TWI437014B - Anionic water-based polyurethane resin and method of producing the same - Google Patents

Description

Anionic waterborne polyurethane resin and method of producing the same

The invention relates to an aqueous polyurethane resin and a manufacturing method and application thereof, in particular to an anionic water-based polyurethane resin with hydrolysis resistance, a manufacturing method thereof and application thereof.

Polyurethane (PU) resins are widely used and widely used materials. Due to the use of conventional solvent-based PU resins in the use or post-processing, organic volatile compounds (VOCs) such as solvents are released into the atmosphere, causing environmental and ecological damage. However, the water-based PU resin replaces the volatile organic solvent with water, is an environmentally friendly product and does not cause an environmental burden, and thus has a tendency to gradually replace the conventional solvent-based PU resin.

According to the hydrophilic functional group of the main chain of the aqueous PU resin, it can be broadly classified into three types: anionic water-based PU resin, cationic water-based PU resin, and non-ionic water-based PU resin. Next, the above aqueous PU resin can be further synthesized by two major types of methods, such as an acetone processing method and a prepolymer mixing processing method.

Briefly, an anionic aqueous PU resin is synthesized by an acetone processing method, which is an addition polymerization reaction of a polyisocyanate with a polypolyol to form a PU pre-cyanide-based terminal. polymer. Next, a hydrophilic functional group is added as an internal emulsifier, and acetone is used as a reaction solvent. The acetone can adjust the viscosity of the polymer without participating in the synthesis reaction of the PU resin, and can form an aqueous phase with the aqueous phase solution. The dispersion, which has a low boiling point, is easily separated and recovered from the aqueous PU dispersion. After the reaction is completed, deionized water and a chain extender are added for chain extension reaction. Thereafter, acetone is separated and recovered by means of concentration under reduced pressure or the like to obtain a self-emulsified aqueous-based PU dispersion containing no organic solvent.

In general, the aqueous PU resin has a small average molecular weight, and its hydrolysis resistance, mechanical strength, stability, heat resistance, and the like are also insufficient, and it is difficult to compare with a conventional solvent-based PU resin. Therefore, many studies have improved the properties of aqueous PU resins by improving the process or post-treatment, but the degree of improvement is rather limited.

In view of the above, there is a need to provide a method for producing an aqueous polyurethane resin to improve the disadvantages of the conventional aqueous polyurethane resin and its process.

Therefore, one aspect of the present invention provides a method for producing an anionic aqueous polyurethane resin by separately adding an organic base type neutralizing agent and an inorganic base type neutralizing agent in different steps, and an organic base. The type neutralizing agent and the inorganic alkali type neutralizing agent have a predetermined ratio to obtain an anionic aqueous polyurethane resin having a good mechanical strength.

Another aspect of the present invention provides an anionic aqueous polyurethane resin having hydrolysis resistance which is obtained by the above method.

According to still another aspect of the present invention, there is provided a composite fabric having hydrolysis resistance, characterized in that the composite fabric is impregnated with a base fabric by an impregnation liquid comprising the anionic aqueous polyurethane resin described above. And then dried to obtain.

Still another aspect of the present invention provides a film having hydrolysis resistance, wherein the film has the above-described anionic water-based polyurethane resin having hydrolysis resistance, when the film is exposed to high temperature and high humidity. After a period of time, for example, a temperature of 70 ° C and a humidity of 95% after 4 days, the tensile strength of the film is from 30 kgf / cm ² to 90 kgf / cm ² , and the elongation of the film is from 150 to 450 percent.

Still another aspect of the present invention provides a composite fabric having hydrolysis resistance, wherein the composite fabric comprises a base fabric and the above-mentioned film directly attached thereto.

According to the above aspect of the invention, a method for producing an anionic water-based polyurethane resin having hydrolysis resistance is proposed. In one embodiment, first, the diisocyanate compound (A) and the polyether polyol (B) are prepolymerized to form a first prepolymer. Next, the first prepolymer is reacted with the carboxylic acid group-containing compound (C) in an organic solvent (D) to form a second prepolymer, wherein the second prepolymer has at least one hydrophilic side chain group. Then, an organic base type neutralizing agent (E-1) is added to the second prepolymer. Thereafter, the second prepolymer is uniformly dispersed in a dispersion containing the inorganic base type neutralizing agent (E-2) to form an anionic aqueous polyurethane resin. The molar percentage of the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) is from 80:20 to 20:80.

According to an embodiment of the present invention, the above-mentioned organic base type neutralizing agent (E-1) may include, but is not limited to, tri-n-propylamine, N-methylmorpholine or any combination thereof.

According to an embodiment of the present invention, the above inorganic base type neutralizing agent (E-2) may include, but not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide or any combination thereof.

According to an embodiment of the invention, the dispersion further comprises at least inorganic cerium oxide (F) and water.

According to another aspect of the present invention, an anionic aqueous polyurethane resin having hydrolysis resistance is obtained which is obtained by the above method.

According to still another aspect of the present invention, a composite fabric having hydrolysis resistance is provided, wherein the composite fabric is impregnated with a base fabric by an impregnation liquid comprising the anionic aqueous polyurethane resin described above, and dried. Processed.

According to still another aspect of the present invention, there is provided a film having hydrolysis resistance, wherein the film has an anionic aqueous polyurethane resin as described above, when the film is exposed to a temperature of 70 ° C and a humidity of 95% After 4 days, the tensile strength of the film was 30 kgf/cm ² to 90 kgf/cm ² , and the elongation of the film was 150% to 450%.

According to still another aspect of the present invention, a composite fabric having hydrolysis resistance is provided, wherein the composite fabric comprises a base fabric and a film directly attached to one of the base fabrics, and the film is the above-mentioned film having hydrolysis resistance.

The invention relates to an anionic aqueous polyurethane of the invention, a preparation method thereof and an application thereof, which are respectively added with an organic alkali type neutralizing agent and an inorganic alkali type neutralizing agent in different steps, and an organic alkali type neutralizing agent and an inorganic agent The alkali type neutralizing agent has a predetermined ratio, thereby producing an anionic aqueous polyurethane resin which is excellent in hydrolysis resistance and mechanical strength.

As described above, the present invention provides an anionic aqueous polyurethane resin and a method for producing the same, which are respectively added with an organic alkali type neutralizing agent and an inorganic alkali type neutralizing agent in a predetermined step, and the organic alkali type is neutralized. The anionic aqueous polyurethane resin having a hydrolysis resistance and mechanical strength is preferably obtained by a predetermined ratio of the agent and the inorganic alkali-type neutralizing agent.

In one embodiment, the anionic aqueous polyurethane resin of the present invention contains at least a diisocyanate compound (A), a polyether polyol (B), a carboxylic acid group-containing compound (C), an organic solvent (D), Alkaline neutralizing agent (E-1) and inorganic base type neutralizing agent (E-2). The following is described.

Anionic waterborne polyurethane resin

Diisocyanate compound (A)

The diisocyanate compound (A) of the present invention may be any organic diisocyanate compound used for the production of a PU emulsion, including but not limited to aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate or any of the above. combination.

Specific examples of the aforementioned aliphatic diisocyanate are: isophorone diisocyanate, 1,6-hexamethylene diisocyanate (HDI), (tetramethylxylylene diisocyanate; TMXDI) , dihexyl diisocyanate, and the like. The aforementioned alicyclic diisocyanate may be, for example but not limited to, 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI) or the like. Specific examples of the aforementioned aromatic diisocyanate are: 2,4-tolylene diisocyanate, 2,6-benzylidene diisocyanate, diisocyanate 4,4'-diphenylmethane acid, p-benzoylene diisocyanate, dimethylene diisocyanate, 1,5-naphthyl diisocyanate, and the like.

The diisocyanate compound (A) is from 6 to 12% by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin.

Polyol (B)

The polyol (B) used in the present invention may be a difunctional or polyfunctional polyol, which may include, but is not limited to, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol. A polyacrylate polyol or a combination of any of the above is preferred, and a polyether polyol is preferred. In one example, the polyether polyol (B) has an arithmetic mean molecular weight of from 200 to 5,000, preferably an arithmetic average molecular weight of from 500 to 2,000, more preferably an arithmetic average molecular weight of from 800 to 1,500.

Further, suitable polyether polyols as described above may include, but are not limited to, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetrahydrofuran ether, and the like.

The above-mentioned suitable polyester polyols include aliphatic diols, alicyclic diols, triols, tetraols and the like, and more preferably an aliphatic diol or an alicyclic diol. Specific examples of the aforementioned aliphatic polyester polyol are, for example, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexyl Glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,10-nonanediol, butanediol-adipate copolymer [poly(butanediol-co-adipate)glycol; PBA], polytetramethylene glycol (PTMEG) , hexanediol-co-adipate glycol; PHA, Poly-ethylene-co-adipate glycol; PEA, Polypropylene Glycol ), polyethylene glycol (Polyethylene Glycol), polytetrahydrofuran ether (PTG-1000), and the like. The aforementioned alicyclic diols such as cyclohexane-dimethanol, cyclohexane diol and the like.

The above-mentioned suitable polycarbonate polyol can be reacted by a carbonate and a polyol, wherein the specific ones of the carbonates are, for example, dialkyl carbonates, alkylene carbonates, and diaryl carbonate. Esters and the like. Specific examples of the dialkyl carbonates include dimethyl carbonate and diethyl carbonate. Specific examples of the alkylene carbonate are, for example, ethylene carbonate. Specific examples of the diaryl carbonates are, for example, diphenyl carbonate.

Suitable polycaprolactone polyols described above may, for example, be those having an average molecular weight of from 200 to 5,000.

Suitable polyacrylate polyols described above can be reacted via a acrylate with a polyol.

In addition, polyester polycarbonate polyols may also be used, which are obtained by simultaneously reacting all of the polyol, the polycarboxylic acid and the polycarbonate compound; and reacting the polyester polyol and the carbonate obtained previously. Obtainer; obtained by reacting a polycarbonate polyol previously prepared with a polycarboxylic acid; or obtaining a polyester polyol obtained by previously reacting with a polycarbonate polyol previously obtained.

The above polyol (B) may be used singly or in combination of plural kinds. The polyol (B) is 15% by weight to 28% by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin.

Carboxylic acid-containing compound (C)

The carboxylic acid group-containing compound (C) used in the present invention can impart an anionic aqueous polyurethane resin having a hydrophilic side chain group such as a carboxylic acid group, a sulfonic acid group (-SO ₃ H), or a phosphoric acid group (- OPO ₃ H ₂ ) or phosphonic acid group (-PO ₃ H ₂ ). Specific examples of the above carboxylic acid group-containing compound (C) may include, but are not limited to, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, a tricarboxylic acid, and the like.

Specific examples of the aforementioned aliphatic dicarboxylic acid are: succinic acid, glutaric acid, adipic acid, suberic acid, azelic acid, azelaic acid, dodecanedioic acid, 2-methyl Succinic acid, 2-methyladipate, 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 the like. Specific examples of the above aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, phthalic acid, naphthalene dicarboxylic acid and the like. Specific examples of the aforementioned alicyclic dicarboxylic acid include 1,4-cyclohexane-dicarboxylic acid and the like. Specific examples of the aforementioned tricarboxylic acid include trimellitic acid, trimesic acid, and the like. Further, the carboxylic acid group-containing compound (C) further includes an ester derivative formed by the above compound, for example, an ester or an anhydride thereof.

Among the above-mentioned carboxylic acid group-containing compound (C), an aliphatic carboxylic acid and an ester derivative formed thereof are preferable, for example, dimethylolpropionic acid. The above-mentioned carboxylic acid group-containing compound (C) may be used singly or in combination of two or more kinds.

The carboxylic acid group-containing compound (C) is from 1.5% by weight to 3.5% by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin.

Organic solvent (D)

In the present invention, the organic solvent (D) is such that it can dissolve the diisocyanate compound (A), the polyol (B), the carboxylic acid group-containing compound (C), and does not react with the above components, and has appropriate volatility. good.

The organic solvent (D) used in the present invention may include, but is not limited to, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl Acetone (dimethylacetamide; DMAc), dimethylsulfoxide (DMSO), acetone (acetone), methyl ethylketone (MEK), toluene, etc., preferably acetone.

The organic solvent (D) is from 1.5% by weight to 3.0% by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin.

Alkaline neutralizer (E)

The alkali type neutralizing agent (E) of the present invention includes an organic base type neutralizing agent (E-1) and an inorganic base type neutralizing agent (E-2). Among them, suitable organic base type neutralizing agents (E-1) may include, but are not limited to, ammonia, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, monoethanolamine, Porphyrin, N-methylmorpholine, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, N,N-dimethylethanolamine, N,N- Ethylethanolamine, N-methyl-diethanolamine, N-phenyl-diethanolamine or any combination of the above is preferably tri-n-propylamine, triethanolamine or N-methylmorpholine. Suitable inorganic base type neutralizing agents (E-2) may include, but are not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide or any combination of the above. The above-mentioned organic base type neutralizing agent (E-1) and inorganic base type neutralizing agent (E-2) may be used alone or in combination of two or more kinds.

In general, the molar percentage of the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) is from 80:20 to 20:80. The total weight of the anionic aqueous polyurethane resin is 100% by weight, the organic base type neutralizing agent (E-1) is 0.5% by weight to 2% by weight, and the inorganic base type neutralizing agent (E-2) is 0.05 weight percent to 0.5 weight percent.

Further, the inorganic base type neutralizing agent (E-2) described above may be further optionally added with inorganic cerium oxide (F) and water. The inorganic cerium oxide (F) is from 0.10% by weight to 0.50% by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin.

The water used in the present invention is not particularly limited. Specific examples thereof include 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 have been proposed in recent years. Various functional waters, etc. The water (D) 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, distillation treatment, irradiation with ultraviolet light if necessary, or passing through a filter. The total weight of the anionic aqueous polyurethane resin is 100% by weight, and the water is 60% by weight to 70% by weight.

Anionic waterborne polyurethane resin and method of producing the same

The anionic aqueous polyurethane resin of the present invention is obtained from a self-emulsifying aqueous dispersion. In an example, first, as shown in the formula (I), the diisocyanate compound (A) and the polyether polyol (B) are prepolymerized at 80 ° C to 90 ° C for about 2 hours to form a first a prepolymer:

In the formula (I), the formula (I-1) means a diisocyanate compound (A), the formula (I-2) means a polyol (B), and the formula (I-3) means a first prepolymer. 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 foregoing catalyst may include, but is not limited to, tin octylate, monobutyltin triacetate, monobutyltin monooctanate, monobutyltin monoacetate, monobutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, distearate. Organotin compounds such as butyltin, dibutyltin dilaurate, dibutyltin maleate; organotitanium compounds such as tetraisopropyl titanate and tetra-n-butyl titanate; triethylamine, N,N-diethylcyclohexane Tertiary amines such as hexylamine, N,N,N',N'-tetramethylethylethylamine, and triethylethylenediamine. 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 and poly(two Propylene glycol) phenyl phosphite (PDP) or the like.

In addition, in the reaction of the formula (I), the above polyol (B) may be more selectively used in combination with a chain extender, wherein a suitable chain extender may include a diamine compound or a diol compound, for example, for example, : ethylene glycol (EG), 1,4 butanediol (1,4-Bene), 1,6-hexanediol (1,6-hexanediol; 1,6- HD), ethylenediamine, hydrazine, and the like.

After the first prepolymer is cooled to about 65 ° C or lower, the first prepolymer and the remaining diisocyanate compound (A) of the formula (I-4) are obtained as shown in the formula (II), And a carboxylic acid group-containing compound (C), which is reacted in an organic solvent (D) at 68 ° C to 73 ° C to form a second prepolymer, wherein the second prepolymer has at least one hydrophilic side chain group, For example, 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 (C), 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 5000 cps (test temperature: 70 ° C), but the invention is not limited thereto.

Then, in one example, the present invention is to add an organic base type neutralizing agent (E-1) to the second prepolymer to form a dispersion containing the second prepolymer represented by the formula (III).

It is worth mentioning that the present invention separates the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) in different steps, and excludes the addition of the organic base type neutralization in the same step. The agent and the inorganic base type neutralizing agent are used to obtain an anionic aqueous polyurethane resin which is excellent in hydrolysis resistance and mechanical strength.

Thereafter, the dispersion containing the second prepolymer represented by the formula (III) is uniformly dispersed in an aqueous dispersion containing the inorganic base type neutralizer (E-2) to form an anionic aqueous polyurethane. Acid ester resin. In one example, the molar percentage of the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) is from 80:20 to 20:80. If the molar percentage of the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) is higher than 80:20 or lower than 20:80, the strength of the subsequently produced film is insufficient.

The aforementioned aqueous dispersion further contains at least inorganic cerium oxide (F) and water. In one example, the inorganic cerium oxide (F) is from 0.1% by weight to 0.5% by weight based on the total weight of the anionic aqueous polyurethane resin, and the water is from 60% by weight to 70% by weight.

The aqueous dispersion containing the inorganic base type neutralizer (E-2), the inorganic cerium oxide (F) and water may be stirred, before the dispersion containing the second prepolymer represented by the formula (III) is added. Highly dispersed aqueous dispersions are prepared in advance by means of ultrasonic and/or high-speed dispersion. In an example, the aqueous dispersion containing the inorganic alkali type neutralizer (E-2), the inorganic cerium oxide (F), and water is a transparent and highly dispersed aqueous dispersion. The dispersion containing the second prepolymer represented by the formula (III) is added to an aqueous dispersion containing an inorganic base type neutralizer (E-2), inorganic cerium oxide (F) and water to prepare an anionic type. Aqueous polyurethane resin. In another illustration, an appropriate amount of isopropanal (IPA) may be used in combination.

When the film is exposed to a high temperature and high humidity environment for a period of time, for example, a temperature of 70 ° C and a humidity of 95% after 4 days, the tensile strength of the film can still reach 30 kgf / cm ² to 90 kgf / cm ² , and the film The elongation still has a percentage of 150 to 450, which does have better hydrolysis resistance and mechanical strength.

Since the above anionic aqueous polyurethane resin has better hydrolysis resistance and mechanical strength, it can be applied to the production of a composite fabric having hydrolysis resistance. In one embodiment, the conventional base fabric may be impregnated with the impregnation liquid of the anionic aqueous polyurethane resin described above and then dried. Please refer to FIG. 2A, which is a partial flow chart showing the preparation of a composite fabric having hydrolysis resistance according to an embodiment of the present invention. First, the base fabric 201 is introduced into the impregnation liquid 205 by means of a roller 203, wherein the impregnation liquid comprises the above-described anionic water-based polyurethane resin. Next, the resin-impregnated base fabric 201 is subjected to a drying treatment 209 by means of a roller 207 to obtain a composite fabric 221 having hydrolysis resistance.

In another embodiment, the anionic aqueous polyurethane resin can also be used to obtain a film, and after bonding with a conventional base fabric, a composite fabric having hydrolysis resistance can be obtained. Referring to FIGS. 2B-2C, a partial flow diagram of preparing a composite fabric having hydrolysis resistance according to another embodiment of the present invention is shown. First, the anionic aqueous polyurethane resin dispersion is formed into a film 211 by a known process. Next, the film 211 is conveyed by the roller 207, and the skin resin 211 is applied to the film 211 by the doctor blade 204, and then the drying process 209 is performed. Then, the adhesive resin 206 is applied onto the film 211 having the skin resin 202 by the doctor blade 204, and the base fabric 201 (for example, leather) is introduced by the roller 207, and bonded to the film 211. After the drying treatment 209, a composite fabric 223 having hydrolysis resistance was obtained.

The base fabric 201 is introduced into the impregnation liquid 205 by means of a roller 203, wherein the impregnation liquid comprises the above anionic aqueous polyurethane resin. Next, the resin-impregnated base fabric 201 is subjected to a drying treatment 209 by means of a roller 207 to obtain a composite fabric 221 having hydrolysis resistance.

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 anionic waterborne polyurethane resin

Example 1

This example is 8.69 parts by weight of hexamethylene diisocyanate (HMDI; A-1), 20.41 parts by weight of polytetrahydrofuran ether (PTG-1000; B-1; arithmetic mean molecular weight Mn is 1000), and 0.03 parts by weight. The antioxidant is prepolymerized at 80 ° C to 90 ° C for about 2 hours to synthesize the first prepolymer.

After the reactant of the first prepolymer is cooled to about 65 ° C or lower, then 2.09 parts by weight of dimethylolpropionic acid (DMPA; C-1) is added, in acetone (acetone; D- 1) The temperature is gradually raised to about 70 ° C to synthesize a second prepolymer.

When the reactant of the second prepolymer reaches a preset viscosity (for example, 2500 cps to 5000 cps, 70 ° C), the temperature is lowered to about 65 ° C or lower, and 1.85 parts by weight of tri-n-propylamine is added. T-npa; E-1-1) After the neutralization reaction, 65.19 parts by weight of pure water is added, and the mixture is continuously stirred and dispersed, ultrasonically dispersed or dispersed at high speed for 3 hours to 4 hours to form a second prepolymer. The dispersion of the organic base type neutralizing agent (E-1) and the inorganic base type neutralizing agent (E-2) has a molar percentage of 80:20 to 20:80. Thereafter, the anionic aqueous polyurethane resin was tested to form a film, and the hydrolysis resistance and mechanical strength after the preparation and the temperature of exposure to 70 ° C and 95% humidity for 4 days were measured, and the detection method was followed. Repeated.

Examples 2 to 9

The method for preparing an anionic aqueous polyurethane resin of the first embodiment differs in that the examples 2 to 9 change the type and amount of the raw material in the anionic aqueous polyurethane resin, and the formulation and test results thereof are as follows. Table 1 shows.

In Examples 2 to 9, the formulation was additionally supplemented with an inorganic base type neutralizing agent (E-2), wherein Examples 6 and 9 were added to water and/or the day before the preparation of the dispersion containing the second prepolymer. Add sodium hydroxide (E-2-1) and inorganic cerium oxide (F) to isopropanol, stir for 3 hours to 4 hours by stirring, ultrasonic and/or high-speed dispersion, and prepare for high dispersion in advance. An aqueous dispersion wherein the aqueous dispersion has a viscosity of about 100 cps.

Further, in the synthesis of the first prepolymer and the second prepolymer, Examples 8 and 9 further added 0.02 parts by weight of a dibutyltin dilaurate (DBTDL) catalyst.

Comparative example

The method for producing an anionic aqueous polyurethane resin of the same embodiment 8 is different in that the comparative example changes the kind and amount of the raw material in the anionic aqueous polyurethane resin, and the formulation and test results are as shown in Table 1. Shown.

Preparation of resin film

The resin dispersions obtained in Examples 1 to 9 and Comparative Examples were diluted and mixed with water in a volume ratio of 2:1, and then applied to a glass plate to a thickness of about 200 μm. After drying naturally for 2 days to 3 days, the dried coating film is removed from the glass plate, placed in an oven, and heated at about 90 ° C to 150 ° C for about 5 minutes to 30 minutes to prepare an anionic aqueous polyurethane. Acid ester resin film.

Evaluate the effectiveness of resin films

The resin film prepared as described above can be tested for tensile strength, tensile strength, elongation at rest in a static state after being made and after exposure to a temperature of 70 ° C and a humidity of 95% for 4 days according to the tensile test specification of JIS K7127 of Japan. Rate and tensile strength retention rate to assess its efficacy.

Please refer to FIG. 3, which is a schematic view of a tensile test apparatus according to an embodiment of the present invention. First, the resin film prepared as described above is cut to a fixed size, for example, the width ( w ₁ ) is 10 mm but the length ( l ₁ ) is greater than 20 mm, and the marking line is marked (the distance between the marking lines is 20 mm), and then the resin film is applied. The strip 301 is fixed at both ends of the clamp 305 of the clamp 303 of the tensile test apparatus 300 (for example, tensile tester, PT-1202, manufactured by Intertek Scientific Instruments Co., Ltd.) at room temperature (for example, about 25 ° C). The lowering speed was carried out at a stretching speed of 200 mm/min. During the stretching process, both ends of the resin film strip 301 are clamped and simultaneously subjected to a tensile force in the axial direction (for example, the upper and lower directions indicated by the arrow 307), with the result that the resin film strip 301 is elongated in a direction parallel to the force. phenomenon, becomes gradually longer and even rupture, wherein the width of the resin film strip 301 'is of w _2, a length l _2, as shown in FIG. 3B, the hydrolysis resistance and to evaluate the mechanical strength of the resin film of the following items.

1. Film strength:

The above-mentioned stress (kgf) of the resin film strip 301' at 100% modulus (md) is divided by the original area (i.e., length ( l ₁ ) × width ( w ₁ )), that is, film strength (kgf/). Cm ² ).

2. Tensile strength (TS):

The maximum value of the stress (kgf) received by the foregoing resin film strip 301' before breaking is divided by the original area (i.e., length ( l ₁ ) × width ( w ₁ )), that is, tensile strength (kgf/cm ² ) The tensile strength of the resin film strip 301 measured after the preparation was TS ₁ , and the tensile strength measured after 4 days of exposure to a temperature of 70 ° C and 95% humidity was TS ₂ .

3. Elongation (EL):

The change in the length of the fracture surface of the resin film strip 301' before and after the test is as shown in the formula (IV):

4. Tensile strength retention rate (TS retention rate):

The tensile strength of the resin film prepared as described above after the preparation and after exposure to a temperature of 70 ° C and a humidity of 95% for 4 days, as shown in the formula (V):

Please refer to Table 1 and FIG. 4 , wherein FIG. 4 is a graph showing tensile strength of a film subjected to an anionic aqueous polyurethane resin process exposed to a high temperature and high humidity environment according to an embodiment of the present invention. The horizontal axis is the percentage of molars of tri-n-propylamine (T-npa; E-1-1) and sodium hydroxide (NaOH; E-2-1), and the vertical axis is tensile strength (kgf/cm ² ). 401 represents the tensile strength measured after the resin film strip was produced, and curve 403 represents the tensile strength of the resin film strip measured after exposure to a temperature of 70 ° C and a humidity of 95% for 4 days.

From the results of the first table and the fourth graph, it is understood that tri-n-propylamine (T-npa; E-1-1) and sodium hydroxide (NaOH; E-2-1) are separately added to the resin dispersion. When the percentage of moles of tri-n-propylamine (T-npa; E-1-1) and sodium hydroxide (NaOH; E-2-1) is from 80:20 to 20:80, the obtained resin film is exposed to 70. After 4 days, the temperature of °C and the humidity of 95% have better tensile strength, elongation and tensile strength retention, which are representative of its hydrolysis resistance and mechanical strength, and indeed achieve the object of the present invention.

Further, in the resin dispersion, when the inorganic alkali-type neutralizing agent (E-2) is further used in combination with the inorganic cerium oxide (F), the elongation and the tensile strength retention ratio of the obtained resin film are more preferable.

In summary, the method of the present invention is to separately add an organic base type neutralizing agent and an inorganic base type neutralizing agent in different steps, and the organic base type neutralizing agent and the inorganic alkali type neutralizing agent have a preset ratio to prepare It is an environmentally friendly resin which is excellent in hydrolysis resistance and is applied to various fabrics. However, it should be noted that the present invention describes an anionic aqueous polyurethane resin of the present invention and a method for producing the same, with specific components, specific reaction conditions, specific analytical methods, specific tests, specific equipment, and the like as an example. However, it is to be understood by those skilled in the art that the present invention is not limited thereto, and the anionic aqueous polyurethane resin of the present invention and the method for producing the same may be used without departing from the spirit and scope of the present invention. Use other ingredients, other reaction conditions, other analytical methods, other tests, or other equivalent equipment.

It can be seen from the above examples of the present invention that the anionic aqueous polyurethane resin of the present invention and the method for producing the same have the advantages of separately adding an organic alkali type neutralizing agent and an inorganic alkali type neutralizing agent in an initial step, and an organic base. The type of neutralizing agent and the inorganic alkali type neutralizing agent have a predetermined ratio, and an anionic aqueous polyurethane resin having a good mechanical strength can be obtained.

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.

Compound

A-1: hexamethylene diisocyanate (HDI)

B-1: Polytetrahydrofuran ether (PTG-1000)

C-1: dimethylolpropionic acid (DMPA)

D-1: acetone (acetone)

D-2; isopropyl alcohole (IPA)

E-1-1: tri-n-propylamine (T-npa)

E-1-2: N-methylmorpholine (N-mmp)

E-1-3: triethylamine (TEA)

E-2-1: sodium hydroxide

*: Dibutyltin dilaurate (DBTDL)

^# :tetraphenyl dipropyleneglycol diphosphite (TDD)

100. . . method

101. . . Step of forming the first prepolymer

103. . . Forming a second prepolymer wherein the second prepolymer has at least one hydrophilic side chain group

105. . . Step of adding an organic base type neutralizing agent to the second prepolymer

107. . . The step of uniformly dispersing the second prepolymer in the dispersion containing the inorganic base type neutralizing agent to form the anionic aqueous polyurethane resin

201. . . Base cloth

202. . . Skin resin

203/207. . . roller

204. . . scraper

205. . . Impregnation solution

206. . . Resin resin

209. . . Drying treatment

211. . . film

221/223. . . Composite fabric

300. . . Tensile test equipment

301/301’. . . Resin film strip

303. . . Fixture

305. . . Chuck

307. . . arrow

401/403. . . curve

w ₁ / w ₂ . . . width

l ₁ / l ₂ . . . length

The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.

Fig. 1 is a partial flow chart showing a method of producing an anionic aqueous polyurethane resin according to an embodiment of the present invention.

2A to 2C are partial flow diagrams showing the preparation of a composite fabric having hydrolysis resistance according to several embodiments of the present invention.

3A to 3B are schematic views showing a tensile test apparatus according to an embodiment of the present invention.

Fig. 4 is a graph showing tensile strength of a film subjected to an anionic aqueous polyurethane resin process in a high temperature and high humidity environment according to an embodiment of the present invention.

100. . . method

101. . . Step of forming the first prepolymer

103. . . Forming a second prepolymer wherein the second prepolymer has at least one hydrophilic side chain group

105. . . Step of adding an organic base type neutralizing agent to the second prepolymer

107. . . The step of uniformly dispersing the second prepolymer in the dispersion containing the inorganic base type neutralizing agent to form the anionic aqueous polyurethane resin

Claims (17)

The method for producing an anionic aqueous polyurethane resin comprises at least prepolymerizing a diisocyanate compound (A) and a polyol (B) with a chain extender to form a first prepolymer. Wherein the chain extender comprises a diamine compound or a diol compound; reacting the first prepolymer with the carboxylic acid group-containing compound (C) in an organic solvent (D) to form a second prepolymer, Wherein the second prepolymer has at least one hydrophilic side chain group; an organic base type neutralizing agent (E-1) is added to the second prepolymer to form a dispersion; and the dispersion is homogeneous Dispersing in an aqueous dispersion containing one of an inorganic base type neutralizing agent (E-2) to form an anionic aqueous polyurethane resin, wherein the organic base type neutralizing agent (E-1) and the inorganic base The molar percentage of the type neutralizing agent (E-2) is from 80:20 to 20:80. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the polyol (B) is selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols, and polyhexans. A group of lactone polyols, polyacrylate polyols, and any combination of the foregoing. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the polyol (B) is a polyether polyol. The method for producing an anionic aqueous polyurethane resin according to claim 3, wherein the polyether polyol (B) has an arithmetic mean molecular weight of 200 to 5,000. The method for producing an anionic aqueous polyurethane resin according to claim 3, wherein the polyether polyol (B) has an arithmetic mean molecular weight of from 500 to 2,000. The method for producing an anionic aqueous polyurethane resin according to claim 3, wherein the polyether polyol (B) has an arithmetic mean molecular weight of from 800 to 1,500. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the hydrophilic side chain group of the second prepolymer comprises a carboxylic acid group, a sulfonic acid group (-SO ₃ H), Phosphate group (-OPO ₃ H ₂ ) or phosphonic acid group (-PO ₃ H ₂ ). The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the organic base type neutralizing agent (E-1) is selected from the group consisting of tri-n-propylamine, N-methylmorpholine, and the above A group of any combination of any combination. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the inorganic base type neutralizing agent (E-2) is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, and A group consisting of any combination of the above. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the diisocyanate compound (A) is 6 by weight based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin. Percentage to 12% by weight, the polyol (B) is from 15% by weight to 33% by weight, the carboxylic acid group-containing compound (C) is from 1.5% by weight to 3.5% by weight, and the organic solvent (D) is from 1.5% by weight to 3.0% by weight, the organic base type neutralizing agent (E-1) is from 0.5% by weight to 2.5% by weight, and the inorganic base type neutralizing agent (E-2) is from 0.05% by weight to 0.5% by weight. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the aqueous dispersion further contains at least inorganic cerium oxide (F) and water. The method for producing an anionic aqueous polyurethane resin according to claim 11, wherein the inorganic cerium oxide (F) is 0.1 based on 100% by weight based on the total weight of the anionic aqueous polyurethane resin. The weight percentage is 0.5% by weight, and the water is 60% by weight to 70% by weight. The method for producing an anionic aqueous polyurethane resin according to claim 1, wherein the chain extender comprises ethylene glycol (EG), 1,4-butylene glycol; 1,4-BG), 1,6-hexanediol (1,6-hexanediol; 1,6-HD), ethylenediamine Or hydrazine. An anionic aqueous polyurethane resin produced by the method of any one of the claims 113. A composite fabric having hydrolysis resistance, wherein the composite fabric is obtained by impregnating a base fabric with an impregnation liquid comprising the anionic aqueous polyurethane resin according to claim 14 and then subjecting it to a drying treatment. A film having hydrolysis resistance, wherein the film has the anionic water-based polyurethane resin according to claim 14, when the film is exposed to a temperature of 70 ° C and a humidity of 95% for 4 days, the film is A tensile strength is from 30 kgf/cm ² to 90 kgf/cm ² , and an elongation of the film is from 150 to 450 percent. A composite fabric having hydrolysis resistance, wherein the composite fabric comprises a base fabric and a film directly attached to the base fabric, and the film is the film according to claim 16.