JP6674244B2 - Thermosensitive coagulable water-based polyurethane resin composition, method for producing leather-like material using the composition, and leather-like material produced by the method - Google Patents

Description

  The present invention relates to a thermosetting water-soluble polyurethane resin composition, a method for producing a leather-like material using the composition, and a leather-like material produced by the method, and particularly excellent in storage stability and migration prevention. The present invention relates to a heat-coagulable water-based polyurethane resin composition, a method for producing a leather-like material having excellent hand and antibacterial properties using the composition, and a leather-like material produced by the method.

  Leather-like materials used as substitutes for natural leather include artificial leather composed of resin and non-woven fabric, and synthetic leather composed of resin and woven or knitted fabric, such as clothing, shoes, and bags. It is used as an interior material including fashion materials, furniture, and vehicles. Polyurethane resins are often used for these leather-like materials.

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 composition is a poor solvent for the polyurethane resin, and a coagulation liquid that is compatible with the organic solvent. There is a wet coagulation method in which the polyurethane resin is coagulated by immersion in the same, then washed with water and dried to produce a leather-like material.
In the wet coagulation method, water is generally used as a coagulation liquid, and dimethylformamide or the like is often used as an organic solvent compatible with water, but an organic solvent causes a fire because of high flammability. In addition, due to the high toxicity and the problems of manufacturing suitability and environmental suitability such as pollution to the environment and human body, studies have been made to shift from solvent-based polyurethane resins to water-based polyurethane resins.

  As a method of producing a leather-like material using an aqueous polyurethane resin composition, a heat coagulation method of coagulating a resin composition by drying a resin-coated or impregnated fiber base material with hot water, steam or hot air is used. As an alternative to the wet coagulation method. The heat coagulation method uses a water-based polyurethane resin composition instead of a solvent-based polyurethane resin, so it is a production method that is friendly to the environment and the human body.On the other hand, when heated and dried, the urethane resin that was uniformly dispersed in the fiber base material There is a problem that a so-called migration phenomenon, in which particles of the composition move to the surface of the substrate, is likely to occur. Due to this phenomenon, the effect of causing the urethane resin to exist inside the fiber and imparting flexibility and texture to the leather may be lost.

  In order to solve the problem of migration of a leather-like material, a method of applying an aqueous resin composition obtained by dissolving inorganic salts to an emulsified emulsion to a nonwoven sheet and drying by heating (for example, Patent Document 1), heat-sensitive coagulation temperature A method of coagulating an aqueous resin composition comprising an aqueous polyurethane resin having a temperature of 40 to 90 ° C. and an associative thickener with steam (for example, Patent Document 2), a nonionic surfactant having an HLB of 10 to 18 and an inorganic salt A heat coagulation method such as a method of applying a carboxylate-type polyurethane resin containing the above to a fibrous material substrate and heat coagulation (for example, Patent Document 3) has already been disclosed.

However, although the above-mentioned heat coagulation method shows improvement in migration prevention properties, due to the effects of surfactants, inorganic salts and thickeners remaining in the leather-like material, the texture and the texture of the obtained leather-like material are reduced. There was a disadvantage that the hot water resistance was not sufficiently satisfactory.
In addition, the aqueous polyurethane resin composition used in the heat coagulation method generally has a drawback that storage stability is poor.

As a heat-sensitive coagulant capable of improving the texture, hot water resistance, and storage stability of the leather, a method using a quaternary ammonium salt having an adduct of ethylene oxide and propylene oxide as a functional group is known. (For example, Patent Document 4). However, with the growing trend toward cleanliness and hygiene, leathers with antibacterial properties using fibers made of various antibacterial agents and bacteriostatic agents have been required in artificial leather and synthetic leather applications. In recent years, the above method has a drawback that when an antibacterial agent is added, a urethane resin aggregates and precipitates, and a satisfactory aqueous polyurethane resin composition cannot be obtained.
Examples of the method for imparting antibacterial properties include a method using a metal such as silver, copper, or zinc or a compound thereof (for example, Patent Documents 5 and 6), but these methods are wet methods using a solvent. It is only carried out in the coagulation method, and in the case of the heat coagulation method using an environmental or human body-friendly water-based polyurethane resin, even if the above antibacterial agent is used, good results are obtained for the antibacterial property However, it was difficult to prevent migration during production, and a leather-like material having a good texture could not be obtained.

JP-A-06-316877 JP 2000-290879 A JP 2003-138131 A JP 2013-170176 A JP 2001-98468 A JP-A-2002-38380

Therefore, a first object of the present invention is to provide a heat-sensitive coagulable water-based polyurethane resin composition having excellent storage stability and excellent migration prevention properties.
A second object of the present invention is to provide a method for producing a leather-like material having excellent hand and antibacterial properties using a heat-coagulable water-based polyurethane resin composition.
Further, a third object of the present invention is to provide a leather-like material which is manufactured by a heat coagulation method and has excellent texture and antibacterial properties.

  Accordingly, the present inventors have conducted intensive studies to achieve the above objects, and as a result, the polyurethane resin containing a carboxyl group and / or a sulfonic acid group, and a specific quaternary ammonium salt compound that is a thermosensitive coagulant. The heat-coagulable water-based polyurethane resin composition is excellent not only in storage stability and heat-coagulation at a low temperature, but also excellent in anti-migration property at the time of heat-coagulation, and a leather-like material thus obtained. However, they have found that they have excellent texture and antibacterial properties, and have reached the present invention.

上記式（１）中のＲ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して炭素数が２〜８のアルキル基、フェニル基又はベンジル基を表し、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４に含まれる芳香環の数は０又は１であり、Ｘは塩素原子、臭素原子又はヨウ素原子である。
本発明においては、前記（Ａ）成分が、ポリオール、ポリイソシアネート及びアニオン性基導入剤を反応させてなるウレタンプレポリマーを原料とする成分であって、前記ポリオール、ポリイソシアネート及びアニオン性導入剤が、ポリオール及びアニオン性基導入剤の全水酸基当量に対するポリイソシアネートの全イソシアネート基当量の比であるＮＣＯ／ＯＨが、１．１〜２．５となる如く配合されてなることが好ましく（請求項２）、前記ウレタンプレポリマーの酸価が５〜５０ｍｇＫＯＨ／ｇであることが好ましい（請求項３）。
また、前記アニオン性基１当量に対し、０．２〜２．０当量のアニオン性基中和剤（Ｃ）を更に含有することが好ましく（請求項４）、前記（Ｂ）成分の含有量は、前記（Ａ）成分１００質量部に対して５〜２０質量部であることが好ましい（請求項５）。 That is, the present invention relates to a heat-coagulable water-based polyurethane resin composition comprising (A) a polyurethane resin having at least one anionic group selected from a carboxyl group and a sulfonic acid group in a molecule, and (B) a thermocoagulant. Wherein the component (B) is a quaternary ammonium salt compound represented by the following general formula (1), and the component (B) is contained in an amount of 0.1 to 100 parts by mass of the component (A). A heat-coagulable water-based polyurethane resin composition characterized by being blended in an amount of 1 to 50 parts by mass, a method for producing a leather-like material having excellent texture and antibacterial properties using the composition, and the method Leather-like material with excellent texture and antibacterial properties, manufactured by:

R ¹ , R ² , R ³ and R ⁴ in the above formula (1) each independently represent an alkyl group having 2 to 8 carbon atoms, a phenyl group or a benzyl group, and R ¹ , R ² , R ³ And the number of aromatic rings contained in R ⁴ is 0 or 1, and X is a chlorine atom, a bromine atom or an iodine atom.
In the present invention, the component (A) is a component obtained from a urethane prepolymer obtained by reacting a polyol, a polyisocyanate, and an anionic group-introducing agent, and the polyol, the polyisocyanate, and the anion-introducing agent are used as components. It is preferable that NCO / OH, which is the ratio of the total isocyanate group equivalents of the polyisocyanate to the total hydroxyl group equivalents of the polyol and the anionic group-introducing agent, is 1.1 to 2.5 (claim 2). ), The urethane prepolymer preferably has an acid value of 5 to 50 mgKOH / g (Claim 3).
Further, it is preferable that 0.2 to 2.0 equivalents of the anionic group neutralizing agent (C) is further contained per 1 equivalent of the anionic group (Claim 4), and the content of the component (B). Is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component (A) (Claim 5).

  The heat-coagulable water-based polyurethane resin composition of the present invention has excellent storage stability and migration-preventing property during heat coagulation, and is coated or impregnated with the heat-coagulable water-based polyurethane resin composition of the present invention. The leather-like material obtained by heating and coagulating after heating has an effect of being excellent in texture and antibacterial properties.

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. The composition and the production method of such a polyurethane resin (A) are not particularly limited, and examples thereof include the following production methods.
(1) A urethane prepolymer is produced by reacting a polyol, a polyisocyanate and an anionic group-introducing agent, and after adding an anionic group-neutralizing agent as necessary, an aqueous solution containing an emulsifier as necessary is A prepolymer is added and dispersed (prepolymer mixing method).
Or
(2) A urethane prepolymer is produced by reacting a polyol, a polyisocyanate and an anionic group-introducing agent, and an aqueous solution containing an anionic group-neutralizing agent and / or an emulsifier, if necessary, is prepared. Is added to the prepolymer and dispersed (phase inversion method).
The urethane resin dispersed in water by the method (1) or (2) is subjected to chain extension in water using a chain extender.
In the production of the prepolymer, a solvent which is inert to the reaction and has high affinity for water may be used, if necessary.

The polyol is not particularly limited, and examples thereof include polyether polyols, polyester polyols, polyester polycarbonate polyols, and crystalline or non-crystalline polycarbonate polyols.
The number average molecular weight of these polyols is not particularly limited, but is preferably from 300 to 5,000, more preferably from 500 to 3,000.

  Examples of the polyether polyols include 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, Ethylene oxide and / or propylene oxide adducts of low molecular weight polyols having a molecular weight of less than 200, such as glycerin, polyglycerin, and pentaerythritol; ethylene oxide and / or propylene oxide adducts of aromatic polyols such as bisphenol A; ethylenediamine And ethylene oxide and / or propylene oxide adducts such as amine compounds; and polytetramethylene ether glycol.

  As the polyester polyols, a direct esterification reaction or transesterification between a low molecular weight polyol having a molecular weight of less than 200 and a polyvalent carboxylic acid in an amount smaller than the stoichiometric amount, or an ester-forming derivative of the polyvalent carboxylic acid. Polyester polyols obtained by a reaction; polyester polyols obtained by a direct esterification reaction of the low-molecular polyol with a lactone or a hydroxycarboxylic acid obtained by a hydrolytic ring-opening reaction thereof.

  Examples of the low-molecular polyol 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, 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, 1,8-octanediol, 2-methyl-1,8-octanediol, 1, Aliphatic diols such as nonanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; and trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, A trivalent or higher polyol such as tetramethylolpropane is exemplified.

  Examples of the polycarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, 2-methylsuccinic acid, and 2-methyladipin Fats such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid and dimer acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Tricarboxylic acids such as trimeric acid, trimesic acid, and trimer of castor oil fatty acid Acids; and tetravalent or higher carboxylic acids such as pyromellitic acid.

  Examples of the ester-forming derivative of the polycarboxylic acid include carboxylic acid anhydrides, carboxylic acid chlorides, and carboxylic acid halides such as carboxylic acid bromide; polycarboxylic acid methyl esters, ethyl esters, propyl esters, and isopropyl esters. And lower aliphatic esters such as butyl ester, 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 a reaction product 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. Products.

  Examples of the crystalline or non-crystalline polycarbonate polyols 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 a diaryl carbonate such as phosgene and diphenyl carbonate, or a cyclic carbonate such as propylene carbonate.

In the present invention, among the polyols described above, polyester polyols having excellent heat resistance and abrasion resistance are preferred, and in particular, neopentyl glycol, 3-methyl-1,5-pentanediol or 1,6-hexanediol, Polyester polyols obtained by reacting adipic acid are preferred.
In the present invention, in order to change the physical properties of the water-based polyurethane resin composition, a low-molecular-weight polyol having a molecular weight of less than 200 may be used in addition to the polyols.

The polyisocyanate is not particularly limited, and examples thereof include a diisocyanate and a polyisocyanate having three or more isocyanate groups in one molecule.
Examples of the diisocyanate include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, and 3,3′-dimethyldiphenyl-4,4′-diisocyanate. , Dianisidine diisocyanate, aromatic diisocyanates such as tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexane diisocyanate, cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate Alicyclic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate Aliphatic diisocyanates such as socyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; and mixtures thereof.

  Examples of the polyisocyanate having three or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethanetetraisocyanate, and mixtures thereof. Tri- or more functional isocyanates; carbodiimide-modified, isocyanurate-modified, biuret-modified, etc. of these tri- or more-functional isocyanates; blocked isocyanates obtained by blocking these modified products with various blocking agents; Examples include isocyanurate trimers and biuret trimers.

  In the present invention, among these, aliphatic diisocyanates or alicyclic diisocyanates are preferable from the viewpoint that they are easily available and that a coating film of a polyurethane resin having excellent weather resistance and strength is obtained. It is particularly preferred to use 6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate or isophorone diisocyanate.

  Examples of the anionic group-introducing agent include polyols containing a carboxyl group such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, and 1,4-butanediol-2-sulfonic acid. And other polyols containing a sulfonic acid group. In the present invention, among these, from the viewpoint of availability, it is preferable to use a polyol containing a carboxyl group, and 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 equivalents of the polyisocyanate to the total hydroxyl group equivalents of the polyol (NCO / OH) is less than 1.0, the urethane prepolymer having a hydroxyl group at the terminal is used. Generate. However, a terminal isocyanate prepolymer is used in the present invention in view of the fact that a terminal isocyanate prepolymer is easier to increase the molecular weight by water dispersibility and chain extension than a urethane prepolymer having a hydroxyl group at a terminal. Is preferred.

  Therefore, in the present invention, the NCO / OH is preferably set to 1.0 or more, but the NCO / OH is preferably set to 1.1 or more so that the urethane prepolymer does not have a very high molecular weight. Thereby, the dispersibility of the urethane prepolymer in water can be adjusted, and the storage stability and the like of the aqueous polyurethane resin can be adjusted. On the other hand, if the NCO / OH exceeds 2.5, the urethane resin foams rapidly due to the generation of carbon dioxide due to the reaction between the isocyanate groups and water during the aqueous dispersion of the prepolymer during production, There may be a problem that the adhesiveness to the base material is poor.

  Therefore, in the thermosetting aqueous polyurethane resin composition of the present invention, the blending amount of the polyol, polyisocyanate and anionic group-introducing agent is the total isocyanate group equivalent of the polyisocyanate with respect to the total hydroxyl equivalents of the polyol and the anionic group-introducing agent. The ratio (NCO / OH) is preferably from 1.1 to 2.5, more preferably from 1.2 to 2.0, and more preferably from 1.3 to 1.8. Particularly preferred is an amount.

  Furthermore, 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 composed of the polyol, polyisocyanate and anionic group-introducing agent is 5 to 50 mgKOH / g. Is preferable, and more preferably 10 to 30 mgKOH / g. When the acid value is less than 5 mgKOH / g, the water dispersibility of the urethane prepolymer may be poor or the storage stability of the aqueous polyurethane resin may be deteriorated. In some cases, the dispersion becomes difficult due to an increase in viscosity, or the water resistance of the polyurethane resin coating film may be poor.

  Examples of the anionic group neutralizer 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; tertiary amine compounds of trialkanolamines such as N-alkyl-N, N-dialkanolamines and triethanolamine; ammonia And basic compounds such as trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide.

  In the present invention, among these anionic group neutralizers, from the viewpoint of improving the weather resistance and water resistance after drying, those having a high volatility that is easily dissociated by heat are preferable, and in particular, trimethylamine And triethylamine are preferred. These neutralizers may be used alone or in combination of two or more.

  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 equivalent of the anionic group. If the amount of the anionic group neutralizer is too large or too small, not only the storage stability of the aqueous polyurethane resin composition, but also the aqueous polyurethane resin film, mechanical properties such as strength and various physical properties such as water resistance, It may decrease.

  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, and amphoteric surfactants such as betaine type, sulfate ester type and sulfonic acid type can be mentioned.

  Examples of the anionic surfactant include alkyl 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; Ammonium salts of alkylsulfonates such as sodium sulfolicinolate, alkali metal salts of sulfonated paraffin and ammonium salts of sulfonated paraffin; fatty acid salts such as sodium laurate, triethanolamine oleate, triethanolamine aviate; Alkali metal sulfur of sodium benzene sulfonate and alkali phenol hydroxyethylene Alkylarylsulfonates such as salts of high alkyl naphthalenesulfonate, naphthalenesulfonic acid formalin condensate, dialkylsulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene ether phosphate Salt, polyoxyethylene alkyl ether acetate, N-acyl amino acid salt, N-acylmethyl 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; Ethylene oxide and / or propylene oxide adducts of alcohols; ethylene oxide and / or propylene oxide adducts of alkylphenols; and ethylene oxide and / or propylene oxide adducts of alkylene glycol and / or alkylenediamine.

  Examples of the alcohol having 1 to 18 carbon atoms constituting the nonionic surfactant include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tert-butanol, amyl alcohol, isoamyl alcohol, 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-tertiary octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, and Bisphenol F and the like.

  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, , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol and the like. No. Examples of the alkylene diamine include those in which the alcoholic hydroxyl group of these alkylene glycols is substituted with an amino group. Further, the ethylene oxide and propylene oxide adducts may be random adducts or block adducts.

  Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, lauryl benzyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, alkyl pyridinium bromide and imidazolinium Laurate and the like.

  Examples of the amphoteric surfactant include coconut oil fatty acid amide propyl dimethyl acetate betaine, lauryl dimethyl amino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, lauryl hydroxysulfobetaine, lauroylamidoethyl hydroxyethyl. Betaine types such as carboxymethyl betaine and metal salts of hydroxypropyl phosphoric acid; amino acid types, sulfate ester types and sulfonic acid types such as metal salts of β-laurylaminopropionic acid;

  Among the above-mentioned emulsifiers, nonionic surfactants are preferable because when they are mixed with a heat-sensitive coagulant or an anionic group neutralizer, aggregates and the like hardly occur. In the present invention, fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate, which are easily available and inexpensive to use; and ethylene oxide and / or alcohol having 1 to 18 carbon atoms. It is more preferred to use a propylene oxide adduct.

  The amount of the emulsifier is not particularly limited, but from the viewpoint of the water resistance of a coating film obtained by applying the aqueous polyurethane resin composition, from 0 to 100 parts by mass of the total amount of the polyurethane resin solid content. The amount is preferably 30 parts by mass, more preferably 0 to 20 parts by mass, and most preferably no emulsifier component is used.

  Examples of the chain extender for elongating the water-dispersed urethane resin in water 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, 7,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-o Aliphatic diols such as tandiol and 1,9-nonanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; low molecular weight compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, piperazine and 2-methylpiperazine Diamines; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; mensendiamine, isophoronediamine, norbornenediamine, aminoethylaminoethanol, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, Alicyclic diamines such as bis (aminomethyl) cyclohexane and 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane M-xylenediamine, α- (m / p-aminophenyl) ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, Polyamines such as aromatic diamines such as α'-bis (4-aminophenyl) -p-diisopropylbenzene; succinic dihydrazide, adipic dihydrazide, sebacic dihydrazide, phthalic dihydrazide, hydrazine hydrate, 1,6-hexa Hydrazines such as methylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide; and water. It is.

In the present invention, among these, it is preferable to use diamines, hydrazines or water from the viewpoint of availability and ease of reaction, and particularly to use ethylenediamine, adipic dihydrazide, hydrated hydrazine or water. Is particularly preferred.
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 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.

  Suitable solvents which are inert to the reaction and have a high affinity for water include, for example, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone and the like. The use amount of these solvents is preferably 3 to 200 parts by mass based on 100 parts by mass of the urethane prepolymer. When a solvent having a boiling point of 100 ° C. or less is used as these solvents, it is preferable to remove the solvent by distillation under reduced pressure after synthesizing the aqueous polyurethane resin.

上記式（１）中のＲ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して炭素数が２〜８のアルキル基、フェニル基又はベンジル基を表し、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４に含まれる芳香環の数は０又は１である。また、Ｘは塩素原子、臭素原子、又はヨウ素原子を表す。 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 , R ³ and R ⁴ in the above formula (1) each independently represent an alkyl group having 2 to 8 carbon atoms, a phenyl group or a benzyl group, and R ¹ , R ² , R ³ And the number of aromatic rings contained in R ⁴ is 0 or 1. X represents a chlorine atom, a bromine atom, or an iodine atom.

In order to improve the water solubility of the thermosetting aqueous polyurethane resin composition of the present invention and to enhance the antibacterial property of a leather material using the aqueous polyurethane resin, in the present invention, R ¹ in the above formula (1) is used. , R ² , R ^3, and R ⁴ are preferably an alkyl group having 2 to 7 carbon atoms, a phenyl group, or a benzyl group, and in particular, none of R ¹ , R ² , R ^3, and R ⁴ Alternatively, one is preferably a phenyl group or a benzyl group, and the remaining three or all of R ^{1 to} R ⁴ are preferably an alkyl group having 3 to 5 carbon atoms. When the number of carbon atoms in the alkyl group is 1, or when the number of phenyl groups and benzyl groups is more than 2, the compatibility with the aqueous polyurethane resin is deteriorated, and a high-quality aqueous polyurethane resin composition cannot be obtained. .
X in the general formula (1) is a chlorine atom, a bromine atom or an iodine atom. From the viewpoint of the heat-sensitive coagulation property of the obtained aqueous polyurethane resin composition, X is a chlorine atom or a bromine atom. Is preferred.

  From the viewpoint of the water resistance of the leather-like material obtained after drying, the amount of the heat-sensitive coagulant is preferably 5 to 20 parts by mass, and preferably 10 to 15 parts by mass with respect to 100 parts by mass of the aqueous polyurethane resin. Is more preferred. If the amount is less than 5 parts by mass, the water-based polyurethane resin does not coagulate at a low temperature, and if it exceeds 20 parts by mass, the water resistance of the leather-like material obtained after drying is significantly reduced.

Various commonly used additives can be added to the heat-coagulable water-based polyurethane resin composition of the present invention, if necessary, as long as the effects of the present invention are not impaired.
Specific examples of these additives include, for example, a crosslinking agent, various weathering agents (hindered amine-based light stabilizer, ultraviolet absorber and antioxidant), a silane coupling agent for particularly strengthening the adhesion to the substrate, and a colloidal agent. Inorganic colloid sol such as silica or colloidal alumina, tetraalkoxysilane and its condensation polymer, chelating agent, epoxy compound, pigment, dye, film forming aid, curing agent, external crosslinking agent, viscosity modifier, leveling agent, defoaming 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, wax, Fogging agents, antibacterial agents, fungicides, antiseptic agents, rust preventives and the like can be mentioned.

  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; Functional isocyanate compounds; blocked isocyanate compounds; polyfunctional aziridine compounds, and the like. Specific examples of these include oxazoline compounds, epoxy compounds, carbodiimide compounds, aziridine compounds, melamine compounds, and zinc complexes.

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; 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-third Butyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 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] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl 2- (2-hydroxyphenyl) such as benzotriazole 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-C 12 ~C ₁₃ 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-allylphen Ru) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1, 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-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- Benzoates such as di-tert-butyl-4-hydroxy) benzoate and behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 ' Substituted oxanilides such as -dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; Various metal salts or metal chelates, especially nickel or chromium salts or chelates, may be mentioned.

Examples of the antioxidant include a phosphorus-based, phenol-based or sulfur-based antioxidant. Examples of the phosphorus antioxidant 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-, di-mixed nonylphenyl) phosphite, diphenylacid phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octylphosphite Phyte, diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite , Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phyte, bis (2,5-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tetra (mixed alkyl of C ₁₂ alkyl to C ₁₅ alkyl) -4,4′-isopropylidene diphenyl phosphite, bis [2,2′-methylenebis ( 4,6-diami 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) biphenylenediphosphonite, tris (2-[(2,4,7,9-tetrakis 3-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-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] dioxaphospho N-6-yl) oxy] ethyl amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-tetrakis (1,1-dimethylethyl)] Dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl] oxy] propyl] phenol and 2-butyl-2-ethylpropanediol-2,4,6-tri-tert-butylphenol Monophosphite and the like can be mentioned.

  Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-di-tert-butyl-4-). (Hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-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] butylic 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-tris (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′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyl 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) p Pioneto], and tocopherol, and the like.

  Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, distearyl ester of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkylmercaptopropionates of polyols.

The amount of the weathering agent (hindered amine light stabilizer, ultraviolet absorber and antioxidant) used 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. In particular, it is more preferably 0.01 to 5 parts by mass. If the amount is less than 0.001 part by mass, a sufficient effect of addition may not be obtained. If the amount is more than 10 parts by mass, the water dispersion stability and the 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 polyol of a urethane raw material, a method of adding to a urethane prepolymer, a method of adding to a water phase at the time of aqueous 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.

  The leather-like material of the present invention can be obtained by heating or coagulating after applying or impregnating the heat-coagulable water-based polyurethane resin composition of the present invention to a fiber base material. The fibrous base material used for 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 a fabric in which a woven fabric or the like is laminated inside or on the surface for the purpose of reinforcement or the like, and the fiber material may be any of natural fibers and chemical fibers.

  Examples of natural fibers include cotton, wool, silk, and asbestos. Examples of the chemical fibers include recycled fibers such as rayon and Tencel, semi-synthetic fibers such as acetate and triacetate, polyamide fibers such as nylon, polyester fibers, polyolefin fibers, and acrylic fibers. Further, fibers obtained by mixing and using these may be used as appropriate. In the present invention, it is particularly preferable to use a polyamide fiber or a polyester fiber from the viewpoint that a feeling and quality close to those of natural leather can be obtained.

  The method for producing the leather-like material of the present invention is not particularly limited, and the heat-coagulable aqueous polyurethane resin composition of the present invention is applied or impregnated on the fiber base material by a commonly used method, and then the polyurethane resin composition Can be produced by heating to coagulate and drying in a dryer.

Examples of the application method include a method using knife coating, air knife coating, roll coating, spray coating, and the like.
In addition, as the impregnation method, for example, a method of impregnating a non-woven fabric with a heat-coagulable water-based polyurethane resin composition and squeezing with a press roll or the like, or by using a doctor knife or the like to obtain an appropriate amount of impregnation Is mentioned.
Thus, after applying the heat-coagulable water-based polyurethane resin composition of the present invention to the fiber base material or impregnating the same, the polyurethane resin composition is heat-coagulated and dried in a dryer to form a leather-like sheet. Obtainable.

  The heat-sensitive coagulation temperature of the resin needs to be from 40 to 90 ° C, preferably from 50 to 80 ° C, and particularly preferably from 55 to 75 ° C. In the case of a composition which heat-coagulates at a temperature lower than 40 ° C., the storage stability of the heat-coagulable water-based polyurethane resin composition is deteriorated. Migration of the resin composition is likely to occur, and the texture of the leather-like material is reduced.

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

  In the leather-like material of the present invention, the amount of the heat-coagulable water-based polyurethane resin composition adhered to the substrate is from 3 to 100 parts by mass of the fiber substrate after drying from the viewpoint of the coagulability of the polyurethane resin composition. It is preferably 100 parts by mass, more preferably 5 to 70 parts by mass, and particularly preferably 10 to 30 parts by mass. When the attached amount of the polyurethane resin composition is less than 3 parts by mass, the feeling of fulfillment of the resulting sheet tends to be insufficient, and the texture of the leather-like sheet tends to be insufficient. It tends to be hard and the texture of the leather worsens.

The leather-like material of the present invention can be used in the fields of vehicles, furniture, clothing, shoes, bags, bags, sandals, miscellaneous goods, etc., for example, automotive interior materials such as car seats, wall materials, mattresses, cushions It can be used for grounds, bag lining materials, sports shoes, men's shoes and the like.
The heat-coagulable water-based polyurethane resin composition of the present invention also includes, in addition to leather-like materials, paints, adhesives, surface modifiers, organic and / or inorganic powder binders, molded products, building materials, 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 lamination, film coating agents for agricultural use, thermal paper coating agents, binders for inkjet recording paper, printing for gravure Ink binder, paint for steel plate, paint for inorganic structural materials such as glass, slate, concrete, wood paint, fiber treatment agent, fiber coating agent, coating agent for electronic material parts, sponge, puff, glove, and condom And the like.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The percentages in the following Examples and the like are mass% unless otherwise specified.

[Production Example 1: Production of water-based polyurethane resin PUD-1]
<Production process of urethane prepolymer>
As a polyol, 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, and as a polyisocyanate, 221 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) ( 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. Then, the mixture was reacted at 85 to 95 ° C. for 2 hours under a nitrogen atmosphere, and it was confirmed that the isocyanate content (NCO%) was 3.1%, thereby obtaining a urethane prepolymer UP-1.

<Water dispersion / high molecular weight process>
To 560 g of water were added 0.1 g of an antifoaming agent (product name: Adecanol B-1016, manufactured by ADEKA Corporation) and 14.4 g (0.142 mol) of triethylamine, and 500 g of UP-1 was added, and 20 to After stirring at 40 ° C for 15 minutes, 18.0 g (0.075 mol of ethylenediamine) of a mixed solution having a mass ratio (ethylenediamine / water) of 1/3 was dropped as a chain extender, and the mixture was stirred at 20 to 40 ° C for 10 minutes. did. Further, as a chain extender, 52.4 g (0.075 mol of adipic dihydrazide) of a mixed solution having a mass ratio (adipic dihydrazide / water) of 1/3 was added, and NCO group was added at 20 to 40 ° C. for 1 to 2 hours. Stirring was continued until disappeared. Then, the methyl ethyl ketone solvent was distilled off to obtain an aqueous polyurethane resin PUD-1 having a solid content of 40%.

[Production Example 2: Production of aqueous polyurethane resin PUD-2]
<Production process of urethane prepolymer>
As the polyol, 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, and as a polyisocyanate, 294 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) ( 1.12 mol), 60 g (0.50 mol) of N-methyldiethanolamine, and 150 g of methyl ethyl ketone as a solvent. Then, the mixture was reacted at 85 to 95 ° C. for 3 hours in a nitrogen atmosphere. When it was confirmed that the isocyanate content (NCO%) was 4.2%, a urethane prepolymer UP-2 was obtained.

<Water dispersion / high molecular weight process>
0.1 g of an antifoaming agent (product name: Adecanol B-1016, manufactured by ADEKA Corporation) and 63.1 g (0.50 mol) of dimethyl sulfate were added to 500 g of water, and then 500 g of UP-2 was added. After stirring was continued at 20 to 40 ° C. for 1 to 2 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%.

[Production Example 3: Production of water-based polyurethane resin PUD-3]
<Production process of urethane prepolymer>
As a polyol, 268 g (0.268 mol) of a polyester polyol having a number average molecular weight of 1000 obtained by reacting neopentyl glycol and adipic acid, and 169 g of dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI) as a polyisocyanate ( 0.645 mol), 27.8 g (0.163 mol) of 1,4-butanediol-2-sulfonic 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 did. Then, the mixture was reacted at 85 to 95 ° C. for 2 hours in a nitrogen atmosphere. When it was confirmed that the isocyanate content (NCO%) was 2.4%, a urethane prepolymer UP-3 was obtained.

<Water dispersion / high molecular weight process>
To 538 g of water, 41.5 g of an emulsifier (product name: Adecapluronic L-64, manufactured by ADEKA Corporation) was added, and then 500 g of the above UP-3 was added. After stirring at 20 to 40 ° C. for 15 minutes, a chain extender was added. Then, 14.0 g (0.058 mol of ethylenediamine) of an aqueous solution having a mass ratio (ethylenediamine / water) of 1/3 was dropped, and the mixture was stirred at 20 to 40 ° C for 10 minutes.
Further, 40.0 g (0.057 mol of adipic dihydrazide) of a mixed solution having a mass ratio (adipic dihydrazide / water) of 1/3 was added as a chain extender, and 1% until the NCO group disappeared at 20 to 40 ° C. After stirring was continued for ２2 hours, the methyl ethyl ketone solvent was distilled off to obtain an aqueous polyurethane resin PUD-3 having a solid content of 40%.

[Production Example 4: Production of water-based polyurethane resin PUD-4]
<Production process of urethane prepolymer>
620.8 g (0.310 mol) of a polycarbonate polyol having a number average molecular weight of 2000 (manufactured by Asahi Kasei Chemicals Corporation, product name: Duranol S6002) and 120.5 g (0.543 mol) of isophorone diisocyanate (IPDI) as a polyisocyanate And 5.4 g (0.040 mol) of dimethylolpropionic acid as an anionic group-introducing agent, and reacted at 90 to 100 ° C. for 2 hours under a nitrogen atmosphere to obtain an isocyanate content (NCO%) of 2. After confirming that it was 2%, a urethane prepolymer UP-4 was obtained.

<Water dispersion / high molecular weight process>
To 337 g of water, 24.3 g of an emulsifier (product name: Adecapluronic F-108, manufactured by ADEKA Corporation) and 2.9 g (0.029 mol) of triethylamine were added, and then 485 g of UP-4 was added, followed by addition of 15 to 50. Stirred at 60 ° C. for 60 minutes. Next, after adding 65 g of water, 22.8 g (0.095 mol of ethylenediamine) of a mixed solution having a mass ratio (ethylenediamine / water) of 1/3 was added dropwise as a chain extender, and the NCO group disappeared at 20 to 40 ° C. The stirring was continued for 1 to 2 hours to obtain an aqueous polyurethane resin PUD-4 having a solid content of 55.0%.

[Production Example 5: Water-based polyurethane resin PUD-5]
<Production process of urethane prepolymer>
As the polyol, 310.4 g (0.155 mol) of a polycarbonate polyol having a number average molecular weight of 2,000 (manufactured by Asahi Kasei Chemicals Corporation, product name: Duranol S6002) and a polypropylene glycol having a number average molecular weight of 1,000 (manufactured by ADEKA Corporation, product name: ADEKA) 310.4 g (0.310 mol) of polyether P-1000, 175.7 g (0.791 mol) of isophorone diisocyanate (IPDI) as a polyisocyanate, and 5.8 g of dimethylolpropionic acid as an anionic group introducing agent ( 0.043 mol). Then, the mixture was reacted at 90 to 100 ° C. for 2 hours under a nitrogen atmosphere. When it was confirmed that the isocyanate content (NCO%) was 3.0%, a urethane prepolymer UP-5 was obtained.

<Water dispersion / high molecular weight process>
To 337 g of water were added 24.3 g of an emulsifier (product name: Adecapluronic F-108, manufactured by ADEKA Corporation) and 2.9 g (0.029 mol) of triethylamine, and then 485 g of the above UP-5 was added to the mixture. Stirred at 60 ° C. for 60 minutes. Next, 60 g of water is added, and 31.0 g (0.129 mol of ethylenediamine) of a mixed solution having a mass ratio (ethylenediamine / water) of 1/3 is dropped as a chain extender, and the NCO group disappears at 20 to 40 ° C. The stirring was continued for 1 to 2 hours to obtain an aqueous polyurethane resin PUD-5 having a solid content of 55.0%.

[Example 1-1: Production of aqueous polyurethane resin composition PUD-1-1]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 12.5 parts by mass of quaternary ammonium salt-1 were added to obtain an aqueous polyurethane resin composition PUD-1-1. The quaternary ammonium salt-1 is a quaternary ammonium salt in which R ¹ in the structural formula (1) is a benzyl group, R ^{2 to} R ⁴ are butyl groups, and X is a chlorine atom.

[Example 1-2: Production of water-based polyurethane resin composition PUD-1-2]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 12.5 parts by mass of quaternary ammonium salt-2 were added to obtain an aqueous polyurethane resin composition PUD-1-2. The quaternary ammonium salt-2 is a quaternary ammonium salt in which R ^{1 to} R ⁴ in the structural formula (1) are all ethyl groups and X is a chlorine atom.

[Example 1-3: Production of aqueous polyurethane resin composition PUD-3-1]
As shown in Table 1, 100 parts by mass of PUD-3 obtained in Production Example 3 and 12.5 parts by mass of quaternary ammonium salt-1 were added to obtain an aqueous polyurethane resin composition PUD-3-1.

[Example 1-4: Production of water-based polyurethane resin composition PUD-4-1]
As shown in Table 1, 100 parts by mass of PUD-4 obtained in Production Example 4 and 12.5 parts by mass of quaternary ammonium salt-1 were added to obtain an aqueous polyurethane resin composition PUD-4-1.

[Example 1-5: Production of aqueous polyurethane resin composition PUD-5-2]
As shown in Table 1, 100 parts by mass of PUD-5 obtained in Production Example 5 and 12.5 parts by mass of quaternary ammonium salt-2 were added to obtain an aqueous polyurethane resin composition PUD-5-2.

[Comparative Example 1-1: Production of water-based polyurethane resin composition PUD-1-3]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 12.5 parts by mass of quaternary ammonium salt-3 were added to obtain an aqueous polyurethane resin composition PUD-1-3. The quaternary ammonium salt-3 is a quaternary ammonium salt in which R ^{1 to} R ⁴ in the structural formula represented by the formula (1) are all methyl groups and X is a chlorine atom.

[Comparative Example 1-2: Production of aqueous polyurethane resin composition PUD-1-4 (1)]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 12.5 parts of quaternary ammonium salt-4 were added to obtain an aqueous polyurethane resin composition PUD-1-4 (1). Was. In the quaternary ammonium salt-4, R ¹ and R ² in the structural formula represented by the formula (1) are an ethyl group, R ³ is a methyl group, R ⁴ is a group represented by the following formula (2), and X Is a quaternary ammonium salt of a chlorine atom.

[Comparative Example 1-3: Production of water-based polyurethane resin composition PUD-1-4 (2)]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 25 parts by mass of quaternary ammonium salt-4 were added to obtain an aqueous polyurethane resin composition PUD-1-4 (2). .

[Comparative Example 1-4: Production of water-based polyurethane resin composition PUD-2-1]
As shown in Table 1, 100 parts by mass of PUD-2 obtained in Production Example 2 and 12.5 parts by mass of quaternary ammonium salt-1 were added to obtain an aqueous polyurethane resin composition PUD-2-1.

[Comparative Example 1-5: Production of water-based polyurethane resin composition PUD-1-6]
As shown in Table 1, 100 parts by mass of PUD-1 obtained in Production Example 1 and 1.3 parts by mass of a silver-based antibacterial agent were added to obtain an aqueous polyurethane resin composition PUD-1-6.

The storage stability and the heat-sensitive coagulation temperature of Examples 1-1 to 1-5 and Comparative examples 1-1 to 1-5 were evaluated. Table 1 shows the results.
The storage stability was evaluated by leaving the aqueous polyurethane resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 in an atmosphere at 30 ° C. for 3 months. The state of separation was visually evaluated.
: No separation was observed. △: Separation or sedimentation of resin was slightly observed. X: Separation or sedimentation of resin was observed. Thermal coagulation temperature was measured in a 100 ml beaker. Was gradually heated while stirring in a hot water bath at 95 ° C., and the temperature at which the aqueous resin solidified was measured.

  In Examples 1-2, 1-3, and 1-4 in Table 1, in the storage stability test, a slight separation of the aqueous polyurethane resin composition was observed. In Comparative Examples 1-2 and 1-3, the evaluations of storage stability and heat-sensitive coagulation temperature were good. In Comparative Examples 1-1 and 1-4, agglomerates were observed at the stage when the quaternary ammonium salt was added, so that a favorable aqueous polyurethane resin composition could not be obtained. Therefore, the evaluation of the heat-sensitive coagulation temperature and the production of the leather-like material described below were not performed.

[Examples 2-1 to 2-5: Production of leather-like material]
As shown in Table 2, the obtained aqueous polyurethane resin composition PUD-1-1, PUD-1-2, PUD-3-1, PUD-4-1 and PUD-5 were used for 100 parts by mass of the nonwoven fabric. After impregnating 200 parts by mass of each of -2, using a hot air drier, drying was performed at 100 ° C. for 5 minutes and at 150 ° C. for 3 minutes to obtain a leather-like material. Each of the obtained materials was evaluated for anti-migration properties, leather texture, and antibacterial properties.

[Comparative Examples 2-1 to 2-6: Production of leather-like material]
As shown in Table 2, the obtained aqueous polyurethane resin composition PUD-1-4 (1), PUD-1-4 (2), PUD-1-6, PUD-1, After 200 parts by mass of PUD-2 and PUD-3 were respectively impregnated, they were dried at 100 ° C. for 5 minutes and at 150 ° C. for 3 minutes using a hot air drier to obtain a leather-like material.

With respect to the leather-like materials obtained in each of the examples and comparative examples, anti-migration properties, texture, and antibacterial properties were evaluated. Table 2 shows the results. The methods for evaluating the anti-migration property, texture, and antibacterial property are as follows.
[Evaluation of migration prevention]
The cross section of each leather-like sheet was observed for migration using an electron microscope (JSM-6390LA, manufactured by JEOL Ltd.), and evaluated based on the following criteria.
: No migration 若干: Some migration occurred ×: Many migrations occurred

[Texture evaluation]
The softness of the leather-like sheet was observed by touch, and the texture was evaluated based on the following criteria.
：: Same flexibility as natural leather 柔軟 性: Slightly lower flexibility than natural leather ×: Flexibility significantly lower than natural leather

[Antibacterial evaluation]
The evaluation of antibacterial properties was carried out in accordance with JIS Z2801 "Antibacterial processed product-Antibacterial test method and antibacterial effect". Staphylococcus aureus and Escherichia coli were used as test bacteria.
A predetermined number of the above two types of bacteria were inoculated on the leather-like materials obtained in the examples and comparative examples, and the number of bacteria (Y ₁ ) was measured after culturing for 24 hours at 35 ° C. and 90% RH. . As a blank, a nonwoven fabric not impregnated with the aqueous polyurethane resin composition was used, and the number of bacteria (Y ₀ ) after culturing for 24 hours was measured in the same manner. From these values, the antibacterial activity value (the average value of n = 3) was determined using the following formula (3), and those having an antibacterial activity value exceeding 2.0 were evaluated as having antibacterial properties.
Antibacterial activity value = logY ₀ −logY ₁ (3)

  From the results of Example 2 and Comparative Example 2, Comparative Examples 2-1 and 2-2 using the quaternary ammonium salts that do not satisfy the requirement of the general formula (1) (Comparative Examples 1-2 and 1) In the case of using each of the water-based polyurethane compositions having a favorable evaluation of -3), it was confirmed that the anti-migration property and the texture of the leather were good, but the antibacterial properties were not exhibited. In Comparative Example 2-3 containing a silver-based antibacterial agent, the evaluation of antibacterial properties was good, but the evaluation of anti-migration properties and leather texture was extremely poor. In Comparative Examples 2-4 to 2-6, all of the evaluations of the anti-migration property, the texture of the leather, and the antibacterial property were remarkably inferior. In contrast, it was confirmed that the heat-coagulable water-based polyurethane resin composition of the present invention was excellent in heat-coagulability and exhibited good results in all of the properties as a leather-like material.

The heat-coagulable water-based polyurethane resin composition of the present invention has excellent storage stability and can be used not only for various resin products and paints, but also for a sheet material obtained by heat-coagulating this resin composition. Since it becomes a leather-like material having excellent physical properties, it is suitable for vehicle interiors, furniture, clothing, shoes, bags, bags, sandals, miscellaneous goods, and the like, and is extremely useful in industry.

Claims (6)

A thermosetting water-soluble polyurethane resin composition comprising (A) a polyurethane resin having at least one kind of anionic group selected from a carboxyl group and a sulfonic acid group in a molecule, and (B) a thermosetting 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-coagulable water-based polyurethane resin composition, characterized by being compounded;

R ¹ , R ² , R ³ and R ⁴ in the above formula (1) each independently represent an alkyl group having 2 to 8 carbon atoms, a phenyl group or a benzyl group, and R ¹ , R ² , R ³ And the number of aromatic rings contained in R ⁴ is 0 or 1, and X represents any one of a chlorine atom, a bromine atom and an iodine atom.   The component (A) is a component starting from a urethane prepolymer obtained by reacting a polyol, a polyisocyanate and an anionic group-introducing agent, wherein the polyol, polyisocyanate and anionic introducing agent are a polyol and an anionic agent. The heat-coagulable aqueous system according to claim 1, wherein NCO / OH, which is the ratio of the total isocyanate group equivalent of the polyisocyanate to the total hydroxyl group equivalent of the group-introducing agent, is 1.1 to 2.5. Polyurethane resin composition.   The heat-coagulable water-based polyurethane resin composition according to claim 1 or 2, wherein the urethane prepolymer has an acid value of 5 to 50 mgKOH / g.   The heat-coagulable water-based polyurethane resin according to any one of claims 1 to 3, further comprising 0.2 to 2.0 equivalents of the anionic group neutralizer (C) based on 1 equivalent of the anionic group. Composition.   The thermosetting aqueous polyurethane resin composition according to any one of claims 1 to 4, 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).   A method for producing a leather-like material, comprising heating or coagulating a fiber base material after applying or impregnating the heat-sensitive coagulable aqueous polyurethane resin composition according to any one of claims 1 to 5. .