JP2007063482A - Aqueous fluorine-containing polymer composition and coated article - Google Patents
Aqueous fluorine-containing polymer composition and coated article Download PDFInfo
- Publication number
- JP2007063482A JP2007063482A JP2005254049A JP2005254049A JP2007063482A JP 2007063482 A JP2007063482 A JP 2007063482A JP 2005254049 A JP2005254049 A JP 2005254049A JP 2005254049 A JP2005254049 A JP 2005254049A JP 2007063482 A JP2007063482 A JP 2007063482A
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- Prior art keywords
- fluoropolymer
- water
- resin
- coating
- aqueous
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
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- 239000011737 fluorine Substances 0.000 title claims abstract description 17
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- 239000002253 acid Substances 0.000 claims description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
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- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
Description
本発明は、含フッ素重合体水性組成物及び被覆物品に関する。 The present invention relates to an aqueous fluoropolymer composition and a coated article.
ポリテトラフルオロエチレン〔ＰＴＦＥ〕等の含フッ素重合体は、耐熱性、電気絶縁性等の特性に優れ、その成形体が低摩擦係数を有し、非粘着性にも優れている。この表面特性は、耐薬品性、撥水撥油性、離型性、摺動性等を発揮する。 Fluoropolymers such as polytetrafluoroethylene [PTFE] are excellent in properties such as heat resistance and electrical insulation, the molded product has a low coefficient of friction, and is excellent in non-adhesiveness. This surface property exhibits chemical resistance, water / oil repellency, releasability, slidability, and the like.
含フッ素重合体は、このような性質を有するので、例えば、被覆用の組成物に調製し、被塗装物上に塗装して含フッ素重合体からなる塗膜を設けることにより、成形金型離型材、オフィスオートメーション〔ＯＡ〕機器用ロール、アイロン等の家庭用品、フライパンやホットプレート等の厨房器具、食品工業、電気工業、機械工業等の分野で幅広い用途がある。 Since the fluoropolymer has such properties, for example, it is prepared as a coating composition, and is applied to an object to be coated to provide a coating film made of the fluoropolymer, thereby separating the mold. Wide range of applications in fields such as mold materials, office automation (OA) equipment rolls, household items such as irons, kitchen utensils such as frying pans and hot plates, food industry, electrical industry, and machine industry.
含フッ素重合体は、一方、その非粘着性により、被塗装物との密着性に乏しいという問題を生じていた。この密着性の向上を目的として、耐熱樹脂等のバインダー樹脂と含フッ素重合体とを配合したプライマーを下塗りとして予め被塗装物上に塗装することが行われている。 On the other hand, the fluorine-containing polymer has a problem of poor adhesion to an object to be coated due to its non-adhesiveness. For the purpose of improving the adhesion, a primer containing a binder resin such as a heat-resistant resin and a fluorine-containing polymer is preliminarily coated on an object to be coated as an undercoat.
プライマーとしては、例えば、それぞれ所定のコロイド状シリカとポリアミド酸の塩とからなる結合剤、該酸塩を溶解するＮ−メチルピロリドン他の有機液体、水、及び、フルオロ重合体からなるプライマー組成物が提案されている（例えば、特許文献１参照。）。しかしながら、このプライマー組成物は、ポリアミド酸塩が比較的多数のカルボキシル基を有するので耐食性に劣るという欠点があった。 Examples of the primer include a binder composed of a predetermined colloidal silica and a polyamic acid salt, N-methylpyrrolidone and other organic liquids that dissolve the acid salt, water, and a primer composition composed of a fluoropolymer. Has been proposed (see, for example, Patent Document 1). However, this primer composition has a drawback in that the polyamic acid salt has a relatively large number of carboxyl groups and thus is inferior in corrosion resistance.
プライマーとしては、また、ポリエーテルスルホン、ポリアミドイミド及び／又はポリイミド、フッ素樹脂、並びに、金属粉末を有機溶媒中に溶解又は分散させたプライマー組成物が提案されている（例えば、特許文献２参照。）。このプライマー組成物は、分散媒がＮ−メチルピロリドン等の有機溶媒であるため、環境上好ましくない場合があり、塗装時の簡便性や作業性に劣る問題があった。 As a primer, a primer composition in which polyethersulfone, polyamideimide and / or polyimide, fluororesin, and metal powder are dissolved or dispersed in an organic solvent has been proposed (see, for example, Patent Document 2). ). In this primer composition, since the dispersion medium is an organic solvent such as N-methylpyrrolidone, there are cases where it is not preferable from the viewpoint of environment, and there is a problem in that it is inferior in convenience and workability during coating.
水性プライマー組成物としては、ポリエーテルスルホン、ポリアミドイミド及び／又はポリイミド、並びに、ＰＴＦＥ等のフッ素樹脂からなるものがある（例えば、特許文献３及び４参照。）。しかしながら、これらの水性プライマー組成物は、塗料としてスプレー塗装した場合、ハジキや塗装ムラが起き易く塗装性に劣る問題点があった。
本発明の目的は、上記現状に鑑み、耐食性が良好で、ハジキや塗装ムラが起きにくく、塗装性に優れた含フッ素重合体組成物を提供することにある。 An object of the present invention is to provide a fluorine-containing polymer composition that has good corrosion resistance, is less likely to cause repellency and uneven coating, and has excellent paintability.
本発明は、水溶性ポリアミドイミド樹脂（Ｐ）、上記水溶性ポリアミドイミド樹脂とは異なる耐熱樹脂（Ｑ）及び含フッ素重合体（Ｒ）を含有する水性分散体からなることを特徴とする含フッ素重合体水性組成物である。 The present invention comprises a water-soluble polyamideimide resin (P), an aqueous dispersion containing a heat-resistant resin (Q) different from the water-soluble polyamideimide resin, and a fluorine-containing polymer (R). It is a polymer aqueous composition.
本発明は、上記含フッ素重合体水性組成物を塗装することにより得られることを特徴とする被覆物品である。
以下に本発明を詳細に説明する。
The present invention is a coated article obtained by coating the above fluoropolymer aqueous composition.
The present invention is described in detail below.
本発明の含フッ素重合体水性組成物は、水溶性ポリアミドイミド樹脂（Ｐ）、上記水溶性ポリアミドイミド樹脂とは異なる耐熱樹脂（Ｑ）及び含フッ素重合体（Ｒ）を含有する水性分散体からなるものである。 The aqueous fluoropolymer composition of the present invention comprises an aqueous dispersion containing a water-soluble polyamideimide resin (P), a heat-resistant resin (Q) different from the water-soluble polyamideimide resin, and a fluoropolymer (R). It will be.
本発明の含フッ素重合体水性組成物は、被塗装物に塗装することにより、上記被塗装物上に塗膜を形成することができるものである。本明細書において、上記含フッ素重合体水性組成物についての「塗装」とは、上記含フッ素重合体水性組成物を塗布し、必要に応じて乾燥し、次いで焼成することよりなる工程を意味する。 The aqueous fluoropolymer composition of the present invention can form a coating film on the object to be coated by coating the object to be coated. In the present specification, “coating” for the fluoropolymer aqueous composition means a process comprising applying the fluoropolymer aqueous composition, drying it if necessary, and then baking it. .
上記塗膜は、上記耐熱樹脂（Ｑ）と含フッ素重合体（Ｒ）とが表面張力に差を有することから、焼成時に上記含フッ素重合体（Ｒ）が浮上し、塗膜の表面側に主として上記含フッ素重合体（Ｒ）が配置し、被塗装物側に主として上記耐熱樹脂（Ｑ）が配置しているものである。上記塗膜は、上記耐熱樹脂（Ｑ）が被塗装物との接着性を有するので、被塗装物に対して優れた密着性を有し得るものである。 Since the heat-resistant resin (Q) and the fluoropolymer (R) have a difference in surface tension, the fluoropolymer (R) floats on the surface side of the coating film. The fluoropolymer (R) is mainly disposed, and the heat-resistant resin (Q) is mainly disposed on the object to be coated. Since the heat-resistant resin (Q) has adhesiveness to the object to be coated, the coating film can have excellent adhesion to the object to be coated.
上記塗膜は、必要に応じ、該塗膜の上に上塗り塗膜を積層させてもよい。上記上塗り塗膜は、通常、上塗り用含フッ素重合体からなる上塗り塗料を塗装することにより形成されるものである。上記塗膜は、該塗膜の上に上塗り塗膜を積層させる場合、上記含フッ素重合体（Ｒ）が上記上塗り用含フッ素重合体と親和性を有するので、上塗り塗膜との密着性にも優れている。 The above-mentioned coating film may be laminated with a top coating film on the coating film, if necessary. The top coat film is usually formed by applying a top coat composed of a fluoropolymer for top coat. When the top coat film is laminated on the coating film, the fluoropolymer (R) has an affinity with the topcoat fluoropolymer, so that the adhesion to the top coat film is improved. Is also excellent.
本明細書において、上記被塗装物及び上記塗膜を有するものを被覆物品という。上記被覆物品は、更に、上記上塗り塗膜を有するものであってもよい。 In this specification, what has the said to-be-coated article and the said coating film is called coated article. The coated article may further have the top coat film.
本明細書において、上記被覆物品を作製する方法は、上記塗膜の上に上記上塗り塗膜を積層させない場合、ワンコート法という。上記ワンコート法は、上記被塗装物上に上記含フッ素重合体水性組成物を塗布し、必要に応じて乾燥し、次いで焼成することよりなるものである。 In this specification, the method for producing the coated article is referred to as a one-coat method when the top coat film is not laminated on the coat film. The one-coat method comprises coating the fluoropolymer aqueous composition on the article to be coated, drying as necessary, and then firing.
本明細書において、上記被覆物品を作製する方法は、上記塗膜の上に上記上塗り塗膜を積層させる場合、ツーコート法という。上記ツーコート法は、通常、上記被塗装物上に上記含フッ素重合体水性組成物を塗布し、必要に応じて乾燥し、次に焼成することなく、上記上塗り塗料を塗布し、必要に応じて乾燥し、次いで焼成することよりなるものである。上記ツーコート法の場合、上記含フッ素重合体水性組成物は、上記上塗り塗膜の下塗り塗料として用いられ、プライマーとして機能する。 In this specification, the method for producing the coated article is referred to as a two-coat method when the top coat film is laminated on the coat film. In the two-coat method, usually, the fluoropolymer aqueous composition is applied onto the object to be coated, dried as necessary, and then applied without applying the top coat without firing. It consists of drying and then firing. In the case of the two-coating method, the fluoropolymer aqueous composition is used as an undercoat paint for the top coat film and functions as a primer.
本発明の含フッ素重合体水性組成物において、上記水性分散体は、含フッ素重合体（Ｒ）からなるものである。
上記含フッ素重合体（Ｒ）は、主鎖又は側鎖を構成する炭素原子に直接結合しているフッ素原子を有する重合体である。上記含フッ素重合体は、非溶融加工性であってもよいし、溶融加工性であってもよい。
In the aqueous fluoropolymer composition of the present invention, the aqueous dispersion is made of the fluoropolymer (R).
The fluoropolymer (R) is a polymer having a fluorine atom that is directly bonded to a carbon atom constituting the main chain or side chain. The fluoropolymer may be non-melt processable or melt processable.
上記含フッ素重合体（Ｒ）は、含フッ素モノエチレン系不飽和炭化水素（ａ）を重合することにより得られるものである。
上記含フッ素モノエチレン系不飽和炭化水素（ａ）（以下、「不飽和炭化水素（ａ）」という。）は、フッ素原子により水素原子の一部又は全部が置換されているビニル基を、分子中に１個有する不飽和炭化水素である。
The fluorine-containing polymer (R) is obtained by polymerizing the fluorine-containing monoethylenically unsaturated hydrocarbon (a).
The fluorine-containing monoethylenically unsaturated hydrocarbon (a) (hereinafter referred to as “unsaturated hydrocarbon (a)”) is a molecule in which a vinyl group in which some or all of the hydrogen atoms are substituted by fluorine atoms It is an unsaturated hydrocarbon having one in it.
上記不飽和炭化水素（ａ）は、塩素原子等のフッ素原子以外のハロゲン原子、及び／又は、トリフルオロメチル基等のフッ素化メチル基により置換されているものであってもよい。但し、上記不飽和炭化水素（ａ）は、後述のトリフルオロエチレンを除く。 The unsaturated hydrocarbon (a) may be substituted with a halogen atom other than a fluorine atom such as a chlorine atom and / or a fluorinated methyl group such as a trifluoromethyl group. However, the unsaturated hydrocarbon (a) excludes trifluoroethylene described later.
上記不飽和炭化水素（ａ）としては特に限定されず、例えば、テトラフルオロエチレン〔ＴＦＥ〕、ヘキサフルオロプロピレン〔ＨＦＰ〕、クロロトリフルオロエチレン〔ＣＴＦＥ〕、ビニリデンフルオライド〔ＶｄＦ〕、フッ化ビニル〔ＶＦ〕等が挙げられ、これらは、１種又は２種以上を用いることができる。 The unsaturated hydrocarbon (a) is not particularly limited. For example, tetrafluoroethylene [TFE], hexafluoropropylene [HFP], chlorotrifluoroethylene [CTFE], vinylidene fluoride [VdF], vinyl fluoride [ VF] and the like, and one or more of these can be used.
上記含フッ素重合体（Ｒ）は、また、少なくとも１種の上記不飽和炭化水素（ａ）と、上記不飽和炭化水素（ａ）と共重合し得る不飽和化合物（ｂ）との共重合体であってもよい。 The fluoropolymer (R) is also a copolymer of at least one type of the unsaturated hydrocarbon (a) and an unsaturated compound (b) that can be copolymerized with the unsaturated hydrocarbon (a). It may be.
上記不飽和化合物（ｂ）は、１種又は２種以上の不飽和化合物（ｂ）のみを重合することにより得られる重合体を上記含フッ素重合体（Ｒ）として用いないものであるが、上記不飽和炭化水素（ａ）が１種又は２種以上の上記不飽和炭化水素（ａ）のみを重合することにより得られる重合体を上記含フッ素重合体として用い得るものである点で、上記不飽和炭化水素（ａ）と異なるものである。 The unsaturated compound (b) does not use a polymer obtained by polymerizing only one or two or more unsaturated compounds (b) as the fluoropolymer (R). In view of the fact that the unsaturated hydrocarbon (a) can be used as the fluoropolymer, a polymer obtained by polymerizing only one or more of the unsaturated hydrocarbons (a). It is different from the saturated hydrocarbon (a).
上記不飽和化合物（ｂ）としては特に限定されず、例えば、トリフルオロエチレン〔３ＦＨ〕；エチレン〔Ｅｔ〕、プロピレン〔Ｐｒ〕等のハロゲン原子を有しないモノエチレン系不飽和炭化水素等が挙げられる。これらは、１種又は２種以上を用いることができる。 The unsaturated compound (b) is not particularly limited, and examples thereof include trifluoroethylene [3FH]; monoethylenically unsaturated hydrocarbons having no halogen atom such as ethylene [Et] and propylene [Pr]. . These can use 1 type (s) or 2 or more types.
上記含フッ素重合体（Ｒ）は、単独重合体であってもよいし、共重合体であってよいし、単独重合体及び少なくとも１種以上の共重合体からなる混合物であってもよいし、少なくとも２種以上の共重合体からなる混合物であってもよい。 The fluoropolymer (R) may be a homopolymer, a copolymer, or a mixture of a homopolymer and at least one copolymer. A mixture of at least two or more types of copolymers may be used.
上記単独重合体としては特に限定されず、例えば、ポリテトラフルオロエチレン〔ＰＴＦＥ〕、ポリクロロトリフルオロエチレン〔ＰＣＴＦＥ〕、ポリビニリデンフルオライド〔ＰＶｄＦ〕、ポリフッ化ビニル〔ＰＶＦ〕等が挙げられる。 The homopolymer is not particularly limited, and examples thereof include polytetrafluoroethylene [PTFE], polychlorotrifluoroethylene [PCTFE], polyvinylidene fluoride [PVdF], and polyvinyl fluoride [PVF].
上記共重合体としては特に限定されず、例えば、２元共重合体、３元共重合体等が挙げられる。上記２元共重合体としては、例えば、ＴＦＥ／ＨＦＰ共重合体〔ＦＥＰ〕、ＴＦＥ／ＣＴＦＥ共重合体、ＴＦＥ／ＶｄＦ共重合体、ＴＦＥ／３ＦＨ共重合体、Ｅｔ／ＴＦＥ共重合体〔ＥＴＦＥ〕、ＴＦＥ／Ｐｒ共重合体等のＴＦＥ系共重合体；ＶｄＦ／ＨＦＰ共重合体；Ｅｔ／ＣＴＦＥ共重合体〔ＥＣＴＦＥ〕；Ｅｔ／ＨＦＰ共重合体等が挙げられる。本明細書において、上記「ＴＦＥ系共重合体」とは、ＴＦＥと、ＴＦＥ以外のその他の単量体の１種又は２種以上とを共重合して得られるものを意味する。上記ＴＦＥ系共重合体は、通常、上記ＴＦＥ系共重合体中に付加されているＴＦＥ以外のその他の単量体の割合が、上記ＴＦＥと上記その他の単量体との合計質量の１質量％を超えていることが好ましい。
上記３元共重合体としては、ＶｄＦ／ＴＦＥ／ＨＦＰ共重合体等が挙げられる。
It does not specifically limit as said copolymer, For example, a binary copolymer, a ternary copolymer, etc. are mentioned. Examples of the binary copolymer include TFE / HFP copolymer [FEP], TFE / CTFE copolymer, TFE / VdF copolymer, TFE / 3FH copolymer, Et / TFE copolymer [ETFE]. ], TFE copolymers such as TFE / Pr copolymer; VdF / HFP copolymer; Et / CTFE copolymer [ECTFE]; Et / HFP copolymer. In the present specification, the “TFE copolymer” means a copolymer obtained by copolymerizing TFE and one or more monomers other than TFE. In the TFE copolymer, the proportion of other monomers other than TFE added to the TFE copolymer is usually 1 mass of the total mass of the TFE and the other monomers. % Is preferably exceeded.
Examples of the ternary copolymer include VdF / TFE / HFP copolymer.
上記ＴＦＥ系共重合体における上記ＴＦＥ以外のその他の単量体としては、下記のＴＦＥと共重合し得るその他の単量体（ｃ）であってもよい。上記その他の単量体（ｃ）は、下記一般式：
Ｘ−（ＣＦ２）ｍ−（Ｏ）ｎ−ＣＦ＝ＣＦ２
（式中、Ｘは、水素原子、塩素原子又はフッ素原子を表し、ｍは、１〜６の整数を表し、ｎは、０又は１の整数を表す。）で表される化合物（但し、ＨＦＰを除く。）、下記一般式：
Ｃ３Ｆ７Ｏ［ＣＦ（ＣＦ３）ＣＦ２Ｏ］ｐ−ＣＦ＝ＣＦ２
（式中、ｐは、１又は２の整数を表す。）で表される化合物、又は、下記一般式：
Ｘ（ＣＦ２）ｑＣＹ＝ＣＨ２
（式中、Ｘは、上記と同じであり、Ｙは、水素原子又はフッ素原子を表し、ｑは、１〜６の整数を表す。）で表される化合物である。これらは、１種又は２種以上を用いることができる。
The other monomer other than the TFE in the TFE copolymer may be another monomer (c) that can be copolymerized with the following TFE. The other monomer (c) has the following general formula:
X- (CF 2) m - ( O) n -CF = CF 2
(Wherein X represents a hydrogen atom, a chlorine atom or a fluorine atom, m represents an integer of 1 to 6, and n represents an integer of 0 or 1) (however, HFP The following general formula:
C 3 F 7 O [CF ( CF 3) CF 2 O] p -CF = CF 2
(Wherein p represents an integer of 1 or 2), or the following general formula:
X (CF 2 ) q CY═CH 2
(Wherein X is the same as above, Y represents a hydrogen atom or a fluorine atom, and q represents an integer of 1 to 6). These can use 1 type (s) or 2 or more types.
上記その他の単量体（ｃ）としては、上記一般式で表されるものであれば特に限定されず、例えば、パーフルオロブチレン等の炭素数４以上のパーフルオロオレフィン；パーフルオロ（メチルビニルエーテル）、パーフルオロ（エチルビニルエーテル）等のパーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕等が挙げられる。
ＴＦＥとその他の単量体（ｃ）とを共重合することにより得られるＴＦＥ系共重合体としては、例えば、ＴＦＥ／ＰＡＶＥ共重合体〔ＰＦＡ〕等が挙げられる。
The other monomer (c) is not particularly limited as long as it is represented by the above general formula. For example, perfluoroolefin having 4 or more carbon atoms such as perfluorobutylene; perfluoro (methyl vinyl ether) And perfluoro (alkyl vinyl ether) [PAVE] such as perfluoro (ethyl vinyl ether).
Examples of the TFE copolymer obtained by copolymerizing TFE and the other monomer (c) include TFE / PAVE copolymer [PFA].
上記「単独重合体及び少なくとも１種以上の共重合体からなる混合物」としては特に限定されず、例えば、ＰＴＦＥとＰＦＡとの混合物、ＰＴＦＥとＦＥＰとの混合物、ＰＴＦＥとＰＦＡとＦＥＰとの混合物等が挙げられる。上記「少なくとも２種以上の共重合体からなる混合物」としては特に限定されず、例えば、ＰＦＡとＦＥＰとの混合物等が挙げられる。 The “mixture comprising a homopolymer and at least one copolymer” is not particularly limited, and examples thereof include a mixture of PTFE and PFA, a mixture of PTFE and FEP, a mixture of PTFE, PFA and FEP, and the like. Is mentioned. The “mixture comprising at least two types of copolymers” is not particularly limited, and examples thereof include a mixture of PFA and FEP.
上記含フッ素重合体（Ｒ）は、また、パーフルオロアルキル基を有するパーフルオロアルキル基含有エチレン性不飽和単量体（ｄ）（以下、「ＰＡＥ（ｄ）」という。）を重合することにより得られるものであってもよい。上記ＰＡＥ（ｄ）は、下記一般式： The fluoropolymer (R) is also obtained by polymerizing a perfluoroalkyl group-containing ethylenically unsaturated monomer (d) having a perfluoroalkyl group (hereinafter referred to as “PAE (d)”). It may be obtained. The PAE (d) is represented by the following general formula:
（式中、Ｒｆは、炭素数４〜２０のパーフルオロアルキル基を表し、Ｒ１は、水素原子又は炭素数１〜１０のアルキル基を表し、Ｒ２は、炭素数１〜１０のアルキレン基を表し、Ｒ３は、水素原子又はメチル基を表し、Ｒ４は、炭素数１〜１７のアルキル基を表し、ｒは、１〜１０の整数を表し、ｓは、０〜１０の整数を表す。）で表されるものである。 (In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 represents an alkylene group having 1 to 10 carbon atoms. R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group having 1 to 17 carbon atoms, r represents an integer of 1 to 10, and s represents an integer of 0 to 10 It is expressed by.)
上記含フッ素重合体（Ｒ）は、上記ＰＡＥ（ｄ）の単独重合体であってもよいし、また、上記ＰＡＥ（ｄ）と上記ＰＡＥ（ｄ）と共重合し得る単量体（ｅ）との共重合体であってもよい。上記単量体（ｅ）としては特に限定されず、例えば、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジルエステル、ジ（メタ）アクリル酸ポリエチレングリコール、Ｎ−メチロールプロパンアクリルアミド、（メタ）アクリル酸アミド、アルキル基の炭素数が１〜２０である（メタ）アクリル酸のアルキルエステル等の（メタ）アクリル酸誘導体；エチレン、塩化ビニル、フッ化ビニル、スチレン、α−メチルスチレン、ｐ−メチルスチレン等の置換又は非置換エチレン；アルキル基の炭素数が１〜２０であるアルキルビニルエーテル、アルキル基の炭素数が１〜２０であるハロゲン化アルキルビニルエーテル等のビニルエーテル類；アルキル基の炭素数が１〜２０であるビニルアルキルケトン等のビニルケトン類；無水マレイン酸等の脂肪族不飽和ポリカルボン酸及びその誘導体；ブタジエン、イソプレン、クロロプレン等のポリエン等が挙げられる。 The fluoropolymer (R) may be a homopolymer of the PAE (d), or a monomer (e) that can be copolymerized with the PAE (d) and the PAE (d). And a copolymer thereof. The monomer (e) is not particularly limited, and examples thereof include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol di (meth) acrylate, N-methylolpropane acrylamide, (meth) acrylic. (Meth) acrylic acid derivatives such as acid amides and alkyl esters of (meth) acrylic acid having an alkyl group having 1 to 20 carbon atoms; ethylene, vinyl chloride, vinyl fluoride, styrene, α-methylstyrene, p-methyl Substituted or unsubstituted ethylene such as styrene; alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group; vinyl ethers such as halogenated alkyl vinyl ethers having 1 to 20 carbon atoms in the alkyl group; Vinyl ketones such as vinyl alkyl ketones of ˜20; Aliphatic unsaturated polycarboxylic acids and derivatives thereof such as phosphate; butadiene, isoprene, polyenes such as chloroprene.
上記含フッ素重合体（Ｒ）は、非粘着性、滑り性、耐熱性等に優れる点から、ＰＴＦＥ、ＦＥＰ及び／又はＰＦＡが好ましく、例えば、ＰＴＦＥ、ＦＥＰ、ＰＦＡ及び／又はＰＴＦＥとＦＥＰとの混合物、ＰＴＦＥとＰＦＡとの混合物等が挙げられる。 The fluoropolymer (R) is preferably PTFE, FEP and / or PFA from the viewpoint of excellent non-adhesiveness, slipperiness, heat resistance, etc., for example, PTFE, FEP, PFA and / or PTFE and FEP. Examples thereof include a mixture and a mixture of PTFE and PFA.
上記ＰＴＦＥはＴＦＥ、ＦＥＰはＴＦＥとＨＦＰ、ＰＦＡはＴＦＥとＰＡＶＥがそれぞれ必須単量体であるが、これらの必須単量体以外のその他の微量単量体が付加されているものであってもよい。 The PTFE is TFE, FEP is TFE and HFP, and PFA is TFE and PAVE, respectively. However, other trace monomers other than these essential monomers are added. Good.
上記微量単量体としては特に限定されず、例えば、ＣＴＦＥ等の上記不飽和炭化水素（ａ）；３ＦＨ等の上記不飽和化合物（ｂ）；パーフルオロ（アルコキシビニルエーテル）、（パーフルオロアルキル）エチレン等の上記その他の単量体（ｃ）等が挙げられる。上記微量単量体としては、含フッ素重合体（Ｒ）が上記ＰＴＦＥである場合、更に、ＨＦＰ、ＰＡＶＥが挙げられ、上記ＦＥＰである場合、更に、ＰＡＶＥが挙げられ、上記ＰＦＡである場合、更に、ＨＦＰが挙げられる。上記微量単量体は、１種又は２種以上を用いることができる。 The trace monomer is not particularly limited. For example, the unsaturated hydrocarbon (a) such as CTFE; the unsaturated compound (b) such as 3FH; perfluoro (alkoxy vinyl ether), (perfluoroalkyl) ethylene. And other monomers (c) and the like. When the fluoropolymer (R) is the PTFE, examples of the trace monomer include HFP and PAVE, and examples of the FEP include PAVE and the PFA. Furthermore, HFP is mentioned. The said trace amount monomer can use 1 type (s) or 2 or more types.
上記微量単量体は、その種類によって異なるが、通常、含フッ素重合体の質量の１質量％以下であることが好ましい。より好ましい上限は０．５質量％であり、更に好ましい上限は０．３質量％であり、好ましい下限は、０．０１質量％である。 Although the said trace amount monomer changes with kinds, it is preferable normally that it is 1 mass% or less of the mass of a fluoropolymer. A more preferred upper limit is 0.5% by mass, a still more preferred upper limit is 0.3% by mass, and a preferred lower limit is 0.01% by mass.
上記含フッ素重合体（Ｒ）は、ＰＴＦＥ及び／又はＦＥＰがより好ましい。上記「ＰＴＦＥ及び／又はＦＥＰ」とは、ＰＴＦＥ、ＦＥＰ、又は、ＰＴＦＥとＦＥＰとの混合物を意味する。 The fluoropolymer (R) is more preferably PTFE and / or FEP. The above “PTFE and / or FEP” means PTFE, FEP, or a mixture of PTFE and FEP.
上記含フッ素重合体（Ｒ）は、例えば、乳化重合、懸濁重合等の従来公知の重合方法を用いて重合することにより得ることができる。上記重合方法により得られる含フッ素重合体（Ｒ）は、所望により、上述の範囲内の平均粒子径を有するように粉砕する。上記粉砕の方法としては特に限定されず、例えば、上記含フッ素重合体（Ｒ）をロールでシート状に圧縮し、粉砕機により粉砕し分級する方法等が挙げられる。 The fluoropolymer (R) can be obtained by polymerization using a conventionally known polymerization method such as emulsion polymerization or suspension polymerization. The fluoropolymer (R) obtained by the above polymerization method is pulverized so as to have an average particle diameter within the above range, if desired. The pulverization method is not particularly limited, and examples thereof include a method in which the fluoropolymer (R) is compressed into a sheet with a roll, pulverized with a pulverizer, and classified.
上記含フッ素重合体（Ｒ）は、乳化重合や懸濁重合を用いて得る場合、得られる重合体成分のみを単離することなくディスパージョンのまま含フッ素重合体水性組成物の調製に用いてもよいし、上記ディスパージョンは、得られる重合体成分からなる分散液に界面活性剤（Ｓ１）を添加することにより上記分散液を濃縮し、必要に応じ更に界面活性剤（Ｓ２）を添加して、含フッ素重合体水性組成物として調製したものであってもよい。 When the fluoropolymer (R) is obtained by emulsion polymerization or suspension polymerization, it is used for the preparation of the fluoropolymer aqueous composition as a dispersion without isolating only the polymer component obtained. Alternatively, the dispersion may be obtained by concentrating the dispersion by adding the surfactant (S1) to the dispersion comprising the polymer component obtained, and further adding the surfactant (S2) as necessary. In addition, it may be prepared as a fluoropolymer aqueous composition.
本発明の含フッ素重合体水性組成物において、上記含フッ素重合体（Ｒ）は水性媒体に粒子として分散したものである。上記含フッ素重合体（Ｒ）は、平均粒子径が０．０１〜５０μｍである粒子からなるものが好ましい。０．０１μｍ未満であると、含フッ素重合体（Ｒ）からなる粒子の分散性が悪く、得られる含フッ素重合体水性組成物が機械的安定性及び貯蔵安定性に劣るおそれがある。５０μｍを超えると、含フッ素重合体（Ｒ）からなる粒子の均一分散性に欠け、得られる含フッ素重合体水性組成物を用いて塗装する際、表面が平滑な塗膜が得られず、塗膜物性が劣る場合がある。より好ましい上限は、５μｍであり、更に好ましい上限は、０．５μｍであり、より好ましい下限は、０．０５μｍである。上記機械的安定性は、送液・再分散の際、ホモジナイザー等による強い攪拌や剪断力を与えても、再分散不可能な凝集体を生成しにくい性質のことである。 In the fluoropolymer aqueous composition of the present invention, the fluoropolymer (R) is dispersed as particles in an aqueous medium. The fluoropolymer (R) is preferably composed of particles having an average particle diameter of 0.01 to 50 μm. If it is less than 0.01 μm, the dispersibility of the particles comprising the fluoropolymer (R) is poor, and the resulting fluoropolymer aqueous composition may be inferior in mechanical stability and storage stability. If it exceeds 50 μm, the uniform dispersion of the particles comprising the fluoropolymer (R) is lacking, and when coating with the resulting fluoropolymer aqueous composition, a coating film with a smooth surface cannot be obtained. The film properties may be inferior. A more preferred upper limit is 5 μm, a still more preferred upper limit is 0.5 μm, and a more preferred lower limit is 0.05 μm. The mechanical stability is a property that hardly produces aggregates that cannot be redispersed even when strong stirring or shearing force is applied by a homogenizer or the like during liquid feeding and redispersion.
本発明の含フッ素重合体水性組成物において、上記水溶性ポリアミドイミド樹脂〔ＰＡＩ〕（Ｐ）は、好ましくは下記一般式（ｉ）： In the fluoropolymer aqueous composition of the present invention, the water-soluble polyamideimide resin [PAI] (P) is preferably the following general formula (i):
（式中、Ｒ５は３価の有機基を表し、Ｒ６は２価の有機基を表す。）で表される繰り返し単位（ｉ）を有するものである。 (Wherein R 5 represents a trivalent organic group and R 6 represents a divalent organic group).
上記水溶性ＰＡＩ（Ｐ）は、例えば、ジイソシアネート化合物又はジアミン化合物と多塩基酸無水物又は多塩基酸無水物クロライドとを反応させて得られる。 The water-soluble PAI (P) is obtained, for example, by reacting a diisocyanate compound or diamine compound with a polybasic acid anhydride or polybasic acid anhydride chloride.
上記水溶性ＰＡＩ（Ｐ）は下記一般式（ｉｉ）： The water-soluble PAI (P) is represented by the following general formula (ii):
（式中、→は異性化を意味し、Ｇは水素原子又はカルボキシル基であり、Ｒ７は４価の有機基を表し、Ｒ８は２価の有機基を表す。）で表される繰り返し単位（ｉｉ）をも有するものであってよく、また、ポリマー鎖末端にカルボキシル基を有するものであってよい。これらのポリアミド酸は、化学量論的量の塩基性化合物で中和したものが、ＰＡＩの水溶性を高める点で好ましい。上記Ｒ５〜Ｒ８としては、芳香環を有する炭素数６〜２０の有機基が好ましい。 (In the formula, → means isomerization, G is a hydrogen atom or a carboxyl group, R 7 represents a tetravalent organic group, and R 8 represents a divalent organic group). It may also have unit (ii) and may have a carboxyl group at the end of the polymer chain. These polyamic acids are preferably neutralized with a stoichiometric amount of a basic compound from the viewpoint of increasing the water solubility of PAI. As the R 5 to R 8, an organic group having 6 to 20 carbon atoms having an aromatic ring is preferable.
上記ジイソシアネート化合物としては、例えば、４，４’−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、３，３’−ジフェニルメタンジイソシアネート、パラフェニレンジイソシアネート等が挙げられる。 Examples of the diisocyanate compound include 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-diphenylmethane diisocyanate, paraphenylene diisocyanate, and the like.
上記ジアミン化合物としては、例えば、フェニレンジアミン、キシリレンジアミン、ビス−（４−アミノフェニル）エーテル、ベンチジン、２，２’−（４’−アミノフェニル）プロパン、ビス−（４−アミノフェニル）メタン、ビス−（４−アミノフェニル）スルホン、ビス−（４−アミノフェニル）スルフィド、又は、２，２’−ヘキサメチレンジアミン等が挙げられる。 Examples of the diamine compound include phenylenediamine, xylylenediamine, bis- (4-aminophenyl) ether, benzidine, 2,2 ′-(4′-aminophenyl) propane, and bis- (4-aminophenyl) methane. Bis- (4-aminophenyl) sulfone, bis- (4-aminophenyl) sulfide, 2,2′-hexamethylenediamine, and the like.
上記多塩基酸無水物としては、例えば、ピロメリト酸ジ無水物、トリメリト酸無水物、２，２’−ビス（３’，４’−ジカルボキシフェニル）プロパンジ無水物、又は、ビス（３，４−ジカルボキシフェニル）エーテルジ無水物等が挙げられる。 Examples of the polybasic acid anhydride include pyromellitic dianhydride, trimellitic acid anhydride, 2,2′-bis (3 ′, 4′-dicarboxyphenyl) propane dianhydride, or bis (3,4). -Dicarboxyphenyl) ether dianhydride and the like.
上記多塩基酸無水物クロライドとしては、例えば、トリメリト酸無水物クロライド等が挙げられる。 Examples of the polybasic acid anhydride chloride include trimellitic acid anhydride chloride.
上記塩基性化合物としては、例えば、水酸化ナトリウムや水酸化カリウム等の苛性アルカリやアンモニア；トリメチルアミン、トリエチルアミン、トリブチルアミン、トリエチレンジアミン、ピリジン、Ｎ−メチルピロール、Ｎ−メチルモルフォリン等のアルキルアミン；メチルアニリン、ジメチルアニリン、Ｎ，Ｎ−ジメチルアニリン等のアルキルアニリン；ジエチル２−ヒドロキシエチルアミン、トリス（２−ヒドロキシエチル）アミン、エチルビス（２−ヒドロキシエチル）アミン、Ｎ，Ｎ−ジメチルエタノールアミン等のアルカノールアミンが挙げられ、これらを２種以上混合して用いてもよい。 Examples of the basic compound include caustic and ammonia such as sodium hydroxide and potassium hydroxide; alkylamines such as trimethylamine, triethylamine, tributylamine, triethylenediamine, pyridine, N-methylpyrrole, and N-methylmorpholine; Alkyl anilines such as methylaniline, dimethylaniline, N, N-dimethylaniline; diethyl 2-hydroxyethylamine, tris (2-hydroxyethyl) amine, ethylbis (2-hydroxyethyl) amine, N, N-dimethylethanolamine, etc. Examples thereof include alkanolamines, and two or more of these may be used in combination.
上記塩基性化合物は、反応媒体中において反応により得られるポリアミドイミド中に含まれるカルボキシル基と、イミド結合を開環させたカルボキシル基とを合わせた酸価に対して、１〜２０当量用いることが好ましい。１当量未満では樹脂の水溶化が困難となりやすく、２０当量を超えると樹脂の加水分解が促進される場合がある。 The basic compound is used in an amount of 1 to 20 equivalents relative to the acid value of the carboxyl group contained in the polyamideimide obtained by the reaction in the reaction medium and the carboxyl group having the ring-opened imide bond. preferable. If it is less than 1 equivalent, water-solubilization of the resin tends to be difficult, and if it exceeds 20 equivalents, hydrolysis of the resin may be accelerated.
上記水溶性ＰＡＩ（Ｐ）は、数平均分子量が５０００〜５００００であることが好ましい。数平均分子量が５０００未満であると、得られる途膜の耐熱性や機械的特性等が低下することがあり、数平均分子量が５００００を超えると、含フッ素重合体水性組成物の粘度が高くなり、塗装性に劣ることがある。上記数平均分子量は、１００００〜３００００であることが好ましく、１５０００〜２５０００であることがより好ましい。 The water-soluble PAI (P) preferably has a number average molecular weight of 5,000 to 50,000. If the number average molecular weight is less than 5,000, the heat resistance and mechanical properties of the resulting film may be lowered. If the number average molecular weight exceeds 50,000, the viscosity of the aqueous fluoropolymer composition will increase. The paintability may be inferior. The number average molecular weight is preferably 10,000 to 30,000, and more preferably 15,000 to 25,000.
上記数平均分子量は、ゲルパーミエーションクロマトグラフィー［ＧＰＣ］により測定し、ポリスチレン換算した値である。本明細書において、ゲルパーミエーションクロマトグラフィー［ＧＰＣ］は、０．１〜０．２重量％に調製した含フッ素ポリマーのテトラヒドロフラン［ＴＨＦ］溶液をディスポーザルメンブランフィルターユニットＤＩＳＭＩＣ−２５ＨＰ（親水性ポリテトラフルオロエチレン［ＰＴＦＥ］、アドバンテック製）に通したものをサンプルとして行う。使用するＧＰＣ装置はＨＬＣ−８０２０（東ソー社製）であり、使用カラムはＴＳＫｇｅｌ Ｇ２０００ＨＨＲ、Ｇ３０００ＨＨＲ、Ｇ４０００ＨＨＲ、Ｇ５０００ＨＨＲである。測定中、カラム内には上記サンプルを１．０ｍｌ／分にて導入し、圧力を５５ｋｇ／ｃｍ２に、温度を４０℃に保持する。検出器には示差屈折計（ＲＩ）を用いる。 The number average molecular weight is a value measured by gel permeation chromatography [GPC] and converted to polystyrene. In this specification, gel permeation chromatography [GPC] is obtained by using a tetrahydrofuran [THF] solution of a fluorine-containing polymer prepared at 0.1 to 0.2% by weight as a disposable membrane filter unit DISMIC-25HP (hydrophilic polytetra A sample passed through fluoroethylene [PTFE] (manufactured by Advantech) is used as a sample. The GPC apparatus used is HLC-8020 (manufactured by Tosoh Corporation), and the columns used are TSKgel G2000H HR , G3000H HR , G4000H HR , G5000H HR . During the measurement, the sample is introduced into the column at 1.0 ml / min, the pressure is maintained at 55 kg / cm 2 , and the temperature is maintained at 40 ° C. A differential refractometer (RI) is used as the detector.
上記水溶性ＰＡＩ（Ｐ）は、カルボキシル基及びイミド結合〔−ＣＯ−Ｎ−ＣＯ−〕（ｉｍｉｄｏ）を開環させたカルボキシル基を合わせた酸価が１０〜１００であることが好ましい。酸価が１０未満であると、多塩基酸無水物又は多塩基酸無水物クロライドと反応するカルボキシル基が不足するため水溶化が困難になり、１００を超えると、得られる含フッ素重合体水性組成物がゲル化しやすくなる。上記酸価は、２０〜８０であることが好ましく、３０〜６０とすることがより好ましい。 The water-soluble PAI (P) preferably has an acid value of 10 to 100, which is a combination of a carboxyl group and a carboxyl group obtained by ring-opening an imide bond [—CO—N—CO—] (imido). When the acid value is less than 10, the carboxyl group that reacts with the polybasic acid anhydride or polybasic acid chloride is insufficient, so that water-solubilization becomes difficult. When the acid value exceeds 100, the resulting fluoropolymer aqueous composition is obtained. Things are easily gelled. The acid value is preferably 20 to 80, and more preferably 30 to 60.
上記酸価は、以下の方法により得られる値である。すなわち、水溶性ＰＡＩ（Ｐ）を約０．５ｇとり、これに１，４−ジアザビシクロ〔２，２，２〕オクタンを約０．１５ｇ加え、更にＮ−メチル−２−ピロリドンを約６０ｇ及びイオン交換水を約１ｍｌ加え、水溶性ＰＡＩ（Ｐ）が完全に溶解するまで攪拌する。これを０．０５モル／Ｌエタノール性水酸化カリウム溶液を使用して電位差滴定装置で滴定し、水溶性ＰＡＩ（Ｐ）の酸価を得る。 The acid value is a value obtained by the following method. That is, about 0.5 g of water-soluble PAI (P) is added, about 0.15 g of 1,4-diazabicyclo [2,2,2] octane is added thereto, and about 60 g of N-methyl-2-pyrrolidone and ions are added. Add about 1 ml of exchange water and stir until the water-soluble PAI (P) is completely dissolved. This is titrated with a potentiometric titrator using a 0.05 mol / L ethanolic potassium hydroxide solution to obtain the acid value of water-soluble PAI (P).
上記水溶性ＰＡＩ（Ｐ）は、通常、溶液として、含フッ素重合体水性組成物の調製に用いる。該水溶性ＰＡＩ（Ｐ）溶液は、有機溶剤を含む水に上記水溶性（Ｐ）を溶解することにより容易に得ることができる。 The water-soluble PAI (P) is usually used as a solution for preparing a fluoropolymer aqueous composition. The water-soluble PAI (P) solution can be easily obtained by dissolving the water-soluble (P) in water containing an organic solvent.
上記有機溶剤としては、極性が高く高沸点を有するものであれば特に限定されないが、例えば、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、クレゾール酸、スルホラン、ホルムアルデヒド等が挙げられる。上記有機溶剤としては、入手の容易性からＮ−メチル−２−ピロリドンが好ましい。
上記有機溶剤は、本発明の含フッ素重合体水性組成物における後述の水性分散体に含有され得る有機液体と同じものであってもよい。
The organic solvent is not particularly limited as long as it has a high polarity and a high boiling point, and examples thereof include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, cresolic acid, sulfolane, and formaldehyde. It is done. As the organic solvent, N-methyl-2-pyrrolidone is preferable because of its availability.
The organic solvent may be the same as the organic liquid that can be contained in the aqueous dispersion described later in the aqueous fluoropolymer composition of the present invention.
水溶性ＰＡＩ（Ｐ）は、粘度の点で、水溶性ＰＡＩ（Ｐ）溶液の１〜５０質量％の濃度であることが好ましく、より好ましくは５〜４０質量％である。
水溶性ＰＡＩ（Ｐ）は、水溶性ＰＡＩ（Ｐ）溶液において、溶媒中に分子の状態で分散していると考えられ、該水溶性ＰＡＩ（Ｐ）溶液を用いて調製した本発明の含フッ素重合体水性組成物においても同様に分子の状態で分散し、水性媒体中に溶解した状態で存在することができると考えられる。
The water-soluble PAI (P) is preferably 1 to 50% by mass of the water-soluble PAI (P) solution in terms of viscosity, and more preferably 5 to 40% by mass.
The water-soluble PAI (P) is considered to be dispersed in a molecular state in the solvent in the water-soluble PAI (P) solution, and the fluorine-containing product of the present invention prepared using the water-soluble PAI (P) solution It is considered that the aqueous polymer composition can also be dispersed in a molecular state and dissolved in an aqueous medium.
本発明の含フッ素重合体水性組成物において、上記水性分散体は、上述の水溶性ＰＡＩ（Ｐ）、含フッ素重合体（Ｒ）、及び、上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）からなるものである。 In the aqueous fluoropolymer composition of the present invention, the aqueous dispersion is composed of the water-soluble PAI (P), the fluoropolymer (R), and the heat-resistant resin (Q) different from the water-soluble PAI. It will be.
上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）は、耐熱性を有すると通常認識されている樹脂であればよく、連続使用可能温度が１５０℃以上の樹脂が好ましい。
上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）としては特に限定されず、例えば、ポリエーテルスルホン樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン樹脂、芳香族ポリエステル樹脂、ポリアリレンサルファイド樹脂、及び、非水溶性ポリアミドイミド樹脂等が挙げられる。上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）としては、１種又は２種以上を用いることができる。
The heat-resistant resin (Q) different from the water-soluble PAI may be any resin that is normally recognized as having heat resistance, and is preferably a resin having a continuous usable temperature of 150 ° C. or higher.
The heat-resistant resin (Q) different from the water-soluble PAI is not particularly limited. For example, a polyethersulfone resin, a polyetherimide resin, a polyetheretherketone resin, an aromatic polyester resin, a polyarylene sulfide resin, and A water-insoluble polyamide-imide resin is exemplified. As the heat resistant resin (Q) different from the water-soluble PAI, one or more kinds can be used.
上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）は、被塗装物との密着性に優れ、上記塗膜を形成する際に焼成時の温度下でも充分な耐熱性を有し、得られる塗膜が耐食性及び耐水蒸気性に優れる点から、ポリエーテルスルホン樹脂〔ＰＥＳ〕が好ましい。 The heat-resistant resin (Q) different from the water-soluble PAI has excellent adhesion to an object to be coated and has sufficient heat resistance even at the firing temperature when forming the coating film, and the resulting coating film However, polyethersulfone resin [PES] is preferable because it is excellent in corrosion resistance and water vapor resistance.
本発明の含フッ素重合体水性組成物において、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）は、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）と水溶性ＰＡＩ（Ｐ）との合計質量の１０〜９９質量％であることが好ましく、２０〜９５質量％であることがより好ましい。
本発明の含フッ素重合体水性組成物において、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）がＰＥＳである場合、ＰＥＳは、ＰＥＳと水溶性ＰＡＩ（Ｐ）との合計質量の６５〜８５質量％であることが好ましい。６５質量％未満であると、含フッ素重合体水性組成物から得られる塗膜の耐水蒸気性が低下するおそれがあり、８５質量％を超えると、塗膜の耐食性が低下するおそれがある。
In the fluoropolymer aqueous composition of the present invention, the heat-resistant resin (Q) different from the water-soluble PAI is 10 to 10 times the total mass of the heat-resistant resin (Q) different from the water-soluble PAI and the water-soluble PAI (P). It is preferable that it is 99 mass%, and it is more preferable that it is 20-95 mass%.
In the fluoropolymer aqueous composition of the present invention, when the heat resistant resin (Q) different from the water-soluble PAI is PES, the PES is 65 to 85% by mass of the total mass of the PES and the water-soluble PAI (P). It is preferable that If it is less than 65% by mass, the water vapor resistance of the coating film obtained from the fluoropolymer aqueous composition may be reduced, and if it exceeds 85% by mass, the corrosion resistance of the coating film may be reduced.
本発明の含フッ素重合体水性組成物において、上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）は、後述の水性媒体に粒子として分散したもの、又は、水性媒体に溶解したものである。上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）が水性媒体に粒子として分散している場合、上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）からなる粒子は、上記水性媒体に粒子として分散した平均粒子径が０．１〜１０μｍである粒子であることが好ましい。上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）の平均粒子径が上記範囲内であると、含フッ素重合体水性組成物から得られる塗膜の耐食性が良好である。
上記平均粒子径は、遠心沈降法により測定して得られる値である。
In the aqueous fluoropolymer composition of the present invention, the heat resistant resin (Q) different from the water-soluble PAI is dispersed as particles in an aqueous medium described later or dissolved in an aqueous medium. When the heat-resistant resin (Q) different from the water-soluble PAI is dispersed as particles in the aqueous medium, the particles made of the heat-resistant resin (Q) different from the water-soluble PAI are averaged as particles dispersed in the aqueous medium. It is preferable that the particle diameter is 0.1 to 10 μm. When the average particle diameter of the heat-resistant resin (Q) different from the water-soluble PAI is within the above range, the corrosion resistance of the coating film obtained from the fluoropolymer aqueous composition is good.
The average particle diameter is a value obtained by measurement by a centrifugal sedimentation method.
本発明の含フッ素重合体水性組成物において、上述の水性分散体は、上記水溶性ＰＡＩ（Ｐ）、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）及び含フッ素重合体（Ｒ）とともに、必要に応じ、その他の樹脂からなるものであってもよい。上記その他の樹脂を配合することにより、含フッ素重合体水性組成物から得られる塗膜の造膜性、耐食性等を向上させることができる。 In the fluoropolymer aqueous composition of the present invention, the above-mentioned aqueous dispersion is necessary together with the water-soluble PAI (P), the heat-resistant resin (Q) different from the water-soluble PAI, and the fluoropolymer (R). Accordingly, it may be made of other resins. By blending the above-mentioned other resins, it is possible to improve the film forming property, corrosion resistance, and the like of the coating film obtained from the fluoropolymer aqueous composition.
上記その他の樹脂としては特に限定されず、例えば、フェノール樹脂、尿素樹脂、エポキシ樹脂、ウレタン樹脂、メラミン樹脂、ポリエステル樹脂、ポリエーテル樹脂、アクリル樹脂、アクリルシリコーン樹脂、シリコーン樹脂、シリコーンポリエステル樹脂等が挙げられる。 The other resin is not particularly limited, and examples thereof include phenol resin, urea resin, epoxy resin, urethane resin, melamine resin, polyester resin, polyether resin, acrylic resin, acrylic silicone resin, silicone resin, and silicone polyester resin. Can be mentioned.
本発明の含フッ素重合体水性組成物において、上記水性分散体は、含フッ素重合体（Ｒ）からなる粒子を主に分散質とし、水性媒体を分散媒とするものである。上記水性媒体は水を含むものであれば特に限定されず、例えば、水及び有機液体との混合物、水等が挙げられる。 In the aqueous fluoropolymer composition of the present invention, the aqueous dispersion is mainly composed of particles comprising the fluoropolymer (R) as a dispersoid and an aqueous medium as a dispersion medium. The aqueous medium is not particularly limited as long as it contains water, and examples thereof include a mixture of water and an organic liquid, and water.
上記有機液体としては特に限定されず、例えば、トルエン、キシレン、トリメチルベンゼン、メチルエチルベンゼン、プロピルベンゼン、ブチルベンゼン等の芳香族炭化水素系溶剤；炭素数が６〜１２の飽和炭化水素系溶剤；Ｎ−メチル−２−ピロリドン、２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド等の含窒素系溶剤；γ−ブチロラクトン等のラクトン類；酢酸ブチル等の非環状エステル類；メチルイソブチルケトン、メチルエチルケトン等のケトン類；ブチルセロソルブ等のグリコールエーテル類；エチレングリコール、トリエチレングリコール、プロピレングリコール等のグリコール類；１−ブタノール、ジアセトンアルコール等のモノアルコール類等が挙げられる。 The organic liquid is not particularly limited, and is, for example, an aromatic hydrocarbon solvent such as toluene, xylene, trimethylbenzene, methylethylbenzene, propylbenzene, or butylbenzene; a saturated hydrocarbon solvent having 6 to 12 carbon atoms; N Nitrogen-containing solvents such as methyl-2-pyrrolidone, 2-pyrrolidone and N, N-dimethylacetamide; Lactones such as γ-butyrolactone; Acyclic esters such as butyl acetate; Ketones such as methyl isobutyl ketone and methyl ethyl ketone Glycol ethers such as butyl cellosolve; glycols such as ethylene glycol, triethylene glycol and propylene glycol; monoalcohols such as 1-butanol and diacetone alcohol;
本発明の含フッ素重合体水性組成物において、上述の水溶性ＰＡＩ（Ｐ）溶液中に含有し得る有機溶剤、及び、上記水性分散体中に含有し得る有機液体の含有量は合計で、上記水溶性ＰＡＩ（Ｐ）１００質量部に対し４０〜５００質量部の割合で存在することが好ましく、８０〜３００質量部であることがより好ましい。 In the aqueous fluoropolymer composition of the present invention, the total amount of the organic solvent that can be contained in the water-soluble PAI (P) solution and the organic liquid that can be contained in the aqueous dispersion is as described above. It is preferable that it exists in the ratio of 40-500 mass parts with respect to 100 mass parts of water-soluble PAI (P), and it is more preferable that it is 80-300 mass parts.
上記芳香族炭化水素系溶剤としては、市販品であるソルベッソ１００、ソルベッソ１５０、ソルベッソ２００（何れも商品名、エクソン化学社製）等を用いてもよい。上記飽和炭化水素系溶剤としては、市販品であるミネラルスピリット（日本工業規格、工業ガソリン４号）等を用いてもよい。上記有機液体は、単独で用いてもよいし、２種以上を併用してもよい。
上記有機液体としては、含窒素系溶剤を用いることが好ましく、Ｎ−メチル−２−ピロリドン、ジメチルアセトアミドを用いることがより好ましい。
As the aromatic hydrocarbon solvent, commercially available products such as Solvesso 100, Solvesso 150, Solvesso 200 (all trade names, manufactured by Exxon Chemical) may be used. As the saturated hydrocarbon solvent, a commercially available mineral spirit (Japanese Industrial Standard, Industrial Gasoline No. 4) or the like may be used. The said organic liquid may be used independently and may use 2 or more types together.
As the organic liquid, a nitrogen-containing solvent is preferably used, and N-methyl-2-pyrrolidone and dimethylacetamide are more preferably used.
上記水性媒体は、例えば、後述の各種添加剤が溶解又は分散しているものであってもよい。上記水性媒体は、含フッ素重合体（Ｒ）の重合に用いた水性媒体であってもよいし、重合に用いた水性媒体とは別に用意したものであってもよいが、上記含フッ素重合体（Ｒ）を乳化重合や懸濁重合により得る場合、含フッ素重合体（Ｒ）の重合に用いた水性媒体をそのまま用いることができる。 The aqueous medium may be, for example, one in which various additives described below are dissolved or dispersed. The aqueous medium may be the aqueous medium used for the polymerization of the fluoropolymer (R) or may be prepared separately from the aqueous medium used for the polymerization. When (R) is obtained by emulsion polymerization or suspension polymerization, the aqueous medium used for the polymerization of the fluoropolymer (R) can be used as it is.
本発明の含フッ素重合体水性組成物は、塗装性、含フッ素重合体水性組成物から得られる塗膜の性質向上等を目的として、更に、一般的なコーティング用組成物に通常用いられる各種添加剤を配合してなるものであってもよい。上記各種添加剤としては特に限定されず、本発明の含フッ素重合体水性組成物を用いることにより得られる後述の被覆物品の用途に応じて選択され、例えば、レベリング剤、固体潤滑剤、顔料、充填材、顔料分散剤、沈降防止剤、水分吸収剤、表面調整剤、チキソトロピー性付与剤、粘度調節剤、ゲル化防止剤、紫外線吸収剤、光安定剤、可塑剤、色分かれ防止剤、皮張り防止剤、スリ傷防止剤、防カビ剤、抗菌剤、酸化防止剤、帯電防止剤、シランカップリング剤等が挙げられる。 The aqueous fluorinated polymer composition of the present invention has various additions that are commonly used in general coating compositions for the purpose of improving paint properties and the properties of the coating film obtained from the aqueous fluorinated polymer composition. An agent may be blended. The various additives are not particularly limited, and are selected according to the use of a coated article described later obtained by using the fluoropolymer aqueous composition of the present invention. For example, a leveling agent, a solid lubricant, a pigment, Fillers, pigment dispersants, anti-settling agents, moisture absorbers, surface conditioners, thixotropic agents, viscosity modifiers, anti-gelling agents, UV absorbers, light stabilizers, plasticizers, color separation inhibitors, leather Examples thereof include anti-tension agents, anti-scratch agents, anti-fungal agents, antibacterial agents, antioxidants, antistatic agents, and silane coupling agents.
本発明の含フッ素重合体水性組成物は、２５℃における粘度が０．１〜５００００ｍＰａ・ｓであることが好ましい。粘度が０．１ｍＰａ・ｓ未満であると、被塗装物上への塗布時にタレ等を生じやすく、目的とする膜厚を得ることが困難となる場合があり、５００００ｍＰａ・ｓを超えると、塗装作業性が悪くなる場合があり、得られる塗膜の膜厚が均一とならず、表面平滑性等に劣る場合がある。より好ましい下限は、１ｍＰａ・ｓであり、より好ましい上限は、３００００ｍＰａ・ｓである。上記粘度は、ＢＭ型単一円筒型回転粘度計（東京計器社製）を用いて測定することにより得られる値である。 The aqueous fluoropolymer composition of the present invention preferably has a viscosity at 25 ° C. of 0.1 to 50000 mPa · s. If the viscosity is less than 0.1 mPa · s, sagging or the like is likely to occur during application on the object to be coated, and it may be difficult to obtain the desired film thickness. The workability may be deteriorated, the film thickness of the obtained coating film may not be uniform, and the surface smoothness and the like may be inferior. A more preferred lower limit is 1 mPa · s, and a more preferred upper limit is 30000 mPa · s. The said viscosity is a value obtained by measuring using a BM type single cylinder type rotational viscometer (made by Tokyo Keiki Co., Ltd.).
本発明の含フッ素重合体水性組成物は、上述のワンコート法に用いる塗料組成物であってもよいし、上述のツーコート法に用いるプライマー組成物であってもよいが、プライマー組成物に好適である。 The fluoropolymer aqueous composition of the present invention may be a coating composition used in the above-mentioned one-coat method or a primer composition used in the above-mentioned two-coat method, but is suitable for a primer composition. It is.
本発明の含フッ素重合体水性組成物をプライマー組成物として用いる場合、上記水溶性ＰＡＩ（Ｐ）と水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）の合計固形分質量（Ｗ）は、Ｗと含フッ素重合体（Ｒ）の合計固形分質量の１５〜５０質量％であることが好ましい。 When the fluoropolymer aqueous composition of the present invention is used as a primer composition, the total solid content mass (W) of the water-soluble PAI (P) and the heat-resistant resin (Q) different from the water-soluble PAI is W and It is preferable that it is 15-50 mass% of the total solid content mass of a fluoropolymer (R).
本明細書において、上記「Ｗと含フッ素重合体（Ｒ）の合計固形分質量」とは、本発明の含フッ素重合体水性組成物を被塗装物上に塗布したのち８０〜１００℃以下の温度で乾燥し、３８０〜４００℃で４５分間焼成した後の残渣における上記水溶性ＰＡＩ（Ｐ）と水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）、及び、含フッ素重合体（Ｒ）との合計質量を意味する。 In the present specification, the above-mentioned “total solid mass of W and fluoropolymer (R)” refers to a temperature of 80 to 100 ° C. or less after the fluoropolymer aqueous composition of the present invention is applied on an object to be coated. Total of the water-soluble PAI (P) and the heat-resistant resin (Q) different from the water-soluble PAI and the fluoropolymer (R) in the residue after drying at a temperature and baking at 380 to 400 ° C. for 45 minutes It means mass.
上記Ｗは、Ｗと含フッ素重合体（Ｒ）の固形分合計量の１５質量％未満であると、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）が少ないので、含フッ素重合体水性組成物から得られる塗膜と被塗装物との密着性が不充分である場合がある。５０質量％を超えると、含フッ素重合体（Ｒ）が少ないので、上記塗膜と上塗り塗膜との密着性が不充分であるおそれがある。より好ましい下限は、２０質量％であり、より好ましい上限は、４０質量％である。 When the W is less than 15% by mass of the total solid content of W and the fluoropolymer (R), since there is little heat-resistant resin (Q) different from the water-soluble PAI, from the fluoropolymer aqueous composition, There are cases where the adhesion between the resulting coating film and the object to be coated is insufficient. When it exceeds 50 mass%, since there are few fluoropolymers (R), there exists a possibility that the adhesiveness of the said coating film and topcoat film may be inadequate. A more preferable lower limit is 20% by mass, and a more preferable upper limit is 40% by mass.
本発明の含フッ素重合体水性組成物は、従来公知の方法等により調製することができ、例えば、有機溶剤を含んだ水に分子分散の状態で溶解している上記水溶性ＰＡＩ（Ｐ）と、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）、含フッ素重合体（Ｒ）、及び、必要に応じて配合するその他の樹脂を適宜混合して上記水性媒体に分散又は溶解することにより水性ディスパージョンを得、必要に応じて粘度調節剤等を用いて塗装しやすい粘度に調整し、所望に応じて上記粘度調節剤以外の各種添加剤を配合する方法等が挙げられる。本発明の含フッ素重合体水性組成物において、上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）、含フッ素重合体（Ｒ）、顔料等は、また、それぞれの分散体を予め調製し、得られる分散体を混合することより調製を行うものであってもよい。 The aqueous fluoropolymer composition of the present invention can be prepared by a conventionally known method, for example, the above water-soluble PAI (P) dissolved in water containing an organic solvent in a molecular dispersion state. An aqueous dispersion obtained by appropriately mixing a heat-resistant resin (Q) different from the water-soluble PAI, a fluoropolymer (R), and other resins blended as necessary, and dispersing or dissolving in the aqueous medium. And adjusting the viscosity so that it can be easily applied using a viscosity modifier or the like, if necessary, and blending various additives other than the viscosity modifier as desired. In the aqueous fluoropolymer composition of the present invention, the heat-resistant resin (Q), the fluoropolymer (R), the pigment and the like different from the water-soluble PAI can be obtained by preparing respective dispersions in advance. You may prepare by mixing a dispersion.
本発明の含フッ素重合体水性組成物は、塗装性に優れ、例えばスプレー塗装に用いた場合であっても、被塗装物に霧状の塗料が到達した際にハジキや塗装ムラを生じにくい。この効果を奏する機構は、明確ではないが、水溶性ＰＡＩ（Ｐ）を含有することから、該水溶性ＰＡＩ（Ｐ）が水性分散体中に分子分散の状態で溶解しており、噴霧中の塗料粒子が従来品よりも小さいことによるものと考えられる。 The aqueous fluoropolymer composition of the present invention is excellent in paintability, and even when used for spray coating, for example, it is difficult to cause repelling or coating unevenness when a mist-like paint reaches the object to be coated. Although the mechanism that exerts this effect is not clear, since it contains water-soluble PAI (P), the water-soluble PAI (P) is dissolved in a state of molecular dispersion in the aqueous dispersion, This is probably because the paint particles are smaller than the conventional product.
本発明の含フッ素重合体水性組成物は、更に、水溶性ＰＡＩ（Ｐ）を含有するにもかかわらず、耐食性が良好であり、水溶性ＰＡＩ（Ｐ）が有するカルボキシル基数が比較的多くても耐食性を維持することができる。本発明における耐食性は、水溶性ＰＡＩ（Ｐ）の代わりに非水溶性ＰＡＩを用いた場合に比べ少なくとも同等程度に維持することも可能である。 Although the fluoropolymer aqueous composition of the present invention further contains water-soluble PAI (P), it has good corrosion resistance, and the water-soluble PAI (P) has a relatively large number of carboxyl groups. Corrosion resistance can be maintained. The corrosion resistance in the present invention can be maintained at least at the same level as compared with the case where water-insoluble PAI is used instead of water-soluble PAI (P).
本発明の含フッ素重合体水性組成物は、また、含フッ素重合体（Ｒ）からなるものであり、含フッ素重合体水性組成物が上述のワンコート法に用いる塗料組成物である場合、被塗装物に非粘着性、潤滑性等を付与することができ、上述のツーコート法に用いるプライマー組成物である場合、塗装することにより得られる塗膜と上述の上塗り塗膜との密着性を向上させることができるものである。 The fluoropolymer aqueous composition of the present invention is also composed of a fluoropolymer (R), and when the fluoropolymer aqueous composition is a coating composition used in the above-mentioned one-coat method, Non-adhesiveness, lubricity, etc. can be imparted to the coated material, and in the case of the primer composition used in the above-mentioned two-coating method, the adhesion between the coating film obtained by coating and the above-mentioned top coating film is improved. It can be made to.
本発明の含フッ素重合体水性組成物は、また、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）からなるものであり、上記水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）が上述のように被塗装物との接着性を有するので、塗装することにより得られる塗膜が被塗装物への密着性に優れたものである。 The fluoropolymer aqueous composition of the present invention is also composed of a heat-resistant resin (Q) different from the water-soluble PAI, and the heat-resistant resin (Q) different from the water-soluble PAI is coated as described above. Since it has adhesiveness with an object, the coating film obtained by coating is excellent in adhesion to an object to be coated.
本発明の含フッ素重合体水性組成物は、上述の構成からなるものであるので、塗料組成物として被覆物品の作製に好適に用いることができる。 Since the fluoropolymer aqueous composition of the present invention has the above-described configuration, it can be suitably used as a coating composition for producing a coated article.
本発明の被覆物品は、本発明の含フッ素重合体水性組成物を被塗装物上に塗布し、必要に応じて乾燥することにより得られるものである。 The coated article of the present invention is obtained by applying the fluoropolymer aqueous composition of the present invention on an object to be coated and drying it as necessary.
上記被塗装物は、その種類に応じて予め脱脂処理、粗面化処理等の表面処理を行ったものであってもよい。上記粗面化処理の方法としては特に限定されず、例えば、酸又はアルカリによるケミカルエッチング、陽極酸化（アルマイト処理）、サンドブラスト等が挙げられる。上記表面処理は、上記含フッ素重合体水性組成物をハジキを生じず均一に塗布することができる点、及び、被塗装物と塗布膜との密着性が向上する点から、行うことが好ましい。 The object to be coated may be subjected to a surface treatment such as a degreasing treatment or a roughening treatment in advance according to the type. The surface roughening treatment method is not particularly limited, and examples thereof include chemical etching with acid or alkali, anodization (alumite treatment), and sandblasting. The surface treatment is preferably performed from the viewpoint that the aqueous fluoropolymer composition can be uniformly applied without causing repellency and the adhesion between the object to be coated and the coating film is improved.
上記塗布の方法としては特に限定されず、例えば、スプレー塗装、ロール塗装、ドクターブレードによる塗装、ディップ（浸漬）塗装、含浸塗装、スピンフロー塗装、カーテンフロー塗装等が挙げられる。
上記乾燥としては特に限定されず、例えば、従来公知の方法等が用いられ、６０〜３００℃の温度で５〜６０分間行うことが好ましい。
The application method is not particularly limited, and examples thereof include spray coating, roll coating, doctor blade coating, dip (immersion) coating, impregnation coating, spin flow coating, and curtain flow coating.
It does not specifically limit as said drying, For example, a conventionally well-known method etc. are used, and it is preferable to carry out for 5 to 60 minutes at the temperature of 60-300 degreeC.
本発明の被覆物品の作製は、上記塗膜の上に上塗り塗膜を積層させない上述のワンコート法の場合、上記塗布膜を得た後、この塗布膜を焼成することにより塗膜を得るものである。上記焼成としては特に限定されず、例えば、従来公知の方法等が用いられ、上記水溶性ＰＡＩ（Ｐ）、水溶性ＰＡＩとは異なる耐熱樹脂（Ｑ）、含フッ素重合体（Ｒ）等の種類によるが、通常、２６０〜４１０℃で１０〜３０分間行う。 In the case of the above-mentioned one-coating method in which the top coat film is not laminated on the above-mentioned coating film, the coated article of the present invention is obtained by obtaining the above-mentioned coating film and then firing the coating film to obtain the coating film. It is. The firing is not particularly limited, and for example, a conventionally known method is used, and the water-soluble PAI (P), a heat-resistant resin (Q) different from the water-soluble PAI, a fluorine-containing polymer (R), and the like. However, it is usually performed at 260 to 410 ° C. for 10 to 30 minutes.
本発明の被覆物品の作製は、上記塗膜の上に上塗り塗膜を積層させる上述のツーコート法の場合、上記塗布膜を得た後、この塗布膜上に上塗り塗料を塗布し、必要に応じて乾燥し、次いで焼成することにより含フッ素重合体水性組成物からなる塗膜と、上塗り塗料からなる上塗り塗膜とを得るものである。 In the case of the above-mentioned two-coating method in which a top coat film is laminated on the above-mentioned coating film, the coated article of the present invention is obtained by applying the top coating material on this coating film after obtaining the above-mentioned coating film. The coating film made of the fluoropolymer aqueous composition and the top coating film made of the top coating are obtained by drying and then firing.
本明細書において、上記「上塗り塗料」は、上記塗布膜上に塗布する塗料であって、上塗り用含フッ素重合体からなるものである。上記上塗り用含フッ素重合体は、主鎖又は側鎖を構成する炭素原子に直接結合しているフッ素原子を有する重合体である。上記上塗り用含フッ素重合体は、主鎖又は側鎖を構成する炭素原子に直接結合しているフッ素原子を有する重合体である点で上記含フッ素重合体（Ｒ）と共通するが、上記上塗り塗料に配合されている点で、本発明の含フッ素重合体水性組成物に配合されている上記含フッ素重合体（Ｒ）とは概念上異なるものである。上記上塗り用含フッ素重合体は、上記上塗り塗膜中に存在することにより、被塗装物に非粘着性、潤滑性等を付与することができ、上記含フッ素重合体（Ｒ）と親和性を有するので上記塗膜との密着性も向上することができる。 In the present specification, the “top coating material” is a coating material applied on the coating film, and is made of a fluoropolymer for top coating. The topcoat fluoropolymer is a polymer having a fluorine atom directly bonded to a carbon atom constituting the main chain or side chain. The topcoat fluoropolymer is common to the fluoropolymer (R) in that it is a polymer having a fluorine atom directly bonded to a carbon atom constituting the main chain or side chain. It is conceptually different from the fluoropolymer (R) blended in the aqueous fluoropolymer composition of the present invention in that it is blended in the paint. When the above-mentioned fluoropolymer for topcoat is present in the above-mentioned topcoat film, it can impart non-adhesiveness, lubricity, etc. to the object to be coated, and has an affinity for the above-mentioned fluoropolymer (R). Since it has, adhesiveness with the said coating film can also be improved.
上記上塗り用含フッ素重合体としては特に限定されず、例えば、ＰＴＦＥ、ＰＦＡ、ＦＥＰ等が挙げられるが、上記塗膜と上塗り塗膜との層間密着性を向上させる点から、本発明の含フッ素重合体水性組成物における上記含フッ素重合体（Ｒ）と同じもの、又は、溶融加工性の有無等の性質が類似するものが好ましい。上記上塗り塗料としては、主成分がＰＴＦＥであるＰＴＦＥ系塗料、主成分がＰＦＡであるＰＦＡ系塗料、主成分がＦＥＰであるＦＥＰ系塗料等が挙げられる。 The topcoat fluorine-containing polymer is not particularly limited, and examples thereof include PTFE, PFA, FEP and the like. From the viewpoint of improving the interlayer adhesion between the above-mentioned coating film and the topcoat film, the fluorine-containing polymer of the present invention. The same thing as the said fluoropolymer (R) in a polymer aqueous composition, or the thing similar in properties, such as the presence or absence of melt processability, is preferable. Examples of the top coating include a PTFE paint whose main component is PTFE, a PFA paint whose main component is PFA, an FEP paint whose main component is FEP, and the like.
上記上塗り塗料は、上記上塗り用含フッ素重合体とともに、塗装性、得られる塗膜の性質向上等を目的として、更に、上述の含フッ素重合体水性組成物に用い得る各種添加剤と同様の添加剤を配合してなるものであってもよい。
上記上塗り塗料は、例えば、主成分がＰＴＦＥ、ＰＦＡ又はＦＥＰである場合、水性ディスパージョン系塗料、溶剤系塗料等の液状塗料が挙げられ、主成分がＰＦＡ又はＦＥＰである場合、粉体塗料が挙げられる。
In addition to the above-mentioned fluoropolymer for topcoat, the above topcoat is further added in the same manner as various additives that can be used in the above-mentioned aqueous fluoropolymer composition for the purpose of improving the coating properties and properties of the resulting coating film. An agent may be blended.
For example, when the main component is PTFE, PFA or FEP, examples of the top coat include liquid coatings such as aqueous dispersion-based paints and solvent-based paints. When the main component is PFA or FEP, Can be mentioned.
上記塗布膜は、通常、上記上塗り塗料を塗布する前に焼成を行わないが、必要に応じて焼成を行ってもよい。上記上塗り塗料を塗布する前の焼成は、工程の簡略化や、エネルギー、労力、時間等の低減を図ることができる点で、行わないことが好ましい。 The coating film is usually not fired before the top coating is applied, but may be fired as necessary. It is preferable not to perform the baking before applying the top coating because it can simplify the process and reduce energy, labor, time, and the like.
上記上塗り塗料の塗布の方法としては特に限定されず、例えば、上記上塗り塗料が液状塗料である場合、本発明の含フッ素重合体水性組成物を塗布する方法と同様の方法等が挙げられ、上記上塗り塗料が粉体塗料である場合、静電スプレー塗装、流動浸漬塗装、ロトライニング法等が挙げられる。
上記上塗り塗料を塗布した後の乾燥及び焼成は、それぞれ上述の含フッ素重合体水性組成物を塗布した後に行う乾燥及び焼成と同様の条件で行うことができる。
The method for applying the top coating is not particularly limited. For example, when the top coating is a liquid coating, examples thereof include the same method as the method for applying the aqueous fluoropolymer composition of the present invention. When the top coating material is a powder coating material, electrostatic spray coating, fluidized dip coating, and a rolining method may be used.
Drying and baking after applying the above-mentioned top coat can be performed under the same conditions as drying and baking after applying the above-mentioned fluoropolymer aqueous composition, respectively.
本発明の被覆物品の作製は、上述のツーコート法の場合、上記上塗り塗料の代わりにフィルムを用いることにより上記上塗り塗膜を得るものであってもよい。
本明細書において、上記フィルムは、主として上記上塗り用含フッ素重合体からなるものであり、フィルム状に成形されたものである。上記上塗り塗膜の形成に上記フィルムを用いる場合、上記塗布膜上に上記フィルムを載置し、加熱圧着することにより上記塗布膜と上記フィルムとを密着させる等の従来公知の方法等を用いることができる。
In the case of the above-described two-coating method, the coated article of the present invention may be obtained by using the film instead of the top coating material to obtain the top coating film.
In the present specification, the film is mainly composed of the above-mentioned fluoropolymer for topcoat, and is formed into a film shape. When the film is used for forming the top coat film, a conventionally known method such as placing the film on the coating film and bringing the coating film and the film into close contact by thermocompression bonding is used. Can do.
焼成後における上記塗膜の膜厚及び上記上塗り塗膜の膜厚としては特に限定されず、被覆物品の用途によるが、上記塗膜の膜厚が１〜１００μｍであり、上記上塗り塗膜の膜厚が１０〜２００μｍであることが好ましい。 The film thickness of the coating film after baking and the film thickness of the top coating film are not particularly limited, and depending on the use of the coated article, the film thickness of the coating film is 1 to 100 μm, and the film of the top coating film The thickness is preferably 10 to 200 μm.
上記塗膜は、上述のワンコート法により上記被塗装物上に形成されたものである場合、上記含フッ素重合体（Ｒ）が有する非粘着性、潤滑性等を被塗装物に付与することができ、上述のツーコート法により上記塗膜の上に上塗り塗膜が積層されたものである場合、被塗装物との密着性と上記上塗り塗膜との密着性の両方に優れたものである。 When the coating film is formed on the object to be coated by the above-mentioned one-coat method, the non-adhesiveness, lubricity, etc. of the fluoropolymer (R) are imparted to the object to be coated. When the top coat film is laminated on the above-mentioned coating film by the above-mentioned two-coating method, it is excellent in both the adhesion with the object to be coated and the adhesion with the above-mentioned top coating film. .
本発明の被覆物品は、被塗装物と、上記塗膜とからなるものであって、上記塗膜は、上記被塗装物上に塗装することにより得られたものである。本発明の被覆物品は、少なくとも上記被塗装物と上記塗膜とからなるものであれば、更に、上記上塗り塗膜を有するものであってもよい。 The coated article of the present invention comprises an object to be coated and the coating film, and the coating film is obtained by painting on the object to be coated. As long as the coated article of the present invention comprises at least the article to be coated and the coating film, the coated article may further have the top coating film.
上記被塗装物としては特に限定されず、例えば、鉄、アルミニウム、銅等の金属単体及びこれらの合金類等の金属；ホーロー、ガラス、セラミックス等の非金属無機材料等が挙げられる。上記合金類としては、ステンレス等が挙げられる。 The material to be coated is not particularly limited, and examples thereof include simple metals such as iron, aluminum, and copper and metals such as alloys thereof; nonmetallic inorganic materials such as enamel, glass, and ceramics. Examples of the alloys include stainless steel.
本発明の被覆物品は、上述のワンコート法に用いた含フッ素重合体（Ｒ）、又は、上述のツーコート法に用いた上塗り用含フッ素重合体が有する特性を利用した用途に使用することができる。 The coated article of the present invention can be used for applications utilizing the properties of the fluoropolymer (R) used in the above-mentioned one-coat method or the topcoat fluoropolymer used in the above-mentioned two-coat method. it can.
本発明の被覆物品としては特に限定されず、例えば、上記特性として非粘着性を利用する場合、フライパン、グリル鍋、圧力鍋、その他の各種鍋、炊飯器、餅つき器、オーブン、ホットプレート、パン焼き型、包丁、ガステーブル等の調理器具；電気ポット、製氷トレー等の飲食用容器；練りロール、圧延ロール、コンベアホッパー等の食品工業用部品；オフィスオートメーション機器〔ＯＡ〕用ロール、ＯＡ用ベルト、製紙ロール、フィルム製造用カレンダーロール等の工業用品；発泡スチロール成形用等の金型、合板・化粧板製造用離型板等の成形金型離型；レンジフード等の厨房用品；コンベアーベルト等の冷凍食品製造装置等が挙げられる。 The coated article of the present invention is not particularly limited, for example, when using non-adhesiveness as the above characteristics, frying pan, grill pan, pressure cooker, other various pans, rice cooker, rice bowl, oven, hot plate, Cooking utensils such as baking pans, kitchen knives, gas tables; food and beverage containers such as electric pots and ice trays; food industry parts such as kneading rolls, rolling rolls, and conveyor hoppers; rolls for office automation equipment [OA], belts for OA Industrial articles such as paper rolls and calendar rolls for film production; Molds for foamed polystyrene molding, mold release molds such as release plates for plywood and decorative board production; Kitchen articles such as range hoods; Conveyor belts, etc. Examples include frozen food manufacturing equipment.
本発明の被覆物品としては、また、上記特性として滑り性を利用する場合、のこぎり、やすり等の工具；アイロン等の家庭用品；金属箔；食品加工機、包装機、紡繊機械等のすべり軸受；カメラ・時計の摺動部品；自動車部品等が挙げられる。 As the coated article of the present invention, when sliding is used as the above property, tools such as saws and files; household items such as irons; metal foils; sliding bearings for food processing machines, packaging machines, textile machines, etc. ; Sliding parts of cameras and watches; automobile parts and the like.
本発明の含フッ素重合体水性組成物は、上述の構成を有するので、耐食性が良好で、ハジキや塗装ムラが起きにくく、塗装性に優れた含フッ素重合体組成物を得ることができるものである。
本発明の被塗装物は、上述の構成を有するので、塗装ムラがなく、各種飲食用容器等として好適に用いることができるものである。
Since the fluoropolymer aqueous composition of the present invention has the above-described configuration, it can provide a fluoropolymer composition that has excellent corrosion resistance, is resistant to repelling and uneven coating, and has excellent paintability. is there.
Since the article to be coated of the present invention has the above-described configuration, it has no coating unevenness and can be suitably used as various food and drink containers.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。以下、「％」「部」は、それぞれ質量％、質量部を表す。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Hereinafter, “%” and “part” represent mass% and mass part, respectively.
製造例１
ポリエーテルスルホン樹脂水性分散体の調製
数平均分子量約２４０００のポリエーテルスルホン樹脂〔ＰＥＳ〕６０部及び脱イオン水６０部を、セラミックボールミル中でＰＥＳからなる粒子が完全に粉砕されるまで約１０分間攪拌した。次いで、Ｎ−メチル−２−ピロリドン〔ＮＭＰ〕１８０部を添加し、更に、４８時間粉砕し、分散体を得た。得られた分散体を更にサンドミルで１時間粉砕し、ＰＥＳ濃度が約２０％のＰＥＳ水性分散体を得た。ＰＥＳ水性分散体中のＰＥＳからなる粒子の粒子径は、２〜３μｍであった。
Production Example 1
Preparation of aqueous dispersion of polyethersulfone resin 60 parts of a polyethersulfone resin [PES] having a number average molecular weight of about 24,000 and 60 parts of deionized water are mixed for about 10 minutes in a ceramic ball mill until the particles composed of PES are completely pulverized. Stir. Next, 180 parts of N-methyl-2-pyrrolidone [NMP] was added and further pulverized for 48 hours to obtain a dispersion. The obtained dispersion was further pulverized with a sand mill for 1 hour to obtain a PES aqueous dispersion having a PES concentration of about 20%. The particle diameter of the particles composed of PES in the PES aqueous dispersion was 2 to 3 μm.
製造例２
水溶性ポリアミドイミド樹脂溶液の調製
数平均分子量が２００００で１ｇ当りの酸価が８０ｍｇ（ＫＯＨ）のポリアミドイミド樹脂〔ＰＡＩ〕１１１．１部、ＮＭＰ１５６．３６部、フルフリルアルコール１７．３７部、ジエタノールアミン４４．９２部、アンモニア水（２８％）３．５７部、イオン交換水３３３．３３部を攪拌し、ＰＡＩを溶解させ、水溶性ＰＡＩ溶液を得た。水溶性ＰＡＩ溶液中のＰＡＩの濃度は、１５％であった。
Production Example 2
Preparation of water-soluble polyamideimide resin solution Polyamideimide resin [PAI] having a number average molecular weight of 20000 and an acid value per gram of 80 mg (KOH) 111.1 parts, NMP 156.36 parts, furfuryl alcohol 17.37 parts, diethanolamine 44.92 parts, ammonia water (28%) 3.57 parts, and ion-exchanged water 333.33 parts were stirred to dissolve PAI to obtain a water-soluble PAI solution. The concentration of PAI in the aqueous PAI solution was 15%.
製造例３
ポリアミドイミド樹脂水性分散体の調製
固形分２９％のポリアミドイミド樹脂〔ＰＡＩ〕ワニス（ＮＭＰを７１％含む）を水中に投入してＰＡＩを析出させた。これをボールミル中で４８時間粉砕してＰＡＩ水性分散体を得た。得られたＰＡＩ水性分散体中の固形分は、２０％であり、ＰＡＩからなる粒子の平均粒子径は、２μｍであった。
Production Example 3
Preparation of Polyamideimide Resin Aqueous Dispersion Polyamideimide resin [PAI] varnish (containing 71% NMP) having a solid content of 29% was poured into water to precipitate PAI. This was pulverized for 48 hours in a ball mill to obtain an aqueous PAI dispersion. The solid content in the obtained PAI aqueous dispersion was 20%, and the average particle size of the particles composed of PAI was 2 μm.
実施例１
製造例１で得られたＰＥＳ水性分散体、及び、製造例２で得られた水溶性ＰＡＩ溶液を、ＰＥＳが、ＰＥＳと水溶性ＰＡＩとの合計固形分質量の８５％となるように混合し、これにポリテトラフルオロエチレン〔ＰＴＦＥ〕水性分散体（平均粒子径０．２８μｍ、固形分６０％、分散剤としてポリエーテル系ノニオン界面活性剤（ＨＬＢ値＝１４）をＰＴＦＥの固形分１００部に対して６部含有している）を、ＰＥＳ及び水溶性ＰＡＩが、ＰＥＳ、水溶性ＰＡＩ及びＰＴＦＥの合計固形分質量の２０％となるように加え、分散安定剤としてポリオキシエチレントリデシルエーテル（ＨＬＢ値＝１０）をＰＴＦＥの固形分１００部に対して６部添加して、固形分３３％の塗料組成物を得た。
Example 1
The PES aqueous dispersion obtained in Production Example 1 and the water-soluble PAI solution obtained in Production Example 2 were mixed so that PES was 85% of the total solid mass of PES and water-soluble PAI. Polytetrafluoroethylene [PTFE] aqueous dispersion (average particle size 0.28 μm, solid content 60%, polyether nonionic surfactant (HLB value = 14) as a dispersant to 100 parts of PTFE solid content) 6 parts), so that PES and water-soluble PAI are 20% of the total solid mass of PES, water-soluble PAI and PTFE, and polyoxyethylene tridecyl ether (as a dispersion stabilizer) is added. 6 parts of HLB value = 10) was added to 100 parts of solid content of PTFE to obtain a coating composition having a solid content of 33%.
（評価用塗装板の作製）
厚さ２．０ｍｍ、大きさ５×１０ｃｍのアルミニウム板（Ａ−１０５０）の表面をアセトンで脱脂した後、ＪＩＳ Ｂ １９８２に準拠して測定した表面粗度Ｒａ値が２．５〜３．５μｍとなるようにサンドブラストを行い、粗面化した。エアーブローにより表面のダストを除去した後、下塗り塗料として、得られた塗料組成物を、重力式スプレーガンＲＧ−２型（商品名、アネスト岩田社製、ノズル径１．０ｍｍ）を用い、乾燥膜厚が１０〜１５μｍとなるように、吹き付け圧力０．２ＭＰａでスプレー塗装により塗布した。得られた塗布膜を８０〜１００℃で１５分間乾燥し、室温まで冷却した。得られた塗布膜の上に、上塗り塗料としてＰＴＦＥを含有する水性塗料ポリフロンＰＴＦＥ ＥＫ−３７００Ｃ−２０１（商品名、ダイキン工業社製）を同様の条件でスプレー塗装により塗布し、８０〜１００℃で１５分間乾燥した。その後３８０℃で２０分間焼成し、膜厚約２０μｍの上塗り塗膜を作製し、評価用塗装板を得た。
(Preparation of evaluation paint plate)
After the surface of an aluminum plate (A-1050) having a thickness of 2.0 mm and a size of 5 × 10 cm is degreased with acetone, the surface roughness Ra value measured according to JIS B 1982 is 2.5 to 3.5 μm. Sandblasting was performed to obtain a rough surface. After removing dust on the surface by air blow, the resulting coating composition is dried as a primer by using a gravity spray gun RG-2 (trade name, manufactured by Anest Iwata, nozzle diameter: 1.0 mm). The film was applied by spray coating at a spraying pressure of 0.2 MPa so that the film thickness was 10 to 15 μm. The obtained coating film was dried at 80 to 100 ° C. for 15 minutes and cooled to room temperature. On the obtained coating film, an aqueous paint polyflon PTFE EK-3700C-201 (trade name, manufactured by Daikin Industries) containing PTFE as a top coat is applied by spray coating under the same conditions, and at 80 to 100 ° C. Dry for 15 minutes. Thereafter, it was baked at 380 ° C. for 20 minutes to produce an overcoat film having a film thickness of about 20 μm, and an evaluation coated plate was obtained.
得られた塗料組成物、及び、評価用塗装板について、下記の評価を行った。 The following evaluation was performed about the obtained coating composition and the coating plate for evaluation.
（塗装性）
得られた塗料組成物を、ガラス板に塗料の粒子径がわかるように塗布し（吹き付け圧力０．２ＭＰａ、ガラス板と重力式スプレーガンとの距離３０ｃｍ、塗布時間１秒間。）、乾燥後、顕微鏡で観察して平均粒子径を求めた。
得られた塗料組成物の霧化性は良く、塗装性は良好で、ガラス板上の塗料の平均粒子径は２８μｍであった。
(Paintability)
The obtained coating composition was applied to a glass plate so that the particle diameter of the coating was known (spraying pressure 0.2 MPa, distance between glass plate and gravity spray gun 30 cm, application time 1 second), and after drying, The average particle size was determined by observation with a microscope.
The resulting coating composition had good atomization properties and good paintability, and the average particle size of the coating material on the glass plate was 28 μm.
（塗膜外観）
得られた評価用塗装板の外観を目視で観察し、評価を行った。
得られた評価用塗装板は、上塗り塗料を塗装、焼成後の塗膜外観も均一で良好であった。
(Appearance of coating film)
The appearance of the obtained coating plate for evaluation was visually observed and evaluated.
The obtained coated plate for evaluation was uniform and good in the appearance of the coated film after the top coating was applied and baked.
（耐食性）
得られた評価用塗装板にカッターナイフでクロスカット（切り傷）を入れ、水１Ｌに対しておでんの素（エスビー社製）２０ｇを溶かした溶液に浸漬し、７０℃に保温した。１０００時間経過した後、塗膜に膨れが発生していないかを目視で観察した。
得られた評価用塗装板は、１０００時間経過後も塗膜に膨れの発生はなく、良好であった。
(Corrosion resistance)
The obtained coated plate for evaluation was cross-cut (cut) with a cutter knife, immersed in a solution in which 20 g of Oden element (manufactured by Esby) was dissolved in 1 L of water, and kept at 70 ° C. After 1000 hours, it was visually observed whether the coating film was swollen.
The obtained coated plate for evaluation was satisfactory with no swelling of the coating film even after 1000 hours.
比較例１
水溶性ＰＡＩ溶液に代えて製造例３で得られたポリアミドイミド樹脂水性分散体を使用した以外は、実施例と同様に塗料組成物を得た。
得られた塗料組成物を用いて、実施例と同様に評価用塗装板を作製し、評価を行った。
Comparative Example 1
A coating composition was obtained in the same manner as in Example except that the aqueous polyamideimide resin dispersion obtained in Production Example 3 was used instead of the water-soluble PAI solution.
Using the obtained coating composition, an evaluation coated plate was prepared and evaluated in the same manner as in the Examples.
（塗装性）
得られた塗料組成物の霧化性は劣り、一部でハジキが発生し、塗装性に劣っていた。ガラス板上の塗料の平均粒子径は６０μｍであった。
（塗膜外観）
得られた評価用塗装板の塗膜外観は、下塗り塗料として塗料組成物を塗装した際に発生したハジキの箇所に斑点が認められ、劣っていた。
（耐食性）
得られた評価用塗装板は、１０００時間経過後も塗膜に膨れの発生はなく、良好であった。
(Paintability)
The resulting coating composition was poor in atomization, partially repelled, and inferior in paintability. The average particle size of the paint on the glass plate was 60 μm.
(Appearance of coating film)
The coating film appearance of the obtained coated plate for evaluation was inferior because spots were observed at the repellant spots generated when the coating composition was applied as an undercoat.
(Corrosion resistance)
The obtained coated plate for evaluation was satisfactory with no swelling of the coating film even after 1000 hours.
比較例２
製造例２で得られた水溶性ＰＡＩ溶液にＰＴＦＥ水性分散体（平均粒子径０．２８μｍ、固形分６０％、分散剤としてポリエーテル系ノニオン界面活性剤（ＨＬＢ値＝１４）をＰＴＦＥの固形分１００部に対して６部含有している）を、水溶性ＰＡＩが、水溶性ＰＡＩ及びＰＴＦＥの合計固形分質量の２０％となるように加え、分散安定剤としてポリオキシエチレントリデシルエーテル（ＨＬＢ値＝１０）をＰＴＦＥの固形分１００部に対して６部添加して、固形分２１％の塗料組成物を得た。
得られた塗料組成物を用いて、実施例と同様に評価用塗装板を作製し、評価を行った。
Comparative Example 2
An aqueous PTFE dispersion (average particle size 0.28 μm, solid content 60%, polyether nonionic surfactant (HLB value = 14) as a dispersant) was added to the water-soluble PAI solution obtained in Production Example 2. 6 parts per 100 parts) is added so that the water-soluble PAI is 20% of the total solid content of water-soluble PAI and PTFE, and polyoxyethylene tridecyl ether (HLB) is added as a dispersion stabilizer. Value = 10) was added in an amount of 6 parts per 100 parts of the solid content of PTFE to obtain a coating composition having a solid content of 21%.
Using the obtained coating composition, an evaluation coated plate was prepared and evaluated in the same manner as in the Examples.
（塗装性）
得られた塗料組成物の霧化性は良く、塗装性は良好で、ガラス板上の塗料の平均粒子径は２６μｍであった。
（塗膜外観）
得られた評価用塗装板は、上塗りを塗装、焼成後の塗膜外観も均一で良好であった。
（耐食性）
得られた評価用塗装板は、３００時間経過後、塗膜に膨れの発生が認められ、不良であった。
(Paintability)
The resulting coating composition had good atomization properties and good paintability, and the average particle size of the coating material on the glass plate was 26 μm.
(Appearance of coating film)
The obtained coated plate for evaluation was uniform and good in appearance of the coated film after coating and baking.
(Corrosion resistance)
The obtained coated plate for evaluation was defective because the coating film was swollen after 300 hours.
本発明の含フッ素重合体水性組成物は、耐食性が良好で、ハジキや塗装ムラが起きにくく、塗装性に優れているので、各種被塗装物品の製造に幅広く用いることができる。
本発明の被塗装物は、上記含フッ素重合体水性組成物を塗装してなるものであるので、塗装ムラがなく、各種飲食用容器等として好適に用いることができる。
The aqueous fluorinated polymer composition of the present invention has good corrosion resistance, hardly causes repelling or coating unevenness, and is excellent in paintability. Therefore, it can be widely used in the production of various articles to be coated.
Since the article to be coated of the present invention is obtained by coating the above fluoropolymer aqueous composition, there is no coating unevenness and it can be suitably used as various food and beverage containers.
Claims (7)
ことを特徴とする含フッ素重合体水性組成物。 A fluoropolymer aqueous composition comprising an aqueous dispersion containing a water-soluble polyamideimide resin (P), a heat-resistant resin (Q) different from the water-soluble polyamideimide resin, and a fluoropolymer (R) object.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009014009A1 (en) * | 2007-07-24 | 2009-01-29 | Daikin Industries, Ltd. | Coating composition |
| JP2009061591A (en) * | 2007-09-04 | 2009-03-26 | Konica Minolta Holdings Inc | Ink jet recording head |
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| JP2010037506A (en) * | 2008-08-08 | 2010-02-18 | Toho Chem Ind Co Ltd | Method for producing aqueous polyimide resin dispersion |
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