Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2003-02-21
2004-11-16
Pezzuto, Helen L. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S243000, C526S255000, C526S273000, C526S307000, C526S307700, C526S320000, C526S328500, C526S329200, C526S329300, C526S329400, C428S326000, C428S422000, C428S507000, C428S510000
Reexamination Certificate
active
06818717
ABSTRACT:
FIELD OF THE INVENTION
The present invention concerns novel internally or externally applied fluorine containing polymers which impart oil and grease resistance to paper and soil-release properties to textile products. More particularly it concerns copolymerization products of (a) a perfluoroalkyl-substituted (meth)acrylate or (meth)acrylamide, (b) a secondary or, tertiary amino or quaternary ammonium group-containing (meth)acrylate or (meth)acrylamide and (c) vinylidene chloride and, optionally, d) other copolymerizable vinyl monomers, their preparation and use.
BACKGROUND OF THE INVENTION
The use of perfluoroalkyl-substituted compounds to impart oil and grease repellency to textile and paper substrates is along established practice. For paper treatment the most important products have traditionally been phosphate diesters of a perfluoroalkylalkanol or di-perfluoroalkyl-substituted carboxylic acids, as described in U.S. Pat. Nos. 4,485,251, 4,898,981 and 5,491,261. These compounds are applied either in the wet-end—that is they are added to the pulp—or applied by rollers, a size press or other means to the finished paper as a coating. The fluorochemicals used for treating textiles are all polymers; the vast majority are copolymers of poly-perfluoroalkyl (meth)acrylates. More recently such polymers have also been used as external paper sizes since polymers provide the extra benefit of water resistance which is a desirable feature in many food packaging and fast-food applications.
To achieve water repellency by internal sizing, alkyl-ketene-dimer (AKD; sold under the trade name HERCON by Hercules Inc., among others) is most commonly used since the small amount of fluorine add-on (typically 0.08-0.12%) is inadequate for this purpose. In addition, the commonly used internal fluorochemical oil-sizing agents, even while impart oil sizing, have, due to their inherently surfactant-like “head-tail” structure, a deleterious effect on water resistance by inhibiting the AKD curing reaction.
The present invention concerns fluorochemical polymers which are useful as an internally or externally applied oil- and grease proofing paper size which imparts, in addition to oil resistance, excellent water resistance. It has further been discovered that the polymers of the present invention impart excellent soil-release and anti-soiling properties to textiles.
The polymer of the present invention is a copolymer of
a) 45-90% by weight of a perfluoroalkyl-substituted (meth)acrylate or acrylamide,
b) 5-30% by weight of a secondary or tertiary amino or quaternary ammonium group-containing (meth)acrylate or (meth)acrylamide,
c) 1-20% by weight of vinylidene chloride (VDC), and, optionally,
d) 0-10% by weight of a nonfluorinated vinyl monomer.
Relevant prior art includes U.S. Pat. No. 3,919,183 (Jager et al.), which discloses polymers useful as oil repellent coatings for porous substrates such as textile materials and paper which comprise a perfluoroalkylethyl acrylate, optionally copolymerized with up to 95% by weight of other monomers. Among other possible co-monomers, vinylidene chloride and N,N-dialkyl-aminoethyl methacrylate are mentioned. However no vinylidene chloride-containing compositions are exemplified.
U.S. Pat. No. 4,013,627 (Temple) describes textile finishes which are copolymers of 20-99% by weight of a perfluoroalkylethyl acrylate, 1-80% of a vinyl monomer having no non-vinylic fluorine atoms and 0.1-4% of a (meth)acrylate bearing a quarternary ammonium group. Among the possible co-monomers, vinylidene chloride is mentioned but not employed.
U.S. Pat. No. 4,100,340 (Waldmann et al.) describes textile finishes which are copolymers of a perfluoroalkylethyl acrylate, a higher alkyl acrylate, vinylidene chloride and acroylbutylurethane in weight ratios of 1/0.22-0.39/0.45-0.85/0.01-0.14.
U.S. Pat. No. 4,582,882 (Lynn et al.) describes fluorinated paper sizes which are copolymers of 60-80% by weight of a perfluoroalkylalkyl acrylate; 1-30% of a halogenated alkyl or alkoxyalkyl acrylate, 1-15% of glycidyl methacrylate, 1-6% of a (meth)acrylate bearing a quaternary ammonium group and 0-20% vinylidene chloride.
U.S. Pat. No. 4,742,140 (Greenwood et al.) describes copolymers for use on textiles which comprise 40-75% by weight of a perfluoroalkylethyl acrylate, 10-35% of vinylidene chloride and 10-25% of a C
2
-C
18
alkyl-(meth)acrylate. An earlier Japanese Patent Application No. 50-54729 (Asahi Glass Co.) discloses similar polymers, but specifies 35-60% of vinylidene chloride and 0.5-5% of N-methylol (meth)acrylamide.
It has now been unexpectedly found that copolymers comprising a perfluoroalkylalkyl (meth)acrylate, a secondary- or tertiary-aminoalkyl(meth)acrylate, vinylidene chloride and up to 10% of copolymerizable nonfluorinated vinyl monomers give superior oil and water resistance to paper products, especially when applied as internal sizes. None of the cited prior art discloses the use of vinylidene chloride and a secondary- or tertiary-aminoalkyl(meth)acrylate as sole comonomers with a perfluoroalkylalkyl (meth)acrylate.
It has further been discovered that the copolymers of the present invention impart excellent soil-release and anti-soiling properties to textile fibers.
DETAILED DISCLOSURE
The present invention concerns compounds which act either as internally or externally applied oil- and grease proofing paper sizes or as soil-release agents for textile fibers. The preferred compounds are copolymers comprising monomers copolymerized in the following percentages by weight, relative to the total weight of the copolymers:
a) 45-90% by weight of a monomer of formula
R
F
—W—X—C(═O)—C(R
1
)═CH
2
(1),
wherein
R
F
is a straight or branched-chain perfluoroalkyl group containing 4 to 20 carbon atoms,
R
1
is H or CH
3
,
X is O, S or N(R
2
), wherein R
2
is H or an alkyl group with 1 to 4 carbon atoms,
W is alkylene with 1 to 15 carbon atoms, hydroxyalkylene with 3 to 15 carbon atoms,
—(C
n
H
2n
)(O C
m
H
2m
)
q
—, —SO
2
NR
2
—(C
n
H
2n
)— or —CONR
2
—(C
n
H
2n
)—, wherein n is 1 to 12, m is 2 to 4,
q is 1 to 10 and R
2
is as defined above;
b) 5-30% by weight of a monomer of formula
(R
2
)
2
N—(CH
2
)
k
—X
1
—C(═O)—C(R
1
)═CH
2
(2),
in which the nitrogen atom is partially or completely quaternized or in the form of a salt and X
1
is O or N(R
2
) and wherein
R
1
and R
2
are defined as above, each R
2
is the same or different, and k is 2 to 4;
c) 1-20% by weight of vinylidene chloride, and, optionally,
d) 0-10% by weight of a copolymerizable nonfluorinated vinyl monomer.
Preferably d) is zero.
Especially referred are copolymers in which the monomers are copolymerized in the following percentages by weight, relative to the total weight of the copolymers: a), 70-85% by weight; b), 3-12% by weight; c), 10-20% by weight, and d), zero.
In preferred copolymers, R
F
is a straight chain perfluoroalkyl group with 6-16 carbon atoms, X and X
1
are oxygen and W is an alkylene with 1 to 12 carbon atoms, or X is N(R
2
), X
1
is oxygen and W is —SO
2
NR
2
—(C
n
H
2n
)—, wherein R
2
and n are as defined above.
The most preferred copolymers are those in which R
F
is a straight chain perfluoroalkyl group with 6 to 16 carbon atoms, R
1
is hydrogen, X and X
1
are oxygen and W is —CH
2
CH
2
—.
A mixture of compounds of the formula (1) with 6 to 16 carbon atoms is advantageously employed to prepare the inventive copolymers. The most especially preferred monomer of the formula (1) to prepare the polymers of this invention is an R
F
-ethyl acrylate which is available from Clariant Chemical Corp. under the trade name FLOWET AC-812. It has a chain-length distribution of R
F
-chains of 13±2% C
6
F
13
, 48±2% C
8
F
17
, 23±2% C
10
F
21
and 1.6% C
12
F
25
or higher.
Preferred compounds of the formula (2) are N,N-dimethylaminoethyl (meth)acrylate; N,N-diethylaminoethyl (meth)acrylate; N,N-dimethylaminopropyl methacrylamide and N-tert. butylaminoethyl methacrylate and their salts.
Useful as co-monomers (d) are a large number of commerci
Ciba Specialty Chemicals Corporation
Mansfield Kevin T.
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