WO2017208680A1 - 凝固物の製造方法 - Google Patents
凝固物の製造方法 Download PDFInfo
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- WO2017208680A1 WO2017208680A1 PCT/JP2017/016301 JP2017016301W WO2017208680A1 WO 2017208680 A1 WO2017208680 A1 WO 2017208680A1 JP 2017016301 W JP2017016301 W JP 2017016301W WO 2017208680 A1 WO2017208680 A1 WO 2017208680A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/14—Manufacture of cellular products
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
- C08G85/002—Post-polymerisation treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- 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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
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- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
Definitions
- the present invention relates to a method for producing a coagulated product having a porous structure.
- Patent Document 1 a method of forming a porous structure by applying a heat treatment using wet heat and microwaves after applying an aqueous urethane resin composition to a substrate; in Patent Document 2, wet heat heating by steam Or a method of making a water-based urethane resin composition porous by heating combined with high-frequency heating or high-frequency dielectric heating; in Patent Document 3, a fiber base material is impregnated with a water-based urethane resin composition and then subjected to thermal gelation treatment. And a method for forming a porous structure is disclosed.
- JP 2000-160484 A JP 2002-249985 A JP2013-083031A JP 2005-273083 A JP-T 2006-511727 Special table 2006-524754 gazette Special table 2009-527658
- the problem to be solved by the present invention is to provide a method for easily producing a coagulated product having a porous structure using a water-based urethane resin composition without undergoing steps such as heating and foaming. .
- the present invention relates to an aqueous urethane resin composition containing an aqueous urethane resin (A) having an acid value of 0.01 mgKOH / g or more, and a thickening agent having an oxyethylene group content of 2 ⁇ 10 ⁇ 2 mol / g or less.
- the agent (B) is blended in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the aqueous urethane resin (A) and thickened, and then a coagulant containing the metal salt (c-1) (
- the present invention provides a method for producing a coagulated product characterized by coagulating in C).
- the aqueous urethane resin composition can be made porous without undergoing heating or foaming steps, and thus a solidified product having a porous structure can be obtained easily and stably.
- the term “porous” means having a large number of fine pores.
- the content of oxyethylene groups is 2 ⁇ 10 ⁇ 2 mol relative to the aqueous urethane resin composition containing the aqueous urethane resin (A) having an acid value of 0.01 mgKOH / g or more.
- / G or less thickener (B) is blended in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the water-based urethane resin (A), and then the metal salt (c-1 It is essential to coagulate with a coagulant (C) containing).
- the water-based urethane resin (A) used in the present invention it is essential to use a resin having an acid value of 0.01 mgKOH / g or more for easily obtaining a porous structure.
- the acid value of the aqueous urethane resin (A) is in the above range, the synthesized aqueous urethane resin is stable and can be easily solidified with the coagulant (C), so that a good porous structure can be formed.
- the acid value is preferably in the range of 0.01 to 70 mgKOH / g, more preferably in the range of 1 to 50 mgKOH / g, in view of obtaining a more favorable porous structure.
- a range is more preferred, with a range of 6-30 mg KOH / g being particularly preferred.
- the measuring method of the acid value of the said water-based urethane resin (A) is described in the Example mentioned later.
- the aqueous urethane resin (A) has the acid value, that is, has a structure derived from an anionic group such as a carboxyl group or a sulfonic acid group.
- examples of the aqueous urethane resin (A) include a polyol (a-1), a compound (a-2) imparting an anionic group, a chain extender (a-3), and a polyisocyanate (a-4).
- a reactant can be used.
- polystyrene resin examples include polyether polyol, polycarbonate polyol, polyester polyol, polyacryl polyol, polybutadiene polyol, castor oil polyol, and the like. These polyols (a-1) may be used alone or in combination of two or more. Among these, it is preferable to use one or more polyols selected from the group consisting of polyether polyols, polycarbonate polyols, and polyester polyols because the porous structure can be formed more stably.
- the number average molecular weight of the polyol (a-1) is preferably in the range of 500 to 15,000, more preferably in the range of 600 to 10,000, from the viewpoints of flexibility and production stability of the aqueous urethane resin.
- the range of 700 to 8,000 is more preferable, and the range of 800 to 5,000 is particularly preferable.
- the number average molecular weight of the polyol (a-1) is a value measured under the following conditions by gel permeation 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.
- Examples of the compound (a-2) imparting an anionic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-valeric acid and the like.
- Compounds having a carboxyl group 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl) -2-aminoethyl
- a compound having a sulfonyl group such as sulfonic acid can be used. These compounds may be used alone or in combination of two or more. Among these, since the reactivity with respect to a coagulant (C) is favorable, it is preferable to use the compound which has a carboxyl group from the point which can form a much more favorable porous structure.
- the anionic group may be partially or completely neutralized with a basic compound in the aqueous urethane resin composition.
- a basic compound examples include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like.
- the chain extender (a-3) has a number average molecular weight in the range of 50 to 490, such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethyl.
- Chain extenders having amino groups such as 1,4-cyclohexanediamine and hydrazine; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1 , 4-butane
- a chain extender having a hydroxyl group such as alcohol, hexamethylene glycol
- chain extenders may be used alone or in combination of two or more.
- the amount of the chain extender (a-3) used is in the range of 0.01 to 8% by mass with respect to the total mass of the raw material of the water-based urethane resin (A) from the viewpoint of the mechanical strength of the solidified product.
- the range of 0.01 to 5% by mass is more preferable.
- polyisocyanate (a-4) examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate.
- aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate.
- Cycloaliphatic diisocyanate isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, or other aliphatic or cycloaliphatic polyisocyanates. These polyisocyanates may be used alone or in combination of two or more.
- the aqueous urethane resin (A) is, for example, in the absence of a solvent or in the presence of an organic solvent, the polyol (a-1), the compound imparting the anionic group (a-2), the chain extender (a- 3) and the polyisocyanate (a-4) can be mixed and, for example, urethanated at a temperature of 50 to 100 ° C. for 3 to 10 hours.
- the aqueous urethane resin (A) is, for example, in the absence of a solvent or in the presence of an organic solvent, the polyol (a-1), the compound (a-2) imparting the anionic group, and the polyisocyanate ( a-4) and reacting, for example, at a temperature of 50 to 100 ° C. for 3 to 10 hours to obtain a urethane prepolymer having an isocyanate group at the molecular end, and then the urethane prepolymer and a chain extender It can also be produced by reacting with (a-3).
- Examples of the organic solvent that can be used for producing the aqueous urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; Nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone can be used.
- the said organic solvent may be used independently or may use 2 or more types together.
- the average particle diameter of the aqueous urethane resin (A) is preferably in the range of 0.01 to 1 ⁇ m, more preferably in the range of 0.05 to 0.9 ⁇ m, from the viewpoint of preventing the formation of precipitates. .
- the measuring method of the average particle diameter of the said water-based urethane resin (A) is described in the Example mentioned later.
- the weight average molecular weight of the water-based urethane resin (A) is preferably in the range of 10,000 to 1,000,000 from the viewpoint of physical properties such as flexibility and strength of the processed product, and processability. More preferably, it is in the range of 5,000 to 500,000.
- the weight average molecular weight of the water-based urethane resin (A) is a value obtained by measurement in the same manner as the number average molecular weight of the polyol (a-1).
- the content of the water-based urethane resin (A) in the water-based urethane resin composition is in the range of 10 to 60% by mass in the water-based urethane resin composition from the viewpoint of obtaining good viscosity and coating workability. Preferably, it is in the range of 20 to 50% by mass.
- the aqueous urethane resin composition preferably contains an aqueous medium (Z) in addition to the aqueous urethane resin (A) from the viewpoints of coatability and storage stability.
- aqueous medium (Z) 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-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycol solvents such as ethylene glycol, diethylene glycol and propylene glycol; An alkyl ether solvent of polyol; a lactam solvent such as N-methyl-2-pyrrolidone can be used.
- the aqueous urethane resin (A) is produced in the absence of a solvent or in the presence of the organic solvent, and then an anionic property in the aqueous urethane resin (A).
- the method include neutralizing the group as necessary, supplying the aqueous medium (Z), and dispersing the aqueous urethane resin (A) in the aqueous medium (Z).
- a machine such as a homogenizer may be used as necessary.
- an emulsifier may be used from the viewpoint of improving the dispersion stability of the aqueous urethane resin (A) in the aqueous medium (Z).
- emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
- nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
- Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
- Anionic emulsifiers; cationic amines such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts It can be used. These emulsifiers may be used alone or in combination of two or more.
- the aqueous polyurethane composition may contain other additives in addition to the aqueous urethane resin (A) and the aqueous medium (Z).
- the additive examples include an antifoaming agent, a urethanization catalyst, a silane coupling agent, a filler, a wax, a heat stabilizer, a light stabilizer, a pigment, a dye, an antistatic agent, an oil repellent, a flame retardant, and an antiblocking agent.
- An agent or the like can be used. These additives may be used alone or in combination of two or more.
- the thickener (B) is relatively insoluble in the aqueous medium (Z), and thus when the solidified product is obtained, the thickener remaining in the aqueous urethane resin (A) is It is considered that a porous structure could be easily formed because of cavitation during drying.
- a thickener having an oxyethylene group content exceeding 2 ⁇ 10 ⁇ 2 mol / g is used, since water-solubilization is strong, cavitation as described above does not occur.
- the content of the oxyethylene group in the thickener (B) is preferably 1.8 ⁇ 10 ⁇ 2 mol / g or less from the viewpoint that a more favorable porous structure can be formed. 10 ⁇ 2 mol / g or less is more preferable.
- thickener (B) oxyethylene group to the total mass of all the compounds included in the [CH 2 CH 2 It is calculated using the total number of moles of O].
- an additive such as an emulsifier, and water as the thickener (B)
- water is removed, that is, the urethane compound and the additive. It is calculated by the total number of moles of the oxyethylene group in the urethane compound and additive with respect to the total mass of the agent.
- the blending amount of the thickener (B) is less than 0.01 parts by mass, there is a problem that a desired thickening effect cannot be obtained and coating properties are poor, and a porous structure cannot be formed.
- the amount exceeds 30 parts by mass not only a porous structure cannot be formed, but also a brittle membrane makes it impossible to obtain an industrially usable film.
- the blending amount of the thickener (B) is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the water-based urethane resin (A) from the viewpoint that an even better porous structure is obtained.
- the range of 0.15 to 10 parts by mass is more preferable, and the range of 0.2 to 7 parts by mass is even more preferable.
- the compounding quantity of the said thickener (B) shall be calculated by solid content. For example, when carboxymethylcellulose is diluted with water as the thickener (B), the blending amount of the thickener (B) is calculated based on the amount of carboxymethylcellulose itself used.
- a urethane thickener containing an urethane compound an additive such as an emulsifier, and water is used as the thickener (B), water is removed, that is, the urethane compound and The blending amount of the thickener (B) is calculated from the total mass of the additive.
- the thickener (B) include cellulose thickeners; acrylic thickeners; urethane thickeners; protein thickeners such as casein, sodium caseinate, and ammonium caseinate; polyvinyl alcohol , Polyvinyl pyrrolidone, polyvinyl benzyl ether copolymer, etc .; polyether thickeners such as pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy modified product; vinyl methyl ether-anhydrous maleic A maleic anhydride thickener such as an acid copolymer; a polyamide thickener such as a polyamidoamine salt can be used. These thickeners may be used alone or in combination of two or more.
- the compounded liquid containing the aqueous urethane resin (A) and the thickener (C) is in a dispersed state suitable for forming a porous structure, and an even better porous structure. It is preferable to use a cellulose thickener and / or a urethane thickener from the viewpoint that can be formed.
- cellulose thickener for example, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and the like can be used. These thickeners may be used alone or in combination of two or more. Among these, it is preferable to use methylcellulose because the compounded liquid containing the aqueous urethane resin (A) and the thickener (C) is in a dispersed state suitable for the formation of a porous structure and can form a more favorable porous structure. preferable.
- urethane thickener for example, one containing a urethane compound which is a reaction product of oxyalkylene polyol and polyisocyanate can be used.
- oxyalkylene polyol for example, a polymer of polyhydric alcohol and alkylene oxide can be used.
- polyhydric alcohol examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane Glycols such as 1,4-diol and cyclohexane-1,4-dimethanol; polyester polyols and the like can be used. These compounds may be used alone or in combination of two or more.
- alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These compounds may be used alone or in combination of two or more.
- polyethylene glycol is preferably used from the viewpoint of production stability and thickening.
- the number average molecular weight of the polyoxyalkylene polyol is preferably in the range of 2,000 to 12,000, more preferably in the range of 2,500 to 10,000, from the viewpoint of improving processability when adjusting the blended liquid. It is more preferable that In addition, the number average molecular weight of the said polyoxyalkylene polyol shows the value measured similarly to the number average molecular weight of the said polyol (a1).
- the polyoxyalkylene polyol may be used in combination with other polyols as necessary.
- the other polyol include polycarbonate polyol, polyester polyol, polyacryl polyol, polybutadiene polyol, and the like. These polyols may be used alone or in combination of two or more.
- polyisocyanate examples include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone.
- aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate,
- Aliphatic or alicyclic polyisocyanates such as diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic or alicyclic polyisocyanates are preferably used, and hexane diisocyanate is more preferable from the viewpoint that an even better multilayer structure can be formed.
- the urethane compound may further include a hydroxyl group or an amino group and a hydrophobic group, and the end of the urethane compound may be a hydrophobic group.
- Examples of the compound having a hydroxyl group or an amino group and a hydrophobic group include 2-butyl-1-octanol, 2-butyl-1-decanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol, Branched aliphatic alcohols such as isononyl alcohol, isodecyl alcohol, isoundecyl alcohol; 1-hexadecanol, 1-tetradecanol, 1-dodecanol, 1-undecanol, 1-decanol, 1-nonanol, 1-hexanol Linear aliphatic alcohols such as octanol and 1-hexanol; alkylaryl alcohols such as nonylphenol and tristyrylphenol; aliphatic amines such as 1-decylamine, 1-octylamine, 1-hexylamine, dioctylamine and dihexylamine; Polyethylene glycol
- the weight average molecular weight of the urethane compound is preferably in the range of 2,000 to 100,000, more preferably in the range of 10,000 to 90,000, from the viewpoint that an even better porous structure can be formed.
- the range of 20,000 to 80,000 is more preferable.
- the weight average molecular weight of the said urethane compound shows the value measured similarly to the number average molecular weight of the said polyol (a1).
- the urethane thickener may contain an additive in addition to the urethane compound.
- an aqueous medium an emulsifier, an antifoamer, a dispersing agent etc. can be used, for example, These additives may be used independently or may use 2 or more types together.
- an emulsifier the thing similar to the said emulsifier which can be used when manufacturing the said water-based urethane resin composition can be used, for example.
- a urethane thickener as the thickener (B), as a method for adjusting the content of oxyethylene groups, for example, a polyoxyalkylene polyol used as a raw material having a low content of oxyethylene groups
- the method of using, the method of reducing the usage-amount of polyethyleneglycol, the method of using what has little content of an oxyethylene group as an emulsifier, the method of reducing the usage-amount of the emulsifier which has an oxyethylene group, etc. are mentioned.
- an aqueous urethane resin composition containing the thickener (B) is obtained from the point that a better porous structure is obtained. It is preferable to increase the viscosity to 400 mPa ⁇ s or more, more preferable to increase the viscosity to a range of 450 to 10,000 mPa ⁇ s, and even more preferable to increase the viscosity to a range of 500 to 8,000 mPa ⁇ s.
- the measuring method of the viscosity of the water-based urethane resin composition (including a thickener) after thickening shows a value measured with a B-type viscometer (M3 rotor, 30 rotations) at 25 ° C.
- a B-type viscometer M3 rotor, 30 rotations
- the thickener (B) and the aqueous urethane resin composition may be brought into contact.
- the (B) And a method of mixing the aqueous urethane resin composition.
- a stirring bar, a mechanical mixer, or the like can be used.
- the thickened aqueous urethane resin composition is coagulated with a coagulant (C) containing a metal salt (c-1).
- the metal salt (c-1) 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, it is preferable to use calcium nitrate because the coagulation property can be further improved by the magnitude of the electric double layer compression effect.
- the coagulant (C) may contain a solvent.
- the solvent examples include an aqueous medium similar to the aqueous medium (Z); methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pen
- alcohol solvents such as butanol, 2-pentanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, cyclohexanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, etc. be able to.
- the content of the metal salt (c-1) in the coagulant (C) is preferably in the range of 1 to 40% by mass from the viewpoint of satisfactory salt coagulation. A range is more preferred.
- the method for producing the solidified product for example, after the aqueous urethane resin composition is thickened using the thickener (B), the thickened aqueous urethane resin composition is applied to a substrate or A method of producing a coagulated product by dipping in the coagulant (C) after dipping and then drying; after coating or dipping the substrate in the coagulant (C), and further after the thickening And a method for producing a coagulated product by coating or dipping the aqueous urethane resin composition and then drying.
- These methods can be appropriately determined depending on the substrate and the application used.
- the substrate examples include fiber substrates such as non-woven fabrics, woven fabrics, and knitted fabrics: wooden substrates such as plates, MDF (medium density fiberboard), and particle boards; metal substrates such as aluminum and iron; polycarbonate substrates, Cycloolefin resin substrate, acrylic resin substrate, silicon resin substrate, epoxy resin substrate, fluororesin substrate, polystyrene resin substrate, polyester resin substrate, polysulfone resin substrate, polyarylate resin substrate, polyvinyl chloride Resin base material, polyvinylidene chloride base material, amorphous polyolefin resin base material, polyimide resin base material, alicyclic polyimide resin base material, cellulose resin base material, TAC (triacetyl cellulose) base material, COP (cycloolefin polymer) ) Base material, PC (polycarbonate) base material, PBT (polybutylene terephthalate) ) Base materials, modified PPE (polyphenylene ether) base materials, PEN (polyethylene n
- Examples of the method for applying the thickened aqueous urethane resin composition to the substrate include a knife coater method, a spray method, a curtain coater method, a flow coater method, a roll coater method, and a brush coating method. It is done.
- the coating thickness at this time is appropriately determined depending on the intended use, and is, for example, in the range of 10 to 2,000 ⁇ m.
- a method of immersing the coated material coated with the aqueous urethane resin composition in the coagulant (C) for example, the coated material is directly placed in a tank in which the coagulant (C) is stored.
- a method of immersing and allowing salt coagulation to proceed is exemplified.
- the immersion / solidification time at this time is, for example, 1 second to 30 minutes.
- Examples of the method of immersing the substrate in the coagulant (C) include a method of directly immersing the substrate in a tank storing the coagulant (C).
- the immersion time is, for example, 1 second to 5 minutes.
- the immersion material is directly immersed in a tank in which the aqueous urethane resin composition after the thickening is stored, and salt coagulation is performed.
- the method of advancing is mentioned.
- the immersion / solidification time at this time is, for example, 1 second to 10 minutes.
- the solidified product may be immersed in water for 10 minutes to 8 hours, or immersed in running water, and unnecessary coagulant may be washed away. Further, it may be dried with hot air at 60 to 120 ° C. for 1 minute to 3 hours.
- the aqueous urethane resin composition can be made porous without being heated or foamed, and thus a solidified product having a porous structure can be obtained easily and stably. .
- Preparation Example 1 Preparation of aqueous urethane resin composition (X-1) In a nitrogen-substituted container equipped with a thermometer, nitrogen gas, an introduction tube, and a stirrer, polytetramethylene ether glycol (number average molecular weight; 2000) 500 parts by mass, 2,2′-dimethylolpropionic acid (hereinafter abbreviated as “DMPA”) 25 parts by mass, dicyclohexylmethane diisocyanate (hereinafter abbreviated as “H 12 MDI”) 128 parts by mass, and methyl ethyl ketone In the presence of 620 parts by mass, the reaction was carried out at 70 ° C.
- DMPA 2,2′-dimethylolpropionic acid
- H 12 MDI dicyclohexylmethane diisocyanate
- the obtained emulsion and 3.2 parts by mass of a chain extender aqueous solution containing 2.6 parts by mass of hydrazine were mixed and subjected to a chain extension reaction to obtain an aqueous dispersion of urethane resin (A-1). Subsequently, the aqueous dispersion was desolvated to obtain an aqueous urethane resin composition (X-1) having a nonvolatile content of 30% by mass.
- Preparation Example 2 Preparation of water-based urethane resin composition (X-2) Polycarbonate diol ("Ethanacol” manufactured by Ube Industries, Ltd.) was placed in a nitrogen-substituted container equipped with a thermometer, nitrogen gas, introduction pipe, and stirrer. UH-200 ”, number average molecular weight; 2000) In the presence of 250 parts by weight, DMPA 18 parts by weight, H 12 MDI 90 parts by weight, and methyl ethyl ketone 236 parts by weight, the reaction is carried out at 70 ° C. until reaching the specified NCO% of the reactants.
- a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the terminal was obtained.
- 16 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the urethane prepolymer and stirred, and further 797 parts by mass of water was added and stirred to obtain an emulsion in which the urethane prepolymer was dispersed in water. .
- the obtained emulsion and 6.3 parts by mass of a chain extender aqueous solution containing 5.0 parts by mass of hydrazine were mixed and subjected to a chain extension reaction to obtain an aqueous dispersion of urethane resin (A-2).
- the aqueous dispersion was desolvated to obtain an aqueous urethane resin composition (X-2) having a nonvolatile content of 35% by mass.
- Preparation Example 3 Preparation of aqueous polyurethane composition (X-3) 1,6-hexanediol (hereinafter “HG”) in a nitrogen-substituted container equipped with a thermometer, nitrogen gas, an introduction tube, and a stirrer 155 parts by mass, 137 parts by mass of neopentyl glycol, and 424 parts by mass of adipic acid were added and melted at 120 ° C. Next, the temperature was raised to 220 ° C. over 3 hours to 4 hours with stirring and held for 5 hours, and then cooled to 150 ° C., then 88 parts by mass of DMPA was added, and stirred at 150 ° C. for 5 hours to 10 hours.
- HG 1,6-hexanediol
- methyl ethyl ketone solution (X-3-a) of a polyester polyol having a carboxyl group having a nonvolatile content of 70% by mass 300 parts by mass of methyl ethyl ketone was added to prepare a methyl ethyl ketone solution (X-3-a) of a polyester polyol having a carboxyl group having a nonvolatile content of 70% by mass.
- a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the terminal was obtained.
- 17.2 parts by mass of triethylamine as a neutralizing agent is added to an organic solvent solution of the urethane prepolymer and stirred, and then 653 parts by mass of water and 7.7 parts by mass of piperazine are added and mixed to carry out chain elongation reaction.
- An aqueous dispersion of resin (A-3) was obtained.
- the aqueous dispersion was desolvated to obtain an aqueous urethane resin composition (X-3) having a nonvolatile content of 40% by mass.
- an aqueous dispersion of an aqueous urethane resin was obtained by adding 2,566 parts by mass of water to the organic solvent solution of the urethane prepolymer and stirring.
- the obtained emulsion and 135 parts by mass of a chain extender aqueous solution containing 13.5 parts by mass of piperazine were mixed and subjected to a chain extension reaction to obtain an aqueous dispersion of urethane resin (A′-1).
- the aqueous dispersion was desolvated to obtain an aqueous urethane resin composition (X′-1) having a nonvolatile content of 40% by mass.
- Example 1 Methyl cellulose diluted to 10% by mass with water in 100 parts by mass of the aqueous urethane resin composition (X-1) (“MOTOLOSE SM-15” manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as “MC”) 6.3
- MC aqueous urethane resin composition
- the mass part was stirred with a mechanical mixer at 800 rpm for 10 minutes, and then defoamed using a centrifugal defoamer to prepare a blended solution.
- the viscosity of the blended liquid (aqueous urethane resin composition containing a thickener) was 560 mPa ⁇ s. Further, the compounded solution was applied onto the release-treated polypropylene film using a knife coat.
- the coated product was immersed in a 5% by mass calcium nitrate aqueous solution for 3 minutes to solidify the blended solution. Thereafter, the coagulated product was immersed in running water for 5 hours, and the excess coagulant was washed away. Next, the coagulum was dried at 70 ° C. for 20 minutes and at 120 ° C. for 20 minutes to obtain a dried coagulum.
- Examples 2 to 7, Comparative Examples 1 to 4 A coagulum was prepared in the same manner as in Example 1 except that the type of aqueous urethane resin composition used, the type and amount of thickener (B) were changed as shown in Tables 1 to 4.
- a phenolphthalein indicator was mixed with the mixed solution, and then titrated with a 0.1 mol / L potassium hydroxide aqueous solution that had been standardized in advance. From the amount of the potassium hydroxide aqueous solution used for the titration, the following calculation formula (2) Then, the acid value (mgKOH / g) of the aqueous urethane resin (A) was determined.
- Formula A (B ⁇ f ⁇ 5.611) / S (2)
- A is the solid content acid value of the resin (mgKOH / g)
- B is the amount of 0.1 mol / L potassium hydroxide aqueous solution used for titration (mL)
- f is the 0.1 mol / L potassium hydroxide aqueous solution.
- S is the mass (g) of resin particles
- 5.611 is the formula weight of potassium hydroxide (56.11 / 10).
- Comparative Example 1 is an embodiment in which, instead of the thickener (B), a thickener having an oxyethylene group content exceeding the range specified in the present invention is used, the obtained coagulated product has a porous structure. It turned out that it did not form.
- Comparative Example 2 is an embodiment using a nonionic urethane resin having no acid value in place of the aqueous urethane resin (A), but a coagulated product was not obtained.
- Comparative Example 3 is an embodiment in which the amount of the thickener (B) used is below the range specified in the present invention, but it was found that the obtained coagulum did not form a porous structure. Moreover, the desired thickening effect was not obtained, the coating property was extremely poor, and it was extremely difficult to produce a uniform film.
- Comparative Example 4 is an embodiment in which the amount of thickener (B) used exceeds the range specified in the present invention, but it was found that the obtained coagulum does not form a porous structure. Further, the obtained film was brittle and was not industrially usable.
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Abstract
Description
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。
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」
温度計、窒素ガス、導入管、及び撹拌機を備えた窒素置換された容器中で、ポリテトラメチレンエーテルグリコール(数平均分子量;2000)500質量部、2,2’-ジメチロールプロピオン酸(以下「DMPA」と略記する。)25質量部、ジシクロヘキシルメタンジイソシアネート(以下「H12MDI」と略記する。)128質量部、及びメチルエチルケトン620質量部の存在下、反応物の規定のNCO%に達する時点まで70℃で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、前記ウレタンプレポリマーの有機溶剤溶液に、中和剤としてトリエチルアミン23質量部加えて攪拌し、更に水830質量部加え撹拌することにより、前記ウレタンプレポリマーが水に分散した乳化液を得た。
得られた乳化液とヒドラジン2.6質量部を含む鎖伸長剤水溶液3.2質量部とを混合し鎖伸長反応することによってウレタン樹脂(A-1)の水分散体を得た。次いで、この水分散体を脱溶剤することにより、不揮発分;30質量%の水性ウレタン樹脂組成物(X-1)を得た。
温度計、窒素ガス、導入管、及び撹拌機を備えた窒素置換された容器中で、ポリカーボネートジオール(宇部興産株式会社製「エタナコールUH-200」、数平均分子量;2000)250質量部、DMPA18質量部、H12MDI90質量部、及びメチルエチルケトン236質量部の存在下、反応物の規定のNCO%に達する時点まで70℃で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、前記ウレタンプレポリマーの有機溶剤溶液に、中和剤としてトリエチルアミン16質量部加えて攪拌し、更に水797質量部加え撹拌することにより、前記ウレタンプレポリマーが水に分散した乳化液を得た。
得られた乳化液とヒドラジン5.0質量部を含む鎖伸長剤水溶液6.3質量部とを混合し鎖伸長反応することによってウレタン樹脂(A-2)の水分散体を得た。次いで、この水分散体を脱溶剤することにより、不揮発分;35質量%の水性ウレタン樹脂組成物(X-2)を得た。
温度計、窒素ガス、導入管、及び撹拌機を備えた窒素置換された容器中で、1,6-ヘキサンジオール(以下「HG」と略記する。)155質量部、ネオペンチルグリコール137質量部、アジピン酸424質量部添加し、120℃でそれらを溶融した。次いで、撹拌しながら3時間~4時間かけて220℃へ昇温し5時間保持した後、150℃まで冷却した後、DMPAを88質量部添加し、150℃で撹拌しながら5時間~10時間保持した後、メチルエチルケトン300質量部添加することによって、不揮発分70量%のカルボキシル基を有するポリエステルポリオールのメチルエチルケトン溶液(X-3-a)を調製した。
温度計、窒素ガス、導入管、及び撹拌機を備えた窒素置換された容器中で、上記カルボキシル基を有するポリエステルポリオール(X-3-a)のメチルエチルケトン溶液198質量部、ポリエステルポリオール(DIC株式会社製「クリスボンCMA-654」、数平均分子量;1,500)160質量部、HG19質量部、トリレンジイソシアネート75質量部、及びメチルエチルケトン152質量部の存在下、反応物の規定のNCO%に達する時点まで70℃で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、ウレタンプレポリマーの有機溶剤溶液に、中和剤としてトリエチルアミン17.2質量部加えて攪拌し、更に水を653質量部、ピペラジン7.7質量部を加え混合し鎖伸長反応することによってウレタン樹脂(A-3)の水分散体を得た。次いで、この水分散体を脱溶剤することにより、不揮発分;40質量%の水性ウレタン樹脂組成物(X-3)を得た。
温度計、窒素ガス、導入管、及び撹拌機を備えた窒素置換された容器中で、ポリテトラメチレングリコール(三菱化学株式会社製、数平均分子量:2,000)1,000質量部、日油株式会社製「ユニルーブ75DE-60」(ポリオキシエチレンオキシプロピレングリコール、ポリオキシエチレン構造/ポリオキシプロピレン構造(質量割合)=75/25、数平均分子量:約3,000)50質量部、日油株式会社製「ユニルーブ75MB-900」(ポリオキシエチレンオキシプロピレングリコールモノブチルエーテル、ポリオキシエチレン構造/ポリオキシプロピレン構造(質量割合)=75/25、数平均分子量約3,400)50質量部、H12MDI183質量部、及びメチルエチルケトン1,283質量部の存在下、反応物の規定のNCO%に達する時点まで70℃で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーのメチルエチルケトン溶液を得た。
次いで、ウレタンプレポリマーの有機溶剤溶液に、水を2,566質量部加え撹拌することにより、水性ウレタン樹脂の水分散体を得た。得られた乳化液と、ピペラジン13.5質量部を含む鎖伸長剤水溶液135質量部とを混合し鎖伸長反応することによってウレタン樹脂(A’-1)の水分散体を得た。次いで、この水分散体を脱溶剤することにより、不揮発分;40質量%の水性ウレタン樹脂組成物(X’-1)を得た。
水性ウレタン樹脂組成物(X-1)100質量部に、水で10質量%に希釈したメチルセルロース(信越化学工業株式会社製「MOTOLOSE SM-15」、以下「MC」と略記する。)6.3質量部をメカニカルミキサーにて800rpmで10分間撹拌し、次いで遠心脱泡器を使用して脱泡させて配合液を作製した。前記配合液(増粘剤を含む水性ウレタン樹脂組成物)の粘度は、560mPa・sであった。更に、離型処理されたポリプロピレンフィルム上にナイフコートを使用して配合液を塗工した。次いで、該塗工物を5質量%の硝酸カルシウム水溶液中に3分間浸漬させて配合液を凝固させた。その後、凝固物を5時間流水に浸し、余分な凝固剤を洗浄除去した。次いで、この凝固物を70℃で20分間、及び120℃で20分間乾燥することによって乾燥した凝固物を得た。
用いる水性ウレタン樹脂組成物の種類、増粘剤(B)の種類、及び量を表1~4に示す通りに変更した以外は、実施例1と同様にして凝固物を作製した。
調製例にて得た水性ウレタン樹脂組成物をレーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製「LA-910」)を使用して、分散液として水を使用し、相対屈折率=1.10、粒子径基準が面積の時の平均粒子径を測定した。
調整例にて得た水性ウレタン樹脂組成物を乾燥し、乾燥固化した樹脂粒子の0.05g~0.5gを、300mL三角フラスコに秤量し、次いで、テトラヒドロフランとイオン交換水との質量割合[テトラヒドロフラン/イオン交換水]が80/20の混合溶媒約80mLを加えそれらの混合液を得た。
次いで、前記混合液にフェノールフタレイン指示薬を混合した後、あらかじめ標定された0.1mol/Lの水酸化カリウム水溶液で滴定し、滴定に用いた水酸化カリウム水溶液の量から下記計算式(2)に従い、水性ウレタン樹脂(A)の酸価(mgKOH/g)を求めた。
計算式 A=(B×f×5.611)/S (2)
式中、Aは樹脂の固形分酸価(mgKOH/g)、Bは滴定に用いた0.1mol/L水酸化カリウム水溶液の量(mL)、fは0.1mol/L水酸化カリウム水溶液のファクター、Sは樹脂粒子の質量(g)、5.611は水酸化カリウムの式量(56.11/10)である。
実施例及び比較例で得られた凝固物を、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:2,000倍)を使用して観察し、以下のように評価した。
「T」;電子顕微鏡写真のウレタン樹脂層の断面図において、孔が多数確認される。 「F」;上記以外のもの。
・「L75N」:Borchers社「Borch Gel L75N」(1,6-ヘキサンジイソシアネート、数平均分子量が3,000のポリエチレングリコール及び数平均分子量が6,000のポリエチレングリコールの反応物と、ポリオキシエチレンジスチレン化フェニルエーテルと、アセチレングリコールと、水(含有率:50質量%)とを含むもの、オキシエチレン基の含有量:1.6×10-2mol/g)
・「T10」:DIC株式会社製「アシスター T10」(1,6-ヘキサンジイソシアネート及び数平均分子量が6,000のポリエチレングリコールの反応物と、ポリオキシエチレンジスチレン化フェニルエーテルと、水(含有率:75質量%)とを含むもの、オキシエチレン基の含有量:2.1×10-2mol/g)
Claims (1)
- 酸価が0.01mgKOH/g以上の水性ウレタン樹脂(A)を含む水性ウレタン樹脂組成物に対して、
オキシエチレン基の含有量が2×10-2mol/g以下の増粘剤(B)を、
前記水性ウレタン樹脂(A)100質量部に対して0.01~30質量部の範囲で配合して増粘させた後に、
金属塩(c-1)を含む凝固剤(C)で凝固することを特徴とする凝固物の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017542204A JP6323620B1 (ja) | 2016-06-01 | 2017-04-25 | 凝固物の製造方法 |
KR1020187030756A KR102116292B1 (ko) | 2016-06-01 | 2017-04-25 | 응고물의 제조 방법 |
US16/304,651 US11046805B2 (en) | 2016-06-01 | 2017-04-25 | Method for producing coagulate |
CN201780032142.8A CN109196050B (zh) | 2016-06-01 | 2017-04-25 | 凝固物的制造方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09272753A (ja) * | 1996-04-03 | 1997-10-21 | Sanyo Chem Ind Ltd | 微多孔性シートの製造方法および微多孔性シート |
JP2002179758A (ja) * | 2000-12-13 | 2002-06-26 | Asahi Kasei Corp | ポリウレタンエマルジョンおよびそれを用いて製造する合成皮革及び人工皮革 |
JP2006096852A (ja) * | 2004-09-29 | 2006-04-13 | Sanyo Chem Ind Ltd | 水系ポリウレタン樹脂エマルション |
WO2015012117A1 (ja) * | 2013-07-22 | 2015-01-29 | Dic株式会社 | 手袋 |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3619250A (en) | 1968-07-18 | 1971-11-09 | Kanegafuchi Spinning Co Ltd | Method for making microporous sheet material |
JPS60122760A (ja) | 1983-12-08 | 1985-07-01 | 株式会社間組 | 水中セメント質物質組成物 |
JPH0219503A (ja) | 1988-07-07 | 1990-01-23 | Dai Ichi Kogyo Seiyaku Co Ltd | 作業用手袋の製造法 |
US5352711A (en) | 1991-08-12 | 1994-10-04 | The Proctor & Gamble Company | Method for hydrophilizing absorbent foam materials |
JP3196139B2 (ja) | 1998-11-25 | 2001-08-06 | 株式会社市金テクニカル | 人工皮革の製造方法 |
TWI256340B (en) * | 1999-02-01 | 2006-06-11 | Dainippon Ink & Chemicals | Aqueous urethane resin composition for forming pores, process for producing fiber sheet-shape composite |
JP2001011254A (ja) | 1999-06-30 | 2001-01-16 | Mitsui Chemicals Inc | サック製造用水性樹脂組成物 |
JP2001123306A (ja) | 1999-10-22 | 2001-05-08 | Seikoh Chem Co Ltd | Nbr製手袋およびその製造方法 |
JP3981242B2 (ja) | 2000-12-21 | 2007-09-26 | 日華化学株式会社 | 多孔性構造体の製造方法 |
DE10140206A1 (de) * | 2001-08-16 | 2003-03-06 | Bayer Ag | Einkomponentige isocyanatvernetzende Zweiphasen-Systeme |
US7306825B2 (en) | 2002-12-20 | 2007-12-11 | Dow Global Technologies Inc. | Process to make synthetic leather and synthetic leather made therefrom |
JP4249069B2 (ja) | 2004-03-25 | 2009-04-02 | 第一工業製薬株式会社 | 繊維積層体の製造方法、繊維積層体及び合成皮革 |
GB2400051B (en) | 2004-03-31 | 2005-03-09 | John Ward Ceylon | Polymeric garment material |
US7814571B2 (en) | 2006-02-23 | 2010-10-19 | Ansell Healthcare Products Llc | Lightweight thin flexible polymer coated glove and a method therefor |
KR100969041B1 (ko) | 2008-03-25 | 2010-07-09 | 현대자동차주식회사 | 생체질감을 갖는 무용제 폴리우레탄계 인조피혁 및 이의제조방법 |
CN101328383A (zh) * | 2008-07-17 | 2008-12-24 | 安徽大学 | 用于衬里手套水性聚氨酯涂层连接料的生产方法 |
JP5407911B2 (ja) | 2009-02-18 | 2014-02-05 | 東ソー株式会社 | 水性ポリウレタン樹脂組成物およびこれを用いたフィルム成型体 |
CN101717487A (zh) * | 2009-11-20 | 2010-06-02 | 天津碧海蓝天水性高分子材料有限公司 | 一种用于针织内衬手套水性涂饰剂的聚氨酯乳液和涂饰剂及其制备方法和涂覆方法 |
JP6004621B2 (ja) | 2011-09-13 | 2016-10-12 | 株式会社東和コーポレーション | 手袋 |
CN102875769A (zh) | 2011-07-15 | 2013-01-16 | 株式会社Lg化学 | 聚氨酯树脂组合物及聚氨酯支撑垫片 |
JP5158459B1 (ja) * | 2011-07-29 | 2013-03-06 | Dic株式会社 | ポリウレタンフィルム及びそれを用いたフィルム加工品 |
JP2013083031A (ja) | 2011-09-29 | 2013-05-09 | Kuraray Co Ltd | 多孔性構造体の製造方法 |
CN103343457B (zh) * | 2013-07-11 | 2015-12-02 | 丽水市优耐克水性树脂科技有限公司 | 一种利用水性聚氨酯制备湿法贝斯的方法 |
JP5858314B2 (ja) | 2013-09-06 | 2016-02-10 | Dic株式会社 | 皮革様シート |
WO2015146334A1 (ja) | 2014-03-26 | 2015-10-01 | Dic株式会社 | 手袋 |
JP6408842B2 (ja) | 2014-09-12 | 2018-10-17 | ショーワグローブ株式会社 | 耐切創性手袋及び耐切創性手袋の製造方法 |
CN104497258A (zh) | 2014-12-16 | 2015-04-08 | 安徽灵达化工科技有限公司 | 一种超弹耐磨水性聚氨酯树脂、组合物及其应用 |
JP6597007B2 (ja) | 2015-07-16 | 2019-10-30 | Dic株式会社 | 凝固物の製造方法 |
EP3327066A4 (en) | 2015-07-21 | 2019-03-20 | DIC Corporation | METHOD FOR PRODUCING A COAGULATED ARTICLE |
JP2017036516A (ja) | 2015-08-07 | 2017-02-16 | 住友ゴム工業株式会社 | 手袋の製造方法 |
US11229248B2 (en) | 2015-12-02 | 2022-01-25 | Showa Glove Co. | Supporting glove and method for manufacturing the supporting glove |
JP6631218B2 (ja) | 2015-12-09 | 2020-01-15 | Dic株式会社 | 凝固物の製造方法 |
WO2017208681A1 (ja) * | 2016-06-01 | 2017-12-07 | Dic株式会社 | 多孔体の製造方法 |
-
2017
- 2017-04-25 WO PCT/JP2017/016301 patent/WO2017208680A1/ja unknown
- 2017-04-25 EP EP17806240.2A patent/EP3467036A4/en active Pending
- 2017-04-25 CN CN201780032142.8A patent/CN109196050B/zh active Active
- 2017-04-25 KR KR1020187030756A patent/KR102116292B1/ko active IP Right Grant
- 2017-04-25 JP JP2017542204A patent/JP6323620B1/ja active Active
- 2017-04-25 US US16/304,651 patent/US11046805B2/en active Active
- 2017-05-24 TW TW106117195A patent/TWI732874B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09272753A (ja) * | 1996-04-03 | 1997-10-21 | Sanyo Chem Ind Ltd | 微多孔性シートの製造方法および微多孔性シート |
JP2002179758A (ja) * | 2000-12-13 | 2002-06-26 | Asahi Kasei Corp | ポリウレタンエマルジョンおよびそれを用いて製造する合成皮革及び人工皮革 |
JP2006096852A (ja) * | 2004-09-29 | 2006-04-13 | Sanyo Chem Ind Ltd | 水系ポリウレタン樹脂エマルション |
WO2015012117A1 (ja) * | 2013-07-22 | 2015-01-29 | Dic株式会社 | 手袋 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3467036A4 * |
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KR20180127445A (ko) | 2018-11-28 |
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US11046805B2 (en) | 2021-06-29 |
TW201819481A (zh) | 2018-06-01 |
CN109196050A (zh) | 2019-01-11 |
KR102116292B1 (ko) | 2020-05-29 |
JP6323620B1 (ja) | 2018-05-16 |
US20190211133A1 (en) | 2019-07-11 |
EP3467036A4 (en) | 2020-01-08 |
EP3467036A1 (en) | 2019-04-10 |
CN109196050B (zh) | 2021-09-21 |
TWI732874B (zh) | 2021-07-11 |
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