JPS5951958A - Cationic electrodeposition paint composition - Google Patents
Cationic electrodeposition paint compositionInfo
- Publication number
- JPS5951958A JPS5951958A JP57162494A JP16249482A JPS5951958A JP S5951958 A JPS5951958 A JP S5951958A JP 57162494 A JP57162494 A JP 57162494A JP 16249482 A JP16249482 A JP 16249482A JP S5951958 A JPS5951958 A JP S5951958A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- layer
- resin
- coating film
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
- B05D7/546—No clear coat specified each layer being cured, at least partially, separately
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Wood Science & Technology (AREA)
- Electrochemistry (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
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.
(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.
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)
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.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57162494A JPS5951958A (en) | 1982-09-18 | 1982-09-18 | Cationic electrodeposition paint composition |
GB08324737A GB2129807A (en) | 1982-09-18 | 1983-09-15 | Cationic electrocoating paint compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57162494A JPS5951958A (en) | 1982-09-18 | 1982-09-18 | Cationic electrodeposition paint composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS5951958A true JPS5951958A (en) | 1984-03-26 |
Family
ID=15755683
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57162494A Pending JPS5951958A (en) | 1982-09-18 | 1982-09-18 | Cationic electrodeposition paint composition |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS5951958A (en) |
GB (1) | GB2129807A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5677367A (en) * | 1995-08-15 | 1997-10-14 | Savin; Ronald R. | Graphite-containing compositions |
US5792803A (en) * | 1994-08-09 | 1998-08-11 | Ronald R. Savin | Cathodic coating compositions comprising lightweight hollow glass microspheres and zinc powder |
US6067439A (en) * | 1991-12-04 | 2000-05-23 | Canon Kabushiki Kaisha | Delivery member, and apparatus employing the same |
JP2023507510A (en) * | 2019-12-19 | 2023-02-22 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | ELECTRODEPOSITION PAINT COMPOSITION CONTAINING LAMP BLACK PIGMENT |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3538792C1 (en) * | 1985-10-31 | 1987-05-07 | Basf Lacke & Farben | Electrophoretically overcoatable coatings applied in the electrocoating process |
DE4339084A1 (en) * | 1993-11-16 | 1995-05-18 | Herberts Gmbh | Aqueous electrophoretically depositable dip lacquer and coating process using it |
DE19515089C1 (en) * | 1995-04-25 | 1996-09-19 | Herberts Gmbh | Aqueous cathodic electrodeposition paint and coating process using it |
DE19519665C1 (en) * | 1995-05-30 | 1996-09-05 | Herberts Gmbh | Multi-coat lacquering process for vehicle or component |
DE19519667C1 (en) * | 1995-05-30 | 1997-02-06 | Herberts Gmbh | Process for multi-layer painting |
DE19643082C2 (en) * | 1995-10-18 | 2003-10-30 | Volkswagen Ag | Process for the interior and exterior coating of a body with cavities |
US6423425B1 (en) | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
US20020056641A1 (en) * | 1999-12-15 | 2002-05-16 | December Timothy S. | Cured multilayer coating providing improved edge corrosion resistance to a substrate and a method of making same |
DE10064733A1 (en) * | 2000-12-22 | 2002-07-11 | Doerken Ewald Ag | Piece of material, refined with a zinc coating and with applied electro-dip lacquer, and process for its production |
US6508922B2 (en) | 2001-05-10 | 2003-01-21 | E. I. Du Pont De Nemours And Company | Process for multi-layer coating |
JP2006002003A (en) * | 2004-06-16 | 2006-01-05 | Nippon Paint Co Ltd | Cathodic electrodeposition coating composition |
US10358735B2 (en) | 2011-05-23 | 2019-07-23 | Axalta Coating Systems Ip Co., Llc | Anti-corrosion electrocoat |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3960795A (en) * | 1974-08-13 | 1976-06-01 | Ppg Industries, Inc. | Hydrolyzed reaction product of a polyepoxide with a phenolic compound having a group hydrolyzable to carboxyl |
DE2457437B2 (en) * | 1974-12-05 | 1978-02-23 | Basf Farben + Fasern Ag, 2000 Hamburg | COATING BATH FOR CATAPHORETIC COATING OF IRON METAL SURFACES |
CA1063295A (en) * | 1975-03-21 | 1979-09-25 | Joseph F. Bosso | N-heterocyclic-containing quaternary and ternary onium salt resins for cationic electrodeposition |
CA1111598A (en) * | 1976-01-14 | 1981-10-27 | Joseph R. Marchetti | Amine acide salt-containing polymers for cationic electrodeposition |
GB1531621A (en) * | 1976-01-21 | 1978-11-08 | Ppg Industries Inc | Cationic electrodepositable compositions |
AU507206B2 (en) * | 1976-08-18 | 1980-02-07 | Celanese Polymer Specialities Company | Modified epoxy resins |
US4102863A (en) * | 1976-11-24 | 1978-07-25 | Ppg Industries, Inc. | Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers |
CA1111590A (en) * | 1976-12-01 | 1981-10-27 | Isidor Hazan | Cathodic electrodeposition of paints |
JPS555933A (en) * | 1978-06-27 | 1980-01-17 | Nippon Soda Co Ltd | Cation electrodeposition coating composition |
US4192929A (en) * | 1978-08-31 | 1980-03-11 | Ford Motor Company | Corrosion resistant primers |
JPS5536247A (en) * | 1978-09-08 | 1980-03-13 | Nippon Soda Co Ltd | Electrophoretic paint composition for cathode deposition |
GB2041381B (en) * | 1979-01-08 | 1983-02-16 | Sumitomo Chemical Co | Electrophoretic coating compositions |
JPS55127472A (en) * | 1979-03-26 | 1980-10-02 | Kansai Paint Co Ltd | Resin composition for cation electrodeposition coating |
FR2459272A1 (en) * | 1979-06-13 | 1981-01-09 | Nippon Soda Co | ELECTROLYTIC COATING PAINT COMPOSITION OF THE CATHODE SEDIMENT TYPE |
US4260720A (en) * | 1979-10-31 | 1981-04-07 | Ppg Industries, Inc. | Novel mercapto chain extended products and their use in cationic electrodeposition |
JPS56151777A (en) * | 1980-04-28 | 1981-11-24 | Nippon Oil Co Ltd | Production of cathode-deposition type electrocoating |
GB2104537B (en) * | 1980-11-19 | 1985-01-30 | Ici Plc | Electrodeposition coating process and composition |
-
1982
- 1982-09-18 JP JP57162494A patent/JPS5951958A/en active Pending
-
1983
- 1983-09-15 GB GB08324737A patent/GB2129807A/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6067439A (en) * | 1991-12-04 | 2000-05-23 | Canon Kabushiki Kaisha | Delivery member, and apparatus employing the same |
US5792803A (en) * | 1994-08-09 | 1998-08-11 | Ronald R. Savin | Cathodic coating compositions comprising lightweight hollow glass microspheres and zinc powder |
US5677367A (en) * | 1995-08-15 | 1997-10-14 | Savin; Ronald R. | Graphite-containing compositions |
JP2023507510A (en) * | 2019-12-19 | 2023-02-22 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | ELECTRODEPOSITION PAINT COMPOSITION CONTAINING LAMP BLACK PIGMENT |
Also Published As
Publication number | Publication date |
---|---|
GB8324737D0 (en) | 1983-10-19 |
GB2129807A (en) | 1984-05-23 |
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