JP6114079B2 - Method for producing leather material and leather material - Google Patents

Description

  The present invention relates to a method for manufacturing a leather material and a leather material. More specifically, the present invention relates to a method for manufacturing a leather material that can be suitably used as artificial leather or synthetic leather by using an aqueous polyurethane resin.

  Conventionally, as an alternative to natural leather, there are many artificial leathers composed of polyurethane resin and non-woven fiber substrate, and synthetic leather composed of polyurethane resin and woven or knitted fiber substrate. Kinds have been manufactured. Such artificial leather and synthetic leather, for example, those obtained by impregnating or coating a fiber base material with an organic solvent solution of a polyurethane resin are poor solvents for the polyurethane resin and are compatible with the organic solvent. It has been produced by a method called a wet coagulation method in which it is solidified by passing it through a coagulation liquid (usually water), then washed with water and dried.

  However, organic solvents such as dimethylformamide, which are often used in such wet coagulation methods, are highly flammable and highly toxic. There were also concerns about environmental pollution such as air and water quality. In addition, in order to solve such problems, a manufacturing method incorporating a process for recovering the generated organic solvent has been implemented, but there remains a problem that a large amount of disposal cost and labor are required. Furthermore, in artificial leather and synthetic leather obtained by using an organic solvent solution of polyurethane resin, the organic solvent remains in the leather, so that the influence on the human body such as skin damage has been a problem. Therefore, studies have been made to shift the polyurethane resin fixed to the fiber base material from an organic solvent type to an aqueous polyurethane resin.

  The manufacturing method of artificial leather using water-based polyurethane resin does not use organic solvent, so the cost required for recovery can be eliminated, and improvement of working environment, air pollution, water pollution, etc. Is excellent. However, artificial leather and the like using a water-based polyurethane resin have a problem that texture and physical properties are inferior compared with artificial leather and synthetic leather obtained using a conventional organic solvent solution. Also, in the step of dry drying after impregnating the inside of the fiber base material with the aqueous polyurethane resin, the aqueous polyurethane resin moves to the fiber base material surface following the movement of water evaporated from the fiber base material surface. There was also a problem that so-called migration occurred.

  For this reason, in methods for producing artificial leather and the like using an aqueous polyurethane resin, studies have been made to improve the texture and physical properties and prevent migration. For example, in Japanese Patent Application Laid-Open No. 52-28904 (Patent Document 1), a synthetic resin emulsion to which a heat-sensitive gelling agent is added to impart heat-sensitive coagulation property is impregnated into a fiber base material, and the synthetic resin emulsion is added in hot water. A method for producing a leather-like product for coagulating a material is disclosed.

  However, in such a method, although the migration prevention property is improved to some extent, a part of the impregnating liquid flows out into the bath and solidifies, and the solidified gel is reattached to the surface of the workpiece. There was a problem that the appearance and texture of the leather material deteriorated. Further, in such a method, when the heat-sensitive coagulation property decreases as the polyurethane resin concentration decreases, a part of the impregnating liquid easily flows out into the hot water, and the appearance and texture of the obtained leather material further deteriorates. It also had the problem of end up.

  Further, in JP-A-6-316877 (Patent Document 2), a treatment liquid prepared by dissolving inorganic salts in a forcedly emulsified nonionic polyurethane emulsion is applied to a fiber substrate such as a nonwoven sheet. A method for producing heat-dried artificial leather is disclosed. However, in such a method, although the migration prevention property is improved to some extent, there is a processing problem that the stability of the treatment bath is deteriorated depending on the concentration of the inorganic salt to be blended. Moreover, since emulsifiers and inorganic salts such as nonionic surfactants remain in the fiber base material, the obtained leather material has a rough texture, and the fastness to friction is not sufficient.

  In JP-A-2000-290879 (Patent Document 3), a fiber base material is impregnated with an aqueous resin composition comprising an aqueous urethane resin having a thermal coagulation temperature of 40 to 90 ° C. and an associative thickener. Or the manufacturing method of the fiber sheet-like composite material which apply | coats and heat-coagulates this aqueous resin composition with steam is disclosed. However, even with such a method, although the migration prevention property is improved to some extent, the non-ionic surfactant (nonionic emulsifier) and the associative thickener remain in the fiber base material, so that the obtained leather material still has a texture. However, it was coarse and the friction fastness was not sufficient.

  Further, in Japanese Patent Application Laid-Open No. 2003-138131 (Patent Document 4), a carboxylate type polyurethane resin containing a nonionic surfactant (nonionic surfactant) of HLB 10-18 and an inorganic salt is imparted to a fiber base material. A method for producing a leather sheet material obtained by heat-coagulation is disclosed. However, even in such a method, problems with surfactants and inorganic salts occur as in the methods described in Patent Documents 2 and 3, and the obtained leather material is still rough and has sufficient friction fastness. It was not a thing.

  In the methods described in Patent Documents 2 to 4, residues such as nonionic surfactants, inorganic salts, and associative thickeners can be removed to some extent by repeating the steps of washing with water or washing with hot water. However, the above problem is unavoidable because it is difficult to remove completely. In addition, repeated steps such as water washing or hot water washing increase the number of processing steps and lead to an economic problem. Accordingly, there is a demand for a production method that can reduce the number of steps of washing with water or hot water as much as possible, easily remove the residue, and obtain a leather material having sufficient texture and friction fastness.

  In JP-A-2006-36960 (Patent Document 5), a leather material is produced by impregnating a fiber substrate with a mixed solution containing a carboxy group-containing polyurethane resin, an ammonium salt of carboxylic acid and water, and then drying the mixture. A method is disclosed.

  However, although such a method can solve the migration problem, a new problem has arisen in that an odor due to ammonia gas is generated during drying. Further, when an ammonium salt of a carboxylic acid having a small carbon number such as ammonium formate or ammonium acetate is used as the ammonium carboxylate, there has been a problem that the apparatus is corroded by the carboxylic acid that volatilizes by heating and drying. On the other hand, when an ammonium salt of a carboxylic acid having a large number of carbon atoms is used, volatilization of the carboxylic acid during heating and drying is suppressed, but a large amount of ammonium salt of carboxylic acid is used to obtain the desired migration prevention property. Need to be used. Furthermore, when a polycarbodiimide compound is used in combination for the purpose of improving durability such as heat resistance of the resin, it reacts with the ammonium salt of the carboxylic acid, so that it is sufficient to use a large amount of the ammonium salt of the carboxylic acid. It tends to be difficult to obtain migration prevention.

  In JP-A-2002-249985 (Patent Document 6), an aqueous thermoplastic binder solution such as polyurethane resin, an inorganic compound, a water-soluble organic polymer, a poorly water-soluble organic polymer, and a high cloud point surfactant are used. A method for producing a porous structure is disclosed in which a mixed liquid in combination with at least one selected from the group consisting of is applied to a substrate and dried after wet heat heating with steam, etc., according to such a method, It is possible to express the texture of natural leather. However, even in the porous structure obtained by the method described in Patent Document 6, the texture and the migration prevention property are still not sufficient.

Japanese Patent Laid-Open No. 52-28904 JP-A-6-316877 JP 2000-290879 A JP 2003-138131 A JP 2006-36960 A JP 2002-249985 A

  Furthermore, as a result of investigations by the present inventors, it has been found that the thickness retention rate of the fiber base material tends to be low when the migration preventing property is insufficient in the conventional leather material.

  The present invention has been made in view of the above-described problems of the prior art, and is a method for manufacturing a leather material using a water-based polyurethane resin in consideration of environmental load and VOC problems, migration is suppressed, and A method for producing a leather material capable of efficiently and surely obtaining a leather material having excellent friction fastness while maintaining the thickness of the fiber base material without causing odor at a suitable coagulation temperature, and its production method It aims at providing the material for leather obtained.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a specific aqueous polyurethane resin and at least one inorganic acid ammonium salt selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride, By impregnating the fiber base material with a mixed liquid containing a specific nonionic surfactant and water, and then drying, the aqueous polyurethane resin does not migrate and become unevenly distributed during drying. It was found that a polyurethane resin can be uniformly fixed to the inside, the thickness of the fiber base material is maintained, and a leather material having sufficient friction fastness can be obtained. In addition, the present inventors have a heat-sensitive coagulation temperature of such a mixture within a suitable range (preferably 30 to 90 ° C.) and can coagulate even at a relatively low coagulation temperature (drying temperature). Therefore, it has been found that the leather material can be obtained efficiently and reliably within the range of a suitable solidification temperature (drying temperature). Furthermore, according to such a method, generation | occurrence | production of the odor by ammonia gas and corrosion of the apparatus by carboxylic acid were discovered, and it came to complete this invention.

That is, the first method for producing a leather material of the present invention comprises (A) an aqueous polyurethane resin having an anionic group, (B) at least one inorganic acid selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride. Ammonium salt, (D) a nonionic surfactant having a weight average molecular weight of 2,000 to 10,000,000 and containing 75% by mass or more of oxyalkylene groups in the molecule, and (E) a mixed solution containing water Is impregnated into a fiber base material and dried to obtain a leather material , and
The (A) aqueous polyurethane resin has the following conditions (i) to (ii):
(I) It has a carboxyl group and / or a carboxylate group, and the total content of the carboxyl group and the carboxylate group is 0.5 to 4.0% by mass,
(Ii) It has a sulfo group and / or a sulfonate group, and the total content of the sulfo group and the sulfonate group is 0.1 to 1.0% by mass,
A polyurethane resin satisfying at least one of
It is characterized by.

As a mixed liquid according to the first method for producing a leather material of the present invention , a mixing ratio of the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, and the (D) nonionic surfactant ( A: B: D) is preferably 100: 0.1 to 50: 2 to 100 in terms of mass ratio.

Further, the second method for producing a leather material of the present invention includes (A) an aqueous polyurethane resin having an anionic group, (B) at least one inorganic acid selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride. Ammonium salt, (D) a nonionic surfactant having a weight average molecular weight of 2,000 to 10,000,000 and containing 75% by mass or more of oxyalkylene groups in the molecule, and (E) a mixed solution containing water Is impregnated into a fiber base material and then dried to obtain a leather material, and the mixed solution further contains (C) a water-soluble organic polymer . As the mixed solution , a blending ratio (A) of the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, the (C) water-soluble organic polymer, and the (D) nonionic surfactant is used. : B: C: D) is 100 weight ratio: 0.1-50: 0.1-50: it is good preferable is 2-100. Further, the (C) water-soluble organic polymer is preferably at least one selected from the group consisting of hydroxyethyl cellulose, xanthan gum and sodium alginate.

Further , the (A) aqueous polyurethane resin according to the second method for producing a leather material of the present invention has at least one anionic group selected from the group consisting of a carboxy group, a carboxylate group, a sulfo group, and a sulfonate group. It is preferable that it is a polyurethane resin having the following conditions (i) to (ii):
(I) It has a carboxyl group and / or a carboxylate group, and the total content of the carboxyl group and the carboxylate group is 0.5 to 4.0% by mass,
(Ii) It has a sulfo group and / or a sulfonate group, and the total content of the sulfo group and the sulfonate group is 0.1 to 1.0% by mass,
It is preferable that it is a polyurethane resin which satisfy | fills at least any one of these.

Furthermore, as the (A) aqueous polyurethane resin according to the present invention,
(I) (a) Organic polyisocyanate, (b) polyol and (c) neutralized isocyanate group-terminated prepolymer having a carboxylate group obtained by reacting a compound having a carboxy group and two or more active hydrogens Having a carboxy group and / or a carboxylate group obtained by emulsifying and dispersing in water by self-emulsification and (d) a chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin, and
(II) (a) organic polyisocyanate, (b) polyol and (e) sulfonate group obtained by reacting two or more amino groups and / or imino groups with a polyamine compound having a sulfo group and / or a sulfonate group It was obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer neutralized product having water in water by self-emulsification and (d) a chain extension reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin having sulfo group and / or sulfonate group,
It is preferably at least one polyurethane resin selected from the group consisting of

  Moreover, as a liquid mixture which concerns on this invention, it is preferable that a thermosensitive coagulation temperature is 30-80 degreeC. Furthermore, in the production method of the present invention, the mixed solution is applied to the fiber base material so that the component derived from the water-based polyurethane resin (A) is fixed up to 10% of the central portion in the thickness of the leather material. It is preferable to impregnate.

The (D) nonionic surfactant according to the present invention may be at least one selected from the group consisting of an addition polymer of alkylene oxide having 2 to 4 carbon atoms and an alkylene oxide adduct of glycerin. Is preferred .

  According to the present invention, a method for manufacturing a leather material using an aqueous polyurethane resin in consideration of environmental load and VOC problems, migration is suppressed, the thickness of a fiber base material is maintained, and friction fastness is also achieved. It is possible to provide a method for producing a leather material capable of obtaining an excellent leather material efficiently and reliably at a suitable coagulation temperature without generating an odor, and a leather material obtained by the production method.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The method for producing a leather material of the present invention comprises (A) an aqueous polyurethane resin having an anionic group, (B) at least one inorganic acid ammonium salt selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride, (D A nonionic surfactant having a weight average molecular weight of 2,000 to 10,000,000 and containing 75% by mass or more of oxyalkylene groups in the molecule, and (E) a mixed solution containing water, After being impregnated, the leather material is dried to obtain a leather material.

(A) Aqueous polyurethane resin The aqueous polyurethane resin according to the present invention is an aqueous polyurethane resin having an anionic group in the resin skeleton. In the present invention, the water-based polyurethane resin refers to a polyurethane resin in which separation or sedimentation is not observed even when an aqueous emulsion dispersion having a polyurethane resin concentration in water of 40% by mass is left at 20 ° C. for 12 hours.

  Examples of the anionic group include a carboxy group, a carboxylate group, a sulfo group, and a sulfonate group. The aqueous polyurethane resin according to the present invention has at least one anionic group selected from the group consisting of a carboxy group, a carboxylate group, a sulfo group, and a sulfonate group from the viewpoint that emulsion dispersion stability tends to be excellent. It is preferably a polyurethane resin, more preferably a polyurethane resin having a carboxy group and a carboxylate group, or a polyurethane resin having a sulfo group and a sulfonate group. In addition, as the aqueous polyurethane resin according to the present invention, one kind may be used alone, or two or more kinds may be used in combination.

  The anionic group content in the aqueous polyurethane resin according to the present invention is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 2.5% by mass. Moreover, (i) When the aqueous polyurethane resin which concerns on this invention has a carboxyl group and / or a carboxylate group, the total content of a carboxyl group and a carboxylate group is 0.5-4.0 mass%. Is more preferable, and it is still more preferable that it is 0.7-2.5 mass%. Furthermore, (ii) when the aqueous polyurethane resin according to the present invention has a sulfo group and / or a sulfonate group, the total content of the sulfo group and the sulfonate group is further 0.1 to 1.0% by mass. Preferably, it is more preferable that it is 0.2-1.0 mass%. (Iii) When the aqueous polyurethane resin according to the present invention has a carboxy group and / or a carboxylate group, and a sulfo group and / or a sulfonate group, the total content of the carboxyl group and the carboxylate group is 0.00. It is particularly preferably 1 to 4.0% by mass and the total content of sulfo group and sulfonate group is 0.1 to 1.0% by mass.

  When the content of the anionic group is less than the lower limit, the storage stability of the aqueous polyurethane resin tends to be deteriorated. On the other hand, when the content exceeds the upper limit, the thermal coagulation temperature of the resulting mixture is high. Thus, the migration prevention effect of the leather material tends to decrease.

  In the present invention, the 100% modulus value of the aqueous polyurethane resin is preferably 0.5 to 25 MPa, and more preferably 1 to 20 MPa. When the value of the 100% modulus is less than the lower limit, a leather material with a soft texture can be obtained, but the wear resistance tends to be lowered. On the other hand, when the upper limit is exceeded, it is obtained. There is a tendency that the texture of the leather material becomes stiff, and fuzzing and fiber dropout are likely to occur. In the present invention, the value of 100% modulus was measured using a dumbbell-shaped No. 3 test piece as in JIS K 6251 (2010), and the distance between the marked lines was increased by 100% (doubled). A predetermined elongation tensile stress (MPa).

As such an aqueous polyurethane resin,
(I) (a) Organic polyisocyanate, (b) polyol and (c) neutralized isocyanate group-terminated prepolymer having a carboxylate group obtained by reacting a compound having a carboxy group and two or more active hydrogens Having a carboxy group and / or a carboxylate group obtained by emulsifying and dispersing in water by self-emulsification and (d) a chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin, and
(II) (a) organic polyisocyanate, (b) polyol and (e) sulfonate group obtained by reacting two or more amino groups and / or imino groups with a polyamine compound having a sulfo group and / or a sulfonate group It was obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer neutralized product having water in water by self-emulsification and (d) a chain extension reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin having sulfo group and / or sulfonate group,
Can be suitably used. Hereinafter, as a method for producing an aqueous polyurethane resin according to the present invention, these resins will be described as examples.

(I) Polyurethane resin having a carboxy group and / or a carboxylate group (a) Organic polyisocyanate The organic polyisocyanate is not particularly limited, and is an aliphatic polyisocyanate or alicyclic polyisocyanate having two or more isocyanate groups. And aromatic polyisocyanates can be used. Examples of such organic polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanato). And cycloaliphatic diisocyanate compounds such as methyl) cyclohexane; aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

  Among such organic polyisocyanates, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds can be suitably used because they impart a non-yellowing property to leather materials. In particular, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane. Diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be preferably used.

(B) Polyol The polyol is not particularly limited as long as it has two or more hydroxyl groups. In addition to polyester polyol, polycarbonate polyol, polyether polyol, etc., a polyether ester polyol having an ether bond and an ester bond. Silicone polyols and fluorine polyols can also be used.

  Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, and polybutylene sebacate. Diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol, adipic acid and dimer acid And polycondensates of nonanediol and dimer acid, ethylene glycol, adipic acid and dimer acid, and the like.

  Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, and 1,6-hexanediol polycarbonate polyol.

  Examples of the polyether polyol include a diol that is a homoaddition polymer or a coaddition polymer of an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, and tetramethylene oxide; And a polyol in which the alkylene oxide having 2 to 4 carbon atoms is randomly or block-added to a polyhydric alcohol such as trimethylolpropane.

  Examples of the silicone polyol include those in which two or more hydroxy groups and / or organic groups having a hydroxy group are introduced into the terminal and / or side chain of dimethylpolysiloxane. For example, carbinol-modified silicone oil, polyether Examples thereof include modified silicone oil and silanol-terminated silicone oil.

  Examples of the fluorine polyol include polyols containing fluorine in the molecule, and examples thereof include Zeffle GK510, GK570 (manufactured by Daikin Industries, Ltd.), Lumiflon LF200, LF400 (manufactured by Asahi Glass Co., Ltd.). .

  These polyols may be used alone or in combination of two or more. Moreover, as a weight average molecular weight of such a polyol, it is preferable that it is 500-5,000, and it is more preferable that it is 1,000-3,000. In addition, from the viewpoint that the obtained polyurethane resin can impart sufficient durability to the leather material, it is preferable to use polycarbonate polyol and / or polyether polyol as the polyol. Moreover, it is preferable to use a silicone polyol and / or a fluorine polyol from a viewpoint that the texture of the obtained leather material tends to be further improved.

(C) Compound having a carboxy group and two or more active hydrogens Examples of the compound having a carboxy group and two or more active hydrogens include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutane. Examples include acids. Furthermore, as such a compound, a polyester polyol having a pendant carboxy group obtained by reacting a diol having a carboxy group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or the like can also be used. Moreover, the compound which has such a carboxy group and two or more active hydrogens may be used individually by 1 type, or may be used in combination of 2 or more type.

(D) Polyamine compounds having two or more amino groups and / or imino groups Examples of polyamine compounds having two or more amino groups and / or imino groups include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, and diamino. Diamines such as cyclohexylmethane, piperazine, hydrazine, 2-methylpiperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine, xylylenediamine; Polyamines such as 2-aminoethyl) amine; amidoamines derived from diprimary amines and monocarboxylic acids; water-soluble amines such as monoketimines of diprimary amines Mine derivatives; oxalic acid dihydrazide, malonic acid dihydrazide, oxalic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1′-ethylenehydrazine, 1,1 ′ -Hydrazine derivatives such as trimethylenehydrazine and 1,1 '-(1,4-butylene) dihydrazine. These polyamine compounds having two or more amino groups and / or imino groups may be used singly or in combination of two or more.

  The (I) polyurethane resin having a carboxyl group and / or a carboxylate group is a neutralized product of an isocyanate group-terminated prepolymer having a carboxylate group (hereinafter sometimes referred to as “CA isocyanate group-terminated prepolymer neutralized product”). It can be obtained as an emulsified dispersion of the polyurethane resin by emulsification and dispersion in water by self-emulsification and chain elongation reaction.

The CA isocyanate group-terminated prepolymer neutralized product is an isocyanate having a carboxylate group (—COO ⁻ ) in which a carboxy group derived from the compound (c) having a carboxy group and two or more active hydrogens is neutralized. It is a group-terminal prepolymer neutralized product, and is obtained by reacting (a) organic polyisocyanate, (b) polyol and (c) a compound having a carboxy group and two or more active hydrogens.

  A specific method for obtaining such a CA isocyanate group-terminated prepolymer neutralized product is not particularly limited, and for example, by a conventionally known one-stage so-called one-shot method, multi-stage isocyanate polyaddition reaction method, or the like. Can be manufactured. The reaction temperature at this time is preferably 40 to 150 ° C.

  In such a reaction, a low molecular weight chain extender having two or more active hydrogen atoms can be used as necessary. The low molecular weight chain extender preferably has a molecular weight of 400 or less, particularly preferably 300 or less. Examples of the low molecular weight chain extender include, for example, low molecular weight high molecular weights such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Examples thereof include low-molecular weight polyamines such as ethylene diamine, propylene diamine, hexamethylene diamine, diaminocyclohexyl methane, piperazine, 2-methylpiperazine, isophorone diamine, diethylene triamine, and triethylene tetramine. Further, as the low molecular weight chain extender, one kind may be used alone, or two or more kinds may be used in combination.

  Furthermore, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, or N-methylmorpholine may be added as necessary during the reaction. Can do. Moreover, the organic solvent which does not react with an isocyanate group can be added at the time of reaction or after completion | finish of reaction. Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, and methyl isobutyl ketone.

  The neutralization of the carboxy group derived from the compound (c) having a carboxy group and two or more active hydrogens may be performed simultaneously with the preparation of the isocyanate group-terminated prepolymer, or before or after the preparation. It may be. Such neutralization can be appropriately performed using a known method, and the compound used for such neutralization is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, and tributylamine. , N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, N, N-diethylmonoethanolamine, amines such as triethanolamine; potassium hydroxide; sodium hydroxide; ammonia and the like. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.

  There is no restriction | limiting in particular in the emulsification dispersion | distribution method in water of the said CA isocyanate group terminal prepolymer neutralized material, For example, the method using emulsification apparatuses, such as a homomixer, a homogenizer, and a disper, can be mentioned. In addition, when the CA isocyanate group-terminated prepolymer neutralized product is emulsified and dispersed in water, the prepolymer neutralized product is emulsified in water by self-emulsification in the temperature range of room temperature to 40 ° C. without using an emulsifier. It is preferable to disperse and suppress the reaction between the isocyanate group and water as much as possible. Furthermore, when emulsifying and dispersing in this way, reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, benzoyl chloride are added as necessary. be able to.

  In the chain elongation reaction of the neutralized product of CA isocyanate group-terminated prepolymer, is the (d) polyamine compound having two or more amino groups and / or imino groups added to the neutralized product of CA isocyanate group-terminated prepolymer? Alternatively, it can be carried out by adding the neutralized product of the CA isocyanate group-terminated prepolymer to the polyamine compound having two or more amino groups and / or imino groups (d). Such a chain extension reaction is preferably performed at a reaction temperature of 20 to 40 ° C., and is usually completed in 30 to 120 minutes.

  In the method for producing a polyurethane resin having (I) a carboxyl group and / or a carboxylate group, the emulsification dispersion and the chain extension reaction may be performed simultaneously, and the CA isocyanate group-terminated prepolymer neutralized product is emulsified. The chain extension reaction may be performed after the dispersion, or the emulsion may be dispersed after the chain extension reaction. Moreover, when the above-mentioned organic solvent is used when producing the neutralized product of CA isocyanate group-terminated prepolymer, it is preferable to remove the organic solvent by, for example, vacuum distillation after the chain extension reaction or emulsification dispersion.

(II) Polyurethane resin having sulfo group and / or sulfonate group (II) (a) Organic polyisocyanate, (b) polyol and (d) amino group used for production of polyurethane resin having sulfo group and / or sulfonate group Examples of the polyamine compound having two or more imino groups include the same as those described in the production of the polyurethane resin having (I) carboxy group and / or carboxylate group.

(E) Polyamine compound having two or more amino groups and / or imino groups and a sulfo group and / or sulfonate group Polyamine having two or more amino groups and / or imino groups and a sulfo group and / or sulfonate group The compound may have at least two amino groups and / or imino groups and may have a sulfo group and / or a sulfonate group. For example, 2- (2-aminoethylamino) -ethane Examples include sodium sulfonate, sodium 2- (3-aminopropylamino) -ethanesulfonate, sodium 2,4-diaminobenzenesulfonate, and the like. These compounds may be used alone or in combination of two or more.

  The polyurethane resin having (II) sulfonate group and / or sulfonate group is a self-polymerization of a neutralized product of an isocyanate group-terminated prepolymer having a sulfonate group (hereinafter sometimes referred to as “SU isocyanate group-terminated prepolymer neutralized product”). It can be obtained as an emulsified dispersion of the polyurethane resin by emulsification dispersion in water by emulsification and a chain elongation reaction.

In the SU isocyanate group-terminated prepolymer neutralized product, the (e) sulfo group derived from a polyamine compound having two or more amino groups and / or imino groups and a sulfo group and / or a sulfonate group was neutralized. It is an isocyanate group-terminated prepolymer neutralized product having a sulfonate group (—SO ₃ ⁻ ), and includes (a) an organic polyisocyanate, (b) a polyol, and (e) two or more amino groups and / or imino groups. And a polyamine compound having a sulfo group and / or a sulfonate group.

  A specific method for obtaining such a SU isocyanate group-terminated prepolymer neutralized product is not particularly limited, and instead of (c) the compound having a carboxy group and two or more active hydrogens (e) Except for using a polyamine compound having two or more amino groups and / or imino groups and a sulfo group and / or sulfonate group, it is the same as the neutralized prepolymer of CA isocyanate group. The method of obtaining the polyurethane resin having the sulfo group and / or the sulfonate group by emulsifying dispersion and chain extension reaction of the SU isocyanate group-terminated prepolymer neutralized product is also included in the CA isocyanate group-terminated prepolymer neutralization. It is as having described in the manufacturing method of the polyurethane resin which has the said (I) carboxy group and / or carboxylate group except using the said SU isocyanate group terminal prepolymer neutralized material instead of a thing.

  The aqueous polyurethane resin is usually obtained as a water-emulsified dispersion of resin and is distributed in the market. The aqueous polyurethane resin according to the present invention is preferably used in a state of being emulsified and dispersed in water, and the concentration is not particularly limited, but the mixed liquid according to the present invention can be easily obtained in a uniform state. In view of the tendency, and considering the amount of the resin component fixed to the fiber base material, it is preferably 15 to 60% by mass. In the present invention, when the water-based polyurethane resin is used in a state of being emulsified and dispersed in water, the mass of the water-based polyurethane resin means that the water-based emulsion dispersion of the water-based polyurethane resin is heated at a temperature of 105 ° C. for 3 hours. The remainder (non-volatile content).

(B) Inorganic acid ammonium salt The inorganic acid ammonium salt according to the present invention is at least one selected from the group consisting of ammonium sulfate, ammonium phosphate, and ammonium chloride, and one of these may be used alone. Two or more kinds may be used in combination. In the present invention, examples of the ammonium phosphate include triammonium phosphate ((NH ₄ ) ₃ PO ₄ ), di-ammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), and ammonium dihydrogen phosphate ((NH ₄ )). H ₂ PO ₄ ). As these inorganic acid ammonium salts, one kind may be used alone or two or more kinds may be used in combination. However, when ammonium dihydrogen phosphate is used as the inorganic acid ammonium salt according to the present invention, phosphorus It is preferable to use in combination with diammonium hydrogen phosphate from the viewpoint that when the ammonium dihydrogen acid is used alone, the mixed solution tends to be gelled before heating.

  In the present invention, the inorganic acid ammonium salt may be used as it is in a solid (powder) state, but from the viewpoint of maintaining the stability of the emulsion dispersion of the (A) aqueous polyurethane resin, It is preferable that an ammonium salt is contained in water and used in the form of an aqueous solution. As a density | concentration of the aqueous solution of the said inorganic acid ammonium salt, it is preferable that it is 1-50 mass%, and it is more preferable that it is 10-30 mass%. When the concentration is less than the lower limit, a large amount of the aqueous solution is required to exhibit the migration-preventing property at the time of drying, and accordingly, the concentration of the (A) aqueous polyurethane resin in the mixed solution decreases. become. Therefore, a large amount of liquid mixture is required to obtain the target leather material, so that the amount of water to be volatilized increases, the drying time becomes longer, and the economy tends to decrease. However, this problem is a heat-sensitive gelling formulation in which the mixed liquid according to the present invention senses heat and the resin gels, and the method of the present invention tends to be improved by being a method with high production efficiency. is there. On the other hand, when the concentration exceeds the upper limit, the stability of the emulsified dispersion tends to be impaired, for example, a precipitate is generated when the (A) aqueous polyurethane resin is mixed with the emulsified dispersion.

(C) Water-soluble organic polymer The mixed solution according to the present invention preferably further contains (C) a water-soluble organic polymer. By further containing the water-soluble organic polymer (C), it is possible to obtain a leather material that is further suppressed in migration and excellent in friction fastness. Moreover, when the present inventors examined, in the case of the conventional leather material, the thickness retention of the fiber base material tends to be low even when the texture is insufficient. It was found that by further containing a water-soluble organic polymer, the thickness of the fiber base material can be maintained and a leather material with a soft texture can be obtained.

  Examples of the water-soluble organic polymer include natural water-soluble organic polymers, semi-synthetic water-soluble organic polymers, and synthetic water-soluble organic polymers. In the present invention, the water-soluble organic polymer is an organic compound having a molecular weight of 10,000 to 50,000,000, and an aqueous solution having an organic compound concentration in water of 0.1% by mass at 20 ° C. An organic compound in which no separation or sedimentation is observed even after standing for a period of time.

  Examples of the natural water-soluble organic polymer include starch such as potato starch, candy starch, wheat starch, rice starch, tapioca starch, corn starch, dextrin; resin polysaccharides such as gum arabic, tragacanth gum, karaya gum, trooaoi; guar gum, tara gum , Locust bean gum, tamarind seed polysaccharide, etc .; seaweed polysaccharides such as sodium alginate, carrageenan, agar (galactan), funari; microbial fermentation polysaccharides such as xanthan gum, pullulan, curdlan, dextran, levan; casein And proteins such as gelatin, albumin, glue and collagen; pectin, chitin, chitosan and the like.

  Examples of the semi-synthetic water-soluble organic polymer include cellulose derivatives such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and sodium cellulose sulfate; soluble starch, oxidized starch, carboxymethyl starch, hydroxyethyl starch, hydroxypropyl Starch derivatives such as starch, dialdehyde starch, phosphate starch and acetyl starch; propylene glycol alginate and the like.

  Examples of the synthetic water-soluble organic polymer include polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polyvinylpyrrolidone, polyvinyl alkyl ether, maleic anhydride copolymer, maleic acid copolymer, maleate copolymer Examples include coalescence.

  Among such water-soluble organic polymers, the solubility is good and can be easily removed by washing with hot water or water washing, the thickness retention of the fiber base material is further improved, and the texture of the leather material obtained and From the viewpoint of further improving physical properties such as friction fastness, resin polysaccharides, seed polysaccharides, seaweed polysaccharides, microbial fermentation polysaccharides, proteins, cellulose derivatives and the like are preferable. Among them, hydroxyethyl cellulose, xanthan gum and sodium alginate are preferable. More preferred.

(D) Nonionic surfactant The nonionic surfactant according to the present invention has a weight average molecular weight of 2,000 to 10,000,000 and contains 75% by mass or more of oxyalkylene groups in the molecule. It is.

  The weight average molecular weight is 2,000 to 10,000,000, preferably 5,000 to 1,000,000, and more preferably 5,000 to 500,000. When the weight average molecular weight is less than the lower limit, the thickness retention rate of the fiber base material is decreased, and physical properties such as texture and friction fastness of the obtained leather material tend to be decreased, on the other hand, exceeding the upper limit. In some cases, the liquid mixture becomes highly viscous, making it difficult to use. In the present invention, the weight average molecular weight refers to the weight average molecular weight determined by the gel permeation chromatography method when the value is 100,000 or less, and when it exceeds 100,000, the weight average molecular weight is determined by the viscosity method. Refers to the viscosity average molecular weight obtained.

  In the present invention, the gel permeation chromatography (GPC) method uses GPC (HLC-8220GPC, manufactured by Tosoh Corporation), mobile phase: tetrahydrofuran (THF), detector: RI, UV (254 nm). , Flow rate: 0.25 ml / min, column: Tsk-gel SuperHZ2000 × 25 cm × 2 / SuperHZ4000 × 15 cm × 1, temperature control: column oven (40 ° C.) / Inlet oven (40 ° C.) / RI detector (35 ° C), sample concentration: 0.2% THF solution, sample injection amount: 5 μl, and converted using a calibration curve obtained from the measurement results of a standard substance (polyethylene glycol) with a known weight average molecular weight Thus, the weight average molecular weight can be determined.

In the present invention, in the viscosity method, first, using an Ostwald viscometer, the specific viscosity (η ^sp ) of the sample in pure water under the conditions of sample concentration: c [g / dl], temperature: 35 ° C. And the sample concentration (c) is extrapolated to 0 from the reduced viscosity (η ^sp / c) obtained by dividing the specific viscosity by the sample concentration and the sample concentration (c) to obtain the ultimate concentration of the sample ([ η]) is calculated. Then the following formula:
[Η] = K × M ^a
[In formula, K and a show the coefficient determined by the kind of solvent and a sample, and M shows a viscosity average molecular weight. ]
Can be used to determine the viscosity average molecular weight. In the present invention, the values of K and a were 6.4 × 10 ⁻⁵ [dl / g] and 0.82, which are the values of polyethylene oxide in pure water, respectively.

  The nonionic surfactant which concerns on this invention is a nonionic surfactant, and is a compound which contains 75 mass% or more of oxyalkylene groups with respect to the molecular weight in a molecule | numerator. The content of the oxyalkylene group is preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass. When the oxyalkylene group in the molecular weight is less than the lower limit, the resin is plasticized, so that the physical properties such as friction fastness of the obtained leather material tend to be lowered. In addition, content of the oxyalkylene group with respect to the molecular weight of the nonionic surfactant which concerns on this invention can be calculated | required from content of the oxyalkylene group with respect to the weight average molecular weight of this nonionic surfactant.

  Such compounds include, for example, homoaddition polymers or coaddition polymers of alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide and tetramethylene oxide; methanol, ethanol, Alkylene oxide adducts of aliphatic alcohols having 1 to 22 carbon atoms such as butanol, octanol, lauryl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol; phenol, naphthol, cumylphenol, phenylphenol, methylphenol, butylphenol, octylphenol, nonylphenol , Dodecylphenol, methyl naphthol, butyl naphthol, octyl naphthol, nonyl naphthol, dodecyl naphthol, Zyl alcohol, phenylethanol, phenylpropanol, 1-benzyl-2-methylpropanol, diphenylmethanol, triphenylmethanol, p-methylbenzyl alcohol or their styrenes (styrene, α-methylstyrene, vinyltoluene), or Alkylene oxide adducts of aromatic hydroxy compounds having 6 to 50 carbon atoms such as benzyl chloride reactants; C 2-22 carbon atoms such as caprylic acid, lauric acid, stearic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, etc. Examples include an alkylene oxide adduct of a fatty acid. In addition, alkylene oxide adducts of trivalent alcohols such as trimethylolpropane and glycerol; alkylene oxide adducts of tetravalent alcohols such as pentaerythritol, diglycerin, erythritol, sorbitan, ditrimethylolpropane, and xylose; glucose, fructose, Alkylene oxide adducts of pentavalent alcohols such as galactose, xylitol, triglycerin; hexavalent alcohols such as dipentaerythritol, sorbitol, mannitol; octavalent alcohols such as tripentaerythritol, sucrose, lactose, maltose, trehalose Alkylene oxide adducts; alkylene oxide adducts of 10-valent alcohols such as tetrapentaerythritol; raffinose, maltotriose, melezite Alkylene oxide adducts of 11-valent alcohols such as sugars; alkylene oxide adducts of tetrasaccharides such as acarbose and stachyose; alkylene oxide adducts of polyhydric alcohols such as polysaccharides such as starch, dextrin, cyclodextrin and glycogen It is done. Furthermore, metalamine, ethylamine, butylamine, octylamine, laurylamine, stearylamine, oleylamine, behenylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibehenylamine, etc. Alkylene oxide adduct of aliphatic amine having 1 to 44 carbon atoms; alkylene oxide adduct of fatty acid amide having 2 to 22 carbon atoms such as caprylic acid amide, lauric acid amide, stearic acid amide, oleic acid amide, behenic acid amide; Alkylene oxide adducts of aromatic amines such as aniline, toluidine, 2,4,6-trimethylaniline; monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diamine Chirentoriamin, triethylenetetramine, N, N-dihydroxyethyl - alkylene oxide adducts of alkanolamines and polyalkylene polyamines such as ethylenediamine.

Among these, the nonionic surfactant according to the present invention is excellent in water solubility, the thickness retention of the fiber base material is further improved, and the texture and friction fastness of the obtained leather material (particularly the friction fastness in wet conditions). From the viewpoint that physical properties such as) tend to be further improved, the following general formula (1):
R ^1- [O— (R ² —O) _b —H] _m (1)
[In Formula (1), m represents an integer of 1 or more, R ¹ represents a hydrogen atom or a residue obtained by removing m hydroxy groups from a hydroxy compound having m hydroxy groups, and R ² represents the number of carbon atoms. Represents an alkylene group of 2 to 4, b represents an integer of 0 or more, and when b is 2 or more, R ² may be the same or different. ]
It is preferable that it is a compound represented by these.

In the said General formula (1), m is 1-6 from a viewpoint that the thickness retention of a fiber base material improves more, and there exists a tendency which physical properties, such as the texture of a leather material obtained, and friction fastness, also improve more. It is preferable that As the residue obtained by removing the m hydroxy groups from the hydroxy compound having m hydroxy groups represented by R ^1, it may be a cyclic be a chain, a carbon number 1 to 50 And an m-valent saturated hydrocarbon group or an m-valent unsaturated hydrocarbon group having 2 to 50 carbon atoms. As R ¹ , the water solubility of the nonionic surfactant is excellent, the thickness retention rate of the fiber base material is further improved, and physical properties such as the texture and friction fastness of the obtained leather material tend to be further improved. From the viewpoint, a saturated hydrocarbon group having 1 to 6 carbon atoms and m valence (m is preferably 1 to 4), an unsaturated hydrocarbon having 2 to 6 carbon atoms and m valence A group (m is preferably 1 to 4) and a hydrogen atom are preferable, and a residue obtained by removing a hydroxy group from glycerin and a hydrogen atom are more preferable.

Further, in the general formula (1), ^{R 2} is an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group and a propylene group are preferable, and an ethylene group is more preferable from the viewpoint that the water solubility of the nonionic surfactant tends to be excellent. In the compound represented by the general formula (1), from the same viewpoint as described above, it is preferable that 10% by mass or more, more preferably 20% by mass or more of the oxyalkylene groups are oxyethylene groups. Furthermore, b is preferably 75 to 10,000 from the viewpoint that the thickness retention of the fiber base material is further improved, and physical properties such as texture and friction fastness of the obtained leather material tend to be further improved. .

  Moreover, as such (D) nonionic surfactant, from the viewpoint that the friction fastness of the obtained leather material tends to be superior in both wet and dry conditions, the alkylene oxide having 2 to 4 carbon atoms is used. An addition polymerization product and an alkylene oxide addition product of glycerin are preferable, and an alkylene oxide addition product of polyoxyethylene and glycerol is more preferable.

(E) Water (E) Water according to the present invention comprises the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, the (D) nonionic surfactant, and, if necessary, the (C) water-soluble. When mixing the organic polymer, it has a role as a solvent, and ion-exchanged water or distilled water can be suitably used.

  In the present invention, (A) water-based polyurethane resin, (B) inorganic acid ammonium salt, (D) nonionic surfactant, (E) water and, if necessary, (C) water-soluble organic polymer The method for preparing the mixed solution is not particularly limited, and a known method can be used as appropriate.

  In the mixed solution according to the present invention, the blending ratio (A: B) of the (A) aqueous polyurethane resin and the (B) inorganic acid ammonium salt is 100: 0.05 to 100: 60 in mass ratio. It is preferably 100: 0.1 to 100: 60, more preferably 100: 0.1 to 100: 50, and particularly preferably 100: 2 to 100: 10. When the blending ratio of the inorganic acid ammonium salt (B) is less than the lower limit, the effect of preventing migration in the drying process tends to be reduced. On the other hand, when the blending ratio exceeds the upper limit, In a temperature atmosphere, the mixed solution tends to gel, or the mixed solution tends to cause poor dispersion. Moreover, even if it mix | blends the said upper limit (B) inorganic acid ammonium salt, since it exists in the tendency for a performance to not improve any more, it becomes economically disadvantageous.

  Moreover, in the liquid mixture which concerns on this invention, when it further contains (C) water-soluble organic polymer, the compounding ratio (A: C) of said (A) water-based polyurethane resin and said (C) water-soluble organic polymer ) Is preferably 100: 0.05 to 100: 70, more preferably 100: 0.1 to 100: 50, and more preferably 100: 0.1 to 100: 20. More preferably, it is particularly preferably 100: 0.5 to 100: 20. When the blending ratio of the (C) water-soluble organic polymer is less than the lower limit, the thickness retention rate of the fiber base material and the texture of the obtained leather material tend to decrease. On the other hand, when the upper limit is exceeded, the thickness retention of the fiber base material and the texture of the resulting leather material tend to be lowered, and the mixed liquid tends to be highly viscous and difficult to use.

  Furthermore, in the liquid mixture which concerns on this invention, the compounding ratio (A: D) of the said (A) aqueous polyurethane resin and the said (D) nonionic surfactant is 100: 1-100: 150 by mass ratio. It is preferably 100: 2 to 100: 100, more preferably 100: 5 to 100: 70. When the blending ratio of the (D) nonionic surfactant is less than the lower limit and exceeds the upper limit, the thickness retention of the fiber base material and the texture and friction fastness of the resulting leather material are lowered. There is a tendency.

  Moreover, in the liquid mixture which concerns on this invention, from the same viewpoint as the above, the compounding ratio ((A) aqueous | water-based polyurethane resin, the said (B) inorganic acid ammonium salt, and the said (D) nonionic surfactant ( A: B: D) is preferably 100: 0.05 to 60: 1 to 150, more preferably 100: 0.1 to 50: 2 to 100, and 100: 2 to A: B: D). More preferably, it is 10: 5-70. When the mixed liquid according to the present invention further contains the (C) water-soluble organic polymer, the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, and the (C) water-soluble The mixing ratio (A: B: C: D) of the conductive organic polymer and the (D) nonionic surfactant is 100: 0.05 to 60: 0.05 to 70: 1 to 150 by mass ratio. It is preferably 100: 0.1-50: 0.1-50: 2-100, more preferably 100: 2-10: 0.5-20: 5-70. .

  Furthermore, the content of the (A) aqueous polyurethane resin in the mixed liquid according to the present invention is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the mixed liquid. . When the content of the (A) water-based polyurethane resin is less than the lower limit, a large amount of liquid mixture is required to obtain the target leather material. Therefore, the economy tends to decrease. On the other hand, when it exceeds the upper limit, the stability of the mixed solution tends to decrease.

  In such a mixed liquid according to the present invention, the thermal coagulation temperature can be set within a suitable range (preferably 30 to 90 ° C.), migration is suppressed, and the thickness of the fiber substrate is maintained and friction is maintained. A leather material excellent in fastness can be obtained efficiently and reliably. The heat-sensitive coagulation temperature is more preferably 30 to 80 ° C, and further preferably 40 to 70 ° C. In the present invention, the thermal coagulation temperature means that 5 to 10 g of the mixed solution is taken in a 20 mL glass test tube, the test tube is left in a water bath, and the temperature of the water bath is raised at 1 ° C./min. And the temperature at which the contents lose their fluidity and solidify. If the thermal coagulation temperature is less than the lower limit, the mixture tends to gel in a relatively high temperature atmosphere such as summer, while if the upper limit is exceeded, the thermal coagulation is sharply expressed. Therefore, coagulation is weakened in the coagulation step, and the migration prevention property tends to be lowered. In particular, this tendency becomes remarkable when drying (coagulation) at a relatively low temperature of about 85 to 120 ° C.

  It does not restrict | limit especially as a fiber base material which concerns on this invention, A woven fabric, a knitted fabric, or a nonwoven fabric etc. can be used suitably. Further, the fiber base material is not particularly limited, but polyamide fibers and polyester fibers are preferable from the viewpoint that the thickness is sufficiently maintained and a texture and quality closer to natural leather tend to be obtained. .

When using a nonwoven fabric as the fiber base material, the thickness of the yarn is preferably 2.0 dtex or less from the viewpoint of further improving the texture and quality of the obtained leather material. If the yarn thickness of the nonwoven fabric exceeds the above upper limit, the texture of the obtained leather material becomes coarse and hard, and the quality tends to be impaired. As the density of such a nonwoven fabric is preferably 0.1 to 0.8 g / cm ^3, more preferably 0.30~0.55g / cm ^3. When the density of the non-woven fabric is less than the lower limit, the wear resistance of the obtained leather material tends to be reduced, and when a large amount of polyurethane resin is fixed to make up for it, the texture of the obtained leather material is coarse. There is a tendency to deteriorate the quality. On the other hand, if the density of the non-woven fabric exceeds the upper limit, the texture of the obtained leather material becomes coarse and hard, and the quality tends to be impaired. Further, the thickness of the fiber substrate is not particularly limited, but is preferably 0.1 to 1 cm, and more preferably 0.1 to 0.5 cm.

  In the present invention, an additive may be further added to the mixed solution for the purpose of imparting processability to the obtained leather material within a range not impairing the effects of the present invention. Examples of such additives include lower alcohols, glycol-based solvents, alcohol-based nonionic surfactants, acetylene glycol-based special surfactants, silicone-based surfactants, fluorine-based surfactants, anions Surfactants, cationic surfactants, various penetrants such as surfactants other than the nonionic surfactant according to the present invention; various stabilizers such as antioxidants, light-resistant stabilizers, UV inhibitors; mineral oils And various antifoaming agents such as silicones; urethanization catalysts; plasticizers; colorants such as pigments; pot life extenders; and fillers such as acrylic resin beads and urethane resin beads. Such additives may be used alone or in combination of two or more. When these additives are added to the liquid mixture according to the present invention, the total addition amount is preferably an amount that is 50% by mass or less with respect to the total mass of the nonvolatile content of the liquid mixture. In the present invention, the total mass of the non-volatile content of the mixed solution means (A) an aqueous polyurethane resin, (B) an inorganic acid ammonium salt, (C) a water-soluble organic polymer, (D) This refers to the total mass of the nonionic surfactant. In addition, when these compounds are used in the form of a water-emulsified dispersion obtained by emulsifying and dispersing these compounds in water, the mass refers to the residue (nonvolatile) when the water-emulsified dispersion is heated at a temperature of 105 ° C. for 3 hours. Minutes).

  Further, in the present invention, when a polyurethane resin having a carboxy group is used as the (A) aqueous polyurethane resin, the object is to impart processability to the obtained leather material within a range not impairing the effects of the present invention. As described above, a crosslinking agent that reacts with the carboxy group can be further added to the mixed solution. Examples of such crosslinking agents include oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, blocked isocyanate crosslinking agents, water-dispersed isocyanate crosslinking agents, and melamine crosslinking agents. Etc. As the crosslinking agent, one kind may be used alone, or two or more kinds may be used in combination. Among these crosslinking agents, a carbodiimide-based crosslinking agent is preferred from the viewpoint that the light resistance, heat resistance, and water resistance of the obtained leather material tend to be further improved. It is preferable that it is 0.5-10 mass% with respect to water-based polyurethane resin.

  In the present invention, the method for impregnating the fiber base material with the mixed liquid is not particularly limited, and a known method can be used as appropriate. As the impregnation method, for example, conventionally known methods such as impregnation processing using a dip-nip method, spray treatment, and a method of impregnation while coating with a coater can be preferably employed, and the concentration and treatment conditions of the mixed solution Etc. can be appropriately selected according to the method employed. The fiber base material can be pretreated before the fiber base material is impregnated with the mixed liquid. As such a pretreatment step, in order to adjust the adhesive force between the fiber base material and the polyurethane resin component, a polymer aqueous solution composed of polyvinyl alcohol, carboxymethyl cellulose, etc., a silicone water repellent, a fluorine water repellent It is preferable to process the said fiber base material using etc.

  The amount of the mixed liquid impregnated into the fiber base material is obtained from the viewpoint that the thickness retention rate of the fiber base material is further improved, and physical properties such as the texture and fastness to friction of the obtained leather material are further improved. The material is preferably impregnated so that the component derived from the aqueous polyurethane resin (A) is 5 to 75% by mass.

  Furthermore, as the impregnation according to the present invention, it is preferable to impregnate the component derived from the water-based polyurethane resin (A) sufficiently to the inside of the obtained leather material. According to the production method of the present invention, since migration is suppressed, the component derived from the (A) aqueous polyurethane resin can be sufficiently fixed in this way, and the thickness of the fiber base material is maintained, which is excellent. Friction fastness is achieved. Moreover, especially when the said mixed liquid further contains the said (C) water-soluble organic polymer, the thickness of a fiber base material is fully hold | maintained and the outstanding texture is also achieved. As the fixing state of the component derived from the aqueous polyurethane resin (A), not only the surface of the leather material but also the leather when the cross section of the leather material is observed at a magnification of 150 times using a scanning electron microscope. It is preferable that the component derived from the (A) water-based polyurethane resin is also fixed in 10% of the central portion of the thickness of the material, and the resin fixing amount is completely different between the central portion and the surface portion of the leather material. More preferably no difference is observed.

  In the present invention, the fiber base material is impregnated with the mixed solution, and then dried and solidified. In the present invention, the drying method is not particularly limited, and for example, dry drying using hot air; high-tempered steamer (HTS), high pressure steamer (HPS) is used. Wet drying; microwave irradiation drying and the like can be used, and among them, from the viewpoint of resin solidification and shortening of the coagulation time, it is preferable to wet and heat coagulate by wet drying using humidity (steam). These drying methods may be used singly or in combination of two or more. Moreover, as drying conditions (coagulation conditions), it is preferable that it is 1 to 30 minutes at the temperature of 80-180 degreeC, and it is 2 to 10 minutes at the temperature of 80-130 degreeC (more preferably 85-120 degreeC). It is more preferable. Thus, by drying and solidifying the mixed solution impregnated in the fiber base material, the polyurethane resin can be fixed inside the fiber base material. In the present invention, after the mixed solution is solidified, dry heat drying for drying water at 100 to 200 ° C. (preferably 120 to 180 ° C.) for 1 to 60 minutes (preferably 2 to 30 minutes) is performed. It is preferable.

  Thus, it contains the (A) polyurethane resin, the (B) inorganic acid ammonium salt, the (D) nonionic surfactant, (E) water, and, if necessary, the (C) water-soluble organic polymer. The leather material of the present invention can be obtained by allowing the fiber base material to be impregnated into the fiber substrate and then drying.

  Further, the leather material of the present invention can be dyed. The leather material of the present invention can sufficiently maintain its texture and thickness even after being dyed. Such a dyeing method is not particularly limited, and the polyurethane resin is fixed after the fiber base material is dyed even in the post-impregnation dyeing method in which dyeing is performed after fixing the polyurethane resin to the fiber base material. A post-impregnation dyeing method may also be used.

  Furthermore, the leather material of the present invention can be formed into a leather material with a silver surface by forming a skin layer. The method for forming such a skin layer may be any conventionally known method, and is not particularly limited. For example, a skin layer material is applied to a release paper, and the skin material is evaporated to evaporate water. After forming the layer, an adhesive is applied to the surface of the skin layer and bonded to the leather material of the present invention, and the adhesive layer is formed by evaporating the moisture of the adhesive or evaporating the moisture to form the adhesive layer. And a method of bonding them together (release paper transfer method). Also, after forming a skin layer on the release paper, a thermal transfer method in which the skin layer and the leather material of the present invention are bonded by heat; a spray method in which the material for the skin layer is sprayed directly on the leather material of the present invention; gravure coater And a direct coating method in which the material for the skin layer is applied onto the leather material of the present invention using a knife coater, comma coater, air knife coater or the like. Among the methods for forming such a skin layer, a release paper transfer method is preferable from the viewpoint of improving physical properties such as friction fastness of the obtained skin layer. The material for the skin layer and the adhesive used in the release paper transfer method are not particularly limited as long as they can be bonded to the leather material of the present invention, but the thickness of the fiber base material can be further maintained. Polyurethane resins are preferable from the viewpoint of obtaining more excellent physical properties such as texture and friction fastness, and water-based or solvent-free ones are desirable from the viewpoint of reducing VOC and reducing environmental burden.

  The leather material of the present invention can be used in the fields of vehicles, furniture, clothing, shoes, bags, bags, sandals, miscellaneous goods, polishing, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, each measurement and evaluation in each synthesis example, example, and comparative example were performed by the following methods, respectively.

(1) Measurement of thermal coagulation temperature 5.0 g of polyurethane resin water emulsified dispersion obtained in each polyurethane resin synthesis example or 5.0 g of the mixed solution obtained in each example and each comparative example was put into a 20 mL glass test tube. Each test tube was allowed to stand in a water bath, and the temperature of the water bath was raised at 1 ° C./min. The temperature at which the contents lost the fluidity and solidified was measured to obtain the thermal coagulation temperature.

(2) Measurement of value of 100% modulus Using the polyurethane resin water-emulsified dispersion obtained in each polyurethane resin synthesis example, JIS K 6250 (2006) 8. A dumbbell-shaped No. 3 test piece was produced in the same manner as the specimen collection and production, and the distance between the marked lines was increased by 100% in the same manner as in JIS K 6251 (2010) (doubled). The value of the predetermined elongation tensile stress (MPa) was measured to obtain a value of 100% modulus.

(3) Texture evaluation About the leather material after dyeing process obtained by each Example and each comparative example, the following references | standards by tactile sensation:
Grade 5: Soft and extremely rich in impact resilience Grade 4: Soft and impact-rich texture 3rd grade: Soft but somewhat lacking in impact resilience Grade 2: Slightly coarse and paper-like (like paper ) Texture Grade 1: Evaluation was performed according to a rough and paper-like (paper-like) texture.

(4) Migration prevention evaluation About the leather material after dyeing processing obtained by each Example and each comparative example, the cross section of the leather material is 150 times using a scanning electron microscope (JSM-6010LA (made by JEOL)). Observed at a magnification, the following criteria were compared between the fixed state of the polyurethane resin present at the center of the nonwoven fabric and the fixed state of the polyurethane resin present at the surface portion of the nonwoven fabric:
Grade 5: No difference in the amount of resin fixed between the center and the surface of the leather material cross section, and no migration occurred. Class 4: The resin fixed between the center and the surface of the leather material cross section. There is almost no difference in the amount, and no migration has occurred. Grade 3: In the leather material cross section, there is a slight difference in the amount of resin fixation between the center and the surface, and the central part occupies the total thickness. Resin adhesion is not recognized in the 10% portion. Second grade: In the leather material cross section, there is a considerable difference in the amount of resin adhesion between the central portion and the surface portion, and in the central portion accounting for 30% of the total thickness. Resin adhesion is not recognized Grade 1: In the leather material cross section, there is a marked difference in the amount of resin adhesion between the central part and the surface part, and resin adhesion is observed in 50% of the central part of the total thickness. Follow not allowed And evaluated. In addition, when the fixed state of the polyurethane resin was between two standards, for example, when it was between the fourth grade and the fifth grade, it was evaluated as “4-5 grade”.

(5) Thickness Retention Evaluation The thickness of the post-dyeing leather material obtained in Examples and Comparative Examples and the thickness of the unprocessed cloth used in the production of each leather material were measured with a precision thickness measuring instrument (OZAKI MFG. CO., LTD DIAL THICKNESS GUAGE H-MT), and the following formula:
Thickness retention (%) = D1 × 100 / D2
[D1: Thickness of leather material obtained in Examples and Comparative Examples, D2: Thickness of raw cloth]
The thickness retention rate (%) is calculated by the following criteria:
Evaluation A: Retention ratio 80% or more Evaluation B: Retention ratio 60% or more to less than 80% Evaluation C: Evaluation was performed according to a retention ratio of less than 60%. When the thickness retention rate differs depending on the measurement location, for example, when the location of evaluation A and the location of evaluation B coexist, it was evaluated as “AB”.

(6) Odor Evaluation In each of the examples and comparative examples, the odor of ammonia and acid when performing wet heat coagulation and dry heat drying is functional, and the following criteria:
Evaluation A: No odor Evaluation B: Slight odor Evaluation C: Evaluated by a strong odor that pierces the nose.

(7) Friction fastness evaluation About the leather material after dyeing processing obtained by each example and comparative example, according to JIS L 0849 (2004), using a Gakushin type friction tester (manufactured by Daiei Chemical Seiki Seisakusho). In wet and dry processes, friction with a load of 200 g was performed 100 times, and the fastness to friction was evaluated. The above-mentioned friction fastness is based on the following criteria:
5th grade: No contamination was observed 4th grade: Slight contamination was observed 3rd grade: Contamination was clearly recognized 2nd grade: Slightly significant contamination was observed 1st grade: Evaluation was made according to the markedly recognized contamination.

(Polyurethane resin synthesis example 1)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 188.3 g of polytetramethylene glycol (weight average molecular weight 1,000), 8.9 g of 2,2-dimethylolpropionic acid, After adding 0.001 g of dibutyltin dilaurate and 75 g of methyl ethyl ketone and mixing them uniformly, 102.8 g of dicyclohexylmethane diisocyanate is added and reacted at 80 ° C. for 300 minutes to give a carboxy group having a free isocyanate group content of 3.1% by mass. A methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having the following was obtained.

  After cooling the solution to 50 ° C. or lower, 6.7 g of triethylamine was added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or less, and 432.3 g of water is gradually added using a disper blade to emulsify and disperse the neutralized product of the isocyanate group-terminated prepolymer having a carboxy group. A dispersion was obtained. Then, an aqueous polyamine solution in which 8.2 g of ethylenediamine is dissolved in 33.0 g of water is added to the emulsified dispersion and subjected to a chain extension reaction at 35 ° C. for 60 minutes, and then the solvent is removed under reduced pressure at 35 ° C. A water-emulsified dispersion of a polyurethane resin having a stable carboxy group and carboxylate group having a weight of 40.0% by mass, a viscosity of 220 mPa · s (BM viscometer, No. 2 rotor, 60 rpm) and an average particle size of 120 nm was obtained.

  The total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and a carboxylate group was 1.0% by mass, and the value of 100% modulus was 10 MPa. Moreover, the water-emulsified dispersion of the polyurethane resin having a carboxyl group and a carboxylate group did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Polyurethane resin synthesis example 2)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 241.8 g of 1,6-hexanediol carbonate diol (weight average molecular weight 2,000), 2,2-dimethylolpropionic acid 5.5 g, 0.6 g of trimethylolpropane, 0.001 g of dibutyltin dilaurate and 75 g of methyl ethyl ketone were mixed and mixed uniformly. Then, 31.7 g of dicyclohexylmethane diisocyanate and 20.3 g of hexamethylene diisocyanate were added, and the mixture was heated at 80 ° C. for 300 minutes. A methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a carboxy group having a free isocyanate group content of 1.6% by mass was obtained.

  After cooling the solution to 50 ° C. or lower, 53.6 g of methyl ethyl ketone and 4.2 g of triethylamine were added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or less, and 435.0 g of water is gradually added using a disperse blade to emulsify and disperse the neutralized product of the isocyanate group-terminated prepolymer having a carboxy group. A dispersion was obtained. Then, an aqueous polyamine solution in which 4.4 g of ethylenediamine is dissolved in 17.4 g of water is added to the emulsified dispersion and subjected to a chain extension reaction at 35 ° C. for 60 minutes. A water-emulsified dispersion of a polyurethane resin having a stable carboxyl group and carboxylate group having a weight of 40.0% by mass, a viscosity of 160 mPa · s (BM viscometer, No. 2 rotor, 60 rpm) and an average particle diameter of 250 nm was obtained.

  The total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and a carboxylate group was 0.6% by mass, and the value of 100% modulus was 7 MPa. Moreover, the water-emulsified dispersion of the polyurethane resin having a carboxyl group and a carboxylate group did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Polyurethane resin synthesis example 3)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 64.3 g of 1,6-hexanediol carbonate diol (weight average molecular weight 1,000), polytetramethylene glycol (weight average molecular weight) 1,000) 64.3 g, 1,4-butanediol 11.6 g, 2,2-dimethylolpropionic acid 34.5 g, dibutyltin dilaurate 0.002 g and methyl ethyl ketone 75 g, and after mixing uniformly, isophorone diisocyanate 71.4 g and hexamethylene diisocyanate 54.0 g were added and reacted at 80 ° C. for 360 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a carboxy group having a free isocyanate group content of 2.9% by mass.

  After cooling the solution to 50 ° C. or lower, 53.6 g of methyl ethyl ketone and 24.7 g of triethylamine were added, and a neutralization reaction was performed at 40 ° C. for 30 minutes. Next, the neutralized solution is cooled to 30 ° C. or less, and 406.0 g of water is gradually added using a disper blade to emulsify and disperse the neutralized product of the isocyanate group-terminated prepolymer having a carboxy group. A dispersion was obtained. Then, an aqueous polyamine solution in which 7.7 g of ethylenediamine is dissolved in 30.9 g of water is added to the emulsified dispersion and subjected to a chain extension reaction at 35 ° C. for 60 minutes, and then the solvent is removed under reduced pressure at 35 ° C. A water-emulsified dispersion of a polyurethane resin having a stable carboxyl group and carboxylate group having a weight of 40.0% by mass, a viscosity of 510 mPa · s (BM viscometer, No. 3, rotor, 60 rpm) and an average particle diameter of 30 nm was obtained.

  The total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and a carboxylate group was 3.8% by mass, and the value of 100% modulus was 15 MPa. Moreover, the water-emulsified dispersion of the polyurethane resin having a carboxyl group and a carboxylate group did not gel when heated at 90 ° C., and had no heat-sensitive coagulation property.

(Polyurethane resin synthesis example 4)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube was charged with 233.2 g of polytetramethylene glycol (weight average molecular weight 1,000), 0.002 g of dibutyltin dilaurate and 75 g of acetone, After uniformly mixing, 40.7 g of dicyclohexylmethane diisocyanate and 26.1 g of hexamethylene diisocyanate were added and reacted at 80 ° C. for 120 minutes, and an acetone-terminated prepolymer of acetone having a free isocyanate group content of 1.7% by mass was obtained. A solution was obtained.

  After cooling the solution to 50 ° C. or lower, 625.0 g of acetone was added, and further cooled to 30 ° C. or lower, and 17.6 g of sodium 2- (2-aminoethylamino) -ethanesulfonate (45 mass% aqueous solution) was added. Immediately after that, 442.1 g of water was gradually added using a disper blade to obtain an emulsified dispersion in which an isocyanate group-terminated prepolymer having a sulfo group and a sulfonate group was emulsified and dispersed. Then, an aqueous polyamine solution in which 2.6 g of ethylenediamine is dissolved in 10.4 g of water is added to the emulsified dispersion and subjected to a chain extension reaction at 35 ° C. for 60 minutes, and then the solvent is removed under reduced pressure at 35 ° C. A water-emulsified dispersion of a polyurethane resin having a stable sulfo group and a sulfonate group having a weight of 40.0% by mass, a viscosity of 150 mPa · s (BM viscometer, No. 2 rotor, 60 rpm) and an average particle diameter of 80 nm was obtained.

  The total of the sulfo group content and the sulfonate group content in the polyurethane resin having sulfo groups and sulfonate groups was 0.9% by mass, and the value of 100% modulus was 2 MPa. Moreover, the water-emulsified dispersion of the polyurethane resin having a sulfo group and a sulfonate group did not gel when heated at 90 ° C. and had no heat-sensitive coagulation property.

(Polyurethane resin synthesis example 5)
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 213.8 g of 1,6-hexanediol carbonate diol (weight average molecular weight 1,000), 0.002 g of dibutyltin dilaurate and acetone After 75 g was charged and mixed uniformly, 86.2 g of dicyclohexylmethane diisocyanate was added and reacted at 80 ° C. for 90 minutes to obtain an acetone solution of an isocyanate group-terminated polymer having a free isocyanate group content of 2.6% by mass. .

  After cooling the solution to 50 ° C or lower, 625.0 g of acetone was added, and further cooled to 30 ° C or lower, and 10.2 g of sodium 2- (2-aminoethylamino) -ethanesulfonate (45% aqueous solution) was added. Immediately after that, 425.7 g of water was gradually added using a disper blade to obtain an emulsified dispersion in which an isocyanate group-terminated prepolymer having a sulfo group and a sulfonate group was emulsified and dispersed. Then, an aqueous polyamine solution in which 6.6 g of ethylenediamine is dissolved in 26.4 g of water is added to the emulsified dispersion, and a chain extension reaction is performed at 35 ° C. for 60 minutes, and then the solvent is removed at 35 ° C. under reduced pressure. A water-emulsified dispersion of a polyurethane resin having a stable sulfo group and a sulfonate group having a weight of 40.0% by mass, a viscosity of 50 mPa · s (BM viscometer, No. 1 rotor, 60 rpm) and an average particle diameter of 650 nm was obtained.

  The total of the sulfo group content and the sulfonate group content in the polyurethane resin having sulfo groups and sulfonate groups was 0.1% by mass, and the value of 100% modulus was 10 MPa. Moreover, the water-emulsified dispersion of the polyurethane resin having a sulfo group and a sulfonate group did not gel when heated at 90 ° C. and had no heat-sensitive coagulation property.

(Polyurethane resin comparative synthesis example 1)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 167.9 g of polytetramethylene glycol (weight average molecular weight 1,000), a random co-addition polymer of ethylene oxide and propylene oxide ( (Weight average molecular weight 1,000, oxyethylene group content 70% by mass) 36.9 g, 1,4-butanediol 3.2 g, trimethylolpropane 4.0 g, dibutyltin dilaurate 0.002 g and methyl ethyl ketone 128.6 g After uniformly mixing, 88.0 g of dicyclohexylmethane diisocyanate was added and reacted at 80 ° C. for 300 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated prepolymer having a free isocyanate group content of 1.0% by mass.

  After cooling the solution to 30 ° C. or lower, 0.5 g of decyl phosphate and 12.0 g of tristyrylphenol ethylene oxide adduct (weight average molecular weight: 2,000) were added and mixed uniformly, and then the disperse blade was removed. Then, 435.0 g of water was gradually added to perform phase inversion emulsification and dispersion to obtain an emulsified dispersion. Then, an aqueous polyamine solution prepared by dissolving 3.9 g of piperazine hexahydrate and 2.1 g of diethylenetriamine in 23.9 g of water was added to the emulsified dispersion, and the chain elongation reaction was performed for 90 minutes, and then at 35 ° C. under reduced pressure. Solvent removal was performed to obtain a water-emulsified dispersion of a stable aqueous polyurethane resin having a nonvolatile content of 40.0% by mass, a viscosity of 250.0 mPa · s (BM viscometer, No. 2 rotor, 60 rpm), and an average particle size of 550 nm.

  The content of carboxy group, carboxylate group, sulfo group and sulfonate group in this aqueous polyurethane resin was 0.0% by mass, and the 100% modulus was 2 MPa. Further, this water-based emulsified dispersion of the aqueous polyurethane resin was gelled at 65 ° C. and had heat-sensitive coagulation properties.

(Surfactant Synthesis Example 1)
After mixing 92 parts by mass (1.0 mol) of glycerin and 5.0 parts by mass of caustic soda and heating to 130 ° C. in an autoclave, 2,500 parts by mass of ethylene oxide (56.8 mol) and propylene oxide A mixture of 2,500 parts by mass (43.1 mol) was added and reacted under conditions of a pressure of 0.39 MPa or less and a temperature of 150 to 160 ° C. Glacial acetic acid was added to the reaction solution after the reaction to adjust the pH to 7, which was designated as surfactant 1 (ethylene oxide / propylene oxide random adduct of glycerin, mass ratio: ethylene oxide / propylene oxide = 50/50). When the weight average molecular weight of the obtained surfactant 1 was determined by the GPC method, it was 5,050, and the oxyalkylene group content was 98.2% by mass.

(Surfactant Synthesis Example 2)
After mixing 74 parts by weight (1.0 mol) of normal butanol and 2.0 parts by weight of caustic soda, heating up to 130 ° C. in an autoclave, 1,000 parts by weight of ethylene oxide (22.7 moles) and propylene A mixture of 1,000 parts by mass (17.2 mol) of oxide was added and reacted under conditions of a pressure of 0.39 MPa or less and a temperature of 150 to 160 ° C. Glacial acetic acid was added to the reaction solution after the reaction to adjust the pH to 7, which was designated as Surfactant 2 (ethylene oxide / propylene oxide random adduct of normal butanol, mass ratio: ethylene oxide / propylene oxide = 50/50). . When the weight average molecular weight of the obtained surfactant 2 was determined by the GPC method, it was 2,013 and the oxyalkylene group content was 96.3% by mass.

(Surfactant Synthesis Example 3)
First, 94 parts by mass (1.0 mol) of phenol and 0.1 part by mass of sulfuric acid were placed in a reaction vessel, heated with stirring under a nitrogen gas stream, and 312 parts by mass (3 mols) of styrene monomer at 110 to 130 ° C. ) Was added dropwise at 125 to 135 ° C. for 3 hours, and then cooled to obtain a brown transparent viscous liquid tristyrenated phenol. Next, 406 parts by mass (1.0 mol) of the obtained tristyrenated phenol and 2.5 parts by mass of caustic soda were mixed, heated to 130 ° C. in an autoclave, and then 1,700 parts by mass of ethylene oxide ( 38.6 mol) is added and the reaction is carried out under conditions of a pressure of 0.39 MPa or less and a temperature of 150 to 160 ° C., and glacial acetic acid is added to the reaction solution after the reaction to adjust the pH to 7. Styrylphenol ethylene oxide adduct). When the weight average molecular weight of the obtained surfactant 3 was determined by GPC method, it was 2,038 and the oxyalkylene group content was 80.1% by mass.

(Surfactant Synthesis Example 4)
After mixing 92 parts by mass (1.0 mol) of glycerin and 30.0 parts by mass of caustic soda and heating to 130 ° C. in an autoclave, 15,200 parts by mass (345.5 mol) of ethylene oxide and propylene oxide A mixture of 15,200 parts by mass (262.1 mol) was added and reacted under conditions of a pressure of 0.39 MPa or less and a temperature of 150 to 160 ° C. Glacial acetic acid was added to the reaction solution after the reaction to adjust the pH to 7, which was designated as surfactant 4 (ethylene oxide / propylene oxide random adduct of glycerol, mass ratio: ethylene oxide / propylene oxide = 50/50). When the weight average molecular weight of the obtained surfactant 4 was determined by the GPC method, it was 30,337, and the oxyalkylene group content was 99.7% by mass.

(Surfactant Synthesis Example 5)
270 parts by mass (1.0 mol) of stearyl alcohol and 1.0 part by mass of caustic soda were mixed and heated to 130 ° C. in an autoclave, and then 430 parts by mass (9.8 mol) of ethylene oxide and 430 of propylene oxide. A part by mass (7.4 mol) of a mixture was added and reacted under conditions of a pressure of 0.39 MPa or less and a temperature of 150 to 160 ° C. Glacial acetic acid was added to the reaction solution after completion of the reaction to adjust the pH to 7, which was designated as surfactant 8 (ethylene oxide / propylene oxide random adduct of stearyl alcohol, mass ratio: ethylene oxide / propylene oxide = 50/50). . When the weight average molecular weight of the obtained surfactant 8 was determined by GPC method, it was 1,080, and the oxyalkylene group content was 75.0% by mass.

Example 1
250 parts by mass (A) water-emulsified dispersion of polyurethane resin obtained in Polyurethane Resin Synthesis Example 1 (100 parts by mass of resin solid content), (B) 0.25 parts by mass of 20% by mass aqueous solution of ammonium sulfate (ammonium sulfate 0.05 Parts by mass), (C) 2.5 parts by mass of hydroxyethyl cellulose (“AL-15” manufactured by Sumitomo Seika Co., Ltd.), (D) 30 parts by mass of surfactant 1 obtained in surfactant synthesis example 1, and (E) 50.8 parts by mass of water was uniformly mixed to prepare a mixed solution having an aqueous polyurethane resin concentration of 30% by mass. The thermal coagulation temperature in the mixed solution was 83 ° C.

This mixed solution was impregnated into a raw cloth (nonwoven fabric made of polyester fiber, 0.5 dtex, density 0.3 g / cm ³ ) using a slit mangle so that the pickup would be 100% by mass, and then wet. Drying (wet heat coagulation) was performed at a relative humidity of 60% and a temperature of 90 ° C. for 10 minutes, and then dry heat drying was performed at 130 ° C. for 5 minutes to obtain artificial leather (leather material). Furthermore, the obtained artificial leather was dyed and RC soaped under the following conditions to obtain an artificial leather dyed cloth (leather material after dyeing).

<Dyeing conditions>
Dyeing machine: Mini color dyeing machine (Texam Giken Co., Ltd.)
Dye: Kaylon Microester Blue DX-LS conc (manufactured by Nippon Kayaku Co., Ltd.) 0.10% o. w. f.
Kayalon Microester Yellow DX-LS (manufactured by Nippon Kayaku Co., Ltd.) 2.00% o. w. f.
Kayalon Microester Red DX-LS (manufactured by Nippon Kayaku Co., Ltd.) 0.80% o. w. f.
Dyeing assistant: Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.) 0.5 g / L
pH adjuster: 90% mass acetic acid 0.3cc / L
Bath ratio: (1:20)
Dyeing conditions: 130 ° C. × 60 minutes (heating rate 2 ° C./min).

<RC conditions>
RC bath: Sodium hydroxide 2g / L
Hydrosulfite 2g / L
Bath ratio: (1:20)
RC condition: 80 ° C. × 20 minutes (temperature increase rate 2 ° C./min).

  Odor evaluation at the time of wet heat coagulation and dry heat drying, and texture evaluation, migration prevention evaluation, thickness retention evaluation, and friction fastness of the obtained artificial leather dyed fabric (dyed leather material) The results of the evaluation (wet / dry) are shown in Table 1 together with the composition of the mixed solution, the concentration of the aqueous polyurethane resin in the mixed solution, the pickup and the thermal coagulation temperature.

(Examples 2-9)
Artificial leather (leather material) and artificial leather dyed cloth (dyeing) in the same manner as in Example 1 except that ammonium sulfate in the mixed liquid, aqueous polyurethane resin concentration and pickup in the mixed liquid are as shown in Table 1, respectively. After processing, a leather material) was obtained. Odor evaluation during wet heat coagulation and dry heat drying, and texture evaluation, migration prevention evaluation, thickness retention evaluation and friction fastness evaluation for the obtained artificial leather dyed fabric (dyed leather material) ( The results of wet and dry) are shown in Table 1 together with the composition of each liquid mixture, the aqueous polyurethane resin concentration in the liquid mixture, the pickup, and the thermal coagulation temperature.

(Examples 10 to 19)
In the same manner as in Example 5 except that ammonium sulfate, hydroxyethyl cellulose, and pickup in the mixed solution are as shown in Table 2, artificial leather (leather material) and artificial leather dyed cloth (dyed leather material) Obtained. Odor evaluation during wet heat coagulation and dry heat drying, and texture evaluation, migration prevention evaluation, thickness retention evaluation and friction fastness evaluation for the obtained artificial leather dyed fabric (dyed leather material) ( The results of wet and dry) are shown in Table 2 together with the composition of each liquid mixture, the concentration of the aqueous polyurethane resin in the liquid mixture, the pickup and the thermal coagulation temperature.

(Examples 20 to 27)
Artificial leather (leather material) and artificial leather dyed cloth (dyed leather after dyeing), except that the content of surfactant 1 in the mixed solution was the mass shown in Table 3 in the same manner as in Example 5. Material). Odor evaluation during wet heat coagulation and dry heat drying, and texture evaluation, migration prevention evaluation, thickness retention evaluation and friction fastness evaluation for the obtained artificial leather dyed fabric (dyed leather material) ( The results of wet and dry) are shown in Table 3 together with the composition of each liquid mixture, the concentration of the aqueous polyurethane resin in the liquid mixture, the pickup and the thermal coagulation temperature.

(Example 28)
(B) Instead of 25 parts by mass of 20% by mass aqueous solution of ammonium sulfate (5 parts by mass of ammonium sulfate), 25% by mass of 20% by mass aqueous solution of ammonium phosphate (3 ammonium phosphate / diammonium hydrogen phosphate (mass ratio 50/50)) Parts (artificial leather (leather material)) and artificial leather dyed cloth (external leather 3 parts 2.5 parts by weight / hydrogenammonium hydrogen phosphate 2.5 parts by weight) in the same manner as in Example 5. A leather material was obtained after dyeing.

(Example 29)
(B) It replaced with 25 mass parts of 20 mass% aqueous solution of ammonium sulfate (5 mass parts of ammonium sulfate), and it was the same as that of Example 5 except having used 25 mass parts of 20 mass% aqueous solution of ammonium chloride (5 mass parts of ammonium chloride). Thus, an artificial leather (leather material) and an artificial leather dyed cloth (dyed leather material) were obtained.

(Example 30)
(C) In place of hydroxyethyl cellulose (“AL-15” manufactured by Sumitomo Seika Co., Ltd.), xanthan gum (“Rhodopol 23” manufactured by Rhodia) was used in the same manner as in Example 5, and artificial leather (leather material) In addition, an artificial leather dyed cloth (leather material after dyeing process) was obtained.

(Example 31)
(C) In place of hydroxyethyl cellulose (“AL-15” manufactured by Sumitomo Seika Co., Ltd.), sodium alginate (“Snow Algin M” manufactured by Fuji Chemical Industry Co., Ltd.) was used. Leather (leather material) and artificial leather dyed cloth (dyed leather material) were obtained.

(Examples 32-37)
(D) In place of surfactant 1, surfactants 2 to 4 obtained in surfactant synthesis examples 2 to 4 and the following surfactants 5 to 7:
Surfactant 5: “ADEKA Pluronic F-88” manufactured by ADEKA, polyoxyethylene-polyoxypropylene-polyoxyethylene block polymer, weight average molecular weight: 10,800, oxyalkylene group content: 100% by mass,
Surfactant 6: “PEO-1Z” manufactured by Sumitomo Seika Co., Ltd., polyoxyethylene, (weight average molecular weight (viscosity average molecular weight): 200,000, oxyalkylene group content: 100% by mass,
Surfactant 7: “PEO-27” manufactured by Sumitomo Seika Co., Ltd., polyoxyethylene, weight average molecular weight (viscosity average molecular weight): 7 million, oxyalkylene group content: 100% by mass,
In the same manner as in Example 5 except that the composition of the mixed solution was changed to the composition shown in Table 4, artificial leather (leather material) and artificial leather dyed cloth (dyeed leather material) were obtained. I got each.

(Examples 38 to 41)
(A) The polyurethane resin obtained in polyurethane resin synthesis examples 2 to 5 instead of 250 parts by mass of the water-emulsified dispersion of polyurethane resin (100 mass parts of resin solid content) obtained in polyurethane resin synthesis example 1 Artificial leather (leather material) and artificial leather dyed cloth (dyeed leather material) in the same manner as in Example 5 except that 250 parts by mass of the water-emulsified dispersion (100 mass parts of resin solids) was used. Respectively.

(Examples 42 to 52)
(C) Artificial leather (leather material) and artificial leather dyed cloth (dyeing process) were carried out in the same manner as in Example 5 except that hydroxyethyl cellulose was not used and the composition of the mixed solution was as shown in Table 6. The material for the rear leather was obtained.

  Odor evaluation when performing wet heat coagulation and dry heat drying in Examples 28 to 52, and texture evaluation, migration prevention evaluation, and thickness retention evaluation of the obtained artificial leather dyed processed fabric (dyed leather material) Tables 4 to 6 show the results of the friction fastness evaluation (wet / dry), together with the composition of each liquid mixture, the aqueous polyurethane resin concentration in the liquid mixture, the pickup, and the thermal coagulation temperature.

(Comparative Examples 1-25)
Artificial leather (leather material) and artificial leather-dyed cloth (dye-finished leather material) were obtained in the same manner as in Example 5 except that the composition of the mixed solution was as shown in Tables 7-8. It was. In Tables 7 to 8, the compounds used as salts and surfactants are as follows. In addition, the liquid mixture in Comparative Examples 1, 4, 5, 8, 13-17, and 19-25 did not gel at 95 ° C., and had no heat-sensitive coagulation property. In Comparative Example 18, an insoluble material was generated and a mixture could not be obtained. Furthermore, the mixed solution in Comparative Example 9 was poor in storage stability, and the emulsification dispersibility sometimes deteriorated over time.

<Salts>
Sodium sulfate: 25 parts by mass of a 20% by mass aqueous solution of sodium sulfate (5 parts by mass of sodium sulfate),
Ammonium acetate: 25 mass parts of 20 mass% aqueous solution of ammonium acetate (5 mass parts of ammonium acetate),
Sodium phosphate: 25 parts by mass of a 20% by mass aqueous solution of trisodium phosphate / disodium hydrogen phosphate (mass ratio 50/50) (2.5 parts by mass of trisodium phosphate 2.5 / 2.5 parts by mass of disodium hydrogen phosphate)
Ammonium carbonate: 25 parts by mass of a 20% by mass aqueous solution of ammonium carbonate (5 parts by mass of ammonium carbonate),
Magnesium sulfate: 25 parts by mass of a 20% by mass aqueous solution of anhydrous magnesium sulfate (magnesium sulfate 5 parts by mass),
Colloidal silica: “Adelite AT-20A” (solid content 20% by mass) 25 parts by mass (5 parts by mass of colloidal silica) manufactured by Asahi Denka
Aluminum chloride: 25 parts by mass of a 20% by mass aqueous solution of aluminum chloride (5 parts by mass of aluminum chloride),
Calcium carbonate: 25 parts by mass of a 20% by mass aqueous dispersion of calcium carbonate (5 parts by mass of calcium carbonate),
Aluminum hydroxide: 25 parts by weight of a 20% by weight aqueous dispersion of aluminum hydroxide (5 parts by weight of aluminum hydroxide),
Silica: 5 parts by weight of “Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.
Sodium chloride: 25 parts by mass of a 20% by mass aqueous solution of sodium chloride (5 parts by mass of sodium chloride),
Calcium chloride: 25 parts by weight of a 20% by weight aqueous solution of calcium chloride (5 parts by weight of calcium chloride),
Aluminum sulfate: 25 parts by mass of a 20% by mass aqueous solution of aluminum sulfate (5 parts by mass of aluminum sulfate),
Sodium carbonate: 25 parts by mass of a 20% by mass aqueous solution of sodium carbonate (5 parts by mass of sodium carbonate).

<Surfactant>
Surfactant 8: Surfactant 8 obtained in Surfactant Synthesis Example 5
Surfactant 9: “Reodol 440V” manufactured by Kao Corporation, polyoxyethylene 40 mol sorbitol tetraoleate, weight average molecular weight: 3,115, oxyalkylene group content: 60.8 mass%.

  Odor evaluation when wet heat coagulation and dry heat drying were performed in Comparative Examples 1 to 25, and texture evaluation, migration prevention evaluation, thickness retention evaluation of the obtained artificial leather dyed cloth (leather material after dyeing process) Tables 7 to 8 show the results of the friction fastness evaluation (wet / dry), together with the composition of each liquid mixture, the aqueous polyurethane resin concentration in the liquid mixture, the pickup, and the thermal coagulation temperature.

  As is clear from the results shown in Tables 1 to 8, in the leather materials obtained in Examples 1 to 52, migration was suppressed and the thickness of the fiber base material was maintained, and excellent friction fastness. It was confirmed to have a degree. In particular, in the leather material obtained in Examples 2 to 52, no migration was observed, and the resin was uniformly fixed to the inside of the nonwoven fabric. Furthermore, in the leather materials obtained in Examples 1-41 (especially Examples 1-9, 11-16, 21-26, 28-41), the thickness is sufficiently maintained even after dyeing, and the texture Also confirmed to be very flexible.

  As described above, according to the present invention, a method for manufacturing a leather material using a water-based polyurethane resin in consideration of environmental load and VOC problems, migration is suppressed, and the thickness of the fiber substrate is maintained. A method for producing a leather material capable of efficiently and reliably obtaining a leather material with excellent friction fastness without causing odor at a suitable coagulation temperature, and a leather material obtained by the production method are provided. It becomes possible to do.

  Therefore, the production method of the present invention is particularly useful as an industrial production method for leather materials, and the leather material obtained by the production method of the present invention has no organic solvent remaining in the leather materials. Since the adverse effects on the human body such as skin disorders have also been eliminated, it can be used as it is in industrial fields such as vehicles, furniture, clothing, bags, shoes, bags, sundries, polishing, etc. It can also be used as a stable and high-quality leather material.

Claims (11)

(A) an aqueous polyurethane resin having an anionic group, (B) at least one inorganic acid ammonium salt selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride, (D) a weight average molecular weight of 2,000 to 10 A nonionic surfactant containing 75% by mass or more of an oxyalkylene group in the molecule and (E) a mixed solution containing water is impregnated into a fiber base material and then dried, and then a leather material As well as
The (A) aqueous polyurethane resin has the following conditions (i) to (ii):
(I) It has a carboxyl group and / or a carboxylate group, and the total content of the carboxyl group and the carboxylate group is 0.5 to 4.0% by mass,
(Ii) It has a sulfo group and / or a sulfonate group, and the total content of the sulfo group and the sulfonate group is 0.1 to 1.0% by mass,
A polyurethane resin satisfying at least one of
A method for producing a leather material characterized by the above.   In the mixed solution, the mixing ratio (A: B: D) of the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, and the (D) nonionic surfactant is 100: It is 0.1-50: 2-100, The manufacturing method of the leather material of Claim 1 characterized by the above-mentioned. (A) an aqueous polyurethane resin having an anionic group, (B) at least one inorganic acid ammonium salt selected from the group consisting of ammonium sulfate, ammonium phosphate and ammonium chloride, (D) a weight average molecular weight of 2,000 to 10 A nonionic surfactant containing 75% by mass or more of an oxyalkylene group in the molecule and (E) a mixed solution containing water is impregnated into a fiber base material and then dried, and then a leather material As well as
The mixed solution further contains (C) a water-soluble organic polymer ;
Method of manufacturing a skin leather timber it said.   In the mixed solution, a blending ratio of the (A) aqueous polyurethane resin, the (B) inorganic acid ammonium salt, the (C) water-soluble organic polymer, and the (D) nonionic surfactant (A: B: C: D) is 100: 0.1-50: 0.1-50: 2-100 by mass ratio, The manufacturing method of the material for leathers of Claim 3 characterized by the above-mentioned.   The method for producing a leather material according to claim 3 or 4, wherein the water-soluble organic polymer (C) is at least one selected from the group consisting of hydroxyethyl cellulose, xanthan gum and sodium alginate. (A) the aqueous polyurethane resin, according to claim 3-5, characterized in that a polyurethane resin having a carboxy group, a carboxylate group, at least one anionic group selected from the group consisting of a sulfo group and sulfonate group The manufacturing method of the leather material as described in any one of these. The (A) aqueous polyurethane resin has the following conditions (i) to (ii):
(I) It has a carboxyl group and / or a carboxylate group, and the total content of the carboxyl group and the carboxylate group is 0.5 to 4.0% by mass,
(Ii) It has a sulfo group and / or a sulfonate group, and the total content of the sulfo group and the sulfonate group is 0.1 to 1.0% by mass,
Method for producing a leather timber according to any one of claims 3-6, characterized in that the polyurethane resins satisfying at least any one of. The (A) aqueous polyurethane resin is
(I) (a) Organic polyisocyanate, (b) polyol and (c) neutralized isocyanate group-terminated prepolymer having a carboxylate group obtained by reacting a compound having a carboxy group and two or more active hydrogens Having a carboxy group and / or a carboxylate group obtained by emulsifying and dispersing in water by self-emulsification and (d) a chain elongation reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin, and
(II) (a) organic polyisocyanate, (b) polyol and (e) sulfonate group obtained by reacting two or more amino groups and / or imino groups with a polyamine compound having a sulfo group and / or a sulfonate group It was obtained by emulsifying and dispersing an isocyanate group-terminated prepolymer neutralized product having water in water by self-emulsification and (d) a chain extension reaction using a polyamine compound having two or more amino groups and / or imino groups. Polyurethane resin having sulfo group and / or sulfonate group,
It is at least 1 polyurethane resin selected from the group which consists of, The manufacturing method of the material for leathers as described in any one of Claims 1-7 characterized by the above-mentioned.   The method for producing a leather material according to any one of claims 1 to 8, wherein the mixed solution has a heat-sensitive coagulation temperature of 30 to 80 ° C.   2. The fiber base material is impregnated with the mixed solution so that a component derived from the water-based polyurethane resin (A) is fixed up to 10% of the central portion in the thickness of the leather material. The manufacturing method of the leather material as described in any one of -9.   The (D) nonionic surfactant is at least one selected from the group consisting of an alkylene oxide addition polymer having 2 to 4 carbon atoms and an alkylene oxide addition product of glycerol. The method for producing a leather material according to any one of 10.