CN109517565A - A kind of preparation method of polyurethane artificial leather adhesive layer - Google Patents

A kind of preparation method of polyurethane artificial leather adhesive layer Download PDF

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Publication number
CN109517565A
CN109517565A CN201811317472.4A CN201811317472A CN109517565A CN 109517565 A CN109517565 A CN 109517565A CN 201811317472 A CN201811317472 A CN 201811317472A CN 109517565 A CN109517565 A CN 109517565A
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parts
polyurethane
artificial leather
preparation
adhesive layer
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张海涛
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Hefei Kaida New Material Technology Co Ltd
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Hefei Kaida New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • 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
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    • 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
    • C08G18/4027—Mixtures of compounds of group C08G18/54 with other macromolecular compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/54—Polycondensates of aldehydes
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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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
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    • 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
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

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  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
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  • Emergency Medicine (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention belongs to artificial leather processing technique fields, more particularly to a kind of preparation method of polyurethane artificial leather adhesive layer, it foams including polyurethane artificial leather material, then polyurethane binder is coated on obtained artificial leather material surface, press base fabric, it is obtained after drying, described polyurethane binder includes following raw material: aliphatic polyester polyols, resol, polycaprolactone polyol, 2, 2- dihydromethyl propionic acid, ethoxylated trimethylolpropane triacrylate, tetraisocyanate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, Diacetone Acrylamide, peroxidating double 2, 4- dichloro-benzoyl.The present invention is had the advantage that in the present invention compared with prior art by reasonably selecting the raw material and proportion of polyurethane adhesive, is cooperated processing conditions appropriate, is stablized gained polyurethane adhesive performance, guarantees the stability of polyurethane adhesive under alkaline condition；Comprehensive performance is preferable, organic solvent-free, is suitable for promoting the use of.

Description

A kind of preparation method of polyurethane artificial leather adhesive layer
Technical field
The invention belongs to artificial leather processing technique fields, and in particular to a kind of preparation side of polyurethane artificial leather adhesive layer Method.
Background technique
Before this, occupy main status in synthetic leather circle is PVC artificial leather, it mainly adds plasticizer, steady by PVC Determine thickener made of agent etc., after coloring, coating gel, it is similar to leather that various appearances are made in stamp, embossing or embossing Product, the features such as PVC artificial leather is with its approximate natural leather, appearance is bright-coloured, soft, wear-resisting, folding, acid and alkali-resistance, from The 1970s is developed so far, and has had sizable scale, but the gas permeability and hygroscopicity due to PVC artificial leather are all There is certain limitation, is typically now replaced with PU, skilledization of production technology greatly reduces the production cost of PU synthetic leather, Much all built standing in area completely produces industrial chains in China, with hardness is adjustable, flexibility is good, cryogenic property is excellent Different, the advantages that intensity is big, polyurethane is widely used in artificial leather adhesive, the preparation method of traditional waterborne polyurethane Internal emulsification method is mainly used, a small amount of organic solvent is added in aqueous polyurethane preparation prepolymerisation stage and adjusts viscosity, causes aqueous Have therefore how a small amount of organic solvent residual removes adhesive layer organic solvent needs during preparing artificial leather in polyurethane Further research.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of preparation method of polyurethane artificial leather adhesive layer is provided.
The present invention is achieved by the following technical solutions: a kind of preparation method of polyurethane artificial leather adhesive layer, including Then the foaming of polyurethane artificial leather material is coated with polyurethane binder on obtained artificial leather material surface, after pressing base fabric, drying It arrives, described polyurethane binder includes the raw material of following parts by weight: 60-70 parts of aliphatic polyester polyols, first stage phenolic tree 2-6 parts of rouge, 18-24 parts of polycaprolactone polyol, 2-5 parts of 2,2- dihydromethyl propionic acid, ethoxylated trimethylolpropane 3 third 3-5 parts of olefin(e) acid ester, 16-20 parts of tetraisocyanate, 2-3 parts of polypropylene glycol glycidol ether, 1-2 parts of acrylic ester cross-linking agent, 2.2-2.8 parts of Diacetone Acrylamide, double 0.2-0.4 parts of 2, the 4- dichloro-benzoyls of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 85-95 DEG C, reaction 1.5-2.5 hours, Diacetone Acrylamide, polycaprolactone polyol, first stage phenolic is added Resin, through 12-16kGy's60Co- gamma-ray irradiation, then keeping temperature is 60-70 DEG C, and 2,2- dihydromethyl propionic acid, second is added Oxygroup trimethylolpropane trimethacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, peroxidating double 2,4- Dichloro-benzoyl is stirred to react 3-4 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product.
As further improvement of these options, the viscosity of described polyurethane binder is 2600-2800Pas.
As further improvement of these options, the viscosity of described polyurethane binder is adjusted by Silica hydrogel.
As further improvement of these options, coating weight of the described adhesive on artificial leather surface is 60-70g/m2.
As further improvement of these options, the aliphatic polyester polyols are adipic acid system polyester-diol.
As further improvement of these options, the polycaprolactone polyol be polyethylene glycol adipate glycol, Polyadipate castor oil ester polyalcohol, polyadipate -1,4- butyl glycol ester diol, polyadipate neopentyl glycol -1,6-HD At least two in ester diacid, polyadipate ethylene glycol-diglycol ethylene esterdiol.
As further improvement of these options, the acrylic ester cross-linking agent is diacrylate -1,4-butanediol Any one in ester, ethylene glycol dimethacrylate.
As further improvement of these options, the polyurethane artificial leather material includes the raw material of following parts by weight: poly- 100 parts of urethane resin, 35-45 parts of calcium carbonate, 25-32 parts of dioctyl terephthalate, 12-18 parts of phthalic anhydride, tetrem 4-6 parts of alkenyl tetramethyl-ring tetrasiloxane, 1-3 parts of low-molecular-weight hydroxyl silicone oil, 2-6 parts of trifluoro propyl silicone oil, foaming agent 2-3 Part, 1-2 parts of peroxidating -2- butanone.
As further improvement of these options, the polyurethane artificial leather material is in coating adhesive, after pressing base fabric, It is dried under conditions of temperature is 95-105 DEG C.
2, the 2- dihydromethyl propionic acid has preferable heat resistance and water resistance, polyurethane can be made obtained from emulsibility Energy.
The present invention has the advantage that the raw material in the present invention by reasonably selecting polyurethane adhesive compared with prior art And proportion, cooperate processing conditions appropriate, stablizes gained polyurethane adhesive performance, there is preferable low temperature flexibility and resistance to Hou Xing contains polyester-diol in aliphatic polyester polyols, facilitates the cohesive strength for enhancing polyurethane adhesive, and then guarantees poly- The peel strength of urethane polyalcohol, ethoxylated trimethylolpropane triacrylate, acrylic ester cross-linking agent, diacetone third The mating reaction of acrylamide can effectively disperse in polyurethane adhesive, improve its intermolecular force, and guarantee polyurethane The stability of binder under alkaline condition；Comprehensive performance is preferable, organic solvent-free, safety and environmental protection, is suitable for promoting the use of.
Specific embodiment
For the technology contents that the present invention will be described in detail, the purpose and effect realized, give below in conjunction with embodiment Explanation.
The most critical design of the present invention is: cooperation is appropriate by the raw material and proportion that reasonably select polyurethane adhesive Processing conditions, make gained polyurethane adhesive performance stablize, have preferable low temperature flexibility and weatherability, aliphatic polyester Contain polyester-diol in polyalcohol, facilitates the cohesive strength for enhancing polyurethane adhesive, and then guarantee the stripping of polyurethane polyol From intensity, ethoxylated trimethylolpropane triacrylate, acrylic ester cross-linking agent, matching for Diacetone Acrylamide cooperate With can effectively disperse in polyurethane adhesive, improve its intermolecular force, obtain the viscoelastic polyurethane of excellent combination property Tie agent.
Part material source used is as follows in the present invention: the polyurethane resin is to be mentioned by Zhejiang Luoxing Industrial Co., Ltd. The aqueous polyurethane AMS-2066 of confession；The calcium carbonate is the model 1205 that Jiangxi Province Bai Rui calcium carbonate Co., Ltd provides Fine ultrawhite precipitated calcium carbonate；The low-molecular-weight hydroxyl silicone oil is the hydroxyl silicon provided by Jinan Xing Feilong Chemical Co., Ltd. Oil 209；The foaming agent is the dipropylene glycol methyl ether provided by Shandong Shang Hekai Chemical Co., Ltd..
The present invention provides a kind of preparation method of polyurethane artificial leather adhesive layer, including the foaming of polyurethane artificial leather material, so It is coated with polyurethane binder on obtained artificial leather material surface afterwards, is obtained after pressing base fabric, drying, polyurethane binder packet Include the raw material of following parts by weight: 60-70 parts of aliphatic polyester polyols, 2-6 parts of resol, polycaprolactone polyol 18-24 parts, 2-5 parts of 2,2- dihydromethyl propionic acid, 3-5 parts of ethoxylated trimethylolpropane triacrylate, tetraisocyanate 16-20 parts, 2-3 parts of polypropylene glycol glycidol ether, 1-2 parts of acrylic ester cross-linking agent, Diacetone Acrylamide 2.2-2.8 Part, double 0.2-0.4 parts of 2, the 4- dichloro-benzoyls of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 85-95 DEG C, reaction 1.5-2.5 hours, Diacetone Acrylamide, polycaprolactone polyol, first stage phenolic is added Resin, through 12-16kGy's60Co- gamma-ray irradiation, then keeping temperature is 60-70 DEG C, and 2,2- dihydromethyl propionic acid, second is added Oxygroup trimethylolpropane trimethacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, peroxidating double 2,4- Dichloro-benzoyl is stirred to react 3-4 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product.
Seen from the above description, polyalcohol of different nature cooperates respective material, is made viscous under appropriate processing conditions The polyurethane adhesive of the excellent organic solvent-free of degree, alkaline resistance properties, safety and environmental protection are applied widely.
As further improvement of these options, the viscosity of described polyurethane binder is 2600-2800Pas；Institute The viscosity for stating polyurethane binder is adjusted by Silica hydrogel.
Seen from the above description, it can guarantee the preparation of polyurethane artificial leather, guarantee peel strength.
As further improvement of these options, coating weight of the described adhesive on artificial leather surface is 60-70g/m2.
Seen from the above description, the effective preparation that can guarantee polyurethane artificial leather makes it have structural stability and resistance to Cryogenic property.
As further improvement of these options, the aliphatic polyester polyols are adipic acid system polyester-diol.
Seen from the above description, aliphatic polyester polyols help to enhance the cohesive strength of polyurethane adhesive, in turn Guarantee the peel strength of polyurethane polyol.
As further improvement of these options, the polycaprolactone polyol be polyethylene glycol adipate glycol, Polyadipate castor oil ester polyalcohol, polyadipate -1,4- butyl glycol ester diol, polyadipate neopentyl glycol -1,6-HD At least two in ester diacid, polyadipate ethylene glycol-diglycol ethylene esterdiol.
Seen from the above description, a variety of polycaprolactone polyols can make gained polyurethane adhesive stretching with higher Intensity and alkaline resistance properties.
As further improvement of these options, the acrylic ester cross-linking agent is diacrylate -1,4-butanediol Any one in ester, ethylene glycol dimethacrylate.
Seen from the above description, it can be improved its intermolecular force, the removing for helping to enhance polyurethane adhesive is strong Degree.
As further improvement of these options, the polyurethane artificial leather material includes the raw material of following parts by weight: poly- 100 parts of urethane resin, 35-45 parts of calcium carbonate, 25-32 parts of dioctyl terephthalate, 12-18 parts of phthalic anhydride, tetrem 4-6 parts of alkenyl tetramethyl-ring tetrasiloxane, 1-3 parts of low-molecular-weight hydroxyl silicone oil, 2-6 parts of trifluoro propyl silicone oil, foaming agent 2-3 Part, 1-2 parts of peroxidating -2- butanone.
As further improvement of these options, the polyurethane artificial leather material is in coating adhesive, after pressing base fabric, It is dried under conditions of temperature is 95-105 DEG C.
Seen from the above description, the stable artificial leather material of performance can be obtained, effectively making for polyurethane adhesive is facilitated With.
Embodiment 1
A kind of preparation method of polyurethane artificial leather adhesive layer, including the foaming of polyurethane artificial leather material, it is then artificial what is obtained Leather material surface is coated with polyurethane binder, and coating weight of the described adhesive on artificial leather surface is 65g/m2, base fabric is pressed, in temperature Degree obtains after drying under conditions of being 100 DEG C, and described polyurethane binder includes the raw material of following parts by weight: aliphatic polyester is more 65 parts of first alcohol, 4 parts of resol, 21 parts of polycaprolactone polyol, 3.5 parts of 2,2- dihydromethyl propionic acid, ethoxylation 4 parts of trimethylolpropane trimethacrylate, 18 parts of tetraisocyanate, 2.5 parts of polypropylene glycol glycidol ether, esters of acrylic acid are handed over Join 1.5 parts of agent, 2.5 parts of Diacetone Acrylamide, double 0.3 part of dichloro-benzoyl of 2, the 4- of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 90 DEG C, reaction 2 hours, Diacetone Acrylamide, polycaprolactone polyol, resol, warp is added 14kGy's60Co- gamma-ray irradiation, then keeping temperature is 65 DEG C, and 2,2- dihydromethyl propionic acid, three hydroxyl first of ethoxylation is added Base propane triacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, double 2, the 4- dichloro-benzoyls of peroxidating, It is stirred to react 3.5 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product；
The polyurethane artificial leather material includes the raw material of following parts by weight: 100 parts of polyurethane resin, 40 parts of calcium carbonate, to benzene two 27 parts of formic acid dioctyl ester, 15 parts of phthalic anhydride, 5 parts of tetravinyl tetramethyl-ring tetrasiloxane, low-molecular-weight hydroxyl silicone oil 2 Part, 3.5 parts of trifluoro propyl silicone oil, 2.5 parts of foaming agent, 1.5 parts of peroxidating -2- butanone；
Wherein, the viscosity of described polyurethane binder is 2700Pas；The viscosity of described polyurethane binder is by Silica hydrogel tune Section.
Wherein, the polycaprolactone polyol be polyethylene glycol adipate glycol, polyadipate castor oil ester polyalcohol, Polyadipate -1,4- butyl glycol ester diol is mixed to get with weight ratio 4:1:1；The acrylic ester cross-linking agent is two propylene Acid -1,4-butanediol ester.
Embodiment 2
A kind of preparation method of polyurethane artificial leather adhesive layer, including the foaming of polyurethane artificial leather material, it is then artificial what is obtained Leather material surface is coated with polyurethane binder, and coating weight of the described adhesive on artificial leather surface is 60g/m2, base fabric is pressed, in temperature Degree obtains after drying under conditions of being 105 DEG C, and described polyurethane binder includes the raw material of following parts by weight: aliphatic polyester is more 60 parts of first alcohol, 6 parts of resol, 24 parts of polycaprolactone polyol, 5 parts of 2,2- dihydromethyl propionic acid, ethoxylation three 3 parts of hydroxymethyl-propane triacrylate, 20 parts of tetraisocyanate, 3 parts of polypropylene glycol glycidol ether, acrylic ester cross-linking agent 2 parts, 2.8 parts of Diacetone Acrylamide, double 0.2 part of dichloro-benzoyl of 2, the 4- of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 85 DEG C, reaction 1.5 hours, Diacetone Acrylamide, polycaprolactone polyol, resol, warp is added 16kGy's60Co- gamma-ray irradiation, then keeping temperature is 70 DEG C, and 2,2- dihydromethyl propionic acid, three hydroxyl first of ethoxylation is added Base propane triacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, double 2, the 4- dichloro-benzoyls of peroxidating, It is stirred to react 4 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product；
The polyurethane artificial leather material includes the raw material of following parts by weight: 100 parts of polyurethane resin, 45 parts of calcium carbonate, to benzene two 25 parts of formic acid dioctyl ester, 18 parts of phthalic anhydride, 4 parts of tetravinyl tetramethyl-ring tetrasiloxane, low-molecular-weight hydroxyl silicone oil 3 Part, 2 parts of trifluoro propyl silicone oil, 3 parts of foaming agent, 1 part of peroxidating -2- butanone；
Wherein, the viscosity of described polyurethane binder is 2600Pas；The viscosity of described polyurethane binder is by Silica hydrogel tune Section.
Wherein, the polycaprolactone polyol is polyadipate castor oil ester polyalcohol, polyadipate neopentyl glycol -1,6- Hexylene glycol ester diacid, polyadipate ethylene glycol-diglycol ethylene esterdiol are mixed to get with weight ratio 6:3:1；The acrylic acid Esters crosslinking agent is diacrylate -1,4-butanediol ester.
Embodiment 3
A kind of preparation method of polyurethane artificial leather adhesive layer, including the foaming of polyurethane artificial leather material, it is then artificial what is obtained Leather material surface is coated with polyurethane binder, and coating weight of the described adhesive on artificial leather surface is 70g/m2, base fabric is pressed, in temperature Degree obtains after drying under conditions of being 95 DEG C, and described polyurethane binder includes the raw material of following parts by weight: aliphatic polyester is more 70 parts of first alcohol, 2 parts of resol, 18 parts of polycaprolactone polyol, 2 parts of 2,2- dihydromethyl propionic acid, ethoxylation three 5 parts of hydroxymethyl-propane triacrylate, 16 parts of tetraisocyanate, 2 parts of polypropylene glycol glycidol ether, acrylic ester cross-linking agent 1 part, 2.2 parts of Diacetone Acrylamide, double 0.4 part of dichloro-benzoyl of 2, the 4- of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 95 DEG C, reaction 2.5 hours, Diacetone Acrylamide, polycaprolactone polyol, resol, warp is added 12kGy's60Co- gamma-ray irradiation, then keeping temperature is 60 DEG C, and 2,2- dihydromethyl propionic acid, three hydroxyl first of ethoxylation is added Base propane triacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, double 2, the 4- dichloro-benzoyls of peroxidating, It is stirred to react 3 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product；
The polyurethane artificial leather material includes the raw material of following parts by weight: 100 parts of polyurethane resin, 35 parts of calcium carbonate, to benzene two 32 parts of formic acid dioctyl ester, 12 parts of phthalic anhydride, 6 parts of tetravinyl tetramethyl-ring tetrasiloxane, low-molecular-weight hydroxyl silicone oil 1 Part, 6 parts of trifluoro propyl silicone oil, 2 parts of foaming agent, 2 parts of peroxidating -2- butanone；
Wherein, the viscosity of described polyurethane binder is 2800Pas；The viscosity of described polyurethane binder is by Silica hydrogel tune Section.
Wherein, the polycaprolactone polyol is polyadipate neopentyl glycol -1,6- hexylene glycol ester diacid, polyadipate second Glycol-diglycol ethylene esterdiol is mixed to get with weight ratio 3:1；The acrylic ester cross-linking agent is dimethacrylate second Diol ester.
Control group 1 is set, aliphatic polyester polyols in embodiment 1 are replaced with etc. to the polypropylene glycol diols of weight, Remaining content is constant；
Control group 2 is set, polycaprolactone polyol in embodiment 1 is replaced with etc. to the polypropylene glycol diols of weight, in remaining Hold constant；
Control group 3 is set, polycaprolactone polyol in embodiment 1 is replaced with etc. to the aliphatic polyester polyols of weight, remaining Content is constant；
Control group 4 is set, resol in embodiment 1 is removed, remaining content is constant；
Control group 5 is set, acrylic ester cross-linking agent in embodiment 1 is removed, remaining content is constant；
Control group 6 is set, Diacetone Acrylamide in embodiment 1 is removed, remaining content is constant；
Control group 7 is set, double 2, the 4- dichloro-benzoyls of peroxidating in embodiment 1 are removed, remaining content is constant；
Control group 8 is set, it will be in embodiment 160Co- gamma-ray irradiation step is removed, remaining content is constant；
After polyurethane adhesive is adjusted to corresponding viscosity, using NDJ-5S viscosity determinator, under conditions of temperature is 25 DEG C The viscosity of each group sample is detected, every group of data seek 5 cell means；Polyurethane adhesive is measured according to GB/T 6753.3-1986 Stability judges whether there is 6 months storage stabilities；According to GB/T 2791-1995 to the peel strength of polyurethane adhesive It is detected；Then last gained artificial leather test specimen is put into the sodium hydrate aqueous solution that mass concentration is 1%, is in temperature It is kept for 24 hours under conditions of 20 DEG C, detects adhesion strength again according to GB/T 2791-1995, be denoted as alkaline peel strength, it will Alkaline peel strength (× 100%) compared with aforementioned peel strength, gained ratio are denoted as resistance to base number；
It detects according to the method described above, obtains following result:
Table 1
As data in table 1 can be seen that according to the present invention formula and preparation condition preparation obtained by polyurethane binder application In polyurethane artificial leather, comprehensive performance is preferable, environment friendly and pollution-free.
In conclusion the present invention provides a kind of preparation method of polyurethane artificial leather adhesive layer, by reasonably selecting poly- ammonia The raw material and proportion of ester binder, cooperate processing conditions appropriate, stablize gained polyurethane adhesive performance, have preferable Low temperature flexibility and weatherability contain polyester-diol in aliphatic polyester polyols, facilitate the cohesion for enhancing polyurethane adhesive Intensity, and then guarantee the peel strength of polyurethane polyol, ethoxylated trimethylolpropane triacrylate, esters of acrylic acid The mating reaction of crosslinking agent, Diacetone Acrylamide can effectively disperse in polyurethane adhesive, improve its intermolecular interaction Power obtains the polyurethane adhesive of excellent combination property.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair In bright scope of patent protection.

Claims (9)

1. a kind of preparation method of polyurethane artificial leather adhesive layer, including the foaming of polyurethane artificial leather material, then in obtained people Fabricate-leather material surface is coated with polyurethane binder, obtains after pressing base fabric, drying, it is characterized in that, described polyurethane binder Raw material including following parts by weight: 60-70 parts of aliphatic polyester polyols, 2-6 parts of resol, polycaprolactone polyol 18-24 parts of alcohol, 2-5 parts of 2,2- dihydromethyl propionic acid, 3-5 parts of ethoxylated trimethylolpropane triacrylate, four isocyanic acids 16-20 parts of ester, 2-3 parts of polypropylene glycol glycidol ether, 1-2 parts of acrylic ester cross-linking agent, Diacetone Acrylamide 2.2-2.8 Part, double 0.2-0.4 parts of 2, the 4- dichloro-benzoyls of peroxidating；
The preparation method of described polyurethane binder includes the following contents: aliphatic polyester polyols, tetraisocyanate mixed, After hotter to 85-95 DEG C, reaction 1.5-2.5 hours, Diacetone Acrylamide, polycaprolactone polyol, first stage phenolic is added Resin, through 12-16kGy's60Co- gamma-ray irradiation, then keeping temperature is 60-70 DEG C, and 2,2- dihydromethyl propionic acid, second is added Oxygroup trimethylolpropane trimethacrylate, polypropylene glycol glycidol ether, acrylic ester cross-linking agent, peroxidating double 2,4- Dichloro-benzoyl is stirred to react 3-4 hours, obtains polyurethane binder prepolymer, by viscosity-adjusting agent to obtain the final product.
2. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the viscoelastic polyurethane The viscosity of mixture is 2600-2800Pas.
3. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the viscoelastic polyurethane The viscosity of mixture is adjusted by Silica hydrogel.
4. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that described adhesive exists The coating weight on artificial leather surface is 60-70g/m2.
5. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the aliphatic poly Ester polyol is adipic acid system polyester-diol.
6. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the polycaprolactone Polyalcohol is polyethylene glycol adipate glycol, polyadipate castor oil ester polyalcohol, polyadipate -1,4- butanediol ester two In alcohol, polyadipate neopentyl glycol -1,6-HD ester diacid, polyadipate ethylene glycol-diglycol ethylene esterdiol at least Two kinds.
7. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the acrylate Class crosslinking agent is diacrylate -1,4-butanediol ester, any one in ethylene glycol dimethacrylate.
8. a kind of preparation method of polyurethane artificial leather adhesive layer as described in claim 1, which is characterized in that the polyurethane people Fabricate-leather material includes the raw material of following parts by weight: 100 parts of polyurethane resin, 35-45 parts of calcium carbonate, dioctyl terephthalate 25- 32 parts, 12-18 parts of phthalic anhydride, 4-6 parts of tetravinyl tetramethyl-ring tetrasiloxane, 1-3 parts of low-molecular-weight hydroxyl silicone oil, 2-6 parts of trifluoro propyl silicone oil, 2-3 parts of foaming agent, 1-2 parts of peroxidating -2- butanone.
9. a kind of preparation method of polyurethane artificial leather adhesive layer as claimed in claim 8, which is characterized in that the polyurethane people Fabricate-leather material is in coating adhesive, after pressing base fabric, dries under conditions of temperature is 95-105 DEG C.
CN201811317472.4A 2018-11-07 2018-11-07 A kind of preparation method of polyurethane artificial leather adhesive layer Pending CN109517565A (en)

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