CN108468226A - A kind of composite modified waterborne polyurethane synthetic leather - Google Patents

A kind of composite modified waterborne polyurethane synthetic leather Download PDF

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Publication number
CN108468226A
CN108468226A CN201810190987.6A CN201810190987A CN108468226A CN 108468226 A CN108468226 A CN 108468226A CN 201810190987 A CN201810190987 A CN 201810190987A CN 108468226 A CN108468226 A CN 108468226A
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China
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parts
synthetic leather
waterborne polyurethane
aqueous
emulsion
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CN201810190987.6A
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Chinese (zh)
Inventor
汪国水
李清
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JIANGXI MINGCHUAN SCIENCE AND TECHNOLOGY INDUSTRIAL Co Ltd
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JIANGXI MINGCHUAN SCIENCE AND TECHNOLOGY INDUSTRIAL Co Ltd
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Priority to CN201810190987.6A priority Critical patent/CN108468226A/en
Publication of CN108468226A publication Critical patent/CN108468226A/en
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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
    • 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
    • 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
    • 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
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • 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
    • 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
    • D06N3/147—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 characterised by the isocyanates used
    • 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
    • D06N3/147—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 characterised by the isocyanates used
    • D06N3/148—(cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • 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
    • 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
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1635—Elasticity
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    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Abstract

The invention belongs to synthetic leather material technology and synthetic leather manufacturing fields, and in particular to a kind of composite modified waterborne polyurethane synthetic leather, the waterborne polyurethane synthetic leather include constituent of the aqueous polyurethane emulsion of modified processing as base and surface layer slurry；The aqueous polyurethane emulsion includes following raw material components composition：200~300 parts of 100 parts of diisocyanate, polyethers or polyester polyol, 12~20 parts of alcohols chain extender, 3~10 parts of aqueous epoxy resin emulsion, 1~5 part of crosslinking agent, 5~10 parts of polysiloxane, 8~20 parts of hydrophilic agent, 10~20 parts of neutralizer, 50~100 parts of solvent, 400~1000 parts of deionized water；In the present invention, by using aqueous epoxy resin emulsion as crosslinking agent, the addition of polysiloxane；So that the aqueous polyurethane emulsion formed has three dimensional network structure, the elasticity of aqueous polyurethane emulsion is improved, secondly, the formation of reticular structure improves the surface strength of the waterborne polyurethane synthetic leather product of formation also using adjacent intermolecular bonding strength is enhanced.

Description

A kind of composite modified waterborne polyurethane synthetic leather
Technical field
The invention belongs to synthetic leather material technology and synthetic leather manufacturing fields, and in particular to a kind of composite modified aqueous poly- ammonia Lipase absobed is removed from office.
Background technology
Aqueous polyurethane as a kind of excellent filmogen, excellent penetrability, outstanding wearability, scratch resistance and Impayable low-temperature pliability is constantly recognized by people, and has obtained overall application on corium and spinning coating.Water Property polyurethane compared to using organic solvent polyurethane resin as synthesize leather goods base's knead dough layer, prevent from source The pollution of Synthetic Leather industry.
But due to containing hydrophilic ionic group, comprehensive performance during aqueous polyurethane molecular weight is small and strand It cannot still compare favourably with solvent borne polyurethane, limit its use in special occasions, therefore expert proposes difference both at home and abroad Modified method, improve the comprehensive performance of aqueous polyurethane emulsion, expand aqueous polyurethane emulsion use field, such as organosilicon Modification, epoxy resin modification, acrylate modified, organic fluorine richness etc., although its modified emulsion improves aqueous polyurethane breast Liquid certain aspect of performance deficiency, but most of single modified aqueous polyurethanes can also cause other aspect performances drop It is low.Therefore, in order to meet industrial production, it is often necessary to be carried out to aqueous polyurethane multiple modified to improve aqueous polyurethane emulsion Comprehensive performance.
Invention content
For the problems of the prior art, the purpose of the present invention is to provide a kind of composite modified waterborne polyurethane synthetic leathers Method, improve the comprehensive performance of waterborne polyurethane synthetic leather.
To achieve the goals above, the present invention is achieved by the following scheme：
A kind of composite modified waterborne polyurethane synthetic leather, the waterborne polyurethane synthetic leather include the water of modified processing Constituent of the property polyaminoester emulsion as base and surface layer slurry；
The aqueous polyurethane emulsion includes following raw material components composition：100 parts of diisocyanate, polyethers or polyester are more It is 200~300 parts of first alcohol, 12~20 parts of alcohols chain extender, 3~10 parts of aqueous epoxy resin emulsion, 1~5 part of crosslinking agent, poly- organic 5~10 parts of siloxanes, 8~20 parts of hydrophilic agent, 10~20 parts of neutralizer, 50~100 parts of solvent, 400~1000 parts of deionized water.
Preferably, the aqueous polyurethane emulsion includes following raw material components composition：100 parts of diisocyanate, Polyethers or 220~280 parts of polyester polyol, 14~18 parts of alcohols chain extender, 5~8 parts of aqueous epoxy resin emulsion, crosslinking agent 2 ~5 parts, 6~9 parts of polysiloxane, 12~16 parts of hydrophilic agent, 12~15 parts of neutralizer, 60~90 parts of solvent, deionized water 500~800 parts.
According to the present invention, alcohols chain extender is in the building-up process of aqueous polyurethane for adjusting molecular weight and soft, hard section Ratio, preferably, heretofore described alcohols chain extender be selected from 1,4-butanediol, ethylene glycol or diglycol In any one.
According to the present invention, the crosslinking agent is at least one of trimethylolpropane, glycerine or castor oil.
According to the present invention, hydrophilic agent introduces the chain extender of hydrophilic radical on aqueous polyurethane macromolecular main chain, it is water Property polyurethane prepare in the function monomer that uses, the polyurethane that is combined with such group is neutralized, ionization, that is, presents water-soluble Property, heretofore described hydrophilic agent is any one in 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids or tartaric acid Kind.
According to the present invention, neutralizer is a kind of reagent that can be with carboxyl, sulfonic group or tertiary amine groups at salt, heretofore described Neutralizer be triethylamine, ammonium hydroxide, hydrochloric acid or acetic acid in one kind.
In the present invention, the diisocyanate is isoflurane chalcone diisocyanate, hexamethylene diisocyanate, toluene At least one of diisocyanate and '-diphenylmethane diisocyanate.The polyethers or polyester polyol constitutes polyurethane Soft segment, specifically can be selected from polytetrahydrofuran diol, Polyoxypropylene diol, polybutylene glyool adipate, gather oneself At least one of naphthalate glycol, polycaprolactone glycol and polycarbonate glycol.
According to the present invention, viscosity when being prepared due to Waterborne Polyurethane Prepolymer is larger, in order to facilitate mass transfer, heat transfer, especially It is the emulsification in later stage, it is necessary to solvent appropriate be added, solvent of the present invention is dimethylformamide, dimethylacetylamide Or any one in N-Methyl pyrrolidone.
The modification processing method of above-mentioned aqueous polyurethane emulsion is：
(1) by diisocyanate, polyethers or polyester polyol, the alcohols chain extender for being formulated half amount, aqueous epoxy resins Lotion, crosslinking agent and solvent are added in reactor, in 60~90 DEG C of back flow reaction 2h, hydrophilic agent are added and continues back flow reaction 2h, Obtain base polyurethane prepolymer for use as；
(2) base polyurethane prepolymer for use as is cooled to 40 DEG C hereinafter, polysiloxane and neutralizer is added, stirring makes wherein With 30~40min of reaction, be added remaining alcohols chain extender and deionized water, 2~3h of high-speed stirred, obtain solid content 30~ The aqueous polyurethane emulsion of 45wt%.
Compared with prior art, the present invention has the following technical effects：
In the present invention, by using aqueous epoxy resin emulsion as crosslinking agent, there are two containing in epoxy molecule Or more than two epoxy groups, there can be the group of active H to react with the alcoholic extract hydroxyl group etc. in polyester polyol, to realize big point Crosslinking between son so that the aqueous polyurethane emulsion of formation has three dimensional network structure, improves the elasticity of aqueous polyurethane emulsion.
In the present invention, by the addition of polysiloxane, multiple hydroxyls on molecule can be with the alcohol of polyester polyol Hydroxyl reaction forms three-dimensional netted resin structure so that the crosslink density of product increases, and increases returning for aqueous polyurethane emulsion Elastic energy, so that the crumpling resistance for the waterborne polyurethane synthetic leather being prepared can greatly improve；Secondly, the shape of reticular structure Enhance adjacent intermolecular bonding strength at also utilizing, improves the surface strength of the waterborne polyurethane synthetic leather product of formation.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below Specific embodiment is closed, the present invention is furture elucidated.
The present invention provides a kind of composite modified waterborne polyurethane synthetic leather, the waterborne polyurethane synthetic leather includes warp Constituent of the aqueous polyurethane emulsion of modification as base and surface layer slurry.
Base's slurry includes the raw material components of following parts by weight：
100 parts of aqueous polyurethane emulsion, 5 parts of foaming agent (azodicarbonamide), the levelling agent (Silok of modified processing Leveling8255 is purchased from Guangzhou Si Luoke Chemical Co., Ltd) 0.3 part, antifoaming agent (Foamex 800, purchased from German enlightening Gao companies) 0.2 part, 0.4 part of thickener (COSIE FT-835, Lan Ya trade Co., Ltds), it is 2800mPas to be made into viscosity Base's slurry.
The surface layer slurry includes the raw material components of following parts by weight：
18 parts of 100 parts of aqueous polyurethane emulsion, aqueous color paste, the levelling agent (Silok of modified processing Leveling8255 is purchased from Guangzhou Si Luoke Chemical Co., Ltd) 0.7 part, antifoaming agent (Foamex 800, purchased from German enlightening Gao companies) 0.3 part, 3 parts of aqueous epoxy resin emulsion (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), thickener 0.4 part of (COSIE FT-835, Lan Ya trade Co., Ltds).
Waterborne polyurethane synthetic leather applies the technique that four dry using three and is prepared in the present invention, that is, applies shaving layer-drying- Cooling-painting foamed slurry-drying-cooling-painting adhesive linkage-drying to half-dried-patch-foaming-cooling-paper leather divides From, it is coiled.
Specific step is：
S1：The painting of aqueous polyurethane surface layer slurry is scraped in release paper, starching amount is 90g/m2, it is subsequently placed into baking oven and does Dry solidification, the temperature setting range of baking oven and drying time are respectively set to：One section 80~100 DEG C, 1min, two section 110~120 DEG C, 45s, three sections 120~130 DEG C, 30s；
S2：In the face of S1, Tu Gua bases slurry on the basis of layer, starching amount are 250g/m2, dry, baking is then placed in baking oven The temperature setting range of case and drying time are respectively set to：One section 80~100 DEG C, 1min, two sections 110~120 DEG C, 1min, Three sections 120~130 DEG C, 1min；
S3：It is applied on the basis of the base of S2 and scrapes bonded adhesives, starching amount is 110g/m2, 90s is toasted into baking oven, then It is bonded with base fabric, paper, leather separation；
S4：The leather that S3 is obtained is put into baking oven and is foamed, temperature setting is 200~250 DEG C, and foamed time is 2~3min.
S5：Synthesis leather goods arrangement after foaming be can be obtained into foaming synthetic leather finished product, arranging process includes changing colour, pressing It spends, be surface-treated, rubbing the same common process of line.
The aqueous polyurethane emulsion of above-mentioned modified processing includes the specific embodiment of following embodiment.
Embodiment 1
A kind of aqueous polyurethane emulsion, including following raw material components composition：
100 parts of isoflurane chalcone diisocyanate, 250 parts of polytetrahydrofuran diol, 16 parts of 1,4- butanediols, water-base epoxy tree 6 parts of fat liquor (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), 3 parts of trimethylolpropane, polysiloxane (BT- 200 dimethicones are purchased from Guangzhou Ba Tai Chemical Co., Ltd.s) 8 parts, 15 parts of 2,2- dihydromethyl propionic acids, 13 parts of triethylamine, two 80 parts of methylformamide, 700 parts of deionized water.
Embodiment 2
A kind of aqueous polyurethane emulsion, including following raw material components composition：
100 parts of isoflurane chalcone diisocyanate, 220 parts of polytetrahydrofuran diol, 14 parts of 1,4- butanediols, water-base epoxy tree 5 parts of fat liquor (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), 2 parts of trimethylolpropane, polysiloxane (BT- 200 dimethicones are purchased from Guangzhou Ba Tai Chemical Co., Ltd.s) 6 parts, 12 parts of 2,2- dihydromethyl propionic acids, 12 parts of triethylamine, two 60 parts of methylformamide, 500 parts of deionized water.
Embodiment 3
A kind of aqueous polyurethane emulsion, including following raw material components composition：
100 parts of isoflurane chalcone diisocyanate, 280 parts of polytetrahydrofuran diol, 18 parts of 1,4- butanediols, water-base epoxy tree 8 parts of fat liquor (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), 5 parts of trimethylolpropane, polysiloxane (BT- 200 dimethicones are purchased from Guangzhou Ba Tai Chemical Co., Ltd.s) 9 parts, 16 parts of 2,2- dihydromethyl propionic acids, 15 parts of triethylamine, two 90 parts of methylformamide, 800 parts of deionized water.
Embodiment 4
A kind of aqueous polyurethane emulsion, including following raw material components composition：
100 parts of isoflurane chalcone diisocyanate, 200 parts of polytetrahydrofuran diol, 12 parts of ethylene glycol, aqueous epoxy resins breast 3 parts of liquid (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), 1 part of trimethylolpropane, polysiloxane (BT-200 Dimethicone is purchased from Guangzhou Ba Tai Chemical Co., Ltd.s) 5 parts, 8 parts of 2,2- dihydromethyl propionic acids, 10 parts of triethylamine, dimethyl 50 parts of formamide, 400 parts of deionized water.
Embodiment 5
A kind of aqueous polyurethane emulsion, including following raw material components composition：
100 parts of isoflurane chalcone diisocyanate, 300 parts of polytetrahydrofuran diol, 20 parts of ethylene glycol, aqueous epoxy resins breast 10 parts of liquid (WS-500 is purchased from Xin Hua new materials Science and Technology Ltd.), 5 parts of trimethylolpropane, polysiloxane (BT-200 Dimethicone is purchased from Guangzhou Ba Tai Chemical Co., Ltd.s) 10 parts, 20 parts of 2,2- dihydromethyl propionic acids, 20 parts of triethylamine, diformazan 100 parts of base formamide, 1000 parts of deionized water.
Comparative example 1
With 32% polyaminoester emulsion (hard) purchased from Shanghai Tuo Jia printing materials Co., Ltd, the trade mark be AB-1 as a comparison Example.
Table 1 is above-described embodiment 1-5, the aqueous polyurethane emulsion of comparative example 1 is aqueous polyurethane that raw material is prepared The technical indicator of synthetic leather compares
The basic principles and main features and the features of the present invention of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement is both fallen in the range of claimed invention.The scope of protection of present invention is by appended claims And its equivalent thereof.

Claims (6)

1. a kind of composite modified waterborne polyurethane synthetic leather, it is characterised in that：The waterborne polyurethane synthetic leather includes through changing Property processing constituent of the aqueous polyurethane emulsion as base and surface layer slurry；
The aqueous polyurethane emulsion includes following raw material components composition：100 parts of diisocyanate, polyethers or polyester polyol 200~300 parts, 12~20 parts of alcohols chain extender, 3~10 parts of aqueous epoxy resin emulsion, 1~5 part of crosslinking agent, poly organo 5~10 parts of alkane, 8~20 parts of hydrophilic agent, 10~20 parts of neutralizer, 50~100 parts of solvent, 400~1000 parts of deionized water.
2. composite modified waterborne polyurethane synthetic leather according to claim 1, wherein the aqueous polyurethane emulsion packet Include following raw material components composition：100 parts of diisocyanate, polyethers or 220~280 parts of polyester polyol, alcohols chain extender 14~ 18 parts, 5~8 parts of aqueous epoxy resin emulsion, 2~5 parts of crosslinking agent, 6~9 parts of polysiloxane, 12~16 parts of hydrophilic agent, in With 12~15 parts of agent, 60~90 parts of solvent, 500~800 parts of deionized water.
3. composite modified waterborne polyurethane synthetic leather according to claim 1, wherein the alcohols chain extender is selected from 1, Any one in 4- butanediols, ethylene glycol or diglycol.
4. composite modified waterborne polyurethane synthetic leather according to claim 1, wherein the crosslinking agent is trihydroxy methyl At least one of propane, glycerine or castor oil.
5. composite modified waterborne polyurethane synthetic leather according to claim 1, wherein the hydrophilic agent is 2,2- dihydroxies Any one in methylpropanoic acid, 2,2- dimethylolpropionic acids or tartaric acid.
6. composite modified waterborne polyurethane synthetic leather according to claim 1, wherein the neutralizer be triethylamine, One kind in ammonium hydroxide, hydrochloric acid or acetic acid.
CN201810190987.6A 2018-03-08 2018-03-08 A kind of composite modified waterborne polyurethane synthetic leather Pending CN108468226A (en)

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CN112851248A (en) * 2021-01-29 2021-05-28 烟台华宝新材料科技有限公司 High-strength concrete and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN109371699A (en) * 2018-09-12 2019-02-22 福建隆上超纤有限公司 A kind of preparation method of high-temperature resistant waterborne polyurethane artificial leather
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CN112851248A (en) * 2021-01-29 2021-05-28 烟台华宝新材料科技有限公司 High-strength concrete and preparation method thereof
CN114349930A (en) * 2022-01-17 2022-04-15 万华化学集团股份有限公司 Waterborne polyurethane resin emulsion, preparation method and earphone cover leather
CN114349930B (en) * 2022-01-17 2023-07-04 万华化学集团股份有限公司 Aqueous polyurethane resin emulsion and preparation method thereof, and earphone sleeve leather

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Application publication date: 20180831