WO2018186141A1 - Procédé de production de corps poreux - Google Patents

Procédé de production de corps poreux 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
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English (en)
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/ja
Publication of WO2018186141A1 publication Critical patent/WO2018186141A1/fr

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

Abstract

La présente invention concerne un procédé d'obtention pratique d'un corps poreux par coagulation d'une composition de résine d'uréthane aqueuse à l'aide d'un agent coagulant spécifique. Spécifiquement, la présente invention concerne un procédé de production d'un corps poreux, le procédé étant caractérisé par le revêtement d'une composition de résine d'uréthane aqueuse sur un matériau de base puis par l'immersion de celui-ci dans une solution aqueuse d'un sel métallique chauffé à 40 °C ou plus. Le sel métallique utilisé dans l'agent coagulant est de préférence le chlorure de sodium. De plus, la composition de résine d'uréthane aqueuse contient de préférence une résine d'uréthane aqueuse (A) ayant un cycle aromatique. La teneur en cycle aromatique dans la résine d'uréthane aqueuse (A) est de préférence dans la plage de 0,8 à 8 mol/kg. La résine d'uréthane aqueuse (A) est de préférence obtenue en utilisant un polyisocyanate aromatique, spécifiquement du diisocyanate de diphénylméthane, en tant que matière première. Selon le procédé de production de la présente invention, un corps poreux ayant une excellente texture peut être obtenu de façon pratique sans utiliser de solvant organique.
PCT/JP2018/010189 2017-04-04 2018-03-15 Procédé de production de corps poreux WO2018186141A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021084923A1 (fr) * 2019-10-28 2021-05-06 Dic株式会社 Composition de résine uréthanique, cuir synthétique et procédé de fabrication d'un cuir synthétique
CN113417151A (zh) * 2021-07-08 2021-09-21 江苏聚杰微纤科技集团股份有限公司 一种仿油性泡孔结构的环保pu人造革及其制备方法
WO2021251053A1 (fr) * 2020-06-11 2021-12-16 Dic株式会社 Procédé de fabrication de produit coagulé
US20220186431A1 (en) * 2019-03-29 2022-06-16 Toray Industries, Inc. Sheet-shaped article and manufacturing method therefor

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