Composition for treating paper and paper treated therewith

Details Composition for treating paper and paper treated therewith Composition for treating paper and paper treated therewith

1999-11-23

2001-10-23

Cain, Edward J. (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...

C524S376000, C524S544000

Reexamination Certificate

active

06306944

ABSTRACT:

The present invention relates to a composition for treating paper and a paper treated with this composition.
In recent years, material of containers or packages for foods, confectionery, etc. has been changed from plastics to papers with an increasing interest in protection for the environment. Water- and oil-repellant treatments of papers are conducted to avoid penetration of oil or water contained in foods, confectionery, etc. to papers.
Heretofore, as a water and oil repellent for papers, various agents have been proposed as follows: (1) a treating agent comprising a phosphate containing a polyfluoroalkyl group (hereinafter referred as a R
f
) (JP-A-64-6196, JP-A-3-123786), (2) a treating agent comprising a copolymer composed of polymer units of an acrylate having a R
f
group, polymer units of an alkyl(meth)acrylate and polymer units of a methacrylate having a polyethylene oxide group (JP-A-8-59751), (3) a treating agent comprising a copolymer of an acrylate having a R
f
group and vinylidene chloride (JP-A-55-69677, JP-A-51-133511, JP-B-53-22547). Further, as a water and oil repellent for fibers, (4) a copolymer comprising polymer units of an acrylate having a R
f
group and polymer units of octadecyl(meth)acrylate has been known.
However, a treating agent (1) comprising a phosphate containing a polyfluoroalkyl group has a problem that it can not impart adequate oil repellency to papers since the phosphate is a water soluble compound. Further, its oil repellency substantially decreases when it is used with a sizing agent together.
Meanwhile, as a general oil resistance treatment for papers, the post-application method has been known wherein papers are impregnated or coated with a treating agent. In this method, a size press and various coating machines may be used, and drying is conducted in a short time of from a few seconds to several tens seconds at from 80 to 100° C. When the post-application method is used, it is necessary to select a treating agent which can impart high water resistance and oil resistance under drying at a low temperature and in a short time.
When the treating agent (2) is used in the post-application method, however, a problem has been observed that adequate property is not shown. When the treating agent (3) diluted with water is applied to papers, dipping, nipping, circulation, etc. at high speed cause various drawbacks such as instability of the agent, occurrence of scum in the agent, stains of rolls, inadequate adhesion to papers. Thus, the agent (3) has such problem that it can not impart adequate property to papers. When the treating agent (4) is applied to papers and dried at low temperature and in a short time, adequate water repellency to the papers has not been attained.
It is an object of the present invention to solve the above-mentioned problems and to provide a composition for treating papers without such problems.
It is another object of the present invention to provide a paper having superior water repellency and oil resistance treated with such a composition for treating papers.
The inventors of the present invention have found that superior water repellency and oil resistance can be attained even under drying condition of at low temperature and in a short time, if papers are treated with a composition comprising, as an essential component, a copolymer comprising particular polymer units.
Further, it has also been found that said composition has such high mechanical stability that the scum in the liquid of the agents and stains of the rolls scarcely occur.
The present invention provides a composition for treating papers comprising, as essential components, a polymer (A), a surfactant (B) and a medium (C), wherein said polymer (A) comprises polymer units of (meth)acrylate having a R
f
group, polymer units of a vinylidene halide and/or polymer units of a long chain alkyl(meth)acylate, and polymer units of the following formula 1:
—[CH
2
—C(R)[CO—Q—(CH
2
)
n
CHR
4
—CH
2
N
+
(R
1
)(R
2
)(R
3
).X
−
]]—,  Formula 1
wherein R is a hydrogen atom or a methyl group; Q is —O— or —NR
5
—, wherein R
5
is a hydrogen atom or an alkyl group; each of R
1
, R
2
and R
3
which are independent of one another is a hydrogen atom or an alkyl group; R
1
and R
2
may together form a bivalent organic group; R
4
is a hydrogen atom or a hydroxyl group; n is a number from 1 to 4 and X
−
is a counter ion.
Now, the present invention will be described in detail with reference to the preferred embodiments.
In the present invention, an acrylate and a methacrylate are referred collectively as a (meth)acrylate. The same applies to the description of an (meth)acrylamide, etc.
The R
f
group is a alkyl group having at least two hydrogen atoms substituted with fluorine atoms. The R
f
group may have a straight chain structure or a branched chain structure. The carbon number of the R
f
group is preferably from 2 to 20, particularly preferably from 4 to 18.
The number of the fluorine atoms in the R
f
group is at least 60%, more preferably at least 80%, particularly preferably 100% in substantial, when the number is represented by the formula of [(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)]×100(%). Further, an alkyl group having all hydrogen atoms substituted with fluorine atoms will be described as a perfluoroalkyl group.
The R
f
group may contain a chlorine atom, etc. An etheric oxygen atom may be inserted between the carbon-carbon bond in the R
f
group. Thus, the R
f
group may be a group having a moiety of polyfluorooxyalkylene.
The following groups may be mentioned as specific examples of the R
f
group.
C
4
F
9
— [any one of structural isomers such as F(CF
2
)
4
—, (CF
3
)
2
CFCF
2
—, (CF
3
)
3
C— and CF
3
CF
2
CF(CF
3
)—], C
5
F
11
— [such as F(CF
2
)
5
—], C
6
F
13
— [such as (CF
2
)
6
—], C
7
F
15
— [such as F(CF
2
)
7
—], C
8
F
17
— [such as F(CF
2
)
8
—], C
9
F
19
— [such as F(CF
2
)
9
—], C
10
F
21
— [such as F(CF
2
)
10
—], C
12
F
25
— [such as F(CF
2
)
12
—], C
14
F
29
— [such as F(CF
2
)
14
—], C
16
F
33
— [such as F(CF
2
)
16
—], Cl(CF
2
)
s
— (wherein s is an integer of from 2 to 16), H(CF
2
)
t
— (wherein t is an integer of from 2 to 16), (CF
3
)
2
CF(CF
2
)e- (wherein e is an integer of from 1 to 14), etc.
The following groups may be mentioned as specific examples of the case where the R
f
group is a group having an etheric oxygen atom inserted between the 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
— (wherein each of r and z is an integer of from 1 to 10, u is an integer of from 2 to 6, v is an integer of from 1 to 11, and w is an integer of from 1 to 11).
The R
f
group is preferably a perfluoroalkyl group. The perfluoroalkyl group has a straight chain structure and is preferably represented by F(CF
2
)
p
— (wherein p is an integer of from 4 to 16, preferably from 6 to 12).
The (meth)acrylate having a R
f
group in the present invention is a compound wherein a R
f
group exists in a ester residual group of (meth)acrylate. The (meth)acrylate having a R
f
group may be composed of one type, or two or more types. In the case of two or more types, a mixture of at least two types having different numbers of carbon atoms one another in the R
f
group is preferred.
The following compounds may be mentioned as the (meth)acrylate having a R
f
group. In the compounds, R
6
represents a hydrogen atom or a methyl group and R
f
represents a R
f
group mentioned above, preferably a perfluoroalkyl group.
CH
2
═CR
6
COOCH
2
CH
2
R
f
,
CH
2
═CR
6
COOCH
2
CH
2
N(CH
2
CH
2
CH
3
)COR
f
,
CH
2
═CR
6
COOCH(CH
3
)CH
2
R
f
,
CH
2
═CR
6
COOCH
2
CH
2
N(CH
3
)SO
2
R
f
,
CH
2
═CR

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