JP5901338B2 - Heat-sensitive coagulating water-based polyurethane resin composition and method for producing leather-like material using the same - Google Patents

Description

The present invention relates to a heat-sensitive coagulable water-based polyurethane resin composition and a method for producing a leather-like material obtained by heat-coagulating the heat-sensitive coagulable water-based polyurethane resin composition. More particularly, the present invention relates to a heat-sensitive coagulating water-based polyurethane resin composition excellent in storage stability and a method for producing a leather-like material excellent in migration prevention, crack resistance, texture and hot water resistance.

Leather-like materials used as substitutes for natural leather include artificial leather made of resin and non-woven fabric, and synthetic leather made of resin and woven fabric or knitted fabric. In many cases, polyurethane resin is used.
As a method for producing a leather-like material, for example, a fiber base material impregnated or coated with an organic solvent-based polyurethane resin is coagulated in a coagulating liquid which is a poor solvent for polyurethane resin and is compatible with the organic solvent. There is a wet coagulation method in which a leather material is produced by washing with water and then drying.

  In the wet coagulation method, water is generally used as a coagulant, and dimethylformamide is often used as an organic solvent compatible with water. However, organic solvents are highly flammable and may cause fire. In addition, since it is highly toxic and has problems such as environmental and human contamination, studies have been made to shift from solvent-based polyurethane resins to water-based polyurethane resins.

  As a method for producing a leather-like material using an aqueous polyurethane resin, there is a heat-sensitive coagulation method in which a fiber base material coated or impregnated with resin is subjected to hot water, steam or hot air drying to solidify the resin. In the heat-sensitive coagulation method, if a heat-sensitive coagulable water-based resin with low sensitivity to heat is used, when the resin is impregnated or coated and then solidified in hot water, the water-based resin flows out into the hot water bath or hot air When solidified or dried in a dryer, the phenomenon that the resin impregnated in the fiber base material migrates to the base material surface, that is, migration easily occurs, and the uniformity of the leather-like material is lost or strong. There are problems such as significantly adversely affecting physical properties such as elongation and flexibility, and texture.

  As described above, the leather-like material using the water-based polyurethane resin is satisfactory in physical properties such as migration prevention, crack resistance, texture, and hot water resistance as compared with the leather-like material using the organic solvent-based polyurethane resin. It was not a thing.

  In order to solve the problem of migration of leather-like materials, a water-based resin composition in which inorganic salts are dissolved in a forcedly emulsified emulsion is applied to an insensitive sheet and dried by heating (Patent Document 1), and the thermal coagulation temperature is 40. A method of thermally coagulating an aqueous resin composition comprising an aqueous urethane resin and an associative thickener at ~ 90 ° C with steam (Patent Document 2), a carboxylate salt type containing a nonionic surfactant of HLB 10-18 and an inorganic salt A thermal coagulation method such as a method in which a polyurethane resin is applied to a fiber material substrate and thermally coagulated (Patent Document 3) is disclosed.

However, in the case of the leather-like material obtained by the above-mentioned heat-sensitive coagulation method, although improvement is observed in the migration prevention property, due to the influence of the surfactant, inorganic salt, thickener, etc. remaining in the leather-like material, A sufficiently satisfactory texture and hot water resistance were not obtained.
Moreover, the water-based polyurethane resin composition used for the thermal coagulation method has a problem that it is inferior in storage stability.

Japanese Patent Laid-Open No. 06-316877 JP 2000-290879 A JP 2003-138131 A

Accordingly, a first object of the present invention is to provide an aqueous polyurethane resin composition that can provide a leather-like material that is excellent in storage stability and excellent in migration prevention, crack resistance, texture, and hot water resistance. There is to do.
The second object of the present invention is to provide a method for producing a leather-like material excellent in migration prevention, crack resistance, texture and hot water resistance.

  As a result of intensive studies to achieve the above objects, the present inventors have made a polyurethane resin having a carboxyl group and / or a sulfonic acid group, and a specific quaternary ammonium salt compound which is a heat-sensitive coagulant. The water-based polyurethane resin composition containing the water-based polyurethane resin composition has good storage stability and has been found to be heat-coagulated at a low temperature without greatly increasing the blending amount of the heat-sensitive coagulant. It has been found that a leather-like material excellent in various properties such as migration prevention, crack resistance, texture and hot water resistance can be obtained by using a product.

但し、上記式（１）中のＲ^１、Ｒ^２及びＲ^３は、それぞれ独立して炭素数が１〜８のアルキル基、Ｒ^４は炭素数が１〜８のアルキル基、又は、下記一般式（２）で表される基であり、Ｘ⁻は塩素イオン、臭素イオン又はヨウ素イオンである。

但し、上記式（２）中のａ及びｂは下記関係式を満たす整数である。
０≦ａ≦３、
５≦ａ＋ｂ≦５０、及び
ａ／(ａ＋ｂ)＜０．２。 That is, the present invention relates to (A) a polyurethane resin having at least one anionic group selected from a carboxyl group and a sulfonic acid group in the molecule, and (B) a heat-sensitive coagulable water-based polyurethane resin containing a heat-sensitive coagulant. It is a composition, Comprising: The said (B) component is a quaternary ammonium salt compound represented by following General formula (1), The said (B) component is 0.00 with respect to 100 mass parts of said (A) components. heat-sensitive coagulable aqueous polyurethane resin composition characterized by comprising a 1 to 50 parts by mass, and, after the heat-sensitive coagulable aqueous polyurethane resin composition was applied to the fiber material, or impregnated, heat-sensitive a method for producing a leather-like material, characterized by solidifying.

However, R ¹ , R ² and R ³ in the above formula (1) are each independently an alkyl group having 1 to 8 carbon atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, or the following general group It is group represented by Formula (2), and X < ^- > is a chlorine ion, a bromine ion, or an iodine ion.

However, a and b in the above formula (2) are integers satisfying the following relational expression.
0 ≦ a ≦ 3,
5 ≦ a + b ≦ 50, and a / (a + b) <0.2.

In the heat-sensitive coagulable water-based polyurethane resin composition of the present invention, the component (A) is a polyurethane resin comprising a polyol, a polyisocyanate and an anionic group introducing agent, and the polyol, polyisocyanate and anionic introducing agent are It is preferable that the ratio of the total isocyanate group equivalent of the polyisocyanate to the total hydroxyl group equivalent of the polyol and the anionic group introducing agent (NCO / OH) is 1.1 to 2.5.
Further, the compounding amount of the anionic group introducing agent is such that the acid value based on the anionic group of the anionic group introducing agent in the urethane prepolymer comprising the polyol, polyisocyanate and anionic group introducing agent is 5 to 50 mgKOH / g. It is preferable that the amount is as follows.
The component (A) preferably further contains 0.2 to 2.0 equivalents of an anionic group neutralizing agent with respect to 1 equivalent of the anionic group.
R ⁴ in the formula (1) is preferably a group represented by the general formula (2), a in the general formula (2) is 0, and b is 10 to 20, It is preferable that content of (B) component is 5-20 mass parts with respect to 100 mass parts of said (A) component.

  According to the present invention, a heat-sensitive coagulable water-based polyurethane resin composition excellent in storage stability can be obtained, and a leather-like material excellent in migration prevention, crack resistance, texture and hot water resistance can be obtained.

The polyurethane resin used as the component (A) of the present invention has at least one anionic group selected from a carboxyl group and a sulfonic acid group in the molecule.
Although the composition and manufacturing method of a polyurethane resin (A) are not specifically limited, For example, the method of manufacturing with the following method is mentioned.
(1) A urethane prepolymer is produced by reacting a polyol, polyisocyanate and an anionic group introducing agent, and an anionic group neutralizing agent is added to the prepolymer and / or water, and then in an anionic group as necessary. A prepolymer is added and dispersed in water containing a compatibilizer and / or an emulsifier (prepolymer mixing method).
(2) A urethane prepolymer is produced by reacting a polyol, polyisocyanate and an anionic group introducing agent, an anionic group neutralizing agent is added to the prepolymer and / or water, and then into the prepolymer, if necessary. Then, water containing an anionic group neutralizing agent and / or an emulsifier is added and dispersed (phase inversion method).
The urethane resin dispersed in water by the method (1) or (2) is chain-extended using a chain extender in water.
In the production of the prepolymer, if necessary, a solvent that is inert to the reaction and has a high affinity with water may be used.

The polyol is not particularly limited, and examples thereof include polyether polyols having a number average molecular weight of 300 to 5,000, polyester polyols, polyester polycarbonate polyols, and crystalline or non-crystalline polycarbonate polyols. Can be mentioned.
The number average molecular weight of these polyols is more preferably 500 to 3000.
In the present invention, the polyols and low molecular weight polyols having a molecular weight of less than 200 can be used in combination.

  Examples of the polyether polyols include ethylene oxides of low molecular weight polyols having a molecular weight of less than 200 such as 1,2-propanediol, 1,3-propanediol, trimethylolpropane, glycerin, polyglycerin, pentaerythritol, and / or the like. Examples include propylene oxide adducts; ethylene oxide and / or propylene oxide adducts of aromatic polyols such as bisphenol A; ethylene oxide and / or propylene oxide adducts such as amine compounds such as ethylenediamine; and polytetramethylene ether glycol.

  Examples of the polyester polyols include a direct esterification reaction between a polyol such as a low-molecular-weight polyol having a molecular weight of less than 200 and a polyvalent carboxylic acid having an amount less than the stoichiometric amount or an ester-forming derivative of the polyvalent carboxylic acid. Or the polyester polyol obtained by transesterification; and the polyester polyol obtained by the direct esterification reaction of the said low molecular weight polyol and the hydroxy carboxylic acid obtained by the hydrolytic ring-opening reaction thereof.

  Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipine. Fats such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid, castor oil fatty acid trimer Acids: Examples include tetravalent or higher carboxylic acids such as pyromellitic acid.

  Examples of the ester-forming derivative of the polyvalent carboxylic acid include polyhydric carboxylic acid anhydrides; carboxylic acid halides such as chloride and bromide; polyvalent carboxylic acid methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, And lower aliphatic esters such as isobutyl ester and amyl ester.

  Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

  Examples of the polyester polycarbonate polyols include reaction products obtained by reacting an organic dicarboxylic acid with a reaction product of a polyester glycol such as polycaprolactone polyol and an alkylene carbonate, and a reaction product of ethylene carbonate and a polyhydric alcohol. Is mentioned.

  Examples of the crystalline or non-crystalline polycarbonate polyol include diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polypropylene glycol, and polytetramethylene glycol. And a reaction product of phosgene, diaryl carbonate such as diphenyl carbonate, or cyclic carbonate such as propylene carbonate.

  Examples of the low-molecular polyols having a molecular weight of less than 200 include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 2- Butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3, 5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1 Aliphatic diol such as 9-nonanediol, cycloaliphatic diol such as cyclohexanedimethanol and cyclohexanediol; trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, tetra Examples thereof include trivalent or higher polyols such as methylolpropane.

  The polyisocyanate is not particularly limited, and examples thereof include diisocyanate and polyisocyanate having 3 or more isocyanate groups in one molecule. Examples of the diisocyanate include tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate. , P-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate and the like; isophorone Diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexane diisocyanate, cis-1,4-cyclohexanediiso Alicyclic diisocyanates such as anate and norbornene diisocyanate; Aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate Etc .; and mixtures thereof.

  Examples of the polyisocyanate having three or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and mixtures thereof. Of these trifunctional or higher isocyanates; modified products of these trifunctional or higher isocyanates such as carbodiimide modification, isocyanurate modification and biuret modification; blocked isocyanates in which these are blocked with various blocking agents; isocyanurate trimers of the aforementioned diisocyanates And biuret trimer.

  Among these, aliphatic diisocyanate or alicyclic diisocyanate is preferable because it is easily available and a polyurethane resin coating film having excellent weather resistance and strength is obtained. Among them, 1,6-hexamethylene diisocyanate and dicyclohexyl are preferred. It is particularly preferable to use methane-4,4′-diisocyanate or isophorone diisocyanate.

Examples of the anionic group-introducing agent include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, and 1,4-butanediol-2-sulfonic acid. And polyols containing a sulfonic acid group such as
Furthermore, from the viewpoint of availability, it is preferable to use a polyol containing a carboxyl group, and it is particularly preferable to use dimethylolpropionic acid.

  In the production of the polyurethane resin in the present invention, when the ratio of the total isocyanate group equivalent of the polyisocyanate to the total hydroxyl equivalent of the polyol (NCO / OH) is less than 1.0, a urethane prepolymer having a hydroxyl group at the terminal is formed. However, the terminal isocyanate prepolymer is generally used more favorably than the urethane prepolymer having a hydroxyl group at the terminal in terms of water dispersibility and easier molecular weight increase due to chain extension. The

Therefore, in the present invention, (NCO / OH) needs to be 1.0 or more, but even if (NCO / OH) is 1.0 or more, the urethane prepolymer is relatively high at less than 1.1. Since the molecular weight is increased, the dispersibility of the urethane prepolymer in water tends to be poor, and the storage stability of the water-based polyurethane resin may deteriorate.
On the other hand, if (NCO / OH) exceeds 2.5, production problems such as rapid foaming due to the generation of carbon dioxide accompanying the reaction of isocyanate groups with water during water dispersion of the prepolymer, and the base material of the coating film There may be a problem that the adhesiveness to is poor.

  Therefore, in the heat-sensitive coagulable water-based polyurethane resin composition of the present invention, the blending amount of the polyol, polyisocyanate and anionic group introducing agent is the total isocyanate of the polyisocyanate relative to the total hydroxyl equivalent of the polyol and anionic group introducing agent. The group equivalent ratio (NCO / OH) ratio is preferably 1.1 to 2.5, more preferably 1.2 to 2.0, and 1.3 to 1. It is particularly preferable that the amount is 8.

  Further, the compounding amount of the anionic group introducing agent is such that the acid value based on the anionic group of the anionic group introducing agent in the urethane prepolymer comprising the polyol, polyisocyanate and anionic group introducing agent is 5 to 50 mgKOH / g. The amount is preferably 10 to 30 mg KOH / g. When the acid value is less than 5 mgKOH / g, the water dispersibility of the urethane prepolymer tends to be poor, and the storage stability of the water-based polyurethane resin tends to deteriorate. When the acid value exceeds 50 mgKOH / g, the viscosity of the urethane prepolymer is high. This causes problems such as difficulty in water dispersion and poor water resistance of the polyurethane resin coating film.

  Examples of the anionic group neutralizing agent include trialkylamines such as trimethylamine, triethylamine, and tributylamine; N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1- N, N-dialkylalkanolamines such as dimethylamino-2-methyl-2-propanol; N-alkyl-N, N-dialkanolamines; tertiary amine compounds of trialkanolamines such as triethanolamine; ammonia And basic compounds such as trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  The amount of the anionic group neutralizing agent used is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, per 1 equivalent of anionic group. If the amount of the anionic group neutralizing agent used is too large or insufficient, not only the storage stability of the water-based urethane resin composition, but also the physical properties such as the strength of the water-based urethane resin film and the water resistance will decrease. There is a fear.

  Examples of the emulsifier include ordinary anionic surfactants and nonionic surfactants; primary amine salts, secondary amine salts, tertiary amine salts, and quaternary amines other than the component (B). Known surfactants such as cationic surfactants such as salts and pyridinium salts; amphoteric surfactants such as betaine type, sulfate ester type and sulfonic acid type;

  Examples of the anionic surfactant include sodium sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium dodecyl sulfate; polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; sodium Sulfolicinolate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abiates; Sodium benzene sulfonate, Alkaline phenol hydroxyethylene Alkyl aryl sulfonates such as alkali metal sulfate High alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkyl aryl sulfate salt; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetate N-acyl amino acid salt; N-acyl methyl taurine salt and the like.

  Examples of the nonionic surfactant include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; and alcohols having 1 to 18 carbon atoms. Examples include ethylene oxide and / or propylene oxide adduct; ethylene oxide and / or propylene oxide adduct of alkylphenol; ethylene glycol and / or propylene oxide adduct of alkylene glycol and / or alkylene diamine. Examples of the alcohol having 1 to 18 carbon atoms constituting these nonionic surfactants include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol. Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.

  Examples of the alkylphenol include phenol, methylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4- (1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F etc. are mentioned.

  Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. It is done. Moreover, as alkylenediamine, what substituted the alcoholic hydroxyl group of these alkylene glycol by the amino group etc. are mentioned. Further, the ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

  Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazolinium. Examples thereof include laurate.

  Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethyl Examples include betaine types such as metal salts of carboxymethyl betaine and hydroxypropyl phosphate, amino acid types such as metal salts of β-laurylaminopropionic acid, sulfate ester types, and sulfonic acid types.

  Although the usage-amount of the said emulsifier is not restrict | limited in particular, from viewpoints, such as water resistance of the coating film obtained by apply | coating a water-based urethane resin composition, it is 0 with respect to 100 mass parts of total amounts of polyurethane resin solid content. It is preferably 30 parts by mass, more preferably 0 to 20 parts by mass, and most preferably no emulsifier component.

Examples of the chain extender include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, and 2-butyl-2-ethyl. -1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, Fats such as 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol Diols; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; low molecular diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, piperazine, 2-methylpiperazine; polyoxypropylenediamine, polyoxyethylenediamine, etc. Polyether diamines of: Mensen diamine, isophorone diamine, norbornene diamine, aminoethylaminoethanol, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and other alicyclic diamines; m-xylenediamine, α- (m / p aminophene) Nyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α'-bis (4-aminophenyl) -p-diisopropyl Polyamines such as aromatic diamines such as benzene; succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, hydrated hydrazine, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1 , 1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide and the like; and water.
Among these, it is preferable to use diamines, hydrazines or water from the viewpoints of availability and reaction easiness, and it is particularly preferable to use ethylenediamine, adipic acid dihydrazide, hydrazine hydrate or water.

  The amount of the chain extender used is such that the equivalent ratio of the isocyanate reactive group of the chain extender to 1 equivalent of the isocyanate group in the urethane prepolymer before the chain extension reaction is 0 from the viewpoint of the physical properties of the coating film of the aqueous polyurethane resin. The amount is preferably in the range of 1 to 1.0.

  Examples of suitable solvents that are inert to the reaction and have a high affinity for water include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, and the like. It is preferable that the usage-amount of these solvents is 3-200 mass parts with respect to 100 mass parts of urethane prepolymers. When a solvent having a boiling point of 100 ° C. or lower is used as these solvents, it is preferable to synthesize the aqueous polyurethane resin and then remove the solvent by distillation under reduced pressure or the like.

上記式（１）中のＲ^１、Ｒ^２及びＲ^３は、それぞれ独立して炭素数が１〜８のアルキル基である。更に、得られる感熱凝固性水系ポリウレタン樹脂組成物の水溶性を良好にするためには、Ｒ^１、Ｒ^２及びＲ^３は炭素数が１〜４のアルキル基であることが好ましく、特にメチル基又はエチル基であることが好ましい。 In the present invention, a quaternary ammonium salt compound represented by the following general formula (1) is used as the heat-sensitive coagulant of the component (B).

R ¹ , R ² and R ³ in the above formula (1) are each independently an alkyl group having 1 to 8 carbon atoms. Furthermore, in order to improve the water solubility of the heat-sensitive coagulable water-based polyurethane resin composition obtained, R ¹ , R ² and R ³ are preferably alkyl groups having 1 to 4 carbon atoms, particularly methyl groups. Or it is preferable that it is an ethyl group.

Moreover, X < ^- > in the said General formula (1) is a chlorine ion, a bromine ion, or an iodine ion. Furthermore, from the viewpoint of the heat-sensitive coagulation property of the resulting resin composition, X ⁻ is preferably a chlorine ion or a bromine ion.

Further, R ⁴ in the general formula (1) is an alkyl group having 1 to 8 carbon atoms, or a group represented by the following general formula (2). Furthermore, in order to improve the water solubility and the heat-sensitive coagulation property of the heat-sensitive coagulable water-based polyurethane resin composition, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms or a group represented by the general formula (2). Preferably there is.

上記一般式（２）において、ａ及びｂは親水性に影響を及ぼす指数であり、ポリウレタン樹脂塗膜の耐水性が悪化することを防ぐためには、ａ及びｂが下記関係式を満たす整数であることが必要である。
０≦ａ≦３
ａ／(ａ＋ｂ)＜０．２
更に、ａ及びｂは下記の関係式を満たすことが必要である。
５≦ａ＋ｂ≦５０
上記関係式の値が５より小さいと、水系ポリウレタン樹脂の保存安定性が劣る傾向となり、また、５０を超えると感熱性が悪くなる傾向がある。
また、本発明においては、ａが０であると共に、ｂが１０〜２０の整数であることが好ましい。

In the above general formula (2), a and b are indices that affect hydrophilicity, and a and b are integers satisfying the following relational expression in order to prevent deterioration of the water resistance of the polyurethane resin coating film. It is necessary.
0 ≦ a ≦ 3
a / (a + b) <0.2
Furthermore, a and b must satisfy the following relational expression.
5 ≦ a + b ≦ 50
When the value of the relational expression is smaller than 5, the storage stability of the water-based polyurethane resin tends to be inferior, and when it exceeds 50, the thermal sensitivity tends to be deteriorated.
In the present invention, it is preferable that a is 0 and b is an integer of 10 to 20.

Examples of the compound in which R ^{1 to} R ⁴ in the general formula (1) are alkyl groups having 1 to 8 carbon atoms include, for example, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrahexylammonium, and tetraoctyl. ammonium, Application Benefits methyl ammonium, triethylhexylammonium, trioctyl methyl ammonium, such as trioctyl-butyl ammonium Niu arm, chloride, bromide or iodide and the like.

If necessary, various commonly used additives can be added to the heat-sensitive coagulable water-based polyurethane resin composition of the present invention.
Specific examples of the additive include, for example, a crosslinking agent, various weathering agents (hindered amine light stabilizers, ultraviolet absorbers and antioxidants), a silane coupling agent that particularly enhances adhesion to a substrate, and colloidal silica. Or inorganic colloidal sol such as colloidal alumina, tetraalkoxysilane and its condensation polymer, chelating agent, epoxy compound, pigment, dye, film-forming aid, curing agent, external cross-linking agent, viscosity modifier, leveling agent, antifoaming agent, Anticoagulant, radical scavenger, heat resistance imparting agent, inorganic or organic filler, plasticizer, lubricant, antistatic agent such as fluorine or siloxane, reinforcing agent, catalyst, thixotropic agent, waxes, antifogging Agents, antibacterial agents, antifungal agents, antiseptic agents, and rust inhibitors.

  Examples of the crosslinking agent include adducts of urea, melamine, benzoguanamine and the like with formaldehyde, amino resins such as alkyl ether compounds composed of these adducts and alcohols having 1 to 6 carbon atoms, polyfunctional epoxy compounds, A functional isocyanate compound, a block isocyanate compound, a polyfunctional aziridine compound, etc. are mentioned, For example, an oxazoline type compound, an epoxy-type compound, a carbodiimide type compound, an aziridine type compound, a melamine type compound, a zinc complex etc. are mentioned.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6- Tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracar Xylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) .Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperidi Amino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8 , 12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8 , 12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] -1,5,8,1 2-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4 , 8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy] ) Butyl Ruboniruokishi] ethyl] -2,4,8,10-spiro [5.5] undecane.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-C13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylpheny ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 1,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5 Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5 -Di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, octadecyl (3,5-di) Benzoates such as 3 butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyl Substituted oxanilides such as oxanilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metals Examples thereof include salts or metal chelates, particularly nickel or chromium salts or chelates.

Examples of the antioxidant include phosphorus-based, phenol-based, and sulfur-based antioxidants. Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl phosphite, Diphenyl decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra _{(C 12} alkyl _{-C 15} mixed alkyl alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis ( 4,6-diamil Phenyl)] isopropylidene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl -5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis) 3-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphipi N-6-yl) oxy] ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) ) Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] propyl] phenol, 2-butyl-2-ethylpropanediol-2,4,6-tritert-butylphenol Monophosphite etc. are mentioned.

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditertiarybutyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acroyl) Oxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) pro Onato], tocopherol and the like.

  Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic esters of polyols.

  The use amount of the weathering agent (hindered amine light stabilizer, ultraviolet absorber and antioxidant) is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the solid content of the aqueous polyurethane resin composition, It is more preferable that it is especially 0.01-5 mass parts. When the amount is less than 0.001 part by mass, a sufficient addition effect may not be obtained. When the amount is more than 10 parts by mass, the water dispersion stability and physical properties of the coating film may be adversely affected.

  As a method of adding these weathering agents, any of a method of adding to a urethane raw material polyol, a method of adding to a urethane prepolymer, a method of adding to a water phase during water dispersion of a urethane resin, and a method of adding after water dispersion However, from the viewpoint of easy operation, it is preferable to use a method of adding to the raw material polyol and a method of adding to the urethane prepolymer.

Method for producing a leather-like material of the present invention, the heat-sensitive coagulable aqueous polyurethane resin composition of the present invention, after application to the fiber substrate or after impregnation, an essential requirement be heat-sensitive coagulation.
The fiber base material used in the method for producing the leather-like material of the present invention is not particularly limited, and for example, a nonwoven fabric or a woven fabric can be used.
The nonwoven fabric may be one in which a knitted fabric or the like is laminated on the inside or the surface for the purpose of reinforcement or the like, and the fiber material may be either natural fiber or chemical fiber.

Examples of natural fibers include cotton, wool, silk, and asbestos. Examples of chemical fibers include regenerated fibers such as rayon and tencel; semi-synthetic fibers such as acetate and triacetate; and synthetic fibers such as polyamide fibers such as nylon, polyester fibers, polyolefin fibers, and acrylic fibers. It is done. Moreover, you may use suitably the fiber which mixedly used these.
In particular, since a texture and quality close to natural leather can be obtained, it is preferable to use polyamide fibers or polyester fibers.

A method of coating or impregnating the heat sensitive coagulable polyurethane resin composition ,, the present invention in the production method of the leather-like material of the present invention is not particularly limited, it is possible to use a method commonly performed.
Examples of the application method include methods using knife coating, air knife coating, roll coating, spray coating, and the like.
Examples of the impregnation method include a method of impregnating a non-woven fabric with a heat-sensitive coagulable polyurethane resin composition and squeezing with a press roll or the like, or using a doctor knife or the like to obtain an appropriate amount of impregnation.

As described above, after applying or impregnating the heat-sensitive coagulable water-based polyurethane resin composition of the present invention to a fiber base material, the polyurethane resin is heat-coagulated and dried in a dryer to obtain a leather-like sheet. Can do.
The temperature of the resin during heat-sensitive coagulation needs to be 40 to 90 ° C, preferably 50 to 80 ° C, and particularly preferably 55 to 75 ° C. When the temperature of the resin is less than 40 ° C., the storage stability of the heat-sensitive coagulable water-based polyurethane resin composition is deteriorated, and when it exceeds 90 ° C., migration of the polyurethane resin tends to occur and the texture of the leather-like material is lowered.

Examples of the coagulation method include a method of coagulating in a hot water bath at 70 ° C. or more, a method of coagulating in a steam atmosphere, and a method of coagulating by directly blowing hot air of 50 to 150 ° C. in a dryer.
As the coagulation method, a hot water bath at 70 ° C. or higher from the viewpoint that the heat transfer rate is high, the water-based polyurethane resin can be uniformly and instantaneously coagulated, and migration of the resin can be better prevented. It is preferable to use a method of solidifying in a method or a method of solidifying in a steam atmosphere.

In the leather-like material obtained by the production method of the present invention, the adhesion amount of the heat-sensitive coagulable aqueous polyurethane resin composition is 3 to 100 parts by mass with respect to 100 parts by mass of the fiber base material after the polyurethane resin is solidified and dried. It is preferably 5 to 70 parts by mass, particularly preferably 10 to 30 parts by mass. When the applied amount of the polyurethane resin is less than 3 parts by mass, the resulting sheet is insufficiently filled, and the leather-like texture tends to deteriorate. When the amount exceeds 100 parts by mass, the resulting sheet becomes hard, There is a tendency to feel bad.

The leather-like material obtained by the production method of the present invention can be used in the fields of vehicles, furniture, clothing, shoes, bags, bags, sandals, sundries, etc., for example, automobile interior materials such as car seats, wall materials, etc. It can be used for applications such as mattresses, cushions, lining materials, sports shoes, and men's shoes.

In addition to the leather-like material, the heat-sensitive coagulable water-based polyurethane resin composition of the present invention includes a paint, an adhesive, a surface modifier, an organic powder and / or an inorganic powder binder, a molded body, a building material, There are various uses such as sealing agents, casting materials, elastomers, foams, plastic raw materials, and fiber treatment agents.
More specifically, coating agents for plastics such as polyethylene, polypropylene, polyester and polycarbonate, glass fiber sizing agents, adhesives for laminates, agricultural film coating agents, thermal paper coating agents, binders for inkjet recording paper, gravure printing Ink binder agent, steel plate paint, glass, slate, paint for inorganic structural materials such as concrete, wood paint, fiber treatment agent, fiber coating agent, electronic material component coating agent, sponge, puff, glove, condom, etc. Is mentioned.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by these Examples.
[Production Example 1: Production of water-based polyurethane resin PUD-1]
<Urethane prepolymer production process>
350 g (0.350 mol) of a polyester polyol having a number average molecular weight of 1000 obtained by reacting neopentyl glycol and adipic acid as a polyol, and 221 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) as a polyisocyanate ( 0.844 mol), 28.7 g (0.214 mol) of dimethylolpropionic acid as an anionic group introducing agent, 150 g of methyl ethyl ketone as a solvent, and 0.018 g of octyltin dilaurate as a catalyst, and 85 to 85 under nitrogen atmosphere. It was made to react at 95 degreeC for 2 hours, it was confirmed that isocyanate content (NCO%) became 3.1%, and it was set as urethane prepolymer UP-1.

<Water dispersion / high molecular weight process>
In 560 g of water, 0.1 g of an antifoaming agent (manufactured by ADEKA, product name Adecanol B1016) and 14.4 g (0.142 mol) of triethylamine are added, 500 g of UP-1 is added, and the temperature is 20 to 40 ° C. After stirring for 15 minutes, 18.0 g (ethylenediamine 0.075 mol) of a mixed solution having a (ethylenediamine / water) mass ratio of 1/3 was added dropwise as a chain extender, and the mixture was stirred at 20 to 40 ° C. for 10 minutes.
Further, 52.4 g (adipic acid dihydrazide / water) having a mass ratio of 1/3 as a chain extender (0.075 mol adipic acid dihydrazide) was added, and the NCO group was added at 20 to 40 ° C. for 1 to 2 hours. Stirring was continued until disappeared, and then the methyl ethyl ketone solvent was distilled off to obtain an aqueous polyurethane resin PUD-1 having a solid content of 40%.

[Comparative Production Example 1: Production of water-based polyurethane resin PUD-2]
<Urethane prepolymer production process>
246 g (0.246 mol) of a polyester polyol having a number average molecular weight of 1000 obtained by reacting neopentyl glycol and adipic acid as a polyol, and 294 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) as a polyisocyanate ( 1.12 mol), 60 g (0.50 mol) of N-methyldiethanolamine, and 150 g of methyl ethyl ketone as a solvent and reacted at 85 to 95 ° C. for 3 hours in a nitrogen atmosphere, and the isocyanate content (NCO%) is 4.2. % And urethane prepolymer UP-2 was obtained.

<Water dispersion / high molecular weight process>
In 571 g of water, 0.2 g of an antifoaming agent (manufactured by ADEKA, product name Adecanol B1016) and 30.2 g (0.503 mol) of acetic acid were added, 500 g of the urethane prepolymer UP-2 was added, and 20 to 20 After stirring at 40 ° C. for 2 to 3 hours until the NCO group disappeared, the methyl ethyl ketone solvent was distilled off to obtain an aqueous polyurethane resin PUD-2 having a solid content of 40%.

[Comparative Production Example 2: Production of water-based polyurethane resin PUD-3]
<Urethane prepolymer production process>
As the polyol, 431 g (0.431 mol) of a polyester polyol having a number average molecular weight of 1000 obtained by reacting neopentyl glycol and adipic acid, 169 g (0.645) of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI). Mol), 150 g of methyl ethyl ketone as a solvent, and 0.018 g of octyl tin dilaurate as a catalyst were reacted at 85 to 95 ° C. for 2 hours in a nitrogen atmosphere, and the isocyanate content (NCO%) was 2.4%. This was confirmed and urethane prepolymer UP-3 was obtained.

<Water dispersion / high molecular weight process>
41.5 g of an emulsifier (manufactured by ADEKA, product name Adeka Pluronic L-64) was added to 538 g of water, 500 g of UP-3 was added, and the mixture was stirred at 20 to 40 ° C. for 15 minutes, and then a chain extender. As a solution, 14.0 g (ethylenediamine 0.058 mol) of an aqueous solution having a (ethylenediamine / water) mass ratio of 1/3 was added dropwise and stirred at 20 to 40 ° C. for 10 minutes.
Furthermore, 40.0 g (adipic acid dihydrazide) / (water) 4/3 g (adipic acid dihydrazide 0.057 mol) was added as a chain extender (adipic acid dihydrazide) / (water), and the NCO group disappeared at 20 to 40 ° C. After stirring for 1 to 2 hours, the methyl ethyl ketone solvent was distilled off to obtain an aqueous polyurethane resin PUD-3 having a solid content of 40%.

[Example 1-1]
The following quaternary ammonium salt compound-1 50% by mass aqueous solution is blended with respect to 100 parts by mass of the polyurethane resin solid content of the aqueous polyurethane resin PUD-1, so that the compound-1 is 5 parts by mass. The aqueous polyurethane resin composition PUD-1-1 was obtained.
The quaternary ammonium salt compound-1 is a group represented by the general formula (1) in which R ¹ and R ³ are ethyl groups, R ² is a methyl group, and R ⁴ is the general formula (2). In the formula (2), a is 0 and b is 15.

[Example 1-2]
An aqueous polyurethane resin composition PUD-1-2 was obtained in the same manner as in Example 1-1 except that the following quaternary ammonium salt compound-2 was used instead of the quaternary ammonium salt compound-1. It was.
In the general quaternary ammonium salt compound-2, R ¹ and R ³ in the general formula (1) are ethyl groups, R ² is a methyl group, and R ⁴ is a group represented by the general formula (2). In the formula (2), a is 2 and b is 30.

[Example 1-3]
An aqueous polyurethane resin composition PUD-1-3 was obtained in the same manner as in Example 1-1 except that the following quaternary ammonium salt compound-3 was used instead of the quaternary ammonium salt compound-1. It was.
In the quaternary ammonium salt compound-3, R ¹ and R ³ in the general formula (1) are ethyl groups, R ² is a methyl group, and R ⁴ is a group represented by the general formula (2). In the formula (2), a is 0 and b is 10.

[Example 1-4]
A water-based polyurethane resin composition PUD-1-4 was obtained in the same manner as in Example 1-1, except that tetramethylammonium chloride was used instead of the quaternary ammonium salt compound-1.

[Comparative Example 1-1]
In the same manner as in Example 1-1, except that 100 parts by mass of the solid content of the aqueous polyurethane resin composition PUD-2 was used instead of 100 parts by mass of the solid content of the aqueous polyurethane resin PUD-1, an aqueous polyurethane was obtained. Resin composition PUD-1-5 was obtained.

[Comparative Example 1-2]
The same as Example 1-1 except that 100 parts by mass of the polyurethane resin solid content of the aqueous polyurethane resin composition PUD-3 was used instead of 100 parts by mass of the polyurethane resin solid content of the aqueous polyurethane resin PUD-1. A water-based polyurethane resin composition PUD-1-6 was obtained by the method.

[Comparative Example 1-3]
An aqueous polyurethane resin PUD-1-7 was produced in the same manner as in Example 1-1 except that quaternary ammonium salt compound-4 was used instead of quaternary ammonium salt compound-1. Since an aggregate appeared immediately after production, a good aqueous resin could not be obtained.
In the quaternary ammonium salt compound-4, R ¹ and R ³ in the general formula (1) are ethyl groups, R ² is a methyl group, and R ⁴ is a group represented by the general formula (2). In the formula (2), a is 0 and b is 2.

[Comparative Example 1-4]
An aqueous polyurethane resin composition PUD-1-8 was obtained in the same manner as in Example 1-1 except that quaternary ammonium salt compound-5 was used instead of quaternary ammonium salt compound-1. .
In the quaternary ammonium salt compound-5, R ¹ and R ³ in the general formula (1) are ethyl groups, R ² is a methyl group, and R ⁴ is a group represented by the general formula (2). In the formula (2), a is 5 and b is 15.

[Comparative Example 1-5]
An aqueous polyurethane resin composition PUD-1-9 was produced in the same manner as in Example 1-1 except that the quaternary ammonium salt compound-1 was replaced with tetramethylammonium hydroxide. As a result, a good aqueous resin composition could not be obtained.

[Comparative Example 1-6]
A water-based polyurethane resin composition PUD-1-10 was obtained in the same manner as in Example 1-1 except that the quaternary ammonium salt compound-1 was replaced with a 20% ammonium sulfate aqueous solution.

  The water-based polyurethane resin compositions PUD-1-1 to PUD-1-10 obtained above were evaluated for storage stability and thermal coagulation temperature. The results are shown in Table 1.

[Storage stability evaluation method]
The sample was left in an atmosphere of 30 ° C. for 3 months, and the separated state was visually evaluated.
○: No separation at all △: Slight separation or resin sedimentation ×: Many separation or resin sedimentation

[Measurement of thermal coagulation temperature]
50 g of each of PUD-1-1 to PUD-1-10 was put into a 100 ml beaker, and this was gradually heated while stirring in a 95 ° C. hot water bath, and the temperature at which the water-based resin solidified was measured.

From Example 1 and Comparative Examples 1-3 to 1-5, an aqueous polyurethane resin composition having excellent storage stability can be obtained by using the specific quaternary ammonium salt compound used in the present invention. Was confirmed.
Also from the results of Comparative Example 1-6, the aqueous polyurethane resin composition using the quaternary ammonium salt compound is superior in storage stability to the aqueous polyurethane resin composition using a general-purpose heat-sensitive coagulant. It was confirmed that

As for PUD-1-7 (Comparative Example 1-3) and PUD-1-9 (Comparative Example 1-5), as described above, a good water-based resin composition could not be obtained. The temperature was not measured.
Moreover, about PUD-1-5 (Comparative Example 1-1) and PUD-1-6 (Comparative Example 1-2), since it did not solidify even if it exceeded 90 degreeC, the said specific quaternary ammonium It was confirmed that a resin composition having heat-sensitive coagulation properties could not be obtained even when a salt compound and a urethane resin having no anionic group were combined.
As is clear from these results, it is impossible to use the above PUD-1-5 to PUD-1-7 and PUD-1-9 as a heat-sensitive coagulable water-based urethane resin composition, and therefore the following comparison In Examples 2 and 3, these resin compositions were not used.

[Examples 2-1 to 2-4: Production of leather-like material]
After impregnating 200 parts by mass of each of the heat-sensitive coagulable water-based polyurethane resin compositions PUD-1-1 to PUD-1-4 with respect to 100 parts by mass of the nonwoven fabric, using a hot air drier for 5 minutes at 100 ° C. Then, it was dried at 150 ° C. for 3 minutes to obtain a leather-like material.
The adhesion amount of the polyurethane resin after drying the leather-like materials of Examples 2-1 to 2-4 was 23, 21, 24, and 20 parts by mass with respect to 100 parts by mass of the nonwoven fabric, respectively.

[Comparative Examples 2-1 and 2-2]
A leather-like material was obtained in the same manner as in Example 2 except that the heat-sensitive coagulating water-based polyurethane resin compositions PUD-1-8 and PUD-1-10 were used.
The adhesion amount of the polyurethane resin after drying the leather-like materials of Comparative Examples 2-1 and 2-2 was 19 and 18 parts by mass with respect to 100 parts by mass of the nonwoven fabric, respectively.

  The leather-like material obtained in each example and comparative example was evaluated for migration prevention, crack resistance and texture. The results are shown in Table 2.

[Migration prevention evaluation]
The cross section of each leather-like sheet was observed for the presence or absence of migration using an electron microscope (manufactured by JEOL Ltd .: JSM-6390LA) and evaluated based on the following criteria.
○: No migration △: Some migration occurred ×: Many migrations occurred

[Crack resistance evaluation]
The surface of the leather-like sheet was visually evaluated based on the following.
○: No cracks occurred △: Some cracks occurred ×: Overall cracks occurred

[Texture evaluation]
The softness of the leather-like sheet was observed by tactile sensation, and the texture was evaluated based on the following criteria.
○: flexibility similar to natural leather △: flexibility slightly inferior to natural leather ×: flexibility inferior to natural leather

[Examples 3-1 to 3-4: Preparation of coating film]
On the glass plate, heat-sensitive coagulable water-based polyurethane resins PUD-1-1 to PUD-1-4 were applied using a bar coater to a thickness of 100 μm, dried at 100 ° C. for 5 minutes, and then 120 ° C. And dried for 2 hours to prepare a coating film.
[Comparative Examples 3-1, 3-2]
A coating film was produced in the same manner as in Example 3 except that the aqueous polyurethane resin was changed to PUD-1-8 and PUD-1-10.

[Evaluation of hot water resistance]
After immersing the obtained coating film in 90 degreeC hot water for 30 minutes, the area swelling rate of the coating film was measured and hot water resistance was evaluated based on the following reference | standard. The results are shown in Table 3.
○: Area swelling rate of less than 3% Δ: Area swelling rate of 3 to 5%
×: Area swelling rate over 5%

  From the results of Examples 2 and 3 and Comparative Examples 2 and 3, an aqueous polyurethane resin composition containing a quaternary ammonium salt that does not satisfy the requirement of the general formula (1) and a leather-like material using the composition are as follows: Various performances were inferior, and it was confirmed that the specific heat-sensitive coagulable water-based polyurethane resin composition of the present invention was excellent in heat-sensitive coagulation, and showed good results in all of the various performances as a leather-like material.

  The heat-sensitive coagulable water-based polyurethane resin composition of the present invention is excellent in storage stability and has various uses such as resin products and paints, but can provide a leather-like material having particularly excellent physical properties. It is effective in the production of interiors, furniture, clothing, shoes, bags, bags, sandals, sundries, etc., and is extremely useful in industry.

Claims (7)

(A) a polyurethane resin having at least one anionic group selected from a carboxyl group and a sulfonic acid group in the molecule, and (B) a heat-sensitive coagulable water-based polyurethane resin composition containing a heat-sensitive coagulant. The component (B) is a quaternary ammonium salt compound represented by the following general formula (1), and the component (B) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (A). A heat-sensitive coagulable water-based polyurethane resin composition comprising:

However, R ¹ , R ² and R ³ in the above formula (1) are each independently an alkyl group having 1 to 8 carbon atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, or the following general group A group represented by formula (2), wherein X ⁻ is a chlorine ion, a bromine ion or an iodine ion;

However, a and b in the above formula (2) are integers satisfying the following relational expression;
0 ≦ a ≦ 3,
5 ≦ a + b ≦ 50, and a / (a + b) <0.2.   The component (A) is a polyurethane resin comprising a polyol, a polyisocyanate, and an anionic group introducing agent, and the polyol, the polyisocyanate, and the anionic introducing agent are polyvalent to the total hydroxyl equivalent of the polyol and the anionic group introducing agent. The heat-sensitive coagulable water-based polyurethane resin composition according to claim 1, which is blended so that a ratio (NCO / OH) of all isocyanate group equivalents of isocyanate is 1.1 to 2.5.   The compounding amount of the anionic group introducing agent is 5 to 50 mgKOH / g based on the anionic group of the anionic group introducing agent in the urethane prepolymer comprising the polyol, polyisocyanate and anionic group introducing agent. The heat-sensitive coagulable aqueous polyurethane resin composition according to claim 2, which is an amount.   The heat sensitive component according to any one of claims 1 to 3, wherein the component (A) further contains 0.2 to 2.0 equivalents of an anionic group neutralizing agent with respect to 1 equivalent of the anionic group. Solidifying water-based polyurethane resin composition. R ⁴ in the formula (1) is a group represented by the general formula (2), a in the general formula (2) is 0, and b is 10-20. The heat-sensitive coagulable water-based polyurethane resin composition described in any of the above.   The heat-sensitive coagulable water-based polyurethane resin composition according to any one of claims 1 to 5, wherein the content of the component (B) is 5 to 20 parts by mass with respect to 100 parts by mass of the component (A). . The heat-sensitive coagulable aqueous polyurethane resin composition according to any one of 請 Motomeko 1-6, was applied to the fiber base material, or after impregnating, leather-like material, characterized in that to heat-sensitive coagulation Manufacturing method .