JP3633970B2 - Water-based polyurethane resin - Google Patents
Water-based polyurethane resin Download PDFInfo
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【０００１】
【産業上の利用分野】
本発明は水性ポリウレタン樹脂に関するものであり、更に詳しくは低温領域でのより柔軟でかつ、エラスティクな水性ポリウレタン樹脂に関する。本発明において水性とは、水分散性および水溶性の総称である。
【０００２】
【従来の技術】
近年、公害、環境汚染等の観点より従来の有機溶剤系樹脂に代わって水性樹脂に対する関心が高まってきているが、その中でも水性ポリウレタン樹脂はその優れた機械的性質から人工皮革、繊維用処理剤、あるいは接着剤として幅広い分野で使用されている。
従来ポリオール成分としてポリテトラメチレンエーテルグリコールを用いる水性ポリウレタン樹脂は比較的温度依存性の少ない優れたゴム弾性を有し、さらに耐加水分解性にも優れた樹脂であることは知られている。
【０００３】
【発明が解決しようとする課題】
しかし、この樹脂においてもフィルム物性では温度低下に伴って、伸び率の低下、応力の上昇が確認され、柔軟性が失われてしまい低温時における物性変化の大きいことがしばしば指摘されその改善が要望されていた。
【０００４】
【課題を解決するための手段】
本発明者等はポリテトラメチレンエーテルグリコールを成分とする水性ポリウレタンの優位性を損なわずかつ低温時における物性変化の少ない水性ポリウレタン樹脂の検討を行ったところ、以下に示す水性ポリウレタン樹脂により改善されることを見い出した。
【０００５】
すなわち、本発明は、−ＣＨ２ＣＨ（Ｒ１）ＣＨ（Ｒ２）ＣＨ２Ｏ−基（Ｒ１、Ｒ２はどちらか一方が水素でもう一方がメチル基である。）で表される基（化１）と、−ＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−で表される基（化２）から構成され、（化１）の比率が５〜３０重量％であるランダム共重合ポリオール（Ａ）と、少なくとも１個のカルボキシル基と少なくとも２個の水酸基を有する親水性付与物質（数平均分子量９０〜３０００）（Ｂ）と、ポリイソシアネート化合物（Ｃ）を、（Ｃ）成分のイソシアネート当量／（Ａ）成分＋（Ｂ）成分のヒドロキシル当量比１ ． １〜２ ． ５の範囲で反応させて、分子中にカルボキシル基が０ ． ２〜２ ． ０重量％の範囲で導入された両末端イソシアネートウレタンプレポリマーとし、カルボキシル基と逆のイオン性を有する化合物が溶解された水溶液中に入れ、中和反応で親水性塩を形成させ、水中に安定的に分散させて得られたポリウレタン水分散物であり、また前記したポリウレタン水分散物の製造方法である。
【０００６】
本発明に用いる水性ポリウレタン樹脂を構成する（Ａ）成分であるポリオール化合物は、ーＣＨ２ＣＨ（Ｒ１）ＣＨ（Ｒ２）ＣＨ２Ｏ−（Ｒ１、Ｒ２はどちらか一方が水素で、もう一方がメチル基である）で表される基（化１）と、ーＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−で表される基（化２）から構成されており、これらの構成単位の重合様式はランダム共重合である。
このようなポリオール（Ａ）は例えば、テトラヒドロフラン（以下ＴＨＦ）と３ーメチルテトラヒドロフランとのモル比８５／１５ないし２０／８０の混合物をＴＨＦを開環しうる強酸、例えばクロロスルホン酸、フロロスルホン酸、過塩素酸などにより、通常０℃〜５０℃の温度で共重合して得られるランダム共重合ポリエーテルジヒドロキシ化合物である。
このポリエーテルＡの使用できる分子量は６００〜５０００で、好ましくは １５００〜３５００である。
ポリエーテルＡの分子量が６００より小さいと得られた水性ポリウレタン樹脂がゴム弾性に乏しい樹脂になり、分子量が５０００より大きいとウレタン化反応の際の粘度上昇が激しく、作業性を著しく悪化させる。
（化１）で表されるーＣＨ２ＣＨ（Ｒ１）ＣＨ（Ｒ２）ＣＨ２Ｏ−基は、３ーメチルテトラヒドロフラン（以下３メチルＴＨＦ）によって与えられる基で本発明に用いるポリオール（Ａ）中に５〜３０重量％含まれている。
【０００７】
本発明に用いる、少なくとも１個のカルボキシル基（生成するポリウレタン化合物を乳化するための基）と少なくとも２個の水酸基を有する親水性付与物質（Ｂ）は、例えば２、２ージメチロールプロピオン酸、トリメチロールプロパン又はグリセリン等と開始剤としてエチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド等のモノマーが付加重合した３官能ポリオール類とイソフタル酸、マレイン酸等の環状酸無水物とがモル比１：１で開環による付加反応して得られるその分子中に少なくとも１個のカルボキシル基と少なくとも２個の水酸基を有する半エステル化合物（数平均分子量９０〜３０００）が挙げられる。
【０００８】
本発明に使用するポリイソシアネート化合物（Ｃ）は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，４，４−’ジフェニルメタンジイソシアネート，１、３ーキシリレンジイソシアネート，１、４ーキシリレンジイソシアネート，１，４−テトラメチレンジイソシアネート，１，６−ヘキサメチレンジイソシアネート，１，３，５ートリメチルヘキサメチ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’ージメチルー３、３’ージフェニルジイソシアネート，１、５ーナフタレンジイソシアネート、ｐ−フェニレンジイソシアネート、ｍ−フェニレンジイソシアネート等の周知のイソシアネート類であり、これらの２種以上が混合された系てあっても差し支えない。
【０００９】
本発明にかかる水性ポリウレタン樹脂は先ず（Ａ）成分のポリオールと（Ｃ）成分のポリイソシネート化合物を（Ｃ）のイソシアネート当量／（Ａ）のヒドロキシル当量比が１．０〜４．７の範囲で反応させて、両末端イソシアネートウレタンプレポリマーを製造し、次いで（Ｂ）成分である少なくとも１個のカルボキシル基と少なくとも２個の水酸基を有する親水性付与物質との反応によって鎖延長され、分子中にカルボキシル基が導入された両末端イソシアネートのプレポリマーを構成するがその構成比率は（Ｃ）のイソシアネート当量／（Ａ）＋（Ｂ）のヒドロキシル当量比が１．１〜２．５の範囲であり且つプレポリマー中のカルボキシル基含有率が０．２〜２．０重量％の範囲となるよう調製される。（Ｃ）のイソシアネート当量／（Ａ）＋（Ｂ）のヒドロキシル当量比が１．１より小さいと耐熱性が悪くなり、２．５を超えると熱溶融性が悪くなり目的を達成できない。また、プレポリマー中の親水基含有率が０．２より少ないと、親水性に乏しく乳化分散せず、２．０を越えると著しく耐水性が悪くなる。
【００１０】
ワンシヨット法の場合は、（Ｃ）のイソシアネート当量／（（Ａ）成分のポリオール＋（Ｂ）成分のヒドロキシル）当量比が１．１〜２．５の範囲で反応させて分子中にカルボキシル基が導入された両末端イソシアネートウレタンプレポリマーを構成する。
【００１１】
これらのウレタン化反応は有機溶剤の存在下或いは無溶媒下何れによっても製造され、更に少量の反応触媒例えば有機スズ系や第三アミン類等の存在下または無触媒下でも製造されるウレタン化反応である。
【００１２】
こうして得られたカルボキシル基が導入されたウレタンプレポリマーをアルカリ金属、アルカリ土類金属または有機塩基等のカルボキシル基と逆のイオン性を有する化合物が溶解された水溶液中に入れ、中和反応で親水性塩を形成させ、高分子量体として水中に安定的に分散させて水性ポリウレタン樹脂が製造される。ここで言う有機塩基としては第三および第四アミン化合物類を使用することができる。またその際に生じるカルボン酸塩基としてはーＣＯＯＨ，ーＣＯＯＮａ，ーＣＯＯＮＨ４等があげられる。
【００１３】
【実施例】
以下 実施例を挙げて更に詳細に説明する。
ーＣＨ２ＣＨ（Ｒ１）ＣＨ（Ｒ２）ＣＨ２Ｏ−（Ｒ１、Ｒ２は前記定義の通り）で表される基と、ーＣＨ２ＣＨ２ＣＨ２ＣＨ２Ｏ−で表される基から構成されているポリオール（Ａ）をＰＴＧ−Ｌと略す。
ＰＴＧ−Ｌ２０００：保土谷化学工業社製，平均分子量が２０００、 ーＣＨ２ＣＨ（Ｒ１）ＣＨ（Ｒ２）ＣＨ２Ｏ−基を１５重量％含有
コロネートＴ−８０：日本ポリウレタン社製、２、４と２、６の異性対が８：２のトリレンジイソシアネート
［実施例１］
温度計，攪拌装置，乾燥管付き冷却管を取り付けた四つ口フラスコに水酸基価５６．１のＰＴＧ−Ｌ２０００を３９６重量部を仕込み、コロネートＴ−８０を７０重量部を加え系内の温度８５℃で、３．５時間反応させ、活性イソシアネート３．６８重量％を含むウレタンプレポリマーが得られた。その後８５℃を保ちながら、水酸基価４０２．８のトリオールと無水マレイン酸の等モル反応から得られた水酸基価が２１５．６の半エステル化合物を３５重量部加え、４時間反応し活性イソシアネートが２．３１重量％を含有する分子中にカルボキシル基が導入された分子両末端イソシアネートのウレタンプレポリマーが得られた。
こうして得られたウレタンプレポリマーの４００重量部を３５７重量部の水に水酸化ナトリウム２重量部を溶解した温度４０℃水中にホモジナイザーを使用して５分間強制分散させ、次に３００ｒｐｍの速度で回転する攪拌羽根をセットした容器に移し、温度７０℃に保ちながら１時間の鎖延長反応を行った。この反応は分子末端のイソシアネートが水と反応する脱炭酸反応である。
こうして得られたポリウレタン水分散物の固形分は５３％であり、水素イオン指数（ＰＨ）が７．１であり、粘度６００ｃｐｓ／２０℃の分散安定性に優れたエマルジョンであった。
【００１４】
［比較例１］
温度計，攪拌装置，乾燥管付き冷却管を取り付けた四つ口フラスコに水酸基価５６．１のＰＴＧ２０００を３９６重量部を仕込み、コロネートＴ−８０を７０重量部を加え系内の温度８５℃で、３．５時間反応させ活性イソシアネート３．６８重量％を含むウレタンプレポリマーが得られた。その後８５℃を保ちながら水酸基価４０２．８のトリオールと無水マレイン酸の等モル反応から得られた水酸基価が２１５．６の半エステル化合物を３５重量部加え、４時間反応し活性イソシアネートが２．３１重量％を含有する分子中にカルボキシル基が導入された分子両末端イソシアネートのウレタンプレポリマーが得られた。
こうして得られたウレタンプレポリマーの４００重量部を３５７重量部の水に水酸化ナトリウム２重量部を溶解した温度４０℃水中にホモジナイザーを使用して５分間強制分散させ、次に３００ｒｐｍの速度で回転する攪拌羽根をセットした容器に移し、温度７０℃に保ちながら１時間の鎖延長反応を行った。この反応は分子末端のイソシアネートが水と反応する脱炭酸反応である。
こうして得られたポリウレタン水分散物お固形分は５３％であり、水素イオン指数（ＰＨ）が７．１であり、粘度６９０ｃｐｓ／２０℃の分散安定性に優れたエマルジョンであった。
【００１５】
試験体の製造
実施例並びに比較例で得られた水性ポリウレタンエマルジョンとＢ−２０（保土谷化学工業社製、耐水性向上剤）及び水を１００：１：９９の比率で配合し数分間攪拌した。その後、予め水平に固定した２０ｃｍ×３０ｃｍ×０．２ｃｍのガラス型枠に配合液の４５ｇを流し込み、２０℃の恒温室で４８時間の自然乾燥を行い厚さ０．１５±０．０５ｍｍのフィルムを得た。次いでガラスの型枠からフィルムを取り外し、１１０℃のオーブン中で２時間乾燥した後３号ダンベルで型抜きした。その後１０５℃のオーブンで１時間乾燥し、デシケーター中で放令して試験体とした。
【００１６】
引張り強度
上述のようにして得られた試験体を２０℃並びにー２０℃に設定された引張り試験機用恒温槽の中に１５分間放置後、設定温度下で引張り試験を行った。引張試験はＪＩＳ Ｋ６３０１に準じ（株）オリエンテック製万能引張り試験機（テンシロン・ＵＴＭ−ＩＩＩ ）を使用した。
結果を表１および図１に示す。
【００１７】
【表１】
【発明の効果】
このように本発明によって従来の水性ポリウレタン樹脂では成し得なかった低温領域でのより柔軟でかつエラスティックな水性ポリウレタン樹脂の提供を可能とした。
【００１９】
【図面の簡単な説明】
【図１】図１に表１の物性値をｓｔｒｅｓｓ−ｓｔｒａｉｎ曲線で示した。[0001]
[Industrial application fields]
The present invention relates to an aqueous polyurethane resin, and more particularly to an aqueous polyurethane resin that is more flexible and elastic in a low temperature region. In the present invention, “aqueous” is a generic term for water dispersibility and water solubility.
[0002]
[Prior art]
In recent years, interest in water-based resins has been increasing in place of conventional organic solvent-based resins from the viewpoints of pollution, environmental pollution, etc. Among them, water-based polyurethane resins are treating agents for artificial leather and fibers because of their excellent mechanical properties. Or, it is used in a wide range of fields as an adhesive.
Conventionally, it is known that an aqueous polyurethane resin using polytetramethylene ether glycol as a polyol component has excellent rubber elasticity with relatively little temperature dependency and is also excellent in hydrolysis resistance.
[0003]
[Problems to be solved by the invention]
However, even in this resin, the film physical properties are confirmed to decrease in elongation and stress as the temperature decreases, and the flexibility is lost, and it is often pointed out that the physical properties change greatly at low temperatures. It had been.
[0004]
[Means for Solving the Problems]
The present inventors have examined water-based polyurethane resins that do not impair the superiority of water-based polyurethanes containing polytetramethylene ether glycol as components and have little change in physical properties at low temperatures, and are improved by the following water-based polyurethane resins. I found out.
[0005]
That is, the present invention relates to a group represented by a —CH 2 CH (R 1) CH (R 2) CH 2 O— group (one of R 1 and R 2 is hydrogen and the other is a methyl group). And a random copolymer polyol (A) composed of a group represented by —CH 2 CH 2 CH 2 CH 2 O— (Chemical Formula 2), wherein the ratio of (Chemical Formula 1) is 5 to 30% by weight; Hydrophilic substance (number average molecular weight 90 to 3000) (B) having at least one carboxyl group and at least two hydroxyl groups, and polyisocyanate compound (C) , isocyanate equivalent of component (C) / (A) Component + (B) component hydroxyl equivalent ratio 1 . 1-2 . 5 reaction, the carboxyl group in the molecule is 0 . 2-2 . Saturated urethane urethane prepolymer introduced in the range of 0% by weight is placed in an aqueous solution in which a compound having ionicity opposite to the carboxyl group is dissolved, and a hydrophilic salt is formed by a neutralization reaction, which is stable in water. This is a polyurethane water dispersion obtained by mechanically dispersing and a method for producing the polyurethane water dispersion described above.
[0006]
The polyol compound that is the component (A) constituting the aqueous polyurethane resin used in the present invention is —CH 2 CH (R 1 ) CH (R 2 ) CH 2 O— (R 1 , R 2 is either hydrogen. The other is a methyl group) and a group represented by —CH 2 CH 2 CH 2 CH 2 O— (Chemical 2), and these structural units The polymerization mode is random copolymerization.
Such a polyol (A) is, for example, a strong acid capable of ring-opening THF, such as a mixture of tetrahydrofuran (hereinafter referred to as THF) and 3-methyltetrahydrofuran in a molar ratio of 85/15 to 20/80, such as chlorosulfonic acid or fluorosulfonic acid. , A random copolymerized polyether dihydroxy compound obtained by copolymerization with perchloric acid at a temperature of usually 0 ° C. to 50 ° C.
The molecular weight that can be used for the polyether A is 600 to 5000, preferably 1500 to 3500.
When the molecular weight of the polyether A is smaller than 600, the obtained aqueous polyurethane resin becomes a resin having poor rubber elasticity, and when the molecular weight is larger than 5,000, the viscosity is greatly increased during the urethanization reaction, and workability is remarkably deteriorated.
The —CH 2 CH (R 1 ) CH (R 2 ) CH 2 O— group represented by (Chemical Formula 1 ) is a group given by 3-methyltetrahydrofuran (hereinafter 3 methyl THF) and is used in the present invention for the polyol (A) 5 to 30% by weight is contained.
[0007]
The hydrophilicity-imparting substance (B) having at least one carboxyl group (group for emulsifying the resulting polyurethane compound) and at least two hydroxyl groups used in the present invention is, for example, 2,2-dimethylolpropionic acid, Trifunctional polyols obtained by addition polymerization of monomers such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide as initiators and cyclic acid anhydrides such as isophthalic acid and maleic acid have a molar ratio of 1: 1. And a half-ester compound (number average molecular weight of 90 to 3000) having at least one carboxyl group and at least two hydroxyl groups in the molecule obtained by addition reaction by ring opening.
[0008]
The polyisocyanate compound (C) used in the present invention is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-'diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diene. Isocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3,5-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dimethyl-3,3'-diphenyl diisocyanate, 1,5-naphthalene Known isocyanates such as diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and the like, and a system in which two or more of these are mixed may be used.
[0009]
In the aqueous polyurethane resin according to the present invention, first, the polyol (A) and the polyisocyanate compound (C) are reacted in the range of isocyanate equivalent (C) / hydroxyl equivalent ratio (A) of 1.0 to 4.7. To produce a chain-terminated isocyanate urethane prepolymer, which is then chain-extended by the reaction of at least one carboxyl group as component (B) and a hydrophilicity-imparting substance having at least two hydroxyl groups, Constituting a prepolymer of both end-isocyanates into which groups have been introduced, the proportion of which is (C) isocyanate equivalent weight / (A) + (B) hydroxyl equivalent ratio in the range of 1.1 to 2.5 and It is prepared so that the carboxyl group content in the prepolymer is in the range of 0.2 to 2.0% by weight. If the isocyanate equivalent ratio of (C) / (A) + (B) hydroxyl equivalent ratio is less than 1.1, the heat resistance will be poor, and if it exceeds 2.5, the heat meltability will be poor and the purpose cannot be achieved. Further, when the hydrophilic group content in the prepolymer is less than 0.2, the hydrophilicity is poor and emulsification does not occur, and when it exceeds 2.0, the water resistance is remarkably deteriorated.
[0010]
In the case of the one-shoulder method, the carboxyl group is reacted in the molecule by reacting the isocyanate equivalent of (C) / (polyol of component (A) + hydroxyl of component (B)) equivalent ratio of 1.1 to 2.5. It constitutes the introduced both-end isocyanate urethane prepolymer.
[0011]
These urethanization reactions can be produced either in the presence or absence of organic solvents, and also in the presence or absence of small amounts of reaction catalysts such as organotins and tertiary amines. It is.
[0012]
The urethane prepolymer introduced with the carboxyl group thus obtained is placed in an aqueous solution in which a compound having an ionicity opposite to that of the carboxyl group such as an alkali metal, alkaline earth metal or organic base is dissolved, and is neutralized by a neutralization reaction. An aqueous polyurethane resin is produced by forming a functional salt and stably dispersing it in water as a high molecular weight product. Tertiary and quaternary amine compounds can be used as the organic base here. Examples of the carboxylate group generated at that time include —COOH, —COONa, —COONH 4 and the like.
[0013]
【Example】
Examples will be described in more detail below.
A group represented by —CH 2 CH (R 1 ) CH (R 2 ) CH 2 O— (where R 1 and R 2 are as defined above), and —CH 2 CH 2 CH 2 CH 2 O—. The polyol (A) composed of a group is abbreviated as PTG-L.
PTG-L2000: manufactured by Hodogaya Chemical Co., Ltd., average molecular weight of 2000, containing 15% by weight of —CH 2 CH (R 1 ) CH (R 2 ) CH 2 O— group Coronate T-80: manufactured by Nippon Polyurethane Co., Ltd. 2 Tolylene diisocyanate having an isomeric pair of 4, 2 and 6 of 8: 2 [Example 1]
A four-necked flask equipped with a thermometer, a stirrer, and a cooling tube with a drying tube was charged with 396 parts by weight of PTG-L2000 having a hydroxyl value of 56.1, 70 parts by weight of Coronate T-80, and a temperature of 85 in the system. The reaction was carried out at 3.5 ° C. for 3.5 hours to obtain a urethane prepolymer containing 3.68% by weight of active isocyanate. Thereafter, while maintaining the temperature at 85 ° C., 35 parts by weight of a half ester compound having a hydroxyl value of 215.6 obtained from an equimolar reaction of a hydroxyl group having a hydroxyl value of 402.8 and maleic anhydride was added, and reacted for 4 hours. A urethane prepolymer of a molecularly terminal isocyanate in which a carboxyl group was introduced into the molecule containing .31% by weight was obtained.
400 parts by weight of the urethane prepolymer thus obtained was forcibly dispersed for 5 minutes in water at a temperature of 40 ° C. in which 2 parts by weight of sodium hydroxide was dissolved in 357 parts by weight of water, and then rotated at a speed of 300 rpm. The mixture was transferred to a container equipped with stirring blades, and a chain extension reaction was performed for 1 hour while maintaining the temperature at 70 ° C. This reaction is a decarboxylation reaction in which the isocyanate at the molecular end reacts with water.
The polyurethane water dispersion thus obtained had an solid content of 53%, a hydrogen ion index (PH) of 7.1, and an emulsion having a viscosity of 600 cps / 20 ° C. and excellent dispersion stability.
[0014]
[Comparative Example 1]
A four-necked flask equipped with a thermometer, a stirrer, and a cooling tube with a drying tube was charged with 396 parts by weight of PTG2000 having a hydroxyl value of 56.1, and 70 parts by weight of Coronate T-80 was added. And a urethane prepolymer containing 3.68% by weight of active isocyanate was obtained by reacting for 3.5 hours. Thereafter, 35 parts by weight of a half ester compound having a hydroxyl value of 215.6 obtained from an equimolar reaction of a triol having a hydroxyl value of 402.8 and maleic anhydride was added while maintaining the temperature at 85 ° C., and the reaction was carried out for 4 hours. A urethane prepolymer of molecular end-isocyanate having a carboxyl group introduced into the molecule containing 31% by weight was obtained.
400 parts by weight of the urethane prepolymer thus obtained was forcibly dispersed for 5 minutes in water at a temperature of 40 ° C. in which 2 parts by weight of sodium hydroxide was dissolved in 357 parts by weight of water, and then rotated at a speed of 300 rpm. The mixture was transferred to a container equipped with stirring blades, and a chain extension reaction was performed for 1 hour while maintaining the temperature at 70 ° C. This reaction is a decarboxylation reaction in which the isocyanate at the molecular end reacts with water.
The polyurethane water dispersion thus obtained had an solid content of 53%, a hydrogen ion index (PH) of 7.1, and a viscosity of 690 cps / 20 ° C. with excellent dispersion stability.
[0015]
The aqueous polyurethane emulsion obtained in the test example and comparative example of the test body, B-20 (manufactured by Hodogaya Chemical Co., Ltd., water resistance improver) and water were blended at a ratio of 100: 1: 99 and stirred for several minutes. . Then, 45 g of the blended solution is poured into a 20 cm × 30 cm × 0.2 cm glass mold fixed horizontally in advance, and is naturally dried for 48 hours in a constant temperature room at 20 ° C., and a film having a thickness of 0.15 ± 0.05 mm Got. Next, the film was removed from the glass mold, dried in an oven at 110 ° C. for 2 hours, and then punched with a No. 3 dumbbell. Thereafter, it was dried in an oven at 105 ° C. for 1 hour and released in a desiccator to obtain a test specimen.
[0016]
Tensile strength The specimen obtained as described above was left in a thermostat for a tensile tester set at 20 ° C. and −20 ° C. for 15 minutes, and then a tensile test was performed at a set temperature. The tensile test was performed according to JIS K6301 using an orientec universal tensile tester (Tensilon / UTM-III).
The results are shown in Table 1 and FIG.
[0017]
[Table 1]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a more flexible and elastic water-based polyurethane resin in a low temperature region, which could not be achieved with a conventional water-based polyurethane resin.
[0019]
[Brief description of the drawings]
FIG. 1 shows physical property values shown in Table 1 as stress-strain curves.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25968394A JP3633970B2 (en) | 1994-09-30 | 1994-09-30 | Water-based polyurethane resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25968394A JP3633970B2 (en) | 1994-09-30 | 1994-09-30 | Water-based polyurethane resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08100043A JPH08100043A (en) | 1996-04-16 |
| JP3633970B2 true JP3633970B2 (en) | 2005-03-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP25968394A Expired - Lifetime JP3633970B2 (en) | 1994-09-30 | 1994-09-30 | Water-based polyurethane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042135A1 (en) * | 2002-11-04 | 2004-05-21 | Invista Technologies S.À.R.L. | Articles treated with aqueous dispersions of poly(urea/urethanes) |
| WO2004041893A1 (en) * | 2002-11-04 | 2004-05-21 | Invista Technologies S.À.R.L. | Aqueous dispersions of poly(urea/urethanes) |
| AU2003286898A1 (en) * | 2002-11-04 | 2004-06-07 | Invista Technologies S.A.R.L. | Articles comprising aqueous dispersions using poly(urea/urethanes) |
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| JPH08100043A (en) | 1996-04-16 |
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