JP7428915B2 - Fluorine-containing resin solvent-based primer composition, coating film, fluorine-containing resin laminate, and articles - Google Patents
Fluorine-containing resin solvent-based primer composition, coating film, fluorine-containing resin laminate, and articles Download PDFInfo
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- JP7428915B2 JP7428915B2 JP2021200857A JP2021200857A JP7428915B2 JP 7428915 B2 JP7428915 B2 JP 7428915B2 JP 2021200857 A JP2021200857 A JP 2021200857A JP 2021200857 A JP2021200857 A JP 2021200857A JP 7428915 B2 JP7428915 B2 JP 7428915B2
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- fluororesin
- mass
- primer composition
- coating film
- composition
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Description
本開示は、含フッ素樹脂溶剤型プライマー組成物、塗膜、含フッ素樹脂積層体、および、物品に関する。 The present disclosure relates to a fluororesin solvent-based primer composition, a coating film, a fluororesin laminate, and an article.
フッ素樹脂は、塗料組成物に調製し、パン金型、炊飯釜等の耐蝕性、非粘着性、耐熱性等が要求されるものの基材に塗装してフッ素樹脂層を形成させることに幅広い用途がある。しかしながら、フッ素樹脂は、その非粘着性ゆえに、金属、セラミック等からなる基材との接着性に乏しいという問題もあった。 Fluororesins are used in a wide range of applications, such as preparing paint compositions and coating them on substrates that require corrosion resistance, non-stick properties, heat resistance, etc., such as bread molds and rice cookers, to form a fluororesin layer. There is. However, due to its non-adhesive nature, fluororesin also has the problem of poor adhesion to base materials made of metals, ceramics, and the like.
そこで、フッ素樹脂を金属、セラミック、ガラス等の基材表面に塗装する際には、これら基材表面にサンドブラスト、エッチング等の方法で物理的な凹凸を形成させた後、接着性を有するプライマー組成物を基材表面に塗布してプライマー層を形成させ、このプライマー層を介して、基材とトップコート層であるフッ素樹脂を接着させる方法が一般的に広く行なわれている。 この方法において基材表面とプライマー層との接着には、基材表面の凹凸によりプライマー層と基材表面との接着面積が増大し接着力が向上するアンカー効果（投錨効果）が利用されている。 Therefore, when applying fluororesin to the surface of base materials such as metals, ceramics, and glass, it is necessary to form physical irregularities on the surface of these base materials by methods such as sandblasting or etching, and then apply a primer composition that has adhesive properties. A widely used method is to form a primer layer by applying a substance to the surface of a base material, and to adhere the base material and a fluororesin, which is a top coat layer, through the primer layer. In this method, the adhesion between the base material surface and the primer layer utilizes the anchor effect, which increases the adhesion area between the primer layer and the base material surface due to the unevenness of the base material surface and improves the adhesive force. .
また、プライマー層は金属、セラッミック、ガラス等の基材表面に接着すると共に、トップコート層であるフッ素樹脂とも接着しなければならないため、プライマー層の形成には、トップコート層と同じ材料であるフッ素樹脂粉末とバインダー樹脂と呼ばれる接着性を有する物質とを、液状媒体中に均一に分散させたプライマー組成物を基材表面に塗布する方法が用いられている。プライマー組成物に用いられるフッ素樹脂粉末としては、分散性、トップコート層のフッ素樹脂粉末との接着性等の点から、従来、平均粒径１μｍ未満のフッ素樹脂微粉末が一般的に広く使用されていた。 In addition, the primer layer must adhere to the surface of the base material such as metal, ceramic, glass, etc., and must also adhere to the fluororesin top coat layer, so the primer layer must be formed using the same material as the top coat layer. A method is used in which a primer composition in which fluororesin powder and an adhesive substance called binder resin are uniformly dispersed in a liquid medium is applied to the surface of a substrate. As the fluororesin powder used in the primer composition, fine fluororesin powder with an average particle size of less than 1 μm has traditionally been widely used from the viewpoint of dispersibility and adhesion to the fluororesin powder of the top coat layer. was.
特許文献１には、基材上に形成されるプライマー層と、該プライマー層上に形成されるトップコート層とからなるフッ素樹脂塗膜を有する物品において、プライマー層が、その膜厚以上の平均粒径を有する少なくとも１種のフッ素樹脂粉末（Ａ）と、その膜厚未満の平均粒径を有する少なくとも１種のフッ素樹脂粉末（Ｂ）とを、（Ａ）：（Ｂ）の重量比１０～１００：９０～０の割合で液状媒体中に均一に分散したプライマー組成物により形成されてなるフッ素樹脂塗膜を有する物品が開示され、上記フッ素樹脂粉末（Ａ）および（Ｂ）の少なくとも一方が、ポリテトラフルオロエチレン、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／エチレン共重合体、ポリビニリデンフルオライド、ポリクロロトリフルオロエチレン、或いはこれらの混合物であることが好ましいと開示されている。 Patent Document 1 describes that in an article having a fluororesin coating film consisting of a primer layer formed on a base material and a top coat layer formed on the primer layer, the primer layer has an average film thickness greater than or equal to the average thickness of the primer layer. At least one type of fluororesin powder (A) having a particle size and at least one type of fluororesin powder (B) having an average particle size less than the film thickness at a weight ratio of (A):(B) 10 Disclosed is an article having a fluororesin coating film formed of a primer composition uniformly dispersed in a liquid medium in a ratio of ~100:90~0, wherein at least one of the fluororesin powders (A) and (B) is However, polytetrafluoroethylene, tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/ethylene copolymer, polyvinylidene fluoride, polychlorotrifluoride It is disclosed that ethylene or a mixture thereof is preferred.
また、特許文献２には、含フッ素重合体、耐熱樹脂、及び、水溶性無機塩を含み、 上記含フッ素重合体は、ポリテトラフルオロエチレン、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体及びテトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体からなる群より選択される少なくとも１種であり、かつ、平均粒子径が０．０１～５μｍであり、 上記耐熱樹脂は、平均粒子径が０．１～１０．０μｍであり、 上記耐熱樹脂と上記含フッ素重合体との固形分質量比が１５：８５～５０：５０であり、 上記水溶性無機塩は、上記含フッ素重合体及び上記耐熱樹脂の合計固形分に対して０．０ ００１～１０質量％である ことを特徴とする被覆用組成物が開示されている。 Further, Patent Document 2 discloses that the fluoropolymer includes a fluoropolymer, a heat-resistant resin, and a water-soluble inorganic salt, and the fluoropolymer includes polytetrafluoroethylene, a tetrafluoroethylene/hexafluoropropylene copolymer, and a tetrafluoroethylene copolymer. is at least one selected from the group consisting of ethylene/perfluoro(alkyl vinyl ether) copolymers, and has an average particle size of 0.01 to 5 μm, and the heat-resistant resin has an average particle size of 0.1 ~10.0 μm, the solid content mass ratio of the heat resistant resin and the fluoropolymer is 15:85 to 50:50, and the water-soluble inorganic salt is the fluoropolymer and the heat resistant resin. Coating compositions are disclosed which are characterized in that the total solids content is from 0.0 001 to 10% by weight.
本開示は、フッ素樹脂層のプライマーとして好適な、基材及びフッ素樹脂層に対して高い密着性を得ることができる含フッ素樹脂溶剤型プライマー組成物を提供することを目的とする。更に詳しくは、フッ素樹脂層との充分な接着力を有するプライマー層を設けることにより得られる、接着力の優れたフッ素樹脂積層体を提供する。 An object of the present disclosure is to provide a fluororesin solvent-based primer composition that is suitable as a primer for a fluororesin layer and can obtain high adhesion to a base material and a fluororesin layer. More specifically, the present invention provides a fluororesin laminate with excellent adhesive strength, which is obtained by providing a primer layer having sufficient adhesive strength with the fluororesin layer.
本開示は、フッ素樹脂及びバインダー樹脂を液状媒体に分散させた含フッ素樹脂溶剤型プライマー組成物であって、
上記フッ素樹脂は、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）であるテトラフルオロエチレン〔ＴＦＥ〕／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕、及び、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）である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〕共重合体〔ＦＥＰ〕を含み、
〔ＰＦＡ〕／〔ＦＥＰ〕の質量比は、１０／９０～９０／１０の範囲にあり、
上記バインダー樹脂は、ポリアミドイミド〔ＰＡＩ〕及びポリエーテルサルフォン〔ＰＥＳ〕を含み、〔ＰＡＩ〕／〔ＰＥＳ〕の質量比が１／９９～６０／４０の範囲にあり、
〔ＰＦＡ〕及び〔ＦＥＰ〕の合計含有量が組成物の１０～４０質量％、並びに、〔ＰＡＩ〕及び〔ＰＥＳ〕の合計含有量が組成物の１０～４０質量％の範囲にあり、
さらに、沸点１００℃未満の液状媒体（Ａ）を組成物中に１～３０質量％、及び、沸点１００～１５０℃の液状媒体（Ｂ）を組成物中に１～３０質量％含む
ことを特徴とする含フッ素樹脂溶剤型プライマー組成物に関する。
The present disclosure provides a fluororesin solvent-based primer composition in which a fluororesin and a binder resin are dispersed in a liquid medium,
The above fluororesin is a tetrafluoroethylene [TFE]/perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] having a melt flow rate (MFR) of 10 to 30 (g/10 min), and a melt flow rate Contains a tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer [FEP] having a (MFR) of 10 to 30 (g/10 min),
The mass ratio of [PFA]/[FEP] is in the range of 10/90 to 90/10,
The binder resin includes polyamideimide [PAI] and polyethersulfone [PES], and the mass ratio of [PAI ] / [PES] is in the range of 1/99 to 60/40,
The total content of [PFA] and [FEP] is in the range of 10 to 40% by mass of the composition, and the total content of [PAI] and [PES] is in the range of 10 to 40% by mass of the composition,
Further, the composition contains 1 to 30% by mass of a liquid medium (A) with a boiling point of less than 100°C, and 1 to 30% by mass of a liquid medium (B) with a boiling point of 100 to 150°C. The present invention relates to a fluorine-containing resin solvent-type primer composition.
上記含フッ素樹脂溶剤型プライマー組成物は、組成物中のＮ－メチル－２－ピロリドンの含有量は、１質量％未満であってもよい。 The content of N-methyl-2-pyrrolidone in the fluororesin solvent-based primer composition may be less than 1% by mass.
本開示は、上述の含フッ素樹脂溶剤型プライマー組成物により形成されてなる塗膜でもある。
本開示は、被塗装物、上述の塗膜、および、ＰＦＡを含むフッ素樹脂層からなり、上記被塗装物、上記塗膜および上記フッ素樹脂層は、この順に積層していることを特徴とする含フッ素樹脂積層体でもある。
本開示は、上記含フッ素樹脂積層体を有する物品でもある。
The present disclosure also relates to a coating film formed from the above-described fluororesin solvent-based primer composition.
The present disclosure is characterized in that it consists of an object to be painted, the above-mentioned coating film, and a fluororesin layer containing PFA, and the object to be painted, the above-mentioned coating film, and the fluororesin layer are laminated in this order. It is also a fluororesin laminate.
The present disclosure also provides an article having the fluororesin laminate described above.
本開示の含フッ素樹脂溶剤型プライマー組成物により、金属基材との密着性、及び、フッ素樹脂層との密着性に優れるプライマー層を形成することができる。 With the fluororesin solvent-based primer composition of the present disclosure, it is possible to form a primer layer that has excellent adhesion to a metal substrate and to a fluororesin layer.
以下、本開示を詳細に説明する。
本開示は、フッ素樹脂及びバインダー樹脂を液状媒体に分散させた含フッ素樹脂溶剤型プライマー組成物であって、
上記フッ素樹脂は、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）であるテトラフルオロエチレン〔ＴＦＥ〕／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕、及び、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）である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〕共重合体〔ＦＥＰ〕を含み、
〔ＰＦＡ〕／〔ＦＥＰ〕の質量比は、１０／９０～９０／１０の範囲にあり、
上記バインダー樹脂は、ポリアミドイミド〔ＰＡＩ〕及びポリエーテルサルフォン〔ＰＥＳ〕を含み、〔ＰＡＩ〕／〔ＰＥＳ〕の質量比が１／９９～６０／４０の範囲にあり、
沸点１００℃未満の液状媒体（Ａ）を組成物中に１～３０質量％の範囲で含有し、さらに、沸点１００～１５０℃の液状媒体（Ｂ）を組成物中に１～３０質量％の範囲で含むことを特徴とする含フッ素樹脂溶剤型プライマー組成物である。
The present disclosure will be described in detail below.
The present disclosure provides a fluororesin solvent-based primer composition in which a fluororesin and a binder resin are dispersed in a liquid medium,
The above fluororesin is a tetrafluoroethylene [TFE]/perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] having a melt flow rate (MFR) of 10 to 30 (g/10 min), and a melt flow rate Contains a tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer [FEP] having a (MFR) of 10 to 30 (g/10 min),
The mass ratio of [PFA]/[FEP] is in the range of 10/90 to 90/10,
The binder resin includes polyamideimide [PAI] and polyethersulfone [PES], and the mass ratio of [PAI]/[PES] is in the range of 1/99 to 60/40,
The composition contains a liquid medium (A) with a boiling point of less than 100°C in an amount of 1 to 30% by mass, and further contains a liquid medium (B) with a boiling point of 100 to 150°C in an amount of 1 to 30% by mass. This is a fluorine-containing resin solvent-type primer composition characterized in that it contains a fluorine-containing resin within a range.
本開示の含フッ素溶剤型プライマー組成物（以下、プライマー組成物と表す）は、特定の範囲のＭＦＲを有するＰＦＡ及びＦＥＰを特定の質量比の範囲で含み、バインダー樹脂となるＰＡＩ及びＰＥＳを特定の質量比の範囲で含み、さらに、沸点１００℃未満の液状媒体（Ａ）と沸点１００～１５０℃の液状媒体（Ｂ）とを特定量配合することにより、被塗装物との密着性に優れ、かつ、フッ素樹脂層との密着性も改善された塗膜を形成することができるものである。 The fluorine-containing solvent-based primer composition of the present disclosure (hereinafter referred to as primer composition) contains PFA and FEP having MFR in a specific range in a specific mass ratio range, and specifies PAI and PES as binder resins. In addition, by blending a specific amount of a liquid medium (A) with a boiling point of less than 100°C and a liquid medium (B) with a boiling point of 100 to 150°C, it has excellent adhesion to the object to be coated. Moreover, it is possible to form a coating film with improved adhesion to the fluororesin layer.
フッ素樹脂とバインダー樹脂とを含むプライマー組成物を塗布した場合、フッ素樹脂とバインダー樹脂とが表面張力に差を有するゆえ、焼成するとフッ素樹脂が浮上するので、塗膜表面側に主としてフッ素樹脂が配置し、被塗装物側に主としてバインダー樹脂が配置した塗膜を形成する。従来のプライマー組成物は、上述のように塗膜表面側に配向しているフッ素樹脂が上塗り塗膜中のフッ素樹脂と親和性を示すゆえ、上塗り塗膜との間に優れた密着性を示す性質を利用したものであった。 When a primer composition containing a fluororesin and a binder resin is applied, since the fluororesin and the binder resin have a difference in surface tension, the fluororesin floats when fired, so the fluororesin is mainly placed on the surface of the coating film. Then, a coating film containing mainly binder resin is formed on the side of the object to be coated. Conventional primer compositions exhibit excellent adhesion with the top coat because the fluororesin oriented toward the surface of the paint film has an affinity for the fluororesin in the top coat as described above. It took advantage of its nature.
本開示のプライマー組成物は、さらに上記フッ素樹脂のＭＦＲを特定の範囲に限定することで、フッ素樹脂の流動性を制御したものである。上記範囲のＭＦＲを有するフッ素樹脂は、焼成時に速やかに浮上することができるため、塗膜表面にフッ素樹脂が配置した塗膜を効果的に形成することができるものである。 In the primer composition of the present disclosure, the fluidity of the fluororesin is controlled by further limiting the MFR of the fluororesin to a specific range. A fluororesin having an MFR within the above range can be quickly floated during firing, so that a coating film in which the fluororesin is disposed on the coating surface can be effectively formed.
さらに、本開示のプライマー組成物は、沸点が１５０℃以下である低沸点の液状媒体を含有するものである。これまでも、比較的低沸点の液状媒体が配合されたプライマー組成物は検討されてきたが、１６０～１８０℃程度の沸点を有する液状媒体が主であり、１５０℃以下となるものは検討されていなかった。本開示は、沸点１００℃未満の液状媒体（Ａ）と沸点１００～１５０℃の液状媒体（Ｂ）とを併用することで、より優れた密着性を有する塗膜を形成することができるものである。このような作用は、おそらく、塗膜焼成時に上記二種の液状媒体が順次塗膜表面へ移行することで、上記フッ素樹脂もより速やかに塗膜表面に上昇することができるためであると考えられる。 Furthermore, the primer composition of the present disclosure contains a low boiling point liquid medium having a boiling point of 150° C. or lower. Until now, primer compositions containing liquid media with relatively low boiling points have been studied, but liquid media with boiling points of about 160 to 180°C have been the main ones, and primer compositions with boiling points below 150°C have not been studied. It wasn't. The present disclosure makes it possible to form a coating film with better adhesion by using a liquid medium (A) with a boiling point of less than 100°C and a liquid medium (B) with a boiling point of 100 to 150°C together. be. This effect is probably due to the fact that the two types of liquid media mentioned above move sequentially to the coating surface during coating baking, allowing the fluororesin to rise to the coating surface more quickly. It will be done.
（フッ素樹脂）
本開示のプライマー組成物は、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）であるＰＦＡ、及び、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）であるＦＥＰをフッ素樹脂として含むものである。
上記ＦＥＰは、共重合体中のＨＦＰ単位が２質量％を超え、２０質量％以下であることが好ましく、１０～１５質量％であることがより好ましい。
(fluororesin)
The primer composition of the present disclosure combines PFA with a melt flow rate (MFR) of 10 to 30 (g/10 min) and FEP with a melt flow rate (MFR) of 10 to 30 (g/10 min) with a fluororesin. It is included as
In the above-mentioned FEP, the HFP unit in the copolymer is preferably more than 2% by mass and 20% by mass or less, more preferably 10 to 15% by mass.
上記ＰＦＡにおけるＰＡＶＥとしては、炭素数１～６のアルキル基を有するものが好ましく、パーフルオロ（メチルビニルエーテル）〔ＰＭＶＥ〕、パーフルオロ（エチルビニルエーテル）〔ＰＥＶＥ〕又はパーフルオロ（プロピルビニルエーテル）〔ＰＰＶＥ〕がより好ましい。上記ＰＦＡは、共重合体中のＰＡＶＥ単位が２質量％を超え、５質量％以下であることが好ましく、２．５～４．０質量％であることがより好ましい。
本明細書において、上記ＨＦＰ単位等の「単量体単位」は、フッ素樹脂の分子構造上の一部分であって、対応する単量体に由来する部分を意味する。
PAVE in the above PFA is preferably one having an alkyl group having 1 to 6 carbon atoms, such as perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], or perfluoro(propyl vinyl ether) [PPVE]. is more preferable. In the above-mentioned PFA, the PAVE unit in the copolymer is preferably more than 2% by mass and 5% by mass or less, more preferably 2.5 to 4.0% by mass.
In the present specification, a "monomeric unit" such as the above-mentioned HFP unit means a part of the molecular structure of a fluororesin and is derived from a corresponding monomer.
上記ＰＦＡ、ＦＥＰは、それぞれ上述の組成を有するものであれば、更に、その他の単量体を重合させたものであってよい。上記その他の単量体として、例えば、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。上記その他の単量体は、１種又は２種以上を用いることができる。
上記その他の単量体は、その種類によって異なるが、通常、フッ素樹脂の質量の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％である。
The above-mentioned PFA and FEP may be those obtained by polymerizing other monomers, as long as they each have the above-mentioned composition. Examples of the above-mentioned other monomers include, for example, when the above-mentioned FEP is used, PAVE is further included, and when the above-mentioned PFA is used, further includes HFP. One type or two or more types of the above-mentioned other monomers can be used.
Although the amount of the other monomers mentioned above varies depending on the type thereof, it is usually preferable that the amount of the other monomers is 1% by mass or less based on the mass of the fluororesin. A more preferable upper limit is 0.5% by mass, and an even more preferable upper limit is 0.3% by mass.
上記ＰＦＡ、ＦＥＰは、それぞれＭＦＲが１０～３０（ｇ／１０ｍｉｎ）の範囲にあるものである。ＭＦＲが１０（ｇ／１０ｍｉｎ）未満であると、塗膜表面への移行が不充分となるおそれがある。ＭＦＲが３０（ｇ／１０ｍｉｎ）を超えると、分子量が低く塗膜強度が低下するため好ましくない。 The above PFA and FEP each have an MFR in the range of 10 to 30 (g/10 min). If the MFR is less than 10 (g/10 min), the transfer to the coating surface may be insufficient. If the MFR exceeds 30 (g/10 min), the molecular weight will be low and the strength of the coating will decrease, which is not preferable.
本明細書において、ＭＦＲは、ＡＳＴＭ Ｄ３３０７、Ｄ２１１６に準拠して、温度３７２℃、荷重５．０ｋｇの条件下で測定し得られる値である。
上記ＭＦＲは、１５～２８（ｇ／１０ｍｉｎ）がより好ましい。
In this specification, MFR is a value measured under conditions of a temperature of 372° C. and a load of 5.0 kg in accordance with ASTM D3307 and D2116.
The above MFR is more preferably 15 to 28 (g/10min).
上記ＰＦＡ、ＦＥＰは、それぞれ平均粒子径が０．０１～５μｍであることが好ましい。０．０１μｍ未満であると、フッ素樹脂からなる粒子の機械的安定性が悪く、得られるプライマー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。５μｍを超えると、フッ素樹脂からなる粒子の均一分散性に欠け、得られるプライマー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０．５μｍであり、より好ましい下限は０．０５μｍである。 The above PFA and FEP each preferably have an average particle diameter of 0.01 to 5 μm. If it is less than 0.01 μm, the mechanical stability of the fluororesin particles may be poor, and the resulting primer composition may have poor mechanical stability and storage stability. If it exceeds 5 μm, the fluororesin particles will lack uniform dispersibility, and when the resulting primer composition is used for coating, a coating film with a smooth surface may not be obtained, and the physical properties of the coating film may be poor. A more preferable upper limit is 0.5 μm, and a more preferable lower limit is 0.05 μm.
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。
本明細書において、上記フッ素樹脂の平均粒子径は、透過型電子顕微鏡観察により測定したものである。
The above-mentioned mechanical stability refers to the property that it is difficult to form aggregates that cannot be redispersed even when strong stirring or shearing force is applied using a homogenizer or the like during liquid feeding and redispersion.
In this specification, the average particle diameter of the fluororesin is measured by transmission electron microscopy.
上記ＰＦＡ及びＦＥＰは、合計含有量が組成物の１０～４０質量％の範囲であることが好ましい。上記合計含有量が１０質量％未満であると、プライマー層とトップコート層との密着性が低下するおそれがある。上記合計含有量が４０質量％を超えると、プライマー層の強度が低下しやすく、さらに基材との密着性も低下するおそれがある。上記ＰＦＡ及びＦＥＰの合計含有量が組成物の１５～３５質量％の範囲であることがより好ましい。 The total content of the PFA and FEP is preferably in the range of 10 to 40% by mass of the composition. If the total content is less than 10% by mass, the adhesion between the primer layer and the top coat layer may be reduced. If the total content exceeds 40% by mass, the strength of the primer layer tends to decrease, and the adhesion to the base material may also decrease. More preferably, the total content of PFA and FEP is in the range of 15 to 35% by mass of the composition.
また、上記〔ＰＦＡ〕／〔ＦＥＰ〕の質量比は、１０／９０～９０／１０の範囲にある。
上記質量比は、２０／８０～８０／２０の範囲がより好ましい。
Further, the mass ratio of [PFA]/[FEP] is in the range of 10/90 to 90/10.
The above mass ratio is more preferably in the range of 20/80 to 80/20.
本開示のプライマー塗料組成物は、本願の効果を損なわない範囲で、ポリテトラフルオロエチレン〔ＰＴＦＥ〕等の他のフッ素樹脂を含むものであってもよい。また、本願の効果を損なわない範囲で、ＭＦＲが上記範囲外であるＰＦＡ及びＦＥＰを含むものであってもよい。 The primer coating composition of the present disclosure may contain other fluororesins such as polytetrafluoroethylene [PTFE] as long as the effects of the present application are not impaired. Further, PFA and FEP whose MFR is outside the above range may be included as long as the effects of the present application are not impaired.
（バインダー樹脂）
本開示のプライマー組成物は、バインダー樹脂を含有することにより、被塗装物との密着性に優れ、 更に耐食性や耐水蒸気性が良い塗膜を得ることができる。
上記バインダー樹脂は、１５０℃以上の温度で耐熱性を示すものである。上記バインダー樹脂は、一般 に、アミド結合やイミド結合等、被塗装物との接着性を示す分子構造や官能基を有するので、被塗装物との接着性を示す。
(binder resin)
By containing the binder resin, the primer composition of the present disclosure has excellent adhesion to the object to be coated, and can also provide a coating film with good corrosion resistance and water vapor resistance.
The binder resin exhibits heat resistance at a temperature of 150° C. or higher. The above-mentioned binder resin generally has a molecular structure or a functional group, such as an amide bond or an imide bond, that exhibits adhesiveness to the object to be coated, and thus exhibits adhesiveness to the object to be coated.
本開示のプライマー組成物は、バインダー樹脂として、ポリアミドイミド〔ＰＡＩ〕及びポリエーテルサルフォン〔ＰＥＳ〕を必須として含むものである。
上記ＰＡＩは、分子構造中にアミド結合及びイミド結合を有する重合体からなる樹脂である。上記ＰＡＩとしては特に限定されず、例えば、アミド結合を分子内に有する芳香族ジアミンとピロメリット酸等の芳香族四価カルボン酸との反応；無水トリメリット酸等の芳香族三価カルボン酸と４，４－ジアミノフェニルエーテル等のジアミンやジフェニルメタンジイソシアネート等のジイソシアネートとの反応；芳香族イミド環を分子内に有する二塩基酸とジアミンとの反応等の各反応により得られる高分子量重合体からなる樹脂等が挙げられる。上記ＰＡＩとしては、耐熱性に優れる点から、主鎖中に芳香環を有する重合体からなるものが好ましい。
The primer composition of the present disclosure essentially contains polyamideimide [PAI] and polyether sulfone [PES] as binder resins.
The above-mentioned PAI is a resin made of a polymer having an amide bond and an imide bond in its molecular structure. The above-mentioned PAI is not particularly limited, and includes, for example, the reaction between an aromatic diamine having an amide bond in its molecule and an aromatic tetravalent carboxylic acid such as pyromellitic acid; Consists of high molecular weight polymers obtained by various reactions such as reaction with diamines such as 4,4-diaminophenyl ether and diisocyanates such as diphenylmethane diisocyanate; reaction with diamines and dibasic acids having an aromatic imide ring in the molecule. Examples include resin. The above-mentioned PAI is preferably made of a polymer having an aromatic ring in the main chain from the viewpoint of excellent heat resistance.
上記ＰＥＳは、下記式： The above PES is the following formula:
で表される繰り返し単位を有する重合体からなる樹脂である。
It is a resin made of a polymer having a repeating unit represented by:
上記ＰＥＳとしては特に限定されず、例えば、ジクロロジフェニルスルホンとビスフェノールとの重縮合により得られる重合体からなる樹脂等が挙げられる。 The above-mentioned PES is not particularly limited, and examples thereof include resins made of polymers obtained by polycondensation of dichlorodiphenylsulfone and bisphenol.
上記ＰＡＩとＰＥＳの合計含有量は、組成物の１０～４０質量％であることが好ましく、１５～３５質量％であることがより好ましい。
また、ＰＡＩ／ＰＥＳの質量比は、１／９９～６０／４０である。上記質量比が１／９９未満であると、プライマー組成物から得られる塗膜の基材との密着性が低下するおそれがあり、６０／４０を超えると、塗膜のトップコート層との密着性が低下するおそれがある。
The total content of PAI and PES is preferably 10 to 40% by weight, more preferably 15 to 35% by weight of the composition.
Further, the mass ratio of PAI/PES is 1/99 to 60/40. If the above mass ratio is less than 1/99, there is a risk that the adhesion of the paint film obtained from the primer composition to the base material will decrease, and if it exceeds 60/40, the adhesion of the paint film to the top coat layer may decrease. There is a risk that performance may deteriorate.
上記バインダー樹脂は、平均粒子径が０．１～１０μｍであることが好ましい。上記バインダー樹脂の平均粒子径が上記範囲内であると、得られる塗膜の耐食性が良好である。上記バインダー樹脂の平均粒子径が０．２～８μｍであることがより好ましい。 The binder resin preferably has an average particle diameter of 0.1 to 10 μm. When the average particle diameter of the binder resin is within the above range, the resulting coating film has good corrosion resistance. It is more preferable that the average particle diameter of the binder resin is 0.2 to 8 μm.
本明細書において、上記バインダー樹脂の平均粒子径は、株式会社堀場製作所製超遠心式自動粒度分布測定装置ＣＡＰＡ－７００型を用いて測定したものである。 In this specification, the average particle diameter of the binder resin is measured using an ultracentrifugal automatic particle size distribution analyzer model CAPA-700 manufactured by Horiba, Ltd.
本開示のプライマー組成物は、他のバインダー樹脂を含むものであってもよい。他のバインダー樹脂としては、例えば、ポリイミド樹脂〔ＰＩ〕、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、ポリフェニレンサルファイド〔ＰＰＳ〕で代表されるポリアリレンサルファイド樹脂等を挙げることができる。 The primer composition of the present disclosure may also contain other binder resins. Examples of other binder resins include polyimide resin [PI], polyetherimide resin, polyetheretherketone resin, aromatic polyester resin, and polyarylene sulfide resin represented by polyphenylene sulfide [PPS]. can.
本開示のプライマー組成物において、フッ素樹脂とバインダー樹脂との固形分質量比は、バインダー樹 脂：フッ素樹脂＝１５：８５～８５：１５であることが好ましい。上記バインダー樹脂が上記フッ素樹脂と上記バインダー樹脂との合計固形分質量の１５質量％未満であると、上記バインダー樹脂が少ない ので、得られる塗膜と被塗装物との密着性が不充分となる。５０質量％を超えると、上記フッ素樹脂が少ないので、上記塗膜と上塗り塗膜との密着性が不充分となる。 In the primer composition of the present disclosure, the solid content mass ratio of the fluororesin to the binder resin is preferably binder resin:fluororesin = 15:85 to 85:15. If the binder resin is less than 15% by mass of the total solid mass of the fluororesin and the binder resin, the binder resin will be so small that the adhesion between the resulting coating film and the object to be coated will be insufficient. . When it exceeds 50% by mass, the amount of the fluororesin is so small that the adhesion between the coating film and the top coating film becomes insufficient.
上記固形分質量比は、バインダー樹脂：フッ素樹脂＝２５：７５～７５：２５であることがより好ましく、バインダー樹脂：フッ素樹脂＝３５：６５～６５：３５であることがさらに好ましい。 The solid content mass ratio is more preferably binder resin: fluororesin = 25:75 to 75:25, and even more preferably binder resin: fluororesin = 35:65 to 65:35.
上記固形分質量比は、調製時に配合したフッ素樹脂とバインダー樹脂の量から算出したものである。 The above solid content mass ratio is calculated from the amounts of fluororesin and binder resin blended at the time of preparation.
（液状媒体（Ａ））
上記液状媒体（Ａ）は、沸点が１００℃未満の液状媒体である。上記液状媒体（Ａ）としては特に限定されず、フッ素樹脂への濡れ性を有するものであればよい。
上記液状媒体（Ａ）としては具体的に、メチルエチルケトン、エタノール、アセトン、ベンゼン等が挙げられ、１種又は２種以上用いることができる。
(Liquid medium (A))
The liquid medium (A) has a boiling point of less than 100°C. The liquid medium (A) is not particularly limited, and may be any medium as long as it has wettability to the fluororesin.
Specific examples of the liquid medium (A) include methyl ethyl ketone, ethanol, acetone, and benzene, and one or more of them can be used.
上記液状媒体（Ａ）の含有量は、組成物中に１～３０質量％である。上記含有量が１質量％未満であると、フッ素樹脂の移行が不充分となるおそれがある。上記含有量が３０質量％を超えると、フッ素樹脂の移行が過多となりプライマー層中の凝集破壊が発生し易くなるため好ましくない。上記液状媒体（Ａ）の含有量は、組成物中３～２５質量％がより好ましい。 The content of the liquid medium (A) in the composition is 1 to 30% by mass. If the content is less than 1% by mass, the transfer of the fluororesin may become insufficient. If the content exceeds 30% by mass, the fluororesin transfers excessively and cohesive failure in the primer layer is likely to occur, which is not preferable. The content of the liquid medium (A) is more preferably 3 to 25% by mass in the composition.
（液状媒体（Ｂ））
上記液状媒体（Ｂ）は、沸点が１００～１５０℃の液状媒体である。上記液状媒体（Ｂ）としては特に限定されず、上記液状媒体（Ａ）と同様フッ素樹脂への濡れ性を有するものであればよい。
上記液状媒体（Ｂ）としては具体的に、１－ブタノール、メチルイソブチルケトン、酢酸ブチル、トルエン、キシレン等が挙げられ、１種又は２種以上用いることができる。上記液状媒体（Ｂ）の含有量は、組成物中３～２５質量％がより好ましい。
(Liquid medium (B))
The liquid medium (B) has a boiling point of 100 to 150°C. The liquid medium (B) is not particularly limited as long as it has wettability to the fluororesin like the liquid medium (A).
Specific examples of the liquid medium (B) include 1-butanol, methyl isobutyl ketone, butyl acetate, toluene, xylene, etc., and one or more of them can be used. The content of the liquid medium (B) is more preferably 3 to 25% by mass in the composition.
上記液状媒体（Ｂ）の含有量は、組成物中に１～３０質量％である。上記含有量が１質量％未満であると、フッ素樹脂の移行が不充分となるおそれがある。上記含有量が３０質量％を超えると、フッ素樹脂の移行が過多となりプライマー層中の凝集破壊が発生し易くなるため好ましくない。
上記液状媒体（Ａ）及び（Ｂ）の含有量は、２種以上を併用する場合、その合計含有量である。
The content of the liquid medium (B) in the composition is 1 to 30% by mass. If the content is less than 1% by mass, the transfer of the fluororesin may become insufficient. If the content exceeds 30% by mass, the fluororesin transfers excessively and cohesive failure in the primer layer is likely to occur, which is not preferable.
The content of the liquid media (A) and (B) is the total content when two or more types are used together.
本開示のプライマー組成物は、分散媒として上記液状媒体（Ａ）（Ｂ）以外の有機溶剤を使用するものであることが好ましい。上記分散媒としての有機溶剤は、上記フッ素樹脂の分散性、及び、上記バインダー樹脂の分散性又は溶解性に優れた化合物であることが好ましい。このような有機溶剤としては特に限定されず、具体的には、バインダー樹脂の溶解、分散が可能であり沸点２００℃以上という性質を満たすものであることが好ましい。
具体的には、例えば、ジアセトンアルコール等の低級アルコール類；ケトン類；エステル類；Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－ブチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド等のアミド類；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類等が挙げられ、１種又は２種以上用いることができる。
上記分散媒としては、水と上記有機溶剤との混合溶剤も使用可能である。
The primer composition of the present disclosure preferably uses an organic solvent other than the liquid media (A) and (B) above as a dispersion medium. The organic solvent as the dispersion medium is preferably a compound that has excellent dispersibility of the fluororesin and excellent dispersibility or solubility of the binder resin. Such an organic solvent is not particularly limited, and specifically, it is preferably one that can dissolve and disperse the binder resin and has a boiling point of 200° C. or higher.
Specifically, for example, lower alcohols such as diacetone alcohol; ketones; esters; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N,N- Amides such as dimethylacetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropanamide; aromatic hydrocarbons such as trimethylbenzene, methylethylbenzene, propylbenzene, butylbenzene, etc.; One species or two or more species can be used.
As the dispersion medium, a mixed solvent of water and the organic solvent can also be used.
なお、上記「液状媒体（Ａ）（Ｂ）以外の有機溶剤」は、上述した液状媒体（Ａ）（Ｂ）の配合量においては、いずれにも該当しないものとして扱うべきものである。 Note that the above-mentioned "organic solvents other than liquid media (A) and (B)" should be treated as not corresponding to any of the above-mentioned blending amounts of liquid media (A) and (B).
上記液状媒体（Ａ）（Ｂ）以外の有機溶剤の含有量は、組成物中に２０～５０質量％であることが好ましい。上記含有量が２０質量％未満であると、バインダー樹脂の溶解、分散が不充分となるおそれがある。上記含有量が５０質量％を超えると、フッ素樹脂の割合が低下するため好ましくない。 The content of organic solvents other than the liquid medium (A) and (B) in the composition is preferably 20 to 50% by mass. If the content is less than 20% by mass, the binder resin may be insufficiently dissolved and dispersed. If the content exceeds 50% by mass, the proportion of the fluororesin decreases, which is not preferable.
本開示のプライマー組成物は、実質的にＮ－メチル－２－ピロリドンを含有しないものであってもよい。本明細書において、実質的に含有しないとは、Ｎ－メチル－２－ピロリドンの含有量が組成物の１質量％未満であることを意味する。Ｎ－メチル－２－ピロリドンは溶解能に優れた溶媒であるが、表面張力が高すぎて基材への濡れ性が不充分で、良好な接着性が得ることが困難であるという問題もあった。Ｎ－メチル－２－ピロリドンを実質的に使用しないプライマー組成物とすることで、より良好な接着性を得ることができる点で好ましい。
さらに、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミドの様にＮ－メチル－２－ピロリドンより表面張力の低い溶剤を主溶剤とすることで、フッ素樹脂を良く濡らし塗料中の凝集を防ぐため、貯蔵安定性が良好になる。フッ素樹脂の凝集が発生した場合、焼成時にフッ素樹脂が塗膜表面に移行し難くなり、剥離強度が低下する。
The primer composition of the present disclosure may be substantially free of N-methyl-2-pyrrolidone. As used herein, "substantially not containing" means that the content of N-methyl-2-pyrrolidone is less than 1% by mass of the composition. Although N-methyl-2-pyrrolidone is a solvent with excellent solubility, it also has problems in that its surface tension is too high and its wettability to the substrate is insufficient, making it difficult to obtain good adhesion. Ta. It is preferable to use a primer composition that does not substantially use N-methyl-2-pyrrolidone because better adhesion can be obtained.
Furthermore, by using a solvent such as 3-methoxy-N,N-dimethylpropanamide, which has a lower surface tension than N-methyl-2-pyrrolidone, as the main solvent, it wets the fluororesin well and prevents agglomeration in the paint. Good storage stability. When agglomeration of the fluororesin occurs, it becomes difficult for the fluororesin to migrate to the coating surface during baking, resulting in a decrease in peel strength.
本開示のプライマー組成物は、必要に応じ、その他の樹脂を含有す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、プライマー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。 The primer composition of the present disclosure may contain other resins as necessary. By blending the other resins mentioned above, the film forming properties, corrosion resistance, etc. of the coating film obtained from the primer composition can be improved.
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 resins mentioned above are not particularly limited, and include, for example, phenol resin, urea resin, epoxy resin, urethane resin, melamine resin, polyester resin, polyether resin, acrylic resin, acrylic silicone resin, silicone resin, silicone polyester resin, etc. Can be mentioned.
本開示のプライマー組成物は、塗装性、プライマー組成物から得られる塗膜の性質向上等を目的として、本開示の特徴を損なわない範囲で、更に一般的なコーティング用組成物に用いられる添加剤を配合してなるものであってもよい。 The primer composition of the present disclosure further includes additives used in general coating compositions, to the extent that the characteristics of the present disclosure are not impaired, for the purpose of improving paintability and properties of the coating film obtained from the primer composition. It may also be made by blending.
上記添加剤としては特に限定されず、得られる被覆物品の用途に応じて選択することができ、例えば、レベリング剤、固体潤滑剤、木粉、石英砂、カーボンブラック、ダイヤモンド、トルマリン、ゲルマニウム、アルミナ、窒化珪素、蛍石、クレー、タルク、体質顔料、各種増量材、導電性フィラー、光輝材、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。
上記光輝材としては、例えば、マイカ、金属粉末、ガラスビーズ、ガラスバブル、ガラスフレーク、ガラス繊維等が挙げられる。
The above additives are not particularly limited and can be selected depending on the intended use of the resulting coated article, such as leveling agents, solid lubricants, wood flour, quartz sand, carbon black, diamond, tourmaline, germanium, alumina, etc. , silicon nitride, fluorite, clay, talc, extender pigments, various extenders, conductive fillers, bright materials, pigments, fillers, pigment dispersants, anti-settling agents, moisture absorbers, surface conditioning agents, thixotropic agents , viscosity modifier, anti-gelling agent, ultraviolet absorber, light stabilizer, plasticizer, anti-color separation agent, anti-skinning agent, anti-scratch agent, anti-mold agent, anti-bacterial agent, antioxidant, anti-static agent , silane coupling agents, and the like.
Examples of the glittering material include mica, metal powder, glass beads, glass bubbles, glass flakes, and glass fibers.
上記金属粉末としては特に限定されず、例えば、アルミニウム、鉄、すず、亜鉛、金、銀、銅等の金属単体の粉末；アルミニウム合金、ステンレス等の合金の粉末等が挙げられる。上記金属粉末の形状としては特に限定されず、例えば、粒子状、フレーク状等が挙げられる。本開示のプライマー組成物は、このような光輝材を含有する場合、優れた外観を有する塗膜を形成することができる。上記光輝材の含有量は、上記プライマー組成物の固形分に対して０．１～１０．０質量％であることが好ましい。 The above-mentioned metal powder is not particularly limited, and examples thereof include powders of simple metals such as aluminum, iron, tin, zinc, gold, silver, and copper; powders of alloys such as aluminum alloys and stainless steel; and the like. The shape of the metal powder is not particularly limited, and examples thereof include particles, flakes, and the like. When the primer composition of the present disclosure contains such a glittering material, it is possible to form a coating film having an excellent appearance. The content of the glittering material is preferably 0.1 to 10.0% by mass based on the solid content of the primer composition.
上記粘度調節剤としては、例えば、メチルセルロース、アルミナゾルが挙げられる。 Examples of the viscosity modifier include methyl cellulose and alumina sol.
本開示のプライマー組成物は、例えば、（１）フッ素樹脂、液状媒体（Ａ）、液状媒体（Ｂ）及び分散媒からなる分散液を調製した後、（２）得られた分散液にバインダー樹脂、必要に応じ、添加剤等を添加することにより得ることができる。なお、ここで、バインダー樹脂は、上記「液状媒体（Ａ）（Ｂ）以外の有機溶剤」に溶解した状態で使用することが好ましい。 In the primer composition of the present disclosure, for example, after (1) preparing a dispersion consisting of a fluororesin, a liquid medium (A), a liquid medium (B), and a dispersion medium, (2) adding a binder resin to the obtained dispersion, , can be obtained by adding additives and the like, if necessary. Here, the binder resin is preferably used in a state dissolved in the above-mentioned "organic solvent other than the liquid medium (A) and (B)".
本開示のプライマー組成物は、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、上記プライマー組成物についての「塗装」とは、上記プライマー組成物を塗布し、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 primer composition of the present disclosure is capable of forming a coating film on the object to be painted by applying the primer composition to the object. As used herein, "coating" with respect to the primer composition means a process consisting of applying the primer composition, drying if necessary, and then baking.
本開示のプライマー組成物は、被塗装物との密着性に加え、上塗り塗膜との密着性が良い塗膜を形成することができる。
本開示のプライマー組成物から得られる塗膜上に塗装する上塗り塗料としては、フッ素樹脂を含有する塗料が好ましい。この場合、上記塗膜は、上述のように塗膜表面側に配向しているフッ素樹脂が上塗り塗膜中のフッ素樹脂と親和性を示すゆえ、上塗り塗膜との間に優れた密着性を示す。
The primer composition of the present disclosure can form a coating film that has good adhesion to an object to be coated and also has good adhesion to an overcoat film.
As the top coating paint to be applied on the coating film obtained from the primer composition of the present disclosure, a paint containing a fluororesin is preferable. In this case, the above coating film has excellent adhesion with the top coating film because the fluororesin oriented on the surface side of the coating film has an affinity with the fluororesin in the top coat film as described above. show.
本開示のプライマー組成物から得られる塗膜は、上記プライマー組成物を被塗装物上に塗布し、乾燥することにより塗布膜を得た後、更に必要に応じ焼成することにより形成することができる。 The coating film obtained from the primer composition of the present disclosure can be formed by applying the primer composition onto an object to be coated, drying to obtain a coating film, and then further baking as necessary. .
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 object to be coated is not particularly limited, and includes, for example, metals such as iron, aluminum, copper, and alloys thereof; and non-metallic inorganic materials such as enamel, glass, and ceramics. Examples of the above-mentioned alloys include stainless steel and the like.
上記被塗装物は、上記プライマー組成物を均一に塗布することができる点、及び、被塗装物との密着性が向上する点で、予め脱脂処理、粗面化処理等の表面処理を行うことが好ましい。上記粗面化処理の方法としては特に限定されず、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。 The object to be painted should be subjected to surface treatment such as degreasing or roughening treatment in advance so that the primer composition can be applied uniformly and the adhesion to the object can be improved. is preferred. The method for the surface roughening treatment is not particularly limited, and examples thereof include chemical etching with acid or alkali, anodization (alumite treatment), sandblasting, and the like.
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。 The coating method is not particularly limited, and examples thereof include spray coating, roll coating, coating with a doctor blade, dip coating, impregnation coating, spin flow coating, curtain flow coating, and the like.
上記乾燥は、従来公知の方法により行うことができるが、６０～２００℃の温度で５～６０分間行うことが好ましい。 The above-mentioned drying can be carried out by a conventionally known method, but it is preferably carried out at a temperature of 60 to 200°C for 5 to 60 minutes.
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 above-mentioned coating film is usually not baked before applying the above-mentioned top coat, but may be baked if necessary. It is preferable not to perform baking before applying the above-mentioned top coat, since this can simplify the process and reduce energy, labor, time, and the like.
上記上塗り塗膜は、例えば、上記塗布膜上又は上記塗膜上に上塗り塗料を塗布し、次いで焼成することにより形成させることができる。 The above-mentioned top coat film can be formed by, for example, applying a top coat paint on or onto the above-mentioned coat film, and then baking it.
上記上塗り塗料におけるフッ素樹脂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、本開示のプライマー組成物における上記フッ素樹脂と同じもの、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。 The fluororesin in the top coat is not particularly limited, and examples thereof include PTFE, PFA, FEP, etc., but from the viewpoint of improving the interlayer adhesion between the above paint film and the top coat film, the primer composition of the present disclosure It is preferable to use the same fluororesin as the above-mentioned fluororesin, or one having similar properties such as the presence or absence of melt processability.
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が、ＰＦＡ系塗料が好ましい。 Examples of the top coating include PTFE-based paints whose main component is PTFE, PFA-based paints whose main component is PFA, and FEP-based paints whose main component is FEP, with PFA-based paints being preferred.
上記上塗り塗料は、塗装性、得られる塗膜の性質向上等を目的として、更に、上述のプライマー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。 The above-mentioned top coating may further contain additives similar to the various additives that can be used in the above-mentioned primer composition, for the purpose of improving the coating properties and the properties of the resulting coating film.
上記上塗り塗料は、主成分がＰＦＡ又はＦＥＰである場合、粉体塗料とすることができる。 The above-mentioned top coating can be a powder coating when the main component is PFA or FEP.
上記上塗り塗料の塗布の方法としては、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。 Examples of methods for applying the top coat, in the case of powder coatings, include electrostatic spray coating, fluidized dip coating, rotolining, and the like.
上記上塗り塗料を塗布した後の焼成は、それぞれ上述のプライマー組成物を塗布、乾燥した後に行う焼成と同様の条件で行うことができる。 The firing after applying the above-mentioned top coat can be performed under the same conditions as the firing performed after applying and drying the above-mentioned primer composition.
本開示のプライマー組成物から得られる塗膜及び上記上塗り塗膜の各膜厚は、特に限定されないが、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 thickness of the coating film obtained from the primer composition of the present disclosure and the top coating film are not particularly limited, but the thickness of the coating film is 1 to 100 μm, and the thickness of the top coating film is 10 to 100 μm. Preferably, it is 200 μm.
本開示の含フッ素樹脂積層体は、被塗装物、塗膜、及び、フッ素樹脂層からなるものである。上記塗膜は、上述のように、本開示のプライマー組成物の塗装により得られるものであり、上記含フッ素樹脂積層体において、上記被塗装物に本開示のプライマー組成物を塗装することにより得られるものである。上記フッ素樹脂層は、上述のフッ素樹脂を含有する上塗り塗料の塗装により得られるものである。本開示の含フッ素樹脂積層体において、上記被塗装物、上記塗膜及び上記フッ素樹脂層は、この順に積層している。 The fluorine-containing resin laminate of the present disclosure includes a coated object, a coating film, and a fluororesin layer. As mentioned above, the coating film is obtained by coating the primer composition of the present disclosure, and in the fluororesin laminate, the coating film is obtained by coating the object to be coated with the primer composition of the present disclosure. It is something that can be done. The above-mentioned fluororesin layer is obtained by applying a top coat containing the above-mentioned fluororesin. In the fluororesin laminate of the present disclosure, the object to be painted, the coating film, and the fluororesin layer are laminated in this order.
本開示の含フッ素樹脂積層体の用途としては特に限定されず、例えば、基材表面に耐熱性、非粘着性、滑り性等を要する製品として適用することができる。 The use of the fluororesin laminate of the present disclosure is not particularly limited, and can be applied, for example, to products that require heat resistance, non-adhesiveness, slipperiness, etc. on the surface of the base material.
このような用途として、例えば、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、ＯＡ用分離爪、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；のこぎり、やすり等の工具；アイロン、鋏等の家庭用品；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；自動車部品が挙げられる。 Examples of such uses include frying pans, grill pans, pressure cookers, various other pots, rice cookers, rice cake makers, ovens, hot plates, bread molds, knives, cooking utensils such as gas stoves; electric pots, ice trays, etc. Containers for food and drink such as kneading rolls, rolling rolls, conveyor hoppers, etc.; food industry parts such as kneading rolls, rolling rolls, conveyor hoppers; industries such as rolls for office automation equipment [OA], belts for OA, separation claws for OA, paper rolls, calendar rolls for film production, etc. Supplies: Molds for molding polystyrene foam, mold release plates such as release plates for plywood and decorative laminate production; Kitchen supplies such as range hoods; Frozen food production equipment such as conveyor belts; Tools such as saws and files; Household items such as irons and scissors; metal foils; sliding bearings for food processing machines, packaging machines, textile machines, etc.; sliding parts for cameras and watches; and automobile parts.
以上に例示した、上記含フッ素樹脂積層体を有する被覆物品もまた、本開示の一つである。 The coated article having the fluororesin laminate described above is also part of the present disclosure.
以下、本開示を実施例に基づいて具体的に説明する。
以下の実施例においては特に言及しない場合は、「部」「％」はそれぞれ「質量部」「質量％」を表す。
Hereinafter, the present disclosure will be specifically described based on Examples.
In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.
使用したフッ素樹脂粉末を以下に示す。
ＰＦＡ粒子Ａ：
ＭＦＲ：７（ｇ／１０ｍｉｎ）、融点：３０６℃、平均粒径：２３μｍ
ＰＦＡ粒子Ｂ：
ＭＦＲ：２８（ｇ／１０ｍｉｎ）、融点：３０１℃、平均粒径：２４μｍ
ＰＦＡ粒子Ｃ
ＭＦＲ：３７（ｇ／１０ｍｉｎ）、融点：２９８℃、平均粒径：２０μｍ
ＰＦＡ粒子Ｄ
ＭＦＲ：２９（ｇ／１０ｍｉｎ）、融点：３０１℃、平均粒径：０．３μｍ
The fluororesin powder used is shown below.
PFA particles A:
MFR: 7 (g/10min), melting point: 306°C, average particle size: 23 μm
PFA particles B:
MFR: 28 (g/10min), melting point: 301°C, average particle size: 24 μm
PFA particles C
MFR: 37 (g/10min), melting point: 298°C, average particle size: 20 μm
PFA particles D
MFR: 29 (g/10min), melting point: 301°C, average particle size: 0.3 μm
ＦＥＰ粒子Ａ
ＭＦＲ：２２（ｇ／１０ｍｉｎ）、融点：２５６℃、平均粒径：２０μｍ
ＦＥＰ粒子Ｂ
ＭＦＲ：９（ｇ／１０ｍｉｎ）、融点：２５４℃、平均粒径：０．３μｍ
ＦＥＰ粒子Ｃ
ＭＦＲ：２０（ｇ／１０ｍｉｎ）、融点：２５８℃、平均粒径：０．３μｍ
ＦＥＰ粒子Ｄ
ＭＦＲ：３５（ｇ／１０ｍｉｎ）、融点：２５６℃、平均粒径：０．２μｍ
FEP particle A
MFR: 22 (g/10min), melting point: 256°C, average particle size: 20 μm
FEP particles B
MFR: 9 (g/10min), melting point: 254°C, average particle size: 0.3 μm
FEP particle C
MFR: 20 (g/10min), melting point: 258°C, average particle size: 0.3 μm
FEP particles D
MFR: 35 (g/10min), melting point: 256°C, average particle size: 0.2 μm
実施例１～８、比較例１～１３
フッ素樹脂としてＰＦＡ粒子Ａ～Ｄのいずれか、および、ＦＥＰ粒子Ａ～Ｄのいずれか、バインダー樹脂としてポリアミドイミド（ＰＡＩ）ワニスＡ（昭和電工マテリアルズ社製、固形分２８％、Ｎ－メチルピロリドン溶液）、および、ポリエーテルサルフォン（ＰＥＳ）粉末（住友化学社製、数平均分子量２４０００）、Ｎ－メチルピロリドン、メチルイソブチルケトン、１－ブタノール、メチルエチルケトン、エタノール、ジアセトンアルコールを表１～３に示した所定の質量比で混合し、含フッ素溶剤型プライマー組成物を得た。
アルミナ粉（宇治電化学工業社製、トサエメリー＃４０）を用いて吹付け圧１．０ＭＰａでブラスト処理した鉄板（ＳＳ４００、表面粗度Ｒａ：２～３μｍ）上に、上記の含フッ素溶剤型プライマー組成物をスプレー塗装し、１５０℃で３０分間乾燥させた。さらにその上層にＰＦＡ粉末（ダイキン工業社製、ＡＣＸ－３４）を静電塗装し、３８０℃で２０分間焼成して、総膜厚４０μｍの積層体を得た。
Examples 1 to 8, Comparative Examples 1 to 13
Any of PFA particles A to D and any of FEP particles A to D were used as the fluororesin, and polyamideimide (PAI) varnish A (manufactured by Showa Denko Materials Co., Ltd., solid content 28%, N-methylpyrrolidone) was used as the binder resin. solution), and polyethersulfone (PES) powder (manufactured by Sumitomo Chemical Co., Ltd., number average molecular weight 24,000), N-methylpyrrolidone, methyl isobutyl ketone, 1-butanol, methyl ethyl ketone, ethanol, diacetone alcohol in Tables 1 to 3. A fluorine-containing solvent type primer composition was obtained by mixing at a predetermined mass ratio shown in .
The above fluorine-containing solvent-based primer was applied onto an iron plate (SS400, surface roughness Ra: 2 to 3 μm) that had been blasted with alumina powder (manufactured by Ujiden Chemical Industry Co., Ltd., Tosa Emery #40) at a spray pressure of 1.0 MPa. The composition was spray painted and dried at 150°C for 30 minutes. Furthermore, PFA powder (manufactured by Daikin Industries, Ltd., ACX-34) was electrostatically coated on the upper layer and baked at 380° C. for 20 minutes to obtain a laminate with a total film thickness of 40 μm.
使用した溶剤の沸点を以下に示す。
エタノール ７８．３℃
メチルエチルケトン ８０℃
メチルイソブチルケトン １１６℃
１－ブタノール １１７℃
ジアセトンアルコール １６６℃
Ｎ－メチル－２－ピロリドン ２０２℃
３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド ２１５℃
The boiling points of the solvents used are shown below.
Ethanol 78.3℃
Methyl ethyl ketone 80℃
Methyl isobutyl ketone 116℃
1-Butanol 117℃
Diacetone alcohol 166℃
N-methyl-2-pyrrolidone 202℃
3-methoxy-N,N-dimethylpropanamide 215°C
実施例９～１０
フッ素樹脂としてＰＦＡ粒子ＢとＦＥＰ粒子Ｃ、バインダー樹脂としてポリアミドイミド（ＰＡＩ）ワニスＢ（エランタス社製、固形分３６％、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド溶液）、および、ポリエーテルサルフォン（ＰＥＳ）粉末（住友化学社製、数平均分子量２４０００）、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、メチルイソブチルケトン、メチルエチルケトンを表３に示した所定の質量比で混合し、含フッ素溶剤型プライマー組成物を得た。
その後は実施例１と同様の手順を実施し、積層体を得た。
Examples 9-10
PFA particles B and FEP particles C as fluororesins, polyamideimide (PAI) varnish B (manufactured by Elantus, solid content 36%, 3-methoxy-N,N-dimethylpropanamide solution) as binder resins, and polyether sal. PES powder (manufactured by Sumitomo Chemical Co., Ltd., number average molecular weight 24,000), 3-methoxy-N,N-dimethylpropanamide, methyl isobutyl ketone, and methyl ethyl ketone were mixed at the predetermined mass ratio shown in Table 3, and fluorine-containing A solvent-based primer composition was obtained.
Thereafter, the same procedure as in Example 1 was carried out to obtain a laminate.
（剥離強度）
上記得られた積層体の剥離強度を以下の方法により測定した。
ＪＩＳ Ｋ ６８５４－１に準拠して、テンシロン万能試験機を用いて試験片に対して９０°方向に引張速度５０ｍｍ／ｍｉｎにて剥離強度を測定した。
また、剥離が生じた箇所を以下のように示す。
Ａ：トップコート層の破壊
Ｂ：プライマー層の破壊
Ｃ：トップコート層／プライマー層間の剥離
(Peel strength)
The peel strength of the laminate obtained above was measured by the following method.
In accordance with JIS K 6854-1, the peel strength of the test piece was measured in a 90° direction at a tensile rate of 50 mm/min using a Tensilon universal testing machine.
In addition, the locations where peeling occurred are shown below.
A: Destruction of top coat layer B: Destruction of primer layer C: Peeling between top coat layer/primer layer
（塗料貯蔵後の剥離強度）
また、実施例５、６、９、１０で得た含フッ素溶剤型プライマー組成物については、さらに、５０℃で１ヶ月間静置させた後にも、実施例１と同様の手順を実施し、積層体の接着性を評価した。
(Peel strength after paint storage)
Furthermore, for the fluorine-containing solvent-based primer compositions obtained in Examples 5, 6, 9, and 10, the same procedure as in Example 1 was carried out after allowing them to stand at 50°C for one month. The adhesion of the laminate was evaluated.
表１～３の結果より、実施例で得られた含フッ素樹脂積層体は、充分な剥離強度を有することが示された。また、実施例で得られた含フッ素樹脂積層体は、トップコート層の破壊が生じているのに対し、比較例ではプライマー層の破壊、または、トップコート層/プライマー層の剥離が生じていることからも、本開示のプライマー組成物が充分な塗膜強度と密着性とを有することが明らかである。
さらに、実施例５、６、９及び１０のプライマー組成物において、５０℃で１ヶ月間静置させた後に得られた含フッ素樹脂積層体も良好な剥離強度を有することから、本開示のプライマー組成物は優れた貯蔵安定性を有することが示された。
From the results in Tables 1 to 3, it was shown that the fluororesin laminates obtained in Examples had sufficient peel strength. Furthermore, in the fluororesin laminates obtained in the examples, the top coat layer was destroyed, whereas in the comparative examples, the primer layer was destroyed or the top coat layer/primer layer peeled off. From this, it is clear that the primer composition of the present disclosure has sufficient coating film strength and adhesion.
Furthermore, in the primer compositions of Examples 5, 6, 9, and 10, the fluororesin laminates obtained after being allowed to stand at 50°C for one month also had good peel strength. The composition was shown to have excellent storage stability.
本開示のプライマー組成物は、被塗装物に対する密着性と、フッ素樹脂層に対する密着性とを同時に有する塗膜を形成できる塗料組成物であり、フッ素樹脂層のプライマーとして好適に使用することができる。 The primer composition of the present disclosure is a coating composition that can form a coating film that has both adhesion to an object to be coated and adhesion to a fluororesin layer, and can be suitably used as a primer for a fluororesin layer. .
Claims (5)
前記フッ素樹脂は、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）であるテトラフルオロエチレン〔ＴＦＥ〕／パーフルオロ（アルキルビニルエーテル）〔ＰＡＶＥ〕共重合体〔ＰＦＡ〕、及び、メルトフローレート（ＭＦＲ）が１０～３０（ｇ／１０ｍｉｎ）である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〕共重合体〔ＦＥＰ〕を含み、
〔ＰＦＡ〕／〔ＦＥＰ〕の質量比は、１０／９０～９０／１０の範囲にあり、
前記バインダー樹脂は、ポリアミドイミド〔ＰＡＩ〕及びポリエーテルサルフォン〔ＰＥＳ〕を含み、〔ＰＡＩ〕／〔ＰＥＳ〕の質量比が１／９９～６０／４０の範囲にあり、
〔ＰＦＡ〕及び〔ＦＥＰ〕の合計含有量が組成物の１０～４０質量％、並びに、〔ＰＡＩ〕及び〔ＰＥＳ〕の合計含有量が組成物の１０～４０質量％の範囲にあり、
さらに、沸点１００℃未満の液状媒体（Ａ）を組成物中に１～３０質量％、及び、沸点１００～１５０℃の液状媒体（Ｂ）を組成物中に１～３０質量％含む
ことを特徴とする含フッ素樹脂溶剤型プライマー組成物。 A fluororesin solvent-based primer composition in which a fluororesin and a binder resin are dispersed in a liquid medium,
The fluororesin is a tetrafluoroethylene [TFE]/perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA] having a melt flow rate (MFR) of 10 to 30 (g/10 min), and a melt flow rate Contains a tetrafluoroethylene [TFE]/hexafluoropropylene [HFP] copolymer [FEP] having a (MFR) of 10 to 30 (g/10 min),
The mass ratio of [PFA]/[FEP] is in the range of 10/90 to 90/10,
The binder resin includes polyamideimide [PAI] and polyethersulfone [PES], and the mass ratio of [PAI ] / [PES] is in the range of 1/99 to 60/40,
The total content of [PFA] and [FEP] is in the range of 10 to 40% by mass of the composition, and the total content of [PAI] and [PES] is in the range of 10 to 40% by mass of the composition,
Furthermore, the composition contains 1 to 30% by mass of a liquid medium (A) with a boiling point of less than 100°C, and 1 to 30% by mass of a liquid medium (B) with a boiling point of 100 to 150°C. A fluorine-containing resin solvent-type primer composition.
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| JP4034784B2 (en) * | 2005-01-12 | 2008-01-16 | 日本フッソ工業株式会社 | Primer layer |
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| WO2016147790A1 (en) * | 2015-03-13 | 2016-09-22 | ダイキン工業株式会社 | Coating composition and coated article |
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