JP5838856B2 - Fluorine-based graft copolymer and coating agent - Google Patents
Fluorine-based graft copolymer and coating agent Download PDFInfo
- Publication number
- JP5838856B2 JP5838856B2 JP2012041359A JP2012041359A JP5838856B2 JP 5838856 B2 JP5838856 B2 JP 5838856B2 JP 2012041359 A JP2012041359 A JP 2012041359A JP 2012041359 A JP2012041359 A JP 2012041359A JP 5838856 B2 JP5838856 B2 JP 5838856B2
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- JP
- Japan
- Prior art keywords
- fluorine
- functional group
- graft copolymer
- crosslinkable functional
- side chain
- 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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- 229910052731 fluorine Inorganic materials 0.000 title claims description 126
- 229920000578 graft copolymer Polymers 0.000 title claims description 108
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 94
- 239000011737 fluorine Substances 0.000 title claims description 94
- 239000011248 coating agent Substances 0.000 title claims description 73
- 125000000524 functional group Chemical group 0.000 claims description 111
- 239000000178 monomer Substances 0.000 claims description 85
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 229920002554 vinyl polymer Polymers 0.000 claims description 34
- 125000001153 fluoro group Chemical group F* 0.000 claims description 32
- 229920002313 fluoropolymer Polymers 0.000 claims description 22
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- 239000004811 fluoropolymer Substances 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 40
- -1 perfluoro Chemical group 0.000 description 22
- 238000012360 testing method Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 17
- 239000011247 coating layer Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
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- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
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- CDXFIRXEAJABAZ-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDXFIRXEAJABAZ-UHFFFAOYSA-N 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
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- 239000004632 polycaprolactone Substances 0.000 description 4
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 3
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- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 3
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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Description
本発明は、フッ素系グラフト共重合体およびこれを用いてなるコーティング剤に関する。さらに詳しくは、特定のフッ素系グラフト共重合体を含んでなる、十分な基材密着性及び塗膜強度等を有し、かつ撥水・撥油性及び耐汚染性等の良好なコーティング剤に関する。 The present invention relates to a fluorine-based graft copolymer and a coating agent using the same. More specifically, the present invention relates to a coating agent comprising a specific fluorine-based graft copolymer, having sufficient substrate adhesion and coating strength, and having good water / oil repellency and stain resistance.
従来から、撥水・撥油性並びに耐汚染性を付与するコーティング剤として、フッ素系重合体を含むコーティング剤が用いられている。ここで、当該フッ素系重合体としては、パーフルオロ（メタ）アクリレートと、これ以外のラジカル重合性単量体とのランダム共重合体が知られているが、高い撥水・撥油性並びに耐汚染性を得るためには共重合体中のパーフルオロ（メタ）アクリレートの含有量を十分高くする必要がある。しかしながら、このような共重合体を含むコーティング剤を使用する際には塗膜強度や基材への密着性が劣るという問題があった。 Conventionally, a coating agent containing a fluoropolymer has been used as a coating agent imparting water / oil repellency and stain resistance. Here, as the fluorine-based polymer, a random copolymer of perfluoro (meth) acrylate and other radical polymerizable monomer is known, but has high water / oil repellency and contamination resistance. In order to obtain the properties, it is necessary to sufficiently increase the content of perfluoro (meth) acrylate in the copolymer. However, when a coating agent containing such a copolymer is used, there is a problem that the coating film strength and the adhesion to the substrate are poor.
これに対し、パーフルオロ（メタ）アクリレートの含有量を少なくしつつ、高い撥水・撥油性並びに耐汚染性を示す共重合体を得る手段として、パーフルオロ（メタ）アクリレート単位からなる重合体を枝、または幹セグメントとするグラフト共重合体及びこれを用いた塗料が提案されている。
例えば、特許文献１では枝セグメントとして非フッ素系重合体、幹セグメントとしてパーフルオロ（メタ）アクリレートを必須の重合体成分とするグラフト共重合体が開示されている。また、特許文献２〜４には、パーフルオロアルキル基を有する重合体を枝セグメントとするグラフト共重合体、並びにこれを用いたコーティング剤が開示されている。
On the other hand, as a means for obtaining a copolymer exhibiting high water / oil repellency and stain resistance while reducing the content of perfluoro (meth) acrylate, a polymer comprising perfluoro (meth) acrylate units is used. A graft copolymer having branches or trunk segments and a paint using the same have been proposed.
For example, Patent Document 1 discloses a graft copolymer having a non-fluorinated polymer as a branch segment and perfluoro (meth) acrylate as an essential polymer component as a trunk segment. Patent Documents 2 to 4 disclose a graft copolymer having a polymer having a perfluoroalkyl group as a branch segment, and a coating agent using the same.
しかしながら、特許文献１に開示されるフッ素系グラフト共重合体を用いたコーティング剤は、フッ素系重合体を主鎖成分とするためにフッ素セグメントの自由度が制限されるものであった。このため、撥水・撥油性及び耐汚染性等のフッ素による特性を発現させるためにはフッ素含有量を一定以上のものとする必要があり、コスト高となる傾向があった。また、耐久性にも課題があるものであった。
また、特許文献２〜４に開示されるフッ素系グラフト共重合体を用いたコーティング剤では、側鎖をフッ素セグメントとすることによりフッ素含有量をより低減することは可能であったが、耐久性の点では依然として十分なレベルには至らないものであった。
However, the coating agent using the fluorine-based graft copolymer disclosed in Patent Document 1 has a limitation on the degree of freedom of the fluorine segment because the fluorine-based polymer is a main chain component. For this reason, in order to express the characteristics of fluorine such as water repellency / oil repellency and stain resistance, the fluorine content needs to be a certain level or more, and the cost tends to increase. In addition, there is a problem in durability.
Moreover, in the coating agent using the fluorine-type graft copolymer disclosed by patent documents 2-4, it was possible to reduce fluorine content more by making a side chain into a fluorine segment, but durability However, it was still not enough.
本発明は、上記問題点に鑑みてなされたものであり、撥水・撥油性及び耐汚染性等のフッ素特性、並びに基材密着性、塗膜強度及び耐久性等を高度にバランス化した性能を発揮するグラフト共重合体およびこれを用いたコーティング剤を提供することを課題とするものである。 The present invention has been made in view of the above-mentioned problems, and is a highly balanced performance of fluorine characteristics such as water / oil repellency and stain resistance, as well as substrate adhesion, coating strength and durability. It is an object of the present invention to provide a graft copolymer exhibiting the above and a coating agent using the same.
本発明は以下の通りである。
〔１〕主鎖に架橋性官能基を有し、側鎖は架橋性官能基が導入されたフッ素系重合体からなるフッ素系グラフト共重合体であって、
上記側鎖に配される架橋性官能基がω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体に由来するものであり、
上記側鎖たる上記フッ素系重合体を構成する全単量体に対するフッ素原子含有ビニル単量体の割合が４０〜９５質量％であり、
上記フッ素原子含有ビニル単量体として下記一般式（１）で表されるビニル単量体が含まれることを特徴とするフッ素系グラフト共重合体。
〔２〕上記主鎖と上記側鎖との比率が、主鎖４０〜９０質量％に対して側鎖が１０〜６０質量％であり、
上記分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体における、カプロラクトンの平均付加モル数が２モル以上であり
上記一般式（１）におけるｎが６〜２０である、上記〔１〕に記載のフッ素系グラフト共重合体。
〔３〕上記側鎖たるフッ素系重合体の重量平均分子量が５，０００〜２２，５００であり、
上記側鎖に配される架橋性官能基が水酸基である上記〔１〕又は〔２〕に記載のフッ素系グラフト共重合体。
〔４〕上記フッ素原子含有ビニル単量体、及び上記ω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体がアクリレート型である請求項〔１〕〜〔３〕のいずれかに記載のフッ素系グラフト共重合体。
〔５〕上記主鎖中の架橋性官能基の導入量が０．７〜３．０ｍｅｑ／ｇの範囲であることを特徴とする上記〔１〕〜〔４〕のいずれかに記載のフッ素系グラフト共重合体。
〔６〕上記側鎖中の架橋性官能基の導入量が０．２〜１．０ｍｅｑ／ｇの範囲であることを特徴とする上記〔１〕〜〔５〕のいずれかに記載のフッ素系グラフト共重合体。
〔７〕上記フッ素系グラフト共重合体の側鎖が、フッ素原子含有ビニル単量体及びω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体をその構成単位に含み、片末端に重合性不飽和結合を有するマクロモノマーに由来するものであることを特徴とする上記〔１〕〜〔６〕に記載のフッ素系グラフト共重合体。
〔８〕上記主鎖及び側鎖に配される架橋性官能基が水酸基であることを特徴とする上記〔１〕〜〔７〕のいずれかに記載のフッ素系グラフト共重合体。
〔９〕主鎖に架橋性官能基を有し、側鎖は架橋性官能基が導入されたフッ素系重合体からなるフッ素系グラフト共重合体の製造方法であって、
末端に重合性不飽和官能基を有し、かつ架橋性官能基が導入されたフッ素系重合体からなるマクロモノマーの存在下に架橋性官能基含有ビニル単量体を含む単量体混合物を共重合するものであり、
上記マクロモノマーが、フッ素原子含有ビニル単量体及びω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体を構成単量体とするフッ素系グラフト共重合体の製造方法。
〔１０〕上記フッ素系重合体の重量平均分子量が５，０００〜２２，５００であり、該フッ素系重合体を構成する全単量体に対するフッ素原子含有ビニル単量体の割合が４０〜９５質量％であって、
上記側鎖に配される架橋性官能基が水酸基であり、
上記フッ素原子含有ビニル単量体として下記一般式（１）で表されるビニル単量体が含まれることを特徴とする上記〔９〕に記載のフッ素系グラフト共重合体の製造方法。
〔１１〕上記〔１〕〜〔８〕のいずれかに記載のフッ素系グラフト共重合体を含むコーティング剤。
〔１２〕上記フッ素系グラフト共重合体に加え、さらに架橋剤を含んでなる上記〔１１〕に記載のコーティング剤。
The present invention is as follows.
[1] having a backbone crosslinking functional group, the side chain is a full Tsu Motokei graft copolymer of a fluorine-based polymer has crosslinkable functional group is introduced,
The crosslinkable functional group arranged in the side chain has a crosslinkable functional group at the ω position, and is derived from a monomer having 10 or more carbon atoms having a structure derived from caprolactone in the molecule,
The ratio of the fluorine atom-containing vinyl monomer to the total monomer constituting the fluoropolymer as the side chain is 40 to 95% by mass,
A fluorine-based graft copolymer comprising a vinyl monomer represented by the following general formula (1) as the fluorine atom-containing vinyl monomer .
[2] The ratio of the main chain to the side chain is 10 to 60% by mass of the side chain with respect to 40 to 90% by mass of the main chain,
In the monomer having a structure derived from caprolactone in the molecule and having 10 or more carbon atoms, the average added mole number of caprolactone is 2 moles or more.
The fluorine-type graft copolymer as described in said [1] whose n in the said General formula (1) is 6-20.
[3] The fluoropolymer as the side chain has a weight average molecular weight of 5,000 to 22,500,
The fluorine-based graft copolymer according to the above [1] or [2], wherein the crosslinkable functional group arranged in the side chain is a hydroxyl group.
[4] The fluorine atom-containing vinyl monomer, and the monomer having a crosslinkable functional group at the ω position and having a structure derived from caprolactone in the molecule is an acrylate type. The fluorine-based graft copolymer according to any one of Items [1] to [3].
[5] The fluorine-based system as described in any one of [1] to [4] above, wherein the introduction amount of the crosslinkable functional group in the main chain is in the range of 0.7 to 3.0 meq / g. Graft copolymer.
[6] The fluorine system according to any one of [1] to [5], wherein the amount of the crosslinkable functional group introduced into the side chain is in the range of 0.2 to 1.0 meq / g. Graft copolymer.
[7] the side chain of the fluorine-based graft copolymer, have a crosslinkable functional group into the fluorine-containing vinyl monomer and ω positions, and, carbon atoms which have a structure derived from caprolactone in a molecule 10 or more The fluorine-based graft copolymer according to any one of [1] to [6] above, wherein the monomer is derived from a macromonomer having a polymerizable unsaturated bond at one end. Coalescence.
[8] The fluorine-based graft copolymer according to any one of the above [1] to [7], wherein the crosslinkable functional group arranged in the main chain and the side chain is a hydroxyl group.
[9] A method for producing a fluorinated graft copolymer comprising a fluorinated polymer having a crosslinkable functional group in a main chain and a side chain introduced with a crosslinkable functional group,
A monomer mixture containing a crosslinkable functional group-containing vinyl monomer in the presence of a macromonomer composed of a fluoropolymer having a polymerizable unsaturated functional group at the terminal and having a crosslinkable functional group introduced therein Is to polymerize,
The macromonomer has a fluorine atom-containing vinyl monomer and a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position and a structure derived from caprolactone in the molecule. A method for producing a fluorine-based graft copolymer.
[10] The weight average molecular weight of the fluoropolymer is 5,000 to 22,500, and the ratio of the fluorine atom-containing vinyl monomer to the total monomer constituting the fluoropolymer is 40 to 95 mass. %,
The crosslinkable functional group arranged in the side chain is a hydroxyl group,
The method for producing a fluorine-based graft copolymer as described in [9] above, wherein the fluorine atom-containing vinyl monomer includes a vinyl monomer represented by the following general formula (1).
[11] A coating agent comprising the fluorine-based graft copolymer according to any one of [1] to [8].
[12] The coating agent according to [ 11 ], further comprising a crosslinking agent in addition to the fluorine-based graft copolymer.
本発明は以下の通りである。
〔１〕主鎖に架橋性官能基を有し、側鎖は架橋性官能基が導入されたフッ素系重合体からなることを特徴とするフッ素系グラフト共重合体。
〔２〕上記主鎖中の架橋性官能基の導入量が０．７〜３．０ｍｅｑ／ｇの範囲であることを特徴とする上記〔１〕に記載のフッ素系グラフト共重合体。
〔３〕上記フッ素系重合体を構成する単量体として、下記一般式（１）で表されるビニル単量体が含まれることを特徴とする上記〔１〕又は〔２〕に記載のフッ素系グラフト共重合体。
〔４〕上記一般式（１）において、ｎが４〜１２であることを特徴とする上記〔３〕に記載のフッ素系グラフト共重合体。
〔５〕上記側鎖中の架橋性官能基の導入量が０．２〜１．０ｍｅｑ／ｇの範囲であることを特徴とする上記〔１〕〜〔４〕のいずれかに記載のフッ素系グラフト共重合体。
〔６〕上記側鎖に配される架橋性官能基がω位に架橋性官能基を有する炭素数１０以上の単量体に由来することを特徴とする上記〔１〕〜〔５〕のいずれかに記載のフッ素系グラフト共重合体。
〔７〕上記フッ素系グラフト共重合体の側鎖が、フッ素原子含有ビニル単量体及びω位に架橋性官能基を有する炭素数１０以上の単量体をその構成単位に含み、片末端に重合性不飽和結合を有するマクロモノマーに由来するものであることを特徴とする上記〔６〕に記載のフッ素系グラフト共重合体。
〔８〕上記主鎖及び側鎖に配される架橋性官能基が水酸基であることを特徴とする上記〔１〕〜〔７〕のいずれかに記載のフッ素系グラフト共重合体。
〔９〕上記〔１〕〜〔８〕のいずれかに記載のフッ素系グラフト共重合体を含むコーティング剤。
〔１０〕上記フッ素系グラフト共重合体に加え、さらに架橋剤を含んでなる上記〔９〕に記載のコーティング剤。
The present invention is as follows.
[1] A fluorine-based graft copolymer having a crosslinkable functional group in the main chain and a side chain comprising a fluorine polymer into which a crosslinkable functional group is introduced.
[2] The fluorine-based graft copolymer as described in [1] above, wherein the introduction amount of the crosslinkable functional group in the main chain is in the range of 0.7 to 3.0 meq / g.
[3] The fluorine as described in [1] or [2] above, wherein the monomer constituting the fluoropolymer includes a vinyl monomer represented by the following general formula (1): Graft copolymer.
[4] The fluorine-based graft copolymer as described in [3] above, wherein in the general formula (1), n is 4 to 12.
[5] The fluorine-based material according to any one of [1] to [4], wherein the amount of the crosslinkable functional group introduced into the side chain is in the range of 0.2 to 1.0 meq / g. Graft copolymer.
[6] Any of the above [1] to [5], wherein the crosslinkable functional group arranged in the side chain is derived from a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position. A fluorine-based graft copolymer according to any one of the above.
[7] The side chain of the fluorine-based graft copolymer contains a fluorine atom-containing vinyl monomer and a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position in its constituent unit, The fluorine-based graft copolymer as described in [6] above, which is derived from a macromonomer having a polymerizable unsaturated bond.
[8] The fluorine-based graft copolymer according to any one of the above [1] to [7], wherein the crosslinkable functional group arranged in the main chain and the side chain is a hydroxyl group.
[9] A coating agent comprising the fluorine-based graft copolymer according to any one of [1] to [8].
[10] The coating agent according to [9], further including a crosslinking agent in addition to the fluorine-based graft copolymer.
本発明のフッ素系グラフト共重合体は、グラフト構造を有することにより各種基材に対する良好な密着性と撥水・撥油性及び耐汚染性といったフッ素特性との両立を図ることができるため、コーティング剤として有用である。また、フッ素セグメントを側鎖に配することによりフッ素特性を有効に示すことができるため、フッ素含有量が比較的少ない共重合体を用いた場合でもフッ素系コーティング剤として優れた性能が発揮される。
さらに、主鎖及び側鎖に配された架橋性官能基により架橋を施すことで、耐久性にも優れた強靭なコーティング層が得られる。
Since the fluorine-based graft copolymer of the present invention has a graft structure, it can achieve both good adhesion to various substrates and fluorine characteristics such as water repellency / oil repellency and stain resistance. Useful as. In addition, since the fluorine characteristics can be effectively shown by arranging the fluorine segment in the side chain, excellent performance as a fluorine-based coating agent is exhibited even when a copolymer having a relatively small fluorine content is used. .
Furthermore, a tough coating layer having excellent durability can be obtained by crosslinking with a crosslinkable functional group arranged on the main chain and side chain.
本発明は、特定の構造を有するフッ素系グラフト共重合体およびこれを用いてなるコーティング剤に関するものである。
以下、本発明について詳しく説明する。尚、本願明細書においては、アクリル酸及びメタクリル酸を、（メタ）アクリル酸と表す。
The present invention relates to a fluorine-based graft copolymer having a specific structure and a coating agent using the same.
The present invention will be described in detail below. In the present specification, acrylic acid and methacrylic acid are represented as (meth) acrylic acid.
本発明におけるグラフト共重合体は、その主鎖に架橋性官能基を有する。
当該架橋性官能基は、グラフト共重合体における主鎖の構成成分に架橋性官能基含有ビニル単量体を含めることにより導入することができる。当該架橋性官能基含有ビニル単量体の具体的な例としては（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル及び（メタ）アクリル酸ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキル、ヒドロキシエチル（メタ）アクリレートにε−カプロラクトンを付加させた化合物〔例えばダイセル化学工業（株）製商品名プラクセルＦＭ２Ｄ、プラクセルＦＭ３、プラクセルＦＭ５、プラクセルＦＡ１ＤＤＭ、プラクセルＦＡ２Ｄ、プラクセルＦＡ１０Ｌ等〕等の水酸基含有単量体；（メタ）アクリル酸、クロトン酸、マレイン酸、無水マレイン酸およびイタコン酸等のカルボキシル基含有単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミドおよびＮ−イソブトキシメチル（メタ）アクリルアミド等のＮ−メチロール基又はＮ−アルコキシメチル基含有化合物；（メタ）アクリル酸グリシジル等のエポキシ基含有単量体等が挙げられる。
また、上記とは別に水酸基含有不飽和単量体を共重合した後に、二塩基酸無水物、例えば無水コハク酸、無水マレイン酸または無水フタル酸等を付加反応させることにより架橋性官能基としてカルボキシル基を導入することも可能である。
更に、例えば重合体にエポキシ基を導入した後に（メタ）アクリル酸等の重合性不飽和結合を有するカルボン酸化合物を付加させる等、官能基が導入された重合体に対して該官能基と反応可能な官能基及び重合性ビニル基の双方を有する化合物を反応させることにより架橋性官能基として（メタ）アクリロイル基等の重合性ビニル基を導入することもできる。
上記架橋性官能基の中でも製造上の安定性、架橋反応の制御のし易さ、架橋後の塗膜物性等の観点から水酸基及び（メタ）アクリロイル基が好ましく、水酸基が特に好ましい。
The graft copolymer in the present invention has a crosslinkable functional group in its main chain.
The said crosslinkable functional group can be introduce | transduced by including a crosslinkable functional group containing vinyl monomer in the structural component of the principal chain in a graft copolymer. Specific examples of the crosslinkable functional group-containing vinyl monomer include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and (meth) acrylic acid. A compound obtained by adding ε-caprolactone to hydroxyalkyl (meth) acrylate such as hydroxybutyl, hydroxyethyl (meth) acrylate [for example, Daicel Chemical Industries, Ltd., trade name: Placcel FM2D, Placcel FM3, Placcel FM5, Placcel FA1DDM, Hydroxyl group-containing monomers such as (Placcel FA2D, Plaxel FA10L, etc.); carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride and itaconic acid; N-methylol (meth) acrylamide, N-methoxymethyl N-methylol group or N-alkoxymethyl group-containing compounds such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide; epoxy group-containing compounds such as glycidyl (meth) acrylate Examples include a polymer.
In addition to the above, after copolymerizing a hydroxyl group-containing unsaturated monomer, a dibasic acid anhydride such as succinic anhydride, maleic anhydride or phthalic anhydride is added to form a carboxyl group as a crosslinkable functional group. It is also possible to introduce groups.
Furthermore, after introducing an epoxy group into the polymer, for example, a carboxylic acid compound having a polymerizable unsaturated bond such as (meth) acrylic acid is added, and the functional group is reacted with the functional group. It is also possible to introduce a polymerizable vinyl group such as a (meth) acryloyl group as a crosslinkable functional group by reacting a compound having both a functional group and a polymerizable vinyl group.
Among the crosslinkable functional groups, a hydroxyl group and a (meth) acryloyl group are preferred, and a hydroxyl group is particularly preferred from the viewpoints of production stability, ease of control of the crosslinking reaction, coating film properties after crosslinking, and the like.
架橋性官能基を主鎖に導入したグラフト共重合体に対し必要に応じて後記する架橋剤を添加した後、熱または活性エネルギー線等のエネルギーを与えて架橋することにより強靭なコーティング層が得られるため、長期に渡る使用においてもコーティング層の削れや剥がれ等がなく耐久性の高い塗膜が得られるようになる。 After adding a crosslinking agent as described later to the graft copolymer having a crosslinkable functional group introduced into the main chain as needed, a tough coating layer is obtained by crosslinking by applying energy such as heat or active energy rays. Therefore, even when used for a long period of time, the coating layer will not be scraped or peeled off, and a highly durable coating film can be obtained.
主鎖中の架橋性官能基の導入量は０．７〜３．０ｍｅｑ／ｇの範囲であることが好ましく、１．０〜２．５ｍｅｑ／ｇの範囲がより好ましい。架橋性官能基の導入量が０．７ｍｅｑ／ｇ未満の場合はコーティング剤の耐久性が十分でなく、３．０ｍｅｑ／ｇを超える場合はコーティング層表面が汚染されやすくなる。
尚、上記導入量はグラフト共重合体から側鎖部分を除いた主鎖部分に導入された官能基量を意味し、当該導入量は単量体の仕込み比率から求められる。
The introduction amount of the crosslinkable functional group in the main chain is preferably in the range of 0.7 to 3.0 meq / g, and more preferably in the range of 1.0 to 2.5 meq / g. When the introduction amount of the crosslinkable functional group is less than 0.7 meq / g, the durability of the coating agent is not sufficient, and when it exceeds 3.0 meq / g, the surface of the coating layer is easily contaminated.
The introduction amount means the amount of the functional group introduced into the main chain portion excluding the side chain portion from the graft copolymer, and the introduction amount is determined from the monomer charge ratio.
主鎖を形成する重合体は、主鎖自身のガラス転移温度（以下、「Ｔｇ」という）が３０℃以上であることが好ましく、６０℃以上であることがより好ましい。Ｔｇが３０℃以上であれば耐汚染性および耐擦傷性等が良好な塗膜が得られ易い。 The polymer forming the main chain preferably has a glass transition temperature (hereinafter referred to as “Tg”) of the main chain itself of 30 ° C. or higher, and more preferably 60 ° C. or higher. When Tg is 30 ° C. or higher, a coating film having good stain resistance, scratch resistance and the like is easily obtained.
主鎖を形成する重合体を構成する他の単量体としては、例えば（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）アクリル酸シクロヘキシルおよび（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸オクタデシル等の（メタ）アクリル酸アルキルエステル；スチレン、α−メチルスチレンおよびｐ−メチルスチレン等のスチレン誘導体；（メタ）アクリロニトリル；（メタ）アクリルアミド等が挙げられ、これらの内の１種又は２種以上を使用することができる。
これらの中でもメタクリル酸メチル及び／又はメタクリル酸イソボルニルの使用が主鎖全体のＴｇが高くなるために好ましく、特にメタクリル酸メチルの場合は強靭なコーティング層が得られるために好ましい。
尚、本発明において主鎖中にはフッ素原子は含まれない。
Examples of other monomers constituting the polymer forming the main chain include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate; styrene, α-methylstyrene and Examples thereof include styrene derivatives such as p-methylstyrene; (meth) acrylonitrile; (meth) acrylamide and the like, and one or more of them can be used.
Among these, the use of methyl methacrylate and / or isobornyl methacrylate is preferable because the Tg of the entire main chain is increased, and methyl methacrylate is particularly preferable because a tough coating layer can be obtained.
In the present invention, the main chain does not contain a fluorine atom.
本発明におけるグラフト共重合体は、架橋性官能基が導入されたフッ素系重合体からなる側鎖を有する。ここで、「フッ素系重合体」とはフッ素原子を含有する重合体を意味するものであり、フッ素原子含有ビニル単量体を構成単量体とすることにより得られる。この他にも、例えばカルボキシル基を導入した重合体に含フッ素エポキシ化合物を反応させる等、反応性官能基を導入した重合体にフッ素を含む反応剤を反応させる方法によっても得ることができる。これらのうち、フッ素原子含有単量体を構成単量体とすることによりフッ素系重合体を得る方法が、目的とする重合体が高純度で簡便に得られることから好ましい。 The graft copolymer in the present invention has a side chain made of a fluoropolymer having a crosslinkable functional group introduced therein. Here, the “fluorine polymer” means a polymer containing a fluorine atom, and can be obtained by using a fluorine atom-containing vinyl monomer as a constituent monomer. In addition to this, for example, it can also be obtained by a method of reacting a polymer containing a reactive functional group with a reactive agent containing fluorine, such as reacting a polymer containing a carboxyl group with a fluorine-containing epoxy compound. Among these, a method of obtaining a fluorine-based polymer by using a fluorine atom-containing monomer as a constituent monomer is preferable because the target polymer can be easily obtained with high purity.
上記フッ素原子含有ビニル単量体としては特に制限はなく、例えばトリフルオロメチル（メタ）アクリレート、ペンタフルオロエチル（メタ）アクリレート、ヘプタフルオロプロピル（メタ）アクリレート、ノナフルオロブチル（メタ）アクリレート、ウンデカフルオロペンチル（メタ）アクリレート、トリデカフルオロヘキシル（メタ）アクリレート、ペンタデカフルオロヘプチル（メタ）アクリレート、及び下記一般式（１）で表される単量体等の（メタ）アクリロイル型単量体；モノフルオロエチレン、ジフルオロエチレン、トリフルオロエチレン、クロロトリフルオロエチレン、テトラフルオロエチレン等のフルオロエチレン類；フッ化ビニリデン、フッ化ビニル、ヘキサフルオロプロピレン等が挙げられるが、共重合性及び取扱いの容易さ等から（メタ）アクリロイル型単量体が好ましく、入手のし易さ及びコストの点から下記一般式（１）で表される単量体が用いられる。
The fluorine atom-containing vinyl monomer is not particularly limited. For example, trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, heptafluoropropyl (meth) acrylate, nonafluorobutyl (meth) acrylate, undeca (Meth) acryloyl type monomers such as fluoropentyl (meth) acrylate, tridecafluorohexyl (meth) acrylate, pentadecafluoroheptyl (meth) acrylate, and monomers represented by the following general formula (1); Fluoroethylenes such as monofluoroethylene, difluoroethylene, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene; vinylidene fluoride, vinyl fluoride, hexafluoropropylene, etc., but copolymerizability and handling (Meth) acryloyl type monomer is preferable from the easiness, the monomers are used, represented by the following general formula (1) in terms of easy availability and cost.
上記一般式（１）で表されるフッ素原子含有ビニル単量体の実例としては、商品名でケミノックスＦＡＡＣ−４、ケミノックスＦＡＡＣ−６、ケミノックスＦＡＭＡＣ−４、ケミノックスＦＡＭＡＣ−６（以上、ユニマテック社製）、Ｒ−１４２０、Ｒ−１６２０、Ｒ−５４１０、Ｒ−５６１０、Ｍ−１４２０、Ｍ−１６２０、Ｍ−５４１０、Ｍ−５６１０（以上、ダイキン社製）、ライトアクリレートＦＡ−１０８（共栄社化学社製）、ビスコート−８Ｆ、ビスコート−８ＦＭ（以上、大阪有機化学工業社製）等が挙げられ、これらの内の１種または２種以上を用いることができる。
Examples of the fluorine atom-containing vinyl monomer represented by the general formula (1) include, as trade names, Cheminox FAAC-4, Cheminox FAAC-6, Cheminox FAMAC-4, Cheminox FAMAC-6 (above, manufactured by Unimatec) ), R- 1420, R-1620, R- 5410, R-5610, M- 1420, M-1620, M- 5410, M-5610 (manufactured by Daikin), Light acrylate FA-108 (Kyoeisha Chemical Co., Ltd.) Ltd.), bi squat -8F, Viscoat -8FM (above, include Osaka Organic Chemical Industry Co., Ltd.), may be used alone or two or more of these.
上記一般式（１）におけるＺについてはフッ素の特性が顕著となることからフッ素原子であることが好ましく、ｍについては入手し易さの点からｍ＝１もしくは２が好ましい。ｎについては１〜２０のものを用いることができるが、ｎが小さいとフッ素特性が十分に発揮されない場合があり、ｎが大きすぎると溶剤への溶解性や他の配合物との相溶性が低下し、特にマクロモノマーの合成が困難となる場合がある。これらの観点からｎ＝４〜１２が好ましく、ｎ＝６〜８が更に好ましいが、本発明ではｎ＝４以上のものを用いる。ただし、ｎ＝８以上のものは化合物の安全性の観点では若干懸念される。
また、フッ素の特性が現れ易く耐久性も高くなる傾向があることからメタクリレート型よりもアクリレート型の方が好ましい。
上記フッ素原子含有ビニル単量体を使用することにより表面エネルギーの低いコーティング層を与えるコーティング剤が得られ、耐汚染性に優れたものとすることができる。
Z in the general formula (1) is preferably a fluorine atom since the characteristics of fluorine are remarkable, and m is preferably 1 or 2 from the viewpoint of availability. About n, the thing of 1-20 can be used, However, When n is small, a fluorine characteristic may not fully be exhibited, When n is too large, the solubility to a solvent and compatibility with another compound may be sufficient. In particular, the synthesis of the macromonomer may be difficult. From these viewpoints, n = 4 to 12 is preferable, and n = 6 to 8 is more preferable . In the present invention, n = 4 or more is used . However, those with n = 8 or more are slightly concerned from the viewpoint of the safety of the compound.
In addition, the acrylate type is preferred to the methacrylate type because fluorine characteristics tend to appear and durability tends to be high.
By using the fluorine atom-containing vinyl monomer, a coating agent that gives a coating layer having a low surface energy can be obtained, and it can be excellent in stain resistance.
本発明のグラフト共重合体を構成するフッ素系重合体（側鎖）を構成する単量体混合物におけるフッ素原子含有ビニル単量体の割合は側鎖を構成する全単量体に対して２０〜９５質量％が好ましく、４０〜９０質量％が更に好ましい。フッ素原子含有ビニル単量体が２０質量％未満の場合は撥水・撥油性及び耐汚染性等のフッ素の特性が十分発現されない場合がある。一方、９５質量％を超える場合はコーティング層の強度および耐久性の点が懸念され、またフッ素系重合体がグラフト共重合体製造時の重合媒体への溶解性が不十分となるために製造上の扱いが困難となる場合がある。本発明では、グラフト共重合体を構成するフッ素系重合体（側鎖）を構成する単量体混合物におけるフッ素原子含有ビニル単量体の割合は、側鎖を構成する全単量体に対して４０〜９５質量％である。
The ratio of the fluorine atom-containing vinyl monomer in the monomer mixture constituting the fluoropolymer (side chain) constituting the graft copolymer of the present invention is from 20 to the total monomer constituting the side chain. 95 mass% is preferable and 40-90 mass% is still more preferable. When the fluorine atom-containing vinyl monomer is less than 20% by mass, the characteristics of fluorine such as water / oil repellency and stain resistance may not be sufficiently exhibited. On the other hand, when it exceeds 95% by mass, there are concerns about the strength and durability of the coating layer, and the fluorine-based polymer is insufficient in solubility in the polymerization medium when the graft copolymer is produced. May be difficult to handle. In the present invention, the proportion of the fluorine atom-containing vinyl monomer in the monomer mixture constituting the fluoropolymer (side chain) constituting the graft copolymer is based on the total monomers constituting the side chain. It is 40-95 mass%.
側鎖を形成するフッ素系重合体の好ましい重量平均分子量（以下、「Ｍｗ」という）は４，０００〜２０，０００であり、より好ましくは５，０００〜１０，０００である。Ｍｗが２０，０００を超えるとグラフト共重合体の重合性が劣り溶解性不良の原因となる場合があり、また側鎖が導入されないリニア型重合体の割合が増加するためにフッ素の特性が効果的に示されない恐れがある。一方、Ｍｗが４，０００未満の場合はフッ素特性が不十分となる傾向がある。 The preferred weight average molecular weight (hereinafter referred to as “Mw”) of the fluoropolymer forming the side chain is 4,000 to 20,000, more preferably 5,000 to 10,000. If the Mw exceeds 20,000, the graft copolymer may be poorly polymerized and may cause poor solubility, and the proportion of linear polymers in which side chains are not introduced increases, so the characteristics of fluorine are effective. There is a risk that it will not be shown. On the other hand, when Mw is less than 4,000, the fluorine characteristics tend to be insufficient.
本発明のグラフト共重合体は上記の通り架橋性官能基を有する主鎖、及び架橋性官能基を有するフッ素系重合体からなる側鎖とからなる。主鎖と側鎖の比率は主鎖が４０〜９５質量％に対して側鎖が５〜６０質量％であることが好ましく、より好ましくは主鎖が６０〜９０質量％に対して側鎖が１０〜４０質量％である。
主鎖が９５質量％を超える（側鎖が５質量％未満）の場合はフッ素の特性が損なわれる傾向がある。一方、主鎖が４０質量％未満（側鎖が６０質量％を超える）場合はグラフト共重合体が柔らかく、かつ架橋も甘くなるために密着性及び耐久性が劣る場合がある。また、フッ素系重合体の割合が多くなるためにコスト高となる。
As described above, the graft copolymer of the present invention comprises a main chain having a crosslinkable functional group and a side chain composed of a fluoropolymer having a crosslinkable functional group. The ratio of the main chain to the side chain is preferably 5 to 60% by mass with respect to 40 to 95% by mass of the main chain, and more preferably the side chain with respect to 60 to 90% by mass of the main chain. It is 10-40 mass%.
When the main chain exceeds 95% by mass (the side chain is less than 5% by mass), the characteristics of fluorine tend to be impaired. On the other hand, when the main chain is less than 40% by mass (the side chain exceeds 60% by mass), the graft copolymer is soft and the cross-linking becomes sweet, so that the adhesion and durability may be inferior. Moreover, since the ratio of a fluoropolymer increases, cost becomes high.
グラフト共重合体のＭｗは１０，０００〜１００，０００が好ましく、１５，０００〜５０，０００がより好ましい。Ｍｗが１０，０００未満の場合はコーティング層の強度が劣るために耐久性が不十分となり、Ｍｗが１００，０００を超える場合は溶液の粘度が高くなるため塗工適性が不十分となる場合があり、均一なコーティング層を得難くなる傾向がある。 The Mw of the graft copolymer is preferably 10,000 to 100,000, more preferably 15,000 to 50,000. When the Mw is less than 10,000, the coating layer is inferior in strength, so that the durability is insufficient. When the Mw is greater than 100,000, the viscosity of the solution is increased and the coating suitability may be insufficient. There is a tendency that it is difficult to obtain a uniform coating layer.
グラフト共重合体の製法について特に制限はなく、主鎖に架橋性官能基を有し、側鎖が架橋性官能基を有するフッ素系重合体からなるグラフト共重合体を製造し得る方法であればいずれの方法で製造しても良い。 There is no restriction | limiting in particular about the manufacturing method of a graft copolymer, If it is a method which can manufacture the graft copolymer which has a crosslinkable functional group in a principal chain and consists of a fluoropolymer in which a side chain has a crosslinkable functional group You may manufacture by any method.
上記したグラフト共重合体の製造方法としては、例えば、
（i）末端に重合性不飽和官能基を有し、かつ架橋性官能基を含有するフッ素系重合体からなるマクロモノマーの存在下に架橋性官能基含有ビニル単量体を含む単量体混合物を共重合してグラフト共重合体を得る方法（マクロモノマー法）；
（ii）重合体セグメント中にアゾ基やパーオキサイド基等の重合開始基を有し、かつ架橋性官能基を有する重合体の存在下に、架橋性官能基含有単量体及びフッ素原子含有単量体を含む単量体混合物を共重合してグラフト共重合体を得る方法。
（iii）官能基を含有する重合体に対し、該官能基と反応可能な官能基を有する１種又は２種以上の重合体を反応させることによりグラフト共重合体を得る方法。
As a manufacturing method of the above-mentioned graft copolymer, for example,
(I) A monomer mixture containing a crosslinkable functional group-containing vinyl monomer in the presence of a macromonomer comprising a fluoropolymer having a polymerizable unsaturated functional group at the terminal and containing a crosslinkable functional group A method of obtaining a graft copolymer by copolymerizing (macromonomer method);
(Ii) A crosslinkable functional group-containing monomer and a fluorine atom-containing monomer in the presence of a polymer having a polymerization initiating group such as an azo group or a peroxide group in the polymer segment and a crosslinkable functional group. A method of obtaining a graft copolymer by copolymerizing a monomer mixture containing a monomer.
(Iii) A method of obtaining a graft copolymer by reacting a polymer containing a functional group with one or more polymers having a functional group capable of reacting with the functional group.
上記した製法のうちでも、上記（i）のマクロモノマー法が、グラフト共重合体を効率よく製造できる点から好ましい。
また、該マクロモノマーにおける末端重合性不飽和官能基は、共重合性の観点から（メタ）アクリロイル基又はスチリル基が好ましく、中でも（メタ）アクリロイル基が特に好ましい。
Among the above-described production methods, the macromonomer method (i) is preferable from the viewpoint that the graft copolymer can be produced efficiently.
In addition, the terminal polymerizable unsaturated functional group in the macromonomer is preferably a (meth) acryloyl group or a styryl group from the viewpoint of copolymerizability, and among them, a (meth) acryloyl group is particularly preferable.
本発明のグラフト共重合体は、架橋性官能基を有する主鎖、及び架橋性官能基を有するフッ素系重合体からなる側鎖とから構成される。フッ素セグメントを側鎖に配することによりフッ素特性を有効に示すことができるため、フッ素含有量が比較的少ない共重合体を用いた場合でもフッ素系コーティング剤として優れた性能が発揮される。
さらに、主鎖及び側鎖に配された架橋性官能基により架橋を施すことで、耐久性にも優れた強靭なコーティング層が得られる。
The graft copolymer of the present invention comprises a main chain having a crosslinkable functional group and a side chain made of a fluoropolymer having a crosslinkable functional group. Since the fluorine characteristic can be effectively shown by arranging the fluorine segment in the side chain, even when a copolymer having a relatively small fluorine content is used, excellent performance as a fluorine-based coating agent is exhibited.
Furthermore, a tough coating layer having excellent durability can be obtained by crosslinking with a crosslinkable functional group arranged on the main chain and side chain.
本発明のグラフト共重合体の側鎖に導入される架橋性官能基量は、０．２〜１．０ｍｅｑ／ｇの範囲であることが好ましく、０．２〜０．７ｍｅｑ／ｇの範囲であることがより好ましい。側鎖に０．２ｍｅｑ／ｇ以上の架橋性官能基が導入されることにより、コーティング層の耐久性が一段と向上する。また、１．０ｍｅｑ／ｇ以下の場合には、撥水・撥油性及び耐汚染性等のフッ素の特性を効果的に発現し易くなる傾向がある。
本発明のグラフト共重合体を製造するに当たり上記したように各種公知の方法を採用し得るが、いずれの方法においてもグラフト構造を有さない側鎖成分のみの重合体（フッ素系リニアポリマー）が少量生成する。該フッ素系リニアポリマーは塗膜化された際の強靭性が十分でなく、長期使用時にはコーティング層から脱離し得るために耐久性の悪化を招く場合がある。フッ素特性を損なわない範囲で側鎖に上記量の架橋性官能基を導入することにより、該フッ素系リニアポリマーも少量の架橋性官能基を有することとなり、コーティング層におけるマトリックス成分に結合されるために耐久性が向上するものと推察される。
The amount of the crosslinkable functional group introduced into the side chain of the graft copolymer of the present invention is preferably in the range of 0.2 to 1.0 meq / g, and in the range of 0.2 to 0.7 meq / g. More preferably. By introducing a crosslinkable functional group of 0.2 meq / g or more into the side chain, the durability of the coating layer is further improved. Moreover, in the case of 1.0 meq / g or less, there is a tendency that the characteristics of fluorine such as water repellency / oil repellency and stain resistance are easily expressed effectively.
In producing the graft copolymer of the present invention, various known methods can be adopted as described above, but in any method, a polymer having only a side chain component (fluorine-based linear polymer) having no graft structure is used. A small amount is produced. The fluorine-based linear polymer does not have sufficient toughness when formed into a coating film, and may be detached from the coating layer when used for a long period of time. By introducing the above-mentioned amount of crosslinkable functional group into the side chain within a range that does not impair the fluorine characteristics, the fluorine-based linear polymer also has a small amount of crosslinkable functional group and is bonded to the matrix component in the coating layer. It is estimated that the durability is improved.
側鎖に導入される架橋性官能基は上記した主鎖に導入される官能基と同様の官能基を使用することができるが、側鎖に導入された架橋性官能基と同種類の官能基を導入することが好ましい。主鎖及び側鎖に導入された架橋性官能基の種類が別種の場合はそれぞれに対応する架橋剤を配合する必要性が生じる場合もあり、操作が煩雑となる。
また、主鎖の際と同様に製造上の安定性、架橋反応の制御のし易さ、架橋後の塗膜物性等の観点から水酸基、カルボキシル基及び（メタ）アクリロイル基が好ましく、水酸基が特に好ましい。
The crosslinkable functional group introduced into the side chain may be the same functional group as the functional group introduced into the main chain, but the same type of functional group as the crosslinkable functional group introduced into the side chain. Is preferably introduced. When the type of the crosslinkable functional group introduced into the main chain and the side chain is different, it may be necessary to add a crosslinking agent corresponding to each type, and the operation becomes complicated.
Further, as in the case of the main chain, a hydroxyl group, a carboxyl group and a (meth) acryloyl group are preferred from the viewpoints of production stability, ease of control of the crosslinking reaction, coating film properties after crosslinking, etc. preferable.
上記の側鎖に導入される架橋性官能基は、ω位に架橋性官能基を有する炭素数１０以上の単量体に由来するものであることが好ましい。例えばヒドロキシエチル（メタ）アクリレートにε−カプロラクトンを付加させた化合物がこれに該当し、具体例としては商品名でプラクセルＦＡ１ＤＤＭ、プラクセルＦＡ２Ｄ、プラクセルＦＡ３Ｄ、プラクセルＦＡ１０Ｌ、プラクセルＦＭ２Ｄ、プラクセルＦＭ３及びプラクセルＦＭ５（いずれもダイセル社製）等が挙げられる。この他にもポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート及びポリエチレン／ポリプロピレンブロック体の（メタ）アクリレート化物等のポリアルキレングリコールモノ（メタ）アクリレート類、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート（例えば、東亞合成社製、商品名「アロニックスＭ−５３００」）等が挙げられ、これらの内の１種又は２種以上を使用することができる。
これらの化合物により側鎖に架橋性官能基が導入された場合は側鎖から離れた位置に架橋点が存在し、比較的フッ素セグメントの表面配向を妨げにくいために好適である。
The crosslinkable functional group introduced into the side chain is preferably derived from a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position. For example, a compound obtained by adding ε-caprolactone to hydroxyethyl (meth) acrylate corresponds to this, and specific examples include, for example, Plaxel FA1DDM, Plaxel FA2D, Plaxel FA3D, Plaxel FA10L, Plaxel FM3D, Plaxel FM3 and Plaxel FM5 ( All of them are manufactured by Daicel Corporation). Other than these, polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and (meth) acrylates of polyethylene / polypropylene block bodies, ω-carboxy-polycaprolactone mono (Meth) acrylate (for example, trade name “Aronix M-5300” manufactured by Toagosei Co., Ltd.) and the like can be used, and one or more of these can be used.
When a crosslinkable functional group is introduced into the side chain by these compounds, it is preferable because a crosslinking point exists at a position away from the side chain and the surface orientation of the fluorine segment is relatively difficult to be disturbed.
上記したω位に架橋性官能基を有する炭素数１０以上の単量体の中でも、分子内にカプロラクトン由来の構造を有するものであるヒドロキシエチル（メタ）アクリレートにε−カプロラクトンを付加させた化合物及びω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレートが撥水・撥油性及び耐久性がより良好となることから好ましい。さらには、官能基が水酸基であるω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレートがより好ましい。本発明では、ω位に架橋性官能基を有する炭素数１０以上の単量体として、分子内にカプロラクトン由来の構造を有するものを用いる。
また、重合性不飽和基としては、摩擦耐久性及び耐汚染性が良好となる点からアクリレート型が好ましい。
Among the monomers having 10 or more carbon atoms having a crosslinkable functional group at the ω position, a compound obtained by adding ε-caprolactone to hydroxyethyl (meth) acrylate having a structure derived from caprolactone in the molecule, and ω-Carboxy-polycaprolactone mono (meth) acrylate is preferred because it provides better water / oil repellency and durability. Furthermore, ω-carboxy-polycaprolactone mono (meth) acrylate whose functional group is a hydroxyl group is more preferable. In the present invention, a monomer having a structure derived from caprolactone in the molecule is used as the monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position.
The polymerizable unsaturated group is preferably an acrylate type in terms of good friction durability and stain resistance.
本発明のグラフト共重合体の側鎖を構成するフッ素系重合体は、上記フッ素原子含有ビニル単量体および架橋性官能基以外にも、フッ素の特性を損なわない範囲で他のビニル単量体を共重合させることができる。
該共重合可能なビニル単量体としては、（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）アクリル酸シクロヘキシルおよび（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸オクタデシル等の（メタ）アクリル酸アルキルエステル；スチレン、α−メチルスチレンおよびｐ−メチルスチレン等のスチレン誘導体；（メタ）アクリロニトリル；（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、ジメチルアミノエチル（メタ）アクリルアミド等のアミノアルキル（メタ）アクリルアミド等が挙げられる。
The fluorine-based polymer constituting the side chain of the graft copolymer of the present invention is not limited to the above-mentioned fluorine atom-containing vinyl monomer and crosslinkable functional group. Can be copolymerized.
Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and ( (Meth) acrylic acid alkyl esters such as isobornyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate; styrene such as styrene, α-methylstyrene and p-methylstyrene Derivatives; (meth) acrylonitrile; aminoalkyl (meth) acrylamides such as (meth) acrylamide, dimethylaminomethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide and the like.
上記したとおり、本発明のコーティング剤では必要に応じてグラフト共重合体に加えてさらに架橋剤を使用することができる。用いる架橋剤は導入された架橋性官能基と架橋反応し得るものであれば特に限定はされないが、例えばエポキシ系、イソシアネート系、アミノ樹脂系、ヒドラジド系、カルボジイミド系及びオキサゾリン系等の架橋剤から選ばれる１種又は２種以上を用いることができる。これらの中でも反応性及び制御のし易さ等からイソシアネート系の架橋剤が好ましい。架橋剤の添加量はグラフト共重合体の架橋性官能基量に対して０．１〜１０当量の範囲で用いることが好ましく、より好ましくは０．２〜５当量であり、さらに好ましくは０．５〜２当量である。
架橋反応は例えば８０〜２００℃程度の加熱下条件で実施することができるが、使用する架橋性官能基及び架橋剤の種類に応じて適宜設定される。
As described above, in the coating agent of the present invention, a crosslinking agent can be further used in addition to the graft copolymer, if necessary. The cross-linking agent to be used is not particularly limited as long as it can cross-link with the introduced cross-linkable functional group, but examples thereof include epoxy-based, isocyanate-based, amino resin-based, hydrazide-based, carbodiimide-based, and oxazoline-based crosslinking agents. One kind or two or more kinds selected can be used. Among these, an isocyanate-based crosslinking agent is preferable from the viewpoint of reactivity and ease of control. The addition amount of the crosslinking agent is preferably used in the range of 0.1 to 10 equivalents, more preferably 0.2 to 5 equivalents, and still more preferably 0.1 to 10 equivalents relative to the amount of the crosslinkable functional group of the graft copolymer. 5 to 2 equivalents.
The crosslinking reaction can be carried out under heating conditions of, for example, about 80 to 200 ° C., but is appropriately set according to the type of the crosslinkable functional group and the crosslinking agent used.
イソシアネート系架橋剤は分子内に２個以上のイソシアネート基を有するものであれば種々のものが使用可能であり、具体的な例としては、ｐ−フェニレンジイソシアネート、４,４'−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、４,４'−ジフェニレンジイソシアネート、１,５−オクチレンジイソシアネート、トリメチレンジイソシアネート、テトラメチレンジイネシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１,３−シクロペンタンジイソシアネート、１,４−シクロヘキサンジイソシアネート、４,４'−メチレンビス（シクロヘキシルイソシアネート）、メチル２,４−シクロヘキサンジイソシアネート、メチル２,６−シクロヘキサンジイソシアネート、ジフェニルメタンジイソシアネート、１,４−ビス（イソシアネートメチル）シクロヘキサン、１,３−ビス（イソシアネートメチル）シクロヘキサン、イソホロンジイソシアネート及びカルボジイミド変性４,４'−ジフェニルメタンジイソシアネート等が挙げられる。
これらの中でも、ヘキサメチレンジイソシアネート及びイソホロンジイソシアネート等の脂肪族イソシアネートが、コーティング層の耐汚染性の点から好ましい。
A variety of isocyanate crosslinking agents can be used as long as they have two or more isocyanate groups in the molecule. Specific examples thereof include p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, Range isocyanate, 4,4'-diphenylene diisocyanate, 1,5-octylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4- Cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, diphenylmethane diiso Aneto, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and carbodiimide-modified 4,4'-diphenylmethane diisocyanate.
Among these, aliphatic isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate are preferable from the viewpoint of stain resistance of the coating layer.
エポキシ系架橋剤も分子内に２個以上のエポキシ基を有する化合物であれば特に制限なく使用が可能である。具体的な例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ系樹脂、ビスフェノールＺ型エポキシ樹脂及び水添ビスフェノール型エポキシ樹脂等のビスフェノール型のエポキシ樹脂；エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン及び１，３−ビス(Ｎ，Ｎ’−ジグリシジルアミノメチル)シクロヘキサンなどを挙げることができる。 Epoxy crosslinking agents can also be used without particular limitation as long as they are compounds having two or more epoxy groups in the molecule. Specific examples include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol Z type epoxy resins and hydrogenated bisphenol type epoxy resins; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylamine, N, N, N ′, N′-tetraglycidyl- Examples thereof include m-xylenediamine and 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane.
アミノ樹脂系架橋剤としては、アルキルエーテル化メラミン、アルキルエーテル化尿素樹脂及びアルキルエーテル化ベンゾグアナミン等が挙げられる。これらのうち、アルキルエーテル化メラミンとしては、ヘキサメトキシメチロールメラミン、ヘキサブトキシメチロールメラミン等の完全アルキルエーテル化メラミンもしくはアルキルエーテル化度が５以下の部分アルキルエーテル化メラミン等が使用できる。また、アルキルエーテル化メラミンの２量体、３量体等の多量体も使用できる。 Examples of the amino resin-based crosslinking agent include alkyl etherified melamine, alkyl etherified urea resin and alkyl etherified benzoguanamine. Among these, as the alkyl etherified melamine, a completely alkyl etherified melamine such as hexamethoxymethylol melamine or hexabutoxymethylol melamine or a partially alkyl etherified melamine having an alkyl etherification degree of 5 or less can be used. In addition, multimers such as alkyl etherified melamine dimers and trimers can also be used.
架橋性官能基が重合性ビニル基の場合は、必要に応じて光重合開始剤を添加することにより活性エネルギー線硬化型のコーティング剤とすることができる。
光重合開始剤を配合する場合において、該光重合開始剤としてはベンゾインとそのアルキルエーテル類、アセトフェノン類、アントラキノン類、チオキサントン類、ケタール類、ベンゾフェノン類、キサントン類、アシルホスフィンオキシド類及びα−ジケトン類等が挙げられ、これらの中でもベンゾフェノン類及びチオキサントン類のものが重合速度が速い点で好ましい。光重合開始剤の使用量は本発明のグラフト共重合体１００質量部に対して０．０１〜１０質量部が好ましい。
また、活性エネルギー線による感度を向上させるため、光増感剤を併用することもできる。該光増感剤としては、安息香酸系及びアミン系光増感剤等が挙げられ、これらは２種以上を組み合わせて用いることもできる。
When the crosslinkable functional group is a polymerizable vinyl group, an active energy ray-curable coating agent can be obtained by adding a photopolymerization initiator as necessary.
In the case of blending a photopolymerization initiator, the photopolymerization initiator includes benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, acylphosphine oxides, and α-diketones. Among these, benzophenones and thioxanthones are preferred because of their high polymerization rate. The amount of the photopolymerization initiator used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the graft copolymer of the present invention.
Moreover, in order to improve the sensitivity by an active energy ray, a photosensitizer can also be used together. Examples of the photosensitizer include benzoic acid and amine photosensitizers, and these may be used in combination of two or more.
活性エネルギー線としては可視光線、紫外線、Ｘ線及び電子線等が挙げられ、安価な装置を使用できることから紫外線を使用することが好ましい。紫外線を使用する際の光源としては、超高圧、高圧、中圧又は低圧水銀灯、メタルハライド灯、キセノンランプ、無電極放電ランプ及びカーボンアーク灯等が挙げられ、数秒乃至数分間照射すれば良い。 Examples of active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, and ultraviolet rays are preferably used because inexpensive devices can be used. Examples of the light source when using ultraviolet rays include ultra-high pressure, high pressure, medium pressure or low pressure mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge lamp, and carbon arc lamp, and irradiation may be performed for several seconds to several minutes.
本発明のコーティング剤には、さらに単独でコーティング層を形成可能なフッ素非含有のバインダー成分を配合することができる。配合されるバインダーとしては、公知汎用の各種ポリマー及びオリゴマー等を用いることができるが、本発明のグラフト共重合体と同種の架橋性官能基を有するアクリル系ポリマーを配合するのが特に好ましい。
配合量としては、グラフト共重合体の重量１（固形分）に対し、バインダー成分の配合量を５（固形分）以下にすることが好ましく、２以下にするのがより好ましい。バインダー成分の配合量が５を超える場合にはコーティング層中のフッ素濃度が薄まるため、フッ素特性が損なわれる。
The coating agent of the present invention may further contain a fluorine-free binder component capable of forming a coating layer alone. As the binder to be blended, various known general-purpose polymers and oligomers can be used, and it is particularly preferable to blend an acrylic polymer having the same kind of crosslinkable functional group as the graft copolymer of the present invention.
As a compounding quantity, it is preferable to make the compounding quantity of a binder component into 5 (solid content) or less with respect to the weight 1 (solid content) of a graft copolymer, and it is more preferable to set it as 2 or less. When the blending amount of the binder component exceeds 5, the fluorine concentration in the coating layer becomes thin, so that the fluorine characteristics are impaired.
本発明のコーティング剤は、フッ素の特性及びコーティング層の耐久性を損なわない範囲で塗膜強度向上及び堆積低効率調整の目的でシリカや酸化チタン等を配合することもできる。 The coating agent of the present invention can be blended with silica, titanium oxide or the like for the purpose of improving the coating film strength and adjusting the deposition efficiency, as long as the properties of fluorine and the durability of the coating layer are not impaired.
以下、実施例に基づいて本発明を具体的に説明する。以下の記載において「部」は質量部を意味し、「％」は質量％を意味する。
また、各例において得られたマクロモノマー、グラフト共重合体、コーティング剤及びキャリアについては、以下の物性及び性質を測定することにより評価した。
（１）マクロモノマー及びグラフト共重合体の特性
ａ）固形分
測定サンプル約１ｇを秤量（ａ）し、次いで、通風乾燥機１５５℃、３０分間乾燥後の残分を測定（ｂ）し、以下の式より算出した。測定には秤量ビンを使用した。その他の操作については、ＪＩＳ Ｋ ００６７−１９９２（化学製品の減量及び残分試験方法）に準拠した。
［固形分（％）］＝（ｂ／ａ）×１００
Hereinafter, the present invention will be specifically described based on examples. In the following description, “part” means part by mass, and “%” means mass%.
Further, the macromonomer, graft copolymer, coating agent and carrier obtained in each example were evaluated by measuring the following physical properties and properties.
(1) Characteristics of Macromonomer and Graft Copolymer a) About 1 g of solid content measurement sample is weighed (a), and then the residue after drying for 30 minutes in an air dryer 155 ° C. is measured (b). It was calculated from the following formula. A weighing bottle was used for the measurement. Other operations were in accordance with JIS K 0067-1992 (chemical product weight loss and residue test method).
[Solid content (%)] = (b / a) × 100
ｂ）分子量
試料をテトラヒドロフラン（以下、「ＴＨＦ」という）に溶解して濃度０．２％の溶液を調整した後、該溶液１００μＬをカラム（東ソー社製、「ＴＳＫ−ＧＥＬ ＭＵＬＴＩＰＯＲＥ ＨＸＬ−Ｍ」（４本））に注入し、カラム温度４０℃でＴＨＦを流速１．０ｍＬ／分でカラムに通してカラムに吸着した成分を溶離させるゲル浸透クロマトグラフ（ＧＰＣ法）により測定した。数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）は分子量が既知のポリスチレンを標準物質と用いてあらかじめ作成しておいた検量線から算出した。
b) Molecular weight After a sample was dissolved in tetrahydrofuran (hereinafter referred to as “THF”) to prepare a solution having a concentration of 0.2%, 100 μL of the solution was added to a column (manufactured by Tosoh Corporation, “TSK-GEL MULTIPIORE HXL-M” ( 4)), and was measured by gel permeation chromatography (GPC method) in which THF was passed through the column at a flow rate of 1.0 mL / min at a column temperature of 40 ° C. to elute the components adsorbed on the column. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated from a calibration curve prepared in advance using polystyrene having a known molecular weight as a standard substance.
（２）コーティング剤の特性
ａ）接触角
自動接触角測定装置「ＯＣＡ−２０」（Ｄａｔａｐｈｙｓｉｃｓ社製）を用い、各試験用塗膜サンプルに対する純水、ｎ−ヘキサデカンの接触角をそれぞれ測定した。
その後、塗膜サンプル上にナイロンたわしをのせ、ラビングテスター（大英科学精器製作所製、学振型染色物摩擦堅牢度試験機）で２ｋｇの荷重をかけて５０往復の摩擦試験を行い、上記と同様に純水、ｎ−ヘキサデカンの接触角を測定した。また、摩擦耐久性の指標として［試験後の接触角／試験前の接触角］を算出した。
(2) Characteristics of Coating Agent a) Contact Angle Using an automatic contact angle measuring device “OCA-20” (manufactured by Dataphysics), the contact angles of pure water and n-hexadecane with respect to each test coating film sample were measured.
After that, a nylon scrubber is put on the coating film sample, and a 50-round reciprocating friction test is performed by applying a load of 2 kg with a rubbing tester (manufactured by Daiei Kagaku Seiki Seisakusho, Gakushin type dyeing friction fastness tester). Similarly, contact angles of pure water and n-hexadecane were measured. Further, [contact angle after test / contact angle before test] was calculated as an index of friction durability.
ｂ）鉛筆硬度
各試験用塗膜サンプルについてＪＩＳ Ｋ ５６００−５−４（引っかき硬度（鉛筆法））に準じて鉛筆引っ掻き試験を実施し、塗膜が傷つかない最大の硬度を測定した。
b) Pencil hardness A pencil scratch test was carried out according to JIS K 5600-5-4 (scratch hardness (pencil method)) for each test paint film sample, and the maximum hardness at which the paint film was not damaged was measured.
ｃ）密着性
各試験用塗膜サンプルについてＪＩＳ Ｋ ５６００−５−６（付着性（クロスカット法））に準じて碁盤目剥離試験を実施し、碁盤目２５ピース中の剥離されなかったピース数を記録した。
c) Adhesiveness For each test film sample, a cross-cut peel test was performed according to JIS K 5600-5-6 (adhesiveness (cross-cut method)), and the number of pieces not peeled in 25 cross-cut pieces Was recorded.
ｄ）耐マジック汚染性
各試験用サンプルに対して黒色マジックインキで線を引き、１時間後にペーパータオルでインキのふき取りを行った。その際のインキのふき取り易さを以下の基準に従い評価した。
◎：軽い力でふき取ることができ、痕跡が残らない
○：やや強い力をかければふき取ることができるが、僅かな痕跡が残る
△：強い力をかければふき取ることができるが、明らかな痕跡が残る
×：ほとんどふき取ることができない
d) Magic stain resistance A line was drawn with black magic ink on each test sample, and the ink was wiped off with a paper towel after 1 hour. The ease of ink wiping at that time was evaluated according to the following criteria.
◎: It can be wiped off with light force, and no trace remains ○: It can be wiped off with a little strong force, but a slight trace remains △: It can be wiped off with a strong force, but there is an obvious trace Remaining ×: Can hardly be wiped off
ｅ）耐粉体汚染性
各試験塗膜サンプル板を２枚用意し、当該サンプル板間にカーボン粉末（三菱化学社製、商品名「ＭＡ１００」）を挟み込み、一定の力でこすり付けを行った。その後ペーパータオルでカーボン粉末のふき取りを行い、以下の基準に従いそのふき取り易さを評価した。
○：完全にふき取ることができる
△：ふき取り後に痕跡が残る
×：ふき取り後に明確にカーボン粉末の跡が確認できる
e) Powder contamination resistance Two test coating sample plates were prepared, carbon powder (Mitsubishi Chemical Co., Ltd., trade name “MA100”) was sandwiched between the sample plates, and rubbed with a certain force. . Thereafter, the carbon powder was wiped off with a paper towel, and the ease of wiping was evaluated according to the following criteria.
○: Completely wiped off △: Traces remain after wiping off: Marks of carbon powder can be clearly confirmed after wiping off
ｆ）耐候性
各試験用塗膜サンプルをメタリングウェザーメーター「ＤＡＩＰＬＡ ＭＥＴＡＬ ＷＥＡＴＨＥＲ ＫＵ−Ｒ５ＮＣＩ−Ａ」（ダイプラ・ウィンテス社製）を使用して１００時間の耐候性試験を行った。その後塗膜の表面を観察し、以下の基準に従い評価した。
○：試験前と比較して外観上の差異が認められない
△：試験前と比較して塗膜表面の光沢が低下している
×：塗膜に凹凸や剥がれが確認される
f) Weather resistance The coating film samples for each test were subjected to a weather resistance test for 100 hours using a metalling weather meter “DAIPLA METAL WEATHER KU-R5NCI-A” (manufactured by Daipura Wintes). Thereafter, the surface of the coating film was observed and evaluated according to the following criteria.
○: No difference in appearance compared to before the test △: The gloss of the coating film surface is lower than before the test ×: Concavities and convexities or peeling are confirmed on the coating film
＜マクロモノマーの製造＞
合成例１：マクロモノマーＡの製造
攪拌機、滴下ロート、還流冷却器、窒素ガス導入管および温度計を備えたガラス製フラスコに、単量体としてパーフルオロヘキシルエチルアクリレート（ユニマテック社製、商品名「ケミノックスＦＡＡＣ６」）８０部、ヒドロキシエチルアクリレートのカプロラクトン２ｍｏｌ付加品（ダイセル社製、商品名「プラクセルＦＡ２Ｄ」）２０部、重合溶剤としてメチルイソブチルケトン（以下、「ＭＩＢＫ」という）１００部、連鎖移動剤として３−メルカプトプロピオン酸（以下、「ＭＰＡ」という）１．５部を仕込み、窒素気流下で９０℃に加熱攪拌した。別容器にてＭＩＢＫ２０部に２，２’−アゾビス（２−メチルブチロニトリル）（日本ファインケム社製、商品名「ＡＢＮ−Ｅ」）０．５部を添加、溶解して重合開始剤溶液を調整し、フラスコ内溶液を９０℃に保ったままこの重合開始剤溶液を３時間かけてフラスコへ滴下した。さらに３時間加熱攪拌を継続することにより重合を完結させ、片末端にカルボキシル基を有する重合体を得た。
窒素気流を空気バブリングに切り替えて、引き続き同じフラスコ内にメトキシフェノール０．０２部、テトラブチルアンモニウムブロミド１．０部、グリシジルメタクリレート（以下、「ＧＭＡ」という）２．０部を加えて１１０℃で８時間加熱した後に室温まで冷却し、ＭＩＢＫを添加して固形分を５０％に調整することにより片末端にメタクリロイル基を有するマクロモノマーＡのＭＩＢＫ溶液を得た。
得られたマクロモノマーＡの分子量を測定したところ、数平均分子量（Ｍｎ）＝４，９００、重量平均分子量（Ｍｗ）＝１０，８００であった。また、このマクロモノマーＡは架橋性官能基として０．５６ｍｅｑ／ｇ相当の水酸基を有する。
<Manufacture of macromonomer>
Synthesis Example 1 Production of Macromonomer A Perfluorohexyl ethyl acrylate (manufactured by Unimatec Co., Ltd., trade name "") was added to a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas inlet tube and a thermometer. Cheminox FAAC6 ") 80 parts, hydroxyethyl acrylate caprolactone 2 mol addition product (product name" Placcel FA2D "manufactured by Daicel), 20 parts, polymerization solvent 100 parts methyl isobutyl ketone (hereinafter referred to as" MIBK "), chain transfer agent As described above, 1.5 parts of 3-mercaptopropionic acid (hereinafter referred to as “MPA”) was charged and stirred at 90 ° C. under a nitrogen stream. In a separate container, 0.5 part of 2,2′-azobis (2-methylbutyronitrile) (manufactured by Nippon Finechem Co., Ltd., trade name “ABN-E”) is added and dissolved in 20 parts of MIBK to obtain a polymerization initiator solution. The polymerization initiator solution was dropped into the flask over 3 hours while adjusting and maintaining the solution in the flask at 90 ° C. Furthermore, the polymerization was completed by continuing heating and stirring for 3 hours to obtain a polymer having a carboxyl group at one end.
The nitrogen stream was switched to air bubbling, and subsequently 0.02 part of methoxyphenol, 1.0 part of tetrabutylammonium bromide and 2.0 parts of glycidyl methacrylate (hereinafter referred to as “GMA”) were added to the same flask at 110 ° C. After heating for 8 hours, the mixture was cooled to room temperature, and MIBK was added to adjust the solid content to 50% to obtain a MIBK solution of macromonomer A having a methacryloyl group at one end.
When the molecular weight of the obtained macromonomer A was measured, the number average molecular weight (Mn) was 4,900 and the weight average molecular weight (Mw) was 10,800. The macromonomer A has a hydroxyl group corresponding to 0.56 meq / g as a crosslinkable functional group.
合成例２〜１４、１７〜２０：マクロモノマーＢ〜Ｎ、Ｑ〜Ｔの製造
単量体、連鎖移動剤およびＧＭＡを表１に示す通り用いた以外は合成例１と同様の操作を行い、マクロモノマーＢ〜Ｎ、Ｑ〜ＴのＭＩＢＫ溶液を得た。
得られた各マクロモノマーの物性値について表１に示す。
Synthesis Examples 2 to 14 and 17 to 20: Production of Macromonomer B to N and Q to T The same operation as in Synthesis Example 1 was performed except that the monomer, chain transfer agent and GMA were used as shown in Table 1. MIBK solutions of macromonomers B to N and Q to T were obtained.
It shows in Table 1 about the physical-property value of each obtained macromonomer.
合成例１５：マクロモノマーＯの製造
攪拌機、滴下ロート、還流冷却器、窒素ガス導入管および温度計を備えたガラス製フラスコに、単量体としてケミノックスＦＡＡＣ６を８０部、（東亞合成社製、商品名「アロニックスＭ−５３００」）２０部、重合溶剤としてＭＩＢＫ１００部、連鎖移動剤として２−メルカプトエタノール（以下、「ＭＴＧ」という）１．１部を仕込み、窒素気流下で９０℃に加熱攪拌した。別容器にてＭＩＢＫ２０部にＡＢＮ−Ｅ１．０部を添加、溶解して重合開始剤溶液を調整し、フラスコ内溶液を９０℃に保ったままこの重合開始剤溶液を３時間かけてフラスコへ滴下した。さらに３時間加熱攪拌を継続することにより重合を完結させ、片末端に水酸基を有する重合体を得た。
窒素気流を空気バブリングに切り替えて、引き続き同じフラスコ内にメトキシフェノール０．０２部、ジオクチルスズジラウレート（日東化成社製、商品名「ネオスタンＵ−８１０」）０．０１部、２−イソシアナトエチルメタクリレート（昭和電工社製、商品名「カレンズＭＯＩ」）２．２部を加えて１１０℃で３時間加熱した後に室温まで冷却し、ＭＩＢＫを添加して固形分を５０％に調整することにより、片末端にメタクリロイル基を有し官能基としてエポキシ基を持つマクロモノマーＯのＭＩＢＫ溶液を得た。
得られたマクロモノマーＯの物性値について表１に示す。
Synthesis Example 15: Production of macromonomer O In a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas inlet tube and a thermometer, 80 parts of Cheminox FAAC6 as a monomer (manufactured by Toagosei Co., Ltd., product) (Name "Aronix M-5300") 20 parts, MIBK 100 parts as a polymerization solvent, 1.1 parts 2-mercaptoethanol (hereinafter referred to as "MTG") as a chain transfer agent, and heated and stirred at 90 ° C under a nitrogen stream . In a separate container, 1.0 part of ABN-E is added to 20 parts of MIBK and dissolved to prepare a polymerization initiator solution, and this polymerization initiator solution is dropped into the flask over 3 hours while maintaining the solution in the flask at 90 ° C. did. Furthermore, the polymerization was completed by continuing heating and stirring for 3 hours to obtain a polymer having a hydroxyl group at one end.
The nitrogen stream was switched to air bubbling, and subsequently 0.02 part of methoxyphenol, 0.01 part of dioctyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-810”), 2-isocyanatoethyl methacrylate By adding 2.2 parts (made by Showa Denko KK, trade name “Karenz MOI”), heating at 110 ° C. for 3 hours, cooling to room temperature, adding MIBK to adjust the solid content to 50%, A MIBK solution of macromonomer O having a methacryloyl group at the end and an epoxy group as a functional group was obtained.
The physical property values of the obtained macromonomer O are shown in Table 1.
合成例１６：マクロモノマーＰの製造
単量体、連鎖移動剤およびカレンズＭＯＩを表１に示す通り用いた以外は合成例１５と同様の操作を行い、マクロモノマーＰのＭＩＢＫ溶液を得た。
得られた各マクロモノマーＰの物性値について表１に示す。
Synthesis Example 16: Production of Macromonomer P A MIBK solution of Macromonomer P was obtained in the same manner as in Synthesis Example 15 except that the monomer, chain transfer agent and Karenz MOI were used as shown in Table 1.
It shows in Table 1 about the physical-property value of each obtained macromonomer P. FIG.
表１で用いた化合物の詳細を以下に示す。
３ＦＭ：トリフルオロメチルメチルメタクリレート
（大阪有機化学工業社製、商品名「ビスコート−３ＦＭ」）
ＦＡＡＣ−４：パーフルオロブチルエチルアクリレート
（ユニマテック社製、商品名「ケミノックスＦＡＡＣ４」）
ＦＡＡＣ−６：パーフルオロヘキシルエチルアクリレート
（ユニマテック社製、商品名「ケミノックスＦＡＡＣ６」）
ＦＡＭＡＣ−６：パーフルオロヘキシルエチルメタクリレート
（ユニマテック社製、商品名「ケミノックスＦＡＭＡＣ６」）
ＦＡ−１０８：パーフルオロオクチルエチルアクリレート
（共栄社化学社製、商品名「ライトアクリレートＦＡ−１０８」）
ＨＥＡ：２−ヒドロキシエチルアクリレート
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＦＡ１ＤＤＭ：ＨＥＡのカプロラクトン１ｍｏｌ付加物
（ダイセル化学社製、商品名「プラクセルＦＡ１ＤＤＭ」）
ＦＡ２Ｄ：ＨＥＡのカプロラクトン２ｍｏｌ付加物
（ダイセル化学社製、商品名「プラクセルＦＡ２Ｄ」）
ＦＭ−２：ＨＥＭＡのカプロラクトン２ｍｏｌ付加物
（ダイセル化学社製、商品名「プラクセルＦＭ２Ｄ」）
ＦＡ３Ｄ：ＨＥＡのカプロラクトン３ｍｏｌ付加物
（ダイセル化学社製、商品名「プラクセルＦＡ３Ｄ」）
ＡＥ−２００：ポリエチレングリコールモノアクリレート
（日油社製、商品名「ブレンマーＡＥ−２００」）
Ｍ５３００：ω−カルボキシ−ポリカプロラクトン（ｎ≒２）モノアクリレート
（東亞合成社製、商品名「アロニックスＭ−５３００」）
ＧＭＡ：グリシジルメタクリレート
ＭＭＡ：メチルメタクリレート
ＭＰＡ：３−メルカプトプロピオン酸
ＭＴＧ：２−メルカプトエタノール
カレンズＭＯＩ：２−イソシアナトエチルメタクリレート（昭和電工社製）
Details of the compounds used in Table 1 are shown below.
3FM: trifluoromethyl methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “Biscoat-3FM”)
FAAC-4: Perfluorobutyl ethyl acrylate
(Product name “Cheminox FAAC4” manufactured by Unimatec)
FAAC-6: Perfluorohexyl ethyl acrylate
(Product name "Cheminox FAAC6" manufactured by Unimatec)
FAMAC-6: Perfluorohexyl ethyl methacrylate
(Product name "Cheminox FAMAC6" manufactured by Unimatec)
FA-108: Perfluorooctyl ethyl acrylate
(Kyoeisha Chemical Co., Ltd., trade name “Light Acrylate FA-108”)
HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate FA1DDM: 1 mol caprolactone adduct of HEA
(Daicel Chemical Co., Ltd., trade name "Placcel FA1DDM")
FA2D: 2 mol of caprolactone adduct of HEA
(Product name "Placcel FA2D" manufactured by Daicel Chemical Industries, Ltd.)
FM-2: caprolactone 2 mol adduct of HEMA
(Product name "PLAXEL FM2D" manufactured by Daicel Chemical Industries, Ltd.)
FA3D: 3 mol of caprolactone adduct of HEA
(Daicel Chemical Industries, trade name "Placcel FA3D")
AE-200: Polyethylene glycol monoacrylate
(Manufactured by NOF Corporation, trade name "Blemmer AE-200")
M5300: ω-carboxy-polycaprolactone (n≈2) monoacrylate
(Product name "Aronix M-5300", manufactured by Toagosei Co., Ltd.)
GMA: glycidyl methacrylate MMA: methyl methacrylate MPA: 3-mercaptopropionic acid MTG: 2-mercaptoethanol Karenz MOI: 2-isocyanatoethyl methacrylate (manufactured by Showa Denko)
＜グラフト共重合体の製造＞
製造例１：グラフト共重合体Ａ１の製造
攪拌機、滴下ロート、還流冷却器、窒素ガス導入管および温度計を備えたガラス製フラスコに、上記で得られたマクロモノマーＡのＭＩＢＫ溶液を３０部（固形分として１５部）、メチルメタクリレート（以下、「ＭＭＡ」という）６７部、２−ヒドロキシエチルメタクリレート（以下、「ＨＥＭＡ」という）１８部、及びＭＩＢＫ１０６部を仕込み、窒素気流下で９０℃に加熱攪拌した。別容器にてＭＩＢＫ３０部にＡＢＮ−Ｅ１．５部を添加、溶解して重合開始剤溶液を調整し、フラスコ内溶液を９０℃に保ったままこの重合開始剤溶液を３時間かけてフラスコへ滴下した。さらに３時間加熱攪拌を継続することにより重合を完結させ、グラフト共重合体Ａ１を得た。
得られたグラフト共重合体Ａ１の分子量を測定したところ、数平均分子量（Ｍｎ）＝１４，０００、重量平均分子量（Ｍｗ）＝３０，０００であった。また、このグラフト共重合体Ａ１は主鎖中の架橋性官能基として１．６３ｍｅｑ／ｇ、側鎖中の架橋性官能基として０．５６ｍｅｑ／ｇ相当の水酸基を有する。
<Production of graft copolymer>
Production Example 1: Production of Graft Copolymer A1 Into a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas inlet tube and a thermometer, 30 parts of the above-obtained macromonomer A MIBK solution ( 15 parts as solids), 67 parts of methyl methacrylate (hereinafter referred to as “MMA”), 18 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”), and 106 parts of MIBK are charged and heated to 90 ° C. under a nitrogen stream. Stir. In a separate container, add 1.5 parts of ABN-E to 30 parts of MIBK, dissolve to prepare a polymerization initiator solution, and drop the polymerization initiator solution into the flask over 3 hours while keeping the solution in the flask at 90 ° C. did. Further, the polymerization was completed by continuing the heating and stirring for 3 hours to obtain a graft copolymer A1.
When the molecular weight of the obtained graft copolymer A1 was measured, the number average molecular weight (Mn) was 14,000, and the weight average molecular weight (Mw) was 30,000. The graft copolymer A1 has a hydroxyl group corresponding to 1.63 meq / g as a crosslinkable functional group in the main chain and 0.56 meq / g as a crosslinkable functional group in the side chain.
製造例２〜１７、１９〜２８：グラフト共重合体Ａ２〜Ａ１７、Ａ１９〜Ａ２８の製造
主鎖を構成する単量体及び側鎖となるマクロモノマーを表２−１〜表２−４に示す通り用いた以外は製造例１と同様の操作を行い、グラフト共重合体Ａ２〜Ａ１７並びにＡ１９〜Ａ２８を得た。
得られた各グラフト共重合体の物性値について表２−１〜表２−４に示す。
Production Examples 2 to 17 and 19 to 28: Production of Graft Copolymers A2 to A17 and A19 to A28 Tables 2-1 to 2-4 show monomers constituting the main chain and macromonomers serving as side chains. The same operations as in Production Example 1 were carried out except that the graft copolymers were used, and graft copolymers A2 to A17 and A19 to A28 were obtained.
It shows to Table 2-1-Table 2-4 about the physical-property value of each obtained graft copolymer.
製造例１８：グラフト共重合体Ａ１８の製造
攪拌機、滴下ロート、還流冷却器、窒素ガス導入管および温度計を備えたガラス製フラスコに、上記で得られたマクロモノマーＰのＭＩＢＫ溶液を３０部（固形分として１５部）、ＭＭＡ６５部、ＧＭＡ２０部、ＭＩＢＫ１０６部を仕込み、窒素気流下で９０℃に加熱攪拌した。別容器にてＭＩＢＫ２０部にＡＢＮ−Ｅ１．５部を添加、溶解して重合開始剤溶液を調整し、フラスコ内溶液を９０℃に保ったままこの重合開始剤溶液を３時間かけてフラスコへ滴下した。さらに３時間加熱攪拌を継続することにより重合を完結させた。
窒素気流を空気バブリングに切り替えて、引き続き同じフラスコ内にメトキシフェノール０．０５部、テトラブチルアンモニウムブロミド０．５部、ω−カルボキシポリカプロラクトン（ｎ≒２）モノアクリレート（東亞合成社製、商品名「アロニックスＭ−５３００」）４５．３部を加え、９０℃で１２時間加熱し、グラフト共重合体Ａ１８を得た。
得られたグラフト共重合体Ａ１８の物性値について表２−１に示す。
Production Example 18 Production of Graft Copolymer A18 To a glass flask equipped with a stirrer, a dropping funnel, a reflux condenser, a nitrogen gas introduction tube and a thermometer, 30 parts of the MIBK solution of the macromonomer P obtained above ( The solid content was 15 parts), 65 parts of MMA, 20 parts of GMA, and 106 parts of MIBK, and the mixture was heated and stirred at 90 ° C. under a nitrogen stream. In a separate container, 1.5 parts of ABN-E is added to 20 parts of MIBK and dissolved to prepare a polymerization initiator solution. The polymerization initiator solution is dropped into the flask over 3 hours while maintaining the solution in the flask at 90 ° C. did. The polymerization was completed by continuing heating and stirring for 3 hours.
The nitrogen stream was switched to air bubbling, and subsequently 0.05 parts of methoxyphenol, 0.5 parts of tetrabutylammonium bromide, and ω-carboxypolycaprolactone (n≈2) monoacrylate (trade name, manufactured by Toagosei Co., Ltd.) in the same flask. “Aronix M-5300”) 45.3 parts was added and heated at 90 ° C. for 12 hours to obtain a graft copolymer A18.
The physical property values of the obtained graft copolymer A18 are shown in Table 2-1.
表２−１〜２−４で用いた化合物の詳細を以下に示す。
ＥＨＭＡ：２−エチルヘキシルメタアクリレート
ＭＡＡ：メタクリル酸
Details of the compounds used in Tables 2-1 to 2-4 are shown below.
EHMA: 2-ethylhexyl methacrylate MAA: methacrylic acid
比較製造例１〜７：共重合体Ｂ１〜Ｂ７の製造
単量体及びマクロモノマーを表３に示す通り用いた以外は製造例１と同様の操作を行い、共重合体Ｂ１〜Ｂ７を得た。
得られた共重合体Ｂ１〜Ｂ７の物性値について表３に示す。
Comparative Production Examples 1 to 7: Production of Copolymers B1 to B7 Except that the monomers and macromonomers were used as shown in Table 3, the same operations as in Production Example 1 were performed to obtain copolymers B1 to B7. .
It shows in Table 3 about the physical-property value of obtained copolymer B1-B7.
実施例１
製造例１で得られたグラフト共重合体Ａ１を固形分で１００部、架橋剤としてコロネートＨＸ（日本ポリウレタン社製、イソシアネート系架橋剤）２９．０（グラフト共重合体の架橋性官能基量と当量）及び硬化促進触媒としてネオスタンＵ−８１０ ０．０１部（対グラフト共重合体１００ｐｐｍ）を混合し、固形分２０％になるようにメチルエチルケトン（以下、「ＭＥＫ」という）で希釈してコーティング液を調整した。
このコーティング液をバーコーターＮｏ．１２を用いてアロジン処理アルミ試験板「Ａ５０５２Ｐ」（ＴＰ技研社製）上に塗布した後、通風乾燥機にて１２０℃で３０分間乾燥・架橋することにより試験用塗膜サンプルＡ１を得た。
塗膜サンプルＡ１に関し、コーティング剤の各種特性評価を行った結果を表５に示す。
Example 1
100 parts of graft copolymer A1 obtained in Production Example 1 in solid content, coronate HX (manufactured by Nippon Polyurethane Co., Ltd., isocyanate-based crosslinking agent) as a crosslinking agent 29.0 (crosslinkable functional group amount of graft copolymer) Equivalent) and 0.01 part of Neostan U-810 (100 ppm of graft copolymer) as a curing accelerating catalyst are mixed and diluted with methyl ethyl ketone (hereinafter referred to as “MEK”) to a solid content of 20%. Adjusted.
This coating solution was applied to bar coater no. 12 was applied onto an allodin-treated aluminum test plate “A5052P” (manufactured by TP Giken Co., Ltd.), and then dried and crosslinked at 120 ° C. for 30 minutes with a draft dryer to obtain a test coating sample A1.
Table 5 shows the results of various characteristics evaluations of the coating agent with respect to the coating film sample A1.
実施例２〜４、９〜１１、１３〜１５、２０〜２８、参考例５〜８、１２、比較例１６及び１９
共重合体、架橋剤及び硬化促進剤を表４に示す通り用いた以外は実施例１と同様の操作により塗膜サンプルおよびキャリアを得た。
各塗膜サンプルの評価結果を表５に示す。
Examples 2 to 4 , 9 to 11, 13 to 15, 20 to 28 , Reference Examples 5 to 8, 12, Comparative Examples 16 and 19
A coating film sample and a carrier were obtained by the same operation as in Example 1 except that the copolymer, the crosslinking agent, and the curing accelerator were used as shown in Table 4.
The evaluation results of each coating film sample are shown in Table 5.
実施例１７
製造例１７で得られたグラフト共重合体Ａ１７を固形分で１００部、架橋剤としてｊＥＲ８２８（三菱化学社製、エポキシ系架橋剤）２８．３部（グラフト共重合体の架橋性官能基量と当量）及び硬化促進触媒としてＤＢＵ（１，８−ジアザビシクロ［５．４．０］ウンデセン）０．５部（対グラフト共重合体０．５％）を混合し、固形分２０％になるようにＭＥＫで希釈してコーティング液を調整した。
このコーティング液を実施例１と同様の操作によりアルミ試験版にコーティングした後に加熱することにより塗膜サンプルＡ１７を得た。
塗膜サンプルＡ１７の評価結果を表５に示す。
Example 17
100 parts by weight of the graft copolymer A17 obtained in Production Example 17 and 28.3 parts of jER828 (manufactured by Mitsubishi Chemical Corporation, epoxy-based crosslinking agent) as a crosslinking agent (the amount of crosslinking functional groups of the graft copolymer) Equivalent) and 0.5 part of DBU (1,8-diazabicyclo [5.4.0] undecene) (0.5% of graft copolymer) as a curing accelerating catalyst are mixed so that the solid content is 20%. The coating liquid was prepared by diluting with MEK.
A coating sample A17 was obtained by coating this coating solution on an aluminum test plate in the same manner as in Example 1 and then heating.
Table 5 shows the evaluation results of the coating film sample A17.
実施例１８
製造例１８で得られたグラフト共重合体Ａ１８を固形分で１００部及びＩＲＧＡＣＵＲＥ９０７（ＢＡＳＦ社製、光重合開始剤）１．０部（対グラフト共重合体１％）を混合し、固形分２０％になるようにＭＥＫで希釈してコーティング液を調整した。実施例１と同様の操作によりアルミ試験板にコーティングした後、８０Ｗ／ｃｍ高圧水銀灯により５００ｍＪ／ｃｍ２の紫外線を照射することにより塗膜サンプルＡ１８を得た。
塗膜サンプルＡ１８の評価結果を表５に示す。
Example 18
100 parts by weight of the graft copolymer A18 obtained in Production Example 18 and 1.0 part of IRGACURE907 (manufactured by BASF, photopolymerization initiator) (1% of the graft copolymer) were mixed to obtain a solid content of 20 The coating solution was prepared by diluting with MEK so that the concentration was 1%. After coating an aluminum test plate by the same operation as in Example 1, a coating film sample A18 was obtained by irradiating with an ultraviolet ray of 500 mJ / cm 2 with an 80 W / cm high-pressure mercury lamp.
Table 5 shows the evaluation results of the coating film sample A18.
実施例２９
製造例１で得られたグラフト共重合体Ａ１を固形分で３３部と比較製造例７で得られたリニア共重合体Ｂ７を固形分で６７部を混合し、ここに架橋剤としてコロネートＨＸ（日本ポリウレタン社製、イソシアネート系架橋剤）３８．０部（共重合体混合物の架橋性官能基量と当量）及び硬化促進触媒としてネオスタンＵ−８１０ ０．０１部（対共重合体混合物１００ｐｐｍ）を混合し、固形分２０％になるようにＭＥＫで希釈してコーティング液を調整した。このコーティング液を実施例１と同様の操作によりアルミ試験板にコーティングした後に加熱することにより、塗膜サンプルＡ２９を得た。
塗膜サンプルＡ２９の評価結果を表５に示す。
Example 29
33 parts by weight of the graft copolymer A1 obtained in Production Example 1 and 67 parts by weight of the linear copolymer B7 obtained in Comparative Production Example 7 were mixed, and this was mixed with Coronate HX ( Nippon Polyurethane Co., Ltd., isocyanate-based crosslinking agent) 38.0 parts (equivalent to the amount of crosslinkable functional groups of the copolymer mixture) and 0.01 part of Neostan U-810 (100 ppm of the copolymer mixture) as a curing accelerator catalyst. The coating liquid was prepared by mixing and diluting with MEK to a solid content of 20%. A coating film sample A29 was obtained by coating the aluminum test plate with this coating solution in the same manner as in Example 1 and then heating.
Table 5 shows the evaluation results of the coating film sample A29.
比較例１〜７
共重合体、架橋剤及び硬化促進剤を表４に示す通り用いた以外は実施例１と同様の操作により塗膜サンプルを得た。
各塗膜サンプルの評価結果を表５に示す。
Comparative Examples 1-7
A coating film sample was obtained by the same operation as in Example 1 except that the copolymer, the crosslinking agent and the curing accelerator were used as shown in Table 4.
The evaluation results of each coating film sample are shown in Table 5.
表４で用いた化合物の詳細を以下に示す。
ｊＥＲ８２８：エポキシ樹脂、三菱化学社製
ＤＢＵ：ジアザビシクロウンデセン
キャタリスト２９６−９：リン酸系触媒、三井サイテック社製
Details of the compounds used in Table 4 are shown below.
jER828: Epoxy resin, manufactured by Mitsubishi Chemical Corporation DBU: Diazabicycloundecene Catalyst 296-9: Phosphate catalyst, manufactured by Mitsui Cytec
本発明によるグラフト共重合体を含むコーティング剤を用いた実施例１〜４、９〜１１、１３〜１５、１７、１８、２０〜２９では、いずれも撥水・撥油性及び耐汚染性等のフッ素による特性と基材密着性及び塗膜強度等との両立の点で良好なバランスを有するものであった。
In Examples 1 to 4 , 9 to 11 , 13 to 15 , 17, 18, 20, and 29 using the coating agent containing the graft copolymer according to the present invention, all have water repellency, oil repellency, stain resistance, and the like. It had a good balance in terms of compatibility between the properties due to fluorine, substrate adhesion, coating film strength, and the like.
また、側鎖の官能基量について見ると、官能基量が０．２〜１．０ｍｅｑ／ｇの範囲にある実施例１は、官能基量が０．２ｍｅｑ／ｇ未満である実施例４に比較して摩擦試験後の接触角の保持率が高く、耐久性において一段と優れていることが判る。一方、当該官能基量が１．０ｍｅｑ／ｇを超えた参考例５に比較すると、実施例１は汚染性についても優れた性能を示す結果が得られた。
さらに、側鎖の架橋性官能基がアクリル酸ヒドロキシエチル由来の比較例１９に比較して、ω位に架橋性官能基を有する炭素数１０以上の単量体に由来する実施例１及び１３〜１５は、撥水性、撥油性、及び汚染性といったフッ素特性において、より優れたバランスの良いコーティング剤である結果が示された。
Moreover, when it sees about the functional group amount of a side chain, Example 1 in which the functional group amount is in the range of 0.2 to 1.0 meq / g is similar to Example 4 in which the functional group amount is less than 0.2 meq / g. It can be seen that the contact angle retention after the friction test is high and the durability is further improved. On the other hand, when compared with Reference Example 5 in which the amount of the functional group exceeded 1.0 meq / g, Example 1 showed a result showing excellent performance in terms of contamination.
Furthermore, compared with Comparative Example 19 in which the crosslinkable functional group of the side chain is derived from hydroxyethyl acrylate, Examples 1 and 13 to 13 derived from a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position. No. 15 was a coating agent with a better balance in fluorine characteristics such as water repellency, oil repellency and contamination.
これに対して、フッ素系リニアポリマーからなる比較例２及び３、並びにフッ素を有さないポリマーからなる比較例５及び７は、いずれも撥水性、撥油性、及び汚染性といったフッ素特性が不十分なものであった。
また、側鎖若しくは主鎖に架橋性官能基を有さないグラフトポリマーからなる比較例１及び４は、摩擦試験後の接触角から明らかなように、ともに耐久性が大きく劣るものであった。
比較例６は本願発明のグラフト共重合体における主鎖と側鎖を入れ替えたタイプのポリマーを用いた場合の例であるが、フッ素特性において十分な性能が示されていないことが判る。
On the other hand, Comparative Examples 2 and 3 made of a fluorine-based linear polymer and Comparative Examples 5 and 7 made of a polymer having no fluorine have insufficient fluorine characteristics such as water repellency, oil repellency, and contamination. It was something.
Further, Comparative Examples 1 and 4 comprising a graft polymer having no crosslinkable functional group in the side chain or main chain were both inferior in durability as apparent from the contact angle after the friction test.
Comparative Example 6 is an example in which a polymer of a type in which the main chain and the side chain in the graft copolymer of the present invention are exchanged is used, but it can be seen that sufficient performance is not shown in fluorine characteristics.
本発明のグラフト共重合体は、撥水・撥油性及び耐汚染性等のフッ素による特性と基材密着性及び塗膜強度等との両立の点で良好なバランスを有するコーティング剤として有用である。具体的な用途としては、上記フッ素特性を要する一般コーティング剤の他にも、インクジェットプリンターのインク吐出部、並びに感光体、ゴムロール、キャリア及びその他内部部品等の複写機周辺部材のコーティング剤としても好適である。 The graft copolymer of the present invention is useful as a coating agent having a good balance in terms of coexistence of properties due to fluorine such as water / oil repellency and stain resistance, and substrate adhesion and coating strength. . As a specific application, in addition to the general coating agent that requires the above-mentioned fluorine characteristics, it is also suitable as a coating agent for ink jet parts of ink jet printers and peripheral members of copying machines such as photoreceptors, rubber rolls, carriers, and other internal parts. It is.
Claims (12)
上記側鎖に配される架橋性官能基がω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体に由来するものであり、
上記側鎖たる上記フッ素系重合体を構成する全単量体に対するフッ素原子含有ビニル単量体の割合が４０〜９５質量％であり、
上記フッ素原子含有ビニル単量体として下記一般式（１）で表されるビニル単量体が含まれることを特徴とするフッ素系グラフト共重合体。
The crosslinkable functional group arranged in the side chain has a crosslinkable functional group at the ω position, and is derived from a monomer having 10 or more carbon atoms having a structure derived from caprolactone in the molecule,
The ratio of the fluorine atom-containing vinyl monomer to the total monomer constituting the fluoropolymer as the side chain is 40 to 95% by mass,
A fluorine-based graft copolymer comprising a vinyl monomer represented by the following general formula (1) as the fluorine atom-containing vinyl monomer .
上記分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体における、カプロラクトンの平均付加モル数が２モル以上でありIn the monomer having a structure derived from caprolactone in the molecule and having 10 or more carbon atoms, the average added mole number of caprolactone is 2 moles or more.
上記一般式（１）におけるｎが６〜２０である、請求項１に記載のフッ素系グラフト共重合体。The fluorine-type graft copolymer of Claim 1 whose n in the said General formula (1) is 6-20.
上記側鎖に配される架橋性官能基が水酸基である請求項１又は２に記載のフッ素系グラフト共重合体。The fluorine-based graft copolymer according to claim 1 or 2, wherein the crosslinkable functional group arranged in the side chain is a hydroxyl group.
末端に重合性不飽和官能基を有し、かつ架橋性官能基が導入されたフッ素系重合体からなるマクロモノマーの存在下に架橋性官能基含有ビニル単量体を含む単量体混合物を共重合するものであり、A monomer mixture containing a crosslinkable functional group-containing vinyl monomer in the presence of a macromonomer composed of a fluoropolymer having a polymerizable unsaturated functional group at the terminal and having a crosslinkable functional group introduced therein Is to polymerize,
上記マクロモノマーが、フッ素原子含有ビニル単量体及びω位に架橋性官能基を有し、且つ、分子内にカプロラクトン由来の構造を有する炭素数１０以上の単量体を構成単量体とするフッ素系グラフト共重合体の製造方法。The macromonomer has a fluorine atom-containing vinyl monomer and a monomer having 10 or more carbon atoms having a crosslinkable functional group at the ω position and a structure derived from caprolactone in the molecule. A method for producing a fluorine-based graft copolymer.
上記側鎖に配される架橋性官能基が水酸基であり、The crosslinkable functional group arranged in the side chain is a hydroxyl group,
上記フッ素原子含有ビニル単量体として下記一般式（１）で表されるビニル単量体が含まれることを特徴とする請求項９に記載のフッ素系グラフト共重合体の製造方法。The method for producing a fluorine-based graft copolymer according to claim 9, wherein the fluorine atom-containing vinyl monomer includes a vinyl monomer represented by the following general formula (1).
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