JPS5825350B2 - Water-dispersed thermosetting coating composition - Google Patents
Water-dispersed thermosetting coating compositionInfo
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- JPS5825350B2 JPS5825350B2 JP53035147A JP3514778A JPS5825350B2 JP S5825350 B2 JPS5825350 B2 JP S5825350B2 JP 53035147 A JP53035147 A JP 53035147A JP 3514778 A JP3514778 A JP 3514778A JP S5825350 B2 JPS5825350 B2 JP S5825350B2
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Description
【発明の詳細な説明】 本発明は水分散型熱硬化性樹脂被覆組成物に関する。[Detailed description of the invention] The present invention relates to water-dispersible thermosetting resin coating compositions.
さらに詳しくは、塗膜の加熱成膜時にワキやヒビ割れを
生じるこさがなく、かつ平滑性、光沢その他の物理的性
質に於て優れた性能を与える水分散型熱硬化性被覆組成
物に関する。More specifically, the present invention relates to a water-dispersible thermosetting coating composition that does not cause wrinkles or cracks during heat-forming of a coating film and provides excellent performance in terms of smoothness, gloss, and other physical properties.
近時、塗料及び塗装の低公害、無公害化ならびに省資源
化が要望され、かつ進められ、これに適するものとして
スラリー状塗料が開発され、使用に供され始めている。BACKGROUND ART In recent years, there has been a growing demand for low-pollution, non-pollution, and resource-saving paints and coatings, and slurry-type paints have been developed as suitable for this purpose and are beginning to be put into use.
ところで周知の如くこのようなスラリー状塗料は、粒子
径が1〜80μ程度の樹脂粉末を水を主体とする媒体中
に20〜70重量%の固形分濃度で分散したものであり
、それ故、有機溶剤による環境汚染や毒性がなく、シか
も通常の液状塗料の塗装方法が適用出来、また一回の塗
装で厚膜塗装が得られるという長所を有している。By the way, as is well known, such a slurry paint is made by dispersing resin powder with a particle size of about 1 to 80 microns in a medium mainly composed of water at a solid content concentration of 20 to 70% by weight. It has the advantage that it does not cause environmental pollution or toxicity due to organic solvents, can be applied with ordinary liquid paint coating methods, and can provide a thick coating with a single coating.
更に、構成4分として多量の界面活性剤を使用しないた
め、それから得られる塗膜の耐水性、耐湿性及び耐薬品
性が他の形態の塗料より優れているという特長を有する
。Furthermore, since a large amount of surfactant is not used as a component, the resulting coating film has superior water resistance, moisture resistance, and chemical resistance compared to other types of paints.
しかしながらこのような各種長所を有する一方、なお特
性上多少の難点を有していた。However, while it has these various advantages, it still has some drawbacks in terms of characteristics.
その1つは樹脂粒子を安定な分散状態で水中に存在させ
るために、従来水溶性増粘剤の使用がさけられなかった
が、(通常、樹脂粒子に対して0.05〜1.0重量%
程度の水溶性増粘剤を使用)、それは塗膜の加熱成膜時
に樹脂粒子の溶融流動性を阻害し、したがって得られる
塗膜の平滑性、光沢等を著しく低下させる傾向があった
。One of them is that in order to make the resin particles exist in water in a stable dispersed state, it has been necessary to use a water-soluble thickener (usually 0.05 to 1.0% by weight based on the resin particles). %
However, when a water-soluble thickener is used at a certain level, it tends to inhibit the melt flowability of the resin particles during heating of the coating film, thereby significantly reducing the smoothness, gloss, etc. of the resulting coating film.
また分散媒として水を使用しているため、スプレー塗装
時に雰囲気湿度の影響を受は易く、例えば低湿度時には
ドライスプレーになり易いという欠点があった。Furthermore, since water is used as a dispersion medium, spray coating is easily affected by atmospheric humidity, and has the disadvantage that, for example, dry spray tends to occur at low humidity.
加えて加熱成膜時に雰囲気温度が水の沸点より30〜1
00℃高いため水の急激な蒸発ないしは突沸により塗膜
ζこヒビワレやワキを生じ易いというような各種難点が
あった。In addition, the ambient temperature during heating film formation is 30 to 1
Since the temperature is 00°C, there are various problems such as rapid evaporation or bumping of water, which tends to cause cracks and wrinkles in the coating film.
本発明は上記の問題を解決ないしは改良した新規な水分
散型熱硬化性被覆組成物、すなわち塗装作業性が優れ、
得られる塗膜の平滑性、光沢が良好でしかもヒビワレや
ワキの発生の無い、優れた塗膜仕上り性を有する水分散
型熱硬化性樹脂被覆組成物に関する。The present invention is a novel water-dispersible thermosetting coating composition that solves or improves the above problems, that is, has excellent coating workability,
The present invention relates to a water-dispersible thermosetting resin coating composition which has excellent coating film finishing properties, such as good smoothness and gloss of the resulting coating film, and no occurrence of cracks or wrinkles.
即ち、本発明は、
(イ)水媒体 50〜70重量部(O
)平均粒子径5〜50ハ軟化温度が30〜120℃のア
クリル樹脂、ポリエステル樹脂、及びエポキシ樹脂から
選ばれた熱硬化性樹脂粉末50〜30重量部ならびに
(/→ 前記(イ)及び(ロ)成分合計100重量部に
対して、一般式
で表わされ、かつm及びnが各々整数でmとnの和(混
合物の場合には和の平均値)が3から40である化合物
(以下便宜上「ポリエーテル化合物」と云う)0.5〜
7重量部より成り、前記水媒体が、水媒体と熱硬化性樹
脂粉末の総和に対して、0.01〜1.0重量%の水溶
性増粘剤を溶解し、かつ前記熱硬化性樹脂粉末が0.5
〜1重量%の流動助剤を含有していることを特徴とする
水分散型熱硬化性被覆組成物に関する。That is, the present invention provides (a) 50 to 70 parts by weight of an aqueous medium (O
) 50 to 30 parts by weight of thermosetting resin powder selected from acrylic resins, polyester resins, and epoxy resins having an average particle size of 5 to 50 and a softening temperature of 30 to 120°C, and (/→ the above (a) and (b) ) Compounds represented by the general formula, where m and n are each integers and the sum of m and n (in the case of a mixture, the average value of the sums) is from 3 to 40, based on 100 parts by weight of the total components (hereinafter referred to as (referred to as "polyether compound" for convenience) 0.5~
7 parts by weight, the aqueous medium dissolves 0.01 to 1.0% by weight of a water-soluble thickener based on the total of the aqueous medium and the thermosetting resin powder, and the thermosetting resin powder is 0.5
The present invention relates to a water-dispersed thermosetting coating composition characterized in that it contains ~1% by weight of a flow aid.
本発明に使用する前記「熱硬化性樹脂粉末」は、公知の
熱硬化性樹脂であり、更に必要により架橋剤、硬化剤、
触媒、顔料その他各種添加剤を含んでもよい。The "thermosetting resin powder" used in the present invention is a known thermosetting resin, and if necessary, a crosslinking agent, a curing agent,
It may also contain catalysts, pigments and other various additives.
該熱硬化性樹脂の軟化温度は、樹脂粉末の製造効率やス
ラリー状塗料の特に異常高温時の貯蔵安定性などを向上
するために30℃以上であることが好ましく、かつ平滑
な塗面を得るために120℃以下であることが好ましい
。The softening temperature of the thermosetting resin is preferably 30°C or higher in order to improve the production efficiency of the resin powder and the storage stability of the slurry paint, especially at abnormally high temperatures, and to obtain a smooth painted surface. Therefore, the temperature is preferably 120°C or less.
本発明Oこ使用される前記熱硬化性樹脂粉は、アクリル
樹脂、ポリエステル樹脂及びエポキシ樹脂から選ばれた
樹脂粉末であり、その熱硬化機構は自己硬化性、架橋剤
又は硬化剤硬化性のいずれでもよい。The thermosetting resin powder used in the present invention is a resin powder selected from acrylic resins, polyester resins, and epoxy resins, and its thermosetting mechanism is self-curing, crosslinking agent-curing, or curing agent-curing. But that's fine.
特に貯蔵時の安定性、塗膜の平滑性、仕上り外観などの
観点から、上記の熱硬化性樹脂のうちアクリル樹脂及び
/又はポリエステル樹脂の使用が好ましい。Among the above thermosetting resins, it is preferable to use acrylic resins and/or polyester resins, especially from the viewpoint of stability during storage, smoothness of the coating film, finished appearance, etc.
これらの樹脂相互、あるいは樹脂と硬化剤との組合せか
らなる架橋反応の形式は、たとえばヒドロキシル基とア
ルコキシ基の反応9.ヒドロキシル基とイソシアネート
基の反応、ヒドロキシル基とカルボキシル基の反応、カ
ルボキシル基とエポキシ基の反応、アルコキシ基の自己
架橋、カルボキシル基とアルコキシ基の反応、エポキシ
基とアルコキシ基の反応などである。The type of crosslinking reaction consisting of a combination of these resins or a combination of a resin and a curing agent is, for example, a reaction between a hydroxyl group and an alkoxy group.9. These include reactions between hydroxyl groups and isocyanate groups, reactions between hydroxyl groups and carboxyl groups, reactions between carboxyl groups and epoxy groups, self-crosslinking of alkoxy groups, reactions between carboxyl groups and alkoxy groups, and reactions between epoxy groups and alkoxy groups.
前記架橋反応の組合せではヒドロキシル基とカルボキシ
ル基の反応、ヒドロキシル基とアルコキシ基の反応、ヒ
ドロキシル基とインシアネート基の反応、カルボキシル
基とアルコキシ基の反応、アルコキシ基の自己反応など
が好適である。Suitable combinations of crosslinking reactions include reaction between a hydroxyl group and a carboxyl group, a reaction between a hydroxyl group and an alkoxy group, a reaction between a hydroxyl group and an incyanate group, a reaction between a carboxyl group and an alkoxy group, a self-reaction of an alkoxy group, and the like.
特に前記ポリエーテル化合物のヒドロキシル基が架橋反
応に関与する組合せが好ましい。Particularly preferred is a combination in which the hydroxyl group of the polyether compound participates in the crosslinking reaction.
本発明に使用されるアクリル樹脂ポリエステル樹脂及び
エポキシ樹脂を更に詳しく説明すれば、アクリル樹脂は
官能基含有単量体及びその他の共重合性単量体の適宜の
組合せを常法に従って重合して得られるものである。To explain in more detail the acrylic resin polyester resin and epoxy resin used in the present invention, the acrylic resin is obtained by polymerizing an appropriate combination of a functional group-containing monomer and other copolymerizable monomers according to a conventional method. It is something that can be done.
前記官能基含有単量体として例えばβ−ヒドロキシエチ
ルアクリレート、β−ヒドロキシプロピルアクリレート
、β−ヒドロキシエチルメタクリレート、β−ヒドロキ
シプロピルメタクリレート、メチロールアクリルアミド
、メチロールメタクリルアミドなどのヒドロキシル基含
有単量体ニアクリル酸、メタクリル酸、イタコン酸、マ
レイン酸、フマル酸、及びマレイン酸やフマル酸のモノ
アルコールとのモノエステルなどのカルボキシル基含有
単量体;N−ブトキシメチルメタクリルアミド、N−ブ
トキシメチルアクリルアミドなどのアルコキシル基含有
単量体;グリシジメタクリレート、グリシジルアクリレ
ート、アリルグリシジルエーテルなどのエポキシ基含有
単量体;又、加熱によりイソシアネート基を再成する潜
在イソシアネート単量体として、たとエバトリメチルア
ミンメタクリルイミド、1,1−ジメチル−1−(2ヒ
ドロキシプロピル)アミンメタクリルイミド、1,1−
ジメチル−1−(2,3ジヒドロキシプロピル)アミン
メタクリルイミドなどのアミンイミド単量体:N−アル
ケニルアルキルカーバメート、N−アルケニルアリノル
カーバメ−1−,N−アルケニルアルキルカーバメート
、N−スチリルアルキルカーバメートなどカーバメート
基を含む単量体;及びヒドロキシル基を含む単量体と部
分ブロックイソシアネートとを反応させたブロックイソ
シアネート基を含む単重量体などが挙げられる。Examples of the functional group-containing monomer include hydroxyl group-containing monomers such as niacrylic acid, β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, methylol acrylamide, and methylol methacrylamide; Carboxyl group-containing monomers such as methacrylic acid, itaconic acid, maleic acid, fumaric acid, and monoesters of maleic acid and fumaric acid with monoalcohols; alkoxyl groups such as N-butoxymethylmethacrylamide and N-butoxymethylacrylamide Containing monomers: Epoxy group-containing monomers such as glycidimethacrylate, glycidyl acrylate, and allyl glycidyl ether; Also, as latent isocyanate monomers that regenerate isocyanate groups by heating, and evatrimethylamine methacrylimide, 1,1 -dimethyl-1-(2hydroxypropyl)amine methacrylimide, 1,1-
Amine imide monomers such as dimethyl-1-(2,3 dihydroxypropyl)amine methacrylimide: N-alkenylalkyl carbamate, N-alkenylalinolcarbame-1-, N-alkenylalkyl carbamate, N-styrylalkyl carbamate, etc. Monomers containing a carbamate group; and monomers containing a blocked isocyanate group obtained by reacting a monomer containing a hydroxyl group with a partially blocked isocyanate.
これらの単量体は1種もしくは2種以上の組合せとして
使用される。These monomers may be used alone or in combination of two or more.
またこれらの官能基含有単量体と共重合する単量体とし
て、例えばエチレン、プロピレン、イソブチレンなどの
オレフィン性不飽和単量体;スチレン、ユビニルトルエ
ン、α−メチルスチレンなどの芳香族単量体; (メタ
)アクリル酸メチル、(メタ)アクリル酸エチル、(メ
タ)アクリル酸プロピル。Monomers that copolymerize with these functional group-containing monomers include, for example, olefinically unsaturated monomers such as ethylene, propylene, and isobutylene; aromatic monomers such as styrene, ubivinyltoluene, and α-methylstyrene. Body: Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate.
(メタ)アクリル酸−n−ブチル、(メタ)アクリル酸
−イソブチル、(メタ)アクリル酸シクロ2ヘキシル、
(メタ)アクリル酸−2−エチルヘキシル、(メタ)ア
クリル酸ラウリル等の(メタ)アクリル酸と炭素原子1
〜18個のアルコールとのエステル類:酢酸ビニル、プ
ロピオン酸ビニル。n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclo2hexyl (meth)acrylate,
(Meth)acrylic acid such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and 1 carbon atom
Esters with ~18 alcohols: vinyl acetate, vinyl propionate.
2−エチルヘキシル酸ビニル等の炭素原子2〜 ご11
個のカルボン酸のビニルエステル類;その他項化ビニル
、アクリロニトリル、メタクリレートリルなどが挙げら
れ、これらは1種もしくは2種以上の組合せで使用でき
る。2-11 carbon atoms such as vinyl 2-ethylhexylate
vinyl esters of carboxylic acids; other examples include nitrogenated vinyl, acrylonitrile, methacrylate trile, etc., and these can be used alone or in combination of two or more.
また、ポリエステル樹脂は多価カルボン酸類とJ多価ア
ルコール類とより公知の方法で重合することにより得ら
れるものである。Further, the polyester resin is obtained by polymerizing polyhydric carboxylic acids and J polyhydric alcohols by a known method.
前記多価カルボン酸としては、例えばテレフタル酸、
イソフタル酸、 無水フタル酸、 ヘキサヒドロ無水フ
タル酸、 無水トリメリット酸、−無水マレイン酸、
無水コハク酸などが使用され。Examples of the polyhydric carboxylic acid include terephthalic acid,
Isophthalic acid, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, -maleic anhydride,
Succinic anhydride is used.
また多価アルコールとしては、例えばエチレングリコー
ル、 プロピレングリコール、 ジエチレングリコール
、 グリセリン、 トリメチロールプロパン、 トリ
メチロールエタン、 ペンタエリスリトール、 ビスフ
ェノールAなどが使用される。Further, as the polyhydric alcohol, for example, ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, bisphenol A, etc. are used.
特に芳香族環を含む多価カルボン酸及び多価アルコール
を20重量係以上使用することが貯蔵安定性を向上する
点で好ましい。In particular, it is preferable to use a polyhydric carboxylic acid and a polyhydric alcohol containing an aromatic ring in a weight ratio of 20 or more in order to improve storage stability.
これ等の樹脂の架橋剤として使用できるものとしては、
例えばメラミン、尿素、ベンゾグアナミン、 スピログ
アナミンなどのアミン化合物にホルマリンを反応させ、
更にメタノール、 エタノール、 ブタノールなど炭素
原子4個以下のアルコールで処理したアルキルエーテル
化アミン樹脂。Things that can be used as crosslinking agents for these resins include:
For example, by reacting formalin with amine compounds such as melamine, urea, benzoguanamine, and spiroguanamine,
Furthermore, alkyl etherified amine resins treated with alcohols having 4 or less carbon atoms such as methanol, ethanol, butanol.
多価インシアネート類を活性水素化合物でマスクしたブ
ロックイソシアネート化合物、ジェポキシ化合物、多価
カルボン酸類、及び多価アルコール類などがある。Examples include blocked isocyanate compounds in which polyvalent incyanates are masked with active hydrogen compounds, jepoxy compounds, polyvalent carboxylic acids, and polyhydric alcohols.
更に、本発明で使用するエポキシ樹脂は、例えばエピク
ロルヒドリンとビスフェノールAとから得られるビスフ
ェノール型エポキシ樹脂、ノボラック型エポキシ樹脂等
通常熱硬化性粉体塗料用として用いられる分子中に少く
とも2個以上のエポキシ基を含有する樹脂が使用可能で
ある。Furthermore, the epoxy resin used in the present invention is a bisphenol type epoxy resin obtained from epichlorohydrin and bisphenol A, a novolac type epoxy resin, etc., which are usually used for thermosetting powder coatings, and have at least two or more molecules in the molecule. Resins containing epoxy groups can be used.
これらの樹脂の架橋剤あるいは硬化剤としては、例えば
多価イソシアネート類を活性水素化合物でマスクしたブ
ロックイソシアネート化合物、無水トリメリット酸等の
多価カルボン酸類、アジピン酸ジヒドラジド等のジヒド
ラジド類、ジシアンジアミド、アミン樹脂ポリエステル
樹脂等、通常熱硬化性粉体塗料用として使用されるもの
が支障なく使用出来る。Examples of crosslinking agents or curing agents for these resins include blocked isocyanate compounds in which polyvalent isocyanates are masked with active hydrogen compounds, polyvalent carboxylic acids such as trimellitic anhydride, dihydrazides such as adipic acid dihydrazide, dicyandiamide, and amines. Resins such as polyester resins that are normally used for thermosetting powder coatings can be used without any problem.
本発明においては上記熱硬化性樹脂中に公知の流動助剤
、例えばアクリル系オリゴマー、シリコンオイル等を添
加する。In the present invention, a known flow aid such as an acrylic oligomer, silicone oil, etc. is added to the thermosetting resin.
これら公知の流動助剤としては、塗料の貯蔵安定性、塗
膜の硬度、耐水性、耐食性等の実用性を損わない程度、
即ち樹脂粉末中0.5〜1重量%包含せしめる。These known flow aids may be used to the extent that they do not impair the storage stability of the paint, the hardness of the paint film, the water resistance, the corrosion resistance, etc.
That is, it is included in the resin powder in an amount of 0.5 to 1% by weight.
本発明で使用する前記熱硬化性樹脂粉末は平均粒子径が
5〜50μの樹脂粉末である。The thermosetting resin powder used in the present invention has an average particle size of 5 to 50 μm.
前記に於て平均粒子径が5μより小さい場合には、粒子
同志の凝集性が大きくなり、また加熱成膜時に発泡し易
い等の水溶性塗料に近い性質をおびてくるため不適であ
る。In the above case, if the average particle diameter is smaller than 5 μm, the cohesiveness of the particles becomes large, and properties similar to those of water-soluble paints, such as easy foaming during heating film formation, are exhibited, which is unsuitable.
逆に50μより大きい場合には、貯蔵中に樹脂粉末が沈
澱凝集し易くなり、さらに薄膜で平滑な塗面が得られな
いため1本発明の目的に合致しなくなる。On the other hand, if it is larger than 50μ, the resin powder tends to precipitate and agglomerate during storage, and furthermore, a thin and smooth coated surface cannot be obtained, which does not meet the object of the present invention.
特に平均粒子径7〜30μの樹脂粉末により貯蔵安定性
が優れ発泡のない平滑な塗膜を与える塗料の得られるこ
とが判明した。In particular, it has been found that a resin powder with an average particle size of 7 to 30 .mu.m can provide a coating material with excellent storage stability and a smooth coating film without foaming.
本発明に於ては更に軟化温度30〜120°Cの樹脂粉
末を使用する。In the present invention, a resin powder having a softening temperature of 30 to 120°C is further used.
該樹脂粉末の軟化温度は、J主として前記熱硬化性樹脂
の軟化温度により決定される。The softening temperature of the resin powder is mainly determined by the softening temperature of the thermosetting resin.
勿論硬化剤、顔料、その他の添加剤の種類及び添加量に
よりそれは幾分変化する。Of course, it will vary somewhat depending on the types and amounts of curing agents, pigments, and other additives.
前記に於て樹脂粒子の軟化温度が、30℃より低い場合
には、貯蔵中沈澱した粒子を撹拌し再び1均一化しよう
とするとき、その粘着性のため充分に単独粒子にまでも
どすことが出来ない。In the above, if the softening temperature of the resin particles is lower than 30°C, when the particles that have precipitated during storage are stirred and attempted to be homogenized again, it is difficult to sufficiently return them to single particles due to their stickiness. Can not.
また逆に軟化温度が120℃より高い場合には、通常の
塗膜の成膜温度すなわち130o−200°Cの加熱温
度で、充分に流動平滑化しなくなる。On the other hand, if the softening temperature is higher than 120°C, sufficient fluidization and smoothing will not be achieved at the usual coating film forming temperature, that is, heating temperature of 130°C to 200°C.
1最適な軟化温度は40〜80℃である。 1. The optimum softening temperature is 40-80°C.
そのため顔料等塗料の加熱成膜温度で溶融しない部分の
添加量は、樹脂粒子中に50重量係以下とすることが好
ましい。Therefore, it is preferable that the amount of the pigment, etc., which does not melt at the heating film forming temperature of the paint, added to the resin particles is 50% by weight or less.
また熱硬化性樹脂と相溶する添加剤は、軟化源2度5〜
100℃のものから選択して使用することが好ましい。Additives that are compatible with thermosetting resins should be
It is preferable to use one selected from those with a temperature of 100°C.
本発明に於て使用する前記熱硬化性樹脂の樹脂粒子は公
知の製法により得られる。The resin particles of the thermosetting resin used in the present invention can be obtained by a known manufacturing method.
例えば粒子を構成する各成分の混合物を熱溶融練合した
後機械工粉砕する方法、該混合物と有機溶剤を混合ある
いは練合した溶液もしくは分散液を噴霧乾燥する方法、
該混合物と親水性有機溶剤からなる溶液又は分散液を水
中に撹拌乳化すると共に親水性有機溶剤を水中へ抽出移
行させる方法等が使用出来る。For example, a method of hot-melting and kneading a mixture of components constituting the particles and then mechanically crushing the mixture, a method of spray-drying a solution or dispersion obtained by mixing or kneading the mixture and an organic solvent,
A method can be used in which a solution or dispersion of the mixture and a hydrophilic organic solvent is stirred and emulsified in water, and the hydrophilic organic solvent is extracted and transferred into the water.
5本発明に於て水媒体と前記熱硬化性樹脂粒子の混合比
は、重量で70〜50/30〜50とする。5 In the present invention, the mixing ratio of the aqueous medium and the thermosetting resin particles is 70-50/30-50 by weight.
しかして樹脂が前記混合比より少ない組成のときには、
塗料の固形分濃度が低く、かつ低粘度であるため、一度
に通常の塗膜の厚さ、例えば205〜80μに塗布した
場合塗膜にダレ等の現象を生じ、これを避けるためには
数回の重ね塗りが必要である等、塗装作業性に問題が生
じる。However, when the composition of the resin is less than the above mixing ratio,
Since the solid content of the paint is low and its viscosity is low, if it is applied to a normal paint film thickness of 205 to 80 μm at a time, phenomena such as sagging will occur in the paint film. Problems arise with painting workability, such as the need for multiple coats.
一方樹脂粒子が前記混合比より多い場合には、塗料製造
時の撹拌、練合等による均一化が困難と−なり、また粘
度特性が各種の塗装法、例えばスプレー塗装、静電塗装
、浸漬塗装、カーテンフローコート、シャワーコート及
びロールコート等の適正値から外れるため塗装作業性が
悪く実用性が低下する。On the other hand, if the amount of resin particles exceeds the above mixing ratio, it will be difficult to make the paint uniform by stirring, kneading, etc. during paint production, and the viscosity characteristics will vary depending on various coating methods, such as spray coating, electrostatic coating, and dipping coating. , curtain flow coat, shower coat, roll coat, etc., which deviates from the appropriate values, resulting in poor painting workability and reduced practicality.
本発明においては前記の如く塗装及び塗膜特性を向上す
るために特定のポリエーテル化合物すなわち一般式
(但し、m及びnは各々整数で、m(!:nの和(混合
化合物の場合は和の平均値)が3〜40である)で表さ
れる化合物(混合化合物を含む。In the present invention, in order to improve coating and coating properties as described above, a specific polyether compound, that is, a general formula (where m and n are each an integer, and m (!: the sum of n (in the case of a mixed compound, the sum average value) is 3 to 40) (including mixed compounds).
以下同じ)を用いる。(same below) is used.
前記一般式においてmとnの和又は平均値が3より小さ
い化合物は沸点が低く、また加熱成膜時の揮散量が著し
いため、塗膜にヒビワレやワキが残り易い。In the above general formula, a compound in which the sum or average value of m and n is less than 3 has a low boiling point, and the amount of volatilization during heating film formation is significant, so that cracks and wrinkles are likely to remain in the coating film.
またその和が40より大きくなれば、高分子量になるた
め塗料の溶融流動性を増加する効果が低下し、塗膜の平
滑性が悪くなる。Moreover, if the sum is greater than 40, the molecular weight becomes high and the effect of increasing the melt fluidity of the coating material decreases, and the smoothness of the coating film deteriorates.
特に5〜30程度が好適である。上記ポリエーテル化合
物は、イの水媒体と口の熱硬化性樹脂粒子固形分との和
、100重量部の対して0.5〜1.7重量部の割合で
添加する。In particular, about 5 to 30 is suitable. The polyether compound is added in an amount of 0.5 to 1.7 parts by weight based on 100 parts by weight of the sum of the aqueous medium (A) and the solid content of the thermosetting resin particles (A).
前記範囲に於て、その添加量が0.5重量部より少くな
れば本発明の効果、就中塗装作業性及び塗膜特性の向上
が不充分になる。Within the above range, if the amount added is less than 0.5 parts by weight, the effects of the present invention, especially the improvements in coating workability and coating properties, will be insufficient.
逆に7重量部より多くなれば塗膜中に残存する量も多く
なり、そのため塗膜の耐水性、硬度、耐汚染性等が低下
する。On the other hand, if the amount exceeds 7 parts by weight, the amount remaining in the coating film will increase, resulting in a decrease in water resistance, hardness, stain resistance, etc. of the coating film.
前記理由などから特に1〜5重量部程度の添加が好まし
い。For the reasons mentioned above, it is particularly preferable to add about 1 to 5 parts by weight.
尚、上記ポリエーテル化合物は下記の方法により製造す
ることが出来る。Incidentally, the above polyether compound can be manufactured by the following method.
先ずメチルイソブチルケトンとアセチレン乃至はアセチ
レンカルビノールをアルカリ金属の水酸化物、酸化物又
はアルコラードなどの触媒の存在下に液体アンモニア中
で反応させて2,4,7゜9−テトラメチル−5−デシ
ン−4,7−ジオールを得る。First, methyl isobutyl ketone and acetylene or acetylene carbinol are reacted in liquid ammonia in the presence of a catalyst such as an alkali metal hydroxide, oxide, or alcolade to form 2,4,7°9-tetramethyl-5-. Decyne-4,7-diol is obtained.
この生成物とポリエチレングリコールを常法によりエー
テル化反応させ、生成物を減圧蒸留して該ポリエーテル
化合物を得る。This product and polyethylene glycol are subjected to an etherification reaction using a conventional method, and the product is distilled under reduced pressure to obtain the polyether compound.
前記n及びmの大きさは使用するポリエチレングリコー
ルの重合度により調整する。The sizes of n and m are adjusted depending on the degree of polymerization of the polyethylene glycol used.
本発明の組成物においては塗料の貯蔵安定性、塗装作業
性及び塗装時の塗膜のずり落ち等を改良するために、増
粘剤を添加する。In the composition of the present invention, a thickener is added in order to improve the storage stability of the paint, the workability of painting, and the slippage of the paint film during painting.
使用出来る増粘剤としては、通常水系塗料の増粘に用い
られるもの、例えばカルボキシル基含有アクリル共重合
体のアルカリ塩、ポリビニルピロリドン、ポリアクリル
アミド、セルローズ誘導体、ポリエチレンオキサイド等
の有機系増粘剤及びモンモリナイト、ベントナイト等の
無機系増粘剤が挙げられる。Thickeners that can be used include those normally used for thickening water-based paints, such as alkali salts of carboxyl group-containing acrylic copolymers, organic thickeners such as polyvinylpyrrolidone, polyacrylamide, cellulose derivatives, and polyethylene oxide; Examples include inorganic thickeners such as montmorinite and bentonite.
該増粘剤は水媒体と熱硬化性樹脂粒子の総和100重量
部に対して0.01〜1.0重量部添加することが好ま
しい。The thickener is preferably added in an amount of 0.01 to 1.0 parts by weight per 100 parts by weight of the aqueous medium and thermosetting resin particles.
該添加量が0.01重量部より少くなれば上記した増粘
効果が得られない。If the amount added is less than 0.01 parts by weight, the above-mentioned thickening effect cannot be obtained.
一方、1.0部より添加量を多くすると増粘効果は多少
向上するが、逆に増粘剤が樹脂粒子の溶融流動性を著し
く阻害するため、加熱成膜時に塗膜が充分に流動平滑化
する前に樹脂の硬化反応が進行し、平滑な塗膜が得られ
なくなる。On the other hand, if the amount added is greater than 1.0 part, the thickening effect will improve somewhat, but on the other hand, the thickener will significantly inhibit the melt fluidity of the resin particles, so the coating film will not be sufficiently fluid and smooth during heating film formation. The curing reaction of the resin progresses before it hardens, making it impossible to obtain a smooth coating.
上記した増粘剤の中カルボキシル基含有アクリジル共重
合体のアルカリ塩は塗膜の加熱成膜時にヒドロキシル基
、グリシジル基、イソシアネート基、アミン基などを有
する樹脂と反応して水不溶性になり塗膜の耐水性を低下
しないため本発明に特に好適である。The alkali salt of the carboxyl group-containing acridyl copolymer in the above-mentioned thickener reacts with resins containing hydroxyl groups, glycidyl groups, isocyanate groups, amine groups, etc. during heating to form a coating film, and becomes water-insoluble, resulting in a coating film. It is particularly suitable for the present invention because it does not reduce the water resistance of the material.
又本発明の被覆組成物に於ては、貯蔵安定性をさらに確
実にするために、必要により被覆組成物に対し界面活性
剤を1重量係以下、又親水性溶剤を5重量係以下添加す
ることができる。In addition, in the coating composition of the present invention, in order to further ensure storage stability, if necessary, a surfactant may be added to the coating composition by 1 weight part or less, and a hydrophilic solvent may be added to the coating composition by 5 weight part or less. be able to.
該界面活性剤としてはノニオン界面活性剤、ア。The surfactant includes a nonionic surfactant, a.
ニオン界面活性剤、カチオン界面活性剤、両性界面活性
剤など公知のものが使用可能である。Known surfactants such as ionic surfactants, cationic surfactants, and amphoteric surfactants can be used.
ノニオン界面活性剤としては、例えばソルビタン脂肪酸
エステル、ポリオキシエチレンソルビタン脂肪酸エステ
ル、ポリオキシエチレンソルビトール脂肪酸エステル、
ポリオキシエチレン脂肪酸エステル、ホリオキシエチレ
ンアルコールエーテル、グリセリン脂肪酸エステル、プ
ロピレンクリコール脂肪酸エステル、ポリオキシエチレ
ンヒマシ油誘導体、ポリオキシエチレンアルキルフェニ
ールエーテル、アルキルリン酸エステル、ホリオキシエ
チレンリン酸エステル等が挙げられ、又アニオン界面活
性剤としてはアルキル硫酸エステル塩、ポリオキシエチ
レンアルキルエーテル硫酸エステル塩、アルキルスルホ
コハク酸塩、N−アシルサルコシン塩、ならびにカチオ
ン活性剤としては第4級アンモニウム塩、ピリジニウム
塩などが使用出来る。Examples of nonionic surfactants include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
Examples include polyoxyethylene fatty acid ester, holoxyethylene alcohol ether, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene alkyl phenyl ether, alkyl phosphate ester, holoxyethylene phosphate ester, etc. Examples of anionic surfactants include alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, alkyl sulfosuccinates, N-acyl sarcosine salts, and cationic surfactants include quaternary ammonium salts and pyridinium salts. Can be used.
熱硬fヒ性樹脂粉末の分散安定性及び塗膜性能などの点
から、非イオン界面活性剤が好ましく特にHLBが8〜
18のものが好適である。From the viewpoint of dispersion stability and coating performance of the thermosetting resin powder, nonionic surfactants are preferred, especially those with an HLB of 8 to 8.
18 is preferred.
又、前記親水性溶剤としては通常水溶性塗料及びスラリ
ー状塗料に加えられるものが使用出来る。Further, as the hydrophilic solvent, those usually added to water-soluble paints and slurry paints can be used.
特に好適なものとしては樹脂粒子に対して常温で溶解性
を有せずかつ沸点が180℃以上のものであり、具体的
には、エチレングリコール、ジエチレングリコール、ト
リエチレングリコール、フロピレンゲリコール、ジプロ
ピレングリコール、1,4−ブタンジオール、1,3−
ブチレンクリコール、ヘキシレングリコール、ジプロピ
レングリコール、トリプロピレングリコール、ベンタン
ジオール、ヘプタンジオール等である。Particularly preferred are those that have no solubility in resin particles at room temperature and have a boiling point of 180°C or higher; specifically, ethylene glycol, diethylene glycol, triethylene glycol, fluoropylene gelicol, and diethylene glycol are preferred. Propylene glycol, 1,4-butanediol, 1,3-
These include butylene glycol, hexylene glycol, dipropylene glycol, tripropylene glycol, bentanediol, heptanediol, and the like.
本発明の水分散型熱硬化性被覆組成物は、雰囲気湿度が
低い場合でも前記ポリエーテル化合物の保水性によりド
ライスプレーを防止することが出来る。The water-dispersed thermosetting coating composition of the present invention can prevent dry spraying due to the water-retaining properties of the polyether compound even when the atmospheric humidity is low.
また該ポリエーテル化合物が水媒体の表面張力を低下す
るため被塗物に対する塗料のヌレが向上し、塗装適応中
が広くかつ均質に塗装することが出来るという特長を有
する。In addition, since the polyether compound lowers the surface tension of the aqueous medium, the wetting of the paint on the object to be coated is improved, and the paint can be applied over a wide area and uniformly.
更に従来のものは塗膜を加熱成膜させる際に水の沸点が
加熱温度より低いため水の急激な蒸発ないしは突沸によ
り塗膜にヒビワレやワキを生じ易く、才た増粘剤を含む
場合には増粘剤が樹脂粒子の溶融流動性を阻害し、塗膜
の平滑性、光沢等が著しく低下するが、本発明の被覆組
成物に於ては加熱成膜時に該ポリエーテル化合物が先ず
溶融し、該熱硬化性樹脂の溶剤として作用し、その結果
、塗膜の溶融粘度が低下すると共に溶融流動性が増加し
ヒビワレやワキが閉塞されて平滑な塗膜が形成されると
いう特長を有する。Furthermore, when conventional coatings are formed by heating, the boiling point of water is lower than the heating temperature, so rapid evaporation or bumping of water tends to cause cracks and wrinkles in the coating. However, in the coating composition of the present invention, the polyether compound is first melted during heating and film formation. It has the feature that it acts as a solvent for the thermosetting resin, and as a result, the melt viscosity of the coating film decreases and the melt fluidity increases, sealing cracks and wrinkles and forming a smooth coating film. .
すなわち、本発明の被覆組成物はより高い加熱雰囲気中
で迅速な加熱成膜が可能であるという特長を有している
。That is, the coating composition of the present invention has the feature that rapid heating film formation is possible in a higher heating atmosphere.
加えて、従来のものはスラリー状塗料の媒体が水である
ため鉄素地面に塗装した場合数分から十数分程度で点サ
ビが発生し加熱成膜後の塗面に浮き出ることがあるが、
本発明の組成物、就中ポリエーテル化合物はこのような
点サビの防止に有効に作用する。In addition, since conventional paints use water as a medium for slurry paint, when painted on a steel surface, spot rust may occur within a few minutes to over ten minutes and may appear on the painted surface after heating.
The composition of the present invention, particularly the polyether compound, effectively acts to prevent such spot rust.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
尚、実施例中で部及び係はすべて重量部及び重量部を表
わす。In the examples, all parts and parts represent parts by weight.
先ず、実施に先立って樹脂A−Dを次のように調製した
。First, prior to implementation, resins A to D were prepared as follows.
(1)樹脂溶液A
酢酸エチル 100部メタクリル
酸メチル 311/スチレン
3211メタクリル酸2−エチルへ
キシル 13〃メタクリル酸β−ヒドロキシエチル
8/lメタクリル酸グリシジル 15〃メ
タクリル酸 1〃アゾビスイソ
ブチロニトリル 3 //を公知の方法で溶液
重合し、酸価7、不揮発分50%の透明粘稠な樹脂溶液
Aを得た。(1) Resin solution A Ethyl acetate 100 parts Methyl methacrylate 311/Styrene
3211 2-ethylhexyl methacrylate 13 β-hydroxyethyl methacrylate
8/l glycidyl methacrylate 15 methacrylic acid 1 azobisisobutyronitrile 3 // was solution polymerized by a known method to obtain a transparent viscous resin solution A having an acid value of 7 and a non-volatile content of 50%.
該樹脂溶液から溶剤を除去し融点を測定した所75〜7
6°Cであった。When the solvent was removed from the resin solution and the melting point was measured, it was 75-7.
It was 6°C.
(2)樹脂溶液B
メチルエチルケトン 100部メタクリル
酸メチル 42〃メタクリル酸2−エチ
ルヘキシル 33〃アクリル酸2−エチルヘキシル
2.5/スチレン
5 ttメタクリル酸2−ヒドロキシプロピル15.5
//アクリル酸 2.07$2
,2’アゾビス−(2,4−ジメチ
ルバレロニトリル) 3 it’
ドデシルメルカプタン l //を公
知の方法で溶液重合し、酸価15.5、ヒドロキシル価
60、不揮発分50%の透明な樹脂溶液Bを得た。(2) Resin solution B Methyl ethyl ketone 100 parts Methyl methacrylate 42 2-ethylhexyl methacrylate 33 2-ethylhexyl acrylate
2.5/styrene
5 tt 2-hydroxypropyl methacrylate 15.5
//Acrylic acid 2.07$2
,2'azobis-(2,4-dimethylvaleronitrile) 3 it'
Dodecyl mercaptan 1 // was solution polymerized by a known method to obtain a transparent resin solution B having an acid value of 15.5, a hydroxyl value of 60, and a non-volatile content of 50%.
該樹脂溶液から溶剤を除去して融点を測定したところ8
1〜85℃であった。When the solvent was removed from the resin solution and the melting point was measured, 8
The temperature was 1-85°C.
(3)樹脂溶液C
メチルエチルケトン 100部メタクリ
ル酸メチル l Q //スチレン
30〃アクリル酸エチル
10〃メタクリル酸ブチル
10//ブロツクイソシアネート基含有モ
ノマー(注1) 2511メタクリ
ル酸2ヒドロキシエチル 13〃メタクリル酸
2〃アゾビスイソブチロニトリル
2//ドデシルメルカプタン
1〃(注1)ブランクィソシアネート基含
有モノマー
メタクリル酸2ヒドロキシエチル1モルとインホロンジ
イソシアネート1モル及びシクロへキサノンオキシム1
モルとより合成した下記の構造のもの。(3) Resin solution C Methyl ethyl ketone 100 parts Methyl methacrylate l Q //Styrene
30 Ethyl acrylate
10 Butyl methacrylate
10//Blocked isocyanate group-containing monomer (Note 1) 2511 2-hydroxyethyl methacrylate 13. Methacrylic acid
2〃Azobisisobutyronitrile
2//Dodecyl mercaptan
1 (Note 1) Blank isocyanate group-containing monomer 2-hydroxyethyl methacrylate 1 mol, inphorone diisocyanate 1 mol and cyclohexanone oxime 1
The following structure was synthesized from moles.
上記化合物を公知の方法で溶液重合し、酸価 J13で
不揮発分50%の自己架橋性の透明粘稠な樹脂溶液Cを
得た。The above compound was solution polymerized by a known method to obtain a self-crosslinkable transparent viscous resin solution C having an acid value of J13 and a non-volatile content of 50%.
溶液を除去し融点を測定した所、75〜80℃であった
。When the solution was removed and the melting point was measured, it was 75-80°C.
(4)樹脂D
テレフタル酸58部、トリメチロールプロ4(パン50
部、トリメチルヘキサンジオール37部を公知の方法で
エステル化し酸価16、ヒドロキシル価140、融点5
6〜60℃のポリエステル樹脂を得た。(4) Resin D: 58 parts of terephthalic acid, trimethylolpro 4 (pan 50 parts)
37 parts of trimethylhexanediol were esterified by a known method to obtain an acid value of 16, a hydroxyl value of 140, and a melting point of 5.
A polyester resin having a temperature of 6 to 60°C was obtained.
(5)樹脂溶液E
メチルエチルケトン 100部メタクリル
酸メチル 30〃スチレン
101!アクリル酸エチル
30〃メタクリル酸ブチル 1
0〃トリメチルアミンメタクリルイミド 10〃
メタクリル酸2−ヒドロキシプロピル 10//アゾビ
スイソブチロニトリル 3〃ドデシルメルカプ
タン 1〃を公知の方法で溶液重合し
、不揮発分50係の透明粘稠な樹脂溶液Eを得た。(5) Resin solution E Methyl ethyl ketone 100 parts Methyl methacrylate 30 Styrene
101! ethyl acrylate
30 Butyl methacrylate 1
0〃Trimethylamine methacrylimide 10〃
2-hydroxypropyl methacrylate 10 // azobisisobutyronitrile 3 and dodecyl mercaptan 1 were solution polymerized by a known method to obtain a transparent viscous resin solution E with a non-volatile content of 50 parts.
該樹脂溶液から溶剤を除去し融点を測定した所80〜8
1℃であった。When the solvent was removed from the resin solution and the melting point was measured, it was 80-8.
The temperature was 1°C.
(6)樹脂溶液F
メチルエチルケトン 100部メタクリル
酸メチル 331/アクリル酸2−エチ
ルヘキシル 3〃メタクリル酸2−エチルヘ
キシル 3 Q ttN−ブトキシメチルアクリル
アミド 2011メタクリル酸2−ヒドロキシエチ
ル 1211アクリル酸
2 //アゾビスイソブチロニトリル 3〃ド
デシルメルカプタン 1〃を公知の方
法で溶液重合し、酸価15.5、ヒドロキシル価48、
不揮発分50係の透明な樹脂溶液Fを得た。(6) Resin solution F Methyl ethyl ketone 100 parts Methyl methacrylate 331/2-ethylhexyl acrylate 3 2-ethylhexyl methacrylate 3 Q ttN-butoxymethylacrylamide 2011 2-hydroxyethyl methacrylate 1211 Acrylic acid
2 // Azobisisobutyronitrile 3 Dodecyl mercaptan 1 was solution polymerized by a known method to obtain an acid value of 15.5, a hydroxyl value of 48,
A transparent resin solution F with a non-volatile content of 50% was obtained.
該樹脂溶液から溶剤を除去して融点を測定したところ7
5〜78℃であった。When the solvent was removed from the resin solution and the melting point was measured, 7
The temperature was 5-78°C.
(7)樹脂溶液G
メチルエチルケトン 100部メタクリル
酸メチル 42〃メタクリル酸2−エチ
ルヘキシル 3711アクリル酸2−エチルヘキシ
ル 3〃メタクリル酸
2//メタクリル酸2−ヒドロキシエチル 15
〃アゾビスイソブチロニトリル 3 tt
を公知の方法で溶液重合し、酸価13、ヒドロキシル価
60、不揮発分50係の透明な樹脂溶液Gを得た。(7) Resin solution G Methyl ethyl ketone 100 parts Methyl methacrylate 42 2-ethylhexyl methacrylate 3711 2-ethylhexyl acrylate 3 Methacrylic acid
2//2-hydroxyethyl methacrylate 15
〃Azobisisobutyronitrile 3 tt
was solution-polymerized by a known method to obtain a transparent resin solution G having an acid value of 13, a hydroxyl value of 60, and a non-volatile content of 50.
該樹脂溶液から溶剤を除去して融点を測定したところ7
5〜78℃であった。When the solvent was removed from the resin solution and the melting point was measured, 7
The temperature was 5-78°C.
(8)樹脂溶液H
メチルエチルケトン 100部メタクリル
酸2−エチルヘキシル 371/アクリル酸2−エ
チルヘキシル 311スチレン
42〃メタクリル酸2−ヒドロキシエチ
ル 15〃メタクリル酸 2
〃を公知の方法で溶液重合し、酸価13、ヒドロキシル
価60、不揮発分50係の透明な樹脂溶液Hを得た。(8) Resin solution H Methyl ethyl ketone 100 parts 2-ethylhexyl methacrylate 371/2-ethylhexyl acrylate 311 styrene
42〃2-Hydroxyethyl methacrylate 15〃Methacrylic acid 2
was solution polymerized by a known method to obtain a transparent resin solution H having an acid value of 13, a hydroxyl value of 60, and a non-volatile content of 50.
該樹脂溶液から溶剤を除去して融点を測定したところ7
9〜83℃であった。When the solvent was removed from the resin solution and the melting point was measured, 7
The temperature was 9-83°C.
(9)樹脂溶液■
メチルエチルケトン 100部メタクリル
酸メチル 35〃アクリル酸エチル
50〃メタクリル酸2−ヒドロキシエチ
ル 151/アゾビスイソブチロニトリル
3〃を公知の方法で溶液重合し、ヒドロキシル価60
、不揮発分50係の透明な樹脂溶液■を得た。(9) Resin solution ■ Methyl ethyl ketone 100 parts Methyl methacrylate 35 Ethyl acrylate
50〃2-Hydroxyethyl methacrylate 151/Azobisisobutyronitrile
3 was solution polymerized by a known method to obtain a hydroxyl value of 60.
A transparent resin solution (2) with a non-volatile content of 50 parts was obtained.
該樹脂溶液から溶剤を除去して融点を測定したところ6
0〜70℃であった。When the solvent was removed from the resin solution and the melting point was measured, 6
The temperature was 0-70°C.
(10)樹脂溶液J
メチルエチルケトン 100部スチレン
35〃アクリル酸エチル
50〃メタクリル酸2−ヒl−’o
キシエチル 15〃アゾビスイソブチロニトリル
3〃を公知の方法で溶液重合し、ヒドロキシル価
60、不揮発分50係の透明な樹脂溶液Jを得た。(10) Resin solution J methyl ethyl ketone 100 parts styrene
35 Ethyl acrylate
50〃Methacrylic acid 2-hy-l-'o
Xyethyl 15 Azobisisobutyronitrile
3 was solution-polymerized by a known method to obtain a transparent resin solution J having a hydroxyl value of 60 and a non-volatile content of 50.
該樹脂溶液から溶剤を除去して融点を測定したところ7
0〜73℃であった。When the solvent was removed from the resin solution and the melting point was measured, 7
The temperature was 0-73°C.
(1υ樹脂溶液に
メチルエチルケトン 100部スチレン
40〃メタクリル酸2−ヒ
ドロキシエチル 16〃アクリル酸エチル
22〃アクリル酸ブチル 2
0〃メタクリル酸 2〃アゾビ
スイソブチロニトリル 3〃を公知の方法で溶
液重合し、酸価13、ヒドロキシル価67、不揮発分5
0係の透明な樹脂溶液Kを得た。(Methyl ethyl ketone 100 parts styrene in 1υ resin solution)
40〃2-Hydroxyethyl methacrylate 16〃Ethyl acrylate
22 Butyl acrylate 2
0 methacrylic acid 2 azobisisobutyronitrile 3 were solution polymerized by a known method to obtain an acid value of 13, a hydroxyl value of 67, and a non-volatile content of 5.
A transparent resin solution K of zero coefficient was obtained.
該樹脂溶液から溶剤を除去して融点を測定したところ7
1〜74℃であった。When the solvent was removed from the resin solution and the melting point was measured, 7
The temperature was 1-74°C.
(12)樹脂溶液L
メチルエチルケトン 100部メタクリル
酸メチル 3411スチレン
4〃メタクリル酸2−エチルヘキ
シル 27〃アクリル酸2−エチルヘキシル
2〃メタクリル酸2−ヒドロキシプロピル 31〃
アクリル酸 2〃アゾビスイ
ソブチロニトリル 3〃を公知の方法で溶液重
合し、酸価15.5、ヒドロキシル価120、不揮発分
50係の透明な樹脂溶液りを得た。(12) Resin solution L Methyl ethyl ketone 100 parts Methyl methacrylate 3411 Styrene
4〃2-ethylhexyl methacrylate 27〃2-ethylhexyl acrylate
2〃2-Hydroxypropyl methacrylate 31〃
Acrylic acid 2 and azobisisobutyronitrile 3 were solution polymerized by a known method to obtain a transparent resin solution having an acid value of 15.5, a hydroxyl value of 120, and a non-volatile content of 50.
該樹脂溶液から溶剤を除去して融点を測定したところ8
0〜83°Gであった。When the solvent was removed from the resin solution and the melting point was measured, 8
It was 0-83°G.
α3)樹脂溶液M
メチルエチルケトン 100部メタクリ
ル酸メチル 30/lスチレン
13〃アクリル酸エチル
35/N−ブトキシメチルアクリルアミド
20〃アクリル酸 2〃
アゾビスイソブチロニトリル 3〃を公知の方
法で溶液重合し、酸価15.5、不揮発分50係の透明
粘稠な樹脂溶液Mを得た。α3) Resin solution M Methyl ethyl ketone 100 parts Methyl methacrylate 30/l styrene
13〃Ethyl acrylate
35/N-butoxymethylacrylamide
20〃Acrylic acid 2〃
Azobisisobutyronitrile 3 was solution polymerized by a known method to obtain a transparent viscous resin solution M having an acid value of 15.5 and a nonvolatile content of 50%.
該樹脂溶液から溶剤を除去し融点を測定した所74〜7
7℃であった。The solvent was removed from the resin solution and the melting point was measured. 74-7
The temperature was 7°C.
04)樹脂溶液N
メチルエチルケトン 100部メタクリル
酸メチル 10〃スチレン
3011アクリル酸エチル
30〃ブロツクイソシアネート基含有
モノマー(前記性1 ) 3 Q //
アゾビスイソブチロニトリル 3 //を公知
の方法で溶液重合し、酸価15.5、不揮発分50係の
透明粘稠な樹脂溶液Nを得た。04) Resin solution N Methyl ethyl ketone 100 parts Methyl methacrylate 10 Styrene
3011 Ethyl acrylate
30〃Blocked isocyanate group-containing monomer (above property 1) 3 Q //
Azobisisobutyronitrile 3 // was solution polymerized by a known method to obtain a transparent viscous resin solution N having an acid value of 15.5 and a nonvolatile content of 50%.
該樹脂溶液から溶剤を除去し融点を測定した所72〜7
5°Cであった。The solvent was removed from the resin solution and the melting point was measured. 72-7
It was 5°C.
実施例 に
酸化チタン 29.5部樹脂溶液
A IIQ//。Example 29.5 parts of titanium oxide resin solution A IIQ//.
1.10デカンジカルボン酸 (硬化剤) 、。1.10 Decanedicarboxylic acid (hardening agent).
27アクリル酸エステルオリゴマー
(商品名モダフロー;モンサン
ト社製流動助剤)0.51/
酢酸エチル 40 ”からな
る混合組成物を、均一に練合分散して白色塗料溶液を得
た。A mixed composition consisting of 27 acrylic acid ester oligomer (trade name: Modaflow; flow aid manufactured by Monsanto Co., Ltd.) consisting of 0.51"/40" ethyl acetate was uniformly kneaded and dispersed to obtain a white paint solution.
この塗料溶液を高速撹拌下の水4000部に加え、微細
な乳濁液滴にすると共に溶剤を水中に溶出せしめ、つい
で水及び溶剤の混液を戸別し、さらに炉別、洗條を繰り
返し含水樹脂粉末ケーキを得た。This paint solution is added to 4000 parts of water under high speed stirring to form fine emulsion droplets and the solvent is eluted into the water.Then, the mixture of water and solvent is poured from door to door, and then the water-containing resin is separated into ovens and washed repeatedly. A powder cake was obtained.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分58%) 84部ポリエ
ーテル化合物(混合物)
(m + nの平均値;35) 1.0部
ノニオン界面活性剤(商品名
エマルゲン≠9.35;花王ア
トラス社製HLB 17.5 ) 0,
3 〃ベントナイト系増粘剤(商品名
ベントン;白石工業製100%) 0.111水
1611を均
一に練合分散し、固形分48.4係、pH7,1平均樹
脂粒子径25μのスラリー状塗料を得た。Water-containing resin powder cake (solid content 58%) 84 parts Polyether compound (mixture) (average value of m + n: 35) 1.0 part Nonionic surfactant (trade name Emulgen≠9.35; HLB manufactured by Kao Atlas Co., Ltd. 17.5) 0,
3 Bentonite thickener (trade name Benton; 100% manufactured by Shiraishi Kogyo) 0.111 Water
1611 was uniformly kneaded and dispersed to obtain a slurry-like paint having a solid content of 48.4%, a pH of 7, and an average resin particle diameter of 25 μm.
この塗料100部に水10部を加えて希釈し鉄板上にス
プレー塗装した後80℃で10分子熱し、続いて160
°Cで20分加熱乾燥して塗膜を形成した。Add 10 parts of water to 100 parts of this paint to dilute it, spray paint it on an iron plate, heat 10 molecules at 80°C, and then
A coating film was formed by heating and drying at °C for 20 minutes.
この塗膜は平滑性にすぐれたものであった又、この塗料
を密閉容器内に保ち50℃で1週間貯蔵した所沈殿、凝
集等をおこすことがなかった実施例 2
樹脂溶液B 100部ブチル化
メラミン樹脂(商品名メラ
ン27;日立化成工業■製) 25 //二
酸化チタン 30〃流動助剤
(前記モダフロー) 0.63〃をサンドミル
で均一に分散し、白色塗料溶液を得た。This coating film had excellent smoothness.Also, when this coating material was kept in a closed container at 50°C for one week, no precipitation or agglomeration occurred.Example 2 Resin Solution B 100 parts Butyl Melamine resin (trade name Melan 27; manufactured by Hitachi Chemical Co., Ltd.) 25 // titanium dioxide 30 flow aid (Modaflow) 0.63 was uniformly dispersed in a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値;10) 4〃ノニオン
界面活性剤(商品名エマゾ
ール4130 ;花王アトラス社製
HLB 15.3 ) 0.2
〃アクリル酸−アクリル酸エステル
共重合体(商品名アクリゾール
ASE95;ローム、アンド、ハー
ス社製増粘剤;固形分20係) 1,5//中
和剤(ジメチルアミンエタノール)0.21/水
30.0//を均一に
練合分散し、固形分40係、pH8,2、平均粒子径1
5μの実症例1と同じく貯蔵安定性の優れたスラリー状
塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4. Nonionic surfactant (trade name Emazol 4130; HLB 15.3 manufactured by Kao Atlas Co., Ltd.) 0.2
〃Acrylic acid-acrylic acid ester copolymer (trade name Acrysol ASE95; thickener manufactured by Rohm &Haas; solid content 20%) 1,5//neutralizing agent (dimethylamine ethanol) 0.21/water
30.0// was uniformly kneaded and dispersed, solid content 40%, pH 8.2, average particle size 1.
A slurry-like paint with excellent storage stability as in Example 1 of 5μ was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実施例 3
樹脂溶液8 98部インホロ
ンジイソシアネート誘導体
のカプロラクタムブロック体(商品
名クレランU−1;バイエル社製) 19.01!ジ
ブチルチンジラウレート
(解離触媒) 1.0#二酸
化チタン 30.011シリコス
オイル(商品名バイシロ
ンPL;バイエル社製流動助剤) 1.o/lメ
チルエチルケトン 30. O//をボ
ールミルで練合して、白色の塗料溶液とし、この塗料溶
液を実施例1と同様に湿式粉砕して含水樹脂粉末ケーキ
を得た。Example 3 Resin solution 8 98 parts Caprolactam block of inphorone diisocyanate derivative (trade name Kleran U-1; manufactured by Bayer AG) 19.01! Dibutyltin dilaurate (dissociation catalyst) 1.0# Titanium dioxide 30.011 Silicos oil (trade name Bisilon PL; flow aid manufactured by Bayer) 1. o/l methyl ethyl ketone 30. O// was kneaded in a ball mill to obtain a white paint solution, and this paint solution was wet-pulverized in the same manner as in Example 1 to obtain a water-containing resin powder cake.
さらにこの樹脂粉末ケーキを用いて下記の配合でスラリ
ー状塗料を作成した。Further, using this resin powder cake, a slurry-like paint was prepared with the following formulation.
含水樹脂粉末ケーキ
固形分54係) so部界面活
性剤(前記エマルゲン
+935) 0・5″中和
剤(水酸化ナトリウム) 0.01//アクリ
ル酸−アクリル酸エステル
共重合体〔商品名ビスコパール
EX180;高松油脂■製増粘剤) 0.031/水
20 uポリ
エーテル化合物(混合物)
(m+nの平均値;30) 2.0//こ
を均一に練合分散し、固形分43%、pH7,5及び平
均粒子径114の白色スラリー状塗料を得た。Water-containing resin powder cake solid content: 54) So part surfactant (the above Emulgen + 935) 0.5″ Neutralizing agent (sodium hydroxide) 0.01//Acrylic acid-acrylic acid ester copolymer [Product name: Viscopal EX180; thickener manufactured by Takamatsu Yushi ■) 0.031/water
20 u polyether compound (mixture) (average value of m+n; 30) 2.0// was uniformly kneaded and dispersed to obtain a white slurry-like paint with solid content of 43%, pH of 7.5, and average particle size of 114. Ta.
該スラリー状塗料をリン酸亜鉛処理した鉄板上に塗布し
、80℃で10分間予熱したのち、180℃で20分加
熱乾燥して得た塗膜は光沢、平滑性(耐食性にすぐれた
ものであった。The slurry paint was applied onto a zinc phosphate-treated iron plate, preheated at 80°C for 10 minutes, and then heated and dried at 180°C for 20 minutes.The resulting coating film was glossy and smooth (with excellent corrosion resistance). there were.
実施例 4
実施例3において前記ポリエーテル化合物(混合物)の
代りにmとnと和の平均値が20のポリエーテル化合物
(混合物)3部を添加した他はす。Example 4 Example 3 was repeated except that 3 parts of a polyether compound (mixture) having an average sum of m and n of 20 was added instead of the polyether compound (mixture).
べて同じ条件で塗料及び塗膜を形成した。Paints and coatings were formed under the same conditions in all cases.
得られた塗膜は優れた平滑性を有するものであった。The resulting coating film had excellent smoothness.
実施例 5
樹脂溶液C100部
流動助剤(前記バイシロンPL) 0.5部カー
ボンブラック 1〃メチルエチル
ケトン 201!ジブチルチンジラ
ウレート 1〃をボールミルで均一に練合
分散したのち、湿式粉砕し、含水樹脂粉末ケーキを得た
。Example 5 Resin solution C 100 parts Flow aid (Bisilon PL) 0.5 parts Carbon black 1. Methyl ethyl ketone 201! Dibutyltin dilaurate 1 was uniformly kneaded and dispersed in a ball mill, and then wet-pulverized to obtain a water-containing resin powder cake.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分60%) 75部ポリエ
ーテル化合物(混合物)
(m +nの平均値;10) 10〃界面活
性剤(前記エマルゲン
≠935) 0.1#中和
剤(ジメチルアミノエタ
ノール) 0.2//
アクリル酸−アクリル酸エステル
共重合体〔商品名ハイビスワコー
104;和光紬薬■製増粘剤〕 0.05〃水
18.5 //を均
一に練合分散して、固形分45係、pH8,8、平均樹
脂粒子径11μのスラリー状塗料を得た。Water-containing resin powder cake (solid content 60%) 75 parts Polyether compound (mixture) (Average value of m + n; 10) 10〃Surfactant (the above Emulgen≠935) 0.1# Neutralizing agent (dimethylaminoethanol) 0.2//
Acrylic acid-acrylic acid ester copolymer [trade name Hibiswako 104; thickener manufactured by Wako Tsumugi Pharmaceutical ■] 0.05 water
18.5// was uniformly kneaded and dispersed to obtain a slurry-like paint having a solid content of 45%, a pH of 8.8, and an average resin particle diameter of 11 μm.
この塗料は貯蔵安定性に優れ、またこれより得られる塗
膜は実施例5同様にすぐれた特性を有するものであった
。This paint had excellent storage stability, and the coating film obtained therefrom had excellent properties similar to Example 5.
実施例 6
樹脂D 40部ブロッ
クイソシアネート樹脂
(前記フレランU −1) 30 /
/ジブチルチンジラウレート
(解離触媒) 1.0#流
動助剤(前記モダフロー) 1,0//二酸
化チタン 30. Ottの均質
な混合物を熱ローラで溶融練合したのち、パンタムミル
で粉砕し平均粒子径25μの樹脂粉末を得た。Example 6 Resin D 40 parts Blocked isocyanate resin (Fleran U-1) 30/
/Dibutyltin dilaurate (dissociation catalyst) 1.0#Flow aid (Modaflow) 1,0//Titanium dioxide 30. A homogeneous mixture of Ott was melt-kneaded using a heated roller and then ground using a pantum mill to obtain a resin powder having an average particle size of 25 μm.
この樹脂粉末を用いて下記の配合でスラリー状塗料を作
成した。Using this resin powder, a slurry paint was prepared with the following formulation.
樹脂粉末 100部ポリエー
テル化合物(混合物)
(、m+nの平均値;30) :2部界
面活性剤(商品名デモールN。Resin powder 100 parts Polyether compound (mixture) (average value of m+n; 30): 2 parts Surfactant (trade name Demol N.
花王アトラス社製) 0.2〃増
粘剤(ポリエチレンオキサイド、
分子量100,000) 0.9〃中
和剤(ジメチルアミノエタノール)0.5〃水
100部エチレングリコ
ール 5//を均一に練合分散し
、固形分49%、pH8,6及び平均樹脂粒子径25μ
の白色スラリー状塗料を得た。Kao Atlas Co., Ltd.) 0.2 Thickener (polyethylene oxide, molecular weight 100,000) 0.9 Neutralizing agent (dimethylaminoethanol) 0.5 Water
100 parts of ethylene glycol 5// were uniformly kneaded and dispersed to give a solid content of 49%, a pH of 8.6, and an average resin particle size of 25μ.
A white slurry paint was obtained.
この塗料は貯蔵安定性に優れ、又これより得られる塗膜
は平滑性、耐食性の優れたものであった。This paint had excellent storage stability, and the coating film obtained from it had excellent smoothness and corrosion resistance.
実施例 7
エポキシ当量450〜525、軟化温度64〜76°C
のビスフェノール型エポキシ樹脂〔商品名エピコート1
001;シェル化学■製〕83部、シリコンオイル流動
助剤(前記バイシロンPL)0.5部、アジピン酸ジヒ
ドラジド6部、チタン白10部及びフタロシアニンブル
ー0.5部よりなる混合物を溶融練合し、機械粉砕及び
篩分けして200メツシユ以下の樹脂粒子を得た。Example 7 Epoxy equivalent weight 450-525, softening temperature 64-76°C
Bisphenol type epoxy resin [Product name Epicote 1]
001; manufactured by Shell Kagaku ■], 0.5 parts of silicone oil flow aid (Bisilon PL), 6 parts of adipic acid dihydrazide, 10 parts of titanium white, and 0.5 parts of phthalocyanine blue were melt-kneaded. , mechanically crushed and sieved to obtain resin particles of 200 mesh or less.
前記樹脂粒子 40部ポリエー
テル化合物(混合物)
(m 十nの平均値;10) 47ノニ
オン界面活性剤(商品名エマ
ゾール4130 ;花王アトラス社
製HLB 15.3 ) 0.2
ll増粘剤(前記アクリゾールASE
95) 1,5//
中和剤(ジメチルアミンエタノール) 0,2tt。Said resin particles 40 parts Polyether compound (mixture) (average value of m 10 n; 10) 47 Nonionic surfactant (trade name Emazol 4130; manufactured by Kao Atlas Co., Ltd. HLB 15.3) 0.2
Thickener (acrysol ASE 95) 1,5//
Neutralizing agent (dimethylamine ethanol) 0.2tt.
水 60.011
を均一に練合分散し、固形分42係、pH8,2、平均
粒子径15μの実施例1と同じく貯蔵安定性の優れたス
ラリー状塗料を得た。Water 60.011
were uniformly kneaded and dispersed to obtain a slurry-like paint having a solid content of 42%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1.
この塗料をリン酸亜鉛処理した鋼板に塗布し 。This paint was applied to a steel plate treated with zinc phosphate.
80℃で10分子熱後、140℃、20分加熱乾燥して
得た膜厚40μの塗膜は平滑性、仕上り外観のすぐれた
ものであった。After heating 10 molecules at 80°C, the resulting coating film with a thickness of 40μ was obtained by heating and drying at 140°C for 20 minutes and had excellent smoothness and finished appearance.
実施例 8
樹脂溶液E 100部二酸化チ
タン 30〃流動助剤(前記モ
ダフロー) 0.5〃をサンドミルで均一に
分散し、白色塗料溶液を得た。Example 8 Resin solution E 100 parts Titanium dioxide 30 Flow aid (Modaflow) 0.5 was uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ
(固形分55係) 70部ポリエー
テル化合物(混合物)
(m+nの平均値; 10 ) 4
//ノニオン界面活性剤(前記エマ
ゾール4130) 0.2//カ
ルボキシル基含有増粘剤(前
記アクリゾールASE95) 1.5//中
和剤(ジメチルアミンエタノール) 0.2//水
30.0/を均一
に練合分散し、固形分40係、pH8,2、平均粒子径
15μの実症例1と同じく貯蔵安定性の優れたスラリー
状塗料を得た。Water-containing resin powder cake (solid content: 55 parts) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4
//Nonionic surfactant (the above Emazol 4130) 0.2//Carboxyl group-containing thickener (the above Acrisol ASE95) 1.5//Neutralizing agent (dimethylamine ethanol) 0.2//Water
30.0/ was uniformly kneaded and dispersed to obtain a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実施例 9
樹脂溶液F 100部二酸化チ
タン 3011流動助剤(前
記モダフロー)、0.51/をサンドミルで均一に分散
し、白色塗料溶液を得たO
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 9 Resin solution F 100 parts Titanium dioxide 3011 flow aid (Modaflow), 0.51% was uniformly dispersed in a sand mill to obtain a white paint solution O The paint solution was added to 4000 parts of water under high speed stirring. Additional Example 1
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値;10) 4〃ノニオ
ン界面活性剤(前記エマ
ゾール4130) 0.2//カ
ルボキシル基含有増粘剤(前記
アクリゾールASE95) ■、5//中
和剤(ジメチルアミンエタノール)0.2〃水
30.O〃を均一に練合
分散し、固形分40%、pH8,2、平均粒子径15μ
の実施例1と同じく貯蔵安定性の優れたスラリー状塗料
を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4. Nonionic surfactant (Emazol 4130 mentioned above) 0.2 // Carboxyl group-containing thickener (mentioned above) Acrisol ASE95) ■, 5 // Neutralizing agent (dimethylamine ethanol) 0.2 water
30. Uniformly kneaded and dispersed O〃, solid content 40%, pH 8.2, average particle size 15μ
A slurry paint having excellent storage stability was obtained as in Example 1.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実施例 10
樹脂溶液G 100部ブチル化
メラミン樹脂(前記
メラン27) 25部二酸化
チタン 3011流動助剤(前
記モダフロー) 0,5//をサンドミルで
均一に分散し、白色塗料溶液を得た。Example 10 Resin solution G 100 parts Butylated melamine resin (Melan 27) 25 parts Titanium dioxide 3011 flow aid (Modaflow) 0.5// was uniformly dispersed in a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値;10) 4〃ノニオ
ン界面活性剤(前記エマゾー
ル4130) 0.2//カルボ
キシル基含有増粘剤(前記ア
クリゾールASE95) 1.5〃中和
剤(ジメチルアミンエタノール) 0,2//水
30. O//を均
一に練合分散し、固形分40係、pH8,2、平均粒子
径15μの実施例1と同じく貯蔵安定性の優れたスラリ
ー状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4. Nonionic surfactant (Emazol 4130 mentioned above) 0.2 // Carboxyl group-containing thickener (mentioned above) Acrysol ASE95) 1.5 Neutralizing agent (dimethylamine ethanol) 0,2//Water
30. By uniformly kneading and dispersing O//, a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1 was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実施例 11
樹脂溶液H100部
ブチル化メラミン樹脂(前記
メラン27 ) 25 //二
酸化チタン 3011流動助剤
(前記モダフロー) 0,5ttをサンドミ
ルで均一に分散し、白色塗料溶液を得た。Example 11 100 parts of resin solution H 25 butylated melamine resin (Melan 27) // 0.5 tt of titanium dioxide 3011 flow aid (Modaflow) were uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値: 10 ) 4 u
ノニオン界面活性剤(前記エマゾー
ル4130) 0.2〃カルボキシ
ル基含有増粘剤(前記ア
クリゾールASE95) 1.5部中和
剤(ジメチルアミンエタノール)0.211水
30.0//を均一に練
合分散し、固形分40%、pH8,2、平均粒子径15
μの実施例1と同じく貯蔵安定性の優れたスラリー状塗
料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n: 10) 4 u
Nonionic surfactant (Emazol 4130 above) 0.2 Carboxyl group-containing thickener (Acrisol ASE95 above) 1.5 parts Neutralizing agent (dimethylamine ethanol) 0.211 Water
30.0// was uniformly kneaded and dispersed, solid content 40%, pH 8.2, average particle size 15.
A slurry paint having excellent storage stability was obtained as in Example 1 of μ.
この塗料をリン酸亜鉛処理した鋼板に塗布し80°Cで
10分子熱後、140°Cで20分加熱乾燥して得た膜
厚40μの塗膜は平滑性、仕上り外観のすぐれたもので
あった。This paint was applied to a steel plate treated with zinc phosphate, heated at 80°C for 10 molecules, and then heated and dried at 140°C for 20 minutes.The resulting coating film with a thickness of 40μ was excellent in smoothness and finished appearance. there were.
実施例 12
樹脂溶液1 100部ブロックイ
ソシアネート樹脂
(前記フレランU−I) 20〃ジブ十
ルチンジラウレート
(解離触媒) 1.0//
二酸化チタン 30. O//
流動助剤(前記モダフロー) 0.5〃をサ
ンドミルで均一に分散し、白色塗料溶液を得た。Example 12 Resin solution 1 100 parts Blocked isocyanate resin (the above-mentioned Fulleran U-I) 20〃Dibuturutine dilaurate (dissociation catalyst) 1.0//
Titanium dioxide 30. O//
0.5 of the flow aid (Modaflow) was uniformly dispersed using a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエー
テル化合物(混合物)
(m +nの平均値; 10 ) 4
//ノニオン界面活性剤(前記エマゾー
ル4130) 0,2//カルボ
キシル基含有増粘剤(前記
アクリゾールASE95) 1.511中
和剤(ジメチルアミンエタノール)0.211水
30. O//を均一
に練合分散し、固形分40係、pH8,2、平均粒子径
15μの実施例1と同じく貯蔵安定性の優れたスラリー
状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m + n; 10) 4
//Nonionic surfactant (the above Emazol 4130) 0,2//Carboxyl group-containing thickener (the above Acrisol ASE95) 1.511 Neutralizing agent (dimethylamine ethanol) 0.211 Water
30. By uniformly kneading and dispersing O//, a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1 was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140°Cで20分加熱乾燥して得た膜厚
40μの塗膜は平滑性、仕上り外観のすぐれたものであ
った。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
After heating, the coating film with a thickness of 40 μm obtained by heating and drying at 140° C. for 20 minutes had excellent smoothness and finished appearance.
実施例 13
樹脂溶液J 100部ブロック
イソシアネート樹脂
(前記フレランU−I) 20〃ジブチ
ルチンジラウレート
(解離触媒)1.0部
二酸化チタン 30.O〃流動
助剤(前記モダフロー) 0,5//をサン
ドミルで均一に分散し、白色塗料溶液を得た。Example 13 Resin solution J 100 parts Blocked isocyanate resin (Fulleran U-I) 20. Dibutyltin dilaurate (dissociation catalyst) 1.0 part Titanium dioxide 30. O〃Flow aid (Modaflow) 0.5// was uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエー
テル化合物(混合物)
(m + nの平均値;10) 4〃ノ
ニオン界面活性剤(前記エマゾー
ル4130) 0.2//カルボ
キシル基含有増粘剤(前記ア
クリゾールASE95 ) 1.5 u
中和剤(ジメチルアミンエタノール)0,2//水
30. O//を均
一に練合分散し、固形分40係、pH8,2、平均粒子
径15μの実施例1と同じく貯蔵安定性の優れたスラリ
ー状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m + n; 10) 4. Nonionic surfactant (Emazol 4130 mentioned above) 0.2 // Carboxyl group-containing thickener (Acrisol ASE95) 1.5 u
Neutralizing agent (dimethylamine ethanol) 0,2//water
30. By uniformly kneading and dispersing O//, a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1 was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実施例 14
樹脂溶液K 50部樹脂溶
液M 50〃二酸化チタン
3o〃流動助剤(前記モダフロ
ー) 0,5//をサンドミルで均一に分散
し、白色塗料溶液を得た。Example 14 Resin solution K 50 parts Resin solution M 50 titanium dioxide
3o Flow aid (Modaflow) 0.5// was uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m + nの平均値; 10 ) 4
//ノニオン界面活性剤(前記エマゾー
ル4130) 0.211カルボ
キシル基含有増粘剤(前記ア
クリゾールASE95) 1.511中
和剤(ジメチルアミンエタノール)0.2部水
30. O//を均一に
練合分散し、固形分40係、pl」8.2、平均粒子径
15μの実施例1と同じく貯蔵安定性の優れたスラリー
状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m + n; 10) 4
//Nonionic surfactant (the above Emazol 4130) 0.211 Carboxyl group-containing thickener (the above Acrisol ASE95) 1.511 Neutralizing agent (dimethylamine ethanol) 0.2 parts water
30. By uniformly kneading and dispersing O//, a slurry-like paint having a solid content of 40%, a PL of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1 was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80°Cで
10分子熱後、140℃で20分加熱乾燥して得た膜厚
40μの塗膜は平滑性、仕上り外観のすぐれたものであ
った。This paint was applied to a steel plate treated with zinc phosphate, heated at 80°C for 10 molecules, and then heated and dried at 140°C for 20 minutes to obtain a 40μ thick film with excellent smoothness and finished appearance. Ta.
実施例 15
樹脂溶液L 50部樹脂溶
液N 50 //ジブチル
チンジラウレート
(解離触媒) 1,0//二
酸化チタン 30. O//流動
助剤(前記モダフロー)0.511
をサンドミルで均一に分散し、白色塗料溶液を得た。Example 15 Resin solution L 50 parts Resin solution N 50 //Dibutyltin dilaurate (dissociation catalyst) 1,0 //Titanium dioxide 30. A white paint solution was obtained by uniformly dispersing 0.511 of O//flow aid (Modaflow) using a sand mill.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値; 10 ) 4 /
/ノニオン界面活性剤(前記エマゾー
ル4130) 0.2//カルボ
キシル基含有増粘剤(前記ア
クリゾールASE95) 1.5//中
和剤(ジメチルアミンエタノール)0.21/水
30. O//を均一
に練合分散し、固形分40%、pH8,2、平均粒子径
15μの実施例1と同じく貯蔵安定性の優れたスラリー
状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4/
/nonionic surfactant (the above Emazol 4130) 0.2//carboxyl group-containing thickener (the above Acrisol ASE95) 1.5//neutralizing agent (dimethylamine ethanol) 0.21/water
30. By uniformly kneading and dispersing O//, a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1 was obtained.
この塗料をリン酸亜鉛処理した鋼板に塗布し80℃で1
0分子熱後、140℃で20分加熱乾燥して得た膜厚4
0μの塗膜は平滑性、仕上り外観のすぐれたものであっ
た。This paint was applied to a steel plate treated with zinc phosphate and heated to 80℃ for 1
Film thickness 4 obtained by heating and drying at 140°C for 20 minutes after heating 0 molecules
The 0 μ coating film had excellent smoothness and finished appearance.
実症例 16
樹脂溶液0 50部樹脂溶液
M 5oll二酸化チタン
30ノ!流動助剤(前記モダフ
ロー) 0,5//をサンドミルで均一に分
散し、白色塗料溶液を得た。Actual case 16 Resin solution 0 50 parts Resin solution M 5oll titanium dioxide
30 no! A flow aid (Modaflow) 0.5// was uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m+nの平均値; 10 ) 4
//ノニオン界面活性剤(前記エマゾー
ル4130) 0.2〃カルボキ
シル基含有増粘剤(前記ア
クリゾールASE95) 1.5//中
和剤(ジメチルアミンエタノール)0.2//水
30.Ollを均一に
練合分散し、固形分40%、pH8,2、平均粒子径1
5μの実施例1と同じく貯蔵安定性の優れたスラリー状
塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m+n; 10) 4
//Nonionic surfactant (the above Emazol 4130) 0.2 Carboxyl group-containing thickener (the above Acrysol ASE95) 1.5 // Neutralizing agent (dimethylamine ethanol) 0.2 // Water
30. Oll was uniformly kneaded and dispersed, solid content 40%, pH 8.2, average particle size 1.
A slurry-like paint with excellent storage stability was obtained as in Example 1 with a 5μ coating.
この塗料をリン酸亜鉛処理した鋼板に塗布し80°Cで
10分子熱後、140℃で20分加熱乾燥して得た膜厚
40μの塗膜は平滑性、仕上り外。This paint was applied to a steel plate treated with zinc phosphate, heated at 80°C for 10 molecules, and then heated and dried at 140°C for 20 minutes.The resulting coating film with a thickness of 40μ was smooth and unfinished.
観のすぐれたものであった。It was an excellent sight to see.
実施例 17
樹脂溶液I 50部樹脂溶
液N 50〃ジブチルチン
ジラウレート
(解離触媒) 1,0//
二酸化チタン 30. O//流
動助剤(前記モダフロー) 0,5//をサ
ンドミルで均一に分散し、白色塗料溶液を得た。Example 17 Resin solution I 50 parts Resin solution N 50 Dibutyltin dilaurate (dissociation catalyst) 1,0//
Titanium dioxide 30. O//flow aid (Modaflow) 0,5// was uniformly dispersed with a sand mill to obtain a white paint solution.
該塗料溶液を高速撹拌下の水4000部に加え実施例1
と同様に湿式粉砕して含水樹脂粉末ケーキを得た。Example 1: The coating solution was added to 4000 parts of water under high speed stirring.
A water-containing resin powder cake was obtained by wet grinding in the same manner as above.
この樹脂粉末ケーキを用いて下記の配合でスラリー状塗
料を作成した。Using this resin powder cake, a slurry paint was prepared with the following formulation.
含水樹脂粉末ケーキ(固形分55%) 70部ポリエ
ーテル化合物(混合物)
(m + nの平均値;10) 411
ノニオン界面活性剤(前記エマゾー
ル4130) 0.2//カルボ
キシル基含有増粘剤(前記ア
クリゾールASE95) 1.511
中和剤(ジメチルアミンエタノール)0.211水
30.0/lを均一
に練合分散し、固形分40%、pH8,2、平均粒子径
15μの実施例1と同じく貯蔵安定性の優れたスラリー
状塗料を得た。Water-containing resin powder cake (solid content 55%) 70 parts Polyether compound (mixture) (Average value of m + n; 10) 411
Nonionic surfactant (the above Emazol 4130) 0.2//Carboxyl group-containing thickener (the above Acrisol ASE95) 1.511
Neutralizing agent (dimethylamine ethanol) 0.211 water
30.0/l was uniformly kneaded and dispersed to obtain a slurry-like paint having a solid content of 40%, a pH of 8.2, and an average particle size of 15 μm and having excellent storage stability as in Example 1.
この塗料をリン酸亜鉛処理した鋼板に塗布し80°Cで
10分子熱後、140°Cで20分加熱乾燥して得た膜
厚40μの塗膜は平滑性、仕上り外観のすぐれたもので
あった。This paint was applied to a steel plate treated with zinc phosphate, heated at 80°C for 10 molecules, and then heated and dried at 140°C for 20 minutes.The resulting coating film with a thickness of 40μ was excellent in smoothness and finished appearance. there were.
比較例 1
実施例1においてポリエーテル化合物(混合■を除去し
た他はすべて同じ配合量でスラリー状塗料を調製した。Comparative Example 1 A slurry paint was prepared using the same amount of the polyether compound (mixture ①) as in Example 1 except that it was removed.
この塗料を用いて実施例1と同様にして塗膜を形成した
ところ点サビやワレが発生し、平滑性、可撓性に劣るも
のであった。When a coating film was formed using this coating material in the same manner as in Example 1, spot rust and cracking occurred, and the smoothness and flexibility were poor.
比較例 2
実施例2において樹脂粒子の平均粒子径を3μとした他
はすべて同様にしてスラリー状塗料を調製した。Comparative Example 2 A slurry paint was prepared in the same manner as in Example 2 except that the average particle diameter of the resin particles was changed to 3 μm.
この塗料を実施例2と同様にして塗装したところワキ膜
厚が薄く実用的な塗膜が得られなかった。When this paint was applied in the same manner as in Example 2, the armpit film thickness was so thin that a practical paint film could not be obtained.
比較例 3
実施例6においてポリエーテル化合物(混合物)を、等
量のmとnの和の平均値が50のポリエーテル化合物(
混合物)に変えた他は、実施例6と同様にしてスラリー
状塗料を調製した。Comparative Example 3 In Example 6, the polyether compound (mixture) was replaced with a polyether compound (mixture) in which the average value of the sum of equal amounts of m and n was 50 (
A slurry-like paint was prepared in the same manner as in Example 6, except that the mixture was changed to (mixture).
この塗料を実施例6と同様にして塗装したところ平滑性
の劣るものであった。When this paint was applied in the same manner as in Example 6, the smoothness was poor.
比較例 4
実施例5においてポリエーテル化合物(混合物)の添加
量を0.2部に変えた他は同様にして塗料及び塗膜を形
成した。Comparative Example 4 A paint and a coating film were formed in the same manner as in Example 5, except that the amount of polyether compound (mixture) added was changed to 0.2 parts.
この塗膜は点サビが発生し可撓性及び平滑性の劣るもの
であった。This coating film had spot rust and was poor in flexibility and smoothness.
比較例 5
実施例1においてポリエーテル化合物(混合物)を、等
量のmとnの和の平均値が2のポリエーテル化合物(混
合物)に変えた他は同様にして、塗料及び塗膜を形成し
た。Comparative Example 5 A paint and a coating film were formed in the same manner as in Example 1 except that the polyether compound (mixture) was changed to a polyether compound (mixture) in which the average value of the sum of m and n in equal amounts was 2. did.
この塗膜は実施例1に比較して平滑性の劣るものであっ
た。This coating film was inferior in smoothness compared to Example 1.
比較例 6
実施例6において樹脂粒子径を60μに変えた他は同様
にして塗料及び塗膜を形成した。Comparative Example 6 A paint and a coating film were formed in the same manner as in Example 6 except that the resin particle size was changed to 60μ.
この塗料は貯蔵安定性が劣り、また塗膜の平滑性も不充
分であった。This paint had poor storage stability, and the smoothness of the coating film was also insufficient.
比較例 7
実施例3においてポリエーテル化合物(混合物)の添加
量を10部に変えた他は同様にして塗料及び塗膜を形成
した。Comparative Example 7 A paint and a coating film were formed in the same manner as in Example 3, except that the amount of polyether compound (mixture) added was changed to 10 parts.
この塗膜は密着性及び耐水性が劣るものであった。This coating film had poor adhesion and water resistance.
以上の各実施例及び比較例で調製した塗料及び塗膜の特
性試験結果を第1表に示す。Table 1 shows the characteristics test results of the paints and coating films prepared in each of the above Examples and Comparative Examples.
Claims (1)
)平均粒子径5〜50μ、軟化温度が30〜120℃の
アクリル樹脂、ポリエステル樹脂、及びエポキシ樹脂か
ら選ばれた熱硬化性樹脂粉末 50〜30重量部、ならびに (/→ 前記(イ)及び(D)成分合計100重量部(
こ対して、一般式 で表わされ、かつm及びnが各々整数でmとnの和(混
合物の場合には和の平均値)が3から40である化合物
0.5〜7重量部よりなり、前記水媒体が
、水媒体と熱硬化性樹脂粉末の総和に対して、0.01
〜1,0重量%の水溶性増粘剤を溶解し、かつ前記熱硬
化性樹脂粉末が0.5〜1重量%の流動助剤を含有して
いることを特徴とする水分散型熱硬化性被覆組成物O[Claims] 1 (a) Aqueous medium: 50 to 70 parts by weight (b) Thermosetting resin selected from acrylic resin, polyester resin, and epoxy resin having an average particle diameter of 5 to 50 μ and a softening temperature of 30 to 120°C 50 to 30 parts by weight of synthetic resin powder, and (/→ Total 100 parts by weight of components (A) and (D) above (
On the other hand, compounds represented by the general formula, where m and n are each integers, and the sum of m and n (in the case of a mixture, the average value of the sums) is from 3 to 40.
The amount of the aqueous medium is 0.01 to 7 parts by weight based on the total amount of the aqueous medium and the thermosetting resin powder.
Water-dispersed thermosetting, characterized in that ~1.0% by weight of a water-soluble thickener is dissolved, and the thermosetting resin powder contains 0.5-1% by weight of a flow aid. coating composition O
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP53035147A JPS5825350B2 (en) | 1978-03-27 | 1978-03-27 | Water-dispersed thermosetting coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP53035147A JPS5825350B2 (en) | 1978-03-27 | 1978-03-27 | Water-dispersed thermosetting coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS54127438A JPS54127438A (en) | 1979-10-03 |
JPS5825350B2 true JPS5825350B2 (en) | 1983-05-26 |
Family
ID=12433782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP53035147A Expired JPS5825350B2 (en) | 1978-03-27 | 1978-03-27 | Water-dispersed thermosetting coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5825350B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60258332A (en) * | 1984-06-02 | 1985-12-20 | Toyo House Kk | Method of piling-up retaining wall block |
JPH03122133U (en) * | 1990-03-27 | 1991-12-13 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4320666B2 (en) * | 2006-09-08 | 2009-08-26 | 日信化学工業株式会社 | Glass fiber coating composition containing acetylene compound |
-
1978
- 1978-03-27 JP JP53035147A patent/JPS5825350B2/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60258332A (en) * | 1984-06-02 | 1985-12-20 | Toyo House Kk | Method of piling-up retaining wall block |
JPH03122133U (en) * | 1990-03-27 | 1991-12-13 |
Also Published As
Publication number | Publication date |
---|---|
JPS54127438A (en) | 1979-10-03 |
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