TWI525148B - Water-based polyurethane resin with high chromaticity, method of producing the same, and application on suede composite material thereof - Google Patents

Description

High chroma water-based polyurethane resin and its manufacturing method and application thereof in suede composite material

The present invention relates to an aqueous polyurethane resin and a method for producing the same, and more particularly to a high chroma waterborne polyurethane resin and a method for producing the same, and to the use of the suede composite material.

There are many leather products such as leather, synthetic leather and artificial leather on the market as substitutes for natural leather. The leather product is mainly in the interior or surface of a substrate such as a woven fabric, a knit fabric or a non-woven fabric, and forms a foaming layer mainly composed of a polyurethane (PU) resin, so that the hand feeling, the porous structure and the like are closer to the natural leather.

The method for producing the PU resin foamed layer is quite diverse. For example, a polymer such as a PU resin can be dissolved in a water-soluble organic solvent such as dimethylformamide by a wet PU process, and various additives are added. The substrate is then immersed therein or coated onto a substrate. After that, the use can be combined with the aforementioned water solubility. The leather product is prepared by treating a solvent in which the solvent is mixed with each other, solidifying the polymer, and then performing a solvent removal and drying step.

However, the above wet PV process still has the following problems. First of all, the wet PU process is used in the process of processing or in the latter stage, and the amount of the water-soluble organic solvent is large, and the water-soluble organic solvent is mostly a solvent which is highly flammable and highly toxic, not only the drying time. Long, there is a risk of fire, and the resulting organic volatile compounds (VOC) will be released into the atmosphere, which will worsen the working environment and cause environmental pollution. Further, in the obtained leather product, in order to impart a texture and a porous structure similar to that of the natural leather, the amount of the wet PU resin to be formed must be sufficient, but this also increases the residual of the water-soluble organic solvent, resulting in a subsequent costly equivalent. Labor and cost to remove residual organic solvents and recover organic solvents.

Therefore, water-based PU resins have been developed to gradually replace conventional solvent-based PU resins. In short, the aqueous PU resin replaces the above water-soluble organic solvent with water to be environmentally friendly and does not impose an environmental burden. However, the aqueous PU resin has a small average molecular weight, and its hydrolysis resistance, mechanical strength, stability, heat resistance, hand feeling, porosity, and chroma are also insufficient.

At present, the base fabric made of ultrafine fibers is used in combination with grinding to improve the problem of poor hand feeling. In addition, powder additives and coagulants may be additionally added to the aqueous PU resin to increase the porosity thereof. However, the above-mentioned process method can be improved to a relatively limited extent, and the steps are complicated, and the chroma cannot be improved.

In view of the above, it is urgent to propose a high chroma water-based polyurethane resin and a method for producing the same to improve various disadvantages of the conventional PU resin process.

Accordingly, an object of the present invention is to provide a method for producing an aqueous polyurethane (PU) resin by controlling the content of a carboxylic acid group and a polycarbonate polyol of an aqueous PU resin, and adding an appropriate amount A water-based PU resin can be obtained by dispersing a dispersant and a diamine compound.

Another object of the present invention is to provide an aqueous PU resin which is obtained by the above method.

Still another object of the present invention is to provide a method for producing a porous layer for a high-color aqueous PU resin-like suede composite material, which comprises using the above-mentioned aqueous PU resin, pigment, foaming auxiliary agent and a dry coating step. A high-color aqueous PU resin composition such as a bridging agent is uniformly coated on a substrate and then heat-treated.

According to the above object of the present invention, a method for producing an aqueous polyurethane resin is proposed. In one embodiment, the diisocyanate compound (a), the polycarbonate polyol (b), and the first hydroxyl group-containing compound (c-1) are first subjected to a prepolymerization reaction to obtain a first prepolymer. Next, the first prepolymer, the second hydroxyl group-containing compound (c-2) and the carboxylic acid group-containing compound (d) are subjected to a polymerization reaction to obtain a second prepolymer, wherein the second prepolymerization is performed. The substance has at least one carboxylic acid group. Then, neutralizing agent (e) is added to neutralize the second prepolymer. Further, the neutralized second prepolymer was diluted with a solvent (h). Then, it will be diluted The second prepolymer is added to a mixed solution of the dispersing agent (f) and water to form a dispersion, wherein the dispersing agent (f) is an ethoxy-containing nonionic dispersing agent or an ethoxy group-containing An anionic dispersant. Next, the above dispersion liquid and a diamine compound (g) are subjected to a chain extension reaction to obtain an aqueous PU resin (A), and the above aqueous PU resin (A) is a self-emulsification type aqueous PU resin. .

The aqueous PU resin (A) has 0.9 parts by weight to 1.3 parts by weight of a carboxylic acid group and 60 parts by weight to 68 parts by weight of a polycarbonate polyol based on the total solid content of the above aqueous PU resin (A) being 100 parts by weight. (b), and the content of the dispersing agent (f) is from more than 0 parts by weight to less than 7 parts by weight.

According to an embodiment of the present invention, the above polycarbonate polyol (b) may be a polycarbonate diol, and the polycarbonate diol has an arithmetic mean molecular weight of 700 to 3,000.

According to an embodiment of the present invention, the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2) may be an aliphatic polyol. In another embodiment, the first hydroxyl group-containing compound (c-1) may include 1,3-buthylene glycol (col), and the second hydroxyl group-containing compound (c-2) comprises Trimethylolpropane or glycerol.

According to an embodiment of the present invention, the above-mentioned carboxylic acid group-containing compound (d) may be a carboxylic acid group-containing short-chain polyol having a molecular weight or an arithmetic mean molecular weight of from 100 to 1,000. In another embodiment, the above carboxylic acid group-containing compound (d) may comprise dimethylol propionoc acid (DMPA) and dimethylol butanoic acid (DMBA).

According to an embodiment of the present invention, the neutralizing agent (e) may be an organic neutralizing agent or an inorganic neutralizing agent.

According to an embodiment of the present invention, it is preferred that the above aqueous PU resin (A) has 3 parts by weight to 5 parts by weight of the dispersant (f) and 0.05 parts by weight to 1 part by weight of the diamine compound (g).

According to an embodiment of the present invention, the solvent (h) may comprise acetone, methyl ethyl ketone (MEK), and any combination thereof.

According to an embodiment of the present invention, after the chain extension reaction described above, the stirring step is more selectively performed.

According to an embodiment of the present invention, it is preferred that the aqueous PU resin (A) has from 0.9 part by weight to 1.0 part by weight of the carboxylic acid group and from 64 to 68 parts by weight of the polycarbonate polyol (b).

According to another object of the present invention, there is provided an aqueous PU resin which is produced by the above-described method for producing an aqueous PU resin. Moreover, the aqueous PU resin (A) has 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group and 60 parts by weight to 68 parts by weight of the polycarbonate polyol based on 100 parts by weight of the total solid content of the aqueous PU resin (A). (b).

According to still another object of the present invention, a method for producing a porous layer for a high chroma water-based PU resin-like suede composite material is provided. First, the high chroma water-based PU resin composition (F) is applied onto a substrate by a dry coating step. The high chroma water-based PU resin composition (F) includes an aqueous PU resin (A), a pigment (B), a foaming auxiliary (C), and a bridging agent (D), and the above pigment (B) may be water-soluble. An anionic dispersion type pigment, and the above-mentioned foaming aid has a volatilization rate lower than that of water, and is insoluble in water and does not bind to water-based PU trees. Lipid (A) is mutually soluble. Wherein the use amount of the aqueous PU resin (A) is 100 parts by weight, the amount of the pigment (B) is 2 to 6 parts by weight, the amount of the foaming auxiliary (C) is 20 to 60 parts by weight, and bridging The agent (D) is used in an amount of from 0.5 to 4 parts by weight.

Next, the coated substrate is subjected to heat treatment to form a porous layer of the high-color aqueous PU resin composition (F), wherein the heat treatment is performed to remove moisture of the high-color aqueous PU resin composition (F). The coating layer is cured and formed, and then a plurality of continuous pores are formed by volatilization of the foaming aid (C) to form a porous layer.

The obtained porous layer was not subjected to raising treatment, and the porous layer was directly coated with the substrate, and there was no adhesive layer. Further, the obtained porous layer has a chroma of not less than 5 and a frictional fastness of not less than 4 grades.

According to an embodiment of the present invention, the high-color aqueous PU resin composition (F) may optionally contain an additive (E), and the additive (E) may comprise a tackifier, an antifoaming agent, a film former or a heat-sensitive coagulant. .

100‧‧‧ method

110, 120, 130, 140, 150, 160‧ ‧ steps

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; Part of the flow chart.

The invention provides a high chroma water-based polyurethane (PU) resin and a preparation method thereof, which firstly control the content of a carboxylic acid group and a polycarbonate polyol of an aqueous PU resin to obtain an aqueous PU resin, and reuse the same. The obtained water-based PU resin is added with a pigment, a foaming aid, a bridging agent or other additives to obtain a high-color water-based PU resin.

In one embodiment, the aqueous PU resin of the present invention comprises at least Diisocyanate compound (a), polycarbonate polyol (b), first hydroxyl group-containing compound (c-1), second hydroxyl group-containing compound (c-2), carboxylic acid group-containing compound (d), neutralizer (e), a dispersing agent (f), a diamine compound (g), and a solvent (h), which are described below.

Waterborne polyurethane resin Diisocyanate compound (a)

The diisocyanate compound (a) suitable for use in the present invention may be any of the organic diisocyanate compounds used in the manufacture of PU emulsions, including but not limited to aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates or the above. random combination.

Specific examples of the aforementioned aliphatic diisocyanate are: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), diisocyanate Tetramethylxylylene diisocyanate (TMXDI) and dihexyl diisocyanate. The aforementioned alicyclic diisocyanate may be, for example but not limited to, 4,4'-dicyclohexylmethane diisocyanate (4,4'-dicyclohexylmethane) Diisocyanate; H12MDI) and so on. Specific examples of the aforementioned aromatic diisocyanate are: 2,4-tolylene diisocyanate, 2,6-benzylidene diisocyanate, diisocyanate 4, 4'-diphenylmethane ester, p-benzylidene diisocyanate, dimethylene diisocyanate and 1,5-naphthyl diisocyanate, among which diisocyanate A ketone ester (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) are preferred.

Polycarbonate polyol (b)

The polycarbonate polyol (b) suitable for use in the present invention is preferably a reactant derived from a carbonate and a polyol, wherein specific examples of the carbonate are, for example, dialkyl carbonates or alkylene carbonates ( Alkene carbonates) and diaryl carbonates. As for the dialkyl carbonates, they may include, but are not limited to, dimethyl carbonate and diethyl carbonate. The alkylene carbonates can include, but are not limited to, ethylene carbonate. Diaryl carbonates can include, but are not limited to, diphenyl carbonate.

The above polycarbonate polyol (b) is preferably a polycarbonate diol having an arithmetic mean molecular weight of, for example, 700 to 3,000, preferably 1,000 to 2,000. Specific examples thereof include Nippollan-965 (Pc-1000; manufactured by Japan Poly Co., Ltd.) and Nippollan-963 (Pc-2000; manufactured by Japan Poly Co., Ltd.).

The amount of the above polycarbonate polyol (b) is from 60 parts by weight to 68 parts by weight, based on 100 parts by weight of the aqueous polyurethane resin (A), and is from 64 parts by weight to 68 parts by weight. Preferably.

When the content of the polycarbonate polyol (b) is less than 60 parts by weight, the predetermined chroma will not be obtained, and if the content of the polycarbonate polyol (b) is more than 68 parts by weight, the system is produced. The water-based PU resin (A) has poor stability and is easy to aggregate.

It is to be noted that if the above polycarbonate polyol (b) is changed to a polyester, the obtained product has poor hydrolysis resistance. Further, if the above polycarbonate polyol (b) is changed to a polyether, the finished product cannot achieve a predetermined chroma and feel. Therefore, the aqueous PU resin of the present invention excludes the use of polyesters and polyethers.

Hydroxy-containing compound (c)

The hydroxyl group-containing compound (c) used in the present invention is generally preferably an aliphatic polyol, and may include, but is not limited to, an aliphatic diol and an aliphatic triol. In one embodiment, the hydroxyl group-containing compound (c) may include, but is not limited to, the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2).

Specific examples of the above-mentioned first hydroxyl group-containing compound (c-1) which is an aliphatic diol may include, but are not limited to, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol. (1,3-butanediol; 1,3-BG), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol , neopentyl glycol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-anthracene The alcohol is preferably 1,3-butanediol.

Specific examples of the above-mentioned second hydroxyl group-containing compound (c-2) which is an aliphatic triol may include, but are not limited to, glycerin, trimethylmethane, trimethylolethane, and trimethylolpropane (TMP). Trimethylolpropane (TMP) and glycerol are preferred.

Carboxylic acid-containing compound (d)

The carboxylic acid group-containing compound (d) used in the present invention may impart a hydrophilic side chain group to the aqueous PU resin, and may optionally contain other hydrophilic side chain groups such as a sulfonic acid group (-SO ₃ H), phosphoric acid. Base (-OPO ₃ H ₂ ) and/or phosphonic acid group (-PO ₃ H ₂ ).

In an exemplary embodiment, the carboxylic acid group-containing compound (d) is a carboxylic acid group-containing short-chain polyol, and its molecular weight or arithmetic mean molecular weight is generally from 100 to 1,000, and specific examples thereof may include, but are not limited to, aliphatic two. Carboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelic acid, azelaic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyl Adipic acid, 3-methyladipate, 3-methylpentane-dibasic acid, 2-methyloctane-dibasic acid, 3,8-dimethyl and alkane-dibasic acid, 3 , 7-dimethyl and alkane-dibasic acid, dimethylolpropionic acid (DMPA) and dimethylol butanoic acid (DMBA). Among them, dimethylolpropionic acid (DMPA) and dimethylolbutanoic acid (DMBA) are preferred to impart a hard touch to the aqueous PU resin.

The carboxylic acid group-containing compound (d) may have a carboxylic acid group content of from 0.9 part by weight to 1.3 parts by weight, based on the amount of the aqueous PU resin (A), and may be from 0.9 part by weight to 1.0 part by weight. The serving is preferred.

When the carboxylic acid group content is less than 0.9 parts by weight, the aqueous PU resin (A) is less likely to be dispersed, and if the carboxylic acid group content is more than 1.3 parts by weight, the high-color aqueous PU resin-like suede composite prepared as described later is used. The porous layer for materials has a poor hand.

In addition, when the content of the carboxylic acid group in the present invention is less than 2 parts by weight, there is a problem that the dispersion cannot be uniformly dispersed. However, in the present invention, the above-mentioned problem is improved by the dispersant (f) added later, and thus the present invention can be achieved. The effect of the invention.

Neutralizer (e)

The neutralizing agent (e) of the present invention is used to prevent cracks from occurring after the aqueous PU resin is formed into a film. In an embodiment, the neutralizing agent (e) may further comprise an organic neutralizing agent (e-1) and/or an inorganic neutralizing agent (e-2). The aforementioned suitable organic neutralizing agent (e-1) may include, but is not limited to, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N-methylmorpholine (N- Methylmorphorine; NMMP) or any combination of the above, preferably N-methylmorpholine. The aforementioned inorganic neutralizing agent (e-2) may include, but is not limited to, potassium hydroxide, sodium hydroxide, lithium hydroxide or any combination of the above. The aforementioned neutralizing agent (e) may be used singly or in combination of two or more kinds.

Dispersing agent (f)

The dispersing agent (f) of the present invention is used as an external emulsifier and does not react with the diisocyanate compound (a), the polycarbonate polyol (b), the first hydroxyl group-containing compound (c-1), and the second hydroxyl group-containing compound ( C-2), containing a carboxylic acid group-containing compound (d), a neutralizing agent (e), a diamine compound (g), and a solvent (h). The above dispersing agent (f) may be an ethoxylated nonionic dispersing agent or an ethoxylated anionic dispersing agent, and the hydrophilicity-lipophilic balance (HLB) of the selected dispersing agent (f) is 11 to 16 is preferred.

The above ethoxylated nonionic dispersing agent may include, but is not limited to, a polyethoxylated alkylphenol such as polyethoxylated p-nonylphenol, p-octyl Phenol or p-dodecyl phenol, polyethoxylated linear alcohol, polyethoxylated polyoxypropylene diol, polyethoxylated thiol, polyethoxylated fatty acid, polyethoxylated ruthenium Oxylkane, ethoxylated cocoamine, octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol or any combination of the above.

Specific examples of the above-mentioned ethoxy group-containing nonionic dispersing agent are, for example, Tergitol TMN 100 and Triton X-100 manufactured by Dow Chemical Co., Ltd., and manufactured by Shell Chemical Co., Ltd. under the trade name Neodol 25-7, Neodol 23-6.5, Neodol. 1-5 and Neodol23-9, trade names are Dobanol91-5 and Dobanol 25-7, or products of the United States Union Carbide Corporation under the trade names of Tergitol 15-S-7 and Tergitol 15-S-9 or above. random combination.

The above ethoxylated anionic dispersant may comprise ethoxylated sodium alkyl sulphate (AES), such as: ethoxylated sodium lauryl ether sulfate (SLES), other B having a carbon number of 12 to 22. Sodium oxyalkyl sulfate or any combination of the above.

The amount of the dispersing agent (f) to be used is preferably from 0 part by weight to 7 parts by weight, based on 100 parts by weight of the aqueous PU resin (A), and preferably from 3 parts by weight to 5 parts by weight.

The dispersing agent (f) according to the present invention is such that the aqueous PU resin (A) can be uniformly dispersed. If the dispersing agent (f) is not used or more than 7 parts by weight of the dispersing agent (f) is used, the aqueous PU resin is caused. (A) It is not possible to disperse evenly.

Diamine compound (g)

The diamine compound (g) used in the present invention is a chain extender, and specific examples thereof may include, but are not limited to, ethylenediamine, Hexamethylenediamine, diethylenetriamine, hydrazine, diterpene succinate, diterpene terephthalate, piperazine, etc., of which piperazine is preferred.

The content of the above diamine compound (g) is from 0.05 part by weight to 1 part by weight based on 100 parts by weight of the aqueous polyurethane resin (A). In use, the above diamine compound (g) may be formulated, for example, as an aqueous solution containing 10% by weight of a diamine compound.

Solvent (h)

The second prepolymer formed by the present invention may be diluted with a solvent (h), except that the solvent (h) is not combined with the diisocyanate compound (a), the polycarbonate polyol (b), and the first hydroxyl group-containing compound (c) -1), a second hydroxyl group-containing compound (c-2), a carboxylic acid group-containing compound (d), a neutralizing agent (e), a dispersing agent (f), and a diamine compound (g), the above solvent (h) ) may include, but is not limited to, acetone, methyl ethylketone (MEK), dimethylacetamide (DMA), toluene, etc., but acetone, methyl ethyl ketone or any combination thereof is preferred. .

Further, the water system of the present invention is used for dissolving or dispersing the above components, and is not particularly limited. Specifically, for example, distilled water, pure water (water obtained by deionization treatment by ion exchange resin, etc.), ultrapure water (excluding inorganic ions, containing no organic matter, bacteria, fine particles, and dissolved gas) and various functions that have been disclosed Water, etc. The water used in the present invention is preferably pure water or ultrapure water, more preferably ultrapure water. The ultrapure water may be obtained by passing the tap water through activated carbon, ion exchange treatment, and distillation treatment, and if necessary, sterilizing by ultraviolet light irradiation or passing through a filter.

Method for producing waterborne polyurethane resin

The aqueous polyurethane (PU) resin of the present invention is obtained by controlling the content of a carboxylic acid group in the polycarbonate polyol (b) and the aqueous PU resin. Please refer to FIG. 1 , which is a partial flow chart showing a method for manufacturing an aqueous PU resin according to an embodiment of the present invention, which is described in detail below.

In one embodiment, the diisocyanate compound (a), the polycarbonate polyol (b) and the first hydroxyl-containing compound (c-1) are prepolymerized at 80 ° C to 90 ° C for about 2.5 hours. A first prepolymer is formed, as shown in step 110 of FIG.

In the formula (I), the formula (I-1) means a diisocyanate compound (a), the formula (I-2) means a polycarbonate polyol (b), and the formula (I-3) means a first pre- The polymer, and the formula (I-4) means the diisocyanate compound (a) remaining in the reaction. Further, a may be from 2.5 to 3.5, b may be from 0.5 to 1.5, and c may be from 0.5 to 1.5.

In the reaction of the formula (I), a catalyst and/or an antioxidant may be selectively added depending on actual needs. The aforementioned catalyst may include, but is not limited to, tin octylate, monobutyltin triacetate, monobutyltin monooctanate, monobutyltin monoacetate, and cis-butane. Organotin compounds such as monobutyltin diene, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate; tetraisopropyl titanate, titanic acid Organic titanium compound such as tetra-n-butyl ester; triethylamine, N,N-diethylcyclohexylamine, N,N,N',N'-tetramethylethylethylamine and tri-ethylenediamine Third-grade amines. The aforementioned antioxidant may include, but is not limited to, an organic phosphite compound, which is specifically, for example, tetraphenyl dipropyleneglycol diphosphite (TDD), diphenyl pentaerythritol diphosphite, diphenylisoindole. Phosphite trimethyl isodecyl phosphite, diphenyl phosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, di(2,4-di Tert-butylphenyl)pentaerythritol diphosphite, di(octadecyl)pentaerythritol diphosphite, triphenylphosphite, tris(nonylphenol) phosphite, tetra (2,4-di-tert Butylphenol)-4,4'-biphenyldiphosphite, phenyldiisodecylphosphite, poly-4,4'-isopropylidenediphenol tetraphenol phosphite, poly(two Propylene glycol) phenyl phosphite (PDP) and an esterification catalyst for organometallic compounds, etc., among which are environmentally friendly esterification catalysts of organometallic compounds (ES CAT-100E, Seho Tech Inc., Korea ) is better.

Next, after the first prepolymer of the above formula (I-3) is cooled to about 75 ° C or lower, as shown in the formula (II), the first prepolymer, the remaining diisocyanate compound ( a), the second hydroxyl group-containing compound (c-2) and the carboxylic acid group-containing compound (d) are subjected to a polymerization reaction at a temperature of 70 to 75 ° C to form a second prepolymer, as shown in step 120 of FIG. Show. Wherein the second prepolymer has at least one hydrophilic side chain group, such as a carboxylic acid group, a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-OPO ₃ H ₂ ) or a phosphonic acid group (-PO ₃ H ₂ ).

In the reaction of the formula (II), the formula (II-1) means a carboxylic acid group-containing compound (d), and the formula (II-2) means a second prepolymer, a, b, c are as described above. , d may be from 0.8 to 1.5, and n varies depending on actual needs, and the arithmetic average molecular weight of the second prepolymer of the formula (II-2) may be, for example, from 2,000 to 6,000, and the viscosity may be, for example, 2,500 cps, within a certain range. Up to 30,000 cps (test temperature: 70 ° C), but the invention is not limited thereto.

Then, as shown in step 130, after the second prepolymer is cooled to 60-70 ° C, the neutralizing agent (e) is added and the dispersion step is carried out for about 5 minutes to neutralize the second prepolymer. The second prepolymer is represented by the formulae (III-1) to (III-3), and the formulae (III-1) and (III-3) are preferred.

Then, as shown in step 140, the neutralized second prepolymer is added to the solvent (h) to dilute the second prepolymer.

Next, as shown in step 150, the diluted second prepolymer is added to the mixed solution of the dispersant (f) and water, and a dispersion step is carried out to form a dispersion.

The above dispersion step can be carried out by using a commercially available stirring, mixing, shaking apparatus or the like, and the neutralized second prepolymer is uniformly dispersed in the dispersing agent (f) and water to form a dispersion.

Thereafter, the dispersion containing the second prepolymer and the diamine compound (g) are subjected to a chain extension reaction at 30 ° C to 50 ° C for about 1 hour to about 20 hours, and then for about 1 hour to about 16 hours. Preferably, the aqueous PU resin (A) is produced as shown in step 160 of FIG.

The aqueous PU resin (A) obtained by the above method can be subjected to a dispersion step, which can be continuously stirred for about 16 hours at room temperature, for example, at a room temperature to obtain a uniformly dispersed aqueous PU resin ( A).

One of the features of the present invention is that the water-soluble PU resin (A) is defined. The content of the medium polycarbonate polyol (b) and the carboxylic acid group is advantageous for the production of a porous layer for a high-color aqueous PU resin-like suede composite material to be described later. The obtained 100 parts by weight of the aqueous PU resin (A) contains 60 parts by weight to 68 parts by weight of the polycarbonate polyol (b) and 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group.

Method for producing porous layer for high chroma water-based polyurethane resin-like suede composite material First, the dry coating step

First, in one embodiment, a dry coating step is performed to apply a high chroma waterborne polyurethane (PU) composition (F) to at least one surface of the substrate. The high chroma water-based PU resin composition (F) coated by the above dry coating step may be unpatterned (for example, as an undercoat layer) or have a pattern (for example, as a top coat layer).

In one example, the substrate used in the present invention is not limited, and may be a paper, a nonwoven fabric, a woven fabric or a resin film. In general, the high-color aqueous PU resin composition (F) may be applied to one surface or both surfaces of the substrate, and the coating amount of the high-color aqueous PU resin composition (F) on the surface of the substrate is generally 100 gr/ Cm ² to 200 gr/cm ² .

In the above embodiment, the high chroma water-based PU resin composition (F) may include the aforementioned aqueous PU resin (A), pigment (B), foaming auxiliary (C), and bridging agent (D), wherein the aqueous PU resin ( A) As mentioned above, there is no longer a rumor here, and the other components are described below.

Pigment (B)

The pigment (B) of the present invention may be a water-soluble anionic dispersion type pigment, and may be an inorganic pigment or an organic pigment, wherein the inorganic pigment is a metal compound such as a metal oxide or a metal-stack salt, and specific examples thereof include iron and cobalt. A metal oxide of aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, bismuth, or the like, and a composite oxide of the foregoing metals. Specific examples of organic pigments are: CI Pigment Yellow 1,3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81 , 83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175; CI Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63, 64,71,73; CI Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23 ,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53 :1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178 ,17 9,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; CI Pigment Violet 1,19,23,29,32,36,38,39;CI Pigment Blue 1,2,15,15:3,15:4,15:6,16,22,60,66, WUB Blue 1C059 (Da Gong Chemical); CI Pigment Green 7,36,37; CI Pigment Brown 23,25,28; CI Pigment Black 1,7, WUB Black 1C058 (Da Gong Chemical), etc. The above pigments may be used alone or in combination. A variety of uses. The pigment (B) is used in an amount of 2 parts by weight to 6 parts by weight based on 100 parts by weight of the aqueous PU resin (A).

If the amount of the above pigment (B) used is less than 2 parts by weight, the predetermined chroma cannot be achieved. If the amount of the above pigment (B) is more than 6 parts by weight, although the chroma can be improved, the waste of the pigment causes a problem that the friction fastness is poor and the color is easily lost.

Foaming aid (C)

The foaming aid (C) used in the present invention, wherein the foaming assistant (C) may include, but is not limited to, a hydrocarbon solvent having a carbon number of 5 to 17, which is insoluble in water but has a volatilization rate It is lower than the evaporation rate of water.

Specific examples of the above-mentioned suitable foaming auxiliaries (C) are, for example, IP SOLVENT (for example, IP SOLVENT 1016, IP SOLVENT 1620 and IP SOLVENT 2028, etc.) series products (produced by Nippon Ignaku Co., Ltd.); trade name NA SOLVENT series products ( Nippon Oil Co., Ltd.; trade name ISOPAR series products (manufactured by ExxonMobil Chemical Co., USA), preferably IP SOLVENT 1620. The above foaming aid (C) can be used alone One or a mixture of multiple uses. In general, the amount of the foaming auxiliary (C) used is from 20 parts by weight to 60 parts by weight based on 100 parts by weight of the aqueous PU resin (A).

When the amount of the above-mentioned foaming auxiliary (C) is less than 20 parts by weight, the obtained porous layer may have disadvantages such as a rough surface of the porous layer, a poor touch, and insufficient softness due to insufficient continuous pores. When the amount of the foaming aid (C) used exceeds 60 parts by weight, it is difficult to disperse and the porous layer obtained in the subsequent manner may be disadvantageous in that it is too soft and has poor formability due to excessive continuous pores.

Bridging agent (D)

In one embodiment, the bridging agent (D) suitable for use in the present invention is formed by mixing a bridging agent stock solution and water in a volume ratio of 1:1. Specific examples of the above-mentioned bridging agent stock solution may include, but are not limited to, polycarbodiimide, water-dispersed isocyanate compounds (for example, blocked or unblocked isocyanate compounds and polyisocyanates), and amine compounds. [e.g., melamine], aziridine compound (e.g., polyaziridine), and epoxy resin, and any combination thereof. The above-mentioned bridging agent (D) may be used singly or in combination of plural kinds.

In general, the bridging agent (D) can be used in an amount of from 0.5 part by weight to 4 parts by weight based on 100 parts by weight of the aqueous PU resin (A). If the amount of the bridging agent (D) used is less than 0.5 parts by weight, the strength of the subsequently produced porous layer is insufficient. If the amount of the bridging agent (D) used is more than 4 parts by weight, the subsequently obtained porous layer has disadvantages such as excessive hardness and poor flexibility.

Additive (E)

In one embodiment, the present invention may optionally add an additive such as a tackifier (E-1), an antifoaming agent (E-2), a film former (E-3) or a heat sensitive coagulant (E-4). (E) to produce a porous layer with better hand and chroma.

Any of the commercially available products may be used as the tackifier (E-1), and specifically, for example, a tackifier (IV3800) manufactured by Taichang Resin Co., Ltd. or a tackifier (NEOSTECKER) made by Taiwan Rihua Chemical Co., Ltd., but the present invention is not limited thereto. this.

Specific examples of the antifoaming agent (E-2) described above include compounds such as polyoxymethylene, higher alcohols, polyethers, fatty acid esters, polyethylene glycols, and mineral oils. The above antifoaming agents may be used singly or in combination of plural kinds.

Any commercially available product can be used as the above-mentioned film-forming agent (E-3), and specifically, for example, a filming agent (RY903) is produced by Lidesheng Co., Ltd., but the present invention is not limited thereto.

The above-mentioned thermosensitive coagulant (E-4) can be used in any commercially available product, more preferably a steroidal thermosetting agent, and the chroma of the obtained porous layer can be improved. For example, the thermosensitive coagulant (E-4) is specifically, for example, a compound having an ethylene oxide group in the molecule, FA-3031 (purchased from Shin-Etsu Chemical Co., Ltd.), TPA4380 (purchased from Momentive Corporation), and Coagulant W. (purchased from Bayer), of which FA-3031 is preferred. Further, an inorganic salt such as NaCl or CaCl ₂ may be added to the thermosensitive coagulant (E-4).

In general, the amount of the tackifier (E-1) used is from 0 parts by weight to 6 parts by weight based on 100 parts by weight of the aqueous PU resin (A), and the amount of the antifoaming agent (E-2) is used. From 0 parts by weight to 0.3 parts by weight, a film former (E-3) is used in an amount of from 0 part by weight to 3 parts by weight, and the heat-sensitive coagulant (E-4) is used in an amount of from 0 part by weight to 3 parts by weight.

Further, in addition to the above-mentioned additive (E), the high-color aqueous PU resin composition (F) of the present invention may further contain a dispersing agent (for example, Rheodol AO-15V, HLB3.5 manufactured by Kao Co., Ltd.) to improve the preparation. The hand of the porous layer is obtained without reducing the friction fastness.

After coating the substrate with the high-color aqueous PU resin composition (F) described above, the substrate is then subjected to heat treatment to obtain a porous layer.

It should be noted that when the surface of the substrate to be used is not flat, the primer coating step of the above dry coating step may be performed first. The primer step referred to herein may be a high chroma water-based PU resin composition (F), or an aqueous PU resin (A) and a commercially available acrylic resin or polyester resin (for example, Dali Chemical Co., Ltd. under the trade name R-235). Acrylic resin is blended in an amount of 50 parts by weight, and further added 0 to 4 parts by weight of the pigment (B), 0 to 100 parts by weight of the foaming aid (C), 2 parts by weight of the bridging agent (D), and 0 to The undercoat composition formed by 5 parts by weight of the tackifier (E-1) is applied to a substrate having an uneven surface to obtain a flat surface.

Second, heat treatment

Next, the substrate coated with the above-described high chroma water-based PU resin composition (F) is subjected to heat treatment to form a porous layer.

The above heat treatment is carried out at a temperature of 80 ° C to 130 ° C to remove moisture of the high chroma water-based PU resin composition (F), to cure the high chroma water-based PU resin composition (F) and form a coating layer, and to borrow a foaming aid (C) volatilizes to form a porous layer, and the porous layer has a plurality of One continuous hole. In particular, the lower the temperature of the above heat treatment, the better the chroma and the hand feeling. However, if the temperature is too low, the generation of bubbles is caused, so the above range is preferred.

Further, the obtained porous layer does not need to be subjected to raising treatment, and there is no adhesive layer between the porous layer and the substrate layer.

The aqueous PU resin (A) obtained by the above method does not require the use of a large amount of organic solvent, and the high-color aqueous PU resin composition (F) obtained by using the aqueous PU resin (A) does not require the addition of ultrafine fibers and powders. Additive or foaming agent. Further, the porous layer obtained by using the high chroma water-based PU resin composition (F) has a chroma of not less than 5, a friction fastness of not less than 4 grades, and a good suede feel.

The following examples are provided to illustrate the application of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.

Preparation of waterborne PU resin Synthesis Example 1

This synthesis example is 100.8 parts by weight of hexamethylenediisocynate (HMDI; a), 256.6 parts by weight of a polycarbonate diol (Nippollan-965, manufactured by Nippon Poly; b-1), and 3.6 parts by weight. 1,3-Buthyleneglycol (c-1) was stirred and heated at 80 to 90 ° C for 2.5 hours to form a first prepolymer. After cooling the first prepolymer to 70-75 ° C, 0.27 parts by weight of trimethylolpropane (c-2) and 13.41 parts by weight are further added. Dimethylol propionoc acid (DMPA; d) is reacted at a temperature of 70 to 75 ° C to synthesize a second prepolymer.

When the second prepolymer reaches a specific viscosity (for example, 4400 cps/70 ° C), after cooling to 65 ° C, 17.2 parts by weight of N-methylmorpholine (N-methylp; e) is added and stirred for 5 minutes. Thereafter, 30 parts by weight of acetone (acetone; h) was further added for dilution. Thereafter, 11.94 parts by weight of a dispersant (Triton X-100, Dow Chemical Co., Ltd.; HLB 14.1; f-2) was added, and the dispersion was continuously stirred or rapidly stirred (speed: 6000 to 10000 rpm) for 15 minutes to prepare a dispersion. .

Next, 20.7 parts by weight of an aqueous solution (piperazine; g) containing 10% by weight of piperazine was added, stirred at 40 to 50 ° C for 1 hour, and further stirred at room temperature for 16 hours to obtain an aqueous polyamino group. Polyurethane (PU) resin (A).

Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8

Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8 used the same production method as in Synthesis Example 1, except that Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8 were used to change the kind and amount of raw materials; Relevant physical properties are listed in Tables 1 to 2.

Preparation of porous layer for high chroma waterborne PU resin suede fabric Example 1

Example 1 is 100 parts by weight of the aqueous PU resin (A) of Synthesis Example 1 and 2 parts by weight of a bridging agent (150HD; Taichang Resin; D) After mixing and stirring (500 rpm) for 1 minute, 40 parts by weight of foaming aid (IP SOLVENT 1620; Japan Idemitsu Co., Ltd.; C-1) was added in two portions, and the stirring speed was increased from 500 rpm to 2000 rpm and continued. 1 minute, add 4 parts by weight of pigment (WUB Black 1C058; Da Kung Chemical; B-2), stir at 2000 rpm for 1 minute, then add 0.44 parts by weight of tackifier (trade name NEOSTECKER; Taiwan Rihua Chemical E-1) Stir and adjust the viscosity (for example, 15000 cps/25 ° C) to form a high chroma water-based polyurethane resin composition (F).

Examples 2 to 18 and Comparative Examples 1 to 9

In Examples 2 to 18 and Comparative Examples 1 to 9, the same production method as in Example 1 was used, except that Examples 2 to 18 and Comparative Examples 1 to 9 were used to change the kind and amount of the raw materials. The formulation and related evaluation results are listed in Tables 1 to 4.

Porous layer coating process for high chroma water-based PU resin-like suede fabric

Next, the high chroma water-based PU resin composition (F) was applied onto the substrate by a dry coating method at a coating amount of 150 gr/cm ² . Next, the coated substrate is placed in an oven at about 110 ° C and baked for about 3 minutes to remove the moisture of the high chroma water-based PU resin composition (F) while curing to form a coating layer, and The foaming aid (C) is volatilized to form a porous layer. Thereafter, the chroma, the hand feeling, the film strength, and the rubbing fastness in the dry/wet state of the porous layer were evaluated, and the results are shown in Tables 3 to 4, and the relevant evaluation methods will be described later.

Evaluation method

1. chroma

The chroma referred to in the present invention is a C* value measured by a DATACOLOR 600 spectrophotometer, and the C* is calculated by the following formula (IV):

The a and b of the above formula (IV) are parameters measured by a spectrophotometer and the color difference from the standard. The larger the C* obtained by the above formula (IV), the higher the chroma.

2. feel

The surfaces of the porous layers prepared in the above Examples 1 to 18 and Comparative Examples 1 to 9 were touched by hand to evaluate the touch and softness, and the relevant evaluation criteria were as follows:

○: better (the surface is finer, the touch is moist, and the softness is good)

△: Normal (surface, touch and softness)

×: Poor (the surface is thicker, the touch is dryer, and the softness is poor)

In particular, when the symbol "~" is on the left side of the above-mentioned legend, it indicates a difference from the evaluation standard represented by the legend. For example, "~△" means that it is a little worse than Δ. Conversely, when the symbol "~" is on the right side of the above legend, it means that it is better than the evaluation standard represented by the legend.

3. Film strength

The film strength according to the present invention means the degree of peeling resistance of the high chroma water-based polyurethane resin (F) applied to the substrate. In the evaluation method, the surface of the substrate coated with the high chroma water-based PU resin (F) was scraped with a nail to determine the degree of peeling of the high chroma water-based PU resin (F). The relevant evaluation criteria are as follows:

○: preferably (the surface of the aqueous polyurethane resin is not easy to fall off)

△: Normal (the surface of the waterborne polyurethane resin will peel off a little)

×: Poor (the surface of the water-based polyurethane resin is easy to fall off)

4. Friction fastness (dry)

The friction fastness described in this case is divided into dry and wet. Dry friction fastness was carried out by using a dry white cotton cloth on a friction tester, and rubbing the substrate coated with the high chroma water-based PU resin composition (F) of the present invention back and forth at a frequency of 10 times 10 times to confirm the coating. The fastness of the high chroma water-based PU resin composition (F) on the substrate under dry rubbing. The evaluation criteria are represented by numbers 1 to 5. The greater the number, the better the table fastness.

5. Friction fastness (wet)

The test method of wet friction fastness is the same as the above-mentioned friction dry fastness, except that the above-mentioned dry white cotton cloth is replaced with a wet white cotton cloth to confirm that the high chroma water-based PU resin composition (F) coated on the substrate is in a wet state. Friction fastness under friction. The evaluation criteria are represented by numbers 1 to 5. The greater the number, the better the table fastness.

From the results of Tables 3 to 4, in the aqueous PU resin (A) used in Examples 1 to 18, the carboxylic acid group content was from 0.9 part by weight to 1.3 parts by weight, and the content of the polycarbonate polyol (b) The high-color aqueous PU resin composition (F) obtained by applying the appropriate amount of the pigment (B), the foaming auxiliary (C), and the bridging agent (D) in an amount of 60 parts by weight to 68 parts by weight After the substrate, the porous layer obtained by heat treatment may have a chroma of more than 5 and a friction fastness of not less than 4 grades.

In contrast, as shown in Table 4, in Comparative Example 2, a porous layer was obtained by using a polyether, and the predetermined chroma and hand were not obtained. When the polycarbonate polyol contained in Comparative Example 4 was too small, the predetermined chroma could not be obtained. On the other hand, in Comparative Example 5, when the amount of the carboxylic acid group contained in the aqueous PU resin was too large, there was a problem that the hand feeling was not good. Further, as shown in Comparative Example 6, when the diamine compound was not added to the aqueous PU resin, the obtained porous layer film had low strength.

In addition, the porous layer obtained by the method of the invention does not need to add additional powder additives or ultrafine fibers, and does not need to be subjected to raising treatment to obtain a porous layer with a leather-like feel, which is advantageous for the suede composite material. Applications.

It should be noted that the present invention describes a high chroma water-based polyurethane resin of the present invention and a method for producing the same according to specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments, and the likes thereof. The use of the composite material, but it is to be understood by those skilled in the art that the present invention is not limited thereto, and the high chroma water-based polyurethane resin of the present invention is not deviated from the spirit and scope of the present invention. The method of manufacture and its methods of manufacture can also be carried out using other compounds, compositions, reaction conditions, processes, analytical methods or equipment.

It can be seen from the above embodiments of the present invention that the high chroma water-based polyurethane resin and the method for producing the same of the present invention have an advantage in that the content of the carboxylic acid group and the polycarbonate polyol contained in the aqueous PU resin is not required to be controlled. The ultra-fine fiber, the powder filler and the high-color water-based polyurethane resin obtained by directly coating the obtained high-color water-based polyurethane resin on the substrate can be obtained with good chroma and suede hand feeling. The substrate and the resulting substrate also have good friction fastness.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

a: hexamethylenediisocynate (HMDI)

B-1: polycarbonate diol (Nippollan-965, manufactured by Japan Poly)

B-2: polycarbonate diol (Nippollan-963, manufactured by Japan Poly)

b': polytetrahydrofuran ether (PTG-1000)

C-1: 1,3-butanediol (1,3-buthyleneglycol; 1,3-BG)

C-2: trimethylolpropane (TMP)

d: dimethylol propionoc acid (DMPA)

e: N-methylmorpholine (N-mmp)

F-1: Tergitol TMN 100 (The Dow Chemical Company; HLB 14.4)

F-2: TritonX-100 (The Dow Chemical Company)

g: piperazine

h: acetone (acetone)

B-1: WUB Blue 1C059 (大恭化学)

B-2: WUB Black 1C058 (大恭化学)

C-1: IP SOLVENT 1620 (Japan Idemitsu Kosan)

C-2: IP SOLVENT 1016 (Japan Idemitsu Kosan)

D: 150HD (Taichang Resin)

E-1: Trade name NEOSTECKER (Taiwan Rihua Chemical Co., Ltd.) or Taichang Tackifier (IV3800)

E-3: trade name RY903 (Lide Desheng Co., Ltd.)

E-4: FA-3031 (Shin-Etsu Chemical Co., Ltd.)

100‧‧‧ method

110, 120, 130, 140, 150, 160‧ ‧ steps

Claims (16)

A method for producing an aqueous polyurethane resin, comprising: prepolymerizing a diisocyanate compound (a), a polycarbonate polyol (b) and a first hydroxyl group-containing compound (c-1) to form a first prepolymer; a polymerization reaction of the first prepolymer, a second hydroxyl group-containing compound (c-2) and a carboxylic acid group-containing compound (d) to form a second prepolymer, Wherein the second prepolymer has at least one carboxylic acid group; neutralizing the second prepolymer with a neutralizing agent (e); and adding the neutralized second prepolymer to a solvent (h) Diluting the second prepolymer; adding the diluted second prepolymer to a mixed solution of a dispersing agent (f) and water to form a dispersion, wherein the dispersing agent (f) is a An ethoxylated nonionic dispersant or an ethoxylated anionic dispersant; and a chain extension reaction of the dispersion with the diamine compound (g) to form the aqueous polyurethane resin (A) wherein the aqueous polyurethane resin (A) is a self-emulsifiable aqueous polyurethane resin, and wherein the aqueous polyurethane is based thereon The urethane resin (A) has a total solid content of 100 parts by weight, and the aqueous polyurethane resin (A) has 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group and 60 parts by weight to 68 parts by weight. The polycarbonate polyol (b), the dispersant (f) is contained in an amount of more than 0 parts by weight to less than 7 parts by weight, and the total amount of the solvent (h) and the water is 136.09 parts by weight to 144.07 parts by weight. The method for producing an aqueous polyurethane resin according to claim 1, wherein the polycarbonate polyol (b) comprises a polycarbonate diol, and the arithmetic mean molecular weight of the polycarbonate diol is 700 to 3000. The method for producing an aqueous polyurethane resin according to claim 1, wherein the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2) are aliphatic polyols. The method for producing an aqueous polyurethane resin according to claim 3, wherein the first hydroxyl group-containing compound (c-1) comprises 1,3-butylene glycol, and the second hydroxyl group-containing compound ( C-2) contains trimethylolpropane or glycerol. The method for producing an aqueous polyurethane resin according to claim 1, wherein the carboxylic acid group-containing compound (d) is a carboxylic acid group-containing short-chain polyol, and the carboxylic acid group-containing The short chain polyol has a molecular weight or an arithmetic mean molecular weight of from 100 to 1000. The method for producing an aqueous polyurethane resin according to claim 5, wherein the carboxylic acid group-containing short-chain polyol comprises dimethylolpropionic acid and dimethylolbutanoic acid. The method for producing an aqueous polyurethane resin according to claim 1, wherein the neutralizing agent (e) comprises an organic neutralizing agent or an inorganic neutralizing agent. The method for producing an aqueous polyurethane resin according to the above aspect of the invention, wherein the aqueous polyurethane resin (A) has 3 parts by weight to 5 parts by weight of the dispersing agent (f). The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has 0.05 to 1 part by weight of the diamine compound (g) based on the aqueous polyurethane resin (A). . The method for producing an aqueous polyurethane resin according to claim 1, wherein the solvent (h) is acetone, methyl ethyl ketone, and a combination thereof. According to the method for producing an aqueous polyurethane resin according to the first aspect of the invention, after the chain extension reaction, a stirring step is further included. The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has from 0.9 part by weight to 1.0 part by weight of the carboxylic acid group. The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has 64 parts by weight to 68 parts by weight of the polycarbonate polyol (b) ). An aqueous polyurethane resin obtained by the method according to any one of claims 1 to 13, and based on the total solid content of the aqueous polyurethane resin (A) is 100 The aqueous polyurethane resin (A) has 0.9 parts by weight to 1.3 parts by weight of a carboxylic acid group and 60 parts by weight to 68 parts by weight of the polycarbonate polyol (b) in parts by weight. A method for producing a porous layer for a high chroma water-based polyurethane resin-like suede composite material, comprising: performing a dry coating step of coating a high chroma water-based polyurethane resin composition (F) on a a surface of one of the substrates, wherein the high-color aqueous polyurethane resin composition (F) comprises: the aqueous polyurethane resin (A) according to claim 14; a pigment (B), Wherein the pigment (B) is a water-soluble anion-dispersed pigment; a foaming aid (C), wherein a volatilization rate of one of the foaming assistants (C) is lower than a volatilization rate of water, and the foaming aid Agent (C) is insoluble in water And not miscible with the aqueous polyurethane resin (A); and a bridge (D), and wherein the pigment (B) is used in an amount of 100 parts by weight based on the aqueous polyurethane resin (A) Used in an amount of 2 to 6 parts by weight, the foaming auxiliary (C) is used in an amount of 20 to 60 parts by weight, and the bridging agent (D) is used in an amount of 0.5 to 4 parts by weight; The substrate of the high-color aqueous polyurethane resin composition (F) is subjected to heat treatment to form the high-color aqueous polyurethane resin composition (F) to form a porous layer, wherein the heat treatment comprises: removing the a water of a high chroma waterborne polyurethane resin composition (F); curing the high chroma waterborne polyurethane resin composition (F) and forming a coating layer; and forming a porous layer, wherein the porous The layer has a plurality of continuous pores formed by volatilization of the foaming aid (C), and wherein the porous layer is not subjected to raising treatment, and the porous layer is directly coated with the substrate and is not There is any adhesive layer, and the color of the porous layer is not less than 5, and the friction fastness of the porous layer is Less than four. The method for producing a porous layer for a high-color aqueous polyurethane resin-like suede composite material according to the fifteenth aspect of the invention, wherein the high-color aqueous polyurethane resin composition (F) further comprises an additive (E), and the additive (E) is selected from the group consisting of a tackifier, an antifoaming agent, a film former or a heat-sensitive coagulant.