CN110229301B - Preparation method and application of waterborne polyurethane resin synthetic leather - Google Patents
Preparation method and application of waterborne polyurethane resin synthetic leather Download PDFInfo
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- CN110229301B CN110229301B CN201910397079.9A CN201910397079A CN110229301B CN 110229301 B CN110229301 B CN 110229301B CN 201910397079 A CN201910397079 A CN 201910397079A CN 110229301 B CN110229301 B CN 110229301B
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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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
- D06N3/12—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
- D06N3/145—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 two or more layers of polyurethanes
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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
- D06N2211/26—Vehicles, transportation
- D06N2211/263—Cars
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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
Abstract
The invention discloses a preparation method and application of waterborne polyurethane resin synthetic leather, wherein the preparation method comprises the steps of respectively taking waterborne polyurethane resin as a fabric layer, a middle material layer and a primer layer, coating the waterborne polyurethane resin on release paper, and drying; and (3) attaching the waterborne space leather base on the primer layer, drying, and stripping the release paper to obtain the waterborne polyurethane resin synthetic leather. The flame-retardant waterborne polyurethane emulsion is prepared and applied to the automobile leather surface, the middle and the bottom materials, and on the basis, the flame-retardant waterborne base 636E/flame-retardant waterborne space leather base is adopted as a base material to prepare the flame-retardant automobile leather of a full waterborne system. Compared with the traditional PVC automobile leather, the synthetic leather prepared by the invention is applied to the automobile leather, has the characteristics of no VOC release, no toxicity, environmental protection, full water-based system and the like, and further improves the additional value and the application range of the environment-friendly polyurethane material product.
Description
Technical Field
The invention belongs to the technical field of polyurethane resin synthesis, and particularly relates to a preparation method and application of waterborne polyurethane resin synthetic leather.
Background
With the rapid development of polyurethane synthesis technology, polyurethane synthetic leather materials of polyurethane systems have been widely applied in numerous fields of national economy. For example, automobile leather is widely applied to automobile interiors and seats for household and automobile as special artificial synthetic leather, but most of the automobile synthetic leather on the market at present is synthetic leather prepared from solvent type polyurethane slurry, and environmental protection problems such as a large amount of organic solvent residues and VOCs (volatile organic compounds) release exist in the processes of polyurethane synthesis and automobile leather preparation and coating, so that great potential harm is caused to human health. In recent years, with the gradual maturity of the synthetic technology of waterborne polyurethane, a few products adopting a waterborne surface layer to attach a solvent-free middle layer and a solvent-based bottom layer are further developed in the market, and although the residual content of organic solvents and the release of VOCs are effectively reduced to a certain extent, the problem of bonding deviation commonly occurs when the waterborne surface layer and the solvent-free middle layer are directly attached, a transition layer is further adopted between the waterborne surface layer and the solvent-free middle layer, so that the cost is increased, and meanwhile, the application performance and the service life of automobile leather are greatly influenced. Therefore, the automobile leather of a high-performance all-aqueous system still needs to be further developed.
Based on the situation, the invention provides a preparation method of waterborne polyurethane resin synthetic leather, aiming at overcoming the technical defects of the existing preparation of automobile leather products and providing polyurethane resin for fully waterborne and flame-retardant automobile leather and a preparation method of the synthetic leather.
Disclosure of Invention
The invention aims to provide a preparation method and application of waterborne polyurethane resin synthetic leather, mainly aims to overcome the technical defects of the existing automobile leather products, enhances the comprehensive properties such as flame retardance and the like, and provides fully-waterborne flame-retardant polyurethane resin for automobile leather and a preparation method of synthetic leather thereof.
In order to solve the problems, the invention is realized by the following technical scheme: an aqueous polyurethane resin, which comprises the following raw materials,
10-80 parts of polyester polyol, 30-120 parts of polyether polyol, 20-80 parts of melamine organic polyol, 15-55 parts of polyisocyanate, 3-20 parts of hydrophilic chain extender, 1-15 parts of micromolecular non-hydrophilic chain extender, 0.1-10 parts of catalyst, 0.1-8 parts of internal crosslinking agent, 2-18 parts of neutralizing agent, 1-5 parts of post chain extender, 30-100 parts of acetone and 400-800 parts of deionized water.
Optionally, the polyester polyol is one or a mixture of two of liquid or solid polycarbonate diol.
Optionally, the polyether polyol is one or more of high activity polyether glycol, polytetrahydrofuran glycol, tetrahydrofuran copolymer glycol and tetrahydrofuran-ethylene oxide copolymer glycol.
Optionally, the melamine-based organic polyol is a polyether melamine resin polyol.
Optionally, the hydrophilic chain extender includes a carboxylic acid type anionic group hydrophilic chain extender and a sulfonic acid type anionic group hydrophilic chain extender.
Optionally, the small molecule non-hydrophilic chain extender is one or more of 1,4 butanediol, ethylene glycol, 1,4 dimethylolcyclohexane, diethylene glycol and neopentyl glycol, dodecanediol, and spiroglycol.
Optionally, the catalyst is one or more of dibutyl tin dilaurate, zinc carboxylate, bismuth carboxylate, and tetrabutyl titanate.
Optionally, the post-chain extender is one or more of isophorone diamine, ethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine, and diamino dicyclohexyl methane.
The preparation method of the synthetic leather of the waterborne polyurethane resin comprises the steps of respectively using the waterborne polyurethane resin as a fabric layer, a middle material layer and a primer layer, coating the waterborne polyurethane resin on release paper, and drying; and (3) attaching the waterborne space leather base on the primer layer, drying, and stripping the release paper to obtain the waterborne polyurethane resin synthetic leather.
Optionally, the aqueous polyurethane resin synthetic leather is applied to automobile leather.
In the invention, a melamine flame-retardant structure is introduced in the synthesis stage of the polyurethane emulsion to prepare the flame-retardant waterborne polyurethane emulsion, the flame-retardant waterborne polyurethane emulsion is applied to the leather surface, the middle and the bottom materials of the automobile, and on the basis, the flame-retardant waterborne bass 636E/flame-retardant waterborne space leather bass is adopted as a base material to prepare the flame-retardant synthetic leather of the full waterborne system. The aqueous synthetic leather prepared by the invention is applied to automobiles, the application performance of the aqueous synthetic leather can meet the application requirements of the front parts of automobile interior trim seats, backrests and headrests, and compared with the traditional PVC automobile leather, the aqueous synthetic leather has the characteristics of no Volatile Organic Compound (VOC) release, no toxicity, environmental protection, full aqueous system and the like, and the additional value and the application range of an environment-friendly polyurethane material product are further improved. In addition, the flame retardance can reach the B1-grade combustion characteristic standard specified in the GB 8410 + 2006 automobile leather interior material standard, the normal-temperature folding resistance (23 ℃) is not less than 15 ten thousand, the low-temperature folding resistance (15 ℃) is not less than 8 ten thousand, the Taber abrasion resistance is not less than 2000, other physical property test performance indexes reach and meet the standards of QB/T4194 + 2011 automobile polyurethane synthetic leather and QB/T4043 + 2010 automobile polyvinyl chloride artificial leather, and the prepared synthetic leather meets the application requirements of the automobile leather A-class seat part; the invention can be applied to automobile leather and other synthetic leather.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
Preparing the aqueous polyurethane resin: firstly, reacting 10-80 parts by mass of polyester polyol, 30-120 parts by mass of polyether polyol, 20-80 parts by mass of melamine type organic polyol and 15-55 parts by mass of polyisocyanate at 85-100 ℃ for 3-5h according to a set weight ratio; then adding 3-20 parts of hydrophilic chain extender, 1-15 parts of micromolecular chain extender, 0.1-8 parts of internal crosslinking agent and 0.1-10 parts of catalyst, and continuously reacting for 2-4h at 75-90 ℃; cooling to 40-60 ℃, adding viscosity-reducing acetone, cooling, adding 2-18 parts of neutralizing agent at 20-40 ℃ for neutralization for 3-5 min, discharging, mixing with 800 parts of deionized water (made into ice water) under the high-speed shearing action of an IKA disperser for emulsification, and dripping the chain extender within 1-2 min to obtain the waterborne polyurethane emulsion; during the reaction period, a proper amount of acetone is intermittently added to reduce the viscosity.
Preparing synthetic leather of aqueous polyurethane resin: after acetone is removed from the polyurethane emulsion at the temperature of 40-55 ℃, 0.1-10 parts of external cross-linking agent, 0.1-5 parts of defoaming agent, 0.1-10 parts of film-forming aid, 0.05-5 parts of thickening agent, 0.1-5 parts of leveling wetting agent and 1-10 parts of color paste are added, stirred at a low speed and uniformly mixed for 10-20 min to prepare flame-retardant waterborne polyurethane surface, middle and bottom material resins, and waterborne natural waterborne base 636E/flame-retardant waterborne space leather base is adopted as a base material.
In addition, the invention also discloses a preparation method of the fully-aqueous system polyurethane synthetic leather prepared by adopting the surface, middle and bottom material resins and the base material of the Bass in a dry method, a method for adopting the surface, middle and bottom materials to prepare the prepared resins and a method for adopting the surface, middle and bottom materials to prepare the resinsThe method for preparing the full-aqueous system flame-retardant synthetic leather by the Bass substrate dry method comprises the following specific steps: firstly, coating one surface of a fabric layer on release paper and coating the other surface of the fabric layer on a middle material layer by adopting a release paper transfer method through the prepared surface and middle material resin, wherein the coating weight is 100-300 g/m2And drying by gradient heating at 100-130 deg.C at a heating rate of 2-5 deg.C/min, wherein the heating rate is further optimized to increase gradually, drying, and coating with a coating weight of 100-200 g/m2Further adopting a wet pasting method to laminate a flame-retardant water-based bass 636E/a flame-retardant water-based space leather bass; and secondly, drying the synthetic leather at the temperature of 120-150 ℃ at the heating rate of 3-5 ℃/min in a gradient heating mode, and stripping to obtain the full-water-based synthetic leather product. The gradient drying and heating are adopted in the temperature range, so that the coating film is uniformly heated and is not easy to peel off early, and the like, and the coating film is dried quickly.
And (3) performance testing: the prepared waterborne polyurethane resin is applied to automobile leather, and the flame retardance is tested according to the standard of GB 8410-; according to the test standards of QB/T4194-2011 polyurethane synthetic leather for automobiles and QB/T4043-2010 polyvinyl chloride artificial leather for automobiles, the obtained full-aqueous system polyurethane resin synthetic leather is used for testing mechanical indexes such as tensile strength, peeling strength, tearing strength, seam strength and the like of a film material through an Instron universal testing machine; the abrasion resistance of the synthetic leather is tested by adopting a Taber method, and the normal and low temperature folding resistance of the synthetic leather is tested by adopting a folding strength tester.
The following are specific examples:
example 1
Preparing the aqueous polyurethane resin: firstly, weighing 18 parts of liquid polycarbonate diol, 60 parts of polytetrahydrofuran diol and 45 parts of melamine organic diol according to a given weight ratio, placing the materials in a glass container, carrying out vacuum dehydration for 1-2 h at 90 ℃, then cooling to 65 ℃, adding 25 parts of isophorone diisocyanate, and heating to 85 ℃ for reaction for 3 h; then cooling to 75 ℃, adding 5 parts of dimethylolpropionic acid, 3 parts of 1, 4-butanediol, 0.35 part of trimethylolpropane and 0.28 part of bismuth carboxylate into the mixture, and keeping the temperature at 75 ℃ for reaction for 3 hours; cooling to 40-60 ℃, adding 100 parts of viscosity-reducing acetone, cooling, adding 4.8 parts of triethylamine at 20-40 ℃ for neutralization for 3-5 min, discharging, mixing with 350 parts of deionized water (prepared into ice water) under the high-speed shearing action of an IKA dispersing machine for emulsification, and dripping 2 parts of isophorone diamine within 1-2 min to obtain the flame-retardant waterborne polyurethane emulsion; and intermittently adding a proper amount of 30-50 parts of acetone during the reaction period to reduce the viscosity.
Preparing synthetic leather of aqueous polyurethane resin: after acetone is removed from the polyurethane emulsion at the temperature of 40-55 ℃, 0.35 part of aziridine, 0.3 part of polysiloxane copolymer defoaming agent, 2 parts of dodecyl alcohol ester, 1 part of hydroxymethyl cellulose, 0.5 part of dicarboxylic acid alkyl ammonium salt propylene glycol solution and 5 parts of aqueous color paste are added, stirred at a low speed and mixed uniformly for 10-20 min to prepare aqueous polyurethane surface, middle and bottom material resins, and aqueous weather flame-retardant aqueous base bass 636E/flame-retardant aqueous space leather bass is used as a base material.
In addition, the invention also discloses a preparation method of the fully-aqueous system polyurethane synthetic leather prepared by adopting the surface, middle and bottom material resins and the base material of the Bass in a dry method, which comprises the following steps: firstly, coating one surface of a fabric layer on release paper and coating the other surface of the fabric layer on a middle material layer by adopting a release paper transfer method through the prepared surface and middle material resins, wherein the coating weights are respectively 150g/m and 200g/m2And drying by gradient heating at 100-130 deg.C at a heating rate of 2-5 deg.C/min, wherein the heating rate is further optimized to increase gradually, drying, and coating with a coating weight of 180g/m2Further adopting a wet pasting method to laminate a flame-retardant water-based bass 636E/a flame-retardant water-based space leather bass; and then drying the synthetic leather at the temperature of 120-.
And (3) performance testing: the prepared waterborne polyurethane resin is applied to automobile leather, and the flame retardance is tested according to the standard of GB 8410-; according to the test standards of QB/T4194 plus 2011 polyurethane synthetic leather for automobiles and QB/T4043 plus 2010 polyvinyl chloride artificial leather for automobiles, the obtained full-aqueous system polyurethane resin synthetic leather provided by the invention is used for testing mechanical indexes such as tensile strength, peeling strength, tearing strength, seam strength and the like of a film material through an Instron universal testing machine; testing the wear resistance of the synthetic leather by adopting a Taber method, and testing the normal and low temperature folding resistance of the synthetic leather by adopting a folding strength tester; specific test results are shown in table 1.
Example 2
Preparing the aqueous polyurethane resin: firstly, weighing 15 parts of liquid polycarbonate diol, 8 parts of solid polycarbonate diol, 80 parts of polytetrahydrofuran diol and 56 parts of melamine organic diol according to a given weight ratio, placing the materials in a glass container, carrying out vacuum dehydration for 1-2 h at 90 ℃, then cooling to 65 ℃, adding 30 parts of hexamethylene diisocyanate, and heating to 88 ℃ for reaction for 3 h; then cooling to 80 ℃, adding 6 parts of dimethylolbutyric acid, 4 parts of 1,6 hexanediol, 1.35 parts of trimethylolpropane and 0.38 part of bismuth carboxylate into the mixture, and keeping the temperature at 80 ℃ for reaction for 3 hours; cooling to 40-60 ℃, adding 120 parts of viscosity-reducing acetone, cooling, adding 5.8 parts of triethylamine at 20-40 ℃ for neutralization for 3-5 min, discharging, mixing with 420 parts of deionized water (prepared into ice water) under the high-speed shearing action of an IKA disperser for emulsification, and dripping 3.5 parts of ethylenediamine within 1-2 min to obtain the flame-retardant waterborne polyurethane emulsion; and intermittently adding a proper amount of 30-50 parts of acetone during the reaction period to reduce the viscosity.
Preparing synthetic leather of aqueous polyurethane resin: after acetone is removed from the polyurethane emulsion at the temperature of 40-55 ℃, 1.5 parts of aziridine, 1 part of polysiloxane copolymer defoaming agent, 3 parts of dodecanol ester, 2 parts of hydroxymethyl cellulose, 3 parts of dicarboxylic acid alkyl ammonium salt propylene glycol solution and 10 parts of aqueous color paste are added, stirred at a slow speed and uniformly mixed for 10-20 min to prepare aqueous polyurethane surface, middle and bottom material resins, and aqueous scientific flame-retardant aqueous bass 636E/flame-retardant aqueous space leather bass is used as a base material.
In addition, the invention also discloses the mining methodThe preparation method of the fully-aqueous system polyurethane synthetic leather prepared by using the surface, middle and bottom material resins and the base material of the Bass in a dry method comprises the following steps: firstly, coating one surface of a fabric layer on release paper and coating the other surface of the fabric layer on a middle material layer by adopting a release paper transfer method through the prepared surface and middle material resins, wherein the coating weights are respectively 140 g/m and 180g/m2And drying by gradient heating at 100-130 deg.C at a heating rate of 2-5 deg.C/min, wherein the heating rate is further optimized to increase gradually, drying, and coating with a coating weight of 180g/m2Further adopting a wet pasting method to laminate a flame-retardant water-based bass 636E/a flame-retardant water-based space leather bass; and then drying the synthetic leather at the temperature of 120-.
And (3) performance testing: the prepared waterborne polyurethane resin is applied to automobile leather, and the flame retardance is tested according to the standard of GB 8410-; according to the test standards of QB/T4194 plus 2011 polyurethane synthetic leather for automobiles and QB/T4043 plus 2010 polyvinyl chloride artificial leather for automobiles, the obtained full-aqueous system polyurethane resin synthetic leather provided by the invention is used for testing mechanical indexes such as tensile strength, peeling strength, tearing strength, seam strength and the like of a film material through an Instron universal testing machine; testing the wear resistance of the synthetic leather by adopting a Taber method, and testing the normal and low temperature folding resistance of the synthetic leather by adopting a folding strength tester; specific test results are shown in table 1.
Example 3
Preparing the aqueous polyurethane resin: firstly, weighing 30 parts of liquid polycarbonate diol, 100 parts of polytetrahydrofuran diol and 60 parts of melamine organic diol according to a given weight ratio, placing the materials in a glass container, dehydrating the materials in vacuum at 90 ℃ for 1 to 2 hours, then cooling the materials to 65 ℃, adding 50 parts of tetramethyl cyclohexyl methane diisocyanate, and heating the materials to 88 ℃ for reacting for 3 hours; then cooling to 78 ℃, adding 10 parts of dimethylolbutyric acid, 5 parts of 1, 4-dimethylolcyclohexane, 0.85 part of trimethylolpropane and 0.44 part of tetrabutyl titanate into a container, and continuously reacting for 3 hours at 78 ℃; cooling to 40-60 ℃, adding 150 parts of viscosity-reducing acetone, cooling, adding 9.5 parts of triethylamine at 20-40 ℃ for neutralization for 3-5 min, discharging, mixing with 500 parts of deionized water (prepared into ice water) under the high-speed shearing action of an IKA dispersing machine for emulsification, and dripping 5 parts of isophorone diamine within 1-2 min to obtain the flame-retardant waterborne polyurethane emulsion; and intermittently adding a proper amount of 30-50 parts of acetone during the reaction period to reduce the viscosity.
Preparing synthetic leather of aqueous polyurethane resin: after acetone is removed from the polyurethane emulsion at the temperature of 40-55 ℃, 0.8 part of aziridine, 2 parts of polysiloxane copolymer defoaming agent, 3 parts of dodecyl alcohol ester, 3 parts of polyether associative thickener, 3 parts of dicarboxylic acid alkyl ammonium salt propylene glycol solution and 10 parts of aqueous color paste are added, stirred at a low speed and uniformly mixed for 10-20 min to prepare aqueous polyurethane surface, middle and bottom material resins, and aqueous weather flame-retardant aqueous base bass 636E/flame-retardant aqueous space leather bass is used as a base material.
In addition, the invention also discloses a preparation method of the fully-aqueous system polyurethane synthetic leather prepared by adopting the surface, middle and bottom material resins and the base material of the Bass in a dry method, which comprises the following steps: firstly, coating one side of the fabric layer on release paper and coating the other side of the fabric layer on the middle material layer by adopting a release paper transfer method through the prepared fabric and middle material resins, wherein the coating weights are respectively 150g/m and 180g/m2And drying by gradient heating at 100-130 deg.C at a heating rate of 2-5 deg.C/min, wherein the heating rate is further optimized to increase gradually, drying, and coating with 160g/m of resin as water-based primer2Further adopting a wet pasting method to laminate a flame-retardant water-based bass 636E/a flame-retardant water-based space leather bass; and then drying the synthetic leather at the temperature of 120-.
And (3) performance testing: the prepared waterborne polyurethane resin is applied to automobile leather, and the flame retardance is tested according to the standard of GB 8410-; according to the test standards of QB/T4194 plus 2011 polyurethane synthetic leather for automobiles and QB/T4043 plus 2010 polyvinyl chloride artificial leather for automobiles, the obtained full-aqueous system polyurethane resin synthetic leather provided by the invention is used for testing mechanical indexes such as tensile strength, peeling strength, tearing strength, seam strength and the like of a film material through an Instron universal testing machine; testing the wear resistance of the synthetic leather by adopting a Taber method, and testing the normal and low temperature folding resistance of the synthetic leather by adopting a folding strength tester; specific test results are shown in table 1.
Example 4
Preparing the aqueous polyurethane resin: firstly, 50 parts of liquid polycarbonate diol, 110 parts of tetrahydrofuran-ethylene oxide copolymerized glycol and 65 parts of melamine organic diol are weighed according to a given weight ratio and placed in a glass container, vacuum dehydration is carried out for 1-2 h at 90 ℃, then the temperature is reduced to 65 ℃, 45 parts of dicyclohexylmethane diisocyanate are added, and the temperature is increased to 85 ℃ for reaction for 3 h; then cooling to 75 ℃, adding 8 parts of dimethylolpropionic acid, 3 parts of 1, 4-dimethylolcyclohexane, 1.53 parts of trimethylolpropane and 0.38 part of zinc carboxylate into the mixture, and keeping the temperature of the mixture at 75 ℃ for reaction for 3 hours; cooling to 40-60 ℃, adding 130 parts of viscosity-reducing acetone, adding 5 parts of 50% sodium diaminosulfonate aqueous solution, carrying out heat preservation reaction at 40-60 ℃ for 20min, continuously cooling, adding 12.5 parts of triethylamine at 20-40 ℃ for neutralization for 3-5 min, discharging, mixing with 550 parts of deionized water (prepared into ice water) under the high-speed shearing action of an IKA (IKA) dispersion machine for emulsification, and dripping 3.8 parts of isophorone diamine within 1-2 min to obtain the flame-retardant waterborne polyurethane emulsion; and intermittently adding a proper amount of 30-50 parts of acetone during the reaction period to reduce the viscosity.
Preparing synthetic leather of aqueous polyurethane resin: after acetone is removed from the polyurethane emulsion at the temperature of 40-55 ℃, 1.2 parts of aziridine, 2 parts of polysiloxane copolymer defoaming agent, 3 parts of dodecyl alcohol ester, 3 parts of polyether associative thickener, 2 parts of dicarboxylic acid alkyl ammonium salt propylene glycol solution and 10 parts of aqueous color paste are added, stirred at a low speed and uniformly mixed for 10-20 min to prepare aqueous polyurethane surface, middle and bottom material resins, and aqueous weather flame-retardant aqueous base bass 636E/flame-retardant aqueous space leather bass is used as a base material.
In addition, the invention also discloses a preparation method of the fully-aqueous system polyurethane synthetic leather prepared by adopting the surface, middle and bottom material resins and the base material of the Bass in a dry method, which comprises the following steps: firstly, coating one surface of a fabric layer on release paper and coating the other surface of the fabric layer on a middle material layer by adopting a release paper transfer method through the prepared surface and middle material resins, wherein the coating weights are respectively 180g/m and 180g/m2And drying by gradient heating at 100-130 deg.C at a heating rate of 2-5 deg.C/min, wherein the heating rate is further optimized to increase gradually, drying, and coating with 150g/m of resin as water-based primer2Further adopting a wet pasting method to laminate a flame-retardant water-based bass 636E/a flame-retardant water-based space leather bass; and then drying the synthetic leather at the temperature of 120-.
And (3) performance testing: the prepared waterborne polyurethane resin is applied to automobile leather, and the flame retardance is tested according to the standard of GB 8410-; according to the test standards of QB/T4194 plus 2011 polyurethane synthetic leather for automobiles and QB/T4043 plus 2010 polyvinyl chloride artificial leather for automobiles, the obtained full-aqueous system polyurethane resin synthetic leather provided by the invention is used for testing mechanical indexes such as tensile strength, peeling strength, tearing strength, seam strength and the like of a film material through an Instron universal testing machine; testing the wear resistance of the synthetic leather by adopting a Taber method, and testing the normal and low temperature folding resistance of the synthetic leather by adopting a folding strength tester; specific test results are shown in table 1.
In the embodiment, the polyester polyol can react with isocyanate to generate polyurethane, and simultaneously plays a role in enhancing the mechanical property of subsequent automobile leather to a greater extent; the polyester polyol is selected from one or a mixture of liquid or solid polycarbonate diols; the polyether glycol is one or more selected from high-activity polyether glycol, polytetrahydrofuran glycol, tetrahydrofuran copolymer glycol and tetrahydrofuran-ethylene oxide copolymer glycol; the melamine organic polyol is polyether melamine resin polyol, in particular EDS-5083 series products produced and prepared by Jiangsu Changteng energy-saving new material science and technology limited company; the polyisocyanate is aliphatic or aromatic diisocyanate, more specifically one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,6 hexyl diisocyanate, tetramethylcyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate and norbornane diisocyanate, p-phenylene diisocyanate and 1, 4-cyclohexane diisocyanate; the hydrophilic chain extender is selected from anionic group hydrophilic chain extenders, including carboxylic acid type and sulfonic acid type, more specifically one or more of dimethylolpropionic acid, dimethylolbutyric acid, 50% of solid content of sodium diaminosulfonate aqueous solution, 90% of solid content of sodium diaminosulfonate aqueous solution; the micromolecular non-hydrophilic chain extender is selected from one or more of 1,4 butanediol, glycol, 1,4 dimethylol cyclohexane, diethylene glycol and neopentyl glycol, dodecanediol and spiroglycol; the catalyst is selected from one or more of dibutyltin dilaurate, zinc carboxylate, bismuth carboxylate and tetrabutyl titanate; the internal crosslinking agent or the external crosslinking agent is selected from one or more of trimethylolpropane, silane coupling agent, aziridine, triethanolamine, carbodiimide and epoxy silane; the neutralizing agent is selected from one or more of triethylamine and diethanol amine; the rear chain extender is selected from one or more of isophorone diamine, ethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine and diamino dicyclohexyl methane; the defoaming agent is polysiloxane copolymer defoaming agent; the film forming auxiliary agent is one or more of N-methyl pyrrolidone and dodecyl alcohol ester; the thickening agent is hydroxymethyl cellulose or polyether associative thickening agent; the leveling wetting agent is a dicarboxylic acid alkyl ammonium salt propylene glycol solution.
TABLE 1 test performance results for examples 1 to 4
Note: the flame-retardant Bass base material is provided by combined-fertilizer science chemical industry Co.Ltd, and the flame-retardant grade of the product is B1 grade.
Description of Table 1: the second column is the index standard, and it can be seen that the performance tests of examples 1 to 4 all reach and far exceed the standard value. By adopting the preparation method, the melamine flame-retardant structure is introduced into the synthesis process of the waterborne polyurethane, so that a better flame-retardant effect is realized, and the mechanical property of the synthetic leather prepared from the waterborne polyurethane is enhanced; the fully-aqueous system flame-retardant polyurethane automobile leather with excellent performance is prepared by adopting a method of mixing materials at the surface, the middle and the bottom and combining a flame-retardant base material, not only overcomes the technical defects of the existing automobile leather product preparation, but also provides the polyurethane resin for the fully-aqueous system flame-retardant automobile leather and the preparation method of the synthetic leather thereof.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of waterborne polyurethane resin synthetic leather is characterized in that waterborne polyurethane resin is respectively used as a fabric layer, a middle material layer and a primer layer, coated on release paper and dried; attaching water-based space leather base on the primer layer, drying, and stripping release paper to obtain the water-based polyurethane resin synthetic leather; wherein the raw materials of the waterborne polyurethane comprise,
10-80 parts of polyester polyol, 30-120 parts of polyether polyol, 20-80 parts of melamine organic polyol, 15-55 parts of polyisocyanate, 3-20 parts of hydrophilic chain extender, 1-15 parts of micromolecular non-hydrophilic chain extender, 0.1-10 parts of catalyst, 0.1-8 parts of internal crosslinking agent, 2-18 parts of neutralizing agent, 1-5 parts of post chain extender, 30-100 parts of acetone and 400-800 parts of deionized water.
2. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the polyester polyol is one or a mixture of two of liquid or solid polycarbonate diol.
3. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the polyether glycol is one or a mixture of more of high-activity polyether glycol, polytetrahydrofuran glycol, tetrahydrofuran copolymer glycol and tetrahydrofuran-ethylene oxide copolymerization glycol.
4. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the melamine organic polyol is polyether melamine resin polyol.
5. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the hydrophilic chain extender comprises a carboxylic acid type anionic group hydrophilic chain extender and a sulfonic acid type anionic group hydrophilic chain extender.
6. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the micromolecule non-hydrophilic chain extender is one or a combination of more than one of 1,4 butanediol, ethylene glycol, 1, 4-dimethylolcyclohexane, diethylene glycol, neopentyl glycol, dodecanediol and spiroglycol.
7. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the catalyst is one or more of dibutyltin dilaurate, zinc carboxylate, bismuth carboxylate and tetrabutyl titanate.
8. The preparation method of the waterborne polyurethane resin synthetic leather according to claim 1, wherein the preparation method comprises the following steps: the rear chain extender is one or a combination of more of isophorone diamine, ethylene diamine, hexamethylene diamine, trimethyl hexamethylene diamine and diamino dicyclohexyl methane.
9. Use of a synthetic leather prepared by the preparation method according to any one of claims 1 to 8 in automotive leather.
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| CN111040118B (en) * | 2020-01-08 | 2022-02-01 | 嘉兴学院 | Waterborne polyurethane for microfiber leather as well as preparation method and application of waterborne polyurethane |
| CN113105602A (en) * | 2020-01-13 | 2021-07-13 | 浙江诚迅新材料有限公司 | Microfiber superfine fold line bonding layer resin and production process thereof |
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| CN112694583A (en) * | 2021-01-04 | 2021-04-23 | 山东天庆科技发展有限公司 | Wear-resistant scratch-resistant polyurethane resin for water-based synthetic leather and preparation method thereof |
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