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
2000-11-29
2002-05-28
Yoon, Tae H. (Department: 1714)
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...
C524S544000, C526S245000, C525S374000, C525S375000, C428S375000
Reexamination Certificate
active
06395821
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a water dispersion type water and oil repellent composition.
BACKGROUND ART
Heretofore, it has been known that a polymer having polymer units based on a polymerizable monomer having a polyfluoroalkyl group (hereinafter referred to as a R
f
group), exhibits water and oil repellency. And it has been known that water and oil repellency can be imparted to the surface of a fiber, etc. by treating the fiber, etc. with a water and oil repellent composition containing such a polymer.
In recent years, the application of the water and oil repellent treatment has been expanded to such outdoor fields as sports wears and mountaineering wears. In the outdoor fields, better water and oil repellency is desired.
Further, the durability of water and oil repellency against repeated washing or the durability of hydrostatic pressure resistance of fabric is used as a practical index showing the durability of water and oil repellency. And, the water and oil repellent composition is recommended to be in the form of an aqueous dispersion from the viewpoint of a problem of working environment or a problem of the influence over the environment.
The following cases may be mentioned as methods for solving the above problems and giving durability against repeated washing.
A method of applying an aqueous dispersion of a fluorine-containing copolymer together with a water-soluble amino resin such as an N-methylol-modified melamine resin. A method of applying a fluorine-containing copolymer together with an isocyanate compound (JP-A-56-165072, JP-A-61-19684). A method of treating with an aqueous dispersion containing a fluorine-containing copolymer having isocyanate groups and hydroxyl groups and a blocked isocyanate compound (U.S. Pat. No. 4,834,764)
However, the above methods have had a problem that the durability of water and oil repellency against repeated washing is not sufficient, or a problem that the durability of hydrostatic pressure resistance is not sufficient. Further, for application to fibers, it is not desirable to use the combined resin such as the water-soluble amino resin or the blocked isocyanate compound in a large amount for the purpose of improving the hydrostatic pressure resistance, because such a combined resin tends to harden the hand and feel of the fibers or to impair the air permeability which the fibers inherently have.
An object of the present invention is to provide a water dispersion type water and oil repellent composition which satisfies both repeated washing durability of water and oil repellency and durability of hydrostatic pressure resistance.
DISCUSSION OF THE INVENTION
The present invention is a water dispersion type water and oil repellent composition comprising the following copolymer (A), the following copolymer (B), the following compound (C) and an amino resin (D):
Copolymer (A): a copolymer having polymer units based on a polymerizable monomer having a hydroxyl group and polymer units based on a polymerizable monomer having a polyfluoroalkyl group;
Copolymer (B): a copolymer having polymer units based on a polymerizable monomer having an epoxy group and polymer units based on a polymerizable monomer having a polyfluoroalkyl group; and
Compound (C): a compound having a blocked isocyanate group and no polymerizable carbon-carbon unsaturated bond.
BEST MODE FOR CARRYING OUT THE INVENTION
In this specification, acrylic acid and metacrylic acid are generally referred to as (meth)acrylic acid. The same applies also to a representation by a (meth)acrylate or the like.
The water dispersion type water and oil repellent composition of the present invention comprises the copolymer (A) and the copolymer (B). The copolymer (A) and the copolymer (B) respectively have polymer units based on a polymerizable monomer (hereinafter referred to also as a monomer (f)) having a polyfluoroalkyl group. As the monomer (f), a (meth)acrylate having a R
f
group is preferred. The (meth)acrylate having a R
f
group is a compound wherein a R
f
group is present in the alcohol residue moiety of a (meth)acrylic acid ester.
The R
f
group is a group having at least two hydrogen atoms of an alkyl group substituted by fluorine atoms. The carbon number of the R
f
group is preferably from 2 to 20, particularly preferably from 6 to 16. Further, the R
f
group may have a straight chain structure or a branched structure, preferably a straight chain structure. In the case of a branched structure, it is preferred that the branched moiety is present at the terminal portion of the R
f
group, and it is a short chain with a carbon number of from about 1 to 4. The R
f
group may contain a halogen atom other than a fluorine atom. The halogen atom other than the fluorine atom is preferably a chlorine atom.
The structure of the terminal moiety of the R
f
group may, for example, be —CF
2
CF
3
, —CF(CF
3
)
2
, —CF
2
H, —CFH
2
, or —CF
2
Cl, preferably —CF
2
CF
3
. Further, an etheric oxygen atom or a thioetheric sulfur atom may be inserted between a carbon-carbon bond in the R
f
group.
The number of fluorine atoms in the R
f
group is preferably at least 60%, particularly preferably at least 80%, when it is represented by [(number of fluorine atoms in the R
f
group)/(number of hydrogen atoms contained in an alkyl group having the same carbon number as in the R
f
group)]×1000(%). Further, the R
f
group is preferably a group having all hydrogen atoms in an alkyl group substituted by fluorine atoms, i.e. a perfluoroalkyl group (hereinafter referred to as a R
F
group), or a group having a R
F
group at the terminal portion.
The carbon number of the R
F
group is preferably from 2 to 20, particularly preferably from 6 to 16. If the carbon number is less than 2, the water and oil repellency tends to be low. If the carbon number exceeds 20, the copolymer tends to be solid at room temperature, and the sublimation property tends to increase, whereby handling tends to be difficult.
Specific examples for the R
f
group will be given below. The following examples include “structurally isomeric groups” which are groups different in the structure, having the same molecular formula.
C
4
F
9
—[F(CF
2
)
4
—, (CF
3
)
2
CFCF
2
— or (CF
3
)
3
C—], C
5
F
11
— [such as F(CF
2
)
5
— or (CF
3
)
3
CCF
2
—], C
6
F
13
— [such as F(CF
2
)
6
—, C
7
F
15
—, C
8
H
17
—, C
9
F
19
—, C
10
F
21
—, Cl(CF
2
)
s
— (s is an integer of from 2 to 16), H(CF
2
)
t
— (t is an integer of from 1 to 16), (CF
3
)
2
CF(CF
2
)
y
— (y is an integer of from 1 to 14), etc.
Specific examples will be given below wherein the R
f
group is a group having an etheric oxygen atom or a thioetheric sulfur atom inserted between a carbon-carbon bond.
F(CF
2
)
5
OCF(CF
3
)—, F[CF(CF
3
)CF
2
O]
r
CF(CF
3
)CF
2
CF
2
—, F[CF(CF
3
)CF
2
O]
z
CF(CF
3
)—, F[CF(CF
3
)CF
2
O]
u
CF
2
CF
2
—, F(CF
2
CF
2
CF
2
O)
v
CF
2
CF
2
—, F(CF
2
CF
2
O)
w
CF
2
CF
2
— (r is an integer of from 1 to 6, z is an integer of from 1 to 5, u is an integer of from 2 to 6, v is an integer of from 1 to 6, and w is an integer of from 1 to 9), etc.
As the (meth)acrylate having a R
2
group, a compound represented by the following formula 1 is preferred. However, in the formula 1, R
f
is a R
f
group, Q is a bivalent organic group, and R
1
is a hydrogen atom or a methyl group.
R
f
—Q—OCOCR
1
═CH
2
Formula 1
The R
f
group in the formula 1 is preferably a R
f
group containing no etheric oxygen atom or no thioetheric sulfur atom, particularly preferably a R
F
group. Especially preferred is a group represented by —(CF
2
)
n
F (wherein n is an integer of from 2 to 20), and n is preferably an integer of from 5 to 17. Particularly preferred is a group wherein n is an integer of from 7 to 13.
Q in the Formula 1 may, for example, be preferably —(CH
2
)
p+q
—, —(CH
2
)
p
CONH(CH
2
)
q
—, —(CH
2
)
p
OCONH(CH
2
)
q
—, —(CH
2
)
p
SO
2
NR
2
(CH
2
)
q
—, —(CH
2
)
p
NHCONH (CH
2
)
q
— or —(CH
2
)
p
CH(OH)—(CH
2
)
q
—, wherein R
2
is a hydrogen atom or an alkyl group, and each
Maekawa Takashige
Shimada Toyomichi
Asahi Glass Company Limited
Yoon Tae H.
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