JP2012092316A - Acryl-fluorine composite polymer particle - Google Patents
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Abstract
Description
本発明は、各種の基材の塗装用の塗料用組成物のバインダーに適した新規な含フッ素共重合体粒子、該含フッ素共重合体粒子を含む水性分散体、および該水性分散体を含む水性塗料用組成物に関する。 The present invention includes a novel fluorine-containing copolymer particle suitable for a binder of a coating composition for coating various substrates, an aqueous dispersion containing the fluorine-containing copolymer particle, and the aqueous dispersion The present invention relates to an aqueous coating composition.
塗装用の塗料組成物として、有機溶剤系の塗料のほか、自然環境への配慮や塗装作業環境の改善の点から水を分散媒とする水性塗料が知られている。また、建材、特に屋根材、外壁などの建材の塗装という面からは、耐候性に優れることが要求され、特に耐候性、耐水性、耐薬品性、造膜性などに優れたフッ素樹脂をバインダーとする水性塗料組成物が開発されている。 As paint compositions for coating, in addition to organic solvent-based paints, water-based paints using water as a dispersion medium are known from the viewpoint of consideration of the natural environment and improvement of the painting work environment. In addition, from the viewpoint of coating building materials, especially roofing materials and exterior walls, it is required to have excellent weather resistance, and in particular, a fluororesin that has excellent weather resistance, water resistance, chemical resistance, film-forming properties, etc. is used as a binder. A water-based coating composition has been developed.
しかし、フッ素樹脂は本質的に他材との密着性に劣るため、基材との密着性の改良が種々行われてきている。たとえば、特許文献１では、フッ化ビニリデン（ＶＤＦ）系のフッ素樹脂をシード粒子の存在下に、（メタ）アクリル酸エステルとエチレン性不飽和単量体とからなる単量体混合物をシード重合させる際に、単量体混合物中にシクロヘキシル基を有する単量体を０．５〜４５質量％含ませると共に、単量体混合物をフッ素樹脂に対して５０質量％以下にすることにより、得られる含フッ素系重合体水性分散液が密着性に優れた塗膜を提供することが記載されている。 However, since the fluororesin is essentially inferior in adhesion to other materials, various improvements in adhesion to the substrate have been made. For example, in Patent Document 1, a vinylidene fluoride (VDF) -based fluororesin is seed-polymerized with a monomer mixture comprising a (meth) acrylic acid ester and an ethylenically unsaturated monomer in the presence of seed particles. At this time, the monomer mixture contains 0.5 to 45% by mass of the monomer having a cyclohexyl group, and the monomer mixture is made to contain 50% by mass or less based on the fluororesin. It is described that an aqueous dispersion of a fluoropolymer provides a coating film having excellent adhesion.
水性塗料組成物は溶剤系の塗料組成物に比して乾燥に時間を要するため、通常、強制的に乾燥させている。強制乾燥は、一般的に６０〜２００℃（基材の温度）で３秒間〜１０分間行われており、その結果、樹脂組成によっては、造膜が不充分になるため、塗膜の強度が低下するほか、耐水性が低下し、基材との界面接着が損なわれてしまうことがある。 Since the water-based coating composition requires time for drying as compared with the solvent-based coating composition, it is usually forcibly dried. Forced drying is generally performed at 60 to 200 ° C. (base material temperature) for 3 seconds to 10 minutes. As a result, depending on the resin composition, film formation may be insufficient. In addition to lowering, water resistance may be reduced, and interfacial adhesion with the substrate may be impaired.
また別の観点、特に高価なフッ素樹脂の低減の観点から、フッ素樹脂の割合を減らす検討も行われているが、フッ素樹脂の特性を発揮させるためには限度があり、フッ素樹脂の割合を少なくとも５０質量％以上、実用上は６０〜７０質量％にする必要があった。 Further, from the viewpoint of reducing the expensive fluororesin, there is a study to reduce the ratio of the fluororesin, but there is a limit to exert the characteristics of the fluororesin, and the ratio of the fluororesin is at least It was necessary to be 50% by mass or more, and practically 60 to 70% by mass.
これらの観点から、特許文献１に記載の含フッ素系重合体水性分散液は、強制乾燥による密着性の低下に改善の余地があり、また、アクリル樹脂の割合も多くする必要がある。 From these viewpoints, the fluorine-containing polymer aqueous dispersion described in Patent Document 1 has room for improvement in the decrease in adhesion due to forced drying, and the proportion of the acrylic resin needs to be increased.
本発明者らはかかる課題を解決するべく鋭意検討した結果、含フッ素重合体とアクリル系単量体とのアクリル−フッ素複合重合体粒子において、粒子を構成する架橋性アクリル系重合体の組成を工夫することにより、強制乾燥法によっても耐水性が確保でき、しかも、耐候性や耐薬品性を維持したままフッ素樹脂量を低減化できることを見出し、本発明を完成した。 As a result of intensive studies to solve such problems, the present inventors have determined the composition of the crosslinkable acrylic polymer constituting the particles in the acrylic-fluorine composite polymer particles of the fluoropolymer and the acrylic monomer. By devising, it was found that the water resistance can be secured even by the forced drying method, and the amount of fluororesin can be reduced while maintaining the weather resistance and chemical resistance, and the present invention has been completed.
すなわち本発明は、
（Ａ）構造単位としてテトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびクロロトリフルオロエチレン単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン単位を含むフッ化ビニリデン系重合体と、
（Ｂ）該フッ化ビニリデン系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル単位（ｂ１）、該フッ化ビニリデン系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル単位（ｂ２）および加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体単位（ｂ３）を含む架橋性アクリル系重合体（Ｂ）とからなるアクリル−フッ素複合重合体粒子であって、フッ化ビニリデン系重合体（Ａ）／架橋性アクリル系重合体（Ｂ）が質量比で１０／９０〜９０／１０であるアクリル−フッ素複合重合体粒子に関する。
That is, the present invention
(A) a vinylidene fluoride polymer containing at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as a structural unit, and a vinylidene fluoride unit;
(B) The (meth) acrylic acid ester unit (b1) compatible with the vinylidene fluoride polymer (A), and the (meth) acrylic acid ester unit incompatible with the vinylidene fluoride polymer (A). An acrylic-fluorine composite polymer particle comprising (b2) and a crosslinkable acrylic polymer (B) containing a (meth) acrylic monomer unit (b3) having a crosslinkable group capable of being crosslinked by heating, Further, the present invention relates to acrylic-fluorine composite polymer particles in which the vinylidene fluoride polymer (A) / crosslinkable acrylic polymer (B) has a mass ratio of 10/90 to 90/10.
本発明はまた、本発明のアクリル−フッ素複合重合体粒子を含む水性分散体、さらには、該水性分散体を含む水性塗料用組成物にも関する。 The present invention also relates to an aqueous dispersion containing the acrylic-fluorine composite polymer particles of the present invention, and further to an aqueous coating composition containing the aqueous dispersion.
本発明によれば、強制乾燥法によっても耐水性が確保でき、しかも、耐候性や耐薬品性を維持したままフッ素樹脂量を低減化できるアクリル−フッ素複合重合体粒子を提供することができる。 According to the present invention, it is possible to provide acrylic-fluorine composite polymer particles that can ensure water resistance even by a forced drying method and can reduce the amount of fluororesin while maintaining weather resistance and chemical resistance.
本発明のアクリル−フッ素複合重合体粒子は、
（Ａ）構造単位としてテトラフルオロエチレン（ＴＦＥ）単位、ヘキサフルオロプロピレン（ＨＦＰ）単位およびクロロトリフルオロエチレン（ＣＴＦＥ）単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン（ＶＤＦ）単位を含むＶＤＦ系重合体と、
（Ｂ）該ＶＤＦ系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル単位（ｂ１）、該ＶＤＦ系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル単位（ｂ２）および加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体単位（ｂ３）を含む架橋性アクリル系重合体（Ｂ）とからなるアクリル−フッ素複合重合体粒子であって、ＶＤＦ系重合体（Ａ）／架橋性アクリル系重合体（Ｂ）が質量比で１０／９０〜９０／１０であるアクリル−フッ素複合重合体粒子である。
ＶＤＦ系重合体（Ａ）及び架橋性アクリル系重合体（Ｂ）は単一粒子中に存在する。ＶＤＦ系重合体（Ａ）及び架橋性アクリル系重合体（Ｂ）は化学的に結合していてもよいし、結合していなくてもよい。ＶＤＦ系重合体（Ａ）及び架橋性アクリル系重合体（Ｂ）の質量比は、単一粒子を構成するＶＤＦ系重合体（Ａ）及び架橋性アクリル系重合体（Ｂ）の単一粒子中の質量比である。
The acrylic-fluorine composite polymer particles of the present invention are
(A) At least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene (TFE) unit, a hexafluoropropylene (HFP) unit, and a chlorotrifluoroethylene (CTFE) unit as a structural unit, and vinylidene fluoride (VDF) A VDF polymer containing units;
(B) The (meth) acrylic acid ester unit (b1) compatible with the VDF polymer (A), the (meth) acrylic acid ester unit (b2) incompatible with the VDF polymer (A), and An acrylic-fluorine composite polymer particle comprising a crosslinkable acrylic polymer (B) containing a (meth) acrylic monomer unit (b3) having a crosslinkable group capable of being crosslinked by heating, wherein the VDF heavy polymer These are acrylic-fluorine composite polymer particles in which the combined (A) / crosslinkable acrylic polymer (B) is 10/90 to 90/10 in mass ratio.
The VDF polymer (A) and the crosslinkable acrylic polymer (B) are present in a single particle. The VDF polymer (A) and the crosslinkable acrylic polymer (B) may be chemically bonded or may not be bonded. The mass ratio of the VDF polymer (A) and the crosslinkable acrylic polymer (B) is in the single particle of the VDF polymer (A) and the crosslinkable acrylic polymer (B) constituting the single particle. Mass ratio.
以下、各成分について説明する。 Hereinafter, each component will be described.
本発明におけるＶＤＦ系重合体（Ａ）としては、ＶＤＦのほか、構造単位としてテトラフルオロエチレン（ＴＦＥ）単位、ヘキサフルオロプロピレン（ＨＦＰ）単位およびクロロトリフルオロエチレン（ＣＴＦＥ）単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位を含む。本発明におけるＶＤＦ系重合体（Ａ）としては、テトラフルオロエチレン単位およびクロロトリフルオロエチレン単位を含むことが好ましい。 The VDF polymer (A) in the present invention is selected from the group consisting of tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) units and chlorotrifluoroethylene (CTFE) units as structural units in addition to VDF. At least one fluoroolefin unit. The VDF polymer (A) in the present invention preferably contains a tetrafluoroethylene unit and a chlorotrifluoroethylene unit.
ＶＤＦ系重合体（Ａ）として特に好ましいＶＤＦ系重合体は、ＶＤＦ／ＴＦＥ共重合体、ＶＤＦ／ＴＦＥ／ＣＴＦＥ共重合体、ＶＤＦ／ＨＦＰ共重合体、ＶＤＦ／ＴＦＥ／ＨＦＰ共重合体、ＶＤＦ／ＣＴＦＥ共重合体などがあげられる。 Particularly preferred VDF polymers as the VDF polymer (A) are VDF / TFE copolymer, VDF / TFE / CTFE copolymer, VDF / HFP copolymer, VDF / TFE / HFP copolymer, VDF / CTFE copolymer and the like.
要すれば、他のフルオロオレフィン、フルオロオレフィンと共重合可能な非フッ素系単量体に由来する構造単位を含んでいてもよい。 If necessary, it may contain a structural unit derived from another fluoroolefin or a non-fluorinated monomer copolymerizable with the fluoroolefin.
他のフルオロオレフィンとしては、たとえばパーフルオロ（アルキルビニルエーテル）、
また、官能基含有フルオロオレフィンも使用できる。官能基含有フルオロオレフィンとしては、たとえば式（１）：
ＣＸ１ ２＝ＣＸ２−（Ｒｆ）ｍ−Ｙ１ （１）
（式中、Ｙ１は−ＯＨ、−ＣＯＯＨ、−ＳＯ２Ｆ、−ＳＯ３Ｍ２（Ｍ２は水素原子、ＮＨ４基またはアルカリ金属）、カルボン酸塩、カルボキシエステル基、エポキシ基またはシアノ基；Ｘ１およびＸ２は同じかまたは異なりいずれも水素原子またはフッ素原子；Ｒｆは炭素数１〜４０の２価の含フッ素アルキレン基、炭素数１〜４０の含フッ素オキシアルキレン基または炭素数２〜４０のエーテル結合を含有する２価の含フッ素アルキレン基；ｍは０または１）で示される化合物があげられる。
Moreover, a functional group-containing fluoroolefin can also be used. As the functional group-containing fluoroolefin, for example, formula (1):
CX 1 2 = CX 2- (Rf) m -Y 1 (1)
(Wherein Y 1 is —OH, —COOH, —SO 2 F, —SO 3 M 2 (M 2 is a hydrogen atom, NH 4 group or alkali metal), carboxylate, carboxyester group, epoxy group or cyano. A group; X 1 and X 2 are the same or different and each is a hydrogen atom or a fluorine atom; Rf is a divalent fluorinated alkylene group having 1 to 40 carbon atoms, a fluorinated oxyalkylene group having 1 to 40 carbon atoms, or a carbon number A divalent fluorine-containing alkylene group containing 2 to 40 ether bonds; and m is 0 or 1).
具体例としては、たとえば
重合体（Ａ）は、ヨウ素含有モノマーに基づく繰り返し単位を含んでいてもよい。ヨウ素含有モノマーとしては、たとえば特公平５−６３４８２号公報や特開昭６２−１２７３４号公報に記載されているパーフルオロ（６，６−ジヒドロ−６−ヨード−３−オキサ−１−ヘキセン）、パーフルオロ（５−ヨード−３−オキサ−１−ペンテン）などのパーフルオロビニルエーテルのヨウ素化物も使用できる。 The polymer (A) may contain a repeating unit based on an iodine-containing monomer. Examples of the iodine-containing monomer include perfluoro (6,6-dihydro-6-iodo-3-oxa-1-hexene) described in JP-B-5-63482 and JP-A-62-212734, Periodinated vinyl ethers such as perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
重合体（Ａ）は、フルオロオレフィンと共重合可能な非フッ素系単量体に基づく繰り返し単位を含んでいてもよい。 The polymer (A) may contain a repeating unit based on a non-fluorinated monomer copolymerizable with a fluoroolefin.
ＶＤＦ系重合体のフッ素元素含有量は、５０〜７６質量％、さらには６０〜７０質量％が好ましい。 The fluorine element content of the VDF polymer is preferably 50 to 76 mass%, more preferably 60 to 70 mass%.
ＶＤＦ系重合体（Ａ）の製造方法は特に限定されず、従来公知の乳化重合法で行うことができる。 The manufacturing method of VDF type polymer (A) is not specifically limited, It can carry out by a conventionally well-known emulsion polymerization method.
本発明における架橋性アクリル系重合体（Ｂ）は、ＶＤＦ系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル単位（ｂ１）、ＶＤＦ系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル単位（ｂ２）、および加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体単位（ｂ３）を含む。 The crosslinkable acrylic polymer (B) in the present invention comprises a (meth) acrylic acid ester unit (b1) compatible with the VDF polymer (A) and an incompatible (meta) (V) polymer (A). ) An acrylic ester unit (b2) and a (meth) acrylic monomer unit (b3) having a crosslinkable group that can be cross-linked by heating.
（ｂ１）ＶＤＦ系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル（以下、「相溶性（メタ）アクリル酸エステル」ということもある） (B1) A (meth) acrylic acid ester compatible with the VDF polymer (A) (hereinafter sometimes referred to as “compatible (meth) acrylic acid ester”)
相溶性（メタ）アクリル酸エステル（ｂ１）は、ＶＤＦ系重合体（Ａ）と架橋性アクリル系重合体（Ｂ）との相溶性を高め、アクリル−フッ素複合重合体の一体性を高める働きをすると共に、常温乾燥時の造膜性を良好にする。 The compatible (meth) acrylic acid ester (b1) increases the compatibility between the VDF polymer (A) and the crosslinkable acrylic polymer (B), and increases the integrity of the acrylic-fluorine composite polymer. In addition, the film-forming property at room temperature drying is improved.
相溶性（メタ）アクリル酸エステル（ｂ１）の具体例としては、炭素数１〜４の鎖状のアルキルエステル、たとえばメチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、メチルメタクリレート、ｎ−プロピルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、イソプロピルメタクリレートなどの１種または２種以上が例示できる。なかでも、ＶＤＦ系重合体への溶解性が良好な点から、メチルメタクリレート（ＭＭＡ）、エチルメタクリレート（ＥＭＡ）、ｎ−ブチルメタクリレート（ｎ−ＭＢＡ）、ｎ−ブチルアクリレート（ｎ−ＢＡ）、エチルアクリレート（ＥＡ）、メチルアクリレートなどの１種または２種以上が好ましい。 Specific examples of the compatible (meth) acrylic acid ester (b1) include linear alkyl esters having 1 to 4 carbon atoms such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl Examples thereof include one or more of methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate and the like. Of these, methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (n-MBA), n-butyl acrylate (n-BA), ethyl are preferred because of their good solubility in VDF polymers. One type or two or more types such as acrylate (EA) and methyl acrylate are preferable.
相溶性（メタ）アクリル酸エステル（ｂ１）の含有量は、塗膜の透明性が良好な点から架橋性アクリル系重合体（Ｂ）の１０〜９０質量％、さらには２０〜７５質量％が好ましい。 The content of the compatible (meth) acrylic acid ester (b1) is 10 to 90% by mass, more preferably 20 to 75% by mass of the crosslinkable acrylic polymer (B) from the viewpoint that the transparency of the coating film is good. preferable.
（ｂ２）ＶＤＦ系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル（以下、「非相溶性（メタ）アクリル酸エステル」ということもある） (B2) VDF polymer (A) and incompatible (meth) acrylic acid ester (hereinafter sometimes referred to as “incompatible (meth) acrylic acid ester”)
非相溶性（メタ）アクリル酸エステル（ｂ２）は、強制乾燥時のアクリル−フッ素複合重合体の造膜性を改善し、基材との密着性を高める働きをすると共に、塗膜の耐水性を良好にする。 The incompatible (meth) acrylic acid ester (b2) improves the film-forming property of the acrylic-fluorine composite polymer during forced drying, enhances the adhesion to the substrate, and water resistance of the coating film. Make it better.
なお、「ＶＤＦ系重合体（Ａ）と相溶性」および「ＶＤＦ系重合体（Ａ）と非相溶性」とは、ＶＤＦ系重合体（Ａ）を単量体と混合したとき、透明である場合を「ＶＤＦ系重合体（Ａ）と相溶性」といい、また、混合時、白く濁る場合を「ＶＤＦ系重合体（Ａ）と非相溶性」という。 “VDF polymer (A) compatible” and “VDF polymer (A) incompatible” are transparent when VDF polymer (A) is mixed with a monomer. The case is referred to as “compatible with VDF polymer (A)”, and the case where it becomes cloudy when mixed is referred to as “incompatible with VDF polymer (A)”.
非相溶性（メタ）アクリル酸エステル（ｂ２）の具体例としては、炭素数６〜２０の鎖状アルキルエステル、炭素数６〜２０の脂環構造を有するアルキルエステル、または炭素数６〜２０のアリールエステルがあげられる。たとえばヘキシルアクリレート、２−エチルヘキシルアクリレート、２−ヒドロキシアクリレート、２−ヒドロキシプロピルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、イソブチルアクリレート、ターシャリーブチルアクリレート、ラウリルアクリレート、トリデシルアクリレート、ステアリルアクリレート、２−エトキシエチルアクリレート、２−メトキシエチルアクリレート、ヘキシルメタクリレート、２−エチルヘキシルメタクリレート、２−ヒドロキシメタクリレート、２−ヒドロキシプロピルメタクリレート、ｎ−プロピルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、イソブチルメタクリレート、ターシャリーブチルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート、２−エトキシエチルメタクリレート、２−メトキシエチルメタクリレートなど鎖状アルキルエステル；シクロヘキシルアクリレート、イソボルニルアクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレートなどの脂環式アルキルエステル；ベンジルアクリレート、ベンジルメタクリレートなどのアリールエステルの１種または２種以上が例示できる。なかでも、塗膜の耐候性が良好な点から、炭素数６〜２０の鎖状アルキルエステルおよび／または炭素数６〜２０の脂環構造を有するアルキルエステル、特に２−エチルヘキシルアクリレート（２−ＥＨＡ）および／またはシクロヘキシルメタクリレート（ＣＨＭＡ）が好ましい。 Specific examples of the incompatible (meth) acrylic acid ester (b2) include chain alkyl esters having 6 to 20 carbon atoms, alkyl esters having an alicyclic structure having 6 to 20 carbon atoms, or those having 6 to 20 carbon atoms. Examples include aryl esters. For example, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, tertiary butyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, 2-ethoxyethyl Acrylate, 2-methoxyethyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxy methacrylate, 2-hydroxypropyl methacrylate, n-propyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, lauryl methacrylate, tridecyl Chain alkyl esters such as tacrylate, stearyl methacrylate, 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate; alicyclic alkyl esters such as cyclohexyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate; benzyl acrylate, benzyl methacrylate Examples thereof include one or more aryl esters. Among these, from the viewpoint of good weather resistance of the coating film, a chain alkyl ester having 6 to 20 carbon atoms and / or an alkyl ester having an alicyclic structure having 6 to 20 carbon atoms, particularly 2-ethylhexyl acrylate (2-EHA). ) And / or cyclohexyl methacrylate (CHMA).
非相溶性（メタ）アクリル酸エステル（ｂ２）の含有量は、造膜性、密着性が良好な点から架橋性アクリル系重合体（Ｂ）の５〜８５質量％、さらには１５〜７０質量％が好ましい。 The content of the incompatible (meth) acrylic acid ester (b2) is from 5 to 85% by mass of the crosslinkable acrylic polymer (B), more preferably from 15 to 70% by mass from the viewpoint of good film forming properties and adhesion. % Is preferred.
（ｂ３）加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体（以下、「架橋性基含有（メタ）アクリル系単量体」ということもある） (B3) A (meth) acrylic monomer having a crosslinkable group that can be cross-linked by heating (hereinafter, also referred to as “crosslinkable group-containing (meth) acrylic monomer”).
架橋性基含有（メタ）アクリル系単量体（ｂ３）は、強制乾燥時のアクリル−フッ素複合重合体の造膜時に、アクリル系重合体（Ｂ）中の非相溶性（メタ）アクリル酸エステル単位（ｂ２）とＶＤＦ系重合体（Ａ）との分離や膜の白濁などを抑える働きをすると共に、基材への密着性を良好にする。 The crosslinkable group-containing (meth) acrylic monomer (b3) is an incompatible (meth) acrylic acid ester in the acrylic polymer (B) during film formation of the acrylic-fluorine composite polymer during forced drying. While acting to suppress separation of the unit (b2) and the VDF polymer (A), membrane turbidity, etc., the adhesion to the substrate is improved.
架橋性基含有（メタ）アクリル系単量体（ｂ３）が有する架橋性基は、加熱により架橋可能な官能基である。したがって、常温架橋する非ブロック型イソシアネート基などの架橋性基は本発明における架橋性基含有（メタ）アクリル系単量体（ｂ３）の架橋性基ではない。 The crosslinkable group possessed by the crosslinkable group-containing (meth) acrylic monomer (b3) is a functional group that can be crosslinked by heating. Therefore, a crosslinkable group such as a non-blocking isocyanate group that is crosslinked at room temperature is not a crosslinkable group of the crosslinkable group-containing (meth) acrylic monomer (b3) in the present invention.
加熱により架橋可能な架橋性基としては、たとえばエポキシ基、カルボキシル基、水酸基、アミノ基、メチロールアミド基、シリル基、カルボジイミド基、オキサゾリン基、ブロックイソシアネート基、エチレンイミン基などがあげられ、エマルションの安定性が良好な点から、エポキシ基、カルボキシル基が好ましい。 Examples of the crosslinkable group that can be crosslinked by heating include an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a methylolamide group, a silyl group, a carbodiimide group, an oxazoline group, a blocked isocyanate group, and an ethyleneimine group. From the viewpoint of good stability, an epoxy group and a carboxyl group are preferable.
エポキシ基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえばグリシジルアクリレート、グリシジルメタクリレート（ＧＭＡ）などのグリシジル化合物があげられ、重合時の安定性が良好な点から、グリシジルアクリレート、グリシジルメタクリレートの１種または２種以上が好ましい。架橋性基含有（メタ）アクリル系単量体がエポキシ基を含有する場合、塗装時の粒子間の造膜性や基材との密着性がさらに良好になる。 Examples of the crosslinkable group-containing (meth) acrylic monomer having an epoxy group include glycidyl compounds such as glycidyl acrylate and glycidyl methacrylate (GMA). From the viewpoint of good stability during polymerization, glycidyl acrylate, One or more glycidyl methacrylates are preferred. When the crosslinkable group-containing (meth) acrylic monomer contains an epoxy group, the film-forming property between particles at the time of coating and the adhesion to the substrate are further improved.
カルボキシル基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえばアクリル酸、フタル酸２−アクリロイルオキシエチル、ヘキサヒドロフタル酸２−アクリロイルオキシエチル、メタクリル酸、フタル酸２−メタクリロイルオキシエチル、ヘキサヒドロフタル酸２−メタクリロイルオキシエチルなどの１種または２種以上があげられ、エマルションの安定性が良好な点から、アクリル酸（ＡＡ）、メタクリル酸（ＭＡＡ）の１種または２種以上が好ましい。架橋性基含有（メタ）アクリル系単量体がカルボキシル基を含有する場合、塗装時の粒子間の造膜性や基材との密着性がさらに良好になる。 Examples of the crosslinkable group-containing (meth) acrylic monomer having a carboxyl group include acrylic acid, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, methacrylic acid, and 2-methacryloyloxy phthalate. 1 type or 2 or more types such as ethyl, 2-methacryloyloxyethyl hexahydrophthalate and the like, and 1 or 2 types of acrylic acid (AA) and methacrylic acid (MAA) from the viewpoint of good emulsion stability. The above is preferable. When the crosslinkable group-containing (meth) acrylic monomer contains a carboxyl group, the film-forming property between particles at the time of coating and the adhesion to the substrate are further improved.
水酸基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえば２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレートなどの１種または２種以上があげられる。 Examples of the crosslinkable group-containing (meth) acrylic monomer having a hydroxyl group include one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and the like. Can be given.
アミノ基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえば、アミノエチルアクリレート、ジメチルアミノアクリレート、ジエチルアミノエチルアクリレート、アミノエチルメタクリレート、ジメチルアミノメタクリレート、ジエチルアミノエチルメタクリレート、２−（Ｏ−〔１’−メチルプロピリデンアミノ〕カルボキシアミノ）エチルメタクリレートなどの１種または２種以上があげられる。 Examples of the crosslinkable group-containing (meth) acrylic monomer having an amino group include aminoethyl acrylate, dimethylamino acrylate, diethylaminoethyl acrylate, aminoethyl methacrylate, dimethylamino methacrylate, diethylaminoethyl methacrylate, 2- (O— One or more of [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate and the like.
メチロールアミド基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえば、メチロール化アクリルアミド、アルコキシメチルアクリルアミドなどの１種または２種以上があげられる。 Examples of the crosslinkable group-containing (meth) acrylic monomer having a methylolamide group include one or more of methylolated acrylamide, alkoxymethylacrylamide and the like.
シリル基を有する架橋性基含有（メタ）アクリル系単量体としては、たとえば、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣ２Ｈ５）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣ２Ｈ５）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）２（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）１１Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）１１Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
などの１種または２種以上があげられる。
As a crosslinkable group-containing (meth) acrylic monomer having a silyl group, for example,
CH 2 = CHCOO (CH 2) 3 Si (OCH 3) 3,
CH 2 = CHCOO (CH 2) 3 Si (CH 3) (OCH 3) 2,
CH 2 = CHCOO (CH 2) 3 Si (OC 2 H 5) 3,
CH 2 = CHCOO (CH 2) 3 Si (CH 3) (OC 2 H 5) 2,
CH 2 = C (CH 3) COO (CH 2) 3 Si (OCH 3) 3,
CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
CH 2 = C (CH 3) COO (CH 2) 3 Si (OC 2 H 5) 3,
CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) (OC 2 H 5) 2,
CH 2 = C (CH 3) COO (CH 2) 2 O (CH 2) 3 Si (OCH 3) 3,
CH 2 = C (CH 3) COO (CH 2) 2 (CH 2) 3 Si (CH 3) (OCH 3) 2,
CH 2 = C (CH 3) COO (CH 2) 11 Si (OCH 3) 3,
CH 2 = C (CH 3) COO (CH 2) 11 Si (CH 3) (OCH 3) 2,
1 type, or 2 or more types.
これらの架橋性基含有（メタ）アクリル系単量体（ｂ３）は、架橋性基の種類に限らず、２種以上を併用してもよい。たとえば、エポキシ基含有アクリル系単量体とカルボキシル基含有アクリル系単量体、エポキシ基含有アクリル系単量体と水酸基含有アクリル系単量体、エポキシ基含有アクリル系単量体とアミノ基含有アクリル系単量体、エポキシ基含有アクリル系単量体とメチロールアミド基含有アクリル系単量体、カルボキシル基含有アクリル系単量体とカルボジイミド基含有アクリル系単量体、カルボキシル基含有アクリル系単量体とオキサゾリン基含有アクリル系単量体、水酸基含有アクリル系単量体とブロックイソシアネート基含有アクリル系単量体、水酸基含有アクリル系単量体とエチレンイミン基含有アクリル系単量体、水酸基含有アクリル系単量体とカルボキシル基含有アクリル系単量体、水酸基含有アクリル系単量体とメチロールアミド基含有アクリル系単量体、メチロールアミド基含有アクリル系単量体とエチレンイミン基含有アクリル系単量体、メチロールアミド基含有アクリル系単量体とカルボキシル基含有アクリル系単量体、アミノ基含有アクリル系単量体とエチレンイミン基含有アクリル系単量体との併用などがあげられ、なかでも、エポキシ基含有アクリル系単量体とカルボキシル基含有アクリル系単量体とを併用するときは、エマルションの安定性が特に優れたものになる。 These crosslinkable group-containing (meth) acrylic monomers (b3) are not limited to the type of crosslinkable group, and two or more types may be used in combination. For example, epoxy group-containing acrylic monomer and carboxyl group-containing acrylic monomer, epoxy group-containing acrylic monomer and hydroxyl group-containing acrylic monomer, epoxy group-containing acrylic monomer and amino group-containing acrylic Monomer, epoxy group-containing acrylic monomer and methylolamide group-containing acrylic monomer, carboxyl group-containing acrylic monomer and carbodiimide group-containing acrylic monomer, carboxyl group-containing acrylic monomer And oxazoline group-containing acrylic monomer, hydroxyl group-containing acrylic monomer and block isocyanate group-containing acrylic monomer, hydroxyl group-containing acrylic monomer and ethyleneimine group-containing acrylic monomer, hydroxyl group-containing acrylic Monomer and carboxyl group-containing acrylic monomer, hydroxyl group-containing acrylic monomer and methylolamide -Containing acrylic monomer, methylolamide group-containing acrylic monomer and ethyleneimine group-containing acrylic monomer, methylolamide group-containing acrylic monomer and carboxyl group-containing acrylic monomer, amino group-containing acrylic When using an epoxy group-containing acrylic monomer and a carboxyl group-containing acrylic monomer together, an emulsion is used. The stability of the is particularly excellent.
架橋性基含有（メタ）アクリル系単量体（ｂ３）の含有量は、エマルションの安定性が良好な点から架橋性アクリル系重合体（Ｂ）の１〜２０質量％、さらには１〜５質量％が好ましい。また、架橋性基含有（メタ）アクリル系単量体単位（ｂ３）を２種以上含有する場合、合計量が上記の範囲において、適宜選定すればよい。たとえば、エポキシ基含有アクリル系単量体とカルボキシル基含有アクリル系単量体を併用する場合、質量比で７０／３０〜３０／７０の範囲が好ましい。 The content of the crosslinkable group-containing (meth) acrylic monomer (b3) is 1 to 20% by mass of the crosslinkable acrylic polymer (B), more preferably 1 to 5 from the viewpoint of good emulsion stability. Mass% is preferred. Moreover, what is necessary is just to select a total amount suitably in said range, when two or more types of crosslinkable group containing (meth) acrylic-type monomer units (b3) are contained. For example, when an epoxy group-containing acrylic monomer and a carboxyl group-containing acrylic monomer are used in combination, the mass ratio is preferably in the range of 70/30 to 30/70.
架橋性アクリル系重合体（Ｂ）は、上記（ｂ１）〜（ｂ３）以外に、本発明の効果を損なわない範囲で、上記（ｂ１）〜（ｂ３）以外の他の構造単位を含んでいてもよい。他の構造単位としては、たとえば芳香族ビニル単量体単位、上記（ｂ３）以外のエポキシ基含有単量体単位、上記（ｂ３）以外の不飽和カルボン酸系単量体単位、ビニルエーテル系単量体、オレフィン系単量体、加水分解性シリル基含有ビニル系単量体、ビニルエステル系単量体などがあげられる。 The crosslinkable acrylic polymer (B) contains other structural units other than the above (b1) to (b3), as long as the effects of the present invention are not impaired, in addition to the above (b1) to (b3). Also good. Examples of other structural units include aromatic vinyl monomer units, epoxy group-containing monomer units other than the above (b3), unsaturated carboxylic acid monomer units other than the above (b3), vinyl ether single monomers Olefin monomers, hydrolyzable silyl group-containing vinyl monomers, vinyl ester monomers, and the like.
芳香族ビニル単量体としては、スチレン、α−メチルスチレンなどのスチレン類が例示できる。エポキシ基含有単量体としては、アリルグリシジルエーテルなどが例示できる。 Examples of the aromatic vinyl monomer include styrenes such as styrene and α-methylstyrene. Examples of the epoxy group-containing monomer include allyl glycidyl ether.
不飽和カルボン酸系単量体としては、たとえばビニル酢酸、クロトン酸、桂皮酸、３−アリルオキシプロピオン酸、３−（２−アリロキシエトキシカルボニル）プロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニル、ウンデシレン酸などがあげられる。 Examples of unsaturated carboxylic acid monomers include vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid, itaconic acid monoester, malee Examples thereof include acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and undecylenic acid.
ビニルエーテル系単量体としては、アルキルビニルエーテル類、水酸基含有ビニルエーテル類などが、水酸基含有ビニルエーテルとしては、たとえば２−ヒドロキシエチルビニルエーテル、３−ヒドロキシプロピルビニルエーテル、２−ヒドロキシプロピルビニルエーテル、２−ヒドロキシ−２−メチルプロピルビニルエーテル、４−ヒドロキシブチルビニルエーテル、４−ヒドロキシ−２−メチルブチルビニルエーテル、５−ヒドロキシペンチルビニルエーテル、６−ヒドロキシヘキシルビニルエーテル、２−ヒドロキシエチルアリルエーテル、４−ヒドロキシブチルアリルエーテル、グリセロールモノアリルエーテルなどがあげられる。 Examples of vinyl ether monomers include alkyl vinyl ethers and hydroxyl group-containing vinyl ethers. Examples of hydroxyl group-containing vinyl ethers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, and 2-hydroxy-2-vinyl ether. Methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether Etc.
オレフィン系単量体としては、たとえばエチレン、プロピレン、ｎ−ブテン、イソブテン、スチレンなどがあげられる。 Examples of the olefin monomer include ethylene, propylene, n-butene, isobutene, and styrene.
加水分解性シリル基含有ビニル系単量体としては、たとえば
ＣＨ２＝ＣＨＳｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＳｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝Ｃ（ＣＨ３）Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝Ｃ（ＣＨ３）Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ５）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ３Ｈ７）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ４Ｈ９）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ６Ｈ１３）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ８Ｈ１７）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ１０Ｈ２１）３、
ＣＨ２＝ＣＨＳｉ（ＯＣ１２Ｈ２５）３、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ｏ−Ｃ６Ｈ４）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ｏ−Ｃ６Ｈ４）ＣＯＯ（ＣＨ２）３Ｓｉ（ＣＨ３）（ＯＣＨ３）２、
ＣＨ２＝ＣＨ（ＣＨ２）４Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨ（ＣＨ２）８Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、
ＣＨ２＝ＣＨＣＨ２ＯＣＯ（ＣＨ２）１０Ｓｉ（ＯＣＨ３）３
などがあげられる。
Examples of the hydrolyzable silyl group-containing vinyl monomer include CH 2 ═CHSi (OCH 3 ) 3 ,
CH 2 = CHSi (CH 3 ) (OCH 3 ) 2 ,
CH 2 = C (CH 3) Si (OCH 3) 3,
CH 2 = C (CH 3) Si (CH 3) (OCH 3) 2,
CH 2 = CHSi (OC 2 H 5) 3,
CH 2 = CHSi (OC 3 H 7) 3,
CH 2 = CHSi (OC 4 H 9) 3,
CH 2 = CHSi (OC 6 H 13 ) 3 ,
CH 2 = CHSi (OC 8 H 17) 3,
CH 2 = CHSi (OC 10 H 21) 3,
CH 2 = CHSi (OC 12 H 25) 3,
CH 2 = CHCH 2 OCO (o -C 6 H 4) COO (CH 2) 3 Si (OCH 3) 3,
CH 2 = CHCH 2 OCO (o -C 6 H 4) COO (CH 2) 3 Si (CH 3) (OCH 3) 2,
CH 2 = CH (CH 2) 4 Si (OCH 3) 3,
CH 2 = CH (CH 2) 8 Si (OCH 3) 3,
CH 2 = CHO (CH 2) 3 Si (OCH 3) 3,
CH 2 = CHCH 2 O (CH 2) 3 Si (OCH 3) 3,
CH 2 = CHCH 2 OCO (CH 2) 10 Si (OCH 3) 3
Etc.
ビニルエステル系単量体としては、たとえば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、シクロヘキシルカルボン酸ビニル、安息香酸ビニル、パラ−ｔ−ブチル安息香酸ビニルなどのカルボン酸ビニルエステル類などがあげられる。 Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and benzoic acid. Examples thereof include carboxylic acid vinyl esters such as vinyl acid vinyl and vinyl para-t-butylbenzoate.
上記（ｂ１）〜（ｂ３）以外の他の単量体の架橋性アクリル系重合体（Ｂ）中の含有量は、単量体の種類にもよるが１０質量％以下が好ましい。 The content of the monomer other than the above (b1) to (b3) in the crosslinkable acrylic polymer (B) is preferably 10% by mass or less although it depends on the kind of the monomer.
本発明において、架橋性アクリル系重合体（Ｂ）の好ましい具体的な組成としては、たとえばＭＭＡ／２−ＥＨＡ／ＭＡＡ／ＧＭＡ（６０〜８０／１０〜３０／０．５〜５／０．５〜１０質量比）、ｎ−ＢＡ／ＣＨＭＡ／ＭＡＡ／ＧＭＡ（１０〜３０／５５〜８０／０．５〜１０／０．５〜５質量比）、ＭＭＡ／ｎ−ＢＡ／ＣＨＭＡ／ＭＡＡ／ＧＭＡ（１〜５０／５〜４０／１〜７０／０．５〜５／０．５〜１０質量比）などがあげられるが、これらのみに限定されるものではない。 In the present invention, preferred specific composition of the crosslinkable acrylic polymer (B) is, for example, MMA / 2-EHA / MAA / GMA (60-80 / 10-30 / 0.5-5 / 0.5). 10 mass ratio), n-BA / CHMA / MAA / GMA (10-30 / 55-80 / 0.5-10 / 0.5-5 mass ratio), MMA / n-BA / CHMA / MAA / GMA (1-50 / 5-40/1-70 / 0.5-5 / 0.5-10 mass ratio) etc. are mentioned, However, It is not limited only to these.
本発明のアクリル−フッ素複合重合体におけるＶＤＦ系重合体（Ａ）と架橋性アクリル系重合体（Ｂ）の割合は、ＶＤＦ系重合体（Ａ）／架橋性アクリル系重合体（Ｂ）が質量比で１０／９０〜９０／１０であり、１０／９０〜７０／３０であることが好ましい。たとえば（Ａ）／（Ｂ）が７０／３０より大きくなる、すなわちＶＤＦ系重合体（Ａ）が７０質量％を超えると塗装時の造膜性、基材への密着性という利点が損なわれる。より好ましくは、（Ａ）／（Ｂ）が２０／８０〜５０／５０である。更に好ましくは、（Ａ）／（Ｂ）が３０／７０〜４０／６０である。 The ratio of the VDF polymer (A) and the crosslinkable acrylic polymer (B) in the acrylic-fluorine composite polymer of the present invention is such that the VDF polymer (A) / crosslinkable acrylic polymer (B) is in mass. The ratio is 10/90 to 90/10, and preferably 10/90 to 70/30. For example, if (A) / (B) is greater than 70/30, that is, if the VDF polymer (A) exceeds 70% by mass, the advantages of film-forming properties during coating and adhesion to the substrate are impaired. More preferably, (A) / (B) is 20/80 to 50/50. More preferably, (A) / (B) is 30/70 to 40/60.
本発明のアクリル−フッ素複合重合体粒子の製造に用いる重合法は、従来公知の重合法、特に乳化重合法が採用でき、たとえばシード重合法が特に好ましく採用できる。シード重合法は特に限定されず、従来公知の方法と条件で行うことができる。 As a polymerization method used for producing the acrylic-fluorine composite polymer particles of the present invention, a conventionally known polymerization method, particularly an emulsion polymerization method can be adopted, and for example, a seed polymerization method can be particularly preferably adopted. The seed polymerization method is not particularly limited, and can be performed by a conventionally known method and conditions.
たとえば、アクリル系単量体混合物のシード重合は、ＶＤＦ系重合体粒子の存在下に、反応系にアクリル系単量体混合物の全量を一括して仕込む方法、アクリル系単量体混合物の一部を仕込み反応させた後、残りを連続または分割して仕込む方法、アクリル系単量体混合物の全量を連続して仕込む方法などによって行うことができる。 For example, seed polymerization of an acrylic monomer mixture is a method in which the entire amount of the acrylic monomer mixture is charged into the reaction system in the presence of VDF polymer particles, or a part of the acrylic monomer mixture. Can be carried out by, for example, a method in which the remainder is continuously or dividedly charged and a method in which the entire amount of the acrylic monomer mixture is continuously charged.
また、このシード重合の重合条件は、通常の乳化重合と同様である。たとえば、ＶＤＦ系重合体粒子を含む水性媒体中に、乳化剤、重合開始剤、連鎖移動剤、場合によってはキレート化剤、ｐＨ調整剤などを添加し、１０〜９０℃の温度で０．５〜６時間反応を行うことにより重合することができる。 The polymerization conditions for the seed polymerization are the same as those for normal emulsion polymerization. For example, in an aqueous medium containing VDF polymer particles, an emulsifier, a polymerization initiator, a chain transfer agent, in some cases a chelating agent, a pH adjuster, and the like are added, and a temperature of 10 to 90 ° C. is 0.5 to It can superpose | polymerize by reacting for 6 hours.
乳化剤としては、反応性乳化剤でも非反応性乳化剤でも、またはそれらの併用でもよい。非反応性乳化剤としては、従来公知のアニオン性乳化剤、非イオン性乳化剤を単独またはこれらの併用があげられる。場合によっては両性乳化剤を用いることもできる。 The emulsifier may be a reactive emulsifier, a non-reactive emulsifier, or a combination thereof. As the non-reactive emulsifier, conventionally known anionic emulsifiers and nonionic emulsifiers may be used alone or in combination thereof. In some cases, an amphoteric emulsifier can be used.
シード重合の際に用いる重合開始剤としては、水性媒体中でフリーラジカル反応に供し得るものであれば特に限定されず、場合によっては、還元剤と組み合せて用いることも可能である。使用可能な水溶性の重合開始剤としては、たとえば過硫酸塩、過酸化水素、還元剤としては、ピロ重亜硫酸ナトリウム、亜硫酸水素ナトリウム、Ｌ−アスコルビン酸ナトリウム、ロンガリットなどをあげることができる。油溶性の重合開始剤としては、たとえばジイソプロピルパーオキシジカーボネート（ＩＰＰ）、過酸化ベンゾイル、過酸化ジブチル、アゾビスイソブチロニトリル（ＡＩＢＮ）などをあげることができる。重合開始剤の使用量は、通常、アクリル系単量体混合物１００質量部あたり、０．０５〜２．０質量部である。 The polymerization initiator used in the seed polymerization is not particularly limited as long as it can be used for a free radical reaction in an aqueous medium. In some cases, it can be used in combination with a reducing agent. Examples of the water-soluble polymerization initiator that can be used include persulfate, hydrogen peroxide, and examples of the reducing agent include sodium pyrobisulfite, sodium hydrogensulfite, sodium L-ascorbate, Rongalite, and the like. Examples of the oil-soluble polymerization initiator include diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN), and the like. The usage-amount of a polymerization initiator is 0.05-2.0 mass parts normally per 100 mass parts of acrylic-type monomer mixtures.
シード重合の際に用いてもよい連鎖移動剤としては、たとえばクロロホルム、四塩化炭素などのハロゲン化炭化水素；ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、ｎ−オクチルメルカプタンなどのメルカプタン類などをあげることができる。連鎖移動剤の使用量は、通常、アクリル系単量体混合物１００質量部あたり、０〜５．０質量部である。 Examples of chain transfer agents that may be used for seed polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. Can do. The amount of the chain transfer agent used is usually 0 to 5.0 parts by mass per 100 parts by mass of the acrylic monomer mixture.
本発明のアクリル−フッ素複合重合体粒子の製造において、ＶＤＦ系重合体粒子と上記（ｂ１）〜（ｂ３）を含むアクリル系単量体混合物との比率は、ＶＤＦ系重合体粒子１００質量部に対してアクリル系単量体混合物は１００質量部以上である。さらには、塗装時の造膜性が良好な点から、ＶＤＦ系重合体粒子１００質量部に対してアクリル系単量体混合物を１１０質量部以上、特に１５０質量部以上である。 In the production of the acrylic-fluorine composite polymer particles of the present invention, the ratio of the VDF polymer particles and the acrylic monomer mixture containing the above (b1) to (b3) is 100 parts by mass of the VDF polymer particles. On the other hand, the acrylic monomer mixture is 100 parts by mass or more. Furthermore, the acrylic monomer mixture is 110 parts by mass or more, particularly 150 parts by mass or more with respect to 100 parts by mass of the VDF polymer particles from the viewpoint of good film-forming properties at the time of coating.
本発明は、上述のアクリル−フッ素複合重合体粒子を含む水性分散体でもある。本発明において水性分散体中でのアクリル−フッ素複合重合体粒子の粒子径は、５０〜３００ｎｍが好ましい。より好ましくは、５０〜２５０ｎｍである。粒子径が５０ｎｍ未満であると、水性分散体のアクリル−フッ素複合重合体粒子の濃度が実用的範囲である３０質量％以上において水性分散体の粘度が著しく増大し、塗料化の作業に支障を来すことがある。一方３００ｎｍを超えると、得られる水性分散体の沈降安定性が低下する傾向があり、また、アクリル−フッ素複合重合体粒子の最低成膜温度の上昇を招くことがある。 The present invention is also an aqueous dispersion containing the above-mentioned acrylic-fluorine composite polymer particles. In the present invention, the particle diameter of the acrylic-fluorine composite polymer particles in the aqueous dispersion is preferably 50 to 300 nm. More preferably, it is 50-250 nm. When the particle diameter is less than 50 nm, the viscosity of the aqueous dispersion is remarkably increased when the concentration of the acrylic-fluorine composite polymer particles in the aqueous dispersion is 30% by mass or more, which is within the practical range, and this hinders the work of coating. May come. On the other hand, if it exceeds 300 nm, the sedimentation stability of the resulting aqueous dispersion tends to decrease, and the minimum film-forming temperature of the acrylic-fluorine composite polymer particles may increase.
本発明のアクリル−フッ素複合重合体粒子の水性分散体の固形分濃度は、塗料用途の観点からは３０〜６５質量％であることが好ましく、より好ましくは３５〜５０質量％である。 The solid content concentration of the aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention is preferably 30 to 65% by mass, more preferably 35 to 50% by mass from the viewpoint of coating application.
本発明のアクリル−フッ素複合重合体粒子の水性分散体は、種々の形態で各種の用途に利用できる。 The aqueous dispersion of acrylic-fluorine composite polymer particles of the present invention can be used for various applications in various forms.
たとえば、各種の塗料用組成物の塗膜形成成分、フィルムやシートの成形材料のほか、接着剤組成物、インキ用組成物などが例示できるが、これらに限定されるものではない。水性塗料用組成物として用いる場合は、強制乾燥で造膜した場合でも基材との接着性が向上する。 Examples thereof include, but are not limited to, coating composition components of various coating compositions, molding materials for films and sheets, adhesive compositions, ink compositions, and the like. When used as a composition for water-based paints, adhesion to a substrate is improved even when a film is formed by forced drying.
本発明のアクリル−フッ素複合重合体粒子の水性分散体は、上述したシード重合法により製造することができる。
本発明のアクリル−フッ素複合重合体粒子の水性分散体は、ＶＤＦ系重合体（Ａ）からなる粒子を含む水性分散液に、ＶＤＦ系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル（ｂ１）、ＶＤＦ系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル（ｂ２）、加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体（ｂ３）、及び、重合開始剤を添加する工程、並びに、
（メタ）アクリル酸エステル（ｂ１）、（メタ）アクリル酸エステル（ｂ２）、及び、（メタ）アクリル系単量体（ｂ３）を反応させる工程、
を含む製造方法により好適に製造することができる。
The aqueous dispersion of acrylic-fluorine composite polymer particles of the present invention can be produced by the seed polymerization method described above.
The aqueous dispersion of acrylic-fluorine composite polymer particles of the present invention is a (meth) acrylic acid ester compatible with the VDF polymer (A) in an aqueous dispersion containing particles comprising the VDF polymer (A). (B1), a (meth) acrylic acid ester (b2) that is incompatible with the VDF polymer (A), a (meth) acrylic monomer (b3) having a crosslinkable group that can be crosslinked by heating, and Adding a polymerization initiator, and
A step of reacting (meth) acrylic acid ester (b1), (meth) acrylic acid ester (b2), and (meth) acrylic monomer (b3);
It can manufacture suitably by the manufacturing method containing.
本発明は、上述の水性分散体を含む水性塗料用組成物でもある。本発明の水性塗料用組成物は、膜形成材として前記のアクリル−フッ素複合重合体粒子を用いるほかは、従来公知の添加剤や配合割合が採用できる。たとえば、アクリル−フッ素複合重合体粒子の濃度としては、たとえば１０〜６０質量％程度の範囲から選定すればよい。 The present invention is also an aqueous coating composition containing the above-mentioned aqueous dispersion. The water-based coating composition of the present invention can employ conventionally known additives and blending ratios, except that the acrylic-fluorine composite polymer particles are used as a film forming material. For example, the concentration of the acrylic-fluorine composite polymer particles may be selected from a range of about 10 to 60% by mass, for example.
また、顔料入りの水性塗料用組成物を調製する場合は、アクリル−フッ素複合重合体粒子の水性分散液に、あらかじめサンドミル等の顔料分散機で水、酸化チタンなどの顔料、消泡剤、顔料分散剤、ｐＨ調整剤等を分散した顔料分散体の所定量と造膜補助剤の所定量を撹拌混合したのち、増粘剤を所定量加えて混合し、その他必要な添加剤を適宜加えればよい。顔料を加えない水性塗料用組成物を調製する場合は、アクリル−フッ素複合重合体粒子の水性分散液に、必要に応じ、水、造膜補助剤、消泡剤、増粘剤、ｐＨ調整剤、その他所要の添加剤を加えて公知方法で撹拌混合すればよい。 When preparing a pigment-containing aqueous coating composition, water, a pigment such as titanium oxide, an antifoaming agent, a pigment, etc. in an aqueous dispersion of acrylic-fluorine composite polymer particles in advance with a pigment dispersing machine such as a sand mill. After stirring and mixing a predetermined amount of a pigment dispersion in which a dispersant, a pH adjuster, etc. and a predetermined amount of a film-forming auxiliary agent are mixed, a predetermined amount of a thickener is added and mixed, and other necessary additives may be added as appropriate. Good. When preparing an aqueous coating composition without adding a pigment, water, a film-forming auxiliary, an antifoaming agent, a thickener, a pH adjuster, if necessary, in an aqueous dispersion of acrylic-fluorine composite polymer particles In addition, other necessary additives may be added and stirred and mixed by a known method.
塗料用途の添加剤としては、必要に応じ、造膜補助剤、凍結防止剤、顔料、充填剤、顔料分散剤、消泡剤、レベリング剤、レオロジー調整剤、防腐剤、紫外線吸収剤、酸化防止剤、つや消し剤、潤滑剤、加硫剤等を添加することもできる。 Additives for paint applications include film-forming aids, antifreeze agents, pigments, fillers, pigment dispersants, antifoaming agents, leveling agents, rheology modifiers, preservatives, UV absorbers, and antioxidants as necessary. Agents, matting agents, lubricants, vulcanizing agents and the like can also be added.
本発明の水性塗料用組成物を適用する基材としては特に限定されず、溶融めっき鋼板、ステンレススチール板、アルミニウム鋼板、などの金属系基材；スレート、窯業系サイジング材、発泡コンクリート、ガラスなどのセラミック系基材；塩ビシート、ＰＥＴフィルム、ポリカーボネート、アクリルフィルムなどのプラスチック基材に適用できる。溶融めっき鋼板としては、たとえば溶融亜鉛めっき鋼板、溶融亜鉛―アルミニウム―マグネシウム合金めっき鋼板、溶融アルミニウム−亜鉛めっき鋼板、溶融アルミニウムめっき鋼板などがあげられる。 The substrate to which the composition for water-based paint of the present invention is applied is not particularly limited, and is a metal-based substrate such as a hot dip plated steel plate, stainless steel plate, aluminum steel plate, slate, ceramic sizing material, foamed concrete, glass, etc. It can be applied to a plastic substrate such as a vinyl chloride sheet, a PET film, a polycarbonate, and an acrylic film. Examples of the galvanized steel sheet include a galvanized steel sheet, a galvanized steel sheet, a galvanized steel sheet, a galvanized steel sheet, and a galvanized steel sheet.
本発明の水性塗料用組成物を各種の基材に塗装する方法としては従来公知の方法と条件が採用できる。たとえば、基材にスプレーコーティングやロールコーティング、フローコーティング、ローラー、刷毛による塗装などの塗装方法が採用できる。 Conventionally known methods and conditions can be adopted as a method for coating the water-based paint composition of the present invention on various substrates. For example, a coating method such as spray coating, roll coating, flow coating, roller, or brush painting can be employed on the substrate.
塗装後の乾燥方法は特に制限されず、周囲温度での自然乾燥でもよいし、乾燥時間を掛けての低温（５〜６０℃）での乾燥でもよいが、本発明の塗料用組成物は、常温〜２００℃、特に６０〜２００℃（基材温度）での強制乾燥においても、耐候性、耐水性、強度、基材密着性、造膜性に優れた塗膜を形成することができる。強制乾燥に要する時間は、通常３秒間〜１０分間である。 The drying method after coating is not particularly limited and may be natural drying at ambient temperature or drying at a low temperature (5 to 60 ° C.) over a drying time. Even in forced drying at room temperature to 200 ° C., particularly 60 to 200 ° C. (base material temperature), it is possible to form a coating film excellent in weather resistance, water resistance, strength, base material adhesion, and film forming property. The time required for forced drying is usually 3 seconds to 10 minutes.
塗料用組成物としては、耐候性塗料用組成物、特に建築・建材用の耐候性塗料用組成物、自動車の内・外装用塗料用組成物、電気製品の内・外装塗料用組成物、事務機器あるいは厨房器具類の塗料用組成物などが例示でき、特に耐候性・耐久性が良好な点から建材用の耐候性塗料用組成物に有利に適用できる。 The coating composition includes a weather-resistant coating composition, particularly a weather-resistant coating composition for construction and building materials, an automotive interior / exterior coating composition, an electrical product interior / exterior coating composition, and office work. Examples thereof include paint compositions for equipment or kitchen appliances, and can be advantageously applied to weather-resistant paint compositions for building materials from the viewpoint of good weather resistance and durability.
つぎに本発明を実施例に基づいて説明するが、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described based on examples, but the present invention is not limited only to these examples.
実施例１
（ＶＤＦ系重合体（Ａ）の水性分散液の製造）
ＶＤＦ系重合体粒子としてＶｄＦ／ＴＦＥ／ＣＴＦＥ共重合体（＝７２．１／１４．９／１３（モル％））（ＶＴＣ）の粒子の水性分散液（固形分濃度４５．５質量％）６５９．３ｇを２．０Ｌ容のガラス製セパラブルフラスコに入れ、そこに乳化剤としてニューコール７０７ＳＦ（日本乳化剤（株）製）３７．１ｇと、水５６．８ｇを加えて充分に混合して水性分散液を調製した。
Example 1
(Production of aqueous dispersion of VDF polymer (A))
An aqueous dispersion of VdF / TFE / CTFE copolymer (= 72.1 / 14.9 / 13 (mol%)) (VTC) particles (solid content concentration 45.5 mass%) 659 as VDF polymer particles. .3 g was put into a 2.0 L glass separable flask, and 37.1 g of New Coal 707SF (manufactured by Nippon Emulsifier Co., Ltd.) and 56.8 g of water were added as an emulsifier and mixed thoroughly to obtain an aqueous dispersion. A liquid was prepared.
つぎに１．０Ｌ容のガラス製フラスコに、メチルメタクリルレート（ＭＭＡ）１８５．２ｇ（７１．２質量％）、２−エチルヘキシルアクリレート（２ＥＨＡ）４９．９ｇ（１９．２質量％）、グリシジルメタクリレート（ＧＭＡ）１４．３ｇ（５．５質量％）、メタクリル酸（ＭＡＡ）１０．７ｇ（４．１質量％）を加え、モノマー溶液を調製した。 Next, 185.2 g (71.2 mass%) of methyl methacrylate (MMA), 49.9 g (19.2 mass%) of 2-ethylhexyl acrylate (2EHA), glycidyl methacrylate ( GMA) 14.3 g (5.5% by mass) and methacrylic acid (MAA) 10.7 g (4.1% by mass) were added to prepare a monomer solution.
セパラブルフラスコの内温を８０℃にまで昇温し、モノマー溶液の全量を前記ＶＤＦ／ＴＦＥ／ＣＴＦＥ共重合体粒子の水性分散液に３時間かけて添加した。また、モノマー溶液滴下と同時に過硫酸アンモニウム（ＡＰＳ）（１質量％水溶液）４１．１ｇを３０分ごとに７回に分けて添加しながら重合を進めた。重合開始から５時間後に反応溶液を室温まで冷却して反応を終了し、アクリル−フッ素複合重合体粒子の水性分散体を得た（固形分濃度５２．０質量％）。得られたアクリル−フッ素複合重合体中のアクリル系重合体部分の組成は、ＭＭＡ／２ＥＨＡ／ＭＡＡ／ＧＭＡ＝７１．２／１９．２／４．１／５．５（質量％比）であった。また、得られたアクリル−フッ素複合重合体粒子におけるＶＤＦ系重合体部分とアクリル系重合体部分との質量比（ＶＤＦ／アクリル）は、５０／５０であった。 The internal temperature of the separable flask was raised to 80 ° C., and the entire amount of the monomer solution was added to the aqueous dispersion of the VDF / TFE / CTFE copolymer particles over 3 hours. At the same time when the monomer solution was dropped, 41.1 g of ammonium persulfate (APS) (1 mass% aqueous solution) was added in 7 portions every 30 minutes, and the polymerization was advanced. Five hours after the start of polymerization, the reaction solution was cooled to room temperature to complete the reaction, and an aqueous dispersion of acrylic-fluorine composite polymer particles was obtained (solid content concentration 52.0% by mass). The composition of the acrylic polymer portion in the obtained acrylic-fluorine composite polymer was MMA / 2EHA / MAA / GMA = 71.2 / 19.2 / 4.1 / 5.5 (mass% ratio). It was. Moreover, mass ratio (VDF / acryl) of the VDF polymer part and the acrylic polymer part in the obtained acrylic-fluorine composite polymer particles was 50/50.
（水性塗料の調製）
得られたアクリル−フッ素複合重合体の水性分散液を用い、トリエチルアミンでｐＨ７．５まで中和した。水性分散液に成膜助剤（アジピン酸ジエチル）を５質量％／固形分添加し、スリーワンモーターで３０分撹拌して、クリア塗料用の水性塗料用組成物を調製した。
(Preparation of water-based paint)
The obtained aqueous dispersion of acrylic-fluorine composite polymer was neutralized with triethylamine to pH 7.5. A film-forming auxiliary (diethyl adipate) was added to the aqueous dispersion at 5% by mass / solid content, and the mixture was stirred with a three-one motor for 30 minutes to prepare an aqueous coating composition for clear coating.
（ワンコート塗装および試験片の作製）
得られた水性塗料用組成物をガルバリウム鋼板（日本テストパネル（株）製）にバーコーターにより塗装し、１４０℃にて７秒間の条件で乾燥して厚さ４μｍのクリア塗膜を有する試験片を作製した。
(One-coat coating and test piece preparation)
A test piece having a clear coating film having a thickness of 4 μm, which was coated on a galvalume steel sheet (manufactured by Nippon Test Panel Co., Ltd.) with a bar coater and dried at 140 ° C. for 7 seconds. Was made.
得られた試験片を用いて、つぎの特性を評価した。結果を表１に示す。 The following characteristics were evaluated using the obtained test piece. The results are shown in Table 1.
（造膜性）
（評価基準）
１０質量％の水酸化ナトリウム水溶液２０μＬを試験片に滴下した。滴下後、気泡発生までの時間をつぎの５段階で評価した。１：滴下後２分以内に発生、２：滴下後２〜５分の間に発生、３：滴下後５〜１０分の間に発生、４：滴下後１０〜１５分の間に発生、５：滴下後１５分後以上に発生または発生せず。
(Film forming property)
(Evaluation criteria)
20 μL of 10 mass% sodium hydroxide aqueous solution was dropped on the test piece. After dropping, the time until bubble generation was evaluated in the following five stages. 1: Generated within 2 minutes after dropping, 2: Generated within 2 to 5 minutes after dropping, 3: Generated between 5 and 10 minutes after dropping, 4: Generated within 10 to 15 minutes after dropping, 5 : Generated or not generated more than 15 minutes after dropping.
（外観）
（評価基準）
作製した試験片に凝集物、ふくれ、割れ等があるか否かを目視により判断する。○はふくれ、割れ等が全くないもの、△はふくれ、割れ等が１つ以上で５つ以内のもの、×はふくれ、割れ等が５つより多いものである。
(appearance)
(Evaluation criteria)
It is visually determined whether the produced test piece has aggregates, blisters, cracks, or the like. ○ indicates that there are no blisters, cracks, etc., Δ indicates one or more blisters, cracks, etc. and no more than five, and × indicates blisters, cracks, etc. greater than five.
（初期密着性）
塗膜の乾燥後２４時間放置した後、試験片に対してＪＩＳ Ｄ０２０２−１９８８に準拠して碁盤目テープ剥離試験を行う。セロハンテープ（「ＣＴ２４」、ニチバン（株）製）を用い、指の腹でフィルムに密着させた後剥離する。判定は２５マスの内、剥離しないマス目の数で表す。
(Initial adhesion)
After leaving the coating film to stand for 24 hours, a cross-cut tape peeling test is performed on the test piece in accordance with JIS D0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film is adhered to the film with the belly of the finger and then peeled off. The determination is represented by the number of squares that do not peel out of 25 squares.
（耐候性）
（試験方法）
作製した試験片を促進耐候性試験機に入れ、３２２時間後の赤外分光スペクトルをＡＴＲ法（減衰全反射法）を用い測定する。アクリレート由来のＣ−Ｈ伸縮振動（１７００ｃｍ−１付近）の吸収の減衰率によって、耐侯性を評価する。
(Weatherability)
(Test method)
The prepared test piece is put into an accelerated weathering tester, and the infrared spectrum after 322 hours is measured using the ATR method (attenuated total reflection method). The weather resistance is evaluated by the attenuation rate of absorption of acrylate-derived C—H stretching vibration (around 1700 cm −1 ).
促進耐候性試験機（ＳＵＶ）：スーパーＵＶテスター、岩崎電気（株）製
試験サイクル：純水スプレー（１０秒毎）１時間→露光１１時間（ブラックパネル温度６３℃、相対湿度７０％）→結露１１時間（ブラックパネル温度３０℃、相対湿度１００％）。このサイクルを１サイクル（２３時間）とする。
試験時間：３２２時間（１４サイクル）
Accelerated weathering tester (SUV): Super UV tester, Iwasaki Electric Co., Ltd. test cycle: pure water spray (every 10 seconds) 1 hour → exposure 11 hours (black panel temperature 63 ° C, relative humidity 70%) → condensation 11 hours (black panel temperature 30 ° C., relative humidity 100%). This cycle is defined as one cycle (23 hours).
Test time: 322 hours (14 cycles)
（評価基準）
試験後の試験片表面部をＡＴＲ法（減衰全反射法）を用い、赤外分光スペクトルを測定する。促進耐候性試験前の試験片と試験後（３２２時間後）の試験片を比較する。１１５０ｃｍ−１付近のＣ−Ｆ伸縮振動の吸収を規格化し、１７００ｃｍ−１付近のアクリレート由来のＣ−Ｈ伸縮振動の吸収が試験前後で減衰していないかを確認する。○は試験前と比較し、１７００ｃｍ−１付近のアクリレート由来のＣ−Ｈ伸縮振動の吸収の減衰が１０％以内のもの、△は減衰が１０％より大きく、２５％以内のもの、×は減衰が２５％より大きいものである。
ＡＴＲ測定：Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製 ＦＴ−ＩＲ Ｓｐｅｃｔｒｏｍｅｔｅｒ Ｓｐｅｃｔｏｒｕｍ１００を使用
(Evaluation criteria)
An infrared spectrum is measured on the surface of the test piece after the test using the ATR method (attenuated total reflection method). The specimen before the accelerated weathering test is compared with the specimen after the test (after 322 hours). 1150cm normalized absorption of C-F stretching vibration in the vicinity of -1, the absorption of C-H stretching vibration derived from acrylate near 1700 cm -1 confirms that no decay before and after the test. ○ is less than 10% of absorption of C—H stretching vibration derived from acrylate near 1700 cm −1 compared to before the test, Δ is greater than 10% and within 25%, × is attenuated Is greater than 25%.
ATR measurement: FT-IR Spectrometer Spectrum 100 manufactured by Perkin Elmer is used.
（トップクリア塗装および試験片の作製）
得られた水性塗料用組成物をガルバリウム鋼板（日本テストパネル社製）に下塗り：ダイキン社製（ゼッフル遮熱塗料下塗り）、中塗り：ダイキン社製（ゼッフル遮熱塗料下塗り）を塗布した塗板に、バーコーターを用いて塗布し、１日乾燥して厚さ１０μｍのクリア塗膜を有する試験片を作製した。
(Top clear coating and test piece preparation)
The resulting aqueous coating composition is applied to a coated plate coated with a galvalume steel plate (manufactured by Nippon Test Panel Co., Ltd.) by Daikin Co., Ltd. (Zeffle thermal barrier paint undercoat) and intermediate coating: Daikin Co., Ltd. A test piece having a clear coating film having a thickness of 10 μm was prepared by applying using a bar coater and drying for one day.
（初期密着試験）
試験片に対してＪＩＳ Ｄ０２０２−１９８８に準拠して碁盤目テープ剥離試験を行う。セロハンテープ（「ＣＴ２４」、ニチバン（株）製）を用い、指の腹でフィルムに密着させた後剥離する。判定は２５マスの内、剥離しないマス目の数で表す。
(Initial adhesion test)
A cross-cut tape peeling test is performed on the test piece in accordance with JIS D0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film is adhered to the film with the belly of the finger and then peeled off. The determination is represented by the number of squares that do not peel out of 25 squares.
（初期耐水試験）
得られた試験片を２３℃で１日没水処理し、取り出した直後の膨れ（ＪＩＳ Ｋ５６００−８−２）、割れ（ＪＩＳ Ｋ５６００−８−４）、はがれ（ＪＩＳ Ｋ５６００−８−５）の等級を評価する。
(Initial water resistance test)
The obtained test piece was treated with water at 23 ° C. for one sunset, and immediately after being taken out, it was swollen (JIS K5600-8-2), cracked (JIS K5600-8-4), and peeled (JIS K5600-8-5). Evaluate the grade.
（２次密着性試験）
また、没水処理後取り出し、２３℃で１日乾燥した後、ＪＩＳ Ｄ０２０２−１９８８に準拠して碁盤目テープ剥離試験を行う。セロハンテープ（「ＣＴ２４」、ニチバン（株）製）を用い、指の腹でフィルムに密着させた後剥離する。判定は２５マスの内、剥離しないマス目の数で表す。
(Secondary adhesion test)
Moreover, after taking out after a water immersion process and drying at 23 degreeC for 1 day, a cross-cut tape peeling test is done based on JISD0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film is adhered to the film with the belly of the finger and then peeled off. The determination is represented by the number of squares that do not peel out of 25 squares.
（膨れ）
膨れの等級（ＪＩＳ Ｋ５６００−８−２）の評価基準
密度を０〜５の等級（小さい方が０）に、大きさをＳ１〜Ｓ５の等級（Ｓ１の方が小さい）に分け、たとえば２（Ｓ１）のように記載する。
（割れ）
割れの等級（ＪＩＳ Ｋ５６００−８−４）の評価基準
密度を０〜５の等級（小さい方が０）に、大きさをＳ０〜Ｓ５の等級（Ｓ０の方が小さい）に、深さをａ〜ｃの等級（ａの方が浅い）に分け、たとえば２（Ｓ１）ｂのように記載する。
（はがれ）
はがれの等級（ＪＩＳ Ｋ５６００−８−５）の評価基準
密度を０〜５の等級（小さい方が０）に、大きさをＳ１〜Ｓ５の等級（Ｓ１の方が小さい）に、深さをａ〜ｂの等級（ａの方が浅い）に分け、たとえば２（Ｓ１）ａのように記載する。
(Bulging)
Evaluation criteria for blister grade (JIS K5600-8-2) Density is divided into grades 0-5 (smaller is 0), and sizes are divided into grades S1-S5 (smaller S1). It is described as S1).
(Crack)
Evaluation criteria of cracking grade (JIS K5600-8-4) Density is graded from 0 to 5 (smaller is 0), size is from S0 to S5 (S0 is smaller), and depth is a It is divided into ˜c grades (a is shallower), and is described as, for example, 2 (S1) b.
(Peeling)
Evaluation standard of peeling grade (JIS K5600-8-5) Density is graded 0-5 (smaller is 0), size is graded S1-S5 (smaller is S1), depth is a It is divided into ˜b grades (a is shallower), and is described as 2 (S1) a, for example.
（一般耐水試験）
試験片を２３℃で６日没水処理し、取り出した直後の膨れ（ＪＩＳ Ｋ５６００−８−２）、割れ（ＪＩＳ Ｋ５６００−８−４）、はがれ（ＪＩＳ Ｋ５６００−８−５）の等級を評価する。
(General water resistance test)
The test piece was treated with sunset water for 6 days at 23 ° C., and the grade of blistering (JIS K5600-8-2), cracking (JIS K5600-8-4), and peeling (JIS K5600-8-5) immediately after removal was evaluated. To do.
（２次密着性試験）
また、没水処理後取り出し、２３℃で１週間乾燥した後、ＪＩＳ Ｄ０２０２−１９８８に準拠して碁盤目テープ剥離試験を行う。セロハンテープ（「ＣＴ２４」、ニチバン（株）製）を用い、指の腹でフィルムに密着させた後剥離する。判定は２５マスの内、剥離しないマス目の数で表す。
(Secondary adhesion test)
Moreover, after taking out after a water immersion process and drying at 23 degreeC for 1 week, a cross-cut tape peeling test is done based on JISD0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film is adhered to the film with the belly of the finger and then peeled off. The determination is represented by the number of squares that do not peel out of 25 squares.
（耐候性）
作製した試験片を促進耐候性試験機に入れ、一定サイクルごとに光沢値、Ｌ値、ａ値、ｂ値を測定する。その結果から光沢保持率を算出し、塗膜の耐侯性を評価する。
(Weatherability)
The prepared test piece is put into an accelerated weathering tester, and the gloss value, L value, a value, and b value are measured every fixed cycle. The gloss retention is calculated from the result, and the weather resistance of the coating film is evaluated.
促進耐候性試験機（ＳＵＶ）：スーパーＵＶテスター、岩崎電気（株）製
試験サイクル：純水スプレー（１０秒毎）１時間→露光１１時間（ブラックパネル温度６３℃、相対湿度７０％）→結露１１時間（ブラックパネル温度３０℃、相対湿度１００％）。このサイクルを１サイクル（２３時間）とする。
試験時間：９６６時間（４２サイクル）〜１６１０時間（７０サイクル）
Accelerated weathering tester (SUV): Super UV tester, Iwasaki Electric Co., Ltd. test cycle: pure water spray (every 10 seconds) 1 hour → exposure 11 hours (black panel temperature 63 ° C, relative humidity 70%) → condensation 11 hours (black panel temperature 30 ° C., relative humidity 100%). This cycle is defined as one cycle (23 hours).
Test time: 966 hours (42 cycles) to 1610 hours (70 cycles)
実施例２〜４
アクリル系重合体用のアクリル系単量体混合物として、表１に示す単量体混合物を用いたほかは実施例１と同様にしてシード重合を行い、それぞれアクリル−フッ素複合重合体を得た。
Examples 2-4
Seed polymerization was carried out in the same manner as in Example 1 except that the monomer mixture shown in Table 1 was used as the acrylic monomer mixture for the acrylic polymer to obtain an acrylic-fluorine composite polymer.
得られたアクリル−フッ素複合重合体粒子の水性分散液を用い、実施例１と同様にしてクリア塗料用の水性塗料用組成物を調製し、実施例１と同様にして塗膜を形成し試験片を作製し、各種の特性を調べた。結果を表１に示す。 Using the obtained aqueous dispersion of acrylic-fluorine composite polymer particles, an aqueous coating composition for clear coating was prepared in the same manner as in Example 1, and a coating film was formed and tested in the same manner as in Example 1. Pieces were made and examined for various properties. The results are shown in Table 1.
比較例１
アクリル系重合体用のアクリル系単量体混合物として、ＭＭＡ／ｎ−ＢＡ／ＡＡ＝９８．０／１．０／１．０（質量％比）の比較用単量体混合物を用いたほかは実施例１と同様にしてシード重合を行い、比較用のアクリル−フッ素複合重合体を得た。アクリル系重合体部分の組成は、ＭＭＡ／ｎ−ＢＡ／ＡＡ＝９８．０／１．０／１．０（質量％比）であった。また、得られたアクリル−フッ素複合重合体粒子におけるＶＤＦ系重合体部分とアクリル系重合体部分との質量比（ＶＤＦ／アクリル）は、７０／３０であった。
Comparative Example 1
As the acrylic monomer mixture for the acrylic polymer, a comparative monomer mixture of MMA / n-BA / AA = 98.0 / 1.0 / 1.0 (mass% ratio) was used. Seed polymerization was carried out in the same manner as in Example 1 to obtain a comparative acrylic-fluorine composite polymer. The composition of the acrylic polymer portion was MMA / n-BA / AA = 98.0 / 1.0 / 1.0 (mass% ratio). Moreover, mass ratio (VDF / acryl) of the VDF polymer part and the acrylic polymer part in the obtained acrylic-fluorine composite polymer particles was 70/30.
得られたアクリル−フッ素複合重合体粒子の水性分散液を用い、実施例１と同様にしてクリア塗料用の水性塗料用組成物を調製し、実施例１と同様にして塗膜を形成し試験片を作製し、各種の特性を調べた。結果を表１に示す。 Using the obtained aqueous dispersion of acrylic-fluorine composite polymer particles, an aqueous coating composition for clear coating was prepared in the same manner as in Example 1, and a coating film was formed and tested in the same manner as in Example 1. Pieces were made and examined for various properties. The results are shown in Table 1.
表１における単量体の略号は、以下の化合物を示す。
ＭＭＡ：メチルメタクリレート
ｎ−ＢＡ：ｎ−ブチルアクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
２−ＥＨＡ：２−エチルへキシルアクリレート
ＧＭＡ：グリシジルメタクリレート
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＭＰＴＥＳ：３−メタクリロキシプロピルトリエトキシシラン
Abbreviations of monomers in Table 1 indicate the following compounds.
MMA: methyl methacrylate n-BA: n-butyl acrylate CHMA: cyclohexyl methacrylate 2-EHA: 2-ethylhexyl acrylate GMA: glycidyl methacrylate MAA: methacrylic acid AA: acrylic acid MPTES: 3-methacryloxypropyltriethoxysilane
表１から、成分（ｂ１）、成分（ｂ２）、成分（ｂ３）を含むアクリル−フッ素複合重合体が、基材との密着性を向上させていることが分かる。 From Table 1, it can be seen that the acrylic-fluorine composite polymer containing the component (b1), the component (b2), and the component (b3) improves the adhesion to the substrate.
実施例５
ＶＤＦ系重合体粒子としてＶｄＦ／ＴＦＥ共重合体（＝８０／２０（モル％））（ＶＴ）の粒子の水性分散液（固形分濃度１０．０質量％）を用いたほかは実施例３と同様にしてシード重合を行い、アクリル−フッ素複合重合体を得た。
Example 5
Example 3 except that an aqueous dispersion (solid content concentration: 10.0% by mass) of VdF / TFE copolymer (= 80/20 (mol%)) (VT) was used as the VDF polymer particles. Similarly, seed polymerization was performed to obtain an acrylic-fluorine composite polymer.
得られたアクリル−フッ素複合重合体粒子の水性分散液を用い、実施例１と同様にしてクリア塗料用の水性塗料用組成物を調製し、実施例１と同様にして塗膜を形成し試験片を作製し、各種の特性を調べた。結果を表２に示す。 Using the obtained aqueous dispersion of acrylic-fluorine composite polymer particles, an aqueous coating composition for clear coating was prepared in the same manner as in Example 1, and a coating film was formed and tested in the same manner as in Example 1. Pieces were made and examined for various properties. The results are shown in Table 2.
実施例６
ＶＤＦ系重合体粒子としてＶｄＦ／ＨＦＰ共重合体（＝９１／９（モル％））（ＶＨ）の粒子の水性分散液（固形分濃度１０．０質量％）を用いたほかは実施例３と同様にしてシード重合を行い、アクリル−フッ素複合重合体を得た。
Example 6
Example 3 except that an aqueous dispersion (solid content concentration 10.0 mass%) of VdF / HFP copolymer (= 91/9 (mol%)) (VH) was used as the VDF polymer particles. Similarly, seed polymerization was performed to obtain an acrylic-fluorine composite polymer.
得られたアクリル−フッ素複合重合体粒子の水性分散液を用い、実施例１と同様にしてクリア塗料用の水性塗料用組成物を調製し、実施例１と同様にして塗膜を形成し試験片を作製し、各種の特性を調べた。結果を表２に示す。 Using the obtained aqueous dispersion of acrylic-fluorine composite polymer particles, an aqueous coating composition for clear coating was prepared in the same manner as in Example 1, and a coating film was formed and tested in the same manner as in Example 1. Pieces were made and examined for various properties. The results are shown in Table 2.
表２から、成分（ｂ１）、成分（ｂ２）、成分（ｂ３）を含むアクリル−ＶＤＦ系フッ素複合重合体が、基材との密着性を向上させていることが分かる。 From Table 2, it can be seen that the acrylic-VDF fluorine composite polymer containing the component (b1), the component (b2), and the component (b3) improves the adhesion to the substrate.
Claims (9)
（Ｂ）該フッ化ビニリデン系重合体（Ａ）と相溶性の（メタ）アクリル酸エステル単位(ｂ１)、該フッ化ビニリデン系重合体（Ａ）と非相溶性の（メタ）アクリル酸エステル単位(ｂ２)および加熱により架橋可能な架橋性基を有する（メタ）アクリル系単量体単位(ｂ３)を含む架橋性アクリル系重合体（Ｂ）と、
からなるアクリル−フッ素複合重合体粒子であって、フッ化ビニリデン系重合体（Ａ）／架橋性アクリル系重合体（Ｂ）が質量比で１０／９０〜９０／１０であるアクリル−フッ素複合重合体粒子。 (A) a vinylidene fluoride polymer containing at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as a structural unit, and a vinylidene fluoride unit;
(B) (Meth) acrylic acid ester unit (b1) compatible with the vinylidene fluoride polymer (A), (meth) acrylic acid ester unit incompatible with the vinylidene fluoride polymer (A) a crosslinkable acrylic polymer (B) comprising (b2) and a (meth) acrylic monomer unit (b3) having a crosslinkable group capable of being crosslinked by heating;
Acrylic-fluorine composite polymer particles comprising a vinylidene fluoride polymer (A) / crosslinkable acrylic polymer (B) in a mass ratio of 10/90 to 90/10. Coalesced particles.
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| WO2013047880A1 (en) * | 2011-09-30 | 2013-04-04 | ダイキン工業株式会社 | Composition and coated article |
| JP2014152186A (en) * | 2013-02-05 | 2014-08-25 | Jsr Corp | Aqueous fluororesin composition |
| WO2015068751A1 (en) * | 2013-11-07 | 2015-05-14 | 株式会社日本触媒 | Film-forming auxiliary |
| JP2015091914A (en) * | 2013-10-01 | 2015-05-14 | Jsr株式会社 | Composition for coating, coating and coated body |
| WO2019124215A1 (en) * | 2017-12-20 | 2019-06-27 | ダイキン工業株式会社 | Core-shell type particle, dispersion and powder |
| WO2020090749A1 (en) * | 2018-10-29 | 2020-05-07 | Ａｇｃ株式会社 | Aqueous coating material and coated article |
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| US11859075B2 (en) | 2017-12-20 | 2024-01-02 | Daikin Industries, Ltd. | Core-shell type particle, dispersion and powder |
| WO2020090749A1 (en) * | 2018-10-29 | 2020-05-07 | Ａｇｃ株式会社 | Aqueous coating material and coated article |
| KR20210093845A (en) | 2018-11-22 | 2021-07-28 | 도레이 카부시키가이샤 | Fluorine-containing polymer particles |
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