CN113929860A - Water-based polyurethane resin emulsion for microfiber impregnation and preparation method and application thereof - Google Patents
Water-based polyurethane resin emulsion for microfiber impregnation and preparation method and application thereof Download PDFInfo
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- CN113929860A CN113929860A CN202111233150.3A CN202111233150A CN113929860A CN 113929860 A CN113929860 A CN 113929860A CN 202111233150 A CN202111233150 A CN 202111233150A CN 113929860 A CN113929860 A CN 113929860A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The invention relates to a water-based polyurethane resin emulsion for microfiber impregnation, a preparation method and application thereof, wherein the raw material formula of the water-based polyurethane resin emulsion comprises the following components: a first polyol component, a second polyol component, an isocyanate, and other ingredients, the first polyol component including a combination of one or more of polytetrahydrofuran diol, polyoxypropylene diol; the second polyol component is a nonionic polyol containing a polyoxyethylene group structure, the number average molecular weight is 800-1200, and the mass of the second polyol component is 5-10% of the total mass of the first polyol component, the second polyol component and the isocyanate. The invention solves the defects of poor hand feeling, low tearing strength and poor fiber opening effect of the existing waterborne polyurethane resin for microfiber by introducing a certain amount of nonionic polyol component with polyoxyethylene group into the molecular structure of the polyurethane resin and matching with other polyol components, isocyanate and the use of the components thereof.
Description
Technical Field
The invention belongs to the technical field of polyurethane emulsion, and particularly relates to an aqueous polyurethane resin emulsion for microfiber impregnation, and a preparation method and application thereof.
Background
The microfiber synthetic leather is also called microfiber synthetic leather, is superior to common PU and PVC artificial leather in strength, hand feeling and other aspects, is the synthetic leather closest to genuine leather at present, and is mainly used for preparing microfiber synthetic leather from microfiber non-woven fabrics and polyurethane resin. Because the base cloth adopts superfine fiber, the strength is high, the elasticity is good, the air permeability is good, the hand feeling is soft, many physical properties of the high-grade synthetic leather are mostly superior to those of natural leather, and the external surface has the characteristics of the natural leather. In industrial sense, the method is suitable for modern mass production, can protect ecology, reduce environmental pollution, fully utilizes non-natural resources, and has original skin characteristics on the surface. The polyurethane resin is used for the impregnation process of the microfiber base cloth, the impregnated base cloth can form a polyurethane/microfiber composite structure through drying → decrement → washing → drying, and then a microfiber synthetic leather finished product can be obtained through dyeing, veneering and other post-finishing.
Most of microfiber synthetic leather in the market at present is prepared by adopting oil-based polyurethane resin, and the residual and volatilization of organic solvents in the production process pollute the environment and waste resources. With the increasing strictness of environmental protection pressure, the use and recovery of organic solvents greatly increase the production cost. The market demands pollution-free water-based polyurethane resin, and the water-based microfiber synthetic leather in the market at present has a difference from oil-based microfiber synthetic leather in the aspects of hand feeling, dyeing, tearing strength and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the aqueous polyurethane resin emulsion for the impregnation of the microfiber and the preparation method thereof, and the prepared microfiber synthetic leather has good fiber opening effect, soft hand feeling, strong meat feeling and tear strength equivalent to that of oily microfiber synthetic leather.
In order to achieve the purpose, the invention adopts the technical scheme that:
the aqueous polyurethane resin emulsion comprises the following components in percentage by weight: a first polyol component, a second polyol component, isocyanate, a hydrophilic carboxylic acid type chain extender, an alcohol chain extender, an amine chain extender, a cross-linking agent, a neutralizing agent and water, wherein,
the first polyol component comprises one or more of polytetrahydrofuran diol and polypropylene oxide diol;
the second polyol component is a nonionic polyol containing a polyoxyethylene structure, the number average molecular weight of the second polyol component is 800-1200, and the mass of the second polyol component is 5-10% of the total mass of the first polyol component, the second polyol component and the isocyanate.
In some preferred and specific embodiments, the second polyol component has a mass of 5 to 8% of the total mass of the first polyol component, the second polyol component and the isocyanate.
According to some embodiments of the invention, the second polyol component is one or a combination of polyethylene glycol monomethyl ether, linear polyethylene glycol difunctional monoether. Such as polyethylene glycol monomethyl ether (MPEG1000) having a number average molecular weight of about 1000, and linear polyethylene glycol bifunctional monoether having a number average molecular weight of about 1000.
According to some embodiments of the invention, the first polyol component has a number average molecular weight of 1800 to 2200. For example, polytetrahydrofuran diol (PTMG2000) with a number average molecular weight of about 2000 and polyoxypropylene diol (polypropylene glycol) with a number average molecular weight of about 2000 (PPG2000) are selected.
According to some embodiments of the invention, the isocyanate is a combination of one or more of isophorone diisocyanate (IPDI), hexamethylene diisocyanate, dicyclohexylmethane diisocyanate.
According to some embodiments of the invention, the crosslinker is one or more of Diethylenetriamine (DETA), trimethylolpropane, or combinations thereof.
According to some embodiments of the invention, the hydrophilic carboxylic acid type chain extender is a combination of one or more of 2, 2-dimethylolpropionic acid (DMPA), 2-dimethylolbutyric acid (DMBA).
According to some embodiments of the invention, the alcoholic chain extender is a combination of one or more of 1,6 hexanediol, Ethylene Glycol (EG), 2-methylpropanediol, neopentyl glycol, 1,4 butanediol.
According to some embodiments of the invention, the amine chain extender is a combination of one or more of isophorone diamine, Ethylene Diamine (EDA).
According to some embodiments of the invention, the catalyst is an organo-bismuth based catalyst. Such as BCAT-BY 20.
According to some embodiments of the invention, the mass of the first polyol component is 72 to 76% of the total mass of the first polyol component, the second polyol component and the isocyanate.
In some preferred and specific embodiments, the molar addition amount of the isocyanate to the total molar ratio of the first polyol component, the second polyol component, the carboxylic acid type chain extender, and the alcohol type chain extender is from 1:0.6 to 0.95; the addition amount of the cross-linking agent accounts for 0.5-5% of the total mass of the first polyol component, the second polyol component and the isocyanate; the addition amount of the amine chain extender accounts for 0.2-1.5% of the total mass of the first polyol component, the second polyol component and the isocyanate; the mole ratio of the neutralizing agent to the hydrophilic carboxylic acid type chain extender is 0.95-1.05: 1; the addition amount of the catalyst accounts for 0.01-0.1% of the total mass of the first polyol component, the second polyol component and the isocyanate; the water accounts for 50-55% of the total mass of the waterborne polyurethane resin emulsion.
Preferably, the molar ratio of the hydrophilic carboxylic acid type chain extender to the alcohol type chain extender is 1.2-1.6: 1.
Preferably, the molar addition amount of the isocyanate to the total molar ratio of the first polyol component, the second polyol component, the carboxylic acid type chain extender and the alcohol type chain extender is 1: 0.85-0.95.
The second technical scheme adopted by the invention is as follows: a preparation method of the aqueous polyurethane resin emulsion comprises the following steps:
(1) reacting a first polyol component, a second polyol component, a hydrophilic carboxylic acid type chain extender, an alcohol type chain extender and isocyanate in the presence of a catalyst to obtain a polyurethane prepolymer;
(2) and (2) adding Acetone (AC) into the polyurethane prepolymer obtained in the step (1), stirring, cooling, then adding a neutralizing agent, cooling, then adding water for emulsification, adding a cross-linking agent and an amine chain extender, stirring, and removing acetone to obtain the aqueous polyurethane resin emulsion.
In some preferred and specific embodiments, in step (1), the reaction is carried out at 90 to 95 ℃ for 3 to 4 hours.
In some preferred and specific embodiments, in the step (2), after the acetone is added, the temperature of the system is reduced to 35-45 ℃, and then the neutralizing agent is added.
In some preferred and specific embodiments, in the step (2), before the water is added, the temperature of the system is reduced to 20-25 ℃, and then the water is added.
According to some embodiments of the present invention, the moisture content of the first polyol component, the second polyol component, the alcohol chain extender, and the acetone is required to be less than 500 ppm.
The third technical scheme adopted by the invention is as follows: the aqueous polyurethane resin emulsion is applied to the impregnation preparation of microfiber synthetic leather.
The fourth technical scheme adopted by the invention is as follows: a preparation method of microfiber synthetic leather comprises the steps of immersing microfiber non-woven fabric into the waterborne polyurethane resin emulsion, drying, then putting the microfiber non-woven fabric into an alkali solution for decrement treatment, washing and drying to obtain the microfiber synthetic leather.
According to the invention, a certain amount of specific nonionic polyol is introduced into the polyurethane resin, and the nonionic polyol forms bonding with the microfiber non-woven fabric in the drying process of the synthetic leather, so that the resin molecules are prevented from migrating from inside to outside, and the full hand feeling of the microfiber is maintained.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, a certain amount of nonionic polyol component with polyoxyethylene group is introduced into the molecular structure of polyurethane resin, and is matched with other polyol components, isocyanate and the use of the components thereof, so that the aqueous polyurethane resin emulsion with the modulus of more than 1.5MPa and the breaking strength of more than 5MPa is prepared.
Drawings
FIG. 1 is a drawing showing the effect of opening synthetic leather of each sample, wherein (a) is a drawing showing the effect of opening microfiber synthetic leather prepared using the aqueous polyurethane resin emulsion of example 1; (b) the opening effect diagram of the microfiber synthetic leather prepared by the aqueous polyurethane resin emulsion of the comparative example 1 is shown; (c) the opening effect diagram of the microfiber synthetic leather prepared by the aqueous polyurethane resin emulsion of the comparative example 2 is shown; (d) is a fiber opening effect diagram of the microfiber synthetic leather prepared by adopting the oil-based polyurethane resin.
Detailed Description
As mentioned in the background art, the existing water-based microfiber synthetic leather is different from oil-based microfiber synthetic leather in hand feeling, dyeing, tearing strength and the like. The inventor researches the mechanism of the water-based microfiber synthetic leather with poor hand feeling, low tearing strength and the like, and finds that the polyurethane resin molecular chain is volatilized along with the moisture in the impregnation and drying process of the water-based microfiber synthetic leather, so that the interior of the microfiber synthetic leather is empty, the hand feeling is poor, and the tearing strength is low. The inventor discovers through a large amount of researches that a part of special structure-polyoxyethylene structure is introduced into the polyurethane resin structure, the polyoxyethylene structure has heat sensitivity, the polyoxyethylene structure has hydrophobicity in the high-temperature drying process, the adhesive force between the polyoxyethylene structure and microfiber base cloth is enhanced, and the migration of resin molecular chains in the drying process is effectively avoided, so that the microfiber synthetic leather with good fiber opening effect, soft and plump hand feeling and high tearing strength is obtained.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents may fall within the scope of the invention as defined by the appended claims.
Example 1
The raw material composition of the aqueous polyurethane resin emulsion provided in this example is shown in table 1.
The aqueous polyurethane resin emulsion in this example was prepared by the following method:
(1) adding a first polyol component, a second polyol component, a carboxylic acid type chain extender and an alcohol type chain extender into a reaction kettle, uniformly stirring, then adding isocyanate and a catalyst, and carrying out prepolymerization reaction at 90 ℃ for 4 h.
(2) After the prepolymerization reaction is finished, sampling from a sampling port, carrying out titration test on the content of residual isocyanate by adopting a di-n-butylamine method, adding 660kg of acetone for dilution after the theoretical NCO value reaches 1.65%, adding acetone, stirring for 30min to obtain a homogeneous prepolymer solution, then controlling the temperature to be 38-42 ℃, adding triethylamine, stirring for 15min to neutralize and form salt, then cooling to 20-25 ℃, adding water for emulsification, stirring for 10min after emulsification, adding a mixed solution of diethylenetriamine and ethylenediamine, continuing stirring for 30min, then starting heating to 40-50 ℃, removing acetone, cooling to below 30 ℃, metering and packaging to obtain the aqueous polyurethane resin emulsion.
Example 2
The difference between the aqueous polyurethane resin emulsion provided in this example and example 1 is that: linear polyethylene glycol bifunctional methyl ether (number average molecular weight about 1000) was used in place of MPEG 1000.
In this example, the method for producing the aqueous polyurethane resin emulsion was the same as in example 1.
Example 3
The raw material formulation of the aqueous polyurethane resin emulsion provided in this example is shown in table 1.
In this example, the method for producing the aqueous polyurethane resin emulsion was the same as in example 1.
Example 4
The raw material formulation of the aqueous polyurethane resin emulsion provided in this example is shown in table 1.
In this example, the method for producing the aqueous polyurethane resin emulsion was the same as in example 1.
Comparative example 1
The formulation of the raw materials of the aqueous polyurethane resin emulsion provided in this comparative example is shown in table 1, and the rest is the same as that of example 1.
Comparative example 2
The formulation of the raw materials of the aqueous polyurethane resin emulsion provided in this comparative example is shown in table 1, and the rest is the same as that of example 1.
Comparative example 3
The formulation of the raw materials of the aqueous polyurethane resin emulsion provided in this comparative example is shown in table 1, and the rest is the same as that of example 1.
Table 1 shows the raw material formulations (unit Kg) of the aqueous polyurethane resin emulsions of examples 1 to 3 and comparative examples 1 to 3
Performance tests were carried out on the aqueous polyurethane resin emulsions of examples 1 to 4 and comparative examples 1 to 3 in accordance with the reference standard GB/T19250-2013, and the results are shown in Table 2.
Table 2 shows the results of the performance tests of the aqueous polyurethane resin emulsions of examples 1 to 4 and comparative examples 1 to 3
The aqueous polyurethane resin emulsions of examples 1-4 and comparative examples 1-3 are respectively used for preparing microfiber synthetic leather, and the process is as follows: impregnating the microfiber non-woven fabric into the aqueous polyurethane resin emulsion, rolling the microfiber non-woven fabric for three times on a squeezing roller after impregnation, and completely drying the microfiber non-woven fabric in a 120 ℃ drying oven. And then placing the completely dried impregnated non-woven fabric into a 10% sodium hydroxide aqueous solution, boiling for 1h at 80 ℃, taking out the non-woven fabric, repeatedly extruding the non-woven fabric on an extrusion roller, soaking and cleaning the non-woven fabric by deionized water to obtain reduced microfiber, and placing the microfiber into a 120 ℃ oven to dry to obtain the water-based microfiber synthetic leather.
The mechanical properties of the synthetic leather prepared from the aqueous polyurethane resin emulsions of examples 1 to 4 and comparative examples 1 to 3 and the synthetic leather commercially available and prepared from the oil-based polyurethane resin were tested with reference to GB/T1040.2-2006 "cloth tear test", and the results are shown in table 3.
The synthetic leather prepared by the aqueous polyurethane resin emulsions of example 1 and comparative examples 1 to 2 was observed for the splitting effect by a scanning electron microscope, as shown in fig. 1, and the synthetic leather prepared by the commercially available oleoresin was observed for the splitting effect by a scanning electron microscope, and the results are shown in fig. 1. As can be seen from the fiber opening effect diagram in fig. 1, the synthetic leather prepared by using the aqueous polyurethane resin emulsion of example 1 has good fiber opening effect, equivalent to the fiber opening effect of the oily microfiber synthetic leather on the market, and equivalent to the tear strength. The comparative example 1 has the problem of hollow inside, causing hand feeling holes and no meat feeling, and the comparative example 2 has the problem of incomplete weight reduction, which shows that the defects of incomplete weight reduction of the microfiber, low tear strength of the microfiber and the like are caused by the excessively high using amount of the nonionic polyol. Therefore, the microfiber synthetic leather prepared by the aqueous polyurethane resin emulsion of the embodiments 1 to 3 overcomes the defects of the existing products, and has high industrial utilization value.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. The aqueous polyurethane resin emulsion is characterized in that the raw material formula of the aqueous polyurethane resin emulsion comprises the following components: a first polyol component, a second polyol component, isocyanate, a hydrophilic carboxylic acid type chain extender, an alcohol chain extender, an amine chain extender, a cross-linking agent, a neutralizing agent and water, wherein,
the first polyol component comprises one or more of polytetrahydrofuran diol and polypropylene oxide diol;
the second polyol component is a nonionic polyol containing a polyoxyethylene structure, the number average molecular weight of the second polyol component is 800-1200, and the mass of the second polyol component is 5-10% of the total mass of the first polyol component, the second polyol component and the isocyanate.
2. The aqueous polyurethane resin emulsion according to claim 1, characterized in that: the second polyol component is one or the combination of polyethylene glycol monomethyl ether and linear polyethylene glycol bifunctional monoether.
3. The aqueous polyurethane resin emulsion according to claim 1, characterized in that: the number average molecular weight of the first polyol component is 1800-2200; and/or the isocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate.
4. The aqueous polyurethane resin emulsion according to claim 1, characterized in that: the cross-linking agent is one or a combination of two or more of diethylenetriamine and trimethylolpropane; and/or the hydrophilic carboxylic acid type chain extender is one or a combination of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid; and/or the alcohol chain extender is one or more of 1,6 hexanediol, ethylene glycol, 2-methyl propylene glycol, neopentyl glycol and 1,4 butanediol; and/or the amine chain extender is one or a combination of more of isophorone diamine and ethylene diamine.
5. The aqueous polyurethane resin emulsion according to claim 1, characterized in that: the mass of the first polyol component is 72-76% of the total mass of the first polyol component, the second polyol component and the isocyanate.
6. The aqueous polyurethane resin emulsion according to any one of claims 1 to 5, wherein: the molar addition amount of the isocyanate and the total molar ratio of the first polyol component, the second polyol component, the carboxylic acid type chain extender and the alcohol type chain extender are 1: 0.6-0.95; and/or the addition amount of the cross-linking agent accounts for 0.5-5% of the total mass of the first polyol component, the second polyol component and the isocyanate; and/or the addition amount of the amine chain extender accounts for 0.2-1.5% of the total mass of the first polyol component, the second polyol component and the isocyanate; and/or the molar ratio of the neutralizing agent to the hydrophilic carboxylic acid type chain extender is 0.95-1.05: 1; and/or the addition amount of the catalyst accounts for 0.01-0.1% of the total mass of the first polyol component, the second polyol component and the isocyanate; and/or the water accounts for 50-55% of the total mass of the waterborne polyurethane resin emulsion.
7. A preparation method of the aqueous polyurethane resin emulsion according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) reacting a first polyol component, a second polyol component, a hydrophilic carboxylic acid type chain extender, an alcohol type chain extender and isocyanate in the presence of a catalyst to obtain a polyurethane prepolymer;
(2) and (2) adding acetone into the polyurethane prepolymer obtained in the step (1), stirring, cooling, then adding a neutralizing agent, cooling, then adding water for emulsification, adding a cross-linking agent and an amine chain extender, stirring, and removing acetone to obtain the aqueous polyurethane resin emulsion.
8. The method for producing an aqueous polyurethane resin emulsion according to claim 7, characterized in that: in the step (1), the reaction is carried out at 90-95 ℃ for 3-4 h; and/or, in the step (2), after adding acetone, cooling the system to 35-45 ℃, and then adding the neutralizer; and/or in the step (2), before adding water, cooling the system to 20-25 ℃, and then adding water.
9. The use of the aqueous polyurethane resin emulsion according to any one of claims 1 to 6 for preparing microfiber synthetic leather by impregnation.
10. A preparation method of microfiber synthetic leather is characterized by comprising the following steps: the method comprises the steps of immersing microfiber non-woven fabrics in the aqueous polyurethane resin emulsion of any one of claims 1 to 6, drying, then placing in an alkaline solution for decrement treatment, washing with water, and drying to obtain microfiber synthetic leather.
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