Drug – bio-affecting and body treating compositions – Effervescent or pressurized fluid containing – Organic pressurized fluid
Reexamination Certificate
1998-12-09
2001-02-27
Page, Thurman K. (Department: 1615)
Drug, bio-affecting and body treating compositions
Effervescent or pressurized fluid containing
Organic pressurized fluid
C424S040000
Reexamination Certificate
active
06193955
ABSTRACT:
This application is the national phase under 35 U.S.C. §371 of prior PCT International Application Ser. No. PCT/JP97/01823 which has an International filing date of May 29, 1997 which designated the United States of America.
1. Field of the Invention
The present invention relates to a novel copolymer, a process for producing the same, and use thereof.
2. Related Arts
Heretofore, various water- and oil-repellent agents have been proposed.
Japanese Laid-Open Patent Publication No. 507438/1994 discloses a water- and oil-repellent agent comprising a polymer or copolymer obtained by polymerization of a (meth)acrylate ester reaction product of a diisocyanate, a perfluoro compound or an epichlorohydrin adduct, and a compound containing three hydroxyl groups. However, its water-repellency is insufficient.
Japanese Laid-Open Patent Publication Nos. 330027/1994 and 313166/1994 disclose a water- and oil-repellent base material prepared by polymerization or copolymerization of polymerizable &agr;, &bgr;-mono-ethylenically unsaturated monomers having at least two monovalent groups having perfluoroalkyl groups and having a skeleton in which all the monovalent groups are bound to the same carbon atom. However, its water- and oil-repellency is insufficient.
Japanese Laid-Open Patent Publication No. 132850/1987 discloses a water- and oil-repellent made of a polymer comprising a monomer prepared by reacting toluene-2,4-diisocyanate, a compound having a perfluoroalkyl group and an acrylate ester having a hydroxyl group. However, its water-repellency is insuffient.
Japanese Laid-Open Patent Publication No. 214325/1993 discloses a water- and oil-repellent agent composition containing a blocked polyisocyanate compound and a copolymer obtained by copolymerization of at least two monomers comprising an acrylate or methacrylate containing a polyfluoroalkyl group and a polyacrylate or polymethacrylate having an urethane linkage. However, this water- and oil-repellent agent composition is poor in emulsion stability and insoluble in an alcohol solvent.
Conventional water- and oil-repellent polymers are poor in solubility in an alcohol solvent. Further, fluorine-containing urethane compounds having relatively high solubility in the alcohol solvent are poor in water-repellent performance.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a copolymer giving excellent water- and oil-repellency and being dissolved in an alcohol solvent.
The present invention provides a copolymer comprising:
(I) a repeating unit derived from a monomer having a fluorine atom; and
(II) a repeating unit derived from a fluorine-free monomer having at least one urethane or urea linkage and having one carbon—carbon double bond.
The present invention also provides a treatment agent comprising said copolymer and a solvent.
DETAILED DESCRIPTION OF THE INVENTION
The monomer (I) having a fluorine atom may be (meth)acrylate having a C
3
to C
21
polyfluoroalkyl group. The monomer (I) may be a compound represented by the formula:
wherein R
11
is a hydrogen atom or a methyl group, and R
f
is a C
3
to C
21
fluoroalkyl group wherein a nitrogen atom, a sulfonyl group and/or an amide group may be present in a C—C bond.
Examples of the monomer (I) having a fluorine atom are as follows:
CF
3
(CF
2
)
4
CH
2
OCOC(CH
3
)═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
)
2
CF(CF
2
)
4
(CH
2
)
2
OCOCH═CH
2
CF
3
(CF
2
)
7
SO
2
N(C
3
H
7
)(CH
2
)
2
OCOCH═CH
2
CH
3
(CF
2
)
7
(CH
2
)
4
OCOCH═CH
2
CF
3
(CF
2
)
7
SO
2
N(CH
3
)(CH
2
)
2
OCOC(CH
3
)═CH
2
CF
3
(CF
2
)
7
SO
2
N(C
2
H
5
)(CH
2
)
2
OCOCH═CH
2
CF
3
(CF
2
)
7
CONH(CH
2
)
2
OCOCH═CH
2
(CH
3
)
2
CF(CF
2
)
6
(CH
2
)
3
OCOCH═CH
2
(CF
3
)
2
CF(CF
2
)
6
CH
2
CH(OCOCH
3
)CH
2
OCOC(CH
3
)═CH
2
(CF
3
)
2
CF(CF
2
)
6
CH
2
CH(OH)CH
2
OCOCH═CH
2
CF
3
(CF
2
)
9
(CH
2
)
2
OCOCH═CH
2
CF
3
(CF
2
)
9
(CH
2
)
2
OCOC(CH
3
)═CH
2
CF
3
(CF
2
)
9
CONH(CH
2
)
2
OCOC(CH
3
)═CH
2
(CF
2
Cl)(CF
3
)CF(CF
2
)
6
CONH(CH
2
)
2
OCOCH═CH
2
H (CF
2
)
10
CH
2
OCOCH═CH
2
CF
2
Cl(CF
2
)
10
CH
2
OCOC(CH
3
)═CH
2
The monomer (II) being free of a fluorine atom, having at least one urethane or urea bond and having one carbon—carbon double bond can be obtained by reacting:
(A) a compound having at least two isocyanate groups;
(B) a compound having one carbon—carbon double bond and at least one hydroxyl group or amino group; and
(C) a compound having one hydroxyl group or amino group.
Examples of the compound (A) are as follows:
The compound (A) is preferably diisocyanate. However, triisocyanate and polyisocyanate can also be used in the reaction.
For example, a trimer of diisocyanate, polymeric MDI (diphenylmethane diisocyanate), and adducts between a polyhydric alcohol (such as trimethylolpropane, trimethylolethane and glycerin) and a diisocyanate can also be used in the reaction.
Examples of the triisocyanate and polyisocyanate are as follows:
The compound (B) may be a compound represented by e.g. the formulae:
In the formulae, R
1
is a hydrogen atom or a methyl group. X is as follows:
In the formulae, m and n are numbers of 1 to 300.
The compound (C) may be a compound represented by e.g. the formula:
R
2
—OH
R
2
—NH
2
or
R
2
—NH—R
3
.
In the formulae, R
2
and R
3
are the same or different and represent a C
1
-C
22
alkyl group which may contain a heteroatom, an aromatic group and/or an alicyclic moiety. The R
2
and R
3
groups are preferably C
8
H
17
, C
17
H
35
, C
4
H
9
and cyclohexyl.
Examples of the compound (C) include butyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, cyclohexyl alcohol, 2-ethylhexyl amine, and stearyl amine.
The compounds (A), (B) and (C) may be reacted in 1 mole of (A) and 1 mole each of (B) and (C) when (A) is diisocyanate or in 1 mole of (A), 1 mole of (B) and 2 moles of (C) when (A) is triisocyanate.
In addition to the monomers (I) and (II), other copolymerizable monomers may be used in the present invention.
The other copolymerizable monomers may be (meth)acrylate esters. Examples of the (meth)acrylate esters include 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, poly(oxyalkylene) (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, isocyanatoethyl (meth)acrylate, aziridinyl (meth)acrylate, polysiloxane-containing (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and acetoacetoxyethyl (meth)acrylate. If N,N-dimethylaminoethyl (meth)acrylate is used, the water repellency of cotton is improved.
Additional examples of the other copolymerizable monomers include ethylene, butadiene, isoprene, chloroprene, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, &agr;-methylstyrene, p-methylstyrene, acrylic acid, methacrylic acid, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol(meth)acrylamide, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, maleic anhydride, N-vinylcarbazole, and acrylonitrile.
A weight ratio of the monomer (I) to the monomer (II) in the copolymer of the present invention is preferably from 5:95 to 95:5, more preferably from 20:80 to 95:5. The amount of the other copolymerizable monomers is at most 90% by weight of the copolymer, for example, from 5 to 90% by weight. The molecular weight of the copolymer may be from 500 to 1,000,000.
The copolymer can be produced by a solution polymerization, an emulsion polymerization or a suspension polymerization.
The copolymer of the present invention can be produced by a solution polymerization in an organic solvent. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; alcohols such as ethanol, isopropanol, butanol, 1,3-butanediol and 1,5-pentanediol; halogenated hydrocarbons such as perchloroethylene, Trichlene, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1
Enomoto Takashi
Hayashi Kazunori
Yamana Masayuki
Birch & Stewart Kolasch & Birch, LLP
Daikin Industries Ltd.
Page Thurman K.
Tran S.
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