WO2017043634A1 - Laminated article - Google Patents

Laminated article Download PDF

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Publication number
WO2017043634A1
WO2017043634A1 PCT/JP2016/076643 JP2016076643W WO2017043634A1 WO 2017043634 A1 WO2017043634 A1 WO 2017043634A1 JP 2016076643 W JP2016076643 W JP 2016076643W WO 2017043634 A1 WO2017043634 A1 WO 2017043634A1
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WIPO (PCT)
Prior art keywords
group
acid
vinyl
polymer
acrylic
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PCT/JP2016/076643
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French (fr)
Japanese (ja)
Inventor
百合愛 坂本
井本　克彦
秀実 吉田
卓司 石川
良成 福原
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ダイキン工業株式会社
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Publication of WO2017043634A1 publication Critical patent/WO2017043634A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a laminate including a coating layer and a hydrophilic layer.
  • 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.
  • 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.
  • 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 is characterized by having a top coat film formed from a paint obtained by adding 0.5 to 100 parts by weight of alkoxysilane or a partial hydrolysis condensate of alkoxysilane to 100 parts by weight of a vinylidene-based fluororesin paint. Precoated metal plates have been proposed.
  • 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 7-109435 A Japanese Patent Laid-Open No. 10-128232 JP 2007-181951 A
  • Patent Documents 1 and 2 since the methods proposed in Patent Documents 1 and 2 are not sufficiently hydrophilized, a method capable of further hydrophilization is required.
  • patent document 3 since the binder which forms a protective layer with a photocatalyst decomposes
  • 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.
  • 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 present invention is 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 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) are preferably 90/10 to 10/90 in mass ratio (A / B).
  • 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 at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorosulfonic acid resins, transition metal polyvalent ions and metal oxides, and water. It is preferable.
  • the laminated body further includes a base material, and the base material, the coating layer, and the hydrophilic layer are laminated in this order.
  • 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.
  • 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 with water as a solvent.
  • PCA-1 manufactured by Kyowa Interface Science
  • 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 using a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as an apparatus and n-hexadecane and water as solvents.
  • PCA-1 manufactured by Kyowa Interface Science
  • 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.
  • fluorine-containing polymer having a curable functional group examples 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.
  • 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.
  • 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.
  • curable functional group-containing monomer examples 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 polymerized units based on the curable functional group-containing monomer is preferably 8 to 30 mol% with respect to the total polymerized 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%.
  • curable functional group-containing monomer examples include, but are not limited to, the following. In addition, these 1 type (s) or 2 or more types can be used.
  • hydroxyl group-containing monomer examples 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.
  • hydroxyl group-containing vinyl ethers are preferable from the viewpoint of excellent polymerization reactivity and functional group curability, 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 the other hydroxyl group-containing monomer include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • carboxyl group-containing monomer examples 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.
  • 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.
  • carboxyl group-containing vinyl ether monomer examples 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.
  • 3- (2-allyloxyethoxycarbonyl) propionic acid is preferable because it is advantageous in terms of good stability of the monomer and polymerization reactivity.
  • Silyl group-containing monomer examples include silicone-based vinyl monomers.
  • silicone vinyl monomer examples 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.
  • the curable functional group-containing fluorine-containing polymer preferably has a polymerized unit based on a fluorine-containing vinyl monomer.
  • the polymerization unit based on the fluorine-containing vinyl monomer is preferably 20 to 49 mol% with respect to all the polymerization units of the curable functional group-containing fluorine-containing 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).
  • TFE tetrafluoroethylene
  • VdF vinylidene fluoride
  • CTFE chlorotrifluoroethylene
  • vinyl fluoride vinyl fluoride
  • perfluoro (alkyl vinyl ether) perfluoro (alkyl vinyl ether
  • 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
  • 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 thereof include vinyl para-t-butylbenzoate.
  • alkyl vinyl ether examples 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.
  • fluorine-containing polymer into which the curable functional group is introduced examples include the following, depending on the polymer units constituting the polymer.
  • fluorine-containing polymer into which a curable functional group is introduced examples include (1) perfluoroolefin-based polymer mainly composed of perfluoroolefin units, and (2) CTFE-based mainly composed of chlorotrifluoroethylene (CTFE) units.
  • CTFE chlorotrifluoroethylene
  • 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.
  • Perfluoroolefin-based polymer mainly composed of perfluoroolefin units
  • the perfluoroolefin-based polymer has 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.
  • 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 based on 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%.
  • 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.
  • TFE / vinyl versatate / hydroxybutyl vinyl ether / copolymer of other monomers TFE / VdF / hydroxybutyl vinyl ether / copolymer of other monomers, etc.
  • a curable polymer paint examples include Zaffle (registered trademark) GK series manufactured by Daikin Industries, Ltd.
  • 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.
  • 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 Co., Ltd. ) Etc. can be illustrated.
  • 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.
  • fluoroalkyl group-containing polymer examples include Unidyne (registered trademark) manufactured by Daikin Industries, Ltd., FTONE (registered trademark), Zonyl (registered trademark) manufactured by DuPont, and the like.
  • the fluoropolymer to which a curable functional group is introduced is preferably a perfluoroolefin polymer, and a TFE polymer mainly composed of TFE units.
  • a CTFE polymer mainly composed of CTFE units is more preferable.
  • the curable functional group-containing fluorine-containing polymer can be produced, for example, by the method disclosed in JP-A-2004-204205.
  • 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.
  • the number of carbon atoms in the alkyl group of the (meth) acrylic acid alkyl ester is, for example, 1 to 10.
  • “(Meth) acrylic acid alkyl ester” includes acrylic acid alkyl ester and methacrylic acid alkyl ester.
  • 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) comprises 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.
  • 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 ⁇ -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.
  • (Meth) acrylates having an aromatic group for example, (Meth)
  • acrylic copolymers of acrylic polymer (i) include, for example, Hitaloid (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.
  • 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.
  • a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a glycidyl group a hydroxyl group, a carboxyl group, an amino group, a cyano group, and a glycidyl group.
  • 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.
  • 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.
  • the ethylenically unsaturated monomer includes (meth) acrylates having an aromatic group, (meth) acrylates having a fluorine atom or a chlorine atom at the ⁇ -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.
  • acrylic polymer (ii) 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 , ACRIDIC A814, ACRICID 47-540, etc. (all manufactured by Dainippon Ink & Chemicals, Inc., trade name); Dianar LR-620, Dianar SS-1084, Dianar SS-792, etc. (all Mitsubishi) Made by Rayon Co., Ltd. (trade name); Olester (registered trademark) Q166, Olester Q185, Olester Q612, Olester Q723, etc. (all are made 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 1,000 to 200,000. More preferably, it is 2000 to 100,000. 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 in an amount to make the hydroxyl value 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.
  • perhaloolefin examples include one or more of tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and the like.
  • TFE tetrafluoroethylene
  • CFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • Preferred fluoroolefins include TFE or HFP, particularly TFE because of excellent weather resistance.
  • the content of the perhaloolefin unit is preferably 30 to 70 mol% because of excellent weather resistance. Further, 35 to 55 mol%, particularly 40 to 50 mol% is preferable.
  • non-fluorinated vinyl monomer a non-fluorinated vinyl monomer having 2 to 4 carbon atoms is preferable.
  • ethylene, propylene, n-butylene, isobutylene, vinyl acetate, etc. are mentioned.
  • 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 is excellent in compatibility with the curing agent. Furthermore, 15 to 30 mol% is preferable.
  • R 22 is, for example, one having 1 to 3, preferably 1 hydroxyl group bonded to a linear or branched alkyl group having 1 to 8 carbon atoms.
  • Examples of these are, 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-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. Of these, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferred because 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.
  • 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.
  • an amount that makes the acid value in the range of 10 to 80 mgKOH / g, particularly 15 to 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.
  • 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.
  • an ammonium salt, an amine salt or an alkali metal salt is preferable.
  • 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.
  • 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.
  • 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.
  • 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) between the fluoropolymer (A) and the acrylic polymer (B) of 95/5 to 10/90.
  • a / B mass ratio between the fluoropolymer (A) and the acrylic polymer (B) of 95/5 to 10/90.
  • a / B mass ratio between the fluoropolymer (A) and the acrylic polymer (B) of 95/5 to 10/90.
  • a / B mass ratio
  • 90/10 or less is more preferable, 20/80 or more is more preferable, and 25/75 or more is still more preferable.
  • 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.
  • fluoroolefin unit a repeating unit based on a fluoroolefin.
  • fluoroolefin examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE),
  • Perfluoroolefins such as chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene, trifluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoro
  • CTFE chlorotrifluoroethylene
  • VF vinyl fluoride
  • VdF vinylidene fluoride
  • 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.
  • perfluoro (alkyl vinyl ether) examples include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), and the like.
  • a functional group-containing fluoroolefin can also be used as the fluoroolefin.
  • fluoroolefin examples 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. Periodinated vinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
  • 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.
  • 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.
  • 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.
  • 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%)
  • 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.
  • an alkyl acrylate ester having an alkyl group having 1 to 10 carbon atoms is preferable.
  • the acrylate is at least one alkyl acrylate selected from the group consisting of 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.
  • the methacrylic acid ester is preferably a methacrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms, and is 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.
  • the acrylic polymer (B) further preferably 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.
  • ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, and ⁇ -methacryloxypropylmethyl are preferable because of their 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.
  • RUVA-93 manufactured by Otsuka Chemical Co., Ltd.
  • RUVA-93 which is a methacrylate having a benzotriazole type ultraviolet absorption site
  • a cyanoacrylate type etc. can be mentioned.
  • 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.
  • benzophenone compound having an ethylenically unsaturated group-containing monomer include, but are not limited to, 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.
  • benzotriazole-based compound having an ethylenically unsaturated group-containing monomer include, but are not limited to, 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 ′-( ⁇ - (me Ta) acryl
  • a specific triazine compound having an ethylenically unsaturated group-containing monomer is not limited.
  • 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.
  • ethylenically unsaturated group-containing monomer having a light stabilizing site examples 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) comprises non-fluorinated olefin units such as unsaturated carboxylic acids, hydroxyl group-containing alkyl vinyl ethers, carboxylic acid vinyl esters, ⁇ -olefins, aromatic vinyl monomers, and epoxy group-containing monomers. It may be included.
  • 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.
  • 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.
  • hydroxyl-containing alkyl vinyl ethers 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- Examples thereof 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.
  • at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable.
  • 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. And vinyl benzoate and vinyl para-t-butylbenzoate.
  • carboxylic acid vinyl esters it is possible to impart properties such as improved gloss and increased glass transition temperature to the resulting coating film.
  • ⁇ -olefins include ethylene, propylene, n-butene, isobutene, styrene, and the like.
  • properties such as improved flexibility can be imparted to the resulting coating film.
  • aromatic vinyl monomer examples include styrenes such as styrene and ⁇ -methylstyrene.
  • epoxy group-containing monomer examples 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).
  • it contains 90% to 98% by weight of methacrylic acid ester units, 8% to 1.9% by weight 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.
  • 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.
  • 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.
  • Formula (3) CH 2 ⁇ C (CH 3 ) CH 2 CH 2 —O— (BO) m — (EO) n —SO 3 NH 4 (Wherein BO is a butylene oxide unit; EO is a CH 2 CH 2 O or CH (CH 3 ) O unit; m is an integer from 0 to 50; n is an integer from 0 to 100; m + n is an integer from 0 to 150.
  • Examples of commercially available compounds (3) include Latemul PD-104 manufactured by Kao Corporation.
  • 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).
  • Y is NH 4 or an alkali metal.
  • Na and K are preferable.
  • the oxyalkylene group include linear or branched oxyalkylene groups having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide.
  • Examples of the compound represented by the formula (4) include the formula (4a):
  • R 1 ′ is a linear or branched hydrocarbon chain that 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; Preferred examples include compounds (4a) represented by an alkylene group; n is an integer of 1 to 100; and X is SO 3 Y (Y is NH 4 or an alkali metal atom).
  • R 1 ′ has preferably 1 to 51 carbon atoms, more preferably 5 to 21 carbon atoms, and still more preferably 10 to 16 carbon atoms.
  • 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.
  • alkali metal atom Na and K are preferable.
  • R 3 ′ is a linear or branched hydrocarbon chain having 1 to 50 carbon atoms which may contain a phenyl group or a phenylene group; 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) The following formula (4a-2);
  • 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.
  • 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.
  • Examples of the commercially available compound (4a-1) include the SE series and SR series of ADEKA rear soap (both manufactured by ADEKA).
  • 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 viewpoint of dispersion stability and water resistance.
  • X is preferably SO 3 NH 4 .
  • AO is preferably ethylene oxide.
  • Examples of the commercially available compound (4a-2) include Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • the amount of the reactive anionic surfactant added is preferably 0.15 to 100 parts by weight, more preferably 0.77 parts by weight or more, and 1.5 parts by weight with respect to 100 parts by weight 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.
  • 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.
  • 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.
  • a non-reactive surfactant when the paint is an aqueous paint, it preferably contains a non-reactive surfactant.
  • non-reactive surfactant for example, a non-reactive anionic surfactant, a non-reactive nonionic surfactant or a combination thereof can be used.
  • a non-reactive amphoteric surfactant, a non-reactive surfactant can be used.
  • Cationic surfactants can also be used.
  • 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.
  • preferred examples include sodium alkylbenzene sulfonate, sodium lauryl sulfate, polyoxyethylene alkyl (or alkylphenyl) ether sulfonate, and the like.
  • 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.
  • non-reactive amphoteric surfactant lauryl betaine is suitable.
  • non-reactive cationic surfactant for example, alkyl pyridinium chloride, alkyl ammonium chloride and the like can be used.
  • 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.
  • 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.
  • an isocyanate curing agent 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.
  • 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.
  • non-blocking polyisocyanate compound examples 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.
  • non-block type aliphatic polyisocyanate compound or a non-block type aromatic polyisocyanate compound modified with a polyethylene oxide compound is exemplified.
  • non-block type aliphatic polyisocyanate compounds are preferable from the viewpoint of excellent weather resistance.
  • examples of the alicyclic polyisocyanate compound include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1-isocyanato-3,3,5.
  • non-blocking aromatic polyisocyanate compounds examples include tolylene diisocyanate.
  • polyethylene oxide compound that is a modifier examples 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.
  • 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 to the modifier is 0.01 to 0.034 equivalent, preferably 0.015 to 0.03 equivalent, of the 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 Bihijoule 3100, Bihijoule TPLS2150 manufactured by Sumitomo Bayer Urethane Co., Ltd., and Duranate WB40-100 manufactured by Asahi Kasei 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.
  • 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.
  • crosslinking agent having an aziridine group examples include XAMA2 and XAMA7 supplied from BF-Goodrich.
  • examples of the crosslinking agent having a carbodiimide group include UCARLNK Crosslinker XL-29SE supplied by Union Carbide, Carbodilite E-02, E-04, SV-02, V-02V-02-L2, V, Nisshinbo Chemical Co., Ltd. -04, V-10 and the like are exemplified.
  • cross-linking agents having an oxazoline group examples 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.
  • An example is Epocros WS-500.
  • 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.
  • the curing agent is preferably added in an amount of 0.1 to 5 molar equivalents, more preferably 0.5 to 1.5 molar equivalents relative to 1 equivalent of the curable functional group of the resin.
  • 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.
  • curing accelerator examples 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.
  • the mixing 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.
  • the acidic side colloidal silica include the trade name SNOWTEX-O or SNOWTEX-OL (Nissan).
  • Non-stabilized silica (pH 2 to 4) commercially available from Chemical Industry Co., Ltd. can be used.
  • 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.
  • 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.
  • non-hydrolyzable group examples 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 ⁇ -chloropropyl group.
  • Epoxyalkyl such as haloalkyl group, ⁇ -aminopropyl group, aminoalkyl group such as ⁇ - (2-aminoethyl) aminopropyl group, ⁇ -glycidoxypropyl group, ⁇ - (3,4-epoxycyclohexyl) ethyl group Groups, methacryloyloxyalkyl groups such as ⁇ -mercaptoalkyl groups, ⁇ -methacryloyloxypropyl groups, and hydroxyalkyl groups such as ⁇ -hydroxypropyl groups.
  • substituents therefor 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.
  • 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.
  • organosilicon compound examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ⁇ -Chloropropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, and ⁇
  • organosilicate examples 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.
  • organosilicate examples include a formula: Si (OR 41 ) 4 (Wherein R 41 is an organic group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, such as 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).
  • An organosilicate compound having 1 to 3 functional groups may be used as long as it has hydrophilicity.
  • tetrafunctional organosilicate compound examples include tetrahydroxysilane; tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane; and condensates thereof.
  • 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.
  • the propylene oxide chain and the butylene oxide chain may be included.
  • alkylene oxide-modified organosilicate and ethylene oxide-modified organosilicate are preferred from the viewpoint of good storage stability.
  • 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 is at least a trivalent valence
  • the metal atom R 51 may be the same or different and each of them may contain 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 is the same or different and each represents an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom
  • 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 includes 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.
  • 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.
  • 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 CFZ (2)
  • Z is H, Cl, F, or a perfluoroalkyl group having 1 to 3 carbon atoms.
  • 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.
  • EW of the perfluorocarbon sulfonic acid resin tends to be low and the hydrophilicity tends to be high.
  • 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.
  • m is more preferably 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.
  • 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 fluorine-containing 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
  • 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 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.
  • MI melt index
  • 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.
  • 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.
  • the reaction solution further contains a swellable organic compound such as methyl alcohol, ethyl alcohol, acetone and DMSO. Further, the content of the swellable organic compound is preferably 1 to 30% by mass with respect to the entire reaction solution.
  • 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.
  • 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 to 700, particularly preferably 250 to 600, and most preferably 400 to 500.
  • 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.
  • 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.
  • cerium ions are particularly preferable from the viewpoint of effectively improving radical resistance.
  • 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.
  • the transition metal polyvalent ion is preferably capable of ionic bonding with the sulfonic acid group of the perfluorocarbon sulfonic acid resin. .
  • cerium ions description will be made by taking cerium ions as an example.
  • cerium ions are blended in the perfluorocarbon sulfonic acid resin.
  • 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.
  • 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.
  • cerium carbonate 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.
  • the sulfonic acid groups are ion-exchanged with cerium ions, Ce 3+ is three -SO 3 - bound to.
  • 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 — , a sulfonic acid group ion-exchanged with a cerium ion is ion-exchanged with a sulfonic acid group and a cerium ion.
  • This is synonymous with 0.9 to 90% of the total amount of sulfonic acid groups formed (hereinafter, this ratio is referred to as “substitution rate”).
  • the content of cerium ions is more preferably 0.6 to 20 equivalent%, and further 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.
  • 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.
  • the metal oxide a metal oxide having a photocatalytic function is preferable.
  • 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.
  • a layered oxide having at least one element selected from Ti, Nb, Ta, and V Japanese Patent Laid-Open Nos. 62-74452, 2-172535, and 7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10 -244165, etc.
  • 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.
  • the metal oxide has a crystal particle diameter (primary particle diameter) of preferably 1 to 200 nm, more preferably 1 to 50 nm.
  • the crystal particle diameter refers to a value measured by a scattering method using a laser.
  • the hydrophilizing layer is formed from a hydrophilizing paint containing at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorosulfonic 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.
  • the laminate further includes a base material.
  • a base material suitably according to the use mentioned later.
  • 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.
  • 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.
  • 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.
  • a siding material is preferable.
  • the siding material include ceramic siding materials, metal siding materials, plastic siding materials, and the like.
  • 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.
  • 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, organosilicate, organometallic compound, perfluorosulfonic 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.
  • 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.
  • 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. After application, it may be dried at 5 to 200 ° C.
  • the laminate can be used in a wide range of applications.
  • 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
  • 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, perfluorosulfonic acid resin, transition metal polyvalent ion and metal oxide, and water or alcohol.
  • a hydrophilization layer can be formed with a water-based hydrophilization coating on the coating layer formed with the water-based coating.
  • 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.
  • 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. It is preferably ⁇ 10 / 90.
  • 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). It is preferable to contain 90% by mass of a hydrolyzable silyl group-containing monomer unit, 90 to 98% by mass of a methacrylic acid ester unit, 8 to 1.9% by mass of a methacrylic acid unit, 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
  • colloidal silica organosilicate, organometallic compound, perfluorosulfonic 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 perfluorosulfonic 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.
  • 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.
  • a substrate having an acrylic resin coating film on the substrate surface is preferable.
  • 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 ⁇ L 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 an apparatus 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.
  • An aqueous dispersion was prepared by adding 9 parts by weight of ammonium polyoxy-1- (allyloxy) alkyl ether sulfate to 1018 parts by weight of an aqueous dispersion of particles of / 15/13 (mol%).
  • 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 ⁇ -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.
  • perfluorocarbon sulfonic acid resin solution Copolymer composed of tetrafluoroethylene (“CF 2 ⁇ CF 2 ”, hereinafter abbreviated as “TFE”) and CF 2 ⁇ CFO (CF 2 ) 2 SO 3 H
  • TFE tetrafluoroethylene
  • CF 2 ⁇ CF 2 tetrafluoroethylene
  • CF 2 ⁇ CFO CF 2 ) 2 SO 3 H
  • 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.
  • an aluminum plate chemical conversion aluminum plate (JIS H4000 A1050P, AM-712 treatment, thickness 0.5 mm) previously mixed with a water-based acrylic resin and a black pigment paste as a base material) 2
  • the film-forming aid Texanol addition amount 10PHR, manufactured by EASTMAN
  • 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 ⁇ -methacryloxypropyltriethoxysilane, and 40 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • APS ammonium persulfate
  • 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 ⁇ -methacryloxypropyltriethoxysilane, and 30 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • BA butyl acrylate
  • APS ammonium persulfate
  • 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 ⁇ -methacryloxypropyltriethoxysilane, and 63 parts by mass of ammonium persulfate (APS) (1% aqueous solution) were added dropwise over 1 hour.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • BA butyl acrylate
  • APS ammonium persulfate
  • 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. Part, 5 parts by mass of ⁇ -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.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • APS ammonium persulfate
  • 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.
  • 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 ⁇ -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.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • APS ammonium persulfate
  • 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.
  • 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 ⁇ -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.
  • MMA methyl methacrylate
  • BMA n-butyl methacrylate
  • APS ammonium persulfate
  • 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.

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Abstract

To provide a laminated article having exceptional weather resistance and hydrophilicity. A laminated article characterized in comprising a cover layer having a surface free energy of 30-40 mJ/m2 and a hydrophobicized layer.

Description

積層体Laminated body
本発明は、被覆層及び親水化層を含む積層体に関する。 The present invention relates to a laminate including a coating layer and a hydrophilic layer.
フッ素樹脂塗料から形成された塗膜は、優れた耐候性を有することから、屋外で使用される物品の表面をフッ素樹脂塗料から形成された塗膜で覆い、物品に耐候性を付与することが行われている。 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.
しかし、フッ素樹脂塗料から形成された塗膜は、耐候性に優れるものの、表面に汚れが付着しやすい欠点があったことから、この欠点を解決するために、上記塗膜を親水化する方法や、上記塗膜の上に親水性の塗膜を形成する方法が提案されている。 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.
例えば、特許文献１では、特に雨すじ汚れの発生を防止するための塗膜表面を有する屋外物品として、水中でのオクタン接触角が１０２度以上である塗膜表面を有する屋外物品が提案されており、該塗膜を、疎水性合成樹脂塗膜表面を有する屋外物品の前記塗膜表面上にケイ素化合物（Ａ）と塗料用フッ素樹脂等の合成樹脂造膜成分（Ｂ）とを含む表面処理剤を塗布することにより形成することが提案されている。 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.
特許文献２では、大気中のカーボン系汚染物質等による汚れが付着し難いプレコート金属板として、金属板上にプライマー層及びポリフッ化ビニリデン系フッ素塗料の中塗り塗膜を有し、更に、ポリフッ化ビニリデン系フッ素樹脂塗料に、塗料樹脂１００重量部に対してアルコキシシラン又はアルコキシシランの部分加水分解縮合物を０．５～１００重量部添加した塗料から形成した上塗り塗膜を有することを特徴とするプレコート金属板が提案されている。 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 is characterized by having a top coat film formed from a paint obtained by adding 0.5 to 100 parts by weight of alkoxysilane or a partial hydrolysis condensate of alkoxysilane to 100 parts by weight of a vinylidene-based fluororesin paint. Precoated metal plates have been proposed.
特許文献３では、金属板の少なくとも一面に光触媒を含有しない無機質塗料にて形成された保護層と、光触媒及びフッ素樹脂ワックスを含有する無機質塗料にて形成された光触媒層とが積層して形成されていることを特徴とする塗装金属板が提案されている。 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.
特開平７－１０９４３５号公報JP 7-109435 A 特開平１０－１２８２３２号公報Japanese Patent Laid-Open No. 10-128232 特開２００７－１８１９５１号公報JP 2007-181951 A
しかしながら、特許文献１及び２で提案された方法では、親水化が十分ではないことから、更に親水化できる方法が求められている。
特許文献３では、光触媒により保護層を形成するバインダーが分解し耐候性が十分でないことから、耐候性の改良が求められている。 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.
本発明の目的は、上記現状に鑑み、耐候性及び親水性に優れた積層体を提供することにある。 The objective of this invention is providing the laminated body excellent in the weather resistance and hydrophilicity in view of the said present condition.
本発明者らは、基材の表面に耐候性に優れた含フッ素ポリマー層又はアクリルポリマー層を被覆層として形成し、該層の上に更に親水化層を設けることにより、上記課題を解決しようと試みた。しかしながら、含フッ素ポリマー層又はアクリルポリマー層の上に親水化層を形成させることは容易でなく、仮に形成できたとしても、耐候性試験後には積層体の親水性が消失することが判明した。 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.
そこで、本発明者らは、積層体の構成を鋭意検討した結果、被覆層が特定の表面自由エネルギーを有する場合のみ、親水化層を被覆層上に形成することができ、耐候性試験後でも積層体の親水性が維持されていることを見出し、本発明を完成するに至った。 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.
すなわち、本発明は、表面自由エネルギーが３０～４０ｍＪ／ｍ２である被覆層と、親水化層とを含むことを特徴とする積層体である。 That is, the present invention is a laminate comprising a coating layer having a surface free energy of 30 to 40 mJ / m 2 and a hydrophilic layer.
上記被覆層は、樹脂を配合した塗料の乾燥塗膜からなることが好ましい。 The coating layer is preferably made of a dry coating film of a paint blended with a resin.
上記被覆層は、樹脂を含み、上記樹脂は、硬化性官能基を有する含フッ素ポリマー又はアクリルポリマーであることが好ましい。 The coating layer includes a resin, and the resin is preferably a fluorine-containing polymer or an acrylic polymer having a curable functional group.
上記被覆層は、樹脂を含み、上記樹脂は、複合重合体粒子であり、上記複合重合体粒子は、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）とを同一粒子内に含み、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）が９０／１０～１０／９０であることが好ましい。 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) are preferably 90/10 to 10/90 in mass ratio (A / B).
フルオロポリマー（Ａ）は、ビニリデンフルオライド単位を含むことが好ましい。 The fluoropolymer (A) preferably contains vinylidene fluoride units.
フルオロポリマー（Ａ）は、ビニリデンフルオライド単位と、テトラフルオロエチレン、ヘキサフルオロプロピレン及びクロロトリフルオロエチレンからなる群より選ばれる少なくとも１種のフルオロオレフィン単位とを含むことが好ましい。 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.
アクリルポリマー（Ｂ）は、アクリル酸、アクリル酸エステル、メタクリル酸及びメタクリル酸エステルからなる群より選択される少なくとも１種のアクリルモノマー単位を含むことが好ましい。 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.
アクリルポリマー（Ｂ）は、メタクリル酸エステル単位と、メタクリル酸単位とを含むことが好ましい。 The acrylic polymer (B) preferably contains a methacrylic acid ester unit and a methacrylic acid unit.
上記親水化層は、コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種並びに水を含む塗料から形成されることが好ましい。 The hydrophilic layer is formed of a paint containing at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorosulfonic acid resins, transition metal polyvalent ions and metal oxides, and water. It is preferable.
上記積層体は、更に、基材を含み、上記基材、上記被覆層及び上記親水化層がこの順に積層されていることが好ましい。 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.
本発明の積層体は、上記構成を有していることから、耐候性及び親水性に優れており、耐候性試験後でも優れた親水性を示す。 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.
以下、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described.
本発明の積層体は、被覆層と親水化層とを含む。 The laminate of the present invention includes a coating layer and a hydrophilic layer.
上記親水化層は、水に対する接触角が７０°以下であることが好ましい。上記接触角としては、６０°以下がより好ましく、下限は特に限定されないが、０°であってよく、１３°であってよい。 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 °.
上記接触角は、装置として接触角計「ＰＣＡ－１」（協和界面科学製）を用い、溶媒として水により測定する。 The contact angle is measured with a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as a device and with water as a solvent.
上記被覆層は、表面自由エネルギーが３０～４０ｍＪ／ｍ２である。上記表面自由エネルギーとしては、３２ｍＪ／ｍ２以上が好ましく、３８ｍＪ／ｍ２以下が好ましい。 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.
上記表面自由エネルギーは、装置として接触角計「ＰＣＡ－１」（協和界面科学製）を用い、溶媒としてｎ－ヘキサデカンと水により測定する。 The surface free energy is measured using a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as an apparatus and n-hexadecane and water as solvents.
本発明の積層体は、上記被覆層が特定の表面自由エネルギーを有することによって、上記親水化層と上記被覆層とが強固に接着しており、耐候性試験後でも両層が剥離しないことから、耐候性試験後でも優れた親水性を示す。 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.
上記被覆層は、樹脂を含むことが好ましい。上記樹脂は、硬化性官能基を有する含フッ素ポリマー又はアクリルポリマーであることが好ましい。 The coating layer preferably contains a resin. The resin is preferably a fluorine-containing polymer or an acrylic polymer having a curable functional group.
上記硬化性官能基を有する含フッ素ポリマーとしては、含フッ素ポリマーに硬化性の官能基を導入したポリマーが挙げられる。なお、硬化性官能基含有含フッ素ポリマーには明確な融点を有する樹脂性のポリマー、ゴム弾性を示すエラストマー性のポリマー、その中間の熱可塑性エラストマー性のポリマーが含まれる。 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.
上記含フッ素ポリマーに硬化性を与える官能基は、ポリマーの製造の容易さや硬化系に併せて適宜選択されるが、例えば、水酸基（但し、カルボキシル基に含まれる水酸基は除く。以下、同じ。）、カルボキシル基、－ＣＯＯＣＯ－で表される基、シアノ基、アミノ基、グリシジル基、シリル基、シラネート基等が挙げられる。なかでも、硬化反応性が良好な点から、水酸基、カルボキシル基、－ＣＯＯＣＯ－で表される基、アミノ基、シアノ基、及び、シリル基からなる群より選択される少なくとも１種の基が好ましく、水酸基、カルボキシル基、アミノ基、及び、シリル基からなる群より選択される少なくとも１種の基がより好ましく、水酸基、及び、カルボキシル基からなる群より選択される少なくとも１種の基が更に好ましい。これらの硬化性官能基は、通常、硬化性官能基を有する単量体を共重合することにより含フッ素ポリマーに導入される。 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.
上記硬化性官能基含有単量体としては、水酸基含有単量体、カルボキシル基含有単量体、アミノ基含有単量体、シリコーン系ビニル単量体等を挙げることができ、これらの１種又は２種以上を用いることができる。 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.
上記硬化性官能基含有含フッ素ポリマーは、含フッ素単量体に基づく重合単位と、水酸基含有単量体、カルボキシル基含有単量体、アミノ基含有単量体、及び、シリコーン系ビニル単量体からなる群より選択される少なくとも１種の硬化性官能基含有単量体に基づく重合単位とを含むことが好ましい。また、上記硬化性官能基含有含フッ素ポリマーは、含フッ素単量体に基づく重合単位と、水酸基含有単量体及びカルボキシル基含有単量体からなる群より選択される少なくとも１種の硬化性官能基含有単量体に基づく重合単位とを含むことがより好ましい。 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.
硬化性官能基含有単量体に基づく重合単位は、硬化性官能基含有含フッ素ポリマーの全重合単位に対して、８～３０モル％であることが好ましい。より好ましい下限は１０モル％であり、より好ましい上限は２０モル％である。 The polymerized units based on the curable functional group-containing monomer is preferably 8 to 30 mol% with respect to the total polymerized 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%.
硬化性官能基含有単量体としては、たとえばつぎのものが例示できるが、これらのみに限定されるものではない。なお、これらの１種又は２種以上を用いることができる。 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）水酸基含有単量体：
水酸基含有単量体としては、例えば、２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル等の水酸基含有ビニルエーテル類；２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等の水酸基含有アリルエーテル類等が挙げられる。これらのなかでも、重合反応性、官能基の硬化性が優れる点で、水酸基含有ビニルエーテル類が好ましく、４－ヒドロキシブチルビニルエーテル、及び、２ーヒドロキシエチルビニルエーテルからなる群より選択される少なくとも１種の単量体が特に好ましい。 (1-1) Hydroxyl-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 from the viewpoint of excellent polymerization reactivity and functional group curability, and at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether. Monomers are particularly preferred.
他の水酸基含有単量体としては、たとえばアクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル等の（メタ）アクリル酸のヒドロキシアルキルエステル等も挙げられる。 Examples of the other hydroxyl group-containing monomer include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
（１－２）カルボキシル基含有単量体：
カルボキシル基含有単量体としては、たとえば、式：
ＣＲ１１Ｒ１２＝ＣＲ１３（ＣＨ２）ｎＣＯＯＨ
（式中、Ｒ１１、Ｒ１２およびＲ１３は、同じかまたは異なり、水素原子、アルキル基、カルボキシル基またはエステル基である。ｎは、０または１である。）で表わされる不飽和カルボン酸類（例えば、不飽和モノカルボン酸、不飽和ジカルボン酸等）、それらのエステル並びに酸無水物、及び、式：
ＣＨ２＝ＣＨ（ＣＨ２）ｎＯ（Ｒ１４ＯＣＯ）ｍＲ１５ＣＯＯＨ
（式中、Ｒ１４およびＲ１５は、同じかまたは異なり、いずれも飽和または不飽和の直鎖、分岐または環状のアルキレン基である。ｎは、０または１であり、ｍは、０または１である。）で表わされるカルボキシル基含有ビニルエーテル単量体からなる群より選択される少なくとも１種の単量体が好ましい。 (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
上記カルボキシル基含有単量体の具体例としては、たとえば、アクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、３－アリルオキシプロピオン酸、３－（２－アリロキシエトキシカルボニル）プロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニル等が挙げられる。それらのなかでも、単独重合性が低く単独重合体ができにくいことから、クロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、及び、３－アリルオキシプロピオン酸からなる群より選択される少なくとも１種の酸が好ましい。 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.
上記カルボキシル基含有ビニルエーテル単量体の具体例としては、たとえば、３－（２－アリロキシエトキシカルボニル）プロピオン酸、３－（２－アリロキシブトキシカルボニル）プロピオン酸、３－（２－ビニロキシエトキシカルボニル）プロピオン酸、３－（２－ビニロキシブトキシカルボニル）プロピオン酸等が挙げられる。これらの中でも、単量体の安定性や重合反応性がよい点で有利であることから、３－（２－アリロキシエトキシカルボニル）プロピオン酸が好ましい。 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 stability of the monomer and polymerization reactivity.
（１－３）アミノ基含有単量体：
アミノ基含有単量体としては、たとえばＣＨ２＝ＣＨ－Ｏ－（ＣＨ２）ｘ－ＮＨ２（ｘ＝０～１０）で示されるアミノビニルエーテル類；ＣＨ２＝ＣＨ－Ｏ－ＣＯ（ＣＨ２）ｘ－ＮＨ２（ｘ＝１～１０）で示されるアリルアミン類；そのほかアミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミド等が挙げられる。 (1-3) Amino group-containing monomer:
Examples of amino group-containing monomers 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 ) X- NH 2 (x = 1 to 10); allylamines such as aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide and the like.
（１－４）シリル基含有単量体：
シリル基含有単量体としては、例えば、シリコーン系ビニル単量体が挙げられる。シリコーン系ビニル単量体としては、たとえばＣＨ２＝ＣＨＣＯ２（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２＝ＣＨＣＯ２（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、ＣＨ２＝ＣＨＣＯ２（ＣＨ２）３ＳｉＣＨ３（ＯＣ２Ｈ５）２、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３ＳｉＣ２Ｈ５（ＯＣＨ３）２、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３Ｓｉ（ＣＨ３）２（ＯＣ２Ｈ５）、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＨ、ＣＨ２＝ＣＨ（ＣＨ２）３Ｓｉ（ＯＣＯＣＨ３）３、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３ＳｉＣ２Ｈ５（ＯＣＯＣＨ３）２、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３ＳｉＣＨ３（Ｎ（ＣＨ３）ＣＯＣＨ３）２、ＣＨ２＝ＣＨＣＯ２（ＣＨ２）３ＳｉＣＨ３〔ＯＮ（ＣＨ３）Ｃ２Ｈ５〕２、ＣＨ２＝Ｃ（ＣＨ３）ＣＯ２（ＣＨ２）３ＳｉＣ６Ｈ５〔ＯＮ（ＣＨ３）Ｃ２Ｈ５〕２等の（メタ）アクリル酸エステル類；ＣＨ２＝ＣＨＳｉ［ＯＮ＝Ｃ（ＣＨ３）（Ｃ２Ｈ５）］３、ＣＨ２＝ＣＨＳｉ（ＯＣＨ３）３、ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ５）３、ＣＨ２＝ＣＨＳｉＣＨ３（ＯＣＨ３）２、ＣＨ２＝ＣＨＳｉ（ＯＣＯＣＨ３）３、ＣＨ２＝ＣＨＳｉ（ＣＨ３）２（ＯＣ２Ｈ５）、ＣＨ２＝ＣＨＳｉ（ＣＨ３）２ＳｉＣＨ３（ＯＣＨ３）２、ＣＨ２＝ＣＨＳｉＣ２Ｈ５（ＯＣＯＣＨ３）２、ＣＨ２＝ＣＨＳｉＣＨ３〔ＯＮ（ＣＨ３）Ｃ２Ｈ５〕２、ビニルトリクロロシランまたはこれらの部分加水分解物等のビニルシラン類；トリメトキシシリルエチルビニルエーテル、トリエトキシシリルエチルビニルエーテル、トリメトキシシリルブチルビニルエーテル、メチルジメトキシシリルエチルビニルエーテル、トリメトキシシリルプロピルビニルエーテル、トリエトキシシリルプロピルビニルエーテル等のビニルエーテル類等が例示される。 (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.
上記硬化性官能基含有含フッ素ポリマーは、含フッ素ビニルモノマーに基づく重合単位を有することが好ましい。 The curable functional group-containing fluorine-containing polymer preferably has a polymerized unit based on a fluorine-containing vinyl monomer.
含フッ素ビニルモノマーに基づく重合単位は、硬化性官能基含有含フッ素ポリマーの全重合単位に対して、２０～４９モル％であることが好ましい。より好ましい下限は３０モル％であり、更に好ましい下限は４０モル％である。より好ましい上限は４７モル％である。 The polymerization unit based on the fluorine-containing vinyl monomer is preferably 20 to 49 mol% with respect to all the polymerization units of the curable functional group-containing fluorine-containing 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%.
含フッ素ビニルモノマーとしては、テトラフルオロエチレン〔ＴＦＥ〕、フッ化ビニリデン〔ＶｄＦ〕、クロロトリフルオロエチレン〔ＣＴＦＥ〕、フッ化ビニル、へキサフルオロプロピレン及びパーフルオロ（アルキルビニルエーテル）からなる群より選択される少なくとも１種であることが好ましく、分散性、耐湿性、耐熱性、難燃性、接着性、共重合性及び耐薬品性等に優れている点で、ＴＦＥ、ＣＴＦＥ及びＶｄＦからなる群より選択される少なくとも１種であることがより好ましく、耐候性に優れ、更に耐湿性により優れている点で、ＴＦＥ及びＣＴＦＥからなる群より選択される少なくとも１種であることが特に好ましく、ＴＦＥが最も好ましい。 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.
上記硬化性官能基含有含フッ素ポリマーは、カルボン酸ビニルエステル、アルキルビニルエーテル及び非フッ素化オレフィンからなる群より選択される少なくとも１種のフッ素非含有ビニルモノマーに基づく重合単位を含むことが好ましい。
カルボン酸ビニルエステルは、相溶性を改善する作用を有する。カルボン酸ビニルエステルとしては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル、安息香酸ビニル、パラ－ｔ－ブチル安息香酸ビニル等が挙げられる。
アルキルビニルエーテルとしては、メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル等が挙げられる。
非フッ素化オレフィンとしては、エチレン、プロピレン、ｎ－ブテン、イソブテン等が挙げられる。 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 thereof 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.
上記フッ素非含有ビニルモノマーに基づく重合単位は、硬化性官能基含有ビニルモノマーに基づく重合単位、及び、含フッ素ビニルモノマーに基づく重合単位以外の全重合単位を構成することが好ましい。 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.
硬化性官能基が導入される含フッ素ポリマーとしては、該ポリマーを構成する重合単位に応じて、たとえば次のものが例示できる。 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.
硬化性官能基が導入される含フッ素ポリマーとしては、例えば、（１）パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマー、（２）クロロトリフルオロエチレン（ＣＴＦＥ）単位を主体とするＣＴＦＥ系ポリマー、（３）ビニリデンフルオライド（ＶｄＦ）単位を主体とするＶｄＦ系ポリマー、（４）フルオロアルキル単位を主体とするフルオロアルキル基含有ポリマー等が挙げられる。 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）パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマー
パーフルオロオレフィン系ポリマーは、パーフルオロオレフィン系ポリマーの全重合単位に対して、パーフルオロオレフィン単位が２０～４９モル％であることが好ましい。より好ましい下限は３０モル％であり、更に好ましい下限は４０モル％である。より好ましい上限は４７モル％である。具体例としては、テトラフルオロエチレン（ＴＦＥ）の単独重合体、若しくは、ＴＦＥと、ヘキサフルオロプロピレン（ＨＦＰ）、パーフルオロ（アルキルビニルエーテル）（ＰＡＶＥ）等との共重合体、これらの単量体と共重合可能な他の単量体との共重合体等が挙げられる。 (1) Perfluoroolefin-based polymer mainly composed of perfluoroolefin units The perfluoroolefin-based polymer has 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.
上記共重合可能な他の単量体としては、たとえば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル、安息香酸ビニル、パラ－ｔ－ブチル安息香酸ビニル等のカルボン酸ビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテル等のアルキルビニルエーテル類；エチレン、プロピレン、ｎ－ブテン、イソブテン等の非フッ素系オレフィン類；ビニリデンフルオライド（ＶｄＦ）、クロロトリフルオロエチレン（ＣＴＦＥ）、ビニルフルオライド（ＶＦ）、フルオロビニルエーテル等のフッ素系単量体等が挙げられるが、これらのみに限定されるものではない。 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.
パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマーの中でも、顔料分散性や耐候性、共重合性及び耐薬品性に優れる点で、ＴＦＥ単位を主体とするＴＦＥ系ポリマーが好ましい。ＴＦＥ系ポリマーは、ＴＦＥ系ポリマーの全重合単位に対して、ＴＦＥ単位が２０～４９モル％であることが好ましい。より好ましい下限は３０モル％であり、更に好ましい下限は４０モル％である。より好ましい上限は４７モル％である。 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 based on 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%.
パーフルオロオレフィン単位を主体とするパーフルオロオレフィン系ポリマーに硬化性官能基を導入した硬化性官能基含有含フッ素ポリマーとしては、例えば、ＴＦＥ／イソブチレン／ヒドロキシブチルビニルエーテル／他の単量体の共重合体、ＴＦＥ／バーサチック酸ビニル／ヒドロキシブチルビニルエーテル／他の単量体の共重合体、ＴＦＥ／ＶｄＦ／ヒドロキシブチルビニルエーテル／他の単量体の共重合体等が挙げられ、特に、ＴＦＥ／イソブチレン／ヒドロキシブチルビニルエーテル／他の単量体の共重合体、及び、ＴＦＥ／バーサチック酸ビニル／ヒドロキシブチルビニルエーテル／他の単量体の共重合体からなる群より選択される少なくとも１種の共重合体が好ましい。このような硬化性ポリマーの塗料としては、たとえばダイキン工業（株）製のゼッフル（登録商標）ＧＫシリーズ等が例示できる。 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）クロロトリフルオロエチレン（ＣＴＦＥ）単位を主体とするＣＴＦＥ系ポリマー
ＣＴＦＥ単位を主体とするＣＴＦＥ系ポリマーに硬化性官能基を導入した硬化性官能基含有含フッ素ポリマーとしては、たとえばＣＴＦＥ／ヒドロキシブチルビニルエーテル／他の単量体の共重合体等が挙げられる。ＣＴＦＥ系ポリマーの硬化性ポリマー塗料としては、たとえば旭硝子（株）製のルミフロン（登録商標）、大日本インキ製造（株）製のフルオネート（登録商標）、セントラル硝子（株）製のセフラルコート（登録商標）等が例示できる。 (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 Co., Ltd. ) Etc. can be illustrated.
（３）ビニリデンフルオライド（ＶｄＦ）単位を主体とするＶｄＦ系ポリマー
ＶｄＦ単位を主体とするＶｄＦ系ポリマーに硬化性官能基を導入した硬化性官能基含有含フッ素ポリマーとしては、たとえばＶｄＦ／ＴＦＥ／ヒドロキシブチルビニルエーテル／他の単量体の共重合体等が挙げられる。 (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）フルオロアルキル単位を主体とするフルオロアルキル基含有ポリマー
フルオロアルキル単位を主体とするフルオロアルキル基含有ポリマーに硬化性官能基を導入した硬化性官能基含有含フッ素ポリマーとしては、たとえばＣＦ３ＣＦ２（ＣＦ２ＣＦ２）ｎＣＨ２ＣＨ２ＯＣＯＣＨ＝ＣＨ２（ｎ＝３と４の混合物）／２－ヒドロキシエチルメタクリレート／ステアリルアクリレート共重合体等が挙げられる。フルオロアルキル基含有ポリマーとしては、たとえばダイキン工業（株）製のユニダイン（登録商標）やエフトーン（登録商標）、デュポン社製のゾニール（登録商標）等が例示できる。 (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.
上記（１）～（４）の中でも、耐候性及び防湿性の観点から、硬化性官能基が導入される含フッ素ポリマーは、パーフルオロオレフィン系ポリマーが好ましく、ＴＦＥ単位を主体とするＴＦＥ系ポリマー又はＣＴＦＥ単位を主体とするＣＴＦＥ系ポリマーがより好ましい。 Among the above (1) to (4), from the viewpoint of weather resistance and moisture resistance, the fluoropolymer to which a 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.
上記硬化性官能基含有含フッ素ポリマーは、例えば、特開２００４－２０４２０５号公報に開示される方法により製造することができる。 The curable functional group-containing fluorine-containing polymer can be produced, for example, by the method disclosed in JP-A-2004-204205.
上記アクリルポリマーは、アクリル基を有する単量体に基づく重合単位が、全重合単位に対して、５質量％以上であることが好ましい。より好ましくは、１０質量％以上である。更に好ましくは、２０質量％以上である。また、耐候性に優れる点から、９８質量％以下が好ましく、９６質量％以下がより好ましく、９０質量％以下が更に好ましく、８０質量％以下が特に好ましい。 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.
アクリルポリマーは、例えば、（メタ）アクリル酸アルキルエステルに基づく重合単位からなる重合体であることが好ましい。上記（メタ）アクリル酸アルキルエステルのアルキル基の炭素数は、例えば、１～１０である。
なお、「（メタ）アクリル酸アルキルエステル」は、アクリル酸アルキルエステル、及び、メタクリル酸アルキルエステルを含むものである。 The acrylic polymer is preferably a polymer comprising polymerized units based on (meth) acrylic acid alkyl ester, for example. The number of carbon atoms in the alkyl group of the (meth) acrylic acid alkyl ester is, for example, 1 to 10.
“(Meth) acrylic acid alkyl ester” includes acrylic acid alkyl ester and methacrylic acid alkyl ester.
アクリルポリマーは、耐候性に優れることから、（メタ）アクリル酸アルキルエステルに基づく重合単位の含有量が５質量％以上であることが好ましい。より好ましくは１０質量％以上であり、更に好ましくは、２０質量％以上である。また、耐候性に優れる点から、９８質量％以下が好ましく、９６質量％以下がより好ましく、９０質量％以下が更に好ましく、８０質量％以下が特に好ましい。 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.
アクリルポリマーは、例えば、（ｉ）側鎖および／または主鎖末端に硬化性官能基を有さない、（メタ）アクリル酸アルキルエステルに基づく重合単位からなる重合体（以下、アクリルポリマー（ｉ）ともいう。）、並びに、（ｉｉ）側鎖および／または主鎖末端に硬化性官能基を有し、（メタ）アクリル酸アルキルエステルに基づく重合単位からなる共重合体（以下、アクリルポリマー（ｉｉ）ともいう。）からなる群より選択される少なくとも１種の重合体が好ましい。耐候性に優れることから、アクリルポリマー（ｉｉ）が好ましい。 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.
アクリルポリマー（ｉ）は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及び、シクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種の単量体に基づく重合単位からなる重合体が好ましい。アクリルポリマー（ｉ）は、これらの単量体のみからなる重合体であってもよいし、更に、これらの単量体と共重合可能なエチレン性不飽和単量体に基づく重合単位からなる共重合体でもよい。 The acrylic polymer (i) comprises 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.
アクリルポリマー（ｉ）は、耐候性が優れる点から、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及び、シクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種の単量体に基づく重合単位からなる重合体が好ましく、更に、これらの単量体と共重合可能なエチレン性不飽和単量体に基づく重合単位からなる共重合体がより好ましい。 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.
イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及び、シクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種の単量体と共重合可能なエチレン性不飽和モノマーとしては、たとえば、芳香族基を有する（メタ）アクリレート類、α位にフッ素原子または塩素原子を有する（メタ）アクリレート類、アルキル基がフッ素原子で置換されたフルオロアルキル（メタ）アクリレート類、ビニルエーテル類、ビニルエステル類、スチレン等の芳香族ビニルモノマー類、エチレン、プロピレン、イソブチレン、塩化ビニル、塩化ビニリデン等のオレフィン類、フマル酸ジエステル類、マレイン酸ジエステル類、（メタ）アクリロニトリル等が挙げられる。 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.
アクリルポリマー（ｉ）の市販アクリル共重合体としては、たとえばヒタロイド（登録商標）１００５、ヒタロイド１２０６、ヒタロイド２３３０－６０、ヒタロイド４００１、ヒタロイド１６２８Ａ等（いずれも日立化成工業社製。商品名）；ダイヤナール（登録商標）ＬＲ－１０６５、ダイヤナールＬＲ－９０等（いずれも三菱レイヨン社製。商品名）；パラロイド（登録商標）Ｂ－４４、パラロイドＡ－２１、パラロイドＢ－８２等（いずれもダウケミカル社製。商品名）；ＥＬＶＡＣＩＴＥ２０００等（ルーサント・インターナショナル社製。商品名）；アルマテックス（登録商標）Ｌ１０４４Ｐ（三井化学社製。商品名）等が挙げられる。 Commercially available acrylic copolymers of acrylic polymer (i) include, for example, Hitaloid (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.
アクリルポリマー（ｉｉ）は、側鎖および／または主鎖末端に硬化性官能基を有する。硬化性官能基としては、水酸基、カルボキシル基、エポキシ基、シアノ基、アミノ基、グリシジル基、シリル基、シラネート基等が挙げられ、なかでも、水酸基、カルボキシル基、アミノ基、シアノ基、グリシジル基、及び、シリル基からなる群より選択される少なくとも１種の基がより好ましく、水酸基、アミノ基、及び、グリシジル基からなる群より選択される少なくとも１種の基が更に好ましく、硬化反応性が良好な点から水酸基が特に好ましい。 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.
アクリルポリマー（ｉｉ）は、（メタ）アクリル酸アルキルエステルに基づく重合単位からなる共重合体であり、上記（メタ）アクリル酸アルキルエステルのアルキル基の炭素数は１～１０であることが好ましい。 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.
アクリルポリマー（ｉｉ）は、（メタ）アクリル酸アルキルエステルに基づく重合単位、及び、該（メタ）アクリル酸アルキルエステルと共重合可能な単量体に基づく重合単位からなり、該共重合可能な単量体は、硬化性官能基を有するものであることが好ましい。
硬化性官能基を有する（メタ）アクリル酸アルキルエステルと共重合可能な単量体に基づく重合単位の含有量は、耐候性が優れることから、５０質量％以下が好ましく、より好ましくは４０質量％以下である。また耐候性が優れる点から、２質量％以上が好ましく、より好ましくは４質量％以上である。 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.
アクリルポリマー（ｉｉ）において、（メタ）アクリル酸アルキルエステルは、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及び、シクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種の単量体が好ましい。 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.
（メタ）アクリル酸アルキルエステルと共重合可能である硬化性官能基を有する単量体としては、例えば、ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシエチルビニルエーテル、（メタ）アクリル酸、グリシジル（メタ）アクリレート、２－アミノエチル（メタ）アクリレート、及び、２－アミノプロピル（メタ）アクリレートからなる群より選択される少なくとも１種の単量体が好ましい。 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.
アクリルポリマー（ｉｉ）は、（メタ）アクリル酸アルキルエステルに基づく重合単位、（メタ）アクリル酸アルキルエステルと共重合可能である硬化性官能基を有する単量体に基づく重合単位、及び、これらの単量体と共重合可能なエチレン性不飽和単量体に基づく重合単位からなる共重合体であってもよい。 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.
アクリルポリマー（ｉｉ）において、上記エチレン性不飽和単量体としては、芳香族基を有する（メタ）アクリレート類、α位にフッ素原子または塩素原子を有する（メタ）アクリレート類、アルキル基がフッ素原子で置換されたフルオロアルキル（メタ）アクリレート類、ビニルエーテル類、ビニルエステル類、スチレン等の芳香族ビニルモノマー類、エチレン、プロピレン、イソブチレン、塩化ビニル、塩化ビニリデン等のオレフィン類、フマル酸ジエステル類、マレイン酸ジエステル類、（メタ）アクリロニトリル等が好ましい。 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.
アクリルポリマー（ｉｉ）の市販品としては、ヒタロイド３００４、ヒタロイド３０１８、ヒタロイド３０４６Ｃ、ヒタロイド６５００Ｂ、ヒタロイド６５００等（いずれも日立化成工業（株）製。商品名）；アクリディック（登録商標）Ａ８１０－４５、アクリディックＡ８１４、アクリディック４７－５４０等（いずれも大日本インキ化学工業（株）製。商品名）；ダイヤナールＬＲ－６２０、ダイヤナールＳＳ－１０８４、ダイヤナールＳＳ－７９２等（いずれも三菱レイヨン（株）製。商品名）；オレスター（登録商標）Ｑ１６６、オレスターＱ１８５、オレスターＱ６１２、オレスターＱ７２３等（いずれも三井化学（株）製。商品名）；ハリアクロン８３６０Ｇ－５５、ハリアクロン８３６０ＨＳ－１３０、ハリアクロン８１６０（いずれもハリマ化成（株）製。商品名）等がある。 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 , ACRIDIC A814, ACRICID 47-540, etc. (all manufactured by Dainippon Ink & Chemicals, Inc., trade name); Dianar LR-620, Dianar SS-1084, Dianar SS-792, etc. (all Mitsubishi) Made by Rayon Co., Ltd. (trade name); Olester (registered trademark) Q166, Olester Q185, Olester Q612, Olester Q723, etc. (all are made by Mitsui Chemicals, Inc., trade name); Hariacron 8360G-55, Hariacron 8360HS-130, Hariacron 816 (Both Harima Kasei Co., Ltd.. Trade name) and the like.
アクリルポリマーの数平均分子量は、１０００～２０００００が好ましい。より好ましくは２０００～１０００００である。数平均分子量が大きすぎると塗布が困難になる傾向にあり、小さすぎると耐侯性に問題が生じる傾向にある。 The number average molecular weight of the acrylic polymer is preferably 1,000 to 200,000. More preferably, it is 2000 to 100,000. 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.
上記樹脂として、また、パーハロオレフィン単位と非フッ素ビニル単量体単位とウンデシレン酸単位と水酸基含有ビニル単量体単位とを含む含フッ素共重合体またはその中和物を挙げることもできる。
上記樹脂としては、３０～７０モル％のパーハロオレフィン単位と、５～３５モル％の非フッ素ビニル単量体単位と、水酸基価を１０～２００ｍｇＫＯＨ／ｇの範囲にする量の水酸基含有ビニル単量体単位と、酸価を１０～１００ｍｇＫＯＨ／ｇの範囲にする量のウンデシレン酸単位とを含む含フッ素共重合体又はその中和物であることも好ましい。 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 in an amount to make the hydroxyl value 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.
パーハロオレフィンとしては、テトラフルオロエチレン（ＴＦＥ）、クロロトリフルオロエチレン（ＣＴＦＥ）、ヘキサフルオロプロピレン（ＨＦＰ）等の１種または２種以上が挙げられる。好ましいフルオロオレフィンとしては、耐候性に優れることから、ＴＦＥまたはＨＦＰ、特にＴＦＥが挙げられる。 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.
パーハロオレフィン単位の含有量は、耐候性に優れることから、３０～７０モル％が好ましい。さらには３５～５５モル％、特に４０～５０モル％が好ましい。 The content of the perhaloolefin unit is preferably 30 to 70 mol% because of excellent weather resistance. Further, 35 to 55 mol%, particularly 40 to 50 mol% is preferable.
非フッ素ビニル単量体としては、炭素数２～４の非フッ素ビニル単量体が好ましい。例えば、エチレン、プロピレン、ｎ－ブチレン、イソブチレン、酢酸ビニル等が挙げられ、これらのなかでも、特にパーハロオレフィンとの共重合性が良好で、透明性の向上やガラス転移温度を下げて柔軟性を改善する点からイソブチレンが好ましい。 As the non-fluorinated vinyl monomer, a non-fluorinated vinyl monomer having 2 to 4 carbon atoms is preferable. For example, ethylene, propylene, n-butylene, isobutylene, vinyl acetate, etc. are 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.
非フッ素ビニル単量体単位の含有量は、製造が容易であり、硬化剤との相溶性にも優れることから、５～３５モル％が好ましい。さらには１５～３０モル％が好ましい。 The content of the non-fluorine vinyl monomer unit is preferably 5 to 35 mol% because it is easy to produce and is excellent in compatibility with the curing agent. Furthermore, 15 to 30 mol% is preferable.
水酸基含有ビニル単量体としては、たとえば式：
ＣＨ２＝ＣＨＲ２１
（式中、Ｒ２１は－ＯＲ２２または－ＣＨ２ＯＲ２２（ただし、Ｒ２２は水酸基を有するアルキル基である））で表わされる水酸基含有アルキルビニルエーテルや水酸基含有アルキルアリルエーテルが挙げられる。Ｒ２２としては、たとえば炭素数１～８の直鎖状または分岐鎖状のアルキル基に１～３個、好ましくは１個の水酸基が結合したものである。これらの例としては、たとえば２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等が挙げられる。これらのなかでも、４－ヒドロキシブチルビニルエーテル、２－ヒドロキシエチルビニルエーテルが重合反応性、硬化性が優れる点で好ましい。 Examples of the hydroxyl group-containing vinyl monomer include the formula:
CH 2 = CHR 21
(Wherein R 21 is —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 and a hydroxyl group-containing alkyl allyl ether. R 22 is, for example, one having 1 to 3, preferably 1 hydroxyl group bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these are, 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-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. Of these, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferred because of excellent polymerization reactivity and curability.
他の水酸基含有ビニル単量体としては、たとえばアクリル酸２－ヒドロキシエチル、メタクリル酸２－ヒドロキシエチル等が例示できる。 Examples of other hydroxyl group-containing vinyl monomers include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
水酸基含有ビニル単量体単位の含有量は、上記含フッ素共重合体の水酸基価を１０～２００ｍｇＫＯＨ／ｇの範囲にする量が好ましい。水酸基価としては、１０ｍｇＫＯＨ／ｇ以上、さらには３０ｍｇＫＯＨ／ｇ以上、特に５０ｍｇＫＯＨ／ｇ以上の水酸基価を有していることが、耐候性に優れる点で好ましい。また水酸基価の上限は２００ｍｇＫＯＨ／ｇ、好ましくは１５０ｍｇＫＯＨ／ｇであることが塗膜に可とう性を付与する点で有利である。 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.
ウンデシレン酸は炭素数１１の直鎖の不飽和カルボン酸であり、クロトン酸に比べて炭化水素鎖が長く硬化剤との相溶性を大きく改善でき、また、トリメリット酸を用いてのカルボキシル基を導入した場合に生じるようなエステル結合を生じないので、エステルの開裂による貯蔵安定性の低下もない。しかも、単独重合体ができにくく、重合反応性が良好で難加水分解性である等の点で好ましい。 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.
ウンデシレン酸単位の含有量は、得られる含フッ素共重合体の酸価を１０～１００ｍｇＫＯＨ／ｇの範囲にする量が好ましい。なかでも、酸価を１０～８０ｍｇＫＯＨ／ｇ、特に１５～６０ｍｇＫＯＨ／ｇの範囲にする量が好ましい。 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. Among them, an amount that makes the acid value in the range of 10 to 80 mgKOH / g, particularly 15 to 60 mgKOH / g is preferable.
上記含フッ素共重合体の分子量は数平均分子量で１００，０００以下、好ましくは５０，０００以下のものが製造が容易である観点から好ましく、４，０００以上、特に８，０００以上のものが耐候性に優れる点で好ましい。 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.
以下に好ましい具体的な含フッ素共重合体を例示するが、これらに限定されるものではない。 Specific preferred fluorine-containing copolymers are illustrated below, but are not limited thereto.
ＴＦＥ／ヒドロキシブチルビニルエーテル（ＨＢＶＥ）／イソブチレン（ＩＢ）／ウンデシレン酸／安息香酸ビニル（ＶＢｚ）／ピバリン酸ビニル共重合体、ＴＦＥ／ヒドロキシブチルビニルエーテル（ＨＢＶＥ）／酢酸ビニル／ウンデシレン酸／安息香酸ビニル／ピバリン酸ビニル共重合体、ＴＦＥ／ヒドロキシブチルビニルエーテル（ＨＢＶＥ）／イソブチレン／バーサティック酸ビニル／ウンデシレン酸共重合体、ＴＦＥ／酢酸ビニル／イソブチレン／バーサティック酸ビニル／ウンデシレン酸共重合体。 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.
ウンデシレン酸によって導入されるカルボキシル基は、含フッ素共重合体を水に分散しやすくし、安定な水性分散体を形成するためのものだけでなく、架橋に用いてもよい。 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.
カルボキシル基はそのままでも水分散性を与えるが、アルカリで中和して水溶性または水分散性とすることにより、より一層水分散性が向上する。具体的には、たとえばアンモニウム塩、アミン塩またはアルカリ金属塩等とすることが好ましい。 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.
中和は、水と混合する前、混合する際、または混合後に行ない、水溶性または水分散性の官能基に変換する。 Neutralization takes place before, during or after mixing with water to convert to water-soluble or water-dispersible functional groups.
中和に使用する中和剤としては、アンモニア；ジエチルアミン、エチルエタノールアミン、ジエタノールアミン、モノエタノールアミン、モノプロパノールアミン、イソプロパノールアミン、エチルアミノエチルアミン、ヒドロキシエチルアミン、ジエチレントリアミン、トリエチルアミン等の有機アミン類；水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物等が挙げられる。これらのうちアンモニア、トリエチルアミン、ジエタノールアミンが入手の利便性、エマルションの安定性等の点で好ましく、特にアンモニアとトリエチルアミンが取り扱い性容易の点で有利である。 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.
中和剤は、水溶液の形態で使用することが好ましいが、ガスまたは固形分の形態で使用してもよい。 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.
中和は、含フッ素共重合体が有する酸価のうち、５ｍｇＫＯＨ／ｇ以上、好ましくは１０ｍｇＫＯＨ／ｇ以上、また７０ｍｇＫＯＨ／ｇ以下、そして好ましくは５０ｍｇＫＯＨ／ｇ以下に相当するカルボキシル基を中和剤で中和すればよい。 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
なお、本発明における酸価および水酸基価は、つぎの方法で算出した計算値である。 The acid value and hydroxyl value in the present invention are calculated values calculated by the following method.
（水酸基価算出方法）
生成したポリマー、ポリマー溶液、残存モノマー量の分析およびモノマー仕込み量から、ポリマー中のモノマー組成を算出する。つぎに、その全モノマー組成と水酸基含有モノマーの組成からポリマー中の水酸基価を算出する。 (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.
（酸価算出方法）
生成したポリマー、ポリマー溶液、残存モノマー量の分析およびモノマー仕込み量から、ポリマー中のモノマー組成を算出する。つぎに、その全モノマー組成とカルボキシル基含有モノマーの組成からポリマー中の酸価を算出する。 (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.
上記樹脂は、複合重合体粒子であることも好ましい。上記複合重合体粒子は、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）とを同一粒子内に含むことが好ましい。フルオロポリマー（Ａ）及びアクリルポリマー（Ｂ）は単一粒子中に存在する。この点で上記含フッ素複合重合体粒子は、フルオロポリマー（Ａ）の粒子及びアクリルポリマー（Ｂ）の粒子を単に混合することにより得られる粒子とは相違する。フルオロポリマー（Ａ）及びアクリルポリマー（Ｂ）は化学的に結合していない。 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.
上記複合重合体粒子は、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）が９５／５～１０／９０であることが好ましい。質量比（Ａ／Ｂ）としては、９０／１０以下がより好ましく、２０／８０以上がより好ましく、２５／７５以上が更に好ましい。質量比（Ａ／Ｂ）が上記範囲内にあると、上記表面自由エネルギーを有する上記被覆層を容易に形成することができる。 The composite polymer particles preferably have a mass ratio (A / B) between the fluoropolymer (A) and 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.
フルオロポリマー（Ａ）は、フルオロオレフィンに基づく繰り返し単位（フルオロオレフィン単位）を含むものである。上記フルオロオレフィンとしては、例えば、テトラフルオロエチレン（ＴＦＥ）、ヘキサフルオロプロピレン（ＨＦＰ）、パーフルオロ（アルキルビニルエーテル）（ＰＡＶＥ）、 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),
Figure JPOXMLDOC01-appb-C000001
 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。
Figure JPOXMLDOC01-appb-C000001
 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.
また、上記フルオロオレフィンとして、官能基含有フルオロオレフィンも使用できる。
上記官能基含有フルオロオレフィンとしては、例えば、式：
ＣＸ３ ２＝ＣＸ４－（Ｒｆ）ｍ－Ｙ１
（式中、Ｙ１は－ＯＨ、－ＣＯＯＭ２、－ＳＯ２Ｆ、－ＳＯ３Ｍ２（Ｍ２は水素原子、ＮＨ４基またはアルカリ金属）、カルボン酸塩、カルボキシエステル基、エポキシ基またはシアノ基；Ｘ３およびＸ４は同じかまたは異なりいずれも水素原子またはフッ素原子；Ｒｆは炭素数１～４０の２価の含フッ素アルキレン基若しくは含フッ素オキシアルキレン基、または炭素数２～４０のエーテル結合を含有する２価の含フッ素アルキレン基若しくは含フッ素オキシアルキレン基；ｍは０または１）で示される化合物が挙げられる。 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).
上記官能基含有フルオロオレフィンの具体例としては、例えば、 Specific examples of the functional group-containing fluoroolefin include, for example,
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
等が挙げられる。 Etc.
上記フルオロオレフィンとして、ヨウ素含有モノマー、例えば、特公平５－６３４８２号公報や特開昭６２－１２７３４号公報に記載されているパーフルオロ（６，６－ジヒドロ－６－ヨード－３－オキサ－１－ヘキセン）、パーフルオロ（５－ヨード－３－オキサ－１－ペンテン）等のパーフルオロビニルエーテルのヨウ素化物も使用できる。 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. Periodinated vinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
なかでも、上記フルオロオレフィンとしては、フッ化ビニル、ビニリデンフルオライド、テトラフルオロエチレン、ヘキサフルオロプロピレン、及び、クロロトリフロロエチレンからなる群より選択される少なくとも１種であることが好ましい。 Among these, the fluoroolefin is preferably at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.
また、上記フルオロオレフィンとしては、ビニリデンフルオライドがより好ましく、ビニリデンフルオライドと、テトラフルオロエチレン、ヘキサフルオロプロピレン及びクロロトリフルオロエチレンからなる群より選択される少なくとも１種と、であることが更に好ましい。 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. .
フルオロポリマー（Ａ）は、上記フルオロオレフィン単位の他に、フルオロオレフィンと共重合可能な非フッ素系単量体単位を含んでいてもよい。上記フルオロオレフィンと共重合可能な非フッ素系単量体としては、例えば、エチレン、プロピレン、イソブチレン等のオレフィン類、ビニルエーテル系単量体、アリルエーテル系単量体、ビニルエステル系単量体、アクリル系単量体、メタクリル系単量体等が挙げられる。 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.
フルオロポリマー（Ａ）は、フルオロオレフィン単位として、ビニリデンフルオライド単位を含むことが好ましい。アクリルポリマー（Ｂ）との相溶性の観点からは、フルオロポリマー（Ａ）は、ビニリデンフルオライド単位が、フルオロポリマー（Ａ）を構成する全重合単位に対して５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９５モル％以下であることが好ましい。フルオロポリマー（Ａ）は、ビニリデンフルオライド単位と、更に、テトラフルオロエチレン、ヘキサフルオロプロピレン及びクロロトリフルオロエチレンからなる群より選択される少なくとも１種のフルオロオレフィンの単位を含むことがより好ましい。 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.
フルオロポリマー（Ａ）としては、ＶｄＦ／ＴＦＥ／ＣＴＦＥ共重合体、ＶｄＦ／ＴＦＥ共重合体、ＶｄＦ／ＴＦＥ／ＨＦＰ共重合体、ＶｄＦ／ＣＴＦＥ共重合体、ＶｄＦ／ＨＦＰ共重合体、及び、ＰＶｄＦからなる群より選択される少なくとも１種であることが好ましく、ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝４０～９９／１～５０／０～３０（モル％）、ＶｄＦ／ＴＦＥ＝５０～９９／１～５０（モル％）、ＶｄＦ／ＴＦＥ／ＨＦＰ＝４５～９９／０～３５／５～５０（モル％）、ＶｄＦ／ＣＴＦＥ＝４０～９９／１～３０（モル％）、及び、ＶｄＦ／ＨＦＰ＝５０～９９／１～５０（モル％）からなる群より選択される少なくとも１種であることがより好ましい。 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%).
アクリルポリマー（Ｂ）は、アクリルモノマーに基づく繰り返し単位（アクリルモノマー単位）を含む。上記アクリルモノマーとしては、アクリル酸、アクリル酸エステル、メタクリル酸及びメタクリル酸エステルからなる群より選択される少なくとも１種であることが好ましい。 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.
アクリルポリマー（Ｂ）は、アクリル酸、アクリル酸エステル、メタクリル酸及びメタクリル酸エステルからなる群より選択される少なくとも１種のアクリルモノマー単位を含むことが好ましく、メタクリル酸エステル単位と、アクリル酸、メタクリル酸及びアクリル酸エステルからなる群より選択される少なくとも１種のアクリルモノマー単位とを含むことがより好ましい。 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.
アクリル酸エステルとしては、アルキル基の炭素数が１～１０のアクリル酸アルキルエステルが好ましく、メチルアクリレート、エチルアクリレート、ｎ－プロピルアクリレート、イソプロピルアクリレート、ｎ－ブチルアクリレート、２－エチルへキシルアクリレート、シクロヘキシルアクリレート、及び、グリシジルアクリレートからなる群より選択される少なくとも１種のアクリル酸アルキルエステルであることがより好ましく、ｎ－ブチルアクリレート及び２－エチルへキシルアクリレートからなる群より選択される少なくとも１種のアクリル酸アルキルエステルであることが更に好ましい。 As the acrylate ester, an alkyl acrylate ester having an alkyl group having 1 to 10 carbon atoms is preferable. Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl More preferably, the acrylate is at least one alkyl acrylate selected from the group consisting of 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.
メタクリル酸エステルとしては、アルキル基の炭素数が１～１０のメタクリル酸アルキルエステルが好ましく、メチルメタクリレート、プロピルメタクリレート、エチルメタクリレート、ブチルメタクリレート、２－エチルヘキシルメタクリレート、シクロヘキシルメタクリレート、及び、グリシジルメタクリレートからなる群より選択される少なくとも１種のメタクリル酸アルキルエステルであることがより好ましく、メチルメタクリレート、ブチルメタクリレート及び、シクロヘキシルメタクリレートからなる群より選択される少なくとも１種のメタクリル酸アルキルエステルであることが更に好ましい。 The methacrylic acid ester is preferably a methacrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms, and is 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.
アクリルポリマー（Ｂ）は、上記被覆層の上記表面自由エネルギーを容易に調整する観点から、メタクリル酸エステル単位と、アクリル酸、メタクリル酸及びアクリル酸エステルからなる群より選択される少なくとも１種のアクリルモノマー単位とを含むことが好ましく、造膜性に優れ、上記被覆層の上記表面自由エネルギーを容易に調整する観点から、メタクリル酸エステル単位とメタクリル酸単位とを含むことがより好ましい。 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.
アクリルポリマー（Ｂ）は、アクリルポリマー（Ｂ）の全構成単位に対して、５～９８質量％のメタクリル酸エステル単位と、９５～２質量％のメタクリル酸単位とを含むことが更に好ましい。 The acrylic polymer (B) further preferably 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).
アクリルポリマー（Ｂ）は、加水分解性シリル基含有単量体単位を含むものであってもよい。加水分解性シリル基含有単量体としては、
ＣＨ２＝ＣＨＳｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＳｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ３Ｈ７）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ４Ｈ９）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ６Ｈ１３）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ８Ｈ１７）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ１０Ｈ２１）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ１２Ｈ２５）３、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣ２Ｈ５）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣ２Ｈ５）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）１１Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）１１Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ｏ－Ｃ６Ｈ４）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ｏ－Ｃ６Ｈ４）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨ（ＣＨ２）８Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ＣＨ２）１０Ｓｉ（ＯＣＨ３）３
等が挙げられる。これらの加水分解性シリル基含有単量体は、単独で用いてもよいし、２種以上を併用してもよい。 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.
密着性、貯蔵安定性が良好な点から、なかでも、γ－メタクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルメチルジメトキシシラン、γ－メタクリロキシプロピルトリエトキシシラン、及び、γ－メタクリロキシプロピルメチルジエトキシシランからなる群より選択される少なくとも１種が好ましい。 Among these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropylmethyl are preferable because of their good adhesion and storage stability. At least one selected from the group consisting of diethoxysilane is preferred.
加水分解性シリル基含有単量体単位の含有量は、アクリルポリマー（Ｂ）の全構成単位に対して、０．１～２質量％であることが好ましい。０．１質量％より少ないと密着性が不充分となるおそれがあり、２質量％を超えると造膜性及び貯蔵安定性が不安定となるおそれがある。より好ましい上限は１．５質量％である。より好ましい下限は０．２質量％である。 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.
アクリルポリマー（Ｂ）は、更に、紫外線吸収部位を有するエチレン性不飽和基含有単量体、及び、光安定化部位を有するエチレン性不飽和基含有単量体からなる群より選択される少なくとも１種の単量体に基づく重合単位を含むことが好ましい。 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.
紫外線吸収部位を有するエチレン性不飽和基含有単量体としては、べンゾトリアゾール型の紫外線吸収部位を有するメタクリレートであるＲＵＶＡ－９３（大塚化学（株）製）（以下ＲＵＶＡ－９３という）、シアノアクリレート系等を挙げることができる。また、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系等の水酸基を含有する公知の紫外線吸収剤とメタクリル酸クロリド、アクリル酸クロリド等の酸ハロゲン化物との反応により得られる紫外線吸収剤のメタクリル酸エステル、アクリル酸エステル等も挙げることができる。これらは、単独で用いても、２種以上を併用してもよい。
紫外線吸収部位は、ベンゾトリアゾール系の水酸基を有する部位であることが好ましい。 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.
具体的なエチレン性不飽和基含有単量体を有するベンゾフェノン系化合物としては、限定はされず、例えば、２－ヒドロキシ－４－［２－（メタ）アクリロイルオキシ］エトキシベンゾフェノン、２－ヒドロキシ－４－［２－（メタ）アクリロイルオキシ］ブトキシベンゾフェノン、２，２´－ジヒドロキシ－４－［２－（メタ）アクリロイルオキシ］エトキシベンゾフェノン、２－ヒドロキシ－４－［２－（メタ）アクリロイルオキシ］エトキシ－４´－（２－ヒドロキシエトキシ）ベンゾフェノン、２－ヒドロキシ－３－ｔｅｒｔ－ブチル－４－［２－（メタ）アクリロイルオキシ］エトキシベンゾフェノン、及び、２－ヒドロキシ－３－ｔｅｒｔ－ブチル－４－［２－（メタ）アクリロイルオキシ］ブトキシベンゾフェノン等が好ましく挙げられる。これらは単独で用いても２種類以上を併用してもよい。 Specific examples of the benzophenone compound having an ethylenically unsaturated group-containing monomer include, but are not limited to, 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.
具体的なエチレン性不飽和基含有単量体を有するベンゾトリアゾール系化合物としては、限定はされず、例えば、２－［２´－ヒドロキシ－５´－（メタ）アクリロイルオキシメチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２´－ヒドロキシ－５´－（メタ）アクリロイルオキシエチルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２´－ヒドロキシ－５´－（メタ）アクリロイルオキシプロピルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２´－ヒドロキシ－５´－（メタ）アクリロイルオキシヘキシルフェニル］－２Ｈ－ベンゾトリアゾール、２－［２´－ヒドロキシ－３´－ｔｅｒｔ－ブチル－５´－（メタ）アクリロイルオキシエチルフェニル］－２Ｈ－ベンゾトリアゾール、及び、２－〔２´－ヒドロキシ－５´－（β－（メタ）アクリロイルオキシエトキシ）－３´－ｔｅｒｔ－ブチルフェニル〕－５－ｔｅｒｔ－ブチル－２Ｈ－ベンゾトリアゾール、２－［２´－ヒドロキシ－５´－（メタクロイルオキシエチル）フェニル］－２Ｈ－ベンゾトリアゾール（ＲＵＶＡ－９３）等が好ましく挙げられる。これらは単独で用いても２種類以上を併用してもよい。 Specific examples of the benzotriazole-based compound having an ethylenically unsaturated group-containing monomer include, but are not limited to, 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) and the like are preferred. These may be used alone or in combination of two or more.
具体的なエチレン性不飽和基含有単量体を有するトリアジン系化合物としては、限定はされず、例えば、２，４－ジフェニル－６－［２－ヒドロキシ－４－（２－アクリロイルオキシエトキシ）］－ｓ－トリアジン、２，４－ビス（２－メチルフェニル）－６－［２－ヒドロキシ－４－（２－アクリロイルオキシエトキシ）］－ｓ－トリアジン、及び、２，４－ビス（２－メトキシフェニル）－６－［２－ヒドロキシ－４－（２－アクリロイルオキシエトキシ）］－ｓ－トリアジン等が好ましく挙げられる。これらは単独で用いても２種類以上を併用してもよい。 A specific triazine compound having an 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.
光安定化部位を有するエチレン性不飽和基含有単量体としては、たとえばアデカスタブＬＡ８２（旭電化工業（株）製）、アデカスタブＬＡ８７（旭電化工業（株）製）等のほか、水酸基を有する光安定化剤とメタクリル酸、アクリル酸とのエステル等も挙げることができる。これらは、単独で用いても、２種以上を併用してもよい。 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.
具体的な光安定化部位を有するエチレン性不飽和基含有単量体としては、１，２，２，６，６－ペンタメチル－４－ピペリジルメタクリレート、１，２，２，６，６－ペンタメチル－４－ピペリジルアクリレート、２，２，６，６－テトラメチル－４－ピペリジルメタクリレート、２，２，６，６－テトラメチル－４－ピペリジルアクリレート、１，２，２，６，６－ペンタメチル－４－イミノピペリジルメタクリレート、２，２，６，６，－テトラメチル－４－イミノピペリジルメタクリレート、４－シアノ－２，２，６，６－テトラメチル－４－ピペリジルメタクリレート、４－シアノ－１，２，２，６，６－ペンタメチル－４－ピペリジルメタクリレート等が挙げられる。 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.
アクリルポリマー（Ｂ）は、不飽和カルボン酸類、水酸基含有アルキルビニルエーテル類、カルボン酸ビニルエステル類、α－オレフィン類、芳香族ビニル単量体、エポキシ基含有単量体等の非フッ素化オレフィン単位を含むものであってもよい。 The acrylic polymer (B) comprises 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.
不飽和カルボン酸類の具体例としては、たとえばビニル酢酸、クロトン酸、桂皮酸、３－アリルオキシプロピオン酸、３－（２－アリロキシエトキシカルボニル）プロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニル、ウンデシレン酸等が挙げられる。なかでも、単独重合性が低く単独重合体ができにくい点、カルボキシル基の導入を制御しやすい点から、ビニル酢酸、クロトン酸、イタコン酸、マレイン酸、マレイン酸モノエステル、フマル酸、フマル酸モノエステル、３－アリルオキシプロピオン酸、及び、ウンデシレン酸からなる群より選択される少なくとも１種が好ましい。 Specific examples of 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.
水酸基含有アルキルビニルエーテル類の具体例としては、たとえば２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、２－ヒドロキシプロピルビニルエーテル、２－ヒドロキシ－２－メチルプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、４－ヒドロキシ－２－メチルブチルビニルエーテル、５－ヒドロキシペンチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、２－ヒドロキシエチルアリルエーテル、４－ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテル等が挙げられる。重合反応性が優れる点で、４－ヒドロキシブチルビニルエーテル、及び、２－ヒドロキシエチルビニルエーテルからなる群より選択される少なくとも１種が好ましい。 Specific examples of hydroxyl-containing alkyl vinyl ethers 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- Examples thereof 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.
カルボン酸ビニルエステル類の具体例としては、たとえば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル、安息香酸ビニル、パラ－ｔ－ブチル安息香酸ビニル等が挙げられる。カルボン酸ビニルエステル類を用いることで、得られる塗膜に、光沢の向上、ガラス転移温度の上昇等の特性を付与できる。 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. And vinyl benzoate and vinyl para-t-butylbenzoate. 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.
α－オレフィン類の具体例としては、たとえばエチレン、プロピレン、ｎ－ブテン、イソブテン、スチレン等が挙げられる。α－オレフィン類を用いることで、得られる塗膜に、可とう性の向上等の特性を付与できる。 Specific examples of α-olefins include ethylene, propylene, n-butene, isobutene, styrene, and the like. By using α-olefins, properties such as improved flexibility can be imparted to the resulting coating film.
芳香族ビニル単量体の具体例としては、スチレン、α－メチルスチレン等のスチレン類が例示できる。エポキシ基含有単量体の具体例としては、アリルグリシジルエーテル等が例示できる。 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.
アクリルポリマー（Ｂ）は、アクリルポリマー（Ｂ）の全構成単位に対して、５～９８質量％のメタクリル酸エステル単位と、９３～１．９質量％のメタクリル酸単位と、０．１～２質量％の加水分解性シリル基含有単量体単位とを含むことが好ましく、９０～９８質量％のメタクリル酸エステル単位と、８～１．９質量％のメタクリル酸単位と、０．１～２質量％の加水分解性シリル基含有単量体単位とを含むことがより好ましい。 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). Preferably, it contains 90% to 98% by weight of methacrylic acid ester units, 8% to 1.9% by weight of methacrylic acid units, and 0.1% to 2%. More preferably, it contains a mass% hydrolyzable silyl group-containing monomer unit.
上記複合重合体粒子は、上記フルオロオレフィンを水性分散重合して、フルオロポリマー（Ａ）粒子を含む水性分散体を得る工程、上記フルオロポリマー（Ａ）粒子を含む水性分散体中で、少なくとも上記アクリルモノマーを、フルオロポリマー（Ａ）粒子にシード重合する工程を含む製造方法により得られたものであることが好ましい。 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.
上記水性分散重合及び上記シード重合は、所望により、非反応性アニオン界面活性剤、反応性アニオン界面活性剤、非反応性ノニオン界面活性剤、反応性ノニオン界面活性剤等の存在下に実施することもできる。 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.
上記被覆層の上記表面自由エネルギーを容易に調整する観点から、上記シード重合を、反応性アニオン界面活性剤及び反応性ノニオン界面活性剤からなる群より選択される少なくとも１種の存在下に実施することが好ましく、反応性アニオン界面活性剤の存在下に実施することがより好ましい。 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.
上記反応性アニオン界面活性剤としては、
式（３）：ＣＨ２＝Ｃ（ＣＨ３）ＣＨ２ＣＨ２－Ｏ－（ＢＯ）ｍ－（ＥＯ）ｎ－ＳＯ３ＮＨ４
（式中、ＢＯはブチレンオキサイド単位；ＥＯはＣＨ２ＣＨ２ＯまたはＣＨ（ＣＨ３）Ｏ単位；ｍは０～５０の整数；ｎは０～１００の整数；ｍ＋ｎは０～１５０の整数である。）で示される化合物（３）、
式（４）：ＣＨ２＝ＣＨＣＨ２－Ｏ－Ｒ１－Ｘ
（式中、Ｒ１は酸素原子および／または窒素原子を有していてもよい炭化水素鎖、ＸはＳＯ３Ｙ（ＹはＮＨ４またはアルカリ金属）である。）で示される化合物（４）等が挙げられる。 As the reactive anionic surfactant,
Formula (3): CH 2 ═C (CH 3 ) CH 2 CH 2 —O— (BO) m — (EO) n —SO 3 NH 4
(Wherein BO is a butylene oxide unit; EO is a CH 2 CH 2 O or CH (CH 3 ) O unit; m is an integer from 0 to 50; n is an integer from 0 to 100; m + n is an integer from 0 to 150. Compound (3) represented by:
Formula (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.
化合物（３）の市販品としては、例えば、花王（株）製のラテムルＰＤ－１０４等が挙げられる。 Examples of commercially available compounds (3) include Latemul PD-104 manufactured by Kao Corporation.
式（４）中のＲ１は、酸素原子および／または窒素原子を有していてもよい炭化水素鎖である。
上記Ｒ１は、オキシアルキレン基を含む炭化水素基であることが好ましい。
Ｘは、ＳＯ３Ｙ（ＹはＮＨ４またはアルカリ金属）である。アルカリ金属としては、Ｎａ、Ｋが好ましい。
上記オキシアルキレン基としては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等の炭素数２～４の直鎖状または分岐鎖状のオキシアルキレン基が挙げられる。 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.
Examples of the oxyalkylene group include linear or branched oxyalkylene groups having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide.
式（４）で示される化合物としては、式（４ａ）： Examples of the compound represented by the formula (4) include the formula (4a):
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ１’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ＳＯ３Ｙ（ＹはＮＨ４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。
Ｒ１’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。
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 1 ′ is a linear or branched hydrocarbon chain that 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; Preferred examples include compounds (4a) represented by an alkylene group; n is an integer of 1 to 100; and X is SO 3 Y (Y is NH 4 or an alkali metal atom).
R 1 ′ has preferably 1 to 51 carbon atoms, more preferably 5 to 21 carbon atoms, and still more preferably 10 to 16 carbon atoms.
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.
式（４ａ）としては、次の式（４ａ－１）： As the formula (4a), the following formula (4a-1):
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ３’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ＳＯ３Ｙ（ＹはＮＨ４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）；
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 3 ′ is a linear or branched hydrocarbon chain having 1 to 50 carbon atoms which may contain a phenyl group or a phenylene group; 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) The following formula (4a-2);
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ４’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ＳＯ３Ｙ（ＹはＮＨ４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。
Figure JPOXMLDOC01-appb-C000006
 (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.
式（４ａ－１）において、Ｒ３’は炭素数１～５０であり、好ましくは５～２０であり、より好ましくは１０～１５である。ｎは、１～１００の整数であり、分散安定性および耐水性の点から１～６０の整数であることが好ましく、５～３０の整数であることがより好ましく、１０～１５の整数であることが更に好ましい。
Ｘは、ＳＯ３ＮＨ４が好ましい。
ＡＯは、エチレンオキサイドであることが好ましい。 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.
化合物（４ａ－１）の市販品としては、例えば、アデカリアソープのＳＥシリーズ、ＳＲシリーズ（いずれも、ＡＤＥＫＡ社製）等を挙げることができる。 Examples of the commercially available compound (4a-1) include the SE series and SR series of ADEKA rear soap (both manufactured by ADEKA).
式（４ａ－２）において、Ｒ４’は炭素数１～５０のアルキル基であり、好ましくは５～２０であり、より好ましくは１０～１５である。ｎは、１～１００の整数であり、分散安定性および耐水性の点から１～２０の整数であることが好ましく、５～１５であることが更に好ましい。
Ｘは、ＳＯ３ＮＨ４が好ましい。
ＡＯは、エチレンオキサイドであることが好ましい。 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 viewpoint of dispersion stability and water resistance.
X is preferably SO 3 NH 4 .
AO is preferably ethylene oxide.
化合物（４ａ－２）の市販品としては、例えば、アクアロンＫＨ－１０（第一工業製薬（株）製）等が挙げられる。 Examples of the commercially available compound (4a-2) include Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
上記シード重合において、上記反応性アニオン界面活性剤の添加量は、上記シード粒子１００質量部に対し、０．１５～１００質量部が好ましく、０．７７質量部以上がより好ましく、１．５質量部以上が更に好ましく、７０質量部以下がより好ましく、５０質量部以下が更に好ましい。 In the seed polymerization, the amount of the reactive anionic surfactant added is preferably 0.15 to 100 parts by weight, more preferably 0.77 parts by weight or more, and 1.5 parts by weight with respect to 100 parts by weight 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.
上記被覆層は、上記樹脂を配合した塗料の乾燥塗膜からなることが好ましく、上記塗料を塗布した後、乾燥してなることがより好ましい。 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.
上記塗料は、溶剤塗料、水性塗料、粉体塗料等であってよいが、溶剤塗料又は水性塗料であることが好ましく、水性塗料であることがより好ましい。すなわち、上記塗料は、上記樹脂及び水を含むことが好ましい。 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.
溶剤塗料における溶剤としては、有機溶剤が好ましく、酢酸エチル、酢酸ブチル、酢酸イソプロピル、酢酸イソブチル、酢酸セロソルブ、プロピレングリコールメチルエーテルアセテート等のエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；テトラヒドロフラン、ジオキサン等の環状エーテル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド類；キシレン、トルエン、ソルベントナフサ等の芳香族炭化水素類；プロピレングリコールメチルエーテル、エチルセロソルブ等のグリコールエーテル類；カルビトールアセテート等のジエチレングリコールエステル類；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、ｎ－ノナン、ｎ－デカン、ｎ－ウンデカン、ｎ－ドデカン、ミネラルスピリット等の脂肪族炭化水素類；これらの混合溶剤等が挙げられる。
中でも、エステル類がより好ましく、酢酸ブチルが更に好ましい。 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.
上記樹脂を配合した塗料の固形分濃度は、塗装効率がよいことから通常２０質量％以上、好ましくは３０質量％以上であり、また貯蔵安定性の点から７０質量％以下、好ましくは６０質量％以下である。 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.
上記塗料は、更に、非反応性界面活性剤を含むものであってもよい。特に、上記塗料が水性塗料である場合、非反応性界面活性剤を含むことが好ましい。 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.
上記非反応性界面活性剤としては、たとえば非反応性アニオン界面活性剤、非反応性ノニオン界面活性剤またはそれらの組み合わせを使用することができ、場合により非反応性両性界面活性剤、非反応性カチオン界面活性剤を使用することもできる。 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.
非反応性アニオン界面活性剤としては、たとえば高級アルコールの硫酸エステルのナトリウム塩、アルキルベンゼンスルホン酸ナトリウム、ジアルキルスクシネートスルホン酸のナトリウム塩またはアルキルジフェニルエーテルスルホン酸のナトリウム塩等を使用することができる。これらの中で好ましい具体例は、アルキルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、ポリオキシエチレンアルキル（またはアルキルフェニル）エーテルスルホネート等である。非反応性非イオン界面活性剤としては、たとえばポリオキシエチレンアルキルエーテルまたはポリオキシエチレンアルキルアリールエーテル等を使用することができる。好ましい具体例は、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等である。非反応性両性界面活性剤としては、ラウリルベタイン等が好適である。非反応性カチオン界面活性剤としては、たとえばアルキルピリジニウムクロリド、アルキルアンモニウムクロリド等を使用することができる。また、単量体と共重合性の乳化剤、たとえばスチレンスルホン酸ナトリウム、アルキルアリールスルホン酸ナトリウム等も使用することができる。 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.
非反応性ノニオン界面活性剤としては、また、ポリオキシエチレンアルキルエーテル、ポリオキシポリアルキレンアルキルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリベンジルフェニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。ポリオキシエチレンアルキルエーテルとしては、エマルゲン１２０（花王株式会社）等が挙げられる。 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).
非反応性アニオン界面活性剤としては、脂肪酸塩、アルケニルコハク酸塩、高級アルコール硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、ナフタリンスルホン酸ホルマリン縮合物、特殊カルボン酸型高分子界面活性剤等が挙げられる。非反応性アニオン界面活性剤の具体例としては、ニューコール７０７－ＳＦ（日本乳化剤株式会社）、ハイテノールＮＦ－０８（第一工業製薬株式会社）等が挙げられる。 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.
上記塗料には、更に、要求特性に応じて各種の添加剤を配合することができる。添加剤としては、成膜助剤、硬化剤、硬化促進剤、硬化遅延剤、顔料、顔料分散剤、消泡剤、レベリング剤、紫外線吸収剤、光安定剤、増粘剤、密着改良剤、つや消し剤等が挙げられる。 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.
硬化剤としては、上記樹脂の硬化性官能基の種類に応じて選択され、たとえば水酸基含有含フッ素ポリマーに対しては、イソシアネート系硬化剤、メラミン樹脂、シリケート化合物、イソシアネート基含有シラン化合物等が好ましく例示できる。また、カルボキシル基含有含フッ素ポリマーに対してはアミノ系硬化剤やエポキシ系硬化剤が、アミノ基含有含フッ素ポリマーに対してはカルボニル基含有硬化剤やエポキシ系硬化剤、酸無水物系硬化剤が通常採用される。 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.
上記硬化剤としては、また、非ブロック型ポリイソシアネート化合物、ブロック型ポリイソシアネート化合物、メラミン樹脂、アジリジン基、カルボジイミド基及びオキサゾリン基からなる群より選択される少なくとも１種の基を有する架橋剤、ヒドラジン誘導体等が挙げられる。 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.
非ブロック型ポリイソシアネート化合物は、常温での硬化性に優れており、また架橋反応性の点でも優れている。 Non-blocking polyisocyanate compounds are excellent in curability at room temperature and also in terms of crosslinking reactivity.
なお非ブロック型ポリイソシアネート化合物とは、アルコールやオキシム化合物とイソシアネート化合物との反応で得られるブロック型ポリイソシアネート化合物以外の、通常のイソシアネート化合物のことをいう。 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.
非ブロック型ポリイソシアネート化合物としては、特開平１１－３１０７００号公報、特開平７－３３０８６１号公報、特開昭６１－２９１６１３号公報等に記載されているポリエチレンオキシド化合物で変性された非ブロック型ポリイソシアネート化合物が好適である。 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.
具体的には、ポリエチレンオキシド化合物で変性した非ブロック型脂肪族ポリイソシアネート化合物または非ブロック型芳香族ポリイソシアネート化合物が例示される。これらのなかでは、耐候性に優れる点から非ブロック型脂肪族系ポリイソシアネート化合物が好ましい。 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.
非ブロック型脂肪族ポリイソシアネート化合物のうち鎖状脂肪族ポリイソシアネート化合物としては、たとえばトリメチレンジイソシアネート、テトラメチレンジイソシアネート、１，６－ジイソシアナトヘキサン（＝ヘキサメチレンジイソシアネート）、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、２，４，４－または２，２，４－トリメチルヘキサメチレンジイソシアネート、２，６－ジイソシアネートメチルカプトロエート等のジイソシアネート類；リジンエステルトリイソシアネート、１，４，８－トリイソシアネートオクタン、１，６，１１－トリイソシアネートウンデカン、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－トリイソシアネートヘキサン、２，５，７－トリメチル－１，８－ジイソシアネート－５－イソシアネートメチルオクタン等のポリイソシアネート類が例示できる。 Among the non-block type aliphatic polyisocyanate compounds, examples of the chain aliphatic polyisocyanate compound include 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.
非ブロック型脂肪族ポリイソシアネート化合物のうち脂環族ポリイソシアネート化合物としては、たとえば１，３－シクロペンテンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート、１－イソシアナト－３，３，５－トリメチル－５－イソシアナトメチル－シクロヘキサン（＝イソホロンジイソシアネート）、４，４’－メチレンビス（シクロヘキシルイソシアネート）、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、１，３－または１，４－ビス（イソシアネートメチル）シクロヘキサン等のジイソシアネート類；１，３，５－トリイソシアネートシクロヘキサン、１，３，５－トリメチルイソシアネートシクロヘキサン、２－（３－イソシアネートプロピル）－２，５－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、２－（３－イソシアネートプロピル）－２，６－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、３－（３－イソシアネートプロピル）－２，５－ジ（イソシアネートメチル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアネートエチル）－２－イソシアネートメチル－３－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン、６－（２－イソシアネートエチル）－２－イソシアネートメチル－３－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアネートエチル）－２－イソシアネートメチル－２－（３－イソシアネートプロピル）－ビシクロ（２．２．１）－ヘプタン、６－（２－イソシアネートエチル）－２－イソシアネートメチル－２－（３－イソシアネートプロピル）－ビシクロ（２．２．１）ヘプタン等のポリイソシアネート類が例示できる。 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)- Examples of polyisocyanates such as cyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane it can.
非ブロック型芳香族系ポリイソシアネート化合物としては、たとえばトリレンジイソシアネート等が挙げられる。 Examples of non-blocking aromatic polyisocyanate compounds include tolylene diisocyanate.
これらのイソシアネート化合物は単独でまたは２種以上組合わせて使用してもよい。 These isocyanate compounds may be used alone or in combination of two or more.
変性剤であるポリエチレンオキシド化合物としては、たとえばポリオキシエチレンモノオクチルエーテル、ポリオキシエチレンモノラウリルエーテル、ポリオキシエチレンモノデシルエーテル、ポリオキシエチレンモノセチルエーテル、ポリオキシエチレンモノステアリルエーテル、ポリオキシエチレンモノオレイルエーテル等のポリオキシエチレンＣ８～２４アルキルエーテル、好ましくはポリオキシエチレンＣ１０～２２アルキルエーテル、特にポリオキシエチレンＣ１２～１８アルキルエーテル等のポリオキシエチレンアルキルエーテル類；たとえばポリオキシエチレンモノオクチルフェニルエーテル、ポリオキシエチレンモノノニルフェニルエーテル、ポリオキシエチレンモノデシルフェニルエーテル等のポリオキシエチレンＣ８～１２アルキル－Ｃ６～１２アリールエーテル等のポリオキシエチレンモノアルキルアリールエーテル類；たとえばポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタンジステアレート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン－モノ、ジまたはトリＣ１０～２４脂肪酸エステル等のポリオキシエチレンソルビタン高級脂肪酸エステル類；たとえばポリオキシエチレンモノラウリン酸エステル、ポリオキシエチレンモノステアリン酸エステル等のポリオキシエチレンモノＣ１０～２４脂肪酸エステル等のポリオキシエチレンモノ高級脂肪酸エステル類等のノニオン性乳化剤として知られている化合物が例示できる。これらの化合物は単独でまたは２種以上組合わせて使用できる。好ましいものとしては、水分散性が容易である点からポリオキシエチレンＣ８～２４アルキルエーテル、ポリオキシエチレンＣ８～１２アルキルフェニルエーテルが挙げられる。 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.
変性は、たとえば、溶液中にてポリイソシアネート化合物を変性剤と混合し、加熱して反応させる等の方法で行なうことができる。 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.
上記ポリイソシアネート化合物と変性剤との割合は、ポリイソシアネート化合物中のイソシアネート基１当量に対して、変性剤の活性水素原子０．０１～０．０３４当量、好ましくは０．０１５～０．０３当量程度の範囲から選択できる。 The ratio of the polyisocyanate compound to the modifier is 0.01 to 0.034 equivalent, preferably 0.015 to 0.03 equivalent, of the 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.
ポリエチレンオキシド変性の非ブロック型ポリイソシアネート化合物の市販品としては、たとえば住友バイエルウレタン（株）製のバイヒジュール３１００、バイヒジュールＴＰＬＳ２１５０等；旭化成（株）製のデュラネートＷＢ４０－１００等が挙げられるが、これらに限定されるものではない。 Examples of commercially available polyethylene oxide-modified non-blocking polyisocyanate compounds include Bihijoule 3100, Bihijoule TPLS2150 manufactured by Sumitomo Bayer Urethane Co., Ltd., and Duranate WB40-100 manufactured by Asahi Kasei Co., Ltd. It is not limited.
非ブロック型ポリイソシアネート化合物は、通常、水溶液または水分散液の形態で使用する。 The non-blocking polyisocyanate compound is usually used in the form of an aqueous solution or an aqueous dispersion.
ブロック型ポリイソシアネート化合物としては、住化バイエルウレタン（株）製スミジュールＢＬ３１７５、旭化成（株）製のデュラネートＴＰＡ－Ｂ８０Ｅ等の公知の硬化剤が使用できる。 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.
アジリジン基を有する架橋剤の例としては、ＢＦ－グッドリッチ（ＢＦ－Ｇｏｏｄｒｉｃｈ）社から供給されるＸＡＭＡ２、ＸＡＭＡ７などが例示される。
カルボジイミド基を有する架橋剤の例としては、ユニオンカーバイド社から供給されるＵＣＡＲＬＮＫ　Ｃｒｏｓｓｌｉｎｋｅｒ　ＸＬ－２９ＳＥ、日清紡ケミカル社のカルボジライトＥ－０２、Ｅ－０４、ＳＶ－０２、Ｖ－０２Ｖ－０２－Ｌ２、Ｖ－０４、Ｖ－１０などが例示される。
オキサゾリン基を有する架橋剤の例としては、（株）日本触媒から供給されるエポクロスＫ－１０１０Ｅ、エポクロスＫ－１０２０Ｅ、エポクロスＫ－１０３０Ｅ、エポクロスＫ－２０１０Ｅ、エポクロスＫ－２０２０Ｅ、エポクロスＫ－２０３０Ｅ、エポクロスＷＳ－５００などが例示できる。 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 by Union Carbide, Carbodilite E-02, E-04, SV-02, V-02V-02-L2, V, Nisshinbo Chemical Co., Ltd. -04, V-10 and the like 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. An example is Epocros WS-500.
上記ヒドラジン誘導体は少なくとも２個のヒドラジン残基を有し、そしてとくに有利には飽和脂肪酸ジカルボン酸から導かれるものであってよい。とくに重要なものは、２～１０個の炭素原子を有する脂肪族カルボン酸ジヒドラジドである。この種の好適なジヒドラジドは、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジドおよび／またはセバシン酸ジヒドラジドである。炭酸のポリヒドラジドたとえば炭酸ジヒドラジドなどが例示される。 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.
硬化剤は、上記樹脂の硬化性官能基１当量に対して、０．１～５モル当量となるように添加することが好ましく、より好ましくは０．５～１．５モル当量である。 The curing agent is preferably added in an amount of 0.1 to 5 molar equivalents, more preferably 0.5 to 1.5 molar equivalents relative to 1 equivalent of the curable functional group of the resin.
上記樹脂の硬化性官能基の含有量は、ＮＭＲ、ＦＴ－ＩＲ、元素分析、蛍光Ｘ線分析、中和滴定を単量体の種類によって適宜組み合わせることで算出できる。 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.
硬化促進剤としては、例えば有機スズ化合物、酸性リン酸エステル、酸性リン酸エステルとアミンとの反応物、飽和または不飽和の多価カルボン酸またはその酸無水物、有機チタネート化合物、アミン系化合物、オクチル酸鉛等が挙げられる。 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.
硬化促進剤は１種を用いてもよく、２種以上を併用してもよい。硬化促進剤の配合割合は上記樹脂１００質量部に対して１．０×１０－６～１．０×１０－２質量部が好ましく、５．０×１０－５～１．０×１０－３質量部程度がより好ましい。 1 type may be used for a hardening accelerator and it may use 2 or more types together. The mixing 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.
上記親水化層は、コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロカーボンスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種を含むことが好ましく、上記金属酸化物を含むことがより好ましい。 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.
上記コロイダルシリカとしては、たとえば水ガラスの脱ナトリウム（イオン交換法、酸分解法、解膠法）によって製造され、一次粒子径としては、４～１５０ｎｍであり、好ましくは５～５０ｎｍで、このものは通常水性分散液として供給されており、それをそのまま使用できる。 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.
上記コロイダルシリカは、水分散性の状態で酸性側、塩基性側のいずれかであっても用いることができ、酸性側コロイダルシリカとしては、たとえば商品名スノーテックス－Ｏまたはスノーテックス－ＯＬ（日産化学工業（株）製）として市販されている非安定化シリカ（ｐＨ２～４）が利用できる。一方、塩基性側のコロイダルシリカとしては、微量のアルカリ金属イオン、アルミニウムイオン、アンモニウムイオンまたはアミンの添加によって安定化したシリカ（ｐＨ８．４～１０）があり、たとえば商品名スノーテックス２０、スノーテックスＣ、スノーテックスＮ、（以上は日産化学工業（株）製）、商品名ルドックスＨＳ－４０、ＨＳ－３０、ＬＳ、ＳＭ－３０、ＴＭ、ＡＳ、ＡＭ（以上は米国、デュポン社製）、商品名ナルコーク（米国、ナルコケミカル社製）、商品名ミトン（米国、モンサントケミカル社製）等として市販されているものを挙げることができる。前記ｐＨが６～８であるとコロイダルシリカの安定性だけでなく、塗料化したときの塗料の安定性が低下し、凝集、ゲル化の傾向がある。 The colloidal silica can be used on either the acidic side or the basic side in a water-dispersible state. Examples of the acidic side colloidal silica include the trade name SNOWTEX-O or SNOWTEX-OL (Nissan). Non-stabilized silica (pH 2 to 4) commercially available from 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 (the above is manufactured by Nissan Chemical Industries, Ltd.), trade name Ludox HS-40, HS-30, LS, SM-30, TM, AS, AM (the above is 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.
上記コロイダルシリカとともに有機ケイ素化合物を用いることができ、その目的は、塗料化したときに、前記無機質基材、有機質基材への密着性、耐候性、耐薬品性、成膜性に加え、可撓性をさらに向上させることにある。該有機ケイ素化合物としては、式：
Ｒ３１ ａＳｉ（ＯＲ３２）４－ａ
（式中、Ｒ３１は非加水分解性基または水素原子を示し、Ｒ３２はアルキル基、アリール基、アルケニル基または水素原子を示し、ａは０、１または２である）で示される単量体である。 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.
上記非加水分解性基としては、たとえばメチル、エチル、プロピル等のアルキル基、フェニル基、トリル基、メシチル基等のアリール基、ビニル基、アリル基等のアルケニル基、γ－クロロプロピル基等のハロアルキル基、γ－アミノプロピル基、γ－（２－アミノエチル）アミノプロピル基等のアミノアルキル基、γ－グリシドキシプロピル基、β－（３，４－エポキシシクロヘキシル）エチル基等のエポキシアルキル基、γ－メルカプトアルキル基、γ－メタクリロイルオキシプロピル基等のメタクリロイルオキシアルキル基、γ－ヒドロキシプロピル基等のヒドロキシアルキル基等が挙げられる。これらの置換基の中で本発明にとり好ましいものは、置換基の炭素数が多いと反応性が低下するという点から、炭素数８以下、さらに好ましくは炭素数４以下のアルキル基およびそれに置換基の付加したアミノアルキル基、エポキシアルキル基、メタクリロイルオキシアルキル基、ヒドロキシアルキル基およびアリール基の一種であるフェニル基、炭素数２～３のアルケニル基である。また、Ｒ３２のアルキル基、アリール基、アルケニル基に関しても前記Ｒ３１と同様であるが、とくに好ましいものは、置換基の炭素数が多いと反応性が低下するという点から、炭素数４以下のアルキル基である。 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 Groups, methacryloyloxyalkyl groups such as γ-mercaptoalkyl groups, γ-methacryloyloxypropyl groups, and hydroxyalkyl groups such as γ-hydroxypropyl groups. 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 a phenyl group which is one of aryl groups, 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.
上記有機ケイ素化合物としては、たとえばテトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ビニルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、γ－クロロプロピルトリメトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－（β－アミノエチル）アミノプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－メタクリロイルオキシプロピルトリメトキシシラン、γ－ヒドロキシプロピルトリメトキシシラン等が挙げられるが、反応性、成膜性、可撓性等の点からメチルトリメトキシシラン、フェニルトリメトキシシラン、γ－メタクリロイルオキシプロピルトリメトキシシラン等が好ましい。 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 viewpoint of properties and flexibility, methyltrimethoxysilane, phenyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane and the like are preferable.
上記オルガノシリケートとしては、特開平１１－３４３４６２号公報、特開２００２－１２９１１１号公報、特開２００２－１２９１１０号公報、特開２００７－１５３９３０号公報、特開２００８－０１３７７１号公報、国際公開第９４／０６８７０号に記載されている化合物が本発明においても使用でき、加水分解性基が加水分解することにより親水性基となり、塗膜表面を親水化することによって汚染付着防止効果が奏される。 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.
上記オルガノシリケートとしては、たとえば式：
Ｓｉ（ＯＲ４１）４
（式中、Ｒ４１は水素原子またはハロゲン原子で置換されていてもよい炭素数１～２０の有機基、たとえば直鎖または分岐鎖状のアルキル基、単環でも多環でもよいアリール基等）で示される４官能オルガノシリケート化合物、またはその縮合物；または上記式の４官能オルガノシリケート化合物またはその縮合物の少なくとも１つのＯＲ４１基がノニオン性基、たとえばポリオキシアルキレン鎖（ポリオキシエチレン鎖を必ず含む）を含む有機基で置換されたノニオン変性アルキル基を有するオルガノシリケート化合物；たとえばテトラジエトキシシラン、テトラトリエトキシシラン、テトラプロポキシシラン、テトラジプロポキシシラン、ジポリエトキシシラン、エトキシトリプロポキシシラン、エトキシトリブトキシシラン等が挙げられる。なお、親水化能を有する限り、官能基数が１～３のオルガノシリケート化合物であってもよい。 Examples of the organosilicate include a formula:
Si (OR 41 ) 4
(Wherein R 41 is an organic group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, such as 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.
４官能オルガノシリケート化合物としては、たとえばテトラヒドロキシシラン；テトラメトキシシラン、テトラエトキシシラン等のテトラアルコキシシラン等；およびこれらの縮合物が例示できる。 Examples of the tetrafunctional organosilicate compound include tetrahydroxysilane; tetraalkoxysilane such as tetramethoxysilane and tetraethoxysilane; and condensates thereof.
オルガノシリケートとしては、ノニオン変性されたアルキル基を有するものが特に好ましい。ノニオン変性オルガノシリケート化合物としては、たとえば少なくとも１つの加水分解性基がアルキレンオキサイド鎖、たとえばエチレンオキサイド鎖を含む、変性されたオルガノシリケート化合物が好ましく挙げられる。なお、プロピレンオキサイド鎖、ブチレンオキサイド鎖を含んでいてもよい。なかでも、貯蔵安定性が良好な点から、アルキレンオキサイド変性オルガノシリケート、エチレンオキサイド変性オルガノシリケートが好ましい。 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.
上記有機金属化合物としては、式：
ＸｂＭ（ＯＲ５１）ａＲ５２ ｃ
［式中、ａは０～６の整数、ｂは０～５の整数、ｃは０～６の整数（ただし、ａ＋ｂ＋ｃ≧３であり、ａとｃとは同時に０にはならない）、Ｘは同じかまたは異なりいずれも酸素原子、チッ素原子、フッ素原子および／または塩素原子を含んでいてもよい炭素数１～５０００の１価の有機基または水素原子、Ｍは少なくとも３価の原子価を有する金属原子、Ｒ５１は同じかまたは異なりいずれも酸素原子、チッ素原子、フッ素原子および／または塩素原子を含んでいてもよい炭素数１～１０００の１価の有機基、シロキサン残基または水素原子、Ｒ５２は同じかまたは異なりいずれも酸素原子、チッ素原子、フッ素原子および／または塩素原子を含んでいてもよいキレート化の能力を有する炭素数１～２０の有機基を表す］で示される加水分解性有機金属化合物、そのオリゴマーまたは該有機金属化合物の２種以上からなるコオリゴマーが挙げられる。 As the organometallic compound, the formula:
X b M (OR 51 ) a R 52 c
[Wherein, a is an integer of 0 to 6, b is an integer of 0 to 5, c is an integer of 0 to 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 is at least a trivalent valence The metal atom R 51 may be the same or different and each of them may contain 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 is the same or different and each represents an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom and may represent a C 1-20 organic group having a chelating ability] Water Solution organometallic compound, co-oligomers comprising two or more of the oligomers or organometallic compounds.
上記パーフルオロカーボンスルホン酸樹脂は、パーフルオロカーボンにスルホン酸基（場合により一部が塩の形になっていてもよい）が結合した樹脂である。 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.
上記パーフルオロカーボンスルホン酸樹脂は、－（ＣＦ２－ＣＦＺ）－で表される重合単位（式中、Ｚは、Ｈ、Ｃｌ、Ｆ又は炭素数１～３のパーフルオロアルキル基である。）と、－（ＣＦ２－ＣＦ（－Ｏ－（ＣＦ２）ｍ－ＳＯ３Ｈ））－で表される重合単位（式中、ｍは１～１２の整数である。）と、を含む共重合体である。上記親水化層が上記構造のパーフルオロカーボンスルホン酸樹脂を含むと、高い耐久性と親水性を、優れた耐汚染性を示す。高い親水性が得られる観点から、上記ｍは１～６の整数であることが好ましく、また、ＺはＦであることが好ましい。 The perfluorocarbon sulfonic acid resin includes 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.
上記パーフルオロカーボンスルホン酸樹脂としては、下記一般式（１）で表されるフッ化ビニルエーテル化合物と下記一般式（２）で表されるフッ化オレフィンモノマーとの共重合体からなるパーフルオロカーボンスルホン酸樹脂前駆体を加水分解して得られるものが好ましい。 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.
ＣＦ２＝ＣＦ－Ｏ－（ＣＦ２）ｍ－Ｗ　　　（１）
（式中、ｍは１～１２の整数である。Ｗは加水分解により－ＳＯ３Ｈに転換し得る官能基である。）
ＣＦ２＝ＣＦＺ　　　（２）
（式中、Ｚは、Ｈ、Ｃｌ、Ｆ又は炭素数１～３のパーフルオロアルキル基である。） 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.)
上記式（１）中の加水分解により－ＳＯ３Ｈに転換しうる官能基であるＷとしては、ＳＯ２Ｆ、ＳＯ２Ｃｌ又はＳＯ２Ｂｒが好ましい。ｍは１～６の整数であることが好ましい。ｍが１～６の整数であると、パーフルオロカーボンスルホン酸樹脂の当量重量ＥＷが低くなり、親水性が高くなる傾向にある。
また、上記式（１）及び（２）において、ＷはＳＯ２Ｆであり、ＺはＦであるパーフルオロカーボンスルホン酸樹脂前駆体が好ましく、中でも、高い親水性及び高い樹脂濃度の溶液が得られる観点から、ｍは１～６の整数、ＷはＳＯ２Ｆ、かつＺはＦであるものがより好ましい。また、上記構造を有する共重合体であると、光触媒作用で生成するラジカル種への耐性が強くなる点でも好ましい。 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 perfluorocarbon sulfonic 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, m is more preferably 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.
上記パーフルオロカーボンスルホン酸樹脂前駆体は、公知の手段により合成できる。例えば、ラジカル発生剤の過酸化物を利用した重合法等にて、含フッ素炭化水素等の重合溶剤を使用し、上記加水分解により－ＳＯ３Ｈに転換しうる官能基を有するフッ化ビニル化合物とテトラフルオロエチレン（ＴＦＥ）等のフッ化オレフィンのガスを充填溶解して反応させ重合する方法（溶液重合）、含フッ素炭化水素等の溶媒を使用せずフッ化ビニル化合物そのものを重合溶剤として重合する方法（塊状重合）、界面活性剤の水溶液を媒体として、フッ化ビニル化合物とフッ化オレフィンのガスとを充填して反応させ重合する方法（乳化重合）、界面活性剤及びアルコール等の助乳化剤の水溶液に、フッ化ビニル化合物とフッ化オレフィンのガスを充填乳化して反応させ重合する方法（ミニエマルジョン重合、マイクロエマルジョン重合）及び懸濁安定剤の水溶液にフッ化ビニル化合物とフッ化オレフィンのガスを充填懸濁して反応させ重合する方法（懸濁重合）等が知られているが、本実施形態においてはいずれの重合方法で作製されたものでも使用することができる。 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 fluorine-containing 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.
上記のようにして作製されたパーフルオロカーボンスルホン酸樹脂前駆体は、メルトインデックス（ＭＩ）が０．０５～５０ｇ／１０分であることが好ましく、より好ましくは０．１～３０ｇ／１０分であり、もっとも好ましくは０．２～２０ｇ／１０分である。ＭＩは、ＪＩＳ　Ｋ　７２１０に従って２７０℃、荷重２．１６ｋｇの条件下で、メルトインデクサーを用いて測定し、押し出されたポリマーの質量を１０分間あたりのグラム数で表したものである。 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.
上記のようにして作製されたパーフルオロカーボンスルホン酸樹脂前駆体は、押し出し機を用いてノズル又はダイ等で押し出し成型することが好ましい。この際の成型方法及び成型体の形状は特に限定されるものではない。後述の加水分解処理及び酸処理において処理速度を速めるには、成型体が０．５ｃｍ３以下のペレット状であることが好ましいが、重合後の粉末状態のものを利用してもよい。 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.
上記のようにして成型されたパーフルオロカーボンスルホン酸樹脂前駆体を、引き続き塩基性反応液体中に浸漬し、加水分解処理を行う。 The perfluorocarbon sulfonic acid resin precursor molded as described above is subsequently immersed in a basic reaction liquid and subjected to a hydrolysis treatment.
この加水分解処理に使用する塩基性反応液としては、特に限定されるものではないが、ジメチルアミン、ジエチルアミン、モノメチルアミン、モノエチルアミン等のアミン化合物の水溶液や、アルカリ金属又はアルカリ土類金属の水酸化物の水溶液が好ましく、水酸化ナトリウム又は水酸化カリウムの水溶液が特に好ましい。アルカリ金属又はアルカリ土類金属の水酸化物の含有量は特に限定されないが、反応液全体に対して１０～３０質量％であることが好ましい。上記反応液は、さらにメチルアルコール、エチルアルコール、アセトン及びＤＭＳＯ等の膨潤性有機化合物を含有することがより好ましい。また膨潤性の有機化合物の含有量は、反応液全体に対して１～３０質量％であることが好ましい。 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. Further, the content of the swellable organic compound is preferably 1 to 30% by mass with respect to the entire reaction solution.
パーフルオロカーボンスルホン酸樹脂前駆体は、前記塩基性反応液体中で加水分解処理された後、温水等で十分に水洗され、その後、酸処理が行われる。酸処理に使用する酸としては、特に限定されないが、塩酸、硫酸及び硝酸等の鉱酸類や、シュウ酸、酢酸、ギ酸及びトリフルオロ酢酸等の有機酸類が好ましく、これらの酸と水との混合物がより好ましい。また、上記の酸類が２種類以上同時に使用されても構わない。この酸処理によってパーフルオロカーボンスルホン酸樹脂前駆体はプロトン化され、－ＳＯ３Ｈを有するものとなる。プロトン化することによって得られたパーフルオロカーボンスルホン酸樹脂は、プロトン性有機溶媒、水、又は両者の混合溶媒に溶解することが可能となる。 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.
パーフルオロカーボンスルホン酸樹脂は、当量重量ＥＷ（プロトン交換基１当量あたりのパーフルオロカーボンスルホン酸樹脂の乾燥重量グラム数）が２００～１０００である。上記パーフルオロカーボンスルホン酸樹脂の当量重量ＥＷとしては、好ましくは２００～９５０、より好ましくは２００～８００である。更に好ましくは２００～７００であり、特に好ましくは２５０～６００であり、最も好ましくは４００～５００である。当量重量ＥＷが上記範囲であることによって、パーフルオロカーボンスルホン酸樹脂に優れた親水性を付与することができる。その結果、親水性に優れた親水化層を形成でき、優れた耐汚染性効果を発現することができる。当量重量ＥＷが小さすぎると、水に可溶となるため、上記親水化層が上記被覆層から剥離しやすくなるおそれがあり、大きすぎると、親水性が低下するおそれがある。 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 to 700, particularly preferably 250 to 600, and most preferably 400 to 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.
ここで、パーフルオロカーボンスルホン酸樹脂の当量重量ＥＷは、パーフルオロカーボンスルホン酸樹脂を塩置換し、その溶液をアルカリ溶液で逆滴定することにより測定することができる。 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.
上記遷移金属多価イオンとしては、ラジカル耐性を効果的に向上させる観点から、セリウムイオンが特に好ましい。なお、セリウムイオンは＋３価又は＋４価の状態を取り得るが、本実施形態においては特に限定されない。上記被覆層は、パーフルオロカーボンスルホン酸樹脂及び遷移金属多価イオンを含むことが好ましく、この場合の遷移金属多価イオンは、パーフルオロカーボンスルホン酸樹脂のスルホン酸基とイオン結合可能であるものが好ましい。以下、セリウムイオンを例に取って説明する。 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.
上記被覆層において、パーフルオロカーボンスルホン酸樹脂中にセリウムイオンが配合されていることが好ましい。パーフルオロカーボンスルホン酸樹脂中にセリウムイオンを配合させる方法は特に限定されないが、例えば以下の方法が挙げられる。
（１）セリウムイオンが含まれる溶液中にパーフルオロカーボンスルホン酸樹脂を浸漬する方法。
（２）パーフルオロカーボンスルホン酸樹脂の溶液内にセリウムイオンを含む塩を添加する方法。
（３）セリウムイオンを含む溶液とパーフルオロカーボンスルホン酸樹脂の溶液を混合する方法。
上記の方法によって得られるパーフルオロカーボンスルホン酸樹脂は、スルホン酸基の一部がセリウムイオンによりイオン交換されていると考えられる。 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.
ここでセリウムイオンは＋３価でも＋４価でもよく、セリウムイオンを含む溶液を得るために各種のセリウム塩が使用される。＋３価のセリウムイオンを含む塩を具体例に挙げると、例えば、酢酸セリウム（Ｃｅ（ＣＨ３ＣＯＯ）３・Ｈ２Ｏ）、塩化セリウム（ＣｅＣｌ３・６Ｈ２Ｏ）、硝酸セリウム（Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ）、硫酸セリウム（Ｃｅ２（ＳＯ４）３・８Ｈ２Ｏ）、炭酸セリウム（Ｃｅ２（ＣＯ３）３・８Ｈ２Ｏ）等が挙げられる。＋４価のセリウムイオンを含む塩としては、例えば、硫酸セリウム（Ｃｅ（ＳＯ４）２・４Ｈ２Ｏ）、硝酸二アンモニウムセリウム（Ｃｅ（ＮＨ４）２（ＮＯ３）６）、硫酸四アンモニウムセリウム（Ｃｅ（ＮＨ４）４（ＳＯ４）４・４Ｈ２Ｏ）等が挙げられる。また、セリウムの有機金属錯塩としては、セリウムアセチルアセトナート（Ｃｅ（ＣＨ３ＣＯＣＨＣＯＣＨ３）３・３Ｈ２Ｏ）等が挙げられる。上記の中でも、特に炭酸セリウムが好ましい。水を含有したパーフルオロカーボンスルホン酸樹脂の溶液に、炭酸セリウムを加えると、炭酸ガスを発生しながら溶解する。この場合、パーフルオロカーボンスルホン酸樹脂の溶液にアニオン種が残存しないためアニオン種除去の工程を必要としないという利点を有する。 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.
例えば、セリウムイオンが＋３価である場合、スルホン酸基がセリウムイオンによりイオン交換されると、Ｃｅ３＋が３個の－ＳＯ３ －と結合する。本実施形態において、パーフルオロカーボンスルホン酸樹脂中に含まれるセリウムイオンの数は、樹脂中の－ＳＯ３ －基の数に対して０．３～３０当量％であることが好ましい（以下、この割合を「セリウムイオンの含有率」という。）。この数値範囲は、＋３価のセリウムイオンが完全に３個の－ＳＯ３ －と結合している場合には、セリウムイオンでイオン交換されたスルホン酸基が、スルホン酸基とセリウムイオンでイオン交換されたスルホン酸基との合計量に対して０．９～９０％であることと同義である（以下、この割合を「置換率」という。）。セリウムイオンの含有率は、より好ましくは０．６～２０当量％、さらに好ましくは１～１５当量％である。上記置換率で表すと、１．８～６０％がより好ましく、３～４５％がさらに好ましい。セリウムイオンの含有率を上記範囲（０．３～３０当量％）に調整することにより、良好な親水性を維持したまま、高耐久性を有する塗膜を作製することができる。また、乾燥硬化して得られた塗膜は、柔軟性に優れ、更には、光触媒作用で生成するラジカル種に対する耐久性にも優れ、長期間光触媒機能を発揮することもできる。 For example, if cerium ions are trivalent, the sulfonic acid groups are ion-exchanged with cerium ions, Ce 3+ is three -SO 3 - bound to. 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 — , a sulfonic acid group ion-exchanged with a cerium ion is ion-exchanged with a sulfonic acid group and a cerium ion. This is synonymous with 0.9 to 90% of the total amount of sulfonic acid groups formed (hereinafter, this ratio is referred to as “substitution rate”). The content of cerium ions is more preferably 0.6 to 20 equivalent%, and further 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 in 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.
上記金属酸化物としては、光触媒機能を有する金属酸化物が好ましい。上記金属酸化物としては、ＴｉＯ２、ＺｎＯ、ＳｒＴｉＯ３、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ３、ＢａＴｉＯ４、ＢａＴｉ４Ｏ９、Ｋ２ＮｂＯ３、Ｎｂ２Ｏ５、Ｆｅ２Ｏ３、Ｔａ２Ｏ５、Ｋ３Ｔａ３、Ｓｉ２Ｏ３、ＷＯ３、ＳｎＯ２、Ｂｉ２Ｏ３、ＢｉＶＯ４、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＳｉＯ２、ＭｏＳ２、ＩｎＰｂ、ＲｕＯ２、ＣｅＯ２等を挙げることができる。 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.
また、Ｔｉ、Ｎｂ、Ｔａ、Ｖから選ばれた少なくとも１種の元素を有する層状酸化物（特開昭６２－７４４５２号公報、特開平２－１７２５３５号公報、特開平７－２４３２９号公報、特開平８－８９７９９号公報、特開平８－８９８００号公報、特開平８－８９８０４号公報、特開平８－１９８０６１号公報、特開平９－２４８４６５号公報、特開平１０－９９６９４号公報、特開平１０－２４４１６５号公報等参照）を用いることもできる。
更に、これらの金属酸化物に、Ｐｔ、Ｒｈ、Ｒｕ、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅ等の金属及び／又はこれらの酸化物を添加あるいは固定化したものや、多孔質リン酸カルシウム等で被覆された光触媒（特開平１０－２４４１６６号公報参照）等を使用することもできる。 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, and 7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10 -244165, etc.) 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.
更に、これらの他に、公知の増感剤を添加して可視光線領域における光触媒機能を付与したものも使用することができる。
これらの光触媒機能を有する金属酸化物のうち、ＴｉＯ２（酸化チタン）は無毒であり、化学的安定性にも優れるためより好ましい。
酸化チタンには、アナターゼ型、ルチル型、ブルッカイト型の３つの結晶形が知られているが、これらのうちのいずれを使用してもよい。
好ましくは光活性が一番高いアナターゼ型である。
上記金属酸化物の結晶粒子径（１次粒子径）は１～２００ｎｍであることが好ましく、より好ましくは１～５０ｎｍである。ここで、結晶粒子径は、レーザーを利用した散乱法により測定した値をいう。 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 metal oxide has a crystal particle diameter (primary particle diameter) of 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.
上記親水化層は、コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種並びに水を含む親水化塗料から形成されることが好ましい。上記親水化層が上記親水化塗料から形成されるものであると、環境に負荷をかけずに上記親水化層を形成できる。本発明の積層体は、上記親水化層が水を含む親水化塗料から形成されたものであっても、上記親水化層と上記被覆層とが強固に接着している。上記親水化塗料は、水に加えてアルコールを含むものであってよく、上記アルコールとしては、メタノール、エタノール、プロパノール等が挙げられる。 The hydrophilizing layer is formed from a hydrophilizing paint containing at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorosulfonic 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.
上記積層体は、更に、基材を含むことが好ましい。上記基材は、後述する用途にあわせて適宜選択すればよい。例えば、サイディング材、窯業系基材、金属系基材、スレート基材、発泡コンクリートパネル、コンクリートパネル、アルミカーテンウォール、鋼板、亜鉛メッキ鋼板、ステンレス鋼板、塩ビシート、ＰＥＴフィルム、ポリカーボネート基材、アクリルフィルム、ガラス等が挙げられる。 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.
上記積層体は、上記基材、上記被覆層及び上記親水化層がこの順に積層されていることが好ましい。上記基材と上記被覆層との間に他の層を含むものであってもよい。上記他の層としては、アクリル樹脂層（但し、表面自由エネルギーが３０～４０ｍＪ／ｍ２である層を除く）が挙げられる。上記被覆層及び上記親水化層は、直接接着していることが好ましい。 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.
上記基材としては、サイディング材が好ましい。上記サイディング材としては、例えば、窯業系サイディング材、金属系サイディング材、プラスチック系サイディング材等が挙げられる。 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.
特に、窯業系サイディング材では、耐水性、耐候性や外観の向上等のため、表面にアクリル系、アクリルシリコン系、アクリルウレタン系の塗膜が形成されることが多いが、上記被覆層は、アクリル系の塗膜にも強固に接着し、耐温水性に優れ、更に透明性にも優れる。窯業系サイディング材は、例えば、窯業系基材と、上記組成物を窯業系基材に塗装して得られる塗膜とを有するものであり、窯業系基材は、表面がアクリル樹脂からなるものであってもよい。 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.
窯業系基材としては、従来公知のものを用いることができる。たとえばセメントを主とする水性スラリーの抄造により湿潤シートを得て、これを脱水プレス成形し、乾燥、養生硬化させたものや、セメント等の水性混練物を、押し出し成形、注型成形等することにより得られた成形体を硬化させたもの等、従来より公知の組成のものを使用することができる。窯業系基材は、成形体の表面にアクリル樹脂層を有するものであってもよい。 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.
上記積層体は、上記樹脂を配合した塗料を上記基材に塗布して上記被覆層を形成する工程、並びに、上記被覆層上にコロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種並びに水を含む塗料を塗布して、上記親水化層を形成する工程を含む製造方法により製造できる。 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, organosilicate, organometallic compound, perfluorosulfonic 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.
上記被覆層を形成する塗料は、水性塗料であることが好ましい。従来の方法では、水性塗料により被覆層を形成した後、該被覆層上に水を含む塗料を塗布すると、該塗料が該被覆層に弾かれて、親水化層を形成できなかったり、形成できたとしても、両層の接着性が不十分であったりした。上記製造方法では、上記被覆層が上記樹脂を配合した塗料からなるので、該塗料が水性塗料であっても、上記被覆層と上記親水化層とが強固に接着した積層体を製造できる。 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.
上記被覆層及び上記親水化層を形成するための塗料を塗布する方法としては、例えば、スプレーコーティング、ロールコーティング、フローコーティング、ローラー、刷毛による塗装等の塗装方法が挙げられる。塗布後、５～２００℃で乾燥してもよい。 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. After application, it may be dried at 5 to 200 ° C.
上記積層体は、幅広い用途で使用可能である。例えば、電気製品（電子レンジ、トースター、冷蔵庫、洗濯機、ヘアードライアー、テレビ、ビデオ、アンプ、ラジオ、電気ポット、炊飯機、ラジオカセット、カセットデッキ、コンパクトディスクプレーヤー、ビデオカメラ等）、エアーコンディショナーの室内機、室外機、吹き出口およびダクト、空気清浄機、暖房機、蛍光燈、シャンデリア、反射板等の照明器具、家具、機械部品、装飾品、くし、めがねフレーム、天然繊維、合成繊維（糸状のもの、およびこれらから得られる織物）、事務機器（電話機、ファクシミリ、複写機（ロールを含む）、写真機、オーバーヘッドプロジェクター、実物投影機、時計、スライド映写機、机、本棚、ロッカー、書類棚、いす、ブックエンド、電子白板等）、自動車（ホイール、ドアミラー、モール、ドアのノブ、ナンバープレート、ハンドル、インスツルメンタルパネル等）、厨房器具類（レンジフード、流し台、調理台、包丁、まな板、水道の蛇口、ガスレンジ、換気扇等）、間仕切り、バスユニット、シャッター、ブラインド、カーテンレール、アコーディオンカーテン、壁、天井、床、外壁、手摺り、門扉、シャッター等が挙げられる。 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.
また、特に好ましい態様として、次の製造方法が挙げられる。
すなわち、基材の上に水性塗料を塗布し、乾燥させることにより、被覆層を形成する工程、及び、
上記被覆層上に親水化塗料を塗布することにより、親水化層を形成する工程、
を含む製造方法であって、
上記水性塗料は、複合重合体粒子及び水を含み、
上記親水化塗料は、コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種、並びに、水又はアルコールを含む
ことを特徴とする製造方法である。 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, perfluorosulfonic acid resin, transition metal polyvalent ion and metal oxide, and water or alcohol. Is a manufacturing method characterized by
上記製造方法は、上記の構成を有することから、水性塗料により形成された被覆層の上に、水性の親水化塗料により親水化層を形成できるという効果を奏する。従来の被覆層の上に親水化塗料を塗布すると、造膜性が良くなく、良好な外観を有する親水化層を形成できなかった。 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.
上記複合重合体粒子としては、上述したものが、上記製造方法でも同様に使用できる。 As said composite polymer particle, what was mentioned above can be used similarly with the said manufacturing method.
上記複合重合体粒子は、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）とを同一粒子内に含み、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）が９０／１０～１０／９０であることが好ましい。 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. It is preferably ˜10 / 90.
フルオロポリマー（Ａ）としては、ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝４０～９９／１～５０／０～３０（モル％）、ＶｄＦ／ＴＦＥ＝５０～９９／１～５０（モル％）、ＶｄＦ／ＴＦＥ／ＨＦＰ＝４５～９９／０～３５／５～５０（モル％）、ＶｄＦ／ＣＴＦＥ＝４０～９９／１～３０（モル％）、及び、ＶｄＦ／ＨＦＰ＝５０～９９／１～５０（モル％）からなる群より選択される少なくとも１種が好ましい。 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 = 45-99 / 0-35 / 5-50 (mol%), VdF / CTFE = 40-99 / 1-30 (mol%), and VdF / HFP = 50-99 / 1-50 (mol%) At least one selected from the group consisting of:
アクリルポリマー（Ｂ）は、アクリルポリマー（Ｂ）の全構成単位に対して、５～９８質量％のメタクリル酸エステル単位と、９３～１．９質量％のメタクリル酸単位と、０．１～２質量％の加水分解性シリル基含有単量体単位とを含むことが好ましく、９０～９８質量％のメタクリル酸エステル単位と、８～１．９質量％のメタクリル酸単位と、０．１～２質量％の加水分解性シリル基含有単量体単位とを含むことがより好ましい。
メタクリル酸エステル単位としては、メチルメタクリレート、ブチルメタクリレート、及び、シクロヘキシルメタクリレートからなる群より選択される少なくとも１種の単位が好ましい。 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). It is preferable to contain 90% by mass of a hydrolyzable silyl group-containing monomer unit, 90 to 98% by mass of a methacrylic acid ester unit, 8 to 1.9% by mass of a methacrylic acid unit, 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.
上記被覆層は、表面自由エネルギーが３０～４０ｍＪ／ｍ２であることが好ましい。上記表面自由エネルギーとしては、３２ｍＪ／ｍ２以上がより好ましく、３８ｍＪ／ｍ２以下がより好ましい。
上記製造方法は、更に、上記フルオロオレフィンを水性分散重合して、フルオロポリマー（Ａ）粒子を含む水性分散体を得る工程、上記フルオロポリマー（Ａ）粒子を含む水性分散体中で、上記反応性アニオン界面活性剤の存在下に、少なくとも上記アクリルモノマーを、フルオロポリマー（Ａ）粒子にシード重合する工程を含むものであってもよい。 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.
上記水性塗料は、造膜助剤を含むものであってよい。上記造膜助剤としては特に限定されず、例えば、アセトン、メチルエチルケトン、メチルアミルケトン等のケトン類；酢酸エチル、酢酸ブチル、アジピン酸ジメチル、アジピン酸ジエチル等のエステル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ヘキサン、ヘプタン等の脂肪族炭化水素；メタノール、エタノール、イソプロパノール、ブタノール等のアルコール類；四塩化炭素、メチレンジクロライド、ヘキサフルオロイソプロパノール等の含ハロゲン溶剤；エチレングリコール等のエステル類又はエーテル類；「テキサノール」（イーストマンケミカル社製）、「ＣＳ－１２」（チッソ社製）等の水性塗料用可塑剤等を挙げることができる。上記造膜助剤は、上記水性塗料中の固形分に対して、０．１～１５質量％であってよい。 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.
コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物としては、それぞれ、上述したものが、上記製造方法でも同様に使用できる。 As the colloidal silica, organosilicate, organometallic compound, perfluorosulfonic acid resin, transition metal polyvalent ion, and metal oxide, those described above can be similarly used in the above production method.
上記親水化塗料は、金属酸化物及び水を含むことが好ましく、パーフルオロスルホン酸樹脂、金属酸化物、及び、水を含むことがより好ましい。上記親水化塗料は、水に加えてアルコールを含むものであってよく、上記アルコールとしては、メタノール、エタノール、プロパノール等が挙げられる。 The hydrophilic coating preferably contains a metal oxide and water, and more preferably contains a perfluorosulfonic 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.
上記基材としては、サイディング材、窯業系基材、金属系基材、スレート基材、発泡コンクリートパネル、コンクリートパネル、アルミカーテンウォール、鋼板、亜鉛メッキ鋼板、ステンレス鋼板、塩ビシート、ＰＥＴフィルム、ポリカーボネート基材、アクリルフィルム、ガラス基材等が挙げられる。上記基材としては、基材表面にアクリル樹脂塗膜を備える基材が好ましい。 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.
つぎに本発明を実施例をあげて説明するが、本発明はかかる実施例のみに限定されるものではない。 Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.
実施例の各数値は以下の方法により測定した。 Each numerical value of the examples was measured by the following method.
複合重合体粒子（被覆層）の表面自由エネルギーは、複合重合体粒子の水性分散体から得た膜について、装置として接触角計「ＰＣＡ－１」（協和界面科学製）を用い、溶媒としてｎ－ヘキサデカンと水により測定した。
親水化層（親水化塗料）の造膜性は、目視と色彩色差計（色差計ＣＲ３００（ミノルタ（株）製））で測定、被覆層の色彩と親水化層の色彩の明度差ΔＬを造膜性の指標とした。 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.
親水化層の接触角の測定は、装置として接触角計「ＰＣＡ－１」（協和界面科学製）を用い、溶媒として水により測定した。また、次の条件で実施する耐候性試験後の接触角も測定した。
＜耐候性試験後の接触角＞
ダイプラウィンテス製メタルウェザーによる耐候性試験を実施した。試験条件は、照度６５ｍＷ／ｃｍ２、ブラックパネル温度５３℃、ＬＩＧＨＴ照射時条件（５３℃／７０％ＲＨ／２時間）とした。試験を２時間実施した後、接触角の評価を行った。 The contact angle of the hydrophilic layer was measured using a contact angle meter “PCA-1” (manufactured by Kyowa Interface Science) as an apparatus 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.
実施例１
複合重合体粒子の合成
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液１０１８質量部にポリオキシ－１－（アリルオキシ）アルキルエーテル硫酸アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）４７質量部、ｎ－ブチルメタクリレート（ＢＭＡ）３９４質量部、メタクリル酸１８質量部、γ－メタクリロキシプロピルトリエトキシシラン１質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）４０質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は５０／５０であった。 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 weight of ammonium polyoxy-1- (allyloxy) alkyl ether sulfate to 1018 parts by weight 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.
パーフルオロカーボンスルホン酸樹脂溶液の調製
テトラフルオロエチレン（「ＣＦ２＝ＣＦ２」、以下「ＴＦＥ」と略記する。）とＣＦ２＝ＣＦＯ（ＣＦ２）２ＳＯ３Ｈからなる共重合体（パーフルオロカーボンスルホン酸樹脂）をエタノール水溶液（水：エタノール＝５０：５０（質量比））に分散し５質量％の水溶液を作製した。次に、１００ｇの５質量％パーフルオロカルボンスルホン酸水溶液に純水１００ｇを添加し、固形分濃度２０質量％になるまで濃縮し、２０質量％パーフルオロスルホン酸樹脂水溶液を得た。 Preparation of perfluorocarbon sulfonic acid resin solution Copolymer (perfluorocarbon) composed of 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 100 g 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 perfluorosulfonic acid resin aqueous solution.
親水化塗料の調製
酸化チタン１０質量部、２０％パーフルオロカーボンスルホン酸樹脂水溶液５０質量部、エタノール４０質量部を配合して親水化塗料を調製した。 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.
積層体の製造方法
基材としてアルミ板（化成アルミ板（ＪＩＳ　Ｈ４０００　Ａ１０５０Ｐ、ＡＭ－７１２処理。厚さ０．５ｍｍ）に予め下塗りとして水性アクリル系樹脂に黒顔料ペーストを混ぜたものを１００ｇ／ｍ２となるように塗装し、室温で１日間乾燥させたもの）に上記複合体粒子の水性分散体に造膜助剤テキサノール（添加量１０ＰＨＲ、ＥＡＳＴＭＡＮ　ＣＨＥＭＩＣＡＬ製）を添加し、エアスプレーで塗布し、１００℃で３分乾燥させ被覆層を形成した。
更に、親水化塗料を上記被覆層上に塗布し、８０℃で５分間乾燥し、本発明の積層体を含むアルミ試験板を得た。 Laminate production method 100 g / m of an aluminum plate (chemical conversion aluminum plate (JIS H4000 A1050P, AM-712 treatment, thickness 0.5 mm) previously mixed with a water-based acrylic resin and a black pigment paste as a base material) 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.
実施例２
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液１０１８質量部にポリオキシ－１－（アリルオキシ）アルキルエーテル硫酸アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）４５質量部、ｎ－ブチルメタクリレート（ＢＭＡ）３５０質量部、シクロヘキシルメタクリレート４４質量部、メタクリル酸１６質量部、γ－メタクリロキシプロピルトリエトキシシラン５質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）４０質量部を１時間かけて滴下した。滴下終了から熟成３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は５０／５０であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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 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.
実施例３
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液９４５質量部にポリオキシ－１－（アリルオキシ）アルキルエーテル硫酸アンモニウム塩を１７質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）１３質量部、ｎ－ブチルメタクリレート（ＢＭＡ）９質量部、ｎ－ブチルアクリレート（ＢＡ）１５３質量部、メタクリル酸１２質量部、γ－メタクリロキシプロピルトリエトキシシラン２質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）３０質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は７０／３０であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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.
実施例４
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液４８６質量部にポリオキシ－１－（アリルオキシ）アルキルエーテル硫酸アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）１６２質量部、ｎ－ブチルメタクリレート（ＢＭＡ）４０質量部、ｎ－ブチルアクリレート（ＢＡ）１９３質量部、メタクリル酸４質量部、γ－メタクリロキシプロピルトリエトキシシラン４質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）６３質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は３５／６５であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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 weight, 9 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., 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.
比較例１
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液１０１８質量部にポリオキシアルキレン・多環フェニルエーテル・サルフェート・アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）２８８質量部、ブチルアクリレート（ＢＡ）１５７質量部、アクリル酸１０質量部、γ－メタクリロキシプロピルトリエトキシシラン５質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）４０質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は５０／５０であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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. Part, 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.
比較例２
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液１０１８質量部にポリオキシ－１－（アリルオキシ）アルキルエーテル硫酸アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）４７質量部、ｎ－ブチルメタクリレート（ＢＭＡ）３９４質量部、メタクリル酸１２質量部、γ－メタクリロキシプロピルトリエトキシシラン１質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）４０質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は５０／５０であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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 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.
比較例３
撹拌機、還流管、温度計、滴下ロートを備えた内容量２リットルのガラス製四つ口セパラブルフラスコに、ＶｄＦ／ＴＦＥ／ＣＴＦＥ重合体（ＶｄＦ／ＴＦＥ／ＣＴＦＥ＝７２／１５／１３（モル％））の粒子の水性分散液１０１８質量部にポリオキシアルキレン多環フェニルエーテル硫酸アンモニウム塩を９質量部加え水性分散液を調製した。
つぎに、上記水性分散液を攪拌下に水浴中で加温し、槽温が８０℃に達したところで、メチルメタクリレート（ＭＭＡ）４７質量部、ｎ－ブチルメタクリレート（ＢＭＡ）３９４質量部、メタクリル酸１８質量部、γ－メタクリロキシプロピルトリエトキシシラン１質量部、および過硫酸アンモニウム（ＡＰＳ）（１％水溶液）４０質量部を１時間かけて滴下した。滴下終了から３０分後に室温まで冷却して反応を終了し、ｐＨ調整剤で中和を行い、複合重合体粒子の水性分散体を得た。フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）は５０／５０であった。
親水化塗料として、東亞合成（株）製「ハイチタン　ＡＢＦＳ－２」を用いた。
実施例１と同様にして、アルミ試験板を得た。 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.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Claims (10)

  1. 表面自由エネルギーが３０～４０ｍＪ／ｍ２である被覆層と、親水化層とを含むことを特徴とする積層体。 A laminate comprising a coating layer having a surface free energy of 30 to 40 mJ / m 2 and a hydrophilic layer.
  2. 被覆層は、樹脂を配合した塗料の乾燥塗膜からなる請求項１記載の積層体。 The laminate according to claim 1, wherein the coating layer comprises a dry coating film of a paint blended with a resin.
  3. 被覆層は、樹脂を含み、前記樹脂は、硬化性官能基を有する含フッ素ポリマー又はアクリルポリマーである請求項１又は２記載の積層体。 The laminate according to claim 1 or 2, wherein the coating layer contains a resin, and the resin is a fluorine-containing polymer or an acrylic polymer having a curable functional group.
  4. 被覆層は、樹脂を含み、前記樹脂は、複合重合体粒子であり、
    前記複合重合体粒子は、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）とを同一粒子内に含み、フルオロポリマー（Ａ）とアクリルポリマー（Ｂ）との質量比（Ａ／Ｂ）が９０／１０～１０／９０である
    請求項１、２又は３記載の積層体。     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. The laminate according to claim 1, 2 or 3, which is ~ 10/90.
  5. フルオロポリマー（Ａ）は、ビニリデンフルオライド単位を含む請求項４記載の積層体。 The laminate according to claim 4, wherein the fluoropolymer (A) contains vinylidene fluoride units.
  6. フルオロポリマー（Ａ）は、ビニリデンフルオライド単位と、テトラフルオロエチレン、ヘキサフルオロプロピレン及びクロロトリフルオロエチレンからなる群より選ばれる少なくとも１種のフルオロオレフィン単位とを含む請求項４又は５記載の積層体。 The laminate according to claim 4 or 5, wherein the fluoropolymer (A) comprises a vinylidene fluoride unit and at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene. .
  7. アクリルポリマー（Ｂ）は、アクリル酸、アクリル酸エステル、メタクリル酸及びメタクリル酸エステルからなる群より選択される少なくとも１種のアクリルモノマー単位を含む請求項４、５又は６記載の積層体。 The laminate according to claim 4, 5 or 6, wherein the acrylic polymer (B) contains at least one acrylic monomer unit selected from the group consisting of acrylic acid, acrylic ester, methacrylic acid and methacrylic ester.
  8. アクリルポリマー（Ｂ）は、メタクリル酸エステル単位と、メタクリル酸単位とを含む請求項４、５、６又は７記載の積層体。 The laminate according to claim 4, 5, 6, or 7, wherein the acrylic polymer (B) includes a methacrylic acid ester unit and a methacrylic acid unit.
  9. 親水化層は、コロイダルシリカ、オルガノシリケート、有機金属化合物、パーフルオロスルホン酸樹脂、遷移金属多価イオン及び金属酸化物からなる群より選択される少なくとも１種並びに水を含む塗料から形成される請求項１、２、３、４、５、６、７又は８記載の積層体。 The hydrophilizing layer is formed from a paint containing water and at least one selected from the group consisting of colloidal silica, organosilicates, organometallic compounds, perfluorosulfonic acid resins, transition metal polyvalent ions and metal oxides. Item 11. A laminate according to item 1, 2, 3, 4, 5, 6, 7 or 8.
  10. 更に、基材を含み、前記基材、被覆層及び親水化層がこの順に積層されている請求項１、２、３、４、５、６、７、８又は９記載の積層体。 Furthermore, the laminated body of Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 which contains a base material and the said base material, a coating layer, and the hydrophilization layer are laminated | stacked in this order.
PCT/JP2016/076643 2015-09-09 2016-09-09 Laminated article WO2017043634A1 (en)

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