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
2000-11-15
2002-10-29
Dawson, Robert (Department: 1712)
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...
C442S081000, C528S038000, C528S042000
Reexamination Certificate
active
06472468
ABSTRACT:
BACKGROUND OF THE INVENTION
In the prior art, a variety of organopolysiloxanes including dimethylpolysiloxane, epoxy group-containing polysiloxanes, and aminoalkyl group-containing polysiloxanes are widely used as a treating agent for imparting softness, smoothness and other desirable properties to various fibers and fibrous materials. Among others, aminoalkyl group-containing polysiloxanes are most often used since they can impart satisfactory softness to various fibers and fibrous materials. JP-B 48-1480, JP-B 54-43614, JP-B 57-43673, JP-A 60-185879, JP-A 60-185880, and JP-A 64-61576 disclose fiber or fabric treating agents comprising as an active ingredient organopolysiloxanes having aminoalkyl groups such as —C
3
H
6
NH
2
and —C
3
H
6
NHC
2
H
4
NH
2
. These fiber or fabric treating agents are widely used because of softness improvement.
Recently, fluorochemical fiber or fabric treating agents are used for imparting water and oil repellency. Since the treated fabric is deteriorated in texture, it becomes customary to use silicone softeners in combination with fluorochemical water/oil repellents.
However, when the prior art dimethylpolysiloxanes, especially organopolysiloxanes having aminoalkyl groups such as —C
3
H
6
NH
2
and —C
3
H
6
NHC
2
H
4
NH
2
are used in combination with the fluorochemical water/oil repellents, they are incompatible, and water and oil repellency is rather exacerbated.
More particularly, an aminoalkyl group-containing organopolysiloxane of a polyether chain having a relatively low molecular weight is relatively compatible with the fluorochemical water/oil repellents, but adversely affects water repellency because of the hydrophilicity of polyether.
An attempt was made to introduce a fluorinated group into a silicone softener for imparting water and oil repellency while a variety of fluorinated organopolysiloxanes were proposed. For example, Japanese Patent No. 2,544,935 discloses a method of synthesizing a fluorinated organopolysiloxane by reacting an amino-modified silicone (e.g., modified with —C
3
H
6
NHC
2
H
4
NH
2
) with a methyl perfluoroakylcarboxylate. JP-A 5-86197 discloses a method of synthesizing a fluorinated organopolysiloxane by reacting an amino-modified silicone with a perfluoroalkylsulfonic amide. JP-A 8-109580 discloses a method of synthesizing a fluorinated organopolysiloxane by reacting an amino-modified silicone with methyl carboxylate-modified hexafluoropropylene oxide.
These fluorinated organopolysiloxanes, however, have the problem that they improve oil repellency, but not to a fully satisfactory extent, and need a long time of reaction upon their synthesis.
SUMMARY OF THE INVENTION
An object of the invention is to provide a fluorinated polysiloxane which is easy to synthesize, can impart both water and oil repellency when used alone as a silicone softener, and does not exacerbate water repellency when used in combination with a fluorochemical water/oil repellent. Another object is to provide a method for preparing the same. A further object is to provide a fiber or fabric treating agent composition comprising the same.
It has been found that a fluorinated polysiloxane containing a linkage or group in which a monovalent hydrocarbon group containing at least three fluorine atoms and an organoxy group are attached to a common silicon atom as represented by the formula (1) or (2) and at least one aminoalkyl group attached to a silicon atom in a molecule, is obtained by effecting alcohol-elimination reaction among a both end hydroxyl-blocked organopolysiloxane of the formula (5), a fluorinated triorganoxysilane of the formula (6), and an aminoalkyl group-containing organoxysilane of the formula (7), all the formulas being shown later. This fluorinated polysiloxane, when fibers are treated therewith, can impart both water and oil repellency to the fibers and maintain a better texture than conventional fluorochemical oil repellents, and is thus suitable as a fiber or fabric treating agent. It has also been found that the fluorinated polysiloxane is effective as a paint additive, releasing agent and lubricant.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In a first aspect, the invention provides a fluorinated polysiloxane comprising at least one unit of the following general formula (1) and containing at least one aminoalkyl group attached to a silicon atom in a molecule.
In a second aspect, the invention provides a fluorinated polysiloxane having at least one terminal group of the following general formula (2) and containing at least one aminoalkyl group attached to a silicon atom in a molecule.
In formulas (1) and (2), R
1
is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20 carbon atoms, R
2
is a monovalent hydrocarbon group containing at least three fluorine atoms, R
3
is an organoxy group represented by —OR
1
wherein R
1
is as defined above, and p is a positive number of from 2 to 200.
Illustrative examples of the monovalent hydrocarbon group represented by R
1
include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, and eicosyl, alkenyl groups such as vinyl and allyl, aryl groups such as phenyl and tolyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, and substituted ones of the foregoing groups in which some or all of the hydrogen atoms attached to carbon atoms are replaced by halogen atoms, such as chloromethyl, trifluoropropyl, and chlorophenyl. Of these, methyl, phenyl and/or trifluoropropyl account for at least 90 mol % of R
1
.
R
2
is a monovalent hydrocarbon group containing at least three fluorine atoms, as exemplified by a group of the following general formula (3).
—CH
2
CH
2
C
n
F
2n+1
(3)
The letter n is a positive number of at least 3, preferably 3 to 10 and more preferably 5 to 8. If n is less than 3, satisfactory water repellency does not manifest. With n in excess of 10, water repellency is no longer enhanced and the organopolysiloxane becomes expensive. Illustrative examples of R
2
are —CH
2
CH
2
C
5
F
11
, —CH
2
CH
2
C
6
F
13
, —CH
2
CH
2
C
7
F
15
, —CH
2
CH
2
C
8
F
17
, —CH
2
CH
2
C
9
F
19
, and —CH
2
CH
2
C
10
F
21
.
R
3
is an organoxy group represented by —OR
1
wherein R
1
is as defined above, preferably an alkoxy group of 1 to 6 carbon atoms. Illustrative examples of R
3
are methoxy, ethoxy and propoxy, with the methoxy being most preferred.
The letter p is a positive number of from 2 to 200, and preferably from 10 to 100.
The fluorinated polysiloxane contains at least one aminoalkyl group attached to a silicon atom. The aminoalkyl group is preferably represented by the following general formula (4):
—R
4
(NR
5
CH
2
CH
2
)
a
NR
6
2
(4)
wherein R
4
is a divalent hydrocarbon group of 1 to 6 carbon atoms, R
5
and R
6
each are hydrogen or a monovalent hydrocarbon group of 1 to 8 carbon atoms, and “a” is equal to 0, 1 or 2.
The divalent hydrocarbon groups represented by R
4
include alkylene groups. The monovalent hydrocarbon groups represented by R
5
and R
6
include alkyl groups, aryl groups such as phenyl, and alkenyl groups such as vinyl. Two R
6
groups may be the same or different.
The aminoalkyl group is incorporated as the unit shown below.
Herein, R
0
is an aminoalkyl group such as a group of formula (4); R
1
is as defined above; and q is such a number that the aminoalkyl group may account for 0.2 to 10 mol % based on the entire silicon atoms.
It is requisite that at least one alkylamino group be included in the molecule although it is preferred that the aminoalkyl group account for 0.2 mol % to 10 mol % and especially 0.5 mol % to 5.5 mol %, based on the entire silicon atoms. If the aminoalkyl group content is less than 0.2 mol%, full reaction may not take place between a fluorinated triorganoxysilane and a both end hydroxyl-blocked organopolysiloxane. An aminoalkyl group content of more than 10 mol % may cause yellowing of treated fibers.
The fluorinated polysiloxane containing at least one unit of formula (1) may have any desired terminal group. Exemplary termina
Shin-Etsu Chemical Co. , Ltd.
Zimmer Marc S
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