HK1018791B - Water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers - Google Patents
Water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers Download PDFInfo
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Description
The present invention relates to water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers.
Redispersible powders prepared by spray drying of acrylic film-forming polymer dispersions, in particular dispersions of vinyl ester polymers, are known.
Film-forming polymers prepared from ethylenically unsaturated monomers are generally used as adjuvants in hydraulic inorganic binder compositions to improve their use and properties after hardening, such as adhesion to various substrates, leaktightness, flexibility and mechanical properties.
Redispersible powders have the advantage, compared with aqueous dispersions, of being able to be premixed with cement in the form of ready-to-use powder compositions which can be used, for example, for producing mortars and concretes to be adhered to building materials, for producing adhesive mortars or for coating protective and decorative coatings inside and outside buildings.
It is customary to add relatively large amounts of inert materials and protective colloids to the powder in order to obtain, under the action of pressure and temperature, a powder which does not agglomerate during storage and which is suitably redispersible in water.
In order to prepare readily redispersible polymer powders, it has been proposed to add melamine-formaldehyde-sulfonates (U.S. Pat. No. 3, 3784648) or naphthalene-formaldehyde-sulfonates (DE-A-3143070) condensation products and/or vinylpyrrolidone-vinyl acetate copolymers (EP-78449) to the dispersion before pulverization.
The object of French patent FR-A2245723 is a stable, water-dispersible formulation obtained by congealing and containing a polymer latex powder and a water-soluble dispersant (saccharide).
The object of the present invention is to provide novel powder compositions which are completely or almost completely redispersible in water and which are based on film-forming polymers prepared from ethylenically unsaturated monomers.
It is a further object of the present invention to provide a redispersible powder of the above type which is stable on storage and does not agglomerate.
The invention also relates to a process for preparing a powder of the above type from a film-forming polymer latex.
Another object of the invention is a powder of the above-mentioned type, which may be a powder or a pseudolatex formed after redispersion in water, which can be used in any of the various fields of application in which latexes are used for the production of coatings, in particular coating and papercoating compositions, or adhesive compositions, in particular pressure-sensitive adhesives and tiling adhesives.
It is an object of the present invention to provide a redispersible powder of the above type (or a pseudolatex prepared therefrom), in particular with a view to making it an additive to hydraulic binders of the mortar or concrete type and to making these binders improved in terms of adhesion after immersion in a wet medium.
These and other objects are achieved by the present invention which relates in fact to a water-redispersible pulverulent composition comprising:
a)100 parts by weight of a water-insoluble film-forming polymer powder made from at least one ethylenically unsaturated monomer and at least one monomer selected from the group consisting of monomers having carboxylic acid functionality and acrylamide or methacrylamide,
b)2 to 40 parts by weight, preferably 8 to 22 parts by weight, of at least one amino acid or a salt thereof.
The invention also relates to a process for preparing such a powder composition comprising:
removing water from an aqueous emulsion containing said insoluble film-forming polymer prepared by emulsion polymerization and containing an appropriate amount of additive b),
-forming the dried residue into a powder having the desired particle size.
The invention also relates to a pseudolatex prepared by redispersing the above-mentioned pulverulent composition in water.
Finally, the invention relates to the use of said pseudolatex and of the above-mentioned pulverulent composition as additives for hydraulic binders, adhesives, paper-coating compositions and paints.
The present invention relates, in a first aspect, to a water-redispersible pulverulent composition comprising:
a)100 parts by weight of a water-insoluble film-forming polymer powder made from at least one ethylenically unsaturated monomer and at least one monomer selected from the group consisting of monomers having carboxylic acid functionality and acrylamide or methacrylamide,
b)2 to 40 parts by weight, preferably 8 to 22 parts by weight, of at least one amino acid or a salt thereof.
The ethylenically unsaturated monomers are selected from: styrene, butadiene, C1-C12Alkyl acrylic or methacrylic esters, and their corresponding acids or vinyl esters. The pulverulent compositions according to the invention advantageously contain an insoluble film-forming polymer prepared from styrene/butadiene or styrene/butadiene/acrylic acid mixtures as ethylenically unsaturated monomers.
The monomer containing a carboxylic acid function is chosen from ethylenically unsaturated carboxylic acids. Preferably they are ethylenically unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, crotonic acid, maleic anhydride, mesaconic acid, glutaconic acid or mixtures thereof.
The film-forming polymer is preferably prepared by polymerization of a mixture of monomers comprising 99.9 to 92% by weight of at least one ethylenically unsaturated monomer and 0.1 to 8%, preferably 2 to 5% by weight of at least one monomer containing carboxylic acid functionality. The particle size of the film-forming polymer powder is 0.05-5 microns, preferably 0.12-0.18 microns, and more preferably 0.10-0.20 microns.
Preferably, the glass transition temperature (Tg) of the water-insoluble film-forming polymer is not more than 20 ℃, preferably between-20 and 20 ℃.
The water-insoluble film-forming polymer may be prepared by emulsion polymerization of the monomers. Such polymerizations are usually carried out in the presence of an emulsifier and a polymerization initiator.
The monomers can be added to the reaction medium either as a mixture or separately and simultaneously before the start of the one-stage polymerization or during the successive stepwise or continuous polymerization.
As emulsifiers, use is generally made of the customary anionic agents, which are, in particular, salts of fatty acids, alkyl sulfates, alkyl sulfonates, alkylaryl sulfates, alkylaryl sulfonates, aryl sulfates, aryl sulfonates, sulfosuccinates, alkali metal alkyl phosphates. They are used in an amount of 0.01 to 5 wt.% relative to the total amount of monomers.
The emulsion polymerization initiator is water-soluble and is represented more specifically by hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, and persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate. The amount thereof is 0.05 to 2 wt% relative to the total amount of the monomers. These initiators may be optionally combined with reducing agents such as sodium bisulfite or sodium formaldehyde sulfoxylate, polyvinylamines, sugars: dextrose, sucrose or metal salts. The amount of the reducing agent is 0 to 3 wt% based on the total amount of the monomers.
The reaction temperature varies depending on the initiator used, and is usually 0 to 100 ℃ and preferably 50 to 80 ℃.
The transfer agent is used in an amount of 0 to 3% by weight with respect to the monomers and is generally chosen from mercaptans, such as N-dodecyl mercaptan, tert-butyl mercaptan or their esters, such as methylthiopropionate; cyclohexene; halogenated hydrocarbons such as chloroform, bromoform and carbon tetrachloride.
The powder composition of the invention also contains at least one amino acid or one amino acid salt. The amino acids are preferably selected from:
-a mono-carboxylated mono-amino acid,
-or a di-carboxylated mono-amino acid,
-or monocarboxylated diamino acids.
The monocarboxylated monoamino acids can be chosen in particular from glycine, alanine, leucine and phenylalanine, the dicarboxylated monoamino acids are chosen from aspartic acid, glutamic acid and hydroxyglutamic acid, and the monocarboxylated diamino acids can be chosen from arginine, lysine, histidine and cystine.
It is advantageous that the amino acids added to the composition of the invention have good water solubility; thus, the amino acids of the composition may be in the form of salts, particularly water soluble or alkali soluble salts. They may be, for example, sodium, potassium, ammonium or calcium salts.
The powder composition according to the invention may also contain at least one water-soluble compound c) chosen from polyelectrolytes of weak polybasic acids. More specifically, the compound is a solid.
According to a particular embodiment of the invention, the water-soluble compound is chosen from polyelectrolytes in the organic state resulting from the polymerization of monomers of general formula:
wherein R isiWhich may be the same or different, represent H, CH3、CO2H、(CH2)nCO2H，n＝0～4。
Non-limiting examples which may be mentioned are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid.
Also suitable for use in the present invention are the monomers of the formula and copolymers prepared from these monomers and other monomers, in particular vinyl derivatives, such as vinyl alcohol and copolymerizable amides, such as acrylamide or methacrylamide. Mention may also be made of copolymers prepared from alkyl vinyl ethers and from maleic acid and copolymers prepared from vinyl styrene and from maleic acid, which are described in detail in Kirk-Othmer encyclopedia entitled "encyclopedia of chemical technology" -volume 18-3 rd edition, Wiley Interscience Press-1982. Peptide polymers formed by the polycondensation reaction of amino acids, particularly aspartic acid and glutamic acid or precursors of diamino diacids, are also suitable for use in the present invention. These polymers may be homopolymers derived from aspartic acid or glutamic acid and copolymers derived from aspartic acid and glutamic acid in any proportion, or copolymers derived from aspartic acid and/or glutamic acid and from other amino acids. Among the copolymerizable amino acids, mention may be made of glycine, alanine, leucine, isoleucine, phenylalanine, methionine, histidine, proline, lysine, serine, threonine, cysteine, and the like.
Preferred polyelectrolytes have a low degree of polymerization.
The weight-average molecular weight of the polyelectrolytes is in particular less than 20000 g/mol. Preferably 1000 to 5000 g/mol.
It is obviously fully conceivable to use these different types of water-soluble compounds in combination.
The composition of the invention may additionally contain a polymer selected from the group consisting of polyacrylamide and polyvinylpyrrolidone or mixtures thereof. Preferably the polyacrylamide used has a weight average molecular weight of at most 10000, or alternatively at most 2000.
The composition of the present invention may contain 5 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 2 to 10 parts by weight of the water-soluble compound per 100 parts by weight of the film-forming polymer powder.
The compositions of the present invention may also contain an inorganic filler d) having a particle size of less than about 20 microns.
Inorganic fillers, in particular from the group consisting of silica, calcium carbonate, kaolin, barium sulfate, titanium dioxide, talc, hydrated alumina, bentonite and calcium thioaluminate (satin white), are proposed.
The presence of these inorganic fillers facilitates the production of the powder and increases its storage stability by preventing the powder from agglomerating, i.e. caking.
The inorganic filler may be added directly to the powder composition or it may be prepared by the process of preparing the composition. The amount of the inorganic filler may be 0.5 to 60, preferably 10 to 20 parts by weight per 100 parts by weight of the water-insoluble film-forming polymer powder.
The powder compositions obtained are storage-stable, they can be readily dispersed in water in the form of pseudolatices, and can be employed in the form of powders or pseudolatices in all known latex applications. They also have excellent flow properties.
The invention also relates to a process for the preparation of these powder compositions, which comprises:
removing water from an aqueous emulsion consisting of said insoluble film-forming polymer prepared by emulsion polymerization and containing appropriate amounts of additives b) and optionally c) and d),
-spraying the dried residue into a powder having the desired particle size.
First, an aqueous emulsion of the water-insoluble film-forming polymer powder prepared by emulsion polymerization as described above is employed. Such emulsions are commonly referred to as latexes.
Mixing the other components of the powder composition: amino acids or amino acid salts (b), optionally water-soluble compounds (c) and inorganic fillers (d) are added to the aqueous emulsion. The relative amounts of the various components are selected so that the dry powder composition has the composition previously described.
It may be preferred to use initially an emulsion having a solids content (film-forming polymer + amino acid or amino acid salt + water-soluble compound + inorganic filler) of from 30 to 70% by weight.
When conventional additives are employed, it is apparent that they may be added during the formation of the emulsion.
An aqueous solution of about 30% by weight of sodium hydrogen glutamate is for example added to the stirred latex. The respective amounts are calculated to yield a mixture containing about 15 to 20 wt% sodium hydrogen glutamate and 80 to 85 wt% film forming polymer on an active basis.
In this case, the resulting mixture has a solids content of about 45% by weight, a pH of about 5 and a viscosity of 7 to 100mPa.s, as measured by a Brookfield RVT-DVII instrument at 50 rpm.
The water content of the emulsion was then removed and the resulting product was sprayed to give a powder. The step for removing moisture from the colloidal emulsion and the step for obtaining the powder may be performed separately or simultaneously. Thus, a coagulation process followed by a sublimation step, either freeze-drying, drying or spray-drying (spray-drying) may be employed.
Spray drying is the preferred method since it directly yields a powder with the desired particle size without having to go through a milling step. The particle size of the powder is generally less than 500 microns, preferably less than 100 microns, more preferably greater than 50 microns.
Spray drying may be carried out in a conventional manner in any known apparatus, for example a spray tower where the spraying is accomplished by means of a nozzle or a turbine with a hot gas stream.
The inlet temperature of the hot gas (usually air) at the top of the tower is preferably 120 to 70 ℃ and the outlet temperature is preferably 50 to 70 ℃.
The inorganic filler d) may be added to the aqueous base polymer emulsion. All or a portion of the inorganic filler may also be added to the spray drying process during the spraying step. Finally, the inorganic filler may be added directly to the final powder composition, for example in a rotary mixer.
According to a preferred embodiment, inorganic particles of small particle size, for example about 3 microns, may be added to the spray tower in an amount such that the powder composition leaving the tower has a particle content of about 10% by weight; 20% by weight of particles having an average particle size of, for example, about 15 μm may be added to the powder and the mixture homogenized in a rotary mixer.
In most cases, the pulverulent compositions according to the invention are completely redispersible in water at room temperature by simple stirring. By fully redispersible it is meant that the powder of the invention, after addition of a suitable amount of water, forms a pseudolatex having a particle size substantially the same as the particle size of the latex particles present in the starting emulsion. They therefore have excellent water-wetting properties and are redispersed in deionized water or in CaCl by means of the powder2Redispersion in solution (1M) was achieved spontaneously, rapidly and fully. The particle size distribution of the pseudolatex obtained by redispersing the powder in water was determined using a Brookhaven DCP1000 photosedimentometer and the results were identical to those of the starting latex.
The invention also relates to a pseudolatex obtained by dispersing the above-mentioned powder composition in water.
Finally, the invention relates to the use of the aforementioned pulverulent compositions in the construction industry as additives for the preparation of hydraulic inorganic binder mixtures for the production of protective and decorative coatings, adhesive mortars and adhesive cements for the laying of floors and for covering floors. They have proven to be particularly suitable for the preparation of ready-to-use powder products based on cement and gypsum.
When added to a cement mortar, the powder composition of the invention gives the mortar the same properties as the starting latex from which it is prepared, i.e. a marked improvement in adhesion to various substrates, irrespective of the conditions of the mortar (drying, immersion in water, heating to 80 ℃), flexural strength, adhesive strength and impact strength. It also significantly reduces the water uptake of the adjuvant-containing mortar coating.
The powder compositions according to the invention or the pseudolatices prepared therefrom can also be used in all other fields of application of latices, in particular in the field of adhesives, paper coatings and paints. The powder compositions according to the invention may also contain the usual additives, in particular biocides, bacteriostats and organosilicone defoamers.
Examples
Example 1
A latex prepared by the polymerization of styrene, butadiene, acrylic acid and an ethylenically unsaturated dicarboxylic acid is employed. The polymer particle size, determined using a Brookhaven DCP1000 sedimentation camera, was 0.17. + -. 0.1. mu.m.
The latex was added to a reactor equipped with a stirrer.
A 30% by weight aqueous solution of sodium hydrogen glutamate was added to the stirred latex. The respective amounts are calculated so that the resulting mixture contains 15% by weight of sodium hydrogen glutamate and 85% of film-forming polymer, calculated as active substance.
The resulting mixture has the following characteristics:
-solids content: 45.5% by weight
-pH：5.5
Viscosity measured at 50rpm using a Brookhaven RVT-DVII instrument: 90 mPa.s.
The mixture was converted to powder by spray drying. Drying was done in a spray tower with hot air inlet temperature of 105 ℃ and outlet temperature of 60 ℃.
During the spraying, kaolin particles having an average particle size of 3 μm were added to the tower in such an amount that the kaolin content of the powder composition exiting the spraying tower was 10% by weight.
To this powder was added 20% by weight of calcium carbonate particles having an average particle size of 15 μm and the mixture was homogenized in a rotary mixer.
The powder obtained had the following characteristics:
-average particle size: the thickness of the film is 80 microns,
-a good flowability of the melt,
-a good storage stability of the composition,
-a good water wettability,
in deionized water and in concentrated CaCl2All redispersed spontaneously, rapidly and completely in solution (1M).
The particle size distribution of the pseudolatex obtained by redispersing this powder in water, determined with a Brookhaven DCP1000 sedimentation camera, was identical to that of the starting latex.
When added to a cement mortar, the powder gives the mortar the same properties as the starting latex, i.e. a marked improvement in the adhesion to various substrates, irrespective of the conditions of the mortar (drying, immersion in water, heating to 80 ℃), flexural strength, adhesive strength and impact strength. It also significantly reduces the water uptake of the adjuvant-containing mortar coating.
Example 2
A latex prepared by the polymerization of styrene, butadiene, acrylic acid and an ethylenically unsaturated dicarboxylic acid is employed. The polymer particle size, determined using a Brookhaven DCP1000 sedimentation camera, was 0.14. + -. 0.1. mu.m.
The latex was added to a reactor equipped with a stirrer.
A 30% by weight aqueous solution of sodium hydrogen glutamate was added to the stirred latex. The respective amounts are calculated so that the resulting mixture contains 20% by weight of sodium hydrogen glutamate and 80% of film-forming polymer, calculated as active substance.
The resulting mixture has the following characteristics:
-solids content: 44.2% by weight
-pH：5.5
Viscosity measured at 50rpm using a Brookhaven RVT-DVII apparatus: 70 mPa.s.
The mixture was converted to powder by spray drying. Drying was done in a spray tower with hot air inlet temperature of 105 ℃ and outlet temperature of 60 ℃.
During the spraying, kaolin particles having an average particle size of 3 μm were added to the tower in such an amount that the kaolin content of the powder composition exiting the spraying tower was 10% by weight.
To this powder was added 20% by weight of calcium carbonate particles having an average particle size of 15 μm and the mixture was homogenized in a rotary mixer.
The powder obtained had the following characteristics:
-average particle size: the thickness of the film is 80 microns,
-a good flowability of the melt,
-a good storage stability of the composition,
-a good water wettability,
in deionized water and in concentrated CaCl2All redispersed spontaneously, rapidly and completely in solution (1M).
The particle size distribution of the pseudolatex obtained by redispersing this powder in water, determined with a Brookhaven DCP1000 sedimentation camera, was identical to that of the starting latex.
When added to a cement mortar, the powder composition gives the mortar the same properties as the starting latex, i.e. a marked improvement in the adhesion to various supports, irrespective of the conditions of the mortar (drying, immersion in water, heating to 80 ℃), flexural strength, adhesive strength and impact strength. It also significantly reduces the water uptake of the adjuvant-containing mortar coating.
Example 3
A latex prepared by the polymerization of styrene, butadiene, acrylic acid and an ethylenically unsaturated dicarboxylic acid is employed. The polymer particle size, determined using a Brookhaven DCP1000 sedimentation camera, was 0.17. + -. 0.1. mu.m.
The latex was added to a reactor equipped with a stirrer.
A 30% by weight aqueous solution of sodium hydrogen glutamate and a solution of sodium polyacrylate with a molecular weight of 2000 were added to the stirred latex. The respective amounts are calculated so that the resulting mixture contains, on an active substance basis, 10% by weight of sodium hydrogen glutamate, 10% by weight of sodium polyacrylate and 80% of film-forming polymer.
The resulting mixture has the following characteristics:
-solids content: 44.2% by weight
-pH：5.5
Viscosity measured at 50rpm using a Brookhaven RVT-DVII apparatus: 100 mpa.s.
The mixture was converted to powder by spray drying. Drying was done in a spray tower with hot air inlet temperature of 105 ℃ and outlet temperature of 60 ℃.
During the spraying, kaolin particles having an average particle size of 3 μm were added to the tower in such an amount that the kaolin content of the powder composition exiting the spraying tower was 10% by weight.
To this powder was added 20% by weight of calcium carbonate particles having an average particle size of 15 μm and the mixture was homogenized in a rotary mixer.
The powder obtained had the following characteristics:
-average particle size: the thickness of the film is 80 microns,
-a good flowability of the melt,
-a good storage stability of the composition,
-a good water wettability,
in deionized water and in concentrated CaCl2All redispersed spontaneously, rapidly and completely in solution (1M).
The particle size distribution of the pseudolatex obtained by redispersing this powder in water, determined with a Brookhaven DCP1000 sedimentation camera, was identical to that of the starting latex.
When added to a cement mortar, the powder composition gives the mortar the same properties as the starting latex, i.e. a marked improvement in adhesion to various substrates, irrespective of the conditions of the mortar (drying, immersion in water, heating to 80 ℃), flexural strength, adhesive strength and impact strength. It also significantly reduces the water uptake of the adjuvant-containing mortar coating.
Comparative example 4
The latex of example 1 was used. The latex is converted into powder by spray drying. Drying was done in a spray tower with hot air inlet temperature of 105 ℃ and outlet temperature of 60 ℃.
During the spraying, kaolin particles having an average particle size of 3 μm were added to the tower in such an amount that the kaolin content of the powder composition exiting the spraying tower was 10% by weight.
To this powder was added 20% by weight of calcium carbonate particles having an average particle size of 15 μm and the mixture was homogenized in a rotary mixer.
The average particle size of the resulting powder was 80 microns.
When mixed with water, the powder composition does not disperse. Its average particle size was maintained at about 80 microns. This non-redispersibility in water of this powder makes it to exhibit poor properties in mortars, in contrast to the powders of the above examples.
Claims (17)
1. A water-redispersible powdered composition comprising:
a)100 parts by weight of a water-insoluble film-forming polymer powder made from at least one ethylenically unsaturated monomer and at least one monomer selected from the group consisting of monomers having carboxylic acid functionality and acrylamide or methacrylamide,
b)2 to 40 parts by weight of at least one amino acid or a salt thereof.
2. A powder composition according to claim 1, characterized by comprising 8 to 22 parts by weight of at least one amino acid or a salt thereof.
3. The powder composition according to claim 1, characterized in that the ethylenically unsaturated monomer is selected from the group consisting of: styrene, butadiene, C1-C12Alkyl acrylic or methacrylic esters and their corresponding acids or vinyl esters.
4. A powder composition according to claim 1 or 2, characterised in that the monomer containing a carboxylic acid function is selected from ethylenically unsaturated carboxylic acids.
5. A pulverulent composition according to claim 4, wherein the monomer having a carboxylic acid function is chosen from ethylenically unsaturated dicarboxylic acids.
6. A pulverulent composition according to claim 5, wherein the monomer having a carboxylic acid function is selected from itaconic acid, fumaric acid, crotonic acid, maleic anhydride, mesaconic acid, glutaconic acid or mixtures thereof.
7. A powder composition according to claim 1 characterised in that the water-insoluble polymer is prepared from a monomer mixture comprising 99.9 to 92% by weight of at least one ethylenically unsaturated monomer and 0.1 to 8% by weight of at least one monomer containing a carboxylic acid functional group.
8. Powder composition according to claim 1, characterized in that the amino acid is selected from the group consisting of:
-a mono-carboxylated mono-amino acid,
-a di-carboxylated mono-amino acid,
mono-carboxylated diamino acids.
9. Powder composition according to claim 8, characterized in that the amino acid is selected from the group consisting of glycine, alanine, leucine, phenylalanine, aspartic acid, glutamic acid, hydroxyglutamic acid, arginine, histidine, lysine, cystine.
10. Powder composition according to claim 1, characterized in that the amino acid salt is a water-soluble or alkali-soluble salt.
11. Powder composition according to claim 1, characterized in that it comprises at least one water-soluble compound (c) chosen from polyelectrolytes belonging to the weak polybasic group.
12. A powder composition according to claim 1, characterised in that the composition contains a powdered inorganic filler (d) having a particle size of less than 20 μm.
13. A process for the preparation of a redispersible powders composition as claimed in any one of claims 1 to 12, characterized in that:
removing water from an aqueous emulsion consisting of the insoluble film-forming polymer prepared by emulsion polymerization and containing appropriate amounts of additives b) and optionally c) and d),
-spraying the dried residue into a powder having the desired particle size.
14. The method of claim 13, characterized in that the selected method is a spray drying method.
15. The process according to claim 13 or 14, characterized in that all or part of the inorganic filler (d) is added in the spraying step.
16. A pseudolatex prepared by redispersing the powder composition of any one of claims 1 to 12 in water.
17. Use of the pseudolatex of claim 16 and of the pulverulent composition of any one of claims 1 to 12 as additives in hydraulic binders, adhesives, paper coating compositions and paints.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR96/00188 | 1996-01-10 | ||
| FR9600188A FR2743368B1 (en) | 1996-01-10 | 1996-01-10 | WATER REDISPERSABLE POWDERS OF FILM-FORMING POLYMERS PREPARED FROM ETHYLENICALLY UNSATURATED MONOMERS |
| PCT/FR1997/000030 WO1997025371A1 (en) | 1996-01-10 | 1997-01-08 | Water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1018791A1 HK1018791A1 (en) | 2000-01-07 |
| HK1018791B true HK1018791B (en) | 2002-08-09 |
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