KR101665719B1 - Method for producing leather material and leather material - Google Patents

Abstract

The present invention relates to a leather material for impregnating a fiber substrate with a mixed liquid containing (A) a polyurethane resin having a carboxyl group and / or a carboxylate group, (B) an ammonium salt of an inorganic acid and (C) water, Of the present invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a leather-

The present invention relates to a method for producing a leather-like material and a leather-like material, and more particularly, to a method for producing a leather-like material which is manufactured using an aqueous polyurethane resin and can be preferably used as artificial leather or synthetic leather, The present invention relates to a leather wearing material.

BACKGROUND ART [0002] As a substitute for natural leather, synthetic leather composed of an artificial leather and a polyurethane resin composed of a fiber base material including a polyurethane resin and a nonwoven fabric and a fiber base material including a fabric or a knitted fabric has been produced in many cases. Such artificial leather and synthetic leather are, for example, impregnated or coated with an organic solvent solution of a polyurethane resin in a fiber base material so as to be similar to natural leather, and the polyurethane resin is compatible with the organic solvent as a poor solvent Which is then passed through a coagulating solution (usually water) to coagulate, followed by washing with water and drying.

However, since organic solvents such as dimethylformamide, which are widely used in the wet coagulation method, are highly flammable and have high toxicity, there is a risk of fire, and there is a risk of environmental pollution such as deterioration of working environment, I was also concerned about the problem. In addition, although a manufacturing method including a step of recovering an organic solvent generated to solve such a problem is also performed, there remains a problem that a large amount of disposal cost and labor force are required. In addition, the artificial leather and the synthetic leather obtained by using the organic solvent solution of the polyurethane resin have an influence on the human body such as skin trouble because the organic solvent remains in the leather. For this reason, studies have been made to shift the polyurethane resin fixed on the fiber substrate from an organic solvent type to an aqueous polyurethane resin.

The manufacturing method of the artificial leather using such an aqueous polyurethane resin does not use an organic solvent, and therefore it is possible to reduce the cost required for recovery and to improve the working environment, to improve the environment such as air pollution, But artificial leather and synthetic leather having satisfactory feel and physical properties were not obtained when compared with artificial leather and synthetic leather obtained by using an organic solvent solution of a polyurethane resin. A major cause of such a problem is so-called migration, in which when the aqueous polyurethane resin is impregnated into the fiber substrate and dry-dried by hot air, the aqueous polyurethane resin migrates to the fiber substrate surface as the water evaporates from the fiber substrate surface . That is, due to such migration, in the production method of artificial leather using an aqueous polyurethane resin, the aqueous polyurethane resin migrates to the surface of the fiber substrate, and the polyurethane resin hardly adheres to the inside of the fiber substrate, Artificial leather, synthetic leather, which has a hard feel and lacks nap sensation. Therefore, various attempts have been made to solve the problem of migration in a method of producing an artificial leather or the like using an aqueous polyurethane resin.

For example, in Japanese Patent Publication (Kokoku) No. 55-51076 (Patent Document 1), a synthetic resin emulsion imparted with heat-coagulation property by adding a thermal gelling agent is impregnated into a fiber cloth, A process for producing a leather-like product by solidifying a synthetic resin emulsion is disclosed.

In this method, however, migration inhibition is improved, but a part of the impregnation solution flows out to the bath and solidifies, and the coagulated gel material is reattached to the surface of the workpiece, resulting in a problem that the feeling of the obtained leather is deteriorated. Further, in such a method, there is a problem that the thermal coagulation property is lowered as the polyurethane resin concentration is lowered, and a part of the impregnation liquid tends to flow out into the hot water, and the feeling of the obtained leather-like material is further deteriorated.

Japanese Patent Application Laid-Open No. 6-316877 (Patent Document 2) discloses a method for producing artificial leather wherein a water-based resin composition obtained by dissolving inorganic salts in a forced emulsified nonionic emulsion is applied to a non- .

However, in such a method, migration inhibition is improved, but there is a processing problem that the stability of the treatment bath is deteriorated depending on the concentration of the inorganic salt to be compounded. Further, since the nonionic surfactant and the inorganic salt remain in the fibrous base material, the obtained leather-like wood material is not only tough but hard to touch, low in abrasion resistance, and insufficient in rubbing fastness.

Further, in Japanese Patent Application Laid-Open No. 2000-290879 (Patent Document 3), a water-based resin composition comprising a water-based urethane resin having a thermal coagulation temperature of 40 to 90 ° C and an associative thickener is impregnated or coated on a fiber material gas, There is disclosed a method for producing a fiber sheet-like composite material in which the water-based resin composition is thermally coagulated with steam.

However, since the nonionic surfactant and the associative thickener remain in the fibrous material gas, the resultant leather-like material is also hard to touch, hard, low in abrasion resistance, and insufficient in fastness to rubbing, although migration prevention is improved by such a method .

Further, in Japanese Patent Application Laid-Open No. 2003-138131 (Patent Document 4), a carboxylic acid salt type polyurethane resin containing a nonionic surfactant having an HLB of 10 to 18 and an inorganic salt is added to a fibrous material gas and heat coagulated And a method for producing the sheet material for leather.

However, also in this method, problems such as surfactants and inorganic salts occurred in the same manner as in the methods described in the above Patent Documents 2 and 3, and the leather extrudate obtained was also hard in texture and hard in rubbing fastness.

In the methods described in the above Patent Documents 2 to 4, residues such as nonionic surfactant and associative thickener can be removed to some extent by repeating the steps such as washing with water or bathing. However, This problem can not be avoided because it is difficult. In addition, repeating the process such as washing with water or hot water causes an increase in the number of processing steps, leading to an economical problem. Therefore, there is a demand for a production method capable of obtaining a leather-like material having a sufficient feeling and physical properties, which can be easily removed by washing with water or washing as little as possible.

Japanese Patent Application Laid-Open No. 2006-36960 (Patent Document 5) discloses a method for producing a leather-like material in which a fiber base material is impregnated with a mixed solution containing a carboxyl group-containing polyurethane resin, an ammonium salt of a carboxylic acid and water, .

However, although this method can solve the problem of migration, there are new problems such as odor due to ammonia gas generated during drying. Further, when an ammonium salt of a carboxylic acid having a small number of carbon atoms such as ammonium formate or ammonium acetate is used as the carboxylic acid ammonium salt, there arises a problem that the apparatus is corroded by the carboxylic acid volatilized by heating and drying, Process improvement is needed. On the other hand, when an ammonium salt of a carboxylic acid having a large number of carbon atoms is used, the carboxylic acid is not volatilized during heating and drying, but it is necessary to use a large amount of the carboxylic acid if it is desired to obtain a desired migration inhibition. Further, when a polycarbodiimide compound is used in combination to improve the durability of the resin such as heat resistance, since it reacts with the carboxylic acid ammonium salt, it becomes difficult to obtain sufficient migration inhibition even by using a large amount of the carboxylic acid ammonium salt.

As described above, in the method for producing artificial leather using an aqueous polyurethane resin, it is possible to sufficiently prevent migration, fix the polyurethane resin uniformly to the fiber base material, A method for producing a leather-like material having a feel and quality has not been obtained, and measures against VOC (volatile organic compound) generated in the process are required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a method of manufacturing a leather-like material using an aqueous polyurethane resin, A method of manufacturing a leather material capable of efficiently and reliably obtaining a leather-like material excellent in physical properties such as wear resistance, friction fastness, and the like, which is free from odor and apparatus corrosion caused by generated gas, The present invention has been made in view of the above problems.

As a result of intensive researches to achieve the above object, the present inventors have found that, by impregnating a fibrous substrate with a mixed liquid containing a specific aqueous polyurethane resin, an inorganic acid salt, and water and then drying the aqueous polyurethane resin, A polyurethane resin is uniformly adhered to the inside of the fibrous base material to obtain a leather wearing material having a soft feeling and a sufficient physical property.

That is, the method for producing a leather-like material of the present invention comprises the steps of (A) impregnating a fiber substrate with a mixed solution containing a polyurethane resin having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid and (C) , Followed by drying to obtain a leather stock.

(A) :( B) = 100: 0.1 to 10: 1 as the mass ratio of the solid content of the polyurethane resin (A) having carboxyl group and / or carboxylate group and the ammonium salt of inorganic acid (B) 100: 50. The pH of the mixed solution is preferably 5.0 to 7.0, and the thermal coagulation temperature is preferably 30 to 80 ° C.

As the inorganic acid in the ammonium salt of the inorganic acid (B) according to the present invention, sulfuric acid and / or phosphoric acid are preferable.

The polyurethane resin (A) having a carboxyl group and / or a carboxylate group according to the present invention is obtained by reacting (a) an organic diisocyanate, (b) a polyol and (c) a carboxyl group with a compound having two or more active hydrogen Neutralizing the resulting isocyanate-terminated prepolymer having a carboxyl group by emulsion-dispersing in water by emulsification, and (d) subjecting the carboxyl group and / or carboxyl group obtained by a chain extension reaction using a polyamine compound having two or more amino groups and / Or a polyurethane resin having a carboxylate group is preferable. The polyurethane resin having carboxyl group and / or carboxylate group (A) preferably has a total of carboxyl group content and carboxylate group content of 0.5 to 4.0% by mass.

The leather-like material of the present invention is obtained by the production method of the present invention.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to sufficiently prevent migration even though it is a method for producing a leather-like material using a water-based polyurethane resin taking into account the problems of the environment and the VOC, It is possible to efficiently and reliably obtain a leather-like material excellent in physical properties such as abrasion resistance, friction fastness, and the like, without the use of a leather-like material, and a leather-like material obtained by the manufacturing method thereof .

Hereinafter, the present invention will be described in detail based on its preferred embodiments.

The method for producing a leather-like material of the present invention comprises impregnating a fibrous substrate with a mixed liquid comprising (A) a polyurethane resin having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid, and (C) water, To obtain a leather stock material.

The polyurethane resin (A) having a carboxyl group and / or a carboxylate group according to the present invention is a polyurethane resin having a carboxyl group and / or a carboxylate group as a hydrophilic component in the urethane resin skeleton. Examples of the polyurethane resin having (A) carboxyl group and / or carboxylate group include (a) an organic diisocyanate, (b) a polyol and (c) a carboxyl group having a carboxyl group obtained by reacting a carboxyl group with a compound having two or more active hydrogen (D) a carboxyl group and / or carboxylate obtained by performing a chain extension reaction using a polyamine compound having two or more amino groups and / or an imino group, after neutralizing the isocyanate-terminated prepolymer and emulsifying it in water by self- Group can be preferably used.

The organic diisocyanate (a) is not particularly limited, and an aliphatic diisocyanate having two isocyanate groups, an alicyclic diisocyanate and an aromatic diisocyanate can be used. Examples of the organic diisocyanate (a) include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornene Alicyclic diisocyanate compounds such as nandi isocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; alicyclic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolylidine diisocyanate, xylylene diisocyanate, And aromatic diisocyanate compounds such as isocyanate. These diisocyanate compounds may be used singly or in combination of two or more. Among these organic diisocyanates (a), the aliphatic diisocyanate compound and the alicyclic diisocyanate compound can be preferably used because they provide non-sulfur modification to the leather stock, and in particular, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane Diisocyanate, norbornadiisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane can be preferably used.

The polyol (b) is not particularly limited as long as it has two or more hydroxyl groups, and a polyether ester polyol having an ether bond and an ester bond in addition to a polyester polyol, polycarbonate polyol and polyether polyol Can be used.

Examples of such polyester polyols include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene Poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate, polycondensation of 1,6-hexanediol with dimer acid, 1,6- hexanediol and adipic acid A condensation product of dimer acid, a condensation product of nonanediol and dimer acid, a condensation product of ethylene glycol and 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, 1,6-hexanediol Polycarbonate polyol, and the like.

Examples of the polyether polyol include homopolymers, block copolymers and random copolymers of polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and copolymers of ethylene oxide and propylene oxide, ethylene oxide and butylene oxide Random copolymers and block copolymers.

These polyols (b) may be used singly or in combination of two or more. The average molecular weight of the polyol (b) is preferably 500 to 5000, more preferably 1000 to 3000. From the viewpoint that sufficient durability can be imparted to the leather-like material by the obtained polyurethane resin having a carboxyl group and / or carboxylate group, it is preferable to use polycarbonate polyol or polyether polyol as the polyol (b) desirable.

Examples of the compound (c) having a carboxyl group and two or more active hydrogens include 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. As a compound having such a carboxyl group and two or more active hydrogens, a polyester polyol having a pendant-type carboxyl group obtained by reacting a diol having a carboxyl group with an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid may be used. Further, instead of the diol having a carboxyl group, a diol having no carboxyl group as a diol component may be mixed and reacted. The compound having such a carboxyl group and two or more active hydrogens may be used singly or in combination of two or more.

When preparing an isocyanate-terminated prepolymer having a carboxyl group by reacting (a) an organic diisocyanate, (b) a polyol, and (c) a carboxyl group and a compound having two or more active hydrogens, A low molecular weight double-side-chain agent having a hydrogen atom can be used.

The low molecular weight double-chain extender having two or more active hydrogen atoms preferably has a molecular weight of 400 or less, and particularly preferably 300 or less. Examples of the low-molecular weight double-bladder extender include low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylol propane, pentaerythritol, sorbitol ; And low molecular weight polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine and triethylenetetramine. These low molecular weight double-chain extenders having two or more active hydrogen atoms may be used singly or in combination of two or more.

In the present invention, a specific method for producing an isocyanate-terminated prepolymer having a carboxyl group is not particularly limited, and for example, there can be used a so-called one-shot method, a multi-step isocyanate- . ≪ / RTI > The reaction temperature at this time is preferably 40 to 150 ° C. In this reaction, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine or N-methylmorpholine may be added Can be added. Further, an organic solvent which does not react with isocyanate groups during or after the reaction can be added. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone and the like can be used.

In the present invention, neutralization of the isocyanate-terminated prepolymer having a carboxyl group in the present invention can be carried out by appropriately known methods before or after the production of the isocyanate-terminated prepolymer having a carboxyl group. The compound used for neutralizing the isocyanate-terminated prepolymer having a carboxyl group is not particularly limited and includes, for example, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N, N-dimethyl monoethanol amine, N, N-diethyl monoethanol amine, triethanol amine and other amines, potassium hydroxide, sodium hydroxide and ammonia. Among these compounds, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.

In the present invention, the emulsifying apparatus used for emulsifying and dispersing the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group in water is not particularly limited, and examples thereof include a homomixer, a homogenizer and a dispenser . When the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group is emulsified and dispersed in water, the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group is dissolved in water at a temperature ranging from room temperature to 40 ° C It is preferable that the reaction between the isocyanate group and water is suppressed to the maximum by emulsion and dispersion. When emulsifying and dispersing as described above, a reaction inhibitor such as phosphoric acid, sodium dihydrogenphosphate, disodium hydrogenphosphate, p-toluenesulfonic acid, adipic acid or benzoyl chloride may be added as needed.

Also, in the present invention, after neutralization of an isocyanate-terminated prepolymer having carboxyl groups is emulsified and dispersed in water, (d) a polyamine compound having two or more amino groups and / or imino groups is subjected to a chain extension reaction, (A) an emulsified dispersion of a polyurethane resin having a carboxyl group and / or a carboxylate group can be obtained.

Examples of the polyamine compound having two or more amino groups and / or imino groups (d) include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, Diamines such as piperazine, isophoronediamine, norbornenediamine, diaminodiphenylmethane, tolylene diamine, and xylylenediamine; Polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and tris (2-aminoethyl) amine; Amide amines derived from di-primary amines and monocarboxylic acids; Water-soluble amine derivatives such as monoketimines of di-primary amines; 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, Hydrazine derivatives such as 1'-ethylenehydrazine, 1,1'-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.

In the present invention, the chain extension reaction of a neutralized product of an isocyanate-terminated prepolymer having a carboxyl group is carried out by reacting an emulsified dispersion of a neutralized product of an isocyanate-terminated prepolymer having a carboxyl group with (d) an amino group and / Can be added. Also, (d) an emulsified dispersion of a neutralized product of an isocyanate-terminated prepolymer having a carboxyl group may be added to a polyamine compound having two or more amino groups and / or imino groups. The reaction for the chain extension is preferably carried out at a reaction temperature of 20 to 40 DEG C, and is usually completed within a period of 30 to 120 minutes. When an organic solvent is used to prepare an isocyanate group-terminated prepolymer having a carboxyl group, it is preferable to remove the organic solvent by, for example, distillation under reduced pressure after completing the chain extension reaction.

In the present invention, the value of the 100% modulus of the (A) polyurethane resin having a carboxyl group and / or a carboxylate group is preferably 0.5 to 20 MPa, more preferably 2 to 6 MPa. When the value of 100% modulus is less than the above lower limit, a leather article with a soft touch feeling can be obtained, but wear resistance tends to be weak. On the other hand, when the value is above the upper limit, the obtained leather- . Here, the 100% modulus value was measured using a dumbbell top three test piece in accordance with JIS K 6251 (2004), and the elongation at a predetermined elongation at 100% elongation (at 2 times elongation) Stress (MPa) is the value.

In the present invention, the total of the carboxyl group content and the carboxylate group content in the (A) polyurethane resin having a carboxyl group and / or carboxylate group is preferably 0.5 to 4.0 mass%, more preferably 1.0 to 2.0 mass% More preferable. When the sum of the carboxyl group content and the carboxylate group content is less than the above lower limit, the storage stability of the obtained polyurethane resin having carboxyl group and / or carboxylate group (A) tends to deteriorate, while if it exceeds the upper limit, The heat-coagulating temperature which is generated when mixed with the ammonium salt of the inorganic acid (B) is high, and the effect of prevention of migration tends to be weakened at the time of producing the leather-like material.

Examples of the inorganic acid in the ammonium salt of the inorganic acid (B) according to the present invention include perchloric acid, carbonic acid, sulfuric acid, persulfuric acid, sulfurous acid, phosphoric acid and nitric acid. Of these inorganic acids, sulfuric acid and / or phosphoric acid are preferable because of excellent migration prevention effect. Specific examples of the ammonium salt of the inorganic acid (B) include ammonium persulfate, ammonium perchlorate, ammonium carbonate, ammonium sulfate, ammonium hydrogen sulfate, ammonium sulfite, ammonium hydrogen sulfite, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium persulfate, Ammonium and the like. Of the ammonium salts of the inorganic acid (B), ammonium sulfate, ammonium dihydrogen phosphate (ammonium hydrogen sulfate) and the like can be easily removed from the ammonium salt of the inorganic acid (B) due to safety of handling, volatilization during drying, And ammonium dihydrogenphosphate can be preferably used. The ammonium dihydrogenphosphate can be used alone, but it is preferable to use the ammonium dihydrogenphosphate in combination with ammonium dihydrogenphosphate.

In the method for producing a leather-like material of the present invention, when the (B) ammonium salt of an inorganic acid is mixed with the emulsified dispersion of the polyurethane resin (A) having a carboxyl group and / or carboxylate group, the ammonium salt of the inorganic acid (B) ), It is possible to mix (A) the emulsified dispersion of a polyurethane resin having a carboxyl group and / or a carboxylate group, (A) the stability of the emulsion dispersion of a polyurethane resin having a carboxyl group and / It is preferable to mix the ammonium salt of the inorganic acid (B) in an aqueous solution.

The concentration of the ammonium salt of the inorganic acid in the aqueous solution of the ammonium salt of the inorganic acid (B) is preferably 1 to 50% by mass, more preferably 10 to 30% by mass. In the case where the concentration of the ammonium salt of the inorganic acid (B) in the aqueous solution is less than the lower limit described above, in order to exhibit the migration-preventing property at the time of drying, (A) an emulsified dispersion of a polyurethane resin having a carboxyl group and / It is necessary to add a large amount of the above-mentioned aqueous solution, thereby lowering the concentration of the polyurethane resin having a carboxyl group and / or a carboxylate group in the mixed solution (A). Therefore, in order to fix a polyurethane resin having a necessary amount of carboxyl group and / or carboxylate group to the fiber substrate, it is necessary to impregnate the fiber substrate with a large amount of the mixed solution, and the amount of moisture to be volatilized during drying is increased, Economic tends to deteriorate. On the other hand, when the concentration of the ammonium salt of the inorganic acid (B) in the above aqueous solution exceeds the upper limit, precipitates are formed upon mixing with the emulsified dispersion of the polyurethane resin (A) having a carboxyl group and / or a carboxylate group, The stability of the emulsified dispersion tends to be impaired.

The water (C) according to the present invention has a role as a solvent when mixing (A) a polyurethane resin having a carboxyl group and / or a carboxylate group and (B) an ammonium salt of an inorganic acid, Can be preferably used.

In the present invention, a method for producing a mixed liquid containing (A) a polyurethane resin having a carboxyl group and / or a carboxylate group, (B) an ammonium salt of an inorganic acid and (C) water is not particularly limited, Can be used.

(A) :( B) = 100: 0.1 to 100 (mass%) in terms of the solid content in the mixture liquid of the polyurethane resin (A) having a carboxyl group and / or carboxylate group and the ammonium salt : 50, and more preferably 100: 1 to 100: 40. When the compounding ratio is more than 100: 0.1, that is, when the compounding ratio of the ammonium salt of the inorganic acid is less than 0.1, the migration preventing effect tends to be weakened in the drying step. When the compounding ratio is less than 100: 50, When the compounding ratio is more than 50, the mixed liquid tends to gel in the summer air temperature atmosphere. The solid content in the present invention refers to a residue after heating the sample for 3 hours under a condition of a temperature of 105 占 폚.

Further, the temperature of the heat-coagulation of the mixed liquid is preferably 30 to 80 캜, more preferably 40 to 70 캜. Here, the heat coagulation temperature is a temperature at which the contents are lost in flowability and solidified when 50 g of the above mixed solution is taken in a 100-mL glass beaker and the beaker is gradually heated in a hot water bath at 95 캜 while stirring the contents. When the thermal coagulation temperature is lower than the lower limit, the mixture tends to gel in the atmospheric temperature of summer. When the upper limit is exceeded, the thermal stability is not clearly expressed, and migration prevention tendency is weakened in the drying process .

The content of the carboxyl group and / or carboxylate group-containing polyurethane resin (A) in the mixed solution is preferably 5 to 40% by mass, more preferably 10 to 30% by mass in terms of solid content. If the content of the polyurethane resin having a carboxyl group and / or carboxylate group is less than the above lower limit, since a large amount of the mixed solution is impregnated to the fibrous base material in order to fix the required amount of the polyurethane resin, The drying time becomes longer and the economical efficiency tends to deteriorate. On the other hand, when the content of the carboxyl group and / or the carboxyl group-containing polyurethane resin exceeds the upper limit, the stability of the mixed solution tends to deteriorate.

When the mixed liquid containing the conventional carboxyl group and / or carboxylate group-containing polyurethane resin becomes acidic, the emulsion stability is lowered, so that it is difficult to use it in the production of leather materials. However, (Preferably 5.0 to 7.0, more preferably 5.5 to 6.8, particularly preferably 6.0 to 6.5), the emulsification of the polyurethane resin having a carboxyl group and / or a carboxylate group is stable, It is possible to use.

Further, the fibrous substrate according to the present invention is not particularly limited, and a woven fabric, a knitted fabric, or a nonwoven fabric can be preferably used. As a material for such a fiber base material, a feeling and quality close to that of natural leather can be obtained, and therefore polyamide fibers and polyester fibers are preferably used.

The thickness of the nonwoven fabric thread in the nonwoven fabric used as the fiber base material is preferably 2.0 dtex or less from the viewpoint of improving the feeling of the resultant leather-like sheet material. If the thickness of the yarn of the nonwoven fabric exceeds 2.0 dtex, the texture of the leather-like material tends to be rough, hard, and dignified.

The density of such a nonwoven fabric is preferably 0.2 to 0.7 g / cm3, more preferably 0.30 to 0.55 g / cm3. If the density of the nonwoven fabric is less than the lower limit described above, the abrasion resistance of the resultant leather stock tends to deteriorate. If a large amount of the polyurethane resin is fixed in order to compensate for this, the texture of the resultant leather stock becomes rough and hard, There is a tendency. On the other hand, if the density of the nonwoven fabric exceeds the upper limit, the resulting leather-like material tends to feel rough and hard, and the durability tends to be impaired.

In the method for producing a leather-like member of the present invention, a mixed liquid containing (A) a polyurethane resin having a carboxyl group and / or a carboxylate group, (B) an ammonium salt of an inorganic acid and (C) water, Various additives may be added to impart processing aptitude in the range. Examples of such additives include various penetrating agents such as lower alcohols, glycol solvents, alcohol-based nonionic surfactants, acetylene glycol-based special surfactants, silicone surfactants, and fluorine surfactants; Various stabilizers such as antioxidants, photostabilizers, and ultraviolet absorbers; Various antifoaming agents such as mineral oil system and silicone system; Coloring agents such as urethane catalysts, plasticizers and pigments, and time-lengthening agents for solubility. These additives may be used alone or in combination of two or more.

Among these additives, it is particularly preferable to add a penetrating agent. By using the penetrating agent, it is possible to rapidly impregnate the fiber base material with the mixed solution, and at the same time, an effect of uniformly bonding the polyurethane resin to the fiber base material can be obtained. The penetrating agent is not particularly limited as long as it is generally used, but it is particularly preferable to use a lower alcohol, a glycol solvent, or an alcoholic nonionic surfactant.

Further, in the method for producing a leather-like material of the present invention, the objective of the present invention is impaired in a mixed liquid comprising (A) a polyurethane resin having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid, and (C) A cross-linking agent capable of reacting with a carboxyl group may be added in order to impart processing aptitude in a range not to be used. Examples of such crosslinking agents include oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, block isocyanate crosslinking agents, water dispersing isocyanate crosslinking agents and melamine crosslinking agents. These crosslinking agents may be used alone or in combination of two or more.

(A) a polyurethane resin having a carboxyl group and / or a carboxylate group, (B) an ammonium salt of an inorganic acid, and (C) water is used as a fiber for a fabric, a knitted fabric, The substrate is impregnated and then dried.

The method of impregnating the fiber substrate with the mixed solution is not particularly limited and conventionally known methods such as impregnation and atomization treatment including a deep nip method can be preferably used and the concentration of the mixed solution and the treatment conditions Etc. can be appropriately selected. Also, before impregnating a fiber substrate such as a fabric, a knitted fabric or a nonwoven fabric with a mixed solution containing (A) a polyurethane resin having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid, and (C) water, It is possible to perform the pre-treatment. In this pretreatment step, the fiber substrate is preferably treated with a polymer aqueous solution containing polyvinyl alcohol, carboxymethyl cellulose or the like, a silicone-based water repellent agent, a fluorine-based water repellent agent or the like in order to adjust the adhesive force between the fiber substrate and the polyurethane resin component.

Further, in the method for producing a leather-like member of the present invention, the method of impregnating the mixed liquid into the fiber substrate and then drying is not particularly limited, and for example, dry drying using hot air; Wet drying with a high tempering steamer (H.T.S.), a high pressure steamer (H.P.S.); And microwave irradiation drying can be used. Dry drying using hot air can be preferably used in view of continuous processability. These drying methods may be used singly or in combination of two or more kinds. When dry drying using the hot air is used, the treatment temperature is preferably 60 to 190 DEG C and the treatment time is preferably 1 to 20 minutes, more preferably 100 to 170 DEG C, and the treatment time is 2 To 5 minutes. By performing such drying, the polyurethane resin can be fixed to the inside of the fiber substrate.

In this manner, the fiber substrate is impregnated with a mixed liquid containing (A) a polyurethane resin having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid and (C) water, Can be obtained.

In the leather-like material of the present invention, the solid solid content of the polyurethane resin or the like in the leather-like material is not particularly limited, but a component derived from a polyurethane resin having (A) a carboxyl group and / or a carboxylate group in the leather- 10 to 90% by mass, and the component (B) derived from the ammonium salt of an inorganic acid is about 0.5 to 7.0% by mass.

Further, the leather-like material of the present invention can be dyed. Such a dyeing method is not particularly limited, and a dyeing method after line impregnation in which dyeing is performed after fixing a polyurethane resin to a fiber substrate, and a dyeing method after impregnating a polyurethane resin after dyeing the fiber substrate can be performed.

Further, the leather-like material of the present invention may be formed into a leather-like leather-like material by forming a skin layer. As a method for forming such a skin layer, any conventionally known method may be used and there is no particular limitation. For example, a skin layer material is applied to a release paper and water is evaporated to form a skin layer, an adhesive is applied on the skin layer, A release paper transfer method of bonding the leather-like material of the present invention to evaporate water or to bond after moisture is evaporated; A thermal transfer method in which a skin layer material is applied to a release paper sheet to form a skin layer by evaporating moisture, and a skin layer is bonded to the leather sheet material of the present invention by heat; A spraying method of directly spraying the skin layer material on the leather material of the present invention; A direct coating method in which a material for a skin layer is applied on a leather wearing material of the present invention by a gravure coater, a knife coater, a comer coater, an air knife coater or the like. Of these methods for forming a skin layer, the release paper transfer method is most preferable from the viewpoint of further improving the physical properties of the obtained skin layer. The material for the skin layer and the adhesive used in this release paper transfer method may be any material as long as it can be bonded to the leather-like material of the present invention. However, polyurethane resin is preferable from the viewpoints of surface and physical properties, It is preferable to use an aqueous or non-aqueous system.

The leather-like material of the present invention can be used for applications such as automobiles, furniture, medical supplies, shoes, bags, bag-shaped articles, sandals, miscellaneous goods, and polishing.

[Example]

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

The leather-like materials obtained by the respective Examples and Comparative Examples were evaluated by the following methods.

(1) Migration prevention property

The cross section of the leather-like material was observed at a magnification of 60 times using a scanning electron microscope (Scanning Electron Microscope S-2400 (Hitachi)) with respect to the leather-like material obtained by each example and each comparative example, Was compared with the fixing state of the polyurethane resin present on the surface portion of the nonwoven fabric and evaluated according to the following criteria.

Grade 5: There is no difference in the amount of resin fixation between the central portion and the surface portion of the cross section of the leather, and migration does not occur.

Level 4: There is almost no difference in the amount of resin adhesion between the center portion and the surface portion of the cross section of the leather, and migration does not occur.

Grade 3: There is a slight difference in the amount of resin fixation between the central portion and the surface portion of the cross section of the leather, and no resin fixation is observed in the 10% portion of the central portion of the total thickness.

Grade 2: Significant differences were observed in the amount of resin adherence at the central portion and the surface portion of the cross section of the leather sheet, and resin adhesion was not observed in the 30% portion of the central portion of the total thickness.

Class 1: In the cross section of the cross section of the leather, a remarkable difference was observed in the amount of resin adhesion at the center portion and the surface portion, and no resin adhesion was observed in the 50% portion of the central portion.

(2) Abrasion test

(Soft wheel) CS (soft wheel) was produced by a Taber abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with the Taber method of JIS L 1096 (1999) with respect to the leather material obtained by each example and each comparative example. -10, and the weight loss amount of the leather material after 1,000 times and 3000 times of abrasion was expressed as abrasion amount. In addition, as the wear amount is smaller, the wear resistance of the leather-like member is improved.

(3) Friction fastness

200 g of a load was applied to the leather-like material obtained by each example and each comparative example according to JIS L 0849 (2004) by a class-type friction tester (manufactured by Dai-ichi Kogei Seiki Seisakusho Co., Ltd.) The wet friction fastness was measured. The rubbing fastness was measured by comparing the degree of contamination of cotton calico using the gray scale for contamination according to the following criteria.

Class 5: No contamination observed.

Class 4: Some contamination is observed.

Class 3: Pollution is clearly observed.

Class 2: Pollution is observed somewhat prominently.

Class 1: Significantly observed contamination.

(4) presence or absence of residues

With respect to the content of the components other than the nonwoven fabric and the polyurethane resin (residues such as surfactants) in the leather-like material, the leather-like material obtained in each of the Examples and Comparative Examples was subjected to a Soxhlet extractor , And the extraction amount was 1.0% by mass or more and the residual amount was less than 1.0% by mass.

(5) texture

The feel of the leather material obtained by each example and each comparative example was evaluated according to the following criteria in five levels of 5th grade (flexible) to 1st grade (coarse and hard).

Grade 5: Flexible, very resilient texture of rebound.

Grade 4: Flexible, resilient, rich texture.

Grade 3: Texture lacking flexibility and elasticity of steam and repulsion.

Grade 2: slightly rough, hard, and paper-like (like paper) texture.

Level 1: Rough but hard, like paper (like paper) texture.

(6) odor during drying

In each of the Examples and Comparative Examples, odor of ammonia and acid when dried with a hot-air dryer was evaluated by sensory evaluation.

A: No odor.

B: There is a little odor.

C: A stinking stink of nose.

[Synthesis Examples and Comparative Synthesis Examples]

Hereinafter, comparative synthesis examples of a polyurethane resin having a carboxyl group and a carboxylate group used in the present invention, and an aqueous polyurethane resin used in a comparative example are shown.

(Synthesis Example 1)

Neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 157.0 g of 1,6-hexanediol polycarbonate polyol (average molecular weight: 2000), 7.5 g of neopentyl glycol, 1.3 g of trimethylolpropane, , 9.5 g of 2-dimethylol propionic acid, 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone were charged and mixed homogeneously, 69.7 g of isophorone diisocyanate was added, and the mixture was reacted at 80 DEG C for 300 minutes To obtain a methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a carboxyl group in which the content of free isocyanate groups relative to nonvolatile matters was 1.9% by mass.

After the solution was cooled to 50 캜 or lower, 6.8 g of triethylamine was added and neutralization reaction was carried out at 40 캜 for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 421.9 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, an aqueous polyamine solution obtained by dissolving 5.2 g of a hydrogenated hydrazine of 60% by mass and 1.1 g of diethylene triamine in 20 g of water was added to the above dispersion, followed by a chain reaction at 35 DEG C for 60 minutes, followed by removal at 35 DEG C And a water dispersion of a polyurethane resin having a non-volatile content of 35.0 mass%, a viscosity of 120 mPa.s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 7.8 and a stable carboxyl group and carboxylate group with an average particle diameter of 90 nm ≪ / RTI >

The total of the carboxyl group content and the carboxylate group content in the polyurethane resin having carboxyl group and carboxylate group was 1.3% by mass and the value of 100% modulus was 2 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Synthesis Example 2)

A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 178.0 g of 1,6-hexanediol polycarbonate polyol (average molecular weight 2000), 0.9 g of trimethylolpropane, 2,2-dimethylolpropionic acid , 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone were charged and uniformly mixed. Thereafter, 56.9 g of dicyclohexylmethane diisocyanate was added, and the mixture was reacted at 80 DEG C for 420 minutes, A methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a carboxyl group with a content of a free isocyanate group of 1.2% by mass was obtained.

After the solution was cooled to 50 DEG C or lower, 6.7 g of triethylamine was added and the neutralization reaction was carried out at 40 DEG C for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 424.4 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, a polyamine aqueous solution obtained by dissolving 3.3 g of hydrogenated hydrazine (60% by mass) and 0.7 g of diethylene triamine in 20 g of water was added to the above dispersion, followed by chain reaction at 35 ° C for 60 minutes, And a water dispersion of a polyurethane resin having a non-volatile content of 35.0 mass%, a viscosity of 70 mPa ((BM viscometer, No. 1 rotor, 60 rpm), a pH value of 7.6 and a stable carboxyl group and carboxylate group with an average particle diameter of 120 nm ≪ / RTI >

The total of the carboxyl group content and the carboxylate group content in the carboxyl group and carboxyl group-containing polyurethane resin was 1.3% by mass, and the 100% modulus was 5 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Synthesis Example 3)

A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 141.9 g of polytetramethylene glycol (average molecular weight 2000), 30.8 g of 2,2-dimethylolpropionic acid, 0.001 g of dibutyltin dilaurate, And 105 g of ethyl ketone were charged and mixed homogeneously. Then, 72.3 g of hexamethylene diisocyanate was added and reacted at 80 DEG C for 180 minutes to obtain an isocyanate having a carboxyl group having 3.1% by mass of a free isocyanate group relative to the nonvolatile fraction To obtain a methyl ethyl ketone solution of a terminal prepolymer.

After the solution was cooled to 50 캜 or lower, 22.1 g of triethylamine was added and neutralization reaction was carried out at 40 캜 for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 402.6 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, a polyamine aqueous solution obtained by dissolving 8.6 g of a hydrogenated hydrazine of 60% by mass and 1.8 g of diethylene triamine in 20 g of water was added to the above dispersion, and the mixture was subjected to a chain reaction at 35 DEG C for 60 minutes. Then, And a water dispersion of a polyurethane resin having a nonvolatile matter content of 35.0% by mass, a viscosity of 50 mPa.s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 7.9 and a stable carboxyl group and carboxylate group with an average particle size of 150 nm ≪ / RTI >

The total of the carboxyl group content and carboxylate group content in the polyurethane resin having carboxyl group and carboxylate group was 4.2 mass% and the 100% modulus was 8 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Synthesis Example 4)

Neck flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 157.0 g of 1,6-hexanediol polycarbonate polyol (average molecular weight: 2000), 7.5 g of neopentyl glycol, 1.3 g of trimethylolpropane, , 9.5 g of 2-dimethylol propionic acid, 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone were charged and mixed homogeneously, 69.7 g of isophorone diisocyanate was added, and the mixture was reacted at 80 DEG C for 300 minutes To obtain a methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a carboxyl group in which the content of free isocyanate groups relative to nonvolatile matters was 1.9% by mass.

After the solution was cooled to 50 캜 or lower, 8.6 g of triethylamine was added and neutralization reaction was carried out at 40 캜 for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 420.1 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, an aqueous polyamine solution obtained by dissolving 5.2 g of a hydrogenated hydrazine of 60% by mass and 1.1 g of diethylene triamine in 20 g of water was added to the above dispersion, followed by a chain reaction at 35 DEG C for 60 minutes, followed by removal at 35 DEG C And a water dispersion of a polyurethane resin having a non-volatile content of 35.0 mass%, a viscosity of 180 mPa.s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 9.5 and a stable carboxyl group and carboxylate group with an average particle diameter of 70 nm ≪ / RTI >

The total of the carboxyl group content and the carboxylate group content in the carboxyl group and carboxyl group-containing polyurethane resin was 1.3% by mass and the 100% modulus was 2 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Synthesis Example 5)

Hexanediol polycarbonate polyol (average molecular weight: 2000), 2.9 g of 1,4-butanediol, 1.7 g of trimethylolpropane, and 0.35 g of trimethylolpropane were placed in a four-necked flask equipped with a stirrer, a reflux condenser, , 11.1 g of 2,2-dimethylolpropionic acid, 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone were charged and uniformly mixed, followed by addition of 83.2 g of dicyclohexylmethane diisocyanate, The reaction was carried out for 240 minutes to obtain a methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a carboxyl group having a content of free isocyanate groups relative to nonvolatile matters of 3.8% by mass.

After the solution was cooled to 50 DEG C or lower, 7.9 g of triethylamine was added and neutralization reaction was carried out at 40 DEG C for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 403.3 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, an aqueous polyamine solution obtained by dissolving 7.7 g of hydrogenated hydrazine of 60 mass% and 1.3 g of diethylene triamine in 20 g of water was added to the above dispersion, followed by chain reaction at 35 DEG C for 60 minutes, followed by degassing at 35 DEG C And a water dispersion of a polyurethane resin having a non-volatile content of 35.0 mass%, a viscosity of 40 mPa ((BM viscometer, No. 1 rotor, 60 rpm), a pH value of 8.0 and a stable carboxyl group and carboxylate group with an average particle diameter of 40 nm ≪ / RTI >

The total of the carboxyl group content and the carboxylate group content in the polyurethane resin having carboxyl group and carboxylate group was 1.5% by mass and the 100% modulus was 18 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Synthesis Example 6)

A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 134.3 g of 1,6-hexanediol polycarbonate polyol (average molecular weight 2000), 3.5 g of 1,4-butanediol, 3.8 g of trimethylolpropane , 10.9 g of 2,2-dimethylol propionic acid, 0.001 g of dibutyltin dilaurate and 105 g of methyl ethyl ketone were charged and uniformly mixed. Then, 92.6 g of dicyclohexylmethane diisocyanate was added, The reaction was carried out for 210 minutes to obtain a methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a carboxyl group having a content of free isocyanate groups relative to nonvolatile matters of 4.2 mass%.

After the solution was cooled to 50 DEG C or lower, 7.8 g of triethylamine was added and neutralization reaction was carried out at 40 DEG C for 30 minutes. Subsequently, the neutralized solution was cooled to 30 DEG C or lower, and 405.0 g of water was gradually added using a disper wing to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer having a carboxyl group to obtain a dispersion. Further, a polyamine aqueous solution obtained by dissolving 6.9 g of a hydrogenated hydrazine of 60% by mass and 2.0 g of diethylene triamine in 20 g of water was added to the above dispersion, followed by a chain reaction at 35 DEG C for 60 minutes, followed by filtration under reduced pressure at 35 DEG C And a water dispersion of a polyurethane resin having a nonvolatile matter content of 35.0 mass%, a viscosity of 230 mPa.s (BM viscometer, No. 2 rotor, 60 rpm), a pH value of 8.7 and a stable carboxyl group and carboxylate group with an average particle diameter of 90 nm ≪ / RTI >

The total of the carboxyl group content and the carboxylate group content in the carboxyl group and carboxyl group-containing polyurethane resin was 1.5% by mass and the 100% modulus was 23 MPa. The aqueous dispersion of the carboxyl group and the carboxylate group-containing polyurethane resin was not gelled even at 90 占 폚 heating and had no thermal coagulation property.

(Comparative Synthesis Example 1)

Necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 76.1 g of polytetramethylene glycol (average molecular weight 1000), a polyoxyethylene polypropylene glycol random copolymer glycol (average molecular weight 1000, oxyethylene group content 70 Mass%), 1.5 g of 1,4-butanediol, 1.9 g of trimethylol propane, 0.001 g of dibutyltin dilaurate and 60 g of methyl ethyl ketone were charged and uniformly mixed and then dicyclohexylmethane diisocyanate And the reaction was carried out at 80 DEG C for 300 minutes to obtain a methyl ethyl ketone solution of an isocyanate-terminated prepolymer having a content of free isocyanate groups relative to the nonvolatile matters of 2.1% by mass.

After cooling the solution to 30 占 폚 or lower, 0.1 g of decyl phosphate and 6.0 g of polyoxyethylene tristyryl phenyl ether (HLB = 15) were added and uniformly mixed. g was gradually added, and phase inversion emulsification and dispersion were carried out to obtain a dispersion. Further, an aqueous polyamine solution obtained by dissolving 2.0 g of piperazine hexahydrate and 0.8 g of diethylene triamine in 11.3 g of water was added to the above dispersion, subjected to a coloring-extension reaction at 35 DEG C for 90 minutes, and then a solvent was removed at 35 DEG C under reduced pressure , A nonvolatile matter content of 35.0% by mass, a viscosity of 50 mPa.s (BM viscometer, No. 1 rotor, 60 rpm), a pH value of 8.0, and an average particle diameter of 550 nm.

The total of the carboxyl group content and the carboxylate group content in the aqueous polyurethane resin was 0.0% by mass, and the 100% modulus was 2 MPa. The water dispersion of the aqueous polyurethane resin was gelatinized at 45 캜 and had heat-coagulability.

The properties of Synthesis Examples 1 to 6 and Comparative Synthesis Example 1 are collectively shown in Table 1 below.

[Examples 1 to 10 and Comparative Examples 1 to 6]

(Example 1)

100 g of the aqueous dispersion of the polyurethane resin having carboxyl group and carboxylate group obtained in Synthesis Example 1, 17.5 g of 20% by mass aqueous solution of ammonium sulfate, and 10 g of a Texport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The blending ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to ammonium sulfate was 100:10, the pH value was 6.2, the thermal coagulation temperature was 57 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

This mixed solution was impregnated into a nonwoven fabric (0.5 dtex, density 0.3 g / cm3) containing polyester fibers so as to be 250 mass% in a pickup using a slit mangle, followed by heating in a hot air drier [TBA SAFETY Oven SPH-200] Lt; 0 > C for 3 minutes and then at 150 < 0 > C for 3 minutes to obtain artificial leather. Further, the obtained artificial leather (leather-applied material) was dyed under the following conditions and subjected to RC soaping to obtain an artificial leather-dyed cloth (dyed leather-like material).

<Conditions for dyeing>

Dyeing machine: Mini color dyeing machine [TECSUNG KIKEN CO., LTD]

dyes:

Kayalon Microester Blue DX-LS conc [Nippon Kayaku Co., Ltd.] 0.10% o.w.f.

Kayaron Microester Yellow DX-LS [Nippon Kayaku Co., Ltd.] 2.00% o.w.f.

Kayaron Micro-ester Red DX-LS [Nippon Kayaku Co., Ltd.] 0.80% o.w.f.

Dyeing aid: Nikkasan Salt RM-340 (Nikkaga Chemical Co., Ltd.) 0.5 g / L

pH adjuster: 90% mass acetic acid 0.3 cc / L

Waste: (1:20)

Dyeing condition: 130 占 폚 占 60 minutes (heating rate 2 占 폚 / min).

<RC condition>

RC Bath: Sodium hydroxide 2 g / L

      Hydrosulfite 2 g / L

Waste: (1:20)

RC condition: 80 占 폚 × 20 minutes (heating rate 2 占 폚 / min).

(Example 2)

100 g of the aqueous dispersion of the carboxyl group-containing and polyurethane resin obtained in Synthesis Example 1, 23.3 g of a 30 mass% aqueous solution of ammonium sulfate, and 20 g of Texex BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 10.7 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to ammonium sulfate was 100:20, the pH value was 6.0, the thermal coagulation temperature was 45 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Example 3)

100 g of a water dispersion of a carboxyl group-containing and polyurethane resin obtained in Synthesis Example 1, 30.6 g of a 40% by mass aqueous solution of ammonium sulfate, 10 g of Texex BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 31.4 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group and ammonium sulfate in the mixed solution was 100:35, the pH value was 5.8, the heat coagulation temperature was 59 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 21% by mass.

An artificial leather-dyed cloth (leather-finished dyed leather) was obtained in the same manner as in Example 1 except that the mixed solution was impregnated so as to be 300% by mass of pickup.

(Example 4)

100 g of the aqueous dispersion of the carboxyl group-containing and polyurethane resin obtained in Synthesis Example 1, 1.8 g of a 40% by mass aqueous solution of ammonium sulfate and 1.8 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to ammonium sulfate was 100: 2, the pH value was 6.8, the thermal coagulation temperature was 70 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 34% by mass.

An artificial leather-dyed cloth (dyed leather-like material) was obtained in the same manner as in Example 1 except that the mixed solution was impregnated so as to have a pickup of 185 mass%.

 (Example 5)

100 g of a water dispersion of a carboxyl group and carboxylate group-containing polyurethane resin obtained in Synthesis Example 2, 17.5 g of a 20% by mass aqueous solution of ammonium sulfate, 10 g of Texexport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having carboxyl group and carboxylate group and ammonium sulfate in the mixed solution was 100:10, the pH value was 6.3, the heat coagulation temperature was 55 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Example 6)

100 g of the aqueous dispersion of the polyurethane resin having carboxyl group and carboxylate group obtained in Synthesis Example 3, 17.5 g of 20% by mass aqueous solution of ammonium sulfate, 10 g of Texex BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to ammonium sulfate was 100:10, the pH value was 6.2, the heat coagulation temperature was 52 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Example 7)

100 g of the polyurethane resin aqueous dispersion of the carboxyl group and carboxylate group obtained in Synthesis Example 4, 17.5 g of 20% by mass aqueous solution of ammonium sulfate, 10 g of Texexport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to ammonium sulfate was 100:10, the pH value was 6.2, the thermal coagulation temperature was 66 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Example 8)

100 g of the water dispersion of the carboxyl group and carboxylate group-containing polyurethane resin obtained in Synthesis Example 1, 17.5 g of a 20 mass% aqueous solution of diammonium hydrogenphosphate / ammonium dihydrogenphosphate (weight ratio 50/50), Carbodite E-02 [ 1.0 g of a carbodiimide crosslinking agent, trade name, manufactured by Nisshinbo K.K.), 6.0 g of a 50 mass% aqueous solution of Texapot BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) and 15.5 g of water And mixed to prepare a mixed solution. The mixing ratio of the carboxyl group and carboxylate group-containing polyurethane resin to the inorganic acid ammonium salt in the mixed solution was 100:10, the pH value was 6.3, the thermal coagulation temperature was 45 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Example 9)

100 g of the aqueous dispersion of the carboxyl group-containing and polyurethane resin obtained in Synthesis Example 5, 17.5 g of 20% by mass aqueous solution of ammonium sulfate, 10 g of Texex BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having carboxyl group and carboxylate group and ammonium sulfate in the mixed solution was 100:10, the pH value was 6.3, the heat coagulation temperature was 55 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

An artificial leather-dyed cloth (leather-finished dyed leather article) was obtained in the same manner as in Example 1 except that the mixed solution was impregnated so as to be 125% by mass of the pickup.

(Example 10)

100 g of the aqueous dispersion of the polyurethane resin having carboxyl group and carboxylate group obtained in Synthetic Example 6, 17.5 g of 20% by mass aqueous solution of ammonium sulfate, and 20 g of the aqueous solution of Texpot BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to the ammonium sulfate was 100:10, the pH value was 6.2, the thermal coagulation temperature was 50 ° C, the content of the polyurethane resin having a carboxyl group and a carboxylate group 25% by mass.

An artificial leather-dyed cloth (leather-finished dyed leather article) was obtained in the same manner as in Example 1 except that the mixed solution was impregnated so as to be 125% by mass of the pickup.

(Comparative Example 1)

100 g of a water dispersion of a carboxyl group and carboxylate group-containing polyurethane resin obtained in Synthesis Example 1, 6.0 g of a 50 mass% aqueous solution of Texport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) and 34.0 g Were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to the ammonium salt of an inorganic acid was 100: 0, the pH value was 7.5, the thermal coagulation temperature was 90 ° C or higher, the content of the carboxyl group and carboxyl group in the polyurethane resin The content was 25 mass%.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Comparative Example 2)

100 g of a water dispersion of a carboxyl group and a carboxylate group-containing polyurethane resin obtained in Synthesis Example 1, 17.5 g of a 10 mass% aqueous solution of sulfuric acid, 50 g of Texex BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0% by mass aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to sulfuric acid was 100: 5, the temperature of the coagulation was 10 ° C or lower, and the content of the polyurethane resin having a carboxyl group and a carboxylate group was 25% by mass.

Further, when the 10% by mass aqueous solution of sulfuric acid was added to the mixed solution, precipitates were observed from the mixed solution instantaneously, and therefore, no artificial leather-dyed cloth was produced. In addition, it was difficult to measure the pH.

(Comparative Example 3)

100 g of the aqueous dispersion of the aqueous polyurethane resin obtained in Comparative Synthesis Example 1, 6.0 g of a 50 mass% aqueous solution of Texport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) and 34.0 g of water were uniformly mixed To prepare a mixed solution. The mixing ratio of the aqueous polyurethane resin to the ammonium salt of the inorganic acid in the mixed solution was 100: 0, the pH value was 8.0, the thermal coagulation temperature was 45 占 폚, and the content of the aqueous polyurethane resin was 25 mass%.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Comparative Example 4)

100 g of the aqueous dispersion of the aqueous polyurethane resin obtained in Comparative Synthesis Example 1, 17.5 g of a 20 mass% aqueous solution of ammonium sulfate, and 50 mass% aqueous solution of Texapot BG (alcohol-based penetrant, trade name, manufactured by Nikkagaku K.K.) g and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the aqueous polyurethane resin to the ammonium salt of the inorganic acid in the mixed solution was 100:10, the pH value was 6.5, the heat coagulation temperature was 45 ° C, and the content of the aqueous polyurethane resin was 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Comparative Example 5)

100 g of the aqueous dispersion of the aqueous polyurethane resin obtained in Comparative Synthesis Example 1, 17.5 g of a 10 mass% aqueous solution of calcium chloride, and 6.0 g of a 50 mass% aqueous solution of Texpot BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) And 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the aqueous polyurethane resin and calcium chloride in the mixed solution was 100: 5, the pH value was 8.1, the heat coagulation temperature was 35 占 폚, and the content of the aqueous polyurethane resin was 25 mass%.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

(Comparative Example 6)

100 g of a water dispersion of a carboxyl group and a carboxylate group-containing polyurethane resin obtained in Synthesis Example 1, 17.5 g of a 10% by mass aqueous solution of ammonium formate, and 20 g of Texexport BG (alcohol-based penetrant, trade name, manufactured by Nikkaga Chemical Co., Ltd.) 6.0 g of a 50 mass% aqueous solution and 16.5 g of water were uniformly mixed to prepare a mixed solution. The mixing ratio of the polyurethane resin having a carboxyl group and a carboxylate group in the mixed solution to the ammonium formate was 100: 5, the pH value was 7.9, the thermal coagulation temperature was 45 ° C, the content of the carboxyl group and carboxyl group- 25% by mass.

The same process as in Example 1 was carried out except that such a mixed solution was used to obtain an artificial leather-dyed cloth (leather-dyed leather).

The evaluation results of the artificial leather dyed fabrics (dyed leather dyed fabrics) obtained in Examples 1 to 10 are shown in Table 2, and the evaluation of the artificial leather dyed fabrics (dyed leather dyed fabrics) obtained in Comparative Examples 1 and 3 to 6 The results are shown in Table 3.

Migration was not observed in the leather stocks obtained in Examples 1 to 9, and the resin was uniformly fixed to the inside of the nonwoven fabric. It was confirmed that by preventing migration as described above, a leather fastening material exhibiting excellent abrasion resistance is obtained that is very flexible in texture and has almost no change in wear amount at 1000 times and 3000 times in the abrasion resistance test. When the 100% modulus of the carboxyl group and the carboxyl group of the polyurethane resin is large (Example 10), the feeling of roughness is hard and hard, and the abrasion resistance test of 3000 times is slightly insufficient, If this is not the case, it can be used sufficiently. Further, it was confirmed that in the leather extrudate obtained in Examples 1 to 10, the amount of the residue remaining in the leather extrudate was very small, and the influence of the residue on the fastness to rubbing was also small.

On the other hand, in the leather-like material obtained in Comparative Example 1 using only a polyurethane resin having a carboxyl group and a carboxylate group without containing an ammonium salt of an inorganic acid, remarkable migration was observed at the time of drying, and the feeling was rough and hard. Further, in the abrasion resistance test of the leather material obtained in Comparative Example 1, when abraded 1,000 times, abrasion resistance was good, but when abrasion was performed 3,000 times, remarkable abrasion amount was observed and abrasion resistance was insufficient.

Further, in Comparative Example 2, an aqueous solution of sulfuric acid was used instead of the ammonium salt of inorganic acid. However, since the mixed solution was gelled, it was impossible to produce a leather-like material and it was confirmed that the processability was insufficient.

The leather-like material obtained in Comparative Example 3 using only an aqueous polyurethane resin having heat-coagulation property obtained by emulsifying with a surfactant without using an ammonium salt of an inorganic acid exhibited remarkable migration during drying Respectively. In addition, the leather extrudate obtained in Comparative Example 3 was rough and hard in texture, and when abraded 1,000 times in the abrasion resistance test, the abrasion resistance was good, but when abraded 3000 times, remarkable abrasion amount was observed and abrasion resistance was insufficient .

Further, in the leather wearing material obtained in Comparative Example 4 using an aqueous polyurethane resin having thermal coagulation property obtained by emulsifying with a surfactant and an ammonium salt of an inorganic acid, the same results as those of the leather-like material obtained in Comparative Example 3 were observed, It was confirmed that the effect of preventing the migration by the ammonium salt of inorganic acid or the like could not be obtained with respect to the aqueous polyurethane resin having heat coagulation property.

Further, in the leather-like material obtained in Comparative Example 5 using a mixed solution obtained by using an aqueous solution of calcium chloride instead of an inorganic acid salt and mixing with an aqueous polyurethane resin obtained by emulsifying with a surfactant, the temperature of the thermal coagulation was lowered by the aqueous solution of calcium chloride, The anti-migration properties were slightly improved, but the migration preventive properties were insufficient as compared with the leather-like materials obtained in Examples 1 to 10. In addition, the leather extrudate obtained in Comparative Example 5 was rough and hard in texture, and when abraded 1,000 times in the abrasion resistance test, the abrasion resistance was good, but when abraded 3000 times, remarkable abrasion amount was observed and abrasion resistance was insufficient . Further, it was confirmed that the surfactant remained in the leather-like material, and it was confirmed that the effect on the fastness to rubbing by the residue was great.

Further, the leather-like material obtained in Comparative Example 6 using an aqueous solution containing an ammonium formate salt instead of the ammonium salt of an inorganic acid is excellent in terms of migration inhibition, abrasion resistance, rubbing fastness, residue and texture, but decomposition of ammonium formate ㆍ A bad odor due to volatilization was confirmed. In addition, formic acid generated at this time is a cause of device corrosion, and environmental problems may arise if formic acid and ammonia gas are released to the atmosphere.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to sufficiently prevent migration even though it is a method for producing a leather-like material using a water-based polyurethane resin taking into account the problems of the environment and the VOC, And a leather-like material obtained by the method for producing the leather-like material, which makes it possible to efficiently and reliably obtain a leather-like material excellent in physical properties such as abrasion resistance, friction fastness and the like, .

Therefore, the manufacturing method of the present invention is particularly useful as an industrial manufacturing method of a leather wearing material, and the leather wearing material obtained by the manufacturing method of the present invention does not remain in the leather wearing material and adversely affects the human body It can be used as it is in an industrial field such as a vehicle, a furniture, a medical bag, a shoe, a bag-shaped article, a sundry goods, a polishing, etc., and can be used as a leather material excellent in stability and durability by providing a skin layer .

Claims (8)

(A) a polyurethane resin having a carboxyl group and / or a carboxylate group, (B) an ammonium salt of an inorganic acid, and (C) water and impregnating the fiber substrate with a mixed solution having a pH of 5.0 to 6.8, By weight. (A) :( B) = 100: 1 in terms of the solid content of the polyurethane resin (A) having a carboxyl group and / or a carboxylate group and the ammonium salt of the inorganic acid (B) 0.1 to 100: 50. The process according to claim 1, wherein the inorganic acid (B) in the ammonium salt of the inorganic acid is sulfuric acid and / or phosphoric acid. The polyester resin composition according to claim 1, wherein the polyurethane resin (A) having a carboxyl group and / or carboxylate group, (B) an ammonium salt of an inorganic acid and (C) water has a heat coagulation temperature of 30 to 80 ° C. Gt; The polyurethane resin composition according to claim 1, wherein the polyurethane resin (A) having a carboxyl group and / or a carboxylate group is obtained by reacting (a) an organic diisocyanate, (b) a polyol, and (c) a carboxyl group with a compound having two or more active hydrogen Neutralizing the resulting isocyanate-terminated prepolymer having a carboxyl group by emulsion-dispersing in water by emulsification, and (d) subjecting the carboxyl group and / or carboxyl group obtained by a chain extension reaction using a polyamine compound having two or more amino groups and / Or a polyurethane resin having a carboxylate group. The method according to claim 1, wherein (A) the total of the carboxyl group content and the carboxylate group content in the polyurethane resin having a carboxyl group and / or carboxylate group is 0.5 to 4.0 mass%. A leather material obtained by the production method according to any one of claims 1 to 6. delete