JP2024008429A - Aqueous fluororesin coating composition - Google Patents
Aqueous fluororesin coating composition Download PDFInfo
- Publication number
- JP2024008429A JP2024008429A JP2022110302A JP2022110302A JP2024008429A JP 2024008429 A JP2024008429 A JP 2024008429A JP 2022110302 A JP2022110302 A JP 2022110302A JP 2022110302 A JP2022110302 A JP 2022110302A JP 2024008429 A JP2024008429 A JP 2024008429A
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- Japan
- Prior art keywords
- fluororesin
- water
- resin
- coating composition
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 abstract description 23
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000004446 fluoropolymer coating Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WHIVNJATOVLWBW-SNAWJCMRSA-N methylethyl ketone oxime Chemical compound CC\C(C)=N\O WHIVNJATOVLWBW-SNAWJCMRSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical class [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
Description
本発明は、様々な金属基材に強固に接着し、１回の塗装で耐水蒸気性・耐食性に優れた十分な厚みのある塗膜を形成できる水性フッ素樹脂塗料組成物、それを塗装してなる塗膜、その塗膜を有する物品に関する。 The present invention relates to a water-based fluororesin coating composition that firmly adheres to various metal substrates and can form a sufficiently thick coating film with excellent water vapor resistance and corrosion resistance in a single application, and a coating composition using the composition. The present invention relates to a coating film and an article having the coating film.
フッ素樹脂は、優れた耐熱性、耐薬品性、電気的性質及び機械的性質を有し、また極めて低い摩擦係数、非粘着性、撥水撥油性を有しているため、化学、機械、電機などあらゆる工業分野において広く利用されている。 Fluororesins have excellent heat resistance, chemical resistance, electrical properties, and mechanical properties, as well as extremely low coefficients of friction, non-stick properties, and water and oil repellency, so they are used in chemical, mechanical, and electrical equipment. It is widely used in all industrial fields.
特に、フッ素樹脂の非粘着性、撥水撥油性を利用して、フッ素樹脂コーティングが、フライパン・炊飯器などの調理器具の塗装、ＯＡ機器のトナーを定着させる定着ロール・ベルトなど様々な分野で利用され、近年では、インクジェットノズル、化学プラントの設備など、利用分野はさらに広がっている。 In particular, by taking advantage of the non-adhesive, water- and oil-repellent properties of fluororesin, fluororesin coatings are used in various fields such as painting cooking utensils such as frying pans and rice cookers, and fixing rolls and belts that fix toner in office automation equipment. In recent years, the field of use has expanded further, including inkjet nozzles and chemical plant equipment.
ところが、各種基材にフッ素樹脂をコーティングする場合、フッ素樹脂の特性である非粘着性のために、フッ素樹脂を直接基材に塗装することは接着不良が生じ、極めて困難である。そのため、フッ素樹脂コーティングを行なう場合には、基材に対する接着性を有し、かつその上に塗装されるフッ素樹脂コーティング（トップコート塗料）の塗膜とも接着性を有するプライマー塗料組成物が通常利用されてきた。 However, when coating various base materials with a fluororesin, it is extremely difficult to directly apply the fluororesin to the base material because of the non-adhesive properties of the fluororesin, as this will result in poor adhesion. Therefore, when applying a fluororesin coating, a primer paint composition that has adhesive properties to the base material and also to the fluororesin coating (top coat paint) that is applied on top is usually used. It has been.
このようなプライマー塗料組成物には、基材との接着性を有し、かつフッ素樹脂の融点以上の高温に耐えうる耐熱性樹脂（いわゆるエンジニアリングプラスチック）が用いられており、例えば、特許文献１には、ポリイミド、ポリアミドイミド、ポリエーテルスルホンなどのプレカーサー及びポリフェニレンサルファイドなどの微粒子が開示されている。このような耐熱性樹脂をバインダーと呼ぶ。 Such primer paint compositions use heat-resistant resins (so-called engineering plastics) that have adhesive properties with the base material and can withstand high temperatures higher than the melting point of the fluororesin; for example, Patent Document 1 discloses precursors such as polyimide, polyamideimide, polyethersulfone, and fine particles such as polyphenylene sulfide. Such heat-resistant resin is called a binder.
一方、プライマー塗料組成物を含むフッ素樹脂塗料組成物の媒体には、有機溶剤（溶剤系塗料）か水（水性塗料）が用いられており、環境負荷や人体への有害性の観点から、特に近年では水性（水系）塗料組成物が好ましく用いられている。水性塗料組成物において、基材との接着性を付与する耐熱性樹脂（バインダー）は、通常非水溶性であるため、その粒子を塗料組成物の液中に分散させて用いられるが、このとき、水溶性のポリアミドイミドを用いることもできる（特許文献２）。 On the other hand, organic solvents (solvent-based paints) or water (water-based paints) are used as the medium for fluororesin paint compositions, including primer paint compositions. In recent years, aqueous (water-based) coating compositions have been preferably used. In water-based paint compositions, the heat-resistant resin (binder) that provides adhesion to the substrate is usually water-insoluble, so its particles are dispersed in the liquid of the paint composition. , water-soluble polyamideimide can also be used (Patent Document 2).
耐熱性樹脂（バインダー）として水溶性ポリアミドイミド（水溶性ＰＡＩ）を用いた場合、水性フッ素樹脂塗料組成物中に均一に溶解するため、少量でも高い接着力が得られる。 When water-soluble polyamideimide (water-soluble PAI) is used as the heat-resistant resin (binder), it is uniformly dissolved in the water-based fluororesin coating composition, so high adhesive strength can be obtained even with a small amount.
さらに、水溶性ポリアミドイミドは粘度が高いことから、増粘剤を低減するか不使用とすることができ、塗膜の純粋性を高め、より良好な性能を得ることができる。さらに、水溶性ポリアミドイミドを用いることで、耐熱性樹脂（バインダー）として一般的な各種エンジニアリングプラスチックの粉体を用いる場合に必要な分散工程や分散度合いの管理が不要となり、生産性に優れ、かつ品質管理もし易いという利点も有する。 Furthermore, since water-soluble polyamideimide has a high viscosity, thickeners can be reduced or eliminated, increasing the purity of the coating film and providing better performance. Furthermore, by using water-soluble polyamide-imide, the dispersion process and control of the degree of dispersion that are required when using powders of general engineering plastics as heat-resistant resins (binder) are not required, resulting in excellent productivity and It also has the advantage of easy quality control.
したがって、水性塗料組成物において、基材との接着性を付与する耐熱性樹脂（バインダー）として水溶性ポリアミドイミドを用いることが望まれている。
しかし、従来の水溶性ポリアミドイミドを用いたフッ素樹脂組成物から得られる塗膜では、耐水蒸気性と耐食性が不十分であった。
Therefore, in water-based coating compositions, it is desired to use water-soluble polyamide-imide as a heat-resistant resin (binder) that provides adhesiveness to the substrate.
However, coating films obtained from conventional fluororesin compositions using water-soluble polyamideimide have insufficient water vapor resistance and corrosion resistance.
これまで、耐水蒸気性と耐食性に優れた水性塗料組成物としては、水溶性ポリアミドイミドと共にポリエーテルスルホン樹脂を用いたフッ素樹脂塗料組成物が提案されている（特許文献３）。 Until now, as a water-based coating composition with excellent water vapor resistance and corrosion resistance, a fluororesin coating composition using a polyether sulfone resin together with a water-soluble polyamide-imide has been proposed (Patent Document 3).
また、水溶性ポリアミドイミド樹脂、ポリエーテルイミド、及びフッ素樹脂を含み、ポリエーテルイミドが水溶性ポリアミドイミド樹脂とポリエーテルイミドの合計質量％の５０～７５質量％である、水性フッ素樹脂塗料組成物も提案されている（特許文献４）。 Also, a water-based fluororesin coating composition containing a water-soluble polyamideimide resin, polyetherimide, and a fluororesin, wherein the polyetherimide accounts for 50 to 75% by mass of the total mass% of the water-soluble polyamideimide resin and polyetherimide. has also been proposed (Patent Document 4).
さらに、水溶性ポリアミドイミド樹脂、ポリエーテルエーテルケトン及びフッ素樹脂を含み、フッ素樹脂がパーフルオロ樹脂である、水性フッ素樹脂塗料組成物も提案されている（特許文献５）。 Furthermore, an aqueous fluororesin coating composition has also been proposed that contains a water-soluble polyamideimide resin, polyetheretherketone, and a fluororesin, and the fluororesin is a perfluororesin (Patent Document 5).
一方、水溶性ポリアミドイミドは水性フッ素樹脂塗料組成物中に均一に溶解し、少量でも高い接着力が得られることから、水溶性ポリアミドイミドを用いた水性フッ素樹脂塗料組成物は、１回の塗装のみで使用するワンコート塗料としての利用も期待できる。ワンコート塗料は、プライマー塗料及びトップコート塗料を使用せず、塗装回数を少なくできることから、コストや生産性が優れる。 On the other hand, water-soluble polyamide-imide dissolves uniformly in water-based fluororesin coating compositions, and high adhesive strength can be obtained even in small amounts. It is also expected to be used as a one-coat paint. One-coat paints are superior in cost and productivity because they do not use primer paints or top coat paints and can reduce the number of times of painting.
またワンコート塗料から得られるフッ素樹脂塗膜は、通常のプライマー塗料とトップコート塗料からなる塗膜に比べて、バインダー樹脂として用いた耐熱性樹脂により塗膜の硬さや耐摩耗性の改善もできる。
これらの利点から、ワンコート塗料に適した水性フッ素樹脂塗料組成物は様々な用途への展開が可能となる。
In addition, the fluororesin coating film obtained from one-coat paint can improve the hardness and abrasion resistance of the coating film due to the heat-resistant resin used as the binder resin, compared to a coating film made of ordinary primer paint and top coat paint. .
Because of these advantages, water-based fluororesin coating compositions suitable for one-coat coatings can be used in a variety of applications.
ワンコート塗料に適した水性フッ素樹脂塗料組成物には、フッ素樹脂塗料としての性能に加えて、１回の塗装で十分な耐久性のある厚い塗膜を形成できる厚塗り性や、様々な基材へ適用できることが求められる。
しかしながら、これまで提案されたフッ素樹脂塗料組成物は、プライマー塗料としては満足できる性能を示すものの、ワンコート塗料としては、厚塗り性や様々な基材へ適用できる汎用性の面から、十分な性能を発揮できるものではなかった。
In addition to the performance of a fluororesin paint, water-based fluororesin paint compositions suitable for one-coat paints have the ability to coat thickly to form a sufficiently durable and thick film with one coat, and have various base properties. It is required that it can be applied to materials.
However, although the fluororesin paint compositions proposed so far show satisfactory performance as primer paints, they are insufficient as one-coat paints in terms of thick coating properties and versatility that can be applied to various substrates. It was not possible to demonstrate its performance.
本発明の目的は、様々な金属基材に強固に接着し、1回の塗装で耐水蒸気性・耐食性に優れた十分な厚みのある塗膜を形成できる水性フッ素樹脂塗料組成物、それを塗装してなる塗膜、その塗膜を有する物品を提供することである。 The purpose of the present invention is to provide a water-based fluororesin coating composition that can firmly adhere to various metal substrates and form a sufficiently thick coating film with excellent water vapor resistance and corrosion resistance in one application, and a coating composition using the composition. An object of the present invention is to provide a coating film made of the same, and an article having the coating film.
上記目的を達成するため、本発明の水性フッ素樹脂塗料組成物は、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン、フッ素樹脂及び充填材を含み、フッ素樹脂がパーフルオロ樹脂であり、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン及びその他のバインダー樹脂からなるバインダー樹脂の総量とフッ素樹脂の量の合計量（樹脂固形分）におけるバインダー樹脂の割合が３５～５５質量％であることを特徴とする。 In order to achieve the above object, the water-based fluororesin coating composition of the present invention contains a water-soluble polyamide-imide resin, an aromatic polyetherketone, a fluororesin, and a filler, the fluororesin is a perfluoro resin, and the water-soluble polyamide-imide resin It is characterized in that the ratio of binder resin in the total amount of binder resin consisting of imide resin, aromatic polyether ketone and other binder resins and the amount of fluororesin (resin solid content) is 35 to 55% by mass. .
すなわち、本発明は以下のとおりのものである。
（１）水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン、フッ素樹脂及び充填材を含み、フッ素樹脂がパーフルオロ樹脂であり、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン及びその他のバインダー樹脂からなるバインダー樹脂の量とフッ素樹脂の量の合計量（樹脂固形分）におけるバインダー樹脂の割合が３５～５５質量％である、水性フッ素樹脂塗料組成物。
（２）充填材が鱗片状充填材である、（１）の水性フッ素樹脂塗料組成物。
（３）充填材がマイカである、（１）又は（２）の水性フッ素樹脂塗料組成物。
（４）水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン及びその他のバインダー樹脂からなるバインダー樹脂の量とフッ素樹脂の量の合計量における水溶性ポリアミドイミド樹脂の割合が１５～５０質量％である、（１）～（３）の水性フッ素樹脂塗料組成物。
（５）フッ素樹脂が非溶融流動性ポリテトラフルオロエチレンを含む、（１）～（４）のいずれかに記載の水性フッ素樹脂塗料組成物。
（６）水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン及びその他のバインダー樹脂からなるバインダー樹脂の総量とフッ素樹脂の量の合計量（樹脂固形分）における非溶融流動性ポリテトラフルオロエチレンの割合が３５質量％以上である、（５）の水性フッ素樹脂塗料組成物。
（７）（１）～（６）の水性フッ素樹脂塗料組成物の塗膜。
（８）厚さ４０μｍ以上のワンコート塗膜である、（７）の塗膜。
（９）（１）～（６）の水性フッ素樹脂塗料組成物の塗膜を有する物品。
That is, the present invention is as follows.
(1) Contains water-soluble polyamide-imide resin, aromatic polyether ketone, fluororesin, and filler, the fluororesin is perfluoro resin, and consists of water-soluble polyamide-imide resin, aromatic polyether ketone, and other binder resins. An aqueous fluororesin coating composition in which the proportion of binder resin in the total amount of binder resin and fluororesin (resin solid content) is 35 to 55% by mass.
(2) The aqueous fluororesin coating composition of (1), wherein the filler is a scale-like filler.
(3) The aqueous fluororesin coating composition of (1) or (2), wherein the filler is mica.
(4) The proportion of water-soluble polyamide-imide resin in the total amount of the binder resin consisting of water-soluble polyamide-imide resin, aromatic polyether ketone, and other binder resins and the amount of fluororesin is 15 to 50% by mass. Aqueous fluororesin coating compositions (1) to (3).
(5) The aqueous fluororesin coating composition according to any one of (1) to (4), wherein the fluororesin contains non-melt flowable polytetrafluoroethylene.
(6) The proportion of non-melt flowable polytetrafluoroethylene in the total amount of binder resin consisting of water-soluble polyamideimide resin, aromatic polyether ketone and other binder resins and the total amount of fluororesin (resin solid content) The aqueous fluororesin coating composition of (5), which has a content of 35% by mass or more.
(7) A coating film of the aqueous fluororesin coating composition of (1) to (6).
(8) The coating film of (7), which is a one-coat coating film with a thickness of 40 μm or more.
(9) An article having a coating film of the aqueous fluororesin coating composition of (1) to (6).
本発明によれば、様々な金属基材に強固に接着し、1回の塗装で耐水蒸気性・耐食性に優れた十分な厚みのある塗膜を形成できる水性フッ素樹脂塗料組成物、それを塗装してなる塗膜、その塗膜を有する物品を提供することができる。 According to the present invention, a water-based fluororesin coating composition that firmly adheres to various metal substrates and can form a sufficiently thick coating film with excellent water vapor resistance and corrosion resistance in a single coating, and a coating composition using the same, is provided. It is possible to provide a coating film made of the same, and an article having the coating film.
以下、本発明について詳細に説明する。
１．水性フッ素樹脂塗料組成物
本発明の水性フッ素樹脂塗料組成物は、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン、フッ素樹脂及び充填材を含むものである。
The present invention will be explained in detail below.
1. Aqueous Fluororesin Coating Composition The aqueous fluororesin coating composition of the present invention contains a water-soluble polyamideimide resin, an aromatic polyetherketone, a fluororesin, and a filler.
＜水性フッ素樹脂塗料組成物＞
本発明の「水性フッ素樹脂塗料組成物」は、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン、フッ素樹脂及び充填材を含む水性（水系）分散体であり、フッ素樹脂がパーフルオロ樹脂であり、水溶性ポリアミドイミド樹脂、芳香族ポリエーテルケトン及びその他のバインダー樹脂からなるバインダー樹脂の総量とフッ素樹脂の量の合計量（樹脂固形分）におけるバインダー樹脂の割合が３５～５５質量％である。本発明の水性フッ素樹脂塗料組成物は、1回の塗装で耐水蒸気性・耐食性に優れた十分な厚みのあるフッ素樹脂塗膜を様々な基材上に形成できるので、ワンコート塗料として特に優れた性能を発揮する。
<Aqueous fluororesin coating composition>
The "aqueous fluororesin coating composition" of the present invention is an aqueous (aqueous) dispersion containing a water-soluble polyamideimide resin, an aromatic polyether ketone, a fluororesin, and a filler, and the fluororesin is a perfluororesin, The proportion of the binder resin in the total amount of the binder resin consisting of water-soluble polyamideimide resin, aromatic polyether ketone and other binder resins and the amount of fluororesin (resin solid content) is 35 to 55% by mass. The water-based fluororesin coating composition of the present invention is particularly effective as a one-coat coating because it can form a sufficiently thick fluororesin coating film with excellent water vapor resistance and corrosion resistance on various substrates in one coating. Demonstrates excellent performance.
＜水溶性ポリアミドイミド樹脂（水溶性ＰＡＩ）＞
本発明に用いられる「水溶性ポリアミドイミド樹脂（水溶性ＰＡＩ）」とは、アミド結合とイミド結合とを主鎖に持つ水溶性樹脂であり、好ましくは下記一般式：
The "water-soluble polyamide-imide resin (water-soluble PAI)" used in the present invention is a water-soluble resin having an amide bond and an imide bond in the main chain, and preferably has the following general formula:
本発明で用いられる水溶性ＰＡＩは、極性溶媒中で、アミン成分としてジイソシアネート化合物又はジアミン化合物と、酸成分として三塩基酸無水物又は三塩基酸ハライドとを共重合させることで得られる。水溶性ＰＡＩの合成条件は多様であり、特に限定されないが、通常、８０～１８０℃の温度で行われ、空気中の水分の影響を低減するため、窒素等の雰囲気下で行うことが好ましい。 The water-soluble PAI used in the present invention is obtained by copolymerizing a diisocyanate compound or diamine compound as an amine component and a tribasic acid anhydride or tribasic acid halide as an acid component in a polar solvent. Synthesis conditions for water-soluble PAI vary and are not particularly limited, but it is usually carried out at a temperature of 80 to 180°C, and preferably carried out under an atmosphere of nitrogen or the like to reduce the influence of moisture in the air.
ジイソシアネート化合物としては、特に限定されないが、例えば、下記式（１）で表されるジイソシアネート化合物が挙げられる。式（１）中、Ｘは２価の有機基を示す。
Ｘで示される２価の有機基としては、例えば、炭素数１～２０のアルキレン基；未置換、メチル基等の炭素数１～５の低級アルキル基、又はメトキシ基等の炭素数１～５の低級アルコキシ基で置換されているフェニレン基、ナフチレン基等のアリーレン基；単結合、炭素数１～５の低級アルキレン基、オキシ基（－Ｏ－）、カルボニル基（－ＣＯ－）、又はスルホニル基（－ＳＯ2－）を介して上記アリーレン基が２つ結合してなる２価の有機基；上記アリーレン基を介して炭素数１～５の低級アルキレン基が２つ結合してなる２価の有機基などが挙げられる。アルキレン基の炭素数は、好ましくは１～１８であり、より好ましくは１～１２であり、更に好ましくは１～６であり、特に好ましくは１～４である。 Examples of the divalent organic group represented by An arylene group such as a phenylene group or naphthylene group substituted with a lower alkoxy group; a single bond, a lower alkylene group having 1 to 5 carbon atoms, an oxy group (-O-), a carbonyl group (-CO-), or a sulfonyl group A divalent organic group formed by bonding two of the above arylene groups via a group (-SO 2 -); A divalent organic group formed by bonding two lower alkylene groups having 1 to 5 carbon atoms via the above arylene group Examples include organic groups such as The alkylene group preferably has 1 to 18 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
Ｘで示される２価の有機基は、反応性、塗膜の接着強度向上等の観点から、好ましくは、単結合、炭素数１～５の低級アルキレン基、オキシ基（－Ｏ－）、カルボニル基（－ＣＯ－）、又はスルホニル基（－ＳＯ2－）を介して上記アリーレン基が２つ結合してなる２価の有機基であり、より好ましくは単結合又は炭素数１～５の低級アルキレン基を介して上記アリーレン基が２つ結合してなる２価の有機基であり、更に好ましくは単結合又は炭素数１～５の低級アルキレン基を介してフェニレン基が２つ結合してなる２価の有機基である。ジイソシアネート化合物を２種以上組み合わせて用いる場合も、これらの好ましい態様の中から２種以上を選択して使用することが好ましい。また、アリーレン基は、反応性の観点からは、未置換であることが好ましく、塗膜の接着強度向上の観点からは、メチル基等の炭素数１～５の低級アルキル基、又はメトキシ基等の炭素数１～５の低級アルコキシ基で置換されていることが好ましい。 The divalent organic group represented by X is preferably a single bond, a lower alkylene group having 1 to 5 carbon atoms, an oxy group (-O-), a carbonyl group, etc. A divalent organic group formed by bonding two of the above arylene groups via a group (-CO-) or a sulfonyl group (-SO 2 -), more preferably a single bond or a lower group having 1 to 5 carbon atoms. A divalent organic group formed by bonding two of the above arylene groups via an alkylene group, more preferably two phenylene groups bonded via a single bond or a lower alkylene group having 1 to 5 carbon atoms. It is a divalent organic group. Even when using a combination of two or more types of diisocyanate compounds, it is preferable to select and use two or more types from these preferred embodiments. In addition, the arylene group is preferably unsubstituted from the viewpoint of reactivity, and from the viewpoint of improving the adhesive strength of the coating film, it is preferable to use a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, or a methoxy group. is preferably substituted with a lower alkoxy group having 1 to 5 carbon atoms.
ジイソシアネート化合物として、具体的には、キシリレンジイソシアネート、パラフェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート、３，３'－ジフェニルメタンジイソシアネート、４，４'－ジフェニルメタンジイソシアネート、３，３'－ジメチルビフェニル－４，４'－ジイソシアネート、３，３'－ジメトキシビフェニル－４，４'－ジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアレート等が挙げられる。 Specific examples of the diisocyanate compound include xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, 3,3'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenyl-4, Examples include 4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
ジアミン化合物としては、特に限定されないが、上記式（１）において、イソシアネート基をアミノ基に置き換えた化合物が挙げられる。ジアミン化合物として、具体的には、キシリレンジアミン、フェニレンジアミン、４，４'－ジアミノジフェニルメタン、４，４'－ジアミノジフェニルエーテル、４，４'－ジアミノジフェニルスルホン、３，３'－ジアミノジフェニルスルホン、３，３'－ジメチルビフェニル－４，４'－ジアミン、イソホロンジアミン等が挙げられる。 Examples of the diamine compound include, but are not particularly limited to, compounds obtained by replacing the isocyanate group with an amino group in the above formula (1). Specific examples of the diamine compound include xylylene diamine, phenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, Examples include 3,3'-dimethylbiphenyl-4,4'-diamine and isophorone diamine.
アミン成分（ジイソシアネート化合物、ジアミン化合物）として、３，３'－ジメチルビフェニル－４，４'－ジイソシアネート及び／又は３，３'－ジメチルビフェニル－４，４'－ジアミンを用いることが、塗膜の基材接着強度と耐水蒸気性を向上させることができるため、好ましい。更に、作業環境を向上させる観点から、３，３'－ジメチルビフェニル－４，４'－ジイソシアネートを用いることが好ましい（国際公開ＷＯ２０１６／１７５０９９号）。 The use of 3,3'-dimethylbiphenyl-4,4'-diisocyanate and/or 3,3'-dimethylbiphenyl-4,4'-diamine as the amine component (diisocyanate compound, diamine compound) improves the coating film. This is preferable because it can improve the base material adhesive strength and water vapor resistance. Furthermore, from the viewpoint of improving the working environment, it is preferable to use 3,3'-dimethylbiphenyl-4,4'-diisocyanate (International Publication No. WO2016/175099).
反応には、ジイソシアネート化合物を単独で用いても、ジアミン化合物を単独で用いても、ジイソシアネート化合物とジアミン化合物を併用してもよい。反応を容易に行う観点から、ジイソシアネート化合物が好ましく使用される。 In the reaction, a diisocyanate compound may be used alone, a diamine compound may be used alone, or a diisocyanate compound and a diamine compound may be used in combination. From the viewpoint of facilitating the reaction, diisocyanate compounds are preferably used.
三塩基酸無水物としては、トリカルボン酸無水物が挙げられる。特に限定されないが、好ましくは芳香族三塩基酸無水物であり、より好ましくは芳香族トリカルボン酸無水物であり、更に好ましくは下記式（２）又は式（３）で表される化合物である。耐熱性、コスト等の観点からトリメリット酸無水物が特に好ましい。 Tricarboxylic acid anhydrides include tricarboxylic acid anhydrides. Although not particularly limited, it is preferably an aromatic tribasic acid anhydride, more preferably an aromatic tricarboxylic acid anhydride, and even more preferably a compound represented by the following formula (2) or formula (3). Trimellitic anhydride is particularly preferred from the viewpoints of heat resistance, cost, etc.
三塩基酸ハライドとしては、三塩基酸無水物ハライドが好ましく使用され、例えば、トリカルボン酸無水物ハライドが挙げられる。三塩基酸無水物ハライドは、三塩基酸無水物クロライドであることが好ましい。特に限定されないが、好ましくは芳香族三塩基酸無水物クロライドであり、より好ましくは芳香族トリカルボン酸無水物クロライドであり、更に好ましくは上記式（２）又は（３）において－ＣＯＯＲ基を－ＣＯＣｌ基に置き換えた化合物である。耐熱性、コスト等の観点から、トリメリット酸無水物クロライド（無水トリメリット酸クロライド）が特に好ましい。 As the tribasic acid halide, tribasic acid anhydride halides are preferably used, such as tricarboxylic acid anhydride halides. The tribasic acid anhydride halide is preferably a tribasic acid anhydride chloride. Although not particularly limited, aromatic tribasic acid anhydride chloride is preferred, aromatic tricarboxylic acid anhydride chloride is more preferred, and -COOR group in the above formula (2) or (3) is replaced with -COCl. This is a compound in which a group is replaced with a group. From the viewpoint of heat resistance, cost, etc., trimellitic anhydride chloride (trimellitic anhydride chloride) is particularly preferred.
環境への負荷を軽減させる観点から、トリカルボン酸無水物が好ましく使用され、トリメリット酸無水物が特に好ましい。 From the viewpoint of reducing the burden on the environment, tricarboxylic anhydride is preferably used, and trimellitic anhydride is particularly preferred.
酸成分としては、三塩基酸無水物及び三塩基酸ハライドの他に、親水性を向上させるために、ジカルボン酸、テトラカルボン酸二無水物等の多塩基酸又は多塩基酸無水物を、水溶性ＰＡＩの耐熱性等の特性を損なわない範囲で用いることができる。 As acid components, in addition to tribasic acid anhydrides and tribasic acid halides, polybasic acids or polybasic acid anhydrides such as dicarboxylic acids and tetracarboxylic dianhydrides can be used to improve hydrophilicity. It can be used within a range that does not impair the properties such as heat resistance of PAI.
ジカルボン酸としては、特に限定されないが、テレフタル酸、イソフタル酸、アジピン酸、セバシン酸等が挙げられる。テトラカルボン酸二無水物としては、特に限定されないが、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物等が挙げられる。多塩基酸及び多塩基酸無水物は、それぞれ１種のみ使用しても、２種以上を組み合わせて使用してもよい。 Examples of dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, adipic acid, sebacic acid, and the like. Examples of the tetracarboxylic dianhydride include, but are not particularly limited to, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and the like. Each of the polybasic acids and polybasic acid anhydrides may be used alone or in combination of two or more.
三塩基酸無水物及び三塩基酸ハライド以外の多塩基酸及び多塩基酸無水物（例えば、ジカルボン酸、テトラカルボン酸二無水物）の使用量は、水溶性ＰＡＩの耐熱性等の特性を保つ観点から、全酸成分中に０～５０モル％が好ましく、０～３０モル％がより好ましく、０～１５モル％が更に好ましい。 The amount of polybasic acids and polybasic acid anhydrides other than tribasic acid anhydrides and tribasic acid halides (e.g., dicarboxylic acids, tetracarboxylic dianhydrides) should be adjusted to maintain properties such as heat resistance of water-soluble PAI. From this point of view, it is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and even more preferably 0 to 15 mol% in the total acid component.
ジイソシアネート化合物及び／又はジアミン化合物と、酸成分（三塩基酸無水物及び／又は三塩基酸ハライド、並びに、必要に応じて用いられるジカルボン酸及び／又はテトラカルボン酸二無水物等）の使用比率は、生成させる水溶性ＰＡＩの分子量及び架橋度の観点から、酸成分の総量１．０モルに対してジイソシアネート化合物及び／又はジアミン化合物の総量が０．８～１．１モルであることが好ましく、０．９５～１．０８モルであることがより好ましく、１．０～１．０８モルであることが更に好ましい。 The usage ratio of the diisocyanate compound and/or diamine compound and the acid component (tribasic acid anhydride and/or tribasic acid halide, dicarboxylic acid and/or tetracarboxylic dianhydride used as necessary, etc.) is From the viewpoint of the molecular weight and degree of crosslinking of the water-soluble PAI to be produced, it is preferable that the total amount of the diisocyanate compound and/or diamine compound is 0.8 to 1.1 mol per 1.0 mol of the total amount of acid components, The amount is more preferably 0.95 to 1.08 mol, and even more preferably 1.0 to 1.08 mol.
水溶性ＰＡＩとして、ジイソシアネート化合物及び／又はジアミン化合物と、酸成分とを反応させて得られるＰＡＩをそのまま使用することができる。また、ブロック剤で保護した後に使用することも可能である。
原料化合物としてジイソシアネート化合物を使用する場合、ＰＡＩを安定化させる目的で、末端イソシアネート基のブロック剤（末端ブロック剤）を任意で使用してもよい。ブロック剤で保護することにより、水溶性ＰＡＩは、イソシアネート基（－ＮＣＯ基）を有しないか、又は、イソシアネート化合物と酸成分とを反応させて得られるものと比べ、イソシアネート基（－ＮＣＯ基）の量が低減されたものとなる。
As the water-soluble PAI, a PAI obtained by reacting a diisocyanate compound and/or a diamine compound with an acid component can be used as is. It is also possible to use it after protecting it with a blocking agent.
When a diisocyanate compound is used as a raw material compound, a terminal isocyanate group blocking agent (end blocking agent) may be optionally used for the purpose of stabilizing PAI. By protecting with a blocking agent, water-soluble PAI has no isocyanate groups (-NCO groups) or has less isocyanate groups (-NCO groups) than those obtained by reacting an isocyanate compound with an acid component. The amount of is reduced.
ブロック剤としてアルコールが挙げられ、アルコールとしては、メタノール、エタノール、プロパノール等の炭素数１～６の低級アルコールが挙げられる。また、ブロック剤として、２－ブタノンオキシム、δ－バレロラクタム、ε－カプロラクタム等が挙げられる。ブロック剤は、これらの例示化合物に限定されることはない。ブロック剤を、１種を単独で、又は、２種以上を組み合わせて使用してもよい。 Examples of the blocking agent include alcohol, and examples of the alcohol include lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, and propanol. Further, examples of blocking agents include 2-butanone oxime, δ-valerolactam, and ε-caprolactam. Blocking agents are not limited to these exemplified compounds. One type of blocking agent may be used alone or two or more types may be used in combination.
重合に使用される極性溶媒としては、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、Ｎ－エチルモルフォリン、Ｎ－ホルミルモルフォリン、Ｎ－アセチルモルフォリン、Ｎ，Ｎ′－ジメチルエチレンウレア、Ｎ，Ｎ－ジメチルアセトアミド又はＮ，Ｎ－ジメチルホルムアミド、及びγ―ブチロラクトン等を用いることができる。入手容易であり、高沸点であることから、これまでＮＭＰが好ましく用いられてきたが、人体への影響や、ＲＥＡＣＨ規制や米国ＦＤＡなどの法規制の観点から、Ｎ－エチルモルフォリン、Ｎ－ホルミルモルフォリンを用いることが好ましい。 Polar solvents used in the polymerization include N-methyl-2-pyrrolidone (NMP), N-ethylmorpholine, N-formylmorpholine, N-acetylmorpholine, N,N'-dimethylethyleneurea, N, N-dimethylacetamide or N,N-dimethylformamide, γ-butyrolactone, etc. can be used. Up until now, NMP has been preferred because it is easily available and has a high boiling point, but N-ethylmorpholine, N-ethylmorpholine, N- Preferably, formylmorpholine is used.
溶媒の使用量に特に制限はないが、アミン成分と酸成分の総量１００質量部に対して５０～５００質量部とすることが、得られる樹脂の溶解性の観点から好ましい。 There is no particular restriction on the amount of the solvent used, but it is preferably from 50 to 500 parts by weight based on 100 parts by weight of the total amount of the amine component and acid component from the viewpoint of solubility of the resulting resin.
水溶性ＰＡＩの数平均分子量は、塗膜の強度を確保する観点から、５，０００以上が好ましく、１０，０００以上がより好ましく、１３，０００以上が更に好ましく、１５，０００以上が特に好ましい。また、数平均分子量は、水への溶解性を確保する観点から、５０，０００以下が好ましく、３０，０００以下がより好ましく、２５，０００以下が更に好ましく、２０，０００以下が特に好ましい。 The number average molecular weight of the water-soluble PAI is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 13,000 or more, and particularly preferably 15,000 or more, from the viewpoint of ensuring the strength of the coating film. Moreover, from the viewpoint of ensuring solubility in water, the number average molecular weight is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 25,000 or less, and particularly preferably 20,000 or less.
水溶性ＰＡＩの数平均分子量は、合成時にＰＡＩをサンプリングして、数平均分子量を測定し、目的とする数平均分子量が得られるまで合成を継続することによって管理できる。数平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）により、標準ポリスチレンの検量線を用いて測定することができる。 The number average molecular weight of water-soluble PAI can be controlled by sampling PAI during synthesis, measuring the number average molecular weight, and continuing the synthesis until the desired number average molecular weight is obtained. The number average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
水溶性ＰＡＩは、樹脂中のカルボキシル基と酸無水物基を開環させたカルボキシル基とを合わせた酸価が、１０ｍｇＫＯＨ／ｇ以上であることが好ましい。より好ましくは２５ｍｇＫＯＨ／ｇ以上、更に好ましくは３５ｍｇＫＯＨ／ｇ以上である。これらの範囲は、水溶性ＰＡＩの溶解又は分散を容易にする観点から、好ましい範囲である。また、後述する塩基性化合物を含有する場合に、塩基性化合物と反応するカルボキシル基の量が十分となり、水溶化が容易になることからも好ましい範囲である。 The water-soluble PAI preferably has an acid value of 10 mgKOH/g or more, which is the sum of the carboxyl group in the resin and the carboxyl group ring-opened by the acid anhydride group. More preferably, it is 25 mgKOH/g or more, and still more preferably 35 mgKOH/g or more. These ranges are preferred from the viewpoint of facilitating dissolution or dispersion of water-soluble PAI. Furthermore, when the basic compound described below is contained, the amount of carboxyl groups that react with the basic compound is sufficient, and water solubilization becomes easy, which is also a preferable range.
また、酸価は、最終的に得られるフッ素樹脂塗料組成物について、経日によりゲル化を防止する観点から、８０ｍｇＫＯＨ／ｇ以下が好ましい。より好ましくは６０ｍｇＫＯＨ／ｇ以下、更には５０ｍｇＫＯＨ／ｇ以下である。 Further, the acid value is preferably 80 mgKOH/g or less from the viewpoint of preventing gelation of the finally obtained fluororesin coating composition over time. More preferably it is 60 mgKOH/g or less, further preferably 50 mgKOH/g or less.
酸価は、以下の方法で得ることができる。まず、水溶性ＰＡＩを０．５ｇ採取し、これに１，４－ジアザビシクロ［２，２，２］オクタンを０．１５ｇ加え、更にＮ－メチル－２－ピロリドン６０ｇとイオン交換水１ｍＬを加え、ＰＡＩが完全に溶解するまで撹拌し、評価用溶液を調製する。評価用溶液を用いて、電位差滴定法により、０．０５ｍｏｌ／Ｌの水酸化カリウムエタノール溶液で滴定し、酸価を得る。酸価は、樹脂中のカルボキシル基と酸無水物基を開環させたカルボキシル基とを合わせた酸価である。 Acid value can be obtained by the following method. First, 0.5 g of water-soluble PAI was collected, 0.15 g of 1,4-diazabicyclo[2,2,2]octane was added, and 60 g of N-methyl-2-pyrrolidone and 1 mL of ion-exchanged water were added. Stir until PAI is completely dissolved to prepare a solution for evaluation. The evaluation solution is titrated with a 0.05 mol/L potassium hydroxide ethanol solution by potentiometric titration to obtain the acid value. The acid value is the sum of the carboxyl groups in the resin and the carboxyl groups formed by opening the acid anhydride group.
さらに、ＰＡＩの水への溶解性を高めるために、塩基性化合物を作用させてもよい。塩基性化合物は、ＰＡＩに含まれるカルボキシル基と反応し、塩基性化合物とＰＡＩとによる塩が形成される。塩基性化合物の作用により、ＰＡＩの水への溶解性を高めることができる。 Furthermore, a basic compound may be used to increase the solubility of PAI in water. The basic compound reacts with the carboxyl group contained in PAI to form a salt between the basic compound and PAI. The solubility of PAI in water can be increased by the action of the basic compound.
本発明において、塩基性化合物としては、トリエチルアミン、トリブチルアミン、Ｎ，Ｎ－ジメチルシクロヘキシルアミン、Ｎ，Ｎ－ジメチルベンジルアミン、トリエチレンジアミン、Ｎ－メチルモルホリン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ'，Ｎ"，Ｎ"－ペンタメチルジエチレントリアミン、Ｎ，Ｎ'，Ｎ'－トリメチルアミノエチルピペラジン、ジエチルアミン、ジイソプロピルアミン、ジブチルアミン、エチルアミン、イソプロピルアミン、ブチルアミン等のアルキルアミン類；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジプロパノールアミン、トリプロパノールアミン、Ｎ－エチルエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、シクロヘキサノールアミン、Ｎ－メチルシクロヘキサノールアミン、Ｎ－ベンジルエタノールアミン等のアルカノールアミン類；水酸化ナトリウム、水酸化カリウム等の苛性アルカリ；又はアンモニア等が挙げられる。ＰＡＩの水への溶解性を高める観点から、アルキルアミン類及び／又はアルカノールアミン類が適している。 In the present invention, basic compounds include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylenediamine, N-methylmorpholine, N,N,N',N'-tetra Alkyl such as methylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N',N'-trimethylaminoethylpiperazine, diethylamine, diisopropylamine, dibutylamine, ethylamine, isopropylamine, butylamine, etc. Amines; monoethanolamine, diethanolamine, triethanolamine, dipropanolamine, tripropanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, cyclohexanolamine, N-methyl Examples include alkanolamines such as cyclohexanolamine and N-benzylethanolamine; caustic alkalis such as sodium hydroxide and potassium hydroxide; or ammonia. From the viewpoint of increasing the solubility of PAI in water, alkylamines and/or alkanolamines are suitable.
塩基性化合物は、ＰＡＩの水溶化を容易とし、かつ、塗膜の強度を向上させる観点から、樹脂中に含まれるカルボキシル基及び開環させた酸無水物基に対して、２．５当量以上となる量で使用されることが好ましく、より好ましくは３．５当量以上、更に好ましくは４当量以上である。また、塩基性化合物の含有量は、強度を維持する観点から、１０当量以下となる量で使用されることが好ましく、より好ましくは８当量以下、更に好ましくは６当量以下である。 The basic compound should be used in an amount of 2.5 equivalents or more based on the carboxyl group and ring-opened acid anhydride group contained in the resin, from the viewpoint of facilitating water solubilization of PAI and improving the strength of the coating film. It is preferably used in an amount such that the amount is more preferably 3.5 equivalents or more, still more preferably 4 equivalents or more. Further, from the viewpoint of maintaining strength, the content of the basic compound is preferably used in an amount of 10 equivalents or less, more preferably 8 equivalents or less, still more preferably 6 equivalents or less.
具体的な水溶性ＰＡＩ及びその製造法は、特許文献３、国際公開ＷＯ２０１６／１７５０９９号、特開２０１６－８９０１６号、特開２０１６－１７０８４号、特開２０１８－２８０２号などに記載されている。 Specific water-soluble PAI and its manufacturing method are described in Patent Document 3, International Publication WO 2016/175099, JP 2016-89016, JP 2016-17084, JP 2018-2802, etc.
本発明に用いられる水溶性ＰＡＩは、通常、溶液として、フッ素樹脂塗料組成物の調製に用いられる。水溶性ＰＡＩ溶液は、有機溶剤を含む水に水溶性ＰＡＩを溶解することにより容易に得ることができる。 The water-soluble PAI used in the present invention is usually used in the form of a solution to prepare a fluororesin coating composition. A water-soluble PAI solution can be easily obtained by dissolving water-soluble PAI in water containing an organic solvent.
上記有機溶剤としては、極性が高く高沸点を有するものであれば特に限定されず、ＰＡＩの重合に用いることのできる各種の極性溶媒が利用可能である。重合に用いる溶媒と同様に、入手容易であり、高沸点であることから、これまでＮＭＰが好ましく用いられてきたが、人体への影響や、ＲＥＡＣＨ規制や米国ＦＤＡなどの法規制の観点から、Ｎ－エチルモルフォリン、Ｎ－ホルミルモルフォリン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、Ｎ－エチル－２－ピロリドンを用いることが好ましい。
上記有機溶剤は、本発明のフッ素樹脂塗料組成物における後述の水性媒体に含有され得る溶剤と同じものであってもよい。
The organic solvent is not particularly limited as long as it is highly polar and has a high boiling point, and various polar solvents that can be used in the polymerization of PAI can be used. Like the solvent used in polymerization, NMP has been preferred because it is easy to obtain and has a high boiling point, but from the viewpoint of the impact on the human body and regulations such as REACH regulations and the US FDA, It is preferable to use N-ethylmorpholine, N-formylmorpholine, 3-methoxy-N,N-dimethylpropanamide, and N-ethyl-2-pyrrolidone.
The organic solvent may be the same as the solvent that can be contained in the aqueous medium described below in the fluororesin coating composition of the present invention.
水溶性ＰＡＩは、粘度の点で、水溶性ＰＡＩ溶液の１～５０質量％の濃度であることが好ましく、より好ましくは５～４０質量％である。 In terms of viscosity, the water-soluble PAI preferably has a concentration of 1 to 50% by weight, more preferably 5 to 40% by weight of the water-soluble PAI solution.
このような水溶性ＰＡＩ溶液の市販品としては、日立化成工業（株）製ＨＰＣ－１０００－２８、ＨＰＣ－２１００Ｄ－２８が挙げられ、好ましくはＨＰＣ－２１００Ｄ－２８である。 Commercially available water-soluble PAI solutions include HPC-1000-28 and HPC-2100D-28 manufactured by Hitachi Chemical Co., Ltd., with HPC-2100D-28 being preferred.
＜芳香族ポリエーテルケトン＞
本発明に用いられる芳香族ポリエーテルケトンは、ベンゼン環がエーテルとケトンにより結合した直鎖状ポリマー構造を持つ、結晶性の熱可塑性樹脂に属するポリマーである。
<Aromatic polyetherketone>
The aromatic polyetherketone used in the present invention is a polymer that belongs to crystalline thermoplastic resins and has a linear polymer structure in which benzene rings are bonded through ether and ketone.
芳香族ポリエーテルケトンとしては、ポリエーテルケトン（ＰＥＫ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリエーテルケトンケトン（ＰＥＫＫ）、ポリエーテルエーテルケトンケトン（ＰＥＥＫＫ）、ポリエーテルケトンエステル等が例示できる。上記芳香族ポリエーテルケトンは、１種を単独で、又は２種以上を組み合わせて使用できる。
上記芳香族ポリエーテルケトンとしては、ＰＥＫ、ＰＥＥＫ、ＰＥＫＫ、ＰＥＥＫＫ及びポリエーテルケトンエステルからなる群より選択される少なくとも１種が好ましく、ＰＥＥＫがより好ましい。
Examples of aromatic polyetherketones include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), and polyetherketone ester. The above-mentioned aromatic polyetherketones can be used alone or in combination of two or more.
The aromatic polyetherketone is preferably at least one selected from the group consisting of PEK, PEEK, PEKK, PEEKK, and polyetherketone ester, and PEEK is more preferred.
本発明に用いられるポリエーテルエーテルケトン（ＰＥＥＫ）は、少なくとも下記の繰り返し単位を有する高分子化合物であり、その単独重合体又は共重合体のいずれも用いることができる。
ポリエーテルエーテルケトン（ＰＥＥＫ）は、通常、ジフェニルスルホン中で、炭酸アルカリ金属、例えば、炭酸カリウム及び／又は炭酸ナトリウムの存在下で、４，４’－ジフルオロベンゾフェノンとヒドロキノンを反応させることにより製造される。
本発明に用いられるポリエーテルエーテルケトン（ＰＥＥＫ）の市販品としては、ビクトレックス社製 ＶＩＣＯＴＥ（登録商標）などが挙げられる。
Polyetheretherketone (PEEK) is usually produced by reacting 4,4'-difluorobenzophenone with hydroquinone in the presence of an alkali metal carbonate, such as potassium carbonate and/or sodium carbonate, in diphenylsulfone. Ru.
Commercially available polyether ether ketone (PEEK) used in the present invention includes VICOTE (registered trademark) manufactured by Victrex.
＜フッ素樹脂＞
本発明において、フッ素樹脂としてはパーフルオロ樹脂が使用される。パーフルオロ樹脂とは、分子鎖中の水素原子が全てフッ素に置き換えられたフッ素樹脂を意味し、具体的には、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン・パーフルオロ（アルキルビニルエーテル）共重合体（ＰＦＡ）、テトラフルオロエチレン・ヘキサフルオロプロピレン・パーフルオロ（アルキルビニルエーテル）共重合体などが挙げられる。
<Fluororesin>
In the present invention, perfluoro resin is used as the fluororesin. Perfluoro resin refers to a fluororesin in which all hydrogen atoms in the molecular chain have been replaced with fluorine. ), tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene/hexafluoropropylene/perfluoro(alkyl vinyl ether) copolymer, and the like.
本発明において、ＰＦＡを使用する場合、ＰＦＡ中のパーフルオロ（アルキルビニルエーテル）のアルキル基は、炭素数が１～５であることが好ましく、１～３であることがより好ましい。またここで、ＰＦＡ中のパーフルオロ（アルキルビニルエーテル）の量としては、１～５０質量％の範囲にあることが好ましい。 In the present invention, when PFA is used, the alkyl group of perfluoro(alkyl vinyl ether) in PFA preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Further, the amount of perfluoro(alkyl vinyl ether) in PFA is preferably in the range of 1 to 50% by mass.
本発明においては、パーフルオロ樹脂として非熱溶融性ポリテトラフルオロエチレン（ＰＴＦＥ）を用いることが好ましい。非熱溶融性ポリテトラフルオロエチレンとは、融点以上で溶融流動性を示さない高分子量のポリテトラフルオロエチレン（ＰＴＦＥ）であり、テトラフルオロエチレン（ＴＦＥ）の単独重合体（ＴＦＥのホモポリマー）、ＴＦＥと共重合可能な単量体が１質量％以下の範囲で含まれるＴＦＥ共重合体（変性ＰＴＦＥ）の何れでも良く、又はその両者を組合せて使用することもできる。 In the present invention, it is preferable to use non-thermofusible polytetrafluoroethylene (PTFE) as the perfluoro resin. Non-thermofusible polytetrafluoroethylene is a high molecular weight polytetrafluoroethylene (PTFE) that does not exhibit melt flowability above its melting point, and is a homopolymer of tetrafluoroethylene (TFE) (homopolymer of TFE), Any TFE copolymer (modified PTFE) containing a monomer copolymerizable with TFE in a range of 1% by mass or less may be used, or a combination of both may be used.
本発明においては、非熱溶融性ポリテトラフルオロエチレン（ＰＴＦＥ）と共に、さらに熱溶融性パーフルオロ樹脂を併用しても良い。熱溶融性パーフルオロ樹脂としては、例えば、低分子量の熱溶融性ポリテトラフルオロエチレン（熱溶融性ＰＴＦＥ）、テトラフルオロエチレン・パーフルオロ（アルキルビニルエーテル）共重合体（ＰＦＡ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン・ヘキサフルオロプロピレン・パーフルオロ（アルキルビニルエーテル）共重合体が挙げられ、これらは、溶液重合、乳化重合、懸濁重合等の従来公知の方法によって製造することができる。
さらに必要に応じてその他のフッ素樹脂を加えても良い。
In the present invention, a thermofusible perfluoro resin may be used in combination with non-thermofusible polytetrafluoroethylene (PTFE). Examples of heat-melting perfluoro resins include low molecular weight heat-melting polytetrafluoroethylene (heat-melting PTFE), tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), and tetrafluoroethylene/hexafluoroethylene. Examples include fluoropropylene copolymer (FEP) and tetrafluoroethylene/hexafluoropropylene/perfluoro(alkyl vinyl ether) copolymer, which can be produced by conventionally known methods such as solution polymerization, emulsion polymerization, and suspension polymerization. can do.
Furthermore, other fluororesins may be added as necessary.
本発明のフッ素樹脂は、公知の重合方法により得た樹脂を分離・乾燥することにより得られる粉体や、それを更に粉砕した粉体、また、特公昭５２－４４５７６に記載の方法などにより微細造粒化された粉体を、塗料組成物中に分散させて用いることができる。さらに、乳化重合により重合されたままのフッ素樹脂分散液（ディスパージョン）を、そのまま用いることもできるし、フッ素樹脂分散液に界面活性剤を添加して安定化させたもの、米国特許第３，０３７，９５３号に記載の方法などの公知の技術により濃縮してフッ素樹脂の濃度を高く調整したものを用いることもできる。安定化させたフッ素樹脂分散液は、フッ素樹脂が凝集や沈降せずに長期にわたって分散状態を維持できるため好ましい。 The fluororesin of the present invention can be obtained as a powder obtained by separating and drying a resin obtained by a known polymerization method, as a powder obtained by further pulverizing the same, or as a fine powder obtained by the method described in Japanese Patent Publication No. 52-44576. The granulated powder can be used by being dispersed in a coating composition. Furthermore, the fluororesin dispersion that has been polymerized by emulsion polymerization can be used as it is, or the fluororesin dispersion can be stabilized by adding a surfactant to it. It is also possible to use a fluororesin that has been concentrated to a high concentration using known techniques such as the method described in No. 037,953. A stabilized fluororesin dispersion is preferable because the fluororesin can maintain a dispersed state for a long period of time without agglomerating or settling.
本発明のフッ素樹脂塗料組成物において、フッ素樹脂は、水性媒体に粒子として分散したものである。上記フッ素樹脂は、平均粒子径が０．０１～５０μｍである粒子からなるものが好ましい。０．０１μｍ未満であると、粒子の分散性が悪く、得られる塗料組成物が機械的安定性及び貯蔵安定性に劣るおそれがある。５０μｍを超えると、粒子の均一分散性に欠け、得られる塗料組成物を用いて塗装する際、表面が平滑な塗膜が得られず、塗膜物性が劣る場合がある。より好ましい上限は、５μｍであり、更に好ましい上限は、０．５μｍであり、より好ましい下限は、０．０５μｍである。上記機械的安定性とは、送液・再分散の際、ホモジナイザー等による強い攪拌や剪断力を与えても、再分散不可能な凝集体を生成しにくい性質のことである。 In the fluororesin coating composition of the present invention, the fluororesin is dispersed in the form of particles in an aqueous medium. The above-mentioned fluororesin preferably consists of particles having an average particle diameter of 0.01 to 50 μm. If it is less than 0.01 μm, the particles may have poor dispersibility, and the resulting coating composition may have poor mechanical stability and storage stability. If it exceeds 50 μm, the particles will lack uniform dispersibility, and when the resulting coating composition is used for coating, a coating film with a smooth surface may not be obtained, and the physical properties of the coating film may be poor. A more preferable upper limit is 5 μm, an even more preferable upper limit is 0.5 μm, and a more preferable lower limit is 0.05 μm. The above-mentioned mechanical stability refers to the property that it is difficult to form aggregates that cannot be redispersed even when strong stirring or shearing force is applied using a homogenizer or the like during liquid feeding and redispersion.
本発明の塗料組成物に用いられるフッ素樹脂分散液の濃度としては、２０～７０質量％であることが好ましく、濃縮により４０～７０質量％としたものを用いることが、塗料組成物中のフッ素樹脂濃度の調整が容易となり好ましい。本発明に用いられるフッ素樹脂分散液の市販品としては、三井・ケマーズ フロロプロダクツ（株）製テフロン（登録商標）ＰＴＦＥ ３１－ＪＲ、ＰＴＦＥ ３４－ＪＲ、ＰＦＡ ３３４－ＪＲ、ＰＦＡ ３３５－ＪＲ、ＦＥＰ １２０－ＪＲが例示される。 The concentration of the fluororesin dispersion used in the coating composition of the present invention is preferably 20 to 70% by mass, and it is preferable to use a concentration of 40 to 70% by mass. This is preferable because the resin concentration can be easily adjusted. Commercial products of the fluororesin dispersion used in the present invention include Teflon (registered trademark) PTFE 31-JR, PTFE 34-JR, PFA 334-JR, PFA 335-JR, and FEP manufactured by Mitsui Chemours Fluoro Products Co., Ltd. 120-JR is exemplified.
本発明において、「樹脂固形分」とは、フッ素樹脂塗料組成物から得られた塗膜中に含まれるフッ素樹脂及びバインダー樹脂の重量を意味する。具体的には、本発明のフッ素樹脂塗料組成物を被塗装物上に塗布したのち８０～１００℃以下の温度で乾燥し、約３８０℃で４５分間焼成した後の残渣におけるバインダー樹脂（水溶性ＰＡＩ、芳香族ポリエーテルケトン、その他のバインダー樹脂）とフッ素樹脂との合計質量を意味する。 In the present invention, "resin solid content" means the weight of the fluororesin and binder resin contained in the coating film obtained from the fluororesin coating composition. Specifically, the binder resin (water-soluble It means the total mass of PAI, aromatic polyetherketone, other binder resin) and fluororesin.
本発明の水性フッ素樹脂塗料組成物は、ワンコート塗料として好適に利用することができる。ワンコート塗料には、基材との強い接着性、長期の使用を可能にする塗膜の耐久性・耐摩耗性、及び、十分な膜厚が求められ、一般に、膜厚としては、少なくとも２０μｍ以上、好ましくは３０μｍ以上であるが、膜厚のバラツキを考慮すれば、それよりも厚い４０μｍ以上の膜厚がクラックなどの不具合無く形成できることから特に望まれている。 The aqueous fluororesin coating composition of the present invention can be suitably used as a one-coat coating. One-coat paints are required to have strong adhesion to the base material, durability and abrasion resistance of the coating film to enable long-term use, and sufficient film thickness. Generally, the film thickness is at least 20 μm. As mentioned above, the thickness is preferably 30 μm or more, but considering the variation in film thickness, a thicker film of 40 μm or more is particularly desired because it can be formed without problems such as cracks.
本発明の水性フッ素樹脂塗料組成物において、樹脂固形分中のバインダー樹脂の割合を、３５～５５質量％とすることにより、４０μｍ以上の膜厚がクラックなどの不具合無く形成できる優れたワンコート塗料を提供することができる。 In the aqueous fluororesin coating composition of the present invention, by setting the proportion of binder resin in the resin solid content to 35 to 55% by mass, an excellent one-coat coating can form a film thickness of 40 μm or more without defects such as cracks. can be provided.
本発明の水性フッ素樹脂塗料組成物において、樹脂固形分（フッ素樹脂及びバインダー樹脂）のうちの水溶性ポリアミドイミドの占める割合は１５～５０質量％の範囲であることが好ましく、１５～４０質量％の範囲がさらに好ましく、１５～３０質量％の範囲が特に好ましい。 In the aqueous fluororesin coating composition of the present invention, the proportion of water-soluble polyamideimide in the resin solid content (fluororesin and binder resin) is preferably in the range of 15 to 50% by mass, and 15 to 40% by mass. More preferably, the range is 15 to 30% by mass.
本発明の水性フッ素樹脂塗料組成物において、芳香族ポリエーテルケトンは
塗膜の基材への接着力、成膜性、耐加水分解性能に寄与すると考えられ、樹脂固形分（フッ素樹脂及びバインダー樹脂）のうち芳香族ポリエーテルケトンの占める割合が５質量％以上を維持することが好ましい。
In the aqueous fluororesin coating composition of the present invention, the aromatic polyetherketone is thought to contribute to the adhesion of the coating film to the substrate, film formability, and hydrolysis resistance. ), it is preferable that the proportion of aromatic polyetherketone is maintained at 5% by mass or more.
上記の通り、本発明の水性フッ素樹脂塗料組成物におけるパーフルオロ樹脂として非熱溶融性ポリテトラフルオロエチレン（ＰＴＦＥ）を用いることが、特に塗膜の耐水蒸気性・耐食性の観点から好ましく、非熱溶融性ポリテトラフルオロエチレン（ＰＴＦＥ）の樹脂固形分（フッ素樹脂及びバインダー樹脂）に占める割合は３５質量％以上であることが好ましく、４０質量％以上がより好ましく、４５質量％以上が更に好ましく、５０質量％以上が特に好ましい。 As mentioned above, it is preferable to use non-thermal melting polytetrafluoroethylene (PTFE) as the perfluoro resin in the aqueous fluororesin coating composition of the present invention, especially from the viewpoint of water vapor resistance and corrosion resistance of the coating film. The proportion of meltable polytetrafluoroethylene (PTFE) in the resin solid content (fluororesin and binder resin) is preferably 35% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, Particularly preferred is 50% by mass or more.
＜充填材＞
本発明の水性フッ素樹脂塗料組成物には、充填材が含まれる。本発明における充填材は、求める特性に応じて、各種の有機物・無機物を選択することができる。有機物としては、例えば、ポリフェニレンサルファイド、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリフェニルスルホン、ポリアミド、ポリイミド、フェノール樹脂、尿素樹脂、エポキシ樹脂、ウレタン樹脂、メラミン樹脂、ポリエステル樹脂、ポリエーテル樹脂、アクリル樹脂、アクリルシリコーン樹脂、シリコーン樹脂、シリコーンポリエステル樹脂などのエンジニアリングプラスチックが挙げられる。無機物としては、金属粉、金属酸化物（酸化アルミ、酸化亜鉛、酸化スズ、酸化チタン等）、ガラス、セラミックス、炭化珪素、酸化珪素、弗化カルシウム、カーボンブラック、グラファイト、マイカ、硫酸バリウムなどが挙げられる。本発明の水性フッ素樹脂塗料組成物に使用される充填材の形状としては、粒子状、繊維状、鱗片状（フレーク状）など、各種の形状の物質が使用可能であるが、なかでも、鱗片状の充填材は、比較的少量でも効率的にクラック発生を抑止するため、好ましく用いられる。鱗片状の充填材としては、マイカ、グラファイト、金属フレーク等を挙げることができる。
<Filling material>
The aqueous fluororesin coating composition of the present invention contains a filler. The filler in the present invention can be selected from various organic and inorganic materials depending on the desired properties. Examples of organic substances include polyphenylene sulfide, polyetheretherketone, polyethersulfone, polyphenylsulfone, polyamide, polyimide, phenol resin, urea resin, epoxy resin, urethane resin, melamine resin, polyester resin, polyether resin, and acrylic resin. Examples include engineering plastics such as acrylic silicone resin, silicone resin, and silicone polyester resin. Inorganic substances include metal powder, metal oxides (aluminum oxide, zinc oxide, tin oxide, titanium oxide, etc.), glass, ceramics, silicon carbide, silicon oxide, calcium fluoride, carbon black, graphite, mica, barium sulfate, etc. Can be mentioned. The filler used in the aqueous fluororesin coating composition of the present invention can be in various shapes such as particles, fibers, and flakes. A filler in the form of a filler is preferably used because it effectively suppresses crack generation even in a relatively small amount. Examples of the scaly filler include mica, graphite, and metal flakes.
鱗片状充填材として、マイカのような絶縁性の鱗片状充填材は、塗装した金属基材の耐食性をいっそう向上させる観点から好ましいが、一方、グラファイトや金属フレーク等はそれ自身が導電性があるため導電性のある塗膜が得られる点で好ましく、用途によって選択することができる。
本発明の水性フッ素樹脂塗料組成物において、充填材の平均粒径は物質、形状や求められる特性に応じて、適宜選択することができるが、例えば、鱗片状の充填材の平均粒径は１～１００μｍであることが好ましく、５～５０μｍであることがより好ましい。充填材の平均粒径は、レーザー回折法による積算値５０％（体積基準）での粒径（ｄ５０）として求められる。
As a scale-like filler, insulating scale-like fillers such as mica are preferable from the viewpoint of further improving the corrosion resistance of the painted metal base material, but on the other hand, graphite, metal flakes, etc. are themselves electrically conductive. Therefore, it is preferable in that a conductive coating film can be obtained, and can be selected depending on the application.
In the aqueous fluororesin coating composition of the present invention, the average particle size of the filler can be appropriately selected depending on the substance, shape, and desired properties. For example, the average particle size of the scaly filler is 1. It is preferably from 100 μm to 50 μm, more preferably from 5 to 50 μm. The average particle size of the filler is determined as the particle size (d50) at an integrated value of 50% (volume basis) by laser diffraction method.
＜その他の成分＞
本発明の水性フッ素樹脂塗料組成物には、分散性・導電性・発泡防止・耐摩耗改善など求める特性に応じて通常の塗料に使用される各種の添加剤、例えば、界面活性剤（例えば、ライオン(株)製レオコール、ダウケミカルカンパニー製ＴＲＩＴＯＮ、ＴＥＲＧＩＴＯＬシリーズ、花王(株)製エマルゲンなどのポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル系の非イオン系界面活性剤や、ライオン(株)製リパール、花王(株)製エマール、ぺレックスなどのスルホコハク酸塩、アルキルエーテルスルホン酸ナトリウム塩、硫酸モノ長鎖アルキル系の陰イオン系界面活性剤、ライオン(株)製レオアール、ダウケミカルカンパニー製ＯＲＯＴＡＮなどのポリカルボン酸塩、アクリル酸塩系の高分子界面活性剤、モメンティブ社製Ｌ－７７、ＡｉｒＰｒｏｄｕｃｔ製サーフィノールシリーズ（サーフィノール４２０、サーフィノール４４０、サーフィノール４６５、サーフィノール４８５など））、造膜剤（例えば、ポリアミドやポリアミドイミド、アクリル、アセテートなどの高分子系造膜剤、高級アルコールやエーテル、造膜効果を有する高分子界面活性剤）、増粘剤（水溶性セルロール類や、溶剤分散系増粘剤、アルギン酸ソーダ、カゼイン、カゼイン酸ソーダ、キサンタンガム、ポリアクリル酸、アクリル酸エステル）なども加えることができる。
<Other ingredients>
The aqueous fluororesin coating composition of the present invention contains various additives used in ordinary coatings, such as surfactants (e.g., Nonionic surfactants based on polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers such as Lion Co., Ltd.'s Rheocol, Dow Chemical Company's TRITON, TERGITOL series, Kao Corporation's Emulgen, and Lion Co., Ltd. Sulfosuccinates, alkyl ether sulfonic acid sodium salts, mono-long chain alkyl sulfate anionic surfactants such as Riparl manufactured by Kao Corporation, Emar manufactured by Kao Corporation, and Perex, Leoard manufactured by Lion Corporation, manufactured by The Dow Chemical Company. Polycarboxylate salts such as OROTAN, acrylate-based polymer surfactants, L-77 manufactured by Momentive, Surfynol series manufactured by AirProduct (Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, etc.)) , film-forming agents (e.g., polymeric film-forming agents such as polyamide, polyamide-imide, acrylic, acetate, higher alcohols and ethers, polymeric surfactants with film-forming effects), thickeners (water-soluble cellulose, etc.), , solvent-dispersed thickeners, sodium alginate, casein, sodium caseinate, xanthan gum, polyacrylic acid, acrylic esters), etc. can also be added.
＜水性媒体＞
本発明の水性フッ素樹脂塗料組成物は、水を主な媒体とするものである。ただし、環境面やコスト面からは好ましくないが、水性フッ素樹脂塗料組成物の液体粘度などのレオロジー特性の適切な調整や、芳香族ポリエーテルケトンや充填材などの分散性改善のために、水と相溶性のある極性溶剤を加えたり、水と非相溶性の有機溶剤を分散させることもできる。また、極性溶剤を加えることで、耐熱性樹脂（バインダー）を溶解させ、塗装後の乾燥過程において耐熱性樹脂（バインダー）がより均一になり、塗膜が緻密化することや、基材の凹凸の凹部に耐熱性樹脂（バインダー）が入り込みやすくなることで基材との接着力向上といった効果が期待できる。
<Aqueous medium>
The aqueous fluororesin coating composition of the present invention uses water as a main medium. However, although it is unfavorable from an environmental and cost perspective, it is necessary to use water to properly adjust the rheological properties such as liquid viscosity of water-based fluoropolymer coating compositions and to improve the dispersibility of aromatic polyether ketones and fillers. It is also possible to add a polar solvent that is compatible with water, or to disperse an organic solvent that is incompatible with water. In addition, by adding a polar solvent, the heat-resistant resin (binder) is dissolved, and during the drying process after painting, the heat-resistant resin (binder) becomes more uniform, and the coating film becomes denser and the unevenness of the base material becomes more uniform. By making it easier for the heat-resistant resin (binder) to enter the recesses, it is expected that the adhesive strength with the base material will be improved.
＜ステンレス（ＳＵＳ）＞
ステンレス（ＳＵＳ）とは、鉄にクロム、ニッケルなどを加えて製造される合金であり、オーステナイト系ステンレス、マルテンサイト系ステンレス、フェライト系ステンレス、オーステナイト・フェライト系ステンレスに大別され、合金の成分により多様な種類があり、ＪＩＳ規格では、代表的なものではＳＵＳ３０４、ＳＵＳ３０３、ＳＵＳ３１６、ＳＵＳ４１０、ＳＵＳ４３０、ＳＵＳ６３０などが規定されている。
<Stainless steel (SUS)>
Stainless steel (SUS) is an alloy manufactured by adding chromium, nickel, etc. to iron, and is broadly classified into austenitic stainless steel, martensitic stainless steel, ferritic stainless steel, and austenitic/ferritic stainless steel, depending on the alloy composition. There are various types, and the JIS standards specify SUS304, SUS303, SUS316, SUS410, SUS430, SUS630, etc. as typical ones.
＜水性フッ素樹脂塗料組成物の製造プロセス＞
本発明の水性フッ素樹脂塗料組成物は、従来公知の方法等により調製することができ、例えば、有機溶剤を含んだ水に溶解している上記水溶性ＰＡＩ溶液と、芳香族ポリエーテルケトン、フッ素樹脂、充填材及び必要に応じて配合するその他の添加剤を適宜混合することにより得られる。本発明の水性フッ素樹脂塗料組成物において、芳香族ポリエーテルケトン、フッ素樹脂、充填材等は、それぞれの分散体（分散液）を予め調製し、得られる分散体を混合することより調製を行うこともできる。
<Manufacturing process of water-based fluororesin coating composition>
The aqueous fluororesin coating composition of the present invention can be prepared by a conventionally known method. For example, the water-soluble PAI solution dissolved in water containing an organic solvent, aromatic polyether ketone, fluorine It is obtained by appropriately mixing a resin, a filler, and other additives blended as necessary. In the aqueous fluororesin coating composition of the present invention, the aromatic polyetherketone, fluororesin, filler, etc. are prepared by preparing respective dispersions (dispersions) in advance and mixing the resulting dispersions. You can also do that.
本発明の水性フッ素樹脂塗料組成物は、２５℃における粘度が０．１～５００００ｍＰａ・ｓであることが好ましい。粘度が０．１ｍＰａ・ｓ未満であると、被塗装物上への塗布時にタレ等を生じやすく、目的とする膜厚を得ることが困難となる場合があり、５００００ｍＰａ・ｓを超えると、塗装作業性が悪くなる場合があり、得られる塗膜の膜厚が均一とならず、表面平滑性等に劣る場合がある。より好ましい下限は、１ｍＰａ・ｓであり、より好ましい上限は、３００００ｍＰａ・ｓである。上記粘度は、ＢＭ型単一円筒型回転粘度計（東京計器社製）を用いて測定することにより得られる値である。 The aqueous fluororesin coating composition of the present invention preferably has a viscosity of 0.1 to 50,000 mPa·s at 25°C. If the viscosity is less than 0.1 mPa・s, sagging, etc. may easily occur when coating on the object to be coated, and it may be difficult to obtain the desired film thickness. If the viscosity exceeds 50,000 mPa・s, the coating Workability may deteriorate, the thickness of the resulting coating film may not be uniform, and surface smoothness may be poor. A more preferable lower limit is 1 mPa·s, and a more preferable upper limit is 30000 mPa·s. The above viscosity is a value obtained by measurement using a BM type single cylinder rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).
２．塗膜
本発明の「塗膜」は、本発明の水性フッ素樹脂塗料組成物を塗装してなる塗膜である。本発明の水性フッ素樹脂塗料組成物は、ワンコート塗料として優れた性能を発揮し、本発明の「塗膜」としては、ワンコート塗装による塗膜が含まれるのは当然であるが、本発明の水性フッ素樹脂塗料組成物を基材と接着するプライマー層とし、その上に複数の層を塗装して積層した塗膜も含まれる。
本発明の「塗膜」は、各種既存の塗装方法、例えば、スプレー塗装、ディップ塗装、スピンコート等通常一般的に用いられる方法により形成することができ、溶融流動させ均一な塗膜を得るために、フッ素樹脂の融点以上に加熱しておくことが好ましい。
ワンコート塗料の塗膜としては、上述のとおり、一般に、膜厚が、少なくとも２０μｍ以上、好ましくは３０μｍ以上であるが、膜厚が４０μｍ以上のものは、長期間に亘って十分な性能を得る上で、特に望ましいものである。
2. Coating Film The "coating film" of the present invention is a coating formed by applying the aqueous fluororesin coating composition of the present invention. The aqueous fluororesin coating composition of the present invention exhibits excellent performance as a one-coat coating, and the "coating film" of the present invention naturally includes a coating film formed by one-coat painting. It also includes a coating film in which a water-based fluororesin coating composition is used as a primer layer that adheres to a base material, and multiple layers are coated and laminated thereon.
The "coating film" of the present invention can be formed by various existing coating methods, such as spray coating, dip coating, spin coating, etc., and can be formed by melting and flowing to obtain a uniform coating film. It is preferable to heat the fluororesin to a temperature higher than its melting point.
As mentioned above, the film of a one-coat paint generally has a film thickness of at least 20 μm or more, preferably 30 μm or more, but one with a film thickness of 40 μm or more provides sufficient performance over a long period of time. The above is particularly desirable.
３．塗装物品
本発明の「塗装物品」は、本発明の水性フッ素樹脂塗料組成物を塗装してなる塗膜を有する物品である。
本発明の「塗装物品」としては、フライパン・炊飯器などの調理器具、工場ラインなどでの耐熱離型性トレイ（パン焼き工程など）、定着ロール・ベルト・インクジェットノズルなどのＯＡ機器関連物品、各種摺動部材、配管などの化学プラントの工業設備関連物品等、非粘着性、撥水撥油性が要求される物品が挙げられる。
3. Coated Article The "coated article" of the present invention is an article having a coating film formed by coating the aqueous fluororesin coating composition of the present invention.
The "coated articles" of the present invention include cooking utensils such as frying pans and rice cookers, heat-resistant release trays for factory lines (for bread baking processes, etc.), OA equipment-related articles such as fixing rolls, belts, and inkjet nozzles, and various other items. Examples include articles that require non-adhesion, water and oil repellency, such as sliding members, piping and other articles related to industrial equipment for chemical plants.
以下、実施例により本発明の水性フッ素樹脂塗料組成物の調製及び性能評価について説明するが、本発明はこれらの実施例に何ら限定されるものでない。 EXAMPLES Hereinafter, the preparation and performance evaluation of the aqueous fluororesin coating composition of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples in any way.
本実施例及び比較例には、以下の試薬を使用した。
水溶性ポリアミドイミド（ＰＡＩ）樹脂
日立化成工業(株)製 ＨＰＣ－２１００Ｄ－２８（ＰＡＩ濃度約２８質量％、水２２－３２質量％、Ｎ－ホルミルモルフォリン３０－４０質量％の溶液）
芳香族ポリエーテルケトン
ＰＥＥＫ粉末：ビクトレックス社製 ＶＩＣＯＴＥ（登録商標） Ｃｏａｔｉｎｇｓ７０４
その他のバインダー樹脂
ポリエーテルスルホン（ＰＥＳ）樹脂
ＰＥＳ粉末：住友化学(株)製 スミカエクセル ４１００ＭＰ
フッ素樹脂
ＰＴＦＥ水性分散液：三井・ケマーズ フロロプロダクツ(株)製テフロン（登録商標）ＰＴＦＥ ３４－ＪＲ（ＰＴＦＥ濃度５８質量％）
ＦＥＰ水性分散液：三井・ケマーズ フロロプロダクツ(株)製テフロン（登録商標）ＦＥＰ １２０－ＪＲ（ＦＥＰ濃度５４質量％）
充填材
マイカ： メルクパフォーマンスマテリアルズ合同会社製 イリオジン１２３
カーボンブラック： カーボンブラック水性分散液（濃度２５質量％）
The following reagents were used in the present examples and comparative examples.
Water-soluble polyamideimide (PAI) resin
Hitachi Chemical Co., Ltd. HPC-2100D-28 (solution of PAI concentration approximately 28% by mass, water 22-32% by mass, and N-formylmorpholine 30-40% by mass)
aromatic polyetherketone
PEEK powder: VICOTE (registered trademark) Coatings704 manufactured by Victrex
Other binder resins
Polyether sulfone (PES) resin PES powder: Sumika Excel 4100MP manufactured by Sumitomo Chemical Co., Ltd.
Fluororesin
PTFE aqueous dispersion: Mitsui Chemours Fluoro Products Co., Ltd. Teflon (registered trademark) PTFE 34-JR (PTFE concentration 58% by mass)
FEP aqueous dispersion: Teflon (registered trademark) FEP 120-JR manufactured by Mitsui Chemours Fluoro Products Co., Ltd. (FEP concentration 54% by mass)
filling material
Mica: Iriodin 123 manufactured by Merck Performance Materials LLC
Carbon black: Carbon black aqueous dispersion (concentration 25% by mass)
実施例１
１Ｌステンレス容器に純水１１７ｇを入れ、攪拌機（ＹＡＭＡＴＯ ＳＣＩＥＮＴＩＦＩＣ ＣＯ．ＬＴＤ．製）を用いて、１４０回転／分で攪拌しながら、非イオン系界面活性剤水溶液（濃度８１質量％）を２０ｇ添加した。この界面活性剤分散液にＰＥＥＫ粉末を７２ｇ加え１０分間撹拌して分散させた。更に、カーボンブラック水性分散液（２５質量％）を５０ｇ加えて、１０分間攪拌し、次いでこれに、ＰＴＦＥ水性分散液を３４２ｇ、マイカを１０ｇと順次加え、１０分間攪拌した後、水溶性ＰＡＩを２１０ｇ加えて、更に１０分間攪拌を行い、水性フッ素樹脂塗料組成物を得た。
Example 1
117 g of pure water was placed in a 1 L stainless steel container, and 20 g of nonionic surfactant aqueous solution (concentration 81% by mass) was added while stirring at 140 revolutions/min using a stirrer (manufactured by YAMATO SCIENTIFIC CO. LTD.). . 72 g of PEEK powder was added to this surfactant dispersion and stirred for 10 minutes to disperse it. Furthermore, 50 g of carbon black aqueous dispersion (25% by mass) was added and stirred for 10 minutes. Next, 342 g of PTFE aqueous dispersion and 10 g of mica were sequentially added thereto, and after stirring for 10 minutes, water-soluble PAI was added. 210 g was added and stirred for an additional 10 minutes to obtain an aqueous fluororesin coating composition.
実施例２～７
下表１に記載の塗料組成（質量％）となるように、各成分の量を調整して、実施例１と同様の手順（例えば、実施例２では、ＰＥＥＫ粉末７２ｇに代えてＰＥＥＫ粉末２４ｇとＰＥＳ粉末４８ｇ、ＰＴＦＥ水性分散液３４２ｇに代えてＦＥＰ水性分散液１２８ｇとＰＴＦＥ水性分散液２２４ｇ）にて水性フッ素樹脂塗料組成物を得た。
Examples 2 to 7
The amount of each component was adjusted so that the coating composition (mass%) was as shown in Table 1 below, and the same procedure as in Example 1 was followed (for example, in Example 2, 24 g of PEEK powder was used instead of 72 g of PEEK powder). An aqueous fluororesin coating composition was obtained by replacing 48 g of PES powder and 342 g of PTFE aqueous dispersion with 128 g of FEP aqueous dispersion and 224 g of PTFE aqueous dispersion.
比較例１～４
下表１の比較例１～３に記載の塗料組成（質量％）となるように、各成分の量を調整して、実施例１と同様の手順にてフッ素樹脂塗料組成物を得た。また、比較例４として、市販の溶剤系ＰＴＦＥワンコート塗料（ポリフロン（登録商標）ＰＴＦＥタフコートエナメル ＴＣ－７８０９ＢＫ）を使用した。
Comparative examples 1 to 4
A fluororesin coating composition was obtained in the same manner as in Example 1 by adjusting the amount of each component so that the coating composition (mass %) was as described in Comparative Examples 1 to 3 in Table 1 below. Furthermore, as Comparative Example 4, a commercially available solvent-based PTFE one-coat paint (Polyflon (registered trademark) PTFE Tough Coat Enamel TC-7809BK) was used.
性能評価に使用する塗膜を以下の手順で作成した。
＜基材接着強度用試験片の作成＞
まず、９５ｍｍ×５０ｍｍのアルミニウム（ＪＩＳ Ａ１０５０準拠品、厚み１ｍｍ）を基材として用い、イソプロピルアルコールで拭き取った後、＃６０アルミナによるショットブラストを施し表面粗度（Ｒａ）を１～５μｍとした後に、各実施例及び比較例のフッ素樹脂塗料組成物をスプレーガン（Ｗ－１０１－１０１Ｇ、アネスト岩田社製）を用いてスプレー塗装し（塗料組成物０．５～０．７ｇ）、１２０℃にて２０分間、続いて３９０℃にて２０分間焼成させ、塗膜を形成した。
A coating film used for performance evaluation was created using the following procedure.
<Creation of test piece for base material adhesive strength>
First, a 95 mm x 50 mm aluminum (JIS A1050 compliant product, thickness 1 mm) was used as a base material, wiped with isopropyl alcohol, and then shot blasted with #60 alumina to give a surface roughness (Ra) of 1 to 5 μm. The fluororesin coating compositions of Examples and Comparative Examples were spray-coated using a spray gun (W-101-101G, manufactured by Anest Iwata Co., Ltd.) (0.5 to 0.7 g of coating composition), and heated to 120°C. The film was then baked at 390° C. for 20 minutes to form a coating film.
アルミニウムに替えて、ステンレス（ＪＩＳ ＳＵＳ３０４、厚み１ｍｍ）及び鉄（ＪＩＳ ＳＳ４００、厚み２ｍｍ）を使用して、同様に評価用試験片を作成した。 Evaluation test pieces were similarly created using stainless steel (JIS SUS304, thickness 1 mm) and iron (JIS SS400, thickness 2 mm) instead of aluminum.
（性能評価方法）
得られた試験片（アルミニウム基材、ステンレス基材及び鉄基材）について、ＪＩＳ Ｋ５６００－５－６クロスカット法 に準じて塗膜の基材接着強度評価を行った（初期値）。ただし、カット数を１１個とし、１００マスで剥離しなかった個数を評価した。
続いて、試験片を１５０℃で０．４メガパスカルの水蒸気中に１００時間放置した後、常温になるまで静置して冷却し、塗膜の状態を観察し、上記と同じ方法（クロスカット法）にて塗膜の基材接着強度を測定した。水蒸気暴露を１００時間毎に２００時間まで、２回水蒸気加圧処理を行い、それぞれに対し同様の観察及びクロスカット法による塗膜の基材接着強度評価を行った。
２回水蒸気加圧処理後に剥離しなかったマスの個数を表１に示した。（測定を行わなかった水準については「未測定」と記載した。）
(Performance evaluation method)
For the obtained test pieces (aluminum base material, stainless steel base material, and iron base material), the adhesion strength of the coating film to the base material was evaluated according to the JIS K5600-5-6 cross-cut method (initial value). However, the number of cuts was 11, and the number of pieces that did not peel off after 100 squares was evaluated.
Next, the test piece was left in water vapor at 0.4 MPa at 150°C for 100 hours, then left to cool down to room temperature, and the condition of the coating film was observed. The adhesion strength of the coating film to the substrate was measured using the following method. Steam pressurization treatment was performed twice for every 100 hours of water vapor exposure up to 200 hours, and the adhesion strength of the coating film to the substrate was evaluated using the same observation and cross-cut method for each time.
Table 1 shows the number of masses that did not peel off after the steam pressure treatment twice. (Levels that were not measured were written as "not measured.")
（厚塗り性能評価）
実施例及び比較例の塗料組成物を、基材接着強度評価用試験片の場合と同様の方法により、９５ｍｍ×２５０ｍｍのアルミ基材（ＪＩＳ Ａ１０５０準拠品、厚み１ｍｍ）に長辺方向に塗着量をグラデーション状に塗布し、焼成後の膜厚が約１０～５０μｍとなるように試験片を作成した。これをデジタルマイクロスコープ（ＨＩＲＯＸ社製ＫＨ－１３００）を用い、３５倍の倍率で観察を行い、良好な塗膜の部分と、クラック等の不具合が発生した境界を確認した。境界付近の良好な塗膜側の膜厚をケット社製過電流膜厚計ＬＺ３７０で測定し、これを不具合なく塗装が可能な最大の膜厚とした。
結果を表１に示す。ここで、例えば実施例１では「＞ ４９」としているが、これは作成した試験片中の最大の膜厚が４９μｍであり、この部分を含む全ての箇所でクラック等の不具合が発生しなかったことを意味する。また比較例２では、「＜ ２０」としているが、これは作成した試験片中の最小の膜厚が２０μｍであり、その最も薄い膜の箇所でもクラックが発生したことを意味する。
(Thick coating performance evaluation)
The coating compositions of Examples and Comparative Examples were applied to a 95 mm x 250 mm aluminum base material (JIS A1050 compliant product, thickness 1 mm) in the long side direction using the same method as in the case of the test piece for base material adhesion strength evaluation. A test piece was prepared by applying the amount in a gradation pattern so that the film thickness after firing was about 10 to 50 μm. This was observed using a digital microscope (KH-1300 manufactured by HIROX Co., Ltd.) at a magnification of 35 times to confirm areas with good coating film and boundaries where defects such as cracks had occurred. The film thickness on the good coating film side near the boundary was measured using an overcurrent film thickness meter LZ370 manufactured by Kett Co., Ltd., and this was taken as the maximum film thickness that could be coated without any defects.
The results are shown in Table 1. Here, for example, in Example 1, it is set as ">49", which means that the maximum film thickness in the prepared test piece was 49 μm, and no defects such as cracks occurred at all locations including this part. It means that. Furthermore, in Comparative Example 2, "<20" means that the minimum film thickness in the prepared test piece was 20 μm, and cracks occurred even at the thinnest film.
本発明の水性フッ素樹脂塗料組成物は、アルミ、ステンレス、鉄のいずれについても極めて優れた接着性を示すことが確認できたが、市販の溶剤系ＰＴＦＥワンコート塗料は、ステンレスにはほとんど接着できなかった。 It was confirmed that the water-based fluororesin coating composition of the present invention exhibits extremely excellent adhesion to aluminum, stainless steel, and iron, but commercially available solvent-based one-coat PTFE coatings hardly adhere to stainless steel. There wasn't.
実施例１～７の本発明の水性フッ素樹脂塗料組成物は、４０μｍ以上の厚さ迄クラックが生成することなく塗布することができたが、樹脂成分中のバインダー比率がより高い比較例１、バインダー比率がより低い比較例２、及び芳香族ポリエーテルケトンを含まない比較例３では、クラックが生成することなく４０μｍ以上の厚さの塗膜を得ることができなかった。 The aqueous fluororesin coating compositions of the present invention in Examples 1 to 7 could be coated to a thickness of 40 μm or more without generating cracks, but Comparative Example 1, in which the binder ratio in the resin component was higher, In Comparative Example 2, which had a lower binder ratio, and Comparative Example 3, which did not contain aromatic polyetherketone, it was not possible to obtain a coating film with a thickness of 40 μm or more without generating cracks.
本発明の水性フッ素樹脂塗料組成物は、様々な金属基材に強固に接着し、1回の塗装で耐水蒸気性・耐食性に優れた十分な厚みのある塗膜を形成できるため、優れたワンコート塗料として利用することができる。 The water-based fluororesin coating composition of the present invention can firmly adhere to various metal substrates and form a sufficiently thick coating film with excellent water vapor resistance and corrosion resistance in a single application, making it an excellent one-on-one product. It can be used as a coat paint.
Claims (9)
An article having a coating film of the aqueous fluororesin coating composition according to any one of claims 1 to 6.
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| JP6953685B2 (en) | 2016-06-29 | 2021-10-27 | 昭和電工マテリアルズ株式会社 | Polyamide-imide resin composition and paint |
| JP7382813B2 (en) * | 2019-12-06 | 2023-11-17 | 三井・ケマーズ フロロプロダクツ株式会社 | Water-based fluororesin coating composition |
| JP2023087722A (en) * | 2021-12-14 | 2023-06-26 | 三井・ケマーズ フロロプロダクツ株式会社 | Fluororesin liquid coating composition |
-
2022
- 2022-07-08 JP JP2022110302A patent/JP2024008429A/en active Pending
-
2023
- 2023-07-06 WO PCT/US2023/026967 patent/WO2024010835A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024010835A1 (en) | 2024-01-11 |
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