JPS60203677A - Coating compound composition for precoating of metallic material - Google Patents

Abstract

PURPOSE:The titled composition for coating body of automobile, etc., having improved welding properties, processing properties, and corrosion resistance, obtained by blending a resin for coating compound with an organic lubricant, electrically-conductive pigment consisting essentially of iron phosphide, a decomposition inhibitor for iron phosphide, etc. in a specific ratio. CONSTITUTION:(A) 10-35wt% resin for coating compound (e.g., epoxy resin, etc.) containing 0-50wt% aromatic ring is blended with (B) 4-30wt% organic lubricant (e.g., polyolefinic compound), (C) 15-85wt% electrically-conductive pigment consisting essentially of iron phosphide, (D) 1-71wt% decomposition inhibitor for iron phosphide (e.g., pigment providing suspension at 6-13pH), (E) 0-70wt% another inorganic pigment (e.g., chromium pigment, etc.) in such a way that total amounts of the components C, D, and E are 35-86wt% based on solid materials of the coating compound, to give the desired composition.

Description

【発明の詳細な説明】 本発明は溶接性、加工性、耐食性に優れた金属材プレコ
ート用塗料組成物に係り、就中自動車ボデー用鋼材に適
した連続スポット溶接性に優れ、高加工性、高耐食性の
鋼板プレコート用塗料組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint composition for precoating metal materials that has excellent weldability, workability, and corrosion resistance, and in particular, has excellent continuous spot weldability, high workability, and is suitable for steel materials for automobile bodies. The present invention relates to a coating composition for precoating steel sheets with high corrosion resistance.

プレコート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ている。From the point of view of spot weldability of pre-coated 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 welding 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５８−１３８７５８号
、特開昭５８−１７４５８２号等）、あるいは顔料の工
夫により塗膜導電性をさらに向上させる技術（例えば特
開昭５１−７９１３８、特公昭５８−１９７０６）など
ではスポット溶接は可能であっても２０００点あるいは
それ以上の連続スポット溶接性を確保するための要件、
すなわち電極汚染に対す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１稈に於ては可及的に大な
る、例えば２０００〜５０００点の連続スポット溶接性
が要望せられる。Techniques to make the coating film conductive using conductive pigments (e.g., Japanese Patent Publication No. 44569/1982, Japanese Patent Application Laid-open No. 138758/1982, Japanese Patent Application Laid-open No. 174582/1983), or techniques to further improve the electrical conductivity of the coating film by devising pigments. Even if spot welding is possible in techniques to improve (for example, JP-A-51-79138, JP-A-58-19706), there are requirements to ensure continuous spot welding of 2000 points or more,
In other words, there is no consideration given to electrode contamination, resulting in unsatisfactory results. Moreover, in recent automobile production, continuous spot welding of as large as possible, for example 2,000 to 5,000 points, is required.

また、塗装材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付着して加工キズ
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離し、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, when pressing or deep drawing painted materials, the paint film may peel off into powder during processing and adhere to the press machine, causing processing scratches, requiring frequent cleaning of the press machine, or During processing, the coating film must not peel off from the base or crack, thereby reducing the corrosion resistance of the area.

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！ｊ−ることは公知である。Inorganic or organic lubricants are added to improve the workability of this coating! It is known that j-.

しかしながら元来、溶接可能な塗膜は心電性確保のため
顔料リッチな組成となる傾向があって、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
充分発揮される最配合覆ることは、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, weldable coatings originally tend to have a pigment-rich composition to ensure electrocardiac properties, and for example, inorganic pigments such as molybdenum disulfide, carbon, and lead oxide are used to fully demonstrate their effects. There is a problem in that over-mixing leads 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Ｗ！ｉ３ｇ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（６）に含む塗料では塗膜の耐食性は低下す
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うる
うえで特に重要である。Furthermore, in the production of automobiles, various parts of the body, such as rocker panels, doors, fenders, etc., are usually made from steel plates by press working, assembled by spot welding, and then degreased and rinsed. Since it is electrodeposited through i3g treatment, it is required to have good workability, spot weldability, adhesion to the electrodeposited coating, 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, paints that contain relatively large amounts of conductive pigments and lubricants (6) tend to have a reduced corrosion resistance, and in some cases, the conductive pigments themselves or their decomposition products may exhibit a corrosion-promoting effect. The type of conductive pigment and the conditions under which it is used are particularly important in obtaining highly corrosion-resistant coatings.

従って本発明の目的は加工性のみならず特に耐食性なら
びに連続スポット溶接性に優れた塗料膜を与えうる金属
材プレコート用塗料組成物を提供するにある。Accordingly, an object of the present invention is to provide a coating composition for precoating metal materials that can provide a coating film that is excellent not only in processability but also in particular in corrosion resistance and continuous spot weldability.

本発明者らは連続スポット溶接性と塗膜組成との関連性
につき研究の結果、塗膜バインダー樹脂の熱分解性がこ
の連続スポット溶接性に大きく関与し、また該熱分解性
は４刺脂分子中の芳香族環含有率と、易熱分解性物質の
共存の有無により変化し、芳香族環含有率が０あるいは
ある限度内であり、且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著しく向上せしめられ
ることを見出した。また、加工性の向上に関しては無機
顔料がかなりの量共存するため、なるべく少量でしかも
低比重、大容積のもの、す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 spot weldability and coating film composition, the present inventors found that the thermal decomposition of the coating film binder resin is greatly involved in this continuous spot weldability. It varies depending on the aromatic ring content in the molecule and the presence or absence of easily thermally decomposable substances, and if the aromatic ring content is 0 or within a certain limit and an appropriate amount of easily thermally decomposable substances are added, continuous It has been found that spot weldability is significantly improved. In addition, in order to improve processability, since a considerable amount of inorganic pigment coexists, it is preferable to use a lubricant with a small amount, low specific gravity, and large volume, that is, an organic lubricant. For what we do, we learned that the selection of the appropriate type and amount of lubricant, as well as the total amount of conductive pigments and other inorganic pigments, is important.

さらにまた導電顔料のうちリン化鉄を主成分とする顔料
が本発明目的に対し最適であること、またこの特定顔料
を使用するに際し、その分解を抑制する顔料との併用が
特に高度の耐食性を得る上で有用であることを見出し、
本発明を完成するに至った。Furthermore, among conductive pigments, pigments whose main component is iron phosphide are most suitable for the purpose of the present invention, and when using this specific pigment, a particularly high degree of corrosion resistance can be achieved by using it in combination with a pigment that suppresses its decomposition. found it useful in obtaining
The present invention has now been completed.

すなわち本発明に従えば塗料固形分として、（Ａ）芳香
族環を含まぬか、あるいはその含有率が５０重量％以下
の少なくとも１種の塗料用樹脂　１０〜３５重量％ （Ｂ）有機潤滑剤　４〜３０重量％ （Ｃ）リン化鉄主成分の導電顔料 １５〜８５重量％ （Ｄ）リン化鉄分解抑制材　１〜７１重量％（Ｅ）その
他の無機顔料　０〜７０重量％を含み、導電顔料（Ｃ）
、リン化鉄分解抑制剤（Ｄ）およびその他の無機顔料（
Ｅ）の総量が塗料固形分中３５〜８６重量％である塗料
組成物が提供せられる。That is, according to the present invention, the solid content of the paint is (A) at least one paint resin that does not contain aromatic rings or has a content of 50% by weight or less (B) 10 to 35% by weight (B) an organic lubricant 4 -30% by weight (C) 15-85% by weight of a conductive pigment mainly composed of iron phosphide (D) 1-71% by weight of an iron phosphide decomposition inhibitor (E) Contains 0-70% by weight of other inorganic pigments, conductive Pigment (C)
, iron phosphide decomposition inhibitor (D) and other inorganic pigments (
A coating composition is provided in which the total amount of E) is 35 to 86% by weight of the coating solids.

本発明の塗料組成物に用いられる樹脂成分は分子中の芳
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で有機溶剤タイプあるいは水性化さ
れたタイプで使用せられる。The resin component used in the coating composition of the present invention is a coating resin whose aromatic ring content in the molecule is O or up to 50% by weight, such as epoxy resin, alkyd resin, acrylic resin, 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, polyolefin resin, etc. organic solvent type or water-based type. used in

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、組合ゼ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重量％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 resin, 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℃まで２０℃／
分の速度で樹脂を昇 温（Ｎ２気流中）させ、ザンプ ル温度が５５０℃に達した時の 重量を熱重量分析器ぐ測定（ザ ンブ）Ｌ、Ｎ５〜１０１１１１１１＞ が著しく低下し、それと共に連続スポット溶接性も著し
く低下すること。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ろこと
を見出した。The present inventors have determined that the aromatic ring content in resin molecules is closely related to continuous spot weldability, and that when it exceeds 50%, the thermal decomposition rate is measured by the following method.Resin weight after heating...from room temperature to 550℃ 20℃/
The resin was heated at a rate of 550°C (in a N2 gas flow), and when the sample temperature reached 550°C, the weight was measured using a thermogravimetric analyzer (Zanbu). Spot weldability is also significantly 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%,
We have found a scale that can sufficiently withstand continuous spot welding of up to 5,000 points.

尚、樹脂の塗料固形分中の含有率は１０〜３５重量％、
好ましくは１５〜２５重最％で、１０重量％を下まわる
と加工性の低下が著しく、また３５重世％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,
Preferably, the maximum content is 15 to 25% by weight, and it has been found that if the content is less than 10% by weight, workability is significantly reduced, and if it exceeds 35% by weight, continuous spot weldability is reduced.

本発明組成物中に使用せられる有機潤滑剤は、加工用冶
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す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の容積
分率が大きい有機性物質であるだ【プでなく、熱分解性
が良好（分解温度３００〜５００℃）で発熱反応を示し
大部分が揮発して連続スポット溶接に悪影響を与えるカ
ーボンを残さずざ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、アイソタクチックポ
リプロピレン、ポリブテン等、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、セバシン酸などのカルボン酸と、ｎ−ブタノール
、５ｅＣ１−ブタノール、３−メチルブタノール、２−
エチルヘキサノール、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。The organic lubricant used in the composition of the present invention is a so-called slip agent that reduces the friction between the processing jig and the coating film, weakens the force applied to the coating film, and reduces damage to the coating film during processing. It is an organic substance that has a low specific gravity and a large volume fraction in the coating film even in small amounts. It is preferable to use a resin thermal decomposition promoting substance that coexists with the resin without leaving behind carbon, most of which volatilizes and adversely affects continuous spot welding.In this sense, polyolefin compounds such as polyethylene, isotactic Polymers of unsaturated aliphatic olefin hydrocarbons such as polypropylene and polybutene (preferably molecular weight 1000-10
000); Carboxylic acid ester compounds, such as stearic acid, oleic acid, adipic acid, azelaic acid, sebacic acid, and n-butanol, 5eC1-butanol, 3-methylbutanol, 2-
Seven-, di-, or poly-esters with alcohols such as ethylhexanol and neopentyl alcohol; polyalkylene glycol compounds such as polypropylene glycol, polyethylene glycol, etc. are recommended as particularly preferred substances.

加工性、熱分解性、耐食性、上塗塗膜の密着性等の観点
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５
０μ以下のポリエチレン微粉末である。Polyethylene waxes are particularly preferred from the viewpoint of processability, thermal decomposition properties, corrosion resistance, adhesion of the top coat, etc., and the most preferred waxes have a molecular weight of 1,000 to 10,000. Particle size 5
It is a polyethylene fine powder of 0μ 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重量％をこえても、それ以上の加工性の向上は認
められづ゛、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 may be used alone or in combination of two or more, but the amount added is 4 to 30% by weight, preferably 4 to 20% by weight, based on the solid content of the paint. If it is less than 4% by weight, processability will decrease. However, no effect of accelerating thermal decomposition of the resin was observed, and on the other hand, even if the amount exceeded 30% by weight, no further improvement in processability was observed, and on the contrary, corrosion resistance tended to decrease as the amount increased.

本発明の組成物にはまた導電性付与の目的で導電顔料を
含有せしめるのであるが、ががる導電顔料としては電気
抵抗が安定して低く、少量で充分な通電効果の得られる
こと、溶接時の発熱により溶融せず高融点物質であって
、溶融−接触面積増大−電流密度の低下とか電極付着汚
染などの欠点のないもの、また硬度が高（、溶接時の加
圧で導電粒子が絶縁体塗ＲＭ樹脂層を破壊し導通性をよ
り良好ならしめうること、およびなるべく低価格で大量
供給せられるものであることが好ましいことは言うまで
もない。The composition of the present invention also contains a conductive pigment for the purpose of imparting conductivity, and as a conductive pigment, it has a stable and low electrical resistance, and a sufficient current carrying effect can be obtained with a small amount. A material with a high melting point that does not melt due to heat generated during welding, and does not have drawbacks such as melting, increased contact area, reduced current density, and electrode adhesion contamination. It goes without saying that it is preferable that the insulator-coated RM resin layer can be destroyed to improve conductivity, and that it can be supplied in large quantities at as low a price as possible.

本発明者らは以上の長所をもち、なお且つ他の金属粉な
どに此し不活性で耐食性にも優れている顔料としてリン
化鉄（ＦｅｚＰ）を主成分とする２０μ以下、好ましく
は１０μ以下の粒径をもつ顔料が最適であることを見出
した。The present inventors have developed a pigment with iron phosphide (FezP) as a main component that has the above advantages, is inert to other metal powders, and has excellent corrosion resistance, and is less than 20μ, preferably less than 10μ. It was found that a pigment with a particle size of .

リン化鉄を主成分とづる導電顔料はフェロホス等として
各種市販されておりそれらが単独あるいは組合せの形で
用いられる。リン化鉄を主成分とづる導電顔料は塗料固
形分中１５〜８５重量％、好ましくは３０〜７０重量％
の割合で用いられる。Various conductive pigments containing iron phosphide as a main component are commercially available as ferrophos and the like, and these can be used alone or in combination. The conductive pigment whose main component is iron phosphide is 15 to 85% by weight, preferably 30 to 70% by weight in the solid content of the paint.
used at a rate of

というのは３０重量％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、また１５重量％未満では
明らかに導電性不足でスポット溶接ができない。７０重
量％をこえると塗膜加工性が低下する場合があり、８６
重量％をこえると明らかに加工性が劣化し実用的でなく
なる。This is because if it is less than 30% by weight, the electrical conductivity may be insufficient when the coating thickness is 10 μm or more, and if it is less than 15% by weight, the electrical conductivity is clearly insufficient and spot welding cannot be performed. If it exceeds 70% by weight, the processability of the coating may deteriorate;
If it exceeds % by weight, the processability will obviously deteriorate and it will become impractical.

このように本発明では導電顔料として知られるもののう
ち、特にリン化鉄主成分の顔料が発明目的に対し最も優
れた結果を与えることの発見にその基礎の一つをおくも
のであるが、それでもなお腐食環境下、特に塗膜が酸性
雰囲気におがれる場合、リン化鉄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するが、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す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、リン化畝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ｐＨ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て有効
な手段であることを見出した。As described above, one of the foundations of the present invention is the discovery that among the known conductive pigments, pigments mainly containing iron phosphide give the most excellent results for the purpose of the invention. It has been found that in a corrosive environment, particularly when the coating film is exposed to an acidic atmosphere, iron phosphide decomposes and the decomposed products accelerate corrosion. Whether or not the coating film becomes an acidic atmosphere depends on the coating composition, base metal,
Although it depends on the corrosive environment conditions, it would be better if a composition that shows a higher degree of corrosion resistance can be obtained in severe tests such as complex corrosion tests in which several types of corrosive environments and alternating dry and wet conditions are set. There isn't. In order to obtain such a composition, the present inventors believe that it is necessary to suppress the decomposition of the phosphide ridges or to render the decomposed products harmless, and for this purpose, the pH of the suspension water is 6 to 13,
It has been found that the coexistence of pigments, preferably from 7 to 11, is an extremely effective means as it keeps the coating film on the neutral or alkaline side.

従って本発明組成物にはリン化鉄主成分の導電顔料と共
にリン化鉄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おく目的のものであって、
懸濁水ｐＨが６〜１３の顔料が好都合に使用せられる。Therefore, the composition of the present invention contains an iron phosphide decomposition inhibitor as an essential component along with a conductive pigment mainly composed of iron phosphide. As mentioned above, such decomposition inhibitors are used for the purpose of keeping the coating film continuously on the neutral or alkaline side.
Pigments with a suspension water pH of 6 to 13 are advantageously used.

具体的には例えば下記化合物があげられる。Specific examples include the following compounds.

（１）アルカリ土類金属石油スルホネート（２）クロム
酸亜鉛、クロム酸亜鉛カリウム、クロム酸鉛、塩基性ク
ロム酸鉛、クロム酸カルシウム、クロム酸ストロンチウ
ム等のクロム酸塩顔料 （３）リン酸亜鉛、リン酸鉄、トリポリリン酸アルミニ
ウム等のリン酸塩顔料 （４）鉛酸カルシウム、ケイ酸鉛等の鉛化合物顔料 （５）タルク、炭酸カルシウム、シリカ等の体質顔料 （６）亜鉛末（リン化鉄と同量以下） 但し、これらの添加Ｒは塗料固形分中、１重量％以上で
、次に記述する無機顔料の総量を越えない量とする。(1) Alkaline earth metal petroleum sulfonates (2) Chromate pigments such as zinc chromate, potassium zinc chromate, lead chromate, basic lead chromate, calcium chromate, strontium chromate, etc. (3) Zinc phosphate , iron phosphate, aluminum tripolyphosphate, etc. (4) lead compound pigments such as calcium leadate, lead silicate, etc. (5) extender pigments such as talc, calcium carbonate, silica, etc. (6) zinc powder (phosphide) However, the amount of these additives R should be 1% by weight or more based on the solid content of the paint, and should not exceed the total amount of 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ｐＨの点で本発明に於（はリ
ン化鉄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 iron phosphide decomposition inhibitors in terms of the pH of the suspended water.

本発明組成物にはまた所望によりその伯の無機顔料、例
えば耐食性向上のためのクロム顔料（クロム酸亜鉛末、
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）、リン酸塩顔料（リン酸曲鉛、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（！ＡＩ酸カルシウム、クイ酸鉛等）；樹脂量の
調整、塗膜吐１調整のＩｃ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（酸化ク
ロム、酸化鉄、酸化鉛等〉を加えることができる。The composition of the present invention may also optionally contain inorganic pigments, such as chromium pigments (zinc chromate powder,
Lead chromate-based, calcium chromate-based, strontium chromate-based pigments, etc.), phosphate pigments (bent lead phosphate, iron phosphate, aluminum tripolyphosphate-based pigments, etc.), lead compound pigments (!Calcium AI phosphate, (acid lead, etc.); adjustment of resin amount, coating film discharge 1 adjustment, Ic extender pigments (silica, calcium carbonate, talc, alumina, etc.); coloring pigments (chromium oxide, iron oxide, lead oxide, etc.) can be added. can.

こういった無機顔料を加える場合はやはり次に述べる無
機顔料の総量をこえてはならない。When adding such inorganic pigments, the total amount of inorganic pigments described below must not be exceeded.

すなわち、本発明組成物においてはリン化鉄主成分の導
電顔料、リン生鉱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、３５〜８
６重Ｍ％、好ましくは３５〜７０重量％の範囲内にある
ことが重要である。That is, in the composition of the present invention, the total amount of the conductive pigment mainly composed of iron phosphide, the phosphate mineral decomposition inhibitor, and other inorganic pigments added as desired is 35 to 8% in the solid content of the paint.
It is important that the amount is 6% by weight, preferably in the range of 35 to 70% by weight.

というのは、前記総量が３５重Ｍ％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、８６重用％をこえると明らかに大
幅な加工性低下が認められるからである。This is because when the total amount is less than 35% by weight, the processability of the coating decreases, and even when it exceeds 70% by weight, a decrease in processability may be observed, and when it exceeds 86% by weight, it is clearly significantly reduced. This is because a significant decrease in workability is observed.

本発明の塗料組成物は前記各成分を常法により混合して
調整せられる。通常まず樹脂をあらかじめ溶剤により液
状にしておく。リン化ｖＹ導電顔料ａ３よびリン生鉱分
解抑制剤、ならびに所望により添加せられるその仙の無
機顔料を前記樹脂液の一部と混合し、ペイントシェーカ
ー、三本ロールミル、サンドグラインドミル、ボールミ
ル、デシルバーなど公知の塗料用分散機を用いて分散し
、この分散液に樹脂液の残余、潤滑剤を加え均一にかき
まぜ、また必要によっては再度分散して塗料とする。塗
料固形分濃度は塗装方法により相違づるが通常１０〜７
０重量％の範囲に調整せられる。The coating composition of the present invention can be prepared by mixing the above-mentioned components in a conventional manner. Usually, the resin is first liquefied with a solvent. The phosphorized vY conductive pigment A3, the phosphorite decomposition inhibitor, and the inorganic pigments added thereto if desired are mixed with a part of the resin liquid, and then mixed with a paint shaker, three-roll mill, sand grind mill, ball mill, or mill. Disperse using a known dispersing machine for paints such as silver, add the remainder of the resin liquid and a lubricant to this dispersion, stir evenly, and if necessary, disperse again to form a paint. The solid content concentration of the paint varies depending on the coating method, but is usually 10 to 7.
It is adjusted to a range of 0% by weight.

勿論、上記以外の任意の公知手段により塗料の調整は可
能であり、また所望により他の塗料添加剤を加えること
もできる。Of course, the paint can be adjusted by any known means other than those mentioned above, and other paint additives can be added if desired.

なお、塗料調整に際し、溶剤としては通常の塗料用溶剤
、例えばキシレン、トルエン、ミネラルスピリット、メ
タノール、エタノール、ブタノール、イソプロパツール
、メチルエチルケトン、１チルフチルケトン、メチルイ
ソブヂルケトン、エチレングリコールモノブチルエーテ
ル、エチレングリコールモノエヂル１−デル、］ニヂレ
ングリコールモノエヂルアセテート、エチルアセデー１
・、ブチルアセテート、シクロヘキサノン、水等を用い
ることができる。When preparing the paint, use ordinary paint solvents such as xylene, toluene, mineral spirit, methanol, ethanol, butanol, isopropanol, methyl ethyl ketone, 1-tylphthyl ketone, methyl isobutyl ketone, ethylene glycol monobutyl ether, and ethylene. glycol monoedyl 1-del, ]nidylene glycol monoedyl acetate, ethyl acede 1
・Butyl acetate, cyclohexanone, water, etc. can be used.

本発明の組成物は冷延鋼板、亜鉛メッキ鋼板、合金亜鉛
メッキ鋼板、アルミメッキ鋼板、亜鉛おにび亜鉛合金板
、アルミおよびアルミ合金板、ステンレス鋼板など各種
鋼板ならびに金属素材に常法により適用せられる。The composition of the present invention can be applied to various steel sheets and metal materials such as cold-rolled steel sheets, galvanized steel sheets, alloy galvanized steel sheets, aluminium-plated steel sheets, zinc-coated steel sheets, aluminum and aluminum alloy sheets, and stainless steel sheets, as well as metal materials. be given

すなわち、これら金属素材表面が油等で汚染されている
場合は、まずアルカリ化合物と界面活性剤を含むアルカ
リｎＩＪ脂剤あるいは有＋ｉ溶剤で洗浄して脱脂する。That is, if the surfaces of these metal materials are contaminated with oil or the like, they are first cleaned and degreased with an alkaline nIJ fat agent or a +i solvent containing an alkaline compound and a surfactant.

必要により水洗し、通常化成処理が行なわれる。この化
成処理はリン酸塩皮膜、クロム酸塩皮膜を形成せしめる
のが通常で、化成処理液をスプレー法、浸漬法、ロール
塗布法などで適用し、必要により水洗、乾燥せしめる。If necessary, it is washed with water, and chemical conversion treatment is usually performed. This chemical conversion treatment usually forms a phosphate film or a chromate film, and the chemical conversion treatment solution is applied by a spray method, dipping method, roll coating method, etc., followed by washing with water and drying if necessary.

このように予備処理された金属素材に対し、本発明組成
物はロールコート法、カーテン７０−法、スプレー法な
ど任意の常法で適用され、通常その塗膜厚はく乾燥膜厚
で＞１＝２０μ、好ましくは２〜１０μとなされる。次
いで焼付が行なわれるが、焼付条件は樹脂量により適宜
選択され、一般に最高到達板温１００〜３００℃で、３
０秒〜２分程度の焼付条件が用いられる。The composition of the present invention is applied to the metal material pretreated in this way by any conventional method such as roll coating, curtain method, or spraying, and usually the coating film thickness is >1 in terms of dry film thickness. =20μ, preferably 2 to 10μ. Baking is then carried out, and the baking conditions are appropriately selected depending on the amount of resin. Generally, the maximum board temperature is 100 to 300°C, and
A baking condition of approximately 0 seconds to 2 minutes is used.

かくして得られる塗装材は１■れた加工性、耐食性と共
に極めて優れた連続スポット溶接性を示す。The coating material thus obtained exhibits excellent workability and corrosion resistance as well as extremely excellent continuous spot weldability.

以下実施例により本発明を説明する。尚、例文中、部と
あるは重量品を示す。The present invention will be explained below with reference to Examples. In the example sentences, parts and parts indicate heavy items.

実施例１ ウレタン変性エポキシ樹脂（特開１１ｒ（５７−３０７
１７号実施例３により製造、ベンゼン環含有率４５重ω
％）Ｂとレゾール型フェノール樹脂（昭和ユニオン合成
■’ＩＢＫｓ−３１６、ベンゼン環含有率５５重石％）
Ｃとを８／２に配合した樹脂（平均ベンゼン環含有率４
７重量％）２０部をミクロへキサノン６６部に溶解させ
、次に７エロホストＩＲ８２１３２（リン化鉄主成分の
導電顔料、フーカーケミカルズアンドプラスチックスコ
ーポ製）６０部とストロンチウムクロメートＮ（クロム
酸塩顔料、懸濁水１）Ｈ８〜９、菊池色素製）５部を添
加し、ペイントシェーカーで２時間スチールピーズ分散
した。セリダスト３６２０（微粉化ポリエチレンワック
ス、ヘキスト社製）１５部を加え、ディスパーで均一に
混合し、不揮発分６５重量％の塗料組成物を得た。Example 1 Urethane modified epoxy resin (Unexamined Japanese Patent Publication No. 11r (57-307)
No. 17 Manufactured according to Example 3, benzene ring content 45 w
%) B and resol type phenolic resin (Showa Union Gosei IBKs-316, benzene ring content 55%)
Resin blended with C in a ratio of 8/2 (average benzene ring content 4
7% by weight) was dissolved in 66 parts of microhexanone, and then 60 parts of 7Erohost IR82132 (iron phosphide-based conductive pigment, manufactured by Hooker Chemicals and Plastics Scopo) and strontium chromate N (chromate pigment) were dissolved in 66 parts of microhexanone. , Suspension Water 1) H8-9, manufactured by Kikuchi Color Co., Ltd.) was added, and the steel peas were dispersed in a paint shaker for 2 hours. 15 parts of Ceridust 3620 (micronized polyethylene wax, manufactured by Hoechst) was added and mixed uniformly with a disperser to obtain a coating composition with a non-volatile content of 65% by weight.

実施例２〜６　ｄ３よび比較例１〜３ 実施例１と同様方法で、但し樹脂、導電顔料、リン生鉱
分解抑制剤、潤滑剤の種類と割合については第１表に示
した通りに変更し、各種Ｗ　Ｅ組成物を得た。Examples 2 to 6 d3 and Comparative Examples 1 to 3 The same method as in Example 1, except that the types and proportions of the resin, conductive pigment, phosphorite decomposition inhibitor, and lubricant were changed as shown in Table 1. Various WE compositions were obtained.

尚、第１表において イムシルＡ−１０８ アモルファスソフトシリカ １、ＬＬＩＮＯＩＳ’　ＭＩＮＥＲＡＬＳＣＯ０製 亜鉛末 塗料用亜鉛末 三井金属鉱業■社製 ＳＡＣ■　７００ 石油スルホネートのカルシウム塩と炭 酸カルシウムの混合物 Ｗｉｔｃｏ社製 ５ｉｃＯｒ　Ｚ　ｍｐ／　Ｓ リン酸亜鉛顔料 ＢＡＳＦ社製 ＶＵＬＣＡＮ　ＸＣ−７２Ｒ カーボンブラック キャボット社製 電気亜鉛ニッケル合金メッキ鋼板（目付１４０ｇ／ｌｌ
１２）をアルカリ脱脂し表面汚染物を除去後、水洗、乾
燥させ、クロメート液をロールコータ−でクロム付着＠
２００ｍｇ／ｍ２になる用に塗布後、乾燥させて予備処
理鋼板を作った。尚、クロメート液としては無水クロム
酸水溶液をホルマリンで還元しＣｌ−６”　／Ｃ＋−３
＋＝　７／３の総クロム２０Ｑ／ｅの液を調整し、アエ
ロジル３００（日本アエロジル社製、ヒユームドシリカ
）を１５　ｇ／ｅの濃度に添加し、ペイントシェーカー
で１時間ガラスピーズ分散した液を用いｌＣ０ 上記鋼板に各実施例ならびに比較例で得られた塗料組成
物（固形分６０％）をロールコータ−で、乾燥膜厚５μ
となるように塗布し、板温最高到達温度が２００℃にな
るよう６０秒間直接熱民ガス炉で焼付し、冷却して試験
片を作った。各試験片を用い下記のごとき実験を行ない
性能評価し、それらの結果を第２表に示した。In addition, in Table 1, IMUSIL A-108 Amorphous Soft Silica 1, LLINOIS' MINERALSCO0 Zinc powder for paint Zinc powder manufactured by Mitsui Mining Co., Ltd. SAC■ 700 Mixture of calcium salt of petroleum sulfonate and calcium carbonate manufactured by Witco Co., Ltd. 5ic Or Z mp / S Zinc phosphate pigment BASF VULCAN
12) After removing surface contaminants by alkaline degreasing, washing with water, drying, and applying chromate solution using a roll coater to remove chromium adhesion @
After coating to a concentration of 200 mg/m2, it was dried to produce a pretreated steel plate. In addition, as a chromate solution, an aqueous chromic acid anhydride solution is reduced with formalin to obtain Cl-6''/C+-3.
+ = 7/3 total chromium 20Q/e solution was prepared, Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd., humid silica) was added to a concentration of 15 g/e, and glass beads were dispersed in a paint shaker for 1 hour. lC0 The coating compositions (solid content 60%) obtained in each example and comparative example were applied to the above steel plate using a roll coater to give a dry film thickness of 5 μm.
It was coated so that the plate temperature reached a maximum of 200°C, and baked directly in a hot gas oven for 60 seconds, and then cooled to prepare a test piece. The following experiments were conducted using each test piece to evaluate its performance, and the results are shown in Table 2.

試験方法及び評価基準 １、連続スポット溶接性 電極径５１ＩＩＩＩ１１加圧力２００ｋ（］、通電時間
１０サイクル、電流８０００Ａの条件でスポット溶接を
実施し、連続打点可能な打点数を調べた。Test method and evaluation criteria 1. Continuous spot welding. Spot welding was carried out under the conditions of electrode diameter 51III11 pressure 200 k (), energization time 10 cycles, and current 8000 A, and the number of continuous dots that could be made was investigated.

評ω）１ ◎：　５０００点以上　電極汚れ少ない○：　５０００
点以上　電極汚れ多い Δ：３０００点〜５００点点 ５０００点０点未満 ２、塗膜加工性 円筒深絞り試験器（エリクセン社製、モデルＢ１−１４
２型）を使用し、しわ押え圧３！・ン、ポンチ径５０ｍ
ｍφ、ダイス径５２．４１１１＋１１φ、絞り深さ４０
ｍｍ、ブランク径９５ｍｎ＋）Ｆ加工し、塗膜のキズ、
剥離を調べた。Review ω) 1 ◎: 5000 points or more Electrode dirt is low ○: 5000
point or more Electrode contamination Δ: 3000 points to 500 points 5000 points Less than 0 points 2, Coating film processability cylindrical deep drawing tester (manufactured by Eriksen, model B1-14
2 type), the wrinkle presser pressure is 3!・Punch diameter 50m
mφ, die diameter 52.4111+11φ, drawing depth 40
mm, blank diameter 95mm +)F processing, scratches on the paint film,
Checked for peeling.

評価 ◎：塗面異常なし ○：塗面キズ（素地金属未到達）有り （１０％以下） △：素地金属に達するキズ有り、また、塗面キズ多い ×：原板ワレ ３、耐食性 ■複合腐食試験（１ザイクルー塩水＠霧（５％賜Ｃ１，
３５℃）、２時間→乾燥（（３０’Ｃ）、２時間→湿潤
（９８％ＲＨ≦、５０℃）４時間２００ザイクル後の平
面部の赤す−ピ、白ザビの発生状態を調べた。Evaluation: ◎: No abnormality on the painted surface ○: There are scratches on the painted surface (not reaching the base metal) (10% or less) △: There are scratches that reach the base metal, and there are many scratches on the painted surface ×: Original plate cracking 3, corrosion resistance ■ Combined corrosion test (1xycru salt water @ fog (5% give C1,
35℃), 2 hours → drying ((30'C), 2 hours → wet (98%RH≦, 50℃), 4 hours and 200 cycles, and then the occurrence of red and white rust on the flat surface was investigated. .

評価 ◎：白サビ、赤９ビ発生なし Ｏ：白サビ発生面積５％以下、赤ナビなし入：　６％以
上、〃 ×：赤サビす％以上発生 ■塩水噴霧試験（ＪＩＳ−２２３７１に準ず）２０００
時間後の平面部の赤サビ、白サビの発生状態を調べた。Evaluation: ◎: No white rust, no red rust O: 5% or less of white rust, no red rust: 6% or more, ×: % or more of red rust ■Salt spray test (according to JIS-22371) 2000
After some time, the state of red rust and white rust on the flat surface was examined.

評価 ◎：白サビ、赤サビ発生なし ○：白サす発生面積５％以下、赤サビなし△：　６％以
上、 ×：赤ナビ１％以上発生Evaluation: ◎: No white rust or red rust ○: White rust occurs on 5% or less of the area, no red rust △: 6% or more, ×: 1% or more of red rust occurs

Claims (7)

【特許請求の範囲】[Claims] （１）塗料固形分として （Ａ）芳香族環を含まぬかあるいはその含有率が最大限
５０重量％までの少なくとも１種の塗料用樹脂　１０〜
３５重量％ （Ｂ）有機潤滑剤　４〜３０重量％ （Ｃ）リン化鉄主成分の導電顔料 １５〜８５重量％ （Ｄ）リン化鉄分解抑制剤　１〜７１重量％（Ｅ）その
他の無奢幾顔１′３１　０〜７０重量％を含み、（Ｃ）
、（Ｄ）および（Ｅ）の総量が塗料固形分中３５〜８６
重量％であることを特徴とする金属材プレコート用塗料
組成物。(1) At least one resin for paint that does not contain aromatic rings or whose content is up to 50% by weight (A) as paint solid content 10~
35% by weight (B) Organic lubricant 4 to 30% by weight (C) Conductive pigment mainly composed of iron phosphide 15 to 85% by weight (D) Iron phosphide decomposition inhibitor 1 to 71% by weight (E) Other additives Deluxe face 1'31 Contains 0 to 70% by weight, (C)
, (D) and (E) in the solid content of the paint.
% by weight. （２）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、フェノール樹
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
ン樹脂である特許請求の範囲第１項記載の組成物。(2) Paint resins include epoxy resins, alkyd resins, acrylic resins, melamine resins, urethane resins, phenolic resins, vinyl resins, polyvinyl butyral resins, polyvinyl acetate resins, chlorinated rubber, oil-free polyester resins, and phthalate resins. The composition according to claim 1, which is a styrene resin or a polyolefin resin. （３）有機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項記載の組成物。(3) The composition according to claim 1, wherein the organic lubricant is a compound selected from polyolefin compounds, carboxylic acid ester compounds, and polyalkylene compounds. （４）有機潤滑剤が３００〜５００℃で発熱的分解を示
す化合物である特許請求の範囲第３項記載の組成物。(4) The composition according to claim 3, wherein the organic lubricant is a compound that exhibits exothermic decomposition at 300 to 500°C. （５）リン化鉄分解抑制剤がｐｔ−１６〜１３の懸濁ｐ
１−１を示す顔料である特許請求の範囲第Ｉ　ＩＪｌｉ
ｉ記載の組成物。(5) Iron phosphide decomposition inhibitor is a suspension of pt-16 to pt-13
Claim I IJli which is a pigment showing 1-1
The composition according to i. （６）その伯の無機顔料がクロム顔料、リン酸塩顔料、
鉛顔料あるいは着色顔料である特許請求の範囲第１項記
載の組成物。(6) The most important inorganic pigments are chromium pigments, phosphate pigments,
The composition according to claim 1, which is a lead pigment or a colored pigment. （７）導電顔料、リン化鉄分解抑制剤およびその他の無
機顔料の合計量が塗料固形分中３５〜７０重量％である
特許請求の範囲第１項記載の組成物。(7) The composition according to claim 1, wherein the total amount of the conductive pigment, iron phosphide decomposition inhibitor, and other inorganic pigments is 35 to 70% by weight based on the solid content of the paint.