by introducing a curable functional group into a fluorine-containing polymer. The curable functional group-containing fluorine-containing polymer includes a resinous polymer having a clear melting point, an elastomeric polymer exhibiting rubber elasticity, and an intermediate thermoplastic elastomeric polymer.

The functional group that imparts curability to the fluorine-containing polymer is appropriately selected according to the ease of production of the polymer and the curing system. For example, a hydroxyl group (however, the hydroxyl group contained in the carboxyl group is excluded. The same applies hereinafter). , A carboxyl group, a group represented by —COOCO—, a cyano group, an amino group, a glycidyl group, a silyl group, a silanate group, and the like. Of these, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by —COOCO—, an amino group, a cyano group, and a silyl group is preferable from the viewpoint of good curing reactivity. More preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a silyl group, and more preferably at least one group selected from the group consisting of a hydroxyl group and a carboxyl group. . These curable functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer having a curable functional group.

Examples of the curable functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, a silicone vinyl monomer, and the like. Two or more kinds can be used.

The curable functional group-containing fluorine-containing polymer includes a polymer unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. And a polymerized unit based on at least one curable functional group-containing monomer selected from the group consisting of: The curable functional group-containing fluorine-containing polymer is a polymer unit based on a fluorine-containing monomer, and at least one curable functional group selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer. More preferably, it contains polymerized units based on group-containing monomers.

The polymerization unit based on the curable functional group-containing monomer is preferably 8 to 30 mol% with respect to all the polymerization units of the curable functional group-containing fluoropolymer. A more preferred lower limit is 10 mol%, and a more preferred upper limit is 20 mol%.

Examples of the curable functional group-containing monomer include, but are not limited to, the following. In addition, these 1 type (s) or 2 or more types can be used.

(1-1) Hydroxyl group-containing monomer:
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2- Hydroxyl-containing vinyl ethers such as methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether It is done. Among these, hydroxyl group-containing vinyl ethers are preferable in that polymerization reactivity and functional group curability are excellent, and at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether. Monomers are particularly preferred.

Examples of other hydroxyl group-containing monomers include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

(1-2) Carboxyl group-containing monomer:
Examples of the carboxyl group-containing monomer include a formula:
CR ¹¹ R ¹² = CR ¹³ (CH ₂ ) _n COOH
(Wherein R ¹¹ , R ¹² and R ¹³ are the same or different and each represents a hydrogen atom, an alkyl group, a carboxyl group or an ester group. N is 0 or 1). (For example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, etc.), their esters and acid anhydrides, and the formula:
^{_{CH 2 = CH (CH 2)}} n O (R 14 OCO) m R 15 COOH
Wherein R ¹⁴ and R ¹⁵ are the same or different and both are saturated or unsaturated linear, branched or cyclic alkylene groups. N is 0 or 1 and m is 0 or 1 And at least one monomer selected from the group consisting of carboxyl group-containing vinyl ether monomers represented by

Specific examples of the carboxyl group-containing monomer include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid and the like can be mentioned. Among them, since homopolymerization is low and it is difficult to form a homopolymer, from crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid. At least one acid selected from the group is preferred.

Specific examples of the carboxyl group-containing vinyl ether monomer include, for example, 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, and 3- (2-vinyloxyethoxy). And carbonyl) propionic acid and 3- (2-vinyloxybutoxycarbonyl) propionic acid. Among these, 3- (2-allyloxyethoxycarbonyl) propionic acid is preferable because it is advantageous in terms of good monomer stability and polymerization reactivity.

(1-3) Amino group-containing monomer:
Examples of the amino group-containing monomer include amino vinyl ethers represented by CH ₂ ═CH—O— (CH ₂ ) _x —NH ₂ (x = 0 to 10); CH ₂ ═CH—O—CO (CH ₂ ) allylamines represented by _{x -NH 2 (x = 1~10)} ; other aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide or the like.

(1-4) Silyl group-containing monomer:
Examples of the silyl group-containing monomer include silicone-based vinyl monomers. Examples of the silicone vinyl monomer include CH ₂ ═CHCO ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ═CHCO ₂ (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , CH ₂ ═C. _{(CH 3) CO 2 (CH} 2) 3 Si (OCH 3) 3, CH 2 = C (CH 3) CO 2 (CH 2) 3 Si (OC 2 H 5) 3, CH 2 = CHCO 2 (CH 2 _{) 3 SiCH 3 (OC 2 H} 5) 2, CH 2 = C (CH 3) CO 2 (CH 2) 3 SiC 2 H 5 (OCH 3) 2, CH 2 = C (CH 3) CO 2 (CH 2 ) ₃ Si (CH ₃ ) ₂ (OC ₂ H ₅ ), CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ ) ₃ Si (CH ₃ ) ₂ OH, CH ₂ ═CH (CH ₂ ) ₃ Si (OCOCH) _{3) 3, CH 2 = C} ( _{H 3) CO 2 (CH 2} ) 3 SiC 2 H 5 (OCOCH 3) 2, CH 2 = C (CH 3) CO 2 (CH 2) 3 SiCH 3 (N (CH 3) COCH 3) 2, CH 2 _{= CHCO 2 (CH 2) 3} SiCH 3 _{[ON (CH 3) C 2 H} 5 ] _{2, CH 2 = C (CH} 3) CO 2 (CH 2) 3 SiC 6 H 5 [ON _(CH 3) _{C 2} H _5] (meth) acrylic acid esters such as _{2; CH 2 = CHSi [ON} = C (CH 3) (C 2 H 5)] 3, CH 2 = CHSi (OCH 3) 3, CH 2 = CHSi ( _{OC 2 H 5) 3, CH} 2 = CHSiCH 3 (OCH 3) 2, CH 2 = CHSi (OCOCH 3) 3, CH 2 = CHSi (CH 3) 2 (OC 2 H 5), CH 2 = CHSi (CH ₃ ) ₂ SiCH ₃ (OCH ₃ ) ₂ , CH ₂ = CHSiC ₂ H ₅ (OCOCH ₃ ) ₂ , CH ₂ = CHSiCH ₃ [ON (CH ₃ ) C ₂ H ₅ ] ₂ , vinyltrichlorosilane or a partial hydrolyzate thereof And vinyl silanes such as trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, and triethoxysilylpropyl vinyl ether.

The curable functional group-containing fluorine-containing polymer preferably has a polymerized unit based on a fluorine-containing vinyl monomer.

The polymerized units based on the fluorinated vinyl monomer is preferably 20 to 49 mol% based on all polymerized units of the curable functional group-containing fluorinated polymer. A more preferred lower limit is 30 mol%, and a still more preferred lower limit is 40 mol%. A more preferred upper limit is 47 mol%.

The fluorine-containing vinyl monomer is selected from the group consisting of tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene and perfluoro (alkyl vinyl ether). From the group consisting of TFE, CTFE and VdF, in that it is excellent in dispersibility, moisture resistance, heat resistance, flame retardancy, adhesion, copolymerization and chemical resistance, etc. It is more preferable that it is at least one selected, and it is particularly preferable that it is at least one selected from the group consisting of TFE and CTFE in terms of excellent weather resistance and further excellent moisture resistance. Most preferred.

The curable functional group-containing fluorine-containing polymer preferably contains polymerized units based on at least one fluorine-free vinyl monomer selected from the group consisting of carboxylic acid vinyl esters, alkyl vinyl ethers and non-fluorinated olefins.
Carboxylic acid vinyl ester has the effect | action which improves compatibility. Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, vinyl benzoate, Examples include vinyl para-t-butylbenzoate.
Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.
Non-fluorinated olefins include ethylene, propylene, n-butene, isobutene and the like.

The polymerized units based on the non-fluorine-containing vinyl monomer preferably constitute all polymerized units other than polymerized units based on the curable functional group-containing vinyl monomer and polymerized units based on the fluorine-containing vinyl monomer.

Examples of the fluorine-containing polymer into which the curable functional group is introduced include the following, depending on the polymer units constituting the polymer.

Examples of the fluorine-containing polymer into which a curable functional group is introduced include (1) perfluoroolefin-based polymer mainly composed of perfluoroolefin units, and (2) CTFE-based mainly composed of chlorotrifluoroethylene (CTFE) units. Examples thereof include polymers, (3) VdF polymers mainly composed of vinylidene fluoride (VdF) units, and (4) fluoroalkyl group-containing polymers mainly composed of fluoroalkyl units.

(1) Perfluoroolefin-based polymer mainly composed of perfluoroolefin units The perfluoroolefin-based polymer contains 20 to 49 mol% of perfluoroolefin units with respect to all polymerized units of the perfluoroolefin-based polymer. preferable. A more preferred lower limit is 30 mol%, and a still more preferred lower limit is 40 mol%. A more preferred upper limit is 47 mol%. Specific examples include tetrafluoroethylene (TFE) homopolymers, or copolymers of TFE with hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), and the like. Examples thereof include copolymers with other monomers capable of copolymerization.

Examples of the other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and cyclohexyl. Carboxylic acid vinyl esters such as vinyl carboxylate, vinyl benzoate and vinyl para-t-butylbenzoate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; ethylene, propylene, n-butene and isobutene Non-fluorinated olefins such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether and the like. It is not limited only thereto.

Among the perfluoroolefin polymers mainly composed of perfluoroolefin units, TFE polymers mainly composed of TFE units are preferable in terms of excellent pigment dispersibility, weather resistance, copolymerization properties, and chemical resistance. The TFE polymer preferably has 20 to 49 mol% of TFE units with respect to all polymerized units of the TFE polymer. A more preferred lower limit is 30 mol%, and a still more preferred lower limit is 40 mol%. A more preferred upper limit is 47 mol%.

Examples of the curable functional group-containing fluorine-containing polymer obtained by introducing a curable functional group into a perfluoroolefin polymer mainly composed of perfluoroolefin units include, for example, TFE / isobutylene / hydroxybutyl vinyl ether / copolymer of other monomers. For example, TFE / vinyl versatate / hydroxybutyl vinyl ether / copolymer of other monomers, TFE / VdF / hydroxybutyl vinyl ether / copolymer of other monomers, etc. In particular, TFE / isobutylene / And at least one copolymer selected from the group consisting of a copolymer of hydroxybutyl vinyl ether / other monomers and a copolymer of TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomers. preferable. Examples of such a curable polymer paint include Zaffle (registered trademark) GK series manufactured by Daikin Industries, Ltd.

(2) CTFE-based polymer mainly composed of chlorotrifluoroethylene (CTFE) unit A curable functional group-containing fluoropolymer obtained by introducing a curable functional group into a CTFE-based polymer mainly composed of a CTFE unit includes, for example, CTFE / hydroxy Examples thereof include butyl vinyl ether / other monomer copolymers. Examples of the curable polymer coating for the CTFE polymer include Lumiflon (registered trademark) manufactured by Asahi Glass Co., Ltd., Fluonate (registered trademark) manufactured by Dainippon Ink Manufacturing Co., Ltd., and Cefral Coat (registered trademark) manufactured by Central Glass ) Etc. can be illustrated.

(3) VdF polymer mainly composed of vinylidene fluoride (VdF) unit As a curable functional group-containing fluorine-containing polymer in which a curable functional group is introduced into a VdF polymer mainly composed of VdF unit, for example, VdF / TFE / Examples thereof include copolymers of hydroxybutyl vinyl ether / other monomers.

(4) Fluoroalkyl group-containing polymer mainly composed of fluoroalkyl units As a curable functional group-containing fluorinated polymer in which a curable functional group is introduced into a fluoroalkyl group-containing polymer mainly composed of fluoroalkyl units, for example, CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH═CH ₂ (mixture of n = 3 and 4) / 2-hydroxyethyl methacrylate / stearyl acrylate copolymer. Examples of the fluoroalkyl group-containing polymer include Unidyne (registered trademark) manufactured by Daikin Industries, Ltd., FTONE (registered trademark), Zonyl (registered trademark) manufactured by DuPont, and the like.

Among the above (1) to (4), from the viewpoint of weather resistance and moisture resistance, the fluoropolymer into which the curable functional group is introduced is preferably a perfluoroolefin polymer, and a TFE polymer mainly composed of TFE units. Alternatively, a CTFE polymer mainly composed of CTFE units is more preferable.

The said curable functional group containing fluorine-containing polymer can be manufactured by the method disclosed by Unexamined-Japanese-Patent No. 2004-204205, for example.

In the acrylic polymer, the polymer unit based on the monomer having an acrylic group is preferably 5% by mass or more based on the total polymer units. More preferably, it is 10 mass% or more. More preferably, it is 20 mass% or more. Moreover, from the point which is excellent in a weather resistance, 98 mass% or less is preferable, 96 mass% or less is more preferable, 90 mass% or less is still more preferable, 80 mass% or less is especially preferable.

The acrylic polymer is preferably a polymer comprising polymerized units based on (meth) acrylic acid alkyl ester, for example. Carbon number of the alkyl group of the said (meth) acrylic-acid alkylester is 1-10, for example.
“(Meth) acrylic acid alkyl ester” includes acrylic acid alkyl ester and methacrylic acid alkyl ester.

Since an acrylic polymer is excellent in weather resistance, the content of polymerized units based on (meth) acrylic acid alkyl ester is preferably 5% by mass or more. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, from the point which is excellent in a weather resistance, 98 mass% or less is preferable, 96 mass% or less is more preferable, 90 mass% or less is still more preferable, 80 mass% or less is especially preferable.

The acrylic polymer is, for example, a polymer comprising polymerized units based on (meth) acrylic acid alkyl ester having no curable functional group at the side chain and / or main chain terminal (hereinafter referred to as acrylic polymer (i)). And (ii) a copolymer (hereinafter referred to as acrylic polymer (ii) having a curable functional group at the side chain and / or main chain terminal and comprising a polymer unit based on (meth) acrylic acid alkyl ester). And at least one polymer selected from the group consisting of: Acrylic polymer (ii) is preferred because of excellent weather resistance.

The acrylic polymer (i) is composed of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Polymers comprising polymerized units based on at least one monomer selected from the group are preferred. The acrylic polymer (i) may be a polymer composed only of these monomers, or a copolymer composed of polymerized units based on an ethylenically unsaturated monomer copolymerizable with these monomers. It may be a polymer.

The acrylic polymer (i) has at least one monomer selected from the group consisting of isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate because of its excellent weather resistance. Polymers composed of polymerized units based on these are preferred, and copolymers composed of polymerized units based on ethylenically unsaturated monomers copolymerizable with these monomers are more preferred.

As the ethylenically unsaturated monomer copolymerizable with at least one monomer selected from the group consisting of isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate, for example, (Meth) acrylates having an aromatic group, (meth) acrylates having a fluorine atom or a chlorine atom at the α-position, fluoroalkyl (meth) acrylates in which the alkyl group is substituted with a fluorine atom, vinyl ethers, vinyl esters And aromatic vinyl monomers such as styrene, olefins such as ethylene, propylene, isobutylene, vinyl chloride, and vinylidene chloride, fumaric acid diesters, maleic acid diesters, and (meth) acrylonitrile.

Commercially available acrylic copolymers of acrylic polymer (i) include, for example, Hitaroid (registered trademark) 1005, Hitaroid 1206, Hitaroid 2330-60, Hitaroid 4001, Hitaroid 1628A (all manufactured by Hitachi Chemical Co., Ltd., trade name); Naral (registered trademark) LR-1065, Dianal LR-90, etc. (all manufactured by Mitsubishi Rayon Co., Ltd., trade name); Paraloid (registered trademark) B-44, Paraloid A-21, Paraloid B-82, etc. (all Dow Chemical Corporation. (Trade name); ELVACITE 2000 and the like (Rusant International Co., Ltd. trade name); Almatex (registered trademark) L1044P (Mitsui Chemicals, trade name) and the like.

The acrylic polymer (ii) has a curable functional group at the side chain and / or main chain terminal. Examples of the curable functional group include a hydroxyl group, a carboxyl group, an epoxy group, a cyano group, an amino group, a glycidyl group, a silyl group, and a silanate group. Among them, a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a glycidyl group. And at least one group selected from the group consisting of silyl groups is more preferable, at least one group selected from the group consisting of hydroxyl groups, amino groups, and glycidyl groups is more preferable, and the curing reactivity is high. A hydroxyl group is particularly preferred from the viewpoint of goodness.

The acrylic polymer (ii) is a copolymer composed of polymerized units based on (meth) acrylic acid alkyl ester, and the alkyl group of the (meth) acrylic acid alkyl ester preferably has 1 to 10 carbon atoms.

The acrylic polymer (ii) comprises a polymerized unit based on a (meth) acrylic acid alkyl ester and a polymerized unit based on a monomer copolymerizable with the (meth) acrylic acid alkyl ester. The monomer preferably has a curable functional group.
The content of the polymerization unit based on the monomer copolymerizable with the (meth) acrylic acid alkyl ester having a curable functional group is preferably 50% by mass or less, more preferably 40% by mass, because of excellent weather resistance. It is as follows. Moreover, 2 mass% or more is preferable from the point which is excellent in a weather resistance, More preferably, it is 4 mass% or more.

In the acrylic polymer (ii), the (meth) acrylic acid alkyl ester includes methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, And at least 1 sort (s) of monomer selected from the group which consists of cyclohexyl (meth) acrylates is preferable.

Examples of the monomer having a curable functional group copolymerizable with (meth) acrylic acid alkyl ester include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, ( At least one monomer selected from the group consisting of (meth) acrylic acid, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and 2-aminopropyl (meth) acrylate is preferred.

The acrylic polymer (ii) is a polymerized unit based on a (meth) acrylic acid alkyl ester, a polymerized unit based on a monomer having a curable functional group copolymerizable with the (meth) acrylic acid alkyl ester, and these The copolymer which consists of a polymerization unit based on the ethylenically unsaturated monomer copolymerizable with a monomer may be sufficient.

In the acrylic polymer (ii), the ethylenically unsaturated monomer includes (meth) acrylates having an aromatic group, (meth) acrylates having a fluorine atom or a chlorine atom at the α-position, and the alkyl group is a fluorine atom. Substituted fluoroalkyl (meth) acrylates, vinyl ethers, vinyl esters, aromatic vinyl monomers such as styrene, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, fumaric acid diesters, malein Acid diesters, (meth) acrylonitrile and the like are preferable.

Commercially available products of acrylic polymer (ii) include Hitaroid 3004, Hitaroid 3018, Hitaroid 3046C, Hitaroid 6500B, Hitaroid 6500, etc. (all manufactured by Hitachi Chemical Co., Ltd., trade name); Acridic (registered trademark) A810-45 , ACRYDIC A814, ACRICID 47-540, etc. (all manufactured by Dainippon Ink & Chemicals, Inc., trade name); Dialnal LR-620, Dialnal SS-1084, Dialnal SS-792, etc. (all Mitsubishi) Manufactured by Rayon Co., Ltd. (trade name); Olester (registered trademark) Q166, Olester Q185, Olester Q612, Olester Q723, etc. (all manufactured by Mitsui Chemicals, Inc., trade name); Hariacron 8360G-55, Hariacron 8360HS-130, Hariacron 816 (Both Harima Kasei Co., Ltd.. Trade name) and the like.

The number average molecular weight of the acrylic polymer is preferably 1000 to 200000. More preferably, it is 2000-100000. If the number average molecular weight is too large, coating tends to be difficult, and if it is too small, there is a tendency to cause problems with weather resistance.

Examples of the resin also include a fluorine-containing copolymer containing a perhaloolefin unit, a non-fluorine vinyl monomer unit, an undecylenic acid unit, and a hydroxyl group-containing vinyl monomer unit, or a neutralized product thereof.
Examples of the resin include 30 to 70 mol% perhaloolefin unit, 5 to 35 mol% non-fluorine vinyl monomer unit, and a hydroxyl group-containing vinyl unit having an amount of hydroxyl group in the range of 10 to 200 mgKOH / g. A fluorine-containing copolymer containing a monomer unit and an undecylenic acid unit having an acid value in the range of 10 to 100 mgKOH / g or a neutralized product thereof is also preferable.

Examples of the perhaloolefin include one or more of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and the like. Preferred fluoroolefins include TFE or HFP, particularly TFE because of excellent weather resistance.

Since content of a perhaloolefin unit is excellent in weather resistance, 30-70 mol% is preferable. Furthermore, 35 to 55 mol%, particularly 40 to 50 mol% is preferable.

As a non-fluorine vinyl monomer, a C2-C4 non-fluorine vinyl monomer is preferable. For example, ethylene, propylene, n-butylene, isobutylene, vinyl acetate and the like can be mentioned. Among these, copolymerization with perhaloolefin is particularly good, and transparency is improved and flexibility is lowered by lowering the glass transition temperature. Isobutylene is preferable from the viewpoint of improving the viscosity.

The content of the non-fluorine vinyl monomer unit is preferably 5 to 35 mol% because it is easy to produce and excellent in compatibility with the curing agent. Furthermore, 15-30 mol% is preferable.

Examples of the hydroxyl group-containing vinyl monomer include the formula:
CH ₂ = CHR ²¹
(Wherein, R ²¹ represents —OR ²² or —CH ₂ OR ²² (where R ²² is an alkyl group having a hydroxyl group)), and a hydroxyl group-containing alkyl vinyl ether or a hydroxyl group-containing alkyl allyl ether. R ²² is, for example, a group in which 1 to 3, preferably 1 hydroxyl group is bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether. , 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like. Among these, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable in view of excellent polymerization reactivity and curability.

Examples of other hydroxyl group-containing vinyl monomers include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

The content of the hydroxyl group-containing vinyl monomer unit is preferably such that the hydroxyl value of the fluorine-containing copolymer is in the range of 10 to 200 mgKOH / g. The hydroxyl value is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more, from the viewpoint of excellent weather resistance. The upper limit of the hydroxyl value is 200 mgKOH / g, preferably 150 mgKOH / g, which is advantageous in terms of imparting flexibility to the coating film.

Undecylenic acid is a straight-chain unsaturated carboxylic acid having 11 carbon atoms, has a long hydrocarbon chain compared to crotonic acid, and can greatly improve compatibility with the curing agent. In addition, undecylenic acid has a carboxyl group using trimellitic acid. Since the ester bond that occurs when introduced is not generated, there is no decrease in storage stability due to cleavage of the ester. Moreover, it is preferable in that it is difficult to form a homopolymer, the polymerization reactivity is good, and it is difficult to hydrolyze.

The content of the undecylenic acid unit is preferably such that the acid value of the resulting fluorinated copolymer is in the range of 10 to 100 mgKOH / g. Especially, the quantity which makes an acid value the range of 10-80 mgKOH / g, especially 15-60 mgKOH / g is preferable.

The molecular weight of the fluorinated copolymer is 100,000 or less, preferably 50,000 or less in terms of number average molecular weight from the viewpoint of easy production, and 4,000 or more, particularly 8,000 or more is weather resistant. It is preferable at the point which is excellent in property.

Specific preferred fluorine-containing copolymers are illustrated below, but are not limited thereto.

TFE / hydroxybutyl vinyl ether (HBVE) / isobutylene (IB) / undecylenic acid / vinyl benzoate (VBz) / vinyl pivalate copolymer, TFE / hydroxybutyl vinyl ether (HBVE) / vinyl acetate / undecylenic acid / vinyl benzoate / Vinyl pivalate copolymer, TFE / hydroxybutyl vinyl ether (HBVE) / isobutylene / vinyl versatate / undecylene acid copolymer, TFE / vinyl acetate / isobutylene / vinyl versatate / undecylenic acid copolymer.

The carboxyl group introduced by undecylenic acid may be used not only for facilitating dispersion of the fluorinated copolymer in water and forming a stable aqueous dispersion, but also for crosslinking.

The carboxyl group gives water dispersibility as it is, but the water dispersibility is further improved by neutralizing with alkali to make it water-soluble or water-dispersible. Specifically, for example, an ammonium salt, an amine salt or an alkali metal salt is preferable.

Neutralization takes place before, during or after mixing with water to convert to water-soluble or water-dispersible functional groups.

The neutralizing agent used for neutralization is ammonia; organic amines such as diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, diethylenetriamine, triethylamine; Examples include alkali metal hydroxides such as sodium and potassium hydroxide. Among these, ammonia, triethylamine, and diethanolamine are preferable in terms of convenience of availability and stability of the emulsion, and ammonia and triethylamine are particularly advantageous in terms of easy handling.

The neutralizing agent is preferably used in the form of an aqueous solution, but may be used in the form of gas or solid content.

Neutralization is performed by neutralizing a carboxyl group corresponding to 5 mg KOH / g or more, preferably 10 mg KOH / g or more, 70 mg KOH / g or less, and preferably 50 mg KOH / g or less of the acid value of the fluorine-containing copolymer. Neutralize with

The acid value and hydroxyl value in the present invention are calculated values calculated by the following method.

(Hydroxyl value calculation method)
The monomer composition in the polymer is calculated from the generated polymer, polymer solution, analysis of residual monomer amount and monomer charge amount. Next, the hydroxyl value in the polymer is calculated from the total monomer composition and the composition of the hydroxyl group-containing monomer.

(Acid value calculation method)
The monomer composition in the polymer is calculated from the generated polymer, polymer solution, analysis of residual monomer amount and monomer charge amount. Next, the acid value in the polymer is calculated from the total monomer composition and the composition of the carboxyl group-containing monomer.

The resin is preferably composite polymer particles. The composite polymer particles preferably contain the fluoropolymer (A) and the acrylic polymer (B) in the same particle. The fluoropolymer (A) and the acrylic polymer (B) are present in a single particle. In this respect, the fluorine-containing composite polymer particles are different from the particles obtained by simply mixing the particles of the fluoropolymer (A) and the particles of the acrylic polymer (B). The fluoropolymer (A) and the acrylic polymer (B) are not chemically bonded.

The composite polymer particles preferably have a mass ratio (A / B) of the fluoropolymer (A) to the acrylic polymer (B) of 95/5 to 10/90. As a mass ratio (A / B), 90/10 or less is more preferable, 20/80 or more is more preferable, and 25/75 or more is still more preferable. When the mass ratio (A / B) is within the above range, the coating layer having the surface free energy can be easily formed.

The fluoropolymer (A) contains a repeating unit (fluoroolefin unit) based on a fluoroolefin. Examples of the fluoroolefin include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE),

等のパーフルオロオレフィン；クロロトリフルオロエチレン（ＣＴＦＥ）、フッ化ビニル（ＶＦ）、ビニリデンフルオライド（ＶｄＦ）、トリフルオロエチレン、トリフルオロプロピレン、ヘキサフルオロイソブテン、２，３，３，３−テトラフルオロプロペン、１，３，３，３−テトラフルオロプロペン、１，１，３，３，３−ペンタフルオロプロペン等の非パーフルオロオレフィンが挙げられる。パーフルオロ（アルキルビニルエーテル）としては、パーフルオロ（メチルビニルエーテル）（ＰＭＶＥ）、パーフルオロ（エチルビニルエーテル）（ＰＥＶＥ）、パーフルオロ（プロピルビニルエーテル）（ＰＰＶＥ）等が挙げられる。

Perfluoroolefins such as chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene, trifluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoro Non-perfluoroolefins such as propene, 1,3,3,3-tetrafluoropropene, and 1,1,3,3,3-pentafluoropropene are exemplified. Examples of perfluoro (alkyl vinyl ether) include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), and the like.

Moreover, a functional group-containing fluoroolefin can also be used as the fluoroolefin.
Examples of the functional group-containing fluoroolefin include a formula:
_{^{CX 3 2 = CX 4 - (}} Rf) m -Y 1
Wherein Y ¹ is —OH, —COOM ² , —SO ₂ F, —SO ₃ M ² (M ² is a hydrogen atom, NH ₄ group or alkali metal), carboxylate, carboxyester group, epoxy group or A cyano group; X ³ and X ⁴ are the same or different and both are hydrogen atoms or fluorine atoms; Rf is a divalent fluorine-containing alkylene group or fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, or 2 to 40 carbon atoms And a divalent fluorine-containing alkylene group or fluorine-containing oxyalkylene group containing an ether bond; m is 0 or 1).

Specific examples of the functional group-containing fluoroolefin include, for example,

Etc.

Examples of the fluoroolefin include iodine-containing monomers such as perfluoro (6,6-dihydro-6-iodo-3-oxa-1 described in JP-B-5-63482 and JP-A-62-12734. Iodinated compounds of perfluorovinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.

Among these, the fluoroolefin is preferably at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.

The fluoroolefin is more preferably vinylidene fluoride, more preferably vinylidene fluoride and at least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. .

The fluoropolymer (A) may contain a non-fluorinated monomer unit copolymerizable with the fluoroolefin in addition to the fluoroolefin unit. Examples of the non-fluorine monomer copolymerizable with the fluoroolefin include olefins such as ethylene, propylene, and isobutylene, vinyl ether monomers, allyl ether monomers, vinyl ester monomers, acrylics, and the like. And monomers based on methacrylic monomers and methacrylic monomers.

The fluoropolymer (A) preferably contains a vinylidene fluoride unit as the fluoroolefin unit. From the viewpoint of compatibility with the acrylic polymer (B), in the fluoropolymer (A), the vinylidene fluoride unit is preferably 50 mol% or more with respect to all the polymerized units constituting the fluoropolymer (A). 70 mol% or more, more preferably 95 mol% or less. More preferably, the fluoropolymer (A) contains a vinylidene fluoride unit and at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene.

The fluoropolymer (A) includes VdF / TFE / CTFE copolymer, VdF / TFE copolymer, VdF / TFE / HFP copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, and PVdF. It is preferably at least one selected from the group consisting of: VdF / TFE / CTFE = 40 to 99/1 to 50/0 to 30 (mol%), VdF / TFE = 50 to 99/1 to 50 ( Mol%), VdF / TFE / HFP = 45 to 99/0 to 35/5 to 50 (mol%), VdF / CTFE = 40 to 99/1 to 30 (mol%), and VdF / HFP = 50 to More preferably, it is at least one selected from the group consisting of 99/1 to 50 (mol%).

The acrylic polymer (B) includes a repeating unit (acrylic monomer unit) based on an acrylic monomer. The acrylic monomer is preferably at least one selected from the group consisting of acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester.

The acrylic polymer (B) preferably contains at least one acrylic monomer unit selected from the group consisting of acrylic acid, acrylic acid ester, methacrylic acid and methacrylic acid ester. More preferably, it comprises at least one acrylic monomer unit selected from the group consisting of acids and acrylic esters.

As the acrylic ester, an alkyl alkyl ester having 1 to 10 carbon atoms in the alkyl group is preferable, and methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl. More preferably, it is at least one alkyl acrylate selected from the group consisting of acrylate and glycidyl acrylate, and at least one selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate. More preferably, it is an acrylic acid alkyl ester.

As the methacrylic acid ester, a methacrylic acid alkyl ester having 1 to 10 carbon atoms in the alkyl group is preferable, and a group consisting of methyl methacrylate, propyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and glycidyl methacrylate. More preferably, it is at least one alkyl methacrylate selected more preferably, and more preferably at least one alkyl methacrylate selected from the group consisting of methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

The acrylic polymer (B) is at least one acrylic selected from the group consisting of methacrylic acid ester units and acrylic acid, methacrylic acid and acrylic acid esters from the viewpoint of easily adjusting the surface free energy of the coating layer. It is preferable that a monomer unit is included, and it is more preferable to include a methacrylic acid ester unit and a methacrylic acid unit from the viewpoint of excellent film forming property and easy adjustment of the surface free energy of the coating layer.

More preferably, the acrylic polymer (B) contains 5 to 98% by mass of methacrylic acid ester units and 95 to 2% by mass of methacrylic acid units with respect to all the structural units of the acrylic polymer (B).

The acrylic polymer (B) may contain a hydrolyzable silyl group-containing monomer unit. As a hydrolyzable silyl group-containing monomer,
CH ₂ = CHSi (OCH ₃ ) ₃ ,
CH ₂ = CHSi (CH ₃ ) (OCH ₃ ) ₂ ,
_{CH 2 = C (CH 3)} Si (OCH 3) 3,
_{CH 2 = C (CH 3)} Si (CH 3) (OCH 3) 2,
_{CH 2 = CHSi (OC 2 H} 5) 3,
_{CH 2 = CHSi (OC 3 H} 7) 3,
_{CH 2 = CHSi (OC 4 H} 9) 3,
CH ₂ = CHSi (OC ₆ H ₁₃ ) ₃ ,
_{CH 2 = CHSi (OC 8 H} 17) 3,
_{CH 2 = CHSi (OC 10 H} 21) 3,
_{CH 2 = CHSi (OC 12 H} 25) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (OCH 3) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = CHCOO (CH 2)} 3 Si (OC 2 H 5) 3,
_{CH 2 = CHCOO (CH 2)} 3 Si (CH 3) (OC 2 H 5) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (OC 2 H 5) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 3 Si (CH 3) (OC 2 H 5) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 2 O (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 2 (CH 2) 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = C (CH 3)} COO (CH 2) 11 Si (OCH 3) 3,
_{CH 2 = C (CH 3)} COO (CH 2) 11 Si (CH 3) (OCH 3) 2,
_{CH 2 = CHCH 2 OCO (o} -C 6 H 4) COO (CH 2) 3 Si (OCH 3) 3,
_{CH 2 = CHCH 2 OCO (o} -C 6 H 4) COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
_{CH 2 = CH (CH 2)} 4 Si (OCH 3) 3,
_{CH 2 = CH (CH 2)} 8 Si (OCH 3) 3,
_{CH 2 = CHO (CH 2)} 3 Si (OCH 3) 3,
_{CH 2 = CHCH 2 O (CH} 2) 3 Si (OCH 3) 3,
_{CH 2 = CHCH 2 OCO (CH} 2) 10 Si (OCH 3) 3
Etc. These hydrolyzable silyl group-containing monomers may be used alone or in combination of two or more.

Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropylmethyl are preferable because of good adhesion and storage stability. At least one selected from the group consisting of diethoxysilane is preferred.

The content of the hydrolyzable silyl group-containing monomer unit is preferably 0.1 to 2% by mass with respect to all the structural units of the acrylic polymer (B). If it is less than 0.1% by mass, the adhesion may be insufficient, and if it exceeds 2% by mass, the film forming property and storage stability may be unstable. A more preferred upper limit is 1.5% by mass. A more preferred lower limit is 0.2% by mass.

The acrylic polymer (B) is further at least one selected from the group consisting of an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site and an ethylenically unsaturated group-containing monomer having a light stabilization site. It preferably contains polymerized units based on seed monomers.

As the ethylenically unsaturated group-containing monomer having an ultraviolet absorption site, RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) (hereinafter referred to as RUVA-93), which is a methacrylate having a benzotriazole type ultraviolet absorption site, A cyanoacrylate type etc. can be mentioned. Further, methacrylic acid esters and acrylic esters of UV absorbers obtained by reaction of known UV absorbers containing hydroxyl groups such as benzophenone, benzotriazole, and triazine with acid halides such as methacrylic acid chloride and acrylic acid chloride. Acid ester etc. can also be mentioned. These may be used alone or in combination of two or more.
The ultraviolet absorbing site is preferably a site having a benzotriazole-based hydroxyl group.

Specific examples of the benzophenone-based compound having an ethylenically unsaturated group-containing monomer include, but are not limited to, for example, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4 -[2- (meth) acryloyloxy] butoxybenzophenone, 2,2'-dihydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy -4 '-(2-hydroxyethoxy) benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (meth) acryloyloxy] ethoxybenzophenone, and 2-hydroxy-3-tert-butyl-4- [2- (Meth) acryloyloxy] butoxybenzophenone and the like are preferable Can be mentioned. These may be used alone or in combination of two or more.

The specific benzotriazole-based compound having an ethylenically unsaturated group-containing monomer is not limited, and, for example, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H— Benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H- Benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyl Oxyethylphenyl] -2H-benzotriazole and 2- [2′-hydroxy-5 ′-(β- (me Ta) acryloyloxyethoxy) -3'-tert-butylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzo Triazole (RUVA-93) etc. are mentioned preferably. These may be used alone or in combination of two or more.

The triazine-based compound having a specific ethylenically unsaturated group-containing monomer is not limited. For example, 2,4-diphenyl-6- [2-hydroxy-4- (2-acryloyloxyethoxy)] -S-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine, and 2,4-bis (2-methoxy) Preferred examples include phenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy)]-s-triazine. These may be used alone or in combination of two or more.

Examples of the ethylenically unsaturated group-containing monomer having a light stabilizing site include Adeka Stub LA82 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub LA87 (Asahi Denka Kogyo Co., Ltd.), etc. Mention may also be made of esters of stabilizers with methacrylic acid and acrylic acid. These may be used alone or in combination of two or more.

Specific examples of the ethylenically unsaturated group-containing monomer having a light stabilizing site include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl- 4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4 -Iminopiperidyl methacrylate, 2,2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2, 2,6,6-pentamethyl-4-piperidyl methacrylate and the like.

The acrylic polymer (B) is composed of non-fluorinated olefin units such as unsaturated carboxylic acids, hydroxyl group-containing alkyl vinyl ethers, carboxylic acid vinyl esters, α-olefins, aromatic vinyl monomers, and epoxy group-containing monomers. It may be included.

Specific examples of the unsaturated carboxylic acids include, for example, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid, itaconic acid monoester, maleic acid Maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, undecylenic acid and the like. Among these, vinyl acetate, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, and fumaric acid monoester are preferred because of their low homopolymerizability and difficulty in forming homopolymers and easy control of the introduction of carboxyl groups. At least one selected from the group consisting of esters, 3-allyloxypropionic acid, and undecylenic acid is preferred.

Specific examples of the hydroxyl group-containing alkyl vinyl ethers include, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy- Examples include 2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. In view of excellent polymerization reactivity, at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable.

Specific examples of vinyl carboxylates include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate. , Vinyl benzoate, vinyl para-t-butylbenzoate and the like. By using carboxylic acid vinyl esters, it is possible to impart properties such as improved gloss and increased glass transition temperature to the resulting coating film.

Specific examples of α-olefins include ethylene, propylene, n-butene, isobutene, styrene, and the like. By using α-olefins, properties such as improvement in flexibility can be imparted to the resulting coating film.

Specific examples of the aromatic vinyl monomer include styrenes such as styrene and α-methylstyrene. Specific examples of the epoxy group-containing monomer include allyl glycidyl ether.

The acrylic polymer (B) is 5 to 98% by mass of methacrylic acid ester units, 93 to 1.9% by mass of methacrylic acid units, and 0.1 to 2 with respect to all the structural units of the acrylic polymer (B). The hydrolyzable silyl group-containing monomer unit is preferably contained in an amount of 90% by mass, 90 to 98% by mass of methacrylic acid ester units, 8 to 1.9% by mass of methacrylic acid units, and 0.1 to 2%. More preferably, it contains a mass% hydrolyzable silyl group-containing monomer unit.

The composite polymer particles are obtained by subjecting the fluoroolefin to aqueous dispersion polymerization to obtain an aqueous dispersion containing fluoropolymer (A) particles, and at least the acrylic polymer in the aqueous dispersion containing fluoropolymer (A) particles. It is preferable that the monomer is obtained by a production method including a step of seed polymerization of the fluoropolymer (A) particles.

The aqueous dispersion polymerization and the seed polymerization are carried out in the presence of a non-reactive anionic surfactant, a reactive anionic surfactant, a non-reactive nonionic surfactant, a reactive nonionic surfactant, etc., if desired. You can also.

From the viewpoint of easily adjusting the surface free energy of the coating layer, the seed polymerization is performed in the presence of at least one selected from the group consisting of a reactive anionic surfactant and a reactive nonionic surfactant. It is preferable to carry out in the presence of a reactive anionic surfactant.

As the reactive anionic surfactant,
Equation _{(3): CH 2 = C} (CH 3) CH 2 CH 2 -O- (BO) m - (EO) n -SO 3 NH 4
(In the formula, BO is a butylene oxide unit; EO is a CH ₂ CH ₂ O or CH (CH ₃ ) O unit; m is an integer of 0 to 50; n is an integer of 0 to 100; m + n is an integer of 0 to 150. Compound (3) represented by:
Equation _{(4): CH 2 = CHCH} 2 -O-R 1 -X
(Wherein R ¹ is a hydrocarbon chain optionally having an oxygen atom and / or a nitrogen atom, X is SO ₃ Y (Y is NH ₄ or an alkali metal)) (4) Etc.

As a commercial item of a compound (3), Lathel PD-104 by Kao Corporation etc. are mentioned, for example.

R ¹ in Formula (4) is a hydrocarbon chain that may have an oxygen atom and / or a nitrogen atom.
R ¹ is preferably a hydrocarbon group containing an oxyalkylene group.
X is SO ₃ Y (Y is NH ₄ or an alkali metal). As an alkali metal, Na and K are preferable.
As said oxyalkylene group, C2-C4 linear or branched oxyalkylene groups, such as ethylene oxide, propylene oxide, butylene oxide, are mentioned.

Examples of the compound represented by the formula (4) include the formula (4a):

（式中、Ｒ^１’は直鎖状又は分岐状であり、酸素原子、フェニル基またはフェニレン基を含んでもよい炭化水素鎖；ＡＯは炭素数２〜４の直鎖状または分岐鎖状のオキシアルキレン基；ｎは１〜１００の整数；ＸはＳＯ_３Ｙ（ＹはＮＨ_４またはアルカリ金属原子）である。）で示される化合物（４ａ）が好ましく挙げられる。
Ｒ^１’の炭素数は１〜５１が好ましく、５〜２１がより好ましく、１０〜１６が更に好ましい。
ｎは、１〜６０の整数が好ましく、５以上の整数がより好ましく、１０以上の整数が更に好ましく、３０以下の整数がより好ましく、２０以下の整数が更に好ましく、１５以下の整数が特に好ましい。
上記アルカリ金属原子としては、Ｎａ、Ｋが好ましい。

(Wherein R ¹ ′ is a linear or branched hydrocarbon chain which may contain an oxygen atom, a phenyl group or a phenylene group; AO is a linear or branched oxy group having 2 to 4 carbon atoms; alkylene group; n is an integer 1 to 100;. X is _SO 3 Y (Y is NH ₄ or an alkali metal atom) is a compound represented by) (4a) are preferably mentioned.
The number of carbon atoms in R ¹ 'is preferably 1 to 51, more preferably from 5 to 21, more preferably 10 to 16.
n is preferably an integer of 1 to 60, more preferably an integer of 5 or more, further preferably an integer of 10 or more, more preferably an integer of 30 or less, still more preferably an integer of 20 or less, and particularly preferably an integer of 15 or less. .
As the alkali metal atom, Na and K are preferable.

As the formula (4a), the following formula (4a-1):

（式中、Ｒ^３’は直鎖状又は分岐状であり、フェニル基またはフェニレン基を含んでもよい炭素数１〜５０の炭化水素鎖；ＡＯは炭素数２〜４の直鎖状または分岐鎖状のオキシアルキレン基；ｎは１〜１００の整数；ＸはＳＯ_３Ｙ（ＹはＮＨ_４またはアルカリ金属原子、たとえばＮａ、Ｋ）である。）で示される化合物（４ａ−１）、又は、下記式（４ａ−２）；

(In the formula, R ³ ′ is linear or branched, and may have a phenyl group or a phenylene group. The hydrocarbon chain having 1 to 50 carbon atoms; AO is a linear or branched chain having 2 to 4 carbon atoms; N is an integer of 1 to 100; X is SO ₃ Y (Y is NH ₄ or an alkali metal atom such as Na, K)), or (4a-1) Following formula (4a-2);

（式中、Ｒ^４’は炭素数１〜５０のアルキル基；ＡＯは炭素数２〜４の直鎖状または分岐鎖状のオキシアルキレン基；ｎは１〜１００の整数；ＸはＳＯ_３Ｙ（ＹはＮＨ_４またはアルカリ金属原子、たとえばＮａ、Ｋ）である。）で示される化合物（４ａ−２）が好ましく挙げられる。

Wherein R ⁴ ′ is an alkyl group having 1 to 50 carbon atoms; AO is a linear or branched oxyalkylene group having 2 to 4 carbon atoms; n is an integer of 1 to 100; X is SO ₃ Y (Y is NH ₄ or an alkali metal atom such as Na, K).) (4a-2) is preferred.

In the formula (4a-1), R ³ ′ has 1 to 50 carbon atoms, preferably 5 to 20 and more preferably 10 to 15. n is an integer of 1 to 100, preferably an integer of 1 to 60 from the viewpoint of dispersion stability and water resistance, more preferably an integer of 5 to 30, and an integer of 10 to 15. More preferably.
X is preferably SO ₃ NH ₄ .
AO is preferably ethylene oxide.

As a commercial item of a compound (4a-1), SE series, SR series (all are the products made by ADEKA) etc. of ADEKA rear soap can be mentioned, for example.

In the formula (4a-2), R ⁴ ′ is an alkyl group having 1 to 50 carbon atoms, preferably 5 to 20, and more preferably 10 to 15. n is an integer of 1 to 100, preferably an integer of 1 to 20, and more preferably 5 to 15 from the viewpoints of dispersion stability and water resistance.
X is preferably SO ₃ NH ₄ .
AO is preferably ethylene oxide.

As a commercial item of a compound (4a-2), Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd. product) etc. are mentioned, for example.

In the seed polymerization, the amount of the reactive anionic surfactant added is preferably 0.15 to 100 parts by mass, more preferably 0.77 parts by mass or more, and 1.5 parts by mass with respect to 100 parts by mass of the seed particles. Part or more is more preferable, 70 parts by mass or less is more preferable, and 50 parts by mass or less is still more preferable.

The coating layer is preferably made of a dry paint film of a paint blended with the resin, and more preferably dried after the paint is applied.

The paint may be a solvent paint, a water paint, a powder paint or the like, but is preferably a solvent paint or a water paint, and more preferably a water paint. That is, the paint preferably contains the resin and water.

The solvent in the solvent coating is preferably an organic solvent, and esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; propylene glycol methyl ether and ethyl cellosolve Diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n Undecane, n- dodecane, aliphatic hydrocarbons such as mineral spirit; a mixed solvent, and the like.
Among these, esters are more preferable, and butyl acetate is more preferable.

The solid content concentration of the paint blended with the resin is usually 20% by mass or more, preferably 30% by mass or more from the viewpoint of good coating efficiency, and 70% by mass or less, preferably 60% by mass from the viewpoint of storage stability. It is as follows.

The paint may further contain a non-reactive surfactant. In particular, when the paint is an aqueous paint, it preferably contains a non-reactive surfactant.

As the non-reactive surfactant, for example, a non-reactive anionic surfactant, a non-reactive nonionic surfactant or a combination thereof can be used. In some cases, a non-reactive amphoteric surfactant, a non-reactive surfactant can be used. Cationic surfactants can also be used.

As the non-reactive anionic surfactant, for example, a sodium salt of a higher alcohol sulfate, a sodium alkylbenzene sulfonate, a sodium salt of a dialkyl succinate sulfonic acid or a sodium salt of an alkyl diphenyl ether sulfonic acid can be used. Among these, preferred examples include sodium alkylbenzene sulfonate, sodium lauryl sulfate, polyoxyethylene alkyl (or alkylphenyl) ether sulfonate, and the like. As the non-reactive nonionic surfactant, for example, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether can be used. Preferred specific examples are polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like. As the non-reactive amphoteric surfactant, lauryl betaine is suitable. As the non-reactive cationic surfactant, for example, alkyl pyridinium chloride, alkyl ammonium chloride and the like can be used. In addition, an emulsifier that is copolymerizable with the monomer, such as sodium styrenesulfonate, sodium alkylarylsulfonate, and the like can also be used.

Non-reactive nonionic surfactants include polyoxyethylene alkyl ether, polyoxypolyalkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters. Examples of the polyoxyethylene alkyl ether include Emulgen 120 (Kao Corporation).

Non-reactive anionic surfactants include fatty acid salts, alkenyl succinates, higher alcohol sulfates, alkylbenzene sulfonates, alkyl sulfonates, alkyl diphenyl ether disulfonates, naphthalene sulfonic acid formalin condensates, special carboxylic acids Type polymer surfactants. Specific examples of the non-reactive anionic surfactant include New Coal 707-SF (Nippon Emulsifier Co., Ltd.), Haitenol NF-08 (Daiichi Kogyo Seiyaku Co., Ltd.) and the like.

Various additives can be further blended in the paint according to the required characteristics. Additives include film forming aids, curing agents, curing accelerators, curing retardants, pigments, pigment dispersants, antifoaming agents, leveling agents, ultraviolet absorbers, light stabilizers, thickeners, adhesion improvers, Examples include matting agents.

The curing agent is selected according to the type of curable functional group of the resin. For example, for a hydroxyl group-containing fluorine-containing polymer, an isocyanate curing agent, a melamine resin, a silicate compound, an isocyanate group-containing silane compound, and the like are preferable. It can be illustrated. In addition, amino-based curing agents and epoxy-based curing agents are used for carboxyl group-containing fluorine-containing polymers, and carbonyl-group-containing curing agents, epoxy-based curing agents, acid anhydride-based curing agents are used for amino group-containing fluorine-containing polymers. Is usually adopted.

The curing agent also includes a non-blocking polyisocyanate compound, a block polyisocyanate compound, a melamine resin, a crosslinking agent having at least one group selected from the group consisting of an aziridine group, a carbodiimide group, and an oxazoline group, hydrazine Derivatives and the like.

Non-blocking polyisocyanate compounds are excellent in curability at room temperature and also in terms of crosslinking reactivity.

The non-block type polyisocyanate compound means a normal isocyanate compound other than the block type polyisocyanate compound obtained by reacting an alcohol or oxime compound with an isocyanate compound.

Examples of the non-blocking polyisocyanate compound include non-blocking polyisocyanate modified with a polyethylene oxide compound described in JP-A-11-310700, JP-A-7-330861, JP-A-61-291613 and the like. Isocyanate compounds are preferred.

Specifically, a non-block type aliphatic polyisocyanate compound or a non-block type aromatic polyisocyanate compound modified with a polyethylene oxide compound is exemplified. Among these, non-block type aliphatic polyisocyanate compounds are preferable from the viewpoint of excellent weather resistance.

As the chain aliphatic polyisocyanate compound among the non-block type aliphatic polyisocyanate compounds, for example, trimethylene diisocyanate, tetramethylene diisocyanate, 1,6-diisocyanatohexane (= hexamethylene diisocyanate), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl Diisocyanates such as captroate; lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8- Isocyanate-4-isocyanate methyl octane, 1,3,6-triisocyanate hexane, polyisocyanates such as 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane can be exemplified.

Among the non-block type aliphatic polyisocyanate compounds, examples of the alicyclic polyisocyanate compound include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1-isocyanato-3,3,5. -Trimethyl-5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or Diisocyanates such as 1,4-bis (isocyanatomethyl) cyclohexane; 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethyl isocyanate cyclohexane 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo ( 2.2.1) Heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatemethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl -3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl)- Illustrative are polyisocyanates such as cyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane. it can.

Examples of non-block type aliphatic polyisocyanate compounds include tolylene diisocyanate.

These isocyanate compounds may be used alone or in combination of two or more.

Examples of the polyethylene oxide compound that is a modifier include polyoxyethylene monooctyl ether, polyoxyethylene monolauryl ether, polyoxyethylene monodecyl ether, polyoxyethylene monocetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene mono Polyoxyethylene C8-24 alkyl ethers such as oleyl ether, preferably polyoxyethylene C10-22 alkyl ethers, especially polyoxyethylene alkyl ethers such as polyoxyethylene C12-18 alkyl ethers; for example, polyoxyethylene monooctylphenyl ether , Polyoxyethylene monononyl phenyl ether, polyoxyethylene monodecyl phenyl ether, etc. Polyoxyethylene monoalkylaryl ethers such as 2-alkyl-C6-12 aryl ethers; for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan distea Polyoxyethylene sorbitan mono-, di- or tri-C10-24 fatty acid esters such as polyoxyethylene sorbitan tristearate; polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate Nonionic emulsifiers such as polyoxyethylene mono C10-24 fatty acid esters such as acid esters, polyoxyethylene mono higher fatty acid esters, etc. Compounds known to can be exemplified. These compounds can be used alone or in combination of two or more. Preferable examples include polyoxyethylene C8-24 alkyl ether and polyoxyethylene C8-12 alkylphenyl ether from the viewpoint of easy water dispersibility.

The modification can be performed, for example, by a method in which a polyisocyanate compound is mixed with a modifying agent in a solution and reacted by heating.

The ratio of the polyisocyanate compound and the modifier is 0.01 to 0.034 equivalent, preferably 0.015 to 0.03 equivalent of an active hydrogen atom of the modifier with respect to 1 equivalent of isocyanate group in the polyisocyanate compound. You can choose from a range of degrees.

Examples of commercially available polyethylene oxide-modified non-blocking polyisocyanate compounds include, but are not limited to, Bayhijur 3100, Bayhjul TPLS2150, etc. manufactured by Sumitomo Bayer Urethane Co., Ltd .; It is not limited.

The non-blocking polyisocyanate compound is usually used in the form of an aqueous solution or an aqueous dispersion.

As the block type polyisocyanate compound, known curing agents such as Sumidur BL3175 manufactured by Sumika Bayer Urethane Co., Ltd. and Duranate TPA-B80E manufactured by Asahi Kasei Co., Ltd. can be used.

Examples of the crosslinking agent having an aziridine group include XAMA2 and XAMA7 supplied from BF-Goodrich.
Examples of the crosslinking agent having a carbodiimide group include UCARLNK Crosslinker XL-29SE supplied from Union Carbide, Carbodilite E-02, E-04, SV-02, V-02V-02-L2, V, Nisshinbo Chemical Co., Ltd. -04, V-10, etc. are exemplified.
Examples of cross-linking agents having an oxazoline group include Epocross K-1010E, Epocross K-1020E, Epocross K-1030E, Epocross K-2010E, Epocross K-2020E, Epocross K-2030E supplied from Nippon Shokubai Co., Ltd. Epocros WS-500 can be exemplified.

The hydrazine derivative has at least two hydrazine residues and may particularly preferably be derived from saturated fatty acid dicarboxylic acids. Of particular importance are aliphatic carboxylic acid dihydrazides having 2 to 10 carbon atoms. Suitable dihydrazides of this type are malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide and / or sebacic acid dihydrazide. Carbonic polyhydrazide such as carbonic dihydrazide is exemplified.

It is preferable to add a hardening | curing agent so that it may become 0.1-5 molar equivalent with respect to 1 equivalent of curable functional groups of the said resin, More preferably, it is 0.5-1.5 molar equivalent.

The content of the curable functional group of the resin can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and neutralization titration depending on the type of monomer.

Examples of the curing accelerator include organic tin compounds, acidic phosphate esters, reaction products of acidic phosphate esters and amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, organic titanate compounds, amine compounds, Examples include lead octylate.

1 type may be used for a hardening accelerator and it may use 2 or more types together. The blending ratio of the curing accelerator is preferably 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻² parts by mass with respect to 100 parts by mass of the resin, and 5.0 × 10 ^{−5 to} 1.0 × 10 ^−3. A mass part is more preferable.

The hydrophilic layer preferably contains at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorocarbon sulfonic acid resins, transition metal polyvalent ions, and metal oxides. It is more preferable that a product is included.

The colloidal silica is produced, for example, by sodium removal of water glass (ion exchange method, acid decomposition method, peptization method), and the primary particle size is 4 to 150 nm, preferably 5 to 50 nm. Is usually supplied as an aqueous dispersion and can be used as it is.

The colloidal silica can be used on either the acidic side or the basic side in a water-dispersible state, and examples of the acidic colloidal silica include a trade name SNOWTEX-O or SNOWTEX-OL (Nissan). Non-stabilized silica (pH 2 to 4) commercially available as Chemical Industry Co., Ltd.) can be used. On the other hand, the colloidal silica on the basic side includes silica (pH 8.4 to 10) stabilized by addition of a trace amount of alkali metal ions, aluminum ions, ammonium ions or amines. C, Snowtex N, (manufactured by Nissan Chemical Industries, Ltd.), trade name Ludox HS-40, HS-30, LS, SM-30, TM, AS, AM (above, manufactured by DuPont, USA), Examples include commercial names such as Narcoque (US, manufactured by Narco Chemical Co., Ltd.) and commercial names Mitten (US, manufactured by Monsanto Chemical Co., Ltd.). When the pH is 6 to 8, not only the stability of the colloidal silica but also the stability of the paint when it is made into a paint tends to agglomerate and gel.

An organosilicon compound can be used together with the colloidal silica, and its purpose is that, in addition to the adhesion to the inorganic substrate and organic substrate, weather resistance, chemical resistance, and film formability when formed into a paint. The purpose is to further improve the flexibility. The organosilicon compound has the formula:
R ³¹ _a Si (OR ³² ) _4-a
Wherein R ³¹ represents a non-hydrolyzable group or a hydrogen atom, R ³² represents an alkyl group, an aryl group, an alkenyl group or a hydrogen atom, and a is 0, 1 or 2. Is the body.

Examples of the non-hydrolyzable group include alkyl groups such as methyl, ethyl and propyl, aryl groups such as phenyl group, tolyl group and mesityl group, alkenyl groups such as vinyl group and allyl group, and γ-chloropropyl group. Epoxyalkyl such as haloalkyl group, γ-aminopropyl group, aminoalkyl group such as γ- (2-aminoethyl) aminopropyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group Group, γ-mercaptoalkyl group, methacryloyloxyalkyl group such as γ-methacryloyloxypropyl group, hydroxyalkyl group such as γ-hydroxypropyl group, and the like. Among these substituents, preferred for the present invention are alkyl groups having 8 or less carbon atoms, more preferably 4 or less carbon atoms, and substituents therefor, because the reactivity decreases when the number of carbon atoms in the substituent is large. Are an aminoalkyl group, an epoxyalkyl group, a methacryloyloxyalkyl group, a hydroxyalkyl group and an aryl group, a phenyl group, and an alkenyl group having 2 to 3 carbon atoms. The alkyl group, aryl group, and alkenyl group of R ³² are the same as those of R ³¹ described above, but particularly preferable ones are those having 4 or less carbon atoms because the reactivity decreases when the number of carbon atoms in the substituent is large. It is an alkyl group.

Examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ -Chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane. From the viewpoints of properties and flexibility, methyltrimethoxysilane, phenyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and the like are preferable.

Examples of the organosilicate include JP-A-11-343462, JP-A-2002-129111, JP-A-2002-129110, JP-A-2007-153930, JP-A-2008-013771, and International Publication No. 94. The compound described in No. 06870 can also be used in the present invention, and when the hydrolyzable group is hydrolyzed, it becomes a hydrophilic group.

Examples of the organosilicate include a formula:
Si (OR ⁴¹ ) ₄
(In the formula, R ⁴¹ is an organic group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, for example, a linear or branched alkyl group, an aryl group which may be monocyclic or polycyclic, etc.) Or at least one OR ⁴¹ group of the tetrafunctional organosilicate compound or its condensate of the above formula is a nonionic group such as a polyoxyalkylene chain (polyoxyethylene chain (polyoxyethylene chain). Organosilicate compounds having a nonion-modified alkyl group substituted with an organic group containing, necessarily including); for example, tetradiethoxysilane, tetratriethoxysilane, tetrapropoxysilane, tetradipropoxysilane, dipolyethoxysilane, ethoxytripropoxysilane And ethoxytributoxysilane It is. An organosilicate compound having 1 to 3 functional groups may be used as long as it has hydrophilicity.

Examples of the tetrafunctional organosilicate compound include tetrahydroxysilane; tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane; and condensates thereof.

As the organosilicate, those having a nonion-modified alkyl group are particularly preferable. Preferred examples of nonionic modified organosilicate compounds include modified organosilicate compounds in which at least one hydrolyzable group contains an alkylene oxide chain, such as an ethylene oxide chain. In addition, the propylene oxide chain and the butylene oxide chain may be included. Of these, alkylene oxide-modified organosilicate and ethylene oxide-modified organosilicate are preferred from the viewpoint of good storage stability.

As the organometallic compound, the formula:
X _b M (OR ⁵¹ ) _a R ⁵² _c
[Wherein, a is an integer of 0-6, b is an integer of 0-5, c is an integer of 0-6 (provided that a + b + c ≧ 3, and a and c are not 0 at the same time), X is Either the same or different, a monovalent organic group having 1 to 5000 carbon atoms or a hydrogen atom, which may contain an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom, M represents at least a trivalent valence. The metal atoms, R ⁵¹ may be the same or different, each having an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom, a monovalent organic group having 1 to 1000 carbon atoms, a siloxane residue or hydrogen Atom, R ⁵² are the same or different and each represents an organic group having 1 to 20 carbon atoms having the ability to chelate which may contain oxygen atom, nitrogen atom, fluorine atom and / or chlorine atom] Water Solution organometallic compound, co-oligomers comprising two or more of the oligomers or organometallic compounds.

The perfluorocarbon sulfonic acid resin is a resin in which a sulfonic acid group (some of which may be in the form of a salt) is bonded to perfluorocarbon.

The perfluorocarbon sulfonic acid resin is a polymer unit represented by — (CF ₂ —CFZ) — (wherein Z is H, Cl, F, or a perfluoroalkyl group having 1 to 3 carbon atoms). ,-(CF ₂ -CF (—O— (CF ₂ ) _m —SO ₃ H)) — (wherein m is an integer of 1 to 12) It is a coalescence. When the hydrophilized layer contains a perfluorocarbon sulfonic acid resin having the above structure, it exhibits high durability and hydrophilicity and excellent stain resistance. From the viewpoint of obtaining high hydrophilicity, m is preferably an integer of 1 to 6, and Z is preferably F.

As the perfluorocarbon sulfonic acid resin, a perfluorocarbon sulfonic acid resin comprising a copolymer of a fluorinated vinyl ether compound represented by the following general formula (1) and a fluorinated olefin monomer represented by the following general formula (2): Those obtained by hydrolyzing the precursor are preferred.

_{CF 2 = CF-O- (CF} 2) m -W (1)
(In the formula, m is an integer of 1 to 12. W is a functional group that can be converted to —SO ₃ H by hydrolysis.)
CF ₂ = CFZ (2)
(In the formula, Z is H, Cl, F, or a perfluoroalkyl group having 1 to 3 carbon atoms.)

As W which is a functional group that can be converted to —SO ₃ H by hydrolysis in the above formula (1), SO ₂ F, SO ₂ Cl, or SO ₂ Br is preferable. m is preferably an integer of 1 to 6. When m is an integer of 1 to 6, the equivalent weight EW of the perfluorocarbonsulfonic acid resin tends to be low and the hydrophilicity tends to be high.
In the above formulas (1) and (2), a perfluorocarbon sulfonic acid resin precursor in which W is SO ₂ F and Z is F is preferable, and among them, a solution having high hydrophilicity and high resin concentration is obtained. From the viewpoint, it is more preferable that m is an integer of 1 to 6, W is SO ₂ F, and Z is F. A copolymer having the above structure is also preferable in that the resistance to radical species generated by photocatalysis is enhanced.

The perfluorocarbon sulfonic acid resin precursor can be synthesized by known means. For example, a vinyl fluoride compound having a functional group that can be converted to —SO ₃ H by hydrolysis using a polymerization solvent such as a fluorinated hydrocarbon in a polymerization method using a peroxide of a radical generator A method of polymerizing a solution by filling and dissolving a fluorinated olefin gas such as tetrafluoroethylene (TFE) and polymerizing it (solution polymerization), and using a vinyl fluoride compound itself as a polymerization solvent without using a solvent such as fluorine-containing hydrocarbon Method (bulk polymerization), a method in which a vinyl fluoride compound and a fluorinated olefin gas are charged and reacted using an aqueous solution of a surfactant as a medium (emulsion polymerization), a co-emulsifier such as a surfactant and alcohol. A method of polymerizing by emulsifying and reacting with an aqueous solution of vinyl fluoride compound and fluorinated olefin gas (miniemulsion polymerization, microemulsion) And a polymerization method by suspending and reacting a gas of a vinyl fluoride compound and a fluorinated olefin in an aqueous solution of a suspension stabilizer (suspension polymerization) is known. Those prepared by a polymerization method can also be used.

The perfluorocarbon sulfonic acid resin precursor produced as described above preferably has a melt index (MI) of 0.05 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes. Most preferably, it is 0.2 to 20 g / 10 min. MI is measured using a melt indexer under conditions of 270 ° C. and a load of 2.16 kg according to JIS K 7210, and represents the mass of the extruded polymer in grams per 10 minutes.

The perfluorocarbon sulfonic acid resin precursor produced as described above is preferably extruded using a nozzle or die using an extruder. The molding method and the shape of the molded body at this time are not particularly limited. In order to increase the treatment speed in the hydrolysis treatment and acid treatment described later, the molded body is preferably in the form of pellets of 0.5 cm ³ or less, but a powdered state after polymerization may be used.

The perfluorocarbon sulfonic acid resin precursor molded as described above is subsequently immersed in a basic reaction liquid and subjected to a hydrolysis treatment.

The basic reaction solution used for this hydrolysis treatment is not particularly limited, but is an aqueous solution of an amine compound such as dimethylamine, diethylamine, monomethylamine, monoethylamine, or water of an alkali metal or alkaline earth metal. An aqueous solution of an oxide is preferred, and an aqueous solution of sodium hydroxide or potassium hydroxide is particularly preferred. The content of the alkali metal or alkaline earth metal hydroxide is not particularly limited, but is preferably 10 to 30% by mass with respect to the entire reaction solution. More preferably, the reaction solution further contains a swellable organic compound such as methyl alcohol, ethyl alcohol, acetone and DMSO. Moreover, it is preferable that content of a swelling organic compound is 1-30 mass% with respect to the whole reaction liquid.

The perfluorocarbon sulfonic acid resin precursor is hydrolyzed in the basic reaction liquid, then sufficiently washed with warm water or the like, and then acid-treated. The acid used for the acid treatment is not particularly limited, but preferred are mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as oxalic acid, acetic acid, formic acid and trifluoroacetic acid, and a mixture of these acids and water. Is more preferable. Two or more of the above acids may be used simultaneously. By this acid treatment, the perfluorocarbon sulfonic acid resin precursor is protonated and has —SO ₃ H. The perfluorocarbon sulfonic acid resin obtained by protonation can be dissolved in a protic organic solvent, water, or a mixed solvent of both.

The perfluorocarbon sulfonic acid resin has an equivalent weight EW (dry weight gram of perfluorocarbon sulfonic acid resin per equivalent of proton exchange group) of 200 to 1,000. The equivalent weight EW of the perfluorocarbon sulfonic acid resin is preferably 200 to 950, more preferably 200 to 800. More preferably, it is 200-700, Most preferably, it is 250-600, Most preferably, it is 400-500. When the equivalent weight EW is within the above range, excellent hydrophilicity can be imparted to the perfluorocarbon sulfonic acid resin. As a result, a hydrophilic layer excellent in hydrophilicity can be formed, and an excellent stain resistance effect can be exhibited. If the equivalent weight EW is too small, it becomes soluble in water, so that the hydrophilic layer may be easily peeled off from the coating layer, and if it is too large, the hydrophilicity may be lowered.

Here, the equivalent weight EW of the perfluorocarbon sulfonic acid resin can be measured by subjecting the perfluorocarbon sulfonic acid resin to salt substitution and back-titration of the solution with an alkaline solution.

As the transition metal polyvalent ions, cerium ions are particularly preferable from the viewpoint of effectively improving radical resistance. In addition, although cerium ion can take the state of +3 valence or +4 valence, it is not specifically limited in this embodiment. The coating layer preferably contains a perfluorocarbon sulfonic acid resin and a transition metal polyvalent ion. In this case, the transition metal polyvalent ion is preferably capable of ionic bonding with the sulfonic acid group of the perfluorocarbon sulfonic acid resin. . Hereinafter, description will be made by taking cerium ions as an example.

In the coating layer, it is preferable that cerium ions are blended in the perfluorocarbon sulfonic acid resin. Although the method of mix | blending a cerium ion in a perfluorocarbon sulfonic acid resin is not specifically limited, For example, the following method is mentioned.
(1) A method of immersing perfluorocarbon sulfonic acid resin in a solution containing cerium ions.
(2) A method of adding a salt containing cerium ions into a solution of perfluorocarbon sulfonic acid resin.
(3) A method of mixing a solution containing cerium ions and a solution of perfluorocarbon sulfonic acid resin.
In the perfluorocarbon sulfonic acid resin obtained by the above method, it is considered that a part of the sulfonic acid group is ion-exchanged with cerium ions.

Here, the cerium ion may be +3 or +4, and various cerium salts are used to obtain a solution containing cerium ions. Specific examples of salts containing + trivalent cerium ions include cerium acetate (Ce (CH ₃ COO) ₃ .H ₂ O), cerium chloride (CeCl ₃ .6H ₂ O), and cerium nitrate (Ce (NO _{3) 3 · 6H 2 O)} , cerium sulfate _{(Ce 2 (SO 4) 3} · 8H 2 O), cerium carbonate _{(Ce 2 (CO 3) 3} · 8H 2 O) and the like. Examples of the salt containing +4 valent cerium ions include cerium sulfate (Ce (SO ₄ ) ₂ .4H ₂ O), diammonium cerium nitrate (Ce (NH ₄ ) ₂ (NO ₃ ) ₆ ), and tetraammonium cerium sulfate. (Ce (NH ₄ ) ₄ (SO ₄ ) ₄ · 4H ₂ O) and the like. Examples of the organometallic complex salt of cerium include cerium acetylacetonate (Ce (CH ₃ COCHCOCH ₃ ) ₃ .3H ₂ O). Among the above, cerium carbonate is particularly preferable. When cerium carbonate is added to a solution of perfluorocarbon sulfonic acid resin containing water, it dissolves while generating carbon dioxide gas. In this case, there is an advantage that the step of removing the anion species is not required because no anion species remain in the solution of the perfluorocarbon sulfonic acid resin.

For example, when the cerium ion is trivalent, Ce ³⁺ is bonded to _three —SO ₃ ^— when the sulfonic acid group is ion-exchanged with the cerium ion. In the present embodiment, the number of cerium ions contained in the perfluorocarbon sulfonic acid resin is preferably 0.3 to 30 equivalent% with respect to the number of —SO ₃ ^— groups in the resin (hereinafter, this ratio). Is referred to as "cerium ion content"). This numerical range shows that when a trivalent cerium ion is completely bonded to _three —SO ₃ ^— , the sulfonic acid group ion-exchanged with the cerium ion is ion-exchanged with the sulfonic acid group and the cerium ion. It is synonymous with 0.9 to 90% with respect to the total amount with the sulfonic acid group formed (hereinafter, this ratio is referred to as “substitution rate”). The content of cerium ions is more preferably 0.6 to 20 equivalent%, still more preferably 1 to 15 equivalent%. In terms of the above substitution rate, 1.8 to 60% is more preferable, and 3 to 45% is more preferable. By adjusting the content of cerium ions to the above range (0.3 to 30 equivalent%), a highly durable coating film can be produced while maintaining good hydrophilicity. Moreover, the coating film obtained by drying and curing is excellent in flexibility, and further excellent in durability against radical species generated by photocatalytic action, and can also exhibit a photocatalytic function for a long time.

As the metal oxide, a metal oxide having a photocatalytic function is preferable. Examples of the metal oxide include TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, 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, SiC, SiO 2, MoS 2, InPb, RuO 2, CeO 2 or the like Can be mentioned.

Further, a layered oxide having at least one element selected from Ti, Nb, Ta and V (Japanese Patent Laid-Open Nos. 62-74452, 2-172535, 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 publication etc.) can also be used.
Furthermore, these metal oxides are coated with metals such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or those oxides added or immobilized, porous calcium phosphate, or the like. A photocatalyst (see JP-A-10-244166) or the like can also be used.

In addition to these, those imparted with a photocatalytic function in the visible light region by adding a known sensitizer can also be used.
Of these metal oxides having a photocatalytic function, TiO ₂ (titanium oxide) is more preferable because it is non-toxic and excellent in chemical stability.
As titanium oxide, three crystal forms of anatase type, rutile type and brookite type are known, and any of these may be used.
The anatase type having the highest photoactivity is preferred.
The crystal particle diameter (primary particle diameter) of the metal oxide is preferably 1 to 200 nm, more preferably 1 to 50 nm. Here, the crystal particle diameter refers to a value measured by a scattering method using a laser.

The hydrophilization layer is formed from a hydrophilization paint containing at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorocarbon sulfonic acid resins, transition metal polyvalent ions and metal oxides, and water. It is preferred that When the hydrophilic layer is formed from the hydrophilic paint, the hydrophilic layer can be formed without placing a burden on the environment. In the laminate of the present invention, even if the hydrophilic layer is formed from a hydrophilic coating containing water, the hydrophilic layer and the coating layer are firmly bonded. The hydrophilic paint may contain alcohol in addition to water, and examples of the alcohol include methanol, ethanol, propanol and the like.

It is preferable that the laminate further includes a base material. What is necessary is just to select the said base material suitably according to the use mentioned later. For example, siding material, ceramic base material, metal base material, slate base material, foam concrete panel, concrete panel, aluminum curtain wall, steel plate, galvanized steel plate, stainless steel plate, PVC sheet, PET film, polycarbonate base material, acrylic A film, glass, etc. are mentioned.

In the laminate, the substrate, the coating layer, and the hydrophilic layer are preferably laminated in this order. Another layer may be included between the base material and the coating layer. Examples of the other layer include an acrylic resin layer (excluding a layer having a surface free energy of 30 to 40 mJ / m ² ). The coating layer and the hydrophilic layer are preferably directly bonded.

As the base material, a siding material is preferable. Examples of the siding material include ceramic siding materials, metal siding materials, plastic siding materials, and the like.

In particular, in ceramic-based siding materials, acrylic, acrylic silicon, and acrylic urethane coatings are often formed on the surface to improve water resistance, weather resistance, and appearance. It adheres firmly to acrylic coatings, has excellent hot water resistance, and is also excellent in transparency. The ceramic siding material has, for example, a ceramic base material and a coating obtained by coating the ceramic composition on the ceramic base material. The ceramic base material is made of an acrylic resin on the surface. It may be.

A conventionally well-known thing can be used as a ceramic base material. For example, a wet sheet is obtained by papermaking of an aqueous slurry mainly composed of cement, and this is subjected to dehydration press molding, dried and cured, and aqueous kneaded materials such as cement are extruded and cast molded. Conventionally known compositions such as those obtained by curing the molded product obtained by the above can be used. The ceramic base material may have an acrylic resin layer on the surface of the molded body.

The laminate includes a step of coating the base material with a paint blended with the resin to form the coating layer, and colloidal silica, an organosilicate, an organometallic compound, a perfluorocarbon sulfonic acid resin on the coating layer, It can be manufactured by a manufacturing method including the step of forming the hydrophilic layer by applying a paint containing at least one selected from the group consisting of transition metal multivalent ions and metal oxides and water.

The coating material forming the coating layer is preferably an aqueous coating material. In the conventional method, if a coating layer containing water is applied to the coating layer after forming the coating layer with an aqueous coating material, the coating layer is repelled by the coating layer, and a hydrophilic layer cannot be formed or cannot be formed. Even if it was, the adhesiveness of both layers was inadequate. In the manufacturing method, since the coating layer is made of a paint containing the resin, a laminate in which the coating layer and the hydrophilic layer are firmly bonded can be manufactured even if the coating is an aqueous paint.

Examples of the method for applying the coating material for forming the coating layer and the hydrophilic layer include coating methods such as spray coating, roll coating, flow coating, roller, and brush painting. You may dry at 5-200 degreeC after application | coating.

The laminate can be used in a wide range of applications. For example, electrical products (microwave oven, toaster, refrigerator, washing machine, hair dryer, TV, video, amplifier, radio, electric kettle, rice cooker, radio cassette, cassette deck, compact disc player, video camera, etc.), air conditioner Indoor units, outdoor units, air outlets and ducts, air purifiers, heaters, fluorescent lamps, chandeliers, light reflectors such as reflectors, furniture, machine parts, ornaments, combs, eyeglass frames, natural fibers, synthetic fibers (thread-like And textiles obtained from these), office equipment (telephones, facsimiles, copiers (including rolls), photographers, overhead projectors, real projectors, watches, slide projectors, desks, bookshelves, lockers, document shelves, Chairs, bookends, electronic white boards, etc.), automobiles (wheels, door mirrors, motors) , Door knobs, license plates, handles, instrument panels, etc.), kitchen appliances (range hood, sink, kitchen table, kitchen knife, cutting board, water faucet, gas range, ventilation fan, etc.), partition, bath unit, shutter , Blinds, curtain rails, accordion curtains, walls, ceilings, floors, outer walls, handrails, gates, shutters and the like.

Moreover, the following manufacturing method is mentioned as an especially preferable aspect.
That is, a step of forming a coating layer by applying a water-based paint on a substrate and drying, and
A step of forming a hydrophilic layer by applying a hydrophilic coating on the coating layer;
A manufacturing method comprising:
The water-based paint includes composite polymer particles and water,
The hydrophilic paint includes at least one selected from the group consisting of colloidal silica, organosilicate, organometallic compound, perfluorocarbon sulfonic acid resin, transition metal polyvalent ion and metal oxide, and water or alcohol. Is a manufacturing method characterized by

Since the said manufacturing method has said structure, there exists an effect that a hydrophilization layer can be formed with a water-based hydrophilization coating on the coating layer formed with the water-based coating. When a hydrophilic coating was applied on a conventional coating layer, the film forming property was not good and a hydrophilic layer having a good appearance could not be formed.

As said composite polymer particle, what was mentioned above can be used similarly with the said manufacturing method.

The composite polymer particle contains the fluoropolymer (A) and the acrylic polymer (B) in the same particle, and the mass ratio (A / B) of the fluoropolymer (A) to the acrylic polymer (B) is 90/10. 10/90 is preferable.

As fluoropolymer (A), VdF / TFE / CTFE = 40 to 99/1 to 50/0 to 30 (mol%), VdF / TFE = 50 to 99/1 to 50 (mol%), VdF / TFE / HFP = 45 to 99/0 to 35/5 to 50 (mol%), VdF / CTFE = 40 to 99/1 to 30 (mol%), and VdF / HFP = 50 to 99/1 to 50 (mol%) At least one selected from the group consisting of:

The acrylic polymer (B) is 5 to 98% by mass of methacrylic acid ester units, 93 to 1.9% by mass of methacrylic acid units, and 0.1 to 2 with respect to all the structural units of the acrylic polymer (B). The hydrolyzable silyl group-containing monomer unit is preferably contained in an amount of 90% by mass, 90 to 98% by mass of methacrylic acid ester units, 8 to 1.9% by mass of methacrylic acid units, and 0.1 to 2%. More preferably, it contains a mass% hydrolyzable silyl group-containing monomer unit.
The methacrylic acid ester unit is preferably at least one unit selected from the group consisting of methyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

The coating layer preferably has a surface free energy of 30 to 40 mJ / m ² . The surface free energy is more preferably 32 mJ / m ² or more, and more preferably 38 mJ / m ² or less.
The production method further includes a step of aqueous dispersion polymerization of the fluoroolefin to obtain an aqueous dispersion containing the fluoropolymer (A) particles, and the reactivity in the aqueous dispersion containing the fluoropolymer (A) particles. It may include a step of seed polymerizing at least the acrylic monomer into the fluoropolymer (A) particles in the presence of an anionic surfactant.

The aqueous paint may contain a film-forming aid. The film-forming aid is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; esters such as ethyl acetate, butyl acetate, dimethyl adipate, and diethyl adipate; benzene, toluene, xylene, and the like Aromatic hydrocarbons such as hexane and heptane; alcohols such as methanol, ethanol, isopropanol and butanol; halogen-containing solvents such as carbon tetrachloride, methylene dichloride and hexafluoroisopropanol; esters such as ethylene glycol Or, ethers; plasticizers for water-based paints such as “Texanol” (manufactured by Eastman Chemical Co., Ltd.), “CS-12” (manufactured by Chisso Corp.), and the like. The film-forming aid may be 0.1 to 15% by mass with respect to the solid content in the water-based paint.

As the colloidal silica, organosilicate, organometallic compound, perfluorocarbon sulfonic acid resin, transition metal polyvalent ion, and metal oxide, those described above can be similarly used in the above production method.

The hydrophilic coating preferably contains a metal oxide and water, and more preferably contains a perfluorocarbon sulfonic acid resin, a metal oxide, and water. The hydrophilic paint may contain alcohol in addition to water, and examples of the alcohol include methanol, ethanol, propanol and the like.

As the above-mentioned base materials, siding materials, ceramic base materials, metal base materials, slate base materials, foamed concrete panels, concrete panels, aluminum curtain walls, steel plates, galvanized steel plates, stainless steel plates, PVC sheets, PET films, polycarbonate A base material, an acrylic film, a glass base material, etc. are mentioned. As the substrate, a substrate having an acrylic resin coating film on the substrate surface is preferable.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Each numerical value of the examples was measured by the following method.

The surface free energy of the composite polymer particles (coating layer) was determined using a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as the device and n as the solvent for the film obtained from the aqueous dispersion of composite polymer particles. -Measured with hexadecane and water.
The film forming property of the hydrophilic layer (hydrophilic coating) is measured visually and with a color difference meter (color difference meter CR300 (manufactured by Minolta Co., Ltd.)), and the difference in brightness ΔL between the color of the coating layer and the color of the hydrophilic layer is created. It was used as an index of film property.

The contact angle of the hydrophilic layer was measured using a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as a device and water as a solvent. Moreover, the contact angle after the weather resistance test implemented on the following conditions was also measured.
<Contact angle after weather resistance test>
A weather resistance test was conducted using a metal weather manufactured by Daipura Wintes. The test conditions were an illuminance of 65 mW / cm ² , a black panel temperature of 53 ° C., and a LIGHT irradiation condition (53 ° C./70% RH / 2 hours). After the test was conducted for 2 hours, the contact angle was evaluated.

Example 1
A composite polymer particle synthesis stirrer, a reflux tube, a thermometer, a dropping funnel, and a 2-liter glass four-necked separable flask equipped with a VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72). An aqueous dispersion was prepared by adding 9 parts by mass of polyoxy-1- (allyloxy) alkyl ether ammonium sulfate to 1018 parts by mass of an aqueous dispersion of particles of / 15/13 (mol%).
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 47 parts by mass of methyl methacrylate (MMA), 394 parts by mass of n-butyl methacrylate (BMA), methacrylic acid 18 parts by mass, 1 part by mass of γ-methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 50/50.

Preparation of aqueous solution of perfluorocarbon sulfonic acid resin Copolymer (perfluorocarbon) comprising tetrafluoroethylene (“CF ₂ ═CF ₂ ”, hereinafter abbreviated as “TFE”) and CF ₂ ═CFO (CF ₂ ) ₂ SO ₃ H A sulfonic acid resin) was dispersed in an aqueous ethanol solution (water: ethanol = 50: 50 (mass ratio)) to prepare a 5% by mass aqueous solution. Next, 100 g of pure water was added to 100 g of a 5% by mass perfluorocarboxylic sulfonic acid aqueous solution and concentrated to a solid content concentration of 20% by mass to obtain a 20% by mass perfluorocarbon sulfonic acid resin aqueous solution.

Preparation of hydrophilized paint A hydrophilized paint was prepared by blending 10 parts by mass of titanium oxide, 50 parts by mass of a 20% aqueous solution of perfluorocarbonsulfonic acid resin, and 40 parts by mass of ethanol.

Manufacturing method of laminated body 100 g / m of aluminum plate (chemical conversion aluminum plate (JIS H4000 A1050P, AM-712 treatment, thickness 0.5 mm) previously mixed with a black pigment paste in an aqueous acrylic resin as an undercoat. ² ), and the film-forming aid Texanol (addition amount 10PHR, manufactured by EASTMAN CHEMICAL) was added to the aqueous dispersion of the composite particles, and applied by air spray. And dried at 100 ° C. for 3 minutes to form a coating layer.
Further, a hydrophilic paint was applied on the coating layer and dried at 80 ° C. for 5 minutes to obtain an aluminum test plate containing the laminate of the present invention.

Example 2
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) In an aqueous dispersion of 1018 parts by mass of polyoxy-1- (allyloxy) alkyl ether ammonium sulfate was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 45 parts by mass of methyl methacrylate (MMA), 350 parts by mass of n-butyl methacrylate (BMA), cyclohexyl methacrylate. 44 parts by mass, 16 parts by mass of methacrylic acid, 5 parts by mass of γ-methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after ripening, the reaction was terminated by cooling to room temperature and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 50/50.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Example 3
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) Particles in an aqueous dispersion of 945 parts by weight, 17 parts by weight of polyoxy-1- (allyloxy) alkyl ether ammonium sulfate was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 13 parts by mass of methyl methacrylate (MMA), 9 parts by mass of n-butyl methacrylate (BMA), n- 153 parts by mass of butyl acrylate (BA), 12 parts by mass of methacrylic acid, 2 parts by mass of γ-methacryloxypropyltriethoxysilane, and 30 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 70/30.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Example 4
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) Particles in an aqueous dispersion of 486 parts by mass, 9 parts by mass of polyoxy-1- (allyloxy) alkyl ether ammonium sulfate was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 162 parts by mass of methyl methacrylate (MMA), 40 parts by mass of n-butyl methacrylate (BMA), n- 193 parts by mass of butyl acrylate (BA), 4 parts by mass of methacrylic acid, 4 parts by mass of γ-methacryloxypropyltriethoxysilane, and 63 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) of the fluoropolymer (A) and the acrylic polymer (B) was 35/65.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Comparative Example 1
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) Particles in an aqueous dispersion of 1018 parts by weight, 9 parts by weight of polyoxyalkylene, polycyclic phenyl ether, sulfate, ammonium salt was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 288 parts by mass of methyl methacrylate (MMA), 157 parts by mass of butyl acrylate (BA), and 10 parts by mass of acrylic acid. Parts, 5 parts by mass of γ-methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 50/50.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Comparative Example 2
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) In an aqueous dispersion of 1018 parts by mass of polyoxy-1- (allyloxy) alkyl ether ammonium sulfate was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 47 parts by mass of methyl methacrylate (MMA), 394 parts by mass of n-butyl methacrylate (BMA), methacrylic acid 12 parts by mass, 1 part by mass of γ-methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 50/50.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Comparative Example 3
VdF / TFE / CTFE polymer (VdF / TFE / CTFE = 72/15/13 (mole) was added to a 2 liter glass four-necked separable flask equipped with a stirrer, reflux tube, thermometer and dropping funnel. %)) Particles in an aqueous dispersion of 1018 parts by mass, 9 parts by mass of polyoxyalkylene polycyclic phenyl ether ammonium sulfate was added to prepare an aqueous dispersion.
Next, the aqueous dispersion was heated in a water bath with stirring, and when the bath temperature reached 80 ° C., 47 parts by mass of methyl methacrylate (MMA), 394 parts by mass of n-butyl methacrylate (BMA), methacrylic acid 18 parts by mass, 1 part by mass of γ-methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour. 30 minutes after the completion of dropping, the reaction was terminated by cooling to room temperature, and neutralization was performed with a pH adjuster to obtain an aqueous dispersion of composite polymer particles. The mass ratio (A / B) between the fluoropolymer (A) and the acrylic polymer (B) was 50/50.
“Hitachi ABFS-2” manufactured by Toagosei Co., Ltd. was used as the hydrophilic coating.
In the same manner as in Example 1, an aluminum test plate was obtained.

Claims (8)

A laminate comprising a coating layer having a surface free energy of 30 to 40 mJ / m ² and a hydrophilic layer ,
The coating layer includes a resin, and the resin is a composite polymer particle,
The composite polymer particle contains the fluoropolymer (A) and the acrylic polymer (B) in the same particle, and the mass ratio (A / B) of the fluoropolymer (A) to the acrylic polymer (B) is 90/10. 10/90 . A laminate characterized in that it is 10/90 . The laminate according to claim 1, wherein the coating layer comprises a dry coating film of a paint blended with a resin. The laminate according to claim 1 or 2 , wherein the fluoropolymer (A) contains vinylidene fluoride units. Fluoropolymer (A) is a vinylidene fluoride units, tetrafluoroethylene, according to claim 1, wherein and at least one fluoroolefin unit selected from the group consisting of hexafluoropropylene and chlorotrifluoroethylene Laminated body. Acrylic polymer (B), acrylic acid, acrylic acid ester, laminate according to claim 1, 2, 3 or 4, wherein at least one acrylic monomer units selected from the group consisting of methacrylic acid and methacrylic acid esters. The laminate according to claim 1, 2, 3, 4, or 5, wherein the acrylic polymer (B) comprises a methacrylic acid ester unit and a methacrylic acid unit. The hydrophilic layer is formed from a paint containing colloidal silica, organosilicate, organometallic compound, perfluorocarbon sulfonic acid resin, at least one selected from the group consisting of transition metal polyvalent ions and metal oxides, and water. Claim | item 1, 2, 3, 4, 5 or the laminated body of 6 . Furthermore, the laminated body of Claim 1, 2, 3, 4, 5, 6 or 7 which contains a base material and the said base material, a coating layer, and the hydrophilization layer are laminated | stacked in this order.