TW202030397A - Method for manufacturing leather material - Google Patents

Method for manufacturing leather material Download PDF

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TW202030397A
TW202030397A TW108146573A TW108146573A TW202030397A TW 202030397 A TW202030397 A TW 202030397A TW 108146573 A TW108146573 A TW 108146573A TW 108146573 A TW108146573 A TW 108146573A TW 202030397 A TW202030397 A TW 202030397A
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Taiwan
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aforementioned
polyurethane resin
water
group
acid
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TW108146573A
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Chinese (zh)
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福岡秀幸
鄭旻時
辛正援
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日商日華化學股份有限公司
南韓商韓國日華股份有限公司
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Publication of TW202030397A publication Critical patent/TW202030397A/en

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    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/04—Processes in which the treating agent is applied in the form of a foam
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • 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
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Abstract

The present invention provides an easier and more efficient method for manufacturing leather material than conventional method. The present invention is a method for manufacturing leather material, it is characterized by impregnating fibrous substrate with the mixture of (A) waterborne polyurethane, (B) foaming agent made by heating and / or adding acid to generate dioxide, (C) formic ester compound, and (D) water mixture, and then drying by heating to obtain a leather material.

Description

皮革用材料之製造方法Manufacturing method of leather materials

本發明係關於一種皮革用材料之製造方法，更詳細而言，係關於一種使用水性聚胺基甲酸酯樹脂的可適合用作人工皮革或合成皮革的皮革用材料之製造方法。 The present invention relates to a method for manufacturing a leather material, and more specifically, to a method for manufacturing a leather material suitable for artificial leather or synthetic leather using an aqueous polyurethane resin.

以往，作為天然皮革的代替品，製造了各種由聚胺基甲酸酯樹脂與纖維基材構成的人工皮革或合成皮革。如此的人工皮革或合成皮革例如利用如下的被稱為濕式凝固法的方法進行製造，所述方法為藉由含浸或塗布向纖維基材賦予聚胺基甲酸酯樹脂的有機溶劑溶液後，使其藉由相對於聚胺基甲酸酯樹脂為不良溶劑並且與前述有機溶劑具有相溶性的凝固液(通常為水)中並使之凝固，接著進行水洗、乾燥。 然而，在如此的濕式凝固法中大量使用的二甲基甲醯胺等有機溶劑大多數可燃性或毒性高，因此，存在火災的危險性、操作環境的惡化、空氣或水質等環境污染的問題，對人體的影響已成為問題。因此，正在進行使固著於纖維基材的聚胺基甲酸酯樹脂從有機溶劑型向水性聚胺基甲酸酯樹脂轉變的研究。 例如，在日本特開2003-138131號公報(專利文獻1)中公開了一種將包含HLB10~18的非離子界面活性劑與無機鹽的羧酸鹽型聚胺基甲酸酯樹脂的水性分散體賦予纖維基材並使其熱敏凝固而成的皮革用片材的製造方法。然而，在如此的方法中，由於界面活性劑及無機鹽的影響，具有處理浴的穩定性因所添加的無機鹽的濃度而變差這般的加工上的問題，或由於纖維基材中殘留有非離子界面活性劑或無機鹽，具有所得到的皮革用材料的質感變得粗硬般之問題。 另外，例如，在日本特開2002-249985號公報(專利文獻2)中公開了一種多孔性構造體之製造方法，該製造方法為將聚胺基甲酸酯系樹脂等熱塑性黏合劑水性液與選自由無機化合物、水溶性有機高分子、水難溶性有機高分子，及高濁點界面活性劑所構成之群組中之至少一種組合得到混合液，將該混合液賦予基材，在利用蒸氣進行濕熱加熱等之後，使其乾燥。利用如此的方法，可表現出天然皮革的質感。然而，即使在如此的多孔性構造體中，亦具有質感的柔軟性方面尚不充分如此的問題。 另外，近年來還研究了向水性聚胺基甲酸酯樹脂中加入發泡劑及熱敏凝固劑(熱敏膠凝劑)，使其含浸於纖維基材之後，進行乾燥的方法。例如，在國際公開第2013/065608號(專利文獻3)中記載了一種包含向包含超細纖維表現型纖維而成的纖維基材賦予含有發泡劑的水分散型聚胺基甲酸酯液(水性聚胺基甲酸酯樹脂)的步驟的片狀物的製造方法，並且記載了前述水分散型聚胺基甲酸酯液在被加熱後發泡，使所得到的水分散型聚胺基甲酸酯形成多孔構造，由此含有該聚胺基甲酸酯的片狀物的質感變得柔軟。然而，通常難以取得藉由加熱產生二氧化碳的發泡劑的發泡溫度與聚胺基甲酸酯液的凝固溫度的平衡，難以得到安全且均勻的發泡構造，因此，具有難以高效率且容易地得到柔軟的質感優異的皮革用材料這般的問題。進一步，在乾燥溫度低或乾燥時間短等乾燥條件不是比較充分的情況下，由於乾燥時纖維基材內部的溫度達不到發泡溫度，或者達到發泡溫度需要長時間這般的主要原因，亦具有發泡不充分、難以高效率且容易地得到柔軟的質感優異的皮革用材料這般的問題。 [先前技術文獻] [專利文獻] [專利文獻1] 日本特開2003-138131號公報 [專利文獻2] 日本特開2002-249985號公報 [專利文獻3] 國際公開第2013/065608號 In the past, as a substitute for natural leather, various artificial leathers or synthetic leathers composed of polyurethane resins and fiber substrates have been manufactured. Such artificial leather or synthetic leather is produced by, for example, the following method called wet coagulation, which is to impregnate or apply an organic solvent solution of polyurethane resin to the fiber substrate, It is coagulated in a coagulation liquid (usually water) that is a poor solvent for the polyurethane resin and has compatibility with the aforementioned organic solvent, followed by washing and drying. However, most of the organic solvents such as dimethylformamide used in such a wet coagulation method are highly flammable or toxic. Therefore, there is a risk of fire, deterioration of the operating environment, and environmental pollution such as air or water quality. The problem, the impact on the human body has become a problem. Therefore, research is being conducted to convert the polyurethane resin fixed to the fiber substrate from an organic solvent type to an aqueous polyurethane resin. For example, Japanese Patent Laid-Open No. 2003-138131 (Patent Document 1) discloses an aqueous dispersion of a nonionic surfactant containing HLB10-18 and an inorganic salt carboxylate polyurethane resin. A method for producing a leather sheet formed by providing a fiber substrate and thermally coagulating it. However, in such a method, due to the influence of surfactants and inorganic salts, the stability of the treatment bath is deteriorated due to the concentration of the added inorganic salt, or there is a processing problem due to remaining in the fiber base material. There are nonionic surfactants or inorganic salts, and there is a problem that the texture of the obtained leather material becomes rough. In addition, for example, Japanese Patent Application Laid-Open No. 2002-249985 (Patent Document 2) discloses a method of manufacturing a porous structure by mixing an aqueous solution of a thermoplastic binder such as polyurethane resin with At least one selected from the group consisting of inorganic compounds, water-soluble organic polymers, poorly water-soluble organic polymers, and high cloud point surfactants is combined to obtain a mixed solution. After damp heat heating etc., let it dry. Using such a method, the texture of natural leather can be expressed. However, even in such a porous structure, there is a problem that the softness of the texture is not yet sufficient. In addition, in recent years, a method of adding a foaming agent and a heat-sensitive coagulant (heat-sensitive gelling agent) to an aqueous polyurethane resin, impregnating the fiber substrate, and then drying it has also been studied. For example, in International Publication No. 2013/065608 (Patent Document 3), it is described that a water-dispersed polyurethane liquid containing a foaming agent is applied to a fibrous substrate containing ultrafine fiber phenotype fibers. (Aqueous polyurethane resin) step of the production method of the sheet, and it is described that the water-dispersed polyurethane liquid is heated and foamed to make the resulting water-dispersed polyamine Since the urethane forms a porous structure, the texture of the sheet-like article containing the polyurethane becomes soft. However, it is generally difficult to balance the foaming temperature of the foaming agent that generates carbon dioxide by heating and the solidification temperature of the polyurethane liquid. It is difficult to obtain a safe and uniform foaming structure. Therefore, it is difficult to achieve high efficiency and easy The problem of obtaining a soft leather material with excellent texture. Furthermore, when the drying conditions such as low drying temperature or short drying time are not sufficient, the main reason is that the temperature inside the fiber base material does not reach the foaming temperature during drying, or it takes a long time to reach the foaming temperature. There are also problems such as insufficient foaming and difficulty in efficiently and easily obtaining a leather material with excellent soft texture. [Prior Technical Literature] [Patent Literature] [Patent Document 1] JP 2003-138131 A [Patent Document 2] JP 2002-249985 A [Patent Document 3] International Publication No. 2013/065608

[發明所欲解決的技術課題] 本發明係鑒於上述現有技術所具有的技術問題而完成的，其目的在於提供一種可更容易且高效地得到柔軟的質感優異的皮革用材料的皮革用材料之製造方法。 [用以解決課題的技術方案] 為了上述目的，本發明者們重複專門研究，其結果發現，藉由使含有水性聚胺基甲酸酯樹脂、藉由加熱及/或酸產生二氧化碳之發泡劑、甲酸酯化合物，與水的混合液含浸於纖維基材後，進行加熱乾燥，由此即使不使條件的管理等如以往之製造方法那樣嚴格，亦可更容易且高效地得到柔軟的質感優異的皮革用材料，以完成本發明。 即，本發明的皮革用材料之製造方法如下所述。 [1]一種皮革用材料的製造方法，其特徵為：使含有(A)水性聚胺基甲酸酯樹脂、(B)藉由加熱及/或酸產生二氧化碳的發泡劑、(C)甲酸酯化合物，及(D)水的混合液含浸於纖維基材後，進行加熱乾燥，得到皮革用材料。 [2]如[1]之皮革用材料的製造方法，其中前述(B)發泡劑為碳酸鹽。 [3]如[1]或[2]之皮革用材料之製造方法，其中在前述混合液中，前述(A)水性聚胺基甲酸酯樹脂、前述(B)發泡劑，與前述(C)甲酸酯化合物的添加量比(A:B:C)以質量比計為100:1~50:1~75。 [4]如[1]~[3]中任一項之皮革用材料之製造方法，其中前述混合液近一步含有(E)增黏劑。 [5]如[1]~[4]中任一項之皮革用材料之製造方法，其中前述混合液近一步含有(F)熱敏膠凝劑。 [6]如[1]~[5]中任一項之皮革用材料之製造方法，其中前述(A)水性聚胺基甲酸酯樹脂為具有選自由羧基、羧酸酯基、磺基，及磺酸酯基所構成之群組中之至少1種陰離子性基的聚胺基甲酸酯樹脂。 [7]如[1]~[6]中任一項之皮革用材料之製造方法，其中前述混合液之熱敏凝固溫度為30~80℃。 [8]如[1]~[7]中任一項之皮革用材料之製造方法，其中以來自前述(A)水性聚胺基甲酸酯樹脂的成分固著至佔據皮革用材料之厚度中央部的10%部分的方式，使前述混合液含浸於前述纖維基材。 另外，藉由本發明的皮革用材料之製造方法可更容易且高效地得到柔軟的質感優異的皮革用材料的理由尚不明確，本發明者們推測如下。即，在使含有水性聚胺基甲酸酯樹脂及發泡劑的混合液含浸於纖維基材後進行乾燥的方法中，例如，在只使用酸產生物質使前述發泡劑發泡而產生二氧化碳的方法中，由於發泡的時機過早；另一方面，在只利用加熱使前述發泡劑發泡而產生二氧化碳的方法中，由於發泡的時機過晚，因此，都難以得到均勻的發泡構造。相對於此，本發明者們可以完成：在本發明的皮革用材料的製造方法中，藉由使含有水性聚胺基甲酸酯樹脂與利用加熱及/或酸產生二氧化碳之發泡劑的混合液近一步含有甲酸酯化合物，甲酸酯化合物隨著溫度的上升而緩慢分解，由此隨著溫度上升，pH緩慢下降，可在可得到均勻的發泡構造的時機由發泡劑產生二氧化碳，因此，可容易且高效地得到柔軟的質感優異的皮革用材料。 [發明之效果] 根據本發明，可提供一種可與以往相比更容易且高效地得到柔軟的質感優異的皮革用材料的皮革用材料之製造方法。[Technical Problem to be Solved by Invention] The present invention was made in view of the technical problems of the above-mentioned prior art, and its object is to provide a method for producing a leather material that can obtain a soft leather material with excellent texture more easily and efficiently. [Technical solution to solve the problem] For the above-mentioned purpose, the inventors of the present invention have repeated special studies, and as a result, they have found that a foaming agent containing water-based polyurethane resin, carbon dioxide generated by heating and/or acid, a formate compound, and water After impregnating the fibrous base material, the mixture is heated and dried. This makes it easier and more efficient to obtain a soft leather material with excellent texture even if the management of conditions is not as strict as the previous manufacturing method. this invention. That is, the manufacturing method of the leather material of this invention is as follows. [1] A method for producing a leather material, characterized in that: (A) an aqueous polyurethane resin, (B) a foaming agent that generates carbon dioxide by heating and/or acid, and (C) a After the fiber base material is impregnated with a mixed solution of an acid ester compound and (D) water, it is heated and dried to obtain a leather material. [2] The method for producing a leather material according to [1], wherein the aforementioned foaming agent (B) is carbonate. [3] The method for producing a leather material according to [1] or [2], wherein in the aforementioned mixture, the aforementioned (A) aqueous polyurethane resin, the aforementioned (B) foaming agent, and the aforementioned ( C) The addition amount ratio (A:B:C) of the formate compound is 100:1-50:1-75 by mass ratio. [4] The method for manufacturing leather materials as in any one of [1] to [3], wherein the aforementioned mixed solution further contains (E) a tackifier. [5] The method for manufacturing leather materials as described in any one of [1] to [4], wherein the aforementioned mixed liquid further contains (F) a heat-sensitive gelling agent. [6] The method for producing leather materials according to any one of [1] to [5], wherein the aforementioned (A) aqueous polyurethane resin has a carboxyl group, a carboxylate group, and a sulfo group, And at least one anionic polyurethane resin in the group consisting of sulfonate groups. [7] The method for manufacturing leather materials as in any one of [1] to [6], wherein the heat-sensitive solidification temperature of the aforementioned mixture is 30 to 80°C. [8] The method for manufacturing leather material as in any one of [1] to [7], wherein the component from the aforementioned (A) aqueous polyurethane resin is fixed to occupy the center of the thickness of the leather material The fiber base material is impregnated with the mixed liquid in the 10% part of the part. In addition, the reason why a leather material with a soft texture and excellent texture can be obtained more easily and efficiently by the method for producing a leather material of the present invention is not clear, but the present inventors speculate as follows. That is, in a method of impregnating a fiber base material with a mixed liquid containing an aqueous polyurethane resin and a foaming agent and then drying, for example, only an acid generating substance is used to foam the foaming agent to generate carbon dioxide. In the method, because the timing of foaming is too early; on the other hand, in the method of using only heating to foam the aforementioned foaming agent to generate carbon dioxide, the timing of foaming is too late, so it is difficult to obtain uniform hair泡结构。 Bubble structure. In contrast to this, the present inventors can complete: in the method for producing leather materials of the present invention, by mixing an aqueous polyurethane resin with a foaming agent that generates carbon dioxide by heating and/or acid The liquid contains a formate compound in the next step, and the formate compound is slowly decomposed as the temperature rises, so as the temperature rises, the pH slowly drops, and carbon dioxide can be generated from the foaming agent when a uniform foaming structure can be obtained. Therefore, it is possible to easily and efficiently obtain a soft leather material with excellent texture. [Effects of Invention] According to the present invention, it is possible to provide a method for producing a leather material that can obtain a soft leather material with excellent texture more easily and efficiently than before.

以下，基於其較佳的實施方式對本發明進行詳細地說明。 本發明的皮革用材料之製造方法其特徵為：使含有(A)水性聚胺基甲酸酯樹脂、(B)藉由加熱及/或酸產生二氧化碳之發泡劑、(C)甲酸酯化合物，及(D)水之混合液含浸於纖維基材後，進行加熱乾燥，得到皮革用材料。 (A)水性聚胺基甲酸酯樹脂 作為本發明所關於之(A)水性聚胺基甲酸酯樹脂，較佳為選自由具有親水性官能基之自乳化型水性聚胺基甲酸酯樹脂及強制乳化型水性聚胺基甲酸酯樹脂所構成之群組中之至少1種。 ＜自乳化型水性聚胺基甲酸酯樹脂＞ 在本發明中，前述自乳化型水性聚胺基甲酸酯樹脂為樹脂骨架中具有陰離子性基的水性聚胺基甲酸酯樹脂。在本發明中，作為前述自乳化型水性聚胺基甲酸酯樹脂，較佳為即使將聚胺基甲酸酯樹脂的水中濃度為40質量%的水乳化分散液在20℃下靜置12小時亦觀察不到分離或沉降的聚胺基甲酸酯樹脂。 作為上述陰離子性基，可列舉羧基、羧酸酯基、磺基、磺酸酯基等。作為本發明所關於之自乳化型水性聚胺基甲酸酯樹脂，從有乳化分散穩定性優異的傾向的這般觀點看來，較佳為具有選自由羧基、羧酸酯基、磺基，及磺酸酯基所構成之群組中的至少1種陰離子性基的聚胺基甲酸酯樹脂，更較佳為具有羧基及/或羧酸酯基之聚胺基甲酸酯樹脂或者具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂。 作為前述自乳化型水性聚胺基甲酸酯樹脂中的陰離子性基的含量，較佳為0.1~5.0質量%，更較佳為0.2~2.5質量%。另外，(i)在本發明所關於之自乳化型水性聚胺基甲酸酯樹脂具有羧基及/或羧酸酯基時，羧基及羧酸酯基的合計含量進一步較佳為0.5~4.0質量%，更進一步較佳為0.7~2.5質量%。另外，(ii)在本發明所關於之自乳化型水性聚胺基甲酸酯樹脂具有磺基及/或磺酸酯基時，磺基及磺酸酯基的合計含量進一步較佳為0.1~1.0質量%，更進一步較佳為0.2~1.0質量%。另外，(iii)在本發明所關於之自乳化型水性聚胺基甲酸酯樹脂具有羧基及/或羧酸酯基並且具有磺基及/或磺酸酯基時，特別較佳羧基及羧酸酯基的合計含量為0.1~4.0質量%，並且磺基及磺酸酯基的合計含量為0.1~1.0質量%。 前述陰離子性基的含量小於前述下限時，有自乳化型水性聚胺基甲酸酯樹脂的水分散液的儲存穩定性變差的傾向；另一方面，超過前述上限時，所得到的混合液的熱敏凝固溫度變高，有皮革用材料的遷移(水性聚胺基甲酸酯樹脂向纖維基材表面移動的現象)抑制效果下降的傾向。 另外，在本發明中，作為前述自乳化型水性聚胺基甲酸酯樹脂的100%模量的值，較佳為0.5~25MPa，更較佳為1~20MPa。100%模量的值小於前述下限時，雖然可得到柔軟的質感的皮革用材料，但有耐磨性下降的傾向；另一方面，超過前述上限時，所得到的皮革用材料的質感變硬，有容易發生起毛或纖維脫落的傾向。另外，在本發明中，100%模量的值是與JIS K 6251(2010)同樣地使用啞鈴狀3號形狀的試驗片進行測定而得到的標距長度伸長100%時(伸長至2倍時)的規定伸長拉伸應力(MPa)的值。 作為如此的自乳化型水性聚胺基甲酸酯樹脂，例如較佳使用： 使(a)有機多異氰酸酯、(b)多元醇，及(c)具有羧基與2個以上的活性氫的化合物進行反應，使所得到的具有羧酸酯基的異氰酸酯基封端預聚物中和物藉由自乳化而乳化分散於水中，使用(d)具有2個以上的胺基及/或亞胺基的多胺化合物，使其發生鏈增長反應而得到的具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂；及/或 (II)使(a)有機多異氰酸酯、(b)多元醇，及(e)具有2個以上的胺基和/或亞胺基且具有磺基和/或磺酸酯基的多胺化合物進行反應，使所得到的具有磺酸酯基的異氰酸酯基封端預聚物中和物藉由自乳化而乳化分散於水中，使用(d)具有2個以上的胺基及/或亞胺基的多胺化合物，使其發生鏈增長反應而得到的具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂。 以下，作為前述自乳化型水性聚胺基甲酸酯樹脂之製造方法，列舉該等樹脂為例進行說明。 (I)具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂 (a)有機多異氰酸酯 作為有機多異氰酸酯，沒有特別限制，可使用具有2個以上的異氰酸酯基的脂肪族多異氰酸酯、脂環式多異氰酸酯，及芳香族多異氰酸酯。作為如此的有機多異氰酸酯，例如可列舉六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等脂肪族二異氰酸酯化合物；異佛爾酮二異氰酸酯、氫化苯二亞甲基二異氰酸酯、二環己基甲烷二異氰酸酯、降冰片烷二異氰酸酯、1,3-雙(異氰酸甲酯基)環己烷等脂環式二異氰酸酯化合物；甲苯二異氰酸酯、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、苯二亞甲基二異氰酸酯、四甲基苯二亞甲基二異氰酸酯等芳香族二異氰酸酯化合物等。該等多異氰酸酯化合物可單獨使用1種，亦可將2種以上組合使用。 在如此的有機多異氰酸酯中，脂肪族二異氰酸酯化合物及脂環式二異氰酸酯化合物對皮革用材料賦予無黃化性，因此可較佳使用，特別較佳使用六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、降冰片烷二異氰酸酯及1,3-雙(異氰酸甲酯基)環己烷。 (b)多元醇 作為多元醇，只要是具有2個以上的羥基的多元醇，就沒有特別限制(但是，下述的(c)具有羧基與2個以上的活性氫的化合物除外)，除了聚酯多元醇、聚碳酸酯多元醇、聚醚多元醇等以外，亦可使用具有醚鍵與酯鍵的聚醚酯多元醇、有機矽多元醇、氟多元醇。 作為前述聚酯多元醇，例如可列舉聚己二酸乙二醇酯二醇(Polyethylene adipate diol)、聚己二酸丁二醇酯二醇、聚己二酸乙二醇丁二醇酯二醇、聚六亞甲基間苯二甲酸酯己二酸酯二醇、聚丁二酸乙二醇酯二醇(polyethylene succinate diol)、聚丁二酸丁二醇酯二醇、聚癸二酸乙二醇酯二醇、聚癸二酸丁二醇酯二醇、聚-ε-己內酯二醇、聚(3-甲基-1,5-亞戊基)己二酸酯二醇、1,6-己二醇與二聚酸的縮聚物、1,6-己二醇與己二酸與二聚酸的共縮聚物、壬二醇與二聚酸的縮聚物、乙二醇與己二酸與二聚酸的共縮聚物等。 作為前述聚碳酸酯多元醇，例如可列舉聚四亞甲基碳酸酯二醇、聚六亞甲基碳酸酯二醇、聚1,4-環己烷二亞甲基碳酸酯二醇、1,6-己二醇聚碳酸酯多元醇等。 作為前述聚醚多元醇，例如可列舉：作為環氧乙烷、環氧丙烷、環氧丁烷、氧雜環丁烷及氧雜環戊烷等碳數2~4的環氧烷烴的均聚加聚物或共聚加聚物的二元醇；在甘油、三羥甲基丙烷等多元醇上無規加成或嵌段加成有前述碳數2~4的環氧烷烴而成的多元醇。 作為前述有機矽多元醇，可列舉向二甲基聚矽氧烷的末端及/或側鏈導入2個以上的羥基及/或具有羥基的有機基而成的化合物，例如可列舉甲醇改性矽油、聚醚改性矽油、矽烷醇封端矽油。 作為前述氟多元醇，可列舉分子內包含氟之多元醇，例如可列舉Zeffle GK510、GK570(以上由大金工業(股)製造)、LUMIFLON LF200、LF400(以上由旭哨子(股)製造)。 該等多元醇可單獨使用1種，亦可將2種以上組合使用。另外，作為如此的多元醇的重量平均分子量，較佳為500~5,000，更較佳為1,000~3,000。另外，從可利用所得到的聚胺基甲酸酯樹脂對皮革用材料賦予充分的耐久性這般的觀點看來，作為前述多元醇，較佳使用聚碳酸酯多元醇及/或聚醚多元醇。另外，從有進一步提高所得到的皮革用材料的質感的傾向這般的觀點看來，較佳使用有機矽多元醇及/或氟多元醇。 (c)具有羧基與2個以上之活性氫之化合物 作為具有羧基與2個以上的活性氫之化合物，例如可列舉2,2-二羥甲基丙酸、2,2-二羥甲基丁酸。另外，作為如此的化合物，亦可使用使具有羧基的二元醇與芳香族二羧酸、脂肪族二羧酸等反應而得到的具有懸掛型羧基的聚酯多元醇。另外，如此的具有羧基與2個以上的活性氫的化合物可單獨使用1種，亦可將2種以上組合使用。 (d)具有2個以上的胺基及/或亞胺基的多胺化合物 作為具有2個以上的胺基及/或亞胺基的多胺化合物，例如可列舉：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、呱嗪、肼、2-甲基呱嗪、異佛爾酮二胺、降冰片烷二胺、二胺基二苯甲烷、甲苯二胺、二甲苯二胺等二胺；二亞乙基三胺、三亞乙基四胺、四亞乙基五胺、亞胺基二丙胺、三(2-胺基乙基)胺等多胺；由二伯胺及單羧酸衍生的醯胺胺；二伯胺的單酮亞胺等水溶性胺衍生物；草酸二醯肼、丙二酸二醯肼、琥珀酸二醯肼、戊二酸二醯肼、己二酸二醯肼、癸二酸二醯肼、馬來酸二醯肼、富馬酸二醯肼、衣康酸二醯肼、1,1’-亞乙基肼、1,1’-三亞甲基肼、1,1’-(1,4-亞丁基)二肼等肼衍生物。該等具有2個以上的胺基及/或亞胺基的多胺化合物可單獨使用1種，亦可將2種以上組合使用。 前述(I)具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂可藉由具有羧酸酯基的異氰酸酯基封端預聚物的中和物(以下，根據情況稱為「 CA異氰酸酯基封端預聚物中和物」)的利用自乳化向水中的乳化分散及鏈增長反應，形成該聚胺基甲酸酯樹脂的乳化分散液而得到。 前述CA異氰酸酯基封端預聚物中和物為具有來自前述(c)具有羧基與2個以上的活性氫的化合物的羧基被中和而成的羧酸酯基(-COO- )的異氰酸酯基封端預聚物中和物，並且為使前述(a)有機多異氰酸酯、前述(b)多元醇及前述(c)具有羧基與2個以上的活性氫的化合物反應而得到的。 作為用於得到如此的CA異氰酸酯基封端預聚物中和物的具體方法，沒有特別限制，例如可利用以往公知的一段式的所謂一步法、多段式的異氰酸酯加聚反應法等進行製造。此時的反應溫度較佳為40~150℃。 另外，如此的反應時，可根據需要使用具有2個以上的活性氫原子的低分子量擴鏈劑。作為前述低分子量擴鏈劑，分子量較佳400以下，特別較佳300以下。另外，作為前述低分子量擴鏈劑，例如可列舉：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、呱嗪、2-甲基呱嗪、異佛爾酮二胺、二亞乙基三胺、三亞乙基四胺等低分子量多胺。另外，作為上述低分子量擴鏈劑，可單獨使用1種，亦可將2種以上組合使用。 另外，上述反應時，可根據需要添加二月桂酸二丁基錫、辛酸亞錫、2-乙基己酸二丁基錫、三乙胺、三亞乙基二胺、N-甲基嗎啉等反應催化劑。另外，在反應時或反應結束後，可添加不與異氰酸酯基反應的有機溶劑。作為前述有機溶劑，例如可列舉丙酮、甲乙酮、甲苯、四氫呋喃、二噁烷、二甲基甲醯胺、N-甲基吡咯烷酮、乙酸乙酯、甲基異丁基酮等。 來自前述(c)具有羧基與2個以上的活性氫的化合物的羧基的中和可與異氰酸酯基封端預聚物的調製同時進行，亦可在調製前進行，亦可在調製後進行。如此的中和可適當使用公知的方法進行，作為用於如此的中和的化合物，沒有特別限制，例如可列舉：三甲胺、三乙胺、三正丙胺、三丁胺、N-甲基-二乙醇胺、N,N-二甲基單乙醇胺、N,N-二乙基單乙醇胺、三乙醇胺等胺類；氫氧化鉀；氫氧化鈉；胺等。該等中，特別較佳三甲胺、三乙胺、三正丙胺、三丁胺等叔胺類。 前述CA異氰酸酯基封端預聚物中和物向水中的乳化分散方法沒有特別限制，例如可列舉使用均質混合器、均化器、分散機等乳化設備的方法。另外，在使前述CA異氰酸酯基封端預聚物中和物乳化分散在水中時，較佳不特別使用乳化劑，而在室溫~40℃的溫度範圍內，藉由自乳化使該預聚物中和物乳化分散在水中，盡可能抑制異氰酸酯基與水的反應。另外，如此使之乳化分散時，可根據需要添加磷酸、磷酸二氫鈉、磷酸氫二鈉、對甲苯磺酸、己二酸、苯甲醯氯等反應抑制劑。 前述CA異氰酸酯基封端預聚物中和物的鏈增長反應可藉由向前述CA異氰酸酯基封端預聚物中和物中添加前述(d)具有2個以上的胺基及/或亞胺基的多胺化合物來進行，或者藉由向前述(d)具有2個以上的胺基和/或亞胺基的多胺化合物中添加前述CA異氰酸酯基封端預聚物中和物來進行。如此的鏈增長反應較佳以反應溫度20~40℃進行，通常在30~120分鐘內完成。 在前述(I)具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂的製造方法中，前述乳化分散及前述鏈增長反應可同時進行，亦可在使前述CA異氰酸酯基封端預聚物中和物乳化分散後進行鏈增長反應，亦可在進行鏈增長反應後進行乳化分散。另外，製造CA異氰酸酯基封端預聚物中和物時，在使用前述有機溶劑的情況下，例如較佳在鏈增長反應或乳化分散後，利用減壓蒸餾等除去有機溶劑。 (II)具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂 用於製造(II)具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂的(a)有機多異氰酸酯、(b)多元醇，及(d)具有2個以上的胺基及/或亞胺基的多胺化合物可列舉與前述(I)具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂的製造中所列舉的化合物相同的化合物。 (e)具有2個以上的胺基及/或亞胺基且具有磺基及/或磺酸酯基的多胺化合物 作為具有2個以上的胺基及/或亞胺基且具有磺基及/或磺酸酯基的多胺化合物，只要具有2個以上的胺基及/或亞胺基並且具有磺基及/或磺酸酯基即可，例如可列舉2-(2-胺基乙基胺基)-乙烷磺酸鈉、2-(3-胺基丙基胺基)-乙烷磺酸鈉、2,4-二胺基苯磺酸鈉等。該等化合物可單獨使用1種，亦可將2種以上組合使用。 前述(II)具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂可藉由具有磺酸酯基的異氰酸酯基封端預聚物的中和物(以下，根據情況稱為「SU異氰酸酯基封端預聚物中和物」)的利用自乳化向水中的乳化分散及鏈增長反應，形成該聚胺基甲酸酯樹脂的乳化分散液而得到。 前述SU異氰酸酯基封端預聚物中和物為具有來自前述(e)具有2個以上的胺基及/或亞胺基且具有磺基及/或磺酸酯基的多胺化合物的磺基被中和而成的磺酸酯基(-SO3 - )的異氰酸酯基封端預聚物中和物，並且可使前述(a)有機多異氰酸酯、前述(b)多元醇及(e)前述具有2個以上的胺基及/或亞胺基且具有磺基和/或磺酸酯基的多胺化合物反應而得到。 作為用於得到如此的SU異氰酸酯基封端預聚物中和物的具體方法，沒有特別限制，可列舉除了使用(e)前述具有2個以上的胺基及/或亞胺基且具有磺基及/或磺酸酯基的多胺化合物來代替前述(c)具有羧基與2個以上的活性氫的化合物以外，與前述CA異氰酸酯基封端預聚物中和物同樣的方法。另外，使前述SU異氰酸酯基封端預聚物中和物乳化分散並發生鏈增長反應而得到前述(II)具有磺基及/或磺酸酯基的聚胺基甲酸酯樹脂的方法亦可除了使用前述SU異氰酸酯基封端預聚物中和物來代替前述CA異氰酸酯基封端預聚物中和物以外，採用與前述(I)具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂的製造方法中所述的方法同樣的方法。 前述自乳化型水性聚胺基甲酸酯樹脂通常以樹脂的水乳化分散物的形態而得到，已在市場上流通，可適當使用。作為前述自乳化型水性聚胺基甲酸酯樹脂，較佳以乳化分散於水中的狀態使用，作為其濃度，沒有特別限制，但若考慮有可以均勻的狀態容易地得到本發明所關於之混合液的傾向，另外，樹脂成分對纖維基材的固著量，則較佳為15~60質量%。 另外，在本發明中，以乳化分散於水中的狀態使用自乳化型水性聚胺基甲酸酯樹脂及下述的強制乳化型水性聚胺基甲酸酯樹脂時，(A)水性聚胺基甲酸酯樹脂的質量(在2種以上的水性聚胺基甲酸酯樹脂的混合物時，為此等的合計質量)為指將該水性聚胺基甲酸酯樹脂的水乳化分散液在溫度105℃的條件下加熱3小時時的剩餘部分(固體成分、不揮發成分)的質量。 (強制乳化型水性聚胺基甲酸酯樹脂) 在本發明中，前述強制乳化型水性聚胺基甲酸酯樹脂為不具有前述陰離子性基(磺基、磺酸酯基、羧基、羧酸酯基等)，不具有自乳化性，為了使其在水中乳化而需要添加乳化劑(在本發明中，包含界面活性劑)，並且可利用前述乳化劑使其強制乳化的類型(強制乳化型)的水性聚胺基甲酸酯樹脂。在本發明中，作為前述強制乳化型水性聚胺基甲酸酯樹脂，較佳為如下的聚胺基甲酸酯樹脂：以該聚胺基甲酸酯樹脂在水中濃度成為40質量%的方式，適當使用前述乳化劑，使其強制乳化而得到水乳化分散液，即使將該水乳化分散液在20℃下靜置12小時，亦觀察不到分離或沉降。 作為如此的強制乳化型水性聚胺基甲酸酯樹脂，例如較佳使用： (III)使前述(a)有機多異氰酸酯與前述(b)多元醇反應，使所得到的異氰酸酯基封端預聚物在乳化劑的存在下乳化分散在水中，使用前述(d)具有2個以上的胺基及/或亞胺基的多胺化合物進行鏈增長反應而得到的聚胺基甲酸酯樹脂。 以下，作為前述強制乳化型水性聚胺基甲酸酯樹脂的製造方法，列舉如此的樹脂為例進行說明。 調製前述強制乳化型水性聚胺基甲酸酯樹脂時，首先，使前述(a)有機多異氰酸酯與前述(b)多元醇反應，調製異氰酸酯基封端預聚物。作為用於調製如此的異氰酸酯基封端預聚物的方法，沒有特別限制，除了不使用前述(c)具有羧基與2個以上的活性氫的化合物或前述(e)具有2個以上的胺基及/或亞胺基且具有磺基及/或磺酸酯基的多胺化合物，並且不需要羧基或磺基的中和以外，可採用與用於得到前述的CA異氰酸酯基封端預聚物中和物或SU異氰酸酯基封端預聚物中和物的方法同樣的方法。 調製前述強制乳化型水性聚胺基甲酸酯樹脂時，接著，使所得到的異氰酸酯基封端預聚物乳化分散並發生鏈增長反應，得到強制乳化型水性聚胺基甲酸酯樹脂。作為如此的異氰酸酯基封端預聚物的乳化分散及鏈增長反應的方法，沒有特別限制，除了使用前述異氰酸酯基封端預聚物來代替前述的CA異氰酸酯基封端預聚物中和物或SU異氰酸酯基封端預聚物中和物，並且在乳化分散時使用前述乳化劑以外，可採用與前述自乳化型水性聚胺基甲酸酯樹脂的製造方法中所說明的方法同樣的方法。即，只要使用前述末端具有異氰酸酯基的胺基甲酸酯預聚物來代替前述的CA異氰酸酯基封端預聚物中和物或SU異氰酸酯基封端預聚物中和物，並且在使前述異氰酸酯基封端預聚物乳化分散在水中時，使用乳化劑，進行乳化分散同時進行鏈增長反應即可，作為乳化分散於水中的方法或鏈增長反應，可採用分別與前述自乳化型水性聚胺基甲酸酯樹脂的製造方法中所說明的乳化分散方法或鏈增長反應相同的方法。 在調製前述強制乳化型水性聚胺基甲酸酯樹脂時，作為前述乳化劑，可列舉非離子界面活性劑及陽離子界面活性劑。作為前述非離子界面活性劑，例如可列舉聚氧乙烯二苯乙烯基苯基醚型非離子界面活性劑、聚氧乙烯丙烯二苯乙烯基苯基醚型非離子界面活性劑、聚氧乙烯三苯乙烯基苯基醚型非離子界面活性劑、聚氧乙烯丙烯三苯乙烯基苯基醚型非離子界面活性劑、普盧蘭尼克(Pluronic)型非離子界面活性劑。另外，作為前述陰離子界面活性劑，例如可列舉高級醇硫酸酯鹽、高級烷基醚硫酸酯鹽、聚亞烷基二醇硫酸酯鹽、聚氧化烯芳基醚硫酸酯鹽、聚氧化烯芳基醚磷酸酯鹽硫酸化油、硫酸化脂肪酸酯、烷基苯磺酸鹽、烷基萘磺酸鹽、萘磺酸鹽及其聚合物、石蠟磺酸鹽、二烷基磺基琥珀酸鹽、聚苯乙烯磺酸鹽、木質素磺酸鹽、烷基醚磷酸酯鹽。 作為前述乳化劑，可單獨使用該等中的1種，亦可將2種以上組合使用，較佳為前述非離子界面活性劑中的至少1種，其中，從強制乳化型水性聚胺基甲酸酯樹脂的水分散液的儲存穩定性與加工穩定性的觀點看來，較佳使用HLB為7~16的化合物。另外，在本發明中，HLB的值是由下式得到的值。 非離子界面活性劑中的氧乙烯基部分的分子量×20/非離子界面活性劑的分子量 作為前述乳化劑的添加量，根據作為被乳化物的異氰酸酯基封端預聚物的聚氧乙烯基含量等所產生的親水性而不同，不能一概而論，相對於前述異氰酸酯基封端預聚物100質量份較佳為0.5~10質量份，更較佳為1~6質量份。如此的乳化劑的添加量小於前述下限時，有難以得到充分穩定的乳化分散狀態的傾向，另一方面，超過前述上限時，有所得到的發泡構造的耐水性下降的傾向。 前述強制乳化型水性聚胺基甲酸酯樹脂可以藉由異氰酸酯基封端預聚物在乳化劑的存在下向水中的乳化分散及鏈增長反應，形成該聚胺基甲酸酯樹脂的乳化分散物而得到。作為如此的強制乳化型水性聚胺基甲酸酯樹脂，較佳以乳化分散於水中的狀態使用，作為其濃度，沒有特別限制，但若考慮有可以均勻的狀態容易地得到本發明所關於之混合液的傾向，另外，樹脂成分對纖維基材的固著量，則較佳為15~60質量%。 (B)發泡劑 本發明所關於之(B)發泡劑為藉由加熱、或藉由酸、或藉由加熱及酸(藉由加熱及/或酸)產生二氧化碳的發泡劑。作為本發明所關於之(B)發泡劑，較佳為熱分解型化學發泡劑，更較佳為碳酸鹽。作為前述(B)發泡劑，可單獨使用1種，亦可將2種以上組合使用，其中，從混合液的加工穩定性的觀點看來，較佳為選自由碳酸鈉、碳酸鉀、碳酸銨、碳酸氫鈉(重碳酸鈉)、碳酸氫鉀，及碳酸氫銨(重碳酸銨)所構成之群組中之至少1種碳酸鹽。 在本發明中，可直接以固體(粉體)之狀態使用前述(B)發泡劑，但從保持前述(A)水性聚胺基甲酸酯樹脂的乳化分散液的穩定性這般觀點看來，較佳使前述(B)發泡劑包含於水中而以水溶液之狀態使用。作為前述(B)發泡劑的水溶液的濃度，沒有特別限制，可為1~50質量%左右。 (C)甲酸酯化合物 本發明所關於之(C)甲酸酯化合物為羥基化合物之甲酸酯。作為前述羥基化合物，可列舉碳數1~4的低級醇、單或聚亞烷基二醇、三羥甲基丙烷、單或聚甘油等，可單獨使用該等中的1種，亦可將2種以上組合使用。該等中，作為前述羥基化合物，從所得到的皮革用材料的柔軟性的觀點看來，較佳為單或聚亞烷基二醇，更較佳為乙二醇、二乙二醇、三乙二醇、聚合度3~10的聚乙二醇，進一步較佳為乙二醇。 另外，作為本發明所關於之(C)甲酸酯化合物，可使用三甲基原甲酸酯(原甲酸三甲酯)、三乙基原甲酸酯等原甲酸酯。作為該等甲酸酯化合物，可單獨使用1種，亦可將2種以上組合使用。 (D)水 本發明所關於之(D)水在將前述(A)水性聚胺基甲酸酯樹脂、前述(B)發泡劑、前述(C)甲酸酯化合物，及根據需要的後述的各成分混合時，具有作為溶劑的作用，較佳使用離子交換水或蒸餾水。 另外，作為如此的(D)水，例如在使用使前述(A)水性聚胺基甲酸酯樹脂乳化分散在水中而成的乳化分散液的情況下，或在使各成分成為水溶液而使用的情況下，不將該乳化分散液或該水溶液中的水蒸餾除去而直接利用，可將該水直接用作本發明所關於之(D)水。 (E)增黏劑 作為本發明所關於之混合液，較佳進一步含有(E)增黏劑。藉由近一步含有前述(E)增黏劑，可抑制遷移，可充分保持纖維基材的厚度，可得到更柔軟的質感優異的皮革用材料。 作為前述(E)增黏劑，沒有特別限制，可適當利用水性聚胺基甲酸酯樹脂的水分散液中可利用的公知的增黏劑，其中較佳為選自由締合型增黏劑及水溶性高分子增黏劑所構成之群組中之至少1種。 作為前述締合型增黏劑，例如可列舉：日本特開昭54-80349號公報、日本特開昭58-213074號公報、日本特開昭60-49022號公報、日本特公昭52-25840號公報、日本特開平9-67563號公報、日本特開平9-71766號公報等中記載之胺基甲酸酯系的締合型增黏劑；日本特開昭62-292879號公報、日本特開平10-121030號公報等中記載的將非離子性胺基甲酸酯單體作為締合性單體並與其他的丙烯酸單體共聚而得到之締合型增黏劑；WO9640815等中記載的具有胺基塑膠骨架的締合型增黏劑等。該等中，作為前述締合型增黏劑，較佳非離子性的性質強的締合型增黏劑，從所得到的發泡構造(多孔性構造)中的孔的緻密性及強度保持力的觀點看來，更較佳分子鏈中具有聚乙二醇鏈與胺基甲酸酯鍵之締合型增黏劑。作為如此的締合型增黏劑，例如可適當使用NEOSTECKER S(日華化學公司製造)、VISRIZER AP-2(三洋化成工業股份有限公司)等市售品。 作為前述水溶性高分子增黏劑，例如可列舉甲基纖維素、乙基纖維素、羥乙基纖維素、羥丙基纖維素、甲基羥丙基纖維素、羧甲基纖維素等纖維素系衍生物；可溶性澱粉、羧甲基澱粉、甲基澱粉等澱粉系衍生物；藻酸鈉、藻酸丙二醇酯等藻酸系；瓜爾膠、卡拉膠、半乳聚糖、阿拉伯膠、刺槐豆膠、榅桲籽(quince seed)、黃蓍膠、果膠、甘露聚糖、澱粉、黃原膠、葡聚糖、琥珀醯聚糖(Succinoglycan)、凝膠多糖、透明質酸及其鹽等天然多糖系；酪蛋白、明膠、膠原蛋白、白蛋白等天然蛋白質系；聚亞烷基二醇、聚氧乙二醇二硬脂酸酯、肉豆蔻醯聚氧乙烯硬脂基醚、聚氧乙烯山梨糖醇酐三異硬脂酸酯、聚氧乙烯甲基葡萄糖(單、二或三)月桂酸酯、聚氧乙烯甲基葡萄糖(單、二或三)肉豆蔻酸酯、聚氧乙烯甲基葡萄糖(單、二或三)棕櫚酸酯、聚氧乙烯甲基葡萄糖(單、二或三)硬脂酸酯、聚氧乙烯甲基葡萄糖(單、二或三)異硬脂酸酯、聚氧乙烯甲基葡萄糖(單、二或三)油酸酯等聚氧化烯系非離子型聚合物；聚乙烯醇、聚乙烯基吡咯烷酮、聚乙烯基甲基醚等乙烯基系聚合物等以及該等的混合物，該等中更較佳非離子性的性質強的化合物。作為如此的水溶性高分子增黏劑，亦可適當使用HEC AX-15(住友精化股份有限公司製造、羥乙基纖維素)、Kelzan(三晶股份有限公司製造、高分子多糖類(黃原膠))等市售品。 (F)熱敏膠凝劑 作為本發明所關於之混合液，從藉由抑制加熱乾燥時的發泡構造的收縮、抑制遷移而可使質感進一步柔軟化如此的觀點看來，較佳進一步含有(F)熱敏膠凝劑。 作為前述(F)熱敏膠凝劑，沒有特別限制，可適當使用公知的熱敏膠凝劑(在所謂的包含水性聚胺基甲酸酯樹脂的以往的發泡體形成用組合物中，為了使組合物熱敏凝膠化(熱敏凝固)而被利用的公知的熱敏膠凝劑等)，例如可列舉無機酸的鈉鹽、無機酸的銨鹽、水溶性丙烯酸系聚合物等，可單獨使用該等中的1種，也可以將2種以上組合使用。 作為前述無機酸的鈉鹽或無機酸之銨鹽中之無機酸，可列舉高氯酸、碳酸、硫酸、過硫酸、亞硫酸、磷酸、硝酸等。其中，作為前述無機酸，從遷移抑制效果優異的觀點看來，較佳硫酸、磷酸。 作為前述無機酸的鈉鹽，例如可列舉硫酸鈉(芒硝)。另外，作為前述無機酸的銨鹽，例如可列舉過硫酸銨、高氯酸銨、碳酸銨、硫酸銨、硫酸氫銨、亞硫酸銨、亞硫酸氫銨、磷酸三銨、磷酸氫二銨、磷酸二氫銨、過硫酸銨、硝酸銨、氯化銨等，可單獨使用該等中的1種，亦可將2種以上組合使用，從操作的安全性、乾燥中的揮發問題以及乾燥後藉由水洗可容易地去除、皮革用材料中殘留少如此的觀點看來，較佳使用選自由硫酸銨、磷酸氫二銨及磷酸二氫銨所構成之群組中之至少1種。另外，使用磷酸二氫銨作為前述無機酸的銨鹽時，更較佳與磷酸氫二銨組合使用。 作為前述水溶性丙烯酸系聚合物，沒有特別限制，較佳為下述成分(1)、下述成分(2)、下述成分(3)、下述成分(4)，及下述成分(5)中的至少1種。 [成分(1)] 選自由丙烯酸、甲基丙烯酸，及馬來酸所構成之群組中之至少1種單體的聚合物、該聚合物的鹼金屬鹽以及該聚合物的胺鹽中的至少1種。 [成分(2)] 聚-α-羥基丙烯酸、聚-α-羥基丙烯酸的鹼金屬鹽，及聚-α-羥基丙烯酸的胺鹽中的至少1種。 [成分(3)] 使選自由丙烯酸、甲基丙烯酸、馬來酸、丙烯酸的鹼金屬鹽、甲基丙烯酸的鹼金屬鹽、馬來酸的鹼金屬鹽、丙烯酸的胺鹽、甲基丙烯酸的胺鹽，及馬來酸的胺鹽所構成之群組中的至少1種單體與選自由聚-α-羥基丙烯酸、聚-α-羥基丙烯酸的鹼金屬鹽及聚-α-羥基丙烯酸的胺鹽所構成之群組中的至少1種進行自由基聚合而得到的聚合物、該聚合物的鹼金屬鹽以及該聚合物的胺鹽中的至少1種。 [成分(4)] 使選自由丙烯酸、甲基丙烯酸、馬來酸、聚-α-羥基丙烯酸、丙烯酸的鹼金屬鹽、甲基丙烯酸的鹼金屬鹽、馬來酸的鹼金屬鹽、聚-α-羥基丙烯酸的鹼金屬鹽、丙烯酸的胺鹽、甲基丙烯酸的胺鹽、馬來酸的胺鹽，及聚-α-羥基丙烯酸的胺鹽所組成之群組中的至少1種丙烯酸類單體與2-丙烯醯胺-2-甲基丙磺酸、苯乙烯磺酸，及此等的鹼金屬及/或胺鹽等磺酸系單體進行自由基聚合而得到的聚合物中的至少1種。 [成分(5)] 使丙烯酸類單體與非離子類單體進行自由基聚合而得到的聚合物，以及使由丙烯酸系單體、磺酸類單體，與非離子系單體構成的單體混合物進行自由基聚合而得到的聚合物並且前述單體混合物中的丙烯酸系單體與磺酸類單體的含量(合計量)為30質量%以上的聚合物中的至少1種。 作為前述成分(5)中的非離子系單體，可列舉丙烯酸(碳數1~22)烷基酯、乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、二丙酮(甲基)丙烯醯胺、羥甲基化二丙酮(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、3-氯-2-羥基丙基(甲基)丙烯酸酯、乙烯基烷基醚、鹵代烷基乙烯基醚、乙烯基烷基酮、丁二烯、異戊二烯、氯丁二烯、(甲基)丙烯酸吖丙啶基乙酯、(甲基)丙烯酸吖丙啶酯、聚氧化烯(甲基)丙烯酸酯、聚氧化烯(甲基)丙烯酸甲酯、聚氧化烯(甲基)丙烯酸2-乙基己酯、聚氧化烯二(甲基)丙烯酸酯、氰脲酸三烯丙酯、烯丙基縮水甘油醚、乙酸烯丙酯、N-乙烯基哢唑、馬來醯亞胺、N-甲基馬來醯亞胺、(2-二甲基胺基)乙基(甲基)丙烯酸酯、(甲基)丙烯酸甘油酯、二(甲基)丙烯酸亞烷基酯、乙烯基矽烷、(甲基)丙烯酸三甲氧基甲矽烷基酯等側鏈具有矽酮的(甲基)丙烯酸酯、具有聚矽氧烷的(甲基)丙烯酸酯、含有封端化異氰酸酯基的(甲基)丙烯酸酯、具有胺基甲酸酯鍵的(甲基)丙烯酸酯等。 另外，作為前述水溶性丙烯酸系聚合物(較佳成分(1)~(5)中的至少1種)，例如也可適當使用Aron A-50P(東亞合成股份有限公司製造、磺酸單體共聚型丙烯酸系增黏劑)等市售品。 本發明所關於之混合液進一步含有前述(F)熱敏膠凝劑時，該(F)熱敏膠凝劑可直接以固體(粉體)的狀態使用，但從保持前述(A)水性聚胺基甲酸酯樹脂的乳化分散液的穩定性這般的觀點看來，較佳使前述(F)熱敏膠凝劑包含於水而以水溶液的狀態使用。作為前述(F)熱敏膠凝劑的水溶液的濃度，較佳為1~50質量%，更較佳為10~30質量%。前述濃度小於前述下限時，為了發揮乾燥時的遷移抑制性，需要大量的前述水溶液，隨之混合液中的前述(A)水性聚胺基甲酸酯樹脂的濃度降低。因此，為了得到目標的皮革用材料，需要大量的混合液，因此，有所揮發的水分量變多、乾燥時間變長、經濟性下降的傾向。然而，由於本發明的方法為生產效率高的方法，該問題有被改善的傾向。另一方面，前述濃度超過前述上限時，有在與前述(A)水性聚胺基甲酸酯樹脂的乳化分散液混合時產生析出物等損害乳化分散液的穩定性的傾向。 ＜混合液＞ 在本發明的皮革用材料的製造方法中，調製含有前述(A)水性聚胺基甲酸酯樹脂、前述(B)發泡劑、前述(C)甲酸酯化合物、前述(D)水，以及根據需要的前述(E)增黏劑及/或前述(F)熱敏膠凝劑的混合液。 在本發明所關於之混合液中，作為前述(A)水性聚胺基甲酸酯樹脂的含量，相對於前述混合液總量，較佳為5~50質量%，更較佳為10~35質量%。前述(A)水性聚胺基甲酸酯樹脂的含量小於前述下限時，為了得到目標的皮革用材料，需要大量的混合液，因此，有所揮發的水分量變多、乾燥時間變長、經濟性下降的傾向。另一方面，超過前述上限時，有混合液的穩定性下降的傾向。 另外，在本發明中，所謂含量或添加量，在其成分為2種以上的混合物時，其值表示此等的合計含量或添加量。 在本發明所關於之混合液中，作為前述(A)水性聚胺基甲酸酯樹脂與前述(B)發泡劑的添加量比(A:B)，以質量比計較佳為100:1~50，更較佳為100:5~50，進一步較佳為100:5~30。前述(B)發泡劑的添加量小於前述下限時，有對所得到的皮革用材料賦予柔軟的質感的效果下降的傾向；另一方面，超過前述上限時，有混合液的經時穩定性下降的傾向。另外，超過前述上限時，即使添加前述(B)發泡劑，亦有無法進一步提高性能的傾向，因此，在經濟上不利。 另外，在本發明所關於之混合液中，作為前述(A)水性聚胺基甲酸酯樹脂與前述(C)甲酸酯化合物的添加量比(A:C)，以質量比計較佳為100:1~75，更較佳為100:5~75，進一步較佳為100:5~50。前述(C)甲酸酯化合物的添加量小於前述下限時，有對所得到的皮革用材料賦予柔軟的質感的效果下降的傾向；另一方面，超過前述上限時，在夏天等比較高溫的氣溫氣氛下，有混合液發泡或混合液的經時穩定性下降的傾向。另外，超過前述上限時，即使添加(C)甲酸酯化合物，亦有無法進一步提高性能的傾向，因此，在經濟上不利。 進一步，在本發明所關於之混合液中，作為前述(A)水性聚胺基甲酸酯樹脂與前述(B)發泡劑與前述(C)甲酸酯化合物的添加量比(A:B:C)，從與上述相同的觀點看來，以質量比計較佳為100:1~50:1~75，更較佳為100:5~50:5 ~75，進一步較佳為100:5~30:5~50。 另外，本發明所關於之混合液進一步含有前述(E)增黏劑時，作為前述(A)水性聚胺基甲酸酯樹脂與前述(E)增黏劑的添加量比(A:E)，以質量比計較佳為100:0.01~50，更較佳為100:0.1~30，進一步較佳為100:0.1~10。前述(E)增黏劑的添加量小於前述下限時，有對所得到的皮革用材料賦予更柔軟的質感的效果下降的傾向；另一方面，超過前述上限時，有混合液成為高黏度而使用性下降的傾向。 另外，本發明所關於之混合液更進一步含有前述(F)熱敏膠凝劑時，作為前述(A)水性聚胺基甲酸酯樹脂與前述(F)熱敏膠凝劑的添加量比(A:F)，以質量比計較佳為100:0.1~15，更較佳為100:0.2~10。前述(F)熱敏膠凝劑的添加量小於前述下限時，有乾燥步驟的遷移抑制效果下降、對所得到的皮革用材料賦予更柔軟的質感的效果下降的傾向；另一方面，超過前述上限時，在夏天等比較高溫的氣溫氣氛下，有混合液凝膠化或混合液容易發生分散不良的傾向。另外，超過前述上限時，即使添加(F)熱敏凝膠劑，亦有無法進一步提高性能的傾向，因此，在經濟上不利。 另外，本發明所關於之混合液更進一步含有前述(F)熱敏膠凝劑時，作為其含量，從可更充分地保持發泡體的乾燥後的厚度的觀點及混合液的穩定性的觀點看來，相對於前述(A)水性聚胺基甲酸酯樹脂的添加量100質量份，亦較佳為0.01~10質量份，亦較佳為0.05~5質量份。 作為本發明所關於之混合液的熱敏凝固溫度，較佳為30~80℃，更較佳為40~70℃。在本發明中，熱敏凝固溫度為將前述混合液5~10g放入20mL的玻璃製試管中，將該試管在水浴中靜置，對水浴以1℃/分鐘進行升溫時，內容物喪失流動性而凝固時的溫度。熱敏凝固溫度小於前述下限時，在夏天等比較高溫的氣溫氣氛下，有混合物凝膠化的傾向；另一方面，超過前述上限時，由於熱敏凝固不明顯表現，因此，有在凝固步驟中凝固變弱、遷移抑制性下降的傾向；特別是在85~120℃左右的比較低的溫度下使其乾燥(凝固)時，該傾向變得顯著。 另外，作為本發明所關於之混合液之黏度，從有進一步提高所得到之皮革用材料之柔暖之質感之傾向的觀點看來，以25℃之黏度計較佳為10~2,000mP‧s，更較佳為10~2,000 mP‧s。作為本發明所關於之混合液的調製方法，沒有特別限制，可適當利用公知的方法將上述成分混合而調製。 ＜纖維基材＞ 在本發明的皮革用材料的製造方法中，使前述混合液含浸於纖維基材後，進行加熱乾燥，得到皮革用材料。 作為本發明所關於之纖維基材，沒有特別限制，可適當使用機織物、針織物或無紡布等。另外，作為如此的纖維基材的原材料，沒有特別限制，從充分保持厚度、有得到更接近天然的皮革的質感及品質的傾向這般的觀點看來，較佳聚醯胺纖維、聚酯纖維。 使用無紡布作為上述纖維基材時，作為其紗的粗細，從進一步提高所得到的皮革用材料的質感及品質這般的觀點看來，較佳為2.0dtex以下。無紡布的紗的粗細超過前述上限時，有所得到的皮革用材料的質感變得粗硬而質量受損的傾向。另外，作為如此的無紡布的密度，較佳為0.1~0.8g/cm3 ，更較佳為0.30~0.55g/cm3 。無紡布的密度小於前述下限時，有所得到的皮革用材料的耐磨性下降的傾向，另外，若為了彌補其而固著大量的聚胺基甲酸酯樹脂，則有所得到的皮革用材料的質感變得粗硬而質量受損的傾向。另一方面，無紡布的密度超過前述上限時，有所得到的皮革用材料的質感變得粗硬而品質受損的傾向。另外，作為前述纖維基材的厚度，沒有特別限制，較佳為0.1~1cm，更較佳為0.1~0.5cm。 在本發明中，在不損害本發明的效果範圍內，以對所得到之皮革用材料賦予加工適應性為目的，進一步可向前述混合液中添加添加劑。作為如此的添加劑，例如可列舉：低級醇、二醇系溶劑、醇系的非離子界面活性劑、炔二醇系的特殊界面活性劑、矽酮系的界面活性劑、氟系的界面活性劑、陰離子界面活性劑、陽離子界面活性劑等各種浸透劑；抗氧化劑、耐光穩定劑、防紫外線劑等各種穩定化劑；礦物油系、矽酮系等各種消泡劑；聚胺基甲酸酯化催化劑；增塑劑；顏料等著色劑；使用壽命延長劑；丙烯酸樹脂珠、聚胺基甲酸酯樹脂珠等填充劑等。如此的添加劑可單獨使用1種，亦可將2種以上組合使用。向本發明所關於之混合液中添加此等添加劑時，作為其合計添加量，將前述混合液中所添加的(A)水性聚胺基甲酸酯樹脂、(B)發泡劑、(C)甲酸酯化合物的合計質量設為100質量份時，較佳為成為50質量份以下的量。另外，以乳化分散於水中而成的水乳化分散液的狀態使用該等化合物時，其質量係指將該水乳化分散液在溫度105℃的條件下加熱3小時時的剩餘部分(固體成分、不揮發成分)的質量。 另外，在本發明中，使用前述具有羧基及/或羧酸酯基的聚胺基甲酸酯樹脂作為前述(A)水性聚胺基甲酸酯樹脂時，在不損害本發明的效果的範圍內，以對所得到的皮革用材料賦予加工適應性為目的，進一步可向前述混合液中添加與前述羧基反應的交聯劑。作為如此的交聯劑，可列舉噁唑啉系交聯劑、環氧系交聯劑、異氰酸酯系交聯劑、碳二亞胺系交聯劑、氮丙啶系交聯劑、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。作為前述交聯劑，可單獨使用1種，亦可將2種以上組合使用。此等交聯劑中，從有進一步提高所得到的皮革用材料的耐光性、耐熱性、耐水性的傾向這般的觀點考慮，較佳碳二亞胺系交聯劑，作為其添加量，將前述(A)水性聚胺基甲酸酯樹脂設為100質量份時，較佳為成為0.5~10質量份的量。 在本發明中，作為使前述混合液含浸於前述纖維基材的方法，沒有特別限制，可適當使用公知的方法。作為前述含浸方法，例如較佳採用由浸軋(dip-nip)方式構成的含浸加工、噴霧處理、一邊利用塗布機進行塗布一邊浸入的方法等一直以來公知的方法，前述混合液的濃度及處理條件等亦可根據所採用的方法適當選擇。另外，在使前述混合液含浸於前述纖維基材之前，可對前述纖維基材進行前處理。作為如此的前處理步驟，為了調整前述纖維基材與聚胺基甲酸酯樹脂成分的接著力，較佳使用由聚乙烯醇、羧甲基纖維素等構成的高分子水溶液、矽酮系撥水劑、氟系撥水劑等對前述纖維基材進行處理。 作為前述混合液相對於前述纖維基材的含浸量，從進一步提高纖維基材的厚度保持率，所得到的皮革用材料的質感及摩擦牢度等的物性亦進一步提高這般的觀點看來，較佳以來自前述(A)水性聚胺基甲酸酯樹脂的成分在所得到的皮革用材料中成為5~75質量%的方式進行含浸。 另外，作為本發明所關於的含浸，較佳以來自前述(A)水性聚胺基甲酸酯樹脂的成分充分固著至所得到的皮革用材料的內部的方式進行含浸。根據本發明的製造方法，為了抑制遷移，可如此充分地使來自前述(A)水性聚胺基甲酸酯樹脂的成分固著，保持纖維基材的厚度，實現優異的摩擦牢度。作為如此的來自(A)水性聚胺基甲酸酯樹脂的成分的固著狀態，在利用掃描型電子顯微鏡以150倍的倍率觀察所得到的皮革用材料的截面時，較佳不僅在該皮革用材料的表面，而且在佔據該皮革用材料的厚度中央部的10%部分的都可觀察到來自前述(A)水性聚胺基甲酸酯樹脂的成分的固著，更較佳在該皮革用材料的中央部與表面部，樹脂固著量完全看不出差異。 在本發明中，使前述混合液含浸於前述纖維基材後，進行加熱乾燥，由前述(B)發泡劑產生二氧化碳，使前述混合液發泡並凝固。在本發明中，作為前述加熱乾燥方法，沒有特別限制，例如可使用：利用熱風的乾熱乾燥；利用高溫蒸汽機(H.T.S.)、高壓蒸汽機(H.P.S.)的濕式乾燥；微波照射式乾燥等，其中，從樹脂凝固性、縮短凝固時間的觀點看來，較佳藉由利用濕度(蒸氣)的濕式乾燥而使其濕熱凝固。此等乾燥方法可單獨使用1種，亦可將2種以上組合使用。另外，作為加熱乾燥條件(凝固條件)，較佳以80~180℃的溫度加熱乾燥1~30分鐘，更較佳以80~130℃(更較佳85~120℃)的溫度加熱乾燥2~10分鐘。藉由如此地使含浸於前述纖維基材的前述混合液乾燥並凝固，可使聚胺基甲酸酯樹脂固著於纖維基材內部。在本發明中，較佳在使前述混合液凝固後，進一步實施以100~200℃(較佳120~180℃)用於使水分乾燥的乾熱乾燥1~60分鐘(較佳2~30分鐘)。 藉由如此地使含浸於前述纖維基材的前述混合液加熱乾燥，使其發泡(產生二氧化碳)並凝固，可使均勻的發泡構造的聚胺基甲酸酯樹脂固著於纖維基材內部，得到本發明的皮革用材料。 如此得到的本發明的皮革用材料可實施染色。本發明的皮革用材料即使實施染色，亦可充分維持其柔軟的質感。作為如此的染色方法，沒有特別限制，可為使聚胺基甲酸酯樹脂固著於前述纖維基材後進行染色的先浸漬後染色方法，亦可為對前述纖維基材進行染色後使聚胺基甲酸酯樹脂固著的後含浸先染色法。 另外，本發明的皮革用材料亦可形成表皮層而製成帶銀面的皮革用材料。作為形成如此的表皮層的方法，可為以往公知的任意的方法，沒有特別限制，例如可列舉：在脫模紙上塗布表皮層用材料，使表皮用材料的水分蒸發而形成表皮層之後，在表皮層的表面塗布接著劑，使其與本發明的皮革用材料貼合，使接著劑的水分蒸發而貼合的方法；或在使水分蒸發而形成接著劑層之後使兩者貼合的方法(脫模紙轉印法)。另外，還可列舉：在脫模紙上形成表皮層後，利用熱使表皮層與本發明的皮革用材料貼合的熱轉印法；在本發明的皮革用材料上直接噴霧表皮層用材料的噴霧法；利用凹版塗布機、刮刀塗布機、逗號塗布機、氣刀塗布機等在本發明的皮革用材料上塗布表皮層用材料的直接塗布法等。在形成如此的表皮層的方法中，從所得到的表皮層的摩擦牢度等物性進一步提高這般的觀點看來，較佳脫模紙轉印法。前述脫模紙轉印法中所使用的表皮層用材料及接著劑只要是可與本發明的皮革用材料貼合的，就沒有特別限制，從可進一步保持纖維基材的厚度，得到更優異的質感及摩擦牢度等物性這般的觀點考慮，較佳聚胺基甲酸酯樹脂，另外，從不產生VOC及降低環境負荷這般的觀點考慮，較佳水性或無溶劑系的物質。 本發明的皮革用材料可用於車輛、傢俱、衣物、鞋、包、袋狀物、涼鞋、雜貨、研磨等領域。 [實施例] 以下，基於實施例及比較例對本發明進行更具體地說明，但本發明並不限定於以下的實施例。另外，各合成例、實施例及比較例中的各測定及評估分別按照以下的方法進行。 (1)熱敏凝固溫度測定 將各聚胺基甲酸酯樹脂合成例中得到的水性聚胺基甲酸酯樹脂的水乳化分散物以及各實施例及比較例中得到的混合液5.0g放入20mL的玻璃制試管中，將各試管在水浴中靜置，對水浴以1℃/分鐘進行升溫，測定內容物喪失流動性而凝固時的溫度並作為熱敏凝固溫度。 (2)100%模量的值測定 使用各聚胺基甲酸酯樹脂合成例中得到的水性聚胺基甲酸酯樹脂的水乳化分散物，按照與JIS K 6250(2006)的8.試驗片的採集．製作相同的方法製作啞鈴狀3號形狀的試驗片，按照與JIS K 6251(2010)相同的方法測定標距長度伸長100%時(伸長至2倍時)的規定伸長拉伸應力(MPa)的值並作為100%模量的值。 (3)黏度測定 使用單圓筒型旋轉黏度計(B型黏度計)，按照基於JIS K7117-1(1999)的方法測定個實施例及比較例中得到之混合液之25℃下之黏度[mPa・s]。 (4)柔軟度(softness)測定 對於於各實施例及個比較例所得到之染色加工後皮革用材料，按照ISO 17235：2015(IULTCS/IUP 36)，使用柔軟度測試儀(皮革柔軟度測量裝置ST300：英國、MSA ENGINEERING SYSTEMS LTD.製造)，測定柔軟度(softness、硬挺度)[mm]。另外，硬挺度的數值表示侵入深度，數值越大則表示越柔軟。 (5)質感評估 對於由各實施例及各比較例所得到的染色加工後皮革用材料，藉由觸感按照以下的基準進行評估。 5級：柔軟且極富回彈性的質感 4級：柔軟且富有回彈性的質感 3級：柔軟但略微欠缺回彈性的質感 2級：略微粗硬且紙質感的(紙那樣的)質感 1級：粗硬且紙質感的(紙那樣的)質感 (水性聚胺基甲酸酯樹脂的合成例1) 向裝有攪拌機、迴流冷卻管、溫度計，及氮導入管的四口燒瓶中加入聚丁二醇(重量平均分子量1,000)167.9g、環氧乙烷及環氧丙烷的無規共聚加聚物(重量平均分子量1,000、氧化乙烯基含量70質量%)36.9g、1,4-丁二醇3.2g、三羥甲基丙烷4.0g、二月桂酸二丁基錫0.002g及甲乙酮128.6g，均勻混合後，加入二環己基甲烷二異氰酸酯88.0g，在80℃下反應300分鐘，得到遊離異氰酸酯基的含量為1.0質量%的異氰酸酯基封端預聚物的甲乙酮溶液。 將所得到的前述異氰酸酯基封端預聚物的甲乙酮溶液冷卻至30℃以下後，添加磷酸癸酯0.5g及三苯乙烯基苯酚的環氧乙烷20莫耳加成物12.0g，均勻混合後，使用分散機葉片，緩慢加入水435.0g，進行轉相乳化、分散，得到乳化分散液。然後，將呱嗪6水合物3.9g與二亞乙基三胺2.1g溶解在水23.9g中，將所得到的多胺水溶液添加至前述乳化分散液中，進行90分鐘鏈增長反應後，在減壓下以35℃進行脫溶劑，得到不揮發成分40.0質量%、黏度250.0 mPa・s(BM黏度計、2號轉子、60rpm)、平均粒子徑550nm的穩定的水性聚胺基甲酸酯樹脂的水乳化分散物。 該水性聚胺基甲酸酯樹脂中的羧基、羧酸酯基、磺基，及磺酸酯基的含量均為0.0質量%，100%模量的值為2MPa。另外，該水性聚胺基甲酸酯樹脂的水乳化分散物在65℃時發生凝膠化，具有熱敏凝固性。 (水性聚胺基甲酸酯樹脂的合成例2) 向裝有攪拌機、迴流冷卻管、溫度計，及氮導入管的四口燒瓶中加入1,6-己二醇聚碳酸酯多元醇(平均分子量2,000)157.0g、新戊二醇7.5g、三羥甲基丙烷1.3g、2,2-二羥甲基丙酸9.5g、二月桂酸二丁基錫0.001g及甲乙酮105g，均勻混合後，加入異佛爾酮二異氰酸酯69.7g，在80℃下反應300分鐘，得到遊離異氰酸酯基相對於不揮發成分的含量為1.9質量%的具有羧基的異氰酸酯基封端預聚物的甲乙酮溶液。 將所得到的前述異氰酸酯基封端預聚物的甲乙酮溶液冷卻至50℃以下後，加入三乙胺6.8g，在40℃下進行30分鐘中和反應。接著，將進行過中和的溶液冷卻至30℃以下，使用分散機葉片，緩慢加入水421.9g，使具有羧基的異氰酸酯基封端預聚物的中和物乳化分散，得到分散液。然後，將60質量%的水合肼5.2g與二亞乙基三胺1.1g溶解在水20g中，將所得到的多胺水溶液添加至前述分散液中，在35℃下進行60分鐘鏈增長反應後，在減壓下以35℃進行脫溶劑，得到不揮發成分35.0質量%、黏度120mPa・s(BM黏度計、2號轉子、60rpm)、pH值7.8、平均粒子徑90nm的穩定的具有羧基及羧酸酯基的水性聚胺基甲酸酯樹脂的水分散物。 該水性聚胺基甲酸酯樹脂中的羧基含量與羧酸酯基含量的合計為1.3質量%，100%模量的值為2MPa。另外，該具有羧基及羧酸酯基的聚胺基甲酸酯樹脂的水乳化分散物即使在90℃加熱也不凝膠化，沒有熱敏凝固性。 (實施例1) 將水性聚胺基甲酸酯樹脂的合成例1中得到的(A)水性聚胺基甲酸酯樹脂的水乳化分散物65質量份(固體成分26質量份)、(B)碳酸氫鈉8%水溶液16質量份(固體成分(碳酸氫鈉)1.3質量份)、(C)甲酸乙二醇酯1質量份、(D)水18質量份均勻混合，調製水性聚胺基甲酸酯樹脂濃度為26質量%的混合液。所得到之混合液之熱敏凝固溫度為60℃，25℃之黏度為40mPa・s。 使用狹縫軋液機，使該混合液含浸於未加工布(由聚酯纖維構成的無紡布、0.5dtex、密度0.3g/cm3 )，以滲入量成為100質量%的方式進行含漬，之後，以相對濕度60%、溫度100℃進行濕式乾燥(濕熱凝固)5分鐘，接著，以130℃進行乾熱乾燥5分鐘，得到人工皮革(皮革用材料)。然後，對所得的人工皮革在下述條件下進行染色及RC皂洗，得到人工皮革染色加工布(染色加工後的皮革用材料)。 ＜染色條件＞ 染色機：MINI COLOR染色機((股)TEXAM技研製造) 染料：Kayalon Microester Blue DX-LS conc(日本化藥(股)製造)　　0.10%o.w.f. Kayalon Maicroester Yellow DX-LS(日本化藥(股)製造)　　2.00%o.w.f. Kayalon Maicroester Red DX-LS(日本化藥(股)製造)　　0.80%o.w.f. 染色助劑：NICCA SUNSOLT RM-3406(日華化學(股)製造)0.5g/L pH調節劑：90%質量乙酸　0.3cc/L 浴比：(1:20) 染色條件：130℃×60分鐘(升溫速度2℃/分鐘)。 ＜RC條件＞ RC浴：氫氧化鈉　2g/L 亞硫酸鹽(hydrosulfite)　2g/L 浴比：(1:20) RC條件：80℃×20分鐘(升溫速度2℃/分鐘)。 對所得到的人工皮革染色加工布(染色加工後皮革用材料)進行柔軟度測定及質感評估，將所得到的結果與混合液的組成及黏度一起示於下述的表1。 (實施例2~6) 除了使混合液的組成分別成為下述的表1所示的組成以外，與實施例1同樣地操作，得到人工皮革(皮革用材料)及人工皮革染色加工布(染色加工後皮革用材料)。對所得到的人工皮革染色加工布(染色加工後皮革用材料)進行柔軟度測定及質感評估，將所得到的結果與混合液的組成與黏度一起分別示於下述的表1。另外，表中的水一欄所記載的質量份表示形成各分散物或水溶液所混合的水以外加入的水的量(以下相同)。

Figure 02_image001
(實施例7~13) 除了使混合液的組成分別為下述的表2所示的組成以外，與實施例1同樣地操作，分別得到人工皮革(皮革用材料)及人工皮革染色加工布(染色加工後皮革用材料)。對所得到的人工皮革染色加工布(染色加工後皮革用材料)進行柔軟度測定及質感評估，將所得到的結果與混合液的組成及黏度一起分別示於下述的表2。
Figure 02_image003
(比較例1~5) 除了使混合液的組成分別為下述的表3所示的組成以外，與實施例1同樣地操作，分別得到人工皮革(皮革用材料)及人工皮革染色加工布(染色加工後皮革用材料)。對所得到的人工皮革染色加工布(染色加工後皮革用材料)進行柔軟度測定及質感評估，將所得到的結果與混合液的組成及黏度一起分別示於下述的表3。另外，在比較例4中，在調製混合液時發生了發泡，無法對纖維基材實施處理。
Figure 02_image005
如表1~3所示的結果可知，在實施例1~13中得到的皮革用材料中，確認了柔軟的質感優異，確認了利用本發明的皮革用材料的製造方法可容易且高效地得到柔軟的質感優異的皮革用材料。另外，使用進一步含有(E)增黏劑及/或(F)熱敏膠凝劑的混合液時(例如實施例3~6、8~13)，確認了可得到具有更柔軟的質感的皮革用材料。 另一方面，使用(B)發泡劑及(C)甲酸酯化合物中的任1種都不含有的混合液時(例如比較例1、2)，在所得到的皮革用材料中，確認了柔軟的質感差。另外，即使在使用含有作為藉由加熱產生酸的物質的硫酸銨來代替本發明所關於之(C)甲酸酯化合物的混合液時(例如比較例3、5)，在所得到的皮革用材料中，亦確認了柔軟的質感差，另外，使用含有檸檬酸的混合液時(例如比較例4)，在調製混合液時發生了發泡，無法對纖維基材實施處理。 [產業上的可利用性] 如以上所說明的那般，根據本發明，可提供一種可相比以往更容易且高效地得到柔軟的質感優異的皮革用材料的皮革用材料的製造方法。 另外，根據本發明，可在無紡布等的纖維基材內高效且容易地形成多孔化的樹脂層，因此，除了抑制使纖維集束、固定化而損害質感以外，亦可利用樹脂層填充前述纖維基材內的空隙，因此，亦可期待回彈感的提高及人工皮革的物理強度(拉伸強度、撕裂強度、耐彎曲性)的提高。因此，本發明的皮革用材料的製造方法作為皮革用材料的工業製造方法為特別有用的，另外，利用本發明的製造方法得到的皮革用材料可在車輛、傢俱、衣物、包、鞋、袋狀物、雜貨、研磨等產業領域中合適地利用，進而亦可作為設置表皮層、穩定且高質量的皮革用材料合適地利用。Hereinafter, the present invention will be described in detail based on its preferred embodiments. The manufacturing method of the leather material of the present invention is characterized by containing (A) an aqueous polyurethane resin, (B) a foaming agent that generates carbon dioxide by heating and/or acid, and (C) a formate The mixture of the compound and (D) water is impregnated into the fiber base material, and then heated and dried to obtain a leather material. (A) Water-based polyurethane resin As the (A) water-based polyurethane resin of the present invention, it is preferably selected from self-emulsifying water-based polyurethane having hydrophilic functional groups At least one of the group consisting of resin and forced emulsification type water-based polyurethane resin. <Self-emulsifying type aqueous polyurethane resin> In the present invention, the self-emulsifying type aqueous polyurethane resin is an aqueous polyurethane resin having an anionic group in the resin skeleton. In the present invention, as the aforementioned self-emulsifying water-based polyurethane resin, it is preferable to leave a water-emulsified dispersion liquid having a water concentration of 40% by mass of the polyurethane resin at 20°C. No separation or sedimentation of polyurethane resin was observed for a few hours. As said anionic group, a carboxyl group, a carboxylate group, a sulfo group, a sulfonate group, etc. are mentioned. As the self-emulsifying water-based polyurethane resin according to the present invention, it is preferable to have a carboxyl group, a carboxylate group, and a sulfo group from the general viewpoint that it tends to be excellent in emulsion dispersion stability. And a polyurethane resin having at least one anionic group in the group consisting of a sulfonate group, more preferably a polyurethane resin having a carboxyl group and/or a carboxylate group or having Sulfonate and/or sulfonate based polyurethane resin. As content of the anionic group in the said self-emulsifying type aqueous polyurethane resin, 0.1-5.0 mass% is preferable, and 0.2-2.5 mass% is more preferable. In addition, (i) when the self-emulsifying water-based polyurethane resin of the present invention has a carboxyl group and/or carboxylate group, the total content of the carboxyl group and carboxylate group is more preferably 0.5 to 4.0 mass %, more preferably 0.7 to 2.5% by mass. In addition, (ii) when the self-emulsifying water-based polyurethane resin of the present invention has a sulfo group and/or sulfonate group, the total content of the sulfonate group and the sulfonate group is more preferably 0.1~ 1.0% by mass, more preferably 0.2 to 1.0% by mass. In addition, (iii) when the self-emulsifying water-based polyurethane resin of the present invention has a carboxyl group and/or a carboxylate group and a sulfo group and/or a sulfonate group, a carboxyl group and a carboxyl group are particularly preferred. The total content of acid ester groups is 0.1 to 4.0% by mass, and the total content of sulfo groups and sulfonate groups is 0.1 to 1.0% by mass. When the content of the aforementioned anionic group is less than the aforementioned lower limit, the storage stability of the aqueous dispersion of the self-emulsifying water-based polyurethane resin tends to deteriorate; on the other hand, when the aforementioned upper limit is exceeded, the resulting mixture The heat-sensitive coagulation temperature of the leather becomes higher, and the migration (a phenomenon in which the water-based polyurethane resin moves to the surface of the fiber substrate) of the leather material tends to decrease. In addition, in the present invention, the value of the 100% modulus of the self-emulsifying water-based polyurethane resin is preferably 0.5 to 25 MPa, and more preferably 1 to 20 MPa. When the value of 100% modulus is less than the aforementioned lower limit, although a soft texture leather material can be obtained, the abrasion resistance tends to decrease; on the other hand, when the aforementioned upper limit is exceeded, the texture of the obtained leather material becomes hard , There is a tendency for fluffing or fiber shedding. In addition, in the present invention, the value of 100% modulus is measured using a dumbbell-shaped No. 3 test piece as in JIS K 6251 (2010). The gauge length is obtained when the gauge length is extended by 100% (when extended to twice ) Specifies the value of elongation tensile stress (MPa). As such a self-emulsifying water-based polyurethane resin, it is preferable to use, for example, (a) organic polyisocyanate, (b) polyol, and (c) a compound having a carboxyl group and two or more active hydrogens. Reaction, the resulting neutralized isocyanate group-terminated prepolymer having carboxylate groups is emulsified and dispersed in water by self-emulsification, using (d) having two or more amine groups and/or imine groups Polyamine compound, a polyurethane resin having a carboxyl group and/or carboxylate group obtained by causing a chain extension reaction; and/or (II) using (a) organic polyisocyanate, (b) polyol , And (e) a polyamine compound having two or more amine groups and/or imine groups and a sulfo group and/or sulfonate group is reacted to block the resulting isocyanate group having a sulfonate group The prepolymer neutralized product is emulsified and dispersed in water by self-emulsification, and (d) a polyamine compound having two or more amine groups and/or imine groups is used to cause chain extension reaction to obtain a sulfo group And/or sulfonate-based polyurethane resin. Hereinafter, as a manufacturing method of the aforementioned self-emulsifying water-based polyurethane resin, these resins will be cited as examples for description. (I) Polyurethane resins having carboxyl groups and/or carboxylate groups (a) Organic polyisocyanates are not particularly limited as organic polyisocyanates, and aliphatic polyisocyanates having two or more isocyanate groups can be used, Alicyclic polyisocyanate, and aromatic polyisocyanate. Examples of such organic polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate Alicyclic diisocyanate compounds such as cyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane; toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate , Toluidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and other aromatic diisocyanate compounds. These polyisocyanate compounds may be used individually by 1 type, and may be used in combination of 2 or more types. Among such organic polyisocyanates, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds impart non-yellowing properties to leather materials, so they can be preferably used, and hexamethylene diisocyanate and isophor are particularly preferably used. Ketone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. (b) Polyol As a polyol, there are no particular restrictions as long as it is a polyol having two or more hydroxyl groups (except for the following (c) compounds having a carboxyl group and two or more active hydrogen), except for polyols. In addition to ester polyols, polycarbonate polyols, polyether polyols, etc., polyether ester polyols, silicone polyols, and fluorine polyols having ether bonds and ester bonds may also be used. Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, and polyethylene adipate diol. , Polyhexamethylene isophthalate adipate diol, polyethylene succinate diol (polyethylene succinate diol), polybutylene succinate diol, poly sebacic acid Ethylene glycol ester diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-pentylene) adipate diol, Polycondensate of 1,6-hexanediol and dimer acid, copolycondensate of 1,6-hexanediol and adipic acid and dimer acid, polycondensate of nonanediol and dimer acid, ethylene glycol and Copolycondensate of adipic acid and dimer acid, etc. Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly 1,4-cyclohexane dimethyl carbonate diol, 1, 6-hexanediol polycarbonate polyol, etc. Examples of the aforementioned polyether polyol include: homopolymerization of alkylene oxides with 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, oxetane, and oxolane. Dihydric alcohol of addition polymer or copolymerization addition polymer; a polyol formed by random addition or block addition of the aforementioned alkylene oxides with carbon number 2 to 4 to polyols such as glycerol and trimethylolpropane . Examples of the aforementioned organosilicon polyol include compounds in which two or more hydroxyl groups and/or organic groups having hydroxyl groups are introduced into the end and/or side chain of dimethylpolysiloxane, such as methanol-modified silicone oil , Polyether modified silicone oil, silanol terminated silicone oil. Examples of the fluorine polyol include polyols containing fluorine in the molecule, such as Zeffle GK510, GK570 (manufactured by Daikin Industry Co., Ltd. above), LUMIFLON LF200, and LF400 (manufactured by Asahi Whistle Co., Ltd. above). These polyols may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, the weight average molecular weight of such a polyol is preferably 500 to 5,000, and more preferably 1,000 to 3,000. In addition, from the viewpoint that the obtained polyurethane resin can impart sufficient durability to leather materials, it is preferable to use polycarbonate polyol and/or polyether polyol as the aforementioned polyol. alcohol. In addition, from the viewpoint that there is a tendency to further improve the texture of the obtained leather material, it is preferable to use an organosilicon polyol and/or a fluorine polyol. (c) A compound having a carboxyl group and two or more active hydrogens As a compound having a carboxyl group and two or more active hydrogens, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutane acid. In addition, as such a compound, a polyester polyol having a pendant carboxyl group obtained by reacting a diol having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or the like can also be used. In addition, such a compound having a carboxyl group and two or more active hydrogens may be used alone or in combination of two or more kinds. (d) Polyamine compound having two or more amine groups and/or imine groups As the polyamine compound having two or more amine groups and/or imine groups, for example, ethylene diamine and propylene diamine can be cited , Tetramethylene diamine, hexamethylene diamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methyl piperazine, isophorone diamine, norbornane diamine, diamino group Diphenylmethane, toluene diamine, xylene diamine and other diamines; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminodipropylamine, tris(2-aminoethyl) ) Polyamines such as amines; amide amines derived from diprimary amines and monocarboxylic acids; water-soluble amine derivatives such as monoketimines of diprimary amines; dihydrazine oxalate, dihydrazine malonate, and dibasic succinate Dihydrazine, dihydrazine glutarate, dihydrazide adipic acid, dihydrazine sebacate, dihydrazine maleate, dihydrazine fumarate, dihydrazine itaconic acid, 1,1'- Hydrazine derivatives such as ethylene hydrazine, 1,1'-trimethylene hydrazine, and 1,1'-(1,4-butylene) dihydrazine. These polyamine compounds having two or more amine groups and/or imine groups may be used alone or in combination of two or more kinds. The aforementioned (I) polyurethane resin having a carboxyl group and/or a carboxylate group can be neutralized by an isocyanate group-terminated prepolymer having a carboxylate group (hereinafter, referred to as "CA Isocyanate group-terminated prepolymer neutralized product") is obtained by forming an emulsified dispersion of the polyurethane resin by emulsifying and dispersing from self-emulsification to water and a chain extension reaction. Carboxy preceding CA isocyanate group-terminated prepolymer and a composition having the compound from the preceding (c) having a carboxyl group with two or more active hydrogens are neutralized from carboxylic acid ester group (-COO -) isocyanate groups The blocked prepolymer neutralized product is obtained by reacting the aforementioned (a) organic polyisocyanate, the aforementioned (b) polyol, and the aforementioned (c) a compound having a carboxyl group and two or more active hydrogens. The specific method for obtaining such a CA isocyanate group-terminated prepolymer neutralized product is not particularly limited. For example, it can be produced by a conventionally known one-stage so-called one-step method, a multi-stage isocyanate addition polymerization method, or the like. The reaction temperature at this time is preferably 40 to 150°C. In addition, during such a reaction, a low-molecular-weight chain extender having two or more active hydrogen atoms can be used as needed. As the aforementioned low molecular weight chain extender, the molecular weight is preferably 400 or less, particularly preferably 300 or less. In addition, examples of the aforementioned low molecular weight chain extenders include ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Low molecular weight polyols such as sugar alcohols; ethylene diamine, propylene diamine, hexamethylene diamine, diaminocyclohexyl methane, piperazine, 2-methyl piperazine, isophorone diamine, diethylene Low molecular weight polyamines such as triamine and triethylenetetramine. In addition, as the low molecular weight chain extender, one type may be used alone, or two or more types may be used in combination. In addition, during the above reaction, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin 2-ethylhexanoate, triethylamine, triethylenediamine, and N-methylmorpholine may be added as needed. In addition, an organic solvent that does not react with the isocyanate group may be added during the reaction or after the completion of the reaction. As said organic solvent, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, methyl isobutyl ketone, etc. are mentioned, for example. The neutralization of the carboxyl group derived from the compound having a carboxyl group and two or more active hydrogens described above may be performed simultaneously with the preparation of the isocyanate group-terminated prepolymer, or may be performed before or after the preparation. Such neutralization can be carried out appropriately using a known method, and the compound used for such neutralization is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and N-methyl- Diethanolamine, N,N-dimethylmonoethanolamine, N,N-diethylmonoethanolamine, triethanolamine and other amines; potassium hydroxide; sodium hydroxide; amines, etc. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, and tributylamine are particularly preferred. The method for emulsifying and dispersing the neutralized CA isocyanate group-terminated prepolymer into water is not particularly limited, and examples thereof include methods using emulsifying equipment such as a homomixer, homogenizer, and disperser. In addition, when emulsifying and dispersing the aforementioned neutralized CA isocyanate group-terminated prepolymer in water, it is preferable not to use an emulsifier in particular, and to self-emulsify the prepolymer in the temperature range of room temperature to 40°C. The neutralized product is emulsified and dispersed in water to suppress the reaction of isocyanate groups with water as much as possible. In addition, when emulsifying and dispersing in this way, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid, and benzyl chloride may be added as necessary. The chain extension reaction of the aforementioned neutralized CA isocyanate group-terminated prepolymer can be achieved by adding the aforementioned (d) amine group and/or imine having more than two amine groups to the aforementioned neutralized CA isocyanate group-terminated prepolymer. Or by adding the aforementioned CA isocyanate group-terminated prepolymer neutralized product to the aforementioned (d) polyamine compound having two or more amine groups and/or imine groups. Such chain extension reaction is preferably carried out at a reaction temperature of 20-40°C, and is usually completed within 30-120 minutes. In the aforementioned (I) method for producing a polyurethane resin having a carboxyl group and/or a carboxylate group, the aforementioned emulsification and dispersion and the aforementioned chain extension reaction may be performed simultaneously, or the CA isocyanate group may be blocked beforehand. After the polymer neutralized product is emulsified and dispersed, it undergoes a chain extension reaction, or it can be emulsified and dispersed after the chain extension reaction. When the neutralized CA isocyanate group-terminated prepolymer is produced, when the aforementioned organic solvent is used, it is preferable to remove the organic solvent by vacuum distillation or the like after chain extension reaction or emulsification dispersion, for example. (II) Polyurethane resin with sulfo group and/or sulfonate group is used to manufacture (II) (a) Organic of polyurethane resin with sulfo group and/or sulfonate group Examples of polyisocyanates, (b) polyols, and (d) polyamine compounds having two or more amine groups and/or imine groups include those having a carboxyl group and/or carboxylate group as described in (I) The compound mentioned in the manufacture of the formate resin is the same compound. (e) A polyamine compound having two or more amine groups and/or imino groups and having sulfo groups and/or sulfonate groups as having two or more amine groups and/or imino groups and having sulfo groups and The polyamine compound of/or sulfonate group may have two or more amine groups and/or imino groups and sulfonate groups and/or sulfonate groups. For example, 2-(2-aminoethyl Amino)-sodium ethane sulfonate, sodium 2-(3-aminopropylamino)-ethane sulfonate, sodium 2,4-diaminobenzene sulfonate, etc. These compounds may be used individually by 1 type, and may be used in combination of 2 or more types. The aforementioned (II) polyurethane resin having sulfonate groups and/or sulfonate groups can be neutralized by isocyanate group-terminated prepolymers having sulfonate groups (hereinafter, referred to as " SU isocyanate group-terminated prepolymer neutralized product") is obtained by forming an emulsified dispersion of the polyurethane resin by emulsification and dispersion from self-emulsification to water and a chain extension reaction. The aforementioned neutralized SU isocyanate group-terminated prepolymer is a sulfo group derived from a polyamine compound having two or more amine groups and/or imino groups and having a sulfo group and/or sulfonate group in the aforementioned (e) neutralized sulfonate group (-SO 3 -) obtained by the isocyanate group-terminated prepolymer was neutralized, and the can (a) an organic polyisocyanate, the (b) a polyol and (e) the It is obtained by reacting a polyamine compound having two or more amine groups and/or imino groups and having a sulfo group and/or sulfonate group. The specific method for obtaining such a neutralized product of the SU isocyanate group-terminated prepolymer is not particularly limited, except for using (e) the aforementioned having two or more amine groups and/or imino groups and having sulfo groups. And/or the polyamine compound of a sulfonate group instead of the compound having a carboxyl group and two or more active hydrogens in the above (c), and the same method as the neutralized CA isocyanate group-terminated prepolymer. In addition, a method of emulsifying and dispersing the neutralized SU isocyanate group-terminated prepolymer and causing a chain extension reaction to obtain the aforementioned (II) polyurethane resin having a sulfo group and/or sulfonate group may also be used. In addition to using the aforementioned neutralized SU isocyanate group-terminated prepolymer instead of the aforementioned neutralized CA isocyanate group-terminated prepolymer, a polyurethane having a carboxyl group and/or carboxylate group with the aforementioned (I) The method is the same as the method described in the manufacturing method of the acid ester resin. The aforementioned self-emulsifying water-based polyurethane resin is usually obtained in the form of a water-emulsified dispersion of the resin, is already distributed in the market, and can be suitably used. As the aforementioned self-emulsifying water-based polyurethane resin, it is preferable to use it in a state of being emulsified and dispersed in water. The concentration is not particularly limited, but it can be easily obtained in a uniform state if it is considered. The tendency of liquid, and the fixing amount of the resin component to the fiber base material is preferably 15-60% by mass. In addition, in the present invention, when a self-emulsifying type water-based polyurethane resin and the following forced emulsification type water-based polyurethane resin are used in a state of being emulsified and dispersed in water, (A) water-based polyurethane The mass of the formate resin (in the case of a mixture of two or more water-based polyurethane resins, the total mass of the same) refers to the water emulsified dispersion of the water-based polyurethane resin at a temperature The mass of the remaining part (solid content, non-volatile content) when heated at 105°C for 3 hours. (Forced emulsification type water-based polyurethane resin) In the present invention, the aforementioned forced emulsification type water-based polyurethane resin does not have the aforementioned anionic groups (sulfo group, sulfonate group, carboxyl group, carboxylic acid Ester group, etc.), does not have self-emulsifying properties. In order to emulsify in water, it is necessary to add an emulsifier (in the present invention, a surfactant is included), and the aforementioned emulsifier can be used to force emulsification (forced emulsification type) ) Of water-based polyurethane resin. In the present invention, as the aforementioned forced emulsification type water-based polyurethane resin, a polyurethane resin is preferably used such that the concentration of the polyurethane resin in water becomes 40% by mass , The aforementioned emulsifier was suitably used and forced to emulsify to obtain a water-emulsified dispersion. Even if the water-emulsified dispersion was allowed to stand at 20°C for 12 hours, no separation or sedimentation was observed. As such a forced emulsification type water-based polyurethane resin, for example, it is preferable to use: (III) The aforementioned (a) organic polyisocyanate and the aforementioned (b) polyol are reacted, and the obtained isocyanate group is blocked and prepolymerized. A polyurethane resin obtained by emulsifying and dispersing in water in the presence of an emulsifier, and using the aforementioned (d) polyamine compound having two or more amine groups and/or imine groups to carry out a chain extension reaction. Hereinafter, as a manufacturing method of the aforementioned forced emulsification type aqueous polyurethane resin, such a resin will be cited as an example for description. When preparing the aforementioned forced emulsification type aqueous polyurethane resin, first, the aforementioned (a) organic polyisocyanate and the aforementioned (b) polyol are reacted to prepare an isocyanate group-terminated prepolymer. The method for preparing such an isocyanate group-terminated prepolymer is not particularly limited, except that the aforementioned (c) compound having a carboxyl group and two or more active hydrogens or the aforementioned (e) having two or more amine groups are not used. And/or imino group and polyamine compound with sulfo group and/or sulfonate group, and does not need carboxyl or sulfo group neutralization, can be used and used to obtain the aforementioned CA isocyanate group-terminated prepolymer The method of the neutralized product or SU isocyanate group-terminated prepolymer neutralized product is the same method. When preparing the aforementioned forced emulsification type water-based polyurethane resin, next, the obtained isocyanate group-terminated prepolymer is emulsified and dispersed to cause a chain extension reaction to obtain a forced emulsification type water-based polyurethane resin. The method of emulsification and dispersion of such isocyanate group-terminated prepolymer and chain extension reaction is not particularly limited, except that the aforementioned isocyanate group-terminated prepolymer is used instead of the aforementioned CA isocyanate group-terminated prepolymer neutralized product or In addition to the neutralized SU isocyanate group-terminated prepolymer and using the emulsifier for emulsification and dispersion, the same method as the method described in the method for producing the self-emulsifying aqueous polyurethane resin can be adopted. That is, as long as the aforementioned urethane prepolymer having an isocyanate group at the end is used instead of the aforementioned CA isocyanate group-terminated prepolymer neutralized product or SU isocyanate group-terminated prepolymer neutralized product, and the aforementioned When the isocyanate group-terminated prepolymer is emulsified and dispersed in water, an emulsifier can be used to carry out emulsification and dispersion at the same time as the chain extension reaction. As the method of emulsification and dispersion in water or the chain extension reaction, it can be used separately with the aforementioned self-emulsifying aqueous polymer The method similar to the emulsification dispersion method or the chain extension reaction described in the manufacturing method of the urethane resin. When preparing the aforementioned forced emulsification type aqueous polyurethane resin, examples of the aforementioned emulsifier include nonionic surfactants and cationic surfactants. As the aforementioned nonionic surfactants, for example, polyoxyethylene stilbene phenyl ether type nonionic surfactants, polyoxyethylene propylene stilbene phenyl ether type nonionic surfactants, polyoxyethylene three Styryl phenyl ether type nonionic surfactant, polyoxyethylene propylene tristyryl phenyl ether type nonionic surfactant, Pluronic type nonionic surfactant. In addition, as the aforementioned anionic surfactants, for example, higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, polyalkylene glycol sulfate ester salts, polyoxyalkylene aryl ether sulfate ester salts, polyoxyalkylene aromatic Sulfated oil, sulfated fatty acid ester, alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate and its polymer, paraffin sulfonate, dialkyl sulfosuccinic acid Salt, polystyrene sulfonate, lignosulfonate, alkyl ether phosphate salt. As the aforementioned emulsifier, one of these can be used alone, or two or more of them can be used in combination. Preferably, at least one of the aforementioned nonionic surfactants is used. Among them, from the forced emulsification type aqueous polyurethane From the viewpoint of storage stability and processing stability of the aqueous dispersion of the acid ester resin, it is preferable to use a compound having an HLB of 7 to 16. In addition, in the present invention, the value of HLB is a value obtained by the following formula. The molecular weight of the oxyethylene moiety in the nonionic surfactant×20/the molecular weight of the nonionic surfactant is used as the addition amount of the aforementioned emulsifier, according to the polyoxyethylene content of the isocyanate group-terminated prepolymer as the emulsified product The resulting hydrophilicity is different and cannot be generalized. It is preferably 0.5 to 10 parts by mass, and more preferably 1 to 6 parts by mass relative to 100 parts by mass of the aforementioned isocyanate group-terminated prepolymer. When the addition amount of such an emulsifier is less than the aforementioned lower limit, it tends to be difficult to obtain a sufficiently stable emulsified dispersion state. On the other hand, when the aforementioned upper limit is exceeded, the water resistance of the obtained foam structure tends to decrease. The aforementioned forced emulsification type waterborne polyurethane resin can be emulsified and dispersed in water by isocyanate group-terminated prepolymer in the presence of an emulsifier and chain extension reaction to form an emulsified dispersion of the polyurethane resin From things. As such a forced emulsification type waterborne polyurethane resin, it is preferably used in a state of being emulsified and dispersed in water, and its concentration is not particularly limited, but it can be easily obtained in a uniform state if considered. The tendency of the mixed liquid, and the amount of the resin component fixed to the fiber base material is preferably 15-60% by mass. (B) Foaming agent The (B) foaming agent related to the present invention is a foaming agent that generates carbon dioxide by heating, or by acid, or by heating and acid (by heating and/or acid). As the (B) foaming agent related to the present invention, a thermal decomposition type chemical foaming agent is preferred, and a carbonate is more preferred. As the aforementioned (B) foaming agent, one type may be used alone, or two or more types may be used in combination. Among them, from the viewpoint of the processing stability of the mixed solution, it is preferably selected from sodium carbonate, potassium carbonate, and carbonic acid. At least one carbonate in the group consisting of ammonium, sodium bicarbonate (sodium bicarbonate), potassium bicarbonate, and ammonium bicarbonate (ammonium bicarbonate). In the present invention, the aforementioned (B) foaming agent can be used directly in a solid (powder) state, but from the viewpoint of maintaining the stability of the aforementioned (A) aqueous polyurethane resin emulsion dispersion Now, it is preferable that the aforementioned (B) foaming agent is contained in water and used in the state of an aqueous solution. The concentration of the aqueous solution of the aforementioned (B) foaming agent is not particularly limited, and may be about 1 to 50% by mass. (C) Formate Compound The (C) Formate Compound referred to in the present invention is a formate of a hydroxy compound. Examples of the aforementioned hydroxy compounds include lower alcohols with 1 to 4 carbon atoms, mono- or polyalkylene glycols, trimethylolpropane, mono- or polyglycerols, etc., and one of these may be used alone, or Use 2 or more in combination. Among them, as the aforementioned hydroxy compound, from the viewpoint of the flexibility of the leather material obtained, mono- or polyalkylene glycol is preferred, and ethylene glycol, diethylene glycol, triethylene glycol is more preferred. Ethylene glycol and polyethylene glycol having a degree of polymerization of 3 to 10 are more preferably ethylene glycol. In addition, as the (C) formate compound related to the present invention, orthoformates such as trimethyl orthoformate (trimethyl orthoformate) and triethyl orthoformate can be used. As these formate compounds, one type may be used alone, or two or more types may be used in combination. (D) Water The (D) water referred to in the present invention is composed of the aforementioned (A) aqueous polyurethane resin, the aforementioned (B) foaming agent, the aforementioned (C) formate compound, and the following as required When mixing the components, it acts as a solvent, and ion-exchanged water or distilled water is preferably used. In addition, as such (D) water, for example, when an emulsified dispersion obtained by emulsifying and dispersing the aforementioned (A) aqueous polyurethane resin in water is used, or when each component is used as an aqueous solution In this case, the water in the emulsified dispersion or the aqueous solution is not distilled off and used as it is, and the water can be used directly as the (D) water in the present invention. (E) Tackifier As the mixed liquid related to the present invention, it is preferable to further contain (E) a tackifier. By further containing the aforementioned (E) tackifier, migration can be suppressed, the thickness of the fiber substrate can be sufficiently maintained, and a softer leather material with excellent texture can be obtained. The aforementioned (E) thickener is not particularly limited, and known thickeners that can be used in aqueous dispersions of aqueous polyurethane resins can be suitably used, and among them, it is preferred to be selected from associative thickeners. And at least one of the group consisting of water-soluble polymer tackifiers. As the aforementioned associative type thickener, for example, Japanese Patent Application Publication No. 54-80349, Japanese Patent Application Publication No. 58-213074, Japanese Patent Application Publication No. 60-49022, Japanese Patent Application Publication No. 52-25840 Urethane-based associative tackifiers described in Bulletin, Japanese Patent Application Publication No. 9-67563, Japanese Patent Application Publication No. 9-71766, etc.; Japanese Patent Application Publication No. 62-292879, Japanese Patent Application Publication No. 62-292879 Associative thickeners obtained by copolymerizing nonionic urethane monomers as associative monomers and other acrylic monomers described in Bulletin 10-121030, etc.; WO9640815, etc. Associative tackifier of amino-based plastic skeleton, etc. Among them, as the aforementioned associative tackifier, an associative tackifier with strong nonionic properties is preferred. The density and strength of the pores in the resulting foamed structure (porous structure) are maintained From the viewpoint of strength, it is more preferable to have an associative tackifier having a polyethylene glycol chain and a urethane bond in the molecular chain. As such an associative thickener, for example, commercially available products such as NEOSTECKER S (manufactured by Nikka Chemical Co., Ltd.) and VISRIZER AP-2 (Sanyo Chemical Industry Co., Ltd.) can be suitably used. Examples of the aforementioned water-soluble polymer thickener include fibers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, and carboxymethyl cellulose. Primer derivatives; soluble starch, carboxymethyl starch, methyl starch and other starch derivatives; sodium alginate, propylene glycol alginate and other alginic acid derivatives; guar gum, carrageenan, galactan, gum arabic, Locust bean gum, quince seed (quince seed), tragacanth, pectin, mannan, starch, xanthan gum, dextran, succinoglycan, curdlan, hyaluronic acid and its Natural polysaccharides such as salt; natural protein such as casein, gelatin, collagen, albumin, etc.; polyalkylene glycol, polyoxyethylene glycol distearate, myristyl polyoxyethylene stearyl ether, Polyoxyethylene sorbitan triisostearate, polyoxyethylene methyl glucose (mono, two or three) laurate, polyoxyethylene methyl glucose (mono, two or three) myristate, poly Oxyethylene methyl glucose (mono, two or three) palmitate, polyoxyethylene methyl glucose (mono, two or three) stearate, polyoxyethylene methyl glucose (mono, two or three) isostearyl Polyoxyalkylene-based nonionic polymers such as acid esters, polyoxyethylene methyl glucose (mono, di, or tri) oleate; vinyl-based polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinyl methyl ether Among them, compounds with strong non-ionic properties are more preferable among them and their mixtures. As such a water-soluble polymer thickener, HEC AX-15 (manufactured by Sumitomo Seiki Co., Ltd., hydroxyethyl cellulose), Kelzan (manufactured by Sanjing Co., Ltd., polymer polysaccharides (yellow) Raw rubber)) and other commercially available products. (F) The heat-sensitive gelling agent, as the mixed liquid related to the present invention, is preferably further contained from the viewpoint of suppressing the shrinkage of the foamed structure during heating and drying and suppressing migration to further soften the texture. (F) Heat-sensitive gelling agent. The heat-sensitive gelling agent (F) is not particularly limited, and a known heat-sensitive gelling agent (in the so-called conventional foam-forming composition containing an aqueous polyurethane resin, Known heat-sensitive gelling agents used for heat-sensitive gelation (heat-sensitive coagulation) of the composition), for example, sodium salts of inorganic acids, ammonium salts of inorganic acids, water-soluble acrylic polymers, etc. One of these may be used alone, or two or more of them may be used in combination. Examples of the inorganic acid in the sodium salt of the aforementioned inorganic acid or the ammonium salt of the inorganic acid include perchloric acid, carbonic acid, sulfuric acid, persulfuric acid, sulfurous acid, phosphoric acid, nitric acid, and the like. Among them, as the aforementioned inorganic acid, sulfuric acid and phosphoric acid are preferred from the viewpoint of excellent migration inhibition effect. As a sodium salt of the said inorganic acid, sodium sulfate (glauber's salt) is mentioned, for example. In addition, as the ammonium salt of the aforementioned inorganic acid, for example, ammonium persulfate, ammonium perchlorate, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, triammonium phosphate, diammonium hydrogen phosphate, Ammonium dihydrogen phosphate, ammonium persulfate, ammonium nitrate, ammonium chloride, etc., can be used alone or in combination of two or more. From the safety of operation, the volatilization problem during drying and after drying From the viewpoint that it can be easily removed by washing with water and there is little residue in the leather material, it is preferable to use at least one selected from the group consisting of ammonium sulfate, diammonium hydrogen phosphate, and ammonium dihydrogen phosphate. In addition, when using ammonium dihydrogen phosphate as the ammonium salt of the aforementioned inorganic acid, it is more preferably used in combination with diammonium phosphate. The aforementioned water-soluble acrylic polymer is not particularly limited, but is preferably the following component (1), the following component (2), the following component (3), the following component (4), and the following component (5) ) At least one of. [Component (1)] A polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and maleic acid, an alkali metal salt of the polymer, and an amine salt of the polymer At least one. [Component (2)] At least one of poly-α-hydroxyacrylic acid, alkali metal salt of poly-α-hydroxyacrylic acid, and amine salt of poly-α-hydroxyacrylic acid. [Component (3)] is selected from acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, methacrylic acid Amine salt, and at least one monomer from the group consisting of amine salt of maleic acid and one selected from the group consisting of poly-α-hydroxy acrylic acid, alkali metal salt of poly-α-hydroxy acrylic acid and poly-α-hydroxy acrylic acid At least one of a polymer obtained by radical polymerization of at least one of the group consisting of an amine salt, an alkali metal salt of the polymer, and an amine salt of the polymer. [Component (4)] is selected from acrylic acid, methacrylic acid, maleic acid, poly-α-hydroxyacrylic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, poly- At least one acrylic in the group consisting of alkali metal salt of α-hydroxy acrylic acid, amine salt of acrylic acid, amine salt of methacrylic acid, amine salt of maleic acid, and amine salt of poly-α-hydroxy acrylic acid Among the polymers obtained by radical polymerization of monomers and sulfonic acid monomers such as 2-acrylamide-2-methylpropanesulfonic acid, styrene sulfonic acid, and these alkali metals and/or amine salts At least one. [Component (5)] Polymers obtained by radical polymerization of acrylic monomers and nonionic monomers, and monomers composed of acrylic monomers, sulfonic acid monomers, and nonionic monomers The mixture is a polymer obtained by radical polymerization of the mixture, and the content (total amount) of the acrylic monomer and the sulfonic acid monomer in the monomer mixture is at least one polymer of 30% by mass or more. As the nonionic monomer in the aforementioned component (5), acrylic acid (carbon number 1 to 22) alkyl ester, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, (formaldehyde) Base) glycidyl acrylate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, diacetone (meth)acrylamide, methylolated diacetone (meth) Acrylic amide, N-hydroxymethyl (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone , Butadiene, isoprene, chloroprene, aziridinyl ethyl (meth)acrylate, aziridinyl (meth)acrylate, polyoxyalkylene (meth)acrylate, polyoxyalkylene Methyl (meth)acrylate, polyoxyalkylene (meth)acrylate 2-ethylhexyl, polyoxyalkylene di(meth)acrylate, triallyl cyanurate, allyl glycidyl ether, acetic acid Allyl ester, N-vinyl azole, maleimide, N-methyl maleimide, (2-dimethylamino)ethyl (meth)acrylate, (meth)acrylic acid Glycerides, alkylene di(meth)acrylates, vinyl silanes, trimethoxysilyl (meth)acrylates, etc. (meth)acrylates with silicone on the side chain, and polysiloxanes (Meth)acrylates, (meth)acrylates containing blocked isocyanate groups, (meth)acrylates having urethane bonds, and the like. In addition, as the aforementioned water-soluble acrylic polymer (at least one of the preferred components (1) to (5)), for example, Aron A-50P (manufactured by Toagosei Co., Ltd., sulfonic acid monomer copolymer Type acrylic tackifier) and other commercially available products. When the mixed liquid related to the present invention further contains the aforementioned (F) heat-sensitive gelling agent, the (F) heat-sensitive gelling agent can be used as it is in a solid (powder) state, but it does not retain the aforementioned (A) aqueous polymer From the viewpoint of the stability of the emulsified dispersion liquid of the urethane resin, it is preferable to use the aforementioned (F) heat-sensitive gelling agent in water and use it in the state of an aqueous solution. The concentration of the aqueous solution of the aforementioned (F) heat-sensitive gelling agent is preferably 1 to 50% by mass, and more preferably 10 to 30% by mass. When the aforementioned concentration is less than the aforementioned lower limit, a large amount of the aforementioned aqueous solution is required in order to exhibit migration inhibition during drying, and accordingly the concentration of the aforementioned (A) aqueous polyurethane resin in the mixed solution is reduced. Therefore, in order to obtain the desired leather material, a large amount of mixed liquid is required. Therefore, the amount of volatilized water increases, the drying time becomes longer, and the economic efficiency tends to decrease. However, since the method of the present invention is a method with high production efficiency, this problem tends to be improved. On the other hand, when the aforementioned concentration exceeds the aforementioned upper limit, the stability of the emulsion dispersion tends to be impaired by the formation of precipitates when mixed with the aforementioned (A) aqueous polyurethane resin emulsion dispersion. <Mixed liquid> In the manufacturing method of the leather material of the present invention, the preparation contains the aforementioned (A) aqueous polyurethane resin, the aforementioned (B) foaming agent, the aforementioned (C) formate compound, and the aforementioned ( D) Water, and a mixture of the aforementioned (E) thickener and/or the aforementioned (F) heat-sensitive gelling agent as needed. In the mixed liquid related to the present invention, as the content of the (A) aqueous polyurethane resin, relative to the total amount of the mixed liquid, it is preferably 5-50% by mass, and more preferably 10-35 quality%. When the content of the aforementioned (A) aqueous polyurethane resin is less than the aforementioned lower limit, in order to obtain the desired leather material, a large amount of mixed liquid is required. Therefore, the amount of volatilized water increases, the drying time becomes longer, and it is economical. The tendency to decline. On the other hand, when the upper limit is exceeded, the stability of the mixed solution tends to decrease. In addition, in the present invention, the content or addition amount means the total content or addition amount when the components are a mixture of two or more kinds. In the mixed liquid related to the present invention, the addition amount ratio (A:B) of the aforementioned (A) aqueous polyurethane resin to the aforementioned (B) foaming agent is preferably 100:1 in terms of mass ratio ~50, more preferably 100:5~50, still more preferably 100:5~30. When the addition amount of the aforementioned (B) foaming agent is less than the aforementioned lower limit, the effect of imparting a soft texture to the obtained leather material tends to decrease; on the other hand, when the aforementioned upper limit is exceeded, the time-dependent stability of the mixture The tendency to decline. In addition, if the above upper limit is exceeded, even if the above-mentioned (B) foaming agent is added, there is a tendency that the performance cannot be further improved, which is economically disadvantageous. In addition, in the mixed liquid related to the present invention, as the addition amount ratio (A:C) of the aforementioned (A) aqueous polyurethane resin to the aforementioned (C) formate compound, the mass ratio is preferably 100:1~75, more preferably 100:5~75, still more preferably 100:5~50. When the addition amount of the aforementioned (C) formate compound is less than the aforementioned lower limit, the effect of imparting a soft texture to the obtained leather material tends to decrease; on the other hand, when the aforementioned upper limit is exceeded, it is relatively high temperature in summer, etc. Under the atmosphere, the mixed liquid foams or the stability of the mixed liquid decreases with time. In addition, if the upper limit is exceeded, even if the (C) formate compound is added, there is a tendency that the performance cannot be further improved, which is economically disadvantageous. Furthermore, in the mixed solution of the present invention, the ratio of the (A) aqueous polyurethane resin to the (B) foaming agent to the (C) formate compound added (A:B) : C), from the same viewpoint as above, it is preferably 100:1-50:1-75 in terms of mass ratio, more preferably 100:5-50:5-75, and still more preferably 100:5 ~30:5~50. In addition, when the mixed liquid related to the present invention further contains the aforementioned (E) thickener, it is regarded as the addition amount ratio of the aforementioned (A) aqueous polyurethane resin to the aforementioned (E) thickener (A:E) , The mass ratio is preferably 100:0.01-50, more preferably 100:0.1-30, and still more preferably 100:0.1-10. When the amount of the aforementioned (E) thickener added is less than the aforementioned lower limit, the effect of imparting a softer texture to the obtained leather material tends to decrease; on the other hand, when the aforementioned upper limit is exceeded, the mixed solution may become highly viscous. The tendency of usability to decline. In addition, when the mixed solution of the present invention further contains the aforementioned (F) heat-sensitive gelling agent, the ratio of the addition amount of the aforementioned (A) aqueous polyurethane resin to the aforementioned (F) heat-sensitive gelling agent is (A:F), the mass ratio is preferably 100:0.1-15, more preferably 100:0.2-10. When the addition amount of the aforementioned (F) heat-sensitive gelling agent is less than the aforementioned lower limit, the migration inhibitory effect of the drying step tends to decrease, and the effect of imparting a softer texture to the obtained leather material tends to decrease; on the other hand, it exceeds the aforementioned When the upper limit is reached, in a relatively high temperature atmosphere such as summer, the mixed solution gels or the mixed solution tends to cause poor dispersion. In addition, when the upper limit is exceeded, even if the heat-sensitive gel (F) is added, there is a tendency that the performance cannot be further improved, which is economically disadvantageous. In addition, when the mixed liquid related to the present invention further contains the aforementioned (F) heat-sensitive gelling agent, the content thereof is determined from the viewpoint of maintaining the thickness of the foam after drying and the stability of the mixed liquid more sufficiently. From a standpoint, it is also preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass relative to 100 parts by mass of the added amount of the aforementioned (A) aqueous polyurethane resin. As the thermosensitive coagulation temperature of the mixed liquid related to the present invention, it is preferably 30 to 80°C, more preferably 40 to 70°C. In the present invention, the heat-sensitive coagulation temperature is such that when 5-10 g of the aforementioned mixture is put into a 20 mL glass test tube, the test tube is allowed to stand in a water bath, and the water bath is heated at a temperature of 1° C./min. The temperature at which it freezes. When the heat-sensitive solidification temperature is lower than the aforementioned lower limit, the mixture tends to gel under relatively high temperature atmospheres such as summer; on the other hand, when the aforementioned upper limit is exceeded, heat-sensitive solidification is not obvious, so there is a solidification step It tends to weaken the coagulation and decrease the migration inhibition; especially when it is dried (solidified) at a relatively low temperature of about 85 to 120°C, this tendency becomes significant. In addition, as the viscosity of the mixed solution in the present invention, from the viewpoint of the tendency to further increase the soft and warm texture of the leather material obtained, it is preferably 10 to 2,000 mP‧s in terms of the viscosity at 25°C. More preferably, it is 10~2,000 mP‧s. There is no particular limitation on the method of preparing the mixed solution according to the present invention, and the above-mentioned components can be mixed and prepared by a well-known method as appropriate. <Fiber base material> In the method for producing a leather material of the present invention, the fiber base material is impregnated with the mixed liquid, and then heated and dried to obtain a leather material. There are no particular restrictions on the fiber substrate in the present invention, and woven fabrics, knitted fabrics, non-woven fabrics, etc. can be suitably used. In addition, there are no particular restrictions on the raw material of such a fiber substrate. From the viewpoint of sufficient thickness retention and a tendency to obtain texture and quality closer to natural leather, polyamide fibers and polyester fibers are preferred. . When a nonwoven fabric is used as the above-mentioned fiber base material, the thickness of the yarn is preferably 2.0 dtex or less from the viewpoint of further improving the texture and quality of the leather material obtained. When the thickness of the yarn of the nonwoven fabric exceeds the aforementioned upper limit, the texture of the obtained leather material tends to become rough and the quality is impaired. In addition, the density of such a nonwoven fabric is preferably 0.1 to 0.8 g/cm 3 , and more preferably 0.30 to 0.55 g/cm 3 . When the density of the non-woven fabric is less than the aforementioned lower limit, the abrasion resistance of the leather material obtained tends to decrease. In addition, if a large amount of polyurethane resin is fixed to compensate for this, the leather obtained The texture of the material used becomes rough and the quality tends to be impaired. On the other hand, when the density of the nonwoven fabric exceeds the aforementioned upper limit, the texture of the obtained leather material tends to become rough and the quality is impaired. In addition, the thickness of the aforementioned fiber substrate is not particularly limited, but is preferably 0.1 to 1 cm, and more preferably 0.1 to 0.5 cm. In the present invention, within the scope of not impairing the effects of the present invention, for the purpose of imparting processing adaptability to the obtained leather material, additives may be further added to the aforementioned mixed solution. Examples of such additives include lower alcohols, glycol solvents, alcohol-based nonionic surfactants, acetylene glycol-based special surfactants, silicone-based surfactants, and fluorine-based surfactants. , Anionic surfactants, cationic surfactants and other penetrating agents; various stabilizers such as antioxidants, light-resistant stabilizers, and UV protection agents; various defoamers such as mineral oil series and silicone series; polyurethane Chemical catalysts; plasticizers; coloring agents such as pigments; life extension agents; fillers such as acrylic resin beads and polyurethane resin beads. Such additives may be used individually by 1 type, and may be used in combination of 2 or more types. When adding these additives to the mixed solution of the present invention, as the total addition amount, the (A) aqueous polyurethane resin, (B) foaming agent, (C) ) When the total mass of the formate compound is 100 parts by mass, it is preferably 50 parts by mass or less. In addition, when these compounds are used in the form of a water-emulsified dispersion liquid emulsified and dispersed in water, the quality refers to the remaining part (solid content, solid content, Non-volatile components) quality. In addition, in the present invention, when the polyurethane resin having a carboxyl group and/or a carboxylate group is used as the (A) aqueous polyurethane resin, it is within a range that does not impair the effect of the present invention. Within, for the purpose of imparting processing suitability to the obtained leather material, a crosslinking agent that reacts with the carboxyl group may be further added to the mixed liquid. Examples of such crosslinking agents include oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, and blocked isocyanates. Crosslinking agent, water-dispersed isocyanate crosslinking agent, melamine crosslinking agent, etc. As the aforementioned crosslinking agent, one type may be used alone, or two or more types may be used in combination. Among these crosslinking agents, from the viewpoint that there is a tendency to further improve the light resistance, heat resistance, and water resistance of the obtained leather material, a carbodiimide-based crosslinking agent is preferred, and as its addition amount, When the said (A) aqueous polyurethane resin is made into 100 mass parts, it is preferable that it becomes an amount of 0.5-10 mass parts. In the present invention, the method for impregnating the fiber base material with the mixed liquid is not particularly limited, and a known method can be suitably used. As the aforementioned impregnation method, for example, it is preferable to adopt a conventionally known method such as an impregnation process constituted by a dip-nip method, a spray process, and a method of immersing while coating with a coater. The concentration and treatment of the mixture Conditions etc. can also be appropriately selected according to the method used. In addition, before impregnating the fibrous base material with the mixed liquid, the fibrous base material may be pretreated. As such a pretreatment step, in order to adjust the adhesion between the aforementioned fiber substrate and the polyurethane resin component, it is preferable to use a polymer aqueous solution composed of polyvinyl alcohol, carboxymethyl cellulose, etc., or a silicone-based rubber Aqueous agents, fluorine-based water-repellent agents, etc. treat the aforementioned fiber base material. Regarding the impregnation amount of the mixed liquid phase to the fibrous base material, from the viewpoint that the thickness retention rate of the fibrous base material is further increased, and the physical properties such as texture and rubbing fastness of the obtained leather material are further improved, It is preferable to impregnate so that the component derived from the said (A) aqueous polyurethane resin may become 5 to 75 mass% in the material for leather obtained. In addition, as the impregnation related to the present invention, it is preferable to perform impregnation so that the component derived from the aforementioned (A) aqueous polyurethane resin is sufficiently fixed to the inside of the obtained leather material. According to the manufacturing method of the present invention, in order to suppress migration, the component derived from the aforementioned (A) aqueous polyurethane resin can be sufficiently fixed to maintain the thickness of the fiber base material and achieve excellent rubbing fastness. As the fixed state of the component derived from (A) aqueous polyurethane resin, when observing the cross section of the obtained leather material with a scanning electron microscope at 150 times magnification, it is preferable not only in the leather On the surface of the material used for leather, and 10% of the central part of the thickness of the material for leather, fixation of the component from the aforementioned (A) aqueous polyurethane resin can be observed, more preferably on the leather There is no difference in the amount of resin fixation between the center part and the surface part of the material. In the present invention, after impregnating the fibrous substrate with the mixed liquid, it is heated and dried to generate carbon dioxide from the foaming agent (B), and the mixed liquid is foamed and solidified. In the present invention, the heating and drying method is not particularly limited. For example, dry heat drying using hot air; wet drying using high temperature steam engine (HTS) or high pressure steam engine (HPS); microwave irradiation drying, etc. can be used. From the standpoint of resin coagulability and shortening the coagulation time, it is preferable to coagulate by wet heat by wet drying using humidity (steam). These drying methods can be used alone or in combination of two or more. In addition, as the heating and drying conditions (coagulation conditions), it is preferable to heat and dry at a temperature of 80 to 180°C for 1 to 30 minutes, and more preferably to heat to dry at a temperature of 80 to 130°C (more preferably 85 to 120°C) for 2 to 10 minutes. By drying and coagulating the mixed liquid impregnated in the fibrous base material in this way, the polyurethane resin can be fixed to the inside of the fibrous base material. In the present invention, it is preferable to further implement dry heat drying at 100-200°C (preferably 120-180°C) for drying moisture for 1-60 minutes (preferably 2-30 minutes) after solidifying the aforementioned mixed liquid. ). By heating and drying the mixed liquid impregnated in the fibrous base material in this way to foam (generate carbon dioxide) and solidify, the polyurethane resin with a uniform foam structure can be fixed to the fibrous base material Inside, the leather material of the present invention is obtained. The leather material of the present invention thus obtained can be dyed. The leather material of the present invention can sufficiently maintain its soft texture even if it is dyed. As such a dyeing method, there is no particular limitation, and it may be a method of dipping and then dyeing after fixing the polyurethane resin to the aforementioned fiber base material, or it may be a method of dyeing the aforementioned fiber base material and then polymerizing it. The urethane resin fixation method after impregnation and dyeing first. In addition, the leather material of the present invention may form a skin layer to form a leather material with a silver surface. The method of forming such a skin layer may be any conventionally known method, and is not particularly limited. For example, it can be mentioned that the material for the skin layer is coated on the release paper to evaporate the moisture of the skin material to form the skin layer. A method of applying an adhesive to the surface of the skin layer and bonding it to the leather material of the present invention to evaporate the moisture of the adhesive and bonding; or a method of bonding the two after evaporating the water to form an adhesive layer (Release paper transfer method). In addition, there can also be mentioned: a thermal transfer method in which the skin layer is formed on the release paper and the skin layer is bonded to the leather material of the present invention by heat; the method of directly spraying the skin layer material on the leather material of the present invention Spray method; direct coating method of coating the material for the skin layer on the leather material of the present invention using a gravure coater, knife coater, comma coater, air knife coater, etc. Among the methods for forming such a skin layer, the release paper transfer method is preferred from the viewpoint that the physical properties such as rubbing fastness of the obtained skin layer are further improved. The skin layer material and adhesive used in the aforementioned release paper transfer method are not particularly limited as long as they can be bonded to the leather material of the present invention. The thickness of the fiber base material can be further maintained, resulting in better From the viewpoints of physical properties such as texture and rubbing fastness, polyurethane resins are preferred. In addition, from the viewpoints of not generating VOCs and reducing environmental load, water-based or solvent-free materials are preferred. The leather material of the present invention can be used in the fields of vehicles, furniture, clothing, shoes, bags, bags, sandals, sundries, grinding and the like. [Examples] Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. In addition, each measurement and evaluation in each synthesis example, example, and comparative example were performed in accordance with the following methods. (1) Thermosensitive coagulation temperature measurement Put 5.0 g of the water-emulsified dispersion of the water-based polyurethane resin obtained in each polyurethane resin synthesis example and the mixed solution obtained in each example and comparative example. Put each test tube in a 20 mL glass test tube, stand each test tube in a water bath, and raise the temperature of the water bath at a rate of 1° C./min. The temperature at which the content loses fluidity and solidifies is measured as the heat-sensitive coagulation temperature. (2) Measurement of the value of 100% modulus The water-emulsified dispersion of the aqueous polyurethane resin obtained in each polyurethane resin synthesis example was used, and the test was conducted in accordance with 8. Test of JIS K 6250 (2006) Film collection. The same method is used to make a dumbbell-shaped No. 3 test piece, and the specified elongation tensile stress (MPa) when the gauge length is extended by 100% (when extended to 2 times) is measured according to the same method as JIS K 6251 (2010) The value is taken as the value of 100% modulus. (3) Viscosity measurement Using a single-cylinder rotary viscometer (B-type viscometer), the viscosity at 25°C of the mixture obtained in each of the examples and comparative examples was measured according to the method based on JIS K7117-1 (1999) [ mPa·s]. (4) Measurement of softness (softness) measurement For the dyed leather materials obtained in each of the Examples and Comparative Examples, according to ISO 17235:2015 (IULTCS/IUP 36), use a softness tester (leather softness measurement) Device ST300: UK, manufactured by MSA ENGINEERING SYSTEMS LTD.), to measure softness (softness, stiffness) [mm]. In addition, the value of stiffness indicates the depth of penetration, and the larger the value, the softer it is. (5) Texture evaluation The material for leather after dyeing and processing obtained in each example and each comparative example was evaluated according to the following criteria by touch. Grade 5: Soft and very resilient texture Grade 4: Soft and resilient texture Grade 3: Soft but slightly lacking in resilience Grade 2: Slightly hard and paper-like (paper-like) texture Grade 1 : Rough and paper-like (paper-like) texture (Synthesis example 1 of aqueous polyurethane resin) Polybutylene is added to a four-necked flask equipped with a stirrer, reflux cooling tube, thermometer, and nitrogen introduction tube Diol (weight average molecular weight 1,000) 167.9 g, random copolymer addition polymer of ethylene oxide and propylene oxide (weight average molecular weight 1,000, oxyethylene content 70% by mass) 36.9 g, 1,4-butanediol 3.2g, 4.0g trimethylolpropane, 0.002g dibutyltin dilaurate and 128.6g methyl ethyl ketone, after uniformly mixing, add 88.0g dicyclohexylmethane diisocyanate, and react at 80°C for 300 minutes to obtain free isocyanate A methyl ethyl ketone solution of an isocyanate group-terminated prepolymer with a content of 1.0% by mass. After cooling the obtained methyl ethyl ketone solution of the isocyanate group-terminated prepolymer to below 30°C, 0.5 g of decyl phosphate and 12.0 g of ethylene oxide 20 mol adduct of tristyryl phenol were added and mixed uniformly After that, using a disperser blade, 435.0 g of water was slowly added to perform phase inversion emulsification and dispersion to obtain an emulsified dispersion. Then, 3.9 g of piperazine hexahydrate and 2.1 g of diethylene triamine were dissolved in 23.9 g of water, and the obtained polyamine aqueous solution was added to the aforementioned emulsified dispersion, and the chain extension reaction was carried out for 90 minutes. The solvent was removed under reduced pressure at 35°C to obtain a stable aqueous polyurethane resin with a non-volatile content of 40.0% by mass, a viscosity of 250.0 mPa·s (BM viscometer, No. 2 rotor, 60 rpm), and an average particle diameter of 550 nm. The water emulsified dispersion. The content of the carboxyl group, carboxylate group, sulfo group, and sulfonate group in the water-based polyurethane resin are all 0.0% by mass, and the value of the 100% modulus is 2 MPa. In addition, the water-emulsified dispersion of the aqueous polyurethane resin gels at 65°C and has heat-sensitive coagulability. (Synthesis example 2 of aqueous polyurethane resin) 1,6-hexanediol polycarbonate polyol (average molecular weight) was added to a four-necked flask equipped with a stirrer, reflux cooling tube, thermometer, and nitrogen introduction tube 2,000) 157.0g, neopentyl glycol 7.5g, trimethylolpropane 1.3g, 2,2-dimethylolpropane 9.5g, dibutyltin dilaurate 0.001g and methyl ethyl ketone 105g, after uniformly mixing, add iso 69.7 g of phorone diisocyanate was reacted at 80° C. for 300 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a carboxyl group in which the content of free isocyanate groups relative to the nonvolatile content was 1.9% by mass. After cooling the obtained methyl ethyl ketone solution of the isocyanate group-terminated prepolymer to 50°C or lower, 6.8 g of triethylamine was added, and the neutralization reaction was performed at 40°C for 30 minutes. Next, the neutralized solution was cooled to 30°C or lower, and 421.9 g of water was slowly added using a disperser blade to emulsify and disperse the neutralized product of the isocyanate group-terminated prepolymer having a carboxyl group to obtain a dispersion. Then, 5.2 g of 60% by mass hydrazine hydrate and 1.1 g of diethylene triamine were dissolved in 20 g of water, and the resulting polyamine aqueous solution was added to the aforementioned dispersion, and the chain extension reaction was performed at 35°C for 60 minutes Then, the solvent was removed at 35°C under reduced pressure to obtain a stable carboxyl group with 35.0 mass% non-volatile content, 120 mPa·s viscosity (BM viscometer, No. 2 rotor, 60 rpm), pH 7.8, and average particle diameter of 90 nm. And carboxylate-based aqueous polyurethane resin water dispersion. The total of the carboxyl group content and the carboxylate group content in this aqueous polyurethane resin was 1.3% by mass, and the value of the 100% modulus was 2 MPa. In addition, the water-emulsified dispersion of polyurethane resin having a carboxyl group and a carboxylate group does not gel even if heated at 90°C, and has no heat-sensitive coagulability. (Example 1) The (A) water-emulsified dispersion of the water-based polyurethane resin obtained in Synthesis Example 1 of the water-based polyurethane resin 65 parts by mass (26 parts by mass of solid content), (B ) 16 parts by mass of sodium bicarbonate 8% aqueous solution (solid content (sodium bicarbonate) 1.3 parts by mass), 1 part by mass of (C) ethylene formate, and 18 parts by mass of (D) water are uniformly mixed to prepare an aqueous polyamine base A mixed solution with a formate resin concentration of 26% by mass. The heat-sensitive coagulation temperature of the obtained mixture is 60℃, and the viscosity at 25℃ is 40mPa·s. Using a slit mill, impregnate the mixed solution into unprocessed cloth (non-woven fabric made of polyester fiber, 0.5dtex, density 0.3g/cm 3 ), and impregnate so that the penetration amount becomes 100% by mass After that, wet drying (moist heat coagulation) was performed at a relative humidity of 60% and a temperature of 100°C for 5 minutes, and then dry heat dried at 130°C for 5 minutes to obtain an artificial leather (leather material). Then, the obtained artificial leather was dyed and RC soaped under the following conditions to obtain an artificial leather dyed processed cloth (dyed leather material). <Dyeing conditions> Dyeing machine: MINI COLOR dyeing machine (made by TEXAM Giken) Dye: Kayalon Microester Blue DX-LS conc (manufactured by Nippon Kayaku Co., Ltd.) 0.10%owf Kayalon Maicroester Yellow DX-LS (Nippon Kayaku (Stock) Manufacturing) 2.00% owf Kayalon Maicroester Red DX-LS (Nippon Kayaku Co., Ltd.) 0.80% owf Dyeing auxiliary: NICCA SUNSOLT RM-3406 (Nippon Chemical Co., Ltd.) 0.5g/L pH adjustment Agent: 90% mass acetic acid 0.3cc/L Bath ratio: (1:20) Dyeing conditions: 130°C×60 minutes (heating rate 2°C/min). <RC conditions> RC bath: sodium hydroxide 2g/L hydrosulfite (hydrosulfite) 2g/L bath ratio: (1:20) RC conditions: 80°C×20 minutes (heating rate 2°C/min). The obtained artificial leather dyed fabric (material for leather after dyeing) was subjected to softness measurement and texture evaluation, and the obtained results are shown in Table 1 below together with the composition and viscosity of the mixed solution. (Examples 2 to 6) Except that the composition of the mixed solution was set to the composition shown in Table 1 below, the same procedure as in Example 1 was carried out to obtain artificial leather (leather material) and artificial leather dyed fabric (dyed Leather material after processing). The obtained artificial leather dyed fabric (material for leather after dyeing) was subjected to softness measurement and texture evaluation, and the obtained results are shown in Table 1 below together with the composition and viscosity of the mixture. In addition, the part by mass described in the column of water in the table represents the amount of water added other than the water mixed to form each dispersion or aqueous solution (the same applies hereinafter).
Figure 02_image001
(Examples 7 to 13) Except that the composition of the mixed solution was set to the composition shown in Table 2 below, the same procedure as in Example 1 was carried out to obtain artificial leather (leather material) and artificial leather dyed fabric ( Leather material after dyeing process). The obtained artificial leather dyed fabric (material for leather after dyeing) was subjected to softness measurement and texture evaluation, and the obtained results are shown in Table 2 below together with the composition and viscosity of the mixture.
Figure 02_image003
(Comparative Examples 1 to 5) Except that the composition of the mixed solution was set to the composition shown in Table 3 below, in the same manner as in Example 1, artificial leather (leather material) and artificial leather dyed fabric ( Leather material after dyeing process). Softness measurement and texture evaluation of the obtained artificial leather dyed fabric (material for leather after dyeing) were performed, and the obtained results are shown in Table 3 below together with the composition and viscosity of the mixed solution. In addition, in Comparative Example 4, foaming occurred when the mixed liquid was prepared, and the fiber base material could not be processed.
Figure 02_image005
As shown in the results shown in Tables 1 to 3, it was confirmed that the leather materials obtained in Examples 1 to 13 were excellent in soft texture, and it was confirmed that the leather material production method of the present invention can be easily and efficiently obtained A soft leather material with excellent texture. In addition, when using a mixed solution that further contains (E) a thickener and/or (F) heat-sensitive gelling agent (for example, Examples 3 to 6, 8 to 13), it was confirmed that leather with a softer texture can be obtained Use materials. On the other hand, when using a mixed solution that does not contain any of (B) foaming agent and (C) formate compound (for example, Comparative Examples 1 and 2), it was confirmed that the obtained leather material The soft texture is poor. In addition, even when a mixture containing ammonium sulfate as a substance that generates acid by heating is used instead of the (C) formate compound related to the present invention (for example, Comparative Examples 3 and 5), the resulting leather Among the materials, it was also confirmed that the soft texture was poor, and when a mixed liquid containing citric acid was used (for example, Comparative Example 4), foaming occurred when the mixed liquid was prepared, and the fiber substrate could not be processed. [Industrial Applicability] As described above, according to the present invention, it is possible to provide a method for producing a leather material that can obtain a soft leather material with excellent texture more easily and efficiently than before. In addition, according to the present invention, a porous resin layer can be efficiently and easily formed in a fibrous base material such as a nonwoven fabric. Therefore, in addition to suppressing fiber bundles and fixation to damage the texture, the resin layer can also be filled with the aforementioned Because of the voids in the fibrous base material, improvement of the resilience and improvement of the physical strength (tensile strength, tear strength, and bending resistance) of the artificial leather can also be expected. Therefore, the manufacturing method of the leather material of the present invention is particularly useful as an industrial manufacturing method of leather materials. In addition, the leather material obtained by the manufacturing method of the present invention can be used in vehicles, furniture, clothing, bags, shoes, and bags. It can be suitably used in industrial fields such as articles, miscellaneous goods, and grinding, and can also be suitably used as a stable and high-quality leather material with a skin layer.

Claims (8)

一種皮革用材料之製造方法，其特徵為： 使含有(A)水性聚胺基甲酸酯樹脂、(B)藉由加熱及/或酸產生二氧化碳之發泡劑、(C)甲酸酯化合物，及(D)水之混合液含浸於纖維基材後，進行加熱乾燥，得到皮革用材料。A method for manufacturing leather materials, characterized by: The fiber is impregnated with a mixture containing (A) water-based polyurethane resin, (B) foaming agent that generates carbon dioxide by heating and/or acid, (C) formate compound, and (D) water After the substrate is heated and dried, a leather material is obtained. 如請求項1之皮革用材料之製造方法，其中 前述(B)發泡劑為碳酸鹽。Such as the method of manufacturing leather materials in claim 1, where The aforementioned (B) blowing agent is carbonate. 如請求項1或2之皮革用材料之製造方法，其中 在前述混合液中，前述(A)水性聚胺基甲酸酯樹脂、前述(B)發泡劑，與前述(C)甲酸酯化合物的添加量比A:B:C以質量比計為100:1～50:1～75。Such as the method of manufacturing leather materials in claim 1 or 2, where In the aforementioned mixed solution, the aforementioned (A) aqueous polyurethane resin, the aforementioned (B) foaming agent, and the aforementioned (C) formate compound are added in a ratio A:B:C in terms of mass ratio 100:1～50:1～75. 如請求項1或2之皮革用材料之製造方法，其中 前述混合液進一步含有(E)增黏劑。Such as the method of manufacturing leather materials in claim 1 or 2, where The aforementioned mixed solution further contains (E) a thickener. 如請求項1或2之皮革用材料之製造方法，其中 前述混合液進一步含有(F)熱敏膠凝劑。Such as the method of manufacturing leather materials in claim 1 or 2, where The aforementioned mixed solution further contains (F) a heat-sensitive gelling agent. 如請求項1或2之皮革用材料之製造方法，其中 前述(A)水性聚胺基甲酸酯樹脂為具有選自由羧基、羧酸酯基、磺基，及磺酸酯基所構成之群組中之至少1種陰離子性基的聚胺基甲酸酯樹脂。Such as the method of manufacturing leather materials in claim 1 or 2, where The aforementioned (A) aqueous polyurethane resin is a polyurethane formic acid having at least one anionic group selected from the group consisting of carboxyl group, carboxylate group, sulfo group, and sulfonate group Ester resin. 如請求項1或2之皮革用材料之製造方法，其中 前述混合液之熱敏凝固溫度為30～80℃。Such as the method of manufacturing leather materials in claim 1 or 2, where The thermosensitive coagulation temperature of the aforementioned mixture is 30 to 80°C. 如請求項1或2之皮革用材料之製造方法，其中 以來自前述(A)水性聚胺基甲酸酯樹脂的成分固著至佔據皮革用材料之厚度中央部的10%部分的方式，使前述混合液含浸於前述纖維基材。Such as the method of manufacturing leather materials in claim 1 or 2, where The fiber base material is impregnated with the mixed liquid so that the component derived from the (A) aqueous polyurethane resin is fixed to occupy 10% of the central portion of the thickness of the leather material.
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