US20220081588A1 - Waterborne polyurethane dispersion and method for preparing the same - Google Patents

Waterborne polyurethane dispersion and method for preparing the same Download PDF

Info

Publication number
US20220081588A1
US20220081588A1 US17/419,635 US201917419635A US2022081588A1 US 20220081588 A1 US20220081588 A1 US 20220081588A1 US 201917419635 A US201917419635 A US 201917419635A US 2022081588 A1 US2022081588 A1 US 2022081588A1
Authority
US
United States
Prior art keywords
isocyanate
groups
polyurethane dispersion
waterborne polyurethane
catalyst
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.)
Abandoned
Application number
US17/419,635
Other languages
English (en)
Inventor
Xiaolian Hu
Chao Zhang
Xiangyang Tai
Yanli Feng
Lili Shi
Jiawen Xiong
Biao Ma
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.)
Dow Global Technologies LLC
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Dow Silicones Corp
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 Dow Global Technologies LLC, Dow Silicones Corp filed Critical Dow Global Technologies LLC
Publication of US20220081588A1 publication Critical patent/US20220081588A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • 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
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/0238—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0246—Acrylic resin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • B32B2262/065—Lignocellulosic fibres, e.g. jute, sisal, hemp, flax, bamboo
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2437/00—Clothing
    • 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
    • B32B2437/00—Clothing
    • B32B2437/02—Gloves, shoes
    • 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
    • B32B2601/00—Upholstery
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/10—Properties of the materials having mechanical properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/14—Furniture, upholstery
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24438—Artificial wood or leather grain surface

Definitions

  • the present disclosure relates to a waterborne polyurethane dispersion and a method for preparing the same, a laminated synthetic leather article comprising a skin film derived from the waterborne polyurethane dispersion and a method for preparing the same.
  • the laminated synthetic leather article prepared by said waterborne polyurethane dispersion exhibits superior anti-stickiness and mechanical properties.
  • Synthetic leather gets popular applications in people's daily life, from clothes, footwear, bag and luggage, home upholstery to seats in automobile. It provides similar performance and hand feeling to natural leather with much better cost advantage.
  • Synthetic leather is fabricated by coating polymer(s) on a fabric substrate or impregnating polymer(s) into a fabric substrate, and the most commonly used polymer is polyurethane. Traditional processes are performed with the solution of polyurethane resin(s) in volatile organic solvents such as dimethylformamide (DMF), methylethyl ketone (MEK) and toluene.
  • DMF dimethylformamide
  • MEK methylethyl ketone
  • Porous structure of PU is created by precipitating PU polymer chain in a controlled manner through leading the coated or impregnated fabric substrate into water bath.
  • Waterborne polyurethane dispersion is a green alternative to PU solution in the volatile organic solvents such as DMF.
  • PUD Waterborne polyurethane dispersion
  • polyester polyol based PUD's have many problems, e.g. poor hydrolysis resistance, high cost and low dispersity in water due to high viscosity of polyester prepolymer).
  • Polyether polyol based PUD's don't have such problems, but the mechanical properties and anti-stickiness performance are poor due to the intrinsic softness of polyether polyol.
  • a newly developed technology for producing a synthetic leather is to laminate a externally emulsified skin layer derived from a polyurethane dispersion with a non-solvent 2k PU foam layer, but the skin layer of the laminated synthetic leather exhibits unfavorable anti-stickiness performance which cannot meet the requirements of the synthetic leather application as any slight stickiness in the skin film would not be acceptable to the customer.
  • siloxane compound with both hydrophilic group and amine group can be used in the preparation of said PUD and impart the resultant synthetic leather article with significantly improved anti-stickiness performance while maintaining good PUD film mechanical properties like tensile strength, elongation and modulus.
  • the present disclosure provides a unique waterborne polyurethane dispersion and a laminated synthetic leather article prepared by using the same.
  • the present disclosure provides a waterborne polyurethane dispersion comprising polyurethane particles dispersed in water, wherein the waterborne polyurethane dispersion is derived from:
  • an isocyanate component comprising one or more compounds having at least two isocyanate groups
  • an isocyanate-reactive component comprising one or more compounds having at least two isocyanate-reactive groups
  • each R independently represents methyl, ethyl, n-propyl, i-propyl, n-butyl, butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, tert-pentyl, neo-pentyl, cyclohexyl, phenyl, vinyl, allyl or —(OCH 2 CH 2 ) a —O—CH 2 —CH ⁇ CH 2 ;
  • R 1 is —(CH 2 ) m NH 2 or —(CH 2 ) s —NH—(CH 2 ) t NH 2 ;
  • R 2 is —CH 2 CH 2 CH 2 O(CH 2 CH 2 O) n H
  • each of R 3 , R 4 , R 5 , R 6 and R 7 is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, tert-pentyl, neo-pentyl, cyclohexyl and phenyl;
  • n is an integer of 5-20;
  • the waterborne polyurethane dispersion is an externally emulsified polyurethane that does not comprise cationic or anionic hydrophilic pendant group or a group which can be converted into the cationic or anionic hydrophilic pendant group covalently attached to the backbone chain of the polyurethane.
  • the present disclosure provides a method for producing the waterborne polyurethane dispersion of the first aspect, comprising (i) reacting the isocyanate component (A) with the isocyanate-reactive component (B) in the presence of the catalyst (D) to form a prepolymer comprising free isocyanate groups; and (ii) reacting the prepolymer with the hydrophilic amino siloxane compound (C) and the chain extender (F) in the presence of the surfactant (E) and water (G) to form the waterborne polyurethane dispersion.
  • the present disclosure provides a synthetic leather article, comprising, from top to bottom:
  • the present disclosure provides a method for preparing the synthetic leather article of the third aspect, comprising:
  • FIG. 1 is a schematic illustration of a cross-section of one embodiment of a synthetic leather article described herein.
  • composition refers to a physical blend of different components, which is obtained by mixing simply different components by a physical means.
  • the isocyanate component (A) has an average functionality of at least about 2.0, preferably from about 2 to 10, more preferably from about 2 to about 8, and most preferably from about 2 to about 6.
  • the isocyanate component includes a polyisocyanate compound comprising at least two isocyanate groups. Suitable polyisocyanate compounds include aromatic, aliphatic, cycloaliphatic and araliphatic polyisocyanates having two or more isocyanate groups.
  • the polyisocyanate component comprises polyisocyanate compounds selected from the group consisting of C 4 -C 12 aliphatic polyisocyanates comprising at least two isocyanate groups, C 6 -C 15 cycloaliphatic or aromatic polyisocyanates comprising at least two isocyanate groups, C 7 -C 15 araliphatic polyisocyanates comprising at least two isocyanate groups, and combinations thereof.
  • suitable polyisocyanate compounds include m-phenylene diisocyanate, 2,4-toluene diisocyanate and/or 2,6-toluene diisocyanate (TDI), the various isomers of diphenylmethanediisocyanate (MDI), carbodiimide modified MDI products, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, hydrogenated MDI, naphthylene-1,5-diisocyanate, isophorone diisocyanate (IPDI), or mixtures thereof.
  • MDI diphenylmethanediisocyanate
  • MDI diphenylmethanediisocyanate
  • carbodiimide modified MDI products hexamethylene-1,6-diisocyanate
  • the polyisocyanate component may also comprise a isocyanate prepolymer having an isocyanate functionality in the range of 2 to 10, preferably from 2 to 8, more preferably from 2 to 6.
  • the isocyanate prepolymer can be obtained by reacting the above stated monomeric isocyanate components with one or more isocyanate-reactive compounds selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl-glycol, bis(hydroxy-methyl) cyclohexanes such as 1,4-bis(hydroxymethyl)cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol
  • Suitable prepolymers for use as the polyisocyanate component are prepolymers having NCO group contents of from 2 to 40 weight percent, more preferably from 4 to 30 weight percent. These prepolymers are preferably prepared by reaction of the di- and/or poly-isocyanates with materials including lower molecular weight diols and triols.
  • aromatic polyisocyanates containing urethane groups preferably having NCO contents of from 5 to 40 weight percent, more preferably 20 to 35 weight percent, obtained by reaction of diisocyanates and/or polyisocyanates with, for example, lower molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols, or polyoxyalkylene glycols having molecular weights up to about 800.
  • diols preferably having NCO contents of from 5 to 40 weight percent, more preferably 20 to 35 weight percent
  • diisocyanates and/or polyisocyanates with, for example, lower molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols, or polyoxyalkylene glycols having molecular weights up to about 800.
  • These polyols can be employed individually or in mixtures as di- and/or polyoxyalkylene glycols.
  • diethylene glycols, dipropylene glycols, polyoxyethylene glycols, ethylene glycols, propylene glycols, butylene glycols, polyoxypropylene glycols and polyoxypropylene-polyoxyethylene glycols can be used.
  • Polyester polyols can also be used, as well as alkane diols such as butane diol.
  • Other diols also useful include bishydroxyethyl- or bishydroxypropyl-bisphenol A, cyclohexane dimethanol, and bishydroxyethyl hydroquinone.
  • isocyanate component is advantageously used for the isocyanate component.
  • modified multifunctional isocyanates that is, products which are obtained through chemical reactions of the above isocyanates compounds.
  • exemplary are polyisocyanates containing esters, ureas, biurets, allophanates and preferably carbodiimides and/or uretoneimines.
  • NCO isocyanate groups
  • the amount of the isocyanate component may vary based on the actual requirement of the synthetic leather article.
  • the content of the isocyanate component can be from about 5 wt % to about 50 wt %, preferably from about 10 wt % to about 40 wt %, preferably from about 15 wt % to about 30 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D).
  • the isocyanate-reactive component comprises one or more polyols selected from the group consisting of aliphatic polyhydric alcohols comprising at least two hydroxy groups, cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, araliphatic polyhydric alcohols comprising at least two hydroxy groups, polyether polyol, polyester polyol, vegetable oil having at least two hydroxyl groups and mixture thereof.
  • the polyol is selected from the group consisting of C2-C16 aliphatic polyhydric alcohols comprising at least two hydroxy groups, C6-C15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxy groups, C7-C15 araliphatic polyhydric alcohols comprising at least two hydroxy groups, polyester polyols having a molecular weight from 100 to 5,000, polyether polyols having a molecular weight from 1,500 to 12,000, and combinations thereof.
  • the polyol comprises a polyether polyols (e.g., a polyether polyols as stated above), a castor oil, or a mixture thereof.
  • the isocyanate-reactive component comprises a mixture of two or more different polyols, such as a mixture of two or more polyether polyols, a mixture of two or more polyester polyols, a mixture of at least one polyether polyols with at least one polyester polyols, a mixture of two or more vegetable oils having at least two hydroxyl groups, or a mixture of a polyether polyols and a castor oil.
  • the isocyanate-reactive component is a polyether polyols having a functionality (average number of isocyanate-reactive groups, particularly, hydroxyl group, in a polyol molecule) of 1.0 to 3.0 and a weight average molecular weight (Mw) of 1,500 to 12,000 g/mol, preferably from 2,000 to 8,000 g/mol, more preferably from 2,000 to 6,000 g/mol.
  • a functionality average number of isocyanate-reactive groups, particularly, hydroxyl group, in a polyol molecule
  • Mw weight average molecular weight
  • the polyether polyols is generally prepared by polymerization of one or more alkylene oxides selected from propylene oxide (PO), ethylene oxide (EO), butylene oxide, tetrahydrofuran and mixtures thereof, with proper starter molecules in the presence of catalyst.
  • Typical starter molecules include compounds having at least 2, preferably from 4 to 8 hydroxyl groups or having two or more primary amine groups in the molecule.
  • Suitable starter molecules are for example selected from the group comprising aniline, EDA, TDA, MDA and PMDA, more preferably from the group comprising TDA and PMDA, an most preferably TDA. When TDA is used, all isomers can be used alone or in any desired mixtures.
  • 2,4-TDA, 2,6-TDA, mixtures of 2,4-TDA and 2,6-TDA, 2,3-TDA, 3,4-TDA, mixtures of 3,4-TDA and 2,3-TDA, and also mixtures of all the above isomers can be used.
  • starter molecules having at least 2 and preferably from 2 to 8 hydroxyl groups in the molecule it is preferable to use trimethylolpropane, glycerol, pentaerythritol, castor oil, sugar compounds such as, for example, glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines, and also melamine.
  • trimethylolpropane glycerol, pentaerythritol, castor oil
  • sugar compounds such as, for example, glucose, sorbitol, mannitol and sucrose
  • polyhydric phenols such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines, and also melamine.
  • Catalyst for the preparation of polyether polyols may include alkaline catalysts, such as potassium hydroxide, for anionic polymerization or Lewis acid catalysts, such as boron trifluoride, for cationic polymerization.
  • Suitable polymerization catalysts may include potassium hydroxide, cesium hydroxide, boron trifluoride, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate or quaternary phosphazenium compound.
  • DMC double cyanide complex
  • the polyether polyol includes (methoxy) polyethylene glycol (MPEG), polyethylene glycol (PEG), poly(propylene glycol) or copolymer of ethylene epoxide and propylene epoxide with primary hydroxyl ended group and secondary hydroxyl ended group.
  • MPEG polyethylene glycol
  • PEG polyethylene glycol
  • PEG poly(propylene glycol) or copolymer of ethylene epoxide and propylene epoxide with primary hydroxyl ended group and secondary hydroxyl ended group.
  • the content of the isocyanate-reactive component used herein may range from about 50 wt % to about 95 wt %, preferably from about 60 wt % to about 85 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D).
  • Catalyst may include any substance that can promote the reaction between the isocyanate group and the isocyanate-reactive group.
  • the catalysts can include, for example, glycine salts; tertiary amines; tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; morpholine derivatives; piperazine derivatives; chelates of various metals, such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate and the like with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; acidic metal salts of strong acids such as ferric chloride and stannic chloride; salts of organic acids with variety of metals, such as alkali metals, alkaline earth metals
  • Tertiary amine catalysts include organic compounds that contain at least one tertiary nitrogen atom and are capable of catalyzing the hydroxyl/isocyanate reaction.
  • the tertiary amine, morpholine derivative and piperazine derivative catalysts can include, by way of example and not limitation, triethylenediamine, tetramethylethylenediamine, pentamethyl-diethylene triamine, bis(2-dimethylaminoethyl)ether, triethylamine, tripropylamine, tributyl-amine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine, N-ethylmorpholine, 2-methylpropanediamine, methyltriethylenediamine, 2,4,6-tridimethylamino-methyl)phenol, N,N′,N′′-tris(dimethyl amino-propyl)sym-hexahydro triazine, or mixtures thereof.
  • the content of the catalyst used herein is larger than zero and is at most 1.0 wt %, preferably at most 0.5 wt %, more preferably at most 0.05 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D).
  • the hydrophilic amino siloxane compound is a compound comprising a silicon-oxygen back bone chain to which nitrogen-containing side chain and hydrophilic side chain are attached.
  • the molecular structure of the hydrophilic amino siloxane compound may be represented by Formula I:
  • each R independently represents methyl, ethyl, n-propyl, i-propyl, n-butyl, butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, tert-pentyl, neo-pentyl, cyclohexyl, phenyl, vinyl, allyl or —(OCH 2 CH 2 ) a —O—CH 2 —CH ⁇ CH 2 ;
  • R 1 is —(CH 2 ) m NH 2 or —(CH 2 ) s —NH—(CH 2 ) t NH 2 ;
  • R 2 is —CH 2 CH 2 CH 2 O(CH 2 CH 2 O) n H
  • each of R 3 , R 4 , R 5 , R 6 and R 7 is independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, tert-pentyl, neo-pentyl, cyclohexyl and phenyl;
  • the amine group in R 1 and the hydroxyl group in R 2 may react with the remaining isocyanate group in the prepolymer to produce a polyurethane comprising the above siloxane structure in the polyurethane back bone chain, thus significantly improve the anti-stickiness of the resultant PU skin film.
  • the hydrophilic amino siloxane compound has a structure presented by Formula II:
  • R, R 1 , R 2 , x, y and z are as described above.
  • the content of the hydrophilic amino siloxane compound used herein is from 2 wt % to 10 wt %, preferably from 2 wt % to 8 wt %, more preferably from 2 wt % to 5 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D). It can be seen that the content of the hydrophilic amino siloxane compound is calculated as an additional amount while taking the total amount of the prepolymer as 100 wt %.
  • hydrophilic amino siloxane compound should be firstly dissolved/dispersed in water via mixing to get an aqueous solution and then degassed.
  • the amino silicone oil was added during the dispersion stage and was not added into polymer backbone during the prepolymer synthesis. The reason is that some degree of polymer gel will be formed if the siloxane was added during the prepolymer synthesis stage.
  • the waterborne polyurethane dispersion is an externally emulsified dispersion, i.e., the waterborne polyurethane dispersion is preferably prepared exclusively by using “external surfactant/emulsifier” and substantially comprises no “internal surfactant/emulsifier”.
  • externally emulsified polyurethane dispersion refers to a polyurethane dispersion comprising limited amount of internally emulsifying ionic components and thus mainly relying on the emulsifying function of “external surfactant/emulsifier” [i.e. ionically or nonionically emulsifiers that are not covalently bonded to the backbone chain within the polyurethane particles dispersed in the liquid medium, especially via the urethane bond derived from the reaction between an isocyanate group and an isocyanate-reactive group (such as a hydroxyl group)] so as to stabilize the polyurethane dispersion.
  • external surfactant/emulsifier i.e. ionically or nonionically emulsifiers that are not covalently bonded to the backbone chain within the polyurethane particles dispersed in the liquid medium, especially via the urethane bond derived from the reaction between an isocyanate group
  • the externally emulsified polyurethane dispersion is prepared by (i) reacting one or more monomeric or prepolymeric polyisocyanates with one or more compounds having at least two isocyanate-reactive groups as stated above to form a prepolymer comprising an urethane prepolymer chain and at least one, preferably at least two free isocyanate groups per molecule; (ii) dispersing the prepolymer obtained in step (i) in an aqueous solvent (e.g.
  • the prepolymer prepared in the step (i) does not comprise any ionic internal emulsifier or residual moieties of the ionic internal emulsifier covalently bonded to the urethane prepolymer chain.
  • the polyurethane chain in the prepolymer prepared in the step (i) does not comprise any cationic or anionic pendant group.
  • a typical process for preparing an internally emulsified PUD comprises the steps of (i) reacting an monomeric isocyanate or a prepolymer of the monomeric isocyanate with polyols and cationic or anionic precursor which has at least one isocyanate-reactive groups (i.e., an ionic internal emulsifier) to form a PUD prepolymer comprising pendant cationic or anionic hydrophilic groups attached to the PU chain; (ii) dispersing the PUD prepolymer into an aqueous solvent (e.g.
  • the polyurethane particles prepared by the present application comprise residual groups of the chain extenders and the hydrophilic amino siloxane compound attached to the polyurethane main chain, but these residual groups are different from the above stated ionic internal emulsification function groups at least in the charge neutrality and hence shall be excluded from the definition of the ionic internal emulsifying function groups.
  • the emulsifying of the polyurethane is conducted mainly or solely by using the external emulsifier, and the chain extender and hydrophilic amino siloxane compound are not added until an emulsion of PU has been formed. That is why the PU dispersion of the present disclosure is identified as an externally emulsified system.
  • the above stated ionic internal emulsifying component is not added during the preparation of the externally emulsified PUD.
  • the externally emulsified polyurethane dispersion is free of anionic or cationic salt group in the backbone chain of the polyurethane prepolymer particles dispersed in the externally emulsified PUD.
  • the waterborne polyurethane dispersion of the present disclosure may be prepared by using any anionic surfactant, cationic surfactant, amphoteric surfactant or non-ionic surfactant.
  • Suitable classes of surfactant include, but are not restricted to, sulfates of ethoxylated phenols such as poly(oxy-1,2-ethanediyl) ⁇ -sulfo- ⁇ (nonylphenoxy) salt; alkali metal fatty acid salts such as alkali metal oleates and stearates; alkali metal C 12 -C 16 alkyl sulfates such as alkali metal lauryl sulfates; amine C 12 -C 16 alkyl sulfates such as amine lauryl sulfates, more preferably triethanolamine lauryl sulfate; alkali metal C 12 -C 16 alkylbenzene sulfonates such as branched and linear sodium dodecylbenz
  • the surfactant is one that can react with a multivalent cation present in a neutral salt to form an insoluble multivalent cation water insoluble salt of an organic acid.
  • exemplary preferred surfactant includes disodium octadecyl sulfosuccinate, sodium dodecylbenzene sulfonate, sodium stearate and ammonium stearate.
  • the content of the surfactant is larger than zero and no more than 10 wt %, preferably no more than 5 wt %, more preferably no more than 3.5 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D). It can be seen that the content of the surfactant is calculated as an additional amount while taking the total amount of the prepolymer as 100 wt %.
  • the chain extender may be a diamine or an amine compound having another isocyanate reactive group, but is preferably selected from the group consisting of: an aminated polyether diol; piperazine; aminoethylethanolamine; C 2 -C 16 aliphatic polyamine comprising at least two amine groups, e.g., ethylenediamine; C 4 -C 15 cycloaliphatic or aromatic polyamine comprising at least two amine groups, such as cyclohexanediamine and p-xylenediamine; C 7 -C 15 araliphatic polyamine comprising at least two amine groups; aminated C 2 -C 8 alcohol, e.g., ethanolamine; and mixtures thereof.
  • the chain extender is a polyamine having a functionality of 2 and comprising primary amine group or secondary amine group.
  • the amine chain extender is dissolved in the water used to make the PU dispersion
  • the content of the chain extender is from 1.0 wt % to 15 wt %, preferably from 2 wt % to 10 wt %, more preferably from 3 wt % to 9 wt %, based on the total weight of all the components for preparing the prepolymer in the first stage, i.e., based on the total weight of the isocyanate component (A), the isocyanate-reactive component (B) and the catalyst (D). It can be seen that the content of the chain extender is calculated as an additional amount while taking the total amount of the prepolymer as 100 wt %.
  • the waterborne polyurethane dispersion is prepared by a two-stage reaction.
  • a prepolymer is prepared by reacting the isocyanate groups in the isocyanate component (A) with the isocyanate-reactive groups in the isocyanate-reactive component (B) in the presence of the catalyst (D).
  • a polyurethane back bone chain can be formed in the prepolymer by the above stated reaction.
  • the prepolymer is mixed with the surfactant (E) and reacts with the chain extender (F) and the hydrophilic amino siloxane compound (C).
  • the chain extender (F) and the hydrophilic amino siloxane compound (C) comprise isocyanate-reactive groups, e.g. amine group, which react with the free isocyanate groups remained in the prepolymer, hence their structural moieties are also introduced into the resultant polyurethane back bone chain.
  • the chain of the prepolymer is further extended by the chain extender (F) and the hydrophilic amino siloxane compound (C) so as to form the waterborne polyurethane dispersion comprising polyurethane particles dispersed in water.
  • the waterborne polyurethane dispersion may be heated and dried to form a skin film exhibiting superior improved anti-stickiness performance while maintaining good PUD film mechanical properties.
  • the waterborne polyurethane dispersion may have any suitable solids loading of polyurethane particles, but the solids loading is generally between about 1% to about 70% solids by weight of the total dispersion weight, preferably at least about 2%, more preferably at least about 4%, more preferably at least about 6%, more preferably at least about 15%, more preferably at least about 25%, more preferably at least about 35%, most preferably at least about 40%, to at most about 70%, preferably at most 68%, more preferably at most about 65%, more preferably at most about 60% and most preferably at most about 50% by weight.
  • the waterborne polyurethane dispersion may also contain a rheological modifier such as thickeners that enhance the dispersability and stability of the dispersion.
  • a rheological modifier such as thickeners that enhance the dispersability and stability of the dispersion.
  • Any suitable rheological modifier may be used such as those known in the art.
  • the rheological modifier is one that does not cause the dispersion to become unstable. More preferably, the rheological modifier is a water soluble thickener that is not ionized.
  • rheological modifiers examples include methyl cellulose ethers, alkali swellable thickeners (e.g., sodium or ammonium neutralized acrylic acid polymers), hydrophobically modified alkali swellable thickeners (e.g., hydrophobically modified acrylic acid copolymers) and associative thickeners (e.g., hydrophobically modified ethylene-oxide-based urethane block copolymers).
  • the rheological modifier is a methylcellulose ether.
  • the amount of thickener is from at least about 0.2% to about 5% by weight of the total weight of the waterborne polyurethane dispersion, preferably from about 0.5% to about 2% by weight.
  • the waterborne polyurethane dispersion has a viscosity from at least about 10 cp to at most about 10,000 cp, preferably, from at least about 20 cp to at most about 5000 cp, more preferably, from at least about 30 cp to at most about 3000 cp.
  • the dispersion of the PU particles in the waterborne polyurethane dispersion can be promoted by the surfactant and high shear stirring action, wherein the shear force and stirring speed can be properly adjusted based on specific requirement.
  • the waterborne polyurethane dispersion may further comprise one or more pigment, dyes and/or colorant, all of which are generally termed as “color masterbatch” in the present disclosure.
  • the color masterbatch may be added so as to impart a transparent or translucent film with a desired color.
  • pigments dyes and/or colorants may include iron oxides, titanium oxide, carbon black and mixtures thereof.
  • the amount of the pigment, dyes and/or colorant may be 0.1% to 15%, preferably 0.5-10%, more preferably 1% to 5% by weight, based on the total weight of the waterborne polyurethane dispersion.
  • Suitable commercially available black pigments useful in the present invention may include for example EUDERMTM black B-N carbon black dispersion available from Lanxess Deutschland GmbH.
  • FIG. 1 is a schematic illustration of a cross-section of one embodiment of the synthetic leather article described herein.
  • the synthetic leather article comprises, from top to bottom, a top skin film formed by the waterborne polyurethane dispersion, a 2K PU foam base layer, and a backing substrate (e.g. a textile fabric cloth).
  • a backing substrate e.g. a textile fabric cloth.
  • the leather article is not necessarily shown in actual proportion, and the dimensions of one or more layers may be exaggerated so as to clearly show the configuration thereof.
  • the 2K PU foam used in the present disclosure is preferably a non-solvent PU foam and comprises a continuous PU matrix that defines a plurality of pores and/or cells therein.
  • solvent free can be used interchangeably for describing the PU foam or any other dispersion, mixture, etc., and shall be interpreted that the mixture of all the raw materials used for preparing the PU foam or PU dispersion comprise less than 3% by weight, preferably less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, more preferably less than 0.2% by weight, more preferably less than 0.1% by weight, more preferably less than 100 ppm by weight, more preferably less than 50 ppm by weight, more preferably less than 10 ppm by weight, more preferably less than 1 ppm by weight of any organic or inorganic solvents, based on the total weight of the mixture of raw materials.
  • solvent refers to organic and inorganic liquids whose function is solely dissolving one or more solid, liquid or gaseous materials without incurring any chemical reaction.
  • organic compounds e.g. ethylene glycol and propylene glycol, and water, which are generally considered as “solvent” in the polymerization technology, are used in the preparation of the 2k PU foam, none of them belongs to “solvent” since they mainly function as isocyanate-reactive functional substance, chain extending agent or foaming agent, etc. by incurring chemical reactions.
  • the 2k PU foam layer has a thickness in the range from 0.01 ⁇ m to 2,000 ⁇ m, preferably in the range from 0.05 ⁇ m to 1,000 ⁇ m, more preferably in the range from 0.1 ⁇ m to 750 ⁇ m and more preferably in the range from 0.2 ⁇ m to 600 ⁇ m.
  • the foamed polyurethane in the polyurethane foam layer is prepared with a solvent-free polyurethane system comprising (i) one or more second isocyanate components, (ii) one or more second isocyanate-reactive components, (iii) one or more foaming agent, second catalyst and any other additives.
  • the second isocyanate component (i) includes one or more polyisocyanates and/or isocyanate prepolymers which are used for the isocyanate component (A).
  • the second isocyanate-reactive components (ii) comprise compounds having two or more isocyanate-reactive groups selected from OH groups, SH groups, NH groups, NH 2 groups and carbon-acid groups, for example (3-diketo groups.
  • the isocyanate-reactive components (ii) comprise those used for (B).
  • the second isocyanate components (i) and second the isocyanate-reactive components (ii) react with each other in the presence of a foaming/blowing agent, and the foaming agent is used in combination with the isocyanate-reactive components.
  • Useful foaming agents include commonly known chemically or physically reactive compounds.
  • Physical blowing agents may be selected from one or more of a group consisting of carbon dioxide, nitrogen, noble gases, (cyclo)aliphatic hydrocarbons having from 4 to 8 carbon atoms, dialkyl ethers, esters, ketones, acetal and fluoroalkanes having from 1 to 8 carbon atoms.
  • the chemically reactive blowing agent preferably comprises water, which is preferably contained as a constituent of the blend with the isocyanate-reactive components (ii).
  • the amount of the foaming agent is in the range from 0.05 to 10%, preferably in the range from 0.1 to 5%, more preferably from 0.1 to 2%, and most preferably from 0.1 to 0.5% by weight, based on the overall weight of all the raw materials used for preparing the 2k PU foam layer.
  • the 2K PU layer typically has a density of 0.3 to 1.1 kg/liter and preferably has a density of 0.4 to 0.9 kg/liter.
  • the second isocyanate components (i) reacts with the second isocyanate-reactive components (ii) in the presence of a catalyst selected from organotin compounds, such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and/or strongly basic amines such as diazabicyclooctane, triethylamine, triethylenediamine or bis(N,N-dimethylaminoethyl) ether in an amount from 0.01% to 5% by weight, preferably from 0.05% to 4% by weight, more preferably from 0.05% to 3% by weight, based on the overall weight of all the raw materials used for preparing the 2k PU foam layer.
  • organotin compounds such as tin diacetate, tin dioctoate, dibutyltin dilaurate, and/or strongly basic amines such as diazabicyclooctane, triethylamine, triethylened
  • the categories and molar contents of the second isocyanate components (i) and the second isocyanate-reactive components (Bii) are particularly selected so that the overall equivalence ratio of NCO groups to NCO-reactive hydrogen atoms (e.g. hydrogen atom in the hydroxyl group) is in the range from 0.9:1 to 1.8:1, preferably from 0.92:1 to 1.6:1, preferably in the range from 0.95:1 to 1.5:1, and more preferably in the range from 1:1 to 1.45:1, more preferably in the range from 1.05:1 to 1.4:1, and more preferably in the range from 1.10:1 to 1.35:1.
  • the overall equivalence ratio of NCO groups to NCO-reactive hydrogen atoms e.g. hydrogen atom in the hydroxyl group
  • Suitable release layers are typically known in the prior art as “release paper”. Examples of suitable release layers include foils of metal, plastic or paper.
  • the release layer is a paper layer optionally coated with a plastic membrane.
  • the paper layer disclosed herein is coated with a polyolefin, more preferably polypropylene.
  • the paper layer is preferably coated with silicone.
  • the release layer used herein is a PET layer optionally coated with plastic membrane.
  • the PET layer can be is coated with a polyolefin, more preferably polypropylene.
  • the PET layer is preferably coated with silicone. Examples of suitable release layers are commercially available.
  • the release layers used in the present disclosure may have a flat, embossed or patterned surface so that corresponding or complementary surface profile can be formed on the outermost surface of the synthetic leather article.
  • the release layer is textured in the mode of leather grain so as to impart the synthetic leather article with good haptic property comparable with that of high grade natural leather.
  • the release layer generally has a thickness of 0.001 mm to 10 mm, preferably from 0.01 mm to 5 mm, and more preferably from 0.1 mm to 2 mm.
  • the material and the thickness of the release layer can be properly adjusted, as long as the release layer is able to endure the chemical reaction, mechanical processing and thermal treatments experienced during the manufacturing procedures and can be readily peeled from the resultant synthetic leather without bringing about the delamination between the skin film and the 2k PU foam base layer.
  • the PU skin film and the 2K PU foam base layer may independently and optionally comprise any additional auxiliary agents and/or additives for specific purposes.
  • one or more of the auxiliary agents and/or additives may be selected from the group consisting of fillers, cell regulators, release agents, colorants/pigments, surface-active compounds, handfeeling agents, dullers, thickeners, crosslinkers and stabilizers.
  • suitable fillers comprise glass fibers, mineral fibers, natural fibers, such as flax, jute or sisal for example, glass flakes, silicates such as mica or glimmer, salts, such as calcium carbonate, chalk or gypsum.
  • the fillers are typically used in an amount from 0.5% to 60% by weight, preferably from 3% to 30% by weight, and more preferably from 3% to 10% by weight, based on the overall dry weight of the skin film or the 2K PU foam base layer.
  • the backing substrate has a thickness of in the range from 0.01 mm to 50 mm, preferably in the range from 0.05 mm to 10 mm and more particularly in the range from 0.1 mm to 5 mm.
  • the backing substrate may comprise one or more selected from the group consisting of fabric, preferably woven or nonwoven fabric, impregnated fabrics, knit fabric, braid fabric or microfiber; foil of metal or plastic, e.g. rubber, PVC or polyamides; and leather, preferably split leather.
  • the backing substrate can be made of a woven or nonwoven textile.
  • the textile is a nonwoven textile.
  • the textile may be made by any suitable method such as those known in the art.
  • the textile may be prepared from any suitable fibrous material. Suitable fibrous materials include, but are not limited to, synthetic fibrous materials and natural or semi synthetic fibrous materials and mixtures or blends thereof. Examples of synthetic fibrous materials include polyesters, polyamides, acrylics, polyolefins, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols and blends or mixtures thereof. Examples of natural semi-synthetic fibrous materials include cotton, wool and hemp.
  • the waterborne polyurethane dispersion may be applied by conventional coating technologies such as spraying coating, blade coating, die coating, cast coating, etc.
  • the skin film can be either partially or completely dried before the application of the next layer.
  • the skin film is completely dried so as to minimize the moisture entrapped therein, and then the next layer is applied thereon.
  • only part of the moisture is removed from the skin film on the release layer, then the skin film is completely dried together with the 2K PU foam layer applied thereon.
  • the second isocyanate component (i) and the second isocyanate-reactive component (ii) for the 2K non-solvent PU foam are mixed together, applied to the skin film, and pre-cured by being heated in an oven at a temperature of e.g. from 70° C. to 120° C., preferably from 75° C. to 110° C. for a short duration of 10 seconds to 5 minutes, preferably from 30 seconds to 2 minutes, more preferably from 45 to 90 seconds.
  • the backing substrate e.g. a textile fabric
  • the backing substrate is applied to the pre-cured 2k PU foam layer with the assistance of a pressing roller, followed by being post cured at a higher temperature of e.g. from 100° C.
  • the above stated two-step curing process aims to ensure high adhesion strength between the pre-cured 2k PU foam and the backing substrate.
  • the release layer is removed after the 2k PU foam has been fully cured.
  • the release layer can be peeled off via any ordinary technologies.
  • a top finishing layer can be applied onto the surface of the synthetic leather (i.e. on the outermost surface of the skin film) and dried to form a protection film layer.
  • the presence of the finishing layer can further increase abrasion resistance of the multilayer synthetic leather.
  • the protection film layer may be formed by using any suitable raw materials and technologies.
  • the finishing layer may optionally comprise additives such as wetting agent, crosslinking agent, binder, matting agent, hand-feel modifier, pigments and/or colorants, thickener or other additives used for the skin film.
  • the synthetic leather disclosed herein can further comprise one or more than one optional additional layer such as a color layer between the skin film and the finishing layer.
  • Other suitable optional additional layers can be selected from a water repellent layer, UV protective layer and tactile (touch/feel) modification layer.
  • the process of the present invention may be carried out continuously or batchwise.
  • the multilayer structure synthetic leather disclosed herein can be cut or otherwise shaped so as to have a shape suitable for any desired purpose, such as shoe manufacturing.
  • the synthetic leathers can be further treated or post-treated similarly to natural leathers, for example by brushing, filling, milling or ironing.
  • the synthetic leathers may (like natural leather) be finished with the customary finishing compositions. This provides further possibilities for controlling their character.
  • the multilayer structure disclosed herein may be used in various applications particularly suitable for use as synthetic leather, for example, footwear, handbags, belts, purses, garments, furniture upholstery, automotive upholstery, and gloves.
  • the multilayer structure is particular suitable for use in automotive applications.
  • OFX-7700 a hydrophilic amino siloxane compound Dow Chemical of the present application
  • OFX-8209 a hydrophobic amino siloxane compound Dow Chemical Euderm Black B-N Black color master batch Lanxess Acrysol RM 825 Thickener Dow Chemical 1,2-Propanediol (PG) Fast drying agent Sinopharm A2 additive
  • PG Thickener Dow Chemical 1,2-Propanediol
  • Sinopharm A2 additive A mixture of silicone and fluorine based Dow/DuPont slipping agent Polyol in 2k PU composite See, Table 2 Dow Chemical Prepolymer in 2k PU composite Voralast* GE 143 ISO Dow Chemical
  • the 2K non-solvent PU foam is prepared by combining the isocyanate prepolymer (VoralastTM GE 143 ISO) shown in table 1 and the raw materials listed in table 2.
  • synthetic leather articles comprising a skin film derived from the waterborne polyurethane dispersion and a 2k PU foam base layer were prepared by the following Steps 1) to 4).
  • Voranol 222-056 317.5 g
  • castor oil (27.5 g) and MPEG1000 (10 g) were charged into a 1000 ml three neck flask and dehydrated at 115° C. under 76 mmHg pressure for one hour, then naturally cooled down to a temperature of about 72° C.
  • IPDI 145 g
  • the catalyst T12 (0.03 g) was added into the flask.
  • the reaction lasted for one hour at about 72° C., and then was heated to a temperature of about 82° C. and continued for additional 2.5 hours.
  • the product (prepolymer H1) was packaged in a plastic bottle and stored hermetically under nitrogen protection. It was measured that the prepolymer H1 had a NCO % of 7.3%.
  • Voranol 4000LM polyol (130 g), Voranol 4240 polyol (207.5 g), castor oil (27.5 g) and MPEG1000 (10 g) were charged into a 1000 ml three neck flask and dehydrated at 115° C. under 76 mmHg pressure for one hour, then naturally cooled down to a temperature of about 72° C.
  • IPDI (125 g) was poured into the dehydrated polyol mixture at about 72° C. under the protection of nitrogen (N 2 ) flow and mechanical stirring, then the catalyst T12 (0.03 g) was added into the flask. The reaction lasted for one hour at about 72° C., and then was heated to a temperature of about 82° C. and continued for additional 2.5 hours.
  • the product (prepolymer H2) was packaged in a plastic bottle and stored hermetically under nitrogen protection. It was measured that the prepolymer H2 had a NCO % of 7.1%.
  • the waterborne polyurethane dispersion prepared in 2) was mixed with color masterbatch, thickener, slipping agent and fast-drying agent as shown in table 3 at high speed (1000 ⁇ 3000 rpm) for several minutes.
  • the formulated PUD was coated on a release paper to a wet film thickness of 150 ⁇ m.
  • the coated release paper was dried in oven at 100° C. for 3 min and then at 130° C. for 2 min.
  • the release paper with dried PU skin layer was taken out of the oven and cooled down to ambient temperature.
  • the formulated 2k PU composite was coated on the dried PU skin film on the release paper to a wet film thickness of 300 ⁇ m.
  • the release paper with the PU skin film and the coated 2k PU composite was transferred into a 100° C.
  • the tensile strength, elongation at break, modulus at 100% elongation and tear strength of the PUD skin films obtained in Step 3) were characterized according to the standard ASTM D412-15a.
  • the anti-stickiness of the synthetic leather articles prepared in above Step 4) were characterized according to the standard GB/T 8948-2008.
  • two 90 mm ⁇ 60 mm samples of the synthetic leather article were pasted together face to face under a pressure of 1 kg and heated in an oven at 85° C. for 3 h.
  • the anti-stickiness was ranked from 1 to 5 according to the degree of stickiness between the two samples during detaching of the two samples at room temperature:
  • Rank 3 can be detached with a certain force, and the surface is not destroyed;
  • Rank 4 can be detached with a large force and incomplete damage occurs on the surface
  • the formulations and characterization results of the Comparative Examples 1-2 and the Inventive Examples 1-2 were summarized in Table 4.
  • the prepolymer H1 was prepared with a polyether polyol having a Mw of 2,000 and was used in the Inventive Example 1 and Comparative Example 1.
  • the prepolymer H2 was prepared with a polyether polyol having a Mw of 4,000 and was used in the Inventive Example 2 and Comparative Example 2.
  • the difference between the inventive examples and the comparative examples is that a hydrophilic amino siloxane compound (OFX-7700) was used in the inventive examples.
  • the inventive examples a small amount of the OFX-7700, 2.5 wt % of the prepolymer weight, was added during the PUD preparation, while the comparative examples do not comprise said hydrophilic amino siloxane compound. Since the equivalent molecule weight of the hydrophilic amino siloxane (3700 g/mol) is significantly higher than that of piperazine (43 g/mol), the influence of the hydrophilic amino siloxane on chain extension coefficient can be ignored, thus the inventive example and comparative example had almost same chain extension coefficient ( ⁇ 88%).
  • Comparative Example 3 Inventive Example 3 and Inventive Example 4 were performed by repeating the procedures of the Inventive Example 1, except that the content of the hydrophilic amino siloxane compound (OFX-7700) was adjusted to 1.25 wt %, 3.75 wt % and 5.0 wt %, respectively, and the anti-stickiness rank were as follows:
  • the Comparative Example 4 was performed by following the procedures of the Inventive Example 1, except that the OFX-7700 was replaced with a hydrophobic amino siloxane compound (OFX-8209). It was found that there were many bulges on the PUD film, implying that some gels were formed during the forming of the PUD. Since we cannot get a homogeneous and transparent PUD film via this hydrophobic amino siloxane, we did not prepare a synthetic leather with this PUD for further evaluation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
US17/419,635 2019-03-05 2019-03-05 Waterborne polyurethane dispersion and method for preparing the same Abandoned US20220081588A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/076936 WO2020177068A1 (en) 2019-03-05 2019-03-05 Waterborne polyurethane dispersion and method for preparing the same

Publications (1)

Publication Number Publication Date
US20220081588A1 true US20220081588A1 (en) 2022-03-17

Family

ID=72337409

Family Applications (2)

Application Number Title Priority Date Filing Date
US17/419,635 Abandoned US20220081588A1 (en) 2019-03-05 2019-03-05 Waterborne polyurethane dispersion and method for preparing the same
US17/435,593 Active 2040-12-26 US11981827B2 (en) 2019-03-05 2019-08-14 Waterborne polyurethane dispersion and method for preparing the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US17/435,593 Active 2040-12-26 US11981827B2 (en) 2019-03-05 2019-08-14 Waterborne polyurethane dispersion and method for preparing the same

Country Status (6)

Country Link
US (2) US20220081588A1 (ja)
EP (1) EP3935098B1 (ja)
JP (2) JP2022531822A (ja)
KR (2) KR20210135275A (ja)
CN (2) CN113454137A (ja)
WO (2) WO2020177068A1 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113454137A (zh) * 2019-03-05 2021-09-28 陶氏环球技术有限责任公司 水性聚氨酯分散体及其制备方法
WO2022151459A1 (en) * 2021-01-18 2022-07-21 Dow Global Technologies Llc Internally emulsified polyurethane dispersion and method for preparing the same
CN112979911B (zh) * 2021-02-03 2022-04-22 合肥科天水性科技有限责任公司 氟化聚氨酯、壳层雾化喷液、人工仿生皮肤及制备方法
CN113789114A (zh) * 2021-09-17 2021-12-14 卢超 一种自修复抗菌聚氨酯涂层及其制备方法
KR20240102940A (ko) * 2021-11-18 2024-07-03 디아이씨 가부시끼가이샤 우레탄 수지 조성물, 및, 적층체
CN115044011B (zh) * 2022-07-04 2023-09-19 清远市宏图助剂有限公司 一种符合蓝标生态纺织品认证的环保型水性聚氨酯及其制备方法
WO2024011580A1 (en) * 2022-07-15 2024-01-18 Dow Global Technologies Llc Multi-layer synthetic leather products
CN115536802B (zh) * 2022-10-31 2023-06-13 广州海豚新材料有限公司 一种水性聚乳酸改性有机硅聚氨酯及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010034413A1 (en) * 2000-03-07 2001-10-25 Dainichiseika Color & Chem. Mfg. Co., Ltd. Fluorine-containing diols and use thereof

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5874602A (ja) 1981-10-29 1983-05-06 Toray Silicone Co Ltd 毛髪用調整剤
JPS6013841A (ja) * 1983-07-04 1985-01-24 Toray Silicone Co Ltd 成形用エポキシ樹脂組成物
US5554686A (en) * 1993-08-20 1996-09-10 Minnesota Mining And Manufacturing Company Room temperature curable silane-terminated polyurethane dispersions
JPH11511506A (ja) * 1995-09-26 1999-10-05 アメロン インターナショナル コーポレイション ポリシロキサンポリウレタン組成物
EP1035144B1 (de) * 1999-03-12 2006-03-22 Basf Aktiengesellschaft Wasserlösliche oder wasserdispergierbare polymere Salze
DE10216896A1 (de) * 2002-04-17 2003-11-13 Goldschmidt Ag Th Wässrige Polysiloxan-Polyurethan-Dispersion, ihre Herstellung und Verwendung in Beschichtungsmitteln
DE102004015430A1 (de) * 2004-03-30 2005-10-20 Bayer Chemicals Ag Wässrige Polyurethandispersionen
DE102004027003A1 (de) * 2004-06-03 2005-12-22 Wacker-Chemie Gmbh Hydrophile Siloxancopolymere und Verfahren zu deren Herstellung
JP2008527145A (ja) * 2005-01-14 2008-07-24 エヌディーエスユー リサーチ ファウンデーション 表面ミクロドメインを形成するポリマー材料
CN101959914B (zh) * 2007-12-26 2014-02-12 陶氏环球技术有限责任公司 聚氨酯分散体和从该分散体制得的涂层
CN101307181B (zh) 2008-07-02 2010-06-02 天津大学 阴离子聚氨酯与氨基硅油复合的水分散液及其制备和应用
DE102010021465A1 (de) * 2010-05-25 2011-12-01 Clariant International Ltd. Wässrige Polyurethan-Polyharnstoff-Dispersionen
CN102167795A (zh) 2010-12-31 2011-08-31 王奇 一种氨基硅改性水性聚氨酯及其制备方法
JP6073151B2 (ja) * 2013-02-20 2017-02-01 日華化学株式会社 機能性繊維製品の製造方法及びそれに用いる繊維用紫外線吸収剤
CN103497308B (zh) * 2013-10-22 2015-05-20 武汉纺织大学 低温高弹型拒水防污水性聚氨酯涂饰剂的制备方法及其产品
CN103739811B (zh) 2013-12-18 2016-04-27 上海东和胶粘剂有限公司 一种水性聚氨酯及其制备方法
CN105647372A (zh) 2014-11-14 2016-06-08 天津市耀新科技发展有限公司 一种有机硅聚氨酯防水涂料及其制备方法
WO2016124251A1 (en) * 2015-02-06 2016-08-11 Taminco Aqueous polyurethane dispersions
CN104962192A (zh) 2015-06-25 2015-10-07 合肥聚合辐化技术有限公司 耐水、耐候聚酯型水性聚氨酯乳液及其制备方法
CN106243316A (zh) * 2016-07-29 2016-12-21 肇庆浩城树脂科技有限公司 一种水性聚氨酯分散体及其应用
CN108250390B (zh) * 2016-12-29 2020-07-28 万华化学集团股份有限公司 一种聚氨酯或聚氨酯-脲的水分散体、制备方法和用途
CN106632964B (zh) 2016-12-30 2019-03-01 佛山市顺德区德美瓦克有机硅有限公司 一种含超支化结构硅油侧链水性聚氨酯的制备方法
CN107057032A (zh) * 2017-04-26 2017-08-18 合肥科天水性科技有限责任公司 一种用于纺织涂层的高性能水性聚氨酯树脂及制备方法
CN107722236B (zh) 2017-11-07 2020-06-09 陕西科技大学 一种合成革用有机硅改性自消光水性聚氨酯的制备方法及应用
CN109081897A (zh) * 2018-08-01 2018-12-25 万华化学集团股份有限公司 耐湿热性能优异的聚氨酯或聚氨酯脲的水分散体及其制备方法和用途
CN113454137A (zh) * 2019-03-05 2021-09-28 陶氏环球技术有限责任公司 水性聚氨酯分散体及其制备方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010034413A1 (en) * 2000-03-07 2001-10-25 Dainichiseika Color & Chem. Mfg. Co., Ltd. Fluorine-containing diols and use thereof

Also Published As

Publication number Publication date
KR20210137092A (ko) 2021-11-17
CN113631616A (zh) 2021-11-09
US20220154038A1 (en) 2022-05-19
JP2022523233A (ja) 2022-04-21
JP2022531822A (ja) 2022-07-12
EP3935098B1 (en) 2023-11-22
CN113631616B (zh) 2023-06-16
US11981827B2 (en) 2024-05-14
WO2020177068A1 (en) 2020-09-10
KR20210135275A (ko) 2021-11-12
CN113454137A (zh) 2021-09-28
EP3935098A1 (en) 2022-01-12
WO2020177276A1 (en) 2020-09-10
EP3935098A4 (en) 2022-11-09

Similar Documents

Publication Publication Date Title
US11981827B2 (en) Waterborne polyurethane dispersion and method for preparing the same
US20220153915A1 (en) Waterborne polyurethane dispersion and method for preparing same
KR20230106678A (ko) 엠보싱 가능한 비용매 pu 시트, 이를 포함하는 적층체 및 합성 피혁
WO2020097839A1 (en) Synthetic leather article and method for preparing the same
CN113079700A (zh) 合成皮革制品及其制备方法
US20240003079A1 (en) Internally emulisified polyurethane dispersion and method for preparing the same
US20240247094A1 (en) Waterborne polyurethane dispersions for preparing polyurethane foam for synthetic leather and synthetic leather articles prepared with the same
US20220289893A1 (en) A preparation comprising thermoplastic polyisocyanate polyaddition product, a process for preparing the same and the use thereof
WO2024011580A1 (en) Multi-layer synthetic leather products
US20210269576A1 (en) Rigid polyurethane foam with low odor

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION