Self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, resin material containing same, method for producing same, artificial leather comprising same, and thermoplastic polyolefin skin material comprising same

Patent metadata

Field	Value
Publication number	US-10000609-B2
Application number	US-201113818552-A
Country	US
Kind code	B2
Filing date	Aug 11, 2011
Priority date	Aug 26, 2010
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

Provided are a self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin derived from a reaction of a 5-membered cyclic carbonate polysiloxane compound represented by the following formula (1) and an amine compound and having polysiloxane segments and masked isocyanate groups in its structure:

wherein A means

and its production process. The present invention can provide a polyhydroxy polyurethane resin, the development of applications of which has not moved ahead in the prior art, as a novel self-crosslinking polyhydroxy polyurethane resin that enables to provide products excellent in lubricity, abrasion resistance, chemical resistance, non-tackiness, heat resistance and the like, is useful from the viewpoint of the reduction of warming gas, and is responsive to the environment.

First claim

The invention claimed is:

1. A self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, comprising in a structure thereof:
polysiloxane-modified polyhydroxy polyurethane resin having polysiloxane segments; and
masked isocyanate groups,
wherein the polysiloxane-modified polyhydroxy polyurethane resin having the polysiloxane segments is a reaction product of a 5-membered cyclic carbonate polysiloxane compound represented by following formula (1) and a diamine compound:

wherein A means

in which R 1 means an alkylene group which has from 1 to 12 carbon atoms and may be connected therein via an element of 0, S or N and/or —(C 2 H 4 O) b —, R 2 means a direct bond or an alkylene group having from 2 to 20 carbon atoms, R 2 may be linked to an alicyclic group or aromatic group, b stands for a number of from 1 to 300, and a stands for a number in a range from 1 to 300,
the masked isocyanate groups are present in at least one portion attached to the polysiloxane-modified polyhydroxy polyurethane resin so as to form the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, and
the attached portion is bound to the polysiloxane-modified polyhydroxy polyurethane resin at at least one free hydroxyl group having been present in the polysiloxane-modified polyhydroxy polyurethane resin via a bond formed as a result of a reaction between (i) at least one free isocyanate group having been present in the attached portion and (ii) the at least one free hydroxyl group having been present in the polysiloxane-modified polyhydroxy polyurethane resin and bound to a carbon atom in a main chain of the polysiloxane-modified polyhydroxy polyurethane resin.

2. The self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 ,
wherein the 5-membered cyclic carbonate polysiloxane compound is a reaction product of an epoxy-modified polysiloxane compound and carbon dioxide, and
the 5-membered cyclic carbonate polysiloxane compound contains, in a structure thereof, carbon dioxide in a range from 1 to 25 mass %.

3. The self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 , wherein a content of the polysiloxane segments in the resin is in a range from 1 to 75 mass % relative to a siloxane content in resin molecules.

4. The self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 ,
wherein the masked isocyanate groups are reaction products of organic polyisocyanate groups in an organic polyisocyanate compound and a masking agent, and
when subjected to heat treatment, the masked isocyanate groups are demasked and form free isocyanate groups, which are reactable with hydroxyl groups in the structure of the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin such that the resin undergoes self-crosslinking.

5. The resin according to claim 4 ,
wherein the organic polyisocyanate compound having the organic polyisocyanate groups is at least one compound selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4′-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-nephthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, and adducts thereof.

6. The resin according to claim 4 ,
wherein the masking agent is at least one agent selected from the group consisting of alcohol-based masking agents, phenol-based masking agents, active methylene-based masking agents, acid amide-based masking agents, imidazole-based masking agents, urea based-masking agents, oxime-based masking agents, and pyridine-based masking agents.

7. A resin material comprising;
the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 ; and
another binder resin blended therewith.

8. An imitation leather comprising:
a base fabric; and
a resin composition composed, as a principal component, of the self-crosslinking polysiloxane-modified polyurethane resin according to claim 1 ,
where in the resin composition is impregnated in or laminated on the base fabric.

9. The imitation leather according to claim 8 , wherein the resin composition further comprises another resin different from the self-crosslinking polysiloxane-modified polyurethane resin.

10. A skin material made of a thermoplastic polyolefin resin, comprising:
a thermoplastic polyolefin resin sheet; and
a first top coat layer formed directly on the resin sheet or a second top coat layer formed on a primer layer that is formed on the resin sheet,
wherein the first and second top coat layers are formed of a resin composition, as a principal component, comprising the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 .

11. The skin material according to claim 10 ,
wherein the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin is formed by modifying, with a modifier, the polysiloxane-modified polyhydroxy polyurethane resin as the reaction product of the 5-membered cyclic carbonate polysiloxane compound and the diamine compound.

12. The skin material according to claim 10 ,
wherein each of the top coat layers is formed of a composition comprising the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin and a material,
the material comprises one fine powder or a combination of two or more fine powders selected from the group consisting of organic fine powders and inorganic fine powders,
the material is added to the composition as a matting agent at a proportion from 1 to 150 parts by mass per 100 parts by mass of the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin.

13. The skin material according to claim 10 ,
wherein each of the top coat layers is formed of a resin composition comprising, in addition to the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, another resin different from the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin.

14. A process for producing the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin according to claim 1 ,
reacting a modifier comprising the at least one free isocyanate group and the at least one of the masked isocyanate groups, with the polysiloxane-modified polyhydroxy polyurethane resin having the at least one free hydroxyl group bound to the carbon atom in the main chain thereof, so as to form the bond between (i) the at least one free isocyanate group of the modifier forming the attached portion and (ii) the at least one hydroxyl group bound to the main chain of the polysiloxane-modified polyhydroxy polyurethane resin, so that the self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin comprising in the structure thereof the masked isocyanate groups is formed.

15. The process according to claim 14 ,
wherein the 5-membered cyclic carbonate polysiloxane compound is a reaction product of an epoxy-modified polysiloxane compound and carbon dioxide, and
the polysiloxane-modified polyhydroxy polyurethane resin as a reaction product of the 5-membered cyclic carbonate polysiloxane compound and the diamine compound incorporates in its structure the carbon dioxide in a range from 1 to 25 mass % in the pol

Assignees

• Hanada Kazuyuki
• Kimura Kazuya
• Takahashi Kenichi
• Kawakami Osamu
• Uruno Manabu
• Dainichiseika Color Chem
• Ukima Colour & Chem Mfg

Inventors

• Hanada Kazuyuki
• Kimura Kazuya
• Takahashi Kenichi
• Kawakami Osamu
• Uruno Manabu

Classifications

• C08J7/0427

  with only one layer of a composition containing a polymer binder (with more layers C08J7/042) · CPC title

• C08J2323/02

  not modified by chemical after treatment · CPC title

• D06N3/14

  with polyurethanes · CPC title

• C08G18/8074

  Lactams · CPC title

• C08J2475/04

  Polyurethanes · CPC title