Latex binder for coating composition

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

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C523S402000, C523S406000, C523S408000, C523S409000, C523S410000, C523S412000, C524S517000

Reexamination Certificate

active

06465562

ABSTRACT:

The present invention relates to aqueous coating compositions used, for example, as water-based paints, and which crosslink at room temperature.
Coating compositions which crosslink under ambient conditions are known in the prior art. The best known compositions are based on reactions between epoxides and carboxylic acids, between isocyanates and water, between polyaziridine and carboxylic acids, and between activated methylene and acrylic acid.
Compositions involving the reaction between an epoxide and a carboxylic acid comprise a binder which is either the mixture of a latex containing a carboxylic acid function and a latex containing an epoxide function, or a latex containing both of these functions at the same time, such as, for example, the one described in EP 653,469.
It has been observed that these binders are highly unstable on storage: the crosslinking reactions between the two acid and epoxide functions take place during this storage, to the extent that the reactive function of the binder does not take place during use of the binder as a coating. This creates a film with poor properties, in particular one with poor chemical resistance.
One aim of the present invention is thus to propose coating compositions based on a mixture of latex containing carboxylic acid functions and epoxy functions, which behave satisfactorily on storage and have good reactivity at the time of use.
With these aims, the invention relates to a binder for a coating composition, comprising:
at least one latex (A) prepared from ethylenically unsaturated monomers and containing a carboxylic acid function, and
at least one latex (B) prepared from ethylenically unsaturated monomers and containing an epoxide function, and for which the particle size of the said latices is not more than 50 nm.
The invention also relates to a coating composition based on a binder as defined above.
Other details and advantages of the invention will emerge even more clearly on reading the description and the examples.
The invention thus relates, firstly, to a binder for a coating composition, comprising:
at least one latex (A) prepared from ethylenically unsaturated monomers and containing a carboxylic acid function, and
at least one latex (B) prepared from ethylenically unsaturated monomers and containing an epoxide function, and for which the particle size of the said latices is not more than 50 nm.
The term latex is understood to refer to an aqueous dispersion of polymer particles.
According to the invention, the binder is a mixture of latices prepared from ethylenically unsaturated monomers. This mixture comprises at least one latex containing a carboxylic acid function and at least one latex containing an epoxide function. The essential characteristic of the binder according to the invention is that the particles of these latices contain carboxylic acid and epoxide functions and are not more than 50 nm in size, preferably between 20 and 40 nm in size. The term size is understood to refer to the particle diameter. The particle size distribution of the particles in each latex is relatively unimportant. On the other hand, it is essential for all of the particles in the latex to be not more than 50 nm in size: the coarsest latex particles are thus not more than 50 nm in size. The particle size is measured by transmission electron microscopy (TEM).
Preferably, the molecular mass {overscore (M)}
n
of the polymer in the latex (A), which contains a carboxylic acid function, is between 40,000 and 500,000 g/mol, preferably between 100,000 and 400,000 g/mol.
For the latex (B), which contains an epoxide function, the molecular mass {overscore (M)}n is preferably between 4000 and 50,000 g/mol, even more preferably between 20,000 and 40,000 g/mol.
These molecular masses are measured by gel chromatography (GPC).
In general, the minimum film-forming temperature (MFFT) of the polymer in the latex (A), which contains a carboxylic acid function, is between 0 and 15° C., preferably between 6 and 12° C., and that of the polymer in the latex (B), which contains an epoxide function, is between 30 and 50° C., preferably between 35 and 45° C.
In general, the latex (A), which contains a carboxylic acid function, and the latex (B), which contains an epoxide function, are present in the binder in an “equimolar” ratio, i.e. the latices are introduced in amounts such that the mixture contains one carboxylic acid function per epoxide function.
It has been observed that the best results are obtained when the epoxide groups in the latex (B) are at the surface of the particles in the said latex. It is thus preferable to use a latex (B) in which most of the epoxide functions are at the surface of the polymer particles.
The binder according to the invention is obtained by simple mixing of the latices (A) and (B).
The latices (A) and (B) are generally derived from the polymerization of ethylenically unsaturated monomers such as:
(meth)acrylic esters in which the alkyl group contains from 1 to 20 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, decyl acrylate, lauryl methacrylate or benzyl acrylate,
vinylaromatics such as styrene, vinyltoluene or &agr;-methylstyrene.
The latex (A) is derived from the polymerization of at least one of the said ethylenically unsaturated monomers and from at least one monomer carrying the carboxylic acid function. In general, the carboxylic acid function originates from a mono- or polycarboxylic acid containing one polymerizable bond per molecule. In general, such acids contain 3 to 24 carbon atoms and one or two carboxylic acid groups per molecule. They may be, for example:
acrylic, methacrylic, maleic, fumaric, itaconic, ethacrylic, crotonic or citraconic acid,
semi-esters of dicarboxylic acids in which the esterified alcohol group comprises 1 to 20 carbon atoms, such as: methyl hydrogen fumarate, benzyl hydrogen maleate, octyl hydrogen itaconate or dodecyl hydrogen citraconate, and the like.
The preferred carboxylic acids are acrylic acid and methacrylic acid.
The monomers carrying the carboxylic acid function generally represent at least 15% by weight of the sum of the monomers forming the polymer in the latex (A).
The latex (B) is derived from the polymerization of at least one of the above ethylenically unsaturated monomers and of at least one monomer carrying the epoxide function. Preferably, the epoxide function originates from a glycidyl (meth)acrylate monomer. Such a monomer can be obtained commercially. It can be derived from the esterification reaction of acrylic acid or methacrylic acid with glycidol or epichlorohydrin, followed by a adehydrohalogenation.
The monomers carrying the epoxide function generally represent 10 to 40% by weight of the sum of the monomers forming the polymer in the latex (B), preferably 20 to 30%.
These latices (A) and (B), which have a particle size of not more than 50 nm, can be obtained by the standard polymerization processes such as, for example, the one described in patent application EP 644,205, and in particular Example 4 of that application. This involves polymerization of monomers emulsified in water. Preferably, these processes are carried out continuously. According to this Example 4, the latex is obtained by preparing an aqueous solution comprising the surfactant and the polymerization initiator, into which the monomer mixture is introduced portionwise and continuously.
The surfactants used to emulsify the monomers are especially anionic surfactants.
As examples of anionic surfactants which may be used, mention may be made of linear sodium and potassium alkyl sulphates such as sodium lauryl sulphate, sodium alkylaryl sulphates, ethoxylated alkylphenol sulphates and sulphonates, ethoxylated fatty alcohol sulphates and sulphonates, and sulphosuccinates.
The molecular masses of the latices (A) and (B) are controlled by the amount of transfer agent introduced during the polymerization.
The amounts of surfactants used in the emulsion polymerization

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