JPH0741702A - Water-base rustproof resin coating composition applicable to oily surface - Google Patents
Water-base rustproof resin coating composition applicable to oily surfaceInfo
- Publication number
- JPH0741702A JPH0741702A JP20452293A JP20452293A JPH0741702A JP H0741702 A JPH0741702 A JP H0741702A JP 20452293 A JP20452293 A JP 20452293A JP 20452293 A JP20452293 A JP 20452293A JP H0741702 A JPH0741702 A JP H0741702A
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- water
- copolymer resin
- resin emulsion
- weight
- rust preventive
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は建物の金属製内外装用材
料、金属製家具、自動車の車体シャーシ、エンジン周囲
部および缶等金属構造物や鋳物、さらにはコンクリート
やＡＬＣ等の各種発泡コンクリートで被覆される鉄芯や
ラス等、特に脱脂処理工程前に金属面にディッピングま
たはその他の塗装手段により直接塗布または塗装するに
際し、これら各種金属面を塗装するための水系防錆剤と
して極めて有用な完全リサイクル型油面防錆性水系樹脂
塗料組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to metal interior and exterior materials for buildings, metal furniture, car body chassis of automobiles, metal structures and castings such as engine surrounding parts and cans, and various foamed concrete such as concrete and ALC. Completely useful as a water-based rust preventive for coating various metal surfaces such as iron cores and laths to be coated, especially when directly applying or coating to metal surfaces by dipping or other coating means before the degreasing process. The present invention relates to a recycle type oil surface rust preventive water-based resin coating composition.
【０００２】[0002]
【従来の技術】普通金属表面に塗料を塗装する場合、金
属表面には防錆油が塗布されているため、何らかの処置
なしに直接その上に塗料を施すことは不可能に近かっ
た。少なくとも水系塗料（エマルジョン塗料）は油面塗
装性が全くなく、金属表面の油によりはじかれ、濡れ性
もなく、塗りムラが生じ、更に金属との密着も全くない
というような状態であった。従って、従来は特殊な油吸
収能を有する薬剤を配合した一部の溶剤系塗料の独壇場
となっていた。2. Description of the Related Art When a paint is applied to a normal metal surface, it is almost impossible to apply the paint directly on the metal surface because rust preventive oil is applied to the metal surface. At least the water-based paint (emulsion paint) had no oil surface coatability, was repelled by the oil on the metal surface, had no wettability, had coating unevenness, and had no adhesion to the metal at all. Therefore, conventionally, some solvent-based paints containing a special oil-absorbing agent have been the exclusive venue.
【０００３】またスプレー塗装などにおいては飛散する
塗料ミストによる塗料ロスあるいは塗料ミストの回収な
どにもコストがかかることになる。これはたとえ環境対
応型水系塗料であってもスプレー、静電塗装などの霧化
型塗装方式を用いれば、被着物に付着しない多量の塗料
ミストはブース水中に分散また溶解するので、排水時に
は凝集沈殿リサイクル方式によって水と塗料ミストスラ
ッジを分離して処理しなければならない。それにはその
ための設備とランニング時の凝集沈殿剤、更に水を多量
に含んだスラッジの廃棄処理など、その処理に膨大な費
用を要する。それゆえに塗装時には全部の塗料を使い切
ったり、リサイクルしたりなどの方法により外部には一
切廃棄物を出さない完全リサイクル方式となる浸漬塗装
方式（ディッピング）が有効である。この方式は棒、シ
ートなど単純な形状のものの塗装には有効であるが、ラ
ス網のような複雑形状物には塗膜の付着が部位により不
均一になり、塗膜の性能、外観が非常に劣化する。Further, in spray painting and the like, it is costly to collect the paint loss or the paint mist due to the scattered paint mist. This is because even if it is an environmentally friendly water-based paint, if you use an atomization-type coating method such as spraying or electrostatic coating, a large amount of paint mist that does not adhere to the adherend will disperse or dissolve in the booth water, so it will aggregate during drainage. Water and paint mist sludge must be separated and treated by sedimentation recycling method. For that purpose, a huge amount of cost is required for the treatment, such as equipment and a flocculating precipitant at the time of running, and further disposal of sludge containing a large amount of water. Therefore, it is effective to use the dip coating method (dipping), which is a complete recycling method in which all the paint is used up or is recycled at the time of painting, and no waste is discharged outside. This method is effective for coating simple shapes such as rods and sheets, but on complicated shapes such as lath nets, the adhesion of the coating becomes uneven depending on the site, and the performance and appearance of the coating are extremely poor. Deteriorates.
【０００４】例えば、網目に膜を張ったり、針金の交差
部には塗料がたまり、このタマリ部は加熱乾燥時、フク
レ現象を起こし、その部分の防錆性が極端に劣化する。
また上部と下部では上部が薄く下部が厚いという膜厚不
均一現象を生ずるので、防錆性能が不均一となる。For example, a film is formed on the mesh or paint is accumulated at the intersections of the wires, and this lumpy portion causes a blistering phenomenon when heated and dried, and the rust preventive property of the portion is extremely deteriorated.
In addition, the unevenness of the film thickness occurs in the upper part and the lower part, that is, the upper part is thinner and the lower part is thicker, resulting in uneven rust prevention performance.
【０００５】溶剤系塗料は溶剤の大気へ揮散による環境
汚染、引火性、着火性の高い溶剤による火災の危険性、
さらには溶剤の作業環境の悪化等、多くの問題点を有す
るところから溶剤系塗料から水系塗料へのスムーズな置
換が要求されるところであるが、水系塗料は本質的に油
とは相溶せず、防錆油が塗布された金属表面または油性
塗料塗布金属面への直接塗布可能な塗料への要求は不可
能または実現にはほど遠いものであった。[0005] Solvent-based paints are environmental pollution caused by volatilization of the solvent into the atmosphere, risk of fire due to highly flammable and ignitable solvents,
Furthermore, since there are many problems such as the deterioration of the working environment of the solvent, it is required to smoothly replace the solvent-based paint with the water-based paint, but the water-based paint is essentially incompatible with oil. However, the demand for a paint that can be directly applied to a metal surface coated with rust preventive oil or a metal surface coated with an oil-based paint has been impossible or far from being realized.
【０００６】従来水系塗料を使用する場合は、まず防錆
油が付着した金属基材をアルカリ水溶液により脱脂し、
湯洗いし、次に水洗、表面調整を行い、更に水洗し、化
成処理工程を経て更に水洗を繰り返すといった各種の工
程を経た後、初めて塗装可能の条件を得るという莫大な
労力と費用が係る作業を経なければならなかった。その
上、廃アルカリ水溶液、廃水洗液等の処理、更にそれら
から副生する廃油、スラッジ、処理のための中和剤など
脱脂液、化成処理液を安全に廃棄するために莫大な費用
が要求されている。In the case of using a conventional water-based paint, first degrease a metal base material to which rust preventive oil is adhered with an alkaline aqueous solution,
A work that requires enormous labor and cost to obtain the condition that can be coated for the first time after undergoing various processes such as washing with hot water, then washing with water, surface conditioning, further washing with water, repeating chemical conversion treatment and further washing with water. Had to go through. Moreover, enormous cost is required to safely dispose of waste alkaline aqueous solution, waste water washing liquid, etc., and waste oil, sludge, neutralizing agent for treatment such as degreasing liquid and chemical conversion liquid safely produced from them. Has been done.
【０００７】以上のようなことから前記脱脂工程、化成
処理工程、それに伴う廃塗料、廃油問題の全くない防錆
油などの油類が付着した金属基材そのままに何の処理工
程も要さず直接塗装が可能な油面塗装性の防錆性水系樹
脂塗料組成物の登場が望まれている。From the above, the degreasing step, the chemical conversion treatment step, the accompanying waste paint, and the metal base material on which the oil such as rust preventive oil having no waste oil problem adheres as it is without any treatment step. It has been desired to introduce a rust-preventive water-based resin coating composition that can be directly coated on the oil surface.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、防錆油など
の油類が付着した複雑形状の金属基材表面に直接塗装が
可能であり、複雑形状被塗物（例えばラス網）のごとき
ものであっても、一度で大量にディッピング塗装すると
きには余分な塗料が速やかに流れ落ち、しかもタレ、タ
マリ、ハジキがなく、エッジカバーがよく、かつ防錆
性、金属基材表面への塗装性と付着性に優れ、耐水性の
良好な安全無公害型水系防錆塗料として極めて有用な油
面防錆性水系樹脂塗料組成物を開発することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention is capable of directly coating the surface of a metal substrate having a complicated shape, to which oils such as rust preventive oil adheres, such as an object to be coated with a complicated shape (for example, lath net). Even if it is a thing, when a large amount of dipping coating is done at one time, excess paint runs off quickly, there is no sagging, tampering, cissing, good edge cover, rust prevention, and coatability on the metal substrate surface. It is an object of the present invention to develop a water-based resin coating composition having an oil surface rust preventive property, which is excellent in adhesion and has good water resistance, and which is extremely useful as a safety pollution-free water rust preventive paint.
【０００９】[0009]
【課題を解決するための手段】本発明は、塗料組成物中
に水系共重合樹脂エマルジョン（樹脂分として）を１０
〜４０重量％、リン酸塩系、モリブデン酸塩系、メタホ
ウ酸塩系、炭酸塩系、酸化物系およびフェライト系の無
機系防錆顔料および有機系防錆顔料から選ばれた少なく
とも一種の防錆顔料を０．５〜３０重量％、親水性有機
溶剤を０．５〜２０重量％、増粘剤を０．１〜３重量
％、分散剤を０．１〜３重量％、湿潤剤を０．１〜２重
量％、消泡剤を０．０５〜２重量％を含み、かつ不揮発
分濃度２０〜６０％、顔料体積濃度（ＰＶＣ）１０〜５
０％であることを特徴とする油面防錆性水系樹脂塗料組
成物を開発することにより上記の目的を達成した。According to the present invention, an aqueous copolymer resin emulsion (as a resin component) is used in a coating composition.
-40% by weight, at least one anticorrosive selected from phosphate-based, molybdate-based, metaborate-based, carbonate-based, oxide-based and ferrite-based inorganic anticorrosion pigments and organic anticorrosion pigments. Rust pigment 0.5 to 30% by weight, hydrophilic organic solvent 0.5 to 20% by weight, thickener 0.1 to 3% by weight, dispersant 0.1 to 3% by weight, wetting agent 0.1 to 2% by weight, antifoaming agent 0.05 to 2% by weight, and non-volatile content concentration 20 to 60%, pigment volume concentration (PVC) 10 to 5
The above object was achieved by developing an oil surface rust preventive water-based resin coating composition characterized by being 0%.
【００１０】本発明に使用する水系共重合樹脂エマルジ
ョンとしては、スチレン／（メタ）アクリル酸エステル
／不飽和カルボン酸共重合樹脂エマルジョン、エチレン
／カルボン酸ビニルエステル共重合樹脂エマルジョン、
（メタ）アクリル酸エステル／不飽和カルボン酸共重合
樹脂エマルジョン、エチレン／カルボン酸ビニルエステ
ル／（メタ）アクリル酸エステル共重合樹脂エマルジョ
ン、スチレン／ブタジエン共重合樹脂エマルジョン等を
挙げることができる。The aqueous copolymer resin emulsion used in the present invention includes styrene / (meth) acrylic acid ester / unsaturated carboxylic acid copolymer resin emulsion, ethylene / carboxylic acid vinyl ester copolymer resin emulsion,
Examples thereof include (meth) acrylic acid ester / unsaturated carboxylic acid copolymer resin emulsion, ethylene / vinyl carboxylate ester / (meth) acrylic acid ester copolymer resin emulsion, and styrene / butadiene copolymer resin emulsion.
【００１１】（メタ）アクリル酸エステルとしては、ア
クリル酸またはメタクリル酸の炭素数１〜１２のアルキ
ルエステル、例えばアクリル酸メチル、アクリル酸エチ
ル、アクリル酸ブチル、アクリル酸プロピル、アクリル
酸イソプロピル、アクリル酸イソブチル、アクリル酸２
−エチルヘキシル、アクリル酸デシル、アクリル酸ドデ
シル、アクリル酸イソボルニル、メタクリル酸メチル、
メタクリル酸エチル、メタクリル酸プロピル、メタクリ
ル酸イソプロピル、メタクリル酸ブチル、メタクリル酸
イソブチル、メタクリル酸ラウリル、メタクリル酸２−
エチルヘキシル、イソボルニルメタアクリレート等を挙
げることができる。またこのほかアクリル酸２−ヒドロ
キシエチル、アクリル酸ヒドロキシイソプロピル、メタ
クリル酸２−ヒドロキシエチル、グリシジル（メタ）ア
クリレート、ポリエチレングリコールモノメタクリレー
トなども含まれる。The (meth) acrylic acid ester is an alkyl ester of acrylic acid or methacrylic acid having 1 to 12 carbon atoms, for example, methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, acrylic acid. Isobutyl, acrylic acid 2
-Ethylhexyl, decyl acrylate, dodecyl acrylate, isobornyl acrylate, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, lauryl methacrylate, 2-methacrylic acid
Examples thereof include ethylhexyl and isobornyl methacrylate. In addition, 2-hydroxyethyl acrylate, hydroxyisopropyl acrylate, 2-hydroxyethyl methacrylate, glycidyl (meth) acrylate, polyethylene glycol monomethacrylate and the like are also included.
【００１２】カルボン酸ビニルエステルとしては、酢酸
ビニル、バーサティック酸ビニル等を挙げることができ
る。Examples of vinyl carboxylic acid esters include vinyl acetate and vinyl versatate.
【００１３】不飽和カルボン酸としては一価または二価
の不飽和カルボン酸が含まれ、アクリル酸、メタクリル
酸、マレイン酸、フマル酸、イタコン酸等を挙げること
ができる。The unsaturated carboxylic acid includes monovalent or divalent unsaturated carboxylic acids, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.
【００１４】上記以外にアクリルアミド、α−メチロー
ルアクリルアミド、スチレン、α−メチルスチレン、ア
クリロニトリル、塩化ビニリデン、エチレン、ブタジエ
ン等、それぞれのモノマーと共重合可能な場合に組み合
わせて使用できる。これらモノマーの中でエチレン、ス
チレンとアクリロニトリルが実用的にもっとも有用であ
る。In addition to the above, acrylamide, α-methylolacrylamide, styrene, α-methylstyrene, acrylonitrile, vinylidene chloride, ethylene, butadiene and the like can be used in combination when they can be copolymerized with the respective monomers. Among these monomers, ethylene, styrene and acrylonitrile are practically the most useful.
【００１５】本発明に使用する水系共重合樹脂エマルジ
ョンの代表例としては、エチレン／酢酸ビニル／バーサ
ティック酸ビニル共重合樹脂エマルジョン、スチレン／
アクリロニトリル／アクリル酸２−エチルヘキシル／グ
リシジルメタクリレート／メタクリル酸共重合樹脂エマ
ルジョンが挙げられる。Typical examples of the water-based copolymer resin emulsion used in the present invention include ethylene / vinyl acetate / vinyl versatic acid copolymer emulsion, styrene /
Examples thereof include acrylonitrile / 2-ethylhexyl acrylate / glycidyl methacrylate / methacrylic acid copolymer resin emulsion.
【００１６】本発明において、ホモポリマーのエマルジ
ョンを使用した場合は、油面塗装性に劣り、ポリマーの
種類によっては付着性や耐水性に劣る欠点がある。例え
ば酢酸ビニル重合体エマルジョンを使用した場合は、油
面塗装性や耐水性に劣り、油面防錆性としては好ましく
ない。In the present invention, when a homopolymer emulsion is used, there is a drawback that the oil surface coating property is poor, and the adhesion and water resistance are poor depending on the type of polymer. For example, when a vinyl acetate polymer emulsion is used, the oil surface coatability and water resistance are poor, and the oil surface rust resistance is not preferable.
【００１７】防錆顔料としては、エマルジョン塗料にお
いて薄膜で防錆効果があり、環境汚染がなく、廃棄物処
理対策上問題が少ないリン酸塩系Ｚｎ，Ａｌ，Ｃａ等の
顔料、モリブデン酸塩系Ｚｎ，Ａｌ，Ｃａ等の顔料、メ
タホウ酸塩系Ｂａ，Ｚｎ，Ｃａ等の顔料、炭酸塩系Ｚｎ
等の顔料、酸化物系Ａｌ，Ｃａ顔料、フェライト系の無
機系防錆顔料および有機系防錆顔料（Ｚｎ−ニトロ化合
物）等が挙げられ、これらの１種またはそれらを組み合
わせて使用することができる。これらの防錆顔料の中で
リン酸亜鉛、リン酸アルミニウム、メタホウ酸バリウム
がもっとも重要で、実用的である。As the rust-preventive pigment, phosphate-based pigments such as Zn, Al, and Ca, molybdate-based pigments, which have a thin-film rust-preventive effect in emulsion paints, have no environmental pollution, and have few problems in waste treatment measures. Zn, Al, Ca, etc. pigments, metaborate-based pigments such as Ba, Zn, Ca, etc., carbonate-based Zn
And the like, oxide-based Al and Ca pigments, ferrite-based inorganic rust-preventive pigments and organic rust-preventive pigments (Zn-nitro compounds), and the like, and it is possible to use one of these or a combination thereof. it can. Among these anticorrosion pigments, zinc phosphate, aluminum phosphate and barium metaborate are the most important and practical.
【００１８】親水性の有機溶剤としては、メタノール、
エタノール、イソプロピルアルコール、エチレングリコ
ール、プロピレングリコール等のアルコール類、エチレ
ングリコールモノアルキルエーテル、ジエチレングリコ
ールモノアルキルエーテル、プロピレングリコールモノ
アルキルエーテル、ジプロピレングリコールモノアルキ
ルエーテル等のグリコール誘導体類、ジオキサンのよう
なエーテル類、アセトンのようなケトン類、その他ｎ−
メチルピロリドン等の親水性溶剤が挙げられる。これら
の溶剤の中で、プロピレングリコール、プロピレングリ
コール誘導体類は毒性が少なく労働安全衛生上問題がな
く性能的にも優れ、実用的である。As the hydrophilic organic solvent, methanol,
Alcohols such as ethanol, isopropyl alcohol, ethylene glycol and propylene glycol, glycol derivatives such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether and dipropylene glycol monoalkyl ether, ethers such as dioxane. , Ketones such as acetone, and other n-
A hydrophilic solvent such as methylpyrrolidone may be used. Among these solvents, propylene glycol and propylene glycol derivatives are practical because they are less toxic, have no problems in occupational safety and health, and have excellent performance.
【００１９】増粘剤としては繊維素誘導体、例えばヒド
ロキシエチルセルロース、メチルセルロース、ポリアク
リル酸系、ポリエーテル系等が挙げられ、繊維素誘導体
はエッジカバー性の点から重要で、実用的である。Examples of the thickener include fibrin derivatives such as hydroxyethyl cellulose, methyl cellulose, polyacrylic acid type, and polyether type. The fibrin derivative is important and practical from the viewpoint of edge covering property.
【００２０】抑泡性のある分散剤（界面活性剤）として
は、ポリカルボン酸塩、スルホン酸塩、硫酸エステル
塩、リン酸エステル塩が挙げられ、湿潤剤としては非シ
リコーン系アクリルゴマー［アクリルオリゴマーであ
り、（メタ）アクリル酸または（メタ）アクリル酸と
（メタ）アクリル酸エステル共重合体である。］、ポリ
カルボン酸塩系などが挙げられ、特に非シリコーン系界
面活性剤が好ましい。これらと消泡剤との組み合わせに
より、抑泡性のある塗料が得られる。Examples of the dispersant (surfactant) having a foam suppressing property include polycarboxylic acid salts, sulfonic acid salts, sulfuric acid ester salts and phosphoric acid ester salts, and the wetting agent is a non-silicone acrylic gomer [acryl]. It is an oligomer and is (meth) acrylic acid or a (meth) acrylic acid and (meth) acrylic acid ester copolymer. ], A polycarboxylic acid salt type, and the like, and a non-silicone type surfactant is particularly preferable. By combining these with an antifoaming agent, a paint having a foam suppressing property can be obtained.
【００２１】消泡剤としてはメチル（α−アミノプロピ
ル）シロキサンとジメチルシロキサンの共重合物からな
るエマルジョン系、アルキル変性ポリシロキサン系、フ
ッ素系等が挙げられ、有機変性ポリシロキサン系が消泡
効果とハジキ、流下性の点から重要で、実用的である。Examples of the defoaming agent include emulsion type composed of a copolymer of methyl (α-aminopropyl) siloxane and dimethylsiloxane, alkyl modified polysiloxane type, fluorine type, etc., and organic modified polysiloxane type defoaming effect. It is important and practical in terms of cissing and drainage.
【００２２】不揮発分濃度は一定の塗膜厚を確保し、防
錆性の良い塗膜を得るために作業粘度と関連しながら不
揮発分濃度を２０〜６０％に調整することが重要で、実
用的である。It is important to adjust the concentration of non-volatile matter to 20 to 60% in relation to the working viscosity in order to obtain a coating film having a constant thickness and to obtain a coating film with good rust prevention. Target.
【００２３】顔料体積濃度（ＰＶＣ）は造膜性、基材へ
の密着性、防錆性、塗膜表面のベタツキよりＰＶＣを１
０〜５０％に調整することは重要で、実用的である。The pigment volume concentration (PVC) is 1 for PVC because of its film-forming property, adhesion to a substrate, rust prevention, and stickiness of the coating film surface.
Adjusting to 0-50% is important and practical.
【００２４】本発明の油面防錆性水系樹脂塗料組成物に
おける水系共重合樹脂エマルジョンの配合量は、樹脂分
として１０〜４０重量％であり、好ましくは１５〜３５
重量％である。１０重量％より少ない場合は被塗物への
接着性に乏しく、４０重量％より多い場合はブロッキン
グ性等の問題が生じる。The amount of the water-based copolymer resin emulsion in the oil-based rust preventive water-based resin coating composition of the present invention is 10 to 40% by weight, preferably 15 to 35% by weight as a resin component.
% By weight. When the amount is less than 10% by weight, the adhesion to the article to be coated is poor, and when the amount is more than 40% by weight, problems such as blocking property occur.
【００２５】防錆顔料の配合量は０．５〜３０重量％で
あり、好ましくは０．５〜２０重量％である。０．５重
量％より少ない場合は防錆性が不十分であり、３０重量
％より多い場合は塗料としての貯蔵安定性などに問題が
生ずる。防錆顔料は各種の金属塩であり、エマルジョン
の安定性に影響を与えるので、その選択と組成について
は注意が必要である。The amount of the rust preventive pigment compounded is 0.5 to 30% by weight, preferably 0.5 to 20% by weight. If the amount is less than 0.5% by weight, the rust preventive property is insufficient, and if the amount is more than 30% by weight, problems occur in the storage stability as a paint. Antirust pigments are various metal salts that affect the stability of emulsions, so care must be taken in their selection and composition.
【００２６】親水性有機溶剤の使用量は０．５〜２０重
量％である。より好ましくは引火性、着火性を考慮する
とＣ3 以上のアルコールまたはプロピレングリコールエ
ーテルを２〜１５重量％配合したものが良い。配合量が
０．５重量％より少ない場合は油面に対する塗料として
の親和性が劣り、ハジキ、付着不良等の欠陥を生ずる。
２０重量％より多い場合は安定性に劣り、環境対応上の
問題が生じる。The amount of hydrophilic organic solvent used is 0.5 to 20% by weight. More preferably, in consideration of flammability and ignitability, it is preferable to blend 2 to 15% by weight of C 3 or more alcohol or propylene glycol ether. If the blending amount is less than 0.5% by weight, the affinity as a paint for the oil surface is poor and defects such as cissing and poor adhesion occur.
If it is more than 20% by weight, the stability is poor and an environmental problem occurs.
【００２７】増粘剤の使用量は０．１〜３重量％が望ま
しく、より好ましくは０．１５〜２重量％である。０．
１重量％より少ない場合は粘度が低く、油面上でハジキ
が発生し、均一な膜が得られない。３重量％より多い場
合は粘度が高く、ディッピング作業性に劣る。The amount of the thickener used is preferably 0.1 to 3% by weight, more preferably 0.15 to 2% by weight. 0.
When the amount is less than 1% by weight, the viscosity is low, cissing occurs on the oil surface, and a uniform film cannot be obtained. If it exceeds 3% by weight, the viscosity is high and the dipping workability is poor.
【００２８】分散剤の使用量は０．１〜３重量％が望ま
しく、より好ましくは０．５〜１重量％である。０．１
重量％より少ない場合は顔料分散性が不十分で、３重量
％より多い場合は抑泡性に劣るため流下性が不十分で、
また緻密な塗膜ができず防錆性にも劣る。The amount of the dispersant used is preferably 0.1 to 3% by weight, more preferably 0.5 to 1% by weight. 0.1
When it is less than 5% by weight, the pigment dispersibility is insufficient, and when it is more than 3% by weight, the foaming property is poor and the flowability is insufficient.
In addition, a dense coating film cannot be formed and rust resistance is poor.
【００２９】湿潤剤の使用量は０．１〜２重量％、より
好ましくは０．３〜１重量％である。０．１重量％より
少ない場合は濡れ性が悪く、２重量％より多い場合は耐
水性が低下する。The amount of the wetting agent used is 0.1 to 2% by weight, more preferably 0.3 to 1% by weight. If it is less than 0.1% by weight, the wettability is poor, and if it is more than 2% by weight, the water resistance is lowered.
【００３０】消泡剤の使用量は０．０５〜２重量％が望
ましく、より好ましくは０．１〜１重量％である。０．
０５重量％より少ない場合は抑泡性に劣るため流下性が
不十分で、２重量％より多い場合はハジキが発生し緻密
な塗膜ができず防錆性にも劣る。The antifoaming agent is preferably used in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1% by weight. 0.
When the amount is less than 05% by weight, the foaming property is poor and the flowability is insufficient. When the amount is more than 2% by weight, cissing occurs and a dense coating film cannot be formed and the rust preventive property is also poor.
【００３１】不揮発分濃度は２０〜６０％が望ましく、
より好ましくは４０〜５０％である。２０％よりも低い
と塗着量が少なく、特にエッジカバーが不足し、防錆性
に劣る。６０％より高い場合は塗料粘度が高く、ディッ
ピング作業性に劣る。The non-volatile concentration is preferably 20 to 60%,
It is more preferably 40 to 50%. If it is lower than 20%, the amount of coating is small, especially the edge cover is insufficient, and the rust resistance is poor. If it is higher than 60%, the viscosity of the paint is high and the dipping workability is poor.
【００３２】顔料体積濃度は１０〜５０％が望ましく、
より好ましくは２０〜３５％である。１０％よりも低い
場合は塗膜に粘着性があり、実用的でない。５０％より
高い場合は、塗膜の緻密性が不足し、防錆性が劣る。The pigment volume concentration is preferably 10 to 50%,
It is more preferably 20 to 35%. If it is less than 10%, the coating film has tackiness and is not practical. If it is higher than 50%, the denseness of the coating film will be insufficient and the rust resistance will be poor.
【００３３】本発明の完全リサイクル型油面防錆性水系
樹脂塗料組成物には、必要に応じて当業者において慣用
されている防腐剤が適宜使用され、安全性に優れ、公害
のない、前記した完全リサイクル型であって油面塗装性
と防錆性を兼ね備えた塗料が得られる。In the completely recycle type oil surface rust preventive water-based resin coating composition of the present invention, an antiseptic agent commonly used by those skilled in the art is appropriately used, if necessary, excellent in safety and free from pollution. A completely recycle type paint that has both oil surface paintability and rust prevention can be obtained.
【００３４】[0034]
【作用】本発明は、水系共重合樹脂エマルジョン、防錆
顔料、親水性有機溶剤、増粘剤、分散剤、湿潤剤および
消泡剤からなる完全リサイクル型油面防錆性水系樹脂塗
料組成物に関するものであり、水系塗料でありながら防
錆油等の塗布されている金属面に直接塗布することが可
能であり、特にディッピング塗装に伴う浸漬引き上げ後
に複雑形状被塗物より余分な塗料が速やかに流れ落ち、
泡立ちがなく、しかもエッジカバー性を確保することと
共に防錆性、密着性、耐水性が優れた塗膜を形成するこ
とができる。The present invention is a completely recycle type oil surface rust preventive water-based resin coating composition comprising an aqueous copolymer resin emulsion, a rust preventive pigment, a hydrophilic organic solvent, a thickener, a dispersant, a wetting agent and a defoaming agent. Since it is a water-based paint, it can be applied directly to a metal surface coated with rust preventive oil, etc. To the
It is possible to form a coating film that is free from foaming, secures edge cover properties, and is excellent in rust prevention, adhesion, and water resistance.
【００３５】これらの成分の油面塗装性への作用は、親
水性有機溶剤の使用により塗液の表面張力を下げ、金属
表面の油分との親和性を高め、乾燥後に緻密な塗膜を被
塗物表面に形成することを助け、消泡剤と分散剤、湿潤
剤のそれぞれの適切な配合量の組み合わせを選択したこ
とにより抑泡性を高め、シックナーの種類と不揮発分濃
度の調整により塗着量を高め、適正な顔料体積濃度範囲
に調整することにより、密着性が良く、更に防錆顔料の
発錆抑制の結果、水系エマルジョン樹脂塗料であっても
油面に塗装が可能であり、また防錆性に優れた安全かつ
無公害の塗料が得られるものである。The effect of these components on the oil surface coatability is that the use of a hydrophilic organic solvent lowers the surface tension of the coating liquid, increases the affinity with the oil content on the metal surface, and coats a dense coating film after drying. It helps to form on the surface of the coating, and enhances the foam suppression by selecting the appropriate combination of defoaming agent, dispersant, and wetting agent, and adjusts the type of thickener and the concentration of non-volatile components. By increasing the amount of coating and adjusting it to an appropriate pigment volume concentration range, good adhesion, and as a result of suppressing rusting of the rust preventive pigment, even an aqueous emulsion resin paint can be painted on the oil surface, Further, it is possible to obtain a safe and pollution-free coating excellent in rust prevention.
【００３６】[0036]
【実施例】以下、実施例および比較例を挙げて本発明を
更に詳細に説明する。なお、実施例および比較例におい
て、水系共重合樹脂エマルジョン、防錆顔料（ペース
ト）、添加剤等は次に示すものを使用した。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples and comparative examples, the following water-based copolymer resin emulsions, rust preventive pigments (pastes) and additives were used.
【００３７】水系共重合樹脂エマルジョンＡ（エマルジ
ョンＡ）：ＡＰ−６７２０［昭和高分子（株）；スチレ
ン／アクリロニトリル／アクリル酸２−エチルヘキシル
／グリシジルメタクリレート／メタクリル酸＝６３／６
／２４／４／３（重量比）共重合樹脂エマルジョン、固
形分４５％］Aqueous copolymer resin emulsion A (emulsion A): AP-6720 [Showa Polymer Co., Ltd .; styrene / acrylonitrile / 2-ethylhexyl acrylate / glycidyl methacrylate / methacrylic acid = 63/6
/ 24/4/3 (weight ratio) copolymer resin emulsion, solid content 45%]
【００３８】水系共重合樹脂エマルジョンＢ（エマルジ
ョンＢ）：ＥＶＡＰ−５５０［昭和高分子（株）；エチ
レン／酢酸ビニル／バーサティック酸ビニル＝１０／８
０／１０（重量比）共重合樹脂エマルジョン、固形分５
５％］Aqueous copolymer resin emulsion B (emulsion B): EVAP-550 [Showa Highpolymer Co., Ltd .; ethylene / vinyl acetate / vinyl versatic acid = 10/8
0/10 (weight ratio) copolymer resin emulsion, solid content 5
5%]
【００３９】水系共重合樹脂エマルジョンＣ（エマルジ
ョンＣ）：ポリゾールＰＳ−３ＨＡ［昭和高分子
（株）；酢酸ビニル重合体エマルジョン、固形分５０
％］Aqueous copolymer resin emulsion C (emulsion C): Polysol PS-3HA [Showa Highpolymer Co., Ltd .; vinyl acetate polymer emulsion, solid content 50]
%]
【００４０】シックナー（Ａ）；ナトロゾール２５０Ｈ
Ｒ［ハーキュレス社、ヒドロキシエチルセルロース］ シックナー（Ｂ）；ナトロゾール２５０ＬＲ［ハーキュ
レス社、ヒドロキシエチルセルロース］Thickener (A); Natrosol 250H
R [Hercules, hydroxyethyl cellulose] Thickener (B); Natrosol 250LR [Hercules, hydroxyethyl cellulose]
【００４１】ｐＨ調整剤：アンモニア水PH adjuster: Ammonia water
【００４２】分散剤（Ａ）：オロタン７３１ＳＤ［ロー
ムアントハース社、ポリカルボン酸型界面活性剤］Dispersant (A): Orotan 731SD [Rohm Anthaas, polycarboxylic acid type surfactant]
【００４３】分散剤（Ｂ）：ノイゲンＥＡ−１２０［第
一工業製薬（株）、ポリオキシエチレンノニルフェニル
エーテル］Dispersant (B): Neugen EA-120 [Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene nonylphenyl ether]
【００４４】湿潤剤；ポリフローＷＳ［共栄油脂化学工
業（株）、非シリコーン系アクリルオリゴマー］Wetting agent; Polyflow WS [Kyoei Yushi Kagaku Kogyo KK, non-silicone acrylic oligomer]
【００４５】防錆顔料：Ｋ−ホワイト８４Ｓ［テイカ
（株）、トリポリリン酸アルミニウム］Anticorrosion pigment: K-White 84S [Taika Co., Ltd., aluminum tripolyphosphate]
【００４６】着色顔料：ベンガラＥＰ−２０［日本弁柄
工業（株）］ 体質顔料：ファイザータルク１０−５２［ファイザー−
ＭＳＰ（株）］ なお、以下において、部および％はすべて重量基準であ
る。Coloring pigment: Bengal EP-20 [Nippon Benji Industry Co., Ltd.] Extender pigment: Pfizer Talc 10-52 [Pfizer-
MSP Co., Ltd.] In the following, all parts and% are by weight.
【００４７】（顔料ペーストの調製）ディスパー型かく
はん機を設けた混合容器に表１に示した配合割合でこの
順に原料を添加した後、２，０００ｒｐｍで６０分間撹
拌して調製した。(Preparation of Pigment Paste) Raw materials were added in this order to the mixing container provided with a disperser type agitator at the compounding ratio shown in Table 1, and the mixture was stirred at 2,000 rpm for 60 minutes for preparation.
【００４８】[0048]
【表１】 [Table 1]
【００４９】（実施例１）エマルジョンＡを６１部、顔
料ペーストＡ３４部をディスパー型かくはん機を設けた
混合容器中で撹拌しながら、溶剤としてプロピレングリ
コールｎ−ブチルエーテル５部を添加後、１，５００ｒ
ｐｍで１５分間更に混合し、油面防錆性水系樹脂塗料組
成物を得た。Example 1 61 parts of Emulsion A and 34 parts of Pigment Paste A were stirred in a mixing vessel equipped with a disperser type agitator while adding 5 parts of propylene glycol n-butyl ether as a solvent, and then 1,500 r.
The mixture was further mixed at pm for 15 minutes to obtain an oil surface rust preventive water-based resin coating composition.
【００５０】（実施例２）消泡剤量を０．５部に増量し
た以外は実施例１と同様の操作により、油面防錆水系樹
脂塗料組成物を得た。Example 2 An oil surface rust preventive water-based resin coating composition was obtained by the same operation as in Example 1 except that the amount of the defoaming agent was increased to 0.5 part.
【００５１】（実施例３）顔料ペーストＡの代りに顔料
ペーストＢを４６部、エマルジョンＡ６１部に代え、エ
マルジョンＢ６１部を使用する以外は、実施例１と同様
の操作により、油面防錆性水系樹脂塗料組成物を得た。Example 3 The same procedure as in Example 1 was carried out except that instead of the pigment paste A, 46 parts of the pigment paste B and 61 parts of the emulsion A were used, and 61 parts of the emulsion B was used. An aqueous resin coating composition was obtained.
【００５２】（実施例４）顔料ペーストＡの代りに顔料
ペーストＢを４６部使用した以外は、実施例１と同様の
操作により、油面防錆性水系樹脂塗料組成物を得た。Example 4 An oil surface rust preventive water-based resin coating composition was obtained by the same procedure as in Example 1 except that 46 parts of the pigment paste B was used in place of the pigment paste A.
【００５３】（実施例５）エマルジョンＡを３７．５
部、プロピレングリコール−ｎ−ブチルエーテル３．５
部を使用した以外は、実施例１と同様の操作により油面
防錆性水系樹脂塗料組成物を得た。Example 5 Emulsion A was added to 37.5
Parts, propylene glycol-n-butyl ether 3.5
An oil surface rust preventive water-based resin coating composition was obtained by the same operation as in Example 1 except that the parts were used.
【００５４】（比較例１）エマルジョンＡに代えてエマ
ルジョンＣを６１部使用した以外は、実施例１と同様の
操作により油面防錆性水系樹脂組成物を得た。Comparative Example 1 An oil surface rust preventive aqueous resin composition was obtained in the same manner as in Example 1 except that 61 parts of Emulsion C was used instead of Emulsion A.
【００５５】（比較例２）エマルジョンＡを１１部、顔
料ペーストＡを６８部使用した以外は、実施例１と同様
の操作により油面防錆性水系樹脂組成物を得た。Comparative Example 2 An oil surface rust preventive aqueous resin composition was obtained by the same procedure as in Example 1 except that 11 parts of emulsion A and 68 parts of pigment paste A were used.
【００５６】（比較例３）エマルジョンＡを９００部使
用した以外は、実施例１と同様の操作により油面防錆性
水系樹脂組成物を得た。Comparative Example 3 An oil surface rust preventive water-based resin composition was obtained by the same procedure as in Example 1 except that 900 parts of Emulsion A was used.
【００５７】（比較例４）顔料ペーストＡに代えて、顔
料ペーストＣを３４部使用した以外は、実施例１と同様
の操作により油面防錆性水系樹脂組成物を得た。Comparative Example 4 An oil surface rust preventive aqueous resin composition was obtained in the same manner as in Example 1 except that 34 parts of the pigment paste C was used instead of the pigment paste A.
【００５８】（比較例５）顔料ペーストＡに代えて、顔
料ペーストＤを７２．９部使用した以外は、実施例１と
同様の操作により油面防錆性水系樹脂組成物を得た。Comparative Example 5 An oil surface rust preventive aqueous resin composition was obtained in the same manner as in Example 1 except that 72.9 parts of the pigment paste D was used instead of the pigment paste A.
【００５９】（比較例６）溶剤として使用しているプロ
ピレングリコールｎ−ブチルエーテルを使用しなかった
以外は実施例１と同様の操作により油面防錆性水系樹脂
組成物を得た。Comparative Example 6 An oil surface rust preventive aqueous resin composition was obtained by the same operation as in Example 1 except that propylene glycol n-butyl ether used as a solvent was not used.
【００６０】（比較例７）溶剤として使用しているプロ
ピレングリコールｎ−ブチルエーテルの使用量を４０部
使用した以外は実施例１と同様の操作により油面防錆性
水系樹脂組成物を得た。Comparative Example 7 An oil surface rust preventive aqueous resin composition was obtained by the same procedure as in Example 1 except that the amount of propylene glycol n-butyl ether used as a solvent was 40 parts.
【００６１】（比較例８）顔料ペーストＡの代りに、顔
料ペーストＥを３４部使用した以外は実施例１と同様の
操作により水系樹脂塗料組成物を得た。Comparative Example 8 An aqueous resin coating composition was obtained in the same manner as in Example 1 except that 34 parts of the pigment paste E was used instead of the pigment paste A.
【００６２】（比較例９）塗料の不揮発残分を１９％に
した以外は、実施例１と同様の操作により水系樹脂塗料
組成物を得た。(Comparative Example 9) An aqueous resin coating composition was obtained in the same manner as in Example 1 except that the nonvolatile content of the coating was changed to 19%.
【００６３】（比較例１０）消泡剤量を０．０１％にし
た以外は、実施例１と同様の操作により水系樹脂塗料組
成物を得た。Comparative Example 10 An aqueous resin coating composition was obtained by the same procedure as in Example 1 except that the amount of defoaming agent was 0.01%.
【００６４】[0064]
【表２】 [Table 2]
【００６５】[0065]
【表３】 [Table 3]
【００６６】[0066]
【表４】 [Table 4]
【００６７】上記により得られた各種塗料を、防錆油の
付着したラス網（冷間圧延鋼板より加工）をディッピン
グし、２０℃で２分間放置して液切れを行い、８０℃、
１０分間乾燥後各種テストを行った。The various paints obtained as described above were dipped in a lath net (processed from a cold rolled steel plate) to which rust preventive oil was adhered and left at 20 ° C. for 2 minutes to drain the liquid, and then at 80 ° C.
After drying for 10 minutes, various tests were conducted.
【００６８】塗装性は粘度を１８秒（フォードカップＮ
ｏ．４）に調整した塗料の浸漬槽中に、防錆油の付着し
たラス網をディップし、ラス網内の膜張、ハジキ、交絡
点のタマリ、エッジカバー性を評価した。The paintability has a viscosity of 18 seconds (Ford Cup N
o. The lath net to which rust preventive oil was adhered was dipped in the coating solution dipping bath adjusted in 4), and film tension, cissing, entanglement point tampering, and edge covering property in the lath net were evaluated.
【００６９】防錆性はＪＩＳＫ−５４００に準じた塩水
噴霧性試験後に発生する錆幅により評価した。The rust preventive property was evaluated by the rust width generated after the salt spray test according to JIS K-5400.
【００７０】耐水性は２０℃の水に４８時間浸漬し、フ
クレの発生状況を評価した。結果を表５に示す。Water resistance was evaluated by immersing in water at 20 ° C. for 48 hours and evaluating the occurrence of blisters. The results are shown in Table 5.
【００７１】[0071]
【表５】 [Table 5]
【００７２】評価基準 塗装性 ラス網内の膜張り 良好 ◎−○−△−× 不良 ハジキ 〃 タマリ 〃 エッジカバー 〃 碁盤目試験 ◎100/100 ○80〜99/100 △50〜80
/100 ×50以下/100 耐塩水噴霧試験48時間 ◎錆幅１mm ○錆幅３mm以内 △錆幅３mm以上 ×全面
錆 耐水性 ◎フクレなし ○フクレわずか △フクレ部
分的 ×フクレ全面Evaluation Criteria Paintability Good film formation in lath mesh ◎ − ○ − △ − × Poor repellency 〃 Tamari 〃 Edge cover 〃 Cross-cut test ◎ 100/100 ○ 80〜99 / 100 △ 50〜80
/ 100 x 50 or less / 100 48 hours salt spray resistance test ◎ Rust width 1mm ○ Rust width 3mm or less △ Rust width 3mm or more × Full surface rust Water resistance ◎ No swelling ○ Small swelling △ Partial swelling
【００７３】[0073]
【発明の効果】本発明は、防錆油、圧延油等が塗布され
ている金属表面に、脱脂処理などをせずにディッピング
塗装が可能であって、複雑な形状の被塗物であっても余
分の塗料は速やかに流れ落ち、しかもタレ、タマリ、ハ
ジキがなくエッジカバーが良く、付着性、耐水性に優
れ、かつ直接塗装可能な防錆作用を有するディッピング
塗装用の水系樹脂塗料の開発に成功した。INDUSTRIAL APPLICABILITY The present invention is an object to be coated which has a complicated shape and can be subjected to dipping coating on a metal surface coated with rust preventive oil, rolling oil, etc. without degreasing treatment. For the development of water-based resin coatings for dipping coatings, which has a good edge coverage with no dripping, lumps or cissing, has excellent adhesion and water resistance, and has a rust preventive effect that can be directly coated. Successful.
【００７４】このため脱脂処理および化成処理に伴う工
数の削減、廃アルカリ水溶液、廃水洗液等の処理、副生
する廃油、スラッジ等の処理、アルカリ、および中和剤
などのコストダウンが可能となった。Therefore, it is possible to reduce the man-hours associated with the degreasing treatment and the chemical conversion treatment, to treat the waste alkaline aqueous solution and the waste water washing liquid, to treat the waste oil and sludge produced as a by-product, to reduce the cost of the alkali and the neutralizing agent. became.
【００７５】更に本発明は水系樹脂塗料であるため、溶
剤系塗料に比し、溶剤揮散による作業環境の悪化、大気
汚染の心配もなく、更に引火性、着火性もない安全な油
面防錆性水系樹脂塗料組成物である。Further, since the present invention is a water-based resin paint, it is a safer oil surface rust preventive than a solvent-based paint, without causing deterioration of working environment due to volatilization of solvent, no fear of air pollution, flammability and ignitability. Water-based resin coating composition.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 可知 勇 神奈川県横浜市戸塚区上矢部町143−１− 418 (72)発明者 桜庭 寿彦 大阪府豊中市新千里南町３丁目８番Ａ５− 303 (72)発明者 冨島 和憲 兵庫県龍野市龍野町日山16 (72)発明者 橘 良信 神奈川県横浜市戸塚区上倉田町1372−15 (72)発明者 築山 文俊 兵庫県姫路市梅ケ谷町６−27 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isamu Kachi 143-1-418 Kamiyabe-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture (72) Toshihiko Sakuraba 3-8, Shinsenri-minami-cho, Toyonaka-shi, Osaka A5-303 ( 72) Inventor Kazunori Tomijima 16 Tatsunocho, Tatsuno-cho, Tatsuno-shi, Hyogo Prefecture (72) Yoshinobu Tachibana 1372-15 Kamigurata-cho, Totsuka-ku, Yokohama-shi Kanagawa (72) Futoshi Tsukiyama 6-27 Umegaya-cho, Himeji-shi Hyogo
Claims (3)
ジョンを樹脂分として１０〜４０重量％、リン酸塩系、
モリブデン酸塩系、メタホウ酸塩系、炭酸塩系、酸化物
系およびフェライト系の無機系防錆顔料および有機系防
錆顔料から選ばれた少なくとも一種の防錆顔料を０．５
〜３０重量％、親水性有機溶剤を０．５〜２０重量％、
増粘剤を０．１〜３重量％、分散剤を０．１〜３重量
％、湿潤剤を０．１〜２重量％、消泡剤を０．０５〜２
重量％含み、かつ不揮発分濃度２０〜６０％、顔料体積
濃度（ＰＶＣ）１０〜５０％であることを特徴とする完
全リサイクル型油面防錆性水系樹脂塗料組成物。1. A coating composition containing 10 to 40% by weight of a water-based copolymer resin emulsion as a resin component, a phosphate-based emulsion,
0.5 or more of at least one rust preventive pigment selected from molybdate, metaborate, carbonate, oxide and ferrite inorganic and organic rust preventive pigments.
~ 30 wt%, 0.5-20 wt% hydrophilic organic solvent,
0.1 to 3% by weight of thickener, 0.1 to 3% by weight of dispersant, 0.1 to 2% by weight of wetting agent, and 0.05 to 2 of antifoaming agent.
A completely recyclable oil-based rust preventive water-based resin coating composition containing 20% by weight of nonvolatile content and 10 to 50% of pigment volume concentration (PVC).
ン／（メタ）アクリル酸エステル／不飽和カルボン酸共
重合樹脂エマルジョン、エチレン／カルボン酸ビニルエ
ステル共重合樹脂エマルジョン、（メタ）アクリル酸エ
ステル／不飽和カルボン酸共重合樹脂エマルジョン、エ
チレン／カルボン酸ビニルエステル／（メタ）アクリル
酸エステル共重合樹脂エマルジョン、スチレン／ブタジ
エン共重合樹脂エマルジョンから選ばれた少なくとも一
種の水系共重合樹脂エマルジョンである請求項１記載の
完全リサイクル型油面防錆性水系樹脂塗料組成物。2. An aqueous copolymer resin emulsion comprising styrene / (meth) acrylic acid ester / unsaturated carboxylic acid copolymer resin emulsion, ethylene / vinyl carboxylic acid ester copolymer resin emulsion, (meth) acrylic acid ester / unsaturated The at least one water-based copolymer resin emulsion selected from a carboxylic acid copolymer resin emulsion, ethylene / carboxylic acid vinyl ester / (meth) acrylic acid ester copolymer resin emulsion, and styrene / butadiene copolymer resin emulsion. Completely recycle type oil surface rust preventive water based resin coating composition.
またはその誘導体類である請求項１記載の完全リサイク
ル型油面防錆性水系樹脂塗料組成物。3. The completely recycle type oil surface rust preventive water-based resin coating composition according to claim 1, wherein the hydrophilic organic solvent is propylene glycol or a derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20452293A JPH0741702A (en) | 1993-07-27 | 1993-07-27 | Water-base rustproof resin coating composition applicable to oily surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20452293A JPH0741702A (en) | 1993-07-27 | 1993-07-27 | Water-base rustproof resin coating composition applicable to oily surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0741702A true JPH0741702A (en) | 1995-02-10 |
Family
ID=16491932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20452293A Pending JPH0741702A (en) | 1993-07-27 | 1993-07-27 | Water-base rustproof resin coating composition applicable to oily surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0741702A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009503206A (en) * | 2005-08-04 | 2009-01-29 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Chromium-free and zinc-poor corrosion-resistant pigment mixture, process for its preparation and use of the pigment mixture |
| US7927707B2 (en) | 2003-10-09 | 2011-04-19 | Daikin Industries, Ltd. | Plate material and manufacturing method thereof |
| JP2018172504A (en) * | 2017-03-31 | 2018-11-08 | 大日本塗料株式会社 | Aqueous coating material composition and coating method |
-
1993
- 1993-07-27 JP JP20452293A patent/JPH0741702A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7927707B2 (en) | 2003-10-09 | 2011-04-19 | Daikin Industries, Ltd. | Plate material and manufacturing method thereof |
| JP2009503206A (en) * | 2005-08-04 | 2009-01-29 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Chromium-free and zinc-poor corrosion-resistant pigment mixture, process for its preparation and use of the pigment mixture |
| JP2018172504A (en) * | 2017-03-31 | 2018-11-08 | 大日本塗料株式会社 | Aqueous coating material composition and coating method |
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