JP3816670B2 - Hydrophilic polyurethane resin and method for producing the same - Google Patents

Description

【００１２】
（ここで、Ｒ₁は炭素数２０以下のアルキル基、脂環族基、芳香族基（ハロゲン、アルキル基で置換されていてもよい）であり、Ｒ₂及びＲ₃は−Ｏ−、−ＣＯ−、−ＣＯＯ−、−ＮＨＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−等で連結されていてもよい低級アルキレン基であり、Ｘ及びＹは−ＯＨ、−ＣＯＯＨ、−ＮＨ₂、−ＮＨＲ₁、−ＳＨ等の反応性基であり、Ｘ及びＹは同一か異なってもよい。又、これらの基に誘導できるエポキシ基、アルコキシ基、酸ハライド基、酸無水物基、又はカルボキシルエステル基でもよい。）
【００１３】
【化２】
一般式（２）で表される化合物。

（ここで、Ｒ₁、Ｒ₂及びＲ₃は前記と同意義を有するが、但し二つのＲ₁同士は環状構造を形成するものであってもよい。Ｒ₄は−（ＣＨ₂）_n−（ｎ＝０〜２０）であり、Ｒ₂又はＲ₃は前記と同意義を有し、Ｚは炭素原子又は窒素原子を表す。）
【００１４】
【化３】
一般式（３）で表される化合物。

（ここで、Ｘ及びＹと前記と同意義を有し、Ｗは窒素含有複素環、窒素と酸素含有複素環、又は窒素と硫黄含有複素環を表す。）
【００１５】
一般式（１）、（２）又は（３）で表される化合物の具体例としては以下のものが挙げられる。
Ｎ，Ｎ−ジヒドロキシエチル−メチルアミン、
Ｎ，Ｎ−ジヒドロキシエチル−エチルアミン、
Ｎ，Ｎ−ジヒドロキシエチル−イソプロピルアミン、
Ｎ，Ｎ−ジヒドロキシエチル−ｎ−ブチルアミン、
Ｎ，Ｎ−ジヒドロキシエチル−ｔ−ブチルアミン、
メチルイミノビスプロピルアミン、
Ｎ，Ｎ−ジヒドロキシエチルアニリン、
Ｎ，Ｎ−ジヒドロキシエチル−ｍ−トルイジン、
Ｎ，Ｎ−ジヒドロキシエチル−ｐ−トルイジン、
Ｎ，Ｎ−ジヒドロキシエチル−ｍ−クロロアニリン、
Ｎ，Ｎ−ジヒドロキシエチルベンジルアミン、
Ｎ，Ｎ−ジメチル−Ｎ’，Ｎ’−ジヒドロキシエチル−１，３−ジアミノプロパン、
Ｎ，Ｎ−ジエチル−Ｎ’，Ｎ’−ジヒドロキシエチル−１，３−ジアミノプロパン、
Ｎ−ヒドロキシエチル−ピペラジン、
Ｎ，Ｎ’−ジヒドロキシエチル−ピペラジン、
Ｎ−ヒドロキシエトキシエチル−ピペラジン、
１，４−ビスアミノプロピル−ピペラジン、
Ｎ−アミノプロピル−ピペラジン、
ジピコリン酸、
２，３−ジアミノピリジン、
２，５−ジアミノピリジン、
２，６−ジアミノピリジン、
２，６−ジアミノ−４−メチルピリジン、
２，６−ジヒドロキシピリジン、
２，６−ピリジン−ジメタノール、
２−（４−ピリジル）−４，６−ジヒドロキシピリミジン、
２，６−ジアミノトリアジン、
２，５−ジアミノトリアゾール、
２，５−ジアミノオキサゾール等がある。
【００１６】
又、これら第３級アミノ化合物のエチレンオキサイド付加物やプロピレンオキサイド付加物等も本発明に使用できる。その付加物としては、例えば、
【化４】

【００１７】
【化５】

【化６】

【００１８】
【化７】

【化８】

【００１９】
【化９】

【化１０】

（上記式中のｎは１〜６０の整数を、ｍは１〜６の整数を表す。）
上記の第３級アミノ化合物を構成成分とするポリウレタン系樹脂は、従来の公知の方法に準じて得ることができる。
【００２０】
有機ポリイソシアネートとしては、従来公知のいずれのものも使用できるが、例えば、好ましいものとして、４，４−ジフェニルメタンジイソシアネート（ＭＤＩ）、水素添加ＭＤＩ、イソホロンジイソシアネート、１，３−キシリレンジイソシアネート、１，４−キシリレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，５−ナフタリンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート等があり、或いはこれらの有機ポリイソシアネートと低分子量のポリオールやポリアミンを末端イソシアネートとなる様に反応させて得られるポリウレタンプレポリマー等も当然使用することができる。
【００２１】
本発明で使用する高分子量親水性ポリオール又はポリアミンは分子量が４００乃至８，０００の範囲のものである。末端が水酸基で親水性を有するポリオールとしては、例えば、
ポリエチレングリコール、
ポリエチレングリコール／ポリテトラメチレングリコール共重合ポリオール、
ポリエチレングリコール／ポリプロピレングリコール共重合ポリオール、
ポリエチレングリコールアジペート、
ポリエチレングリコールサクシネート、
ポリエチレングリコール／ポリ−ε−ラクトン共重合ポリオール、
ポリエチレングリコール／ポリ−バレロラクトン共重合ポリオールが挙げられる。
【００２２】
又、末端がアミノ基で親水性を有するポリエチレンオキサイド誘導体としては、例えば、
ポリエチレンオキサイドジアミン、
ポリエチレンオキサイドプロピレンオキサイドジアミン、
ポリエチレンオキサイドトリアミン、
ポリエチレンオキサイドプロピレンオキサイドトリアミンが挙げられる。その他、カルボキシル基やビニル基を有したエチレンオキサイド付加物等が挙げられる。
但し、ポリウレタン系樹脂の製造に際しては、得られる樹脂に他の性能を付与するため、上記の如き親水性鎖を有しない他のポリオール、ポリアミン、ポリカルボン酸等を共重合することも可能である。
【００２３】
上記の如き材料から得られる分子鎖中に第３級アミノ基を有する親水性ポリウレタン系樹脂の好ましい分子量は、数千乃至８０万のものであり、最も好ましいものは重量平均分子量が５，０００〜５００，０００のものである。本発明の樹脂は、無溶剤で調製してもよいし、水溶液や溶剤中で調製したものでもよい。
【００２４】
本発明の親水性ポリウレタン系樹脂中の第３級アミノ基は、主鎖或は側鎖中又は両方に含有してよく、樹脂中における含有量は０．１〜５０ｍｅｑ／ｇ、好ましくは０．５〜２０ｍｅｑ／ｇである。第３級アミノ基の含有量が、０．１ｍｅｑ／ｇ以下、すなわち分子量１０，０００当たり１個以下では、本発明の所期の目的である耐水性、耐ブロッキング性といった特性の発現が不十分となり、一方、第３級アミノ基の含有量が５０ｍｅｑ／ｇ以上、すなわち分子量２０当たり１個以上では樹脂中の親水性部分の減少による撥水性が強くなり、吸水性能や防曇性に劣るようになるので好ましくない。
【００２５】
以上の如き本発明で得られる親水性ポリウレタン系樹脂は、各種素材に対する接着性に優れ、且つ吸水性、防曇性、透明性、可撓性、水性インクの筆記性並びに耐水性、耐ブロッキング性に優れ、インクジェット受像シートの受像層用コーティング剤として、各種フイルムの防曇性の塗料として、内装用樹脂製壁紙の結露防止用表面処理剤として、吸水性の衣料用コーティング剤として、更には合成皮革用材料、合成紙の水性インク筆記用処理剤等として非常に有用である。
【００２６】
【実施例】
次に実施例及び比較例を挙げて本発明を更に具体的に説明する。尚、文中部又は％とあるのは特に断りのない限り重量基準である。
実施例１（ポリウレタン樹脂の合成）
ポリエチレングリコール（分子量２，０４０）１５０部、Ｎ−メチルジエタノールアミン２０部、ジエチレングリコール５部を１５０部のメチルエチルケトンと２１０部のジメチルホルムアミドとの混合溶剤中に溶解し、６０℃でよく攪拌しながら、７４部の水素添加ＭＤＩを１００部のメチルエチルケトンに溶解したものを徐々に滴下し、滴下終了後８０℃で６時間反応させた後、６０部のメチルエチルケトンを加え本発明のポリウレタン樹脂溶液を得た。
【００２７】
この溶液は固形分３５％で５３０ｄＰａ．ｓ（２５℃）の粘度を有し、第３級アミノ基の含有量は０．６７ｍｅｑ／ｇで、重量平均分子量は８万７千であった。又、この溶液から形成したフイルムの破断強度は２４．５ＭＰａで、破断伸度は４５０％で、且つ軟化点は１１５℃であった。
【００２８】
実施例２（ポリウレア樹脂の合成）
ポリエチレンオキサイドジアミン（ジェファーミンＥＤ；分子量２，０００）１５０部、及びメチルイミノビスプロピルアミン３０部及び１，４−ジアミノブタン４部をジメチルホルムアミド２００部に溶解し、内温を２０〜３０℃でよく攪拌しながら、８３部の水素添加ＭＤＩを１００部のジメチルホルムアミドに溶解したものを徐々に滴下して反応させた。滴下終了後、次第に内温を上昇させ、５０℃に達したところで更に６時間反応させた後、１９５部のジメチルホルムアミドを加え本発明のポリウレア樹脂溶液を得た。この溶液は固形分３５％で２３０ｄＰａ．ｓ（２５℃）の粘度を有し、第３級アミノ基の含有量は０．７６ｍｅｑ／ｇで、重量平均分子量は６万３千であった。又、この溶液から形成したフイルムの破断強度は２７．６ＭＰａで、破断伸度は３１０％で、且つ軟化点は１４５℃であった。
【００２９】
実施例３（ポリウレタン−ポリウレア樹脂の合成）
ポリエチレンオキサイドジアミン（ジェファーミンＥＤ；分子量２，０００）１５０部、Ｎ，Ｎ−ジメチル−Ｎ’，Ｎ’−ジヒドロキシエチル−１，３−ジアミノプロパン３０部、トリエチレングリコール６部を１４０部のジメチルホルムアミド中に溶解し、内温を２０〜３０℃でよく攪拌しながら、７０部の水素添加ＭＤＩを２００部のメチルエチルケトン７５部に溶解したものを徐々に滴下し、滴下終了後８０℃で６時間反応させて反応終了後、メチルエチルケトン１３５部を加え本発明のポリウレタン−ポリウレア樹脂溶液を得た。この溶液は固形分３５％で２８０ｄＰａ．ｓ（２５℃）の粘度を有し、第３級アミノ基の含有量は１．２３ｍｅｑ／ｇで、重量平均分子量は６万９千であった。又、この溶液から形成したフイルムの破断強度は１４．７ＭＰａで、破断伸度は４５０％で、且つ軟化点は１０７℃であった。
【００３０】
比較例１
実施例１の処方でＮ−メチルジエタノールアミンを使用せず、他は実施例１と同じ材料と処方によるポリウレタン樹脂溶液を得た。この溶液は固形分３５％で５００ｄＰａ．ｓ（２５℃）の粘度を有し、重量平均分子量は８万４千であった。又、この溶液から形成したフイルムの破断強度は２１．５ＭＰａで、破断伸度は４００％で、且つ軟化点は１０２℃であった。
【００３１】
比較例２
実施例２の処方でメチルイミノビスプロピルアミンを使用せず、他は実施例２と同じ材料と処方によるポリウレア樹脂溶液を得た。この溶液は固形分３５％で３００ｄＰａ．ｓ（２５℃）の粘度を有し、重量平均分子量は７万であった。又、この溶液から形成したフイルムの破断強度は２６．０ＭＰａで、破断伸度は２６０％で、且つ軟化点は１４５℃であった。
【００３２】
比較例３
実施例３の処方でＮ，Ｎ−ジメチル−Ｎ’，Ｎ’−ジヒドロキシエチル−１，３−ジアミノプロパンを使用せず、他は実施例３と同じ材料と処方によるポリウレタン−ポリウレア樹脂溶液を得た。この溶液は固形分３５％で２２０ｄＰａ．ｓ（２５℃）の粘度を有し、重量平均分子量は６万５千であった。又、この溶液から形成したフイルムの破断強度は１３．０ＭＰａで、破断伸度は４７０％で、且つ軟化点は８８℃であった。
【００３３】
比較例４
鹸化度９８．５％のポリビニルアルコール（重合度５５０）の５％水溶液を調製した。
【００３４】
インクジェット用受像層への応用
実施例１〜３及び比較例１〜４で得られた樹脂溶液を１００μｍのＰＥＴフイルムに乾燥後の厚みが２０μｍとなるように塗工し、透明シートを作製し、カラーインクジェットプリンター（セイコーエプソン社；ＰＭ−７５０Ｃ）で印字記録を行い、以下の項目の評価を行って後記表１の結果を得た。
【００３５】
「耐ブロッキング性」
樹脂コーティング面に未処理ＰＥＴフイルムを、荷重０．２９Ｍｐａ、温度４０℃で１日放置後のブロッキング性の評価を行った。
○・・・ブロッキング性なし。
△・・・ややブロッキング性あり。
×・・・ブロッキング性あり。
【００３６】
「プリンター搬送性」
インクジェットプリンターでの印字記録の際のプリンター搬送性を評価した。
○・・・搬送性良好。
△・・・わずかに異音を生じる。
×・・・搬送性不良。
【００３７】
「発色鮮明性」
インクジェットプリンターでカラー画像を印字後、得られたカラー画像の発色鮮明性について目視により観察した。
○・・・良い。
△・・・普通。
×・・・悪い。
【００３８】
「印字画像の耐水性」
インクジェットプリンターでカラー印字後、記録シートを水中に漬け（２０℃、２４時間）、その後室温で乾燥した際の記録画像の滲み、発色の変化を目視により観察した。
○・・・変化なし。
△・・・変色が認められる。
×・・・完全に溶解してなくなる。
【００３９】
【表１】

【００４０】
防曇・帯電防止塗料への応用
比較例５
比較例１で得られた樹脂に、非イオン性界面活性剤（ポリオキシエチレンノニルフェニルエーテル；日本油脂（株）製）を固形分重量比で９５：５に混合した。
比較例６
ポリビニルブチラール（重合度７００、積水化学（株）製）１００部、トリオクチルフォスフェート５０部及びポリオキシエチレンラウリルエーテルリン酸エステル（リン酸エステル系界面活性剤、第一工業製薬（株）製）３部をエタノール４００部に混合溶解した。
【００４１】
実施例１〜３及び比較例１、５及び６で得られた樹脂溶液を、透明なアクリル樹脂板に刷毛塗りして試料板とし、防曇性及び帯電防止性の評価を行って後記表２の結果を得た。
「防曇性」
沸騰水浴上、５ｃｍのところに試料板をセットして５０℃の水蒸気に１０分間曝した時の試料板の曇りを評価した。
○・・・曇りなし。
△・・・部分的に曇り。
×・・・曇り。
【００４２】
「耐水性」
沸騰水浴上、５ｃｍのところに試料板をセットして５０℃の水蒸気に１０分間曝した時の試料板の状態を評価した。
○・・・変化なし。
△・・・少し状態の変化あり。
×・・・塗膜の剥離又は溶解が生じた。
【００４３】
「帯電防止性」
ダストチェンバーテストにより帯電カーボンの付着性を評価した。
○・・・カーボンの付着なし。
△・・・一部カーボンの付着あり。
×・・・カーボン付着あり。
【００４４】
【表２】

【００４５】
【発明の効果】
上記のように、本発明で得られる親水性ポリウレタン樹脂は、各種素材に対する接着性に優れ、且つ吸水性、防曇性、透明性、可撓性、水性インクの筆記性並びに耐水性、耐ブロッキング性に優れ、インクジェット受像シートの受像層用コーティング剤として、各種フイルムの防曇性の塗料として、内装用樹脂製壁紙の結露防止用表面処理剤として、吸水性の衣料用コーティング剤として、合成擬革用材料として非常に有用である効果を与える。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrophilic polyurethane-based resin and a method for producing the same, and more specifically, has excellent adhesion to various materials, and has water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties and water resistance, The present invention relates to a hydrophilic polyurethane resin excellent in blocking resistance.
[0002]
[Prior art]
Polyurethane resin is excellent in abrasion resistance, adhesiveness, flexibility, chemical resistance, etc., and also excellent in suitability for various processing methods, so various binders such as coating agents, paints, inks, and films, It is widely used as a sheet or other molded body, and a polyurethane resin suitable for each application has been proposed. The polyurethane resin is a generic term for polyurethane resin, polyurea resin, and polyurethane-polyurea resin. These polyurethane-based resins are basically obtained by reacting a high-molecular-weight polyol component, an organic polyisocyanate component, and, if necessary, a chain extender component. Physical properties of polyurethane resins are provided.
[0003]
[Problems to be solved by the invention]
However, regarding the use of polyurethane resins, for example, surface treatment agents for agricultural resin sheet anti-fogging paints, interior resin wallpaper, fiber coating agents, inkjet image-receiving sheet coating agents, etc., are hydrophilic. Usually, blocking resistance is also required at the same time. Among these, when polyethylene glycol obtained from ring-opening polymerization of ethylene oxide is used as the high molecular weight hydrophilic polyol component, a polyurethane resin having high strength, high elasticity and excellent hydrophilicity can be obtained, but the water resistance is high. The water is badly swollen, whitened and the strength is lowered, and there is a problem that it is not suitable for various paints, binders for printing inks, molded articles, films, sheets and the like.
[0004]
Accordingly, an object of the present invention is a hydrophilic polyurethane resin excellent in adhesiveness to various materials and excellent in water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, and blocking resistance. Is to provide.
[0005]
[Means for Solving the Problems]
The above object is achieved by the present invention described below. That is, the present invention is an organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine, at least one active hydrogen group and one or more tertiary amino groups and optionally the compounds and should have in the same molecule chain extender (Excluding those having a polyoxyethylene chain in the side chain), containing a tertiary amino group in an amount of 0.1 to 50 m eq / g, and a weight average molecular weight of 5,000 to It is a hydrophilic polyurethane resin characterized by being 500,000 and a method for producing the same.
[0006]
By introducing a tertiary amino group into the polyurethane resin, it has excellent adhesion to various materials, water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, and blocking resistance. A hydrophilic polyurethane resin having excellent properties is provided.
[0007]
First, dye / pigment molecules of printing inks and inkjet inks have an anionic carboxyl group or sulfonic acid group in the molecule, and a tertiary amino group is introduced into the chain of the hydrophilic polyurethane resin. When the obtained resin and the above dye / pigment are mixed or contacted, an ionic bond is formed between the dye / pigment and the tertiary amino group in the resin, and the dye / pigment fixability and water resistance It is considered that the intermolecular force of the polyurethane resin is increased by the introduction of the tertiary amino group, and the water resistance is improved.
[0008]
However, considering the ionic bondability as described above, which is easily dissociated in the presence of moisture, the reason for this improvement in water resistance is not clear, but the resin of the present invention is hydrophilic, but hydrophobic in its molecule. Since the ionic bond is formed between the hydrophilic part in the resin and the tertiary amino group and the dye / pigment, the hydrophobic part surrounds the ionic bond part. It seems that the water resistance is improved.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to preferred embodiments.
Hydrophilic polyurethane resin of the present invention, an organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine and optionally reacting the chain extender with upon producing a hydrophilic polyurethane resin, at least one active hydrogen group And a compound having at least one tertiary amino group in the same molecule.
[0010]
First, in the present invention, the compound used for introducing a tertiary amino group into the molecular chain constituting the hydrophilic polyurethane resin is one or more reactive groups such as an amino group in the molecule. , An epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, an alkoxy group, an acid halide group, a carboxyester group, an acid anhydride group, and the like, and a tertiary amino group in the molecular chain.
[0011]
Preferable examples of the tertiary amino group-containing compound having a reactive group include the following compounds.
[Chemical 1]
The compound represented by General formula (1).

[0012]
(Here, R ₁ is an alkyl group having 20 or less carbon atoms, an alicyclic group, or an aromatic group (which may be substituted with a halogen or an alkyl group), and R ₂ and R ₃ are —O—, — CO -, - COO -, - NHCO -, - S -, - SO -, - SO 2 - is also substituted lower alkylene group optionally linked by such, X and Y are -OH, -COOH, -NH ₂ , —NHR ₁ , —SH, etc., X and Y may be the same or different, and can be derived from these groups, such as an epoxy group, an alkoxy group, an acid halide group, an acid anhydride group, or (It may be a carboxyl ester group.)
[0013]
[Chemical 2]
A compound represented by the general formula (2).

(Wherein R ₁ , R ₂ and R ₃ have the same meaning as described above, but two R _{1 s} may form a cyclic structure. R ₄ represents — (CH ₂ ) _n — (N = 0 to 20), R ₂ or R ₃ has the same meaning as described above, and Z represents a carbon atom or a nitrogen atom.)
[0014]
[Chemical 3]
A compound represented by the general formula (3).

(Here, X and Y have the same meaning as described above, and W represents a nitrogen-containing heterocycle, nitrogen and oxygen-containing heterocycle, or nitrogen and sulfur-containing heterocycle.)
[0015]
Specific examples of the compound represented by the general formula (1), (2) or (3) include the following.
N, N-dihydroxyethyl-methylamine,
N, N-dihydroxyethyl-ethylamine,
N, N-dihydroxyethyl-isopropylamine,
N, N-dihydroxyethyl-n-butylamine,
N, N-dihydroxyethyl-t-butylamine,
Methyliminobispropylamine,
N, N-dihydroxyethylaniline,
N, N-dihydroxyethyl-m-toluidine,
N, N-dihydroxyethyl-p-toluidine,
N, N-dihydroxyethyl-m-chloroaniline,
N, N-dihydroxyethylbenzylamine,
N, N-dimethyl -N ', N'-dihydroxyethyl - 1,3-diaminopropane,
N, N-diethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane,
N-hydroxyethyl-piperazine,
N, N′-dihydroxyethyl-piperazine,
N-hydroxyethoxyethyl-piperazine,
1,4-bisaminopropyl-piperazine,
N-aminopropyl-piperazine,
Dipicolinic acid,
2,3-diaminopyridine,
2,5-diaminopyridine,
2,6-diaminopyridine,
2,6-diamino-4-methylpyridine,
2,6-dihydroxypyridine,
2,6-pyridine-dimethanol,
2- (4-pyridyl) -4,6-dihydroxypyrimidine,
2,6-diaminotriazine,
2,5-diaminotriazole,
There are 2,5-diaminooxazole and the like.
[0016]
Also, ethylene oxide adducts and propylene oxide adducts of these tertiary amino compounds can be used in the present invention. As the adduct, for example,
[Formula 4]

[0017]
[Chemical formula 5]

[Chemical 6]

[0018]
[Chemical 7]

[Chemical 8]

[0019]
[Chemical 9]

[Chemical Formula 10]

(In the above formula, n represents an integer of 1 to 60, and m represents an integer of 1 to 6.)
The polyurethane resin containing the above-mentioned tertiary amino compound as a constituent component can be obtained according to a conventionally known method.
[0020]
As the organic polyisocyanate, any conventionally known one can be used. For example, 4,4-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1, 4- xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 Torirenjiiso shea Aneto, 1,5 naphthalene diisocyanate, m- phenylene diisocyanate, there is p- phenylene diisocyanate, etc., or low and these organic polyisocyanates Of course, a polyurethane prepolymer obtained by reacting a molecular weight polyol or polyamine so as to be a terminal isocyanate can also be used.
[0021]
The high molecular weight hydrophilic polyol or polyamine used in the present invention has a molecular weight in the range of 400 to 8,000. As a polyol having a hydroxyl group at the end and having hydrophilicity, for example,
Polyethylene glycol,
Polyethylene glycol / polytetramethylene glycol copolymer polyol,
Polyethylene glycol / polypropylene glycol copolymer polyol,
Polyethylene glycol adipate,
Polyethylene glycol succinate,
Polyethylene glycol / poly-ε-lactone copolymer polyol,
Examples thereof include polyethylene glycol / poly-valerolactone copolymer polyol.
[0022]
In addition, as a polyethylene oxide derivative having a terminal amino group and hydrophilicity, for example,
Polyethylene oxide diamine,
Polyethylene oxide, propylene oxide diamine,
Polyethylene oxide triamine,
A polyethylene oxide propylene oxide triamine is mentioned. Other examples include ethylene oxide adducts having a carboxyl group or a vinyl group.
However, in the production of polyurethane resins, it is possible to copolymerize other polyols, polyamines, polycarboxylic acids, etc. that do not have a hydrophilic chain as described above in order to impart other performance to the resulting resin. .
[0023]
The preferred molecular weight of the hydrophilic polyurethane-based resin having a tertiary amino group in the molecular chain obtained from the material as described above is from several thousand to 800,000, and most preferred is a weight average molecular weight of 5,000 to 500,000. The resin of the present invention may be prepared without a solvent, or may be prepared in an aqueous solution or a solvent.
[0024]
The tertiary amino group in the hydrophilic polyurethane resin of the present invention may be contained in the main chain, the side chain or both, and the content in the resin is 0.1 to 50 m eq / g, preferably 0.5 to 20 m eq / g. When the content of the tertiary amino group is 0.1 m eq / g or less, that is, 1 or less per 10,000 molecular weight, the characteristics such as water resistance and blocking resistance, which are the intended purposes of the present invention, are exhibited. On the other hand, when the content of the tertiary amino group is 50 m eq / g or more, that is, 1 or more per 20 molecular weight, the water repellency increases due to the decrease of the hydrophilic portion in the resin, and the water absorption performance and anti-fogging are increased. Since it becomes inferior in property, it is not preferable.
[0025]
The hydrophilic polyurethane-based resin obtained by the present invention as described above is excellent in adhesiveness to various materials and has water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, and blocking resistance. Excellent as an image-receiving layer coating agent for inkjet image-receiving sheets, as an anti-fogging paint for various films, as a surface treatment agent for anti-condensation of interior resin wallpaper, and as a water-absorbing clothing coating agent It is very useful as a material for leather, a processing agent for water-based ink writing on synthetic paper, and the like.
[0026]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, “%” or “%” is based on weight unless otherwise specified.
Example 1 (Synthesis of polyurethane resin)
While dissolving 150 parts of polyethylene glycol (molecular weight 2,040), 20 parts of N-methyldiethanolamine, and 5 parts of diethylene glycol in a mixed solvent of 150 parts of methyl ethyl ketone and 210 parts of dimethylformamide, A solution obtained by dissolving 100 parts of hydrogenated MDI in 100 parts of methyl ethyl ketone was gradually added dropwise. After completion of the addition, the mixture was reacted at 80 ° C. for 6 hours, and then 60 parts of methyl ethyl ketone was added to obtain a polyurethane resin solution of the present invention.
[0027]
This solution had a solids content of 35% and 530 dPa.s. It had a viscosity of s (25 ° C.), the tertiary amino group content was 0.67 m eq / g, and the weight average molecular weight was 87,000. The film formed from this solution had a breaking strength of 24.5 MPa, a breaking elongation of 450%, and a softening point of 115 ° C.
[0028]
Example 2 (Synthesis of polyurea resin)
150 parts of polyethylene oxide diamine (Jephamine ED; molecular weight 2,000), 30 parts of methyliminobispropylamine and 4 parts of 1,4-diaminobutane are dissolved in 200 parts of dimethylformamide, and the internal temperature is 20-30 ° C. While stirring well, 83 parts of hydrogenated MDI dissolved in 100 parts of dimethylformamide was gradually added dropwise to react. After completion of the dropwise addition, the internal temperature was gradually raised, and when the temperature reached 50 ° C., the mixture was further reacted for 6 hours, and 195 parts of dimethylformamide was added to obtain a polyurea resin solution of the present invention. This solution has a solid content of 35% and 230 dPa.s. It had a viscosity of s (25 ° C.), the tertiary amino group content was 0.76 m eq / g, and the weight average molecular weight was 63,000. The film formed from this solution had a breaking strength of 27.6 MPa, a breaking elongation of 310%, and a softening point of 145 ° C.
[0029]
Example 3 (Synthesis of polyurethane-polyurea resin)
Polyethylene oxide diamine (Jephamine ED; molecular weight 2,000) 150 parts, N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane 30 parts, triethylene glycol 6 parts 140 parts dimethyl While dissolving in formamide and stirring well at an internal temperature of 20-30 ° C., 70 parts of hydrogenated MDI dissolved in 200 parts of methyl ethyl ketone was gradually added dropwise. After completion of the reaction, 135 parts of methyl ethyl ketone was added to obtain a polyurethane-polyurea resin solution of the present invention. This solution had a solids content of 35% and 280 dPa.s. It had a viscosity of s (25 ° C.), the tertiary amino group content was 1.23 m eq / g, and the weight average molecular weight was 69,000. The film formed from this solution had a breaking strength of 14.7 MPa, a breaking elongation of 450%, and a softening point of 107 ° C.
[0030]
Comparative Example 1
In the formulation of Example 1, N-methyldiethanolamine was not used, and a polyurethane resin solution having the same material and formulation as in Example 1 was obtained. This solution had a solid content of 35% and 500 dPa.s. The viscosity was s (25 ° C.) and the weight average molecular weight was 84,000. The film formed from this solution had a breaking strength of 21.5 MPa, a breaking elongation of 400%, and a softening point of 102 ° C.
[0031]
Comparative Example 2
A polyurea resin solution having the same material and formulation as in Example 2 was obtained except that methyliminobispropylamine was not used in the formulation of Example 2. This solution had a solid content of 35% and 300 dPa.s. The viscosity was s (25 ° C.), and the weight average molecular weight was 70,000. The film formed from this solution had a breaking strength of 26.0 MPa, a breaking elongation of 260%, and a softening point of 145 ° C.
[0032]
Comparative Example 3
The formulation of Example 3 does not use N, N-dimethyl-N ′, N′-dihydroxyethyl-1,3-diaminopropane, and a polyurethane-polyurea resin solution with the same material and formulation as in Example 3 is obtained. It was. This solution has a solid content of 35% and is 220 dPa.s. The viscosity was s (25 ° C.), and the weight average molecular weight was 65,000. The film formed from this solution had a breaking strength of 13.0 MPa, a breaking elongation of 470%, and a softening point of 88 ° C.
[0033]
Comparative Example 4
A 5% aqueous solution of polyvinyl alcohol (polymerization degree 550) having a saponification degree of 98.5% was prepared.
[0034]
Application to Inkjet Image Receiving Layer The resin solutions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were applied to a 100 μm PET film so that the thickness after drying was 20 μm, and a transparent sheet was produced. Printing was recorded with a color inkjet printer (Seiko Epson Corporation; PM-750C), and the following items were evaluated to obtain the results shown in Table 1 below.
[0035]
"Blocking resistance"
The blocking property after leaving untreated PET film on the resin coating surface for 1 day at a load of 0.29 Mpa and a temperature of 40 ° C. was evaluated.
○: No blocking property.
Δ: Slightly blocking.
X: There is blocking property.
[0036]
"Printer transportability"
The printer transportability during printing and recording with an inkjet printer was evaluated.
○ ... Good transportability.
Δ: Slightly abnormal noise is generated.
X: poor transportability.
[0037]
"Color clarity"
After printing a color image with an ink jet printer, the resulting color image was visually observed for color clarity.
○ ・ ・ ・ Good.
Δ: Normal.
× ... Bad.
[0038]
"Water resistance of printed images"
After color printing with an inkjet printer, the recording sheet was immersed in water (20 ° C., 24 hours), and then the bleeding of the recorded image and the change in color development were observed visually when dried at room temperature.
○: No change.
Δ: Discoloration is observed.
X: Dissolved completely.
[0039]
[Table 1]

[0040]
Application to anti-fogging and anti-static coatings Comparative Example 5
The resin obtained in Comparative Example 1 was mixed with a nonionic surfactant (polyoxyethylene nonylphenyl ether; manufactured by Nippon Oil & Fats Co., Ltd.) at a solid content weight ratio of 95: 5.
Comparative Example 6
Polyvinyl butyral (degree of polymerization 700, manufactured by Sekisui Chemical Co., Ltd.) 100 parts, trioctyl phosphate 50 parts, and polyoxyethylene lauryl ether phosphate (phosphate ester surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 3 parts were mixed and dissolved in 400 parts of ethanol.
[0041]
The resin solutions obtained in Examples 1 to 3 and Comparative Examples 1, 5 and 6 were brush-coated on a transparent acrylic resin plate to obtain a sample plate, and the antifogging property and antistatic property were evaluated, as shown in Table 2 below. The result was obtained.
"Anti-fogging property"
The sample plate was set at 5 cm on a boiling water bath, and the cloudiness of the sample plate when exposed to 50 ° C. water vapor for 10 minutes was evaluated.
○ ... No cloudiness.
Δ: Partly cloudy.
×: Cloudy.
[0042]
"water resistant"
The state of the sample plate was evaluated when the sample plate was set at 5 cm on a boiling water bath and exposed to water vapor at 50 ° C. for 10 minutes.
○: No change.
Δ: Some change in state.
X: Peeling or dissolution of the coating film occurred.
[0043]
"Antistatic properties"
The adhesion of charged carbon was evaluated by a dust chamber test.
○ ... No carbon adhesion.
Δ: Some carbon adhered.
X: There is carbon adhesion.
[0044]
[Table 2]

[0045]
【The invention's effect】
As described above, the hydrophilic polyurethane resin obtained in the present invention is excellent in adhesiveness to various materials and has water absorption, antifogging properties, transparency, flexibility, water-based ink writing properties, water resistance, and blocking resistance. As a coating agent for image-receiving layers of inkjet image-receiving sheets, as an anti-fogging paint for various films, as a surface treatment agent for preventing condensation on interior resin wallpaper, and as a coating agent for water-absorbing clothing, The effect is very useful as a leather material.

Claims (4)

Organic polyisocyanates, obtained by reacting a high molecular weight hydrophilic polyol or polyamine, at least one active hydrogen group and one or more tertiary amino groups and optionally the compounds and should have in the same molecule chain extender (Excluding those having a polyoxyethylene chain in the side chain), containing a tertiary amino group in an amount of 0.1 to 50 m eq / g and a weight average molecular weight of 5,000 to 500,000. Hydrophilic polyurethane resin characterized by   2. The hydrophilic polyurethane resin according to claim 1, wherein the high molecular weight hydrophilic polyol or polyamine comprises an ethylene oxide segment, and the proportion of the segment in the hydrophilic polyurethane resin is 30 to 80 wt%. . Organic polyisocyanate, a high molecular weight hydrophilic polyol or polyamine, at least one active hydrogen group and one or more tertiary amino groups and optionally the compounds and should have in the same molecule chain extender, polyurethane obtained The tertiary amino group in the resin (excluding those having a polyoxyethylene chain in the side chain) is 0.1 to 50 m eq / g, and the weight average molecular weight is 5,000 to 500,000. A process for producing a hydrophilic polyurethane resin, characterized by reacting at a ratio of   The hydrophilic polyurethane system according to claim 3, wherein the high molecular weight hydrophilic polyol or polyamine comprises an ethylene oxide segment and is reacted in an amount such that the proportion of the segment in the hydrophilic polyurethane resin is 30 to 80% by weight. Manufacturing method of resin.