WO2018186141A1 - Method for producing porous body - Google Patents

Method for producing porous body Download PDF

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Publication number
WO2018186141A1
WO2018186141A1 PCT/JP2018/010189 JP2018010189W WO2018186141A1 WO 2018186141 A1 WO2018186141 A1 WO 2018186141A1 JP 2018010189 W JP2018010189 W JP 2018010189W WO 2018186141 A1 WO2018186141 A1 WO 2018186141A1
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WO
WIPO (PCT)
Prior art keywords
urethane resin
aqueous urethane
aqueous
porous body
mass
Prior art date
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PCT/JP2018/010189
Other languages
French (fr)
Japanese (ja)
Inventor
智博 鉄井
Original Assignee
Dic株式会社
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Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2018553503A priority Critical patent/JP6521191B2/en
Publication of WO2018186141A1 publication Critical patent/WO2018186141A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising 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
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • 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
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • 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 porous body that can be used for producing, for example, synthetic leather.
  • a water-based urethane resin composition in which a urethane resin is dispersed in an aqueous medium can reduce the environmental burden compared to conventional organic solvent-based urethane resin compositions, so that materials for producing synthetic leather, coating agents, adhesives, etc. In recent years, it has been used favorably.
  • 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.
  • a fiber base material such as nonwoven fabric impregnated with an aqueous urethane resin composition and heat-coagulated (impregnated layer) is used.
  • aqueous urethane resin composition for impregnation of the fiber base material examples 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).
  • the viscosity of the urethane resin compound is once lowered by heating, the intermediate layer coating solution is absorbed by the fiber base material, and further the resin is applied to the fiber intersection by capillary action. It has been pointed out that the film obtained is inferior in flexibility and flexibility and easily damaged because the resin tends to adhere and the resin restrains the fibers.
  • the problem to be solved by the present invention is to provide a production method in which an organic solvent is not used and a porous body having an excellent texture can be obtained.
  • the present invention provides a method for producing a porous body characterized in that an aqueous urethane resin composition is applied to a substrate and immersed in an aqueous metal salt solution heated to 40 ° C. or higher.
  • a porous body having excellent texture can be obtained. Therefore, the said porous body can be used conveniently for manufacture of synthetic leather.
  • the method for producing a porous body of the present invention requires that an aqueous urethane resin composition is applied to a substrate and immersed in an aqueous metal salt solution heated to 40 ° C. or higher.
  • an aqueous metal coagulant solution as the coagulant.
  • the uniformity of the resin adhesion state is improved and porous, so that a porous body having an excellent texture can be obtained.
  • rate improves by heating a coagulant to 40 degreeC or more, the water-based urethane resin can be coagulated and the coagulation
  • the temperature of the coagulant is less than 40 ° C., the aqueous urethane resin cannot be coagulated.
  • the heating temperature of the coagulant is preferably in the range of 40 to 100 ° C., more preferably 40 to 80 ° C.
  • “porous body” refers to a material having a large number of pores.
  • the metal salt for example, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride and the like can be used. These metal salts may be used alone or in combination of two or more. Among these, the thickening and coagulation speed of the aqueous urethane resin composition is fast, and the fiber adhesion and restraint of the resin due to the capillary phenomenon can be suppressed, so that sodium chloride is used from the point that an even better texture is obtained. preferable.
  • water used for the coagulant for example, ion exchange water, distilled water, tap water and the like can be used. These waters may be used alone or in combination of two or more.
  • the content of the metal salt is preferably in the range of 1 to 50% by mass, and more preferably in the range of 2 to 20% by mass in the metal salt aqueous solution.
  • the base material examples include a base fabric; polyester such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide, polyimide, and the like.
  • the obtained sheet or film can be used.
  • a base fabric when the porous body obtained by the present invention is used as a synthetic leather, it is preferable to use a base fabric because an excellent texture can be obtained.
  • a nonwoven fabric for example, a nonwoven fabric, a woven fabric, a knitted fabric, or the like can be used.
  • 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.
  • the porous body is formed by applying an aqueous urethane resin composition to a substrate and immersing it in the aqueous metal salt solution heated to 40 ° C. or higher.
  • Examples of the method of applying the water-based urethane resin composition to the substrate include a method using a roll coater, knife coater, spray coater, gravure coater, comma coater, T-die coater, applicator and the like. .
  • the urethane resin in the aqueous urethane resin composition is solidified by immersing the coated product in a coagulation bath containing the aqueous metal salt solution heated to 40 ° C. or higher, whereby a porous body is obtained.
  • the immersion / solidification time is, for example, in the range of 1 to 30 minutes.
  • the porous body After obtaining the porous body, if necessary, it can be immersed in running water for 10 minutes to 2 hours after solidification to wash away unnecessary coagulants.
  • aqueous urethane resin composition examples include those containing an aqueous urethane resin (A) and an aqueous medium (B).
  • 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.
  • an aqueous urethane resin having a hydrophilic group it is preferable to use an aqueous urethane resin having a hydrophilic group, the solidification property to the coagulant is further improved by the electric double layer compression effect, and the texture is further improved.
  • an aqueous urethane resin having an anionic group it is more preferable to use an aqueous urethane resin having an anionic group.
  • 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, and the like. . 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 copolymers; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates Anionic emulsifiers such as salts, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; alkyl amine salts, alkyl trimethyl
  • stretching agent (a3) as a raw material can be used.
  • These reactions can use known urethanization reactions.
  • water-based urethane resin (A) an aromatic ring is used because of its low solubility in the coagulant used in the present invention, easy maintenance of a good solidified state and easy porosity, and a further improved texture. It is preferable to use an aqueous urethane resin.
  • 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.
  • the aromatic ring is supplied from either the polyisocyanate (a1) or the polyol (a2) as a raw material, but is supplied from the polyisocyanate (a1) from the viewpoint of easy availability of the raw material and production stability. That is, it is preferable to use an aromatic polyisocyanate.
  • 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.
  • polyether polyol 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.
  • 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.
  • the number average molecular weight of the said polyol (a2) shows the value measured by the gel permeation column chromatography (GPC) method.
  • 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 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.
  • 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.
  • 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).
  • 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.
  • the molar ratio of the total hydroxyl group and 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 amino group)] are preferably in the range of 0.8 to 1.2, more preferably in the range of 0.9 to 1.1.
  • 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).
  • an organic solvent may be used.
  • 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.
  • aqueous medium (B) for example, water, an organic solvent miscible with water, a mixture thereof, or the like can be used.
  • 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.
  • 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 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).
  • additives examples 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.
  • 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.
  • 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, it is preferable to use a nonionic emulsifier from the point which can improve the water dispersion stability of water-based urethane resin (A), and the point which a texture improves further.
  • 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 neutralizing agent neutralizes the carboxyl group when an anionic aqueous urethane resin is used as the aqueous urethane resin (A).
  • 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.
  • 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).
  • aqueous urethane resin composition used in the present invention aromatic polyisocyanate from the point that it becomes easier to coagulate with the coagulant, the point that the texture is further improved, and the water dispersion stability is improved. It is preferable to use an aqueous urethane resin composition containing an aqueous urethane resin (A) having an anionic group obtained by reacting a polyol and a chain extender, an aqueous medium (B), and a nonionic emulsifier.
  • A aqueous urethane resin having an anionic group obtained by reacting a polyol and a chain extender, an aqueous medium (B), and a nonionic emulsifier.
  • a synthetic leather having a base fabric and an intermediate layer of the porous body can be obtained by using a base fabric as the base material. Moreover, you may provide a skin layer on the said intermediate
  • a method for producing a skin layer on the intermediate layer include, for example, a method in which a material for forming a skin layer is applied on the intermediate layer and dried; the skin layer produced on a release paper is the intermediate layer. And the like.
  • aqueous urethane resin for example, a known aqueous urethane resin, solvent-based urethane resin, solventless urethane resin, aqueous acrylic resin, silicone resin, polypropylene resin, polyester resin, or the like can be used. These resins may be used alone or in combination of two or more.
  • the synthetic leather After the synthetic leather is produced, it may be aged at 30 to 100 ° C. for 1 to 10 days, if necessary.
  • aqueous urethane resin composition (X-1) having a nonvolatile content of 40% by mass.
  • 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 20,000 mPa After reacting at 70 ° C.
  • aqueous urethane resin composition (X-2) having a nonvolatile content of 40% by mass.
  • aqueous urethane resin composition (X-3) 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 100 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. Subsequently, the said liquid mixture was apply
  • the coating substrate was immersed in a 20% by mass aqueous solution of sodium chloride heated to 60 ° C. for 3 minutes to solidify the coating film. Then, it was immersed in water for 60 minutes, the excess coagulant was wash
  • Example 2 to 3 A porous body 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 2 In Example 1, it carried out like Example 1 except having used the coagulation bath of 20 mass% sodium chloride aqueous solution of 10 degreeC instead of the coagulation bath of 20 mass% sodium chloride heated at 60 degreeC.
  • the aqueous urethane resin composition (X-1) did not solidify.
  • the number average molecular weight of the polyol or the like used in the synthesis examples shows a value measured under the following conditions by gel permeation column chromatography (GPC) method.
  • 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 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Comparative Example 1 is a form in which coagulation was performed by thermal coagulation, but the texture was poor.
  • Comparative Example 2 was an embodiment in which the coagulation bath was not heated and was used at 10 ° C., but did not coagulate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention provides a method for conveniently obtaining a porous body by coagulating an aqueous urethane resin composition using a specific coagulating agent. Specifically, the present invention provides a method for producing a porous body, the method being characterized by coating an aqueous urethane resin composition on a base material and then immersing the same in an aqueous solution of a metal salt heated to 40ºC or higher. The metal salt used in the coagulating agent is preferably sodium chloride. In addition, the aqueous urethane resin composition preferably contains an aqueous urethane resin (A) having an aromatic ring. The aromatic ring content in the aqueous urethane resin (A) preferably falls within the range 0.8-8 mol/kg. The aqueous urethane resin (A) is preferably obtained using an aromatic polyisocyanate, specifically, diphenylmethane diisocyanate, as a raw material. According to the production method of the present invention, a porous body having an excellent texture can be conveniently obtained without using an organic solvent.

Description

多孔体の製造方法Method for producing porous body
　本発明は、例えば、合成皮革等の製造に使用可能な多孔体の製造方法に関する。 The present invention relates to a method for producing a porous body that can be used for producing, for example, synthetic leather.
　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、環境負荷を低減できることから、合成皮革、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。 A water-based urethane resin composition in which a urethane resin is dispersed in an aqueous medium can reduce the environmental burden compared to conventional organic solvent-based urethane resin compositions, so that materials for producing synthetic leather, coating agents, adhesives, etc. In recent years, it has been used favorably.
　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、繊維基材に中間層塗工液が吸収され、さらに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 coagulation of the aqueous urethane resin composition by heat-sensitive coagulation, the viscosity of the urethane resin compound is once lowered by heating, the intermediate layer coating solution is absorbed by the fiber base material, and further the resin is applied to the fiber intersection by capillary action. It has been pointed out that the film obtained is inferior in flexibility and flexibility and easily damaged because the resin tends to adhere and the resin restrains the fibers.
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、風合いに優れる多孔体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 in which an organic solvent is not used and a porous body having an excellent texture can be obtained.
　本発明は、水性ウレタン樹脂組成物を基材に塗工し、４０℃以上に加熱した金属塩水溶液に浸漬させることを特徴とする多孔体の製造方法を提供するものである。 The present invention provides a method for producing a porous body characterized in that an aqueous urethane resin composition is applied to a substrate and immersed in an aqueous metal salt solution heated to 40 ° C. or higher.
　本発明の製造方法によれば、風合いに優れる多孔体が得られる。よって、前記多孔体は、合成皮革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 porous body having excellent texture can be obtained. Therefore, the said porous body can be used conveniently for manufacture of synthetic leather.
　本発明の多孔体の製造方法は、水性ウレタン樹脂組成物を基材に塗工し、４０℃以上に加熱した金属塩水溶液に浸漬させることを必須の要件とするものである。 The method for producing a porous body of the present invention requires that an aqueous urethane resin composition is applied to a substrate and immersed in an aqueous metal salt solution heated to 40 ° C. or higher.
　本発明においては、凝固剤として金属凝固剤水溶液を用いることが必須である。前記凝固剤を使用することにより、樹脂付着状態の均一性が向上し、多孔化するため、優れた風合いを有する多孔体が得られる。また、凝固剤を４０℃以上に加熱することにより、凝固速度が向上するため、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４０℃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。前記凝固剤の加熱温度としては、４０～１００℃、さらには４０～８０℃の範囲であることが好ましい。なお、本発明において、「多孔体」とは、多数の孔を有するものを示す。 In the present invention, it is essential to use an aqueous metal coagulant solution as the coagulant. By using the coagulant, the uniformity of the resin adhesion state is improved and porous, so that a porous body having an excellent texture can be obtained. Moreover, since a coagulation | solidification speed | rate improves by heating a coagulant to 40 degreeC or more, the water-based urethane resin can be coagulated and the coagulation | solidification which has the further outstanding texture is obtained. If the temperature of the coagulant is less than 40 ° C., the aqueous urethane resin cannot be coagulated. The heating temperature of the coagulant is preferably in the range of 40 to 100 ° C., more preferably 40 to 80 ° C. In the present invention, “porous body” refers to a material having a large number of pores.
　前記金属塩としては、例えば、硝酸カルシウム、塩化カルシウム、硝酸亜鉛、塩化亜鉛、酢酸マグネシウム、硫酸アルミニウム、塩化ナトリウム等を用いることができる。これらの金属塩は単独で用いても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・拘束を抑制できるため、より一層優れた風合いが得られる点から、塩化ナトリウムを用いることが好ましい。 As the metal salt, for example, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride and the like can be used. These metal salts may be used alone or in combination of two or more. Among these, the thickening and coagulation speed of the aqueous urethane resin composition is fast, and the fiber adhesion and restraint of the resin due to the capillary phenomenon can be suppressed, so that sodium chloride is used from the point that an even better texture is obtained. preferable.
　前記凝固剤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 coagulant, for example, ion exchange water, distilled water, tap water and the like can be used. These waters may be used alone or in combination of two or more.
　前記金属塩の含有量としては、前記金属塩水溶液中、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 metal salt is preferably in the range of 1 to 50% by mass, and more preferably in the range of 2 to 20% by mass in the metal salt aqueous solution.
　前記基材としては、例えば、基布；ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル、ポリオレフィン、ポリアクリレート、ポリ塩化ビニル、ポリエチレン、ポリプロピレンエチレンビニルアルコール、ポリウレタン、ポリアミド、ポリイミドなどを用いて得られるシート又はフィルムなどを用いることができる。これらの中でも、本発明で得られる多孔体が合成皮革として使用される場合には、優れた風合いが得られることから、基布を用いることが好ましい。 Examples of the base material include a base fabric; polyester such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyolefin, polyacrylate, polyvinyl chloride, polyethylene, polypropylene ethylene vinyl alcohol, polyurethane, polyamide, polyimide, and the like. The obtained sheet or film can be used. Among these, when the porous body obtained by the present invention is used as a synthetic leather, it is preferable to use a base fabric because an excellent texture can be obtained.
　前記基布としては、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 base fabric, 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.
　前記多孔体は、水性ウレタン樹脂組成物を基材に塗工し、４０℃以上に加熱した前記金属塩水溶液に浸漬することにより形成される。 The porous body is formed by applying an aqueous urethane resin composition to a substrate and immersing it in the aqueous metal salt solution heated to 40 ° C. or higher.
　前記水性ウレタン樹脂組成物を基材に塗工する方法としては、例えば、例えば、ロールコーター、ナイフコーター、スプレーコーター、グラビアコーター、コンマコーター、Ｔ－ダイコーター、アプリケーター等を使用する方法が挙げられる。 Examples of the method of applying the water-based urethane resin composition to the substrate include a method using a roll coater, knife coater, spray coater, gravure coater, comma coater, T-die coater, applicator and the like. .
　次いで、塗工物を更に前記４０℃以上に加熱した前記金属塩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、多孔体が得られる。この際の浸漬・凝固時間としては、例えば１～３０分の範囲である。 Next, the urethane resin in the aqueous urethane resin composition is solidified by immersing the coated product in a coagulation bath containing the aqueous metal salt solution heated to 40 ° C. or higher, whereby a porous body is obtained. In this case, the immersion / solidification time is, for example, in the range of 1 to 30 minutes.
　多孔体を得た後は、必要に応じて、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。 After obtaining the porous body, if necessary, it can be immersed in running water for 10 minutes to 2 hours after solidification to wash away unnecessary coagulants.
　本発明において用い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。 Examples of the aqueous urethane resin composition that can be used in the present invention include those containing an aqueous urethane resin (A) and an aqueous medium (B).
　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凝固剤に対する凝固性がより一層向上する点、及び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 an aqueous urethane resin having a hydrophilic group, the solidification property to the coagulant is further improved by the electric double layer compression effect, and the texture is further improved. In view of the above, it is more preferable to use an aqueous urethane resin having an anionic group.
　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, and the like. . 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 copolymers; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates 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く多孔化しやすい点、及び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), an aromatic ring is used because of its low solubility in the coagulant used in the present invention, easy maintenance of a good solidified state and easy porosity, and a further improved texture. It is preferable to use an aqueous urethane resin.
　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（ａ１）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 (a1) 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 in 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）法により測定した値を示す。 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 measured by the gel permeation column chromatography (GPC) method.
　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 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 amino group)] are 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, it is preferable to use a nonionic emulsifier from the point which can improve the water dispersion stability of water-based urethane resin (A), and the point which a texture improves further.
　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、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 mentioned above, as the aqueous urethane resin composition used in the present invention, aromatic polyisocyanate from the point that it becomes easier to coagulate with the coagulant, the point that the texture is further improved, and the water dispersion stability is improved, It is preferable to use an aqueous urethane resin composition containing an aqueous urethane resin (A) having an anionic group obtained by reacting a polyol and a chain extender, an aqueous medium (B), and a nonionic emulsifier.
　本発明の多孔体が、合成皮革として使用される場合には、前記基材として基布を使用することにより、基布、及び、多孔体による中間層を有する合成皮革を得ることができる。また、前記中間層の上には、必要に応じて、表皮層を設けてもよい。前記中間層上に、表皮層を作製する方法としては、例えば、前記中間層上に、表皮層を形成する材料を塗工し、乾燥させる方法；離型紙上に作製した表皮層を前記中間層と貼り合わせる方法等が挙げられる。 When the porous body of the present invention is used as a synthetic leather, a synthetic leather having a base fabric and an intermediate layer of the porous body can be obtained by using a base fabric as the base material. Moreover, you may provide a skin layer on the said intermediate | middle layer as needed. Examples of a method for producing a skin layer on the intermediate layer include, for example, a method in which a material for forming a skin layer is applied on the intermediate layer and dried; the skin layer produced on a release paper is the intermediate layer. And the like.
　前記表皮層を形成する材料としては、例えば、公知の水性ウレタン樹脂、溶剤系ウレタン樹脂、無溶剤ウレタン樹脂、水性アクリル樹脂、シリコーン樹脂、ポリプロピレン樹脂、ポリエステル樹脂等を用いることができる。これらの樹脂は単独で用いても２種以上を併用してもよい。 As the material for forming the skin layer, for example, a known aqueous urethane resin, solvent-based urethane resin, solventless urethane resin, aqueous acrylic resin, silicone resin, polypropylene resin, polyester resin, or the like can be used. These resins may be used alone or in combination of two or more.
　前記合成皮革を製造した後は、必要に応じて、例えば、３０～１００℃で１～１０日エージングしてもよい。 After the synthetic leather is produced, it may be aged at 30 to 100 ° C. for 1 to 10 days, if necessary.
　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 20,000 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-2) 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-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 · s. Then, the reaction was stopped at 70 ° C. until the temperature reached, the reaction was stopped by adding 3 parts by mass of methanol to obtain a methyl ethyl ketone solution of the aqueous urethane resin (A-3). 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.
［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１００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、不織布基材表面にナイフコーティング（クリアランス１００μｍ）にて前記配合液を塗工した。続いて、６０℃に加熱した塩化ナトリウム２０質量％水溶液へコーティング基材を３分間浸漬し、コーティング皮膜を凝固させた。その後、水に６０分間浸漬させて余分な凝固剤を洗浄し、１２０℃で３０分間乾燥させることにより、多孔体を得た。 [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 100 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.
Subsequently, the said liquid mixture was apply | coated to the nonwoven fabric base material surface by knife coating (clearance of 100 micrometers). Subsequently, the coating substrate was immersed in a 20% by mass aqueous solution of sodium chloride heated to 60 ° C. for 3 minutes to solidify the coating film. Then, it was immersed in water for 60 minutes, the excess coagulant was wash | cleaned, and the porous body was obtained by making it dry at 120 degreeC for 30 minutes.
［実施例２～３］
　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と同様にして多孔体を得た。 [Examples 2 to 3]
A porous body 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.
［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、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１００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、不織布基材表面にナイフコーティング（クリアランス１００μｍ）にて前記配合液を塗工した。次いで、それを前記ギアー式熱風乾燥機により１００℃で１０分乾燥することによって、感熱凝固による物品を得た。 [Comparative 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 100 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.
Subsequently, the said liquid mixture was apply | coated to the nonwoven fabric base material surface by knife coating (clearance of 100 micrometers). Subsequently, it was dried at 100 ° C. for 10 minutes by the gear type hot air dryer, thereby obtaining an article by thermal coagulation.
［比較例２］
　実施例１において、６０℃に加熱した塩化ナトリウム２０質量％水溶液の凝固浴に代えて、１０℃の塩化ナトリウム２０質量％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, it carried out like Example 1 except having used the coagulation bath of 20 mass% sodium chloride aqueous solution of 10 degreeC instead of the coagulation bath of 20 mass% sodium chloride heated at 60 degreeC. The aqueous urethane resin composition (X-1) did not solidify.
［数平均分子量の測定方法］
　合成例で用いたポリオール等の数平均分子量は、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、下記の条件により測定した値を示す。 [Measurement method of number average molecular weight]
The number average molecular weight of the polyol or the like used in the synthesis examples shows a value measured under the following conditions 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
［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状態の評価方法］
　実施例及び比較例で得られた物品を、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」；基布表面に形成した水性ウレタン樹脂層に多孔構造が確認される。
　「Ｆ」；基布表面に形成した水性ウレタン樹脂層に多孔構造が確認されない。 [Evaluation Method for Adhesion State of Aqueous Urethane Resin to Fiber Substrate]
Articles obtained in Examples and Comparative Examples were observed using a scanning electron microscope “SU3500” (200 times magnification) manufactured by Hitachi High-Technologies Corporation, and evaluated as follows.
“T”; a porous structure is confirmed in the aqueous urethane resin layer formed on the surface of the base fabric.
“F”: No porous structure is confirmed in the aqueous urethane resin layer formed on the surface of the base fabric.
［風合いの評価方法］
　実施例及び比較例で得られた物品を、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 articles obtained in Examples and Comparative Examples were 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
表１中の略語について説明する。
「ＭＤＩ」；ジフェニルメタンジイソシアネート Abbreviations in Table 1 will be described.
"MDI"; diphenylmethane diisocyanate
　本発明である実施例１～３にて得られた合成皮革用中間層は、風合いに優れることが分かった。また、有機溶剤を使用していないため臭気の問題も発生しなかった。 It was found that the intermediate layer for synthetic leather obtained in Examples 1 to 3 according to the present invention was excellent in texture. Moreover, since no organic solvent was used, the problem of odor did not occur.
　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。 On the other hand, Comparative Example 1 is a form in which coagulation was performed by thermal coagulation, but the texture was poor.
　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 (6)

  1. 水性ウレタン樹脂組成物を基材に塗工し、４０℃以上に加熱した金属塩水溶液に浸漬させることを特徴とする多孔体の製造方法。 A method for producing a porous body, comprising applying a water-based urethane resin composition to a substrate and immersing the substrate in an aqueous metal salt solution heated to 40 ° C or higher.
  2. 前記金属塩が、塩化ナトリウムである請求項１記載の多孔体の製造方法。 The method for producing a porous body according to claim 1, wherein the metal salt is sodium chloride.
  3. 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又は２記載の多孔体の製造方法。 The method for producing a porous body according to claim 1 or 2, wherein the aqueous urethane resin composition contains an aqueous urethane resin (A) having an aromatic ring.
  4. 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３記載の多孔体の製造方法。 The method for producing a porous body according to claim 3, wherein the content of the aromatic ring in the aqueous urethane resin (A) is in the range of 0.8 to 8 mol / kg.
  5. 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３又は４記載の多孔体の製造方法。 The method for producing a porous body according to claim 3 or 4, wherein the aqueous urethane resin (A) is made from aromatic polyisocyanate.
  6. 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５記載の多孔体の製造方法。 The method for producing a porous body according to claim 5, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate.
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