JP2938239B2 - Photocurable aqueous resin composition - Google Patents
Photocurable aqueous resin compositionInfo
- Publication number
- JP2938239B2 JP2938239B2 JP3225584A JP22558491A JP2938239B2 JP 2938239 B2 JP2938239 B2 JP 2938239B2 JP 3225584 A JP3225584 A JP 3225584A JP 22558491 A JP22558491 A JP 22558491A JP 2938239 B2 JP2938239 B2 JP 2938239B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- acrylate
- meth
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Description
【０００１】[0001]
【産業上利用分野】本発明は、耐溶剤性、耐水性に優
れ、かつ保存安定性に優れたコーティング用途に適した
光硬化型水性樹脂組成物であり、無公害で安全性に優れ
た水性樹脂に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable aqueous resin composition which is excellent in solvent resistance and water resistance and has excellent storage stability and is suitable for coating applications. It is about resin.
【０００２】[0002]
【従来の技術】光硬化型樹脂はコーティング、インキ、
接着剤用途等に巾広く用いられているが、諸性能の向上
を考えると、有機溶剤が併用された形で用いられている
場合が多く、有機溶剤による作業環境の悪化や大気汚染
の問題、又、引火による火災の危険性がある。したがっ
て、この種の樹脂の水性化への要求が根強い。水性化の
手段の一つとして、エマルション化の方法があるが、非
反応性の乳化助剤が用いられる為に、樹脂本来の耐水性
が低下したり、水性エマルションを形成する基体ポリマ
ーそれ自体の耐溶剤性が劣るという欠点がある。この様
に未だに諸性能を満足すべき光硬化型水性樹脂組成物が
得られていないというのが実状である。2. Description of the Related Art Photocurable resins are used for coating, ink,
Although widely used for adhesives, etc., considering the improvement of various performances, they are often used in the form of using an organic solvent in combination. There is also a risk of fire due to ignition. Therefore, there is a strong demand for making this type of resin aqueous. One of the means for water-based formation is an emulsion method. However, since a non-reactive emulsification aid is used, the inherent water resistance of the resin is reduced, or the base polymer itself forming the water-based emulsion is used. There is a disadvantage that the solvent resistance is poor. As described above, the actual situation is that a photocurable aqueous resin composition satisfying various properties has not yet been obtained.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは、上述し
た従来技術における欠点の存在に鑑み、加えて業界の強
い要望に添うべく耐溶剤性、耐水性に優れ、かつ保存安
定性に優れた光硬化型水性樹脂組成物を提供するもので
ある。In view of the above-mentioned drawbacks in the prior art, the present inventors have also added excellent solvent resistance, water resistance and storage stability to meet the strong demands of the industry. And a photocurable aqueous resin composition.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討を重ねた結果、本発明を完成さ
せるに至った。すなわち本発明は、ポリヒドロキシ化合
物 (a1) とカルボキシル基含有ポリヒドロキシ化合物(a
2)との比率が当量比で２：８〜８：２の混合物（Ａ）
と、ポリイソシアネート化合物（Ｂ）及び分子中に１個
のヒドロキシ基と１個以上の（メタ）アクリロイル基を
有する不飽和モノヒドロキシ化合物（Ｃ）の三者を反応
させたカルボキシル基及び（メタ）アクリロイル基を有
するポリウレタン（メタ）アクリレート（Ｄ）を塩基性
有機化合物を用いて親水性を付与し、更に単官能不飽和
化合物（Ｅ1)及び／又は多官能不飽和化合物（Ｅ2)を混
合した後に水性化した光硬化型水性樹脂組成物に関す
る。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention provides a polyhydroxy compound (a 1 ) and a carboxyl group-containing polyhydroxy compound (a
2 ) The mixture (A) having an equivalent ratio of 2: 8 to 8: 2 with respect to 2).
And a carboxyl group obtained by reacting a polyisocyanate compound (B) and an unsaturated monohydroxy compound (C) having one hydroxy group and one or more (meth) acryloyl groups in the molecule (C) Polyurethane (meth) acrylate (D) having an acryloyl group is rendered hydrophilic by using a basic organic compound, and further mixed with a monofunctional unsaturated compound (E 1 ) and / or a polyfunctional unsaturated compound (E 2 ). The present invention relates to a photocurable aqueous resin composition which has been made water-soluble after the formation.
【０００５】本発明において用いられる（メタ）アクリ
レートという表現は、アクリレートとメタクリレートの
両方を意味する。その他（メタ）アクリロイル、（メ
タ）アクリル酸などの表現も同様である。本発明におい
て用いられる（Ａ）成分の一つである、ポリヒドロキシ
化合物(a1）としては、例えば、エチレングリコール、
１，４−ブタンジオール、ネオペンチルグリコール等の
ジオールとアジピン酸等のジカルボン酸との脱水縮合反
応で得られるポリエステルポリオール、ポリエチレング
リコール、ポリプロピレングリコール、ポリオキシテト
ラメチレングリコール、プロピレンオキシド−テトラヒ
ドロフラン共重合体等のポリエーテルポリオール、カプ
ロラクトンの開環重合で得られるポリカプロラクトンポ
リオール、ポリカーボネートポリオール等が挙げられ
る。これらは単独あるいは２種以上併用しても良い。
又、これらのポリヒドロキシ化合物は目的、用途に応じ
て適時選択し、硬質、軟質等の必要な物性を容易に設計
する事が出来る。本発明において用いられる（Ａ）成分
の他の一つである、カルボキシル基含有ポリヒドロキシ
化合物 (a 2 ）としては、得られるポリウレタン（メタ）
アクリレート分子中に分枝状にカルボキシル基を付与す
るものなら何れも使用出来るが、ポリウレタン（メタ）
アクリレート中のカルボキシル基量をコントロールする
には、低分子量のものが好ましく、例えば２，２−ジメ
チロールプロピオン酸が挙げられる。ポリヒドロキシ化
合物(a 1 )とカルボキシル基含有ポリヒドロキシ化合物(a
2)の混合比率（a1：a2）は、当量比で２：８〜８：２で
あり、好ましくは４：６〜６：４である。ポリヒドロキ
シ化合物（a1）の混合比率が２未満の上記範囲外では、
樹脂酸価が大きくなり耐水性が劣る。又、８を越える上
記範囲外では、安定した水性樹脂が得にくく、保存安定
性に劣る。[0005] The expression (meth) acrylate used in the present invention means both acrylate and methacrylate. The same applies to other expressions such as (meth) acryloyl and (meth) acrylic acid. Examples of the polyhydroxy compound (a 1 ), which is one of the components (A) used in the present invention, include ethylene glycol,
Polyester polyol, polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, propylene oxide-tetrahydrofuran copolymer obtained by a dehydration condensation reaction of a diol such as 1,4-butanediol and neopentyl glycol with a dicarboxylic acid such as adipic acid And polycaprolactone polyols obtained by ring-opening polymerization of caprolactone, and polycarbonate polyols. These may be used alone or in combination of two or more.
Further, these polyhydroxy compounds can be appropriately selected depending on the purpose and application, and the required physical properties such as hard and soft can be easily designed. The carboxyl group-containing polyhydroxy compound ( a 2 ), which is one of the components (A) used in the present invention, includes polyurethane (meth) obtained.
Any type can be used as long as it has a branched carboxyl group in the acrylate molecule.
In order to control the amount of carboxyl groups in the acrylate, those having a low molecular weight are preferable, and examples thereof include 2,2-dimethylolpropionic acid. Polyhydroxy compound (a 1 ) and carboxyl group-containing polyhydroxy compound (a
Mixing ratio of 2) (a 1: a 2 ) is 2 in an equivalent ratio: 8 to 8: 2, preferably 4: 4: 6 to 6. When the mixing ratio of the polyhydroxy compound (a 1 ) is outside the above-mentioned range of less than 2,
Resin acid value increases and water resistance deteriorates. On the other hand, when the ratio is outside the above range exceeding 8, it is difficult to obtain a stable aqueous resin and the storage stability is poor.
【０００６】本発明に於いて用いられるポリイソシアネ
ート化合物（Ｂ）としては、例えば１，４−テトラメチ
レンジイソシアネート、１，６−ヘキサメチレンジイソ
シアネート、２，４，４−トリメチルヘキサメチレンジ
イソシアネート、２，８−ジイソシアネートメチルカプ
ロエート等の脂肪族ジイソシアネート類、３−イソシア
ネートメチル−３，５，５−トリメチルシクロヘキシル
イソシアネート、ジシクロヘキシルメタン−４，４’−
ジイソシアネート、メチルシクロヘキシル−２，４−ジ
イソシアネート等の脂環族ジイソシアネート類、トリレ
ンジイソシアネート、ジフェニルメタンジイソシアネー
ト、１，５−ナフチレンジイソシアネート、ジフェニル
メチルメタンジイソシアネート、テトラアルキルジフェ
ニルメタンジイソシアネート、４，４’−ジベンジルジ
イソシアネート、１，３−フェニレンジイソシアネート
等の芳香族ジイソシアネート類等が挙げられる。これら
は単独あるいは２種以上併用しても良い。上記ポリイソ
シアネート化合物の中で耐候性の面より脂肪族及び脂環
族ポリイソシアネート化合物が好ましく、更に好ましく
は脂肪族ポリイソシアネート化合物が使用される。The polyisocyanate compound (B) used in the present invention includes, for example, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,8 Aliphatic diisocyanates such as diisocyanate methylcaproate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-
Alicyclic diisocyanates such as diisocyanate, methylcyclohexyl-2,4-diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylmethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl Aromatic diisocyanates such as diisocyanate and 1,3-phenylene diisocyanate are exemplified. These may be used alone or in combination of two or more. Among the above polyisocyanate compounds, aliphatic and alicyclic polyisocyanate compounds are preferable from the viewpoint of weather resistance, and more preferably, aliphatic polyisocyanate compounds are used.
【０００７】本発明において用いられる分子中に１個の
ヒドロキシ基と１個以上の（メタ）アクリロイル基を有
する不飽和モノヒドロキシ化合物（Ｃ）としては、例え
ば、２−ヒドロキシエチル（メタ）アクリレート、２−
ヒドロキシプロピル（メタ）アクリレート等のヒドロキ
シアルキル（メタ）アクリレート、Ｎ−ヒドロキシメチ
ル（メタ）アクリルアミド等のＮ−ヒドロキシアルキル
（メタ）アクリルアミド、エチレングリコールモノ（メ
タ）アクリレート、ジエチレングリコールモノ（メタ）
アクリレート、ポリエチレングリコールモノ（メタ）ア
クリレート、ポリプロピレングリコールモノ（メタ）ア
クリレート等のポリアルキレングリコールモノ（メタ）
アクリレート、グリシジル（メタ）アクリレートと（メ
タ）アクリル酸との等モル反応生成物等が挙げられる。
これらは単独あるいは２種以上併用しても良い。The unsaturated monohydroxy compound (C) having one hydroxy group and one or more (meth) acryloyl groups in the molecule used in the present invention includes, for example, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate; N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide; ethylene glycol mono (meth) acrylate; diethylene glycol mono (meth)
Polyalkylene glycol mono (meth) such as acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate
An acrylate, an equimolar reaction product of glycidyl (meth) acrylate and (meth) acrylic acid, and the like.
These may be used alone or in combination of two or more.
【０００８】本発明により得られるポリウレタン（メ
タ）アクリレート（Ｄ）の製造方法はポリヒドロキシ化
合物（a1）とカルボキシル基含有ポリヒドロキシ化合物
(a2）との混合物とポリイソシアネート化合物（Ｂ）を
反応させ、末端ＮＣＯのプレポリマーを得た後に、更に
分子中に１個のヒドロキシ基と１個以上の（メタ）アク
リロイル基を有する不飽和モノヒドロキシ化合物（Ｃ）
を反応させて製造する事が出来る。又、別に（Ａ）、
（Ｂ）、（Ｃ）を同時に反応させるか、又は（Ｂ）と
（Ｃ）を反応させてから（Ａ）を反応させる方法もあ
る。（Ａ）、（Ｂ）、（Ｃ）の量は、通常（Ａ）１当量
に対して（Ｂ）が１．１〜２．０当量、（Ｃ）が０．１
〜１．２当量であり、好ましくは（Ａ）１当量に対して
（Ｂ）が１．２〜１．８当量、（Ｃ）が０．２〜１．０
当量の範囲が適当である。通常、反応温度は２５℃〜１
５０℃であり、この際に反応促進のためにジブチルスズ
ジラウレート等の通常のウレタン化反応触媒を用いた
り、又、（メタ）アクリロイル基の重合を防止するため
にハイドロキノン、ハイドロキノンモノメチルエーテ
ル、フェノチアジン等の通常のラジカル重合禁止剤を用
いたり、反応系に空気又は酸素を導入しても良い。本発
明で用いられるカルボキシル基と反応して親水性を付与
するための塩基性有機化合物としては、公知のものなら
何れも使用出来るが、特に好ましい例としては、ジメチ
ルエタノールアミン、ジエチルエタノールアミン、トリ
エチルアミン等が挙げられる。本発明により得られるポ
リウレタン（メタ）アクリレート（Ｄ）は、必要に応じ
て有機溶剤を用いる事が出来る。これらの溶剤として
は、メチルエチルケトン、メチルイソブチルケトン、ア
セトン、酢酸エチル、酢酸ブチル、トルエン、キシレ
ン、Ｎ−メチル−２−ピロリドン、ジエチレングリコー
ルジメチルエーテル等が適当である。これらの有機溶剤
は、水性化の後に脱溶剤を行い樹脂系内より取り除く事
が出来る。The process for producing the polyurethane (meth) acrylate (D) obtained according to the present invention comprises a polyhydroxy compound (a 1 ) and a carboxyl group-containing polyhydroxy compound.
After reacting the mixture with (a 2 ) with the polyisocyanate compound (B) to obtain a prepolymer having a terminal NCO, the polymer further contains one hydroxy group and one or more (meth) acryloyl groups in the molecule. Saturated monohydroxy compound (C)
Can be produced by reacting Also, separately (A),
There is also a method in which (B) and (C) are reacted simultaneously, or (B) and (C) are reacted and then (A) is reacted. The amounts of (A), (B) and (C) are usually 1.1 to 2.0 equivalents of (B) and 0.1 equivalents of (C) per equivalent of (A).
To 1.2 equivalents, preferably 1.2 to 1.8 equivalents of (B) and 0.2 to 1.0 equivalents of (C) per equivalent of (A).
An equivalent range is appropriate. Usually, the reaction temperature is between 25 ° C and 1
At this time, a normal urethanization catalyst such as dibutyltin dilaurate is used for accelerating the reaction, and hydroquinone, hydroquinone monomethyl ether, phenothiazine or the like is used for preventing polymerization of (meth) acryloyl group. A normal radical polymerization inhibitor may be used, or air or oxygen may be introduced into the reaction system. As the basic organic compound for imparting hydrophilicity by reacting with the carboxyl group used in the present invention, any known organic compounds can be used, and particularly preferred examples are dimethylethanolamine, diethylethanolamine, and triethylamine. And the like. The polyurethane (meth) acrylate (D) obtained by the present invention can use an organic solvent as needed. As these solvents, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethyl acetate, butyl acetate, toluene, xylene, N-methyl-2-pyrrolidone, diethylene glycol dimethyl ether and the like are suitable. These organic solvents can be removed from the resin system by desolvation after aqueous conversion.
【０００９】本発明において用いられる単官能不飽和化
合物（Ｅ1)としては、例えば、２−エチルヘキシル（メ
タ）アクリレート、ドデシル（メタ）アクリレート、フ
ェノキシエチル（メタ）アクリレート、シクロヘキシル
（メタ）アクリレート、イソボロニル（メタ）アクリレ
ート、ジシクロペンテニル（メタ）アクリレート、ジシ
クロペンテニルオキシエチル（メタ）アクリレート、Ｎ
−ビニル−２−ピロリドン等が挙げられる。これらは単
独あるいは２種以上併用しても良い。多官能不飽和化合
物（Ｅ2)としては、例えば、エチレングリコールジ（メ
タ）アクリレート、プロピレングリコールジ（メタ）ア
クリレート、ネオペンチルグリコールジ（メタ）アクリ
レート、１，４−ブタンジオールジ（メタ）アクリレー
ト、ビスフェノールＡ、エチレンオキシド付加物のジ
（メタ）アクリレート、トリメチロールプロパントリ
（メタ）アクリレート、トリスアクリロイルオキシエチ
ルイソシアヌレート、ジペンタエリスリトールヘキサ
（メタ）アクリレート等が挙げられる。これらは単独あ
るいは２種以上併用しても良い。本発明により用いられ
る水性化のための水は、脱イオン水、蒸留水等が使用さ
れる。The monofunctional unsaturated compound (E 1 ) used in the present invention includes, for example, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N
-Vinyl-2-pyrrolidone and the like. These may be used alone or in combination of two or more. Examples of the polyfunctional unsaturated compound (E 2 ) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate , Bisphenol A, di (meth) acrylate of ethylene oxide adduct, trimethylolpropane tri (meth) acrylate, trisacryloyloxyethyl isocyanurate, dipentaerythritol hexa (meth) acrylate and the like. These may be used alone or in combination of two or more. As the water for making water used according to the present invention, deionized water, distilled water and the like are used.
【００１０】本発明の光硬化型水性樹脂組成物は必要に
応じて光重合開始剤、増感助剤、界面活性剤、消泡剤、
酸化防止剤、増粘剤等の各種添加剤を配合される。光重
合開始剤は、例えば、ダロキュアー２９５９（メルクジ
ャパン社製）の如き水溶性のものが好ましいが、ダロキ
ュアー１１７３（メルクジャパン社製）の如き液体状の
もの、あるいは本発明に用いられる単官能不飽和化合
物、あるいは多官能不飽和化合物に溶解するものであれ
ば良く、これらは単独あるいは２種以上併用しても良
い。これら光重合開始剤の使用割合は、通常、本発明の
樹脂組成物の１重量％以上、１０重量％未満、好ましく
は２重量％から６重量％が適当である。本発明の光硬化
型水性樹脂組成物は、耐溶剤性、耐水性、保存安定性に
優れるという特徴を生かし、水性塗料、水性印刷イン
キ、水性ハードコート剤、水性オーバープリントワニス
等の用途に使用される。[0010] The photocurable aqueous resin composition of the present invention may contain, if necessary, a photopolymerization initiator, a sensitizing aid, a surfactant, an antifoaming agent,
Various additives such as an antioxidant and a thickener are blended. As the photopolymerization initiator, for example, a water-soluble one such as Darocure 2959 (manufactured by Merck Japan) is preferable, but a liquid state initiator such as Darocure 1173 (manufactured by Merck Japan) or the monofunctional non-functional compound used in the present invention is used. Any compound that can be dissolved in a saturated compound or a polyfunctional unsaturated compound may be used, and these may be used alone or in combination of two or more. The use ratio of these photopolymerization initiators is usually 1% by weight or more and less than 10% by weight, preferably 2% by weight to 6% by weight of the resin composition of the present invention. The photocurable aqueous resin composition of the present invention is characterized by having excellent solvent resistance, water resistance and storage stability, and is used for applications such as aqueous paints, aqueous printing inks, aqueous hard coat agents, and aqueous overprint varnishes. Is done.
【００１１】[0011]
【実施例】以下、本発明を更に具体的に説明する為、実
施例及び比較例を挙げて説明するが、本発明はこれらの
実施例に限定されるものではない。 合成例１ 分子量１０００のポリオキシテトラメチレングリコール
（保土ヶ谷化学：ＰＴＧ１０００）２５０重量部、２，
２−ジメチロールプロピオン酸３３．５重量部、Ｎ−メ
チル−２−ピロリドン５０．３重量部、酢酸エチル５
０．３重量部を攪拌機、温度計、冷却器を装備した２０
００ｍｌのフラスコに仕込み、窒素気流下に７０℃まで
昇温し、２，２−ジメチロールプロピオン酸を溶解し
た。次にイソホロンジイソシアネート１６６．５重量部
を添加し７０℃で反応させＮＣＯ基が初期の１／３にな
った時点で次に、この反応液に２−ヒドロキシエチルア
クリレート５８．０重量部、ハイドロキノン０．１重量
部を加え、空気を反応液中にバブリングしながら７０℃
で更に６時間反応を行ってカルボキシル基及びアクリロ
イル基を有するポリウレタンアクリレートを得た。得ら
れたポリウレタンアクリレートにトリエチルアミン２
２．７重量部を加え系内が均一になった時点でイソボロ
ニルアクリレート７２．６重量部、トリスアクリロイル
オキシエチルイソシアヌレート１４５．１重量部を加
え、十分に混合した。次に脱イオン水１０８８．６重量
部を加え水性化した。水性化後も空気のバブリングを続
け内温を徐々に上昇させ脱溶剤を行い、不揮発分４１．
５重量％、酸価７．５／ワニス、ｐＨ７．０の光硬化型
水性樹脂組成物（Ａ−１）を得た。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Synthesis Example 1 250 parts by weight of polyoxytetramethylene glycol having a molecular weight of 1,000 (Hodogaya Chemical: PTG1000), 2,
33.5 parts by weight of 2-dimethylolpropionic acid, 50.3 parts by weight of N-methyl-2-pyrrolidone, 5 parts by weight of ethyl acetate
0.3 parts by weight equipped with a stirrer, thermometer and cooler 20
The mixture was charged into a 00 ml flask, heated to 70 ° C. under a nitrogen stream, and 2,2-dimethylolpropionic acid was dissolved. Next, 166.5 parts by weight of isophorone diisocyanate was added and reacted at 70 ° C., and when the number of NCO groups became 1/3 of the initial value, 58.0 parts by weight of 2-hydroxyethyl acrylate and 0% of hydroquinone were added to the reaction mixture. 1 part by weight, and air was bubbled through the reaction solution at 70 ° C.
For a further 6 hours to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. Triethylamine 2 is added to the obtained polyurethane acrylate.
When 2.7 parts by weight was added and the system became homogeneous, 72.6 parts by weight of isobornyl acrylate and 145.1 parts by weight of trisacryloyloxyethyl isocyanurate were added and mixed well. Next, 1088.6 parts by weight of deionized water was added to make the aqueous solution. After the aqueous solution, air bubbling was continued, the internal temperature was gradually increased, and the solvent was removed.
A photocurable aqueous resin composition (A-1) having 5% by weight, an acid value of 7.5 / varnish, and a pH of 7.0 was obtained.
【００１２】合成例２ 分子量１０００のポリエステルポリオール（三井東圧化
学製：Ｑ５００１Ｅ）２５０重量部、２，２−ジメチロ
ールプロピオン酸３３．５重量部、Ｎ−メチル−２−ピ
ロリドン５０．３重量部、酢酸エチル５０．３重量部を
攪拌機、温度計、冷却器を装備した２０００ｍｌのフラ
スコに仕込み、窒素気流下に７０℃まで昇温し、ポリエ
ステルポリオール、２，２−ジメチロールプロピオン酸
を溶解した。次にイソホロンジイソシアネート１６６．
５重量部を添加し７０℃で反応させ、ＮＣＯ基が初期の
１／３になった時点で次に、この反応液に２−ヒドロキ
シエチルアクリレート５８．０重量部、ハイドロキノン
０．１重量部を加え、空気を反応液中にバブリングしな
がら７０℃で更に６時間反応を行ってカルボキシル基及
びアクリロイル基を有するポリウレタンアクリレートを
得た。得られたポリウレタンアクリレートにトリエチル
アミン２２．７重量部を加え系内が均一になった時点で
イソボロニルアクリレート７２．６重量部、トリスアク
リロイルオキシエチルイソシアヌレート１４５．１重量
部を加え、十分に混合した。次に脱イオン水１０８８．
６重量部を加え水性化した。水性化後も空気のバブリン
グを続け内温を徐々に上昇させ脱溶剤を行い、不揮発分
４２．０重量％、酸価７．６／ワニス、ｐＨ７．２の光
硬化型水性樹脂組成物（Ａ−２）を得た。Synthesis Example 2 250 parts by weight of a polyester polyol having a molecular weight of 1,000 (manufactured by Mitsui Toatsu Chemicals: Q5001E), 33.5 parts by weight of 2,2-dimethylolpropionic acid, 50.3 parts by weight of N-methyl-2-pyrrolidone , 50.3 parts by weight of ethyl acetate was charged into a 2000 ml flask equipped with a stirrer, a thermometer, and a cooler, and heated to 70 ° C under a nitrogen stream to dissolve the polyester polyol and 2,2-dimethylolpropionic acid. . Next, isophorone diisocyanate 166.
After adding 5 parts by weight and reacting at 70 ° C., when the NCO group became 1/3 of the initial amount, 58.0 parts by weight of 2-hydroxyethyl acrylate and 0.1 part by weight of hydroquinone were added to the reaction solution. In addition, the reaction was further performed at 70 ° C. for 6 hours while bubbling air through the reaction solution to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. 22.7 parts by weight of triethylamine was added to the obtained polyurethane acrylate, and when the system became homogeneous, 72.6 parts by weight of isobornyl acrylate and 145.1 parts by weight of trisacryloyloxyethyl isocyanurate were added, and mixed thoroughly. did. Next, deionized water 1088.
6 parts by weight were added to make aqueous. After waterification, air bubbling is continued and the internal temperature is gradually increased to remove the solvent, and a photocurable aqueous resin composition (A) having a nonvolatile content of 42.0% by weight, an acid value of 7.6 / varnish, and a pH of 7.2 is used. -2) was obtained.
【００１３】合成例３ 分子量２０００のポリオキシテトラメチレングリコール
（保土ヶ谷化学：ＰＴＧ２０００）３４５重量部、２，
２−ジメチロールプロピオン酸２３．１重量部、Ｎ−メ
チル−２−ピロリドン３４．７重量部、酢酸エチル１０
０重量部を攪拌機、温度計、冷却器を装備した２０００
ｍｌのフラスコに仕込み、窒素気流下に７０℃まで昇温
し、２，２−ジメチロールプロピオン酸を溶解した。次
にイソホロンジイソシアネート１１４．９重量部を添加
し７０℃で反応させＮＣＯ基が初期の１／３になった時
点で次に、この反応液に２−ヒドロキシエチルアクリレ
ート４０重量部、ハイドロキノン０．１重量部を加え、
空気を反応液中にバブリングしながら７０℃で更に６時
間反応を行ってカルボキシル基及びアクリロイル基を有
するポリウレタンアクリレートを得た。得られたポリウ
レタンアクリレートにトリエチルアミン１５．７重量部
を加え、系内が均一になった時点でイソボロニルアクリ
レート７４．６重量部、トリスアクリロイルオキシエチ
ルイソシアヌレート１４９．４重量部を加え、十分に混
合した。次に脱イオン水１１２０．７重量部を加え水性
化した。水性化後も空気のバブリングを続け内温を徐々
に上昇させ脱溶剤を行い、不揮発分４１．８重量％、酸
価５．５／ワニス、ｐＨ７．１の光硬化型水性樹脂組成
物（Ａ−３）を得た。Synthesis Example 3 345 parts by weight of polyoxytetramethylene glycol having a molecular weight of 2,000 (Hodogaya Chemical: PTG2000),
23.1 parts by weight of 2-dimethylolpropionic acid, 34.7 parts by weight of N-methyl-2-pyrrolidone, ethyl acetate 10
0 parts by weight 2000 equipped with stirrer, thermometer and cooler
The mixture was charged in a flask having a capacity of 70 ml and heated to 70 ° C under a nitrogen stream to dissolve 2,2-dimethylolpropionic acid. Next, 114.9 parts by weight of isophorone diisocyanate was added and reacted at 70 ° C., and when the NCO group became 1/3 of the initial amount, 40 parts by weight of 2-hydroxyethyl acrylate and 0.1 part of hydroquinone were added to the reaction mixture. Add the parts by weight,
The reaction was further performed at 70 ° C. for 6 hours while bubbling air through the reaction solution to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. To the obtained polyurethane acrylate, 15.7 parts by weight of triethylamine was added, and when the system became homogeneous, 74.6 parts by weight of isobornyl acrylate and 149.4 parts by weight of trisacryloyloxyethyl isocyanurate were added. Mixed. Next, 1120.7 parts by weight of deionized water was added to make the mixture aqueous. After waterification, air bubbling is continued and the internal temperature is gradually increased to remove the solvent, and a photocurable aqueous resin composition (A) having a nonvolatile content of 41.8% by weight, an acid value of 5.5 / varnish, and a pH of 7.1 is used. -3) was obtained.
【００１４】合成例４ 分子量１０００のポリオキシテトラメチレングリコール
（保土ヶ谷化学：ＰＴＧ１０００）９０重量部、２，２
−ジメチロールプロピオン酸５５重量部、Ｎ−メチル−
２−ピロリドン８２．５重量部、酢酸エチル８２．５重
量部を攪拌機、温度計、冷却器を装備した２０００ｍｌ
のフラスコに仕込み、窒素気流下に７０℃まで昇温し、
２，２−ジメチロールプロピオン酸を溶解した。次にイ
ソホロンジイソシアネート１６６．５重量部を添加し７
０℃で反応させＮＣＯ基が初期の１／３になった時点で
次に、この反応液に２−ヒドロキシエチルアクリレート
５８重量部、ハイドロキノン０．０５重量部を加え、空
気を反応液中にバブリングしながら７０℃で更に６時間
反応を行ってカルボキシル基及びアクリロイル基を有す
るポリウレタンアクリレートを得た。得られたポリウレ
タンアクリレートにトリエチルアミン３７．３重量部を
加え系内が均一になった時点でイソボロニルアクリレー
ト５２．８重量部、トリスアクリロイルオキシエチルイ
ソシアヌレート１０５．５重量部を加え、十分に混合し
た。次に脱イオン水７９１．７重量部を加え水性化し
た。水性化後も空気のバブリングを続け内温を徐々に上
昇させ脱溶剤を行い、不揮発分４２．０重量％、酸価１
７．０／ワニス、ｐＨ７．５の光硬化型水性樹脂組成物
（Ａ−４）を得た。Synthesis Example 4 90 parts by weight of polyoxytetramethylene glycol having a molecular weight of 1,000 (Hodogaya Chemical: PTG1000), 2,2
-Dimethylolpropionic acid 55 parts by weight, N-methyl-
2000 ml of 2-pyrrolidone 82.5 parts by weight and ethyl acetate 82.5 parts by weight equipped with a stirrer, thermometer and cooler
And heated to 70 ° C under a nitrogen stream,
2,2-Dimethylolpropionic acid was dissolved. Next, 166.5 parts by weight of isophorone diisocyanate was added and 7
When the reaction was carried out at 0 ° C. and the NCO group became 1/3 of the initial value, 58 parts by weight of 2-hydroxyethyl acrylate and 0.05 parts by weight of hydroquinone were added to the reaction solution, and air was bubbled into the reaction solution. The reaction was further carried out at 70 ° C. for 6 hours to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. 37.3 parts by weight of triethylamine was added to the obtained polyurethane acrylate, and when the system became homogeneous, 52.8 parts by weight of isobornyl acrylate and 105.5 parts by weight of trisacryloyloxyethyl isocyanurate were added and mixed well. did. Next, 791.7 parts by weight of deionized water was added to make the aqueous solution. After the waterification, air bubbling was continued, the internal temperature was gradually increased, and the solvent was removed. The nonvolatile content was 42.0% by weight and the acid value was 1
A photocurable aqueous resin composition (A-4) having a pH of 7.0 / varnish and a pH of 7.5 was obtained.
【００１５】合成例５ 分子量１０００のポリオキシテトラメチレングリコール
（保土ヶ谷化学：ＰＴＧ１０００）４１０重量部、２，
２−ジメチロールプロピオン酸１２．１重量部、Ｎ−メ
チル−２−ピロリドン１８．１重量部、酢酸エチル５０
重量部を攪拌機、温度計、冷却器を装備した２０００ｍ
ｌのフラスコに仕込み窒素気流下に７０℃まで昇温し、
２，２−ジメチロールプロピオン酸を溶解した。次にイ
ソホロンジイソシアネート１６６．５重量部を添加し７
０℃で反応させＮＣＯ基が初期の１／３になった時点で
次に、この反応液に２−ヒドロキシエチルアクリレート
５８重量部、ハイドロキノン０．１重量部を加え、空気
を反応液中にバブリングしながら７０℃で更に６時間反
応を行ってカルボキシル基及びアクリロイル基を有する
ポリウレタンアクリレートを得た。得られたポリウレタ
ンアクリレートにトリエチルアミン８．２重量部を加
え、系内が均一になった時点でイソボロニルアクリレー
ト９２．４重量部、トリスアクリロイルオキシエチルイ
ソシアヌレート１８４．７重量部を加え、十分に混合し
た。次に脱イオン水１３２７．２重量部を加え水性化し
た。水性化後も空気のバブリングを続け内温を徐々に上
昇させ脱溶剤を行い、不揮発分４２．０重量％、酸価
２．４／ワニス、ｐＨ６．９の光硬化型水性樹脂組成物
（Ａ−５）を得た。Synthesis Example 5 410 parts by weight of polyoxytetramethylene glycol having a molecular weight of 1,000 (Hodogaya Chemical: PTG1000), 2,
12.1 parts by weight of 2-dimethylolpropionic acid, 18.1 parts by weight of N-methyl-2-pyrrolidone, 50 parts of ethyl acetate
2000m with stirrer, thermometer and cooler
1 flask and heated to 70 ° C. under a nitrogen stream,
2,2-Dimethylolpropionic acid was dissolved. Next, 166.5 parts by weight of isophorone diisocyanate was added and 7
When the reaction was carried out at 0 ° C. and the NCO group became 1/3 of the initial state, 58 parts by weight of 2-hydroxyethyl acrylate and 0.1 part by weight of hydroquinone were added to the reaction solution, and air was bubbled into the reaction solution. The reaction was further carried out at 70 ° C. for 6 hours to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. 8.2 parts by weight of triethylamine was added to the obtained polyurethane acrylate, and when the system became homogeneous, 92.4 parts by weight of isobornyl acrylate and 184.7 parts by weight of trisacryloyloxyethyl isocyanurate were added. Mixed. Next, 1327.2 parts by weight of deionized water was added to make the aqueous solution. After waterification, air bubbling is continued and the internal temperature is gradually increased to remove the solvent, and a photocurable aqueous resin composition (A) having a nonvolatile content of 42.0% by weight, an acid value of 2.4 / varnish, and a pH of 6.9 is used. -5) was obtained.
【００１６】合成例６ 分子量１０００のポリオキシテトラメチレングリコール
（保土ヶ谷化学：ＰＴＧ１０００）２５０重量部、２，
２−ジメチロールプロピオン酸３３．５重量部、Ｎ−メ
チル−２−ピロリドン５０．３重量部、酢酸エチル５
０．３重量部を攪拌機、温度計、冷却器を装備した２０
００ｍｌのフラスコに仕込み窒素気流下に７０℃まで昇
温し、２，２−ジメチロールプロピオン酸を溶解した。
次にイソホロンジイソシアネート１６６．５重量部を添
加し７０℃で反応させＮＣＯ基が初期の１／３になった
時点で次に、この反応液に２−ヒドロキシエチルアクリ
レート５８重量部、ハイドロキノン０．１重量部を加
え、空気を反応液中にバブリングしながら７０℃で更に
６時間反応を行ってカルボキシル基及びアクリロイル基
を有するポリウレタンアクリレートを得た。得られたポ
リウレタンアクリレートにトリエチルアミン２２．７重
量部を加え系内が均一になった時点で脱イオン水１０８
８．６重量部を加え水性化した。水性化後も空気のバブ
リングを続け内温を徐々に上昇させ脱溶剤を行った後に
イソボロニルアクリレート７２．６重量部、トリスアク
リロイルオキシエチルイソシアヌレート１４５．１重量
部を加え十分に混合して不揮発分４１．２重量％、酸価
７．４／ワニス、ｐＨ７．０の光硬化型水性樹脂組成物
（Ａ−６）を得た。 実施例１〜４及び比較例１〜３ 表−１に示す配合内容（重量部）にて、合成例で得られ
た所定の光硬化型水性樹脂組成物と所定の光重合開始剤
を加え十分に混合攪拌して、各々の光硬化型水性樹脂組
成物を得た。Synthesis Example 6 250 parts by weight of polyoxytetramethylene glycol having a molecular weight of 1,000 (Hodogaya Chemical: PTG1000), 2,
33.5 parts by weight of 2-dimethylolpropionic acid, 50.3 parts by weight of N-methyl-2-pyrrolidone, 5 parts by weight of ethyl acetate
0.3 parts by weight equipped with a stirrer, thermometer and cooler 20
The flask was charged into a 00 ml flask and heated to 70 ° C. under a nitrogen stream to dissolve 2,2-dimethylolpropionic acid.
Next, 166.5 parts by weight of isophorone diisocyanate was added and reacted at 70 ° C., and when the NCO group became 1/3 of the initial amount, 58 parts by weight of 2-hydroxyethyl acrylate and 0.1 part of hydroquinone were added to the reaction mixture. The reaction mixture was further reacted at 70 ° C. for 6 hours while bubbling air through the reaction solution to obtain a polyurethane acrylate having a carboxyl group and an acryloyl group. 22.7 parts by weight of triethylamine was added to the obtained polyurethane acrylate, and when the system became homogeneous, deionized water 108
8.6 parts by weight were added to make it aqueous. After waterification, air bubbling was continued and the internal temperature was gradually increased to remove the solvent. After that, 72.6 parts by weight of isobornyl acrylate and 145.1 parts by weight of trisacryloyloxyethyl isocyanurate were added and mixed well. A photocurable aqueous resin composition (A-6) having a nonvolatile content of 41.2% by weight, an acid value of 7.4 / varnish, and a pH of 7.0 was obtained. Examples 1 to 4 and Comparative Examples 1 to 3 With the content (parts by weight) shown in Table 1, a predetermined photocurable aqueous resin composition obtained in the synthesis example and a predetermined photopolymerization initiator were added. To obtain a photocurable aqueous resin composition.
【００１７】[0017]
【表１】 [Table 1]
【００１８】実施例及び比較例で得られた光硬化型水性
樹脂組成物について次の評価を行い、その結果を表−
２、３に示した。なお、評価は次の方法によった。 １）保存安定性 各々の光硬化型水性樹脂組成物をガラス製試験管に入
れ、完全に遮光された状態で、かつ、２５℃及び４０℃
に保たれた雰囲気中での経時変化（二層分離）を観察し
た。 ２）耐溶剤性 ブリキ板上に硬化後の厚みが３０μになる様にバーコー
ターにて塗布し、８０℃／５分間で水を揮散後高圧水銀
灯８０ｗ／ｃｍを試料通過方向と垂直に設置した照射装
置を用い、光源下１５ｃｍの位置においてコンベアース
ピード８ｍ／分で硬化させた。上記方法で得られた硬化
塗膜を用いてトルエンラビングテストを行い、トルエン
により塗膜がおかされた時の回数を表示する。 ３）耐水性 ポリカーボネート製テストパネル上に、耐溶剤性と同様
な方法で硬化させた硬化塗膜を用いて ３−１）２５℃の水の２４時間詞浸漬後の表面状態 ３−２）沸騰水に２時間の浸漬後の表面状態 各々観察し白化、フクレ状態を表示する。The following evaluations were performed on the photocurable aqueous resin compositions obtained in Examples and Comparative Examples.
The results are shown in Figs. The evaluation was performed according to the following method. 1) Storage stability Each photocurable aqueous resin composition was placed in a glass test tube, and completely shielded from light, and at 25 ° C and 40 ° C.
Change (bilayer separation) was observed in an atmosphere kept under the following conditions. 2) Solvent resistance The composition was applied on a tin plate with a bar coater so that the thickness after curing became 30 μm. After water was volatilized at 80 ° C. for 5 minutes, a high-pressure mercury lamp 80 w / cm was set perpendicular to the sample passing direction. Using an irradiation device, the composition was cured at a position 15 cm below the light source at a conveyor speed of 8 m / min. A toluene rubbing test is performed using the cured coating film obtained by the above method, and the number of times when the coating film is damaged by toluene is displayed. 3) Water resistance Using a cured coating film cured in the same manner as for the solvent resistance on a polycarbonate test panel. 3-1) Surface state after immersion in 25 ° C water for 24 hours 3-2) Boiling Surface condition after immersion in water for 2 hours Each is observed and whitened and blistered.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【発明の効果】以上説明の如く、本発明の光硬化型水性
樹脂組成物は、耐溶剤性、耐水性に優れ、かつ保存性に
優れ、塗料、印刷インキ、ハードコート、オーバープリ
ントワニス等の用途に好適な樹脂である事は表−２、３
から明らかである。As described above, the photocurable aqueous resin composition of the present invention is excellent in solvent resistance, water resistance and storage stability, and can be used for paints, printing inks, hard coats, overprint varnishes and the like. Tables 2 and 3 show that the resin is suitable for use.
It is clear from
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｄ 175/16 Ｃ０９Ｄ 175/16 (56)参考文献 特開 平３−166216（ＪＰ，Ａ) 特開 昭61−168610（ＪＰ，Ａ) 特開 平２−155957（ＪＰ，Ａ) 特開 昭61−211324（ＪＰ，Ａ) 特開 昭59−138212（ＪＰ，Ａ) 特開 昭54−77795（ＪＰ，Ａ) 特開 昭62−92233（ＪＰ，Ａ) 特開 平４−178418（ＪＰ，Ａ) 特開 平４−80268（ＪＰ，Ａ) 特開 昭63−137916（ＪＰ，Ａ) 特開 昭59−191772（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08F 290/00 - 290/14 C08F 299/00 - 299/08 C08F 2/00 - 2/60 C08G 18/00 - 18/87 C09D 1/00 - 201/10 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 6 Identification symbol FI C09D 175/16 C09D 175/16 (56) References JP-A-3-166216 (JP, A) JP-A-61-168610 (JP) JP-A-2-155957 (JP, A) JP-A-61-212324 (JP, A) JP-A-59-138212 (JP, A) JP-A-54-77795 (JP, A) JP-A-4-178418 (JP, A) JP-A-4-80268 (JP, A) JP-A-63-137916 (JP, A) JP-A-59-191772 (JP, A) A) (58) Field surveyed (Int. Cl. 6 , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/00-2/60 C08G 18/00-18/87 C09D 1/00-201/10
Claims (1)
シル基含有ポリヒドロキシ化合物 (a2) との比率が当量
比で２：８〜８：２の混合物（Ａ）と、ポリイソシアネ
ート化合物（Ｂ）及び分子中に１個のヒドロキシ基と１
個以上の（メタ）アクリロイル基を有する不飽和モノヒ
ドロキシ化合物（Ｃ）の三者を反応させたカルボキシル
基及び（メタ）アクリロイル基を有するポリウレタン
（メタ）アクリレート（Ｄ）を、塩基性有機化合物を用
いて親水性を付与し、更に単官能不飽和化合物（Ｅ1 ）
及び／又は多官能不飽和化合物（Ｅ2 ）を混合した後に
水性化した光硬化型水性樹脂組成物。1. A mixture (A) in which the ratio of the polyhydroxy compound (a 1 ) to the carboxyl group-containing polyhydroxy compound (a 2 ) is an equivalent ratio of 2: 8 to 8: 2, and a polyisocyanate compound (B) And one hydroxy group and one
A polyurethane (meth) acrylate (D) having a carboxyl group and a (meth) acryloyl group obtained by reacting an unsaturated monohydroxy compound (C) having three or more (meth) acryloyl groups with a basic organic compound To impart hydrophilicity and further use a monofunctional unsaturated compound (E 1 )
And / or a water-curable aqueous resin composition obtained by mixing a polyfunctional unsaturated compound (E 2 ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3225584A JP2938239B2 (en) | 1991-09-05 | 1991-09-05 | Photocurable aqueous resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3225584A JP2938239B2 (en) | 1991-09-05 | 1991-09-05 | Photocurable aqueous resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0565323A JPH0565323A (en) | 1993-03-19 |
| JP2938239B2 true JP2938239B2 (en) | 1999-08-23 |
Family
ID=16831607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3225584A Expired - Lifetime JP2938239B2 (en) | 1991-09-05 | 1991-09-05 | Photocurable aqueous resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2938239B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2270917A (en) * | 1992-09-23 | 1994-03-30 | Sericol Ltd | Urethane(meth)acrylates |
| GB2280905A (en) * | 1993-08-06 | 1995-02-15 | Coates Brothers Plc | Ethylenically unsaturated photoinitiator |
| JP4572005B2 (en) * | 1999-06-28 | 2010-10-27 | 日東電工株式会社 | Water-dispersed pressure-sensitive adhesive composition, process for producing the same, and sheet for surface protection |
| WO2002034808A1 (en) * | 2000-10-25 | 2002-05-02 | Akzo Nobel N.V. | Photoactivatable water borne coating composition |
| JP4837312B2 (en) * | 2005-06-22 | 2011-12-14 | 日本ペイント株式会社 | Water-based clear coating composition and method for forming clear coating film |
| JP4837313B2 (en) * | 2005-06-22 | 2011-12-14 | 日本ペイント株式会社 | Water-based clear coating composition and method for forming clear coating film |
| KR100703854B1 (en) * | 2006-01-13 | 2007-04-09 | 에스에스씨피 주식회사 | Solventless uv curable emulsion coating composition |
| JPWO2007139157A1 (en) * | 2006-05-31 | 2009-10-08 | 株式会社日本触媒 | Polyvalent (meth) acrylamide compound and water-based curable resin composition containing the same |
| JP5327496B2 (en) * | 2007-01-31 | 2013-10-30 | 荒川化学工業株式会社 | Water-based paint composition for steel sheet |
| EP2348061A1 (en) * | 2010-01-21 | 2011-07-27 | Bayer MaterialScience AG | Method for producing water emulsion polyurethane polyacrylate hybrid systems |
| JP6112012B2 (en) * | 2011-07-20 | 2017-04-12 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion and use thereof |
-
1991
- 1991-09-05 JP JP3225584A patent/JP2938239B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0565323A (en) | 1993-03-19 |
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