(19) Europäisches Patentamt European Patent Office Office européen des brevets *EP00070702B1* (11) EP 0 707 02 B1 (12) EUROPEAN PATENT SPECIFICATION (4) Date of publication and mention of the grant of the patent: 16.08.01 Bulletin 01/33 (1) Int Cl. 7 : C09D /02, C09D 7/00, C09D 7/12 (21) Application number: 91160.7 (22) Date of filing: 11..199 (4) Waterborne clay-containing emulsion paints with improved application performance Wässrige Ton-enthaltende Emulsionsfarbe mit verbesserten Beschichtungseigenschaften Peinture aqueuse en émulsion contenant d argile avec une utilisation amélioré (84) Designated Contracting States: BE CH DE FR GB IT LI NL PT SE () Priority: 11..1994 US 324189 (43) Date of publication of application: 17.04.1996 Bulletin 1996/16 (73) Proprietor: AQUALON COMPANY Wilmington, Delaware 19894-0001 (US) (72) Inventor: Kroon, Gijsbert NL-3364 AN Sliedrecht (NL) (74) Representative: Hansen, Bernd, Dr. Dipl.-Chem. et al Hoffmann Eitle, Patent- und Rechtsanwälte, Arabellastrasse 4 8192 München (DE) (6) References cited: EP-A- 0 390 2 EP-A- 0 42 997 EP-A- 0 441 037 EP-A- 0 66 911 EP-A- 0 61 093 US-A- 4 298 11 US-A- 4 749 731 US-A- 219 924 EP 0 707 02 B1 Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). Printed by Jouve, 7001 PARIS (FR)
EP 0 707 02 B1 Description 1 2 3 4 [0001] The invention relates to the use of hydroxyethylcellulose-based thickeners in hydrophilic clay-containing emulsion paints. [0002] Similar thickeners have been used in paper coating compositions (EP 0 61 093 A1 which is a prior art document under Art. 4(3,4) EPC), in coating compositions for miscellaneous substrates (US 4,298,11) as well as in waterproof roof coatings (US 4,749,731). [0003] Prior to the present invention, latex paints containing clay as a pigment extender or containing calcium carbonate with clay impurities as the pigment extender, made it difficult to work with hydroxyethylcellulose (HEC) or hydrophobically modified hydroxyethylcellulose (HMHEC) from an application point of view. These paints often showed a gel structure and drew threads when applied with a roller. [0004] In waterborne emulsion paints, cellulose derivatives like hydroxyethylcellulose (HEC), methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose(mhpc), ethylhydroxyethylcellulose (EHEC) and carboxymethylcellulose (CMC) are used as rheology modifiers. These cellulose ethers thicken latex paints, providing the paints with stability, water retention and a pseudoplastic flow behavior. The cellulose ethers are used in an amount of 0.1% w/w up to 4.0% w/w on total paint, depending on the binder content of the paint. Hydroxyethylcellulose (HEC) and hydrophobically modified hydroxyethylcellulose (HMHEC) can be considered as the more popular types of cellulose ethers for use; clays are used as pigment extenders in emulsion paints in the United States while calcium carbonate is the most widely used type in European flat emulsion paint formulations, although in certain European areas, silicates and dolomites are used as well. [000] In paint systems containing hydrophilic clays, strong adsorption of HEC and HMHEC onto these clays occurs. This can affect the performance of the polymers in these paints dramatically. Indistemper paints, which are often based on calcium carbonate containing clay impurities like montmorrillonite or bentonite, this results in a gelly paint structure. This gelly structure does not allow a good flow and application of the paint. For this reason, methylcellulose derivatives and carboxymethylcellulose are the preferred thickeners in these paints, since these cellulose ethers do not strongly adsorb, so do not show the undesired gelation. Modification of HEC or HMHEC is needed in order to make them suitable for use as thickeners for clay containing flat emulsion paints. The above-described performance deficiencies of HEC and HMHEC as a result of their strong adsorption onto clay are also valid for ethylhydroxyethylcellulose (EHEC) and hydrophobically modified ethylhydroxyethylcellulose (HMEHEC). It is in meeting this need that the present invention provides an advance in the state of the art of the use of HEC, HMHEC, EHEC and HMEHEC as thickeners in emulsion paints containing hydrophilic clays or calcium carbonate extenders containing clay impurities. [0006] This invention relates to a water-borne emulsion paint composition comprising a clay containing pigment system, a latex binder, a polysaccharide thickener selected from the group consisting of hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose, ethylhydroxyethylcellulose, hydrophobically modified ethylhydroxyethylcellulose and mixtures thereof, and 0.00% to 2%, based upon the weight of the pigment, of a blocking agent, which is selected from the group consisting of poly(ethylene oxide), poly(ethylene glycol), poly(propylene oxide), poly(propylene glycol), poly(vinyl alcohol), poly(acrylic acid), salt of poly(acrylic acid), salts of poly(methacrylic acid), acrylic acid, methacrylic acid, and non-ionic surfactants of the type alkylarylethoxylate and alkylethoxylate, and which serves to prevent more than % of the polysaccharide thickener from being adsorbed onto the clay pigment surface whereby the paint composition exhibits improved appearance and application performance. Paper coating compositions are excluded from the scope of the present invention. [0007] It has been discovered that the appearance and application properties of clay-containing emulsion paints, thickened with cellulose derivatives as claimed such as HEC, HMHEC, EHEC or HMEHEC, can be enormously improved by combining these cellulose derivatives with so-called pre-blocking agents. These blocking agents limit or even prevent the adsorption of the thickener onto clays and clay-containing extenders. [0008] In accordance with this invention, a cellulose derivative thickening agent for clay-containing latex paints is selected from the group consisting of one or more of the following: 0 a. Hydroxyethylcellulose (HEC) with a molecular weight of from 0,000 to 1,00,000 and a hydroxyethyl molar substitution (HE-MS) of 1. to 4.0; b. Hydrophobically-modified hydroxyethylcellulose (HMHEC) with a molecular weight of from 0,000 to 1,000,000 and a HE-MS of 1. to 4.0 with a hydrophobic modification chain of C 4 to C 22 alkyl or C 8 to C alkylaryl in an amount of 0.01 to 2.0 percent by weight based on total weight of the hydrophobically-modified hydroxyethylcellulose; c. Ethylhydroxyethylcellulose (EHEC) with a molecular weight of from 0,000 to 1,00,000 and a HE-MS of 0. to 3.0 and a degree of ethyl substitution of 0.3 to 1.2; and d. Hydrophobically-modified ethylhydroxyethylcellulose (HMEHEC) with a molecular weight of from 0,000 to 1,000,000 and a HE-MS of 0. to 3. and a degree of ethyoxyl substitution of 0.3 to 1.2 with a hydrophobic mod- 2
EP 0 707 02 B1 ification chain of C 4 to C 22 alkyl or C 8 to C alkylaryl in an amount of 0.01 to 2.0 percent by weight based on total weight of the hydrophobically-modified ethylhydroxyethylcellulose. [0009] In accordance with this invention, the blocking agent is selected from the group consisting of one or more of the following: 1 2 a. Poly(ethylene oxide), poly(ethylene glycol), poly(propylene oxide) and poly(propylene glycol) with a molecular weight of from 0 to 1,000,000; b. Poly(vinyl alcohol) with a molecular weight of from 1,000 to 00,000 and a degree of hydrolysis of from to 90 percent; c. Salts of poly(acrylic acid) and poly(methacrylic acid) and their acid equivalents with a molecular weight of from 1,000 to 1,000,000; d. Nonionic surfactants of the type alkylarylethoxylate and alkylethoxylate with 4 to 0 oxyethylene (OE) units and a hydrophobic chain of C 8 to C alkylaryl or C 4 to C 24 alkyl. [00] The upper limit of the blocking agent in the present invention is 2.0% by weight, based on the total weight of the composition, with the preferred upper limit being 1.0% by weight. The lower limit of the blocking agent is 0.00% by weight, based on the total weight of the composition, with 0.1% by weight being the preferred lower limit. When this combination of thickener and blocking agent is used, the adsorption of the cellulose derivative onto clay or a claycontaminated extender like Bianco Meudon Tipo A does not exceed 3 mg/g. Latex paints with the above-described thickener combinations do not have a gelly structure and can be applied to a substrate by roller without drawing undesired threads. Extender Pigments [0011] The types of extenders that can be used in this invention are basically two groups of products: a) clay-type extenders and b) calcium carbonate extenders contaminated with hydrophilic clay-types. a. Clay-type Extenders [0012] Examples of these clays are generally Kaolinites, chemically composed of SiO 2 (-0 wt. %), Al 2 O 3 (-0 wt. %), small amounts of alkalis (K 2 O, Na 2 O) and iron oxide (Fe 2 O 3 ). Other clays that may be used as extenders in this invention are calcined clays with low loss on ignition. Examples of such clays for use in the instant invention are: 3 4 0 Clays Manufacturer SiO 2 (wt. %) Al 2 O 3 (wt. %) Loss on Ignition (wt. %) Kaolin FP7 Dorfner 48 36 12 Spesswhite ECC* 47 38 13 DB Plate 00 Euroclay - - - China Clay Grade B ECC 48 37 12.1 China Clay Grade C ECC 48 37 11.9 China Clay Grade D ECC 47. 37 12.1 China Clay Grade E ECC 48. 36. 11.0 Polestar 0 ECC 4.7 41.7 - Amazon 88 CADAM 4.1 37.8 13.9 *ECC sands for English China Clay b. Contaminated Carbonates [0013] Calcium carbonates are available in relatively purified form like the Durcal-products, Omyacarb-series and Omyalite-series of OMYA. However, many producers of cheaper and less purified products also exist. These cheaper calcium carbonates can be contaminated with many types of clays. However, the contamination with very hydrophilic clays causes the problems with HEC in heavily pigmented paint systems. Examples of these clay contaminants are attapulgite clay, hectorite clay, montmorrillonites, and bentonite clay. One example of such a problem-causing calcium 3
EP 0 707 02 B1 carbonate is the Bianco Meudon Tipo A used in the Italian paint market. Latex Types [0014] The problem of strong structure build-up in the paint is mainly known in paint systems, where poly(vinyl acetate) VeoVA co-polymer binders are used as latex. [001] Examples of these binders which are partially stabilized with hydroxyethyl cellulose as protective colloid are: 1 Binder Ravemul PC2 Vinavil 03V Uramul VV0 Mowilith DM21 Acrilem VVAC Marketed By Enichem, Italy Montedipe, Italy DSM Resins, The Netherlands Hoechst, Germany ICAP, Italy 2 [0016] Latex paints of this invention provide excellent capacity to hide the substrate that it is to cover. The capacity to hide the substrate is controlled mainly by the pigment volume concentration (PVC) and the coating thickness. The PVC has certain limits dictated by economics and the capacity of the pigment binding vehicle. The latex paint of this invention, for example, when used in flat paints may have a PVC of from 0 to 0%. The coating thickness is determined in part by the viscosity developed in the composition. Other factors exist such as other coating properties and application characteristics, such as brush drag, flow, and leveling of the coating composition for developing the type of viscosity for a particular type of paint. [0017] The practice of the invention is further illustrated by the following examples: [0018] Adsorption experiments in the Examples were performed as follows: A 0 wt. % solids suspension of clay in water was prepared. 0. wt. % of thickener was added and dissolved in the pigment slurry or suspension and then stored for 24 hours at 2 C. The system was then centrifuged at,000 rpm for three hours. The amount of hydroxyethylcellulose or ethylhydroxyethylcellulose of the supernatant was determined via the Sealed Tube Zeisel method for measuring ethoxyl and hydroxyethyoxyl content. These pigment slurries were also made in the presence of blocking agents in order to determine the effect of the blocking agent on the adsorption of the cellulosics onto clay and carbonate extenders. 3 Example 1 [0019] Table 1 The Adsorption of HEC and HMHEC Onto a Clay-Containing Extender As a Function of Different Types of Pre-Blocking Agents Example Blocking Agent Type % w/w Adsorption onto Bianco Meudon Tipo A of HEC a (mg/g) 1A None - 4. 4 1B Calgon N b 0.2 3.7 1C Tamol 731 c 0.2 3. 1D PEG 0 d 0.2 4.8 0 1E Tamol 963 e 0.2 3.8 1F Lutrol E 00 f 0.2 1.9 a - HEC : Natrosol MBR, marketed by Aqualon Company. b - Sodium hexametaphosphate wetting agent, marketed by Benckiser Knapsack. c - Copolymer of di-isobutylene maleic anhydride dispersant, marketed by Rohm & Haas. d - Poly(ethylene glycol) with molecular weight of 0. e - Sodium salt of poly(acrylic acid), dispersant, marketed by Rohm & Haas. f - Poly(ethylene oxide), marketed by BASF. 4
EP 0 707 02 B1 Table 1 (continued) The Adsorption of HEC and HMHEC Onto a Clay-Containing Extender As a Function of Different Types of Pre-Blocking Agents Example Blocking Agent Type % w/w Adsorption onto Bianco Meudon Tipo A of HEC a (mg/g) 1G Lopon 88 g 0.2 4.0 1H Pigment Verteiler A h 0.2 0.0 1I Airvol 803 i 0.2 0.0 1J Sodium Dodecyl Sulfate 0.2 11.2 1K Antarox CO4 j 0.2 4.0 1L Antarox CO970 k 0.2 0.6 1 a - HEC : Natrosol MBR, marketed by Aqualon Company. g - Dispersant, sodium salt of poly(acrylic acid), marketed by Benckiser Knapsack. h - Ammonium salt of poly(acrylic acid) dispersant, marketed by BASF. i - Poly(vinyl alcohol), marketed by Air Products. j - Nonylphenol ethoxylate (4 EOs), marketed by GAF. k - Nonylphenol ethoxylate (0 EOs), marketed by GAF. 2 3 Table 2 Example Blocking Agent Type % w/w Adsorption onto Bianco Meudon Tipo A of HMHEC a (mg/g) 1M None - 6.7 1N Calgon N 0.2 9.4 1O Tamol 731 0.2 12. 1P PEG 0 0.2 4.0 1Q Tamol 963 0.2 4.0 1R Lutrol E 00 0.2 0.0 1S Lopon 88 0.2 4.1 1T Pigment Verteiler A 0.2 0.8 1U Airvol 803 0.2 0.0 1V Sodium Dodecyl Sulfate 0.2 11.7 1W Antarox CO4 0.2.8 1X Antarox CO970 0.2 2. a - HMHEC: Natrosol Plus 3, marketed by Aqualon Company 4 0 [00] The above-given examples 1A through 1X demonstrate that only specific products can be used as a blocking agent to limit the adsorption of HMHEC onto Bianco meudon Tipo A. Lutrol E 00 (as marketed by BASF), a poly (ethylene glycol) with a molecular weight of approximately 00, pigment Verteiler A (as marketed by BASF), an ammonium salt of poly(acrylic acid), Airvol 803 as marketed by Air Products), a poly(vinyl alcohol) (molecular weight about,000; 88-89% hydrolysis) and Antarox CO970 (as marketed by GAF), a nonylphenol ethoxylate (0 EO units) are able to reduce the adsorption of HMHEC onto the extender. These blocking agents are able to form hydrogen bonds with clay or the clay present as contaminant in calcium carbonate extenders. Higher molecular weight poly(ethylene glycol) (Lutrol E 00) is more efficient than lower molecular weight material (PEG 0). Nonylphenol ethoyxylate surfactants become more efficient as a blocking agent when increasing the number of EO-units in the product (see Antarox CO970 versus Antarox CO4). The ammonium salt of poly (acrylic acid) is more efficient as a blocking agent than the sodium salt (see Pigment Verteiler A versus Lopon 88 and Tamol 963).
EP 0 707 02 B1 Example 2 [0021] The differences in adsorption values are reflected in differences in paint properties of the paints based on the Bianco Meudon Tipo A and the various combinations of HMHEC and blocking agents. The following examples (2A- 2T) exhibit the practice of the invention in a flat emulsion paint having a pigment volume concentration (PVC) of 94%. The paint samples were prepared under Cowles conditions with a high speed dissolver. The paint formulation is given in Table 3. Table 3 Paint Formulation Containing Bianco Meudon as Pigment Extender; PVC : 94%; Solids: 8 % w/w Parts by Weight Water 287.1 1 Preservative CA24 1.0 Pigment Verteiler A 1.0 Calgon N 1. Agitan 280 1.0 Ammonia 1.0 Bianco Meudon 66.0 Texanol 2.0 2 Ravemul PC2 33.0 Thickener by demand Blocking Agent 3.0 Water 97. Total 93.1 [0022] The paint was thickened with Natrosol Plus grade 3 HMHEC and Natrosol MBR HEC combined with different blocking agents. The test results are shown in Table 4 and Table. 3 Table 4 Combination of (Natrosol MBR) HEC With Different Pre-blocking Agents in a Flat Emulsion Paint (PVC 94) Based on Ravemul PC2 With Bianco Meudon Tipo A As An Extender Example HEC (Wt. %) Blocking Agent Type SV 1 SYV 2 Appearance 3 Roller Application 4 2A 0.36 None 9 800 -- -- 4 0 2B 0.28 Pigment Verteiler A 0 + + 2C 0. Calgon N 116 1600 -- -- 2D 0.24 Sodium Dodecyl Sulfate 1 900 -- -- 2E 0.31 Tamol 731 7 700 -- -- 2F 0.33 Antarox CO970 112 + + 1. Stormer viscosity. 2. Stormer Yield Value; maximum load in grams before spindle starts to rotate. 3. Appearance of the paint with respect to gelly structure; ranked from strong gelation (--) to non-gelly (+). 4. Applicability by roller in terms of ease of spreading and drawing of threads; ranked from very poor (--) to good (+). 6
EP 0 707 02 B1 Table 4 (continued) Combination of (Natrosol MBR) HEC With Different Pre-blocking Agents in a Flat Emulsion Paint (PVC 94) Based on Ravemul PC2 With Bianco Meudon Tipo A As An Extender Example HEC (Wt. %) Blocking Agent Type 2G 0.34 Antarox Co4 SV 1 SYV 2 Appearance 3 Roller Application 4 6 +- + 2H 0.26 Airvol 803 1 + + 2I 0. Lutrol E 00 114 0 + + 2J 0.37 PEG 0 0 00 +- + 1 1. Stormer viscosity. 2. Stormer Yield Value; maximum load in grams before spindle starts to rotate. 3. Appearance of the paint with respect to gelly structure; ranked from strong gelation (--) to non-gelly (+). 4. Applicability by roller in terms of ease of spreading and drawing of threads; ranked from very poor (--) to good (+). 2 Table Combination of HMHEC (Natrosol Plus 3) With Different blocking Agents in a Flat Emulsion Paint (PVC 94) Based on Ravemul PC2 With Bianco Meudon Tipo A As An Extender Example HEC (Wt. %) Blocking Agent Type SV 1 SYV 2 Appearance 3 Roller Application 4 2K 0.37 None 9 60 - - 2L 0. Pigment Verteiler A 8 0 + + 2M 0.26 Calgon N 114 1800 -- -- 2N 0.26 Sodium Dodecyl Sulfate 112 600 - - 3 2O 0.36 Tamol 731 7 0 - -- 2P 0.27 Antarox CO970 8 + + 2Q 0.28 Antarox CO4 6 +- +- 2R 0.37 Airvol 803 9 0 + + 2S 0.3 Lutrol E 00 114 0 + + 4 0 2T 0.36 PEG 0 0 0 +- + 1. Stormer viscosity. 2. Stormer Yield Value; maximum load in grams before spindle starts to rotate. 3. Appearance of the paint with respect to gelly structure; ranked from strong gelation (--) to non-gelly (+). 4. Applicability by roller in terms of ease of spreading and drawing of threads; ranked from very poor (--) to good (+). Example 3 [0023] Another experiment was performed to demonstrate that the effect of combining the cellulose ether with a blocking agent is also valid for EHEC and HMEHEC. EHEC was Bermocol E 31 FQ polymer and the HMEHEC was Bermocol EHM0 polymer. The influence of using a combination of HMEHEC and a blocking agent on the paint properties is shown in the flat emulsion paint (PVC94) based on Ravemul PC2 material. Examples 3A-3D illustrate these benefits (see Table 6). 7
EP 0 707 02 B1 Table 6 Combination of (HM)EHEC with Lutrol 00 In a Flat Emulsion Paint (PVC 94) Based On Ravemul PC2 With Bianco Meudon Tipo A as an Extender Example EHEC (wt %) HME HEC (wt. %) Lutrol E 00 (wt. %) SV 1 (KU) SYV 2 (g) Appearance 3 Roller Application 4 3A 0.3 - - 6 700 -- -- 3B 0.31-0.2 9 0 + + 3C - 0.34-1 600 - - 3D - 0.29 0.2 111 + + 1 1. Stormer viscosity. 2. Stormer Yield Value; maximum load in grams before spindle rotates. 3. Appearance of the paint; gelly (--) to non-gelly (+). 4. Applicability by roller; good (+) to very poor (--). 2 3 Example 4 [0024] In paint systems with strong hydrophilic clays like Spesswhite, the amount of blocking agent needs to be increased in order to limit the adsorption of HEC, EHEC, HMHEC and HMEHEC onto these types of clay. This is illustrated by the results of adsorption experiments shown in Examples 4A and 4B (see Table 7) using Lutrol E 00 as a blocking agent. Table 7 Influence of the Addition of a Blocking Agent on the Adsorption of HEC (Natrosol MBR) Onto Spesswhite, a Hydrophilic Clay ex ECC. Example Wt % Blocking Agent Adsorption of HEC Onto Spesswhite (mg/g) 4A - -.0 4B 0.2 Lutrol E 00 9.8 4C 0. Lutrol E. 00 3.6 4D 1.0 Lutrol E 00 0.3 [002] The combinations of HEC, EHEC, HMHEC or HMEHEC with blocking agents can be used in the form of a powder blend, fluidized polymer system or as a solution of subject materials. Claims 4 0 1. A water-borne emulsion paint composition excluding paper coating compositions comprising a clay containing pigment system, a latex binder, a polysaccharide thickener selected from the group consisting of hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose, ethylhydroxyethylcellulose, hydrophobically modified ethylhydroxyethylcellulose and mixtures thereof, and 0.00% to 2%, based upon the weight of the pigment, of a blocking agent, which is selected from the group consisting of poly(ethylene oxide), poly(ethylene glycol), poly (propylene oxide), poly(propylene glycol), poly(vinyl alcohol), poly(acrylic acid), salt of poly(acrylic acid), salts of poly(methacrylic acid), acrylic acid, methacrylic acid, and non-ionic surfactants of the type alkylarylethoxylate and alkylethoxylate, and which serves to prevent more than % of the polysaccharide thickener from being adsorbed onto the clay pigment surface whereby the paint composition exhibits improved appearance and application performance. 2. The composition of claim 1 wherein the polysaccharide thickener is hydroxyethylcellulose with a molecular weight of from 0,000 to 1,00,000. 8
EP 0 707 02 B1 3. The composition of claim 2 wherein the hydroxyethylcellulose has a molar substitution of 1. to 4.0. 4. The composition of claim 1 wherein the polysaccharide thickener is hydrophobically modified hydroxyethylcellulose with a molecular weight of from 0,000 to 1,000,000.. The composition of claim 4 wherein the hydrophobically modified hydroxyethyl cellulose has a hydroxyethyl molar substitution of 1. to 4.0. 6. The composition of claim wherein the hydrophobically modified hydroxyethyl cellulose has a hydrophobic modification of C 4 to C 22 alkyl or C 8 to C alkylaryl in an amount of 0.01 to 2.0% by weight based on total weight of the hydrophobically modified hydroxyethylcellulose. 1 2 7. The composition of claim 1 wherein the polysaccharide thickener is ethylhydroxyethylcellulose with a molecular weight of from 0,000 to 1,00,000. 8. The composition of claim 7 wherein the ethylhydroxyethyl-cellulose has a hydroxyethyl molar substitution of 0. to 3.0. 9. The composition of claim 8 wherein the ethylhydroxyethyl cellulose has a degree of ethyl substitution of 0.3 to 1.2.. The composition of claim 1 wherein the polysaccharide thickener is hydrophobically modified ethylhydroxyethylcellulose with a molecular weight of from 0,000 to 1,000,000. 11. The composition of claim wherein the hydrophobically-modified ethylhydroxyethylcellulose has a hydroxyethyl molar substitution of 0. to 3.. 12. The composition of claim 11 wherein the hydrophobically-modified ethylhydroxyethylcellulose has a degree of ethyoxyl substitution of 0.3 to 1.2. 3 13. The composition of claim 12 wherein the hydrophobically-modified ethylhydroxyethylcellulose has a hydrophobic modification of C 4 to C 22 alkyl or C 8 to C alkylaryl in an amount of 0.01 to 2.0% by weight based on total weight of the hydrophobically-modified ethylhydroxyethylcellulose. 14. The composition of claim 1 wherein the blocking agent is selected from the group consisting of poly(ethylene oxide), poly(ethylene glycol), poly(propylene oxide), and poly(propylene glycol), whereby the blocking agent has a molecular weight of from 0 to 1,000,000. 4 0 1. The composition of claim 1 wherein the blocking agent is poly(vinyl alcohol) with a molecular weight of from 1,000 to 00,000. 16. The composition of claim 1 wherein the poly(vinyl alcohol) has a degree of hydrolysis of from to 90 percent. 17. The composition of claim 1 wherein the blocking agent is selected from the group consisting of salts of poly(acrylic acid), salts of poly (methacrylic acid), acrylic acid, and methacrylic acid. 18. The composition of claim 17 wherein the salts have a molecular weight of from 1,000 to 1,000,000. 19. The composition of claim 1 wherein the nonionic surfactants have 4 to 0 oxyethylene units and a hydrophobic chain of C 8 to C alkylaryl or C 4 to C alkyl.. The composition of claim 1 wherein the clay containing pigment system comprises extender pigments selected from the group consisting of clay-types and calcium carbonate-types contaminated with hydrophilic clay types. 21. The composition of claim wherein the clay type extenders are kaolinites or calcined clays with loss ignition. 22. The composition of claim wherein the contaminated calcium carbonate type extenders are selected from the group consisting of attapulgite clay, hectorite clay, montmorrillonites, and bentonite clay. 9
EP 0 707 02 B1 23. The composition of claim 22 wherein the contaminated calcium carbonate type extenders are Bianco Meudon Tipo A extender. 1 24. The composition of claim 1 wherein the paint composition has a pigment volume concentration of from 0 to 0. 2. Use of a clay containing pigment system, a latex binder, a polysaccharide thickener selected from the group consisting of hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose, ethylhydroxyethylcellulose, hydrophobically modified ethylhydroxyethylcellulose and mixtures thereof, and 0.00% to 2%, based upon the weight of the pigment, of a blocking agent, which is selected from the group consisting of poly(ethylene oxide), poly (ethylene glycol), poly(propylene oxide), poly(propylene glycol), poly(vinyl alcohol), poly(acrylic acid), salt of poly (acrylic acid), salts of poly(methacrylic acid), acrylic acid, methacrylic acid, and non-ionic surfactants of the type alkylarylethoxylate and alkylethoxylate, and which serves to prevent more than % of the polysaccharide thickener from being adsorbed onto the clay pigment surface, in the manufacture of a water-borne emulsion paint composition, excluding paper coating compositions. Patentansprüche 2 3 1. Emulsionsfarbenzusammensetzung auf Wasserbasis unter Ausschluss von Papierbeschichtungszusammensetzungen, die ein tonhaltiges Pigmentsystem, ein Latexbindemittel, ein Polysaccharid-Verdickungsmittel, das ausgewählt ist aus der Gruppe, bestehend aus Hydroxyethylcellulose, hydrophob modifizierter Hydroxyethylcellulose, Ethylhydroxyethylcellulose, hydrophob modifizierter Ethylhydroxyethylcellulose und Mischungen davon, sowie 0,00 bis 2 %, bezogen auf das Gewicht des Pigments, eines Blockierungsmittels umfasst, das ausgewählt ist aus der Gruppe, bestehend aus Poly(ethylenoxid), Poly(ethylenglykol), Poly(propylenoxid), Poly(propylenglykol), Poly(vinylalkohol), Poly(acrylsäure), Poly(acrylsäure)salzen, Poly(methacrylsäure)salzen, Acrylsäure, Methacrylsäure und nicht-ionischen Alkylarylethoxylat- und Alkylethoxylat-Tensiden, und das dazu dient, zu verhindern, dass mehr als % des Polysaccharid-Verdickungsmittels auf die Tonpigmentoberfläche adsorbiert werden, wodurch die Farbzusammensetzung verbessertes Aussehen und Applikationsverhalten zeigt. 2. Zusammensetzung gemäss Anspruch 1, wobei das Polysaccharid-Verdickungsmittel Hydroxyethylcellulose mit einem Molekulargewicht von 0.000 bis 1.00.000 ist. 3. Zusammensetzung gemäss Anspruch 2, wobei die Hydroxyethylcellulose eine molare Substitution von 1, bis 4,0 hat. 4. Zusammensetzung gemäss Anspruch 1, wobei das Polysaccharid-Verdickungsmittel hydrophob modifizierte Hydroxyethylcellulose mit einem Molekulargewicht von 0.000 bis 1.000.000 ist.. Zusammensetzung gemäss Anspruch 4, wobei die hydrophob modifizierte Hydroxyethylcellulose eine molare Hydroxyethyl-Substitution von 1, bis 4,0 hat. 4 0 6. Zusammensetzung gemäss Anspruch, wobei die hydrophob modifizierte Hydroxyethylcellulose eine hydrophobe Modifikation von C 4-22 -Alkyl oder C 8- -Alkylaryl in einer Menge von 0,01 bis 2,0 Gew.%, bezogen auf das Gesamtgewicht der hydrophob modifizierten Hydroxyethylcellulose besitzt. 7. Zusammensetzung gemäss Anspruch 1, wobei das Polysaccharid-Verdickungsmittel Ethylhydroxyethylcellulose mit einem Molekulargewicht von 0.000 bis 1.00.000 ist. 8. Zusammensetzung gemäss Anspruch 7, wobei die Ethylhydroxyethylcellulose eine molare Hydroxyethyl-Substitution von 0, bis 3,0 besitzt. 9. Zusammensetzung gemäss Anspruch 8, wobei die Ethylhydroxyethylcellulose einen Ethyl-Substitutionsgrad von 0,3 bis 1,2 besitzt.. Zusammensetzung gemäss Anspruch 1, wobei das Polysaccharid-Verdickungsmittel hydrophob modifizierte Ethylhydroxyethylcellulose mit einem Molekulargewicht von 0.000 bis 1.000.000 ist. 11. Zusammensetzung gemäss Anspruch, wobei die hydrophob modifizierte Ethylhydroxyethylcellulose eine mo-
lare Hydroxyethylsubstitution von 0, bis 3, besitzt. EP 0 707 02 B1 1 12. Zusammensetzung gemäss Anspruch 11, wobei die hydrophob modifizierte Ethylhydroxyethylcellulose einen Ethyoxyl-Substitutionsgrad von 0,3 bis 1,2 besitzt. 13. Zusammensetzung gemäss Anspruch 12, wobei die hydrophob modifizierte Ethylhydroxyethylcellulose eine hydrophobe Modifikation von C 4-22 -Alkyl oder C 8- -Alkylaryl in einer Menge von 0,01 bis 2,0 Gew.%, bezogen auf das Gesamtgewicht der hydrophob modifizierten Ethylhydroxyethylcellulose aufweist. 14. Zusammensetzung gemäss Anspruch 1, wobei das Blockierungsmittel ausgewählt ist aus der Gruppe, bestehend aus Poly(ethylenoxid), Poly(ethylenglykol), Poly(propylenoxid) und Poly(propylenglykol), wobei das Blockierungsmittel ein Molekulargewicht von 0 bis 1.000.000 besitzt. 1. Zusammensetzung gemäss Anspruch 1, wobei das Blockierungsmittel Poly(vinylalkohol) mit einem Molekulargewicht von 1.000 bis 00.000 ist. 16. Zusammensetzung gemäss Anspruch 1, wobei der Poly(vinylalkohol) einen Hydrolysegrad von bis 90 % besitzt. 17. Zusammensetzung gemäss Anspruch 1, wobei das Blockierungsmittel ausgewählt ist aus der Gruppe, bestehend aus Poly(acrylsäure)salzen, Poly(methacrylsäure)salzen, Acrylsäure und Methacrylsäure. 18. Zusammensetzung gemäss Anspruch 17, wobei die Salze ein Molekulargewicht von 1.000 bis 1.000.000 haben. 2 19. Zusammensetzung gemäss Anspruch 1, wobei die nicht-ionischen Tenside 4 bis 0 Oxyethylen-Einheiten und eine hydrophobe Kette von C 8- -Alkylaryl oder C 4- -Alkyl besitzen.. Zusammensetzung gemäss Anspruch 1, wobei das tonhaltige Pigmentsystem Extenderpigmente umfasst, die ausgewählt sind aus der Gruppe bestehend aus Tonen und Calciumcarbonaten, die mit hydrophilen Tonen kontaminiert sind. 21. Zusammensetzung gemäss Anspruch, wobei die Tonextender Kaolinite oder calcinierte Tone mit Glühverlust sind. 3 4 0 22. Zusammensetzung gemäss Anspruch, wobei die kontaminierten Calciumcarbonat-Extender ausgewählt sind aus der Gruppe bestehend aus Attapulgitton, Hectoritton, Montmorrilloniten und Bentonitton. 23. Zusammensetzung gemäss Anspruch 22, wobei die kontaminierten Calciumcarbonat-Extender Bianco Meudon Tipo A-Extender sind. 24. Zusammensetzung gemäss Anspruch 1, wobei die Farbenzusammensetzung eine Pigmentvolumenkonzentration von 0 bis 0 besitzt. 2. Verwendung eines tonhaltigen Pigmentsystems, eines Latex-Bindemittels, eines Polysaccharid-Verdickungsmittels, das ausgewählt ist aus der Gruppe, bestehend aus Hydroxyethylcellulose, hydrophob modifizierter Hydroxyethylcellulose, Ethylhydroxyethylcellulose, hydrophob modifizierter Ethylhydroxyethylcellulose und Mischungen davon, und 0,00 bis 2 %, bezogen auf das Gewicht des Pigments, eines Blockierungsmittels, das ausgewählt ist aus der Gruppe, bestehend aus Poly(ethylenoxid), Poly(ethylenglykol), Poly(propylenoxid), Poly(propylenglykol), Poly(vinylalkohol), Poly(acrylsäure), Poly(acrylsäure)salzen, Poly(methacrylsäure)salzen, Acrylsäure, Methacrylsäure und nicht-ionischen Alkylarylethoxylat- und Alkylethoxylat-Tensiden, und das dazu dient zu verhindern, dass mehr als % des Polysaccharid-Verdickungsmittels auf die Tonpigmentoberfläche adsorbiert wird, für die Herstellung einer Emulsionsfarbenzusammensetzung auf Wasserbasis, wobei Papierbeschichtungs-Zusammensetzungen ausgenommen sind. Revendications 1. Composition de peinture aqueuse en émulsion, à l'exclusion de compositions d'enduction du papier, comprenant 11
EP 0 707 02 B1 un système de pigment contenant une argile, un liant à base de latex, un épaississant polysaccharidique choisi dans le groupe consistant en l'hydroxyéthylcellulose, une hydroxyéthylcellulose à modification hydrophobe, l'éthylhydroxyéthylcellulose, une éthylhydroxyéthylcellulose à modification hydrophobe et leurs mélanges, et 0,00 % à 2 %, sur la base du poids du pigment, d'un agent bloquant, qui est choisi dans le groupe consistant en poly (oxyde d'éthylène), poly(éthylèneglycol), poly(oxyde de propylène), poly(propylèneglycol), poly(alcool vinylique), poly(acide acrylique), sel de poly(acide acrylique), sels de poly(acide méthacrylique), acide acrylique, acide méthacrylique et agents tensio-actifs non ioniques du type produit d'éthoxylation alkylarylique et du type produit d'éthoxylation alkylique, et qui sert à empêcher l'adsorbtion d'une quantité supérieure à % de l'épaississant polysaccharidique sur la surface du pigment à base d'une argile, la composition de peinture présentant ainsi un aspect et des performances d'application améliorées. 2. Composition suivant la revendication 1, dans laquelle l'épaississant polysaccharidique consiste en hydroxyéthylcellulose ayant un poids moléculaire de 0 000 à 1 00 000. 1 2 3. Composition suivant la revendication 2, dans laquelle l'hydroxyéthylcellulose a une substitution molaire de 1, à 4,0. 4. Composition suivant la revendication 1, dans laquelle l'épaississant polysaccharidique consiste en hydroxyéthylcellulose à modification hydrophobe ayant un poids moléculaire de 0 000 à 1 000 000.. Composition suivant la revendication 4, dans laquelle l'hydroxyéthylcellulose à modification hydrophobe a une substitution molaire hydroxyéthyle de 1, à 4,0. 6. Composition suivant la revendication, dans laquelle l'hydroxyéthylcellulose à modification hydrophobe a une modification hydrophobe constituée d'un groupe alkyle en C 4 àc 22 ou alkylaryle en C 8 àc en une quantité de 0,01 à 2,0 % en poids sur la base du poids total de l'hydroxyéthylcellulose à modification hydrophobe. 3 7. Composition suivant la revendication 1, dans laquelle l'épaississant polysaccharidique consiste en éthylhydroxyéthylcellulose ayant un poids moléculaire de 0 000 à 1 00 000. 8. Composition suivant la revendication 7, dans laquelle l'éthylhydroxyéthylcellulose a une substitution molaire hydroxyéthyle de 0, à 3,0. 9. Composition suivant la revendication 8, dans laquelle l'éthylhydroxyéthylcellulose a un degré de substitution éthyle de 0,3 à 1,2.. Composition suivant la revendication 1, dans laquelle l'épaississant polysaccharidique consiste en éthylhydroxyéthylcellulose à modification hydrophobe ayant un poids moléculaire de 0 000 à 1 000 000. 4 0 11. Composition suivant la revendication, dans laquelle l'éthylhydroxyéthylcellulose à modification hydrophobe a une substitution molaire hydroxyéthyle de 0, à 3,. 12. Composition suivant la revendication 11, dans laquelle l'éthylhydroxyéthylcellulose à modification hydrophobe a un degré de substitution éthoxyle de 0,3 à 1,2. 13. Composition suivant la revendication 12, dans laquelle l'éthylhydroxyéthylcellulose à modification hydrophobe a une modification hydrophobe constituée d'un groupe alkyle en C 4 àc 22 ou alkylaryle en C 8 àc en une quantité de 0,01 à 2,0 % en poids sur la base du poids total de l'éthylhydroxyéthylcellulose à modification hydrophobe. 14. Composition suivant la revendication 1, dans laquelle l'agent bloquant est choisi dans le groupe consistant en poly (oxyde d'éthylène), poly(éthylèneglycol), poly-(oxyde de propylène) et poly(propylèneglycol), l'agent bloquant ayant ainsi un poids moléculaire de 0 à 1 000 000. 1. Composition suivant la revendication 1, dans laquelle l'agent bloquant consiste en poly(alcool vinylique) ayant un poids moléculaire de 00 à 00 000. 16. Composition suivant la revendication 1, dans laquelle le poly(alcool vinylique) a un degré d'hydrolyse de à 90 pour cent. 12
EP 0 707 02 B1 17. Composition suivant la revendication 1, dans laquelle l'agent bloquant est choisi dans le groupe consistant en des sels de poly(acide acrylique), des sels de poly(acide méthacrylique), l'acide acrylique et l'acide méthacrylique. 18. Composition suivant la revendication 17, dans laquelle les sels ont un poids moléculaire de 00 à 1 000 000. 19. Composition suivant la revendication 1, dans laquelle les agents tensio-actifs non ioniques ont 4 à 0 motifs oxyéthylène et une chaîne hydrophobe constituée d'un groupe alkylaryle en C 8 à C ou alkyle en C 4 à C.. Composition suivant la revendication 1, dans laquelle le système de pigment contenant une argile comprend des pigments diluants choisis dans le groupe consistant en des pigments du type argile et des pigments du type carbonate de calcium contaminés avec des argiles hydrophiles. 1 2 3 21. Composition suivant la revendication, dans laquelle les diluants du type argile sont des kaolinites ou des argiles calcinées présentant une perte au feu. 22. Composition suivant la revendication, dans laquelle les diluants du type carbonates de calcium contaminés sont choisis dans le groupe consistant en une argile attapulgite, une argile hectorite, des montmorillonites et une argile bentonite. 23. Composition suivant la revendication 22, dans laquelle les diluants du type carbonates de calcium contaminés consistent en diluants Bianco Meudon Tipo A. 24. Composition suivant la revendication 1, dans laquelle la composition de peinture a une concentration volumique en pigments de 0 à 0. 2. Utilisation d'une argile contenant un système de pigments, un liant à base de latex, un épaississant polysaccharidique choisi dans le groupe consistant en hydroxyéthylcellulose, hydroxyéthylcellulose à modification hydrophobe, éthylhydroxyéthylcellulose, éthylhydroxyéthylcellulose à modification hydrophobe et leurs mélanges, et 0,00 % à 2 %, sur la base du poids du pigment, d'un agent bloquant, qui est choisi dans le groupe consistant en poly (oxyde d'éthylène), poly(éthylèneglycol), poly(oxyde de propylène), poly(propylèneglycol), poly(alcool vinylique), poly(acide acrylique), sel de poly(acide acrylique), sels de poly(acide méthacrylique), acide acrylique, acide méthacrylique et agents tensio-actifs non ioniques du type produit d'éthoxylation alkylarylique et produit d'éthoxylation alkylique, et qui sert à empêcher l'adsorbtion d'une quantité supérieure à % de l'épaississant polysaccharidique sur la surface du pigment contenant une argile, dans la production d'une composition de peinture aqueuse en émulsion, à l'exclusion de compositions d'enduction du papier. 4 0 13