JPS5951958A - Cationic electrodeposition paint composition - Google Patents

Abstract

PURPOSE:To provide a cationic electrodeposition paint compsn. which has excellent uniformity of coating film and high throwing power, containing a specified quantity of fine carbon powder and a water-dilutable resin having basic groups as its main vehicle. CONSTITUTION:A cationic electrodeposition paint compsn. contains 8-50wt%, pref. 15-30wt% (based on the total quantity of solids) fine carbon powder and a water-dilutable resin contg. basic groups as its main vehicle. Examples of fine carbon powders are carbon black and graphite. When the quantity of the fine carbon powder is less than 8wt%, the electrical conductivity of a coating film is insufficient and the film of the second layer is not uniformly electrodeposited, while when the quantity exceeds 50wt%, the surface of the first layer is roughened and hence the finish of the second layer is unfavorably affected. As the main vehicle, a resin compsn. consisting of an amine-modified bisphenol A type epoxy resin and an at least partially blocked isocyanate compd. is preferred from the viewpoints of adhesion of coating, corrosion resistance, throwing power and stability with time.

Description

【発明の詳細な説明】 本発明は導電性塗膜を形成するカチオン電着塗料組成物
および該組成物を用いる電着塗装方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cationic electrodeposition coating composition for forming a conductive coating film and an electrodeposition coating method using the composition.

従来より金属被塗物１に導電性塗膜を施し、その上に電
Ｓ塗装する方法については公知であり、例えば、特開昭
５０−１．５９３０号、特開昭５２−４７０７４号、特
開昭５３．−４００３５号、特開昭５３−９１９４号、
特開昭５３−１１５７５７号、および特開昭５５−５８
３９７号各公報等がみられるが、これらの導電性塗膜は
゛電着塗膜で（」ない。Conventionally, a method of applying a conductive coating film to a metal object 1 and then applying electrical conductive coating thereon has been known. 1973. -40035, JP-A No. 53-9194,
JP-A-53-115757 and JP-A-55-58
No. 397, etc., but these conductive coatings are not "electrodeposition coatings."

電着塗装法により金属被塗物上に一度析出した塗膜の上
に、更に第二層を電着塗装するととは、第一層塗膜が絶
縁体となるために、原理的に不ロ丁能であるとされてい
た。僅かに特公昭４９−２４５６６号公報に電１看［有
］装によるこのような二層電着の例がみられる。Applying a second layer by electrodeposition on top of a coating that has already been deposited on a metal object using the electrodeposition coating method is fundamentally safe because the first layer of coating becomes an insulator. It was said that he was a master of Ding Noh. There is a small example of such two-layer electrodeposition using an electronic device in Japanese Patent Publication No. 49-24566.

この特公昭４９−２４５６６号公報には微粉砕黒〔色順
イ、・（を木質的な成分としたアニオン型１北蕾塗櫃［
、阻成物を展色剤を用いて、金属被塗物りに導電性フィ
ルムを析出させ焼成した後、更に同じ展色剤７＝用いた
第２層目のアニオン型１睡着保Ｒｙｌ覆を形成させる方
法が示され、「黒「ム酸［ヒ鉄含有被覆物を含む物品は
、基質に対する密着力、導電性、表面特性、および耐食
性に関して顕著な性質を示した。」とある。This Japanese Patent Publication No. 49-24566 describes an anion type 1 north bud coating with woody components of finely pulverized black [color order I,...].
, a conductive film is deposited on the metal coating object using a color vehicle, and then fired, and then a second layer of anionic type 1-retainer Ryl is coated using the same color vehicle 7. ``Articles containing arsenate-containing coatings exhibited remarkable properties with respect to adhesion to substrates, electrical conductivity, surface properties, and corrosion resistance.''

特番こその５頁目には、導電性物質として黒色酸（シ鉄
に比ベカーボンブラックを含む被覆物は、電圧融通性、
外観、ａ蔽力更には耐塩水噴霧性について劣ると述べら
れている。On page 5 of the special program, it is stated that coatings containing carbon black as a conductive material (compared to iron) have voltage flexibility,
It is said that the appearance, shielding power, and salt spray resistance are inferior.

しかしながら、この黒σ３酸１′ヒ鉄を電着塗装用組成
物に用いた場合、産業上重大な欠点が確認された。However, when this 1' arsenate black sigma 3 acid was used in an electrodeposition coating composition, an industrially serious drawback was confirmed.

即ら、黒色酸化、鉄は比重が大きく、吸、ｒＪｌｌｒｔ
は小さい。しかも電着塗料は稀釈された水溶液（上記特
許公報中の実施例では固形物８重用％）の状態で使用さ
れるので、非常に沈降性が徴しく、被［有］物の形状が
複％Ｍトな場合、各部位への均一な塗膜の形成がなされ
ないこ止である。That is, black oxide, iron has a large specific gravity,
is small. Moreover, since the electrodeposition paint is used in the form of a diluted aqueous solution (in the examples in the above patent publication, the solid content is 8%), it is very prone to settling, and the shape of the object is 8%. In the case of M, it is impossible to form a uniform coating film on each part.

前記発明では、電着塗装法の最大の特徴である均一な膜
ｊｐとつきまわり性が得られない。丑だ、膜厚が不均一
なことから得られた塗膜の導電性も均一でなくなり、電
着塗装により導電性塗膜を形成した意味が全くなくなる
。In the above invention, it is not possible to obtain a uniform film and throwing power, which are the most important features of the electrodeposition coating method. Unfortunately, since the film thickness is not uniform, the conductivity of the resulting paint film is also not uniform, and there is no point in forming a conductive paint film by electrodeposition.

また、上記組成物による被塗装物の耐食性についても心
丈しも満足すべき水準ζこ達していない。Furthermore, the corrosion resistance of the coated objects provided by the above composition has not yet reached a satisfactory level.

本発明者は、上記欠点を解決し、更に実用性の高いもの
番こするために、鋭意研究した結果、アニオン型ではな
くカチオン型這着塗料組成物と微粉炭素を組み合わせる
と庵めて優れた塗膜均一性および７１−ロいついまわり
性が得られることを見出した。In order to solve the above-mentioned drawbacks and create a more practical product, the present inventor conducted extensive research and found that the combination of a cationic type adhesion coating composition, rather than an anionic type, and finely divided carbon was found to be superior. It has been found that coating film uniformity and 71-Ro stability can be obtained.

即ち、本発明は総固形分念用の８〜５０重量％の微粉炭
素および主展１′ハ剤として塩基性基金ｆ１水稀釈性園
指を含汀するカチオン型□七看塗料組成物に関する。ま
た、本発明は上記カチオン型電着塗月７阻成物を用いて
金属被塗物上に電１着顔装しり゛ム成して第１題の膜を
形成させ、該塗膜上に更に電着塗装により第２層重着塗
膜を形成させる塗装法に関する。That is, the present invention relates to a cationic paint composition containing 8 to 50% by weight of total solids finely divided carbon and a basic foundation f1 water-dilutable toxin as the main additive. Further, the present invention uses the above-mentioned cationic electrodeposition coating 7 inhibitor to form an electrodeposition coating film on a metal object to form the film of the first subject, and The present invention further relates to a coating method for forming a second layer overlapping coating film by electrodeposition coating.

本発明（こ用いる微粉炭素はカーボングラツクおよびク
ラファイトが例示される。カーボンブランクはサーマル
ブラック法、アセチレンブラック法。The fine carbon used in the present invention is exemplified by carbon graphite and graphite.The carbon blank is produced by the thermal black method and the acetylene black method.

チャネ少、去、ファーネス法、ランプブラックｌ去その
、−出の製ｌ去１こよりゴ待ス告される。微λ分灰累（
よその分散性と電着塗膜のタ闘、現仕上り性の点から吸
／ｌＩＩ附４５〜ｌ　ｌ　５ｙｔｅ／　ｌ　００　Ｆ／
、粒子径１５〜８５ｒｎαのものが好ましい。From the beginning of the channel, to the furnace process, to the production of lamp black, to the production of lamp black. Differential λ minute gray accumulation (
In view of the battle between other dispersion properties and electrodeposited coatings, and the current finish, the adhesion/lII approx. 45~l 5yte/l 00 F/
, particles having a particle size of 15 to 85rnα are preferable.

微粉炭素の含有量は８〜５０重歇％、より好ましくは１
５〜３０重滑％である。含有量が８重用％より少なくな
ると塗膜の導電性が不十分（こなり、第２層の電着塗膜
が均一に析出しない。また、５０重量・杉より多いと第
１層の電着塗面暑こ肌荒れを生じ、第２層の仕上りにも
悪影ａを学える結果となり好ましくない。本発明では所
望により微粒の金属粉末を配合することもできる。The content of fine carbon is 8 to 50%, more preferably 1
It is 5 to 30 percent smooth. If the content is less than 8% by weight, the conductivity of the coating film will be insufficient (coiling, and the second layer electrodeposited coating will not be deposited uniformly. Also, if the content is more than 50% by weight, the first layer electrodeposition will be poor). This is undesirable since the coated surface becomes hot and rough, and the finish of the second layer is also affected by the adverse effect a.In the present invention, fine metal powder may be added if desired.

この場合、耐食性を更に向上させるため（こ鉛系化合物
、例えばケイ酸鉛、クロム酸鉛、酢酸鉛でｔだは乳酸鉛
を添加するのが好ましい。In this case, in order to further improve the corrosion resistance, it is preferable to add a lead-based compound such as lead silicate, lead chromate, lead acetate, or lead lactate.

捷だ、通常の他の添加剤、例えばノニオン活性剤、カチ
オン活性剤、消泡剤および顔ポ・１等を配合してもよい
。However, other conventional additives such as nonionic activators, cationic activators, antifoaming agents, and other additives may also be included.

微′６）炭素は通常の分散用樹脂で分散して用いるのが
好丑しい。この分散に用いる樹脂は分散性および安定性
の点から第４級アンモニウム塩基含有樹脂が好ましい。6) It is preferable to use carbon by dispersing it with a common dispersing resin. The resin used for this dispersion is preferably a quaternary ammonium base-containing resin from the viewpoint of dispersibility and stability.

第１　／＠のカチオン電着塗膜に用いる主展芭剤として
は、通常のカチオン性樹脂５が使用可能である。As the main spreading agent used in the first cationic electrodeposition coating film, a common cationic resin 5 can be used.

例えば、特公昭４８−５１９ｊ４号公報１杷桟のアミン
変性ビスフェノールＡ型エポキシ樹脂のウレタン硬化系
、特公昭５３−４７１４３号公報のオニウム塩基含有樹
１指系、特公昭４９−２５４２２号公報のアクリル・ビ
ニル重合樹脂系および特開昭５３＝１６０４８号公報の
ポリブタジェン系等が皐げられる。For example, the urethane-curing system of amine-modified bisphenol A type epoxy resin disclosed in Japanese Patent Publication No. 48-519j4, the urethane-curing system of amine-modified bisphenol A epoxy resin disclosed in Japanese Patent Publication No. 1982-47143, the acrylic resin system containing onium base in Japanese Patent Publication No. 53-47143, and the acrylic resin disclosed in Japanese Patent Publication No. 49-25422. - Vinyl polymer resin systems and the polybutadiene system disclosed in JP-A-53-16048 are used.

しかし、塗膜密着性、耐食性、つきまわり性および経時
安定性の点から、現在最も実用化されているアミン変性
ビスフェノールＡ型エボギシ樹脂化合物と少なくとも一
部ブロック化されたポリイソシアネート化合物、とから
なる樹脂Ｊｉ■成物が好ましい。However, from the viewpoint of coating adhesion, corrosion resistance, throwing power, and stability over time, it is made of an amine-modified bisphenol A type epoxy resin compound, which is currently the most practically used, and a polyisocyanate compound that is at least partially blocked. Preference is given to resin compositions.

本発明に用いる樹脂成分は目的に応じて曲の樹脂成分や
塗料原料等、例えばアミン樹脂、フェノール樹脂、ポリ
アミド類、ポリエーテル類、ポリエステル類等で更に変
性するか、あるいはこれらの成分と適宜混合してもよい
。Depending on the purpose, the resin component used in the present invention may be further modified with a song resin component, a paint raw material, etc., such as amine resin, phenol resin, polyamides, polyethers, polyesters, etc., or may be mixed with these components as appropriate. You may.

驚くべきことに、本発明の塗料組成物はかなり多量の導
電性微粉炭素を配合しているにもかかわらす、電着塗装
時（こは導電性はあまり示さず、逆にかなりの膜抵抗を
示し、つきまわり性は低■しないのである。しかも、こ
の電着塗膜を焼成すると導電性が得られる。Surprisingly, although the coating composition of the present invention contains a fairly large amount of conductive finely divided carbon, it does not exhibit much conductivity during electrodeposition coating, and on the contrary exhibits considerable film resistance. The electrodeposited coating film exhibits good conductivity and does not have low throwing power.Furthermore, when this electrodeposited coating film is fired, it becomes conductive.

従って、未焼成の塗膜上に第２層を電着塗装しようとし
てもほとんど塗膜の析出は認められず、第１層塗膜を焼
成すると第２層を電着することが可能になる。Therefore, even if an attempt is made to electrodeposit the second layer on the unfired paint film, almost no deposition of the paint film is observed, and it becomes possible to electrodeposit the second layer by firing the first layer paint film.

この理論的解明は必ずしも充分ではないが、焼成により
未乾燥塗膜中に含有される水分−や有機溶剤が飛散（、
て金属被塗物および微粉炭素の密着性がよくなり導電性
が得られるものと思われる。充分な導電性を示すには、
１００〜２５０°Ｃで１０〜３０分間焼き付けることが
適当である。Although this theoretical elucidation is not necessarily sufficient, the moisture and organic solvents contained in the undried coating film are scattered (,
It is thought that this improves the adhesion between the metal coating object and the finely divided carbon, resulting in conductivity. To exhibit sufficient conductivity,
It is appropriate to bake at 100-250°C for 10-30 minutes.

第２層目の電着′に用いる塗料は、アニオン型、カチオ
ン型にかかわらず使用１打能であるが、アニオン型の場
合、金属被塗物に直接塗装したものに比べｊ硬化性が低
下する傾向がみられる点と耐食性の点よりカチオン型の
方が好ましい。The paint used for the second layer electrodeposition has a one-stroke performance regardless of whether it is an anionic or cationic type, but in the case of anionic type, the curing properties are lower than those applied directly to the metal object. The cationic type is preferable in terms of its tendency to oxidize and its corrosion resistance.

また第２層目の電石塗犯１の樹脂系としてアクリル系の
物を選ぶことにより、例えば下層エポキシ系、上層アク
リル系という耐食性耐候性ともに優れた理想的な２居直
着塗膜が得られる。In addition, by selecting an acrylic resin as the resin system for the second layer, electrified coating material 1, an ideal two-layer direct-adhesive coating film with excellent corrosion resistance and weather resistance, for example, an epoxy-based lower layer and an acrylic-based upper layer, can be obtained. .

金属被塗物としては綱アルミニウム、銅−ングネシウム
等に塗装可能であるばかりでなく亜鉛メッキ銅扱のよう
な表面処理銅板およびそれらの複合材−〇にも適用され
る。As for metal objects to be coated, it can be applied not only to steel aluminum, copper-gnesium, etc., but also to surface-treated copper plates such as galvanized copper, and composite materials thereof.

以上のように本発明による２層重着塗装を実施すること
により、次のような格別の効果が見し）出せる。By carrying out the two-layer coating according to the present invention as described above, the following special effects can be obtained.

Ｃ１）　　沈降性が少なく、高つきまわり性を有する。C1) It has low sedimentation and high throwing power.

従って複雑な形状のものでも均一な導電性塗膜を形成す
るので、均一な２層重着塗装が可能である。Therefore, a uniform conductive coating film is formed even when the shape is complicated, so that uniform two-layer coating is possible.

（２）電着塗装だけで高膜厚が得られる。例えば回動車
ボディの塗装における現在の３コート塗装系の中塗りの
省略が可、指になり、省力化、低公害ＩＬ、性能向上が
期待できる。(2) A high film thickness can be obtained only by electrodeposition coating. For example, it is possible to omit the intermediate coating of the current 3-coat paint system when painting the body of a rotating car, and it is possible to save labor, reduce pollution, and improve performance.

（３）第１層目と第２層目で異った機能を有する市青塗
（１を選ぶことができる。例えば１耐陰性のよいエポキ
シ系を下層に、耐候性のよいアクＩＪ　）し系を上層に
というような好ましい２層塗膜の形成〃；可能である。(3) Ichi blue coating with different functions for the first and second layers (you can choose 1. For example, 1 is an epoxy system with good shade resistance as the lower layer and Aku IJ with good weather resistance). Formation of a preferred two-layer coating with the system as an upper layer is possible.

（４）　　第１層目の単独膜だけでも、導電性を持たな
いｌ一般の電着塗膜に比べてａ色のない高耐食性、高つ
き１わり性を有しているヒに、２層目の電着で膜厚が増
加し、更に耐食性が向上する。特にエツジ部のカバーリ
ングが良くなり、エツジ部からの腐食が抑えられる。(4) The first layer alone has high corrosion resistance without a color and is less expensive than ordinary electrodeposited coatings, which do not have conductivity. Electrodeposition of the eyes increases the film thickness and further improves corrosion resistance. In particular, the covering of the edges is improved, and corrosion from the edges is suppressed.

次に実施例及び比較例・２挙げ本発明をさらに詳しく説
明する。Next, the present invention will be explained in more detail by giving two examples and comparative examples.

〔試剪［の調精〕[Preparation of trial pruning]

（１）アニオン型展色樹脂■（比較例に使用）特公昭４
９−２４５６６号公報の実施例１の記載と同様の方法で
、約１５重、＠％無水マレイン酸により変性された亜麻
ｆ二油から作ったマレイン酸化乾性油’ｔ！Ｉ　ｉ指６
５２．８ｆを１１１　ｍｌの（２９％）水酸１ヒアンモ
ニウムｚ１４５　ｖｔｌのｎ−ブトキシェタノール°お
よび脱イオン水３６．６　ｍｌと配合し、固形分７０％
、ｐＩ−１７，３の長色樹脂を調叫した。(1) Anion type color exhibiting resin ■ (used for comparative example) Special Publication Showa 4
A maleated drying oil made from flax oil modified with about 15% maleic anhydride in a manner similar to that described in Example 1 of Publication No. 9-24566. I i finger 6
52.8f was combined with 111 ml (29%) of 145 vtl of n-butoxycetanol° and 36.6 ml of deionized water to give a solids content of 70%.
, a long-color resin with pI-17.3 was synthesized.

（２）主展色樹脂■ 適当な反応容器にＥＰＯＮｌｏｏｌ［ビスフエノールの
ポリグリシジルエーテル（エポキシ当匿５　Ｑ　８）シ
ｘ　ｔｖ−ケミカル・カンパ＝　−（Ｓｈｅｌｌ　Ｃｈ
ｅｍｉｃａｌＣａｍｐ　ａ　ｎγ）市販品３９７０重量
部およびポリカブロラクトンジオール（商品名Ｐ　Ｃ，
、夕２００　、ユニオン・カーバ、イドーコーボレイシ
ョン（Ｕｎｉｏｎ　Ｃａｒ−ｂｉｄｅ　Ｃｏｒｐｏｒａ
　ｔ　１ｏｎ）市萌品）２６５重量部を仕込んで作る。(2) Main color resin■ Into a suitable reaction vessel, add EPONlool [polyglycidyl ether of bisphenol (epoxy compound 5 Q 8) x tv-chemical campa = -(Shell Ch
3,970 parts by weight of a commercial product and polycabrolactone diol (trade name P C,
, Evening 200, Union Car-bide Corpora
t 1on) Ichimoe product) 265 parts by weight.

この生成物はエチレングリコールによるε−カグロラク
トンの開環で生成する分子置部Ｊ　５４　Ｊのポリマー
と考えられている。この仕込み物を窒素雰囲気下で１０
０°Ｃｊこ加熱しベンジルジメチルアミ２０．４６重量
部を添加する。この反１５混合物をさらに［３０°Ｃｉ
こＩＪＩＩ熱し約１時間半休ってから１１０°Ｃｉｃ　
Ｆ’；　却しメチルイ゛ノブチルケトン１１０重計部を
反応容器へ導入し、ケトオキシム（メチルイソブチルケ
トンとジエチレントリアミンをインブチルケトン溶１県
中で反応させて作る）の７３％不運定性ｒ’Ｅｒ′ｖ、
３９．８重里部を加え、さらにメチルイソブチルケトン
１００重量部を加える。This product is believed to be a polymer of molecular moiety J 54 J formed by ring opening of ε-caglolactone with ethylene glycol. This charge was heated under nitrogen atmosphere for 10
The mixture was heated to 0°C and 20.46 parts by weight of benzyldimethylamine was added. This anti-15 mixture was further heated at [30°Ci
It got hot and after resting for about an hour and a half, it reached 110°Cic.
F'; 110 weight parts of methyl isobutyl ketone were then introduced into the reaction vessel, and 73% unfavorable r'Er'v of ketoxime (made by reacting methyl isobutyl ketone and diethylene triamine in a solution of imbutyl ketone) was obtained. ,
Add 39.8 parts by weight and further add 100 parts by weight of methyl isobutyl ketone.

これを７０°Ｃまで冷却しジエチルアミン５３．１ｆｆ
ｉ＠部を導入し１２０”ｃｉこ再加熱し３時間保持した
後取り出す。Cool this to 70°C and add 53.1ff of diethylamine.
The i@ part was introduced, reheated to 120" ci, held for 3 hours, and then taken out.

上述のポリカプロラクトンジオール連鎖延長ポリエボギ
シド５７６重量部をボリウレｌン架橋剤３１０重Ｍｇｌ
とジグチル錫ジラウレート触媒１３．２重計部（こ混合
し、氷酢酸１２．３重量部で中和（−次いで樹脂固形分
４０％の分散液を作るに十分な竜の脱イオン水で希釈す
る。576 parts by weight of the above-mentioned polycaprolactone diol chain-extended polyebogide was mixed with 310 parts by weight of polyurethane crosslinking agent.
and 13.2 parts by weight of digyltin dilaurate catalyst, neutralized with 12.3 parts by weight of glacial acetic acid, and then diluted with enough deionized water to make a 40% resin solids dispersion. .

、ボリウレメン架橋剤は反応温度を外部冷却により（３
８°Ｃ）程度番こ保しながら２−エチルヘキサノール２
１８重量部を乾燥窒素雰囲気下で攪拌しながら２．４−
７２．６−　）ルエンジイソシアネート（８０／２０の
異性体混合物）２９１重量部へゆっくりと加えて作る。, the polyuremene crosslinker was prepared by lowering the reaction temperature by external cooling (3
8°C) Add 2-ethylhexanol 2 while maintaining
While stirring 18 parts by weight under a dry nitrogen atmosphere, 2.4-
72.6-) Prepared by slowly adding to 291 parts by weight of luene diisocyanate (80/20 isomer mixture).

仕込み物を（３８°Ｃ）にさらに３０分間保ってから（
６０°Ｃ）に加熱し、トリメヂロールプロパン７５重量
部を加え次にジブチル錫ジラウレート触媒００８重量部
を加える。初期の発熱後、赤外吸収走査で調べて実質と
すべてのインシアネート部分が消費されるまで内容物を
（１２１°Ｃ）で約１時間半休つ。この内容物をエチレ
ングリコールモノエチルエーテル２１９重量部で希釈す
る。Keep the mixture at (38°C) for a further 30 minutes and then (
60° C.) and add 75 parts by weight of trimedylolpropane followed by 0.08 parts by weight of dibutyltin dilaurate catalyst. After the initial exotherm, the contents are allowed to rest at (121° C.) for approximately one and a half hours until substantial and all incyanate moieties are consumed as determined by infrared absorption scanning. The contents are diluted with 219 parts by weight of ethylene glycol monoethyl ether.

（３）顔狗分１枚用樹脂○ 顔わ１分散用樹脂を次の処方で調製する。(3) Resin for one face dog ○ A resin for facial wrinkle dispersion is prepared according to the following formulation.

成　分　　　　　　　　　　　　重量部゛　固形分Ｉら
Ｐ　ＯＮ　８２９　　　　　　　　　　　　　　７１０
．０　　６８１．２ビスフエノールＡ　　　　　　　　
　　　２８９．６　２８９．６メチルイソグチルケトン
希釈　　　　　　４０６．４　　３８６゜１２−エチル
ヘキサノール半ギャップ 化トルエンジインシアネ〜ト ４級化剤ＣＩ）　　　　　　　　　　　４９６．３　４
２１．９脱イオン水　　　　　　　　　　７１．２　　
−グチルセロソルブ　　　　　　　５６７．６　　　−
（ａ）次の処方で作るイ１機第３級アミノ酸慝。Ingredients Weight parts゛ Solid content I et al.P ON 829 710
．． 0 681.2 Bisphenol A
289.6 289.6 Methyl isobutyl ketone dilution 406.4 386゜12-ethylhexanol semi-gapped toluenediin cyanate quaternizing agent CI) 496.3 4
21.9 Deionized water 71.2
-Gutyl cellosolve 567.6-
(a) One tertiary amino acid made using the following recipe.

成　分　　　　　　　　　　　重量部　固形分メチルエ
チルケトン稀υぐ２−エチル　３２０．０　３０４ヘキ
サノール半キヤツグ化トルエン ジインシアネート ジメチルエタノールアミン　　　　　　　８７．２　　
８７．’２乳酸７す（溶液　　　　　　　　　　１１７
．６　　８８・２ブチルセロソルブ　　　　　　　　　
　　３９．２　　　−２−エチルヘキサノール半ギャッ
プ化ジイソシアネートを室温で適当な反応容器中のジメ
チルエタノールアミンに加える。混合物は発熱する。こ
れを８０°Ｃで１時間攪拌する。乳酸を仕込み、グチル
セロソルブを加える。反応混合物を６５°ＣてＪ’（Ｊ
１時間攪拌し所望の４級ｆし剤を作る。Ingredients Parts by weight Solid content Methyl ethyl ketone diluted 2-ethyl 320.0 304 Hexanol semi-capped toluene diincyanate dimethylethanolamine 87.2
87. '2 lactic acid 7s (solution 117
．． 6 88.2-butyl cellosolve
39.2 Add the -2-ethylhexanol half-gapped diisocyanate to dimethylethanolamine in a suitable reaction vessel at room temperature. The mixture becomes exothermic. This is stirred at 80°C for 1 hour. Prepare lactic acid and add gutyl cellosolve. The reaction mixture was heated at 65°C to J' (J
Stir for 1 hour to prepare the desired quaternary flossing agent.

順相分散用樹脂を作るためにＥ　Ｐ　ＯＮ　８２９とビ
スフェノールＡを窒素雰囲気下で適当な反応容器に仕込
み、１５０〜１６０°Ｃに加熱すると発熱しはじめる。In order to produce a normal phase dispersion resin, E P ON 829 and bisphenol A are charged into a suitable reaction vessel under a nitrogen atmosphere, and when heated to 150-160°C, heat begins to be generated.

１反応混合物を１時間発熱させてから１２０°Ｃまで冷
却し、２−エチルヘキサノール半ギャッグ化トルエンジ
イソシアネートを加える。1. The reaction mixture is allowed to exotherm for 1 hour, then cooled to 120°C and 2-ethylhexanol semi-gagged toluene diisocyanate is added.

反応混ｊ）物を１１０〜１２０°Ｃて１時間保ぢ、グチ
ルセロソルブを加える。反応混合物を８５〜９０°Ｃま
て冷却し、均一化して水を加えてから４級化剤を添加す
る。酸ｆｌｌｌｌ　ン外ｌになるまで反応混合物の温［
Ｗを８５°Ｃに保つ。j) Keep the reaction mixture at 110-120°C for 1 hour and add glythyl cellosolve. The reaction mixture is cooled to 85-90°C, homogenized and water is added before the quaternizing agent is added. The temperature of the reaction mixture was increased until the acid was completely absorbed.
Keep W at 85°C.

（４）黒色ペースト０ 成　分　　　　　　　　　　　　　　重量部り配顔ｒ１
分散用樹脂◎　　　　　　　　７１．４脱イオン水　　
　　　　　　　　　２０３・６カーボンプラツク　　　
　　　　　　　１００．０上記成分に平均径２ｔｔｔｍ
の〃ラスビーズを３７５重川重用加して混合し、２時間
分散して粒子径１５μにした。その後ガラスピーズを沖
過してとり除き、黒色ペーストＯを得た。(4) Black paste 0 Ingredients Weight part Face arrangement r1
Dispersion resin◎ 71.4 Deionized water
203.6 carbon plaque
100.0 The above components have an average diameter of 2tttm
375 ml of russian beads were added and mixed, and dispersed for 2 hours to give a particle size of 15 μm. Thereafter, the glass beads were removed by filtration to obtain black paste O.

（５）黒色ペースト■ 成　分　　　　　　　　　　　　　　重量部上記）預料
分散用・ｆｔυ脂Ｑ　　　　　　　　　７１．４脱イオ
ン水　　　　　　　　　　　　　　２０３．６カーボン
フ゛ラツク　　　　　　　　　　９０．０ケイ酸錯　　
　　　　　　　　　　　　１０．０上記成分２（４）さ
同様に処理して黒色ペーストのを得た。(5) Black paste ■ Ingredients Parts by weight Above) For deposit dispersion/ftυ fat Q 71.4 Deionized water 203.6 Carbon flakes 90.0 Silicic acid complex
10.0 A black paste was obtained by processing in the same manner as in component 2 (4) above.

（６）白色ペースト■ 成　分　　　　　　　　　　　　　　重量部上記順軒１
分散用、樹脂Ｏ７１，４ 脱イオン水　　　　　　　　　　　　　　２０３．６二
酸化チタン　　　　　　　　　　　　５ｏ・０ケイ酸ア
ルミ　　　　　　　　　　　　　４０．０ケイ酸：Ｃ：
’１　　　　　　　　　　　、　　　１０．０上記成分
を（４）と同様に処理して白色ペースト■を得た。(6) White paste ■ Ingredients Part by weight Junken 1 above
For dispersion, resin O71.4 Deionized water 203.6 Titanium dioxide 5o.0 Aluminum silicate 40.0 Silicic acid: C:
'1, 10.0 The above components were treated in the same manner as in (4) to obtain a white paste (■).

（７）白色電着塗料Ｏ 成　分　　　　　　　　　　　　　重量部上記主展色樹
脂ｏ　　　　　　　　　　３５０．０上記白色ペースト
［Ｆ］　　　　　　　　　１５０．０脱イオン水　　　
　　　　　　　　１５０．０．０−上記樹脂■とペース
ト■を混合した後ゆるやかにかきまぜながら脱イオン水
を徐々に添加して固形分２０％、ｐｌ−１６，４の白色
塗料を得た。(7) White electrodeposition paint O Ingredients Parts by weight Above main color resin O 350.0 Above white paste [F] 150.0 Deionized water
150.0.0 - After mixing the above resin (1) and paste (2), deionized water was gradually added while stirring gently to obtain a white paint having a solid content of 20% and a PL-16.4.

リン酸亜鉛処理鋼阪−ヒに、浴温２８°Ｃ５２００ＶＸ
３分の条件で電着し、１７５°ＣＸ２０分焼成して２０
μの良好な塗膜を得た。これを以後の実４例及び比較例
の第２層目の電着塗料として使用した。Zinc phosphate treated steel, bath temperature 28°C 5200VX
Electrodeposited for 3 minutes, baked at 175°C for 20 minutes,
A coating film with good μ was obtained. This was used as the second layer electrodeposition paint in the following four practical examples and comparative examples.

上表の配合計で〔試イＳＦの調製（７）〕と同様ｔこ処
理して総固形分中のカーボンブラックの含有−＠が１０
１〜４０重Ｍ・形の範囲の電着塗料β種を作製した。Using the total amount in the table above, the carbon black content in the total solid content was reduced to 10 by performing the same treatment as [Preparation of trial SF (7)].
Electrodeposition paint β types with a weight range of 1 to 40 weight M·type were prepared.

各々固形分１５％でＩ）　Ｉ−１は６．２〜６．６の間
であった。I) I-1 was between 6.2 and 6.6 at 15% solids in each case.

これらを用いて浴温２８°Ｃｔ’　ＩＪン酸亜鉛処理鋼
板の上に１５０〜２５０Ｖｘ３分の条件で電着し、１７
５°ＣＸ２０分焼成して各々２０μの第１層目の塗膜を
作った。Using these, electrodeposition was performed on a steel plate treated with zinc oxide at a bath temperature of 28° Ct' under conditions of 150 to 250 V x 3 minutes, and 17
The first coating film was baked at 5° C. for 20 minutes to form a 20 μm thick coating film.

先に調製した白色塗料◎を用いて第２層目の電（カット
部からのフクレ巾３＋り肩以下を合格とした。）上記の
結果からカーボンブラック含有硅の多い程導電性が良く
第２層目の塗膜が析出し易い傾向を示すが、多すぎると
肌荒れ及びの膜性能の低下がみられ、固形分中のカーボ
ンブラックの量は１５〜３０重層％が実用的であると判
断される。Using the previously prepared white paint ◎, conduct the second layer (a blistering width of 3 + shoulder or less from the cut part was considered acceptable).From the above results, the more silicon containing carbon black, the better the conductivity. The coating film tends to precipitate in the layers, but if it is too large, the surface becomes rough and the film performance deteriorates, so it is judged that the amount of carbon black in the solid content is practically 15 to 30%. Ru.

上記の中から実施例２（カーボンプランｆ　ｍ１５％）
を代表例としてとり上げ６種テストを実施した結果を下
記に示す。Example 2 from the above (carbon plan f m15%)
The results of six types of tests taken as a representative example are shown below.

（１）　　第１層目の膜厚を５μ、ｉｏμ、２０μに合
せ、その上に第２層目の電着を施した所、全て２０μの
膜が付８１］、され、第１１會１］の膜厚による差はみ
られなかった。(1) The thickness of the first layer was adjusted to 5μ, ioμ, and 20μ, and the second layer was electrodeposited on top of it, resulting in a 20μ film. No difference was observed depending on the film thickness.

（２）　　２００　Ｖ　ｘ　３分電着した後、水洗し焼
成することなく第２層１」の電着を施した所はとんど膜
の析出はみられなかった。(2) After electrodeposition at 200 V x 3 minutes, no film deposition was observed where the second layer 1'' was electrodeposited without washing with water or baking.

１５０°ＣＸ、ｌＯ分以上の条件で焼成した塗膜４１に
は２０μの膜が析出した◇ （３）　　２００　Ｖ　ｘ　３分（膜厚２０μの条件）
でフォードパ・１７′法ｌこよってつきまわり性を測定
した所、２１　ｃｍと良好な、結果を得た。A 20μ film was deposited on the coating film 41 baked under conditions of 150°CX and 1O minutes or more◇ (3) 200V x 3 minutes (film thickness 20μ conditions)
When the throwing power was measured using the Fordpa 17' method, a good result of 21 cm was obtained.

この卸は第２層１」用に作った白色塗料０のつきまわり
性と同等であった。This product had the same throwing power as the white paint 0 made for the second layer 1.

（４）■・７扱（第゛１図参照〕を作って電着した所、
垂直部（１）、水平部の上面（２）、および下面ｒ３）
の仕上り膜厚に差が７Ｓ＜良好であった。(4) ■・7 treatment (see Figure 1) was made and electrodeposited,
Vertical part (1), top surface (2) of horizontal part, and bottom surface r3)
The difference in finished film thickness was 7S<good.

またこの上に第２層目の電着を施したが各部位とも均一
で良好な塗膜を得た。Further, a second layer was electrodeposited on top of this, and a uniform and good coating film was obtained at each location.

（５）＋２０μ膜ｊｖ（１７５°Ｃｘ２分焼成）　（７
）　上ニアクリル／メラミン系アニオン型１宜岩塗料（
日本ペイント（朱製パワロン＃１０００）を塗装した所
間−焼成条件（１７０°Ｃ×３０分）でリン酸亜鉛処、
５里ｊ側板上に直接塗装した塗膜に比べ１便化性が低丁
した（ＭＩＢＫ−７ピングテスト不合格）。(5) +20μ film jv (baked at 175°C for 2 minutes) (7
) Upper acrylic/melamine-based anion type 1 Yiyan paint (
Areas painted with Nippon Paint (Vermilion Poweron #1000) - Zinc phosphate treatment under firing conditions (170°C x 30 minutes),
Compared to the coating film applied directly onto the side panel, the single layering property was lower (MIBK-7 ping test failed).

第２層目１こカチオン型電管塗利を用いた場合は硬化即
の低Ｆは認められなかった。When a single cationic tube coating was used for the second layer, no low F was observed immediately after curing.

（６）２層重管した塗膜（実施例２の塗膜２０μ＋白１
ジ塗料◎の塗膜２０μ計４０μ）の上に汎用メラミンア
ルキッド系上塗塗料３０μを塗布した塗装系の仕上りは
、白色塗料Ｏの単独膜（２０μ）の上（こ直接り塗りを
伶った２コート２ベーグ系（計５°″ハり明らか６′良
好であり中；、Ｆ利、（ｉイルフリーメラミンアルキッ
ド系）を間に入れた３コート３ベーク系（計８０μ）の
仕上り外観と同等であった。(6) Two-layered coating film (20μ coating film of Example 2 + 1 white layer)
The finish of a paint system in which 30μ of a general-purpose melamine alkyd-based top coat is applied on a 20μ film of Di-Paint◎ (total 40μ) is the same as that of a single film (20μ) of white paint The finished appearance is the same as that of the 3-coat 3-bake system (total of 80μ) with 2-coat 2-bake system (total of 5°'' and clear 6' good and medium;, F-resistance, (i-il-free melamine alkyd system)). Met.

〔実施例１３〕 成　分　　　　　　　　　　　　重量部上記主展色樹脂
（◎　　　　　　　　　５２５上記黒色ペースト■　　
　　　　　　２２５脱イオン水　　　　　　　　　　１
２５０だ 上記配合により電着塗料を作製し固形分１５％△ ｐｌ（６，４であった。[Example 13] Ingredients Parts by weight The above main color resin (◎ 525 The above black paste■
225 Deionized water 1
An electrodeposition paint was prepared using the above formulation and had a solid content of 15% Δpl (6.4).

以下各種テストの結果を示す。The results of various tests are shown below.

（１）　　Ｕン酸亜鉛処亜鋼板上に浴温２８°ＣＣ２０
０ＶＸ３分の条件で電着し、１７５”ＣＸ３分て焼成し
た後膜厚は２０μで塗面状態は良θｆてあった。(1) Bath temperature 28°C20 on zinc oxide treated zinc steel plate
After electrodeposition at 0VX for 3 minutes and baking at 175"CX for 3 minutes, the film thickness was 20μ and the coated surface condition was good θf.

この土に白「Ｌ電着塗料０を用いて第２層目の電着伶装
を施した所史に２０μの塗膜が析出し塗面も均一で良好
であった。A second layer of electrodeposition was applied to this soil using white L electrodeposition paint 0, and a coating film of 20 μm was deposited, and the coated surface was uniform and good.

１：２）上記塗膜の塩水噴霧試験を行った結果、第１層
゛心着塗膜（２０μ）のみて８００時間、２層重着塗膜
〔４０μ）で１２００時間合格であった。1:2) As a result of conducting a salt spray test on the above coating film, only the first layer (adhesive coating film (20μ)) passed for 800 hours, and the two-layer superposition coating film (40μ) passed for 1200 hours.

ｉ：３）　　Ｉ−７板を作って電着した所、垂直部（１
）、水平部の上［１ｉＣ２）及び下面（３）で仕上り膜
厚に大差なくこの上に第２層目の電着をしても、各部位
の膜厚に差なく良好であった。i:3) The vertical part (1
), there was no significant difference in the finished film thickness on the upper [1iC2) and lower surface (3) of the horizontal part, and even when the second layer was electrodeposited thereon, there was no difference in the film thickness at each part, and the result was good.

（４）　　’７オードパイプ法によるつきまわり性は２
００ＶＸ３分で２１　ｏｎと良好であった。(4) The throwing power according to the '7 ord pipe method is 2
00VX for 3 minutes was 21 on, which was good.

〔比較例１〕 成分　　　　　　重量部 主度色樹脂＠　　　　　　　　　　６９３．７５黒虐ベ
ースｌ＋　　　　　　　　　　５６．２５脱イオン水　
　　　　　　　　１２５０．０上記の配合量にカーボン
ブラックを加えて〔試、＋Ｓ＋の調製（７）〕と同様に
処理して、総固形分中のカーボンブラックの含有用が５
重量％の電着塗料を作製した。固形分８１１１Ｆｆ１４
％、ｐ　Ｉ−１は６．２であった。[Comparative Example 1] Ingredients Parts by weight Main color resin @ 693.75 Black brutality base l + 56.25 Deionized water
1250.0 Add carbon black to the above blending amount and process in the same manner as [Trial, Preparation of +S+ (7)] to reduce the carbon black content in the total solids to 5.
An electrodeposition paint of % by weight was prepared. Solid content 8111Ff14
%, p I-1 was 6.2.

これを用いて浴温２８°Ｃでリン酸亜鉛処理鋼板の上に
１５０〜２５０Ｖｘ、３分の条件で電着し、１７５”Ｃ
で２０分間焼成して膜厚２０μの第１層塗膜を形成した
。この第１層塗膜の仕上り外観は良好で耐５ＳＴ５ＱＱ
Ｈは合格であった。Using this, electrodeposition was carried out on a zinc phosphate treated steel plate at 150 to 250Vx for 3 minutes at a bath temperature of 28°C, and 175"C
This was baked for 20 minutes to form a first layer coating film with a thickness of 20 μm. The finished appearance of this first layer coating is good and it is 5ST5QQ resistant.
H passed.

次いで、先に調製した白色塗料を用いて２０μの第２層
塗膜を形成ｊ−だ。その外観はエツジ部等に僅かに析出
があり耐Ｓ　Ｓ　Ｔ　８Ｑ　Ｑ　Ｉ−１は不合格であっ
た。Next, a second layer coating film of 20 μm was formed using the white paint prepared earlier. As for its appearance, there was slight precipitation on the edges, etc., and it failed the SST 8Q Q I-1 test.

〔比較側御３〕 成分　　　　　　重量部 上記゛ｒユニオン展色樹脂の　　　　１６３．５微粉砕
黒１　酸化ｆａ　（０，５ｐ　）　　　　　　５１．０
６％ナフデン酸コバルト　　　　　　　０．７６％ナフ
テン酸マンガン　　　　　　　０７２４％ナフテン酸鉛
　　　　　　　　　５，９脱イオン水　　　　　　　　
　１８４９．５特公昭４９−２４５６６号公報の〔実施
例１〕に従い、上記の通りの自己合で塗料を作成し、固
形分８％、ｐＩ−１３，Ｑであった。しかし攪拌を１に
めると、微粉砕黒ｔハ酸化鉄が非常に沈澱しやすい性質
を示した。[Comparison side 3] Ingredients Parts by weight 163.5 Finely ground black 1 of the above ゛r Union colored resin 1 Oxidation fa (0.5p) 51.0
6% Cobalt naphdate 0.76% Manganese naphthenate 0724% Lead naphthenate 5,9 Deionized water
According to [Example 1] of 1849.5 Japanese Patent Publication No. 49-24566, a paint was prepared by self-assembly as described above, and the solid content was 8% and pI-13,Q. However, when the agitation was set to 1, the finely ground black t iron halide showed a tendency to precipitate very easily.

以下各種テストの結果を示す。The results of various tests are shown below.

（１）リン酸亜鉛処理鋼板−ヒに浴温２４°Ｃで５０Ｖ
×ｉ５０秒の条件で電着し、１５０°ｃＸ３０分焼成し
た塗膜の膜厚は２０μであり塗面状態は・や＼不均一で
あった。(1) Zinc phosphate treated steel plate - 50V at a bath temperature of 24°C
The thickness of the coating film, which was electrodeposited under the conditions of ×i50 seconds and baked at 150°C for 30 minutes, was 20μ, and the coated surface was somewhat non-uniform.

この上に先の実施例で用いた白色塗料Ｏを塗装した所、
更に２０μの塗膜が析出した。塗面状態も比較的均一で
良好であった。On top of this, the white paint O used in the previous example was painted,
A further 20 μm coating was deposited. The coating surface condition was also relatively uniform and good.

（２）上記塗膜の臨水噴霧試、験を行った結果、第１層
ｊｌｉ着塗膜（２０μ）（７）みでは２００時間、２層
′市着塗膜（４０μ）でも４００時間で不合格であった
。(2) As a result of the water spray test of the above coating film, it was found that the first layer (20μ) (7) failed in 200 hours, and the second layer (40μ) failed in 400 hours. I passed the exam.

（３）Ｌ学級を作って電着した所、垂直部（１）、水平
部の上面（２）、及び下面曙：３）で仕上り、膜厚番こ
大きな差がみられた。特に水平部の上面は黒色酸化鉄分
が多く、下面は少なく不均一であった。(3) When the L class was prepared and electrodeposited, the vertical part (1), the horizontal part (2), and the bottom surface (3) were finished, and a large difference in film thickness was observed. In particular, the upper surface of the horizontal part contained a large amount of black iron oxide, while the lower surface contained less and was uneven.

この上に第：２層目の電着りした所、仕上り膜厚ともに
不均一であった。When a second layer was electrodeposited on top of this, the finished film thickness was non-uniform.

（４）　　フォードパイプ法によるつきまわり性を測定
した所５　ｔ：ｍと非常に低かった。(4) The throwing power was measured by the Ford pipe method and was very low at 5 t:m.

〔比較例３〕 成分　　　　　重量部 上記°ｒユニオン展色樹脂の　　　２２８．６カーボン
ブラツク　　　　　　　　４０．０６％ナフテン酸コバ
ルト　　　　　　１．０６％ナフテン酸マンガン　　　
　　　１．０２４％ナフテン酸鉛　　　　　　　　８．
２脱イオン水　　　　　　　　１７２１．２上記配合に
より導’４性物質としてカーボンブラックを用いたアニ
オン電着塗料を作製した。固形分１０％、ｐ［−１８で
あった。以下各種アストの結果を示す。[Comparative Example 3] Ingredients Parts by weight 228.6 of the above °r Union colored resin Carbon black 40.06% Cobalt naphthenate 1.06% Manganese naphthenate
1.024% lead naphthenate 8.
2 Deionized water 1721.2 An anionic electrodeposition paint using carbon black as a conductive substance was prepared using the above formulation. Solid content was 10%, p[-18. The results of various types of asto are shown below.

（１）　　リン酸鉛処理ＷＩｔｒｉ上に浴温２４°Ｃで
、５０Ｖ×６０秒の条件で電着し１５０°Ｃ×３０分焼
成した塗膜の膜厚は１０μで塗面状態は均一で良好であ
った（しかし２０μの塗膜は肌荒れを生じた。）この上
に第２層目の白色塗料Ｑを塗装した所、更に２０μの塗
膜が析出″し塗面状態は均一で良好であった。(1) The coating film was electrodeposited on lead phosphate treated WItri at a bath temperature of 24°C under the conditions of 50V x 60 seconds and baked at 150°C for 30 minutes.The film thickness was 10μ and the coating surface was uniform and in good condition. (However, the 20μ coating caused surface roughness.) When the second layer of white paint Q was applied on top of this, an additional 20μ coating was deposited, and the coated surface was uniform and in good condition. Ta.

（２）上記塗膜の塩水噴霧試験を行った結果、第１層上
着塗膜（１０μ）のみでは１００時間、２層′市着塗膜
（３０μ）でも４００時間で不合格であった。(2) As a result of conducting a salt spray test on the above coating film, the first coat coat (10μ) alone failed after 100 hours, and the second layer's wet coat (30μ) failed after 400 hours.

（３）　　Ｉ−字板を作って電着した所垂直部（１）、
水平部の上面（２）及び下向（３）で仕上り、膜厚とも
に大差なかった。(3) Vertical part (1) where I-shaped plate was made and electrodeposited,
It was finished on the top surface (2) and the bottom surface (3) of the horizontal part, and there was no significant difference in film thickness.

またこの上（１０μ）に第２層目の電着をした所各部位
の差なく良好であった。Moreover, when a second layer was electrodeposited on top of this (10 μm), the results were good with no difference at each site.

（４）　　フォードパイプ法によるつきまわり性は５Ｃ
ｍと非常に低かった。(4) Throwing performance by Ford pipe method is 5C
m, which was very low.

【図面の簡単な説明】[Brief explanation of drawings]

第１図はＬ学級の斜視図である。 図中、（１）・・・垂直部、　（２）・・水平部上面、
　（３）・・・水平部下面、　（４）・・・塗材上面を
表わす。 停止図FIG. 1 is a perspective view of the L class. In the figure, (1)...vertical part, (2)...horizontal part top surface,
(3)...Represents the horizontal lower surface, (4)...Represents the upper surface of the coating material. stop diagram

Claims (1)

【特許請求の範囲】 １、総固形分含量の８〜５０重量％の微粉炭素および主
展色剤として塩基′性基含有水稀釈性樹脂を含イコする
ことを特徴とするカチオン型七看塗相７阻成物。 ２、微粉炭素を総固形分含量の１５〜３０重量・形含有
する第１項記載の組成物。 ３、　主展色剤がアミン変性ビスフェノールＡ型エボ、
やシ樹脂化合物と少なくとも一部ブロックされたポリイ
ソシアネート化合物とからなる第１項記戦の組成物。 ４、微粉炭素を第４級アンモニウム塩含有樹脂で分散す
る第１項記載の組成物。 ５、第１〜４項いずれかに記載の組成物に鉛系化合物を
添加するカチオン型電青め絹組成物。 ６、固形分含量の８〜５０重量％の微粉炭素および主展
色剤として塩基性基含有水稀釈性樹脂を含有する第１〜
５項いずれかに記載のカチオン型Ｎ着塗料組成物を用い
て金属被塗物上に電着塗装し焼成して第１層塗膜を形成
させ、該倹膜上に更に電着塗装により第２層重着塗膜を
形成させる塗装法。 ７、約１００〜２５０°Ｃの温度で焼成して＠１層塗膜
を形成させる第６項記載の塗装法。 ８、第２饗電着塗膜をカチオン型電着塗装により形成さ
せる第１５項記載の塗装法。 ９、第２層電管塗装にアクリル系樹脂組成物を用いる＠
６項記載の塗装法。[Scope of Claims] 1. A cationic type coating characterized by containing 8 to 50% by weight of finely divided carbon based on the total solid content and a basic group-containing water-dilutable resin as a main coloring agent. Phase 7 inhibitor. 2. The composition according to item 1, which contains pulverized carbon in an amount of 15 to 30% by weight of the total solids content. 3. The main color vehicle is amine-modified bisphenol A type EVO,
The composition according to paragraph 1, comprising a polyisocyanate compound and an at least partially blocked polyisocyanate compound. 4. The composition according to item 1, wherein finely divided carbon is dispersed in a quaternary ammonium salt-containing resin. 5. A cationic electro-blue silk composition obtained by adding a lead-based compound to the composition according to any one of items 1 to 4. 6. The 1st to 1st pigment containing finely divided carbon in an amount of 8 to 50% by weight of the solid content and a basic group-containing water-dilutable resin as the main coloring agent.
Using the cationic N-coating composition according to any one of Item 5, a first layer coating film is formed by electrodeposition coating on a metal object and baking, and a second coating film is further formed on the coating film by electrodeposition coating. A coating method that forms a two-layer coating. 7. The coating method according to item 6, wherein a single layer coating film is formed by firing at a temperature of about 100 to 250°C. 8. The coating method according to item 15, wherein the second electrodeposition coating film is formed by cationic electrodeposition coating. 9. Using acrylic resin composition for second layer tube coating @
Coating method described in Section 6.