Fluorine-containing maleic acid terpolymer soil and stain...

Details Fluorine-containing maleic acid terpolymer soil and stain... Fluorine-containing maleic acid terpolymer soil and stain...

1999-06-21

2001-05-29

Wu, David W. (Department: 1713)

Stock material or miscellaneous articles

Coated or structually defined flake, particle, cell, strand,...

Rod, strand, filament or fiber

C526S247000, C526S271000, C428S097000, C428S395000, C428S375000, C428S378000, C428S392000

Reexamination Certificate

active

06238792

ABSTRACT:

BACKGROUND OF THE INVENTION
Stain resist compositions based on hydrolyzed maleic anhydride polymers provide stain resistance towards acid dyes when applied from low pH aqueous solutions onto polyamide fibers. However, the fibers require a further treatment in an additional step with a fluorochemical dispersion to prevent soiling. This additional step can be costly since it requires application equipment and heating. To circumvent the additional costs, attempts have been made to modify maleic anhydride polymers by partial esterification with fluoroalcohols or fluorothiols as described by Pechhold and Murphy in U.S. Pat. No. 5,670,246. However, a drawback of this approach is the limited stability of the fluoroesters in low pH of less than about 2 in aqueous application baths.
Copolymers of non-hydrolyzable perfluoroalkyl monomers with maleic anhydride have been described by Pittman et al. in U.S. Pat. Nos. 3,844,827 and 4,029,867, and by Bildhauer et al. in Canadian Application 2,148,998. These fluorinated maleic acid polymers provide antisoil properties, but, they are unacceptable as anti-stain compositions.
There is thus a need for fluoropolymers which can be introduced into other polymer matrices to lower the surface energy and thus provide simultaneous soil and stain resistance in a single application step. The present invention provides such a polymer.
SUMMARY OF THE INVENTION
The present invention comprises a composition comprising a terpolymer having units of Formula I
wherein
X is a C
2-10
alkyl, C
6-12
aryl, or C
4-12
alkoxy radical,
d is from about 3 to about 50,
R is a fluoroalkyl radical R
f
—(A)
v
—(B)
w
—,
R
f
is a fully fluorinated straight or branched aliphatic radical optionally interrupted by at least one oxygen atom,
A is a divalent radical selected from —SO
2
N(R″)—, —CON(R″)—, —S—, or —SO
2
—, where R″ is H, or a C
1-6
alkyl radical,
B is a divalent linear hydrocarbon radical —C
t
H
2t
—, where t is 1 to 12,
Y is a divalent radical —CH
2
—O—,
u, v, and w are each independently zero or 1,
R′ is hydrogen or methyl,
e is from about 0.05 to about 10,
M is hydrogen, alkali metal, or ammonium, and
f is from about 5 to about 40.
The present invention further comprises a method of providing soil resistance and resistance to staining by acid dyes to fiber substrate comprising application in a single step of an effective amount of a composition of a terpolymer having units of Formula I as defined above.
The present invention further comprises a fiber to which has been applied a composition of a terpolymer having units of Formula I as defined above.
The composition of the present invention for providing stain and soil resistance comprises hydrolyzed maleic anhydride terpolymers as shown above in Formula I prepared from aliphatic/aromatic alpha olefins or alkyl vinyl ethers, small limited amounts of a non-hydrolyzable perfluoroalkyl substituted monomer, and maleic anhydride. The amount of the non-hydrolyzable perfluoroalkyl substituted monomer should not exceed 0.25 mole per mole of maleic anhydride. The hydrolyzed terpolymers are completely water soluble and will absorb at low pH of less than about 3 from the aqueous solution onto the fiber surface.
DETAILED DESCRIPTION OF THE INVENTION
The present invention comprises a composition which provides both stain resistance and soil resistance to polyamide, polyester, polyolefin and wool fibers such as carpets. The composition of the present invention is applied to the substrate in a single application step instead of the usual separate steps used at the textile or carpet mill to apply a stain resist composition and a soil resist composition. The composition of the present invention is a hydrolytically stable perfluoroalkyl-substituted terpolymer which overcomes the shortfalls of earlier attempts to apply a single composition to achieve both stain resistance and soil resistance.
The present invention comprises terpolymers which, after hydrolysis, provide both soil and stain resistance to fibers. The terpolymers are formed by polymerization of the following monomers 1) an aliphatic or aromatic alpha olefin or an alkyl vinyl ether, 2) a non-hydrolyzable perfluoroalkyl substituted monomer, and 3) maleic anhydride.
This invention comprises novel maleic acid terpolymers with perfluoroalkyl side chains of the structure of Formula I shown below which provide both soil and stain resistance to fibers in a single step application.
wherein
X is a C
2-10
alkyl, C
6-12
aryl, or C
4-12
alkoxy radical,
d has a value in the range of from about 3 to about 50,
R is a fluoroalkyl radical R
f
—(A)
v
—(B)
w
—,
R
f
is a fully fluorinated straight or branched aliphatic radical optionally interrupted by at least one oxygen atom,
A is a divalent radical selected from —SO
2
N(R″)—, —CON(R″)—, —S—, or —SO
2
—, wherein R″ is H, or a C
1-6
alkyl radical,
B is a divalent linear hydrocarbon radical —C
t
H
2t
—, where t is 1 to 12,
Y is a divalent radical —CH
2
—O—,
u, v, and w are independently the same or different and are zero or 1,
R′ is hydrogen or methyl,
e is from about 0.05 to about 10,
M is hydrogen, alkali metal, or ammonium, and
f has a value in the range of from about 5 to about 40.
Preferably the precursors of the terpolymers of Formula I (before hydrolysis of the maleic anhydride ring) have molar ratios of alkyl vinyl ether or alpha-olefin to maleic anhydride of from about 0.6:1 to about 1.2:1, and of non-hydrolyzable perfluoroalkyl substituted monomer to maleic anhydride of from about 0.01:1 to about 0.25:1. The number average molecular weights of these preferred maleic anhydride terpolymers are controlled conventionally by the use of chain transfer agents, as further described below, to the approximate range of 1,000 to 20,000.
The preferred terpolymers of Formula I have values of d of from about 5 to about 15, values of e of from about 0.1 to about 3, and values of f of from about 7 to about 20.
The hydrocarbon monomers useful in the preparation of the terpolymers of this invention are alkyl (C
2-10
) vinyl ethers, and aliphatic (C
4-12
) or aromatic (C
8-14
) alpha olefins. Representative examples of preferred monomers are listed below by way of illustration and not limitation: isobutylene, 1-decene, methylstyrene, phenylstyrene, hexyl vinyl ether, and octyl vinyl ether. Most preferred hydrocarbon monomers are: 1-hexene, 1-octene, styrene, and butyl vinyl ether.
The fluorine-containing monomer used in the preparation of the terpolymers of the present invention is a non-hydrolyzable perfluoroalkyl substituted monomer. Preferably R
f
in this monomer contains at least 1 and not more than about 30 carbon atoms. Most preferably R
f
contains 4 to 16 carbon atoms. Representative preferred examples of these monomers prior to polymerization useful in the practice of the present invention are listed below:
CnF
(2n+1)
—CH═CH
2
, wherein n=4, 6, 8, 10, 12, and 14 or a mixture thereof,
CnF
(2n+1)
—CH
2
—CH═CH
2
, wherein n is as previously defined,
CnF
(2n+1)
—(CH
2
)
6
—CH═CH
2
, wherein n is as previously defined,
C
8
F
17
—SO
2
—NH—CH
2
—CH
2
—O—CH
2
—CH═CH
2
,
C
8
F
17
—SO
2
—N(CH
3
)—CH
2
—CH
2
—O—CH
2
—CH═CH
2
,
C
8
F
17
—SO
2
—N(C
2
H
5
)—CH
2
—CH
2
—O—CH
2
—CH═CH
2
,
C
8
F
17
—SO
2
—NH—CH
2
—CH
2
—O—CH
2
—C(CH
3
)═CH
2
,
C
8
F
17
—SO
2
—N(CH
3
)—CH
2
—CH
2
—O—CH
2
—C(CH
3
)═CH
2
,
C
8
F
17
—SO
2
—N(C
2
H
5
)—CH
2
—CH
2
—O—CH
2
—C(CH
3
)═CH
2
,
C
7
F
15
—CO—NH—CH
2
—CH═CH
2
,
C
8
F
17
—SO
2
—NH—CH
2
—CH
2
═CH
2
,
C
n
F
(2n+1)
—CH
2
—CH
2
—S—CH═CH
2
, wherein n is as previously defined,
(CF
3
)
2
CF—O—CH
2
—CH═CH
2
, and
(CF
3
)
2
CF—O—CH
2
—C(CH
3
)═CH
2
Most preferred of these substituted monomers are the following:
C
n
F
(2n+1)
—CH
2
—CH
2
—O—CH
2
—CH═CH
2
, wherein n is as previously defined.
C
n
F
(2n+1)
—CH
2
—CH
2
—O—CH
2
—C(CH
3
)═CH
2
, wherein n is as previously defined, and
F(CF
2
)
n
—CH
2
—CH
2
═CH
2
wherein n is as previously defined.
Thus in the t

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