JP5921695B2 - Rust prevention composition and aqueous dispersion containing the same - Google Patents
Rust prevention composition and aqueous dispersion containing the same Download PDFInfo
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- JP5921695B2 JP5921695B2 JP2014533099A JP2014533099A JP5921695B2 JP 5921695 B2 JP5921695 B2 JP 5921695B2 JP 2014533099 A JP2014533099 A JP 2014533099A JP 2014533099 A JP2014533099 A JP 2014533099A JP 5921695 B2 JP5921695 B2 JP 5921695B2
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Description
本発明は防錆用組成物およびこれを含む水分散体に関し、詳しくはアルカリ処理に対する耐性に優れた防錆塗膜を形成し得る防錆用組成物およびこれを含む水分散体に関する。 The present invention relates to a rust-preventing composition and an aqueous dispersion containing the same, and more particularly to a rust-preventing composition capable of forming a rust-preventing coating film excellent in resistance to alkali treatment and an aqueous dispersion containing the same.
主として炭化水素から構成される高分子鎖からなり、側鎖に有するカルボキシル基の一部が金属陽イオンで中和されている部分中和物であるアイオノマー樹脂は、各種基材、特に、金属と良好な密着性を有することはよく知られている。例えば、日本接着学会誌、Ｖｏｌ．１９、Ｎｏ．３、ｐ９５−１０１（１９８３）にアルカリ金属や２価金属などの架橋イオンの種類によってアイオノマー樹脂の塗膜物性や密着度に違いが生ずることが報告されている。また、このアイオノマー樹脂からなる防錆層は耐水性が優れるため、アイオノマー樹脂を金属基材の防錆材として使用できることも知られている。しかも、Ｎａ、Ｋなどの１価金属イオンやアミンで中和されたアイオノマー樹脂は水中に分散することが可能であるため、アイオノマー樹脂の水分散体を使用した種々の防錆処理材が開発され、現在、各種産業分野に広く用いられている。 The ionomer resin, which is a partially neutralized product consisting of a polymer chain mainly composed of hydrocarbons and in which part of the carboxyl groups in the side chain is neutralized with a metal cation, It is well known that it has good adhesion. For example, Journal of the Adhesion Society of Japan, Vol. 19, no. 3, p95-101 (1983), it has been reported that the coating properties and the degree of adhesion of ionomer resins differ depending on the type of cross-linking ions such as alkali metals and divalent metals. It is also known that an ionomer resin can be used as a rust preventive material for a metal substrate because the rust preventive layer made of this ionomer resin has excellent water resistance. Moreover, since ionomer resins neutralized with monovalent metal ions such as Na and K and amines can be dispersed in water, various rust preventive treatment materials using aqueous dispersions of ionomer resins have been developed. Currently, it is widely used in various industrial fields.
しかし、このようなアイオノマー樹脂の単独処理では顧客が要求する防錆性や密着性などの性能に応え得なかった。このため、アイオノマー樹脂は、主に下地にクロメート処理などを施した有機被覆複合鋼板の製造に使用されてきた。しかし、近年、世界的規模で環境問題に関心が集まり、６価クロムを使用しない表面処理金属製品の要求が高まっている。そのため、クロメート下地処理を行わずに、有機樹脂による１段処理のみで従来と同等の防錆性や密着性などを発現できる防錆塗料が求められるようになった。 However, such an ionomer resin alone cannot meet the performance required by customers, such as rust prevention and adhesion. For this reason, ionomer resins have been used mainly in the production of organic coated composite steel sheets with a chromate treatment applied to the base. However, in recent years, there has been an interest in environmental issues on a global scale, and there is an increasing demand for surface-treated metal products that do not use hexavalent chromium. For this reason, there has been a demand for a rust-preventing paint that can exhibit the same rust-preventing property and adhesion as conventional ones only by one-step treatment with an organic resin without performing a chromate base treatment.
これらの要求に応えるため、すでに種々の検討がなされている。例えば、特開平１１−０１２４１１号公報には、防錆性能を向上するため２価の金属で中和されたアイオノマー樹脂、エポキシ基含有化合物、アイオノマー樹脂とエポキシ基含有化合物の反応物とからなる水性分散体組成物が開示されている。しかし、本発明者らが評価したところでは、上記の開示された組成物により塗膜を形成した鋼板にアルカリ脱脂処理を施した後、塩水噴霧試験すると鋼板が発錆し、防錆性は十分ではなかった（以下、アルカリ脱脂処理後の防錆性を耐アルカリ性と記す）。 Various studies have already been made to meet these requirements. For example, Japanese Patent Application Laid-Open No. 11-012411 discloses an aqueous solution comprising an ionomer resin neutralized with a divalent metal to improve rust prevention performance, an epoxy group-containing compound, and a reaction product of an ionomer resin and an epoxy group-containing compound. Dispersion compositions are disclosed. However, as evaluated by the inventors, the steel sheet formed with the above disclosed composition is subjected to an alkaline degreasing treatment, and then the salt spray test results in rusting and sufficient rust prevention. (Hereinafter, the rust prevention after the alkali degreasing treatment is referred to as alkali resistance).
また、特開２００６−２２１２７号公報には、１価の金属イオンおよび／またはアミンで中和されたアイオノマー樹脂、多官能オキザゾリン樹脂、触媒およびシランカップリング剤を含有する防錆塗料用組成物が開示され、この組成物から形成される塗膜が高い耐アルカリ性を有することが記載されている。 Japanese Patent Application Laid-Open No. 2006-22127 discloses a composition for a rust-preventing coating containing an ionomer resin neutralized with a monovalent metal ion and / or an amine, a polyfunctional oxazoline resin, a catalyst and a silane coupling agent. It is disclosed that the coating film formed from this composition has high alkali resistance.
しかし、最近さらに防錆塗料の薄膜化が進み、防錆塗料には従来に増して高い耐アルカリ性が求められている。本発明の目的は、上記従来技術の問題点を解決すること、すなわち、耐アルカリ性が優れた塗膜を形成し得る防錆用組成物を提供すること、また適切な成分と組み合わせることによりそのような防錆用組成物を作製し得る重合体を提供することにある。 Recently, however, the thickness of the anticorrosive paint has been further reduced, and the antirust paint is required to have higher alkali resistance than ever before. The object of the present invention is to solve the above-mentioned problems of the prior art, that is, to provide a rust-preventing composition capable of forming a coating film excellent in alkali resistance, and in combination with appropriate components. Another object of the present invention is to provide a polymer capable of producing a rustproofing composition.
本発明者らは鋭意研究の結果、塗膜を形成する重合体に酸性基が存在すると防錆塗膜の耐アルカリ性を低下させる場合があるとの知見を得た。そしてモノマー成分として酸モノマーの使用を制限し、その代わりに少なくともニトリル基、水酸基、およびアルコキシシリル基を有する重合体と架橋剤とを組み合わせることにより、優れた基材密着性、耐水性、耐溶剤性および耐食性と優れた耐アルカリ性とを両立した塗膜を形成し得る防錆用組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have obtained the knowledge that the presence of acidic groups in the polymer forming the coating film may reduce the alkali resistance of the rust-proof coating film. And by restricting the use of acid monomers as monomer components, and in combination with a polymer having at least a nitrile group, a hydroxyl group, and an alkoxysilyl group and a crosslinking agent, excellent substrate adhesion, water resistance, solvent resistance The present inventors have found that a rust-preventing composition capable of forming a coating film that is compatible with both properties and corrosion resistance and excellent alkali resistance can be obtained, and the present invention has been completed.
すなわち、本発明は、たとえば、以下の［１］〜［１９］に記載した事項により特定される。
［１］少なくともニトリル基、水酸基、およびアルコキシシリル基を有する重合体（Ａ）ならびに架橋剤（Ｂ）を含有する防錆用組成物。
［２］重合体（Ａ）が、α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）（ただし、前記（ａ−１）成分を除く）から導かれる構造単位、水酸基を有するモノマー（ａ−３）から導かれる構造単位およびアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を含むものである上記［１］に記載の防錆用組成物。
［３］重合体（Ａ）が、重合体（Ａ）に含まれる全構造単位の量を１００重量％としたとき、α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位を３０〜９０重量％、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）（ただし、前記（ａ−１）成分を除く）から導かれる構造単位を１０〜６０重量％、水酸基を有するモノマー（ａ−３）から導かれる構造単位を１〜１０重量％、およびアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を１〜５重量％含むものである上記［１］または［２］に記載の防錆用組成物。
［４］重合体（Ａ）は粒子として存在し、その平均粒径が１０〜５００ｎｍである上記［１］〜［３］のいずれかに記載の防錆用組成物。
［５］重合体（Ａ）は、酸価が３０ｍｇＫＯＨ／ｇ以下である上記［１］〜［４］のいずれかに記載の防錆用組成物。
［６］重合体（Ａ）は、水酸基価が１〜９０ｍｇＫＯＨ／ｇである上記［１］〜［５］のいずれかに記載の防錆用組成物。
［７］さらに、水酸基との反応性を有する水溶性ジルコニウム化合物（Ｄ）を含有する上記［１］〜［６］のいずれかに記載の防錆用組成物。
［８］水溶性ジルコニウム化合物（Ｄ）が炭酸ジルコニウムアンモニウムである上記［７］に記載の防錆用組成物。
［９］架橋剤（Ｂ）が、オキサゾリン化合物（ｂ１）およびシランカップリング剤（ｂ２）から選ばれた少なくとも１種である上記［１］〜［８］のいずれかに記載の防錆用組成物。
［１０］オキサゾリン系化合物（ｂ１）は、水分散性で、かつ、オキサゾリン基当量が２００〜５０００ｇ／当量である上記［９］に記載の防錆用組成物。
［１１］シランカップリング剤（ｂ２）が、グリシジル基、アミノ基、アミド基、またはイソシアネート基を有する化合物である上記［９］または［１０］に記載の防錆用組成物。
［１２］架橋剤（Ｂ）が、オキサゾリン化合物（ｂ１）およびシランカップリング剤（ｂ２）である上記［９］〜［１１］のいずれかに記載の防錆用組成物。
［１３］重合体（Ａ）１００重量部に対して、オキサゾリン系化合物（ｂ１）を１〜４０重量部、シランカップリング剤（ｂ２）を０．１〜１０重量部の割合で含有する上記［１２］に記載の防錆用組成物。
［１４］さらに、水酸基とオキサゾリン基との反応を促進する触媒（Ｃ）を含有する上記［１２］または［１３］に記載の防錆用組成物。
［１５］水酸基との反応性を有する水溶性ジルコニウム化合物（Ｄ）を含有し、重合体（Ａ）１００重量部に対して、オキサゾリン系化合物（ｂ１）を１〜４０重量部、シランカップリング剤（ｂ２）を０．１〜５重量部、触媒（Ｃ）を０．１〜１０重量部、水溶性ジルコニウム化合物（Ｄ）を０．１〜５重量部の割合で含有する上記［１４］に記載の防錆用組成物。
［１６］触媒（Ｃ）がリン酸二水素アンモニウム、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムヒドロキサイド、ハロゲン化リチウムおよび水酸化リチウムから選ばれた化合物である上記［１４］または［１５］に記載の防錆用組成物。
［１７］上記［１］〜［１６］のいずれかに記載の防錆用組成物を含む水分散体。
［１８］上記［１］〜［１６］のいずれかに記載の防錆用組成物の硬化物で鋼板を被覆してなる防錆鋼板。
［１９］α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）（ただし、前記（ａ−１）成分を除く）から導かれる構造単位、水酸基を有するモノマー（ａ−３）から導かれる構造単位およびアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を含む防錆用重合体。That is, this invention is specified by the matter described in the following [1]-[19], for example.
[1] A rust preventive composition containing a polymer (A) having at least a nitrile group, a hydroxyl group, and an alkoxysilyl group, and a crosslinking agent (B).
[2] The polymer (A) is a structural unit derived from a nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group, a monomer having an α, β-monoethylenically unsaturated group ( a-2) (excluding the component (a-1)), a structural unit derived from a hydroxyl group-containing monomer (a-3), and an alkoxysilyl (meth) acrylate (a-4) The composition for rust prevention according to the above [1], which contains a derived structural unit.
[3] Nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group when the amount of the total structural unit contained in the polymer (A) is 100% by weight. The structural unit derived from the monomer (a-2) having an α, β-monoethylenically unsaturated group (except for the component (a-1)) 10 to 60% by weight, 1 to 10% by weight of a structural unit derived from a monomer (a-3) having a hydroxyl group, and 1 to 5% by weight of a structural unit derived from an alkoxysilyl (meth) acrylate (a-4) The composition for rust prevention according to the above [1] or [2], which is contained.
[4] The rust preventive composition according to any one of [1] to [3], wherein the polymer (A) is present as particles and has an average particle diameter of 10 to 500 nm.
[5] The rust preventive composition according to any one of [1] to [4], wherein the polymer (A) has an acid value of 30 mgKOH / g or less.
[6] The composition for rust prevention according to any one of [1] to [5], wherein the polymer (A) has a hydroxyl value of 1 to 90 mgKOH / g.
[7] The composition for rust prevention according to any one of [1] to [6], further comprising a water-soluble zirconium compound (D) having reactivity with a hydroxyl group.
[8] The antirust composition according to [7], wherein the water-soluble zirconium compound (D) is ammonium zirconium carbonate.
[9] The composition for rust prevention according to any one of the above [1] to [8], wherein the crosslinking agent (B) is at least one selected from the oxazoline compound (b1) and the silane coupling agent (b2). object.
[10] The rust-preventing composition according to [9], wherein the oxazoline-based compound (b1) is water-dispersible and has an oxazoline group equivalent of 200 to 5000 g / equivalent.
[11] The antirust composition according to [9] or [10], wherein the silane coupling agent (b2) is a compound having a glycidyl group, an amino group, an amide group, or an isocyanate group.
[12] The antirust composition according to any one of [9] to [11], wherein the crosslinking agent (B) is an oxazoline compound (b1) and a silane coupling agent (b2).
[13] The above-mentioned, which contains 1 to 40 parts by weight of the oxazoline-based compound (b1) and 0.1 to 10 parts by weight of the silane coupling agent (b2) with respect to 100 parts by weight of the polymer (A) [ 12] The composition for rust prevention of description.
[14] The rust-preventing composition according to [12] or [13], further comprising a catalyst (C) that promotes a reaction between a hydroxyl group and an oxazoline group.
[15] A water-soluble zirconium compound (D) having reactivity with a hydroxyl group is contained, and 1 to 40 parts by weight of an oxazoline-based compound (b1) with respect to 100 parts by weight of the polymer (A), a silane coupling agent In the above [14], containing 0.1 to 5 parts by weight of (b2), 0.1 to 10 parts by weight of the catalyst (C), and 0.1 to 5 parts by weight of the water-soluble zirconium compound (D). The composition for rust prevention according to the description.
[16] The above [14] or [15], wherein the catalyst (C) is a compound selected from ammonium dihydrogen phosphate, tetramethylammonium chloride, tetramethylammonium hydroxide, lithium halide and lithium hydroxide. Anti-rust composition.
[17] An aqueous dispersion containing the antirust composition according to any one of [1] to [16].
[18] A rust-proof steel sheet obtained by coating a steel sheet with a cured product of the rust-proofing composition according to any one of [1] to [16].
[19] Structural unit derived from a nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group, a monomer (a-2) having an α, β-monoethylenically unsaturated group (provided that A protective unit comprising a structural unit derived from the above (a-1) component), a structural unit derived from a monomer (a-3) having a hydroxyl group and a structural unit derived from an alkoxysilyl (meth) acrylate (a-4) Rust polymer.
本発明の接着剤組成物から得られる塗膜は耐アルカリ性に優れ、薄膜化しても十分な耐アルカリ性を確保することができる。 The coating film obtained from the adhesive composition of the present invention is excellent in alkali resistance and can secure sufficient alkali resistance even if it is made into a thin film.
本発明の防錆用組成物は、少なくともニトリル基、水酸基、およびアルコキシシリル基を有する重合体（Ａ）ならびに架橋剤（Ｂ）を含有する。 The composition for rust prevention of the present invention contains a polymer (A) having at least a nitrile group, a hydroxyl group, and an alkoxysilyl group, and a crosslinking agent (B).
重合体（Ａ）は、本組成物の主成分であり、架橋剤（Ｂ）と架橋することにより防錆塗膜を形成する。 A polymer (A) is a main component of this composition, and forms a rust prevention coating film by bridge | crosslinking with a crosslinking agent (B).
重合体（Ａ）としては、具体的には、α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）から導かれる構造単位、水酸基含有モノマー（ａ−３）から導かれる構造単位およびアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を含む重合体（Ａ１）を挙げることができる。つまり重合体（Ａ１）は、α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）、水酸基含有モノマー（ａ−３）およびアルコキシシリル（メタ）アクリレート（ａ−４）を共重合させることにより得ることができる。このように重合体（Ａ１）はアクリル酸およびメタクリル酸等の酸モノマーから導かれる構造単位を必須構造単位としては含まない。 Specifically, the polymer (A) includes a structural unit derived from a nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group, an α, β-monoethylenically unsaturated group. Polymer (A1) containing structural unit derived from monomer (a-2) having, structural unit derived from hydroxyl group-containing monomer (a-3) and structural unit derived from alkoxysilyl (meth) acrylate (a-4) Can be mentioned. That is, the polymer (A1) includes a nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group, a monomer (a-2) having an α, β-monoethylenically unsaturated group, and a hydroxyl group-containing It can be obtained by copolymerizing the monomer (a-3) and the alkoxysilyl (meth) acrylate (a-4). Thus, the polymer (A1) does not contain a structural unit derived from an acid monomer such as acrylic acid and methacrylic acid as an essential structural unit.
なお、本発明において（メタ）アクリル酸とはアクリル酸およびメタクリル酸を意味し、（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を意味する。 In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid, and (meth) acrylate means acrylate and methacrylate.
重合体（Ａ１）は、前記（ａ−１）〜（ａ−４）から導かれる構造単位以外の構造単位を含むことができる。ただし、重合体（Ａ）に含まれる酸性基を有する構造単位の量は制限される。 The polymer (A1) can contain structural units other than the structural units derived from the above (a-1) to (a-4). However, the amount of the structural unit having an acidic group contained in the polymer (A) is limited.
重合体（Ａ）の酸価は３０ｍｇＫＯＨ／ｇ以下であることが好ましく、２０ｍｇＫＯＨ／ｇ以下であることがより好ましく、１５ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。ここで、重合体（Ａ）の酸価とは、重合体（Ａ）１ｇ中に含有される酸性成分を中和するために必要な水酸化カリウム（ＫＯＨ）のｍｇ数である。重合体（Ａ）の酸価は、ＪＩＳ Ｋ００７０に準じた方法で求められる。 The acid value of the polymer (A) is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further preferably 15 mgKOH / g or less. Here, the acid value of the polymer (A) is the number of mg of potassium hydroxide (KOH) necessary for neutralizing the acidic component contained in 1 g of the polymer (A). The acid value of the polymer (A) is determined by a method according to JIS K0070.
重合体（Ａ）は、上記のとおり酸性基を有する構造単位の含有比率が小さく、好ましくは酸性基を有する構造単位を含まない。つまり重合体（Ａ）に存在する酸性基の量は少なく、好ましくは酸性基が存在しない。 As described above, the polymer (A) has a small content ratio of structural units having an acidic group, and preferably does not include a structural unit having an acidic group. That is, the amount of acidic groups present in the polymer (A) is small, and preferably no acidic groups are present.
架橋剤（Ｂ）は、重合体（Ａ）と架橋することにより、防錆塗膜の耐水性を向上させることができる。架橋剤（Ｂ）は、重合体（Ａ）と架橋することができる化合物であり、好ましくは、オキサゾリン系化合物、シランカップリング剤、エポキシ系化合物、アミノ系化合物、メラミン系化合物、イソシアネート系化合物、有機ジルコニウム系化合物、有機チタン系化合物、エピクロルヒドリン系化合物、カルボジイミド系化合物、アジリジン系化合物であり、特に好ましくは、オキサゾリン系化合物（ｂ１）およびシランカップリング剤（ｂ２）である。 A crosslinking agent (B) can improve the water resistance of a rust preventive coating film by bridge | crosslinking with a polymer (A). The crosslinking agent (B) is a compound capable of crosslinking with the polymer (A), preferably an oxazoline compound, a silane coupling agent, an epoxy compound, an amino compound, a melamine compound, an isocyanate compound, An organic zirconium compound, an organic titanium compound, an epichlorohydrin compound, a carbodiimide compound, and an aziridine compound, particularly preferably an oxazoline compound (b1) and a silane coupling agent (b2).
従来の防錆用組成物の主成分である重合体はカルボキシル基等の酸性基を一定割合で有していた。これは、主成分である重合体がシランカップリング剤と架橋する上で、重合体に酸性基が一定割合で含有されることが必須であったからである。 The polymer which is the main component of the conventional rust preventive composition has acidic groups such as carboxyl groups at a certain ratio. This is because it is essential for the polymer as the main component to contain an acidic group at a certain ratio in order to crosslink with the silane coupling agent.
ところが、本発明者らの研究により、重合体に酸性基が存在すると防錆塗膜の耐アルカリ性が低下する場合があることが判明した。そこで、本発明の防錆用組成物においては、重合体（Ａ）に存在する酸性基の量を制限することにより防錆塗膜の耐アルカリ性を向上させた。たとえば重合体（Ａ１）は、酸性基を有する構造単位の代わりに水酸基含有モノマー（ａ−３）から導かれる構造単位を含む。つまり重合体（Ａ）は、酸性基の代わりに水酸基を有する。本発明の防錆用組成物においては、重合体（Ａ）が有する水酸基と架橋剤（Ｂ）、たとえばオキサゾリン系化合物（ｂ１）およびシランカップリング剤（ｂ２）の官能基とが反応することにより架橋体が得られる。ただし、架橋に関与する重合体（Ａ）の官能基が水酸基であると、シランカップリング剤（ｂ２）などとの架橋の強度を高めることができない。そこで、本発明の防錆用組成物においては、たとえば重合体（Ａ１）にアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を含有させることにより、重合体（Ａ）のアルコキシシリル基とシランカップリング剤（ｂ２）などの官能基とを水架橋させることによって架橋の強度を高めることを可能にした。本発明の防錆用組成物は、以上のような構成により、従来の防錆用組成物と同等の塗膜強度を保ちながら、従来の防錆用組成物よりもはるかに高い耐アルカリ性を有する塗膜を形成することを可能にした。 However, the inventors' research has revealed that the presence of acidic groups in the polymer may reduce the alkali resistance of the anticorrosive coating film. Then, in the composition for rust prevention of this invention, the alkali resistance of the rust prevention coating film was improved by restrict | limiting the quantity of the acidic group which exists in a polymer (A). For example, the polymer (A1) includes a structural unit derived from the hydroxyl group-containing monomer (a-3) instead of the structural unit having an acidic group. That is, the polymer (A) has a hydroxyl group instead of an acidic group. In the rust preventive composition of the present invention, the hydroxyl group of the polymer (A) reacts with the functional groups of the crosslinking agent (B), for example, the oxazoline compound (b1) and the silane coupling agent (b2). A crosslinked body is obtained. However, when the functional group of the polymer (A) involved in crosslinking is a hydroxyl group, the strength of crosslinking with the silane coupling agent (b2) or the like cannot be increased. Therefore, in the rust-preventing composition of the present invention, for example, by incorporating a structural unit derived from alkoxysilyl (meth) acrylate (a-4) into the polymer (A1), the alkoxysilyl of the polymer (A). It was possible to increase the strength of crosslinking by water-crosslinking groups and functional groups such as the silane coupling agent (b2). The composition for rust prevention of the present invention has a much higher alkali resistance than the conventional rust preventive composition while maintaining the same coating strength as that of the conventional rust preventive composition. It was possible to form a coating film.
重合体（Ａ）の水酸基価は１〜９０ｍｇＫＯＨ／ｇであることが好ましく、１〜５０ｍｇＫＯＨ／ｇであることがより好ましく、１〜２５ｍｇＫＯＨ／ｇであることがさらに好ましい。ここで、重合体（Ａ）の水酸基価とは、重合体（Ａ）１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウム（ＫＯＨ）のｍｇ数である。重合体（Ａ）の水酸基価は、ＪＩＳ Ｋ００７０に準じた方法で求められる。 The hydroxyl value of the polymer (A) is preferably 1 to 90 mgKOH / g, more preferably 1 to 50 mgKOH / g, and further preferably 1 to 25 mgKOH / g. Here, the hydroxyl value of the polymer (A) means the number of mg of potassium hydroxide (KOH) required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the polymer (A) is acetylated. It is. The hydroxyl value of the polymer (A) is determined by a method according to JIS K0070.
α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位は、本防錆用組成物から形成される防錆塗膜の耐溶剤性を向上させるために重合体（Ａ１）に含有される。α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）としては、たとえばアクリロニトリル、メタクリルニトリル等を挙げることができる。 The structural unit derived from the nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group is for improving the solvent resistance of the rust preventive coating film formed from the rust preventive composition. It is contained in the polymer (A1). Examples of the nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group include acrylonitrile and methacrylonitrile.
α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）から導かれる構造単位は重合体（Ａ１）の基本構成単位である。ここで、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）は前記α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）を含まない。 The structural unit derived from the monomer (a-2) having an α, β-monoethylenically unsaturated group is a basic structural unit of the polymer (A1). Here, the monomer (a-2) having an α, β-monoethylenically unsaturated group does not include the nitrile monomer (a-1) having the α, β-monoethylenically unsaturated group.
α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）として、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸等のカルボキシル基含有ビニル類のエステル化物、ビニルイソシアナート、イソプロペニルイソシアナート等のイソシアナート基含有ビニル類、スチレン、α−メチルスチレン、ビニルトルエン、ｔ−ブチルスチレン等の芳香族ビニル類、その他酢酸ビニル、プロピオン酸ビニル、アクリルアミド、メタクリルアミド、メチロールアクリルアミドおよびメチロールメタクリルアミド等を挙げることができる。アクリル酸またはメタアクリル酸のエステル化物としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウロイル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等、およびグリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート等のエポキシ基含有ビニル類を挙げることができる。 As monomers (a-2) having an α, β-monoethylenically unsaturated group, esterified products of vinyls containing carboxyl groups such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, vinyl isocyanate, isopropenyl isocyanate Isocyanate group-containing vinyls such as narate, aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and t-butylstyrene, other vinyl acetate, vinyl propionate, acrylamide, methacrylamide, methylolacrylamide and methylolmethacrylamide Etc. As esterified products of acrylic acid or methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, lauroyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylamino Examples include epoxy group-containing vinyls such as ethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate. It is possible.
これらの中でも、その他モノマーとの共重合性、Ｔｇ調整の観点からｎ−ブチルアクリレートが好ましい。 Among these, n-butyl acrylate is preferable from the viewpoints of copolymerization with other monomers and Tg adjustment.
水酸基を有するモノマー（ａ−３）から導かれる構造単位は、前述のとおり、本防錆用組成物から形成される防錆塗膜の耐アルカリ性を向上させるために重合体（Ａ１）に含有され、架橋剤（Ｂ）と架橋反応する。 As described above, the structural unit derived from the monomer (a-3) having a hydroxyl group is contained in the polymer (A1) in order to improve the alkali resistance of the anticorrosive coating film formed from the present antirust composition. And a crosslinking reaction with the crosslinking agent (B).
水酸基を有するモノマー（ａ−３）としては、たとえばヒドロキシメチルアクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ラクトン変性ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレートを挙げることができる。これらの中でも、その他モノマーとの共重合性の点で２−ヒドロキシエチルメタクリレートが好ましい。 Examples of the monomer (a-3) having a hydroxyl group include hydroxymethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, and 2-hydroxy-3- Examples include hydroxyl group-containing (meth) acrylates such as phenoxypropyl (meth) acrylate. Among these, 2-hydroxyethyl methacrylate is preferable from the viewpoint of copolymerization with other monomers.
アルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位は、前述のとおり、シランカップリング剤（ｂ２）と水架橋させることにより、架橋構造の強度を高めるために重合体（Ａ１）に含有される。アルコキシシリル（メタ）アクリレート（ａ−４）としては、たとえば、トリメトキシシリル（メタ）アクリレート、トリエトキシシリル（メタ）アクリレート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、ｐ−スチリルトリメトキシシラン、等を挙げることができる。これらの中でも、共重合性、塗膜形成時の架橋反応性の点で３−メタクリロキシプロピルトリメトキシシランが好ましい。 As described above, the structural unit derived from the alkoxysilyl (meth) acrylate (a-4) is crosslinked with the silane coupling agent (b2) to form a polymer (A1) in order to increase the strength of the crosslinked structure. Contained. Examples of the alkoxysilyl (meth) acrylate (a-4) include trimethoxysilyl (meth) acrylate, triethoxysilyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. , 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, and the like. it can. Among these, 3-methacryloxypropyltrimethoxysilane is preferable from the viewpoints of copolymerizability and cross-linking reactivity during coating film formation.
重合体（Ａ１）に含まれる全構造単位の量を１００重量％としたとき、重合体（Ａ１）に含まれる前記（ａ−１）〜（ａ−４）から導かれる構造単位の含有比率はそれぞれ以下のとおりである。α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位の含有比率は、好ましくは３０〜９０重量％、より好ましくは５０〜９０重量％、さらに好ましくは５５〜８０重量％である。α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）から導かれる構造単位の含有比率は、好ましくは１０〜６０重量％、より好ましくは１０〜５０重量％、さらに好ましくは２０〜４０重量％である。水酸基含有モノマー（ａ−３）から導かれる構造単位の含有比率は、好ましくは１〜１０重量％、より好ましくは２〜７重量％、さらに好ましくは３〜６重量％である。アルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位の含有比率は、好ましくは１〜５重量％、より好ましくは１〜４重量％、さらに好ましくは１〜３重量％である。 When the amount of all structural units contained in the polymer (A1) is 100% by weight, the content ratio of the structural units derived from the (a-1) to (a-4) contained in the polymer (A1) is Each is as follows. The content ratio of the structural unit derived from the nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group is preferably 30 to 90% by weight, more preferably 50 to 90% by weight, and still more preferably. 55 to 80% by weight. The content ratio of the structural unit derived from the monomer (a-2) having an α, β-monoethylenically unsaturated group is preferably 10 to 60% by weight, more preferably 10 to 50% by weight, and still more preferably 20 to 20%. 40% by weight. The content ratio of the structural unit derived from the hydroxyl group-containing monomer (a-3) is preferably 1 to 10% by weight, more preferably 2 to 7% by weight, and further preferably 3 to 6% by weight. The content ratio of the structural unit derived from the alkoxysilyl (meth) acrylate (a-4) is preferably 1 to 5% by weight, more preferably 1 to 4% by weight, and further preferably 1 to 3% by weight.
重合体（Ａ１）に含まれ得る、前記（ａ−１）〜（ａ−４）から導かれる構造単位以外の構造単位としては、メチレンビス（メタ）アクリルアミド、ジビニルベンゼン、ポリエチレングリコール鎖含有ジ（メタ）アクリレートなどから導かれる構造単位を挙げることができる。重合体（Ａ１）に含まれ得る、前記（ａ−１）〜（ａ−４）から導かれる構造単位以外の構造単位の含有比率は、成膜性を損なわない範囲とすることができ、重合体（Ａ１）に含まれる全構造単位の量を１００重量％としたとき好ましくは０．１〜５重量％、より好ましくは０．１〜３重量％、さらに好ましくは０．１〜１重量％である。 Examples of structural units other than the structural units derived from (a-1) to (a-4) that can be contained in the polymer (A1) include methylene bis (meth) acrylamide, divinylbenzene, and polyethylene glycol chain-containing di (meta). ) Structural units derived from acrylate and the like can be mentioned. The content ratio of structural units other than the structural units derived from (a-1) to (a-4) that can be contained in the polymer (A1) can be within a range that does not impair the film formability. When the amount of all structural units contained in the coalescence (A1) is 100% by weight, it is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, still more preferably 0.1 to 1% by weight. It is.
本防錆用組成物において重合体（Ａ）が粒子として存在する場合は、その平均粒径が１０〜５００ｎｍであることが好ましく、１０〜２００ｎｍであることがより好ましく、１０〜１００ｎｍであることがさらに好ましい。重合体（Ａ）の平均粒径が前記範囲内であると、成膜性が向上し、塗膜の耐水性、耐アルカリ性、耐食性が向上する。また、前述のとおり、本発明の防錆用組成物は、カルボキシル基等の酸性基を有しないか、またはその含有量が少ない。このため、本防錆用組成物から形成される防錆塗膜の鋼板等に対する密着性が低下することが懸念される。重合体（Ａ）の平均粒径が前記範囲内であるような小粒径であると、重合体（Ａ）の鋼板等への接触面積が増大し、防錆塗膜と鋼板等との密着性が向上することも期待できる。 When the polymer (A) is present as particles in the composition for rust prevention, the average particle size is preferably 10 to 500 nm, more preferably 10 to 200 nm, and 10 to 100 nm. Is more preferable. When the average particle size of the polymer (A) is within the above range, the film formability is improved, and the water resistance, alkali resistance, and corrosion resistance of the coating film are improved. Moreover, as above-mentioned, the composition for rust prevention of this invention does not have acidic groups, such as a carboxyl group, or its content is small. For this reason, we are anxious about the adhesiveness with respect to the steel plate etc. of the antirust coating film formed from this antirust composition. When the average particle size of the polymer (A) is a small particle size within the above range, the contact area of the polymer (A) with the steel plate or the like increases, and the adhesion between the anticorrosive coating film and the steel plate or the like increases. It can also be expected to improve the performance.
重合体（Ａ）の平均粒径は、大塚電子（株）製の粒径アナライザーＦＰＡＲ−１０００等の測定器により光散乱法によって求めることができる。 The average particle size of the polymer (A) can be determined by a light scattering method using a measuring instrument such as a particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
重合体（Ａ）の平均粒径を前記範囲内にする方法としては、たとえば、重合体（Ａ）を乳化重合で製造する場合に使用する界面活性剤量を調整する方法等を挙げることができる。 Examples of the method for bringing the average particle diameter of the polymer (A) within the above range include a method for adjusting the amount of surfactant used when the polymer (A) is produced by emulsion polymerization. .
重合体（Ａ）たとえば重合体（Ａ１）の合成方法は特に制約はないが、水を主成分とした溶媒中で行う乳化重合が好ましい。 The method for synthesizing the polymer (A), for example, the polymer (A1) is not particularly limited, but emulsion polymerization performed in a solvent containing water as a main component is preferable.
オキサゾリン系化合物（ｂ１）は、重合体（Ａ）を架橋させ、架橋体を形成する物質である。防錆用組成物がオキサゾリン系化合物（ｂ１）を含むことにより、防錆塗膜の密着性および耐水性が向上する。オキサゾリン系化合物（ｂ１）としては、たとえば、２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン等の付加重合性オキサゾリン化合物と（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ポリエチレングリコール等の（メタ）アクリルエステル類、（メタ）アクリル酸アミド酢酸ビニル、スチレン、α−メチルスチレンスチレンスルホン酸ナトリウム等のオキサゾリン基と反応しない共重合可能な単量体との共重合体の水溶性又は水分散体共重合体を挙げることができる。具体的な例として、日本触媒（株）の製品であるエポクロスＫ−２０１０Ｅ、Ｋ−２０２０Ｅ、Ｋ−２０３０Ｅ、ＷＳ−５００等を挙げることができるが、これらに限定されるものではない。これらの中では、エポクロスＫ−２０２０ＥおよびＫ−２０３０Ｅが好ましい。 The oxazoline-based compound (b1) is a substance that crosslinks the polymer (A) to form a crosslinked body. When the composition for rust prevention contains the oxazoline compound (b1), the adhesion and water resistance of the rust prevention coating film are improved. Examples of the oxazoline compound (b1) include addition polymerizable oxazoline compounds such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and (meth) (Meth) acrylic esters such as methyl acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid vinyl acetate, styrene, α-methylstyrene A water-soluble or water-dispersed copolymer of a copolymer with a copolymerizable monomer that does not react with an oxazoline group such as sodium styrenesulfonate can be mentioned. Specific examples include EPOCROS K-2010E, K-2020E, K-2030E, WS-500 and the like, which are products of Nippon Shokubai Co., Ltd., but are not limited thereto. Of these, Epocross K-2020E and K-2030E are preferred.
オキサゾリン系化合物（ｂ１）のオキサゾリン基当量は、通常、２００〜５０００ｇ／当量、好ましくは２５０〜４０００ｇ／当量、更に好ましくは３００〜３０００ｇ／当量である。オキサゾリン基当量がこの範囲であると、基材密着性、塗膜強度、耐水性、耐アルカリ性の点で好ましい。 The oxazoline group equivalent of the oxazoline compound (b1) is usually 200 to 5000 g / equivalent, preferably 250 to 4000 g / equivalent, and more preferably 300 to 3000 g / equivalent. When the oxazoline group equivalent is in this range, it is preferable in terms of substrate adhesion, coating film strength, water resistance, and alkali resistance.
オキサゾリン系化合物（ｂ１）はポットライフの観点から水分散性であることが好ましい。 The oxazoline-based compound (b1) is preferably water-dispersible from the viewpoint of pot life.
本発明の防錆用組成物においてオキサゾリン系化合物（ｂ１）の含有量は、重合体（Ａ）１００重量部に対して、好ましくは１〜４０重量部、より好ましくは３〜３０重量部、さらに好ましくは５〜２０重量部である。オキサゾリン系化合物（ｂ１）の配合量がこの範囲であると、塗膜強度、基材安定性、耐水性の点で好ましい。 In the rust-preventing composition of the present invention, the content of the oxazoline-based compound (b1) is preferably 1 to 40 parts by weight, more preferably 3 to 30 parts by weight, with respect to 100 parts by weight of the polymer (A). Preferably it is 5-20 weight part. When the amount of the oxazoline-based compound (b1) is within this range, it is preferable in terms of coating film strength, substrate stability, and water resistance.
シランカップリング剤（ｂ２）は、重合体（Ａ）を架橋させ、架橋体を形成する物質である。防錆用組成物がシランカップリング剤（ｂ２）を含むことにより、防錆塗膜の耐水性が向上する。シランカップリング剤（ｂ２）としては、従来使用されている通常のシランカップリング剤を挙げることができる。シランカップリング剤（ｂ２）は、水酸基、カルボキシル基などのアクリル樹脂中の官能基と反応し得る官能基を有することが好ましく、特にグリシジル基、エポキシシクロヘキシル基、ビニル基、アミノ基、アミド基、ウレイド基、チオール基、スルフィド基およびイソシアネート基の中から選ばれる基を有することが好ましい。これらの中でも、グリシジル基、アミノ基、アミド基、またはイソシアネート基を有することが好ましい。 The silane coupling agent (b2) is a substance that crosslinks the polymer (A) to form a crosslinked body. When the composition for rust prevention contains the silane coupling agent (b2), the water resistance of the rust prevention coating film is improved. Examples of the silane coupling agent (b2) include conventionally used normal silane coupling agents. The silane coupling agent (b2) preferably has a functional group capable of reacting with a functional group in the acrylic resin such as a hydroxyl group or a carboxyl group, and in particular, a glycidyl group, an epoxycyclohexyl group, a vinyl group, an amino group, an amide group, It preferably has a group selected from a ureido group, a thiol group, a sulfide group and an isocyanate group. Among these, it is preferable to have a glycidyl group, an amino group, an amide group, or an isocyanate group.
シランカップリング剤（ｂ２）の具体的な例として、信越化学のシランカップリング剤ＫＢＭ−３０３、ＫＢＭ−４０３、ＫＢＭ−６０３、ＫＢＭ−９０３、ＫＢＭ−５８５等を挙げることができるが、これらに限定されるものではない。 Specific examples of the silane coupling agent (b2) include Shin-Etsu Chemical's silane coupling agents KBM-303, KBM-403, KBM-603, KBM-903, and KBM-585. It is not limited.
本発明の防錆用組成物においてシランカップリング剤（ｂ２）の含有比率は、重合体（Ａ）１００重量部に対して、塗膜強度、耐アルカリ性の点で、好ましくは０．１〜１０重量部、より好ましくは０．２〜８重量部、さらに好ましくは０．３〜５重量部である。 In the composition for rust prevention of the present invention, the content ratio of the silane coupling agent (b2) is preferably 0.1 to 10 in terms of coating film strength and alkali resistance with respect to 100 parts by weight of the polymer (A). Parts by weight, more preferably 0.2 to 8 parts by weight, still more preferably 0.3 to 5 parts by weight.
以上のように、本発明の防錆用組成物は重合体（Ａ）および架橋剤（Ｂ）を含有することから、実質的に酸フリーでありながら架橋反応性に優れるので、耐水性、耐アルカリ性、塗膜安定性に優れる。更に、重合体（Ａ）を小径にすることにより、耐水性、耐アルカリ性、塗膜安定性に優れる。 As described above, since the rust-preventing composition of the present invention contains the polymer (A) and the crosslinking agent (B), it is substantially acid-free and has excellent crosslinking reactivity. Excellent alkalinity and coating stability. Furthermore, by making the polymer (A) small, water resistance, alkali resistance and coating film stability are excellent.
本発明の防錆用組成物は、重合体（Ａ）、架橋剤（Ｂ）たとえばオキサゾリン系化合物（ｂ１）およびシランカップリング剤（ｂ２）以外に、必要に応じて、水酸基とオキサゾリン基との反応を促進する触媒（Ｃ）および水酸基との反応性を有する水溶性ジルコニウム化合物（Ｄ）を含有することができる。 In addition to the polymer (A), the crosslinking agent (B), for example, the oxazoline compound (b1) and the silane coupling agent (b2), the rust-preventing composition of the present invention comprises a hydroxyl group and an oxazoline group as necessary. A catalyst (C) for promoting the reaction and a water-soluble zirconium compound (D) having reactivity with a hydroxyl group can be contained.
水酸基とオキサゾリン基の反応を促進する触媒（Ｃ）は、重合体（Ａ）が有する水酸基とオキサゾリン系化合物（ｂ１）との反応を触媒し、架橋反応を促進させるために使用される。触媒（Ｃ）としては、酸、酸エステル、オニウム塩、リチウム塩類等が挙げられる。具体的には、テトラメチルホスホニウムクロライド、テトラエチルホスホニウムクロライド、メチルトリフェニルホスホニウムクロライド、ベンジルトリフェニルホスホニウムクロライド等の第４級ホスホニウム塩、リチウム、ナトリウム、カリウム、セシウム等のハロゲン化物およびその水酸化物等、リン酸、リン酸二水素アンモニウム、リン酸水素二アンモニウム、フェニルリン酸、フィニルリン酸アンモニウム、ｐ−トルエンスルホン酸、ｐ−トルエンスルホン酸アンモニウム等の酸およびそのアンモニウム塩、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、ベンジルジメチルクロライド等の第４級アンモニウム塩およびその水酸化物等を挙げることができる。この中で、テトラメチルホスホニウムクロライド、リチウムブロマイド、リチウムクロライド、水酸化リチウム、リン酸水素二アンモニウム、テトラメチルアンモニウムクロライド、テトラメチルヒドロキサイドが好ましく、特に、リン酸二水素アンモニウム、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムヒドロキサイド、ハロゲン化リチウムおよび水酸化リチウムから選ばれた化合物であることが好ましい。 The catalyst (C) that promotes the reaction between the hydroxyl group and the oxazoline group is used to catalyze the reaction between the hydroxyl group of the polymer (A) and the oxazoline-based compound (b1) and promote the crosslinking reaction. Examples of the catalyst (C) include acids, acid esters, onium salts, lithium salts and the like. Specifically, quaternary phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, methyltriphenylphosphonium chloride, benzyltriphenylphosphonium chloride, halides such as lithium, sodium, potassium, cesium and their hydroxides, etc. , Phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phenyl phosphoric acid, finyl ammonium phosphate, p-toluenesulfonic acid, ammonium p-toluenesulfonate, and ammonium salts thereof, tetramethylammonium chloride, tetraethyl Examples thereof include quaternary ammonium salts such as ammonium chloride, tetrabutylammonium chloride, and benzyldimethyl chloride, and hydroxides thereof. Among these, tetramethylphosphonium chloride, lithium bromide, lithium chloride, lithium hydroxide, diammonium hydrogen phosphate, tetramethylammonium chloride, and tetramethyl hydroxide are preferable. In particular, ammonium dihydrogen phosphate, tetramethylammonium chloride, A compound selected from tetramethylammonium hydroxide, lithium halide and lithium hydroxide is preferred.
本発明の防錆用組成物において触媒（Ｃ）の含有比率は、重合体（Ａ）１００重量部に対して、好ましくは０．１〜１０重量部、より好ましくは０．２〜７重量部、さらに好ましくは０．３〜５重量部である。触媒（Ｃ）の配合量がこの範囲であると、塗膜強度、耐アルカリ性の点で好ましい。 In the composition for rust prevention of the present invention, the content ratio of the catalyst (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 7 parts by weight with respect to 100 parts by weight of the polymer (A). More preferably, it is 0.3 to 5 parts by weight. When the blending amount of the catalyst (C) is within this range, it is preferable in terms of coating film strength and alkali resistance.
水酸基と反応し得る水溶性ジルコニウム化合物（Ｄ）は、基材密着性、耐水性、耐アルカリ性向上のために使用される。水溶性ジルコニウム化合物（Ｄ）としては、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム、硝酸ジルコニウム、酢酸ジルコニウム、塩基性炭酸ジルコニウム、ジルコニウムテトラアセチルアセトネート、ジルコニウムモノアセチルアセトネート、ジルコニウムビスアセチルアセトネート等を挙げることができる。これらの中で、水酸基との反応性、基材密着性の点で炭酸ジルコニウムアンモニウムと炭酸ジルコニウムカリウムが好ましく、特に、炭酸ジルコニウムアンモニウムが好ましい。 The water-soluble zirconium compound (D) capable of reacting with a hydroxyl group is used for improving substrate adhesion, water resistance, and alkali resistance. Examples of the water-soluble zirconium compound (D) include ammonium zirconium carbonate, zirconium carbonate potassium, zirconium nitrate, zirconium acetate, basic zirconium carbonate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium bisacetylacetonate. Can do. Of these, ammonium zirconium carbonate and potassium zirconium carbonate are preferred in terms of reactivity with hydroxyl groups and adhesion to the substrate, and ammonium zirconium carbonate is particularly preferred.
カルボキシル基と反応し得る水溶性ジルコニウム化合物（Ｄ）の含有比率は、樹脂の保存安定性の点で、重合体（Ａ）１００重量部に対して、好ましくは０．１〜５重量部、より好ましくは０．１〜３重量部、さらに好ましくは０．１〜２重量部である。 The content ratio of the water-soluble zirconium compound (D) capable of reacting with a carboxyl group is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymer (A) in terms of storage stability of the resin. Preferably it is 0.1-3 weight part, More preferably, it is 0.1-2 weight part.
本発明の防錆用組成物を水に分散させて水分散体を作製することができる。すなわち、重合体（Ａ）および架橋剤（Ｂ）、さらに必要に応じて添加される触媒（Ｃ）、水溶性ジルコニウム化合物（Ｄ）等を水に分散させて水分散体とすることができる。この水分散体は、本発明の防錆用組成物を調製し、これを水に分散して作製してもよく、本発明の防錆用組成物の各成分を個別に水に分散して作製してもよい。 An aqueous dispersion can be prepared by dispersing the rust-preventing composition of the present invention in water. That is, the polymer (A), the crosslinking agent (B), the catalyst (C) added as necessary, the water-soluble zirconium compound (D) and the like can be dispersed in water to obtain an aqueous dispersion. This water dispersion may be prepared by preparing the rust preventive composition of the present invention and dispersing it in water. Each component of the rust preventive composition of the present invention is individually dispersed in water. It may be produced.
この水分散体の固形分濃度は、特に制限されず、塗装方法、塗装に使用される装置に応じて適宜調整される。通常は（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）成分等の合計量１００重量部に対して水１００〜３０００重量部の割合であり、好ましくは２００〜２０００重量部の割合である。 The solid content concentration of the aqueous dispersion is not particularly limited, and is appropriately adjusted according to the coating method and the apparatus used for coating. Usually, the ratio is 100 to 3000 parts by weight of water, preferably 200 to 2000 parts by weight with respect to 100 parts by weight of the total amount of components (A), (B), (C) and (D). .
本発明の防錆用組成物は、さらにその他の成分を、本発明の目的が損なわれない範囲で含有することができる。本防錆用組成物が含有し得るその他の成分としては、耐食性を向上させることを目的に、無機充填剤を使用することができる。無機充填剤としては、コロイダルシリカ、酸化ジルコニウムなどが挙げられ、その配合量は、重合体（Ａ）、架橋剤（Ｂ）、触媒（Ｃ）およびジルコニウム化合物（Ｄ）の合計１００重量部に対して０〜８０重量部が好ましく、０〜６０重量部がさらに好ましい。その他成分としては、例えば、ｐＨ調整剤、キレート剤、顔料、濡れ剤、帯電防止剤、酸化防止剤、防腐剤、紫外線吸収剤、光安定化剤、蛍光増白剤、着色剤、レベリング剤、濡れ剤、発泡剤、離型剤、消泡剤、制泡剤、流動性改良剤、増粘剤等が挙げられるが、これらに制約されるものでもない。 The rust-preventing composition of the present invention can further contain other components as long as the object of the present invention is not impaired. As other components that can be contained in the composition for rust prevention, an inorganic filler can be used for the purpose of improving the corrosion resistance. Examples of the inorganic filler include colloidal silica and zirconium oxide, and the blending amount thereof is 100 parts by weight in total of the polymer (A), the crosslinking agent (B), the catalyst (C) and the zirconium compound (D). 0 to 80 parts by weight is preferable, and 0 to 60 parts by weight is more preferable. Other components include, for example, pH adjusters, chelating agents, pigments, wetting agents, antistatic agents, antioxidants, preservatives, ultraviolet absorbers, light stabilizers, fluorescent brighteners, colorants, leveling agents, A wetting agent, a foaming agent, a release agent, an antifoaming agent, a foam control agent, a fluidity improving agent, a thickening agent and the like can be mentioned, but are not limited thereto.
本発明の防錆用組成物は、その製造方法には特に制限はなく、前記各成分をブレンドすることにより製造することができる。 There is no restriction | limiting in particular in the manufacturing method, and the composition for rust prevention of this invention can be manufactured by blending said each component.
本発明の防錆用組成物は、そのまま鋼板等に塗布することもできるし、プレ反応させてから鋼板等に塗布することもできる。プレ反応条件としては通常４０〜１２０℃で５〜１００分間、好ましくは５０〜１００℃で１０〜６０分間、より好ましくは５０〜８０℃で１０〜６０分間である。 The rust-preventing composition of the present invention can be applied to a steel plate or the like as it is, or can be applied to a steel plate or the like after being pre-reacted. The pre-reaction conditions are usually 40 to 120 ° C. for 5 to 100 minutes, preferably 50 to 100 ° C. for 10 to 60 minutes, more preferably 50 to 80 ° C. for 10 to 60 minutes.
本発明の防錆用組成物は、そのまま、またはプレ反応させてから鋼板上に塗布し、乾燥させ、硬化させることにより塗膜を形成することができる。組成物の塗布は、スプレー、カーテン、フローコーター、ロールコーター、刷毛塗り、浸せきのいずれの方法によっても行うことができる。塗布された組成物は、自然乾燥を行ってもよいが、焼き付けを行うことが好ましい。通常、焼き付け温度は６０℃〜５００℃で、焼き付け時間は１〜１２０秒間である。焼き付けを行うことにより塗膜の耐水性、耐溶剤性、耐アルカリ性、耐食性を向上させることができる。 The rust-preventing composition of the present invention can form a coating film as it is or after being pre-reacted, applied onto a steel sheet, dried and cured. The composition can be applied by any of spraying, curtaining, flow coating, roll coating, brushing, and dipping methods. The applied composition may be naturally dried, but is preferably baked. Usually, the baking temperature is 60 ° C. to 500 ° C., and the baking time is 1 to 120 seconds. By baking, the water resistance, solvent resistance, alkali resistance, and corrosion resistance of the coating film can be improved.
本発明の防錆用組成物の硬化物で鋼板を被覆することにより防錆鋼板を得ることができる。 A rust-proof steel plate can be obtained by coating a steel plate with a cured product of the rust-proof composition of the present invention.
以下、実施例及び比較例により本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
［鋼板］
鋼板としては亜鉛溶融メッキ鋼板（ＪＩＳ Ｇ３３０２）を用いた。以下の実施例および比較例において得られた防錆用組成物をこの鋼板の片面の全面に塗布後、表面温度１２０℃で６０秒間乾燥することにより厚み２μｍの塗膜を形成し、防錆鋼板試料を作製した。得られた塗膜の特性を以下の評価方法により評価した。
［基材密着性］
塗膜の基材密着性をＪＩＳ Ｋ５６００−５−６に準じた碁盤目試験によって評価した。碁盤目による２５の升目のうち剥がれた升目の数により以下のように評価した。
○：剥がれている升目がない
×：１以上の升目が剥がれている
［耐水性］
作製した防錆鋼板試料を、８０℃温水に１時間浸漬し、その後の表面状態を目視にて評価した。
○：浸漬前と変化なし
△：ブリードが生じた
×：白化した
［耐アルカリ性］
作製した防錆鋼板試料を、５０℃の２％水酸化ナトリウム水溶液に５分間浸漬し、その後の表面状態を目視にて評価した。
○：浸漬前と変化なし
△：黄変したが、剥がれは生じなかった
×：黄変と剥がれが生じた
［耐溶剤性］
得られた塗膜について、メチルエチルケトンによるラビング試験を実施した。メチルエチルケトンを染み込ませたガーゼを用いて、２ｋｇｆの荷重で１０往復ラビングを行い、その後の状態を目視にて評価した。
○：ラビング前と変化なし
△：表面が荒れたが、溶解はしなかった
×：表面が溶解した
［耐食性］
得られた塗膜の表面を基材の金属に届くようにクロスカット後、５％食塩水を噴霧した。２５℃で５日間経過した後の錆の発生状態を目視にて評価した。
○：塗膜面への錆の浸入が５ｍｍ以下である
×：塗膜面への錆の浸入が５ｍｍより大きい
［重合体（Ａ）の酸価の測定方法］
重合体（Ａ）の酸価は、ＪＩＳ Ｋ００７０に準じて測定した。
［重合体（Ａ）の水酸基価の測定方法］
重合体（Ａ）の水酸基価は、ＪＩＳ Ｋ００７０に準じて測定した。
［重合体（Ａ）の平均粒径の測定方法］
重合体（Ａ）の平均粒径は、大塚電子（株）製の粒径アナライザーＦＰＡＲ−１０００により光散乱法によって測定した。
［実施例１］
攪拌機、還流冷却付きのセパラブルフラスコに蒸留水２８５重量部及びラウリル硫酸ナトリウムを２．０重量部仕込み、窒素ガスで置換した後、７５℃に昇温した。次いで過硫酸カリウム０．５重量部を添加してから下記組成のビニル単量体乳化物を４時間かけて連続的に添加し、更に３時間保持し、重合を完結させた。固形分が２４．０重量％である共重合体（重合体（Ａ））の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表1に示した。
（ビニル単量体乳化物）
アクリロニトリル ６５．０重量部
ｎ−ブチルアクリレート ２８．０重量部
２−ヒドロキシエチルメタクリレート ５．０重量部
３−メタクリロキシプロピルトリメトキシシラン ２．０重量部
ラウリル硫酸アンモニウム ０．２重量部
蒸留水 ４０．０重量部
この水分散体を固形分として１００重量部とり、そこへエポクロスＫ−２０３０Ｅ（日本触媒社製オキサゾリン系化合物、オキサゾリン基当量：５５０）を１０重量部、触媒であるリン酸二水素アンモニウムを１重量部、炭酸ジルコニウムアンモニウムを０．５重量部、３−グリシドキシプロピルトリメトキシシラン（シランカップリング剤）を５重量部、を配合し、室温にて攪拌して防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表1に示した。
［実施例２〜５］
ビニル単量体乳化物の組成を表１の実施例２〜５に示した組成に変更する以外は、実施例１と同様の操作を行い、固形分が２４．０重量％である共重合体（重合体（Ａ））の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表１に示した。エポクロスＫ−２０３０Ｅ、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび３−グリシドキシプロピルトリメトキシシランの配合量を表１に示したように変更する以外は実施例１と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表１に示した。
［比較例１、３、４］
ビニル単量体乳化物の組成を表１の比較例１、３および４に示した組成に変更する以外は、実施例１と同様の操作を行い、固形分が２４．０重量％である共重合体の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表１に示した。エポクロスＫ−２０３０Ｅ、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび３−グリシドキシプロピルトリメトキシシランの配合量を表1に示したように変更する以外は実施例１と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表１に示した。
［比較例２］
ビニル単量体乳化物の組成を表１の比較例２に示した組成に変更する以外は、実施例１と同様の操作を行い、固形分が２４．０重量％である共重合体（重合体（Ａ））の水分散体を得た。この共重合体の平均粒径、酸価および水酸基価を上記方法により求めた。その結果を表１に示した。エポクロスＫ−２０３０Ｅ、リン酸二水素アンモニウム、炭酸ジルコニウムアンモニウムおよび３−グリシドキシプロピルトリメトキシシランの配合量を表1に示したように変更する以外は実施例１と同様の操作を行い、防錆用組成物の水分散体を調製した。この水分散体を用いて基材密着性、耐水性、耐アルカリ性、耐溶剤性および耐食性を上記方法により求めた。その結果を表１に示した。EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to these Examples.
[steel sheet]
A galvanized steel sheet (JIS G3302) was used as the steel sheet. After applying the rust preventive composition obtained in the following Examples and Comparative Examples to the entire surface of one side of this steel sheet, it was dried at a surface temperature of 120 ° C. for 60 seconds to form a coating film having a thickness of 2 μm. A sample was prepared. The characteristics of the obtained coating film were evaluated by the following evaluation methods.
[Base material adhesion]
The substrate adhesion of the coating film was evaluated by a cross cut test according to JIS K5600-5-6. Evaluation was performed as follows according to the number of squares peeled out of 25 squares by the grid.
○: No peeling of the squares ×: One or more squares are peeled [water resistance]
The produced rust-proof steel plate sample was immersed in 80 degreeC warm water for 1 hour, and the subsequent surface state was evaluated visually.
○: No change from before immersion Δ: Bleed occurred ×: Whitening [alkali resistance]
The produced rust-proof steel plate sample was immersed in a 2% aqueous sodium hydroxide solution at 50 ° C. for 5 minutes, and the subsequent surface condition was visually evaluated.
○: No change from before immersion Δ: Yellowing but no peeling ×: Yellowing and peeling [solvent resistance]
The obtained coating film was rubbed with methyl ethyl ketone. Using a gauze soaked with methyl ethyl ketone, 10 reciprocating rubs were performed with a load of 2 kgf, and the subsequent state was visually evaluated.
○: No change from before rubbing △: Surface was rough but not dissolved ×: Surface was dissolved [corrosion resistance]
After cross-cutting the surface of the obtained coating film so as to reach the base metal, 5% saline was sprayed. The state of rust generation after 5 days at 25 ° C. was visually evaluated.
○: Infiltration of rust into the coating film surface is 5 mm or less ×: Infiltration of rust into the coating film surface is larger than 5 mm [Method for measuring acid value of polymer (A)]
The acid value of the polymer (A) was measured according to JIS K0070.
[Method for Measuring Hydroxyl Value of Polymer (A)]
The hydroxyl value of the polymer (A) was measured according to JIS K0070.
[Method for Measuring Average Particle Diameter of Polymer (A)]
The average particle size of the polymer (A) was measured by a light scattering method using a particle size analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.
[Example 1]
A separable flask equipped with a stirrer and reflux cooling was charged with 285 parts by weight of distilled water and 2.0 parts by weight of sodium lauryl sulfate, replaced with nitrogen gas, and then heated to 75 ° C. Next, 0.5 part by weight of potassium persulfate was added, and then a vinyl monomer emulsion having the following composition was continuously added over 4 hours and held for another 3 hours to complete the polymerization. An aqueous dispersion of a copolymer (polymer (A)) having a solid content of 24.0% by weight was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1.
(Vinyl monomer emulsion)
Acrylonitrile 65.0 parts by weight n-butyl acrylate 28.0 parts by weight 2-hydroxyethyl methacrylate 5.0 parts by weight 3-methacryloxypropyltrimethoxysilane 2.0 parts by weight Ammonium lauryl sulfate 0.2 parts by weight Distilled water 40.0 Part by weight This aqueous dispersion was taken as 100 parts by weight as solid content, and 10 parts by weight of Epocross K-2030E (Nippon Shokubai Co., Ltd., oxazoline-based compound, oxazoline group equivalent: 550) and ammonium dihydrogen phosphate as a catalyst were added thereto. 1 part by weight, 0.5 parts by weight of ammonium zirconium carbonate and 5 parts by weight of 3-glycidoxypropyltrimethoxysilane (silane coupling agent) were blended and stirred at room temperature to give a composition for rust prevention. An aqueous dispersion was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
[Examples 2 to 5]
A copolymer having a solid content of 24.0% by weight, except that the composition of the vinyl monomer emulsion is changed to the compositions shown in Examples 2 to 5 of Table 1 in the same manner as in Example 1. An aqueous dispersion of (polymer (A)) was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1. The same procedure as in Example 1 was carried out except that the compounding amounts of Epocros K-2030E, ammonium dihydrogen phosphate, ammonium zirconium carbonate and 3-glycidoxypropyltrimethoxysilane were changed as shown in Table 1. An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
[Comparative Examples 1, 3, 4]
The same procedure as in Example 1 was performed except that the composition of the vinyl monomer emulsion was changed to the compositions shown in Comparative Examples 1, 3 and 4 in Table 1, and the solid content was 24.0% by weight. An aqueous dispersion of the polymer was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1. The same procedure as in Example 1 was carried out except that the compounding amounts of Epocros K-2030E, ammonium dihydrogen phosphate, ammonium zirconium carbonate and 3-glycidoxypropyltrimethoxysilane were changed as shown in Table 1. An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
[Comparative Example 2]
The same procedure as in Example 1 was performed except that the composition of the vinyl monomer emulsion was changed to the composition shown in Comparative Example 2 of Table 1. An aqueous dispersion of coalescence (A)) was obtained. The average particle size, acid value, and hydroxyl value of this copolymer were determined by the above methods. The results are shown in Table 1. The same procedure as in Example 1 was carried out except that the compounding amounts of Epocros K-2030E, ammonium dihydrogen phosphate, ammonium zirconium carbonate and 3-glycidoxypropyltrimethoxysilane were changed as shown in Table 1. An aqueous dispersion of the rusting composition was prepared. Using this aqueous dispersion, substrate adhesion, water resistance, alkali resistance, solvent resistance and corrosion resistance were determined by the above methods. The results are shown in Table 1.
Claims (17)
重合体（Ａ）が、重合体（Ａ）に含まれる全構造単位の量を１００重量％としたとき、α，β−モノエチレン性不飽和基を有するニトリル系モノマー（ａ−１）から導かれる構造単位を３０〜８０重量％、α，β−モノエチレン性不飽和基を有するモノマー（ａ−２）（ただし、前記（ａ−１）成分を除く）から導かれる構造単位を１０〜６０重量％、水酸基を有するモノマー（ａ−３）から導かれる構造単位を１〜１０重量％、およびアルコキシシリル（メタ）アクリレート（ａ−４）から導かれる構造単位を１〜５重量％含む防錆用組成物。 Containing at least a polymer (A) having a nitrile group, a hydroxyl group, and an alkoxysilyl group and a crosslinking agent (B) ,
The polymer (A) is derived from a nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group when the amount of all structural units contained in the polymer (A) is 100% by weight. 30 to 80% by weight of the structural unit to be removed and 10 to 60 structural units derived from the monomer (a-2) having an α, β-monoethylenically unsaturated group (excluding the component (a-1)) 1% by weight of structural units derived from the monomer (a-3) having a hydroxyl group and 1 to 5% by weight of structural units derived from the alkoxysilyl (meth) acrylate (a-4) Composition.
When the amount of all structural units is 100% by weight, 30-80% by weight of structural units derived from the nitrile monomer (a-1) having an α, β-monoethylenically unsaturated group, α, β-mono 10 to 60% by weight of structural units derived from the monomer (a-2) having an ethylenically unsaturated group (excluding the component (a-1)), and derived from the monomer (a-3) having a hydroxyl group 1 to 10 wt% of structural units and alkoxysilyl (meth) Anti-corrosive polymer containing 1-5% by weight of structural units derived from acrylate (a-4).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012193127 | 2012-09-03 | ||
| JP2012193127 | 2012-09-03 | ||
| PCT/JP2013/073258 WO2014034828A1 (en) | 2012-09-03 | 2013-08-30 | Composition for rust prevention and aqueous dispersion containing same |
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| JP5921695B2 true JP5921695B2 (en) | 2016-05-24 |
| JPWO2014034828A1 JPWO2014034828A1 (en) | 2016-08-08 |
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| KR (1) | KR101728249B1 (en) |
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| CN104611099A (en) * | 2015-01-28 | 2015-05-13 | 安徽祈艾特电子科技有限公司 | Metal rust-removing and rust-preventing mixed oil |
| CN104629880A (en) * | 2015-01-28 | 2015-05-20 | 安徽祈艾特电子科技有限公司 | High-moist-heat-resistance salt-mist-resistant antirust oil |
| CN104611108A (en) * | 2015-01-28 | 2015-05-13 | 安徽祈艾特电子科技有限公司 | Long-acting quick-drying metal anti-rust oil |
| CN111032789B (en) * | 2017-09-05 | 2022-09-13 | 株式会社日本触媒 | Adhesive composition, anchor body, and method for producing anchor body |
| CN112142903B (en) * | 2019-06-28 | 2022-07-15 | 长兴化学工业(中国)有限公司 | Organic silicon modified acrylic resin and preparation method thereof |
| CN113004517B (en) * | 2021-03-08 | 2022-08-09 | 广州市白云化工实业有限公司 | Modified epoxy resin, adhesive, preparation method and application thereof |
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| JPH11189744A (en) * | 1997-10-24 | 1999-07-13 | Kansai Paint Co Ltd | Coating material composition having high solid content |
| JP2000273386A (en) * | 1999-03-25 | 2000-10-03 | Basf Dispersions Co Ltd | Aqueous resin dispersion composition |
| JP2003327902A (en) * | 2002-05-16 | 2003-11-19 | Nippon Yushi Basf Coatings Kk | Coating material composition and coated article |
| JP2005296789A (en) * | 2004-04-12 | 2005-10-27 | Gunma Univ | Method for coating surface of metallic material with high molecular polymer and metallic material coated with high molecular polymer |
| JP2006022127A (en) * | 2004-07-06 | 2006-01-26 | Mitsui Chemicals Inc | Composition for water dispersion type rust-preventing coating |
| WO2009044912A1 (en) * | 2007-10-05 | 2009-04-09 | Harima Chemicals, Inc. | Hydrophilic coating agent, hydrophilic coating film, and hydrophilic base |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2004215240C1 (en) * | 2003-02-25 | 2010-10-07 | Chemetall Gmbh | Method for coating metallic surfaces with a silane-rich composition |
| CN102337067A (en) * | 2011-07-06 | 2012-02-01 | 江苏金陵特种涂料有限公司 | Aqueous epoxy antirust paint |
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- 2013-08-30 WO PCT/JP2013/073258 patent/WO2014034828A1/en active Application Filing
- 2013-08-30 KR KR1020157002901A patent/KR101728249B1/en active IP Right Grant
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189744A (en) * | 1997-10-24 | 1999-07-13 | Kansai Paint Co Ltd | Coating material composition having high solid content |
| JP2000273386A (en) * | 1999-03-25 | 2000-10-03 | Basf Dispersions Co Ltd | Aqueous resin dispersion composition |
| JP2003327902A (en) * | 2002-05-16 | 2003-11-19 | Nippon Yushi Basf Coatings Kk | Coating material composition and coated article |
| JP2005296789A (en) * | 2004-04-12 | 2005-10-27 | Gunma Univ | Method for coating surface of metallic material with high molecular polymer and metallic material coated with high molecular polymer |
| JP2006022127A (en) * | 2004-07-06 | 2006-01-26 | Mitsui Chemicals Inc | Composition for water dispersion type rust-preventing coating |
| WO2009044912A1 (en) * | 2007-10-05 | 2009-04-09 | Harima Chemicals, Inc. | Hydrophilic coating agent, hydrophilic coating film, and hydrophilic base |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104487611B (en) | 2016-09-21 |
| KR101728249B1 (en) | 2017-04-18 |
| KR20150036354A (en) | 2015-04-07 |
| JPWO2014034828A1 (en) | 2016-08-08 |
| WO2014034828A1 (en) | 2014-03-06 |
| CN104487611A (en) | 2015-04-01 |
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