TW200949044A - Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather - Google Patents

Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather Download PDF

Info

Publication number
TW200949044A
TW200949044A TW97150263A TW97150263A TW200949044A TW 200949044 A TW200949044 A TW 200949044A TW 97150263 A TW97150263 A TW 97150263A TW 97150263 A TW97150263 A TW 97150263A TW 200949044 A TW200949044 A TW 200949044A
Authority
TW
Taiwan
Prior art keywords
water
polyurethane resin
artificial leather
acid
salt
Prior art date
Application number
TW97150263A
Other languages
Chinese (zh)
Other versions
TWI453319B (en
Inventor
Yoshinobu Kibe
Kazuo Tanabe
Original Assignee
Nicca Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nicca Chemical Co filed Critical Nicca Chemical Co
Publication of TW200949044A publication Critical patent/TW200949044A/en
Application granted granted Critical
Publication of TWI453319B publication Critical patent/TWI453319B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

Abstract

Disclosed is an aqueous urethane resin composition for an artificial leather, which comprises a thermally setting aqueous urethane resin having a thermal setting temperature of 40 to 90 DEG C and at least one water-soluble acrylic polymer selected from the following polymers (1), (2) and (3): (1) a polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, or an alkali metal salt and/or an amine salt of the polymer; (2) poly-a-hydroxyacrylic acid, or an alkali metal salt and/or an amine salt thereof; and (3) a polymer produced by the radical polymerization of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, an alkali metal salt of acrylic acid, an alkali metal salt of methacrylic acid, an alkali metal salt of maleic acid, an amine salt of acrylic acid, an amine salt of methacrylic acid and an amine salt of maleic acid and at least one member selected from the group consisting of poly-a-hydroxyacrylic acid and an alkali metal salt and/or an amine salt thereof, or an alkali metal salt and/or an amine salt of the polymer.

Description

200949044 九、發明說明 【發明所屬之技術領域】 本發明係有關一種人造皮革用水系聚胺基甲酸乙酯樹 脂組成物、使用其之人造皮革的製造方法、及人造皮革。 【先前技術】 自古以來，人造皮革係藉由在不織布、織物、編物等 Φ 之基布中實施含浸或塗覆聚胺基甲酸乙酯樹脂組成物之處 理予以製造。一般而言，該製造方法係使用在N，N-二甲 基甲醯胺等之有機溶劑中溶解有聚胺基甲酸乙酯樹脂成分 之溶劑系聚胺基甲酸乙酯樹脂組成物，進行將該物含浸於 基布之處理。藉由使用溶劑系聚胺基甲酸乙酯樹脂組成物 ，可在基布中均勻地形成多孔質之聚胺基甲酸乙酯層，形 成具有類似天然皮革之柔軟性及充實感的質感優異之人造 皮革。然而，使用溶劑系聚胺基甲酸乙酯樹脂組成物之人 φ 造皮革的製造方法，由於基布之加工處理中會排出有害的 溶劑，故會有必須耗費很大的勞力與費用進行爲防止水質 污濁或大氣污染時之溶劑回收處理的問題。 另外，進行使用水系聚胺基甲酸乙酯樹脂組成物製造 人造皮革。該方法係藉由使含有聚胺基甲酸乙酯樹脂之水 分散物的水系聚胺基甲酸乙酯樹脂以水稀釋成適當的濃度 ，且在該稀釋液中含浸基布，予以乾燥、硬化處理，使聚 胺基甲酸乙酯樹脂固定於基布上，形成人造皮革。使用水 系聚胺基甲酸乙酯樹脂組成物之方法，由於沒有使用有機 -5- 200949044 溶劑，故不需回收溶劑。 然而，使用水系聚胺基甲酸乙酯樹脂組成物的方法， 會有在基布中含浸水系聚胺基甲酸乙酯樹脂組成物且予以 加熱乾燥時，在基布中均勻分散的聚胺基甲酸乙酯樹脂之 粒子伴隨溶劑之水移動，移動於基布纖維之表面層上的現 象，容易產生所謂的移行現象之問題。產生該移行現象時 ，聚胺基甲酸乙酯偏存於基布纖維之表面側上，在內部幾 乎完全沒有聚胺基甲酸乙酯存在的狀態。結果，所得的人 造皮革，質感硬、容易產生皺折。特別是對聚胺基甲酸乙 酯樹脂之基布的塡充率高時，在基布纖維之表面側與內部 中聚胺基甲酸乙酯樹脂之濃度差變得顯著，質感粗硬、容 易變得類似紙的質感。因此，使用水系聚胺基甲酸乙酯樹 脂組成物時，對基布而言不易塡充20質量％以上之聚胺 基甲酸乙酯樹脂，不易製得使柔軟性及充實感兩立、具有 充分質感之人造皮革。換言之，使用溶劑系聚胺基甲酸乙 酯組成物時，對可得塡充率爲25〜50質量％、充分的柔 軟性而言，使用水系聚胺基甲酸乙酯樹脂組成物時，必須 使塡充率大幅地降低。 直至目前，進行檢討有關防止聚胺基甲酸乙酯樹脂之 移行現象的方法。例如，於下述專利文獻1中記載，使用 添加感熱凝膠化劑、賦予感熱凝固性之合成樹脂乳液，使 該物在熱水中凝固的方法。而且，於下述專利文獻2中記 載，在以陰離子性界面活性劑予以乳化的具有羧基之聚胺 基甲酸乙酯樹脂水性乳化物中添加有非離子界面活性劑及 -6- 200949044 感熱凝固劑之聚胺基甲酸乙酯乳液配合液含浸或塗覆於基 布後’以熱風或熱水進行加熱且感熱凝固的方法。另外， 於下述專利文獻3中記載，使在經強制乳化的聚胺基甲酸 乙酯乳液中溶解有無機鹽類之處理液賦予基布且進行加熱 乾燥的方法。而且，於下述專利文獻4中記載，使由感熱 凝固溫度爲40〜90°C之水系聚胺基甲酸乙酯樹脂、與在末 端含有疏水基且在分子鏈中含有聚胺基甲酸乙酯鍵之會合 〇 型增黏劑所形成的水系聚胺基甲酸乙酯樹脂組成物含浸或 塗覆於基布後，予以感熱凝固的方法。 專利文獻1:日本特公昭55-51076號公報 專利文獻2:日本特公昭59-1823號公報 專利文獻3:日本特開平6-316877號公報 專利文獻4:日本特開2000-297211號公報 【發明內容】 Φ 然而’於專利文獻1中記載的方法，雖可得防止移行 現象之效果，惟由於部分的樹脂組成物流出於凝固浴中後 予以凝固’該凝固物再附著於處理布之表面的問題，最後 會損及人造皮革之質感的情形。 於專利文獻2中記載的方法，藉由熱風乾燥進行感熱 凝固處理時’在經被膜化的樹脂內部無法形成多孔質層， 伴隨樹脂附著量增加，會有質感變硬的傾向。另外，在感 熱凝固時使用熱水時’由於聚胺基甲酸乙醋樹脂具有陰離 子性，容易溶解於熱水中，容易產生無法得到充分附著量 200949044 的問題。而且，考慮藉由添加感熱凝固性促進劑之無機鹽 (特別是2價以上之金屬鹽）使聚胺基甲酸乙酯樹脂進行 鹽析處理，以提高對基布之樹脂附著量的方法，惟由於聚 胺基甲酸乙酯樹脂具有陰離子性，樹脂組成物之安定性變 得極爲不佳，會有配合上的問題。 於專利文獻3中記載的方法，由於使用多量的無機鹽 類，於加工後之聚胺基甲酸乙酯樹脂中殘留有無機鹽類， 會有樹脂強度大爲降低的問題。樹脂強度低時，因染色時 等強的搓揉效果、導致樹脂脫落的可能性變高。此時，不 易得到具有充分的彈力性之人造皮革。 於專利文獻4中記載的方法，添加的會合型增黏劑雖 具有防止聚胺基甲酸乙酯樹脂之移行現象的能力，惟藉由 會合型增黏劑被粗大化的聚胺基甲酸乙酯樹脂粗粒子沒有 進入纖維中，形成附著於基布表面的狀態，故於染色時或 水洗時會有樹脂與會合型增黏劑容易脫落的問題。 如此仍沒有提供有關可製造具有與使用溶劑系聚胺基 甲酸乙酯樹脂組成物時相同程度的質感及彈力性之人造皮 革的水系聚胺基甲酸乙酯樹脂組成物。 本發明係有鑑於上述情形者，以提供一種可在水系製 造移行之防止性及樹脂強度優異、具有充分的質感及彈力 性之人造皮革的人造皮革用水系聚胺基甲酸乙酯樹脂組成 物、使用它之人造皮革的製造方法、及人造皮革。 本發明人等爲解決上述課題時，再三深入硏究檢討有 關人造皮革用水系聚胺基甲酸乙酯樹脂組成物之結果’發 -8 - 200949044 現含有感熱凝固型水系聚胺基甲酸乙酯樹脂、特定的水溶 性丙烯酸系聚合物之水系聚胺基甲酸乙酯樹脂組成物，即 使沒有提高系中之黏性，仍可形成移行防止能力優異且具 有充分的機械強度之樹脂層，藉由使用該水系聚胺基甲酸 乙酯樹脂組成物’可製造具有充分的柔軟性及充實感，且 彈力性優異的人造皮革，遂而完成本發明。 換言之，本發明提供一種人造皮革用水系聚胺基甲酸 ❹ 乙酯樹脂組成物，係爲在基布中含浸或塗覆水系聚胺基甲 酸乙酯樹脂組成物、製得人造皮革的方法中所使用的水系 聚胺基甲酸乙酯樹脂組成物，其特徵爲含有感熱凝固溫度 爲40〜90 °C之感熱凝固型水系聚胺基甲酸乙酯樹脂（a) 、水溶性丙烯酸系聚合物（b)，且水溶性丙烯酸系聚合 物（b)爲下述（1) 、（2)及（3)之聚合物中之至少一 種， (1) 選自丙烯酸、甲基丙烯酸及馬來酸所成群之至 〇 少一種單體之聚合物、該聚合物之鹼金屬及/或胺鹽， (2) 聚-α-羥基丙烯酸、其鹼金屬及/或胺鹽， (3) 使選自丙烯酸、甲基丙烯酸、馬來酸、丙烯酸 之鹼金屬鹽、甲基丙烯酸之鹼金屬鹽、馬來酸之鹼金屬鹽 、丙烯酸之胺鹽、甲基丙烯酸之胺鹽及馬來酸之胺鹽所成 群之至少一種單體、與選自聚-α-羥基丙烯酸以及其鹼金 屬及/或胺鹽所成群之至少一種進行自由基聚合所得的聚 合物、該聚合物之鹼金屬及/或胺鹽。 藉由本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組 -9 - 200949044 成物時，藉由具有上述構成，可充分防止製造人造皮革時 之移行性，可在水系製造具有充分質感及彈力性之人造皮 革。藉由本發明之水系聚胺基甲酸乙酯樹脂組成物，可得 該效果之理由雖不明確，惟藉由上述特定的水溶性丙烯酸 系聚合物（a)存在，爲可使纖維中經均勻浸透的感熱凝 固型水系聚胺基甲酸乙酯樹脂（b)在加熱時沒有移行情 形、有效地進行凝固，藉此可發揮較習知更爲顯著的感熱 凝固性，且使所形成的樹脂層之機械強度充分的要因之一 ，係爲本發明人所考慮者。 而且，本發明之人造皮革用水系聚胺基甲酸乙酯樹脂 組成物，靜置安定性優異，且凝固方法可藉由熱風、溫水 、蒸氣、紅外線、電磁波，高周波之任何方法，由於可製 得具有充分質感之人造皮革，故可使處理性優異、可提高 人造皮革之製造步驟的自由度。 另外，本發明係提供一種具有在基布中含浸或塗覆本 發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物的步驟 之人造皮革的製造方法 藉由本發明之人造皮革的製造方法，藉由使用本發明 之人造皮革用水系聚胺基甲酸乙酯樹脂組成物’可在水系 製造具有充分質感及彈力性之人造皮革。 此外，本發明係提供藉由本發明之人造皮革的製造方 法所得的人造皮革。 本發明之人造皮革，可藉由本發明之人造皮革的製造 方法所得者，可在水系中製造，且具有充分質感及彈力性 -10- 200949044 [發明之效果] 藉由本發明，可提供在水系中製造移行防止性及樹脂 強度優異、具有充分的質感及彈力性之人造皮革之人造皮 革用水系聚胺基甲酸乙酯樹脂組成物、使用它之人造皮革 的製造方法、及人造皮革。因此，藉由本發明之人造皮革 〇 用水系聚胺基甲酸乙酯樹脂組成物及使用它之人造皮革的 製造方法，可在水系中製造具有與使用溶劑系聚胺基甲酸 乙酯樹脂組成物所得的人造皮革相同程度之質感及彈力性 之人造皮革。 [爲實施發明之最佳形態] <人造皮革用水系聚胺基甲酸乙酯樹脂組成物> 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ® ’可使用作爲於基布中含浸的含浸液或塗覆的塗覆液，感 熱凝固型水系聚胺基甲酸乙酯樹脂（a)、水溶性丙烯酸 系聚合物（b) ’係可（I)預先予以混合，亦可（Π)個 別投予含浸液或塗覆液中，然後予以混合。於本說明書之 (〇 、 （Π)之形態中’含有感熱凝固型水系聚胺基甲 酸乙酯樹脂（a)及水溶性丙烯酸系聚合物（b)之混合物 皆稱爲水系聚胺基甲酸乙酯樹脂組成物。 (感熱凝固型水系聚胺基甲酸乙酯樹脂（a)) -11 - 200949044 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ，必須含有感熱凝固溫度爲40〜90 °C之感熱凝固型水系聚 胺基甲酸乙酯樹脂。而且，於本發明中「感熱凝固型水系 聚胺基甲酸乙酯樹脂」係指含有水系聚胺基甲酸乙酯樹脂 之樹脂液藉由溫度上昇，具有不可逆性增黏且凝固的性質 ，即具有「感熱凝固溫度」，該「感熱凝固溫度」係指使 樹脂液失去流動性、於凝固時之樹脂液溫度。而且，「水 系聚胺基甲酸乙酯樹脂」係指在沒有有機溶劑下，於水中 乳化•分散的聚胺基甲酸乙酯樹脂組成物。 不具感熱凝固性之水系聚胺基甲酸乙酯樹脂，使在基 布中含浸或塗覆樹脂組成物之處理布進行加熱乾燥時，無 法充分防止聚胺基甲酸乙酯樹脂移行於基布表面上，藉由 樹脂偏存於處理布之表面上，處理布變得粗硬，無法在水 系中製造具有充分的質感及彈力性之人造皮革。 本發明所使用的感熱凝固型水系聚胺基甲酸乙酯樹脂 之感熱凝固溫度，必須爲4 0〜9 0 °C，以4 5〜8 0 °C較佳。 感熱凝固溫度未達4 0 °C時，由於水系聚胺基甲酸乙酯樹脂 於保管時（特別是夏天）有凝膠化的可能性，必須充分注 意保管溫度。另外，感熱凝固溫度大於90 °C時，會有容易 引起移行的傾向，人造皮革之質感變得粗硬。 本發明所使用的感熱凝固型水系聚胺基甲酸乙酯樹脂 ，只要是具有感熱凝固性之水系聚胺基甲酸乙酯樹脂即可 ，特別是可在沒有受到組成、構造上之限定下使用。除上 述感熱凝固溫度以外，較佳的條件例如聚胺基甲酸乙酯樹 -12- 200949044 脂之軟化溫度。本發明所使用的感熱凝固型水系聚胺基甲 酸乙酯樹脂之軟化溫度爲100°C以上較佳，以120〜240°C 更佳。軟化溫度未達100°c之聚胺基甲酸乙酯樹脂，由於 容易因水、溶劑、酸、鹼、濕熱、光等變得惡化，故不爲 企求。 本發明所使用的感熱凝固型水系聚胺基甲酸乙酯樹脂 ，例如使（a )多元醇、（b )聚異氰酸酯、與視其所需（ φ c)具有2個以上活性氫原子之低分子鏈伸長劑進行反應 所得的異氰酸酯基末端預聚物，使用HLB爲7〜16之非 離子界面活性劑，在水中強制進行轉相乳化、分散後，以 (d)具有2個以上胺基及/或亞胺基之聚胺化合物予以 鏈伸長反應所得者。而且，HLB係指藉由Griffin之式所 求得的値。 (a)多元醇例如具有2個以上羥基之聚酯多醇、聚 碳酸酯多醇及聚醚多醇等。聚酯多醇例如聚己二酸乙二酯 〇 、聚己二酸丁二酯、聚伸乙基伸丁基己二酸酯、聚六亞甲 基異苯二甲酸己二酸酯、聚琥珀酸乙二酯、聚琥珀酸丁二 酯、聚癸二酸乙二酯、聚癸二酸丁二酯、聚-ε-己內酯二 醇、聚（3-甲基-1,5-伸戊基）己二酸酯、1,6-己二醇與二 聚酸之聚縮合物、1，6-己二醇與己二酸與二元酸之共聚縮 合物、壬二醇與二元酸之聚縮合物、乙二醇與己二酸與二 元酸之共聚縮合物等。聚碳酸酯多醇例如聚四亞甲基碳酸 酯二醇、聚六亞甲基聚碳酸酯二醇、聚-1，4-環己烷二亞甲 基碳酸酯二醇等。聚醚多醇例如分子量200〜6,000之聚 -13- 200949044 乙二醇、聚丙二醇、聚四甲二醇之均聚物、嵌段共聚物及 無規共聚物、氧化乙烯與氧化丙烯、氧化乙烯與氧化丁烯 之無規共聚物或嵌段共聚物等。另外，（a)多元醇可使 用具有醚鍵與酯鍵之聚醚酯多醇等。此等之多元醇可單獨 使用1種或組合2種以上使用。 (b )聚異氰酸酯沒有特別的限制，可使用具有2個 以上異氰酸酯基之芳香族聚異氰酸酯、脂肪族聚異氰酸酯 及脂環式聚異氰酸酯，例如六亞甲基二異氰酸酯、三甲基 六亞甲基二異氰酸酯等之脂肪族聚異氰酸酯化合物、異佛 爾酮二異氰酸酯、氫化苯二甲基二異氰酸酯、二環己基甲 烷二異氰酸酯、原菠烷二異氰酸酯、1，3-雙（異氰酸酯甲 基）環己烷等之脂環式聚異氰酸酯、甲次苯基二異氰酸酯 、二苯基甲烷二異氰酸酯、萘二異氰酸酯、甲次苯基二異 氰酸酯、苯二甲基二異氰酸酯、四甲基苯二甲基二異氰酸 酯等之芳香族聚異氰酸酯等。此等之聚異氰酸酯化合物， 可單獨1種使用或組合2種以上使用。 於上述之聚異氰酸酯化合物中，脂肪族聚異氰酸酯及 脂環式聚異氰酸酯化合物就賦予無變黃性之被膜的理由而 言較佳，例如可使用六亞甲基二異氰酸酯、異佛爾酮二異 氰酸酯、二環己基甲烷二異氰酸酯、原菠烷二異氰酸酯及 1,3-雙（異氰酸酯甲基）環己烷。於此等之中’二環己基 甲烷二異氰酸酯由於耐光性、耐熱性優異，故較佳。 (c )具有2個以上之活性氫原子之低分子鏈伸長劑 ，係爲可視其所需使用者。該低分子鏈伸長劑例如乙二醇 -14- 200949044 、丙二醇、新戊醇、I，4-丁二醇、1,6-己二醇、三羥甲基 丙烷、季戊四醇、山梨糖醇等之低分子量多元醇、乙二胺 、丙二胺、六甲二胺、二胺基環己基甲烷、哌嗪、2-甲基 哌嗪、異佛爾酮二胺、二乙三胺、三乙四胺等之低分子量 聚胺等。此等之低分子鏈伸長劑可單獨1種或組合2種以 上使用。 上述異氰酸酯基末端預聚物之製造方法，沒有特別的 〇 限制，可使用一次注入法之一段式異氰酸酯聚加成反應法 、或多段式異氰酸酯聚加成反應法等之習知製造方法。此 時之反應溫度，以40〜1 50°c較佳。而且，於反應液中視 其所需可添加二丁基二月桂酸錫鹽、辛酸錫鹽、二丁基 錫-2-乙基己酸鹽、三乙胺、三乙二胺、N-甲基嗎啉等之 反應觸媒。而且，於使異氰酸酯基末端預聚物合成的反應 液中，於該反應中或反應完成後可加入不與異氰酸酯基反 應的有機溶劑。有機溶劑例如丙酮、甲基乙酮、甲苯、四 © 氫呋喃、二噁烷、二甲基甲醯胺、N-甲基吡咯烷酮等。惟 於鏈伸長反應完成後，就以藉由減壓蒸餾處理等除去有機 溶劑較佳而言，以丙酮、甲基乙酮、四氫呋喃爲宜》 於本實施形態中’在水中分散異氰酸酯末端預聚物時 ，使用HLB爲7〜16之非離子界面活性劑、較佳者HLB9 〜1 5之非離子界面活性劑。而且，此處所指的HLB爲非 離子界面活性劑全體之HLB，使用數種非離子界面活性劑 時係指其加重平均。使用的非離子界面活性劑之HLB未 達7時’乳化分散物無法形成安定者，非離子界面活性劑 -15- 200949044 之HLB大於16時，在基布中含浸或塗覆水系聚胺基甲酸 乙酯樹脂後，浸漬於溫水時，恐會有聚胺基甲酸乙酯樹脂 分散物溶出的情形。 爲使異氰酸酯末端預聚物分散於水中時所使用的非離 子界面活性劑，HLB爲7〜16之範圍時，可使用習知慣用 的很多非離子界面活性劑，例如聚氧化乙烯二苯乙嫌基苯 醚型非離子界面活性劑、聚氧化乙烯氧化丙烯二苯乙嫌基 苯醚型非離子界面活性劑、聚氧化乙烯三苯乙烯基苯醚型 非離子界面活性劑、聚氧化乙烯氧化丙烯三苯乙烯基苯酸 型非離子界面活性劑、聚氧化乙烯月桂醚、聚氧化乙燃硬 脂醚、聚氧化乙烯油烯醚等之聚氧化乙烯長鏈烷醚類；聚 氧化乙烯山梨糖醇四油酸酯等、或聚氧化乙烯•聚氧化乙 烯醇之嵌段或無規聚合物、聚胺之聚氧化丙烯•聚氧化乙 烯加成物等。 特別是以使用具有下述構造式（I)所示架構的非離 子界面活性劑較佳。 (R-) Ph-O(AO) H --(1) n m R:碳數1〜9之烷基、芳基或芳烷基 η : 1〜3之整數[Technical Field] The present invention relates to a water-based polyurethane resin composition for artificial leather, a method for producing the artificial leather using the same, and an artificial leather. [Prior Art] Since ancient times, artificial leather has been manufactured by impregnating or coating a polyurethane resin composition in a base fabric of Φ, woven fabric, knitted fabric, or the like. In general, the production method is a solvent-based polyurethane resin composition in which a polyurethane resin component is dissolved in an organic solvent such as N,N-dimethylformamide or the like. The material is impregnated with a base fabric. By using a solvent-based polyurethane resin composition, a porous polyurethane layer can be uniformly formed in the base fabric to form an artificial fabric having a texture similar to the softness and fullness of natural leather. leather. However, in the method for producing human φ leather made of a solvent-based polyurethane resin composition, since a harmful solvent is discharged during the processing of the base fabric, it is necessary to take a lot of labor and expense to prevent it. The problem of solvent recovery in the case of water pollution or atmospheric pollution. Further, artificial leather was produced using a water-based polyurethane resin composition. The method is characterized in that the aqueous polyurethane resin containing the aqueous dispersion of the polyurethane resin is diluted with water to an appropriate concentration, and the base cloth is impregnated with the diluted solution to be dried and hardened. The polyurethane resin is fixed on the base fabric to form an artificial leather. In the method of using the aqueous polyurethane resin composition, since the organic -5 - 200949044 solvent is not used, it is not necessary to recover the solvent. However, in the method of using the aqueous polyurethane resin composition, there is a polyaminocarboxylic acid uniformly dispersed in the base fabric when the aqueous cloth is impregnated with the aqueous polyurethane resin composition and heated and dried. The phenomenon in which the particles of the ethyl ester resin move along the surface layer of the base fabric fiber accompanying the movement of the water of the solvent tends to cause a problem of so-called migration. When this migration phenomenon occurs, the polyurethane is partially deposited on the surface side of the base fabric fiber, and there is almost no state in which the polyurethane is present completely. As a result, the resulting human made leather has a hard texture and is prone to wrinkles. In particular, when the charge ratio of the base fabric of the polyurethane resin is high, the difference in concentration between the surface of the base fabric fiber and the interior of the polyurethane resin becomes remarkable, and the texture is rough and easy to change. It has a texture similar to paper. Therefore, when a water-based polyurethane resin composition is used, it is difficult for the base fabric to be filled with a polyurethane resin having a mass content of 20% by mass or more, and it is difficult to obtain a softness and a feeling of fullness. Textured artificial leather. In other words, when a solvent-based polyurethane composition is used, it is necessary to use a water-based polyurethane resin composition when the solvent-based charge ratio is 25 to 50% by mass and sufficient flexibility is obtained. The charge rate is greatly reduced. Up to now, a review has been conducted on a method for preventing migration of polyurethane resin. For example, Patent Document 1 listed below discloses a method of solidifying hot water by adding a sensible gelling agent and a synthetic resin emulsion which imparts thermosensitive coagulability. Further, Patent Document 2 listed below discloses a nonionic surfactant and a -6-200949044 thermosetting coagulant added to an aqueous polyurethane resin having a carboxyl group emulsified by an anionic surfactant. The method of heating or hot-heating by hot air or hot water after impregnating or coating the base polyurethane with the polyurethane emulsion. Further, Patent Document 3 listed below discloses a method in which a treatment liquid in which an inorganic salt is dissolved in a forced emulsified polyurethane emulsion is applied to a base fabric and dried by heating. Further, in Patent Document 4 listed below, an aqueous polyurethane resin having a thermosensitive solidification temperature of 40 to 90 ° C and a hydrophobic group at the terminal and a polyurethane in the molecular chain are used. A method in which a water-based polyurethane resin composition formed by a bond-type tackifier is impregnated or coated on a base fabric to be thermally coagulated. Patent Document 1: Japanese Patent Publication No. Sho 59-51076 (Patent Document 2) Japanese Patent Publication No. Hei. No. Hei. No. Hei. Φ However, in the method described in Patent Document 1, although the effect of preventing the migration phenomenon can be obtained, since a part of the resin composition stream is solidified in the coagulation bath, the coagulum is attached to the surface of the treatment cloth. The problem will eventually damage the texture of the artificial leather. In the method described in Patent Document 2, when the thermosetting coagulation treatment is performed by hot air drying, the porous layer cannot be formed in the film-formed resin, and the texture tends to be hardened as the amount of resin adhesion increases. In addition, when hot water is used during thermal coagulation, the polyurethane resin has an anionic property and is easily dissolved in hot water, which tends to cause a problem that a sufficient amount of adhesion is not obtained. Further, a method of salt-removing a polyurethane resin by adding an inorganic salt (especially a metal salt of two or more valences) of a thermosensitive coagulating accelerator to increase the amount of resin attached to the base fabric is considered. Since the polyurethane resin has an anionic property, the stability of the resin composition becomes extremely poor, and there is a problem in blending. In the method described in Patent Document 3, since a large amount of inorganic salts are used, inorganic salts remain in the processed polyurethane resin, and the resin strength is largely lowered. When the resin strength is low, the possibility of the resin falling off due to a strong enamel effect such as dyeing becomes high. At this time, it is not easy to obtain artificial leather having sufficient elasticity. In the method described in Patent Document 4, the added conforming tackifier has the ability to prevent the migration of the polyurethane resin, but is a polyurethane which is coarsened by the conforming tackifier. Since the resin coarse particles do not enter the fiber and form a state of adhering to the surface of the base fabric, there is a problem that the resin and the bonding type tackifier are easily peeled off during dyeing or water washing. Thus, there has not been provided an aqueous polyurethane resin composition which can produce artificial leather having the same degree of texture and elasticity as that of the solvent-based polyurethane resin composition. In view of the above, the present invention provides an artificial polyurethane water-based polyurethane resin composition which is excellent in the preventability of water-based production migration and has excellent resin strength and has sufficient texture and elasticity. A method for producing artificial leather using the same, and artificial leather. In order to solve the above problems, the inventors of the present invention have further intensively reviewed the results of the composition of the polyurethane-based resin for artificial leather. 'Fa-8 - 200949044 Now contains a thermosetting solidified water-based polyurethane resin. The water-based polyurethane resin composition of the specific water-soluble acrylic polymer can form a resin layer excellent in migration prevention ability and sufficient mechanical strength without improving the viscosity in the system. The water-based polyurethane resin composition can produce artificial leather having sufficient flexibility and a feeling of fullness and excellent elasticity, and the present invention has been completed. In other words, the present invention provides a water-based polyurethane urethane resin composition for artificial leather, which is obtained by impregnating or coating a water-based polyurethane resin composition in a base fabric to obtain artificial leather. The aqueous polyurethane resin composition used is characterized in that it contains a thermosensitive solidification type aqueous polyurethane resin (a) having a thermosensitive solidification temperature of 40 to 90 ° C, and a water-soluble acrylic polymer (b) And the water-soluble acrylic polymer (b) is at least one of the following polymers (1), (2) and (3), and (1) is selected from the group consisting of acrylic acid, methacrylic acid and maleic acid. a group of polymers of a monomer, an alkali metal and/or an amine salt of the polymer, (2) poly-α-hydroxy acrylic acid, an alkali metal and/or an amine salt thereof, and (3) selected from acrylic acid , methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid a group of at least one monomer selected from poly-α-hydroxy acrylic acid and Alkali metal and / or amine salt groups is at least one free-radical polymerization of the resulting polymer is, the polymer of the alkali metal and / or amine salts. When the artificial leather of the present invention is made of a water-based polyurethane resin group -9 - 200949044, the above-described configuration can sufficiently prevent the migration property in the production of artificial leather, and can have sufficient texture and elasticity in water system production. Artificial leather. The reason why the effect can be obtained by the aqueous polyurethane resin composition of the present invention is not clear, but the above-mentioned specific water-soluble acrylic polymer (a) is present, so that the fibers can be uniformly impregnated. The thermosensitive solidification type aqueous polyurethane resin (b) does not migrate during heating and is effectively solidified, whereby a more remarkable thermosensitive coagulability can be exhibited, and the formed resin layer is formed. One of the reasons for the sufficient mechanical strength is considered by the inventors. Further, the artificial leather of the present invention is a polyurethane-based resin composition having excellent static stability, and the solidification method can be carried out by any method such as hot air, warm water, steam, infrared rays, electromagnetic waves, or high frequency. Since the artificial leather having a sufficient texture is obtained, the handleability is excellent, and the degree of freedom in the manufacturing steps of the artificial leather can be improved. Further, the present invention provides a method for producing an artificial leather having a step of impregnating or coating a water-based polyurethane resin composition of the artificial leather of the present invention with a base fabric, and a method for producing the artificial leather of the present invention, Artificial leather having sufficient texture and elasticity can be produced in the water system by using the artificial leather water-based polyurethane resin composition of the present invention. Further, the present invention provides artificial leather obtained by the method for producing artificial leather of the present invention. The artificial leather of the present invention can be produced in a water system by the method for producing the artificial leather of the present invention, and has sufficient texture and elasticity. - 200949044 [Effect of the Invention] By the present invention, it can be provided in a water system An artificial polyurethane water-based polyurethane resin composition having excellent transition resistance and resin strength, and an artificial leather having sufficient texture and elasticity, a method for producing artificial leather using the same, and artificial leather. Therefore, the artificial leather enamel water-based polyurethane resin composition of the present invention and the method for producing the artificial leather using the same can be produced in an aqueous system having a solvent-based polyurethane resin composition. Artificial leather with the same degree of texture and elastic artificial leather. [Best Mode for Carrying Out the Invention] <Artificial Leather Water-Based Polyurethane Resin Composition> The artificial leather water-based polyurethane resin composition of the present invention® can be used as a base fabric The impregnated impregnation liquid or the coating liquid to be impregnated, the thermosetting type water-based polyurethane resin (a), and the water-soluble acrylic polymer (b) may be preliminarily mixed (I) Π) Individually administered to the impregnation or coating solution and then mixed. In the form of (〇, (Π), the mixture containing the thermosetting type water-based polyurethane resin (a) and the water-soluble acrylic polymer (b) is referred to as water-based polyurethane. Ester resin composition. (Thermal solidification type water-based polyurethane resin (a)) -11 - 200949044 The artificial leather water-based polyurethane resin composition of the present invention must contain a thermosensitive solidification temperature of 40~ In the present invention, the "thermosetting type water-based polyurethane resin" means a resin liquid containing an aqueous polyurethane resin. It has a property of irreversibly thickening and solidification, that is, a "heat-sensitive solidification temperature" which is a temperature at which the resin liquid loses fluidity and is solidified at the time of solidification. "Ethyl urethane resin" means a polyurethane resin composition which is emulsified and dispersed in water in the absence of an organic solvent. Water-based polyurethane resin which does not have thermosensitive coagulability The grease is used to heat-dry the treated cloth impregnated or coated with the resin composition in the base fabric, and the polyurethane resin cannot be sufficiently prevented from moving on the surface of the base fabric by the resin being deposited on the surface of the treated cloth. The treated cloth becomes rough and cannot produce artificial leather having sufficient texture and elasticity in the water system. The thermosensitive solidification temperature of the thermosetting type water-based polyurethane resin used in the present invention must be 40%. 9 0 ° C, preferably 4 5 to 80 ° C. When the heat-sensitive solidification temperature is less than 40 ° C, the water-based polyurethane resin may be gelled during storage (especially in summer). In addition, when the thermosensitive solidification temperature is higher than 90 °C, there is a tendency to cause migration, and the texture of the artificial leather becomes rough. The thermosetting type water-based polyurethane for use in the present invention The ester resin may be any water-based polyurethane resin having thermotropic cohesive properties, and may be used without particular limitation in composition and structure. In addition to the above-described thermosensitive solidification temperature, The softening temperature of the polyurethane of the thermosetting type water-based polyurethane resin used in the present invention is preferably 100 ° C or more, preferably 120 to 240. More preferably, the polyurethane resin having a softening temperature of less than 100 ° C is not easily deteriorated due to deterioration of water, solvent, acid, alkali, moist heat, light, etc., which is used in the present invention. A thermosensitive solidification type aqueous polyurethane resin, for example, reacting (a) a polyhydric alcohol, (b) a polyisocyanate, and a low molecular chain extender having two or more active hydrogen atoms as required (φ c) The obtained isocyanate group-terminated prepolymer is subjected to phase inversion emulsification and dispersion in water using a nonionic surfactant having an HLB of 7 to 16 and (d) having two or more amine groups and/or imine groups. The polyamine compound is obtained by a chain elongation reaction. Moreover, HLB refers to the enthalpy obtained by the formula of Griffin. (a) A polyhydric alcohol, for example, a polyester polyol having two or more hydroxyl groups, a polycarbonate polyol, a polyether polyol, or the like. Polyester polyols such as polyethylene adipate bismuth, polybutylene adipate, polyethylidene butyl adipate, polyhexamethylene isophthalate adipate, polysuccinic acid Ethylene glycol ester, polybutylene succinate, polyethylene terephthalate, polybutylene adipate, poly-ε-caprolactone diol, poly(3-methyl-1,5-extension Agglomerates, polycondensates of 1,6-hexanediol and dimer acid, copolymer condensates of 1,6-hexanediol with adipic acid and dibasic acid, decanediol and dibasic acid A polycondensate, a copolymer condensate of ethylene glycol and adipic acid and a dibasic acid, and the like. Polycarbonate polyols such as polytetramethylene carbonate diol, polyhexamethylene polycarbonate diol, poly-1,4-cyclohexane dimethylene carbonate diol, and the like. Polyether polyols such as poly-13-200949044 having a molecular weight of 200 to 6,000, homopolymers of ethylene glycol, polypropylene glycol, polytetramethylene glycol, block copolymers and random copolymers, ethylene oxide with propylene oxide, ethylene oxide A random copolymer or a block copolymer with butylene oxide. Further, (a) the polyhydric alcohol may be a polyether ester polyol having an ether bond and an ester bond. These polyols may be used alone or in combination of two or more. (b) The polyisocyanate is not particularly limited, and an aromatic polyisocyanate having two or more isocyanate groups, an aliphatic polyisocyanate, and an alicyclic polyisocyanate such as hexamethylene diisocyanate or trimethylhexamethylene may be used. Aliphatic polyisocyanate compound such as diisocyanate, isophorone diisocyanate, hydrogenated dimethyl diisocyanate, dicyclohexylmethane diisocyanate, raw spinane diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane An alicyclic polyisocyanate such as an alkane, a methyl phenyl diisocyanate, a diphenylmethane diisocyanate, a naphthalene diisocyanate, a methylphenyl diisocyanate, a benzene dimethyl diisocyanate, a tetramethyl dimethyl diisocyanate An aromatic polyisocyanate or the like. These polyisocyanate compounds may be used alone or in combination of two or more. Among the above polyisocyanate compounds, the aliphatic polyisocyanate and the alicyclic polyisocyanate compound are preferred for imparting a film having no yellowing property, and for example, hexamethylene diisocyanate, isophorone diisocyanate, or the like can be used. Cyclohexylmethane diisocyanate, raw spinane diisocyanate, and 1,3-bis(isocyanatemethyl)cyclohexane. Among them, 'dicyclohexylmethane diisocyanate is preferred because it is excellent in light resistance and heat resistance. (c) A low molecular chain extender having two or more active hydrogen atoms, which is desirable for the user. The low molecular chain extender such as ethylene glycol-14-200949044, propylene glycol, neopentyl alcohol, I,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol, etc. Low molecular weight polyol, ethylenediamine, propylenediamine, hexamethyldiamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine Such as low molecular weight polyamines and the like. These low molecular chain extenders may be used alone or in combination of two or more. The method for producing the above isocyanate group-terminated prepolymer is not particularly limited, and a conventional one-stage isocyanate polyaddition reaction method or a multistage isocyanate polyaddition reaction method can be used. The reaction temperature at this time is preferably 40 to 150 ° C. Further, dibutyl dilaurate tin salt, tin octylate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine may be added to the reaction solution as needed. Wait for the reaction catalyst. Further, in the reaction solution in which the isocyanate group-terminated prepolymer is synthesized, an organic solvent which does not react with the isocyanate group may be added in the reaction or after completion of the reaction. An organic solvent such as acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone or the like. However, after the chain extension reaction is completed, it is preferred to remove the organic solvent by vacuum distillation or the like, preferably acetone, methyl ethyl ketone or tetrahydrofuran. In the present embodiment, the isocyanate terminal prepolymerization is dispersed in water. For the case of the material, a nonionic surfactant having an HLB of 7 to 16 and preferably a nonionic surfactant of HLB 9 to 15 is used. Further, the HLB referred to herein is the HLB of the entire nonionic surfactant, and the use of several nonionic surfactants means the weighted average. When the HLB of the nonionic surfactant used is less than 7, the emulsified dispersion cannot form a stabilizer. When the HLB of the nonionic surfactant -15-200949044 is greater than 16, the water-based polyaminocarboxylic acid is impregnated or coated in the base fabric. After the ethyl ester resin is immersed in warm water, there is a fear that the polyurethane resin dispersion may be eluted. In order to disperse the isocyanate terminal prepolymer in water, when the HLB is in the range of 7 to 16, many conventional nonionic surfactants such as polyethylene oxide diphenyl benzene may be used. Nonylionic surfactant, polyoxyethylene oxypropylene diphenylethyl phenyl ether type nonionic surfactant, polyoxyethylene tristyrylphenyl ether type nonionic surfactant, polyoxyethylene propylene oxide Polystyrene long-chain alkyl ethers such as tristyrylbenzoic acid type nonionic surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene olefinic ether, etc.; polyoxyethylene sorbitol A tetraoleate or a polyoxyethylene/polyoxyethylene alcohol block or a random polymer, a polyamine polyoxypropylene/polyethylene oxide adduct, or the like. Particularly, it is preferred to use a nonionic surfactant having a structure represented by the following structural formula (I). (R-) Ph-O(AO) H --(1) n m R: an alkyl group, an aryl group or an aralkyl group having a carbon number of 1 to 9 η : an integer of 1 to 3

Ph :苯基環殘基 AO:氧化乙烯及/或氧化丙烯 m: AO加成莫耳數 上述之非離子界面活性劑，可單獨1種或2種以上組 -16- 200949044 合使用。 非離子界面活性劑之使用量，沒有特別的限制，對異 氰酸酯末端預聚物而言以0.5〜10質量％較佳，以丨〜6 質量％更佳。非離子界面活性劑之使用量，對異氰酸醋末 端預聚物而言未達0.5質量％時，不易得到安定的乳化分 散狀態。非離子界面活性劑之使用量，對異氰酸酯末端預 聚物而言大於10質量％時，所得的聚胺基甲酸乙酯樹脂 Φ 被膜，變得耐水性不佳者，恐會有染色時或水洗時容易脫 落的情形。 使異氰酸酯基末端預聚物在水中進行轉化乳化、分散 時，可使用機械性切變應力。施予機械切變應力的方法， 沒有特別的限制，例如可使用均混器、均分析器等之乳化 機器。氰酸酯基末端預聚物在5〜40 °c之溫度範圍內，以 在水中進行乳化分散，極力抑制異氰酸酯基與水、或與非 離子界面活性劑之反應較佳。另外，使異氰酸酯基末端預 ❹ 聚物在水中進行轉相乳化、分散時，視其所需可添加磷酸 、磷酸二氫鈉、磷酸氫二鈉、對甲苯磺酸、己二酸、氯化 苯甲醯基等之反應抑制劑。 使異氰酸酯基末端預聚物在水中進行轉化乳化、分散 後’藉由使用（d)具有2個以上胺基及/或亞胺基之聚 胺化合物以進行鏈伸長反應，製得聚胺基甲酸乙酯樹脂水 分散物。 (d)具有2個以上胺基及/或亞胺基之聚胺化合物 ，例如乙二胺、丙二胺、四甲二胺、六甲二胺、二胺基環 -17- 200949044 己基甲烷、哌嗪、聯胺、2 -甲基哌嗪、異佛爾酮二胺、原 菠烷二胺、二胺基二苯基甲烷、甲次苯基二胺、苯二甲基 二胺等之二胺、或二乙三胺、三乙四胺、四乙五胺、亞胺 基丙胺、參（2-胺基乙基）胺等之聚胺、二-一級胺及單 羧酸所衍生的醯胺、二-一級胺之單酮胺等之水溶性胺衍 生物、草酸二聯胺、丙酸二聯胺、琥珀酸二聯胺、戊二酸 二聯胺、己二酸二聯胺、癸二酸二聯胺、馬來酸二聯胺、 富馬酸二聯胺、衣康酸二聯胺、1，1’-伸乙基聯胺、1，1’_ Q 三亞甲基聯胺、1,1’- (1，4-伸丁基）二聯胺等之聯胺衍生 物。此等之聚胺化合物及胺衍生物，可單獨1種或2種以 上組合使用。Ph: phenyl ring residue AO: ethylene oxide and/or propylene oxide m: AO addition mole number The above-mentioned nonionic surfactants may be used alone or in combination of two or more groups -16-200949044. The amount of the nonionic surfactant to be used is not particularly limited, and is preferably from 0.5 to 10% by mass, more preferably from 丨 to 6% by mass, based on the isocyanate terminal prepolymer. When the amount of the nonionic surfactant used is less than 0.5% by mass in the isocyanate end-prepolymer, it is difficult to obtain a stable emulsified dispersion state. When the amount of the nonionic surfactant used is more than 10% by mass based on the isocyanate terminal prepolymer, the obtained polyurethane resin Φ film may become poor in water resistance, and may be stained or washed. It is easy to fall off. When the isocyanate-based terminal prepolymer is subjected to conversion emulsification and dispersion in water, mechanical shear stress can be used. The method of applying the mechanical shear stress is not particularly limited, and for example, an emulsification machine such as a homomixer or a homogenizer can be used. The cyanate-based terminal prepolymer is emulsified and dispersed in water at a temperature of from 5 to 40 ° C, and it is preferred to suppress the reaction of the isocyanate group with water or with a nonionic surfactant as much as possible. Further, when the isocyanate-based terminal prepolymer is subjected to phase inversion emulsification and dispersion in water, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid, chlorinated benzene may be added as needed. A reaction inhibitor such as a thiol group. After the isocyanate-based terminal prepolymer is subjected to conversion emulsification and dispersion in water, the polyamine-based formic acid is obtained by using (d) a polyamine compound having two or more amine groups and/or imine groups for chain elongation reaction. Ethyl resin aqueous dispersion. (d) a polyamine compound having two or more amine groups and/or imine groups, such as ethylenediamine, propylenediamine, tetramethyldiamine, hexamethyldiamine, diamine ring-17-200949044 hexylmethane, piperazine Diamines such as azine, hydrazine, 2-methylpiperazine, isophorone diamine, raw spinane diamine, diaminodiphenylmethane, methyl phenyl diamine, benzene dimethyl diamine Or a polyamine, a di-primary amine or a monocarboxylic acid derived from a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminopropylamine or bis(2-aminoethyl)amine. Water-soluble amine derivative such as mono-amine of mono-amine, oxalic acid diamine, propionic acid diamine, succinic acid diamine, glutaric acid diamine, adipic acid diamine, bismuth Acid diamine, maleic acid diamine, fumaric acid diamine, itaconic acid diamine, 1,1'-extended ethyl hydrazine, 1,1'_ Q trimethylene hydrazine, 1 a hydrazine derivative such as 1'-(1,4-butylene)diamine. These polyamine compounds and amine derivatives may be used alone or in combination of two or more.

異氰酸酯基末端預聚物之鏈伸長反應，可在異氰酸酯 基末端聚合物之乳化分散物中添加（d)聚胺化合物，或 在（d)聚胺化合物中添加預聚物之乳化分散物進行。鏈 伸長反應以在反應溫度爲20〜4(TC下進行較佳。於異氰酸 酯基末端預聚物合成時使用有機溶劑時，以於鏈伸長反應 Q 完成後，藉由減壓蒸餾處理等除去有機溶劑較佳。 經由上述鏈伸長反應，使用有機溶劑時，可再藉由除 去上述有機溶劑之步驟，製得實質上固成分約爲10〜60 質量％ (較佳者爲15〜50質量％)之無溶劑的水分散體 的感熱凝固型水系聚胺基甲酸乙酯樹脂（a)。 本發明所使用的感熱凝固型水系聚胺基甲酸乙酯樹脂 (a)，藉由與水溶性丙烯酸系聚合物（b)組合，發揮顯 著的感熱凝固性，惟就防止乾燥時之移行性而言，以平均 -18- 200949044 粒徑至少爲O.l^m以上較佳。感熱凝固型水系聚胺基甲 酸乙酯樹脂之平均粒徑未達O.l/im時，會有防止移行性 降低的傾向。另外，感熱凝固型水系聚胺基甲酸乙醋樹脂 之平均粒徑以0.15〜5/zm更佳。感熱凝固型水系聚胺基 甲酸乙酯樹脂之平均粒徑爲5;/m以上時，會有水系聚胺 基甲酸乙酯樹脂之安定性降低的傾向。而且，此處所指的 平均粒徑係指使用雷射繞射/散射式粒度分布測定裝置之 0 「LA-9 20」（（股）堀場製作所製），以體積基準測定時 之介質直徑。 (水溶性丙烯酸系聚合物（b )) 本發明所使用的水溶性丙烯酸系聚合物（b)，係爲 下述（1) 、（2)及（3)之聚合物中之至少一種。 (1)選自丙烯酸、甲基丙烯酸及馬來酸所成群之至 少一種單體的聚合物、該聚合物之鹼金屬及/或二胺鹽。 參 （2)聚-α-羥基丙烯酸、其鹼金屬及/或胺鹽， (3)使選自丙烯酸、甲基丙烯酸、馬來酸、丙烯酸 之鹼金屬鹽、甲基丙嫌酸之鹼金屬鹽、馬來酸之驗金屬鹽 、丙烯酸之胺鹽、甲基丙烯酸之胺鹽及馬來酸之胺鹽所成 群之至少一種單體、與選自聚-α-羥基丙烯酸以及其鹼金 屬及/或胺鹽所成群之至少一種進行自由基聚合所得的聚 合物、該聚合物之鹼金屬及/或胺鹽。 藉由含有以上述之水溶性丙烯酸系聚合物與感熱凝固 型水系聚胺基甲酸乙酯樹脂（b)同時作爲必須成分的本 -19- 200949044 發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物時，在 基布中進行含浸或塗覆、且加熱乾燥時，發現感熱凝固型 水系聚胺基甲酸乙酯樹脂較習知更爲顯著的感熱凝固性， 與使用溶劑系聚胺基甲酸乙酯樹脂組成物所得的人造皮革 具有相同程度的質感，特別是可在水系中製造具有充實感 、柔軟性及韌性之質感的人造皮革。 使用不具水溶性之丙烯酸系聚合物取代水溶性丙烯酸 系聚合物時，由於與感熱凝固型水系聚胺基甲酸乙酯樹脂 之相溶性變得不佳，形成不均勻系，無法得到本發明之效 果。 (1)所例舉的聚合物中，選自丙烯酸、甲基丙烯酸 及馬來酸所成群之至少1種單體之聚合物，可藉由進行自 由基聚合製得。而且’聚合物之鹼金屬及/或胺鹽，可藉 由使上述單體之鹼金屬鹽及上述單體之胺鹽中之1種以上 的單體進行自由基聚合、或使部分或全部選自丙烯酸、甲 基丙烯酸及馬來酸所成群之至少1種單體的聚合物之羧基 ，藉由鹼金屬及/或胺進行中和、製得。於自由基聚合時 ，在不會損害本發明效果之範圍內，除上述單體外，可使 其他單體進行共聚合。可共聚合的單體，例如富馬酸、衣 康酸、乙烯、氯化乙烯基、醋酸乙烯酯、丙烯醯胺、丙烯 酸酯、甲基丙烯酸酯等。 聚合物之鹼金屬鹽，例如鋰鹽、鈉鹽、鉀鹽等。而且 ’聚合物之胺鹽例如銨鹽、三乙胺鹽、丁胺鹽、二丁胺鹽 、單乙醇胺鹽、二乙醇胺鹽、三乙醇胺鹽等。於聚合物之 -20- 200949044 ❹ 鹽中亦可含有2種以上之上述鹽。 而且，聚合物之鹽爲鹼土類金屬鹽或重金屬鹽（例如 Fe2+、Fe3 +等）之各種多價離子的鹽時，由於不溶性之鹽 殘留於經感熱凝固的聚胺基甲酸乙酯樹脂被膜中，會有損 害人造皮革之品質的可能性且會有降低樹脂強度的可能性 ，故不爲企求。 (1 )所例舉的聚合物之重量平均分子量，以500〜 1,000,000較佳，以1，000〜150,000更佳。聚合物之重量The chain elongation reaction of the isocyanate group-terminated prepolymer may be carried out by adding (d) a polyamine compound to the emulsion dispersion of the isocyanate group-terminated polymer, or by adding an emulsion dispersion of the prepolymer to the (d) polyamine compound. The chain extension reaction is preferably carried out at a reaction temperature of 20 to 4 (TC). When an organic solvent is used in the synthesis of the isocyanate group-terminated prepolymer, after the chain elongation reaction Q is completed, the organic component is removed by vacuum distillation or the like. The solvent is preferably used. When the organic solvent is used for the chain extension reaction, the step of removing the organic solvent can be further carried out to obtain a substantially solid content of about 10 to 60% by mass (preferably 15 to 50% by mass). The thermosensitive solidification type aqueous polyurethane resin (a) of the solvent-free aqueous dispersion. The thermosetting type aqueous polyurethane resin (a) used in the present invention, and the water-soluble acrylic resin The polymer (b) is combined to exert significant thermotropic coagulability, but in terms of preventing migration during drying, the average particle size of -18-200949044 is preferably at least O?m or more. The thermosetting type water-based polyaminocarboxylic acid is preferred. When the average particle diameter of the ethyl ester resin is less than 0.1 mg, the migration property tends to be lowered. Further, the average particle diameter of the thermosetting type aqueous polyethylene glycol acetate resin is preferably 0.15 to 5/zm. Solidified water system When the average particle diameter of the ethyl urethane resin is 5; / m or more, the stability of the aqueous polyurethane resin tends to be lowered. Moreover, the average particle diameter referred herein means the use of laser diffraction. / "scattering particle size distribution measuring device" 0 "LA-9 20" (manufactured by Horiba, Ltd.), the diameter of the medium when measured by volume. (Water-soluble acrylic polymer (b)) Water-soluble solution used in the present invention The acrylic polymer (b) is at least one of the following polymers (1), (2) and (3). (1) A group selected from the group consisting of acrylic acid, methacrylic acid and maleic acid. a polymer of at least one monomer, an alkali metal and/or a diamine salt of the polymer, (2) poly-α-hydroxy acrylic acid, an alkali metal and/or an amine salt thereof, (3) selected from the group consisting of acrylic acid, A Acrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methyl propylene acid, metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid a group of at least one monomer selected from the group consisting of poly-α-hydroxy acrylic acid and alkali metal and/or amine salts thereof a polymer obtained by radical polymerization of at least one of the group, an alkali metal and/or an amine salt of the polymer, comprising a water-soluble acrylic polymer as described above and a thermosetting type water-based polyurethane resin ( b) In the case of the artificial leather water-based polyurethane resin composition of the invention of the present invention as an essential component, when the impregnation or coating is carried out in the base fabric and the heat is dried, the thermosetting type water-based polymerization is found. The urethane resin has a more pronounced thermocoagulation property than the artificial leather obtained by using the solvent-based polyurethane resin composition, and particularly has a feeling of fullness in the water system. Artificial leather with a soft and tough texture. When the water-soluble acrylic polymer is replaced by an acrylic polymer which is not water-soluble, the compatibility with the thermosensitive solid water-based polyurethane resin is poor, and unevenness is formed, and the effect of the present invention cannot be obtained. . (1) Among the polymers exemplified, a polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid can be obtained by radical polymerization. Further, the 'alkali metal and/or amine salt of the polymer may be subjected to radical polymerization or partial or complete selection of one or more monomers of the alkali metal salt of the above monomer and the amine salt of the above monomer. A carboxyl group of a polymer of at least one monomer grouped from acrylic acid, methacrylic acid, and maleic acid is neutralized by an alkali metal and/or an amine. In the case of radical polymerization, other monomers may be copolymerized in addition to the above monomers insofar as the effects of the present invention are not impaired. Copolymerizable monomers such as fumaric acid, itaconic acid, ethylene, vinyl chloride, vinyl acetate, acrylamide, acrylate, methacrylate, and the like. An alkali metal salt of a polymer such as a lithium salt, a sodium salt, a potassium salt or the like. Further, the amine salt of the polymer is, for example, an ammonium salt, a triethylamine salt, a butylamine salt, a dibutylamine salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt or the like. The polymer may also contain two or more of the above salts in the -20-200949044 ❹ salt. Further, when the salt of the polymer is a salt of various polyvalent ions of an alkaline earth metal salt or a heavy metal salt (for example, Fe2+, Fe3, etc.), the insoluble salt remains in the thermosetting coagulum resin film. There is a possibility of impairing the quality of artificial leather and there is a possibility that the strength of the resin is lowered, so it is not desirable. (1) The weight average molecular weight of the polymer exemplified is preferably from 500 to 1,000,000, more preferably from 1,000 to 150,000. Weight of polymer

平均分子量未達5 0 0時’會有不易得到充分的防止移行效 果之傾向。聚合物之重量平均分子量大於1，〇〇〇,〇〇〇時， 聚胺基甲酸乙酯樹脂被膜變成耐水性與耐鹼性不佳者，恐 會有於染色時或水洗時容易脫落的情形。 (2)所例舉的聚合物、即聚-α-羥基丙烯酸、其鹼 金屬及/或胺鹽’例如可藉由對應以下述式（11)所示之 聚·α -羥基丙烯酸之聚內酯化合物進行水解、製造。 [化1] 〇-When the average molecular weight is less than 50,000, there is a tendency that it is difficult to obtain a sufficient effect of preventing migration. When the weight average molecular weight of the polymer is more than 1, when the ruthenium or osmium is changed, the polyurethane resin film becomes poor in water resistance and alkali resistance, and there is a fear that it may fall off easily during dyeing or washing. . (2) The polymer exemplified, that is, poly-α-hydroxyacrylic acid, an alkali metal and/or an amine salt thereof can be, for example, a poly-α-hydroxyacrylic acid represented by the following formula (11) The ester compound is hydrolyzed and produced. [Chemical 1] 〇-

0II C -ch2—c—ch2-c- c-IIο •ο Ρ (II) (式中，ρ係表示聚合度） 而且，聚-α-羥基丙烯酸亦可藉由高分子量之聚- α- -21 - 200949044 羥基丙烯酸、聚-α-羥基丙烯酸酯等之氧化解聚合、製造 。聚-α-羥基丙烯酸之鹼金屬及/或胺鹽，亦可藉由使高 分子量之聚-α -羥基丙烯酸或聚-α -羥基丙烯酸酯等之氧 化解聚合物，藉由鹼金屬鹽的氫氧化物、水溶性胺進行中 和、製造。 聚合物之鹼金屬鹽例如鋰鹽、鈉鹽、鉀鹽。而且，聚 合物之胺鹽例如銨鹽、三乙胺鹽、丁胺鹽、二丁胺鹽、單 乙醇胺鹽、二乙醇胺鹽、三乙醇胺鹽等。此等之鹽例如使 用氫氧化鈉水溶液、三乙胺、三乙醇胺等，使對應以上述 式（Π)所示之聚-α-羥基丙烯酸的聚內酯化合物進行水 解、製得。於聚合物之鹽中，亦可含有2種以上之上述鹽 〇 而且，聚合物之鹽爲如鹼土類金屬鹽或重金屬鹽（例 如Fe2+、Fe3 +等）之多價離子的鹽時，由於不溶性之鹽殘 留於經感熱凝固的聚胺基甲酸乙酯樹脂被膜中，且會有損 害人造皮革之品質的可能性及降低樹脂強度之可能性，故 不爲企求。 (2) 所例舉的聚合物之重量平均分子量，以5〇〇〜 1，000,000較佳，以1,000〜150,000更佳。聚合物之重量 平均分子量未達5 00時，會有不易得到充分的防止移行效 果的傾向。聚合物之重量平均分子量大於1,000, 〇〇〇時， 恐會有聚胺基甲酸乙酯樹脂被膜變成耐水性與耐鹼性不佳 者，恐會有染色時或水洗時容易脫落的情形。 (3) 所例舉的聚合物，即可藉由選自丙烯酸、甲基 -22- 200949044 丙烯酸、馬來酸、丙烯酸之鹼金屬鹽、甲基丙烯酸之鹼金 屬鹽、馬來酸之鹼金屬鹽、丙烯酸之胺鹽、甲基丙烯酸之 胺鹽及馬來酸之胺鹽所成群之至少一種單體、與選自聚_ α-羥基丙烯酸及其鹼金屬及/或胺鹽所成群之至少一種進 行自由基聚合所得的聚合物、該聚合物之鹼金屬及/或胺 鹽’在含有聚-α-羥基丙烯酸或其鹽之水溶液中混合聚合 的單體’且添加自由基聚合引發劑，在50〜90 °C下加熱2 〇 〜10小時，進行反應的方法，或在含有聚-α-羥基丙烯酸 或其鹽之水溶液中加入自由基聚合引發劑後，滴入聚合的 單體’在50〜90 °C下加熱2〜10小時的方法等製得。此時 ，可在含有聚-α-羥基丙烯酸或其鹽之水溶液中添加甲醇 、乙醇、異丙醇等之醇類或丙酮等之水混合性溶劑。使用 的自由基聚合引發劑，沒有特別的限制，例如組合過硫酸 鉀、過硫酸鈉、過硫酸銨等之過硫酸鹽、過硫酸鹽與重亞 硫酸鈉等之氧化還原系引發劑、過氧化氫、水溶性偶氮系 ® 引發劑等。此等之自由基聚合引發劑，可單獨1種或2種 以上組合使用。自由基聚合引發劑之使用量，對與聚- α-羥基丙烯酸及/或其鹽進行自由基聚合的單體之合計量爲 100質量份而言，以0.1〜1.0質量份較佳。而且，於自由 基聚合時，可添加硫醇酸辛酯等之連鏈移動劑，調整聚合 度。丙烯酸、甲基丙烯酸及馬來酸之鹼金屬鹽，例如鋰鹽 、鈉鹽、鉀鹽等。另外，丙烯酸、甲基丙烯酸及馬來酸之 胺鹽，例如銨鹽、三乙胺鹽、丁胺鹽、二丁胺鹽、單乙醇 胺鹽、二乙醇胺鹽、三乙醇胺鹽等。此外，上述聚合物爲 -23- 200949044 具有自由基者時，使部分或全部其羧基藉由鹼金屬及/或 胺進行中和，可製得上述聚合物之鹼金屬及/或胺鹽。驗 金屬例如鋰、鈉、鉀等。而且，例如銨、三乙胺、丁胺、 二丁胺、單乙醇胺、二乙醇胺、三乙醇胺等。 而且，使選自丙烯酸、甲基丙烯酸、馬來酸、丙烯酸 之鹼金屬鹽、甲基丙烯酸之鹼金屬鹽、馬來酸之鹼金屬鹽 、丙烯酸之胺鹽、甲基丙烯酸之胺鹽及馬來酸之胺鹽所成 群之至少一種單體、與選自聚- 羥基丙烯酸及其鹼金屬 ◎ 及/或胺鹽所成群之至少一種進行聚合，本發明人等係考 慮藉由接枝聚合者。於自由基聚合時，在不會損害本發明 效果之範圍內，除上述之單體外，可使其他單體予以共聚 合。可共聚合的單體，例如富馬酸、衣康酸、乙烯、氯化 乙烯基、醋酸乙烯酯、丙烯醯胺、丙烯酸酯、甲基丙烯酸 酯等。 (3)所例舉的聚合物之重量平均分子量，以500〜 1,000,000較佳，以 1，000〜1 50,000更佳。聚合物之重量 0 平均分子量未達500時，會有不易得到充分的防止移行效 果之傾向。聚合物之重量平均分子量大於1，〇〇〇,〇〇〇時， 聚胺基甲酸乙酯樹脂被膜變成耐水性與耐鹼性不佳者，恐 會有於染色時或水洗時容易脫落的情形。 上述（2)及（3)之聚合物，可直接或以水、或溶解 於水與低元醇、丙酮等之水混合性溶劑的混合溶劑的溶液 ，混合含有感熱凝固型水系聚胺基甲酸乙酯樹脂（a)之 聚胺基甲酸乙酯樹脂水分散液中使用。上述（2)及（3) -24 - 200949044 之聚合物，由於與感熱凝固型水系聚胺基甲酸乙酯樹脂（ a)之鏈伸長基之胺基或亞胺基具有強的親和性，故與感 熱凝固型水系聚胺基甲酸乙酯樹脂之相溶性良好，可適合 使用作爲水溶性丙烯酸系聚合物（b)。 水溶性丙烯酸系聚合物（b)，可使用市售品。市售 品例如日本觸媒（股）製之亞古亞里谷（譯音）DL、TL 、HL、日本純藥（股）製之吉里馬（譯音）AC-10NP、東 ❹ 亞合成（股）製之亞龍（譯音）A-210、T-50、A-10SL、 A-30SL、A-20UN、A-20L、A-6520、千葉•日本（股）製 之 BELCLENE 200LA 等。 水溶性丙烯酸系聚合物（b )之配合量，以固成分比 、對100質量份之感熱凝固型水系聚胺基甲酸乙酯樹脂（ a) 而言’水溶性丙烯酸系聚合物（b)以0.1〜40質量份 較佳’以0.5〜20質量份更佳。水溶性丙烯酸系聚合物（ b) 之配合量，對100質量份感熱凝固型水系聚胺基甲酸 ❹ 乙酯樹脂（a)而言未達〇.1質量份時，會有不易得到充 分的水系聚胺基甲酸乙酯樹脂組成物之防止移行效果的傾 向。另外’水溶性丙烯酸系聚合物（b)之配合量，對 1〇〇質量份感熱凝固型水系聚胺基甲酸乙酯樹脂（a)而 言大於40質量份時’會有聚胺基甲酸乙酯樹脂被膜之耐 水性降低’且人造皮革之質感變硬的傾向。 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ’可藉由使上述的感熱凝固型水系聚胺基甲酸乙酯樹脂（ a)、與水溶性丙烯酸系聚合物（b)，在較感熱凝固型水 -25- 200949044 系聚胺基甲酸乙酯樹脂之感熱凝固溫度更爲充分的低溫度 下進行均勻混合，予以調製。而且，本發明之人造皮革用 水系聚胺基甲酸乙酯樹脂組成物，亦可在感熱凝固型水系 聚胺基甲酸乙酯樹脂（a)之製造過程中，藉由添加配合 水溶性丙烯酸系聚合物（b)予以調製。 於本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成 物中，除感熱凝固型水系聚胺基甲酸乙酯樹脂（a)及水 溶性丙烯酸系聚合物（b)以外，在不會損害本發明效果 之範圍內，可添加作爲其他的水系分散體或水分散液，例 如醋酸乙烯酯系、乙烯醋酸乙烯酯系、丙烯酸系、丙烯酸 苯乙烯酯系等之乳液；苯乙烯.丁二烯系、丙烯腈.丁二 烯系、丙烯酸· 丁二烯系等之乳膠；聚乙烯系、聚烯烴系 等之離子聚合物；聚胺基甲酸乙酯、聚酯、聚醯胺、環氧 系樹脂等之各種水系分散體、水分散液。此等可單獨1種 或2種以上組合使用。而且，此等之水系分散體或水分散 液，亦可添加於感熱凝固型水系聚胺基甲酸乙酯樹脂（a )及/或水溶性丙烯酸系聚合物（b)中，亦可添加於包 含感熱凝固型水系聚胺基甲酸乙酯樹脂（a)及水溶性丙 烯酸系聚合物（b)之水系聚胺基甲酸乙酯樹脂組成物。 而且，於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂組成物中，在不會損害本發明效果之範圍內，爲有效地 吸取蒸氣時之吸濕劑，例如可添加尿素、蛋白、丙三醇、 聚氧化乙烯非離子界面活性劑。此等可單獨1種或2種以 上組合使用。此外，此等之吸濕劑可添加於感熱凝固型水 -26- 200949044 系聚胺基甲酸乙酯樹脂（a)及/或水溶性丙嫌酸系聚合 物（b)中’亦可添加於包含感熱凝固型水系聚胺基甲酸 乙酯樹脂（a)及水溶性丙烯酸系聚合物（b)之水系聚胺 基甲酸乙酯樹脂組成物中。 另外’於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂組成物中’在不會損害本發明效果之範圍內，以降低感 熱凝固型水系聚胺基甲酸乙酯樹脂（a)之感熱凝固溫度 φ 爲目的時，例如可添加矽化鈉、矽氟化鉀；鹽酸、硝酸、 硫酸、磷酸之銨鹽、鈉、鉀、鈣、鎂、鋅、鋇、鎳、錫、 鉛、鐵及鋁等之多價金屬鹽；會合型增黏劑類、鹼性增黏 型聚合物類、聚醚硫醚乙二醇類、聚醚改性聚二甲基砂氧 烷系化合物；烷基苯酚-甲醛縮合物之氧化亞烷基加成物 等之感熱凝固劑。此等可單獨1種或2種以上組合使用。 而且，此等之感熱凝固劑可添加於感熱凝固型水系聚胺基 甲酸乙酯樹脂（a)及/或水溶性丙烯酸系聚合物（b)中 © ’亦可添加於包含感熱凝固型水系聚胺基甲酸乙酯樹脂（ a)及水溶性丙烯酸系聚合物（b)之水系聚胺基甲酸乙酯 樹脂組成物中。 另外’於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂組成物中’以改善造膜性爲目的時可配合烷二醇衍生物 、或脂肪族二羧酸之二烷酯、N -甲基吡咯烷酮等之造膜助 劑’或以改善加工適性爲目的時可配合氟系水平劑、二烷 基磺基琥珀酸酯系之乳化劑、乙炔醇衍生物等之各種水平 劑、浸透劑等。此外’於本發明之人造皮革用水系聚胺基 -27- 200949044 甲酸乙酯樹脂組成物中，以提高藉由機械發泡賦予加工適 性爲目的時，可配合硬脂酸銨、高級脂肪酸之金屬鹽、二 烷基磺基琥珀酸酯系乳化劑等之發泡劑。而且，於本發明 之人造皮革用水系聚胺基甲酸乙酯樹脂組成物中，以抑制 配合液之發泡情形爲目的時，可配合礦物油系、醯胺系、 聚矽氧系等之各種消泡劑或乙醇、異丙醇等之少量醇類。 此外，於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂組成物中，以著色爲目的時可配合水溶性或水分散性之 各種無機、有機顏料，而且，可配合碳酸鈣、滑石、氫氧 化鋁、二氧化矽、玻璃纖維等之無機塡充物、或纖維素粉 末、蛋白質粉末、絲粉末、有機短纖維等之有機塡充物。 而且，於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂中，以改善上述水分散體之耐光性、耐熱性、耐水性、 耐溶劑性等之各種耐久性爲目的時，可配合抗氧化劑、紫 外線吸收劑、防止水解劑等之安定劑。此等之安定劑，亦 可於水系聚胺基甲酸乙酯樹脂之製造步驟中、或其製造後 添加。 另外，於本發明之人造皮革用水系聚胺基甲酸乙酯樹 脂組成物中，可配合環氧樹脂、蜜胺樹脂、異氰酸酯化合 物、吖啶化合物、聚羰二醯亞胺化合物、噁唑啉化合物等 之交聯劑。 於本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成 物中，在不會損害本發明效果之範圍內，可配合爲賦予加 工適性時之各種添加劑。該添加劑例如醇系非離子界面活 -28- 200949044 性劑、乙炔醇系之特殊界面活性劑、脂肪酸鹽、烷基硫酸 酯鹽、烷基苯硫酸鹽、烷基磺基琥珀酸鹽、萘硫酸鹽、鏈 烷基磺酸酯鈉鹽、烷基二苯醚硫酸鈉鹽等之陰離子系乳化 劑；聚氧化乙烯烷基硫酸鹽、聚氧化乙烯烷基苯基硫酸鹽 等之非離子非離子陰離子系乳化劑、聚矽氧系之界面活性 劑、氟系界面活性劑之各種水平劑；抗氧化劑、耐光安定 化劑、紫外線防止劑等之各種安定化劑；礦物油系、聚矽 氧系等之各種消泡劑；聚胺基甲酸乙酯化觸媒、可塑劑、 顏料等之著色劑、可使時間延長劑等。此等可單獨1種或 2種以上組合使用。 上述之添加劑，可於感熱凝固型水系聚胺基甲酸乙酯 樹脂（a)製造途中或製造後添加，或使感熱凝固型水系 聚胺基甲酸乙酯樹脂（a)與水溶性丙烯酸系聚合物（b) 混合時一起添加配合’亦可添加含有作爲人造皮革製造時 之含浸液或塗覆液的感熱凝固型水系聚胺基甲酸乙酯樹脂 ® (a)及水溶性丙烯酸系聚合物（b)之水系聚胺基甲酸乙 酯樹脂中。 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ’以樹脂固成分調整爲5〜65質量％較佳，以調整爲1() 〜60質量％更佳。 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ’由於在常溫下之安定性優異、且具有顯著的感熱凝固性 ’藉由使用對應於天然纖維、合成纖維、無機纖維等之紙 、不織布或編織布等之各種基布而言含浸的含浸液或塗覆 -29- 200949044 的塗覆液，可得匹敵藉由習知的溶劑系 脂組成物之質感、特別是柔軟性及充實 感。 於本發明中，對基布之水系聚胺基 予量，於含浸時對100質量份之基布而 〜1〇〇質量份較佳，於塗覆時以乾燥: 1 0mm較佳。 藉由本發明之人造皮革用水系聚胺 成物所形成的聚胺基甲酸乙酯樹脂被膜 中含浸或塗覆等之方法賦予水系聚胺基 物後，在水系聚胺基甲酸乙酯樹脂組成 以上，藉由熱風、溫水、蒸氣、紅外線 等之加熱處理方法、或組合此等之加熱 熱、製得。加熱溫度以感熱凝固溫度之 未達纖維之脆化溫度較佳。而且，處理 質、厚度、樹脂組成物之含浸或塗覆量 數秒〜數分鐘。爲使本發明之聚胺基甲 特徵發揮至最大極限時，以使用蒸氣、 感熱凝固法較佳，就抑制自基布表面之 以藉由蒸氣之飽和蒸氣中進行加熱處理 藉由本發明之人造皮革用水系聚胺 成物處理的加工布，可使用熱風、紅外 波等之任意乾燥方法進行乾燥。乾燥溫 。乾燥溫度低於80°C時，恐會有水分不 聚胺基甲酸乙酯樹 感與具有韌性之質 甲酸乙酯樹脂的賦 言、以固成分爲5 麦之厚度爲0.1〜 基甲酸乙酯樹脂組 *藉由在上述基布 甲酸乙酯樹脂組成 物之感熱凝固溫度 、電磁波、高周波 處理方法，進行加 1 0 °c以上較佳，以 時間係視基布之材 而不同，通常可爲 酸乙酯樹脂的上述 紅外線、電磁波之 乾燥而言，特別是 更佳。 基甲酸乙酯樹脂組 線、電磁波、高周 度以80°c以上較佳 易蒸發、水系聚胺 200949044 基甲酸乙酯樹脂之造膜性不佳。而且，乾燥溫度以未達纖 維之脆化溫度較佳。 以聚胺基甲酸乙酯樹脂被覆的加工布，可再進行染色 處理。例如基布爲聚酯纖維時，可使用分散染料在125〜 135 °C、30〜90分鐘之條件進行染色處理。而且，經染色 的加工布經由在由鹼劑、還原劑所形成的還原洗淨處理浴 中’以60〜95 °C、1 0〜3 0分鐘進行還原洗淨處理，然後 〇 ’經由在經還原洗淨的染色物中殘留的鹼劑之中和、水洗 、乾燥等步驟。藉由本發明之人造皮革用水系聚胺基甲酸 乙酯樹脂組成物所形成的聚胺基甲酸乙酯樹脂，即使於基 布爲聚酯纖維所形成時之嚴酷的染色及浸潤條件下，仍沒 有容易脫落情形' 可確保作爲人造皮革之優異品質。 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ’於製作使用習知溶劑系聚胺基甲酸乙酯樹脂製作的各種 用途之人造皮革、例如鞋子、靴子、衣料、椅子或沙發椅 © 等家具、車輛座椅或方向盤等之汽車用內裝材料、透濕防 水原料等所使用的各種合成皮革時極爲有用。而且，本發 明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物，作爲硏 磨材料、色筆之芯材等處理劑極爲有用。 【實施方式】 [實施例] 於下述中，藉由實施例說明本發明。本發明不受實施 例所限制。而且，實施例中之「份」係表示「質量份」。 -31 - 200949044 而且，下述合成例1〜11中，固成分之比例（質量係 在試驗盤中量取5g試料溶液，在i〇5°C2乾燥機[塔拜耶 斯貝谷（譯音）（股）、伯菲谷頓（譯音）烤箱PV-210] 中放置3小時後’計量所殘餘的固成分、求取。而且，下 述之合成例7-11中，重量平均分子量係使用凝膠滲透色 譜[東曹（股），HLC-8 020GPC]測定，藉由聚乙烯醇換算 得到。而且，柱係倂用TSK gel G5000PW[東曹（譯音） (股）]與G30 00PW[東曹（股）]，使用磷酸緩衝液（ 0.025 莫耳）/L 之 Na2HP04.12H20 及 0.025 莫耳/L 之 KH2P〇4 )、流量爲1 .OmL/min予以溶出。 [水系聚胺基甲酸乙酯樹脂之合成例] 合成例1(感熱凝固型水系聚胺基甲酸乙酯樹脂（a)) 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之1，6-己二醇聚碳酸酯多醇（ 平均分子量1，〇〇〇) 、16.9份之聚氧化乙烯聚丙烯無規共 聚物乙二醇（平均分子量1，〇〇〇、氧化乙烯基之含有量70 %)、1.5份之1,4-丁二醇、1.9份三羥甲基丙烷、0.001 份二丁基錫二月桂酸鹽及60份甲基乙酮，予以均勻混合 後，加入40.4份二環己基甲烷二異氰酸酯，在75 °C下進 行反應300分鐘，製得對固成分而言自由基異氰酸酯基含 有量爲1.7質量％之聚胺基甲酸乙酯預聚物之甲基乙酮溶 液°使該溶液在30 °C以下予以冷卻後’添加0·1份癸基憐 酸酯及6.0份聚氧化乙烯三苯乙烯基苯醚（HLB = 15) ’ 200949044 予以均勻混合後，移至別容器中，慢慢地加入2 5 4份水， 使用分散翼進行轉相乳化、分散，於其中添加1 1. 3份在 水中溶解有2 · 0份哌嗪與〇 · 8份二乙三胺之聚胺水溶液， 進行攪拌90分鐘，製得聚胺基甲酸乙酯樹脂水分散液。 藉由使所得的聚胺基甲酸乙酯樹脂分散液，再於減壓、 3 5°C下進行脫溶劑處理，製得固成分3 5.0 %、黏度 5(K0mPa.s(BM黏度計、1號滾筒、6 0rpm )、平均粒徑 ❹ 爲0.52 m之安定的感熱凝固型水系聚胺基甲酸乙酯樹脂 (以下稱爲樹脂A)。該水系聚胺基甲酸乙酯樹脂之感熱 凝固溫度爲45 °C，使其乾燥被膜的軟化溫度爲195 °C。 合成例2(感熱凝固型水系聚胺基甲酸乙酯樹脂（b)) 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之聚四甲二醇（平均分子量 1,000 )、16.9份之聚氧化乙烯聚丙烯無規共聚物乙二醇 ❹ （平均分子量1，000、氧化乙烯基之含有量70質量％ )、 1.5份之1，4-丁二醇、1.9份三羥甲基丙烷、0.001份二丁 基二月桂酸錫鹽及60.0份甲基乙酮，予以均勻混合後， 加入40.4份二環己基甲烷二異氰酸酯，在75°C下進行反 應3 00分鐘，製得對不揮發成分而言自由基異氰酸酯基含 有量爲1.7質量％之聚胺基甲酸乙酯預聚物之甲基乙酮溶 液。使該溶液在30°C以下予以冷卻後，添加0.1份癸基磷 酸酯及6.0份聚氧化乙烯三苯乙烯基苯醚（HLB = 15) ’ 予以均勻混合後，移至別容器中，慢慢地加入254.0份水 -33- 200949044 ，使用分散翼進行轉相乳化、分散，於其中添加1 1. 3份 在水中溶解有2.0份哌嗪與〇.8份二乙三胺之聚胺水溶液 ，進行攪拌90分鐘，製得聚胺基甲酸乙酯樹脂水分散液 。藉由使所得的聚胺基甲酸乙酯樹脂分散液，再於減壓、 35 °C下進行脫溶劑處理，製得固成分 35.0%、黏度 45mPa · s ( BM黏度計、1號滾筒、30rpm)、平均粒徑爲 〇· 34 # m之安定的感熱凝固型水系聚胺基甲酸乙酯樹脂（ 以下稱爲樹脂B)。該水系聚胺基甲酸乙酯樹脂之感熱凝 固溫度爲60°C，使其乾燥被膜的軟化溫度爲185°C。 合成例3 (感熱凝固型水系聚胺基甲酸乙酯樹脂（a)) 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之1，6-己二醇聚碳酸酯多醇（ 平均分子量1，000 ) 、16.9份之聚氧化乙烯聚丙烯無規共 聚物乙二醇（平均分子量1,000、氧化乙烯基之含有量70 %)、1.5份之1，4 -丁二醇、1.9份三羥甲基丙烷、0.001 份二丁基二月桂酸錫鹽及52.4份甲基乙酮，予以均勻混 合後，加入25.9份己烷二異氰酸酯，在75 °C下進行反應 3〇〇分鐘，製得對固成分而言自由基異氰酸酯基含有量爲 1.9質量％之聚胺基甲酸乙酯預聚物之甲基乙酮溶液。使 該溶液在30°C以下予以冷卻後，添加0.1份癸基磷酸酯及 6.0份聚氧化乙烯三苯乙烯基苯醚（HLB = 15)，予以均勻 混合後’移至別的容器中，慢慢地加入254份水，使用分 散翼進行轉相乳化、分散，於其中添加1 1 · 3份在水中溶 -34- 200949044 解有2·0份哌嗪與0.8份二乙三胺之聚胺水溶液，進行攪 拌90分鐘，製得聚胺基甲酸乙酯樹脂水分散液。再於減 壓、35 °C下進行脫溶劑處理，製得固成分35.0%、黏度 60.0mPa.s(BM黏度計、1號滾筒、60rpm)、平均粒徑 〇.61/zm之安定的感熱凝固型水系聚胺基甲酸乙酯樹脂（ 以下稱爲樹脂C)。該水系聚胺基甲酸乙酯樹脂之感熱凝 固溫度爲62°C，使其乾燥被膜的軟化溫度爲130°C。 合成例4(感熱凝固型水系聚胺基甲酸乙酯樹脂（a)) 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之1,6-己二醇聚碳酸酯多醇（ 平均分子量1，〇〇〇) 、16.9份之聚氧化乙烯聚丙烯無規共 聚物乙二醇（平均分子量1，000、氧化乙烯基之含有量7〇 % )、1.5份之1，4-丁二醇、1.9份三羥甲基丙烷、0.001 份二丁基二月桂酸錫鹽及60份甲基乙酮，予以均勻混合 Φ 後，加入40.4份二環己基甲烷二異氰酸酯，在75°C下進 行反應3 00分鐘，製得對固成分而言自由基異氰酸酯基含 有量爲1.7質量％之聚胺基甲酸乙酯預聚物的甲基乙酮溶 液。使該溶液在30°C以下予以冷卻後，添加0.1份癸基磷 酸酯及6.0份聚氧化乙烯三苯乙烯基苯醚（HLB=15)， 予以均勻混合後，移至別的容器中，慢慢地加入254份水 ，使用分散翼進行轉相乳化、分散，於其中添加11.3份 在水中溶解有2.0份哌嗪與0_8份二乙三胺之聚胺水溶液 ，進行攪拌90分鐘，製得聚胺基甲酸乙酯樹脂水分散液 -35- 200949044 。再於減壓、35 °C下進行脫溶劑處理’添加1質量％比谷 新（譯音）AG-2 5 (日華化學（股）製陰離子界面活性劑 )，固成分35.0%、黏度50.0mPa.s(BM黏度計、1號 滾筒、6 0rpm)、平均粒徑〇_52"m之安定的感熱凝固型 水系聚胺基甲酸乙酯樹脂（以下稱爲樹脂D)。該水系聚 胺基甲酸乙酯樹脂之感熱凝固溫度爲80°C，使其乾燥被膜 的軟化溫度爲195°C。 合成例5(感熱凝固型水系聚胺基甲酸乙酯樹脂（a)) 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之1，6-己二醇聚碳酸酯多醇（ 平均分子量1，〇〇〇) '16.9份之聚氧化乙烯聚丙烯無規共 聚物乙二醇（平均分子量1,000、氧化乙烯基之含有量70 質量％)、1·5份之1,4-丁二醇、1.9份三羥甲基丙烷、 0.001份二丁基二月桂酸錫鹽及60份甲基乙酮，予以均勻 混合後’加入40.4份二環己基甲烷二異氰酸酯，在75 °C 下進行反應300分鐘，製得對固成分而言自由基異氰酸酯 基含有量爲1.7%之聚胺基甲酸乙酯預聚物之甲基乙酮溶 液。使該溶液在3 0 °C以下予以冷卻後，添加0.1份癸基磷 酸酯及12.0份聚氧化乙烯三苯乙烯基苯醚（HLB=15)， 予以均勻混合後，移至別的容器中，慢慢地加入254份水 ，使用分散翼進行轉相乳化、分散，於其中添加1 1 . 3份 在水中溶解有2.0份哌嗪與〇.8份二乙三胺之聚胺水溶液 ’進行攪拌90分鐘，製得聚胺基甲酸乙酯樹脂水分散液 -36- 2009490440II C -ch2—c—ch2-c- c-IIο •ο Ρ (II) (wherein ρ is a degree of polymerization) Further, poly-α-hydroxyacrylic acid can also be obtained by high molecular weight poly-α- 21 - 200949044 Oxidative depolymerization and production of hydroxyacrylic acid, poly-α-hydroxy acrylate, etc. The metal and/or amine salt of poly-α-hydroxy acrylate may also be obtained by oxidatively depolymerizing a high molecular weight poly-α-hydroxy acrylate or poly-α-hydroxy acrylate, etc., by an alkali metal salt. The hydroxide and the water-soluble amine are neutralized and produced. Alkali metal salts of polymers such as lithium salts, sodium salts, potassium salts. Further, the amine salt of the polymer is, for example, an ammonium salt, a triethylamine salt, a butylamine salt, a dibutylamine salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt or the like. These salts are obtained by, for example, hydrolyzing a polylactone compound corresponding to the poly-α-hydroxyacrylic acid represented by the above formula (Π) using an aqueous sodium hydroxide solution, triethylamine or triethanolamine. In the salt of the polymer, two or more kinds of the above-mentioned salts may be contained, and when the salt of the polymer is a salt of a polyvalent ion such as an alkaline earth metal salt or a heavy metal salt (for example, Fe 2+ , Fe 3 + or the like), the insoluble property The salt remains in the thermosetting cohesive polyurethane resin film, and there is a possibility that the quality of the artificial leather is impaired and the resin strength is lowered, so that it is not desirable. (2) The weight average molecular weight of the polymer exemplified is preferably from 5 Å to 1,000,000, more preferably from 1,000 to 150,000. When the average molecular weight of the polymer is less than 50,000, it is difficult to obtain a sufficient effect of preventing migration. When the weight average molecular weight of the polymer is more than 1,000, in the case of ruthenium, the polyurethane resin film may become poor in water resistance and alkali resistance, and may be liable to fall off during dyeing or washing. (3) The exemplified polymer may be selected from the group consisting of acrylic acid, methyl-22-200949044 acrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal of maleic acid At least one monomer grouped with a salt, an amine salt of an acrylic acid, an amine salt of methacrylic acid and an amine salt of maleic acid, and a group selected from the group consisting of poly-α-hydroxy acrylic acid and an alkali metal and/or amine salt thereof At least one polymer obtained by radical polymerization, an alkali metal and/or an amine salt of the polymer 'mixed polymerized monomer in an aqueous solution containing poly-α-hydroxyacrylic acid or a salt thereof' and added by radical polymerization initiation a method of reacting at 50 to 90 ° C for 2 Torr to 10 hours to carry out a reaction, or adding a radical polymerization initiator to an aqueous solution containing poly-α-hydroxyacrylic acid or a salt thereof, and dropping the polymerized monomer 'It is obtained by heating at 50 to 90 ° C for 2 to 10 hours. In this case, an alcohol such as methanol, ethanol or isopropyl alcohol or a water-miscible solvent such as acetone may be added to the aqueous solution containing poly-α-hydroxyacrylic acid or a salt thereof. The radical polymerization initiator to be used is not particularly limited, and for example, a combination of a persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, a redox initiator such as a persulfate or sodium metabisulfite, or hydrogen peroxide, Water-soluble azo® initiator, etc. These radical polymerization initiators may be used alone or in combination of two or more. The amount of the radical polymerization initiator to be used is preferably 0.1 to 1.0 part by mass based on 100 parts by mass of the total of the monomers which are radically polymerized with the poly-α-hydroxyacrylic acid and/or a salt thereof. Further, in the case of radical polymerization, a chain shifting agent such as octyl thiolate may be added to adjust the degree of polymerization. An alkali metal salt of acrylic acid, methacrylic acid and maleic acid, such as a lithium salt, a sodium salt, a potassium salt or the like. Further, an amine salt of acrylic acid, methacrylic acid or maleic acid, for example, an ammonium salt, a triethylamine salt, a butylamine salt, a dibutylamine salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt or the like. Further, when the above polymer is -23-200949044, when it has a radical, some or all of its carboxyl group is neutralized by an alkali metal and/or an amine, and an alkali metal and/or an amine salt of the above polymer can be obtained. Metals such as lithium, sodium, potassium, etc. are examined. Further, for example, ammonium, triethylamine, butylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine or the like. Further, an alkali metal salt selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid, and horse The at least one monomer grouped with the acid amine salt is polymerized with at least one selected from the group consisting of poly-hydroxy acrylic acid and its alkali metal ◎ and/or amine salt, and the present inventors consider grafting by grafting. Aggregator. In the case of radical polymerization, other monomers may be copolymerized in addition to the above monomers insofar as the effects of the present invention are not impaired. Copolymerizable monomers such as fumaric acid, itaconic acid, ethylene, vinyl chloride, vinyl acetate, acrylamide, acrylate, methacrylate, and the like. (3) The weight average molecular weight of the polymer exemplified is preferably from 500 to 1,000,000, more preferably from 1,000 to 150,000. The weight of the polymer 0 When the average molecular weight is less than 500, there is a tendency that it is difficult to obtain a sufficient effect of preventing migration. When the weight average molecular weight of the polymer is more than 1, when the ruthenium or osmium is changed, the polyurethane resin film becomes poor in water resistance and alkali resistance, and there is a fear that it may fall off easily during dyeing or washing. . The polymer of the above (2) and (3) may be directly mixed with water or a solution of a mixed solvent of water and a water-miscible solvent such as a lower alcohol or acetone, and may contain a thermosetting type aqueous polyaminocarboxylic acid. It is used as an aqueous dispersion of a polyurethane resin of the ethyl ester resin (a). The polymer of the above (2) and (3) -24 - 200949044 has a strong affinity with the amine group or the imine group of the chain elongation group of the thermosetting type aqueous polyurethane resin (a). It has good compatibility with a thermosensitive solidified aqueous polyurethane resin, and can be suitably used as the water-soluble acrylic polymer (b). A commercially available product can be used for the water-soluble acrylic polymer (b). Commercial products such as Yaguyari Valley (transliteration) DL, TL, HL, manufactured by Nippon Shokubai Co., Ltd., Girima (transliteration) AC-10NP, manufactured by Nippon Pure Chemical Co., Ltd. Yalong (transliteration) A-210, T-50, A-10SL, A-30SL, A-20UN, A-20L, A-6520, Chiba • Japan (share) BELCLENE 200LA and so on. The amount of the water-soluble acrylic polymer (b) is, in terms of a solid content ratio, to 100 parts by mass of the thermosensitive solidified aqueous polyurethane resin (a), the water-soluble acrylic polymer (b) 0.1 to 40 parts by mass is more preferably 0.5 to 20 parts by mass. When the amount of the water-soluble acrylic polymer (b) is less than 0.1 part by mass per 100 parts by mass of the thermosensitive solidified aqueous urethane resin (a), it is difficult to obtain a sufficient water system. The tendency of the polyurethane resin composition to prevent migration. In addition, when the amount of the water-soluble acrylic polymer (b) is more than 40 parts by mass per 1 part by mass of the thermosetting type aqueous polyurethane resin (a), there is a polyaminocarbamate The water resistance of the ester resin film is lowered, and the texture of the artificial leather tends to be hard. The artificial leather water-based polyurethane resin composition of the present invention can be obtained by using the above-mentioned thermosetting water-based polyurethane resin (a) and water-soluble acrylic polymer (b). The thermosensitive solidified water-25-200949044 is a polyurethane resin which is uniformly mixed at a low temperature and has a more sensitive temperature. Further, the artificial leather of the present invention is a water-based polyurethane resin composition, and may be added to a water-soluble acrylic polymer during the manufacture of the thermosetting water-based polyurethane resin (a). The substance (b) is prepared. In the water-based polyurethane resin composition of the artificial leather of the present invention, the heat-curable water-based polyurethane resin (a) and the water-soluble acrylic polymer (b) are not damaged. Within the scope of the effects of the present invention, it may be added as another aqueous dispersion or aqueous dispersion, for example, an emulsion of vinyl acetate, ethylene vinyl acetate, acrylic or styrene acrylate; styrene butadiene Latex, acrylonitrile, butadiene, acrylic acid, butadiene, etc.; ionic polymers such as polyethylene or polyolefin; polyurethane, polyester, polyamide, epoxy Various aqueous dispersions such as resins and aqueous dispersions. These may be used alone or in combination of two or more. Further, these aqueous dispersions or aqueous dispersions may be added to the thermosensitive solidified aqueous polyurethane resin (a) and/or the water-soluble acrylic polymer (b), or may be added thereto. A thermosetting type aqueous polyurethane resin (a) and a water-based acrylic polymer (b) aqueous polyurethane resin composition. Further, in the water-based polyurethane resin composition of the artificial leather of the present invention, in order to effectively absorb the vapor absorbent, for example, urea, protein, or the like may be added to the extent that the effect of the present invention is not impaired. Glycerol, polyethylene oxide nonionic surfactant. These may be used alone or in combination of two or more. Further, such a moisture absorbent may be added to the thermosetting type water--26-200949044-based polyurethane resin (a) and/or the water-soluble acrylic acid-based polymer (b). The aqueous polyurethane resin composition containing the thermosensitive solidified aqueous polyurethane resin (a) and the water-soluble acrylic polymer (b). Further, 'in the water-based polyurethane resin composition of the artificial leather of the present invention', the sensible heat of the thermosensitive solidified water-based polyurethane resin (a) is lowered within a range that does not impair the effects of the present invention. For the purpose of setting the solidification temperature φ, for example, sodium telluride, barium fluoride, hydrochloric acid, nitric acid, sulfuric acid, ammonium phosphate, sodium, potassium, calcium, magnesium, zinc, antimony, nickel, tin, lead, iron and aluminum may be added. Multivalent metal salts; convergent tackifiers, basic tackifying polymers, polyether thioether glycols, polyether modified polydimethylsiloxanes; alkylphenols A thermosetting coagulant such as an oxyalkylene adduct of a formaldehyde condensate. These may be used alone or in combination of two or more. Further, these thermosensitive coagulants may be added to the thermosetting coagulating water-based polyurethane resin (a) and/or the water-soluble acrylic polymer (b). The aqueous urethane resin composition of the urethane resin (a) and the water-soluble acrylic polymer (b). Further, 'in the artificial leather of the present invention, the water-based polyurethane resin composition' can be blended with an alkanediol derivative, or a dialkyl ester of an aliphatic dicarboxylic acid, and N- for the purpose of improving film formation. For the purpose of improving the processing suitability, the film-forming auxiliary agent such as methylpyrrolidone can be blended with various levels of a fluorine-based level agent, a dialkyl sulfosuccinate-based emulsifier, an acetylene alcohol derivative, and a penetrating agent. Wait. Further, in the composition of the artificial leather of the present invention, the water-based polyamine -27-200949044 ethyl formate resin composition can be used for the purpose of imparting workability by mechanical foaming, and can be combined with ammonium stearate and a metal of a higher fatty acid. A foaming agent such as a salt or a dialkyl sulfosuccinate-based emulsifier. In addition, in the composition of the water-based polyurethane resin of the artificial leather of the present invention, in order to suppress the foaming of the compounding liquid, various materials such as mineral oil, guanamine, or polyoxygen can be blended. Defoamer or a small amount of alcohol such as ethanol or isopropanol. Further, in the water-based polyurethane resin composition of the artificial leather of the present invention, various inorganic or organic pigments which are water-soluble or water-dispersible can be blended for the purpose of coloring, and calcium carbonate and talc can be blended. An inorganic chelating agent such as aluminum hydroxide, cerium oxide or glass fiber, or an organic chelating agent such as cellulose powder, protein powder, silk powder or organic short fiber. Further, in the artificial polyurethane water-based polyurethane resin of the present invention, in order to improve the various durability of the water dispersion, such as light resistance, heat resistance, water resistance, solvent resistance, etc. An oxidizing agent, a UV absorber, a stabilizer for preventing a hydrolyzing agent, and the like. These stabilizers may also be added in the production step of the aqueous polyurethane resin or after its manufacture. Further, in the water-based polyurethane resin composition of the artificial leather of the present invention, an epoxy resin, a melamine resin, an isocyanate compound, an acridine compound, a polycarbonyldiamine compound, or an oxazoline compound may be blended. Such as crosslinkers. In the composition of the artificial leather water-based polyurethane resin of the present invention, it is possible to blend various additives for imparting workability without departing from the effects of the present invention. The additive is, for example, an alcohol-based nonionic interface active -28-200949044 agent, an ethynyl alcohol-based special surfactant, a fatty acid salt, an alkyl sulfate salt, an alkylbenzene sulfate, an alkyl sulfosuccinate, a naphthalene sulfate Anionic emulsifier such as salt, alkane sulfonate sodium salt, alkyl diphenyl ether sulfate salt; nonionic nonionic anion such as polyoxyethylene alkyl sulfate or polyoxyethylene alkyl phenyl sulfate Emulsifier, polyoxonated surfactant, fluorine level surfactant; various stabilizers such as antioxidants, light stabilizers, UV inhibitors; mineral oils, polyfluorenes, etc. Various defoaming agents; coloring agents such as polyurethane catalyzed catalysts, plasticizers, pigments, etc., and time extension agents. These may be used alone or in combination of two or more. The above additive may be added during or after the production of the thermosetting type aqueous polyurethane resin (a), or the thermosetting type aqueous polyurethane resin (a) and the water-soluble acrylic polymer may be added. (b) Adding and mixing together during mixing. It is also possible to add a thermosetting type water-based polyurethane resin (a) and a water-soluble acrylic polymer (b) containing an impregnation liquid or a coating liquid as an artificial leather. The water is in the polyurethane resin. The water-based polyurethane resin composition of the artificial leather of the present invention is preferably adjusted to have a resin solid content of 5 to 65 mass%, more preferably adjusted to 1 () to 60 mass%. The water-based polyurethane resin composition of the artificial leather of the present invention is excellent in stability at normal temperature and has remarkable thermocoagulation property by using paper corresponding to natural fibers, synthetic fibers, inorganic fibers, and the like. An impregnation solution impregnated with various base fabrics such as non-woven fabrics or woven fabrics or a coating liquid coated with -29-200949044, which is superior to the texture, particularly softness and enrichment of the conventional solvent-based fat composition. sense. In the present invention, the amount of the aqueous polyamine group of the base fabric is preferably from 1 part by mass to 100 parts by mass of the base fabric when impregnated, and is preferably dried at the time of coating: 10 mm. The polyurethane-based resin formed from the water-based polyamine product of the artificial leather of the present invention is impregnated or coated with a film to impart an aqueous polyamine-based material, and is then composed of an aqueous polyurethane resin. It is obtained by a heat treatment method such as hot air, warm water, steam, infrared rays, or the like, or a combination of heating heat. The heating temperature is preferably at a temperature at which the heat is solidified, and the embrittlement temperature of the fiber is not reached. Further, the treatment, the thickness, and the impregnation or coating amount of the resin composition are several seconds to several minutes. In order to maximize the polyamine-based characteristics of the present invention, it is preferred to use a vapor or a thermosensitive coagulation method to suppress the heat treatment in the saturated vapor by vapor from the surface of the base fabric by the artificial leather of the present invention. The processed cloth treated with the water-based polyamine product can be dried by any drying method such as hot air or infrared wave. Dry and warm. When the drying temperature is lower than 80 °C, there is a fear that the moisture is not urethane and the toughness of the ethyl urethane resin, and the solid content is 5 gram of the thickness of 0.1 gram of ethyl urethane. The resin group* is preferably added at a temperature of 10 ° C or more by a thermosensitive solidification temperature, an electromagnetic wave, or a high-frequency treatment method of the ethyl benzoate resin composition of the base fabric, and the time is different depending on the material of the base fabric, and usually The above-mentioned infrared ray and electromagnetic wave drying of the acid ethyl ester resin are particularly preferable. The ethyl urethane resin line, electromagnetic wave, high temperature is preferably 80 ° C or more, easy to evaporate, water-based polyamine 200949044 urethane resin has poor film-forming properties. Moreover, the drying temperature is preferably such that the embrittlement temperature of the fiber is not reached. The processed cloth coated with the polyurethane resin can be further dyed. For example, when the base fabric is a polyester fiber, it can be dyed using a disperse dye at 125 to 135 ° C for 30 to 90 minutes. Further, the dyed processed cloth is subjected to reduction washing treatment at 60 to 95 ° C for 10 to 30 minutes in a reduction washing treatment bath formed of an alkali agent and a reducing agent, and then passed through The steps of neutralizing, washing with water, drying, and the like of the alkali agent remaining in the washed dyeing matter are reduced. The polyurethane resin formed by the water-based polyurethane resin composition of the artificial leather of the present invention does not have any severe dyeing and wetting conditions when the base fabric is formed of a polyester fiber. Easy to fall off' ensures excellent quality as artificial leather. The artificial leather of the present invention is a polyurethane-based resin composition for making various uses of the conventional solvent-based polyurethane resin, such as shoes, boots, clothes, chairs or armchairs. © It is extremely useful when it comes to various synthetic leathers used in automotive interior materials such as furniture, vehicle seats or steering wheels, and moisture-permeable waterproof materials. Further, the artificial leather water-based polyurethane resin composition of the present invention is extremely useful as a treatment agent for a honing material or a core material for a color pen. [Embodiment] [Examples] Hereinafter, the present invention will be described by way of examples. The invention is not limited by the examples. Moreover, the "parts" in the examples mean "parts by mass". -31 - 200949044 Moreover, in the following Synthesis Examples 1 to 11, the ratio of the solid components (the mass is 5 g of the sample solution in the test tray, and the dryer at i〇 5 ° C 2 [Taibayes Bay Valley (transliteration)) In the following, in the following synthesis examples 7-11, the weight average molecular weight is a gel, and the residual solid content of the sample is measured after being placed for 3 hours in the Bofe Gutton oven (PV-210). Permeation chromatography [Dongcao (share), HLC-8 020GPC] was determined by conversion of polyvinyl alcohol. Moreover, the column system was TSK gel G5000PW [Dong Cao] and G30 00PW [Dong Cao ( ()), using phosphate buffer (0.025 mol) / L of Na2HP04.12H20 and 0.025 mol / L of KH2P 〇 4), flow rate of 1.0 mL / min for dissolution. [Synthesis Example of Water-Based Polyurethane Resin] Synthesis Example 1 (Thermal-coagulation type water-based polyurethane resin (a)) A four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1, 〇〇〇), 16.9 parts of polyethylene oxide polypropylene random copolymer ethylene glycol (average molecular weight 1, 〇〇 〇, oxidized vinyl content 70%), 1.5 parts of 1,4-butanediol, 1.9 parts of trimethylolpropane, 0.001 parts of dibutyltin dilaurate and 60 parts of methyl ethyl ketone, uniformly mixed Thereafter, 40.4 parts of dicyclohexylmethane diisocyanate was added, and the reaction was carried out at 75 ° C for 300 minutes to obtain a polyurethane-based prepolymer having a radical isocyanate group content of 1.7% by mass based on the solid content. Methyl ethyl ketone solution ° After cooling the solution below 30 °C, 'add 0·1 part of thiol-acid ester and 6.0 parts of polyoxyethylene tristyrylphenyl ether (HLB = 15) ' 200949044 After that, move to another container and slowly add 2 5 4 parts of water. The wing was subjected to phase inversion emulsification and dispersion, and 11.1 parts of a polyamine aqueous solution in which 2.0 parts of piperazine and 8 parts of diethylenetriamine were dissolved in water was added thereto, and stirred for 90 minutes to obtain a polyamine group. An aqueous dispersion of ethyl formate resin. The obtained polyurethane resin dispersion was subjected to solvent removal treatment under reduced pressure at 35 ° C to obtain a solid component of 35.0% and a viscosity of 5 (K0mPa.s (BM viscosity meter, 1). No. roller, 60 rpm, and a thermosensitive solidification type aqueous polyurethane resin (hereinafter referred to as Resin A) having an average particle diameter ❹ of 0.52 m. The thermal solidification temperature of the aqueous polyurethane resin is The softening temperature of the dried film was 195 ° C at 45 ° C. Synthesis Example 2 (Thermal solidification type water-based polyurethane resin (b)) was equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube. In a four-necked flask, 76.1 parts of polytetramethylene glycol (average molecular weight of 1,000) and 16.9 parts of a polyoxyethylene polypropylene random copolymer ethylene glycol oxime (average molecular weight 1,000, oxyethylene content 70) were added. (% by mass), 1.5 parts of 1,4-butanediol, 1.9 parts of trimethylolpropane, 0.001 part of dibutyltin dilaurate and 60.0 parts of methyl ethyl ketone, uniformly mixed, and then added 40.4 parts Cyclohexylmethane diisocyanate was reacted at 75 ° C for 3 000 minutes to obtain a pair a methyl ethyl ketone solution of a polyethyl methacrylate prepolymer having a radical isocyanate group content of 1.7% by mass in terms of a volatile component. After cooling the solution at 30 ° C or lower, 0.1 part of decyl phosphate is added. And 6.0 parts of polyoxyethylene tristyrylphenyl ether (HLB = 15) 'to be uniformly mixed, transferred to another container, slowly added 254.0 parts of water -33- 200949044, using phased emulsification, dispersion 1 . 3 parts of a polyamine aqueous solution in which 2.0 parts of piperazine and 8 parts of diethylenetriamine were dissolved in water were added thereto, and the mixture was stirred for 90 minutes to obtain an aqueous polyurethane resin dispersion. The obtained polyurethane resin dispersion was subjected to solvent removal treatment under reduced pressure at 35 ° C to obtain a solid component of 35.0% and a viscosity of 45 mPa·s (BM viscometer, No. 1 roller, 30 rpm). a thermosensitive solidified water-based polyurethane resin having an average particle diameter of 〇·34 #m (hereinafter referred to as Resin B). The water-based polyurethane resin has a thermosensitive solidification temperature of 60 ° C. The softening temperature of the dried film was 185 ° C. Synthesis Example 3 (Sense Solidified water-based polyurethane resin (a)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol was added. (average molecular weight: 1,000), 16.9 parts of polyethylene oxide polypropylene random copolymer ethylene glycol (average molecular weight 1,000, oxyethylene content 70%), 1.5 parts of 1,4-butanediol, 1.9 Part of trimethylolpropane, 0.001 part of dibutyltin laurate and 52.4 parts of methyl ethyl ketone were uniformly mixed, and then 25.9 parts of hexane diisocyanate was added, and the reaction was carried out at 75 ° C for 3 minutes. A methyl ethyl ketone solution of a polyurethane-based prepolymer having a radical isocyanate group content of 1.9% by mass based on the solid content was obtained. After the solution was cooled at 30 ° C or lower, 0.1 part of decyl phosphate and 6.0 parts of polyoxyethylene tristyrylphenyl ether (HLB = 15) were added, uniformly mixed, and then moved to another container, slow. Slowly add 254 parts of water, phase inversion emulsification and dispersion using a dispersion wing, and add 1 1 · 3 parts of it dissolved in water -34- 200949044. Polyamine with 2.0 parts of piperazine and 0.8 part of diethylenetriamine The aqueous solution was stirred for 90 minutes to prepare an aqueous polyurethane resin dispersion. Further, desolvent treatment was carried out under reduced pressure at 35 ° C to obtain a sensible heat of 35.0% solid content, 60.0 mPa·s viscosity (BM viscometer, No. 1 roller, 60 rpm), and an average particle diameter of 61.61/zm. A solidified aqueous polyurethane resin (hereinafter referred to as resin C). The water-based polyurethane resin had a thermotropic condensation temperature of 62 ° C and a softening temperature of the dried film of 130 ° C. Synthesis Example 4 (Thermal solidification type aqueous polyurethane resin (a)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube, 76.1 parts of 1,6-hexanediol was added. Polycarbonate polyol (average molecular weight 1, 〇〇〇), 16.9 parts of polyethylene oxide polypropylene random copolymer ethylene glycol (average molecular weight 1,000, oxyethylene content 7% by weight), 1.5 parts 1,4-butanediol, 1.9 parts of trimethylolpropane, 0.001 part of dibutyl dilaurate tin salt and 60 parts of methyl ethyl ketone, uniformly mixed Φ, then added 40.4 parts of dicyclohexylmethane diisocyanate The reaction was carried out at 75 ° C for 300 minutes to obtain a methyl ethyl ketone solution of a polyurethane-based prepolymer having a radical isocyanate group content of 1.7% by mass. After cooling the solution at 30 ° C or lower, 0.1 part of decyl phosphate and 6.0 parts of polyoxyethylene tristyrylphenyl ether (HLB=15) were added, uniformly mixed, and transferred to another container, slow. Slowly add 254 parts of water, phase inversion emulsification and dispersion using a dispersion wing, and add 11.3 parts of a polyamine aqueous solution in which 2.0 parts of piperazine and 0-8 parts of diethylenetriamine are dissolved in water, and stir for 90 minutes to obtain a poly Amino urethane resin aqueous dispersion -35- 200949044. Further, desolvent treatment was carried out under reduced pressure at 35 °C. Add 1% by mass of gluten-free AG-2 5 (anionic surfactant prepared by Rihua Chemical Co., Ltd.), solid content 35.0%, viscosity 50.0 mPa .s (BM viscometer, No. 1 drum, 60 rpm), a thermosensitive solidified water-based polyurethane resin (hereinafter referred to as Resin D) having an average particle diameter of 52 _52 " m. The water-based polyurethane resin had a thermosensitive solidification temperature of 80 ° C and a softening temperature of the dried film of 195 ° C. Synthesis Example 5 (Thermal coagulation type aqueous polyurethane resin (a)) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube, 76.1 parts of 1,6-hexanediol was added. Polycarbonate polyol (average molecular weight 1, 〇〇〇) '16.9 parts of polyethylene oxide polypropylene random copolymer ethylene glycol (average molecular weight 1,000, oxyethylene content 70% by mass), 1.5 parts 1,4-butanediol, 1.9 parts of trimethylolpropane, 0.001 parts of dibutyltin dilaurate and 60 parts of methyl ethyl ketone, uniformly mixed, and then added 40.4 parts of dicyclohexylmethane diisocyanate. The reaction was carried out at 75 ° C for 300 minutes to obtain a methyl ethyl ketone solution of a polyurethane-based prepolymer having a radical isocyanate group content of 1.7% as a solid component. After cooling the solution at 30 ° C or lower, 0.1 part of decyl phosphate and 12.0 parts of polyoxyethylene tristyrylphenyl ether (HLB=15) were added, uniformly mixed, and transferred to another container. Slowly add 254 parts of water, phase inversion emulsification and dispersion using a dispersion wing, and add 11.3 parts of a polyamine aqueous solution in which 2.0 parts of piperazine and 8 parts of diethylenetriamine are dissolved in water. 90 minutes to prepare a polyurethane dispersion aqueous dispersion -36- 200949044

。再於減壓、35°C下進行脫溶劑處理，製得固成分35.0% 、黏度70.0mpa .S(BM黏度計叫號滾筒、6〇rpm)、平 均粒徑〇.18#m之安定的感熱凝固型水系聚胺基甲酸乙酯 樹脂（以下稱爲樹脂E)。該水系聚胺基甲酸乙酯樹脂之 感熱凝固溫度爲48°C，使其乾燥被膜的軟化溫度爲190°C 〇 合成例6(非感熱凝固型水系聚胺基甲酸乙酯樹脂） 在附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，加入76.1份之1,6-己二醇聚碳酸酯多醇（ 平均分子量1，000 ) 、16.9份之聚氧化乙烯聚丙烯無規共 聚物乙二醇（平均分子量1，000、氧化乙烯基之含有量70 質量％) 、1_5份之1，4-丁二醇、1.9份三羥甲基丙烷、 0.001份二丁基二月桂酸錫鹽及60份甲基乙酮，予以均勻 混合後，加入40.4份二環己基甲烷二異氰酸酯，在751 φ 下進行反應3 00分鐘，製得對固成分而言自由基異氰酸酯 基含有量爲1.7質量％之聚胺基甲酸乙酯預聚物之甲基乙 酮溶液。使該溶液在3 0 °C以下予以冷卻後’添加〇.1份癸 基磷酸酯及6.0份聚氧化乙烯三苯乙烯基苯醚（HLB= 15 )，予以均勻混合後’移至別的容器中’慢慢地加入2 5 4 份水，使用分散翼進行轉相乳化、分散，於其中添加1 1 ·3 份在水中溶解有2.0份哌嗪與〇.8份二乙三胺之聚胺水溶 液，進行攪拌90分鐘’製得聚胺基甲酸乙醋樹脂水分散 液。再於減壓、35 °C下進行脫溶劑處理’添加3質量％比 -37- 200949044 谷新AG-2 5 (日華化學（股）製陰離子界面活性劑），製 得固成分35.0%、黏度50_0mPa.s(BM黏度計、1號滾 筒、60rPm)、平均粒徑0.52jam之安定的感熱凝固型水 系聚胺基甲酸乙酯樹脂（以下稱爲比較樹脂A)。該水系 聚胺基甲酸乙酯樹脂之感熱凝固溫度爲1〇〇。(：，使其乾燥 被膜的軟化溫度爲1 9 5 °C。 [水溶性丙烯酸系聚合物（b)之合成例] _ © 合成例7 (水溶性丙烯酸系聚合物（b):聚-α-羥基丙烯 酸鈉） 在具備攪拌機、回流冷卻管及溫度計之四口燒瓶中， 加入5 8 8.0份水及ι50·〇份之48質量％氫氧化鈉水溶液 ’攪拌至均勻爲止。昇溫至50°C後，加入150.0份對應 聚- £Z-羥基丙烯酸之聚內酯化合物（重量平均分子量 1 00,000 ) ’昇溫至70°C。昇溫後，在70〜75°C下進行反 應3小時，製得聚-α -羥基丙烯酸鈉（以下稱爲化合物a Q )之水溶液。該水溶液之黏度爲200mPa · s，固成分爲 25.1%，固成分之聚-α -羥基丙烯酸鈉的重量平均分子量 爲 100,000 〇 合成例8(水溶性丙烯酸系聚合物（b):聚-α-羥基丙烯 酸鈉-丙烯酸鈉） 在具備攪拌機、回流冷卻管及溫度計之四口燒瓶中， 加入163.0份之40質量％之聚-α-羥基丙烯酸鈉（重量平 -38- 200949044 均分子量100,000)水溶液及127.0份水。昇溫至80 °C後 ’在45分鐘內滴入150份之40質量％丙烯酸鈉水溶液， 再添加5份過硫酸鈉。於添加後，在80〜90 °C下進行反應 3小時’然後，加入5 5 5份之6 0 °C之溫水後，予以冷卻， 製得聚-α-羥基丙烯酸鈉-丙烯酸鈉之聚合物（以下稱爲 化合物Β)之水溶液。該水溶液之黏度爲150mPa · s，固 成分爲12.5%，固成分之聚合物的重量平均分子量約爲 〇 20,000 。 合成例9 (水溶性丙烯酸系聚合物（b ):聚-α -羥基丙烯 酸三乙胺鹽） 在具備攪拌機、回流冷卻管及溫度計之四口燒瓶中， 加入180.0份之40質量％亞龍α-IOSL (東亞合成股份有 限公司製、聚丙烯酸水溶液、重量平均分子量6,000)水 溶液及295.7份水。在45分鐘內滴入101.0份三乙胺， Ο 在30〜4(TC下攪拌3小時後，予以冷卻，製得聚丙烯酸三 乙胺鹽（以下稱爲化合物C)之水溶液。該聚合物之黏度 爲80mPa.s，固成分爲30.0%。 合成例1〇(水溶性丙烯酸系聚合物（b):聚丙烯酸三乙 醇胺鹽） 在具備攪拌機、回流冷卻管及溫度計之四口燒瓶中， 加入180.0份之40質量％亞龍a-1〇SL (東亞合成股份有 限公司製、聚丙烯酸水溶液、重量平均分子量6,000 )水 -39- 200949044 溶液及233.88份水。在45分鐘內滴入74.5份二乙醇胺 ，在30〜40。0下進行反應3小時後，予以冷卻’製得聚丙 烯酸三乙醇胺鹽（以下稱爲化合物D)之水溶液。該聚合 物水溶液之黏度爲15〇mpa_s，固成分爲30.0%。 [會合型增黏劑之合成例] 合成例11 (會合型增黏劑） 在具備攪拌機、回流冷卻管及溫度計之四口燒瓶中’ 加入800.0份之分子量4,000的聚乙二醇、230.8份三苯 乙烯化苯酚之氧化乙烯17莫耳加成物，在減壓、105 °C下 進行脫水處理後，加入50.4份六亞甲基二異氰酸酯，使 在80〜90 °C下進行反應5小時者溶解於540.6份水中，製 得聚胺基甲酸乙酯系會合型增黏劑（以下稱爲會合型增黏 劑A)。該聚合物水溶液之黏度爲6000rnPa.s，固成分爲 20.0%。 (實施例1 ) 使5 7.1份以合成例丨所得的樹脂a (水系聚胺基甲 酸乙酯樹脂）、1 0.0份以合成例7所得的化合物A (水溶 性丙烯酸系聚合物）之1 〇質量％水溶液、以及3 2.9份稀 釋水予以混合’調製水系聚胺基甲酸乙酯樹脂組成物。該 水系聚胺基甲酸乙酯樹脂組成物之各成分的固成分比，係 樹脂A/化合物A= 1〇〇份/5份’水系聚胺基甲酸乙酯樹脂 組成物固成分爲21質量％。使該水系聚胺基甲酸乙酯樹 -40- 200949044. Further decompression treatment at 35 ° C under reduced pressure, to obtain a solid content of 35.0%, viscosity of 70.0mpa.S (BM viscosity meter called roller, 6 rpm), average particle size 〇.18#m stability A thermosensitive solidification type aqueous polyurethane resin (hereinafter referred to as resin E). The water-based polyurethane resin has a thermosensitive solidification temperature of 48 ° C, and the softening temperature of the dried film is 190 ° C. 〇 Synthesis Example 6 (non-heat-sensitive solidified water-based polyurethane resin) In a four-necked flask of a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight of 1,000) and 16.9 parts of polyethylene oxide polypropylene were added. Copolymer ethylene glycol (average molecular weight 1,000, oxyethylene content 70% by mass), 1-5 parts of 1,4-butanediol, 1.9 parts of trimethylolpropane, 0.001 part of dibutyl lauric acid After uniformly mixing the acid tin salt and 60 parts of methyl ethyl ketone, 40.4 parts of dicyclohexylmethane diisocyanate was added, and the reaction was carried out at 751 φ for 300 minutes to obtain a free radical isocyanate group content for the solid component. A methyl ethyl ketone solution of a 1.7% by mass of a polyurethane prepolymer. After the solution was cooled at 30 ° C or lower, 'add 1 part of thiol phosphate and 6.0 parts of polyoxyethylene tristyrylphenyl ether (HLB= 15 ), uniformly mix and then move to another container. Medium's slowly added 2 5 4 parts of water, phase-transformed and dispersed using a dispersion wing, and added 1 1 ·3 parts of polyamine dissolved in water with 2.0 parts of piperazine and 8 parts of diethylenetriamine. The aqueous solution was stirred for 90 minutes to prepare an aqueous dispersion of a polyurethane acetal resin. Further, desolvent treatment was carried out under reduced pressure at 35 ° C. '3% by mass ratio -37-200949044 Guxin AG-2 5 (anionic surfactant prepared by Nikko Chemical Co., Ltd.) was added to obtain a solid content of 35.0%. A thermosensitive solidified water-based polyurethane resin (hereinafter referred to as Comparative Resin A) having a viscosity of 50 _0 mPa.s (BM viscous meter, No. 1 roller, 60 rPm) and an average particle diameter of 0.52 Jam. The water-based polyurethane resin had a thermosensitive solidification temperature of 1 Torr. (: The softening temperature of the dried film was 195 ° C. [Synthesis Example of Water-Soluble Acrylic Polymer (b)] _ Synthesis Example 7 (Water-soluble Acrylic Polymer (b): Poly-α - Sodium hydroxy acrylate) In a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer, 5 8 8.0 parts of water and a 48% by mass aqueous sodium hydroxide solution of ι 50·〇 were added until the mixture was stirred until uniform. The temperature was raised to 50 ° C. Thereafter, 150.0 parts of a polylactone compound corresponding to poly-£Z-hydroxyacrylic acid (weight average molecular weight: 100,000) was added to raise the temperature to 70 ° C. After the temperature was raised, the reaction was carried out at 70 to 75 ° C for 3 hours to obtain a poly An aqueous solution of sodium α-hydroxy acrylate (hereinafter referred to as compound a Q ) having a viscosity of 200 mPa·s and a solid content of 25.1%, and a solid content of poly-α-hydroxy acrylate having a weight average molecular weight of 100,000 〇 Example 8 (Water-soluble acrylic polymer (b): sodium poly-α-hydroxy acrylate-sodium acrylate) In a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer, 163.0 parts of 40% by mass of poly-α was added. -Sodium hydroxyacrylate (weight -38-20) 0949044 average molecular weight 100,000) aqueous solution and 127.0 parts of water. After heating to 80 °C, 150 parts of 40% by mass aqueous sodium acrylate solution were added dropwise in 45 minutes, and 5 parts of sodium persulfate was added. After the addition, at 80 to 90 The reaction was carried out at ° C for 3 hours. Then, after adding 5 5 5 parts of warm water at 60 ° C, it was cooled to obtain a polymer of sodium poly-α-hydroxy acrylate-sodium acrylate (hereinafter referred to as a compound hydrazine). The aqueous solution has a viscosity of 150 mPa·s and a solid content of 12.5%, and the solid component polymer has a weight average molecular weight of about 20,000. Synthesis Example 9 (Water-soluble acrylic polymer (b): poly-α - Triethylamine hydroxy acrylate) In a four-necked flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 180.0 parts of 40% by mass of Yalong α-IOSL (manufactured by Toagosei Co., Ltd., aqueous polyacrylic acid solution, weight average molecular weight of 6,000) was added. An aqueous solution and 295.7 parts of water. 101.0 parts of triethylamine was added dropwise over 45 minutes, and hydrazine was stirred at 30 to 4 (TC for 3 hours, and then cooled to obtain a polyethyl methacrylate salt (hereinafter referred to as compound C). Aqueous solution The viscosity of the compound was 80 mPa·s, and the solid content was 30.0%. Synthesis Example 1〇 (water-soluble acrylic polymer (b): polyacrylic acid triethanolamine salt) In a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer 180.0 parts of 40% by mass of Yalong a-1〇SL (manufactured by Toagosei Co., Ltd., aqueous polyacrylic acid solution, weight average molecular weight 6,000) water-39-200949044 solution and 233.88 parts of water were added. 74.5 parts of diethanolamine was added dropwise thereto over 45 minutes, and the reaction was carried out for 3 hours at 30 to 40 ° C, followed by cooling to obtain an aqueous solution of a polytriethanolamine salt of polyacrylic acid (hereinafter referred to as compound D). The aqueous solution had a viscosity of 15 〇 mpa_s and a solid content of 30.0%. [Synthesis Example of Convergence Type Tackifier] Synthesis Example 11 (Conjunction Type Tackifier) In a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer, '800.0 parts of polyethylene glycol having a molecular weight of 4,000 and 230.8 parts of three were added. Ethylene oxide 17 molar addition of styrenated phenol, after dehydration treatment at 105 ° C under reduced pressure, 50.4 parts of hexamethylene diisocyanate was added, and the reaction was carried out at 80 to 90 ° C for 5 hours. It was dissolved in 540.6 parts of water to prepare a polyurethane-based adhesion type tackifier (hereinafter referred to as a meeting type tackifier A). The aqueous polymer solution had a viscosity of 6000 rnPa.s and a solid content of 20.0%. (Example 1) 5 7.1 parts of the resin a (water-based polyurethane resin) obtained by the synthesis example, and 10.0 parts of the compound A (water-soluble acrylic polymer) obtained in Synthesis Example 7 A mass % aqueous solution and 3 2.9 parts of dilution water were mixed to prepare a water-based polyurethane resin composition. The solid content ratio of each component of the aqueous polyurethane resin composition is a resin A / compound A = 1 part / 5 parts 'the aqueous polyurethane resin composition solid content is 21% by mass . Making the water system polyurethanes -40- 200949044

脂組成物在由0.5旦尼爾之聚酯纖維所形成的不織布（單 位面積重量爲200g/m2)中，使用隙縫軋板機，含浸成含 浸率爲200%，使蒸氣壓調整爲39kPa、蒸氣流量調整爲 200L/分之H.T.S (辻井染色工業公司 Type:HT-3 -5 50 )進 行處理5分鐘。於處理完成後，在7〇。(：之溫水浴中加入處 理物，進行湯洗10分鐘，以軋板機扭絞出多餘的水分後 ’以調整爲100°C之熱風乾燥機（TABAI SAFETYOVEN © SPH·200)進行放置乾燥10分鐘，製得實施例1之人造皮 革。 (實施例2 ) 除使用以合成例8所得的化合物B之1 0質量％水溶 液作爲水溶性丙烯酸系聚合物外，與實施例〗相同地進行 處理，製得實施例2之人造皮革。 (實施例3 ) 除使用以合成例9所得的化合物C之10質量％水溶 液作爲水溶性丙烯酸系聚合物外，與實施例1相同地進行 處理’製得實施例3之人造皮革。 (實施例4) 除使用以合成例10所得的化合物D之10質量％水 溶液作爲水溶性丙烯酸系聚合物外，與實施例1相同地進 行處理’製得實施例4之人造皮革。 -41 - 200949044 (實施例5) 除使用以亞龍A-2 10(東亞合成股份有限公司、聚丙 烯酸鈉水溶液、分子量2,000、固成分43%)之10質量 %水溶液作爲水溶性丙烯酸系聚合物外，與實施例1相同 地進行處理，製得實施例5之人造皮革。 (實施例6) 除使用亞龍T-50(東亞合成股份有限公司、聚丙烯 酸鈉水溶液、分子量6,000、固成分43%)之10質量％ 水溶液作爲水溶性丙烯酸系聚合物外，與實施例1相同地 進行處理，製得實施例6之人造皮革。 而且，使所得的人造皮革原材料置於100L之浴中， 藉由設定爲浴比1:30、噴嘴壓2kgf/cm2之微噴射高壓液 流染色機（P-300型 '(股）狄谷塞姆（譯音）技硏公司 製），使用分散染料（C.I.Disperse Blue 79)，以 10% o.w.f、130 °C、30分鐘之條件進行染色。使染色後之人造 皮革藉由含有二氧化硫尿素4 g/Ι及氫氧化鈉4g/l之還原 洗淨劑，在80 °C下進行還原洗淨處理20分鐘，然後，藉 由熱風乾燥機、在乾燥溫度100 °C下進行加工處理。此時 之聚胺基甲酸乙酯樹脂的脫落率，係由染色前後重量變化 所求取之値，約爲4質量％。 (實施例7) -42- 200949044 除使聚胺基甲酸乙酯樹脂組成物含浸於不織布後之乾 燥條件以於蒸氣乾燥後、放置於調整爲100°C之熱風乾燥 機（TABAI SAFEYOVENSPH-200)中10分鐘予以取代外 ，與實施例6相同地進行處理，製得實施例7之人造皮革 (實施例8 ) Q 除使用亞龍A-10SL (東亞合成股份有限公司、聚丙 烯酸鈉水溶液、分子量6,000、固成分40%)之1〇質^ %水溶液作爲水溶性丙烯酸系聚合物外，與實施例1彳目胃 地進行處理，製得實施例8之人造皮革。 (實施例9 ) 除使用亞龍A-30SL (東亞合成股份有限公司、聚丙 稀酸錢水溶液、分子量6, 〇〇〇、固成分40%)之10質量 φ %水溶液作爲水溶性丙烯酸系聚合物外’與實施例1相同 地進行處理，製得實施例9之人造皮革。 (實施例10 ) 除使用亞龍A-20UN (東亞合成股份有限公司、聚丙 烯酸鈉水溶液、分子量20，000、固成分42%)之10質量 %水溶液作爲水溶性丙稀酸系聚合物外’與實施例1相同 地進行處理，製得實施例10之人造皮革。 -43- 200949044 (實施例11 ) 除使用亞龍A-20SL (東亞合成股份有限公司、聚丙 烯酸鈉水溶液、分子量500，000、固成分U%)之10質 量％水溶液作爲水溶性丙烯酸系聚合物外，與實施例1相 同地進行處理，製得實施例11之人造皮革。 (實施例1 2 ) 除使用亞龍A-6520 C東亞合成股份有限公司、聚丙 烯酸鈉水溶液、分子量1，000、固成分40%)之1〇質量 %水溶液作爲水溶性丙烯酸系聚合物外，與實施例1相同 地進行處理，製得實施例12之人造皮革。 (實施例1 3 ) 除使用以合成例2所得的樹脂B作爲水系聚胺基甲酸 乙醋樹脂外’與實施例6相同地進行處理，製得實施例 13之人造皮革。 (實施例1 4 ) 除使用以合成例4所得的樹脂D作爲水系聚胺基甲 酸乙酯樹脂外’與實施例6相同地進行處理，製得實施例 14之人造皮革。 (實施例1 5 ) 除使用以合成例5所得的樹脂E作爲水系聚胺基甲酸 -44- 200949044 乙酯樹脂外，與實施例6相同地進行處理’製得實施例 15之人造皮革。 (實施例1 6 ) 除使用以合成例3所得的樹脂c作爲水系聚胺基甲酸 乙酯樹曰外’與實施例6相同地進行處理，製得實施例 16之人造皮革。 ❹ (比較例1 ) 使5 7 · 1份以口成例1所得的樹脂a (水系聚胺基甲 酸乙酯樹脂）、及42.9份稀釋水混合，調製水系聚胺基 甲酸乙酯樹脂組成物。該水系聚胺基甲酸乙酯樹脂組成物 之固成分爲20質量％。使該水系聚胺基甲酸乙醋樹脂組 成物在由0.5旦尼爾之聚酯纖維所形成的不織布（單位面 積重量200g/m2)中’使用隙縫軋板機，含浸成含浸率爲 © 200%，使蒸氣壓調整爲39kPa、蒸氣流量調整爲200L/分 之H.T.S (辻井染色工業公司 Type:HT-3-550 )進行處理 5分鐘。於處理完成後，在70 °C之溫水浴中加入處理物， 進行湯洗1〇分鐘，以軋板機扭絞出多餘的水分後，以調 整爲 1 〇〇°C 之熱風乾燥機（TAB AI S AFETYOVEN SPH-200 )進行放置乾燥10分鐘，製得比較例1之人造皮革。 (比較例2 ) 使5 7.1份以合成例1所得的樹脂A (水系聚胺基甲 -45- 200949044 酸乙酯樹脂）、10.0份無水芒硝（固成分100%)之10 質量％水溶液、以及32.9份稀釋水混合，調製水系聚胺 基甲酸乙酯樹脂組成物。該水系聚胺基甲酸乙酯樹脂組成 物之各成分的固成分比，係樹脂A/無水芒硝=1 0 0份/5份 ，水系聚胺基甲酸乙酯樹脂組成物固成分爲21質量％。 使該水系聚胺基甲酸乙酯樹脂組成物在由0.5旦尼爾之聚 酯纖維所形成的不織布（單位面積重量200g/m2 )中，使 用隙縫軋板機，含浸成含浸率爲2 00%，使蒸氣壓調整爲 39kPa、蒸氣流量調整爲200L/分之H.T.S(辻井染色工業 公司 Type:HT-3 -5 50 )進行處理5分鐘。於處理完成後， 在70°C之溫水浴中加入處理物，進行湯洗1 0分鐘，以軋 板機扭絞出多餘的水分後，以調整爲100 °C之熱風乾燥機 (TABAI SAFETYOVEN SPH-200 )進行放置乾燥 10 分鐘 ，製得比較例2之人造皮革。 此外，使所得的人造皮革原材料置於100L之浴中， 藉由設定爲浴比1:30、噴嘴壓2kgf/cm2之微噴射高壓液 流染色機（P-300型、（股）狄谷塞姆（譯音）技硏公司 製），使用分散染料（c.disperse Blue 79)，以 10% o.w.f、130 °C、30分鐘之條件進行染色。使染色後之人造 皮革藉由含有二氧化硫尿素4g/l及氫氧化鈉4g/l之還原 洗淨劑，在8(TC下進行還原洗淨處理20分鐘，然後，藉 由熱風乾燥機、在乾燥溫度100 °C下進行加工處理。此時 之聚胺基甲酸乙酯樹脂的脫落率’係由染色前後重量變化 所求取之値，約爲12質量％。 -46- 200949044 (比較例3) 使5 7_1份以合成例1所得的樹脂A (水系聚胺基甲 酸乙酯樹脂）、10.0份以合成例11所得的會合型增黏劑 A之10質量％水溶液、以及32.9份稀釋水混合，調製水 系聚胺基甲酸乙酯樹脂組成物。該水系聚胺基甲酸乙酯樹 脂組成物之各成分的固成分比，係樹脂A/會合型增黏劑 G 100份/5份，水系聚胺基甲酸乙酯樹脂組成物固成分爲 21質量％。使該水系聚胺基甲酸乙酯樹脂組成物在由〇.5 旦尼爾之聚酯纖維所形成的不織布（單位面積重量 200g/m2)中，使用隙縫軋板機，含浸成含浸率爲2〇〇% ’使蒸氣壓調整爲39kPa、蒸氣流量調整爲200L/分之 H.T.S (辻井染色工業公司 Type:HT-3-550)進行處理5 分鐘。於處理完成後，在70 t之溫水浴中加入處理物，進 行湯洗1 〇分鐘’以軋板機扭絞出多餘的水分後，以調整 ❹ 爲 10〇°C 之熱風乾燥機（TABAI SAFETYOVEN SPH-200 ) 進行放置乾燥10分鐘，製得比較例3之人造皮革。 (比較例4 ) 使5 7·1份以合成例丨所得的樹脂a (水系聚胺基甲 酸乙酯樹脂）、1〇.〇 份之 OPTIFLO M-210(R〇ckWood 公 司疏水改性環氧酸酯胺基電漿系會合性增黏劑、固成分 20·0% )之10質量％水溶液、以及32·9份稀釋水混合， 調製水系聚胺基甲酸乙酯樹脂組成物。該水系聚胺基甲酸 -47- 200949044 乙酯樹脂組成物之各成分的固成分比，係樹脂 A/OPTIFLO M-210 = 100份/5份，水系聚胺基甲酸乙酯樹 脂組成物固成分爲21質量％。使該水系聚胺基甲酸乙酯 樹脂組成物在由0.5旦尼爾之聚酯纖維所形成的不織布（ 單位面積重量2 00g/m2 )中’使用隙縫軋板機，含浸成含 浸率爲200%，使蒸氣壓調整爲39kPa、蒸氣流量調整爲 200L/分之H.T.S (辻井染色工業公司Type:HT_3_550 )進 行處理5分鐘。於處理完成後，在7〇i之溫水浴中加入處 理物’進行湯洗10分鐘，以軋板機扭絞出多餘的水分後 ’以調整爲1 〇〇°C之熱風乾燥機（TAB AI S AFETYO VEN SPH-200 )進行放置乾燥1〇分鐘，製得比較例4之人造皮 革。 (比較例5) 除使用以合成例6所得的樹脂A作爲水系聚胺基甲 酸乙酯樹脂外，與實施例6相同地進行處理，製得比較例 Q 5之人造皮革。 (參考例1 ) 使53 _3份溶劑系聚胺基甲酸乙酯樹脂ALS-30 (曰華 化學股份有限公司製、N,N_二甲基甲醯胺溶劑）、36.7份 N，N-二甲基甲醯胺、5份NK系列F-100 (日華化學股份 有限公司製、非離子活性劑）、及5份NK系列F-200 ( 曰華化學股份有限公司製、非離子活性劑）混合，調製溶 -48- 200949044 劑系聚胺基甲酸乙酯樹脂組成物。使該溶劑系聚胺基甲酸 乙酯樹脂組成物在由〇_5旦尼爾之聚酯纖維所形成的不織 布（單位面積重量200g/m2 )中，使用隙縫軋板機，含浸 成含浸率爲250%。處理完成後，在經調整爲25。(：之水槽 中進行水凝固處理1 〇分鐘後，在經調整爲8 0 r之溫水槽 中進行湯洗處理20分鐘。然後，以軋板機扭絞多餘的水 分後，以調整爲120°C之熱風乾燥機（TABAI 〇 SAFETYOVEN S P Η - 2 0 0 )進行放置乾燥！ 〇分鐘，製得參 考例1之人造皮革。 藉由下述所示之方法，評估實施例1〜16、比較例1 〜5及參考例1所得的水系聚胺基甲酸乙酯樹脂組成物之 靜置安定性、以及是否有人造皮革之移行性及質感。其評 估結果如表1〜3所示。 <評估方法> ® 水系聚胺基甲酸乙酯樹脂組成物之靜置安定性： 觀察使水系聚胺基甲酸乙酯樹脂組成物在30°C下靜置 1日時之狀態。 判斷在水系聚胺基甲酸乙酯樹脂組成物中沒有分離、 沉澱、增黏等之變化情形時爲「〇」，有分離、沉澱、增 黏等之變化情形時爲「X」。 是否有移行現象： 藉由人造皮革之截面的電子顯微照片，目視觀察聚胺 -49- 200949044 基甲酸乙酯樹脂之塡充狀態。 聚胺基甲酸乙酯樹脂塡充於人造皮革全體截面者判斷 爲「◎」，人造皮革表面上稍有樹脂、惟沒有移行現象、 直至內部皆塡充有樹脂者爲「〇」，人造皮革表面有樹脂 之移行現象、惟實用上沒有問題者爲「〇△」，內部樹脂 少，樹脂移行至人造皮革表面者判斷爲「△」，大部分的 樹脂移行至人造皮革表面判斷爲「X」。 人造皮革質感： 藉由觸感評估人造皮革。 具有如天然皮革之質感時判斷爲「〇」，與天然皮革 相比時稍微不佳、惟實用上沒有問題時爲「〇△」’與天 然皮革相比時柔軟性不充分時或充實趕不充分時或彈力性 不充分時、不具如天然皮革之質感時爲「△」’質感硬時 爲「x」。 -50- 200949044 [表i] 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 1 2 3 4 5 6 7 8 水系聚胺基甲酸乙酯樹 脂組成物之靜置安定性 〇 〇 〇 〇 〇 〇 〇 〇 凝固方法 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 熱風 蒸氣 是否有撕現象 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 人造皮革質感 〇 〇 〇 〇 〇 〇 〇 〇△ [表2] 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 9 10 11 12 13 14 15 16 水系聚胺基甲酸乙酯樹 脂組成物之靜置安定性 〇 〇 〇 〇 〇 〇 〇 〇 凝固方法 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 是否有移行現象 ◎ ◎ 〇 ◎ ◎ 〇 ◎ ◎ 人造皮革質感 〇 〇 〇△ 〇 〇 〇△ 〇 〇 [表3] 比較例1 比較例2 比較例3 比較例4 比較例5 參考例1 水系聚胺基甲酸乙酯樹脂 組成物之靜置安定性 〇 〇 〇 〇 〇 〇 凝固方法 蒸氣 蒸氣 蒸氣 蒸氣 蒸氣 濕式 是否有移行現象 X 〇△ 〇△ △ Δ ◎ 人造皮革質感 X 〇△ Δ Δ Δ 〇The fat composition was a non-woven fabric (weight per unit area: 200 g/m 2 ) formed of a polyester fiber of 0.5 denier, and was subjected to a slit rolling machine, impregnated to an impregnation rate of 200%, and adjusted to a vapor pressure of 39 kPa. The HTS (Hajing Dyeing Industry Co. Type: HT-3 - 5 50) whose flow rate was adjusted to 200 L/min was treated for 5 minutes. After the processing is completed, at 7 〇. (: The treated material was added to the warm water bath, and the soup was washed for 10 minutes, and the excess water was twisted by the rolling mill. Then, the hot air dryer (TABAI SAFETYOVEN © SPH·200) adjusted to 100 ° C was placed and dried. In the next, the artificial leather of Example 1 was obtained. (Example 2) The treatment was carried out in the same manner as in Example except that the 10% by mass aqueous solution of the compound B obtained in Synthesis Example 8 was used as the water-soluble acrylic polymer. The artificial leather of Example 2 was obtained. (Example 3) A treatment was carried out in the same manner as in Example 1 except that a 10% by mass aqueous solution of the compound C obtained in Synthesis Example 9 was used as the water-soluble acrylic polymer. Artificial leather of Example 3. (Example 4) The same procedure as in Example 1 was carried out except that a 10% by mass aqueous solution of the compound D obtained in Synthesis Example 10 was used as the water-soluble acrylic polymer. Artificial leather. -41 - 200949044 (Example 5) A 10% by mass aqueous solution of Yalong A-2 10 (Australian Synthetic Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 2,000, solid content 43%) was used as water. The artificial leather of Example 5 was obtained in the same manner as in Example 1 except that the acrylic polymer was used. (Example 6) In addition to using Yalong T-50 (East Asia Synthetic Co., Ltd., sodium polyacrylate aqueous solution, molecular weight A 10% by mass aqueous solution of 6,000 and 43% by weight of the solid content was treated in the same manner as in Example 1 except that the aqueous solution was a water-soluble acrylic polymer, and the artificial leather of Example 6 was obtained. In the bath, a micro-injection high-pressure flow dyeing machine (P-300 type '(share) Digu Sem (Technology) Co., Ltd.) set to a bath ratio of 1:30 and a nozzle pressure of 2 kgf/cm 2 was used. Disperse dye (CI Disperse Blue 79), dyed at 10% owf, 130 ° C, 30 minutes. The dyed artificial leather was washed by reducing the sulfur dioxide containing urea 4 g / Ι and sodium hydroxide 4 g / l The cleaning agent was subjected to a reduction washing treatment at 80 ° C for 20 minutes, and then processed by a hot air dryer at a drying temperature of 100 ° C. The dropping rate of the polyurethane resin at this time was Weight change before and after dyeing The amount of enthalpy is about 4% by mass. (Example 7) -42- 200949044 The drying condition of the polyurethane resin composition after impregnation with the nonwoven fabric is adjusted to 100 ° C after steam drying. The artificial air of Example 7 was obtained by treating in the same manner as in Example 6 except that it was replaced by a hot air dryer (TABAI SAFEYOVENSPH-200) for 10 minutes. (Example 8) Q In addition to using Aaron A-10SL (East Asian synthesis) A hydrazine-based aqueous solution of a company, a sodium polyacrylate aqueous solution, a molecular weight of 6,000, and a solid content of 40% was used as a water-soluble acrylic polymer, and was treated in the same manner as in Example 1 to obtain a sample of Example 8. artificial leather. (Example 9) A 10 mass% φ% aqueous solution using Yalong A-30SL (East Asia Synthetic Co., Ltd., polyacrylic acid aqueous solution, molecular weight 6, hydrazine, solid content 40%) as a water-soluble acrylic polymer The same procedure as in Example 1 was carried out to obtain an artificial leather of Example 9. (Example 10) A 10% by mass aqueous solution of Yalong A-20UN (East Asia Synthetic Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 20,000, solid content 42%) was used as a water-soluble acrylic polymer. The artificial leather of Example 10 was obtained by treating in the same manner as in Example 1. -43- 200949044 (Example 11) A 10% by mass aqueous solution of Yalong A-20SL (East Asia Synthetic Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 500,000, solid content U%) was used as the water-soluble acrylic polymer. Further, the same procedure as in Example 1 was carried out to obtain an artificial leather of Example 11. (Example 1 2) Except that a 1% by mass aqueous solution of Yalong A-6520 C East Asia Synthetic Co., Ltd., a sodium polyacrylate aqueous solution, a molecular weight of 1,000, and a solid content of 40%) was used as the water-soluble acrylic polymer, The artificial leather of Example 12 was obtained by the same treatment as in Example 1. (Example 1 3) The artificial leather of Example 13 was obtained by treating in the same manner as in Example 6 except that the resin B obtained in Synthesis Example 2 was used as the aqueous polyurethane acetal resin. (Example 1 4) The artificial leather of Example 14 was obtained by treating in the same manner as in Example 6 except that the resin D obtained in Synthesis Example 4 was used as the aqueous polyurethane resin. (Example 1 5) The artificial leather of Example 15 was obtained by the same treatment as in Example 6 except that the resin E obtained in Synthesis Example 5 was used as the aqueous polyaminocarbamate-44-200949044 ethyl ester resin. (Example 1 6) The artificial leather of Example 16 was obtained by treating in the same manner as in Example 6 except that the resin c obtained in Synthesis Example 3 was used as the water-based polyurethane.比较 (Comparative Example 1) 5 7 · 1 part of the resin a (aqueous polyurethane resin) obtained in the mouth example 1 and 42.9 parts of dilution water were mixed to prepare a water-based polyurethane resin composition . The solid content of the aqueous polyurethane resin composition was 20% by mass. The water-based polyurethane urethane resin composition was used in a non-woven fabric (unit weight: 200 g/m 2 ) formed of a polyester fiber of 0.5 denier, using a slit rolling machine, and the impregnation rate was 0.1%. The HTS (Haijing Dyeing Industry Co., Ltd. Type: HT-3-550) adjusted to a vapor pressure of 39 kPa and a vapor flow rate of 200 L/min was treated for 5 minutes. After the treatment is completed, the treated material is added to a warm water bath at 70 ° C, and the soup is washed for 1 minute, and the hot water dryer (TAB) adjusted to 1 〇〇 ° C is twisted by the rolling mill to remove excess water. AI S AFETYOVEN SPH-200) was left to stand for 10 minutes to prepare artificial leather of Comparative Example 1. (Comparative Example 2) 57.1 parts of a 10% by mass aqueous solution of Resin A (aqueous polyaminomethyl-45-200949044 acid ethyl ester resin) obtained in Synthesis Example 1 and 10.0 parts of anhydrous Glauber's salt (100% solid content), and 32.9 parts of diluted water was mixed to prepare a water-based polyurethane resin composition. The solid content ratio of each component of the aqueous polyurethane resin composition is resin A / anhydrous sodium sulfate = 10 parts / 5 parts, and the aqueous polyurethane resin composition has a solid content of 21% by mass. . The water-based polyurethane resin composition was impregnated into an impregnation rate of 200% in a non-woven fabric (unit weight: 200 g/m 2 ) formed of a polyester fiber of 0.5 denier. The HTS (Hajing Dyeing Industry Co., Ltd. Type: HT-3 - 5 50) whose vapor pressure was adjusted to 39 kPa and whose steam flow rate was adjusted to 200 L/min was treated for 5 minutes. After the treatment was completed, the treated material was added to a warm water bath at 70 ° C, and the mixture was washed for 10 minutes, and the excess water was twisted by a rolling mill to adjust the temperature to 100 ° C. (TABAI SAFETYOVEN SPH) -200) It was left to stand and dried for 10 minutes to obtain artificial leather of Comparative Example 2. In addition, the obtained artificial leather raw material was placed in a 100 L bath, and a micro-injection high-pressure liquid flow dyeing machine (P-300 type, (share) Digusai set to a bath ratio of 1:30 and a nozzle pressure of 2 kgf/cm 2 was set. Using a disperse dye (c. disperse Blue 79), dyeing was carried out at 10% owf, 130 ° C, and 30 minutes. The dyed artificial leather was subjected to a reduction washing treatment at 8 (TC) for 20 minutes by a reducing detergent containing 4 g/l of sulfur dioxide urea and 4 g/l of sodium hydroxide, and then dried by a hot air dryer. The processing was carried out at a temperature of 100 ° C. The detachment rate of the polyurethane resin at this time was about 12% by mass from the change in weight before and after dyeing. -46- 200949044 (Comparative Example 3) 5 7 1 part of the resin A (water-based polyurethane resin) obtained in Synthesis Example 1 and 10.0 parts of the 10% by mass aqueous solution of the meeting-type tackifier A obtained in Synthesis Example 11 and 32.9 parts of diluted water were mixed. A water-based polyurethane resin composition is prepared. The solid content ratio of each component of the aqueous polyurethane resin composition is 100 parts by weight of the resin A/confining type tackifier G, and the aqueous polyamine The solid content of the ethyl urethane resin composition was 21% by mass, and the water-based polyurethane resin composition was formed into a nonwoven fabric (unit weight: 200 g/m 2 ) composed of a polyester fiber of 〇.5 denier. Medium, using a slit rolling machine, impregnating into an impregnation rate of 2〇 〇% 'HTS (Haijing Dyeing Industry Co., Ltd. Type: HT-3-550) adjusted to a vapor pressure of 39 kPa and a steam flow rate of 200 L/min for 5 minutes. After the treatment was completed, it was added to a 70 t warm water bath. The treated material was washed for 1 〇 minutes. After the excess water was twisted by the rolling mill, the hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 10 °C was placed and dried for 10 minutes to prepare a comparison. Artificial leather of Example 3. (Comparative Example 4) 57.1 parts of resin a (water-based polyurethane resin) obtained by the synthesis example, and OPTIFLO M-210 (R〇ckWood) of 1 part. The company's hydrophobic modified epoxy ester amine-based plasma is a synergistic tackifier, a solid content of 20% by weight of a 10% by mass aqueous solution, and 32.9% of a dilution water is mixed to prepare a water-based polyurethane resin. Composition: The solid ratio of each component of the aqueous polyaminocarbamate-47-200949044 ethyl ester resin composition, resin A/OPTIFLO M-210 = 100 parts/5 parts, water-based polyurethane resin composition The solid content component is 21% by mass. The water-based polyurethane resin composition is made up of A non-woven fabric (weight per unit area of 200 g/m2) formed by a polyester fabric of 0.5 denier is used in a slot rolling machine, impregnated to an impregnation rate of 200%, a vapor pressure of 39 kPa, and a vapor flow rate of 200 L/ The HTS (Hajing Dyeing Industry Co., Ltd. Type: HT_3_550) was treated for 5 minutes. After the treatment was completed, the treated material was added to the warm water bath of 7〇i for 10 minutes to twist the excess water. After that, it was left to stand by a hot air dryer (TAB AI S AFETYO VEN SPH-200) adjusted to 1 ° C for 1 minute to prepare artificial leather of Comparative Example 4. (Comparative Example 5) An artificial leather of Comparative Example Q 5 was obtained by treating in the same manner as in Example 6 except that the resin A obtained in Synthesis Example 6 was used as the aqueous polyurethane resin. (Reference Example 1) 53 _3 parts of solvent-based polyurethane resin ALS-30 (manufactured by Suga Chemical Co., Ltd., N,N-dimethylformamide solvent), 36.7 parts of N,N-II Methylformamide, 5 parts of NK series F-100 (made by Rihua Chemical Co., Ltd., nonionic active agent), and 5 parts of NK series F-200 (made by Yuhua Chemical Co., Ltd., nonionic active agent) The mixture was prepared by dissolving the -48-200949044 agent-based polyurethane resin composition. The solvent-based polyurethane resin composition was impregnated into a non-woven fabric (unit weight: 200 g/m 2 ) formed of a polyester fiber of 〇 5 denier using a slit rolling machine. 250%. After the processing is completed, it is adjusted to 25. (: The water is solidified in the water tank for 1 minute, and then treated in a warm water tank adjusted to 80 ° for 20 minutes. Then, the excess water is twisted by a rolling mill to adjust to 120°. The hot air dryer of C (TABAI 〇SAFETYOVEN SP Η - 00 0 ) was left to dry! 〇 Min, the artificial leather of Reference Example 1 was prepared. Examples 1 to 16 and Comparative Examples were evaluated by the methods shown below. The static stability of the aqueous polyurethane resin composition obtained in 1 to 5 and Reference Example 1, and whether or not the artificial leather was transferred and textured. The evaluation results are shown in Tables 1 to 3. Method > ® Static Stability of Water-Based Polyurethane Resin Composition: The state in which the aqueous polyurethane resin composition was allowed to stand at 30 ° C for one day was observed. When the ethyl formate resin composition is not separated, precipitated, or thickened, it is "〇", and when it is separated, precipitated, or thickened, it is "X". Is there a migration phenomenon: by artificial leather Electron micrograph of the cross section Observe the filling state of polyamine-49-200949044 ethyl urethane resin. The polyurethane resin is judged as "◎" when it is filled with the entire cross section of artificial leather, and the artificial leather has a slight resin on the surface, but there is no migration phenomenon. It is "〇" until the inside is filled with resin. The surface of the artificial leather has a resin migration phenomenon. However, if there is no problem in practical use, it is "〇△", the internal resin is small, and the resin is transferred to the artificial leather surface. Most of the resin was transferred to the surface of the artificial leather and judged to be "X". Artificial leather texture: The artificial leather was evaluated by the touch. The texture of the natural leather was judged as "〇", and it was slightly different from the natural leather. Good, but when there is no problem in practical use, "〇△" is "△" when the softness is insufficient when compared with natural leather, or when the filling is insufficient or when the elasticity is insufficient, and the texture of natural leather is not the same. When the texture is hard, it is "x". -50- 200949044 [Table i] EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Example 1 2 3 4 5 6 7 8 Water-based polyamine group Static stability of ethyl formate resin composition 〇〇〇〇〇〇〇〇 Solidification method Steam vapor vapor vapor vapor steam hot air vapor tearing ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 artificial leather texture 〇〇〇〇〇〇 〇〇 △ [Table 2] EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES EXAMPLES Example 9 10 11 12 13 14 15 16 Static stability of aqueous polyurethane resin composition〇〇〇〇 〇〇〇〇Coagulation method Whether the vapor vapor vapor vapor vapor vapor vapor has a migration phenomenon ◎ ◎ 〇 ◎ ◎ 〇 ◎ ◎ Artificial leather texture 〇〇〇 △ 〇〇〇 〇〇 表 [Table 3] Comparative Example 1 Comparative Example 2 Comparison Example 3 Comparative Example 4 Comparative Example 5 Reference Example 1 Static stability of aqueous polyurethane resin composition 〇〇〇〇〇〇 Solidification method Steam vapor vapor vapor vapor wet type transition phenomenon X 〇 △ 〇 △ △ Δ ◎ artificial leather texture X 〇 △ Δ Δ Δ 〇

此外，有關實施例1〜1 6、比較例1〜5及參考例1， 藉由下述所示之方法，評估有關水系聚胺基甲酸乙酯樹脂 組成物之凝固狀態、及由聚胺基甲酸乙酯樹脂組成物所形 成的薄膜之物性。其評估結果如表4〜6所示。 -51 - 200949044 凝固狀態： 使l〇g水系聚胺基甲酸乙酯樹脂組成物置於試驗管中 ，評估在90°C之恆溫熱水浴中靜置時的狀態。凝固成寒天 狀者判斷爲「〇」，粗大粒子化者判斷爲「△」，沒有凝 固者判斷爲「X」。而且，此處所指的「寒天狀」係指水 系聚胺基甲酸乙酯樹脂組成物在試驗管全體中均勻地凝固 ，且具有彈力性的狀態。此外，「粗大粒子化」係指水系 聚胺基甲酸乙酯樹脂在試驗管中形成嵌段狀粗大粒子者。 薄膜物性： (1 )薄膜之製作 在縱12cm、橫10cm、高lcm之不錄鋼製箱中，使聚Further, in Examples 1 to 16 and Comparative Examples 1 to 5 and Reference Example 1, the solidification state of the aqueous polyurethane resin composition and the polyamine group were evaluated by the method shown below. The physical properties of the film formed by the ethyl formate resin composition. The evaluation results are shown in Tables 4 to 6. -51 - 200949044 Solidification state: The l〇g water-based polyurethane resin composition was placed in a test tube, and the state at the time of standing at 90 ° C in a constant temperature hot water bath was evaluated. Those who have solidified into a cold weather are judged as "〇", those who are coarse particles are judged as "△", and those who do not have solidification are judged as "X". In addition, the term "cold weather" as used herein refers to a state in which the aqueous polyurethane resin composition is uniformly solidified in the entire test tube and is elastic. Further, "coarse particle formation" means a water-based polyurethane resin which forms block-like coarse particles in a test tube. Film properties: (1) Production of film In a non-recorded steel box with a length of 12 cm, a width of 10 cm, and a height of 1 cm,

胺基甲酸乙酯薄膜於乾燥後之厚度爲〇.3mm下，加入水 系聚胺基甲酸乙酯樹脂組成物，在調整爲20°C、65% RH 恆溫恆濕室中、2日內以鑄造法予以成膜。然後，在 Q 130 °C下進行熱處理30分鐘，製得聚胺基甲酸乙酯薄膜。 (2 )聚胺基甲酸乙酯薄膜之物性測定 製作由以（1 )所得的聚胺基甲酸乙酯薄膜所形成的 聚胺基甲酸乙酯薄膜之啞鈴狀3號形試驗片，使該試驗片 以20°C、65% RH進行狀態調整，以JIS K 625 1 - 1 993爲 基準，使用拉伸試驗[股份有限公司島津製作所、 AUTOGRAPH AG-500D]，以拉伸速度 300mm/min 測定拉 -52- 200949044 伸斷裂強度及拉伸率。 [表4] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 凝固狀態 〇 〇 〇 〇 〇 〇 〇 〇 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 薄膜物性拉伸 斷裂強度 18 19 17 16 19 19 19 20 (MPa) 拉伸率 350 370 320 380 350 365 365 310 (%) [表5] 實施例9 實施例1” 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 凝固狀態 〇 〇 〇 〇 〇 〇 〇 〇 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 寒天狀 薄膜物性拉伸 斷裂強度 20 17 16 18 16 18 18 17 (MPa) 拉伸率 330 310 300 350 450 375 390 420 (%) [表6] 比較例1 比較例2 比較例3 比較例4 比較例5 參考例1 凝固狀態 〇 寒天狀 〇 寒天狀 △ 粗粒子化 (沉澱） Δ 粗粒子化 (沉澱） X - 薄膜物性 拉伸斷裂強度 19 5 12 10 17 20 (MPa) 拉伸率 340 200 355 275 400 410 (%) -53- 200949044 由上述結果可知，藉由實施例1〜16之水系聚胺基甲 酸乙酯樹脂組成物’可得靜置安定性優異，在常溫下充分 安定，且不會有因顯著的感熱凝固性之移行現象，可均句 地塡充於纖維間，很少會有樹脂之強度降低情形，且具有 與天然皮革同等的質感，即具有柔軟性、充實感及彈力性 之人造皮革。 [產業上之利用價値] 本發明之人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ，在常溫下安定且具有顯著的感熱凝固性，即使在基布中 進行含浸加工處理或塗覆加工處理時，可充分防止移行現 象。而且，藉由本發明之人造皮革用水系聚胺基甲酸乙酯 樹脂組成物及使用它之人造皮革之製造方法，可在水系中 製造與使用溶劑系聚胺基甲酸乙酯樹脂組成物所得的人造 皮革相同程度的質感，特別是具有柔軟性、充實感及彈力 性人造皮革。 ϋ -54-The ethyl urethane film was dried to a thickness of 〇.3 mm, and a water-based polyurethane resin composition was added, and the casting method was carried out in a constant temperature and humidity chamber adjusted to 20 ° C and 65% RH for 2 days. Film formation. Then, heat treatment was carried out at Q 130 ° C for 30 minutes to prepare a polyurethane film. (2) Physical Property Measurement of Polyurethane Film A dumbbell-shaped No. 3 test piece of a polyurethane film formed of the polyurethane film obtained in (1) was prepared to make the test. The sheet was adjusted at a temperature of 20 ° C and 65% RH, and the tensile test was performed using a tensile test [Shimadzu Corporation, AUTOGRAPH AG-500D] at a tensile speed of 300 mm/min based on JIS K 625 1 - 993. -52- 200949044 Strength at break and elongation. [Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Solidification state Cold weather cold weather cold weather cold weather cold weather Cold weather-like film physical tensile tensile strength 18 19 17 16 19 19 19 20 (MPa) Tensile rate 350 370 320 380 350 365 365 310 (%) [Table 5] Example 9 Example 1" Example 11 Implementation Example 12 Example 13 Example 14 Example 15 Example 16 Solidification state Cold weather cold weather cold weather cold weather cold weather cold weather cold weather film physical tensile fracture strength 20 17 16 18 16 18 18 17 (MPa) Tensile rate 330 310 300 350 450 375 390 420 (%) [Table 6] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Reference Example 1 Solidification state Cold weather like cold weather Shape △ coarse particle formation (precipitation) Δ coarse particle formation (precipitation) X - film physical tensile strength at break 19 5 12 10 17 20 (MPa) elongation 340 200 355 275 400 410 (%) -53- 200949044 The result shows that The aqueous polyurethane resin compositions of Examples 1 to 16 are excellent in standing stability, are sufficiently stable at normal temperature, and have no significant migration phenomenon due to thermosensitive coagulability. When the mantle is filled between the fibers, there is little possibility that the strength of the resin is lowered, and the texture is the same as that of the natural leather, that is, the artificial leather having flexibility, fullness, and elasticity. [Industrial use price] The present invention The artificial leather is a water-based polyurethane resin composition which is stable at normal temperature and has remarkable thermocoagulation property, and can sufficiently prevent migration even when subjected to impregnation processing or coating processing in the base fabric. By using the artificial polyurethane water-based polyurethane resin composition of the present invention and the method for producing the artificial leather using the same, the artificial leather obtained by using the solvent-based polyurethane resin composition can be produced in the water system. The degree of texture, especially soft, full and elastic artificial leather. ϋ -54-

Claims (1)

200949044 十、申請專利範圍 1· 一種人造皮革用水系聚胺基甲酸乙酯樹脂組成物 ’其係爲在基布中含浸或塗覆水系聚胺基甲酸乙酯樹脂組 成物’製得人造皮革的方法中所使用的水系聚胺基甲酸乙 酯樹脂組成物， 其特徵爲含有感熱凝固溫度爲40〜90。(：之感熱凝固型 水系聚胺基甲酸乙酯樹脂（a)、水溶性丙烯酸系聚合物 ©(b)’ 前述水溶性丙烯酸系聚合物（b)爲下述（1) 、（2 )及（3)之聚合物中之至少一種， (1) 選自丙烯酸、甲基丙烯酸及馬來酸所成群之至 少一種單體之聚合物、該聚合物之鹼金屬及/或胺鹽， (2) 聚_〇：-羥基丙烯酸、其鹼金屬及/或胺鹽， (3) 使選自丙烯酸、甲基丙烯酸、馬來酸、丙烯酸 之鹼金屬鹽、甲基丙烯酸之鹼金屬鹽、馬來酸之鹼金屬鹽 Φ 、丙烯酸之胺鹽、甲基丙烯酸之胺鹽及馬來酸之胺鹽所成 群之至少一種單體、與選自聚-α-羥基丙烯酸以及其鹼金 屬及/或胺鹽所成群之至少一種進行自由基聚合所得的聚 合物、該聚合物之鹼金屬及/或胺鹽。 2. —種人造皮革之製造方法，其特徵爲具有在基布 中含浸或塗覆申請專利範圍第1項之人造皮革用水系聚胺 基甲酸乙酯樹脂組成物的步驟。 3. —種人造皮革，其特徵爲藉由申請專利範圍第2 項之人造皮革的製造方法所得者。 -55- 200949044 七、指定代表圖·· (一） 、本案指定代表闽為：無 (二） 、本代表圖之元件代表符號簡單說明··無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無200949044 X. Patent Application Scope 1. An artificial leather water-based polyurethane resin composition is obtained by impregnating or coating a water-based polyurethane resin composition in a base fabric to obtain artificial leather. The aqueous polyurethane resin composition used in the method is characterized in that it contains a thermosensitive solidification temperature of 40 to 90. (: thermosensitive solidification type aqueous polyurethane resin (a), water-soluble acrylic polymer © (b)' The water-soluble acrylic polymer (b) is the following (1), (2) and At least one of the polymers of (3), (1) a polymer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, at least one monomer, an alkali metal and/or an amine salt of the polymer, ( 2) Poly-〇:-hydroxyacrylic acid, its alkali metal and/or amine salt, (3) selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, horse At least one monomer grouped from an acid base metal Φ, an amine amine salt, an amine salt of methacrylic acid, and an amine salt of maleic acid, and a poly-α-hydroxy acrylate and an alkali metal thereof and/or Or a polymer obtained by radical polymerization of at least one of a group of amine salts, an alkali metal and/or an amine salt of the polymer. 2. A method for producing artificial leather, characterized by having an impregnation in a base fabric or The artificial leather water-based polyurethane resin group coated with the patent application scope 1 Step of the object 3. An artificial leather characterized by the method of manufacturing the artificial leather of the second application of the patent scope. -55- 200949044 VII. Designation of the representative figure (1), the designated representative of the case 闽For: No (2), the representative symbol of the representative figure is a simple description of the symbol. · No. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: None
TW097150263A 2007-12-25 2008-12-23 Water-based artificial leather the polyurethane resin composition, a method for producing artificial leather and artificial leather TWI453319B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2007332679 2007-12-25

Publications (2)

Publication Number Publication Date
TW200949044A true TW200949044A (en) 2009-12-01
TWI453319B TWI453319B (en) 2014-09-21

Family

ID=40801119

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097150263A TWI453319B (en) 2007-12-25 2008-12-23 Water-based artificial leather the polyurethane resin composition, a method for producing artificial leather and artificial leather

Country Status (5)

Country Link
JP (1) JP5432723B2 (en)
KR (1) KR20100099701A (en)
CN (1) CN101861425B (en)
TW (1) TWI453319B (en)
WO (1) WO2009081815A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI808496B (en) * 2020-10-02 2023-07-11 日商大日精化工業股份有限公司 Urethane prepolymer, moisture-curing urethane hot-melt resin composition, and laminate

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408698A (en) * 2011-09-02 2012-04-11 福建宝利特集团有限公司 Preparation method for waterborne polyurethane foaming slurry
JP5401522B2 (en) * 2011-09-15 2014-01-29 富士フイルム株式会社 Coating composition, and image forming material, lithographic printing plate precursor and oxygen-barrier film using the composition
CN103388266B (en) * 2013-07-16 2015-09-30 山东泽辉高科涂层有限公司 A kind of high poisture-penetrability polyurethane resin for superfine fibre soaking and preparation method thereof
CN105369631A (en) * 2015-12-25 2016-03-02 江苏宝泽高分子材料股份有限公司 Non-yellowing high-gloss oil leather for synthetic leather and preparation method of oil leather
CN107190521B (en) * 2017-05-24 2019-10-29 贝内克-长顺汽车内饰材料（张家港）有限公司 A kind of low smell PVC artificial leather and preparation method thereof
CN109722094A (en) * 2017-10-31 2019-05-07 宇部兴产株式会社 Emulsion compositions
US20210040315A1 (en) * 2018-04-20 2021-02-11 Dic Corporation Resin composition and synthetic leather
TWI691630B (en) * 2018-11-16 2020-04-21 劉玉文 Artificial leather and production method thereof
CN110284335B (en) * 2019-07-26 2022-04-19 凤阳加松新型材料科技有限公司 Preparation method of environment-friendly silica gel synthetic leather
CN112195663B (en) * 2020-09-30 2022-09-09 安徽安利材料科技股份有限公司 Regenerated silk water-based solvent-free polyurethane synthetic leather for packaging and preparation method thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3047951B2 (en) * 1993-04-30 2000-06-05 旭化成工業株式会社 Manufacturing method of artificial leather with good soft abrasion resistance
JP3972234B2 (en) * 1999-02-08 2007-09-05 大日本インキ化学工業株式会社 Aqueous urethane resin composition for porous formation
JP3626418B2 (en) * 2000-03-07 2005-03-09 三洋化成工業株式会社 Textile treatment agent
JP4532758B2 (en) * 2001-02-20 2010-08-25 日華化学株式会社 Method for producing porous structure
JP4055419B2 (en) * 2002-01-23 2008-03-05 東レ株式会社 Method for producing napped leather-like sheet
JP2003277600A (en) * 2002-03-22 2003-10-02 Nicca Chemical Co Ltd Stabilizer for polyurethane resin, method for stabilizing polyurethane resin, and polyurethane resin composition
JP3967629B2 (en) * 2002-05-13 2007-08-29 三洋化成工業株式会社 Leather-like sheet material
CN1696226A (en) * 2004-05-14 2005-11-16 湖南亚大新材料科技股份有限公司 Ultraviolet light solidified water born paint in use for leather or leatheroid
JP2006028248A (en) * 2004-07-13 2006-02-02 Kuraray Co Ltd Heat-sensitive gelling emulsion
JP4452139B2 (en) * 2004-07-28 2010-04-21 日華化学株式会社 Method for manufacturing leather materials
CN1757690A (en) * 2005-07-12 2006-04-12 东莞市德富皮革制品有限公司 Environmental protection and water type leather coating used for leather and artificial leather, and its prepn. method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI808496B (en) * 2020-10-02 2023-07-11 日商大日精化工業股份有限公司 Urethane prepolymer, moisture-curing urethane hot-melt resin composition, and laminate

Also Published As

Publication number Publication date
JPWO2009081815A1 (en) 2011-05-06
KR20100099701A (en) 2010-09-13
CN101861425B (en) 2013-04-24
CN101861425A (en) 2010-10-13
JP5432723B2 (en) 2014-03-05
WO2009081815A1 (en) 2009-07-02
TWI453319B (en) 2014-09-21

Similar Documents

Publication Publication Date Title
TW200949044A (en) Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather
TWI529188B (en) Aqueous polyurethane resin dispersion, method for making the same and its use
TWI712648B (en) Water dispersible polycarbonate-based polyurethane resin composition, textile product treated with same, and method for producingwater dispersible polycarbonate-based polyurethane resin composition
EP1164169B1 (en) Aqueous urethane resin composition for forming microporous material, method for preparing fiber sheet composite and synthetic leather
JP4042016B2 (en) Method for producing fiber sheet composite and artificial leather
JP7261143B2 (en) Foam-forming composition, foam, method for producing foam, and leather material
JP3972234B2 (en) Aqueous urethane resin composition for porous formation
JP2008081877A (en) Air-permeable coated fabric
JP3741247B2 (en) Method for producing fiber sheet composite and artificial leather
JP7242287B2 (en) Manufacturing method for leather materials
JP4204711B2 (en) Leather-like sheet manufacturing method
JP4257564B2 (en) Aqueous dry laminate adhesive composition for synthetic leather and method for producing synthetic leather using the same
JP2015534597A (en) Polyurethane dispersion-based coatings with enhanced removability
JP4458976B2 (en) Manufacturing method of fiber composite material and fiber composite material
JP4927621B2 (en) Aqueous polyurethane resin composition for skin layer formation and leather-like laminate using the same
JP3940013B2 (en) Leather-like sheet material
JP4226755B2 (en) Method for producing composite resin emulsion
JP2004019016A (en) Finishing agent for fiber and resin-finished fibrous base material
JP3944782B2 (en) Aqueous polyurethane resin dispersion, aqueous adhesive containing the same, and aqueous primer coating agent
TW200404936A (en) Leather-like sheet and method for producing it
JP2008520820A (en) Improved filled polyurethane dispersion
JP3961130B2 (en) Heat-sensitive gelling polyurethane emulsion and method for producing the same
JP6978930B2 (en) Foam forming composition, foam, foam manufacturing method and leather material
JP2022022566A (en) Composition for foam formation, foam, method for producing foam and leather material
JP2010189556A (en) Aqueous polyurethane resin composition and film molded body using the same