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

Patent metadata

Field	Value
Publication number	US-2019177908-A1
Application number	US-201716323736-A
Country	US
Kind code	A1
Filing date	Aug 8, 2017
Priority date	Aug 12, 2016
Publication date	Jun 13, 2019
Grant date	—

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

1 . 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 of Component (B) and Component (C), 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 Component (C) comprises one or more polycarbodiimide compounds.

2 . The fluorine-free treating composition of claim 1 , comprising:
from 1 wt-% to 99 wt-% of Component A, based on the total weight of Component A and Components B and/or C; and from 1 wt-% to 99 wt-% of Component B, Component C, or both, based on the total weight of Component A and Components B and/or C.

3 . The fluorine-free treating composition 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 comprising at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group.

4 . The fluorine-free treating composition 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.

5 . The fluorine-free treating composition 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.

6 . The fluorine-free treating composition of claim 1 , wherein the isocyanate-reactive oligomer used to make the one or more compounds of Component B is made by the radical-initiated reaction of at least one (meth)acrylate monomer in the presence of at least one mercaptan, wherein the at least one (meth)acrylate monomer comprises at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group.

7 . The fluorine-free treating composition of claim 1 , wherein the one or more compounds of Component B comprises a blocked isocyanate group.

8 . The fluorine-free treating composition of claim 1 , wherein the one or more polycarbodiimide compounds of Component C are derived from a carbodiimidization 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; and (iii) optionally at least one additional isocyanate-reactive compound; 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 wherein the at least one (meth)acrylate monomer comprises at least one hydrocarbon group having from 1 to 60 carbon atoms.

9 . The fluorine-free treating composition of claim 8 , wherein the isocyanate-reactive oligomer used to make the one or more polycarbodiimide compounds of Component C is made by the radical-initiated reaction of at least one (meth)acrylate monomer, in the presence of a mercaptan, wherein the at least one (meth)acrylate monomer comprises at least one hydrocarbon group having from 1 to 60 carbon atoms and at least one isocyanate-derived group.

10 . The fluorine-free treating composition of claim 1 , wherein the one or more polycarbodiimide compounds of Component C has the following formula:
Q 2 -(X 5 —C(O)NH-(A 1 -(N═C═N)) r —(Z 2 ) q -A 2 -NHC(O)—X 6 ) p -Q 3   (Formula IX)
wherein:
X 5 and X 6 are each O;
A 1 and A 2 each represents the residue of an organic di-isocyanate compound;
q is 0;
p is 1;
r is 3; and
Q 2 and Q 3 are independently selected from: a hydrocarbon group having at least 2 carbon atoms; and a group having the formula:
—(CH 2 ) a —S—U  (Formula XI)

wherein:
a is an integer from 1 to 10;
S is sulfur; and
U is selected from:
an oligomer comprising 2 to 20 repeating units of (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms;
an oligomer comprising 2 to 20 repeating units of urethane-containing (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms;
an oligomer comprising 2 to 20 repeating units of urea-containing (meth)acrylate monomers, each repeating unit independently comprising an alkyl group having at least 16 carbon atoms; and
a combination thereof.

11 . The fluorine-free treating composition 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 and/or Component C 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.

12 . The fluorine-free treating composition of claim 1 , wherein the isocyanate-reactive oligomer for making the one or more compounds of Component B and/or Component C is made by the oligomerization of a (meth)acrylate monomer in the presence of a mercaptan, wherein the molar ratio of the mercaptan with the (meth)acrylate is 1:4 to 1:20.

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

Assignees

• 3M Innovative Properties Co

Inventors

• Coppens Dirk M
• Dams Rudolf J

Classifications

• D21H19/12

  applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds · CPC title

• C09D179/08

  Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors · 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

• C09D175/14

  Polyurethanes having carbon-to-carbon unsaturated bonds · CPC title

• D21H19/30

  Polyamides; Polyimides · CPC title