EP4532441A1 - Composition for waterproofing membranes - Google Patents

Composition for waterproofing membranes

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Publication number
EP4532441A1
EP4532441A1 EP23729401.2A EP23729401A EP4532441A1 EP 4532441 A1 EP4532441 A1 EP 4532441A1 EP 23729401 A EP23729401 A EP 23729401A EP 4532441 A1 EP4532441 A1 EP 4532441A1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
powdery
component
monomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23729401.2A
Other languages
German (de)
French (fr)
Inventor
Klaus Seip
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP4532441A1 publication Critical patent/EP4532441A1/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04Portland cements
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045Polymers chosen for their physico-chemical characteristics
    • C04B2103/0057Polymers chosen for their physico-chemical characteristics added as redispersable powders
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045Polymers chosen for their physico-chemical characteristics
    • C04B2103/0065Polymers characterised by their glass transition temperature (Tg)
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
    • C04B2111/00801Membranes; Diaphragms
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/27Water resistance, i.e. waterproof or water-repellent materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34Non-shrinking or non-cracking materials

Definitions

  • the present invention relates to compositions for producing waterproofing membranes comprising a pozzolanic material, at least one powdery filler and an organic polymer P having a glass transition temperature of at most +15°C either in form of an aqueous polymer dispersion or of a polymer powder obtained from the aqueous polymer dispersion.
  • calcium aluminate cement in particular a high alumina cement (HAC), calcium sulfonaluminate cement (CSA) and combinations thereof with OPC have been suggested as mineral binders.
  • these systems often require a lithium based accelerator, such as lithium carbonate, which is expensive and of limited availability due to high demand for electromobility.
  • composition of the invention is not necessarily a physical mixture of components A, B, C and D and optionally further components disclosed herein, but can constitute any desired combination of sub-compositions or of components thereof in which they are not necessarily formulated together.
  • a composition is a two-com- ponent kit comprising a first composition (I) which comprises the components A, B and C and a second composition (II) which comprises the component D.
  • This composition form is for example expedient when a component of one of the compositions interferes with one or more of the components of the other composition. For instance, if composition (II) is aqueous, the water contained therein may start the reaction of components A and B, which is of course to be prevented until the composition is put into application at the desired point of time.
  • the first composition may principally also be formulated as a kit of parts, but is preferably formulated as a physical mixture. It is also possible to formulate the composition of the present invention as a 1 K formulation comprising the polymer P in the form of a polymer powder. Moreover, it is possible to formulate the components A and B as a first powdery composition and to add the components C and D and optionally water immediately before the composition is used for providing the aqueous slurry forming the water-proofing membrane.
  • pozzolanic material refers to natural and artificial pozzolans.
  • Pozzolans are natural or artificial siliceous or siliceous and aluminous rock materials and have been used as construction material since antiquity, e.g. as alphabet caementitium in ancient Rome. They are generally formed of silicium dioxide, clay, limestone, iron oxide and alkaline substances under heat. In themselves, they possess little or no value as binders, but, in finely divided form and in the presence of water, react chemically with calcium hydroxide at ordinary temperature to form a material possessing cementitious properties.
  • Natural pozzolans are either magmatic rock, like volcanic tuff or volcanic trass, or sedimentary rock containing a substantial amount of soluble silicic acid and partially also aluminium oxide (clay).
  • Other pozzolan sources originate from rock metamorphosis caused by meteor strike, like Bavarian trass, Ries trass or Suevit. Trass can thus be of volcanic origin or originate from meteor impact.
  • volcanic trass is poz- zolanic volcanic tuff originating from a volcanic eruption of the Laacher See volcano in the Eifel, Germany and occurring in the Brohl and the Nette valleys.
  • “volcanic trass” relates however to any pozzolanic volcanic tuff, irrespective of its origin.
  • Artificial pozzolans are for example brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations, waste slag, such as blast furnace slag and steel furnace slag resulting from the manufacture of iron and steel.
  • non-slaked lime refers to calcium oxide (CaO) and may also be called burnt lime or quicklime.
  • the term “powdery” with respect to a powdery material means that the material has a particle size of at most 1000 pm, in particular of at most 750 pm.
  • “powdery” pozzolanic material means that the pozzolanic material has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically at most 100 pm.
  • “Powdery” cement means that the cement has a particle size of at most 500 pm, in particular of at most 400 pm, preferably of at most 300 pm or of at most 250 pm and specifically of at most 200 pm.
  • “Powdery” non-slaked lime means that the non-slaked lime has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically of at most 100 pm.
  • the particle size in the filler is not very critical and may be somewhat larger than the particles of the powdery components A and B. It is typically at most 1000 pm, in particular of at most 700 pm.
  • the polymer P of component D may be used in the composition as a polymer powder or as an aqueous polymer dispersion. If the polymer P of component D is present in the form of a polymer powder, the particle size of the polymer powder is not very critical, but is such that the polymer powder can be easily dispersed in water. It is often in the range given above for the pozzolanic material and typically has a particle size of at most 300 pm or at most 250 pm or at most 200 pm. Particle sizes and particle size distributions can be determined using a wide variety of measurement methods known per se to the person skilled in the art, for example via sieve analyses according to DIN 66165-2:2016-08, sedimentation or light scattering, e.g. laser diffraction in accordance with DIN ISO 13321 :2004-10. In the present case, given particle sizes of the components of the powdery composition A are either such as indicated by the commercial producer or as determined using sieve analyses according to DIN 66165-2:2016-08.
  • the pozzolanic material comprises trass (in powdery form, of course).
  • trass preference is given to volcanic trass. More preference is given to volcanic trass.
  • the trass, in particular the volcanic trass constitutes at least 15% by weight, in particular at least 20% by weight, preferably at least 25% by weight and especially at least 30% by weight of the total amount of the pozzolanic material of the component A and may constitute up to 100% by weight of the component A.
  • the component A is essentially free of non-pozzolanic cements, i. e. the amount of non- pozzolanic cement in the component A is at most 10% by weight, in particular at most 5% by weight, based on the total weight of the component A.
  • the pozzolanic material additionally comprises artificial pozzolanic material, such as brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations.
  • the artificial pozzolanic material is preferably brick powder or powdery waste slag.
  • the brick powder also called brick dust or clay dust, is preferably a recycled material, obtained e.g. from comminuting brick waste, e.g. discarded building bricks and roof tiles.
  • Powdery waste slag is ground waste slag, e.g. ground waste slag, such as ground blast furnace slag and ground steel furnace slag resulting from the manufacture of iron and steel.
  • the artificial pozzolanic material not only reduces the amount of natural pozzolanes, thus allowing to preserve pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system.
  • the pozzolanic material comprises or consists of i. 15 to 90% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and ii. 10 to 85% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
  • the pozzolanic material comprises or consists of i. 20 to 85% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
  • the pozzolanic material comprises or consists of i. 25 to 80% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
  • the pozzolanic material comprises or consists of i. 30 to 75% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
  • the cement component B is a cement classified as CEM I.
  • CEM I a cement of class CEM I, contains at least 95% of Portland cement clinker.
  • OPC ordinary Portland cement
  • the cement of class CEM I may be any type of OPC, including Portland cement classified as CEM I 52.5 N, CEM I 42.5 N, CEM I 32.5 N, CEM I 52.5 R, CEM I 42.5 R or CEM I 32.5 R.
  • component B may be replaced by another hydraulic binder, hereinafter component B’, such as gypsum, calcium sulfoaluminate cements (CSA) and/or calcium aluminate cements (HAC), provided that the amount of Portland cement clinker and its ratio to trass is as given above.
  • component B such as gypsum, calcium sulfoaluminate cements (CSA) and/or calcium aluminate cements (HAC), provided that the amount of Portland cement clinker and its ratio to trass is as given above.
  • the relative amount of the component B will be at least 60% by weight, in particular at least 75% by weight and may be as high as 100% by weight, based on the overall weight of the components B and B’ in the composition of the invention.
  • the component B’ is absent or amounts to less than 5% by weight, based on the overall weight of the components B and B’ in the composition of the invention.
  • the weight ratio of the component A to the component B is preferably in the range of 25 : 75 to 95 : 5, in particular in the range of 30 : 70 to 85 : 15 and especially in the range of 40 : 60 to 80 : 20.
  • the overall amount of the component A is preferably in the range of 25 to 50 % by weight, in particular in the range of 30 to 45% by weight, based on the total weight of the components A, B optionally B’ and C.
  • the composition comprises 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the component A, B and C and optionally B’, of volcanic trass and 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the components A, B and C and optionally B’, of brick powder.
  • the overall amount of the components A and B and optionally B’ is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’.
  • the component C hereinafter also termed filler typically comprises a particulate mineral material, in particular a particulate stone material customarily used as reinforcement material to add strength to the overall composite material.
  • the filler as used in the present composition may be any of the usual construction filler, including mineral filler such as rock powder and sand; and recycle filler produced from the recycling of concrete, which is itself chiefly manufactured from mineral filler.
  • Mineral fillers such as powdery dolomite, granites, gravel, sandstone, limestone, basalt and the like can also be used as filler.
  • the present powdery filler may also organic concrete “filler”, such as rubber or bitumen.
  • the present powdery filler typically includes also mixtures of two or more of the above-listed fillers.
  • the overall amount of the powdery filler is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’.
  • the powdery filler comprises sand.
  • the powdery filler comprises preferably at least 50% by weight, more preferably at least 60% by weight, and up to 100% by weight, based on the total weight of the component C, of sand.
  • the sand is a combination of medium sand and fine sand.
  • Fine sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.063-0.2 mm.
  • Medium sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.2-0.63 mm.
  • Medium sand and fine sand are preferably present in a weight ratio of from 2: 1 to 1 :5, more preferably from 1 :1 to 1 :3, in particular from 1 :1.5 to 1 :3.
  • the filler comprises an organic powdery recycling material, such as powdered rubber.
  • the powdered rubber is a recycle material obtained, for example from comminuting discarded tires and the like.
  • the powdered rubber not only reduces the amount of natural mineral fillers, such as sand, thus allowing to preserve their pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system.
  • the organic powdery recycling material has preferably a particle size of at most 500 pm and typically of at least 50 pm.
  • the organic powdery recycling material if contained in the composition, is preferably present in an amount of from 5 to 50% by weight, more preferably from 10 to 40% by weight, in particular 10 to 35% by weight, based on the total weight of the component C. Its amount, if present, is typically in the range of 2 to 25% by weight, in particular 5 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
  • the composition may contain other ingredients.
  • an additional ingredient is kaolin, hereinafter component E.
  • the composition of the invention additionally comprises powdery kaolin.
  • Kaolin also known as China clay, is a hydrated aluminum silicate, which can be approximately described by the simplistic and idealized formula AI2O3 ⁇ 2SiC>2 ⁇ 2H2O. It is a natural, fine-grained and well crystallized clay mineral with a layered structure.
  • Kaolin if contained in the composition, is preferably present in an amount of from 1 to 10% by weight, more preferably from 1 to 5% by weight, in particular from 2 to 3% by weight, based on the total weight of the components A, B and C and optionally B’.
  • the kaolin has preferably a particle size of at most 500 pm, more preferably of at most 300 pm, in particular of at most 100 pm.
  • the composition of the invention may also contain non-slaked lime as a component F.
  • non-slaked lime as a component F.
  • the use of non-slaked lime in the present composition leads to a distinctly faster setting. Moreover, it allows to reduce the amount of calcium needed for setting.
  • the amount of the non-slaked lime is preferably in the range of 5 to 20% by weight, in particular in the range of 8 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
  • a particular group of embodiment of the invention relates to compositions which do not contain non-slaked lime or less than 5% by weight of non-slaked lime, based on the total weight of the components A, B and C and optionally B’.
  • composition of the invention may moreover contain other additives typical for such formulations, such as rheology modifiers (e.g. thickeners, plasticizers), accelerators or retardants (for the setting process) and wetting agents or dispersants, respectively.
  • rheology modifiers e.g. thickeners, plasticizers
  • accelerators or retardants for the setting process
  • wetting agents or dispersants wetting agents or dispersants, respectively.
  • component G The total amount of these additives is usually at most 5% by weight, preferably at most 2% by weight, based on the total weight of components A, B and C and optionally B’ and e. g. in the range of 0.1 to 5 % by weight or in the range of 0.2 to 2% by weight, if present.
  • wetting agents and “dispersants” are used synonymously. They allow for reducing the amount of make-up water required for producing the slurry.
  • Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1 -diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts.
  • polymeric dispersants such as alkali metal salts and ammonium salts of acrylic acid polymers or maleic anhydride polymers.
  • a metal salt of polyacrylic acid is used as a dispersant or wetting agent, respectively.
  • the composition of the invention contains the dispersant, in particular the polymeric dispersant, in an amount of from 0.1 to 5% by weight, in particular of from 0.3 to 3% by weight, based on the total weight of the components A and B.
  • the composition is formulated as a 2K composition which comprises a first powdery composition (I), which contains the powdery components A, B and C and optionally the powdery components B’, E, F and G, and a second composition (I) which contains the polymer P, in particular in the form of an aqueous polymer dispersion.
  • a first powdery composition (I) which contains the powdery components A, B and C and optionally the powdery components B’, E, F and G
  • a second composition (I) which contains the polymer P, in particular in the form of an aqueous polymer dispersion.
  • composition (I) comprises or consists of:
  • component C 35 to 65% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
  • composition (I) comprises or consists of:
  • component A 30 to 45% by weight of the component A, in particular a combination of volcanic trass and brick powder;
  • component C 40 to 55% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
  • a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of in the range of 45 to 59% by weight, and where the weight ratio of the trass of component A to the cement clinker of the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
  • a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
  • the composition comprises or consists of: (a.1 ) 15 to 30% of trass, in particular volcanic trass;
  • a further additive in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of 44 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
  • the composition of the invention further comprises a polymer P.
  • the polymer P of the component B may be present either as an aqueous polymer dispersion or as a polymer powder, in particular a polymer powder which is obtained by spray-drying of an aqueous polymer dispersion of the polymer P.
  • the polymer P comprises a polymer powder obtained from the above-described aqueous polymer dispersion, where the polymer of the aqueous polymer dispersion has a glass transition temperature Tg of at most +15°C, in particular at most +10°C, more particularly at most +5°C, especially at most 0°C.
  • the glass transition temperature Tg is at least -60°C, frequently at least -50°C, in particular at least -40°C more particularly at least -30°C and especially at least -25°C.
  • the Tg of the polymer is in the range of -60 to +15°C.
  • the polymers P are insoluble in water and are present in the form of discrete polymer particles.
  • the average diameter of the polymer particles present in aqueous dispersion is generally in the range from 10 to 1000 nm, frequently in the range from 20 to 850 nm, e.g. from 100 to 700 nm.
  • this specification means the Z average particle diameter as determined by dynamic light scattering (also termed quasielastic light scattering) of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5% by weight at 22°C by means of a HPPS from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321 ).
  • the aqueous dispersion of the polymer P is generally a polymer obtained by emulsion polymerization of ethylenically unsaturated monomers M, hereinafter also referred to as polymer emulsions.
  • Polymer emulsions are familiar to the skilled person and are prepared, for example, in the form of an aqueous polymer dispersion by means of radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers M. This technique has been exhaustively described in the art, and is therefore well known to the skilled person [cf., e.g., Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; D. C.
  • the radically initiated aqueous emulsion polymerization is normally accomplished by dispersing the ethylenically unsaturated monomers in aqueous medium, generally with accompanying use of dispersing assistants, such as emulsifiers and/or protective colloids, and polymerizing them by means of at least one water- soluble radical polymerization initiator.
  • dispersing assistants such as emulsifiers and/or protective colloids
  • the residual amounts of unreacted ethylenically unsaturated monomers are frequently lowered by chemical and/or physical techniques that are likewise known to the skilled person [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586, and 19847115]; the polymer solids content is adjusted to a desired level by dilution or concentration; or the aqueous polymer dispersion is admixed with further customary adjuvants, such as bactericidal, foam-modifying or viscositymodifying additives, for example.
  • further customary adjuvants such as bactericidal, foam-modifying or viscositymodifying additives, for example.
  • водородн ⁇ е ⁇ ок ком ⁇ онент ⁇ As well as these so-called primary aqueous polymer dispersions, the skilled person also knows of what are called secondary aqueous polymer dispersions. These are understood to be aqueous polymer dispersions in whose preparation the polymer is generated outside of the aqueous dispersing medium, as for example in solution in a suitable nonaqueous solvent. This solution is subsequently transferred into the aqueous dispersing medium, and the solvent is separated off with dispersing, generally by distillation.
  • secondary aqueous polymer dispersions These are understood to be aqueous polymer dispersions in whose preparation the polymer is generated outside of the aqueous dispersing medium, as for example in solution in a suitable nonaqueous solvent. This solution is subsequently transferred into the aqueous dispersing medium, and the solvent is separated off with dispersing, generally by distillation.
  • the aqueous polymer dispersion of the polymer P is a primary aqueous polymer dispersion, in particular an aqueous polymer dispersion, which is obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M.
  • the polymer P is a copolymer of ethylenically unsaturated monomers M.
  • copolymer refers to polymers which are made of two or more, e.g. 2, 3, 4, 5 or 6 or more different ethylenically unsaturated monomers M.
  • the copolymer comprises both ethylenically unsaturated comonomers with a rather low and with a higher solubility in water, where the comonomers of rather low solubility preferably constitute the major part of the polymer.
  • Ethylenically unsaturated monomers of low water-solubility are those having a solubility in water of not more than 50 g/l at 20°C and 1 bar.
  • monomers M 1 Monomers of higher water-solubility are those having a solubility in water of at least 60 g/l at 20°C and 1 bar. These monomers are hereinafter referred to as monomers M2.
  • the polymer P is composed of i) 80 to 99.9 pphm, more particularly 85 to 99.5 pphm, of at least one neutral, nonfunctional monoethylenically monomer M.1 having a water-solubility in deionized water of not more than 50 g/l at 20°C and 1 bar, e. g. in the range of 0.01 to 50 g/l; and ii) 0.1 to 20 pphm, more particularly 0.5 to 15 pphm, of at least one further ethyleni- cally unsaturated monomer other than the monomers M 1 .
  • pphm means part per hundred parts of monomers and is an abbreviation of the term “% by weight, based on the total amount of monomers”.
  • neutral means that the monomer has neither a basic or acidic group nor a ionic group.
  • non-functional means that the monomer has no functional group, which is capable to undergo a polymer analogue reaction, i. e. a bond-forming reaction with another group of the polymer or with a crosslinking agent or with inorganic matter.
  • unsaturated monomer other than the monomers M1 refers to monoethylenically unsaturated neutral monomers having a water-solubility in deionized water of more than 50 g/l at 20°C and 1 bar, e. g. at least 60 g/l at 20°C and 1 bar; monoethylenically unsaturated monomers having a basic or acidic group or a ionic group, e. g.
  • a keto carbonyl group an aldehyde group, an isocyanate group, a 1 ,3-dicarbonyl group, a urea group, an N- alkylolamide group or a hydrolysable silane group; and ethylenically unsaturated monomers having at least 2 ethylenically unsaturated double bonds.
  • Examples of neutral, non-functional monoethylenically unsaturated monomers M.1 are: esters of acrylic and/or methacrylic acid with alkanols having 1 to 20 C atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2- octyl acrylate, 2-ethylhexyl acrylate, 2-propylpentyl acrylate, n-decyl acrylate, 2- propylheptyl acrylate, Cw isoamyl guerbet acrylate, 1
  • C1-C20 alkyl esters of methacrylic acid include, but are not limited to methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylpentyl methacrylate, n- decyl methacrylate, 2-propylheptyl methacrylate, Cw isoamyl guerbet methacrylate, 1 -propylheptyl methacryl
  • Preferred monomers M1 are esters of acrylic with alkanols having 1 to 10 C atoms esters of methacrylic acid with alkanols having 1 to 10 C atoms, esters of acrylic with cycloalkanols having 5 to 10 C atoms esters of methacrylic acid with cycloalkanols having 5 to 10 C atoms, furfuryl acrylate, furfuryl methacrylate, vinylaromatic hydrocarbon compounds, specifically styrene, conjugated alkadienes, specifically butadiene, vinyl esters of saturated Ci-Cs alkanoic acids, specifically vinylacetate, and olefins, specifically ethylene and combinations thereof.
  • the polymers P are selected from copolymers of a vinylaromatic compound M 1 a, in particular styrene and at least one further monomer M 1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cio-alkylesters of acrylic acid, alkylesters, in particular Ci-Cw-a Iky I esters of methacrylic acid, cycloalkylesters, in particular Cs-Cw-cy- cloalkylesters of acrylic acid and cycloalkylesters, in particular Cs-Cw-cycloal- kylesters of methacrylic acid and mixtures thereof, e.g.
  • the polymers P are selected from styrene-acrylate copolymers, styrenebutadiene copolymers, all-acrylic copolymers, acrylonitrile-acrylate copolymers, vinyl acetate polymers and ethylene-vinylacetate copolymers with particular preference given to styrene-acrylate copolymers and styrene-butadiene copolymers.
  • the monomers M which form the polymer P comprise: i. 80 to 99.9% by weight, in particular 85 to 99.5% by weight, based on the total amount of monomers M, of at least one monomer M1 , which is selected from a combination of at least one monovinylaromatic monomer M1 a and at least one further monomer M1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid and/or methacrylic acid and cycloalkylesters, in particular Cs-Cw-cycloalkylesters of acrylic acid and/or methacrylic acid and mixtures thereof;
  • the monomers M2 are as defined above and preferably selected from primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms, such as acrylamide and methacrylamide, and esters of acrylic and/or methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate.
  • primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms such as acrylamide and methacrylamide
  • M2 is selected from acrylamide, methacrylamide and esters of methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate.
  • M2 is selected from the group consisting of acrylamide, methacrylamide, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • the monomers M3 are as defined above and preferably selected from methacrylic acid, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, and 2- acrylamido-2-methylpropanesulfonic and their salts, in particular their sodium, potassium or ammonium salts, and the monomers of the formula M3c-I, such as mono- (meth)acryloxyethyl phosphate, mono-(meth)acryloxypropyl phosphate, mono- (meth)acryl(oxy-l ,2-ethanediyl)i-2o phosphate and mono-(meth)acryl(oxy-1 ,2- propandiyl)i-2o phosphate and their salts, in particular their sodium, potassium or ammonium salts.
  • the monomers M4 are as defined above and preferably selected from the group consisting of the monomers M4a and M4c with particular preference given to monomers M4a bearing a 1 ,3-dicarbonyl moiety, such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, acetoacetoxyethyl methacrylate, and epoxy functionalized (meth)acrylate monomers, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate.
  • a 1 ,3-dicarbonyl moiety such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacryl
  • a hydrolysable silane group which are in particular selected from vinyltrial- koxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular methacryloxypropyltrimethoxysilane.
  • the monomers M which form the polymer P may be of petrochemical origin or may be of bio-renewable sources. In particular at least 30% by weight of the monomers M, preferably at least 40% by weight or at least 50% by weight of the monomers M are based on bio-renewable sources, which means that their content of bio carbon is at least 30 mol-%, in particular at least 40 mol-%, based on the total amount of carbon in the monomers from bio-renewable sources.
  • bio-carbon indicates that the carbon is of biological origin and comes from a biomaterial/renewable resources.
  • the content in bio-carbon and the content in biomaterial are expressions that indicate the same value.
  • a material of renewable origin or biomaterial is an organic material wherein the carbon comes from the CO2 fixed recently (on a human scale) by photosynthesis from the atmosphere.
  • a biomaterial Carbon of 100% natural origin
  • the isotopic 14 C is formed in the atmosphere and is then integrated via photosynthesis, according to a time scale of a few tens of years at most. The half-life of the 14 C is 5,730 years.
  • the materials coming from photosynthesis namely plants in general, necessarily have a maximum content in isotope 14 C.
  • the determination of the content of biomaterial or of bio-carbon is can be carried out in accordance with the standards ASTM D 6866-12, the method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
  • bio-renewable sources refer to organic materials in which the carbon comes from non-fossil biological sources.
  • bio-renewable sources include, but are not limited to, sugars, such as glucose or saccharose, and starches obtained from plants, such as corn, cereals, sugarcanes, beets, potatoes, sweet potatoes or cassava, other polysaccharides of plant origin, such as celluloses, lignocelluoses, hemicelluloses, pectin, chitin, levan and pullulan, plant oils, biomass obtained from plants or agriculturaly waste and the like.
  • sugars such as glucose or saccharose
  • starches obtained from plants, such as corn, cereals, sugarcanes, beets, potatoes, sweet potatoes or cassava
  • other polysaccharides of plant origin such as celluloses, lignocelluoses, hemicelluloses, pectin, chitin, levan and pullulan
  • plant oils biomass obtained from plants or agriculturaly waste and the like
  • the monomers and monomer precursors such as alcohols and fatty acids, can be directly produced from such biological recources via biological processes, including fermentation and the like.
  • Examples of monomers and monomer precursors which can be directly obtained from biorenewable sources are acrylic acid, methacrylic acid, itaconic acid, the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid, wherein the at least the carbon atoms of the alkyl and cycloalkyl group, respectively, are of biological origin, i.e. e. they are at least partly made of bio-carbon.
  • the respective alkanols and cycloalkanols used for the production of the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid preferably have a content of bio-carbon of at least 70 mol-%, based on the total amount of carbon atoms in the respective monomers. This content is advantageously higher, in particular greater than or equal to 80 mol-%, preferably greater than or equal to 90 mol-% and advantageously equal to 100 mol-%.
  • itaconic acid, citraconic acid and mesaconic acid can be produced on large scale from renewable materials, e.g. by fermentation of glucose, saccharose, starch or cellulose containing raw materials.
  • acrylic acid and methacrylic acid may be produced from biorenewable sources. Further examples are vinyl esters of alkanoic acid, where at least the alkanoic acid is produced from biorenewable sources.
  • the polymer content is preferably from 20 to 65% by weight, more preferably from 30 to 60% by weight and in particular from 35 to 55% by weight, based on the total weight of the aqueous composition (II).
  • the surface active compound may be an emulsifier, a protective colloid or a mixture of both of them.
  • the emulsifier and the protective colloid are distinct from each other by their weight-average molar mass M w .
  • An emulsifier has typically a weight-average molar mass M w in general below 2000, while the weight-average molar mass M w of the protective colloid may be up to 50 000, in particular from above 2000 to up to 50000.
  • the amount of the surface active compound is in the range from 0.1 to 10% by weight, in partiuclar in the range from 0.5 to 5% by weight, based on the total amount of polymer in the aqueous polymer dispersion.
  • the surface active compound comprises one or more emulsifiers.
  • the emulsifier is non-ionic, anionic, or cationic. In case of employing a mixture of emulsifiers, their compatibility has to assured, which can be evaluated in case of doubt by preliminary tests.
  • an anionic emulsifier is compatible with another anionic emulsifier or a non-ionic emulsifier.
  • a cationic emulsifier is typically compatible with another cationic emulsifier or a non-ionic emulsifier.
  • the emulsifier is an anionic emulsifier, a combination of two or more anionic emulsifier or a combination of at least one anionic emulsifier and at least one non-ionic emulsifier.
  • Examples of customary nonionic emulsifiers are the Emulgin B grades (cetyl/stearyl alcohol ethoxylates, RTM BASF), Dehydrol LS grades (fatty alcohol ethoxylates, EO units: 1-10, RTM BASF), Lutensol A grades (Ci2Ci4-fatty alcohol ethoxylates, EO units: 3-8, RTM BASF), Lutensol AO grades (C13C15-OXO alcohol ethoxylates, EO units: 3-30), Lutensol AT grades (Ci 6 Ci8-fatty alcohol ethoxylates, EO units: 11-80), Lutensol ON grades (Cw-oxo alcohol ethoxylates, EO units: 3-11) and Lutensol TO grades (C -oxo alcohol ethoxylates, EO units: 3-20).
  • EO units means the number average of ethylene oxide repeating units in the emulsifier.
  • Anionic emulsifiers include for example the alkali metal salts of dialkyl esters of sulfosuccinic acid, the alkali metal salts and the ammonium salt of C8-C12 alkyl sulfates, the alkali metal salts and the ammonium salts of C12-C18 alkylsulfonic acids, the alkali metal salts and the ammonium salts of C9-C18 alkylarylsulfonic acid, the alkali metal salts and the ammonium salts of sulfuric acid monoesters of ethoxylated C12-C18 alkanols (EO units: 4-30) or a sulfuric acid monoester of an ethoxylated (C4-C12 alkyl)phe- nol (EO units: 3-50).
  • R a and R b are each a H atom or C4-C24-alkyl and are not both H atoms at the same time, and Mi + and M2 + can be alkali metal ions and/or ammonium, are also useful.
  • R a and R b are preferably linear or branched alkyl radicals having from 6 to 18 carbon atoms, in particular 6, 12 or 16 carbon atoms, or hydrogen atoms, where R a and R b are not both hydrogen atoms at the same time.
  • Mi + and M2 + are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • a compound of general formula I, in which Mi + and M2 + are both sodium, R a is a branched alkyl radical having 12 carbon atoms and R b is hydrogen or R a is particularly advantageous.
  • Use is frequently made of industrial mixtures which have a proportion of from 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (RTM The Dow Chemical Corp.).
  • the compounds of general formula I are commonly known, e.g. from US-A 4 269 749, and commercially available.
  • emulsifiers are fatty alcohol phosphates, alkylphenol phosphates, alkyl polyglycol ether phosphates, alkyl polyalkylene oxide phosphates, and fatty alcohol ether phosphates and the salts thereof, in particular the alkalimetal salts and ammonium salts thereof, with particular preference given to the alkalimetal salts such as sodium salts.
  • suitable emulsifiers may be found in Houben-Weyl, Methoden der organischen Chemie, volume XIV/1 , Makromolekulare Stoffe, Georg- Thieme-Verlag, Stuttgart, 1961 , pages 192 to 208.
  • suitable protective colloids may be non-ionic, anionic or cationic.
  • protective colloids are poly(vinyl alcohols), poly(alkylene glycols), poly(acrylic acids) and the alkali metal salt thereof, poly(methacrylic acids) and the alkali metal salt thereof and gelatin derivatives.
  • Anionic protective colloid can also be a copolymer, containing a suitable amount of at least one anionic monomer, such as acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, para-vinylphenyl sulfonic acid or salt forms thereof, preferably alkali metal salts thereof, in polymerized form.
  • cationic protective colloids are homopolymers and copolymers containing a sufficient amount of cationic monomers, in particular monoethylenically unsaturated monomers having one or more amino groups, which are N-protonated or N-alkylated.
  • Examples include N-protonated and N-alkylated derivatives of homopolymers or copolymers of N -vinylform am ide in their at least partly hydrolyzed form, homopolymers or copolymers of N-vinylacetamide in their at least partly hydrolyzed form, N-protonated and N-alkylated derivatives of homopolymers or copolymers of N-vinylcarbazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 1-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylpyridine, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 4-vinylpyridine, N-proton
  • the protective colloids are distinct from the polymers dispersed in the aqueous polymer dispersion as they are water-soluble or water dispersible.
  • water-soluble or water dispersible is understood that the corresponding protective colloid can be dissolved or dispersed in deionized water at 20°C and 1013 mbar in an amount of at least 10 g/L polymer such that the resulting aqueous solution has either no measurable particle size or a particle size of at most 20 nm as determined by dynamic light scattering in accordance with DIN 22412:2008.
  • composition of the invention may moreover contain further auxiliaries, such as
  • composition of the invention is formulated as a 2K formulation
  • the auxiliaries are generally incorporated in composition (II).
  • Flow control agents and defoamers may however also be incorporated in composition (I).
  • Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1- diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts.
  • polymeric dispersants such as alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers.
  • a metal salt of polyacrylic acid is used.
  • the polymeric dispersant is contained in an amount of from 0.1 to 2% by weight, in particular from 0.1 to 1 % by weight, based on the total weight of the polymer of composition (II).
  • Acronal® 5400 from BASF SE; aqueous anionic copolymer dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 57%, Tg: -8°C; viscosity (250 s -1 at 23°C; DIN EN ISO 3219): 50-350 mPa-s, pH 5.5-7.5.
  • - Acronal 5442® from BASF SE; aqueous, self-cross-linking dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 53.5%, Tg: ca. -15°C; viscosity (100 s -1 at 23°C; DIN EN ISO 3219): 10-100 mPa-s, pH 5.5-8.5.
  • 300 g of the formulations were mixed in a 500 ml plastic cup (yoghurt pot). Immediately after mixing, the mass was checked for consistency with a knife spatula. The creaminess and stickiness of the mass was assessed. The dripping from the knife spatula was also assessed. Furthermore, the compound was applied to a concrete block with a 6 mm notched trowel and the processing properties were also assessed.
  • compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
  • compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
  • compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec. The obtained mixture was directly coated onto a mortar prism according to DIN EN 14891 A8. After coating of a very fine coat (scratch spatula) and drying ( ⁇ 20 min) the first waterproofing coating was applied (thickness 1 .2 mm wet). After drying (approx. 3h) a second layer was coated (thickness also 1 .2 mm wet). For each test formulation a preparation of three samples were done (3 samples for 23°C test, 3 samples for -5°C test and 3 samples for -20°C test).
  • the samples obtained in a) were kept at ambient conditions for 28 days and then stored in chlorine water for 7 days.
  • Chlorine water was prepared from 200 mg/l NaCI, 200 mg/l of Na2SC>4 and NaOCI kept at a concentration of 0.3 to 0.6 mg/l.
  • the pH was kept at 6.5 to 7.8. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b).
  • the samples obtained in a) were kept at ambient conditions for 28 days and then stored in 3% by weight aqueous solution of potassium hydroxide for 14 days at 40°C. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b).
  • compositions 1 to 6, 8 and 9 showed good water tightness at > 2.5 bar and low water absorption. The test results are summarized in table 7.
  • compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed whereby slurries were obtained which can be used for producing the water-tight coverings.
  • Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape.
  • 300 g of the thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel.
  • the film thickness was thus 2.5 mm for wet application.
  • the test was performed as follows: A film of the waterproofing composition was applied to a Teflon foil in a layer thickness of 4 mm (dry film thickness). After 28 days of drying, the film was then placed on the slit pressure plate (in contrast to the standard, a rectangular shaped plate of 20x20 cm was used. The slit width was 1 mm and the slit length was 25 mm). A water pressure of 2.5 bar was then applied to the sealing surface for 24 hours.
  • the sealing films prepared from all compositions 1 to 9 provided good water tightness, as can be seen from the test results summarized in table 9.
  • a waterproofing slurry film of 3mm dry film thickness was produced.
  • the film had a width of 50 mm and a length of 200 mm.
  • the films and the test mandrel were stored at 0°C for at least 1 h and then the film was slowly bent over the mandrel within 3s. The film must not tear in the process.
  • the test results are summarized in table 10.
  • the early rain resistance was measured according to DIN EN 15816.
  • the waterproofing was applied to a concrete slab in a wet layer thickness of 3 mm. After 4 or 8 hours drying time, the spray water test was carried out. The spraying time was

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Abstract

The present invention relates to compositions for producing waterproofing membranes comprising a) a powdery pozzolanic material as a component A, which comprises a powdery trass in an amount of at least 15% by weight, in particular at least 20% by weight especially at least 25% by weight or at least 30% by weight, based on the total amount of the component A, i. e. of the powdery pozzolanic material; b) a powdery cement as a component B comprising Portland cement clinker in an amount of at least 15% by weight, in particular at least 25% by weight, especially at least 35% by weight or at least 45% by weight of the total amount of the component B; c) at least one powdery filler as a component C; d) an organic polymer P as a component D in the form of an aqueous polymer dispersion or in the form of a polymer powder, where the polymer P has a glass transition temperature Tg of at most +10°C, in particular at most +5°C, preferably in the range of -30 to +10°C, especially in the range of -20 to +5°C, as determined by the differential scanning calorimetry (DSC) method according to ISO 11357-2:2013; wherein the weight ratio of the trass to the Portland cement clinker is in the range of 5 : 95 to 95 : 5, in particular in the range of 10 : 90 to 90 : 10 and especially in the range of 20 : 80 to 80 : 20. The invention also relates to the use of said composition for providing waterproofing membranes. Moreover, the invention relates to a method for providing waterproofing membranes which comprises providing the composition as described herein in the form of an aqueous slurry of the components of the composition, e. g. by mixing the components of the composition with water or by mixing a powdery composition comprising the components A, B and C and optionally further powdery components with an aqueous dispersion of the polymer P, and applying the aqueous slurry to a surface, where a water-tight covering is required. Upon hardening of the thus obtained coating, the water-proofing membrane is obtained.

Description

Composition for waterproofing membranes
The present invention relates to compositions for producing waterproofing membranes comprising a pozzolanic material, at least one powdery filler and an organic polymer P having a glass transition temperature of at most +15°C either in form of an aqueous polymer dispersion or of a polymer powder obtained from the aqueous polymer dispersion.
TECHNICAL BACKGROUND
In construction, waterproofing membranes as used for example in water drains, such as sewage or rainwater drains and lines, for waterproofing of buildings and parts of buildings, for example for waterproofing of basements or as water barrier under tiles in wet rooms (e.g. bathrooms), swimming pools or water tanks are typically based on a cement - organic polymer system. Due to the content of cement binders and optinally mineral fillers, they are also termed mineral coverings. Typically, the compositions for waterproofing membranes contain a cement binder of the cement groups CEM I according to EN 197-1 :2011 (ordinary Portland cement, also termed OPC), in particular a quick setting type or a mixture thereof, as a main constituent of the mineral binder. Alternatively, calcium aluminate cement, in particular a high alumina cement (HAC), calcium sulfonaluminate cement (CSA) and combinations thereof with OPC have been suggested as mineral binders. A combination of OPC, HAC and gypsum have also been described for quick-setting compositions. However, these systems often require a lithium based accelerator, such as lithium carbonate, which is expensive and of limited availability due to high demand for electromobility.
Compositions for waterproofing membranes containing OPC as mineral binder have been frequently described, e. g. in US 2018/0179108.
WO 2016/142339 describes a composition for sealing slurries comprising a hydraulic binder, silica sand, limestone powder and a polymer, where the hydraulic binder comprises a calcium aluminate cement, in particular a high alumina cement (HAC), a calcium sulfonaluminate cement (CSA) or a mixture thereof.
US 2018/0327310 describes a two-component composition for making a water-proofing membrane, comprsing as one component an emulsion polymer and as a separate component, a fast curing dry mix powder composition of a conventional OPC and a high alumina cement. Mineral waterproofing membranes based on these cement-polymer systems are, however, not satisfying as regards their flexibility or elasticity, which becomes manifest in a dissatisfying crack bridging ability, especially at low temperatures, probably due to the quick setting of typical cement-based binding systems. Good crack bridging properties are not only important for the resistance of waterproofing membranes against mechanical or temperature stress, but also for the suitability of such systems as mending materials, for example for water-bearing construction, such as rain drains or sewage pipes. Moreover, these cement based systems become brittle over time because the cement contained in them is only partially converted and therefore postreacts. Moreover, mineral waterproofing membranes based on cement-polymer systems are not entirely satisfying as regards their resistance against acidic and corrosive substances.
Moreover, there is an urgent need to reduce the production and consumption of cement. The currently prevalent cement type, hydraulic cement, is obtained by sintering limestone and aluminosilicate materials such as clay at ca. 1450°C. During sintering, limestone (CaCOs) is calcinated to lime (CaO), setting free CO2. Given the high energy consumption yet for providing the required temperature (generally by burning fossil fuel), the CO2 formation both inherently from the calcination process and from energy production, and of course the sheer amount used worldwide in construction, cement production has become a massive source of the world's CO2 emissions. It is therefore desirable to replace cement at least partially by a material with a smaller carbon footprint.
Earlier patent application PCT/EP2021/083482 describes a 2K composition for providing water-proofing membranes which comprise a pozzolanic material, such as volcanic tuff, non-slaked lime and a filmforming polymer having a glass transition temperature of at most +15°C.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide compositions for waterproofing applications, in particular for waterproofing membranes, which, after setting, are watertight, resistent against acidic and alkaline substances and also against other corrosive substances, in patricular chlorine-containing substances, which have a high elasticity or flexibility, becoming manifest for example in a good crack bridging ability, especially at low temperatures, and has a high bond strength. Setting times should also be satisfactory and the composition should not tend to become brittle over time. Moreover, its production shall be less energy-intensive and CO2 release shall be reduced as compared to cement binder systems. Further, it shall be combinable with recycled materials, e.g. brick powder or powdered rubber, thus allowing to reduce the amount of mineral fillers such as sand, the natural reservoirs of which have been running off lately.
The object is achieved by compositions comprising a powdery pozzolanic material comprising powdery trass as a component A, a powdery cement comprising Portland cement clinker as a component B, where the weight ratio of the trass to the Portland cement clinker of component B in the range of 5 : 95 to 95 : 5, further comprising one or more powdery fillers and a polymer based on ethylenically unsaturated monomers with a glass transition temperature Tg of at most +10°C.
The invention thus relates to compositions for producing waterproofing membranes, which comprise a) a powdery pozzolanic material as a component A, which comprises a powdery trass in an amount of at least 15% by weight, in particular at least 20% by weight especially at least 25% by weight or at least 30% by weight, based on the total amount of the component A, i. e. of the powdery pozzolanic material; b) a powdery cement as a component B comprising Portland cement clinker in an amount of at least 15% by weight, in particular at least 25% by weight, especially at least 35% by weight or at least 45% by weight of the total amount of the component B; c) at least one powdery filler as a component C; d) an organic polymer P as a component D in the form of an aqueous polymer dispersion or in the form of a polymer powder, where the polymer P has a glass transition temperature Tg of at most +10°C, in particular at most +5°C, preferably in the range of -30 to +10°C, especially in the range of -20 to +5°C, as determined by the differential scanning calorimetry (DSC) method according to ISO 11357-2:2013; wherein the weight ratio of the trass to the Portland cement clinker is in the range of 5 : 95 to 95 : 5, in particular in the range of 10 : 90 to 90 : 10 and especially in the range of 20 : 80 to 80 : 20.
The invention also relates to the use of said composition for providing waterproofing membranes.
Moreover, the invention relates to a method for providing waterproofing membranes which comprises providing the composition as described herein in the form of an aqueous slurry of the components of the composition, e. g. by mixing the components of the composition with water or by mixing a powdery composition comprising the components A, B and C and optionally further powdery components with an aqueous dispersion of the polymer P, and applying the aqueous slurry to a surface, where a watertight covering is required. Upon hardening of the thus obtained coating, the waterproofing membrane is obtained.
DETAILED DESCRIPTION OF THE INVENTION
The composition of the invention is not necessarily a physical mixture of components A, B, C and D and optionally further components disclosed herein, but can constitute any desired combination of sub-compositions or of components thereof in which they are not necessarily formulated together. One example of a composition is a two-com- ponent kit comprising a first composition (I) which comprises the components A, B and C and a second composition (II) which comprises the component D. This composition form is for example expedient when a component of one of the compositions interferes with one or more of the components of the other composition. For instance, if composition (II) is aqueous, the water contained therein may start the reaction of components A and B, which is of course to be prevented until the composition is put into application at the desired point of time. The first composition may principally also be formulated as a kit of parts, but is preferably formulated as a physical mixture. It is also possible to formulate the composition of the present invention as a 1 K formulation comprising the polymer P in the form of a polymer powder. Moreover, it is possible to formulate the components A and B as a first powdery composition and to add the components C and D and optionally water immediately before the composition is used for providing the aqueous slurry forming the water-proofing membrane.
The term “pozzolanic material” refers to natural and artificial pozzolans. Pozzolans are natural or artificial siliceous or siliceous and aluminous rock materials and have been used as construction material since antiquity, e.g. as opus caementitium in ancient Rome. They are generally formed of silicium dioxide, clay, limestone, iron oxide and alkaline substances under heat. In themselves, they possess little or no value as binders, but, in finely divided form and in the presence of water, react chemically with calcium hydroxide at ordinary temperature to form a material possessing cementitious properties.
Natural pozzolans are either magmatic rock, like volcanic tuff or volcanic trass, or sedimentary rock containing a substantial amount of soluble silicic acid and partially also aluminium oxide (clay). Other pozzolan sources originate from rock metamorphosis caused by meteor strike, like Bavarian trass, Ries trass or Suevit. Trass can thus be of volcanic origin or originate from meteor impact. Strictly speaking, volcanic trass is poz- zolanic volcanic tuff originating from a volcanic eruption of the Laacher See volcano in the Eifel, Germany and occurring in the Brohl and the Nette valleys. In the present invention, “volcanic trass” relates however to any pozzolanic volcanic tuff, irrespective of its origin.
Artificial pozzolans are for example brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations, waste slag, such as blast furnace slag and steel furnace slag resulting from the manufacture of iron and steel.
The term “non-slaked lime” refers to calcium oxide (CaO) and may also be called burnt lime or quicklime.
In general, the term “powdery” with respect to a powdery material means that the material has a particle size of at most 1000 pm, in particular of at most 750 pm.
For example, “powdery” pozzolanic material means that the pozzolanic material has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically at most 100 pm.
“Powdery” cement means that the cement has a particle size of at most 500 pm, in particular of at most 400 pm, preferably of at most 300 pm or of at most 250 pm and specifically of at most 200 pm.
“Powdery” non-slaked lime means that the non-slaked lime has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm and specifically of at most 100 pm.
The particle size in the filler is not very critical and may be somewhat larger than the particles of the powdery components A and B. It is typically at most 1000 pm, in particular of at most 700 pm.
The polymer P of component D may be used in the composition as a polymer powder or as an aqueous polymer dispersion. If the polymer P of component D is present in the form of a polymer powder, the particle size of the polymer powder is not very critical, but is such that the polymer powder can be easily dispersed in water. It is often in the range given above for the pozzolanic material and typically has a particle size of at most 300 pm or at most 250 pm or at most 200 pm. Particle sizes and particle size distributions can be determined using a wide variety of measurement methods known per se to the person skilled in the art, for example via sieve analyses according to DIN 66165-2:2016-08, sedimentation or light scattering, e.g. laser diffraction in accordance with DIN ISO 13321 :2004-10. In the present case, given particle sizes of the components of the powdery composition A are either such as indicated by the commercial producer or as determined using sieve analyses according to DIN 66165-2:2016-08.
The remarks made in the following to suitable and preferred embodiments of the invention, in particular to suitable and preferred features of the components of the composition of the invention and their application apply both on their own as well as in any combination with each other.
According to the invention, the pozzolanic material comprises trass (in powdery form, of course). Among the trass, preference is given to volcanic trass. More preference is given to volcanic trass. The trass, in particular the volcanic trass, constitutes at least 15% by weight, in particular at least 20% by weight, preferably at least 25% by weight and especially at least 30% by weight of the total amount of the pozzolanic material of the component A and may constitute up to 100% by weight of the component A. The component A is essentially free of non-pozzolanic cements, i. e. the amount of non- pozzolanic cement in the component A is at most 10% by weight, in particular at most 5% by weight, based on the total weight of the component A.
In a particular embodiment, the pozzolanic material additionally comprises artificial pozzolanic material, such as brick powder or fly ash as obtained, for example, from brown coal- or hard coal-fired power stations. The artificial pozzolanic material is preferably brick powder or powdery waste slag. The brick powder, also called brick dust or clay dust, is preferably a recycled material, obtained e.g. from comminuting brick waste, e.g. discarded building bricks and roof tiles. Powdery waste slag is ground waste slag, e.g. ground waste slag, such as ground blast furnace slag and ground steel furnace slag resulting from the manufacture of iron and steel. The artificial pozzolanic material not only reduces the amount of natural pozzolanes, thus allowing to preserve pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system.
In a preferred embodiment, the pozzolanic material comprises or consists of i. 15 to 90% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and ii. 10 to 85% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
More preferably, the pozzolanic material comprises or consists of i. 20 to 85% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
II. 15 to 80% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
More preferably, the pozzolanic material comprises or consists of i. 25 to 80% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
II. 20 to 75% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
More preferably, the pozzolanic material comprises or consists of i. 30 to 75% by weight, based on the total amount of pozzolanic material, of powdery trass, in particular powdery volcanic trass; and
II. 25 to 70% by weight, based on the total amount of pozzolanic material, of a powdery artificial pozzolanic material, in particular brick powder, where the total amount of powdery trass and brick powder is preferably at least 90% by weight, in particular at least 95% by weight, based on the total amount of the component A.
As already explained above, the pozzolanic material has a particle size of at most 500 pm, in particular of at most 300 pm, preferably of at most 250 pm or of at most 200 pm. In case of volcanic trass or tuff, the material has in particular a particle size of at most 250 pm, more particularly of at most 200 pm and specifically at most 100 pm. Preferably, the trass has a Blaine specific surface area of at least 5000 cm2/g, more preferably from 5500 to 8500 cm2/g, in particular from 6500 to 7500 cm2/g.
According to the invention, the composition contains at least one powdery cement as a component B, which comprises Portland cement clinker in an amount of at least 15% by weight, based on the total weight of the component B. According to EN 197-1 :2011 , these cements are also denominated as common cement. Preference is given to common cements containing at least 25% by weight, in particular at least 35% by weight, especially at least 45% by weight, based on the total weight of the component B, of Portland cement clinker. The component B includes in particular cements selected from common cements classified as CEM I, CEM II, CEM IV and CEM V and mixtures thereof. The terms CEM I, CEM II, CEM IV and CEM V refer to the cement classification according to EN 197-1 :2011 .
As was observed by the present inventors, the presence of a sufficient amount of Portland cement clinker in the present composition instead of slaked lime, which is customarily used in pozzolanic systems, leads to a distinctly faster setting.
In a particularly preferred group of embodiments, the cement component B is a cement classified as CEM I. According to cement classification EN 197-1 :2011 a cement of class CEM I, contains at least 95% of Portland cement clinker. Such a cement is usually termed ordinary Portland cement (OPC). The cement of class CEM I may be any type of OPC, including Portland cement classified as CEM I 52.5 N, CEM I 42.5 N, CEM I 32.5 N, CEM I 52.5 R, CEM I 42.5 R or CEM I 32.5 R.
The component B may also be a cement comprising 65% to < 95% by weight of Portland cement clinker and > 5 to 35% by weight of cementitious matter other than Portland cement clinker, such as slag, granulated blast furnace slag, fly ash, natural or natural calcined pozzolanic material, silica flour, metakaolin, limestone and calcined oil shale. These cements are typically classified as cements CEM II according to cement classification EN 197-1 :2011 and include Portland-slag cement, Portland-silica fume cement, Portland-pozzolana cement, Portland-fly ash cement, Portland-burnt shale cement, Portland-limestone cement, and Portland-composite cement.
In another particular group of embodiments, the component B is a cement of class CEM IV, i. e. a pozzolanic cement. In this case, the trass of component A may be present as a mixture with Portland cement clinker in the weight ratios given above. In this case, a portion or the complete amount of the trass of component A may be included in the cement of component B and thus be a mixture comprising both Portland cement clinker and trass. In other words, the trass of component A and the Portland cement clinker of component B may be premixed to form a cement of group CEM IV.
In any case, the weight ratio of trass and Portland cement clinker in the compositions of the invention is in the ranges given herein.
A portion of the component B may be replaced by another hydraulic binder, hereinafter component B’, such as gypsum, calcium sulfoaluminate cements (CSA) and/or calcium aluminate cements (HAC), provided that the amount of Portland cement clinker and its ratio to trass is as given above. Preferably, the relative amount of the component B will be at least 60% by weight, in particular at least 75% by weight and may be as high as 100% by weight, based on the overall weight of the components B and B’ in the composition of the invention. In particular, the component B’ is absent or amounts to less than 5% by weight, based on the overall weight of the components B and B’ in the composition of the invention.
In the composition of the invention, the weight ratio of the trass to the Portland cement clinker is in the range of 5 : 95 to 95 : 5, in particular in the range of 10 : 90 to 90 : 10, preferably in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
In composition of the invention, in particular if the components A and B are provided separately, the weight ratio of the component A to the component B is preferably in the range of 25 : 75 to 95 : 5, in particular in the range of 30 : 70 to 85 : 15 and especially in the range of 40 : 60 to 80 : 20.
The overall amount of the component A is preferably in the range of 25 to 50 % by weight, in particular in the range of 30 to 45% by weight, based on the total weight of the components A, B optionally B’ and C. In a specific embodiment, the composition comprises 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the component A, B and C and optionally B’, of volcanic trass and 10 to 40% by weight, in particular 15 to 30% by weight, based on the total weight of the components A, B and C and optionally B’, of brick powder.
The overall amount of the components A and B and optionally B’ is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’. The component C, hereinafter also termed filler typically comprises a particulate mineral material, in particular a particulate stone material customarily used as reinforcement material to add strength to the overall composite material. The filler as used in the present composition may be any of the usual construction filler, including mineral filler such as rock powder and sand; and recycle filler produced from the recycling of concrete, which is itself chiefly manufactured from mineral filler. Mineral fillers such as powdery dolomite, granites, gravel, sandstone, limestone, basalt and the like can also be used as filler. The present powdery filler may also organic concrete “filler”, such as rubber or bitumen. The present powdery filler typically includes also mixtures of two or more of the above-listed fillers.
The overall amount of the powdery filler is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, based on the total weight of the components A, B and C and optionally B’.
Preferably, the powdery filler comprises sand. Preferably, the powdery filler comprises preferably at least 50% by weight, more preferably at least 60% by weight, and up to 100% by weight, based on the total weight of the component C, of sand.
Preferably, the sand is a combination of medium sand and fine sand. Fine sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.063-0.2 mm. Medium sand in terms of the present invention is defined in accordance with DIN 4022:1987 and is sand with an equivalent diameter of 0.2-0.63 mm. Medium sand and fine sand are preferably present in a weight ratio of from 2: 1 to 1 :5, more preferably from 1 :1 to 1 :3, in particular from 1 :1.5 to 1 :3.
In a preferred embodiment, the filler comprises an organic powdery recycling material, such as powdered rubber. The powdered rubber is a recycle material obtained, for example from comminuting discarded tires and the like. The powdered rubber not only reduces the amount of natural mineral fillers, such as sand, thus allowing to preserve their pristine natural resources, but also contributes to the flexibility and elasticity and thus crack resistance of the set system. The organic powdery recycling material has preferably a particle size of at most 500 pm and typically of at least 50 pm.
The organic powdery recycling material, if contained in the composition, is preferably present in an amount of from 5 to 50% by weight, more preferably from 10 to 40% by weight, in particular 10 to 35% by weight, based on the total weight of the component C. Its amount, if present, is typically in the range of 2 to 25% by weight, in particular 5 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
Apart from components A, B, C and D (and optionally B’) the composition may contain other ingredients. One example for an additional ingredient is kaolin, hereinafter component E. As was observed, the presence of kaolin leads to a fibrous structure of the set system which enhances its flexibility and crack stability. Thus, in a preferred embodiment, the composition of the invention additionally comprises powdery kaolin. Kaolin, also known as China clay, is a hydrated aluminum silicate, which can be approximately described by the simplistic and idealized formula AI2O3 ■ 2SiC>2 ■ 2H2O. It is a natural, fine-grained and well crystallized clay mineral with a layered structure. Kaolin, if contained in the composition, is preferably present in an amount of from 1 to 10% by weight, more preferably from 1 to 5% by weight, in particular from 2 to 3% by weight, based on the total weight of the components A, B and C and optionally B’. The kaolin has preferably a particle size of at most 500 pm, more preferably of at most 300 pm, in particular of at most 100 pm.
The composition of the invention may also contain non-slaked lime as a component F. As was observed by the present inventors, the use of non-slaked lime in the present composition leads to a distinctly faster setting. Moreover, it allows to reduce the amount of calcium needed for setting. If present, the amount of the non-slaked lime is preferably in the range of 5 to 20% by weight, in particular in the range of 8 to 15% by weight, based on the total weight of the components A, B and C and optionally B’.
A particular group of embodiment of the invention relates to compositions which do not contain non-slaked lime or less than 5% by weight of non-slaked lime, based on the total weight of the components A, B and C and optionally B’.
The composition of the invention may moreover contain other additives typical for such formulations, such as rheology modifiers (e.g. thickeners, plasticizers), accelerators or retardants (for the setting process) and wetting agents or dispersants, respectively. These additives are hereinafter referred to as component G. The total amount of these additives is usually at most 5% by weight, preferably at most 2% by weight, based on the total weight of components A, B and C and optionally B’ and e. g. in the range of 0.1 to 5 % by weight or in the range of 0.2 to 2% by weight, if present.
Here, the terms “wetting agents” and “dispersants” are used synonymously. They allow for reducing the amount of make-up water required for producing the slurry. Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1 -diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts. Among the above dispersants, preference is given to polymeric dispersants, such as alkali metal salts and ammonium salts of acrylic acid polymers or maleic anhydride polymers. Specifically, a metal salt of polyacrylic acid is used as a dispersant or wetting agent, respectively.
Preferably, the composition of the invention contains the dispersant, in particular the polymeric dispersant, in an amount of from 0.1 to 5% by weight, in particular of from 0.3 to 3% by weight, based on the total weight of the components A and B.
In a preferred group of embodiments, the composition is formulated as a 2K composition which comprises a first powdery composition (I), which contains the powdery components A, B and C and optionally the powdery components B’, E, F and G, and a second composition (I) which contains the polymer P, in particular in the form of an aqueous polymer dispersion.
Frequently, the composition (I) comprises or consists of:
(a) 25 to 50% by weight of the component A, in particular a combination of volcanic trass and brick powder;
(b) 10 to 40% by weight of the component B or of a combination of components B and B’;
(c) 35 to 65% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
(e) 0 to 10% by weight, e. g. 1 to 10% by weight, in particular 1 to 5% by weight of powdery kaolin;
(f) 0 to 20% by weight of powdery non-slaked lime;
(g) 0 to 5% by weight of a further additive; in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, and where the weight ratio of the trass of component A to the cement clinker of the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30. In particular, the composition (I) comprises or consists of:
(a) 30 to 45% by weight of the component A, in particular a combination of volcanic trass and brick powder;
(b) 15 to 35% by weight of the component B or of a combination of components B and B’;
(c) 40 to 55% by weight of the filler (component C), in particular a combination of sand and an organic powdery recycling material, in particular powdery rubber;
(e) 1 to 10% by weight, in particular 1 to 5% by weight of powdery kaolin;
(f) 0 to 15% by weight of powdery non-slaked lime;
(g) 0 to 2% by weight of a further additive; in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of in the range of 45 to 59% by weight, and where the weight ratio of the trass of component A to the cement clinker of the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
In a particular embodiment, the composition comprises or consists of: (a.1 ) 10 to 40% of trass, in particular volcanic trass;
(a.2) 10 to 40% by weight of brick powder; where the total weight of trass and brick powder is in the range of 25 to 50% by weight;
(b) 10 to 40% by weight of the component B or of a combination of components B and B’;
(c.1 ) 25 to 63% by weight of sand;
(c.2) 2 to 25% by weight of powdery rubber; and
(e) 0 to 10% by weight, e. g. 1 to 10% by weight, in particular 1 to 5% by weight of kaolin;
(f) 0 to 20% by weight of non-slaked lime
(g) 0 to 5% by weight of a further additive; in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B is preferably in the range of 35 to 65 % by weight, in particular in the range of 40 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
In a very particular embodiment, the composition comprises or consists of: (a.1 ) 15 to 30% of trass, in particular volcanic trass;
(a.2) 14 to 30% by weight of brick powder; where the total weight of trass and brick powder is in the range of 30 to 45% by weight,
(b) 15 to 35% by weight of the component B or of a combination of components B and B’;
(c.1 ) 30 to 50% by weight of sand;
(c.2) 5 to 15% by weight of powdery rubber; and
(e) 1 to 10% by weight, in particular 1 to 5% by weight of kaolin;
(f) 0 to 15% by weight of non-slaked lime
(g) 0 to 2% by weight of a further additive; in particular a rheology modifier, especially a thickener; where the above percentages add to 100% by weight, where the overall amount of the components A and B and optionally B’ is preferably in the range of 44 to 60% by weight, and where the weight ratio of the trass of component A to the component B is preferably in the range of 10 : 90 to 90 : 10, in particular in the range of 20 : 80 to 80 : 20 and especially in the range of 30 : 70 to 70 : 30.
The composition of the invention further comprises a polymer P. The polymer P of the component B may be present either as an aqueous polymer dispersion or as a polymer powder, in particular a polymer powder which is obtained by spray-drying of an aqueous polymer dispersion of the polymer P.
The polymer P is made of polymerized ethylenically unsaturated monomers M, where the polymer has a glass transition temperature Tg of at most +15°C, in particular at most +10°C, more particularly at most +5°C, especially at most 0°C. Here and in the specification the values given for the glass transition temperature Tg refer to values which are determined by the differential scanning calorimetry (DSC) method according to ISO 11357-2:2013, preferably with sample preparation according to ISO 16805:2003. In case that the polymer P is powdery, it comprises a polymer powder obtained from the above-described aqueous polymer dispersion, where the polymer of the aqueous polymer dispersion has a glass transition temperature Tg of at most +15°C, in particular at most +10°C, more particularly at most +5°C, especially at most 0°C. Generally, the glass transition temperature Tg is at least -60°C, frequently at least -50°C, in particular at least -40°C more particularly at least -30°C and especially at least -25°C. Generally, the Tg of the polymer is in the range of -60 to +15°C. Preferably, the Tg of the polymer is in the range of -50 to +10°C, in particular in the range of - 40 to +5°C or -30 to +5°C, especially in the range of -30 to 0°C or -25 to 0°C. The following remarks regarding the polymer apply both for the liquid and the powdery forms of the polymer P.
The amount of polymer P of the component D in the composition is usually such that the weight ratio of the polymer P to the total weight of the components A, B, C and the optional components E and F, if present, is in the range of 1 :10 to 1 :1 and in particular in the range of 1 :6 to 1 :1 .1 . Preferably, the organic polymer P is present in the composition for producing the waterproofing membrane in amount in the range of 10 to 50% by weight, in particular in the range of 15 to 45% by weight, based on the total weight of dry matter of the composition for producing the waterproofing membrane and calculated as polymer P.
The polymers P are insoluble in water and are present in the form of discrete polymer particles.
If the polymer P is present in the form of an aqueous polymer dispersion of polymer particles of the polymer P, the average diameter of the polymer particles present in aqueous dispersion is generally in the range from 10 to 1000 nm, frequently in the range from 20 to 850 nm, e.g. from 100 to 700 nm. By average particle diameter this specification means the Z average particle diameter as determined by dynamic light scattering (also termed quasielastic light scattering) of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5% by weight at 22°C by means of a HPPS from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321 ).
The aqueous dispersion of the polymer P is generally a polymer obtained by emulsion polymerization of ethylenically unsaturated monomers M, hereinafter also referred to as polymer emulsions. Polymer emulsions are familiar to the skilled person and are prepared, for example, in the form of an aqueous polymer dispersion by means of radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers M. This technique has been exhaustively described in the art, and is therefore well known to the skilled person [cf., e.g., Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; D. C. Blackley, Emulsion Polymerisation, pages 155 to 465, Applied Science Publishers, Ltd., Essex, 1975; D. C. Blackley, Polymer Latices, 2nd edition, vol. 1 , pages 33 to 415, Chapman & Hall, 1997; H. Warson, The Applications of Synthetic Resin Emulsions, pages 49 to 244, Ernest Benn, Ltd., London, 1972; J. Piirma, Emulsion Polymerisation, pages 1 to 287, Academic Press, 1982; F. Holscher, Dispersionen synthetischer Hochpolymerer, pages 1 to 160, Springer-Verlag, Berlin, 1969, and patent specification DE-A 40 03422], The radically initiated aqueous emulsion polymerization is normally accomplished by dispersing the ethylenically unsaturated monomers in aqueous medium, generally with accompanying use of dispersing assistants, such as emulsifiers and/or protective colloids, and polymerizing them by means of at least one water- soluble radical polymerization initiator. In the aqueous polymer dispersions obtained, the residual amounts of unreacted ethylenically unsaturated monomers are frequently lowered by chemical and/or physical techniques that are likewise known to the skilled person [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586, and 19847115]; the polymer solids content is adjusted to a desired level by dilution or concentration; or the aqueous polymer dispersion is admixed with further customary adjuvants, such as bactericidal, foam-modifying or viscositymodifying additives, for example.
As well as these so-called primary aqueous polymer dispersions, the skilled person also knows of what are called secondary aqueous polymer dispersions. These are understood to be aqueous polymer dispersions in whose preparation the polymer is generated outside of the aqueous dispersing medium, as for example in solution in a suitable nonaqueous solvent. This solution is subsequently transferred into the aqueous dispersing medium, and the solvent is separated off with dispersing, generally by distillation.
Preferably, the aqueous polymer dispersion of the polymer P is a primary aqueous polymer dispersion, in particular an aqueous polymer dispersion, which is obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M.
Preferably, the polymer P is a copolymer of ethylenically unsaturated monomers M. The term copolymer as used herein refers to polymers which are made of two or more, e.g. 2, 3, 4, 5 or 6 or more different ethylenically unsaturated monomers M. Preferably the copolymer comprises both ethylenically unsaturated comonomers with a rather low and with a higher solubility in water, where the comonomers of rather low solubility preferably constitute the major part of the polymer. Ethylenically unsaturated monomers of low water-solubility are those having a solubility in water of not more than 50 g/l at 20°C and 1 bar. These monomers are hereinafter referred to as monomers M 1 . Monomers of higher water-solubility are those having a solubility in water of at least 60 g/l at 20°C and 1 bar. These monomers are hereinafter referred to as monomers M2.
Preferably, the polymer P is composed of i) 80 to 99.9 pphm, more particularly 85 to 99.5 pphm, of at least one neutral, nonfunctional monoethylenically monomer M.1 having a water-solubility in deionized water of not more than 50 g/l at 20°C and 1 bar, e. g. in the range of 0.01 to 50 g/l; and ii) 0.1 to 20 pphm, more particularly 0.5 to 15 pphm, of at least one further ethyleni- cally unsaturated monomer other than the monomers M 1 .
The term “pphm” means part per hundred parts of monomers and is an abbreviation of the term “% by weight, based on the total amount of monomers”.
The term “neutral” means that the monomer has neither a basic or acidic group nor a ionic group.
The term “non-functional” means that the monomer has no functional group, which is capable to undergo a polymer analogue reaction, i. e. a bond-forming reaction with another group of the polymer or with a crosslinking agent or with inorganic matter.
The term unsaturated monomer other than the monomers M1 refers to monoethylenically unsaturated neutral monomers having a water-solubility in deionized water of more than 50 g/l at 20°C and 1 bar, e. g. at least 60 g/l at 20°C and 1 bar; monoethylenically unsaturated monomers having a basic or acidic group or a ionic group, e. g. an acidic group such as carboxyl group (COOH), a SO3H group, a PO3H2 or O-PO3H2 group and the salts thereof, a basic group such as a dialkylamino group or a ionic group, such as the corresponding anionic group of one of the aforementioned acidic groups, or a cationic group, such as a quaternized amino group; monoethylenically unsaturated monomers having a functional group which is capable of undergoing a polymer analogue reaction, e. g. a keto carbonyl group, an aldehyde group, an isocyanate group, a 1 ,3-dicarbonyl group, a urea group, an N- alkylolamide group or a hydrolysable silane group; and ethylenically unsaturated monomers having at least 2 ethylenically unsaturated double bonds.
Examples of neutral, non-functional monoethylenically unsaturated monomers M.1 are: esters of acrylic and/or methacrylic acid with alkanols having 1 to 20 C atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2- octyl acrylate, 2-ethylhexyl acrylate, 2-propylpentyl acrylate, n-decyl acrylate, 2- propylheptyl acrylate, Cw isoamyl guerbet acrylate, 1 -propylheptyl acrylate, lauryl acrylate and stearyl acrylate. Examples of C1-C20 alkyl esters of methacrylic acid include, but are not limited to methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-octyl methacrylate, 2-ethylhexyl methacrylate, 2-propylpentyl methacrylate, n- decyl methacrylate, 2-propylheptyl methacrylate, Cw isoamyl guerbet methacrylate, 1 -propylheptyl methacrylate, lauryl methacrylate and stearyl methacrylate; esters of acrylic and/or methacrylic acid with cycloalkanols having 3 to 10 C atoms, in particular 5 to 10 C atoms, such as cyclopropylacrylate, cyclopentyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexyl methacrylate and 4-tert-butylcyclohexyl methacrylate; esters of acrylic and/or methacrylic acid with heterocyclic alcohols, such as furfuryl acrylate and furfuryl methacrylate; vinylaromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene or 4-n-decylstyrene; conjugated alkadienes, such as butadiene or isoprene; olefins and haloolefins such as ethylene, propene, vinyl chloride, and vinylidene chloride; vinyl esters and allyl esters of saturated C1-C12 alkanoic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl stearate, vinyl esters of Versatic acid, allyl formate, allyl acetate, allyl propionate, allyl butyrate or allyl laurate.
Preferred monomers M1 are esters of acrylic with alkanols having 1 to 10 C atoms esters of methacrylic acid with alkanols having 1 to 10 C atoms, esters of acrylic with cycloalkanols having 5 to 10 C atoms esters of methacrylic acid with cycloalkanols having 5 to 10 C atoms, furfuryl acrylate, furfuryl methacrylate, vinylaromatic hydrocarbon compounds, specifically styrene, conjugated alkadienes, specifically butadiene, vinyl esters of saturated Ci-Cs alkanoic acids, specifically vinylacetate, and olefins, specifically ethylene and combinations thereof.
Further ethylenically unsaturated monomers other than the monomers M1 include, but are not limited to, monoethylenically unsaturated neutral monomers M2 having a solubility in deionized water of at least 60 g/L, such as primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms such as acrylamide and methacrylamide, and esters of acrylic and/or methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate;
The total amount of monomers M2 is preferably in the range of 0 to 15% by weight in particular in the range of 0 to 10% by weight, e. g. in the range of 0.1 to 15% by weight, in particular in the range of 0.5 to 10% by weight, based on the total amount of monomers M.
Further ethylenically unsaturated monomers other than the monomers M1 include, but are not limited to monoethylenically unsaturated monomers M3 having at least one acidic group or a such as carboxyl group (COOH), a SO3H group, a PO3H2 or O-PO3H2 group and the salts thereof, e. g. their sodium salts, potassium salts or ammonium salts. Particular groups of such monomers include: monoethylenically unsaturated monomers bearing 1 or 2 COOH groups (monomers M3a), e. g. monocarboxylic acids having 3 to 8 C atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 8 C atoms such as acrylic acid, methacrylic acid, itaconic acid and citraconic acid with particular preference given to methacrylic acid; monoethylenically unsaturated sulfonic acids (monomers M3b) and their salts such as vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3- acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, and 2-acrylamido-2-methylpropanesulfonic acid, especially their salts, more particularly their sodium salts, potassium salts or ammonium salts; monoethylenically unsaturated monomers bearing a O-PO3H2 group (phosphate group - monomers M3c) and their salts, in particular their sodium, potassium or ammonium salts, e. g. monomers of the formula (M3c-I)
H2C=C(R)-C(=O)-O-A-[O-Alk]n-O-P(=O)(OH)2 (M3c-I) wherein A is C2-C4-alkandiyl, in particular 1 ,2-ethanediyl, 1 ,3-propandiyl or 1 ,2-pro- pandiyl,
Aik within the repeating unit [Alk-O]n is identical or different and 1 ,2-ethanediyl or 1 ,2-propandiyl, n is 0 or an integer from 1 to 20, in particular 0 or an integer from 1 to 10, and R is hydrogen or methyl, examples of monomers M3c being mono-(meth)acryloxyethyl phosphate, mono- (meth)acryloxypropyl phosphate, mono-(meth)acryl(oxy-1 ,2-ethanediyl)i-2o phosphate and mono-(meth)acryl(oxy-1 ,2-propandiyl)i-2o phosphate and their salts, in particular their sodium, potassium or ammonium salts.
Preferably, the polymer P contains not more than 2 pphm of monoethylenically unsaturated monomers M3. Preferably, the total amount of monomers M3 will be at most 2 pphm, e. g. 0.1 to 2 pphm, or at most 1 .5 pphm, e. g. 0.2 to 1 .5 pphm.
In particular, the polymer of the polymer P contains at most 1.5 pphm, e. g. 0.1 to 1.5 pphm, of one or more monomers M3a having a carboxylic acid group, such as acrylic acid, methacrylic acid or itaconic acid, with particular preference given to methacrylic acid. Preferably, the polymer contains at most 1 pphm, e. g. 0.01 to 1.0 pphm, of one or more monomers M3b having a sulfonic acid group. Preferably, the polymer contains at most 1 pphm, e. g. 0.01 to 1 .0 pphm, of one or more monomers M3b. Preferably, the polymer contains at most 1 .5 pphm, e. g. 0.1 to 1 .5 pphm, of one or more monomers M3c. Preferably, the total amount of monomers M3 will be at most 2 pphm, e. g. 0.1 to 2 pphm, or at most 1 .5 pphm, e. g. 0.2 to 1 .5 pphm.
The total amount of monomers M2+M3 is preferably in the range of 0.1 to 15% by weight in particular in the range of 0.2 to 10% by weight, based on the total amount of monomers M.
In addition to the aforementioned monoethylenically unsaturated monomers M1 and the optional monomers M2 and/or M3, the monomers M may comprise a small amount of monoethylenically unsaturated monomers M4, which have one unsaturated double bond and a further reactive group susceptible to a post-crosslinking reaction, including monoethylenically unsaturated monomers containing a keto group (monomers M4a), e.g., acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, acetoacetoxyethyl methacrylate, diacetoneacrylamide (DAAM) and diacetonemethacrylamide; monoethylenically unsaturated monomers which carry one or more urea groups (monomers M4b) such as 2-(2-oxoimidazolidin-1-yl)ethyl (meth)acrylate, 2-ureido(meth)acrylate, N-[2-(2-oxo-oxazolidin-3-yl)ethyl] methacrylate; monoethylenically unsaturated monomers, which bear an epoxy group (monomers M4c), such as monoeglycidyl allyl ether, glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3- glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate, 4-glycidyloxybutyl acrylate 4-glycidyloxybutyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 4,5-epoxypent-2-yl acrylate or 4,5-epoxypent-2-yl methacrylate with preference given to epoxy functionalized (meth)acrylate monomers; N-alkylolamides of a,p-monoethylenically unsaturated carboxylic acids having 3 to 10 carbon atoms and esters thereof with alcohols having 1 to 4 carbon atoms, e.g. N-methylolacrylamide and N-methylolmethacrylamide (monomers M4d).
Amongst the aforementioned monomers M4, preference is given to monomers M4a and M4c.
The total amount of monomers M4 is preferably in the range of 0 to 5% by weight, e. g. in the range of 0.1 to 5.0% by weight, in particular in the range of 0.2 to 4.0% by weight, based on the total amount of monomers M.
In addition to the aforementioned monoethylenically unsaturated monomers M1 and the optional monomers M2, M3 and/or M4, the monomers M may comprise a small amount of monoethylenically unsaturated monomers M5, which have one unsaturated double bond and a hydrolysable silane group. In the context of the present invention a hydrolysable silane group refers to a silane group, which bears 1 , 2 or 3 radicals, which are cleaved off from the silicon atom in the presence of water to form Si-OH groups. Typically the radicals are O-bound, such as alkoxy, cycloalkoxy or phenoxy. The hydrolysable silane group is typically bound to a carbon atom of the monomer. In particular, the silicon atom of the hydrolysable silane group bears n alkoxy groups and n-3 alkyl groups, with n being 1 , 2 or 3, where the aforementioned groups are bound to the silicon atom. In this context, alkoxy is preferably selected from Ci-C4-alkoxy and in particular selected from methoxy and ethoxy, while alkyl moiety is preferably selected from Ci-C4-alkyl, such as methyl or ethyl. The hydrolysable silane group of a suitable monomer M2 is preferably a trialkoxysilane group (n=3) or a alkyldialkoxysilane group (n=2), where the alkoxy moieties of the trialkoxysilane group or the alkyldialkoxysilane group, independently from each other, are preferably selected from Ci-C4-alkoxy and in particular selected from methoxy and ethoxy, while the alkyl moiety of the alkyldialkoxysilane group is preferably selected from Ci-C4-alkyl and in particular selected from methyl and ethyl. Particular preference is given to monomers M2 that bear a trialkoxysilane group or a alkyldialkoxysilane group, where in each case all alkoxy moieties are identical and are selected from Ci-C4-alkoxy, especially from methoxy and ethoxy, while the alkyl moiety of the alkyldialkoxysilane group is Ci-C4-alkyl and specifically methyl or ethyl.
Preferred monomers M5 are selected from the group consisting of vinyltrialkoxysilanes, such as in particular vinyltrimethoxysilane or vinyltriethoxysilane, alkylvinyldial- koxysilanes, such as in particular methylvinyldimethoxysilane, methylvinyldiethox- ysilane or ethylvinyldiethoxysilane, acryloxyalkyltrialkoxysilanes, such as in particular acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, acryloxypropyltrimethox- ysilane or acryloxypropyltriethoxysilane, methacryloxyalkyltrialkoxysilanes, such as in particular methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, methacryloxypropyltrimethoxysilane or methacryloxypropyltriethoxysilane, acryloxyalkyl-al- kyldialkoxysilanes, such as in particular acryloxyethyl-methyldimethoxysilane, acryloxy- ethyl-methyldiethoxysilane, acryloxypropyl-methyldimethoxysilane or acryloxypropyl- methyldiethoxysilane, and methacryloxyalkyltrialkoxysilanes, such as in particular methacryloxyethyl-methyldimethoxysilane, methacryloxyethyl-methyldiethoxysilane, methacryloxypropyl-methyldimethoxysilane or methacryloxypropyl-methyldiethox- ysilane.
Particular preference is given to monomers M5 selected from the group consisting of vinyltrialkoxysilanes, such as in particular vinyltrimethoxysilane or vinyltriethoxysilane, acryloxyalkyltrialkoxysilanes, such as in particular acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, acryloxypropyltrimethoxysilane or acryloxypropyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, such as in particular methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, methacryloxypropyltrimethoxysilane or methacryloxypropyltriethoxysilane.
In a particularly preferred embodiment of the invention, the monomers M5 are selected from vinyltrialkoxysilanes, such as in particular vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular are methacryloxypropyltrimethoxysilane.
The total amount of monomers M5 will generally not exceed 1 pphm and, if present, is usually in the range of 0.01 to 1 pphm, preferably from 0.03 to 0.7 pphm, more preferably 0.05 to 0.5 pphm, in particular from 0.07 to 0.4 pphm, and specifically from 0.1 to 0.3 pphm. In addition ot the aformementioned monoethylenically unsaturated monomers monomers M1 , M2, M3, M4 and M5, the monomers M may comprise a small amount of ethylenically unsaturated monomers M6, which bear at least 2, e.g. 2 to 6 non-conju- gated ethylenically unsaturated double bonds. These monomers will result in a crosslinking of the polymer chain during polymerization and thus are referred to as crosslinking monomers M6. Exemplary crosslinking monomers include divinylbenzene, diesters or triesters of dihydric and trihydric alcohols with monoethylenically unsaturated C3-C6 monocarboxylic acids, e.g., di(meth)acrylates, tri(meth)acrylates), and tetra(meth)acry- lates, e.g. alkylene glycol diacrylates and dimethacrylates, such as ethylene glycol diacrylate, 1 ,3-butylene glycol diacrylate, 1 ,4-butylene glycol diacrylate and propylene glycol diacrylate, trimethylolpropan triacrylate and tri meth acrylate, pentaerythrit triacrylate and pentaerythrit tetraacrylate, but also vinyl and allyl esters of ethylenically unsaturated acids such as vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, and divinyl and diallyl esters of dicarboxyilic acids, such as diallyl maleate and diallyl fumarate and also methylenebisacrylamide. The amount of said monomers M3 will usually not exceed 2 pphm and is in particular below 1 pphm.
More preferably, the polymer P is a copolymer of at least one monovinylaromatic monomer M1 a and at least one further monomer M1 b selected from conjugated aliphatic dienes, Ci-Cw-a Iky I esters of acrylic acid, Ci-Cw-a Iky I esters of methacrylic acid, C5-C10- cycloalkylesters of acrylic acid and Cs-Cw-cycloalkylesters of methacrylic acid and mixtures thereof, optionally one or more further comonomers M2 and optionally one or more further comonomers M3, M4, M5 and/or M6.
The monovinylaromatic monomer M1 a is preferably styrene.
Monomer M1 b is preferably selected from conjugated aliphatic dienes, especially butadine, Ci-Cw-a Iky I esters of acrylic acid, hereinafter referred to as C1-C10- a I kyl acylates, and Ci-Cw-a Iky I esters of methacrylic acid, hereinafter referred to as Ci-Cio-alkylmethacylates. In particular, M 1 b is selected from butadiene, C1-C10- alkylacrylates Ci-C4-alkyl methacylates. Examples of Ci-Cw-a I kyl acrylates are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-butyl acrylate, tertbutylacrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate. Among these, preference is given to n-butyl acrylate, isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate. Examples of C1-C4- al kyl methacrylates are methylmethacrylate, ethylmethacrylate, tert.-butyl methacrylate and n-butylmethacrylate. Herein, polymers P, wherein the monomer M1a is styrene and the further monomers M1 b is selected from alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid and/or methacrylic acid and cycloalkylesters, in particular Cs-Cw-cycloalkylesters of acrylic acid and/or methacrylic acid and mixtures thereof are termed styrene-acrylate copolymers. The styrene acrylate copolymers may contain one or more polymerized monomers M2, M3, M4, M5 and/or M6.
Herein, polymers P, wherein the monomer M1a is styrene and the further monomer M1 b comprises butadiene or is butadiene are termed styrene-butadiene copolymers. The styrene butadiene copolymers in these dispersions may contain one or more polymerized monomers M2, M3, M4, M5 and/or M6.
Also suitable are polymers P wherein the monomers M1 comprise vinylacetate, in particular a combination of vinylacetate and at least one C2-C6-monoolefine, such as ethylene, or a combination of vinylacetate, at least one C2-C6-monoolefine, such as ethylene, and a further monomer M1 b as defined above, which is preferably selected from vinylesters of C2-C12 alkanoic acids, in particular vinylesters of branched C4-C12 alka- noic acids, e. g. Koch acids, such as pivalic acid or Verstatic® acids, such as VeoVa 9 vinyl ester, VeoVa 10 vinyl ester and VeoVa EH vinyl ester of Hexion, C2-Cw-al- kylesters of acrylic acid, Ci-Cw-a Iky I esters of methacrylic acid, Cs-Cw-cycloalkylesters of acrylic acid and Cs-Cw-cycloalkylesters of methacrylic acid and mixtures thereof. Hereinafter polymers P, wherein the monomers M1 comprise combination of vinylacetate, ethylene, and optionally a further monomer M1 b as defined above, are also termed ethylene-vinylacetate copolymers or EVA copolymers, respectively.
Also suitable are polymers P, which are similar to the styrene acrylates, where at least a portion of the styrene is replaced by acrylonitrile. In these polymers P the monomers M comprise acrylonitrile and optionally styrene as monomers M1a”, and at least one further monomer M1 b”, which is selected from the group of Ci-Cw-a Iky I esters of acrylic acid, Ci-Cw-a Iky I esters of methacrylic acid, Cs-Cw-cycloalkylesters of acrylic acid and Cs-Cw-cycloalkylesters of methacrylic acid and mixtures thereof, optionally one or more further comonomers M2 and optionally one or more further comonomers M3 and/or M4. These polymers P are herein termed acrylonitrile-acrylate copolymers.
Also suitable are all acrylic-polymers. In these polymers P the monomers M comprise at least one Ci-C4-a Iky I esters as a monomer M 1a’, in particular methyl methacrylate, and at least one further monomer M1 b’, which is selected from the group of Ci-Cw-al- kylesters of acrylic acid, Cs-Cw-a Iky I esters of methacrylic acid, Cs-Cw-cycloalkylesters of acrylic acid and Cs-Cio-cycloalkylesters of methacrylic acid and mixtures thereof, optionally one or more further comonomers M2 and optionally one or more further comonomers M3, M4, M5 and/or M6.
Even more preferably, the polymers P are selected from copolymers of a vinylaromatic compound M 1 a, in particular styrene and at least one further monomer M 1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cio-alkylesters of acrylic acid, alkylesters, in particular Ci-Cw-a Iky I esters of methacrylic acid, cycloalkylesters, in particular Cs-Cw-cy- cloalkylesters of acrylic acid and cycloalkylesters, in particular Cs-Cw-cycloal- kylesters of methacrylic acid and mixtures thereof, e.g. styrene-butadiene copolymers or styrene-acrylate copolymers; and copolymers of vinylesters and a-olefins, such as ethylene, e.g ethylene-vi- nylacetate copolymers.
Here and in the following, the term “copolymer” refers to polymers containing at least two different types of polymerized monomers. Thus, the term “copolymer” includes polymers made of two different types of monomers and polymers made of three or more different types of monomers (terpolymers and the like).
In particular, the polymers P are selected from styrene-acrylate copolymers, styrenebutadiene copolymers, all-acrylic copolymers, acrylonitrile-acrylate copolymers, vinyl acetate polymers and ethylene-vinylacetate copolymers with particular preference given to styrene-acrylate copolymers and styrene-butadiene copolymers.
In a more preferred group of embodiments, the monomers M which form the polymer P comprise: i. 80 to 99.9% by weight, in particular 85 to 99.5% by weight, based on the total amount of monomers M, of at least one monomer M1 , which is selected from a combination of at least one monovinylaromatic monomer M1 a and at least one further monomer M1 b selected from conjugated aliphatic dienes, alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid and/or methacrylic acid and cycloalkylesters, in particular Cs-Cw-cycloalkylesters of acrylic acid and/or methacrylic acid and mixtures thereof;
II. O to 15% by weight, in particular 0 to 10% by weight, e. g. 0.1 to 15 % by weight or 0.5 to 10% by weight, in based on the total amount of monomers M, of one or more monomers M2 selected from monoethylenically unsaturated neutral monomers having a solubility in water of at least 60 g/L at 20°C; iii. O to 2.0% by weight, in particular 0 to 1.5% by weight, e. g. 0.1 to 2.0% by weight or 0.2 to 1 .5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M3 having at least one acid group; iv. 0 to 5% by weight, e. g. 0.1 to 5.0% by weight, in particular 0.2 to 4.0% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M4 which effect self-crosslinking of the polymer; v. 0 to 1 .0% by weight, e. g. 0.01 to 1 .0% by weight, in particular 0.03 to 0.7% by weight or 0.05 to 0.5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M5 having a hydrolysable silane group, which are in particular selected from vinyltrialkoxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular methacryloxypropyltrimethoxysilane; where the total amount of monomers M2, M3, M4 and M5 is in the range of 0.1 to 20% by weight, in particular in the range of 0.2 to 15% by weight, based on the total amount of monomers M, and where the total amount of monomers M2 and M3 is preferably at most 15% by weight, especially at most 10% by weight, based on the total amount of monomers M.
In this more preferred group of embodiments, the monomers M2 are as defined above and preferably selected from primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 C atoms, such as acrylamide and methacrylamide, and esters of acrylic and/or methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate. More preferably, M2 is selected from acrylamide, methacrylamide and esters of methacrylic acid with alkandiols having 2 to 4 C atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate or 4-hydroxybutyl methacrylate. Specifically, M2 is selected from the group consisting of acrylamide, methacrylamide, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
In this more preferred group of embodiments, the monomers M3 are as defined above and preferably selected from methacrylic acid, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acids, and 2- acrylamido-2-methylpropanesulfonic and their salts, in particular their sodium, potassium or ammonium salts, and the monomers of the formula M3c-I, such as mono- (meth)acryloxyethyl phosphate, mono-(meth)acryloxypropyl phosphate, mono- (meth)acryl(oxy-l ,2-ethanediyl)i-2o phosphate and mono-(meth)acryl(oxy-1 ,2- propandiyl)i-2o phosphate and their salts, in particular their sodium, potassium or ammonium salts.
In this more preferred group of embodiments, the monomers M4 are as defined above and preferably selected from the group consisting of the monomers M4a and M4c with particular preference given to monomers M4a bearing a 1 ,3-dicarbonyl moiety, such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, acetoacetoxyethyl methacrylate, and epoxy functionalized (meth)acrylate monomers, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl acrylate, 3-glycidyloxypropyl methacrylate.
In a special group of embodiments, the monomers M which form the polymer P comprise: i. 80 to 99.9% by weight, in particular 85% to 99.5% by weight, based on the total amount of monomers M, of at least one monomer M1 , which is selected from a combination of styrene and at least one further monomer M1 b selected from butadiene and alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid;
II. 0.1 to 15% by weight, in particular 0.5% to 10% by weight, based on the total amount of monomers M, of at least one monomer M2 selected from acrylamide, methacrylamide and esters of methacrylic acid with alkandiols having 2 to 4 C atoms; ill. optionally 0 to 2.0% by weight, in particular 0 to 1 .5% by weight, e. g. 0.1 to 2.0% by weight or 0.2 to 1 .5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M3 having at least one acid group, in particular selected from the monomers methacrylic acid and monomers M3c and combinations thereof; iv. optionally 0 to 5% by weight, e. g. 0.1 to 5.0% by weight, in particular 0.2 to 4.0% by weight, based on the total amount of monomers M, of one or more of the above-listed monomers M4, in particular selected from the monomers M4a and M4c; and. v. optionally 0 to 1 % by weight, e. g. 0.01 to 1 .0% by weight, in particular 0.03 to 0.7% by weight or 0.05 to 0.5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M5 having a hydrolysable silane group, which are in particular selected from vinyltrial- koxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular methacryloxypropyltrimethoxysilane. In another special group of embodiments, the monomers M which form the polymer P comprise: i. 80 to 99.9% by weight, in particular 85% to 99.5% by weight, based on the total amount of monomers M, of at least one monomer M1 , which is selected from a combination of styrene and at least one further monomer M1 b selected from butadiene and alkylesters, in particular Ci-Cw-a Iky I esters of acrylic acid;
II. optionally 0 to 10% by weight, e. g. 0.1 % to 5% by weight, based on the total amount of monomers M, of at least one monomer M2 selected from acrylamide, methacrylamide and esters of methacrylic acid with alkandiols having 2 to 4 C atoms; ill. 0.1 to 1 .5% by weight, in particular 0.2 to 1 .0% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M3 having at least one acid group, in particular selected from the monomers methacrylic acid and monomers M3c and combinations thereof; iv. optionally 0 to 5% by weight, e. g. 0.1 to 5.0% by weight, in particular 0.2 to 4.0% by weight, based on the total amount of monomers M , of one or more of the above-listed monomers M4, in particular selected from the monomers M4a and M4c; and v. optionally 0 to 1 % by weight, e. g. 0.01 to 1 .0% by weight, in particular 0.03 to 0.7% by weight or 0.05 to 0.5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M5 having a hydrolysable silane group, which are in particular selected from vinyltrial- koxysilanes, such as vinyltrimethoxysilane or vinyltriethoxysilane, and methacryloxyalkyltrialkoxysilanes, in particular methacryloxypropyltrimethoxysilane.
The monomers M which form the polymer P may be of petrochemical origin or may be of bio-renewable sources. In particular at least 30% by weight of the monomers M, preferably at least 40% by weight or at least 50% by weight of the monomers M are based on bio-renewable sources, which means that their content of bio carbon is at least 30 mol-%, in particular at least 40 mol-%, based on the total amount of carbon in the monomers from bio-renewable sources.
The term “bio-carbon” indicates that the carbon is of biological origin and comes from a biomaterial/renewable resources. The content in bio-carbon and the content in biomaterial are expressions that indicate the same value. A material of renewable origin or biomaterial is an organic material wherein the carbon comes from the CO2 fixed recently (on a human scale) by photosynthesis from the atmosphere. A biomaterial (Carbon of 100% natural origin) has an isotopic ratio 14C/12C greater than 10-12, typically about 1 .2*10-12, while a fossil material has a zero ratio. Indeed, the isotopic 14C is formed in the atmosphere and is then integrated via photosynthesis, according to a time scale of a few tens of years at most. The half-life of the 14C is 5,730 years. Thus, the materials coming from photosynthesis, namely plants in general, necessarily have a maximum content in isotope 14C. The determination of the content of biomaterial or of bio-carbon is can be carried out in accordance with the standards ASTM D 6866-12, the method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
The term "bio-renewable sources" refer to organic materials in which the carbon comes from non-fossil biological sources. Examples of bio-renewable sources include, but are not limited to, sugars, such as glucose or saccharose, and starches obtained from plants, such as corn, cereals, sugarcanes, beets, potatoes, sweet potatoes or cassava, other polysaccharides of plant origin, such as celluloses, lignocelluoses, hemicelluloses, pectin, chitin, levan and pullulan, plant oils, biomass obtained from plants or agriculturaly waste and the like.
The monomers and monomer precursors, such as alcohols and fatty acids, can be directly produced from such biological recources via biological processes, including fermentation and the like.
Examples of monomers and monomer precursors which can be directly obtained from biorenewable sources are acrylic acid, methacrylic acid, itaconic acid, the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid, wherein the at least the carbon atoms of the alkyl and cycloalkyl group, respectively, are of biological origin, i.e. e. they are at least partly made of bio-carbon. In particular, the respective alkanols and cycloalkanols used for the production of the alkyl esters and cycloalkyl esters of acrylic acid and methacrylic acid, respectively, preferably have a content of bio-carbon of at least 70 mol-%, based on the total amount of carbon atoms in the respective monomers. This content is advantageously higher, in particular greater than or equal to 80 mol-%, preferably greater than or equal to 90 mol-% and advantageously equal to 100 mol-%. Likewise itaconic acid, citraconic acid and mesaconic acid can be produced on large scale from renewable materials, e.g. by fermentation of glucose, saccharose, starch or cellulose containing raw materials. Similarly, acrylic acid and methacrylic acid may be produced from biorenewable sources. Further examples are vinyl esters of alkanoic acid, where at least the alkanoic acid is produced from biorenewable sources.
It is also possible to produce monomers enriched with isotope 14C by the so-called Biomass Balance Approach. Here, the biomass or organic waste of natural origin, e. g. agricultural waste, are converted into methane or unsaturated hydrocarbons (naphtha) via fermentation or non-biological classical chemical processes. The thus obtained methane and/or unsaturated hydrocarbons, optionally in combination with methane and/or unsaturated hydrocarbons of petrochemical origin, are converted by non- biological, conventional chemical processes into the monomers or monomer precursors having a isotopic ratio 14C/12C greater than zero, e. g. > 5x10 14.
In an aqueous composition (II), the polymer content is preferably from 20 to 65% by weight, more preferably from 30 to 60% by weight and in particular from 35 to 55% by weight, based on the total weight of the aqueous composition (II).
The aqueous polymer dispersions of the polymers P, in particular the aqueous polymer dispersions of the styrene-butadiene copolymers, the aqueous polymer dispersions of styrene-acrylate copolymers, the aqueous polymer dispersions of all-acrylic copolymers, the aqueous polymer dispersions of acrylonitrile-acrylate copolymers and the aqueous polymer dispersions of vinyl acetate homo and copolymers, typically contain at least one surface active compound. The surface active compound serves to stabilize the aqueous dispersion of the polymer P by keeping the particles of the polymer P dispersed. The surface active compound may be an emulsifier, a protective colloid or a mixture of both of them. The emulsifier and the protective colloid are distinct from each other by their weight-average molar mass Mw. An emulsifier has typically a weight-average molar mass Mw in general below 2000, while the weight-average molar mass Mw of the protective colloid may be up to 50 000, in particular from above 2000 to up to 50000. Typically, the amount of the surface active compound is in the range from 0.1 to 10% by weight, in partiuclar in the range from 0.5 to 5% by weight, based on the total amount of polymer in the aqueous polymer dispersion.
Preferably, the surface active compound comprises one or more emulsifiers. The emulsifier is non-ionic, anionic, or cationic. In case of employing a mixture of emulsifiers, their compatibility has to assured, which can be evaluated in case of doubt by preliminary tests. Typically, an anionic emulsifier is compatible with another anionic emulsifier or a non-ionic emulsifier. Similarly, a cationic emulsifier is typically compatible with another cationic emulsifier or a non-ionic emulsifier. Preferably, the emulsifier is an anionic emulsifier, a combination of two or more anionic emulsifier or a combination of at least one anionic emulsifier and at least one non-ionic emulsifier.
Non-ionic emulsifier are, for example, ethoxylated Cs-Cse fatty alcohols having a degree of ethoxylation of from 3 to 50 (= ethylene oxide units [EO]: 3-50) and ethoxylated mono-, di- and tri-C4-Ci2 alkylphenols having a degree of ethoxylation of from 3 to 50. Examples of customary nonionic emulsifiers are the Emulgin B grades (cetyl/stearyl alcohol ethoxylates, RTM BASF), Dehydrol LS grades (fatty alcohol ethoxylates, EO units: 1-10, RTM BASF), Lutensol A grades (Ci2Ci4-fatty alcohol ethoxylates, EO units: 3-8, RTM BASF), Lutensol AO grades (C13C15-OXO alcohol ethoxylates, EO units: 3-30), Lutensol AT grades (Ci6Ci8-fatty alcohol ethoxylates, EO units: 11-80), Lutensol ON grades (Cw-oxo alcohol ethoxylates, EO units: 3-11) and Lutensol TO grades (C -oxo alcohol ethoxylates, EO units: 3-20). Here and in the following the phrase “EO units” means the number average of ethylene oxide repeating units in the emulsifier.
Anionic emulsifiers include for example the alkali metal salts of dialkyl esters of sulfosuccinic acid, the alkali metal salts and the ammonium salt of C8-C12 alkyl sulfates, the alkali metal salts and the ammonium salts of C12-C18 alkylsulfonic acids, the alkali metal salts and the ammonium salts of C9-C18 alkylarylsulfonic acid, the alkali metal salts and the ammonium salts of sulfuric acid monoesters of ethoxylated C12-C18 alkanols (EO units: 4-30) or a sulfuric acid monoester of an ethoxylated (C4-C12 alkyl)phe- nol (EO units: 3-50). As further anionic emulsifiers, compounds of the general formula I wherein Ra and Rb are each a H atom or C4-C24-alkyl and are not both H atoms at the same time, and Mi+ and M2+ can be alkali metal ions and/or ammonium, are also useful. In the general formula I, Ra and Rb are preferably linear or branched alkyl radicals having from 6 to 18 carbon atoms, in particular 6, 12 or 16 carbon atoms, or hydrogen atoms, where Ra and Rb are not both hydrogen atoms at the same time. Mi+ and M2+ are preferably sodium, potassium or ammonium, with sodium being particularly preferred. A compound of general formula I, in which Mi+ and M2+ are both sodium, Ra is a branched alkyl radical having 12 carbon atoms and Rb is hydrogen or Ra is particularly advantageous. Use is frequently made of industrial mixtures which have a proportion of from 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (RTM The Dow Chemical Corp.). The compounds of general formula I are commonly known, e.g. from US-A 4 269 749, and commercially available. Further anionic emulsifiers are fatty alcohol phosphates, alkylphenol phosphates, alkyl polyglycol ether phosphates, alkyl polyalkylene oxide phosphates, and fatty alcohol ether phosphates and the salts thereof, in particular the alkalimetal salts and ammonium salts thereof, with particular preference given to the alkalimetal salts such as sodium salts. A comprehensive description of suitable emulsifiers may be found in Houben-Weyl, Methoden der organischen Chemie, volume XIV/1 , Makromolekulare Stoffe, Georg- Thieme-Verlag, Stuttgart, 1961 , pages 192 to 208.
Like the aforementioned emulsifiers, suitable protective colloids may be non-ionic, anionic or cationic. Examples of protective colloids are poly(vinyl alcohols), poly(alkylene glycols), poly(acrylic acids) and the alkali metal salt thereof, poly(methacrylic acids) and the alkali metal salt thereof and gelatin derivatives. Anionic protective colloid can also be a copolymer, containing a suitable amount of at least one anionic monomer, such as acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, para-vinylphenyl sulfonic acid or salt forms thereof, preferably alkali metal salts thereof, in polymerized form. Examples of cationic protective colloids are homopolymers and copolymers containing a sufficient amount of cationic monomers, in particular monoethylenically unsaturated monomers having one or more amino groups, which are N-protonated or N-alkylated. Examples include N-protonated and N-alkylated derivatives of homopolymers or copolymers of N -vinylform am ide in their at least partly hydrolyzed form, homopolymers or copolymers of N-vinylacetamide in their at least partly hydrolyzed form, N-protonated and N-alkylated derivatives of homopolymers or copolymers of N-vinylcarbazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 1-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylimidazole, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 2-vinylpyridine, N-protonated and N-alkylated derivatives of homopolymers or copolymers of 4-vinylpyridine, N-protonated and N-al- kylated derivatives of homopolymers or copolymers of amine-group-bearing acrylates, N-protonated and N-alkylated derivatives of homopolymers or copolymers of amine- group-bearing methacrylates, wherein the nitrogen of the amine-group is protonated at a pH below 7 or is permanently positively charged, for example by alkylation. Further comonomers in such cationic protective colloids may be acrylamide, methacrylamide and N-vinyl pyrrolidone.
The protective colloids are distinct from the polymers dispersed in the aqueous polymer dispersion as they are water-soluble or water dispersible. The term “water-soluble or water dispersible” is understood that the corresponding protective colloid can be dissolved or dispersed in deionized water at 20°C and 1013 mbar in an amount of at least 10 g/L polymer such that the resulting aqueous solution has either no measurable particle size or a particle size of at most 20 nm as determined by dynamic light scattering in accordance with DIN 22412:2008. A comprehensive description of suitable protective colloids may be found in Houben- Weyl, Methoden der organischen Chemie, volume XIV/1 , Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961 , pages 411 to 420.
The composition of the invention contains the polymer - either in powdery form or in dispersion - in such an amount that the weight ratio of polymer to the powdery composition A is in the range of 1 :10 to 1 :1 and in particular in the range of 1 :5 to 1 :1.
The composition of the invention may moreover contain further auxiliaries, such as
- wetting agents or dispersants,
- thickeners,
- flow control agents, biocides, and defoamers.
If composition of the invention is formulated as a 2K formulation, the auxiliaries are generally incorporated in composition (II). Flow control agents and defoamers may however also be incorporated in composition (I).
Suitable wetting agents or dispersants are, for example, sodium, potassium or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers, polyphosphonates, such as sodium 1-hydroxyethane-1 ,1- diphosphonate, and also salts of naphthalenesulfonic acids, more particularly their sodium salts. Among the above dispersants, preference is given to polymeric dispersants, such as alkali metal salts and ammonium salts of acrylic or maleic anhydride polymers. Specifically, a metal salt of polyacrylic acid is used.
Preferably, the polymeric dispersant is contained in an amount of from 0.1 to 2% by weight, in particular from 0.1 to 1 % by weight, based on the total weight of the polymer of composition (II).
Suitable thickeners are, for example, associative thickeners, such as polyurethane thickeners.
Suitable defoamers are for example silicone antifoams and magnesium stearate. Preferably, the defoamer is contained in an amount of from 0.05 to 2% by weight, in particular from 0.1 to 1 % by weight, based on the total weight of the polymer of composition (II). In case that polymer P is used as an aqueous polymer dispersion, it is expedient to keep solid components A, B, C and optionally E and F physically apart from the polmyer P in order to preclude setting of the components A, B, C and optionally E and F by the presence of water in aqueous polymer dispersoin. In this case, the composition of the invention is preferably formulated as a two kits of part formulation of the powdery composition (I) containing the components A, B, C and optionally E and F as a first part of the formulation and the liquid composition (II) containing the aqueous polymer dispersion of the polymer P as a separately formulated second part of the formulation.
In case that polymer P is powdery, it is principally also possible to formulate the composition of the invention as a two kits of part formulation. Preference is however given to formulate the composition of the invention as a physical mixture of the powdery composition components A, B, C and optionally E and F and the powdery polymer P.
The composition of the invention in form of a physical mixture is obtained by intimately mixing the various components in suitable mixing apparatuses.
The present invention relates moreover to the use of the composition of the invention for providing waterproofing membranes, and to a method for providing waterproofing membranes which comprises mixing the components A, B, C, D and optionally E and F and water to obtain a flowable slurry and applying the flowable slurry to a surface where a waterproofing membrane is required.
In the method of the invention, the amount of water is preferably chosen such that the weight ratio of water to the pozzolanic material is in the range of 1 :1 to 2:1.
The covering resulting after setting of the applied material is watertight and resistant against acidic substances, alkaline substances and chlorine-containing substances, such as various acids of chlorine, e.g. hypochloric acid, as occurring in swimmingpools and other water tanks in which water is treted against fouling. The covering has a high bond strength and has a high flexibility and elasticity also at low and very low temperatures. This makes the composition of the invention particularly suitable for use in all types of surfaces in contact with water, such as rain drains, sewage pipes, drains or tunnels, water barrier coverings under tiles in wetrooms, in swimmimg pools and other water tanks. The composition is also suitable as mending material for such coverings. The invention is further illustrated by the folowing examples.
Examples
1. Materials:
- Trass powder from Meurin, Germany; particle size < 100 pm
- CEM I 52.5 R: a Portland cement of HeidelbergCement AG, Germany.
- CEM I 52.5 N: a Portland cement of HeidelbergCement AG, Germany.
- Trass cement: mixture of volcanic trass and Portland cement clinker in a weight ratio of 40:60 (quick mix TZ of Sievert Baustoffe GmbH, Germany)
- Brick powder: from Schafer Kalk, Germany; particle size < 250 pm; produced from discarded bricks and tiles
- CaO powder 1 from Schafer Kalk, Germany; Precal 30 N; particle size <90 pm
- CaO powder 2 from Schafer Kalk, Germany; Precal 641 ; particle size <90 pm
- Sand 1 : particle size 0.06-0.2 mm
- Sand 2: particle size 0.2-0.6 mm
- Sand 3: F36; particle size 0.09-0.35 mm
- Rubber powder type K0002 from MRH (Muelsener Rohstoff- und Handelsgesellschaft mbH), particle size < 0.23 mm; produced from discarded tyres
- Rheovis® HS 1980; powdery thickener from BASF SE
- Acronal® 5400; from BASF SE; aqueous anionic copolymer dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 57%, Tg: -8°C; viscosity (250 s-1 at 23°C; DIN EN ISO 3219): 50-350 mPa-s, pH 5.5-7.5.
- Acronal 5442®; from BASF SE; aqueous, self-cross-linking dispersion of a copolymer of an acrylic acid ester and styrene; solids content: ca. 53.5%, Tg: ca. -15°C; viscosity (100 s-1 at 23°C; DIN EN ISO 3219): 10-100 mPa-s, pH 5.5-8.5.
- Foamstar® SI2210: defoamer from BASF SE
- Dispex® AA 4135: sodium polyacrylate dispersant from BASF SE
- Omyacarb 15 GU: limestone (calcium carbonate) powder from Omya
- Vinapor® DF 2922F: powdery defoamer based on surfactants and minerals; from BASF SE 2. Compositions
2.1 Compositions according to the invention Following composition of the invention were prepared by intimately mixing the ingredients in the below-indicated amounts. Compositions (I) and (II) were formulated separately. Composition 1 was composed of composition (1.1 ) and composition (11.1), composition 2 was composed of composition (1.2) and composition (11.1), composition 3 was composed of composition (1.3) and composition (11.1 ), composition 4 (not accord- ing to the invention) was composed of composition (1.4) and composition (11.1 ), composition 5 was composed of composition (1.5) and composition (11.1), composition 6 was composed of composition (1.6) and composition (11.1 ), composition 7 was composed of composition (1.7) and composition (11.1 ) and composition 8 was composed of composition (1.8) and composition (11.2).
Table 1
* not according to the invention
2.2 Comparative cementitious compositions The following cementitious composition 9 (not according to the invention) was prepared by intimately mixing the ingredients in the amounts indicated in table 2.
Table 2 3. Application tests
3.1 Fresh properties The fresh properties (density, potlife, workability and recoating time) were assessed as follows: a) Sample preparation
For this purpose, the respective compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. b) Determination of density
The densities of the obtained slurries were measured with a 50 ml pycnometer at a temperature of 23°C. The pycnometer was first filled halfway with a slurry, then vigorously knocked three times on the laboratory bench to drive out air bubbles, and finally filled to the brim. Any protruding material was scraped off with a mortar knife. The pycnometer was weighed both filled and empty and the mass difference was used to determine the density. c) Assessment of potlife and workability
300 g of the formulations were mixed in a 500 ml plastic cup (yoghurt pot). Immediately after mixing, the mass was checked for consistency with a knife spatula. The creaminess and stickiness of the mass was assessed. The dripping from the knife spatula was also assessed. Furthermore, the compound was applied to a concrete block with a 6 mm notched trowel and the processing properties were also assessed.
In certain time intervals (immediately, after 15 min, 30 min, 45 min, 60 min) a partial quantity was taken from the 500 ml cup and the working properties were tested. If the mass could only be applied to the concrete block with considerable effort and poorly, the end of the pot life had been reached. The results are summarized in table 3. d) Assessment of recoating time at 23°C
For this purpose, the respective compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
The test was carried out at 23°C and 50% humidity. The strength of the film was tested at intervals of approx. 30 min. For this purpose, the surface of the film was first spread by simple thumb pressure, then with a 6 mm toothed spatula under light pressure. The "recoating time" was reached when no indentations or grooves appeared on the surface of the film spread with the toothed spatula. The results are summarized in table 3.
Table 3:
* not according to the invention; n.d. = not determined
3.2 Mechanical Properties of the coatings
The mechanical properties of waterproofing membranes obtained from the compositions of the invention were measured according to DIN EN 527-1 and -2. a) Sample preparation
For this purpose, the respective compositions A and B given in table 1 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec, whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. The thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
After 24 hours, the dried films were removed from the substrate. The films were dried for another 6 days at 23°C/50% r.h.. Then 3 test specimens (dumb-bells S2) for dry storage and 3 test specimens (dumb-bells S2) for wet storage were cut from the films of the dried sealing slurry using a punch. b) Film properties after dry storage under ambient conditions
The samples obtained in a) were kept at ambient conditions (50% r.h. and 23°C) for 28 days. Mechanical properties were then determined by the protocol outlined in DIN EN 527-1 and -2. For this, the test specimens were clamped in the testing machine and pulled at a speed of 50 mm/min. The elongation and associated force were registered. The results are summarized in table 4. c) Film properties after storage under water (wet storage) The samples obtained in a) were kept at ambient conditions for 7 days followed by storage in tap water for 21 days at 23°C. Mechanical properties were then determined by as outlined in b) above. The results are summarized in table 4. Table 4:
1> not according to the invention
3.3 Flexibility - determination of crack bridging properties of the waterproofing membranes obtained from the inventive compositions at low temperatures
The crack bridging ability at low temperatures was tested according to DIN EN 14891.
For this purpose, the respective compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed. Mixing was done by a basket lab mixer for 2 min at a speed of 600 1/sec. The obtained mixture was directly coated onto a mortar prism according to DIN EN 14891 A8. After coating of a very fine coat (scratch spatula) and drying (~ 20 min) the first waterproofing coating was applied (thickness 1 .2 mm wet). After drying (approx. 3h) a second layer was coated (thickness also 1 .2 mm wet). For each test formulation a preparation of three samples were done (3 samples for 23°C test, 3 samples for -5°C test and 3 samples for -20°C test). According to DIN EN 14891 a drying of 28d at 23°C/50% r.h. followed. After drying period the samples were cracked in that way that only the substrate was cracked. The samples which were measured at -5°C and -20°C were stored for 4h in a climate chamber. Samples then were put in an elongation equipment and pulled apart without shearing at a defined rate according to EN 14891 until cracks were visible on the coating surface. The gap width at that point was measured and noted. The broader the gap width, the higher the flexibility. Measurement at - 5°C and -20°C was done complete in a climate chamber. The results are given as averages of 3 tests and compiled in table 5.
Table 5
* not according to the invention
As can be seen, the waterproofing membranes obtained from the compositions of the invention have superior flexibility and crack bridging properties at -20°C as compared to the water-tight coverings obtained from the prior art cementitious compositions.
3.4 Bond strength
The bond strength was measured according to DIN EN 14891 :2017. The samples were measured after storage at ambient conditions, after storage in water and after storage in chlorine water. a) Sample preparation
For this purpose, the respective compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed as described above.
The obtained mixture was directly coated onto mortar prism according to EN 12004- 2:2016 by first applying fine coat (scratch spatula) and drying (~ 20 min), secondly applying a first waterproofing coating (thickness 1.2 mm wet) and after drying (approx. 3h) a second layer (thickness also 1 .2 mm wet). The thus allowed coating was allowed to set for 24h under ambient conditions. An adhesive coating was applied. After 5 min, 9 tiles of the type V1 according to EN 14411 :2016 were placed on the adhesive coating at a distance of 50 mm and pressed with a loading of 20 ± 0.05 N. b) Storage under ambient conditions (bond strength dry)
The samples obtained in a) were kept at ambient conditions for 27 days. Then, tie rod plates were glued to the tiles with a high-strength adhesive. After 28 days of overall storage, the bond strength was measured by applying a force with a constant rate of 250 ± N/s. c) Storage under water (bond strength wet)
The samples obtained in a) were kept at ambient conditions for 7 days followed by storage in water of ambient temperature for 21 days. After drying, tie rod plates were glued and the bond strength was measured as described in b). d) Storage under chlorine water (bond strength chlorine water)
The samples obtained in a) were kept at ambient conditions for 28 days and then stored in chlorine water for 7 days. Chlorine water was prepared from 200 mg/l NaCI, 200 mg/l of Na2SC>4 and NaOCI kept at a concentration of 0.3 to 0.6 mg/l. The pH was kept at 6.5 to 7.8. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b). e) Storage under aqueous KOH (bond strength aq. KOH)
The samples obtained in a) were kept at ambient conditions for 28 days and then stored in 3% by weight aqueous solution of potassium hydroxide for 14 days at 40°C. After storage, the sample was rinsed with water and dried. After drying, tie rod plates were glued and the bond strength was measured as described in b).
The results are compiled in Table 6. Table 6
* not according to the invention
3.5 Water tightness
According to DIN EN 14891 A7 the water tightness was measured, but at a higher pressure of 2.5 bar. For this, unglazed concrete specimens were prepared by analogy to the procedures described in DIN EN 14891 A7 and kept at ambient conditions for 28 days. The 3 hardened specimens were coated on one surface as described in section 3.1 . Then the other surfaces were sealed with a shaft seal ring. The inner diameter was 100mm. The sealing ring height was approx. 2cm. The upper side of the sealing ring was pressed against a steel plate, which had an access for pressurised water in the middle. The uncoated back of the stone was observed for moisture penetration. The specimens were weighed and was stored under water pressure of 2.5 bar for 7 days and then weighed again. The coating was considered water-tight, if the weight gain of the 3 specimens was on average less than 25 g and if no penetrated water was observed on the backside. Compositions 1 to 6, 8 and 9 showed good water tightness at > 2.5 bar and low water absorption. The test results are summarized in table 7.
Table 7 not according to the invention Table 7 cont.
* not according to the invention
3.6 Capillary water uptake a) Sample preparation
For this purpose, the respective compositions (I) and (II) given in tables 1 and 2 were thoroughly mixed whereby slurries were obtained which can be used for producing the water-tight coverings. Two welding wires with a diameter of 2.5 mm were placed on a Teflon-coated plate at a distance of approx. 10 cm and fixed with adhesive tape. 300 g of the thus obtained slurries were applied to the gap with a knife spatula and then levelled over the welding wires with a trowel. The film thickness was thus 2.5 mm for wet application.
After 24 hours, the dried films were removed from the substrate. The films were dried for another 28 days at 23°C/50% r.h.. Then rectangular test specimens (5 cm x 10 cm) were cut from the films of the dried sealing slurry.
The weight of the films was determined on a laboratory balance. Then each film was placed in a shallow rectangular bowl of tap water so that the film was completely covered with water. The films were removed from the bowl at specific times, dabbed with an absorbent cloth and weighed again. The change in weight was determined and recorded. The results are given in % weight gain, based on the staring weight. The test results are summarized in table 8.
Table 8: Water uptake after x days in [%]
* not according to the invention 3.7 Slid pressure
The slit pressure test was carried out by analogy to the procedure described in DIN EN 15820. Although this standard is for bitumen applications, it is also used in Germany for mineral construction waterproofing.
The test was performed as follows: A film of the waterproofing composition was applied to a Teflon foil in a layer thickness of 4 mm (dry film thickness). After 28 days of drying, the film was then placed on the slit pressure plate (in contrast to the standard, a rectangular shaped plate of 20x20 cm was used. The slit width was 1 mm and the slit length was 25 mm). A water pressure of 2.5 bar was then applied to the sealing surface for 24 hours. The sealing films prepared from all compositions 1 to 9 provided good water tightness, as can be seen from the test results summarized in table 9.
Table 9
1> 2.5 bar water pressure for 24h, measured after 28d of film drying
2> not according to the invention
3.8 Low temperature flexibility (Mandrel test)
The flexibility was tested according to DIN EN 15813. This standard is also normally used for bitumen products, but is applied for mineral waterproofing as well.
A waterproofing slurry film of 3mm dry film thickness was produced. The film had a width of 50 mm and a length of 200 mm. After 28d drying, the films and the test mandrel (see standard) were stored at 0°C for at least 1 h and then the film was slowly bent over the mandrel within 3s. The film must not tear in the process. The test results are summarized in table 10.
Table 10
1> measured at 0°C; 1 = ok (no cracks), 0 = not ok (cracks) 2> not according to the invention
3.9 Early rain resistance
The early rain resistance was measured according to DIN EN 15816. For this purpose, the waterproofing was applied to a concrete slab in a wet layer thickness of 3 mm. After 4 or 8 hours drying time, the spray water test was carried out. The spraying time was
15 min. The test conditions are summarized in table 11 . No leaching was observed in any of the tested coatings prepared with one of the compositions 1 to 3 and 5 to 9. Table 11
1> sprayed with 2 bar water for 15 min; no leaching (drying for 4 or 8 hours before test)
2> not according to the invention

Claims

Claims
1 . A composition for producing mineral waterproofing membranes comprising: a) a powdery pozzolanic material as a component A, which comprises a powdery trass in an amount of at least 15% by weight of the total amount of the component A; b) a powdery cement as a component B comprising Portland cement clinker in an amount of at least 15% by weight of the total amount of the component B; c) at least one powdery filler as a component C; d) an organic polymer P as a component D in the form of an aqueous polymer dispersion or in the form of a polymer powder, where the polymer P has a glass transition temperature Tg of at most +10°C, in particular in the range of -30 to +10°C, especially in the range of -20 to +5°C, as determined by the differential scanning calorimetry (DSC) method according to ISO 11357-2:2013, wherein the weight ratio of the powdery trass to the Portland cement clinker is in the range of 5 : 95 to 95 : 5.
2. The composition of claim 1 , wherein the powdery trass is a powdery volcanic trass.
3. The composition of any one of the preceding claims, wherein the pozzolanic material additionally comprises brick powder.
4. The composition of claim 3, wherein the component A comprises i. 15 to 90% by weight, based on the total amount of the component A, of powdery trass, in particular powdery volcanic trass; and
II. 10 to 85% by weight, based on the total amount of the component A, of brick powder.
5. The composition of any one of the preceding claims, wherein the component B comprises at least 45% by weight of Portland cement clinker.
6. The composition of any one of the preceding claims, wherein the weight ratio of the powdery trass to the Portland cement clinker of the component B is in the range of 10 : 90 to 90 : 10 and especially in the range of 20 : 80 to 80 : 20.
7. The composition of any one of the preceding claims, wherein the weight ratio of the component A to the component B is in the range of 25 : 75 to 95 : 5, in particular in the range of 30 : 70 to 85 : 15 and especially in the range of 40 : 60 to 80 : 20.
8. The composition of any one of the preceding claims, wherein the total amount of components A and B is in the range of 35 to 65% by weight, based on the total weight of the components A, B and C.
9. The composition of any one of the preceding claims, wherein the component C comprises sand, in particular a combination of medium sand and fine sand.
10. The composition of claim 8, wherein the component C additionally comprises an organic powdery recycling material, such as powdered rubber.
11 . The use of any one of the preceding claims, which additionally comprises powdery kaolin as a component E.
12. The composition of any one of the preceding claims, which additionally comprises non-slaked lime as a component F.
13. The composition of claim 12, wherein the amount of the non-slaked lime is in the range of 5 to 20% by weight, based on the total weight of the components A, B and C.
14. The composition of any one of the claims 1 to 11 , which does not contain nonslaked lime or less than 5% by weight of non-slaked lime, based on the total weight of the components A, B and C.
15. The composition of any one of the preceding claims, wherein the polymer P is selected from the group consisting of styrene-butadiene copolymers, vinylacetate homo- and copolymers, styrene-acrylate copolymers and all-acrylic copolymers.
16. The composition of any one of the preceding claims, wherein the polymer of the polymer dispersion is made of ethylenically unsaturated monomers M, which comprise i. 80 to 99.9% by weight, based on the total amount of monomers M, of at least one monomer M 1 , which is selected from a combination of at least one monovinylaromatic monomer M1a and at least one further monomer M1 b selected from conjugated aliphatic dienes, alkylesters of acrylic acid or methacrylic acid and cycloalkylesters of acrylic acid or methacrylic acid and mixtures thereof,
II. 0 to 15% by weight, based on the total amount of monomers M, of one or more monomers M2 selected from monoethylenically unsaturated neutral monomers having a solubility in water of at least 60 g/L at 20°C, ill. 0 to 2% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M3 having at least one acid group; iv. 0 to 5% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M4 which effect selfcrosslinking of the polymer, v. 0 to 1 .0% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M5 having a hydrolysable silane group; where the total amount of monomers M2, M3, M4 and M5 is in the range of 0.1 to 20% by weight, based on the total amount of monomers M.
17. The composition of any one of the preceding claims, where the relative amount of the polymer P of the component D and the total weight of the components A, B,
C and the optional components E and F, if present, is in the range of 1 :10 to 1 :1 and in particular in the range of 1 :6 to 1 :1.1 .
18. The composition of any one of the preceding claims, where the relative amount of the organic polymer P is present in the composition for producing the waterproofing membrane in amount in the range of 10 to 50% by weight, in particular in the range of 15 to 45% by weight, based on the total weight of dry matter of the composition for producing the waterproofing membrane and calculated as polymer P.
19. The composition of any one of the preceding claims, which additionally contains a polymeric dispersant.
20. The composition of any one of the preceding claims, where the composition is formulated as a two kits of part formulation wherein a powdery composition (I) is a first part of the composition and a liquid composition (II) is a separately formulated second part of the composition, where the powdery composition (I) contains the components A, B and C and, if present, the optional components E and F, and where the liquid composition contains the polymer as an aqueous polymer dispersion. The composition of any one of claims 1 to 19, where the composition is formulated as a powdery formulation which comprises the components A, B and C and the polymer P of component D, and, if present, the optional components E and F. Use of the composition of any one of the preceding claims for producing mineral waterproofing membranes. A method for producing mineral waterproofing membranes which comprises providing the composition of any one of claims 1 to 21 in the form of an aqueous slurry of the components of the composition and applying the aqueous slurry to a surface, where a water-tight covering is required.
EP23729401.2A 2022-06-01 2023-05-31 Composition for waterproofing membranes Pending EP4532441A1 (en)

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PCT/EP2023/064472 WO2023232832A1 (en) 2022-06-01 2023-05-31 Composition for waterproofing membranes

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