JP2021175763A - Coating material, coating film-equipped substrate, and method for producing coating film-equipped substrate - Google Patents

Coating material, coating film-equipped substrate, and method for producing coating film-equipped substrate Download PDF

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Publication number
JP2021175763A
JP2021175763A JP2018135259A JP2018135259A JP2021175763A JP 2021175763 A JP2021175763 A JP 2021175763A JP 2018135259 A JP2018135259 A JP 2018135259A JP 2018135259 A JP2018135259 A JP 2018135259A JP 2021175763 A JP2021175763 A JP 2021175763A
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Prior art keywords
coating film
paint
mass
fluorine
graphene
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Inventor
チン ヤン シェン セドリック
Chin Yan Sheng Cedric
俊 齋藤
Takashi Saito
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2018135259A priority Critical patent/JP2021175763A/en
Priority to CN201980048054.6A priority patent/CN112437795A/en
Priority to PCT/JP2019/028134 priority patent/WO2020017563A1/en
Publication of JP2021175763A publication Critical patent/JP2021175763A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • 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
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Abstract

To provide a coating material capable of forming a coating film which exhibits excellent light resistance, a coating film-equipped substrate, and a method for producing a coating film-equipped substrate.SOLUTION: A coating material contains graphene and a fluorine-containing polymer, where the layer thickness of the graphene is 0.1-100 nm, the specific surface area thereof is 50-1,500 m2/g, and the fluorine-containing polymer has a hydroxyl value and/or acid value of 10-150 mgKOH/g.SELECTED DRAWING: None

Description

本発明は、塗料、塗膜付き基材、および塗膜付き基材の製造方法に関する。 The present invention relates to a coating material, a coated base material, and a method for producing a coated base material.

橋梁、高速道路、送電鉄塔といった屋外構造物は、過酷な環境に長期に渡って曝されるため、重防食用塗料の塗膜で保護されている。特許文献１には、金属基材表面に下地層および上塗り層を有する重防食塗装構造が開示されている。 Outdoor structures such as bridges, highways, and transmission towers are protected by heavy-duty anticorrosion paints because they are exposed to harsh environments for long periods of time. Patent Document 1 discloses a heavy-duty anticorrosion coating structure having a base layer and a topcoat layer on the surface of a metal base material.

特開２０１４−２００９９７号公報Japanese Unexamined Patent Publication No. 2014-200997

重防食用塗料の塗膜は、太陽光にも長期に渡って曝されうる。この場合、太陽光に含まれる紫外線によって塗膜が劣化する場合がある。本発明者らは、特許文献１に記載の塗膜を有する塗膜付き基材では、紫外線に対する耐光性が充分でなく、重防食用塗料の塗膜として要求される耐候性に課題があることを知見した。 The coating film of heavy-duty anticorrosion paint can also be exposed to sunlight for a long period of time. In this case, the coating film may be deteriorated by the ultraviolet rays contained in sunlight. The present inventors have insufficient light resistance to ultraviolet rays in the coated base material having the coating film described in Patent Document 1, and have a problem in the weather resistance required as a coating film of a heavy-duty anticorrosion paint. Was found.

本発明は、耐光性に優れる塗膜を形成できる塗料、塗膜付き基材、および塗膜付き基材の製造方法の提供を目的とする。 An object of the present invention is to provide a coating film capable of forming a coating film having excellent light resistance, a base material with a coating film, and a method for producing a base material with a coating film.

本発明者らは、鋭意検討した結果、以下の構成により課題を解決できるのを見出した。 As a result of diligent studies, the present inventors have found that the problem can be solved by the following configuration.

［１］グラフェンおよび含フッ素重合体を含む塗料であって、上記グラフェンは、層厚みが０．１〜１００ｎｍであり、比表面積が５０〜１，５００ｍ２／ｇであり、上記含フッ素重合体は、水酸基価および酸価の一方または両方が１０〜１５０ｍｇＫＯＨ／ｇであることを特徴とする塗料。
［２］上記グラフェンは、平均最長粒子径が０．００１〜５０μｍである、［１］の塗料。
［３］上記グラフェンは、上記グラフェンの全質量に対して８５質量％以上の炭素原子を含む、［１］または［２］の塗料。
［４］上記塗料の固形分質量に対して上記グラフェンを０．０１〜１０質量％含む、［１］〜［３］のいずれかの塗料。
［５］酸化チタン顔料を含む、［１］〜［４］のいずれかの塗料。
［６］上記含フッ素重合体は、数平均分子量が２，０００〜３０，０００である、［１］〜［５］のいずれかの塗料。
［７］数平均分子量が１００〜９００である硬化剤を含む、［１］〜［６］のいずれかの塗料。
［８］上記塗料がさらに溶媒を含み、上記塗料の全質量に対する上記溶媒の質量が、２０〜３５質量％である、［１］〜［７］のいずれかの塗料。
［９］２５℃における粘度が３００〜３，０００ｍＰａ・ｓである、［８］の塗料。
［１０］上記含フッ素重合体は、フルオロオレフィンに基づく単位と、ヒドロキシ基およびカルボキシ基の一方または両方を有しフッ素原子を有さない単位と、を含む、［１］〜［９］のいずれかの塗料。
［１１］［１］〜［１０］のいずれかの塗料から形成される、膜厚が５０〜１００μｍである塗膜。
［１２］基材と、亜鉛末およびグラフェンを含む下塗り層と、［１１］の塗膜からなる上塗り層と、をこの順に有する塗膜付き基材。
［１３］基材上に、下塗り塗料を塗布して下塗り層を形成し、上記下塗り層上に、［１］〜［１０］のいずれかの塗料を塗布して上塗り層を形成して、前記基材と、上記下塗り層および上記上塗り層を有する塗膜とをこの順に有する塗膜付き基材を得る、塗膜付き基材の製造方法。 [1] A coating material containing graphene and a fluorine-containing polymer, wherein the graphene has a layer thickness of 0.1 to 100 nm, a specific surface area of 50 to 1,500 m 2 / g, and the fluorine-containing polymer. Is a coating material characterized in that one or both of the hydroxyl value and the acid value are 10 to 150 mgKOH / g.
[2] The graphene is the coating material of [1], which has an average longest particle size of 0.001 to 50 μm.
[3] The graphene is the coating material of [1] or [2], which contains 85% by mass or more of carbon atoms with respect to the total mass of the graphene.
[4] The coating material according to any one of [1] to [3], which contains 0.01 to 10% by mass of the graphene with respect to the solid content mass of the coating material.
[5] The paint according to any one of [1] to [4], which contains a titanium oxide pigment.
[6] The fluorine-containing polymer is the coating material according to any one of [1] to [5], which has a number average molecular weight of 2,000 to 30,000.
[7] The coating material according to any one of [1] to [6], which comprises a curing agent having a number average molecular weight of 100 to 900.
[8] The coating material according to any one of [1] to [7], wherein the coating material further contains a solvent, and the mass of the solvent is 20 to 35% by mass with respect to the total mass of the coating material.
[9] The coating material of [8] having a viscosity at 25 ° C. of 300 to 3,000 mPa · s.
[10] Any of [1] to [9], wherein the fluorine-containing polymer contains a unit based on a fluoroolefin and a unit having one or both of a hydroxy group and a carboxy group and no fluorine atom. That paint.
[11] A coating film having a film thickness of 50 to 100 μm, which is formed from the paint according to any one of [1] to [10].
[12] A base material with a coating film having a base material, an undercoat layer containing zinc powder and graphene, and a topcoat layer composed of the coating film of [11] in this order.
[13] An undercoat paint is applied onto the base material to form an undercoat layer, and any of the paints [1] to [10] is applied onto the undercoat layer to form an overcoat layer. A method for producing a base material with a coating film, which obtains a base material with a coating film having the base material, the undercoat layer, and the coating film having the topcoat layer in this order.

本発明によれば、耐光性に優れる塗膜を形成できる塗料、塗膜付き基材、および塗膜付き基材の製造方法を提供できる。 According to the present invention, it is possible to provide a coating material capable of forming a coating film having excellent light resistance, a base material with a coating film, and a method for producing a base material with a coating film.

本発明における用語の意味は以下の通りである。
「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
「（メタ）アクリレート」とは、「アクリレート」および「メタクリレート」の総称であり、「（メタ）アクリル」とは、「アクリル」および「メタクリル」の総称である。
「単位」とは、単量体が重合して直接形成された、上記単量体１分子に基づく原子団と、上記原子団の一部を化学変換して得られる原子団との総称である。なお、重合体が含む全単位に対する、それぞれの単位の含有量（モル％）は、重合体を核磁気共鳴スペクトル（ＮＭＲ）法により分析して求められる。
「酸価」と「水酸基価」は、それぞれ、ＪＩＳ Ｋ ００７０−３（１９９２）の方法に準じて測定される値である。
「ガラス転移温度」は、示差走査熱量測定（ＤＳＣ）法で測定される、重合体の中間点ガラス転移温度である。「ガラス転移温度」は「Ｔｇ」ともいう。
「最低造膜温度」は、含フッ素重合体を乾燥させたとき、亀裂のない均一な塗膜が形成される最低温度であり、造膜温度測定装置ＩＭＣ−１５３５型（株式会社井元製作所製）を用いて測定される値である。「最低造膜温度」は、「ＭＦＴ」ともいう。
「軟化温度」は、ＪＩＳ Ｋ ７１９６（１９９１）の方法に準じて測定される値である。
「数平均分子量」および「重量平均分子量」は、ポリスチレンを標準物質としてゲルパーミエーションクロマトグラフィーで測定される値である。「数平均分子量」は「Ｍｎ」ともいい、「重量平均分子量」は「Ｍｗ」ともいう。
塗膜の膜厚は、渦電流式膜厚計（商品名「ＥＤＹ−５０００」、サンコウ電子社製）を用いて測定される値である。塗膜が複数種の塗膜が積層されている積層構造を有する場合、各層の厚みは、エネルギー分散型Ｘ線分析装置を備えた走査型電子顕微鏡によって塗膜の断面を観察して得られる各層の厚みの比と、塗膜全体の膜厚とから算出される値である。
グラフェンの層厚みは、エネルギー分散型Ｘ線分析装置を備えた走査型電子顕微鏡によって測定される値の平均値である。
グラフェンの比表面積は、ＢＥＴ法により得られる値の平均値である。
グラフェンまたはグラファイトの平均最長粒子径は、エネルギー分散型Ｘ線分析装置を備えた走査型電子顕微鏡によって測定される、グラフェンまたはグラファイトの層厚さ方向に垂直な平面における最長長さの平均値である。
亜鉛末または粉体塗料の平均粒子径は、レーザー回折法を測定原理とした公知の粒度分布測定装置（Ｓｙｍｐａｔｅｃ社製、商品名「Ｈｅｌｏｓ−Ｒｏｄｏｓ」等）を用いて測定される粒度分布より体積平均を算出して求められる５０％径の値である。
「全光線透過率」は、ＪＩＳ Ｋ ７３６１−１：１９９７に準拠し、Ｄ光源にて測定される値である。
「紫外線透過率」は、全光線透過率のうち、波長１０〜４００ｎｍにおける光線透過率の値である。
塗料の「固形分質量」とは、塗料が溶媒を含む場合に、塗料から溶媒を除去した質量である。なお、溶媒以外の組成物の固形分を構成する成分に関して、その性状が液体状であっても、固形分とみなす。塗料の固形分質量は、塗料を１３０℃で２０分加熱した後に残存する質量として求められる。 The meanings of the terms in the present invention are as follows.
The numerical range represented by "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
"(Meta) acrylate" is a general term for "acrylate" and "methacrylic acid", and "(meth) acrylic" is a general term for "acrylic" and "methacrylic acid".
The "unit" is a general term for an atomic group based on one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. .. The content (mol%) of each unit with respect to all the units contained in the polymer is determined by analyzing the polymer by a nuclear magnetic resonance spectrum (NMR) method.
The "acid value" and "hydroxyl value" are values measured according to the method of JIS K 0070-3 (1992), respectively.
The "glass transition temperature" is the midpoint glass transition temperature of the polymer as measured by the differential scanning calorimetry (DSC) method. The "glass transition temperature" is also referred to as "Tg".
The "minimum film forming temperature" is the minimum temperature at which a uniform coating film without cracks is formed when the fluorine-containing polymer is dried, and is a film forming temperature measuring device IMC-1535 type (manufactured by Imoto Seisakusho Co., Ltd.). It is a value measured using. The "minimum film formation temperature" is also referred to as "MFT".
The "softening temperature" is a value measured according to the method of JIS K 7196 (1991).
The "number average molecular weight" and the "weight average molecular weight" are values measured by gel permeation chromatography using polystyrene as a standard substance. The "number average molecular weight" is also referred to as "Mn", and the "weight average molecular weight" is also referred to as "Mw".
The film thickness of the coating film is a value measured using an eddy current type film thickness meter (trade name "EDY-5000", manufactured by Sanko Denshi Co., Ltd.). When the coating film has a laminated structure in which a plurality of types of coating films are laminated, the thickness of each layer is obtained by observing the cross section of the coating film with a scanning electron microscope equipped with an energy dispersive X-ray analyzer. It is a value calculated from the ratio of the thickness of the coating film and the thickness of the entire coating film.
The layer thickness of graphene is an average value of values measured by a scanning electron microscope equipped with an energy dispersive X-ray analyzer.
The specific surface area of graphene is the average value of the values obtained by the BET method.
The average maximum particle size of graphene or graphite is the average value of the longest length of graphene or graphite in a plane perpendicular to the layer thickness direction, as measured by a scanning electron microscope equipped with an energy dispersive X-ray analyzer. ..
The average particle size of zinc powder or powder coating is larger than the particle size distribution measured using a known particle size distribution measuring device (manufactured by Symbolec, trade name "Hellos-Rodos", etc.) based on the laser diffraction method. It is a value of 50% diameter obtained by calculating the average.
The "total light transmittance" is a value measured with a D light source in accordance with JIS K 7361-1: 1997.
The "ultraviolet transmittance" is a value of the light transmittance at a wavelength of 10 to 400 nm among the total light transmittance.
The "solid content mass" of a paint is the mass of the paint from which the solvent has been removed when the paint contains a solvent. It should be noted that the components constituting the solid content of the composition other than the solvent are regarded as the solid content even if the properties are liquid. The solid content mass of the coating material is determined as the mass remaining after heating the coating material at 130 ° C. for 20 minutes.

本発明の塗料から形成される塗膜は、耐光性に優れる。この理由は必ずしも明らかではないが、以下のように考えられる。
本発明の塗料は、所定の物性を有するグラフェンおよび含フッ素重合体を含む。これにより、本発明の塗料および本発明の塗料から形成される塗膜において、含フッ素重合体とグラフェンとの親和性および均一分散性が良好になる。さらに、塗膜中に均一分散したグラフェンによって、塗膜に照射する紫外線が熱に変換され、かつ迅速に拡散されるため、塗膜における紫外線透過率が低下する。その結果、塗膜の耐光性が向上し、塗膜の耐候性に優れると考えられる。 The coating film formed from the coating film of the present invention has excellent light resistance. The reason for this is not always clear, but it can be considered as follows.
The coating material of the present invention contains graphene and a fluorine-containing polymer having predetermined physical properties. As a result, in the coating film of the present invention and the coating film formed from the coating film of the present invention, the affinity and uniform dispersibility between the fluorine-containing polymer and graphene are improved. Further, the graphene uniformly dispersed in the coating film converts the ultraviolet rays irradiating the coating film into heat and rapidly diffuses them, so that the ultraviolet transmittance in the coating film is lowered. As a result, it is considered that the light resistance of the coating film is improved and the weather resistance of the coating film is excellent.

本発明の塗料（以下、本塗料ともいう。）は、グラフェンおよび含フッ素重合体を含む。
本発明におけるグラフェンは、炭素原子が結合した六角形格子構造を有するシート状物質である。グラフェンは、炭素原子１個分の層厚みを有する単層の状態であってもよく、多層の状態であってもよい。グラフェンは、炭素原子のほかに、酸素原子、水素原子等を含んでいてもよい。
グラフェンの層厚みは、０．１〜１００ｎｍであり、０．５〜８０ｎｍが好ましく、１．０〜４０ｎｍがより好ましく、３．０〜１０ｎｍが特に好ましい。グラフェンの層厚みが上記範囲にあることで、本塗料から形成される塗膜（以下、本塗膜ともいう。）の耐光性がより向上する。
グラフェンの比表面積は、５０〜１，５００ｍ２／ｇであり、１００〜１，０００ｍ２／ｇが好ましく、１２０〜４００ｍ２／ｇがさらに好ましく、１５０〜３００ｍ２／ｇが特に好ましい。グラフェンの比表面積が上記範囲にあることで、本塗膜中の耐光性がより向上する。
グラフェンの平均最長粒子径は、グラフェンの均一分散性の点から、０．００１〜５０μｍが好ましく、０．０１〜３０μｍがより好ましく、０．１〜２０μｍが特に好ましい。
グラフェンの全質量に対する炭素原子の含有量は、耐候性の点から、８５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が特に好ましい。グラフェンの全質量に対する炭素原子の含有量の上限値は、通常１００質量％である。
本塗料におけるグラフェンの含有量は、グラフェンの均一分散性および本塗膜の耐光性の点から、本塗料の固形分質量に対して、０．０１〜１０質量％が好ましく、０．０５〜５．０質量％がより好ましく、０．１〜２．０質量％が特に好ましい。 The paint of the present invention (hereinafter, also referred to as the present paint) includes graphene and a fluorine-containing polymer.
Graphene in the present invention is a sheet-like substance having a hexagonal lattice structure in which carbon atoms are bonded. Graphene may be in a single layer state having a layer thickness equivalent to one carbon atom, or may be in a multi-layer state. Graphene may contain oxygen atoms, hydrogen atoms and the like in addition to carbon atoms.
The layer thickness of graphene is 0.1 to 100 nm, preferably 0.5 to 80 nm, more preferably 1.0 to 40 nm, and particularly preferably 3.0 to 10 nm. When the layer thickness of graphene is within the above range, the light resistance of the coating film formed from the present coating film (hereinafter, also referred to as the present coating film) is further improved.
The specific surface area of the graphene is 50~1,500m 2 / g, preferably from 100~1,000m 2 / g, more preferably 120~400m 2 / g, 150~300m 2 / g is particularly preferred. When the specific surface area of graphene is in the above range, the light resistance in the present coating film is further improved.
The average longest particle size of graphene is preferably 0.001 to 50 μm, more preferably 0.01 to 30 μm, and particularly preferably 0.1 to 20 μm from the viewpoint of uniform dispersibility of graphene.
From the viewpoint of weather resistance, the content of carbon atoms with respect to the total mass of graphene is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The upper limit of the carbon atom content with respect to the total mass of graphene is usually 100% by mass.
The content of graphene in the present coating material is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the solid content mass of the present coating material, from the viewpoint of uniform dispersibility of the graphene and the light resistance of the present coating film. .0% by mass is more preferable, and 0.1 to 2.0% by mass is particularly preferable.

本発明における含フッ素重合体は、フルオロオレフィンに基づく単位（以下、「単位Ｆ」ともいう。）と、ヒドロキシ基およびカルボキシ基の一方または両方を有する単位（以下、単位１ともいう。）とを含む含フッ素重合体であるのが好ましい。
フルオロオレフィンは、水素原子の１個以上がフッ素原子で置換されたオレフィンである。フルオロオレフィンは、フッ素原子で置換されていない水素原子の１個以上が塩素原子で置換されていてもよい。 The fluorine-containing polymer in the present invention comprises a unit based on a fluoroolefin (hereinafter, also referred to as “unit F”) and a unit having one or both of a hydroxy group and a carboxy group (hereinafter, also referred to as unit 1). It is preferably a fluorine-containing polymer containing.
A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted with fluorine atoms may be substituted with chlorine atoms.

フルオロオレフィンの具体例としては、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣＦ３、ＣＦ２＝ＣＨＣＦ３、ＣＦ３ＣＨ＝ＣＨＦ、ＣＦ３ＣＦ＝ＣＨ２、式ＣＨ２＝ＣＸｆ１（ＣＦ２）ｎ１Ｙｆ１（式中、Ｘｆ１およびＹｆ１は、独立に水素原子またはフッ素原子であり、ｎ１は２〜１０の整数である。）で表される単量体が挙げられ、本塗膜の耐候性に優れる点から、ＣＦ２＝ＣＦ２、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ３ＣＨ＝ＣＨＦ、ＣＦ３ＣＦ＝ＣＨ２が好ましく、ＣＦ２＝ＣＦＣｌが特に好ましい。フルオロオレフィンは、二種以上を併用してもよい。 Specific examples of fluoroolefins include CF 2 = CF 2 , CF 2 = CFCl, CF 2 = CHF, CH 2 = CF 2 , CF 2 = CFCF 3 , CF 2 = CHCF 3 , CF 3 CH = CHF, CF 3 CF = CH 2 , formula CH 2 = CX f1 (CF 2 ) n1 Y f1 (in the formula, X f1 and Y f1 are independently hydrogen or fluorine atoms, and n1 is an integer of 2 to 10). CF 2 = CF 2 , CH 2 = CF 2 , CF 2 = CFCl, CF 3 CH = CHF, CF 3 CF = CH from the viewpoint of excellent weather resistance of this coating film. 2 is preferable, and CF 2 = CFCl is particularly preferable. Two or more kinds of fluoroolefins may be used in combination.

単位Ｆの含有量は、本塗膜の耐候性の点から、含フッ素重合体が含む全単位に対して、２０〜１００モル％が好ましく、３０〜７０モル％がより好ましく、４０〜６０モル％が特に好ましい。 The content of the unit F is preferably 20 to 100 mol%, more preferably 30 to 70 mol%, and more preferably 40 to 60 mol% with respect to all the units contained in the fluorine-containing polymer from the viewpoint of weather resistance of the present coating film. % Is particularly preferable.

単位１は、フッ素原子を有さない単位であることが好ましい。単位１は、ヒドロキシ基およびカルボキシ基の一方または両方を有する単量体（以下、「単量体１」ともいう。）に基づく単位であってもよく、ヒドロキシ基またはカルボキシ基に変換可能な基を有する単位を含む含フッ素重合体において、該基をヒドロキシ基およびカルボキシ基の一方または両方に変換させて得られる単位であってもよい。このような単位としては、ヒドロキシ基を有する単位を含む含フッ素重合体に、ポリカルボン酸やその酸無水物等を反応させて、ヒドロキシ基の一部または全部をカルボキシ基に変換させて得られる単位が挙げられる。
単位１は、本塗料の貯蔵安定性の点からは、ヒドロキシ基を有する単位であることが好ましい。 The unit 1 is preferably a unit having no fluorine atom. The unit 1 may be a unit based on a monomer having one or both of a hydroxy group and a carboxy group (hereinafter, also referred to as “monomer 1”), and is a group that can be converted into a hydroxy group or a carboxy group. In a fluorine-containing polymer containing a unit having, the unit may be obtained by converting the group into one or both of a hydroxy group and a carboxy group. Such a unit can be obtained by reacting a fluorine-containing polymer containing a unit having a hydroxy group with a polycarboxylic acid, an acid anhydride thereof, or the like to convert a part or all of the hydroxy group into a carboxy group. The unit is mentioned.
The unit 1 is preferably a unit having a hydroxy group from the viewpoint of storage stability of the present coating material.

ヒドロキシ基を有する単量体としては、ヒドロキシ基を有する、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、（メタ）アクリル酸エステル、アリルアルコール等が挙げられる。ヒドロキシ基を有する単量体は、本塗膜の耐候性の点から、ビニルエーテルが好ましい。
ヒドロキシ基を有する単量体１の具体例としては、ＣＨ２＝ＣＨＯ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２Ｏ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯ−ＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２−（ＯＣＨ２ＣＨ２）１５ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ、およびＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨが挙げられ、フルオロオレフィンとの共重合性の点から、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨまたはＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨが好ましい。
なお、「−ｃｙｃｌｏＣ６Ｈ１０−」はシクロへキシレン基を表し、「−ｃｙｃｌｏＣ６Ｈ１０−」の結合部位は、通常１，４−である。 Examples of the monomer having a hydroxy group include vinyl ether, vinyl ester, allyl ether, allyl ester, (meth) acrylic acid ester, allyl alcohol and the like having a hydroxy group. The monomer having a hydroxy group is preferably vinyl ether from the viewpoint of weather resistance of the present coating film.
Specific examples of the monomer 1 having a hydroxy group include CH 2 = CHO-CH 2- cycloC 6 H 10- CH 2 OH, CH 2 = CHCH 2 O-CH 2- cycloC 6 H 10- CH 2 OH, CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 - (OCH 2 CH 2) 15 OH, CH 2 = CHOCH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 OH, CH 2 = CHOCH 2 CH 2 CH 2 CH 2 OH, and CH 2 = CHCH 2 OCH 2 CH 2 CH 2 CH 2 OH and the like, from the viewpoint of copolymerizability with the fluoroolefin, CH 2 = CHCH 2 OCH 2 CH 2 OH or CH 2 = CHOCH 2 CH 2 CH 2 CH 2 OH is preferable.
In addition, "-cycloC 6 H 10- " represents a cyclohexylene group, and the binding site of " -cycloC 6 H 10-" is usually 1,4-.

カルボキシ基を有する単量体としては、不飽和カルボン酸、（メタ）アクリル酸、上記ヒドロキシ基を有する単量体のヒドロキシ基にカルボン酸無水物を反応させて得られる単量体等が挙げられる。
カルボキシ基を有する単量体の具体例としては、ＣＨ２＝ＣＨＣＯＯＨ、ＣＨ（ＣＨ３）＝ＣＨＣＯＯＨ、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＨ、ＨＯＯＣＣＨ＝ＣＨＣＯＯＨ、ＣＨ２＝ＣＨ（ＣＨ２）ｎ１１ＣＯＯＨで表される単量体（ただし、ｎ１１は１〜１０の整数を示す。）、ＣＨ２＝ＣＨＯ（ＣＨ２）ｎ１２ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨで表される単量体（ただし、ｎ１２は１〜１０の整数を示す。）が挙げられ、フルオロオレフィンとの共重合性の点から、ＣＨ２＝ＣＨ（ＣＨ２）ｎ１１ＣＯＯＨで表される単量体またはＣＨ２＝ＣＨＯ（ＣＨ２）ｎ１２ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨで表される単量体が好ましい。 Examples of the monomer having a carboxy group include unsaturated carboxylic acid, (meth) acrylic acid, and a monomer obtained by reacting a hydroxy group of the above-mentioned monomer having a hydroxy group with a carboxylic acid anhydride. ..
Specific examples of the monomer having a carboxy group include CH 2 = CHCOOH, CH (CH 3 ) = CHCOOH, CH 2 = C (CH 3 ) COOH, HOOCCH = CHCOOH, CH 2 = CH (CH 2 ) n11 COOH. Monomer represented by (where n11 represents an integer of 1 to 10), CH 2 = CHO (CH 2 ) n12 OC (O) CH 2 CH 2 Monomer represented by COOH (where, however, n12 represents an integer of 1 to 10), and from the viewpoint of copolymerizability with a fluoroolefin, a monomer represented by CH 2 = CH (CH 2 ) n11 COOH or CH 2 = CHO (CH). 2 ) A monomer represented by n12 OC (O) CH 2 CH 2 COOH is preferable.

単量体１は、二種以上を併用してもよい。
単位１の含有量は、含フッ素重合体とグラフェンとの親和性に優れる点、および本塗料が硬化剤を含む場合に、本塗膜の架橋密度が高くなり本塗膜の耐久性（耐水性、耐薬品性等）に優れる点から、含フッ素重合体が含む全単位に対して、０．５〜４０モル％が好ましく、１０〜３５モル％がより好ましく、１５〜３０モル％が特に好ましい。 Two or more kinds of monomer 1 may be used in combination.
The content of unit 1 is that the affinity between the fluoropolymer and graphene is excellent, and when the coating film contains a curing agent, the crosslink density of the coating film becomes high and the durability (water resistance) of the coating film becomes high. From the viewpoint of excellent chemical resistance, etc.), 0.5 to 40 mol% is preferable, 10 to 35 mol% is more preferable, and 15 to 30 mol% is particularly preferable with respect to all the units contained in the fluoropolymer. ..

含フッ素重合体は、さらに、ヒドロキシ基およびカルボキシ基を有さない単量体（以下、単量体２ともいう。）に基づく単位（以下、単位２ともいう。）を含んでよい。単位２は、フッ素原子を有さない単位であることが好ましい。
単位２は、ヒドロキシ基およびカルボキシ基以外の架橋性基等を有していてもよい。このような基としては、アミノ基、エポキシ基、オキセタニル基、加水分解性シリル基等が挙げられる。 The fluorine-containing polymer may further contain a unit (hereinafter, also referred to as unit 2) based on a monomer having no hydroxy group and a carboxy group (hereinafter, also referred to as monomer 2). The unit 2 is preferably a unit having no fluorine atom.
The unit 2 may have a crosslinkable group or the like other than the hydroxy group and the carboxy group. Examples of such a group include an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group and the like.

単量体２としては、アルケン、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、および（メタ）アクリル酸エステルからなる群から選択される１種以上が挙げられる。単量体２としては、フルオロオレフィンとの共重合性および含フッ素重合体の耐候性の点から、ビニルエーテルおよびビニルエステルの一方または両方が好ましく、ビニルエーテルが特に好ましい。 Examples of the monomer 2 include one or more selected from the group consisting of alkene, vinyl ether, vinyl ester, allyl ether, allyl ester, and (meth) acrylic acid ester. As the monomer 2, one or both of vinyl ether and vinyl ester are preferable, and vinyl ether is particularly preferable, from the viewpoint of copolymerizability with fluoroolefin and weather resistance of fluorine-containing polymer.

単量体２の具体例としては、エチレン、プロピレン、１−ブテン、エチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル、酢酸ビニル、ピバル酸ビニルエステル、ネオノナン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ９」）、ネオデカン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ１０」）、安息香酸ビニルエステル、ｔｅｒｔ−ブチル安息香酸ビニルエステル、ｔｅｒｔ−ブチル（メタ）アクリレート、ベンジル（メタ）アクリレートが挙げられる。
単量体２は、二種以上を併用してもよい。
含フッ素重合体が単量体２を含む場合、単位２の含有量は、含フッ素重合体が含む全単位に対して、５〜６０モル％が好ましく、１０〜５０モル％が特に好ましい。 Specific examples of the monomer 2 include ethylene, propylene, 1-butene, ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl acid pivalate, and vinyl neononanoic acid ester (manufactured by HEXION). , Trade name "Beova 9"), Neodecanoic acid vinyl ester (manufactured by HEXION, trade name "Beova 10"), Vinyl benzoate ester, tert-butyl Vinyl benzoate ester, tert-butyl (meth) acrylate, benzyl (meth) ) Acrylate can be mentioned.
Two or more types of monomer 2 may be used in combination.
When the fluorine-containing polymer contains the monomer 2, the content of the unit 2 is preferably 5 to 60 mol%, particularly preferably 10 to 50 mol%, based on all the units contained in the fluorine-containing polymer.

含フッ素重合体は、含フッ素重合体が含む全単位に対して、単位Ｆと単位１と単位２とを、この順に２０〜７０モル％、０．５〜４０モル％、５〜６０モル％含むのが好ましい。 The fluorine-containing polymer contains units F, unit 1 and unit 2 in this order of 20 to 70 mol%, 0.5 to 40 mol%, and 5 to 60 mol% with respect to all the units contained in the fluorine-containing polymer. It is preferable to include it.

含フッ素重合体のＴｇは、０〜１２０℃が好ましく、１０〜４０℃が特に好ましい。含フッ素重合体のＴｇが上記範囲内にあると、含フッ素重合体の流動性が向上する。
含フッ素重合体のＭＦＴは、０〜１００℃が好ましく、１０〜４０℃が特に好ましい。
含フッ素重合体のＭｎは、１，０００〜１００，０００であり、２，０００〜３０，０００が好ましく、２，０００〜１０，０００がより好ましく、２，５００〜４，５００がさらに好ましく、３，０００〜４，０００が特に好ましい。含フッ素重合体のＭｎが上記範囲内にあると、本塗膜の耐久性（耐水性、耐薬品性等）および含フッ素重合体の流動性が向上する。 The Tg of the fluorine-containing polymer is preferably 0 to 120 ° C, particularly preferably 10 to 40 ° C. When the Tg of the fluorine-containing polymer is within the above range, the fluidity of the fluorine-containing polymer is improved.
The MFT of the fluorine-containing polymer is preferably 0 to 100 ° C, particularly preferably 10 to 40 ° C.
The Mn of the fluorine-containing polymer is 1,000 to 100,000, preferably 2,000 to 30,000, more preferably 2,000 to 10,000, still more preferably 2,500 to 4,500. 3,000 to 4,000 is particularly preferable. When the Mn of the fluorine-containing polymer is within the above range, the durability (water resistance, chemical resistance, etc.) of the present coating film and the fluidity of the fluorine-containing polymer are improved.

含フッ素重合体が水酸基価を有する場合、含フッ素重合体の水酸基価は、１０〜１５０ｍｇＫＯＨ／ｇであり、５０〜１３０ｍｇＫＯＨ／ｇがより好ましく、７０〜１２０ｍｇＫＯＨ／ｇが特に好ましい。
含フッ素重合体が酸価を有する場合、含フッ素重合体の酸価は、１０〜１５０ｍｇＫＯＨ／ｇであり、５０〜１３０ｍｇＫＯＨ／ｇがより好ましく、７０〜１２０ｍｇＫＯＨ／ｇが特に好ましい。
含フッ素重合体は、酸価または水酸基価のどちらか一方のみを有してもよく、両方を有してもよい。含フッ素重合体が酸価および水酸基価の両方を有する場合、酸価および水酸基価の合計が、１０〜１５０ｍｇＫＯＨ／ｇであるのが好ましい。
含フッ素重合体の酸価および水酸基価の一方または両方が上記範囲内にあると、含フッ素重合体とグラフェンとの親和性に優れ、グラフェンの均一分散性に優れる。また、本塗料が硬化剤を含む場合は、本塗膜の架橋密度が高くなり、本塗膜の耐久性にも優れる。
含フッ素重合体は、本塗料の安定性の点からは、水酸基価を有することが好ましい。 When the fluorine-containing polymer has a hydroxyl value, the hydroxyl value of the fluorine-containing polymer is 10 to 150 mgKOH / g, more preferably 50 to 130 mgKOH / g, and particularly preferably 70 to 120 mgKOH / g.
When the fluorine-containing polymer has an acid value, the acid value of the fluorine-containing polymer is 10 to 150 mgKOH / g, more preferably 50 to 130 mgKOH / g, and particularly preferably 70 to 120 mgKOH / g.
The fluorine-containing polymer may have either an acid value or a hydroxyl value, or may have both. When the fluorine-containing polymer has both an acid value and a hydroxyl value, the total of the acid value and the hydroxyl value is preferably 10 to 150 mgKOH / g.
When one or both of the acid value and the hydroxyl value of the fluorine-containing polymer are within the above ranges, the affinity between the fluorine-containing polymer and graphene is excellent, and the uniform dispersibility of graphene is excellent. Further, when the present coating material contains a curing agent, the crosslink density of the main coating film becomes high, and the durability of the main coating film is also excellent.
The fluorine-containing polymer preferably has a hydroxyl value from the viewpoint of stability of the present coating material.

含フッ素重合体は、公知の方法で製造される。例えば、含フッ素重合体は、溶媒とラジカル重合開始剤の存在下、各単量体を共重合させて得られる。含フッ素重合体の製造方法としては、溶液重合、乳化重合が挙げられる。含フッ素重合体の製造時または製造後には、必要に応じて、重合安定剤、重合禁止剤、界面活性剤等が使用されていてもよい。 The fluorine-containing polymer is produced by a known method. For example, the fluorine-containing polymer can be obtained by copolymerizing each monomer in the presence of a solvent and a radical polymerization initiator. Examples of the method for producing a fluorine-containing polymer include solution polymerization and emulsion polymerization. If necessary, a polymerization stabilizer, a polymerization inhibitor, a surfactant, or the like may be used during or after the production of the fluorine-containing polymer.

含フッ素重合体としては、市販品を用いてもよく、具体例としては、「ルミフロン」シリーズ（ＡＧＣ社製）、「Ｆｌｕｏｎ」シリーズ（ＡＧＣ社製）、「Ｋｙｎａｒ」シリーズ（アルケマ社製）、「ゼッフル」シリーズ（ダイキン工業社製）、「Ｅｔｅｒｆｌｏｎ」シリーズ（エターナル社製）、「Ｚｅｎｄｕｒａ」シリーズ（Ｈｏｎｅｙｗｅｌｌ社製）が挙げられる。 As the fluorine-containing polymer, a commercially available product may be used, and specific examples thereof include "Lumiflon" series (manufactured by AGC), "Fluon" series (manufactured by AGC), "Kynar" series (manufactured by Arkema), and the like. Examples include the "Zeffle" series (manufactured by Daikin Industries, Ltd.), the "Eterflon" series (manufactured by Eternal), and the "Zendura" series (manufactured by Honeywell).

本塗料は、本塗料の固形分質量に対して、含フッ素重合体を１０〜９０質量％含むのが好ましく、３０〜７０質量％含むのが特に好ましい。 The present coating material preferably contains a fluorine-containing polymer in an amount of 10 to 90% by mass, particularly preferably 30 to 70% by mass, based on the solid content mass of the present coating material.

本塗料は、グラフェンおよび含フッ素重合体以外の成分の少なくとも一種を含んでもよい。該成分としては、含フッ素重合体以外の樹脂、添加剤等が挙げられる。
含フッ素重合体以外の樹脂としては、（メタ）アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂、シリコーン樹脂等が挙げられる。
添加剤としては、硬化剤、硬化触媒、フィラー（シリカ等の無機フィラー、樹脂ビーズ等の有機フィラー等）、着色剤（染料、有機顔料、無機顔料、金属またはマイカ等を用いた光輝顔料等）、紫外線吸収剤、光安定剤、つや消し剤、レベリング剤、表面調整剤、脱ガス剤、充填剤、熱安定剤、増粘剤、分散剤、界面活性剤、帯電防止剤、防錆剤、シランカップリング剤、防汚剤、低汚染化処理剤、可塑剤、接着剤等が挙げられる。 The present coating material may contain at least one of components other than graphene and a fluorine-containing polymer. Examples of the component include resins other than fluorine-containing polymers, additives and the like.
Examples of the resin other than the fluorine-containing polymer include (meth) acrylic resin, polyester resin, urethane resin, epoxy resin, silicone resin and the like.
As additives, curing agents, curing catalysts, fillers (inorganic fillers such as silica, organic fillers such as resin beads, etc.), colorants (dye, organic pigments, inorganic pigments, bright pigments using metal, mica, etc.) , UV absorber, light stabilizer, matting agent, leveling agent, surface conditioner, degassing agent, filler, heat stabilizer, thickener, dispersant, surfactant, antistatic agent, rust preventive, silane Coupling agents, antifouling agents, decontamination treatment agents, plasticizers, adhesives and the like can be mentioned.

本塗料は、酸化チタン顔料等の光触媒活性のある無機顔料を含む場合にも本塗膜の耐候性に優れる。通常、塗膜が光触媒活性のある無機顔料を含むと、光触媒活性により塗膜が劣化しやすい。しかしながら、本塗膜においては、光触媒活性により生じる電子をグラフェンが塗膜外に放出するため、本塗膜の劣化が抑制できると考えられる。
酸化チタン顔料としては、光触媒反応が進行しにくくなるような表面処理がなされたものが好ましく、具体的には、シリカ、アルミナ、ジルコニア、セレン、ポリオール等の有機成分等で表面処理された酸化チタン顔料が好ましく、これらの表面処理によって、酸化チタン含有量が、８３〜９０質量％に調整された酸化チタン顔料がより好ましい。
酸化チタン顔料の市販品としては、石原産業社製「タイペーク ＰＦＣ１０５」（酸化チタン含有量：８７質量％）、「タイペーク ＣＲ９５」（酸化チタン含有量：９０質量％）、堺化学社製「Ｄ９１８」（酸化チタン含有量：８５質量％）、デュポン社製「Ｔｉ−Ｐｕｒｅ Ｒ９６０」（酸化チタン含有量：８９質量％）、「Ｔｉ−Ｓｅｌｅｃｔ 」（酸化チタン含有量：９０質量％）等が挙げられる。
本塗料がグラフェンおよび無機顔料を含む場合、本塗膜の意匠性と耐光性とがバランスする点から、無機顔料の質量に対するグラフェンの質量比（グラフェンの質量／無機顔料の質量）は、０．００１〜１．０が好ましく、０．０１〜０．１０が特に好ましい。
本塗料が無機顔料を含む場合、本塗料が含む含フッ素重合の全質量に対する無機顔料の含有量は、本塗膜の耐候性と意匠性とがバランスする点から、２０〜２００質量％が好ましく、５０〜１５０質量％が特に好ましい。 The present coating material has excellent weather resistance of the present coating film even when it contains an inorganic pigment having photocatalytic activity such as a titanium oxide pigment. Generally, when the coating film contains an inorganic pigment having photocatalytic activity, the coating film tends to deteriorate due to photocatalytic activity. However, in this coating film, since graphene releases electrons generated by photocatalytic activity to the outside of the coating film, it is considered that deterioration of the main coating film can be suppressed.
The titanium oxide pigment preferably has a surface treatment that makes it difficult for the photocatalytic reaction to proceed. Specifically, titanium oxide that has been surface-treated with an organic component such as silica, alumina, zirconia, selenium, or polyol. Pigments are preferable, and titanium oxide pigments whose titanium oxide content is adjusted to 83 to 90% by mass by these surface treatments are more preferable.
Commercially available titanium oxide pigments include "Titanium PFC105" manufactured by Ishihara Sangyo Co., Ltd. (titanium oxide content: 87% by mass), "Titanium CR95" (titanium oxide content: 90% by mass), and "D918" manufactured by Sakai Chemical Co., Ltd. (Titanium oxide content: 85% by mass), Dupont's "Ti-Pure R960" (titanium oxide content: 89% by mass), "Ti-Select" (titanium oxide content: 90% by mass) and the like. ..
When the present paint contains graphene and an inorganic pigment, the mass ratio of graphene to the mass of the inorganic pigment (mass of graphene / mass of inorganic pigment) is 0. 001-1.0 is preferable, and 0.01-0.10 is particularly preferable.
When the present coating material contains an inorganic pigment, the content of the inorganic pigment with respect to the total mass of the fluorine-containing polymerization contained in the present coating material is preferably 20 to 200% by mass from the viewpoint of balancing the weather resistance and the design property of the present coating film. , 50-150% by mass is particularly preferable.

本塗料は、硬化剤を含むことが好ましい。本塗料が硬化剤を含むと、含フッ素重合体が有する所定量のヒドロキシ基およびカルボキシ基の一方または両方によって本塗料中に均一分散しているグラフェンが、塗膜形成時において含フッ素重合体の架橋反応とともに均一分散している状態で固定されるため、本塗膜におけるグラフェンの均一分散性に優れる。さらに、本塗膜の架橋密度が高くなり、本塗膜の耐久性（耐水性、耐薬品性等）にも優れる。 The coating material preferably contains a curing agent. When the coating material contains a curing agent, graphene uniformly dispersed in the coating material by one or both of a predetermined amount of hydroxy groups and carboxy groups of the fluorine-containing polymer is formed in the fluorine-containing polymer at the time of forming the coating film. Since it is fixed in a uniformly dispersed state together with the cross-linking reaction, the uniform dispersibility of graphene in this coating film is excellent. Further, the crosslink density of the main coating film is increased, and the durability (water resistance, chemical resistance, etc.) of the main coating film is also excellent.

硬化剤は、含フッ素重合体が有する架橋性基と反応し得る基を１分子中に２以上有する化合物である。硬化剤と、含フッ素重合体が有するヒドロキシ基またはカルボキシ基とが反応すると、含フッ素重合体が硬化剤を介して架橋し、フッ素樹脂が形成される。硬化剤は、ヒドロキシ基またはカルボキシ基と反応し得る基を、通常２〜３０個有する。
硬化剤としては、イソシアネート基、エポキシ基、オキサゾリン基、β−ヒドロキシアルキルアミド基等を１分子中に２以上有する化合物が挙げられる。
含フッ素重合体がヒドロキシ基を有する場合、硬化剤としては、イソシアネート基を１分子中に２以上有する化合物であるポリイソシアネートが好ましい。
含フッ素重合体がカルボキシ基を有する場合、硬化剤としては、エポキシ基、オキサゾリン基、β−ヒドロキシアルキルアミド基等を１分子中に２以上有する化合物が好ましい。 The curing agent is a compound having two or more groups in one molecule that can react with the crosslinkable groups of the fluorine-containing polymer. When the curing agent reacts with the hydroxy group or the carboxy group of the fluorine-containing polymer, the fluorine-containing polymer is crosslinked via the curing agent to form a fluororesin. The curing agent usually has 2 to 30 groups capable of reacting with a hydroxy group or a carboxy group.
Examples of the curing agent include compounds having two or more isocyanate groups, epoxy groups, oxazoline groups, β-hydroxyalkylamide groups and the like in one molecule.
When the fluorine-containing polymer has a hydroxy group, the curing agent is preferably polyisocyanate, which is a compound having two or more isocyanate groups in one molecule.
When the fluorine-containing polymer has a carboxy group, the curing agent is preferably a compound having two or more epoxy groups, oxazoline groups, β-hydroxyalkylamide groups and the like in one molecule.

ポリイソシアネートとは、イソシアネート基またはブロック化イソシアネート基を１分子中に２以上有する化合物である。
ポリイソシアネートとしては、ポリイソシアネート単量体、ポリイソシアネート誘導体が好ましい。
ポリイソシアネート単量体としては、脂環族ポリイソシアネート、脂肪族ポリイソシアネート、芳香族ポリイソシアネートが好ましい。ポリイソシアネート誘導体としては、ポリイソシアネート単量体の多量体または変性体（アダクト体、アロファネート体、ビウレット体、イソシアヌレート体等）が好ましい。 Polyisocyanate is a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.
As the polyisocyanate, a polyisocyanate monomer and a polyisocyanate derivative are preferable.
As the polyisocyanate monomer, alicyclic polyisocyanate, aliphatic polyisocyanate, and aromatic polyisocyanate are preferable. As the polyisocyanate derivative, a multimer or a modified form of the polyisocyanate monomer (adduct form, allophanate form, biuret form, isocyanurate form, etc.) is preferable.

脂肪族ポリイソシアネートの具体例としては、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチル−１，６−ジイソシアナトヘキサン、リジンジイソシアネート等の脂肪族ジイソシアネート、リジントリイソシアネート、４−イソシアナトメチル−１，８−オクタメチレンジイソシアネート、ビス（２−イソシアナトエチル）２−イソシアナトグルタレートが挙げられる。
脂環族ポリイソシアネートの具体例としては、イソホロンジイソシアネート、１，３−ビス（イソシアナトメチル）−シクロヘキサン、４，４’−ジシクロヘキシルメタンジイソシアネート、ノルボルネンジイソシアネート、水添キシリレンジイソシアネート等の脂環族ジイソシアネートが挙げられる。
芳香族ポリイソシアネートの具体例としては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート等の芳香族ジイソシアネートが挙げられる。 Specific examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate, and lysine triisocyanate. , 4-Isocyanatomethyl-1,8-octamethylene diisocyanate, bis (2-isocyanatoethyl) 2-isocyanatoglutarate.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate. Can be mentioned.
Specific examples of the aromatic polyisocyanate include aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, and xylylene diisocyanate.

ポリイソシアネートは、上述したポリイソシアネート単量体またはポリイソシアネート誘導体が有する２以上のイソシアネート基が、ブロック化剤によってブロックされている化合物であってもよい。
ブロック化剤は、活性水素を有する化合物であり、具体例としては、アルコール、フェノール、活性メチレン、アミン、イミン、酸アミド、ラクタム、オキシム、ピラゾール、イミダゾール、イミダゾリン、ピリミジン、グアニジンが挙げられる。 The polyisocyanate may be a compound in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked by a blocking agent.
The blocking agent is a compound having active hydrogen, and specific examples thereof include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine, and guanidine.

硬化剤のＭｎは、１００〜９００であるのが好ましく、２００〜５００であるのが特に好ましい。
Ｍｎが２，０００〜３０，０００である含フッ素重合体と、Ｍｎが１００〜９００である硬化剤とを用いると、含フッ素重合体と硬化剤との相溶性に優れ、含フッ素重合体と硬化剤との架橋反応が好適に進行する。また、含フッ素重合体と硬化剤の低温における流動性にも優れるため、低温硬化性にも優れる。なお、本明細書において、低温硬化性とは、５℃以下での硬化を意味する。
硬化剤の２５℃における粘度は、含フッ素重合体と硬化剤との相溶性の点から、１００〜９００ｍＰａ・ｓであるのが好ましく、２００〜６００ｍＰａ・ｓであるのが特に好ましい。
本塗料が硬化剤を含む場合、硬化剤の含有量は、本塗料が含む含フッ素重合体の全質量に対して、２〜５０質量％が好ましく、５〜３０質量％が特に好ましい。硬化剤は、二種以上を併用してもよい。 The Mn of the curing agent is preferably 100 to 900, and particularly preferably 200 to 500.
When a fluorine-containing polymer having a Mn of 2,000 to 30,000 and a curing agent having a Mn of 100 to 900 are used, the compatibility between the fluorine-containing polymer and the curing agent is excellent, and the fluorine-containing polymer can be used. The cross-linking reaction with the curing agent proceeds favorably. In addition, since the fluorine-containing polymer and the curing agent have excellent fluidity at low temperatures, they also have excellent low-temperature curability. In addition, in this specification, low temperature curability means curing at 5 degreeC or less.
The viscosity of the curing agent at 25 ° C. is preferably 100 to 900 mPa · s, particularly preferably 200 to 600 mPa · s, from the viewpoint of compatibility between the fluorine-containing polymer and the curing agent.
When the present coating material contains a curing agent, the content of the curing agent is preferably 2 to 50% by mass, particularly preferably 5 to 30% by mass, based on the total mass of the fluorine-containing polymer contained in the present coating material. Two or more kinds of curing agents may be used in combination.

本塗料が、グラフェンおよび含フッ素重合体以外の成分を含む場合、該成分の含有量は、本塗膜の耐候性の点から、本塗料の固形分質量に対して、７０質量％以下が好ましく、１〜５０質量％が特に好ましい。 When the coating material contains components other than graphene and a fluorine-containing polymer, the content of the components is preferably 70% by mass or less with respect to the solid content mass of the coating material from the viewpoint of weather resistance of the coating film. , 1 to 50% by mass is particularly preferable.

本塗料は、グラフェンおよび含フッ素重合体が溶媒（水、有機溶剤等）に溶解または分散している塗料（水系塗料、溶剤型塗料等）であってもよく、溶媒を実質的に含まない塗料（粉体塗料等）であってもよい。本塗料は、特に耐候性が求められる重防食用途において、緻密な塗膜を形成でき耐候性に優れる点からは、溶剤型塗料であるのが好ましい。
有機溶剤としては、アルコール系溶剤、ケトン系溶剤、エステル系溶剤、炭化水素系溶剤が挙げられる。
本塗料が溶媒を含む場合、本塗料における溶媒の含有量は、本塗料の全質量に対して、１０〜９０質量％が好ましく、１０〜４０質量％がより好ましく、２０〜３５質量％が特に好ましい。つまり、本塗料における固形分の含有量は、本塗料の全質量に対して、１０〜９０質量％が好ましく、６０〜９０質量％がより好ましく、６５〜８０質量％が特に好ましい。 This paint may be a paint (water-based paint, solvent-based paint, etc.) in which graphene and a fluorine-containing polymer are dissolved or dispersed in a solvent (water, organic solvent, etc.), and is a paint that does not substantially contain a solvent. (Powder paint, etc.) may be used. This paint is preferably a solvent-based paint from the viewpoint of being able to form a dense coating film and having excellent weather resistance, particularly in heavy-duty anticorrosion applications where weather resistance is required.
Examples of the organic solvent include alcohol solvents, ketone solvents, ester solvents, and hydrocarbon solvents.
When the present coating material contains a solvent, the content of the solvent in the present coating material is preferably 10 to 90% by mass, more preferably 10 to 40% by mass, particularly preferably 20 to 35% by mass, based on the total mass of the present coating material. preferable. That is, the solid content in the present coating material is preferably 10 to 90% by mass, more preferably 60 to 90% by mass, and particularly preferably 65 to 80% by mass, based on the total mass of the present coating material.

近年、環境保護の観点から、塗料から塗膜を形成する際における、揮発性有機化合物（ＶＯＣ）の発生量の低減が求められている。ＶＯＣの発生量を低減させる方法としては、溶媒を含まない粉体塗料を用いる方法、溶媒が水である水系塗料を用いる方法、溶媒が有機溶剤である溶剤型塗料のうち、溶媒の含有量が少なく塗料中の固形分質量が大きい高固形分塗料を用いる方法等が挙げられる。高固形分塗料において、塗料の全質量に対する溶媒の含有量は、通常２０〜３５質量％であり、好ましくは２８〜３２質量％である。 In recent years, from the viewpoint of environmental protection, it has been required to reduce the amount of volatile organic compounds (VOCs) generated when forming a coating film from a paint. As a method for reducing the amount of VOC generated, a method using a powder paint containing no solvent, a method using a water-based paint in which the solvent is water, and a solvent-type paint in which the solvent is an organic solvent, the solvent content is high. Examples thereof include a method of using a high solid content paint having a small amount of solid content in the paint and a large solid content mass. In the high solid content coating material, the content of the solvent with respect to the total mass of the coating material is usually 20 to 35% by mass, preferably 28 to 32% by mass.

含フッ素重合体を含む高固形分塗料は、塗料中の溶媒の含有量が少ないと塗料粘度が高くなりやすく、塗料中の各成分の均一分散性が低下する場合がある。本塗料であれば、グラフェンおよび含フッ素重合体の物性が上述した範囲内にあるため、本塗料中の溶媒の含有量が少なくとも、含フッ素重合体とグラフェンとの親和性および均一分散性に優れる。したがって、本塗料を高固形分塗料として用いる場合においても、本塗膜の耐光性に優れ、耐候性にも優れる。
特に、含フッ素重合体のＭｎを低くすると、塗料粘度が下がりやすく、高固形分塗料としてより好適である。一方で、含フッ素重合体のＭｎを低くして塗料粘度を下げようとすると、得られる塗膜の耐久性（耐衝撃性や耐薬品性等）に劣る場合がある。これに対し、さらに硬化剤を含む本塗料であれば、水酸基価および酸価の一方または両方が上述した範囲内にあるため、本塗膜の架橋密度が好適となる。したがって、含フッ素重合体のＭｎが低くとも、耐久性に優れる塗膜を形成できる。
本塗料を高固形分塗料として用いる場合の含フッ素重合体のＭｎは、グラフェンの均一分散性と、塗料粘度と、塗膜の耐久性とがバランスする点から、２，５００〜４，５００が好ましく、３，０００〜４，０００が特に好ましい。 In a high solid content paint containing a fluorine-containing polymer, if the content of the solvent in the paint is small, the viscosity of the paint tends to be high, and the uniform dispersibility of each component in the paint may decrease. In the case of this paint, since the physical properties of graphene and the fluorine-containing polymer are within the above-mentioned range, the content of the solvent in this paint is at least excellent in the affinity and uniform dispersibility between the graphene and graphene. .. Therefore, even when the present coating material is used as a high solid content coating material, the present coating film is excellent in light resistance and weather resistance.
In particular, when the Mn of the fluorine-containing polymer is lowered, the viscosity of the coating material tends to decrease, which is more suitable as a high solid content coating material. On the other hand, if an attempt is made to lower the Mn of the fluorine-containing polymer to lower the paint viscosity, the durability (impact resistance, chemical resistance, etc.) of the obtained coating film may be inferior. On the other hand, in the case of the present coating material further containing a curing agent, one or both of the hydroxyl value and the acid value are within the above-mentioned ranges, so that the crosslink density of the present coating film is suitable. Therefore, even if the Mn of the fluorine-containing polymer is low, a coating film having excellent durability can be formed.
When this paint is used as a high solid content paint, the Mn of the fluorine-containing polymer is 2,500 to 4,500 from the viewpoint of balancing the uniform dispersibility of graphene, the viscosity of the paint, and the durability of the paint film. It is preferable, and 3,000 to 4,000 is particularly preferable.

本塗料を高固形分塗料として用いる場合、本塗料は、具体的には、本塗料の全質量に対して固形分質量が７０質量％である場合の塗料粘度が３００〜３，０００ｍＰａ・ｓであり、好ましくは１，０００〜２，５００ｍＰａ・ｓであり、特に好ましくは１，３００〜２，０００ｍＰａ・ｓである。塗料粘度が３００ｍＰａ・ｓ以上であれば、グラフェンの均一分散性に優れ、３，０００ｍＰａ・ｓ以下であれば、塗布が容易であるとともに均一な塗膜が形成でき、塗膜の耐久性に優れる。なお、上記塗料粘度は、２５℃にて５０ｒｐｍで塗料を撹拌した場合の粘度である。
本塗料を高固形分塗料として用いる場合、本塗料に含まれるＶＯＣを４２０ｇ／Ｌ以下にでき、環境にやさしい。 When this paint is used as a high solid content paint, specifically, this paint has a paint viscosity of 300 to 3,000 mPa · s when the solid content mass is 70% by mass with respect to the total mass of the paint. Yes, preferably 1,000 to 2,500 mPa · s, and particularly preferably 1,300 to 2,000 mPa · s. If the viscosity of the paint is 300 mPa · s or more, the uniform dispersibility of graphene is excellent, and if it is 3,000 mPa · s or less, the coating film can be easily applied and a uniform coating film can be formed, and the durability of the coating film is excellent. .. The paint viscosity is the viscosity when the paint is stirred at 25 ° C. and 50 rpm.
When this paint is used as a high solid content paint, the VOC contained in this paint can be reduced to 420 g / L or less, which is environmentally friendly.

固形分質量が７０質量％である場合の粘度が上記範囲内である本塗料を高固形分塗料として用いれば、塗布が容易であるとともに、厚塗りが可能である。つまり、本塗膜の膜厚を、１コートで５０〜１００μｍの厚さにできる。したがって、例えば高耐候性が要求される重防食用の塗膜において、中塗り層を設けることなく、下塗り層と、厚塗りの本塗膜である上塗り層とからなる高耐候性および防錆効果を有する塗膜を形成でき、塗膜形成の工程削減も可能である。さらには、本塗膜が厚膜であるため、本塗料以外の塗料を用いて中塗り層を形成する場合と比較して、耐光性にもより優れる。
また、本塗料が上述した範囲のＭｎを有する硬化剤を含む場合、上記のように本塗膜を厚塗りで形成する場合でも、含フッ素重合体と硬化剤との相溶性に優れ架橋反応が好適に進行するため、塗膜が均一に硬化する。したがって、本塗膜を厚塗りで形成する場合でも本塗膜の硬化性および耐久性に優れる。さらには、本塗膜を厚塗りで形成し、低温硬化させる場合でも、低温硬化性および本塗膜の耐久性に優れる。 If this paint having a viscosity of 70% by mass in solid content within the above range is used as a high solid content paint, it is easy to apply and thick coating is possible. That is, the film thickness of the present coating film can be increased to 50 to 100 μm with one coating. Therefore, for example, in a coating film for heavy corrosion protection that requires high weather resistance, a high weather resistance and rust preventive effect composed of an undercoat layer and a topcoat layer which is a thick main coating film without providing an intermediate coating layer. It is possible to form a coating film having a coating film, and it is possible to reduce the number of coating film forming steps. Furthermore, since the present coating film is a thick film, it is more excellent in light resistance as compared with the case where the intermediate coating layer is formed by using a coating material other than the present coating film.
Further, when the present coating material contains a curing agent having Mn in the above-mentioned range, even when the present coating film is formed by a thick coating as described above, the compatibility between the fluorine-containing polymer and the curing agent is excellent and the cross-linking reaction is performed. Since it proceeds favorably, the coating film is uniformly cured. Therefore, even when the present coating film is formed by a thick coating, the present coating film is excellent in curability and durability. Further, even when the present coating film is formed by a thick coating and cured at a low temperature, the low temperature curability and the durability of the present coating film are excellent.

本塗料の固形分は、本塗料の固形分質量に対して、グラフェンの０．０１〜１０質量％、含フッ素重合体の３０〜７０質量％、グラフェンおよび含フッ素重合体以外の成分の１〜５０質量％からなるのが好ましい。
本塗料は、本塗料の全質量に対して、グラフェンの０．００１〜１０質量％、含フッ素重合体の１０〜７０質量％、グラフェンおよび含フッ素重合体以外の成分の０．１〜５０質量％、および溶媒の１０〜４０質量％からなるのが好ましい。 The solid content of this coating material is 0.01 to 10% by mass of graphene, 30 to 70% by mass of fluorine-containing polymer, and 1 to 1 of components other than graphene and fluorine-containing polymer with respect to the solid content mass of this coating material. It is preferably composed of 50% by mass.
This paint contains 0.001 to 10% by mass of graphene, 10 to 70% by mass of fluorine-containing polymer, and 0.1 to 50% by mass of components other than graphene and fluorine-containing polymer, based on the total mass of this paint. %, And preferably 10 to 40% by weight of the solvent.

本塗膜は、基材上、または基材上にさらに形成された本塗膜以外の塗膜上に本塗料を塗布し、必要に応じて乾燥し、加熱硬化して形成すればよい。
本塗料が水系塗料または溶剤型塗料である場合、塗布方法としては、スプレーコート法、スキージコート法、フローコート法、バーコート法、スピンコート法、ディップコート法、スクリーン印刷法、グラビア印刷法、ダイコート法、インクジェット法、カーテンコート法、はけやへらを用いる方法等が挙げられる。
本塗料が粉体塗料である場合、塗装方法としては、静電塗装法、静電吹付法、静電浸漬法、噴霧法、流動浸漬法、吹付法、スプレー法、溶射法、プラズマ溶射法等が挙げられる。
本塗料が溶媒を含む場合、塗布後に乾燥させて溶媒を除去するのが好ましい。乾燥温度は、通常、０〜５０℃であり、乾燥時間は、通常、１分〜２週間である。
本塗料が硬化剤を含む場合、塗布後に加熱硬化させるのが好ましい。加熱硬化温度は、通常５０℃〜３００℃であり、加熱硬化時間は、通常１分〜２４時間である。ただし、本塗料は、含フッ素重合体のＭｎが２，５００〜４，５００であり、かつ好ましくはＭｎが１００〜９００である硬化剤を含む場合には、５℃以下、さらには０℃以下の低温での硬化であっても、硬化性に優れる。 The present coating film may be formed by applying the present coating film on a base material or a coating film other than the main coating film further formed on the base material, drying the coating film as necessary, and heat-curing the coating film.
When this paint is a water-based paint or a solvent-based paint, the coating methods include spray coating method, squeegee coating method, flow coating method, bar coating method, spin coating method, dip coating method, screen printing method, and gravure printing method. Examples include a die coating method, an inkjet method, a curtain coating method, and a method using a brush or spatula.
When this paint is a powder paint, the coating methods include electrostatic coating method, electrostatic spraying method, electrostatic immersion method, spraying method, flow immersion method, spraying method, spraying method, thermal spraying method, plasma spraying method, etc. Can be mentioned.
When the present coating material contains a solvent, it is preferable to remove the solvent by drying after application. The drying temperature is usually 0 to 50 ° C., and the drying time is usually 1 minute to 2 weeks.
When the present coating material contains a curing agent, it is preferably heat-cured after application. The heat curing temperature is usually 50 ° C. to 300 ° C., and the heat curing time is usually 1 minute to 24 hours. However, when the present coating material contains a curing agent having a fluorine-containing polymer having a Mn of 2,500 to 4,500 and preferably a Mn of 100 to 900, the temperature is 5 ° C. or lower, further 0 ° C. or lower. It has excellent curability even when it is cured at a low temperature.

本塗膜の膜厚は、本塗膜の耐候性の点から、１０〜１，０００μｍが好ましく、２５〜５００μｍがより好ましく、５０〜１００μｍが特に好ましい。本塗膜においては、塗膜形成の工程削減の点から、溶剤型塗料である本塗料を用いて１コートで形成される塗膜の膜厚が５０〜１００μｍであることが好ましい。 The film thickness of the present coating film is preferably 10 to 1,000 μm, more preferably 25 to 500 μm, and particularly preferably 50 to 100 μm from the viewpoint of weather resistance of the main coating film. In the present coating film, the film thickness of the coating film formed by one coat using the present coating film, which is a solvent type coating film, is preferably 50 to 100 μm from the viewpoint of reducing the process of forming the coating film.

本塗料を用いれば、基材と、基材上に形成された本塗膜とを有する塗膜付き基材が得られる。
本発明における基材の材質の具体例としては、無機物、有機物、有機無機複合材が挙げられる。
無機物の具体例としては、コンクリート、自然石、ガラス、金属材料が挙げられる。
有機物の具体例としては、プラスチック、ゴム、接着剤、木材が挙げられる。
有機無機複合材の具体例としては、繊維強化プラスチック、樹脂強化コンクリート、繊維強化コンクリートが挙げられる。
基材は、公知の表面処理がなされていてもよい。表面処理としては、金属皮膜処理、化成処理等が挙げられる。金属皮膜処理としては、電気めっき、溶融めっき、蒸着めっきが挙げられる。化成処理としては、クロメート処理、リン酸塩処理等が挙げられる。 When this coating material is used, a coated base material having a base material and the main coating film formed on the base material can be obtained.
Specific examples of the material of the base material in the present invention include inorganic substances, organic substances, and organic-inorganic composite materials.
Specific examples of inorganic substances include concrete, natural stone, glass, and metal materials.
Specific examples of organic substances include plastics, rubbers, adhesives, and wood.
Specific examples of the organic-inorganic composite material include fiber reinforced plastic, resin reinforced concrete, and fiber reinforced concrete.
The base material may be subjected to a known surface treatment. Examples of the surface treatment include metal film treatment and chemical conversion treatment. Examples of the metal film treatment include electroplating, hot-dip plating, and thin-film plating. Examples of the chemical conversion treatment include chromate treatment and phosphate treatment.

基材は、本発明における塗膜付き基材の耐候性の点から、金属からなるのが好ましい。金属としては、鉄、アルミニウム、亜鉛、錫、チタン、鉛、銅、マグネシウム、マンガン、ケイ素、クロム、ジルコニウム、バナジウム、ニッケル、ビスマス等の金属を含む材料が挙げられる。金属としては、鉄またはアルミニウムが特に好適である。金属は、二種以上の金属を含む合金でもよい。
金属としては、耐候性の点から、鉄合金（鉄鋼、ステンレス等）またはアルミニウム合金が好ましく、鉄鋼が特に好ましい。 The base material is preferably made of metal from the viewpoint of weather resistance of the base material with a coating film in the present invention. Examples of the metal include materials containing metals such as iron, aluminum, zinc, tin, titanium, lead, copper, magnesium, manganese, silicon, chromium, zirconium, vanadium, nickel and bismuth. As the metal, iron or aluminum is particularly suitable. The metal may be an alloy containing two or more kinds of metals.
As the metal, an iron alloy (steel, stainless steel, etc.) or an aluminum alloy is preferable, and steel is particularly preferable, from the viewpoint of weather resistance.

本発明における塗膜付き基材は、基材と本塗膜との間に、下塗り層を有していてもよい。この場合、基材と、下塗り層および本塗膜からなる上塗り層からなる塗膜とをこの順に有する塗膜付き基材が得られる。 The base material with a coating film in the present invention may have an undercoat layer between the base material and the main coating film. In this case, a base material with a coating film having a base material and a coating film composed of an undercoat layer and a topcoat layer composed of the main coating film in this order can be obtained.

下塗り層は、基材と基材以外の層との接着性に寄与する層である。任意の樹脂および樹脂以外の成分を含めばよい。下塗り層が含む樹脂としては、（メタ）アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂、シリコーン樹脂等が挙げられる。下塗り層は、基材との密着性の点からは、エポキシ樹脂またはシリコーン樹脂を含むことが好ましい。
エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂が挙げられる。
シリコーン樹脂としては、ジメチルポリシロキサン等のジアルキルポリシロキサン、ポリジフェニルシロキサン等のポリアリールシロキサン、メチルフェニルポリシロキサン等のポリアルキルアリールシロキサン等からなるシリコーン樹脂、アミノ変性シリコーン、エポキシ変性シリコーン、カルボキシ変性シリコーン、アルコール変性シリコーン、ポリエーテル変性シリコーン等の変性シリコーン樹脂等が挙げられる。
下塗り層は、樹脂の二種以上を含んでいてもよい。樹脂以外の成分としては、本塗膜が含んでいてもよい成分として上述した添加剤が挙げられる。 The undercoat layer is a layer that contributes to the adhesiveness between the base material and a layer other than the base material. Any resin and non-resin components may be included. Examples of the resin contained in the undercoat layer include (meth) acrylic resin, polyester resin, urethane resin, epoxy resin, and silicone resin. The undercoat layer preferably contains an epoxy resin or a silicone resin from the viewpoint of adhesion to the base material.
Examples of the epoxy resin include bisphenol A type epoxy resin and bisphenol F type epoxy resin.
Examples of the silicone resin include a silicone resin composed of dialkylpolysiloxane such as dimethylpolysiloxane, polyarylsiloxane such as polydiphenylsiloxane, and polyalkylarylsiloxane such as methylphenylpolysiloxane, amino-modified silicone, epoxy-modified silicone, and carboxy-modified silicone. , Alcohol-modified silicone, modified silicone resin such as polyether-modified silicone, and the like.
The undercoat layer may contain two or more types of resin. Examples of the components other than the resin include the above-mentioned additives as components that the coating film may contain.

下塗り層は、グラフェンを含むことが好ましい。下塗り層が含むグラフェンについては、本塗料が含むグラフェンと同様である。
下塗り層がグラフェンを含む場合、下塗り層におけるグラフェンの含有量は、下塗り層の耐光性の点から、下塗り層の全質量に対して、０．０１〜１０質量％が好ましく、０．０５〜５．０質量％がより好ましく、０．１〜２．０質量％が特に好ましい。 The undercoat layer preferably contains graphene. The graphene contained in the undercoat layer is the same as the graphene contained in the present paint.
When the undercoat layer contains graphene, the content of graphene in the undercoat layer is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the undercoat layer from the viewpoint of light resistance of the undercoat layer. .0% by mass is more preferable, and 0.1 to 2.0% by mass is particularly preferable.

下塗り層は、亜鉛末を含むことが好ましい。下塗り層が亜鉛末を含む場合、防錆効果が求められる重防食用途の塗膜付き基材としても好適に使用できる。特に基材が鉄鋼等の鉄合金である場合、亜鉛末が基材中の鉄のかわりにイオン化するため、防錆効果に優れる。 The undercoat layer preferably contains zinc powder. When the undercoat layer contains zinc powder, it can be suitably used as a base material with a coating film for heavy corrosion prevention, which is required to have a rust preventive effect. In particular, when the base material is an iron alloy such as steel, the zinc powder is ionized instead of the iron in the base material, so that the rust preventive effect is excellent.

亜鉛末とは、金属亜鉛の粒子である。亜鉛末の形状は、球状であっても鱗片状であってもよく、球状が好ましい。亜鉛末の平均粒子径は、下塗り層において亜鉛末が密充填され防錆効果に優れる点から、０．１〜３０μｍが好ましく、０．５〜１０μｍがより好ましく、１〜５μｍが特に好ましい。
下塗り層における亜鉛末の含有量は、下塗り層の防錆効果の点から、下塗り層の全質量に対して、５０〜９９質量％が好ましく、６０〜９５質量％が特に好ましい。 Zinc powder is metallic zinc particles. The shape of the zinc powder may be spherical or scaly, and a spherical shape is preferable. The average particle size of the zinc powder is preferably 0.1 to 30 μm, more preferably 0.5 to 10 μm, and particularly preferably 1 to 5 μm, from the viewpoint that the zinc powder is densely packed in the undercoat layer and the rust preventive effect is excellent.
The content of zinc powder in the undercoat layer is preferably 50 to 99% by mass, particularly preferably 60 to 95% by mass, based on the total mass of the undercoat layer from the viewpoint of the rust preventive effect of the undercoat layer.

下塗り層は、グラフェンと亜鉛末とをともに含むことが好ましい。この場合、下塗り層における、亜鉛末の質量に対するグラフェンの質量の比（グラフェンの質量／亜鉛末の質量）は、防錆効果に優れる点から、１．０×１０−４〜１．０が好ましく、１．０×１０−３〜０．１５がより好ましく、０．０１〜０．１が特に好ましい。この場合、亜鉛末とグラフェンとの接触面積が好適であり、下塗り層と基材との間の電子の受け渡し効率が上がるため、亜鉛末による防錆効果が向上し、本発明の塗膜付き基材の防錆効果も向上すると考えられる。また、グラフェンが亜鉛末と接触していることで、亜鉛末のイオン化を抑制することができるため、下塗り層における亜鉛末の含有量を減らすことができ、下塗り層の薄膜化も可能である。特に、グラフェンの比表面積が大きいほど、グラフェンと亜鉛との接触面積も大きくなり、防錆効果により優れる。
下塗り層の厚さは、１〜３００μｍが好ましく、１０〜２００μｍがより好ましく、５０〜１００μｍが特に好ましい。 The undercoat layer preferably contains both graphene and zinc powder. In this case, the ratio of the mass of graphene to the mass of zinc powder (mass of graphene / mass of zinc powder) in the undercoat layer is preferably 1.0 × 10 -4 to 1.0 from the viewpoint of excellent rust prevention effect. , 1.0 × 10 -3 to 0.15 is more preferable, and 0.01 to 0.1 is particularly preferable. In this case, the contact area between the zinc powder and graphene is suitable, and the efficiency of electron transfer between the undercoat layer and the base material is increased, so that the rust preventive effect of the zinc powder is improved, and the coated group of the present invention is used. It is considered that the rust preventive effect of the material is also improved. Further, since graphene is in contact with zinc powder, ionization of zinc powder can be suppressed, so that the content of zinc powder in the undercoat layer can be reduced, and the undercoat layer can be thinned. In particular, the larger the specific surface area of graphene, the larger the contact area between graphene and zinc, which is more excellent in rust prevention effect.
The thickness of the undercoat layer is preferably 1 to 300 μm, more preferably 10 to 200 μm, and particularly preferably 50 to 100 μm.

下塗り層は、上述した樹脂等を含む下塗り塗料から形成されればよい。下塗り塗料は、上述した樹脂等のかわりに、架橋性基を有する樹脂または架橋性基を有するプレポリマーを含んでいてもよい。この場合、下塗り塗料は、硬化剤を含むのが好ましい。下塗り塗料が、架橋性基を有する樹脂または架橋性基を有するプレポリマーを含む場合、下塗り塗料を塗布して硬化させて塗膜を形成すれば、樹脂を含む下塗り層が得られる。
下塗り層の形成方法は、本塗料にかえて下塗り塗料を用いる以外、本塗膜の形成方法として上述した方法と同様である。 The undercoat layer may be formed from an undercoat paint containing the above-mentioned resin or the like. The undercoat coating material may contain a resin having a crosslinkable group or a prepolymer having a crosslinkable group instead of the above-mentioned resin or the like. In this case, the undercoat paint preferably contains a curing agent. When the undercoat paint contains a resin having a crosslinkable group or a prepolymer having a crosslinkable group, the undercoat layer containing the resin can be obtained by applying the undercoat paint and curing it to form a coating film.
The method for forming the undercoat layer is the same as the method described above as the method for forming the main coating film, except that the undercoat paint is used instead of the present paint.

下塗り塗料における亜鉛末の含有量は、下塗り塗料の固形分質量に対して、５０〜９９質量％が好ましく、８５〜９５質量％が特に好ましい。
下塗り塗料におけるグラフェンの含有量は、下塗り塗料の固形分質量に対して、０．０１〜１０質量％が好ましく、０．０５〜５．０質量％がより好ましく、０．１〜２．０質量％が特に好ましい。
下塗り塗料における樹脂の含有量は、下塗り塗料の固形分質量に対して、０．５〜３５質量％が好ましく、１〜３０質量％が特に好ましい。
下塗り塗料における、亜鉛末の質量に対するグラフェンの質量比（グラフェンの質量／亜鉛末の質量）は、防錆効果に優れる塗膜を形成できる点から、１．０×１０−４〜１．０が好ましく、１．０〜１０−３〜０．１５がより好ましく、０．０１〜０．１が特に好ましい。 The content of zinc powder in the undercoat paint is preferably 50 to 99% by mass, particularly preferably 85 to 95% by mass, based on the solid content mass of the undercoat paint.
The content of graphene in the undercoat paint is preferably 0.01 to 10% by mass, more preferably 0.05 to 5.0% by mass, and 0.1 to 2.0% by mass with respect to the solid content mass of the undercoat paint. % Is particularly preferable.
The content of the resin in the undercoat paint is preferably 0.5 to 35% by mass, particularly preferably 1 to 30% by mass, based on the solid content mass of the undercoat paint.
The mass ratio of graphene to the mass of zinc powder (mass of graphene / mass of zinc powder) in the undercoat paint is 1.0 × 10 -4 to 1.0 because it can form a coating film with excellent rust prevention effect. Preferably, 1.0 to 10 -3 to 0.15 is more preferable, and 0.01 to 0.1 is particularly preferable.

下塗り塗料は、下塗り塗料が含む固形分が、溶媒（水、有機溶剤等）に溶解または分散している塗料（水系塗料、溶剤型塗料等）であってもよく、溶媒を実質的に含まない塗料（粉体塗料等）であってもよい。
下塗り塗料が溶媒を含む場合、下塗り塗料における溶媒の含有量は、下塗り塗料が含む全質量に対して、１０〜９０質量％が好ましく、３０〜６０質量％が特に好ましい。
下塗り塗料は、下塗り塗料の全質量に対して、亜鉛末の４０〜９５質量％、グラフェンの０．００５〜８質量％、バインダー樹脂の０．１〜３０質量％、添加剤の０〜１０質量％、溶媒の１０〜６０質量％からなるのが好ましい。 The undercoat paint may be a paint (water-based paint, solvent-type paint, etc.) in which the solid content contained in the undercoat paint is dissolved or dispersed in a solvent (water, organic solvent, etc.), and does not substantially contain the solvent. It may be a paint (powder paint or the like).
When the undercoat paint contains a solvent, the content of the solvent in the undercoat paint is preferably 10 to 90% by mass, particularly preferably 30 to 60% by mass, based on the total mass contained in the undercoat paint.
The undercoat paint is 40 to 95% by mass of zinc powder, 0.005 to 8% by mass of graphene, 0.1 to 30% by mass of binder resin, and 0 to 10% by mass of additives with respect to the total mass of the undercoat paint. It is preferably composed of 10 to 60% by mass of the solvent.

本発明の塗膜付き基材は、下塗り層と上塗り層との間に中塗り層を有していてもよい。中塗り層は、単層でもよく、複層でもよい。ただし、上述したように、本塗料が高固形分塗料であり本塗膜を上塗り層として用いる場合、厚塗りが可能であるため、必ずしも中塗り層を有する必要はない。 The base material with a coating film of the present invention may have an intermediate coating layer between the undercoat layer and the topcoat layer. The intermediate coating layer may be a single layer or a plurality of layers. However, as described above, when the present coating material is a high solid content coating material and the present coating film is used as the top coating layer, it is possible to apply a thick coating, so that it is not always necessary to have an intermediate coating layer.

中塗り層は、任意の樹脂および樹脂以外の成分を含めばよい。中塗り層が含む樹脂としては、（メタ）アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂、シリコーン樹脂等が挙げられる。中塗り層は、樹脂の二種以上を含んでいてもよい。樹脂以外の成分としては、本塗料が含んでいてもよい成分として上述した添加剤が挙げられる。 The intermediate coating layer may contain any resin and components other than the resin. Examples of the resin contained in the intermediate coating layer include (meth) acrylic resin, polyester resin, urethane resin, epoxy resin, and silicone resin. The intermediate coating layer may contain two or more kinds of resins. Examples of the components other than the resin include the above-mentioned additives as components that may be contained in the present coating material.

中塗り層は、グラフェンを含んでもよい。好ましいグラフェンとしては、本塗料が含むグラフェンと同様である。
中塗り層がグラフェンを含む場合、中塗り層に入射した紫外線が、上記グラフェンによって熱に変換され、かつ迅速に拡散されるため、塗膜における紫外線透過率が低減すると考えられる。その結果、塗膜の耐光性が向上し、塗膜の耐候性にも優れると考えられる。
また、中塗り層が添加剤として無機顔料（特に、酸化チタン顔料等の光触媒活性のある無機顔料）を含む場合、無機顔料の光触媒活性により生じる電子をグラフェンが塗膜外に放出するため、中塗り層の劣化がさらに抑制できると考えられる。 The intermediate coating layer may contain graphene. The preferred graphene is the same as the graphene contained in the present paint.
When the intermediate coating layer contains graphene, the ultraviolet rays incident on the intermediate coating layer are converted into heat by the graphene and rapidly diffused, so that it is considered that the ultraviolet transmittance in the coating film is reduced. As a result, it is considered that the light resistance of the coating film is improved and the weather resistance of the coating film is also excellent.
Further, when the intermediate coating layer contains an inorganic pigment (particularly, an inorganic pigment having photocatalytic activity such as titanium oxide pigment) as an additive, graphene releases electrons generated by the photocatalytic activity of the inorganic pigment to the outside of the coating film. It is considered that the deterioration of the coating layer can be further suppressed.

中塗り層がグラフェンを含む場合、中塗り層におけるグラフェンの含有量は、中塗り層の全質量に対して、０．０１〜１０質量％が好ましく、０．０５〜５質量％がより好ましく、０．１〜２．０質量％が特に好ましい。
中塗り層がグラフェンを含み、かつ無機顔料を含む場合、中塗り層の意匠性と耐光性とがバランスする点から、無機顔料の質量に対するグラフェンの質量比（グラフェンの質量／無機顔料の質量）は、０．００１〜１．０が好ましく、０．０１〜０．１０が特に好ましい。 When the intermediate coating layer contains graphene, the content of graphene in the intermediate coating layer is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the intermediate coating layer. 0.1 to 2.0% by mass is particularly preferable.
When the intermediate coating layer contains graphene and contains an inorganic pigment, the mass ratio of graphene to the mass of the inorganic pigment (mass of graphene / mass of inorganic pigment) from the viewpoint of balancing the design and light resistance of the intermediate coating layer. Is preferably 0.001 to 1.0, and particularly preferably 0.01 to 0.10.

中塗り層は、任意の樹脂および樹脂以外の成分を含む中塗り塗料から形成されればよい。中塗り層の形成方法は、本塗料にかえて中塗り塗料を用いる以外、本塗膜の形成方法として上述した方法と同様である。 The intermediate coating layer may be formed from an intermediate coating coating material containing any resin and components other than the resin. The method for forming the intermediate coating layer is the same as the method described above as the method for forming the main coating film, except that the intermediate coating is used instead of the main coating.

本発明の塗膜付き基材は、基材上に下塗り塗料を塗布して下塗り層を形成し、得られた下塗り層上に、本塗料を塗布して上塗り層を形成して得ればよい。この場合、下塗り層を形成したのち、さらに下塗り層上に中塗り塗料を塗布して中塗り層を形成し、得られた中塗り層上に、本塗料を塗布して上塗り層を形成してもよい。中塗り層は、二種以上を形成してもよい。
各塗料を塗布した後に乾燥や加熱硬化等が必要である場合、各層の塗布、乾燥、および加熱硬化の順番は制限されない。つまり、各層ごとに乾燥や加熱硬化を行ってもよく、全ての層を塗布してから同時に乾燥や加熱硬化を行ってもよい。 The base material with a coating film of the present invention may be obtained by applying an undercoat paint on the base material to form an undercoat layer, and then applying the present paint on the obtained undercoat layer to form an overcoat layer. .. In this case, after the undercoat layer is formed, the intermediate coat layer is further applied on the undercoat layer to form the intermediate coat layer, and the present paint is applied on the obtained intermediate coat layer to form the top coat layer. May be good. Two or more types of intermediate coating layers may be formed.
When drying, heat curing, or the like is required after applying each paint, the order of coating, drying, and heat curing of each layer is not limited. That is, each layer may be dried or heat-cured, or all the layers may be applied and then dried or heat-cured at the same time.

本発明の塗膜付き基材は、耐光性に優れるため、橋梁、高速道路、送電鉄塔といった、太陽光に長期に渡って曝されうる屋外構造物の保護に使用される重防食用塗料として、好適に使用できる。 Since the coated base material of the present invention has excellent light resistance, it is used as a heavy-duty anticorrosion paint used for protecting outdoor structures that may be exposed to sunlight for a long period of time, such as bridges, highways, and transmission towers. Can be preferably used.

以下、例を挙げて本発明を詳細に説明する。ただし本発明はこれらの例に限定されない。例１〜９、２１〜２４および３１〜３８は実施例であり、例１０〜１２は比較例である。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. Examples 1-9, 21-24 and 31-38 are examples, and examples 10-12 are comparative examples.

＜使用した成分の略称と詳細＞
〔単量体〕
ＡＶ：酢酸ビニル
ＢＭＡ：ｎ−ブチルメタクリレート
ＣＴＦＥ：クロロトリフルオロエチレン
ＣＨＶＥ：シクロヘキシルビニルエーテル
ＣＨＭＶＥ：シクロヘキサンジメタノールモノビニルエーテル
ＣＭＥＯＶＥ：ＣＨ２＝ＣＨＯＣＨ２−ｃｙｃｌｏＣ６Ｈ１０−ＣＨ２Ｏ（ＣＨ２ＣＨ２Ｏ）ｎＨ（ｎ＝１５）
ＥＶＥ：エチルビニルエーテル
ＨＥＡＥ：２−ヒドロキシエチルアリルエーテル
ＨＢＶＥ：４−ヒドロキシブチルビニルエーテル
ＭＭＡ：メチルメタクリレート
ＴＦＥ：テトラフルオロエチレン
ＶｄＦ：フッ化ビニリデン
ＶＢｎ：安息香酸ビニルエステル
ＶＶ：バーサチック酸ビニルエステル <Abbreviations and details of the ingredients used>
[Monomer]
AV: Vinyl acetate BMA: n-Butyl methacrylate CTFE: Chlorotrifluoroethylene CHVE: Cyclohexyl vinyl ether CHMVE: Cyclohexanedimethanol Monovinyl ether CMEOVE: CH 2 = CHOCH 2- cycloC 6 H 10- CH 2 O (CH 2 CH 2 O) n H (n = 15)
EVE: Ethyl vinyl ether HEAE: 2-Hydroxyethyl allyl ether HBVE: 4-Hydroxybutyl vinyl ether MMA: Methyl methacrylate TFE: Tetrafluoroethylene VdF: Vinylidene fluoride VBn: Vinyl benzoate VV: Vinyl ester Versatic acid

〔グラフェンおよびグラファイト〕
グラフェン１：比表面積２８０ｍ２／ｇ、平均最長粒子径１０μｍ、炭素原子含有量９３質量％以上、層厚み６ｎｍであるグラフェン
グラフェン２：比表面積３５０ｍ２／ｇ、平均最長粒子径１０μｍ、炭素原子含有量９３質量％以上、層厚み４ｎｍであるグラフェン
グラファイト：比表面積７０ｍ２／ｇ、平均最長粒子径５０μｍ、炭素原子含有量９０質量％、層厚み１１０ｎｍであるグラファイト [Graphene and graphite]
Graphene 1: Specific surface area 280 m 2 / g, average longest particle diameter 10 μm, carbon atom content 93% by mass or more, layer thickness 6 nm Graphene Graphene 2: Specific surface area 350 m 2 / g, average longest particle diameter 10 μm, carbon atom content Graphene graphite having an amount of 93% by mass or more and a layer thickness of 4 nm: graphite having a specific surface area of 70 m 2 / g, an average longest particle diameter of 50 μm, a carbon atom content of 90% by mass, and a layer thickness of 110 nm.

〔含フッ素重合体〕
含フッ素重合体１：重合体が含む全単位に対して、ＴＦＥに基づく単位を４５モル％、ＨＥＡＥに基づく単位を１４モル％、ＶＶに基づく単位を３１モル％、ＶＢｎに基づく単位を６モル％、ＡＶに基づく単位を４モル％含む含フッ素重合体（水酸基価５５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ１１，４００、Ｔｇ３５℃）
含フッ素重合体２：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を５０モル％、ＥＶＥに基づく単位を２４モル％、ＣＨＶＥに基づく単位を１５モル％、ＨＢＶＥに基づく単位を１１モル％含む含フッ素重合体（水酸基価５２ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ２０，０００、Ｔｇ４０℃）
含フッ素重合体３：重合体が含む全単位に対して、ＣＦ３ＣＨ＝ＣＨＦに基づく単位を６７モル％、ＶＶに基づく単位を１２モル％、ＨＢＶＥに基づく単位を７モル％、ＥＶＥに基づく単位を１４モル％含む含フッ素重合体（水酸基価４０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ８，０００、Ｔｇ３２℃）
含フッ素重合体４：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を５０モル％、ＥＶＥに基づく単位を１９モル％、ＣＨＶＥに基づく単位を１５モル％、ＨＢＶＥに基づく単位を１６モル％含む含フッ素重合体（水酸基価８０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ３，９００、Ｔｇ３５℃）
含フッ素重合体５：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を５０モル％、ＥＶＥに基づく単位を１５モル％、ＣＨＶＥに基づく単位を１５モル％、ＨＢＶＥに基づく単位を１７モル％、ＨＢＶＥに基づく単位におけるヒドロキシ基を無水コハク酸で酸変性させて得られる単位（側鎖に−Ｏ（ＣＨ２）４ＯＣ（Ｏ）ＣＨ２ＣＨ２ＣＯＯＨを有する単位）を３モル％含む含フッ素重合体（水酸基価８５ｍｇＫＯＨ／ｇ、酸価１４ｍｇＫＯＨ／ｇ、Ｔｇ２０℃、ＭＦＴ３０℃）
含フッ素重合体６：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を５０モル％、ＥＶＥに基づく単位を４６モル％、ＣＨＭＶＥに基づく単位を３モル％、ＣＭＥＯＶＥに基づく単位を１モル％含む含フッ素重合体（水酸基価１５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｔｇ１６℃、ＭＦＴ２７℃）
含フッ素重合体７：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を４１モル％、ＡＶに基づく単位を３７モル％、ＶＶに基づく単位を１３モル％、ＨＥＡＥに基づく単位を９モル％含む含フッ素重合体（水酸基価４０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ１３，０００、Ｔｇ４０℃）
含フッ素重合体８：重合体が含む全単位に対して、ＣＴＦＥに基づく単位を５０モル％、ＣＨＶＥに基づく単位を４０モル％、ＨＢＶＥに基づく単位を１０モル％含む含フッ素重合体（水酸基価５２ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｍｎ１０，０００、Ｔｇ５２℃）
含フッ素重合体９：重合体が含む全単位に対して、ＴＦＥに基づく単位を２１モル％、ＶｄＦに基づく単位を５４モル％、ＭＭＡに基づく単位を１６モル％、ＢＭＡに基づく単位を９モル％含む含フッ素重合体（水酸基価０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、Ｔｇ５℃、ＭＦＴ１５℃） [Fluorine-containing polymer]
Fluorine-containing polymer 1: 45 mol% of TFE-based units, 14 mol% of HEAE-based units, 31 mol% of VV-based units, and 6 mol% of VBn-based units with respect to all the units contained in the polymer. Fluorine-containing polymer containing 4 mol% of units based on% and AV (hydroxyl value 55 mgKOH / g, acid value 0 mgKOH / g, Mn11,400, Tg35 ° C.)
Fluorine-containing polymer 2: 50 mol% of CTFE-based units, 24 mol% of EVE-based units, 15 mol% of CHVE-based units, and 11 mol% of HBVE-based units with respect to all units contained in the polymer. Fluorine-containing polymer containing% (hydroxyl value 52 mgKOH / g, acid value 0 mgKOH / g, Mn20,000, Tg40 ° C.)
Fluorine-containing polymer 3: 67 mol% of units based on CF 3 CH = CHF, 12 mol% of units based on VV, 7 mol% of units based on HBVE, based on EVE, based on all units contained in the polymer. Fluorine-containing polymer containing 14 mol% of units (hydroxyl value 40 mgKOH / g, acid value 0 mgKOH / g, Mn 8,000, Tg 32 ° C)
Fluorine-containing polymer 4: 50 mol% of CTFE-based units, 19 mol% of EVE-based units, 15 mol% of CHVE-based units, and 16 mol% of HBVE-based units with respect to all units contained in the polymer. Fluorine-containing polymer containing% (hydroxyl value 80 mgKOH / g, acid value 0 mgKOH / g, Mn3,900, Tg35 ° C.)
Fluorine-containing polymer 5: 50 mol% of CTFE-based units, 15 mol% of EVE-based units, 15 mol% of CHVE-based units, and 17 mol% of HBVE-based units with respect to all units contained in the polymer. %, 3 mol% of the unit (unit having -O (CH 2 ) 4 OC (O) CH 2 CH 2 COOH in the side chain) obtained by acid-modifying the hydroxy group in the unit based on HBVE with succinic anhydride. Fluorine-containing polymer (hydroxyl value 85 mgKOH / g, acid value 14 mgKOH / g, Tg 20 ° C, MFT 30 ° C)
Fluorine-containing polymer 6: CTFE-based unit is 50 mol%, EVE-based unit is 46 mol%, CHMVE-based unit is 3 mol%, and CMEOVE-based unit is 1 mol% of all units contained in the polymer. Fluorine-containing polymer containing% (hydroxyl value 15 mgKOH / g, acid value 0 mgKOH / g, Tg 16 ° C, MFT 27 ° C)
Fluorine-containing polymer 7: 41 mol% of CTFE-based units, 37 mol% of AV-based units, 13 mol% of VV-based units, and 9 mol of HEAE-based units with respect to all units contained in the polymer. Fluorine-containing polymer containing% (hydroxyl value 40 mgKOH / g, acid value 0 mgKOH / g, Mn13,000, Tg40 ° C.)
Fluorine-containing polymer 8: Fluorine-containing polymer containing 50 mol% of CTFE-based units, 40 mol% of CHVE-based units, and 10 mol% of HBVE-based units with respect to all the units contained in the polymer. 52 mgKOH / g, acid value 0 mgKOH / g, Mn 10,000, Tg 52 ° C.)
Fluorine-containing polymer 9: 21 mol% of TFE-based units, 54 mol% of VdF-based units, 16 mol% of MMA-based units, and 9 mol of BMA-based units with respect to all units contained in the polymer. Fluorine-containing polymer containing% (hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g, Tg 5 ° C, MFT 15 ° C)

〔中塗り塗料〕
中塗り塗料１：エポキシ系塗料
中塗り塗料２：ウレタン系塗料
中塗り塗料３：エポキシ系塗料（グラフェン含有量１質量％）
中塗り塗料４：ウレタン系塗料（グラフェン含有量１質量％）
〔下塗り塗料〕
下塗り塗料１：エポキシ系塗料
下塗り塗料２：塗料の全質量に対して、亜鉛末を７０質量％、シリコーン樹脂を２０質量％、グラフェン１を１質量％、有機溶剤を９質量％含む塗料
下塗り塗料３：塗料の全質量に対して、亜鉛末を７０質量％、エポキシ樹脂を２０質量％、グラフェン１を１質量％、有機溶剤を９質量％含む塗料 [Intermediate paint]
Intermediate paint 1: Epoxy paint Intermediate paint 2: Urethane paint Intermediate paint 3: Epoxy paint (graphene content 1% by mass)
Intermediate paint 4: Urethane paint (graphene content 1% by mass)
[Undercoat paint]
Undercoat paint 1: Epoxy paint Undercoat paint 2: Paint that contains 70% by mass of zinc powder, 20% by mass of silicone resin, 1% by mass of graphene 1, and 9% by mass of organic solvent with respect to the total mass of the paint. 3: A paint containing 70% by mass of zinc powder, 20% by mass of epoxy resin, 1% by mass of graphene 1 and 9% by mass of an organic solvent with respect to the total mass of the paint.

〔添加剤〕
顔料１：酸化チタン顔料（酸化チタン含有量：８９質量％）
顔料２：酸化チタン顔料（酸化チタン含有量：８５質量％）
硬化剤１：ポリイソシアネート系硬化剤（イソシアネート基の含有量２２質量％、２５℃における粘度３，０００ｍＰａ・ｓ）
硬化剤２：ポリイソシアネート系硬化剤（イソシアネート基の含有量１８質量％、２５℃における粘度２，５００ｍＰａ・ｓ）
硬化剤３：ポリイソシアネート系硬化剤（イソシアネート基の含有量２３質量％、２５℃における粘度５００ｍＰａ・ｓ、数平均分子量４００）
硬化触媒：ジブチルスズジラウレートのキシレン溶液（１０，０００倍希釈品） 〔Additive〕
Pigment 1: Titanium oxide pigment (titanium oxide content: 89% by mass)
Pigment 2: Titanium oxide pigment (titanium oxide content: 85% by mass)
Curing agent 1: Polyisocyanate-based curing agent (isocyanate group content 22% by mass, viscosity at 25 ° C. 3,000 mPa · s)
Curing agent 2: Polyisocyanate-based curing agent (isocyanate group content 18% by mass, viscosity at 25 ° C. 2,500 mPa · s)
Curing agent 3: Polyisocyanate-based curing agent (isocyanate group content 23% by mass, viscosity at 25 ° C. 500 mPa · s, number average molecular weight 400)
Curing catalyst: xylene solution of dibutyltin dilaurate (10,000-fold diluted product)

＜塗料の製造＞
表１に記載の各成分を混合して、フッ素系塗料１〜７および１０〜１２を得た。
また、表１に記載の各成分を、２軸押出機（サーモプリズム社製、１６ｍｍ押出機）を用いて、１２０℃のバレル設定温度にて溶融混練し、得られた混練物を冷却し、粉砕機（ＦＲＩＴＳＣＨ社製、製品名：ロータースピードミルＰ１４）を用いて粉砕し、１５０メッシュで分級して、平均粒子径が約４０μｍである粉体状のフッ素系塗料８および９を得た。
フッ素系塗料１〜５、１１および１２は溶剤型塗料であり、フッ素系塗料６、７および１０は水系塗料であり、フッ素系塗料８および９は粉体塗料である。 <Manufacturing of paint>
Each component shown in Table 1 was mixed to obtain fluorine-based paints 1 to 7 and 10 to 12.
Further, each component shown in Table 1 was melt-kneaded at a barrel set temperature of 120 ° C. using a twin-screw extruder (manufactured by Thermoprism, 16 mm extruder), and the obtained kneaded product was cooled. The mixture was pulverized using a pulverizer (manufactured by FRITSCH, product name: rotor speed mill P14) and classified by 150 mesh to obtain powdery fluorine-based paints 8 and 9 having an average particle size of about 40 μm.
Fluorine-based paints 1 to 5, 11 and 12 are solvent-based paints, fluorine-based paints 6, 7 and 10 are water-based paints, and fluorine-based paints 8 and 9 are powder paints.

〔例１〜１２〕
＜塗膜付き基材の製造＞
鉄鋼基材上に、下塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して下塗り層（膜厚３０μｍ）を形成した。次いで、下塗り層上に、中塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して中塗り層（膜厚３０μｍ）を形成した。次いで、中塗り層上に、フッ素系塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して上塗り層（膜厚２５μｍ）を形成した。以上により、基材、下塗り層、中塗り層、上塗り層をこの順に有する塗膜付き基材１を得た。
使用するフッ素系塗料の種類を表１のように変更する以外は同様にして、塗膜付き基材２〜７および１０〜１２を得た。 [Examples 1 to 12]
<Manufacturing of base material with coating film>
The undercoat paint 1 was applied onto the steel substrate using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an undercoat layer (thickness 30 μm). Next, the intermediate coating paint 1 was applied onto the undercoat layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an intermediate coating layer (thickness 30 μm). Next, the fluorine-based paint 1 was applied onto the intermediate coating layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form a top coating layer (thickness 25 μm). From the above, a base material 1 with a coating film having a base material, an undercoat layer, an intermediate coating layer, and a topcoat layer in this order was obtained.
Substrate 2-7 and 10-12 with a coating film were obtained in the same manner except that the type of the fluorine-based coating material used was changed as shown in Table 1.

アルミニウム基材上に、下塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して下塗り層（膜厚３０μｍ）を形成した。次いで、下塗り層上に、中塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して中塗り層（膜厚３０μｍ）を形成した。次いで、中塗り層上に、フッ素系塗料８を静電塗装し、２００℃雰囲気中で２０分間保持したのち２５℃まで冷却して上塗り層（膜厚５５μｍ）を形成した。以上により、基材、下塗り層、中塗り層、上塗り層をこの順に有する塗膜付き基材８を得た。
フッ素系塗料８にかえてフッ素系塗料９を用いる以外は同様にして、塗膜付き基材９を得た。
得られた各塗膜付き基材を、後述の評価に供した。結果を表１に示す。 The undercoat paint 1 was applied onto an aluminum substrate using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an undercoat layer (thickness: 30 μm). Next, the intermediate coating paint 1 was applied onto the undercoat layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an intermediate coating layer (thickness 30 μm). Next, the fluorine-based coating material 8 was electrostatically coated on the intermediate coating layer, held in an atmosphere of 200 ° C. for 20 minutes, and then cooled to 25 ° C. to form an upper coating layer (thickness 55 μm). From the above, a base material 8 with a coating film having a base material, an undercoat layer, an intermediate coating layer, and a topcoat layer in this order was obtained.
A base material 9 with a coating film was obtained in the same manner except that the fluorine-based paint 9 was used instead of the fluorine-based paint 8.
The obtained substrate with a coating film was subjected to the evaluation described later. The results are shown in Table 1.

＜塗膜付き基材の評価＞
（耐候性）
Ａｃｃｅｌｅｒａｔｅｄ Ｗｅａｔｈｅｒｉｎｇ Ｔｅｓｔｅｒ（Ｑ−ＰＡＮＥＬ ＬＡＢ ＰＲＯＤＵＣＴＳ社製、モデル：ＱＵＶ／ＳＥ）を用いた促進耐候性試験機を用い、試験時間を１００００時間として促進耐候性試験を行った。試験前の塗膜の６０度鏡面光沢値を１００％として、試験後の塗膜の６０度鏡面光沢値の保持率（光沢保持率：％）を求め、以下の基準で評価した。６０度鏡面光沢値は、光沢計（ＢＹＫ社商品名 ｍｉｃｒｏ−ＴＲＩ−ｇｒｏｓｓ、入反射角６０度）にて測定した。光沢保持率が高いほど、耐光性に優れ、耐候性が良好である。
ＳＳ：光沢保持率が８５％以上である。
Ｓ：光沢保持率が８０％以上８５％未満である。
Ａ：光沢保持率が６０％以上８０％未満である。
Ｂ：光沢保持率が４０％以上６０％未満である。
Ｃ：光沢保持率が４０％未満である。 <Evaluation of substrate with coating film>
(Weatherability)
An accelerated weathering test was conducted using an accelerated weathering tester using an Accelerated Weathering Tester (manufactured by Q-PANEL LAB PRODUCTS, model: QUV / SE) with a test time of 10,000 hours. The retention rate (gloss retention rate:%) of the 60-degree mirror surface gloss value of the coating film after the test was determined with the 60-degree mirror surface gloss value of the coating film before the test as 100%, and evaluated according to the following criteria. The 60-degree mirror surface gloss value was measured with a gloss meter (BYK trade name micro-TRI-loss, input reflection angle 60 degrees). The higher the gloss retention rate, the better the light resistance and the better the weather resistance.
SS: The gloss retention rate is 85% or more.
S: The gloss retention rate is 80% or more and less than 85%.
A: The gloss retention rate is 60% or more and less than 80%.
B: The gloss retention rate is 40% or more and less than 60%.
C: The gloss retention rate is less than 40%.

Figure 2021175763
Figure 2021175763

〔例２１〜２３〕
表２に記載の各成分を混合して、固形分質量７１質量％、ＶＯＣ含有量４０８ｇ／Ｌである各フッ素系塗料２１〜２３を得た。
鉄鋼基材上に、下塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して下塗り層（膜厚３０μｍ）を形成した。次いで、下塗り層上に、フッ素系塗料２２をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して上塗り層（１コートで膜厚７５μｍ）を形成した。以上により、基材、下塗り層、および上塗り層をこの順に有する塗膜付き基材２１を得た。
フッ素系塗料２２にかえてフッ素系塗料２３を用いた以外は同様にして、フッ素系塗料２４を得た。なお、フッ素系塗料２１は、塗料粘度が高く塗布が困難であったため、塗膜付き基材を製造しなかった。 [Examples 21 to 23]
Each of the components shown in Table 2 was mixed to obtain 21 to 23 of each fluorine-based paint having a solid content of 71% by mass and a VOC content of 408 g / L.
The undercoat paint 1 was applied onto the steel substrate using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an undercoat layer (thickness 30 μm). Next, the fluorine-based paint 22 was applied onto the undercoat layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an overcoat layer (thickness 75 μm in one coat). From the above, a base material 21 with a coating film having a base material, an undercoat layer, and a topcoat layer in this order was obtained.
A fluorine-based paint 24 was obtained in the same manner except that the fluorine-based paint 23 was used instead of the fluorine-based paint 22. Since the fluorine-based paint 21 had a high paint viscosity and was difficult to apply, a base material with a coating film was not manufactured.

〔例２４〕
表２に記載の各成分を混合して、フッ素系塗料２４を得た。
鉄鋼基材上に、下塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して下塗り層（膜厚３０μｍ）を形成した。次いで、下塗り層上に、フッ素系塗料２４をアプリケーターを用いて塗布し、５℃で１週間乾燥および硬化させて上塗り層（１コートで膜厚７５μｍ）を形成した。以上により、基材、下塗り層、および上塗り層をこの順に有する塗膜付き基材２４を得た。
得られた各塗膜付き基材を、上述および後述の評価に供した。結果を表２に示す。 [Example 24]
Each component shown in Table 2 was mixed to obtain a fluorine-based paint 24.
The undercoat paint 1 was applied onto the steel substrate using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an undercoat layer (thickness 30 μm). Next, the fluorine-based paint 24 was applied onto the undercoat layer using an applicator, and dried and cured at 5 ° C. for 1 week to form an overcoat layer (one coat having a film thickness of 75 μm). From the above, a base material 24 with a coating film having a base material, an undercoat layer, and a topcoat layer in this order was obtained.
The obtained substrate with a coating film was subjected to the evaluations described above and described later. The results are shown in Table 2.

＜塗膜付き基材の評価＞
（塗料粘度）
ＪＩＳ Ｋ ５６００−２−３：２０１４に規定されるコーン・プレート粘度計法に準拠し、Ｎｏ．４のローターを使用して、２５℃において回転数５０ｒｐｍにて塗料粘度を測定し、下記評価基準によって評価した。
Ｓ：１，０００ｍＰａ・ｓ未満
Ａ：１，０００ｍＰａ・ｓ以上２，０００ｍＰａ・ｓ未満
Ｂ：２，０００ｍＰａ・ｓ以上３，０００ｍＰａ・ｓ未満
Ｃ：３，０００ｍＰａ・ｓ以上 <Evaluation of substrate with coating film>
(Paint viscosity)
In accordance with the cone-plate viscometer method specified in JIS K 5600-2-3: 2014, No. Using the rotor of No. 4, the paint viscosity was measured at 25 ° C. and a rotation speed of 50 rpm, and evaluated according to the following evaluation criteria.
S: Less than 1,000 mPa ・ s A: 1,000 mPa ・ s or more and less than 2,000 mPa ・ s B: 2,000 mPa ・ s or more and less than 3,000 mPa ・ s C: 3,000 mPa ・ s or more

（塗膜の耐薬品性）
イオン交換水および試薬特級の塩酸により５％塩酸水溶液を作製した。また、イオン交換水および試薬特級の水酸化ナトリウムにより５％水酸化ナトリウム水溶液を作製した。
次に、上記塩酸水溶液、水酸化ナトリウム水溶液をそれぞれ塗膜上に５ｍＬずつ滴下した後に蓋をして、４時間保持した後、水洗した。その後、塗膜上のスポット跡を目視観察し、以下の基準に基づいて耐塩酸性、耐硝酸性を評価した。
Ａ：薬品滴下箇所の塗膜面に異常なし。
Ｂ：薬品滴下箇所の塗膜面にブリスターあり。
Ｃ：薬品滴下箇所の塗膜全剥がれ。 (Chemical resistance of coating film)
A 5% aqueous hydrochloric acid solution was prepared with ion-exchanged water and special grade hydrochloric acid. In addition, a 5% sodium hydroxide aqueous solution was prepared with ion-exchanged water and special grade sodium hydroxide.
Next, 5 mL each of the above hydrochloric acid aqueous solution and sodium hydroxide aqueous solution was dropped onto the coating film, covered with a lid, held for 4 hours, and then washed with water. Then, the spot marks on the coating film were visually observed, and the hydrochloric acid resistance and nitric acid resistance were evaluated based on the following criteria.
A: There is no abnormality on the coating film surface where the chemicals are dropped.
B: There is a blister on the coating film surface where the chemical is dropped.
C: The coating film is completely peeled off at the place where the chemical is dropped.

（塗膜の耐水性）
塗膜付き基材を６０℃の温水に１８時間浸漬後、５℃の冷水に１５時間浸漬し、その後５℃で乾燥し、塗膜の外観について以下の基準に従い評価した。
Ａ：塗膜面の８０％以上の面積に、白化やふくれの発生が認められなかった。
Ｂ：塗膜面の６０％以上８０％未満の面積に、白化やふくれの発生が認められなかった。
Ｃ：塗膜面の４０％超の面積に、白化やふくれの発生が認められた。 (Water resistance of coating film)
The substrate with a coating film was immersed in warm water at 60 ° C. for 18 hours, then immersed in cold water at 5 ° C. for 15 hours, and then dried at 5 ° C., and the appearance of the coating film was evaluated according to the following criteria.
A: No whitening or blistering was observed in an area of 80% or more of the coating film surface.
B: No whitening or blistering was observed in an area of 60% or more and less than 80% of the coating film surface.
C: Whitening and blistering were observed in an area of more than 40% of the coating film surface.

Figure 2021175763
Figure 2021175763

〔例３１〜３８〕
鉄鋼基材上に、下塗り塗料２をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して下塗り層（膜厚７５μｍ）を形成した。次いで、下塗り層上に、中塗り塗料１をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して中塗り層（膜厚３０μｍ）を形成した。次いで、中塗り層上に、フッ素系塗料４をアプリケーターを用いて塗布し、２５℃で３０分間乾燥したのち、８０℃で５分間保持して上塗り層（膜厚２５μｍ）を形成した。以上により、基材、下塗り層、中塗り層、上塗り層をこの順に有する塗膜付き基材３１を得た。
使用する塗料の種類を表１のように変更する以外は同様にして、塗膜付き基材３１〜３８を得た。
得られた各塗膜付き基材を、上述および後述の評価に供した。結果を表３に示す。 [Examples 31-38]
The undercoat paint 2 was applied onto the steel substrate using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an undercoat layer (thickness 75 μm). Next, the intermediate coating paint 1 was applied onto the undercoat layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form an intermediate coating layer (thickness 30 μm). Next, the fluorine-based coating material 4 was applied onto the intermediate coating layer using an applicator, dried at 25 ° C. for 30 minutes, and then held at 80 ° C. for 5 minutes to form a top coating layer (thickness 25 μm). From the above, a base material 31 with a coating film having a base material, an undercoat layer, an intermediate coat layer, and a top coat layer in this order was obtained.
Substrate 31 to 38 with a coating film was obtained in the same manner except that the type of paint used was changed as shown in Table 1.
The obtained substrate with a coating film was subjected to the evaluations described above and described later. The results are shown in Table 3.

＜塗膜付き基材の評価＞
（塗膜の防錆効果）
耐塩水噴霧性試験法（ＪＩＳ Ｋ５６００−７−１：１９９９）によって判定した。塗膜をクロスカットし、塗膜面に塩水噴霧して、４８時間経過後の、クロスカット部分に発生する錆の状態を観察し、以下の基準で評価した。
Ｓ：クロスカット部分に異常なし。
Ａ：クロスカット部分の２０％未満にブリスターまたは錆が発生した。 <Evaluation of substrate with coating film>
(Rust prevention effect of coating film)
Judgment was made by a salt spray resistance test method (JIS K5600-7-1: 1999). The coating film was cross-cut, and the surface of the coating film was sprayed with salt water. After 48 hours, the state of rust generated on the cross-cut portion was observed and evaluated according to the following criteria.
S: There is no abnormality in the cross cut part.
A: Blister or rust occurred on less than 20% of the cross-cut portion.

Figure 2021175763
Figure 2021175763

Claims (13)

グラフェンおよび含フッ素重合体を含む塗料であって、
前記グラフェンは、層厚みが０．１〜１００ｎｍであり、比表面積が５０〜１，５００ｍ２／ｇであり、
前記含フッ素重合体は、水酸基価および酸価の一方または両方が１０〜１５０ｍｇＫＯＨ／ｇであることを特徴とする塗料。 A paint containing graphene and a fluorine-containing polymer.
The graphene has a layer thickness of 0.1 to 100 nm and a specific surface area of 50 to 1,500 m 2 / g.
The fluorine-containing polymer is a coating material having one or both of a hydroxyl value and an acid value of 10 to 150 mgKOH / g. 前記グラフェンは、平均最長粒子径が０．００１〜５０μｍである、請求項１に記載の塗料。 The paint according to claim 1, wherein the graphene has an average longest particle size of 0.001 to 50 μm. 前記グラフェンは、前記グラフェンの全質量に対して８５質量％以上の炭素原子を含む、請求項１または２に記載の塗料。 The coating material according to claim 1 or 2, wherein the graphene contains 85% by mass or more of carbon atoms with respect to the total mass of the graphene. 前記塗料の固形分質量に対して前記グラフェンを０．０１〜１０質量％含む、請求項１〜３のいずれか１項に記載の塗料。 The paint according to any one of claims 1 to 3, which contains 0.01 to 10% by mass of the graphene with respect to the solid content mass of the paint. 酸化チタン顔料を含む、請求項１〜４のいずれか１項に記載の塗料。 The coating material according to any one of claims 1 to 4, which comprises a titanium oxide pigment. 前記含フッ素重合体は、数平均分子量が２，０００〜３０，０００である、請求項１〜５のいずれか１項に記載の塗料。 The coating material according to any one of claims 1 to 5, wherein the fluorine-containing polymer has a number average molecular weight of 2,000 to 30,000. 数平均分子量が１００〜９００である硬化剤を含む、請求項１〜６のいずれか１項に記載の塗料。 The coating material according to any one of claims 1 to 6, which comprises a curing agent having a number average molecular weight of 100 to 900. 前記塗料がさらに溶媒を含み、前記塗料の全質量に対する前記溶媒の質量が、２０〜３５質量％である、請求項１〜７のいずれか１項に記載の塗料。 The coating material according to any one of claims 1 to 7, wherein the coating material further contains a solvent, and the mass of the solvent is 20 to 35% by mass with respect to the total mass of the coating material. ２５℃における粘度が３００〜３，０００ｍＰａ・ｓである、請求項８に記載の塗料。 The coating material according to claim 8, which has a viscosity at 25 ° C. of 300 to 3,000 mPa · s. 前記含フッ素重合体は、フルオロオレフィンに基づく単位と、ヒドロキシ基およびカルボキシ基の一方または両方を有しフッ素原子を有さない単位と、を含む、請求項１〜９のいずれか１項に記載の塗料。 The fluorine-containing polymer according to any one of claims 1 to 9, which comprises a unit based on a fluoroolefin and a unit having one or both of a hydroxy group and a carboxy group and no fluorine atom. Paint. 請求項１〜１０のいずれか１項に記載の塗料から形成される、膜厚が５０〜１００μｍである塗膜。 A coating film having a film thickness of 50 to 100 μm, which is formed from the coating material according to any one of claims 1 to 10. 基材と、亜鉛末およびグラフェンを含む下塗り層と、請求項１１に記載の塗膜からなる上塗り層と、をこの順に有する塗膜付き基材。 A base material with a coating film having a base material, an undercoat layer containing zinc powder and graphene, and a topcoat layer composed of the coating film according to claim 11 in this order. 基材上に、下塗り塗料を塗布して下塗り層を形成し、前記下塗り層上に、請求項１〜１０のいずれか１項に記載の塗料を塗布して上塗り層を形成して、前記基材と、前記下塗り層および前記上塗り層を有する塗膜とをこの順に有する塗膜付き基材を得る、塗膜付き基材の製造方法。 An undercoat paint is applied onto the base material to form an undercoat layer, and the paint according to any one of claims 1 to 10 is applied onto the undercoat layer to form an overcoat layer to form the base. A method for producing a base material with a coating film, which obtains a base material with a coating film having the material, the undercoat layer, and the coating film having the topcoat layer in this order.
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