Fluorine-free fibrous treating compositions, treated substrates, and treating methods

Patent metadata

Field	Value
Publication number	US-11377785-B2
Application number	US-201716323736-A
Country	US
Kind code	B2
Filing date	Aug 8, 2017
Priority date	Aug 12, 2016
Publication date	Jul 5, 2022
Grant date	Jul 5, 2022

Abstract

A fluorine-free treating composition that includes Component A and at least one of Components B and C, wherein: Component (A) includes one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer comprising at least one hydrocarbon group having from 1 to 60 carbon atoms; Component (B) includes one or more compounds derived from reaction, in one or more steps, of components comprising: (i) at least one isocyanate-reactive oligomer comprising 2 to 20 repeating units, or an alcohol having at least one linear or branched hydrocarbon group having from 16 to 40 carbon atoms and optionally one or more ester groups; (ii) at least one polyisocyanate; (iii) optionally at least one additional isocyanate-reactive compound; and (iv) optionally at least one isocyanate blocking agent; and Component (C) includes one or more polycarbodiimide compounds.

First claim

What is claimed is:

1. A method of treating a fibrous substrate in an amount sufficient to make the fibrous substrate water repellent, the method comprising applying to the fibrous substrate a fluorine-free treating composition comprising:
Component (A) comprising one or more polymeric compounds derived from the polymerization of at least one (meth)acrylate monomer comprising at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group; and
Component (B), wherein:
Component (B) comprises one or more compounds derived from reaction, in one or more steps, of components comprising:
(i) at least one isocyanate-reactive oligomer comprising 2 to 20 repeating units, or an alcohol having at least one linear or branched hydrocarbon group having from 16 to 40 carbon atoms and optionally one or more ester groups;
(ii) at least one polyisocyanate;
(iii) optionally at least one additional isocyanate-reactive compound; and
(iv) optionally at least one isocyanate blocking agent;

wherein the isocyanate-reactive oligomer is made by the radical-initiated reaction of at least one (meth)acrylate monomer, in the presence of at least one mercaptan, comprises at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group.

2. The method of claim 1 , wherein the fluorine-free treating composition comprises:
from 1 wt-% to 99 wt-% of Component A, based on the total weight of Component A and Component B; and
from 1 wt-% to 99 wt-% of Component B, based on the total weight of Component A and Component B.

3. The method of claim 1 , wherein the one or more polymeric compounds of Component A are derived from the polymerization of at least one (meth)acrylate monomer having at least one of the following formulas:
R 1 —OC(O)—C(R 2 )=CH 2   (Formula 0)

R 1 —NH—C(O)O- L 1 -OC(O)C(R 2 )=CH 2   (Formula I);

R 3 -X 1 -C(O)NH- L 2 -OC(O)C(R 4 )=CH 2   (Formula II); and

R 5 -X 2 -C(O)NH- Q -NHC(O)O- L 3 -OC(O)C(R 6 )=CH 2   (Formula III);

wherein:
R 1 , R 3 , and R 5 are independently a hydrocarbon group having from 1 to 60 carbon atoms;
R 2 , R 4 , and R 6 are independently H or CH 3 ;
L 1 , L 2 , and L 3 are independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group, or a combination thereof;
X 1 and X 2 are independently O, S, —NH, or —N(R 7 ), wherein R 7 is a hydrocarbon group having 1 to 20 carbon atoms; and
Q is an isocyanate residue.

4. The method of claim 1 , wherein the one or more polymeric compounds of Component A additionally include units derived from a (meth)acrylate monomer with one or more functional groups capable of undergoing additional reactions.

5. The method of claim 1 , wherein the one or more compounds of Component B comprises a blocked isocyanate group.

6. The method of claim 1 , wherein the (meth)acrylate monomer for making the isocyanate-reactive oligomer used in making the one or more compounds of Component B has at least one of the following formulas:
R 1 —OC(O)—C(R 2 )=CH 2   (Formula 0)

R 1 —NH—C(O)O- L 1 -OC(O)C(R 2 )=CH 2   (Formula I);

R 3 -X 1 -C(O)NH- L 2 -OC(O)C(R 4 )=CH 2   (Formula II); or

R 5 -X 2 -C(O)NH- Q -NH—C(O)O- L 3 -OC(O)C(R 6 )=CH 2   (Formula III);

wherein:
R 1 , R 3 , and R 5 are independently a hydrocarbon group having from 1 to 60 carbon atoms;
R 2 , R 4 , and R 6 are independently H or CH 3 ;
L 1 , L 2 , and L 3 are independently a branched or straight chain alkylene group having 2 to 10 carbon atoms, an arylene group (in some embodiments, an arylene group having 5 to 12 carbon atoms), or a combination thereof;
X 1 and X 2 are independently O, S, —NH, or —N(R 7 ), wherein R 7 is a hydrocarbon group having 1 to 20 carbon atoms; and
Q is a divalent isocyanate residue.

7. The method of claim 1 , wherein the isocyanate-reactive oligomer for making the one or more compounds of Component B is made by the oligomerization of a (meth)acrylate monomer in the presence of a mercaptan, wherein the molar ratio of the mercaptan to the (meth)acrylate is 1:4 to 1:20.

8. The method of claim 1 , wherein the (meth)acrylate monomer used in the preparation of the compounds of Components A and/or B comprises at least one hydrocarbon group having from 12 to 60 carbon atoms.

9. A fibrous substrate treated by the method of claim 1 .

10. The fibrous substrate of claim 9 , which is selected from the group of textile, leather, carpet, paper, and nonwoven fabrics.

Assignees

• 3M Innovative Properties Co

Inventors

• Coppens Dirk M
• Dams Rudolf J

Classifications

• C08G18/24

  of tin · CPC title

• C08F220/00

  Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof · CPC title

• C08G18/8116

  esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group · CPC title

• C08G18/2825

  having at least 6 carbon atoms · CPC title

• D06M15/263 Primary

  of unsaturated carboxylic acids; Salts or esters thereof · CPC title