WO2017221455A1 - Method for producing coagulum - Google Patents

Method for producing coagulum Download PDF

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Publication number
WO2017221455A1
WO2017221455A1 PCT/JP2017/005661 JP2017005661W WO2017221455A1 WO 2017221455 A1 WO2017221455 A1 WO 2017221455A1 JP 2017005661 W JP2017005661 W JP 2017005661W WO 2017221455 A1 WO2017221455 A1 WO 2017221455A1
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Prior art keywords
urethane resin
mass
aqueous
aqueous urethane
coagulum
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PCT/JP2017/005661
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French (fr)
Japanese (ja)
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智博 鉄井
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Dic株式会社
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Priority to JP2017528602A priority Critical patent/JP6183577B1/en
Publication of WO2017221455A1 publication Critical patent/WO2017221455A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/82—Post-polymerisation treatment
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—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

Definitions

  • the present invention relates to a method for producing a solidified material that can be used for producing, for example, a leather-like sheet.
  • the aqueous urethane resin composition in which the urethane resin is dispersed in an aqueous medium can reduce the burden on the environment as compared with conventional organic solvent-based urethane resin compositions, so that leather-like sheets such as artificial leather and synthetic leather, In recent years, it has been used favorably as a material for producing coating agents, adhesives and the like.
  • the liquid composition of the urethane resin once decreases in viscosity by heating, and the resin tends to adhere to the fiber intersection due to capillary phenomenon, and the resin restrains the fiber. It was pointed out that the resulting film was inferior in flexibility and flexibility and easily damaged.
  • the present invention provides a method for producing a coagulated product obtained by coagulating an aqueous urethane resin composition with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
  • a solidified product having excellent texture can be obtained.
  • the coagulation bath waste liquid can be easily treated, contributing to the reduction of manufacturing costs. it can.
  • a coagulant containing metal ions is not used, rusting or deterioration of the production apparatus when producing a coagulated product is not caused. Therefore, the solidified product obtained by the production method of the present invention can be suitably used for production of gloves, paints, leather-like sheets and the like.
  • the electron micrograph of sectional drawing of the fiber base material which has the solidified material obtained in Example 1 is shown (magnification 200 times).
  • the electron micrograph of the cross-sectional view of the fiber base material which has the solidified material obtained by the comparative example 1 is shown (magnification 200 times).
  • the method for producing a coagulated product according to the present invention is characterized in that an aqueous urethane resin composition is coagulated with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
  • the viscosity of the aqueous urethane resin composition and the coagulation speed are fast, and because of the ability to suppress resin fiber adhesion / restraint due to capillary phenomenon, an even better work cloth texture is obtained.
  • water used for the non-metal coagulant aqueous solution for example, ion exchange water, distilled water, tap water, or the like can be used. These waters may be used alone or in combination of two or more.
  • the solidified urethane resin is filled up to the inside of the fiber base material, and the state where the solidified material is entangled with the fiber base material is formed. It can be suitably used as an impregnated layer.
  • a urethane coagulated material layer is formed on the surface of the fiber substrate and in the vicinity of the surface, and therefore, it can be suitably used for manufacturing gloves.
  • the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
  • the fibrous base material is used as the fibrous base material.
  • a method of directly impregnating the coagulation bath containing the mixture and squeezing excess with a mangle or the like can be mentioned.
  • the impregnation time is, for example, in the range of 1 to 30 minutes.
  • the impregnated base material is taken out and further immersed in the aqueous urethane resin composition, so that the urethane resin in the aqueous urethane resin composition is solidified, and the urethane solidified material is formed in the surface layer and the vicinity of the surface layer of the fiber base material.
  • a fiber substrate on which a layer is formed is obtained.
  • the impregnation / solidification time at this time is, for example, in the range of 1 to 30 minutes.
  • the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
  • aqueous urethane resin composition that can be used in the present invention, for example, those containing an aqueous urethane resin (A) and an aqueous medium (B) can be used.
  • the aqueous urethane resin (A) can be dispersed in an aqueous medium (B) described later.
  • the aqueous urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group
  • An aqueous urethane resin or the like that is forcibly dispersed in the aqueous medium (B) with an emulsifier can be used.
  • These aqueous urethane resins (A) may be used alone or in combination of two or more.
  • a water-based urethane resin having a hydrophilic group it is preferable to use a water-based urethane resin having a hydrophilic group, the solidification property of the non-metal coagulant is further improved by the electric double layer compression effect, and the fiber group. It is more preferable to use an aqueous urethane resin having an anionic group from the viewpoint that the urethane resin is easily filled and entangled into the material and the texture is further improved.
  • Examples of a method for obtaining the aqueous urethane resin having an anionic group include a method using, as a raw material, one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group.
  • Examples of the compound having a carboxyl group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolpropionic acid, , 2'-valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- 2-Aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.
  • the carboxyl group and sulfonyl group may be partially or completely neutralized with a basic compound in the aqueous urethane resin composition.
  • a basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. Can do.
  • Examples of the method for obtaining the aqueous urethane resin having a cationic group include a method using one or more compounds having an amino group as a raw material.
  • Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl.
  • a compound having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
  • Examples of the method for obtaining the aqueous urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
  • Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.
  • Examples of the emulsifier that can be used in obtaining the aqueous urethane resin that is forcibly dispersed in the aqueous medium (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Nonionic emulsifiers such as polyoxyethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymer; fatty acid salt such as sodium oleate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl sulfosuccinate, naphthalene sulfonate Anionic emulsifiers such as salts, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; alkyl amine salts, alkyl trimethyl Am
  • the content of the aromatic ring of the aqueous urethane resin (A) is preferably in the range of 0.8 to 8 mol / kg, more preferably in the range of 1 to 6 mol / kg.
  • aromatic polyisocyanate examples include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use diphenylmethane diisocyanate from the viewpoint of easy availability of raw materials and texture.
  • polyisocyanates examples include hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and dimer acid diisocyanate.
  • An aliphatic or alicyclic polyisocyanate such as norbornene diisocyanate can be used.
  • These polyisocyanates may be used alone or in combination of two or more.
  • chain extender (a3) examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1, Amino groups such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, etc.
  • Chain extender having: ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharo Scan, glycol, glycerine, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and the like can be used a chain extender having a hydroxyl group such as trimethylol propane. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint that oil grip properties and chemical resistance can be further improved.
  • the aqueous urethane resin (A) When the aqueous urethane resin (A) is produced, it is preferable to deactivate the isocyanate group remaining in the aqueous urethane resin (A). When the isocyanate group is deactivated, it is preferable to use an alcohol having one hydroxyl group such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A).
  • the mass ratio [(A) / (B)] between the aqueous urethane resin (A) and the aqueous medium (B) is preferably in the range of 10/80 to 70/30 from the viewpoint of workability.
  • the range of 20/80 to 60/40 is more preferable.
  • the amount used in the case of using the emulsifier is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A) from the viewpoint of water dispersion stability and texture. A range of 1 to 10 parts by mass is more preferable.
  • the aqueous urethane resin composition used in the present invention is more easily coagulated by the coagulant, more easily filled and entangled inside the fiber base material, further improved in texture, and water dispersion stability.
  • Water-based urethane resin containing an anionic group obtained by reacting an aromatic polyisocyanate, a polyol and a chain extender (A), an aqueous medium (B), and a nonionic emulsifier It is preferable to use a resin composition.
  • Synthesis Example 2 Preparation of Aqueous Urethane Resin Composition (X-2) Polyether polyol (“PTMG2000” Mitsubishi Kasei Co., Ltd.) in the presence of 3,281 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate Manufactured, number average molecular weight: 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20, After reacting at 70 ° C.
  • aqueous urethane resin composition (X-3) having a nonvolatile content of 40% by mass.
  • a methyl ethyl ketone solution of urethane prepolymer (X′-4) having an isocyanate group at the terminal was obtained.
  • phase inversion was performed.
  • a urethane resin composition (X-4) having a nonvolatile content of 40% by mass.
  • Example 1 100 parts by mass of the aqueous urethane resin composition (X-1) obtained in Synthesis Example 1, 5 parts by mass of a thickener (“Borch Gel L75N” manufactured by Borcher), a carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) ⁇ 02 ”) 4 parts by mass and 200 parts by mass of ion-exchanged water were stirred with a mechanical mixer at 2,000 rpm for 2 minutes, and then deaerated with a vacuum deaerator to prepare a blended solution.
  • a thickener (“Borch Gel L75N” manufactured by Borcher)
  • Carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) ⁇ 02 ”
  • the blended solution was solidified by immersing the non-woven fabric containing the blended solution in a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C. for 3 minutes. Finally, it was dried with a hot air dryer at 100 ° C. for 30 minutes to obtain a fiber base material having a coagulum.
  • Examples 2 to 4 A fiber base material having a coagulum was obtained in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used was changed as shown in the table.
  • Example 5 A fiber base material having a coagulated product was obtained in the same manner as in Example 1 except that the temperature of the coagulation bath was changed to 22 ° C.
  • Example 2 In Example 1, a fiber base material was used in the same manner as in Example 1 except that a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C was used instead of a coagulation bath of 5 mass% ammonium sulfate aqueous solution at 10 ° C. However, the aqueous urethane resin composition (X-1) did not coagulate.
  • Examples 1 to 5 according to the present invention can provide a solidified product having an excellent texture. Further, as can be confirmed in FIG. 1, it was found that a solidified product of urethane resin was filled up to the inside of the fiber base material, and a state in which the solidified material was entangled with the fiber base material was formed.
  • Comparative Example 1 is a form in which coagulation was performed by thermal coagulation, but the texture was poor. Further, as can be confirmed in FIG. 2, the urethane resin was not filled up to the inside of the fiber base material, and entanglement of the fiber base material was not confirmed.
  • Comparative Example 2 was an embodiment in which the coagulation bath was not heated and was used at 10 ° C., but did not coagulate.

Abstract

The purpose of the present invention is to provide a method for producing a coagulum that is characterized by being obtained by coagulating an aqueous urethane resin composition using an aqueous solution of a nonmetallic coagulant agent that is heated to 40°C or higher. The present invention addresses the problem of providing a production method by which it is possible to obtain a coagulum having an excellent texture without using an organic solvent. The production method according to the present invention is able to produce a coagulum of excellent texture. In addition, said production method does not employ an organic solvent in a coagulation bath, and thus is free of risk of exposure to harmful volatile substances or diffusion thereof to the environment, and enables a waste liquid of the coagulation bath to be treated by a simplified method, and thereby is able to contribute to curbing production costs. Furthermore, this production method does not use any coagulant agent that contains metal, and thus does not induce rust or deterioration to the production apparatus used for producing the coagulum. Hence, the coagulum obtained by the production method according to the present invention can be suitably used for production of gloves, coating materials, leather-like sheets, etc.

Description

凝固物の製造方法Method for producing coagulum
　本発明は、例えば、皮革様シート等の製造に使用可能な凝固物の製造方法に関する。 The present invention relates to a method for producing a solidified material that can be used for producing, for example, a leather-like sheet.
　ウレタン樹脂が水性媒体中に分散した水性ウレタン樹脂組成物は、従来の有機溶剤系ウレタン樹脂組成物と比較して、環境への負荷を低減できることから、人工皮革、合成皮革等の皮革様シート、コーティング剤、接着剤などを製造する材料として、近年好適に使用され始めている。 The aqueous urethane resin composition in which the urethane resin is dispersed in an aqueous medium can reduce the burden on the environment as compared with conventional organic solvent-based urethane resin compositions, so that leather-like sheets such as artificial leather and synthetic leather, In recent years, it has been used favorably as a material for producing coating agents, adhesives and the like.
　前記皮革様シートは、一般に、不織布等の繊維基材と、必要に応じて多孔層等からなる中間層と、表皮層とによって構成されるものが多く、前記繊維基材としては、皮革様シートの耐屈曲性や風合いの向上を目的として、不織布等の繊維基材に水性ウレタン樹脂組成物を含浸し感熱凝固したもの（含浸層）が使用されている。 The leather-like sheet is generally composed of a fiber base material such as a non-woven fabric, an intermediate layer composed of a porous layer or the like as needed, and a skin layer. The fiber base material is a leather-like sheet. For the purpose of improving the bending resistance and texture, a fiber base material such as nonwoven fabric impregnated with an aqueous urethane resin composition and heat-coagulated (impregnated layer) is used.
　前記繊維基材の含浸用の水性ウレタン樹脂組成物としては、例えば、カルボキシル基及び／又はスルホン酸基を有するポリウレタン樹脂、感熱凝固剤、及び水性媒体を含有する水性ウレタン樹脂組成物が開示されている（例えば、特許文献１を参照。）。 Examples of the aqueous urethane resin composition for impregnation of the fiber base material include an aqueous urethane resin composition containing a polyurethane resin having a carboxyl group and / or a sulfonic acid group, a thermal coagulant, and an aqueous medium. (For example, refer to Patent Document 1).
　しかしながら、感熱凝固による水性ウレタン樹脂組成物の凝固では、ウレタン樹脂の配合液が加熱により一旦低粘度化し、毛細管現象により繊維交洛点に樹脂が付着しやすく、樹脂が繊維を拘束するため、得られる皮膜は柔軟性や屈曲性に劣り、破損しやすいとの指摘があった。 However, in the solidification of the aqueous urethane resin composition by heat-sensitive coagulation, the liquid composition of the urethane resin once decreases in viscosity by heating, and the resin tends to adhere to the fiber intersection due to capillary phenomenon, and the resin restrains the fiber. It was pointed out that the resulting film was inferior in flexibility and flexibility and easily damaged.
特開２０１５－７１７２号公報Japanese Patent Laying-Open No. 2015-7172
　本発明が解決しようとする課題は、有機溶剤を使用せず、風合いに優れる凝固物が得られる製造方法を提供することである。 The problem to be solved by the present invention is to provide a production method capable of obtaining a solidified product having an excellent texture without using an organic solvent.
　本発明は、水性ウレタン樹脂組成物を、１５℃以上の非金属凝固剤水溶液で凝固させることにより得られることを特徴とする凝固物の製造方法を提供するものである。 The present invention provides a method for producing a coagulated product obtained by coagulating an aqueous urethane resin composition with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
　本発明の製造方法によれば、風合いに優れる凝固物が得られる。また、凝固浴として、有機溶剤を使用しないため、有害な揮発性物質の暴露や環境への拡散の恐れもなく、また、凝固浴の廃液の処理も簡便となるため製造コストの抑制にも貢献できる。更に、金属イオンを含有する凝固剤を用いていないため、凝固物を製造する際の製造装置の錆びや劣化を引き起こすことがない。よって、本発明の製造方法により得られる凝固物は、手袋、塗料、皮革様シート等の製造に好適に使用することができる。 According to the production method of the present invention, a solidified product having excellent texture can be obtained. In addition, since no organic solvent is used as the coagulation bath, there is no risk of exposure to harmful volatile substances or diffusion to the environment, and the coagulation bath waste liquid can be easily treated, contributing to the reduction of manufacturing costs. it can. Furthermore, since a coagulant containing metal ions is not used, rusting or deterioration of the production apparatus when producing a coagulated product is not caused. Therefore, the solidified product obtained by the production method of the present invention can be suitably used for production of gloves, paints, leather-like sheets and the like.
実施例１で得られた凝固物を有する繊維基材の断面図の電子顕微鏡写真を示すものである（倍率２００倍）。The electron micrograph of sectional drawing of the fiber base material which has the solidified material obtained in Example 1 is shown (magnification 200 times). 比較例１で得られた凝固物を有する繊維基材の断面図の電子顕微鏡写真を示すものである（倍率２００倍）。The electron micrograph of the cross-sectional view of the fiber base material which has the solidified material obtained by the comparative example 1 is shown (magnification 200 times).
　本発明である凝固物の製造方法は、水性ウレタン樹脂組成物を、１５℃以上の非金属凝固剤水溶液で凝固させることを特徴とするものである。 The method for producing a coagulated product according to the present invention is characterized in that an aqueous urethane resin composition is coagulated with a nonmetallic coagulant aqueous solution at 15 ° C. or higher.
　本発明においては、凝固剤として、非金属凝固剤水溶液を用いること、及びそれを１５℃以上にすることが重要である。本発明においては、凝固剤として非金属凝固剤を用いることにより、樹脂付着状態の均一性が向上するため、優れた風合いを有する凝固物が得られ、更に、金属イオンを含有していないため、凝固物を製造する際の製造装置の錆びや劣化を引き起こすことがない。また、前記凝固剤水溶液を１５℃以上にすることにより、良好な凝固速度が得られるため、水性ウレタン樹脂を凝固させることができ、更に優れた風合いを有する凝固物が得られる。なお、凝固剤の温度が１５℃未満であると、水性ウレタン樹脂を凝固することができない。前記凝固浴の温度としては、１７～１００℃が好ましく、２０～８０℃の範囲であることが好ましい。 In the present invention, it is important to use a non-metal coagulant aqueous solution as the coagulant and to make it 15 ° C. or higher. In the present invention, by using a non-metal coagulant as a coagulant, since the uniformity of the resin adhesion state is improved, a coagulated product having an excellent texture is obtained, and further, it does not contain metal ions, It does not cause rusting or deterioration of the manufacturing equipment when manufacturing the solidified product. Further, by setting the aqueous coagulant solution at 15 ° C. or higher, a good coagulation rate can be obtained, so that the aqueous urethane resin can be coagulated, and a coagulated product having an excellent texture can be obtained. If the temperature of the coagulant is less than 15 ° C., the aqueous urethane resin cannot be coagulated. The temperature of the coagulation bath is preferably 17 to 100 ° C., and preferably in the range of 20 to 80 ° C.
　前記非金属凝固剤としては、例えば、塩化アンモニウム、塩化テトラメチルアンモニウム、塩化テトラエチルアンモニウム、塩化テトラプロピルアンモニウム、塩化テトラブチルアンモニウム、塩化テトラヘキシルアンモニウム、塩化テトラオクチルアンモニウム、塩化テトラフェニルアンモニウム、塩化トリエチルメチルアンモニウム、塩化トリエチルヘキシルアンモニウム、塩化トリオクチルメチルアンモニウム、塩化トリオクチルブチルアンモニウム、塩化トリオクチルベンジルアンモニウム、塩化トリメチルベンジルアンモニウム、塩化トリブチルベンジルアンモニウム、塩化トリフェニルイソブチルアンモニウム、塩化トリフェニルベンジルアンモニウム、臭化アンモニウム、臭化テトラメチルアンモニウム、臭化テトラエチルアンモニウム、臭化テトラプロピルアンモニウム、臭化テトラブチルアンモニウム、臭化テトラヘキシルアンモニウム、臭化テトラオクチルアンモニウム、臭化テトラフェニルアンモニウム、臭化トリエチルメチルアンモニウム、臭化トリエチルヘキシルアンモニウム、臭化トリオクチルメチルアンモニウム、臭化トリオクチルブチルアンモニウム、臭化トリオクチルベンジルアンモニウム、臭化トリメチルベンジルアンモニウム、臭化トリブチルベンジルアンモニウム、臭化トリフェニルイソブチルアンモニウム、臭化トリフェニルベンジルアンモニウム、ヨウ化アンモニウム、ヨウ化テトラメチルアンモニウム、ヨウ化テトラエチルアンモニウム、ヨウ化テトラプロピルアンモニウム、ヨウ化テトラブチルアンモニウム、ヨウ化テトラヘキシルアンモニウム、ヨウ化テトラオクチルアンモニウム、ヨウ化テトラフェニルアンモニウム、ヨウ化トリエチルメチルアンモニウム、ヨウ化トリエチルヘキシルアンモニウム、ヨウ化トリオクチルメチルアンモニウム、ヨウ化トリオクチルブチルアンモニウム、ヨウ化トリオクチルベンジルアンモニウム、ヨウ化トリメチルベンジルアンモニウム、ヨウ化トリブチルベンジルアンモニウム、ヨウ化トリフェニルイソブチルアンモニウム、ヨウ化トリフェニルベンジルアンモニウム等のハロゲン化アンモニウム；塩酸アンモニウム、リン酸アンモニウム、ホウ酸アンモニウム、フッ化水素酸アンモニウム、硫酸アンモニウム、硝酸アンモニウム、ケイ酸アンモニウム、リン酸アンモニウム等の無機酸アンモニウム：ギ酸アンモニウム、酢酸アンモニウム、プロピオン酸アンモニウム、リンゴ酸アンモニウム、スルファミン酸アンモニウム等の有機酸アンモニウム；塩化テトラフェニルホスホニウム、ヨウ化テトラフェニルホスホニウム、臭化テトラメチルホスホニウム、塩化テトラブチルホスホニウム、臭化テトラブチルホスホニウム、ヨウ化テトラブチルホスホニウム等の無機酸ホスホニウム；酢酸テトラブチルホスホニウム等の有機酸ホスホニウムなどを用いることができる。これらの非金属凝固剤は単独で用いても２種以上を併用してもよい。 Examples of the nonmetallic coagulant include ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, tetraphenylammonium chloride, and triethylmethyl chloride. Ammonium, triethylhexylammonium chloride, trioctylmethylammonium chloride, trioctylbutylammonium chloride, trioctylbenzylammonium chloride, trimethylbenzylammonium chloride, tributylbenzylammonium chloride, triphenylisobutylammonium chloride, triphenylbenzylammonium chloride, ammonium bromide , Tetramethylammonium bromide, tetraethyl bromide Ammonium, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrahexylammonium bromide, tetraoctylammonium bromide, tetraphenylammonium bromide, triethylmethylammonium bromide, triethylhexylammonium bromide, trioctylmethylammonium bromide , Trioctylbutylammonium bromide, trioctylbenzylammonium bromide, trimethylbenzylammonium bromide, tributylbenzylammonium bromide, triphenylisobutylammonium bromide, triphenylbenzylammonium bromide, ammonium iodide, tetramethylammonium iodide Tetraethylammonium iodide, Tetrapropylammonium iodide, Tetrabutylammonium iodide, Tetrahedium iodide Silammonium, tetraoctylammonium iodide, tetraphenylammonium iodide, triethylmethylammonium iodide, triethylhexylammonium iodide, trioctylmethylammonium iodide, trioctylbutylammonium iodide, trioctylbenzylammonium iodide, iodide Ammonium halides such as trimethylbenzylammonium iodide, tributylbenzylammonium iodide, triphenylisobutylammonium iodide, triphenylbenzylammonium iodide; ammonium hydrochloride, ammonium phosphate, ammonium borate, ammonium hydrofluoride, ammonium sulfate, ammonium nitrate, Inorganic ammonium such as ammonium silicate and ammonium phosphate: ammonium formate, acetic acid Organic acid ammonium such as ammonium, ammonium propionate, ammonium malate, ammonium sulfamate; tetraphenylphosphonium chloride, tetraphenylphosphonium iodide, tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraiodide An inorganic acid phosphonium such as butylphosphonium; an organic acid phosphonium such as tetrabutylphosphonium acetate can be used. These nonmetallic coagulants may be used alone or in combination of two or more.
　前記非金属凝固剤としては、前記した中でも、水性ウレタン樹脂組成物の増粘、及び凝固速度が速く、毛細管現象による樹脂の繊維付着・拘束を抑制できる理由から、より一層優れた加工布風合いが得られる点から、無機酸アンモニウムを用いることが好ましく、硫酸アンモニウムを用いることがより好ましい。 Among the above-mentioned non-metal coagulants, among the above-mentioned, the viscosity of the aqueous urethane resin composition and the coagulation speed are fast, and because of the ability to suppress resin fiber adhesion / restraint due to capillary phenomenon, an even better work cloth texture is obtained. In view of the obtained point, it is preferable to use inorganic acid ammonium, and it is more preferable to use ammonium sulfate.
　前記非金属凝固剤水溶液に用いる水としては、例えば、イオン交換水、蒸留水、水道水等を用いることができる。これらの水は単独で用いても２種以上を併用してもよい。 As the water used for the non-metal coagulant aqueous solution, for example, ion exchange water, distilled water, tap water, or the like can be used. These waters may be used alone or in combination of two or more.
　前記非金属凝固剤の含有量としては、前記非金属凝固剤水溶液中、１～５０質量％の範囲であることが好ましく、２～２０質量％の範囲であることがより好ましい。 The content of the nonmetallic coagulant is preferably in the range of 1 to 50% by mass, more preferably in the range of 2 to 20% by mass in the nonmetallic coagulant aqueous solution.
　本発明である凝固物の製造方法の具体例としては、例えば、繊維基材を、水性ウレタン樹脂組成物中に含浸し、次いで、この含浸基材を更に１５℃以上の前記非金属凝固剤水溶液を含む凝固浴に浸漬させることで、ウレタン樹脂の凝固物を製造する方法；繊維基材を、１５℃以上の前記非金属凝固剤水溶液を含む凝固浴に含浸し、次いで、この含浸基材を更に水性ウレタン樹脂組成物中に浸漬させることで、ウレタン樹脂の凝固物を製造する方法等が挙げられる。この中で、前者の方法を使用した場合には、繊維基材の内部にまでウレタン樹脂の凝固物が充填し、繊維基材に前記凝固物が絡み付いた状態が形成されるため、皮革様シートの含浸層として好適に使用することができる。また、後者の方法を使用した場合には、繊維基材の表面及び表面付近の内部にウレタン凝固物層が形成されるため、手袋の製造に好適に使用することができる。 As a specific example of the method for producing a coagulated product according to the present invention, for example, a fiber base material is impregnated in an aqueous urethane resin composition, and then the impregnated base material is further heated to 15 ° C. or higher. A method of producing a solidified product of urethane resin by immersing in a coagulation bath containing: a fiber base material is impregnated in a coagulation bath containing the nonmetallic coagulant aqueous solution at 15 ° C. or higher, and then the impregnated base material is Furthermore, the method etc. which manufacture the solidified material of a urethane resin by immersing in an aqueous urethane resin composition are mentioned. In this case, when the former method is used, the solidified urethane resin is filled up to the inside of the fiber base material, and the state where the solidified material is entangled with the fiber base material is formed. It can be suitably used as an impregnated layer. In addition, when the latter method is used, a urethane coagulated material layer is formed on the surface of the fiber substrate and in the vicinity of the surface, and therefore, it can be suitably used for manufacturing gloves.
　前記繊維基材としては、例えば、不織布、織布、編み物等を使用することができる。前記繊維基材を構成するものとしては、例えば、ポリエステル繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、それらの混紡繊維等を使用することができる。 As the fiber base material, for example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used. For example, polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, and blended fibers thereof are used as the fiber substrate. can do.
　前記繊維基材を、前記水性ウレタン樹脂組成物中に含浸する方法としては、例えば、前記繊維基材を、前記水性ウレタン樹脂組成物を貯留した槽に直接含浸し、その後マングル等で余分なものを絞る方法が挙げられる。前記含浸時間としては、例えば、１～３０分の範囲である。 Examples of the method for impregnating the fibrous base material into the aqueous urethane resin composition include, for example, impregnating the fibrous base material directly into a tank in which the aqueous urethane resin composition is stored, and then using an extra mangle or the like. The method of narrowing down is mentioned. The impregnation time is, for example, in the range of 1 to 30 minutes.
　次いで、この含浸基材を取り出し、更に前記１５℃以上の前記非金属凝固剤水溶液を含む凝固浴に浸漬することで、水性ウレタン樹脂組成物中のウレタン樹脂が凝固され、不織布の表面や内部に凝固物が付着した状態の繊維基材が得られる。この際の含浸・凝固時間としては、例えば１～３０分の範囲である。 Next, the impregnated base material is taken out, and further immersed in a coagulation bath containing the non-metallic coagulant aqueous solution at 15 ° C. or higher, so that the urethane resin in the aqueous urethane resin composition is coagulated, and on the surface or inside of the nonwoven fabric. A fiber base material in a state where a coagulum is adhered is obtained. The impregnation / solidification time at this time is, for example, in the range of 1 to 30 minutes.
　ウレタン樹脂の凝固物を有する繊維基材は、必要に応じて、前記含浸・凝固後に例えば１０分～２時間の間流水に浸し、不要な凝固剤を洗浄除去することができる。 If necessary, the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
　また、前記繊維基材を、前記１５℃以上の前記非金属凝固剤水溶液を含む凝固浴に含浸する方法としては、例えば、前記繊維基材を、前記１５℃以上の前記非金属凝固剤水溶液を含む凝固浴に直接含浸し、マングル等で余分なものを絞る方法が挙げられる。前記含浸時間としては、例えば、１～３０分の範囲である。 Moreover, as a method of impregnating the fibrous base material into the coagulation bath containing the non-metallic coagulant aqueous solution at 15 ° C. or higher, for example, the non-metallic coagulant aqueous solution at 15 ° C. or higher is used as the fibrous base material. A method of directly impregnating the coagulation bath containing the mixture and squeezing excess with a mangle or the like can be mentioned. The impregnation time is, for example, in the range of 1 to 30 minutes.
　次いで、この含浸基材を取り出し、更に前記水性ウレタン樹脂組成物中に浸漬することで、水性ウレタン樹脂組成物中のウレタン樹脂が凝固され、繊維基材の表層及び表層付近の内部にウレタン凝固物層が形成された繊維基材が得られる。この際の含浸・凝固時間としては、例えば１～３０分の範囲である。 Next, the impregnated base material is taken out and further immersed in the aqueous urethane resin composition, so that the urethane resin in the aqueous urethane resin composition is solidified, and the urethane solidified material is formed in the surface layer and the vicinity of the surface layer of the fiber base material. A fiber substrate on which a layer is formed is obtained. The impregnation / solidification time at this time is, for example, in the range of 1 to 30 minutes.
　ウレタン樹脂の凝固物を有する繊維基材は、必要に応じて、前記含浸・凝固後に例えば１０分～２時間の間流水に浸し、不要な凝固剤を洗浄除去することができる。 If necessary, the fiber base material having a solidified urethane resin can be immersed in running water for 10 minutes to 2 hours after the impregnation and solidification to wash away unnecessary coagulants.
　本発明において使用することができる水性ウレタン樹脂組成物としては、例えば、水性ウレタン樹脂（Ａ）、及び水性媒体（Ｂ）を含有するものを用いることができる。 As the aqueous urethane resin composition that can be used in the present invention, for example, those containing an aqueous urethane resin (A) and an aqueous medium (B) can be used.
　前記水性ウレタン樹脂（Ａ）は、後述する水性媒体（Ｂ）中に分散等し得るものであり、例えば、アニオン性基、カチオン性基、ノニオン性基等の親水性基を有する水性ウレタン樹脂；乳化剤で強制的に水性媒体（Ｂ）中に分散した水性ウレタン樹脂などを用いることができる。これらの水性ウレタン樹脂（Ａ）は単独で用いても２種以上を併用してもよい。これらの中でも、製造安定性の点から、親水性基を有する水性ウレタン樹脂を用いることが好ましく、電気二重層圧縮効果により前記非金属凝固剤に対し凝固性がより一層向上する点、及び繊維基材内部にまでウレタン樹脂が充填・絡み付きやすく、風合いがより一層向上する点から、アニオン性基を有する水性ウレタン樹脂を用いることがより好ましい。 The aqueous urethane resin (A) can be dispersed in an aqueous medium (B) described later. For example, the aqueous urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; An aqueous urethane resin or the like that is forcibly dispersed in the aqueous medium (B) with an emulsifier can be used. These aqueous urethane resins (A) may be used alone or in combination of two or more. Among these, from the viewpoint of production stability, it is preferable to use a water-based urethane resin having a hydrophilic group, the solidification property of the non-metal coagulant is further improved by the electric double layer compression effect, and the fiber group. It is more preferable to use an aqueous urethane resin having an anionic group from the viewpoint that the urethane resin is easily filled and entangled into the material and the texture is further improved.
　前記アニオン性基を有する水性ウレタン樹脂を得る方法としては、例えば、カルボキシル基を有する化合物及びスルホニル基を有する化合物からなる群より選ばれる１種以上の化合物を原料として用いる方法が挙げられる。 Examples of a method for obtaining the aqueous urethane resin having an anionic group include a method using, as a raw material, one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group.
　前記カルボキシル基を有する化合物としては、例えば、２，２’－ジメチロールプロピオン酸、２，２’－ジメチロールブタン酸、２，２’－ジメチロール酪酸、２，２’－ジメチロールプロピオン酸、２，２’－吉草酸等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the compound having a carboxyl group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolpropionic acid, , 2'-valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.
　前記スルホニル基を有する化合物としては、例えば、３，４－ジアミノブタンスルホン酸、３，６－ジアミノ－２－トルエンスルホン酸、２，６－ジアミノベンゼンスルホン酸、Ｎ－（２－アミノエチル）－２－アミノエチルスルホン酸等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- 2-Aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.
　前記カルボキシル基及びスルホニル基は、水性ウレタン樹脂組成物中で、一部又は全部が塩基性化合物に中和されていてもよい。前記塩基性化合物としては、例えば、アンモニア、トリエチルアミン、ピリジン、モルホリン等の有機アミン；モノエタノールアミン、ジメチルエタノールアミン等のアルカノールアミン；ナトリウム、カリウム、リチウム、カルシウム等を含む金属塩基化合物などを用いることができる。 The carboxyl group and sulfonyl group may be partially or completely neutralized with a basic compound in the aqueous urethane resin composition. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. Can do.
　前記カチオン性基を有する水性ウレタン樹脂を得る方法としては、例えば、アミノ基を有する化合物の１種又は２種以上を原料として用いる方法が挙げられる。 Examples of the method for obtaining the aqueous urethane resin having a cationic group include a method using one or more compounds having an amino group as a raw material.
　前記アミノ基を有する化合物としては、例えば、トリエチレンテトラミン、ジエチレントリアミン等の１級及び２級アミノ基を有する化合物；Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン等のＮ－アルキルジアルカノールアミン、Ｎ－メチルジアミノエチルアミン、Ｎ－エチルジアミノエチルアミン等のＮ－アルキルジアミノアルキルアミンなどの３級アミノ基を有する化合物などを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl. A compound having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.
　前記ノニオン性基を有する水性ウレタン樹脂を得る方法としては、例えば、オキシエチレン構造を有する化合物の１種又は２種以上を原料として用いる方法が挙げられる。 Examples of the method for obtaining the aqueous urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
　前記オキシエチレン構造を有する化合物としては、例えば、ポリオキシエチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール等のオキシエチレン構造を有するポリエーテルポリオールを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.
　前記強制的に水性媒体（Ｂ）中に分散する水性ウレタン樹脂を得る際に用いることができる乳化剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン性乳化剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、ナフタレンスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルフォン酸ナトリウム塩等のアニオン性乳化剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン性乳化剤などを用いることができる。これらの乳化剤は単独で用いても２種以上を併用してもよい。 Examples of the emulsifier that can be used in obtaining the aqueous urethane resin that is forcibly dispersed in the aqueous medium (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Nonionic emulsifiers such as polyoxyethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymer; fatty acid salt such as sodium oleate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl sulfosuccinate, naphthalene sulfonate Anionic emulsifiers such as salts, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; alkyl amine salts, alkyl trimethyl Ammonium salts, such as cationic emulsifiers such as alkyl dimethyl benzyl ammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.
　前記水性ウレタン樹脂（Ａ）としては、具体的には、ポリイソシアネート（ａ１）、ポリオール（ａ２）、前記した親水性基を有する水性ウレタン樹脂を製造するために用いる原料、及び必要に応じて鎖伸長剤（ａ３）を原料として得られるものを用いることができる。これらの反応は公知のウレタン化反応を用いることができる。 Specifically as said water-based urethane resin (A), the polyisocyanate (a1), polyol (a2), the raw material used in order to manufacture the water-based urethane resin which has an above described hydrophilic group, and a chain | strand as needed What can be obtained by using an extending | stretching agent (a3) as a raw material can be used. These reactions can use known urethanization reactions.
　前記水性ウレタン樹脂（Ａ）としては、本発明で用いる前記凝固剤への溶解性が低く、良好な凝固状態を維持しやすい点、及び繊維基材内部にまでウレタン樹脂が充填・絡み付きやすく、風合いがより一層向上する点から、芳香環を有する水性ウレタン樹脂を用いることが好ましい。 As the water-based urethane resin (A), the solubility in the coagulant used in the present invention is low, it is easy to maintain a good solidified state, and the urethane resin is easily filled and entangled even inside the fiber base material. It is preferable to use a water-based urethane resin having an aromatic ring from the viewpoint of further improving.
　前記水性ウレタン樹脂（Ａ）の芳香環の含有量としては、０．８～８ｍｏｌ／ｋｇの範囲であることが好ましく、１～６ｍｏｌ／ｋｇの範囲であることがより好ましい。 The content of the aromatic ring of the aqueous urethane resin (A) is preferably in the range of 0.8 to 8 mol / kg, more preferably in the range of 1 to 6 mol / kg.
　前記芳香環は、原料であるポリイソシアネート（ａ１）、及びポリオール（ａ２）のいずれかから供給されるが、原料入手の容易性、及び製造安定性の点から、ポリイソシアネート（ａ２）から供給されることが好ましく、すなわち芳香族ポリイソシアネートを用いることが好ましい。 The aromatic ring is supplied from either the polyisocyanate (a1) or the polyol (a2) as a raw material, but is supplied from the polyisocyanate (a2) from the viewpoint of easy availability of the raw material and production stability. That is, it is preferable to use an aromatic polyisocyanate.
　前記芳香族ポリイソシアネートとしては、例えば、フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、カルボジイミド化ジフェニルメタンポリイソシアネート等を用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、原料入手の容易性、及び風合いの点から、ジフェニルメタンジイソアシアネートを用いることが好ましい。 Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use diphenylmethane diisocyanate from the viewpoint of easy availability of raw materials and texture.
　前記ポリイソシアネート（ａ１）に用いることができるその他のポリイソシアネートとしては、例えば、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ダイマー酸ジイソシアネート、ノルボルネンジイソシアネート等の脂肪族または脂環式ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。 Examples of other polyisocyanates that can be used for the polyisocyanate (a1) include hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and dimer acid diisocyanate. An aliphatic or alicyclic polyisocyanate such as norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.
　前記ポリオール（ａ２）としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリアクリルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。 As the polyol (a2), for example, polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more.
　前記ポリオール（ａ２）の数平均分子量としては、得られる皮膜の機械的強度の点から、５００～８，０００の範囲であることが好ましく、８００～４，０００の範囲であることがより好ましい。なお、前記ポリオール（ａ２）の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。 The number average molecular weight of the polyol (a2) is preferably in the range of 500 to 8,000, more preferably in the range of 800 to 4,000, from the viewpoint of the mechanical strength of the resulting film. In addition, the number average molecular weight of the said polyol (a2) shows the value obtained by measuring on condition of the following by gel permeation column chromatography (GPC) method.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
　前記鎖伸長剤（ａ３）としては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、１，２－シクロヘキサンジアミン、１，３－シクロヘキサンジアミン、１，４－シクロヘキサンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン、ヒドラジン等のアミノ基を有する鎖伸長剤；エチレングリコール、ジエチレンリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール、ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、トリメチロールプロパン等の水酸基を有する鎖伸長剤などを用いることができる。これらの鎖伸長剤は単独で用いても２種以上を併用してもよい。これらの中でも、オイルグリップ性及び耐薬品性をより一層向上できる点から、水酸基を有する鎖伸長剤を用いることが好ましい。 Examples of the chain extender (a3) include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1, Amino groups such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine, etc. Chain extender having: ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharo Scan, glycol, glycerine, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and the like can be used a chain extender having a hydroxyl group such as trimethylol propane. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint that oil grip properties and chemical resistance can be further improved.
　前記鎖伸長剤（ａ３）を用いる場合の使用量としては、皮膜の耐久性をより一層向上できる点から、前記ポリイソシアネート（ａ１）、前記ポリオール（ａ２）及び前記鎖伸長剤（ａ３）の合計質量中０．５～２０質量％の範囲であることが好ましく、１～１０質量％の範囲であることがより好ましい。 The amount used in the case of using the chain extender (a3) is the sum of the polyisocyanate (a1), the polyol (a2) and the chain extender (a3) from the point that the durability of the film can be further improved. It is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 1 to 10% by mass.
　前記水性ウレタン樹脂（Ａ）としては、風合いを損なわず、更に継時的な変色を制御できる点から、尿素結合の含有量が１．２ｍｏｌ／ｋｇ以下であることが好ましい。 The aqueous urethane resin (A) preferably has a urea bond content of 1.2 mol / kg or less from the viewpoint that the discoloration over time can be controlled without impairing the texture.
　前記尿素結合は、前記アミノ基を有する鎖伸長剤又はイソシアネートが水と反応し生成したアミンと前記ポリイソシアネートが反応した場合に生成するものであるから、アミノ基を有する鎖伸長剤の使用量を調整し、さらに乳化操作をする前にイソシアネートを全てウレタン化させることにより、水性ウレタン樹脂（Ａ）の尿素結合の含有量を調整することができる。なお、前記尿素結合の含有量は、下記一般式（１）で計算した値を示す。 Since the urea bond is formed when the polyisocyanate reacts with a chain extender having an amino group or an amine formed by reacting isocyanate with water, the amount of the chain extender having an amino group used is reduced. The urea bond content of the aqueous urethane resin (A) can be adjusted by adjusting and further urethanizing the isocyanate before emulsification. The urea bond content indicates a value calculated by the following general formula (1).
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　前記水性ウレタン樹脂（Ａ）の製造方法としては、例えば、前記ポリイソシアネート（ａ１）と前記ポリオール（ａ２）とを反応させることによって、イソシアネート基を有するウレタンプレポリマーを製造し、次いで、必要に応じて前記ウレタンプレポリマーと、前記鎖伸長剤（ａ３）とを反応させることによって製造する方法；前記ポリイソシアネート（ａ１）、前記ポリオール（ａ２）及び必要に応じて前記鎖伸長剤（ａ３）を一括に仕込み反応させる方法等が挙げられる。これらの反応は、例えば５０～１００℃で３～１０時間行うことが挙げられる。 As a manufacturing method of the said water-based urethane resin (A), the urethane prepolymer which has an isocyanate group is manufactured by making the said polyisocyanate (a1) and the said polyol (a2) react, for example, Then, as needed The urethane prepolymer and the chain extender (a3) are reacted with each other; the polyisocyanate (a1), the polyol (a2) and, if necessary, the chain extender (a3) in a lump. And the like. These reactions can be carried out, for example, at 50 to 100 ° C. for 3 to 10 hours.
　前記ポリオール（ａ２）が有する水酸基並びに前記鎖伸長剤（ａ３）が有する水酸基及び／又はアミノ基の合計と、前記芳香族ポリイソシアネート（ａ１）が有するイソシアネート基とのモル比［（イソシアネート基）／（水酸基及び／又はアミノ基）］としては、０．８～１．２の範囲であることが好ましく、０．９～１．１の範囲であることがより好ましい。 The molar ratio of the total hydroxyl group and / or amino group of the polyol (a2) and the chain extender (a3) to the isocyanate group of the aromatic polyisocyanate (a1) [(isocyanate group) / (Hydroxyl group and / or amino group)] is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
　前記水性ウレタン樹脂（Ａ）を製造する際には、前記水性ウレタン樹脂（Ａ）に残存するイソシアネート基を失活させることが好ましい。前記イソシアネート基を失活させる場合には、メタノール等の水酸基を１個有するアルコールを用いることが好ましい。前記アルコールの使用量としては、水性ウレタン樹脂（Ａ）１００質量部に対し、０．００１～１０質量部の範囲であることが好ましい。 When the aqueous urethane resin (A) is produced, it is preferable to deactivate the isocyanate group remaining in the aqueous urethane resin (A). When the isocyanate group is deactivated, it is preferable to use an alcohol having one hydroxyl group such as methanol. The amount of the alcohol used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A).
　また、前記ウレタン樹脂（Ａ）を製造する際には、有機溶剤を用いてもよい。前記有機溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン化合物；テトラヒドロフラン、ジオキサン等のエーテル化合物；酢酸エチル、酢酸ブチル等の酢酸エステル化合物；アセトニトリル等のニトリル化合物；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド化合物などを用いることができる。これらの有機溶媒は単独で用いても２種以上を併用してもよい。なお、前記有機溶剤は、水性ウレタン樹脂組成物を得る際には蒸留法等によって除去されることが好ましい。 Further, when the urethane resin (A) is produced, an organic solvent may be used. Examples of the organic solvent include ketone compounds such as acetone and methyl ethyl ketone; ether compounds such as tetrahydrofuran and dioxane; acetate compounds such as ethyl acetate and butyl acetate; nitrile compounds such as acetonitrile; dimethylformamide and N-methylpyrrolidone Amide compounds and the like can be used. These organic solvents may be used alone or in combination of two or more. The organic solvent is preferably removed by a distillation method or the like when obtaining an aqueous urethane resin composition.
　前記水性媒体（Ｂ）としては、例えば、水、水と混和する有機溶剤、これらの混合物等を用いることができる。前記水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ－及びイソプロパノール等のアルコール溶媒；アセトン、メチルエチルケトン等のケトン溶媒；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール溶媒；ポリアルキレングリコールのアルキルエーテル溶媒；Ｎ－メチル－２－ピロリドン等のラクタム溶媒等を用いることができる。これらの水性媒体は単独で用いても２種以上を併用してもよい。これらの中でも、安全性及び環境負荷の軽減化の点から、水のみ、又は、水及び水と混和する有機溶剤との混合物を用いることが好ましく、水のみ用いることがより好ましい。 As the aqueous medium (B), for example, water, an organic solvent miscible with water, a mixture thereof, or the like can be used. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n- and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ether solvents: lactam solvents such as N-methyl-2-pyrrolidone and the like can be used. These aqueous media may be used alone or in combination of two or more. Among these, it is preferable to use only water or a mixture of water and an organic solvent miscible with water, and more preferable to use only water from the viewpoint of safety and reduction of environmental load.
　前記水性ウレタン樹脂（Ａ）と前記水性媒体（Ｂ）との質量比［（Ａ）／（Ｂ）］としては、作業性の点から、１０／８０～７０／３０の範囲であることが好ましく、２０／８０～６０／４０の範囲であることがより好ましい。 The mass ratio [(A) / (B)] between the aqueous urethane resin (A) and the aqueous medium (B) is preferably in the range of 10/80 to 70/30 from the viewpoint of workability. The range of 20/80 to 60/40 is more preferable.
　本発明で用いる水性ウレタン樹脂組成物は、前記ウレタン樹脂（Ａ）、及び前記水性媒体（Ｂ）の他に、必要に応じて、その他の添加剤を含有してもよい。 The aqueous urethane resin composition used in the present invention may contain other additives as needed in addition to the urethane resin (A) and the aqueous medium (B).
　前記その他の添加剤としては、例えば、乳化剤、中和剤、増粘剤、架橋剤、ウレタン化触媒、シランカップリング剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、熱安定剤、耐光安定剤、蛍光増白剤、発泡剤、顔料、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、難燃剤、吸水剤、吸湿剤、消臭剤、整泡剤、ブロッキング防止剤、加水分解防止剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives include, for example, an emulsifier, a neutralizer, a thickener, a crosslinking agent, a urethanization catalyst, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, and light resistance. Stabilizer, fluorescent brightener, foaming agent, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, flame retardant, water absorbent, moisture absorbent, extinguishing agent An odorant, a foam stabilizer, an antiblocking agent, an hydrolysis inhibitor, and the like can be used. These additives may be used alone or in combination of two or more.
　前記乳化剤は、前記強制的に水性媒体（Ｂ）中に分散する水性ウレタン樹脂を得る際に用いることができる乳化剤と同様のものを用いることができる。これらの乳化剤は単独で用いても２種以上を併用してもよい。これらの中でも、水性ウレタン樹脂（Ａ）の水分散安定性を向上できる点、及び繊維基材内部にまでウレタン樹脂が充填・絡み付きやすく、風合いがより一層向上する点から、ノニオン性乳化剤を用いることが好ましい。 The emulsifier may be the same as the emulsifier that can be used to obtain the aqueous urethane resin that is forcibly dispersed in the aqueous medium (B). These emulsifiers may be used alone or in combination of two or more. Among these, a nonionic emulsifier is used from the point that the water dispersion stability of the water-based urethane resin (A) can be improved, and the urethane resin is easily filled / entangled into the fiber base material, and the texture is further improved. Is preferred.
　前記乳化剤を用いる場合の使用量としては、水分散安定性及び風合いの点から、前記水性ウレタン樹脂（Ａ）１００質量部に対して、０．１～３０質量部の範囲であることが好ましく、１～１０質量部の範囲であることがより好ましい。 The amount used in the case of using the emulsifier is preferably in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A) from the viewpoint of water dispersion stability and texture. A range of 1 to 10 parts by mass is more preferable.
　前記中和剤は、前記水性ウレタン樹脂（Ａ）として、アニオン性の水性ウレタン樹脂を用いた場合に、そのカルボキシル基を中和するものであり、例えば、水酸化ナトリウム、水酸化カリウム等の不揮発性塩基；トリメチルアミン、トリエチルアミン、ジメチルエタノールアミン、メチルジエタノールアミン、トリエタノール等の三級アミン化合物などを用いることができる。これらの中和剤は単独で用いても２種以上を併用してもよい。 The neutralizing agent neutralizes the carboxyl group when an anionic aqueous urethane resin is used as the aqueous urethane resin (A). For example, the neutralizing agent is non-volatile such as sodium hydroxide or potassium hydroxide. A tertiary amine compound such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, or triethanol; These neutralizing agents may be used alone or in combination of two or more.
　前記中和剤の使用量としては、前記水性ウレタン樹脂（Ａ）に含まれるカルボキシル基のモル数に対して０．８～１．２倍の範囲であることが好ましい。 The amount of the neutralizing agent used is preferably in the range of 0.8 to 1.2 times the number of moles of carboxyl groups contained in the aqueous urethane resin (A).
　以上、本発明で使用する水性ウレタン樹脂組成物としては、前記凝固剤により一層凝固しやすくなる点、繊維基材内部にまで充填・絡み付きやすく、風合いがより一層向上する点、及び水分散安定性が向上する点から、芳香族ポリイソシアネート、ポリオール及び鎖伸長剤を反応させて得られたアニオン性基を有する水性ウレタン樹脂（Ａ）、水性媒体（Ｂ）、及びノニオン性乳化剤を含有する水性ウレタン樹脂組成物を用いることが好ましい。 As described above, the aqueous urethane resin composition used in the present invention is more easily coagulated by the coagulant, more easily filled and entangled inside the fiber base material, further improved in texture, and water dispersion stability. Water-based urethane resin containing an anionic group obtained by reacting an aromatic polyisocyanate, a polyol and a chain extender (A), an aqueous medium (B), and a nonionic emulsifier It is preferable to use a resin composition.
　以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［合成例１］水性ウレタン樹脂組成物（Ｘ－１）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリカーボネートポリオール（「ニッポラン９８０Ｒ」日本ポリウレタン株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２’－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ジフェニルメタンジイソシアネート３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させて水性ウレタン樹脂（Ａ－１）のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ（以下、「ＨＬＢ」と略記する）；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記水性ウレタン樹脂（Ａ－１）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分４０質量％の水性ウレタン樹脂組成物（Ｘ－１）を得た。 [Synthesis Example 1] Preparation of Aqueous Urethane Resin Composition (X-1) Polycarbonate polyol ("Nipporan 980R" manufactured by Nippon Polyurethane Co., Ltd. in the presence of 3,281 parts by mass of methyl ethyl ketone and 0.1 part by mass of stannous octylate , Number average molecular weight; 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20,000 mPa After reacting at 70 ° C. until reaching s, 3 parts by mass of methanol was added to stop the reaction, and a methyl ethyl ketone solution of the aqueous urethane resin (A-1) was obtained. The urethane resin solution was mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (Hydrophile-Lipophile Balance (hereinafter abbreviated as “HLB”); 14) and 13 parts by mass of triethylamine. An emulsified liquid in which the aqueous urethane resin (A-1) was dispersed in water was obtained by adding part by mass and emulsifying by phase inversion emulsification.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (X-1) having a nonvolatile content of 40% by mass.
［合成例２］水性ウレタン樹脂組成物（Ｘ－２）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエーテルポリオール（「ＰＴＭＧ２０００」三菱化型株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２’－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ジフェニルメタンジイソシアネート３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させて水性ウレタン樹脂（Ａ－２）のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（ＨＬＢ；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記水性ウレタン樹脂（Ａ－２）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分４０質量％の水性ウレタン樹脂組成物（Ｘ－２）を得た。 Synthesis Example 2 Preparation of Aqueous Urethane Resin Composition (X-2) Polyether polyol (“PTMG2000” Mitsubishi Kasei Co., Ltd.) in the presence of 3,281 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate Manufactured, number average molecular weight: 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20, After reacting at 70 ° C. until reaching 000 mPa · s, 3 parts by mass of methanol was added to stop the reaction to obtain a methyl ethyl ketone solution of the aqueous urethane resin (A-2). The urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion-exchanged water is added to effect phase inversion emulsification. An emulsion in which the urethane resin (A-2) was dispersed in water was obtained.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (X-2) having a nonvolatile content of 40% by mass.
［合成例３］水性ウレタン樹脂組成物（Ｘ－３）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリエステルポリオール（「プラクセル２２０」株式会社ダイセル製、数平均分子量；２，０００）１，０００質量部と、２，２’－ジメチロールプロピオン酸１７質量部と、エチレングリコール４７質量部と、ジフェニルメタンジイソシアネート３４４質量部とを溶液粘度が２０，０００ｍＰａ・ｓに達するまで７０℃で反応させた後、メタノール３質量部を加えて反応を停止させて水性ウレタン樹脂（Ａ－３）のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル（ＨＬＢ；１４）７０質量部と、トリエチルアミン１３質量部を混合させた後に、イオン交換水８００質量部を加えて転相乳化させることで前記水性ウレタン樹脂（Ａ－３）が水に分散した乳化液を得た。
　次いで、前記乳化液からメチルエチルケトンを留去することによって、不揮発分４０質量％の水性ウレタン樹脂組成物（Ｘ－３）を得た。 Synthesis Example 3 Preparation of Aqueous Urethane Resin Composition (X-3) In the presence of 3,281 parts by mass of methyl ethyl ketone and 0.1 part by mass of stannous octylate, polyester polyol (“Placcel 220” manufactured by Daicel Corporation, Number average molecular weight; 2,000) 1,000 parts by mass, 17 parts by mass of 2,2′-dimethylolpropionic acid, 47 parts by mass of ethylene glycol, and 344 parts by mass of diphenylmethane diisocyanate have a solution viscosity of 20,000 mPa · After reacting at 70 ° C. until reaching s, 3 parts by mass of methanol was added to stop the reaction, and a methyl ethyl ketone solution of an aqueous urethane resin (A-3) was obtained. The urethane resin solution is mixed with 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB; 14) and 13 parts by mass of triethylamine, and then 800 parts by mass of ion-exchanged water is added to effect phase inversion emulsification. An emulsion in which the urethane resin (A-3) was dispersed in water was obtained.
Subsequently, methyl ethyl ketone was distilled off from the emulsion to obtain an aqueous urethane resin composition (X-3) having a nonvolatile content of 40% by mass.
［合成例４］水性ウレタン樹脂組成物（Ｘ－４）の調製
　メチルエチルケトン３，２８１質量部及びオクチル酸第一錫０．１質量部の存在下、ポリカーボネートポリオール（「ニッポラン９８０Ｒ」日本ポリウレタン株式会社製、数平均分子量；２，０００）１，０００質量部と、２，２’－ジメチロールプロピオン酸１５質量部と、ジシクロヘキシルメタンジイソシアネート２００質量部とを、それらの反応生成物の質量に対するイソシアネート基の質量割合（ＮＣＯ％）が１．１３質量％に達するまで７０℃で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマー（Ｘ’－４）のメチルエチルケトン溶液を得た。
　次いで、前記ウレタンプレポリマー（Ｘ’－４）のメチルエチルケトン溶液２，８５６６質量部と水２，５６６質量部とポリオキシエチレンジスチレン化フェニルエーテル（ＨＬＢ＝１４）７０質量部を混合し、転相乳化することによって、前記ウレタンプレポリマーが水に分散した乳化液を得た。
　得られた乳化液と、イソホロンジアミン２６質量部を含む鎖伸長剤水溶液１３５質量部とを混合し鎖伸長反応することによってウレタン樹脂組成物を得た。
　次いで、前記ウレタン樹脂組成物からメチルエチルケトンを留去することによって、不揮発分４０質量％のウレタン樹脂組成物（Ｘ－４）を得た。 [Synthesis Example 4] Preparation of Aqueous Urethane Resin Composition (X-4) Polycarbonate polyol ("Nipporan 980R" manufactured by Nippon Polyurethane Co., Ltd. in the presence of 3,281 parts by weight of methyl ethyl ketone and 0.1 part by weight of stannous octylate , Number average molecular weight; 2,000) 1,000 parts by mass, 15 parts by mass of 2,2′-dimethylolpropionic acid, and 200 parts by mass of dicyclohexylmethane diisocyanate, with respect to the mass of the reaction product, By reacting at 70 ° C. until the mass ratio (NCO%) reached 1.13 mass%, a methyl ethyl ketone solution of urethane prepolymer (X′-4) having an isocyanate group at the terminal was obtained.
Next, 2,8566 parts by mass of a methyl ethyl ketone solution of the urethane prepolymer (X′-4), 2,566 parts by mass of water, and 70 parts by mass of polyoxyethylene distyrenated phenyl ether (HLB = 14) were mixed, and phase inversion was performed. By emulsifying, an emulsion in which the urethane prepolymer was dispersed in water was obtained.
The obtained emulsion and 135 parts by mass of a chain extender aqueous solution containing 26 parts by mass of isophoronediamine were mixed and subjected to a chain extension reaction to obtain a urethane resin composition.
Next, methyl ethyl ketone was distilled off from the urethane resin composition to obtain a urethane resin composition (X-4) having a nonvolatile content of 40% by mass.
［実施例１］
　合成例１で得られた水性ウレタン樹脂組成物（Ｘ－１）１００質量部、増粘剤（Ｂｏｒｃｈｅｒ社製「Ｂｏｒｃｈ　Ｇｅｌ　Ｌ７５Ｎ」）５質量部、カルボジイミド架橋剤（日清紡ケミカル株式会社製「カルボジライトＳＶ－０２」）４質量部、イオン交換水２００質量部をメカニカルミキサーにて２，０００ｒｐｍで２分間撹拌し、次いで真空脱泡機で脱泡させることで、配合液を調製した。
　次いで、不織布（目付２５０ｇ／ｍ２）を前記配合液に含浸させた後、ゴムローラーマングルを用いて含浸量が２００％となるように不要な配合液を絞り取った。次いで、配合液を含ませた不織布を６０℃に加熱した５質量％の硫酸アンモニウム水溶液の凝固浴に３分浸漬させて、配合液を凝固させた。最後に、１００℃の熱風乾燥機にて３０分乾燥させて凝固物を有する繊維基材を得た。 [Example 1]
100 parts by mass of the aqueous urethane resin composition (X-1) obtained in Synthesis Example 1, 5 parts by mass of a thickener (“Borch Gel L75N” manufactured by Borcher), a carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) −02 ”) 4 parts by mass and 200 parts by mass of ion-exchanged water were stirred with a mechanical mixer at 2,000 rpm for 2 minutes, and then deaerated with a vacuum deaerator to prepare a blended solution.
Next, after impregnating the non-woven fabric (with a basis weight of 250 g / m 2 ) into the compounded solution, an unnecessary compounded solution was squeezed out using a rubber roller mangle so that the amount of impregnation was 200%. Next, the blended solution was solidified by immersing the non-woven fabric containing the blended solution in a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C. for 3 minutes. Finally, it was dried with a hot air dryer at 100 ° C. for 30 minutes to obtain a fiber base material having a coagulum.
［実施例２～４］
　用いる水性ウレタン樹脂組成物の種類を表に示す通り変更した以外は、実施例１と同様にして凝固物を有する繊維基材を得た。 [Examples 2 to 4]
A fiber base material having a coagulum was obtained in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used was changed as shown in the table.
［実施例５］
　凝固浴の温度を２２℃に変更した以外は、実施例１と同様にして凝固物を有する繊維基材を得た。 [Example 5]
A fiber base material having a coagulated product was obtained in the same manner as in Example 1 except that the temperature of the coagulation bath was changed to 22 ° C.
［比較例１］
　合成例１で得られた水性ウレタン樹脂組成物（Ｘ－１）１００質量部、塩化ナトリウム２質量％水溶液１００質量部とをメカニカルミキサーを用い２，０００ｒｐｍの条件で２分間撹拌することによって、それぞれ、含浸用の水性ウレタン樹脂組成物を調製した。
　次いで、不織布（目付２５０ｇ／ｍ２）を、前記で得た含浸用の水性ウレタン樹脂組成物が入った槽に浸漬し、次いで、ゴムローラーのマングルを用いてそれを絞ることによって、前記不織布の質量と同質量のウレタン樹脂組成物が浸漬した浸漬物を得た。次いで、それを前記ギアー式熱風乾燥機を使用して１００℃で１０分乾燥することによって、感熱凝固による凝固物を有する繊維基材を得た。 [Comparative Example 1]
By stirring 100 parts by weight of the aqueous urethane resin composition (X-1) obtained in Synthesis Example 1 and 100 parts by weight of a 2% by weight sodium chloride aqueous solution at 2,000 rpm for 2 minutes using a mechanical mixer, respectively. An aqueous urethane resin composition for impregnation was prepared.
Next, the nonwoven fabric (weighing 250 g / m 2 ) was immersed in a tank containing the aqueous urethane resin composition for impregnation obtained above, and then squeezed using a rubber roller mangle, thereby forming the nonwoven fabric. An immersion product in which a urethane resin composition having the same mass as the mass was immersed was obtained. Subsequently, it was dried at 100 ° C. for 10 minutes using the gear type hot air dryer, thereby obtaining a fiber base material having a coagulated product by heat-sensitive coagulation.
［比較例２］
　実施例１において、６０℃に加熱した５質量％の硫酸アンモニウム水溶液の凝固浴に代えて、１０℃の５質量％の硫酸アンモニウム水溶液の凝固浴を使用した以外は実施例１と同様にして繊維基材の含浸工程を行ったが、水性ウレタン樹脂組成物（Ｘ－１）は凝固しなかった。 [Comparative Example 2]
In Example 1, a fiber base material was used in the same manner as in Example 1 except that a coagulation bath of 5 mass% ammonium sulfate aqueous solution heated to 60 ° C was used instead of a coagulation bath of 5 mass% ammonium sulfate aqueous solution at 10 ° C. However, the aqueous urethane resin composition (X-1) did not coagulate.
［加工時の臭気の評価方法］
　加工中の凝固浴層の１ｍ上方にて、臭いを嗅ぎ、以下のように評価した。
　「Ｔ」；臭気を感じる。
　「Ｆ」；臭気を感じない。 [Evaluation method of odor during processing]
The smell was sniffed 1 m above the coagulation bath layer being processed and evaluated as follows.
“T”; feels odor.
“F”; no odor is felt.
［繊維基材への水性ウレタン樹脂の付着量の測定方法］
　実施例及び比較例で得られた凝固物を有する繊維基材を、５ｃｍ四方に裁断し、精密天秤にて質量を測定した。皮革用に含浸工程前の繊維基材を５ｃｍ四方に裁断し精密天秤にて質量を測定した。両者の質量の差を測定し、水性ウレタン樹脂の付着量（ｇ／ｍ２）を算出した。 [Method for measuring the amount of water-based urethane resin adhered to the fiber substrate]
The fiber base material having a coagulum obtained in Examples and Comparative Examples was cut into 5 cm squares, and the mass was measured with a precision balance. For leather, the fiber base material before the impregnation step was cut into 5 cm square, and the mass was measured with a precision balance. The difference in mass between the two was measured, and the adhesion amount (g / m 2 ) of the aqueous urethane resin was calculated.
［繊維基材への水性ウレタン樹脂の付着状態の評価方法］
　実施例及び比較例で得られた凝固物を有する繊維基材を、日立ハイテクテクノロジー株式会社製走査型電子顕微鏡「ＳＵ３５００」（倍率２００倍）を使用して観察し、以下のように評価した。
　「Ｔ」；水性ウレタン樹脂が繊維基材内部で繊維と絡み付いた状態が確認される。
　「Ｆ」；水性ウレタン樹脂が繊維基材内部で繊維と絡み付いた状態が確認されない。 [Evaluation Method for Adhesion State of Aqueous Urethane Resin to Fiber Substrate]
The fiber base material having a coagulated product obtained in Examples and Comparative Examples was observed using a scanning electron microscope “SU3500” (200 times magnification) manufactured by Hitachi High-Technologies Corporation, and evaluated as follows.
“T”: A state in which the aqueous urethane resin is entangled with the fiber inside the fiber base is confirmed.
“F”: The state in which the aqueous urethane resin is entangled with the fiber inside the fiber base material is not confirmed.
［風合いの評価方法］
　実施例及び比較例で得られた凝固物を有する繊維基材を、手で触った際の触感により以下のように評価した。
　「Ａ」；張り腰感、充実感共に優れている。
　「Ｂ」；張り腰感、充実感が感じられる。
　「Ｃ」；張り腰感、充実感がやや劣る。
　「Ｄ」；張り腰感、充実感が全く感じられない。 [Texture evaluation method]
The fiber base material having a coagulated product obtained in Examples and Comparative Examples was evaluated as follows according to the touch feeling when touched by hand.
“A”: Both the tension and the sense of fulfillment are excellent.
“B”: Feeling tight and full.
“C”; feeling of tightness and fullness are slightly inferior.
“D”; no tightness or fullness is felt.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
表１～２中の略語は、以下のものを示す。
「ＭＤＩ」；ジフェニルメタンジイソシアネート
「Ｈ１２ＭＤＩ」；ジシクロヘキシルメタンジイソシアネート Abbreviations in Tables 1 and 2 indicate the following.
“MDI”; diphenylmethane diisocyanate “H 12 MDI”; dicyclohexylmethane diisocyanate
　本発明である実施例１～５は、風合いに優れる凝固物が得られることが分かった。また、図１において確認できる通り、繊維基材の内部にまでウレタン樹脂の凝固物が充填し、繊維基材に凝固物が絡み付いた状態が形成されていることが分かった。 It has been found that Examples 1 to 5 according to the present invention can provide a solidified product having an excellent texture. Further, as can be confirmed in FIG. 1, it was found that a solidified product of urethane resin was filled up to the inside of the fiber base material, and a state in which the solidified material was entangled with the fiber base material was formed.
　一方、比較例１は、感熱凝固による凝固を行った態様であるが、風合いが不良であった。また、図２において確認できる通り、繊維基材の内部にまでウレタン樹脂が充填されておらず、繊維基材への絡み付きも確認されなかった。 On the other hand, Comparative Example 1 is a form in which coagulation was performed by thermal coagulation, but the texture was poor. Further, as can be confirmed in FIG. 2, the urethane resin was not filled up to the inside of the fiber base material, and entanglement of the fiber base material was not confirmed.
　比較例２は、凝固浴を加熱せず、１０℃の状態で使用した態様であるが、凝固しなかった。 Comparative Example 2 was an embodiment in which the coagulation bath was not heated and was used at 10 ° C., but did not coagulate.

Claims (7)

  1. 水性ウレタン樹脂組成物を、１５℃以上の非金属凝固剤水溶液で凝固させることにより得られることを特徴とする凝固物の製造方法。 A method for producing a coagulated product obtained by coagulating an aqueous urethane resin composition with a nonmetallic coagulant aqueous solution at 15 ° C or higher.
  2. 繊維基材を、水性ウレタン樹脂組成物中に含浸し、次いで、１５℃以上の非金属凝固剤水溶液を含む凝固浴に浸漬させる工程を有する請求項１記載の凝固物の製造方法。 The method for producing a coagulated product according to claim 1, further comprising the step of impregnating the fiber base material in an aqueous urethane resin composition and then immersing the fiber base material in a coagulation bath containing a nonmetallic coagulant aqueous solution at 15 ° C or higher.
  3. 前記非金属凝固剤が無機酸アンモニウムである請求項１又は２記載の凝固物の製造方法。 The method for producing a coagulated product according to claim 1 or 2, wherein the nonmetallic coagulant is an inorganic acid ammonium.
  4. 前記水性ウレタン樹脂組成物が、芳香環を有する水性ウレタン樹脂（Ａ）を含有するものである請求項１～３のいずれか１項記載の凝固物の製造方法。 The method for producing a coagulum according to any one of claims 1 to 3, wherein the aqueous urethane resin composition contains an aqueous urethane resin (A) having an aromatic ring.
  5. 前記水性ウレタン樹脂（Ａ）の芳香環の含有量が、０．８～８ｍｏｌ／ｋｇの範囲である請求項４記載の凝固物の製造方法。 The method for producing a coagulum according to claim 4, wherein the content of the aromatic ring of the aqueous urethane resin (A) is in the range of 0.8 to 8 mol / kg.
  6. 前記水性ウレタン樹脂（Ａ）が、芳香族ポリイソシアネートを原料とするものである請求項４記載の凝固物の製造方法。 The method for producing a solidified product according to claim 4, wherein the aqueous urethane resin (A) is made from aromatic polyisocyanate.
  7. 前記芳香族ポリイソシアネートが、ジフェニルメタンジイソシアネートである請求項６記載の凝固物の製造方法。 The method for producing a coagulum according to claim 6, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate.
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