Non-solvent 2K polyurethane artificial leather composition, artificial leather prepared with same and preparation method thereof

Patent metadata

Field	Value
Publication number	US-12258705-B2
Application number	US-201917597742-A
Country	US
Kind code	B2
Filing date	Sep 25, 2019
Priority date	Sep 25, 2019
Publication date	Mar 25, 2025
Grant date	Mar 25, 2025

Abstract

A non-solvent two-component polyurethane artificial leather composition is provided. The polyurethane composition comprises (A) a polyurethane-prepolymer component, comprising one or more polyurethane-prepolymers prepared by reacting at least one polyisocyanate compound with at least one first polyol, wherein the polyurethane-prepolymer comprises at least two free isocyanate groups; and (B) a polyol component, comprising at least one second polyol; wherein the polyol component further comprises an encapsulated foaming agent comprising at least one foaming core phase encapsulated within an outer shell. The polyurethane leather product derived from the polyurethane composition exhibits enhanced stability, mild bubble generation and improved cost effectiveness. A polyurethane leather product prepared with said composition and the method for preparing the same are also provided.

First claim

What is claimed is:

1. A non-solvent two-component polyurethane artificial leather composition, comprising
(A) a polyurethane-prepolymer component, comprising one or more polyurethane-prepolymers prepared by reacting at least one polyisocyanate compound with at least one first polyol, wherein the polyurethane-prepolymer comprises at least two free isocyanate groups, the polyurethane-prepolymer having a NCO content of 10 to 20 wt % and a viscosity of 50 to 10,000 cSt; and
(B) a polyol component, comprising at least one second polyol;
wherein the polyol component further comprises an encapsulated foaming agent comprising at least one foaming core phase encapsulated within an outer shell.

2. The composition according to claim 1 , wherein the foaming core phase comprises at least one member selected from the group consisting of C 3 -C 16 aliphatic hydrocarbon optionally substituted with at least one chlorine atom and/or fluorine atom, C 6 -C 16 cycloaliphatic or aromatic hydrocarbon optionally substituted with at least one chlorine atom and/or fluorine atom, C 2 to C 16 ether compound optionally substituted with at least one chlorine atom and/or fluorine atom, tetra (C 1 -C 6 alkyl) silane, tetra (C 1 -C 6 alkoxy) silicon, water, carbonamide compound, hydrazide, polyamine, nitrile, carboxylate salt, bicarbonate salt, organic sulfate salt, carbon dioxide, carbon monoxide, and combinations thereof; and
the outer shell comprises at least one member selected from the group consisting of acrylic resin, phenolic resin, alkyd resin, polyester resin, amino resin, epoxy resin, copolymers thereof and blends thereof.

3. The composition according to claim 2 , wherein the foaming core phase comprises at least one member selected from the group consisting of propane, butane, pentane, cyclopentane, trichlorofluoromethane, dichlorodifluoromethane, 1,1-dichlorofluoroethane, dichlorotrifluoroethane, dichlorodifluoroethane, dichlorotetrafluoroethane, trichlorotrifluoro-ethane, 1,1,1,3,3-pentafluoropropane, perfluoropropane, water, azodicarbonamide, benzene-sulfonyl hydrazide, N,N′-dinitrosopentamethylene tetramine, toluenesulfonyl hydrazide, azobisisobutyronitrile, barium azodicarboxylate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, iron bicarbonate, sodium dodecyl sulfate, nitrogen, carbon dioxide, carbon monoxide, and combinations thereof; and/or
the outer shell comprises homopolymer or copolymer formed by at least one monomer selected from the group consisting of acrylonitrile, methacrylonitrile, a-chloroacrylonitrile, a-ethoxyacrylonitrile, fumaronitrile, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl butyrate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, dodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, 2-chloroethyl (meth)acrylate, phenyl (meth)acrylate, isobonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, ethylstyrene, dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, n-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrenechlorostyrene, acrylamide, methacrylamide, N-phenyl maleimide, N-(2-chlorophenyl) maleimide, N-cyclohexyl maleimide, N-laurylmaleimide, ethylene, propylene, butylenes, isobutylene, vinylmethylether, vinylethylether, vinylisobutylether, vinylmethylketone, vinylhexylketone, methylisopropenyllketone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethyloipropane trimethacrylate, pentaerithrityl tetramethacrylate, bis(metacryloyloxymethyl)tricyclodecane, and blends thereof.

4. The composition according to claim 1 , wherein the content of the encapsulated foaming agent is from 2 to 7 wt %, based on the total weight of the polyol component (B).

5. The composition according to claim 1 , wherein the content of the encapsulated foaming agent is from 2.5 to 3.5 wt %, based on the total weight of the polyol component (B).

6. The composition according to claim 1 , wherein the encapsulated foaming agent has at least one of the following parameters:
a) having a particle size of 5 to 40 μm;
b) having a outer shell thickness of 0.1 to 10 μm;
c) being able to expand, irreversibly or reversibly, by 2 to 10 times in particle size when heated;
d) having a pre-expansion density of 30 kg/cm 3 or less;
e) having an expansion starting temperature of 80° C. to 150° C.; and
f) having a softening temperature of 120° C. to 235° C.

7. The composition according to claim 1 , wherein the encapsulated foaming agent has a particle size of 16-24 μm, a expansion starting temperature of 95-115° C., a pre-expansion density of 10 kg/cm 3 or less, softening temperature of 147° C. to 167° C.; and
wherein the outer shell is formed with acrylic resin, and the foaming core phase is C 3 -C 16 aliphatic hydrocarbon optionally substituted with at least one chlorine atom and/or fluorine atom.

8. The composition according to claim 1 , wherein the polyisocyanate compound is selected from the group consisting of C 4 -C 12 aliphatic polyisocyanate comprising at least two isocyanate groups, C 6 -C 15 cycloaliphatic or aromatic polyisocyanate comprising at least two isocyanate groups, C 7 -C 15 araliphatic polyisocyanate comprising at least two isocyanate groups, and any combinations thereof; and
each of the first polyol and the second polyol is independently selected from the group consisting of C 2 -C 16 aliphatic polyhydric alcohols comprising at least two hydroxyl groups, C 6 -C 15 cycloaliphatic or aromatic polyhydric alcohols comprising at least two hydroxyl groups, C 7 -C 15 araliphatic polyhydric alcohols comprising at least two hydroxyl groups, polyester polyols having a molecular weight from 100 to 5,000 and an average hydroxyl functionality of 1.5 to 5.0, a polyether polyol which is a poly(C 2 -C 10 )alkylene glycol or a copolymer of multiple (C 2 -C 10 )alkylene glycols having a molecular weight from 100 to 5,000, polycarbonate diols having a molecular weight from 100 to 5,000, C 2 -C 10 alkanolamine comprising at least one hydroxyl group and at least one amino groups, and combinations thereof.

9. The composition according to claim 1 , wherein the weight ratio between the polyurethane-prepolymer component (A) and the polyol component is from 100:40 to 100:60.

10. The composition according to claim 1 , wherein the second polyol includes a polyether polyol modified with comonomers of styrene and acrylonitrile, having a molecular weight from 2,000 to 3,000, an average OH number of 20 to 25 mg KOH/g, a viscosity of 4500-4900 cSt, and a solid content of 25 wt % to 45 wt %.

11. The composition according to claim 1 , wherein the composition comprises no higher than 2 wt % of water solvent and no higher than 2 wt % of organic solvent; or
the composition is free of water solvent and is free of organic solvent.

12. The composition according to claim 1 , wherein the composition does not comprise any forming agents other than the encapsulated foaming agent; and/or
the composition does not comprise foaming stabilizer.

13. A method for preparing an artificial po

Assignees

• Dow Global Technologies Llc

Inventors

• Zhang Chao
• Feng Yanli
• Qin Shihao

Classifications

• D06N2211/28

  Artificial leather · CPC title

• D06N3/0043

  characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers (foraminous structure obtained by stretching D06N3/0029) · CPC title

• C08G2110/0008

  flexible · CPC title

• C08G18/4072

  Mixtures of compounds of group C08G18/63 with other macromolecular compounds · CPC title

• C08G18/242

  organometallic compounds containing tin-carbon bonds · CPC title