Silicon-containing emulsion powder for use in making cement-based tile adhesive dry mix compositions - Patents.com

Abstract

The present invention relates to a storage stable silicon-containing powder composition suitable for use in a dry mix composition containing cement and filler suitable as a cement-based tile adhesive, comprising: (i) a water redispersible polymer powder (RDP); and (ii) (a) a silicate carrier; (b) a polydiorganosiloxane; (c) a C4-C6 silicate carrier; 12 and (d) a granular composition of a hydrolyzable silane or oligomer thereof containing an alkyl group, and a polymeric encapsulant for the hydrolyzable silane and polydiorganosiloxane, wherein the weight ratio of total RDP to the total weight of the granular composition ranges from 90:10 to 98:2.The present invention provides a method of using a dry mix as a cementitious tile adhesive, wherein the powder composition allows for good open time and excellent tensile adhesion, especially after heat aging.

Description

[Technical field]

[0001] The present invention relates to a water-redispersible polymer powder, a silicate carrier, a C4-C silane such as polydiorganosiloxane, and octyltriethoxysilane. 12 The present invention relates to a storage stable powder composition for use in a cementitious dry mix composition for making a cement-based tile adhesive, comprising a hydrolyzable silane containing an alkyl group and a granular composition of a polymeric encapsulant, as well as cementitious dry mix compositions containing same, mortar or tile adhesives made therefrom, and methods of using said compositions. [Background technology]

[0002] Cementitious tile adhesives generally include dry mix compositions in which cellulose ether, cement, and sand or finely divided fillers are formulated. The dry mix composition is mixed with water, left to build up a suitable consistency of 400-650 Pa·S at 25°C, and then applied to the substrate on which the tile will be placed. Such adhesives can be used for more demanding applications, but may not provide the flexibility and water or heat resistance required for such applications. Water-redispersible polymer powders (RDPs), used in mortars in various construction applications such as cementitious tile adhesives, impart varying degrees of flexibility and water resistance. However, the relatively inexpensive ethylene-vinyl acetate polymer RDPs are unable to impart acceptable tensile bond strength after water immersion and heat aging. More recent attempts to improve the water resistance of cementitious tile adhesives containing RDPs have included silicon-containing organic additives. Nevertheless, such materials generally lack storage stability and do not provide both acceptable open time and improved tensile bond strength after at least one of water immersion or heat aging.

[0003] WO 2012019908(A1) of Wacker Chemie AG (Wacker) discloses a cement-based tile adhesive comprising a polymer powder composition of a water-redispersible addition polymer (RDP) formed from an aqueous dispersion in a relatively storage-stable formulation containing one or more additives selected from organosilicon compounds, fatty acids and their fatty acid derivatives, or hydrocarbon waxes, and one or more protective colloids. The additives may be included in the RDP before or during the addition polymerization, or before drying the polymer dispersion. However, Wacker's composition does not allow all of the improved adhesion and acceptable open time after water immersion or heat aging.

[0004] The present invention seeks to solve the problem of being able to provide a storage stable silicon compound-containing composition that imparts water and heat aging resistance when used in cementitious cement-based tile adhesive compositions while maintaining an acceptable open time. Summary of the Invention

[0005] According to the present invention, the storage stable powder composition comprises: (i) a water redispersible polymer powder (RDP), such as an ethylene-vinyl acetate (VaE) copolymer, an acrylate copolymer, or a styrene acrylate copolymer, preferably a VaE copolymer that does not contain in copolymerized form any monomer containing an alkyl group of C4 or more, such as a VaE copolymer that does not contain in copolymerized form any monomer other than ethylene and vinyl acetate, (ii) (a) a silicate support such as a zeolite or an aluminum silicate, e.g., sodium aluminum silicate; (b) a polydiorganosiloxane; (c) a C4-C 12and (d) a hydrolyzable silane containing an alkyl group or an oligomer thereof, preferably a C6-C9 alkyl group, or more preferably an octyltrialkoxysilane or an oligomer thereof, and a granular composition of (a) a polymeric encapsulant for the hydrolyzable silane and the polydiorganosiloxane, preferably polyvinyl alcohol, wherein the weight ratio of the total RDP to the total granular composition is in the range of 90:10 to 98:2.

[0006] In the storage stable powder composition according to the invention, (ii) the granular composition comprises (a) 54-89%, or preferably 69-85%, by weight of silicate carrier, (b) 4-15%, or preferably 6-12%, by weight of polydiorganosiloxane, (c) 6.5-25%, or preferably 8-15%, by weight of hydrolyzable silane, and (d) 0.5-6%, or preferably 1-4%, by weight of a polymeric encapsulant for the hydrolyzable silane and polydiorganosiloxane. All weight percentages in the granular composition are based on the total weight of the granular composition and add up to 100%.

[0007] In the storage-stable powder composition according to the present invention, (a) the silicate support has an average diameter (X50) in the range of 0.1 to 5000 μm, or preferably 0.2 to 1000 μm, or more preferably 0.2 to 8 μm, or more preferably 1 to 6 μm.

[0008] In the storage-stable powder composition according to the invention, the (b) polydiorganosiloxanes have a room temperature viscosity in undiluted form of 40 to 500 MPa·s, or preferably 50 to 150 MPa·s, or more preferably 60 to 80 MPa·s. More preferably, at least one of the (b) polydiorganosiloxanes is a hydroxyl-terminated polydi(C1-C2 alkyl)siloxane, such as a hydroxyl-terminated polydimethylsiloxane.

[0009] In the storage-stable powder composition according to the present invention, (c) the hydrolyzable silane can be n-octyltriethoxysilane, n-octyltrimethoxysilane, or oligomers thereof.

[0010] According to the present invention, the storage stable powder composition is suitable as a dry mix composition for use in cement-based tile adhesives and comprises 0.5 to 5.5 wt. %, or preferably 1 to 5 wt. %, of (i) a water redispersible polymer powder (RDP) and (ii) a granular composition, further comprising cement and sand, one or more fillers or combinations thereof, all amounts being in wt. % of the total solids in the dry mix composition.

[0011] According to the present invention, a storage stable powder composition suitable for use as a dry mix composition in a cement-based tile adhesive comprises: Dry cement, for example ordinary Portland cement, in an amount of 15-35% by weight, or preferably 18-30% by weight, based on the total weight of the powder composition; 0.5 to 5.5% by weight, or preferably 1 to 5% by weight, of a mixture of (i) a water-redispersible polymer powder (RDP) and (ii) a granular composition, based on the total weight of the storage-stable powder composition; The remainder of the storage-stable powder composition comprises sand, one or more fillers or a combination thereof, for example a filler having a sieve mean particle size of from 80 micrometers to less than 0.8 mm, all weight percentages in the powder composition totaling 100%. The storage-stable powder composition according to the present invention may further comprise one or more cellulose ethers.

[0012] Preferably, the storage stable powder composition according to the present invention, when used as a dry mix composition in a cementitious tile adhesive mixed with water to a viscosity of 400 to 650 Pa s at 25° C. according to EN 12004:2 (2017), has a viscosity of at least 1 N / mm when determined according to EN 1348 after each one of: (i) 28 days of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure, (ii) 7 days+7 hours of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure, and 20 days+17 hours of water immersion at 23° C.±2° C. and standard (101.3 kPa) pressure, and (iii) 14 days of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure followed by 14 days of heat ageing at 70° C. 2, or more preferably at least 1.3 N / mm 2 More preferably, the powder composition according to the invention, when used in an amount of 0.5 to 5.5 wt. %, based on the total weight of the cementitious tile adhesive dry mix composition mixed with water to a viscosity of 400 to 650 Pa s at 25° C. according to EN 12004:2 (2017), exhibits a tensile strength of at least 0.5 N / mm when determined according to EN 1346 20 minutes after embedding the tile adhesive in a substrate, or preferably 30 minutes after embedding the tile adhesive in a substrate. 2 , or more preferably at least 0.9 N / mm 2 Indicates the open time.

[0013] Even more preferably, the storage stable powder composition according to the present invention, when used as a dry mix composition in a cementitious tile adhesive mixed with water to a viscosity of 400 to 650 Pa s at 25°C according to EN 12004:2 (2017), has a viscosity of at least 1 N / mm when determined according to EN 1348 after each one of: (i) 28 days of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure, (ii) 7 days + 7 hours of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure and 20 days + 17 hours of water immersion at 23°C ± 2°C and standard (101.3 kPa) pressure, and (iii) 14 days of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure followed by 14 days of heat ageing at 70°C. 2 , or more preferably at least 1.3 N / mm 2 Furthermore, the storage stable powder composition according to the present invention, when used in an amount of 1 to 5 wt. %, based on the total weight of the cementitious tile adhesive dry mix composition mixed with water to a viscosity of 400 to 650 Pa s at 25° C. according to EN 12004:2 (2017), exhibits a tensile strength of at least 0.5 N / mm when measured according to EN 1346 20 minutes after embedding the tile adhesive in a substrate, or preferably 30 minutes after embedding the tile adhesive in a substrate. 2 , or more preferably at least 0.9 N / mm 2 Indicates the open time.

[0014] In another aspect of the invention, a method of using the storage stable powder composition according to the invention includes mixing the powder composition with water to form a cementitious tile adhesive, applying the adhesive to a substrate to form an adhesive-bearing substrate, and then applying a tile to the adhesive-bearing substrate. The substrate may include a porous substrate, such as concrete, gypsum board, backer board, plywood, wood, fiber cement board, cement primer, hardened mortar, or another unfinished substrate.

[0015] Unless otherwise indicated, all temperatures and pressures are at room temperature (19-23°C) and standard pressure (1 atm). In addition, all conditions include 50% relative humidity (RH) unless otherwise stated.

[0016] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0017] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

[0018] All phrases containing parentheses refer to either or both of the substance contained within the parentheses, or its absence. For example, the phrase "hydrolyzable (alkoxy)silane" includes, in the alternative, hydrolyzable alkoxysilanes and hydrolyzable silanes having hydrolyzable groups other than alkoxysilane groups, such as acetoxy or oxime groups.

[0019] All recited ranges are inclusive and combinable, for example, a disclosure of 6.5-25 weight percent, or preferably 8-15 weight percent, of a hydrolyzable silane includes all of the following: 6.5-25 weight percent, or preferably 8-15 weight percent, or 6.5-8 weight percent, or 8-25 weight percent, or 6.5-15 weight percent, or 15-25 weight percent of the hydrolyzable silane.

[0020] As used herein, the term "anhydroglucose unit" or "AGU" refers to a monosaccharide in (co)polymeric form.

[0021] As used herein, the term "aqueous" means that the continuous phase or medium is water and 0-10% by weight, based on the weight of the medium, of water-miscible compounds. Preferably, "aqueous" means water.

[0022] As used herein, the phrase "on a total solids basis" refers to the weight of all of the non-volatile components in a given composition, including synthetic polymers, cellulose ethers, acids, defoamers, hydraulic cements, fillers, other inorganic materials, and other non-volatile additives. Water, ammonia, and volatile solvents are not considered solids.

[0023] As used herein, the term "DIN EN" or "EN" refers to the European standard version of the German material standards published by Beuth Verlag GmbH, Berlin, DE. Also, as used herein, the term "DIN" refers to the German version of the same material specifications.

[0024] As used herein, the term "dry mix" means a storage stable powder containing cement, cellulose ether, or any other polymeric additives, fillers, and any dry additives. There is no water in the dry mix, so it is storage stable.

[0025] As used herein, the term "DS" is the average number of alkyl-substituted OH groups per anhydroglucose unit in the cellulose ether, and the term "MS" is the average number of hydroxyalkyl-substituted OH groups per anhydroglucose unit, both determined by the Zeisel method. The term "Zeisel method" refers to the Zeisel cleavage procedure for the determination of MS and DS. See G. Bartelmus and R. Ketterer, Fresenius Zeitschrift für Analytische Chemie, Vol. 286 (1977, Springer, Berlin, DE), pages 161 to 190.

[0026] As used herein, unless otherwise indicated, measured values ​​of glass transition temperature (Tg) are used. As used herein, unless otherwise indicated, the term "calculated Tg" refers to the Tg of a polymer calculated by using the Fox equation (TG Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)). As used herein, the term "measured Tg" refers to the Tg measured using differential scanning calorimetry or DSC performed in the range of -100°C to 200°C (heating rate 10°C / min, Tg measured at the midpoint of the inflection).

[0027] As used herein, the term "low or medium viscosity cellulose ether" refers to a rheological mass measured using a Haake Rotovisko™ RV 100 rheometer (Thermo Fisher Scientific, Karlsruhe, DE) at 20° C. and a shear rate of 2.55 s -1 This refers to a cellulose ether having a viscosity of 10,000 to 40,000 MPa·s measured as a 2 wt % aqueous solution.

[0028] As used herein, the term "high viscosity cellulose ether" refers to a cellulose ether having a viscosity of 20° C. and a shear rate of 2.55 s -1 By "cellulose ether" is meant a cellulose ether having a viscosity of more than 40,000 mPas measured as a 2 wt. % aqueous solution using a Haake Rotovisko™ RV100 rheometer (Thermo Fisher Scientific, Karlsruhe, DE) at

[0029] As used herein, the term "ISO" refers to publications of the International Organization for Standardization (Geneva CH).

[0030] As used herein, the term "average diameter" means the value (X50) or the arithmetic mean as determined by light scattering.

[0031] As used herein, the term "mortar viscosity" refers to the viscosity in Ps (Pa s) at 25°C of mortar mixed according to EN 196-1, section 4.4 or as part of EN 1348, measured in a cup (h=80 mm, d=100 mm) using a Brookfield viscometer RVDV II Pro (DVII+) with Helipath stand and spindle number TF 96 at 5 rpm and calibrated according to the manufacturer's instructions. Acceptable room temperature mortar viscosity may be in the range of 400-650 Pa s.

[0032] As used herein, the term "open time" or "open time adhesion" refers to the result when determined according to EN 1346 and indicates the length of time that the wet side, i.e. the back side, of a given tile when placed on a combed bed of a given tile adhesive on a base is still sufficiently wet to adhere. The test involves placing tiles on the bed of the given tile adhesive after each of 5 minute intervals, i.e. 5, 10, 15, 20, 25 and 30 minutes, and pressing down each tile with a 3 kg weight for 30 seconds. After a specified storage period under specified conditions, a tensile plate is adhered to the front side of the tile and the tile is pulled away from the base using a tensile tester. The force required to pull the tile away from the base is measured in N / mm 2 The adhesive is reported as open time in units of 40 minutes. In the "quick open time" test, after 40 minutes, all tiles are removed from the base and the underside is inspected. Wetting of the backside of the tile by the adhesive is determined by counting the area that remains wet and rounding the number to ±5% coverage, or similar to the tensile adhesion test, by determining the force it takes to remove the tile from the substrate using a tensile tester. Quick open time means the period, measured in minutes, during which ≥ 50% of the backside of the tile remains wet.

[0033] As used herein, the term "polymer" refers to a polymer made from one or more different monomers, optionally including copolymers, terpolymers, tetrapolymers, pentapolymers, etc., and may be a random, block, graft, sequential, or gradient polymer.

[0034] As used herein, the term "set" refers to the hardening of the cementitious tile adhesive that occurs under ambient conditions in the presence of water and continues as the cementitious tile adhesive dries.

[0035] As used herein, unless otherwise indicated, the term "sieve mean particle size" refers to the mean particle size determined by a LAVIB sieving machine (Siebtechnik, Muelheim, DE). The term "sieve particle size" can be used interchangeably with the term "sieve mean particle size."

[0036] As used herein, the term "tensile adhesion" refers to the result when a given tile conforming to ISP 13006 is placed on a bed of a given tile adhesive on a given base under a defined set of conditions for a given time, and then a tensile test plate is glued to the top of the tile and the tile is pulled off the base according to EN 1348. The force required to remove the tile from the base is expressed as tensile adhesion in N / mm 2 Report in units.

[0037] As used herein, the term "weight percent of total solids" means the weight of all non-volatile components of a given composition as determined by volatility at or below 40° C. and atmospheric pressure. Volatile materials include solvents such as water, methyl chloride, which evaporate under ambient temperature and pressure conditions.

[0038] As used herein, the term "wt.%" refers to weight percent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] According to the present invention, a storage-stable powder composition of (i) a water-redispersible polymer powder (RDP) and (ii) a granular composition of polydiorganosiloxane and hydrolyzable silane encapsulated in a dispersible encapsulant polymer or colloidal stabilizer polymer and supported on a silicate carrier allows the provision of dry mixes and mortars for use in making cement-based tile adhesives that have both very good open time and very good tensile adhesion when used. Specifically, the inventors have found silicon-containing compositions containing a water-redispersible polymer powder (RDP), a silane and a polydiorganosiloxane used in combination, which allows the open time of the cement-based tile adhesive to be improved, while at the same time allowing improved water and heat aging resistance. Furthermore, the composition allows the provision of a storage-stable dry mix composition containing a silicon-containing additive. The encapsulant polymer allows both the storage stability of the dry mix containing the granular composition and the release of the active silicon-containing component when water is added to the dry mix composition. The silicon-containing (ii) granular composition according to the present invention constitutes 0.05 to 0.55% by weight of the dry mix composition, and the total amount of the polydiorganosiloxane and the hydrolyzable silane together constitutes 0.005 to 0.22% by weight, or preferably 0.007 to 0.1% by weight, of the dry mix composition according to the present invention.

[0040] According to the present invention, the storage stable powder composition comprises: (i) a water redispersible polymer powder (RDP), such as an ethylene-vinyl acetate (VaE) copolymer, an acrylate copolymer, or a styrene acrylate copolymer, preferably a VaE copolymer that does not contain in copolymerized form any monomer containing an alkyl group of C4 or more, such as a VaE copolymer that does not contain in copolymerized form any monomer other than ethylene and vinyl acetate, (ii) (a) a silicate support such as a zeolite or an aluminum silicate, e.g., sodium aluminum silicate; (b) a polydiorganosiloxane, preferably poly(dimethylsiloxane) or poly(diethylsiloxane); (c) a C4-C6 12and (d) a granular composition of a hydrolyzable silane containing an alkyl group or an oligomer thereof, preferably a C6-C9 alkyl group, or more preferably an octyltrialkoxysilane, and a polymeric encapsulant for the hydrolyzable silane and the polydiorganosiloxane, preferably polyvinyl alcohol, wherein the weight ratio of the total RDP to the total granular composition ranges from 90:10 to 98:2. A suitable dry mix composition comprises 0.5 to 5.5 wt. %, or preferably 1 to 5 wt. %, of the combination of (i) the RDP and (ii) the granular composition.

[0041] Further according to the invention, the storage stable powder composition comprises (ii) as a granular composition: (a) 54-89 wt%, or preferably 69-85 wt%, of a silicate carrier; (b) 4-15 wt%, or preferably 6-12 wt%, of a polydiorganosiloxane; (c) 6.5-25 wt%, or preferably 8-15 wt%, of a hydrolyzable silane; and (d) 0.5-6 wt%, or preferably 1-4 wt%, of a polymeric encapsulant for the hydrolyzable silane and the polydiorganosiloxane. All weight percentages in the granular composition are based on the total weight of the granular composition and add up to 100%.

[0042] Furthermore, the polydiorganosiloxane (b) in the granular composition (ii) according to the present invention has a room temperature viscosity in undiluted form of 40 to 500 MPa·s, or preferably 50 to 100 MPa·s, or more preferably 60 to 80 MPa·s.

[0043] Furthermore, at least one (b) polydiorganosiloxane in the (ii) granular composition according to the present invention is a hydroxyl-terminated polydi(C1-C2 alkyl)siloxane, such as a hydroxyl-terminated polydimethylsiloxane.

[0044] Furthermore, the (c) hydrolyzable silane in the (ii) granular composition according to the present invention is n-octyltriethoxysilane, n-octyltrimethoxysilane, or an oligomer thereof.

[0045] Still further, the storage stable powder composition according to the present invention comprises 0.15-0.75 wt.%, or preferably 0.20-0.5 wt.%, or more preferably 0.35-0.45 wt.% of one or more cellulose ethers. Preferably, at least one of the one or more cellulose ethers is selected from unmixed cellulose ethers containing alkyl ether groups, or mixed cellulose ethers containing hydroxyalkyl and alkyl ether groups, such as those selected from alkyl hydroxyethyl celluloses, e.g., hydroxyalkyl methyl celluloses, more preferably selected from hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), methyl hydroxyethyl hydroxypropyl cellulose (MHEHPC), methyl ethyl hydroxyethyl cellulose (MEHEC), and ethyl hydroxyethyl cellulose (EHEC), or even more preferably HEMC.

[0046] Preferably, the storage stable powder composition according to the present invention comprises a cement, which when mixed with water to a viscosity of 400 to 650 Pa s at 25°C according to EN 12004:2 (2017) has a viscosity of at least 1 N / mm when determined according to EN 1348 after each of: (i) 28 days of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure; (ii) 7 days + 7 hours of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure; and (iii) 14 days of ageing at 23°C ± 2°C and standard (101.3 kPa) pressure followed by 14 days of heat ageing at 70°C. 2 , e.g. at least 1.3N / mm 2 The resulting cement-based tile adhesive exhibits a tensile strength of .

[0047] More preferably, the storage stable powder composition according to the present invention comprises cement and sand, one or more fillers or a combination thereof and when mixed with water to a viscosity of 400 to 650 Pa s at 25°C according to EN 12004:2 (2017), has a viscosity of at least 0.5 N / mm when measured according to EN 1346 20 minutes after embedding the tile adhesive in a substrate, or preferably 30 minutes after embedding the tile adhesive in a substrate. 2 , e.g. at least 0.9 N / mm 2 Form a cementitious tile adhesive that exhibits an open time of .

[0048] Even more preferably, the storage stable powder composition according to the present invention comprises cement and sand, one or more fillers or a combination thereof, and when mixed with water to a viscosity of 400 to 650 Pa s at 25° C. according to EN 12004:2 (2017), has a viscosity of at least 1 N / mm when determined according to EN 1348 after each of: (i) 28 days of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure; (ii) 7 days+7 hours of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure and 20 days+17 hours of water immersion at 23° C.±2° C. and standard (101.3 kPa) pressure; and (iii) 14 days of ageing at 23° C.±2° C. and standard (101.3 kPa) pressure followed by 14 days of heat ageing at 70° C. 2 Or at least 1.3N / mm 2 Furthermore, the powder composition according to the invention forms a cementitious tile adhesive that exhibits a tensile strength of at least 0.5 N / mm when determined according to EN 1346 20 minutes after the tile adhesive is embedded in a substrate, or preferably 30 minutes after the tile adhesive is embedded in a substrate. 2 Or at least 0.9N / mm 2 This makes it possible to provide a cement-based tile adhesive that exhibits an open time of

[0049] An example of a suitable (ii) granular composition is a three-component granule consisting of (a) a silicate carrier, (b) a polydiorganosiloxane, (c) a hydrolyzable silane, and (d) a polymeric encapsulant for the hydrolyzable silane and the polydiorganosiloxane. The encapsulant provides storage stability in the powdered composition and release of the active ingredient upon addition of water.

[0050] The silicate carrier (a) according to the present invention may be water-insoluble or water-dispersible. Suitable examples of carrier particles include, for example, aluminosilicates (such as zeolites or metakaolin), clays, or sands. The silicate carrier may have an average diameter (X50 determined by light scattering) of 0.1 to 5000 μm, or preferably 0.2 to 1000 μm, or more preferably 0.2 to 50 μm. The smaller the particle size of the silicate carrier, the less encapsulant polymer can be used to completely encapsulate the remaining materials in the granular composition.

[0051] The polyorganosiloxane (b) according to the present invention has a viscosity that allows storage stability and facilitates processing. The polyorganosiloxane may be a linear polymer or may contain a small percentage of branched repeat units, such as 5% or less. Such branching may result from the presence of hydrolyzable or silanol end groups in the polyorganosiloxane that is subsequently oligomerized.

[0052] The hydrolyzable silane (c) according to the present invention is an alkoxysilane or a C4-C 12 It may include oligomers formed by partial hydrolysis of another hydrolyzable silane containing an alkyl group, and may include condensation products of partially hydrolyzed trialkoxysilanes such as n-octyltrimethoxysilane or n-octyltriethoxysilane. 12The alkyl groups are large enough so that they do not volatilize during processing, storage, or use, and small enough so that they do not become waxy or soft during or after use. Partial hydrolysis can be accomplished by adding small amounts (0.0001-0.05 moles per mole of silane) of aqueous base, such as caustic, or acid, such as an organic acid with a pKa less than 4, such as formic acid, followed by quenching to neutralize the pH.

[0053] The (d) polymeric encapsulating agent may be, for example, a metastable emulsion polymer, such as an acrylic emulsion polymer having up to 5% by weight of repeating units containing carboxylate groups, or a colloidal stabilizer that is itself dispersible in water, such as poly(vinyl alcohol). The amount of polymeric encapsulating agent is such that it encapsulates both the (b) polydiorganosiloxane and the (c) hydrolyzable silane, but is not so great that the resulting granules do not contain all of the materials in the (ii) granular composition, including the silicate carrier.

[0054] (ii) The granular composition may be formed from an aqueous dispersion or emulsion in which (b) polydiorganosiloxane and (c) hydrolyzable silane are granulated by methods known to those skilled in the art. Such methods are disclosed, for example, in U.S. Patent No. 8,445,560 (B2) to Lecomte et al., European Patent No. 0,811,584 to Dow Silicones UK Ltd., or European Patent No. 496,510 to Dow Silicones Belgium SPRL. In the granulation process, (b) polydiorganosiloxane and (c) hydrolyzable silane are emulsified or at least dispersed in an aqueous medium or emulsion of (d) a polymeric encapsulant for the hydrolyzable silane and polydiorganosiloxane. Such dispersion may be carried out by using an in-line mixer or a static mixer. The resulting silane and polysiloxane dispersion or emulsion composition is deposited in liquid form, e.g., by spraying, onto (a) a silicate support, e.g., in a fluidized bed, thereby solidifying the mixture through evaporation of water onto the support, thereby forming a free-flowing powder.

[0055] In another suitable granulation method, the emulsion of (b) polydiorganosiloxane, (c) hydrolyzable silane, and (d) polymer encapsulant is simultaneously sprayed into a drum mixer containing (a) silicate carrier. The spray droplets partially evaporate when they contact the silicate carrier particles, and the resulting particles are then transferred to a fluidized bed where the ambient air completes the evaporation. The granular composition is then (ii) collected from the fluidized bed. Typical equipment useful for granulation can include an Eirich™ general granulator, a Schugi™ mixer, a Paesson-Kelly™ twin-core blender, a Lodige™ plowshare mixer, a Lodige™ continuous ring-bed mixer, or one of many types of fluidized bed equipment, such as an Aeromatic™ fluidized bed granulator. The resulting granules can be further screened by sieving to produce particles of the granular composition that are substantially free of undersized or oversized materials.

[0056] In yet another suitable method, (a) silicate is injected under stirring into an aqueous dispersion of (b) polydiorganosiloxane, (c) hydrolyzable silane, and (d) polymeric encapsulant, followed by drying and granulation of the resulting mixture.

[0057] The storage stable powder composition of the present invention comprises at least one (i) water redispersible polymer powder (RDP). The RDP may be formed in a conventional manner by spray drying an emulsion polymer binder formed by conventional aqueous emulsion polymerization. The aqueous emulsion polymer may be selected from various composition classes such as, for example, vinyl acetate polymers, vinyl acetate-acrylic copolymers, vinyl acetate-ethylene copolymers, acrylic polymers, styrene-acrylic polymers, styrene-butadiene copolymers, and blends thereof. The RDP composition may further comprise an anti-caking agent such as clay and a colloidal stabilizer such as poly(vinyl alcohol), which allows for the formation of a finely divided powder by spray drying. The RDP may improve the adhesion and durability of skim coat mortar. Suitable emulsion polymers may have a glass transition temperature (Tg) of at least -30°C, or not more than 20°C, or preferably at least -15°C, or preferably not more than 15°C, or more preferably at least -10°C. If the Tg is too high to be used in the cement composition, end-use properties such as low temperature flexibility and crack bridging may be compromised. The Tg of the copolymer can be determined in known manner by differential scanning calorimetry (DSC). A suitable RDP composition according to the invention comprises the product of drying a combination of a water-insoluble film-forming polymer, a colloidal stabilizer for colloidal stabilization, and a finely divided anticaking agent such as clay, e.g., kaolin. Conventional colloidal stabilizers such as polyvinyl alcohol (PVOH) may be used as colloidal stabilizers in conventional amounts. A preferred polyvinyl alcohol for use herein is partially hydrolyzed polyvinyl alcohol. The amount of PVOH or other known colloidal stabilizer used to achieve colloidal stability may be at least 1% by weight, for example 2-30% by weight, or preferably 5-20% by weight, based on the weight of the water-insoluble film-forming polymer. Suitable anticaking agents may be kaolin, calcium carbonate, or silicates, etc. The amount of anticaking agent may be up to 40% by weight, based on the weight of the resulting water-redispersible polymer powder (RDP).

[0058] According to the present invention, a water-redispersible polymer powder (RDP) composition may be produced by drying an aqueous mixture of a water-insoluble film-forming polymer and a colloidal stabilizer while introducing an anti-caking agent into the aqueous mixture stream. Such drying may be carried out in a conventional manner using known polymer compositions, such as, for example, the methods described in U.S. Patent Application Publication No. 2010 / 0240819 A1 to Perello et al. or U.S. Patent No. 9,181,130 B2 to Dombrowksi et al. Thus, drying may include spray drying the polymer, the colloidal stabilizer, or both together and the anti-caking agent as a co-feed stream. For example, an aqueous dispersion of a water-insoluble film-forming polymer may be provided by emulsion polymerization, a colloidal stabilizer may be mixed with the aqueous dispersion after polymerization, and the aqueous dispersion may then be spray dried while adding an anti-caking agent to obtain a water-redispersible polymer powder. In one example, the viscosity of the feedstock to be spray dried can be adjusted via the solids content so as to obtain values ​​below 1000 mPa S (Brookfield viscosity at 20 revolutions and 23° C.), preferably below 250 mPa S. The solids content of the dispersion to be spray dried can be generally 25-75% by weight, for example 35-65% by weight, preferably 40-60% by weight, based on the total weight of the dispersion. Spray drying can be carried out in conventional spray drying plants, where atomization is carried out using one-fluid, two-fluid or multi-fluid nozzles or rotating disk atomizers. Generally, air, nitrogen or nitrogen-enriched air can be used as drying gas, the inlet temperature of the drying gas generally not exceeding 200° C., or preferably between 110° C. and 180° C., or more preferably between 130° C. and 170° C. The outlet temperature may be approximately between 45° C. and 120° C., or preferably between 60° C. and 90° C., depending on the plant, the glass transition temperature of the polymer composition, and the desired dryness.

[0059] Suitable cellulose ethers for use in the powders, dry mixes, and cementitious tile adhesives according to the present invention can include, for example, hydroxyalkyl celluloses, alkyl celluloses, or mixtures of such cellulose ethers. Examples of cellulose ether compounds suitable for use in the present invention include, for example, methylcellulose (MC), ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl methylcellulose (HEMC), hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose ("hydroxyethyl cellulose, HEC"), ethylhydroxyethylcellulose (EHEC), methylethylhydroxyethylcellulose (MEHEC), hydrophobically modified ethylhydroxyethylcellulose (HMEHEC), hydrophobically modified hydroxyethylcellulose (HMHEC), sulfoethyl methylhydroxyethylcellulose (SEMHEC), sulfoethyl methylhydroxypropylcellulose (SEMHPC), and sulfoethyl hydroxyethylcellulose (SEHEC).Preferably, the cellulose ether is a mixed cellulose ether containing hydroxyalkyl groups and alkyl ether groups, such as alkyl hydroxyethyl celluloses, e.g., hydroxyalkyl methyl celluloses, e.g., hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), methyl hydroxyethyl hydroxypropyl cellulose (MHEHPC), methyl hydroxyethyl cellulose (MEHEC), and ethyl hydroxyethyl cellulose (EHEC).

[0060] In the cellulose ethers according to the invention, alkyl substitution is described in cellulose ether chemistry by the term "DS". DS is the average number of substituted OH groups per anhydroglucose unit. Methyl substitution can be reported, for example, as DS(methyl) or DS(M). Hydroxyalkyl substitution is described by the term "MS". MS is the average number of moles of etherification reagent bound as ether per mole of anhydroglucose unit. Etherification with the etherification reagent ethylene oxide is reported, for example, as MS(hydroxyethyl) or MS(HE). Etherification with the etherification reagent propylene oxide is correspondingly reported as MS(hydroxypropyl) or MS(HP). Side groups are determined using the Zeisel method (see G. Bartelmus and R. Ketterer, Fresenius Zeitschrift für Analytische Chemie 286 (1977), 161-190).

[0061] Suitable cellulose ethers preferably have a hydroxyalkyl substitution MS (HE) degree of 1.5 to 4.5, or more preferably a substitution MS (HE) degree of 2.0 to 3.0. Preferably, mixed ethers of methylcellulose such as HEMC are used having a methyl substitution DS (M) value in the range of 1.2 to 2.1, or more preferably 1.3 to 1.7, or even more preferably 1.35 to 1.65, and a hydroxyalkyl substitution MS (HE) value in the range of 0.05 to 0.75, or more preferably 0.10 to 0.45, or even more preferably 0.15 to 0.40. In the case of HPMC, the DS (M) value is preferably in the range of 1.2 to 2.1, or more preferably 1.3 to 2.0, and the MS (HP) value is preferably in the range of 0.1 to 1.5, or more preferably 0.15 to 1.2.

[0062] Storage-stable powder compositions according to the invention suitable for use as dry mixes may further comprise finely divided cement, such as hydraulic cement powder. A suitable example of cement is ordinary Portland cement. The dry cement may be used in an amount of 15-33 wt.%, or preferably 18-30 wt.%, based on the total weight of the dry mix.

[0063] Storage-stable powder compositions according to the invention suitable for use as a dry mix may further comprise 59.5-84.5 wt. %, or preferably 65-81 wt. %, of sand, one or more fillers, or both. Suitable fillers may be selected from alkali carbonates and silicates and their calcined, sintered, or ceramic forms, such as dolomite, kaolinite, calcium carbonate, such as ground calcium carbonate, magnesium carbonate, talc, quartz sand, white quartz sand, or alkali metal silicates, such as calcium silicate, sodium silicate, or mixtures thereof. Suitable particle sizes for the sand or fillers may range from 100% <0.8 mm or less, e.g. from 80 micrometers to less than 0.8 mm, or preferably 100% <0.5 mm or less, sieve mean particle size (measured by a LAVIB sieving machine (Siebtechnik, Muelheim, DE)).

[0064] The storage-stable powder composition of the present invention suitable for use as a dry mix may contain up to 1% by weight of any one or more additional ingredients in dry form, such as accelerators such as calcium formate, superplasticizers, additional organic or inorganic thickeners and / or secondary water retention agents, anti-sag agents, wetting agents, defoamers, dispersants, water repellents, biopolymers, or fibers. All of the additional ingredients are known in the art and commercially available. All of the additional ingredients are known in the art and available from commercial sources.

[0065] Preferred storage stable powder compositions suitable for use as cementitious tile adhesive dry mix compositions according to the present invention may further comprise 0.010 to 0.050% by weight of total solids of a starch ether or poly(meth)acrylamide slip aid, and at least 0.1% by weight of total solids of a cellulose ether.

[0066] A storage stable powder composition is formed by mixing all of the materials of the present invention in dry form. The powder composition can be stored for later use. The cementitious composition is generally used as a dry mix powder by adding water thereto and mixing to form a cementitious tile adhesive. The cementitious tile adhesive composition can be sold as a dry mix powder.

[0067] According to the present invention, a method of using the storage stable powder composition includes combining it as a dry mix with water to form a cementitious tile adhesive mortar, optionally wetting a substrate, applying the adhesive to the substrate to form an adhesive-bearing substrate, and then applying a tile to the adhesive-bearing substrate. The cementitious tile adhesive mortar can be applied onto a porous substrate such as plaster, wood, plywood, backer board, concrete, or cementitious primer.

[0068] The compositions of the present invention are utilized as cementitious tile adhesives for use with ceramic tiles, especially heavy or large tiles that require stronger adhesives. Additionally, the compositions of the present invention are utilized in thermal or underwater applications such as tunnels, pools, and outdoor applications.

[0069] The present invention provides the following features: 1. According to the present invention, a storage-stable powder composition for use as a dry mix for making a cement-based tile adhesive mortar comprises 15-33 wt. %, or preferably 18-30 wt. %, of cement, e.g. ordinary Portland cement, 65-83% by weight, or preferably 68-80% by weight, of one or more sands; one or more fillers selected from dolomite, kaolinite, calcium carbonate, talc, silica sand, white silica sand, alkali metal silicates, or mixtures thereof; 0.5 to 5.5 wt. %, or preferably 1 to 5 wt. %, of (i) one or more water redispersible polymer powders (RDP), such as ethylene-vinyl acetate (VaE), and (ii) water dispersible polymer encapsulated polydiorganosiloxane and C4 to C6 12 and a granular composition of a hydrolyzable silane having an alkyl group, wherein all amounts are by weight % of the total solids in the dry mix composition, all percentages add up to 100%, and the weight ratio of total (i) water redispersible polymer powder (RDP) to total (ii) granular composition is in the range of 90:10 to 98:2. 2. A storage-stable powder composition as described in paragraph 1 above, wherein at least one i) water-redispersible polymer powder (RDP) in the powder composition comprises an ethylene-vinyl acetate (VaE) copolymer, an acrylate copolymer, or a styrene-acrylate copolymer, or preferably a VaE copolymer that does not contain in copolymerized form any monomer containing an alkyl group of C4 or higher. 3. The (ii) granular composition comprises: (a) a silicate carrier, such as a zeolite or an aluminum silicate, such as sodium aluminum silicate, calcium silicate, or sodium silicate, and mixtures thereof; (b) a polydiorganosiloxane; and (c) a C4-C 123. The storage-stable powder composition according to any one of claims 1 or 2 above, comprising a hydrolyzable silane containing an alkyl group or an oligomer thereof, preferably a C6-C9 alkyl group, or more preferably an octyltrialkoxysilane, and (d) a polymeric encapsulating agent for the hydrolyzable silane and the polydiorganosiloxane, preferably polyvinyl alcohol. 4. The storage-stable powder composition according to any one of paragraphs 1, 2 or 3 above, wherein the (ii) granular composition comprises: (a) 54 to 89% by weight, or preferably 69 to 85% by weight, of the silicate carrier; (b) 4 to 15% by weight, or preferably 6 to 12% by weight, of the polydiorganosiloxane; (c) 6.5 to 25% by weight, or preferably 8 to 15% by weight, of the hydrolyzable silane; and (d) 0.5 to 6% by weight, or preferably 1 to 4% by weight, of a polymeric encapsulant for the hydrolyzable silane and the polydiorganosiloxane, all weight percentages in the granular composition totaling 100%. 5. A storage-stable powder composition according to any one of paragraphs 1, 2, 3 or 4 above, further comprising 0.15 to 0.75 wt.%, or preferably 0.20 to 0.5 wt.%, or more preferably 0.35 to 0.45 wt.% of one or more cellulose ethers, preferably hydroxyethyl methylcellulose. 6. A storage-stable powder composition according to any one of paragraphs 1, 2, 3, 4 or 5 above, wherein the sand or filler has an average sieve size of 100% of the particles between 80 micrometers and less than 0.8 mm, or preferably 100% of the particles have an average sieve size of 0.1 to 0.5 mm, as determined, for example, by a LAVIB sieving machine (Siebtechnik, Muelheim, DE). 7. When mixed with water to a viscosity of 400 to 650 Pa s at 25°C in accordance with EN 12004:2(2017), it has a viscosity of at least 1 N / mm when determined in accordance with EN 1348 after each of: (i) 28 days aging at 23°C ± 2°C and standard (101.3 kPa) pressure; (ii) 7 days + 7 hours aging at 23°C ± 2°C and standard (101.3 kPa) pressure and 20 days + 17 hours water immersion at 23°C ± 2°C and standard (101.3 kPa) pressure; and (iii) 14 days aging at 23°C ± 2°C and standard (101.3 kPa) pressure followed by 14 days heat aging at 70°C. 2 , or preferably at least 1.3 N / mm 2 7. The storage-stable powder composition of any one of claims 1, 2, 3, 4, 5, or 6, exhibiting a tensile strength of 8. When mixed with water to a viscosity of 400-650 Pa s at 25 °C in accordance with EN 12004:2 (2017), has a viscosity of at least 0.5 N / mm2 when determined in accordance with EN 1346 20 minutes after the tile adhesive has been embedded in the substrate or preferably 30 minutes after the tile adhesive has been embedded in the substrate 2 8. The storage-stable powder composition of any one of paragraphs 1, 2, 3, 4, 5, 6, or 7 above, exhibiting an open time of: 9. When mixed with water to a viscosity of 400-650 Pa s at 25 °C in accordance with EN 12004:2 (2017), has a viscosity of at least 0.9 N / mm2 when determined in accordance with EN 1346 20 minutes after the tile adhesive has been embedded in the substrate or preferably 30 minutes after the tile adhesive has been embedded in the substrate 2 9. The storage-stable powder composition of any one of paragraphs 1, 2, 3, 4, 5, 6, 7, or 8 above, exhibiting an open time of 10. The storage-stable powder composition according to any one of paragraphs 1, 2, 3, 4, 5, 6, 7, 8, or 9, which, when mixed with water to a viscosity of 400 to 650 Pa·s at 25°C according to EN 12004:2 (2017), exhibits a slip resistance of less than 0.5 mm when measured according to EN 1308. 11. In another aspect, the invention provides a method of using the storage-stable powder composition according to any one of paragraphs 1 to 10 above, comprising mixing the powder composition with water to form a cementitious tile adhesive, applying the adhesive to a porous substrate to form an adhesive-bearing substrate, and then applying a tile to the adhesive-bearing substrate. EXAMPLES

[0070] The following examples illustrate the invention. All parts and percentages are by weight and all temperatures are in °C unless otherwise indicated. All conditions are 23°C ± 2°C, 50% ± 5% relative humidity (rh), and air movement less than 0.2 m / s unless otherwise indicated. As used in the examples, the term "standard conditions" refers to room temperature (23°C ± 2°C) and standard pressure (101.3 kPa).

[0071] In the following examples and Tables 1, 2, 3, 4, 5, and 6, the following abbreviations have been used: PDMS: poly(dimethylsiloxane), PVOH: poly(vinyl alcohol), RDP: redispersible polymer powder, VaE: vinyl acetate ethylene.

[0072] In the examples below, the following materials were used: RDP1: DLP2000 redispersible latex powder (Dow, Midland MI (Dow)) is a free-flowing white powder obtained by spray drying an aqueous vinyl acetate ethylene (VaE) copolymer dispersion in the presence of kaolin anticaking agent and colloidal stabilizer. RDP2: VINNAPAS™ 8118 E RDP, a polymer of vinyl acetate / vinyl chloride / ethylene with colloidal stabilizer, Wacker Chemie, AG (Munich, DE (Wacker)). RDP3: VINNAPAS™ 7220E RDP, vinyl acetate / vinyl versatate (VeoVa), polymer of ethylene and acrylic esters, and colloidal stabilizer (Wacker). RDP4: A powder containing 40 wt% VeoVa, 60 wt% VaE polymer, 12 wt% PVOH as a colloidal stabilizer and 15 wt% kaolin as an anti-caking agent.

[0073] Granular composition: 77 wt. % powder carrier (zeolite); 10 wt. % silanol-terminated polydimethylsiloxane (neat viscosity about 60 MPa·s at 25° C.); 10 wt. % n-octyltriethoxysilane; 3 wt. % PVOH.

[0074] Hydrophobic additive: Hydroxyl-functional polydimethylsiloxane fluid aqueous emulsion (60-80 MPa as undiluted polymer at 25°C) * s). Water-resistant silane emulsion: A water-based emulsion containing n-octyltriethoxysilane. Cement: Ordinary Portland cement (OPC CEM 42.5). Sand: Finely divided sand with an average (X50) diameter of 0.09-0.5 mm. Fine sand: Quartz sand F36 (Quarzwerke Frechen, average grain size (X50) reported by manufacturer: 160 μm, specific surface area: 144 cm 2 / g). Medium sand: Quartz sand F32 (Quarzwerke Frechen, average grain size (X50) reported by manufacturer: 240 μm, specific surface area: 102 cm 2 / g) Cellulose ether 1: Hydroxyethyl methylcellulose (HEMC, DS(methyl)=1.55-1.65; MS(hydroxyethyl)=0.25-0.32; viscosity 50,000-58,000 mPa·s, 2 wt% aqueous solution, Haake™ Viscotester™ VT550, shear rate 2.55 s-1, 20°C (Dow)).

[0075] Cementitious tile adhesives having the specified compositions set forth in Tables 1, 2 and 3 below were tested and characterized as discussed below.

[0076] [Table 1] * A comparative example is shown.

[0077] As shown in Table 1 above, the amount of active silane (triethoxy(octyl)silane) in the composition is 1.6 times higher in Comparative Example 4 than in Example 3. The content of active (PDMS) in the composition is half the amount in Comparative Example 5 than in Example 3.

[0078] [Table 2] * A comparative example is shown.

[0079] [Table 3] * A comparative example is shown.

[0080] Unless otherwise indicated below, the designated ingredients in Tables 1, 2 and 3 above were carefully weighed as individual ingredients on an electronic balance, dry blended together as powders, and allowed to stand for 17-24 hours to form a dry mix composition. The dry mix composition was then tested as indicated below.

[0081] Unless otherwise indicated, a wet cementitious tile adhesive was formed according to EN 12004:2 (2017) as follows: take a 1500 g quantity of the specified dry mix composition, combine with water in a container using a Hobart 5-Quart Mixer (Hobart, Troy, Ohio, USA) at speed 1 for 30 seconds, scrape the sides of the container and the mixing blade with a scraper while the mixture stands for 1 minute, mix for a further minute at speed 1, scrape the sides of the container and the mixing blade again while the mixture stands for 10 minutes, then mix again for 15 seconds at speed 1 according to EN 196-1, section 4.4.

[0082] The open time was determined according to EN 1346. Group BIII porous porcelain tiles (5×5 cm, 7-10 mm thick, and a profile back pattern less than 0.25 mm deep, (Deutsche Steinzeug Cremer & Breuer AG, Alfter-Witterschlick, DE),) with a water absorption capacity of 14.4±3% by weight according to EN 14411 were used in the tests. The test substrate was a 40×20 cm gypsum plasterboard (Rigips VARIO™ 12.5). For the tests, the tiled substrate was prepared by applying a thin layer of the specified tile adhesive to the test substrate with a straight-edge trowel, followed by applying a second layer of tile adhesive and using a notched trowel with 4 mm×4 mm notches spaced 8 mm apart to skim in a straight line in a direction parallel to the side of the substrate while holding the trowel at an angle of approximately 60° to the substrate. A stopwatch was set to 0 and started. At 5 minute intervals after embedding the adhesive on the substrate, i.e. 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes and 30 minutes at each, each tile was placed on a bed of the specified tile adhesive at least 50mm away from any other tile and pressed down with a 3kg weight for 30 seconds. The interval periods were recorded and the bonded tiles were aged at the specified conditions described in the Tensile Adhesion Test below. Open time or open time adhesion according to EN 1346 refers to the amount of force it takes to peel a bonded tile from a substrate after a given interval period after storage under specified conditions and is expressed in N / mm 2 The open time is expressed as 30 minutes under standard conditions of 28 days. Thus, a 30 minute open time under standard conditions of 28 days refers to a test in which the tile is placed on the adhesive bed 30 minutes after the adhesive is applied to the base, and the tile and base are allowed to age under standard conditions for 28 days before tensile testing. More force is required to remove the embedded tile after a longer interval, meaning that the adhesive remained wet after the end of the interval. All results are reported as the average of the 10 tiles tested.

[0083] The tensile adhesion was determined after mixing according to EN 1348. Fully porcelained unglazed stoneware tiles of group B1a according to ISO 13006 (50±1 mm × 50±1 mm, Winckelmans, Lomme, FR) were used, with a flat, matt adhesive surface and a water absorption of less than 0.5% by weight. Rectangular concrete test substrates (40±5 mm thick) had a moisture content of less than 3% by weight and a tensile adhesion of 0.5 cm after 4 hours at room temperature. 3 ~1.5cm 3 The tensile tester was a direct pull tensile tester capable of applying a load to the pull head plate at a rate of 250±50 N / s through a suitable fixture that did not exert any bending force, and equipped with a connector for a square metal (50±1 mm x 50±1 mm) pull head plate of at least 10 mm thickness, with suitable fixtures to connect to the tester. The air circulating oven was capable of controlling the temperature to within ±3°C. For testing, tiled substrates were prepared by applying a thin layer of the specified tile adhesive to the test substrate with a straight edge trowel, followed by applying a second layer of tile adhesive and using a notched trowel with 6 mm x 6 mm notches spaced 12 mm apart to skim in a straight line in a direction parallel to the side of the substrate while holding the trowel at an angle of approximately 60° to the substrate. After allowing the applied adhesive to sit for 5 minutes, for each test, ten type B1a tiles were placed on the adhesive at a distance of 50 mm apart and each tile was loaded with a force of 20±0.05 N for 30 seconds to form a tiled substrate. A pull head plate was attached to the tiles on the tiled substrate using epoxy adhesive (Korapox™ 558 epoxy adhesive, Koemmerling Chemische Fabrik GmbH, Pirmasens, DE). All results are reported as an average of the ten tiles tested in N / mm 2reported in . To test the tensile bond strength under standard conditions (28 days), the tiled substrate was stored under standard conditions for 27 days and then a pull head plate was glued to the tile. After another 24 hours of storage under standard conditions, the tensile bond strength of the adhesive was determined by applying a force at a constant rate of 250 ± 50 N / s. Open time adhesion refers to the same tensile bond strength under standard conditions for 28 days when a tile is placed on the adhesive bed after a specified time interval, and indicates the adhesive's ability to function after resting for that time interval. To test the fast-setting tensile bond properties of the adhesive, a pull head plate was glued to the tile in the tiled substrate for a minimum of 2 hours before the tensile bond strength was determined. To test the tensile bond strength after water immersion, the tiled substrate was conditioned under standard conditions for 7 days and immersed in water under standard conditions for 20 days. After 20 days, the tiled substrate was removed from the water, wiped with a cloth, and a pull head plate was glued to the tile. After a further 7 hours of storage under standard conditions, the tiled substrate was immersed in water under standard conditions for a further 17 hours. At the end of the 17 hours, the tiled substrate was removed from the water and the adhesive was immediately tested for tensile bond strength by applying a force at a constant rate of 250±50 N / s. To test the tensile bond strength after heat aging, the tiled substrate was conditioned under standard conditions for 14 days and then placed in an air circulating oven at 70±3°C for a further 14 days. The tiled substrate was then removed from the oven and a pull head plate was bonded to the tile. The tiled substrate was then conditioned under standard conditions for a further 24 hours and then the tensile bond strength was determined by applying a force at a constant rate of 250±50 N / s.

[0084] Slip resistance or slippage was determined according to EN 1308. After mixing to a viscosity of 400-650 Pa·s at 25°C according to EN 12004:2 (2017), the specified freshly mixed cementitious tile adhesive was applied as a thin layer onto the concrete plate substrate using a straight-edged trowel, followed by a second layer of tile adhesive, which was then troweled in a straight line in a direction parallel to the side of the substrate using a notched trowel with 6 mm × 6 mm notches spaced 12 mm apart, while holding the trowel at an angle of approximately 60° to the substrate. After 2 minutes, two tiles (100 × 100 mm) were placed onto the wet adhesive and allowed to cure for 30 seconds under a load of 50 N. After 3 minutes, the complete concrete plate was raised into a vertical position and the distance travelled by the tile on the adhesive was recorded when the tile was fully settled on the wet mortar and no further slippage was observed. Results were reported in mm as the average of five test results.

[0085] Densities were determined by filling each specified tile adhesive into a cylinder of a given volume, weighing the adhesive in the cylinder to determine the mass of the tile adhesive contents, and dividing that mass by its volume. Densities were reported after the adhesive compositions were allowed to stand for the specified time intervals.

[0086] Viscosity is the viscosity of the cementitious tile adhesive or mortar in cPs (mPa s) at 25 °C for cementitious tile adhesive mixed according to EN 196-1, section 4.4, measured in a cup (h = 80 mm, d = 100 mm) using a Brookfield viscometer RVDV II Pro (DVII+) with a Helipath stand and spindle number TF 96 at 5 rpm, the viscometer was calibrated according to the manufacturer's instructions. The viscosity was recorded after the adhesive composition was left for the specified time intervals.

[0087] Workability is a visual test method to determine ease of application, feel, and leveling from a specified cementitious tile adhesive. Workability was measured by applying the adhesive with a notched edge steel trowel (20.48 cm long) at 25°C onto the same gypsum board substrate used to determine the open time. Scores were determined by experienced laboratory technicians. A lower score means better workability. Visual quality was also reported. Scores were as follows: 5 Very bad 4. Bad 3 Good enough 2 good 1 Very good

[0088] The characteristics of the various cellulose ether materials and cement-based tile adhesives tested in the examples are shown in Tables 4, 5, and 6 below.

[0089] [Table 4] * A comparative example is shown.

[0090] As shown in Table 4 above, the addition of the blend of PDMS and hydrolyzable silane in Example 3 does not adversely affect workability, density, or viscosity. However, as shown in Comparative Example 4, the addition of the same hydrolyzable silane in the same amount increases viscosity and density, and worsens workability. Similarly, as shown in Comparative Example 5, the addition of PDMS increases viscosity and density, and worsens workability, even though the concentration of PDMS is only 1 / 3 of the amount used in Inventive Example 3. Furthermore, in Inventive Example 3, the blend PDMS and hydrolyzable silane has a beneficial effect on open time, while the use of (c) hydrolyzable silane alone in Comparative Example 4 significantly reduces open time. Both blends of PDMS and hydrolyzable silane give workability, density, and open time properties that are comparable to or better than RDP1 with VaE polymer.

[0091] [Table 5] * -Comparative examples are shown below. 1. Maximum standard deviation 0.1%. 2. Maximum standard deviation 0.07%. 3. Maximum standard deviation 0.11%.

[0092] As shown in Table 5 above, the introduction of a granular composition having both a hydrolyzable silane and a polyorganosiloxane having a VaE-containing RDP1 (polyVaE) does not impair the workability of the cementitious tile adhesive. See Examples 8, 9, and 10. This is true even when the RDP contains a granular composition at a loading of 5% based on the weight of the RDP, as in Example 10. However, as shown in Examples 9 and 10, the preferred invention contains more than 2% by weight of the granular composition based on the total weight of the RDP in the cementitious tile adhesive. Examples 9 and 10 show improved adhesion after water immersion and heat aging, especially in Example 10. Compare Comparative Example 6. As shown in Examples 8, 9, and 10, when compared to the results of Comparative Example 11, the introduction of triethoxy(octyl)silane as the only silicon-containing additive reduces the open time, but blending the hydrolyzable silane with PDMS improves the open time.

[0093] [Table 6] * A comparative example is shown.

[0094] As shown in Table 6 above, at a 5 wt% loading of conventional PolyVaE water redispersible powder plus the inventive granular composition, the inventive composition of Example 19 exhibits similarly good standard 28 day and water immersion tensile adhesion as the compositions of Comparative Examples 20 and 21, which contain reinforced RDP with copolymerized vinyl chloride or vinyl versatate and alkyl acrylate. However, the compositions of Examples 13 and 19 of the inventive invention exhibit excellent heat aged tensile adhesion, especially when the amount of RDP plus any granular composition is increased from 3 wt% to 5 wt%.

Claims

1. A storage-stable powder composition for use in the preparation of dry mix compositions, (i) Water-redispersible polymer powder (RDP) and (ii) (a) silicate carrier, (b) polydiorganosiloxane, (c) C ４ ~C １２ (i) a granular composition comprising (d) a hydrolyzable silane or its oligomer containing an alkyl group, and a polymer encapsulant for the hydrolyzable silane and the polydiorganosiloxane, wherein the weight ratio of the total (i) RDP to the total (ii) granular composition is in the range of 90:10 to 98:

2. (i) The RDP is an ethylene-vinyl acetate (VaE) copolymer that does not contain monomers other than ethylene and vinyl acetate in copolymer form, and is a storage-stable powder composition.

2. The storage-stable powder composition according to claim 1, wherein the (ii) granular composition comprises (a) 54 to 89% by weight of the silicate carrier, (b) 4 to 15% by weight of the polydiorganosiloxane, (c) 6.5 to 25% by weight of the hydrolyzable silane, and (d) 0.5 to 6% by weight of the polymer encapsulant for the hydrolyzable silane and the polydiorganosiloxane, and all weight percentages in the granular composition are based on the total weight of the granular composition.

3. The storage-stable powder composition according to claim 1, wherein the silicate carrier (a) of the (ii) granular composition has an average diameter (X50) in the range of 0.2 to 8 μm.

4. The storage-stable powder composition according to claim 1, wherein the (b) polydiorganosiloxane of the (ii) granular composition has a room-temperature viscosity of 40 to 500 mPa·s in its undiluted form.

5. The (ii) granular composition (b) polydiorganosiloxane is a hydroxyl-terminated polydi(C) １ ~C ２ The storage-stable powder composition according to claim 1, wherein the powder is an alkyl siloxane.

6. The storage-stable powder composition according to claim 1, wherein the (c) hydrolyzable silane of the (ii) granular composition comprises octyltrialkoxysilane or an oligomer thereof.

7. A dry mix composition comprising the storage-stable powder composition, cement, and filler described in Claim 1, The dry mix composition comprises 0.5 to 5.5% by weight of (i) RDP and (ii) granular composition based on the total weight of the dry mix composition.

8. A dry mix composition comprising the storage-stable powder composition described in Claim 1, The dry mix composition, The above (i) RDP and the above (ii) granular composition in an amount of 0.5 to 5.5% by weight, Cement in an amount of 15-35% by weight, The remainder of the dry mix composition consists of sand, one or more fillers, or a combination thereof. Includes, The dry mix composition, wherein all weight proportions in the dry mix composition are based on the total weight of the dry mix composition.

9. The dry mix composition according to claim 8, further comprising cellulose ether.