MXPA96006040A - Procedure for the preparation of color contrast in articles obtained by molding from part polymerizab compositions - Google Patents

Abstract

Method of molding articles having color contrast zones on the surface comprising the coating of the surface with a polymerized colored composition before filling the mold with a polymerizable fluid composition, wherein the colored composition is a fluid, stable dispersion and redispersible, comprising: a) polymerizable liquid monomers, optionally in admixture with a non-polymerizable volatile organic solvent, as a solvent, b) from 0.1 to 10% by weight of a coloring composition as an inorganic pigment or from 0.0001 to 1% by weight of a pigment or organic dye, c) from 1 to 30% by weight of an acrylic resin soluble in solvent a) and containing reactive functional groups capable of producing crosslinking, component a) being at least 20% by weight of the tot composition

Description

PROCEDURE STOP LFL PREPARATION OF COI OR FN CONTRACTS ARTICLES OBTAINED BY MOLDING FL FROM COMPOSITIONS POLIGIERIZABLES The present invention relates to a method for obtaining a color contrast on a surface of a molded article and to the paint composition for obtaining the color contrast. In particular, the composition containing the color is applied in a specific area of the surface of the mold where the article is to be formed using a polimepable composition. It is known in the art that by molding techniques it is possible to obtain articles having an upper surface finish by using dispersions of a filler in a polymechanizable liquid. These compositions are well known in the art and are fluid dispersions formed by polymetabolizable inoninomers based on methyl meta-platelet containing large amounts of filler. See, for example, European Patent 321193, or US Pat. No. 3,324,074, wherein the dispersions are obtained by using a flux or a dispersant. Other types of compositions are known in which a polymeric dispersant is used to obtain dispersions (see for example GB Patent 1, 493,:) 93).

The characteristic of the dispersions obtained according to the invention resides in that, although they contain a high amount of mineral filler, they are stably deflocculated or easily redissuable in the polymerizable material contained therein when sedimentation of the filler occurs. These compositions are used to form molded articles such as sanitary articles in general, endowed with the essential feature to have a superior finishing surface. It is also known to provide finished surfaces of molded articles having a color contrast on the surface of the article. The problems in this type of color contrasts are that the pigmented composition when applied to the mold should not disappear at the time of injection of the polimerizable composition that the finished article has to form. The finished item with color contrast should have uniform color on the colored surface, exactly reproducing the impression previously placed on the mold, that is, it should not show areas where color is missing or others where the color has a different tone. The methods known in the art for obtaining color contrast in the art are represented by EP 61245 and 217544. In EP 61245, the composition for color contrast requires, as an essential element, to contain a mixture of a filler finely subdivided, such as silica. In the patent it is shown with comparative examples that if the filling is absent, for example silica, it is not possible to obtain a homogeneous color contrast, but surfaces are obtained in which color variations and deshornogeneities appear. From the industrial point of view, the products obtained in the absence of silica have no use. In EP 217544, compared to EP 61245, compositions are described which could represent an improvement of the previously described patent and in particular would avoid any possibility of obtaining dehomogeneous surfaces. The color contrast compositions are characterized in that they contain as an essential element a drying alkyd resin and because the presence of silica is no longer necessary to obtain a homogeneous colored surface, silica being an optional component. Tests carried out by the Applicant have shown that many types of paints indicated as acceptable in the two patents are not capable of providing homogeneous surfaces that may have industrial utility, even in the presence of silica mineral filler. In addition, also the resins that give the most homogeneous surfaces show surface defects at the point where the polyrneable composition is injected. The technical problems raised in the patent applications mentioned above have not been found, therefore, a satisfactory technical solution. In a prior patent application of the Applicant, see European Patent Application No. 95108221.3, colored compositions were described for use in the color contrast techniques indicated above, which make it possible to obtain homogeneous surfaces also at the injection point of the polimerisable composition, which are comprised as an essential component of a particular type of polymer or film forming agent formed by an unsaturated polyester resin. The Applicant has unexpectedly and surprisingly found another specific type of polymer as a film-forming agent, as an essential component of the colored composition, to obtain color contrasts with homogeneous surfaces also at the point of injection of the fluidizable polymerizable composition. The object of the present invention is a method of molding articles having areas of color contrast on the surface, comprising coating the surface or part of the surface of the mold with a polymerized colored composition before filling the mold with a fluidizable, polymerizable composition wherein the colored composition is a fluid, stable and redispersible dispersion comprising a) polytherizable liquid polymers, optionally in admixture with a volatile non-polyrneable organic solvent, <solvent; b) from 0.1 to 10% by weight of a coloring composition as an inorganic pigment or from 0.0001 to 1% by weight of an organic pigment or dye; c) from 1 to 30% by weight of a solvent-based acrylic resin in solvent a) and containing reactive functional groups capable of + reclosing + o; optionally comprising one or more of the following components: d) from 5 to 70% by weight on the total composition of? n finely divided filler, having an average diameter of 0.5 to 10 microns, preferably from? at 6 microns; e) a regulator of polymeric viscosity soluble in the solvent a) in concentrations of 0.1 20% by weight, f) other polyrnepic or non-polyane additives, in amounts of less than 5% by weight on the total of the components, acting as filler dispersants d), diluents, latent solvents, polymerization inhibitors, molecular weight regulators, polymerization activators, surfactants, film-forming agents; Entrepreneurs of Ruzarnlen or; component a) being at least 20% by weight of the total composition. The components used in paints and dispersions are usable, obviously.

It is preferable that inorganic fillers are present to obtain a reduction of the shrinkage phenomenon during the polymerization of the polishable composition to obtain the finished article and increase the hardness of the surface of the painted object. In the preferred compositions, the components vary in the following scales: a) from 30 to 60% by weight; b) from 2 to 6% by weight in the case of inorganic pigments and from 0.01 to 0.5% by weight in the case of organic pigments; c) from 1.5 to 10% by weight. For the optional components, the preferred scales are: d) from 20 to 50% by weight; e) from 1 to 10% by weight. According to the present invention, filler means an insoluble reinforcing substance added to the pigmented composition to confer mechanical properties on the colored surface without having any relevant effect on the color. Both organic and inorganic pigments that can be used are well known in the art. The dispersion of these pigments can be favored with the presence of small amounts of surfactants, for example, of alkylphenol ethoxylates, polyglycols, stearates, etc. Armor fillings that can be used and are described, for example, in an earlier patent application EP 321193 of the Applicant, are also well known, in particular, the sizes must be in the scale of less than 20 microns, with an average diameter of between 0.5 and 10 daughters-in-law, preferably 2 to 6 micras. The acrylic reams of the present invention are well known in the art. They can be subdivided into two main classes: terra-lined and ter-plastic. The thermofused reams usually have a low molecular weight and reactive groups pending the chain to allow a subsequent crosslinking; The thermoplastics have a much higher molecular weight and generally show few reactive groups that serve to confer adhesion properties. According to the present invention, also the thermoplastic resins must contain reactive groups in a number equal to that of the terrnofrained resins. The amount of functional groups, for example, -OH, -C00H, expressed as weight% on the dried resin, is between 1.5 and 25, preferably 2 10, most preferably 3 to 6. Thermosetting resins are preferably used. Acrylic polymers are obtained by polymerization reaction where a peroxide is commonly used in the initial induction phase. Acrylic monomers have the general formula CHa = CRX wherein R can be hydrogen (acrylic monorials), or CH3 (rnonorneros inetacri lieos); X is COOH, COOR ', where R' contains from 1 to 20 carbon atoms. Examples of acrylic monomers are acrylic, necrylic acid; the esters of acrylic or me + acrylic acid are: methyl acrylate, ethyl acrylate, isopy-oplo acrylate, (rnet) butyl acrylate, (et) acp. lato (Je lauplo, decyl, undecyl, propyl, stearate, methyl methacrylate, isopropyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-ethexyl acrylate, (rnet) hydroxyalkyl acrylate with the alkyl of 2 to 5 carbon atoms, etc. Different types of functional groups may be present in the acrylic monomers or inetacr? and to be present at the end acrylic resin. The functional groups commonly known and used for cross-linking are hydroxy, carboxylic, amide and epoxy groups. The carboxylic groups are represented by acrylic acid and ethacrylic acid, as indicated above. Hydroxy groups are represented, for example, by (net) acrylate of 2-hydroxyethyl having the formula CH2 = CR-CO-0 ~ CH2CH20H; R is H, CH 3; or by (me) 2-hydroxypropyl acrylate.

Among the epoxy groups there may be mentioned (et) glycidyl ester, which has the formula preferably glycidyl methacrylate, less toxic than glycidyl acrylate. Among the amides, there may be mentioned (rnet) acrylarnide having the formula CH 2 = CR-CO ~ NH 2. Other groups that may be mentioned for illustrative purposes are amines, isocyanate, n-methylol ether, etc. The acrylic polymers, homopolymers and copolymers described above may also contain units derived from other monomers containing double bonds such as styrene, alpha-ethylstyrene, vinylacetate, vinylpropionate and the esters of versatic acid, acrylonitrile, n-akyl or aryl rnaleirnides, etc. or of monomers with double unsaturation such as, for example, butadiene, ethylene glycol (meth) acrylate, (rnet) propylene glycol acrylate, trimethylolpropane (meth) acrylate, etc. The thermosetting acrylic resins, as already mentioned, are similar to the thermoplastic acrylic resins with the difference that they contain the so-called functional monomers in the monomer mixture to give functional groups pending of the polyester chain. In general, the molecular weight of the thermosetched acrylic resins is lower since the inolecular weight increases during the crosslinking reaction. Having a lower molecular weight, thermosetting acrylic resins are easier to dissolve in solvents and can be formulated with very dry dispersions. The reactive groups pending of the chain can be The following: -R "-CH-CH2 \ / O (R "is part of the glycidyl residue); -R "-NH-CH2 ~ 0H (R" is part of the residue rnetHol) -R "-NH-CH2-0-R" '(R "is part of the residue alq? Ilinetilol) .CH2 -R "-NH-C = 0-N \ CH: (R "is part of the ethyleneureide residue); -R "-C = 0-0-NH-R" -NH-0-R "'(R" is part of the urethane residue); R '' 'being an alkyl of 1 to 20 carbon atoms; -R '' - C0-0H (R "is part of the residue of the carboxylic group); -R "- CH2-0H (R" is part of the hydroxyl group residue); -R "-NH2 (R" is part of the residue of the arninic group); -R '' ~ C0-NH2 (R "is part of the residue of the amide group); -R '' -0-C0-NH2 (R "is part of the residue of the carbamate group).

The Cornonorneros who produce the pendant groups in the polimépca chain are in amounts generally lower than 10%, preferably less than 5%, and preferably from 1 to 3%. The thermosetting acrylic resins are crosslinked either by the addition of catalysts, usually acidic or psychic, to give the degree of cross-linking, or by heating, or by means of peroxides. The acrylic resins which can be used in accordance with the present invention are commercially available and can be mentioned, for example, acrylic resins containing epoxy groups modified with fatty acids such as ACTILANE 310 from AKCROS, acrylic reams containing di-functional epoxy groups. «Ales such as ACTILANER 320, res as acplicas containing OH groups such as DAGOTEX F 232 of Ernst 3aeger. Component a) of the polirnepzable rnonornero type is indicated hereafter. As already mentioned, a) can also be used in admixture with a non-polybleatable solvent. The latter must be sufficiently volatile to be eliminated for the most part before the introduction of the curable composition; in any case there must be a solvent for the acrylic resin. Examples of non-polishable solvents are aromatic hydrocarbons, ketones, saturated esters, ethers, etc. The polymeric viscosity regulating component is a polymer that is polymeric and compatible with the polymer obtained by polymerization of component a), and also as such does not significantly reduce the physical properties of the colored coating. Well-known examples of polymers used for the viscosity variation also when used in small quantities, at most up to 20% by weight with respect to monomer a), preferably from 1 to 10%, are polypropylene furnaces or copolymers of methyl methacrylate with other co -omers, in amounts up to 40% by weight, preferably up to 10% by weight. They are, for example, poly (methyl methacrylate), copolymers of methyl ethyl acrylate / methyl or ethyl acrylate, rnethyl methacrylate / styrene copolymers. These generally have average molecular weight between 10,000 and 1,000,000, preferably between 20,000 and 100,000. The additives f) comprise additives commonly used in the paint dispersion technique. For example, polymeric or non-polymeric dispersants of the dye and filler d), when present. For example, there may be mentioned as polyrheric dispersants: copolymers of methyl methacrylate / methacrylic acid, rnetyl methacrylate / alkoxysilanes containing double-bond copolymers, for example, gamma-inetacri-loxy-propyl-methoxy-silane (A 174, marketed by Uni Carbide), etc. As non-polyineric dispersants there may be mentioned alkoxysilanes, in particular, A-174. These agents also act as agents form film lords, described below. Polyarctic dispersants are described, for example, in UK Patents 1,493,393, UK 1,328,136, and EP 321193. The molecular weight of polymerase dispersants can be regulated, if desired, by introducing molecular weight regulators, for example, mercaptans, terpenes, etc. , in amounts between 0.01 and 1% by weight. The intrinsic viscosity u of the polymeric dispersants is preferably between 20 and 300 1 / g. Other additives f) are latent solvents to regulate the formation of the colored coating; polymerization inhibitors of the type usually employed for acrylic monomers, such as for example hindered phenols, quinones, quinoethers; molecular weight regulators that are involved in the film formation phase by regulating the molecular weight of the film itself, such as for example rnercaptans, terpenes, etc., polymerization activators such as, for example, carboxylic acid salts, among which there are fatty acids (the well-known metal soaps), octoates, acetylacetonates, naphthenates of cobalt, calcium, zirconxo, barium, lead, ceno, selenium; preferably, cobalt salts are used; surface-active agents or wetting agents for dyes and fillers, such as, for example, alkyl enol lets, diluents, are the same as the component). Polymer film-type film-forming agents are well known in the pigment art and contain rnonorders that impart elasticity to the polymer. The polysiloxanes can be mentioned. They can be used for example in amounts of 0. 5 to 10% by weight, preferably, less than 5% by weight. The crosslinking agents, which are preferably contained in the composition of the present invention, are monomers with two or more double bonds well known in the art, such as for example ethylene glycol dimethacrylate (EGDM), tetraethylene glycol dimethacrylate (TEGDM), trirneacrylate of trirnetiiolpropane, etc. The amount of crosslinking agent is that usual in the art, generally between 0.05 and 4% by weight, preferably between 0.1 and 2% by weight. The polyblende composition for use in the formation of the finished article is a fluid, stable, redispersible and hardenable dispersion formed of at least one polimerizable liquid monomer, a finely subdivided mineral filler, a silanizing agent for the mineral filler, and a catalyst of hydrolysis of the chosen silanizing agent by example of the ammonium salts of organic acids. The polyenergizable monomers are preferably alkyl esters of acrylic or methacrylic acid, wherein the alkyl group contains from 1 to 6 carbon atoms. Preferred example is methyl methacrylate alone or in admixture with other acrylic, vinyl or styrene monomers, up to 50% by weight. As cormnorneros there may be mentioned ethyl methacrylate, propyl methacrylate, styrene, etc. These polyzable monomers are the same also as component a) of the colored composition. Mineral fillers are inorganic substances having hydrophilic surfaces characterized by the presence of polar groups, preferably hydroxyl groups.

Examples are amorphous or crystalline silica, alumina, ratified trihi alumina, mineral silicates, oxides. It is preferred that the fillers have a granular or spheroidal shape, however, the use of needle-shaped particles is not excluded. The aforementioned fillers are stably dispersed in the monomer polymerizable by silanization of the surface. Examples of silanes used for silanization are methyl triethoxysilane, gamma-inetacyloxypropyl trirnetoxysilane, vinyl triethoxysilane, etc. The fluid polymerizable compositions summarized herein are described in detail in EP 321193, incorporated herein by reference. As examples of compositions p > Fluid olirnerizables using polymers dispersants are, for example, those of UK patent 1493393, incorporated in the present reference. Polymerizable fluid compositions generally have low viscocities, in the order of 100-1,000 centipoisee, preferably 400-800 centipoise, although they can be used up to higher viscosities, generally of 2,000-5,000 centipoise. The colored compositions of the invention when applied to the surface of the mold give a layer that remains attached to the surface of the mold during the successive filling with the fluidizable polyenergizable composition, becoming an integral part of the molded article during the hardening of the polimerizable fluid composition. The method for producing molded materials with color contrast therefore comprises the application of the colored composition of the invention, which contains the desired contrast color on the surface of the desired mold, the realization of the coating and subsequent introduction of the composition polimerizable fluid to obtain the molded article. To obtain the coating of the color composition, before the application to the surface of the mold, a radical type polymerization initiator, as defined above, is added, of the same type that is used for the polymerization of the polimerizable fluid dispersion. to obtain the finished article. Initiator amounts are comprised L7 generally between 0.01 and?% of the total composition. A polymerization accelerator can also be used as an activator, as already described before. Therefore, during the polymerization, a molded finished article having colored the chosen surface patches is obtained. The polymerization of the polishable composition is carried out with initiators as mentioned above, of radical type, for example peroxides, with decomposition temperature close to that of the mold on which the colored composition is applied. The peroxides can also be used in a mixture of each other, using their different times of sernitransforrnation (decomposition) to obtain a continuous polymerization at different temperature scales. The temperature is generally between R0 ° C and 100 ° C. Examples of peroxides are but dicarbonate of d (4 ~ t-but? Lc? Clohex? Lo), benzoyl peroxide, etc. For the preparation of the article, the mold is maintained at a high temperature during the coating process with the colored compositions and during the subsequent filling of the mold with the flowable polishable composition. After hardening, the finished article is removed from the hot mold. The application of the colored composition for the production of the successive article is carried out immediately. The colored compositions of the present invention have the advantage of hardening in a relatively short time, it is sufficient to leave the coating dry for approximately 5 minutes after have been subjected to spray, whereby the filling operation with the polymerizable fluid composition can be very fast. As already mentioned, the introduction of the polimerizable fluid composition does not cause any color modification or disappearance of the colored surface either at the higher velocity point, that is, at the point of introduction of the polimerizable fluid composition. The fillers and polimerisable monorneros of the colorful compositions of the present invention are preferably the same as the polyenergizable composition that forms the finished article. The following examples are given for illustrative purposes and not limiting the scope of the present invention.

F. TEMPLE 1 P ep ration Je. L COPOSPOSITION. { .plor nte «Je. copolymer «Ja.

MMfl / oama-trirnetoxi «allano dj = rne cp lo inropilo (the dispersion?) Was obtained by loop polymerization at T = 80 ° C with 98: 2 weight ratio, using co or regulator of octylbutyl mercaptan molecular weight (OBM), in quantities "D.2% by weight and as initiator" He polymerized the product "le Lauroyl" (LAUROX) in amounts of 1% by weight, and subsequently it was finely ground. Mw was 100,000.

Poli si loxane (film-forming agent). In a 500 cc flask were added with stirring, 100 g of gamma-p-methoxysilane «Je inetacp loxipropil (if La or A L74 of Union Carbide), 100 g of CH30H, 40 g of distilled water, L g of isopropanol catalyst. It is reacted for 24 hours and the dense layer of polysiloxane is separated in a separating funnel.

Conolfmßro MMA / ethacrylic acid AMA) (polimepco dispersant). It was prepared by polymerization in aqueous suspension with a weight ratio of 98: 2. The "weight average molecular weight was 200,000.

Preparation of rnetacr11.ico syrup. In a 2 1 glass reactor, the following components were mixed under stirring for 5 hours until the (co) polymers were dissolved. % in weigh - MMA inhibited with 200 pprn of TOPANOLR A 90 (2, 4-dirnetyl-6-t.-but.ilphenol) -Copolymer MMA / methyl acrylate 5.32 with ALTUGLASR 9E intrinsic viscosity 65 rnl / g -Copoliriner MMA / AMA 98: 2 by weight (prepared before) 1.36 MMA copolymer / silane al74 98: 2 by weight 1.36 (prepared before) - EGDM (ethylene glycol dirneacrylate) .1.36 -Terpinolene 0.6 Preparation of the coloring paste In a container of 2 1 with a TURAXR type dispenser, the following coloring paste is prepared consisting of the following components with stirring for 10 minutes. % by weight -3AG0TEXR F 232 of the company 3AEGER CHEMIE 33.7 (hydroxylated acrylic resin at 60% by weight in xylene / solvesso / butyl acetate, in proportion 2/1/1) Nonyl phenol-ethoxylate 1.28 -White of Ti02 (from REPI) 7.0 -Red «Je oxide de fierro (from Bayer 13011) 10.5 -Right yellow 3R (from Bayer) 46.4 -Black P Vulcano (from Cabot) 1.1 The acrylic resin of this example is an acrylic resin containing OH groups, the weight percent OH in the solid resin is 3.6. The mixture obtained is passed twice over a three-cylinder refiner to improve the dispersion of the pigment.

Preparation of the dye dispersion - phase I In a 5 1 vessel with ceramic balls the following additives were mixed in parts by weight for 100 parts by weight of composition. parts in p.

-Rethacrylic syrup (prepared before) 47.96 -Polysiloxane (prepared before) 1.85 -Pasta coloring (prepared before) 4.76 - Acrylic resin 3AG0TEX F232 of JAEGER CHEMIE 0.98 - Nonyl phenol ethoxylate 0.14 -Silice finely subdivided 37.93 (SICR0NR B 800 of Sibelco) The mixture is stirred for 16 hours and then (phase II) is added with: parts in p.

? "? - Hydroxyethyl methacrylate (HEIA) 0.9T -Tirne-ethylolpropane trirene-acrylate (TMPTM) 0.2 -MMA (contains 200 ppm «e T0PAN0LR) 5.10 -Zinc stearate 0.1 After 2 hours of mixing the paint is used to form the color contrast.

Test application 16 g of the previously obtained paint are diluted with 4 g of a mixture of non-polyacrylic solvents (butyl acetate, butyl cellosolva, Solvesso 100) and added with 0.08 g of PERKAD0XR 16 (bis eroxydicarbonate). -4-tert-butyicyclohexyl). It is stirred until the PERKAD0XR is dissolved and then the paint is applied by airbrush spray with 0.7 nrn nozzle in one part (male) the nickel mold «Jo, maintained at 80 ° C by water circulation. The spray pressure was 2.5 atr. It was dried for 5 minutes. The mold is then closed and filled with the acrylic dispersion obtained in accordance with Example 2. The patent EP 321193, to which 0.6% by weight of PERKAD0XR 16 and 0.15% stearic acid have been added. The male and female mold temperatures are, respectively, 80 ° C and 70 ° C, by circulating water. Then the temperature is increased after 10 rnin gradually to 90 ° C for both male and female. ?3 It is maintained for 20 minutes at this temperature, then the male is cooled by circulating cold water and the mold is opened. The molded article consists of a bowl on parallelepiped conformation that has a size of 240 x 240 x 180 inrn and thickness «Je 10 inm. It presents perfectly reproduced and incorporated the part of the paint of contrast applied by sprinkling previously on the metal mold, without traces of disappearance on the surface. The color is perfectly homogeneous on the surface part of the molded article.

COMPARATIVE EXAMPLE 1A (To be compared with Example 1) Example 1 was repeated using a corresponding amount of long oil type SC 63 resin from Benasedo Company (dry, white spirit) instead of the acrylic resin of Example 1. The application test on mold indicated on the colored surface of contrast some points where the [unction was not present. These zones are close to the entry point of the flowable fluid composition. With respect to the finished article of Example 1, this article can not be used co nercialrnen t e.

COMPARATIVE EXAMPLE IB (to be compared with example 1) Example 1 was repeated using, instead of the acrylic resin of example 1, a corresponding amount of epoxy resin (epoxy ester resin) EPOBEN® L from Benasedo. The application test has shown that it is not possible to obtain a color contrast since the resin disappears when the fluid, fluid composition is introduced; the part of the surface that has not disappeared shows dehomogeneity.

EXAMPLE 2 Example 1 was repeated but using acetic acid ACTILANER 310 from Akcros Chemicals in the same amount in parts by weight as indicated in phase I of example 1 in place of the resin at 3AG0TEX F232. Acrylic resin ACTILANE 310 is an acrylic resin containing epoxy groups modified with fatty acids. By operating under the same conditions as in example 1, a bowl of optimum aesthetic appearance was obtained. The results are similar to those of example 1. '.j? EJErtPLQ 3 Example 1 was repeated but using acrylic resin ACTTLANFR 320TM75 from Okcros Chemicals in the same amount as parts by weight as indicated in the T phase of example 1. ACTILANE acrylic resin "320TM25 is an acrylic resin containing epoxy groups. Operating under the same conditions as in Example 1, a bowl of optimum esthetic appearance was obtained.The results are similar to those of Example L.

EXAMPLE 4 Example 1 was repeated but using ACTILANER 320TP20 acrylic resin from Akcros Chemicals in the same amount in parts by weight as indicated in phase I of example 1. ACTTLANER 320TP20 acrylic resin is an acrylic resin that contains epoxy groups i. Operating under the same conditions as in Example 1, a bowl was obtained for the optimum aesthetic appearance. The results are similar to those of example 1.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - The method of molding articles having areas of color contrast on the surface, comprising covering the surface or part on the surface of the mold with a colored composition polimeparated before filling the mold with a fluid composition polimepazable, wherein the colored composition is a fluid, stable, and redispersible dispersion comprising, a) liquid poly merizable monomers, optionally in admixture with a non-poly-volatile volatile organic solvent, as a solvent; b) from 0.1 to 10% by weight of a dye composition as an inorganic pigment or from 0.0001 to 1% by weight of a pigment or organic dye; c) from 1 to 30% by weight of an acrylic resin soluble in solvent a) and containing reactive functional groups capable of crosslinking, component a) being at least 20% by weight of the total composition.

2. The method of molding articles having "contrast color" areas according to claim 1, further characterized in that it optionally comprises one or more of the following components: d) from 5 to 70% by weight on the total composition, of a finely subdivided filler, having an average diameter of 0.5 to 10 microns, preferably 2 to 6 microns; e) a regulator of polirneric viscocity soluble in the solvent with concentrations of 0.1 to 20% by weight, f) other polyrneic or non-polymeric additives, in amounts of less than 5% by weight on the total of the components , acting as «Filler Jispersants d), diluents, latent solvents, polymerization inhibitors, molecular weight regulators-, polymerization activators, surfactants, film-forming agents; cross-linking agents.,

3. The process of molding articles having contrasting areas of color, according to claim 2, further characterized in that a) is 30 to 60% by weight; b) is from 2 to 6% by weight in the case of inorganic pigments and from 0.01 to 0.5% by weight in the case of organic pigments; c) is from 1.5 to 10% by weight; d) is from 20 to 50% by weight; e) is from 1 to 10% by weight.

4. The method of molding articles that have areas of color contrast, according to claims 2 and 3, further characterized in that the r-ellen has an average diameter of 0.5 to 10 microns.

5. The method of molding articles that have areas of color contrast, according to claims 1 to 4 further characterized in that the acrylic resins contain pendant functional groups of the main chain, expressed as% by weight of functional group comprised between 3 and 6.

6. - The molding process "Je articles having areas" Contrast color according to claim 5, further characterized in that the functional groups are hydroxyl, carboxyl, anidic, epoxyl g.

7. The method of molding articles that have areas of color contrast according to claims 1 to 6, further characterized in that the fluidizable fluid composition has a viscosity of 400 to 800.

8. The procedure molding of articles having color contrast zones according to claims 1 to 7, further characterized in that the acrylic resin used is a terrazzo resin.

9. The colorful compositions according to claims 1 to 8.