Patent Publication Number: US-2016244367-A1

Title: Cement-free or cement-reduced low dust hybrid flooring compositions

Description:
TECHNICAL FIELD 
     The invention relates to a multi-component composition suitable for the preparation of a flooring or coating or as a grout, a method for the manufacture of the flooring or coating with the multi-component composition and the flooring or coating obtainable by the method. 
     BACKGROUND OF THE INVENTION 
     Cement is a mass product and mainly used for the preparation of concretes or mortars for the building industry. The production of cement is very energy-intensive and emits high levels of CO 2 . For instance, almost 0.8 tons of CO 2  are emitted during the production of each ton of Portland cement. Thus, materials with an improved carbon footprint which are suitable as a substitute for cement are of enormous interest in view of reduction of global CO 2  emission. 
     A further problem is dust formation during production and use of cement. It is usually necessary to spray mineral oil on the cement in order to alleviate this problem which causes loss of time during production. Moreover, incorporation of mineral oil reduces workability of the product and has a negative influence on the product surface since blister, pinholes or crater formation may occur. This necessitates additional incorporation of antifoaming additives. 
     The pulp and paper industry in Europe generates 11 million tons of solid waste each year. Manufacturing processes to produce new paper from the deinking of recycled paper account for 70% of these waste products. The recycling paper is transformed into an aqueous suspension of fibers, while inappropriate materials are eliminated in different cleaning processes. Following this initial treatment, the resultant sludge is subjected to deinking in a froth floatation process, which produces waste known as deinked sludge or paper sludge. 
     Paper sludge has a high humidity content of about 50% and is roughly composed of about 25% of organic material with their origin in paper fibers and about 25% of mineral loads such as calcium carbonate, kaolin, talc and titanium oxide. In addition, various paper manufacturing processes include water treatment plants generating paper sludge of similar composition but higher humidity content as waste. Paper sludge is a potential source for the recovery of saturated biomass and mineral constituents. Possible applications for agriculture purposes, composting or in ceramic and cement industries have been studied. 
     WO 96/06057 describes a process wherein paper waste such as paper sludge is subjected to a calcination process to obtain a material having puzzolanic properties. Also described is a method for the preparation of cement where a part of conventional cement starting materials are replaced by the calcined paper waste. 
     There have been several studies with respect to the use of calcined paper waste in cement products such as concrete or mortar. However, it has been found that only relatively small amounts of cement can be replaced by such heat treated paper waste without significantly affecting the desired properties of the cement products. In the case of mortar product, the maximum is a 10% replacement of cement by calcined paper waste since otherwise the properties such as workability or compressive strength of the obtained products are reduced too much. 
     A specific type of cement products are so called polymer cement concrete (PCC) systems. These systems are hybrid cementitious systems in which a part of the cement binder is replaced by an organic polymer. The organic polymer can be added in form of a polymer latex dispersion or in form of curable monomers or prepolymers in combination with a suitable hardener component. 
     Products based on curable starting materials such as polyurethane cementitious hybrid systems in which the organic binder is based on polyols and an isocyanate hardener and epoxy cementitious hybrid systems in which the organic binder is based on epoxy resins and an amine hardener are known and used in a plurality of applications. The latter systems are conventionally known as epoxy cement concrete (ECC) systems. 
     Common PCC systems also suffer from dust formation by cement. The current approach to avoid dust is to use oil such as mineral oil, paraffin oil and organic oil, or celluluose fibers when the cement containing component is added to the polymer latex containing component or to the mixture of curable organic binder and hardener. 
     JP H10-202229 A relates to a formed product wherein a dried sludge powder obtained by calcining dried paper-making waste sludge at a temperature of 900-1300° C. is mixed with a phenol resin emulsion, a lubricating material and a filler selected from clay and sand, and the mixture obtained is subjected to a heat treatment at 150-250° C. 
     US 2008/006383 A1 discloses a pulp sludge composition for producing building materials containing a pulp sludge ash, an aqueous modified sodium silicate having an acidic group and a polymer emulsion. 
     KR 1020050008417 A relates to a composition for construction comprising 50-65 wt. % pulp sludge incineration ash, 10-25 wt. % waste gypsum, 25-45 wt. % water and a polymer emulsion. 
     KR 2009 0115085 A describes a hydraulic hardened complex product comprising paper-making sludge incineration ash, gypsum, organic emulsion and reinforcing fibers. 
     GB 2480686 A is concerned with a construction product, comprising a mixture of sulphur polymer cement and an aggregate material. 
     JP 2000-302514 A relates to a polyurethane cement composition comprising cement, a compound containing isocyanate groups, compounds containing active hydrogen carrying groups, water and organic acids. A castor oil dispersion is used in the example. 
     SUMMARY OF THE INVENTION 
     The object of the present invention is to provide compositions suitable as inorganic organic hybrid binder compositions or mortars, in particular for flooring applications, to overcome the problems discussed above. In particular, the object is to provide compositions having reduced cement content while substantially maintaining the properties at least to a large extent compared to the conventional cement products. The system should have an improved carbon footprint compared to conventional cement products. Moreover, dust exposure should be minimized so that means for preventing dust formation such as use of oil or cellulose fibers is not necessary. 
     Surprisingly, this object could be achieved by using calcined paper sludge as a partial or complete substitute for cement in specific polymer cement hybrid systems. It was very astonishing that it is possible to replace a large amount and even up to 100% of cement and lime by calcined paper sludge, i.e. the systems can be cement-free or can have a reduced cement content. 
     Accordingly, the present invention relates to a multi-component composition comprising a solid component (A) comprising calcined paper sludge and one or more aggregates, and a binder component (B) comprising an organic binder selected from one or more polyols, one or more epoxy resins and a polymer latex dispersion, and, if the organic binder is one or more polyols or one or more epoxy resins, a hardener component (C) comprising an isocyanate hardener for the polyol or an amine hardener for epoxy resin, wherein the multi-component composition further comprises water which is contained in the binder component (B) and/or, if present, in the hardener component (C). 
     Surprisingly, the properties of the multi-component composition of the invention such as workability, open time, curing time and the mechanical properties and surface properties of floorings prepared therefrom have the same or at least similar properties compared to corresponding common compositions based on cement. The surface of floorings obtained with the inventive multi-component composition is satisfactory, no pinholes, craters or blisters are observed. 
     Further benefits are a significant reduction of dust by the multi-component composition of the invention. Therefore, measures such as addition of oil or cellulose fibers can be avoided and problems related to incorporation of such additives do not occur. 
     Since calcined paper sludge is based on a waste product which otherwise would have to be disposed, the invention is also a valuable contribution for preservation of resources and avoidance of CO 2  emission required for cement production. In this regard, the inventive multi-component composition represents green technology and contributes significantly to sustainability. 
     The inventive multi-component composition is suitable as screed or mortar and in particular for the manufacture of floorings or coatings. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Compound names beginning with “poly” designate substances which formally contain, per molecule, two or more of the functional groups occurring in their names. The compound can be a monomeric, oligomeric or polymeric compound. For instance, a polyol is a compound having two or more hydroxy groups, a polyisocyanate is a compound having two or more isocyanate groups, and a polyamine is a compound having two or more amine groups. 
     Epoxy resins are compounds having two or more epoxide groups. Epoxy resins are preferably oligomeric or polymeric compounds. 
     The term “open time” is understood to mean the duration of processability when the components are mixed with each other. The end of the open time is usually associated with viscosity increase of the composition such that processing of the composition is no longer possible. The term workability encompasses many interrelated terms such as flowability, consistency, mobility, pumpability, plasticity, compactability, stability, and finishibility. 
     The epoxy equivalent weight (EEW) is well known to the skilled person and can be determined by ASTM D1652 (hydrogen bromide-acetic acid method). 
     The average molecular weight is understood to mean the number average molecular weight, as determined using conventional methods, preferably by gel permeation-chromatography (GPC) using polystyrene as standard, styrene-divinylbenzene gel with porosity of 100 Angstrom, 1000 Angstrom and 10000 Angstrom as the column and tetrahydrofuran as a solvent, at 35° C. 
     The composition of the invention is a multi-component composition, i.e. the composition comprises two or more individual components. The components are stored separately in order to avoid spontaneous reaction. The components may be assembled together as a package. For use the components are combined with each other. When the components are mixed together, hydration and/or curing reactions begin so that the composition is to be processed within the open time after mixing the components. 
     The multi-component composition preferably consists of two or three components. Optionally, one or more additional components may be included for specific purposes. The multi-component composition of the invention comprises a solid component (A) comprising calcined paper sludge. The binder component (B) may comprise a polymer latex dispersion as an organic binder. In this case only these two components are necessary. It is however preferred that the binder component (B) comprises one or more polyols or one or more epoxy resins as organic binder. In this case a third component is necessary, namely a hardener component (C) comprising a hardener for polyol or epoxy resin, respectively. 
     Systems comprising such organic binder and optionally a hardener suitable for cementitious applications are known to the skilled person and commercially available, for instance products of Sika Schweiz AG. An example for a commercially available combination of a binder component comprising polyol and an isocyanate hardener component is Sikafloor® PurCem. An example for a commercially available combination of a binder component comprising epoxy resin and an amine hardener component is Sikafloor® EpoCem. An example for a commercially available acrylic polymer latex dispersion is Sikafloor® HyCem. 
     It is clear that the proportion of a certain ingredient in the mixture of the components depends on the content of this ingredient in the respective component and the mixture ratio of the components. In the following, ratios referring to ingredients in different components relate to suitable or correct proportions of each component according to operating instructions, i.e. to the mixing ratios to be used for mixing the components and, in use to the mixture of the components prepared. 
     Solid Component (A) 
     Component (A) is a solid component comprising calcined paper sludge and one or more aggregates. Component (A) is preferably a powder. 
     Solid Component (A) comprises calcined paper sludge. As explained above, paper sludge is a well-known waste product of paper production and in particular a waste product formed during deinking of recycled paper. The latter paper sludge is also called deinked sludge or deinked paper sludge. Paper sludge originating from the deinking process of recycled paper is preferred. 
     The paper sludge is usually dried before it is calcined. The dried paper sludge is calcined to form calcined paper sludge. Calcination is a known process where the product is subjected to heat treatment. The calcination conditions may vary to a large extent depending on the composition of the paper sludge, the desired characteristics of the product and the duration of the heat treatment. By calcining the paper sludge the organic content is at least partially removed and the latent puzzolanic properties of the mineral content are activated. The calcined paper sludge is preferably carbon-free. 
     The calcined paper sludge may be prepared by subjecting the substantially dried paper sludge to temperatures e.g. in the range of from 350 to 900° C., preferably from 500 to 850° C. and more preferably from 650 to 800° C. The heat treatment may last e.g. from 1 to 8 h, preferably 2 to 5 h. The heat treatment may be effected e.g. in a simple furnace or a fluidized bed combustion system. 
     Particularly preferred calcined paper sludge is obtained from the process described in WO 96/06057 by CDEM Minerals BV, Netherlands, where paper sludge is calcined at a temperature in the range of 720 to 850° C. A fluidized bed system is used for heat treatment. 
     Calcined paper sludge is commercially available, for instance from CDEM Minerals BV, Netherlands, under the trade name TopCrete® which is preferably used in the present invention. TopCrete® is a zero carbon material. 
     Calcined paper sludge is usually present in form of a powder. The color typically ranges from white to beige. 
     The precise composition of calcined paper sludge strongly depends on the chemistry of the paper residue inputs and the thermal conditions applied. Usually, the main ingredients of calcined paper sludge are calcium compounds such as CaO, Ca(OH) 2  and CaCO 3 , and kaolinite or preferably metakaolinite. The calcined paper sludge may e.g. comprise, expressed as % oxides, SiO 2  (e.g. 10-40 wt.-%, preferably 15-35 wt. %), CaO (e.g. 20-90 wt. %, preferably 25-60 wt. % or 30-45 wt. %), Al 2 O 3  (e.g. 5-30 wt. %, preferably 13-20 wt. %), MgO (e.g. 1-7 wt. %, preferably 2-4 wt. %), and other metal oxides (e.g. each less than 1 wt. %). The calcined paper sludge may also contain volatile material, for instance in the form of Ca(OH) 2  or CaCO 3  or organic material the content of which strongly depends on raw material used and the heat treatment conditions applied. 
     The content of the oxides increases when volatile material is lost by calcination or further calcination, respectively. The content of volatile material in the calcined paper sludge can be determined as loss on ignition (LOI), e.g. by heat treatment at 1000° C. or higher until no further weight loss is observed. By such heat treatment, Ca(OH) 2  and CaCO 3  will transform into CaO with release of H 2 O or CO 2 , respectively, as volatile material. 
     Only for illustration, a chemical characterization of particular commercial calcined paper sludges is shown below. These examples shall not limit the scope of the invention. As outlined, the chemical composition may vary considerably depending on the kind of paper sludge used and the thermal conditions applied. 
     Chemical composition of an example calcined paper sludge from Holmen Paper Madrid Industrial (% by mass): 
     
       
         
           
               
               
               
             
               
                   
                   
               
             
            
               
                   
                 CaO 
                 31.40 
               
               
                   
                 SiO 2   
                 30.20 
               
               
                   
                 Al 2 O 3   
                 18.00 
               
               
                   
                 Fe 2 O 3   
                 0.70 
               
               
                   
                 SO 3   
                 0.27 
               
               
                   
                 MgO 
                 3.70 
               
               
                   
                 K 2 O 
                 0.32 
               
               
                   
                 Na 2 O 
                 0.21 
               
               
                   
                 TiO 2   
                 0.35 
               
               
                   
                 P 2 O 5   
                 0.19 
               
               
                   
                 Loss on ignition (LOI) 
                 14.53 
               
               
                   
                   
               
            
           
         
       
     
     Other examples of calcined paper sludges wherein the composition is indicated with respect to the compounds contained: 
     
       
         
           
               
             
               
                   
               
               
                 Sample A 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 CaCO 3   
                 30 wt. % 
               
               
                   
                 CaO 
                 25 wt. % 
               
               
                   
                 Ca(OH) 2   
                  2 wt. % 
               
               
                   
                 metakaolinite 
                 36 wt. % 
               
               
                   
                 SiO 2   
                  5 wt. % 
               
               
                   
                 others 
                  2 wt. % 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                   
               
               
                 Sample B 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 CaCO 3   
                 70 wt. % 
               
               
                   
                 CaO 
                 17 wt. % 
               
               
                   
                 metakaolinite 
                  8 wt. % 
               
               
                   
                 others 
                  6 wt. % 
               
               
                   
                   
               
            
           
         
       
     
     Solid component (A) further comprises one or more aggregates. Aggregates are chemically inert, solid particulate materials. Aggregates come in various shapes, sizes, and materials ranging from fine particles of sand to large, coarse rocks. Examples of suitable aggregates are sand, such as silica sand, gravel, and crushed stone, slag, calcined flint, lightweight aggregates such as clay, pumice, perlite, and vermiculite. Sand, in particular silica sand, is preferably used to reach the workability expected and to obtain a smooth surface. 
     The grain size of the aggregates may vary depending on the application, but is preferably rather small, e.g. not more than 6 mm, preferably not more than 4 mm. The aggregate may have, for instance, a grain size in the range of 0.05 to 4 mm, wherein sand, in particular silica sand, having a grain size in the range of 0.1 to 2 mm is particularly preferred. For instance, sand having a grain size ranging from 0.3 to 0.8 mm or from 0.1 to 0.5 mm can be advantageously used in the present invention. For applications such as covering or a heavy duty screed for trowelled finish aggregates such as sand having a size of e.g. 3 mm to 4 mm are suitable. The grain size range can be determined, e.g. by sieve analysis. 
     Optionally, the solid component may comprise cement and/or cement substitutes such as fly ash, slag, silica fume or rice husk. 
     If used, the cement may be any conventional cement type or a mixture of two or more conventional cement types, e.g., cements classified according to DIN EN 197-1: Portland cement (CEM I), Portland composite cement (CEM II), blast furnace cement (CEM III), pozzolanic cement (CEM IV) and composite cement (CEM V). Of course, cements produced in accordance with another standard, such as according to ASTM Standard or Indian Standard are also suitable. 
     Solid component (A) may optionally comprise one or more additives which are commonly used, if desired, and typically known to the persons skilled in the art of cementitous applications. Examples of suitable additives, which may be optionally used in component (A), are superplastizicer such as polycarboxylate ether (PCE); oil such as mineral oil, paraffin oil and organic oil, cellulose fibers, and inorganic or organic pigments. A further additive which may be contained in solid component (A) is lime such as hydrated lime, and burnt lime. Lime may be added, if cement is contained in solid component (A) and also if cement is not contained in solid component (A). 
     As mentioned, in the composition according to the present invention cement is substituted partially or completely by calcined paper sludge. The total content of calcined paper sludge and cement, if present, in component (A) is e.g. in the range of 10 to 40 wt. %, preferably in the range of 20 to 30 wt. %, based on the total weight of solid component (A). The content of one or more aggregates is e.g. in the range of 60 to 90 wt. %, preferably in the range of 70 to 80 wt. %, based on the total weight of solid component (A). Component (A) may comprise also one or more additives as mentioned above. 
     The solid component (A) may e.g. comprise 1 to 100 wt.-%, preferably 10 to 100 wt.-% calcined paper sludge, based on the total weight of cement, if present, and calcined paper sludge in component (A), wherein 100 wt. % means that component (A) is free of cement. The proportion of cement contained in solid component (A), if any, may vary depending on the binder component (B) used. In the case of polyols as binder component (B), component (A) can be free of cement, i.e. the cement can be partially or preferably completely replaced by calcined paper sludge. On the other hand, in the case of epoxy resins or polymer latex dispersions as binder component (B), it is preferred that component (A) comprises cement, i.e. in this case it is preferred that cement is only partially replaced by calcined paper sludge. 
     If the binder component (B) comprises an organic binder selected from one or more epoxy resins or a polymer latex dispersion, preferably an acrylic latex dispersion, the solid component (A) may e.g. comprise from 1 to 60 wt.-%, preferably 10 to 50 wt.-%, more preferably 15 to 50 wt. % calcined paper sludge, based on the total weight of cement and calcined paper sludge in component (A). If the binder component (B) comprises an organic binder selected from one or more polyols, the solid component (A) may e.g. comprise from 10 to 100 wt. %, preferably from 50 to 100 wt.-%, more preferably from 80 to 100 wt. %, in particular about 100 wt. % calcined paper sludge, based on the total weight of cement, if present, and calcined paper sludge in component (A). Hence, the solid component (A) is preferably essentially free or free of cement, if one or more polyols are used as organic binder in binder component (B). 
     The content of calcined paper sludge in the multi-component composition is e.g. in the range of 0.5 to 30 wt. % or 0.5 to 25 wt. %, preferably in the range of 1 to 20 wt. % and more preferably 5 to 20 wt. % or 10 to 20 wt. %, based on the total weight of component (A), component (B) and, if present, component (C). 
     Binder Component (B) 
     The binder component (B) comprises an organic binder selected from one or more polyols, one or more epoxy resins and a polymer latex dispersion. The organic binder is preferably selected from one or more polyols and one or more epoxy resins. In this case the multi-component composition also comprises a hardener component (C) including a hardener for polyol or epoxy resin, respectively. The organic binder is most preferably one or more polyols. When the binder component (B) comprises a polymer latex dispersion, a hardener component (C) is not necessary. It is preferred that the binder component (B) further comprises water. Optionally, one or more additives may be added to component (B). 
     Binder component (B) is preferably a liquid component. The binder component (B) may be viscous but is generally pourable. 
     Examples of suitable polyols are polyoxyalkylenepolyols, also referred to as “polyetherpolyols”, polyesterpolyols, polycarbonatepolyols, poly(meth)acrylate polyols, polyhydrocarbon-polyols, polyhydroxy-functional acrylonitrile/butadiene copolymers and mixtures thereof, in particular diols thereof, and mixtures thereof. 
     Examples of polyetherpolyols are polyoxyethylenepolyols, polyoxypropylenepolyols and polyoxybutylenepolyols, in particular polyoxyethylenediols, polyoxypropylenediols, polyoxybutylenediols, polyoxyethylenetriols and polyoxypropylenetriols. Polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation of less than 0.02 meq/g and having an average molecular weight in the range from 1000 to 30000 g/mol and polyoxyethylenediols, polyoxyethylenetriols, polyoxypropylenediols and polyoxypropylenetriols having an average molecular weight of from 400 to 8000 g/mol are suitable. 
     Further examples of polyetherpolyols are so-called ethylene oxide-terminated (“EO-endcapped”, ethylene oxide-end-capped) polyoxypropylenepolyols, styrene-acrylonitrile-grafted polyetherpolyols, e.g. Lupranol® from Elastogran GmbH, Germany. 
     Particularly preferred polyols to be used in the present invention are poly-hydroxy-functional fats and oils, for example natural fats and oils, such as castor oil, or polyols obtained by chemical modification of natural fats and oils, so-called oleochemical polyols. Castor oil is particularly preferred. 
     Examples of chemically modified natural fats and oils are polyols obtained from epoxypolyesters or epoxypolyethers obtained, for example, by epoxidation of unsaturated oils, by subsequent ring opening with carboxylic acids or alcohols, polyols obtained by hydroformylation and hydrogenation of unsaturated oils, or polyols which are obtained from natural fats and oils by degradation processes, such as alcoholysis or ozonolysis, and subsequent chemical linkage, for example by transesterification or dimerization, of the degradation products thus obtained or derivatives thereof. Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized, for example, by hydroformylation and hydrogenation to give hydroxy-fatty acid esters. 
     The polyols mentioned above usually have a relatively high molecular weight, for instance, an average molecular weight of from 250 to 30000 g/mol, in particular from 1000 to 30000 g/mol, and/or an average OH functionality in the range from 1.6 to 3. 
     Further examples of suitable polyols are low molecular weight di- or polyhydric alcohols, e.g., with a molecular weight of less than 250 g/mol. Examples thereof are 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentylglycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols, such as xylitol, sorbitol or mannitol, sugars, such as sucrose, other alcohols having a higher functionality, low molecular weight alkoxylation products of the abovementioned di- and polyhydric alcohols, and mixtures thereof. 
     While said low molecular weight di- or polyhydric alcohols may be used as the polyol, the use of the polyols mentioned above having a high molecular weight is preferred. In a preferred embodiment at least one high molecular weight polyol and at least one low molecular weight di- or polyhydric alcohol are used in combination. As mentioned, a low molecular weight polyol is considered to have a molecular weight of less than 250 g/mol, whereas a high molecular weight polyol is considered to have an average molecular weight of 250 g/mol or more. 
     In a preferred embodiment binder component (B) comprises at least one low molecular weight polyol, based on the total weight of component (B), preferably in combination with at least one high molecular weight polyol. 
     Particularly preferred is a combination of one or more polyhydroxy-functional fats and oils, such natural fats and oils, or polyols obtained by chemical modification of natural fats and oils, in particular castor oil, and one, two or more low molecular weight di- or polyhydric alcohols. In such combinations, the one or more polyols having a high molecular weight are usually used in higher amounts than the at least one low molecular weight di- or polyhydric alcohol. 
     Examples of suitable epoxy resins are epoxy resins customary in epoxy chemistry. Epoxy resins can be prepared in a known manner, e.g. from the oxidation of the corresponding olefins or from the reaction of epichlorohydrin with the corresponding polyols, polyphenols or amines. Epoxy resins can be classified in liquid epoxy resins which have a glass transition temperature which is typically below 25° C., and solid epoxy resins having a glass transition temperature above 25° C. The epoxy resin may have an epoxy equivalent weight in the range of 65 to 500 g/eq. The epoxy resin is preferably a diepoxide. 
     In one embodiment, the epoxy resin may be an aromatic epoxy resin. Suitable examples are liquid epoxy resins of the following formula (I) 
     
       
         
         
             
             
         
       
     
     where R′ and R″ are each independently a hydrogen atom or a methyl group, and s has an average value of 0 to 1. Preference is given to those liquid resins in which index s has an average value of less than 0.2. 
     The liquid resins of the above formula are diglycidyl ethers of bisphenol A, bisphenol F and bisphenol A/F, where A represents acetone and F formaldehyde, which serve as reactants for preparation of these bisphenols. 
     Further suitable aromatic epoxy resins are the glycidylization products of
         dihydroxybenzene derivatives such as resorcinol, hydroquinone and catechol;   further bisphenols or polyphenols such as bis(4-hydroxy-3-methylphenyl)-methane, 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxy-phenyl)propane, 2,2-bis(4-hydroxy-3-tert.-butyl-phenyl)propane, 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 3,3-bis(4-hydroxyphenyl)pentane, 3,4-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)-heptane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1,1-bis(4-hydrox-yphenyl)-1-phenyl-ethane, 1,4-bis[2-(4-hydroxyphenyl)-2-propylbenzene) (bisphenol P), 1,3-bis[2-(4-hydroxy-phenyl)-2-propyl]benzene) (bisphenol M), 4,4′-dihydroxydiphenyl (DOD), 4,4′-dihydroxybenzophenone, bis(2-hydroxynaphth-1-yl)methane, bis(4-hydroxynaphth-1-yl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxy-phenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bis(4-hydroxy-phenyl)ether, bis(4-hydroxyphenyl)sulfone;   condensation products of phenols with formaldehyde, which are obtained under acidic conditions, such as phenol novolacs or cresol novolacs;   aromatic amines, such as aniline, toluidine, 4-aminophenol, 4,4′-methylenediphenyldiamine (MDA). 4,4′-methylenediphenyldi(N-methyl)amine, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline (bisaniline P), 4,4′-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline (bisaniline M).       

     In a further embodiment, the epoxy resin may be an aliphatic or cycloaliphatic polyepoxide, for example
         diglycidyl ether;   a glycidyl ether of a saturated or unsaturated, branched or unbranched, cyclic or open-chain C 2  to C 30  diol, for example ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, a polypropylene glycol, dimethylolcyclohexane, neopentylglycol;   a glycidyl ether of a tri- or tetrafunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain polyol such as castor oil, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol or glycerol, and alkoxylated glycerol or alkoxylated trimethylolpropane;   a hydrogenated bisphenol A, F or A/F liquid resin, or the glycidylization products of hydrogenated bisphenol A, F or A/F;   a N-glycidyl derivative of amides or heterocyclic nitrogen bases, such as triglycidyl cyanurate and triglycidyl isocyanurate, and reaction products of epichlorohydrin and hydantoin.       

     Further examples of suitable epoxy resins are epoxy resins which have been prepared from the oxidation of olefins, for example from the oxidation of vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadiene or divinylbenzene. 
     The epoxy resin is more preferably a diepoxide selected from the group consisting of a bisphenol A, bisphenol F and bisphenol A/F diglycidyl ether, preferably having an epoxy equivalent weight of 156 to 250 g/eq, which are e.g. commercially available as Araldite®GY 250, Araldite®PY 304, Araldite® GY 282 (from Huntsman); D.E.R®331, D.E.R.®330 (from Dow); Epikote®828, Epikote® 862 (from Hexion); N,N-diglycidylaniline and a polyglycol diglycidyl ether, preferably having an epoxy equivalent weight of 170 to 340 g/eq, which are e.g. commercially available as D.E.R.® 732 and D.E.R.® 736 (from Dow). 
     Suitable examples of an epoxy resin are also a bisphenol A, F or A/F solid resin which is of similar composition to the liquid resins of the formula (I) mentioned above, where the index s has instead a value of 2 to 12. Further examples are one of the epoxy resins mentioned, which has been modified hydrophilic properties by the reaction with at least one polyoxyalkylenepolyol. 
     Preferred epoxy resins are bisphenol A, F or A/F solid or liquid resins, as available commercially, for example, from Dow, Huntsman and Hexion. 
     If the binder component (B) comprises an epoxy resin, component (B) may further comprise what is known as a reactive diluent. Suitable reactive diluents are mono- and polyepoxides, for example the glycidyl ethers of mono- or polyhydric phenols and aliphatic or cycloaliphatic alcohols, especially the polyglycidyl ethers of di- or polyols already mentioned as aliphatic or cycloaliphatic epoxy resins, and additionally especially phenyl glycidyl ether, cresyl glycidyl ether, p-n-butylphenyl glycidyl ether, p-tert.-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, allyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl ethers of natural alcohols, for example C 8 - to C 10 -alkyl glycidyl ethers or C 12 - to C 14 -alkyl glycidyl ethers, commercially available as Erysis® GE-7 and Erysis® GE-8 (from CVC). The addition of a reactive diluent to the epoxy resin causes a reduction in the viscosity and—in the hardened state of the epoxy resin composition—a reduction in the glass transition temperature and in the mechanical values. 
     The epoxy resin is preferably contained as either what is known as an “emulsifiable epoxy resin” or an aqueous epoxy resin emulsion or dispersion. An epoxy resin dispersion preferably comprises, as well as water, at least one epoxy resin as specified above, and preferably additionally at least one emulsifier, especially a nonionic emulsifier, e.g. an alkyl or alkylaryl polyglycol ether, especially a polyalkoxylated alkylphenol such as alkylphenoxypoly-ethyleneoxy)ethanol, e.g. a polyadduct formed from nonylphenol and ethylene oxide, containing up to 30 mol of ethylene oxide per mole of nonylphenol. 
     Commercial epoxy resin dispersions are, e.g., Sika Repair/Sikafloor® EpoCem® Module A (from Sika Schweiz AG), Araldite® PZ 323, Araldite® PZ 756/67, Araldite® PZ 3961 (from Huntsman), XZ 92598.00, XZ 92546.00, XZ 92533.00 (from Dow), Waterpoxy®1422, Waterpoxy®1455 (from Cognis), Beckopox®EP 384w, Beckopox® EP 385w, Beckopox® EP 386w, Beckopox® EP 2340w, Beckopox® VEP 2381w (from Cytec). Epoxy resin dispersions typically have a solids content in the range of 40-65% by weight. 
     An emulsifiable epoxy resin preferably contains at least one emulsifier as already mentioned above as a constituent of an epoxy resin dispersion. Commercial emulsifiable epoxy resins are, for example, Araldite® PY 340 and Araldite® PY 340-2 (from Huntsman), Beckopox® 122w and Beckopox® EP 147w (from Cytec). 
     The binder component (B) may comprise, as a third alternative, a polymer latex dispersion. A polymer latex dispersion is a dispersion, preferably a colloidal dispersion, of polymer particles in water. The polymer is preferably a thermoplastic polymer. Examples of suitable polymers for the polymer latex dispersion are (meth)acrylic ester polymers and copolymers, poly(vinyl acetate), styrene-butadiene copolymers, and vinyl acetate-ethylene copolymers. (Meth)acrylic means methacrylic or acrylic. 
     Preferred is a polymer latex dispersion of (meth)acrylic ester polymers or copolymers also called acrylic latex or acrylic polymer latex. Examples of (meth)acrylic ester polymers or copolymers are poly(meth)acrylic ester such as poly(methyl methacrylate), copolymers of two or more (meth)acrylic ester, such as methyl methacrylate-ethyl acrylate copolymer, styrene-(meth)acrylic ester copolymers such as styrene-butylacrylate copolymer, and styrene-(meth)acrylic ester-butadiene copolymers. Such polymer latices are commercially available. 
     Apart from the organic binder selected from one or more polyols, one or more epoxy resins and a polymer latex dispersion, the binder component (B) may contain further additives. Such additives are commonly used, if desired, and typically known to the persons skilled in the art. As mentioned, the binder component (B) preferably comprises water. Examples of optional further additives are plasticizers, pigments, adhesion promoters, such as silanes, e.g. epoxysilanes, (meth)acrylatosilanes and alkylsilanes, stabilizers against heat light and UV radiation, thixotropic agents, flow improving additives, flame retardants, surface active agents such as defoamers, wetting agents, flow control agents, deaerating agents, biocides and emulsifiers. 
     Preferably used optional additives for component (B) are one or more of plasticizers, such as benzoates, benzyl phthalates, e.g. Santicizer®160, and diisopropylbenzene, e.g. Benzoflex®9-88, pigments, such as inorganic and organic pigments, e.g. Bayferrox® and Heucosin®, defoamers, such as solvent silicon free and polyorganosiloxane, e.g. Tego®Airex and Efka®, and emulsifiers such as calcium hydroxide. Plasticizers are preferably used, if binder component (B) comprises one or more polyols. 
     Hardener Component (C) 
     If the binder component (B) comprises one or more polyols or one or more epoxy resins, the multi-component composition comprises a hardener component (C) which is an isocyanate hardener, if the binder component (B) comprises one or more polyols, or an amine hardener, if the binder component (B) comprises one or more epoxy resins. 
     Hardener component (C) is preferably a liquid component. The binder component (C) may be viscous but is generally pourable. 
     The isocyanate hardener is generally a polyisocyanate. Such polyisocyanates are commercially available and widely used as hardener. Examples for suitable polyisocyanates are hexamethylene diisocyanate (HDI), HDI trimers such as Desmodur®N 3600, toluene diisocyanate (TDI), isophorone diisocyanate (IPDI) such as Vestamat®T 1890, methylene diphenyl diisocyanate and derivatives of these polyisocyanates, wherein HDI and its derivatives, and methylene diphenyl diisocyanate and its derivatives are preferred, and methylene diphenyl diisocyanate is most preferred. 
     In the following, methylene diphenyl diisocyanate is abbreviated as MDI as usual. MDI is a useful compound, e.g. as a starting material for polyurethane production, and produced worldwide in millions of tons annually. A plurality of different product grades of MDI is available. “Methylene diphenyl diisocyanate” as this term is used in the present invention, include, depending on its grade, monomeric, and polymeric methylene diphenyl diisocyanate. 
     MDI is available in the form of three different isomers, namely 4,4′-methylene diphenyl diisocyanate (4,4′-MDI), 2,4′-methylene diphenyl diisocyanate (2,4′-MDI), and 2,2′-methylene diphenyl diisocyanate (2,2′-MDI). Commercially available MDI can be classified into monomeric MDI (also designated MMDI) and polymeric MDI (PMDI) also referred to as technical MDI. Polymeric MDI is the raw product of MDI synthesis containing MDI isomers and oligomeric species. Monomeric MDI is obtained from polymeric MDI by purification. 
     Monomeric MDI refers to “pure” MDI including products of a single MDI isomer or of isomer mixtures of two or three MDI isomers. The isomeric ratio can vary in wide ranges. For instance, 4,4′-MDI is a colorless to yellowish solid having a melting point of 39.5° C. Commercial monomeric MDI is often a mixture of 4,4′-MDI, 2,4′-MDI and typically very low levels of 2,2′-MDI. 
     Polymeric MDI includes oligomeric species in addition to MDI isomers. Thus, polymeric MDI contains a single MDI isomer or isomer mixtures of two or three MDI isomers, the balance being oligomeric species. Polymeric MDI tends to have isocyanate functionalities of higher than 2. The isomeric ratio as well as the amount of oligomeric species can vary in wide ranges in these products. For instance, polymeric MDI may typically contain about 30 to 80 wt.-% of MDI isomers, the balance being said oligomeric species. As in the case of monomeric MDI, the MDI isomers are often a mixture of 4,4′-MDI, 2,4′-MDI and very low levels of 2,2′-MDI. Polymeric MDI is typically a brown or dark amber liquid at room temperature (23° C.). 
     The oligomeric species are oligomers having a NCO functionality of 3 or higher. The oligomeric species are a result of the synthesis process and can be represented by the following formula 
     
       
         
         
             
             
         
       
     
     wherein n is 1 to 4 and higher. The amount of the homologues decreases with increasing chain length. The total content of homologues with n higher than 4 is generally not very high. 
     A wide variety of polymeric MDI grades is available with varying characteristics as to the number, type and content of isomers and oligomeric species, isomeric ratio, and weight distribution of the oligomeric homologues. These characteristics depend on type and conditions of synthesis and purification procedures. Moreover, the characteristics can be adjusted, e.g., by mixing different MDI grades according to the needs of the customer. 
     In the MDI used preferably at least 40 wt.-%, and more preferably at least 45 wt.-% of the MDI isomers are 4,4′-MDI. It is further preferred, that the MDI used comprises 2,4′-MDI and 4,4′-MDI in a ratio of 10:90 to 40:60. 
     The binder component (B) comprising a isocyanate hardener may optionally comprise one or more further additives such as solvents in relatively small amounts, e.g. up to 20 or up to 10 wt.-% of the additives all together, preferably up to 5 wt.-% and more preferably up to 2 wt.-% based on the total weight of the binder component (B). Suitable solvents include but are not limited to esters, ketones, hydrocarbons and chlorinated hydrocarbons. If MDI is used, it is generally preferred however, that the hardener component (C) comprising an isocyanate hardener consists of MDI, i.e. monomeric MDI and/or polymeric MDI. Since the MDI products are technical products, they may, of course, include low quantities of impurities. 
     The amine hardener which is used when the binder component (B) comprises one or more epoxy resins, is a compound having two or more amino groups. The amino groups may be primary or secondary amino groups. Amine hardeners for epoxy resins are known and commercially available. 
     The amine hardener may be a polyamine and is preferably a polyamine adduct. In particular, the amine hardener is preferably a polyamine-polyepoxide adduct, i.e. an adduct formed from polyamines and polyepoxides. Examples of the polyepoxides are the epoxy resins discussed above. The polyamine-polyepoxide adduct is preferably free of epoxy groups and contains secondary and/or primary amino groups. 
     Examples of suitable amine hardeners are e.g. described in EP-A1-2133381, EP-A1-0000605, EP-A1-0567831, EP-A1-0024915, the disclosure of which is incorporated by reference herein. 
     Water 
     The multi-component composition comprises water. The water is contained in the binder component (B) or, if present, in the hardener component (C). It is preferred that the water is contained in binder component (B). 
     If the binder component (B) comprises one or more polyepoxides, water may be comprised in hardener component (C) comprising the amine hardener and/or in the binder component (B). It is usually preferred that the binder component (B) comprising one or more polyepoxides comprises water, whether the hardener component (C) comprising the amine hardener contains water or not. If the hardener component (C) comprises the isocyanate hardener it is usually not preferred that the hardener component (C) comprises water. Hence, the binder component (B) comprising one or more polyols preferably contains water. The binder component (B) comprising the polymer latex dispersion generally also contains water. 
     When the components of the multi-component composition are mixed, the calcined paper sludge reacts with water. This reaction is similar to the reaction of water with cement, generally called hydration. Upon the reaction with the water, the calcined paper sludge is hardened to a solid material. When the organic binder is a polyol or an epoxy resin a further reaction occurs upon mixture where the organic binder is cured by the hardener component. The polymer latex dispersion usually does not react chemically but has rubber-like binding property. Thus, a hybrid solid material comprising an inorganic binder portion and an organic binder portion in which the aggregates are bound is formed. 
     Method for the Manufacture of a Hybrid Flooring or Coating 
     The multi-component composition of the invention is suitable for the manufacture of a flooring or coating, wherein the method comprises
     a) if a hardener component (C) is present, mixing binder component (B) and hardener component (C),   b) mixing solid component (A) with binder component (B) comprising the polymer latex dispersion or with the mixture of binder component (B) and hardener component (C) obtained in step a), to obtain a mixed material,   c) applying the mixed material to a substrate,   d) optionally smoothing the applied mixed material, and   e) curing the applied mixed material, to obtain the flooring or coating.   

     If a hardener component (C) is present, binder component (B) and hardener component (C) are mixed with each other. Both binder component (B) and hardener component (C) are preferably liquid or pourable components. The solid component (A) is added to this mixture. If the binder component (B) comprises the polymer latex dispersion, the solid component (A) is added to this binder component (B). 
     There is only little dust formation during addition of component (A) so that no problems occur in this regard. The mixed material is then processed in the usual way to produce a flooring or coating. 
     A typical layer thickness of a flooring or coating e.g. ranges from 1 mm to 9 mm. However, the thickness may vary depending on the type of floor intended so that a lower or higher thickness is also suitable. The application temperature is e.g. from about 8 to 40° C. The curing time may e.g. range from 15 hours to 72 hours depending on the temperature during hardening. 
     The multi-component composition is suitable as a grout. It is particular suitable as a flooring or coating composition for preparing coatings and especially floorings, in particular as a self-leveling flooring or coating composition. 
     The invention is further explained in the following experimental part which, however shall not be construed as limiting the scope of the invention. The proportions and percentage indicated are by weight, unless otherwise stated. 
     Examples 
     Solid Component (A) 
     The ingredients indicated below are mixed to form component (A) containing calcined paper sludge and aggregates for Example 1 and cement and aggregates for Comparative Example 1. 
     Component (B) 
     Component (B) is MDI (Suprasec® 2652 from Huntsman). 
     Component (C) 
     The ingredients indicated below are mixed to form component (C) containing polyol and water for Example 1 and Comparative Example 1, respectively. 
     Example 1 and Comparative Example 1 
     Components (A), (B) and (C) for Example 1 and Comparative Example 1 are mixed in a weight ratio to obtain a mixture of Example 1 and Comparative Example 1, respectively, as indicated below. The portion of each ingredient is given in % by weight, based on the total weight of the mixture. 
     
       
         
           
               
               
               
             
               
                   
                   
               
               
                   
                 Ex. 1 
                 Comp. Ex. 1 
               
               
                   
                 amount [wt. %] 
                 amount [wt. %] 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Component (A) 
                 hydrated lime 
                 0.1 
                 3.5 
               
               
                   
                 silica sand 
                 44 
                 48 
               
               
                   
                 calcined paper sludge 
                 16 
                 — 
               
               
                   
                 white cement 
                 — 
                 18 
               
               
                   
                 CEM I 52.5 
               
               
                 Component (B) 
                 castor oil 
                 9.1 
                 8.5 
               
               
                   
                 plasticizer 
                 4 
                 2 
               
               
                   
                 defoamer 
                 0.6 
                 0.5 
               
               
                   
                 pigment 
                 1.2 
                 1.5 
               
               
                   
                 water 
                 5 
                 4 
               
               
                 Component (C) 
                 MDI 
                 20 
                 14 
               
            
           
           
               
               
               
            
               
                 total 
                 100.9 
                 100.9 
               
               
                   
               
            
           
         
       
     
     The mixed material according to Example 1 and Comparative Example 1 were applied to a substrate in order to prepare a flooring and tested with respect to handling and properties. The following methods have been used. The results are summarized in the table below. 
     Application Finish/Pinholes 
     The finished flooring is inspected visually for appearance and pinholes. 
     Blistering 
     The separate components including a primed (SR-161) wooden board of approx. 0.30×0.26 m with a wooden frame of 5 mm height were stored at 35° C. for 16-24 h. 1 kg of material was mixed for 3 min at 900 rpm and the material applied on the primed board to obtain a layer thickness of 4 mm. The surface was spike rolled and the board was placed back into the 35° C. oven. After curing, the surface was evaluated for cracks and blisters. Pinholes were not taken into account. 
     Flowability/Consistency 
     The test was carried out at 23° C./50% using the cone described in DIN EN 1015-3, but without tamping the material. 1 kg of material (at 23° C./50%) was mixed for 3 min at 900 rpm. The cone was set on the glass sheet, filled to the rim, lifted and the diameter of the resulting circle was determined after 10 min. The test was also carried out at 35° C. and at 12° C. 
     Pot Life or Working Life 
     Two methods were carried out at 23° C./50%, depending on the amount of material available. In preliminary tests we had determined that both methods resulted in the same time (+/−2 min) for the working life. The materials were kept at the above mentioned temperature prior to mixing. 
     Material was applied in 6 mm thickness in a plastic lid of 25 cm diameter and after a certain time the diameter was scratched with a pallet knife, the time before the mark does not self heal anymore is regarded as the end of the working life. To carry out this test, 1 kg of material was mixed for 3 min at 900 rpm. The test was repeated at a temperature of 35° C. 
     Impact Resistance 
     The test follows DIN EN ISO 6272. An impact resistance tester of Fa. Erichsen, model 304, is used. The mixture to be studied is applied to the surface of the concrete test specimen of 300 mm×300 mm×40 mm. The test specimens are stored and tested at (23±2)° C. and (50±5)% relative humidity. Attach the test specimen to the impact test device. Lift the weight (1000 g) to a height at which no damage is expected. Release the weight so that it drops onto the test specimen. Inspect the coating with the magnifying glass with 10 fold magnification for changes, cracking, and separation. If there are no cracks carry out the test again at new positions with increasing heights of fall till cracks can be found. Increase the height of fall each time by 25 mm or multiples thereof. If necessary, a heavier weight (2000 g) is used. If cracks can be found proceed as follows: Carry out the test at 5 different points with the appropriate weight with the following heights: from the height at which the first cracks were found, 25 mm higher and 25 mm lower. The coating passes the test if there are 4 positions with no cracks and no separating at least. The weight/height-of-fall combination is taken at which the results change from passed to not passed. The impact resistance in N/m (or Joule) results from the weight in N and the height of fall in meters. 
     Shrinkage 
     Using 4×4×16 cm prisms the shrinkage of the material was determined using DIN 52450 gauge type C. The material was filled into moulds and taken out after 24 h. The length of the prism was then determined and compared to the length determined after 1 d, 7 d 28 d after demoulding. The difference indicates the shrinkage. The test is carried out on three specimens and the shrinkage calculated as mm/m. 
     Compressive Strength/Flexural Strength 
     Samples 4×4×16 cm were prepared by filling the moulds with the respective materials, the samples were taken out of the moulds after 1 d and the test carried out according to EN 13892-2 (DIN EN 196-1) after 1 d, 7 d and 28 d of curing at 23° C./50%. The increase of load for the flexural strength is 50±10 N/s and for the compressive strength it is 2400±200 N/s. The result for the flexural strength is the mean out of three and for the compressive strength, the mean out of six. 
     Shore D Hardness 
     Samples of 4 mm (Policrete, Flowfresh, Ucrete) resp. 4.5 mm (SR-21 N Purcems) thickness were cast and cured at the respective temperatures (8° C., 23° C./50% and 35° C.). Shore D was determined with an automatic gauge at 3 s and 15 s. Three measurements were taken at different times over 28 d and the mean is stated in the table. The results are only suitable for comparative evaluation, as the samples contain sand and thus the hardness is not to be determined with the Shore method. 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Product 
                 Comp. Ex. 1 
                 Ex. 1 
               
               
                   
               
             
            
               
                 Application finish 
                 matt 
                 medium gloss 
               
               
                   
                   
                 (60° = 25) 
               
               
                 Application T 
               
            
           
           
               
               
               
               
               
            
               
                 Lower limit 
                 8° 
                 C. 
                 12° 
                 C. 
               
               
                 Upper limit 
                 35° 
                 C. 
                 35° 
                 C. 
               
            
           
           
               
               
               
            
               
                 Blistering 
                 no 
                 no 
               
               
                 Pinholes 
                 no 
                 yes 
               
               
                 Flowability 
               
               
                 23° C. 
                 320 mm-340 mm 
                 305 mm-325 mm 
               
               
                 35° C. 
                 320 mm-345 mm 
                 305 mm-330 mm 
               
               
                 12° C. 
                 275 mm-300 mm 
                 250 mm-275 mm 
               
               
                 Pot life 
               
            
           
           
               
               
               
               
               
            
               
                 23° C. 
                 26 
                 min 
                 26 
                 min 
               
               
                 35° C. 
                 24 
                 min 
                 24 
                 min 
               
               
                 Impact resistance 
                 10 
                 N/m 
                 18 
                 N/m 
               
               
                   
                   
                 (open, 
                   
                 (cracks, but 
               
               
                   
                   
                 cracks) 
                   
                 no openings) 
               
               
                 Shrinkage @ 23° C. 
               
               
                  1 d 
                 −0.5 
                 mm/m 
                 −0.008 
                 mm/m 
               
               
                  7 d 
                 −0.9 
                 mm/m 
                 −0.215 
                 mm/m 
               
               
                 28 d 
                 −1.06 
                 mm/m 
                 n.d. 
               
               
                 Compressive strength @ 
               
               
                 23° C. 
               
               
                  1 d 
                 31.3 
                 N/mm 2   
                 47.3 
                 N/mm 2   
               
               
                  7 d 
                 47.8 
                 N/mm 2   
                 61.8 
                 N/mm 2   
               
               
                 28 d 
                 52.1 
                 N/mm 2   
                 70.0 
                 N/mm 2   
               
               
                 Flexural strength @ 23° C. 
               
               
                  1 d 
                 10 
                 N/mm 2   
                 16.6 
                 N/mm 2   
               
               
                  7 d 
                 14.6 
                 N/mm 2   
                 19.2 
                 N/mm 2   
               
               
                 28 d 
                 16.4 
                 N/mm 2   
                 19.8 
                 N/mm 2   
               
            
           
           
               
               
               
            
               
                 Shore D hardness @23° C. 
                   
                   
               
               
                  1 d 
                 70 
                 74 
               
               
                  2 d 
                 76 
                 79 
               
               
                  3 d 
                 82 
                 81 
               
               
                 Shore D hardness@8° C. 
               
               
                  1 d 
                 10 
                 21 
               
               
                  2 d 
                 60 
                 53 
               
               
                  3 d 
                 68 
                 78 
               
               
                   
               
            
           
         
       
     
     As can be seen from the results, the composition comprising calcined paper sludge has similar, and in some cases even improved, properties compared to the comparative composition using cement. 
     Example 2 
     The following components (A), (B) and (C) were mixed to obtain a mixture for preparing a flooring. The properties of the floorings are sufficient and similar to corresponding common mixtures where only cement is used instead of a combination of calcined paper sludge and cement. The proportions are given in % by weight, based on the mixture. 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Comp. 
                 Ingredients 
                 amount [wt. %] 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 (A) 
                 calcined paper sludge/cement/aggregates/ 
                 82.5 
               
               
                   
                 hydrated lime 
               
               
                 (B) 
                 epoxy resin/water 
                 5 
               
               
                 (C) 
                 Amine/water 
                 12.5 
               
               
                   
               
            
           
         
       
     
     Example 3 
     The following components (A) and (B) were mixed to obtain a mixture for preparing a flooring. The properties of the floorings are sufficient and similar to corresponding common mixtures where only cement is used instead of a combination of calcined paper sludge and cement. The proportions are given in % by weight, based on the mixture. 
     
       
         
           
               
               
               
             
               
                   
               
               
                 Comp. 
                 Ingredients 
                 amount [wt. %] 
               
               
                   
               
             
            
               
                 (A) 
                 calcined paper sludge/cement/aggregates/ 
                 75 
               
               
                   
                 hydrated lime 
               
               
                 (B) 
                 acrylate latex dispersion in water 
                 25