WO2005040488A1 - Process for producing porous structure, artificial leather, and synthetic leather - Google Patents

Abstract

A process for producing a porous structure which comprises: applying to a substrate a liquid mixture comprising (A) an aqueous dispersion of a water-compatible polyurethane, (B) an aqueous dispersion of a urethane prepolymer which has, in the molecular skeleton, 10 to 40% by mass structural unit comprising a polyoxyethylene group having an average molecular weight of 100 to 2,000 and which has been terminated by a blocked isocyanate, and (C) a tertiary amine; and subsequently subjecting the mixture to dry-heat drying or to wet-heat heating and then drying. Also provided are an artificial leather and synthetic leather obtained by the process. By the process, a porous structure having performances comparable to those of porous structures produced by a wet process from a solvent-based polyurethane can be obtained using an aqueous dispersion of a water-compatible polyurethane without using an organic solvent.

Description

 Description Method for manufacturing porous structure, artificial leather and synthetic leather

 The present invention relates to a method for producing a porous structure, artificial leather and synthetic leather. More specifically, the present invention provides a porous structure having performance comparable to that of a porous structure manufactured using a wet solvent-based polyurethane using an aqueous polyurethane without using an organic solvent. The present invention relates to a method for producing a porous structure that can be obtained, and an artificial leather and a synthetic leather obtained by the method. Background art

 Conventionally, various types of leather preparations such as artificial leather, synthetic leather, and artificial leather have been manufactured as substitutes for natural leather. Many products have a porous structure formed inside or above a base material such as woven fabric, knitted fabric, or nonwoven fabric in order to make the texture and air permeability close to that of natural leather. These porous structures are produced by dissolving a polymer such as elastic polyurethane in a water-soluble organic solvent such as dimethylformamide, and impregnating or coating the substrate with a solution containing various additives. After that, the wet coagulation method of solidifying the polymer by treating it with a solvent that is miscible with the water-soluble organic solvent without dissolving the polymer, followed by desolvation and drying is commonly used. I have. However, in this wet coagulation method, since the water-soluble organic solvent used is highly flammable and highly toxic, there are problems such as fire danger, deterioration of working environment, and environmental pollution. . In addition, there is a concern that the manufactured leather preparations may remain with water-soluble organic solvents and the like. Therefore, a great deal of labor and cost are required to prevent these.

In order to solve these problems, studies are being made on a method for producing a porous structure using an aqueous system with a low environmental impact.For example, using a foaming agent in an aqueous polyurethane aqueous dispersion to mix air bubbles inside A method of forming a crosslinked structure by heating and coagulating an aqueous dispersion of an aqueous polyurethane in the presence of a water-soluble polymer such as starch to form a crosslinked structure, followed by washing with water to remove the water-soluble polymer to obtain a porous structure. The aqueous polyurethane aqueous dispersion contains inorganic salts or Is a method of obtaining a porous structure using an inorganic mineral.

 As a method for producing a porous body suitable for artificial leather without using an organic solvent, a water-soluble high-crystalline natural product is added to an aqueous polyurethane resin emulsion, and the water-soluble high-crystalline natural product is further heated by wet heat. A method has been proposed in which a cross-linking agent and an additive that are made water-insoluble in the coagulation process are used in combination, and a portion where moisture was present after drying is converted into a continuous foam porous body (Patent Document 1). Furthermore, without using a highly flammable or toxic water-soluble organic solvent, a method for producing a porous structure having a structure similar to that of natural leather has been developed by using aqueous thermoplastic binder and aqueous polyurethane prepolymer. In addition to the isocyanate block, a method is proposed in which a mixture containing at least one of an inorganic compound, a water-soluble organic polymer, and a high cloud point surfactant is applied to the substrate, and heated and heated with moisture and dried. (Patent Document 2). However, it has been difficult to stably obtain a porous structure by any method.

 [Patent Literature 1] Japanese Patent Application Laid-Open No. 2001-17-172882 (page 2)

 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-249987 (pages 2-3) DISCLOSURE OF THE INVENTION

 According to the present invention, it is possible to obtain a porous structure having a performance comparable to that of a porous structure manufactured using a wet solvent-based polyurethane using an aqueous polyurethane aqueous dispersion without using an organic solvent. An object of the present invention is to provide a method for producing a porous structure, and an artificial leather and a synthetic leather obtained by the method. The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that (A) an aqueous polyurethane water dispersion, and (B) a polyoxyethylene group having an average molecular weight of 100 to 2,000. A urethane pre-bolimer-terminated isocyanate block aqueous dispersion having 10 to 40% by mass of the following structural unit in the molecular skeleton, and (C) a mixed solution containing tertiary amine: The porous structure obtained by applying it to a substrate such as a woven or knitted fabric and then drying it by dry heat drying or wet heat heating and then drying it has strength and texture compared to artificial leather or synthetic leather manufactured using solvent-based polyurethane. The present invention has been found to have comparable performance, and based on this knowledge, the present invention has been completed.

 That is, the present invention

(1) (A) aqueous polyurethane aqueous dispersion, (B) polio having an average molecular weight of 100 to 2,000 Applying a mixed solution containing a urethane prepolymer-terminated isocyanate block aqueous dispersion having 10 to 40% by mass of a structural unit composed of xylene units in a molecular skeleton, and (C) a tertiary amine to a substrate And then drying after dry heat drying or wet heat heating, a method for producing a porous structure,

 (2) (A) Aqueous polyurethane aqueous dispersion contains (a) a polyol compound and (b) an isocyanate group-terminated prepolymer obtained by reacting a polyisocyanate compound, and a nonionic surfactant having an HLB of 7 to 16 is used. (D) a water-based polyurethane resin aqueous dispersion obtained by subjecting (d) a chain extension reaction to a polyamine compound having two or more amino groups and at least two Z or imino groups, and then dispersing in water. A method for producing a structure, (3) (A) an aqueous polyurethane aqueous dispersion comprising: (a) a polyol compound; (b) a polyisocyanate compound; and (c) a chain extender. After dispersing in water using a nonionic surfactant having an HLB of 7 to 16, the resulting product is subjected to a chain extension reaction with (d) a polyamine compound having two or more amino groups and / or two or more imino groups. Manufacturing method of a porous structure according to the first term is an aqueous polyurethane aqueous dispersion that,

 (4) The aqueous dispersion of (A) the aqueous polyurethane is prepared by reacting (a) a polyol compound, (b) a polyisocyanate compound and (e) a compound imparting an ionic hydrophilic group with an isocyanate group-terminated prepolymer. The porosity according to Item 1, which is an aqueous polyurethane aqueous dispersion obtained by dispersing the hydrate in water and then subjecting the chain extension reaction to (d) a polyamine compound having two or more amino groups and / or imino groups. Method for producing a conductive structure,

 (5) The (A) aqueous polyurethane dispersion is reacted with (a) a polyol compound, (b) a polyisocyanate compound, (e) a compound imparting an ionic hydrophilic group, and (c) a chain extender. After dispersing the neutralized product of the obtained isocyanate group-terminated prevolimer in water,

(d) the method for producing a porous structure according to item 1, which is an aqueous polyurethane aqueous dispersion obtained by performing a chain extension reaction with a polyamine compound having two or more amino groups and Z or imino groups,

(6) having a structural unit consisting of (A) an aqueous dispersion of water '1 raw polyurethane and (B) a polyoxyethylene group having an average molecular weight of 100 to 2,000 in a molecular skeleton of 10 to 40% by mass. The mass ratio of the urethane prepolymer-terminated isocyanate block aqueous dispersion is (A): (B) = 1 °: 90 to 90: 10 The method for producing a porous structure according to item 1, wherein

 (7) Artificial leather obtained by the method for producing a porous structure according to any one of (1) to (6), and

 (8) Synthetic leather obtained by the method for producing a porous structure according to any one of (1) to (6),

Is to provide.

 The method for producing a porous structure according to the present invention uses a mixed solution containing an aqueous dispersion of an aqueous polyurethane and an aqueous dispersion of a urethane prepolymer-terminated isocyanate block. It is possible to stably produce an artificial leather or a synthetic leather having a porous structure having open cells having an excellent texture and strength by using a simple method. According to the method of the present invention, air pollution and water pollution caused by the solvent discharged in the case of manufacturing using a conventional solvent-based polyurethane,? It is possible to reduce the labor for collecting containers and the labor environment of workers. Brief Description of Drawings

 FIG. 1 is an electron microscope photograph replacing the drawing showing the cross section of the artificial leather obtained in Example 2, and FIG. 2 is an electron microscope replacing the drawing showing the cross section of the artificial leather obtained in Comparative Example 3. FIG. 3 is an electron micrograph instead of a drawing showing a cross section of the polyurethane layer of the synthetic leather obtained in Example 11, and FIG. 4 is a synthetic leather obtained in Comparative Example 5. 3 is an electron micrograph instead of a drawing showing a cross section of the polyurethane layer of FIG. BEST MODE FOR CARRYING OUT THE INVENTION

 In the method for producing a porous structure of the present invention, (A) an aqueous dispersion of an aqueous polyurethane, and (B) a structural unit composed of a polyoxyethylene group having an average molecular weight of 100 to 2,000 are contained in a molecular skeleton. An aqueous dispersion of a urethane prepolymer-terminated isocyanate block having 10 to 40% by mass of the mixture, and (C) a mixed solution containing a tertiary amine, which is then applied to the base material. It is dried after dry heat drying or wet heat heating.

The aqueous polyurethane dispersion (A) used in the production method of the present invention may be polyurethane An aqueous dispersion obtained by emulsifying and dispersing or dissolving a polymer in water. Among these, a forced emulsification type aqueous polyurethane dispersion obtained by emulsifying and dispersing a polyurethane using an emulsifier, and a self-emulsifying type aqueous polyurethane dispersion which can be emulsified and dispersed without using an emulsifier can be preferably used.

 The aqueous polyurethane dispersion of the forced emulsification type refers to an isocyanate group-terminated prepolymer obtained by reacting (a) a polyol compound, (b) a polyisocyanate compound, and (c) a chain extender, if necessary, with HLB. Is dispersed in water using a nonionic surfactant having a molecular weight of 7 to 16, and then (d) is subjected to a chain extension reaction with a polyamine conjugate having two or more amino groups and Z or imino groups. It is a polyurethane aqueous dispersion. In the method of the present invention, HLB refers to a value calculated by Griffin's formula. The aqueous self-emulsifying polyurethane dispersion includes (a) a polyol compound, (b) a polyisocyanate compound, (e) a compound that imparts an ionizable hydrophilic group, and (c ′) a chain extender as necessary. Is dispersed in water, and then (d) a polyurethane water obtained by a chain extension reaction with a polyamine compound having two or more amino groups and / or imino groups. It is a dispersion.

The (a) polyol compound used in the method of the present invention is not particularly limited, and examples thereof include polyester polyols, polycarbonate polyols, and polyether polyols having two or more hydroxyl groups. Polyester polyols include, for example, polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, poly'ethylene sebacate, polybutylene sepacate, and polybutylene adipate. ε-force prolactone diol, poly (3-methyl-1,5-pentylene) adipate, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol, adipic acid and dimer acid Examples include a copolycondensate, a polycondensate of nonanediol and dimer acid, and a copolycondensate of ethylene glycol, adipic acid and dimer acid. Examples of the polycarbonate polyol include polytetramethylene carbonate diole, polyhexamethylene carbonate diol, and poly-1,4-cyclohexane dimethylene carbonate diol. Examples of the polyether polyol include polyethylene dalicol, Examples include homopolymers such as polypropylene dalicol and polytetramethylene glycol, random copolymers and block copolymers of ethylenoxide and propylene oxide, ethylenoxy and butylene oxide. Further, a polyetherester polyol having an ethereal bond and an ester bond can also be used. One of these polyol compounds can be used alone, or two or more can be used in combination.

The (b) polyisocyanate compound used in the method of the present invention is not particularly limited, and examples thereof include an aliphatic polyisocyanate compound having two or more isocyanate groups, an alicyclic polyisocyanate compound, and an aromatic polyisocyanate. Compounds and the like can be mentioned. Examples of the aliphatic polyisocyanate conjugate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like. Examples of the alicyclic polyisocyanate compound include, for example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dihexyl hexyl methane diisocyanate, norbornane diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexan and the like can be mentioned. Examples of the aromatic polyisocyanate compound include, for example, tolylene dicysinate, diphenylmethane diisocyanate, naphthalene diisocyanate, trizine diisocyanate, xylylene disocyanate, and tetramethyl xylylene diisocyanate. Isocyanate and the like can be mentioned. One of these polyisocyanate compounds can be used alone, or two or more can be used in combination. Among these, aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds can be suitably used because they give a non-yellowing film, and hexamethylene diisocyanate and isophorone can be used. Particularly preferred are diisocyanate, dicyclohexylmethane diisocyanate, norbornane disocyanate and 1,3-bis (isocyanatomethinole) cyclohexa. In the method of the present invention, as the chain extender (c) used as required, for example, ethylene glycolone, propylene glycolone, neopentinole glycolone, 1,4-butanediolone, 1,6-hexanediol, trihexanediol, trihexanediol Low molecular weight polyhydric alcohols such as methylolpropane, pentaerythritol and sorbitol, ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexymethane, piperazi And low-molecular-weight polyamines such as 2-methyl-4-pyrazine, isophoronediamine, diethylenetriamine and triethylenetetramine. One of these chain extenders can be used alone, or two or more can be used in combination.

 In the water dispersion of the self-molding-type polyurethane used in the method of the present invention, there is no particular limitation on the (e) compound that imparts an ionic hydrophilic group to be introduced into the urethane skeleton. For example, a compound that imparts an anionic hydrophilic group, Examples thereof include compounds that impart a cationic hydrophilic group. Examples of the compound imparting an anionic hydrophilic group include a compound in which the anionic hydrophilic group is a carboxyl group and the active hydrogen is a hydrogen of a hydroxyl group. Examples of such a compound include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Further, a polyester polyol having a pendant carboxy group, which is obtained by reacting a dicarponic acid such as an aliphatic dicarponic acid, an alicyclic dicarponic acid, or an aromatic dicarponic acid with a diol having a carboxyl group, can also be used. . In the reaction, a diol having no carboxyl group can be mixed with a diol having a carboxyl group. One of these compounds imparting an anionic hydrophilic group can be used alone, or two or more can be used in combination. These anionic hydrophilic groups include, for example, trimethylamine, triethylamine, tree n-propamine, tributylamine, methylmethylethanolamine, Ν, dimethylmonoethanolamine, triethanolamine, and the like. It is neutralized with amines, potassium hydroxide, sodium hydroxide, ammonia or the like before or after preparation of the isocyanate group-terminated prepolymer.

As the compound imparting a cationic hydrophilic group, alkanolamines can be suitably used, and examples thereof include メ チ ル -methyljetanolamine, ェ -ethyljetanolamine, and triethanolamine. . One of these alkanolamines can be used alone, or two or more can be used in combination. These cationic hydrophilic groups can be neutralized with, for example, an inorganic or organic acid such as hydrochloric acid, nitric acid, formic acid, and acetic acid, dimethyl sulfate, getyl sulfate, shiridani benzene // epichlorohydrin, etc. And use it. The method for producing the isocyanate group-terminated prepolymer used in the present invention is not particularly limited. For example, it can be produced by a one-stage so-called one-shot method or a multi-stage isocyanate polyaddition reaction method. The reaction temperature is preferably from 40 to 150 ° C. At this time, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannasoctoate, dibutyltin-12-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine can be added. . During or after the reaction, an organic solvent that does not react with the isocyanate group can be added. Examples of such an organic solvent include acetone, methylethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylene amide, and dimethylpyrrolidone.

In dispersing the isocyanate-terminated prepolymer in water in the aqueous dispersion of the forced emulsification type polyurethane used in the method of the present invention, it is preferable to use a nonionic surfactant having an HLB of 7 to 16 and an HLB of 9 to 16 It is more preferable to use 15 nonionic surfactants. If the HLB is less than 7, it is difficult to disperse the isocyanate-terminated prepolymer, and even if dispersible, the stability may be poor. When the HLB is more than 16, it is difficult to emulsify and disperse the isocyanate-terminated prepolymer, and even when the isocyanate-terminated prepolymer can be dispersed, the resulting porous structure may have poor water resistance. There is no particular limitation on the structure of the nonionic surfactant having an HLB of 7 to 16, and examples thereof include a polyoxyethylene distyrylphenyl ether type nonionic surfactant, and a polyoxyethylene propylene distyrylphenylinoleate. Ter non-ionic surfactant, polyoxyethylene tristyryl phenyl ether type non-ionic surfactant, polyoxyethylene propylene tristyryl ether ether non-ionic surfactant, Pull-opened non-ionic surfactant, etc. Can be mentioned. One of these nonionic surfactants can be used alone, or two or more can be used in combination. The amount of these nonionic surfactants used can be appropriately selected depending on the hydrophilicity derived from the polyoxyethylene of the isocyanate-terminated prepolymer, which is the substance to be emulsified. Parts by weight, preferably 0.5 to 10 parts by mass, more preferably 1 to 6 parts by mass. 0 The amount of the nonionic surfactant relative Isoshianeto group terminal Pureborima 1 0 0 parts by weight. ⁵ If the amount is less than parts by mass, it may be difficult to obtain a stable emulsified and dispersed state. If the amount of the nonionic surfactant exceeds 10 parts by mass with respect to 100 parts by mass of the isocyanate group-terminated prepolymer, the water resistance of the obtained porous structure may be reduced.

In the aqueous self-emulsifying polyurethane dispersion used in the method of the present invention, a neutralized isocyanate group-terminated prepolymer can be emulsified and dispersed in water without adding an emulsifier. Up to 16 nonionic surfactants can be used. In the case of an isocyanate group-terminated prepolymer having an anionic hydrophilic group, for example, higher fatty acid salts, resin salts, acidic fatty alcohols, sulfate esters, higher alkyl sulfonate salts, alkyl aryl sulfonates, sulfonated castor oil, sulfosuccinate Emulsifiability can be maintained by using an anionic surfactant such as an acid ester in combination. '' In the present invention, when emulsifying and dispersing a neutralized product of an isocyanate group-terminated prepolymer or isocyanate group-terminated prepolymer in water, it is preferable to use mechanical shearing force because phase inversion emulsification occurs. . There is no particular limitation on the emulsifying device that applies mechanical shearing force, and examples thereof include a homomixer and a homogenizer. The isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer is emulsified and dispersed in water at a temperature in the range of room temperature to 40 ° C in order to minimize the reaction between the isocyanate group and water or a nonionic surfactant. That's good ,. Further, if necessary, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid, and benzoyl chloride can be added. In the method of the present invention, after the isocyanate group-terminated prepolymer or the neutralized product of the isocyanate group-terminated prepolymer is dispersed in water, (d) a polyamine conjugate having two or more amino groups and / or imino groups It is preferable to carry out a chain extension reaction by using (A) to obtain an aqueous polyurethane aqueous dispersion. (D) Polyamine compounds having two or more amino groups and _ or imino groups include, for example, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine , 2-methylbiperazine, isophoronediamine, norpolnandiamine, diaminodiphenylmethane, tolylenediamine, ki Polyamines such as diamines such as silylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and tris (2-aminoethyl) amine; and derivatives derived from diprimary amines and monocarboxylic acids. Water-soluble amine derivatives such as midamine and di-primary amine monoketimine, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, Hydrazine derivatives such as fumaric dihydrazide, itaconic dihydrazide, 1,1,1-ethylene hydrazine, 1, -trimethylene hydrazine, 1,1 '-(1,4-butylene) dihydrazine and the like can be mentioned. One of these polyamine compounds can be used alone, or two or more can be used in combination.

 In the method of the present invention, the chain extension reaction of the isocyanate group-terminated prepolymer or the neutralized product of the isocyanate-terminated terminal prepolymer is carried out by: (d) a polyamine compound having two or more amino groups and / or imino groups in an emulsified dispersion of these prepolymers. Alternatively, (d) an emulsified dispersion of a prepolymer can be added to a polyamine compound having two or more amino groups and Z or imino groups. The chain extension reaction is preferably performed at a reaction temperature of 20 to 40 ° C. When an isocyanate group-terminated prepolymer is synthesized using an organic solvent, it is preferable to remove the organic solvent by distillation under reduced pressure after completion of the chain extension reaction.

The aqueous dispersion (B) of urethane prepolymer terminal-isocyanate block used in the production method of the present invention is a urethane prepolymer having hydrophilicity and heat reactivity, and an isocyanate group at the terminal of which is a block copolymer (produced by Jゥ The aqueous dispersion of urethane prepolymer-terminated isocyanate block can be stored for a long time in the form of an aqueous solution, and the blocking agent is released by heating to regenerate active isocyanate groups. , or a poly urethane polymer undergoes a polyaddition reaction between urethane Prevost Rimmer intramolecular or, alternatively, leaving the. blocking agent that can cause addition reaction with other functional groups, the temperature is ⁵ 0 The temperature is preferably 150 ° C. The urethane prepolymer-terminated isocyanate block aqueous dispersion has (f) two or more A compound having an active hydrogen, a (g) polyisobutylene Xia sulfonate compound, optionally 及 Pi (h) a chain extender It can be produced by blocking the terminal isocyanate group of the urethane prepolymer obtained by the reaction with (i) a blocking agent.

The water dispersion (B) ゥ ethane prevolimer-terminated succinate block used in the method of the present invention comprises, as a hydrophilic component, a structural unit composed of a poly (xylethylene) group having an average molecular weight of 100 to 2,000. 1 0-4 0% by weight to molecular bone袼中, more preferably 1 5-3 5 mass ^0. If the average molecular weight of the polyoxyethylene group is less than 100, it is difficult to control the reaction, and the cohesive strength of the polyurethane resin becomes too high, so that the urethane prepolymer having a blocked block is dispersed in water. This can be difficult. When the average molecular weight of the polyoxyethylene group exceeds 2,000, shrinkage during drying is large, and it may be difficult to obtain a sufficient porous structure. When the amount of the structural unit composed of polyoxyethylene groups in the molecular skeleton is less than 10% by mass, it becomes difficult to disperse the urethane prepolymer having a blocked isocyanate group in water. It may cause gelation or separation, which may make it difficult to use. The amount of the structural unit composed of a polyoxyethylene group in the molecular skeleton is 40 mass. If the ratio exceeds / ₀ , the polyurethane resin does not form a film, and it may be difficult to form a porous structure.

(F) The compound having two or more active hydrogens used in the method of the present invention is not particularly limited. For example, a compound having two or more hydroxyl groups, carboxyl groups, amino groups, mercapto groups, etc. at the terminal or in the molecule And the like. Polyether compounds, polyester compounds, polyether ester compounds, polycarbonate compounds and the like can be suitably used. Examples of the polyetherolay conjugate include homopolymers such as ethylene oxide, propylene oxide, styrene oxide, and epichlorohydrin; random or block copolymers of two or more of these; and addition polymers to polyhydric alcohols. be able to. Examples of the polyester compound and the polyetherester compound include polycarboxylic acids such as adipic acid, succinic acid, phthalic acid, and maleic anhydride; polyunsaturated carboxylic acids; Polyhydric alcohols such as 4-butanediol, 1,6-hexanediol, neopentyl glycolone, and trimethylolpropane, unsaturated alcohols, polyalkylene ethers such as polyethylene glycol having a relatively low molecular weight, and polypropylene Daricalol Terdaricol , Mainly linear or branched shrinkage obtained from these mixtures, etc. Examples thereof include polyesters obtained from a synthetic product, ratatone or hydroxy acid, and polyether esters obtained by adding ethylene oxide, propylene oxide, or the like to polyesters produced in advance. Examples of the polycarbonate compound include polytetramethylene carbonate diol, polyhexamethylene carbonate diole, poly-1,4-cyclohexanedimethylene carbonate diole, and the like.

 Examples of the (g) polyisocyanate compound used in the method of the present invention include an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, and an aromatic polyisocyanate compound. Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, and trimethinolehexamethylene diisocyanate. Examples of the alicyclic polyisocyanate compound include, for example, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexyl methane diisocyanate, norbornane diisocyanate, and 1,3-bis (I Socyanatomethyl) cyclohexane. Examples of the aromatic polyisocyanate compound include tolylene diisocyanate, diphenyl methane diisocyanate, naphthalene diisocyanate. I can do it. One of these polyisocyanate compounds can be used alone, or two or more can be used in combination. Among these, an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound can be suitably used because they give a non-yellowing film, and hexamethylene diisocyanate and isophorone diisocyanate can be used. , Dicyclohexylmethane diisocyanate, norpolnandidisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane can be particularly preferably used.

There is no particular limitation on the chain extender (h) used in the method of the present invention. Polyhydric alcohols such as propane and pentaerythritol; diamines such as ethylenediamine, hexamethylenediamine and piperazin; aminoamines such as monoethanolamine and diethanolamine Alcohols, thiodiglycols such as thiodiethylene glycol, and water.

In the method of the present invention, the method for producing a urethane prepolymer obtained by reacting (f) a compound having two or more active hydrogens, (g) a polyisocyanate compound, and (h) a chain extender as necessary, There is no particular limitation, and it can be produced, for example, by a one-stage so-called one-shot method or a multi-stage isocyanate polyaddition reaction method. The reaction conditions are not particularly limited, but the reaction temperature is preferably 150 ° C. or lower, more preferably 50 ° C. to 120 ° C. The equivalent ratio of isocyanate group / active hydrogen is 1 or more, but it is necessary to form a blocked isocyanate group having thermal reactivity, so that a free isocyanate group remains in the obtained urethane prepolymer. There is a need. The content of the free isocyanate group in the urethane prepolymer is preferably from 1 to 10% by mass, more preferably from 2 to 7% by mass. Also content of free Isoshianeto groups shall apply less than 1 mass _^0/0, 1 0 wt _^0/0 even beyond, resulting blocked Isoshianeto group unstable water-dispersible polyurethane prepolymer one having And separation or gelation may occur over time.

In the method of the present invention, the blocking agent of the urethane prepolymer is not particularly limited as long as it reacts with the isocyanate 'group, is hydrophilic, and can be easily released under the conditions of thermal reaction to regenerate the active isocyanate group. But, for example, bisulfite, oxime and the like. Of these, bisulfite can be particularly preferably used because of its low desorption temperature. The reaction between urethane prepolymer and bisulfite is an exothermic reaction, and is a competitive reaction between bisulfite and water.Therefore, in order to selectively perform sufficient blocking with bisulfite, the reaction is required. The temperature is preferably 50 ° C or lower, more preferably 20 to 40 ° C. After completion of the reaction, the mixture is diluted with water to an appropriate concentration to obtain a hydrophilic and heat-reactive urethane prepolymer-terminated isocyanate block aqueous dispersion. This block can be stored for a long time in the form of an aqueous solution, and when heated to 50 to 150 ° C, the bisulfite of the blocking agent dissociates to regenerate the active isocyanate group. Therefore, a polymerization addition reaction is caused within or between the molecules of the prepolymer to form a polyurethane polymer, or an addition reaction to another functional group can be caused. In the production method of the present invention, the mass ratio of (A) the aqueous polyurethane dispersion to the (B) urethane prepolymer terminal isocyanate block aqueous dispersion is expressed by: (A) :( B) = 10: The ratio is preferably from 90 to 90:10, more preferably from 30:70 to 70:30. If the mass ratio in terms of solid content is (A) :( B) = l 0: less than 90 and the amount of the aqueous polyurethane aqueous dispersion is small, the strength of the porous tenside structure becomes insufficient and sufficient. There is a possibility that a porous structure may not be formed. If the mass ratio in terms of solid content exceeds (A) :( B) = 90: 10 and the amount of the urethane prepolymer polymer-terminated isocyanate block aqueous dispersion is small, a sufficient porous structure cannot be formed. There is a risk. In the production method of the present invention, (B) a tertiary amine is used for promoting the polymerization of the (B) urethane prepolymer-terminated isocyanate block aqueous dispersion. There is no particular limitation on the (C) tertiary amine used, and examples thereof include water-soluble tertiary amines such as triethylenediamine, trimethylamine, triethylamine and triallylamine. The mass ratio of the mixture of (A) the aqueous dispersion of the aqueous polyurethane and (B) the aqueous dispersion of the urethane prepolymer-terminated isocyanate block to (C) the tertiary amine is calculated by the solid content conversion of ((A) + (B)}: (C) = preferably from 100: 10 to 100: 1. When the mass ratio in terms of solids is {(A) + (B)} :( C) = less than 100: 10 and the amount of tertiary amine is large, the effect of accelerating the polymerization addition reaction is not changed. There is a possibility that the amount of the catalyst becomes excessive. If the mass ratio in terms of solid content exceeds (A) + (B)} :( C) = l00: 1 and the amount of tertiary amine is small, the catalytic action becomes insufficient and the polymerization addition reaction is accelerated. However, there is a possibility that a satisfactory porous structure cannot be obtained.

 In the production method of the present invention, a mixture of (A) an aqueous dispersion of an aqueous polyurethane and (B) an aqueous dispersion of a urethane prepolymer-terminated isocyanate block may contain, if necessary, a surfactant and a thickener. Additives such as a migration inhibitor, a leveling agent, a preservative, a fungicide, and a crosslinking agent can be added. A mixture of (A) an aqueous polyurethane resin dispersion, (B) an aqueous dispersion of polyurethane prebolimer-terminated isocyanate block, and (C) a tertiary amine solution obtained by mixing these additives until uniform. A porous structure can be obtained.

In the method of the present invention, a mixed solution containing (A) an aqueous dispersion of an aqueous polyurethane, (B) an aqueous dispersion of a urethane prepolymer polymer and an isocyanate block, and (C) a tertiary ammine There is no particular limitation on the substrate to which the resin is applied, as long as the substrate can adhere to the mixed liquid, and after drying, can form a coating with a resin component having a porous structure. Examples of such a base material include release paper, paper, plastic film, glass plate, metal plate, natural fibers such as wool, silk, and cotton; synthetic fibers such as polyamide, polyester, and acrylic; and blends and blends thereof. Fabrics, knits, non-woven fabrics, etc. manufactured by fiber and blend knitting can be exemplified. Among these base materials, non-woven fabrics using polyamide fibers, polyester fibers or acrylic fibers are particularly suitable because they can obtain artificial leather having a texture close to that of natural leather and synthetic leather, and synthetic leather. Can be used.

 In the method of the present invention, artificial leather can be manufactured using a nonwoven fabric having a fiber layer having a three-dimensional structure similar to the collagen fiber structure of leather as a base material. It is preferable to use ultrafine fibers of 0.1 denier or less for the surface portion of the base material. By using microfibers on the surface, an excellent leather-like feel can be obtained. The artificial leather can be of suede type or grain type depending on the surface finish. Synthetic leather can be finished by coating a polyamide resin or polyurethane resin on the formed porous structure, using a woven fabric, a knitted fabric, a nonwoven fabric, or the like as a base material.

In the production method of the present invention, a mixed solution containing (A) an aqueous dispersion of an aqueous polyurethane, (B) an aqueous dispersion of a urethane prepolymer-terminated isocyanate block, and (C) a tertiary amamine is woven or knitted. , Non-woven fabrics, etc. by applying, impregnating, coating, spraying, etc., and then drying the applied substrate by dry heat drying or moist heat by steam, and then useful as artificial leather or synthetic leather A porous structure can be obtained. There is no particular limitation on the machine and method for impregnating, coating, spraying, and the like on the substrate with the above-mentioned mixed solution, and the concentration of the mixed solution and the processing conditions can be appropriately selected. There is no particular limitation on the drying method. For example, dry heat drying using a pin tenter or the like, wet heat heating using a high-tensile steamer (HTS.), A high-pressure steamer (HPS), or the like, Drying methods such as far-infrared heating and microwave heating can be used. After heating and drying, it is also possible to dry through a washing step with hot or cold water. Example Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 In Examples and Comparative Examples, the porous structure was evaluated by the following method.

(1) Porous structure

 The cross section was observed using a scanning electron microscope [Hitachi, Ltd., S-2400].

 〇: Formation of a dense porous structure is observed.

 Δ: Partial formation of a porous structure is observed.

 X: No porous structure was formed.

 (2) Tear strength

 JIS L 1906 5.4. (C) Measured according to the pendulum method.

 (3) Texture

 According to the tactile sensation, evaluation was made on a scale of 1 (coarse hardness) to 5 (soft).

■ In addition, the viscosity is as follows: -7, Synthesis Example 9 and Comparative Synthesis Example 4 were measured at 60 rpm using a BM viscometer and No. 1 rotor, and were measured in Synthesis Example 8, Comparative Synthesis Example 2, Example 11 and Comparative Example 5. Was measured at 60 rpm using a BM viscometer and a No. 4 rotor.

 Synthesis Example 1 (Water-based polyurethane aqueous dispersion)

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 75.9 g of polytetramethylene glycolone (average molecular weight 1,000), polyoxyethylene polyoxypropylene random copolymer glycol ( Average molecular weight 1,000, oxethylene group content 70 mass ⁰ / o) 19.0 g, trimethylolpropane 2.5 g, 0.001 g of dibutyltin dilaurate and 60 g of methylethylketone were charged and mixed uniformly. Hexylmethane diisocyanate (42.6 g) was added, and the mixture was reacted at 75 ° C for 300 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 1.7% by mass based on the solid content. Was. After cooling the solution to 30 ° C, add 0.1 g of decyl phosphate and 6.0 g of polyoxyethylene tristyrylphenyl ether (HLB 15), mix uniformly, and gradually add 260 g of water. Phase inversion emulsification and dispersion. Furthermore, the piperidines Rajin 5. 3 _g and diethylene tri Amin 0.8 g of polyamine aqueous solution prepared by dissolving in water 18.0 g was added, the reaction stirred for 90 minutes Thus, a polyurethane dispersion was obtained. Thereafter, the solvent was removed at 50 ° C. under reduced pressure to obtain a stable aqueous polyurethane water dispersion A having a solid content of 35.0% by mass, a viscosity of 45 mPa · s, and an average particle diameter of 0.32 ^ m. Got one.

Synthesis Example 2 (Aqueous polyurethane aqueous dispersion)

In the same reaction apparatus as in Synthesis Example 1, 74.5 g of polytetramethylene glycol (average molecular weight _: 1,000), random copolymerized glycol of polyoxyethylene polyoxypropylene (average molecular weight _: 1,000, oxyethylene) Group content 70 mass ⁰ /.) 17.2 g, 1,4-butanediol 1.3 g, trimethylonolepropane 1.9 g, dibutynole tin dilate 0.01 g and methyl After adding 60 g of ethyl ketone and mixing uniformly, add 45.1 g of hexyl methane diisocyanate to the mouth of the flask and react at 75 ° C for 300 minutes to obtain a solid content. A solution of urethane prepolymer in methyl ethyl ketone having a free isocyanate group content of 1.9% by mass was obtained. After cooling the solution to 30 ° C, 0.1 g of decyl phosphate and 6.0 g of polyoxyethylene tristyryl ether (HLB 15) were added and mixed uniformly, and 260 g of water was added. Was gradually added to emulsify and disperse phase inversion. Further, a polyamine aqueous solution in which 5.6 g of piperazine and 0.9 g of diethylenetriamine were dissolved in 18.0 g of water was added, and the mixture was stirred and reacted for 90 minutes to obtain a polyurethane dispersion. Thereafter, the solvent was removed at 50 ° C under reduced pressure, and a stable aqueous polyurethane dispersion A 2 having a solid content of 35.0% by mass, a viscosity of 57 mPa · s, and an average particle diameter of 0.30 μm was prepared. Got.

Synthesis Example 3 (Aqueous aqueous polyurethane dispersion)

The same reactor as in Synthesis Example 1, polytetramethylene glycol (average molecular weight 1, 0 0 0) 6 3. 0 g, 2, 2- dimethylol butanoic acid 6. 0 g, trimethylolpropane Nono ⁰ down 1. 4 g, 0.005 g of dibutyltin diallate and 47 g of methyl ethyl ketone were mixed and uniformly mixed, and then 39.6 g of dicyclohexylmethanediisocyanate was added. For 250 minutes with a free isocyanate group content of 1.8 mass ⁰ / to the solid content. To obtain a solution of the urethane prepolymer in methyl ethyl ketone. 30 of this solution. After cooling to C, 4.0 g of triethylamine was added for neutralization, and 160 g of water was gradually added to emulsify and disperse. Further, an aqueous solution of polyamine obtained by dissolving 6.4 g of piperazine in 250 g of water was added, and the mixture was stirred and reacted for 90 minutes to obtain a polyurethane dispersion. Then, the solvent was removed at 50 ° C under reduced pressure, and the solid content was 35.3 mass. /. Thus, a stable aqueous polyurethane dispersion A3 having a viscosity of 4 OmPas and an average particle diameter of 0.13 μm was obtained.

Synthesis Example 4 (Water-based polyurethane aqueous dispersion)

In the same reactor as in Synthesis Example 1, 59.1 g of polytetramethylene glycol (average molecular weight: 1,000), 1.2 g of 1,4-butanediol, 6.0 g of 2,2-dimethylolbutanoic acid, 1.4 g of trimethylolpropane, After charging 0.005 g of dibutyltin diallate and 47 g of methyl ethyl ketone and mixing them uniformly, add 42.3 g of xinolemethanediisocyanate to the mouth of the flask and react at 85 ° C for 250 minutes. A solution of urethane prepolymer in methylethylketone having a free isocyanate group content of 1.7% by mass was obtained. After the solution was cooled to 30 ° C., 4.0 g of triethylamine was added to neutralize the solution, and 160 g of water was gradually added to emulsify and disperse. Further, an aqueous polyamine solution in which 6.3 g of piperazine was dissolved in 25.0 g of water was added, and the mixture was stirred and reacted for 90 minutes to obtain a polyurethane dispersion. After that, the solvent was removed at 50 ° C under reduced pressure, and the solid content was 34.9 mass. / ₀ , a viscosity of 5 OmPa · s, and an average particle diameter of 0.12 μπι, thereby obtaining a stable aqueous polyurethane resin dispersion A4.

Synthesis Example 5 (Water dispersion of polyurethane prepolymer-terminated isocyanate block)

The same reactor as in Synthesis Example 1 was charged with 76.7 g of polytetramethylene glycol (average molecular weight: 1,000), 29.8 g of polyethylene glycol (average molecular weight: 400), and 43.5 g of hexamethylene diisocyanate, and uniformly mixed. Thereafter, the mixture was reacted at 100 ° C. for 60 minutes to obtain a urethane prepolymer having a free isocyanate group content of 6.0% by mass and a polyoxyethylene group content of 19.9% by mass based on the solid content. After cooling this urethane prepolymer to 30 ° C, 40 g of ethanol was added and mixed uniformly, and an aqueous solution in which 22.4 g of anhydrous sodium bisulfite was dissolved in 41.7 g of water was added. The blocking reaction was performed at 30 ° C until the NCO peak disappeared in the measurement. After completion of the reaction, 268 _g of water was added to obtain a stable urethane prepolymer-terminated isocyanate block aqueous dispersion B1 having a solid content of 30.0% by mass and a viscosity of 62 mPa-s.

Synthesis Example 6 (Water dispersion of urethane prepolymer terminal isocyanate block)

In the same reactor as in Synthesis Example 1, polytetramethylene glycol (average molecular weight 1, 000) 82.6 g, polyethylene glycol (average molecular weight 1 000) 30.4 g, hexamethylene diisocyanate 37.0 g, mix uniformly, react at 100 ° C for 60 minutes, release to solids Isoshianeto group content 6.0 mass%, the content of the polyoxyethylene group to obtain a urethane prepolymer 20.3 mass _^0/0. After cooling the urethane prepolymer to 30 ° C, add 40 g of ethanol, mix uniformly, add a water solution of 22.4 g of anhydrous sodium bisulfite in 41.6 g of water, and measure the infrared absorption spectrum. The blocking reaction was carried out at 30 ° C until the NCO peak disappeared. After completion of the reaction, water was added to 268 g, to obtain a solid content 30.0 wt _^0/0 stable urethane prepolymer terminated with a viscosity 37mP a · s iso Xia sulfonates block aqueous dispersion B 2.

Synthesis Example 7 (Water dispersion of urethane prepolymer-terminated isocyanate block)

The same reactor as in Synthesis Example 1 was charged with 67.0 g of polytetramethylene glycol (average molecular weight: 1,000), 29.4 g of polyethylene glycol (average molecular weight: 200), and 53.5 g of hexamethylene diisocyanate, and mixed uniformly. later, 100 ° and allowed to react for 30 minutes at C, 6.0 wt% of free Isoshianeto groups relative to solid content of the polyoxyethylene group to obtain a urethane Prevost Rimmer 19.6 mass _^0/0. 30 of this urethane prepolymer. After cooling to C, add 40 g of ethanol and mix evenly.Then an aqueous solution of 22.2 g of anhydrous sodium bisulfite dissolved in 41.2 g of water is heated, and the NCO peak disappears in the infrared absorption spectrum measurement. The blocking reaction was carried out at 30 ° C until 30 ° C. After completion of the reaction, 269 g of water was added to obtain a solid content of 30.0 mass. /. A stable urethane prepolymer-terminated isocyanate block aqueous dispersion B3 having a viscosity of 52 mPa-s was obtained.

Synthesis Example 8 (Urethane prepolymer-terminated isocyanate block aqueous dispersion)

The same reactor as in Synthesis Example 1 was charged with 85.1 g of polytetramethylene glycol (average molecular weight 1,000), 30.0 g of polyethylene glycol (average molecular weight 1,800), and 34.9 g of hexamethylene diisocyanate. After mixed, to give 10 0 ° and C in reacted for 60 minutes, the free relative to the solid content Isoshianeto group content 6.0 mass _^0/0, the content of the polyoxyethylene group is 20.0 _^0/0 urethane prepolymer Was. After cooling the urethane prepolymer to 30 ° C, 40 g of ethanol The mixture was mixed homogeneously, and an aqueous solution of 22.4 g of anhydrous sodium bisulfite dissolved in 41.3 g of water was added.The blocking reaction was carried out at 30 ° C until the NCO peak disappeared by infrared absorption spectrum measurement. . After completion of the reaction, 269 g of water was added to obtain a stable urethane prepolymer-terminated isocyanate block aqueous dispersion B4 having a solid content of 30.0% by mass and a viscosity of 1,50 OmPa · s.

Synthesis Example 9 (Water dispersion of urethane prepolymer terminal isocyanate block)

 In the same reactor as in Synthesis Example 1, 57.3 g of polytetramethylene glycol (average molecular weight: 1,000), 45.7 g of polyethylene glycol (average molecular weight: 400), and 47.0 g of hexamethylene diisocyanate were added. After charging and mixing evenly, 100. C. for 60 minutes to obtain a urethane prepolymer having a free isocyanate group content of 6.1% by mass and a polyoxyethylene group content of 30.4% by mass based on the solid content. After cooling the urethane prepolymer to 30 ° C, 4 g of ethanol was added and mixed uniformly, and an aqueous solution in which 22.6 g of anhydrous sodium bisulfite was dissolved in 42.0 g of water was added. The blocking reaction was performed at 30 ° C until the NCO peak disappeared in the vector measurement. After completion of the reaction, 268 g of water was added to obtain a stable urethane prepolymer-terminated isocyanate block aqueous dispersion B6 having a solid content of 30.2% by mass and a viscosity of 33 mPa · s.

Comparative Synthesis Example 1 (Water dispersion of polyurethane prepolymer-terminated isocyanate block) In the same reactor as in Synthesis Example 1, 19.8 g of polytetramethylene glycol (average molecular weight: 1,000), 30.7 g of ethylene glycolone And 99.6 g of hexamethylene diisocyanate were charged and uniformly mixed, and then heated and heated. Vigorous heat generation was observed from around 60 ° C, and the reaction proceeded and the viscosity increased. When cooled to around 50 ° C for dispersion in water, the urethane prepolymer was solidified and could not be dispersed in water, and a stable aqueous dispersion of urethane prepolymer-terminated isocyanate block could be obtained. could not.

Comparative Synthesis Example 2 (Urethane prepolymer terminal isocyanate block aqueous dispersion) In the same reactor as in Synthesis Example 1, 85.6 g of polytetramethylene glycol (average molecular weight of 1,000), polyethylene glycol (average molecular weight of 2 , 500) 29.9 g, 34.5 g of hexamethylene diisocyanate, and after mixing evenly, 10 The reaction was carried out at 0 ° C for 60 minutes, and the content of free isocyanate groups relative to the solid content was 6.0 mass ⁰ /. Content of the polyoxyethylene group to obtain a urethane Prevost Rimmer 19.9 mass _^0/0. After cooling the urethane prepolymer to 30 ° C, add 40 g of ethanol, mix uniformly, add a water solution of 22.5 g of anhydrous sodium bisulfite in 41.3 g of water, and measure the infrared absorption spectrum. The block reaction was carried out at 30 ° C until the NCO peak disappeared. After the completion of the reaction, 269 g of water was added to obtain a stable urethane prepoly terminal block aqueous dispersion B5 having a solid content of 30.0% by mass and a viscosity of 3 000 mPa · s.

 Comparative Synthesis Example 3 (Water dispersion of urethane prepoly terminal isocyanate block) In the same reactor as in Synthesis Example 1, 103.6 g of polytetramethylene glycol (average molecular weight 1 000) and 7.7 g of polyethylene glycol (average molecular weight 400) , Hexamethylene diisocyanate 38.7 g was mixed and mixed uniformly, and reacted at 100 ° C for 60 minutes. The content of free isocyanate group to the solid content was 6.0% by mass, and the polyoxyethylene group was A urethane prepolymer having a content of 5.1% by mass was obtained.After cooling the urethane prepolymer to 30 ° C, 40 g of ethanol was added and mixed uniformly, and 22.5 g of anhydrous sodium bisulfite was added to 41.7 g of water. The blocking reaction was carried out at 30 ° C by adding the aqueous solution dissolved in water, but the viscosity rapidly increased and a large amount of scum was generated without dispersing in water, and a stable aqueous dispersion was obtained. I couldn't.

Comparative Synthesis Example 4 (Water Dispersion of Urethane Prepoly Terminal Isocyanate Block) In the same reactor as in Synthesis Example 1, polytetramethylene glycol (average molecular weight 1 000) 21.1 g, polyethylene glycol (average molecular weight 40 75.8 g, 53.1 g of hexamethylene diisocyanate were charged, mixed uniformly, and reacted at 100 ° C. for 60 minutes. The content of free isocyanate group with respect to the solid content was 5.9 mass. / _0, the content of the polyoxyethylene group to obtain a urethane Prevost Rimmer 50.6 mass _^0/0. After cooling the urethane prepolymer to 30 ° C, add 40 g of ethanol and mix evenly.Add an aqueous solution of 22.0 g of anhydrous sodium bisulfite in 40.9 g of water, and add the infrared absorption spectrum. The reaction was blocked at 30 ° C until the NCO peak disappeared in the measurement. After the completion of the reaction, 269 g of water was added, and a stable urethane prepolymer-terminated isocyanate block aqueous dispersion B having a solid content of 30.1% by mass and a viscosity of 34 mPa-s was obtained.

No. 丄

 Polyoxyethylene

 Aqueous dispersion type PEG sweet ^ "-ヽ Stability Synthesis Example 1 A 1 Bow

 Synthesis Example 2 A 2 Stable

Synthesis Example 3 A 6 Self-emulsification type Stable

 Nore TOI

 Synthesis example 4 A 4

 Synthesis example 0 B 丄 i U U ヅ ヅ (JT 4 U U 1 y. Y Stable

 Synthesis Example 6 B 2 J ヅ D ヅ r _h 11 π U U Π Π ϋ 20.3 Stable

Ϊ5 Upper Ν Shino-Reno U P TP Π- 9 Π Π 1

 Womanbiki.

 Synthesis example 8 B4 N C 0 block PEG 1800 20.0 Stable

 Synthesis example 9 B 6 NC〇 block PEG400 30.4 Stable

 Comparative Synthesis Example 1 N CO Block Ethylene Glycol Solidification

Comparative Synthesis Example 2 B5 NC〇 Block PEG2500 19.9 Stable

Comparative synthesis example 3 N CO block PEG400 5.1 Increase in viscosity Comparative synthesis example 4 B 7 N CO block PEG400 50.6 Stable

Example 1 (impregnation)

Fiber thickness 1.0 denier, the polyester nonwoven fabric of density 0.40 g / cm ^3, the aqueous Polyurethane aqueous dispersion A 1 143 g, the urethane prepolymer terminated Isoshianetobu-locking aqueous dispersion B 1 a 167 g (mass ratio (solid (A): (A): (B) = 50: 50), 7 g of triethylenediamine and 183 g of water were mixed, and the resulting solution was pad-treated with a pickup of 250% by mass. After the pad treatment, the work cloth was subjected to wet heat heating for 5 minutes using a high-temper-part steamer adjusted to a temperature of 100 ° C and a vapor pressure of 39 kPa. Next, it was washed with water for 2 minutes, squeezed with a mandal, and dried and dried with a pintenter adjusted to 120 ° C to obtain artificial leather.

 The resulting artificial leather had a dense porous structure. The tear strength was 1.8N in the vertical direction and 1.4N in the horizontal direction. The texture was grade 3.

Example 2 (impregnation)

 143 g of the aqueous polyurethane water dispersion A2, 167 g of the urethane prepolymer terminal dissociate block water dispersion B1 (mass ratio (in terms of solid content) (A): (B) = 50: 50), triethylenediamine An artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 The resulting artificial leather had a dense porous structure as shown in the electron micrograph of the cross section in FIG. The tear strength was 1.7 mm in the longitudinal direction and 1.4 mm in the transverse direction. The texture was grade 3.

Example 3 (impregnation)

 143 g of the aqueous polyurethane water dispersion A 3, 167 g of the urethane prepolymer-terminated disocyanate block water dispersion B 1 (mass ratio (in terms of solid content) (A): (B) = 50: 50), 3 g of triethylamine An artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of triethylenediamine and 183 g of water was used. The resulting artificial leather had a dense porous structure. The tear strength was 2.2N in the vertical direction and 1.7N in the horizontal direction. The texture was second grade.

Example 4 (impregnation)

143 g of the aqueous polyurethane water dispersion A4, 167 g of the urethane prepolymer terminal dissociate block water dispersion B1 (mass ratio (in terms of solid content) (A): (B) = 50: Artificial leather was obtained in the same manner as in Example 1, except that a treatment liquid prepared by mixing 50 g of triethylamine, 7 _{g of} triethylenediamine and 183 g of water was used. The resulting artificial leather had a dense porous structure. The tear strength was 2.2N in the vertical direction and 1.7N in the horizontal direction. The texture was second grade.

Example 5 (impregnation)

Aqueous polyurethane aqueous dispersion A 2 to 143 g, a urethane prepolymer terminated Isoshia sulfonates block aqueous dispersion B 2 and 167 _g (ratio by mass (in terms of solid content) (A): (B) = 50: 50), Toriechirenji Artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 The resulting artificial leather had a dense porous structure. The tear strength was 1.8N in the vertical direction and 1.4N in the horizontal direction. The texture was grade 3.

Example 6 (impregnation)

 143 g of the aqueous polyurethane water dispersion A 2, 167 g of the urethane prepolymer-terminated isocyanate block water dispersion B 3 (mass ratio (in terms of solid content) (A): (B) = 50: 50), triethylene di Artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 'The resulting artificial leather had a dense porous structure. The tear strength was 1.8N in the vertical direction and 1.4N in the horizontal direction. The texture was grade 3.

Example 7 (impregnation)

 143 g of the aqueous polyurethane water dispersion A 2, 167 g of the urethane prepolymer-terminated succinate block water dispersion B 4 (mass ratio (in terms of solid content) (A): (B) = 50: 50), triethylenediamine Artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 The resulting artificial leather had a dense porous structure. The tear strength was 1.7N in the vertical direction and 1.3N in the horizontal direction. The texture was grade 3.

Example 8 (impregnation)

143 g of aqueous polyurethane aqueous dispersion A2, 167 g of urethane prepolymer-terminated dicyanate block aqueous dispersion B6 (mass ratio (in terms of solid content) (A): (B) = 50: 50), triethylenediene 7 g of water and 183 g of water. An artificial leather was obtained in the same manner as in Example 1 except for the difference.

 The resulting artificial leather had a dense porous structure. The tear strength was 1.8 N in the vertical direction and 1.3 N in the horizontal direction. The texture was grade 3.

Example 9 (impregnation)

 57 g of the aqueous polyurethane water dispersion A2, 267 g of the urethane prepolymer-terminated isoblock block water dispersion B1 (mass ratio (in terms of solid content) (A): (B) = 20: 80), triethylene dia An artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of min and 169 g of water was used.

 The resulting artificial leather had a dense porous structure. The bow I crack strength was 1.6N in the vertical direction and 1.1N in the horizontal direction. The texture was grade 4.

Example 10 (impregnation)

 229 g of aqueous polyurethane water dispersion A 2, 67 g of urethane prepolymer-terminated disocyanate block aqueous dispersion B 1 (mass ratio (in terms of solid content) (A): (B) = 80: 20), triethylene di Artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 197 g of water was used.

 The resulting artificial leather had a dense porous structure. The tear strength was 1.6N in the vertical direction and 1.2N in the horizontal direction. The texture was grade 3.

Comparative Example 1 (impregnation)

Solvent-based polyurethane [Nikka Chemical Co., Ltd., Evaphanol ALS-30TD, dimethylformamide solution, solid content 30 mass ⁰ / on polyester nonwoven fabric with a denier of 1.0 denier and a density of 0.40 gcm ³ . The treated solution prepared by mixing 200 g and 100 g of dimethylformamide was padded with a pickup of 330% by mass. The work cloth after the pad treatment was immersed in a water bath for 5 minutes, and then washed with water at 80 ° C for 5 minutes. Next, it was squeezed with a mandal and dried and dried with a pin tenter adjusted to 120 ° C to obtain artificial leather. ·

 The resulting artificial leather had a dense porous structure. The bow I crack strength was 1.8 N in the vertical direction and 1.3 N in the horizontal direction. The texture was grade 3.

Comparative Example 2 (impregnation)

143 g of aqueous dispersion A2 of polyurethane, urethane prepolymer terminal The procedure was performed with the exception that 167 g (mass ratio (in terms of solid content) (A): (B) = 50:50) of the aqueous solution of sodium salt B1 and 190 g of water were used to prepare a solution. An artificial leather was obtained in the same manner as in Example 1.

 No porous structure was formed in the obtained artificial leather. The tear strength was 0.9 N in the vertical direction and 0.7 N in the horizontal direction. The texture was 5th grade.

Comparative Example 3 (impregnation)

 143 g of an aqueous dispersion A2 of an aqueous polyurethane, 167 g of an aqueous dispersion B5 of a urethane prepolymer terminal isocyanate block (mass ratio (in terms of solid content) (A): (B) = 50:50), triethylenediamine Artificial leather was obtained in the same manner as in Example 1 except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 As shown in the electron micrograph of the cross section in Fig. 2, the obtained artificial leather did not have a porous structure. The tear strength was 2.5N in the vertical direction and 2.ON in the horizontal direction. The texture was first class.

Comparative Example 4 (impregnation)

 143 g of the aqueous polyurethane water dispersion A2, 167 g of the urethane prepolymer terminal dissociate block water dispersion B7 (mass ratio (in terms of solid content) (A): (B) = 50: 50), triethylenediamine Artificial leather was obtained in the same manner as in Example 1, except that a treatment solution prepared by mixing 7 g of amine and 183 g of water was used.

 The resulting artificial leather had a porous structure partially formed. The tear strength was 1.3N in the vertical direction and 1.1N in the horizontal direction. The texture was grade 3.

Examples 1 to: L 0 and Comparative Example:! Table 2 shows the results of Nos. 1 to 4.

Table 2

 Water dispersion

 ~ · 'ノ ヽ ¾ Porous structure

 No

 Composition Resin mass ratio Forming state Vertical Example 1 'A1 + B1 50:50 Triethylenediamine Dense 1. Example 2 A2 + B1 50:50 Triethylenediamine Dense 1.

 Triethylamine

Example 3 A3 + B1 50:50 C- 1 · ί5: '

 Tri-Nalennonno, ^ no elaborate 2. Triethylamine

Example 4 A4 + B1 50: 50 dense 2.

 Triethylenediamine

Example 5 A2 + B2 50:50 Triethylenediamine Dense 1. Example 6 A2 + B35.0: 50 Triethylenediamine Dense 1. Example 7 A2 + B4 50:50 Triethylenediamine Dense 1. Example 8 A2 + B 6 50:50 Triethylenediamine Dense 1. Example 9 A2 + B1 20:80 Triethylenediamine Dense 1. Example 10 A2 + B1 80:20 Ethylenediamine Dense 1. Comparative Example 1 Dimethylformamide solution Dense 1. Comparative Example 2 A2 + B 1 50: 50 None Not formed 0. Comparative Example 3 A2 + B 5 50: 50 Triethylenediamine Not formed 2. Comparative Example 4 A2 + B 7 50: 50 Triethylenediamine Partially formed 1.

As can be seen from Table 2, urethane prepolymers having a structural unit consisting of polyoxyethylene groups having an average molecular weight of 200-1,800 in a molecular skeleton of 19.9 to 30.4% by mass. In the artificial leathers of Examples 1 to 10 using the terminal isocyanate block aqueous dispersion, a dense porous structure was formed. The artificial leathers of Examples 1 to 8 have the same performance as the artificial leather using the solvent-based polyurethane of Comparative Example 1 in both tear strength and texture. Resin mass ratio (in terms of solid content) Force S (A): (B) = 20: 80 or (A): (B) = 80: 20 Artificial of Example 9 or Example 10 The leather has a bow / tear strength slightly lower than that of the artificial leathers of Examples 1 to 8, but has a good texture. On the other hand, in the artificial leather of Comparative Example 2 in which no tertiary amine (C) for promoting the polymerization was used, no resin remained in the nonwoven fabric, and no formation of a porous structure was observed. The artificial leather of Comparative Example 3 in which the average molecular weight of the polyoxyethylene group of the constituent unit of the urethane prepolymer-terminated isocyanate block aqueous dispersion is 2,500, has no porous structure, and has no porous membrane. Resin adheres. Therefore, the texture is also coarse and hard. The artificial leather of Comparative Example 4 in which the amount of polyoxyethylene groups in the molecular weight skeleton of the constituent units of the aqueous dispersion of urethane prepolymer-terminated isocyanate block was 50.6% by mass had no porous structure. Although it was found in the-part, a large amount of resin fell off, the amount of resin adhered to the nonwoven fabric was small, and the tear strength was reduced.

Example 11 (coating)

Fluorinated water repellent [Nikka Chemical Co., Ltd., NK Guard ND N-7E] Impregnated in a 0.5% by mass aqueous solution, squeezed with a mandal, dried at 130 ° C for 1 minute, and weakly water-repellent on poly ester fabric which has been subjected to processing, the aqueous polyurethane aqueous dispersion a 1 1 4 3 g, a urethane poly mer terminal iso Xia sulfonates block aqueous dispersion B 1 1. 6 7 _g (mass ratio (in terms of solid content ) (A): (B) = 50: 50), 7 g of triethylenediamine, 183 g of water and nonionic thickener [Nichika Chemical Co., Ltd., Neo Sticker N, solid 30% by mass], 2 _g , and a treatment liquid prepared to have a viscosity of 3.00 OmPa · s, coated with a slit thickness of 25 Ομπι, and then a temperature of 80 ° C. For 30 minutes. Then, it was washed with water for 2 minutes, squeezed with a mandal, and dried by drying with a dryer adjusted to 120 ° C. to obtain synthetic leather.

As shown in the electron micrograph of the cross section in FIG. 3, a dense porous structure was formed in the polyurethane layer of the obtained synthetic leather. Comparative Example 5 (Coating)

 Fluorine-based water repellent [Nika Chemical Co., Ltd., NK Guard ND N-7E] Impregnated in a 0.5% by mass aqueous solution, squeezed with a mandal, dried at 130 ° C for 1 minute, and weakly water-repellent On the processed polyester fabric, 144 g of aqueous polyurethane water dispersion A1 and 167 g of urethane prepolymer terminal isocyanate block water dispersion B5 (mass ratio (solid content conversion)) (A): (B) = 50: 50), 7 g of triethylenediamine, 183 g of water and a nonionic thickener [Nichika Chemical Co., Ltd., Neo Sticker N, solid content 3 0% by mass], and coated with a slit thickness of 250 μ μη, and then treated at a temperature of 80 ° C. Dry heat drying was performed for 0 minutes. Then, it was washed with water for 2 minutes, squeezed with a mandal, and dried by drying with a dryer adjusted to 120 ° C. to obtain synthetic leather. The polyurethane layer of the obtained synthetic leather was a nonporous membrane as shown in the electron micrograph of the cross section in FIG. Industrial applicability

 The artificial leather or the synthetic leather obtained by the method for producing a porous structure of the present invention has the same performance as the artificial leather or the synthetic leather obtained from the conventional solvent-based polyurethane, such as strength and texture, It is possible to replace polyurethane with aqueous polyurethane. Therefore, it is possible to reduce problems such as air pollution and water pollution caused by the solvent discharged during processing, labor for recovering the solvent, and the working environment of workers.

Claims

The scope of the claims

1 · (A) Aqueous dispersion of aqueous polyurethane, (B) 10 to 40 mass% of a structural unit comprising a polyoxyethylene group having an average molecular weight of 100 to 2,000 in a molecular skeleton. /. And (C) applying a mixed solution containing a tertiary amine to a base material, followed by drying with dry heat or wet heat. A method for producing a porous structure.

 2. (A) Aqueous aqueous polyurethane dispersion is prepared by reacting (a) a polyol compound and (b) a polyisocyanate compound with an isocyanate group-terminated prepolymer, using a nonionic surfactant having an HLB of 7 to 16. 2. The porous structure according to claim 1, which is an aqueous polyurethane aqueous dispersion obtained by dispersing in water, followed by (d) chain extension reaction with a polyamine compound having two or more amino groups and / or imino groups. How to make the body.

 3. (A) Aqueous polyurethane aqueous dispersion is prepared by reacting (a) a polyol compound, (b) a polyisocyanate compound and (c) a chain extender with an isocyanate group-terminated prepolymer, having an HLB of 7-16. An aqueous polyurethane resin dispersion obtained by dispersing in water using a nonionic surfactant and then subjecting the chain extension reaction to (d) a polyamine compound having two or more amino groups and / or imino groups. 2. The method for producing a porous structure according to 1.

4. The aqueous dispersion of (A) aqueous polyurethane is prepared by reacting (a) a polyol compound, (b) a polyisocyanate compound, and (e) a compound that imparts an ion-producing hydrophilic group with an isocyanate group-terminated prepolymer. Claims 1 which is an aqueous dispersion of aqueous polyurethane obtained by dispersing a hydrate in water and then subjecting the chain extension reaction to (d) a polyamine conjugate having two or more amino groups and Z or imino groups. 3. The method for producing a porous structure according to item 1.

5. An isocyanate obtained by reacting (A) an aqueous polyurethane aqueous dispersion with (a) a polyol compound, (b) a polyisocyanate compound, (e) a compound imparting an ionic hydrophilic group, and (c) a chain extender. After dispersing the neutralized product of the base terminal prepolymer in water, (d) a polyamine derivative having two or more amino groups and / or imino groups 2. The method for producing a porous structure according to claim 1, which is an aqueous polyurethane aqueous dispersion obtained by a chain extension reaction.

6. (A) Aqueous polyurethane aqueous dispersion) Structural units comprising a polyoxyethylene group having an average molecular weight of 100 to 2,000 are contained in the molecular skeleton in an amount of 10 to 40 mass. / ₀ , the mass ratio of the urethane prepolymer-terminated isocyanate block aqueous dispersion to the solid content conversion

2. The method for producing a porous structure according to claim 1, wherein (A): (B) = 10: 90 to 90: 10.

 7. An artificial leather obtained by the method for producing a porous structure according to any one of claims 1 to 6.

 8. A synthetic leather obtained by the method for producing a porous structure according to any one of claims 1 to 6.