JPS60204320A - Corrosion-resistant coated laminate - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は溶接性、加工性、耐食性に優れた塗装積層体に
係り、就中自動車ボデー用鋼月に適した連続スポット溶
接性に優れ、高加工性、高耐食性の塗装＠図体に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a painted laminate with excellent weldability, workability, and corrosion resistance, and in particular, a coated laminate with excellent continuous spot weldability suitable for steel parts for automobile bodies, and with high workability and high corrosion resistance. It is related to painting @ figure.

プレツー１〜鋼板のスポット溶接性という点からは塗膜
が電気導通性を有することが必要で、従来導電顔料を用
いることにより概ねその目的を達しでいる。From the point of view of spot welding of steel sheets, it is necessary for the coating film to have electrical conductivity, and conventionally, this purpose has generally been achieved by using conductive pigments.

しかしながら、自動車ボデー生産ラインの如く高速かつ
大量、省人のラインにおいては連続スポット溶接性が重
要な課題となる。尚、連続スポット溶接性は、溶接回数
の増大につれ電極が鋼板、メッキ皮膜、塗膜組成物など
で汚染され、その清浄化や交換が必要となるので、該清
浄化あるいは交換を要するまでの溶接回数により評価せ
られる。However, continuous spot weldability is an important issue in high-speed, high-volume, labor-saving lines such as automobile body production lines. Continuous spot welding is important because as the number of welds increases, the electrode becomes contaminated with steel plates, plating films, paint compositions, etc., and must be cleaned or replaced. It is evaluated by the number of times.

導電顔料を用い塗膜に導電性をもたせる技術（例えば特
公昭５２−４４５６９号、特開昭５８３− 一１３８７５８号、１）間開５８−１７４５８２月等）
あるいは顔判の工夫により塗膜導電性をざらに向−１二
させる技術（例えば特開昭５１−７９１３８号、特公昭
５８−１９７０６号）などではスポット溶接は可能ぐあ
っても２０００点あるいはそれ以上の連続スボッ１へ溶
接性を確保するだめの要件、すなわち電極汚染に対Ｍる
配慮がなく不満足な結果となる。しかも近時の自動車生
産工程に於ては可及的に大４Ｔる、例えば２０００〜５
０００点の連続スポット溶接性が要望せられる。Techniques for imparting conductivity to coating films using conductive pigments (e.g., Japanese Patent Publication No. 52-44569, Japanese Unexamined Patent Publication No. 583-1138758, 1) Publication No. 58-174582, etc.)
Alternatively, spot welding is possible at 2,000 or more points using techniques that roughly improve the conductivity of the coating film by devising face size (e.g., JP-A-51-79138, JP-B-Sho 58-19706). There is no consideration given to the requirement of ensuring weldability to continuous slits 1, that is, electrode contamination, resulting in unsatisfactory results. Moreover, in recent automobile production processes, 4T is as large as possible, for example, 2000 to 5
000 continuous spot weldability is required.

また塗８祠のプレスまたは深絞り加工においては、加工
時に塗膜が粉状に剥離しプレス機に１１着して加工キズ
発生の原因となったり、プレス機清掃の頻度が大となっ
たり、また加工時に塗膜が素地から剥ｍ１ｌｌ　Ｌ、、
あるいはクラックを生じ該部位の耐食性を低下せしめる
ことがあってはならない。In addition, in the press or deep drawing process of coating 8 hori, the coating film peels off into powder during processing and adheres to the press machine, causing processing scratches and requiring frequent cleaning of the press machine. Also, the coating film peels off from the base during processing.
In addition, cracks must not be formed and the corrosion resistance of the area must not be reduced.

この塗膜の加工性を向上せしめる目的で無機あるいは有
機性潤滑剤を添加することは公知である。It is known to add an inorganic or organic lubricant for the purpose of improving the workability of this coating film.

しかしながら元来、溶接可能な塗膜は導電性確保のため
顔判りツヂな組成となる傾向があって、４− 例えば二硫化モリブデンや炭素、酸化鉛の様な無機性顔
料をその効果が充分発揮される量配合することは、逆に
塗膜の強度、加工性の低下につながるという問題がある
。However, originally, weldable coatings tend to have a distinct composition in order to ensure conductivity. There is a problem in that adding an amount that will give the desired effect will conversely lead to a decrease in the strength and processability of the coating film.

また自動車などの生産においては通常ボデー各部、例え
ばロッカーパネル、ドア、フェンダ−などが鋼板からプ
レス加工で作られ、スポット溶接で組みたてられ、その
後脱脂、リン酸塩処理を経て電着塗装されるので、加工
性、スポット溶接性と共に、電着塗膜との密着性ならび
に耐食性の良好なことが要求せられる。特に各パーツの
合せ目、カド部分など電着塗装が不充分となる部位など
で耐食性が問題となる。一般に導電顔料や潤滑剤を比較
的多量に含む塗料を適用すると塗膜の耐食性は低下づる
傾向があり、なかには導電顔料それ自体あるいはその分
解生成物が腐食促進効果を示すこともあるので、導電顔
料の種類、その使用条件などが高耐食性塗膜を得るうえ
で特に重要である。In addition, in the production of automobiles, body parts such as rocker panels, doors, fenders, etc. are usually made from steel plates by press processing, assembled by spot welding, and then degreased, treated with phosphate, and then painted by electrodeposition. Therefore, it is required to have good workability and spot weldability, as well as good adhesion to electrodeposited coatings and corrosion resistance. Corrosion resistance becomes a problem, especially in areas where electrodeposition coating is insufficient, such as the joints and edges of parts. In general, when paints containing relatively large amounts of conductive pigments or lubricants are applied, the corrosion resistance of the paint film tends to decrease, and some conductive pigments themselves or their decomposition products can promote corrosion. The type and conditions of use are particularly important in obtaining highly corrosion-resistant coatings.

従って本発明目的の一つは加工性、耐食性に優れ、かつ
連続スポット溶接性に優れた塗装積層体を提供づるにあ
る。本発明の別の［」的は加工性、耐食性、連続スボッ
１〜溶接性に優れていると其に、電着塗装など後塗装置
１．１の塗膜密着す１１、あるいは塗装不充分な部位で
の耐食ｆ１にも優れ、特に自動中等の生産に好適なプレ
ー１−ト塗装鋼板を提供りるにある。Therefore, one of the objects of the present invention is to provide a coated laminate having excellent workability, corrosion resistance, and continuous spot weldability. Another objective of the present invention is that it is excellent in workability, corrosion resistance, and continuous weldability, and it also improves coating adhesion in post-coating processes such as electrodeposition coating11, or in cases where the coating is insufficiently coated. It is an object of the present invention to provide a plate coated steel sheet which is excellent in corrosion resistance f1 at parts and is particularly suitable for automatic production.

本発明者らは連続スボッ１〜溶接性と塗膜組成どの関連
性につき研究の結果、塗膜バインダー樹脂の熱分解性が
この連続スボッＩ・溶接性に大きく関与し、また該熱分
解性は樹脂分子中の芳香族環含有率と、射熱分解ｔａ物
質の共存の有無により変化し、芳香族環含イｉ率がＯあ
るい（よ、ある限度内であり、目つ易熱分解性物質を適
量配合することにより連続スポット溶接性が茗しく向−
１−Ｕシめられることを見出した。また加１．１！ｌの
向上に関しては無機顔料がかなりの吊共存するため、な
るべく少量でしかも低比重、大容積のもの、づなわち有
機性の潤滑剤であることが好ましく、自動車ボデーの如
く高度の加工を行うものについては適切な潤滑剤の種類
と量の選択、ならびに導電顔料とその他の無機顔料の総
量が重要であることを知った。As a result of research into the relationship between continuous sprocket weldability and coating film composition, the present inventors found that the thermal decomposition of the paint film binder resin is greatly involved in this continuous sprocket weldability. It changes depending on the aromatic ring content in the resin molecule and the presence or absence of a thermally decomposable substance. Continuous spot weldability can be improved by blending appropriate amounts of substances.
I found out that it can be reduced by 1-U. Add 1.1 again! Regarding the improvement of l, since inorganic pigments coexist in a considerable amount, it is preferable to use a lubricant with a small amount, low specific gravity, and large volume, that is, an organic lubricant, and it is suitable for high-level processing such as automobile bodies. I learned that it is important to select the appropriate type and amount of lubricant, as well as the total amount of conductive pigments and other inorganic pigments.

溶接可能ならしめるためには導電顔料が当然含有けしめ
られるが、本発明者らは導電顔料を含む塗料層の下に特
定の耐食層をもうけることにより、積層体の耐食性を大
ｒｉＪに改善しうろこと、また導電顔お１中特にリン生
麩を主成分とするものが耐食性、加工性に対する悪影響
が小さく、また電気抵抗が安定して低いとか、溶接時に
溶融せず硬度も大で特に優れていること、ざらにはリン
生麩分解抑制剤を併用し、無機顔料濃度を制御すること
により、より高耐食性で加工性、溶接性、塗膜密着性な
どにも優れた積層体の得られることを見出し本発明を完
成するに至った。In order to make it weldable, a conductive pigment is naturally required to be included, but the present inventors have greatly improved the corrosion resistance of the laminate by providing a specific corrosion-resistant layer under the paint layer containing the conductive pigment. Among scales and conductive materials, those containing phosphorus as a main component have particularly excellent corrosion resistance and processability, and have stable low electrical resistance, do not melt during welding, and have high hardness. By using a phosphorus starch decomposition inhibitor in combination and controlling the inorganic pigment concentration, it is possible to obtain a laminate with higher corrosion resistance and excellent workability, weldability, and paint film adhesion. Heading: The present invention has been completed.

号なわら本発明に従えば、耐食性化成予備処理のほどこ
された、あるいは予備処理のほどこされていない金属基
材上に、溶解度２０〜１０−６の６価クロムを含む化合
物の少なくとも１種と水性シリカおよび／または水性樹
脂バインダーを必須成分とし、所望により溶解度が２０
より大なる水溶性クロム化合物を含む組成物の耐食層な
らびに導７− 電塗利層が順次積層されてなり、該塗オ′！１層が、塗
料固形分として、 （Ａ＞分子中の芳香族環含４４率が０〜５０重如％の塗
料用樹脂　１０〜３５重愼％ 有機ａＶ＋滑剤　４〜５０重部％　おＪ：び導電顔料　
１５〜８６重量％　あるいは（Ｂ）分子中の芳香族環含
有率がＯ〜５０市石％の塗料用樹脂　１０〜３５重鯖％ 有機潤滑剤　４〜３０重−％ リン化鉄主成分の導電顔料 １５〜８５重量％ リン生麩分解抑制剤　１〜７１重１％ その他の無機顔ｆｉｔ　０〜７０重Ｍ％但し、導電顔料
、リン生麩分解抑制剤およびその他の無機顔料の含１１
に１が３５〜８６重量％ の組成を含／ｖでなる層である耐食性塗装積層体が提供
せられる。According to the present invention, at least one compound containing hexavalent chromium having a solubility of 20 to 10-6 is added to a metal substrate that has been subjected to a corrosion-resistant chemical pretreatment or has not been pretreated. Contains water-based silica and/or water-based resin binder as an essential component, and optionally has a solubility of 20%.
A corrosion-resistant layer of a composition containing a larger water-soluble chromium compound and a conductive coating layer are sequentially laminated, and the coating layer is laminated in sequence. The solid content of the paint in one layer is (A> Paint resin with aromatic ring content in the molecule of 0 to 50 parts by weight, 10 to 35 parts by weight, organic aV + lubricant 4 to 50 parts by weight, and J: and conductive pigments
15 to 86% by weight or (B) Paint resin with an aromatic ring content in the molecule of O to 50% by weight 10 to 35% by weight Organic lubricant 4 to 30% by weight Conductive material mainly composed of iron phosphide Pigment 15-85% by weight Phosphorous wheat decomposition inhibitor 1-71% by weight Other inorganic face fit 0-70% by weight However, conductive pigments, phosphorus raw wheat decomposition inhibitors and other inorganic pigments are included.
A corrosion-resistant painted laminate is provided, the layer having a composition of 35 to 86% by weight of 1/v.

本発明の積層体における金属基材は鉄・亜鉛・アルミニ
ウム系金属材、特に冷延鋼板、亜鉛メツ８− キ鋼板、合金亜鉛メッキ鋼板、アルミメッキ鋼板、仙鉛
および亜鉛合金板、アルミおよびアルミ合金板、ステン
レス鋼板、ニッケルあるいは鉄を含む電気亜鉛メッキ鋼
板などである。The metal base material in the laminate of the present invention is an iron/zinc/aluminum metal material, particularly a cold rolled steel plate, a galvanized 8-metal steel plate, an alloy galvanized steel plate, an aluminized steel plate, a lead and zinc alloy plate, aluminum and aluminum. These include alloy plates, stainless steel plates, and electrogalvanized steel plates containing nickel or iron.

これら金属基材は単に洗浄、脱脂処理されたまＪ：のも
のであっても、あるいは耐食性化成予備処理のほどこさ
れたものであってもかまわない。かかる化成予備処理は
リン酸塩皮膜、クロム酸塩皮膜などを形成せしめる通常
の化成処理で当事者衆知技術に属し、その詳細は説明す
る必要がなかろう。These metal substrates may be simply cleaned and degreased, or may be pretreated to provide corrosion resistance. Such pretreatment for chemical conversion is a general chemical conversion treatment for forming a phosphate film, a chromate film, etc., and is well known to those skilled in the art, and there is no need to explain its details.

本発明においては、この金属基材上に溶解度が２０〜１
０−５の６価クロムを含むクロム化合物の少なくとも１
種と、水性シリカおよび／または水性樹脂バインダーを
必須成分とし、所望により溶解度が２０より大なる水溶
性クロム化合物を含む組成物の耐食層が設けられる。こ
の耐食層には必須成分として溶解度２０〜１０−５の６
価クロム含有クロム化合物と、任意成分としての溶解度
２０より大なる水溶性クロム化合物が含まれる。前者の
代表的なものは溶解度２（）・〜・１０のクロム酸カル
シウム、溶解度１０〜１０−１のり１」ム酸亜鉛、クロ
ム酸スト［１ンヂウム、溶解ｔη１０’〜１０−”のク
ロム酸バリウム、クロム酸鉛等ぐある。又、６価クロム
化合物とその仙の金属との混合物あるいは有機物との反
応物であって溶解度が２０〜１０−！１の化合物などで
ある。溶解度が２０をこえる化合物は塗膜樹脂どの反応
が活性にずぎるため、塗膜の経時耐食性を充分に向１−
せしめないし他方溶解度１０−５未満のり［１ム化合物
は防食能が不充分である。かかるクロム化合物は通常１
種あるいは２種以上の組合せで金属クロム換緯０．０１
〜１　（］／　ｍ２程度の割合で耐食層中に存在ｌしめ
られる。所望により相乗り的な初期耐食性、経時耐食性
を得る目的ぐ溶解度が２０をこえる水溶性クロム化合物
、例えば、ＣｒＯ３、Ｃｒ（ＮＯ３）３・９Ｈ２０，Ｃ
ｒｚ　（ＳＯ４）３　・１８１−１２０、Ｃｖ　ＰＯ４
・６日２０、その他のり「１ム酸塩、重クロム酸塩など
が加えられる。耐食層にはかかるクロムと相溶性のある
バインダーとして水性シリカおよび／または水性樹脂が
用いられる。In the present invention, the solubility on this metal base material is 20 to 1.
At least one chromium compound containing 0-5 hexavalent chromium
A corrosion-resistant layer of a composition comprising a seed, an aqueous silica and/or an aqueous resin binder as essential components, and optionally a water-soluble chromium compound having a solubility of greater than 20 is provided. This corrosion-resistant layer has a solubility of 20 to 10-5 as an essential component.
Included are chromium compounds containing valent chromium and optionally water-soluble chromium compounds with solubility greater than 20. Typical examples of the former are calcium chromate with a solubility of 2 () to 10, zinc chromate with a solubility of 10 to 10-1, zinc chromate with a solubility of 1, and chromic acid with a solubility of 10 to 10. There are barium, lead chromate, etc. Also, it is a mixture of a hexavalent chromium compound and its metal, or a reaction product with an organic substance, and it is a compound with a solubility of 20 to 10-!1. Compounds that exceed 100% are active in the reactions of coating resins, so they are highly effective in improving the corrosion resistance of coatings over time.
Compounds with a solubility of less than 10 -5 or less than 10 -5 have insufficient anticorrosion ability. Such chromium compounds usually contain 1
Metallic chromium conversion latitude 0.01 by species or a combination of two or more species
It is present in the corrosion-resistant layer at a ratio of about 1 (]/m2. If desired, water-soluble chromium compounds with a solubility exceeding 20, such as CrO3, Cr(NO3 )3・9H20,C
rz (SO4)3 ・181-120, Cv PO4
- On the 6th, 20, other materials such as murate, dichromate, etc. are added.Aqueous silica and/or aqueous resin is used as a binder compatible with the chromium in the corrosion-resistant layer.

水性シリカは粒子径１００ｍμ以下のコロイダルシリカ
あるいは水分散性シリカが代表的なもので、こういった
コロイダルシリカの具体的例はスノーテックス０（コロ
イダルシリカ、日産化学社製商品名　固形分２０％　平
均粒度２０ｍμ、ｐｌ−１３，０）、スノーテックスＮ
（同、ｐｌ−１９）、スノーテックスＰＬ（同、粒子径
４０〜５０ｍμ、ｒ）ｌ−１３）であり、また水分散性
シリカとしては日本アエロジル社製商品名のアエロジル
３００（粒子径１００ＩＩｌμ以下）、アエロジルＴＴ
−６００（粒子径０．１〜０．３μ）、イムシルＡ１０
８（粒子径５　Ｉｔ　、イリノイスミネラル社製商品名
）等が好ましく用いられる。又、水性樹脂にはクロムと
相溶性のある水溶性樹脂および水分散性樹脂が包含され
、水溶性樹脂の具体例はポリビニルアルコール、アルキ
ルヒドロキシアルキルセルロース、ポリアクリル酸およ
びその誘導体、ポリアクリルアミドおよびその誘導体、
ポリビニルピロリドン、ポリビニルメチル無水マレイン
酸とビニル−１１− あるいはアクリル化合物との陵応体等であり、また水分
散性樹脂の具体例はアルキド樹脂、フェノール樹脂、ア
ミノ樹脂、酢酸ビニル系エマルシ三１ンポリマー、スチ
レン、ブタン１ン系合成ラテうクスりリマー、アクリル
系エマルションポリマー、天然および合成ゴム系エマル
ションポリマーなどがあげられる。Water-based silica is typically colloidal silica or water-dispersible silica with a particle size of 100 mμ or less. A specific example of such colloidal silica is Snowtex 0 (colloidal silica, trade name manufactured by Nissan Chemical Co., Ltd. Solid content 20% average) Particle size 20mμ, pl-13,0), Snowtex N
(the same, pl-19), Snowtex PL (the same, particle size 40-50 mμ, r) l-13), and the water-dispersible silica is Aerosil 300, a trade name manufactured by Nippon Aerosil Co., Ltd. (particle size 100IIlμ or less). ), Aerosil TT
-600 (particle size 0.1-0.3μ), Imucil A10
8 (particle size 5 It , trade name manufactured by Illinois Minerals), etc. are preferably used. In addition, water-based resins include water-soluble resins and water-dispersible resins that are compatible with chromium, and specific examples of water-soluble resins include polyvinyl alcohol, alkylhydroxyalkyl cellulose, polyacrylic acid and its derivatives, polyacrylamide and its derivatives. derivative,
Examples of water-dispersible resins include alkyd resins, phenolic resins, amino resins, and vinyl acetate emulsion polymers. , styrene, butane-based synthetic latte trimmers, acrylic-based emulsion polymers, and natural and synthetic rubber-based emulsion polymers.

これらバインダーは１種あるいは２種以上の組合せで用
いることができ、上記り１ム化合物を金属表面に密着固
定せしめるのにイｊ効である。These binders can be used alone or in combination of two or more, and are effective in tightly fixing the above-mentioned 1M compound to the metal surface.

上記耐食層をもうりることにより、上塗り塗料中の樹脂
成分と反応することなく、熱劣化に対し安定で、長期に
わたり優れた耐食性を示す積層体が提供せられる。尚、
耐食層中、６価りｎムが水溶性全クロムの１０〜９０重
量％を占めることが特に優れた結果を与えることも見出
されている。By adding the above-mentioned corrosion-resistant layer, a laminate that does not react with the resin component in the top coat, is stable against thermal deterioration, and exhibits excellent corrosion resistance over a long period of time can be provided. still,
It has also been found that particularly good results are obtained when hexavalent nm accounts for 10 to 90% by weight of the total water-soluble chromium in the corrosion-resistant layer.

本発明の積層体は前記耐食層の上に、加工性、溶接性、
耐食性などに優れた特定の導電性塗料層がもうけられて
いる。The laminate of the present invention has workability, weldability,
A specific conductive paint layer with excellent corrosion resistance is created.

この塗料層はバインダー樹脂として、分子中の−１２＝ 芳香族環含有率がＯもしくは最大限５０重量％までの塗
料用樹脂、例えばエポキシ系樹脂、アルキド系樹脂、ア
クリル系樹脂、メラミン系樹脂、ウレタン系樹脂、フェ
ノール系樹脂、ビニル系樹脂、ポリビニルブチラール樹
脂、ポリビニルアセテート樹脂、塩素化ゴム、オイルフ
リーポリエステル樹脂、フタル酸樹脂、スチレン樹脂、
ポリオレフィン樹脂等を有機溶剤タイプあるいは水性化
されたタイプで使用することを特徴とＪる。This paint layer is made of a paint resin having a -12= aromatic ring content of O or up to 50% by weight in the molecule as a binder resin, such as an epoxy resin, an alkyd resin, an acrylic resin, a melamine resin, Urethane resin, phenolic resin, vinyl resin, polyvinyl butyral resin, polyvinyl acetate resin, chlorinated rubber, oil-free polyester resin, phthalic acid resin, styrene resin,
It is characterized by using polyolefin resin etc. in organic solvent type or water-based type.

これらの樹脂は単独でもあるいは２種以上の組合せでも
用いられるが、組合せの場合は平均含有率で表現して、
前述の如く芳香族環含有率が５０重石％以下、最も好ま
しくは０％でなくてはならない。These resins can be used alone or in combination of two or more types, but in the case of a combination, it is expressed by the average content,
As mentioned above, the aromatic ring content must be less than 50% by weight, most preferably 0%.

本発明者らは樹脂分子中の芳香族環含有率が連続スポッ
ト溶接性と密接に関係し、５０％をこえると下記測定法
による熱分解率 加熱後の樹脂重量・・・室温から５５０℃ま′ｃ２０℃
／分の速ｔηで樹脂をシｒ 温（Ｎ２気流中）さｌ、サンプ ル温度がｂ　Ｆ）　Ｏ℃に達した時の 重量を熱車吊分析器ｅ測定（リ ンプル間５〜１０１＋１（］） が著しく低下し、でれど共に連続スポット溶接性も著し
く低下り゛ること。芳香族環含有率が０〜５０重量％で
は、樹脂の熱分解による重量減少率は７０〜１００％で
、５０００点までの連続スポット溶接に充分耐えうるこ
とを見出した。The present inventors have found that the aromatic ring content in the resin molecule is closely related to continuous spot weldability, and that when it exceeds 50%, the thermal decomposition rate is measured by the following method.The resin weight after heating...from room temperature to 550℃. 'c20℃
Syrup the resin at a rate of tη/min (in a N2 gas flow) and measure the weight with a heated wheel hanging analyzer when the sample temperature reaches 0°C (5 to 101 + 1 (]) between rims). At the same time, the continuous spot weldability is also markedly reduced.When the aromatic ring content is 0 to 50% by weight, the weight loss rate due to thermal decomposition of the resin is 70 to 100%, and 5000 It has been found that it can sufficiently withstand continuous spot welding up to the point.

尚、樹脂の塗料固形分中の含有率は１０〜３５重量％、
９丁ましくは１５〜２５重間％で、１０Φ量％を下まわ
ると加工性の低下が著しく、また３３５重量％をこえる
と連続スポット溶接性が低下することも見出されている
。In addition, the content of resin in the solid content of the paint is 10 to 35% by weight,
It has also been found that when the amount is less than 10% by weight, workability is significantly reduced, and when it exceeds 335% by weight, continuous spot weldability is reduced.

前記塗料層には第２成分として有機潤滑剤が含有せしめ
られる。有機潤滑剤は、加］二用冶具と塗膜との摩擦を
減じ塗膜にかかる力を弱めて加工時の塗膜損傷を減じよ
うと覆るもので所謂滑り剤として知られるものであるが
、少量でも低比重で塗膜中での容積分率が大きい有機性
物質であるだけでなく、熱分解性が良好（分解温度３０
０〜５００℃）で発熱反応を示し、大部分が揮発して連
続スボッ１〜溶接に悪影響を与えるカーボンを残さずさ
らに共存する樹脂、熱分解促進物質であることが好まし
く、かかる意味に於てポリオレフィン系化合物、例えば
ポリエチレン、アイソタクチックボリブ［ｌピレン、ボ
リブデン等、不飽和脂肪族オレフィン系炭化水素の重合
体（好ましくは分子量１０００〜１０，０００程度のも
の）；カルボン酸エステル系化合物、例えばステアリン
酸、オレイン酸、アジピン酸、アゼライン酸、セバシン
酸等のカルボン酸と、ｎ−ブタノール、ｓｅａ。The paint layer contains an organic lubricant as a second component. Organic lubricants are known as slip agents, which are used to reduce the friction between the jig and the paint film, weaken the force applied to the paint film, and reduce damage to the paint film during processing. It is not only an organic substance with a low specific gravity and a large volume fraction in the coating film even in small amounts, but also has good thermal decomposition (decomposition temperature 30
It is preferable that the resin exhibits an exothermic reaction at a temperature of 0 to 500°C, and most of it volatizes and coexists without leaving any carbon that would adversely affect continuous sprocketing or welding. Polyolefin compounds, such as polyethylene, isotactic bolyb [lpyrene, bolybdenum, etc., polymers of unsaturated aliphatic olefin hydrocarbons (preferably those with a molecular weight of about 1000 to 10,000); carboxylic acid ester compounds, e.g. Carboxylic acids such as stearic acid, oleic acid, adipic acid, azelaic acid, and sebacic acid, n-butanol, and sea.

−ブタノール、３−メチルブタノール、２−エチルヘキ
サノエート、ネオペンチルアルコールなどのアルコール
との七ノー、ジーあるいはポリ−エステル；ポリアルキ
レングリコール系化合物、例えばポリプロピレングリコ
ール、ポリエチレングリコールなどが特に好ましい物質
として推奨せられる。- Seven-, di- or poly-esters with alcohols such as butanol, 3-methylbutanol, 2-ethylhexanoate, neopentyl alcohol; polyalkylene glycol compounds such as polypropylene glycol, polyethylene glycol, etc. are particularly preferred substances. Recommended.

加工性、熱分解性、耐食性、上塗塗膜の密着性等１５− の観点から就中好ましいものはポリエチレンワックスで
、最も好ましいものは分子量が１０００〜１００００、
粒径５０μ以下のポリエチレン微粉末である。From the viewpoint of processability, thermal decomposition, corrosion resistance, adhesion of the top coat, etc., polyethylene waxes are particularly preferred, and the most preferred are polyethylene waxes with a molecular weight of 1,000 to 10,000;
It is a fine polyethylene powder with a particle size of 50μ or less.

かかる有機潤滑剤は単独もしくは２種以上の組合せで用
いられるがその添加量は塗料固形分中、４〜３０重量％
、好ましくは４〜２０重量％で、４重量％未満では加工
性が低下し、樹脂の熱分解促進効果も認められず、他方
３０重吊金こえても、それ以上の加工性の向上は認めら
れず、かえって量の増大につれ耐食性が低下する傾向が
認められる。Such organic lubricants can be used alone or in combination of two or more, and the amount added is 4 to 30% by weight based on the solid content of the paint.
, preferably from 4 to 20% by weight; if it is less than 4% by weight, the processability decreases and no effect of promoting thermal decomposition of the resin is observed; on the other hand, even if the weight exceeds 30 weights, no further improvement in processability is observed. On the contrary, there is a tendency for corrosion resistance to decrease as the amount increases.

本発明で用いられる塗料組成物にはまた導電性付与の目
的で導電顔料が含有せしめられる。The coating composition used in the present invention also contains a conductive pigment for the purpose of imparting conductivity.

かかる導電顔料は通常の任意の型のものでありうるが、
例えば下記があげられ、 金属粉〜ステンレス、金、銀、カドミウム、アルミニウ
ム、亜鉛、錫、銅、グラファ イト等 金属炭化物〜鉄、ニッケル、チタン、タンゲス１６− テン、ニオブ、マンガン等の炭化物 フエ［１７０イ〜フエロマンガン、フェロモリブデン、
フェロシリコン、テエロクロム、フェロチタン、フェロ
ホスホル等 これら化合物の１種又は２種以上の混合物を用いる。Such conductive pigments can be of any conventional type, but
Examples include the following: Metal powders - metal carbides such as stainless steel, gold, silver, cadmium, aluminum, zinc, tin, copper, and graphite - carbides such as iron, nickel, titanium, tanges, niobium, manganese, etc. I ~ Ferromanganese, ferromolybdenum,
One type or a mixture of two or more of these compounds, such as ferrosilicon, theerochrome, ferrotitanium, and ferrophosphor, is used.

導電顔料は耐食性、加工性に悪影響の小さいものを選択
する必要があり、鉄よりも員の電位を示す金属粉は除く
ことが好ましい。It is necessary to select a conductive pigment that has a small negative effect on corrosion resistance and processability, and it is preferable to exclude metal powder that exhibits a higher potential than iron.

又、電気抵抗が安定して低いと、溶接時発熱に対しても
溶融せず（電流密度の低下と電極の汚染がない）、溶接
加圧時にも粉砕されない硬度であることが導電顔料とし
て好ましい。又、比較的多量に使用するため価格の低い
ことも重要である。In addition, it is preferable for a conductive pigment to have a stable and low electrical resistance, to not melt even when heat is generated during welding (no reduction in current density and no electrode contamination), and to have a hardness that does not shatter during welding pressure. . Furthermore, since it is used in relatively large quantities, it is important that it is inexpensive.

これらの観点から炭化鉄、リン生麩の使用が好ましい。From these viewpoints, it is preferable to use iron carbide and phosphorus raw wheat.

導電顔料は２０μ以下、好ましくは１０μ以下の粒径の
ものが塗料固形分中１５〜８６重間％、好ましくは３０
〜７０重量％、を占めるように含有せしめられる。The conductive pigment has a particle size of 20μ or less, preferably 10μ or less, in an amount of 15 to 86% by weight, preferably 30% by weight of the solid content of the paint.
It is contained in an amount of up to 70% by weight.

この顔料濃度が３０重崩％を下まわると塗膜厚１０μ以
上で電導性が不足する場合があり、１り１ｗｔ％を下ま
わるど明らかに電ｌｆｌ不足でスボッｌ〜溶接が出来な
い。７０ｗｔ％を越えると塗膜加ＩＴ、　ｔｅｌ−が低
下する場合があり、８６ｗｔ％を越えるど明らかに塗膜
加工性が低下し実用的でなくなる。If the pigment concentration is less than 30% by weight, conductivity may be insufficient if the coating thickness is 10 μm or more, and if it is less than 1% by weight, there will be a clear lack of electric current and welding will not be possible. If it exceeds 70 wt%, the coating film addition IT and tel- may be lowered, and if it exceeds 86 wt%, the film processability clearly deteriorates, making it impractical.

特に好ましい具体例において、導電顔料どしてリン化鉄
主成分の顔料が用いられ、またより１＠れた耐食性を確
実ならしめるためにはリン生麩分解抑制剤が併用せられ
る。リン生鉱は耐食性、加工性、溶接性等各種性能の良
好なバランスという意味でもっとも好ましい導電ＩＭｉ
別であり、既に述べた如く塗料固形分中１５〜８６重量
％の量で存在せしめせれる。しかしながら耐食性に対す
る悪影響の最も少ないリン化鉄主成分の導電顔ｒ１を選
択しても、なお腐食環境下、特に塗膜が酸性雰囲気にお
かれる場合、リン生鉱の分解が生じ分解物により腐食が
促進されることのあることが見出された。塗膜が酸性雰
囲気になるか否かは塗膜組成物、素地金属、腐食環境条
件に依存づるが、−特に数種の腐食環境や乾湿交番条件
が設定される複合腐食試験等過酷な試験に対し、より高
度の耐食性を示Ｊ組成物が得られるならばこれにまさる
ものはない。本発明者らはかかる組成物を得るためには
リン生鉱の分解を抑制するか分解物の無害化が必要で、
その目的に対し、懸濁水ｐｌ−１が６〜１３、好ましく
は７〜１１になる顔料の共存が塗膜を継続的に中性乃至
はアルカリ性側に置くことになり極めＣ有効な手段であ
ることを見出した。In a particularly preferred embodiment, a pigment containing iron phosphide as a main component is used as the conductive pigment, and in order to ensure even better corrosion resistance, a phosphorus raw product decomposition inhibitor is used in combination. Phosphite is the most preferred conductive IMi in terms of its good balance of various performances such as corrosion resistance, workability, and weldability.
As mentioned above, it is present in an amount of 15 to 86% by weight in the paint solids. However, even if the conductive surface R1, which is mainly composed of iron phosphide and has the least negative effect on corrosion resistance, is selected, under a corrosive environment, especially when the coating film is exposed to an acidic atmosphere, phosphatic ore will decompose and the decomposed products will cause corrosion. It was found that this can be promoted. Whether or not the coating film becomes an acidic atmosphere depends on the coating composition, the base metal, and the corrosive environment conditions; however, it is especially suitable for severe tests such as complex corrosion tests where several types of corrosive environments and alternating wet and dry conditions are set. On the other hand, if it is possible to obtain a composition J that exhibits a higher degree of corrosion resistance, there is nothing better than this composition. In order to obtain such a composition, the present inventors believe that it is necessary to suppress the decomposition of phosphorite or to render the decomposed products harmless.
For that purpose, the coexistence of a pigment with a suspension water pl-1 of 6 to 13, preferably 7 to 11 is an extremely effective means as it keeps the coating film on the neutral or alkaline side. I discovered that.

従って本発明の塗料組成物にはリン化鉄主成分の導電顔
料と共にリン生麩分解抑制剤が必須成分として含有せし
められる。かかる分解抑制剤は既に述べた如く塗膜を継
続的に中性あるいはアルカリ性側にａ３＜目的のもので
あって、懸濁水１）ｌ−１が６〜１３の顔料が好都合に
使用せられる。具体的には例えば下記化合物があげられ
る。Therefore, the coating composition of the present invention contains, as an essential component, a conductive pigment mainly composed of iron phosphide and a phosphorus product decomposition inhibitor. As described above, such decomposition inhibitors are those which are intended to keep the coating film on the neutral or alkaline side continuously, and pigments having a suspension water 1) l-1 of 6 to 13 are conveniently used. Specific examples include the following compounds.

■アルカリ土類金属石油スルホネート ■り［］ム酸亜鉛、クロム酸亜鉛カリウム、クロム酸亜
鉛、塩基性りロム酸鉛、クロム酸カルシウム、クロム酸
ストロンチウム等のクロム１９− 酸塩顔料 ■リン酸亜鉛、リン酸鉄、１−リボリリン酸アルミニウ
ム等のリン酸塩顔料 ■鉛酸カルシウム、ケイ酸鉛等の鉛化合物顔料■タルク
、庚酸カルシウム、シリカ等の体質顔料 ■亜鉛末（リン生鉱と同量以下） 但し、これらの顔料の添加量は塗料固形分中１重崩％以
下で次に記述する無機顔料の総崩を越えない量とする。■Alkaline earth metal petroleum sulfonates ■Chromium-19-acid pigments such as zinc chromate, potassium zinc chromate, zinc chromate, basic lead chromate, calcium chromate, strontium chromate ■Zinc phosphate Phosphate pigments such as , iron phosphate, aluminum 1-ribolyphosphate ■ Lead compound pigments such as calcium leadate and lead silicate ■ Extender pigments such as talc, calcium oxate, and silica ■ Zinc powder (same as phosphate ore) However, the amount of these pigments to be added shall be 1% or less in the solid content of the paint, and the amount shall not exceed the total disintegration of the inorganic pigments described below.

尚、これらの化合物は防錆顔料あるいは体質顔料に分類
されることもあるが懸濁水ｐ１−１の点で本発明に於て
はリン生麩分解抑制剤として認識されるものである。Although these compounds are sometimes classified as antirust pigments or extender pigments, in the present invention they are recognized as phosphorus product decomposition inhibitors in terms of suspension water p1-1.

リン生麩分解抑制剤はこのように塗料固形分中１重量％
以上用いられるからリン化鉄主成分の導電顔料は両者併
用の場合、１５〜８５重量％の範囲内となることが容易
に理解されよう。In this way, the phosphorus raw wheat decomposition inhibitor is 1% by weight in the solid content of the paint.
From the above, it is easily understood that the conductive pigment containing iron phosphide as a main component is in the range of 15 to 85% by weight when both are used in combination.

本発明の塗料層中にはまた所望によりその他の無機顔料
、例えば耐食性向上のためのクロム顔料２０− （り１］ム酸亜鉛系、クロム酸鉛系、クロム酸カルシウ
ム系、クロム酸ストロンチウム系顔料等）、リンＭ塩顔
料（リン酸亜鉛、リン酸鉄、トリポリリン酸アルミニウ
ム系顔料等）、鉛化合物顔料（鉛酸カルシウム、ケイ酸
鉛等）：樹脂量の調整、塗膜ｐＨ調整のための体質顔料
（シリカ、炭酸カルシウム、タルク、アルミナ等）；着
色顔料（酸化り１］ム、酸化鉄、酸化鉛等）を加えるこ
とができる。こういった無機顔料を加える場合は、次に
述べる無機顔料の総量を越えてはならない。The paint layer of the present invention may optionally contain other inorganic pigments, such as chromium pigments for improving corrosion resistance, zinc chromate-based, lead chromate-based, calcium chromate-based, strontium chromate-based pigments. etc.), phosphorus M salt pigments (zinc phosphate, iron phosphate, aluminum tripolyphosphate pigments, etc.), lead compound pigments (calcium leadate, lead silicate, etc.): For adjusting the amount of resin and adjusting the pH of the coating film. Extender pigments (silica, calcium carbonate, talc, alumina, etc.); coloring pigments (oxidized aluminum, iron oxide, lead oxide, etc.) can be added. When adding these inorganic pigments, the total amount of inorganic pigments listed below must not be exceeded.

１なわち本発明で用いられる塗料組成物においてはリン
化鉄主成分の導電顔料、リン生麩分解抑制剤ならびに所
望により加えられるその他の無機顔料の総量が塗料固形
分中、３５〜８６重量、好ましくは３５〜７０重量％の
節囲内にあることが重要である。というのは前記総量が
３５重量％を下まわると塗膜加工性が低下し、また７０
重量％をこえても加工性の低下を認める場合があり、８
６重墨％をこえると明らかに大ｌＪな加■性低下が認め
られるからである。従って最も好ましい実施ｇ様によれ
ば塗＄１１層は、塗料固形分として分子中の芳香族環含
６率が０〜５０小ｍ１％の塗料用樹脂　１０〜３５重量
％ 有機潤滑剤　１・−３０１Ｆ量％ リン化鉄主成分の導電顔料 １５〜８５市間％ リン生鉱分解抑制剤　１〜７１車ｍ１％その他の無機顔
料　Ｏ・〜７０７０％ 但し、導電顔料、リン生鉱分解抑制剤およびその他の無
機顔料の合計量３５〜８６重量％の組成物を含んでなる
。1. That is, in the coating composition used in the present invention, the total amount of the conductive pigment mainly composed of iron phosphide, the phosphorus product decomposition inhibitor, and other inorganic pigments added as desired is 35 to 86% by weight, preferably 35 to 86% by weight, based on the solid content of the coating material. It is important that the amount is within the range of 35 to 70% by weight. This is because if the total amount is less than 35% by weight, the processability of the coating will decrease;
Even if it exceeds 8% by weight, a decrease in workability may be observed.
This is because when the amount of ink exceeds 6%, a significant decrease in lJ strength is clearly observed. Therefore, according to the most preferred embodiment g, the coating $11 layer consists of a coating resin with a molecular aromatic ring content of 0 to 50% by weight (10 to 35% by weight) and an organic lubricant 1.- 301F amount % Conductive pigment mainly composed of iron phosphide 15-85% Phosphate decomposition inhibitor 1-71 m1% Other inorganic pigments O.~7070% However, conductive pigment, phosphate mineral decomposition inhibitor and The composition comprises a total amount of other inorganic pigments of 35-86% by weight.

尚、塗料層の厚みはいずれの場合も１〜２０μ、好まし
くは２〜１０μで焼付処理が行なわれる。In any case, the thickness of the paint layer is 1 to 20 .mu.m, preferably 2 to 10 .mu.m during the baking process.

本発明の積層体は極めて優れた加］二性、耐食性、連続
スポット溶接性、塗膜密盾性を示し、自動車等の工業的
生産ラインに使用され特に有用である。The laminate of the present invention exhibits extremely excellent adhesion properties, corrosion resistance, continuous spot weldability, and coating film tightness, and is particularly useful for use in industrial production lines for automobiles and the like.

以下実施例にｊ−り本発明を説明づる。The present invention will be explained below with reference to Examples.

尚、下配例においで、金属ＩＪ祠どしτは次の如きもの
が使用された。In the examples below, the following metal IJ blades τ were used.

耐食性化成予備処理のほどこされていない金属基ｌＡ： 電気１１ｉ　１１ニッケル合金メッキ鋼板（メッキ目付
１４０　Ｑ／　ｍ２）を市販のアルカリ脱脂剤で清浄化
し、水洗、乾燥させたもの。Metal base 1A that has not been subjected to corrosion-resistant chemical pretreatment: Electric 11i 11 nickel alloy plated steel plate (plating area: 140 Q/m2) cleaned with a commercially available alkaline degreaser, washed with water, and dried.

耐食性化成予備処理のほどこされた金属基材：同一にの
アルカリ１１１２脂処理、水洗、乾燥した電気亜鉛ニッ
ケル合金メッキ鋼板に、無水クロムＭ５％水溶液を５０
℃で３０秒間スプレー【ノ、次いで水洗、乾燥させたも
の。Metal base material subjected to corrosion-resistant chemical pretreatment: An electrolytic zinc-nickel alloy plated steel sheet that has been treated with alkali 1112 oil, washed with water, and dried is treated with 5% aqueous solution of anhydrous chromium M at 50%.
Spray at ℃ for 30 seconds, then wash and dry.

実施例１ 化成予備処理のほどこされていない電気亜鉛ニッケル合
金メッキ鋼板に、下記クロメート処理液をロールコート
法で塗布し、次にガス炉で最高到達板温１５０℃になる
よう１分間乾燥し、６０ｍ０／　１１２のクロム量のク
ロメート皮膜を作った。Example 1 The following chromate treatment solution was applied by roll coating to an electrolytic zinc-nickel alloy plated steel sheet that had not been subjected to chemical pretreatment, and then dried in a gas furnace for 1 minute to reach a maximum plate temperature of 150°C. A chromate film with a chromium content of 60m0/112 was made.

尚、り［１メート処理液としては、溶解度６〜８のクロ
ム酸亜鉛（金属クロム換算１５０）、ポリアクリル＠（
ジコリマーＡＣ−１０１−１日本純薬１１１１１）（固
形分換算１０ｇ）、および水を全量が１ｅになる如く配
合し、ペイントシェーカーで１２３一 時間ガラスピーズ分散して得た液を用いた。別途に下記
塗料組成物を調整した。In addition, the 1M treatment solution includes zinc chromate with a solubility of 6 to 8 (metallic chromium equivalent: 150), polyacrylic @ (
Dicolymer AC-101-1 Nippon Pure Chemical Industries, Ltd. 11111) (solid content: 10 g) and water were blended in a total amount of 1e, and a liquid obtained by dispersing glass beads in a paint shaker for 1 hour was used. The following coating composition was separately prepared.

ウレタン変性１ポキシ樹脂（特開昭５７−３０７１７、
実施例３ににって調整、分子中ベンゼン環含有率４５ｗ
ｔ％）を１６重化部（Ｉｉ’、ｉ形弁換算）、レゾール
型フェノール樹脂（昭和ユニオン合成■製、ＢＫＳ−３
１６、分子中ベンげン環含有率５５Ｖ１ｔ％）を４重量
部（固形分換算）をシクロヘキサノンに溶融せしめ、フ
ェロボスＨＲ８２１３２（ツーカーケミカルスアンドプ
ラスチックス社製リン化鉄主成分導電顔料）を６０重量
部、ストロンチウムクロメートＮ（菊池色素製品、リン
生鉱分解抑制剤のクロム酸塩顔料）５田畑部を添加し、
ペイントシェーカーで、２＃１８１スチ一ルビーズ分散
する。塗料を濾過し、セリダスト３６２０　（ヘキスト
社製、微粉化ポリエチレンワックス）を１５重量部を添
加して、ディスパーで均一に混合し、シクロヘキサノン
で不揮発部約６０Ｗ【％になる様、調整する。Urethane modified 1 poxy resin (Japanese Patent Application Laid-Open No. 57-30717,
Adjusted according to Example 3, benzene ring content in molecule 45w
t%) to 16 parts (Ii', i-type valve equivalent), resol type phenol resin (manufactured by Showa Union Gosei ■, BKS-3)
16. Melt 4 parts by weight (in terms of solid content) of benzene ring content in the molecule (55V 1t%) in cyclohexanone, and add 60 parts by weight of Ferobos HR82132 (iron phosphide-based conductive pigment manufactured by Tsuka Chemicals and Plastics). , strontium chromate N (Kikuchi pigment product, chromate pigment of phosphate mineral decomposition inhibitor) 5 Tabatabe is added,
Using a paint shaker, disperse 2 #181 steel beads. Filter the paint, add 15 parts by weight of Ceridust 3620 (manufactured by Hoechst, micronized polyethylene wax), mix uniformly with a disper, and adjust with cyclohexanone so that the non-volatile content is about 60%.

前記クロメート処理鋼板に対し、該塗料組成物２４− を【、１−ルコート法で塗装し、ガス炉で最高到達板温
２００℃で１分間焼付して、塗膜厚７μの被膜を形成せ
しめ耐食性塗装積層体を得た。The chromate-treated steel sheet was coated with the coating composition 24- by the 1-ru coating method, and baked in a gas furnace at a maximum plate temperature of 200°C for 1 minute to form a film with a coating thickness of 7 μm to improve corrosion resistance. A painted laminate was obtained.

実施例２〜７ならびに比較例１〜４ 実施例１と同様方法で、但し金属ＭＣＩ、耐食層組成、
塗お１組成を夫々下記第１表に記載の如く変更し、塗装
＠囲体を得た。Examples 2 to 7 and Comparative Examples 1 to 4 Same method as Example 1, except that metal MCI, corrosion-resistant layer composition,
The coating composition was changed as shown in Table 1 below to obtain coatings.

尚、実施例２などで用いられている溶解度が２０より大
なる水溶性クロム化合物を含むクロメート処理液は例え
ば次の如くにして調整された。The chromate treatment solution containing a water-soluble chromium compound having a solubility of more than 20, which is used in Example 2, was prepared, for example, as follows.

無水クロム酸く金属クロム換算２０Ｑ＞を水５００＋［
’に溶解し、ホルマリンを加え全クロムの所定％、例え
ば４０％をＣｒ３＋に還元して部分還元クロム酸水溶液
を作り、次に例えばアエロジル３００（日本アエロジル
社製、ヒユームドシリカ）を１５０１溶解痕６〜８のク
ロム酸亜鉛（金属クロム換算１５ｇ）を加え、水で全ω
を１ｅになし、ペイントシェーカーで１時間ガラスピー
ズ分散する。Anhydrous chromium acid (metallic chromium equivalent: 20Q) water: 500+[
', add formalin and reduce a predetermined percentage of the total chromium, for example 40%, to Cr3+ to make a partially reduced chromic acid aqueous solution, then add, for example, Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd., Huumed Silica) to 1501 dissolution marks 6- Add zinc chromate (metallic chromium equivalent: 15g) from step 8, and add water to make the total omega
Disperse the glass beads in a paint shaker for 1 hour.

各実施例ならびに比較例で１ｑられた積層体につき（調
整３日後）、夫々下記の性能試験を行１．ｒい、第２表
の如ぎ結束が得られた。The following performance tests were conducted on the 1q laminates of each Example and Comparative Example (3 days after preparation). A bond as shown in Table 2 was obtained.

試験方法及び評価基準 １、連続スポラ１〜溶接性 電極径５ｍｍ、加圧力２００　ｋＱ、通電時間１０サイ
クル、電流Ｂ　ＯＯＯＡの条１′１でスポット溶接を実
施し、連続打点可能な１１点数を調べた。Test method and evaluation criteria 1, continuous spora 1 - Weldability Electrode diameter 5 mm, pressurizing force 200 kQ, energization time 10 cycles, current BOOOA, spot welding was carried out with strip 1'1, and the number of 11 points that could be continuously welded was investigated. Ta.

評価 ◎：５０００点以−に点本−汚れ少ない○：５０００点
以−Ｖ　電１４！汚れ多いΔ：　３０００点〜５０００
点 Ｘ：３０００点未満 ２、塗膜加］−竹 円筒深絞り試験器（Ｊリクセンネ１製、モデルＢ　１−
１４２型）を使用し、しわ押え圧３１〜ン、ポンチ径５
０１１１ＩＩｌφ、ダイス径５２．４ｔｎｎ＋φ、絞り
深さ４Ｑｍｍ、ブランク径９５ｍｍ）ぐ加工し、塗膜の
キズ、剥対１を調べた。Evaluation: ◎: 5,000 points or more - little dirt ○: 5,000 points or more - V Electric 14! Dirty Δ: 3000 points to 5000 points
Point
142 type), wrinkle presser pressure 31 to
0111IIlφ, die diameter 52.4tnn+φ, drawing depth 4Qmm, blank diameter 95mm), and the coating film was inspected for scratches and peeling 1.

評価 ◎：塗面異常なし ○：塗而面ズ（素地金属未到達）有り （１０％以ト） △：索地金属に達づるキズ有り、また、塗面キズ多い ×：原板ワレ ３、耐食性 ■複合腐食試験（１サイクル−塩水噴１（５％ＮａＣ＋
、３５℃）、２時間→乾燥（６０℃）、２時間−〉湿潤
（９８％ＲＨ≦、５０℃）４時間２００サイクル後の平
面部の赤サビ、白ザビの発生状態を調べた。Evaluation: ◎: No abnormalities on the painted surface ○: There are scratches on the painted surface (not reaching the base metal) (10% or more) △: There are scratches that reach the base metal, and there are many scratches on the painted surface ×: Original plate cracks 3, corrosion resistance ■Combined corrosion test (1 cycle - salt water jet 1 (5% NaC +
, 35° C.), 2 hours→drying (60° C.), 2 hours->wetting (98% RH≦, 50° C.) for 4 hours, and after 200 cycles, the occurrence of red rust and white rust on the flat surface was examined.

評価 ◎：自サビ、赤サビ発生なし Ｏ：白サビ発生面積５％以下、赤サビなし△：　６％以
上、 ×：赤すビ１％以上発生 ■塩水噴霧試験（ＪＴＳ−２２３７１に準ず）２０００
時間後の平面部の赤サビ、白サビの２９− 発生状態を調べた。Evaluation ◎: No natural rust or red rust O: 5% or less area of white rust, no red rust △: 6% or more ×: 1% or more of red rust ■Salt water spray test (according to JTS-22371) 2000
After a period of time, the state of red rust and white rust on the flat surface was examined.

評価 ◎：白４Ｊビ、赤υビ発生なし Ｏ：白４Ｊ−ビ発生而槓５％以下、赤サビなしΔ　：　
６％以」二、 ×：赤すビ１％以−に発生 （以下余白） ３０− 第２表 特許出願代理人 弁理士　伊　藤　武　雄Evaluation: ◎: White 4J-vinyl, no red rust O: White 4J-vinyl 5% or less, no red rust Δ:
6% or more” 2, ×: Occurs in 1% or more of the red squares (blank below) 30- Table 2 Patent application agent Takeo Ito

Claims (11)

【特許請求の範囲】[Claims] （１）耐食性化成半幅処理のほどこされた、あるいは予
備処理のほどこされていない金属Ｍ４４十に、溶解度２
０〜１０″５の６価り１１ムを含むり１］ム化合物の少
なくとも１種と水性シリカおにび／または水性樹脂バイ
ンダーを必須成分とし、所望により溶解度が２０Ｊ：り
人なる水溶↑（１クロム化合物を含む組成物の耐食層な
らびに導電塗料層が順次積層されてなり、該塗料層が、
塗１′＋１固形分どして（Ａ）分子中の芳香族環含有率
が０〜５０重量％の塗料用樹脂　１０〜３５重石％ 有機潤滑剤　４〜５０ｉ１ｆｆ１％　および導電顔１３
１　１５〜８６重量％　あるいは（Ｂ）分子中の芳香族
環含有率がＯ〜５０重四％の塗料用樹脂　１０〜３５重
量％ 有機ｆｉｔｌ滑剤　４〜３０重量％ 重量％リン酸鉄主成電顔１１１５〜８５重量％リン化鉄
分解抑制剤　１〜７１重間％ その他の無機顔料　０〜７０重量％ 但し、導電顔料、リン生鉱分解抑制剤およびその他の無
機顔料の合計量が３５〜８６重量％ の組成を含んでなる層であることを特徴とする耐食性塗
装積層体。(1) Solubility 2 in metal M440 which has been subjected to corrosion resistance chemical conversion half-width treatment or which has not been subjected to pre-treatment.
0 to 10"5 containing at least one hexavalent 11m compound and a water-based silica/or a water-based resin binder as essential components, and optionally has a solubility of 20J: water-soluble ↑ ( A corrosion-resistant layer and a conductive paint layer of a composition containing a chromium compound are sequentially laminated, and the paint layer is
Coating 1'+1 solid content (A) Coating resin with aromatic ring content in the molecule of 0 to 50% by weight 10 to 35 weight% Organic lubricant 4 to 50il1ff1% and conductive face 13
1 15-86% by weight or (B) Paint resin with aromatic ring content in the molecule of O-50% by weight 10-35% by weight Organic Fitl lubricant 4-30% by weight Iron phosphate main electrolyte Face 11 15-85% by weight Iron phosphide decomposition inhibitor 1-71% by weight Other inorganic pigments 0-70% by weight However, the total amount of conductive pigments, phosphate mineral decomposition inhibitors and other inorganic pigments is 35-86% by weight. A corrosion-resistant painted laminate characterized in that the layer comprises a composition of % by weight. （２）金属基材が鉄、亜鉛、アルミニウム系金属あるい
はニッケル又は鉄を含む電気亜鉛メッキ鋼板である特許
請求の範囲第１項記載の積層体。(2) The laminate according to claim 1, wherein the metal base material is an electrogalvanized steel sheet containing iron, zinc, aluminum metal, or nickel or iron. （３）耐食層がクロム化合物を金属クロム換算で０．０
１〜１　（１／　ｒｎ２、特許請求の範囲第１項記載の
積層体。(3) The corrosion-resistant layer contains a chromium compound of 0.0 in terms of metallic chromium.
1 to 1 (1/rn2, laminate according to claim 1. （４）耐食層中、６価り０ムが水溶性全クロムの１０〜
９０重量％を占める特許請求の範囲第１項記載の積層体
。(4) In the corrosion-resistant layer, the hexavalent 0 chromium is 10 to 10 of the water-soluble total chromium.
The laminate according to claim 1, which accounts for 90% by weight. （５）塗料層膜厚が１〜２０μである特許請求の範囲第
１項記載の積層体。(5) The laminate according to claim 1, wherein the paint layer has a thickness of 1 to 20 μm. （６）塗料用樹脂がエポキシ樹脂、アルキド樹脂、アク
リル樹脂、メラミン樹脂、ウレタン樹脂、フエノール樹
脂、ビニル樹脂、ポリビニルブヂラール樹脂、ポリビニ
ル７１′！チー１へ樹脂、塩素化ゴム、オイルフリーポ
リ１ステル樹脂、フタル酸樹脂、スチレン樹脂、ポリオ
レフィン樹脂である’ｌ’ｆ　Ｆｔ請求の範囲第１項記
載の積層体。(6) Paint resins include epoxy resin, alkyd resin, acrylic resin, melamine resin, urethane resin, phenol resin, vinyl resin, polyvinylbutyral resin, and polyvinyl 71'! The laminate according to claim 1, which is a resin, a chlorinated rubber, an oil-free polyester resin, a phthalic acid resin, a styrene resin, or a polyolefin resin. （７）有１１！潤滑剤がポリオレフィン系化合物、カル
ボン酸エステル系化合物、ポリアルキレングリコール系
化合物から選ばれる化合物である特許請求の範囲第１項
記載の積層体。(7) Yes 11! The laminate according to claim 1, wherein the lubricant is a compound selected from polyolefin compounds, carboxylic acid ester compounds, and polyalkylene glycol compounds. （８）有機潤滑剤が３００〜５００°Ｃで発熱的分解を
示す化合物である特許請求の範囲第７項記載の積層体。(8) The laminate according to claim 7, wherein the organic lubricant is a compound that exhibits exothermic decomposition at 300 to 500°C. （９）リン生鉱分解抑制剤がｌｌｌ−１６〜１３の懸濁
ｐＨを示す顔料である特許請求の範囲第１項記載の積層
体。(9) The laminate according to claim 1, wherein the phosphate mineral decomposition inhibitor is a pigment having a suspension pH of lll-16 to lll-13. （１０）その他の無機顔料がり１］ム顔利、リン酸塩顔
料、鉛顔利あるいは着色Ｍｒｊ　ｌ！ｌである特許請求
の範囲第１項記載の積層体。(10) Other inorganic pigments 1] Mu pigments, phosphate pigments, lead pigments, or colored Mrj l! 1. The laminate according to claim 1, which is 1. （１１）導電顔料、リン生鉱分解抑制剤およびその他の
無機顔料の合８１ｍが塗料固形分中３５〜７０重量％で
ある特許請求の範囲第１項記載の積層体。(11) The laminate according to claim 1, wherein the total amount of the conductive pigment, phosphorite decomposition inhibitor, and other inorganic pigments is 35 to 70% by weight in the solid content of the paint.