Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-04-24
2002-03-19
Michl, Paul R. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S535000
Reexamination Certificate
active
06359030
ABSTRACT:
TECHNICAL FIELD
The present invention relates to an aqueous-dispersing composition of composite resin being excellent in film forming property and giving a coating film having excellent chemical resistance, water resistance and mechanical properties and a mixture of aqueous dispersions containing the composite resin.
BACKGROUND ART
In the field of an emulsion paint, giving a good film forming property has been assumed to be contrary to obtaining a coating film having a high modulus of elasticity, and a method of sacrificing an anti-staining property by lowering a glass transition temperature Tg of a resin or a method of forming a film of resin emulsion having a high Tg by using a large amount of plasticizer has been employed. Further it is known that by reducing a molecular weight, an effect of the plasticizer is increased, but as a result, problems with lowering of water resistance and mechanical properties arise.
DISCLOSURE OF INVENTION
In view of the above-mentioned points, the present inventors have made intensive studies and have found that an aqueous-dispersing composition of composite resin which is prepared by seed-polymerizing a monomer in an aqueous medium in the presence of particles of a synthetic resin having a specific range of molecular weight has an excellent film forming property and can form a coating film excellent in chemical resistance, water resistance and mechanical properties and further that a mixture of the aqueous dispersion of composite resin and other aqueous dispersion of a specific synthetic resin can form a coating film excellent in hot water resistance. Thus the present invention was completed.
The present invention relates to an aqueous-dispersing composition of composite resin, which is an aqueous-dispersing composition of a composite resin (C) comprising a synthetic resin (A) of a monomer or monomers (a) and a synthetic resin (B) of a monomer or monomers (b) having different component or proportion from that of the monomer(s) (a); the composite resin (C) is prepared by seed-polymerizing the monomer(s) (b) in an aqueous medium in the presence of particles of the synthetic resin (A) and an intrinsic viscosity “&eegr;” of the synthetic resin (A) is from 0.3 to 2.0 (intrinsic viscosity measured at 35° C. in methyl ethyl ketone (MEK) solvent, hereinafter the same).
The present invention also relates to a mixture of the aqueous dispersion of the above-mentioned composite resin (C) and an aqueous dispersion of synthetic resin (D) having an intrinsic viscosity “&eegr;” of not less than 0.6 which is larger by 0.3 or more than the intrinsic viscosity “&eegr;” of the synthetic resin (A).
As the mixture of aqueous dispersions of resin, preferred is the mixture comprising an aqueous dispersion of fluorine-containing seed polymer (C1) obtained by seed-polymerizing a non-fluorine-containing monomer (b1) having a reactive &agr;,&bgr;-unsaturated group in an aqueous medium in the presence of particles of a fluorine-containing polymer (A1) having an intrinsic viscosity “&eegr;” of from 0.3 to 2.0 and an aqueous dispersion of fluorine-containing seed polymer ((D1) obtained by seed-polymerizing a non-fluorine-containing monomer (g1) having a reactive &agr;,&bgr;-unsaturated group in an aqueous medium in the presence of particles of a fluorine-containing polymer (E1) having an intrinsic viscosity “&eegr;” of not less than 0.6 which is larger by 0.3 or more than the intrinsic viscosity “&eegr;” of the fluorine-containing polymer (A1).
BEST MODE FOR CARRYING OUT THE INVENTION
The composite resin (C) of the present invention is a seed polymer of the synthetic resin (A) comprising the monomer(s) (a) and the synthetic resin (B) comprising the monomer(s) (b).
The synthetic resin (A) is not limited particularly and known synthetic resins are used, for example, a fluorine-containing polymer, acrylic resin, silicon-modified acrylic resin, urethane resin, melamine resin, silicone resin, epoxy resin, polyester, and the like. Among them, preferred is a fluorine-containing polymer from the viewpoint of weather resistance and chemical resistance.
The monomer (a) is not limited particularly. The monomer (a) may be one which can give the above-mentioned synthetic resin by polymerization.
When the synthetic resin (A) is the fluorine-containing polymer (A1), fluoroolefins having about 2 to 4 carbon atoms, for example, vinyl fluoride, vinylidene fluoride (VdF), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene, and the like can be used.
Examples of the polymer (A1) of the above-mentioned fluoroolefin are, for instance, homopolymers of the above-mentioned fluoroolefins and known copolymers of two or more fluoroolefins. There are homopolymers of VdF, TFE and CTFE, VdF/TFE copolymer, VdF/HFP copolymer, VdF/CTFE copolymer, VdF/TFE/CTFE copolymer, VdF/TFE/HFP copolymer and TFE/HFP copolymer.
Aqueous dispersions of particles of those fluoroolefin polymers (A1) are prepared by usual emulsion polymerization. Namely the aqueous dispersions can be obtained by emulsion-polymerizing a fluoroolefin monomer or a mixture of fluoroolefin monomers in the presence of an emulsifying agent of not more than 5% by weight, preferably not more than 1% by weight on the basis of water.
It is preferable that water to be used in the emulsion polymerization is de-ionized water. Also it is preferable that the emulsifing agent is a fluorine-containing surfactant. Further a reactive fluorine-containing emulsifying agent can also be used. Also a slight amount of non-fluorine-containing nonionic emulsifying agent can be used together with the above-mentioned emulsifying agent.
The fluorine-containing emulsifying agent means a compound containing a fluorine atom in its structure and having a surface-activating ability or a mixture of two or more thereof. Examples of the compound are, for instance, 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 a reactive emulsifying agent disclosed in JP-A-8-67795 solely or 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.
Other examples of the fluoroolefin polymer (A1) are, for instance, copolymers of fluoroolefin and a non-fluorine-containing monomer (excluding reactive non-fluorine-containing &agr;,&bgr;-unsaturated monomers (b2) having functional group which are described hereinafter).
As the monomers being copolymerizable with the above-mentioned fluoroolefins, there are, for example, &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 allyl ether; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, and VEOVA9 and VEOVA10 (brand names of Shell Chemical Co., Ltd.); ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid; and the like. Particularly &agr;-olefins, vinyl ethers, vinyl esters and alkenyls are used preferably.
Examples of the above-mentioned copolymers are TFE/propylene copolymer, TFE/ethylene copolymer, TFE/vinyl ester copolymer, TFE/vinyl ether copolymer, HFP/vinyl ether copolymer, HFP/vinyl ester copolymer, CTFE/vinyl ether copolymer, and the like. Further there are polymers comprising three or more monomers, which contain, in addition to the above-mentioned copolymer, a monomer copolymerizable with the above-mentioned fluoroolefin a
Imoto Katsuhiko
Mitsuhata Nobuo
Nagato Masaru
Tsuda Nobuhiko
Daikin Industries Ltd.
Michl Paul R.
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