Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2002-05-30
2004-02-17
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S533000, C524S544000, C524S545000, C526S245000, C526S247000
Reexamination Certificate
active
06693144
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a graft copolymer, and a solvent-based water- and oil-repellent composition comprising the same.
RELATED ART
In view of regulation of fluorocarbons and environmental problems, solvents for water- and oil-repellent products, for example, halogen solvents such as R113 are being replaced by petroleum solvents. However, problems such as solidification or precipitation of products at low temperature arise even if the solvent is merely replaced. When the water- and oil-repellent product is diluted with the petroleum solvent having low solubility such as solvent having a small content of an aromatic compound, problems such as precipitation or concentration distribution arise.
When the fluorine concentration in an active component of the water- and oil-repellent agent is reduced to impart high product stability and high dilution stability to the water- and oil-repellent agent composition, the water- and oil-repellency is lowered.
Japanese Patent Kokoku Publication No. 50082/1986 discloses a water- and oil-repellent agent comprising a graft copolymer obtained by the graft copolymerization which utilizes the reactivity of an OH group. However, the graft copolymer is insufficient in water repellency because a hydroxyl group remains in the polymer.
Japanese Patent Kokai Publication No. 228534/1994 discloses a water- and oil-repellent agent comprising a fluorine-containing graft copolymer. However, the fluorine-containing graft copolymer is insufficient in solubility in the petroleum solvent because a repeating unit derived from a fluorine-containing monomer is contained in only a trunk polymer of the graft copolymer.
Japanese Patent Kokai Publication No. 95516/1997 discloses a water- and oil-repellent agent comprising a copolymer of a perfluoroalkyl vinyl monomer containing an acid anhydride. However, the solubility is insufficient unless a fluorine content is low, because the copolymer is not a graft polymer.
SUMMARY OF THE INVENTION
An object of the present invention is to give a water- and oil-repellent agent having the improved water- repellency (particularly, to cellulose fibers such as cotton fibers) and the improved solubility in a petroleum solvent (particularly nonaromatic solvents).
The present inventors discovered that both of the improved solubility of a water- and oil-repellent agent in petroleum solvents due to high solubility possessed by an acid anhydride structure and the improved water repellency caused by the improved adhesion to fibers due to polarity possessed by the acid anhydride structure (interaction between the acid anhydride structure and a hydroxyl group of cellulose fibers such as cotton fibers) can be imparted to a solvent-based water- and oil-repellent agent by introducing the acid anhydride structure into a graft copolymer.
The present invention provides a solvent-based water- and oil-repellent agent composition comprising a graft copolymer comprising a repeating unit derived from a vinyl monomer having a perfluoroalkyl group and a repeating unit derived from a polymerizable cyclic acid anhydride, and an organic solvent.
The present invention also provides a graft copolymer comprising a repeating unit derived from a vinyl monomer having a perfluoroalkyl group and a repeating unit derived from a polymerizable cyclic acid anhydride.
DETAILED EXPLANATION OF THE INVENTION
For example, the graft copolymer has a trunk polymer comprising:
(A) optionally present, a vinyl monomer having a perfluoroalkyl group,
(B) optionally present, a fluorine-free vinyl monomer,
(C) optionally present, a polymerizable cyclic acid anhydride, and
(D) a vinyl monomer having a group bonding to a branch polymer, and a branch polymer comprising:
(E) optionally present, a vinyl monomer having a perfluoroalkyl group,
(F) optionally present, a fluorine-free vinyl monomer, and
(G) optionally present, a polymerizable cyclic acid anhydride, wherein at least one of the components (A) and (E) is an essential component, and at least one of the components
(C) and (G) is an essential component.
Examples of the graft copolymer include the followings:
(i) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) and the polymerizable cyclic acid anhydride (C) and a branch polymer comprising the vinyl monomer having the perfluoroalkyl group (E) and the polymerizable cyclic acid anhydride (G);
(ii) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) but no polymerizable cyclic acid anhydride (C) and a branch polymer comprising the polymerizable cyclic acid anhydride (G) but no vinyl monomer having the perfluoroalkyl group (E);
(iii) a graft copolymer having a trunk polymer comprising the polymerizable cyclic acid anhydride (C) but no vinyl monomer having the perfluoroalkyl group (A) and a branch polymer comprising the vinyl monomer having the perfluoroalkyl group (E) but no polymerizable cyclic acid anhydride (G);
(iv) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) and the polymerizable cyclic acid anhydride (C) and a branch polymer comprising the vinyl monomer having the perfluoroalkyl group (E) but no polymerizable cyclic acid anhydride (G);
(v) a graft copolymer having a trunk polymer comprising the polymerizable cyclic acid anhydride (C) but no vinyl monomer having the perfluoroalkyl group (A) and a branch polymer comprising the vinyl monomer having the perfluoroalkyl group (E) and the polymerizable cyclic acid anhydride (G);
(vi) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) but no polymerizable cyclic acid anhydride (C) and a branch polymer comprising the vinyl monomer having the perfluoroalkyl group (E) and the polymerizable cyclic acid anhydride (G);
(vii) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) and the polymerizable cyclic acid anhydride (C) and a branch polymer comprising the polymerizable cyclic acid anhydride (G) but no vinyl monomer having the perfluoroalkyl group (E);
(viii) a graft copolymer having a trunk polymer comprising the vinyl monomer having the perfluoroalkyl group (A) and the polymerizable cyclic acid anhydride (C) and a branch polymer comprising the fluorine-free monomer (F) but no polymerizable cyclic acid anhydride (G) and no vinyl monomer having the perfluoroalkyl group (E); and
(ix) a graft copolymer having a trunk polymer comprising the fluorine-free vinyl monomer (B) but no vinyl monomer having the perfluoroalkyl group (A) and no polymerizable cyclic acid anhydride (C) and a branch polymer comprising the polymerizable cyclic acid anhydride (G) and the vinyl monomer having the perfluoroalkyl group (E).
The perfluoroalkyl group-containing vinyl monomers (A) and (D), which constitutes the trunk polymer and/or branch polymer, may be a (meth)acrylate having a perfluoroalkyl group.
The perfluoroalkyl group-containing (meth)acrylate may be represented by the following general formula:
Rf—A
2
—OCOCR
18
═CH
2
wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R
18
is hydrogen or a methyl group, and A
2
is a divalent organic group.
Examples of the perfluoroalkyl group-containing (meth)acrylate include:
Rf—(CH
2
)
n
OCOCR
3
═CH
2
Rf—O—Ar—CH
2
OCOCR
3
═CH
2
wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, R
1
is hydrogen or an alkyl group having 1 to 10 carbon atoms, R
2
is an alkylene group having 1 to 10 carbon atoms, R
3
is hydrogen or a methyl group, Ar is arylene group which optionally has a substituent group, and n is an integer of 1 to 10.
Specific examples of the perfluoroalkyl group-containing (meth)acrylate include the following.
CF
3
(CF
2
)
7
(CH
2
)OCOCH═CH
2
,
CF
3
(CF
2
)
6
(CH
2
)OCOC(CH
3
)═CH
2
,
(CF
3
)
2
CF(CF
2
)
6
(CH
2
)
2
OCOCH═CH
2
,
CF
3
(CF
2
)
7
(CH
2
)
2
OCOC(CH
3
)═CH
2
,
CF
3
(CF
2
)
7
(CH
2
)
2
OCOCH═CH
2
,
CF
3
(CF
2
)
7
SO
Hanazawa Makoto
Hayashi Kazunori
Yamaguchi Fumihiko
Daikin Industries Ltd.
Hu Henry S.
Sughrue & Mion, PLLC
Wu David W.
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