Stock material or miscellaneous articles – Composite – Including interfacial reaction product of adjacent layers
Reexamination Certificate
1999-10-29
2002-01-08
Chen, Vivian (Department: 1773)
Stock material or miscellaneous articles
Composite
Including interfacial reaction product of adjacent layers
C428S421000, C428S447000, C428S448000, C528S010000, C528S028000, C528S030000, C528S042000, C427S299000, C427S301000, C427S302000, C427S407100, C427S419100, C427S419800
Reexamination Certificate
active
06337135
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a fluorine-containing polymer, a process for preparing the polymer, and the use of the polymer, for example, in a stainproof substrate having a stainproof layer of said polymer on a surface thereof.
RELATED ART
Materials such as metals, glass and resins are used as general-purpose substrates for a variety of articles such as automotive parts, OA apparatus and home electric appliances. The surfaces of these substrates are liable to get stained by the adhesion of dust particles suspended in the atmosphere of car interior, office interior, room interior and the like, and by the adhesion of oily substances which are contained in foods, oils for machines and the like and are difficult to be wiped off, and also by the adhesion of fingerprints of users. Therefore, these substrates need to be subjected to a stainproof treatment so that the substrate surface is rendered less adherent to dirt and the dirt once adhered can be easily removed.
As to the stainproof treatment of glass surface, publications such as Japanese Patent Application Laid-Open No. 126244/1989 (JP-A-1-126244) disclose techniques wherein coating films are formed either by direct application of a polymeric substance such as a polydimethylsiloxane to the glass surface or by immersion of glass in a treatment agent containing such a polymeric substance. Also known is a technique wherein a chemical absorption fluorine-containing monomolecular film is formed on the glass surface (see JP-A-4-132637, etc.).
As to the stainproof treatment of metal surface, Japanese Patent Kokoku Publication No. 53913/1995 (JP-B-7-53913) discloses a technique relating to an organic composite-plated steel plate by the steps of forming a chromate coating containing a silica sol silane coupling agent on a galvanized steel and thereafter forming a thin layer with an isocyanate-based paint composition.
However, the above-described treatments of prior arts do not provide a sufficient stainproof against oily dirt. In addition, the prior art treatments are associated with the problem that fingerprints tend to adhere to the substrate surface which is touched with fingers and the removal therefrom of the fingerprints is difficult.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a fluorine-containing polymer which can form on a substrate a stainproof layer exhibiting an excellent stainproof property against oily dirt, particularly fingerprints, as well as a process for preparing the polymer.
A second object of the present invention is to provide a stainproof substrate which exhibits an excellent stainproof property against oily dirt, particularly against fingerprints, as well as a process for preparing the substrate.
According to the present invention, the first object can be achieved by a fluorine-containing polymer having a number-average molecular weight of 500 to 100,000 and represented by the following general formula (I):
Rf—(OC
3
F
6
)
a
—(OC
2
F
4
)
b
—(OCF
2
)
c
—X—Y—Z—MP
n
R
m−n
(I)
wherein
Rf is a perfluroalkyl group;
a, b and c independently represent 0 or a number equal to or greater than 1, with the proviso that the sum of a, b and c is at least 1;
X is a group represented by the formula: —(O)
d
—(CF
2
)
e
—(CH
2
)
f
—(where d, e and f independently represent 0 or a number equal to or greater than 1, with the proviso that the sum of e and f is at least 1, and the presence order of the bracketed repeating units is arbitrary in the formula);
Y is a divalent polar group;
Z is a group represented by the formula: —(CH
2
)
g
—(where g is 0 or a number equal to or greater than 1);
M is a metal atom;
R is a hydrocarbon group;
P is a hydrolyzable polar group;
m is an integer equal to “(valency of M)−1”,
n is an integer of 1 to m;
with the proviso that the presence order of the bracketed repeating units is arbitrary in the formula; —OC
3
F
6
— represents either —OCF
2
CF
2
CF
2
— or —OCF(CF
3
)CF
2
—; and —OC
2
F
4
— represents either —OCF
2
CF
2
— or —OCF(CF
3
)—.
A preferred example of the fluorine-containing polymer (I) is a fluorine-containing polymer having a number-average molecular weight of 500 to 100,000 and represented by the following general formula (III):
Rf—(OCF
2
CF
2
CF
2
)
a
—X—Y—Z—SiP
n
R
3−n
(III)
wherein Rf, X, Y, Z, P and R are the same as defined above, and n is an integer of 1 to 3, with the proviso that a is a number equal to or greater than 1.
Likewise, the first object can be achieved by a fluorine-containing polymer having a number-average molecular weight of 500 to 100,000 and represented by the following general formula (II):
P
n
R
m−n
M—Z—Y—X—(OC
3
F
6
)
a
—(OC
2
F
4
)
b
—(OCF
2
)
c
—X—Y—Z—MP
n
R
m−n
(II)
wherein X, Y, Z, M, P, R, a, b, c, m and n are the same as defined above.
In the general formulae (I) and (III), Rf may be any perfluoroalkyl group contained in known fluorine-containing organic polymers, and may be, for example, a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. Preferably, Rf is CF
3
—, C
2
F
5
— or C
3
F
7
—.
In the general formulae (I) and (II), a, b and c represent, respectively, the numbers of the three-type repeating units in the perfluoropolyethers constituting the main skeleton of the fluorine-containing polymer, wherein a, b and c are each 0 or a positive number equal to or greater than 1, with the proviso that a+b+c is at least 1. Preferably, a, b and c are independently selected from 0 and a number in the range of from 1 to 200. More preferably, a, b and c are each 1 to 100 when the number-average molecular weight of the fluorine-containing polymer is taken into consideration.
The presence orders of the repeating units in brackets having subscripts a, b and c are described according to specific presence orders in the general formulae (I) and (II) for the purpose of convenience. However, the linkage orders of these repeating units are arbitrary without being limited by these orders.
In the general formulae (I), (II) and (III), X is a group represented by the formula: —(O)
d
—(CF
2
)
e
—(CH
2
)
f
—. In this formula, d, e and f independently represent 0 or a positive number equal to or greater than 1 (e.g., 1 to 50), with the proviso that e+f is at least 1, and the presence order of the repeating units in brackets having subscripts d, e and f is not limited in the formula. Preferably, d, e and f are each 0, 1 or 2. More preferably, d is 0 or 1, e is 2, and f is 0 or 1.
In the general formulae (I), (II) and (III), Y is a divalent polar group. Examples of the divalent polar group may include —COO—, —OCO—, —CONH—, —NHCO—, —OCH
2
CH(OH)CH
2
—, —CH
2
CH(OH)CH
2
O— —COS—, —SCO— and —O—. Preferably, Y is —COO—, —CONH—, —OCH
2
CH(OH)CH
2
— or —CH
2
CH(OH)CH
2
O—.
In the general formulae (I), (II) and (III), Z is a group represented by the formula: —(CH
2
)
g
—. In this formula, g represents 0 or a positive number equal to or greater than 1 (e.g., 1 to 50). Preferably, g is 0, 1, 2 or 3.
In the general formulae (I), (II) and (III), M is a metal atom. Examples of the metal atom may include metallic elements which constitute Groups 1 to 15 (e.g., Si, Al and Ti) of the Periodic Table.
In the general formulae (I) and (II), m is equal to “(valency of M)−1” and 0 or a positive number, while n is an integer of 1 to m. The valency of M is ordinarily 1 to 5, for example, 2 to 5, and particularly 3 to 5.
In the general formula (III), n is an integer of 1 to 3.
For example, in the case where M is silicon (Si), m is 3, and n is 1, 2 or 3. Meanwhile, in some cases, the fluorine-containing polymer is present as a mixture of polymers which are represented by the general formula (I), (II) or (III) and have different values for n. If the fluorine-containing polymer is present as a mixture of polymers as described above, n can be given as an average in the mixture.
In the general formulae (I), (II) and (III), the hydrocarbon group represented by R is preferably a hydrocarbon group containing 1 to 5 carbon atoms. Specific exam
Honda Yoshitaka
Yamaguchi Fumihiko
Birch & Stewart Kolasch & Birch, LLP
Chen Vivian
LandOfFree
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