JP4398827B2 - Resin coated metal plate - Google Patents

Resin coated metal plate Download PDF

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JP4398827B2
JP4398827B2 JP2004268685A JP2004268685A JP4398827B2 JP 4398827 B2 JP4398827 B2 JP 4398827B2 JP 2004268685 A JP2004268685 A JP 2004268685A JP 2004268685 A JP2004268685 A JP 2004268685A JP 4398827 B2 JP4398827 B2 JP 4398827B2
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resin
mass
carboxylic acid
unsaturated carboxylic
ethylene
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JP2005246953A (en
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忠繁 中元
富男 梶田
豊 貴答
雅司 今堀
和生 奥村
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Kobe Steel Ltd
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Kobe Steel Ltd
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Priority to JP2004268685A priority Critical patent/JP4398827B2/en
Priority to KR1020050002040A priority patent/KR100621724B1/en
Priority to SG200500304A priority patent/SG114688A1/en
Priority to TW094102525A priority patent/TWI255225B/en
Priority to MYPI20050426A priority patent/MY145754A/en
Priority to CNB2005100078721A priority patent/CN100333896C/en
Publication of JP2005246953A publication Critical patent/JP2005246953A/en
Priority to HK06101436A priority patent/HK1081491A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm

Description

本発明は、家庭用電気製品や建材等の用途に好適に用いることができる耐食性に優れた樹脂塗装金属板に関する。   The present invention relates to a resin-coated metal plate excellent in corrosion resistance that can be suitably used for household electrical appliances and building materials.

従来、家庭用電気製品や建材用途に用いられる金属板としては、アルミニウム板やステンレス鋼板のほか、電気亜鉛めっき鋼板や溶融亜鉛めっき鋼板等の表面処理鋼板が広く用いられている。その中でも、亜鉛めっき系の表面処理鋼板については、従来クロメート処理やリン酸塩処理が施され、家庭用電気製品を中心として、音響機器、コンピュータ部品、電子レンジの底板等、種々の部材に広く用いられている。しかし、近年、これらの表面処理鋼板に対するユーザーニーズは益々高度化し、種々多様な皮膜性能が要求されるに至っている。   Conventionally, as a metal plate used for household electrical appliances and building materials, surface-treated steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets have been widely used in addition to aluminum plates and stainless steel plates. Among them, galvanized surface-treated steel sheets are conventionally chromated and phosphated, and are widely used in various components such as household appliances, such as audio equipment, computer parts, and microwave oven bottom plates. It is used. However, in recent years, user needs for these surface-treated steel sheets have become more and more sophisticated, and various film performances have been required.

例えば、表面処理鋼板が裸使用される場合には、耐食性、アース性、指紋が付着しても目立ちにくい耐指紋性、アルカリや溶剤等に対する耐薬品性、耐汚染性等が要求される。また、プレス加工や打ち抜き加工される場合には、潤滑性、耐疵付き性、深絞り加工性、耐金型摩耗性、打ち抜き性、加工摺動面の耐黒化性、プレス油・速乾性油等に対する耐油性が要求される。   For example, when a surface-treated steel sheet is used barely, corrosion resistance, grounding properties, fingerprint resistance that is not noticeable even if fingerprints are attached, chemical resistance against alkalis, solvents, and the like, and contamination resistance are required. Also, when press working or punching, lubricity, scratch resistance, deep drawing workability, die wear resistance, punching resistance, blackening resistance of the sliding surface, press oil, quick drying Oil resistance against oil is required.

このような要求特性を満たすため、例えば、特許文献１では、クロメート処理層上に、エチレン系アイオノマー中のカルボキシル基の６０〜８０％をナトリウムイオンで中和してなる樹脂皮膜が形成された有機複合被覆鋼板が示されている。また、特許文献２では、イオンクラスターによる分子間会合したポリオレフィン共重合体樹脂エマルジョンとアジリジニル基を有する有機化合物とを含む組成物から得られる皮膜が金属板表面に形成された樹脂塗装金属板が示されている。この特許文献２において、金属板としては、クロメート処理が施されていることが好ましい旨記載されている。   In order to satisfy such required characteristics, for example, in Patent Document 1, an organic resin film formed by neutralizing 60 to 80% of carboxyl groups in an ethylene ionomer with sodium ions is formed on a chromate treatment layer. A composite coated steel sheet is shown. Patent Document 2 discloses a resin-coated metal plate in which a film obtained from a composition containing a polyolefin copolymer resin emulsion intermolecularly associated with ion clusters and an organic compound having an aziridinyl group is formed on the surface of the metal plate. Has been. In this Patent Document 2, it is described that the metal plate is preferably subjected to chromate treatment.

ところが最近では、地球環境保全のためのクロムフリー（クロメート処理を行わないようにする）の動き等により、樹脂皮膜に対して今まで以上の耐食性が要求されるようになってきた。
特開平６−２４６２２９号（請求項１） 特許第２７５９６２０号（請求項１、［００５３］等） However, recently, due to the movement of chromium-free (to avoid chromate treatment) for the preservation of the global environment, more corrosion resistance than ever has been required for resin films.
JP-A-6-246229 (Claim 1) Japanese Patent No. 2759620 (Claim 1, [0053] etc.)

上述のように、クロムフリーの金属板に積層する樹脂皮膜においても、クロメート処理した金属板に被覆した樹脂皮膜と同レベルの耐食性が要求されるようになってきたため、本発明者らは、前記特許文献２の出願後も一貫して検討を続けてきた。特許文献２に記載の樹脂皮膜はクロムフリーの場合にもある程度優れた耐食性を示すが、例えば、プレス加工時に施される潤滑油を脱脂工程で除去した後は、アルカリ処理によって樹脂皮膜が劣化して耐食性が低下するという問題があった。また、樹脂皮膜をクロムフリー金属板に被覆した後、粘着テープを樹脂皮膜表面に貼付し、長時間放置した後に粘着テープを剥がすと樹脂皮膜まで剥がれてしまう、という耐テープ剥離性（金属板と樹脂皮膜の密着性）不足の問題があった。   As described above, even in the resin film laminated on the chromium-free metal plate, the same level of corrosion resistance as the resin film coated on the chromate-treated metal plate has been required. Even after the application of Patent Document 2, the examination has been continued consistently. Although the resin film described in Patent Document 2 exhibits corrosion resistance to some extent even when it is chromium-free, for example, after removing the lubricating oil applied at the time of pressing in the degreasing process, the resin film deteriorates due to alkali treatment. Therefore, there is a problem that the corrosion resistance is lowered. Also, after coating the resin film on the chromium-free metal plate, stick the adhesive tape on the surface of the resin film, and leave it for a long time and then peel off the adhesive tape. There was a problem of insufficient adhesion of the resin film.

そこで本発明では、塗装性、潤滑性、加工性、アース性等の各種特性に優れることを前提として、さらに、脱脂工程後の耐食性および耐テープ剥離性に優れた樹脂皮膜を有する樹脂塗装金属板の提供を課題として掲げた。   Therefore, in the present invention, on the premise that various properties such as paintability, lubricity, workability, and grounding properties are excellent, a resin-coated metal plate having a resin film excellent in corrosion resistance and tape peel resistance after the degreasing process As an issue.

本発明の樹脂塗装金属板は、エチレン−不飽和カルボン酸共重合体を主成分とするエマルジョン組成物から得られる樹脂皮膜を備える樹脂塗装金属板であって、このエマルジョン組成物は、エチレン−不飽和カルボン酸共重合体以外に、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．２〜０．８モルに相当する沸点１００℃以下のアミンと、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．０２〜０．４モルに相当する１価の金属の化合物とを含むと共に、カルボキシル基と反応し得る官能基を２個以上有する架橋剤をエマルジョン組成物の固形分１００質量％に対し１〜２０質量％含み、沸点１００℃超のアミンおよびアンモニアは実質的に含まないものであるところに特徴を有する。   The resin-coated metal plate of the present invention is a resin-coated metal plate provided with a resin film obtained from an emulsion composition containing an ethylene-unsaturated carboxylic acid copolymer as a main component. In addition to the saturated carboxylic acid copolymer, an amine having a boiling point of 100 ° C. or lower corresponding to 0.2 to 0.8 mol per 1 mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer, and ethylene-unsaturated A monovalent metal compound corresponding to 0.02 to 0.4 mol per mol of the carboxyl group of the carboxylic acid copolymer, and having two or more functional groups capable of reacting with the carboxyl group The agent is contained in an amount of 1 to 20% by mass with respect to 100% by mass of the solid content of the emulsion composition, and is substantially free of amine and ammonia having a boiling point of over 100 ° C. With a butterfly.

上記エチレン−不飽和カルボン酸共重合体は、不飽和カルボン酸が１０〜４０質量％共重合されているものであることが好ましく、１５〜２５質量％共重合されているものであることが最も好ましい。また、上記沸点１００℃以下のアミンがトリエチルアミンであることも本発明の好ましい実施態様である。   The ethylene-unsaturated carboxylic acid copolymer is preferably 10-40% by mass of unsaturated carboxylic acid, and most preferably 15-25% by mass. preferable. It is also a preferred embodiment of the present invention that the amine having a boiling point of 100 ° C. or lower is triethylamine.

上記エマルジョン組成物の固形分１００質量％中に、平均粒子径１〜２００ｎｍのシリカ粒子が５〜４０質量％含まれているとよく、球状のポリエチレンワックスが０．５〜２０質量％含まれていることも好ましい。塗装性、潤滑性、加工性、アース性等の各種特性を備えることができ、さらに、脱脂工程後の耐食性および耐テープ剥離性にも優れた樹脂皮膜となる。なお、本発明の樹脂塗装金属板は、クロメート皮膜が形成されていない場合であっても良好な耐食性を示す。   It is preferable that 5 to 40% by mass of silica particles having an average particle size of 1 to 200 nm is contained in 100% by mass of the solid content of the emulsion composition, and 0.5 to 20% by mass of spherical polyethylene wax is contained. It is also preferable. Various properties such as paintability, lubricity, workability, and grounding properties can be provided, and the resin film is excellent in corrosion resistance and tape peel resistance after the degreasing process. Note that the resin-coated metal plate of the present invention exhibits good corrosion resistance even when the chromate film is not formed.

特定量の沸点１００℃以下のアミンと金属化合物を併用し、エチレン−不飽和カルボン酸共重合体を中和してエマルジョン化したので、粒径が非常に小さなエマルジョン組成物を得ることができ、塗装性、潤滑性、加工性、アース性等の各種特性に優れ、かつ、脱脂工程後の耐食性および耐テープ剥離性に優れた皮膜が形成された樹脂塗装金属板を得ることができた。   Since a specific amount of an amine having a boiling point of 100 ° C. or less and a metal compound are used together and the ethylene-unsaturated carboxylic acid copolymer is neutralized and emulsified, an emulsion composition having a very small particle size can be obtained. It was possible to obtain a resin-coated metal plate on which a film excellent in various properties such as paintability, lubricity, workability, and grounding properties and having excellent corrosion resistance and tape peel resistance after the degreasing process was formed.

本発明の樹脂塗装金属板は、金属板の少なくとも片面に、特定のエマルジョン組成物から形成された樹脂皮膜を備えるものである。金属板としては特に限定されないが、例えば、亜鉛または亜鉛系めっき鋼板、アルミニウム板、アルミ系合金板、チタン板等を挙げることができる。また、これらの金属板に、リン酸塩処理等の公知の防錆下地処理やその他の下地処理を施し、その上に樹脂皮膜を形成させてもよい。環境問題の観点からは、クロメート処理を施さないことが好ましい。   The resin-coated metal plate of the present invention is provided with a resin film formed from a specific emulsion composition on at least one surface of the metal plate. Although it does not specifically limit as a metal plate, For example, zinc or a zinc-type plated steel plate, an aluminum plate, an aluminum-type alloy plate, a titanium plate etc. can be mentioned. Further, these metal plates may be subjected to a known rust preventive ground treatment such as phosphate treatment or other ground treatment, and a resin film may be formed thereon. From the viewpoint of environmental problems, it is preferable not to perform chromate treatment.

樹脂皮膜形成のために本発明において用いられるエマルジョン組成物は、エチレン−不飽和カルボン酸共重合体（中和状態も含む）を主成分とし、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．２〜０．８モル（２０〜８０モル％）に相当する沸点１００℃以下のアミンと、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．０２〜０．４モル（２〜４０モル％）に相当する１価の金属の化合物とを含むと共に、カルボキシル基と反応し得る官能基を２個以上有する架橋剤をエマルジョン組成物の固形分１００質量％に対し０．５〜２０質量％含み、沸点１００℃超のアミンおよびアンモニアは、実質的に含まない。   The emulsion composition used in the present invention for forming a resin film has an ethylene-unsaturated carboxylic acid copolymer (including a neutralized state) as a main component and a carboxyl group possessed by the ethylene-unsaturated carboxylic acid copolymer. The amine having a boiling point of 100 ° C. or less corresponding to 0.2 to 0.8 mol (20 to 80 mol%) per mol and 0 mol per mol of carboxyl group of the ethylene-unsaturated carboxylic acid copolymer. A solid component of the emulsion composition containing a cross-linking agent containing at least two functional groups capable of reacting with a carboxyl group, and a monovalent metal compound corresponding to 0.02 to 0.4 mol (2 to 40 mol%). It contains 0.5 to 20% by mass with respect to 100% by mass, and contains substantially no amine or ammonia having a boiling point of more than 100 ° C.

上記エチレン−不飽和カルボン酸共重合体は、エチレンと、エチレン性不飽和カルボン酸の共重合体である。不飽和カルボン酸としては、（メタ）アクリル酸、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、イタコン酸等が挙げられ、これらのうちの１種以上と、エチレンとを、公知の高温高圧重合法等で重合することにより、共重合体を得ることができる。共重合体としては、ランダムが最も好ましいが、ブロック共重合体や、不飽和カルボン酸部分がグラフトしたような共重合体でも良い。なお、不飽和カルボン酸としては、（メタ）アクリル酸が好適である。また、エチレンの一部に変えてプロピレンまたは１−ブテン等のオレフィン系モノマーを用いてもよく、さらに本発明の目的を阻害しない範囲であれば、他の公知のビニル系モノマーを一部共重合（１０質量％程度以下）してもよい。   The ethylene-unsaturated carboxylic acid copolymer is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. A copolymer can be obtained by polymerization using a legal method or the like. The copolymer is most preferably random, but may be a block copolymer or a copolymer grafted with an unsaturated carboxylic acid moiety. In addition, (meth) acrylic acid is suitable as the unsaturated carboxylic acid. Further, an olefin monomer such as propylene or 1-butene may be used instead of a part of ethylene, and other known vinyl monomers are partially copolymerized as long as the object of the present invention is not impaired. (About 10 mass% or less).

エチレンに対する不飽和カルボン酸の共重合比率は、モノマー全量を１００質量％とした時に、不飽和カルボン酸が１０〜４０質量％であることが好ましい。不飽和カルボン酸が１０質量％よりも少ないと、イオンクラスターによる分子間会合の基点、あるいは架橋剤との架橋点となるカルボキシル基が少ないため、皮膜強度効果が発揮されず、耐テープ剥離性や脱脂工程後の耐食性が不充分となることがある上に、エマルジョン組成物の乳化安定性に劣るため好ましくない。より好ましい不飽和カルボン酸の下限は１５質量％である。一方、不飽和カルボン酸が４０質量％を超えると、樹脂皮膜の耐食性や耐水性に劣り、やはり脱脂工程後の耐食性が低下するため好ましくない。より好ましい上限は２５質量％である。   The copolymerization ratio of unsaturated carboxylic acid to ethylene is preferably 10 to 40% by mass of unsaturated carboxylic acid when the total amount of monomers is 100% by mass. When the amount of unsaturated carboxylic acid is less than 10% by mass, there are few carboxyl groups that serve as base points for intermolecular association by ion clusters or cross-linking points with cross-linking agents. The corrosion resistance after the degreasing process may be insufficient, and the emulsion stability of the emulsion composition is inferior. A more preferable lower limit of the unsaturated carboxylic acid is 15% by mass. On the other hand, if the unsaturated carboxylic acid exceeds 40% by mass, the corrosion resistance and water resistance of the resin film are inferior, and the corrosion resistance after the degreasing process is lowered, which is not preferable. A more preferred upper limit is 25% by mass.

上記エチレン−不飽和カルボン酸共重合体はカルボキシル基を有しているので、有機塩基や金属イオンで中和することにより、エマルジョン化（水分散体化）が可能となる。本発明では、有機塩基として沸点１００℃以下のアミンを用いる。沸点が１００℃を超えるアミン類は、樹脂塗膜を乾燥させたときに鋼板上に残存しやすく、樹脂塗膜の吸水性が増すため、耐食性の低下を招く。よって、本発明で皮膜形成のために用いられるエマルジョン組成物には沸点１００℃超のアミン類は含まれない。また、アンモニアの添加効果も認められなかったため、アンモニアも含まれない。上記沸点は、大気圧下での沸点を採用する。   Since the ethylene-unsaturated carboxylic acid copolymer has a carboxyl group, it can be emulsified (aqueous dispersion) by neutralization with an organic base or metal ion. In the present invention, an amine having a boiling point of 100 ° C. or lower is used as the organic base. Amines having a boiling point exceeding 100 ° C. are likely to remain on the steel sheet when the resin coating is dried, and the water absorption of the resin coating increases, resulting in a decrease in corrosion resistance. Therefore, the emulsion composition used for film formation in the present invention does not contain amines having a boiling point of more than 100 ° C. Also, ammonia was not included because the effect of adding ammonia was not recognized. As the boiling point, a boiling point under atmospheric pressure is adopted.

沸点１００℃以下のアミンの具体例としては、トリエチルアミン、Ｎ，Ｎ−ジメチルブチルアミン、Ｎ，Ｎ−ジメチルアリルアミン、Ｎ−メチルピロリジン、テトラメチルジアミノメタン、トリメチルアミン等の３級アミン；Ｎ−メチルエチルアミン、ジイソプロピルアミン、ジエチルアミン等の２級アミン；プロピルアミン、ｔ−ブチルアミン、ｓｅｃ−ブチルアミン、イソブチルアミン、１，２−ジブチルプロピルアミン、３−ペンチルアミン等の１級アミン等が挙げられ、１種または２種以上を混合して使用することができる。これらの中でも３級アミンが好ましく、最も好ましいものはトリエチルアミンである。   Specific examples of amines having a boiling point of 100 ° C. or lower include tertiary amines such as triethylamine, N, N-dimethylbutylamine, N, N-dimethylallylamine, N-methylpyrrolidine, tetramethyldiaminomethane, trimethylamine; N-methylethylamine, Secondary amines such as diisopropylamine and diethylamine; primary amines such as propylamine, t-butylamine, sec-butylamine, isobutylamine, 1,2-dibutylpropylamine, and 3-pentylamine, and the like. A mixture of seeds or more can be used. Of these, tertiary amines are preferred, and triethylamine is the most preferred.

沸点１００℃以下のアミンの量は、エチレン−不飽和カルボン酸共重合体中のカルボキシル基１モルに対し、０．２〜０．８モル（２０〜８０モル％）の範囲とする。この範囲であれば、耐食性や耐テープ剥離性が良好だからである。沸点１００℃以下のアミンが０．２モルより少ないと、エマルジョン中の樹脂粒子の粒径が大きくなって、このために上記効果が発揮されないものと考えられる。また、０．８モルを超えて沸点１００℃以下のアミンを用いると、エマルジョン組成物が増粘してゲル化することがあるため、好ましくない。より好ましい上記アミンの量の上限は０．６モル、さらに好ましくは０．５モルであり、より好ましい上記アミン量の下限は０．３モルである。   The amount of the amine having a boiling point of 100 ° C. or less is in the range of 0.2 to 0.8 mol (20 to 80 mol%) with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. This is because, within this range, the corrosion resistance and tape peel resistance are good. If the amine having a boiling point of 100 ° C. or less is less than 0.2 mol, it is considered that the particle size of the resin particles in the emulsion becomes large and the above effect is not exhibited. Moreover, it is not preferable to use an amine having a boiling point of more than 0.8 mol and a boiling point of 100 ° C. or less because the emulsion composition may thicken and gel. The upper limit of the amount of the amine is more preferably 0.6 mol, still more preferably 0.5 mol, and the lower limit of the amount of the amine is more preferably 0.3 mol.

本発明では、１価の金属イオンも中和のために用いる。耐溶剤性や皮膜硬度の向上に効果的である。従って、エマルジョン組成物には一価の金属の化合物が添加されている。１価の金属の化合物としては、ナトリウム、カリウム、リチウムから選ばれる１種または２種以上の金属を含むことが好ましく、これらの金属の水酸化物、炭酸化物または酸化物が好ましい。中でも、ＮａＯＨ、ＫＯＨ、ＬｉＯＨ等が好ましく、ＮａＯＨが最も性能が良く好ましい。また、２価以上の金属の化合物は添加することによる効果が認められないため、本発明で皮膜形成のために用いられるエマルジョン組成物には、エチレン−不飽和カルボン酸共重合体の反応相手のための２価以上の金属の化合物は含まれない。   In the present invention, monovalent metal ions are also used for neutralization. Effective for improving solvent resistance and film hardness. Therefore, a monovalent metal compound is added to the emulsion composition. The monovalent metal compound preferably contains one or more metals selected from sodium, potassium, and lithium, and a hydroxide, carbonate, or oxide of these metals is preferable. Among these, NaOH, KOH, LiOH and the like are preferable, and NaOH has the best performance and is preferable. In addition, since the effect of adding a metal compound having a valence of 2 or more is not recognized, the emulsion composition used for film formation in the present invention includes a reaction partner of an ethylene-unsaturated carboxylic acid copolymer. Therefore, a compound of a metal having a valence of 2 or more is not included.

この１価の金属の化合物の量は、エチレン−不飽和カルボン酸共重合体中のカルボキシル基１モルに対して、０．０２〜０．４モル（２〜４０モル％）の範囲とする。上記金属化合物量が０．０２モルより少ないと乳化安定性が不充分となるが、０．４モルを超えると、得られる樹脂皮膜の吸湿性（特にアルカリ性溶液に対して）が増大し、脱脂工程後の耐食性が劣化するため好ましくない。より好ましい金属化合物量の下限は０．０３モル、さらに好ましい下限は０．１モルであり、より好ましい金属化合物量の上限は０．５モル、さらに好ましい上限は０．２モルである。   The amount of the monovalent metal compound is in the range of 0.02 to 0.4 mol (2 to 40 mol%) with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. When the amount of the metal compound is less than 0.02 mol, the emulsion stability becomes insufficient. However, when the amount exceeds 0.4 mol, the hygroscopicity (particularly with respect to the alkaline solution) of the resulting resin film increases, and degreasing Since corrosion resistance after a process deteriorates, it is not preferable. The lower limit of the more preferable amount of the metal compound is 0.03 mol, and the more preferable lower limit is 0.1 mol. The upper limit of the more preferable amount of the metal compound is 0.5 mol, and the more preferable upper limit is 0.2 mol.

上記沸点１００℃以下のアミンと上記１価の金属化合物のそれぞれの使用量の好ましい範囲は上記したとおりであるが、これらはいずれもエチレン−不飽和カルボン酸共重合体中のカルボキシル基を中和してエマルジョン化するために用いられる。従って、これらの合計量（中和量）が多すぎると、エマルジョン組成物のの粘度が急激に上昇して固化することがある上に、過剰なアルカリ分は耐食性劣化の原因となるため、揮発させるために多大なエネルギーが必要となるため好ましくない。しかし、中和量が少なすぎると乳化性に劣るため、やはり好ましくない。従って、沸点１００℃以下のアミンと上記１価の金属化合物の合計使用量は、エチレン−不飽和カルボン酸共重合体中のカルボキシル基１モルに対し、０．３〜１．０モルの範囲とすることが好ましい。   The preferred ranges of the respective amounts of the amine having a boiling point of 100 ° C. or less and the monovalent metal compound are as described above, and these all neutralize the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. And used for emulsification. Therefore, if the total amount (neutralization amount) is too large, the viscosity of the emulsion composition may rapidly increase and solidify, and excessive alkali will cause corrosion resistance deterioration. It is not preferable because a large amount of energy is required to make it. However, if the neutralization amount is too small, the emulsifiability is inferior, which is not preferable. Therefore, the total amount of the amine having a boiling point of 100 ° C. or less and the monovalent metal compound is in the range of 0.3 to 1.0 mol with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. It is preferable to do.

本発明で用いられるエマルジョン組成物は、沸点１００℃以下のアミンと１価の金属イオンを併用して乳化したことにより、組成物中の樹脂粒子は５〜５０ｎｍという極めて小さな微粒子（油滴）状態で水性媒体中に安定に存在している。このため、得られる樹脂皮膜の造膜性、金属板への密着性、皮膜の緻密化が達成され、耐食性や耐テープ剥離性が向上したのではないかと推定される。上記水性媒体には、水の他に、アルコールやエーテル等の親水性溶媒が含まれていても良い。なお、エマルジョン中の樹脂粒子の粒子径は、例えば光散乱光度計（大塚電子社製等）を用いたレーザー回折法によって測定することができる。   The emulsion composition used in the present invention is emulsified by combining an amine having a boiling point of 100 ° C. or less and a monovalent metal ion, so that the resin particles in the composition are in a very small fine particle (oil droplet) state of 5 to 50 nm. And stably present in an aqueous medium. For this reason, it is presumed that the film forming property of the resulting resin film, the adhesion to the metal plate, and the densification of the film were achieved, and the corrosion resistance and tape peel resistance were improved. The aqueous medium may contain a hydrophilic solvent such as alcohol or ether in addition to water. The particle size of the resin particles in the emulsion can be measured, for example, by a laser diffraction method using a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd.).

沸点１００℃以下のアミンと１価の金属イオンによるエチレン−不飽和カルボン酸共重合体の中和工程（エマルジョン化工程）では、沸点１００℃以下のアミンと１価の金属の化合物とを略同時に共重合体へと添加するか、沸点１００℃以下のアミンを先に添加することが望ましい。理由は定かではないが、沸点１００℃以下のアミンを後添加すると、耐食性・耐テープ剥離性の向上効果が不充分となることがあるためである。   In the neutralization step (emulsification step) of an ethylene-unsaturated carboxylic acid copolymer with an amine having a boiling point of 100 ° C. or less and a monovalent metal ion, an amine having a boiling point of 100 ° C. or less and a monovalent metal compound are substantially simultaneously mixed. It is desirable to add to the copolymer or to add an amine having a boiling point of 100 ° C. or lower first. The reason is not clear, but if an amine having a boiling point of 100 ° C. or lower is added later, the effect of improving corrosion resistance and tape peel resistance may be insufficient.

上記沸点１００℃以下のアミンおよび１価の金属イオンによって中和されたカルボキシル基を有するエチレン−不飽和カルボン酸共重合体は、イオンクラスターによる分子間会合を形成し（アイオノマー化）、耐食性・耐テープ剥離性に優れた樹脂皮膜を形成する。しかし、より強靱な皮膜を形成するためには、官能基間反応を利用した化学結合によってポリマー鎖同士を架橋させることが望ましい。そこで、本発明のエマルジョン組成物は、カルボキシル基と反応し得る官能基を２個以上有する架橋剤を必須成分として含有する。その量は、エマルジョン組成物中の固形分１００質量％のうち、１〜２０質量％とする。１質量％より少ないと、化学結合による架橋の効果が不充分となり、耐食性・耐テープ剥離性の向上効果が発揮されにくい。一方、２０質量％を超えて配合すると、樹脂皮膜の架橋密度が過度に高くなりすぎて硬度が上昇し、プレス加工時の変形に追従できなくなることからクラックが発生し、その結果耐食性や塗装性を低下させるため好ましくない。より好ましい架橋剤量は、エマルジョン組成物中の固形分１００質量％のうち、５〜１０質量％である。なお、エチレン−不飽和カルボン酸共重合体に対する架橋剤量の比率としては、共重合体中のカルボキシル基量に応じて架橋剤量を適宜変更することが望まれるが、通常、共重合体１００質量部に対し、架橋剤を０．５〜５０質量部（より好ましくは５〜２０質量部）とすることが好ましい。   The ethylene-unsaturated carboxylic acid copolymer having a carboxyl group neutralized by an amine having a boiling point of 100 ° C. or less and a monovalent metal ion forms an intermolecular association by ion clusters (ionomerization), and is resistant to corrosion and resistance. Forms a resin film with excellent tape peelability. However, in order to form a tougher film, it is desirable to crosslink the polymer chains by chemical bonding utilizing a reaction between functional groups. Therefore, the emulsion composition of the present invention contains a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group as an essential component. The amount is 1 to 20% by mass in 100% by mass of the solid content in the emulsion composition. When the amount is less than 1% by mass, the effect of crosslinking by chemical bonding becomes insufficient, and the effect of improving the corrosion resistance and tape peel resistance is hardly exhibited. On the other hand, if it exceeds 20% by mass, the crosslinking density of the resin film becomes excessively high, the hardness increases, and it becomes impossible to follow the deformation at the time of pressing, resulting in cracks, resulting in corrosion resistance and paintability. Is not preferable. A more preferable amount of the crosslinking agent is 5 to 10% by mass in 100% by mass of the solid content in the emulsion composition. In addition, as a ratio of the amount of the crosslinking agent to the ethylene-unsaturated carboxylic acid copolymer, it is desired to appropriately change the amount of the crosslinking agent according to the amount of the carboxyl group in the copolymer. It is preferable to make a crosslinking agent into 0.5-50 mass parts (more preferably 5-20 mass parts) with respect to mass parts.

カルボキシル基と反応し得る官能基を１分子中に２個以上有する架橋剤としては特に限定されないが、ソルビトールポリグリシジルエーテル、（ポリ）グリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、（ポリ）エチレングリコールジグリシジルエーテル等のポリグリシジルエーテル類や、ポリグリシジルアミン類等のグリシジル基含有架橋剤；４，４’−ビス（エチレンイミンカルボニルアミノ）ジフェニルメタン、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ’−ジフェニルメタン−４，４’−ビス（１−アジリジンカルボキシアミド）、トルエンビスアジリジンカルボキシアミド等の２官能アジリジン化合物；トリ−１−アジリジニルホスフィンオキサイド、トリス〔１−（２−メチル）アジリジニル〕ホスフィンオキサイド、トリメチロールプロパントリス（β−アジリジニルプロピオネート）、トリス−２，４，６−（１−アジリジニル）−１，３，５−トリアジン、テトラメチルプロパンテトラアジリジニルプロピオネート等の３官能以上のアジリジン化合物あるいはこれらの誘導体等のアジリジニル基含有架橋剤が好適例として挙げられ、これらのうちの１種または２種以上を用いることができる。中でも、アジリジニル基含有架橋剤が好ましい。なお、多官能アジリジンと、１官能アジリジン（エチレンイミン等）を併用してもよい。   Although it does not specifically limit as a crosslinking agent which has 2 or more of functional groups which can react with a carboxyl group in 1 molecule, A sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, a pentaerythritol polyglycidyl ether, a trimethylol propane polyglycidyl Glycidyl group-containing crosslinking agents such as ether, neopentyl glycol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, and polyglycidyl amines; 4,4'-bis (ethyleneiminecarbonylamino) diphenylmethane N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), toluenebisua Bifunctional aziridine compounds such as lysine carboxamide; tri-1-aziridinylphosphine oxide, tris [1- (2-methyl) aziridinyl] phosphine oxide, trimethylolpropane tris (β-aziridinylpropionate), tris An aziridinyl group-containing crosslinking agent such as a tri- or higher functional aziridine compound such as -2,4,6- (1-aziridinyl) -1,3,5-triazine, tetramethylpropanetetraaziridinylpropionate, or a derivative thereof. Are mentioned as preferred examples, and one or more of them can be used. Of these, aziridinyl group-containing crosslinking agents are preferred. In addition, you may use together polyfunctional aziridine and monofunctional aziridine (ethyleneimine etc.).

本発明で用いられるエマルジョン組成物には、固形分換算で５〜４０質量％のシリカ粒子を含有させてもよい。耐食性、塗装性、耐疵付き性等の向上に効果的であると共に、脱脂後の耐食性および耐テープ剥離性の改善にも有効である。５質量％より少ないとこれらの効果が発現しにくいが、４０質量％を超えると、シリカ粒子の割合が過度に高くなって造膜性が低下し、乾燥工程の際に樹脂皮膜にクラックが入ることがあり、耐食性低下につながるため好ましくない。さらには、シリカ粒子が増磨剤として作用するようになり、皮膜の潤滑性を高め、摩擦係数を低下させて、加工時における金型の摩耗を生じ、金型の寿命を縮めることとなる。より好ましいシリカ粒子量の下限は２０質量％、上限は３０質量％である。   You may make the emulsion composition used by this invention contain 5-40 mass% silica particle in conversion of solid content. It is effective for improving corrosion resistance, paintability, scratch resistance, etc., and also effective for improving corrosion resistance after degreasing and tape peeling resistance. When the amount is less than 5% by mass, these effects are hardly exhibited. However, when the amount exceeds 40% by mass, the ratio of silica particles becomes excessively high and the film forming property is lowered, and the resin film is cracked during the drying process. In some cases, it leads to a decrease in corrosion resistance. Further, the silica particles act as a polishing agent, improving the lubricity of the film and lowering the coefficient of friction, causing wear of the mold during processing, and shortening the life of the mold. A more preferable lower limit of the amount of silica particles is 20% by mass, and an upper limit is 30% by mass.

上記のようなシリカ粒子の効果を最大限に得るには、シリカ粒子の平均粒子径が１〜２００ｎｍの範囲にあることが好ましい。シリカ粒子の粒子径が小さくなるほど皮膜の耐食性が向上する。これは、樹脂皮膜が緻密化し、密着性が向上することにより、耐食性を一層高めると考えられる。このような観点からはシリカ粒子の粒子径は小さいほど良いが、極端に微少な粒子となると、上記効果が飽和してしまうため、粒子径の下限は１ｎｍが好ましい。一方、シリカ粒子の粒子径が２００ｎｍを超えると、樹脂皮膜の表面を粗くして、緻密な樹脂皮膜を形成することができず、さらに、シリカ粒子が増磨剤としても作用するので、加工性の劣化につながるため好ましくない。特に、脱脂後の耐食性を重視する場合は、シリカ粒子の平均粒子径を４〜２０ｎｍの範囲とすることが好ましい。   In order to obtain the maximum effect of the silica particles as described above, the average particle diameter of the silica particles is preferably in the range of 1 to 200 nm. The smaller the particle size of the silica particles, the better the corrosion resistance of the coating. This is considered to further increase the corrosion resistance by densifying the resin film and improving the adhesion. From this point of view, the smaller the particle size of the silica particles, the better. However, when the particles are extremely small, the above effect is saturated, so the lower limit of the particle size is preferably 1 nm. On the other hand, when the particle diameter of the silica particles exceeds 200 nm, the surface of the resin film is roughened, and a dense resin film cannot be formed. Further, the silica particles also act as a polisher. This is not preferable because it leads to deterioration. In particular, when importance is attached to the corrosion resistance after degreasing, the average particle diameter of the silica particles is preferably in the range of 4 to 20 nm.

このようなシリカ粒子は、通常、コロイダルシリカとして知られており、本発明においては、例えば、「スノーテックス」シリーズ（日産化学工業社製のコロイダルシリカ）の「ＸＳ」、「ＳＳ」、「４０」、「Ｎ」、「ＵＰ」等を好適に用いることができる。   Such silica particles are generally known as colloidal silica. In the present invention, for example, “XS”, “SS”, “40” of “Snowtex” series (colloidal silica manufactured by Nissan Chemical Industries, Ltd.) are used. ”,“ N ”,“ UP ”and the like can be preferably used.

本発明のエマルジョン組成物には、ワックスが固形分換算で０．５〜２０質量％の範囲で含まれていてもよい。ワックスは、得られる樹脂皮膜の潤滑性および耐疵付き性の向上に効果がある。さらに、プレス加工や打ち抜き加工の際に必要な深絞り性および打ち抜き性、耐金型摩耗性、加工時における摺動面の耐黒化性を向上させ、優れた加工性を付与するために好ましく使用されるものである。   The emulsion composition of the present invention may contain a wax in a range of 0.5 to 20% by mass in terms of solid content. The wax is effective in improving the lubricity and scratch resistance of the resulting resin film. Furthermore, it is preferable to improve the deep drawability and punchability required during press working and punching, wear resistance of the mold, blackening resistance of the sliding surface during processing, and impart excellent workability. It is what is used.

ワックスの量が固形分換算で０．５質量％より少ない時には、得られる樹脂皮膜の潤滑性が不充分となり、耐疵付き性の向上や、満足すべき加工性を得ることができない。他方、２０質量％を超える場合は、得られる樹脂皮膜の潤滑性は充分であるが、電着塗装や粉体塗装、またはシルク印刷による後塗装が施された際の塗膜密着性（塗装性）に劣る。また、脱脂後の耐食性および耐テープ剥離性も劣化する。これは、後塗装工程での加熱や、経時的な変化によって、ワックスが軟化・液化あるいはブルーミングして、樹脂皮膜と後塗装の塗膜の界面や金属板と樹脂皮膜の界面に濃化するので、後塗装の塗膜との密着性や金属板との密着性が悪くなるためと考えられる。より好ましいワックスの上限値は１０質量％であり、さらに好ましい上限値は５．０質量％である。   When the amount of the wax is less than 0.5% by mass in terms of solid content, the resulting resin film has insufficient lubricity, and it is impossible to improve the scratch resistance and to obtain satisfactory processability. On the other hand, if it exceeds 20% by mass, the resulting resin film has sufficient lubricity, but the film adhesion (paintability) when electrodeposition coating, powder coating, or post-coating by silk printing is applied. ). Moreover, the corrosion resistance and detaping resistance after degreasing also deteriorate. This is because the wax softens, liquefies, or blooms due to heating in the post-coating process or changes over time, and concentrates at the interface between the resin film and the post-coating film or between the metal plate and the resin film. This is thought to be because the adhesion to the post-coating coating film and the adhesion to the metal plate deteriorate. A more preferable upper limit value of the wax is 10% by mass, and a further preferable upper limit value is 5.0% by mass.

ワックスとしては特に限定されず、天然ワックス、合成ワックスこれらの混合物等が使用可能である。天然ワックスとしては、例えば、カルナバワックス、ライスワックス、キャンデリラワックス、モンタン系ワックス及びその誘導体、鉱油系ワックス、マイクロクリスタリンワックス、パラフィンワックス等の他、これらにカルボキシル基を付与した誘導体も使用することができる。   The wax is not particularly limited, and natural wax, synthetic wax, and the like can be used. As natural waxes, for example, carnauba wax, rice wax, candelilla wax, montan wax and derivatives thereof, mineral oil wax, microcrystalline wax, paraffin wax and the like, and derivatives having a carboxyl group added thereto may also be used. Can do.

合成ワックスとしては、ポリエチレン、酸化ポリエチレン、ポリプロピレン、エチレンとプロピレン共重合系ワックス、エチレンと他のモノマーとの共重合ワックスの酸化ワックスがある。この系統は共重合相手の変化でターポリマー系も含め多種使用することができる。さらにマレイン酸の付加ワックス、脂肪酸エステル系等が挙げられる。また、ポリテトラフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、四フッ化エチレン等のフッ素系樹脂のワックスも使用可能である。   Synthetic waxes include polyethylene, polyethylene oxide, polypropylene, ethylene and propylene copolymer wax, and oxide wax of copolymer wax of ethylene and other monomers. This system can be used in various ways including terpolymer systems by changing the copolymerization partner. Furthermore, maleic acid addition wax, fatty acid ester, and the like can be mentioned. In addition, a wax of a fluororesin such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, and tetrafluoroethylene can also be used.

ワックスとしては、上記例示したもののうち、軟化点が８０〜１４０℃のものを選択することが好ましい。軟化点が８０℃よりも低い時は、プレス加工や打ち抜き加工の際に金型温度の上昇に伴ってワックス粒子が軟化・液化してしまい、樹脂塗装鋼板と金型の摺動面において、液化したワックスの液切れ現象が発生し、加工性が低下して、擦り疵や金型との焼き付きが生じるため好ましくない。また、摺動部に黒化物が付着して、製品外観を著しく劣化させることがある。さらに、脱脂工程後の耐食性や耐テープ剥離性の観点からも、軟化点が低すぎると好ましくないことがわかった。他方、軟化点が１４０℃を超える時には、ワックスによる潤滑性が不充分となって、打ち抜き性、耐金型摩耗性、深絞り性等において向上が認められず、脱脂後の耐食性も若干低下する傾向が見られた。   As the wax, it is preferable to select a wax having a softening point of 80 to 140 ° C. among those exemplified above. When the softening point is lower than 80 ° C, the wax particles soften and liquefy as the mold temperature rises during press working and punching, and liquefaction occurs on the sliding surface between the resin-coated steel sheet and the mold. This is not preferable because a wax breakage phenomenon occurs, processability is reduced, and scuffing or seizure with a mold occurs. In addition, blackened material may adhere to the sliding portion and the product appearance may be significantly deteriorated. Furthermore, also from the viewpoint of the corrosion resistance after the degreasing process and the tape peel resistance, it was found that the softening point is too low. On the other hand, when the softening point exceeds 140 ° C., the lubricity by the wax becomes insufficient, the improvement in punchability, die wear resistance, deep drawability, etc. is not recognized, and the corrosion resistance after degreasing is slightly lowered. There was a trend.

ワックスとしては、球形ポリエチレンワックスが最も好適であり、その際に、球形ポリエチレンワックスの効果を最大限に得るには、ワックス粒子の粒子径が０．１〜３μｍであることが好ましい。ワックス粒子の粒子径が０．１μｍより小さいと、潤滑性、打ち抜き性、耐金型摩耗性および深絞り性の顕著な向上を図ることが難しい。他方、ワックス粒子の粒子径が３μｍを超える場合には、微粒子化されているエマルジョン組成物中に均一に分散させることが難しいため、樹脂皮膜の金属板への密着性が低下することがある。より好ましい球形ポリエチレンワックスの粒子径は０．３〜１．０μｍである。   As the wax, spherical polyethylene wax is most preferable. In this case, in order to obtain the maximum effect of the spherical polyethylene wax, the particle diameter of the wax particles is preferably 0.1 to 3 μm. If the particle size of the wax particles is smaller than 0.1 μm, it is difficult to achieve significant improvements in lubricity, punchability, mold wear resistance and deep drawability. On the other hand, when the particle diameter of the wax particles exceeds 3 μm, it is difficult to uniformly disperse in the finely divided emulsion composition, so that the adhesion of the resin film to the metal plate may be lowered. A more preferable spherical polyethylene wax has a particle size of 0.3 to 1.0 μm.

上述のような球形ポリエチレンワックスとしては、例えば、「ダイジェットＥ−１７」（互応化学社製）、「ＫＵＥ−１」、「ＫＵＥ−５」、「ＫＵＥ−８」（三洋化成工業社製）、「ケミパール」シリーズ（三井化学社製）の「Ｗ−１００」、「Ｗ−２００」、「Ｗ−３００」、「Ｗ−４００」、「Ｗ−５００」、「Ｗ−６４０」、「Ｗ−７００」等や、「エレポンＥ−２０」（日華化学社製）等のような市販品を好適に用いることができる。   Examples of the spherical polyethylene wax as described above include “Daijet E-17” (manufactured by Kyoyo Chemical Co., Ltd.), “KUE-1”, “KUE-5”, “KUE-8” (manufactured by Sanyo Chemical Industries). "W-100", "W-200", "W-300", "W-400", "W-500", "W-640", "W" of "Chemical Pearl" series (Mitsui Chemicals) Commercially available products such as “-700” and “Elepon E-20” (manufactured by Nikka Chemical Co., Ltd.) can be suitably used.

本発明で用いられるエマルジョン組成物は、必須成分であるエチレン−不飽和カルボン酸共重合体、沸点１００℃以下のアミン、１価の金属の化合物、アジリジン化合物等の架橋剤、さらに必要に応じて用いられるシリカ粒子、ワックス等を含むものであることが好ましい。エチレン−不飽和カルボン酸共重合体は、これらの樹脂成分がエマルジョン組成物の固形分の５０質量％以上となるように、アジリジン化合物、シリカ粒子、ワックス等の量を調整することが望ましい。   The emulsion composition used in the present invention comprises an essential component of an ethylene-unsaturated carboxylic acid copolymer, an amine having a boiling point of 100 ° C. or less, a monovalent metal compound, a cross-linking agent such as an aziridine compound, and further if necessary. It preferably contains silica particles, wax, etc. used. In the ethylene-unsaturated carboxylic acid copolymer, the amount of the aziridine compound, silica particles, wax and the like is desirably adjusted so that these resin components are 50% by mass or more of the solid content of the emulsion composition.

エマルジョン組成物の調製方法は、まず、必須成分であるエチレン−不飽和カルボン酸共重合体を水性媒体と共に、例えば、ホモジナイザー装置等に投入し、必要により７０〜２５０℃の加熱下とし、沸点１００℃以下のアミンと１価の金属の化合物を適宜水溶液等の形態で添加して（沸点１００℃以下のアミンを先に添加するか、沸点１００℃以下のアミンと１価の金属の化合物とを略同時に添加する）、高剪断力で撹拌する。シリカ粒子、ワックス、架橋剤等はいずれの段階で添加してもよいが、架橋剤添加後は架橋反応が進行してゲル化しないように、熱を掛けないようにすることが望ましい。   The emulsion composition is prepared by first charging the essential component ethylene-unsaturated carboxylic acid copolymer together with an aqueous medium into, for example, a homogenizer apparatus and heating at 70 to 250 ° C. as necessary, with a boiling point of 100 An amine having a boiling point of 100 ° C. or less and a monovalent metal compound are appropriately added in the form of an aqueous solution or the like (an amine having a boiling point of 100 ° C. or less is added first, or an amine having a boiling point of 100 ° C. or less and a monovalent metal compound are added. Stir with high shear force. Silica particles, wax, cross-linking agent and the like may be added at any stage, but it is desirable not to apply heat after the cross-linking agent is added so that the cross-linking reaction proceeds and gelation does not occur.

上記エマルジョン組成物には、本発明の目的を阻害しない範囲で、希釈溶媒、皮張り防止剤、レベリング剤、消泡剤、浸透剤、乳化剤、造膜助剤、着色顔料、増粘剤、シランカップリング剤、他の樹脂等を適宜添加してもよい。   The emulsion composition includes a diluent solvent, an anti-skinning agent, a leveling agent, an antifoaming agent, an emulsifier, an emulsifying agent, a film-forming aid, a coloring pigment, a thickener, and a silane as long as the object of the present invention is not impaired. A coupling agent, other resin, etc. may be added as appropriate.

金属板上に樹脂皮膜を形成するには、上記エマルジョン組成物を、公知の塗布方法、すなわち、ロールコーター法、スプレー法、カーテンフローコーター法等を用いて、金属板表面の片面または両面に塗布して加熱乾燥すればよい。加熱乾燥温度は、用いる架橋剤とカルボキシル基の架橋反応が進行する温度で行うことが好ましい。また、潤滑剤として、球形のポリエチレンワックスを用いる場合は、球形を維持しておく方が後の加工工程での加工性が良好となるので、７０〜１３０℃の範囲で乾燥を行うことが望ましい。   In order to form a resin film on a metal plate, the emulsion composition is applied to one or both surfaces of the metal plate surface using a known coating method, that is, a roll coater method, a spray method, a curtain flow coater method, or the like. And heat drying. The heating and drying temperature is preferably a temperature at which the crosslinking reaction between the crosslinking agent and the carboxyl group proceeds. In addition, when spherical polyethylene wax is used as the lubricant, it is preferable to perform drying in the range of 70 to 130 ° C. because maintaining the spherical shape improves the workability in the subsequent processing step. .

樹脂皮膜の付着量（厚み）は、乾燥後において、０．２〜２．５ｇ／ｍ2が好ましい。薄すぎると、金属板への均一塗工が難しく、加工性、耐食性、塗装性等、目的とするバランスのとれた皮膜特性を得難い。しかし、付着量が２．５ｇ／ｍ2を超えると、コンピュータハウジング等に用いる場合のアース性、すなわち導電性が低下するため好ましくない。さらに、プレス加工の際に樹脂皮膜の剥離量が多くなって、金型への剥離皮膜の付着蓄積が起こり、プレス成形に支障を生じる上、製造コスト的にも無駄である。より好ましい樹脂皮膜付着量の下限は０．５ｇ／ｍ2であり、上限は２．０ｇ／ｍ2である。 The adhesion amount (thickness) of the resin film is preferably 0.2 to 2.5 g / m 2 after drying. If it is too thin, uniform coating on a metal plate is difficult, and it is difficult to obtain the desired balanced film properties such as workability, corrosion resistance, and paintability. However, if the adhesion amount exceeds 2.5 g / m 2 , the grounding property, that is, the conductivity when used in a computer housing or the like is not preferable. Furthermore, the amount of peeling of the resin film is increased during press working, causing adhesion and accumulation of the peeling film on the mold, resulting in trouble with press molding and wasteful manufacturing cost. The lower limit of the more preferable resin film adhesion amount is 0.5 g / m 2 , and the upper limit is 2.0 g / m 2 .

樹脂皮膜を形成することによって本発明の樹脂塗装金属板が得られる。この樹脂塗装金属板は、用途に応じて加工工程を経た後このまま用いたり、あるいは従来条件による電着塗装・粉体塗装・シルク印刷（１３０〜１６０℃、２０〜３０分程度）を施して用いてもよい。   The resin-coated metal plate of the present invention is obtained by forming a resin film. This resin-coated metal plate is used as it is after undergoing a processing step depending on the application, or used after being subjected to electrodeposition coating, powder coating, silk printing (about 130 to 160 ° C., about 20 to 30 minutes) under conventional conditions. May be.

以下実施例によって本発明をさらに詳述するが、下記実施例は本発明を制限するものではなく、本発明の趣旨を逸脱しない範囲で変更実施することは、全て本発明に含まれる。   The present invention will be described in more detail with reference to the following examples. However, the following examples are not intended to limit the present invention, and all modifications are included in the present invention without departing from the spirit of the present invention.

〔試験方法〕
下記実施例で用いた試験方法は下記の通りである。 〔Test method〕
The test methods used in the following examples are as follows.

（１）脱脂工程後の耐食性
６０℃に調製したアルカリ脱脂剤（日本パーカライジング社製「ＣＬ−Ｎ３６４Ｓ」）２０ｇ／リットルに、樹脂塗装鋼板を２分間浸漬してから引き上げ、水洗および乾燥後、塩水噴霧試験をＪＩＳ Ｚ２３７１に従って実施して、白錆が１％発生するまでの時間を測定した。評価基準は、◎：２４０時間以上、○：１２０〜２４０時間未満、△：７２〜１２０時間未満、×：７２時間未満、とした。 (1) Corrosion resistance after degreasing step The resin-coated steel plate is dipped in 20 g / liter of an alkaline degreasing agent (“CL-N364S” manufactured by Nihon Parkerizing Co., Ltd.) prepared at 60 ° C. for 2 minutes, then washed, dried and then brine. The spray test was performed according to JIS Z2371, and the time until 1% of white rust was generated was measured. The evaluation criteria were as follows: ◎: 240 hours or more, ○: 120 to less than 240 hours, Δ: 72 to less than 120 hours, ×: less than 72 hours.

（２）耐テープ剥離性
樹脂塗装鋼板に、粘着テープ（スリオンテック社製フィラメンテープＮｏ．９５１０；ゴム系粘着剤）を貼付し、恒温恒湿装置で４０℃、９８％ＲＨの雰囲気下で２４時間保存した後、ＪＩＳ Ｋ ５４００に準じてテープを剥離し、皮膜の残存面積率を測定した。評価基準は、◎：皮膜残存率１００％、○：皮膜残存率９０〜９９％、△：皮膜残存率８９〜７０％、×：皮膜残存率７０％以下、とした。 (2) Tape peel resistance Adhesive tape (Flamen tape No. 9510 manufactured by Sliontec Co., Ltd .; rubber adhesive) is applied to a resin-coated steel sheet, and the temperature and humidity are kept at 40 ° C. and 98% RH for 24 hours. After storage, the tape was peeled according to JIS K 5400, and the remaining area ratio of the film was measured. The evaluation criteria were as follows: A: film remaining rate 100%, ○: film remaining rate 90-99%, Δ: film remaining rate 89-70%, x: film remaining rate 70% or less.

（３）動摩擦係数
樹脂塗装鋼板の潤滑性を評価するため、摺動試験装置を用いて、加圧力５．４ＭＰａ、引き抜き速度３００ｍｍ／ｍｉｎとしたときの摺動による荷重を測定して、動摩擦係数を算出した。 (3) Coefficient of dynamic friction In order to evaluate the lubricity of the resin-coated steel sheet, a sliding test device is used to measure the load due to sliding when the pressure is 5.4 MPa and the drawing speed is 300 mm / min. Was calculated.

実験例１（有機塩基および金属塩の種類と量の影響）
金属板素材として、電気亜鉛めっき鋼板（Ｚｎ付着量２０ｇ／ｍ2、板厚０．８ｍｍ）を用いた。 Experimental Example 1 (Influence of type and amount of organic base and metal salt)
As the metal plate material, an electrogalvanized steel plate (Zn adhesion amount 20 g / m 2 , plate thickness 0.8 mm) was used.

エマルジョン組成物を調製するため、オートクレーブに、水６２６質量部（以下、単に「部」とする）と、エチレン−アクリル酸共重合体（アクリル酸２０質量％、メルトインデックス（ＭＩ）３００）１６０部とを加え、さらに、表１に示した量の有機塩基と金属化合物を添加して、１５０℃、５Ｐａの雰囲気下で高速撹拌し、エチレン−アクリル酸共重合体のエマルジョンを得た。続いて、上記エマルジョンに、内部架橋剤として、４，４’−ビス（エチレンイミノカルボニルアミノ）ジフェニルメタン（「ケミタイトＤＺ−２２Ｅ」；「ケミタイト」は登録商標；日本触媒社製）を固形分で５質量％（エマルジョン組成物の固形分を１００質量％としたときの値：以下同じ）添加した。   In order to prepare an emulsion composition, 626 parts by mass of water (hereinafter, simply referred to as “parts”) and 160 parts of an ethylene-acrylic acid copolymer (acrylic acid 20% by mass, melt index (MI) 300) were prepared in an autoclave. In addition, an organic base and a metal compound in the amounts shown in Table 1 were added, and the mixture was stirred at a high speed in an atmosphere of 150 ° C. and 5 Pa to obtain an ethylene-acrylic acid copolymer emulsion. Subsequently, 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane (“Chemite DZ-22E”; “Chemite” is a registered trademark; manufactured by Nippon Shokubai Co., Ltd.) is used as an internal cross-linking agent. % By mass (value when the solid content of the emulsion composition is 100% by mass; the same applies hereinafter) was added.

上記混合物に、さらに外部架橋剤としてグリシジル基含有化合物（「エピクロンＣＲ５Ｌ」（以下、ＣＲ５Ｌと略す；「エピクロン」は登録商標；大日本インキ化学工業社製）を固形分で５質量％、粒子径１０〜２０ｎｍのシリカ粒子（「スノーテックス４０」；日産化学工業社製）を固形分で３０質量％、軟化点１２０℃、平均粒径１μｍの球形ポリエチレンワックスを固形分で５質量％となるように配合して撹拌し、エマルジョン組成物を調製した。   To the above mixture, a glycidyl group-containing compound ("Epiclon CR5L" (hereinafter abbreviated as CR5L; "Epiclon" is a registered trademark; manufactured by Dainippon Ink & Chemicals, Inc.)) as a solid content is further contained in an amount of 5% by mass, particle diameter Silica particles of 10 to 20 nm (“Snowtex 40”; manufactured by Nissan Chemical Industries, Ltd.) are 30% by mass in solid content, spherical polyethylene wax having a softening point of 120 ° C. and an average particle diameter of 1 μm is 5% by mass in solid content. Was mixed and stirred to prepare an emulsion composition.

前記電気亜鉛めっき鋼板の片面に各組成物をバーコートで塗布し、板温９０℃で１分加熱乾燥し、付着量１．０ｇ／ｍ2の樹脂皮膜が形成された樹脂塗装鋼板を得た。各評価結果を表１に示した。 Each composition was applied to one side of the electrogalvanized steel sheet by bar coating and dried by heating at a plate temperature of 90 ° C. for 1 minute to obtain a resin-coated steel sheet on which a resin film having an adhesion amount of 1.0 g / m 2 was formed. . The evaluation results are shown in Table 1.

Figure 0004398827
Figure 0004398827

実験例２（架橋剤量の影響）
トリエチルアミンの使用量を４０％、ＮａＯＨの使用量を１５％と一定にし、前記「ケミタイトＤＺ−２２Ｅ」（ＤＺ−２２Ｅ）の量を表２に示したように変更した以外は実験例１と同様にして樹脂塗装鋼板を得て、特性評価した。結果を表２に示した。 Experimental Example 2 (Influence of the amount of crosslinking agent)
The same as Experimental Example 1 except that the amount of triethylamine used was fixed at 40%, the amount of NaOH used was fixed at 15%, and the amount of the “chemitite DZ-22E” (DZ-22E) was changed as shown in Table 2. Thus, a resin-coated steel plate was obtained and evaluated. The results are shown in Table 2.

Figure 0004398827
Figure 0004398827

実験例３（シリカ粒子の影響）
架橋剤量は実験例１と同様にし、シリカ粒子の粒子径と添加濃度を表３に示したように変更した以外は実験例２と同様にして樹脂塗装鋼板を得て、特性評価した。結果を表３に示した。 Experimental Example 3 (Influence of silica particles)
The amount of the crosslinking agent was the same as in Experimental Example 1, and a resin-coated steel sheet was obtained and evaluated in the same manner as in Experimental Example 2 except that the particle size and addition concentration of silica particles were changed as shown in Table 3. The results are shown in Table 3.

Figure 0004398827
Figure 0004398827

実験例４（ワックスの影響）
シリカ粒子の粒子径と添加濃度は実験例１と同様にし、球形ポリエチレンワックスの粒子径、添加濃度、軟化温度を表４に示したように変更した以外は実験例２と同様にして樹脂塗装鋼板を得て、特性評価した。結果を表４に示した。 Experimental Example 4 (Influence of wax)
The particle diameter and addition concentration of silica particles were the same as in Experimental Example 1, and the resin-coated steel sheet was the same as in Experimental Example 2 except that the particle diameter, addition concentration, and softening temperature of the spherical polyethylene wax were changed as shown in Table 4. And characterized. The results are shown in Table 4.

Figure 0004398827
Figure 0004398827

Claims (5)

エチレン−不飽和カルボン酸共重合体を主成分とするエマルジョン組成物から得られる樹脂皮膜を備える樹脂塗装金属板であって、このエマルジョン組成物は、エチレン−不飽和カルボン酸共重合体以外に、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．２〜０．８モルに相当する沸点１００℃以下のアミンと、エチレン−不飽和カルボン酸共重合体が有するカルボキシル基１モルに対して０．０２〜０．４モルに相当する１価の金属の化合物とを含むと共に、カルボキシル基と反応し得る官能基を２個以上有する架橋剤としてのアジリジニル基含有架橋剤をエマルジョン組成物の固形分１００質量％に対し１〜２０質量％含み、球状ポリエチレンワックスをエマルジョン組成物の固形分１００質量％に対し０．５〜２０質量％含み、沸点１００℃超のアミンおよびアンモニアは実質的に含まないことを特徴とする樹脂塗装金属板。 A resin-coated metal plate provided with a resin film obtained from an emulsion composition mainly composed of an ethylene-unsaturated carboxylic acid copolymer, the emulsion composition, in addition to the ethylene-unsaturated carboxylic acid copolymer, An amine having a boiling point of 100 ° C. or less corresponding to 0.2 to 0.8 mol per mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer, and the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer An aziridinyl group-containing crosslinking agent as a crosslinking agent having a monovalent metal compound corresponding to 0.02 to 0.4 mol per mol and having two or more functional groups capable of reacting with a carboxyl group It comprises 1 to 20 mass% relative to the solid content of 100 mass% of the emulsion composition, vs. spherical polyethylene wax solids 100 wt% of the emulsion composition Comprises 0.5 to 20 wt%, the resin coated metal sheet, characterized in that the boiling point 100 ° C. than amines and ammonia substantially free. 上記エチレン−不飽和カルボン酸共重合体は、不飽和カルボン酸が１０〜４０質量％共重合されている請求項１に記載の樹脂塗装金属板。   The resin-coated metal sheet according to claim 1, wherein the ethylene-unsaturated carboxylic acid copolymer is copolymerized with 10 to 40% by mass of an unsaturated carboxylic acid. 上記沸点１００℃以下のアミンがトリエチルアミンである請求項１または２に記載の樹脂塗装金属板。   The resin-coated metal plate according to claim 1 or 2, wherein the amine having a boiling point of 100 ° C or lower is triethylamine. 上記エマルジョン組成物の固形分１００質量％中に、平均粒子径１〜２００ｎｍのシリカ粒子が５〜４０質量％含まれている請求項１〜３のいずれかに記載の樹脂塗装金属板。   The resin-coated metal plate according to any one of claims 1 to 3, wherein 5 to 40% by mass of silica particles having an average particle diameter of 1 to 200 nm is contained in 100% by mass of the solid content of the emulsion composition. クロメート皮膜が形成されていない請求項１〜４のいずれかに記載の樹脂塗装金属板。 The resin-coated metal plate according to any one of claims 1 to 4, wherein a chromate film is not formed.
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