WO2018186142A1 - Procédés de production de corps poreux, de gant et de cuir synthétique - Google Patents

Procédés de production de corps poreux, de gant et de cuir synthétique Download PDF

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Publication number
WO2018186142A1
WO2018186142A1 PCT/JP2018/010190 JP2018010190W WO2018186142A1 WO 2018186142 A1 WO2018186142 A1 WO 2018186142A1 JP 2018010190 W JP2018010190 W JP 2018010190W WO 2018186142 A1 WO2018186142 A1 WO 2018186142A1
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Prior art keywords
urethane resin
aqueous
resin composition
aqueous urethane
porous body
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PCT/JP2018/010190
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English (en)
Japanese (ja)
Inventor
智博 鉄井
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Dic株式会社
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Priority to JP2018553496A priority Critical patent/JP6521348B2/ja
Publication of WO2018186142A1 publication Critical patent/WO2018186142A1/fr

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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/04—Appliances for making gloves; Measuring devices for glove-making
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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, gloves, and synthetic leather.
  • aqueous urethane resin compositions in which urethane resins are dispersed in an aqueous medium can reduce the environmental impact, so synthetic leather, coating agents, adhesives, gloves, etc. are manufactured. In recent years, it has begun to be used favorably as a material to be used.
  • the synthetic leather is generally composed of a fibrous base material such as a nonwoven fabric, an intermediate layer, and a skin layer, and the fibrous base material is intended to improve the flex resistance and texture of the synthetic leather.
  • 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 the impregnation layer for example, an aqueous urethane resin composition containing a urethane resin having a carboxyl group and / or a sulfonic acid group, a heat-sensitive coagulant, and an aqueous medium is disclosed (for example, , See Patent Document 1).
  • 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 coagulated with an aqueous nonmetallic coagulant solution.
  • the present invention is also a method for producing a glove having a solidified film of a water-based urethane resin composition, wherein the solidified film immerses the water-based urethane resin composition in a non-metal coagulant aqueous solution.
  • the manufacturing method of this is provided.
  • this invention provides the manufacturing method of the synthetic leather characterized by apply
  • a porous body excellent in texture can be obtained without using an organic solvent. Moreover, since it does not contain metal ions as a coagulant, it does not cause rusting or deterioration of the production apparatus when producing a coagulated product. Therefore, the porous body obtained by the production method of the present invention can be suitably used for production of gloves and synthetic leather.
  • the method for producing a porous body according to the present invention coagulates an aqueous urethane resin composition with a nonmetallic coagulant aqueous solution.
  • the present invention it is essential to use a non-metal coagulant aqueous solution as the coagulant.
  • a nonmetallic coagulant by using a nonmetallic coagulant, the aqueous urethane resin composition can be thickened, and a porous body having an excellent texture can be obtained.
  • the coagulation rate is improved by increasing the concentration of the coagulant, a porous body having a better texture can be obtained.
  • the temperature of the non-metal coagulant aqueous solution is preferably in the range of 10 to 100 ° C., more preferably in the range of 20 to 80 ° C., because a porous body can be obtained more easily.
  • porous body refers to a material having a large number of pores.
  • nonmetallic coagulant examples include ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, tetraphenylammonium chloride, and triethylmethyl chloride.
  • the thickening and coagulation speed of the aqueous urethane resin composition is fast, it is possible to suppress the fiber adhesion / restraint of the resin due to the capillary phenomenon, and a more excellent texture is obtained.
  • Inorganic acid ammonium is preferably used, and ammonium sulfate is more preferable.
  • 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 aqueous urethane resin (A) can be dispersed in an aqueous medium (B) to be described later.
  • a urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group
  • a urethane resin that is forcibly dispersed in the aqueous medium (B) 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, a solidification property with respect to the non-metal coagulant is further improved by the electric double layer compression effect, and is easily porous. It is more preferable to use a urethane resin having an anionic group from the viewpoint of obtaining an even better texture.
  • Examples of the method for obtaining the 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 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.
  • Examples of the method for obtaining the 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 a method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.
  • stretching agent (a3) as a raw material can be used.
  • These reactions can use known urethanization reactions.
  • 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.
  • 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 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).
  • 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 viewpoint that the water dispersion stability of the aqueous urethane resin (A) can be improved and the texture is further improved, and the HLB (Hydrophile-Lipophile Balance) is 15 or less. Some are preferred, and 2 to 15 are more preferred.
  • Nonionic emulsifiers that can be preferably used include, for example, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene oleyl ether, Oxyethylene stearyl ether, polyoxyethylene sorbitol tetraoleate, or the like can be used. These emulsifiers may be used alone or in combination of two or more.
  • 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 porous body can be easily obtained by coagulating the aqueous urethane resin composition with an aqueous nonmetallic coagulant solution.
  • the method for producing the porous body include a method in which the aqueous urethane resin composition is applied to a substrate and immersed in the non-metal coagulant 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.
  • 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 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.
  • Examples of the method for applying the aqueous urethane resin composition to the substrate include, for example, a method using a roll coater, knife coater, spray coater, gravure coater, comma coater, T-die coater, applicator and the like. It is done.
  • the coated product is further immersed in a coagulation bath of the non-metal coagulant aqueous solution, whereby the urethane resin in the aqueous urethane resin composition is coagulated to obtain a porous body.
  • 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.
  • a porous body excellent in texture can be obtained without using an organic solvent. Moreover, since it does not contain metal ions as a coagulant, it does not cause rusting or deterioration of the production apparatus when producing a coagulated product. Therefore, the porous body obtained by the production method of the present invention can be suitably used for production of gloves and synthetic leather.
  • a hand mold, a pipe mold or the like is first immersed in the aqueous urethane resin composition, and then the hand mold or the like is used for the nonmetal.
  • a method of forming a solidified film on the surface of the hand mold or the like by immersing it in a coagulant aqueous solution, washing the surface with water, and drying the surface.
  • the hand shape or tube shape may be preliminarily equipped with a glove-like material or a tubular material made of knitted material such as nylon fiber.
  • the knitted material is not limited to the nylon fiber, but may be one made of polyester fiber, aramid fiber, cotton or the like.
  • the textile fabric which consists of the said fiber can also be used instead of the said knitting.
  • a glove-like article or a tubular article made of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can be used.
  • the porous body when used for the production of synthetic leather, by using a base fabric as the base material, a synthetic leather having a base fabric and an intermediate layer of the porous body can be obtained. Moreover, you may provide a skin layer on the said intermediate
  • 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.
  • the synthetic leather obtained by such a method can easily produce a smooth porous body without being affected by the unevenness of the base fabric, as compared with a case where a base material is impregnated with an aqueous urethane resin composition. Can do. Further, even when the porous body is a thick film, it is very flexible, and further, since a cushion layer is formed on the surface by the porous body, it is excellent in flexibility.
  • 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. Next, a knitted glove made of nylon fiber was attached to the hand mold, and dipped in the above mixture for 15 seconds and pulled up.
  • a thickener (“Borch Gel L75N” manufactured by Borcher)
  • Carbodiimide crosslinking agent (“Carbodilite SV manufactured by Nisshinbo Chemical Co., Ltd.) ⁇ 02 ”
  • the hand mold was pulled up after being immersed in a coagulation bath of 40 mass% ammonium sulfate aqueous solution heated to 60 ° C. for 3 minutes. Subsequently, the hand mold was immersed in water for 60 minutes to wash away excess coagulant and dried at 120 ° C. for 30 minutes. Thereafter, the knitted gloves were removed from the hand mold to obtain a glove having a solidified film of the aqueous urethane resin composition.
  • Examples 2 to 3 A glove 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 replaced with the coagulation bath of the ammonium sulfate 40 mass% aqueous solution heated at 60 degreeC, it carried out similarly to Example 1 except having used the coagulation bath of the sodium chloride 20 mass% aqueous solution of 60 degreeC, and carried out aqueous urethane. A glove having a solidified film of the resin composition was obtained.
  • 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.
  • Example 4 100 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 for 3 minutes in a 40% by weight ammonium sulfate aqueous solution heated to 60 ° C. to solidify the coating film. After dipping, it was immersed in water for 60 minutes to wash away excess coagulant and dried at 120 ° C. for 30 minutes to obtain an intermediate layer for synthetic leather.
  • Example 5 to 6 An intermediate layer for synthetic leather 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.
  • 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 a metal salt coagulation bath was used instead of the nonmetal coagulant, but the texture was poor.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Gloves (AREA)

Abstract

La présente invention concerne un procédé de production d'un corps poreux, le procédé étant caractérisé par la coagulation d'une composition aqueuse de résine d'uréthane à l'aide d'une solution aqueuse d'un agent coagulant sans métal. La présente invention concerne également un procédé de production d'un gant comprenant un film coagulé de la composition aqueuse de résine d'uréthane, le procédé étant caractérisé en ce que le film coagulé est obtenu par immersion de la composition aqueuse de résine d'uréthane dans une solution aqueuse d'un agent coagulant sans métal. La présente invention concerne également un procédé de production d'un cuir synthétique, le procédé étant caractérisé par le revêtement d'une composition aqueuse de résine d'uréthane sur un tissu de base, puis l'immersion de ce dernier dans une solution aqueuse d'un agent coagulant sans métal. Il est préférable d'utiliser un sel d'ammonium d'un acide inorganique en tant qu'agent coagulant sans métal afin d'obtenir une meilleure texture. Le problème à résoudre par la présente invention est de fournir un procédé de production d'un gant présentant une excellente texture.
PCT/JP2018/010190 2017-04-04 2018-03-15 Procédés de production de corps poreux, de gant et de cuir synthétique WO2018186142A1 (fr)

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CN115461507B (zh) * 2020-06-11 2024-03-19 Dic株式会社 凝固物的制造方法

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