JPH0762188A - Cross-linkable water-dispersed resin composition - Google Patents
Cross-linkable water-dispersed resin compositionInfo
- Publication number
- JPH0762188A JPH0762188A JP13020994A JP13020994A JPH0762188A JP H0762188 A JPH0762188 A JP H0762188A JP 13020994 A JP13020994 A JP 13020994A JP 13020994 A JP13020994 A JP 13020994A JP H0762188 A JPH0762188 A JP H0762188A
- Authority
- JP
- Japan
- Prior art keywords
- water
- cross
- resin composition
- film
- dispersed resin
- 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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- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、接着剤、被覆剤、塗
料、特にコンクリート、織布、木、紙等の水浸透性基質
材の接着剤、被覆剤、塗料として有用な水分散系樹脂組
成物に関するものである。FIELD OF THE INVENTION The present invention relates to a water-dispersible resin useful as an adhesive, a coating agent, a coating material, particularly an adhesive, coating agent, coating material for a water-permeable substrate material such as concrete, woven fabric, wood and paper. It relates to a composition.
【０００２】[0002]
【従来の技術及び問題点】省資源、作業環境衛生、環境
汚染、危険物などの点から、接着剤、被覆剤、塗料など
の分野では溶剤系から水系への移行の傾向が強まってき
ている。例えば塗料分野では水性エマルジョン塗料への
関心が高まっているが、従来の水性エマルジョン塗料
は、その造膜が粒子の融合によるため、有機溶剤系塗料
に比べ塗膜強度がどうしても低いという欠点を有してい
た。これを解決する方法として、ケトン基またはアルデ
ヒド基含有アクリルエマルジョンをポリヒドラジド化合
物で架橋架橋塗膜とすることが考えられ、これらは架橋
型水分散系樹脂組成物として知られている（特開昭５４
−１１０２４８号、特開昭５４−１４４４３２号、特開
昭５５−１４７５６２号、特開昭５７−３８５７号、特
開昭６０−３８４６８号、特開昭６２−７２７４２号、
特開平２−１３８３７６号、特開平２−１７５７４２
号、特開平４−２４９５８７号公報）。この組合せの場
合は常温での架橋反応が可能であるが、ケトン基または
アルデヒド基含有アクリルエマルジョンではないカルボ
キシル基含有のアクリルエマルジョンを用いると、ポリ
ヒドラジド化合物との架橋には加熱を要する。このよう
な配合系において、一般に用いられているポリヒドラジ
ド化合物、例えばアジピン酸ジヒドラジドやコハク酸ジ
ヒドラジドなどは、以下に示すように実用上の欠点があ
った。１：均一な塗膜表面が得られず、密着性などの特
性にも不具合を生じることがある。２：ポリヒドラジド
化合物の常温での水への溶解度が低いため一液配合品と
する時にどうしても水量が増えてしまい、造膜乾燥時間
が長くなってしまう。2. Description of the Related Art In the fields of adhesives, coatings, paints, etc., there is an increasing tendency to shift from solvent-based systems to water-based systems from the viewpoints of resource saving, work environment hygiene, environmental pollution, dangerous substances, etc. . For example, in the field of paints, there is increasing interest in water-based emulsion paints, but conventional water-based emulsion paints have the drawback that the film strength is inevitably lower than that of organic solvent-based paints, because the film formation is due to the fusion of particles. Was there. As a method for solving this, it is conceivable that a ketone group- or aldehyde group-containing acrylic emulsion is formed into a cross-linked and cross-linked coating film with a polyhydrazide compound, and these are known as cross-linked water-dispersed resin compositions (Japanese Patent Laid-Open Publication No. Sho. 54
-110248, JP-A-54-144432, JP-A-55-147562, JP-A-57-3857, JP-A-60-38468, JP-A-62-72742,
JP-A-2-138376, JP-A-2-175742
No. 4-249587). In the case of this combination, the crosslinking reaction can be carried out at room temperature, but when a carboxyl group-containing acrylic emulsion other than the ketone group- or aldehyde group-containing acrylic emulsion is used, the crosslinking with the polyhydrazide compound requires heating. In such a compounding system, generally used polyhydrazide compounds, such as adipic acid dihydrazide and succinic acid dihydrazide, have practical drawbacks as shown below. 1: A uniform coating film surface cannot be obtained, and defects such as adhesion may occur. 2: Since the solubility of the polyhydrazide compound in water at room temperature is low, the amount of water is inevitably increased when it is made into a one-pack formulation, and the film-forming drying time becomes long.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の架橋
型水分散系組成物の造膜状態の不具合と長い造膜乾燥時
間という欠点を克服し、良好な造膜状態と造膜乾燥時間
の短縮を提供することである。DISCLOSURE OF THE INVENTION The present invention overcomes the disadvantages of the conventional crosslinked water-dispersed composition in the film-forming state and the long film-forming drying time, and has a favorable film-forming state and film-forming drying time. Is to provide a shortening of.
【０００４】[0004]
【課題を解決するための手段】本発明者は前記した従来
の架橋型水分散系組成物の問題点を解決すべく鋭意検討
した結果、ポリヒドラジド化合物の２５℃における水に
対する溶解度を２０ｇ／１００ｇＨ2Ｏ以上にするこに
より上記問題が解決できることを見いだし本発明を完成
するに至った。すなわち、本発明は、（Ａ）ケトン基ま
たはアルデヒド基が導入されたアクリル系共重合体水性
樹脂エマルジョンおよび（Ｂ）２５℃における水に対す
る溶解度が２０ｇ／１００ｇＨ2Ｏ以上の水溶性ポリヒ
ドラジド化合物からなることを特徴とする架橋型水分散
系樹脂組成物に関するものである。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the conventional cross-linking type water dispersion composition, the present inventors have found that the solubility of the polyhydrazide compound in water at 25 ° C. is 20 g / 100 gH It has been found that the above problems can be solved by setting it to 20 or more, and the present invention has been completed. That is, the present invention comprises (A) a water-soluble polyhydrazide compound having a ketone group or an aldehyde group-introduced acrylic copolymer aqueous resin emulsion and (B) a solubility in water at 25 ° C. of 20 g / 100 g H 2 O or more. And a cross-linked water-dispersed resin composition.
【０００５】本発明に用いられる（Ａ）成分としては、
例えば、少なくとも(a)ラジカル重合性を有する単量体
と、(b)ケトン基またはアルデヒド基を有する不飽和化
合物と、(c)不飽和カルボン酸を水性分散液中で乳化重
合することにより製造されるものであり、これらは特開
昭５４−１１０２４８号、同５４−１４４４３２号、同
５５−１４７５６２号、同５７−３８５７号、同６２−
７２７４２号公報等に記載されている。上記(a)成分の
ラジカル重合性を有する単量体としては、メチルアクリ
レート、エチルアクリレート等のアクリル酸のエステ
ル、メタクリル酸のエステル、ビニル芳香族化合物、ビ
ニル脂肪族化合物、ハロゲン化ビニル、アクリルアミド
やメタクリルアミド等があげらる。上記(b)成分のケト
ン基またはアルデヒド基を有する不飽和化合物とは、分
子中に少なくとも１個のアルデヒド基またはケトン基と
１個の重合可能な二重結合を有するカルボニル基含有化
合物であって、エステル基(-COO-)、カルボキシル基(-C
OOH)のみを有する化合物は除かれ、アクロレイン、ジア
セトンアクリルアミドやビニルメチルケトン等があげら
る。また、上記(c)成分の不飽和カルボン酸としては、
アクリル酸、メタクリル酸やマレイン酸などが用いられ
るが、これらに限定されるものではない。(a)〜(c)成分
の量比は目的によって選ばれるが、上記(a)成分は、用
途に応じて単独でまたは２種以上で用いられる。本発明
におけるアクリル系共重合体水性樹脂エマルジョンの樹
脂粒子径は、０．０１〜３ミクロンで、分散液の造膜温
度は６０℃以下、好ましくは−４０℃〜＋３０℃であ
る。As the component (A) used in the present invention,
For example, at least (a) a monomer having radical polymerizability, (b) an unsaturated compound having a ketone group or an aldehyde group, and (c) an unsaturated carboxylic acid produced by emulsion polymerization in an aqueous dispersion. These are disclosed in JP-A Nos. 54-110248, 54-144432, 55-147562, 57-3857, and 62-.
No. 72742, etc. Examples of the radically polymerizable monomer of the component (a) include esters of acrylic acid such as methyl acrylate and ethyl acrylate, esters of methacrylic acid, vinyl aromatic compounds, vinyl aliphatic compounds, vinyl halides, acrylamide and Examples include methacrylamide. The unsaturated compound having a ketone group or an aldehyde group as the component (b) is a carbonyl group-containing compound having at least one aldehyde group or ketone group and one polymerizable double bond in the molecule. , Ester group (-COO-), carboxyl group (-C
Compounds having only OOH) are excluded, and examples thereof include acrolein, diacetone acrylamide and vinyl methyl ketone. Further, as the unsaturated carboxylic acid of the component (c),
Acrylic acid, methacrylic acid, maleic acid and the like are used, but not limited thereto. Although the amount ratio of the components (a) to (c) is selected depending on the purpose, the component (a) may be used alone or in combination of two or more depending on the application. The resin particle diameter of the acrylic copolymer aqueous resin emulsion in the present invention is 0.01 to 3 μm, and the film-forming temperature of the dispersion liquid is 60 ° C. or lower, preferably −40 ° C. to + 30 ° C.
【０００６】（Ｂ）成分の水溶性ポリヒドラジド化合物
は、（Ａ）成分と架橋反応して架橋物を与える分子中に
２個以上の−ＮＨ・ＮＨ2基を有し、２５℃における水
に対する溶解度が２０ｇ／１００ｇＨ2Ｏ以上の化合物
であればよいが、例えば１,３‐ビス（ヒドラジノカル
ボエチル）‐５‐イソプロピルヒダントイン、１,３‐
ビス（ヒドラジノカルボエチル）‐５‐（２‐メチルメ
ルカプトエチル）ヒダントイン、１‐ヒドラジノカルボ
エチル‐３‐ヒドラジノカルボイソプロピル‐５‐（２
‐メチルメルカプトエチル）ヒダントイン、チオジプロ
ピオン酸ジヒドラジド、オキシジプロピオン酸ジヒドラ
ジド、オキシジグリコール酸ジヒドラジド、Ｎ,Ｎ'‐ジ
ヒドラジノカルボエチルピペラジンなどがあげられる。
これらの中で１,３‐ビス（ヒドラジノカルボエチル）
‐５‐イソプロピルヒダントインは水溶性が高く、着色
の少ない均一で良好な塗膜が得られるなどのてんで優れ
ている。（Ｂ）成分の架橋剤の水溶性ポリヒドラジド化
合物は、（Ａ）成分のケトン基およびアルデヒド基の和
１当量に対し、（Ｂ）成分の−ＮＨ・ＮＨ2基が０．０
２〜５モル当量、好ましくは０．１〜２モル当量となる
ように用いる。The water-soluble polyhydrazide compound as the component (B) has two or more --NH.NH 2 groups in the molecule which gives a crosslinked product by the crosslinking reaction with the component (A), and is resistant to water at 25 ° C. Any compound having a solubility of 20 g / 100 g H 2 O or more may be used, for example, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, 1,3-
Bis (hydrazinocarboethyl) -5- (2-methylmercaptoethyl) hydantoin, 1-hydrazinocarboethyl-3-hydrazinocarboisopropyl-5- (2
-Methylmercaptoethyl) hydantoin, thiodipropionic acid dihydrazide, oxydipropionic acid dihydrazide, oxydiglycolic acid dihydrazide, N, N'-dihydrazinocarboethylpiperazine and the like.
Among these, 1,3-bis (hydrazinocarboethyl)
-5-Isopropylhydantoin is highly water-soluble, and is excellent in that it gives a uniform and good coating film with little coloring. The water-soluble polyhydrazide compound as the cross-linking agent of the component (B) has 0.04% of —NH.NH 2 groups of the component (B) with respect to 1 equivalent of the sum of the ketone group and the aldehyde group of the component (A).
It is used in an amount of 2 to 5 molar equivalents, preferably 0.1 to 2 molar equivalents.
【０００７】本発明の組成物に、更に消泡剤、造膜助
剤、可塑剤、増粘剤、染料、顔料、充填剤、凍結防止剤
などを配合してもよい。また、本発明の水性樹脂エマル
ジョンに、常温架橋性保水剤である水溶性共重合体、常
温架橋性ポリウレタン・アクリル樹脂水性エマルジョン
や架橋性を阻害しない他の水性エマルジョンを本来の性
能を損なわない範囲で加えることはできる。架橋型水分
散系樹脂組成物は、水の乾燥により架橋反応が起こり、
皮膜が形成される。逆にいえば、系内に水が存在する限
り安定なので、保存安定性は良好である。The composition of the present invention may further contain antifoaming agents, film-forming aids, plasticizers, thickeners, dyes, pigments, fillers, antifreezing agents and the like. Further, in the aqueous resin emulsion of the present invention, a water-soluble copolymer that is a room temperature crosslinkable water retention agent, a room temperature crosslinkable polyurethane / acrylic resin aqueous emulsion, or another aqueous emulsion that does not impair the crosslinkability within a range that does not impair the original performance. Can be added with. The cross-linked water-dispersed resin composition undergoes a cross-linking reaction by drying water,
A film is formed. Conversely, since it is stable as long as water is present in the system, it has good storage stability.
【０００８】[0008]
【実施例】以下本発明を実施例により更に詳細に説明す
る。特にことわらないかぎり、すべての部および％は重
量部および重量％を示す。EXAMPLES The present invention will now be described in more detail with reference to examples. Unless otherwise noted, all parts and percentages are parts by weight and percentages by weight.
【０００９】（ヒドラジド化合物の溶解度）１，３‐ビ
ス（ヒドラジノカルボエチル）‐５‐イソプロピルヒダ
ントイン「アミキュアＶＤＨ（ＶＤＨ）」（味の素
（株）製）、１‐ヒドラジノカルボエチル‐３‐ヒドラ
ジノカルボイソプロピル‐５‐（２‐メチルメルカプト
エチル）ヒダントイン「ＭＨＹＹ’」、オキシジプロピ
オン酸ジヒドラジド「ＯＹ2」、Ｎ，Ｎ’‐ジヒドラジ
ノカルボエチルピペラジン「Ｐｉ（ＮＹ）2」、アジピ
ン酸ジヒドラジド「ＡＤＨ」（日本ヒドラジン工業
（株）製）、イソフタル酸ジヒドラジド「ＩＤＨ」（日
本ヒドラジン工業（株）製）、コハク酸ジヒドラジド
「ＳａＡＤＨ」（Ａｌｄｒｉｃｈ製）、蓚酸ジヒドラジ
ド「ＯＤＨ」（Ａｌｄｒｉｃｈ製）、マロン酸ジヒドラ
ジド「ＭＤＨ」（日本ヒドラジン工業（株）製）の２５
℃における水に対する溶解度を測定した。(Solubility of Hydrazide Compound) 1,3-Bis (hydrazinocarboethyl) -5-isopropylhydantoin "Amicure VDH (VDH)" (manufactured by Ajinomoto Co.) 1-hydrazinocarboethyl-3-hydra Gino carbo-isopropyl-5- (2-methyl-mercaptoethyl) hydantoin "MHYY '" oxy dipropionate acid dihydrazide "OY 2", N, N'-di hydrazinocarboethyl piperazine "Pi (NY) 2", adipic acid Dihydrazide “ADH” (manufactured by Japan Hydrazine Industry Co., Ltd.), isophthalic acid dihydrazide “IDH” (manufactured by Japan Hydrazine Industry Co., Ltd.), dihydrazide succinate “SaADH” (manufactured by Aldrich), oxalic acid dihydrazide “ODH” (manufactured by Aldrich). , Malonic dihydrazide "MDH" (Japan Hydrazide Industry Co., Ltd.) 25
The solubility in water at ° C was measured.
【００１０】[0010]
【表１】 [Table 1]
【００１１】（エマルジョンと架橋剤の配合）カルボニ
ル基含有ポリアクリル酸系エマルジョン「セルナＷＥ−
５１８」（中京油脂（株）製、固型分５０％）に、１，
３‐ビス（ヒドラジノカルボエチル）‐５‐イソプロピ
ルヒダントイン「ＶＤＨ」（味の素（株）製）、「ＶＤ
Ｈ］の１０％水溶液、１‐ヒドラジノカルボエチル‐３
‐ヒドラジノカルボイソプロピル‐５‐（２‐メチルメ
ルカプトエチル）ヒダントイン「ＭＨＹＹ’」、オキシ
ジプロピオン酸ジヒドラジド「ＯＹ2」、Ｎ，Ｎ’‐ジ
ヒドラジノカルボエチルピペラジン「Ｐｉ（Ｎ
Ｙ）2」、アジピン酸ジヒドラジド「ＡＤＨ」（日本ヒ
ドラジン工業（株）製）、［ＡＤＨ］の１０％水溶液、
イソフタル酸ジヒドラジド「ＩＤＨ」（日本ヒドラジン
工業（株）製）、コハク酸ジヒドラジド「ＳａＡＤＨ」
（Ａｌｄｒｉｃｈ製）、蓚酸ジヒドラジド「ＯＤＨ」
（Ａｌｄｒｉｃｈ製）、マロン酸ジヒドラジド「ＭＤ
Ｈ」（日本ヒドラジン工業（株）製）および乾燥性やヌ
レ性を良くするために造膜助剤としてブチルセロソルブ
を表２の組み合せで配合し、実施例１〜５および比較例
１〜６の架橋型水分散系樹脂組成物を得た。(Combining Emulsion and Crosslinking Agent) Carbonyl group-containing polyacrylic acid emulsion "Cerna WE-
518 ”(manufactured by Chukyo Yushi Co., Ltd., solid content 50%)
3-bis (hydrazinocarboethyl) -5-isopropylhydantoin "VDH" (manufactured by Ajinomoto Co., Inc.), "VD
H] 10% aqueous solution, 1-hydrazinocarboethyl-3
-Hydrazinocarboisopropyl-5- (2-methylmercaptoethyl) hydantoin "MHYY '", oxydipropionic acid dihydrazide "OY 2 ", N, N'-dihydrazinocarboethylpiperazine "Pi (N
Y) 2 ", adipic acid dihydrazide" ADH "(manufactured by Japan Hydrazine Industry Co., Ltd.), 10% aqueous solution of [ADH],
Isophthalic acid dihydrazide "IDH" (manufactured by Japan Hydrazine Industry Co., Ltd.), succinic acid dihydrazide "SaADH"
(Manufactured by Aldrich), oxalic acid dihydrazide "ODH"
(Manufactured by Aldrich), malonic acid dihydrazide "MD
H "(manufactured by Japan Hydrazine Industry Co., Ltd.) and butyl cellosolve as a film-forming auxiliary in order to improve the drying property and the wettability, are compounded in the combination shown in Table 2, and the crosslinking of Examples 1 to 5 and Comparative Examples 1 to 6 is performed. A mold water-dispersed resin composition was obtained.
【００１２】（試料評価） 常温硬化の場合；アルミ板に実施例１〜５および比較例
１〜６で得た組成物を、乾燥後５ミクロン程度になるよ
うにアプリケータを用いて膜化し、常温で放置後これを
試料とした。 加熱硬化の場合；アルミ板に実施例１〜５および比較例
１〜６で得た組成物を、乾燥後５０ミクロン程度になる
ようにアプリケータを用いて膜化し、１００℃で１５分
間加熱後これを試料とした。(Evaluation of Samples) In case of normal temperature curing; aluminum plates were coated with the compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 by an applicator so as to be about 5 microns after drying, After standing at room temperature, this was used as a sample. In the case of heat curing; the compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 6 are formed on an aluminum plate using an applicator so as to have a thickness of about 50 μm after drying, and heated at 100 ° C. for 15 minutes. This was used as a sample.
【００１３】（評価方法） 外観；膜の表面状態を目視し、均一で良好な表面の場合
は「○」、ザラザラして不均一な表面の場合は「×」で
表示。 造膜乾燥時間；これは常温硬化の場合のみ計測した。ア
プリケータで膜化後、タックがなくなるまでに要する時
間をストップウォッチで計測した。 クロスカット試験；塗膜面上に１ｍｍ方眼を１００個切
り、セロテープ剥離後の剥離しない方眼の個数表示。(Evaluation method) Appearance: The surface condition of the film is visually inspected, and a uniform and good surface is indicated by "○", and a rough and uneven surface is indicated by "x". Film formation drying time; this was measured only at room temperature curing. After filming with an applicator, the time required for tack to disappear was measured with a stopwatch. Cross-cut test: 100 pieces of 1 mm grid are cut on the surface of the coating film, and the number of grids that are not peeled off after peeling the cellophane tape is displayed.
【００１４】[0014]
【表２】 [Table 2]
【００１５】[0015]
【発明の効果】本発明の架橋型水分散系樹脂組成物は、
造膜状態が良好で均一な膜表面が得られ、造膜に要する
時間が短いことから、クリアーコート剤、トップコート
剤、アンダーコート剤、接着剤、布・紙の含浸剤などの
用途に適している。また、系内に水が存在する限り安定
なため、保存安定性が良い。更に、本発明の組成物は水
系であるため、世間で一般的な溶剤系に比べると環境衛
生、汚染、危険物などの点から非常に有用である。The crosslinked water-dispersed resin composition of the present invention is
Suitable for applications such as clear coating agents, top coating agents, under coating agents, adhesives, cloth / paper impregnating agents, etc. because the film forming state is good and a uniform film surface is obtained, and the time required for film forming is short. ing. Further, since it is stable as long as water is present in the system, it has good storage stability. Further, since the composition of the present invention is water-based, it is very useful from the viewpoint of environmental hygiene, pollution, dangerous substances, etc., as compared with the solvent system which is popular in the world.
Claims (2)
入されたアクリル系共重合体水性樹脂エマルジョンおよ
び（Ｂ）２５℃における水に対する溶解度が２０ｇ／１
００ｇＨ2Ｏ以上の水溶性ポリヒドラジド化合物から成
ることを特徴とする架橋型水分散系樹脂組成物。1. A water-based acrylic copolymer emulsion having (A) a ketone group or an aldehyde group introduced therein and (B) a solubility in water at 25 ° C. of 20 g / 1.
A cross-linked water-dispersed resin composition comprising a water-soluble polyhydrazide compound of 00 gH 2 O or more.
ノカルボエチル）‐５‐イソプロピルヒダントインであ
ることを特徴とする請求項１記載の架橋型水分散系樹脂
組成物。2. The crosslinked aqueous dispersion resin composition according to claim 1, wherein the component (B) is 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13020994A JP3489188B2 (en) | 1993-06-14 | 1994-06-13 | Crosslinked water-dispersed resin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14177693 | 1993-06-14 | ||
| JP5-141776 | 1993-06-14 | ||
| JP13020994A JP3489188B2 (en) | 1993-06-14 | 1994-06-13 | Crosslinked water-dispersed resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0762188A true JPH0762188A (en) | 1995-03-07 |
| JP3489188B2 JP3489188B2 (en) | 2004-01-19 |
Family
ID=26465403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13020994A Expired - Lifetime JP3489188B2 (en) | 1993-06-14 | 1994-06-13 | Crosslinked water-dispersed resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3489188B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10265735A (en) * | 1997-03-26 | 1998-10-06 | Nippon Polyurethane Ind Co Ltd | Aqueous polyurethane acrylic emulsion composition, and an aqueous emulsion coating material obtained by using the same |
-
1994
- 1994-06-13 JP JP13020994A patent/JP3489188B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10265735A (en) * | 1997-03-26 | 1998-10-06 | Nippon Polyurethane Ind Co Ltd | Aqueous polyurethane acrylic emulsion composition, and an aqueous emulsion coating material obtained by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3489188B2 (en) | 2004-01-19 |
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