FR2631629A1 - Coating compounds and process for reducing the formation of blisters employing the said compound - Google Patents

Abstract

Preparation of coating compounds based on aqueous polymer dispersions. These compounds can be prepared from an aqueous dispersion of a polymer which has a ratio of the specific surface to the charge chosen so that there is a surface of at least 0.43 nm<2> per charge. The compound contains a (polyalkylene glycol)-fatty amine, a sulphonate and, optionally, a latent acid. Application: these compounds are useful in a number of fields including floor covering such as carpet reinforcement and the treatment of printing papers and of textile materials.

Description

The present invention relates to a process for reducing blistering in substrates which have been coated with compounds based on aqueous polymeric emulsions. Suitable substrates include carpets, paper, needle felt, textiles, etc.

Blistering is a phenomenon which is considered to occur when vapor, usually water vapor, is trapped below or within a sufficiently cohesive film which is formed or forms on the surface of the coating. applied to a substrate. Seeking to improve the efficiency of drying processes to produce faster, for example, printed paper, foam or underlayered carpet, manufacturers are trying to increase production & line speeds through use. higher temperatures and / or air speeds in the drying ovens or to increase printing speeds, in particular for heat-set sheet offset printing processes. water, or if the substrate contains moisture (eg paper), increased blistering may result. In carpet reinforcement applications, blistering gives rise to surface imperfections, surface "fungus" defects or a puff structure which can be sites of carpet backing delamination. In paper printing, it is known that blistering also occurs when printing high quality papers using heat-set sheet offset printing processes. This can lead to surface imperfections which can cause delamination (peel) problems and uneven fixing of the printing inks, resulting in a motley color.

Various suggestions have been made to reduce blistering of carpet backings by incorporating zinc oxide, starch or starch mixtures: borax into compounds & latex bases intended for carpets. U.S. Patent No. 4,055,694 describes these types of compounds. The present patent application does not contemplate the use of zinc oxide, starch and / or borax to reduce blistering.

British Patent No. 1,520,827 describes the use of poly (C1-C4 alkylene glycols) fatty amines for the gelation of different types of latex.

The British patent does not propose the mixing of a fatty (C1-C4 alkyleneglycol) -amine with an aromatic sulfonate to reduce blistering. Further, nothing is mentioned in the reference regarding the specific surface area to charge ratio of the polymeric latex particles, as required herein.

The article titled "Physical Properties of Non
Wovens: Effect of Binder Distribution and StructureH by
J. Troesch and G. Hoffmann (Sandoz) Tappi, August 1976, vol.

59 No. 8, page 133, describes the use of Cartafix U (trademark of Sandoz AG) for latex sensitization to reduce the migration of binders into non-woven textile materials. Cartafix U is described in the Sandoz professional literature as a fatty amine polyglycolic ether. Sandoz's technical newsletter titled "Cartafen RL
Liquid (Trademark of Sandoz AG) "describes the combination of
Cartafix U and Cartafen RL for sensitizing binders for non-woven textile materials. The
Cartaren RL is described as an aromatic sulfonate.

The trade bulletin does not suggest the use of these agents as a method of reducing blistering in surface coatings based on aqueous dispersions of polymers. In addition, the professional bulletin reveals that Cartafix U and Cartafen RL must be added separately. This is in contrast to the compounds of the present invention which contain both an aromatic sulfonate and a fatty poly (C2 to C4 alkyleneglycol) amine.
The present invention provides a process for reducing blistering in surface coatings based on aqueous dispersions of polymers.

The present invention provides a process for reducing blistering in surface coatings formed from a compound based on an aqueous polymeric dispersion, which comprises selecting as the base for said compound an aqueous dispersion of a polymer having a surface area to area charge chosen so that there is an area of at least 0.43 mm2 per charge and the compound contains per 100 parts of polymer 2 to 10 parts by weight of a poly (alkyleneglycol C2 to C4) fatty amine, 1 to 10 parts by weight of an aromatic (C10 to C25 alkyl) sulfonate and, optionally up to 5 parts by weight of a latent acid.

Without being bound by theoretical considerations, it is believed that by "setting" or "gelation" of a compound based on an aqueous polymeric dispersion prior to film formation, porosity is maintained in the structure or matrix. of the compound sufficient for the vapor to pass through the matrix during drying and possibly subsequently.

As used in this specification, the term "charge" refers to the total electrostatic charge on the surface of the polymer. Sources of loaded species in latexes are described in a number of references, including "Latex Stability Characteristics Related to Surface Chemistry" presented by E.

Polotajko and VG Xanthopoulo i la International Polymer
Latex Conference The Institute of Electrical Engineers, October 31, November 1 and 2, 1978, The Plastics and Rubber
Institute (page 61) and Vanderhoff, JW and Van den Hul, Monodisperse Latexes as Model colloids ", J. Macromol Sci.
Chem., A 7 (3) (1973), 677. Species participating in the electrostatic charge on the surface of polymer particles in a latex include a bonded acid group (eg an acid incorporated into the polymer backbone), emulsifiers , the residue of initiators (eg the sulfate group) and polymerizable carboxylic acid oligomers.

The present invention is useful with aqueous dispersions of polymers, including polymers of styrene-butadiene; nitrile polymers; acrylate type polymers; and ethylene vinyl acetate polymers. The polymers should have a specific surface area to charge ratio chosen such that there is an area of at least 0.43, preferably greater than 0.50 nm2, per charge.

The styrene-butadiene polymers comprise i) 20 to 80, preferably 35 to 70% by weight, of a
mixture comprising 100 to 85% by weight of one or
several vinyl aromatic monomers, C8 to
C12 which are unsubstituted or substituted with
a C1 to C4 alkyl radical or an atom of
chlorine and O at 15% by weight of a (C3 alkenyl
to C8) -nitrile ii) 80 to 20, preferably 20 to 65% by weight of a
or more conjugated aliphatic diolefins
in to & C6 which are unsubstituted or
substituted with a chlorine atom; and iii) optionally 0.5 b 10, preferably less
of 5% by weight of one or more monomers
selected from the group consisting of acids
C3 carboxylic & ethylenic unsaturation
to C6 and acryloyloxy-acid monomers.

Suitable vinyl aromatic monomers include styrene, alpha-methylstyrene, and chlorostyrene. Suitable C3-C8 alkenyl nitriles include acrylonitrile and methacrylonitrile. Suitable C4-C6 aliphatic conjugated diolefins include butadiene, isoprene and chloroprene. Suitable C3-C6 ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, itaconic acid.

dans laquelle R1 représente l'hydrogène ou un radical alkyle ayant 1 à 6 atomes de carbone et R2 répond à la formule i.

dans laquelle n a une valeur de 1 à 6 ii.

Suitable acryloyloxy acid monomers have the formula
Formula I

in which R1 represents hydrogen or an alkyl radical having 1 to 6 carbon atoms and R2 corresponds to the formula i.

where n has a value of 1 to 6 ii.

where a and b are the same or different and have a value of 1 to 4.

Suitable acryloyloxyacid monomers include substituted acryloyloxycarboxylic acid type monomers, such as alpha-acryloyloxyacetic acid, beta-acryloyloxypropionic acid, beta-methacryloyloxypropionic acid, beta-ethacryloyloxypropionic acid, beta-propacryloyloxypropionic acid, beta-butacryloyloxypropionic acid, beta acryloyloxybutanoic acid, gamma-acryloyloxybutanoic acid, beta-methacryloyloxybutanoic acid, deltaacryloyloxypentanoic acid, epsilon-acryloyloxyhexanolque acid.

The styrene-butadiene polymer may optionally include one or more additional functional monomers. If present, these additional functional monomers can be used in amounts of up to about 10, preferably less than 5% by weight. Suitable functional monomers include a) amides of unsaturated carboxylic acids.
ethylene cation in c3 to C6, amides which are
unsubstituted or substituted at the level of
the nitrogen atom with up to S two radicals
selected from the group comprising radicals
alkyl and hydroxyalkyl radicals C1 to
C4; b) C3 ethylenically unsaturated aldehydes
to C6, and c) alkyl or hydroxyalkyl esters in
C1 to C8 unsaturated carboxylic acids
ethylenic C3 to C6.

Suitable amides include acrylamide, methacrylamide, N-methylolacrylamide, and N-methylol methacrylamide. Suitable aldehydes include acrolein. Suitable esters include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate and methacrylate and acidic counterparts. higher of these esters.

Useful nitrile polymers include i) 5 to 40% by weight of a (C3-C8 alkenyl) -
nitrile ii) 94.5 to 59.5% by weight of a mixture comprising
100 to 60% by weight of one or more diolefins
C4 to C6 aliphatic conjugates which are
unsubstituted or substituted with an atom of
chlorine, and up to 40% by weight of one or
several vinyl aromatic monomers, C8 to
C12 which are unsubstituted or substituted with
a C1 to C4 alkyl radical or an atom of
chlorine; and iii) optionally 0.5 to 10, preferably less
of 5% by weight of one or more monomers
selected from the group consisting of acids
C3 ethylenically unsaturated carboxylic acids
to C6 and acryloyloxy-acid monomers
Suitable C3-C8 alkenyl nitriles, conjugated aliphatic diolefins, vinyl aromatic monomers and carboxylic acids have been described above.

The nitrile polymers can optionally comprise one or more of the additional functional monomers described above, in an amount of up to 10-, preferably not more than 5% by weight.

The acrylic type polymers comprise i) 60 to 99.5% by weight of a mixture comprising 80
at 100% by weight of one or more esters
C1 to C8 alkyl or hydroxyalkyl
of carboxylic acids i ethyleni unsaturation
than in C3 to C6 and up to 20% by weight of one or
several monomers chosen from the group
comprising C8 vinyl aromatic monomers
to C12 which are unsubstituted or substituted
with a C1 to C4 alkyl radical or an atom
chlorine, and alkenyl-nitrile monomers
C3 to C8 ii) optionally 0.5 to 40, preferably less
25% by weight of one or more monomers
selected from the group consisting of acids
C3 ethylenically unsaturated carboxylic acids
to C6 and acryloyloxy-acid monomers.

Suitable C1 to C8 alkyl and hydroxyalkyl esters of C3 to C6 ethylenically unsaturated carboxylic acids, C8 to C12 vinyl aromatic monomers, alkenyl nitriles, C3 to C6 ethylenically unsaturated carboxylic acids and acryloyloxy acids have been described above.

Optionally, the acrylic type polymers can contain up to 10, preferably less than 5% by weight of an amide or aldehyde functional monomer, as described above.

The ethylene vinyl acetate polymers comprise i) 60 to 94.5% by weight of one or more esters
C2 to C8 alkenyl or hydroxyalkenyl
of saturated C1 & C8 carboxylic acids ii) 5.0 to 39.5% by weight of a C2 or C3 olefin and iii) 0.5 to 10, preferably 0.5 to 5% by weight of a
or more monomers selected from the group
comprising unsaturated carboxylic acids
ethylene cation in C3 to C6 and acryloyloxy
acids.

C2 to C8 alkenyl or hydroxyalkenyl esters of saturated C1 to C8 carboxylic acids include vinyl acetate, vinyl propionate, vinyl butyrate and vinyl 2-ethylhexanoate.

Ethylene and propylene are suitable olefins in
C2 or C3. Suitable carboxylic acids and acryloyloxyacids have been described above. Optionally, the ethylene vinyl acetate polymers can contain up to 10, preferably less than 5% by weight of one or more of the above functional monomers.

The polymers in the aqueous dispersion should have a specific surface area: filler ratio chosen such that there is an area of at least 0.43 nm2, preferably greater than 0.50 nm2 per charged group on the polymer. As used in the specification, this specific surface area: charge ratio is calculated by determining the specific surface area of 1 g of anhydrous polymer. This is based on the average diameter of the polymer particles in the latex.The surface electrostatic charge of the polymer, in meg / ga the anhydrous state, is then determined.The specific surface area is then divided by the surface electrostatic charge to give 1 ' occupancy of specific surface area in name 2. The filler can be a fixed filler, for example a filler which is polymerized in the backbone of the polymer, such as an acidic group, or it can be a mobile filler, such as that present on surfactants. It should be noted that if a persulfate is used as an initiator, the surface charge from the sulfate groups should also be included in the determination of the surface charge.

dans laquelle R1 est un radical alkyle ou alcényle en C10 à
C25' de préférence en C15 à C22
R2 est un groupe alkyle en C1 à C4 n est un nombre entier de 2 à 4 inclus, de préférence égal à 2 ou 3 m a la valeur 1 ou 0 ;
X est un atome d'halogène, de préférence un chlorure ; et a et b sont des nombres entiers supérieurs à 2, la somme de a et b étant inférieure à 50, avantageusement comprise dans l'intervalle de 10 à 50, de préférence de 20 à 35.The poly (C2-C4 alkylene glycol) fatty amines useful in accordance with the present invention are the reaction products of N-alkyl- or N-alkenylamines. Poly (C2 to C4 alkylene glycol) fatty amines have the formula

in which R1 is a C10 to C10 alkyl or alkenyl radical
C25 'preferably in C15 to C22
R2 is a C1 to C4 alkyl group n is an integer from 2 to 4 inclusive, preferably equal to 2 or 3 m the value 1 or 0;
X is a halogen atom, preferably a chloride; and a and b are integers greater than 2, the sum of a and b being less than 50, preferably in the range of 10 to 50, preferably 20 to 35.

Preferred fatty radicals include steryl radicals and radicals derived from coconut oil or palm and olive oils.

Laminate fat is used in an amount of 2 to 10, preferably 4 to 8, parts by weight per 100 parts by weight of polymer.

The second constituent of the compounds of the present invention are alkyl aromatic sulfonates. The alkyl aromatic sulfonate is preferably a (C12 to C18 alkyl) -naphthalene-, benzene, toluene- or xylene-sulfonate. The aromatic sulfonate is used in an amount of 1 to 10, preferably 4 to 8, parts by weight per 100 parts by dry weight of polymer.

Optionally, the compounds of the present invention contain up to 5 parts by weight of a latent, preferably volatile, acid which lowers the pH of the composition. Suitable inorganic compounds include sulfates and halides, preferably chloride, of ammonium. The compound can be an amine or an ammonium salt of an organic acid, such as ammonium acetate or ammonium sulfonate. If present, the latent acid is preferably used in an amount of 2 to 5 parts by weight per 100 parts of polymer.

The present invention is particularly useful in compounds used for coating and / or laminating applications such as the formation of the bottom coating of substrates, including carpets (carpet backings), carpet tiles, patches of artificial turf, turf blocks (domed stains applied to artificial turf mats) and coated papers, including gravure papers, offset printing papers, coated papers and rigid papers (boards).

For carpet reinforcement, the binder in the compound is usually a carboxylated styrene-butadiene rubber (SBR) latex. In addition to the above components, the compound may contain 0 about 1000, preferably less than about 800, preferably less than about 450 parts by weight per 100 parts of polymer of a particulate inorganic filler. Suitable fillers include calcium carbonate, talc, aluminum trihydrate, clay, sand and barite. The present invention is particularly useful in the absence of filler or with a low filler content (eg 50 to 400 parts of filler per 100 parts of polymer). This is believed to be due to the fact that low filler or no filler compositions contain relatively higher amounts of water.

The compound may further contain a crosslinking agent. Usually, these agents have been melamine-formaldehyde or urea-formaldehyde resins. With current concerns about formaldehyde, these agents don't. generally not incorporated into carpet backing formulations.

The compounds can also include conventional ingredients such as crosslinking agents (eg zinc oxide and / or carbamates etc.), antistatic agents including carbon black, foaming agents such as synthXti surfactants. - ques, such as succinates or a natural soap (for example rosin or a fatty acid), electrolytes, sequestering agents (for example EDTA) and phosphates, the use of which is well known in the art.

For the coating of papers, the polymeric binder can be a styrine-butadiene latex or an acrylate latex. For coating papers, these polymeric binders can be used as co-binders together with up to about 1.5 times their own weight of a starch or casein binder, or as the sole binder in combination with such products. as carboxymethylcellulose, polyvinyl alcohol or polycarboxylic acids and their salts for the purpose of modifying rheology. The compounds for coating papers normally contain a very high filler content, comprising about 5 to 15, preferably about 7 to 12 parts by dry weight of a binder and 95 to about 85, preferably 93 to 88 parts by weight. one or more fillers or one or more pigments.

The pigment or filler can be one or more compounds selected from clay, talc, calcium carbonate, titanium dioxide, glass microspheres and synthetic pigments (e.g. pigments containing more than about 80% styrene). The paper coating compound may also contain small amounts of insolubilizers such as MF or UF resins. In addition, the paper coating compounds contain the agents for preventing blistering, in the above amounts.

For carpets, the compound can be applied at coating weights of about 203 to 1350, preferably 510 to 850 g / m2. After application to the backing of the carpet, the carpet can pass through an oven at a temperature of 80 to 200, preferably 150 µl. The drying time depends on the speed of the production line, the temperature of the oven, the efficiency of the oven and the air speed, to achieve satisfactory drying.

In another method, the coated carpet can be passed under infrared lamp heaters, Kellrod heaters or through a drum lamination apparatus to allow substantial drying of the compound.

The paper is coated to coating compound weights of about 5 to 40, preferably about 6 to about 25 g / m2 per side. The paper then passes through a hot air circulating oven at temperatures of about 90 to 130 ° -C. The speed of passage i through the oven can be very high, of the order of 900 to 1500 m / min. Blistering in the paper was not usually a problem until printing the paper with a high speed press, as is the case in heat set sheet offset printing.

The following examples are intended to illustrate, but not to limit, the present invention. Unless otherwise specified, parts are parts by dry weight (eg, the examples show the dry weight ratio of ingredients).

Example I
A carpet backing compound was prepared according to the following wording
Dry Wet
Latex POLYSAR 3120 100 175 (carboxylated styrene-butadiene latex) calcium carbonate (BL 200 ex.OMYA) 200 200
Water --- - 15
The compounds had a total solids content of 77%. The viscosity of the compound was adjusted to 5000 cps with an acrylate as a thickener.

The pH of the compound was adjusted to 8.3. To the underside of a conventional carpet, the compound of formula I was applied at dry coating weights of 850 g / m2 and 1150 g / m2. Then the underside of the coated carpet was placed 5 cm below an infrared light source for 2-3 minutes to initiate drying of the compound. Light blistering was observed in the sample coated at 850 g / m2. Very severe blistering was observed in the sample coated at 1150 g / m2.

Example It
Another compound for carpet backing has been prepared according to the following formulation
Dry Wet
Latex POLYSAR 3120 100 175 (carboxylated styrene-bgutadiene latex) calcium carbonate (BL200 ex OMYA) 200 200
Poly (C2-C4 alkylene glycol) -amine
oily 5 10 (CARTAFIX U - trademark of
Sandoz AG)
Aromatic sulphonate 2 10 (CARTAFEN RL - trademark of
Sandoz AG) NH4C1 5 5
Water --- 10
The compound had a total solids content of 77%. The viscosity of the compound was adjusted to 5000 cps and the pH was adjusted to 7.9. The compound was coated on the underside with a carpet of the same type as that used in Example 1 at coating dry weights of 850 g / m2 and 1150 g / m2. Then the coated carpet was placed under the coating. infrared light source used in Example 1, at a distance of 5 cm for 2 to 3 minutes to trigger the drying of the coating. No blistering was observed. Some cracking appeared on the surface of the compound.

This demonstrates that blistering can be reduced using coating formulations according to the present invention.

Example III
Paper conditioned for 24 hours at 6% humidity was coated with a low weight offset paper coating paste based on an untreated latex of a carboxylated styrene-butadiene polymer (POLYSAR
D93-505) and the latex was mixed with 10 parts per 100 parts of dry polymer of a (C2 to C4 alkylene glycol) fatty amine (CARTAFIX U), 1 part per 100 parts of polymer of an aromatic sulfonate (CARTAFEN RL) and 5% by weight NH4Cl (based on the dry polymer). Blistering on the coated paper was measured by the oil bath method (eg heating the paper in oil until blistering). The blistering temperature for the paper coated with the untreated latex compound was 176 C. The blistering temperature for the paper coated with the treated latex compound was 194 C.

This shows that the paper coating compounds prepared in accordance with the present invention either raise the blister temperature of the paper or else reduce the blister of the paper at lower temperatures.

Example IV
Example II was repeated with a series of different latexes. With some latexes, the blister inhibitory effect has been observed and, with some others, no blister inhibitory effect has been observed. To determine the reason why the composition was ineffective with certain latexes, a series of experiments were carried out with different latexes. Ten parts of poly (C2-C4 alkyleneglycol) fatty amine, 5 parts of aromatic sulfonate and 5 parts of ammonium chloride were added to 100 parts by dry weight of polymer. The latex was heated in a test tube at 700C to observe its possible gelation. Then the latexes were analyzed to determine the surface charge and the particle diameter. The results of the experiment are as follows.

Latex <SEP> POLYSAR1 <SEP> POLYSAR1 <SEP> EOC1 <SEP> HüLS1 <SEP> Dow1 <SEP> Synthomer1 <SEP> Synthomer1 <SEP> POLYSAR2
<tb><SEP> 3393 <SEP> 3120 <SEP> 7104 <SEP> CT40 <SEP> 852 <SEP> ST <SEP> 044 <SEP> ST <SEP> 143 <SEP> 3701
<tb> Average <SEP> diameter <SEP> 1750 <SEP> 1100/1800 <SEP> 1700 <SEP> 1900 <SEP> 2000 <SEP> 1400 <SEP> 1700 <SEP> --of <SEP> particles <SEP > (Bimodal)
<tb> load * <SEP> 0.140 <SEP> 0.089 <SEP> 0.115 <SEP> 0.121 <SEP> 0.152 <SEP> -0.22 <SEP> -0.229 <SEP> no
<tb> meg / g. <SEP> to <SEP> carboxylated
<tb> state <SEP> sec
<tb> Occupation <SEP> of
<tb> specific <SEP> surface <SEP> 0.43 <SEP> 0.43 <SEP> 0.55 <SEP> 0.49 <SEP> 0.35 <SEP> 0.36 (0.32) <SEP> 0.27 (0.26) <SEP> mm / load *
<tb> Gelation <SEP> Yes, <SEP> but <SEP> Yes <SEP> Yes <SEP> Yes <SEP> No <SEP> No <SEP> No <SEP> Yes
<tb>

* Includes acid and (per) sulfate groups 1 ~ Carboxylated styrene-butadiene latex 2 ~ Styrene-butadiene latex
This shows that with an area occupancy equal to or greater than 0.43 nm2 per load, the latex is useful with the present invention. If the area occupancy is less than 0.43 nma per load, the latex is not useful with the present invention.

It goes without saying that the present invention has been described for explanatory purposes, but in no way limiting, and that numerous modifications can be made to it without departing from its scope.

Claims (10)

1. Process for reducing the formation of blisters in surface coatings formed from a compound based on an aqueous polymeric dispersion, characterized in that it consists in choosing as the base for said compound an aqueous dispersion of a polymer having an area to area charge ratio selected such that there is an area of at least 0.43 nm2 per charge and the compound contains, per 100 parts of polymer, 2 to 10 parts by weight of a fatty poly (C2 to C4 alkylene glycol) amine, 1 to 10 parts by weight of a C10 to C25 aromatic sulfonate and, optionally, up to 5 parts by weight of a latent acid. 2. Method according to claim 1, characterized in that the ratio of the specific surface area of the polymer to the charge of the polymer is chosen so that there is an area of at least 0.50 nm2 per charge. 3. Method according to claim 2, characterized in that the fatty poly (C2 to C4 alkyleneglycol) amine is an amine of formula I

wherein R1 is a C15 to C22 alkenyl radical; R2 is a C1 to C4 alkyl radical; n is 2 or 3 t X is a chlorine atom; and the sum of a and b is in the range of 10 to 50. 4. A method according to claim 3, characterized in that in formula I, n has the value 2 and the sum of a and b is in the range of 20 to 35. 5. Method according to claim 4, characterized in that the aromatic sulfonate is an alkali metal salt of a (C12 to C18 alkyl) - naphthalene-, benzene, toluene- or xylene-sulfonate. 6. Method according to claim 5, characterized in that the latent acid is present in an amount of 2 to 5 parts by weight per 100 parts by weight of polymer and is selected from the group comprising ammonium chloride, ammonium acetate, ammonium sulfate, ammonium sulfamate, and mixtures thereof. 7. Method according to claim 5, characterized in that the polymer is chosen from the group of polymers comprising A) polymers comprising i) 20 to 80% by weight of a mixture comprising 100 to 85% by weight of one or more monomers vinyl aromatics at C8 to C12 which are not substituted or substituted with a C1 radical at C4 or a chlorine atom and 0 to 15% by weight of a C3 to C8 alkenyl nitrile ii) 80 to 20% by weight of one or more diolefins aliphatic C4 to C6 conjugates which are not substituted or substituted with an atom of chlorine; and iii) optionally 0.5 to 10% by weight of one or several monomers chosen from the group comprising unsaturated carboxylic acids C3 to C6 ethylenic cation and acryloyloxyacid monomers; acryloyloxy acids iv) optionally 0 to 10% by weight of one or several monomers chosen from the group including a) carboxylic acid amides to C3 to C6 ethylenic unsaturation, amides which are unsubstituted or substituted at the level of the nitrogen atom with up to two radicals selected from the group comprising radicals C1 to C4 alkyl and hydroxyalkyl; b) ethylenically unsaturated aldehydes in C3 to C6 C) alkyl or hydroxyalkyl esters in C1 to C8 of carboxylic acids to unsaturated ethylene cation, C3 to C6 ;; B) polymers comprising i) 5 to 40% by weight of a C3 to C8 alkenyl nitrile; ii) 94.5 to 59.5% by weight of a mixture comprising 100 to 60% by weight of one or more diolefins C4 to C6 aliphatic conjugates which are unsubstituted or substituted with an atom of chlorine and up to 40% by weight of one or several vinyl aromatic monomers, C8 to C12 which are unsubstituted or substituted with a C1 to C4 alkyl radical or an atom of chlorine; and iii) optionally 0.5 to 10% by weight of one or several monomers chosen from the group comprising å unsaturated carboxylic acids ethylene cation in C3 to C6 and monomers acryloyloxy acids iv) optionally 0 to 10% by weight of one or several monomers chosen from the group including a) carboxylic acid amides to C3 to C6 ethylenic unsaturation, amides which are unsubstituted or substituted at the level of the nitrogen atom with up to two radicals selected from the group comprising radicals C1 to C4 alkyl and hydroxyalkyl b) ethylenically unsaturated aldehydes in C3 to C6 c) alkyl or hydroxyalkyl esters in C1 to C8 of carboxylic acids to unsaturated ethylene cation in C3 to C6 C) polymers comprising i) 60 to 99.5% by weight of a mixture comprising 80 at 100% by weight of one or more esters C1 to C8 alkyl or hydroxyalkyl ethylenically unsaturated carboxylic acids than in C3 to C6 and up to 20% by weight of one or several monomers chosen from the group comprising vinyl aromatic monomers in C8 to C12 which are unsubstituted or substituted with a C1 to C4 alkyl radical or a chlorine atom and alkenyl nitriles in C3 to C8; and ii) optionally 0.5 to 40% by weight of one or several monomers chosen from the group comprising unsaturated carboxylic acids C3 to C6 ethylenic cation and acryloyloxyacid monomers; iii) optionally 0 to 10% by weight of one or several monomers chosen from the group including a) carboxylic acid amides to ethylenic unsaturation, amides which are not substituted or substituted at the atomic level nitrogen with up to two radicals selected from the group comprising alkyl radicals and C1 to C4 hydroxyalkyl; b) ethylenically unsaturated aldehydes in C3 to C6; and D) polymers comprising i) 60 to 94.5% in. weight of one or more esters C2 to C8 alkenyl or hydroxyalkenyl saturated C1 to C8 carboxylic acids ii) 5.0 to 39.5% by weight of a C2 olefin or c3; iii) optionally 0.5 to 10% by weight of one or several monomers chosen from the group comprising unsaturated carboxylic acids ethylene cation in C3 to C6 and monomers acryloyloxy acids; iv) optionally 0 to 10% by weight of one or several monomers chosen from the group including a) carboxylic acid amides to C3 to C6 ethylenic unsaturation, amides which are unsubstituted or substituted at the level of the nitrogen atom with up to two radicals selected from the group comprising radicals C1 to C4 alkyl and hydroxyalkyl; b) ethylenically unsaturated aldehydes in C3 to C6 c) alkyl or hydroxyalkyl esters in C1 to C8 of carboxylic acids to unsaturated ethylene cation in C3 to C6. 8. The method of claim 7, characterized in that the compound further comprises, per 100 parts by weight of a polymer comprising 40 to 60% by weight of styrene or alpha-methylstyrene 40 to 59.5% by weight butadiene, asopropene or chloroprene optionally 0.5 to 5% by weight of one or more carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, alpha-acryloyloxtyacetic acid, beta-acryloyloxypropionic acid and methacryloyloxypropionic acid and, optionally, up to 5% by weight of one or more monomers selected from the group consisting of: acrylamide, methacrylamide, N- methylolacrylamide; acrolein, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate, hydroxyethyl methacrylate, 400 to 800 parts by weight of one or more fillers chosen from the group comprising calcium carbonate, talc, aluminum trihydrate, clay, sand and barite, the substrate being a floor covering. 9. The method of claim 7, characterized in that the compound further comprises, for 5 to 15 parts by weight of a mixture of binders comprising 0 to 50% by weight of starch or casein and 50 to 100% by weight. weight of a polymer comprising 40 to 60% by weight of styrene or alpha-methylstyrene 40 to 59.5% by weight of butadiene, isoproprene or chloroprene optionally 0.5 to 5% by weight of one or several carboxylic acids selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, alpha-acryloyloxyacetic acid, beta-acryloyloxypropionic acid and methacryloyloxypropionic acid; and, optionally, up to 5% by weight of one or more monomers selected from the group consisting of: acrylamide, methacrylamide, N-methylolacrylamide; acrolein, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, ethylhexyl methacrylate and hydroxyethyl methacrylate 95 to 85 parts by weight of one or more particulate inorganic fillers selected from the group consisting of clay , talc, calcium carbonate, titanium dioxide, glass microspheres and polymeric pigments, the substrate being paper. 10. The method of claim 7, characterized in that the compound further comprises, for 5 to 15 parts by weight of a mixture of binders comprising 0 to 50% by weight of starch or casein and 50 to 100% by weight. weight of a polymer comprising 60 to 99.5% by weight of a mixture comprising 100 to 80% by weight of one or more monomers chosen from the group comprising methyl acrylate, ethyl acrylate, l 'hydroxyethyl acrylate, butyl acrylate, hexyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, methacrylate hexyl, ethylhexyl methacrylate, and up to 20% by weight of one or more monomers selected from the group consisting of styrene, alpha-methylstyrene and acrylonitrile optionally 0.5 to 5% by weight one or more carboxylic acids chosen from the group comprising acrylic acid, methacrylic acid, fumaric acid, itaco acid nique, alpha-acryloyloxyacetic acid, beta-acryloyloxypropionic acid and methacryloyloxypropionic acid and optionally up to 5% by weight of one or more monomers selected from the group consisting of acrylamide, methacrylamide, N -methylolacrylamide and acrolein, 95 to 85 parts by weight of one or more inorganic particulate fillers selected from the group consisting of clay, talc, calcium carbonate, titanium dioxide, glass microspheres and synthetic pigments, the substrate being paper.