JPH057432B2 - - Google Patents

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Publication number
JPH057432B2
JPH057432B2 JP60246697A JP24669785A JPH057432B2 JP H057432 B2 JPH057432 B2 JP H057432B2 JP 60246697 A JP60246697 A JP 60246697A JP 24669785 A JP24669785 A JP 24669785A JP H057432 B2 JPH057432 B2 JP H057432B2
Authority
JP
Japan
Prior art keywords
resin
parts
weight
alkyd resin
alkyd
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.)
Expired - Lifetime
Application number
JP60246697A
Other languages
Japanese (ja)
Other versions
JPS62106966A (en
Inventor
Yukie Okumura
Nobuhiro Tahira
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aisin Chemical Co Ltd
Original Assignee
Aisin Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aisin Chemical Co Ltd filed Critical Aisin Chemical Co Ltd
Priority to JP24669785A priority Critical patent/JPS62106966A/en
Publication of JPS62106966A publication Critical patent/JPS62106966A/en
Publication of JPH057432B2 publication Critical patent/JPH057432B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳細な説明】[Detailed description of the invention]

〔産業上の利用分野〕 本発明は、酸化重合による常温乾燥型のアルキ
ツド樹脂塗料組成物に関し、詳しくは乾燥初期の
塗膜硬度に優れた塗膜を形成できるアルキツド樹
脂塗料組成物に関する。 〔従来の技術〕 従来より、自動車、建築物、電気機器及びそれ
らの部品などの塗装には、酸化重合型の常温硬化
型アルキツド樹脂を用いた塗料が多く用いられて
いる。 この塗料は塗装後常温でも硬化するが、生産性
を向上させるために、乾燥炉内で強制乾燥を行
い、できるだけ短時間で硬化させるようにするの
が一般的である。 ところが酸化重合型の塗料では、乾燥炉による
乾燥直後では半硬化状態であり、ガラス転移点
(Tg)が低い。そのため乾燥炉から出た直後の温
度の高い状態では塗膜表面にべたつきが残るとい
う現象がある。このように塗膜にべたつきが残る
と取扱いが困難となり、冷えるまでの時間と場所
にロスが生じる。 従来、このべたつきのない性質、すなわちタツ
クフリー性を向上させる手段として、アルキツド
樹脂の変性油の種類の変更、或いは金属キレート
化合物の添加、などの手段が講じられている(特
開昭52−69437号、特開昭51−8324号)。しかしこ
れらの方法によつても、タツクフリー性の改善は
必ずしも充分とはいえなかつた。 この理由は次のように説明できる。すなわち、
タツクフリー性は半硬化樹脂のTgと大きな関係
があるが、酸化重合型のアルキツド樹脂は架橋反
応が本質的に緩やかであり、変性油やドライヤー
の種類及び量の変更を行つても、低温で短時間の
加熱だけでは充分な架橋によるTgの向上は期待
できない。また、金属キレート化合物を添加すれ
ばタツクフリー性はある程度改善されるが、耐衝
撃性など他の塗膜物性が低下する。 〔発明が解決しようとする課題〕 本発明は、上記欠点を克服するものであり、タ
ツクフリー性及び塗膜初期硬度に優れ、かつ耐水
性、耐食性及び耐衝撃性が損なわれることがない
塗膜を与えるアルキツド樹脂塗料組成物とするこ
とを目的とする。 〔問題点を解決するための手段〕 本発明のアルキツド樹脂塗料組成物は、乾性油
又は半乾性油で変性され酸化重合により常温硬化
可能な常温硬化型アルキツド樹脂100重量部に対
し、短油長アルキツド樹脂及びアクリル樹脂の少
なくとも一方からなる主剤樹脂と、主剤樹脂と架
橋可能なアミノ樹脂からなり主剤樹脂100重量部
に対して1〜50重量部となるように混合された硬
化剤と、からなる加熱硬化型樹脂混合物が11〜
150重量部含まれていることを特徴とする。 常温硬化型アルキツド樹脂とは、酸化重合によ
り常温で硬化可能なアルキツド樹脂をいう。この
ようなアルキツド樹脂としては、アマニ油、桐
油、脱水ヒマシ油などの乾性油、或いは大豆油、
サフラワー油、トール油などの半乾性油で変性さ
れたものが知られている。さらに、これにフエノ
ール樹脂、エポキシ樹脂、アクリル樹脂、ウレタ
ン樹脂などで変性されたものを用いることもでき
る。 本発明の最大の特徴は、この常温硬化型アルキ
ツド樹脂に対し、主剤樹脂と硬化剤とからなる加
熱硬化型樹脂混合物が混合されているところにあ
る。 主剤樹脂は硬化剤としてのアミノ樹脂と反応可
能な樹脂であり、短油長アルキツド樹脂及びアク
リル樹脂のいずれか一方、又は両者の混合物を用
いることができる。ただアクリル樹脂の場合は、
常温硬化型アルキツド樹脂との相溶性が良好なも
のを選ぶ必要がある。 硬化剤はアミノ樹脂から構成される。アミノ樹
脂とはメラミン、尿素、ベンゾグアナミンにホル
ムアルデヒドを付加させ、次いで縮合或いはエー
テル化させて得られる樹脂をいう。低温時の硬化
性を向上させるには、メチロール化度の大きなも
のが望ましく、メチロール化メラミンが特に好ま
しい。 この硬化剤は、主剤樹脂100重量部に対して1
〜50重量部の範囲で用いられる。硬化剤が1重量
部より少ないとタツクフリー性の改善が困難であ
り、50重量部より多くなると塗膜が硬くなり過ぎ
て他の塗膜物性が低下する。特に好ましいのは、
主剤樹脂100重量部に対して3〜20重量部である。 主剤樹脂と硬化剤とが上記の適切な配合比とな
つた加熱硬化型樹脂混合物は、常温硬化型アルキ
ツド樹脂100重量部に対して11〜150重量部の範囲
で混合される。加熱硬化型樹脂混合物が11重量部
より少ないとタツクフリー性の改善が困難であ
り、150重量部を超えると常温及び低温における
硬化性と耐水性など他の塗膜物性が低下する。 硬化剤が主剤樹脂100重量部に対して10重量部
程度の最適な範囲にあれば、加熱硬化型樹脂混合
物は、常温硬化型アルキツド樹脂100重量部に対
して11〜55重量部程度が最適である。この場合
は、実施例に示すようにタツクフリー性及び耐水
性に特に優れている。 なお本発明の塗料組成物には、上記樹脂のみな
らず、顔料、添加剤、溶剤などを種々含むことが
できる。例えば顔料としては、カーボンブラツ
ク、ベンガラ、チタン白などの無機顔料、フタロ
シアニン、キナクリドンなどの有機顔料、或いは
炭酸カルシウム、タルク、クレイ、硫酸バリウム
などの体質顔料を用いることができる。 また添加剤としては、ドライヤー、消泡剤、レ
ベリング剤、分散剤、色分かれ防止剤などを、溶
剤としては従来用いられている各種有機溶剤を用
いることができる。 〔発明の効果〕 本発明のアルキツド樹脂塗料組成物では、従来
の常温硬化型アルキツド樹脂に加えて、加熱硬化
型樹脂混合物を含んでいる。この加熱硬化型樹脂
混合物は架橋速度が常温硬化型アルキツド樹脂よ
り大きく、約100℃以下の低温であつても速やか
に架橋する。したがつて半硬化塗膜のTgが向上
し、タツクフリー性が向上するとともに、塗膜の
初期硬度が向上する。 そしてその後常温硬化型アルキツド樹脂が酸化
重合により除々に架橋し、最終的に塗膜物性に優
れた強靱な塗膜を形成する。 したがつて本発明のアルキツド樹脂塗料組成物
によれば、塗装物を低温で乾燥直後の取扱が容易
となり、生産性が向上する。 〔実施例〕 以下、実施例により具体的に説明する。 実施例1〜3及び比較例1〜3におけるアルキ
ツド樹脂塗料組成物の組成を、第1表に示す。こ
こで、常温硬化型アルキツド樹脂としては、比較
例2以外は半乾性油のトール油変性アルキツド樹
脂(油長51%)を用い、比較例2では乾性油のア
マニ油変性アルキツド樹脂(油長52%)を用い
た。 着色顔料としてはカーボンブラツクを用い、金
属ドライヤーとしてはナフテン酸コバルトを用
い、体質顔料としては炭酸カルシウムを用い、溶
剤はトルエンを用いた。また比較例3の金属キレ
ート化合物としては、エチルアセトアセテートア
ルミニウムジイソプロピレートを用いた。 実施例1〜3において、加熱硬化型樹脂混合物
の主剤樹脂を構成する短油長アルキツド樹脂とし
ては、油長33%のトール油変性アルキツド樹脂
(「ベツコゾールET330」大日本インキ化学工業(株)
製)を用い、硬化剤を構成するアミノ樹脂として
はメチロール化メラミン(「ニカラツク
MW12LF」三和ケミカル(株)製)を用いた。 上記それぞれの塗料組成物の性能評価をするた
めに、それぞれの塗料組成物からテストパネルを
作製した。先ず脱脂軟鋼板(「SPCC−SD」70×
150×0.8mm)を用意し、乾燥膜厚が20μmとなる
ようにエアスプレーでそれぞれ塗装して、5分の
セツテイング後90℃で20分間温風乾燥器により乾
燥させた。 そしてそれぞれの塗膜について、タツクフリー
性、耐食性、耐水性及び耐衝撃性の評価を行い、
結果を第1表に示す。 タツクフリー性は乾燥器から取り出し直後の塗
膜表面のべたつき度合いを指触評価で行つた。第
1表における◎は硬くべたつき無し、○は軟らか
いがべたつき無し、○〜△は若干のべたつき有
り、×はべたつき有り、の意味である。
[Industrial Field of Application] The present invention relates to an alkyd resin coating composition that dries at room temperature by oxidative polymerization, and more particularly relates to an alkyd resin coating composition that can form a coating film with excellent coating hardness in the early stage of drying. [Prior Art] Paints using oxidation-polymerizable room-temperature curing alkyd resins have been widely used for coating automobiles, buildings, electrical equipment, and their parts. This paint hardens even at room temperature after being applied, but in order to improve productivity, it is common to force dry it in a drying oven to harden it in as short a time as possible. However, oxidative polymerization type paints are in a semi-cured state immediately after drying in a drying oven and have a low glass transition point (Tg). For this reason, there is a phenomenon in which stickiness remains on the surface of the coating film when the temperature is high immediately after it comes out of the drying oven. If the paint film remains sticky in this way, it becomes difficult to handle, resulting in loss of time and space until it cools down. Conventionally, as a means to improve this non-stick property, that is, tack-free property, measures such as changing the type of modified oil of alkyd resin or adding a metal chelate compound have been taken (Japanese Patent Laid-Open No. 52-69437). , Japanese Patent Publication No. 51-8324). However, even with these methods, the improvement in tack-free property was not necessarily sufficient. The reason for this can be explained as follows. That is,
Tack-free properties are closely related to the Tg of semi-cured resins, but the crosslinking reaction of oxidation-polymerized alkyd resins is inherently slow, and even if the type and amount of modified oil and dryer are changed, they can be cured quickly at low temperatures. A sufficient improvement in Tg due to crosslinking cannot be expected only by heating for a period of time. Further, if a metal chelate compound is added, the tack-free property is improved to some extent, but other physical properties of the coating film such as impact resistance are deteriorated. [Problems to be Solved by the Invention] The present invention overcomes the above-mentioned drawbacks, and provides a coating film that is excellent in tack-free properties and initial coating film hardness, and that does not impair water resistance, corrosion resistance, and impact resistance. The purpose is to provide an alkyd resin coating composition. [Means for Solving the Problems] The alkyd resin coating composition of the present invention has a short oil length for 100 parts by weight of a cold-curing alkyd resin that is modified with a drying oil or semi-drying oil and can be cured at room temperature by oxidative polymerization. Consisting of a base resin made of at least one of an alkyd resin and an acrylic resin, and a curing agent made of an amino resin crosslinkable with the base resin and mixed in an amount of 1 to 50 parts by weight per 100 parts by weight of the base resin. Heat-curable resin mixture is 11~
It is characterized by containing 150 parts by weight. The room temperature curable alkyd resin refers to an alkyd resin that can be cured at room temperature by oxidative polymerization. Such alkyd resins include drying oils such as linseed oil, tung oil, and dehydrated castor oil, or soybean oil,
Those modified with semi-drying oils such as safflower oil and tall oil are known. Furthermore, those modified with phenol resin, epoxy resin, acrylic resin, urethane resin, etc. can also be used. The greatest feature of the present invention is that a heat-curable resin mixture consisting of a base resin and a curing agent is mixed with this room-temperature-curable alkyd resin. The main resin is a resin that can react with an amino resin as a curing agent, and either one of a short oil length alkyd resin and an acrylic resin, or a mixture of both can be used. However, in the case of acrylic resin,
It is necessary to select a material that has good compatibility with the room temperature curing alkyd resin. The curing agent is composed of an amino resin. Amino resin refers to a resin obtained by adding formaldehyde to melamine, urea, or benzoguanamine, and then condensing or etherifying the mixture. In order to improve the curability at low temperatures, it is desirable to have a high degree of methylolation, and methylolation melamine is particularly preferred. This curing agent is added in an amount of 1 part by weight per 100 parts by weight of the main resin.
It is used in a range of 50 parts by weight. If the amount of the curing agent is less than 1 part by weight, it is difficult to improve tack-free properties, and if it is more than 50 parts by weight, the coating film becomes too hard and other physical properties of the coating film deteriorate. Particularly preferred is
The amount is 3 to 20 parts by weight based on 100 parts by weight of the main resin. The heat-curable resin mixture containing the main resin and the curing agent in the above appropriate blending ratio is mixed in an amount of 11 to 150 parts by weight based on 100 parts by weight of the room-temperature curing alkyd resin. If the amount of the heat-curable resin mixture is less than 11 parts by weight, it will be difficult to improve tack-free properties, and if it exceeds 150 parts by weight, other physical properties of the coating film such as curability and water resistance at room temperature and low temperature will deteriorate. If the curing agent is in the optimal range of about 10 parts by weight based on 100 parts by weight of the main resin, the optimum amount of the heat-curing resin mixture is about 11 to 55 parts by weight based on 100 parts by weight of the room-temperature curing alkyd resin. be. In this case, as shown in the examples, the tack-free property and water resistance are particularly excellent. Note that the coating composition of the present invention can contain not only the above-mentioned resin but also various pigments, additives, solvents, and the like. For example, as pigments, inorganic pigments such as carbon black, red iron oxide, and titanium white, organic pigments such as phthalocyanine and quinacridone, or extender pigments such as calcium carbonate, talc, clay, and barium sulfate can be used. Further, as additives, dryers, antifoaming agents, leveling agents, dispersants, color separation inhibitors, etc. can be used, and as solvents, various conventionally used organic solvents can be used. [Effects of the Invention] The alkyd resin coating composition of the present invention contains a heat-curable resin mixture in addition to the conventional room-temperature-curable alkyd resin. This thermosetting resin mixture has a higher crosslinking rate than a room temperature curing alkyd resin, and is rapidly crosslinked even at a low temperature of about 100°C or less. Therefore, the Tg of the semi-cured coating film is improved, the tack-free property is improved, and the initial hardness of the coating film is improved. Thereafter, the room-temperature curing alkyd resin is gradually crosslinked by oxidative polymerization, ultimately forming a tough coating film with excellent coating properties. Therefore, according to the alkyd resin coating composition of the present invention, the coated article can be easily handled immediately after drying at a low temperature, and productivity is improved. [Example] Hereinafter, the present invention will be explained in detail with reference to Examples. Table 1 shows the compositions of the alkyd resin coating compositions in Examples 1 to 3 and Comparative Examples 1 to 3. Here, as the room temperature curing alkyd resin, except for Comparative Example 2, tall oil-modified alkyd resin (oil length 51%), which is a semi-drying oil, was used; %) was used. Carbon black was used as the coloring pigment, cobalt naphthenate was used as the metal dryer, calcium carbonate was used as the extender pigment, and toluene was used as the solvent. Moreover, as the metal chelate compound of Comparative Example 3, ethyl acetoacetate aluminum diisopropylate was used. In Examples 1 to 3, the short oil length alkyd resin constituting the main resin of the thermosetting resin mixture was a tall oil modified alkyd resin with an oil length of 33% ("Betsukosol ET330" manufactured by Dainippon Ink & Chemicals Co., Ltd.).
The amino resin constituting the curing agent is methylolated melamine (Nikalatsuku Co., Ltd.).
"MW12LF" manufactured by Sanwa Chemical Co., Ltd. was used. In order to evaluate the performance of each of the above coating compositions, test panels were prepared from each of the coating compositions. First, degreased mild steel plate (“SPCC-SD” 70×
150 x 0.8 mm) were prepared, each coated with air spray so that the dry film thickness was 20 μm, and after setting for 5 minutes, it was dried in a hot air dryer at 90°C for 20 minutes. We then evaluated each coating film for its tack-free properties, corrosion resistance, water resistance, and impact resistance.
The results are shown in Table 1. Tack-free property was evaluated by touch evaluation of the degree of stickiness of the coating film surface immediately after removal from the dryer. In Table 1, ◎ means hard and not sticky, ○ means soft but not sticky, ○ to △ means slightly sticky, and × means sticky.

【表】 耐食性は塩水噴霧試験により評価し、○は塩水
噴霧96時間後に錆幅3mm以下であることを意味す
る。 耐水性は、40℃温水中に所定時間浸漬した後の
塗膜の状態を評価し、◎は異常無し、○は白化す
るがブリスター無し、△〜○は若干のブリスター
発生、×〜△はブリスターの発生1/4以下、×は全
面のブリスター発生を意味する。 さらに耐衝撃性は、デユポン式衝撃試験により
評価し、◎は500g×30cm合格、○は500g×20cm
合格、△は500g×10cm合格の意味である。 第1表より、実施例1〜3の塗料組成物から形
成された塗膜は、比較例1〜2に比べてタツクフ
リー性が向上している。これは、短油長アルキツ
ド樹脂とメチロールメラミンからなる加熱硬化型
樹脂混合物を配合した効果であることが明らかで
ある。 なお、常温硬化型アルキツド樹脂100重量部に
対して加熱硬化型樹脂混合物を11〜55重量部とし
た実施例1〜2では、タツクフリー性が格段に向
上し、耐水性にも優れている。しかし実施例3で
は加熱硬化型樹脂混合物が多いために、耐水性が
わずかに低下している。 一方、比較例3では金属キレート化合物の添加
によりタツクフリー性はある程度向上している
が、耐水性及び耐衝撃性についてはむしろ低下し
ている。 以上より、酸化重合型の常温硬化型アルキツド
樹脂に対して加熱硬化型樹脂混合物をさらに加え
た実施例1〜3の塗料組成物によれば、常温硬化
型アルキツド樹脂のみの場合に比べて、耐食性、
耐水性及び耐衝撃性をほとんど損なうことなく、
タツクフリー性を向上できることが明らかであ
る。
[Table] Corrosion resistance was evaluated by a salt spray test, and ○ means that the rust width was 3 mm or less after 96 hours of salt spray. Water resistance is evaluated by evaluating the state of the paint film after immersing it in 40℃ warm water for a specified time. ◎ indicates no abnormality, ○ indicates whitening but no blisters, △ to ○ indicates slight blisters, and × to △ indicates blisters. The occurrence of 1/4 or less, × means the occurrence of blisters on the entire surface. Furthermore, impact resistance was evaluated using the Dupont impact test, where ◎ passed 500g x 30cm, ○ passed 500g x 20cm.
Pass, △ means pass 500g x 10cm. From Table 1, the coating films formed from the coating compositions of Examples 1 to 3 have improved tack-free properties compared to Comparative Examples 1 and 2. This is clearly an effect of blending a heat-curable resin mixture consisting of a short oil length alkyd resin and methylolmelamine. In Examples 1 and 2, in which the heat-curable resin mixture was used in an amount of 11 to 55 parts by weight based on 100 parts by weight of the room-temperature-curable alkyd resin, the tack-free properties were significantly improved and the water resistance was also excellent. However, in Example 3, the water resistance was slightly lowered due to the large amount of the thermosetting resin mixture. On the other hand, in Comparative Example 3, the tack-free property was improved to some extent by the addition of the metal chelate compound, but the water resistance and impact resistance were rather reduced. From the above, the coating compositions of Examples 1 to 3, in which a heat-curing resin mixture was further added to the oxidation-polymerizable room-temperature-curing alkyd resin, had better corrosion resistance than those containing only the room-temperature-curing alkyd resin. ,
without compromising water resistance or impact resistance.
It is clear that tack-free property can be improved.

Claims (1)

【特許請求の範囲】 1 乾性油又は半乾性油で変性され酸化重合によ
り常温硬化可能な常温硬化型アルキツド樹脂100
重量部に対し、 短油長アルキツド樹脂及びアクリル樹脂の少な
くとも一方からなる主剤樹脂と、該主剤樹脂と架
橋可能なアミノ樹脂からなり該主剤樹脂100重量
部に対して1〜50重量部となるように混合された
硬化剤と、からなる加熱硬化型樹脂混合物が11〜
150重量部含まれていることを特徴とするアルキ
ツド樹脂塗料組成物。
[Claims] 1. Cold-curing alkyd resin 100 that is modified with drying oil or semi-drying oil and can be cured at room temperature by oxidative polymerization.
A main resin consisting of at least one of a short oil length alkyd resin and an acrylic resin, and an amino resin crosslinkable with the main resin, so that the amount is 1 to 50 parts by weight based on 100 parts by weight of the main resin. A thermosetting resin mixture consisting of a curing agent mixed with
An alkyd resin coating composition characterized in that it contains 150 parts by weight.
JP24669785A 1985-11-01 1985-11-01 Alkyd resin paint composition Granted JPS62106966A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24669785A JPS62106966A (en) 1985-11-01 1985-11-01 Alkyd resin paint composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24669785A JPS62106966A (en) 1985-11-01 1985-11-01 Alkyd resin paint composition

Publications (2)

Publication Number Publication Date
JPS62106966A JPS62106966A (en) 1987-05-18
JPH057432B2 true JPH057432B2 (en) 1993-01-28

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP24669785A Granted JPS62106966A (en) 1985-11-01 1985-11-01 Alkyd resin paint composition

Country Status (1)

Country Link
JP (1) JPS62106966A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104194590A (en) * 2014-07-28 2014-12-10 铜陵市远程艺术制品有限责任公司 Wear-resisting and anti-aging alkyd resin paint for bronze sculptures

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5242173A (en) * 1975-09-30 1977-04-01 Nippon Telegr & Teleph Corp <Ntt> Method of observing lightning phenomenon by air-ground current
JPS5740187A (en) * 1980-08-23 1982-03-05 Takashi Tatekawa Easy detachable sucking disc type hose holder
JPS5749068A (en) * 1980-09-05 1982-03-20 Sanshin Ind Co Ltd Capacitor discharge type ignition device in internal combustion engine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5242173A (en) * 1975-09-30 1977-04-01 Nippon Telegr & Teleph Corp <Ntt> Method of observing lightning phenomenon by air-ground current
JPS5740187A (en) * 1980-08-23 1982-03-05 Takashi Tatekawa Easy detachable sucking disc type hose holder
JPS5749068A (en) * 1980-09-05 1982-03-20 Sanshin Ind Co Ltd Capacitor discharge type ignition device in internal combustion engine

Also Published As

Publication number Publication date
JPS62106966A (en) 1987-05-18

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