JP6681459B1 - Pre-coated metal plate coating composition, pre-coated metal plate and method for producing the same - Google Patents
Pre-coated metal plate coating composition, pre-coated metal plate and method for producing the same Download PDFInfo
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- JP6681459B1 JP6681459B1 JP2018240130A JP2018240130A JP6681459B1 JP 6681459 B1 JP6681459 B1 JP 6681459B1 JP 2018240130 A JP2018240130 A JP 2018240130A JP 2018240130 A JP2018240130 A JP 2018240130A JP 6681459 B1 JP6681459 B1 JP 6681459B1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- FCDZZFLRLVQGEH-UHFFFAOYSA-N ethane-1,2-diol;prop-2-enoic acid Chemical compound OCCO.OC(=O)C=C FCDZZFLRLVQGEH-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
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- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000010935 stainless steel Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- 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
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/16—Homopolymers or copolymers of vinylidene fluoride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
【課題】特に、耐摩耗性、耐砂塵傷付き性及び耐候性を備える塗膜を形成できる、プレコート金属板用塗料組成物を提供すること。【解決手段】ポリフッ化ビニリデン樹脂（Ａ）と、アクリル樹脂（Ｂ）と、ポリテトラフルオロエチレン粒子（Ｃ）と、ワックス（Ｄ）と、骨材（Ｅ）と、溶剤（Ｆ）とを含み、前記アクリル樹脂（Ｂ）は、少なくとも１種の熱硬化性アクリル樹脂を含み、及び、前記溶剤（Ｆ）は、ケトン構造を有する溶剤（Ｆ−１）を含み、前記溶剤（Ｆ−１）は、沸点が１８０℃以上である、プレコート金属板用塗料組成物。【選択図】図１PROBLEM TO BE SOLVED: To provide a coating composition for a precoated metal plate, which can form a coating film having abrasion resistance, sand scratch resistance and weather resistance. A polyvinylidene fluoride resin (A), an acrylic resin (B), polytetrafluoroethylene particles (C), a wax (D), an aggregate (E), and a solvent (F) are included. The acrylic resin (B) contains at least one thermosetting acrylic resin, and the solvent (F) contains a solvent having a ketone structure (F-1), and the solvent (F-1). Is a coating composition for a precoated metal plate having a boiling point of 180 ° C. or higher. [Selection diagram] Figure 1
Description
本発明は、プレコート金属板用塗料組成物、前記塗料組成物から形成された塗膜を有するプレコート金属板及びその製造方法に関する。 TECHNICAL FIELD The present invention relates to a coating composition for a precoated metal plate, a precoated metal plate having a coating film formed from the coating composition, and a method for producing the same.
塗装金属板、例えば、プレコート鋼板（「ＰＣＭ」ともいう）は、シャッター、雨戸、ドア、屋根及びサイディング等の建築部材、クーラー室外機等の電気機器類の外装材、並びに内装材等の各種の部材として用いられている。
通常、プレコート鋼板は、鋼板の表面に塗装を施し、塗膜を形成させた後、要求される製品へと加工される。このため、プレコート鋼板に形成される塗膜は、柔軟性と、加工の際、例えば、プレコート鋼板を曲げた際に割れたり剥がれたりしない等、高い加工性が要求されている。その上、プレコート鋼板は、上記部材の外観を構成するため、優れた意匠性が求められている。
また、プレコート鋼板は、用途に応じて、耐摩耗性、耐傷付き性、耐食性、耐候性等の各種特性が求められている。
A coated metal plate, for example, a pre-coated steel plate (also referred to as “PCM”) is used for various kinds of building members such as shutters, shutters, doors, roofs and sidings, exterior materials for electric devices such as cooler outdoor units, and interior materials. It is used as a member.
Usually, a precoated steel sheet is processed into a required product after coating the surface of the steel sheet to form a coating film. Therefore, the coating film formed on the precoated steel sheet is required to have flexibility and high workability such that it does not crack or peel off when the precoated steel sheet is bent during processing. In addition, since the precoated steel sheet constitutes the appearance of the above member, excellent designability is required.
Further, the precoated steel sheet is required to have various properties such as wear resistance, scratch resistance, corrosion resistance, and weather resistance depending on the application.
特開平８−１８３９２８号公報（特許文献１）には、ポリエステル樹脂を主成分とし、アクリルポリマービーズ、四フッ化エチレン樹脂粉末及び炭化ケイ素を含む塗料組成物から形成される塗膜を有する塗装金属板が開示されている。
特開平１０−２７８１７０号公報（特許文献２）には、化成処理皮膜を形成した金属板の表面に下塗り塗膜を形成し、その上に球状ガラスビ−ズと樹脂粉末とを含む上塗り塗膜が形成された塗装金属板が開示されている。
特開２００９−２２１７１８号公報（特許文献３）には、塗装された金属板が、その両面に所定量のアクリル樹脂とポリテトラフルオロエチレン樹脂粉末を含む塗膜を有する、シャッタースラットが開示されている。
Japanese Patent Application Laid-Open No. 8-183928 (Patent Document 1) describes a coated metal having a polyester resin as a main component and a coating film formed from a coating composition containing acrylic polymer beads, tetrafluoroethylene resin powder and silicon carbide. A board is disclosed.
Japanese Unexamined Patent Publication No. 10-278170 (Patent Document 2) discloses an undercoating film formed on the surface of a metal plate on which a chemical conversion treatment film is formed, on which a topcoating film containing spherical glass beads and resin powder is provided. A formed coated metal plate is disclosed.
Japanese Unexamined Patent Publication No. 2009-221718 (Patent Document 3) discloses a shutter slat in which a coated metal plate has a coating film containing a predetermined amount of acrylic resin and polytetrafluoroethylene resin powder on both surfaces thereof. There is.
例えば、シャッター、雨戸、ドア、屋根及びサイディング等の建築部材等、屋外で用いるプレコート金属板には、優れた加工性及び意匠性に加えて、耐候性、耐食性等、耐傷付き性及び耐摩耗性等が要求されている。
その上、近年では、プレコート金属板を屋外で使用する場合、土壌及び粉塵等の比較的硬い物質がプレコート鋼板に付着し、それに起因する傷付きが問題となっている。このため、プレコート鋼板には、耐砂塵傷付き性と称する性質が要求されている。
また、これらの性能向上が求められる一方、塗料及び塗装コストを上昇させない塗料設計も求められている。
For example, in addition to excellent workability and designability, pre-coated metal sheets used outdoors, such as shutters, shutters, doors, roofs, and building members such as siding, have weatherability, corrosion resistance, scratch resistance, and abrasion resistance. Etc. are required.
Moreover, in recent years, when a precoated metal plate is used outdoors, relatively hard substances such as soil and dust adhere to the precoated steel plate, causing scratches resulting from the problem. For this reason, the precoated steel sheet is required to have a property referred to as resistance to sand scratches.
Further, while these performance improvements are required, there is also a demand for a paint design that does not increase paints and coating costs.
上記特許文献１及び２に記載される塗装金属板は、加工性、耐摩耗性及び耐候性が不十分であり、より高い性能が要求されている。
上記特許文献３に記載されるシャッタースラットは、耐傷付き性の向上を試みた発明である。しかし、耐傷付き性を向上させると、耐候性が不十分となってしまう問題を有している。また、耐砂塵傷付き性が不十分であり、砂塵等に起因する傷付きが生じやすい。その上、繰り返して使用すると塗膜の摩耗が進行するという問題を有している。
更に、特許文献３において、所望の性能を発揮させるためには、同一の塗膜を鋼板の両面に形成する必要があり、プレコート金属板のコストが上昇する問題を有している。
The coated metal plates described in
The shutter slat described in Patent Document 3 is an invention that attempts to improve scratch resistance. However, when the scratch resistance is improved, there is a problem that the weather resistance becomes insufficient. In addition, the scratch resistance to sand dust is insufficient, and scratches due to sand dust or the like are likely to occur. In addition, there is a problem that the abrasion of the coating film progresses when it is repeatedly used.
Further, in Patent Document 3, it is necessary to form the same coating film on both surfaces of the steel plate in order to exhibit desired performance, which causes a problem of increasing the cost of the precoated metal plate.
本発明は、上記問題を解決することを課題とし、より詳細には、優れた加工性及び意匠性に加えて、耐候性、耐食性等、耐傷付き性及び耐摩耗性を有する塗膜を形成できる、プレコート金属板用塗料組成物を提供することを課題とする。更に、耐砂塵傷付き性及び摺動性に優れた塗膜を形成できる、プレコート金属板用塗料組成物を提供することを課題とする。 The present invention aims to solve the above problems, and more specifically, in addition to excellent processability and designability, a coating film having weather resistance, corrosion resistance, scratch resistance and abrasion resistance can be formed. An object of the present invention is to provide a coating composition for a precoated metal plate. Further, it is an object of the present invention to provide a coating composition for a precoated metal plate, which can form a coating film having excellent resistance to sand scratches and slidability.
上記課題を解決するため、本発明は下記態様を提供する。
［１］ポリフッ化ビニリデン樹脂（Ａ）と、
アクリル樹脂（Ｂ）と、
ポリテトラフルオロエチレン粒子（Ｃ）と、
ワックス（Ｄ）と、
骨材（Ｅ）と、
溶剤（Ｆ）とを含み、
アクリル樹脂（Ｂ）は、少なくとも１種の熱硬化性アクリル樹脂を含み、及び、
溶剤（Ｆ）は、ケトン構造を有する溶剤（Ｆ−１）を含み、
上記溶剤（Ｆ−１）は、沸点が１８０℃以上である、
プレコート金属板用塗料組成物。
［２］ある態様において、本開示のプレコート金属板用塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、５４質量部以上８０質量部以下で含む。
［３］ある態様において、本開示のプレコート金属板用塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径は、３μｍ以上３０μｍ以下である。
［４］ある態様において、本開示のプレコート金属板用塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）は、焼成ポリテトラフルオロエチレン粒子である。
［５］ある態様において、本開示のプレコート金属板用塗料組成物は、ワックス（Ｄ）が、ポリエチレン、酸化ポリエチレン、ポリプロピレン、マイクロクリスタリン、酸化マイクロクリスタリン、脂肪酸アマイド、及びカルナバワックスからなる群から選択される少なくとも１種を含む。
［６］ある態様において、本開示のプレコート金属板用塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、１０質量部以上２５質量部以下で含み、並びにワックス（Ｄ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．５質量部以上５．０質量部以下含む。
［７］ある態様において、本開示のプレコート金属板用塗料組成物は、骨材（Ｅ）が、アクリル樹脂粒子、ガラスビーズ、アクリロニトリル樹脂粒子、尿素樹脂粒子、セラミック繊維及びシリカ粒子からなる群から選択される少なくとも１種を含む。
［８］ある態様において、本開示のプレコート金属板用塗料組成物は、溶剤（Ｆ）が、更に、ケトン構造を有する溶剤（Ｆ−２）を含み、溶剤（Ｆ−２）は、沸点が１８０℃未満である。
［９］ある態様において、本開示は、金属板の少なくとも一方の面に、上記プレコート金属板用塗料組成物から形成された塗膜を有する、プレコート金属板を提供する。
［１０］ある態様において、本開示のプレコート金属板は、上記プレコート金属板用塗料組成物から形成された塗膜の膜厚が１０μｍ以上２５μｍ以下である。
［１１］ある態様において、本開示のプレコート金属板は、金属板が、シャッタースラット材である。
［１２］ある態様において、本開示のプレコート金属板は、膜厚３μｍ以上１０μｍ以下の下塗り塗膜を有する。
［１３］ある態様において、本開示は、金属板の少なくとも一方の面に、上記プレコート金属板用塗料組成物を、硬化後の膜厚が１０μｍ以上２５μｍ以下となるよう塗装する工程、プレコート金属板用塗料組成物を、金属板の到達温度が２３０℃以上２７０℃以下であり、乾燥及び硬化時間が２０秒以上１２０秒以下の条件下で、乾燥及び硬化させる工程を含む、プレコート金属板の製造方法を提供する。
In order to solve the above problems, the present invention provides the following aspects.
[1] Polyvinylidene fluoride resin (A),
Acrylic resin (B),
Polytetrafluoroethylene particles (C),
Wax (D),
Aggregate (E),
Including a solvent (F),
The acrylic resin (B) contains at least one thermosetting acrylic resin, and
The solvent (F) includes a solvent (F-1) having a ketone structure,
The solvent (F-1) has a boiling point of 180 ° C. or higher,
Pre-coated metal plate coating composition.
[2] In one embodiment, the coating composition for a precoated metal plate of the present disclosure includes a polyvinylidene fluoride resin (A) as a total of a solid content of the polyvinylidene fluoride resin (A) and a solid content of the acrylic resin (B). It is contained in an amount of 54 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass.
[3] In one aspect, in the coating composition for a precoated metal plate of the present disclosure, the average particle size of the polytetrafluoroethylene particles (C) is 3 μm or more and 30 μm or less.
[4] In one embodiment, in the coating composition for a precoated metal plate of the present disclosure, the polytetrafluoroethylene particles (C) are calcined polytetrafluoroethylene particles.
[5] In one aspect, in the coating composition for a precoated metal plate of the present disclosure, the wax (D) is selected from the group consisting of polyethylene, polyethylene oxide, polypropylene, microcrystalline, oxidized microcrystalline, fatty acid amide, and carnauba wax. At least one of
[6] In one embodiment, the coating composition for a precoated metal plate of the present disclosure comprises polytetrafluoroethylene particles (C) in a solid content of polyvinylidene fluoride resin (A) and a solid content of acrylic resin (B). 100 parts by mass or more and 10 parts by mass or more and 25 parts by mass or less, and the wax (D) in total 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 0.5 parts by mass or more and 5.0 parts by mass or less in terms of solid content with respect to parts.
[7] In one aspect, in the coating composition for a precoated metal plate of the present disclosure, the aggregate (E) is selected from the group consisting of acrylic resin particles, glass beads, acrylonitrile resin particles, urea resin particles, ceramic fibers and silica particles. At least one selected is included.
[8] In one aspect, in the coating composition for a precoated metal plate of the present disclosure, the solvent (F) further contains a solvent (F-2) having a ketone structure, and the solvent (F-2) has a boiling point of It is less than 180 ° C.
[9] In one aspect, the present disclosure provides a precoated metal plate having a coating film formed from the above coating composition for a precoated metal plate on at least one surface of the metal plate.
[10] In one aspect, in the precoated metal sheet of the present disclosure, the film thickness of the coating film formed from the above coating composition for a precoated metal sheet is 10 μm or more and 25 μm or less.
[11] In one aspect, in the precoated metal plate of the present disclosure, the metal plate is a shutter slat material.
[12] In one embodiment, the precoated metal plate of the present disclosure has an undercoat coating film having a film thickness of 3 μm or more and 10 μm or less.
[13] In one aspect, the present disclosure provides a step of applying the coating composition for a precoated metal plate on at least one surface of the metal plate so that the film thickness after curing is 10 μm or more and 25 μm or less, the precoat metal plate. Of a pre-coated metal plate, which comprises a step of drying and curing the coating composition for a metal plate under the conditions that the ultimate temperature of the metal plate is 230 ° C. or higher and 270 ° C. or lower and the drying and curing time is 20 seconds or longer and 120 seconds or shorter. Provide a way.
本発明のプレコート金属板用塗料組成物は、優れた加工性及び意匠性に加えて、耐候性、耐食性、耐傷付き性及び耐摩耗性を有する塗膜を形成でき、更に、耐砂塵傷付き性及び摺動性を備える塗膜を形成できる。 The coating composition for a precoated metal plate of the present invention can form a coating film having weatherability, corrosion resistance, scratch resistance and abrasion resistance, in addition to excellent workability and designability, and further has a dust scratch resistance. Also, a coating film having slidability can be formed.
本発明に至った経緯を説明する。
プレコート金属板は、上述のように、シャッター、雨戸、ドア、屋根及びサイディング等の建築部材にも多用されている。建築部材のうち、例えば、ビル、住宅の出入口部等の開口部に設けられるシャッターは、プレコート金属板、例えば、プレコート鋼板、プレコートアルミ板から構成される複数のスラットと呼ばれる短冊状の部材を、各長辺部に形成される連結部を介して可動できるように、相互に連結した構造を有している。シャッターは、構造上、開閉時に、隣り合うスラット同士を連結している部材を軸にして折りたたまれ、隣り合うスラット同士の表面と裏面とが繰り返し摺動して擦り合わされる。そのため、シャッターを使用するうちに、繰り返しの摺動による摩耗によって、スラット表面に傷が発生し、及び／又は塗膜自体が摩耗（損耗）し、外観を損ねるだけでなく、錆の発生原因となったり、摺動性及び／又は静音性が悪化したり等の問題が生じている。
同様に、他の建築部材についても、繰り返しの摺動による摩耗と同様に、部材同士の接触により生る傷及び塗膜自体の損耗に起因する問題を有している。例えば、屋根材及び内外壁材等は、プレコート金属板製造時や成型された部材の輸送時に、部材同士の接触（擦り合せ）による傷、塗膜の損耗が生じ得る。また、屋根等は、部材が相互に重なるように配置されており、風雨等により、部材同士の接触面における傷、塗膜の損耗が生じ得る。
The background of the present invention will be described.
As described above, the precoated metal plate is also frequently used for building members such as shutters, shutters, doors, roofs and sidings. Among building members, for example, a shutter provided in an opening such as a building and a doorway of a house is a precoated metal plate, for example, a strip-shaped member called a plurality of slats composed of a precoated steel plate and a precoated aluminum plate, It has a mutually connected structure so that it can be moved through a connecting part formed on each long side. The shutter is structurally folded at the time of opening and closing with a member connecting adjacent slats as an axis, and the front surface and the back surface of the adjacent slats repeatedly slide and rub against each other. Therefore, while the shutter is used, abrasion due to repeated sliding causes scratches on the slat surface, and / or the coating film itself is abraded (damaged), which not only impairs the appearance but also causes rust. And the slidability and / or the quietness are deteriorated.
Similarly, other building members also have a problem due to scratches caused by contact between members and damage to the coating film itself, as well as wear due to repeated sliding. For example, roofing materials, inner and outer wall materials, and the like may have scratches due to contact (rubbing) between members and damage to the coating film at the time of manufacturing a precoated metal plate or transporting a molded member. In addition, the roof and the like are arranged so that the members overlap with each other, and scratches on the contact surface between the members and wear of the coating film may occur due to wind and rain.
更に、砂塵等に起因する傷付きを防止できる性質（耐砂塵傷付き性）が要求されている。例えば、砂塵に起因する傷は、比較的硬い粒状物である砂の噛み込みによる傷、風による砂埃の飛散等、衝撃に起因する傷、砂が付着した状態で部材同士が擦り合わされることにより発生する傷等を含むので、従来要求されてきた耐傷付き性よりも、更に高い傷付き防止性能を備える必要がある。
例えば、砂塵の飛来に起因する傷等、金属板、例えば、鋼板素地まで到達し得る傷の発生を抑制する塗膜物性が求められている。
Further, a property capable of preventing scratches due to dust etc. (sand dust scratch resistance) is required. For example, scratches caused by dust are scratches caused by biting of sand, which is a relatively hard granular material, scratches caused by impact such as scattering of dust by wind, etc. Since it includes scratches and the like that occur, it is necessary to have a higher scratch resistance than the conventionally required scratch resistance.
For example, there is a demand for coating film physical properties that suppress the occurrence of scratches that can reach a metal plate, for example, a steel plate substrate, such as scratches caused by flying dust.
このように、プレコート金属板用塗料組成物において、特定の理論に限定して理解すべきでは無いが、通常の使用により生じる傷、繰り返しの摺動による摩耗、及び砂塵等に起因する傷等、様々な条件で傷及び摩耗が生じ得る。これらは、一言で傷、摩耗等と称されているが、その発生のメカニズムは多岐に亘る。このため、本発明者等は、種々の傷と摩耗を低減、予防できる塗膜形成可能な塗料組成物の開発を試みた。 Thus, in the coating composition for a precoated metal plate, which should not be understood as limited to a particular theory, scratches caused by normal use, wear due to repeated sliding, and scratches caused by dust etc., Scratches and wear can occur under various conditions. These are called scratches, abrasions, etc. in a word, but the mechanisms of their occurrence are diverse. Therefore, the present inventors have tried to develop a coating composition capable of forming a coating film capable of reducing and preventing various scratches and abrasion.
プレコート金属板用塗料組成物で汎用されている、ポリエステル系樹脂にワックスを含む塗料組成物では、塗膜の摩耗性、摺動性向上のため、樹脂を硬く、かつ、ワックス含有量を高くする必要がある。しかし、この様な組成物において、ポリエステル系樹脂では、樹脂の硬度化に限界があり、また、ワックスを塗料組成物中に大量に配合すると、塗料組成物の貯蔵安定性等、安定性を低下させてしまうという問題がある。 A coating composition containing wax in a polyester resin, which is widely used in coating compositions for precoated metal plates, hardens the resin and increases the wax content in order to improve the abrasion resistance and slidability of the coating film. There is a need. However, in such a composition, the polyester resin has a limit in hardening the resin, and when a large amount of wax is mixed in the coating composition, the stability such as the storage stability of the coating composition is deteriorated. There is a problem of letting it go.
一方、ポリエステル系樹脂に代わり、ポリフッ化ビニリデン樹脂とアクリル樹脂とを含むマトリックス樹脂からなる塗料組成物も検討されている。しかし、既知の塗料組成物は、耐候性、耐摩耗性、更に砂塵付着時の耐傷付き性（耐砂塵傷付き性）が不十分である。
例えば、従来のプレコート金属板用塗料組成物の場合、耐傷付き性の向上を試みるために、ポリフッ化ビニリデン樹脂の添加量を少量に抑える必要がある。その結果、得られる塗膜の耐候性等の耐久性が悪くなる傾向がある。
また、耐摩耗性、耐傷付き性の向上を試みると、アクリル樹脂の配合量を多くする必要がある。しかし、アクリル樹脂の配合量が多くなると、得られる塗膜の耐候性が悪くなるといったトレードオフの問題を有している。
更に、近年においては、より長期にわたる耐久性も要求されているので、機械的物性を向上させるために耐候性を犠牲にすることは望ましくない。
On the other hand, a coating composition made of a matrix resin containing a polyvinylidene fluoride resin and an acrylic resin instead of the polyester resin is also under study. However, the known coating composition is insufficient in weather resistance, wear resistance, and scratch resistance at the time of dust adhesion (sand dust scratch resistance).
For example, in the case of the conventional coating composition for a precoated metal plate, it is necessary to suppress the addition amount of the polyvinylidene fluoride resin to a small amount in order to improve the scratch resistance. As a result, the durability of the resulting coating film such as weather resistance tends to deteriorate.
In addition, when trying to improve wear resistance and scratch resistance, it is necessary to increase the amount of the acrylic resin compounded. However, when the amount of the acrylic resin compounded is large, there is a trade-off problem that the weather resistance of the resulting coating film deteriorates.
Further, in recent years, longer-term durability is also required, and it is not desirable to sacrifice weather resistance in order to improve mechanical properties.
そこで、本発明者等は鋭意検討し、本発明を完成させた。
本発明は、所定の組成を有することで、塗料組成物は、アクリル樹脂含有量が比較的低く、ポリフッ化ビニリデン樹脂の添加量を比較的多く含むことも可能であり、耐摩耗性、特に繰り返し使用時の耐摩耗性及び摺動性を確保できる塗膜を形成できる。その上、良好な耐候性を有することができるので、トレードオフの関係にあった物性をバランスよく有することができる。
更に、本発明の塗料組成物であれば、従来から要求されている性能を良好に満たすだけで無く、近年注目されている耐砂塵傷付き性を向上させることができる。
Therefore, the inventors of the present invention have made earnest studies and completed the present invention.
The present invention, by having a predetermined composition, the coating composition has a relatively low acrylic resin content, it is also possible to include a relatively large amount of polyvinylidene fluoride resin added, abrasion resistance, especially repeated A coating film that can secure wear resistance and slidability during use can be formed. In addition, since it can have good weather resistance, it can have well-balanced physical properties in a trade-off relationship.
Further, the coating composition of the present invention can not only satisfactorily satisfy the performance that has been conventionally required, but also improve the resistance to sand scratches, which has been attracting attention in recent years.
本発明によると、上述した効果を含めて種々の効果を有する塗膜を形成できる。例えば、優れた加工性、優れた意匠性、耐候性、耐食性及び耐傷付き性等、プレコート金属板用塗料組成物に対して、従来から要求されている性能を満たすことができる。
その上、塗膜の摩耗防止（損耗防止）、繰返し摺動による塗膜の摩耗防止性等と関係する耐摩耗性を良好に有する。特に、本発明によると、繰り返し使用時の耐摩耗性に優れた塗膜を形成できるので、繰り返して摺動させる部材であっても、塗膜の摩耗、損耗による
塗膜外観の劣化、耐食性の低下等を抑制できる。
According to the present invention, a coating film having various effects including the above-mentioned effects can be formed. For example, it is possible to satisfy the performance conventionally required for a coating composition for a precoated metal plate, such as excellent processability, excellent designability, weather resistance, corrosion resistance and scratch resistance.
In addition, it has excellent wear resistance, which is related to the prevention of wear of the coating film (prevention of wear) and the wear resistance of the coating film due to repeated sliding. In particular, according to the present invention, it is possible to form a coating film having excellent wear resistance during repeated use, so even if it is a member that is repeatedly slid, abrasion of the coating film, deterioration of the coating film appearance due to wear, and corrosion resistance It is possible to suppress the deterioration.
また、従来、フッ素系樹脂を含む塗料組成物において、十分な効果を得ることができなかった耐砂塵傷付き性について、所定の組成を有する本発明は、優れた耐砂塵傷付き性を有する塗膜を形成できる。
このため、本発明は、比較的硬い粒状物である砂、小石等の噛み込みによる傷だけでなく、風による砂埃の飛散等、衝撃を伴う外的要因に起因し得る傷に対する耐性が向上した塗膜を形成できる。
Further, conventionally, in the coating composition containing a fluorine-based resin, the present invention having a predetermined composition, with respect to the dust scratch resistance which could not obtain a sufficient effect, is a coating having excellent dust scratch resistance. A film can be formed.
Therefore, the present invention has improved resistance to not only scratches caused by sand, pebbles, etc., which are relatively hard granular materials, but also scratches that may be caused by external factors accompanied by impact, such as scattering of dust due to wind. A coating film can be formed.
更に、本発明は、優れた摺動性を有する塗膜を形成できる。例えば、部材同士の抵抗が少なく、プレコート金属板に良好な滑り性をもたらすことができる。このため、例えば、金属板、例えば、鋼板がシャッタースラットである態様において、シャッター部材の良好な巻き取り性、静音性等をもたらすことができる。 Furthermore, the present invention can form a coating film having excellent slidability. For example, the resistance between the members is small, and the precoated metal plate can be provided with good slipperiness. Therefore, for example, in a mode in which a metal plate, for example, a steel plate is a shutter slat, it is possible to provide good winding property and quietness of the shutter member.
また、塗膜の耐傷付き性が大幅に向上した結果、金属板、例えば、鋼板の表面のみに本発明に係る塗料組成物を塗装し、裏面には、より安価な金属板用塗料組成物を塗装できるので、プレコート金属板のコスト上昇を抑制できる。
以下、本発明の塗料組成物について説明する。
Further, as a result that the scratch resistance of the coating film is significantly improved, a metal plate, for example, the coating composition according to the present invention is applied only to the front surface of the steel plate, the back surface, a cheaper coating composition for metal plate. Since it can be painted, the cost increase of the precoated metal plate can be suppressed.
The coating composition of the present invention will be described below.
本開示に係るプレコート金属板用塗料組成物は、
ポリフッ化ビニリデン樹脂（Ａ）と、
アクリル樹脂（Ｂ）と、
ポリテトラフルオロエチレン粒子（Ｃ）と、
ワックス（Ｄ）と、
骨材（Ｅ）と、
溶剤（Ｆ）とを含み、
前記アクリル樹脂（Ｂ）は、少なくとも１種の熱硬化性アクリル樹脂を含み、及び、
前記溶剤（Ｆ）は、ケトン構造を有する溶剤（Ｆ−１）を含み、
前記溶剤（Ｆ−１）は、沸点が１８０℃以上である、
プレコート金属板用塗料組成物である。
The coating composition for a precoated metal plate according to the present disclosure,
Polyvinylidene fluoride resin (A),
Acrylic resin (B),
Polytetrafluoroethylene particles (C),
Wax (D),
Aggregate (E),
Including a solvent (F),
The acrylic resin (B) contains at least one thermosetting acrylic resin, and
The solvent (F) includes a solvent having a ketone structure (F-1),
The solvent (F-1) has a boiling point of 180 ° C. or higher,
It is a coating composition for a precoated metal plate.
本開示の塗料組成物は、塗膜形成樹脂として、ポリフッ化ビニリデン樹脂（Ａ）と、
アクリル樹脂（Ｂ）とを含む。本開示の塗料組成物であれば、上記塗膜形成樹脂を含むことにより、繰り返し摩耗性及び耐砂塵傷付き性の低下を抑制しながら、耐候性の向上をもたらすことができる。
The coating composition of the present disclosure comprises a polyvinylidene fluoride resin (A) as a coating film forming resin,
Acrylic resin (B) is included. With the coating composition of the present disclosure, by including the above-mentioned coating film-forming resin, it is possible to improve weather resistance while suppressing deterioration of repeated abrasion resistance and sand scratch resistance.
ポリフッ化ビニリデン樹脂（Ａ）
ポリフッ化ビニリデン樹脂（Ａ）は、フッ化ビニリデンの単独重合体、又は主成分であるフッ化ビニリデンと他のモノマーとの共重合体であってよい。ポリフッ化ビニリデン樹脂（Ａ）を含むことで、得られる塗膜に耐候性を付与できる。更に、本発明の塗料組成物であれば、ポリフッ化ビニリデン樹脂（Ａ）を用いることにより、特に、繰り返し摩耗性及び耐砂塵傷付き性の低下を抑制しながら、耐候性の向上をもたらすことができる。
Polyvinylidene fluoride resin (A)
The polyvinylidene fluoride resin (A) may be a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride as a main component and another monomer. By including the polyvinylidene fluoride resin (A), weather resistance can be imparted to the obtained coating film. Furthermore, in the case of the coating composition of the present invention, by using the polyvinylidene fluoride resin (A), it is possible to bring about an improvement in weather resistance while suppressing a decrease in repeated abrasion resistance and dust scratch resistance. it can.
ポリフッ化ビニリデン樹脂（Ａ）は、例えば、高温高圧下でラジカル重合開始剤等を用いた重合により得ることができる。前記他のモノマーは、エチレン性炭素−炭素二重結合を有するモノマーであれば特に限定されない。他のモノマーがフッ素原子を含有していると、共重合体の耐候性がより向上する。このため、他のモノマーとしては、ヘキサフルオロプロピレン、テトラフルオロエチレン等のフッ素含有モノマーが好ましい。 The polyvinylidene fluoride resin (A) can be obtained, for example, by polymerization using a radical polymerization initiator or the like under high temperature and high pressure. The other monomer is not particularly limited as long as it is a monomer having an ethylenic carbon-carbon double bond. When the other monomer contains a fluorine atom, the weather resistance of the copolymer is further improved. Therefore, the other monomer is preferably a fluorine-containing monomer such as hexafluoropropylene or tetrafluoroethylene.
ポリフッ化ビニリデン樹脂（Ａ）は、カルボキシル基、スルホン酸基等の官能基が導入されていてもよい。ある態様において、本発明のポリフッ化ビニリデン樹脂は、フッ化ビニリデンの単独重合体である。フッ化ビニリデンの単独重合体であることにより、良好な耐候性と塗料組成物の安定性（例えば、貯蔵安定性）をバランスよく備え得る。 The polyvinylidene fluoride resin (A) may have a functional group such as a carboxyl group or a sulfonic acid group introduced therein. In some embodiments, the polyvinylidene fluoride resin of the present invention is a vinylidene fluoride homopolymer. By being a vinylidene fluoride homopolymer, good weather resistance and stability of the coating composition (for example, storage stability) can be provided in a well-balanced manner.
ポリフッ化ビニリデン樹脂（Ａ）は、例えば、重量平均分子量が１００，０００以上７００，０００以下、例えば、１５０，０００以上５００，０００以下、１５０，０００以上４００，０００以下である。
なお、本明細書中において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法による測定値をポリスチレン標準で換算した値である。
The polyvinylidene fluoride resin (A) has a weight average molecular weight of 100,000 or more and 700,000 or less, for example, 150,000 or more and 500,000 or less, or 150,000 or more and 400,000 or less.
In addition, in this specification, a weight average molecular weight is the value which converted the measured value by a gel permeation chromatography (GPC) method by the polystyrene standard.
ある態様において、ポリフッ化ビニリデン樹脂（Ａ）は、融点が１４０℃以上１９０℃以下であり、例えば、１５０℃以上１８０℃以下である。 In one embodiment, the polyvinylidene fluoride resin (A) has a melting point of 140 ° C or higher and 190 ° C or lower, for example, 150 ° C or higher and 180 ° C or lower.
ポリフッ化ビニリデン樹脂（Ａ）は、市販のものを使用してもよい。例えば、ＨＹＬＡＲ５０００（ソルベイ社製）、Ｋｙｎａｒ５００（カイナー５００）（アルケマ社製）等を例示できる。 As the polyvinylidene fluoride resin (A), a commercially available product may be used. For example, HYLAR5000 (manufactured by Solvay), Kynar500 (Kyner 500) (manufactured by Arkema) and the like can be exemplified.
ある態様において、ポリフッ化ビニリデン樹脂（Ａ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、５４質量部以上８０質量部以下で含む。
別の態様において、ポリフッ化ビニリデン樹脂（Ａ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、６０質量部超８０質量部以下で含み、例えば、６０質量部超７５質量部以下で含む。
ある態様において、ポリフッ化ビニリデン樹脂（Ａ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、６０．１質量部以上７５質量部以下で含み、例えば、６０．１質量部以上７２質量部以下で含む。
In one aspect, the polyvinylidene fluoride resin (A) is used in an amount of 54 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). Including.
In another embodiment, the polyvinylidene fluoride resin (A) is used in an amount of more than 60 parts by mass and 80 parts by mass with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). Included below, for example, more than 60 parts by weight and 75 parts by weight or less.
In one aspect, the polyvinylidene fluoride resin (A) is used in an amount of 60.1 parts by mass or more and 75 parts by mass or more with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). It is contained in an amount of 6 parts by mass or less, for example, 60.1 parts by mass or more and 72 parts by mass or less.
所定の組成を有する本発明の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）を上記関係で含むことにより、耐候性を十分に確保でき、更に、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び優れた摺動性を有する塗膜を形成できる。特に、従来は、困難であった、耐候性と耐傷付き性とを共に向上させることができる。
また、本発明に係る所定の溶剤を用いるので、ポリフッ化ビニリデン樹脂（Ａ）を良好に溶解させることができ、塗料組成物の貯蔵安定性を長期に亘り維持できる。
By including the polyvinylidene fluoride resin (A) in the above relationship, the coating composition of the present invention having a predetermined composition can sufficiently secure weather resistance, and further has scratch resistance, abrasion resistance, and dust scratch resistance. A coating film having excellent properties and excellent slidability can be formed. In particular, it is possible to improve both weather resistance and scratch resistance, which were difficult in the past.
Further, since the predetermined solvent according to the present invention is used, the polyvinylidene fluoride resin (A) can be satisfactorily dissolved, and the storage stability of the coating composition can be maintained for a long period of time.
アクリル樹脂（Ｂ）
本発明の塗料組成物は、アクリル樹脂（Ｂ）を含むことにより、塗膜の表面硬度を高めることができ、耐食性、耐傷付き性をより高めることができる。また、耐候性を大幅に低下させることなく、塗料組成物中に含み得る着色顔料の分散性を高め、意匠性の高い塗装金属板を製造することができる。
更に、本発明に係るアクリル樹脂（Ｂ）は、少なくとも１種の熱硬化性アクリル樹脂を含む。熱硬化性アクリル樹脂を含むことで、優れた加工性を維持しつつ、耐摩耗性、耐候性、耐水性、耐薬品性等を付与できる。また、経時による加工性の低下、及び加工時に発生する熱による加工性の低下を抑制することができる。
Acrylic resin (B)
When the coating composition of the present invention contains the acrylic resin (B), the surface hardness of the coating film can be increased, and the corrosion resistance and the scratch resistance can be further improved. Further, the dispersibility of the coloring pigment that can be contained in the coating composition can be enhanced without significantly reducing the weather resistance, and a coated metal plate with high designability can be manufactured.
Furthermore, the acrylic resin (B) according to the present invention contains at least one thermosetting acrylic resin. By containing the thermosetting acrylic resin, abrasion resistance, weather resistance, water resistance, chemical resistance and the like can be imparted while maintaining excellent workability. Further, it is possible to suppress deterioration of workability due to aging and deterioration of workability due to heat generated during processing.
ある態様において、本開示の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、アクリル樹脂（Ｂ）を、２０質量部以上４５質量部以下で含む。 In one embodiment, the coating composition of the present disclosure contains 20 parts by mass of the acrylic resin (B) based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). Included in the range of 45 parts by mass or more and 45 parts by mass or less.
ある態様において、本開示の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、アクリル樹脂（Ｂ）を、２０質量部以上４６質量部以下で含み、例えば、２０質量部以上４０質量部以下で含む。別の態様において、本開示の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、アクリル樹脂（Ｂ）を、２５質量部以上４０質量部以下で含み、例えば、２５質量部以上３９．９質量部以下で含む。別の態様において、２８質量部以上３９．９質量部以下で含む。 In one embodiment, the coating composition of the present disclosure contains 20 parts by mass of the acrylic resin (B) based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). It is contained in an amount of not less than 46 parts by mass and not more than 46 parts by mass, for example, not less than 20 parts by mass and not more than 40 parts by mass. In another embodiment, the coating composition according to the present disclosure includes 25 parts of the acrylic resin (B) based on 100 parts by mass of the total solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). It is contained in an amount of 40 parts by mass or more and 40 parts by mass or less, for example, 25 parts by mass or more and 39.9 parts by mass or less. In another embodiment, the content is 28 parts by mass or more and 39.9 parts by mass or less.
例えば、本開示に係るアクリル樹脂（Ｂ）が、熱硬化性アクリル樹脂から構成される場合、本開示の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、熱硬化性アクリル樹脂、すなわち、熱硬化性アクリル樹脂を、２０質量部以上４６質量部以下で含み得る。ある態様において、本開示の塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、熱硬化性アクリル樹脂を、２５質量部以上３９．９質量部以下で含み、例えば、２８質量部以上３９．９質量部以下含む。 For example, when the acrylic resin (B) according to the present disclosure is composed of a thermosetting acrylic resin, the coating composition of the present disclosure has a solid content of the polyvinylidene fluoride resin (A) and a solid content of the acrylic resin (B). The thermosetting acrylic resin, that is, the thermosetting acrylic resin may be contained in an amount of 20 parts by mass or more and 46 parts by mass or less based on 100 parts by mass in total. In one embodiment, the coating composition of the present disclosure comprises a thermosetting acrylic resin in an amount of 25 parts by mass based on 100 parts by mass of the total solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). It is contained in an amount of not less than 3 parts and not more than 39.9 parts by mass, for example, not less than 28 parts by mass and not more than 39.9 parts by mass.
ある態様において、アクリル樹脂（Ｂ）は、２種以上の熱硬化性アクリル樹脂を含んでもよい。２種以上の熱硬化性アクリル樹脂を含む態様において、本開示の塗料組成物は、熱硬化性アクリル樹脂の合計が、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、２０質量部以上４６質量部以下で含まれるよう、配合量を適宜調整できる。同様に、上記範囲内で、配合量を適宜調整できる。 In one aspect, the acrylic resin (B) may include two or more thermosetting acrylic resins. In an embodiment containing two or more thermosetting acrylic resins, in the coating composition of the present disclosure, the total of the thermosetting acrylic resins is the solid content of polyvinylidene fluoride resin (A) and the solid content of acrylic resin (B). With respect to 100 parts by mass in total, the compounding amount can be appropriately adjusted so that the content is 20 parts by mass or more and 46 parts by mass or less. Similarly, the blending amount can be appropriately adjusted within the above range.
ある態様において、アクリル樹脂（Ｂ）が２種以上のアクリル樹脂を含む態様において、少なくとも１種は熱硬化性アクリル樹脂であり、他は熱可塑性アクリル樹脂であってもよい。
アクリル樹脂（Ｂ）が熱硬化性アクリル樹脂と、熱可塑性アクリル樹脂とを含む場合、本開示の塗料組成物は、熱硬化性アクリル樹脂と熱可塑性アクリル樹脂のそれぞれの固形分の合計１００質量部に対して、熱硬化性アクリル樹脂が、２０質量部以上、好ましくは３０質量部以上となるように調整され得る。熱硬化性アクリル樹脂と熱可塑性アクリル樹脂の割合が上記範囲内であることで、上述した熱硬化性アクリル樹脂の利点に加えて、得られる塗膜の加工性を更に向上させる効果がある。
In one aspect, in the aspect in which the acrylic resin (B) contains two or more types of acrylic resins, at least one type may be a thermosetting acrylic resin and the other may be a thermoplastic acrylic resin.
When the acrylic resin (B) contains a thermosetting acrylic resin and a thermoplastic acrylic resin, the coating composition of the present disclosure has a total solid content of 100 parts by mass of each of the thermosetting acrylic resin and the thermoplastic acrylic resin. On the other hand, the thermosetting acrylic resin can be adjusted to be 20 parts by mass or more, preferably 30 parts by mass or more. When the ratio of the thermosetting acrylic resin and the thermoplastic acrylic resin is within the above range, in addition to the above-mentioned advantages of the thermosetting acrylic resin, there is an effect of further improving the processability of the obtained coating film.
ある態様において、アクリル樹脂（Ｂ）が２種以上のアクリル樹脂を含む場合、少なくとも１種は熱硬化性アクリル樹脂であり、他は熱可塑性アクリル樹脂である。熱硬化性のアクリル樹脂と、熱可塑性アクリル樹脂とを有することで、上述した、熱硬化性アクリル樹脂を含むことで奏される利点に加えて、加工性を良好にできる。更に、下塗り塗膜との密着性を良好にできる。その結果、プレコート金属板が既知の下塗り塗膜を有する態様であっても、本開示の塗料組成物は良好な密着性を有することができる。 In one aspect, when the acrylic resin (B) contains two or more acrylic resins, at least one is a thermosetting acrylic resin and the other is a thermoplastic acrylic resin. By having the thermosetting acrylic resin and the thermoplastic acrylic resin, in addition to the above-described advantages achieved by including the thermosetting acrylic resin, the workability can be improved. Further, the adhesion with the undercoat film can be improved. As a result, the coating composition of the present disclosure can have good adhesion even if the precoated metal plate has a known undercoat coating film.
本開示において、熱硬化性アクリル樹脂は、熱（例えば１４０℃以上）を加えることにより、重合・硬化反応が起こり得るアクリル系モノマーの共重合体を含む樹脂を意味する。ある態様において、熱硬化性アクリル樹脂は、１６０℃以上の温度、例えば２００℃以上の熱を加えることにより、重合・硬化反応が起こり得る。
また、選択する樹脂の構造応じて、架橋剤を用いてもよい。
なお、本開示に係る熱硬化性アクリル樹脂には、上記温度以上で、樹脂単独でゲル化が進行する樹脂も含まれる。
In the present disclosure, a thermosetting acrylic resin means a resin containing a copolymer of an acrylic monomer that can undergo a polymerization / curing reaction when heat (for example, 140 ° C. or higher) is applied. In one embodiment, the thermosetting acrylic resin can undergo a polymerization / curing reaction by applying a temperature of 160 ° C. or higher, for example, 200 ° C. or higher.
A cross-linking agent may be used depending on the structure of the resin selected.
In addition, the thermosetting acrylic resin according to the present disclosure also includes a resin in which gelation progresses by the resin alone at the above temperature or higher.
ある態様において、熱硬化性アクリル樹脂は、Ｎ−ヒドロキシアクリルアミド、Ｎ−アルコキシアクリルアミド、Ｎ−アルキロールアクリルアミド、ジアセトンアクリルアミド等のモノマー成分を共重合させた自己架橋型のアクリル樹脂であってもよく、ヒドロキシル基等の置換基を有するアクリル系モノマーと、メラミン等の架橋剤とを併用することにより架橋する硬化剤併用型のアクリル樹脂であってよい。 In one aspect, the thermosetting acrylic resin may be a self-crosslinking acrylic resin obtained by copolymerizing monomer components such as N-hydroxyacrylamide, N-alkoxyacrylamide, N-alkylolacrylamide, and diacetoneacrylamide. A curing agent-combined acrylic resin that crosslinks by using an acrylic monomer having a substituent such as a hydroxyl group and a crosslinking agent such as melamine together may be used.
一方、本開示において、熱可塑性アクリル樹脂は、熱硬化性アクリル樹脂以外のアクリル樹脂を意味する。通常、熱可塑性アクリル樹脂は、ガラス転移温度又は融点に達すると軟化する。 On the other hand, in the present disclosure, the thermoplastic acrylic resin means an acrylic resin other than the thermosetting acrylic resin. Generally, thermoplastic acrylic resins soften when they reach a glass transition temperature or melting point.
例えば、アクリル樹脂（Ｂ）は、上記モノマーの他に、水酸基含有モノマー（ｂ−１）及び他のモノマー（ｂ−２）を共重合することによって調製できる。
水酸基含有モノマー（ｂ−１）として、例えば、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸２，３−ジヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチル、これら水酸基含有の（メタ）アクリル酸エステルとε−カプロラクトンとの反応物及びポリエチレングリコールモノ（メタ）アクリレート等の多価アルコールと（メタ）アクリル酸とのエステル化物等が挙げられる。更に、上記多価アルコールと、（メタ）アクリル酸とのモノエステル化物にε−カプロラクトンを開環重合した反応物を用いることもできる。これらの水酸基含有モノマー（ｂ−１）は、１種を単独で用いてもよく、２種以上を併用してもよい。
なお、本明細書において、（メタ）アクリル酸は、アクリル酸又はメタクリル酸を意味する。
For example, the acrylic resin (B) can be prepared by copolymerizing a hydroxyl group-containing monomer (b-1) and another monomer (b-2) in addition to the above monomers.
Examples of the hydroxyl group-containing monomer (b-1) include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, and 4-hydroxy (meth) acrylate. Examples thereof include butyl, a reaction product of these hydroxyl group-containing (meth) acrylic acid ester with ε-caprolactone, and an esterified product of a polyhydric alcohol such as polyethylene glycol mono (meth) acrylate with (meth) acrylic acid. Further, a reaction product obtained by ring-opening polymerization of ε-caprolactone with a monoester product of the above polyhydric alcohol and (meth) acrylic acid can also be used. These hydroxyl group-containing monomers (b-1) may be used alone or in combination of two or more.
In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid.
他のモノマー（ｂ−２）として、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸等の、カルボキシル基含有モノマー及びマレイン酸エチル、マレイン酸ブチル、イタコン酸エチル、イタコン酸ブチル等のジカルボン酸モノエステルモノマー；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ、ｉ又はｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸アルキルエステルモノマー；（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸トリシクロデカニル、（メタ）アクリル酸アダマンチル等の脂環基含有モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ブチルアミノエチル等の（メタ）アクリル酸アミノアルキルエステルモノマー；アミノエチル（メタ）アクリルアミド、ジメチルアミノメチル（メタ）アクリルアミド、メチルアミノプロピル（メタ）アクリルアミド等のアミノアルキル（メタ）アクリルアミドモノマー；アクリルアミド、メタクリルアミド等のその他のＮ−置換（メタ）アクリルアミド系モノマー；（メタ）アクリロニトリル、α−クロルアクリロニトリル等のシアン化ビニル系モノマー；酢酸ビニル、プロピオン酸ビニル等の飽和脂肪族カルボン酸ビニルエステルモノマー；スチレン、α−メチルスチレン、ビニルトルエン等のスチレン系モノマー；ジビニルベンゼン、（メタ)アクリル酸エチレングリコール等の２官能モノマー等を挙げることができる。これらの他のモノマー（ｂ−２）は、１種を単独で用いてもよく、２種以上を併用してもよい。
上記他のモノマー（ｂ−２）のうち、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸シクロヘキシル等が好ましく用いられる。
As the other monomer (b-2), for example, a carboxyl group-containing monomer such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid and fumaric acid, and ethyl maleate, butyl maleate, ethyl itaconate, itacone Dicarboxylic acid monoester monomers such as butyl acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n, i or t-butyl (meth) acrylate, and (meth) acrylic acid 2 -(Meth) acrylic acid alkyl ester monomers such as ethylhexyl and lauryl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate And alicyclic group-containing monomers such as adamantyl (meth) acrylate An aminoalkyl ester monomer of (meth) acrylic acid such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate; aminoethyl (meth) acrylamide, dimethylaminomethyl (meth ) Aminoalkyl (meth) acrylamide monomers such as acrylamide and methylaminopropyl (meth) acrylamide; other N-substituted (meth) acrylamide monomers such as acrylamide and methacrylamide; and cyan such as (meth) acrylonitrile and α-chloroacrylonitrile. Vinyl monomer; saturated aliphatic carboxylic acid vinyl ester monomer such as vinyl acetate and vinyl propionate; styrene monomer such as styrene, α-methylstyrene and vinyltoluene; divinylbenzene (Meth) can be exemplified difunctional monomers such as acrylic acid ethylene glycol. These other monomers (b-2) may be used alone or in combination of two or more.
Among the above-mentioned other monomers (b-2), (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Cyclohexyl acrylate and the like are preferably used.
水酸基含有モノマー（ｂ−１）及び他のモノマー（ｂ−２）の重合方法として、当業者に通常用いられる方法を用いることができる。重合方法として、例えば、ラジカル重合開始剤を用いた、塊状重合法、溶液重合法、塊状重合後に懸濁重合を行う塊状−懸濁二段重合法等を用いることができる。これらの中でも、溶液重合法が特に好ましく用いることができる。溶液重合法として、例えば、上記モノマー混合物を、ラジカル重合開始剤の存在下で、例えば８０〜２００℃の温度で撹拌しながら加熱する方法等が挙げられる。 As a method for polymerizing the hydroxyl group-containing monomer (b-1) and the other monomer (b-2), a method usually used by those skilled in the art can be used. As the polymerization method, for example, a bulk polymerization method using a radical polymerization initiator, a solution polymerization method, a bulk-suspension two-step polymerization method in which suspension polymerization is performed after bulk polymerization, and the like can be used. Among these, the solution polymerization method can be particularly preferably used. Examples of the solution polymerization method include a method in which the monomer mixture is heated in the presence of a radical polymerization initiator at a temperature of 80 to 200 ° C. with stirring.
本開示の塗料組成物に含まれるアクリル樹脂（Ｂ）の数平均分子量は、３，０００〜１５０，０００であってよく、ある態様において、３，０００〜５０，０００であり、例えば３，５００〜３０，０００であり、別の態様において３，５００〜２０,０００である。アクリル樹脂（Ｂ）の数平均分子量が上記の範囲内にあることにより、良好な塗膜硬度と加工性を両立させることができ、更に、耐候性に優れた塗膜を形成できる。
また、アクリル樹脂（Ｂ）の数平均分子量が上記の範囲内にあることにより、塗料組成物は良好な乾燥性を有することができる。
なお、本明細書中において、数平均分子量は、ＧＰＣ（ゲル浸透クロマトグラフィー）によって測定したポリスチレン換算による値である。
なお、複数種のアクリル樹脂（Ｂ）を含む場合、本開示の塗料組成物に含まれるアクリル樹脂（Ｂ）の数平均分子量は、これらの混合物の数平均分子量を示す。
The acrylic resin (B) contained in the coating composition of the present disclosure may have a number average molecular weight of 3,000 to 150,000, and in one embodiment, 3,000 to 50,000, for example 3,500. ˜30,000, and in another embodiment, 3,500˜20,000. When the number average molecular weight of the acrylic resin (B) is within the above range, good coating film hardness and processability can both be achieved, and a coating film having excellent weather resistance can be formed.
When the number average molecular weight of the acrylic resin (B) is within the above range, the coating composition can have good drying properties.
In the present specification, the number average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography).
When a plurality of types of acrylic resins (B) are included, the number average molecular weight of the acrylic resin (B) contained in the coating composition of the present disclosure indicates the number average molecular weight of these mixtures.
アクリル樹脂（Ｂ）は、例えば、固形分水酸基価は０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下であり、ある態様においては０ｍｇＫＯＨ／ｇ以上１００ｍｇＫＯＨ／ｇ以下であり、例えば、０ｍｇＫＯＨ／ｇ以上７０ｍｇＫＯＨ／ｇ以下である。
固形分水酸基価が上記の範囲内にあることにより、熱硬化性アクリル樹脂としての良好な反応性、及び着色顔料の良好な分散性、下塗り塗膜との良好な付着性を確保することができる。
なお、本明細書中において、樹脂の水酸基価は、固形分換算での値を示し、ＪＩＳ Ｋ ００７０に準拠した方法により測定された値である。
また、複数種のアクリル樹脂を含む場合、固形分水酸基価は、アクリル樹脂の固形分水酸基価が上記範囲に含まれることが好ましい。別の態様において、各アクリル樹脂の水酸基価の平均値が上記範囲に含まれ得る。
The acrylic resin (B) has, for example, a solid content hydroxyl value of 0 mgKOH / g or more and 250 mgKOH / g or less, and in one aspect, 0 mgKOH / g or more and 100 mgKOH / g or less, for example, 0 mgKOH / g or more and 70 mgKOH / g or less. Is.
When the solid content hydroxyl value is within the above range, good reactivity as a thermosetting acrylic resin, good dispersibility of a color pigment, and good adhesion to an undercoat film can be secured. .
In addition, in this specification, the hydroxyl value of a resin shows the value in terms of solid content, and is the value measured by the method based on JIS K0070.
Further, when a plurality of types of acrylic resins are contained, the solid content hydroxyl value is preferably within the above range of the solid content hydroxyl value of the acrylic resin. In another aspect, the average value of the hydroxyl value of each acrylic resin may be included in the above range.
ある態様において、アクリル樹脂（Ｂ）のガラス転移温度（ＴｇＢ）は１０℃以上１２０℃以下、例えば、２０℃以上８０℃以下である。このような範囲にガラス転移温度を有することにより、塗膜の硬度、耐擦り傷性、耐水性、耐薬品性、耐食性を確保しつつ、優れた加工性を付与することができる。また、塗膜を良好に乾燥させることができる。
なお、本明細書において、ガラス転移温度は、示差熱走査熱量計によって測定した値であり、例えば、示差走査熱量計ＤＳＣ−６１００（セイコーインスツルメンツ社製）等により測定できる。
In one embodiment, the acrylic resin (B) has a glass transition temperature (Tg B ) of 10 ° C. or higher and 120 ° C. or lower, for example, 20 ° C. or higher and 80 ° C. or lower. By having the glass transition temperature in such a range, excellent workability can be imparted while ensuring hardness, scratch resistance, water resistance, chemical resistance, and corrosion resistance of the coating film. Further, the coating film can be dried well.
In this specification, the glass transition temperature is a value measured by a differential scanning calorimeter, and can be measured by, for example, a differential scanning calorimeter DSC-6100 (manufactured by Seiko Instruments Inc.).
アクリル樹脂（Ｂ）として、市販されるアクリル樹脂を用いてもよい。このようなアクリル樹脂の具体例として、アクリディックシリーズ（ＤＩＣ社製）、ダイヤナールシリーズ（三菱ケミカル社製）、ヒタロイドシリーズ（日立化成工業社製）、ＰＡＲＡＬＯＩＤシリーズ（ダウ・ケミカル社製）等が挙げられる。これらを単独で用いてもよく、２種以上を混合してもよい。 A commercially available acrylic resin may be used as the acrylic resin (B). Specific examples of such acrylic resin include Acridic series (manufactured by DIC), Dinal series (manufactured by Mitsubishi Chemical Co., Ltd.), Hitaroid series (manufactured by Hitachi Chemical Co., Ltd.), PARALOID series (manufactured by Dow Chemical Co., Ltd.), etc. Is mentioned. These may be used alone or in combination of two or more.
ポリテトラフルオロエチレン粒子（Ｃ）
本発明の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）を含む。塗料組成物がポリテトラフルオロエチレン粒子（Ｃ）を含むことにより、良好な耐摩耗性及び摺動性を有する塗膜を形成できる。また、本開示に係るポリフッ化ビニリデン樹脂（Ａ）とアクリル樹脂（Ｂ）と、ポリテトラフルオロエチレン粒子（Ｃ）とを組合せることで、高い表面硬度を有し、良好な耐摩耗性、特に繰り返し使用時の耐摩耗性及び摺動性（例えば、潤滑性)を確保できる。
Polytetrafluoroethylene particles (C)
The coating composition of the present invention contains polytetrafluoroethylene particles (C). When the coating composition contains the polytetrafluoroethylene particles (C), a coating film having good wear resistance and slidability can be formed. Further, by combining the polyvinylidene fluoride resin (A), the acrylic resin (B), and the polytetrafluoroethylene particles (C) according to the present disclosure, a high surface hardness is obtained, and good wear resistance, particularly Wear resistance and slidability (for example, lubricity) during repeated use can be secured.
ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径は、３μｍ以上３０μｍ以下であり、８μｍ以上３０μｍ以下であってよく、例えば、１０μｍ以上２５μｍ以下である。別の態様において、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径は、１２μｍ以上２４μｍ以下である。
なお、本明細書中において、平均粒子径は、粒子の体積平均粒子径を意味し、例えば、レーザ回折式粒子径分布測定装置ＳＡＬＤ−２２００（島津製作所社製）等を用いて測定することができる。
In one aspect, the average particle size of the polytetrafluoroethylene particles (C) is 3 μm or more and 30 μm or less, and may be 8 μm or more and 30 μm or less, for example, 10 μm or more and 25 μm or less. In another aspect, the average particle size of the polytetrafluoroethylene particles (C) is 12 μm or more and 24 μm or less.
In addition, in this specification, an average particle diameter means the volume average particle diameter of a particle, for example, it can measure using a laser diffraction type particle size distribution measuring device SALD-2200 (made by Shimadzu Corporation) etc. it can.
ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径がこのような関係を有することにより、塗膜の摩耗防止（損耗防止）、繰返し摺動による塗膜の摩耗防止性を良好に有することができ、耐摩耗性を良好に有することができる。特に、繰り返し使用時の耐摩耗性に優れた塗膜を形成できるので、繰り返して摺動させる部材であっても、塗膜の摩耗、損耗による塗膜外観の劣化、耐食性の低下等を抑制できる。更に、従来、フッ素系樹脂を含む塗料組成物において、十分な効果を得ることができなかった耐砂塵傷付き性についても、所定の組成を有する本発明は、優れた耐砂塵傷付き性を有する塗膜を形成できる。 When the average particle diameter of the polytetrafluoroethylene particles (C) has such a relationship, it is possible to favorably prevent abrasion of the coating film (prevention of wear) and abrasion resistance of the coating film due to repeated sliding, It can have good wear resistance. In particular, since a coating film having excellent wear resistance during repeated use can be formed, wear of the coating film, deterioration of the coating film appearance due to wear, deterioration of corrosion resistance, etc. can be suppressed even for members that are repeatedly slid. . Furthermore, in the conventional coating composition containing a fluorine-based resin, the present invention having a predetermined composition also has excellent dust scratch resistance even with respect to the dust scratch resistance which was not able to obtain a sufficient effect. A coating film can be formed.
ポリテトラフルオロエチレン粒子（Ｃ）は、四フッ化エチレンの単独重合体、及び主成分であるは四フッ化エチレンと他のモノマーとの共重合体から選択される少なくとも１種を含む粒子である。また、粒子全体の主成分が、四フッ化エチレン又はその誘導体である粒子である。前記他のモノマーは、エチレン性炭素二重結合を有するモノマーが好ましく、例えば、エチレン、パーフルオロ（アルキルビニルエーテル）、ヘキサフルオロプロピレン等が含まれる。
入手の容易性等から、ポリテトラフルオロエチレン粒子（Ｃ）は、四フッ化エチレンの単独重合体であることが好ましい。
The polytetrafluoroethylene particles (C) are particles containing at least one selected from a homopolymer of tetrafluoroethylene and a copolymer of ethylene tetrafluoride as a main component and another monomer. . In addition, the main component of the whole particles is particles of tetrafluoroethylene or its derivative. The other monomer is preferably a monomer having an ethylenic carbon double bond, and includes, for example, ethylene, perfluoro (alkyl vinyl ether), hexafluoropropylene and the like.
From the viewpoint of easy availability, the polytetrafluoroethylene particles (C) are preferably homopolymers of tetrafluoroethylene.
ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）の融点は、３００℃以上３５０℃以下であり、例えば３１０℃以上３３５℃以下である。なお、本明細書において、融点は、示差熱走査熱量計によって測定した値であり、例えば、ＤＳＣ−６１００（セイコーインスツルメンツ社製）等により測定できる。 In one embodiment, the melting point of the polytetrafluoroethylene particles (C) is 300 ° C or higher and 350 ° C or lower, for example, 310 ° C or higher and 335 ° C or lower. In the present specification, the melting point is a value measured by a differential scanning calorimeter, and can be measured by, for example, DSC-6100 (manufactured by Seiko Instruments Inc.).
ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）は、半焼成又は焼成ポリテトラフルオロエチレン粒子である。半焼成又は焼成したポリテトラフルオロエチレン粒子を用いることにより、形成される塗膜の耐傷付き性が更に向上する。また、耐砂塵傷付き性がより良好な塗膜を形成できる。好ましくは、焼成ポリテトラフルオロエチレン粒子である。焼成ポリテトラフルオロエチレン粒子は、より高い耐傷付き性及び耐砂塵傷付き性を有する塗膜を形成できる。 In one aspect, the polytetrafluoroethylene particles (C) are semi-calcined or calcined polytetrafluoroethylene particles. By using semi-baked or baked polytetrafluoroethylene particles, the scratch resistance of the coating film formed is further improved. Further, a coating film having a better resistance to sand scratches can be formed. Preferred are calcined polytetrafluoroethylene particles. The baked polytetrafluoroethylene particles can form a coating film having higher scratch resistance and dust scratch resistance.
ある態様において、本発明の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、９質量部以上２５質量部以下で含み、例えば、１２質量部以上２５質量部以下で含む。ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、１５質量部以上２４質量部以下で含み、例えば、１６質量部以上２３質量部以下で含む。
ポリテトラフルオロエチレン粒子（Ｃ）を上記範囲で含むことにより、塗膜の摩耗防止（損耗防止）、繰返し摺動による塗膜の摩耗防止性を良好に有し、耐摩耗性を良好に有する。特に、繰り返し使用時の耐摩耗性に優れた塗膜を形成できるので、繰り返して摺動させる部材であっても、塗膜の摩耗、損耗による塗膜外観の劣化、耐食性の低下等を抑制できる。
また、本発明の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）と、ワックス（Ｄ）とを共に含むことによって、得られる塗膜は優れた耐摩耗性、耐砂塵傷付き性等の効果を発揮できる。このため、塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）を上記範囲内で含むことにより、ワックス（Ｄ）との相乗効果を、更に良好に発揮できる。
In one embodiment, the coating composition of the present invention contains polytetrafluoroethylene particles (C) in a total amount of 100 parts by mass of a solid content of polyvinylidene fluoride resin (A) and a solid content of acrylic resin (B). , 9 parts by mass or more and 25 parts by mass or less, for example, 12 parts by mass or more and 25 parts by mass or less. In one aspect, the polytetrafluoroethylene particles (C) are used in an amount of 15 parts by mass or more and 24 parts by mass or more with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). Included below, for example, 16 parts by mass or more and 23 parts by mass or less.
By including the polytetrafluoroethylene particles (C) in the above range, the coating film is prevented from being worn (damage is prevented), the coating film is prevented from being worn by repeated sliding, and the wear resistance is also excellent. In particular, since a coating film having excellent wear resistance during repeated use can be formed, wear of the coating film, deterioration of the coating film appearance due to wear, deterioration of corrosion resistance, etc. can be suppressed even for members that are repeatedly slid. .
Further, the coating composition of the present invention contains both the polytetrafluoroethylene particles (C) and the wax (D), so that the resulting coating film has excellent wear resistance, dust scratch resistance, etc. Can be demonstrated. Therefore, the coating composition can more effectively exhibit the synergistic effect with the wax (D) by including the polytetrafluoroethylene particles (C) within the above range.
ポリテトラフルオロエチレン粒子（Ｃ）の市販品として、例えば、ホスタロンＴＦ９２０２（ヘキストジャパン社製、融点：３１５℃）、ホスタロンＴＦ９２０５（ヘキストジャパン社製、融点：３１５℃）、ＫＴＬシリーズ（喜多村製、融点：３１０〜３３５℃）等を挙げられる。これらを単独で使用してもよく、組合せて使用してもよい。 As commercially available products of polytetrafluoroethylene particles (C), for example, Hostalon TF9202 (Hoechst Japan, melting point: 315 ° C), Hostalon TF9205 (Hoechst Japan, melting point: 315 ° C), KTL series (Kitamura, melting point) : 310-335 ° C.) and the like. These may be used alone or in combination.
ワックス（Ｄ）
本開示の塗料組成物は、ワックス（Ｄ）を含む。本開示の塗料組成物は、上記ポリテトラフルオロエチレン粒子（Ｃ）とワックス（Ｄ）とを共に含むことによって、得られる塗膜は、優れた耐摩耗性、耐砂塵傷付き性、優れた摺動性等を効果的に発揮できる。更に、耐候性の低下を抑制できる。
Wax (D)
The coating composition of the present disclosure includes wax (D). When the coating composition of the present disclosure contains both the polytetrafluoroethylene particles (C) and the wax (D), the coating film obtained has excellent abrasion resistance, sand scratch resistance, and excellent sliding property. It is possible to effectively exhibit motility and the like. Further, it is possible to suppress deterioration of weather resistance.
ワックス（Ｄ）は、常温（約２３℃）で固体であり、例えば、融点は、３０℃以上２００℃以下であり、ある態様において、４０℃以上１６０℃以下であり、例えば、８０℃以上１５０℃以下である。
融点より１０℃高い温度に加熱した場合、比較的低粘度の液体又はペースト状になる有機物である。また、上記温度で加熱した場合、分解することなく溶融する有機物である。
特定の理論に限定して解釈すべきではないが、ワックス（Ｄ）は、焼き付け時に溶融して塗膜表面に浮き機能を発現する傾向が高いと考えられる。その結果、塗膜は優れた耐摩耗性を有し、更に、優れた意匠性を有することができる。
また、融点（軟化点）が上記の範囲に設計されることにより、塗料組成物中での安定性と、塗膜形成時の摺動性を両立させることができる。
The wax (D) is solid at room temperature (about 23 ° C.), for example, the melting point is 30 ° C. or higher and 200 ° C. or lower, and in one aspect, 40 ° C. or higher and 160 ° C. or lower, for example, 80 ° C. or higher and 150 ° C. or higher. It is below ℃.
When heated to a
Although it should not be interpreted as being limited to a particular theory, it is considered that the wax (D) has a high tendency to be melted during baking and exhibit a floating function on the coating film surface. As a result, the coating film has excellent wear resistance, and further has excellent designability.
Further, by designing the melting point (softening point) within the above range, both stability in the coating composition and slidability during coating film formation can be achieved.
ワックスは大きく分けると石油ワックス、動植物ワックス、合成ワックスに分類できる。更に、石油ワックスにはパラフィンワックス、マイクロクリスタリンワックス等の高級炭化水素があり、動植物ワックスにはカルナバワックス、キャンデリラワックス、木ろう、密ろう等の高級エステルがある。また、合成ワックスにはポリエチレンワックス、フィッシャー・トロプシュワックス等の高級炭化水素がある。 The wax can be roughly classified into petroleum wax, animal and vegetable wax, and synthetic wax. Further, petroleum waxes include higher hydrocarbons such as paraffin wax and microcrystalline wax, and animal and vegetable waxes include higher esters such as carnauba wax, candelilla wax, wood wax and beeswax. Further, synthetic waxes include higher hydrocarbons such as polyethylene wax and Fischer-Tropsch wax.
ある態様において、ワックス（Ｄ）は、ポリエチレン、酸化ポリエチレン、ポリプロピレン、マイクロクリスタリン、酸化マイクロクリスタリン、脂肪酸アマイド、及びカルナバワックスからなる群から選択される少なくとも１種を含む。
このようなワックス（Ｄ）を含むことにより、塗膜は優れた耐摩耗性、耐砂塵傷付き性等を有し、更に、優れた意匠性を有することができる。
In one embodiment, the wax (D) contains at least one selected from the group consisting of polyethylene, polyethylene oxide, polypropylene, microcrystalline, oxidized microcrystalline, fatty acid amide, and carnauba wax.
By including such a wax (D), the coating film can have excellent wear resistance, resistance to dust scratches, and the like, and further can have excellent designability.
ある態様において、ワックス（Ｄ）は、マイクロクリスタリンを含む。マイクロクリスタリンを含むことで、塗膜は、より優れた耐摩耗性、耐砂塵傷付き性及び優れた意匠性を有することができる。更に、滑り性が良好で、加工性により優れた塗膜を形成できる。 In one aspect, wax (D) comprises microcrystalline. By containing microcrystalline, the coating film can have more excellent abrasion resistance, dust scratch resistance, and excellent designability. Further, it is possible to form a coating film having good slipperiness and excellent workability.
ワックス（Ｄ）の平均粒子径は、５μｍ以上３０μｍ以下であり、５μｍ以上２５μｍ以下であってよく、例えば、５μｍ以上２４μｍ以下である。別の態様において、ワックス（Ｄ）の平均粒子径は、５μｍ以上２２μｍ以下である。ワックス（Ｄ）の平均粒子径がこのような範囲内であることにより、更に良好な外観を有し、優れた耐磨耗性及び耐砂塵傷付き性を有し、並びに塗料組成物の貯蔵安定性を良好にできる。 The average particle diameter of the wax (D) is 5 μm or more and 30 μm or less, and may be 5 μm or more and 25 μm or less, for example, 5 μm or more and 24 μm or less. In another embodiment, the wax (D) has an average particle size of 5 μm or more and 22 μm or less. When the average particle diameter of the wax (D) is within such a range, the wax (D) has a better appearance, excellent abrasion resistance and dust-scratch resistance, and storage stability of the coating composition. It is possible to improve the property.
上述のように、本開示の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）とワックス（Ｄ）とを共に含むことによって本開示の塗料組成物が有する効果を発揮できる。ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径と、ワックス（Ｄ）の平均粒子径は略同一範囲である。
別の態様においては、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径＞ワックス（Ｄ）の平均粒子径の関係を有する。ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径が、ワックス（Ｄ）の平均粒子径よりも大きいことで、より優れた耐磨耗性及び耐砂塵傷付き性を有する塗膜を形成できる。
As described above, the coating composition of the present disclosure can exhibit the effect of the coating composition of the present disclosure by including both the polytetrafluoroethylene particles (C) and the wax (D). In one aspect, the average particle size of the polytetrafluoroethylene particles (C) and the average particle size of the wax (D) are substantially in the same range.
In another aspect, there is a relationship of average particle diameter of polytetrafluoroethylene particles (C)> average particle diameter of wax (D). When the average particle diameter of the polytetrafluoroethylene particles (C) is larger than the average particle diameter of the wax (D), a coating film having more excellent abrasion resistance and dust scratch resistance can be formed.
ワックス（Ｄ）は、塗料組成物中での分散性を向上させるために、更に既知の溶剤を含んでもよい。ただし、本開示の塗料組成物の効果を損なわない範囲で選択され、特に、溶剤（Ｆ）の物性を損なわない範囲で選択される。 The wax (D) may further contain a known solvent in order to improve dispersibility in the coating composition. However, it is selected in a range that does not impair the effects of the coating composition of the present disclosure, and particularly in a range that does not impair the physical properties of the solvent (F).
ワックス（Ｄ）は、市販品を用いてもよい。例えば、融点が３０℃以上２００℃以下である市販品を用いることが好ましい。
市販品は、例えば、ポリエチレンワックスとして、スリップエイド（サンノプコ社製、融点：１４０℃）、ハイディスパーＴ−１６Ｐ−２Ｈ（岐阜セラック製造所社製、融点：１１０℃）、ハイディスパーＸ−１５Ｐ−２（岐阜セラック製造所社製、融点：１２０℃）、ハイディスパーＴ−１３Ｐ−５（岐阜セラック製造所社製、融点１２０℃）等が挙げられる。
As the wax (D), a commercially available product may be used. For example, it is preferable to use a commercially available product having a melting point of 30 ° C. or higher and 200 ° C. or lower.
Commercially available products include, for example, polyethylene wax as slip-aid (manufactured by San Nopco, melting point: 140 ° C.), High Disper T-16P-2H (manufactured by Gifu Shellac Manufacturing, melting point: 110 ° C.), High Disper X-15P-. 2 (manufactured by Gifu Shellac Mfg. Co., melting point: 120 ° C.), High Disper T-13P-5 (manufactured by Gifu Shellac Mfg. Co., melting point 120 ° C.) and the like.
酸化型ポリエチレンワックスの市販品として、例えば、デスパロン５１０−１０Ｘ（楠本化成工業社製、融点：１３０℃）、ハイディスパー２３５２（岐阜セラック製造所社製、融点：１３０℃）、ハイディスパー１４５９（岐阜セラック製造所社製、融点：１００℃）等が挙げられる。 Examples of commercially available oxidized polyethylene waxes include Desparon 510-10X (Kusumoto Kasei Kogyo KK, melting point: 130 ° C.), High Disper 2352 (Gifu Shellac Mfg., Melting point: 130 ° C.), High Disper 1459 (Gifu). Shellac Mfg. Co., melting point: 100 ° C.) and the like.
マイクロクリスタリンの市販品としては、ＳＲ−１６（興洋化学社製、マイクロクリスタリンワックス）、ハイディスパー １２５０（岐阜セラック製造所社製、マイクロクリスタリンワックス）、トプコＳ９２３（東洋ペトロライト社製、マイクロクリスタリンワックス）等が挙げられる。 Commercially available products of microcrystalline are SR-16 (manufactured by Koyo Chemical Co., Ltd., microcrystalline wax), High Disper 1250 (manufactured by Gifu Shellac Manufacturing Co., microcrystalline wax), Topco S923 (manufactured by Toyo Petrolite, microcrystalline). Wax) and the like.
ある態様において、ワックス（Ｄ）を、前記ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．５質量部以上５．０質量部以下含み、例えば、固形分で０．７質量部以上４．５質量部以下含む。
別の態様において、ワックス（Ｄ）を、固形分で０．８質量部以上４．０質量部以下含む。
本開示の塗料組成物は、このような関係でワックス（Ｄ）を含むことにより、得られる塗膜は、より優れた耐摩耗性、耐砂塵傷付き性及び優れた意匠性を有することができる。更に、滑り性が良好で、加工性により優れた塗膜を形成できる。
In one embodiment, the wax (D) is contained in a solid content of 0.5 parts by mass or more and 5 parts by mass or more with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 0.0 mass part or less, for example, 0.7 mass part or more and 4.5 mass part or less by solid content.
In another embodiment, the wax (D) is contained in a solid content of 0.8 parts by mass or more and 4.0 parts by mass or less.
When the coating composition of the present disclosure contains the wax (D) in such a relationship, the resulting coating film can have more excellent abrasion resistance, sand scratch resistance and excellent designability. . Further, it is possible to form a coating film having good slipperiness and excellent workability.
上述のように、本開示の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）とワックス（Ｄ）とを共に含むことによって本開示の塗料組成物が有する効果を発揮できる。
ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、１０質量部以上２５質量部以下で含み、並びに
ワックス（Ｄ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．５質量部以上５．０質量部以下含む。 このような関係を有することで、より優れた耐磨耗性及び耐砂塵傷付き性を有する塗膜を形成できる。
なお、本開示の塗料組成物は、ポリテトラフルオロエチレン粒子（Ｃ）とワックス（Ｄ）とを、本明細書に記載の数値範囲内であれば、任意の量で配合できる。
As described above, the coating composition of the present disclosure can exhibit the effect of the coating composition of the present disclosure by including both the polytetrafluoroethylene particles (C) and the wax (D).
In one aspect, the polytetrafluoroethylene particles (C) are used in an amount of 10 parts by mass or more and 25 parts by mass with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 0.5 parts by mass or more in terms of solid content relative to 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B), including the wax (D) below. Includes up to 0.0 parts by mass. By having such a relationship, a coating film having more excellent abrasion resistance and dust scratch resistance can be formed.
In addition, the coating composition of the present disclosure can be blended with the polytetrafluoroethylene particles (C) and the wax (D) in any amount within the numerical range described in the present specification.
別の態様において、ポリテトラフルオロエチレン粒子（Ｃ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、１６質量部以上２４質量部以下で含み、並びにワックス（Ｄ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．８質量部以上４．５質量部以下含む。 In another embodiment, the polytetrafluoroethylene particles (C) are used in an amount of 16 parts by mass or more and 24 parts by mass or more with respect to 100 parts by mass of the total solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). The amount of the wax (D) is 0.8 parts by mass or more based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). Includes 4.5 parts by mass or less.
骨材（Ｅ）
本開示の塗料組成物は、骨材（Ｅ）を含む。塗料組成物は、骨材（Ｅ）を含むことにより、耐傷付き性、耐砂塵傷付き性に優れた塗膜を形成できる。
更に、本開示の塗料組成物は、所定のポリテトラフルオロエチレン粒子（Ｃ）、ワックス（Ｄ）及び骨材（Ｅ）を併用し、所定の溶剤（Ｆ）を含むことにより、塗料組成物は、ポリフッ化ビニリデン樹脂（Ａ）を、アクリル樹脂（Ｂ）よりも多く含むことができる。
特定の理論に限定して解釈すべきではないが、本開示の塗料組成物は所定の配合を有することにより、特に、繰り返し摩耗性及び耐砂塵傷付き性の低下を抑制し、良好な摺動性を確保しながら、更に、耐候性の向上をもたらすことができる。また、良好な耐候性を長期間保持できる。
Aggregate (E)
The coating composition of the present disclosure includes an aggregate (E). By including the aggregate (E), the coating composition can form a coating film having excellent scratch resistance and sand dust scratch resistance.
Furthermore, the coating composition of the present disclosure contains the predetermined polytetrafluoroethylene particles (C), the wax (D) and the aggregate (E) in combination, and contains the predetermined solvent (F). The polyvinylidene fluoride resin (A) can be contained more than the acrylic resin (B).
Although it should not be construed as being limited to a particular theory, the coating composition of the present disclosure has a predetermined composition, and thus, in particular, suppresses deterioration of repetitive wear resistance and dust scratch resistance and provides good sliding. It is possible to further improve the weather resistance while securing the property. In addition, good weather resistance can be maintained for a long time.
ある態様において、骨材（Ｅ）は、アクリル樹脂粒子、ガラスビーズ、アクリロニトリル樹脂粒子、尿素樹脂粒子、セラミック繊維及びシリカ粒子からなる群から選択される少なくとも１種を含む。骨材（Ｅ）は、このような粒子等を含むことで、より良好な耐傷付き性、耐砂塵傷付き性に優れた塗膜を形成できる。
ある態様において、骨材（Ｅ）はアクリル樹脂粒子及び／又はシリカ粒子を含む。骨材（Ｅ）は、アクリル樹脂粒子を含むことにより、塗膜形成樹脂であるアクリル樹脂（Ｂ）等との相溶性がよく、また、シリカ粒子を含むことにより、塗膜の硬度が向上し、耐傷付き性、耐砂塵傷付き性がより向上した塗膜を形成できる。
In one aspect, the aggregate (E) includes at least one selected from the group consisting of acrylic resin particles, glass beads, acrylonitrile resin particles, urea resin particles, ceramic fibers, and silica particles. Since the aggregate (E) contains such particles, it is possible to form a coating film having excellent scratch resistance and dust scratch resistance.
In one embodiment, the aggregate (E) contains acrylic resin particles and / or silica particles. The aggregate (E) has good compatibility with the acrylic resin (B), which is a coating film forming resin, by containing the acrylic resin particles, and the hardness of the coating film is improved by containing the silica particles. It is possible to form a coating film with further improved scratch resistance and sand dust scratch resistance.
骨材（Ｅ）の平均粒子径は、７μｍ以上３０μｍ以下であり、８μｍ以上２５μｍ以下であってよく、例えば、８μｍ以上２２μｍ以下である。平均粒子径が上記範囲に設計されることにより、優れた耐傷付き性、耐砂塵傷付き性と塗料の安定性・塗装作業性を両立することができる。 The aggregate (E) has an average particle size of 7 μm or more and 30 μm or less, and may be 8 μm or more and 25 μm or less, for example, 8 μm or more and 22 μm or less. By designing the average particle diameter in the above range, it is possible to achieve both excellent scratch resistance, dust scratch resistance, and paint stability / painting workability.
ある態様において、ポリテトラフルオロエチレン粒子（Ｃ）の平均粒子径と、ワックス（Ｄ）の平均粒子径と、骨材（Ｅ）の平均粒子径との関係は、次の関係を有する。
（Ｃ）＞（Ｅ）≧（Ｄ）
このような関係を有することにより、特に、繰り返し摩耗性及び耐砂塵傷付き性の低下を抑制し、良好な摺動性と優れた意匠性、塗料組成物の貯蔵安定性を確保することができる。
In one aspect, the relationship between the average particle size of the polytetrafluoroethylene particles (C), the average particle size of the wax (D), and the average particle size of the aggregate (E) has the following relationship.
(C)> (E) ≧ (D)
By having such a relationship, in particular, it is possible to suppress deterioration of repetitive wear resistance and scratch resistance, and ensure good slidability, excellent designability, and storage stability of the coating composition. .
ある態様において、骨材（Ｅ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．１質量部以上１０．０質量部以下含み、例えば、固形分で０．５質量部以上８質量部以下含む。別の態様において、骨材（Ｅ）を、ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で１．０質量部以上８質量部以下含み、例えば、１．５質量部以上８質量部以下含む。
骨材（Ｅ）を、このような量で含むことにより、繰り返し摩耗性及び耐砂塵傷付き性の低下を抑制し、良好な摺動性を確保しながら、十分な塗料組成物の安定性と塗装作業性を確保することができる。
In one aspect, the aggregate (E) is 0.1 parts by mass or more and 10 parts by mass in terms of solid content with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 0.0 mass part or less, for example, 0.5 mass part or more and 8 mass parts or less in terms of solid content. In another embodiment, the aggregate (E) is 1.0 part by mass or more in terms of solid content based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 8 parts by mass or less, for example, 1.5 parts by mass or more and 8 parts by mass or less.
By including the aggregate (E) in such an amount, it is possible to suppress deterioration of repetitive wear resistance and resistance to dust and scratches and to secure good slidability, while maintaining sufficient stability of the coating composition. The paint workability can be secured.
溶剤（Ｆ）
本開示の塗料組成物は、溶剤（Ｆ）を含み、更に、溶剤（Ｆ）は、沸点が１８０℃以上であり、ケトン構造を有する溶剤（Ｆ−１）を含む。
本開示の塗料組成物は、所定の溶剤（Ｆ）中に、所定のポリフッ化ビニリデン樹脂（Ａ）と、アクリル樹脂（Ｂ）と、ポリテトラフルオロエチレン粒子（Ｃ）と、ワックス（Ｄ）と、骨材（Ｅ）とを含むことで、優れた加工性、意匠性、耐候性、耐食性、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び摺動性を有する塗膜を形成できる。
このように、本発明の塗料組成物は、所定の成分（Ａ）〜（Ｅ）及び所定の溶剤（Ｆ）、すなわち、所定の溶剤を含むことにより、塗装作業性、塗料安定性等の生産性を確保しつつ、種々の効果を相乗的に発揮できる。また、種々の効果を相乗的に発揮するだけでなく、例えば、耐摩耗性及び耐傷付き性の向上を試みると耐候性が悪くなる問題等、種々の問題を解決した。
更に、本開示の塗料組成物から形成した塗膜の耐傷付き性等の物性が大幅に向上したので、金属板、例えば、鋼板の表面のみに当該塗料を塗装し、裏面には安価な塗装金属板用裏面塗料を適用しても性能を確保することができ、プレコート金属板としてのコストを大幅に下げることに成功した。
Solvent (F)
The coating composition of the present disclosure includes a solvent (F), and the solvent (F) further includes a solvent having a boiling point of 180 ° C. or higher and a ketone structure (F-1).
The coating composition of the present disclosure comprises a predetermined solvent (F), a predetermined polyvinylidene fluoride resin (A), an acrylic resin (B), polytetrafluoroethylene particles (C), and a wax (D). By including the aggregate (E), it is possible to form a coating film having excellent processability, designability, weather resistance, corrosion resistance, scratch resistance, abrasion resistance, dust scratch resistance, and slidability.
As described above, the coating composition of the present invention contains the predetermined components (A) to (E) and the predetermined solvent (F), that is, the predetermined solvent, thereby producing coating workability, coating stability and the like. It is possible to exert various effects synergistically while ensuring the property. Further, in addition to synergistically exerting various effects, various problems have been solved, such as a problem that weather resistance deteriorates when an attempt is made to improve wear resistance and scratch resistance.
Furthermore, since the physical properties such as scratch resistance of the coating film formed from the coating composition of the present disclosure are significantly improved, the coating material is applied only to the surface of a metal plate, for example, a steel plate, and the back surface is made of inexpensive coating metal. The performance can be secured even if the backside paint for the plate is applied, and the cost as a pre-coated metal plate was successfully reduced significantly.
本開示において、沸点は、ＪＩＳ Ｋ ５６０１に規定の方法に従い測定できる。 In the present disclosure, the boiling point can be measured according to the method specified in JIS K5601.
本開示において、ケトン構造を有する溶剤は、分子中にカルボニル基（−Ｃ（＝Ｏ）−）を有する溶剤である。ケトン構造を有する溶剤は、直鎖状構造であってもよく、環状構造を有してもよい。 In the present disclosure, the solvent having a ketone structure is a solvent having a carbonyl group (-C (= O)-) in the molecule. The solvent having a ketone structure may have a linear structure or a cyclic structure.
ある態様において、溶剤（Ｆ−１）は、沸点が１８０℃以上であり、ケトン構造と環状構造とを有する溶剤を含む。塗料組成物がこのような構造を有することにより、塗料組成物に含まれる成分（Ａ）〜（Ｅ）が有する特性を、より効果的に発揮することができる。 In one aspect, the solvent (F-1) has a boiling point of 180 ° C. or higher and includes a solvent having a ketone structure and a cyclic structure. When the coating composition has such a structure, the characteristics of the components (A) to (E) contained in the coating composition can be more effectively exhibited.
溶剤（Ｆ−１）
溶剤（Ｆ−１）は、沸点が１８０℃以上であり、ケトン構造を有する。ある態様において、溶剤（Ｆ−１）の沸点は１８０℃以上２５０℃以下である。溶剤（Ｆ−１）の沸点は、例えば、１８０℃以上２２５℃以下であってよい。溶剤（Ｆ）は、単独の溶剤（Ｆ−１）を含んでもよく、複数の溶剤（Ｆ−１）を含んでもよい。
Solvent (F-1)
The solvent (F-1) has a boiling point of 180 ° C. or higher and has a ketone structure. In one embodiment, the boiling point of the solvent (F-1) is 180 ° C or higher and 250 ° C or lower. The boiling point of the solvent (F-1) may be, for example, 180 ° C. or higher and 225 ° C. or lower. The solvent (F) may include a single solvent (F-1) or a plurality of solvents (F-1).
溶剤（Ｆ−１）として、例えば、イソホロン（沸点：２１５℃）、フェニルアセトン（沸点：２１５℃）、アセトフェノン（沸点：２０２℃）、プロピレンカーボネート（沸点：２４２℃）及びγ−ブチロラクトン（沸点：２０４℃）、２−ノナノン（沸点：１９５℃）、３−ノナノン（沸点：１９０℃）、４−ノナノン（沸点：１８７℃）、５−ノナノン（沸点：１８６℃）、ジイソペンチルケトン（沸点：２０８℃）、アセトニルアセトン（沸点：１８８℃）等を挙げることができる。ある態様において、溶剤（Ｆ）は、溶剤（Ｆ−１）として、イソホロン（沸点：２１５℃）を含む。溶剤（Ｆ）が、溶剤（Ｆ−１）としてイソホロンを含むことによって、良好な塗膜外観、塗料組成物の貯蔵安定性を得ることができ、また、得られた塗膜に良好な耐候性、加工性等を付与できる。 Examples of the solvent (F-1) include isophorone (boiling point: 215 ° C.), phenylacetone (boiling point: 215 ° C.), acetophenone (boiling point: 202 ° C.), propylene carbonate (boiling point: 242 ° C.) and γ-butyrolactone (boiling point: 204 ° C), 2-nonanone (boiling point: 195 ° C), 3-nonanone (boiling point: 190 ° C), 4-nonanone (boiling point: 187 ° C), 5-nonanone (boiling point: 186 ° C), diisopentyl ketone (boiling point) : 208 ° C.), acetonylacetone (boiling point: 188 ° C.) and the like. In one aspect, the solvent (F) contains isophorone (boiling point: 215 ° C.) as the solvent (F-1). When the solvent (F) contains isophorone as the solvent (F-1), good coating film appearance and storage stability of the coating composition can be obtained, and the coating film obtained has good weather resistance. , Processability and the like can be imparted.
ある態様において、塗料組成物は、溶剤（Ｆ）１００質量部に対して、上記ケトン構造を有する溶剤（Ｆ−１）を、５０質量部以上１００質量部以下で含む。
ある態様において、溶剤（Ｆ）は、更に、他の溶剤を含んでもよい。他の溶剤として、例えば、後述する、ケトン構造を有し、沸点が１８０℃未満である溶剤（Ｆ−２）を含んでもよい。
ある態様において、本開示に係る塗料組成物は、溶剤（Ｆ）１００質量部に対して、ケトン構造を有する溶剤（Ｆ−１）を、５０質量部以上８０質量部以下で含み、例えば、ケトン構造を有する溶剤（Ｆ−１）を、５０質量部以上７５質量部以下で含み得る。いずれの態様においても、溶剤（Ｆ）は、その残りについて、他の溶剤、例えば溶剤（Ｆ−２）を含み得る。
In one aspect, the coating composition contains 50 parts by mass or more and 100 parts by mass or less of the solvent (F-1) having the above ketone structure with respect to 100 parts by mass of the solvent (F).
In one embodiment, the solvent (F) may further contain other solvent. As another solvent, for example, a solvent (F-2) having a ketone structure and having a boiling point of less than 180 ° C., which will be described later, may be included.
In one aspect, the coating composition according to the present disclosure contains the solvent (F-1) having a ketone structure in an amount of 50 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the solvent (F). The solvent (F-1) having a structure may be contained in an amount of 50 parts by mass or more and 75 parts by mass or less. In any of the embodiments, the solvent (F) may contain other solvent, for example, the solvent (F-2) for the rest.
溶剤（Ｆ）は、ケトン構造を有する溶剤（Ｆ−１）に加えて、他の溶剤を含んでよい。
他の溶剤として、ケトン構造を有する溶剤（Ｆ−１）の性質を損なわない限り、既知の溶剤を選択できる。
ある態様において、溶剤（Ｆ）は、上記の、沸点が１８０℃以上であり、ケトン構造を有する溶剤（Ｆ−１）に加えて、更に、他の溶剤として、ケトン構造を有し、沸点が１８０℃未満である溶剤（Ｆ−２）を含んでよい。
例えば、ケトン構造を有する溶剤（Ｆ−２）の沸点は、１００℃以上、１８０℃未満であり、ある態様において、溶剤（Ｆ−２）の沸点は、１３０℃以上１８０℃未満である。
溶剤（Ｆ）が溶剤（Ｆ−１）と、溶剤（Ｆ−２）とを含むことにより、更に良好な塗膜外観および塗料組成物の貯蔵安定性を得ることができ、また、得られた塗膜により良好な耐候性、加工性等を付与できる。
The solvent (F) may contain another solvent in addition to the solvent (F-1) having a ketone structure.
As the other solvent, a known solvent can be selected as long as it does not impair the properties of the solvent (F-1) having a ketone structure.
In one embodiment, the solvent (F) has a ketone structure and a boiling point of 180 ° C. or higher, and further has a ketone structure as another solvent in addition to the solvent (F-1) having a ketone structure. It may include a solvent (F-2) that is less than 180 ° C.
For example, the boiling point of the solvent (F-2) having a ketone structure is 100 ° C or higher and lower than 180 ° C, and in one embodiment, the boiling point of the solvent (F-2) is 130 ° C or higher and lower than 180 ° C.
By including the solvent (F-1) and the solvent (F-2) in the solvent (F), a better coating film appearance and storage stability of the coating composition can be obtained, and obtained. Good weather resistance and workability can be imparted to the coating film.
例えば、溶剤（Ｆ）において、溶剤（Ｆ−１）の量と溶剤（Ｆ−２）の量との比は、
溶剤（Ｆ−１）：溶剤（Ｆ−２）＝１：０．０５〜１：０．５であり、ある態様において、溶剤（Ｆ−１）：溶剤（Ｆ−２）＝１：０．０５〜１：０．３である。
このような関係を有することにより、更に優れた塗膜外観、加工性、意匠性、耐候性、耐食性、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び摺動性を有する塗膜を形成できる。
For example, in the solvent (F), the ratio of the amount of the solvent (F-1) to the amount of the solvent (F-2) is
Solvent (F-1): Solvent (F-2) = 1: 0.05 to 1: 0.5, and in one embodiment, Solvent (F-1): Solvent (F-2) = 1: 0. It is 05 to 1: 0.3.
By having such a relationship, a coating film having excellent coating film appearance, processability, designability, weather resistance, corrosion resistance, scratch resistance, abrasion resistance, dust scratch resistance, and slidability can be formed. it can.
溶剤（Ｆ−１）とは異なる他の溶剤として、例えば、トルエン、キシレン（キシロール）、メチルセロソルブ、ブチルセロソルブ、セロソルブアセテート、ブチルセロソルブアセテート、カルビトール、エチルカルビトール、ブチルカルビトール、酢酸エチル、酢酸ブチル、石油エーテル、石油ナフサ、シクロヘキサノール、１−ブタノール、２−ブタノール、２−プロパノール、ブチルジグリコール、酢酸カービトール、亜リン酸トリエチル等が挙げられる。市販品として、例えば、ソルベッソ１００（エクソン化学社製）、ソルベッソ１５０（エクソン化学社製）、ソルベッソ２００（エクソン化学社製）が挙げられる。
ある態様において、溶剤（Ｆ）は、溶剤（Ｆ−１）とは異なる他の溶剤として、ケトン構造を有し、沸点が１８０℃未満である溶剤（Ｆ−２）を更に含み得る。
例えば、シクロヘキサノン（沸点：１５６℃）、シクロペンタノン（沸点：１３１℃）、３−メチルシクロヘキサノン（沸点：１６９℃）、４−メチルシクロヘキサノン（沸点：１７１℃）、２−オクタノン（沸点：１７３℃）、３−オクタノン（沸点：１６７℃）、４−オクタノン（沸点：１６６℃）、２−ヘプタノン（沸点：１５１℃）、３−ヘプタノン（沸点：１４６℃）、４−ヘプタノン（沸点：１４４℃）、２−ヘキサノン（沸点：１２８℃）、３−ヘキサノン（沸点：１２３℃）、ジイソブチルケトン（沸点：１６８℃）、エチルイソブチルケトン（沸点：１３６℃）等が挙げられる。ある態様において、溶剤（Ｆ−２）は、更に環状構造を有することが好ましい。
Other solvents different from the solvent (F-1) include, for example, toluene, xylene (xylol), methyl cellosolve, butyl cellosolve, cellosolve acetate, butyl cellosolve acetate, carbitol, ethyl carbitol, butyl carbitol, ethyl acetate, butyl acetate. , Petroleum ether, petroleum naphtha, cyclohexanol, 1-butanol, 2-butanol, 2-propanol, butyldiglycol, carbitol acetate, triethyl phosphite and the like. Examples of commercially available products include Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.), Solvesso 150 (manufactured by Exxon Chemical Co., Ltd.), and Solvesso 200 (manufactured by Exxon Chemical Co., Ltd.).
In one embodiment, the solvent (F) may further include a solvent (F-2) having a ketone structure and a boiling point of less than 180 ° C. as another solvent different from the solvent (F-1).
For example, cyclohexanone (boiling point: 156 ° C), cyclopentanone (boiling point: 131 ° C), 3-methylcyclohexanone (boiling point: 169 ° C), 4-methylcyclohexanone (boiling point: 171 ° C), 2-octanone (boiling point: 173 ° C) ), 3-octanone (boiling point: 167 ° C.), 4-octanone (boiling point: 166 ° C.), 2-heptanone (boiling point: 151 ° C.), 3-heptanone (boiling point: 146 ° C.), 4-heptanone (boiling point: 144 ° C.) ), 2-hexanone (boiling point: 128 ° C.), 3-hexanone (boiling point: 123 ° C.), diisobutyl ketone (boiling point: 168 ° C.), ethyl isobutyl ketone (boiling point: 136 ° C.) and the like. In one aspect, the solvent (F-2) preferably further has a cyclic structure.
その他成分
本開示の塗料組成物は、成分（Ａ）〜（Ｆ）に加えて、目的、用途に応じて着色顔料、体質顔料、その他の添加剤等を必要に応じて配合することができる。ただし、その他の添加剤等は、本開示の塗料組成物が有する諸物性を損なわない態様で添加できる。
例えば、ｐ−トルエンスルホン酸、オクトエ酸錫、ジブチル錫ジラウレート、２−エチルヘキソエート鉛等の硬化触媒、炭酸カルシウム、カオリン、クレー、酸化チタン、タルク、硫酸バリウム、マイカ、弁柄、マンガンブルー、カーボンブラック、アルミニウム粉、パールマイカ等の顔料、その他、消泡剤、レベリング剤、増粘剤、可塑剤、酸化防止剤、紫外線吸収剤、ハジキ防止剤、皮張り防止剤等の各種添加剤を選択して配合することができる。
Other Components In addition to the components (A) to (F), the coating composition of the present disclosure may contain a color pigment, an extender pigment, other additives, and the like, if necessary, depending on the purpose and application. However, other additives and the like can be added in a manner that does not impair the physical properties of the coating composition of the present disclosure.
For example, a curing catalyst such as p-toluenesulfonic acid, tin octoate, dibutyltin dilaurate, 2-ethylhexoate lead, calcium carbonate, kaolin, clay, titanium oxide, talc, barium sulfate, mica, rouge, manganese blue. , Carbon black, aluminum powder, pigments such as pearl mica, and other additives such as defoaming agents, leveling agents, thickeners, plasticizers, antioxidants, UV absorbers, cissing inhibitors, anti-skinning agents, etc. Can be selected and blended.
塗料組成物の調製方法
本開示に係る塗料組成物を調製する方法は、特に限定されない。例えば、サンドグラインドミル、ボールミル、ブレンダー、ペイントシェーカー又はディスパー等の混合機、分散機、混練機等を選択して使用し、各成分を混合することにより、調製することができる。
Method for Preparing Coating Composition The method for preparing the coating composition according to the present disclosure is not particularly limited. For example, a sand mill, a ball mill, a blender, a mixer such as a paint shaker or a disper, a disperser, a kneader, and the like can be selected and used, and can be prepared by mixing the respective components.
被塗物
本開示のプレコート金属板用塗料組成物の塗装の対象となる被塗物は、例えば、溶融法又は電解法等により製造される亜鉛めっき鋼板、亜鉛−アルミニウム合金めっき鋼板、アルミニウム合金めっき鋼板、溶融亜鉛−アルミニウム−マグネシウム合金めっき鋼板、ステンレス鋼板、冷延鋼板等が挙げられる。また、これら鋼板又はめっき鋼板以外に、アルミニウム板（アルミニウム合金板を含む）等の金属板も塗装対象とすることができる。
本開示に係る金属板は、表面処理されていることが好ましい。具体的には、本発明の金属板は、アルカリ脱脂処理、湯洗処理、水洗処理等の前処理が施された後に、化成処理が施されていることが好ましい。化成処理は公知の方法で行ってよく、その例にはクロメート処理、リン酸亜鉛処理等の非クロメート処理等が含まれる。
Object to be coated The object to be coated with the coating composition for a precoated metal plate of the present disclosure is, for example, a galvanized steel sheet manufactured by a melting method or an electrolytic method, a zinc-aluminum alloy plated steel sheet, an aluminum alloy plating. A steel plate, a hot-dip zinc-aluminum-magnesium alloy plated steel plate, a stainless steel plate, a cold-rolled steel plate, etc. are mentioned. In addition to these steel plates or plated steel plates, a metal plate such as an aluminum plate (including an aluminum alloy plate) can also be a coating target.
The metal plate according to the present disclosure is preferably surface-treated. Specifically, the metal plate of the present invention is preferably subjected to chemical conversion treatment after being subjected to pretreatment such as alkali degreasing treatment, hot water washing treatment, and water washing treatment. The chemical conversion treatment may be carried out by a known method, and examples thereof include chromate treatment, non-chromate treatment such as zinc phosphate treatment and the like.
ある態様において、プレコート金属板は、一方の面に、本開示に係るプレコート金属板用塗料組成物から形成された塗膜を有する。
例えば、プレコート金属板用塗料組成物から形成された塗膜の膜厚は、１０μｍ以上２５μｍ以下であり、ある態様においては、膜厚は、１５μｍ以上２３μｍ以下である。
プレコート金属板用塗料組成物から形成された塗膜の膜厚が、このような範囲内であることにより、更に優れた加工性、意匠性、耐候性、耐食性、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び摺動性を有する塗膜が備えられた、プレコート金属板を得ることができる。
In one aspect, the precoated metal plate has a coating film formed on one surface from the coating composition for a precoated metal plate according to the present disclosure.
For example, the film thickness of the coating film formed from the coating composition for a pre-coated metal plate is 10 μm or more and 25 μm or less, and in one aspect, the film thickness is 15 μm or more and 23 μm or less.
The film thickness of the coating film formed from the coating composition for precoat metal plate is within such a range, further excellent processability, designability, weather resistance, corrosion resistance, scratch resistance, abrasion resistance, It is possible to obtain a precoated metal plate provided with a coating film having sand scratch resistance and slidability.
プレコート金属板が、一方の面に本開示に係るプレコート金属板用塗料組成物から形成された塗膜を有する場合、他方の面は、既知の塗料組成物から形成される塗膜であってもよい。
例えば、他方の面は、エポキシ樹脂を含む塗料組成物等、公知の塗料組成物から形成された塗膜を有してもよい。
When the precoated metal plate has a coating film formed on one surface from the coating composition for a precoated metal plate according to the present disclosure, the other surface may be a coating film formed from a known coating composition. Good.
For example, the other surface may have a coating film formed from a known coating composition such as a coating composition containing an epoxy resin.
ある態様において、プレコート金属板は、シャッタースラット材である。シャッタースラット材は、少なくとも一方の面に本開示に係るプレコート金属板用塗料組成物から形成された塗膜を有する。本開示の塗料組成物から形成された塗膜を有することにより、シャッタースラット材は、優れた加工性を有するので、加工後も優れた意匠性を保持できる。 In some embodiments, the precoated metal sheet is shutter slat material. The shutter slat material has a coating film formed on at least one surface of the coating composition for a precoated metal sheet according to the present disclosure. By having a coating film formed from the coating composition of the present disclosure, the shutter slat material has excellent processability, and therefore, excellent designability can be retained even after processing.
別の態様において、シャッタースラット材は、一方の面に、本開示に係るプレコート金属板用塗料組成物から形成された塗膜を有し、他方の面に、既知の塗料組成物から形成される塗膜を有してもよい。
図１は、プレコート金属板の一例である、シャッタースラット材１が、金属板２０の一方の面に、本開示に係るプレコート金属板用塗料組成物から形成された塗膜１０を有し、他方の面に、塗料組成物から形成される塗膜３０を有する態様を例示する、断面概略図である。例えば、塗膜３０は、既知の塗料組成物から形成された塗膜であってよく、本開示に係る塗料組成物から形成された塗膜であってよい。
In another aspect, the shutter slat material has a coating film formed on one surface from the coating composition for a precoated metal sheet according to the present disclosure, and the other surface formed from a known coating composition. It may have a coating film.
FIG. 1 shows a
シャッターとして用いる場合、一のシャッタースラット材１における、本開示に係るプレコート金属板用塗料組成物から形成された塗膜１０側に、他のシャッタースラット材１における、既知の塗料組成物から形成される塗膜３０側が配置される。したがって、この態様の場合、本開示に係るプレコート金属板用塗料組成物から形成された塗膜と、例えば、既知の塗料組成物から形成される塗膜とが接触することになる
なお、本開示において、「シャッタースラット材の表面」等、「表面」と記載するときは、特に記載の無い限り、塗膜１０を意味し、すなわち、本開示の塗料組成物から形成した塗膜面を意味し、「裏面」とは塗膜３０を意味し得る。
When used as a shutter, on one side of the
本開示のシャッタースラット材は、同一の塗膜を金属板、例えば、鋼板の両面に形成しなくても、上述の塗膜性能を十分に発揮できるので、シャッタースラット材のコスト上昇を抑制できる。同様に、プレコート金属板のコストも抑制できる。
所望により、シャッタースラット材は、金属板、例えば、鋼板等の金属板に加えて、他の部品を含んでもよい。これらの部品に、本開示の塗料組成物を塗装し、塗膜を形成してもよい。
Since the shutter slat material of the present disclosure can sufficiently exhibit the above-mentioned coating film performance without forming the same coating film on both surfaces of a metal plate, for example, a steel plate, it is possible to suppress the cost increase of the shutter slat material. Similarly, the cost of the precoated metal plate can be suppressed.
If desired, the shutter slat material may include other components in addition to a metal plate, eg, a metal plate such as a steel plate. The coating composition of the present disclosure may be applied to these parts to form a coating film.
プレコート金属板、例えば、シャッタースラット材は、金属板と、本開示の塗料組成物から形成した塗膜との間に、下塗り塗膜を有してもよい。下塗り塗膜を有することで、本開示の塗料組成物から形成された塗膜の密着性、耐食性を高めることができる。また、本開示の塗料組成物から形成された塗膜の性質をより強固に補うことができるので、シャッタースラット材等のプレコート金属板を、より長期間使用できる。
ある態様において、下塗り塗膜の膜厚は、３μｍ以上１５μｍ以下の膜厚であり、例えば５μｍ以上１０μｍ以下である。
A precoated metal sheet, such as a shutter slat, may have a primer coating between the metal sheet and the coating formed from the coating composition of the present disclosure. By having the undercoat coating film, the adhesion and corrosion resistance of the coating film formed from the coating composition of the present disclosure can be improved. Further, since the properties of the coating film formed from the coating composition of the present disclosure can be more strongly supplemented, the precoated metal plate such as the shutter slat material can be used for a longer period of time.
In one aspect, the film thickness of the undercoat coating film is 3 μm or more and 15 μm or less, for example, 5 μm or more and 10 μm or less.
塗膜形成方法
本開示の塗料組成物の塗装は、被塗装金属板等の表面に塗装下地処理としてリン酸塩処理、クロメート処理等の化成処理を施し、その上に塗料組成物を塗装することが好ましい。このように化成処理を施した金属板面上に、本開示の塗料組成物を塗装することにより、塗膜の金属板面に対する密着性が向上するとともに耐食性も向上する。また、化成処理を施した金属板面に下塗り塗膜（プライマー塗膜）を形成し、その上に塗装することもできる。
Coating film formation method The coating of the coating composition of the present disclosure is performed by chemical conversion treatment such as phosphate treatment or chromate treatment as a coating base treatment on the surface of a metal plate to be coated, and the coating composition is coated thereon. Is preferred. By coating the coating composition of the present disclosure on the surface of the metal plate that has been subjected to the chemical conversion treatment, the adhesion of the coating film to the surface of the metal plate is improved and the corrosion resistance is also improved. It is also possible to form an undercoat coating film (primer coating film) on the surface of the metal plate that has been subjected to the chemical conversion treatment, and apply it on it.
塗料組成物の金属板表面への塗装方法は特に限定しないが、ロールコーター、エアレススプレー、静電スプレー、カーテンフローコーター等、従来公知の方法を採用することができ、好ましくはロールコーター、カーテンフローコーターで塗装するのがよい。塗装後、熱風加熱、赤外線加熱、誘導加熱等の加熱手段により塗膜を焼き付け、樹脂を架橋させて硬化塗膜を得る。 The method for coating the surface of the metal plate of the coating composition is not particularly limited, but conventionally known methods such as roll coater, airless spray, electrostatic spray, curtain flow coater and the like can be adopted, preferably roll coater, curtain flow. It is better to paint with a coater. After coating, the coating film is baked by heating means such as hot air heating, infrared heating, and induction heating to crosslink the resin to obtain a cured coating film.
ある態様において、プレコート金属板の製造方法は、
金属板、例えば、鋼板の少なくとも一方の面に、本開示のプレコート金属板用塗料組成物を、硬化後の膜厚が１０μｍ以上２５μｍ以下となるよう塗装すること、
プレコート金属板用塗料組成物を２３０℃以上２６０℃以下の温度、２０秒以上１２０秒以下の条件下で、乾燥及び硬化させることを含む。
ある態様において、塗料組成物を塗装後、素材到達最高温度が２３０℃以上２６０℃以下の温度となる条件で乾燥及び硬化（焼付け）できる。
焼付処理後、常温まで冷却してプレコート金属板を得ることができる。焼付処理後の冷却は、水で板温を常温まで急冷することが好ましい。
In one aspect, the method for producing a precoated metal sheet,
Coating the coating composition for a precoated metal plate of the present disclosure on at least one surface of a metal plate, for example, a steel plate so that the film thickness after curing is 10 μm or more and 25 μm or less,
It includes drying and curing the coating composition for a pre-coated metal plate at a temperature of 230 ° C. or more and 260 ° C. or less and a condition of 20 seconds or more and 120 seconds or less.
In one aspect, after coating the coating composition, the coating composition can be dried and cured (baked) under the condition that the maximum temperature reached by the material is 230 ° C. or higher and 260 ° C. or lower.
After the baking treatment, the precoated metal plate can be obtained by cooling to room temperature. For cooling after the baking treatment, it is preferable to rapidly cool the plate temperature to normal temperature with water.
このようにして形成されたプレコート金属板の硬化塗膜の膜厚は、例えば、１０μｍ以上２５μｍ以下であり、ある態様において、膜厚は、１２μｍ以上２３μｍ以下である。
プレコート金属板用塗料組成物から形成された塗膜の膜厚が、このような範囲内であることにより、更に優れた加工性、意匠性、耐候性、耐食性、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び摺動性を有する塗膜が備えられた、プレコート金属板を得ることができる。
The film thickness of the cured coating film of the precoated metal plate thus formed is, for example, 10 μm or more and 25 μm or less, and in one aspect, the film thickness is 12 μm or more and 23 μm or less.
The film thickness of the coating film formed from the coating composition for precoat metal plate is within such a range, further excellent processability, designability, weather resistance, corrosion resistance, scratch resistance, abrasion resistance, It is possible to obtain a precoated metal plate provided with a coating film having sand scratch resistance and slidability.
本発明のプレコート金属板用塗料組成物は、２コート・２ベーク方式又は３コート・３ベーク方式のトップコートとしての使用が特に好ましい。３コート・３ベーク方式で使用する場合は、本発明のプレコート金属板用塗料組成物による塗膜とプライマー塗膜（下塗り塗膜）との間に、通常の３コート・３ベークで使用される中塗塗膜を設ける。 The precoat metal plate coating composition of the present invention is particularly preferably used as a 2 coat / 2 bake system or a 3 coat / 3 bake top coat. When used in a 3 coat / 3 bake system, it is used in a normal 3 coat / 3 bake between the coating film of the coating composition for a precoated metal plate of the present invention and the primer coating film (undercoating film). Provide an intermediate coating film.
以下の実施例により本発明を更に具体的に説明するが、本発明はこれらに限定されない。実施例中「部」及び「％」は、ことわりのない限り質量基準による。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified.
塗料組成物の調製に用いた各成分は、以下のとおりである。また、アクリル樹脂（Ｂ）については、その調整方法を説明する。
ポリフッ化ビニリデン樹脂（Ａ−１）
Ｋｙｎａｒ５００（アルケマ社製；樹脂固形分濃度：１００質量％）
ポリフッ化ビニリデン樹脂（Ａ−２）
Ｈｙｌａｒ５０００（ソルベイ社製；樹脂固形分濃度：１００質量％）
The components used for preparing the coating composition are as follows. Further, for the acrylic resin (B), the adjusting method will be described.
Polyvinylidene fluoride resin (A-1)
Kynar500 (manufactured by Arkema; resin solid content concentration: 100% by mass)
Polyvinylidene fluoride resin (A-2)
Hylar5000 (manufactured by Solvay; resin solid content concentration: 100% by mass)
（製造例Ｂ−１）
アクリル樹脂（Ｂ−１）（熱硬化性アクリル樹脂）の合成
還流冷却器、滴下ロート、攪拌機、温度計、コンデンサー、窒素ガス導入口を備えた反応容器に、イソホロン６６７．５質量部を仕込み、窒素雰囲気下で９０℃まで昇温した。これに、メタクリル酸７．６５質量部、メタクリル酸メチル３１０．８質量部、アクリル酸ｎ−ブチル１６８．９質量部、ジメタクリル酸エチレングリコール１．０質量部及びＮ−メトキシメチルアクリルアミド１１．６質量部の混合溶液、並びに開始剤として、２，２’−アゾビスイソブチロニトリル１．５質量部及びイソホロン４７．５質量部の混合溶液を、滴下ロートを通じて各々同時に３時間で等速滴下した。滴下終了後、９０℃を保持したまま３０分撹拌を続けた後、反応容器を１２０℃まで昇温した。次に、２，２’−アゾビスイソブチロニトリル５質量部及びイソホロン３５質量部の混合溶液を、３０分で等速滴下した。滴下終了後、１２０℃を保持したまま２時間撹拌し、アクリル樹脂（Ｂ−１）（固形分濃度：４０質量％、固形分酸価：１０ｍｇＫＯＨ／ｇ、固形分水酸基価：０ｍｇＫＯＨ／ｇ、ガラス転移温度：３０℃、数平均分子量：１２０，０００）を得た。
(Production Example B-1)
Synthesis of acrylic resin (B-1) (thermosetting acrylic resin) A reaction vessel equipped with a reflux condenser, a dropping funnel, a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was charged with 667.5 parts by mass of isophorone. The temperature was raised to 90 ° C. under a nitrogen atmosphere. To this, 7.65 parts by weight of methacrylic acid, 310.8 parts by weight of methyl methacrylate, 168.9 parts by weight of n-butyl acrylate, 1.0 part by weight of ethylene glycol dimethacrylate and 11.6 of N-methoxymethylacrylamide. Part by mass of a mixed solution of 1.5 parts by mass of 2,2'-azobisisobutyronitrile and 47.5 parts by mass of isophorone as an initiator are simultaneously dropped at a constant rate in 3 hours through a dropping funnel. did. After completion of the dropping, stirring was continued for 30 minutes while maintaining 90 ° C, and then the temperature of the reaction vessel was raised to 120 ° C. Next, a mixed solution of 5 parts by mass of 2,2′-azobisisobutyronitrile and 35 parts by mass of isophorone was added dropwise at a constant rate over 30 minutes. After completion of dropping, the mixture was stirred for 2 hours while maintaining 120 ° C., acrylic resin (B-1) (solid content concentration: 40 mass%, solid content acid value: 10 mgKOH / g, solid content hydroxyl value: 0 mgKOH / g, glass Transition temperature: 30 ° C., number average molecular weight: 120,000) was obtained.
（製造例Ｂ−２）
アクリル樹脂（Ｂ−２）（熱可塑性アクリル樹脂）の合成
還流冷却器、滴下ロート、攪拌機、温度計、コンデンサー、窒素ガス導入口を備えた反応容器に、イソホロン６６７．５質量部を仕込み、窒素雰囲気下で９０℃まで昇温した。これに、メタクリル酸７．６５質量部、メタクリル酸メチル３１０．８質量部、アクリル酸ｎ−ブチル１６８．９質量部、ジメタクリル酸エチレングリコール１．０質量部及びメタクリル酸２−ヒドロキシエチル１１．６質量部の混合溶液、並びに開始剤として、２，２’−アゾビスイソブチロニトリル１．５質量部及びイソホロン４７．５質量部の混合溶液を、滴下ロートを通じて各々同時に３時間で等速滴下した。滴下終了後、９０℃を保持したまま３０分撹拌を続けた後、反応容器を１２０℃まで昇温した。次に、２，２’−アゾビスイソブチロニトリル５質量部及びイソホロン３５質量部の混合溶液を、３０分で等速滴下した。滴下終了後、１２０℃を保持したまま２時間撹拌し、固形分酸価１０、固形分水酸基価０、Ｔｇ３０℃のアクリル樹脂（Ｂ−２）（固形分濃度：４０質量％、固形分酸価：１０ｍｇＫＯＨ／ｇ、固形分水酸基価：０ｍｇＫＯＨ／ｇ、ガラス転移温度：３０℃、数平均分子量：１０，０００）を得た。
(Production Example B-2)
Synthesis of acrylic resin (B-2) (thermoplastic acrylic resin) A reaction vessel equipped with a reflux condenser, a dropping funnel, a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was charged with 667.5 parts by mass of isophorone and nitrogen. The temperature was raised to 90 ° C. in the atmosphere. To this, 7.65 parts by weight of methacrylic acid, 310.8 parts by weight of methyl methacrylate, 168.9 parts by weight of n-butyl acrylate, 1.0 part by weight of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate. 6 parts by mass of a mixed solution and, as an initiator, 1.5 parts by mass of 2,2′-azobisisobutyronitrile and 47.5 parts by mass of isophorone were mixed at a constant speed for 3 hours at the same time through a dropping funnel. Dropped. After completion of the dropping, stirring was continued for 30 minutes while maintaining 90 ° C, and then the temperature of the reaction vessel was raised to 120 ° C. Next, a mixed solution of 5 parts by mass of 2,2′-azobisisobutyronitrile and 35 parts by mass of isophorone was added dropwise at a constant rate over 30 minutes. After completion of the dropping, the mixture was stirred for 2 hours while maintaining 120 ° C., and the solid content acid value was 10, the solid content hydroxyl value was 0, and the acrylic resin (B-2) had a Tg of 30 ° C. (solid content concentration: 40 mass%, solid content acid value). : 10 mgKOH / g, solid content hydroxyl value: 0 mgKOH / g, glass transition temperature: 30 ° C., number average molecular weight: 10,000).
（製造例Ｂ−３）
アクリル樹脂（Ｂ−３）（熱硬化性アクリル樹脂）の合成
還流冷却器、滴下ロート、攪拌機、温度計、コンデンサー、窒素ガス導入口を備えた反応容器に、イソホロン６６７．５質量部を仕込み、窒素雰囲気下で９０℃まで昇温した。これに、メタクリル酸７．６５質量部、メタクリル酸メチル２７４．２質量部、アクリル酸ｎ−ブチル１６０．２質量部、ジメタクリル酸エチレングリコール１．０質量部及びメタクリル酸２−ヒドロキシエチル５７．０質量部の混合溶液、並びに開始剤として、２，２’−アゾビスイソブチロニトリル１．５質量部及びイソホロン４７．５質量部の混合溶液を、滴下ロートを通じて各々同時に３時間で等速滴下した。滴下終了後、９０℃を保持したまま３０分撹拌を続けた後、反応容器を１２０℃まで昇温した。次に、２，２’−アゾビスイソブチロニトリル５質量部及びイソホロン３５質量部の混合溶液を、３０分で等速滴下した。滴下終了後、１２０℃を保持したまま２時間撹拌し、アクリル樹脂（Ｂ−３）（固形分濃度：４０質量％、固形分酸価：１０ｍｇＫＯＨ／ｇ、固形分水酸基価：５０ｍｇＫＯＨ／ｇ、ガラス転移温度：３０℃、数平均分子量：１０，０００）を得た。
(Production Example B-3)
Synthesis of acrylic resin (B-3) (thermosetting acrylic resin) A reaction vessel equipped with a reflux condenser, a dropping funnel, a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was charged with 667.5 parts by mass of isophorone. The temperature was raised to 90 ° C. under a nitrogen atmosphere. To this, 7.65 parts by weight of methacrylic acid, 274.2 parts by weight of methyl methacrylate, 160.2 parts by weight of n-butyl acrylate, 1.0 part by weight of ethylene glycol dimethacrylate and 2-hydroxyethyl methacrylate 57. A mixed solution of 0 parts by mass and a mixed solution of 1.5 parts by mass of 2,2′-azobisisobutyronitrile and 47.5 parts by mass of isophorone as an initiator were simultaneously fed through a dropping funnel at a constant speed for 3 hours each. Dropped. After completion of the dropping, stirring was continued for 30 minutes while maintaining 90 ° C, and then the temperature of the reaction vessel was raised to 120 ° C. Next, a mixed solution of 5 parts by mass of 2,2′-azobisisobutyronitrile and 35 parts by mass of isophorone was added dropwise at a constant rate over 30 minutes. After completion of dropping, the mixture was stirred for 2 hours while maintaining 120 ° C., and acrylic resin (B-3) (solid content concentration: 40 mass%, solid content acid value: 10 mgKOH / g, solid content hydroxyl value: 50 mgKOH / g, glass Transition temperature: 30 ° C., number average molecular weight: 10,000) was obtained.
・ポリテトラフルオロエチレン粒子（Ｃ−１）：ＫＴＬ−２０Ｎ（喜多村社製；樹脂固形分濃度：１００質量％、平均粒子径：２０μｍ、融点：３１０〜３２０℃）
・ポリテトラフルオロエチレン粒子（Ｃ−２）：ＫＴＬ−８Ｎ（喜多村社製；樹脂固形分濃度：１００質量％、平均粒子径：４μｍ、融点：３１０〜３２０℃）
・ポリテトラフルオロエチレン粒子（Ｃ−３）：ＫＴＬ−１Ｎ（喜多村社製；樹脂固形分濃度：１００質量％、平均粒子径：２μｍ、融点：３１０〜３２０℃）
-Polytetrafluoroethylene particles (C-1): KTL-20N (manufactured by Kitamura; resin solid content concentration: 100% by mass, average particle diameter: 20 μm, melting point: 310 to 320 ° C.)
-Polytetrafluoroethylene particles (C-2): KTL-8N (manufactured by Kitamura; resin solid content concentration: 100% by mass, average particle diameter: 4 μm, melting point: 310 to 320 ° C.)
-Polytetrafluoroethylene particles (C-3): KTL-1N (manufactured by Kitamura; resin solid content concentration: 100% by mass, average particle diameter: 2 μm, melting point: 310 to 320 ° C.)
・ワックス（Ｄ−１）：ＨＩ−ＤＩＳＰＥＲ１２５０（岐阜セラック製造所社製、マイクロクリスタリンワックス；樹脂固形分濃度：１０質量％、平均粒子径：１３μｍ）
・ワックス（Ｄ−２）：ＨＩ−ＦＬＡＴ Ｘ−１５Ｐ−２（岐阜セラック製造所社製、ポリエチレンワックス；樹脂固形分濃度：１５質量％、平均粒子径：１２μｍ）
Wax (D-1): HI-DISPER1250 (manufactured by Gifu Shellac Manufacturing Co., Ltd., microcrystalline wax; resin solid content concentration: 10% by mass, average particle diameter: 13 μm)
Wax (D-2): HI-FLAT X-15P-2 (manufactured by Gifu Shellac Manufacturing Co., polyethylene wax; resin solid content concentration: 15% by mass, average particle diameter: 12 μm)
・骨材（Ｅ−１）：サイリシア４３５（富士シリシア社製、シリカ微粉末、平均粒子径：６μｍ）
・骨材（Ｅ−２）：ガンツパール ＧＭ−１００１(アイカ工業社製、アクリル樹脂粒子、平均粒子径：１０μｍ)
・骨材（Ｅ−３）：サイロイド ＥＤ８０（富士シリシア社製、シリカ微粉末、平均粒子径：１２μｍ）
・骨材（Ｅ−４）：ガンツパール ＧＭ−２００１(アイカ工業社製、アクリル樹脂粒子、平均粒子径：２０μｍ)
-Aggregate (E-1): Sylysia 435 (manufactured by Fuji Silysia Ltd., silica fine powder, average particle size: 6 μm)
-Aggregate (E-2): Ganz Pearl GM-1001 (manufactured by Aika Kogyo Co., Ltd., acrylic resin particles, average particle diameter: 10 μm)
-Aggregate (E-3): Syloid ED80 (manufactured by Fuji Silysia Chemical Ltd., fine silica powder, average particle diameter: 12 μm)
-Aggregate (E-4): Ganz Pearl GM-2001 (manufactured by Aika Kogyo Co., Ltd., acrylic resin particles, average particle diameter: 20 μm)
・溶剤（Ｆ−１１）：イソホロン （ケトン構造を有する溶剤；沸点：２１５℃）
・溶剤（Ｆ−１２）：プロピレンカーボネート （ケトン構造を有する溶剤；沸点：２４２℃）
・溶剤（Ｆ−２）：シクロヘキサノン （ケトン構造を有する溶剤；沸点：１５６℃）
・溶剤（Ｆ−３）：キシレン （ケトン構造を有しない溶剤；沸点：１３９℃）
・溶剤（Ｆ−４）：２−ブタノール （ケトン構造を有しない溶剤；沸点：１０８℃）
・溶剤（Ｆ−５）：ソルベッソ１５０ （エクソン化学社製、ケトン構造を有しない溶剤；沸点：１９５℃）
・顔料：ＬＯＭＯＮ Ｔｉｔａｎｉｕｍ Ｄｉｏｘｉｄｅ Ｒ−９９６（酸化チタン；ＳＩＣＨＵＡＮ ＬＯＭＯＮ ＴＩＴＡＮＩＵＭ ＩＮＤＵＳＴＲＹ社製）
・メラミン樹脂：サイメル３０３ （三井サイアナミッド社製）
・硬化触媒：ドデシルベンゼンスルホン酸
-Solvent (F-11): Isophorone (solvent having a ketone structure; boiling point: 215 ° C)
-Solvent (F-12): Propylene carbonate (solvent having a ketone structure; boiling point: 242 ° C)
-Solvent (F-2): cyclohexanone (a solvent having a ketone structure; boiling point: 156 ° C)
-Solvent (F-3): xylene (solvent having no ketone structure; boiling point: 139 ° C)
-Solvent (F-4): 2-butanol (solvent having no ketone structure; boiling point: 108 ° C)
Solvent (F-5): Solvesso 150 (manufactured by Exxon Chemical Co., solvent having no ketone structure; boiling point: 195 ° C.)
Pigment: LOMON Titanium Dioxide R-996 (titanium oxide; manufactured by SICHUAN LOMON TITANIUM INDUSTRY)
・ Melamine resin: Cymel 303 (manufactured by Mitsui Cyanamid Co., Ltd.)
・ Curing catalyst: dodecylbenzene sulfonic acid
（実施例１）
塗料組成物１の調製
Ｋｙｎａｒ５００（固形分濃度：１００質量％）１９質量部、アクリル樹脂（Ｂ−１、固形分濃度：４０質量％）３１質量部、イソホロン２８質量部、シクロヘキサノン３質量部、キシレン１１質量部及び顔料１７質量部を混合し、サンドミル（分散媒体：ガラスビーズ）を用いて、顔料粗粒の最大粒子径が１０μｍ以下になるまで分散し、分散体組成物１を調製した。得られた分散体組成物１に、ＫＴＬ−２０Ｎ ５．５質量部、ハイディスパー１２５０ ３質量部、サイリシア４３５ ０．５質量部及びガンツパールＧＭ−１００１ １．５質量部を加えて、ディスパーで均一に混合し、塗料組成物１を調製した。
(Example 1)
Preparation of
（実施例２〜２９、比較例１〜９）
各成分の種類及び量を、下記表１〜３に記載のように変更したこと以外は、実施例１と同様にして塗料組成物を調製した。なお、下記表１〜３中に記載の配合量は、荷姿を示し、例えば、アクリル樹脂（Ｂ）であれば、樹脂固形分及び溶剤分を合計した配合量（質量部）を示す。
上記塗料組成物のうち、比較例４、６、７および９については、顔料の最大粒子径が１０μｍ以下にならず、塗料組成物の調製ができなかった。
(Examples 2 to 29, Comparative Examples 1 to 9)
A coating composition was prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Tables 1 to 3 below. In addition, the compounding quantity described in the following Tables 1 to 3 shows a packing style, and, for example, in the case of acrylic resin (B), shows the compounding quantity (mass part) which totaled resin solid content and solvent content.
In Comparative Examples 4, 6, 7 and 9 of the above coating compositions, the maximum particle size of the pigment was not 10 μm or less, and the coating compositions could not be prepared.
（実施例３０）
各成分の種類及び量を、下記表２に記載のように変更し、更に、サイメル３０３ ５．０質量部（メラミン樹脂、三井サイアナミッド社製）及びドデシルベンゼンスルホン酸（硬化触媒）０．１質量部を加えたこと以外は、実施例１と同様にして塗料組成物を調製した。
(Example 30)
The type and amount of each component was changed as shown in Table 2 below, and further 5.0 parts by mass of Cymel 303 (melamine resin, manufactured by Mitsui Cyanamid) and 0.1 part by mass of dodecylbenzenesulfonic acid (curing catalyst). A coating composition was prepared in the same manner as in Example 1 except that parts were added.
スラット材の作製
（実施例Ｍ１）
表裏両面にクロメート処理（塗布量１５０ｍｇ／ｍ２）を施した亜鉛−アルミニウム合金めっき鋼板（３００ｍｍ×２００ｍ×０．３５ｍｍ）の裏面側に、スーパーラックＲ−９０（日本ペイント・インダストリアルコーティングス社製、エポキシ樹脂系塗料：塗料組成物４１）を、乾燥膜厚が５μｍとなるようにバーコーター塗装した後、素材最高到達温度２１０℃で６０秒間焼付けた後、ただちに水没、冷却させることで、裏面塗膜を形成した。
Preparation of slats (Example M1)
Superlace R-90 (manufactured by Nippon Paint Industrial Coatings Co., Ltd.) is provided on the back side of a zinc-aluminum alloy-plated steel sheet (300 mm x 200 m x 0.35 mm) that has been subjected to chromate treatment (coating amount 150 mg / m 2 ) on both sides. , Epoxy resin-based paint: A coating composition 41) was coated with a bar coater so that the dry film thickness was 5 μm, baked for 60 seconds at a maximum material reaching temperature of 210 ° C., immediately submerged in water, and then cooled. A coating film was formed.
一方、表面には、下塗り塗料として、ファインタフＧプライマー（日本ペイント・インダストリアルコーティングス社製、エポキシ樹脂系プライマー：塗料組成物４０）を、乾燥膜厚が５μｍになるようにバーコーター塗装した後、素材到達最高温度２１０℃となる条件で６０秒間焼付けを行い、下塗り塗膜を形成した。次に、製造例１で調製した塗料組成物１を、乾燥膜厚が１５μｍとなるようにバーコーター塗装した後、素材最高到達温度２５０℃で６０秒間焼付けた後、ただちに水没、冷却させることで、上塗り塗膜（塗膜１）を形成した。
このようにして、実施例Ｍ１に係るスラット材を作成した。
On the other hand, after applying a fine tough G primer (manufactured by Nippon Paint Industrial Coatings Co., Ltd., epoxy resin-based primer: coating composition 40) as a base coat on the surface by bar coater coating so that the dry film thickness becomes 5 μm Then, baking was performed for 60 seconds under the condition that the maximum material reaching temperature was 210 ° C. to form an undercoat coating film. Next, the
In this way, the slat material according to Example M1 was produced.
（実施例Ｍ２〜Ｍ３０及び比較例Ｍ１〜Ｍ９）
以下に示す表３及び表４で示した塗料組成物を用いたこと以外は、実施例Ｍ１と同様にして、実施例Ｍ２〜Ｍ３０及び比較例Ｍ１〜Ｍ９に係るスラット材を作成した。
(Examples M2 to M30 and Comparative Examples M1 to M9)
Slat materials according to Examples M2 to M30 and Comparative Examples M1 to M9 were prepared in the same manner as Example M1 except that the coating compositions shown in Tables 3 and 4 below were used.
（実施例Ｍ３１）
裏面塗膜として実施例１に示す塗膜の代わりに、表面と同様の塗料組成物、塗膜形成方法を用いて、塗膜を形成する以外は実施例Ｍ１と同様にして、実施例Ｍ３１に係るスラット材を作成した。
(Example M31)
Instead of the coating film shown in Example 1 as the back surface coating film, the same coating composition and coating film forming method as those for the front surface were used to form the coating film in the same manner as in Example M1 except that the coating film was formed. The slat material concerned was created.
（実施例Ｍ３２）
裏面塗膜として実施例Ｍ１０に示す塗膜の代わりに、表面と同様の塗料組成物、塗膜形成方法を用いて、塗膜を形成する以外は実施例Ｍ１０と同様にして、実施例Ｍ３２に係るスラット材を作成した。
(Example M32)
Instead of the coating film shown in Example M10 as the back surface coating film, the same coating composition and coating film forming method as those for the front surface were used, and the coating film was formed in the same manner as in Example M10 except that the coating film was formed. The slat material concerned was created.
評価方法及び評価基準
以下の評価を行った。評価結果を、表４〜６に示す。
塗膜外観の評価
塗膜外観の評価は、塗膜の平滑性を目視評価した。評価基準は次のとおりである。
目視評価は、スラット材の表面における、上塗り塗膜面について観察した。
○：凹み及びピンホールは認められない。（合格）
○△：若干の凹みは認められるが、ピンホールは認められない。（合格）
△：塗膜の一部に、凹み及びピンホールが認められる。（不合格）
×：凹み及びピンホールが全面に認められる。（不合格）
（２）耐繰り返し摩耗性の評価
耐繰り返し摩耗性の評価は、平面摩耗試験機Ｈ−２６４２（大栄科学精機製作所社製）を用いて行った。
具体的には、各実施例又は比較例で得られた塗装板（塗膜形成後のスラット材）の１枚を、押出試験機を用いて、塗装板の裏面が凸となるよう、３．５ｍｍ押出し、凸形状を有する評価用裏面塗装板を作成した。なお。凸部は曲面状である。
次に、試験機の固定面に、１５０ｍｍ×５０ｍｍの大きさを有する、別の試験板（評価用表面塗装板：平板）を、その表面が上に向くよう固定した。固定した評価用表面塗装板の表面上に、評価用裏面塗装板の凸部が接触するように評価用裏面塗装板を設置した。評価用裏面塗装板に、荷重２ｋｇ、往復速度３０回／分、往復距離１２０ｍｍ、往復回数２０，０００回の条件で往復摩擦を行った。
試験後、摩擦試験に付した評価用表面塗装板における傷付きの程度を目視評価した。評価基準は次のとおりである。
○：傷が下塗り塗膜に達していない。（合格）
○△：傷の一部が下塗り塗膜に達しているが、基材が露出していない。（合格）
△：基材の一部が露出している。（不合格）
×：完全に基材が露出している。（不合格）
Evaluation method and evaluation criteria The following evaluations were performed. The evaluation results are shown in Tables 4-6.
Evaluation of coating film appearance For the evaluation of coating film appearance, the smoothness of the coating film was visually evaluated. The evaluation criteria are as follows.
The visual evaluation was performed on the surface of the top coating film on the surface of the slat material.
◯: No dent or pinhole is observed. (Pass)
○ △: Some dents are recognized, but no pinholes are recognized. (Pass)
Δ: A dent and a pinhole are found in a part of the coating film. (failure)
X: A dent and a pinhole are recognized on the entire surface. (failure)
(2) Evaluation of repeated wear resistance The repeated wear resistance was evaluated using a plane wear tester H-2642 (manufactured by Daiei Kagaku Seiki Seisakusho).
Specifically, one of the coated plates (slat material after forming the coating film) obtained in each of the examples or comparative examples was used to make the back surface of the coated plate convex using an extrusion tester. 5 mm was extruded to form a backside coated plate for evaluation having a convex shape. Incidentally. The convex portion is curved.
Next, another test plate (surface-coated plate for evaluation: flat plate) having a size of 150 mm × 50 mm was fixed to the fixed surface of the tester so that the surface thereof faced upward. The backside coated plate for evaluation was placed so that the convex portions of the backside coated plate for evaluation were in contact with the surface of the fixed front side coated plate for evaluation. The back coated plate for evaluation was subjected to reciprocating friction under the conditions of a load of 2 kg, a reciprocating speed of 30 times / minute, a reciprocating distance of 120 mm, and a reciprocating number of 20,000 times.
After the test, the degree of scratches on the surface-coated evaluation plate subjected to the friction test was visually evaluated. The evaluation criteria are as follows.
◯: The scratch does not reach the undercoat coating film. (Pass)
B: Some of the scratches reach the undercoat film, but the base material is not exposed. (Pass)
Δ: Part of the base material is exposed. (failure)
X: The base material is completely exposed. (failure)
（３）耐砂塵傷付き性の評価
耐砂塵傷付き性の評価は、平面摩耗試験機Ｈ−２６４２（大栄科学精機製作所）を用いて行った。
試験機の固定面に、実施例及び比較例で得られた、１５０ｍｍ×５０ｍｍの大きさを有する、塗膜形成後の試験板（下方試験板）を、その表面が上に向くよう固定した。次に、試験板の表面に６号珪砂（三河珪石社製；最頻粒子径：２００μｍ）０．０５ｇを均一に散布した。
別の、８０ｍｍ×４０ｍｍの大きさを有する、塗膜形成後の試験板（上方試験板）を、上記硅砂を散布した下方試験板の上に、上方試験板の裏面が砂と接触するように配置し、５００ｇの荷重をかけ、上方試験板の長手方向に振動を付した。試験条件は、周期５０回／分、往復距離４０ｍｍ、試験時間５分で行った。
試験後、振動試験機に付した塗装板表面における傷付きの程度を目視評価した。評価基準は次のとおりである。
○：傷が下塗り塗膜に達していない。（合格）
○△：傷の一部が下塗り塗膜に達しているが、基材が露出していない。（合格）
△：基材の一部が露出している。（不合格）
×：完全に基材が露出している。（不合格）
(3) Evaluation of sand scratch resistance The sand scratch resistance was evaluated using a plane wear tester H-2642 (Daiei Kagaku Seiki Seisakusho).
The test plate (lower test plate) having a size of 150 mm × 50 mm obtained in Examples and Comparative Examples and having a coating film formed thereon (lower test plate) was fixed to the fixed surface of the tester so that the surface of the test plate faced upward. Next, 0.05 g of No. 6 silica sand (manufactured by Mikawa Silica Co., Ltd .; most frequent particle size: 200 μm) was uniformly sprayed on the surface of the test plate.
Another test plate after coating film formation (upper test plate) having a size of 80 mm × 40 mm was placed on the lower test plate on which the above-mentioned silica sand was sprinkled, so that the back surface of the upper test plate was in contact with sand. It was placed, a load of 500 g was applied, and vibration was applied in the longitudinal direction of the upper test plate. The test conditions were a cycle of 50 times / minute, a reciprocating distance of 40 mm, and a test time of 5 minutes.
After the test, the degree of scratches on the surface of the coated plate attached to the vibration tester was visually evaluated. The evaluation criteria are as follows.
◯: The scratch does not reach the undercoat coating film. (Pass)
B: Some of the scratches reach the undercoat film, but the base material is not exposed. (Pass)
Δ: Part of the base material is exposed. (failure)
X: The base material is completely exposed. (failure)
（４）耐候性の評価
各実施例及び比較例で得られた試験板を、サンシャインウエザーメーター（スガ試験機社製）を用いて、２，０００時間の促進耐候性試験を行った。運転条件は、ＪＩＳ Ｋ ５６００に準拠して行った。
促進耐候性試験後の各試験板の外観について、目視により評価を行った。評価基準は次のとおりである。
○：試験前の塗装板と外観変化が極めて少ない（合格）
○△：試験前の塗装板と外観変化が少ない（合格）
△：試験前の塗装板との外観変化が大きい（不合格）
×：試験前の塗装板との外観変化が極めて大きい（不合格）
(4) Evaluation of weather resistance The test plates obtained in each of the examples and comparative examples were subjected to an accelerated weather resistance test for 2,000 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.). The operating conditions were based on JIS K 5600.
The appearance of each test plate after the accelerated weather resistance test was visually evaluated. The evaluation criteria are as follows.
○: Very little change in appearance from the painted plate before the test (pass)
○ △: Little change in appearance from the painted plate before the test (pass)
Δ: Large change in appearance with the coated plate before the test (failed)
X: The appearance change with the painted plate before the test is extremely large (failed)
（５）経時加工性劣化の評価
各実施例及び比較例で得られた試験板を、幅５０ｍｍに切断し、２０℃の室内にて、加工性の試験を実施した。
具体的には、加工する試験片と同一の厚み（０．３５ｍｍ）の被塗板２枚を、加工する試験片（塗膜面を外側へ向ける）の内側にはさみ込み、１８０度密着折曲げをした。折曲げた先端を１０倍ルーペで観察し評価を行った。評価基準は次のとおりである。
上記試験を、塗装板製造直後と室温で１か月放置した後に行い、クラックの発生度合いの変化を評価した。
○：クラックの発生度合いが、直後と１か月後で変化なし。（合格）
○△：クラックの発生度合いの変化が、直後と１か月後で少ない。（合格）
△：クラックの発生度合いの変化が、直後と１か月後で大きい。（不合格）
×：クラックの発生度合いの変化が、直後と１か月後で極めて大きい。（不合格）
(5) Evaluation of Workability Deterioration Over Time The test plates obtained in each of the examples and comparative examples were cut into a width of 50 mm, and a workability test was performed in a room at 20 ° C.
Specifically, two coated plates having the same thickness (0.35 mm) as the test piece to be processed are sandwiched inside the test piece to be processed (the coating surface is directed to the outside), and 180 degree close contact bending is performed. did. The bent tip was observed with a 10 times magnifying glass and evaluated. The evaluation criteria are as follows.
The above test was conducted immediately after the production of the coated plate and after leaving it for 1 month at room temperature to evaluate the change in the degree of crack generation.
◯: The degree of crack generation did not change immediately after or one month later. (Pass)
B: The change in the degree of cracking is small immediately after and one month later. (Pass)
Δ: The change in the degree of crack generation is large immediately after and one month later. (failure)
X: The change in the degree of occurrence of cracks is extremely large immediately after and one month later. (failure)
実施例Ｍ１〜Ｍ３２で得られた試験板を、シャッタースラットとして使用することを想定し、加工を行った。その結果、いずれの試験板も塗膜の割れ、クラック等を生じること無く、所望の形状に加工できた。また、実施例Ｍ１〜Ｍ３０におけるスラットは、特に表面において良好な意匠性を有する。実施例Ｍ３１、及びＭ３２におけるスラットは、表面、裏面共に良好な意匠性を有している。
更に、実施例におけるスラットは、特に表面において、良好な耐食性、耐傷付き性及び滑り性（摺動性）を有している。
このように、本開示に係る塗料組成物であれば、優れた加工性、意匠性、耐候性、耐食性、耐傷付き性、耐摩耗性、耐砂塵傷付き性及び優れた摺動性を備える塗膜を形成できる。その上、本開示に係る塗料組成物であれば、シャッタースラット材の少なくとも片面に塗膜を形成することで、前述した種々の効果を奏することができる。
The test plates obtained in Examples M1 to M32 were processed assuming that they will be used as shutter slats. As a result, any test plate could be processed into a desired shape without causing cracks or cracks in the coating film. In addition, the slats in Examples M1 to M30 have good designability especially on the surface. The slats of Examples M31 and M32 have good designability on both the front and back surfaces.
Furthermore, the slats in the examples have good corrosion resistance, scratch resistance, and slidability (sliding property), especially on the surface.
As described above, the coating composition according to the present disclosure has excellent processability, designability, weather resistance, corrosion resistance, scratch resistance, wear resistance, dust scratch resistance, and excellent sliding property. A film can be formed. Moreover, the coating composition according to the present disclosure can achieve the above-mentioned various effects by forming a coating film on at least one surface of the shutter slat material.
その一方で、比較例Ｍ１において、塗料組成物は、本開示に係るポリテトラフルオロエチレン粒子（Ｃ）を含まないため、繰り返し摩耗性の著しく悪い塗膜が形成された。
比較例Ｍ２において、塗料組成物は、本開示に係るワックス（Ｄ）を含まないため、繰り返し摩耗性は不十分であり、更に、耐砂塵傷付き性が著しく悪い塗膜が形成された。
比較例Ｍ３において、塗料組成物は、本開示に係る骨材（Ｅ）を含まないため、繰り返し摩耗性及び耐砂塵傷付き性の著しく悪い塗膜が形成された。
比較例Ｍ４において、塗料組成物は、本開示に係る溶剤（Ｆ）を含まないため、塗膜を形成することができなかった。なお、塗膜の形成ができなかったため、表中に記載の物性等の評価も行っていない。
比較例Ｍ５において、塗料組成物は、本開示に係る熱硬化性アクリル樹脂を含まないので、経時加工性劣化の著しく悪い塗膜が形成された。
比較例Ｍ６及びＭ７において、塗料組成物は、本開示に係る所定の溶剤（Ｆ−１）を含まないため、塗膜を形成することができなかった。なお、塗膜の形成ができなかったため、表中に記載の物性等の評価も行っていない。
比較例Ｍ８において、塗料組成物は、本開示に係るポリフッ化ビニリデン樹脂（Ａ）を含まないので、塗膜外観、耐繰り返し摩耗性、耐砂塵傷付き性及び耐候性の著しく悪い塗膜が形成された。
比較例Ｍ９において、塗料組成物は、本開示に係る所定のアクリル樹脂（Ｂ）を含まないため、塗料の作成及び塗膜の形成ができなかった。また、顔料を十分に分散することもできなかった。なお、塗膜の形成ができなかったため、表中に記載の物性等の評価も行っていない。
On the other hand, in Comparative Example M1, since the coating composition did not contain the polytetrafluoroethylene particles (C) according to the present disclosure, a coating film having remarkably poor abrasion resistance was formed.
In Comparative Example M2, the coating composition did not contain the wax (D) according to the present disclosure, so that the repeated abrasion resistance was insufficient, and further, a coating film having remarkably poor dust scratch resistance was formed.
In Comparative Example M3, the coating composition did not contain the aggregate (E) according to the present disclosure, and thus a coating film having remarkably poor abrasion resistance and dust and scratch resistance was formed.
In Comparative Example M4, the coating composition could not form a coating film because it did not contain the solvent (F) according to the present disclosure. In addition, since the coating film could not be formed, the evaluation of the physical properties described in the table was not performed.
In Comparative Example M5, the coating composition did not contain the thermosetting acrylic resin according to the present disclosure, and thus a coating film with extremely poor deterioration in workability over time was formed.
In Comparative Examples M6 and M7, the coating composition could not form a coating film because it did not contain the predetermined solvent (F-1) according to the present disclosure. In addition, since the coating film could not be formed, the evaluation of the physical properties described in the table was not performed.
In Comparative Example M8, since the coating composition does not contain the polyvinylidene fluoride resin (A) according to the present disclosure, a coating film having significantly poor appearance, repetitive abrasion resistance, dust scratch resistance, and weather resistance is formed. Was done.
In Comparative Example M9, since the coating composition did not contain the predetermined acrylic resin (B) according to the present disclosure, the coating composition and the coating film could not be formed. Further, the pigment could not be sufficiently dispersed. In addition, since the coating film could not be formed, the evaluation of the physical properties described in the table was not performed.
本発明のプレコート金属板用塗料組成物は、優れた加工性及び意匠性に加えて、耐候性、耐食性、耐傷付き性及び耐摩耗性を有する塗膜を形成でき、更に、土壌及び粉塵等の物質に起因する傷付を大きく抑制可能な、耐砂塵傷付き性を備える塗膜を形成できる。 The coating composition for a precoated metal plate of the present invention has excellent processability and designability, and can form a coating film having weather resistance, corrosion resistance, scratch resistance and abrasion resistance, and further, such as soil and dust. It is possible to form a coating film having scratch resistance due to a substance, which can greatly suppress scratches caused by a substance.
１ シャッタースラット材
１０ 本開示に係るプレコート金属板用塗料組成物から形成された塗膜
２０ 金属板
３０ 塗料組成物から形成される塗膜
DESCRIPTION OF
Claims (13)
アクリル樹脂（Ｂ）と、
ポリテトラフルオロエチレン粒子（Ｃ）と、
ワックス（Ｄ）と、
骨材（Ｅ）と、
溶剤（Ｆ）とを含み、
前記アクリル樹脂（Ｂ）は、少なくとも１種の熱硬化性アクリル樹脂を含み、及び、
前記溶剤（Ｆ）は、ケトン構造を有する溶剤（Ｆ−１）を含み、
前記溶剤（Ｆ−１）は、沸点が１８０℃以上である、
プレコート金属板用塗料組成物。 Polyvinylidene fluoride resin (A),
Acrylic resin (B),
Polytetrafluoroethylene particles (C),
Wax (D),
Aggregate (E),
Including a solvent (F),
The acrylic resin (B) contains at least one thermosetting acrylic resin, and
The solvent (F) includes a solvent having a ketone structure (F-1),
The solvent (F-1) has a boiling point of 180 ° C. or higher,
Pre-coated metal plate coating composition.
前記ワックス（Ｄ）を、前記ポリフッ化ビニリデン樹脂（Ａ）の固形分とアクリル樹脂（Ｂ）の固形分との合計１００質量部に対して、固形分で０．５質量部以上５．０質量部以下含む、請求項１から５のいずれか１項に記載の塗料組成物。 10 parts by mass or more and 25 parts by mass or less of the polytetrafluoroethylene particles (C) with respect to a total of 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). 0.5 parts by mass or more in solid content of the wax (D) based on 100 parts by mass of the solid content of the polyvinylidene fluoride resin (A) and the solid content of the acrylic resin (B). The coating composition according to any one of claims 1 to 5, which comprises not more than 0.0 parts by mass.
前記溶剤（Ｆ−２）は、沸点が１８０℃未満である、
請求項１から７のいずれか１項に記載の塗料組成物。 The solvent (F) further contains a solvent having a ketone structure (F-2),
The solvent (F-2) has a boiling point of less than 180 ° C.,
The coating composition according to any one of claims 1 to 7.
前記プレコート金属板用塗料組成物を、前記金属板の到達温度が２３０℃以上２７０℃以下であり、乾燥及び硬化時間が２０秒以上１２０秒以下の条件下で、乾燥及び硬化させる工程を含む、
プレコート金属板の製造方法。 A step of coating the coating composition for a precoated metal plate according to any one of claims 1 to 8 on at least one surface of the metal plate so that the film thickness after curing is 10 μm or more and 25 μm or less,
Including a step of drying and curing the coating composition for a precoated metal plate under the condition that the ultimate temperature of the metal plate is 230 ° C. or higher and 270 ° C. or lower and the drying and curing time is 20 seconds or longer and 120 seconds or shorter.
Manufacturing method of precoated metal sheet.
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| PCT/JP2019/048533 WO2020129781A1 (en) | 2018-12-21 | 2019-12-11 | Coating composition for precoated metal plates, precoated metal plate and method for producing same |
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