JP2004315637A - Polyurethane resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane resin composition excellent in liquid flowability and curability, therefore suitable for reaction injection molding process, and giving a cured product with excellent physical properties including tensile elongation and tensile strength, capable of undergoing mixed spray coating and having high mechanical strength and flexibility, and to provide a printing ink binder consisting of a polymer obtained from the above resin composition and having high adhesion, blocking resistance and heat resistance to printed matter. <P>SOLUTION: The polyurethane resin composition comprises a polyisocyanate, an active hydrogen-containing compound and a chain extender, wherein the chain extender consists of an amino compound obtained by adding styrene to an aliphatic polyamine. The cured product is obtained by curing the polyurethane resin composition. The polymer for printing ink binder is obtained by reaction of the polyurethane resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００４８】
【化２】

【００４９】
【化３】

【００５０】
ポリオキシアルキレンポリアミンの重量平均分子量は、９００〜５００００である。使用するポリオキシアルキレンポリアミンの分子量が上記重量平均分子量の範囲未満であると伸び性能が極端に低下する。一方、ポリオキシアルキレンポリアミンの分子量が上記重量平均分子量の範囲を越えると、ポリアミンの粘度が高くなり、塗装作業性の悪化とポリウレア樹脂の強度の低下を招く。
【００５１】
具体的にポリオキシポリアミン成分の例を挙げると、
▲１▼ 式（１）に示す平均重合度ｎが３３で重量平均分子量が２０００のポリオキシプロピレンジアミン（ハンツマン・コーポレーション社製、商品名：ジェファーミンＤ−２０００）
▲２▼ 式（１）に示す平均重合度ｎが６８で重量平均分子量が４０００のポリオキシプロピレンジアミン（ハンツマン・コーポレーション社製、商品名：ジェファーミンＤ−４０００）
▲３▼ 式（２）に示す平均重合度Ａ＋Ｃ＝２．５およびＢ＝４０．５の重量平均分子量２０００のポリオキシプロピレンオキシエチレンジアミン（ハンツマン・コーポレーション社製、商品名：ジェファーミンＥＤ−２０００）
▲４▼ 式（３）に示すポリオキシプロピレングリセリントリアミンで重量平均分子量３０００のもの（ハンツマン・コーポレーション社製、商品名：ジェファーミンＴ−３０００）
▲５▼ 式（３）に示すポリオキシプロピレングリセリントリアミンで重量平均分子量５０００のもの（ハンツマン・コーポレーション社製、商品名：ジェファーミンＴ−５０００）
【００５２】
本発明（２）における、ポリイソシアネート（Ａ）と重量平均分子量が９００〜５００００のポリオール（Ｂ１）および／またはポリアミン（Ｂ２）とから得られるプレポリマー（Ｄ）は、以下の方法により製造することが出来る。
ポリイソシアネート（Ａ）中に含まれるイソシアネート基に対するポリオール（Ｂ１）および／またはポリアミン（Ｂ２）中に含まれる水酸基および／またはアミノ基の当量比は、０．０１〜０．７、好ましくは０．０５〜０．５である。
上記範囲において、噴霧混合塗装に好ましいプレポリマーの粘度となり、生成された樹脂組成物の可とう性、低温における伸び性能も特に良好なものになる。
【００５３】
反応方法はポリイソシアネート（Ａ）にポリオール（Ｂ１）および／またはポリアミン（Ｂ２）を滴下する方法をとる。一括仕込み、およびポリオール（Ｂ１）および／またはポリアミン（Ｂ２）にポリイソシアネート（Ａ）を滴下する方法は、本発明に使用されるプレポリマー（Ｄ）として機能しない。
【００５４】
本発明（２）における、鎖長延長剤（Ｃ）である脂肪族ポリアミンにスチレンを付加したアミノ化合物としては、本発明（１）における脂肪族ポリアミンにスチレンを付加したアミノ化合物と同じものが挙げられる。脂肪族ポリアミンとは本発明（１）における脂肪族ポリアミンと同じものが挙げられる。それらは単独使用でも２種以上の併用でもよい。この中で特に好ましいのは、メタキシリレンジアミン、１，３−ビス（アミノメチル）シクロヘキサンである。脂肪族ポリアミンにスチレンを付加したアミノ化合物は単独使用でも２種以上の併用でも良い。この中で特に好ましいのは、Ｎ−フェネチル−メタキシリレンジアミン、Ｎ，Ｎ’−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ−ジフェネチル−メタキシリレンジアミン、Ｎ−フェネチル−ビス（１，３−アミノメチル）シクロヘキサン、Ｎ，Ｎ’−ジフェネチル−ビス（１，３−アミノメチル）シクロヘキサン、Ｎ，Ｎ−ジフェネチル−ビス（１，３−アミノメチル）シクロヘキサンである。
【００５５】
また本発明（２）における鎖長延長剤（Ｃ）である脂肪族ポリアミンにスチレンを付加したアミノ化合物は、場合によっては、芳香族ポリアミンと併用しても良く、本発明（１）において併用できる芳香族ポリアミンと同じものが挙げられる。それらは単独使用でも２種以上の併用でも良い。
脂肪族ポリアミンにスチレンを付加したアミノ化合物および芳香族ポリアミンの混合重量比は、５：９５〜１００：０、より好ましくは、５０：５０〜１００：０である。上記範囲において、特に強度および可とう性が優れる。
【００５６】
混合物（Ｅ）を構成するポリアミン（Ｂ２）および鎖長延長剤（Ｃ）の混合重量比は、１０：９０〜９０：１０、好ましくは３０：７０〜７０：３０である。上記範囲において、特に強度および可とう性が優れる。
【００５７】
混合物（Ｅ）を構成するポリアミン（Ｂ２）および鎖長延長剤（Ｃ）の混合方法は、公知の方法で良く、一括仕込み、およびポリアミン（Ｂ２）に鎖長延長剤（Ｃ）を滴下する方法、または鎖長延長剤（Ｃ）にポリアミン（Ｂ２）を滴下する方法等があげられる。混合温度も特に限定はされないが、０〜１００℃、好ましくは２０〜８０℃が作業性の面から好ましい。
【００５８】
プレポリマー（Ｄ）におけるイソシアネート基に対するポリアミン（Ｂ２）および鎖長延長剤（Ｃ）のアミノ基の当量比は０．５〜３．０、好ましくは０．９〜２．０である。
上記範囲において、特に引張強度、および引裂強度が優れたものになる。
上記反応には触媒を添加しても良いが、好都合にも、プレポリマー（Ｄ）と混合物（Ｅ）は、触媒を用いることなく反応し、本発明の樹脂系を形成する。
【００５９】
本発明（２）における噴霧混合塗装用ポリウレタン系樹脂組成物は、衝突混合タイプである大型の高圧噴霧装置を用いた大掛かりでかつ高価な装置は不要であり、より安価で簡便なスタティックミキサー混合タイプの噴霧装置が有効である。この系における噴霧混合塗装用ポリウレタン系樹脂組成物のプレポリマー（Ｄ）と混合物（Ｅ）は、小型のコンプレッサ−によりスタティックミキサー中にて２成分を緊密に混合させ、直接所望の基材に塗布することが出来る。
【００６０】
本発明（３）の主成分であるポリウレタン系樹脂組成物から得られる印刷インキバインダー用ポリマーの構成成分は次の通りである。
【００６１】
ポリウレタン系樹脂組成物の構成成分であるジイソシアネート化合物（Ａ１）としては、芳香族、脂肪族、芳香脂肪族および脂環族のジイソシアネート類がある。例えば、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルジメチ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、１，５−ナフチレンジイソシアネート、ジアルキルジフェニ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、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、シクロヘキサン−１，４−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ダイマージイソシアネート等がその代表例としてあげることができる。
【００６２】
重量平均分子量が５００〜６０００のポリオール（Ｂ３）としては、酸化エチレン、酸化プロピレン、テトラヒドロフラン等の重合体もしくは共重合体等のポリエーテルポリオール類；エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ネオペンチルグリコール、ペンタンジオール、３−メチル−１，５−ペンタンジオール、ヘキサンジオール、オクタンジオール、１，４−ブチンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等の飽和および不飽和の各種公知の低分子グリコール類、またはＮ−ブチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル類のアルキルグリシジルエーテル類、バーサテッィク酸グリシジルエステル等のモノカルボン酸グリシジルエステル類、ダイマー酸を還元して得られるダイマージオールと、アジピン酸、無水フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、コハク酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の二塩基酸もしくはこれらに対応する酸無水物やダイマー酸等を脱水縮合せしめて得られるポリエステルポリオール類；環状エステル化合物を開環重合して得られるポリエステルポリオール類；その他ポリカーボネートポリオール類、ポリブタジエングリコール類、ビスフェノールＡに酸化エチレンもしくは酸化プロピレンを付加して得られるグリコール類等の一般にポリウレタンの製造に用いられる各種公知のポリオールが例示される。
以上の各種ポリオールの重量平均分子量は、得られるポリウレタン樹脂の相溶性、乾燥性、耐ブロッキング性等を考慮して適宜決定され、通常は５００〜６０００の範囲内であることが望ましい。該重量平均分子量が５００未満であれば溶解性の低下に伴い印刷適正が劣る傾向にあり、他方６０００を越えると乾燥性および耐ブロッキング性が低下する傾向がある。
【００６３】
本発明（３）においては、ポリウレタン系樹脂組成物を構成する鎖長延長剤（Ｃ）として、脂肪族ポリアミンにスチレンを付加したアミノ化合物を用いる。具体的には、本発明（１）で使用される脂肪族ポリアミンにスチレンを付加したアミノ化合物と同じものが挙げられる。
【００６４】
本発明（３）において、末端停止剤は、所望の分子量のポリマーを調整する際に、必要に応じ使用されるが、以下に述べる化合物を上記と併用することもできる。鎖長停止剤に用いられる化合物として具体的には、メチルアルコール、エチルアルコール、Ｎ−プロピルアルコール、イソプロピルアルコール、Ｎ−ブチルアルコール、イソブチルアルコール等の一価アルコール；モノエチルアミン、Ｎ−プロピルアミン、ジエチルアミン、ジ−Ｎ−プロピルアミン、ジ−Ｎ−ブチルアミン等のモノアミン；モノエタノールアミン、ジエタノールアミン等のアルカノールアミン等が挙げられる。
【００６５】
本発明（３）のポリウレタン系樹脂組成物から得られる印刷インキバインダー用ポリマーを製造する方法は、例えばポリオール（Ｂ３）とジイソシアネート化合物（Ａ１）とを、イソシアネート基過剰のモル比で反応させ、ポリオールの両末端にイソシアネート基を有するプレポリマーを調整し、溶剤で希釈し、次いで鎖長延長剤で高分子量化するプレポリマー法；あるいはポリオール（Ｂ３）、ジイソシアネート化合物（Ａ１）および鎖長延長剤（Ｃ）を一括で反応させるワンショット法等により行うことができるが、均一なポリマー溶液を得る目的には前者が好ましい。上記プレポリマー法において、末端イソシアネート基のプレポリマー化反応時の構成成分の添加順序には特に制限はなく、各成分の全量を逐次または同時に混合し、あるいは必要に応じてプレポリマー化反応途中に適宜、ジイソシアネート化合物（Ａ１）を再添加することなど、従来本分野で用いられている種々の方法を採用することができる。
【００６６】
プレポリマーを製造するに当たり、イソシアネート基数に対するポリオール（Ｂ３）中の水酸基数の比は、１．１〜３．０であることが望ましい。この比が１．１より小さいと耐熱性および被服強度が低下し、３．０より大きい場合には各種プラスチックフィルムに対する接着性が低下する。
また、ポリマーを製造するに当たり、鎖長延長剤（Ｃ）のアミノ基数は、プレポリマーのイソシアネート基１当量に対して０．８〜１．３当量、好ましくは０．９〜１．２当量である。鎖長延長剤（Ｃ）のアミノ基が０．８当量より小さいと、乾燥性、耐ブロッキング性、皮膜強度が十分ではなく、鎖長延長剤（Ｃ）のアミノ基が１．３当量より大きい場合には、鎖長延長剤（Ｃ）が未反応のまま残存し、印刷物に臭気が残り易くなる。
鎖長延長剤（Ｃ）に対する、末端停止剤中のモノアルコールまたはモノアミンとの当量比は、０．５〜５０の範囲内である。該当量比が０．５より小さい場合、耐薬品性が低下し、５０より大きい場合には高分子量化し、樹脂粘度が増大して作業性が低下する。また末端停止剤は、鎖長延長反応前に完結させる、鎖長延長剤（Ｃ）と同時に添加する、または鎖長延長反応終了後に添加し反応を完結させる等、いずれの方法でも良い。
【００６７】
ポリマー溶液の製造に使用される溶媒としては、例えばメタノール、エタノール、イソプロパノール、Ｎ−ブタノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；ジオキサン、テトラヒドロフラン等のエーテル類；へキサン、シクロヘキサン等の脂肪族炭化水素類；酢酸エチル、酢酸ブチル等のエステル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ジメチルスルホキシド、Ｎ−メチル−２−ビロリドン、ジメチルホルムアミド等の非プロトン性極性溶媒およびそれら二種類以上の混合物が挙げられる。
【００６８】
この反応には触媒を用いることもできる。ウレタン化反応を促進する触媒としては、例えばトリエチルアミン、ジメチルアニリン等の三級アミン系触媒または有機錫、有機亜鉛等の有機金属系触媒等が挙げられる。
【００６９】
このようにして得られた本発明（３）のポリマーの重量平均分子量は５０００〜５０００００、好ましくは１００００〜３０００００である。重量平均分子量が５０００未満の場合には、これをバインダーとして用いた印刷インキおよび塗膜の乾燥性、耐ブロッキング性、耐油性が不良となる。一方、重量平均分子量が５０００００を越える場合には、ポリマー溶液の粘度が高いため取り扱いが困難となり、得られる印刷インキおよび塗膜の光沢が低下し、再溶解性も不良となる。
本発明（３）により得られるポリマー溶液中の樹脂固形分（ポリマー）濃度は、その用途における作業性を考慮して適宜使用する溶剤量を調整することにより幅広く設定することができるが、通常は１５〜６０重量％であり、該溶液の粘度は５０〜１０００００ｍＰａ・ｓが実用上好適である。
【００７０】
本発明（３）のポリマーを用いた印刷インキバインダーの適用する対象としてはポリエステル、ナイロン、ポリエチレン、ポリプロピレンフィルム等が好適である。
また本発明（３）のポリマーを用いた印刷インキバインダーは、従来のインキバインダーの場合と同様に使用できる。すなわち、本発明のバインダーに顔料、顔料分散剤、界面活性剤、ワックス、その他添加剤等を加え、ボールミル等の通常のインキ製造装置を用いて混練することによって印刷インキとすることができる。
【００７１】
また必要に応じて、これと相溶性のある樹脂を副成分として使用することができる。例えば、塩素化ポリエチレン、塩素化ポリプロピレン、塩素化エチレンポリプロピレン等の塩素化ポリオレフィン、クロルスルフォン化ポリオレフィン、硝化綿、エチレン酢酸ビニル共重合体もしくはその塩素化物、クロルスルフォン化物、マレイン酸樹脂、ポリ塩化ビニル樹脂、塩化ビニル酢酸ビニル共重合体、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、フェノール樹脂、アルキッド樹脂およびポリウレタン樹脂等があげられる。
【００７２】
本発明（３）のポリマーを用いた印刷インキバインダーは、接着性および耐熱性が優れていることから、種々の合成樹脂成形品用の装飾、表面保護のための塗料用樹脂およびコーティング剤として極めて有用である。また本発明の印刷インキバインダーは、有機溶媒系のみならず、アニオン系、カチオン系、ノニオン系の水性樹脂として用いた場合にも同様の効果が得られる。
【００７３】
本発明（３）は、ポリウレタン系樹脂組成物中の鎖長延長剤にアミノ基の少なくとも１つが、フェネチル基により２級化された脂肪族ポリアミンを用いることにより、従来のポリウレタン系樹脂組成物から得られるポリマーが均一でなく低分子量化合物等の多くの副生物を含有するために接着性不良の問題を起こしていたことに対し、分子量分布の狭いより均一なポリマーが得られ、各種プラスチックフィルムに対して優れた接着性を有するものになる。
【００７４】
【実施例】
以下に、本発明を実施例により具体的に説明するが、本発明はこれに限定されるものではない。
【００７５】
本発明（１）
実施例および比較例中の原料は以下のものを使用した。
ポリエーテルＡ：グリセリンにプロピレンオキサイドを付加重合して得た重量平均分子量が約５０００のトリオールを、触媒の存在下でアンモニアと反応して得たポリエーテルトリアミンであるポリオキシプロピレントリアミン（ハンツマン・コーポレーション社製、ジェファーミンＴ−５０００）
ポリイソシアネート：４，４’−ジフェニルメタンジイソシアネート（日本ポリウレタン工業（株）製）とトリプロピレングリコール（旭電化工業（株）製、ポリエーテルＰ２０００）を反応させて得たイソシアネート基含有量２２．５％のイソシアネートプレポリマー。
アミンＡ：メタキシリレンジアミンを、触媒の存在下でスチレンと付加反応させ、未反応メタキシリレンジアミンおよび触媒を除去した、Ｎ−フェネチル−メタキシリレンジアミン、Ｎ，Ｎ’−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ，Ｎ’−トリフェネチル−メタキシリレンジアミンからなるポリアミン混合物。
アミンＢ：α，α，α’，α’−テトラメチルーメタキシリレンジアミンをジオキサン溶媒中で、ターシャリーブチルクロライドと反応させて得られるＮ−ターシャリーブチル−α，α，α’，α’−テトラメチル−メタキシリレンジアミン。
ＤＥＴＤＡ：３，５−ジエチル−２，４−ジアミノトルエンと３，５−ジエチル−２，６−ジアミノトルエンの重量比８０：２０の混合物（アルベマール社製、ＥｔｈＡＣｕｒＥ１００）。
Ｂ−７１２：中京油脂（株）製のＲＩＭ用ワックス系外部離型剤。
【００７６】
実施例１および比較例１〜３
実施例および比較例として表１に記載された原料配合で成形を行った。
反応射出成形機は、東邦機械（株）製ＮＲ−２３０およびシンシナチ・ミラクロン社製ＬＲＭ−１５Ｍを使用した。アミン混合液およびポリイソシアネートの液温度をそれぞれ２０℃、４０℃に調節し、アミン混合液中に窒素ガスを４０体積％（大気中での値）になるように溶解させた。原料の配合比は表１に記載の量になるように調整し、射出速度は、表１に記載の速度で金型へ注入した。金型は、５００ｍｍ×４００ｍｍ×３．０ｍｍの平板型を７５℃に加熱し、外部離型剤を塗布した後、さらに乾燥した布でよく拭いた。
注入後３０秒で脱型し、離型性、硬化性の良否を比較した。硬化性は、脱型後直ちにシート成形物を水平台上に乗せ、１分後にシートの先端から２０ｃｍを突出して水平面からの垂れの高さを測定し、その大小で硬化性の良否を決めた。同時に、成形直後の脆さを見るため、シートを折り曲げてひび割れするかどうかを調べた。成形品の表面状態も調べた。
物性は成形品より試験片を切り取り、１２０℃のオーブンで１時間加熱した後、引張強さ、および引張伸びを測定した。
結果を表１に示す。
【００７７】
【表１】

【００７８】
本発明（２）
これらにおいて（部）および（％）は重量基準による。
▲１▼ジェファーミンＤ−２０００は、重量平均分子量約２０００のポリオキシプロピレンジアミンである。
▲２▼試験片および物性試験方法は、ＪＩＳ Ｋ６３０１に準拠した。
実施例２
メタキシリレンジイソシアネート（ＭＸＤＩ）とジェファーミンＤ−２０００とを当量比１１：１、滴下温度を２５℃にしジェファーミンＤ−２０００を７時間かけて滴下した。滴下後の反応温度は滴下温度と同温、反応時間は１時間かけることによってプレポリマ−（Ｄ）を調整した。脂肪族性ポリウレア樹脂のうち鎖長延長剤（Ｃ）は、メタキシリレンジアミンを、触媒の存在下でスチレンと付加反応させ、未反応メタキシリレンジアミンおよび触媒を除去した、Ｎ−フェネチル−メタキシリレンジアミン、Ｎ，Ｎ’−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ，Ｎ’−トリフェネチル−メタキシリレンジアミンからなるポリアミン混合物Ｃ１を用いた。ポリアミン（Ｂ２）および（Ｃ）の混合物（Ｅ）は、ジェファーミンＤ−２０００およびポリアミン混合物Ｃ１の重量比５０：５０の組み合わせによって調整した。以上より調整された（Ｄ）と（Ｅ）のモル比を１：１にし、スタティックミキサーによって噴霧混合塗装し、ポリウレタン系樹脂硬化物を得た。得られた硬化物に関する物理的性質を表２に示す。
【００７９】
実施例３
１，３−（ビスイソシアネート）メチルシクロヘキサン（１，３−ＢＩＣ）とジェファーミンＤ−２０００とを当量比１１：１、滴下温度を２５℃にしジェファーミンＤ−２０００を７時間かけて滴下した。滴下後の反応温度は滴下温度と同温、反応時間は１時間かけることによってプレポリマー（Ｄ）を調整した。脂肪族性ポリウレア樹脂のうち鎖長延長剤（Ｃ）は、１，３−（ビスアミノメチル）シクロヘキサンを、触媒の存在下でスチレンと付加反応させ、未反応１，３−（ビスアミノメチル）シクロヘキサンおよび触媒を除去した、Ｎ−フェネチル−１，３−（ビスアミノメチル）シクロヘキサン、Ｎ，Ｎ’−ジフェネチル−１，３−（ビスアミノメチル）シクロヘキサン、Ｎ，Ｎ−ジフェネチル−１，３−（ビスアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’−トリフェネチル−１，３−（ビスアミノメチル）シクロヘキサンからなるポリアミン混合物Ｃ２を用いた。ポリアミン（Ｂ２）および（Ｃ）の混合物（Ｅ）は、ジェファーミンＤ−２０００およびポリアミン混合物Ｃ２との重量比５０：５０の組み合わせによって調整した。以上より調整された（Ｄ）と（Ｅ）のモル比を１：１にし、スタティックミキサーによって噴霧塗装し、ポリウレタン系樹脂硬化物を得た。得られた硬化物に関する物理的性質を表２に示す。
【００８０】
比較例４
プレポリマー（Ｄ）は実施例１と同様に調整した。脂肪族性ポリウレア樹脂のうち鎖長延長剤は、メタキシリレンジアミン（ＭＸＤＡ）と、アクリロニトリル（ＡＮ）とをモル比１：２、滴下温度１００℃でＡＮを７時間かけて滴下し、滴下後の反応温度は１２０℃、反応時間は５時間反応させることにより得られるポリアミン混合物Ｃ３を用いた。ポリアミン（Ｂ２）および鎖長延長剤の混合物（Ｅ）は、ジェファーミンＤ−２０００およびポリアミン混合物Ｃ３の重量比５０：５０の組み合わせによって調整した。以上より調整された（Ｄ）と（Ｅ）のモル比を１：１にし、スタティックミキサーによって噴霧混合塗装し、ポリウレタン系樹脂硬化物を得た。得られた硬化物に関する物理的性質を表２に示す。
【００８１】
比較例５
プレポリマー（Ｄ）は実施例２と同様に調整した。脂肪族性ポリウレア樹脂のうち鎖長延長剤は、１，３−（ビスアミノメチル）シクロヘキサン（１，３−ＢＡＣ）と、アクリロニトリル（ＡＮ）とをモル比１：２、滴下温度１１０℃でＡＮを１０時間かけて滴下し、滴下後の反応温度は１１０℃、反応時間は９時間反応させることにより得られるポリアミン混合物Ｃ４を用いた。ポリアミン（Ｂ）および鎖長延長剤の混合物（Ｅ）は、ジェファーミンＤ−２０００およびポリアミン混合物Ｃ３の重量比５０：５０の組み合わせによって調整した。以上より調整された（Ｄ）と（Ｅ）のモル比を１：１にし、スタティックミキサーによって噴霧混合塗装し、ポリウレタン系樹脂硬化物を得た。得られた硬化物に関する物理的性質を表２に示す。
【００８２】
【表２】

【００８３】
本発明（３）
実施例４
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いでメタキシリレンジアミン１モルに対し、触媒の存在下でスチレン１モルを付加反応させ、未反応メタキシリレンジアミンおよび触媒を除去した、Ｎ−フェネチル−メタキシリレンジアミン、Ｎ，Ｎ’−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ−ジフェネチル−メタキシリレンジアミン、Ｎ，Ｎ，Ｎ’−トリフェネチル−メタキシリレンジアミンからなるポリアミン混合物（ＭＸＤＡ−ＳＭ）６０．２部、メチルエチルケトン５１６．１部、イソプロパノール５１６．１部によりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂固形分濃度が３０％、粘度が６００ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布をゲルパーミエーションクロマトグラム（ＧＰＣ）［使用カラム（昭和電工製）：ＫＦ−８０１ １本、ＫＦ−８０２．５ １本、ＫＦ−８０４Ｌ ２本、ＫＦ−８０６Ｍ １本］にて測定を行った。結果を表３に示す。
なお表３の分子量分布におけるＭｗは重量平均分子量、Ｍｎは数平均分子量を示し、Ｍｗ／Ｍｎが小さいものほど、分子量分布がシャープであり、均一な樹脂硬化物であることがわかる。
【００８４】
得られたポリマー溶液をバインダーとして用い、次の処方にて印刷インキを調整した。
ポリウレタン系樹脂硬化物溶液 １００部
顔料（ルチル型酸化チタン） ５０部
メチルエチルケトン １５部
トルエン １５部
イソプロパノール ２０部
アルミナビーズ ２００部
上記の原料をそれぞれペントシェイカー（レッドデビル社製）にて４時間練肉し白色印刷インキを得て、バーコーダーＮｏ．４にて片面コロナ放電処理されたポリエチレン（ＰＥ：３０μｍ）、ポリプロピレン（ＰＰ：３０μｍ）、ポリエステル（ＰＥＴ：１００μｍ）、およびナイロン−６（ＮＹ：２５μｍ）の各フィルムの処理面に印刷を施し印刷物を得、乾燥した。乾燥条件は温度５０℃で３０秒加熱した後、温度２３℃湿度５０％で６０秒静置した。
得られた印刷物について次のような試験を行った。接着性、耐ブロッキング性の結果を表４に示す。
（１）接着性
印刷面にニチバンセロテープ（１８ｍｍ巾）を貼り、このセロテープの一端を印刷面に対して垂直方向に急速に引き剥がした時の印刷面の状態を観察した。
◎：極めて良好（剥離なし）
○：良好（０〜１０％剥離）
□：中程度（１０〜３０％剥離）
△：やや不良（３０〜５０％剥離）
×：不良（５０〜１００％剥離）
（２）耐ブロッキング性
印刷面と非印刷面（処理面または未処理面）を重ね合わせ、温度４０℃湿度６０％中で０．１ＭＰａの荷重をかけ、２４時間後それを剥がし表面状態を観察した。乾燥条件は温度５０℃で３０秒加熱した後、温度２３℃湿度５０％で６０秒静置した。
◎：全くブロッキングしていない
○：殆どブロッキングしていない
△：かなりブロッキングしている
×：著しくブロッキングしている
（３）耐熱性試験
上島製作所（株）のギアオーブンを用い、１２０℃の温度条件にて一定時間ごとに色差および光沢を測定した。色差測定、光沢度測定および数値算出はＪＩＳ−Ｚ８７３０およびＺ８７２２に準拠した。
乾燥条件はバインダー塗装後５０℃にて４時間乾燥後２３℃湿度５０％雰囲気下に１日静置後試験に供した。光沢度の結果を表５に、式差（ΔＥ）の結果を表６に式差（ＹＩ）の結果を表７に示す。
【００８５】
比較例６
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いでメタキシリレンジアミン１モルに対し、プロピレンオキシド１モルを付加反応させたポリアミン混合物（ＭＸＤＡ−ＰＯ）５４．４部、メチルエチルケトン５０９．４部、イソプロパノール５０９．４部によりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂硬化物固形分濃度が３０％、粘度が１２００ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布を実施例４と同様に測定を行った。結果を表３に示す。
得られたポリマー溶液を用い実施例４と同様に印刷インキを調整し、印刷物を得て、接着性、耐ブロッキング性の試験を行った。結果を表４に示す。実施例４と同様に印刷物の耐熱性試験を行った。結果を表５〜７に示す。
【００８６】
比較例７
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いでイソホロンジアミン（ＩＰＤＡ）３１．１部、ジ−Ｎ−ブチルアミン（ＤＢＡ）７．９部、メチルエチルケトン４９１．４部、イソプロパノール４９１．４部よりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂硬化物固形分濃度が３０％、粘度が６００ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布を実施例４と同様に測定を行った。結果を表３に示す。
得られたポリマー溶液を用い実施例４と同様に印刷インキを調整し、印刷物を得て、接着性、耐ブロッキング性の試験を行った。結果を表４に示す。実施例４と同様に印刷物の耐熱性試験を行った。結果を表５〜７に示す。
【００８７】
比較例８
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いでエチレンジアミン（ＥＤＡ）１１．０部、ジ−Ｎ−ブチルアミン（ＤＢＡ）７．９部、メチルエチルケトン４６８．０部、イソプロパノール４６８．０部よりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂硬化物固形分濃度が３０％、粘度が３５０ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布を実施例４と同様に測定を行った。結果を表３に示す。
得られたポリマー溶液を用い実施例４と同様に印刷インキを調整し、印刷物を得て、接着性、耐ブロッキング性の試験を行った。結果を表４に示す。実施例４と同様に印刷物の耐熱性試験を行った。結果を表５〜７に示す。
【００８８】
比較例９
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いでメタキシレンジアミン（ＭＸＤＡ）２４．９部、ジ−Ｎ−ブチルアミン（ＤＢＡ）７．９部、メチルエチルケトン４８４．２部、イソプロパノール４８４．２部よりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂固形分濃度が３０％、粘度が４００ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布を実施例４と同様に測定を行った。結果を表３に示す。
得られたポリマー溶液を用い実施例４と同様に印刷インキを調整し、印刷物を得て、接着性、耐ブロッキング性の試験を行った。結果を表４に示す。実施例４と同様に印刷物の耐熱性試験を行った。結果を表５〜７に示す。
【００８９】
比較例１０
撹拌機、温度計、還流冷却管およびドライ窒素ガス導入管を備えた４つ口フラスコに、重量平均分子量２０００のポリ（１，４−ブチレンアジペート）グリコールを４３５．１部とイソホロンジイソシアネートを１００部仕込み、窒素気流下に９０℃で２７時間反応させ、遊離イソシアネート含有２．８％のプレポリマーを製造後、メチルエチルケトン３５６．７部を加えウレタンプレポリマーの均一溶液とした。
次いで１，３−ビス（アミノメチル）シクロヘキサン（１，３−ＢＡＣ）２５．９部、ジ−Ｎ−ブチルアミン（ＤＢＡ）７．９部、メチルエチルケトン４８５．４部、イソプロパノール４８５．４部よりなる混合物を前記ウレタンプレポリマー溶液８９１．８部に添加し、５０℃で６時間反応させた。
得られたポリマー溶液は、樹脂固形分濃度が３０％、粘度が５００ｍＰａ・ｓ／２５℃であった。
ポリマーの分子量分布を実施例４と同様に測定を行った。結果を表３に示す。
得られたポリマー溶液を用い実施例４と同様に印刷インキを調整し、印刷物を得て、接着性、耐ブロッキング性の試験を行った。結果を表４に示す。実施例４と同様に印刷物の耐熱性試験を行った。結果を表５〜７に示す。
【００９０】
【表３】

【００９１】
【表４】

【００９２】
【表５】

【００９３】
【表６】

【００９４】
【表７】

【００９５】
【発明の効果】
以上の実施例から明らかなように、本発明のポリウレタン系樹脂組成物は、液流れ性、硬化性に優れ、反応射出成形法に特に好適で、さらに得られるポリウレタン系樹脂硬化物は引張伸び、引張強度等物性が特に優れ、種々の用途で有用である。
また、本発明のポリウレタン系樹脂組成物は適度の硬化速度を示し、装置が簡便なスタティックミキサー型スプレーガン等で噴霧混合塗装が可能であり、硬化物は優れた強度および可とう性を示し、塗料、成形体、皮膜、電子・電気部品、電子・電気絶縁材料等の用途で有用である。
さらに、本発明のポリウレタン系樹脂組成物から得られるポリマーからなる印刷インキバインダーを用いたインキは、被印刷物である各種プラスチックフィルムに対し、短い乾燥時間に優れた接着性を保持し、十分な耐ブロッキング性を有し、耐熱性も良好であり、印刷、塗料、およびコーティング等の広範な用途に対して、極めて有利に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyurethane, polyurethane urea and polyurea resin composition (hereinafter abbreviated as polyurethane resin composition) and a cured polyurethane resin obtained by curing them. Polyurethane resin compositions and cured products include foams (soft, semi-rigid, hard), elastomers (RIM (reaction injection molding), RRIM (reinforced reaction injection molding), casting, kneading, thermoplastic), paints, Furniture, bedding, automobile seats, products such as coatings, adhesives, binders, elastic fibers, leather (synthetic leather, artificial leather), flooring, waterproofing materials, athletic materials, sealants, caulking, medical materials, fiber treatment agents, etc. Seat back, sundries, cushioning material for automobiles, sound insulation, heat insulation, building materials, structural materials, interior and exterior of automobiles, automotive parts, shoe soles, industrial materials, sports, leisure, medical, shoes, metals, plastics, wood, inorganic materials -Used in a wide range of fields such as painting of rubber, paper, textiles, etc., textiles, textile industry, clothing, natural leather substitute applications, civil engineering / building materials, athletic, vehicles, etc.
[0002]
Among them, the relatively high-density polyurethane resin elastomer produced by the casting method, kneading method, thermoplastic method or reaction injection molding method has excellent physical properties, moldability and appearance, and is used in a wide range of fields. ing. Specific applications include a wide variety of applications, including automotive board materials, sports and leisure goods, housing for office equipment, furniture, agricultural equipment, and medical equipment.
[0003]
In addition, polyurethane-based cured resin for spray-mix coating for use in paints, flooring materials, sealants, road pavements, tank pavements, molded bodies, coatings, electronic / electric parts, electronic / electrical insulating materials, etc. It is obtained by spray molding on an object and hardening at high speed, and is useful because it has excellent wear resistance, mechanical strength, rebound resilience, and elasticity at low temperatures.
[0004]
Further, a printing ink binder obtained from a polyurethane resin composition is used because it has excellent adhesiveness, blocking resistance, and heat resistance to various plastic films.
[0005]
[Prior art]
It is known to form a non-foamed polyurethane resin, a fiber-reinforced elastomer, or a microcellular polyurethane elastomer by a reaction injection molding method by polyaddition of an isocyanate and an active hydrogen-containing compound. Raw materials for these polyurethane resin compositions include polyisocyanates, high-molecular-weight active hydrogen-containing compounds (polyether polyols, polyester polyols, polyether polyamines, etc.), chain extenders (alkane diols, aromatic polyamines, etc.), and And, if necessary, a catalyst, a foaming agent, a foam stabilizer, and an internal mold release agent.
[0006]
RIM is a method in which an isocyanate and an active hydrogen-containing compound are impact-mixed under pressure (often under high pressure) by an injection molding machine, the mixture is filled in a mold, cured, and then a molded article is taken out.
Among the above-mentioned raw materials, the chain extender is particularly important because it greatly affects the moldability and physical properties.
[0007]
As the chain extender, a low molecular weight alkanediol or a certain kind of aromatic polyamine is generally used, but none of them gives sufficient performance in terms of molding or physical properties. Specifically, when ethylene glycol is used, cell roughening, loose skin, pinholes, sink marks, burrs and the like are likely to occur, and the productivity is extremely low and unsatisfactory when industrially practiced.
[0008]
Since the above method has poor curability, there is a method of improving the curability using ethylene glycol and an aromatic polyamine in combination. For example, a method of improving curability by using a polyhedral mixed aromatic polyamine synthesized by condensation of aniline and formalin and ethylene glycol is disclosed (see Patent Document 1).
[0009]
On the other hand, as a method of using an aromatic amine as a main chain extender, for example, hydrogen at the ortho position to each amino group of the aromatic diamine is substituted with a straight-chain alkyl having 1 to 3 carbon atoms. A method has been disclosed in which the reactivity of an amino group is reduced due to the steric hindrance to improve the liquid flowability into a mold (see Patent Document 2).
[0010]
In the method using this kind of aromatic diamine, the demolding time and the curing time are shorter than those of ethylene glycol and 1,4-butanediol, and the material has excellent tensile properties. Products such as Faither use the diethyltoluenediamine (DETDA) shown in the examples of this patent.
However, this method has a problem that when a molded article having a high elastic modulus is manufactured, the molded article is fragile at the time of demolding and easily cracked.
[0011]
Further, as another method, for example, a method of using halogen-containing diaminobenzene having low reactivity as a chain extender is disclosed (see Patent Document 3). This method is too slow in curing and involves molding difficulties.
[0012]
When an aliphatic primary diamine is used as a chain extender other than the above, at least one amino group of the aliphatic primary diamine is substituted with an alkyl group or an aralkyl group in order to reduce the reactivity. A method has been disclosed in which the reactivity of amino groups is reduced to improve the liquid flowability into a mold by grading (see Patent Document 4). According to this method, the demolding time and the curing time are fast, and even when a molded article having a high elastic modulus is produced, the molded article is not fragile at the time of demolding and hardly cracks. However, a molded article obtained by this method has a drawback that physical properties such as tensile elongation and tensile strength are inferior.
[0013]
As a cured resin obtained by coating by spray mixing, a cured polyurethane resin for spray mixing coating is used. There is known a spray-mixed coating cured aromatic polyurea resin produced by reacting an aromatic isocyanate with an active hydrogen component in the presence of an aromatic chain extender. The aromatic isocyanate and the aromatic chain extender mean a compound in which a functional group such as an isocyanate group or an amino group is directly bonded to a carbon atom of an aromatic ring, The term "active compound" means not only the original aliphatic and alicyclic compounds, but also includes those containing an aromatic ring-containing isocyanate and an amine in which the above-mentioned functional group is bonded only to a carbon atom other than the aromatic ring.
[0014]
At present, one of the most widely used aromatic chain extenders is diethyltoluenediamine (DETDA). A cured polyurethane resin for spray-mix coating produced from this substance generally shows good processability, but cannot follow the expansion and contraction and flexibility of the base material to be coated because the resin is too hard. Therefore, there is an urgent need to develop a polyurethane resin cured product for spray mixing coating having good workability and high strength and flexibility.
[0015]
As a conventional technique, there has been disclosed a technique using an aliphatic primary diamine chain extender as a chain extender (see Patent Document 5). However, aliphatic primary diamines react rapidly with isocyanates and cause rapid polymerization, so that painting is impossible unless expensive equipment such as a collision mixing type is used.
[0016]
As the above-mentioned improvement technique, there has been disclosed a technique in which an amino group of a primary diamine is secondary-modified to control the reactivity (see Patent Documents 6 and 7).
The former is an aromatic primary diamine, and the latter is an aliphatic primary diamine in which the amino group is secondary-functionalized by a halide having an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms. An aromatic or aliphatic diamine is used as a chain extender. However, the alkylating agent is relatively expensive, and it is troublesome and costly to synthesize a secondary amine, such as using a neutralizing agent to recover the hydrogen halide produced by the reaction and removing the neutralizing agent.
[0017]
As the above improvement, those using a chain extender obtained by a Michael addition reaction of a primary diamine compound and a (meth) acrylic monomer are disclosed (Patent Documents 8, 9, 10, 11, 12). However, Patent Document 4 is used for printing ink or coating agent used for coating various plastic films, and Patent Documents 5 and 6 are used for reaction injection molding. Patent Documents 7 and 8 are used for spray-mixing coating. However, since the curing speed is high, workability is poor, and a cured polyurethane-based resin for spray-mixing coating having higher strength and flexibility is required. ing.
[0018]
In recent years, plastic films have been generally used as packaging materials, and accordingly, the demand for printing inks for plastic films has also increased. When a plastic film is used as a packaging material, printing is performed to decorate or protect the surface of the plastic film. Printing ink for such printing has adhesiveness and blocking resistance to these various plastic films. High performance such as good performance has been required. Moreover, in order to respond to high-speed printing, its high performance must be exhibited in a short drying time. In addition, with the advancement of packaging technology, higher performance than printing ink is required, and various post-processing appropriateness such as laminating process, boiling process, retort process, etc. are required. In addition, the heat resistance of the printing ink itself has become one of the most important performances.
[0019]
Conventionally, polymers obtained from polyurethane-based resin compositions are often used as printing ink binders required for such printing inks. In general, a printing ink using a polymer obtained from a polyurethane-based resin composition as a binder has excellent adhesion alone to polyester and polynylon films, but has insufficient adhesion to general-purpose polyethylene and polypropylene. Therefore, when printing on a polyethylene or polypropylene film, a two-pack reaction type ink in which a polyisocyanate compound is blended with polyurethane in order to supplement the adhesive strength is used. In addition, printing inks using a polymer obtained from a polyurethane resin composition having excellent adhesive strength alone to polyester and nylon films as a binder also have insufficient heat resistance required for various processing suitability. Liquid reactive inks are used.
[0020]
However, the two-component ink requires a curing agent to be added immediately before printing, which is inconvenient to handle, and has a good adhesion to various plastic films in terms of pot life (pot life). As a result of various researches and developments on polyurethanes which can be used as a binder for one-pack type ink which does not need to be blended with a polyisocyanate compound, the adhesiveness has been improved to some extent. However, obtaining good adhesion results in impairing the blocking resistance at the same time.
[0021]
For example, a method of increasing the adhesion to various plastic films using a modified chlorinated polypropylene having a specific polar group in the molecule (see Patent Documents 13, 14, and 15), as a dibasic acid component of polyester diol A method of increasing the adhesion to various plastic films using a long-chain dibasic acid (see Patent Document 16), and a method of increasing adhesion to various plastic films and low blocking resistance by using a low molecular triol as a polyol component For example, (see Patent Document 17), a method of increasing the adhesion to various plastic films using an alkylene oxide adduct of N, N-dialkylaminoalkylamine as a diol component (see Patent Document 18), chain lengthening Diol as an essential component and a mixture with a diamine component A method for increasing the adhesion to a stick film (see Patent Document 19), a method for increasing the adhesiveness of a compound having an aldehyde group as a chain extender to various plastic films (see Patent Document 20), a chain extender To increase the adhesive strength to various plastic films using long-chain alkylenediamines (see Patent Document 21), and various types using aromatic aliphatic diamines and alicyclic diamines to which alkylene oxide is added as a chain extender. A study to increase the adhesive strength to a plastic film (see Patent Document 22) and the like are disclosed.
Although these all use a special system to improve adhesion and blocking resistance, they have excellent adhesion in a short drying time, sufficient blocking resistance, and good It does not satisfy the heat resistance.
The alkylene oxide adduct is used as a diol component by reacting all active hydrogens of the amino group with an alkylene oxide, and is used at the time of prepolymer synthesis. It is used for a completely different purpose and method from the present invention used as an extension terminator (see Patent Document 18).
The problem of poor adhesion in conventional bonding results from the fact that in the production of a polymer obtained from a conventional polyurethane resin composition, the product is not uniform and contains many by-products such as low molecular weight compounds.
A polymer obtained from a conventional polyurethane resin composition is a general-purpose aliphatic diamine, an alicyclic diamine, an alkylene oxide adduct of an araliphatic diamine and / or an alkylene oxide adduct of an alicyclic diamine as a chain extender. Has been used, the reaction between the terminal isocyanate group in the isocyanate prepolymer and the amino group in the diamine is fast, control is difficult, and a polymer obtained from a uniform polyurethane-based resin composition cannot be obtained, Low molecular weight by-products result and the product is heterogeneous.
Therefore, when trying to increase the average molecular weight in order to obtain a binder for a gravure ink having good adhesiveness, the molecular weight distribution is inevitably high because the product is inevitably non-uniform and contains many by-products such as low molecular weight compounds. This has the further adverse effect of broadening the film and lowering the adhesiveness.
[0022]
[Patent Document 1]
JP-A-52-77200
[Patent Document 2]
Japanese Patent Publication No. 54-17359
[Patent Document 3]
JP-A-58-32626
[Patent Document 4]
Japanese Patent Publication No. 2-41310
[Patent Document 5]
JP-A-5-186560
[Patent Document 6]
JP-A 1-311116
[Patent Document 7]
JP-A-2-41310
[Patent Document 8]
JP-A-2-251515
[Patent Document 9]
JP-A-4-330044
[Patent Document 10]
JP-A-5-155974
[Patent Document 11]
JP-A-8-134162
[Patent Document 12]
JP-A-9-221534
[Patent Document 13]
JP-A-4-159377
[Patent Document 14]
JP-A-7-82337
[Patent Document 15]
JP-A-7-30278
[Patent Document 16]
JP-A-6-68088
[Patent Document 17]
JP-A-5-73154
[Patent Document 18]
JP-A-7-100771
[Patent Document 19]
JP-A-57-98577
[Patent Document 20]
JP-A-5-222331
[Patent Document 21]
JP-A-8-217849
[Patent Document 22]
JP-A-11-269422
[0023]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyurethane resin composition having excellent liquid flowability and curability, and suitable for a reaction injection molding method, wherein the cured product obtained has excellent physical properties such as tensile elongation and tensile strength. It is to provide things.
In addition, even with a static mixer type spray gun that shows an appropriate curing rate and a simple apparatus, by maintaining appropriate reactivity, spray mixing coating can be performed without curing in the mixer, and further excellent strength, Polyurethane resin cured product obtained by spray coating, which is flexible and has excellent processability, is obtained by spray coating for the purpose of using paints, molded products, coatings, electronic / electric parts, electronic / electric insulating materials, etc. To provide.
Furthermore, in view of the above situation of the printing ink binder, a polyurethane resin composition having excellent adhesiveness, blocking resistance and heat resistance to various plastic films such as polyester, nylon, polyethylene, and polypropylene as a printing material. A printing ink binder comprising a polymer obtained from the above.
[0024]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on chain extenders, and as a result, by using an amino compound obtained by adding styrene to an aliphatic polyamine, the liquid flowability and curability of the polyurethane resin composition are excellent, and the reaction injection molding is performed. The present invention was found to be excellent in physical properties such as tensile elongation and tensile strength, and the present invention has been achieved. The present inventors have also found out that the above problem can be solved by using an amino compound obtained by adding styrene to an aliphatic polyamine as a chain extender when obtaining a prepolymer, as a raw material of a cured polyurethane resin for spray mixing coating. Completed the invention. Furthermore, as a component in the printing ink binder, by using an amino compound obtained by adding styrene to an aliphatic polyamine as a chain extender, the reaction between the terminal isocyanate group in the prepolymer and the amino group in the diamine is controlled, The present inventors have found that the above-mentioned problems can be solved, and have completed the present invention.
[0025]
That is, the present invention relates to the following (1) to (3).
(1) In a polyurethane resin composition comprising a polyisocyanate (A), an active hydrogen-containing compound (B), and a chain extender (C), the chain extender is an amino compound obtained by adding styrene to an aliphatic polyamine. A polyurethane-based resin composition, and a cured polyurethane-based resin obtained by curing the same.
(2) The active hydrogen-containing compound (B) is a polyol (B1) and / or polyamine (B2) having a weight average molecular weight of 900 to 50,000, and is a polyisocyanate (A) and a prepolymer obtained from the active hydrogen-containing compound (B). The present invention (1) for spray mixing coating obtained by curing a polymer (D) and a mixture (E) of a polyamine (B2) having a weight average molecular weight of 900 to 50,000 and a chain extender (C) by spray mixing coating. ) A cured polyurethane resin.
(3) The polyurethane resin composition of the present invention (1), wherein the polyisocyanate (A) is a diisocyanate compound (A1) and the active hydrogen-containing compound (B) is a polyol (B3) having a weight average molecular weight of 500 to 6000. A polymer for a printing ink binder having a weight average molecular weight of 5,000 to 500,000 obtained by the reaction.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
The aliphatic polyamine used in the present invention (1) may contain an aromatic hydrocarbon group at another position in the molecule, except that the amino group is bonded to an aromatic carbon atom. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, polyoxypropylenediamine, polyoxypropylenetriamine, mensendiamine, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, N-aminomethylpiperazine, norbornanediamine, metaxylylenediamine, paraxylylenediamine and the like. Can be These may be used alone or in combination of two or more. Among them, preferred are xylylenediamines such as meta-xylylenediamine and para-xylylenediamine, and 4-bis (amino) such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane. Methyl) cyclohexane, and particularly preferred are metaxylylenediamine and 1,3-bis (aminomethyl) cyclohexane.
[0027]
Examples of the amino compound obtained by adding styrene to the aliphatic polyamine used as the chain extender (C) in the present invention (1) include, for example, N-phenethyl-ethylenediamine, N-phenethyl-diethylenetriamine, N-phenethyl-triethylene Tetramine, N-phenethyl-tetraethylenepentamine, N-phenethyl-pentaethylenehexamine, N-phenethyl-hexamethylenediamine, N-phenethyl-polyoxypropylenediamine, N-phenethyl-polyoxypropylenetriamine, N-phenethyl-men Senediamine, N-phenethyl-isophoronediamine, N-phenethyl-1,3-bis (aminomethyl) cyclohexane, N-phenethyl-diaminodicyclohexylmethane, N-phenethyl-bis (4-amino-3-meth Lecyclohexyl) methane, N-phenethyl-N-aminomethylpiperazine, N-phenethyl-norbornanediamine, N-phenethyl-metaxylylenediamine, N-phenethyl-paraxylylenediamine, N, N′-diphenethyl-ethylenediamine, N , N'-diphenethyl-diethylenetriamine, N, N'-diphenethyl-triethylenetetramine, N, N'-diphenethyl-tetraethylenepentamine, N, N'-diphenethyl-pentaethylenehexamine, N, N'-diphenethyl-hexamine Methylenediamine, N, N'-diphenethyl-polyoxypropylenediamine, N, N'-diphenethyl-polyoxypropylenetriamine, N, N'-diphenethyl-mensendiamine, N, N'-diphenethyl-isophoronediamine, N'-di Phenethyl-1,3-bis (aminomethyl) cyclohexane, N, N′-diphenethyl-diaminodicyclohexylmethane, N, N′-diphenethyl-bis (4-amino-3-methylcyclohexyl) methane, N, N′-diphenethyl —N-aminomethylpiperazine, N, N′-diphenethyl-norbornanediamine, N, N′-diphenethyl-metaxylylenediamine, N, N′-diphenethyl-paraxylylenediamine and the like. These may be used alone or in combination of two or more. Among them, particularly preferred are N-phenethyl-metaxylylenediamine, N, N'-diphenethyl-metaxylylenediamine, N-phenethyl-1,3-bis (aminomethyl) cyclohexane, N, N'-diphenethyl -1,3-bis (aminomethyl) cyclohexane.
[0028]
The amino compound obtained by adding styrene to the aliphatic polyamine used as the chain extender (C) in the present invention (1) can be produced by a known method (see JP-A-2002-161076).
[0029]
In the present invention (1), the amino compound obtained by adding styrene to the aliphatic polyamine used as the chain extender (C) may optionally be used in combination with an aromatic polyamine. -Diaminotoluene, 2,6-diaminotoluene, paraphenylenediamine, metaphenylenediamine, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 3-isopropyl-2 , 6-Diaminotoluene, 5-isopropyl-2,4-diaminotoluene, 5-tert-butyl-2,4-diaminotoluene, 4,4'-methylene-bis (2,6-diethylaniline), 4,4 '-Methylene-bis (2,6-diisopropylaniline), 4,4'-methylene-bis (2-ethylaniline), 3,4'-diamine Nodiphenyl-1,1'-ethane, pyrylenediamine, 5,7-diamino-1,1-dimethylindane, 4,6-diamino-1,1-dimethylindane, 4,7-diamino-1,1-dimethyl And indane, 5,7-diamino-1,1,4,6-tetramethylindan. These may be used alone or in combination of two or more.
[0030]
The mixing weight ratio of the amino compound obtained by adding styrene to the aliphatic polyamine and the aromatic polyamine is 5:95 to 100: 0, more preferably 50:50 to 100: 0. In the above range, the liquid flow property, the curability, and the mechanical properties are particularly excellent.
[0031]
The polyisocyanate (A) used in the present invention (1) is, for example, 4,4'-diphenylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, polymethylene polyphenyl polyisocyanate, xylylene diisocyanate , 1,3- (bisisocyanate) methylcyclohexane, isophorone diisocyanate, and dimers, trimers, carbodiimide-modified, allophanate-modified, buret-modified, and prepolymers of these isocyanates. These may be used alone or in combination of two or more.
[0032]
Particularly preferred polyisocyanate (A) is a modified 4,4'-diphenylmethane diisocyanate which is liquid at ordinary temperature. Specific examples of the compound include a urethane group-containing polyisocyanate obtained by reacting 4,4′-diphenylmethane diisocyanate with a low molecular weight diol or triol (preferably polypropylene glycol having a weight average molecular weight of less than 700), or carbodiimide. 4,4'-diphenylmethane diisocyanate-based polyisocyanate having a uretonimine group and / or a mixture of 2,4'- and 4,4'-diphenylmethane diisocyanate and a small amount of diphenylmethane-based trifunctional or higher polyisocyanate, etc. is there.
[0033]
In the present invention (1), the active hydrogen-containing compound (B) preferably used is an active hydrogen-containing compound having a practical weight average molecular weight of 1,000 to 18,000, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, or the like. Ethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3,6-hexanetriol, pentaerythritol, polyhydric alcohols such as sorbitol, or diethanolamine, alkanolamines such as triethanolamine, or ethylenediamine, Amines containing two or more active hydrogens such as diethylenetriamine, ammonia, aniline, tolylenediamine, xylylenediamine, diaminodiphenylmethane, etc. De, butylene oxide, polyether polyol obtained by the alkylene oxide to addition polymerization such as styrene oxide, or include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.
[0034]
Further, a polymer polyol obtained by graft-reacting an ethylenically unsaturated compound such as styrene, acrylonitrile, or methyl methacrylate to the above-mentioned polyol, 1,2- or 1,4-polybutadiene polyol, or a hydrogenated product thereof can also be used.
[0035]
Further, a polyester polyol obtained by reacting a polycarboxylic acid with a low molecular weight polyol, a polyester polyol obtained by ring-opening polymerization of caprolactone, and a polycarbonate polyol can also be used.
[0036]
Further, for example, a primary or secondary amine obtained by aminating a hydroxyl group of the above polyether polyol, specifically, a polyether polyol obtained by addition polymerization of propylene oxide to glycerin is reacted with ammonia in the presence of a catalyst. Alternatively, there is a high molecular weight polyether polyamine obtained by reacting with a monoalkylamine. Further, a polyether polyamine obtained by chemically bonding a high molecular weight polyether and an aromatic amine may be used.
These may be used alone or in combination of two or more.
[0037]
In carrying out the present invention (1), the amount of each raw material used is such that the equivalent ratio of the active hydrogen-containing compound (B) to the isocyanate groups contained in the polyisocyanate (A) is 0.8 to 1.3. Adjust
[0038]
The mixing weight ratio of the active hydrogen-containing compound (B) and the chain extender (C) is from 10:90 to 90:10, preferably from 30:70 to 70:30. In the above range, the liquid flow property, the curability, and the mechanical properties are particularly excellent.
[0039]
In addition to the above-mentioned raw materials, auxiliary agents include a catalyst, a foaming agent, a foam stabilizer, and an internal mold release agent. These are usually used by dispersing them in a component containing a high-molecular-weight active hydrogen-containing compound, but they can also be used by dispersing them in only a component containing a polyisocyanate compound or in both components.
[0040]
Examples of the catalyst include organometallic catalysts such as dibutyltin diacetate, dibutyltin dilaurate, tin oleate and tin octoate, and triethylamine, N, N, N ′, N′-tetramethylpropanediamine, 1,4-diazabicyclo [ 2.2.2] There are amine catalysts such as octane and pentamethyldiethylenetriamine.
[0041]
Examples of the foaming agent include trichlorofluoromethane, trichlorotrifluoroethane, methylene chloride, acetone, ethyl acetate, methanol, ethanol, water, nitrogen gas, carbon dioxide gas and the like. Examples of the foam stabilizer include an organic silane compound.
[0042]
As the internal release agent, a silicon-based chemical or the like is used. As the filler, glass fiber, carbon fiber, synthetic fiber, mineral fiber, flake glass, alumina, clay, mica, talc, inorganic compound whisker and the like are used.
[0043]
Other auxiliary agents include fillers, pigments, antioxidants, plasticizers, viscosity modifiers, flame retardants, colorants, stabilizers, surfactants, germicides, and the like.
[0044]
Examples of the polyisocyanate (A) used as a raw material of the prepolymer (D) used in the present invention (2) include the same polyisocyanates used in the present invention (1). They may be used alone or in combination of two or more. Of these, xylylene diisocyanate and 1,3- (bisisocyanate) methylcyclohexane are most preferred.
[0045]
Examples of the polyol (B1) and the polyamine (B2) having a weight average molecular weight of 900 to 50,000, which are raw materials of the prepolymer (D) of the present invention (2), for example, ethylene glycol, propylene glycol as an initiator, Polyvalent alcohols such as diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3,6-hexanetriol, pentaerythritol and sorbitol, or Alkanolamines such as diethanolamine, diethanolamine and triethanolamine, or amines containing two or more active hydrogens such as ethylenediamine, diethylenetriamine, ammonia, aniline, tolylenediamine, xylylenediamine, diaminodiphenylmethane, and ethylene. Oxide, propylene oxide Polyether polyols obtained by addition polymerization of alkylene oxides such as sulfide, butylene oxide and styrene oxide, or polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran, or styrene, acrylonitrile , A polymer polyol obtained by graft reaction of an ethylenically unsaturated compound such as methyl methacrylate, and 1,2- or 1,4-polybutadiene polyol or a hydrogenated product thereof, or a polycarboxylic acid and a low molecular weight polyol And a polyester polyol obtained by ring-opening polymerization of caprolactone, a polycarbonate polyol, or, for example, obtained by aminating the OH group of the above polyether polyol. High-molecular-weight polyether polyamines obtained by reacting a polyether polyol obtained by addition polymerization of propylene oxide with glycerin with ammonia or a monoalkylamine in the presence of a catalyst. There is. In addition, at least one kind of polyether polyamine obtained by chemically bonding a high molecular weight polyether and an aromatic amine can be used. However, in view of water resistance and storage stability, polyoxypolyamine can be used. Alkylene polyamines are most preferred.
[0046]
Examples of the polyoxyalkylene polyamine include polyoxyalkylene polyamines represented by the following general formulas (1), (2), and (3).
[0047]
Embedded image

[0048]
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[0049]
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[0050]
The weight average molecular weight of the polyoxyalkylene polyamine is 900 to 50,000. If the molecular weight of the polyoxyalkylene polyamine used is less than the above range of the weight average molecular weight, the elongation performance will be extremely lowered. On the other hand, if the molecular weight of the polyoxyalkylene polyamine exceeds the range of the above-mentioned weight average molecular weight, the viscosity of the polyamine increases, resulting in deterioration of coating workability and decrease in strength of the polyurea resin.
[0051]
Specific examples of the polyoxypolyamine component include:
{Circle around (1)} Polyoxypropylenediamine having an average degree of polymerization n of 33 and a weight average molecular weight of 2,000 represented by the formula (1) (manufactured by Huntsman Corporation, trade name: Jeffamine D-2000)
{Circle around (2)} Polyoxypropylenediamine having an average degree of polymerization n of 68 and a weight-average molecular weight of 4000 shown in the formula (1) (manufactured by Huntsman Corporation, trade name: Jeffamine D-4000)
{Circle around (3)} Polyoxypropyleneoxyethylenediamine having an average polymerization degree A + C = 2.5 and B = 40.5 and having a weight average molecular weight of 2,000 represented by the formula (2) (manufactured by Huntsman Corporation, trade name: Jeffamine ED-2000)
(4) Polyoxypropylene glycerin triamine represented by the formula (3) having a weight average molecular weight of 3000 (manufactured by Huntsman Corporation, trade name: Jeffamine T-3000)
(5) Polyoxypropylene glycerin triamine represented by the formula (3) having a weight average molecular weight of 5000 (manufactured by Huntsman Corporation, trade name: Jeffamine T-5000)
[0052]
The prepolymer (D) obtained from the polyisocyanate (A) and the polyol (B1) having a weight average molecular weight of 900 to 50,000 and / or the polyamine (B2) in the present invention (2) is produced by the following method. Can be done.
The equivalent ratio of the hydroxyl group and / or the amino group contained in the polyol (B1) and / or the polyamine (B2) to the isocyanate group contained in the polyisocyanate (A) is 0.01 to 0.7, preferably 0.1 to 0.7. 05 to 0.5.
Within the above range, the viscosity of the prepolymer is favorable for spray-mixing coating, and the flexibility and elongation performance at low temperatures of the produced resin composition are particularly good.
[0053]
The reaction is carried out by dropping the polyol (B1) and / or the polyamine (B2) into the polyisocyanate (A). The method of batch charging and dropping the polyisocyanate (A) to the polyol (B1) and / or the polyamine (B2) does not function as the prepolymer (D) used in the present invention.
[0054]
The amino compound obtained by adding styrene to the aliphatic polyamine which is the chain extender (C) in the present invention (2) is the same as the amino compound obtained by adding styrene to the aliphatic polyamine in the present invention (1). Can be Examples of the aliphatic polyamine include the same as the aliphatic polyamine in the present invention (1). They may be used alone or in combination of two or more. Of these, meta-xylylenediamine and 1,3-bis (aminomethyl) cyclohexane are particularly preferred. The amino compound obtained by adding styrene to the aliphatic polyamine may be used alone or in combination of two or more. Among them, particularly preferred are N-phenethyl-metaxylylenediamine, N, N′-diphenethyl-metaxylylenediamine, N, N-diphenethyl-metaxylylenediamine, N-phenethyl-bis (1,3- Aminomethyl) cyclohexane, N, N'-diphenethyl-bis (1,3-aminomethyl) cyclohexane and N, N-diphenethyl-bis (1,3-aminomethyl) cyclohexane.
[0055]
The amino compound obtained by adding styrene to the aliphatic polyamine which is the chain extender (C) in the present invention (2) may be used together with the aromatic polyamine in some cases, and can be used in the present invention (1). The same as the aromatic polyamine can be used. They may be used alone or in combination of two or more.
The mixing weight ratio of the amino compound obtained by adding styrene to the aliphatic polyamine and the aromatic polyamine is 5:95 to 100: 0, more preferably 50:50 to 100: 0. Within the above range, strength and flexibility are particularly excellent.
[0056]
The mixing weight ratio of the polyamine (B2) and the chain extender (C) constituting the mixture (E) is 10:90 to 90:10, preferably 30:70 to 70:30. Within the above range, strength and flexibility are particularly excellent.
[0057]
The method of mixing the polyamine (B2) and the chain extender (C) constituting the mixture (E) may be a known method, and is a method of batch charging and dropping the chain extender (C) to the polyamine (B2). Or a method of dropping the polyamine (B2) into the chain extender (C). Although the mixing temperature is not particularly limited, it is preferably 0 to 100 ° C, more preferably 20 to 80 ° C, from the viewpoint of workability.
[0058]
The equivalent ratio of the amino group of the polyamine (B2) and the chain extender (C) to the isocyanate group in the prepolymer (D) is 0.5 to 3.0, preferably 0.9 to 2.0.
In the above range, the tensile strength and the tear strength are particularly excellent.
A catalyst may be added to the above reaction, but advantageously, the prepolymer (D) and the mixture (E) react without using a catalyst to form the resin system of the present invention.
[0059]
The polyurethane resin composition for spray mixing and coating in the present invention (2) does not require a large-scale and expensive apparatus using a large-sized high-pressure spraying apparatus which is a collision mixing type, and is a cheaper and simpler static mixer mixing type. Is effective. In this system, the prepolymer (D) and the mixture (E) of the polyurethane resin composition for spray mixing coating are mixed intimately in a static mixer by a small compressor in a static mixer, and directly applied to a desired base material. You can do it.
[0060]
The constituent components of the polymer for a printing ink binder obtained from the polyurethane resin composition as the main component of the present invention (3) are as follows.
[0061]
Examples of the diisocyanate compound (A1) which is a component of the polyurethane resin composition include aromatic, aliphatic, araliphatic and alicyclic diisocyanates. For example, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, methyl Typical examples are cyclohexane diisocyanate and dimer diisocyanate. I can give it.
[0062]
Examples of the polyol (B3) having a weight average molecular weight of 500 to 6000 include polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran; ethylene glycol, 1,2-propanediol, and 1,3. -Propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, diethylene glycol , Triethylene glycol, dipropylene glycol and other known saturated and unsaturated low molecular weight glycols, or alkyl glycidyl ethers such as N-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, versatile Monocarboxylic acid glycidyl esters such as glycidyl ester, dimer diol obtained by reducing dimer acid, and adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid Polyester polyols obtained by dehydrating and condensing dibasic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or their corresponding acid anhydrides or dimer acids; ring-opening polymerization of cyclic ester compounds And other known polyols generally used in the production of polyurethanes, such as polyester polyols obtained by the addition of other polyols such as polycarbonate polyols, polybutadiene glycols, and glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A. .
The weight average molecular weight of the above-mentioned various polyols is appropriately determined in consideration of the compatibility, drying properties, blocking resistance, and the like of the obtained polyurethane resin, and is generally desirably in the range of 500 to 6,000. If the weight average molecular weight is less than 500, the printability tends to be inferior due to the decrease in solubility, while if it exceeds 6000, drying properties and blocking resistance tend to decrease.
[0063]
In the present invention (3), an amino compound obtained by adding styrene to an aliphatic polyamine is used as a chain extender (C) constituting a polyurethane resin composition. Specifically, the same amino compounds as those obtained by adding styrene to the aliphatic polyamine used in the present invention (1) can be mentioned.
[0064]
In the present invention (3), the terminal terminator is used as needed when preparing a polymer having a desired molecular weight, but the following compounds can be used in combination with the above. Specific examples of the compound used for the chain terminator include monohydric alcohols such as methyl alcohol, ethyl alcohol, N-propyl alcohol, isopropyl alcohol, N-butyl alcohol, and isobutyl alcohol; monoethylamine, N-propylamine, and diethylamine. And monoamines such as di-N-propylamine and di-N-butylamine; and alkanolamines such as monoethanolamine and diethanolamine.
[0065]
In the method for producing a polymer for a printing ink binder obtained from the polyurethane resin composition of the present invention (3), for example, the polyol (B3) and the diisocyanate compound (A1) are reacted at an isocyanate group excess molar ratio, A prepolymer method comprising preparing a prepolymer having isocyanate groups at both ends thereof, diluting with a solvent, and then increasing the molecular weight with a chain extender; or a polyol (B3), a diisocyanate compound (A1) and a chain extender ( C) can be carried out by a one-shot method or the like in which the components are reacted at once, but the former is preferred for the purpose of obtaining a uniform polymer solution. In the above prepolymer method, the order of addition of the components during the prepolymerization reaction of the terminal isocyanate groups is not particularly limited, and all the components are sequentially or simultaneously mixed, or if necessary, during the prepolymerization reaction. Various methods conventionally used in this field, such as re-adding the diisocyanate compound (A1), can be employed as appropriate.
[0066]
In producing the prepolymer, the ratio of the number of hydroxyl groups in the polyol (B3) to the number of isocyanate groups is preferably from 1.1 to 3.0. When this ratio is smaller than 1.1, heat resistance and clothing strength are reduced, and when it is larger than 3.0, the adhesiveness to various plastic films is reduced.
In producing the polymer, the number of amino groups of the chain extender (C) is 0.8 to 1.3 equivalents, preferably 0.9 to 1.2 equivalents, per equivalent of the isocyanate group of the prepolymer. is there. When the amino group of the chain extender (C) is smaller than 0.8 equivalent, drying property, blocking resistance and film strength are not sufficient, and the amino group of the chain extender (C) is larger than 1.3 equivalent. In this case, the chain extender (C) remains unreacted, and the odor tends to remain on the printed matter.
The equivalent ratio of the chain extender (C) to the monoalcohol or monoamine in the terminator is in the range of 0.5 to 50. If the corresponding ratio is less than 0.5, the chemical resistance is reduced, and if it is more than 50, the molecular weight is increased, the resin viscosity is increased, and the workability is reduced. The terminating agent may be completed before the chain extension reaction, added simultaneously with the chain extension agent (C), or added after the chain extension reaction to complete the reaction.
[0067]
Examples of the solvent used for producing the polymer solution include alcohols such as methanol, ethanol, isopropanol and N-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as dioxane and tetrahydrofuran; Aliphatic hydrocarbons such as xane and cyclohexane; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; non-hydrocarbons such as dimethylsulfoxide, N-methyl-2-virolidone and dimethylformamide Protic polar solvents and mixtures of two or more thereof.
[0068]
A catalyst can be used for this reaction. Examples of the catalyst that promotes the urethanization reaction include tertiary amine catalysts such as triethylamine and dimethylaniline, and organometallic catalysts such as organotin and organozinc.
[0069]
The polymer of the present invention (3) thus obtained has a weight average molecular weight of 5,000 to 500,000, preferably 10,000 to 300,000. If the weight average molecular weight is less than 5,000, the drying properties, blocking resistance and oil resistance of printing inks and coating films using this as a binder will be poor. On the other hand, when the weight average molecular weight exceeds 500,000, the viscosity of the polymer solution is so high that handling becomes difficult, and the resulting printing ink and coating film have low gloss and poor resolubility.
The resin solid content (polymer) concentration in the polymer solution obtained by the present invention (3) can be set widely by appropriately adjusting the amount of the solvent to be used in consideration of workability in the application. It is 15 to 60% by weight, and the viscosity of the solution is preferably 50 to 100000 mPa · s for practical use.
[0070]
The printing ink binder using the polymer of the present invention (3) is preferably applied to polyester, nylon, polyethylene, polypropylene films and the like.
The printing ink binder using the polymer of the present invention (3) can be used in the same manner as the conventional ink binder. That is, a printing ink can be obtained by adding a pigment, a pigment dispersant, a surfactant, a wax, other additives, and the like to the binder of the present invention and kneading the resulting mixture using an ordinary ink manufacturing apparatus such as a ball mill.
[0071]
If necessary, a resin compatible with the resin can be used as an auxiliary component. For example, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyolefin such as chlorinated ethylene polypropylene, chlorsulfonated polyolefin, nitrified cotton, ethylene vinyl acetate copolymer or its chlorinated product, chlorsulfonated product, maleic acid resin, polyvinyl chloride Resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, polyester resin, polyamide resin, polycarbonate resin, phenol resin, alkyd resin, polyurethane resin and the like.
[0072]
Since the printing ink binder using the polymer of the present invention (3) is excellent in adhesiveness and heat resistance, it is extremely used as a coating resin and a coating agent for decoration and surface protection of various synthetic resin molded products. Useful. The same effect can be obtained when the printing ink binder of the present invention is used not only as an organic solvent but also as an anionic, cationic or nonionic aqueous resin.
[0073]
The present invention (3) is a process for preparing a conventional polyurethane resin composition by using an aliphatic polyamine in which at least one of the amino groups is secondaryized by a phenethyl group as the chain extender in the polyurethane resin composition. While the resulting polymer was not homogeneous and contained many by-products such as low molecular weight compounds, which caused the problem of poor adhesion. It has excellent adhesiveness to this.
[0074]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
[0075]
The present invention (1)
The following raw materials were used in Examples and Comparative Examples.
Polyether A: polyoxypropylene triamine (Huntsman Corporation), which is a polyether triamine obtained by reacting a triol having a weight average molecular weight of about 5000 obtained by addition polymerization of glycerin with propylene oxide with ammonia in the presence of a catalyst. (Manufactured by Jeffamine T-5000)
Polyisocyanate: Isocyanate group content of 22.5% obtained by reacting 4,4′-diphenylmethane diisocyanate (Nippon Polyurethane Industry Co., Ltd.) with tripropylene glycol (Asahi Denka Kogyo Co., Ltd., polyether P2000) Isocyanate prepolymer.
Amine A: meta-xylylenediamine is subjected to an addition reaction with styrene in the presence of a catalyst to remove unreacted meta-xylylenediamine and the catalyst, N-phenethyl-met-xylylenediamine, N, N'-diphenethyl-met-xylylene A polyamine mixture consisting of a diamine, N, N-diphenethyl-metaxylylenediamine, and N, N, N'-triphenethyl-metaxylylenediamine.
Amine B: N-tert-butyl-α, α, α ′, α obtained by reacting α, α, α ′, α′-tetramethyl-metaxylylenediamine with tert-butyl chloride in a dioxane solvent '-Tetramethyl-metaxylylenediamine.
DETDA: a mixture of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene at a weight ratio of 80:20 (EthACurE100, manufactured by Albemarle Co.).
B-712: a wax-based external release agent for RIM manufactured by Chukyo Yushi Co., Ltd.
[0076]
Example 1 and Comparative Examples 1 to 3
Molding was performed using the raw material formulations shown in Table 1 as Examples and Comparative Examples.
As the reaction injection molding machine, NR-230 manufactured by Toho Machinery Co., Ltd. and LRM-15M manufactured by Cincinnati Milacron Co., Ltd. were used. The liquid temperature of the amine mixture and the polyisocyanate were adjusted to 20 ° C. and 40 ° C., respectively, and nitrogen gas was dissolved in the amine mixture to 40 vol% (value in the atmosphere). The mixing ratio of the raw materials was adjusted so as to be the amount shown in Table 1, and the injection speed was injected into the mold at the speed shown in Table 1. The mold was heated to 75 ° C. on a flat plate of 500 mm × 400 mm × 3.0 mm, coated with an external release agent, and then thoroughly wiped with a dry cloth.
The mold was released 30 seconds after the injection, and the releasability and curability were compared. As for the curability, immediately after the mold release, the sheet molded product was placed on a horizontal table, and after 1 minute, 20 cm was projected from the front end of the sheet, and the height of the sag from the horizontal plane was measured. . At the same time, to see the brittleness immediately after molding, it was examined whether the sheet was bent and cracked. The surface condition of the molded article was also examined.
For physical properties, a test piece was cut from a molded product, heated in an oven at 120 ° C. for 1 hour, and then measured for tensile strength and tensile elongation.
Table 1 shows the results.
[0077]
[Table 1]

[0078]
The present invention (2)
In these, (parts) and (%) are based on weight.
{Circle around (1)} Jeffamine D-2000 is a polyoxypropylenediamine having a weight average molecular weight of about 2,000.
{Circle around (2)} The test pieces and physical property test methods conformed to JIS K6301.
Example 2
Metaxylylene diisocyanate (MXDI) and Jeffamine D-2000 were added at an equivalent ratio of 11: 1 and the dropping temperature was set to 25 ° C., and Jeffamine D-2000 was added dropwise over 7 hours. The reaction temperature after the dropping was the same as the dropping temperature, and the reaction time was 1 hour to prepare the prepolymer (D). Among the aliphatic polyurea resins, the chain extender (C) is an N-phenethyl-meta by removing an unreacted metaxylylenediamine and a catalyst by subjecting metaxylylenediamine to an addition reaction with styrene in the presence of a catalyst. A polyamine mixture C1 consisting of xylylenediamine, N, N'-diphenethyl-metaxylylenediamine, N, N-diphenethyl-metaxylylenediamine, N, N, N'-triphenethyl-metaxylylenediamine was used. The mixture (E) of the polyamines (B2) and (C) was prepared by a combination of Jeffamine D-2000 and the polyamine mixture C1 in a weight ratio of 50:50. The molar ratio of (D) and (E) adjusted as described above was set to 1: 1 and spray-mixed and coated with a static mixer to obtain a cured polyurethane resin. Table 2 shows the physical properties of the obtained cured product.
[0079]
Example 3
1,3- (bisisocyanate) methylcyclohexane (1,3-BIC) and Jeffamine D-2000 were added at an equivalent ratio of 11: 1 and the dropping temperature was set to 25 ° C., and Jeffamine D-2000 was added dropwise over 7 hours. The reaction temperature after dropping was the same as the dropping temperature, and the reaction time was 1 hour to prepare the prepolymer (D). Among the aliphatic polyurea resins, the chain extender (C) is obtained by subjecting 1,3- (bisaminomethyl) cyclohexane to an addition reaction with styrene in the presence of a catalyst to form unreacted 1,3- (bisaminomethyl) N-phenethyl-1,3- (bisaminomethyl) cyclohexane, N, N′-diphenethyl-1,3- (bisaminomethyl) cyclohexane, N, N-diphenethyl-1,3-, from which cyclohexane and catalyst were removed. A polyamine mixture C2 consisting of (bisaminomethyl) cyclohexane and N, N, N'-triphenethyl-1,3- (bisaminomethyl) cyclohexane was used. The mixture (E) of the polyamines (B2) and (C) was prepared by a combination of Jeffamine D-2000 and the polyamine mixture C2 in a weight ratio of 50:50. The molar ratio of (D) and (E) adjusted as described above was set to 1: 1 and spray coating was performed with a static mixer to obtain a cured polyurethane resin. Table 2 shows the physical properties of the obtained cured product.
[0080]
Comparative Example 4
The prepolymer (D) was prepared in the same manner as in Example 1. Among the aliphatic polyurea resins, as the chain extender, metaxylylenediamine (MXDA) and acrylonitrile (AN) were added dropwise at a molar ratio of 1: 2, AN at a dropping temperature of 100 ° C. over 7 hours, and after dropping. The reaction temperature was 120 ° C., and the reaction time was 5 hours. A polyamine mixture C3 obtained by reacting was used. The mixture of polyamine (B2) and chain extender (E) was prepared by a combination of Jeffamine D-2000 and polyamine mixture C3 in a weight ratio of 50:50. The molar ratio of (D) and (E) adjusted as described above was set to 1: 1 and spray-mixed and coated with a static mixer to obtain a cured polyurethane resin. Table 2 shows the physical properties of the obtained cured product.
[0081]
Comparative Example 5
The prepolymer (D) was prepared in the same manner as in Example 2. Among the aliphatic polyurea resins, the chain extender used was a mixture of 1,3- (bisaminomethyl) cyclohexane (1,3-BAC) and acrylonitrile (AN) at a molar ratio of 1: 2 and AN at a dropping temperature of 110 ° C. Was added dropwise over 10 hours, the reaction temperature after the addition was 110 ° C., and the reaction time was 9 hours, and a polyamine mixture C4 obtained by reacting was used. The mixture of polyamine (B) and chain extender (E) was prepared by a combination of Jeffamine D-2000 and polyamine mixture C3 in a weight ratio of 50:50. The molar ratio of (D) and (E) adjusted as described above was set to 1: 1 and spray-mixed and coated with a static mixer to obtain a cured polyurethane resin. Table 2 shows the physical properties of the obtained cured product.
[0082]
[Table 2]

[0083]
The present invention (3)
Example 4
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Next, 1 mole of styrene was added to 1 mole of metaxylylenediamine in the presence of a catalyst to remove unreacted metaxylylenediamine and the catalyst. N-phenethyl-metaxylylenediamine, N, N'-diphenethyl 60.2 parts of a polyamine mixture (MXDA-SM) comprising meta-xylylenediamine, N, N-diphenethyl-metaxylylenediamine, N, N, N'-triphenethyl-metaxylylenediamine, 516.1 parts of methyl ethyl ketone And a mixture consisting of 516.1 parts of isopropanol was added to 891.8 parts of the urethane prepolymer solution and reacted at 50 ° C. for 6 hours.
The obtained polymer solution had a resin solid content of 30% and a viscosity of 600 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was determined by gel permeation chromatography (GPC) [columns used (Showa Denko): one KF-801, one KF-802.5, two KF-804L, one KF-806M]. A measurement was made. Table 3 shows the results.
Mw in the molecular weight distribution in Table 3 indicates a weight average molecular weight, and Mn indicates a number average molecular weight. It can be seen that the smaller the Mw / Mn, the sharper the molecular weight distribution and the uniform resin cured product.
[0084]
Using the obtained polymer solution as a binder, a printing ink was prepared according to the following formulation.
100 parts of polyurethane resin cured product solution
50 parts of pigment (rutile type titanium oxide)
15 parts of methyl ethyl ketone
15 parts of toluene
20 parts of isopropanol
Alumina beads 200 parts
Each of the above-mentioned raw materials was kneaded with a pent shaker (manufactured by Red Devil Co., Ltd.) for 4 hours to obtain a white printing ink. Printing is performed on the treated surface of each film of polyethylene (PE: 30 μm), polypropylene (PP: 30 μm), polyester (PET: 100 μm), and nylon-6 (NY: 25 μm) that have been subjected to corona discharge treatment on one side at 4. And dried. The drying conditions were heating at a temperature of 50 ° C. for 30 seconds and then standing at a temperature of 23 ° C. and humidity of 50% for 60 seconds.
The following test was performed on the obtained printed matter. Table 4 shows the results of the adhesion and the blocking resistance.
(1) Adhesiveness
A Nichiban cello tape (18 mm width) was adhered to the printing surface, and the state of the printing surface when one end of the cello tape was rapidly peeled off in a direction perpendicular to the printing surface was observed.
：: extremely good (no peeling)
：: good (0 to 10% peeling)
□: Medium (10-30% peeling)
Δ: Slightly poor (30 to 50% peeling)
×: Poor (50-100% peeling)
(2) Blocking resistance
The printed surface and the non-printed surface (treated surface or untreated surface) were overlapped, a load of 0.1 MPa was applied at a temperature of 40 ° C. and a humidity of 60%, and after 24 hours, it was peeled off and the surface condition was observed. The drying conditions were heating at a temperature of 50 ° C. for 30 seconds and then standing at a temperature of 23 ° C. and humidity of 50% for 60 seconds.
◎: Not blocking at all
：: Almost no blocking
△: fairly blocking
×: remarkably blocking
(3) Heat resistance test
Using a gear oven manufactured by Ueshima Seisakusho Co., Ltd., the color difference and gloss were measured at regular time intervals at a temperature of 120 ° C. The color difference measurement, gloss measurement, and numerical calculation were based on JIS-Z8730 and Z8722.
Drying conditions were as follows: after coating the binder, drying at 50 ° C. for 4 hours, leaving it at 23 ° C. in a 50% humidity atmosphere for one day, and then subjecting it to the test. Table 5 shows the results of glossiness, Table 6 shows the results of equation difference (ΔE), and Table 7 shows the results of equation difference (YI).
[0085]
Comparative Example 6
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Then, a mixture comprising 54.4 parts of a polyamine mixture (MXDA-PO), 509.4 parts of methyl ethyl ketone, and 509.4 parts of isopropanol was reacted with 1 mol of m-xylylenediamine and 1 mol of propylene oxide. The solution was added to 891.8 parts of the solution and reacted at 50 ° C. for 6 hours.
The obtained polymer solution had a resin solid content concentration of 30% and a viscosity of 1200 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was measured in the same manner as in Example 4. Table 3 shows the results.
Using the obtained polymer solution, a printing ink was prepared in the same manner as in Example 4, a printed product was obtained, and tests for adhesion and blocking resistance were performed. Table 4 shows the results. A heat resistance test of the printed matter was performed in the same manner as in Example 4. The results are shown in Tables 5 to 7.
[0086]
Comparative Example 7
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Next, a mixture of 31.1 parts of isophoronediamine (IPDA), 7.9 parts of di-N-butylamine (DBA), 491.4 parts of methyl ethyl ketone, and 491.4 parts of isopropanol was added to 891.8 parts of the urethane prepolymer solution. Then, the reaction was carried out at 50 ° C. for 6 hours.
The obtained polymer solution had a resin cured product solid content concentration of 30% and a viscosity of 600 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was measured in the same manner as in Example 4. Table 3 shows the results.
Using the obtained polymer solution, a printing ink was prepared in the same manner as in Example 4 to obtain a printed product, and the adhesion and the blocking resistance were tested. Table 4 shows the results. A heat resistance test of the printed matter was performed in the same manner as in Example 4. The results are shown in Tables 5 to 7.
[0087]
Comparative Example 8
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Next, a mixture consisting of 11.0 parts of ethylenediamine (EDA), 7.9 parts of di-N-butylamine (DBA), 468.0 parts of methyl ethyl ketone and 468.0 parts of isopropanol was added to 891.8 parts of the urethane prepolymer solution. At 50 ° C. for 6 hours.
The obtained polymer solution had a resin solid content concentration of 30% and a viscosity of 350 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was measured in the same manner as in Example 4. Table 3 shows the results.
Using the obtained polymer solution, a printing ink was prepared in the same manner as in Example 4 to obtain a printed product, and the adhesion and the blocking resistance were tested. Table 4 shows the results. A heat resistance test of the printed matter was performed in the same manner as in Example 4. The results are shown in Tables 5 to 7.
[0088]
Comparative Example 9
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Next, a mixture consisting of 24.9 parts of metaxylenediamine (MXDA), 7.9 parts of di-N-butylamine (DBA), 484.2 parts of methyl ethyl ketone, and 484.2 parts of isopropanol was added to 891.8 parts of the urethane prepolymer solution. The mixture was added and reacted at 50 ° C. for 6 hours.
The obtained polymer solution had a resin solid content concentration of 30% and a viscosity of 400 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was measured in the same manner as in Example 4. Table 3 shows the results.
Using the obtained polymer solution, a printing ink was prepared in the same manner as in Example 4 to obtain a printed product, and the adhesion and the blocking resistance were tested. Table 4 shows the results. A heat resistance test of the printed matter was performed in the same manner as in Example 4. The results are shown in Tables 5 to 7.
[0089]
Comparative Example 10
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and dry nitrogen gas inlet tube, 435.1 parts of poly (1,4-butylene adipate) glycol having a weight average molecular weight of 2000 and 100 parts of isophorone diisocyanate After charging and reacting at 90 ° C. for 27 hours under a nitrogen stream to produce a 2.8% prepolymer containing free isocyanate, 356.7 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer solution.
Next, a mixture consisting of 25.9 parts of 1,3-bis (aminomethyl) cyclohexane (1,3-BAC), 7.9 parts of di-N-butylamine (DBA), 485.4 parts of methyl ethyl ketone, and 485.4 parts of isopropanol. Was added to 891.8 parts of the urethane prepolymer solution and reacted at 50 ° C. for 6 hours.
The obtained polymer solution had a resin solid content of 30% and a viscosity of 500 mPa · s / 25 ° C.
The molecular weight distribution of the polymer was measured in the same manner as in Example 4. Table 3 shows the results.
Using the obtained polymer solution, a printing ink was prepared in the same manner as in Example 4 to obtain a printed product, and the adhesion and the blocking resistance were tested. Table 4 shows the results. A heat resistance test of the printed matter was performed in the same manner as in Example 4. The results are shown in Tables 5 to 7.
[0090]
[Table 3]

[0091]
[Table 4]

[0092]
[Table 5]

[0093]
[Table 6]

[0094]
[Table 7]

[0095]
【The invention's effect】
As is clear from the above examples, the polyurethane resin composition of the present invention is excellent in liquid flowability and curability, and is particularly suitable for the reaction injection molding method. It has particularly good physical properties such as tensile strength and is useful in various applications.
In addition, the polyurethane resin composition of the present invention exhibits an appropriate curing rate, and can be spray-mixed and coated with a simple mixer such as a static mixer type spray gun, and the cured product exhibits excellent strength and flexibility, It is useful in applications such as paints, molded articles, films, electronic and electrical parts, and electronic and electrical insulating materials.
Furthermore, the ink using the printing ink binder composed of the polymer obtained from the polyurethane resin composition of the present invention maintains excellent adhesiveness to various plastic films to be printed in a short drying time and has a sufficient resistance. It has blocking properties and good heat resistance, and can be used very advantageously for a wide range of applications such as printing, paints, and coatings.

Claims (5)

In a polyurethane resin composition comprising a polyisocyanate (A), an active hydrogen-containing compound (B), and a chain extender (C), the chain extender (C) is an amino compound obtained by adding styrene to an aliphatic polyamine. What is claimed is: 1. A polyurethane resin composition, comprising: A cured polyurethane resin obtained by curing the polyurethane resin composition according to claim 1. The polyurethane resin composition according to claim 1, wherein the aliphatic polyamine is xylylenediamine and / or bis (aminomethyl) cyclohexane. The active hydrogen-containing compound (B) is a polyol (B1) and / or polyamine (B2) having a weight average molecular weight of 900 to 50,000, and is a polyisocyanate (A) and a prepolymer (D) obtained from the active hydrogen-containing compound (B). The polyurethane system according to claim 2, which is obtained by curing a mixture (E) of a polyamine (B2) having a weight average molecular weight of 900 to 50,000 and a chain extender (C) by spray mixing coating. Resin cured product. The polyisocyanate (A) is a diisocyanate compound (A1), and the active hydrogen-containing compound (B) is a polyol (B3) having a weight average molecular weight of 500 to 6000, which is obtained by reacting the polyurethane resin composition according to claim 1. Of a printing ink binder having a weight average molecular weight of 5,000 to 500,000.