JPH1036767A - Two pack type aqueous coating composition - Google Patents
Two pack type aqueous coating compositionInfo
- Publication number
- JPH1036767A JPH1036767A JP8195836A JP19583696A JPH1036767A JP H1036767 A JPH1036767 A JP H1036767A JP 8195836 A JP8195836 A JP 8195836A JP 19583696 A JP19583696 A JP 19583696A JP H1036767 A JPH1036767 A JP H1036767A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking agent
- coating composition
- weight
- parts
- reaction product
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、２液型水性塗料組
成物に関し、詳しくは耐候性、耐水性、耐久性に優れる
塗膜を形成できる常温乾燥用の２液型水性塗料組成物に
関する。本発明の組成物は、建築内外装、橋梁、船舶、
自動車、車両などの塗装に適用可能である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-part aqueous coating composition, and more particularly to a two-part aqueous coating composition for drying at room temperature which can form a coating film having excellent weather resistance, water resistance and durability. Composition of the present invention, building interior and exterior, bridges, ships,
It is applicable to painting of automobiles and vehicles.
【０００２】[0002]
【従来技術及びその課題】一般に常温乾燥用水性塗料に
は、ビヒクル成分としてアクリル系共重合体エマルショ
ンが使用されている。該アクリル系共重合体エマルショ
ンは、塗装後のエマルション粒子同士の融着により成膜
するものであり、かかる融着による造膜性を確保する点
から、共重合体のガラス転移温度（Ｔｇ）を高く設計す
ることが困難であった。このため、該アクリル系共重合
体エマルションを用いた水性塗料による塗膜は、耐汚染
性に劣り、耐水性についても脆弱さは否めなかった。2. Description of the Related Art In general, an acrylic copolymer emulsion is used as a vehicle component in a water-based paint for drying at room temperature. The acrylic copolymer emulsion is formed by fusing emulsion particles after coating with each other. From the viewpoint of securing the film forming property by such fusing, the glass transition temperature (Tg) of the copolymer is adjusted. It was difficult to design high. For this reason, the coating film made of the aqueous paint using the acrylic copolymer emulsion was inferior in stain resistance and weak in water resistance.
【０００３】これに対し本出願人は、該水性塗料のエマ
ルションの造膜時の問題を解決するため、エマルション
粒子間を比較的分子量の小さい架橋剤で架橋させること
を提案し（特開平４−２４９５８７号公報）、これによ
り造膜性を補強し、耐汚染性、耐水性だけでなく、耐候
性、初期乾燥性の確保も実現した。On the other hand, the applicant of the present invention has proposed to crosslink between emulsion particles with a crosslinking agent having a relatively small molecular weight in order to solve the problem at the time of forming a film of an emulsion of the water-based paint (Japanese Patent Application Laid-Open No. Hei 4-104). 249587), thereby enhancing the film-forming properties and realizing not only the stain resistance and water resistance but also the weather resistance and the initial drying property.
【０００４】しかしながら該架橋剤による架橋反応は、
塗料中の水分が蒸発しエマルション粒子同士の融着が起
きてから始まるので、低温又は多湿の環境下では水分の
蒸発が遅いため、架橋が進行せず不完全なために、得ら
れる塗膜が白化したり所定の性能が得られないという問
題があった。[0004] However, the crosslinking reaction by the crosslinking agent is
Since the water in the paint evaporates and the emulsion particles start to fuse together, the water evaporates slowly in a low-temperature or high-humidity environment, so the crosslinking does not proceed and the coating film obtained is incomplete. There has been a problem that whitening or a predetermined performance cannot be obtained.
【０００５】一方、特公平８−３２８５１号公報にはイ
ソシアネ−ト硬化の２液型の水性塗料が開示されてい
る。かかる水性塗料では耐溶剤性、硬度に優れる塗膜が
得られるが、造膜性の面からガラス転移温度（Ｔｇ）が
０℃以上の共重合体を用いると常温で均一な膜ができな
いことがあるため、Ｔｇが０℃以下の共重合体を用いざ
るをえない。Ｔｇが低いと耐水性や耐汚染性に悪影響が
あり、常乾用塗料として実用的でなかった。On the other hand, Japanese Patent Publication No. 8-32851 discloses an isocyanate-cured two-pack type water-based paint. Such a water-based paint can provide a coating film having excellent solvent resistance and hardness. However, from the viewpoint of film forming properties, a copolymer having a glass transition temperature (Tg) of 0 ° C. or higher cannot form a uniform film at room temperature. For this reason, a copolymer having a Tg of 0 ° C. or lower must be used. If the Tg is low, the water resistance and stain resistance are adversely affected, and it is not practical as a paint for ordinary drying.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記問題
を解決すべく鋭意検討した結果、２液型のイソシアネ−
ト硬化塗料として特定のアクリル系共重合体エマルショ
ンと可塑剤及び／又は有機溶剤を含むベ−ス塗料を適用
することで、特に低温及び多湿の環境下での架橋性を低
下させることなく、耐汚染性、耐久性、耐水性などに優
れた常温乾燥可能な水性塗料が得られることを見出し本
発明を完成するに至った。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the two-pack type isocyanate
By applying a base paint containing a specific acrylic copolymer emulsion and a plasticizer and / or an organic solvent as a hardening paint, the cross-linking property is not reduced particularly in a low-temperature and high-humidity environment. The present inventors have found that an aqueous paint which can be dried at room temperature and has excellent stain resistance, durability, and water resistance can be obtained, thereby completing the present invention.
【０００７】即ち本発明は、水酸基価５〜１００ｍｇＫ
ＯＨ／ｇ、ガラス転移温度０〜８０℃、重量平均分子量
２０，０００〜４００，０００である水分散型共重合体
（Ａ）をビヒクル成分中に固形分で２０重量％以上含有
し、且つＳＰ値（溶解性パラメ−タ−値）が７．４〜
９．８である可塑剤及び／又は有機溶剤を樹脂固形分１
００重量部に対し１〜５０重量部含有してなるベ−ス塗
料（Ｉ）に、１分子中少なくとも２個以上のイソシアネ
−ト基を含有する化合物を含む架橋剤（II）を、ベ−ス
塗料（Ｉ）中に含まれる水酸基１モルに対して架橋剤
（II）中に含まれるイソシアネ−ト基が０．２〜３．０
モルとなるように使用直前に混合することを特徴とする
２液型水性塗料組成物を提供するものである。That is, the present invention provides a hydroxyl value of 5 to 100 mgK
OH / g, a glass transition temperature of 0 to 80 ° C, a weight-average molecular weight of 20,000 to 400,000, a water-dispersible copolymer (A) having a solid content of 20% by weight or more in the vehicle component, and SP Value (solubility parameter value) is 7.4 to
9.8 plasticizer and / or organic solvent with a resin solid content of 1
A base coating composition (I) containing 1 to 50 parts by weight per 100 parts by weight of a crosslinking agent (II) containing a compound containing at least two or more isocyanate groups in one molecule. The isocyanate group contained in the crosslinking agent (II) is 0.2 to 3.0 with respect to 1 mol of the hydroxyl group contained in the paint (I).
It is intended to provide a two-pack type aqueous coating composition, which is mixed immediately before use so as to become a mole.
【０００８】以下、本発明について説明する。Hereinafter, the present invention will be described.
【０００９】本発明においてベ−ス塗料（Ｉ）に用いら
れる水分散型共重合体（Ａ）は、水酸基価５〜１００ｍ
ｇＫＯＨ／ｇ、好ましくは１０〜５０ｍｇＫＯＨ／ｇ、
ガラス転移温度０〜８０℃、好ましくは１０〜６０℃、
重量平均分子量２０，０００〜４００，０００、好まし
くは８０，０００〜３００，０００の共重合体であり、
通常、水酸基含有モノマ−及びこれと共重合可能な他の
不飽和モノマ−を含むモノマ−混合物を乳化剤の存在下
で乳化重合させることにより得られる。In the present invention, the water-dispersible copolymer (A) used in the base coating material (I) has a hydroxyl value of 5 to 100 m.
gKOH / g, preferably 10-50 mgKOH / g,
Glass transition temperature 0 to 80 ° C, preferably 10 to 60 ° C,
A copolymer having a weight average molecular weight of 20,000 to 400,000, preferably 80,000 to 300,000;
Usually, it is obtained by emulsion polymerization of a monomer mixture containing a hydroxyl group-containing monomer and another unsaturated monomer copolymerizable therewith in the presence of an emulsifier.
【００１０】該共重合体（Ａ）の水酸基価が５ｍｇＫＯ
Ｈ／ｇ未満では架橋点が乏しく塗膜物性が不十分とな
り、一方１００ｍｇＫＯＨ／ｇを越えると初期耐水性が
低下し、さらに塗料粘度が高くなるため塗装作業性も低
下するので好ましくない。該共重合体（Ａ）のガラス転
移温度が０℃未満では形成膜の耐水性、耐汚染性に劣
り、一方８０℃を越えると造膜のための可塑剤や有機溶
剤を過剰量必要とするため初期乾燥性が悪くなり形成膜
にも経時でワレなどが発生しやすくなるので好ましくな
い。The copolymer (A) has a hydroxyl value of 5 mg KO
If it is less than H / g, the crosslinking point is poor and the physical properties of the coating film are insufficient. On the other hand, if it exceeds 100 mgKOH / g, the initial water resistance is lowered and the viscosity of the coating is increased, so that the coating workability is undesirably reduced. If the glass transition temperature of the copolymer (A) is less than 0 ° C., the formed film is inferior in water resistance and stain resistance, while if it exceeds 80 ° C., an excessive amount of a plasticizer or an organic solvent for film formation is required. Therefore, the initial drying property is deteriorated, and cracks and the like easily occur in the formed film over time, which is not preferable.
【００１１】また該共重合体（Ａ）の重量平均分子量が
２０，０００未満では形成膜の耐候性、耐水性に劣り、
一方４００，０００を越えると他の塗料成分との相溶性
に劣り造膜性、硬化性が低下するので好ましくない。When the weight average molecular weight of the copolymer (A) is less than 20,000, the formed film is inferior in weather resistance and water resistance,
On the other hand, if it exceeds 400,000, the compatibility with other paint components is inferior and the film-forming properties and curability deteriorate, which is not preferable.
【００１２】該共重合体（Ａ）に用いられる水酸基含有
モノマ−としては、例えば２−ヒドロキシエチル（メ
タ）アクリレ−ト、２−ヒドロキシプロピル（メタ）ア
クリレ−トなどのアクリル酸又はメタクリル酸の炭素数
１〜６のヒドロキシアルキルエステル；ヒドロキシエチ
ルビニルエ−テルなどのヒドロキシアルキルビニルエ−
テル類；エチレングリコ−ルなどのグリコ−ル（炭素数
２〜２０）やポリエチレングリコ−ルなどのポリエ−テ
ルポリオ−ルと（メタ）アクリル酸などの不飽和カルボ
ン酸との等モル付加物；ポリエチレングリコ−ルなどの
ポリエ−テルポリオ−ルと２−ヒドロキシエチル（メ
タ）アクリレ−トなどの水酸基含有モノマ−とのモノエ
−テルなどが挙げられ、これらは１種又は２種以上適宜
選択して使用できる。Examples of the hydroxyl-containing monomer used in the copolymer (A) include acrylic acid or methacrylic acid such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Hydroxyalkyl esters having 1 to 6 carbon atoms; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether
Ters; equimolar adducts of polyetherpolyols such as ethylene glycol and the like (polycarbonates having 2 to 20 carbon atoms) and polyethylene glycol and unsaturated carboxylic acids such as (meth) acrylic acid; Monoethers of a polyether polyol such as polyethylene glycol and a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate may be used, and one or more of them may be appropriately selected. Can be used.
【００１３】該共重合体（Ａ）に用いられる他の不飽和
モノマ−としては、例えばメチル（メタ）アクリレ−
ト、エチル（メタ）アクリレ−ト、ｎ−ブチル（メタ）
アクリレ−ト、ｉ−ブチル（メタ）アクリレ−ト、ｔ−
ブチル（メタ）アクリレ−ト、２−エチルヘキシル（メ
タ）アクリレ−ト、ラウリル（メタ）アクリレ−ト、イ
ソボルニル（メタ）アクリレ−ト等のアクリル酸又はメ
タクリル酸の炭素数１〜２４のアルキルエステル又はシ
クロアルキルエステル；（メタ）アクリル酸などの不飽
和カルボン酸、スルホエチル（メタ）アクリレ−ト及び
そのナトリウム塩もしくはアンモニウム塩；ジメチルア
ミノエチル（メタ）アクリレ−ト、（メタ）アクリルア
ミド；スチレン、α−メチルスチレン、ビニルトルエン
等のビニル芳香族化合物；酢酸ビニル、塩化ビニル、ビ
ニルエ−テル、（メタ）アクリロニトリル；ビニルトリ
メトキシシラン、γ−（メタ）アクリロイルオキシプロ
ピルトリメトキシシラン等のアルコキシシリル基含有モ
ノマ−；パーフルオロブチルエチル（メタ）アクリレー
ト、パーフルオロオクチルエチル（メタ）アクリレート
等のパーフルオロアルキル（メタ）アクリレート；フル
オロオレフィンなどが挙げられ、これらは１種又は２種
以上適宜選択して使用できる。Other unsaturated monomers used in the copolymer (A) include, for example, methyl (meth) acryl
, Ethyl (meth) acrylate, n-butyl (meth)
Acrylate, i-butyl (meth) acrylate, t-
C1-C24 alkyl esters of acrylic acid or methacrylic acid such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, or Cycloalkyl ester; unsaturated carboxylic acid such as (meth) acrylic acid, sulfoethyl (meth) acrylate and its sodium or ammonium salt; dimethylaminoethyl (meth) acrylate, (meth) acrylamide; styrene, α- Vinyl aromatic compounds such as methylstyrene and vinyltoluene; vinyl acetate, vinyl chloride, vinyl ether, (meth) acrylonitrile; monomers containing alkoxysilyl groups such as vinyltrimethoxysilane and γ- (meth) acryloyloxypropyltrimethoxysilane -; Perfluo Perfluoroalkyl (meth) acrylates such as robutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefins; and one or more of these can be appropriately selected and used.
【００１４】本発明において上記水分散型共重合体
（Ａ）は、ベ−ス塗料（Ｉ）のビヒクル成分中に固形分
で２０重量％以上、好ましくは５０重量％以上、さらに
好ましくは８０重量％以上含有される。該含有量が２０
重量％未満では、耐水性や耐久性などの塗膜性能が十分
得られないので好ましくない。In the present invention, the water-dispersed copolymer (A) is contained in the vehicle component of the base paint (I) in a solid content of at least 20% by weight, preferably at least 50% by weight, more preferably at least 80% by weight. % Or more. The content is 20
When the amount is less than the weight%, it is not preferable because the coating properties such as water resistance and durability cannot be sufficiently obtained.
【００１５】ベ−ス塗料（Ｉ）のビヒクル成分として、
必要に応じて併用される他の樹脂エマルションとして
は、例えば、酢酸ビニルエマルジョン、アクリル樹脂エ
マルジョン、酢ビ−アクリルエマルジョン、エチレン−
酢ビエマルジョン、シリコンアクリルエマルジョン、エ
ポキシ樹脂エマルジョン、ウレタン樹脂エマルジョン、
アルキド樹脂エマルジョン、ポリウレタンエマルジョン
などが挙げられ、また併用される水溶性樹脂としては、
水溶性アクリル樹脂、ポリビニルアルコ−ル、天然もし
くは合成ゴムラテックスなどが挙げられ、これらは１種
又は２種以上適宜選択して使用できる。As a vehicle component of the base paint (I),
Other resin emulsions used in combination as needed include, for example, vinyl acetate emulsion, acrylic resin emulsion, vinyl acetate-acryl emulsion, ethylene-
Vinegar emulsion, silicone acrylic emulsion, epoxy resin emulsion, urethane resin emulsion,
Alkyd resin emulsion, polyurethane emulsion and the like, and as the water-soluble resin used in combination,
Examples thereof include a water-soluble acrylic resin, polyvinyl alcohol, and natural or synthetic rubber latex, and one or more of these can be appropriately selected and used.
【００１６】上記ベ−ス塗料（Ｉ）は、造膜助剤とし
て、ＳＰ値（溶解性パラメ−タ−値）が７．４〜９．８
である可塑剤及び／又は有機溶剤を含有してなる。ＳＰ
値がこの範囲外では樹脂との相溶性に劣り塗料中で分離
する場合があるので好ましくない。The base paint (I) has an SP value (solubility parameter value) of 7.4 to 9.8 as a film-forming aid.
Or a plasticizer and / or an organic solvent. SP
If the value is outside this range, the compatibility with the resin is poor, and the resin may be separated in the paint, which is not preferable.
【００１７】このような可塑剤としては、例えばジ−２
−エチルヘキシルフタレ−ト、ジイソニルフタレ−ト、
ジブチルフタレ−ト、ジイソデシルフタレ−トなどが挙
げられ、有機溶剤としては、例えばテキサノ−ル、テキ
サノ−ルイソブチレ−ト、ブチルセロソルブ、プロピレ
ングリコ−ルモノメチルエ−テル、ブチルカルビト−
ル、アジピン酸ジイソプロピルなどのアルコ−ル系、エ
ステル系、エ−テル系、炭化水素系溶剤が挙げられ、こ
れらは１種又は２種以上適宜選択して使用できる。これ
らの含有量はベ−ス塗料（Ｉ）中に樹脂固形分１００重
量部に対して１〜５０重量部、好ましくは１０〜３０重
量部である。該含有量が１重量部未満では、造膜中に膜
がワレたり均一な膜が得られず、一方５０重量部を越え
ると乾燥性が低下し汚れやすくなるので好ましくない。As such a plasticizer, for example, di-2
-Ethylhexyl phthalate, diisonyl phthalate,
Examples include dibutyl phthalate and diisodecyl phthalate. Examples of the organic solvent include texanol, texanol isobutylate, butyl cellosolve, propylene glycol monomethyl ether, and butyl carbitol.
And alcohol-based solvents such as diisopropyl adipate, ester-based, ether-based, and hydrocarbon-based solvents. One or more of these can be appropriately selected and used. Their content is 1 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the resin solid content in the base paint (I). If the content is less than 1 part by weight, the film may be cracked or a uniform film may not be obtained during film formation. On the other hand, if it exceeds 50 parts by weight, the drying property may be reduced and the film may be easily stained.
【００１８】上記ベ−ス塗料（Ｉ）は、さらに必要に応
じて着色顔料や体質顔料などの顔料類；顔料分散剤、硬
化触媒、消泡剤、増粘剤、防腐剤、凍結防止剤などの塗
料用添加剤を含有してもよい。The base paint (I) may further comprise, if necessary, pigments such as coloring pigments and extender pigments; pigment dispersants, curing catalysts, defoamers, thickeners, preservatives, antifreezing agents and the like. May be added.
【００１９】このうち硬化触媒としては、特に制限なく
従来公知のものが使用でき、例えばトリエチルアミン、
トリプロピルアミン、トリブチルアミン、ジエタノ−ル
アミン、トリエタノ−ルアミンなどのアミン触媒；ジブ
チル錫ジラウレ−ト、ジブチル錫オキサイド、オクチル
酸錫、ナフテン酸鉛、ナフテン酸コバルトなどが使用で
き、また消泡剤としては、例えばポリエ−テル系、ポリ
シロキサンとポリエ−テルの共重合系、ポリシロキサン
とケイ酸の縮合物系、金属石鹸系などが使用できる。Among these, as the curing catalyst, any conventionally known curing catalyst can be used without any particular limitation. For example, triethylamine,
Amine catalysts such as tripropylamine, tributylamine, diethanolamine and triethanolamine; dibutyltin dilaurate, dibutyltin oxide, tin octylate, lead naphthenate and cobalt naphthenate can be used; For example, polyethers, copolymers of polysiloxane and polyether, condensates of polysiloxane and silicic acid, and metal soaps can be used.
【００２０】本発明において架橋剤（II）は、１分子中
少なくとも２個以上のイソシアネ−ト基を含有する化合
物を含むものであり、該架橋剤（II）として、１分子中
にイソシアネ−ト基を少なくとも２個以上含有するポリ
イソシアネ−ト化合物を、このままで或いは界面活性剤
と共に使用して上記ベ−ス塗料（Ｉ）に添加し攪拌混合
することができ、さらに水分散性の点からは該ポリイソ
シアネ−ト化合物を界面活性剤などにより変性して使用
することが好適である。かかる変性物としては、従来公
知の手法により親水性鎖を導入してなるものであれば特
に制限なく使用でき、例えば（ｉ）アルコキシポリアル
キレングリコ−ルとポリイソシアネ−ト化合物との反応
生成物、（ii）ポリイソシアネ−ト化合物にアルコキシ
ポリアルキレングリコ−ルとジアルカノ−ルアミンとを
反応させることにより得られる乳化剤と、ポリイソシア
ネ−ト化合物との混合物、（iii)アルコキシポリアルキ
レングリコ−ルとポリイソシアネ−ト化合物との反応生
成物と、アミノ・ホルムアルデヒド樹脂とからなるポリ
ウレタンアミノ樹脂共重合体、（iv）上記反応生成物
（ｉ）又は混合物（ii）のポリイソシアネートと片末端
に水酸基又はアミノ基をもう片末端にアルコキシシリル
基を有するシランカップリング剤との反応生成物などが
挙げられる。In the present invention, the crosslinking agent (II) contains a compound containing at least two or more isocyanate groups in one molecule, and is used as the crosslinking agent (II) in one molecule. A polyisocyanate compound containing at least two groups can be added to the above base paint (I) as it is or by using it together with a surfactant and mixed by stirring. Further, from the viewpoint of water dispersibility, It is preferable to use the polyisocyanate compound after modifying it with a surfactant or the like. As such a modified product, any one obtained by introducing a hydrophilic chain by a conventionally known method can be used without particular limitation. For example, (i) a reaction product of an alkoxypolyalkylene glycol and a polyisocyanate compound, (Ii) a mixture of an emulsifier obtained by reacting a polyisocyanate compound with an alkoxypolyalkylene glycol and a dialkanolamine, and a polyisocyanate compound; (iii) an alkoxypolyalkylene glycol and a polyisocyanate A polyurethaneamino resin copolymer comprising a reaction product of a compound and an amino-formaldehyde resin; and (iv) a hydroxyl group or an amino group at one end with the polyisocyanate of the reaction product (i) or the mixture (ii). Reaction product with a silane coupling agent having an alkoxysilyl group at one end And the like.
【００２１】該ポリイソシアネ−ト化合物としては、例
えばテトラメチレンジイソシアネ−ト、ヘキサメチレン
ジイソシアネ−ト、トリメチルヘキサメチレンジイソシ
アネ−ト、イソホロンジイソシアネ−トなどの脂肪族ジ
イソシアネ−ト；４・４´−メチレンビス（シクロヘキ
シルイソシアネ−ト）、イソホロンジイソシアネ−トな
どの脂環族ジイソシアネ−ト；キシリレンジイソシアネ
−ト、トリレンジイソシアネ−ト、ジフェニルメタンジ
イソシアネ−ト、ポリフェニルメタンジイソシアネ−ト
（以下ポリメリックＭＤＩ）などの芳香族ジイソシアネ
−ト；及びこれらのイソシアヌレ−ト体やビュウレット
体等の類似の化合物が挙げられ、これらは１種又は２種
以上混合して使用できる。Examples of the polyisocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates such as 4.4'-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate; And aromatic diisocyanates such as polyphenylmethane diisocyanate (hereinafter referred to as polymeric MDI); and similar compounds such as isocyanurates and burettes. These may be used alone or in combination of two or more. Can be used.
【００２２】上記ポリイソシアネ−ト化合物とアルコキ
シポリアルキレングリコ−ルとの反応生成物（ｉ）は、
残存イソシアネ−ト含量が２０〜３０重量％となるよう
に反応せしめてなる水分散可能なポリイソシアネ−トで
あり、具体的には、上記ポリイソシアネ−ト化合物とア
ルコキシポリアルキレングリコ−ルとを、イソシアネ−
ト基／水酸基の当量比が３〜３０好ましくは１０〜２５
程度となるよう反応させるのが適当である。該アルコキ
シポリアルキレングリコ−ルとしては、一般式Ｒ1 Ｏ−
（Ｒ2 Ｏ）n −Ｈ（ここでＲ1 はアルキル基、Ｒ2 はア
ルキレン基、ｎは２〜１００）で示されるものであり、
例えばメトキシポリメチレンエ−テルグリコ−ル、メト
キシポリエチレンエ−テルグリコ−ル、エトキシポリエ
チレンエ−テルグリコ−ル、エトキシポリブチレンエ−
テルグリコ−ルなどが挙げられ、分子量が１００〜４，
０００、好ましくは４００〜２，０００の範囲を有する
ものが使用できる。The reaction product (i) of the polyisocyanate compound with the alkoxypolyalkylene glycol is as follows:
A water-dispersible polyisocyanate which is reacted so that the residual isocyanate content becomes 20 to 30% by weight. Specifically, the above-mentioned polyisocyanate compound and alkoxypolyalkylene glycol are mixed with isocyanate. −
And the equivalent ratio of g-hydroxyl group is 3 to 30, preferably 10 to 25.
It is appropriate to make the reaction to a degree. The alkoxypolyalkylene glycol has a general formula of R 1 O—
(R 2 O) n -H (where R 1 is an alkyl group, R 2 is an alkylene group, and n is 2 to 100),
For example, methoxypolymethylene ether glycol, methoxypolyethylene ether glycol, ethoxypolyethylene ether glycol, ethoxypolybutylene ether
Terglycol and the like.
Those having a range of 000, preferably 400 to 2,000 can be used.
【００２３】次いで上記ポリイソシアネ−ト化合物にア
ルコキシポリアルキレングリコ−ルとジアルカノ−ルア
ミンとを反応させることにより得られる乳化剤と、ポリ
イソシアネ−ト化合物との混合物（ii）は、水分散可能
なポリイソシアネ−ト組成物であり、該乳化剤とポリイ
ソシアネ−ト化合物とをイソシアネ−ト含量が３〜５０
重量％、好ましくは５〜３０重量％となるように混合し
たものが適当であり、これらは一部反応させておいても
よい。Next, a mixture (ii) of an emulsifier obtained by reacting the above-mentioned polyisocyanate compound with an alkoxypolyalkylene glycol and a dialkanolamine with a polyisocyanate compound is a water-dispersible polyisocyanate. A composition comprising an emulsifier and a polyisocyanate compound having an isocyanate content of 3 to 50.
%, Preferably 5 to 30% by weight, and these may be partially reacted.
【００２４】該乳化剤は、ポリイソシアネ−ト化合物と
アルコキシポリアルキレングリコ−ルとをイソシアネ−
ト基／水酸基の当量比が３〜３０、好ましくは１０〜２
５程度となるよう反応させた後、未反応のポリイソシア
ネ−ト化合物を除去し、次いでジアルカノ−ルアミンを
イソシアネ−ト基／アミノ基の当量比が０．５〜２、好
ましくは０．８〜１．２程度となるよう反応させること
により得られる。該乳化剤の製造に用いられるアルコキ
シポリアルキレングリコ−ルは、上記（ｉ）と同様のも
のが使用でき、該ジアルカノ−ルアミンとしては、例え
ばジメタノ−ルアミン、ジエタノ−ルアミン、ジイソプ
ロパノ−ルアミン、ジエタノ−ルアニリン等が使用でき
る。The emulsifier comprises a polyisocyanate compound and an alkoxypolyalkylene glycol, which is an isocyanate compound.
And the equivalent ratio of (g) group / hydroxyl group is 3 to 30, preferably 10 to 2
After the reaction, the unreacted polyisocyanate compound is removed, and then the dialkanolamine is converted to an isocyanate group / amino group equivalent ratio of 0.5-2, preferably 0.8-1. It is obtained by reacting to about 0.2. As the alkoxypolyalkylene glycol used in the production of the emulsifier, the same as those described in the above (i) can be used. As the dialkanolamine, for example, dimethanolamine, diethanolamine, diisopropanolamine, diethanolaniline Etc. can be used.
【００２５】次いでアルコキシポリアルキレングリコ−
ルとポリイソシアネ−ト化合物との反応生成物と、アミ
ノ・ホルムアルデヒド樹脂とからなるポリウレタンアミ
ノ樹脂共重合体（iii)は、前記（ｉ）で得られる反応生
成物にアミノ・ホルムアルデヒド樹脂を、残存イソシア
ネ−ト含量が１５〜３０％となるように反応せしめて得
ることができる。Next, the alkoxypolyalkylene glyco-
(Iii) is a polyurethane amino resin copolymer comprising a reaction product of a polyisocyanate compound with a polyisocyanate compound and an amino-formaldehyde resin. The reaction can be carried out so that the content is 15 to 30%.
【００２６】該共重合体（iii)の製造に用いられるアミ
ノ・ホルムアルデヒド樹脂としては、例えばメラミン、
尿素、ベンゾグアナミン、アセトグアナミンなどのアミ
ノ化合物とホルムアルデヒドとの反応によって得られる
ものが使用でき、さらにこれをアルコ−ルによってエ−
テル化したものも使用できる。エ−テル化に用いられる
アルコ−ルはメタノ−ル、エタノ−ル、ｎ−，ｉ−プロ
パノ−ル、ｎ−，ｉ−，ｔ−ブタノ−ルなどが挙げられ
る。The amino-formaldehyde resin used for producing the copolymer (iii) includes, for example, melamine,
Those obtained by the reaction of an amino compound such as urea, benzoguanamine or acetoguanamine with formaldehyde can be used.
Tellurized materials can also be used. Alcohols used for etherification include methanol, ethanol, n-, i-propanol, n-, i-, t-butanol and the like.
【００２７】次いで上記反応生成物（ｉ）又は混合物
（ii）のポリイソシアネートと片末端に水酸基又はアミ
ノ基をもう片末端にアルコキシシリル基を有するシラン
カップリング剤との反応生成物（iv）は、上記（ｉ）又
は（ii）の水分散可能に親水化されたポリイソシアネ−
トのイソシアネ−ト基にシランカップリング剤の水酸基
又はアミノ基をイソシアネ−ト基／水酸基又はアミノ基
の当量比が３〜３０で反応させることにより得られ、残
存イソシアネ−ト含量が３〜５０重量％、好ましくは５
〜３０重量％であることが適当である。該含量が３重量
％未満では、得られる塗膜の耐水性に劣り、一方５０重
量％を越えると架橋剤の水分散性が悪くなるので望まし
くない。The reaction product (iv) of the above reaction product (i) or the mixture (ii) of the polyisocyanate with a silane coupling agent having a hydroxyl group or an amino group at one end and an alkoxysilyl group at the other end is And the water-dispersible polyisocyanate of the above (i) or (ii).
The hydroxyl group or amino group of the silane coupling agent is reacted with the isocyanate group of the silane coupling agent at an equivalent ratio of isocyanate group / hydroxyl group or amino group of 3 to 30, and the residual isocyanate content is 3 to 50. % By weight, preferably 5%
Suitably, it is about 30% by weight. If the content is less than 3% by weight, the water resistance of the resulting coating film is poor, while if it exceeds 50% by weight, the water dispersibility of the crosslinking agent deteriorates, which is not desirable.
【００２８】上記反応生成物（iv）の製造に用いられる
シランカップリング剤としては、例えばＮ−β−（アミ
ノエチル）−γ−アミノプロピルトリメトキシシラン、
Ｎ−β−（アミノエチル）−γ−アミノプロピルメチル
ジメトキシシラン、γ−アミノプロピルトリエトキシシ
ラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシ
シラン、γ−メルカプトプロピルトリメトキシシランな
どが挙げられる。また上記反応生成物（iv）の製造に用
いられるアルコキシポリアルキレングリコ−ルは、上記
（ｉ）と同様のものが使用できる。Examples of the silane coupling agent used for producing the above reaction product (iv) include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane,
N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. As the alkoxypolyalkylene glycol used in the production of the reaction product (iv), the same one as in the above (i) can be used.
【００２９】上記（ｉ）〜（iv）のうち架橋剤（II）と
しては、特に水分散時の安定性の面から親水性と疎水性
のバランスのとれた（iv）が好適である。Among the above (i) to (iv), as the cross-linking agent (II), (iv) having a good balance between hydrophilicity and hydrophobicity is particularly preferable from the viewpoint of stability during dispersion in water.
【００３０】本発明の２液型水性塗料組成物は、上記ベ
−ス塗料（Ｉ）及び架橋剤（II）からなり、これらはベ
−ス塗料（Ｉ）中に含まれる水酸基１モルに対して架橋
剤（II）中に含まれるイソシアネ−ト基が０．２〜３．
０モル、好ましくは０．５〜２．５モルとなるように使
用直前に混合して使用に供する。The two-pack aqueous coating composition of the present invention comprises the above base paint (I) and a crosslinking agent (II), and these are based on 1 mol of hydroxyl groups contained in the base paint (I). The isocyanate group contained in the crosslinking agent (II) is 0.2 to 3;
The mixture is used immediately before use so as to be 0 mol, preferably 0.5 to 2.5 mol.
【００３１】本発明組成物は、スプレ−塗装、ロ−ラ−
塗装、刷毛塗り、浸漬など従来公知の方法で各種素材に
塗装できる。塗布量は、特に制限はないが、一般には約
５０〜４００ｇ／ｍ2 程度が適当である。The composition of the present invention can be used for spray coating and roller coating.
It can be applied to various materials by a conventionally known method such as painting, brushing, and dipping. The amount of coating is not particularly limited, but generally about 50 to 400 g / m 2 is appropriate.
【００３２】[0032]
【実施例】以下、実施例を挙げて本発明をさらに詳細に
説明する。尚、「部」及び「％」はそれぞれ「重量部」
及び「重量％」を示す。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” are “parts by weight” respectively.
And "% by weight".
【００３３】水分散型共重合体の製造例 製造例１ 攪拌機、温度計、還流管、窒素導入管を備えた容量２リ
ットルの４つ口フラスコに脱イオン水３０９部、Ｎｅｗ
ｃｏｌ７０７ＳＦ（日本乳化剤社製、アニオン界面活性
剤、不揮発分３０％）１．１部を加え窒素置換後攪拌し
ながら８５℃に保った。この中に下記組成をエマルジョ
ン化してなるプレエマルジョンのうち２１部及び過硫酸
アンモニウム０．３２部を添加し、添加２０分後から残
りのプレエマルジョンを４時間かけて滴下した。Production Example of Water-Dispersed Copolymer Production Example 1 309 parts of deionized water was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, and New
1.1 parts of col707SF (manufactured by Nippon Emulsifier Co., anionic surfactant, nonvolatile content: 30%) was added, and the mixture was replaced with nitrogen and kept at 85 ° C with stirring. To this, 21 parts of the pre-emulsion obtained by emulsifying the following composition and 0.32 parts of ammonium persulfate were added, and 20 minutes after the addition, the remaining pre-emulsion was dropped over 4 hours.
【００３４】 脱イオン水 ３２５ 部 Ｎｅｗｃｏｌ７０７ＳＦ ４３．３〃 メチルメタクリレ−ト ３９ 〃 スチレン ７８ 〃 ｎ−ブチルメタクリレ−ト ２４７ 〃 ２−エチルヘキシルメタクリレ−ト ２４７ 〃 ２−ヒドロキシエチルメタクリレ−ト ３２．５〃 アクリル酸 ６．５〃 過硫酸アンモニウム １．３〃 滴下終了時から２時間８５℃に保持した後、４０℃に降
温した。アンモニア水でｐＨ８．５に調整し固形分５０
％、重量平均分子量１５０，０００の水分散型共重合体
（Ａ）を得た。Deionized water 325 parts Newcol 707SF 43.3 {methyl methacrylate 39} styrene 78 {n-butyl methacrylate 247} 2-ethylhexyl methacrylate 247 {2-hydroxyethyl methacrylate 32 5.5〃 Acrylic acid 6.5〃 Ammonium persulfate 1.3〃 After maintaining at 85 ° C. for 2 hours from the end of dropping, the temperature was lowered to 40 ° C. Adjust the pH to 8.5 with aqueous ammonia and adjust the solid content to 50.
%, A water-dispersed copolymer (A) having a weight average molecular weight of 150,000 was obtained.
【００３５】製造例２〜９ 製造例１においてプレエマルジョンのモノマ−量及び触
媒量を表１の通りとする以外は製造例１と同様の操作で
水分散型共重合体（Ｂ）〜（Ｉ）を得た。Production Examples 2 to 9 Water-dispersed copolymers (B) to (I) were prepared in the same manner as in Production Example 1 except that the amounts of monomers and catalysts in the pre-emulsion were changed as shown in Table 1. ) Got.
【００３６】[0036]
【表１】 [Table 1]
【００３７】水性樹脂の製造例 製造例１０ 攪拌機、温度計、還流管、窒素導入管を備えた容量２リ
ットルの４つ口フラスコにエチレングリコ−ルモノブチ
ルエ−テルを６５０部仕込み、これを１２０℃に保持し
た中に、メチルメタクリレ−ト４５．５部、スチレン１
３０部、ｎ−ブチルメタクリレ−ト２０８部、２−エチ
ルヘキシルメタクリレ−ト２０８部、２−ヒドロキシエ
チルメタクリレ−ト３２．５部、アクリル酸２６部、及
びアゾビスイソブチロニトリル３２．５部の混合物を４
時間要して滴下し、滴下終了後２時間反応を続けて固形
分５０％、重量平均分子量６，０００のアクリル共重合
体溶液を得た。Production Example of Aqueous Resin Production Example 10 650 parts of ethylene glycol monobutyl ether was charged into a two-liter four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, and heated to 120 ° C. While maintaining, 45.5 parts of methyl methacrylate, styrene 1
30 parts, n-butyl methacrylate 208 parts, 2-ethylhexyl methacrylate 208 parts, 2-hydroxyethyl methacrylate 32.5 parts, acrylic acid 26 parts, and azobisisobutyronitrile Add 5 parts of mixture to 4
After the addition, the reaction was continued for 2 hours after the completion of the addition to obtain an acrylic copolymer solution having a solid content of 50% and a weight average molecular weight of 6,000.
【００３８】次いで得られたアクリル共重合体溶液１０
０部に、該共重合体中のカルボキシル基に対して１．０
当量のトリエチルアミンを加えて中和し、さらに脱イオ
ン水を加えて固形分２５％の水性樹脂（Ｍ）を得た。Next, the obtained acrylic copolymer solution 10
0 parts, 1.0 to the carboxyl group in the copolymer.
An equivalent amount of triethylamine was added to neutralize, and further deionized water was added to obtain an aqueous resin (M) having a solid content of 25%.
【００３９】製造例１１ 製造例１０において、モノマ−組成をメチルメタクリレ
−ト７８部、スチレン１３０部、ｎ−ブチルメタクリレ
−ト２０８部、２−エチルヘキシルメタクリレ−ト２０
８部、アクリル酸２６部の通りとする以外は製造例１０
と同様の操作で水性樹脂（Ｎ）を得た。Production Example 11 In Production Example 10, the monomer composition was changed to 78 parts of methyl methacrylate, 130 parts of styrene, 208 parts of n-butyl methacrylate, and 20 parts of 2-ethylhexyl methacrylate.
Production Example 10 except that 8 parts and 26 parts of acrylic acid were used.
Water-based resin (N) was obtained by the same operation as described above.
【００４０】架橋剤の作成 作成例１ 攪拌機、温度計、還流管、窒素導入管を備えた４つ口フ
ラスコに、数平均分子量５５０のメトキシポリエチレン
エ−テルグリコ−ル４１部と「タケネ−トＤ１７０Ｈ
Ｎ」（武田薬品工業社製、１，６−ヘキサメチレンジイ
ソシアネ−トの三量体）５０４部を入れ、窒素置換後７
０℃で６時間反応させて水分散可能なポリイソシアネ−
トを得た。イソシアネ−ト含量は２２．９％、粘度１
３００ｃｐｓであった。Preparation of Crosslinking Agent Preparation Example 1 In a four-necked flask equipped with a stirrer, thermometer, reflux tube and nitrogen inlet tube, 41 parts of methoxypolyethylene ether glycol having a number average molecular weight of 550 and "Takenate D170H" were added.
N "(trimer of 1,6-hexamethylene diisocyanate, manufactured by Takeda Pharmaceutical Co., Ltd.)
Water-dispersible polyisocyanate reacted at 0 ° C for 6 hours
I got it. Isocyanate content 22.9%, viscosity 1
It was 300 cps.
【００４１】作成例２ 作成例１と同様のフラスコに、数平均分子量５５０のメ
トキシポリエチレンエ−テルグリコ−ル２２５部と１，
６−ヘキサメチレンジイソシアネ−ト８７１部を入れ、
窒素置換後７０℃で６時間反応させた。得られた反応液
を薄膜蒸留装置にかけ、未反応の１，６−ヘキサメチレ
ンジイソシアネ−トを取り除き、メトキシポリエチレン
エ−テルグリコ−ルを有するモノイソシアネ−ト化合物
を得た。次いで同様の別フラスコに、ジエタノ−ルアミ
ン３７部を入れ、窒素置換後空冷しながら作成例１で得
たメトキシポリエチレンエ−テルグリコ−ルを有するモ
ノイソシアネ−ト化合物２５０部を反応温度が７０℃を
越えないように徐々に滴下した。滴下終了後、約１時間
７０℃で攪拌しイソシアネ−ト基が消失したことを確認
し、乳化剤を得た。Preparation Example 2 In the same flask as in Preparation Example 1, 225 parts of methoxypolyethylene ether glycol having a number average molecular weight of 550 and 1,
871 parts of 6-hexamethylene diisocyanate are added,
After the replacement with nitrogen, the mixture was reacted at 70 ° C. for 6 hours. The resulting reaction solution was applied to a thin film distillation apparatus to remove unreacted 1,6-hexamethylene diisocyanate, thereby obtaining a monoisocyanate compound having methoxypolyethylene ether glycol. Next, 37 parts of diethanolamine was placed in the same separate flask, and 250 parts of the monoisocyanate compound having methoxypolyethylene ether glycol obtained in Preparation Example 1 obtained in Preparation Example 1 was cooled while cooling with nitrogen and the reaction temperature exceeded 70 ° C. Drip slowly so as not to. After completion of the dropwise addition, the mixture was stirred at 70 ° C. for about 1 hour, and it was confirmed that the isocyanate group had disappeared. Thus, an emulsifier was obtained.
【００４２】別フラスコにこの乳化剤４２部と「タケネ
−トＤ１７０ＨＮ」（武田薬品工業社製、１，６−ヘキ
サメチレンジイソシアネ−トの三量体）３５８部を入
れ、７０℃で６時間攪拌することにより、水分散可能な
ポリイソシアネ−ト組成物を得た。イソシアネ−ト含
量は１９．３％、粘度２０００ｃｐｓであった。In a separate flask, 42 parts of this emulsifier and 358 parts of “Takenate D170HN” (trimer of 1,6-hexamethylene diisocyanate, manufactured by Takeda Pharmaceutical Co., Ltd.) are added, and the mixture is placed at 70 ° C. for 6 hours. By stirring, a water-dispersible polyisocyanate composition was obtained. The isocyanate content was 19.3% and the viscosity was 2000 cps.
【００４３】作成例３ 作成例１と同様のフラスコに、「ミリオネ−トＭＲ−２
００」（日本ポリウレタン工業社製、ポリメリックメチ
レンジイソシアネ−ト）９７０部を仕込み、次いで「Ｍ
ＰＧ−０８１」（日本乳化剤工業社製、メトキシポリエ
チレングリコ−ル）３０部を加えて昇温し、７０℃で３
時間反応させて、イソシアネ−ト含量２９．４％の茶褐
色透明のプレポリマ−を得た。さらに７０℃に保持した
ままアミノ・ホルムアルデヒド樹脂８０部を加え３時間
反応させて水分散可能なポリウレタンアミノ樹脂共重合
体を得た。イソシアネ−ト含量は２７．１％、粘度４
５０ｃｐｓであった。Preparation Example 3 In the same flask as in Preparation Example 1, "Millionate MR-2" was added.
00 (manufactured by Nippon Polyurethane Industry Co., Ltd., polymeric methylene diisocyanate).
PG-081 "(manufactured by Nippon Emulsifier Industry Co., Ltd., methoxypolyethylene glycol), and the mixture was heated at 70.degree.
The reaction was carried out for a period of time to obtain a brown transparent prepolymer having an isocyanate content of 29.4%. While maintaining the temperature at 70 ° C., 80 parts of amino-formaldehyde resin was added and reacted for 3 hours to obtain a water-dispersible polyurethaneamino resin copolymer. Isocyanate content 27.1%, viscosity 4
It was 50 cps.
【００４４】作成例４ 作成例１と同様のフラスコに、作成例２で得た乳化剤４
２部と「タケネ−トＤ１７０ＨＮ」（武田薬品工業社
製、１，６−ヘキサメチレンジイソシアネ−トの三量
体）３５８部を入れ、さらにＮ−β−（アミノエチル）
−γ−アミノプロピルトリメトキシシラン１２部を入
れ、７０℃で６時間攪拌することにより、水分散可能な
ポリイソシアネ−トを得た。イソシアネ−ト含量は１
７．７％、粘度８００ｃｐｓであった。Preparation Example 4 Emulsifier 4 obtained in Preparation Example 2 was placed in the same flask as in Preparation Example 1.
2 parts and 358 parts of "Takenate D170HN" (trimer of 1,6-hexamethylene diisocyanate, manufactured by Takeda Pharmaceutical Company Limited) were added, and N-β- (aminoethyl) was further added.
12 parts of -γ-aminopropyltrimethoxysilane was added and stirred at 70 ° C for 6 hours to obtain a water-dispersible polyisocyanate. The isocyanate content is 1
It was 7.7% and the viscosity was 800 cps.
【００４５】実施例及び比較例 ４リットルのステンレス容器に下記配合の原料を入れ、
ディスパ−で３０分間攪拌し、顔料分散ペ−ストを得
た。EXAMPLES AND COMPARATIVE EXAMPLES Raw materials having the following composition were placed in a 4-liter stainless steel container.
The mixture was stirred with a disperser for 30 minutes to obtain a pigment dispersion paste.
【００４６】 上水 ９６０部 「ノプコサントＫ」（サンノプコ社製、顔料分散剤） ４８〃 「アデカノ−ルＶＨ４２０」（旭電化社製、増粘剤） １６〃 「ＳＮデフォ−マ−Ａ６３」（サンノプコ社製、消泡剤） ３２〃 チタン白 ３５２０〃 エタノ−ル ２８８〃 次に１リットルのステンレス容器に、表２に示す配合
で、上記顔料ペ−ストや前記製造例で得た各水分散型共
重合体などを攪拌しながら配合し、各ベ−ス塗料を作成
した。960 parts of tap water “Nopco Santo K” (manufactured by San Nopco, a pigment dispersant) 48〃 “Adecanol VH420” (manufactured by Asahi Denka Co., Ltd., thickener) 16〃 “SN Deformer-A63” (San Nopco 32% Titanium White 3520 {Ethanol 288} Next, in a 1-liter stainless steel container, the above-mentioned pigment paste and each of the aqueous dispersions obtained in the above Production Examples were blended as shown in Table 2. The copolymers and the like were blended with stirring to prepare each base paint.
【００４７】得られたベ−ス塗料に、前記作成例で得た
架橋剤〜を表２に示す組合せ及び配合量で配合し、
攪拌して各水性塗料を得た。表２中の（注１）〜（注
３）は下記の通りである。得られた各水性塗料を下記性
能試験に供した。結果を表２に示す。The crosslinking agent obtained in the above preparation example was blended with the resulting base coating composition in the combinations and amounts shown in Table 2,
Each aqueous paint was obtained by stirring. (Note 1) to (Note 3) in Table 2 are as follows. Each of the obtained water-based paints was subjected to the following performance tests. Table 2 shows the results.
【００４８】（注１）造膜助剤ａ〜ｅは次の通りであ
る。(Note 1) The film-forming assistants a to e are as follows.
【００４９】 ａ：テキサノ−ル（ＳＰ値９．６） ｂ：ブチルセロソルブ（ＳＰ値８．９） ｃ：ジブチルフタレ−ト（ＳＰ値９．４） ｄ：アジピン酸ジイソプロピル（ＳＰ値７．５） ｅ：メチルセロソルブ（ＳＰ値１０．８） （注２）プライマルＴＴ−９３５：ロ−ム・アンド・ハ
−ス社製、増粘剤 （注３）スラオフＳ：武田薬品社製、防腐剤 （試験方法） （１）混和性：ベ−ス塗料に、架橋剤を加えた混合直後
と１時間後にそれぞれ１５０ミクロンのアプリケ−タ−
でガラス板に塗装し、２０℃・６０％ＲＨの雰囲気で１
時間放置した。１時間後の塗膜外観を目視で評価した。A: Texanol (SP value: 9.6) b: Butyl cellosolve (SP value: 8.9) c: Dibutyl phthalate (SP value: 9.4) d: Diisopropyl adipate (SP value: 7.5) e : Methyl cellosolve (SP value 10.8) (Note 2) Primal TT-935: Roam & Haas Co., Ltd., thickener (Note 3) Sluroff S: Takeda Pharmaceutical Co., preservative (Test Method) (1) Miscibility: 150 micron applicator immediately after mixing and 1 hour after adding the crosslinking agent to the base paint.
Paint on a glass plate at 20 ° C / 60% RH.
Left for hours. The appearance of the coating film after one hour was visually evaluated.
【００５０】 ◎：混合直後と１時間後のいずれも、ブツなど異常はみ
られない ○：混合直後ではブツがみられるが、１時間後では異常
はみられない ×：混合直後と１時間後のいずれもブツみられる。均一
な膜にならない （２）乾燥性：（１）と同様にして得られた塗膜の乾燥
性を指触で評価した。◎: No abnormalities such as lumps are observed immediately after mixing and 1 hour after. ：: Abnormalities are observed immediately after mixing, but no abnormality is observed 1 hour after. ×: Immediately after mixing and 1 hour after. All of them can be seen. (2) Drying property: The drying property of the coating film obtained in the same manner as in (1) was evaluated by finger touch.
【００５１】 ◎：完全硬化 ○：半硬化（塗膜を指で押すと跡がつくがしばらくする
と元にもどる） ×：指触乾燥以下（塗膜表面は乾燥しているが、内部が
乾燥していない） （３）屋外汚染性：スレ−ト板（９０×３００×６ｍ
ｍ）に、「ＶＰシ−ラ−白」（関西ペイント社製、溶剤
型シ−ラ−）を塗布量１００ｇ／ｍ2 になるようにロ−
ラ−で塗装・乾燥したものを被塗板とし、この上に上記
で得た各水性塗料（ベ−ス塗料に架橋剤を加え１時間放
置）を塗布量が１５０ｇ／ｍ2 になるようにスプレ−で
２回塗装し、常温で７日間乾燥して各試験塗板を作成し
た。◎: Completely cured ○: Semi-cured (When the coating is pressed with a finger, a mark is formed, but it returns to the original state after a while) ×: Less than touch drying (The coating film surface is dry, but the inside is dry (3) Outdoor pollution: Slate plate (90 × 300 × 6m)
m), VP Sealer White (a solvent-type sealer manufactured by Kansai Paint Co., Ltd.) so that the coating amount becomes 100 g / m 2.
The coated and dried paint was used as a plate to be coated, and each of the aqueous paints obtained above (a cross-linking agent was added to the base paint and left for 1 hour) was sprayed thereon so that the coating amount became 150 g / m 2. The coating was carried out twice at − and dried at room temperature for 7 days to prepare each test coated plate.
【００５２】この試験塗板を、平塚市内で南面に向かっ
て塗面を上に３０°に傾けて６ケ月屋外暴露試験に供
し、試験後の塗面を目視と初期板との色差ΔＥで評価し
た。The test coated plate was subjected to an outdoor exposure test for 6 months by tilting the coated surface upward at 30 ° toward the south side in Hiratsuka city, and the coated surface after the test was evaluated visually and by the color difference ΔE between the initial plate and the test plate. did.
【００５３】 ◎：塗面に汚れがみられず、初期板とのΔＥは５未満 ○：塗面に汚れが僅かにみられるが、初期板とのΔＥは
５以上１０未満 ×：塗面に汚れが著しくみられ、初期板とのΔＥは１０
以上 （４）耐候性：（３）と同様にして得られた試験塗板
を、サンシャインウェザ−メ−タ−で１０００時間促進
耐候試験に供し、試験後の塗膜を目視と光沢保持率で評
価した。光沢保持率（％）＝（１０００時間後の６０°
グロス）／（初期の６０°グロス）×１００ ◎：塗膜にワレ、ハガレ、フクレがなく、光沢保持率が
８０％以上 ○：塗膜にワレ、ハガレ、フクレが僅かにみられるか、
または光沢保持率が６０％以上８０％未満 ×：塗膜にワレ、ハガレ、フクレがみられるか、または
光沢保持率が６０％未満 （５）初期耐水性：前記ベ−ス塗料にさらに「ユニラン
ト８８青」（横浜化成社製、カラ−ペ−スト）５部を加
えた後、架橋剤を加えて水性塗料とし、これを１時間後
に１５０ミクロンのアプリケ−タ−でガラス板に塗装
し、４時間放置した。次いで該塗板を水に３０分間浸漬
し、引上げ後の塗膜状態を目視で評価した。 ◎：浸漬前と比べて変化なし ○：若干白っぽくなるが、３０分以内にもとの色に戻る ×：かなり白くなり、３０分たってもとの色に戻らない◎: No stain is seen on the coated surface, ΔE with the initial plate is less than 5. ：: Stain is slightly seen on the coated surface, but ΔE with the initial plate is 5 or more and less than 10. ×: On the coated surface Stain was remarkably observed, and ΔE with the initial plate was 10
(4) Weather resistance: The test coated plate obtained in the same manner as in (3) was subjected to an accelerated weather test for 1000 hours with a sunshine weather meter, and the coated film after the test was evaluated by visual observation and gloss retention. did. Gloss retention (%) = (60 ° after 1000 hours)
(Gloss) / (initial 60 ° gloss) × 100 ：: No cracks, peeling, or swelling in the coating film, and the gloss retention is 80% or more. ：: Slight cracking, peeling, or swelling in the coating film.
Or gloss retention of 60% or more and less than 80% ×: cracks, peeling, blisters are observed in the coating film, or gloss retention of less than 60% (5) Initial water resistance: “Unilant” is further added to the base paint. 88 Blue "(color paste, manufactured by Yokohama Kasei Co., Ltd.), and then a crosslinking agent was added to form a water-based paint. One hour later, a 150-micron applicator was applied to a glass plate. Left for 4 hours. Next, the coated plate was immersed in water for 30 minutes, and the state of the coated film after pulling was visually evaluated. ：: no change compared to before immersion ：: slightly whitish, but returns to original color within 30 minutes ×: considerably whitened, does not return to original color after 30 minutes
【００５４】[0054]
【発明の効果】本発明組成物によれば、特に低温及び多
湿の環境下でも架橋性を低下させることなく、耐候性、
耐水性、耐久性に優れる塗膜を形成できる。According to the composition of the present invention, the crosslinkability is not deteriorated even in a low-temperature and high-humidity environment,
A coating film having excellent water resistance and durability can be formed.
【００５５】[0055]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｇ 18/62 ＮＥＮ Ｃ０８Ｇ 18/62 ＮＥＮ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location C08G 18/62 NEN C08G 18/62 NEN
Claims (5)
ラス転移温度０〜８０℃、重量平均分子量２０，０００
〜４００，０００である水分散型共重合体（Ａ）をビヒ
クル成分中に固形分で２０重量％以上含有し、且つＳＰ
値（溶解性パラメ−タ−値）が７．４〜９．８である可
塑剤及び／又は有機溶剤を樹脂固形分１００重量部に対
し１〜５０重量部含有してなるベ−ス塗料（Ｉ）に、１
分子中少なくとも２個以上のイソシアネ−ト基を含有す
る化合物を含む架橋剤（II）を、ベ−ス塗料（Ｉ）中に
含まれる水酸基１モルに対して架橋剤（II）中に含まれ
るイソシアネ−ト基が０．２〜３．０モルとなるように
使用直前に混合することを特徴とする２液型水性塗料組
成物。1. A hydroxyl value of 5 to 100 mg KOH / g, a glass transition temperature of 0 to 80 ° C., and a weight average molecular weight of 20,000.
Water-dispersible copolymer (A) having a solid content of at least 20% by weight in the vehicle component, and SP
Paint containing 1 to 50 parts by weight of a plasticizer and / or an organic solvent having a solubility parameter value of 7.4 to 9.8 based on 100 parts by weight of the resin solid content. I)
The crosslinking agent (II) containing a compound containing at least two or more isocyanate groups in the molecule is contained in the crosslinking agent (II) with respect to 1 mol of the hydroxyl group contained in the base paint (I). A two-pack type aqueous coating composition which is mixed immediately before use so that the isocyanate group content is 0.2 to 3.0 mol.
レングリコ−ルとポリイソシアネ−ト化合物との反応生
成物（ｉ）である請求項１記載の塗料組成物。2. The coating composition according to claim 1, wherein the crosslinking agent (II) is a reaction product (i) of an alkoxypolyalkylene glycol and a polyisocyanate compound.
合物にアルコキシポリアルキレングリコ−ルとジアルカ
ノ−ルアミンとを反応させることにより得られる乳化剤
と、ポリイソシアネ−ト化合物との混合物（ii）である
請求項１記載の塗料組成物。3. A cross-linking agent (II) is a mixture (ii) of an emulsifier obtained by reacting a polyisocyanate compound with an alkoxypolyalkylene glycol and a dialkanolamine, and a polyisocyanate compound. The coating composition according to claim 1.
レングリコ−ルとポリイソシアネ−ト化合物との反応生
成物であるプレポリマ−、及びアミノ・ホルムアルデヒ
ド樹脂とからなるポリウレタンアミノ樹脂共重合体（ii
i)である請求項１記載の塗料組成物。4. A polyurethaneamino resin copolymer (ii) wherein the crosslinking agent (II) comprises a prepolymer which is a reaction product of an alkoxypolyalkylene glycol and a polyisocyanate compound, and an amino-formaldehyde resin.
The coating composition according to claim 1, which is i).
又は混合物（ii）のポリイソシアネートと、片末端に水
酸基又はアミノ基をもう片末端にアルコキシシリル基を
有するシランカップリング剤との反応生成物（iv）であ
る請求項１記載の塗料組成物。5. The method according to claim 1, wherein the crosslinking agent (II) comprises the reaction product (i)
The coating composition according to claim 1, which is a reaction product (iv) of the polyisocyanate of the mixture (ii) and a silane coupling agent having a hydroxyl group or an amino group at one end and an alkoxysilyl group at the other end.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19583696A JP4118969B2 (en) | 1996-07-25 | 1996-07-25 | Two-component water-based paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19583696A JP4118969B2 (en) | 1996-07-25 | 1996-07-25 | Two-component water-based paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1036767A true JPH1036767A (en) | 1998-02-10 |
| JP4118969B2 JP4118969B2 (en) | 2008-07-16 |
Family
ID=16347822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19583696A Expired - Fee Related JP4118969B2 (en) | 1996-07-25 | 1996-07-25 | Two-component water-based paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4118969B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11335621A (en) * | 1998-05-25 | 1999-12-07 | Kansai Paint Co Ltd | Clear coating composition giving highly stain-proof coating film |
| JP2002309165A (en) * | 2001-04-10 | 2002-10-23 | Toray Ind Inc | Coating composition |
| WO2002083800A1 (en) * | 2001-04-10 | 2002-10-24 | Toray Fine Chemical Co., Ltd. | Curable coating composition |
| JP2005179614A (en) * | 2003-12-24 | 2005-07-07 | Nippon Synthetic Chem Ind Co Ltd:The | Aqueous coating agent composition |
| JP2008136997A (en) * | 2006-11-06 | 2008-06-19 | Sk Kaken Co Ltd | Coating method |
| JP2009221243A (en) * | 2008-03-13 | 2009-10-01 | Nippon Paint Co Ltd | Water-dispersible resin, two-part thermosetting resin composition and manufacturing method of these |
| JP2011225656A (en) * | 2010-04-16 | 2011-11-10 | Kansai Paint Co Ltd | Emulsion resin-based coating |
| JP2011225655A (en) * | 2010-04-16 | 2011-11-10 | Kansai Paint Co Ltd | Two-pack aqueous coating composition |
| JP2018178082A (en) * | 2017-04-20 | 2018-11-15 | 関西ペイント株式会社 | Multi-component-type water-based undercoat coating composition and coating method |
| CN115190901A (en) * | 2020-03-27 | 2022-10-14 | 旭化成株式会社 | Carbodiimide composition, curing agent composition, coating composition, and resin cured product |
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| JPH07216301A (en) * | 1994-01-26 | 1995-08-15 | Kansai Paint Co Ltd | Two-pack water-based coating composition |
| JPH083437A (en) * | 1994-06-17 | 1996-01-09 | Nippon Paint Co Ltd | Aqueous cold-setting resin composition |
| JPH08157769A (en) * | 1994-12-05 | 1996-06-18 | Chugoku Marine Paints Ltd | Water-base coating composition for wooden material |
Cited By (10)
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| JPH11335621A (en) * | 1998-05-25 | 1999-12-07 | Kansai Paint Co Ltd | Clear coating composition giving highly stain-proof coating film |
| JP2002309165A (en) * | 2001-04-10 | 2002-10-23 | Toray Ind Inc | Coating composition |
| WO2002083800A1 (en) * | 2001-04-10 | 2002-10-24 | Toray Fine Chemical Co., Ltd. | Curable coating composition |
| JP2005179614A (en) * | 2003-12-24 | 2005-07-07 | Nippon Synthetic Chem Ind Co Ltd:The | Aqueous coating agent composition |
| JP2008136997A (en) * | 2006-11-06 | 2008-06-19 | Sk Kaken Co Ltd | Coating method |
| JP2009221243A (en) * | 2008-03-13 | 2009-10-01 | Nippon Paint Co Ltd | Water-dispersible resin, two-part thermosetting resin composition and manufacturing method of these |
| JP2011225656A (en) * | 2010-04-16 | 2011-11-10 | Kansai Paint Co Ltd | Emulsion resin-based coating |
| JP2011225655A (en) * | 2010-04-16 | 2011-11-10 | Kansai Paint Co Ltd | Two-pack aqueous coating composition |
| JP2018178082A (en) * | 2017-04-20 | 2018-11-15 | 関西ペイント株式会社 | Multi-component-type water-based undercoat coating composition and coating method |
| CN115190901A (en) * | 2020-03-27 | 2022-10-14 | 旭化成株式会社 | Carbodiimide composition, curing agent composition, coating composition, and resin cured product |
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