LIQUID CONCENTRATE OF SOLID PARTICLES OF HYBRID PIGMENTS CONTAINING GRAFTED COPOLYMERS AND USE OF SAME FOR PREPARING PAINTS IN AN AQUEOUS AND/OR ORGANIC MEDIUM

Abstract

A liquid concentrate of pigments of mineral and organic hybrid solid particles of 0.5 to 2 m, including a copolymer consisting of: 5 to 40 wt % of anchor sequence(s) consisting of a linear copolymer formed from a first monomer with a basic nitrogenous group added from compound(s) selected from vinylpyridines, and a second monomer of the anchor sequence consists of an ethylene monomer containing an aromatic group, the weight content of the first monomer relative to the second monomer being 40-60 wt %, 25 to 90 wt % of the hydrophobic sequence(s) obtained from a polymer-substituted ethylene macromonomer of which the monomer units contain COOR.sub.10 groups, where R.sub.10 is an optionally substituted C1-C10 alkyl, and 5 to 70 wt % of hydrophilic sequence(s) obtained from an ethylene macromonomer substituted by a hydrophilic sequence comprising a polyethylene glycol sequence substituted by a terminal alkoxy group, or connected to a polypropylene glycol sequence.

Claims

1. A liquid concentrate of pigments of mineral and organic hybrid solid particles of 0.5 to 2 m, useful for the manufacture of paints comprising an aqueous or organic solvent, comprising a grafted copolymer containing at least three sequences of different chemical nature, among which at least one anchor sequence capable of being absorbed on solid particles, at least one hydrophobic sequence, and at least one hydrophilic sequence, wherein said copolymer consists of: 1) 5 to 40 wt % of said anchor sequence(s) consisting of a linear copolymer formed from at least two different monomer units comprising: a) a first monomer with at least one basic nitrogenous group added from one or more compound(s) selected from the vinylpyridines and aminoalkyl(meth)acrylate of formula I: ##STR00016## where R.sub.1 is a hydrogen atom or a (C1-C4) alkyl radical; R.sub.2 and R.sub.3, which may be identical or different, are each a hydrogen or a (C1-C4) alkyl radical, n=0 to 6, and b) a second monomer of the anchor sequence consists of a monomer of formula II: ##STR00017## wherein: R.sub.4, R.sub.5, R.sub.6 are identical or different and are each a hydrogen or a C1-C4 alkyl radical, R.sub.7 is an aromatic group comprising an optionally substituted phenyl group, the weight content of said first monomer relative to said second monomer being between 40 and 60 wt %, and 2) 25 to 90 wt % of said hydrophobic sequence(s) obtained from a macromonomer of formula (III): ##STR00018## wherein: R.sub.4, R.sub.5, R.sub.6 are identical or different and are each a hydrogen or a C1-C4 alkyl radical, and R.sub.8 consists of a polymer whose monomer units contain COOR.sub.10 groups in which R.sub.10 is an optionally substituted C1-C10 alkyl, and 3) 5 to 70 wt % of hydrophilic sequence(s) obtained from a macromonomer of formula (IV): ##STR00019## R.sub.4, R.sub.5, R.sub.6 are identical or different and are each a hydrogen or a C1-C4 alkyl radical, and R.sub.9 is a hydrophilic sequence comprising a polyethylene glycol sequence (a) substituted by a terminal alkoxy group or (b) connected to a polypropylene glycol sequence.

2. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said hybrid solid particles comprise mineral particles having a hollow or porous structure, filled with organic dye pigments.

3. The liquid concentrate of pigments of hybrid solid particles according to claim 2, wherein said hybrid particles comprise clay mineral particles in the form of hollow fibres called sepiolite, inside which fibres of organic dye pigments of plant origin are added.

4. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said hybrid particles comprise particles of complexes of infrared (IR)-radiation-reflecting pigments complexed with organic molecules of dyes.

5. The liquid concentrate of pigments of hybrid solid particles according to claim 4, wherein said particles of complexes of infrared (IR)-radiation-reflecting pigments comprise white metallic oxides, or black metallic oxides.

6. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein the hydrophilic sequence R.sub.9 is obtained from a macromonomer of polypropylene glycol-ethylene glycol methacrylate, R.sub.9 being a polypropylene glycol sequence substituted by a terminal polyethylene glycol sequence.

7. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said hydrophilic sequence is obtained from a macromonomer of methoxy polyethylene glycol methacrylate, R.sub.9 being a hydrophilic sequence comprising a polyethylene glycol sequence substituted by a terminal methoxy group.

8. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein, in said anchor sequence, said first monomer is 2-dimethylaminoethyl methacrylate monomer and said second monomer is styrene.

9. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said hydrophobic sequence is obtained from a polymer macromonomer of ethylhexyl methacrylate units.

10. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein the molecular weight of the grafted copolymer is between 5,000 and 25,000.

11. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said copolymer comprises: a said hydrophilic sequence obtained from a macromonomer of polypropylene glycol-ethylene glycol methacrylate, or a macromer of methoxy polyethyleneglycol methacrylate, a said anchor sequence obtained with a said first monomer which is 2-dimethylaminoethyl methacrylate monomer and said second monomer which is styrene; and a said hydrophobic sequence obtained from a macromonomer of methacrylate polymer of ethylhexyl.

12. The liquid concentrate of pigments of hybrid solid particles according to claim 1, comprising an aqueous solvent.

13. The liquid concentrate of pigments of hybrid solid particles according to claim 1, comprising a dry extract of pigments of hybrid solid particles greater than or equal to 45%.

14. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein the weight content of the dry extract of said grafted copolymers is from 10 to 30 wt % of said liquid concentrate.

15. A process for preparing paint, comprising: mixing a liquid concentrate of pigments of hybrid solid particles according to claim 1 with other components of the paint.

16. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein a relative weight proportion of organic molecules of dyes in said pigments of hybrid solid particles is from 1 to 45 wt %.

17. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein said copolymer consists of: 15 to 35 wt % of said anchor sequence(s), 40 to 80 wt % of said hydrophobic sequence(s), and 15 to 30 wt % of hydrophilic sequence(s).

18. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein R.sub.10 is a C2-C8 alkyl which can be optionally hydroxyl-substituted.

19. The liquid concentrate of pigments of hybrid solid particles according to claim 2, said hybrid solid particles comprise mineral particles having a hollow or porous structure, filled with organic dye pigments with a relative weight proportion of organic dye pigments in said pigments of hybrid solid particles of 1 to 30 wt %.

20. The liquid concentrate of pigments according to claim 4, wherein said hybrid particles comprise particles of complexes of infrared (IR)-radiation-reflecting pigments complexed with organic molecules of dyes with a relative weight proportion of organic dye molecules in said pigments of hybrid solid particles of 1.5 to 15 wt %.

21. The liquid concentrate of pigments of hybrid solid particles according to claim 1, wherein the hydrophilic sequence R.sub.9 is obtained from a macromonomer of polypropylene glycol-ethylene glycol methacrylate of molecular weight of 500 or higher.

22. The liquid concentrate of pigments according to claim 5, wherein said particles of complexes of infrared (IR)-radiation-reflecting pigments comprise white metallic oxides consisting in the titanium dioxide of crystalline form known as rutile, or black metallic oxides consisting in chromium oxide.

Description

EXAMPLE 1: PREPARATION OF COPOLYMERS

[0158] A) The Copolymers

[0159] The copolymers have a comb structure whose main chain is the solid-particle anchor sequence and the side chains consist of hydrophobic and hydrophilic sequences. According to the nature of the particles to which the copolymer will be attached, the hydrophilic and/or hydrophobic sequences may alternatively also be anchor sequences.

[0160] The anchor sequence: consists of amino acrylic monomers (e.g., DMAEMA) or non-amino acrylic monomers (methacrylic acid) and/or vinyl aromatic monomers (e.g., styrene or 2-vinylpyridine).

[0161] The hydrophobic sequence is obtained from the ethylhexyl methacrylate polymer macromer having molar mass 1000 to 3000, polydispersity index 1.3 to 1.5, structure: CH.sub.3(CH.sub.2).sub.3CH(C.sub.2H.sub.5)CH.sub.2OCOC(CH.sub.3)CH.sub.2.

[0162] The hydrophilic sequences are obtained from HEMA 10, PPGEGMA 750, PPGMA, CLA and MPEGMA macromers.

[0163] 3a) PPGEGMA 750Poly-propyleneglycol-ethyleneglycol-methacrylate

Structure:

[0164] ##STR00012##

[0165] PPGEGMA is the ester of methacrylic acid esterified with n units of propylene glycol and m units of ethylene glycol.

[0166] PPGEGMA 750, having a weight average molar mass of about 750 g/mole, corresponds to n=2 to 4 units of propylene glycol and m=8 to 10 units of ethylene glycol.

[0167] 3b) PPGMAPoly-propyleneglycol-methacrylate

[0168] Structure:

##STR00013##

[0169] PPGMA is the mono methacrylate with n units of polypropylene glycol, in particular n=5 for a weight average molar mass of about 376 g/mole.

[0170] 3c) CLACaprolactone acrylate

[0171] Structure:

##STR00014##

[0172] CLA is caprolactone acrylate. Its weight average molar mass is about 344 g/mole.

[0173] 3d) MPEGMAMethoxy Polyethylene glycol mono methacrylate

[0174] Structure:

##STR00015##

[0175] MPEGMA 550 is the mono methacrylate with n=6 units of ethylene glycol. Its weight average molar mass is about 550 g/mole.

[0176] 3e) HEMA 10=Methacrylate of Polyethylene glycol (or hydroxy poly ethoxy (10) methacrylate). Structure: OH(CH.sub.2CH.sub.2O).sub.nCOC(CH.sub.3)CH.sub.2 with n=10.

[0177] Its weight average molar mass when n=10 is about 600 g/mole.

[0178] In Table 1, the information provided corresponds to the relative weight proportions of the various components.

TABLE-US-00001 TABLE 1 Copolymers Composition 1 2 3 4 5 6 Anchor Methacrylic acid 20 20 sequence Styrene 20 20 20 20 20 DMAEMA(1) 20 20 20 20 20 2-Vinylpyridine Hydrophobic pEHMA 2000(2) macromer 100 100 100 100 100 sequence pEHMA 2700(3) macromer 100 Hydrophilic HEMA-10 macromer 22 22 22 22 sequence PPGEGMA 750 macromer 22 PPGMA macromer 22 CLA macromer MPEGMA 550 macromer Polymer Molar mass 14500 19200 12000 11000 15000 17300 characteristics Polydispersity index 1.60 1.72 1.43 1.51 1.78 1.83 Copolymers Composition 7 8 9 10 11 Anchor Methacrylic acid 20 sequence Styrene 20 20 20 DMAEMA(1) 20 20 20 20 2-Vinylpyridine 20 20 Hydrophobic pEHMA 2000(2) macromer 100 100 100 100 sequence pEHMA 2700(3) macromer 100 Hydrophilic HEMA-10 macromer sequence PPGEGMA 750 macromer PPGMA macromer CLA macromer 22 MPEGMA 550 macromer 22 22 22 22 Polymer Molar mass 18700 14000 15500 11800 15500 characteristics Polydispersity index 1.52 1.55 1.64 1.57 1.64 (1)DMAEMA: 2-dimethylaminoethyl methacrylate (2)Molar mass: 2000, Polydispersity index 1.26 (3)Molar mass: 2700, Polydispersity index 1.45

[0179] B) Protocol:

[0180] The various components below are added to a tank, in semi-batch mode, so as to avoid composition drift due to the different reactivity of the various reagents. Copolymerization is carried out at 80 C.

[0181] The conditions are described below:*

[0182] When addition is completed, the reactor is left at 80 C. for about 5 hours to obtain total conversion.

[0183] The solution obtained, once cooled, has a clear appearance with no formation of gel.

[0184] The phase change of the copolymer obtained is achieved by adding it to the aqueous phase and exchange occurs by azeotropic distillation.

[0185] The final suspension of copolymer in aqueous phase is translucent after cooling.

[0186] Copolymer composition added to the tank:

[0187] Hydrophobic macromer: 438 g

[0188] Hydrophilic macromer: 237 g

[0189] Styrene: 54 g

[0190] DMAEMA: 54 g

[0191] Toluene: 748 g

[0192] NBMA: 17.3 g

[0193] NBMA: 17.3 g

[0194] Copolymers no. 1, 2, 5, 6, 7, 8, 9, 10 and 11 comprise anchor sequences of the invention. In view of the comparative results of Example 3 below, copolymers no. 1, 2, 5, 6, 7, 8 and 9 comprise a preferred anchor sequence.

[0195] Among these, copolymers no. 1, 5, 6, 7 and 8 comprise a preferred hydrophobic sequence of the invention (EHMA 2000), and copolymers no. 5, 8, 9 and 10 a preferred hydrophilic sequence of the invention (PPGEGMA 750 and MPEGMA 550).

[0196] Other anchor sequences comprising only one of the two elements were tested but had unsatisfactory results in combination with the best hydrophilic sequences and hydrophobic sequences on the one hand and, on the other hand, other hydrophobic sequences, notably the PLMA macromer, were tested with the best anchor sequences and hydrophilic sequences were tested having poorer results, notably PPGMA and CLA of higher molecular weights.

EXAMPLE 2: PREPARATION OF PIGMENT CONCENTRATES

[0197] A) Protocol:

[0198] Aqueous liquid concentrates of particles of intermediate diameter are prepared by mixing the following components: [0199] Water [0200] Copolymer [0201] Particles of intermediate diameter [0202] Additives: antifoam, bactericides, rheology agents

[0203] The procedure for fabricating concentrates of particles of intermediate diameter is the following:

[0204] 1Placing the water in a tank

[0205] 2Adding the amount of copolymer

[0206] 3Placing the tank under a variable-speed agitator with a dispersion disc suited to the size of the tank

[0207] 4Gradual addition of the particles of intermediate diameter under moderate agitation (500 to 800 rpm).

[0208] This first phase is defined as the coating phase for wetting the surface of the particles of intermediate diameter; the particles of intermediate diameter are not yet in the state of maximum dispersion (complete separation of the particles forming agglomerates of particles of intermediate diameter); a coating time of about 20 minutes to 40 minutes depending on the characteristics of the particles of intermediate diameter. A portion of the additives is also added during this coating phase.

[0209] 5The grinding operation is performed by increasing the dispersion speed to 1500 rpm with a high peripheral speed around 15 to 20 m/second. This grinding step is not a matter of grinding the elementary particles of the particles of intermediate diameter but of dispersing these particles contained in the agglomerates. The grinding time may vary from 20 minutes to 60 minutes depending on the nature of the particles of intermediate diameter, especially their particle size and their specific surface area. The second portion of additives can be added when grinding is completed.

[0210] 6The characteristics of the concentrate of particles of intermediate diameter are checked by measuring: [0211] Dry extract [0212] Rheological characteristics [0213] Stability [0214] Compatibility

[0215] Concentrates in solvent phase with paint thinner as solvent were also successfully prepared.

[0216] The characteristics of the particles of intermediate diameter used in the examples are explained below and in Table 2 below.

[0217] In Table 2 below, the following particles were used:

[0218] aParticles no. 1 to 3: Mayan-type blue (no. 1), red (no. 2) and yellow (no. 3) hybrid pigments

[0219] These particles are marketed by the company PIGM'AZUR (France) under the mark PIGM'ART. They consist of fine small hollow clay fibres like Sepiolite inside which coloured organic or mineral molecules of plant origin are added, namely in particular the colouring molecules selected from indigoids, anthraquinone dyes, flavonoids, azo dyes, melanins, tetrapyrrole dyes, nitrated dyes, nitroso dyes, polymethine dyes, di- or triphenylmethane dyes. The dye material is thus protected from the outside by the clay walls.

[0220] The following pigments below were used: [0221] PIGM'ART BLUE containing indigo blue, [0222] PIGM'ART RED containing anthraquinone hydroxyl derivatives, and [0223] PIGM'ART YELLOW containing flavonoid derivatives.

[0224] The dimensions of the fine particles of small hollow fibres are: [0225] average length of 1 m to 2 m, [0226] fibre diameter (width) of about 0.01 m; [0227] inner diameter and length of the internal tubular axial openings: 3.6 10.6 .

[0228] bParticles no. 4 and 5: solar IR-reflecting pigments complexed with coloured organic pigments.

[0229] Particles no. 4 comprise solar IR-reflecting white pigments based on rutile-type titanium dioxide TiO2 of large size ALTIRIS 800 of 800 nm. Particles no. 5 comprise solar IR-reflecting black pigments based on chromium oxide ALTIRIS 550 pigment of 550 nm.

[0230] Particles no. 4=ALTIRIS 800 complexed with a blue organic pigment of phthalocyanine. Particles no. 5=ALTIRIS 550 complexed with red organic pigments of toluidine.

TABLE-US-00002 TABLE 2 Type of particles of intermediate diameter Particle type particle size No. Hybrid pigments of type Mayan blue 1-2 1 Hybrid pigments of type Mayan red 1-2 2 Hybrid pigments of type Mayan yellow 1-2 3 Solar IR-reflecting pigment ALTARIS 700 nm-900 nm 4 800 nm + organic blue pigment Solar IR-reflecting pigments ALTARIS 500 nm-600 nm 5 550 nm + organic red pigment

[0231] The examples of concentrates of particles of intermediate diameter are summarized in Table 3 below, with copolymers no. 1 to 11 of Example 1.

TABLE-US-00003 TABLE 3 Particle concentrates Weight % A B C D E F G H Water % 29 29 29 29 29 29 29 29 Copolymer No. 1 No. 2 No. 3 No. 4 No. 5 No. 6 No. 7 No. 8 % 25 25 25 25 25 25 25 25 Particle No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 No. 1 % 45 45 45 45 45 45 45 45 Antifoam + 1 1 1 1 1 1 1 1 bactericide Rheology 12 12 35 40 10 27 62 10 Stability 1 1 1 1 3 2 1 3 Compatibility 1 1 1 1 3 2 1 3 Weight % I J K L M N Water % 29 29 29 29 29 29 Copolymer No. 9 No. 10 No. 11 No. 8 No. 8 No. 8 % 25 25 25 25 25 25 Particle No. 1 No. 1 No. 1 No. 2 No. 4 No. 5 % 45 45 45 45 45 45 Antifoam + 1 1 1 1 1 1 bactericide Rheology (P) 25 58 36 15 9 11 Stability 2 1 2 3 3 3 Compatibility 2 2 2 3 3 3 [0232] Rheology: It is measured using a rheometer at 500 s.sup.1, at 20 C. and expressed in poises (P). It is good between 8 and 15 P. [0233] Stability test:

[0234] Scale used in the tables:

[0235] 3good

[0236] 2satisfactory

[0237] 1poor

[0238] The stability test is performed on the concentrates of particles of intermediate diameter but also on paints containing them.

[0239] This test is performed on a sample of concentrate of particles of intermediate diameter which is placed in an oven at 50 C. for 3 weeks. Three 200-ml containers are prepared and inspected before being placed in the oven.

[0240] At the end of each week, a container was taken out of the oven and, after being left overnight for its temperature to stabilize (at room temperature), the following inspections were made to analyse whether its stability was good or not: [0241] Verification of the concentrate of particles of intermediate diameter in the container: presence or absence of surfacing (syneresis) or of settling (presence of a deposit at the bottom of the container, whether hard, soft, large or not). [0242] Measurement of viscosity and comparison relative to the control before oven-heating: analysis to check whether the product has fluidified, thickened or hardened.

[0243] These observations and measurements are made after 1, 2 and 3 weeks; based on the various analyses, the concentrate of particles of intermediate diameter is rated on the scale above. [0244] Compatibility test:

[0245] Scale used in the tables: 3=good, 2=satisfactory, and 1=poor

[0246] The compatibility test is intended to verify the physicochemical behaviour of the concentrate of particles of intermediate diameter in paints, liquid coatings, liquid inks and liquid formulations for coating.

[0247] After mixing with a disc mixer, at a speed of about 600 rpm, the mixture is analysed: [0248] Observation of the mixture: presence of agglomerates, phase separation, sedimentation, etc. [0249] Measurement of viscosities, [0250] Application, with a 100 calibrated applicator, onto a substrate commonly used for paint, ink, coating, contrast card, to check the transparency of the deposited film when wet and then when dry after drying, [0251] Verification of the characteristics of the dry film: opacity, colour, gloss.

[0252] Based on this analysis, the concentrate of particles of intermediate diameter is rated, according to the scale above, substantially compatible.

[0253] From these results, it arises that it is possible to obtain a concentrate of particles of intermediate diameter having good rheology and good or satisfactory compatibility and stability properties only for the copolymers comprising two types of monomers in the anchor sequence, in accordance with the present invention, namely copolymers 5, 6 and 8 to 11.

[0254] Furthermore, the copolymers with hydrophobic sequences obtained with (EHMA) macromers and hydrophilic sequences obtained with PPGEGMA 750 and MPEGMA 550 macromers have the best stabilities and compatibility (copolymers 5 and 8)

EXAMPLE 3: PREPARATION OF PAINTS CONTAINING A CONCENTRATE OF PARTICLES OF THE INVENTION

[0255] A) an aqueous paint is prepared by adding and mixing each concentrate of particles of intermediate diameter in a pastel (P) or transparent (TR) base paint according to use, using a gyroscopic agitator. The characteristics of the paints are checked by measuring the following parameters for the liquid paint: density, weight content of the dry extract, viscosity and stability. The results are rated: 3=good; 2=satisfactory and 1=poor in Table 4.

TABLE-US-00004 TABLE 4 Paints containing a concentrate of particles Paint no. 1 2 3 4 5 P base % 95 95 95 95 95 95 95 95 95 TR base % Concentrate of A B E F G H L M N particles % 5 5 5 5 5 5 5 5 5 Results 1 1 2 1 1 3 1 3 3

[0256] The best results are obtained with the concentrates containing copolymer no. 8.

[0257] The compositions of the P (pastel) base and of the TR (transparent) base are presented in Table 5 below in which the values are weight proportions expressed as a percentage.

TABLE-US-00005 TABLE 5 PASTEL BASE TRANSPARENT BASE 5.500 WATER 5.500 WATER 38.900 FINE CARBONATE 38.900 FINE CARBONATE 30.000 UCAR LATEX DL 30.000 UCAR LATEX DL 0.800 COAPUR W 0.800 COAPUR W 22.000 MOWILITH LDM 22.000 MOWILITH LDM 0.400 ACRYSOL DR 0.400 ACRYSOL DR 0.150 PREVENTOL 0.150 PREVENTOL 0.200 DEA 0.200 DEA 1.700 NEXCOA.NX 1.700 NEXCOA.NX 0.100 CALGON N 0.100 CALGON N 0.250 BYK 023 0.250 BYK 023

[0258] B) Two other types of paints are prepared with aqueous concentrates and organics solvents, respectively.

TABLE-US-00006 Aqueous paint Solvent paint Water Aliphatic, aromatic, isoparaffinic Aqueous binder: vinyl and/or solvents acrylic latex Solvent binders: alkyds, Aqueous filler modules glycerophthalics Additives: bactericides, antifoam, Solvent or universal filler modules rheology agent Additives: rheology agent, drying Dyes agent and plasticizer Dyes

[0259] The modular components are all liquids and therefore can be stored in tanks, pumped, automatically measured and easily mixed.

[0260] A paint can therefore be manufactured quickly and economically.

[0261] The procedure for manufacturing modular paints, which can be applied to all weight or volume combinations of the various liquid components, comprises the following successive steps:

[0262] 1placing the various components in a tank

[0263] 2placing the tank under a variable-speed agitator with a mixing screw suitable for liquid mixtures in relation to the size of the tank, with a mixing time of about 20 minutes at a speed of 700 rpm. The mixture can also be made with a vibration type agitator using 1-to 20-litre containers into which the various liquid components have been measured out. The mixture is prepared after closing the lid and shaking the container with the agitator for about 5 minutes.

[0264] 3The characteristics of the paints are checked by measuring the following parameters: [0265] For the liquid paint: [0266] Density (g/cm.sup.3) [0267] Dry extract [0268] Viscosities [0269] Stability [0270] For the dry film: [0271] Colorimetric coordinates [0272] Opacity [0273] Surface gloss

[0274] The formulas of the prepared paints are presented in Table 5. [0275] The best results are obtained with the concentrates comprising copolymers no. 5 and 8.