Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-04-24
2001-12-04
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C526S250000, C526S255000, C526S328500, C526S332000, C524S545000, C524S560000
Reexamination Certificate
active
06326437
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to an aqueous-dispersing composition of a crosslinkable fluorine-containing resin for an aqueous coating or paint for use in the interior and exterior of a building.
DESCRIPTION OF THE RELATED ART
In the field of paints, various aqueous dispersions have been hitherto proposed. JP-A-5-32841, JP-B-47-15597 and JP-B-49-1458 disclose compositions comprising, as essential components, a synthetic resin crosslinkable with metal and a polyvalent metal compound. However, when these compositions are used in applications for the interior and exterior of a building, since a coating film thereof is easily deteriorated by an aqueous alkali medium, there is a disadvantage in that it is difficult to apply such compositions particularly to alkali substrates of concrete, ALC and slate.
In view of the above, an object of the present invention is to provide an aqueous dispersing composition of a fluorine-containing resin crosslinkable at room temperature, which is useful as a binder for coating and excellent in film forming property, stain-proofing property, weather resistance, chemical resistance and storage stability, by combining a specific fluorine-containing polymer with a polyvalent metal compound which can form a metal crosslinking structure.
SUMMARY OF THE INVENTION
The present invention relates to an aqueous-dispersing composition of crosslinkable fluorine-containing resin, which comprises a metal-crosslinking-formable polyvalent metal compound and an aqueous dispersion of fluorine-containing seed polymer (B) obtained by seed-polymerizing a non-fluorine-containing monomer containing a non-fluorine-containing monomer (a) having a carboxyl group and/or acetoacetyl group and a reactive &agr;,&bgr;-unsaturated group, in an aqueous medium in the presence of particles of a fluorine-containing polymer (A).
DETAILED DESCRIPTION OF THE INVENTION
The aqueous-dispersing composition of resin of the present invention comprises a metal-crosslinking-formable polyvalent metal compound and an aqueous dispersion of a fluorine-containing seed polymer (B) obtained by seed-polymerizing a non-fluorine-containing monomer containing a non-fluorine-containing monomer (a) having a specific functional group in an aqueous medium in the presence of particles of a fluorine-containing polymer (A). Each component is explained below.
1. Aqueous dispersion of Particles of Fluorine-containing Copolymer (A)
Examples of the fluorine-containing polymer (A) are polymers obtained by polymerizing a fluoroolefin as an essential component.
Examples of the fluoroolefin are, for instance, fluoroolefins having about 2 to 4 carbon atoms such as vinyl fluoride, vinylidene fluoride (VdF), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HEP) and trifluoroethylene.
Examples of the fluoroolefin polymer are homopolymers of those fluoroolefins or known copolymers comprising two or more of those fluoroolefins. Examples thereof are homopolymers of VdF, TFE and CTFE, VdF/TFE copolymer, VdF/HFP copolymer, VdF/CTFE copolymer, VdF/TFE/CTFE copolymer, VdF/TFE/HFP copolymer, TFE/HFP copolymer, and the like.
An aqueous dispersion of particles of the fluoroolefin polymers can be prepared through usual emulsion polymerization, namely, by emulsion-polymerizing a fluoroolefin monomer or monomer mixture in the presence of an emulsifying agent in an amount of not more than 5% by weight, preferably not more than 1% by weight on the basis of water.
Water used for the emulsion polymerization is preferably de-ionized water. Also it is preferable that the emulsifying agent is a fluorine-containing surfactant. Further, a reactive fluorine-containing emulsifying agent can be used. It is also possible to use a slight amount of a non-fluorine-containing nonionic emulsifying agent in combination.
The fluorine-containing emulsifying agent is one or a mixture of compounds having a structure containing fluorine atoms and having surface activity. Examples thereof are an acid represented by X(CF
2
)
n
COOH, in which n is an integer of 6 to 20, X is F or H, its metal salt, ammonium salt, amine salt or quaternary ammonium salt; an acid represented by Y(CH
2
CF
2
)
m
COOH, in which m is an integer of 6 to 13, Y is F or Cl, its metal salt, ammonium salt, amine salt or quaternary ammonium salt; and the like. In addition, it is possible to use solely a reactive emulsifying agent disclosed in JP-A-8-67795 and to use the reactive emulsifying agent in combination with the above-mentioned fluorine-containing emulsifying agent. Also it is possible to use a non-fluorine-containing nonionic emulsifying agent disclosed in JP-A-7-90153 together.
Examples of the other fluoroolefin polymer are, for instance, copolymers with a non-fluorine-containing monomer (excluding the above-mentioned non-fluorine-containing monomer (a) having functional group) being copolymerizable with fluoroolefin.
Examples of the non-fluorine-containing monomer copolymerizable with fluoroolefin are, for instance, &agr;-olefins such as ethylene, propylene and isobutylene; vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether and polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol and ally ether; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, and VEOVA9 and VEOVA10 (names of products available from Shell Chemical Co., Ltd.); and the like. Particularly &agr;-olefins, vinyl ethers, vinyl esters and alkenyls are preferably used.
Examples of the copolymers are TFE/propylene copolymer, TFE/ethylene copolymer, TFE/vinyl ester copolymers, TFE/vinyl ether copolymers, HFP/vinyl ether copolymers, HFP/vinyl ester copolymers, CTFE/vinyl ether copolymers, and the like. Further, there are copolymers comprising three or more monomers, i.e. copolymers containing the above-mentioned copolymer and as a modifying monomer, the above-mentioned monomer copolymerizable with fluoroolefin in an amount of not more than 30% by mole.
The aqueous dispersions of particles of the fluoroolefin copolymers can be prepared through usual emulsion polymerization. The emulsion polymerization method may be the same as in the polymerization method of the fluoroolefin polymer of above (1) except that the mixture of the fluoroolefin and monomer copolymerizable with fluoroolefin is used.
It is preferable that the fluoroolefin monomer is contained in the copolymers comprising the fluoroolefin and non-fluorine-containing monomer in an amount of 20 to 80% by mole. When an amount of the fluoroolefin monomer is less than 20% by mole, sufficient weather resistance cannot be exhibited. When the amount is more than 80% by mole, there is a tendency that at the time of making a coating and forming a coating film, a lowering of appearance occurs.
The aqueous dispersion of fluorine-containing seed polymer (B) of the present invention can be prepared by seed-polymerizing a non-fluorine-containing monomer (a) having carboxyl group and/or acetoacetyl group and a reactive &agr;,&bgr;-unsaturated group in an aqueous medium in the presence of particles of the above-mentioned fluorine-containing polymer (A).
The non-fluorine-containing &agr;,&bgr;-unsaturated monomer (a) having a carboxyl group and/or acetoacetyl group functions to impart stain-proofing property and stain removable property to a coating film by coordinate-bonding to a metal compound and forming a crosslinked structure.
Examples of the non-fluorine-containing &agr;,&bgr;-unsaturated monomer having carboxyl group are, for instance, &agr;,&bgr;-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, crotonic acid, maleic acid and maleic anhydride. Among them, acrylic acid and methacrylic acid are preferred from the viewpoint of copolymerizability.
A preferred non-fluorine-containing &agr;
Imoto Katsuhiko
Mitsuhata Nobuo
Nagato Masaru
Tsuda Nobuhiko
Asinovsky Olga
Daikin Industries Ltd.
Seidleck James J.
Sughrue Mion Zinn Macpeak & Seas, PLLC
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