Indian Patents
Title of Invention

"COPOLYMER, METHOD FOR ITS PRODUCTION, AND WATER/OIL REPELLENT COMPOSITION"
Abstract To provide a copolymer which is capable of providing an article surface with a dynamic water repellency and which has extremely excellent washing durability of water repellency and oil repellency, while placing little burden on the environment; a method for its production; and a water/oil repellent composition. A copolymer comprising structural units of the monomer (a) and structural units of the monomer (b), wherein the total of the content of structural units based on the monomer (a) and the content of structural units based on the monomer (b) is at least 85 mass% of all structural units (100 mass%), and the molar ratio ((a)/(b)) of the content of structural units based on the monomer (a) to the content of structural units based on the monomer (b) is from 0.12 to 3; and a water/oil repellent composition containing such a copolymer. Momomer (a): a compound represented by (Z-Y)n-X, wherein Z is a C1-6 polyfluoroalkyl group or the like, Y is a bivalent organic group or a single bond, n is 1 or 2, and when n is 1, and X is a polymerizable unsaturated group. Monomer (b): a halogenated olefin.
Full Text 1
DESCRIPTION
TITLE OF THE INVENTION: COPOLYMER, METHOD FOR ITS PRODUCTION, AND
WATER/OIL REPELLENT COMPOSITION
^TECHNICAL FIELD
The present invention relates to a copolymer, a method for its production and a
water/oil repellent composition containing such a copolymer.
BACKGROUND ART
As a method for imparting water and oil repellency to the surface of an article
(such as a fiber product), a method is known which comprises treating the article with a
water/oil repellent composition made of an emulsion wherein a copolymer having
structural units based on a monomer having a polyfluoroalkyi group (hereinafter a
polyfluoroalkyi group will be referred to as an "R' group") having at least 8 carbon
atoms, is dispersed in a medium.
However, recently, EPA (United States Environmental Protection Agency) has
pointed out that a compound having a perfluoroalkyi group (hereinafter a perfluoroalkyi
group will be referred to as an "R' group") having at least 8 carbon atoms is
decomposed in an environment or a living body and its decomposition product is
accumulated there, thus bringing about a high environmental burden. Accordingly a
copolymer for a water/oil repellent composition having structural units based on a
monomer having an R' group having at most 6 carbon atoms and having structural
units based on a monomer having an R* group having at least 8 carbon atoms reduced
as far as possible is desired.
As a water/oil repellent composition containing such a copolymer, the following
water/oil repellent composition has, for example, been proposed.
A water/oil repellent composition containing, as an essential component, a
copolymer composed substantially of structural units based on the following monomer
(a) and structural units based on the following monomer (b):
Monomer (a): a monomer having an R' group having at most 6 carbon atoms,
etc.
Monomer (b): a (meth)acrylate having an alkyl group having at least 15 carbon
atoms, etc.
However, an article treated with such a water/oil repellent composition is
inadequate in water repellency against water fallen from a high altitude (rainfall)
(hereinafter referred to as dynamic water repellency) and in water repellency after
drying without positively heating after washing (hereinafter referred to as water
repellency after air drying).
PRIOR ART DOCUMENT
PATENT DOCUMENT
Patent Document 1: WO02/083809
SUMMARY OF THE INVENTION
OBJECT TO BE ACCOMPLISHED BY THE INVENTION
The present invention is to provide a copolymer which is capable of imparting
dynamic water repellency to the surface of an article and at the same time, is excellent
in water repellency and oil repellency and which presents little environmental burden; a
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method for its production; and a water/oil repellent composition.
MEANS TO ACCOMPLISH THE OBJECT
The copolymer of the present invention is a copolymer comprising structural units
iBf the following monomer (a) and structural units of the following monomer (b), wherein
the total of the content of structural units based on the monomer (a) and the content of
structural units based on the monomer (b) is at least 85 mass% of all structural units
(100 mass%), and the molar ratio ((a)/(b)) of the content of structural units based on
the monomer (a) to the content of structural units based on the monomer (b) is from
0.12 to 3:
Momomer (a): a compound represented by the following formula (1):
(Z-Y)n-X (1)
wherein Z is a Ci-e polyfluoroalkyi group or a group represented by the following
formula (2), Y is a bivalent organic group or a single bond, n is 1 or 2, and when n is 1,
X is any one of groups represented by the following formulae (3-1) to (3-5) and when n
is 2, X is any one of groups represented by the following formulae (4-1) to (4-4):
CiF2i+iO(CFX^CF20)jCFX2- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0 to 10, and each of X^ and
X^ is a fluorine atom or a trifluoromethyl group,
-CR=CH2 (3-1)
-C(0)0CR=CH2 (3-2)
-0C(0)CR=CH2 (3-3)
-OCH2-(p-CR=CH2 (3-4)
-0CH=CH2 (3-5)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and cp is a
phenylene group,
-CH[-(CH2)mCR=CH2]- (4-1)
-CH[-(CH2)mC(0)OCR=CH2]- (4-2)
-CH[-(CH2)mOC(0)CR=CH2]- (4-3)
-OC(0)CH=CHC(0)0- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an Integer
of from 0 to 4,
Monomer (b): a halogenated olefin.
The copolymer of the present invention is preferably such that the monomer (a)
is a compound represented by the formula (1) wherein Z is a C4-6 R"" group.
The copolymer of the present invention preferably further has structural units
based on the following monomer (c):
Monomer (c): a monomer having a cross-linkable functional group without having
a polyfluoroalkyi group.
The copolymer of the present invention preferably does not have structural units
based on the following monomer (d1):
Monomer (d1): a (meth)acrylate having an alkyl group having at least 18 carbon
atoms.
The copolymer of the present invention is preferably such that based on all
monomers (100 mass%), structural units based on the monomer (a) are from 50 to
98.5 mass%, and structural units based on the monomer (b) are from 1 to 40 mass%.
The method for producing a copolymer of the present invention is a method for
producing a copolymer, which comprises polymerizing a monomer mixture comprising
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the above monomer (a) and the above monomer (b) in a medium in the presence of a
surfactant and a polymerization initiator, wherein the total of the content of the
monomer (a) and the content of the monomer (b) is at least 85 mass% of the monomer
^mixture (100 mass%), and in the monomer mixture, the molar ratio ((a)/(b)) of the
content of the monomer (a) to the content of the monomer (b) is from 0.12 to 3:
The above monomer mixture preferably further contains the above mentioned
monomer (c).
The above monomer mixture preferably does not contain the above-mentioned
monomer (d1).
The water/oil repellent composition of the present invention is one comprising the
copolymer of the present invention and a medium.
ADVANTAGEOUS EFFECTS OF THE INVENTION
The copolymer of the present invention is capable of imparting dynamic water
repellency to the surface of an article and at the same time, is excellent in water
repellency and oil repellency, and it presents little environmental burden.
According to the method for producing a copolymer of the present invention, it is
possible to produce a copolymer which is capable of imparting dynamic water
repellency to the surface of an article and at the same time, is excellent in water
repellency and oil repellency and which presents little environmental burden.
The water/oil repellent composition of the present invention is capable of
imparting dynamic water repellency to the surface of an article and at the same time, is
excellent in water repellency and oil repellency, and it presents little environmental
burden.
BEST MODE FOR CARRYING OUT THE INVENTION
In this specification, a compound represented by the formula (1) will be referred
to as a compound (1). Compounds represented by other formulae will be referred to
in the same manner And, in this specification, a group represented by the formula (2)
will be referred to as a group (2). Groups represented by other formulae will be
referred to in the same manner. And, a (meth)acrylate in this specification means an
acrylate or a methacrylate. And, a monomer in this specification means a compound
having a polymerizable unsaturated group. Further, in this specification, an R^ group
is an alkyl group having some or all of its hydrogen atoms substituted by fluorine atoms,
and an R*" group is an alkyl group having all of its hydrogen atoms substituted by
fluorine atoms.

The copolymer of the present invention has, as essential structural units,
structural units based on a monomer (a) and structural units based on a monomer (b)
and has, as the case requires, structural units based on a monomer (c) and a
monomer (d).
(Monomer (a))
The monomer (a) is a compound (1).
(Z-Y)nX (1)
Z is a Ci-6 R' group (provided that the R' group may contain an etheric oxygen
atom) or a group (2).
CiF2i+iO(CFX^CF20)jCFX2- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0 to 10, and each of X^ and
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X^ which are independent of each other, is a fluorine atom or a trifluoromethyl group.
The R' group is preferably an R*" group. The R^ group may be linear or
branched, preferably linear.
Z may be the following groups.
F(CF2)4-,
F(CF2)5-,
F(CF2)6-,
(CF3)2CF(CF2)2-.
CkF2k.iO[CF(CF3)CF20]h-CF(CF3)-,etc.
wherein k is an integer of from 1 to 6, and h is an integer of from 0 to 10.
Y is an bivalent organic group or a single bond. Here, in the formula (1), the
boundary between Z and Y is determined so that the number of carbon atoms in Z
becomes smallest. The bivalent organic group is preferably an alkylene group. The
alkylene group may be linear or branched. The alkylene group may have -0-, -NH-,
-CO-, -S-, -SO2-, -CD^=CD^- (wherein each of D^ and D^ which are independent of
each other, is a hydrogen atom or a methyl group), etc.
Y may be the following groups.
-CH2-,
-CH2CH2-,
-(CH2)3-,
-CH2CH2CH(CH3)-,
-CH=CH-CH2-,
-S-CH2CH2-,
-CH2CH2-S-CH2CH2-,
-CH2CH2-SO2-CH2CH2-, etc.
n is 1 or 2.
When n is 1, X is any one of groups (3-1) to (3-5), and when n is 2, X is any one
of groups (4-1) to (4-4).
-CR=CH2 (3-1)
-C(0)0CR=CH2 (3-2)
-0C(0)CR=CH2 (3-3)
-OCH2-(p-CR=CH2 (3-4)
-0CH=CH2 (3-5)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and (p is a
phenylene group.
-CH[-(CH2)mCR=CH2]- (4-1)
-CH[-(CH2)mC(0)OCR=CH2]- (4-2)
-CH[-(CH2)mOC(0)CR=CH2]- (4-3)
-OC(0)CH=CHC(0)0- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer
of from 0 to 4.
The compound (1) is preferably a (meth)acrylate having a C4^ R"" group from the
viewpoint of the polymerizability with other monomers, the flexibility of a film of the
copolymer, the adhesion of the copolymer to an article, the solubility in a medium, the
efficiency of emulsion polymerization, etc.
The compound (1) is preferably a compound wherein Z is a C4.6 R"" group, Y is a
Ci^ alkylene group, n is 1, and X is the group (3-3).
(Monomer (b))
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The monomer (b) is a halogenated olefin. As the copolymer has structural units
based on the monomer (b), the strength of a coating film made of the copolymer of the
present invention is improved, and the adhesion property of the coating film made of
vthe copolymer of the present invention to a substrate is improved.
The halogenated olefin is preferably a chlorinated olefin or a fluorinated olefin,
and specifically, it may be vinyl chloride, vinylidene chloride, tetrafluoroethylene or
vinylidene fluoride. When the interaction with the substrate is taken into consideration,
vinyl chloride or vinylidene chloride is particularly preferred. Especially, it is preferred
to combine vinylidene chloride with the monomer (a), whereby the film-forming
property will be improved, and it is possible to impart sufficient water and oil repellency
to a substrate even by processing at a low temperature. Here, processing at a low
temperature means a step of drying the substrate at a temperature of at most 160°C to
form a coating film on the substrate.
(Monomer (c))
The monomer (c) is a monomer having a crosslinkable functional group without
having an R' group.
As the copolymer has structural units based on the monomer (c), the durability is
further improved.
The crosslinkable functional group is preferably a functional group having at least
one bond selected from a covalent bond, an ionic bond and a hydrogen bond, or a
functional group capable of forming a crosslinked structure by an interacfion with such
a bond.
Such a functional group is preferably an isocyanate group, a blocked isocyanate
group, an alkoxysilyl group, an amino group, an alkoxymethylamide group, a silanol
group, an ammonium group, an amide group, an epoxy group, a hydroxy group, an
oxazoline group, a carboxy group, an alkenyl group, a sulfonic acid group or the like,
particularly preferably a hydroxy group, a blocked isocyanate group, an amino group or
an epoxy group.
The monomer (c) is preferably a (meth)acrylate, a (meth)acrylamide, a vinyl ether
or a vinyl ester.
The monomer (c) may be the following compounds:
2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-
isocyanatobutyl (meth)acrylate, a 2-butanone oxime adduct of 2-isocyanatoethyl
(meth)acrylate, a pyrazole adduct of 2-isocyanatoethyl (meth)acrylate, a 3,5-
dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, a 3-methylpyrazole
adduct of 2-isocyanatoethyl (meth)acrylate, an £-caprolactam adduct of 2-
isocyanatoethyl (meth)acrylate, a 2-butanone oxime adduct of 3-isocyanatopropyl
(meth)acrylate, and a pyrazole adduct of 3-isocyanatopropyl (meth)acrylate;
a 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate, a 3-
methylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate, an £-caprolactam adduct
of 3-isocyanatopropyl (meth)acrylate, a 2-butanone oxime adduct of 4-isocyanatobutyl
(meth)acrylate, a pyrazole adduct of 4-isocyanatobutyl (meth)acrylate, a 3,5-
dimethylpyrazole adduct of 4-isocyanatobutyl (meth)acrylate, a 3-methylpyrazole
adduct of 4-isocyanatobutyl (meth)acrylate, and an £-caprolactam adduct of 4-
isocyanatobutyl (meth)acrylate;
methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, butoxymethyl
(meth)acrylamide, diacetone acrylamide, y-methacryloyloxypropyltrimethoxysilane,
trimethoxyvinylsilane, vinyltrimethoxysilane, dimethylaminoethyl (meth)acrylate.
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diethylaminoethyl (meth)acrylate, dimethyiaminopropy! (meth)acrylate,
(meth)acryloylmorpholine, (meth)acryloyloxyethyltrimethylammonium chloride,
(meth)acryloyloxypropyltrimethylammonium chloride,
Umeth)acrylamideethyltrimethylammonium chloride, and
(meth)acrylamidepropyltrimethylammonium chloride;
t-butyl(meth)acrylamide sulfonic acid, (meth)acrylamide, Nmethyl(
meth)acrylamide, N-methylol(meth)acrylamide, Nbutoxymethyl(
meth)acrylamide, diacetone(meth)acrylamide, glycidyl (nneth)acrylate, 2-
hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, a polyoxyalkylene glycol
mono(meth)acrylate, (meth)acrylic acid, 2-(meth)acryloylxyethylsuccinic acid, 2-
(meth)acryloylxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate, allyl
(meth)acrylate, 2-vinyl-2-oxazoline, and a polycaprolactone ester of 2-vinyl-4-methyl-
(2-vinyloxazoline)hydroxyethyl (meth)acrylate; and
tri(meth)allyl isocyanurate (T(M)AIC, manufactured by Nippon Kasei Chemical
Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Chemical Co., Ltd.),
phenylglycidylethylacrylate tolylenediisocyanate (AT-600,manufactured by KYOEISHA
CHEMICAL Co., Ltd.), 3-(methylethylketoxime)isocyanatomethyl-3,5,5-
trimethylcyclohexyl(2-hydroxyethylmethacrylate)cyanate (TECHCOAT HE-6P,
manufactured by Kyoken Kasei), and a polycaprolactone ester of hydroxyethyl
(meth)acrylate (PLACCEL FA, FM series, manufactured by DAICEL CHEMICAL
INDUSTRIES, LTD.).
Monomer (c) is preferably N-methylol(meth)acrylamide, Nbutoxymethyl(
meth)acrylamide, 2-hydroxyethyl (meth)acrylate, a 4-hydroxybutyl
(meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, or a
polycaprolactone ester of hydroxyethyl (meth)acrylate (PLACCEL FA, FM series,
manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.).
Monomer (d):
The monomer (d) is a monomer other than the monomer (a), the monomer (b)
and the monomer (c).
The monomer (d) may be the following compounds:
Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl
(meth)methacrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl
(meth)acrylate, benzyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate,
cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl
acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate, lauryl (meth)acrylate, cetyl
(meth)acrylate, stearyl (meth)acrylate and behenyl (meth)acrylate;
vinyl acetate, vinyl propionate, butene, isoprene, butadiene, ethylene, propylene,
vinyl ethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene,
decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, (1,2-
diethoxycarbonyl)ethylene, (1,2-dipropoxycarbonyl)ethylene, methoxyethylene,
ethoxyethylene, butoxyethylene, 2-methoxypropylene, pentyloxyethylene,
cyclopentanoyloxyethylene, cyclopentylacetoxyethylene, styrene, a-methylstyrene, pmethylstyrene,
hexylstyrene, octylstyrene and nonylstyrene;
N,N-dimethyl(meth)acrylamide, a vinylalkyi ether, an alkyl halide vinyl ether, a
vinylalkyi ketone, aziridinylethyl (meth)acrylate, a 2-ethylhexylpolyoxyalkylene
(meth)acrylate and a polyoxyalkylene di(meth)acrylate; and
an alkyl crotonate, an alkyl maleate, an alkyl fumarate, an alkyl citraconate, an
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alkyl mesaconate, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, Nmethylmaleimide,
a (meth)acrylate having a silicone in its side chain, a (meth)acrylate
having an urethane bond, a (meth)acrylate having a polyoxy alkylene chain with a
terminal Ci^ alkyl group, an alkylene di(meth)acrylate, etc.
From the viewpoint of the dynamic water repellency and the durability of water
repellency, the copolymer of the present invention contains preferably not more than
15 mass%, more preferably not more than 10 mass%, of structural units based on the
following monomer (d1) among monomers (d), and particularly preferably it does not
have structural units based on the monomer (d1).
Monomer (d1): a (meth)acrylate having an alkyl group having at least 18 carbon
atoms.
The monomer (d1) may, for example, be stearyl (meth)acrylate or behenyl
(meth)acrylate.
The proportion of structural units based on the monomer (a) is preferably from 50
to 99 mass%, more preferably from 50 to 98.5 mass%, particularly preferably from 60
to 94 mass%, in all monomers (100 mass%) in view of the dynamic water repellency
and the water repellency after air drying.
The proportion of structural units based on the monomer (b) is preferably from 1
to 50 mass%, more preferably from 1 to 40 mass%, particularly preferably from 5 to 30
mass%, in all monomers (100 mass%) from the viewpoint of the dynamic water
repellency and the water repellency after air drying.
The total of the content of structural units based on the monomer (a) and the
content of structural units based on the monomer (b) is at least 85 mass%, preferably
at least 90 mass%, particularly preferably from 95 to 100 mass%, of all structural units
(100 mass%). By adjusting such a total to be at least 85 mass%, the copolymer can
be provided with both the dynamic water repellency and the water repellency after air
drying.
Further, the molar ratio ((a)/(b)) of the content of structural units based on the
monomer (a) to the content of structural units based on the monomer (b) is preferably
from 0.12 to 3, more preferably from 0.2 to 2.5, particularly preferably from 0.3 to 2.
When (a)/(b) is from 0.12 to 3, the adhesion to a substrate is sufficient, and the water
and oil repellency is high, and excellent durability can be obtained.
The proportion of structural units based on the monomer (c) is preferably from 0
to 10 mass% in all monomers (100 mass%), and from the viewpdint of the durability, it
is more preferably from 0.5 to 10 mass%, particularly preferably from 1 to 10 mass%.
The proportion of stmctural units based on the monomer (d) is preferably from 0
to 15 mass%, more preferably from 0 to 5 mass%, in all monomers (100 mass%).
The proportions of structural units based on the monomers in the present
invention are obtained from the NMR analysis and the elemental analysis. In a case
where they cannot be obtained from the NMR analysis and the elemental analysis,
they may be calculated on the basis of the amount of monomers charged at the time of
the preparation of the copolymer.
(Method for producing copolymer)
The copolymer of the present invention is produced by the following method.
A method which comprises polymerizing a monomer mixture comprising the
monomer (a) and the monomer (b) and, as the case requires, containing the monomer
(c) and the monomer (d), in a medium in the presence of a surfactant and a
polymerization initiator, to obtain a solution, dispersion or emulsion of a copolymer.
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The polymerization method may, for example, be a dispersion polymerization
method, an emulsion polymerization method, a suspension polymerization method,
etc., and an emulsion polymerization method is preferred. And, the method may be
Vsingle-stage polymerization or multistage polymerization.
The method for producing a copolymer of the present invention is preferably a
method which comprises emulsion-polymerizing a monomer mixture comprising the
monomer (a) and the monomer (b) and, as the case requires, containing the monomer
(c) and the monomer (d) in the presence of a surfactant and a polymerization initiator,
to obtain an emulsion of a copolymer.
With a view to improving the yield of the copolymer, it is preferred that a mixture
comprising the monomers, a surfactant and an aqueous medium is pre-emulsified
before the emulsion polymerization. For example, the mixture comprising the
monomers, a surfactant and an aqueous medium is mixed and dispersed by a
homomixer or a high-pressure emulsification equipment.
The medium may be the after-mentioned medium.
The surfactant may be the after-mentioned surfactant.
The amount of the surfactant to be added is preferably from 1 to 10 parts by
mass, per 100 parts by mass of the monomer mixture.
The polymerization initiator may, for example, be a thermal polymerization
initiator, an optical polymerization initiator, a radiation polymerization initiator, a radical
polymerization initiator or an ionic polymerization initiator, and is preferably a watersoluble
or oil-soluble radical polymerization initiator.
As the radical polymerization initiator, a common initiator such as an azo
polymerization initiator, a peroxide polymerization initiator, a redox polymerization
initiator or the like is used depending upon the polymerization temperature. As the
radical polymerization initiator, an azo compound is particularly preferred, and in a
case where polymerization is carried out in an aqueous medium, a salt of an azo
compound is more preferred. The polymerization temperature is preferably from 20 to
150°C.
The amount of the polymerization initiator to be added, is preferably from 0.1 to 5
parts by mass, more preferably from 0.1 to 3 parts by mass, per 100 parts by mass of
the monomer mixture.
At the time of polymerization of the monomer mixture, a molecular weightcontrolling
agent may be employed. The molecular weight controlling agent is
preferably an aromatic compound, a mercapto alcohol or a mercaptan, and an alkyl
mercaptan is particularly preferred. The molecular weight-controlling agent may, for
example, be mercaptoethanol, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl
mercaptan, stearyl mercaptan, a-methylstyrene dimer (CH2=C(Ph)CH2C(CH3)2Ph,
wherein Ph is a phenyl group).
The amount of the molecular weight-controlling agent to be added, is preferably
from 0.01 to 5 parts by mass, more preferably from 0.1 to 3 parts by mass, per 100
parts by mass of the monomer mixture.
Further, the monomer mixture may be polymerized in the presence of a
polyfunctional mercapto compound such as diethylene glycol bis(3-mercaptobutylate),
pentaerythritol tetrakis(3-mercaptobutylate), 2,4,6-trimercaptotriazine or 1,3,5-tris(3-
mercaptobutyloxyethyl)1,3,5-triazine-2,4,6(1 H,3H,5H)-trione.
The proportion of the monomer (a) is preferably from 50 to 99 mass%, more
preferably from 50 to 98.5 mass%, particularly preferably from 60 to 94 mass%, in the
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monomer mixture (100 mass%), from the viewpoint of the dynamic water repellency
and the water repellency after air drying.
The proportion of the monomer (b) is preferably from 1 to 50 mass%, more
\preferably from 1 to 40 mass%, particularly preferably from 5 to 30 mass%, in the
monomer mixture (100 mass%), from the viewpoint of the dynamic water repellency
and the water repellency after air drying.
The total of the content of the monomer (a) and the content of the monomer (b) is
at least 85 mass%, preferably at least 90 mass%, particularly preferably from 95 to 100
mass%, of the monomer mixture (100 mass%). By adjusting the total to be at least 85
mass%, the copolymer can be provided with both the dynamic water repellency and
the water repellency after air drying.
Further, the molar ratio ((a)/(b)) of the content of the monomer (a) to the content
of the monomer (b) is preferably from 0.12 to 3, more preferably from 0.2 to 2.5,
particularly preferably from 0.3 to 2. When (a)/(b) is from 0.12 to 3, the adhesion to a
substrate will be adequate, the water and oil repellency will be high, and excellent
durability will be obtained.
The proportion of the monomer (c) is preferably from 0 to 10 mass% in the
monomer mixture (100 mass%), and from the viewpoint of the durability, it is more
preferably from 0.5 to 10 mass%, particularly preferably from 1 to 10 mass%.
The proportion of the monomer (d) is preferably from 0 to 15 mass%, more
preferably from 0 to 5 mass%, in the monomer mixture (100 mass%).
The mass average molecular weight (Mw) of the copolymer of the present
invention is preferably from 1,000 to 1,000,000, particularly preferably from 3,000 to
1,000,000.
The mass average molecular weight (Mw) of the copolymer is a molecular weight
calculated as polystyrene measured by gel permeation chromatography (GPC).
As described above, the copolymer of the present invention comprises structural
units based on the monomer (a) and structural units based on the monomer (b),
wherein the total of the content of structural units based on the monomer (a) and the
content of structural units based on the monomer (b) is at least 85 mass% of all
structural units (100 mass%), whereby it is possible to impart sufficient dynamic water
repellency and water repellency after air drying to the surface of an article. Further,
the environmental burden is low, since it has no structural units based on a monomer
having an R*" group having at least 8 carbon atoms.

The water/oil repellent composition of the present invention comprises, as
essential components, the copolymer of the present invention and a medium, and as
the case requires, contains a surfactant and additives.
(Medium)
The medium may, for example, be water, an alcohol, a glycol, a glycol ether, a
halogen compound, a hydrocarbon, a ketone, an ester, an ether, a nitrogenous
compound, a sulfur compound, an inorganic solvent, or an organic acid. Among them,
at least one selected from the group consisting of water, an alcohol, a glycol, a glycol
ether and a glycol ester is preferred from the viewpoint of solubility and ease in
handling.
The alcohol may, for example, be methanol, ethanol, 1-propanol, 2-propanol, 1-
butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-
pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-
10
butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-
ethyl-1-butanol, 1-heptanol, 2-heptanol, or 3-heptanol.
The glycol or the glycol ether may, for example, be ethylene glycol, ethylene
glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl
ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether
acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol
monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether,
dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl
ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol
monomethyl ether, polypropylene glycol, or hexylene glycol.
The halogen compound may, for example, be a halogenated hydrocarbon, or a
halogenated ether.
The halogenated hydrocarbon may, for example, be a hydrochlorofluorocarbon, a
hydrofluorocarbon, or a hydrobromocarbon.
The halogenated ether may, for example, be a hydrofluoro ether.
The hydrofluoro ether may, for example, be a separated-type hydrofluoro ether or
a non-separated-type hydrofluoro ether. The separated-type hydrofluoro ether is a
compound wherein an R*" or perfluoroalkylene group, and an alkyl or alkylene group,
are connected via an etheric oxygen atom. The non-separated-type hydrofluoro ether
is a hydrofluoro ether having a partially fluorinated alkyl or alkylene group.
The hydrocarbon may, for example, be an aliphatic hydrocarbon, an alicyclic
hydrocarbon, or an aromatic hydrocarbon.
The aliphatic hydrocarbon may, for example, be pentane, 2-methylbutane, 3-
methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane,
2,2,4-trimethylpentane, 2,2,3-trimethylhexane, decane, undecane, dodecane,
2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, or hexadecane.
The alicyclic hydrocarbon may, for example, be cyclopentane,
methylcyclopentane, cyclohexane, methylcyclohexane, or ethyicyclohexane.
The aromatic hydrocarbon may, for example, be benzene, toluene, or xylene.
The ketone may, for example, be acetone, methyl ethyl ketone, 2-pentanone, 3-
pentanone, 2-hexanone, or methyl isobutyl ketone.
The ester may, for example, be methyl acetate, ethyl acetate, butyl acetate,
methyl propionate, methyl lactate, ethyl lactate, or pentyl lactate.
The ether may, for example, be diisopropyl ether, dioxane, or tetrahydrofuran.
The nitrogenous compound may, for example, be pyridine, N,Ndimethylformaldehyde,
N,N-dimethylacetamide, or N-methylpyrrolidone.
The sulfur compound may, for example, be dimethyl sulfoxide, or sulfolane.
The inorganic solvent may, for example, be liquid carbon dioxide. *
The organic acid may, for example, be acetic acid, propionic acid, malic acid, or
lactic acid.
One of such media may be used alone, or two or more of the them may be used
in combination as a mixture. When two or more of such media are used in
combination as a mixture, one of them is preferably water. By using a mixture of
media, control of solubility and dispersibility of the copolymer may be easy, and control
of permeability and wettability to an article and solvent drying speed at the time of
manufacture may be easy.
(Surfactant)
The surfactant may be a hydrocarbon surfactant or a fluorinated surfactant, and,
11
each of them may, for example, be an anionic surfactant, an nonlonic surfactant, a
cationic surfactant or an amphoteric surfactant.
From the viewpoint of dispersing stability, the surfactant is preferably a nonionic
^surfactant, a cationic surfactant, a combination of a nonionic surfactant and a cationic
surfactant, or an anionic surfactant alone, more preferably a combination of a nonlonic
surfactant and a cationic surfactant.
The mass ratio of a nonionic surfactant to a cationic surfactant (a nonionic
surfactant / a cationic surfactant) is preferably from 97/3 to 40/60.
In a specific combination of a nonionic surfactant and an cationic surfactant, their
total amount in the copolymer (100 mass%) can be adjusted to be at most 5 mass%,
whereby an adverse effect to the water repellency of an article can be reduced.
The nonlonic surfactant is preferably at least one member selected from the
group of surfactants s^ to s^.
Surfactants^:
Surfactant s^ is a polyoxyalkylene monoalkyi ether, a polyoxyalkylene
monoalkenyl ether, a polyoxyalkylene monoalkapolyenyl ether or a polyoxyalkylene
monopolyfluoroalkyi ether.
Surfactant s^ is preferably a polyoxyalkylene monoalkyi ether, a polyoxyalkylene
monoalkenyl ether or a polyoxyalkylene monopolyfluoroalkyi ether. As surfactant sone of such surfactants may be used alone, or two or more of them may be used in
combination.
An alkyl group, an alkenyl group, an alkapolyenyl group or a polyfluoroalkyi group
(hereinafter collectively referred to as an R^ group) preferably has from 4 to 26 carbon
atoms. The R^ group may have a straight chain structure or a branched structure.
The branched-structured R^ group is preferably a secondary alkyl group, a secondary
alkenyl group or a secondary alkapolyenyl group. Some or all of the hydrogen atoms
of the R^ group may be substituted by fluorine atoms.
Specific examples of the R® group include an octyl group, an dodecyl group, a
tetradecyl group, a hexadecyl group, a stearyl group (octadecyl group), a behenyl
group (docosyl group), an oleyl group (9-octadecenyl group), a heptadecylfluorooctyl
group, a tridecylfluorohexyle group, 1H,1H,2H,2H-tridecylfluorooctyl group, and a
1 H,1 H,2H,2H-nonafluorohexyl group.
A polyoxyalkylene (hereinafter referred to as POA) chain is preferably a
catenated chain consisting of two or more of polyoxyethylene (hereinafter referred to
as POE) chains and/or polyoxypropylene (hereinafter referred to as POP) chains.
The POA chain may consist of one type of POA chains or two or more types of POA
chains. When the POA chain consists of two or more types of POA chains, such POA
chains are preferably linked to form blocks.
Surfactant s^ is more preferably compound (s^^):
R^°0[CH2CH(CH3)0]s-(CH2CH20)rH (s^^)
wherein R^° is an alkyl group having at least 8 carbon atoms or an alkenyl group
having at least 8 carbon atoms, r is an integer of from 5 to 50, and s is an integer of
from 0 to 20. Some of hydrogen atoms of the R^°may be substituted by fluorine
atoms.
When r is at least 5, the surfactant is soluble in water and homogeneously
soluble in an aqueous medium, thus the water/oil repellent composition has good
permeability to an article. When r is at most 50, its hydrophilicity is suppressed and
water repellency will be good.
12
When s is at most 20, the surfactant is soluble in water and homogeneously
soluble in an aqueous medium, thus the water/oil repellent composition has good
permeability to an article.
, When r and s are at least 2, the POE chains and the POP chains are linked to
' form blocks.
R^° is preferably a straight chain or a branched chain.
r is preferably an integer of from 10 to 30.
s is preferably an integer of from 0 to 10.
The following compounds may be mentioned as examples of compound (s^^),
wherein the POE chains and the POP chains are linked in block form:
Ci8H370[CH2CH(CH3)0]2-(CH2CH20)3oH,
Ci 8H350-(CH2CH20)3oH,
Ci6H330[CH2CH(CH3)0]5-(CH2CH20)2oH,
Ci2H250[CH2CH(CH3)0]2-(CH2CH20)i5H,
(C8Hi7)(C6Hi3)CHO-(CH2CH20)i5H,
CioH2iO[CH2CH(CH3)0]2-(CH2CH20)i5H,
C6Fi3CH2CH20-(CH2CH20)i5H,
C6Fi3CH2CH20[CH2CH(CH3)0]2-(CH2CH20)i5H, and
C4F9CH2CH20ICH2CH(CH3)0]2-(CH2CH20)i5H.
Surfactant s^:
Surfactant s^ is a nonionic surfactant made of a compound having at least one
carbon-carbon triple bond and at least one hydroxy group in the molecule.
Surfactant s^ is preferably a nonionic surfactant made of a compound having one
carbon-carbon triple bond and one or two hydroxy group(s) in the molecule.
Surfactant s^ may have a POA chain in the molecule. The POA chain may, for
example, be a POE chain, a POP chain, a chain wherein POE chains and POP chains
are linked in a random manner, or a chain wherein POE chains and POP chains are
linked in block form.
Surfactant s^ is preferably compounds (s^^) to (s^^):
HO-C(R^^)(R^2).c=c-C(Ri3)(Ri4).oH (s^^)
H0-(A^0)U-C(R^^)(R^2)-CEC-C(R^^)(R^'*)-(0AV0H (S^^)
HO-C(R^^)(R^^)-C=C-H (s^^)
HO-(A^O)W-C(R^^)(R^^)-C=C-H (S^')
Each of A^ to A^ which are independent of one another, is an alkylene group.
Each of u and v is an integer of at least 0, and (u + v) is an integer of at least 1.
w is at least 1.
When each of u, v and w is at least 2, the plurality of each of A \ A^ and A^ may
be the same or different, respectively.
A POA chain is preferably a POE chain, a POP chain or a chain containing a
POE chain and a POP chain. The number of repeating units of a POA chain is
preferably 1 to 50.
Each of R^^ to R^® which are independent of one another, is a hydrogen atom or
an alkyl group.
The alkyl group is preferably a C1.12 alkyl group, and more preferably a Ci^ alkyl
group. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl
group, a butyl group, or an isobutyl group.
Compound (s^^) is preferably compound (s^^);
13
(CH3)2CHCH2 CH3
, HO(CH2CH20)xC-C=C-C(OCH2CH2)yOH (s^^)
• I I
CH3 CH2CH(CH3)2
wherein each of x and y is an integer of from 0 to 100.
As compound (s^^), one type may be used alone, or two or more types may be
used in combination.
Compound (s^^) is preferably a compound wherein both x and y are 0, the
average of sum of x and y is from 1 to 4, or the average of sum of x and y is from 10 to
30.
Surfactant s^:
Surfactant s^ is a nonionic surfactant made of a compound wherein a POE chain
and a POA chain consisting of two or more consecutively-connected oxyalkylene
having at least 3 carbon atoms are catenated, and both two terminals are hydroxy
groups.
A polyoxytetramethylene (hereinafter referred to as POT) and/or a POP chain is
preferred as such a POA chain.
Surfactant s^ is preferably compound (s^^) or compound (s^^):
HO(CH2CH20)gi (C3H60)t(CH2CH20)g2H (s^^)
HO(CH2CH20)gi(CH2CH2CH2CH20),(CH2CH20)g2H (s^^)
g1 is an integer of from 0 to 200.
t is an integer of from 2 to 100.
g2 is an integer of from 0 to 200.
When g1 is 0, g2 is an integer of at least 2. When g2 is 0, g1 is an integer of at
least 2.
-CsHeO- may be alternatively -CH(CH3)CH20-, -CH2CH(CH3)0-, or mixture of
-CH(CH3)CH20- and -CH2CH(CH3)0-.
The POA chains are in block form.
The following compounds may be mentioned as examples of surfactant s^:
HO-(CH2CH20)i5-(C3H60)35-(CH2CH20)i5H,
HO-(CH2CH20)8-(C3H60)35-(CH2CH20)8H,
HO-(CH2CH20)45-(C3H60)i7-(CH2CH20)45H, and
HO-(CH2CH20)34-(CH2CH2CH2CH20)28-(CH2CH20)34H.
Surfactant s^:
Surfactant s^ is a nonionic surfactant having an amine-oxide portion in the
molecule.
Surfactant s* is preferably compound (s^^);
(R^^) (R^^) (R^^)NHO) (s^^)
wherein each of R^^ to R^^ is a monovalent hydrocarbon group.
A surfactant having an amine oxide (N-^0) is regarded as the nonionic surfactant
in the present invention.
As compound (s*^), one type may be used alone, or two or more types may be
used in combination.
Compound (s"*^) is preferably compound (s'*^) from the viewpoint of dispersion
stability of the copolymer;
14
(R'°)(CH3)2NHO) (s'*^)
wherein R^° is a C6-22 alkyl group, a C6-22 alkenyl group, a phenyl group to which a C6-22
alkyl group is bonded, a phenyl group to which a C6-22 alkenyl group is bonded, or a
vC6-i3 fluoroalkyl group. R^° is preferably a C8-22 alkyl group, a C8-22 alkenyl group or a
C4.9 polyfluoroalkyi group.
The following compounds may be mentioned as examples of compound (s'*^):
[H(CH2)i2](CH3)2NHO),
[H(CH2)i4](CH3)2N(->0),
[H(CH2)i6](CH3)2NHO),
[H(CH2)i8](CH3)2NHO),
[F(CF2)6{CH2)2](CH3)2N(->0), and
[F(CF2)4(CH2)2](CH3)2NHO).
Surfactant s^:
Surfactant s^ is a nonionic surfactant made of a polyoxyethylene
mono(substituted phenyl) ether condensate or a polyoxyethylene mono(substituted
phenyl) ether.
The substituted phenyl group is preferably a phenyl group substituted by a C7.24
monovalent hydrocarbon group, more preferably a phenyl group substituted by an alkyl
group, an alkenyl group or a styryl group.
Surfactant s^ is preferably a polyoxyethylene mono(alkylphenyl) ether
condensate, a polyoxyethylene mono(alkenylphenyl) ether condensate, a
polyoxyethylene mono(alkylphenyl) ether, a polyoxyethylene mono(alkenylphenyl)
ether, or a polyoxyethylene mono[(alkyl)(styryl)phenyl] ether.
The polyoxyethylene mono(substituted phenyl) ether condensate or
polyoxyethylene mono(substituted phenyl) ether may, for example, be a formaldehyde
condensate of polyoxyethylene mono(nonylphenyl) ether, polyoxyethylene
mono(nonylphenyl) ether, polyoxyethylene mono(octylphenyl) ether, polyoxyethylene
mono(oleylpheyl) ether, polyoxyethylene [(nonyl)(styryl)phenyl] ether, or
polyoxyethylene mono[(oleyl)(styryl)phenyl] ether.
Surfactant s®:
Surfactant s^ is a nonionic surfactant made of a fatty acid ester of a polyol.
The polyol represents glycerin, sorbitan, sorbit, polyglycerin, polyethylene glycol,
polyoxyethylene glyceryl ether, polyoxyethylene sorbitan ether or polyoxyethylene
sorbit ether.
Surfactant s^ may, for example, be an ester derived from stearic acid and
polyethylene glycol in 1:1 molar ratio, an ester derived from an ether of sorbit and
polyethylene glycol, and oleic acid in 1:4 molar ratio, an ester derived from an ether of
polyoxyethylene glycol and sorbitan, and stearic acid in 1:1 molar ratio, an ester
derived from an ether of polyethylene glycol and sorbitan, and oleic acid in 1:1 molar
ratio, an ester derived from dodecanoic acid and sorbitan in 1:1 molar ratio, an ester
derived from oleic acid and decaglycerin in 1:1 or 2:1 molar ratio, or an ester derived
from stearic acid and decaglycerin in 1:1 or 2:1 molar ratio.
Surfactant s^:
When the surfactant contains a cationic surfactant, surfactant s^ is preferred as
such a cationic surfactant.
Surfactant s^ is a cationic surfactant having a substituted ammonium salt form.
Surfactant s' is preferably an ammonium salt, wherein at least one hydrogen
atom connected to the nitrogen atom is substituted by an alkyl group, an alkenyl group
15
or a POA chain having a hydroxy group at the terminal, and is more preferably
compound (s^^);
[(R'^)4N1X- (s^^)
jwherein R^^ is a hydrogen atom, a C1.22 alkyl group, a C2-22 alkenyl group, a C1.9
fluoroalkyi group, or a POA chain having a hydroxy group at the terminal. The four
R^^'s may be the same or different, however, all of the four R^^ are not hydrogen atoms
at the same time.
R^^ is preferably a C6-22 long-chain alkyl group, a C6-22 long-chain alkenyl group,
or a C1-9 fluoroalkyi group.
When R^^ is an alkyl group other than a long-chain alkyl group, the R^^ is
preferably a methyl group or an ethyl group.
When R^"* is a POA chain having a hydroxy group at the terminal, the POA chain
is preferably a POE chain.
X" is a counter ion.
X" is preferably a chloride ion, an ethylsulfate ion or an acetate ion.
Compound (s^^) may, for example, be monostearyltrimethylammonium chloride,
monostearyldimethylmonoethylammonium ethylsulfate,
mono(stearyl)monomethyldi(polyethylene glycol)ammonium chloride,
monofluorohexyltrimethylammonium chloride, di(tallow alkyl)dimethylammonium
chloride, or dimethyl mono coconut amine acetate.
Surfactant s^:
When the surfactant contains a zwitterizonic surfactant, surfactant s^ is preferred
as such a surfactant.
Surfactant s® may, for example, be an alanine, an imidazolinium betaine, an
amidebetaine or betaine acetate.
The hydrophobic group in the surfactant s° is preferably a C6-22 long-chain alkyl
group, a C6-22 long-chain alkenyl group, or a C1-9 fluoroalkyi group.
Surfactant s° may, for example, be dodecylbetaine, stearylbetaine,
dodecylcarboxymethylhydroxyethyl imidazolinium betaine,
dodecydimethylaminoacetate betaine, or a fatty acid amidepropyl
dimethylaminoacetate betaine.
Surfactant s^:
Surfactant s^ may used as the surfactant.
Surfactant s^ is a polymeric surfactant made of a block copolymer, a random
copolymer or a hydrophobically modified body of a hydrophilic copolymer, which is
derived from a hydrophilic monomer and a hydrophobic hydrocarbon monomer and/or
a hydrophobic fluoromonomer.
Surfactant s^ may, for example, be a block or random copolymer derived from
polyethylene glycol (meth)acrylate and a long-chain alkyl acrylate, a block or random
copolymer derived from polyethylene glycol (meth)acrylate and a fluoro (meth)acrylate,
a block or random copolymer derived from vinyl acetate and a long-chain alkyl vinyl
ether, a block or random copolymer derived from vinyl acetate and a long-chain
alkylvinyl ester, a polymer derived from styrene and maleic anhydride, a condensate of
polyvinyl alcohol and stearic acid, a condensate of polyvinyl alcohol and stearyl
mercaptan, a condensate of polyallylamine and stearic acid, a condensate of
polyethyleneimine and stearyl alcohol, methylcellulose, hydroxypropylmethylcellulose,
or hydroxyethylmethylcellulose.
Commercial products of surfactant s^ include MP Polymer (item code: MP-103,
16
MP-203) manufactured by Kurary Co., Ltd., SMA resins manufactured by Elf Atochem
Inc., METOLOSE manufactured by Shin-Etsu Chemical Co., Ltd., EPOMIN RP
manufactured by NIPPON SHOKUBAI Co., Ltd., and Surflon (item code: S-381, S-393)
vmanufactured by SEIMI CHEMICAL CO., LTD.
Surfactant s® is preferably surfactant s^^ when the medium is an organic solvent,
or the organic content in the solvent is high;
Surfactant s^^: a polymeric surfactant made of a block or random copolymer (its
polyfluoroalkyi denatured body) of a lipophilic monomer and a fluoromonomer
Surfactant s^^ may, for example, be a copolymer derived from an alkyl acrylate
and fluoro (meth)acrylate, or a copolymer derived from an alkyl vinyl ether and a
fluoroalkyl vinyl ether
Commercial products of surfactant s^^ include Surflon (item code: S-383, SC-100
series) manufactured by SEIMI CHEMICAL CO., LTD.
From the viewpoint of excellence in water repellency, durability of the water/oil
repellent composition and stability of the obtained emulsion, the combination of the
surfactants is preferably a combination of surfactant s\ surfactant s^ and surfactant s^;
a combination of surfactant s\ surfactant s^ and surfactant s^; or a combination of
surfactant s\ surfactant s^, surfactant s^ and surfactant s^, more preferably such
combinations wherein surfactant s^ is compound (s^^).
The total amount of the surfactants is preferably from 1 to 6 parts by mass in the
copolymer (100 parts by mass).
(Additives)
The water/oil repellent composition of the present invention may contain various
additives as the case requires.
Additives may for example, be a penetrant, an anti-foaming agent, a water
absorbent, an anti-static agent, an anti-crease agent, a softener, a film-forming aid, a
water-soluble polymer (polyacrylamide, polyvinyl alcohol, etc.), a thermosetting agent
(melamine resin, urethane resin, etc.), an epoxy curing agent (isophthalic acid
hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid
dihydrazide, 1,6-hexamethylene bis(N,N-dimethylsemicarbazide), 1,1,1',1'-tetramethyl-
4,4'-(methylene-di-p-phenylene)disemicarbazide, spiroglycol, etc.), a thermosetting
catalyst, a cross-linking catalyst, a synthetic resin, a fiber stabilizer, fine inorganic
particles, etc.
The water/oil repellent composition of the present invention preferably contains a
thermosetting agent and a thermosetting catalyst, since the durability is thereby
improved.
Further, the water/oil repellent composition of the present invention may contain a
copolymer having water and/or oil repellency other than the copolymer of the present
invention (e.g. a copolymer containing many structural units based on the monomer (c),
a commercial water repellent agent, a commercial oil repellent agent or a commercial
water/oil repellent agent), a water repellent compound having no fluorine atom, etc., as
the case requires. Such a water repellent compound having no fluorine atom may, for
example, be a paraffin compound, an aliphatic amide compound, an alkylethylene urea
compound or a silicon compound.
(Method for producing water/oil repellent composition)
The water/oil repellent composition of the present invention is produced by the
following method (i) or (ii).
(i) A method which comprises polymerizing a monomer mixture comprising the
17
monomer (a) and the monomer (b) and, as the case requires, containing the monomer
(c) and the monomer (d), in a medium in the presence of a surfactant and a
polymerization initiator, to obtain a solution, dispersion or emulsion of a copolymer, and
V as a case requires, adding other media, other surfactants or additives.
(ii) A method which comprises polymerizing a monomer mixture comprising the
monomer (a) and the monomer (b) and, as the case requires, containing the monomer
(c) and the monomer (d), in a medium in the presence of a surfactant and a
polymerization initiator, to obtain a solution, dispersion or emulsion of a copolymer,
then separating the copolymer, and adding to the copolymer, a medium, a surfactant
and an optional additive.
The polymerization of the monomer mixture may be carried out in the same
manner as the polymerization in the above described method for producing a
copolymer
Regarding the water/oil repellent composition of the present invention, the
copolymer is preferably dispersed in the form of particles in the medium. The average
particle size of the copolymer is preferably from 10 to 1,000 nm, more preferably from
10 to 300 nm, particularly preferably from 10 to 250 nm. When the average particle
size is within such a range, a surfactant, a dispersant, etc. are not required in large
amounts, water/oil repellency is good, dyed fabrics can be treated without color dulling,
and the particles are stably-dispersed without precipitation in the medium. The
average particle size of the copolymer is measured by a dynamic light scattering
device, an electron microscope, etc.
The solid content concentration of the emulsion is preferably from 20 to 40
mass% in the emulsion (100 mass%) immediately after the production of the
copolymer Here, the solid content concentration is the concentration including not
only the copolymer but also an emulsifying agent. The content of the copolymer in
the emulsion is preferably from 18 to 40 mass% immediately after the production of the
copolymer.
The solid content concentration of the water/oil repellent composition is
preferably from 0.2 to 5 mass% in the water/oil repellent composition (100 mass%) at
the time of treating articles.
The solid content concentration of the emulsion or the water/oil repellent
composition is calculated from the mass of the emulsion or the water/oil repellent
composition before heating and the mass of it after drying in the convection-drying
machine at the temperature of 120°C for 4 hours.
The above described water/oil repellent composition of the present invention
contains the copolymer of the present invention, whereby it is possible to impart
sufficient dynamic water repellency and water repellency after air drying to the surface
of an article. Further, the copolymer does not have structural units based on a
monomer having an R*" group having at least 8 carbon atoms, whereby it presents little
environmental burden.
In addition, regarding the water/oil repellent composition of the present invention,
the content (the content when the solid content concentration is 20%) of
perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PROS), their precursors and
their analogues, environmental impact of which is pointed out, can be reduced to a
level lower than the detection limit of analysis value of LC-MS/MS in the method
disclosed in Japanese Patent Application No. 2007-333564.
The water/oil repellent composition of the present invention may be used alone.
18
or as mixed with another water/oil repellent composition. For example, it is used as
combined with a fluorinated soil release agent which has much hydrophilic component
and little water repellent property, whereby wash-durable water/oil repellent soilurelease
finishing is possible.
'^Article>
The water/oil repellent composition of the present invention is used for water/oil
repellent treatment of an article.
The article to be treated with the water/oil repellent composition of the present
invention may, for example, be fibers (natural fibers, synthetic fibers, blended fibers,
etc.), various fiber products, nonwoven fabrics, resins, paper, leather, metal, stone,
concrete, plaster, or glass.
An example of a method for treating the article is to coat or dip the article with the
water/oil repellent composition by a publicly-known coating method and then to dry it.
Additionally, such an article may be finished to be antistatic, softening,
antibacterial, deodorant or waterproof.
An example of water proofing may be to form a water proof membrane. The
water proof membrane may, for example, be a porous membrane obtained from a
urethane resin or an acryl resin, a nonporous membrane obtained from a urethane
resin or an acryl resin, a polytetrafluoroethylene membrane or a moisture-permeable
water proof membrane which is a combination of the above membranes, etc.
When an article is treated with the water/oil repellent composition of the present
invention, it is possible to impart water/oil repellency of high quality to the article.
Further, it is possible to impart the water/oil repellency even by curing at a low
temperature, with excellent adhesion to the substrate surface. Further, the initial
performance of the treatment can stably be maintained with little deterioration of the
performance by abrasion or washing. Further, when paper is treated, even under a
low temperature drying condition, excellent size property and water/oil repellency can
be imparted to the paper. When a resin, glass or metal surface is, for example,
treated, it is possible to form a water/oil repellent coating film which is excellent in the
film-forming property and exhibits good adhesion to the article.
EXAMPLES
Now, the present invention will be described in detail with reference to Examples,
but it should be understood that the present invention is by no means limited to such
Examples.
Examples 1 to 11 and 20 to 22 are working examples of the present invention,
and Examples 12 to 19 are comparative examples.

With respect to a copolymer recovered by the following recovering method A,
measurement of the molecular weight and analysis of the copolymer composition were
carried out.
(Copolymer recovery method A)
6 g of an emulsion was concentrated so that the solid content became about 40
mass% to obtain a concentrated liquid. To this concentrated liquid, about 10 g of
tetrahydrofuran (hereinafter referred to as THF) was dropwise added to dissolve the
solid in the concentrated liquid thereby to obtain a THF solution. In a case where the
solid was hardly dissolved, ultrasonic waves were applied. To 60 g of methanol, the
THF solution was dropwise added, followed by stirring to precipitate a solid. The
19
obtained solid was recovered by filtration under reduced pressure. It was vacuumdried
overnight at 35°C to obtain a copolymer.
(Copolymer composition)
L For the analysis of the copolymer composition of the recovered copolymer, ""^FNMR,
""^C-NMR, pyrolysis GC/MS, and automatic sample combustion device-ion
chromatography were used.
From the ^^F-NMR analysis, information relating to the chain length of structural
units based on the monomer (a) is obtainable. Further, from the ^^C-NMR,
information relating to structural units based on a hydrocarbon monomer is obtainable.
Further, a peak of structural units based on the monomer (d1) is observed in the
vicinity of from 10 to 35 ppm. Peaks of structural units based on vinyl chloride are
observed in the vicinity of 45 ppm and 56 ppm. A peak of structural units based on
vinylidene chloride is observed in the vicinity of from 80 to 90 ppm. A peak of
structural units based on the monomer (a) is observed in the vicinity of from 105 to 120
ppm.
From the GC/MS analysis, it is possible to know the detailed structures of
structural units based on the monomers contained in the copolymer.
In the automatic combustion device-ion chromatography analysis, the amounts of
F and CI in the copolymer were quantified. From the amount of F, the proportion of
structural units based on the monomer (a) can be calculated. Further, from the
amount of CI, the proportion of structural units based on the monomer (b) can be
calculated.
The conditions for the respective analyses are as follows.
(NMR)
Apparatus: ECP 400, manufactured by JEOL Ltd.
Sample: 5 mass% copolymer CDCI3 solution
^^F-NMR external standard: 1,1,2-trichloro-1,2,2-trifluoroethane
Temperature for measurement: room temperature
(Automatic combustion device-ion chromatography (AQF-IC method))
(Automatic sample combustion device)
Apparatus: automatic sample combustion device AQF-100, manufactured by Dia
Instruments Co., Ltd.
Combustion condition: mode for solid sample
Amount of sample: from 2 to 20 mg
(Ion chromatography)
Apparatus: manufactured by Dionex Corporation
Column: lonpacAG12A+lonpacAS12A
Eluent: 2.7 mM-NaaCOs/O.S mM-NaHCOs
Flow rate: 1.3 mUmin
Suppressor: ASRS
Detector: electric conductivity detector
Injected amount: 5 |JL
(Molecular weight)
Measurement of the molecular weight of the recovered copolymer was carried
out by GPC measuring method A or GPC measuring method B.
(GPC measuring method A)
The recovered copolymer was made into a 0.5 mass% THF solution, which was
passed through a 0.45 pm filter to obtain a sample for analysis. With respect to such
20
a sample, the mass average molecular weight (Mw) was measured. The conditions
for the measurement are as follows.
Apparatus: HLC-8220GPC, manufactured byTOSOH CORPORATION
L Column: four types of TSKgel superHZ4000, superHZ3000, superHZ2500 and
superHZ2000 are connected in series.
Temperature for measurement: 40°C
Injected amount: 40 pL
Flow rate: 0.35 mL/min
Eluent: THF
Standard sample: EasiCal PS-2, manufactured by Polymer laboratories
(GPC measuring method B)
The recovered copolymer was dissolved in a solvent mixture of fluorinated
solvent (AK-225, manufactured by Asahi Glass Company, Limited)/THF = 6/4 (volume
ratio) to obtain a 1 mass% solution, which was passed through a 0.2 |jm filter to obtain
a sample for analysis. With respect to such a sample, the number average molecular
weight (Mn) and the mass average molecular weight (Mw) were measured. The
conditions for measurement are as follows.
Apparatus: HLC-8220GPC, manufactured byTOSOH CORPORATION
Column: MIXED-C and 100A, manufactured by Polymer laboratories, are
connected in series.
Temperature for measurement: 37°C
Injected amount: 50 pL
Flow rate: 1 mL/min
Standard sample: EasiCal PM-2, manufactured by Polymer laboratories
Eluent: solvent mixture of fluorinated solvent (AK-225, manufactured by Asahi
Glass Company, Limited)/THF = 6/4 (volume ratio)

(Oil repellency)
With respect to a test cloth, the oil repellency (OR) was evaluated in accordance
with the test method of AATCC-TM118-1966. The oil repellency was represented by
grades as shown in Table 1. The grade followed by + (-) means that the property is
slightly better (worse).
TABLE 1
Oil repellency
No.
8
7
6
5
4
3
2
1
0
Test liquid
n-Heptane
n-Octane
n-Decane
n-Dodecane
n-Tetradecane
n-Hexadecane
65 Parts of Nujol / 35 parts of hexadecane
Nujol
Less than 1
Surface tension
mN/m (25°C)
20.0
21.8
23.5
25.0
26.7
27.3
29.6
31.2
~
(Washing durability)
With respect to a test cloth, washing was repeated 20 times in accordance with
21
the water-washing method of JIS L0217 Attached Table 103. After the washing, air
drying was carried out overnight in a room at a room temperature of 25°C under a
relative humidity of 60%, whereupon the above oil repellency was evaluated.
JWater repellency)
With respect to a test cloth, water repellency (WR) was evaluated in accordance
with the spray test of JIS L1092-1992 . The water repellency was represented by 5
grades of from 1 to 5. The higher the grade, the better the water repellency. One
with grade 3 or higher is regarded as exhibiting water repellency. A grade followed by
+ (-) means that the property is slightly better (worse) as compared with the standard
level of that grade.
(Washing durability)
With respect to a test cloth, washing was repeated 20 times or 50 times in
accordance with the water-washing method of JIS L0217 Attached Table 103. After
the washing, air drying was carried out overnight in a room at a room temperature of
25°C under a relative humidity of 60%, whereupon the above water repellency was
evaluated.
(Dynamic water repellency)
With respect to a test cloth, rainfall was simulated in accordance with the method
disclosed in JIS LI 092, method (C) (Bundesmann Method) under such conditions that
the amount of rainfall was 100 cc/min, the temperature of rainwater was 20°C and the
raining time was 10 minutes, whereby the water repellency was evaluated. The water
repellency was represented by 10 grades of from 1 to 5. The higher the grade, the
better the water repellency. One with grade 3 or higher is regarded as exhibiting
water repellency. A grade followed by + (-) means that the property is slightly better
(worse).
(Washing durability)
With respect to a test cloth, washing was repeated 5 times in accordance with a
water washing method of JIS L0217 Attached Table 103. After the washing, air drying
was carried out overnight in a room at a room temperature of 25°C under a relative
humidity of 50%, whereupon the above dynamic water repellency was evaluated.
(Abbreviations)
CmFA:
F(CF2)mCH2CH20C(0)CH=CH2 (a mixture of ones having m being from 6 to 16,
wherein ones having m being at least 8 are at least 99 mass%, and an average value
of m is 9).
Monomer (a):
C6FMA: C6Fi3C2H40C(0)C(CH3)=CH2
Monomer (b):
VCM: vinyl chloride
VdCI: vinylidene chloride
Monomer (c):
D-BI: 3,5-dimethylpyrazole adduct of 2-isocyanateethyl methacrylate (the
following formula (5))
NMAM: N-methylol acrylamide
HEMA: 2-hydroxyethyl methacrylate
NBM: N-butoxymethyl acrylamide
4HBA: 4-hydroxybutyl acrylate
22
H2C=C-CH3 ^ ,N:^-^"3
, C-O-CH2-CH2-N-C-N'
-r- II II •
0 0
(5)
H3C
Monomer (d):
DOM: dioctyl maleate
Monomer (d1):
STA: stearyl acrylate
BeA: behenyl acrylate
Molecular weight-controlling agent:
nDOSH: n-dodecyl mercaptan
Surfactants^:
PEO-20: an aqueous solution containing 10 mass% of polyoxyethylene oleyl
ether (EMULGEN E430, ethylene oxide about 26 mol adduct, manufactured by Kao
Corporation)
SFY465: an aqueous solution containing 10 mass% of 2,4,7,9-tetramethyl-5-
decyne-4,7-diol ethylene oxide adduct (SURFYNOL465, ethylene oxide 10 mol adduct,
manufactured by NISSIN CHEMICAL INDUSTRY CO., LTD.)
BL-21: polyoxyethylene(21) lauryl ether (manufactured by Nikko Chemicals Co.,
Ltd.)
Surfactant s^:
TMAC: an aqueous solution containing 10 mass% of trimethylammonium chloride
(Arquad 18-63, manufactured by LION K.K.)
AM301: an aqueous solution of betaine lauryldimethyl aminoacetate
(manufactured by Nikko Chemicals Co., Ltd.)
Surfactant s^:
P204: an aqueous solution containing 10 mass% of ethylene oxide propylene
oxide polymer (PLONON 204, proportion of ethylene oxide: 40 mass%, manufactured
by NOP CORPORATION)
Polymerization initiator:
VA061A: an aqueous solution containing 10 mass% of an acetate of 2,2'-
azobis[2-(2-imidazolin-2-yl)propane] (VA-061, manufactured by Wako Pure Chemical
Industries, Ltd.)
V50: 2,2-azobis(2-methylpropioneamidine) dihydrochloride (manufactured by
Wako Pure Chemical Industries, Ltd.)
Medium:
DPG: dipropylene glycol
Water: deionized water
EXAMPLE 1
248.3 g of C6FMA, 2.8 g of HEMA, 2.8 g of nDOSH, 69.0 g of PEO-20, 13.8 g of
TMAC, 13.8 g of P204, 82.8 g of DPG and 328.3 g of water were put in a glass beaker,
heated at 55°C for 30 minutes and then mixed by a homomixer (BIO MIXER,
manufactured by NIHONSEIKI KAISHALTD.) to obtain a mixed liquid.
While maintained at 50°C, the obtained mixed liquid was treated by a high
23
pressure emulsifier (Mini-Lab, manufactured by APV RANNIE) under 40 MPa to obtain
an emulsion. The obtained emulsion was put Into a glass reactor and cooled to at
most 30°C. 24.8 g of VdCI and 13.8 g of VA061A were added thereto, and after
replacing the gas phase with nitrogen, a polymerization reaction was carried out at
65°C for 15 hours with stirring to obtain an emulsion of a copolymer.
The proportions of the respective monomers in the monomer mixture are shown
in Table 3. Further, the recovery method for the copolymer, the copolymer
composition and the molecular weight of the copolymer are shown in Table 4. AA in
the Table is a value representing 100 - [the proportion (calculated value) of structural
units based on the monomer (a) + the proportion (calculated value) of structural units
based on the monomer (b)]. The analyzed values of the copolymer composition
generally agree with the calculated values from the charged amounts. This indicates
that the copolymer contains structural units corresponding to the charged amounts of
the monomers.
EXAMPLES 2 to 10, 13 to 15, 18 and 20 to 22
An emulsion of a copolymer was obtained in the same manner as in Example 1
except that the charged amounts of the respective materials were changed to the
amounts shown in Table 2.
The proportions of the respective monomers in the monomer mixture are shown
in Table 3. Further, with respect to some Examples, measurement of the molecular
weight of the copolymer and analysis of the copolymer composition were carried out.
The recovery method for the copolymer, the copolymer composition and the molecular
weight of the copolymer are shown in Table 4. The analytical values of the copolymer
composition generally agree with the calculated values from the charged amounts.
This indicates that the copolymer contains structural units corresponding to the
charged amounts of the monomers.
EXAMPLE 11
240.0 g of C6FMA, 8.3 g of D-BI, 2.8 g of HEMA, 2.8 g of nDOSH, 69.0 g of
PEO-20, 13.8 g of TMAC, 13.8 g of P204, 82.8 g of DPG and 328.3 g of water were
put into a glass beaker, heated at 60°C for 30 minutes and then mixed by a homomixer
(BIO MIXER, manufactured by NIHONSEIKI KAISHA LTD.) to obtain a mixed liquid.
While maintained at 60°C, the obtained mixed liquid was treated by a high
pressure emulsifier (Mini-Lab, manufactured by APV RANNIE) under 40 MPa to obtain
an emulsion. The obtained emulsion was put into a stainless steel reactor and cooled
to at most 40°C. 13.8 g of VA061A was added, and the gas phase was replaced with
nitrogen, then, 24.8 g of VCM was introduced, and a polymerization reaction was
carried out at 60°C for 15 hours with stirring, to obtain an emulsion of a copolymer.
The proportions of the respective monomers in the monomer mixture are shown
in Table 3.
EXAMPLES 12, 16, 17 and 19
An emulsion of a copolymer was obtained in the same manner as in Example 1
except that the charged amounts of the respective materials were changed to the
amounts shown in Table 2.
The proportions of the respective monomers in the monomer mixture are shown
in Table 3. Further, with respect to some Examples, measurement of the molecular
weight of the copolymer was carried out. The molecular weight of the copolymer is
shown in Table 4.
24
TABLE 2
Charged amounts (g)
Ex.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Cm FA
193.1
(a)
C6FMA
248.3
234.5
220.7
206.9
193.1
165.5
215.2
212.4
198.6
212.4
240.0
204.1
186.2
144.8
110.3
49.1
107.6
55.2
188.8
200.6
212.4
(d1)
STA
35.9
48.3
(d1)
BeA
35.9
62.1
55.2
166.1
55.2
(b)
VCM
24.8
24.8
57.9
110.3
57.9
(b)
VdCI
24.8
38.6
52.4
66.2
80.0
107.6
52.4
49.7
49.7
24.8
24.8
80.0
107.6
0.0
0.0
217.9
44.8
33.0
21.2
(c)
D-BI
8.3
11.0
(d)
DOM
17.4
(c)
NMAM
7.4
(c)
HEMA
2.8
2.8
2.8
2.8
2.8
8.3
13.8
22.1
2.8
2.8
2.8
2.8
2.8
2.8
2.4
2.4
2.4
(c)
NBM
2.8
(c)
4HBA
2.8
5.5
2.8
25
TABLE 2 (Continued)
Charged amounts (g)
Ex.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
-
nDoSH
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.8
2.7
2.4
2.4
2.4
s^
PEO-20
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
69.0
96.0
s^
SFY465
10.7
s'
TMAC
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
s^
P204
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.3
s^
AM-301
94.4
94.4
94.4
s^
BL-21
82.6
82.6
82.6
-
VA061A
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.8
13.3
-
V50
11.8
11.8
11.8
-
DPG
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
82.8
80.0
70.8
70.8
70.8
-
Water
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
328.3
308.1
302.0
302.0
302.0
26
TABLE 3
Proportions (mass%) of the respective monomers in the monomer mixture (100 mass%)
Ex.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
CmFA
70
(a)
C6FMA
90
85
80
75
70
60
78
77
72
77
87
74
67.5
52.5
40
17.8
39
20
80
85
90
(d1)
STA
13
17.5
(d1)
BeA
13
22.5
20
60.2
20
(b)
VCM
9
9
21
40
21
(b)
VdCI
9
14
19
24
29
39
19
18
18
9
9
29
39
79
19
14
9
(c)
D-BI
3
4
(d)
DOM
6.3
(c)
NMAM
2.7
(c)
HEMA
3
5
8
1
1
1
1
1
1
1
1
1
(c)
NBM
1
(c)
4HBA
1
2
1
(a)+(b)
99.0
99.0
99.0
99.0
99.0
99.0
97.0
95.0
90.0
86.0
96.0
83.0
76.5
81.5
79.0
38.8
79.0
99.0
21.0
99.0
99.0
99.0
Molar
ratio
(a)/(b)
2.2
1.3
0.9
0.7
0.5
0.3
0.9
1.0
0.9
1.9
1.4
1.2
1.7
0.4
0.2
0.1
0.1
0.1
0.0
0.9
1.3
2.2
27
TABLE 4
Ex.
1
3
5
7
9
19
Recovery
method for
copolymer
A
A
A
A
A
A
Copolymer composition (mass%)
Calculated from charged
amounts *1
(a)
89
79
69
-
-
-
AA
2
2
2
-
-
-
(b)
9
19
29
-
-
-
Analytical results
(a)
89.2
81
72
-
-
-
AA
3.5
3
1
-
-
-
(b)
7.3
16
27
-
-
-
Molecular weight
GPC method
B
B
A
A
B
B
Mn
24091
24219
10857
11690
22647
23100
Mw
34498
34382
25315
26799
32673
32334
Mw/Mn
1.4
1.4
2.3
2.3
1.4
1.4
"1: Including the initiator and the molecular weight-controlling agent
28

An emulsion of the copolymer in each of Examples 1 to 22 was diluted with
distilled water to adjust the solid content concentration to be 10 mass%, then, a
i trimethyiolmelamine resin (BECKAMINE M-3, manufactured by DIC Corporation) as a
thermosetting agent and an organic amine salt catalyst (Accelerator ACX,
manufactured by DIC Corporation) as a thermosetting catalyst were added so that the
respective concentrations became 0.3 mass%, and further, a blocked isocyanate
(MEIKANATE TP-10, manufactured by Meisei Chemical Works, Ltd.) as a combination
assisting agent was added so that the concentration became 0.6 mass%, thereby to
obtain a water/oil repellent composition.
In the water/oil repellent composition, a dyed nylon cloth was dipped and
squeezed so that the wet pickup became 42 mass%. This cloth was dried under the
following heating condition A or B to obtain a test cloth. With respect to the test cloth,
water repellency (water repellency after air drying), oil repellency and dynamic water
repellency were evaluated. The results are shown in Table 5.
Heating condition A: drying at 110°C for 90 seconds, followed by drying at 170°C
for 60 seconds.
Heating condition B: drying at 140°C for 90 seconds.
It is evident that Examples of the present invention are capable of imparting
dynamic water repellency and at the same time have excellent effects for water
repellency and oil repellency.
29
TABLE 5
K- Number of
washing times
Ex.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Heating
condition
A
A
A
A
A
B
A
B
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
0
6-
5
6-
6
5
5
5
5
6
5-
5
6
6-
6-
6
5
4-
4-
3
3
6
6
5
5
OR
20
2-
3-
3-
3
2
2
2
2
3
3
3-
2
5
2
1
2
4
0
2
2
3-
1
1
1
50
2-
2
2-
2
2
2
2-
2-
2
2
2
2
4-
2
1-
2
2-
0
1-
2
2
-
-
-
0
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5-
5
4+
4+
5
5
5
5
WR
20
5
4+
5
4+
4+
4+
5-
5-
5-
3+
3+
4+
4+
4+
4+
4-
4+
5-
3+
3
5
3+
3+
3+
50
4
4
5-
4
4+
4
4-
3+
4+
4+
3
4+
4
4
3+
3
4-
5-
3+
3
5
-
-
-
Bundesmann
test
0
5-
4+
5-
4-
5-
4.5
4
4
4.5
4
4-
4
3.5
3.5
4
3.5
3-
4.5
3.5
3.5
5-
5
5
5
5
3
3.5
4
4
4-
3+
3+
3
3+
3
3
3
3-
2.5
2.5
2-
1 +
4+
2+
2
5-
3
3+
3
INDUSTRIAL APPLICABILITY
The copolymer and the water/oil repellent composition of the present invention
are useful as water/oil repellents for e.g. fiber products (clothing products (sports wears,
coats, blousons, workwears, uniforms, etc.), bags, industrial materials, etc.), nonwoven
fabrics, leather products, stone materials, concrete building materials, etc.
Further, they are useful as coating agents for filtration materials, or as surface
protecting agents. Further, they are useful for applications to impart water repellency,
as mixed with polypropylene, nylon, etc., followed by forming into fibers.
The entire disclosure of Japanese Patent Application No. 2008-147120 filed on
June 4, 2008 including specification, claims and summary is incorporated herein by
reference in its entirety.









30
CLAIMS
1. A copolymer comprising structural units of the following monomer (a) and
structural units of the following monomer (b), wherein the total of the content of
.structural units based on the monomer (a) and the content of structural units based on
the monomer (b) is at least 85 mass% of all structural units (100 mass%), and the
molar ratio ((a)/(b)) of the content of structural units based on the monomer (a) to the
content of structural units based on the monomer (b) is from 0.12 to 3:
Momomer (a): a compound represented by the following formula (1):
(Z-Y)n-X (1)
wherein Z is a Ci-e polyfluoroalkyi group or a group represented by the following
formula (2), Y is a bivalent organic group or a single bond, n is 1 or 2, and when n is 1,
X is any one of groups represented by the following formulae (3-1) to (3-5) and when n
is 2, X is any one of groups represented by the following formulae (4-1) to (4-4):
CiF2i+iO(CFX^CF20)jCFX2- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0 to 10, and each of X^ and
X^ is a fluorine atom or a trifluoromethyl group.
-CR=CH2
-C(0)0CR=CH2
-0C(0)CR=CH2
-OCH2-(p-CR=CH2
-0CH=CH2
wherein R is a hydrogen atom.
phenylene group.
-CH[-(CH2)mCR=CH2]-
(3-1)
(3-2)
(3-3)
(3-4)
(3-5)
a methyl group or a halogen atom, and cp is a
(4-1)
-CH[-(CH2)mC(0)OCR=CH2]- (4-2)
-CH[-(CH2)mOC(0)CR=CH2]- (4-3)
-OC(0)CH=CHC(0)0- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer
of from 0 to 4,
Monomer (b): a halogenated olefin.
2. The copolymer according to Claim 1, wherein the monomer (a) is a compound
represented by the formula (1) wherein Z is a C4-6 perfluoroalkyi group.
3. The copolymer according to Claim 1 or 2, wherein the monomer (b) is vinyl
chloride or vinylidene chloride
4. The copolymer according to any one of Claims 1 to 3, which further has structural
units based on the following monomer (c):
Monomer (c): a monomer having a cross-linkable functional group without having
a polyfluoroalkyi group.
5. The copolymer according to any one of Claims 1 to 4, which does not have
structural units based on the following monomer (d1):
Monomer (d1): a (meth)acrylate having an alkyl group having at least 18 carbon
atoms.
6. The copolymer according to any one of Claims 1 to 5, wherein based on all
monomers (100 mass%), structural units based on the monomer (a) are from 50 to
98.5 mass%, and structural units based on the monomer (b) are from 1 to 40 mass%.
7. A method for producing a copolymer, which comprises polymerizing a monomer
mixture comprising the following monomer (a) and the following monomer (b) in a
medium in the presence of a surfactant and a polymerization initiator, wherein the total
31
of the content of the monomer (a) and the content of the monomer (b) is at least 85
mass% of the monomer mixture (100 mass%), and in the monomer mixture, the molar
ratio ((a)/(b)) of the content of the monomer (a) to the content of the monomer (b) is
1 from 0.12 to 3:
Momomer (a): a compound represented by the following formula (1):
(Z-Y)n-X (1)
wherein Z is a C i ^ polyfluoroalkyi group or a group represented by the following
formula (2), Y is a bivalent organic group or a single bond, n is 1 or 2, and when n is 1,
X is any one of groups represented by the following formulae (3-1) to (3-5) and when n
is 2, X is any one of groups represented by the following formulae (4-1) to (4-4):
CiF2i+iO(CFX^CF20)jCFX2- (2)
wherein i is an integer of from 1 to 6, j is an integer of from 0 to 10, and each of X^ and
X^ is a fluorine atom or a trifluoromethyl group,
-CR=CH2 (3-1)
-C(0)0CR=CH2 (3-2)
-0C(0)CR=CH2 (3-3)
-OCH2-(p-CR=CH2 (3-4)
-0CH=CH2 (3-5)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and (p is a
phenylene group,
-CH[-(CH2)mCR=CH2]- (4-1)
-CH[-(CH2)mC(0)OCR=CH2]- (4-2)
-CH[-(CH2)mOC(0)CR=CH2]- (4-3)
-OC(0)CH=CHC(0)0- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and m is an integer
of from 0 to 4,
Monomer (b): a halogenated olefin.
8. The method for producing a copolymer according to Claim 7, wherein the
monomer (a) is a compound represented by the formula (1) wherein Z is a C4.6
perfluoroalkyi group.
9. The method for producing a copolymer according to Claim 7 or 8, wherein the
monomer mixture further contains the following monomer (c):
Monomer (c): a monomer having a cross-linkable functional group without having
a polyfluoroalkyi group.
10. The method for producing a copolymer according to any one of Claims 7 to 9,
wherein the monomer mixture does not contain the following monomer (d1):
Monomer (d1): a (meth)acrylate having an alkyl group having at least 18 carbon
atoms.
11. The method for producing a copolymer according to any one of Claims 7 to 10,
wherein based on all monomers (100 mass%), structural units based on the monomer
(a) are from 50 to 98.5 mass%, and structural units based on the monomer (b) are
from 1 to 40 mass%.
12. A water/oil repellent composition comprising the copolymer as defined in any one
of Claims 1 to 6 and a medium.
13. The water/oil repellent composition according to Claim 12, which contains a
nonionic surfactant and a cationic surfactant.
32
14. A copolymer substantially as herein described with reference to the foregoing
description, examples and the accompanying tables.
Dated this 2"" day of December 2010
SHARAOVADEIKRA
(ND KpWSHME
ATTORNEY FOR THE APPLICANTS
To
The Controller of Patents
The Patent Office
India

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Patent Number 280018
Indian Patent Application Number 8568/DELNP/2010
PG Journal Number 06/2017
Publication Date 10-Feb-2017
Grant Date 07-Feb-2017
Date of Filing 02-Dec-2010
Name of Patentee ASAHI GLASS COMPANY, LIMITED
Applicant Address 5-1, MARUNOUCHI 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 SUGIYAMA KAZUNORI C/O ASAHI GLASS COMPANY, LIMITED, 12-1, YURAKUCHO 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
2 SHIMADA TOYOMICHI C/O ASAHI GLASS COMPANY, LIMITED, 12-1, YURAKUCHO 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
3 OTOZAWA, NOBUYUKI C/O ASAHI GLASS COMPANY, LIMITED, 12-1, YURAKUCHO 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
4 OOMORI YUUICHI C/O ASAHI GLASS COMPANY, LIMITED, 12-1, YURAKUCHO 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
5 SHIMADA MINAKO C/O ASAHI GLASS COMPANY, LIMITED, 12-1, YURAKUCHO 1-CHOME, CHIYODA-KU, TOKYO 1008405, JAPAN
PCT International Classification Number C08F 214/00
PCT International Application Number PCT/JP2009/060197
PCT International Filing date 2009-06-03
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2008-147120 2008-06-04 Japan