TW201120275A - Method for producing leather material and leather material. - Google Patents

Method for producing leather material and leather material. Download PDF

Info

Publication number
TW201120275A
TW201120275A TW099127586A TW99127586A TW201120275A TW 201120275 A TW201120275 A TW 201120275A TW 099127586 A TW099127586 A TW 099127586A TW 99127586 A TW99127586 A TW 99127586A TW 201120275 A TW201120275 A TW 201120275A
Authority
TW
Taiwan
Prior art keywords
carboxyl group
leather
group
polyurethane resin
acid
Prior art date
Application number
TW099127586A
Other languages
Chinese (zh)
Inventor
Yoshinobu Kibe
Masakazu Nishino
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 TW201120275A publication Critical patent/TW201120275A/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/62—Complexes of metal oxides or complexes of metal salts with ammonia or with organic amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
    • D06N3/08—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products with a finishing layer consisting of polyacrylates, polyamides or polyurethanes or polyester
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/106—Roughness, anti-slip, abrasiveness
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/108—Slipping, anti-blocking, low friction
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/18—Medical, e.g. bandage, prostheses, catheter
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention provides a method for producing leather material, which is to submerge fiber substrate in the mixed solution containing: (A) Polyurethane (PU) resin having a carboxyl group and/or carboxylic ester group, (B) an ammonium salt of inorganic acid, and (C) water, then drying it to obtain the leather material.

Description

201120275 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種皮革用材料之製造方法 料’更詳而言之，係使用水性聚胺基甲酸酯樹 可適宜使用來作爲人工皮革或合成皮革之皮革 造方法及皮革用材料。 【先前技術】 自以往，就天然皮革之替代品而言，以由 酯樹脂與不織布所構成之纖維基材所構成的人 聚胺基甲酸酯樹脂與織物或編物所構成之纖維 之合成皮革已有多種類被製造。如此之人工皮 革例如爲類似於天然皮革，使聚胺基甲酸酯樹 劑溶液含浸或塗佈於纖維基材者，對於聚胺基 爲弱溶劑’且通過具有與該有機溶劑相溶性之 般爲水）中而凝固，然後，以水洗、乾燥之所 法的方法來製造。 但’在如此之濕式凝固法中常被使用之二 等之有機溶劑係除著火性強，進一步毒性亦高 具有火災之危險性外，亦擔心作業環境之惡化 質等之環境污染的問題。繼而，爲解決如此之 進行組入回收所產生之有機溶劑的步驟之製造 仍殘留昂貴之廢棄成本、或耗費勞力之問題點 聚胺基甲酸酯樹脂之有機溶劑溶液所得到的人 及皮革用材 脂而製造， 用材料的製 聚胺基甲酸 工皮革及以 基材所構成 革' 合成皮 脂之有機溶 甲酸酯樹脂 凝固液（一 謂濕式凝固 甲基甲醯胺 者很多，故 或大氣、水 問題點，亦 方法，但， 。又，使用 工皮革、合 -5- 201120275 成皮革，係於皮革內部殘留有機溶劑，故對皮 人體的影響亦有問題。因此，硏究使固定於纖 胺基甲酸酯樹脂從有機溶劑型移至水性聚胺基 〇 使用如此之水性聚胺基甲酸酯樹脂的人工 造方法，係未使用有機溶劑，故就可刪除回收 的點及就作業環境之改善、大氣污染、水質污 改善而言，係很優異，但與使用聚胺基甲酸酯 溶劑溶液所得到的人工皮革、合成皮革比較時 具有滿足之手感與物性之人工皮革、合成皮革 題很大的原因，係可舉例如使水性聚胺基甲酸 於纖維基材內部之後，以熱風進行乾熱乾燥時 基材表面蒸發之水的移動所引來的水性聚胺基 移動至纖維基材表面即所謂遷移性。亦即，藉 之遷移性，在使用水性聚胺基甲酸酯樹脂之人 製造方法中，係水性聚胺基甲酸酯樹脂移動至 表面而於纖維基材內部係成爲聚胺基甲酸酯樹 定的狀態，成爲手感硬、缺乏起毛感之人工皮 革。因此，使用水性聚胺基甲酸酯樹脂之人工 造方法中，爲解決遷移性之問題，已有各種硏 〇 例如，在特公昭5 5-5 1 076號公報（專利3 係已揭示一種添加感熱凝膠化劑，使賦予感熱 成樹脂乳液含浸於纖維基材，在熱水中凝固該 膚妨礙等之 維基材之聚 甲酸酯樹脂 皮革等的製 所需之成本 濁等的環境 樹脂之有機 ，無法得到 。如此之問 酯樹脂含浸 ，於從纖維 甲酸酯樹脂 由產生如此 工皮革等的 纖維基材的 脂幾乎未固 革、合成皮 皮革等的製 究正在進行 :獻1 )中， 凝固性之合 合成樹脂乳 -6- 201120275 液的皮革狀物之製造方法。 但，在如此之方法中係雖然防止遷移性已提昇，但含 浸液之一部分流出至浴中而凝固，其凝固之凝膠物再附著 於加工物的表面，有所得到之皮革用材料之手感變差的問 題。又，在如此之方法中，隨聚胺基甲酸酯樹脂濃度降低 而感熱凝固性降低，含浸液之一部分易流出至熱水中，亦 有所得到之皮革用材料之手感變更差的問題。 又，在特開平6 - 3 1 6 8 7 7號公報（專利文獻2 )中，係 已揭示一種使於已被強制乳化之非離子性的乳液中溶解無 機鹽類的水性樹脂組成物，賦予至不織片狀物，進行加熱 乾燥之人工皮革的製造方法。 但，在如此之方法中係雖然防止遷移性提昇，但藉所 調配之無機鹽的濃度，所謂處理浴之安定性變差之加工上 的問題仍存在。又，於纖維基材中殘留非離子界面活性劑 及無機鹽，故所得到之皮革用材料係手感粗硬，耐磨耗性 低，摩擦堅牢度亦未充分者。 進一步，在特開2000-290879號公報（專利文獻3 )中 ，已揭示一種使由感熱凝固溫度爲4 0~90°C之水性聚胺基 甲酸酯樹脂與會合型增黏劑所構成之水性樹脂組成物，含 浸或塗佈於纖維材料基體上，使該水性樹脂組成物以蒸氣 感熱凝固之纖維片狀複合物的製造方法。 但，在如此之方法中係雖然防止遷移性提昇，但於纖 維材料基體中殘留非離子界面活性劑、會合型增黏劑，故 所得到之皮革用材料還是手感粗硬，耐磨耗性低，摩擦堅 201120275 牢度亦未充分者。 又，在特開20 03- 1 38 1 3 1號公報（專利文獻4)中係已 揭示一種使含有HLB 10〜18之非離子界面活性劑與無機鹽 之羧酸鹽型聚胺基甲酸酯樹脂賦予至纖維材料基體，使之 感熱凝固而成之皮革用片材料的製造方法。 但，即使在如此之方法中，與前述專利文獻2或3記載 的方法同樣地，產生界面活性劑或無機鹽所造成之問題， 所得到之皮革用材料，還是手感粗硬，摩擦堅牢度亦未充 分者。 又’在前述專利文獻2〜4記載的方法中，所謂非離子 界面活性劑、會合型增黏劑之殘留物，係藉重複水洗或熱 水洗之步驟進行，可除去某程度，但，很難完全地除去， 無法避免前述之問題。又，重複進行水洗或熱水洗之步驟 ’成爲加工步驟數的增加，且與經濟上之問題相關。因此 ’要求儘可能地減少水洗或熱水洗之步驟，且，可容易地 除去殘留物，以得到具有充分的手感或物性之皮革用材料 的製造方法。 又，在特開2〇06-3696〇號公報（專利文獻5 )中係已 揭示使含有：含羧基之聚胺基甲酸酯樹脂、羧酸之銨鹽 及水之混合液，含浸於纖維基材之後，進行乾燥之皮革用 材料的製造方法。 但’在如此之方法中係雖然可解決遷移性之問題，但 產生所謂乾燥時發生之氨氣所造生的臭氣之新問題。又， 使用所謂蟻酸銨或醋酸銨之碳數小的羧酸銨鹽作爲羧酸敍 -8 - 201120275 鹽時，係產生所謂受加熱乾燥進行揮發之羧酸而腐蝕裝置 之問題，必須改善製造步驟。另外，使用碳數大之羧酸的 銨鹽時，係加熱乾燥時很少羧酸揮發，但若欲得到目的之 防止遷移性，必須大量使用。又，爲提昇樹脂之耐熱性等 的耐久性，若併用聚碳二醯亞胺化合物，此與羧酸銨鹽反 應，故即使大量地使用羧酸銨鹽，亦很難得到充分的防止 遷移性。 如此地，在使用水性聚胺基甲酸酯樹脂之人工皮革等 的製造方法中，係可充分防止遷移性而於纖維基材均一地 固定聚胺基甲酸酯樹脂，同時並於工程上發生之氣體的臭 氣及裝置的腐蝕少，無法得到製造具有充分的手感或品質 之皮革用材料的方法，而必須有工程上發生之VOC對策爲 現狀。 【發明內容】 〔發明之槪要〕 本發明係有鑑於上述習知技術具有之課題者，目的在 於提供一種儘管爲使用考量環境負荷或VOC之問題的水性 聚胺基甲酸酯樹脂之皮革用材料的製造方法，而可充分地 防止遷移性’又’工程上發生之氣體的臭氣及裝置的腐蝕 少’可有效率且確實地得到手感爲柔軟且耐磨耗性或摩擦 堅牢度等的物性亦優異之皮革用材料之皮革用材料的製造 方法’以及’依其製造方法所得到之皮革用材料。 本發明人等係爲達成上述目的，累積專心硏究之結果 -9- 201120275 ’發現藉由使含有特定之水性聚胺基甲酸酯樹脂、無機酸 鹽及水之混合液，含浸於纖維基材之後進行乾燥，俾可得 到在乾燥中水性聚胺基甲酸酯樹脂進行遷移而未局部化， 至纖維基材之內部均一地固定聚胺基甲酸酯樹脂而具備柔 軟的手感與充分的物性之皮革用材料，依據此見識而終完 成本發明。 亦即’本發明之皮革用材料之製造方法，其係使含有 (A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（b )無機酸之銨鹽及（C)水之混合液，含浸於纖維基材之 後進行乾燥而得到皮革用材料之方法。 .上述本發明之混合液係宜（A)具有羧基及/或羧酸酯 基之聚胺基甲酸酯樹脂與（B)無機酸之銨鹽的調配比， 以固形成分之質量換算，爲（A) : (B) =100: 〇.1〜1〇〇 ：50 ° 又，前述混合液係宜pH爲5.0〜7 _0者，又，感熱凝固 溫度宜爲30〜80°C者。 上述本發明之（B)無機酸之銨鹽中的無機酸宜爲硫 酸及/或磷酸。 上述本發明之（A)具有羧基及/或羧酸酯基之聚胺基 甲酸酯樹脂係宜使（a)有機二異氰酸酯、（b)多元醇及 (c )具有羧基與2個以上之活性氫的化合物反應所得到之 具有羧基的異氰酸酯基末端預聚物中和而於水中藉自己乳 化而使之乳化分散後，使用（d )具有2個以上胺基及/或 亞胺基之聚胺化合物使其進行鏈延長反應所得到之具有羧 -10- 201120275 基及/或羧酸酯基之聚胺基甲酸酯樹脂。 又’前述（A)具有羧基及/或羧酸酯基之聚胺基甲酸 酯樹脂係宜羧基含量與羧酸酯基含量之合計爲0.5〜4 〇質量 %。 進一步本發明之皮革用材料，係依前述本發明之製造 方法所得到者。 若依本發明，可提供一種儘管爲使用考量環境負荷或 V Ο C之問題的水性聚胺基甲酸酯樹脂之皮革用材料的製造 方法，而可充分地防止遷移性，又，工程上發生之氣體的 臭氣及裝置的腐蝕少’可有效率且確實地得到手感爲柔軟 且耐磨耗性或摩擦堅牢度等的物性亦優異之皮革用材料之 皮革用材料的製造方法，以及’依其製造方法所得到之皮 革用材料。 〔較佳實施例之詳細說明〕 以下，依據其適宜的實施形態而詳細地說明本發明。 本發明之皮革用材料之製造方法，其係使含有（A) 具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（B)無機 酸之銨鹽及（C )水之混合液’含浸於纖維基材之後進行 乾燥而得到皮革用材料之方法。 如此之本發明的（A)具有羧基及/或羧酸酯基之聚胺 基甲酸酯樹脂係於胺基甲酸酯樹脂骨架中具有作爲親水成 分之羧基及/或羧酸酯基之聚胺基甲酸酯樹脂。如此之（A )具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂係可適宜 -11 - 201120275 使用：使（a)有機二異氰酸酯、（b)多元醇及（c)具 有羧基與2個以上之活性氫的化合物反應所得到之具有羧 基的異氰酸酯基末端預聚物中和而於水中藉自己乳化而使 之乳化分散後，使用（d )具有2個以上胺基及/或亞胺基 之聚胺化合物使其鏈延長反應所得到之具有羧基及/或羧 酸酯基之聚胺基甲酸酯樹脂。 如此之（a)有機二異氰酸酯，係無特別限定，可使 用具有2個異氰酸酯基的脂肪族二異氰酸酯、脂環式二異 氰酸酯及芳香族二異氰酸酯。如此之（a)有機二異氰酸 酯，係可舉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二異氰酸酯化合物、異佛爾酮二異氰 酸酯、氫化二甲苯二異氰酸酯、二環己基甲烷二異氰酸酯 、降冰片烷二異氰酸酯、1,3 -雙（異氰酸酯甲基）環己烷 等之脂環式二異氰酸酯化合物、甲苯二異氤酸酯、二苯基 甲烷二異氰酸酯、萘二異氰酸酯、聯甲苯胺二異氰酸酯、 二甲苯伸基二異氰酸酯、四甲基二甲苯伸基二異氰酸酯等 之芳香族二異氰酸醋化合物等。此等之二異氰酸酯化合物 係可1種單獨使用’或組合2種以上而使用。在如此之（a )有機二異氰酸醋之中’脂肪族二異氰酸酯化合物及脂環 式二異氰酸醋化合物係於皮革用材料賦予無黃變性，故可 適宜使用’尤宜使用六亞甲基二異氰酸酯、異佛爾酮二異 氰酸醋、二環己基甲院二異氰酸酯、降冰片烷二異氰酸酯 及1，3-雙（異氰酸酯甲基）環己烷。 又，（b)多元醇係只要爲具有2個以上之羥基者，無 -12- 201120275 特別限定，除了聚酯多元醇、聚碳酸酯多元醇、聚 醇等之外，尙亦可使用具有醚鍵與酯鍵之聚醚酯多； 如此之聚酯多元醇係可舉例如聚乙烯己二酸酯 烯己二酸酯、聚乙烯丁烯己二酸酯、聚六亞甲基異 己二酸酯、聚乙烯琥珀酸酯、聚丁烯琥珀酸酯、聚 二酸酯、聚丁烯癸二酸酯、聚己內酯二醇、聚 基-1,5 -戊烯）己二酸酯、1,6 -己二醇與二聚體酸之 物、1，6 -己二醇與己二酸與二聚體酸之共縮合物、 與二聚體酸之聚縮合物、乙二醇與己二酸與二聚體 縮合物等。 又，前述聚碳酸酯多元醇係可舉例如聚四亞甲 酸酯二醇、聚六亞甲基聚碳酸酯二醇、聚-1，4-環己 甲基聚碳酸酯二醇、1，6-己二醇聚碳酸酯多元醇等。 進一步，前述聚醚多元醇係可舉例如聚乙二醇 Ζ醇、聚四亞甲基甘醇的單獨聚合物、嵌段共聚物 共聚物、環氧乙烷與環氧丙烷、環氧乙烷與環氧丁 機共聚物或嵌段共聚物等。 又，如此之（b)多元醇係可1種單獨使用’驾 種以上而使用。進一步，如此之（b)多元醇的平 量宜爲500〜5000，更宜爲1000〜3000。又，從藉由 之具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂而 用材料賦予充分的耐久性之觀點’前述之（b)多 使用聚碳酸酯多元醇或聚醚多元醇。 又，（c)具有羧基與2個以上之活性氫的化合 醚多元 ΐ醇。 、聚丁 酞酸酯 乙烯癸 (3-甲 聚縮合 壬二醇 酸之共 基聚碳 烷二亞 、聚丙 、隨機 烷之隨 U且合2 均分子 所得到 於皮革 元醇宜 物，可 -13- 201120275 舉例如2,2-二羥甲基丙酸、2,2-羥甲基丁酸等。進一步具 有如此之羧基與2個以上之活性氫的化合物，亦可使用具 有羧基之二醇、與芳香族二羧酸、脂肪族二羧酸等反應所 得到的具垂掛型羧基之聚酯多元醇。又，取代前述具羧基 之二醇，亦可混合不具有羧基之二醇作爲二醇成分而反應 。又，具有如此之羧基與2個以上之活性氫的化合物係可1 種單獨使用，或組合2種以上而使用。 使（a)有機二異氰酸酯、（b)多元醇及（c)具有 羧基與2個以上之活性氫的化合物反應而製造具有羧基的 異氰酸酯基末端預聚物時係依需要而可使用具有2個以上 之活性氫原子的低分子量鏈延伸劑。 如此之具有2個以上之活性氫原子的低分子量鏈延伸 劑係宜分子量爲400以下者，尤宜爲300以下者。又，如此 之低分子量鏈延伸劑，可舉例如乙二醇、丙二醇、新戊二 醇、1,4 -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、六亞 甲基二胺、二胺基環己基甲烷、六氫化吡嗪、2-甲基六氫 化吡嗪、異佛爾酮二胺、二乙二胺、三乙四胺等之低分子 量聚胺等。進一步，如此之具有2個以上之活性氫原子的 低分子量鏈延伸劑係可1種單獨使用，或組合2種以上而使 用。 在本發明中，製造具有羧基的異氰酸酯基末端預聚物 之具體方法並無特別限制，可藉由例如以往公知的一段式 所謂一槍法（one shot )、多段式之異氰酸酯聚加成反應 • 14 - 201120275 法等進行製造。此時之反應溫度宜爲40〜l5〇°C。又，如此 之反應時’依需要而可添加二丁基錫二月桂酸醋、錫辛酸 酯、二丁基錫-2-乙基己酸酯、三乙胺、三乙二胺、Ν·甲 基嗎琳等之反應觸媒。又，反應中或反應終了後，可添加 不與異氰酸酯基反應之有機溶劑。如此之有機溶劑係可舉 例如丙酮、甲乙酮、甲苯、四氣呋喃、二嚼院、二甲基甲 醯胺、Ν-甲基吡咯烷酮等。 在本發明中，具有羧基的異氰酸酯基末端預聚物之中 和係於具有羧基的異氰酸酯基末端預聚物之調製前或調製 後使用適當公知的方法而進行。使用於如此之具有羧基的 異氰酸酯基末端預聚物之中和的化合物係無特別限制，可 舉例如三甲胺、三乙胺、三正丙胺、三丁基胺、Ν-甲基-二乙醇胺、Ν，Ν-二甲基單乙醇胺、Ν，Ν-二乙基單乙醇胺、 三乙醇胺等之胺類、氫氧化鉀、氫氧化鈉、氨等。如此之 前述化合物中，尤宜爲三甲胺、三乙胺、三正丙胺、三丁 基胺等之第3級胺類。 又，在本發明中，使具有羧基的異氰酸酯基末端預聚 物之中和物乳化分散於水時所使用之乳化機器並無特別限 制，可舉例如均混機、均質機、調膠機等。又，具有羧基 的異氰酸酯基末端預聚物之中和物乳化分散於水時係宜使 具有羧基的異氰酸酯基末端預聚物之中和物尤其不使用乳 化劑，而於室溫〜40 °C之溫度範圍乳化分散於水’而極力 抑制異氰酸酯基與水之反應。進一步，如此地’使之乳化 分散時依需要而可添加磷酸、磷酸二氫鈉、磷酸氫二鈉、 -15- 201120275 對甲苯磺酸、己二酸、氯化苯甲醯基等之反應抑制劑。 進一步，在本發明中，具有羧基的異氰酸酯基末端預 聚物之中和物乳化分散於水之後，藉使用（d )具有2個以 上胺基及/或亞胺基之聚胺化合物使其進行鏈延長反應而 可得到目的之（A)具有羧基及/或羧酸酯基之聚胺基甲酸 酯樹脂的乳化分散液。 如此之（d )具有2個以上胺基及/或亞胺基之聚胺化 合物，可舉例如乙二胺、丙二胺、四亞甲基二胺、六亞甲 基二胺、二胺基環己基甲烷、六氫化吡嗪、聯胺、2-甲基 六氫化吡嗪、異佛爾酮二胺、降冰片烷二胺、二乙基二苯 基甲烷、甲苯二胺、二甲苯二胺等之二胺；二乙三胺、三 乙四胺、四乙五胺、亞胺基雙丙胺、三（2-胺基乙基）胺 等之聚胺；二第一級及單羧酸所衍生之醯胺胺；二第一級 胺的單酮亞胺等之水溶性胺衍生物；藻酸二聯胺、丙二酸 二聯胺、琥珀酸二聯胺、戊二酸聯胺、己二酸聯胺、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’-亞乙基聯胺、1，1’-三亞甲基聯胺、1，1’-(1，4-亞丁 基）二聯胺等之聯胺衍生物。此等之具有2個以上胺基及/ 或亞胺基之聚胺化合物，係可1種單獨，或組合2種以上而 使用9 在本發明中，具有羧基的異氰酸酯基末端預聚物之中 和物之鏈延伸反應係於前述具有羧基的異氰酸酯基末端預 聚物之中和物的乳化分散物中，可添加（d)具有2個以上 胺基及/或亞胺基之聚胺化合物而進行。又，亦可於（d) -16- 201120275 具有2個以上胺基及/或亞胺基之聚胺化合物中添加前述具 有羧基的異氰酸酯基末端預聚物之中和物的乳化分散物而 進行。鏈延伸反應係宜在反應溫度20〜40 X：進行，一般在 3 0~ 120分鐘結束。製造具有羧基的異氰酸酯基末端預聚物 之際使用有機溶劑時係宜例如終止鏈延長反應後，藉減壓 蒸餾等除去有機溶劑。 在本發明中，（A)具有羧基及/或羧酸酯基之聚胺基 甲酸酯樹脂的100 %模數之値，宜爲0.5〜20 MPa，更宜爲 2〜6 MPa。100%模數之値未達前述下限時，可得到柔軟之 手感的皮革用材料，但，有耐磨耗性變弱之傾向，另外， 若超過前述上限，所得到之皮革用材料的手感硬，有與纖 維之密著性降低的傾向。此處，1 〇 〇 %模數之値係依據JIS K 625 1 ( 20〇4 )而使用啞鈴狀3號形的試驗片而測定，標 線間距離爲1 00%延伸時（延伸成2倍時）中之特定延伸抗 拉應力（MPa)之値。 又，在本發明中’宜（A)具有羧基及/或羧酸酯基之 聚胺基甲酸酯樹脂中之羧基含量與羧酸酯基含量之合計爲 0.5-4.0質量％，更宜爲1.0〜2.0質量％。羧基含量與羧酸酯 基含量之合計未達前述下限時，係所得到之（A )具有羧 基及/或羧酸酯基之聚胺基甲酸酯樹脂的貯存安定性有變 差之傾向’另外，若超過前述上限，與（B)無機酸之銨 鹽混合時所產生之感熱凝固溫度變高，皮革用材料之製造 時防止遷移性的效果有變弱的傾向》 在本發明中之（B)無機酸的銨鹽中之無機酸，可舉 -17- 201120275 例如過氯酸、碳酸、硫酸、過硫酸、亞硫酸、磷酸、硝酸 等。如此之無機酸中，因防止遷移性效果優異，故宜爲硫 酸及/或磷酸。具體之（B)無機酸的銨鹽，可舉例如過硫 酸銨、過氯酸銨、碳酸銨、硫酸銨、硫酸氫銨、亞硫酸銨 、亞硫酸氫銨、磷酸氫二銨、磷酸二氫銨、過硫酸銨、硝 酸銨等。如此之（B)無機酸的銨鹽中，從處理之安全性 、乾燥中之揮發問題、及藉乾燥後之水洗而可容易地除去 、殘留於皮革用材料很少之觀點，可適宜使用由硫酸銨、 磷酸氫二銨及磷酸二氫銨所構成之群中選出的至少一種。 又，磷酸氫二銨係可單獨使用，但，磷酸二氫銨係宜與磷 酸氫二銨倂用而使用。 在本發明之皮革用材料的製造方法中，使（B)無機 酸的銨鹽混合於（A)具有羧基及/或羧酸酯基之聚胺基甲 酸酯樹脂之乳化分散液時，係亦可使（B )無機酸的銨鹽 以固體（粉體）之狀態混合於（A)具有羧基及/或羧酸酯 基之聚胺基甲酸酯樹脂之乳化分散液，但從保持（A)具 有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂之乳化分散液 之安定性的觀點，宜使（B)無機酸的銨鹽以水溶液的狀 態進行混合。 在如此之（B)無機酸的銨鹽的水溶液中，無機酸的 銨鹽之濃度宜爲1〜50質量％，更宜爲10〜30質量％。在前述 水溶液中之（B)無機酸的銨鹽的濃度未達前述下限的水 溶液時，爲發揮乾燥時之防止遷移性，混合於（A )具有 羧基及/或羧酸酯基之聚胺基甲酸酯樹脂之乳化分散液時 -18- 201120275 ，必須添加大量之前述水溶液，伴隨其而具有混合液中之 (A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂濃度下 降。因此，爲使必需量之具有羧基及/或羧酸酯基之聚胺 基甲酸酯樹脂固定於纖維基材，係必須使大量之混合液含 浸於纖維基材，乾燥中揮發之水分量變多，故有乾燥時間 變長而經濟性變差之傾向。另外，若前述水溶液中之（B )無機酸的銨鹽的濃度超過前述上限，與（A)具有羧基 及/或羧酸酯基之聚胺基甲酸酯樹脂之乳化分散液的混合 時產生析出物等，有損及乳化分散液之安定性的傾向。 又，在本發明中之（C)水係混合（A)具有羧基及/ 或羧酸酯基之聚胺基甲酸酯樹脂及（B)無機酸的銨鹽時 ’具有作爲溶劑之角色者，可適宜使用離子交換水或蒸餾 水。 在本發明中調節含有（A)具有羧基及/或羧酸酯基之 聚胺基甲酸酯樹脂、（B)無機酸之銨鹽及（C)水之混合 液之方法，係無特別限制，而可使用適宜公知之方法。 又，在前述混合液中，（A)具有羧基及/或羧酸酯基 之聚胺基甲酸酯樹脂與（B)無機酸之銨鹽的調配比，以 固形成分之質量換算，宜爲（A) ： (B) =100： 0.1-100 :50’更宜爲 1〇〇: 1〜100: 40。前述調配比超過100: 0.1時’亦即，無機酸之銨鹽的調配比少於0.1時，在乾燥 步驟中有防止遷移性效果變弱的傾向，調配比未達100: 50時’亦即無機酸之銨鹽的調配比多於50時，在夏場之氣 溫環境下，有混合液凝膠化之傾向。又，本發明之固形成 -19- 201120275 分謂使試料在溫度105 °C的條件下加熱3小時後的殘分。 進一步，前述混合液之感熱凝固溫度宜爲30〜80 °C， 更宜爲40〜70°C。此處，感熱凝固溫度係使前述混合液5 0g 取至lOOmL的玻璃製燒杯中，攪拌內容物，同時並使其燒 杯在95 °C的熱水浴中徐緩地加熱，內容物喪失流動性，凝 固時之溫度。感熱凝固溫度未達前述下限時，係在夏場之 氣溫環環境下，有混合液凝膠化之傾向，超過前述上限時 ，感熱凝固未明顯顯現，故在乾燥步驟中有防止遷移性變 弱之傾向。 又，前述混合液中之（A)具有羧基及/或羧酸酯基之 聚胺基甲酸酯樹脂的含量宜就固形成分之質量換算宜爲 5〜40質量％，更宜爲10〜30質量％。若具有羧基及/或羧酸 酯基之聚胺基甲酸酯樹脂的含量未達前述下限，爲固定必 需量之聚胺基甲酸酯樹脂，相對於纖維基材，含浸大量之 前述混合液，故在乾燥揮發之水分量變多而乾燥時間變長 ，有經濟性變差之傾向。另外，若具有羧基及/或羧酸酯 基之聚胺基甲酸酯樹脂的含量超過前述上限，有前述混合 液的安定性變差之傾向。 若含有習知之具有羧基及/或羧酸酯基之聚胺基甲酸 酯樹脂的混合液變成酸性，乳化安定性會降低，故很難使 用於皮革用材料的製造，但本發明之混合液係pH値即使爲 酸性側（較佳係5.0〜7.0，更宜爲5.5~6.8，尤宜爲6.0〜6.5 )，具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂的乳化 會安定，可使用於皮革用材料之製造。 -20- 201120275 進一步’本發明之纖維基材係並無特別限定，可適宜 使用於織物、編物或不織布等。如此之纖維基材的材料， 因可得到近似天然皮革之手感及品質，故可適宜使用〜使 用聚醯胺纖維、聚酯纖維者。 又，可使用來作爲前述纖維基材之前述不織布中，不 織布之絲的粗度係從所得到之皮革用材料的手感提高之觀 點’宜爲2_0 dtex以下。若不織布之絲的粗度超過2〇 dtex ’皮革用材料之手感變成粗硬，有損品質之傾向。 又，如此之不織布的密度宜爲0.2〜〇_7g/cm3，更宜爲 0.3 0~0.5 5g/cm3。若不織布之密度未達前述下限，所得到 之皮革用材料的耐摩耗性有變差之傾向，又，爲彌補其， 若固定大量之聚胺基甲酸酯樹脂，所得到之皮革用材料之 手感變成粗硬’有損品質之傾向。另外，若不織布之密度 超過前述上限’所得到之皮革用材料的手感變成粗硬，有 損品質之傾向。 本發明之皮革用材料的製造方法中，在含有（A)具 有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（B)無機酸 之銨鹽及（C)水之混合液中，係在無損本發明之目的的 範圍’爲賦予加工適性’可添加各種之添加劑。如此之添 加劑’係可舉例如低級醇 '甘醇系溶劑、醇系之非離子界 面活性劑、乙烯二醇系之特殊界面活性劑、矽酮系之界面 活性劑、氟系之界面活性劑等之各種浸透劑；抗氧化劑、 耐光安定化劑、抗紫外線劑等之各種安定化劑；礦物油系 、聚矽氧系等之各種消泡劑；胺基甲酸酯化觸媒、可塑劑 -21 - 201120275 、顏料等之著色劑、可使用時間延長劑等。如此之添加劑 係可1種單獨’或組合2種以上而使用。 又’在如此之添加劑中，尤宜添加浸透劑。使用浸透 劑，可於前述纖維基材迅速含浸前述混合液，同時並可得 到於前述纖維基材均一地固定聚胺基甲酸酯樹脂之效果。 如此之浸透劑，只要爲一般所使用者即可，並無特別限制 ’但尤宜使用低級醇、甘醇系溶劑、醇系之非離子界面活 性劑等。 又’在本發明之皮革用材料的製造方法中，在含有（ A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（b) 無機酸之銨鹽及（C)水之混合液中，在無損本發明之目 的的範圍’爲賦予加工適性，可添加與羧基反應之交聯劑 。如此之交聯劑可舉例如噁唑啉系交聯劑、環氧系交聯劑 、異氰酸酯系交聯劑、羰二醯亞胺系交聯劑、氮丙啶（ aziri dine )系交聯劑、封端異氰酸酯系交聯劑、水分散異 氰酸酯系交聯劑、三聚氰胺系交聯劑等。此等之交聯劑係 可1種單獨，或組合2種以上而使用。 在本發明之皮革用材料的製造方法中，使含有（A) 具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（B)無機 酸之銨鹽及（C)水之混合液，含浸於織物、編物、不織 布等之纖維基材後進行乾燥。 使前述混合液含浸於前述纖維基材之方法，並無特別 限制’較佳係可採用例如由d i p - n i p方式所構成之含浸加工 、噴霧處理等之自以往即公知的方法，亦可適當選擇前述 -22- 201120275 混合液的濃度及處理條件等。又，使含有（A )具 及/或羧酸酯基之聚胺基甲酸酯樹脂、（B)無機酸 及（C )水之混合液，含浸於織物、編物、不織布 維基材之前，可於纖維基材進行前處理。在如此之 步驟中係爲調整纖維基材與聚胺基甲酸酯樹脂成分 力，宜使用由聚乙烯醇、羧甲基纖維素等所構成的 水溶液、聚矽氧系撥水劑、氟系撥水劑等而處理纖 〇 又，在本發明之皮革用材料的製造方法中，使 合液含浸於纖維基材內部後進行乾燥之方法，無特 ，例如可使用：利用熱風之乾式乾燥；高溫蒸 H.T.S )、高壓蒸氣機（H.P.S )之濕式乾燥；微波照 燥等，就連續加工性之點可適宜使用一種利用熱風 乾燥。此等之乾燥方法，係可1種單獨使用，或亦ΐ 種以上而使用。又，在使用前述利用熱風之乾式乾 宜使其處理溫度爲60~190°C，處理時間爲1〜20分鐘 處理溫度爲l〇〇~17(TC，處理時間爲2~5分鐘。藉由 此之乾燥，可於纖維基材內部固定聚胺基甲酸酯樹丨 如此做法而使含有（A )具有羧基及/或羧酸酯 胺基甲酸酯樹脂' (B)無機酸之銨鹽及（C)水之 ，含浸於纖維基材之後進行乾燥，可得到本發明之 材料。 在如此之本發明的皮革用材料中，在皮革用材 聚胺基甲酸酯樹脂等的固定固形成分之量，並無特 有羧基 之銨鹽 等之纖 前處理 的接著 高分子 維基材 前述混 別限制 氣機（ 射式乾 之乾式 Ϊ組合2 燥時係 ，尤宜 進行如 丨旨。 基之聚 混合液 皮革用 料中之 別限制 -23- 201120275 ’但於皮革用材料中’宜源自於（A)具有羧基及/或羧酸 酯基之聚胺基甲酸酯樹脂的成分爲1 0〜90質量％ ,源自於（ B)無機酸的銨鹽之成分爲0.5〜7.0質量％。 又，本發明之皮革用材料係可進行染色。如此之染色 方法並無特別限制’使聚胺基甲酸酯樹脂固定於纖維基材 之後進行染色之先含浸後染色方法、及、染色纖維基材後 固定聚胺基甲酸酯樹脂之後含浸先染色法之任一者均可進 行。 進一步，本發明之皮革用材料係亦可形成表皮層，作 爲附銀面之皮革用材料。形成如此之表皮層的方法，可爲 習知公知之任一者的方法，並無特別限制，但可舉例如藉 由於離型紙塗佈表皮層用材料，使水分蒸發，俾形成表皮 層，進一步於其上塗佈接著劑，直接與本發明之皮革用材 料貼合而蒸發水分’或，於水分之蒸發後貼合之離型紙轉 印法；藉由於離型紙塗佈表皮層用材料，使水分蒸發，俾 形成表皮層，藉熱使表皮層與本發明之皮革用材料貼合之 熱轉印法；於本發明之皮革用材料上直接噴塗表皮層用材 料之噴塗法；以凹版塗佈機、刮刀塗佈機、繞線棒塗佈器 、氣刀塗佈器等’於本發明之皮革用材料上塗佈表皮層用 材料之直接塗佈法等。即使於形成如此之表皮層的方法中 ，就所得到之表皮層的物性面更提高的觀點，最宜爲離型 紙轉印法。在如此之離型紙轉印法中所使用之表皮層用材 料與接著劑，若爲可與本發明之皮革用材料貼合者，任一 者均可，但從手感面及物性面宜爲聚胺基甲酸酯樹脂，又 -24- 201120275 ，從無VOC及環境負荷之面宜爲水性或無溶劑系者。 又，本發明之皮革用材料係就其用途，可使用於車輛 、家倶、衣料、鞋、皮包、袋物、涼鞋、雜貨'硏磨等之 領域。 【實施方式】 〔實施例〕 以下’依據實施例及比較例而更具體地說明本發明， 但本發明係不限定於以下之實施例。 又’依各實施例及各比較例所得到之皮革用材料係依 下述之方法進行評估。 (1 )防止遷移性 有關依各實施例及各比較例所得到之皮革用材料，使 用掃描型電子顯微鏡〔Scanning Electron Microscope S-2400 (H1TACHI)〕而以60倍之倍率觀察皮革用材料的截 面’比較存在於不織布之中央部的聚胺基甲酸酯樹脂的固 著狀態、與存在於不織布之表面部的聚胺基甲酸酯樹脂的 固著狀態而依如下之基準而評估。 5級：在皮革用材料截面中，於中央部與表面部，於 樹脂固定量完全看不出差異，而未產生遷移性。 4級：在皮革用材料截面中，於中央部與表面部，於 樹脂固定量幾乎看不出差異，而未產生遷移性。 3級：在皮革用材料截面中，於中央部與表面部，於 -25- 201120275 樹脂固定量稍看出差異，在全體之厚度占有的中央部之 1 0%部分係看不出樹脂固著。 2級：在皮革用材料截面中，於中央部與表面部，於 樹脂固定量看出相當差異，在全體之厚度占有的中央部之 3 0%部分係看不出樹脂固著。 1級：在皮革用材料截面中，於中央部與表面部，於 樹脂固定量看出明顯差異，在全體之厚度占有的中央部之 5 0%部分係看不出樹脂固著。 (2 )磨耗試驗 有關依各實施例及各比較例所得到之皮革用材料，&amp; 據JIS L 10 96 (19 99 )的推拔形法，藉推抆摩耗試驗機〔 安田精機製作所製〕，使用軟質輪CS-10，施加荷重5〇〇g ，使之摩耗1 000次及3 000次後之以皮革用材料之重量的減 少量作爲摩耗量而表示。又，摩耗量愈少，皮革用材料之 耐摩耗性愈優異。 (3 )摩擦堅牢度 有關依各實施例及各比較例所得到之皮革用材料，依 據JIS L 0 849 ( 2 004 )，藉學振型摩擦試驗機〔大榮化學 精機製作所製〕，施加荷重 200g，摩擦100次，測定濕式 摩擦堅牢度。前述摩擦堅牢度之測定係使用污染用灰度計 比較未漂白綿布的污染度，而依據如下之基準而評估。 5級：看不出污染。 -26- 201120275 4級：稍看出污染。 3級：明確地看出污染。 2級：略明顯地看出污染。 1級：明顯地看出污染。 (4 )殘留物之有無 有關依各實施例及各比較例所得到之皮革用材料，對 於皮革用材料中之不織布及聚胺基甲酸酯樹脂以外的成分 (界面活性劑等之殘留物）之含量，以甲醇作爲萃取溶劑 的Soxhlet萃取器，測定以70°C萃取3小時之時的萃取量， 以萃取量爲1.0質量％以上者作爲有殘留物，以未達10質量 %者作爲無殘留物而進行評估。 (5 )手感 藉觸感，依據如下之基準而使依各實施例及各比較例 所得到之皮革用材料的手感從5級（柔軟）至1級（粗硬） 之5階段而進行評估。 5級：極富柔軟且反撥彈性的手感 4級：富柔軟且反撥彈性的手感 3級：柔軟並略欠缺反撥彈性之手感 2級：略粗硬且類紙（如紙）之手感 1級：粗硬且類紙（如紙）之手感 (6 )乾燥時之臭氣 -27- 201120275 在各實施例及比較例中，以熱風乾燥機進行乾燥時之 氨及酸之臭氣以官能進行評估。 A :無臭氣 B :略有臭氣 C :刺鼻之激烈臭氣 〔合成例及比較合成例〕 以下，表示本發明所使用之具有羧基及羧酸酯基之聚 胺基甲酸酯樹脂的合成例、及使用於比較例的水性聚胺基 甲酸酯樹脂之比較合成例。 (合成例1 ) 於附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，饋入1，6-己二醇聚碳酸酯多元醇（平均分子 量2000 ) 1 57.0g、新戊二醇7.5g'三羥甲基丙烷1.3g、2,2-二羥甲基丙酸9.5g、二丁基錫二月桂酸酯〇.〇〇lg及甲乙酮 105g，均一地混合後，加入異佛爾酮二異氰酸酯 69.7g， 在80 °C下反應3 00分鐘，得到對於不揮發分之游離異氰酸 酯基的含量爲1.9質量％之具有羧基的異氰酸酯基末端預聚 物的甲乙酮溶液。 使前述溶液冷卻至50°C以下後，加入三乙胺6.8g，在 40 °C進行中和反應30分鐘。其次，使進行中和之溶液冷卻 至30 °C以下，使用分散機葉片而徐緩地加入水42 1.9g而使 具有羧基的異氰酸酯基末端預聚物的中和物乳化分散，得 -28- 201120275 到分散液。繼而，將6 0質量％之氫化聯® l.lg溶解於水20g之聚胺水溶液添加於前 °C鏈延伸長反應6 0分鐘後，減壓下，以3 得到不揮發分35.0質量％、黏度120 mPa 2號旋轉子、60rpm) 、pH値7.8、平均粒 具有羧基及羧酸酯基之聚胺基甲酸酯樹脂 此具有羧基及羧酸酯基之聚胺基甲酵 含量與羧酸酯基含量之合計爲1.3質量％， 2MPa。又，此具有羧基及羧酸酯基之聚Jg 水分散物係在9 0 °C加熱中亦不會凝膠化而 者。 (合成例2 ) 於附有攪拌機、回流冷卻管、溫度言1 四口燒瓶中，饋入1，6-己二醇聚碳酸酯多 量2000) 178.0g、三羥甲基丙烷0.9g、 2 9.3g、二丁基錫二月桂酸酯0.001 g及甲乙 混合後，加入二環己基甲烷二異氰酸酯 反應420分鐘，得到對於不揮發分之游離 量爲1.2質量％之具有羧基的異氰酸酯基 酮溶液。 使前述溶液冷卻至50°C以下後，加 40 °C進行中和反應30分鐘。其次，使進 至3 0°C以下，使用分散機葉片而徐緩地 ¥ 5.2g與二乙三胺 述分散液，以3 5 5 °C進行脫溶劑， • s ( B Μ黏度劑' 徑90nm之安定的 之水分散物。 ?酯樹脂中之羧基 1 0 0 %模數之値爲 完基甲酸酯樹脂之 ί爲無感熱凝固性 -及氮氣導入管之 .元醇（平均分子 ，2 -二羥甲基丙酸 ，酮1 0 5 g，均一地 5 6.9 g，在 8 0 °C 下 異氰酸酯基的含 ί端預聚物的甲乙 〈三乙胺6.7g，在 i1中和之溶液冷卻 卩入水4 2 4 _ 4 g而使 -29 - 201120275 具有羧基的異氰酸酯基末端預聚物的中和物乳化分散’得 到分散液。繼而，將60質量％之氫化聯胺3.3g與二乙三胺 〇-7g溶解於水20g之聚胺水溶液添加於前述分散液’以35 °C鏈延伸長反應6 0分鐘後，減壓下，以3 5 °C進行脫溶劑’ 得到不揮發分35.0質量％、黏度70 mPa. s(BM黏度劑、1 號旋轉子、60 rpm) 、pH値7.6、平均粒徑120 nm之安定的 具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之水分散物。 此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂中之羧基 含量與羧酸酯含量之合計爲1.3質量％，100%模數爲5 MPa 。又，此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之水分 散物係在90 °C加熱中亦不會凝膠化而爲無感熱凝固性者。 (合成例3 ) 於附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，饋入聚四亞甲基甘醇（平均分子量2000 ) 141.9g、2,2-二羥甲基丙酸30.8g、二丁基錫二月桂酸酯 〇.〇〇lg及甲乙酮105g，均一地混合後，加入六甲基二異氰 酸酯72.3g ’在8〇。(：下反應18〇分鐘，得到對於不揮發分之 游離異氰酸酯基的含量爲3.1質量％之具有羧基的異氰酸酯 基末端預聚物的甲乙酮溶液。 使前述溶液冷卻至50 °C以下後，加入三乙胺22.1 g， 在4〇°C進行中和反應30分鐘。其次，使進行中和之溶液冷 卻至30°C以下，使用分散機葉片而徐緩地加入水402.6§而 使具有羧基的異氰酸酯基末端預聚物的中和物乳化分散， -30- 201120275 得到分散液。繼而，將60質量％之氫化聯胺 胺1 .8g溶解於水20g之聚胺水溶液添加於前 3 5 °C鏈延伸長反應60分鐘後，減壓下，以3ί ，得到不揮發分35.0質量％、黏度50 mPa . 、1號旋轉子、60rpm ) 、pH値7.9、平均粒名 的具有羧基及羧酸酯基之聚胺基甲酸酯樹脂 此具有羧基及羧酸酯基之聚胺基甲酸酯 含量與羧酸酯基含量之合計爲4.2質量％， MPa。又，此具有羧基及羧酸酯基之聚胺基 水分散物係在9 0 °C加熱中亦不會凝膠化而爲 者。 (合成例4 ) 於附有攪拌機、回流冷卻管、溫度計及 四口燒瓶中，饋入1,6-己二醇聚碳酸酯多元 量2000 ) 1 5 7.0g、新戊二醇7.5g、三羥甲基Ϊ 二羥甲基丙酸9.5g、二丁基錫二月桂酸酯0, l〇5g’均一地混合後，加入異佛爾酮二異彳 在8〇°C下反應300分鐘，得到對於不揮發分 醋基的含量爲1.9質量％之具有羧基的異氰酸 物的甲乙酮溶液。 使前述溶液冷卻至5 0 t以下後，加入三 4〇°C進行中和反應30分鐘。其次，使進行中 至30°C以下，使用分散機葉片而徐緩地加7 :8.6g與二乙三 述分散液，以 ;°C進行脫溶劑 s ( B Μ黏度劑 各1 50nm之安定 之水分散物。 樹脂中之羧基 100%模數爲8 甲酸酯樹脂之 無感熱凝固性 氮氣導入管之 醇（平均分子 g 烷 1.3g 、 2,2-001 g及甲乙酮 R 酸酯 69.7g， 之游離異氰酸 酯基末端預聚 乙胺8 _ 6 g，在 和之溶液冷卻 水4 2 0.1 g而使 -31 - 201120275 具有羧基的異氰酸酯基末端預聚物的中和物乳化分散，得 到分散液。繼而，將60質量％之氫化聯胺5.2g與二乙三胺 溶解於水20g之聚胺水溶液添加於前述分散液，以35 °C鏈延伸長反應60分鐘後，減壓下，以3 5 °C進行脫溶劑， 得到不揮發分3 5.0質量％、黏度1 8 0 mP a · s ( B Μ黏度劑、 2號旋轉子、6(^?111)、？11値9.5、平均粒徑7〇11111之安定的 具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之水分散物。 此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂中之羧基 含量與羧酸酯基含量之合計爲1.3質量％，100%模數爲2 MPa。又，此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之 水分散物係在90°C加熱中亦不會凝膠化而爲無感熱凝固性 者。 (合成例5 ) 於附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中’饋入1，6 -己二醇聚碳酸酯多元醇（平均分子 量 2000) 146.1g、1，4 -丁二醇 2.9g、三羥甲基丙烷 i.7g' 2,2-二羥甲基丙酸11.lg、二丁基錫二月桂酸酯〇〇〇lg及甲 乙酮l〇5g’均一地混合後’加入二環己基甲烷二異氰酸酯 83.2g’在80 °C下反應240分鐘’得到對於不揮發分之游離 異氰酸酯基的含量爲3.8質量％之具有羧基的異氰酸酯基末 端預聚物的甲乙酮溶液。 使前述溶液冷卻至50°C以下後，加入三乙胺7.9g，在 4 0 °C進行中和反應3 0分鐘。其次，使進行中和之溶液冷卻 -32- 201120275 至30 °C以下，使用分散機葉片而徐緩地加入水403.3 g而使 具有羧基的異氰酸酯基末端預聚物的中和物乳化分散，得 到分散液。繼而，將60質量％之氫化聯胺7.7g與二乙三胺 1 . 3 g溶解於水2 0g之聚胺水溶液添加於前述分散液，以3 5 °C鏈延伸長反應60分鐘後，減壓下，以35°C進行脫溶劑， 得到不揮發分35.0質量％、黏度40 mPa· s(BM黏度劑、1 號旋轉子、60rpm) ' pH値8.0、平均粒徑40nm之安定的具 有羧基及羧酸酯基之聚胺基甲酸酯樹脂之水分散物。 此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂中之羧基 含量與羧酸酯基含量之合計爲1.5質量％，100%模數爲18 MPa。又，此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之 水分散物係在90°C加熱中亦不會凝膠化而爲無感熱凝固性 者。 (合成例6 ) 於附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中’饋入1，6-己二醇聚碳酸酯多元醇（平均分子 量 2000) I34.3g、1,4 -丁二醇 3.5g、三羥甲基丙烷 3.8g、 2,2·二羥甲基丙酸i〇.9g、二丁基錫二月桂酸酯0001g及甲 乙酮l〇5g’均一地混合後’加入二環己基甲烷二異氰酸酯 92.6g’在80 °C下反應210分鐘，得到對於不揮發分之游離 異氰酸酯基的含量爲4.2質量％之具有羧基的異氰酸酯基末 端預聚物的甲乙酮溶液。 使則述溶液冷卻至5 0。(：以下後，加入三乙胺7 · 8 g，在 -33- 201120275 4〇°C進行中和反應30分鐘。其次，使進行中和之溶液冷卻 至30 °C以下，使用分散機葉片而徐緩地加入水405.0g而使 具有羧基的異氰酸酯基末端預聚物的中和物乳化分散，得 到分散液。繼而，將60質量％之氫化聯胺6.9g與二乙三胺 2.〇g溶解於水20g之聚胺水溶液添加於前述分散液，以35 °C鏈延伸長反應60分鐘後，減壓下，以3 5 °C進行脫溶劑， 得到不揮發分35.0質量％、黏度230 mPa · s ( BM黏度劑、 2號旋轉子、60rpm) 、pH値8.7、平均粒徑90nm之安定的 具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之水分散物。 此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂中之羧基 含量與羧酸酯基含量之合計爲1.5質量％，100 %模數爲23 MPa。又，此具有羧基及羧酸酯基之聚胺基甲酸酯樹脂之 水分散物係在90t加熱中亦不會凝膠化而爲無感熱凝固性 者。 (比較合成例1 ) 於附有攪拌機、回流冷卻管、溫度計及氮氣導入管之 四口燒瓶中，饋入聚四亞甲基甘醇（平均分子量10 00 ) 76.1g、聚氧乙烯聚丙二醇隨機共聚物甘醇（平均分子量 1000 '氧乙烯基含量70質量％) 16.9g、1，4-丁二醇1.5g、 三羥甲基丙烷1.9g、二丁基錫二月桂酸酯O.OOlg及甲乙酮 6〇g’均一地混合後，加入二環己基甲烷二異氰酸酯40.4g ’在80 °C下反應300分鐘，得到對於不揮發分之游離異氰 酸酯基的含量爲2.1質量％之異氰酸酯基末端預聚物的甲乙 -34- 201120275 酮溶液。 使前述溶液冷卻至3 0 °C以下後，添加癸基磷酸酯 及聚氧乙烯三苯乙烯基苯基醚（HLB = 15) 6.0g，均一 合後，使用分散機葉片而徐緩地加入水254.0 g而進行 乳化，進行分散，得到分散液。繼而，將六氫化吡晴 和物2.0g與二乙三胺0.8 g溶解於水11.3 g之聚胺水溶液 於前述分散液，以35°C鏈延伸長反應90分鐘後，減壓 以3 5 °C進行脫溶劑，得到不揮發分3 5.0質量％、黏 mPa. s(BM黏度劑、1號旋轉子、60rpm) 、pH値8.0 均粒徑5 50nm之安定的水性聚胺基甲酸酯樹脂之水分 〇 此水性聚胺基甲酸酯樹脂中之羧基含量與羧酸酯 量之合計爲〇.〇質量％，100%模數爲2 MPa。又，此水 胺基甲酸酯樹脂之水分散物係在45 °C下產生凝膠化而 感熱凝固性者》 以下，於表1歸納表示合成例1 ~6、比較合成例1 狀。 0.1 g 地混 轉相 i 6水 添加 下， 度50 、平 散物 基含 性聚 具有 之性 -35- 201120275 〔一谳〕 比較合成例1 35.0 § V〇 〇· CO 合成例6 35.0 〇 § ΟΊ csi 摧 〇 σ\ 合成例5 35.0 〇 Ο ΟΟ 摧 〇 合成例4 35.0 § 1 i Ο cn CM 摧 Λ 合成例3 35.0 〇\ r—Η CN ΟΟ 璀 Ο &lt;y\ 合成例2 35.0 〇 \ο· 异 r· 1 cn m 摧 ο 合成例1 35.0 1 &lt; ΟΟ cn CO 摧 ο Os 不揮發分（質量％) 黏度（mPa · s ) pH値 平均粒徑（nm) 羧基含量（質量％) 100%模數（MPa) 乳化劑（有•無） 感熱凝固溫度（°c ) -36 201120275 〔實施例1〜10及比較例1〜6〕 (實施例1 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物1 0 0 g、硫酸銨之2 0質量％水溶液 17.5g、Texport BG〔醇系浸透劑、商品名、日華化學（股 )製〕之50質量％水溶液6.0g及水16.5g均一地混合而調製 混合液。在前述混合液中之具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂與硫酸銨的調配比係100: 10，pH値爲6.2，感 熱凝固溫度爲57 °C，具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂的含量爲25質量％。 將此混合液於由聚酯纖維所構成之不織布（0.5 dt ex、 密度0.3g/cm3 )，使用狹縫軋布機而含浸成爲壓吸率（ pick up) 250質量％後，以熱風乾燥機〔TABAI SAFETYOVEN S P Η - 2 0 0〕，以1 〇 〇 °C進行乾燥3分鐘，然後 以1 5 0 °C進行乾燥3分鐘，得到人工皮革。進一步，使所得 到之人工皮革（皮革用材料）以下述條件下染色，進行RC 吸附，得到人工皮革染色加工布（染色加工之皮革用材料 〈染色條件〉 染色機：Mini color染色機〔（股）Texam技術〕 染料：Kayalon Microester Blue DX-LS cone〔日本化 藥（股）〕〇.l〇%o.w.f.201120275 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a material for leather. In more detail, an aqueous polyurethane tree can be suitably used as artificial leather or Leather making method for synthetic leather and leather material. [Prior Art] As a substitute for natural leather, a synthetic leather of a fiber composed of a human polyurethane resin composed of an ester resin and a non-woven fabric and a fabric or a knitted fabric has been conventionally used. A variety of classes have been manufactured. Such artificial leather is, for example, similar to natural leather, impregnating or coating a polyurethane coating solution on a fibrous substrate, a weak solvent for a polyamine group, and by having compatibility with the organic solvent It is solidified in water, and then it is produced by a method of washing with water and drying. However, the organic solvent which is often used in such a wet coagulation method is highly flammable and has high toxicity. In addition to the risk of fire, it is also concerned about environmental pollution such as deterioration of the working environment. Then, in order to solve the problem of the step of performing the organic solvent generated by the recovery, there are still expensive waste disposal costs or labor problems. The human and leather materials obtained from the organic solvent solution of the polyurethane resin are obtained. Made of fat, made of polyurethane-based leather and a solidified solution of organic sequestrate resin made of a synthetic resin (a type of wet-coagulated methylformamide) Water problem, method, but also, the use of leather, 5-5, 201120275 into leather, the residual organic solvent inside the leather, so the impact on the human body is also problematic. Therefore, the study is fixed The transfer of the urethane resin from the organic solvent type to the aqueous polyamine hydrazine. The artificial method of using such an aqueous polyurethane resin does not use an organic solvent, so the recovery point can be deleted and the operation can be performed. It is excellent in terms of environmental improvement, air pollution, and water pollution improvement, but when compared with artificial leather and synthetic leather obtained by using a polyurethane solvent solution The reason why the artificial leather and the synthetic leather having the feeling of the hand and the physical properties are large are, for example, the movement of water which evaporates on the surface of the substrate when the aqueous polyurethane is inside the fiber substrate and dried by hot air. The induced aqueous polyurethane group moves to the surface of the fibrous substrate, that is, the so-called migration property, that is, by mobility, in the human manufacturing method using the aqueous polyurethane resin, the aqueous polyaminocarboxylic acid The ester resin moves to the surface and is in a state of being set as a polyurethane in the inside of the fiber base material, and is an artificial leather which is hard to handle and lacks a hairiness. Therefore, an artificial method using an aqueous polyurethane resin is used. In order to solve the problem of migration, various kinds of enthalpy have been disclosed, for example, in Japanese Patent Publication No. 5 5-5 1 076 (Patent 3, which discloses the addition of a sensitizing gelling agent to impregnate a heat-sensitive resin emulsion into a fiber. The base material is solidified in hot water, and the organic resin which is required to be turbid or the like required for the production of the polyurethane resin such as the dimensional barrier of the substrate is not available. In the case of impregnation, the production of a fiber base material such as a leather substrate from which a resin such as a leather is produced is almost unfinished, synthetic leather, and the like is being carried out: in 1), the coagulating synthetic resin emulsion-6 - 201120275 Method for producing a leather material in liquid. However, in such a method, although the migration property is prevented from being improved, a part of the impregnation liquid flows out into the bath to be solidified, and the solidified gel is attached to the processed product. On the surface, there is a problem that the hand of the obtained leather material is deteriorated. Further, in such a method, as the concentration of the polyurethane resin is lowered, the thermocoagulability is lowered, and one part of the impregnation liquid is easily discharged into the hot water. In addition, the problem of the change in the feel of the material for the leather is also poor. Further, in Japanese Laid-Open Patent Publication No. Hei 6- 3 1 6 8 7 7 (Patent Document 2), a non-forced emulsification has been disclosed. A method for producing an artificial leather in which an inorganic resin-based aqueous resin composition is dissolved in an ionic emulsion and is applied to a non-woven sheet and heated and dried. However, in such a method, although the migration property is prevented from being improved, the problem of processing in which the stability of the treatment bath is deteriorated is still existing by the concentration of the inorganic salt to be blended. Further, since the nonionic surfactant and the inorganic salt remain in the fibrous base material, the obtained leather material is rough in texture, low in abrasion resistance, and insufficient in frictional fastness. Further, in JP-A-2000-290879 (Patent Document 3), an aqueous polyurethane resin having a thermosensitive solidification temperature of 40 to 90 ° C and a meeting-type tackifier have been disclosed. A method for producing a fibrous sheet-like composite in which an aqueous resin composition is impregnated or coated on a fibrous material substrate to thermally solidify the aqueous resin composition. However, in such a method, although the migration property is prevented from being improved, the nonionic surfactant and the viscous tackifier remain in the matrix of the fibrous material, so that the obtained leather material is still rough and has low abrasion resistance. , friction firm 201120275 is not sufficient. Further, in Japanese Patent Publication No. 20 03-1 38 1 3 1 (Patent Document 4), a carboxylate type polyaminocarboxylic acid containing a nonionic surfactant of HLB 10 to 18 and an inorganic salt has been disclosed. A method for producing a sheet material for leather obtained by imparting a thermosensitive solidification to a matrix of a fibrous material. However, even in such a method, as in the method described in the above Patent Document 2 or 3, a problem caused by a surfactant or an inorganic salt is generated, and the obtained leather material is rough and has a fast rubbing property. Not enough. Further, in the methods described in the above-mentioned Patent Documents 2 to 4, the residue of the non-ionic surfactant and the chelating-type tackifier is carried out by repeating the steps of washing with water or hot water, and it is possible to remove a certain degree, but it is difficult. Completely removed, the aforementioned problems cannot be avoided. Further, the step of repeating the washing with water or the washing of hot water has become an increase in the number of processing steps and is related to economic problems. Therefore, it is required to reduce the steps of washing with water or hot water as much as possible, and the residue can be easily removed to obtain a method for producing a material for leather having sufficient hand or physical properties. Further, in JP-A-2-06-3696 (PTL 5), it is disclosed that a mixture containing a carboxyl group-containing polyurethane resin, an ammonium salt of a carboxylic acid, and water is impregnated into the fiber. A method of producing a material for leather which is dried after the substrate. However, in such a method, although the problem of mobility can be solved, a new problem of odor generated by ammonia gas which occurs during drying is generated. Further, when a carboxylate ammonium salt having a small carbon number of ammonium formate or ammonium acetate is used as the carboxylic acid salt -9 - 201120275, there is a problem that the carboxylic acid which is heated and dried to volatilize the oxidizing device is corroded, and the manufacturing steps must be improved. . Further, when an ammonium salt of a carboxylic acid having a large carbon number is used, little carboxylic acid is volatilized when heated and dried, but it is necessary to use it in a large amount in order to obtain the purpose of preventing migration. Further, in order to improve the durability such as heat resistance of the resin, if a polycarbodiimide compound is used in combination with the ammonium carboxylate salt, it is difficult to obtain sufficient migration prevention even if a large amount of the ammonium carboxylate salt is used. . In the manufacturing method of the artificial leather or the like using the aqueous polyurethane resin, the polyurethane resin can be uniformly fixed to the fibrous substrate while the migration property is sufficiently prevented, and the engineering process occurs. The odor of the gas and the corrosion of the device are small, and a method for producing a material for leather having a sufficient texture or quality cannot be obtained, and it is necessary to have a VOC countermeasure that occurs in engineering. SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems of the prior art, and it is an object of the invention to provide an aqueous polyurethane resin for use in consideration of environmental load or VOC. The method for producing the material can sufficiently prevent the migration and the odor of the gas generated in the project and the corrosion of the device to be less, and the hand feeling can be obtained with high efficiency and abrasion resistance or friction fastness. A method for producing a leather material for leather materials which is excellent in physical properties, and a material for leather obtained by the method for producing the same. The inventors of the present invention have accumulated the results of intensive research to achieve the above object. -9- 201120275 'It was found that by impregnating a fiber base with a mixture containing a specific aqueous polyurethane resin, a mineral acid salt and water After the material is dried, the aqueous polyurethane resin is allowed to migrate and is not localized during drying, and the polyurethane resin is uniformly fixed to the inside of the fiber substrate to have a soft hand and sufficient The material for leather of physical properties is based on this knowledge to complete the present invention. That is, the method for producing a material for leather of the present invention, which comprises (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (b) an ammonium salt of a mineral acid, and (C) A mixture of water, which is impregnated on a fibrous substrate and then dried to obtain a material for leather. . The above mixed liquid of the present invention is preferably a compounding ratio of (A) a urethane resin having a carboxyl group and/or a carboxylate group and (B) an ammonium salt of a mineral acid, and is converted in terms of the mass of the solid component. A) : (B) =100: 〇. 1~1〇〇 :50 ° Further, the above mixture is preferably pH 5. 0~7 _0, again, the heat-curing temperature should be 30~80 °C. The inorganic acid in the ammonium salt of the (B) inorganic acid of the present invention is preferably sulfuric acid and/or phosphoric acid. In the above (A) the polyurethane resin having a carboxyl group and/or a carboxylate group, (a) an organic diisocyanate, (b) a polyhydric alcohol, and (c) have a carboxyl group and two or more. The isocyanate group-terminated prepolymer having a carboxyl group obtained by the reaction of the active hydrogen compound is neutralized and emulsified and dispersed by self-emulsification in water, and (d) a polymer having two or more amine groups and/or imine groups is used. The amine compound is subjected to a chain extension reaction to obtain a urethane resin having a carboxy-10-201120275 group and/or a carboxylate group. Further, the above-mentioned (A) polyaminocarbamate resin having a carboxyl group and/or a carboxylate group is preferably a combination of a carboxyl group content and a carboxylate group content of 0. 5~4 〇 mass %. Further, the material for leather of the present invention is obtained by the above-described production method of the present invention. According to the present invention, it is possible to provide a method for producing a leather material which is an aqueous polyurethane resin which is used for consideration of an environmental load or a problem of V Ο C, and can sufficiently prevent migration and, in engineering, The odor of the gas and the corrosion of the device are small, and the method for producing a leather material for leather materials which is excellent in physical properties such as softness, abrasion resistance, and friction fastness, and the like, and The material for leather obtained by the method of manufacture. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on preferred embodiments thereof. The method for producing a material for leather of the present invention comprises a mixture of (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and (C) water. The liquid is impregnated into the fibrous substrate and then dried to obtain a material for leather. Thus, the (A) polyurethane resin having a carboxyl group and/or a carboxylate group of the present invention has a carboxyl group and/or a carboxylate group as a hydrophilic component in a urethane resin skeleton. A urethane resin. Such a (A) polyurethane resin having a carboxyl group and/or a carboxylate group may be suitably used in the range of -11 - 201120275: (a) an organic diisocyanate, (b) a polyhydric alcohol, and (c) a carboxyl group. The isocyanate group-terminated prepolymer having a carboxyl group obtained by reacting a compound having two or more active hydrogens is neutralized and emulsified and dispersed by self-emulsification in water, and (d) having two or more amine groups and/or The imine group polyamine compound causes a chain extension reaction to obtain a polyurethane resin having a carboxyl group and/or a carboxylate group. The (a) organic diisocyanate is not particularly limited, and an aliphatic diisocyanate having two isocyanate groups, an alicyclic diisocyanate, and an aromatic diisocyanate can be used. The (a) organic diisocyanate may, for example, be an aliphatic diisocyanate compound such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate, isophorone diisocyanate or hydrogenated xylene diisocyanate. An alicyclic diisocyanate compound such as dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene An aromatic diisocyanate compound such as diisocyanate, tolidine diisocyanate, xylene diisocyanate or tetramethyl xylene diisocyanate. These diisocyanate compounds can be used singly or in combination of two or more. In the (a) organic diisocyanate, the 'aliphatic diisocyanate compound and the alicyclic diisocyanate compound are imparted to the leather material to impart yellow-free denaturation, so that it is suitable to use the U.S. Methyl diisocyanate, isophorone diisocyanate, dicyclohexylylene diisocyanate, norbornane diisocyanate and 1,3-bis(isocyanate methyl)cyclohexane. Further, (b) the polyol is not particularly limited as long as it has two or more hydroxyl groups, and may be used in addition to polyester polyols, polycarbonate polyols, polyalcohols, and the like. There are many polyether esters of a bond and an ester bond; such a polyester polyol may, for example, be a polyethylene adipate adipate, a polyvinyl butylene adipate, or a polyhexamethylene isophthalate. , polyethylene succinate, polybutylene succinate, polydiester, polybutylene sebacate, polycaprolactone diol, poly-1,5-pentene) adipate, 1 , a mixture of 6-hexanediol and a dimer acid, a cocondensate of 1,6-hexanediol with adipic acid and a dimer acid, a polycondensate with a dimer acid, ethylene glycol and Diacid and dimer condensate and the like. Further, examples of the polycarbonate polyol include polytetramethylene glycol diol, polyhexamethylene polycarbonate diol, and poly-1,4-cyclohexane methyl polycarbonate diol. 6-hexanediol polycarbonate polyol, and the like. Further, the polyether polyol may, for example, be a polyethylene glycol decyl alcohol, a single polymer of polytetramethylene glycol, a block copolymer copolymer, ethylene oxide and propylene oxide, or ethylene oxide. Copolymer or block copolymer with epoxy butylene. Further, such a (b) polyol may be used alone or in combination of one or more types. Further, the amount of the (b) polyol is preferably from 500 to 5,000, more preferably from 1,000 to 3,000. Further, from the viewpoint of imparting sufficient durability to a material by a polyurethane resin having a carboxyl group and/or a carboxylate group, the above (b) uses a polycarbonate polyol or a polyether polyol. alcohol. Further, (c) a compound ether polynonanol having a carboxyl group and two or more active hydrogens. , polybutyl phthalate vinyl hydrazine (3-methyl polycondensed decanediol acid eutectic polycarbanediamine, polypropylene, random alkane with U and 2 molecules obtained from the leather alcohol suitable, can be - 13- 201120275 For example, 2,2-dimethylolpropionic acid, 2,2-hydroxymethylbutyric acid, etc. Further, a compound having such a carboxyl group and two or more active hydrogens may also be a diol having a carboxyl group. a polyester polyol having a pendant carboxyl group obtained by reacting with an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, etc. Further, in place of the above-mentioned diol having a carboxyl group, a diol having no carboxyl group may be mixed as a diol Further, the compound having such a carboxyl group and two or more active hydrogens may be used singly or in combination of two or more kinds thereof. (a) an organic diisocyanate, (b) a polyhydric alcohol, and (c) When a compound having a carboxyl group and two or more active hydrogens is reacted to produce an isocyanate group-terminated prepolymer having a carboxyl group, a low molecular weight chain extender having two or more active hydrogen atoms may be used as needed. Low scores of more than one active hydrogen atom The sub-chain extender preferably has a molecular weight of 400 or less, particularly preferably 300 or less. Further, such a low molecular weight chain extender may, for example, be ethylene glycol, propylene glycol, neopentyl glycol, or 1,4-butane. a low molecular weight polyol such as an alcohol, 1,6-hexanediol, trimethylolpropane, pentaerythritol or sorbitol; ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, a low molecular weight polyamine such as hexahydropyrazine, 2-methylhexahydropyrazine, isophoronediamine, diethylenediamine or triethylenetetramine, etc. Further, having two or more active hydrogen atoms The low molecular weight chain extender may be used singly or in combination of two or more. In the present invention, a specific method for producing an isocyanate group-terminated prepolymer having a carboxyl group is not particularly limited, and can be known, for example, from the prior art. One-stage one-shot one shot, multi-stage isocyanate polyaddition reaction • 14 - 201120275 method, etc. The reaction temperature should be 40~l5〇 °C. Dibutyltin dilaurate vinegar can be added as needed a reaction catalyst such as tin octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, hydrazine, methylphenidene, etc. Further, after the reaction or after the reaction, it may be added The organic solvent to be reacted with an isocyanate group. Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, tetra-furfuran, di-chewing, dimethylformamide, fluorene-methylpyrrolidone, etc. In the present invention, a carboxyl group is present. The isocyanate group-terminated prepolymer is neutralized before or after the preparation of the isocyanate group-terminated prepolymer having a carboxyl group by a suitably known method, and is used in such an isocyanate group-terminated prepolymer having a carboxyl group. The compound is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, hydrazine-methyl-diethanolamine, hydrazine, hydrazine-dimethylmonoethanolamine, hydrazine, hydrazine-di An amine such as ethyl monoethanolamine or triethanolamine, potassium hydroxide, sodium hydroxide or ammonia. Among the above compounds, a third-grade amine such as trimethylamine, triethylamine, tri-n-propylamine or tributylamine is particularly preferable. Further, in the present invention, the emulsification device used when the isocyanate group-terminated prepolymer having a carboxyl group is emulsified and dispersed in water is not particularly limited, and examples thereof include a homomixer, a homogenizer, a mixer, and the like. . Further, when the isocyanate group-terminated prepolymer having a carboxyl group is emulsified and dispersed in water, it is preferred to use an isocyanate group-terminated prepolymer having a carboxyl group, particularly without using an emulsifier, at room temperature to 40 ° C. The temperature range is emulsified and dispersed in water' and the reaction between the isocyanate group and water is strongly suppressed. Further, in the case of emulsification and dispersion, the reaction inhibition of phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, -15-201120275 p-toluenesulfonic acid, adipic acid, benzylidene chloride, etc. may be added as needed. Agent. Further, in the present invention, the isocyanate group-terminated prepolymer having a carboxyl group is emulsified and dispersed in water, and then (d) a polyamine compound having two or more amine groups and/or imine groups is used. The chain extension reaction allows the objective (A) emulsified dispersion of the urethane resin having a carboxyl group and/or a carboxylate group. Such a (d) polyamine compound having two or more amine groups and/or imine groups may, for example, be ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine or diamine. Cyclohexylmethane, hexahydropyrazine, hydrazine, 2-methylhexahydropyrazine, isophoronediamine, norbornanediamine, diethyldiphenylmethane, toluenediamine, xylylenediamine a diamine, a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminodipropylamine or tris(2-aminoethyl)amine; a second-stage and monocarboxylic acid Derivatized guanamine; water-soluble amine derivative of monoketone and the like of the first-order amine; alginic acid diamine, malonic acid diamine, succinic acid diamine, glutaric acid amide, Diacid diamine, sebacic acid diamine, maleic acid diamine, fumaric acid diamine, itaconic acid diamine, 1,1'-ethylene hydrazine, 1,1'- A bisamine derivative such as a trimethyleneamine or a 1,1'-(1,4-butylene)diamine. These polyamine compounds having two or more amine groups and/or imine groups may be used alone or in combination of two or more. In the present invention, among the isocyanate group-terminated prepolymers having a carboxyl group, The chain extension reaction of the compound is carried out in the emulsified dispersion of the intermediate of the isocyanate group-terminated prepolymer having a carboxyl group, and (d) a polyamine compound having two or more amine groups and/or imine groups may be added. get on. Further, the emulsified dispersion of the isocyanate group-terminated prepolymer having a carboxyl group may be added to the polyamine compound having two or more amine groups and/or imine groups in (d) -16 to 201120275. . The chain extension reaction is preferably carried out at a reaction temperature of 20 to 40 X: and is usually completed at 30 to 120 minutes. When an organic solvent is used in the production of an isocyanate group-terminated prepolymer having a carboxyl group, for example, after the chain extension reaction is terminated, the organic solvent is removed by distillation under reduced pressure or the like. In the present invention, (A) a 100% modulus of the polyurethane resin having a carboxyl group and/or a carboxylate group is preferably 0. 5 to 20 MPa, more preferably 2 to 6 MPa. When the 100% modulus is less than the lower limit, a soft material for leather can be obtained. However, the abrasion resistance tends to be weak, and if the upper limit is exceeded, the leather material obtained is hard. There is a tendency to decrease the adhesion to fibers. Here, the 1% modulus is measured according to JIS K 625 1 (20〇4) using a dumbbell-shaped test piece of No. 3 shape, and the distance between the lines is extended by 100% (extending to 2 times) The specific extension tensile stress (MPa) in time). Further, in the present invention, the total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and/or a carboxylate group (A) is preferably 0. 5-4. 0% by mass, more preferably 1. 0~2. 0% by mass. When the total of the carboxyl group content and the carboxylate group content is less than the above lower limit, the storage stability of the obtained (A) polyurethane resin having a carboxyl group and/or a carboxylate group tends to be deteriorated' In addition, when the temperature exceeds the above upper limit, the thermosensitive solidification temperature generated when it is mixed with the ammonium salt of the inorganic acid (B) becomes high, and the effect of preventing migration during the production of the material for leather is weakened. In the present invention ( B) The inorganic acid in the ammonium salt of the inorganic acid may, for example, be -17-201120275 such as perchloric acid, carbonic acid, sulfuric acid, persulfuric acid, sulfurous acid, phosphoric acid, nitric acid or the like. Among such inorganic acids, sulfuric acid and/or phosphoric acid is preferred because it is excellent in the migration preventing effect. Specific examples of the (B) ammonium salt of the inorganic acid include ammonium persulfate, ammonium perchlorate, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, diammonium hydrogen phosphate, dihydrogen phosphate. Ammonium, ammonium persulfate, ammonium nitrate, and the like. The ammonium salt of the (B) inorganic acid can be suitably used from the viewpoints of the safety of the treatment, the problem of volatilization during drying, and the fact that it can be easily removed by washing with water after drying, and remains small in the material for leather. At least one selected from the group consisting of ammonium sulfate, diammonium phosphate, and ammonium dihydrogen phosphate. Further, diammonium hydrogen phosphate may be used singly, but ammonium dihydrogen phosphate is preferably used in combination with diammonium hydrogen phosphate. In the method for producing a material for leather according to the present invention, when (B) an ammonium salt of a mineral acid is mixed with (A) an emulsified dispersion of a polyurethane resin having a carboxyl group and/or a carboxylate group, The (B) ammonium salt of the inorganic acid may be mixed as a solid (powder) in an emulsified dispersion of (A) a urethane resin having a carboxyl group and/or a carboxylate group, but from the retention ( A) From the viewpoint of the stability of the emulsified dispersion of the urethane resin having a carboxyl group and/or a carboxylate group, it is preferred to mix the (B) ammonium salt of the inorganic acid in the form of an aqueous solution. In the aqueous solution of the ammonium salt of the (B) inorganic acid, the concentration of the ammonium salt of the inorganic acid is preferably from 1 to 50% by mass, more preferably from 10 to 30% by mass. When the concentration of the (B) ammonium salt of the inorganic acid in the aqueous solution is less than the lower limit, it is mixed with (A) a polyamine group having a carboxyl group and/or a carboxylate group in order to exhibit migration prevention during drying. When the emulsified dispersion of the formic acid ester resin is -18-201120275, a large amount of the above aqueous solution must be added, and there is a concentration of the polyurethane resin having a carboxyl group and/or a carboxylate group in the mixed solution (A). decline. Therefore, in order to fix a necessary amount of the polyurethane resin having a carboxyl group and/or a carboxylate group to the fiber substrate, it is necessary to impregnate a large amount of the mixed liquid on the fiber substrate, and the amount of water volatilized during drying becomes large. Therefore, there is a tendency that the drying time becomes longer and the economy deteriorates. Further, when the concentration of the ammonium salt of the (B) inorganic acid in the aqueous solution exceeds the above upper limit, it is produced by mixing with (A) an emulsified dispersion of a polyurethane resin having a carboxyl group and/or a carboxylate group. Precipitates and the like tend to impair the stability of the emulsified dispersion. Further, in the (C) aqueous system of the present invention, (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, and (B) an ammonium salt of a mineral acid 'has a role as a solvent. Ion exchange water or distilled water can be suitably used. In the present invention, a method of adjusting a mixture of (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and (C) water is not particularly limited. A suitable well-known method can be used. Further, in the mixed liquid, the ratio of the (A) carboxyl group-containing resin having a carboxyl group and/or a carboxylate group to the ammonium salt of the (B) inorganic acid is preferably converted to the mass of the solid component. (A) : (B) =100: 0. 1-100 : 50' is more preferably 1 〇〇: 1 to 100: 40. The aforementioned blending ratio exceeds 100: 0. 1 hour', that is, the ratio of the ammonium salt of the inorganic acid is less than 0. At 1 o'clock, there is a tendency to prevent the migration effect from being weakened in the drying step. When the blending ratio is less than 100:50, that is, when the blending ratio of the ammonium salt of the inorganic acid is more than 50, in the temperature environment of the summer field, there is a mixture. The tendency of liquid gelation. Further, the solid form of the present invention -19-201120275 is a residue obtained by heating the sample at a temperature of 105 ° C for 3 hours. Further, the sensible heat setting temperature of the above mixture is preferably from 30 to 80 ° C, more preferably from 40 to 70 ° C. Here, the thermosensitive solidification temperature is obtained by taking 50 g of the mixed liquid into a glass beaker of 100 mL, stirring the contents, and slowly heating the beaker in a hot water bath at 95 ° C to lose the fluidity of the contents. The temperature at which it solidifies. When the sensible heat setting temperature does not reach the above lower limit, there is a tendency for the mixed liquid to gel in the temperature ring environment of the summer field. When the temperature exceeds the upper limit, the sensible heat solidification is not apparent, so the migration resistance is weakened in the drying step. tendency. Further, the content of the polyurethane resin having a carboxyl group and/or a carboxylate group in (A) in the mixed liquid is preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass based on the mass of the solid component. quality%. If the content of the urethane resin having a carboxyl group and/or a carboxylate group is less than the above lower limit, the necessary amount of the polyurethane resin is fixed, and a large amount of the aforementioned mixture is impregnated with respect to the fibrous substrate. Therefore, the amount of water in the dry volatilization becomes large and the drying time becomes long, which tends to be economically deteriorated. Further, when the content of the polyurethane resin having a carboxyl group and/or a carboxylate group exceeds the above upper limit, the stability of the mixed solution tends to be deteriorated. When a mixed liquid containing a conventional urethane resin having a carboxyl group and/or a carboxylate group becomes acidic, the emulsion stability is lowered, so that it is difficult to use for the production of a material for leather, but the mixture of the present invention Is the pH 値 even the acidic side (preferably 5. 0~7. 0, more preferably 5. 5~6. 8, especially suitable for 6. 0~6. 5) The emulsification of a polyurethane resin having a carboxyl group and/or a carboxylate group is stable and can be used for the production of a material for leather. Further, the fiber base material of the present invention is not particularly limited, and can be suitably used for a woven fabric, a knitted fabric, a nonwoven fabric or the like. The material of such a fibrous base material can be suitably used in the case of using a polyamide fiber or a polyester fiber because the texture and quality of the natural leather can be approximated. Further, in the nonwoven fabric used as the fiber base material, the thickness of the non-woven fabric is preferably 2 to 10 dtex or less from the viewpoint of improving the hand feeling of the obtained leather material. If the thickness of the non-woven fabric exceeds 2 inches, the texture of the leather material becomes rough and detracts from the quality. Moreover, the density of such a non-woven fabric is preferably 0. 2~〇_7g/cm3, more preferably 0. 3 0~0. 5 5g/cm3. If the density of the non-woven fabric does not reach the above lower limit, the abrasion resistance of the obtained leather material tends to be deteriorated, and in order to compensate for this, if a large amount of the polyurethane resin is fixed, the obtained leather material is used. The feel becomes rough and tends to impair quality. Further, if the density of the non-woven fabric exceeds the above upper limit, the texture of the leather material becomes rough and the quality tends to be impaired. The method for producing a material for leather according to the present invention comprises a mixture of (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and (C) water. In the range which does not impair the object of the present invention, various additives may be added for the purpose of imparting workability. Examples of such an additive include, for example, a lower alcohol 'glycol solvent, an alcohol-based nonionic surfactant, an ethylene glycol-based special surfactant, an anthrone-based surfactant, a fluorine-based surfactant, and the like. Various soaking agents; various stabilizers such as antioxidants, light stabilizers, anti-UV agents, etc.; various defoamers such as mineral oils, polyfluorenes, etc.; urethane catalysts, plasticizers - 21 - 201120275, coloring agents such as pigments, time extenders, etc. Such an additive may be used singly or in combination of two or more. Further, in such an additive, it is particularly preferable to add a penetrating agent. By using the impregnating agent, the above-mentioned mixed liquid can be rapidly impregnated on the above-mentioned fibrous base material, and at the same time, the effect of uniformly fixing the polyurethane resin to the above fibrous base material can be obtained. The permeating agent is not particularly limited as long as it is a general user, but it is preferable to use a lower alcohol, a glycol solvent, an alcohol-based nonionic surfactant, or the like. Further, in the method for producing a material for leather of the present invention, (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (b) an ammonium salt of a mineral acid, and (C) water are contained. In the mixed liquid, in the range which does not impair the object of the present invention, a crosslinking agent which reacts with a carboxyl group can be added in order to impart workability. Examples of such a crosslinking agent include an oxazoline crosslinking agent, an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and an aziridin-based crosslinking agent. A blocked isocyanate crosslinking agent, a water-dispersed isocyanate crosslinking agent, a melamine crosslinking agent, or the like. These crosslinking agents may be used singly or in combination of two or more. In the method for producing a material for leather of the present invention, a mixture containing (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and (C) water is used. The liquid is impregnated with a fibrous substrate such as a woven fabric, a knitted fabric, a non-woven fabric, or the like, and then dried. The method of impregnating the above-mentioned fiber mixture with the above-mentioned fiber base material is not particularly limited. It is preferably a conventionally known method such as impregnation processing or spray treatment composed of a dip-nip method, and may be appropriately selected. The above-mentioned -22- 201120275 concentration of the mixed solution and processing conditions. Further, the mixture of the polyurethane resin containing (A) and/or the carboxylate group, (B) the inorganic acid, and (C) water may be impregnated into the woven fabric, the knitted fabric, or the non-woven fabric substrate. Pretreatment on the fibrous substrate. In such a step, it is preferable to use an aqueous solution composed of polyvinyl alcohol, carboxymethyl cellulose, or the like, and a polyfluorinated water repellent agent or a fluorine system. In the method for producing a leather material according to the present invention, the method of producing a material for a leather material according to the present invention is a method in which the liquid mixture is impregnated into the inside of the fiber base material and then dried. For example, dry drying by hot air can be used; High temperature steaming H. T. S), high pressure steam engine (H. P. S) wet drying; microwave drying, etc., in terms of continuous processability, a hot air drying can be suitably used. These drying methods can be used singly or in combination of two or more. Further, in the dry drying using hot air, the treatment temperature is 60 to 190 ° C, the treatment time is 1 to 20 minutes, and the treatment temperature is 10 to 17 (TC, and the treatment time is 2 to 5 minutes. This drying can be carried out by fixing the polyurethane gum inside the fibrous substrate so as to contain (A) an ammonium salt having a carboxyl group and/or a carboxylate urethane resin' (B) mineral acid. And (C) water, which is impregnated with a fibrous base material and then dried to obtain the material of the present invention. In the leather material of the present invention, the solid fixing component of the leather urethane resin or the like is used. The amount of the polymer is not particularly limited to the pretreatment of the fiber, such as an ammonium salt of a carboxyl group, and the above-mentioned mixed-restricted gas machine (the dry type of the dry type of the dry type) is particularly suitable for the purpose of the mixing. Other limitations in liquid leather materials -23- 201120275 'But in leather materials' is preferably derived from (A) a component of a polyurethane resin having a carboxyl group and/or a carboxylate group of 10 0~ 90% by mass, derived from (B) the ammonium salt of the inorganic acid is 0. 5~7. 0% by mass. Further, the material for leather of the present invention can be dyed. The dyeing method is not particularly limited to the first impregnation dyeing method after dyeing the polyurethane resin to the fiber substrate, and the impregnation method after fixing the polyurethane resin after dyeing the fiber substrate. Any of the staining methods can be carried out. Further, the material for leather of the present invention may be formed into a skin layer as a material for leather having a silver surface. The method for forming such a skin layer may be any one of the conventionally known methods, and is not particularly limited. However, for example, the surface layer is coated with a material for the skin layer to evaporate water and form a skin layer. Applying an adhesive agent thereon, directly bonding the material for leather of the present invention to evaporate water' or a release paper transfer method which is adhered after evaporation of water; and the material for coating the skin layer by the release paper a heat transfer method in which water is evaporated, a skin layer is formed on the skin layer, and a skin layer is bonded to the leather material of the present invention by heat; a material for directly coating the skin layer on the leather material of the present invention; and a gravure coating method; A direct coating method of coating a material for a skin layer on a material for leather of the present invention, such as a machine, a knife coater, a wire bar coater, and an air knife coater. Even in the method of forming such a skin layer, it is most preferable to use a release paper transfer method from the viewpoint of further improving the physical properties of the obtained skin layer. The material for the skin layer and the adhesive used in the release paper transfer method may be any one that can be bonded to the leather material of the present invention, but the surface and the physical surface are preferably gathered. The urethane resin, again -24-201120275, should be water-based or solvent-free from the surface without VOC and environmental load. Further, the material for leather of the present invention can be used in the fields of vehicles, furniture, clothing, shoes, purses, bags, sandals, and groceries. [Embodiment] [Embodiment] Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples. Further, the materials for leather obtained in each of the examples and the comparative examples were evaluated by the following methods. (1) Prevention of Mobility According to the materials for leather obtained in each of the examples and the comparative examples, a section of the material for leather was observed at a magnification of 60 times using a scanning electron microscope (Scanning Electron Microscope S-2400 (H1TACHI)). 'Compared with the state of fixation of the polyurethane resin present in the central portion of the nonwoven fabric and the state of fixation of the polyurethane resin present on the surface portion of the nonwoven fabric, it was evaluated based on the following criteria. Grade 5: In the cross section of the material for leather, no difference was observed in the central portion and the surface portion at the fixed amount of the resin, and no migration property was produced. Grade 4: In the cross section of the material for leather, there was almost no difference in the amount of resin fixed at the center portion and the surface portion, and no migration property was produced. Level 3: In the cross section of the material for leather, the difference between the fixing amount of the resin at the center portion and the surface portion is -25-201120275, and the resin is fixed at 10% of the central portion occupied by the entire thickness. . Grade 2: In the cross section of the material for leather, the center portion and the surface portion are quite different in the amount of resin fixation, and no resin is observed in the 30% portion of the central portion occupied by the entire thickness. Grade 1: In the cross section of the material for leather, a significant difference was observed in the central portion and the surface portion in the amount of resin fixation, and resin fixation was not observed in the 50% portion of the central portion occupied by the entire thickness. (2) Abrasion test The material for leather obtained in each of the examples and the comparative examples was used in accordance with the pull-out method of JIS L 10 96 (19 99), and the smashing tester (manufactured by Yasuda Seiki Co., Ltd.) was used. The soft wheel CS-10 was used, and the load of 5 〇〇g was applied to make it consume 1,000 times and 3,000 times, and the amount of reduction in the weight of the leather material was expressed as the amount of wear. Further, the less the amount of friction, the more excellent the abrasion resistance of the material for leather. (3) Friction fastness According to JIS L 0 849 (2 004), the material for leather obtained according to each of the examples and the comparative examples is applied by a vibration-type friction tester (manufactured by Daiei Chemical Seiki Co., Ltd.) to apply a load. 200 g, rubbing 100 times, and measuring the wet rubbing fastness. The aforementioned rubbing fastness was measured by comparing the degree of contamination of the unbleached cotton cloth with a gray scale for pollution, and was evaluated based on the following criteria. Level 5: No pollution is seen. -26- 201120275 Level 4: A little bit of pollution. Level 3: Clearly see pollution. Level 2: The pollution is slightly visible. Level 1: Obviously see pollution. (4) Whether or not the residue is related to the materials for leather obtained in each of the examples and the comparative examples, and the components other than the nonwoven fabric and the polyurethane resin in the leather material (residues such as surfactants) The content of the extraction was measured by a Soxhlet extractor using methanol as an extraction solvent at a temperature of 70 ° C for 3 hours, and the extraction amount was 1. When 0% by mass or more is used as a residue, it is evaluated as a residue-free content of less than 10% by mass. (5) Hand feeling The feeling of the leather material obtained in each of the examples and the comparative examples was evaluated from the fifth stage (softness) to the first stage (thickness) in accordance with the following criteria. Level 5: Very soft and anti-elastic hand feeling 4: Soft and anti-elastic feeling 3: Soft and slightly lacking the elasticity of the hand 2: slightly rough and paper-like (such as paper) feel 1: Rough and paper-like (such as paper) hand feeling (6) odor when dry -27- 201120275 In each of the examples and comparative examples, the ammonia and acid odors when dried by a hot air dryer were evaluated by function. . A: odorless B: slightly odorous C: pungent odor of the pungent nose [Synthetic Example and Comparative Synthesis Example] Hereinafter, the urethane resin having a carboxyl group and a carboxylate group used in the present invention is shown. A comparative synthesis example of a synthesis example and an aqueous polyurethane resin used in the comparative example. (Synthesis Example 1) A 1,6-hexanediol polycarbonate polyol (average molecular weight 2000) was fed into a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube. 0g, neopentyl glycol 7. 5g 'trimethylolpropane 1. 3g, 2,2-dimethylolpropionic acid 9. 5g, dibutyltin dilaurate bismuth. 〇〇 lg and methyl ethyl ketone 105g, after homogeneous mixing, add isophorone diisocyanate 69. 7 g, the reaction was carried out at 80 ° C for 300 minutes, and the content of the free isocyanate group for the nonvolatile matter was 1. 9% by mass of a methyl ethyl ketone solution of a carboxyl group-containing isocyanate terminal prepolymer. After cooling the solution to below 50 ° C, adding triethylamine 6. 8 g, neutralization reaction was carried out at 40 ° C for 30 minutes. Next, the neutralized solution is cooled to below 30 ° C, and water 42 is slowly added using the disperser blades. 9 g of the neutralized product of the isocyanate-based terminal prepolymer having a carboxyl group was emulsified and dispersed to obtain a dispersion from -28 to 201120275. Then, 60% by mass of hydrogenation ® l. Lg dissolved in water 20g of polyamine aqueous solution added to the front °C chain extension reaction for 60 minutes, under reduced pressure, to obtain a non-volatile fraction of 35. 0% by mass, viscosity 120 mPa No. 2 rotor, 60 rpm), pH 値 7. 8. Average granules Polyurethane resin having a carboxyl group and a carboxylate group The total content of the polyaminocarbamide and the carboxylate group having a carboxyl group and a carboxylate group is 1. 3 mass%, 2 MPa. Further, the poly Jg aqueous dispersion having a carboxyl group and a carboxylate group does not gel even when heated at 90 °C. (Synthesis Example 2) In a four-necked flask equipped with a stirrer, a reflux cooling tube, and a temperature, a 1,6-hexanediol polycarbonate was fed in an amount of 2,000. 0g, trimethylolpropane 0. 9g, 2 9. 3g, dibutyltin dilaurate 0. After mixing 001 g and methyl ethane, the reaction was carried out by adding dicyclohexylmethane diisocyanate for 420 minutes to obtain a free amount for the nonvolatile matter of 1. 2% by mass of an isocyanate ketone solution having a carboxyl group. After the solution was cooled to 50 ° C or lower, the neutralization reaction was carried out by adding 40 ° C for 30 minutes. Secondly, let it go below 30 °C and use the disperser blades to slowly spur. 2g and diethylenetriamine dispersion, desolventization at 35 ° C, • s (B Μ viscosity agent) aqueous dispersion with a diameter of 90 nm. • carboxyl group in ester resin 1 0 0 % modulus The 完 is a non-inductive thermosetting-and nitrogen-introducing tube. Alcohol (average molecule, 2 - dimethylolpropionic acid, ketone 1 0 5 g, uniform 5 6. 9 g, at 80 ° C, isocyanate-containing y-terminated prepolymer of methyl ethyl < triethylamine 6. 7 g, the solution neutralized in i1 was cooled to 4 4 4 _ 4 g of water, and the neutralized product of the -29 - 201120275 isocyanate-based terminal prepolymer having a carboxyl group was emulsified and dispersed to obtain a dispersion. Then, 60% by mass of hydrogenated hydrazine 3. 3 g of diethylenetriamine hydrazine - 7 g of a polyamine aqueous solution dissolved in 20 g of water was added to the dispersion liquid, and the reaction was carried out by a chain extension reaction at 35 ° C for 60 minutes, and then desolvation was carried out at 35 ° C under reduced pressure. Nonvolatiles 35. 0% by mass, viscosity 70 mPa.  s (BM viscosity agent, No. 1 rotor, 60 rpm), pH 値 7. 6. An aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group having an average particle diameter of 120 nm. The total of the carboxyl group content and the carboxylate content of the urethane resin having a carboxyl group and a carboxylate group is 1. 3 mass%, 100% modulus is 5 MPa. Further, the water-repellent material of the urethane resin having a carboxyl group and a carboxylate group is not gelled at 90 ° C and is not susceptible to thermal coagulability. (Synthesis Example 3) Polytetramethylene glycol (average molecular weight 2000) was fed into a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube. 9g, 2,2-dimethylolpropionic acid 30. 8g, dibutyltin dilaurate 〇. 〇〇 lg and methyl ethyl ketone 105g, after uniform mixing, add hexamethyl diisocyanate 72. 3g ‘at 8〇. (: The reaction was carried out for 18 minutes, and the content of the free isocyanate group for the nonvolatile matter was 3. A methyl ethyl ketone solution of 1% by mass of an isocyanate-based terminal prepolymer having a carboxyl group. After cooling the solution to below 50 ° C, adding triethylamine 22. 1 g, neutralization reaction was carried out at 4 ° C for 30 minutes. Next, the neutralized solution is cooled to below 30 ° C, and the water is slowly added using the disperser blades. 6 § The neutralized product of the isocyanate-based terminal prepolymer having a carboxyl group is emulsified and dispersed, and -30-201120275 is obtained as a dispersion. Then, 60% by mass of hydrogenated hydrazine amine was used. 8 g of a polyamine aqueous solution dissolved in 20 g of water was added to the first 35 ° C chain for a long extension reaction for 60 minutes, and then reduced to 3 ί to obtain a nonvolatile content of 35. 0 mass%, viscosity 50 mPa.  , No. 1 rotor, 60 rpm), pH 値 7. 9. A granule resin having a carboxyl group and a carboxylate group having an average grain name. The total content of the carboxyl group and the carboxylate group of the carboxyl group and the carboxylate group is 4. 2% by mass, MPa. Further, the polyamino-based aqueous dispersion having a carboxyl group and a carboxylate group does not gel at a temperature of 90 °C. (Synthesis Example 4) Into a stirrer, a reflux cooling tube, a thermometer, and a four-necked flask, a 1,6-hexanediol polycarbonate amount of 2000 was fed. 0g, neopentyl glycol 7. 5g, trishydroxymethyl hydrazine dimethylolpropionic acid 9. After 5 g of dibutyltin dilaurate 0, l〇5g' was uniformly mixed, isophorone diisoindole was added and reacted at 8 ° C for 300 minutes to obtain a content of 1.0 for the nonvolatile vinegar group. 9% by mass of a methyl ethyl ketone solution of a carboxyl group-containing isocyanate. After the solution was cooled to 50 t or less, a neutralization reaction was carried out for 30 minutes by adding 3 ° C. Next, let the process proceed to 30 ° C or less, and slowly add 7:8 using the disperser blades. 6g and diethylene three dispersions, desolvent s at °C; (B Μ viscosity agent 1 50nm stable aqueous dispersion. The carboxyl group in the resin 100% modulus is 8 formate resin non-inductive thermal coagulation Alkaline nitrogen introduction tube alcohol (average molecular weight alkane 1. 3g, 2,2-001 g and methyl ethyl ketone R acid ester 69. 7g, the free isocyanate-based end prepolymerized ethylamine 8 _ 6 g, and the solution cooling water 4 2 0. 1 g and -31 - 201120275 The neutralized product of the isocyanate group-terminated prepolymer having a carboxyl group was emulsified and dispersed to obtain a dispersion. Then, 60% by mass of hydrogenated hydrazine 5. 2 g of a polyamine aqueous solution in which diethylenetriamine was dissolved in 20 g of water was added to the above dispersion liquid, and the mixture was reacted for 35 minutes at 35 ° C, and then desolvated at 35 ° C under reduced pressure to obtain a nonvolatile matter. 5. 0% by mass, viscosity 1 800 mP a · s (B Μ viscosity agent, No. 2 rotator, 6 (^? 111), ? 11 値 9. 5. An aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group having an average particle diameter of 7〇11111. The total of the carboxyl group content and the carboxylate group content in the urethane resin having a carboxyl group and a carboxylate group is 1. 3 mass%, 100% modulus is 2 MPa. Further, the aqueous dispersion of the urethane resin having a carboxyl group and a carboxylate group is not gelled even when heated at 90 ° C, and is not susceptible to thermal coagulability. (Synthesis Example 5) 1,6-hexanediol polycarbonate polyol (average molecular weight 2000) was fed into a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube. 1g, 1,4-butanediol 2. 9g, trimethylolpropane i. 7g' 2,2-dimethylolpropionic acid 11. Lg, dibutyltin dilaurate 〇〇〇lg and methyl ethyl ketone l〇5g' are uniformly mixed and then added to dicyclohexylmethane diisocyanate 83. 2g' is reacted at 80 ° C for 240 minutes to give a free isocyanate group content of 3. A methyl ethyl ketone solution of 8 mass% of an isocyanate terminal prepolymer having a carboxyl group. After cooling the solution to below 50 ° C, adding triethylamine 7. 9 g, neutralization reaction at 40 ° C for 30 minutes. Next, the neutralized solution is cooled -32-201120275 to 30 °C, and the water is slowly added using the disperser blades. 3 g of the neutralized product of the isocyanate group-terminated prepolymer having a carboxyl group was emulsified and dispersed to obtain a dispersion. Then, 60% by mass of hydrogenated hydrazine 7. 7g and diethylenetriamine 1 .  3 g of a polyamine aqueous solution dissolved in water of 20 g was added to the above dispersion, and the reaction was carried out for 30 minutes under a chain extension of 35 ° C, and then desolvation was carried out at 35 ° C under reduced pressure to obtain a nonvolatile matter. 0% by mass, viscosity 40 mPa·s (BM viscosity agent, No. 1 rotor, 60 rpm) 'pH値8. An aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group having an average particle diameter of 40 nm. The total of the carboxyl group content and the carboxylate group content in the urethane resin having a carboxyl group and a carboxylate group is 1. 5 mass%, 100% modulus is 18 MPa. Further, the aqueous dispersion of the urethane resin having a carboxyl group and a carboxylate group is not gelled even when heated at 90 ° C, and is not susceptible to thermal coagulability. (Synthesis Example 6) 1,6-hexanediol polycarbonate polyol (average molecular weight 2000) I34 was fed into a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube. 3g, 1,4-butanediol 3. 5g, trimethylolpropane 3. 8g, 2,2·dimethylolpropionic acid i〇. 9 g, dibutyltin dilaurate 0001 g and methyl ethyl ketone 10 ’ 5 g' are uniformly mixed and then added to dicyclohexylmethane diisocyanate 92. 6g' was reacted at 80 ° C for 210 minutes to give a free isocyanate group content of 4. 2% by mass of a methyl ethyl ketone solution of an isocyanate terminal prepolymer having a carboxyl group. The solution was cooled to 50. (: After the following, triethylamine 7 · 8 g was added, and the neutralization reaction was carried out for 30 minutes at -33 - 201120275 4 ° C. Next, the neutralized solution was cooled to 30 ° C or less, using a disperser blade. Slowly add water 405. The neutralized product of the isocyanate group-terminated prepolymer having a carboxyl group was emulsified and dispersed at 0 g to obtain a dispersion. Then, 60% by mass of hydrogenated hydrazine 6. 9g and diethylenetriamine 2. A polyamine aqueous solution in which 〇g was dissolved in 20 g of water was added to the dispersion liquid, and the mixture was reacted for 30 minutes at 35 ° C, and then desolventized at 35 ° C under reduced pressure to obtain a nonvolatile matter. 0% by mass, viscosity 230 mPa · s (BM viscosity agent, No. 2 rotor, 60 rpm), pH 値 8. 7. An aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group having an average particle diameter of 90 nm. The total of the carboxyl group content and the carboxylate group content in the urethane resin having a carboxyl group and a carboxylate group is 1. 5 mass%, 100% modulus is 23 MPa. Further, the aqueous dispersion of the urethane resin having a carboxyl group and a carboxylate group is not gelled even after heating for 90 seconds, and is not susceptible to thermal coagulability. (Comparative Synthesis Example 1) In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen introduction tube, polytetramethylene glycol (having an average molecular weight of 10 00) was fed. 1 g, polyoxyethylene polypropylene glycol random copolymer glycol (average molecular weight 1000 'oxyethylene content 70% by mass) 9g, 1,4-butanediol 1. 5g, trimethylolpropane 1. 9g, dibutyltin dilaurate O. After OOlg and methyl ethyl ketone 6〇g' are uniformly mixed, dicyclohexylmethane diisocyanate is added. 4 g 'reaction at 80 ° C for 300 minutes gave a free isocyanate group content of 2. A 1% by mass isocyanate-based terminal prepolymer of methyl ethyl-34-201120275 ketone solution. After the solution was cooled to below 30 ° C, decyl phosphate and polyoxyethylene tristyrylphenyl ether (HLB = 15) were added. 0g, after the combination, using the disperser blades and slowly adding water 254. After emulsifying with 0 g, dispersion was carried out to obtain a dispersion. Then, the hexahydropyrazine and the substance 2. 0g and diethylenetriamine 0. 8 g dissolved in water 11. 3 g of a polyamine aqueous solution was reacted in the above dispersion liquid at a chain extension of 35 ° C for 90 minutes, and then decompressed at 35 ° C under reduced pressure to obtain a nonvolatile matter. 0% by mass, sticky mPa.  s (BM viscosity agent, No. 1 rotor, 60 rpm), pH 値 8. 0 Moisture of a stable aqueous polyurethane resin with a uniform particle size of 5 50 nm 〇 The total content of carboxyl groups and carboxylate in the aqueous polyurethane resin is 〇. 〇% by mass, 100% modulus is 2 MPa. Further, the aqueous dispersion of the urethane resin was gelated at 45 ° C and the thermosetting property was as follows. The synthesis examples 1 to 6 and the comparative synthesis example 1 are shown in Table 1. 0. 1 g ground mixed phase transition, i 6 water addition, degree 50, flat matter group, containing properties -35- 201120275 [一谳] Comparative Synthesis Example 1 35. 0 § V〇 〇· CO Synthesis Example 6 35. 0 〇 § ΟΊ csi 〇 σ σ\ Synthesis Example 5 35. 0 〇 Ο ΟΟ 〇 〇 Synthesis Example 4 35. 0 § 1 i Ο cn CM Λ Λ Synthesis Example 3 35. 0 〇\r-Η CN ΟΟ 璀 Ο &lt;y\ Synthesis Example 2 35.0 〇 \ο· Different r· 1 cn m Destroy ο Synthesis Example 1 35.0 1 &lt; ΟΟ cn CO Destroy Os Nonvolatiles (% by mass) Viscosity (mPa · s ) pH値 average particle size (nm) Carboxyl group content (% by mass) 100% modulus (MPa) Emulsifier (with/without) Sensible Solidification temperature (°c) -36 201120275 [Examples 1 to 10 and Comparative Examples 1 to 6] (Example 1) A polyurethane resin having a carboxyl group and a carboxylate group obtained in Synthesis Example 1 Water dispersion: 100 g, ammonium sulfate, 20% by mass aqueous solution, 17.5 g, Texport BG (alcohol-based permeant, trade name, manufactured by Nikko Chemical Co., Ltd.), 50% by mass aqueous solution, 6.0 g, and water 16.5 g The mixture was uniformly mixed to prepare a mixed solution. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the above mixture is 100:10, the pH is 6.2, the thermosetting temperature is 57 ° C, and the carboxyl group and the carboxylic acid are present. The content of the ester group polyurethane resin was 25% by mass. This mixed liquid was impregnated with a non-woven fabric made of polyester fiber (0.5 dt ex, density: 0.3 g/cm 3 ), impregnated by a slit mill to a pick up ratio of 250% by mass, and then dried by a hot air dryer. [TABAI SAFETYOVEN SP Η - 2 0 0], dried at 1 ° C for 3 minutes, and then dried at 150 ° C for 3 minutes to obtain artificial leather. Further, the obtained artificial leather (material for leather) was dyed under the following conditions, and subjected to RC adsorption to obtain an artificial leather dyed processing cloth (dyeing material for dyeing processing <dyeing conditions> dyeing machine: Mini color dyeing machine [( )Texam Technology] Dyes: Kayalon Microester Blue DX-LS cone [Nippon Chemicals Co., Ltd.] 〇.l〇%owf

Kayalon Microester Yellow DX-LS〔日本化藥（股） -37- 201120275 〕2 ·00%〇· w_f.Kayalon Microester Yellow DX-LS [Japan Chemicals Co., Ltd. -37- 201120275] 2 ·00%〇· w_f.

Kayalon Microester Red DX-LS〔曰本化藥（股）〕 0.8 0 % ο . w. f. 染色助劑：NICCA SUNSOLT RM-340〔日華化學（股 )〕〇.5g/升 pH調整劑：90%質量醋酸 0.3cc/L 浴比：（1 : 2 0 ) 染色條件：130°C X60分鐘（昇溫速度2°C /分） 〈RC條件〉 RC浴：氫氧化鈉 2g/升 氫硫酸 2g/升 浴比：（1 : 2 0 ) RC條件：80°C x20分鐘（昇溫速度2°C /分） (實施例2 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物l〇〇g、硫酸銨之30質量％水溶液 23.3g、Texport BG〔醇系浸透劑、商品名、日華化學（股 )製〕之50質量％水溶液6.0g及水10.7g均一地混合而調製 混合液。在前述混合液中之具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂與硫酸銨的調配比係100 : 20，pH値爲6.0，感 熱凝固溫度爲45 °C，具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂的含量爲2 5質量％。 除使用如此之混合液以外，其餘係與實施例1同樣處 -38- 201120275 理’得到人工皮革染色加工布（染色加工之皮革用材料） (實施例3 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物1 〇〇g、硫酸銨之40質量％水溶液 3〇_6g、Texport BG〔醇系浸透劑、商品名、日華化學（股 )製〕之50質量％水溶液6.0g及水31.4g均一地混合而調製 混合液。在前述混合液中之具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂與硫酸銨的調配比係1 00 : 35，pH値爲5.8，感 熱凝固溫度爲59°C，具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂的含量爲2 1質量％。 除含浸如此之混合液成爲壓吸率3 0 0質量％以外，其餘 係與實施例1同樣處理，得到人工皮革染色加工布（染色 加工之皮革用材料）。 (實施例4 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物1 〇〇g、硫酸銨之40質量％水溶液 1.8g、水1.8g均一地混合而調製混合液。在前述混合液中 之具有羧基及羧酸酯基之聚胺基甲酸酯樹脂與硫酸銨的調 配比係100: 2’ pH値爲6.8，感熱凝固溫度爲70 °C，具有 羧基及羧酸酯基之聚胺基甲酸酯樹脂的含量爲3 4質量％。 除含浸如此之混合液成爲壓吸率1 85質量％以外，其餘 -39 - 201120275 係與實施例1同樣處理，得到人工皮革染 加工之皮革用材料）。 (實施例5 ) 使於合成例2所得到的具有羧基及羧 甲酸酯樹脂之水分散物l〇〇g、硫酸銨之 17」g、Texport BG〔醇系浸透劑、商品名 )製〕之50質量％水溶液6.0g及水16.5g均 混合液。在前述混合液中之具有羧基及羧 甲酸酯樹脂與硫酸銨的調配比係1 00 ·· 1 〇 熱凝固溫度爲55 °C，具有羧基及羧酸酯基 樹脂的含量爲2 5質量％。 除使用如此之混合液以外，其餘係劈 理，得到人工皮革染色加工布（染色加工 (實施例6 ) 使於合成例3所得到的具有羧基及羧 甲酸酯樹脂之水分散物l〇〇g、硫酸銨之 17.5g、Texport BG〔醇系浸透劑、商品名 )製〕之50質量％水溶液6.0g及水16.5g均 混合液。在前述混合液中之具有羧基及羧 甲酸酯樹脂與硫酸銨的調配比係1 : 1 〇 熱凝固溫度爲52 °C ’具有羧基及羧酸酯基 色加工布（染色 酸酯基之聚胺基 20質量％水溶液 、日華化學（股 一地混合而調製 酸酯基之聚胺基 ’ pH値爲6.3，感 之聚胺基甲酸酯 I實施例1同樣處 之皮革用材料） 酸酯基之聚胺基 20質量％水溶液 、日華化學（股 一地混合而調製 酸酯基之聚胺基 'P Η値爲6 · 2，感 之聚胺基甲酸酯 -40- 201120275 樹脂的含量爲25質量％。 除使用如此之混合液以外，其餘係與實施例1同樣處 理’得到人工皮革染色加工布（染色加工之皮革用材料） (實施例7 ) 使於合成例4所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物1 〇〇g、硫酸銨之20質量％水溶液 17.5g、Texport BG〔醇系浸透劑、商品名、日華化學（股 )製〕之5 0質量％水溶液6.0 g及水1 6.5 g均一地混合而調製 混合液。在前述混合液中之具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂與硫酸銨的調配比係100 : 10，pH値爲6.2，感 熱凝固溫度爲66 °C，具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂的含量爲2 5質量％。 除使用如此之混合液以外，其餘係與實施例1同樣處 理’得到人工皮革染色加工布（染色加工之皮革用材料） (實施例8 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物100g、磷酸氫二銨/磷酸二氫銨（ 質量比 50/50)之 20質量％ 水溶液 17.5g、Carbodilite E-02 〔羰二醯亞胺系交聯劑、商品名、日清紡（股）製〕1 .0g 、Texport BG〔醇系浸透劑、商品名、日華化學（股）製 -41 - 201120275 〕之50質量％水溶液6.0g及水15.5g均 液。在前述混合液中之具有羧基及羧 酯樹脂與無機酸銨的調配比係1 〇〇 : 1 凝固溫度爲45 °C，具有羧基及羧酸酯 脂的含量爲2 5質量％。 除使用如此之混合液以外，其舊 理，得到人工皮革染色加工布（染色 (實施例9 ) 使於合成例5所得到的具有羧基 甲酸酯樹脂之水分散物1 OOg、硫酸 17‘5g、Texport BG〔醇系浸透劑、商 )製〕之5 0質量％水溶液6.0 g及水1 6 · 混合液。在前述混合液中之具有羧基 甲酸酯樹脂與硫酸銨的調配比係1 00 熱凝固溫度爲55 t，具有羧基及羧酸 樹脂的含量爲2 5質量％。 除含浸如此之混合液成爲壓吸率 係與實施例1同樣處理，得到人工皮 加工之皮革用材料）。 (實施例1 0 ) 使於合成例6所得到的具有羧基 一地混合而調製混合 酸酯基之聚胺基甲酸 〇，pH値爲6.3，感熱 基之聚胺基甲酸酯樹 :係與實施例1同樣處 加工之皮革用材料） 及羧酸酯基之聚胺基 銨之20質量％水溶液 品名、日華化學（股 5g均一地混合而調製 及羧酸酯基之聚胺基 :10，pH値爲 6.3，感 酯基之聚胺基甲酸酯 125質量％以外，其餘 革染色加工布（染色 及羧酸酯基之聚胺基 -42- 201120275 甲酸酯樹脂之水分散物1 〇〇g、硫酸銨之20質量。/()水溶液 17‘5g、Texport BG〔醇系浸透劑、商品名、日華化學（股 )製〕之50質量％水溶液6.0g及水16.5g均一地混合而調製 混合液。在前述混合液中之具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂與硫酸銨的調配比係1〇〇: 1〇，pH値爲6.2，感 熱凝固溫度爲50°C ’具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂的含量爲2 5質量％。 除含浸如此之混合液成爲壓吸率125質量％以外，其餘 係與實施例1同樣處理’得到人工皮革染色加工布（染色 加工之皮革用材料）。 (比較例1 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸醋樹脂之水分散物1 00g、Texport BG〔醇系浸透劑、 商品名、日華化學（股）製〕之5 0質量％水溶液6 . 〇 g及水 34.0g均一地混合而調製混合液。在前述混合液中之具有 羧基及羧酸酯基之聚胺基甲酸酯樹脂與無機酸之銨鹽的調 配比係100: 0’ pH値爲7.5’感熱凝固溫度爲90艺以上， 具有羧基及羧酸酯基之聚胺基甲酸酯樹脂的含量爲25質量 %。 除使用如此之混合液以外’其餘係與實施例1同樣處 理，得到人工皮革染色加工布（染色加工之皮革用材料） -43- 201120275 (比較例2 ) 使於合成例1所得到的具有羧基及羧酸酯基之聚胺基 甲酸酯樹脂之水分散物100g、硫酸之10質量％水溶液17.5g 、Texport BG〔醇系浸透劑、商品名、日華化學（股）製 〕之50質量％水溶液6.0g及水16.5g均一地混合而調製混合 液。在前述混合液中之具有羧基及羧酸酯基之聚胺基甲酸 酯樹脂與硫酸的調配比係1 0 0 : 5，感熱凝固溫度爲1 〇 °C以 下’具有羧基及羧酸酯基之聚胺基甲酸酯樹脂的含量爲25 質量％。 又，前述混合液係添加硫酸之10質量％水溶液時，瞬 間可從混合液看到析出物，故人工皮革染色加工布的製造 係斷念。又，很難測定pH。 (比較例3 ) 使於比較合成例1所得到的水性聚胺基甲酸醋M 旨；^ 水分散物l〇〇g、Texport BG〔醇系浸透劑、商品名、日華 化學（股）製〕之5 0質量％水溶液6.0 g及水3 4 · 0 g均―地混 合而調製混合液。在前述混合液中之水性聚胺基甲酸 脂與無機酸的銨鹽之調配比係1〇〇: 〇，pH値爲8·〇，感熱 凝固溫度爲45°C，水性聚胺基甲酸酯樹脂的含量爲25胃胃 %。 除使用如此之混合液以外，其餘係與實施例1同#胃 理，得到人工皮革染色加工布（染色加工之皮革用# -44- 201120275 (比較例4 ) 使於比較合成例1所得到的水性聚胺基甲酸 水分散物l〇〇g、硫酸銨之20質量％水溶液17.5g B G〔醇系浸透劑、商品名、日華化學（股）製〕 %水溶液6.0g及水16.5 g均一地混合而調製混合液 混合液中之水性聚胺基甲酸酯樹脂與無機酸的銨 比係100: 10，pH値爲6.5，感熱凝固溫度爲45 °c 胺基甲酸酯樹脂的含量爲25質量％。 除使用如此之混合液以外，其餘係與實施沿 理，得到人工皮革染色加工布（染色加工之皮革 (比較例5 ) 使於比較合成例1所得到的水性聚胺基甲酸 水分散物1 〇 〇 g、氯化鈣之1 〇質量％水溶液1 7.5 g BG〔醇系浸透劑、商品名、日華化學（股）製〕 %水溶液6.0 g及水1 6 _ 5 g均一地混合而調製混合液 混合液中之水性聚胺基甲酸酯樹脂與氯化鈣之 1〇〇 : 5，pH値爲8.1，感熱凝固溫度爲35 °C，水 甲酸酯樹脂的含量爲25質量％。 除使用如此之混合液以外，其餘係與實施B 理，得到人工皮革染色加工布（染色加工之皮革 酯樹脂之 、Texport 之50質量 。在前述 鹽之調配 ’水性聚 ^ 1同樣處 用材料） 酯樹脂之 、Texp〇rt 之50質量 。在前述 調配比係 性聚胺基 1同樣處 用材料） -45- 201120275 (比較例6 ) 使於合成例1所得到的具有羧基 甲酸酯樹脂之水分散物l〇〇g、蟻酸 17.5g、Texport BG〔醇系浸透劑、商 )製〕之50質量％水溶液6.0g及水16. 混合液。在前述混合液中之具有羧基 甲酸酯樹脂與蟻酸銨的調配比係100 熱凝固溫度爲45 °C，具有羧基及羧酸 樹脂的含量爲25質量％。 除使用如此之混合液以外，其翻 理’得到人工皮革染色加工布（染色 〇 於實施例1〜10所得到之人工皮革 加工之皮革用材料）的評估結果表示 、3〜6所得到之人工皮革染色加工布 用材料）的評估結果表示於表3中。 及羧酸酯基之聚胺基 錢之1 0質量％水溶液 品名、日華化學（股 5g均一地混合而調製 及羧酸酯基之聚胺基 :5’ pH値爲7.9，感 酯基之聚胺基甲酸酯 《係與實施例1同樣處 加工之皮革用材料） 染色加工布（已染色 於表2中。於比較例1 (已染色加工之皮革 -46- 201120275 u撇〕 實施例10 塵 寸 壊 銮 &lt; 實施例9 键 CN 寸 璀 键 m &lt; 實施例8 銮 m 矮 寸 摧 窠 &lt; 實施例7 键 寸 m 藤 寸 璀 m 寸 &lt; 實施例6 握 Os 卜 寸 摧 銮 ΓΟ &lt; 實施例5 藤 寸 銮 寸 摧 键 寸 &lt; 實施例4 寸 CN 銮 寸 摧 矮 寸 &lt; 實施例3 to 卜 〇〇 寸 摧 IT) &lt; 實施例2 Ο 00 寸 鞋 in &lt; 實施例1 銮 r- 寸 摧 銮 &lt; 遷移性 1000 次 3000 次 摩擦堅牢度 殘留物 手感 乾燥時之臭氣 磨耗量 (g/m3) -47- 201120275 〔e漱〕 比較例6 寸 摧 銮 U 比較例5 CO 卜 VO ν/Ί CN 鸾 m &lt; 比較例4 鵄 CN CO 褰 Γ0 键 CN &lt; 比較例3 銮 CN 〇 〇 τ**Η 键 CSJ 銮 CSI &lt; 比較例2 1 1 1 1 1 1 ! 比較例1 銮 1 i CO 寸 璀 璲 Ψ t &lt; 1000 次 3000 次 摩擦堅牢度 殘留物 手感 乾燥時之臭氣 m 磨耗量 (g/m3) -48- 201120275 在實施例1〜9所得到之皮革用材料中，遷移性係看不 出’樹脂均一地固定至不織布內部。如此地，可確認出藉 防止遷移性，手感非常地柔軟，可得到在耐磨耗試驗中之 1000次、3000次的磨耗量幾乎不變且顯示優異之耐磨耗特 性的皮革用材料。在具有羧基及羧酸酯基之聚胺基甲酸酯 樹脂之1 00%模數很大時（實施例1 〇 )係爲手感粗硬者，在 3000次之耐磨耗試驗中略差，但防止遷移性優異，不重視 手感時係足夠充分地使用者。又’在實施例]〜丨〇所得到之 皮革用材料中，確認殘留於皮革用材料內之殘留物極少， 可知殘留物對摩擦堅牢度的影響亦很少。 另外，不含有無機酸之銨鹽，在只使用具有羧基及羧 酸醋基之聚胺基甲酸酯樹脂之比較例1所得到的皮革用材 料中，係可看出乾燥時明顯之遷移性，手感很粗硬。進一 步’在比較例1所得到之皮革用材料的耐磨耗性試驗中， 磨耗1 0 0 0次時係耐磨耗性良好，但磨耗3 〇 0 〇次時可看到明 顯之磨耗量，確認出耐摩耗性不充分。 又’在比較例2中，使用硫酸水溶液取代無機酸之銨 鹽，但混合液凝膠化’故無法製造皮革用材料，而確認出 加工適性不充分。 又’不使用無機酸之銨鹽而在只使用以界面活性劑乳 化所得到之具有感熱凝固性的水性聚胺基甲酸酯樹脂之比 較例3中所得到的皮革用材料中，係具有感熱凝固性，同 時乾燥時可明顯地看出遷移性。又，在比較例3所得到之 皮革用材料係手感粗硬’在耐磨耗性試驗中，磨耗1〇00次 -49 - 201120275 時係耐磨耗性良好，但磨耗3 000次時可看到明顯之磨耗量 ，確認出耐磨耗性不充分》 進一步在使用以界面活性劑乳化所得到之具有感熱凝 固性的水性聚胺基甲酸酯樹脂與無機酸之銨鹽的比較例4 所得到的皮革用材料中，可看出與在比較例3所得到之皮 革用材料同樣的結果，相對於以界面活性劑乳化所得到之 具有感熱凝固性的水性聚胺基甲酸酯樹脂，確認出無法得 到以無機酸之銨鹽所得到的防止遷移性等之效果。 又，使用氯化鈣水溶液取代無機酸之銨鹽，在使用與 以界面活性劑乳化所得到之水性聚胺基甲酸酯樹脂混合之 混合液的比較例5所得到之皮革用材料中，係藉氯化鈣水 溶液，感熱凝固溫度降低，防止遷移性略提高，但與在實 施例1〜1 0所得到的皮革用材料比較時，防止遷移性不充分 。又，在比較例5所得到之皮革用材料係手感粗硬，進一 步在耐磨耗性試驗中，磨耗1 〇〇〇次時係耐磨耗性良好，但 磨耗3 000次時可看到明顯之磨耗量，確認出耐磨耗性不充 分。又，確認出於皮革用材料內殘留界面活性劑，並確認 出殘留物對摩擦堅牢度的影響大。 進一步，在使用由蟻酸銨鹽所構成之水溶液取代無機 酸的銨鹽之比較例6所得到的皮革用材料中，係防止遷移 性、耐磨耗性、摩擦堅牢度、殘留物 '手感之面係優異， 但可確認出乾燥時因蟻酸銨之分解、揮發所產生之臭氣。 又，此時，所產生之蟻酸係裝置腐蝕之原因，進一步，若 蟮酸及氨氣釋出至大氣中，可成爲環境問題。 •50- 201120275 如以上說明般，若依本發明’可提供一種皮革用材料 之製造方法、以及藉其製造方法所得到之皮革用材料，其 係儘管爲使用考量環境負荷或VOC之問題的水性聚胺基甲 酸酯樹脂之皮革用材料的製造方法，而可充分防止遷移，性 ’又’無工程上所產生之氣體造成的臭氣及裝置的腐蝕， 可有效率且確實地得到手感柔軟且耐磨耗性或摩擦堅牢度 等之物性亦優的皮革用材料。 因此’本發明之製造方法係特別可用來作爲皮革用材 料之工業上製造方法’又’依本發明之製造方法所得到的 皮革用材料’於皮革用材料中有機溶劑亦未殘留，對皮膚Kayalon Microester Red DX-LS [曰本化药(股)] 0.8 0 % ο . wf Dyeing Auxiliary: NICCA SUNSOLT RM-340 [日华化学(股)]〇.5g/L pH Adjuster: 90% by mass Acetic acid 0.3cc / L Bath ratio: (1: 2 0) Dyeing conditions: 130 ° C X60 minutes (temperature rising rate 2 ° C / min) <RC conditions> RC bath: sodium hydroxide 2g / liter of hydrogen sulfuric acid 2g / liter bath Ratio: (1: 2 0 ) RC conditions: 80 ° C x 20 minutes (temperature rising rate 2 ° C / min) (Example 2) The polyamino group having a carboxyl group and a carboxylate group obtained in Synthesis Example 1 Water-dispersion of the acid ester resin, 〇〇g, 30% by mass of aqueous solution of ammonium sulfate, 23.3 g, Texport BG (alcohol-based permeant, trade name, manufactured by Nikko Chemical Co., Ltd.), 50% by mass aqueous solution, 6.0 g, and water 10.7 g was uniformly mixed to prepare a mixed solution. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the above mixture is 100:20, the pH is 6.0, the thermotropic temperature is 45 ° C, and the carboxyl group and the carboxylic acid are present. The content of the ester group polyurethane resin was 25 mass%. The same procedure as in Example 1 was carried out except that the above-mentioned mixed solution was used. -38-201120275 The 'artificial leather dyed processing cloth (the material for dyeing leather) was obtained. (Example 3) The obtained product obtained in Synthesis Example 1 was obtained. Aqueous dispersion of carboxyl group and carboxylate-based polyurethane resin 1 〇〇g, 40% by mass aqueous solution of ammonium sulfate 3〇_6g, Texport BG [alcohol-based permeant, trade name, Nikko Chemical ( The mixed solution was prepared by uniformly mixing 6.0 g of a 50% by mass aqueous solution and 31.4 g of water. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the above mixture is 100:35, the pH is 5.8, the thermosetting temperature is 59 ° C, and the carboxyl group and the carboxyl group are present. The content of the acid ester group-containing polyurethane resin was 21% by mass. The artificial leather dyed processing cloth (dye material for dyeing processing) was obtained in the same manner as in Example 1 except that the mixed liquid was impregnated to have a pressure absorption ratio of 300% by mass. (Example 4) 1 g of an aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group obtained in Synthesis Example 1, 1.8 g of a 40% by mass aqueous solution of ammonium sulfate, and 1.8 g of water. The mixture was uniformly mixed to prepare a mixed solution. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the above mixture is 100: 2' pH 値 is 6.8, the thermotropic temperature is 70 ° C, and has a carboxyl group and a carboxylic acid. The content of the ester group polyurethane resin was 34% by mass. The above-mentioned -39 - 201120275 was treated in the same manner as in Example 1 except that the mixed solution was impregnated to a pressure ratio of 185 % by mass, and a leather material for artificial leather dyeing was obtained. (Example 5) The aqueous dispersion having a carboxyl group and a carboxylate resin obtained in Synthesis Example 2, 100 g of ammonium sulfate, and Texport BG (alcohol-based permeant, trade name) were prepared. A mixed liquid of 6.0 g of a 50% by mass aqueous solution and 16.5 g of water. The compounding ratio of the carboxyl group and the carboxyformate resin to the ammonium sulfate in the mixed liquid is 1 00 ·· 1 〇, the heat setting temperature is 55 ° C, and the content of the carboxyl group and the carboxylate-based resin is 25 % by mass. . Except that such a mixed solution was used, the other was treated to obtain an artificial leather dyed processing cloth (dye processing (Example 6). The aqueous dispersion having a carboxyl group and a carboxyformate resin obtained in Synthesis Example 3 was obtained. g, a mixture of 17.5 g of ammonium sulfate, 6.0 g of a 50% by mass aqueous solution of Texport BG [alcohol-based permeation agent, trade name], and 16.5 g of water. The compounding ratio of the carboxyl group and the carboxyformate resin to the ammonium sulfate in the above mixture is 1: 1 〇 The heat setting temperature is 52 ° C. The resin having a carboxyl group and a carboxylate color processing cloth (polyamine dyed with an acid ester group) Base 20% by mass aqueous solution, Nikko Chemical Co., Ltd. (mixed to prepare a polyamine group of an acid ester group), pH 値, 6.3, sensible polyurethane sulphate I, the same leather material as in Example 1) a polyamine-based 20% by mass aqueous solution, a Japanese chemical (mixed to prepare an acid ester group, a polyamino group 'P Η値 is 6.2, a sensitized polycarbamate-40-201120275 resin The content was 25% by mass. The same procedure as in Example 1 was carried out except that the above-mentioned mixed solution was used to obtain an artificial leather dyed processing cloth (dye material for dyeing processing) (Example 7) obtained in Synthesis Example 4. Water dispersion of polyurethane resin having carboxyl group and carboxylate group 1 〇〇g, 20 mass% aqueous solution of ammonium sulfate 17.5 g, Texport BG [alcohol-based permeant, trade name, Nikko Chemical Co., Ltd. ) 50% by mass aqueous solution 6.0 g and water 1 6.5 g uniform Mixing and preparing a mixed liquid. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the above mixture is 100:10, the pH is 6.2, and the thermosetting temperature is 66 °C. The content of the polyurethane resin having a carboxyl group and a carboxylate group was 25 mass%. The same treatment as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather dyed processing cloth (dye processing). (Materials for Leather) (Example 8) 100 g of an aqueous dispersion of a polyurethane resin having a carboxyl group and a carboxylate group obtained in Synthesis Example 1, diammonium hydrogen phosphate / ammonium dihydrogen phosphate (quality) 20% by mass of 50/50) 17.5 g of aqueous solution, Carbodilite E-02 [Carbodiamine-based cross-linking agent, trade name, manufactured by Nisshinbo Co., Ltd.) 1.0 g, Texport BG [alcohol-based permeant, commercial product Name, Nikko Chemical Co., Ltd. -41 - 201120275] 50% by mass aqueous solution 6.0g and water 15.5g liquid. The ratio of carboxyl group and carboxyl ester resin to ammonium mineral acid in the above mixture is 1 〇 〇: 1 The solidification temperature is 45 °C, with carboxyl and carboxylate esters The content was 25.5% by mass. In addition to the use of such a mixed solution, an artificial leather dyed processed cloth was obtained (dyeing (Example 9). The aqueous dispersion having the carboxyformate resin obtained in Synthesis Example 5 was obtained. 1 OOg, 17'5g of sulfuric acid, Texport BG [alcoholic permeation agent, quotient], 50% by mass of aqueous solution, 6.0 g, and water, 1 6 · mixed solution, having carboxyformate resin and sulfuric acid in the above mixture The ammonium compounding ratio was 100 00, and the thermal curing temperature was 55 t, and the content of the carboxyl group and the carboxylic acid resin was 25 mass%. The mixture was impregnated and the pressure-intake ratio was the same as in Example 1 to obtain a leather material for artificial skin processing. (Example 10) The polyaminoformate obtained by mixing the carboxyl group obtained in Synthesis Example 6 to prepare a mixed acid ester group, having a pH of 6.3, a thermosensitive group of polyurethanes: Example 1 The leather material processed in the same manner) and the carboxylate-based polyammonium ammonium 20% by mass aqueous solution product name, Nikko Chemical Co., Ltd. (5 g uniformly mixed to prepare a carboxylate group of polyamine group: 10 , pH 値 is 6.3, and the ester-based polyurethane is 125% by mass, and the other leather dyed processing cloth (dye and carboxylate-based polyamine-42-201120275 for the dispersion of the formate resin) 〇〇g, ammonium sulphate 20%. / () aqueous solution 17 '5g, Texport BG [alcohol-based permeant, trade name, manufactured by Nikko Chemical Co., Ltd.] 50% by mass aqueous solution 6.0g and water 16.5g uniformly Mixing and preparing a mixed liquid. The ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium sulfate in the mixed liquid is 1 〇〇: 1 〇, pH 6.2 is 6.2, and the sensible heat setting temperature is The content of the polyurethane resin having a carboxyl group and a carboxylate group at 50 ° C is 25 mass%. In the same manner as in Example 1, except that the mixture was immersed in a pressure-inhalation ratio of 125% by mass, the artificial leather dyed processing cloth (dyed material for leather processing) was obtained. (Comparative Example 1) The obtained in Synthesis Example 1 was obtained. 00 g of an aqueous dispersion of a polyaminocarbamic acid carboxylic acid resin having a carboxyl group and a carboxylate group, and a 50% by mass aqueous solution of Texport BG [alcohol-based permeating agent, trade name, manufactured by Nikko Chemical Co., Ltd.]. g and water 34.0g are uniformly mixed to prepare a mixed liquid. The compounding ratio of the polyurethane resin having a carboxyl group and a carboxylate group to the ammonium salt of the inorganic acid in the mixed liquid is 100: 0' pH値The content of the 7.5' sensible heat setting temperature is 90 or more, and the content of the urethane resin having a carboxyl group and a carboxylate group is 25% by mass. The same applies to Example 1 except that such a mixed solution is used. Artificial leather dyeing processing cloth (dye material for dyeing processing) - 43 - 201120275 (Comparative Example 2) The aqueous dispersion of the polyurethane resin having a carboxyl group and a carboxylate group obtained in Synthesis Example 1 100g, 10% by mass of sulfuric acid 17.5 g, Texport BG (alcohol-based permeant, trade name, manufactured by Nikko Chemical Co., Ltd.), 6.0 g of a 50% by mass aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed liquid. And the ratio of the carboxylate-based polyurethane resin to sulfuric acid is 1 0 0 : 5, and the thermosetting temperature is below 1 〇 ° C. 'Polyurethane resin having carboxyl group and carboxylate group When the mixed liquid is added with a 10% by mass aqueous solution of sulfuric acid, the precipitate can be seen from the mixed liquid instantaneously, so that the production of the artificial leather dyed processed cloth is interrupted. Also, it is difficult to measure the pH. (Comparative Example 3) The aqueous polyamino carboxylic acid hydrate obtained in Comparative Synthesis Example 1 was prepared; the aqueous dispersion l〇〇g, Texport BG [alcohol-based permeating agent, trade name, and Nikko Chemical Co., Ltd. The 50% by mass aqueous solution 6.0 g and the water 3 4 · 0 g were all mixed to prepare a mixed solution. The compounding ratio of the aqueous polyurethane and the ammonium salt of the inorganic acid in the above mixture is 1 〇〇: 〇, pH 8 8 〇, sensible heat setting temperature is 45 ° C, aqueous polyurethane The content of the resin was 25% of stomach stomach. In addition to the use of such a mixed solution, the same procedure as in Example 1 was carried out to obtain an artificial leather dyed processing cloth (for leather for dyeing processing #-44-201120275 (Comparative Example 4), which was obtained in Comparative Synthesis Example 1. Aqueous polyurethane aqueous dispersion l〇〇g, ammonium sulfate 20% by mass aqueous solution 17.5g BG [alcohol-based permeating agent, trade name, Nikko Chemical Co., Ltd.] % aqueous solution 6.0g and water 16.5 g uniformly The ammonium ratio of the aqueous polyurethane resin to the inorganic acid in the mixed liquid mixture is 100: 10, the pH is 6.5, the thermosetting temperature is 45 °c, and the content of the urethane resin is 25. In addition to the use of such a mixture, the artificial leather dyed processing cloth (dye-treated leather (Comparative Example 5) was obtained by dispersing the aqueous polyurethane water obtained in Comparative Synthesis Example 1 except for the use of the mixed liquid. 1 〇〇g, calcium chloride 1 〇 mass% aqueous solution 1 7.5 g BG [alcohol-based permeant, trade name, Nikko Chemical Co., Ltd.] % aqueous solution 6.0 g and water 1 6 _ 5 g uniformly mixed And preparing the aqueous polyurethane in the mixed liquor mixture 1 树脂 of resin and calcium chloride: 5, pH 8.1 is 8.1, sensible heat setting temperature is 35 ° C, and content of carbamate resin is 25% by mass. Except using such a mixture, the rest is carried out B The artificial leather dyeing processing cloth (the leather ester resin of the dyeing process, the Texport 50 mass. The compound of the above salt is used in the same material as the water-based polymer), and the ester resin has a mass of 50% of Texp〇rt. The same material as the polyamine 1 was prepared. -45-201120275 (Comparative Example 6) The aqueous dispersion of the carboxyformate resin obtained in Synthesis Example 1 was used, and the toluic acid was 17.5 g, Texport. A mixed solution of 50 g of a 50% by mass aqueous solution of BG [alcohol-based permeation agent, quotient] and water 16. The compounding ratio of the carboxyformate resin to the ammonium formate in the mixed liquid was 100. The thermal setting temperature was 45 °C, and the content of the carboxyl group and the carboxylic acid resin was 25% by mass. In addition to the use of such a mixture, the results of the evaluation of the artificial leather dyed processing cloth (the leather material dyed in the artificial leather processed in Examples 1 to 10) are shown in the results of 3 to 6 The evaluation results of the materials for leather dyeing processing fabric are shown in Table 3. And the carboxylate group of the polyamine-based 10% by mass aqueous solution product name, Nikko Chemical (5g uniformly mixed to prepare and the carboxylate group of the polyamine group: 5' pH 値 is 7.9, the ester group Polyurethane "Material for leather processed in the same manner as in Example 1" Dyeing cloth (stained in Table 2. In Comparative Example 1 (dyed leather - 46-201120275 u撇) Example 10 dust 壊銮 &lt; Example 9 key CN inch 璀 key m &lt; Example 8 銮m dwarf inch destruction &lt; Example 7 key inch m 藤 inch 璀 m inch &lt; Example 6 grip Os Bu inch銮ΓΟ &lt; Example 5 藤 inch inch inch key inch &lt; Example 4 inch CN 銮 inch destroy dwarf &lt; Example 3 to 〇〇 〇〇 inch IT) &lt; Example 2 Ο 00 inch shoes in &lt; Example 1 銮r- inch 銮 migrating 1000 times 3000 times rubbing fastness residue odor burning amount when dry (g/m3) -47- 201120275 〔e漱〕 Comparative example 6 inch 銮U Comparative Example 5 CO Bu VO ν/Ί CN 鸾m &lt; Comparative Example 4 鵄CN CO 褰Γ0 key CN &lt;Comparative Example 3 銮CN 〇〇τ**Η Key CSJ 銮CSI &lt;Comparative Example 2 1 1 1 1 1 1 ! Comparative Example 1 銮1 i CO 璀璲Ψ 璀璲Ψ t &lt; 1000 times 3000 times of rubbing fastness The odor of the residue when the hand is dry m The amount of abrasion (g/m3) -48- 201120275 In the materials for leather obtained in Examples 1 to 9, the migration property was not such that the resin was uniformly fixed to the inside of the nonwoven fabric. In addition, it is confirmed that the migration property is extremely soft, and the material for leather which has an abrasion resistance of 1000 times and 3,000 times in the abrasion resistance test and which exhibits excellent wear resistance characteristics can be obtained. When the carboxyl group and the carboxylate-based polyurethane resin have a large modulus of 100% (Example 1 〇), they are rough and hard, and are slightly inferior in the 3000-time abrasion resistance test, but prevent migration. It is excellent in the properties, and it is sufficient for the user to pay attention to the hand. In the leather materials obtained in the examples, it is confirmed that the residue remaining in the leather material is extremely small, and the rubbing fastness of the residue is known. The impact is also very small. In addition, it does not contain inorganic acids. Ammonium salts, the carboxyl group and having only carboxylic groups of the poly vinegar timber feed the leather obtained in Comparative Example 1 urethane resin, based upon drying can be seen that the apparent mobility, feel very stiff. Further, in the abrasion resistance test of the leather material obtained in Comparative Example 1, the abrasion resistance was good when the abrasion was performed for 1,000 times, but the obvious abrasion amount was observed when the abrasion was performed for 3 〇0 times. It was confirmed that the abrasion resistance was insufficient. Further, in Comparative Example 2, an aqueous solution of a mineral acid was used instead of the ammonium salt of the inorganic acid, but the mixture was gelated. Therefore, the material for leather could not be produced, and it was confirmed that the processing property was insufficient. Further, in the material for leather obtained in Comparative Example 3 which does not use an ammonium salt of an inorganic acid and which is obtained by using only an aqueous polyurethane resin having thermosensitive coagulability obtained by emulsification with a surfactant, it has sensible heat. The cohesiveness is clearly observed when drying. Further, the material for leather obtained in Comparative Example 3 was rough in hardness. In the abrasion resistance test, the abrasion resistance was good when the abrasion was performed for 10,000 times -49 - 201120275, but it was observed when the abrasion was 3,000 times. In the case of a significant amount of abrasion, it was confirmed that the abrasion resistance was insufficient. Further, Comparative Example 4 of the aqueous polyurethane resin having thermal coagulability obtained by emulsification with a surfactant and ammonium salt of an inorganic acid was used. In the obtained leather material, it was found that the same results as the leather material obtained in Comparative Example 3 were confirmed with respect to the aqueous polyurethane resin having thermosensitive coagulability obtained by emulsification with a surfactant. The effect of preventing migration and the like obtained by using an ammonium salt of an inorganic acid cannot be obtained. Further, in the leather material obtained by using Comparative Example 5 in which a calcium chloride aqueous solution was used in place of the ammonium salt of the inorganic acid and mixed with an aqueous polyurethane resin obtained by emulsification with a surfactant, The calcium chloride aqueous solution was used, and the thermosensitive solidification temperature was lowered to prevent the migration property from being slightly improved. However, when the leather materials obtained in Examples 1 to 10 were compared, the migration property was insufficient. Further, the material for leather obtained in Comparative Example 5 was rough and hard, and in the abrasion resistance test, the abrasion resistance was good when the abrasion was performed 1 time, but it was obvious when the abrasion was 3,000 times. The abrasion amount was confirmed to be insufficient in abrasion resistance. Further, it was confirmed that the surfactant was left in the material for leather, and it was confirmed that the residue had a large influence on the friction fastness. Further, in the leather material obtained by using Comparative Example 6 in which an ammonium salt of an inorganic acid is replaced by an aqueous solution of an ammonium formate salt, migration, abrasion resistance, friction fastness, and residue 'feeling' are prevented. It is excellent, but it is confirmed that the odor generated by the decomposition and volatilization of ammonium formic acid during drying. Further, at this time, the cause of the generated formic acid-based apparatus is corroded, and further, if tannic acid and ammonia gas are released into the atmosphere, it may become an environmental problem. • 50- 201120275 As described above, according to the present invention, it is possible to provide a method for producing a material for leather and a material for leather obtained by the method for producing the same, which is water-based in consideration of environmental load or VOC. The method for producing a leather material for a polyurethane resin can sufficiently prevent migration, and the odor and the corrosion of the device caused by the gas generated by the engineering can be obtained, and the hand feeling can be obtained efficiently and surely. And leather materials such as abrasion resistance or friction fastness are also excellent. Therefore, the manufacturing method of the present invention is particularly useful as an industrial manufacturing method for leather materials, and the material for leather obtained by the production method of the present invention is not left in the leather material, and the skin is not left on the skin.

攻如響亦被解決，故可在車輛、家俱、 '袋物、雜貨、硏磨等之產業領域中直 亦可利用來作爲設置表皮層而安定且品 -51 -The attack is also solved, so it can be used in the industrial fields of vehicles, furniture, 'bags, groceries, honing, etc. as a set of skin layers and stable.

Claims (1)

201120275 七、申請專利範圍： 1. 一種皮革用材料之製造方法，其係使含有（A)具 有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂、（B)無機酸 之銨鹽及（C )水之混合液，含浸於纖維基材之後進行乾 燥而得到皮革用材料。 2. 如申請專利範圍第1項之皮革用材料之製造方法， 其中在前述混合液中，（A)具有羧基及/或羧酸酯基之聚 胺基甲酸酯樹脂與（B)無機酸之銨鹽的調配比，係以固 形成分之質量換算爲（A) : (B) =100: 〇.1~1〇〇: 50。 3. 如申請專利範圍第1項之皮革用材料之製造方法， 其中（B)無機酸之敍鹽中的無機酸爲硫酸及/或磷酸。 4. 如申請專利範圍第1項之皮革用材料之製造方法， 其中含有（A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹 脂、（B )無機酸之銨鹽及（C )水之混合液的pH爲 5.0〜7_0 。 5. 如申請專利範圍第1項之皮革用材料之製造方法， 其中含有（A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹 脂、（B)無機酸之銨鹽及（C)水之混合液的感熱凝固溫 度爲 30~80°C。 6. 如申請專利範圍第1項之皮革用材料之製造方法， 其中（A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂爲 使（a)有機二異氰酸酯、（b)多元醇及（c)具有羧基 與2個以上之活性氫的化合物反應所得到之具有羧基的異 氰酸酯基末端預聚物中和而於水中藉自己乳化而使之乳化 -52- 201120275 分散後，使用（d)具有2個以上胺基及/或亞胺基之聚胺 化合物使其進行鏈延長反應所得到之具有羧基及/或羧酸 酯基之聚胺基甲酸酯樹脂。 7.如申請專利範圍第1項之皮革用材料之製造方法， 其中（A)具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂中 之羧基含量與羧酸酯基含量之合計爲0.5〜4.0質量％。 8 . —種皮革用材料，其係依如申請專利範圍第〗〜7 項中任一項之製造方法所得到者。 -53- 201120275 四 指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無 201120275 五、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201120275 VII. Patent application scope: 1. A method for producing a leather material, which comprises (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, and (B) an ammonium salt of a mineral acid. And (C) a mixture of water, which is impregnated into a fibrous base material and then dried to obtain a material for leather. 2. The method for producing a leather material according to the first aspect of the invention, wherein in the mixture, (A) a polyurethane resin having a carboxyl group and/or a carboxylate group and (B) a mineral acid The blending ratio of the ammonium salt is converted to (A) by mass of the solid component: (B) = 100: 〇.1~1〇〇: 50. 3. The method for producing a leather material according to claim 1, wherein the inorganic acid in the salt of the inorganic acid is (B) sulfuric acid and/or phosphoric acid. 4. The method for producing a leather material according to claim 1, which comprises (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and ( C) The pH of the water mixture is 5.0~7_0. 5. The method for producing a leather material according to claim 1, which comprises (A) a polyurethane resin having a carboxyl group and/or a carboxylate group, (B) an ammonium salt of a mineral acid, and ( C) The sensible heat setting temperature of the water mixture is 30 to 80 °C. 6. The method for producing a leather material according to claim 1, wherein (A) the polyurethane resin having a carboxyl group and/or a carboxylate group is (a) an organic diisocyanate, (b) The polyisocyanate and (c) an isocyanate-based terminal prepolymer having a carboxyl group obtained by reacting a compound having a carboxyl group and two or more active hydrogens is neutralized and emulsified by self-emulsification in water - 52 - 201120275 (d) A polyurethane resin having a carboxyl group and/or a carboxylate group obtained by subjecting a polyamine compound having two or more amine groups and/or imine groups to a chain extension reaction. 7. The method for producing a leather material according to claim 1, wherein (A) the total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and/or a carboxylate group It is 0.5 to 4.0% by mass. 8. A material for leather, which is obtained according to the manufacturing method of any one of the application claims 7-14. -53- 201120275 IV Designated representative map: (1) The representative representative of the case is: None. (2) Simple description of the symbol of the representative figure: None 201120275 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none
TW099127586A 2009-08-20 2010-08-18 Method for producing leather material and leather material. TW201120275A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009191114A JP5070262B2 (en) 2009-08-20 2009-08-20 Method for producing leather material and leather material

Publications (1)

Publication Number Publication Date
TW201120275A true TW201120275A (en) 2011-06-16

Family

ID=43776965

Family Applications (1)

Application Number Title Priority Date Filing Date
TW099127586A TW201120275A (en) 2009-08-20 2010-08-18 Method for producing leather material and leather material.

Country Status (4)

Country Link
JP (1) JP5070262B2 (en)
KR (1) KR101665719B1 (en)
CN (1) CN101994263B (en)
TW (1) TW201120275A (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971146B (en) * 2010-07-12 2016-01-20 可乐丽股份有限公司 Tunicle formation method and tunicle
WO2012165569A1 (en) 2011-05-31 2012-12-06 宇部興産株式会社 Aqueous polyurethane resin dispersion and coating composition comprising same
JP6674244B2 (en) * 2014-12-12 2020-04-01 株式会社Adeka Thermosensitive coagulable water-based polyurethane resin composition, method for producing leather-like material using the composition, and leather-like material produced by the method
US20180208722A1 (en) * 2015-07-21 2018-07-26 Dic Corporation Method for producing coagulated article
CN105255155B (en) * 2015-10-26 2018-02-06 鹤山市新科达企业有限公司 The urethane composition of use for synthetic leather
US20200263351A1 (en) * 2017-09-22 2020-08-20 Kuraray Co., Ltd. Napped artificial leather
CN112575586A (en) 2019-09-30 2021-03-30 科思创德国股份有限公司 Acid and alkali resistant composition
JP6877665B1 (en) * 2021-02-08 2021-05-26 Ｔｂカワシマ株式会社 Antiviral agent composition and antiviral fabric, antiviral polyurethane sheet and antiviral polyvinyl chloride sheet treated with the composition.
WO2023074788A1 (en) * 2021-10-28 2023-05-04 三菱ケミカル株式会社 Aqueous resin composition, image forming method, and printed matter

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100275511B1 (en) * 1998-11-21 2000-12-15 정선종 Internal terminating call control mathod for the atm subscriber
US6475562B1 (en) * 2000-06-23 2002-11-05 Milliken & Company Textile-lastomer composite preferable for transfer on film coating and method of making said composite
KR100416878B1 (en) * 2000-11-09 2004-02-05 주식회사 코켐 Devlopment the process and the additives of wet-method using waterborne polyurethane resins
JP3940013B2 (en) * 2001-08-22 2007-07-04 三洋化成工業株式会社 Leather-like sheet material
JP4452139B2 (en) * 2004-07-28 2010-04-21 日華化学株式会社 Method for manufacturing leather materials
JP4458976B2 (en) * 2004-07-29 2010-04-28 日華化学株式会社 Manufacturing method of fiber composite material and fiber composite material

Also Published As

Publication number Publication date
CN101994263B (en) 2014-06-25
KR20110019712A (en) 2011-02-28
CN101994263A (en) 2011-03-30
KR101665719B1 (en) 2016-10-12
JP5070262B2 (en) 2012-11-07
JP2011042896A (en) 2011-03-03

Similar Documents

Publication Publication Date Title
TW201120275A (en) Method for producing leather material and leather material.
CN104837637B (en) Fabric for digital printing pre-processes object
JP6114079B2 (en) Method for producing leather material and leather material
KR100501660B1 (en) Aqueous urethane resin composition for forming microporous material, method for preparing fiber sheet composite and synthetic leather
JP2007092195A (en) Aqueous resin composition for fiber laminate skin, method for producing fiber laminate, and synthetic leather
US20170233595A1 (en) Aqueous polymer compositions for printing, digital ink jet inks and printing onto textiles
JP2015535314A5 (en)
JP4420761B2 (en) Polishing sheet manufacturing method and polishing sheet
JP5768043B2 (en) Polyurethane resin aqueous dispersion, nonporous film, moisture-permeable waterproof fabric, and method for producing the same
JP4452139B2 (en) Method for manufacturing leather materials
JP2000297211A (en) Aqueous urethane resin composition for forming porous layer
CN111350079A (en) Method for producing leather material
JP4204711B2 (en) Leather-like sheet manufacturing method
JP3975716B2 (en) Aqueous resin composition for forming fiber laminate skin layer and artificial leather using the same
JP4927621B2 (en) Aqueous polyurethane resin composition for skin layer formation and leather-like laminate using the same
WO2005040488A1 (en) Process for producing porous structure, artificial leather, and synthetic leather
JP2016125155A (en) Method for producing leather material and leather material
KR20030057478A (en) Artificial leather with silver and manufacturing method of floor material for the same
JP2020105445A (en) Aqueous polyurethane resin, method for manufacturing the same, aqueous polyurethane resin composition and leather material
CN116745487A (en) Aqueous polyurethane resin, surface treatment agent, and leather surface-treated with same
JP3980958B2 (en) Urethane resin composition
JP4077701B2 (en) Fiber material treatment method and substrate obtained by the treatment method
TWI261611B (en) High performance adhesives having aromatic water-borne polyurethane and flocking method employing the same
JP2005272618A (en) Normal temperature curing one-pack type water-based polyurethane composition, and water-based coating agent and water-based printing ink using the same
JP2009228179A (en) Grained sheet-like material