CH623847A5 - Aqueous gloss-finishing composition - Google Patents

Description

The present invention relates to coating or impregnating compositions, more particularly aqueous glossing compositions containing at least one low molecular weight polymer of methacrylic acid and / or acrylic acid. The compositions according to the invention do not contain film-forming polymers of high molecular weight. However, they can be used to obtain very shiny coatings that are practically clear as water and self-dispersing. For example, polymers can be used in aqueous gloss products of the encaustic type for solid substrates such as floors, walls, furniture, ornamental doors and appliances. The substrates can be made of a bare material such as for example metal, wood, plastics, mineral materials such as stone, brick, concrete or other composite materials such as slabs or tiles. vinyl resin, rubber and asbestos, or can be painted, varnished, lacquered, covered with paper or coated with other materials producing a hard surface. These low molecular weight polymers, also called oligomers, are well suited for the preparation of a wide variety of self-dispersing coating products, which after application and drying form transparent coatings with a shiny appearance. Mention may be made, as examples, of various coating products (1) water-resistant and detergent-sensitive gloss products for floors and floors for household use, (2) water-resistant and detergent-resistant coating products for floors and floors for industrial use and (3) brightening and cleaning products giving a hard surface, useful on all wall surfaces.

To form protective coatings, in particular coatings for floors, compositions containing aqueous dispersions are known which consist of a copolymer formed in emulsion, insoluble in water, constituting the film-forming polymer or vehicle, in mixture with a wax, an alkali-soluble resin, wetting agents, emulsifiers and dispersants, and a polyvalent metal compound. The copolymers formed in water-insoluble emulsion, which are used as vehicles in these coatings, have a molecular weight

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high area. These brightening compositions exhibit an advantageous free balance of properties, including a high gloss, a |

resistance to detergents, a resilience and a -CH2-C - (A)

good ease of disposal. |

Do classic polish build up over the course? COOY

successive applications on floors or floors or on other solid substrates and finally require an operation- where W represents a hydrogen atom or a methyl radical, laborious and undesirable removal to return to Y represents an alkyl radical or a substituted alkyl radical;

floor a uniform cleanliness. The thin layers of polymeric gloss having an acid number of 50 to 275 and an average level formed from the products according to the invention are self-distributing by weight of molecular weight from 700 to 5000 and being at least persible. When the brightening product is reapplied, it is partially neutralized.

previous layer dissolves and incorporated dirt is The composition may still include, compared to

eliminated and there remains a film which, after drying, has a weight of solid matter dissolved in water, up to 25% in thickness comparable to that of the original film. Therefore, the weight of a wax (B) and / or up to 50% by weight of a resin without accumulation of the layers, the alkali-soluble (C) are obtained in a single stage. It can also include, at three separate stages which normally constitute maintenance, at a rate of 0.1% to 90% of the weight of the sum of (A), (B) and (C), namely cleaning, removal of the gloss coatings from one or more wetting, emulsifying, plasticizing or preceding agents and re-shining. coalescing (D) and / or up to 5% by weight of (A) of a compound

The hard surface you get with versatile metal shine products (E). The water content is preferably in tage and cleaning according to the invention differs from those obtained 20 quantity such that the total weight concentration of the materials with the conventional general purpose cleaning products of the solids is from 1 to 45% . Preferably, the composition does not include

trade in that they leave a thin layer on the surface takes no film-forming polymers of high molecular weight, cleaned. This film regenerates the shiny appearance of the surface. The low molecular weight film-forming polymers are synthesized.

and makes it waterproof so that the substrate is more resistant to ringing by priming by means of free radicals in new soiling. The film formed by drying is soluble in a homogeneous medium, for example by mass polymerization and and dispersible in the fresh polishing and cleaning product, in solution, or in heterogeneous systems, for example so that when it is again cleaning, the old film polymerization in emulsion or in suspension. To produce dissolves by releasing accumulated dirt. The use of pro-polymers having molecular weights of less than 5000, shine and cleaning are reduced, makes it possible to reduce the efforts known in the art to use chain transfer agents and, if there is friction during cleaning and therefore wear and tear and high concentrations of the initiator "radica-alteration of the substrate and facilitate the removal of soil stains" and high temperatures during polymerization,

oily and greasy dust particles, materials In the case of polymerization by free radicals in emulsion,

Soluble in water and other types of household soiling, particularly high concentrations of the chain transfer agent are necessary because, in the absence of such agents, relatively low molecular weight polymers, Molecular weights are generally in the range of one or more of the aqueous alkalis, such as several million adducts. These preparation processes are indeed rosin-acid, styrene and acrylic acid resins naked and decnts in "Encyclopedia of Polymer Science and and styrene and maleic anhydride resins, are Technology (John Wiley & Sounds 1964) Volume I, pages 263-

found capable of imparting good equalizing properties ^ 80, by L. Luskin and R. Myers. Polymers prepared by and from flowability to brightening products containing free radical initiation are characterized by a molecular weight of high molecular weight polymers but these products from about 700 to about 5000, an acid number of about 50 a of shine are ill-suited when they do not contain an approximately 275 and an average content of carboxyl radicals d to the film-forming agent of high molecular weight, since they resist poorly at least 2 and preferably from 2 to approximately 5.

with water, which is unacceptable, have a re-coating ability Can prepare these radically initiated polymers which is not satisfactory, poor wear resistance and / or any of the polymerization methods well or initial color or stability of their defected color known (see "Polymer Process", CE Schildknecht ed., Intuous. Although we can add small proportions terscience Publishers, New York, 1956), but we prefer the d ' polyvalent metal ions (for example zinc ions) for solution polymerization. Polymers are obtained to improve these properties, this addition is generally accompanied by molecular weight by using chain transfer agents a decrease in gloss. 50 and high polymerization temperatures.

The polyvalent metal compound which is used in the com-In the French patent application No 75 13943 filed as a polishing position can be a metallic compound, on May 5, 1975, the proprietor describes and claims complex metallic compositions or a chelate metallic. The metal ions of coatings containing as multipurpose film-forming polymer 55 ques polyvalent can be ions of beryllium, of cad-certain oligomers of hydrolyzed methacrylic ester. The titular mium, copper, calcium, magnesium, zinc, zirco-discovered that certain oligomers, including the units of nium acid, barium, strontium, aluminum, bismuth, methacrylic direct polymerization, by radi- antimony, of lead, cobalt, iron, nickel or any water free of methacrylic acid monomer, are also another polyvalent metal which can be added to the composition useful in brightening compositions. 6o in the form of an oxide, hydroxide or basic salt, acid or

The aqueous brightening composition according to the invention is neutral having appreciable solubility in water as characterized in that it comprises, in an amount of 25 to 100 parts, that at least about 1% by weight. The choice of polyvalent metal for the weight of solid matter dissolved in water of a polymer and of the anion associated with it in the compound, complex or addition (compound A) prepared by radical oligomerization chelate, depends on the solubility of the free water metal complex of a mixture of monomers containing at least 05 obtained, so that the final brightening composition has a mono-unsaturated α, P-ethylenic acid chosen in appropriate clarity. Particularly preferred as ions are the group of acrylic and methacrylic acids, the polyvalent metal polymer zinc and cadmium ions. Complexes containing at least 25 mole% of structural units: ammonia and amines (in particular coordinated amines

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with NH3) of these metals are particularly useful. Dyes soluble in water or oils. Examples of amines capable of forming complexes are morpholine, suitable dyes which can be used are Prussian blue,

monoethanolamine, diethylaminoethanol and ethylenedi- blue and green phthalocyanic and amine brown dyes. Organic complexes (salts) can also be used. The amount of dye can vary considerably-

polyvalent metals of organic acids capable of dissolving according to the desired effect.

be at an alkaline pH. These anions of organic acids are, generally speaking, the alkali-soluble resins ap-

acetate anions, glutamates, formates, carbonates, salicylates, properties have acid numbers from 100 to 300 and average glycollate, octanoate, benzoate, gluconate, oxalate and lac-molecular weights from 500 to 10,000 and preferably from 800 to 10,000

tates. Polyva- 2000 metal chelates can also be used. Examples of slow-soluble resins in which the ligand is an amino acid containing 2 atoms are suitable alkalies, copolymers of styrene or of vinylto-

coordinators such as glycine or alanine. The compound of luene and at least one acid or anhydride with mono-non-satura-

polyvalent metal must be able to dissociate to release P-ethylenic tion such as styrene and anhy-

polyvalent metal ions so that the metal is stiff maleic, the reaction products of rosin and anhy-

available for cross-linking of maleic acid radicals esterified with polyalcohols and free carboxylic resins of the oligomer. 15 alkyds which are soluble in alkalis which are generally polyes-

Compounds, complexes and chelates of polyvalent metals such as aliphatic dicarboxylic acids and polyalcohols

which are preferred are zinc acetate, cadmium acetate, phatics which can be modified with C8 fatty acids to Clg zinc glycinate, cadmium glycinate, zinc carbonate, and esters of glycerol and fatty acids C8 to C18. Cadmium carbonate, zinc benzoate and salicylate can be cited, as examples of dicarboxylic acids, the nia-

zinc, zinc glycollate and cadmium glycollate. Although 2 (leic, fumaric, adipic and sebacic and it is also possible to add the polyvalent metal compound to the compound use their anhydrides. The polyalcohols can be glycerol

tion of gloss in a dry form such as a powder, one king, pentaerythritol, trimethylolethane and glycols com-

first of all prefers to dissolve it using a fleeting ligand carrying from 2 to 8 carbon atoms such as diethylene glycol

such as ammonia. According to the invention, it is considered that a cool ligand and triethylene glycol. As other resins, it may be mentioned that it is fleeting if at least part of the ligand tends to volatilize soluble in Manila alkalies, shellac, copoly-

under normal conditions of film formation. mothers of alkyl acrylate and shellac containing sufficient

Since ammonia can form a complex with a compound such as shellac to be soluble in polyvalent metal alkalis, a compound such as zinc glycinate or (see Example 4 of US Patent No. 3,061,564 ), the gum of zinc carbonate, when it is dissolved in a Loba solution, the copolymers of styrene and of acrylic acid or of dilute aqueous ammonia acid, can be called methacrylic glycinate containing for example 50 % by weight of each zinc-ammine or zinc carbonate-ammonium. monomers, copolymers of maleic anhydride and a

The polyvalent metal compound, when used, can equimolecular and diisobutulene and the like.

be present in an amount such that the ratio of the equivalents of the polyvalent metal to the free carboxy radicals of the oligomer To obtain the optimal values of the gloss and the resistance varies between approximately 0.05 and 0.5 and preferably between approximately 35 to water and wear, the final gloss composition must

0.2 and 0.3. For a ratio of the metal such as Zn ++ to the radicals contain sufficient auxiliary components, such as

-COO ~ or —COOZ, where Z represents a complementary ion than wetting agents, emulsifiers or coalescers or a positive, the stoichiometer corresponds to a ratio of 0.5. solvent for coalescing or plasticizing the films, to ensure that a uniform, hard and continuous film is obtained

If the wax is used and dispersed separately, it can adhere to the substrate. About 0.5 to 90% by weight is used using common dispersing agents, but amine salts of these auxiliary components relative to the weight of the soap wax, such as oleate or stearate d ethanolamine, oligomer and alkali-soluble resins, when these two are also well suited. Homogenous - last types of components can be used simultaneously.

sors suitable for promoting the formation of the dispersion. As, generally, the use of coalescing solvents or

The waxes or mixtures of waxes which are used are plasticizer waxes 45 intended to facilitate the formation of the film, and of vegetable, animal, synthetic and / or mineral origins or which are not always necessary. to make the composition flexible

mixtures thereof, such as Carnauba wax, oligomeric tion wax when it is by nature resistant and flexible candelilla, paraffin obtained in the Fischer process - as is often the case, a fleeting plasticizer or

Tropsch, microcrystalline wax, lanolin, cocoa butter, semi-fugitive with a permanent plasticizer. However we can wax cotton seeds, stearin, Japanese wax, wax; o use permanent plasticizers without getting nutmeg films, palm wax, beeswax, whale white, poor resistance to wear and water. China wax, sheep tallow, oxidized polyethylene or plasticizers can also contribute to obtaining a no and optionally as an emulsion, polypropylene, transparent co-coatings with increased gloss. Certain plasticizers lymers of ethylene and acrylic esters, the waxes obtained by such as tributoxyethyl phosphate also serve as hydrogenation of coconut oil or soybean oil and the waxes 55 as leveling agents, but this property is generally mineral such as paraffin, ceresin, lignite wax, useless with the compositions according to the invention. We can also

ozokerite and the like. If you want the gloss product to use blends of fleeting and permanent plasticizers,

As clear as water, care should be taken to choose it. Examples of plasticizers or suitable wax may be cited. fleeting coalescers, monobutyl ethers, monoethyli-

Up to 50% of the weight of the wax can be replaced by f, <> c, monomethyl and monoalkyl other than diethyl-

resins or gums soluble in waxes. We can also neglycol or dipropylene glycol, isophorone, benzyl alcohol,

use natural or synthetic materials such as diglyme, "Butylcellosolve" and methoxy-3-butanol-l. Resins of terpenes and phenols, copal from Congo treated in general, these materials are mono- and polyalcohols of hot, rosin of wood, petroleum wax oxidized and high boiling point (about 150- 200 ° C) and mono and the like. m lower alkyl diethers (C [-C5) of glycols and diglycols.

The compositions make it possible to obtain shiny coatings. When the polymer is prepared by solution polymerization,

transparent gloves. However, if desired, one can be obtained as described below, and when these colored appearance oxygenated solvents are used by introducing in appropriate proportions during the polymerization, they behave as

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fleeting plasticizers in the shine composition and just branched. The hydrophilic component preferably comprises until diluting the polymer solution to the solids content to only about 14 oxyethylene units. A particular-desired agent using ammonia water. These smokeless plasticizers is an adduct of octylphenol or gace are well known and one can in this regard consult the patent nonylphenol and polyoxyethylene having a coefficient HLB US No. 3,467,610. 5 between 9 and 11. The two most preferred surfactants are the adduct of oc. Examples of substantially permanent plasticizers such as tylphenol and 5 moles of ethylene oxide and the product d 'addi-can be incorporated at low concentrations are phthalate tion of monylphenol and an average of 5.5 moles of ethyl benzyl and butyl oxide, dibutyl phthalate, lene phthalate.

dimethyl, triphenyl phosphate, 2-ethyl phthalate Generally used are oligomers forming consti-hexyl and benzyl, butyl and cryclohexyl phthalate, killing them (A) at a rate of 25 to 99.9 % of the total composition of mixed esters of benzoic acid and fatty acid of oils and nonaqueous and better still from about 65 to about 99%. When a pentaerythritol, poly dibenzoate (propylene adipate), the wax is present in the composition according to the invention, the diethylene glycol dibenzoate, caprolactam, thiodisucci - relative weight proportions of the polymer to the wax are tetrabutyl nate , butylphthalbutyl glycolate, acetylci- generally between 100/0 and 50/50 and preferably tributyl träte, dibenzyl sebacate, phosphate 75/25 by weight. The variation in these relative proportions allows tricresyl, ethyltoluenesulfonamide, the di (ethyl-2-hexyli-) ester to modify various properties and in particular the power of) of hexamethylene glycol diphthalate, the polishing phthalate. The amount of wetting agents, emulsifiers or

(methylcyclohexyl), tributoethyl phosphate and phos-dispersants, plasticizers and coalescers which are used in the tributyl pro-phate. The particular plasticizer is chosen and its aqueous glossing product is generally between 0.1 quantity taking into account compatibility and efficiency and 90%, preferably between 1 and 60% and very particularly for obtaining a product of colorless and transparent shine of between 10 and 35% of the combined weights of the oligomer, wax and optimum quality. alkali-soluble resin. The concentration of solid matter in the aqueous brightening product is so that Examples of wetting and emulsifying agents which can be suitably comprised between 1 and 45% and better still between about 3 and added to the composition of the brightening product are 25% by weight.

alkali metal salts and amine salts of higher fatty acids The oligomers which are preferred for use in the compounds

laughers containing from 12 to 18 carbon atoms, such as tions of the invention containing monomer units of form

sodium, potassium, ammonium oleate or ricinoleate mule:

or morpholine, as well as nonionic surfactants 30

currents. Certain fluorocarbon surfactants consist of W W

also wear as wetting agents and are described I I

in US Patent No. 2,937,098. The addition of a wetting agent - CH2-C - and -CH2-C

lant improves the spread of the brightening product. I |

Useful non-ionic wetting and emulsifying agents 35 COOY COOZ

are those which are prepared by adding ethylene oxide to compounds containing one or more active hydrogen atoms,

such as alkylphenols, fatty alcohols, fatty acids, where W and Y have the same definition as above and Z fatty thiols, fatty amines, fatty amides and polyols. represents a corresponding positively charged ion, derived

In many cases, the fatty radical is replaced in these 40 of an alkali metal, a hydrogen atom, an ammo-starting material group by other types of hydrocarbon radicals or an amino radical and optionally the oligomer ren-

goodies. Polyols are often block polymers or closes units derived from one or more compounds such as propylene oxide and / or butylene oxide copolymers, if acrylonitrile, methacrylonitrile, vinyl acetate, the sty-although in this case the nonionic surfactant can be reene, vinyltoluene, vinyl chloride or chloride considered as a whole as a block polymer 45 vinylidene, the average content of carboxy radicals of the polymer of ethylene oxide attached to a block polymer or copolymer being between 2 and 5.

more hydrophobic. Several blocks of one or the other types can- The oligomers which are preferred as agents of brilliance

may be present. floor for floors and floors are those previously defined

It has been known for a long time that the wetting and emulsifying power having an acid number of between 100 and 135, an average sifier of surfactants is linked to the balance between the extreme weight of the molecular weight between 1,300 and 2,500 and hydrophilic mite of the molecule and the lipophilic end of the an average content of carboxy radicals between 3.5 and molecule. This equilibrium is called hydrophilic lipophilic equilibrium 4.2 or the oligomers having an acid number between 55 and or HLB coefficient (hydrophilic lipophilic balance) of agent 70, a weight average of the molecular weight between surfactant. The scale of the HLB coefficients and of the 2000 and 4000 and a mean content of carboxy radicals can be found in the determination of these coefficients in the book “Nonio-55 between 2.5 and 3.5. Other oligomers of this type are Surfactants ", edited by Martin J. Schick (Marcel Dekker, particularly useful have an acid number between 80 and Inc., New York, 1967) pages 606-613. When the end 125, an average by weight of the molecular weight between the hydrophilic of the molecule consists of a polymer block 1000 and 2500 and an average content of carboxy radicals of ethylene oxide, the coefficient HLB is the percentage will be 3.0 to 3.5.

of this ethylene oxide block divided by 5. 60 The brightening composition should preferably have a pH in the range of about 7.0 to about 11.0. Preferred nonionic surfactants are that a self-dispersing brightener has a pH of the polyoxyethylene alkylphenols and the polyoxyethylene al- from about 9.0 to about 10.0. It is possible to introduce, cools having HLB coefficients between about 5 and to adjust the pH to the desired value, alkaline agents or about 15 and very particularly between about 7.5 and 6s suitable buffering agents such as borax, hydroxide of about 12.5. The hydrophobic constituents which are preferred sodium, phosphates, silicates or alkali carbonates, am-particularly are the alkylphenols whose moniac radical or amines such as diethylamine, triethyl-

alkyl is a radical saturated in C8-C12 and, better, strongly amine, morpholine or triethanolamine.

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In the case of a self-polishing composition which does not require polishing, the wax must not be present in a proportion of more than 25 parts by weight and preferably 15 parts by weight per 100 parts of the sum of the polymer and of the wax . Brightening compositions for floors which do not require polishing without incorporating wax are obtained satisfactorily.

In addition to the polymer and coalescing, plasticizing, wetting and / or emulsifying agents and optional components such as a wax, a metal complex, a resin soluble in the above wax and a dye, the composition according to the invention can also contain resins soluble in alkalis at a rate of 0 to 50% of the total weight of the sum of the copolymer, of the wax, of the resin soluble in the wax and of the resin soluble in the alkalis. is

The compositions can be used to impregnate textiles, leather, paper or other porous or fibrous materials. They can also be applied to plastic sheets such as "Cellophane", polyethylene, "Formica", poly (ethylene terephthalate) and "Sa-ran". They can also be applied to rigid surfaces, including surfaces of metals such as steel, aluminum, copper, brass, bronze, tin, chromium, shaped iron and also wood, stone, bricks, ceramic tiles, glass, asbestos cement roofs or walls, artificial stone and cement and concrete surfaces such as floors. The compounds according to the invention are particularly useful for the shining of floors, walls, woodwork, furniture, doors, etc., and in particular wood, linoleum, rubber, metal and material tiles. plastic, such as linoleum, asphalt, vinyl resins and vinyl resins containing asbestos.

For the shine of floors, the product must be such that the coating obtained initially or very quickly has a Knoop hardness of 0.5 to 23 or more, determined on a thick film of 0.012 to 0.063 mm on a glass substrate. This hardness range corresponds to good abrasion and wear resistance and can be obtained by appropriately choosing the monomers to be polymerized. It is preferred that the 40 Knoop hardness is between 5 and 20.

The coalescing agent, the oligomer and the polyvalent metal compound, the wax and / or the resin can be incorporated when used, in any chosen order.

When the polyvalent metal complex is used, it can be incorporated into the composition at any time; however, usually it is added last.

The compositions according to the invention exhibit good conservation. They can be applied in the usual way, for example with rags, brushes or mops. 50 They dry quickly, forming transparent and colorless films or colored films when they are pigmented, and whose surfaces are hard, resistant and remarkably shiny. There is practically no change in color of the films during aging. The application of the compositions to surfaces bearing prior coatings of compositions capable of being eliminated by the alkalis does not remove appreciable amounts of these coatings and is not accompanied by an alteration in the viscosity or the consistency of the coatings. compositions according to the invention, “o The compositions can therefore be applied uniformly and easily to the surfaces without the formation of streaks, striped areas or other irregularities.

Gloss films containing non-metallic crosslinked carboxy (acid or salt) groups can be removed by using alkaline detergents. When metals are used as crosslinking agents, the metal crosslinking coating is insoluble in water, common soap solutions and most detergent solutions and, as it is soluble in ammonium hydroxide, ammonia solutions are required to remove it.

The following analytical method is used to measure the clarity of the gloss compositions. In the present description, the expression “practically clear as water” indicates that a brightening composition containing 15 to 18% of solids, when analyzed with a Spectronic 20 colorimeter from Bausch and Lomb, calibrated in the range from 0 to 100% with methanol or distilled water, at a wavelength of 600 millimicrons, has a light transmission of at least 50%. The expression "clear as water" indicates that on examination a brightening composition containing 15-18% of solids has a light transmission of at least 85%.

Gloss is determined by subjective visual examination and analysis with a Glossmeter photovoltaic from Leeds and Northrup (catalog no. 7664) with a 60 ° head.

In the self-dispersibility test of the polishing product, a determined quantity of the polishing product is applied, to be studied on a black vinyl resin tile and on a black vinyl resin tile containing asbestos treated with a filling material and allowed to age for one day at ordinary room temperature. Self-dispersing is then carried out by applying a measured amount of the same brightening product to the preceding coating and spreading it uniformly over 2/3 of the coating.

After 10 seconds, the area where the second application was made is lightly rubbed as if to clean it, smoothed and left to dry. The panel is allowed to age for at least 2 hours before evaluating the equalization, the uniformity of the gloss and the absolute gloss compared to the part of the panel where the second application has not been made. the self-dispersion test at selected intervals to determine the variations of this property over time.

The other test methods used in the examples are well known in the art and will be found, for example, described in US Patent No. 3,467,610 and in Resin Review, Volume XVI, No. 2 1966, published by Rohm and Haas Company, Philadelphia, Pa. 19105.

The invention is illustrated by the following nonlimiting examples in which, unless otherwise indicated, the parts and percentages are expressed by weight.

Examples 1 to 5

Oligomers having the composition described in the following table are prepared by so-called radical polymerization of the mixtures of corresponding monomers. These oligomers are then used in brilliantagae products for floors for domestic use, having the following composition:

Polymer (15% solids in water)

Diethylene glycol monoethyl ether

100.0 parts 5.0 parts

Fluorocarbon surfactant, 1% active ingredient 1.0 in water (FC-128.3 M Company) part Tributoxyethyl phosphate 0.4

part

Ammonia in sufficient quantity to raise the pH to 9.5.

A part of each brightening product is modified by adding 2% of zinc ions relative to the weight of the solid oligomeric materials. These compositions are suitable as brightening products for floors for industrial use. 10 samples are thus prepared, the properties of which appear in the following table, under the presentation:

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polish for household use / polish for industrial use.

As previously indicated, the presence of zinc ions improves resistance to water and detergents at the cost of some reduction in self-dispersibility, gloss and leveling. So it is desirable that the products of

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industrial polish, self-dispersing, which must have a strong resistance to detergents, contain zinc. Zinc is generally not used in household polishers which are to provide coatings with maximum gloss and leveling.

Board

Example

1

2

3

4

5

Composition of

MMA / BA / HEMA / AA

MMA / BA / MAA

MMA / St / MAA

MMA / St / AA / MAA

MMA / MAA

the oligomer

40/40/10/10

55/30

12/70/18

70 / 13.5 / 7.5 / 9

86/14

Acid number

78

98

117

117

91

Average in

4970

4690

3550

3640

4400

weight of

molecular weight

Length of the

45

45

37

38

45

chain

Index of

6.9

8

7.4

7.6

7.1

carboxyl

Shine

TB / TB

TB + TB

Exc / -

G

TB / -

Equalization

TB / TB

Exc / TB

Exc / -

Exc- / B

Exc / -

Water resistance

AB / B

B / TB-

TB / -

B / TB

TB - / -

Resistance to

M / AB

ABF / + B +

B + / -

M / B

B / -

detergents

Autoredispersi-

bility

"Streak" effort

mild / moderate

none / slight slight / -

none / moderate

no/-

Redispersion

Comp / Comp

Comp / Comp

Comp - / -

Comp / partial draw

Equalization

TB / TB

Exc / B

TB - / -

TB / -TB-

TB / -

Shine

TB / B

TB / B

TB +/-

B / TB

TB / -

*% by weight of the monomer units represented by the following abbreviations: MMA = methyl methacrylate,

BA = butyl acrylate,

HEMA = ß-hydroxyöthyle methacryIate,

AA = acrylic acid,

MAA = methacrylic acid, and St = styrene

Example 6

A composition is prepared containing an oligomer prepared by redical polymerization.

Oligomer of Example 2 at 12% material

70

solids in water parts

Fluorocarbon surfactant

0.5

at 1% in part water

Tributoxyethyl phosphate

0.5

Ammonia in sufficient quantity to raise the pH up to 9.5

This composition has satisfactory properties.

VS

Claims (17)

623,847 1 I -CH2- C and -CH2- C - I I COOY COOZ where W and Y have the same definition as in claim 1, Z represents a positively charged complementary ion deriving from an alkali metal, a hydrogen atom, an ammonium group or an amine group and optionally a small quantity of units deriving from acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, vinyl chloride or vinylidene chloride, the average content of carboxy radicals in the polymer being between 2 and 5. 1. Aqueous brightening composition, characterized in that it comprises, at a rate of 25 to 100% of the weight of solid matter dissolved in water, an addition polymer (compound A) prepared by radical oligomerization of a mixture of monomers containing at least a mono-unsaturated acid a, P-ethylene chosen from the group of acrylic and methacrylic acids, the polymer containing at least 25 mole% of structural units: W I -CH -.- C I COOY where W represents a hydrogen atom or a methyl radical, Y represents an alkyl radical or a substituted alkyl radical; this polymer having an acid number of 50 to 275 and a weight average molecular weight of 700 to 5000 and being at least partially neutralized. 2. Composition according to claim 1, characterized in that it comprises up to 25% of the weight of solid matter dissolved in water, a wax of which up to half can be replaced by a resin soluble in waxes (B). 2 3. Composition according to claim 1, characterized in that it comprises up to 50% of the weight of solid matter dissolved in water, a resin soluble in alkalis (C). 4. Composition according to claims 1 to 3, characterized in that it comprises from 0.1 to 90% relative to the weight of the sum of (A), (B) and (C) of one or more wetting agents , emulsifiers, plasticizers or coalescers (D). 5. Composition according to claim 1, characterized in that it comprises up to 5% by weight of (A) of a polyvalent metal compound (E). 6. Composition according to claim 1, characterized in that it contains water in an amount such that the total solid content is between 1 and 45% by weight. 7. Composition according to claim 1, characterized in that it does not contain film-forming polymer of high molecular weight. 8. Composition according to claims 1 and 2, characterized in that it contains up to 25 parts by weight of the component (B). 9. Composition according to claim 1, characterized in that the polymer component (A) contains structural units: W W 10. Composition according to claim 1 for application on hard substrate, characterized in that the component (A) has an acid number of 100 to 135, an average by weight of the molecular weight of 1300 to 2500 and an average content of radicals carboxy from 3.5 to 4.2 and in that the hard substrate is a floor. 11. Composition according to claim 1 for application on hard substrate, characterized in that the component (A) has an acid number of 55 to 70, an average by weight of the molecular weight from 2000 to 4000 and an average content of radicals carboxy from 2.5 to 3.5 and in that the hard substrate is a floor. 12. Composition according to claim 1, characterized in that the component (A) has an acid number of 80 to 125, an average by weight of the molecular weight of 1000 to 2500 and an average content of carboxy radicals of 3.0 to 3.5. 13. Composition according to Claims 1 to 4, characterized in that the component (D) consists of a nonionic wetting agent comprising several oxyethylene units. 14. Composition according to claims 1 to 4, characterized in that the wetting agent is present in an amount of 10 to 35% of the weight of the component (A) and has an HLB coefficient of between 5 and 15. 15. Composition according to claim 13, characterized in that the wetting agent contains up to 14 oxyethylene units. 16. Composition according to claims 1 to 4 for application on hard substrate, characterized in that the wetting agent also contains an alkoxyphenoxy unit and in that the hard substrate is a wall. 17. Use of the composition according to claim 1 for coating a substrate, characterized in that a layer of the brightening composition is applied to the substrate and the layer is allowed to dry.