KR20100099701A - Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather - Google Patents

Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather Download PDF

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KR20100099701A
KR20100099701A KR1020107013183A KR20107013183A KR20100099701A KR 20100099701 A KR20100099701 A KR 20100099701A KR 1020107013183 A KR1020107013183 A KR 1020107013183A KR 20107013183 A KR20107013183 A KR 20107013183A KR 20100099701 A KR20100099701 A KR 20100099701A
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urethane resin
water
artificial leather
acid
resin composition
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요시노부 기베
가즈오 다나베
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닛카카가쿠가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to an aqueous leather urethane for artificial leather containing a thermally solidified water-based urethane resin having a thermal solidification temperature of 40 to 90 ° C and at least one water-soluble acrylic polymer in the polymers of the following (1), (2) and (3). It relates to a resin composition. (1) A polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, alkali metals and / or amine salts of the polymer. (2) poly-α-hydroxyacrylic acid, alkali metals and / or amine salts thereof. (3) Group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid A polymer obtained by radical polymerizing at least one monomer selected from the group and at least one selected from the group consisting of poly-α-hydroxyacrylic acid and alkali metals and / or amine salts thereof, alkali metals of the polymer and // Or amine salts.

Description

Aqueous urethane resin composition for artificial leather, method for production of artificial leather, and artificial leather}

This invention relates to the water-based urethane resin composition for artificial leather, the manufacturing method of artificial leather using the same, and artificial leather.

Background Art Conventionally, artificial leather has been produced by impregnating or applying a urethane resin composition to a base fabric such as a nonwoven fabric, a woven fabric, or a knit fabric. In this manufacturing method, generally, the solvent type urethane resin composition which melt | dissolved the urethane resin component in organic solvents, such as N, N- dimethylformamide, is used and the process which impregnates this in a bubble is performed. By using a solvent-based urethane resin composition, a porous urethane layer can be formed uniformly in a bubble, and the artificial leather excellent in the touch which has the softness | flexibility and fidelity close to natural leather can be obtained. However, in the manufacturing method of artificial leather using a solvent-based urethane resin composition, since harmful solvents are discharged during the processing of air bubbles, a huge labor and cost are required for the solvent recovery process to prevent water pollution and air pollution. Have

On the other hand, manufacture of the artificial leather using the water-based urethane resin composition is performed. In this method, the aqueous urethane resin composition containing the water dispersion of the urethane resin is diluted to an appropriate concentration with water, the dilution liquid is impregnated with bubbles, dried and cured to fix the urethane resin to the bubbles to form artificial leather. Since the organic solvent is not used in the method using the water-based urethane resin composition, it is not necessary to collect | recover a solvent.

However, in the method of using the water-based urethane resin composition, when the air is impregnated with the water-based urethane resin composition, the particles of the urethane resin uniformly dispersed in the bubbles move to the surface layer of the bubble fiber in accordance with the movement of water as the solvent. The so-called migration phenomenon is likely to occur. When such a migration phenomenon occurs, a urethane resin is unevenly distributed on the surface side of the bubble fiber, and there is almost no urethane resin inside. As a result, the artificial leather obtained becomes hard to feel and a wrinkle wrinkles generate | occur | produce. In particular, when the filling ratio of the urethane resin to the bubbles is high, the difference in concentration of the urethane resin becomes remarkable on the surface side and inside of the bubble fiber, and the touch is rough and hard, making the paper like. For this reason, when using a water-based urethane resin composition, it is difficult to fill 20 mass% or more with respect to a bubble, and it was difficult to obtain the artificial leather which has sufficient touch by making both flexibility and fidelity compatible. That is, when using a solvent-based urethane resin composition, while sufficient flexibility can be obtained with a filling rate of 25-50 mass%, when using an aqueous urethane resin composition, it was necessary to considerably reduce a filling rate.

Until now, the examination about the method of preventing the migration of a urethane resin is made | formed. For example, Patent Document 1 below describes a method of adding a thermal gelling agent to give a thermal coagulation property and using a synthetic resin emulsion to solidify this in hot water. Further, Patent Document 2 discloses a hot air or hot water after impregnating or applying a polyurethane emulsion formulation liquid containing a nonionic surfactant and a thermal coagulant to an urethane resin aqueous emulsion having a carboxyl group emulsified with an anionic surfactant. A method of thermally solidifying by heating in a furnace is described. In addition, Patent Literature 3 below describes a method in which a treatment liquid in which inorganic salts are dissolved in a polyurethane emulsion that has been forcibly emulsified is applied to bubbles, and then heated and dried. Further, Patent Literature 4 below contains an aqueous urethane resin composition having a thermal coagulation temperature of 40 to 90 ° C. and an aqueous urethane resin composition comprising a hydrophobic group at the terminal and a associative thickener containing a urethane bond in a molecular chain. Or after application, the method of thermal coagulation is described.

Patent Document 1: Japanese Patent Publication No. 55-51076 Patent Document 2: Japanese Patent Publication No. 59-1823 Patent Document 3: Japanese Unexamined Patent Publication No. 6-316877 Patent Document 4: Japanese Unexamined Patent Publication No. 2000-297211

However, in the method described in Patent Literature 1, the effect of preventing migration is obtained. However, artificial leather is coagulated after a part of the resin composition flows out into the coagulation bath, and the coagulated product reattaches to the surface of the treated fabric. The touch as it may be damaged.

In the method described in Patent Literature 2, in the case where thermal coagulation is performed by hot air drying, the porous layer is not formed inside the coated resin, and the touch tends to become hard as the resin adhesion amount increases. On the other hand, when hot water is used for thermal coagulation, the problem that the urethane resin is anionic is easy to dissolve in hot water, and that a sufficient adhesion amount is not obtained. In addition, a method of salting the urethane resin by adding an inorganic salt (particularly a divalent or higher metal salt), which is a thermal coagulation accelerator, to increase the amount of resin attached to the substrate can be considered. However, since the urethane resin is anionic, the stability of the resin composition There is a compounding problem that is very bad.

In the method of patent document 3, since inorganic salt is used in a large quantity, there exists a problem that inorganic salt remains in the urethane resin after processing, and the intensity | strength of resin is greatly reduced. If the resin strength is low, the possibility of resin dropping out due to strong rubbing effects such as dyeing increases. Also in this case, it is difficult to obtain artificial leather having sufficient elasticity.

In the method described in Patent Document 4, the associative thickener to be added has the ability to prevent the migration of the urethane resin, but the urethane resin coarse coarse coagulated by the associative thickener cannot enter into the fiber and remains attached to the bubble surface. Therefore, there is a problem that the resin is easily eliminated together with the associated thickener at the time of dyeing or washing with water.

As described above, it is true that an aqueous urethane resin composition capable of producing artificial leather having the same touch and elasticity as in the case of using the solvent-based urethane resin composition has not yet been provided.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has an aqueous urethane resin composition for artificial leather, which can produce artificial leather having excellent migration resistance and resin strength and having sufficient feel and elasticity in an aqueous system, and an artificial leather using the same. It aims at providing a manufacturing method and artificial leather.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the water-based urethane resin composition for artificial leather in order to solve the said subject, the water-based urethane resin composition containing a thermosetting coagulation type | system | group urethane resin and a specific water-soluble acrylic polymer has a high viscosity of a system. It was found that a resin layer having excellent migration resistance and sufficient mechanical strength can be formed without using a water-based urethane resin composition. By using this aqueous urethane resin composition, it has been found that an artificial leather having sufficient flexibility and fidelity and excellent elasticity can be produced. It was completed.

That is, the present invention is an aqueous urethane resin composition used in a method of impregnating or applying an aqueous urethane resin composition to a bubble to obtain artificial leather, wherein the thermal coagulation temperature is 40 to 90 ° C. And a water-soluble acrylic polymer (b), wherein the water-soluble acrylic polymer (b) is at least one of the polymers of the following (1), (2) and (3), and provides an aqueous urethane resin composition for artificial leather. do.

(1) A polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, alkali metals and / or amine salts of the polymer.

(2) poly-α-hydroxyacrylic acid, alkali metals and / or amine salts thereof.

(3) Group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid A polymer obtained by radical polymerizing at least one monomer selected from the group and at least one selected from the group consisting of poly-α-hydroxyacrylic acid and alkali metals and / or amine salts thereof, alkali metals of the polymer and // Or amine salts.

According to the water-based urethane resin composition for artificial leather of the present invention, by having the above structure, migration at the time of manufacturing artificial leather can be sufficiently prevented, and it becomes possible to manufacture artificial leather having sufficient touch and elasticity in water. . Although the reason why such an effect is obtained by the water-based urethane resin composition of this invention is not necessarily clear, the thermosetting solid-type water-based urethane resin (a) which permeated uniformly in the fiber by the presence of the said specific water-soluble acrylic polymer (b) is The present invention is thought to be effectively solidifying without migrating at the time of heating, and thereby to provide sufficient mechanical strength of the resin layer to be formed while exhibiting sharper thermal coagulation property than before. Doing.

In addition, the water-based urethane resin composition for artificial leather of the present invention is excellent in standing stability and has a sufficient touch even if the solidification method is caused by any means of hot air, hot water, steam, infrared rays, electromagnetic waves, and high frequencies. Since artificial leather can be obtained, it can be said that it is excellent in handleability and can raise the freedom degree of the manufacturing process of an artificial leather.

Moreover, this invention provides the manufacturing method of the artificial leather which has a process which impregnates or apply | coats the water-based urethane resin composition for artificial leather of this invention to foam.

According to the manufacturing method of the artificial leather of this invention, the artificial leather which has sufficient touch and elasticity can be manufactured in water system by using the water-based urethane resin composition for artificial leather of this invention.

Moreover, this invention provides the artificial leather obtained by the manufacturing method of the artificial leather of this invention.

The artificial leather of the present invention can be obtained by the manufacturing method of the artificial leather of the present invention, and can have sufficient touch and elasticity while being produced in an aqueous system.

According to the present invention, a water-based urethane resin composition for artificial leather, an artificial leather using the same, and an artificial leather, which can produce artificial leather having excellent migration resistance and resin strength and having sufficient touch and elasticity in an aqueous system. Can be provided. Therefore, according to the water-based urethane resin composition for artificial leather of the present invention and a method for producing artificial leather using the same, artificial leather having the same touch and elasticity as that of artificial leather obtained using a solvent-based urethane resin composition is produced in water. can do.

<Water-based urethane resin composition for artificial leather>

The water-based urethane resin composition for artificial leather of the present invention can be used as an impregnation liquid to be impregnated into a bubble or a coating liquid to be applied, and the thermally coagulated water-based urethane resin (A) and the water-soluble acrylic polymer (B) are (I) in advance. It may be mixed, or may be respectively administered to (II) impregnation liquid or a coating liquid, and may be mixed there. In this specification, regardless of the form of (I) and (II), the mixture which contains the thermosetting coagulation type | system | group urethane resin (A) and water-soluble acrylic polymer (B) is called water-based urethane resin composition.

(Thermal coagulation type water-based urethane resin (A))

The water-based urethane resin composition for artificial leather of the present invention needs to contain a heat-sensitive coagulation-based urethane resin having a heat-solidification temperature of 40 to 90 ° C. In addition, in this invention, a "thermal solidification type water-based urethane resin" is what has the property which the resin liquid containing an aqueous urethane resin thickens irreversibly and coagulate | solidifies with a rise of temperature, ie, it has a "thermal solidification temperature." The "thermal solidification temperature" refers to the resin liquid temperature when the resin liquid loses fluidity and solidifies. In addition, "aqueous urethane resin" means the urethane resin emulsified and dispersed in water instead of the organic solvent.

In the water-based urethane resin which does not have thermal coagulation property, when heat-drying the processing cloth which impregnated or apply | coated the resin composition to foam, migration of the urethane resin to the bubble surface cannot fully be prevented, and resin is unevenly distributed on the surface of a processing cloth. As a result, the treated fabric becomes rough and hard, and artificial leather having sufficient touch and elasticity cannot be produced in the water system.

Although the thermal coagulation | solidification temperature of the thermal coagulation | solidification type | system | group urethane resin used by this invention needs to be 40-90 degreeC, 45-80 degreeC is preferable. If the thermal coagulation temperature is lower than 40 ° C, the water-based urethane resin may gel during storage (particularly in summer), and therefore, sufficient care must be taken for the storage temperature. On the other hand, when the thermal coagulation temperature exceeds 90 ° C, migration tends to occur, and the artificial leather feels rough and hard.

The thermosetting coagulation-based urethane resin used in the present invention can be used as long as it is a water-based urethane resin having thermal coagulation without particular limitation on composition and structure. As preferable conditions other than the said thermosetting solidification temperature, the softening temperature of a urethane resin is mentioned. It is preferable that it is 100 degreeC or more, and, as for the softening temperature of the thermal coagulation type | system | group urethane resin used by this invention, it is more preferable that it is 120-240 degreeC. Since the urethane resin whose softening temperature is less than 100 degreeC becomes easy to deteriorate by water, a solvent, an acid, alkali, moist heat, light, etc., it is not preferable.

Examples of the thermally coagulated water-based urethane resin used in the present invention include an isocyanate group obtained by reacting (a) a polyol, (b) a polyisocyanate, and optionally (c) a low molecular chain extender having two or more active hydrogen atoms. The terminal prepolymer is obtained by forcible emulsification and dispersion in water using a nonionic surfactant of HLB 7 to 16, followed by chain extension reaction with a polyamine compound having two or more amino groups and / or imino groups. It can be mentioned. In addition, HLB says the value computed by the formula of Griffin.

As (a) polyol, polyester polyol, polycarbonate polyol, polyether polyol, etc. which have two or more hydroxyl groups are mentioned, for example. Examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate and polybutylene. Sebacate, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene) adipate, polycondensates of 1,6-hexanediol and dimer acid, 1,6-hexanediol and adipic acid The cocondensate of dimer acid, the polycondensate of nonanediol, and dimer acid, the cocondensate of ethylene glycol, adipic acid, and dimer acid, etc. are mentioned. Examples of the polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, and the like. Examples of the polyether polyols include polyethylene glycols having a molecular weight of 200 to 6,000, polypropylene glycols, homopolymers of polytetramethylene glycols, block copolymers and random copolymers, ethylene oxides and propylene oxides, ethylene oxides and butylene oxides. Random copolymers, block copolymers, etc. are mentioned. Moreover, as (a) polyol, the polyether ester polyol etc. which have an ether bond and ester bond can be used. These polyols can be used individually by 1 type or in combination of 2 or more type.

(b) There is no restriction | limiting in particular as polyisocyanate, The aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate which have two or more isocyanate groups can be used, For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc. Alicyclic polyisocyanate such as aliphatic polyisocyanate compound, isophorone diisocyanate, hydrogenated xylene diisocyanate, dicyclohexyl methane diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, and triylene diisocyanate Aromatic polyisocyanates such as diphenylmethane diisocyanate, naphthalene diisocyanate, tridine diisocyanate, xylene diisocyanate and tetramethyl xylene diisocyanate Can be mentioned. These polyisocyanate compounds can be used individually by 1 type or in combination of 2 or more types.

Among the polyisocyanate compounds described above, aliphatic polyisocyanates and alicyclic polyisocyanate compounds are preferred for providing a non-yellowing coating, and for example, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, Norbornane diisocyanate and 1, 3-bis (isocyanate methyl) cyclohexane can be used suitably. Among these, dicyclohexyl methane diisocyanate is suitable because it is excellent in light resistance and heat resistance.

(c) The low molecular chain extender which has two or more active hydrogen atoms can be used as needed. Examples of such low molecular chain extenders include low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, sorbitol, and ethylenediamine. And low molecular weight polyamines such as propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine and triethylenetetramine. Such low molecular chain extenders can be used individually by 1 type or in combination of 2 or more types.

There is no restriction | limiting in particular as a manufacturing method of the said isocyanate group terminal prepolymer, A conventionally well-known manufacturing method, such as a one-stage isocyanate polyaddition reaction method called a one-shot method, and a multistage isocyanate polyaddition reaction method, can be used. It is preferable that reaction temperature at this time is 40-150 degreeC. In addition, the reaction liquid, if necessary, reaction catalysts such as dibutyltin dilaurate, stanas octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, and N-methylmorpholine Can be added. Moreover, the organic solvent which does not react with an isocyanate group can be added to the reaction liquid which synthesize | combines an isocyanate group terminal prepolymer during the reaction or after completion | finish of reaction. As an organic solvent, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, etc. are mentioned, for example. However, acetone, methyl ethyl ketone and tetrahydrofuran are suitable in that it is preferable to remove the organic solvent by vacuum distillation or the like after completing the chain extension reaction.

In this embodiment, when dispersing the isocyanate terminated prepolymer in water, a nonionic surfactant of HLB 7 to 16, preferably a nonionic surfactant of HLB 9 to 15 is used. In addition, HLB here is HLB of the whole nonionic surfactant, and when a some nonionic surfactant is used, it points out the weighted average. If the HLB of the nonionic surfactant to be used is less than 7, the emulsion dispersion is not stable. If the HLB of the nonionic surfactant is more than 16, the water-based urethane resin composition is impregnated in air bubbles or immersed in hot water after application. The urethane resin dispersion may be eluted.

As the nonionic surfactant used to disperse the isocyanate terminated prepolymer in water, it is possible to use many conventional nonionic surfactants in the range of HLB 7 to 16, but for example, polyoxyethylene distyrylphenyl Ether type nonionic surfactant, polyoxyethylene oxypropylene distyryl phenyl ether type nonionic surfactant, polyoxyethylene tristyryl phenyl ether type nonionic surfactant, polyoxyethylene oxypropylene tristyryl phenyl ether type nonionic interface Polyoxyethylene long chain alkyl ethers such as activators, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene sorbitol tetraoleate, a polyoxypropylene polyoxyethylene glycol block or random polymer, polyamine polyoxypropylene polyoxyethylene adduct; and the like.

In particular, it is preferable to use nonionic surfactants having a skeleton of the formula (I).

[ Formula I ]

Figure pct00001

Where

R is an alkyl group having 1 to 9 carbon atoms, an aryl group or an arylalkyl group,

n is an integer from 1 to 3,

Ph is a phenyl ring residue.

AO is oxyethylene and / or oxypropylene,

m is the AO addition mole number.

Said nonionic surfactant can be used individually by 1 type or in combination of 2 or more types.

Although the usage-amount of a nonionic surfactant does not have a restriction | limiting in particular, It is preferable that it is 0.5-10 mass% with respect to an isocyanate terminal prepolymer, and it is more preferable that it is 1-6 mass%. When the usage-amount of a nonionic surfactant is less than 0.5 mass% with respect to an isocyanate terminal prepolymer, it will become difficult to obtain a stable emulsion dispersion state. When the usage-amount of a nonionic surfactant exceeds 10 mass% with respect to an isocyanate terminal prepolymer, the urethane resin film obtained will fall in water resistance and may fall easily at the time of dyeing or washing with water.

When the isocyanate group terminal prepolymer is emulsified and dispersed in water, mechanical shearing force can be used. There is no restriction | limiting in particular as a means which gives a mechanical shear force, For example, emulsification apparatuses, such as a homo mixer and a homogenizer, can be used. It is preferable that an isocyanate group terminal prepolymer emulsifies-disperses in water in the temperature range of 5-40 degreeC, and suppresses reaction of an isocyanate group with water, or a nonionic surfactant as much as possible. When the isocyanate group terminal prepolymer is emulsified and dispersed in water, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, benzoyl chloride, or the like is added as necessary. can do.

After the isocyanate group terminal prepolymer is emulsified and dispersed in water, and (d) chain extension reaction is carried out using the polyamine compound which has two or more amino groups and / or imino groups, a urethane resin aqueous product is obtained.

(d) As a polyamine compound which has two or more amino groups and / or imino groups, For example, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methyl Diamines such as piperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, trylenediamine, xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine , Water-soluble amine derivatives such as polyamines such as tris (2-aminoethyl) amine, amideamines derived from diprimary amines and monocarboxylic acids, and monoketimines of diprimary amines, oxalic acid dihydrazide and meronic acid dihydra Gide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydra Hydrazines such as dehydrate, fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1'-ethylene hydrazine, 1,1'-trimethylenehydrazine, 1,1 '-(1,4-butylene) dihydrazine Derivatives. These polyamine compounds and amine derivatives can be used individually by 1 type or in combination of 2 or more types.

The chain extension reaction of the isocyanate group terminal prepolymer can be carried out by adding (d) the polyamine compound to the emulsion dispersion of the isocyanate group terminal prepolymer or (d) adding the emulsion dispersion of the prepolymer to the polyamine compound. have. It is preferable to perform chain extension reaction at reaction temperature 20-40 degreeC. When the organic solvent is used at the time of synthesizing the isocyanate group terminal prepolymer, it is preferable to remove the organic solvent by distillation under reduced pressure after the chain extension reaction.

When the organic solvent is used after the chain extension reaction, the organic solvent is subjected to the step of removing the organic solvent, and the thermal solidification is a substantially solvent-free aqueous dispersion having a solid content of about 10 to 60% by mass, preferably 15 to 50% by mass. Type water-based urethane resin (a) is obtained.

Although the thermal coagulation | solidification type water-based urethane resin (A) used by this invention exhibits sharp thermal coagulation | solidification property by the combination with water-soluble acrylic polymer (B), from an viewpoint of preventing migration at the time of drying, an average particle diameter is It is preferable that it is at least 0.1 micrometer or more. There exists a tendency for migration prevention property to fall that the average particle diameter of the thermosensitive coagulation type | system | group urethane resin is less than 0.1 micrometer. Moreover, it is more preferable that the average particle diameter of the thermal coagulation type | system | group urethane resin is 0.15-5 micrometers. When the average particle diameter of the thermosensitive coagulation-type urethane resin is 5 µm or more, the stability of the water-based urethane resin tends to be lowered. In addition, the average particle diameter here means the median diameter when it measures on a volume basis using "LA-920" which is a laser diffraction / scattering type particle size distribution measuring apparatus (refer: the product made by Horiba Sesaku Sho). Point.

(Water Soluble Acrylic Polymer (B))

The water-soluble acrylic polymer (b) used by this invention is at least 1 sort (s) in the polymer of following (1), (2), and (3).

(1) A polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, alkali metals and / or amine salts of the polymer.

(2) poly-α-hydroxyacrylic acid, alkali metals and / or amine salts thereof.

(3) Group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid A polymer obtained by radical polymerization of at least one monomer selected from the group and at least one selected from the group consisting of poly-α-hydroxyacrylic acid and alkali metals and / or amine salts thereof, alkali metals of the polymers and / or Or amine salts.

According to the water-based urethane resin composition for artificial leather of the present invention containing the above water-soluble acrylic polymer as an essential component together with the thermally solidified water-based urethane resin (A), when the air is impregnated or applied to a bubble and dried under heat, the heat-solidified type Aqueous urethane resins can express sharper thermal coagulation than before, and artificial leathers obtained using the solvent-based urethane resin composition have the same feel as the artificial leathers, in particular, fidelity, flexibility, and elastic touch. It can be prepared from.

In the case of using an acrylic polymer which is not water-soluble in place of the water-soluble acrylic polymer, compatibility with the thermally coagulated water-based urethane resin worsens and it becomes a heterogeneous system, and thus the effect of the present invention cannot be obtained.

The polymer of at least 1 sort (s) of monomer chosen from the group which consists of acrylic acid, methacrylic acid, and maleic acid among the polymers listed in (1) can be obtained by radical polymerization. Further, the alkali metal and / or amine salt of the polymer is at least one selected from the group consisting of radical polymerization of at least one monomer of the alkali metal salt of the monomer and the amine salt of the monomer, or from the group consisting of acrylic acid, methacrylic acid and maleic acid. Some or all of the carboxyl groups of the polymer of the monomers of the species can be obtained by neutralizing with alkali metals and / or amines. In radical polymerization, another monomer other than the said monomer can be copolymerized in the range which does not impair the effect of this invention. Examples of the copolymerizable monomer include fumaric acid, itaconic acid, ethylene, vinyl chloride, vinyl acetate, acrylamide, acrylate ester, methacrylic acid ester, and the like.

As an alkali metal salt of a polymer, a lithium salt, a sodium salt, a potassium salt, etc. are mentioned, for example. Moreover, as an amine salt of a polymer, an ammonium salt, a triethylamine salt, a butylamine salt, a dibutylamine salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, etc. are mentioned, for example. Two or more types of said salt may be contained in the salt of a polymer.

In addition, when the salt of the polymer is a salt of a polyvalent ion such as an alkaline earth metal salt or a heavy metal salt (for example, Fe 2+ , Fe 3+, etc.), an insoluble salt remains in the thermally solidified urethane resin film, and artificial leather It is not preferable because there is a possibility of impairing the quality of the resin and the resin strength may be lowered.

It is preferable that it is 500-1,00,0000, and, as for the weight average molecular weight of the polymer enumerated in (1), it is more preferable that it is 1,000-150,000. When the weight average molecular weight of a polymer is less than 500, it exists in the tendency for a migration prevention effect to become difficult to be fully acquired. When the weight average molecular weight of a polymer exceeds 1,000,0000, a urethane resin film will become inferior to water resistance and alkali resistance, and may fall off easily at the time of dyeing or washing with water.

The polymers listed in (2), i.e., poly-α-hydroxyacrylic acid, alkali metals and / or amine salts thereof, may be, for example, polylactone compounds corresponding to poly-α-hydroxyacrylic acid of formula (II) It can manufacture by hydrolysis.

[ Formula II ]

Figure pct00002

Where

p is the degree of polymerization.

Moreover, poly-alpha-hydroxyacrylic acid can also be manufactured by oxidative depolymerization, such as high molecular weight poly-alpha-hydroxyacrylic acid and poly-alpha-hydroxyacrylate. Alkali metals and / or amine salts of poly-α-hydroxyacrylic acid may be prepared by oxidizing depolymerization such as high molecular weight poly-α-hydroxyacrylic acid or poly-α-hydroxyacrylate with hydroxides of alkali metal salts and water-soluble amines. It can also manufacture by neutralizing.

As an alkali metal salt of a polymer, a lithium salt, a sodium salt, a potassium salt, etc. are mentioned, for example. Moreover, as an amine salt of a polymer, an ammonium salt, a triethylamine salt, a butylamine salt, a dibutylamine salt, a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, etc. are mentioned, for example. Such salts can be obtained, for example, by hydrolyzing a polylactone compound corresponding to poly-α-hydroxyacrylic acid of the formula (II) using aqueous sodium hydroxide solution, triethylamine, triethanolamine, and the like. 2 or more types in said salt may be contained in the salt of a polymer.

In addition, when the salt of the polymer is a salt of a polyvalent ion such as an alkaline earth metal salt or a heavy metal salt (for example, Fe 2+ , Fe 3+, etc.), an insoluble salt remains in the thermally solidified urethane resin film, and artificial leather It is not preferable because there is a possibility of impairing the quality of the resin and the resin strength may be lowered.

It is preferable that it is 500-1,000,000, and, as for the weight average molecular weight of the polymer enumerated in (2), it is more preferable that it is 1,000-150,000. When the weight average molecular weight of a polymer is less than 500, it exists in the tendency for a migration prevention effect to become difficult to be fully obtained. When the weight average molecular weight of a polymer exceeds 1,000,000, a urethane resin film will fall in water resistance and alkali resistance, and there exists a possibility that it may fall easily at the time of dyeing or washing with water.

The polymers listed in (3), that is, acrylic acid, methacrylic acid, maleic acid, alkali metal salts of acrylic acid, alkali metal salts of methacrylic acid, alkali metal salts of maleic acid, amine salts of acrylic acid, amine salts and methacrylic acid A polymer obtained by radically polymerizing at least one monomer selected from the group consisting of amine salts of acids and at least one selected from the group consisting of poly-α-hydroxyacrylic acid and alkali metals and / or amine salts thereof, The alkali metal and / or amine salt of the said polymer is mixed with the monomer to superpose | polymerize to the aqueous solution containing poly- (alpha)-hydroxyacrylic acid or its salt, and also adds a radical polymerization initiator, and it is 2-10 at 50-90 degreeC. A method of heating and reacting for a time, or a radical polymerization initiator in an aqueous solution containing poly-α-hydroxyacrylic acid or a salt thereof After addition, the monomer to superpose | polymerize can be added dropwise and it can obtain by the method of heating at 50-90 degreeC for 2 to 10 hours, etc. At this time, alcohols, such as methanol, ethanol, and isopropyl alcohol, and water-miscible solvents, such as acetone, can be added to the aqueous solution containing poly- (alpha)-hydroxyacrylic acid or its salt. There is no restriction | limiting in particular as a radical polymerization initiator to be used, For example, redox-type initiator which combined persulfates, such as potassium persulfate, sodium persulfate, ammonium persulfate, a persulfate, sodium bisulfite, hydrogen peroxide, water-soluble azo type, Initiator etc. are mentioned. These radical polymerization initiators can be used individually by 1 type or in combination of 2 or more type. It is preferable that the usage-amount of a radical polymerization initiator is 0.1-1.0 mass part with respect to a total of 100 mass parts of poly- (alpha)-hydroxyacrylic acid and / or its salt, and a monomer to radically polymerize. In addition, at the time of radical polymerization, chain transfer agents, such as octyl thioglycolate, can be added and the degree of polymerization can be adjusted. As an alkali metal salt of acrylic acid, methacrylic acid, and maleic acid, a lithium salt, a sodium salt, a potassium salt, etc. are mentioned, for example. As amine salts of acrylic acid, methacrylic acid and maleic acid, for example, ammonium salt, triethylamine salt, butylamine salt, dibutylamine salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt and the like Can be mentioned. In addition, when the said polymer has a carboxyl group, the alkali metal and / or amine salt of the said polymer can be obtained by neutralizing one part or all part of the said carboxyl group with an alkali metal and / or an amine. As an alkali metal, lithium, sodium, potassium, etc. are mentioned, for example. Moreover, as amine, ammonium, triethylamine, butylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, etc. are mentioned, for example.

Furthermore, from the group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid The inventors believe that the at least one polymerization selected from the group consisting of at least one monomer selected and poly-α-hydroxyacrylic acid and its alkali metal and / or amine salts is by graft polymerization. In the radical polymerization, other monomers can be copolymerized in addition to the above monomers within a range that does not impair the effects of the present invention. Examples of the copolymerizable monomer include fumaric acid, itaconic acid, ethylene, vinyl chloride, vinyl acetate, acrylamide, acrylate ester, methacrylic acid ester, and the like.

It is preferable that it is 500-1,000,000, and, as for the weight average molecular weight of the polymer listed in (3), it is more preferable that it is 1,000-150,000. When the weight average molecular weight of a polymer is less than 500, it exists in the tendency for a migration prevention effect to become difficult to be fully acquired. When the weight average molecular weight of a polymer exceeds 1,000,000, a urethane resin film may be inferior to water resistance and alkali resistance, and may fall off easily at the time of dyeing or washing with water.

The polymer of the above (2) and (3) is a solution dissolved as it is or in a mixed solvent of water and a water-miscible solvent such as lower alcohol, acetone, and the like and includes a thermosetting solid-based urethane resin (A). It can be mixed and used for the urethane resin aqueous dispersion. Since the polymers of (2) and (3) have strong affinity with the amino group or imino group which is a chain extension group of the thermal coagulation-based urethane resin (A), it has good compatibility with the thermal coagulation-based urethane resin and is water-soluble. It can be used suitably as an acrylic polymer (b).

A water-soluble acrylic polymer (b) can use a commercial item. As a commercial item, Nihon Shokubai Co., Ltd. Aquaric DL, TL, HL, Nippon Kayaku Co., Ltd. Jurymer AC-10NP, Toagose Co., Ltd. Aron A-210, T-50, A-10SL, A-30SL, A-20UN, A-20L, A-6520, BELCLENE 200LA by Chiba Japan Co., Ltd., etc. are mentioned.

As for the compounding quantity of water-soluble acrylic polymer (B), it is preferable that it is 0.1-40 mass parts with water content acrylic polymer (B) with respect to 100 mass parts of thermal coagulation type | system | group urethane resin (A) by solid content ratio, and it is more preferable that it is 0.5-20 mass parts. desirable. When the compounding quantity of water-soluble acrylic polymer (b) is less than 0.1 mass part with respect to 100 mass parts of thermal coagulation type | system | group urethane resin (A), there exists a tendency for the migration prevention effect of an aqueous urethane resin composition to become difficult to be fully acquired. On the other hand, when the blending amount of the water-soluble acrylic polymer (b) exceeds 40 parts by mass with respect to 100 parts by mass of the thermally coagulated water-based urethane resin (a), the water resistance of the urethane resin film is lowered, and the touch of artificial leather tends to be hard. There is this.

The water-based urethane resin composition for artificial leather of the present invention is uniformly mixed with the above-mentioned heat-solidifying water-based urethane resin (A) and a water-soluble acrylic polymer (B) at a temperature sufficiently lower than the heat-solidification temperature of the heat-solidifying water-based urethane resin. It can prepare by making it. Moreover, the water-based urethane resin composition for artificial leather of this invention can be prepared also by adding and mix | blending a water-soluble acrylic polymer (B) in the manufacturing process of a thermosetting coagulation type | system | group urethane resin (A).

The water-based urethane resin composition for artificial leather of the present invention, in addition to the thermally solidified water-based urethane resin (A) and the water-soluble acrylic polymer (B), is used as other aqueous dispersions or aqueous dispersions in a range that does not impair the effects of the present invention. For example, emulsions, such as vinyl acetate type, ethylene vinyl acetate type, an acryl type, an acryl styrene type; Latexes such as styrene butadiene, acrylonitrile butadiene and acryl butadiene; Ionomers such as polyethylene and polyolefins; Various aqueous dispersions and aqueous dispersions, such as polyurethane, polyester, polyamide, and an epoxy resin, can be added. These can be used individually by 1 type or in combination of 2 or more type. In addition, such an aqueous dispersion and an aqueous dispersion may be added to the thermal coagulation-type urethane resin (A) and / or the water-soluble acrylic polymer (B), and the thermal coagulation-type urethane resin (A) and the water-soluble acrylic polymer (B) You may add to the water-based urethane resin composition contained.

In addition, in the water-based urethane resin composition for artificial leather of the present invention, as an absorbent for efficiently introducing steam, within a range that does not impair the effects of the present invention, for example, urea, protein, glycerin, polyoxyethylene nonionic Surfactants may be added. These can be used individually by 1 type or in combination of 2 or more type. In addition, such a moisture absorbing agent may be added to the thermosetting coagulation-type urethane resin (A) and / or the water-soluble acrylic polymer (B), and the water-based urethane containing the thermosetting coagulation-type urethane resin (A) and the water-soluble acrylic polymer (B). You may add to a resin composition.

In addition, in the aqueous urethane resin composition for artificial leather of the present invention, for the purpose of lowering the thermal solidification temperature of the thermal coagulation-based urethane resin (A) within a range that does not impair the effects of the present invention, for example, silicified Sodium, potassium silicate; Polyvalent metal salts such as ammonium salts of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, sodium, potassium, calcium, magnesium, zinc, barium, nickel, tin, lead, iron and aluminum; Associative thickeners, alkali thickener polymers, polyetherthioetherglycols, polyether-modified polydimethylsiloxane compounds; Thermal coagulants, such as the alkylene oxide adduct of an alkyl phenol formalin condensate, can be added. These can be used individually by 1 type or in combination of 2 or more type. In addition, these thermal coagulants may be added to the thermal coagulation-type urethane resin (A) and / or the water-soluble acrylic polymer (B), and the water-based system containing the thermal coagulation-type urethane resin (A) and the water-soluble acrylic polymer (B). You may add to a urethane resin composition.

In addition, the aqueous urethane resin composition for artificial leather of the present invention includes a film preparation preparation such as an alkylene glycol derivative or a dialkyl ester of an aliphatic dicarboxylic acid or N-methylpyrrolidone for the purpose of improving the film forming property. Moreover, you may mix | blend various leveling agents, penetrants, etc., such as an fluorine-type leveling agent, an emulsifier, such as a dialkylsulfosuccinate type, an acetylene glycol derivative, for the purpose of improving processability. Moreover, you may mix | blend foaming agents, such as ammonium stearate, the metal salt of a higher fatty acid, and the dialkyl sulfosuccinate type emulsifier, with the objective of providing processability by mechanical foaming to the water-based urethane resin composition for artificial leather of this invention. . Moreover, in order to suppress foaming of a compounding liquid, the water-based urethane resin composition for artificial leather of this invention mix | blends various defoaming agents, such as mineral oil type, an amide type, a silicone type, or a small amount of alcohols, such as ethanol and isopropyl alcohol, It is possible.

In addition, the water-based urethane resin composition for artificial leather of the present invention can be blended with various inorganic and organic pigments that are water-soluble or water-dispersible for coloring purposes, and further include calcium carbonate, talc, aluminum hydroxide, silica, glass fibers, and the like. You may mix | blend organic fillers, such as an inorganic filler, a cellulose powder, protein powder, a silk powder, and organic short fiber.

In addition, the aqueous urethane resin composition for artificial leather of the present invention may be blended with stabilizers such as antioxidants, ultraviolet absorbers, and hydrolysis inhibitors for the purpose of improving various durability such as light resistance, heat resistance, water resistance, solvent resistance, etc. of the water dispersion. Can be. Such stabilizers may be added during or after the production process of the aqueous urethane resin.

Moreover, crosslinking agents, such as an epoxy resin, a melamine resin, an isocyanate compound, an aziridine compound, a polycarbodiimide compound, an oxazoline compound, can be mix | blended with the water-based urethane resin composition for artificial leather of this invention.

Various additives can be mix | blended with the water-based urethane resin composition for artificial leather of this invention in order to provide processing suitability, in the range which does not impair the effect of this invention. Examples of such additives include alcohol-based nonionic surfactants, acetylene glycol-based special surfactants, fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylsulfosuccinate salts, naphthalene sulfonates, and alkanesulfonates. Anionic emulsifiers such as sodium salt and sodium alkyldiphenyl ether sulfonate salt; Nonionic anionic emulsifiers such as polyoxyethylene alkyl sulfates and polyoxyethylene alkylphenyl sulfates, various leveling agents of silicone surfactants and fluorine surfactants; Various stabilizers such as antioxidants, light stabilizers, and ultraviolet inhibitors; Various antifoaming agents such as mineral oil and silicone; Urethane-ized catalysts, plasticizers, colorants such as pigments, usable time extenders, and the like. These can be used individually by 1 type or in combination of 2 or more type.

The above additives may be added during or after the production of the thermally solidified water-based urethane resin (A), or may be added and mixed together when the thermally-solidified water-based urethane resin (A) and the water-soluble acrylic polymer (B) are mixed. You may add to the water-based urethane resin composition containing the thermal coagulation | solidification type water-based urethane resin (A) and water-soluble acrylic polymer (B) as an impregnation liquid or coating liquid at the time of leather manufacture.

The water-based urethane resin composition for artificial leather of the present invention is preferably adjusted to 5 to 65 mass% of resin solid content, more preferably 10 to 60 mass%, and used.

Since the water-based urethane resin composition for artificial leather of the present invention is excellent in stability at room temperature and has sharp thermal coagulation property, it is suitable for various bubbles such as paper such as natural fiber, synthetic fiber, inorganic fiber, nonwoven fabric, and knitted fabric. By using it as an impregnation liquid to impregnate or a coating liquid to apply | coat, it can give the touch comparable to the process by the conventional solvent-type urethane resin composition, especially a softness | flexibility, a faithfulness, and an elastic touch.

In the present invention, in the case of impregnation, the deposition amount of the water-based urethane resin into the bubble is preferably 5 to 100 parts by mass with respect to 100 parts by mass of bubbles, and in the case of coating, the thickness after drying is preferably 0.1 to 10 mm. .

The urethane resin film formed by the water-based urethane resin composition for artificial leather of the present invention is impregnated with or coated with the water-based urethane resin composition by a method such as coating, and then hot air at or above the thermal solidification temperature of the water-based urethane resin composition. It is obtained by heating by heat treatment means such as hot water, steam, infrared rays, electromagnetic waves, high frequency, or a combination thereof. It is preferable that heating temperature is 10 degreeC or more of the thermal coagulation | solidification temperature, and it is preferable that it is less than the embrittlement temperature of a fiber. In addition, although processing time changes with a material, thickness, impregnation of a resin composition, or application amount of a bubble, it can be normally several seconds-several minutes. In order to exhibit the above-mentioned characteristic of the water-based urethane resin composition of this invention to the maximum, it is preferable to use the thermal coagulation | solidification method by steam, an infrared ray, and electromagnetic waves, and in the saturated steam by steam in the point which suppresses drying from the bubble surface. Heating is particularly preferred.

The processed cloth treated with the aqueous urethane resin composition for artificial leather of the present invention can be dried using any drying means such as hot air, infrared rays, electromagnetic waves, and high frequencies. As a drying temperature, 80 degreeC or more is preferable. If the drying temperature is lower than 80 ° C., moisture hardly evaporates and there is a fear that the film forming property of the aqueous urethane resin is poor. Moreover, it is preferable that a drying temperature is less than the embrittlement temperature of a fiber.

The processed cloth coated with the urethane resin can also be dyed. For example, when a bubble is a polyester fiber, dyeing can be performed on 125-135 degreeC and the conditions for 30 to 90 minutes using a disperse dye. In addition, the dyed fabric is reduced and washed at 60 to 95 ° C. for 10 to 30 minutes in a reduction washing treatment bath composed of an alkali agent and a reducing agent, and then neutralized, washed with water and dried in the alkaline agent remaining in the reduced washed dyeing. It goes through such a process. The urethane resin formed by the water-based urethane resin composition for artificial leather of the present invention is not easily dropped even under the severe dyeing and soaping conditions when bubbles are made of polyester fibers, and maintains excellent quality as artificial leather. Can be.

The water-based urethane resin composition for artificial leather of the present invention is artificial leather for each use, which has been conventionally manufactured using a solvent-based urethane resin, for example, furniture such as shoes, bags, medical care, chairs, sofas, and vehicle seats. It is useful for producing various synthetic leathers used for interior materials for automobiles, steering wheels, and the like, and moisture-permeable waterproof materials. Moreover, the water-based urethane resin composition for artificial leather of this invention is useful as a processing agent, such as an abrasive and a core material of a felt pen.

Example

Although an Example demonstrates this invention below, this invention is not limited only to an Example. In addition, "part" in an Example represents a "mass part." In addition, in the following synthesis examples 1-11, solid content ratio (mass%) takes 5 g of sample solutions in a curry, and it is 3 hours in a 105 degreeC dryer (Taby specifications, perfect oven PV-210). The solid content remaining after standing was measured and calculated. In addition, in the following Synthesis Examples 7-11, the weight average molecular weight was measured using the gel permeation chromatograph [Tosoh Corporation, HLC-8020GPC], and was calculated by polyethyleneglycol conversion. In the column, TSKgel G5000PW (manufactured by Tosoh Co., Ltd.) and G3000PW (manufactured by Tosoh Co., Ltd.) were used in combination, and a phosphate buffer solution (0.025 mol / L of Na 2 HPO 4 · 12H 2 O and 0.025 mol / Elution was carried out using 1 L of KH 2 PO 4 ) at a flow rate of 1.0 mL / min.

[Synthesis example of water-based urethane resin]

Synthesis Example 1 (thermal coagulation type water-based urethane resin (A))

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1000) and polyoxyethylene polypropylene random copolymer glycol (average molecular weight 1000, oxy 70% of ethylene groups) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 60 parts were injected and mixed uniformly, followed by dicyclohexyl methane. 40.4 parts of diisocyanate was added and reacted at 75 degreeC for 300 minutes, and the methyl ethyl ketone solution of the urethane prepolymer which is 1.7 mass% of free isocyanate group content with respect to solid content was obtained. After cooling this solution to 30 degrees C or less, 0.1 part of decyl phosphate ester and 6.0 parts of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added, after mixing uniformly, it transfers to another container, and gradually adds 254 parts of water, The emulsified and dispersed phase was disperse | distributed using the disper vane, and the polyamine aqueous solution which melt | dissolved 2.0 parts of piperazine and 0.8 parts of diethylenetriamine in 11.3 parts of water was added, and it stirred for 90 minutes, and obtained the urethane resin aqueous dispersion. The obtained urethane resin dispersion was further subjected to desolvent at 35 ° C. under reduced pressure, whereby a solid content of 35.0%, a viscosity of 50.0 mPa · s (BM viscometer, No. 1 rotor, 60 rpm) and an average particle diameter of 0.52 μm was obtained. A urethane resin (hereinafter referred to as resin A) was obtained. The thermal solidification temperature of this aqueous urethane resin was 45 degreeC, and the softening temperature of the film which dried this was 195 degreeC.

Synthesis Example 2 (thermal coagulation type water-based urethane resin (A))

76.1 parts of polytetramethylene glycol (average molecular weight 1,000) and polyoxyethylene oxypropylene random copolymer glycol (average molecular weight 1,000, oxyethylene group content 70 mass) to a four neck flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube. %) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 60.0 parts were injected and mixed uniformly, then 40.4 parts of dicyclohexyl methane diisocyanate It was added and reacted at 75 DEG C for 300 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having a content of 1.7% by mass of free isocyanate groups relative to nonvolatile matters. After cooling this solution to 30 degreeC, 0.1 part of decyl phosphate ester and 6.0 parts of polyoxyethylene tristyryl phenyl ether (HLB15) were added, after mixing uniformly, it transferred to another container, 254.0 parts of water were gradually added, and the disper wing It was subjected to phase emulsification and dispersion using a polyamine solution in which 2.0 parts of piperazine and 0.8 parts of diethylenetriamine were dissolved in 11.3 parts of water, followed by stirring for 90 minutes to obtain a urethane resin dispersion. The obtained urethane resin dispersion was further subjected to desolvent at 35 ° C. under reduced pressure, whereby a solid content of 35.0 mass%, a viscosity of 45 mPa · s (BM viscometer, No. 1 rotor, 30 rpm) and an average particle diameter of 0.34 μm was obtained. A urethane resin (hereinafter referred to as resin B) was obtained. The thermal solidification temperature of this aqueous urethane resin was 60 degreeC, and the softening temperature of the film which dried this was 185 degreeC.

Synthesis Example 3 (thermal coagulation type water-based urethane resin (A))

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1000) and polyoxyethylene polypropylene random copolymer glycol (average molecular weight 1000, oxy 70% of ethylene groups) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 52.4 parts were injected and mixed uniformly, followed by hexane diisocyanate 25.9. Part was added and reacted at 75 ° C. for 300 minutes to obtain a methylethylketone solution of a urethane prepolymer having a free isocyanate group content of 1.9% by mass relative to solid content. After cooling this solution to 30 degrees C or less, 0.1 part of decyl phosphate ester and 6.0 parts of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added, after mixing uniformly, it transfers to another container, and gradually adds 254 parts of water, The emulsified and dispersed phase was disperse | distributed using the disper vane, and the polyamine aqueous solution which melt | dissolved 2.0 parts of piperazine and 0.8 parts of diethylenetriamine in 11.3 parts of water was added, and it stirred for 90 minutes, and obtained the urethane resin aqueous dispersion. Furthermore, the desolvent was performed at 35 degreeC under reduced pressure, the solid content 35.0% of solids, the viscosity 60.0 mPa * s (BM viscometer, No. 1 rotor, 60 rpm), and the stable thermosetting solid-type water-based urethane resin of average particle diameter 0.61 micrometer (hereinafter, resin) C)). The thermal solidification temperature of this aqueous urethane resin was 62 degreeC, and the softening temperature of the film which dried this was 130 degreeC.

Synthesis Example 4 (thermal coagulation type water-based urethane resin (A))

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1000) and polyoxyethylene polypropylene random copolymer glycol (average molecular weight 1000, oxy 70% of ethylene groups) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 60 parts were injected and mixed uniformly, followed by dicyclohexyl methane. 40.4 parts of diisocyanate was added and reacted at 75 degreeC for 300 minutes, and the methyl ethyl ketone solution of the urethane prepolymer which is 1.7 mass% of free isocyanate group content with respect to solid content was obtained. After cooling this solution to 30 degrees C or less, 0.1 part of decyl phosphate ester and 6.0 parts of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added, after mixing uniformly, to another container, and 254 parts of water are added gradually, , Disperse emulsification and dispersion using a disper blade, to which a polyamine aqueous solution in which 2.0 parts of piperazine and 0.8 parts of diethylenetriamine were dissolved in 11.3 parts of water was added, followed by stirring for 90 minutes to obtain a polyurethane aqueous dispersion. Furthermore, after performing a desolvent at 35 degreeC under reduced pressure, 1 mass% of Vicsen AG-25 (made by Nikka Chemical Co., Ltd., anionic surfactant) was added, solid content 35.0%, and the viscosity 50.0 mPa * s (BM viscometer, 1). Arc rotor, 60 rpm), and a stable thermally coagulated water-based urethane resin (hereinafter referred to as resin D) having an average particle diameter of 0.52 m. The thermal solidification temperature of this aqueous urethane resin was 80 degreeC, and the softening temperature of the film which dried this was 195 degreeC.

Synthesis Example 5 (thermal coagulation type water-based urethane resin (A))

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1000) and polyoxyethylene polypropylene random copolymer glycol (average molecular weight 1000, oxy Ethylene group-containing 70% by mass) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 60 parts were injected and mixed uniformly, followed by dicyclohexyl 40.4 parts of methane diisocyanate were added and reacted at 75 degreeC for 300 minutes, and the methyl ethyl ketone solution of the urethane prepolymer whose content of free isocyanate group with respect to solid content is 1.7% was obtained. After cooling this solution to 30 degrees C or less, 0.1 part of decyl phosphate ester and 12.0 parts of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added, after homogeneous mixing, it transfers to another container and 254 parts of water are added gradually, , Disperse emulsification and dispersion using a disper blade, to which a polyamine aqueous solution in which 2.0 parts of piperazine and 0.8 parts of diethylenetriamine were dissolved in 11.3 parts of water was added, followed by stirring for 90 minutes to obtain a polyurethane aqueous dispersion. Furthermore, the desolvent was performed at 35 degreeC under reduced pressure, the solid content 35.0% of solids, the viscosity 70.0 mPa * s (BM viscometer, No. 1 rotor, 60 rpm), and the stable thermosetting solid-type water-based urethane resin of average particle diameter 0.18 micrometer (hereinafter, resin) Is called E). The thermal solidification temperature of this aqueous urethane resin was 48 degreeC, and the softening temperature of the film which dried this was 190 degreeC.

Synthesis Example 6 (Non-sensitizing solidified water-based urethane resin)

In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 76.1 parts of 1,6-hexanediol polycarbonate polyol (average molecular weight 1000) and polyoxyethylene polypropylene random copolymer glycol (average molecular weight 1000, oxy Ethylene group-containing 70% by mass) 16.9 parts, 1,4-butanediol 1.5 parts, trimethylolpropane 1.9 parts, dibutyltin dilaurate 0.001 parts and methyl ethyl ketone 60 parts were injected and mixed uniformly, followed by dicyclohexyl 40.4 parts of methane diisocyanate were added and reacted at 75 degreeC for 300 minutes, and the methyl ethyl ketone solution of the urethane prepolymer whose content of free isocyanate group with respect to solid content is 1.7 mass% was obtained. After cooling this solution to 30 degrees C or less, 0.1 part of decyl phosphate ester and 6.0 parts of polyoxyethylene tristyryl phenyl ether (HLB = 15) are added, after mixing uniformly, it transfers to another container, and gradually adds 254 parts of water, , Disperse emulsification and dispersion using a disper blade, to which a polyamine aqueous solution in which 2.0 parts of piperazine and 0.8 parts of diethylenetriamine were dissolved in 11.3 parts of water was added, followed by stirring for 90 minutes to obtain a polyurethane aqueous dispersion. Furthermore, after performing a desolvent at 35 degreeC under reduced pressure, 3 mass% of Vicsen AG-25 (made by Nikka Chemical Co., Ltd., anionic surfactant) was added, solid content 35.0%, and the viscosity 50.0 mPa * s (BM viscometer, 1). Arc rotor, 60 rpm), and a stable non-thermally coagulated water-based urethane resin (hereinafter referred to as comparative resin A) having an average particle diameter of 0.52 µm was obtained. This water-based urethane resin did not thermally solidify at 100 degreeC. The softening temperature of the film which dried this aqueous urethane resin was 195 degreeC.

[Synthesis example of water-soluble acrylic polymer (B)]

Synthesis Example 7 (Water-soluble acrylic polymer (B): Poly-α-hydroxy acrylate)

Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 588.0 parts of water and 150.0 parts of a 48 mass% sodium hydroxide aqueous solution were injected and stirred until uniform. After heating up to 50 degreeC, 150.0 parts of polylactone compounds (weight average molecular weight 100,000) corresponding to poly- (alpha)-hydroxyacrylic acid were added, and it heated up to 70 degreeC. After the temperature was raised, the mixture was reacted at 70 to 75 ° C. for 3 hours to obtain an aqueous solution of poly-α-hydroxy hydroxy acrylate (hereinafter referred to as compound A). The viscosity of this aqueous solution was 200 mPa * s, solid content was 25.1%, and the weight average molecular weight of poly-alpha-hydroxy acrylate sodium which is solid content was 100,000.

Synthesis Example 8 (Water-soluble acrylic polymer (B): Poly-α-hydroxy hydroxy sodium sodium acrylate)

Into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 163.0 parts of 40% by mass of poly-α-hydroxy hydroxyacrylate (weight average molecular weight 100,000) and 127.0 parts of water were injected. After heating up at 80 degreeC, 150 parts of 40 mass% sodium acrylate aqueous solution were added dropwise over 45 minutes, and 5 parts of sodium persulfate were added. After addition, the mixture was reacted at 80 to 90 ° C. for 3 hours, and then 555 parts of hot water at 60 ° C. was added, followed by cooling to obtain an aqueous solution of a polymer of poly-α-hydroxy acrylate sodium acrylate (hereinafter referred to as compound B). Obtained. The viscosity of this polymer aqueous solution was 150 mPa * s, solid content was 12.5%, and the weight average molecular weight of the polymer which is solid content was about 20,000.

Synthesis Example 9 (Water-soluble acrylic polymer (B): Polyethyl acrylate triethylamine salt)

Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 180.0 parts of an aqueous solution of 40% by mass of Aron A-10SL (manufactured by Toagosei Co., Ltd., polyacrylic acid solution, weight average molecular weight 6,000) and water 295.7 parts were injected. 101.0 parts of triethylamine was added dropwise over 45 minutes, reacted at 30 to 40 ° C for 3 hours, and then cooled to obtain an aqueous solution of polyethyl acrylate triethylamine salt (hereinafter referred to as compound C). The viscosity of this polymer aqueous solution was 80 mPa * s, and solid content was 30.0%.

Synthesis Example 10 (water-soluble acrylic polymer (B): polyacrylate triethanol amine salt)

Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 180.0 parts of an aqueous solution of 40% by mass of Aron A-10SL (manufactured by Toagosei Co., Ltd., polyacrylic acid solution, weight average molecular weight 6,000) and 233.88 parts of water were injected. 74.5 parts of triethanolamine was added dropwise for 45 minutes, reacted at 30 to 40 ° C. for 3 hours, and then cooled to obtain an aqueous solution of the polyacrylate triethanol amine salt (hereinafter referred to as compound D). The viscosity of this polymer aqueous solution was 150 mPa * s, and solid content was 30.0%.

[Synthesis example of association type thickener]

Synthesis Example 11 (Associated Thickener)

Into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 800.0 parts of polyethylene glycol having a molecular weight of 4,000 and 230.8 parts of an ethylene oxide 17 mole adduct of tristyrene phenol were dehydrated and dehydrated at 105 ° C. under reduced pressure, followed by hexamethylenedi. 50.4 parts of isocyanates were added and reacted at 80 to 90 ° C for 5 hours to dissolve in 540.6 parts of water to obtain a urethane-based thickener (hereinafter, referred to as association thickener A). The viscosity of this polymer aqueous solution was 6000 mPa * s, and solid content was 20.0%.

(Example 1)

57.1 parts of Resin A (aqueous urethane resin) obtained in Synthesis Example 1, 10.0 parts of a 10% by mass aqueous solution of Compound A (aqueous acrylic polymer) obtained in Synthesis Example 7, and 32.9 parts of dilution water were mixed to prepare a water-based urethane resin composition. It prepared. Solid content ratio of each component of this aqueous urethane resin composition is resin A / compound A = 100 parts / 5 parts, and solid content of an aqueous urethane resin composition is 21 mass%. The water-based urethane resin composition was impregnated into a non-woven fabric (a basis weight of 200 g / m 2) made of polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 200%, and a vapor pressure of 39 kPa and a steam flow rate of 200 l / min. The process was performed for 5 minutes by HTS (Tsujiisen Shoku Kogyo Kogyo Co., Ltd. Type: HT-3-550) adjusted to the above. After completion of the treatment, the treated material was placed in a 70 ° C hot water bath, washed with hot water for 10 minutes, squeezed out excess moisture with mangle, and left to dry for 10 minutes with a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. Was carried out to obtain artificial leather of Example 1.

(Example 2)

As a water-soluble acrylic polymer, the treatment was carried out in the same manner as in Example 1 except that a 10% by mass aqueous solution of Compound B obtained in Synthesis Example 8 was used to obtain an artificial leather of Example 2.

(Example 3)

As a water-soluble acrylic polymer, except having used the 10 mass% aqueous solution of the compound C obtained by the synthesis example 9, it processed like Example 1, and obtained the artificial leather of Example 3.

(Example 4)

As a water-soluble acrylic polymer, except having used the 10 mass% aqueous solution of the compound D obtained by the synthesis example 10, it processed like Example 1 and obtained the artificial leather of Example 4.

(Example 5)

As a water-soluble acrylic polymer, it processed similarly to Example 1 except having used the 10 mass% aqueous solution of Aron A-210 (Toagose Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 2,000, 43% of solid content). The artificial leather of Example 5 was obtained.

(Example 6)

As a water-soluble acrylic polymer, it processed similarly to Example 1 except having used 10 mass% aqueous solution of Aron T-50 (Toagose Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 6,000, solid content 43%), and performed. The artificial leather of Example 6 was obtained.

In addition, a mini-jet high-pressure liquid dyeing machine (P-300 type, manufactured by Techsumiki Ken Co., Ltd.), obtained by placing the obtained artificial leather disc in a 100 L bath and having a bath ratio of 1:30 and a nozzle pressure of 2 kgf / cm 2. By using a disperse dye (CI Disperse Blue 79), it was dyed under the conditions of 10% owf, 130 ℃, 30 minutes. The artificial leather after dyeing is reduced and washed at 80 ° C. for 20 minutes with a reducing detergent containing 4 g / l of thiourea dioxide and 4 g / l of sodium hydroxide, and then dried by drying at a drying temperature of 100 ° C. with a hot air dryer. It was. The removal rate of the urethane resin at this time was about 4 mass% in the value computed from the weight change before and behind dyeing.

(Example 7)

The treatment was carried out in the same manner as in Example 6 except that the drying conditions after the urethane resin composition was impregnated into the nonwoven fabric were changed from steam drying to standing drying for 10 minutes in a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. The artificial leather of Example 7 was obtained by carrying out.

(Example 8)

As a water-soluble acrylic polymer, it processed similarly to Example 1 except having used the 10 mass% aqueous solution of Aron A-10SL (Toagose Co., Ltd., polyacrylic-acid aqueous solution, molecular weight 6,000, solid content 40%), and carried out similarly to Example 1, and Example 8 artificial leathers were obtained.

(Example 9)

As a water-soluble acrylic polymer, it carried out similarly to Example 1 except having used the 10 mass% aqueous solution of Aron A-30SL (Toagose Co., Ltd., aqueous ammonium polyacrylate, molecular weight 6,000, solid content 40%), and carried out similarly to Example 1, and performed. The artificial leather of Example 9 was obtained.

(Example 10)

As a water-soluble acrylic polymer, it processed similarly to Example 1 except having used the 10 mass% aqueous solution of Aron A-20UN (Toagose Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 20,000, solid content 42%). The artificial leather of Example 10 was obtained.

(Example 11)

As a water-soluble acrylic polymer, it processed and performed like Example 1 except having used the 10 mass% aqueous solution of Aron A-20L (Toagose Co., Ltd., sodium polyacrylate aqueous solution, molecular weight 500,000, solid content 18%). The artificial leather of Example 11 was obtained.

(Example 12)

As a water-soluble acrylic polymer, it processed similarly to Example 1 except having used the 10 mass% aqueous solution of Aron A-6520 (Toagose Co., Ltd., sodium polymaleic acid aqueous solution, molecular weight 1,000, 40% of solid content). The artificial leather of Example 12 was obtained.

(Example 13)

Except having used Resin B obtained by the synthesis example 2 as water-based urethane resin, it processed like Example 6 and obtained the artificial leather of Example 13.

(Example 14)

Except having used Resin D obtained by the synthesis example 4 as water-based urethane resin, it processed like Example 6 and obtained the artificial leather of Example 14.

(Example 15)

Except having used Resin E obtained by the synthesis example 5 as an aqueous urethane resin component, it processed like Example 6 and obtained the artificial leather of Example 15.

(Example 16)

Except having used Resin C obtained by the synthesis example 3 as an aqueous urethane resin component, it processed like Example 6 and obtained the artificial leather of Example 16.

(Comparative Example 1)

57.1 parts of resin A (water-based urethane resin) obtained in Synthesis Example 1 and 42.9 parts of dilution water were mixed to prepare an aqueous urethane resin composition. Solid content of an aqueous urethane resin composition is 20 mass%. The water-based urethane resin composition was impregnated into a non-woven fabric (a basis weight of 200 g / m 2) made of a polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 200%, and adjusted to a vapor pressure of 39 kPa and a steam flow rate of 200 l / min. Treatment was performed for 5 minutes with HTS (Tsujiisen Shoku Kogyo Co., Ltd. Type: HT-3-550). After completion of the treatment, the treated material was placed in a 70 ° C hot water bath, washed with hot water for 10 minutes, squeezed out excess moisture with mangle, and left to dry for 10 minutes with a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. Was carried out to obtain an artificial leather of Comparative Example 1.

(Comparative Example 2)

57.1 parts of Resin A (water-based urethane resin) obtained in Synthesis Example 1, 10.0 parts of an aqueous 10% by mass aqueous sodium sulfate (100% solids) solution, and 32.9 parts of dilution water were mixed to prepare an aqueous urethane resin composition. Solid content ratio of each component of this aqueous urethane resin composition is resin A / sodium anhydride = 100 parts / 5 parts, and solid content of an aqueous urethane resin composition is 21 mass%. The water-based urethane resin composition was impregnated into a non-woven fabric (a basis weight of 200 g / m 2) made of a polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 200%, and adjusted to a vapor pressure of 39 kPa and a steam flow rate of 200 l / min. The treatment was performed for 5 minutes with HTS (Tsujiisen Shoku Kogyo Kogyo Co., Ltd. Type: HT-3-550). After completion of the treatment, the treated material was placed in a 70 ° C hot water bath, washed with hot water for 10 minutes, squeezed out excess moisture with mangle, and left to dry for 10 minutes with a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. Was carried out to obtain an artificial leather of Comparative Example 2.

In addition, the obtained artificial leather disk was placed in a 100-l bath and placed in a mini jet high-pressure liquid dyeing machine (P-300 type, manufactured by Techsumiki Ken Co., Ltd.) having a bath ratio of 1:30 and a nozzle pressure of 2 kgf / cm 2. Then, using a disperse dye (CI Disperse Blue 79), it was stained under the conditions of 10% owf, 130 ℃, 30 minutes. The artificial leather after dyeing is reduced and washed at 80 ° C. for 20 minutes with a reducing detergent containing 4 g / l of thiourea dioxide and 4 g / l of sodium hydroxide, and then dried at a drying temperature of 100 ° C. with a hot air drier. Finished The removal rate of the urethane resin at this time was 12 mass% in the value computed from the weight change before and behind dyeing.

(Comparative Example 3)

57.1 parts of Resin A (aqueous urethane resin) obtained in Synthesis Example 1, 10.0 parts of a 10% by mass aqueous solution of the association type thickener A obtained in Synthesis Example 11, and 32.9 parts of dilution water were mixed to prepare an aqueous urethane resin composition. Solid content ratio of each component of this aqueous urethane resin composition is resin A / association type thickener A = 100 parts / 5 parts, and solid content of an aqueous urethane resin composition is 21 mass%. The water-based urethane resin composition was impregnated into a non-woven fabric (a basis weight of 200 g / m 2) made of a polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 200%, and adjusted to a vapor pressure of 39 kPa and a steam flow rate of 200 l / min. Treatment was performed for 5 minutes with HTS (Tsujiisen Shoku Kogyo Co., Ltd. Type: HT-3-550). After completion of the treatment, the treated material was placed in a 70 ° C hot water bath, washed with hot water for 10 minutes, squeezed out excess moisture with mangle, and left to dry for 10 minutes with a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. Was carried out to obtain an artificial leather of Comparative Example 3.

(Comparative Example 4)

57.1 parts of Resin A (aqueous urethane resin) obtained in Synthesis Example 1, 10.0 parts of 10% by mass aqueous solution of OPTIFLO M-210 (RockWood's hydrophobically modified ethoxylate aminoplast associated thickener, solid content 20.0%), and dilution water 32.9 parts were mixed and the water-based urethane resin composition was prepared. Solid content ratio of each component of this aqueous urethane resin composition is resin A / OPTIFLO M-210 = 100 parts / 5 parts, and solid content of an aqueous urethane resin composition is 21 mass%. The water-based urethane resin composition was impregnated into a non-woven fabric (a basis weight of 200 g / m 2) made of a polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 200%, and adjusted to a vapor pressure of 39 kPa and a steam flow rate of 200 l / min. Treatment was performed for 5 minutes with HTS (Tsujiisen Shoku Kogyo Co., Ltd. Type: HT-3-550). After completion of the treatment, the treated material was placed in a 70 ° C hot water bath, washed with hot water for 10 minutes, squeezed out excess moisture with mangle, and left to dry for 10 minutes with a hot air dryer (TABAI SAFETYOVEN SPH-200) adjusted to 100 ° C. Was carried out to obtain an artificial leather of Comparative Example 4.

(Comparative Example 5)

Except having used Comparative resin A obtained by the synthesis example 6 as an aqueous urethane resin component, it processed like Example 6 and obtained the artificial leather of the comparative example 5.

(Reference Example 1)

Solvent-based urethane resin evapanol ALS-30 (manufactured by Nikka Chemical Co., Ltd., N, N-dimethylformamide solvent) 53.3 parts, 36.7 parts of N, N-dimethylformamide, NK assist F-100 (Niigagaku Chemical Co., Ltd.) 5 parts of Shikisha, nonionic activator) and 5 parts of NK assist F-200 (Nicagagaku Co., Ltd., nonionic activator) were mixed to prepare a solvent-based urethane resin composition. This solvent-based urethane resin composition was impregnated into a non-woven fabric (basic weight of 200 g / m 2) made of polyester fiber of 0.5 denier using a slit mangle so as to have an impregnation rate of 250%. After the completion of the treatment, the water was coagulated for 10 minutes in a water bath adjusted to 25 ° C, and then hot water washed for 20 minutes in a hot water bath adjusted to 80 ° C. Then, after excess moisture was squeezed with mangle, it was left to dry for 10 minutes with a hot air drier (TABAI SAFETYOVEN SPH-200) adjusted to 120 ° C. to obtain artificial leather of Reference Example 1.

By the method shown below, the stationary stability of the water-based urethane resin composition obtained in Examples 1-16, Comparative Examples 1-5, and Reference Example 1, and the presence and feel of migration of artificial leather were evaluated. The evaluation results are shown in Tables 1-3.

<Evaluation method>

Stationary Stability of Water-Based Urethane Resin Composition:

The state when the aqueous urethane resin composition was left to stand at 30 degreeC for 1 day was observed.

The case where there was no change of separation, sedimentation, thickening, etc. in the aqueous urethane resin composition was determined as "(circle)", and the case where there was a change of separation, sedimentation, thickening, etc. was determined as "x".

Is there a migration?

The state of charge of the urethane resin was visually observed by electron micrograph of the cross section of artificial leather.

It is judged that it is "◎" that urethane resin is filled in the whole artificial leather cross section, and resin migrates to the artificial leather surface to some extent, but resin migrates to "○", artificial leather surface that resin is filled to the inside, However, in the case where there was no problem in practical use, it was determined that "△△", the internal resin was small, resin migrated to the artificial leather surface as "△", and that most resin migrated to the artificial leather surface as "x". .

Artificial leather feel:

Artificial leather was evaluated by touch.

When it has a touch like natural leather, it is judged as "○", and when it is slightly lower than natural leather, but when there is no practical problem, "○ △", when it is harder than the natural leather and lacks flexibility or lacks a sense of fidelity Or it was determined that "(DELTA)" and the case where the touch was hard were "x" when the elasticity was insufficient and it did not have a touch like a natural leather.

Figure pct00003

Figure pct00004

Figure pct00005

Moreover, about Examples 1-16, Comparative Examples 1-5, and Reference Example 1, the solidification state of the water-based urethane resin composition and the physical property of the film formed from a urethane resin composition were evaluated by the method shown below. The evaluation results are shown in Tables 4 to 6.

Solidification State:

10 g of water-based urethane resin compositions were taken into a test tube, and the state at the time of standing in 90 degreeC constant temperature hot water bath was evaluated. The thing which solidified on the agar phase was determined as "(circle)", and what coarsened into granules was "(triangle | delta)" and the thing which was not solidified was determined as "x". In addition, the "agar phase" as referred to herein refers to a state in which the aqueous urethane resin composition solidifies uniformly throughout the test tube and has elasticity. In addition, "coarse granulation" means that an aqueous urethane resin composition becomes a floc-like coarse particle in a test tube.

Film Properties:

(1) film production

A water-based urethane resin composition was put into a box made of stainless steel having a length of 12 cm, a width of 10 cm, and a height of 1 cm so that the thickness after drying of the polyurethane film was 0.3 mm, and the temperature was adjusted at 20 ° C. and 65% RH for 2 days. It formed into a film by the cast method. Then, heat processing for 30 minutes was performed at 130 degreeC, and the polyurethane film was obtained.

(2) Measurement of physical properties of polyurethane film

A dumbbell-shaped No. 3 type test piece of a polyurethane film was produced from the polyurethane film obtained in (1), and the test piece was conditioned at 20 ° C. and 65% RH, according to JIS K 6251-1993. Shimazu Sesaku Sho, AUTOGRAPH AG-500D] was used, and the breaking strength and the elongation at break were measured at a tensile speed of 300 mm / min.

Figure pct00006

Figure pct00007

Figure pct00008

From the above results, according to the water-based urethane resin composition of Examples 1-16, it is excellent in stationary stability, it is sufficiently stable at normal temperature, there is no migration, it can be uniformly filled between fibers by sharp thermal coagulation | solidification, and the intensity | strength of resin is little, In addition, it was confirmed that an artificial leather having a touch equivalent to that of natural leather, that is, flexibility, faithfulness, and elasticity can be obtained.

[ Industrial availability ]

The water-based urethane resin composition for artificial leather of the present invention has stable and sharp thermal coagulation property at room temperature, and can sufficiently prevent migration even when impregnated or applied to bubbles. Therefore, according to the water-based urethane resin composition for artificial leather of the present invention and a method for producing an artificial leather using the same, the artificial leather obtained by using the solvent-based urethane resin composition has the same feel, in particular, flexibility, fidelity and elasticity. Artificial leather can be produced in water.

Claims (3)

As a water-based urethane resin composition used by the method of impregnating or apply | coating an aqueous urethane resin composition to a bubble, and obtaining an artificial leather,
It contains a thermal coagulation type water-based urethane resin (A) and a water-soluble acrylic polymer (B) whose thermal coagulation temperature is 40-90 degreeC,
The said water-soluble acrylic polymer (b) is at least 1 sort (s) in the polymer of following (1), (2) and (3), The water-based urethane resin composition for artificial leather.
(1) A polymer of at least one monomer selected from the group consisting of acrylic acid, methacrylic acid and maleic acid, alkali metals and / or amine salts of the polymer.
(2) poly-α-hydroxyacrylic acid, alkali metals and / or amine salts thereof.
(3) Group consisting of acrylic acid, methacrylic acid, maleic acid, alkali metal salt of acrylic acid, alkali metal salt of methacrylic acid, alkali metal salt of maleic acid, amine salt of acrylic acid, amine salt of methacrylic acid and amine salt of maleic acid A polymer obtained by radical polymerizing at least one monomer selected from the group and at least one selected from the group consisting of poly-α-hydroxyacrylic acid and alkali metals and / or amine salts thereof, alkali metals of the polymer and // Or amine salts. The manufacturing method of artificial leather which has a process which impregnates or apply | coats the water-based urethane resin composition for artificial leathers of Claim 1 to a bubble. Artificial leather obtained by the process for producing artificial leather according to claim 2.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103388266A (en) * 2013-07-16 2013-11-13 山东泽辉高科涂层有限公司 Polyurethane resin for impregnating superfine fiber with high moisture penetrability and preparation method of polyurethane resin

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408698A (en) * 2011-09-02 2012-04-11 福建宝利特集团有限公司 Preparation method for waterborne polyurethane foaming slurry
JP5401522B2 (en) * 2011-09-15 2014-01-29 富士フイルム株式会社 Coating composition, and image forming material, lithographic printing plate precursor and oxygen-barrier film using the composition
CN105369631A (en) * 2015-12-25 2016-03-02 江苏宝泽高分子材料股份有限公司 Non-yellowing high-gloss oil leather for synthetic leather and preparation method of oil leather
CN107190521B (en) * 2017-05-24 2019-10-29 贝内克-长顺汽车内饰材料（张家港）有限公司 A kind of low smell PVC artificial leather and preparation method thereof
JP7247516B2 (en) * 2017-10-31 2023-03-29 Ｕｂｅ株式会社 emulsion composition
CN111989372B (en) * 2018-04-20 2022-04-22 Dic株式会社 Resin composition and synthetic leather
TWI691630B (en) * 2018-11-16 2020-04-21 劉玉文 Artificial leather and production method thereof
CN110284335B (en) * 2019-07-26 2022-04-19 凤阳加松新型材料科技有限公司 Preparation method of environment-friendly silica gel synthetic leather
CN112195663B (en) * 2020-09-30 2022-09-09 安徽安利材料科技股份有限公司 Regenerated silk water-based solvent-free polyurethane synthetic leather for packaging and preparation method thereof
JP6888161B1 (en) * 2020-10-02 2021-06-16 大日精化工業株式会社 Urethane prepolymers, moisture-curable urethane hot-melt resin compositions, and laminates.

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3047951B2 (en) * 1993-04-30 2000-06-05 旭化成工業株式会社 Manufacturing method of artificial leather with good soft abrasion resistance
JP3972234B2 (en) * 1999-02-08 2007-09-05 大日本インキ化学工業株式会社 Aqueous urethane resin composition for porous formation
JP3626418B2 (en) * 2000-03-07 2005-03-09 三洋化成工業株式会社 Textile treatment agent
JP4532758B2 (en) * 2001-02-20 2010-08-25 日華化学株式会社 Method for producing porous structure
JP4055419B2 (en) * 2002-01-23 2008-03-05 東レ株式会社 Method for producing napped leather-like sheet
JP2003277600A (en) * 2002-03-22 2003-10-02 Nicca Chemical Co Ltd Stabilizer for polyurethane resin, method for stabilizing polyurethane resin, and polyurethane resin composition
JP3967629B2 (en) * 2002-05-13 2007-08-29 三洋化成工業株式会社 Leather-like sheet material
CN1696226A (en) * 2004-05-14 2005-11-16 湖南亚大新材料科技股份有限公司 Ultraviolet light solidified water born paint in use for leather or leatheroid
JP2006028248A (en) * 2004-07-13 2006-02-02 Kuraray Co Ltd Heat-sensitive gelling emulsion
JP4452139B2 (en) * 2004-07-28 2010-04-21 日華化学株式会社 Method for manufacturing leather materials
CN1757690A (en) * 2005-07-12 2006-04-12 东莞市德富皮革制品有限公司 Environmental protection and water type leather coating used for leather and artificial leather, and its prepn. method

Cited By (2)

* Cited by examiner, † Cited by third party
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CN103388266A (en) * 2013-07-16 2013-11-13 山东泽辉高科涂层有限公司 Polyurethane resin for impregnating superfine fiber with high moisture penetrability and preparation method of polyurethane resin
CN103388266B (en) * 2013-07-16 2015-09-30 山东泽辉高科涂层有限公司 A kind of high poisture-penetrability polyurethane resin for superfine fibre soaking and preparation method thereof

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