JP2018059029A - Coating composition, coated article and fluorine-containing polymer - Google Patents
Coating composition, coated article and fluorine-containing polymer Download PDFInfo
- Publication number
- JP2018059029A JP2018059029A JP2016199312A JP2016199312A JP2018059029A JP 2018059029 A JP2018059029 A JP 2018059029A JP 2016199312 A JP2016199312 A JP 2016199312A JP 2016199312 A JP2016199312 A JP 2016199312A JP 2018059029 A JP2018059029 A JP 2018059029A
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- JP
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- Prior art keywords
- coating composition
- group
- fluoropolymer
- hydroxycycloalkyl
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000008199 coating composition Substances 0.000 title claims abstract description 75
- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000011737 fluorine Substances 0.000 title claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims abstract description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 70
- 239000004811 fluoropolymer Substances 0.000 claims description 69
- -1 hydroxyalkyl vinyl ether Chemical compound 0.000 claims description 68
- 239000011248 coating agent Substances 0.000 claims description 57
- 238000000576 coating method Methods 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 26
- 229920001567 vinyl ester resin Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000005350 hydroxycycloalkyl group Chemical group 0.000 claims description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 14
- 239000000049 pigment Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
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- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
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- 150000001875 compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
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- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
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- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、塗料組成物、塗装物品および含フッ素重合体に関する。 The present invention relates to a coating composition, a coated article, and a fluoropolymer.
従来から、フルオロオレフィンに基づく重合単位と他の単量体に基づく重合単位を含む含フッ素重合体を含有する塗料組成物が知られている。たとえば、特許文献１では、フルオロオレフィンと、２−ノルボルネン、２，５−ノルボルナジエン等の橋かけ脂環構造を有する単量体と、アリルアルコール等のエステル結合およびエーテル結合をいずれも有しないエチレン性単量体と、を共重合させて得られた含フッ素重合体を含有する塗料組成物が開示されている。 Conventionally, a coating composition containing a fluoropolymer containing a polymer unit based on a fluoroolefin and a polymer unit based on another monomer is known. For example, in Patent Document 1, a fluoroolefin, a monomer having a bridged alicyclic structure such as 2-norbornene and 2,5-norbornadiene, and an ethylenic compound having no ester bond and ether bond such as allyl alcohol. A coating composition containing a fluoropolymer obtained by copolymerizing with a monomer is disclosed.
含フッ素重合体を含有する塗料組成物は、環境負荷等の観点から、有機溶剤を実質的に含まない粉体塗料組成物として使用されるのが望しい場合もある。
また、塗料組成物を用いて形成された塗膜は、経年劣化（着色等）しにくいことが望ましい。
特許文献１に記載の橋かけ環構造を有する単量体に基づく重合単位を含む含フッ素重合体は、ガラス転移温度（Ｔｇ）が高く、粉体塗料組成物として使用でき、さらに、その塗膜は耐候性にも優れることが開示されている。
しかし、その塗装時の成膜性が低く、具体的には塗膜にピンホールが発生しやすい傾向があり、さらにその塗膜の柔軟性が低く、具体的にはクラックが生じやすい傾向があることを、本発明者らは知見している。
The coating composition containing the fluoropolymer may be desired to be used as a powder coating composition substantially free of an organic solvent from the viewpoint of environmental load and the like.
Moreover, it is desirable that the coating film formed using the coating composition is less likely to deteriorate over time (coloring or the like).
The fluorine-containing polymer containing a polymer unit based on a monomer having a crosslinked ring structure described in Patent Document 1 has a high glass transition temperature (Tg) and can be used as a powder coating composition. Is also excellent in weather resistance.
However, the film-forming property at the time of coating is low, specifically, there is a tendency that pinholes are likely to occur in the coating film, and the flexibility of the coating film is low, specifically, there is a tendency that cracks are likely to occur. The present inventors know that.
本発明は、上記課題に鑑みてなされたものであって、粉体化しやすく、成膜性と柔軟性に優れ、経年劣化（着色等）しにくい塗膜を形成できる塗料組成物の提供を目的とする。また、本発明は、塗装物品および含フッ素重合体の提供も目的とする。 The present invention has been made in view of the above problems, and it is an object of the present invention to provide a coating composition that can form a coating film that is easily powdered, excellent in film formability and flexibility, and hardly deteriorates over time (coloring, etc.). And Another object of the present invention is to provide a coated article and a fluoropolymer.
本発明者は、上記課題について鋭意検討した結果、塗料組成物に含まれる含フッ素重合体が、後述する式（１）〜式（６）で表される重合単位のうち少なくとも１つを有する重合単位（Ｚ）を所定量含有することで、所望の効果が得られることを見出し、本発明に至った。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
As a result of intensive studies on the above problems, the present inventor has a polymerization in which the fluorine-containing polymer contained in the coating composition has at least one of the polymer units represented by the formulas (1) to (6) described later. It has been found that a desired effect can be obtained by containing a predetermined amount of the unit (Z), and the present invention has been achieved.
That is, the present inventor has found that the above problem can be solved by the following configuration.
［１］
フルオロオレフィンに基づく重合単位（Ｘ）と、架橋性基を側鎖に有する重合単位（Ｙ）と、後述する式（１）〜式（６）で表される重合単位のうち少なくとも１つを有する重合単位（Ｚ）と、を含む含フッ素重合体を含有し、
上記重合単位（Ｚ）の含有量が、上記含フッ素重合体が有する全重合単位のうち、１〜５０モル％である、塗料組成物。
後述する式（１）〜（６）中、環を構成するメチレン基およびメチン基の水素原子は、それぞれ独立に、炭素数１〜３のアルキル基に置換されていてもよい。前記式（３）中、Ｒは炭素数１〜３のアルキル基を表す。
［２］
上記重合単位（Ｘ）が、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌに基づく重合単位である、［１］に記載の塗料組成物。
［３］
上記重合単位（Ｙ）が、ヒドロキシアルキルビニルエーテル、ヒドロキシシクロアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、ヒドロキシシクロアルキルアリルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシシクロアルキルビニルエステル、ヒドロキシアルキルアリルエステル、およびヒドロキシシクロアルキルアリルエステルから選択される少なくとも１種のヒドロキシ基を有する単量体に基づく重合単位である、［１］または［２］に記載の塗料組成物。
［４］
上記塗料組成物が、粉体塗料組成物である、［１］〜［３］のいずれか１つに記載の塗料組成物。
［５］
基材と、［１］〜［４］のいずれか１つに記載の塗料組成物により上記基材上に形成された塗膜と、を有する、塗装物品。
［６］
フルオロオレフィンに基づく重合単位（Ｘ）と、架橋性基を側鎖に有する重合単位（Ｙ）と、下式（１）〜下式（６）で表される重合単位のうち少なくとも１つを有する重合単位（Ｚ）と、を含む、含フッ素重合体であって、
上記重合単位（Ｚ）の含有量が、上記含フッ素重合体が有する全重合単位のうち、１〜５０モル％である、含フッ素重合体。
後述する式（１）〜（６）中、環を構成するメチレン基およびメチン基の水素原子は、それぞれ独立に、炭素数１〜３のアルキル基に置換されていてもよい。前記式（３）中、Ｒは炭素数１〜３のアルキル基を表す。
［７］
上記重合単位（Ｘ）が、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌに基づく重合単位である、［６］に記載の含フッ素重合体。
［８］
上記重合単位（Ｙ）が、ヒドロキシアルキルビニルエーテル、ヒドロキシシクロアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、ヒドロキシシクロアルキルアリルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシシクロアルキルビニルエステル、ヒドロキシアルキルアリルエステル、およびヒドロキシシクロアルキルアリルエステルから選択される少なくとも１種のヒドロキシ基を有する単量体に基づく重合単位である、［６］または［７］に記載の含フッ素重合体。
[1]
It has at least one of polymerized units (X) based on fluoroolefin, polymerized units (Y) having a crosslinkable group in the side chain, and polymerized units represented by formulas (1) to (6) described later. Containing a fluoropolymer containing polymerized units (Z),
The coating composition whose content of the said polymerization unit (Z) is 1-50 mol% among all the polymerization units which the said fluoropolymer has.
In formulas (1) to (6) to be described later, the hydrogen atoms of the methylene group and methine group constituting the ring may be independently substituted with an alkyl group having 1 to 3 carbon atoms. In said formula (3), R represents a C1-C3 alkyl group.
[2]
The coating composition according to [1], wherein the polymer unit (X) is a polymer unit based on CF 2 = CF 2 or CF 2 = CFCl.
[3]
The polymerized unit (Y) is a hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycycloalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ester, or hydroxycycloalkyl allyl ester. The coating composition according to [1] or [2], which is a polymerized unit based on a monomer having at least one hydroxy group selected from:
[4]
The coating composition according to any one of [1] to [3], wherein the coating composition is a powder coating composition.
[5]
A coated article comprising: a base material; and a coating film formed on the base material by the coating composition according to any one of [1] to [4].
[6]
It has at least one of polymerized units (X) based on fluoroolefin, polymerized units (Y) having a crosslinkable group in the side chain, and polymerized units represented by the following formulas (1) to (6). A fluoropolymer containing polymerized units (Z),
The fluoropolymer whose content of the said polymer unit (Z) is 1-50 mol% among all the polymerization units which the said fluoropolymer has.
In formulas (1) to (6) to be described later, the hydrogen atoms of the methylene group and methine group constituting the ring may be independently substituted with an alkyl group having 1 to 3 carbon atoms. In said formula (3), R represents a C1-C3 alkyl group.
[7]
The fluorine-containing polymer according to [6], wherein the polymer unit (X) is a polymer unit based on CF 2 = CF 2 or CF 2 = CFCl.
[8]
The polymerized unit (Y) is a hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycycloalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ester, or hydroxycycloalkyl allyl ester. The fluorine-containing polymer according to [6] or [7], which is a polymerized unit based on a monomer having at least one hydroxy group selected from:
本発明によれば、粉体化しやすく、成膜性と柔軟性に優れ、経年劣化（着色等）しにくい塗膜を形成できる塗料組成物を提供できる。また、本発明によれば、塗装物品および含フッ素重合体を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the coating composition which can form the coating film which is easy to pulverize, is excellent in film forming property and a softness | flexibility, and is hard to age deterioration (coloring etc.) can be provided. Moreover, according to this invention, a coated article and a fluoropolymer can be provided.
以下の用語の定義は、本明細書および特許請求の範囲にわたって適用される。
「重合単位」とは、単量体の重合により直接形成される繰り返し単位と、単量体の重合によって形成される繰り返し単位の一部を化学変換して得られる繰り返し単位との総称である。本発明における各重合単位の割合は、各単量体の仕込み量に基づいて算出する。
「（メタ）アクリレート」とは、「アクリレート」および「メタクリレート」の総称で、「（メタ）アクリル」とは、「アクリル」および「メタクリル」の総称である。
「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
The following definitions of terms apply throughout this specification and the claims.
“Polymerized unit” is a general term for a repeating unit directly formed by polymerization of a monomer and a repeating unit obtained by chemically converting a part of the repeating unit formed by polymerization of a monomer. The ratio of each polymerized unit in the present invention is calculated based on the charged amount of each monomer.
“(Meth) acrylate” is a generic term for “acrylate” and “methacrylate”, and “(meth) acryl” is a generic term for “acryl” and “methacryl”.
The numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
本発明の塗料組成物は、フルオロオレフィンに基づく重合単位（Ｘ）と、架橋性基を側鎖に有する重合単位（Ｙ）と、後述する式（１）〜式（６）で表される重合単位のうち少なくとも１つを有する重合単位（Ｚ）と、を含む含フッ素重合体を含有する。
本発明の塗料組成物によれば、粉体化しやすく、成膜性と柔軟性に優れ、経年劣化（着色等）しにくい塗膜を形成できる。この理由の詳細は未だ明らかになっていない部分もあるが、概ね以下の理由によると推測される。
本発明の塗料組成物に含まれる含フッ素重合体は、重合単位（Ｚ）に基づく、主鎖の炭素原子に直接結合したエーテル性酸素原子を有し、かつ、主鎖を構成する炭素原子が飽和単環構造を形成する。なお、上記エーテル性酸素原子は、上記飽和環構造に含まれるか、上記飽和環構造の置換基に含まれる。
そのため、含フッ素重合体のガラス転移温度が高くなり、塗料組成物の粉体化が容易になる。また、本発明における含フッ素重合体は、主鎖の炭素原子に直接結合したエーテル性酸素原子を有さない、橋掛け環の飽和脂肪族構造を含む含フッ素重合体（特許文献１に記載の含フッ素重合体）に比較して、立体障害が低いと考えられる。そのため、その塗装時の成膜性と、その塗膜の柔軟性とに優れると考えられる。
さらに、本発明における含フッ素重合体は、重合単位（Ｚ）を有するため、側鎖にエーテル性酸素原子を介して飽和脂肪族環構造が結合した含フッ素重合体に比較して、非晶性が高く、その塗膜透明性に優れるだけでなく、環構造基の脱離に伴う経年劣化（着色等）が抑制され得るとも考えられる。
The coating composition of the present invention comprises a polymerization unit (X) based on a fluoroolefin, a polymerization unit (Y) having a crosslinkable group in the side chain, and a polymerization represented by formulas (1) to (6) described later. And a fluoropolymer containing a polymerized unit (Z) having at least one of the units.
According to the coating composition of the present invention, it is possible to form a coating film that is easily powdered, excellent in film formability and flexibility, and hardly deteriorates over time (coloring, etc.). Although details of this reason have not yet been clarified, it is presumed that the reason is as follows.
The fluorine-containing polymer contained in the coating composition of the present invention has an etheric oxygen atom directly bonded to a carbon atom of the main chain based on the polymer unit (Z), and the carbon atoms constituting the main chain are A saturated monocyclic structure is formed. The etheric oxygen atom is included in the saturated ring structure or is included in a substituent of the saturated ring structure.
Therefore, the glass transition temperature of the fluoropolymer is increased, and the coating composition is easily powdered. Further, the fluoropolymer in the present invention is a fluoropolymer having a saturated aliphatic structure of a bridged ring that does not have an etheric oxygen atom directly bonded to a carbon atom of the main chain (described in Patent Document 1). It is considered that the steric hindrance is lower than that of the fluoropolymer). Therefore, it is thought that the film-forming property at the time of the coating and the flexibility of the coating film are excellent.
Furthermore, since the fluoropolymer in the present invention has a polymer unit (Z), it is amorphous compared to a fluoropolymer having a saturated aliphatic ring structure bonded to the side chain via an etheric oxygen atom. In addition to being excellent in transparency of the coating film, it is considered that aging (coloring and the like) associated with elimination of the ring structure group can be suppressed.
含フッ素重合体における重合単位（Ｘ）は、フルオロオレフィンに基づく重合単位であり、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＦＣＦ３またはＣＦ２＝ＣＨ２に基づく重合単位が好ましく、重合単位（Ｙ）および重合単位（Ｚ）を形成する単量体との共重合性の観点から、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌが特に好ましい。フルオロオレフィンは、１種のみを用いてもよいし、２種以上を組み合わせて用いてもよい。 The polymer unit (X) in the fluoropolymer is a polymer unit based on a fluoroolefin, preferably a polymer unit based on CF 2 = CF 2 , CF 2 = CFCl, CF 2 = CFCF 3 or CF 2 = CH 2 , From the viewpoint of copolymerization with the monomer that forms the polymerized unit (Y) and the polymerized unit (Z), CF 2 ═CF 2 or CF 2 ═CFCl is particularly preferred. Only one type of fluoroolefin may be used, or two or more types may be used in combination.
重合単位（Ｘ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、２０〜７０モル％が好ましく、３０〜６０モル％がさらに好ましく、４０〜６０モル％が特に好ましい。重合単位（Ｘ）の含有量が上記下限値以上であれば、塗膜の耐候性がより優れる。重合単位（Ｘ）の含有量が上記上限値以下であれば、含フッ素重合体が非結晶性になりやすく、その塗膜の透明性、密着性、表面平滑性がより優れる。 The content of the polymerization unit (X) is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, and more preferably 40 to 60 mol%, of all the polymerization units (100 mol%) of the fluoropolymer. Particularly preferred. When the content of the polymerization unit (X) is not less than the above lower limit value, the weather resistance of the coating film is more excellent. When the content of the polymerization unit (X) is not more than the above upper limit, the fluoropolymer is likely to be amorphous, and the transparency, adhesion, and surface smoothness of the coating film are more excellent.
含フッ素重合体における重合単位（Ｙ）は、架橋性基を側鎖に有する重合単位である。本発明においては、含フッ素重合体が架橋性を有するので、塗膜形成時に、例えば、後述する硬化剤を使用して、塗膜を硬化させ、塗膜の耐候性、耐水性、耐薬品性、耐熱性等をより向上できる。
架橋性基としては、ヒドロキシ基、カルボキシ基、アミド基、アミノ基、メルカプト基、グリシジル基、ニトリル基、イソシアネート基、アルコキシシリル基などが挙げられる。
The polymer unit (Y) in the fluoropolymer is a polymer unit having a crosslinkable group in the side chain. In the present invention, since the fluoropolymer has crosslinkability, at the time of coating film formation, for example, using a curing agent described later, the coating film is cured, and the weather resistance, water resistance, chemical resistance of the coating film is cured. , Heat resistance and the like can be further improved.
Examples of the crosslinkable group include a hydroxy group, a carboxy group, an amide group, an amino group, a mercapto group, a glycidyl group, a nitrile group, an isocyanate group, and an alkoxysilyl group.
重合単位（Ｙ）は、架橋性基を側鎖に有し、重合単位（Ｘ）および重合単位（Ｚ）と共重合可能な重合性基を有する単量体（以下、単量体（ｙ）と記す。）に基づく重合単位であるのが好ましい。
単量体（ｙ）は、ヒドロキシアルキルビニルエーテル、ヒドロキシシクロアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、ヒドロキシシクロアルキルアリルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシシクロアルキルビニルエステル、ヒドロキシアルキルアリルエステル、ヒドロキシシクロアルキルアリルエステル等のヒドロキシ基を有する単量体、（メタ）アクリル酸、コハク酸、無水コハク酸、ビニル酢酸、クロトン酸、桂皮酸、３−アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、無水マレイン酸、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニル等のカルボキシ基を有する単量体、グリシジル（メタ）アクリレート、グリシジルビニルエーテル、グリシジルアリルエーテル等のグリシジル基を有する単量体、アミノアルキルビニルエーテル、アミノアルキルアリルエーテル等のアミノ基を有する単量体、（メタ）アクリルアミド、メチロール（メタ）アクリルアミド等のアミド基を有する単量体、（メタ）アクリロニトリル等のニトリル基を有する単量体、ビニルイソシアネート、イソシアネートエチルアクリレート等のイソシアネート基を有する単量体等が挙げられる。なお、単量体（ｙ）中の炭素原子−水素結合を形成する水素原子の一部は、フッ素原子で置換されていてもよい。また、単量体（ｙ）は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
単量体（ｙ）は、ヒドロキシ基を有する単量体が好ましく、ヒドロキシアルキルビニルエーテル、ヒドロキシシクロアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、ヒドロキシシクロアルキルアリルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシシクロアルキルビニルエステル、ヒドロキシアルキルアリルエステル、およびヒドロキシシクロアルキルアリルエステルから選択される少なくとも１種の単量体がより好ましい。
The polymerization unit (Y) is a monomer having a crosslinkable group in the side chain and a polymerizable group copolymerizable with the polymerization unit (X) and the polymerization unit (Z) (hereinafter, monomer (y). The polymerization unit is preferably based on the following formula.
Monomer (y) is hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycycloalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ester, hydroxycycloalkyl allyl ester, etc. Monomers having a hydroxy group, (meth) acrylic acid, succinic acid, succinic anhydride, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic Monomers having a carboxy group such as acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, glycidyl (meth) acrylate Monomers having a glycidyl group such as glycidyl vinyl ether and glycidyl allyl ether, monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether, and amide groups such as (meth) acrylamide and methylol (meth) acrylamide Monomers, monomers having a nitrile group such as (meth) acrylonitrile, monomers having an isocyanate group such as vinyl isocyanate and isocyanate ethyl acrylate, and the like. In addition, a part of hydrogen atom which forms the carbon atom-hydrogen bond in the monomer (y) may be substituted with a fluorine atom. Moreover, a monomer (y) may be used individually by 1 type, and may be used in combination of 2 or more type.
The monomer (y) is preferably a monomer having a hydroxy group, and hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycycloalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxy More preferred are at least one monomer selected from alkyl allyl esters and hydroxycycloalkyl allyl esters.
ヒドロキシアルキルビニルエーテルとしては、２−ヒドロキシエチルビニルエーテル、３−ヒドロキシプロピルビニルエーテル、２−ヒドロキシプロピルビニルエーテル、２−ヒドロキシ−２−メチルプロピルビニルエーテル、４−ヒドロキシブチルビニルエーテル、４−ヒドロキシ−２−メチルブチルビニルエーテル、５−ヒドロキシペンチルビニルエーテル、６−ヒドロキシヘキシルビニルエーテル等が挙げられる。
ヒドロキシシクロアルキルビニルエーテルとしては、４−ヒドロキシシクロヘキシルビニルエーテル等が挙げられる。
ヒドロキシアルキルアリルエーテルとしては、２−ヒドロキシエチルアリルエーテル、４−ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどが挙げられる。
ヒドロキシシクロアルキルアリルエーテルとしては、４−ヒドロキシシクロヘキシルアリルエーテル等が挙げられる。
ヒドロキシアルキルビニルエステルとしては、ヒドロキシ酢酸ビニル、ヒドロキシプロピオン酸ビニル、ヒドロキシ酪酸ビニル、ヒドロキシ吉草酸ビニル、ヒドロキシイソ酪酸ビニル等が挙げられる。
ヒドロキシシクロアルキルビニルエステルとしては、ヒドロキシシクロヘキシルカルボン酸ビニル等が挙げられる。
ヒドロキシアルキルアリルエステルとしては、ヒドロキシエチルアリルエステル、ヒドロキシプロピルアリルエステル、ヒドロキシブチルアリルエステル、ヒドロキシイソブチルアリルエステル等が挙げられる。
ヒドロシキシクロアルキルアリルエステルとしては、ヒドロキシシクロヘキシルアリルエステル等が挙げられる。
Examples of the hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, Examples include 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether.
Examples of the hydroxycycloalkyl vinyl ether include 4-hydroxycyclohexyl vinyl ether.
Examples of the hydroxyalkyl allyl ether include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like.
Examples of the hydroxycycloalkyl allyl ether include 4-hydroxycyclohexyl allyl ether.
Examples of hydroxyalkyl vinyl esters include vinyl vinyl acetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, and vinyl hydroxyisobutyrate.
Examples of the hydroxycycloalkyl vinyl ester include vinyl hydroxycyclohexylcarboxylate.
Examples of the hydroxyalkyl allyl ester include hydroxyethyl allyl ester, hydroxypropyl allyl ester, hydroxybutyl allyl ester, hydroxyisobutyl allyl ester, and the like.
Examples of the hydroxycycloalkyl allyl ester include hydroxycyclohexyl allyl ester.
重合単位（Ｙ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、０．５〜２０モル％が好ましく、１〜１５モル％がより好ましい。上記含有量が上記下限値以上であれば、塗膜の硬化性と基材密着性がより向上する。上記含有量が上記上限値以下であれば、塗膜の耐擦傷性が優れる。 The content of the polymerization unit (Y) is preferably from 0.5 to 20 mol%, more preferably from 1 to 15 mol%, based on the total polymerization units (100 mol%) of the fluoropolymer. If the said content is more than the said lower limit, the sclerosis | hardenability of a coating film and base-material adhesiveness will improve more. If the said content is below the said upper limit, the abrasion resistance of a coating film will be excellent.
含フッ素重合体における重合単位（Ｚ）は、下式（１）〜下式（６）で表される重合単位のうち少なくとも１つを有する重合単位であり、重合体の主鎖の炭素原子に直接結合したエーテル性酸素原子を有し、かつ、主鎖を構成する炭素原子が飽和単環構造を有する重合単位である。なお、上記エーテル性酸素原子は、上記飽和環構造に含まれるか、上記飽和環構造の置換基に含まれる。 The polymer unit (Z) in the fluoropolymer is a polymer unit having at least one of the polymer units represented by the following formulas (1) to (6), and is attached to the carbon atom of the main chain of the polymer. A polymer unit having a directly bonded etheric oxygen atom and a carbon atom constituting the main chain having a saturated monocyclic structure. The etheric oxygen atom is included in the saturated ring structure or is included in a substituent of the saturated ring structure.
式（１）〜（６）中、環を構成するメチレン基およびメチン基の水素原子は、それぞれ独立に、炭素数１〜３のアルキル基に置換されていてもよい。
式（３）中、Ｒは炭素数１〜３のアルキル基を表す。
In formulas (1) to (6), the hydrogen atoms of the methylene group and methine group constituting the ring may each independently be substituted with an alkyl group having 1 to 3 carbon atoms.
In formula (3), R represents an alkyl group having 1 to 3 carbon atoms.
重合単位（Ｘ）および（Ｙ）を形成する単量体との共重合性の観点から、式（１）〜式（６）で表される重合単位は、それぞれ、下記式（１ａ）〜下記式（６ａ）で表される単量体に基づく重合単位が好ましい。 From the viewpoint of copolymerization with the monomers forming the polymerization units (X) and (Y), the polymerization units represented by the formulas (1) to (6) are represented by the following formulas (1a) to (6), respectively. Polymerized units based on the monomer represented by formula (6a) are preferred.
式（１ａ）〜式（６ａ）中、環を構成するメチレン基およびメチン基の水素原子は、それぞれ独立に、炭素数１〜３のアルキル基に置換されていてもよい。
式（３ａ）中、Ｒの定義は、前述の通りである。
重合単位（Ｚ）は、本発明の効果がより発揮される観点から、式（１）または式（２）で表される重合単位が好ましい。
In formula (1a) to formula (6a), the hydrogen atoms of the methylene group and methine group constituting the ring may each independently be substituted with an alkyl group having 1 to 3 carbon atoms.
In formula (3a), the definition of R is as described above.
The polymerized unit (Z) is preferably a polymerized unit represented by the formula (1) or the formula (2) from the viewpoint of more exerting the effects of the present invention.
重合単位（Ｚ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、１〜５０モル％であり、５〜４０モル％が好ましい。上記含有量が上記上限値以下であれば、ピンホールの抑制に代表される成膜性とクラック発生の抑制に代表される柔軟性とに優れ、耐候性にも優れる。また、上記含有量が上記下限値以上であれば、含フッ素重合体のガラス転移温度が向上し、粉体塗料組成物を調整しやすい。 Content of a superposition | polymerization unit (Z) is 1-50 mol% among all the polymerization units (100 mol%) which a fluoropolymer has, and 5-40 mol% is preferable. When the content is not more than the above upper limit, the film formability typified by suppression of pinholes and the flexibility typified by suppression of crack generation are excellent, and the weather resistance is also excellent. Moreover, if the said content is more than the said lower limit, the glass transition temperature of a fluoropolymer will improve and it will be easy to adjust a powder coating composition.
本発明における含フッ素重合体は、重合単位（Ｘ）、重合単位（Ｙ）および重合単位（Ｚ）以外の他の重合単位を含んでいてもよい。
他の重合単位は、具体的には、式（１ａ）〜式（６ａ）で表される化合物以外の単量体であって、フッ素原子および架橋性基（架橋性基の具体例は前述の通りである。）をいずれも含まず、重合性基（例えば、ラジカル重合性不飽和基など）を含む単量体に基づく重合単位が好ましい。
他の重合単位の具体例としては、以下の重合単位（Ｉ）〜重合単位（Ｖ）が挙げられる。
The fluorine-containing polymer in the present invention may contain a polymer unit other than the polymer unit (X), polymer unit (Y), and polymer unit (Z).
The other polymerized units are specifically monomers other than the compounds represented by the formulas (1a) to (6a), and a fluorine atom and a crosslinkable group (specific examples of the crosslinkable group are described above). Polymeric units based on monomers that contain no polymerizable groups and contain polymerizable groups (such as radically polymerizable unsaturated groups) are preferred.
Specific examples of the other polymerized units include the following polymerized units (I) to polymerized units (V).
重合単位（Ｉ）は、式（１ａ）〜式（６ａ）で表される化合物以外の単量体であって、フッ素原子および架橋性基をいずれも含まず、側鎖に環式飽和炭化水素基を有する単量体（ｉ）に基づく重合単位である。
単量体（ｉ）の具体例としては、シクロヘキシルビニルエーテル、２−エチルへキシルビニルエーテルが挙げられる。
重合単位（Ｉ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、０〜５０モル％が好ましく、１０〜４０モル％が特に好ましい。
The polymerization unit (I) is a monomer other than the compounds represented by the formulas (1a) to (6a), does not contain any fluorine atom or crosslinkable group, and has a cyclic saturated hydrocarbon in the side chain. It is a polymerization unit based on the monomer (i) having a group.
Specific examples of the monomer (i) include cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether.
The content of the polymerization unit (I) is preferably from 0 to 50 mol%, particularly preferably from 10 to 40 mol%, based on the total polymerization units (100 mol%) of the fluoropolymer.
重合単位（ＩＩ）は、式（１ａ）〜式（６ａ）で表される化合物以外の単量体であって、フッ素原子、架橋性基および環式飽和炭化水素基のいずれも含まず、側鎖に芳香族基を含む単量体（ｉｉ）に基づく重合単位である。
単量体（ｉｉ）の具体例としては、安息香酸ビニル、パラ−ｔ−ブチル安息香酸ビニルなどの安息香酸ビニルモノマーが挙げられる。
重合単位（ＩＩ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、０〜４０モル％が好ましく、０〜２０モル％がより好ましい。
The polymerization unit (II) is a monomer other than the compounds represented by the formulas (1a) to (6a), and does not include any of a fluorine atom, a crosslinkable group, and a cyclic saturated hydrocarbon group. It is a polymerized unit based on the monomer (ii) containing an aromatic group in the chain.
Specific examples of the monomer (ii) include vinyl benzoate monomers such as vinyl benzoate and vinyl para-t-butylbenzoate.
The content of the polymerization unit (II) is preferably from 0 to 40 mol%, more preferably from 0 to 20 mol%, based on the total polymerization units (100 mol%) of the fluoropolymer.
重合単位（ＩＩＩ）は、式（１ａ）〜式（６ａ）で表される化合物以外の単量体であって、フッ素原子、架橋性基、環式飽和炭化水素基および芳香族基のいずれも含まない単量体（ｉｉｉ）に基づく重合単位である。
単量体（ｉｉｉ）の具体例としては、アルキルビニルエーテル（ノニルビニルエーテル、２−エチルヘキシルビニルエーテル、ヘキシルビニルエーテル、エチルビニルエーテル、ｎ−ブチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル等）、アルキルアリルエーテル（エチルアリルエーテル、ヘキシルアリルエーテル等）、カルボン酸（酢酸、酪酸、ピバリン酸、プロピオン酸、バーサチック酸、ラウリン酸、ステアリン酸等）のビニルエステル、カルボン酸（酢酸、酪酸、ピバリン酸、プロピオン酸、バーサチック酸、ラウリン酸、ステアリン酸等）のアリルエステル、エチレン、プロピレン、イソブチレン等が挙げられる。
重合単位（ＩＩＩ）の含有量は、含フッ素重合体が有する全重合単位（１００モル％）のうち、０〜５０モル％が好ましく、０〜４０モル％が特に好ましい。
The polymerization unit (III) is a monomer other than the compounds represented by the formulas (1a) to (6a), and any of a fluorine atom, a crosslinkable group, a cyclic saturated hydrocarbon group, and an aromatic group. It is a polymerization unit based on the monomer (iii) not contained.
Specific examples of the monomer (iii) include alkyl vinyl ether (nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, etc.), alkyl allyl ether (ethyl allyl ether, hexyl). Allyl ethers), carboxylic acids (acetic acid, butyric acid, pivalic acid, propionic acid, versatic acid, lauric acid, stearic acid, etc.) vinyl esters, carboxylic acids (acetic acid, butyric acid, pivalic acid, propionic acid, versatic acid, lauric acid) , Stearic acid and the like), ethylene, propylene, isobutylene and the like.
The content of the polymerization unit (III) is preferably from 0 to 50 mol%, particularly preferably from 0 to 40 mol%, based on the total polymerization units (100 mol%) of the fluoropolymer.
本発明における含フッ素重合体の数平均分子量は、その塗膜の耐水性と表面平滑性の観点から、３，０００〜５０，０００が好ましく、５，０００〜３０，０００がより好ましい。本明細書において、数平均分子量および質量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）法によってポリスチレン換算で求めた値である。 The number average molecular weight of the fluoropolymer in the present invention is preferably from 3,000 to 50,000, more preferably from 5,000 to 30,000, from the viewpoint of the water resistance and surface smoothness of the coating film. In the present specification, the number average molecular weight and the mass average molecular weight are values obtained in terms of polystyrene by a gel permeation chromatography (GPC) method.
本発明における含フッ素重合体のフッ素含有量は、その塗膜の耐候性と表面平滑性の観点から、１０〜７０質量％が好ましく、１５〜５０質量％以上がより好ましく、２５質量％以上が特に好ましい。また、該フッ素含有量は、７０質量％以下が好ましい。含フッ素重合体中のフッ素含有量は、核磁気共鳴（ＮＭＲ）分析により測定できる。 The fluorine content of the fluoropolymer in the present invention is preferably 10 to 70% by mass, more preferably 15 to 50% by mass or more, and 25% by mass or more from the viewpoint of the weather resistance and surface smoothness of the coating film. Particularly preferred. The fluorine content is preferably 70% by mass or less. The fluorine content in the fluoropolymer can be measured by nuclear magnetic resonance (NMR) analysis.
本発明における含フッ素重合体のガラス転移温度は、塗料組成物の粉体化と、塗膜の表面平滑性との観点から、５０〜１５０℃が好ましく、５０〜１００℃がより好ましく、５０〜７５℃がさらに好ましい。
なお、本明細書においてガラス転移温度は、示差走査熱量測定（ＤＳＣ）法で測定した中間点ガラス転移温度を意味する。
The glass transition temperature of the fluoropolymer in the present invention is preferably 50 to 150 ° C, more preferably 50 to 100 ° C, from the viewpoint of powdering the coating composition and the surface smoothness of the coating film, and 50 to More preferred is 75 ° C.
In addition, in this specification, a glass transition temperature means the midpoint glass transition temperature measured by the differential scanning calorimetry (DSC) method.
本発明の塗料組成物における、含フッ素重合体の含有量（固形分）は、塗料組成物の全質量（固形分）に対して、２０〜９９質量％が好ましい。なお、「固形分」とは、溶剤などを含まず、塗膜を構成し得る成分（塗膜の原料）を意図する。 The content (solid content) of the fluoropolymer in the coating composition of the present invention is preferably 20 to 99 mass% with respect to the total mass (solid content) of the coating composition. In addition, "solid content" intends the component (raw material of a coating film) which does not contain a solvent etc. and can comprise a coating film.
本発明における含フッ素重合体の製造方法は、特に限定されず、溶媒とラジカル開始剤の存在下、重合単位（Ｘ）〜重合単位（Ｚ）を構成するそれぞれの単量体を、ラジカル共重合させる方法が挙げられる。重合法は、特に限定されず、溶液重合法、懸濁重合法、乳化重合法が挙げられる。
ラジカル共重合における反応温度は、０〜１３０℃が好ましい。反応時間は１〜５０時間が好ましい。
ラジカル共重合における溶媒としては、エタノール、ブタノール、プロパノール等のアルコール系溶剤、ｎ−へキサン、ｎ−ヘプタン等の飽和炭化水素系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤が挙げられる。
ラジカル重合開始剤としては、パーオキシジカーボネート類、パーオキシエステル類、ケトンパーオキサイド類、パーオキシケタール類、パーオキシカーボネートエステル類、ジアシルパーオキサイド類、ジアルキルパーオキサイド類等が挙げられる。
The production method of the fluoropolymer in the present invention is not particularly limited. In the presence of a solvent and a radical initiator, each monomer constituting the polymerization unit (X) to the polymerization unit (Z) is radical copolymerized. The method of letting it be mentioned. The polymerization method is not particularly limited, and examples thereof include a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
The reaction temperature in radical copolymerization is preferably 0 to 130 ° C. The reaction time is preferably 1 to 50 hours.
Solvents for radical copolymerization include alcohol solvents such as ethanol, butanol and propanol, saturated hydrocarbon solvents such as n-hexane and n-heptane, aromatic hydrocarbon solvents such as toluene and xylene, methyl ethyl ketone and cyclohexanone. And ketone solvents such as ethyl acetate, and ester solvents such as ethyl acetate and butyl acetate.
Examples of the radical polymerization initiator include peroxydicarbonates, peroxyesters, ketone peroxides, peroxyketals, peroxycarbonate esters, diacyl peroxides, dialkyl peroxides, and the like.
本発明の塗料組成物は、溶液タイプ（すなわち、有機溶剤、水などの媒体を含有する塗料組成物）であってもよいが、上述したとおり、含フッ素重合体の粉体化が容易であるため、上記媒体を実質的に含有しない粉体塗料組成物として好適に使用される。
本明細書において、「媒体を実質的に含有しない」とは、塗料組成物中の媒体の含有量が概ね１質量％以下であることをいい、好ましくは０．５質量％以下、より好ましくは０．１質量％以下、さらに好ましくは０質量％である。
The coating composition of the present invention may be of a solution type (that is, a coating composition containing a medium such as an organic solvent or water). However, as described above, the fluoropolymer can be easily powdered. Therefore, it is suitably used as a powder coating composition substantially free of the above medium.
In the present specification, “substantially no medium” means that the content of the medium in the coating composition is approximately 1% by mass or less, preferably 0.5% by mass or less, more preferably It is 0.1 mass% or less, More preferably, it is 0 mass%.
つまり、本発明における含フッ素重合体は、粉末状であることが好ましい。含フッ素重合体の平均粒子径（５０％体積平均粒子径）は、特に限定されず、５〜１００μｍが好ましい。下限値は、１５μｍ以上がより好ましい。また、上限値は６０μｍ以下がより好ましい。
平均粒子径が５μｍ以上であれば、含フッ素重合体の凝集性が低くなり、粉体塗装の際に均一に塗装しやすい。また、平均粒子径が１００μｍ以下であれば、塗膜の表面平滑性がより良好になり、塗膜の外観がよい。
なお、含フッ素重合体の平均粒子径は、レーザー回折法を測定原理とした公知の粒度分布測定装置（例えば、Ｓｙｍｐａｔｅｃ社製、商品名「Ｈｅｌｏｓ−Ｒｏｄｏｓ」）を用いて測定された粒度分布より体積平均を算出して求められる。
That is, the fluorine-containing polymer in the present invention is preferably in a powder form. The average particle diameter (50% volume average particle diameter) of the fluoropolymer is not particularly limited, and is preferably 5 to 100 μm. The lower limit is more preferably 15 μm or more. The upper limit is more preferably 60 μm or less.
When the average particle diameter is 5 μm or more, the cohesiveness of the fluoropolymer is lowered, and it is easy to coat uniformly during powder coating. Moreover, if an average particle diameter is 100 micrometers or less, the surface smoothness of a coating film will become more favorable and the external appearance of a coating film will be good.
The average particle size of the fluoropolymer is determined from the particle size distribution measured using a known particle size distribution measuring apparatus (for example, product name “Helos-Rodos” manufactured by Sympatec, Inc.) based on the laser diffraction method. It is obtained by calculating the volume average.
本発明の塗料組成物は、ポリエステル樹脂、（メタ）アクリル樹脂およびエポキシ樹脂からなる群より選択される少なくとも１種の樹脂（以下、「他の樹脂」ともいう。）を含有してもよい。なお、この場合には、その塗膜において、基材上に、他の樹脂を主とする層と、含フッ素重合体を主とする層とが、この順に積層した塗膜が得られやすい観点から、含フッ素重合体のＳＰ値と、他の樹脂のＳＰ値との差は、絶対値として０．４〜１６（Ｊ／ｃｍ３）１／２が好ましい。 The coating composition of the present invention may contain at least one resin selected from the group consisting of a polyester resin, a (meth) acrylic resin, and an epoxy resin (hereinafter also referred to as “other resin”). In this case, in the coating film, it is easy to obtain a coating film in which a layer mainly composed of another resin and a layer mainly composed of a fluoropolymer are laminated in this order on the substrate. Therefore, the difference between the SP value of the fluoropolymer and the SP value of the other resin is preferably 0.4 to 16 (J / cm 3 ) 1/2 as an absolute value.
他の樹脂を含む場合、本発明の塗料組成物における、含フッ素重合体と他の樹脂の質量比（含フッ素重合体の質量／他の樹脂の質量）は、塗膜の耐候性、耐酸性および隠蔽性の観点から、０．３〜３．５が好ましく、０．３５〜３が特に好ましい。 When other resins are included, the mass ratio of the fluoropolymer to the other resin (the mass of the fluoropolymer / the mass of the other resin) in the coating composition of the present invention is the weather resistance and acid resistance of the coating film. And from a concealing viewpoint, 0.3-3.5 are preferable and 0.35-3 are especially preferable.
他の樹脂は、塗膜の基材との密着性に優れる点、他の樹脂を主とする層に含フッ素重合体が混入しにくい点から、ポリエステル樹脂または（メタ）アクリル樹脂が好ましい。
ポリエステル樹脂としては、ダイセル・オルネクス社製の「ＣＲＹＬＣＯＡＴ（登録商標） ４６４２−３」、「ＣＲＹＬＣＯＡＴ（登録商標） ４８９０−０」、「ＣＲＹＬＣＯＡＴ（登録商標） ４８４２−３」、日本ユピカ社製の「ユピカコート（登録商標） ＧＶ−２５０」、「ユピカコート（登録商標） ＧＶ−７４０」、「ユピカコート（登録商標） ＧＶ−１７５」、ＤＳＭ社製の「Ｕｒａｌａｃ(登録商標) １６８０」等が挙げられる。
The other resin is preferably a polyester resin or a (meth) acrylic resin from the viewpoint that the adhesiveness of the coating film to the substrate is excellent and that the fluoropolymer is hardly mixed in a layer mainly composed of the other resin.
Examples of the polyester resin include “CRYLCOAT (registered trademark) 4642-3”, “CRYLCOAT (registered trademark) 4890-0”, “CRYLCOAT (registered trademark) 4842-3” manufactured by Daicel Ornex Corporation, “ Examples include "Iupica Coat (registered trademark) GV-250", "Iupica Coat (registered trademark) GV-740", "Iupica Coat (registered trademark) GV-175", "Uralac (registered trademark) 1680" manufactured by DSM.
（メタ）アクリル樹脂としては、ＤＩＣ社製の「ファインディック（登録商標） Ａ−２４９」、「ファインディック（登録商標） Ａ−２５１」、「ファインディック（登録商標） Ａ−２６６」、三井化学社製の「アルマテックス（登録商標） ＰＤ６２００」、「アルマテックス（登録商標） ＰＤ７３１０」、三洋化成工業社製の「サンペックス ＰＡ−５５」等が挙げられる。 As the (meth) acrylic resin, “Fine Dick (registered trademark) A-249”, “Fine Dick (registered trademark) A-251”, “Fine Dick (registered trademark) A-266” manufactured by DIC, Mitsui Chemicals, Inc. “Almatex (registered trademark) PD6200” manufactured by the company, “Almatex (registered trademark) PD7310”, “Sanpex PA-55” manufactured by Sanyo Chemical Industries, Ltd., and the like.
エポキシ樹脂としては、三菱化学社製の「エピコート（登録商標） １００１」、「エピコート（登録商標） １００２」、「エピコート（登録商標） ４００４Ｐ」、ＤＩＣ社製の「エピクロン（登録商標） １０５０」、「エピクロン（登録商標） ３０５０」、新日鉄住金化学社製の「エポトート（登録商標） ＹＤ−０１２」、「エポトート（登録商標） ＹＤ−０１４」、ナガセケムテックス社製の「デナコール（登録商標） ＥＸ−７１１」、ダイセル社製の「ＥＨＰＥ３１５０」等が挙げられる。 As the epoxy resin, “Epicoat (registered trademark) 1001”, “Epicoat (registered trademark) 1002”, “Epicoat (registered trademark) 4004P” manufactured by Mitsubishi Chemical Corporation, “Epicron (registered trademark) 1050” manufactured by DIC, "Epicron (registered trademark) 3050", "Epototo (registered trademark) YD-012" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "Epototo (registered trademark) YD-014", "Denacol (registered trademark) EX" manufactured by Nagase ChemteX Corporation -711 "," EHPE3150 "manufactured by Daicel Corporation, and the like.
本発明の塗料組成物は、さらに、防錆顔料、体質顔料、着色顔料等の顔料を含有してもよい。
防錆顔料としては、シアナミド亜鉛、酸化亜鉛、リン酸亜鉛、リン酸カルシウムマグネシウム、モリブデン酸亜鉛、ホウ酸バリウム、シアナミド亜鉛カルシウム等が挙げられる。
体質顔料としては、タルク、硫酸バリウム、マイカ、炭酸カルシウムが挙げられる。
The coating composition of the present invention may further contain pigments such as rust preventive pigments, extender pigments, and colored pigments.
Examples of the rust preventive pigment include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and calcium cyanamide zinc.
Examples of extender pigments include talc, barium sulfate, mica, and calcium carbonate.
着色顔料としては、キナクリドン、ジケトピロロピロール、イソインドリノン、インダンスロン、ペリレン、ペリノン、アントラキノン、ジオキサジン、ベンゾイミダゾロン、トリフェニルメタンキノフタロン、アントラピリミジン、黄鉛、フタロシアニン、ハロゲン化フタロシアニン、アゾ顔料（アゾメチン金属錯体、縮合アゾなど）、酸化チタン、カーボンブラック、酸化鉄、銅フタロシアニン、縮合多環類顔料などが挙げられる。
また、着色顔料として、光輝顔料も挙げられ、具体的には、金属粒子（アルミニウム、亜鉛、銅、ブロンズ、ニッケル、チタン、ステンレス等の金属およびそれらの合金等）、マイカ粒子（雲母粉）、パール粒子、グラファイト粒子、ガラスフレーク、鱗片状酸化鉄粒子が挙げられる。
Color pigments include quinacridone, diketopyrrolopyrrole, isoindolinone, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, triphenylmethanequinophthalone, anthrapyrimidine, yellow lead, phthalocyanine, halogenated phthalocyanine, azo Examples thereof include pigments (azomethine metal complex, condensed azo, etc.), titanium oxide, carbon black, iron oxide, copper phthalocyanine, and condensed polycyclic pigments.
Further, examples of the coloring pigment include bright pigments. Specifically, metal particles (metals such as aluminum, zinc, copper, bronze, nickel, titanium, and stainless steel and alloys thereof), mica particles (mica powder), Examples include pearl particles, graphite particles, glass flakes, and scale-like iron oxide particles.
本発明の塗料組成物における顔料の含有量は、塗料組成物の全質量（固形分）に対して、０〜４０質量％が好ましい。 As for content of the pigment in the coating composition of this invention, 0-40 mass% is preferable with respect to the total mass (solid content) of a coating composition.
本発明の塗料組成物は、さらに、硬化剤を含有してもよい。
本発明における含フッ素重合体は架橋性基を有するため、架橋性基と反応しうる硬化剤を用いることで、その塗膜物性（耐候性、耐酸性、隠蔽性等）をより向上させ得る。たとえば、含フッ素重合体の架橋性基が水酸基である場合には、イソシアナート基、またはブロック化イソシアナート基（加熱等によりイソシアナート基を形成する基）を有する硬化剤を用いることにより、塗膜において含フッ素重合体の架橋・高分子量化が可能である。
The coating composition of the present invention may further contain a curing agent.
Since the fluoropolymer in the present invention has a crosslinkable group, the physical properties of the coating film (weather resistance, acid resistance, hiding property, etc.) can be further improved by using a curing agent capable of reacting with the crosslinkable group. For example, when the crosslinkable group of the fluoropolymer is a hydroxyl group, it can be applied by using a curing agent having an isocyanate group or a blocked isocyanate group (a group that forms an isocyanate group by heating or the like). It is possible to crosslink and increase the molecular weight of the fluoropolymer in the film.
硬化剤は、ブロック化イソシアナート系硬化剤、アミン系硬化剤（メラミン樹脂、グアナミン樹脂、スルホアミド樹脂、尿素樹脂、アニリン樹脂等）、β−ヒドロキシアルキルアミド系硬化剤、トリグリシジルイソシアヌレート系硬化剤などが挙げられる。
含フッ素重合体および任意で用いられる他の樹脂の少なくとも一方が架橋性基として水酸基を有する場合、硬化剤としては、塗膜と基材との密着性、塗装製品の加工性、塗膜の耐水性に優れる点から、ブロック化イソシアナート系硬化剤が好ましい。
Curing agents include blocked isocyanate curing agents, amine curing agents (melamine resins, guanamine resins, sulfoamide resins, urea resins, aniline resins, etc.), β-hydroxyalkylamide curing agents, triglycidyl isocyanurate curing agents. Etc.
When at least one of the fluorine-containing polymer and other resin optionally used has a hydroxyl group as a crosslinkable group, the curing agent includes adhesion between the coating film and the substrate, processability of the coated product, water resistance of the coating film From the viewpoint of excellent properties, a blocked isocyanate curing agent is preferred.
なお、ブロック化イソシアナート系硬化剤は、ジイソシアナート化合物と、活性水素を有する低分子化合物と、を反応させて得たポリイソシアナートを、ブロック剤と反応させて製造できる。
ジイソシアナート化合物としては、トリレンジイソシアナート、４，４’−ジフェニルメタンイソシアナート、キシリレンジイソシアナート、ヘキサメチレンジイソシアナート、４，４’−メチレンビス（シクロヘキシルイソシアナート）、メチルシクロヘキサンジイソシアナート、ビス（イソシアナートメチル）シクロヘキサンイソホロンジイソシアナート、ダイマー酸ジイソシアナート、リジンジイソシアナートが挙げられる。
The blocked isocyanate curing agent can be produced by reacting a polyisocyanate obtained by reacting a diisocyanate compound with a low molecular weight compound having active hydrogen with a blocking agent.
Examples of the diisocyanate compound include tolylene diisocyanate, 4,4′-diphenylmethane isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), methylcyclohexane diisocyanate, Examples thereof include bis (isocyanatomethyl) cyclohexaneisophorone diisocyanate, dimer acid diisocyanate, and lysine diisocyanate.
活性水素を有する低分子化合物としては、水、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン、ソルビトール、エチレンジアミン、エタノールアミン、ジエタノールアミン、ヘキサメチレンジアミン、イソシアヌレート、ウレチジオン、水酸基を含有する低分子量ポリエステル、ポリカプロラクトンが挙げられる。
ブロック剤としては、アルコール類（メタノール、エタノール、ベンジルアルコール等）、フェノール類（フェノール、クレゾーン等）、ラクタム類（カプロラクタム、ブチロラクタム等）、オキシム類（シクロヘキサノン、オキシム、メチルエチルケトオキシム等）が挙げられる。
Low molecular weight compounds having active hydrogen include water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, ethanolamine, diethanolamine, hexamethylenediamine, isocyanurate, uretidione, a low molecular weight polyester containing a hydroxyl group, Polycaprolactone is mentioned.
Examples of the blocking agent include alcohols (methanol, ethanol, benzyl alcohol, etc.), phenols (phenol, crezone, etc.), lactams (caprolactam, butyrolactam, etc.), and oximes (cyclohexanone, oxime, methyl ethyl ketoxime, etc.).
本発明の塗料組成物が硬化剤を含む場合、硬化剤の含有量は、主体樹脂（含フッ素重合体および他の樹脂）の合計量１００質量部に対して、０．１〜５０．０質量部が好ましい。 When the coating composition of this invention contains a hardening | curing agent, content of a hardening | curing agent is 0.1-50.0 mass with respect to 100 mass parts of total amounts of main resin (fluoropolymer and other resin). Part is preferred.
本発明の塗料組成物は、硬化触媒を含有してもよい。
硬化触媒は、上述した硬化剤を用いた際の硬化反応を促進する化合物であり、具体的には、硬化剤としてブロック化イソシアナート系硬化剤を用いる場合の、スズ触媒（オクチル酸スズ、トリブチルスズラウレート、ジブチルスズジラウレート等）が挙げられる。
硬化触媒の含有量は、上記硬化剤の添加量１００質量部（固形分）に対して、０．００００１〜０．０１質量部が好ましい。
The coating composition of the present invention may contain a curing catalyst.
The curing catalyst is a compound that accelerates the curing reaction when the above-described curing agent is used. Specifically, when a blocked isocyanate curing agent is used as the curing agent, a tin catalyst (tin octylate, tributyltin) is used. Laurate, dibutyltin dilaurate, etc.).
The content of the curing catalyst is preferably 0.00001 to 0.01 part by mass with respect to 100 parts by mass (solid content) of the curing agent.
本発明の塗料組成物は、必要に応じて上記以外の成分を含有してもよい。上記以外の成分としては、紫外線吸収剤（各種の有機系紫外線吸収剤、無機系紫外線吸収剤等）、光安定剤（ヒンダードアミン光安定剤等）、つや消し剤（超微粉合成シリカ等）、レベリング剤、表面調整剤（塗膜の表面平滑性を向上させる。）、脱ガス剤、可塑剤、充填剤、熱安定剤、増粘剤、分散剤、帯電防止剤、防錆剤、シランカップリング剤、防汚剤、低汚染化処理剤等が挙げられる。 The coating composition of this invention may contain components other than the above as needed. Components other than the above include UV absorbers (various organic UV absorbers, inorganic UV absorbers, etc.), light stabilizers (hindered amine light stabilizers, etc.), matting agents (ultra fine powder synthetic silica, etc.), leveling agents. , Surface conditioner (improves surface smoothness of coating film), degassing agent, plasticizer, filler, heat stabilizer, thickener, dispersant, antistatic agent, rust preventive agent, silane coupling agent , Antifouling agents, low-contamination treatment agents, and the like.
本発明の塗料組成物の製造方法は、上述した各成分の混合により得られる。以下において、本発明の塗料組成物の製造方法の一例として、塗料組成物を粉体塗料組成物として用いる場合を例に挙げて説明する。
まず、含フッ素重合体の粉体と、必要に応じて、他の成分（他の樹脂の粉体、顔料、硬化剤、硬化触媒、およびその他の添加剤）とをドライブレンドして混合物を得て、得られた混合物を８０〜１３０℃で溶融混練して溶融混練物を得る。次いで、得られた溶融混練物を冷却して、固化した溶融混練物を得る。そして、固化した溶融混練物を粉砕して分級することにより、所望の粒径の粉体塗料組成物を得ることができる。
The manufacturing method of the coating composition of this invention is obtained by mixing of each component mentioned above. Hereinafter, as an example of the method for producing a coating composition of the present invention, a case where the coating composition is used as a powder coating composition will be described as an example.
First, dry blend the fluoropolymer powder and, if necessary, other components (powder of other resin, pigment, curing agent, curing catalyst, and other additives) to obtain a mixture. Then, the obtained mixture is melt-kneaded at 80 to 130 ° C. to obtain a melt-kneaded product. Next, the obtained melt-kneaded product is cooled to obtain a solidified melt-kneaded product. And the powder coating composition of a desired particle size can be obtained by grind | pulverizing and classifying the solidified melt-kneaded material.
本発明の塗装物品は、基材と、上記塗料組成物により上記基材上に形成された塗膜と、を有する。
基材の材質としては、特に限定されず、無機物、有機物、有機無機複合材等が挙げられる。無機物としては、コンクリート、自然石、ガラス、金属（鉄、ステンレス、アルミニウム、銅、真鍮、チタン等）等が挙げられる。有機物としては、プラスチック、ゴム、接着剤、木材等が挙げられる。有機無機複合材としては、繊維強化プラスチック、樹脂強化コンクリート、繊維強化コンクリート等が挙げられる。
また、基材には、公知の表面処理（例えば、化成処理など）を行ったものを用いてもよい。また、基材の表面には、樹脂層（ポリエステル樹脂、アクリル樹脂など）が形成されていてもよい。
上記の中でも、基材は、金属が好ましく、アルミニウムが特に好ましい。アルミニウム製の基材は、防食性に優れ、軽量で、外装部材等の建築材料用途に適している。
基材の形状、サイズ等は、特に限定はされない。
基材の具体例としては、コンポジットパネル、カーテンウォール用パネル、カーテンウォール用フレーム、ウィンドウフレーム等の建築用の外装部材、タイヤホイール等の自動車部材、建機、自動２輪のフレーム等が挙げられる。
The coated article of this invention has a base material and the coating film formed on the said base material with the said coating composition.
The material for the substrate is not particularly limited, and examples thereof include inorganic materials, organic materials, and organic-inorganic composite materials. Examples of the inorganic material include concrete, natural stone, glass, metal (iron, stainless steel, aluminum, copper, brass, titanium, etc.). Examples of the organic material include plastic, rubber, adhesive, and wood. Examples of the organic / inorganic composite material include fiber reinforced plastic, resin reinforced concrete, and fiber reinforced concrete.
Moreover, you may use what performed well-known surface treatment (for example, chemical conversion etc.) for a base material. Further, a resin layer (polyester resin, acrylic resin, or the like) may be formed on the surface of the substrate.
Among the above, the substrate is preferably a metal, and particularly preferably aluminum. The base material made of aluminum is excellent in corrosion resistance, is lightweight, and is suitable for building material applications such as exterior members.
The shape, size, etc. of the substrate are not particularly limited.
Specific examples of the base material include composite exterior panels, curtain wall panels, curtain wall frames, architectural exterior members such as window frames, automobile members such as tire wheels, construction machinery, and motorcycle frames. .
塗膜の表面の水接触角は、１〜５５度が好ましく、３〜５０度がより好ましい。水接触角が上記下限値以上であれば、鳥の糞や虫の死骸に由来する有機酸成分により、塗膜が浸食されにくく、また、塗膜表層でのカビの発生が抑制される（カビの発生は、外観不良につながる）。水接触角が上記上限値以下であれば、耐汚染性に優れる。
水接触角は、例えば、協和界面科学社製の「ＤＭ−０５１」（商品名）を用いて測定される。
The water contact angle on the surface of the coating film is preferably 1 to 55 degrees, and more preferably 3 to 50 degrees. If the water contact angle is equal to or greater than the above lower limit value, the organic acid component derived from bird droppings or dead carcasses is less likely to erode the coating film, and the generation of mold on the coating surface layer is suppressed (molds). Occurrence leads to poor appearance). If a water contact angle is below the said upper limit, it will be excellent in stain resistance.
The water contact angle is measured using, for example, “DM-051” (trade name) manufactured by Kyowa Interface Science Co., Ltd.
塗膜の厚さは、特に制限されないが、２０〜１，０００μｍが好ましく、２０〜５００μｍがより好ましく、２０〜３００μｍがさらに好ましい。アルミニウムカーテンウォール等の高層ビル用の部材等の用途では、２０〜９０μｍが好ましい。海岸沿いに設置してあるエアコンの室外機、信号機のポール、標識等の耐候性の要求が高い用途では、１００〜２００μｍが好ましい。 The thickness of the coating film is not particularly limited, but is preferably 20 to 1,000 μm, more preferably 20 to 500 μm, and still more preferably 20 to 300 μm. In applications such as members for high-rise buildings such as aluminum curtain walls, 20 to 90 μm is preferable. For applications with high weather resistance requirements such as outdoor units of air conditioners, signal poles and signs installed along the coast, 100 to 200 μm is preferable.
本発明の塗装物品の製造方法は、これに限定されないが、（Ｉ）上述した塗料組成物を基材に塗装し、塗料組成物の溶融物からなる溶融膜を形成する工程（以下、工程（Ｉ）とも記す。）と、（ＩＩ）溶融膜を冷却して塗膜を形成する工程（以下、工程（ＩＩ）とも記す。）と、を有することが好ましい。 Although the manufacturing method of the coated article of this invention is not limited to this, (I) The process (henceforth process (hereinafter, process (1)) which coats the base material with the coating composition mentioned above, and forms the molten film which consists of a melt of a coating composition. And (II) a step of cooling the molten film to form a coating film (hereinafter also referred to as step (II)).
工程（Ｉ）は、上述した塗料組成物を基材に塗装して、該基材上に塗料組成物の溶融物からなる溶融膜を形成する工程である。塗料組成物の溶融物からなる溶融膜は、基材への粉体塗料組成物の塗装と同時に形成してもよく、基材に塗料組成物を付着させた後に基材上で塗料組成物を加熱溶融させて形成してもよい。
塗料組成物を加熱して溶融し、その溶融状態を所定時間維持するための加熱温度と加熱維持時間は、塗料組成物の原料成分の種類や組成、所望する塗膜の厚さ等により適宜設定される。該加熱温度は、通常１２０〜３００℃であり、該加熱維持時間は、通常２〜６０分間である。
Step (I) is a step of coating the above-described coating composition on a base material to form a molten film made of a melt of the coating composition on the base material. The molten film composed of the melt of the coating composition may be formed simultaneously with the coating of the powder coating composition on the substrate, and after the coating composition is attached to the substrate, the coating composition is applied on the substrate. It may be formed by heating and melting.
The heating temperature and the heating maintenance time for heating and melting the coating composition and maintaining the molten state for a predetermined time are appropriately set according to the type and composition of the raw material components of the coating composition, the desired coating thickness, etc. Is done. The heating temperature is usually 120 to 300 ° C., and the heating maintenance time is usually 2 to 60 minutes.
工程（ＩＩ）は、溶融状態の溶融膜を室温（２０〜２５℃）まで冷却して塗膜を形成する工程である。焼付け後の冷却は、急冷および徐冷のいずれでもよく、基材から塗膜がはがれにくい点で、徐冷が好ましい。 Step (II) is a step of forming a coating film by cooling the molten film in a molten state to room temperature (20 to 25 ° C.). Cooling after baking may be either rapid cooling or slow cooling, and slow cooling is preferred because the coating film is difficult to peel off from the substrate.
本発明の含フッ素重合体は、フルオロオレフィンに基づく重合単位（Ｘ）と、架橋性基を側鎖に有する重合単位（Ｙ）と、上述の式（１）〜式（６）で表される重合単位のうち少なくとも１つを有する重合単位（Ｚ）と、を含む、含フッ素重合体であって、重合単位（Ｚ）の含有量が、上記含フッ素重合体が有する全重合単位のうち、１〜５０モル％である。
すなわち、本発明の含フッ素重合体は、上述した塗料組成物に好適に使用されるが、これ以外の用途可能な有用な重合体である。
本発明の含フッ素重合体における重合単位（Ｘ）は、上述した本発明の塗料組成物において説明した重合単位（Ｘ）と同義であり、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌに基づく重合単位が特に好ましい。
本発明の含フッ素重合体における重合単位（Ｙ）は、上述した本発明の塗料組成物において説明した重合単位（Ｙ）と同義であり、ヒドロキシアルキルビニルエーテル、ヒドロキシシクロアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、ヒドロキシシクロアルキルアリルエーテル、ヒドロキシアルキルビニルエステル、ヒドロキシシクロアルキルビニルエステル、ヒドロキシアルキルアリルエステル、およびヒドロキシシクロアルキルアリルエステルから選択される少なくとも１種のヒドロキシ基を有する単量体に基づく重合単位が特に好ましい。
重合単位（Ｚ）（式（１）〜式（６）で表される重合単位）は、上述した本発明の塗料組成物において説明した重合単位（Ｚ）（式（１）〜式（６）で表される重合単位）と同義であるので、その説明を省略する。
The fluoropolymer of the present invention is represented by a polymerization unit (X) based on a fluoroolefin, a polymerization unit (Y) having a crosslinkable group in the side chain, and the above formulas (1) to (6). A fluoropolymer comprising a polymer unit (Z) having at least one of the polymer units, wherein the content of the polymer unit (Z) is the total polymer unit of the fluoropolymer, 1 to 50 mol%.
That is, the fluorine-containing polymer of the present invention is suitably used for the above-described coating composition, but is a useful polymer that can be used for other purposes.
The polymer unit (X) in the fluoropolymer of the present invention has the same meaning as the polymer unit (X) described in the above-described coating composition of the present invention, and a polymer unit based on CF 2 = CF 2 or CF 2 = CFCl. Is particularly preferred.
The polymer unit (Y) in the fluoropolymer of the present invention has the same meaning as the polymer unit (Y) described in the above-described coating composition of the present invention, and hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl allyl ether, Polymeric units based on monomers having at least one hydroxy group selected from hydroxycycloalkyl allyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ester, and hydroxycycloalkyl allyl ester are particularly preferred. .
The polymerized unit (Z) (polymerized unit represented by formula (1) to formula (6)) is the polymerized unit (Z) (formula (1) to formula (6) described in the coating composition of the present invention described above. The description thereof will be omitted.
以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらの実施例に限定されない。なお、後述する表中における各成分の配合量は、質量基準を示す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, the compounding quantity of each component in the table | surface mentioned later shows a mass reference | standard.
［合成例１］（含フッ素重合体（Ａ）の製造）
撹拌機を備えた内容積２５０ｍＬのステンレス鋼製オートクレーブ内に、２，３−ジヒドロフラン（ＤＨＰ）（２８．５ｇ）、４−ヒドロキシブチルビニルエーテル（ＨＢＶＥ）（１３．３ｇ）、キシレン（５５．８ｇ）、エタノール（１５．７ｇ）、炭酸カリウム（５．８２ｇ）、ｔｅｒｔ−ブチルペルオキシピバレートの５０質量％キシレン溶液（０．７ｇ）およびクロロトリフルオロエチレン（ＣＴＦＥ）（６３ｇ）を導入した。オートクレーブを徐々に昇温し、５５℃に達した後、２０時間保持した。さらに、オートクレーブを６５℃に昇温し５時間保持した。オートクレーブを冷却した後、オートクレーブ内にヒンダードアミン系光安定剤（ＢＡＳＦ社製、Ｔｉｎｕｖｉｎ（登録商標）１４４）（０．３９ｇ）、重合禁止剤であるハイドロキノン（０．１３ｇ）を加え、１時間撹拌した。ろ過を行って残渣を除去し、真空乾燥することで、含フッ素重合体（Ａ）を得た。
含フッ素重合体（Ａ）の組成は、ＣＴＦＥに基づく重合単位／ＤＨＰに基づく重合単位／ＨＢＶＥに基づく重合単位＝５０／３９／１１モル％であった。
[Synthesis Example 1] (Production of fluoropolymer (A))
In a 250 mL stainless steel autoclave equipped with a stirrer, 2,3-dihydrofuran (DHP) (28.5 g), 4-hydroxybutyl vinyl ether (HBVE) (13.3 g), xylene (55.8 g) ), Ethanol (15.7 g), potassium carbonate (5.82 g), 50% by weight xylene solution of tert-butylperoxypivalate (0.7 g) and chlorotrifluoroethylene (CTFE) (63 g) were introduced. The temperature of the autoclave was gradually raised, and after reaching 55 ° C., it was held for 20 hours. Further, the autoclave was heated to 65 ° C. and held for 5 hours. After cooling the autoclave, a hindered amine light stabilizer (manufactured by BASF, Tinuvin (registered trademark) 144) (0.39 g) and hydroquinone (0.13 g) as a polymerization inhibitor were added to the autoclave and stirred for 1 hour. . Filtration was performed to remove the residue, and vacuum drying was performed to obtain a fluoropolymer (A).
The composition of the fluoropolymer (A) was polymerized units based on CTFE / polymerized units based on DHP / polymerized units based on HBVE = 50/39/11 mol%.
［合成例２］（含フッ素重合体（Ｂ）の製造）
撹拌機を備えた内容積２５０ｍＬのステンレス鋼製オートクレーブ内に、シクロヘキシルビニルエーテル（ＣＨＶＥ）（５１．２ｇ）、ＨＢＶＥ（１３．３ｇ）、キシレン（５５．８ｇ）、エタノール（１５．７ｇ）、炭酸カリウム（５．８２ｇ）、ｔｅｒｔ−ブチルペルオキシピバレートの５０質量％キシレン溶液（０．７ｇ）およびＣＴＦＥ（６３ｇ）を導入した。オートクレーブを徐々に昇温し、５５℃に達した後、２０時間保持した。さらに、オートクレーブを６５℃に昇温し５時間保持した。オートクレーブを冷却した後、オートクレーブ内にヒンダードアミン系光安定剤（ＢＡＳＦ社製、Ｔｉｎｕｖｉｎ（登録商標）１４４）（０．３９ｇ）、重合禁止剤であるハイドロキノン（０．１３ｇ）を加え、１時間撹拌した。ろ過を行って残渣を除去し、真空乾燥することで、含フッ素重合体（Ｂ）を得た。
含フッ素重合体（Ｂ）の組成は、ＣＴＦＥに基づく重合単位／ＣＨＶＥに基づく重合単位／ＨＢＶＥに基づく重合単位＝５０／３９／１１モル％であった。
[Synthesis Example 2] (Production of fluoropolymer (B))
In a 250 mL stainless steel autoclave equipped with a stirrer, cyclohexyl vinyl ether (CHVE) (51.2 g), HBVE (13.3 g), xylene (55.8 g), ethanol (15.7 g), potassium carbonate (5.82 g), 50% by weight xylene solution of tert-butylperoxypivalate (0.7 g) and CTFE (63 g) were introduced. The temperature of the autoclave was gradually raised, and after reaching 55 ° C., it was held for 20 hours. Further, the autoclave was heated to 65 ° C. and held for 5 hours. After cooling the autoclave, a hindered amine light stabilizer (manufactured by BASF, Tinuvin (registered trademark) 144) (0.39 g) and hydroquinone (0.13 g) as a polymerization inhibitor were added to the autoclave and stirred for 1 hour. . Filtration was performed to remove the residue, and vacuum drying was performed to obtain a fluoropolymer (B).
The composition of the fluoropolymer (B) was CTFE-based polymer units / CHVE-based polymer units / HBVE-based polymer units = 50/39/11 mol%.
［粉体塗料組成物の製造］
含フッ素重合体（Ａ）、含フッ素重合体（Ｂ）をそれぞれ用いて、実施例および比較例の各粉体塗料組成物を製造した。
すなわち、後述する表１に記載の各成分を表１に記載の量になるように、高速ミキサーを用いて、粉末状態で各成分を混合して混合物を得た。
次に、２軸押出し機（サーモプリズム社製、１６ｍｍ押出し機）を用いて、１２０℃のバレル設定温度にて上記混合物の溶融混練を行い、ペレットを得た。得られたペレットを粉砕機で常温粉砕し、さらにメッシュにて分級して、実施例１および比較例１の粉体塗料組成物をそれぞれ得た。得られた各粉体塗料組成物の平均粒子径はいずれも、約４０μｍであった。また、いずれの粉体塗料組成物も、着色していなかった。
なお、表１に示す各成分の詳細は以下の通りである。
・含フッ素重合体（Ａ）（上記のようにして調製）
・含フッ素重合体（Ｂ）（上記のようにして調製）
・硬化剤（ブロック化イソシアネート系硬化剤、エボニック社製、商品名：ベスタゴンＢ１５３０、ＩＮＤＥＸ＝１）
・脱ガス剤（ベンゾイン）
・可塑剤（ＥＡＳＴＭＡＮ社製、商品名：Ｂｅｎｚｏｆｌｅｘ ３５２）
・表面調整剤（ビックケミー社製、商品名：ＢＹＫ−３６０Ｐ）
・硬化触媒（ジブチルスズジラウレート）
[Production of powder coating composition]
Using the fluoropolymer (A) and the fluoropolymer (B), the powder coating compositions of Examples and Comparative Examples were produced.
That is, each component described in Table 1 to be described later was mixed in a powder state using a high-speed mixer so as to obtain the amount described in Table 1, thereby obtaining a mixture.
Next, the mixture was melt-kneaded at a barrel setting temperature of 120 ° C. using a twin-screw extruder (manufactured by Thermo Prism, 16 mm extruder) to obtain pellets. The obtained pellets were pulverized at room temperature with a pulverizer and further classified with a mesh to obtain the powder coating compositions of Example 1 and Comparative Example 1, respectively. Each of the obtained powder coating compositions had an average particle size of about 40 μm. Also, none of the powder coating compositions was colored.
The details of each component shown in Table 1 are as follows.
・ Fluoropolymer (A) (prepared as described above)
・ Fluoropolymer (B) (prepared as described above)
Curing agent (blocked isocyanate curing agent, manufactured by Evonik, trade name: Vestagon B1530, INDEX = 1)
・ Degassing agent (benzoin)
・ Plasticizer (product name: Benzoflex 352, manufactured by EASTMAN)
・ Surface conditioner (BIC Chemie, trade name: BYK-360P)
・ Curing catalyst (dibutyltin dilaurate)
［試験片の作製・評価例］
それぞれの粉体塗料組成物を用いて、以下の手順で試験片を作製して、塗膜物性を評価した。
ポリエステル樹脂（ダイセル・オルネクス社製、ＣＲＹＬＣＯＡＴ（登録商標） ４８９０−０、質量平均分子量：４，４００、数平均分子量：２，５００、水酸基価：３０ｍｇＫＯＨ／ｇ）（５２．０ｇ）、ブロック化イソシアネート系硬化剤（エボニック社製、商品名：ベスタゴンＢ１５３０）（７．６ｇ）（ＩＮＤＥＸ＝１）、脱ガス剤としてベンゾイン（０．４ｇ）、表面調整剤（ビックケミー社製、商品名：ＢＹＫ−３６０Ｐ）（１．０ｇ）、硬化触媒としてジブチルスズジラウレート（０．００４２ｇ）、および着色剤として二酸化チタン（デュポン社製、商品名：タイピュアＲ９６０）（３２．１ｇ）を、高速ミキサーを用いて、粉末状態で各成分を混合して、混合物を得た。
得られた混合物を２軸押出し機（サーモプリズム社製、１６ｍｍ押出し機）を用いて、１２０℃のバレル設定温度にて溶融混練を行い、ペレットを得た。得られたペレットを、粉砕機を用いて常温で粉砕し、メッシュによる分級を行い、平均粒子径約４０μｍのポリエステル粉体塗料を得た。
クロメート処理を行ったアルミ製基板の一面に、静電塗装機（小野田セメント社製、商品名：ＧＸ３６００Ｃ）を用いて、以下に示すポリエステル粉体塗料の静電塗装を行い、１８０℃雰囲気中で２０分間保持した後、冷却して、塗装膜厚５５〜６５μｍのポリエステル硬化塗膜が形成された試験片を得た。
次いで、ポリエステル硬化塗膜の上に、実施例および比較例の粉体塗料組成物をそれぞれ静電塗装して、２００℃の雰囲気で２０分間保持した後、冷却して、塗装膜厚５５〜６５μｍの硬化塗膜が形成された試験片を、それぞれ得た。
[Production and evaluation example of test piece]
Using each powder coating composition, a test piece was prepared by the following procedure, and the physical properties of the coating film were evaluated.
Polyester resin (manufactured by Daicel Ornex Co., Ltd., CRYLCOAT (registered trademark) 4890-0, mass average molecular weight: 4,400, number average molecular weight: 2,500, hydroxyl value: 30 mgKOH / g) (52.0 g), blocked isocyanate -Based curing agent (Evonik Co., Ltd., trade name: Vestagon B1530) (7.6 g) (INDEX = 1), degassing agent benzoin (0.4 g), surface conditioner (Bic Chemie, trade name: BYK-360P) ) (1.0 g), dibutyltin dilaurate (0.0042 g) as a curing catalyst, and titanium dioxide (manufactured by DuPont, trade name: Taipure R960) (32.1 g) as a colorant, in a powder state using a high-speed mixer Each component was mixed in to obtain a mixture.
The obtained mixture was melt-kneaded at a barrel set temperature of 120 ° C. using a twin screw extruder (manufactured by Thermo Prism, 16 mm extruder) to obtain pellets. The obtained pellets were pulverized at room temperature using a pulverizer and classified with a mesh to obtain a polyester powder paint having an average particle size of about 40 μm.
Using an electrostatic coating machine (trade name: GX3600C, manufactured by Onoda Cement Co., Ltd.) on one side of the aluminum substrate subjected to chromate treatment, electrostatic coating of the polyester powder paint shown below is performed, and in an atmosphere of 180 ° C. After holding for 20 minutes, it cooled and obtained the test piece in which the polyester cured coating film with the coating film thickness of 55-65 micrometers was formed.
Subsequently, the powder coating compositions of Examples and Comparative Examples were electrostatically coated on the cured polyester coating film, held in an atmosphere of 200 ° C. for 20 minutes, and then cooled to a coating film thickness of 55 to 65 μm. Each of the test pieces on which the cured coating film was formed was obtained.
それぞれの試験片を屋外設置し、２年後の塗膜表面の６０°光沢度を、光沢計を用いて測定した結果、設置直前の塗膜表面の６０°光沢度を基準（１００％）とした場合、実施例の試験片の硬化塗膜の光沢保持率は８０％以上であり、比較例の試験片の硬化塗膜の光沢保持率は６０％未満であった。また、実施例の試験片の硬化塗膜の表面を肉眼観察したが、ピンホールとクラックの発生が認められなかった。 Each test piece was installed outdoors, and the 60 ° glossiness of the coating film surface after 2 years was measured using a gloss meter. As a result, the 60 ° glossiness of the coating film surface just before installation was the standard (100%). In this case, the gloss retention of the cured coating film of the test piece of the example was 80% or more, and the gloss retention of the cured coating film of the test piece of the comparative example was less than 60%. Moreover, when the surface of the cured coating film of the test piece of an Example was observed with the naked eye, the generation | occurrence | production of a pinhole and a crack was not recognized.
Claims (8)
前記重合単位（Ｚ）の含有量が、前記含フッ素重合体が有する全重合単位のうち、１〜５０モル％である、塗料組成物。
The coating composition whose content of the said polymerization unit (Z) is 1-50 mol% among all the polymerization units which the said fluoropolymer has.
前記重合単位（Ｚ）の含有量が、前記含フッ素重合体が有する全重合単位のうち、１〜５０モル％である、含フッ素重合体。
The fluorine-containing polymer whose content of the said polymer unit (Z) is 1-50 mol% among all the polymerization units which the said fluorine-containing polymer has.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58133871A (en) * | 1982-02-05 | 1983-08-09 | Asahi Glass Co Ltd | Corrosion preventive coating method |
| JPH041216A (en) * | 1990-04-19 | 1992-01-06 | Asahi Chem Ind Co Ltd | Fluorinated copolymer and fluorinated coating material based thereon |
| JPH051197A (en) * | 1991-06-27 | 1993-01-08 | Asahi Chem Ind Co Ltd | Fluorine-containing resin, its production and coating composition thereof |
| JPH0532725A (en) * | 1991-06-18 | 1993-02-09 | Asahi Chem Ind Co Ltd | Fluorine-containing copolymer and coating material composed mainly of the same copolymer |
| JPH0910672A (en) * | 1995-06-27 | 1997-01-14 | Asahi Glass Co Ltd | Article with coating film formed by using powdery coating material |
| JPWO2004092235A1 (en) * | 2003-04-11 | 2006-07-06 | ダイキン工業株式会社 | Cyclic ether copolymer, resin composition for coating, optical device, and optical device manufacturing method |
| WO2016080220A1 (en) * | 2014-11-17 | 2016-05-26 | 旭硝子株式会社 | Method for preparing fluoro-olefin copolymer powder for powder coating, composition for powder coating, powder coating, and coated article |
-
2016
- 2016-10-07 JP JP2016199312A patent/JP2018059029A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58133871A (en) * | 1982-02-05 | 1983-08-09 | Asahi Glass Co Ltd | Corrosion preventive coating method |
| JPH041216A (en) * | 1990-04-19 | 1992-01-06 | Asahi Chem Ind Co Ltd | Fluorinated copolymer and fluorinated coating material based thereon |
| JPH0532725A (en) * | 1991-06-18 | 1993-02-09 | Asahi Chem Ind Co Ltd | Fluorine-containing copolymer and coating material composed mainly of the same copolymer |
| JPH051197A (en) * | 1991-06-27 | 1993-01-08 | Asahi Chem Ind Co Ltd | Fluorine-containing resin, its production and coating composition thereof |
| JPH0910672A (en) * | 1995-06-27 | 1997-01-14 | Asahi Glass Co Ltd | Article with coating film formed by using powdery coating material |
| JPWO2004092235A1 (en) * | 2003-04-11 | 2006-07-06 | ダイキン工業株式会社 | Cyclic ether copolymer, resin composition for coating, optical device, and optical device manufacturing method |
| WO2016080220A1 (en) * | 2014-11-17 | 2016-05-26 | 旭硝子株式会社 | Method for preparing fluoro-olefin copolymer powder for powder coating, composition for powder coating, powder coating, and coated article |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020065562A1 (en) * | 2018-09-25 | 2020-04-02 | AGC Inc. | Powder coating composition, method for producing coated article, and coated article |
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