CN112745795B - Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method - Google Patents

Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method Download PDF

Info

Publication number
CN112745795B
CN112745795B CN202011606099.1A CN202011606099A CN112745795B CN 112745795 B CN112745795 B CN 112745795B CN 202011606099 A CN202011606099 A CN 202011606099A CN 112745795 B CN112745795 B CN 112745795B
Authority
CN
China
Prior art keywords
polyol
electrostatic flocking
parts
flocking adhesive
chain extender
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011606099.1A
Other languages
Chinese (zh)
Other versions
CN112745795A (en
Inventor
唐丽
陈剑冰
荣星
陈龙
孙海娥
于广慧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liaoning Fixed Star Fine Chemical Co ltd
Original Assignee
Liaoning Fixed Star Fine Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liaoning Fixed Star Fine Chemical Co ltd filed Critical Liaoning Fixed Star Fine Chemical Co ltd
Priority to CN202011606099.1A priority Critical patent/CN112745795B/en
Publication of CN112745795A publication Critical patent/CN112745795A/en
Application granted granted Critical
Publication of CN112745795B publication Critical patent/CN112745795B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C08G18/3231—Hydrazine or derivatives thereof
    • 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
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/4009—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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/42—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a waterborne polyurethane electrostatic flocking adhesive for injection molding and a preparation method thereof, and relates to the technical field of textile adhesives, wherein the electrostatic flocking adhesive is prepared from the following raw materials in parts by weight: 50-80 parts of diphenylmethane diisocyanate, 20-50 parts of 1, 6-hexamethyl diisocyanate, 100-150 parts of polyester polyol, 20-50 parts of polyether polyol, 25-40 parts of sulfonate modified diisocyanate, 10-20 parts of polyol chain extender, 5-13.5 parts of polyamine chain extender and 360 parts of water. The preparation method of the waterborne polyurethane electrostatic flocking adhesive for injection molding is simple and convenient, the solid content of the prepared electrostatic flocking adhesive reaches 50%, the electrostatic flocking adhesive is soft in hand feeling, good in fastness, excellent in cold resistance, solvent resistance, hydrolysis resistance and heat and humidity resistance, can be used for injection molding, and is water-based and environment-friendly.

Description

Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method
Technical Field
The invention relates to the technical field of textile adhesives, and particularly relates to a waterborne polyurethane electrostatic flocking adhesive for injection molding and a preparation method thereof.
Background
With the development of society, environmental protection is more and more emphasized by people, and waterborne products have no pollution to the environment and no harm to human bodies, so that the waterborne polyurethane has become a necessary trend to replace solvent type polyurethane.
At present, the flocking adhesive for injection molding in the market is mainly solvent type polyurethane, has good injection molding fastness and is widely used, but the solvent type polyurethane contains a large amount of DMF, toluene and other solvents, harmful substances can be emitted in the production and use processes, the human body can be injured, and the environment can be polluted.
Disclosure of Invention
Therefore, the invention provides an aqueous polyurethane electrostatic flocking adhesive for injection molding and a preparation method thereof, and aims to solve the problems that the existing flocking adhesive for injection molding mainly adopts solvent polyurethane, and harmful substances are released in the production and use processes, so that the human body is harmed, and the environment is polluted.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to the first aspect of the invention, the electrostatic flocking adhesive for the waterborne polyurethane for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000011
Figure BDA0002865941960000021
the invention improves the fastness, the initial adhesion and the solvent resistance by the synergistic action of two active isocyanate groups of diphenylmethane diisocyanate and 1, 6-hexamethyl diisocyanate. The raw material diphenylmethane diisocyanate has a cyclic structure, the cyclic structure is stable in the synthesis process, the structure can still exist after a high polymer is formed, the structure can increase the rigidity of a product, the elasticity is good, the water resistance, the solvent resistance and the wear resistance are enhanced, the fastness and the solvent resistance of the flocking fabric are improved, the 1, 6-hexamethyl diisocyanate is a linear chain structure, the hot melting temperature of the product is reduced, and the initial viscosity is improved.
The polyester structure has the characteristic of good solvent resistance, and particularly polyester, polycaprolactone and polycarbonate with even carbon chains (the number of even carbon atoms is more than 4) have good bonding fastness and hydrolysis resistance and solvent resistance.
The ether bond of the polyether chain segment has low polarity at low temperature, can rotate freely and has good cold resistance.
The preferable proportion of the polyester and the polyether ensures that the cold resistance, the solvent resistance and the fastness of the product can be simultaneously met.
The use of the sulfonate modified diisocyanate can effectively reduce the activation temperature while providing a hydrophilic chain segment, and the hot melting temperature is low, thereby being beneficial to injection molding; in addition, due to the unique characteristic of the sulfonate, strong alkali resistance, strong acid resistance, hydrolysis resistance and aging resistance are ensured.
The water-based polyurethane prepared by the chain extension of the small molecular polyol and the polyamine has higher water resistance, solvent resistance and wear resistance, and is polyurethane-urea emulsion (dispersion liquid) which has higher cohesive force and adhesive force than pure polyurethane, and the water resistance of urea bonds is better than that of urethane bonds, so that the dry and wet fastness can be improved.
Further, the polyester polyol is selected from one or two of 1, 6-hexanediol-adipic acid copolymerized diol, 1, 4-butanediol-adipic acid copolymerized polyol, 1, 4-butanediol-1, 6 hexanediol-adipic acid copolymerized polyol, 1, 4-butanediol-neopentyl glycol-adipic acid copolymerized polyol, 1, 6-hexanediol-neopentyl glycol-adipic acid copolymerized polyol, polycarbonate polyol and polycaprolactone polyol.
Further, the molecular weight of the polyester polyol is 500-3000.
Further, the polyether polyol is one or two selected from polyethylene oxide polyol, polypropylene oxide polyol, polytetrahydrofuran polyol, polybutylene oxide polyol, ethylene oxide-propylene oxide copolyol, ethylene oxide-tetrahydrofuran copolyol and polybutadiene polyol.
Further, the polyether polyol has a molecular weight of 500-4000.
Further, the sulfonate modified diisocyanate is selected from chemical products of Beijing Baiyuan.
Further, the polyol chain extender is one or two selected from 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, sorbitol and 1, 4-dimethylolcyclohexane.
Further, the polyamine chain extender is one or two selected from ethylenediamine, diethylenetriamine, triethylene tetramine, hydrazine hydrate and isophorone diamine.
Further, the chemical indexes of the electrostatic flocking adhesive are as follows:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 8 plus or minus 1;
solid content: 50 +/-2 percent.
According to a second aspect of the present invention, the preparation method of the electrostatic flocking glue comprises the following steps:
s1, prepolymerization reaction: adding diphenylmethane diisocyanate, 1, 6-hexamethyl diisocyanate, polyester polyol and polyether polyol into a reaction kettle, heating to 85 +/-2 ℃ for reaction for 1.5-2 hours, then adding sulfonate modified diisocyanate WTDI, and reacting at 90 +/-2 ℃ for 3-4 hours to obtain a prepolymer;
s2, chain extension reaction: adding a polyol chain extender into the prepolymer, reacting for 1-3 hours at 50-80 ℃, and cooling to 40 +/-5 ℃;
s3, dispersion and emulsification reaction: water is added in the mixture after high-speed dispersion and stirring, and the dispersion and emulsification reaction is carried out for 0.5 to 1 hour;
s4, chain extension reaction: and adding polyamine chain extender to react for 2-3 hours at 30-60 ℃, and cooling to below 35 ℃ to obtain the electrostatic flocking adhesive.
The invention has the following advantages:
the preparation method of the waterborne polyurethane electrostatic flocking adhesive for injection molding is simple and convenient, the solid content of the prepared electrostatic flocking adhesive reaches 50%, the electrostatic flocking adhesive is soft in hand feeling, good in fastness, excellent in cold resistance, solvent resistance, hydrolysis resistance and heat and humidity resistance, can be used for injection molding, and is water-based and environment-friendly.
Detailed Description
The present invention is described in terms of specific embodiments, and other advantages and benefits of the present invention will become apparent to those skilled in the art from the following disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The aqueous polyurethane electrostatic flocking adhesive for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000041
the polyester polyol is selected from 1, 4-butanediol-adipic acid copolymerized polyol, and the molecular weight is 500-3000.
The polyether polyol is selected from polypropylene oxide polyol with the molecular weight of 500-4000.
The sulfonate modified diisocyanate is selected from the chemical products of Beijing Baiyuan.
The polyol chain extender comprises 10 parts of 1, 4-butanediol and 10 parts of 1, 6 hexanediol.
The polyamine chain extender is ethylenediamine.
The preparation method of the electrostatic flocking adhesive comprises the following steps:
s1, prepolymerization reaction: adding diphenylmethane diisocyanate, 1, 6-hexamethyl diisocyanate, polyester polyol and polyether polyol into a reaction kettle, heating to 85 +/-2 ℃ for reaction for 1.5-2 hours, then adding sulfonate modified diisocyanate WTDI, and reacting at 90 +/-2 ℃ for 3-4 hours to obtain a prepolymer;
s2, chain extension reaction: adding a polyol chain extender into the prepolymer, reacting for 1-3 hours at 50-80 ℃, and cooling to 40 +/-5 ℃;
s3, dispersion and emulsification reaction: water is added in the mixture after high-speed dispersion and stirring, and the dispersion and emulsification reaction is carried out for 0.5 to 1 hour;
s4, chain extension reaction: and adding a polyamine chain extender to react for 2-3 hours at the temperature of 30-60 ℃, and cooling to below 35 ℃ to obtain the electrostatic flocking adhesive.
The chemical indexes of the electrostatic flocking adhesive are as follows:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 7.8 of;
solid content: 51.1 percent.
Example 2
The aqueous polyurethane electrostatic flocking adhesive for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000051
the polyester polyol is selected from 1, 6-hexanediol-adipic acid copolymerized polyol, and the molecular weight is 500-3000.
The polyether polyol is selected from polypropylene oxide polyol with the molecular weight of 500-4000.
The sulfonate modified diisocyanate is selected from chemical products of Beijing Baiyuan.
The polyol chain extender is 1, 4 butanediol.
The polyamine chain extender is hydrazine hydrate.
The preparation method of the electrostatic flocking adhesive is the same as that of the embodiment 1.
The obtained electrostatic flocking adhesive has the following chemical indexes:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 7.9;
solid content: 49.5 percent.
Example 3
The aqueous polyurethane electrostatic flocking adhesive for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000061
the polyester polyol comprises 100 parts of 1, 4-butanediol-adipic acid copolymer polyol and 30 parts of polycaprolactone polyol, and the molecular weight is 500-3000.
The polyether polyol is selected from polytetrahydrofuran polyol with the molecular weight of 500-4000.
The sulfonate modified diisocyanate is selected from chemical products of Beijing Baiyuan.
The polyol chain extender includes 9 parts 1, 4 butanediol and 5.2 parts neopentyl glycol.
The polyamine chain extender is diethylenetriamine.
The preparation method of the electrostatic flocking adhesive is the same as that of the embodiment 1.
The obtained electrostatic flocking adhesive has the following chemical indexes:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 8.5;
solid content: 50.1 percent.
Example 4
The aqueous polyurethane electrostatic flocking adhesive for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000062
Figure BDA0002865941960000071
the polyester polyol is selected from 1, 6-hexanediol-neopentyl glycol-adipic acid copolymerized polyol, and the molecular weight is 500-3000.
The polyether polyol is selected from ethylene oxide-tetrahydrofuran copolyol, and the molecular weight is 500-4000.
The sulfonate modified diisocyanate is selected from chemical products of Beijing Baiyuan.
The polyol chain extender is selected from trimethylolpropane 3 and 1, 6-hexanediol.
The polyamine chain extender comprises 2.3 parts of ethylenediamine and 5.6 parts of isophorone diamine.
The preparation method of the electrostatic flocking adhesive is the same as that of the embodiment 1.
The obtained electrostatic flocking adhesive has the following chemical indexes:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 8.2;
solid content: 50.1 percent.
Example 5
The aqueous polyurethane electrostatic flocking adhesive for injection molding is prepared from the following raw materials in parts by weight:
Figure BDA0002865941960000072
Figure BDA0002865941960000081
the polyester polyol comprises 100 parts of 1, 6-hexanediol-adipic acid copolymerized polyol and 20 parts of polycarbonate polyol, and the molecular weight is 500-3000.
The polyether polyol is selected from polybutadiene polyols, and the molecular weight is 500-4000.
The sulfonate modified diisocyanate is selected from chemical products of Beijing Baiyuan.
The polyol chain extender comprises 10 parts of diethylene glycol and 10 parts of 1, 6-hexanediol.
The polyamine chain extender comprises 3.5 parts of hydrazine hydrate and 10 parts of triethylene tetramine.
The preparation method of the electrostatic flocking adhesive is the same as that of the embodiment 1.
The obtained electrostatic flocking adhesive has the following chemical indexes:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 8.4 of the total weight of the mixture;
solid content: 50.5 percent.
Examples of the experiments
The electrostatic flocking adhesive obtained in the embodiments 1-5 of the invention and similar products at home and abroad are respectively flocked on synthetic leather, the performance of the flocked synthetic leather is tested, the performance comparison result is shown in table 1, and the specific flocking process comprises the following steps: the electrostatic flocking glue obtained in the examples 1-5 and similar products at home and abroad are respectively thickened by a thickener FS-300H of Liaoning sidereal fine chemical engineering Co., Ltd till the viscosity reaches 2000 +/-100 centipoises (25 ℃), a cross-linking agent DF-810 of Liaoning sidereal fine chemical engineering Co., Ltd is added, then flocking (full planting) is carried out on synthetic leather, and drying is carried out for 2 minutes at the temperature of 150-.
In addition, the electrostatic flocking adhesives obtained in examples 1 to 5 of the invention were tested for hydrolysis resistance and peel strength in injection molding. The result shows that the electrostatic flocking adhesive has good hydrolysis resistance, and the injection peel strength reaches more than 100N.
Table 1 table of experimental results comparing the electrostatic flocking adhesives of examples 1-5 of the present invention with similar products at home and abroad
Figure BDA0002865941960000082
Figure BDA0002865941960000091
Note that the cold resistance test is the test result at 15 ℃ below zero
1. And (3) cold resistance detection: measuring the low temperature resistance of the FZ/T01007-2008 coated fabric; HS-6056 vertical cold-resistance tester.
2. And (3) coating thickness detection: GB/1764-79(89) paint film thickness determination; JR-706 coating thickness tester.
3. And (3) detecting washing fastness: GB/T8629-2001 textile test uses a domestic washing and drying procedure; a swan XPB55-518S washing machine.
4. And (3) detecting the wear resistance: a method for measuring the wear resistance of coated fabrics; fabric plain grinding machine FZ/T01011-91.
5. And (3) detecting the injection molding peel strength: GB/T2791-1995 adhesive T peeling strength test method for flexible material to flexible material
6. And (3) detecting the damp-heat aging: FZ/T75007-1995 coating fabric hot and humid air accelerated aging test method
7. And (3) hydrolysis resistance detection: the flocking fabric is soaked in 10% sodium hydroxide water solution for 24 hours at normal temperature, and the dried fabric surface is kept complete after cleaning.
The test results show that compared with similar products, the electrostatic flocking adhesive has the advantages of good flocking density, uniformity and density, and no phenomena of silk path and silk thread; the polyester fiber has the advantages of soft hand feeling, excellent fastness, cold resistance which can meet the high requirement of 2 ten thousand times, good solvent resistance, hydrolysis resistance, wet and heat aging resistance and obviously better performance than other products; in addition, the injection peel strength of the electrostatic flocking adhesive reaches more than 100N, and the injection molding performance is excellent.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The aqueous polyurethane electrostatic flocking adhesive for injection molding is characterized by being prepared from the following raw materials in parts by weight:
50-80 parts of diphenylmethane diisocyanate
20-50 parts of 1, 6-hexamethylene diisocyanate
100-150 parts of polyester polyol
20-50 parts of polyether polyol
25-40 parts of sulfonate modified diisocyanate
10-20 parts of polyol chain extender
Polyamine chain extender 5-13.5 parts
280 portions of water and 360 portions.
2. The electrostatic flocking paste as claimed in claim 1, wherein said polyester polyol is selected from one or two of 1, 6-hexanediol-adipic acid copolyol, 1, 4-butanediol-1, 6-hexanediol-adipic acid copolyol, 1, 4-butanediol-neopentyl glycol-adipic acid copolyol, 1, 6-hexanediol-neopentyl glycol-adipic acid copolyol, polycarbonate polyol, and polycaprolactone polyol.
3. The electrostatic flocking adhesive as recited in claim 1 wherein the polyester polyol has a molecular weight of 500-3000.
4. The electrostatic flocking paste of claim 1 wherein said polyether polyol is selected from one or two of polyethylene oxide polyol, polypropylene oxide polyol, polytetrahydrofuran polyol, polybutylene oxide polyol, ethylene oxide-propylene oxide copolyol, and ethylene oxide-tetrahydrofuran copolyol.
5. The electrostatic flocking adhesive as defined in claim 1, wherein the polyether polyol has a molecular weight of 500-4000.
6. The electrostatic flocking adhesive of claim 1 wherein said sulfonate modified diisocyanate is selected from the group consisting of chemical products of beijing baiyuan.
7. An electrostatic flocking paste according to claim 1 wherein said polyol chain extender is selected from one or two of 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, sorbitol, 1, 4-dimethylolcyclohexane.
8. An electrostatic flocking adhesive according to claim 1 wherein said polyamine chain extender is selected from one or two of ethylenediamine, diethylenetriamine, triethylenetetramine, hydrazine hydrate, isophoronediamine.
9. An electrostatic flocking paste according to claim 1 wherein said paste has the following chemical specifications:
appearance: a white blue light emulsion;
ionic property: negative;
pH value: 8 plus or minus 1;
solid content: 50 +/-2%.
10. A process for the preparation of an electrostatic flocking glue as claimed in any one of claims 1 to 9, wherein the process comprises the following steps:
s1, prepolymerization reaction: adding diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, polyester polyol and polyether polyol into a reaction kettle, heating to 85 +/-2 ℃ for reacting for 1.5-2 hours, then adding sulfonate modified diisocyanate (WTDI) for reacting for 3-4 hours at 90 +/-2 ℃ to obtain a prepolymer;
s2, chain extension reaction: adding a polyol chain extender into the prepolymer, reacting at 50-80 ℃ for 1-3 hours, and cooling to 40 +/-5 ℃;
s3, dispersion and emulsification reaction: water is added in the mixture after high-speed dispersion and stirring, and the dispersion and emulsification reaction is carried out for 0.5 to 1 hour;
s4, chain extension reaction: and adding a polyamine chain extender to react for 2-3 hours at the temperature of 30-60 ℃, and cooling to below 35 ℃ to obtain the electrostatic flocking adhesive.
CN202011606099.1A 2020-12-28 2020-12-28 Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method Active CN112745795B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011606099.1A CN112745795B (en) 2020-12-28 2020-12-28 Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011606099.1A CN112745795B (en) 2020-12-28 2020-12-28 Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method

Publications (2)

Publication Number Publication Date
CN112745795A CN112745795A (en) 2021-05-04
CN112745795B true CN112745795B (en) 2022-07-15

Family

ID=75647741

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011606099.1A Active CN112745795B (en) 2020-12-28 2020-12-28 Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method

Country Status (1)

Country Link
CN (1) CN112745795B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115584235B (en) * 2022-10-24 2023-08-08 东莞聚力创新材料科技有限公司 PUR adhesive for clothing fabric and preparation method thereof
CN117818321A (en) * 2023-12-24 2024-04-05 太仓恩力成密封件有限公司 Automobile glass guide groove sealing strip flocking belt and production process thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101012362A (en) * 2007-01-29 2007-08-08 上海九元石油化工有限公司 Method of preparing polyurethane flocking rubber for automobile sealing strip
CN106753160A (en) * 2016-11-29 2017-05-31 上海华峰材料科技研究院（有限合伙） Aqueous polyurethane Flock Adhesive and preparation method thereof
CN111423343A (en) * 2020-03-20 2020-07-17 佛山市精信汇明科技有限公司 Hydrophilic diisocyanate and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10055559A1 (en) * 2000-11-09 2002-05-29 Henkel Kgaa UV-resistant flocking adhesive for polymer substrates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101012362A (en) * 2007-01-29 2007-08-08 上海九元石油化工有限公司 Method of preparing polyurethane flocking rubber for automobile sealing strip
CN106753160A (en) * 2016-11-29 2017-05-31 上海华峰材料科技研究院（有限合伙） Aqueous polyurethane Flock Adhesive and preparation method thereof
CN111423343A (en) * 2020-03-20 2020-07-17 佛山市精信汇明科技有限公司 Hydrophilic diisocyanate and preparation method and application thereof

Also Published As

Publication number Publication date
CN112745795A (en) 2021-05-04

Similar Documents

Publication Publication Date Title
CN100480349C (en) Method for preparing modified aqueous adhesion agent of polyurethane
CN107922562B (en) Moisture-curable hot-melt polyurethane composition, method for producing foamed cured product thereof, synthetic leather and method for producing the same
US6485837B2 (en) Coating composition for polyolefin products and polyolefin products coated with such coating composition
KR100389934B1 (en) Aqueous dry laminate adhesive composition for synthetic leather and manufacturing method for synthetic leather using the same
CN101831048A (en) High-gloss polyurethane resins and application thereof
CN101824755A (en) Artificial leather
KR20160027079A (en) Urethane resin composition, leather-like sheet, and method for manufacturing leather-like sheet
CN112745795B (en) Waterborne polyurethane electrostatic flocking adhesive for injection molding and preparation method
CN102618204A (en) Hot-melt adhesive for bonding layer of artificial leather and preparation method as well as application thereof
CN109160994B (en) A kind of waterborne polyurethane dispersion for dry coating primer and its preparation method and use
CN103805122A (en) Waterborne polyurethane patch adhesive and preparation method thereof
CN105131565A (en) A kind of thermoplastic polyurethane with high color fastness, thermoplastic polyurethane synthetic leather and preparation method thereof
TW202003614A (en) Polyurethane prepolymer, adhesive and synthetic imitation leather
CN113372530A (en) Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base
CN112673130B (en) Synthetic leather
KR20200037340A (en) Manufacturing method of synthetic leather
CN113307928B (en) Polyurethane resin and preparation method and application thereof
CN110922563A (en) Waterborne polyurethane adhesive cement emulsion for swimsuit printing and preparation method thereof
CN113840871A (en) Urethane resin composition and laminate
KR100263375B1 (en) Manufacturing method of synthetic leather using waterborne polyurethane resin
CN110684173B (en) Super-soft hydrolysis-resistant wet polyurethane resin and preparation method thereof
CN119119416A (en) A kind of heat aging resistant polyurethane resin and its preparation method and application
CN112745473A (en) High-water-pressure washing-resistant polyurethane primer resin for textile coating and preparation method thereof
CN112961307B (en) Solvent-free polyurethane resin, impregnation slurry, and preparation method and application thereof
CN110685159A (en) Production method of water-based microfiber synthetic leather

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant