阅读说明：本技术 单组分环氧树脂水泥砂浆 (Single-component epoxy resin cement mortar ) 是由 F·乌尔米利 T·穆瑟 于 2018-05-31 设计创作，主要内容包括：本发明涉及一种包含水泥、填料、聚合物和具有环氧基团的化合物以及胺的组合物,其中该组合物含有超过10wt％的水泥和在室温下作为储存稳定的自由流动的粉末和/或颗粒存在。当与水混合时,该组合物使得聚合物改质的砂浆可以具有良好的可加工性、优异的粘附性、强度、水不可渗透性、耐化学性和快速可涂性。(The invention relates to a composition comprising cement, filler, polymer and a compound having epoxide groups and an amine, wherein the composition contains more than 10 wt% cement and is present as a storage-stable, free-flowing powder and/or granules at room temperature. When mixed with water, the composition allows polymer-modified mortars to have good processability, excellent adhesion, strength, water impermeability, chemical resistance, and rapid coatability.)

1. A composition comprising

-at least one cement, at least one of which,

-at least one inorganic filler,

-at least one powder comprising at least one polymer P,

-at least one compound containing epoxy groups,

wherein at least one compound containing epoxy groups is the same as or different from the polymer P, and

at least one amine having at least three amine hydrogens reactive with epoxide groups,

characterized in that the composition contains more than 10% by weight of cement and is present as a storage-stable free-flowing powder and/or granules at room temperature.

2. Composition according to claim 1, characterized in that the polymer P comprises a copolymer of styrene and acrylic esters, in particular styrene and butyl acrylate, containing monomeric building blocks.

3. Composition according to any one of the preceding claims, characterized in that it contains from 0.5 to 20, preferably from 2.5 to 18, more preferably from 3.2 to 15% by weight of polymer P.

4. A composition according to any of claims 1 to 3, characterized in that the compound containing epoxy groups is the same as polymer P and is a copolymer having covalently bound epoxy groups.

5. A composition according to any of claims 1 to 3, characterized in that the compound containing epoxy groups is different from the polymer P and is an epoxy resin.

6. The composition of claim 5, wherein the epoxy resin is present in intimate admixture with the polymer P.

7. A composition according to any of the preceding claims characterised in that the amine having at least three amine hydrogens reactive with epoxide groups is a component of a water dilutable amine or a water dilutable mixture of amines.

8. The composition of claim 7 comprising a water-dilutable amine mixture comprising at least one amine-epoxide adduct having at least three amine hydrogens.

9. A composition according to any of the preceding claims, characterized in that the amine is present in a form applied to an inorganic support material.

10. The composition as claimed in claims 1, 2 and 4 to 9, characterized in that it contains

11-45 wt% of cement, based on the total weight of the cement,

40-85 wt% of an inorganic filler,

0.5 to 20 wt% of a powder comprising polymer P,

0.1 to 7 wt% of an epoxy resin,

0.05 to 6% by weight of an amine, and

0-10 wt.% of other additives.

11. A method of preparing a composition as claimed in any preceding claim, comprising the steps of:

a) providing a premix by spray drying an aqueous dispersion comprising:

at least one polymer P and

-at least one compound containing epoxy groups,

wherein at least one compound containing epoxide groups is identical to or different from the polymer P,

b) providing an amine-containing powder by applying at least one amine having at least three amine hydrogens reactive with epoxide groups, optionally in the form of a water-dilutable amine mixture, to a powdery inorganic support material,

c) the epoxy group-containing powder and the amine-containing powder are mixed with the other ingredients of the composition.

12. A polymer-modified mortar comprising the composition of any one of claims 1-10 and water.

13. Use of a polymer-modified mortar as claimed in claim 12 as masonry mortar, plastering mortar, repair mortar, troweling filler, screed, coating, anti-corrosive coating or self-leveling floor screed for subsequent floor covering.

14. Polymer-modified mortar according to claim 12, characterized in that it has a surface moisture content of less than 4 wt% water, measured as an average of 6 measurements after at most 24 hours, preferably after at most 21 hours, using a Tramex CME4 concrete moisture meter, when applied to dry concrete in a layer thickness of 1.5 to 3mm and then degassed with a nail roller and subsequently stored at 21 ℃ and 65% relative air humidity.

15. Use of a water-dilutable amine mixture comprising as constituents of a pulverulent or granular composition comprising cement, an inorganic filler and a powder comprising at least one polymer P and at least one compound comprising epoxide groups:

-at least one amine-epoxide adduct of formula (I),

-at least one amine-epoxide adduct of formula (II),

at least one amine-epoxide adduct of the formula (III) and

at least one amine having two primary amino groups and being free of further amino groups and ether groups,

wherein

a is an integer of 0 to 10, b is an integer of 1 to 10, n is an integer of 5 to 50 and the sum of (a + b) is an integer of 1 to 10,

p is 0 or 1 and q is 0, 1, 2 or 3,

e is a diepoxide group after removal of two epoxy groups,

R¹is a monovalent organic radical having a molecular weight of from 15 to 150g/mol, in particular pent-3-en-2-one-4-yl or hex-4-en-2-one-5-yl or benzyl,

R²is a monovalent organic radical having a molecular weight of 100-280g/mol, in particular octyl, 2-ethylhexyl, nonyl, decyl, C₁₂To C₁₈-alkyl or C₁₂To C₁₈-alkylaminopropyl, and

a is a divalent organic group having a molecular weight of 28 to 500g/mol, in particular a polyoxypropylene group having a molecular weight of 180-500 g/mol.

Technical Field

The invention relates to one-component polymer-modified compositions containing cement, to the production of such compositions and to their use as mortars, screeds (Estrich), coatings or corrosion protection.

Prior Art

Polymer modified mortars are well known in the construction art.

DE 102010039315 describes water-redispersible polymer powders comprising film-forming base polymers, additives and protective colloids for improving the storage stability of cement-or cement-based dry mortars.

Mortars or concretes modified with epoxy resins are likewise known. These are typically three-component products comprising a liquid component containing an epoxy resin emulsified in water, a further liquid component containing a water-dilutable curing agent for the epoxy resin and a solid component containing cement and admixtures. The three components are stored in separate containers and only mixed with one another during processing, so that the curing reaction of cement and epoxy resin takes place simultaneously. The compositions modified with epoxy resins achieve good adhesion to moist substrates, good water retention and a high degree of water impermeability.

US 2016/152522 describes a multicomponent composition comprising a binder component comprising an epoxy resin, a curing agent component comprising an amine curing agent and a solid component comprising a hydraulic binder.

However, the fact that such a system is a three-component system is accompanied by disadvantages. The handling of the three components is very complicated for the workers and error-prone and can result in considerable waste at the construction site, since the liquid components are stored in water-resistant and robust containers, such as plastic bottles or cans.

Attempts have been made to reduce the number of components in epoxy resin modified mortars.

EP 0409787 describes a cement-containing dry mixture which contains an epoxy resin and a curing agent, wherein the epoxy resin and the curing agent are each present in the form of a separate coating on a small carrier material. However, the mixtures described do not have satisfactory storage stability, in particular at higher temperatures.

EP 0786439 describes a polymer-modified ready-to-use mixture in which two mixing components are mixed: one containing an epoxy resin, cement and latent hydraulic binder, and the other containing an amine curing agent. The ready-to-use mixtures containing the two mixed components have poor storage stability and show an undesirably slow strength development after mixing with water.

EP0580588 describes a dry cement mortar containing cement, aggregate, reactive resin and curing agent. The curing agent is added to the mortar in the form of a reaction product with an organic acid or a functional derivative thereof.

DE3308622 discloses a process for preparing reactive resin-hardener compositions, in which the resin and hardener are sprayed separately and a dusty material is deposited on the surface of the droplets. In another method described in DE3308622, the resin and the curing agent are reacted in the form of a liquid mixture and an organic acid is added before the curing is complete in order to block the remaining free reactive groups of the curing agent. WO 2010/086217 describes a polymer powder composition which contains an epoxy resin. The preferred use is in cement-free or low-cement systems, which are expensive and far from meeting the requirements for epoxy-modified cement mortars.

EP 2537897 discloses the use of a polymer powder consisting of an epoxy resin, a vinyl ester polymer and a surfactant in a cement-based mixture without the use of a curing agent for the epoxy resin.

EP 2537896 describes a water-redispersible polymer powder comprising a thermally curable epoxy resin, a colloidal stabilizer and an interfacial crosslinking agent.

Epoxy resin systems which do not contain amine curing agents require elevated temperatures to cure the epoxy resins, which can only be achieved with great difficulty on the construction site, or they cure only very slowly and/or insufficiently, whereby the high requirements of epoxy resin-modified cement mortars are likewise not met.

For this reason, there is a continuing need for high quality epoxidized resin modified mortars with good storage stability and simplified handling.

Summary of The Invention

It is therefore an object of the present invention to provide storage-stable one-component mortar compositions containing compounds having epoxide groups, which have good processing and final properties after mixing with water.

This object is surprisingly achieved by the composition described in claim 1.

The compositions are one-component, i.e. storage-stable when stored properly and then only have to be mixed with water, which is particularly advantageous compared to three-component epoxy resin-modified mortars according to the prior art. Logistics, storage and transportation are less costly, handling is simpler, faster and less prone to error, and less waste is generated on the construction site. In the case of one-component compositions, incorrect dosing of the components is excluded, in particular when only a portion of the pre-metered packaging material is used.

Although the epoxy group and the amine curing agent are present together in one component, the composition is surprisingly very stable. The presence of the polymer P surprisingly increases the storage stability of the composition. The compositions according to the invention make possible particularly good adhesive properties and strength, high water impermeability, particularly rapid coatability and good chemical resistance.

Other aspects of the invention are the subject of other independent claims. Particularly preferred embodiments of the invention are the subject matter of the dependent claims.

Modes for carrying out the invention

The present invention provides a composition comprising

-at least one cement, at least one of which,

-at least one inorganic filler,

at least one powder comprising at least one polymer P,

-at least one compound containing epoxy groups,

-wherein the at least one compound containing epoxide groups is the same as or different from the polymer P, and

-at least one amine having at least three amine hydrogens reactive with epoxide groups,

the composition contains more than 10% by weight of cement and is present as a storage stable free-flowing powder and/or granules at room temperature.

Compositions are said to be "storage stable" when they are still unrestrictedly usable when used as intended after storage in a suitable container for at least one month, preferably at least three to six months or longer.

Herein, "room temperature" is a temperature of 21 ℃.

In this context, a "redispersible polymer powder" is a powder which contains a polymer and which, after introduction into water, forms a stable dispersion. The term "redispersible polymer powder" includes not only the polymer itself but also its mixture with protective colloids, emulsifiers and carrier materials.

As cement, any available cement type or mixture of two or more types of cement may be used, for example cements classified according to DIN EN 197-1: portland cement (CEM I), portland composite cement (CEM II), blast furnace slag cement (CEM III), pozzolan cement (CEM IV), and composite cement (CEM V). Of course, cements produced according to alternative standards, such as ASTM standards or indian standards, are equally suitable.

Particularly preferred are cements according to european standard EN 197-1, calcium sulpho-aluminates cements, calcium aluminates cements or mixtures thereof, optionally mixed with calcium sulphate.

Most preferred is portland cement according to EN 197-1 or a cement comprising portland cement. Portland cement is particularly readily available and makes possible mortars with good properties.

Also particularly suitable are mixtures of cement, calcium aluminate cement and calcium sulphate or mixtures of cement and calcium sulphoaluminate cement. Such binder mixtures make possible short setting times and high early strengths.

The composition preferably contains no latent hydraulic binders, since the reaction with water and thus the development of strength of these binders proceeds only very slowly.

The proportion of cement in the composition is greater than 10% by weight, preferably greater than 15% by weight, particularly preferably greater than 18% by weight, based on 100% by weight of the dry composition. The composition particularly preferably contains 11 to 45 wt%, more preferably 15 to 40 wt%, most preferably 18 to 40 wt% cement.

Such amounts of cement make it possible for the cured composition to have a particularly high strength.

The composition contains, in addition to cement, at least one inorganic filler. Fillers are chemically inert, solid, particulate materials and are provided in a variety of shapes, sizes and different materials. They can range from fine sand to large coarse stones. Particularly suitable fillers are sand, gravel, crushed stone, calcined pebbles or light fillers, in particular clay, pumice, perlite or vermiculite. Other suitable fillers are alumina, calcium carbonate, fibers or amorphous silica (fumed silica).

The filler preferably contains sand, in particular quartz sand. This results in particularly good processability of the composition and a smooth and attractive surface after curing.

The particle size of the filler is preferably less than 5 mm.

In particular, the filler has a particle size in the range from 0.1 μm to 3.5mm, with sand, in particular quartz sand, being particularly preferred. The particle size may be determined by sieve analysis. The preferred particle size depends on the application.

The proportion of the inorganic filler in the composition is preferably 40% by weight or more, more preferably 40 to 85% by weight, based on 100% by weight of the dry composition.

The composition additionally contains at least one powder comprising at least one polymer P. The polymer P is usually solid at room temperature.

The powder containing polymer P is preferably a water-dispersible polymer powder. Such powders are preferably obtained by drying, in particular by spray drying, of aqueous dispersions containing at least one polymer P.

The polymer P is preferably an organic polymer prepared by free-radical polymerization in water. The polymerization is usually carried out as a dispersion polymerization in the presence of emulsifiers and/or water-soluble protective colloids, in particular polyvinyl alcohols.

If the free-radical polymerization for preparing the polymers P is carried out in the presence of protective colloids and/or emulsifiers, the polymer dispersions and thus the powders obtained by drying likewise contain these protective alternans and/or emulsifiers.

Protective colloids and/or emulsifiers can improve the redispersion properties of the powder.

The polymers P preferably contain styrene, ethylene, butadiene, acrylates, vinyl chloride, vinylidene chloride or vinyl acetate as monomer building blocks. Particularly suitable are polymers P which comprise copolymers comprising the monomer building blocks styrene and acrylates, in particular styrene and butyl acrylate.

Preferably, the minimum film-forming temperature (MFT) of the polymer P is 25 ℃ or less, more preferably less than 19 ℃. Such polymers, when they are present in dispersion form, form films by coagulation at or below the MFT. This film formation occurs in particular when the dispersion dries. A low MFT is advantageous, especially at relatively low temperatures.

The compositions preferably contain from 0.5 to 20, more preferably from 2.5 to 18, even more preferably from 3.2 to 15,% by weight, based on 100% by weight of the dry composition, of the polymer P.

In a preferred embodiment, inert inorganic carrier materials and/or protective colloids are added to the dispersion containing the polymer P before, during or after the spray drying. In this way, the flowability of the powder and/or the redispersibility of the powder can be improved.

In the present invention, the "inorganic carrier material" is a fine inorganic powder. It can be mixed with softer or liquid ingredients to obtain a free flowing powder.

The inorganic support material is preferably a fine powder having a specific surface area of from 0.1 to 500m²/g and/or having a particle size in the range of 10nm to 10 μm. The inorganic support material is preferably inert, i.e. it does not react with the added material. Such powders are preferably calcium or magnesium carbonate, dolomite, quartz powder, amorphous silica, pumice, titanium dioxide, aluminium silicate, talc, mica, diatomaceous earth, gypsum, alumina, kaolin, metakaolin, magnesite, shale powder, stone powder or mixtures thereof. In particularPreferred are calcium carbonate, dolomite, amorphous silica, clay or mixtures thereof.

Preferred protective colloids are, in particular, partially or completely hydrolyzed polyvinyl alcohols, polyvinylpyrrolidone, polyvinyl acetals, polysaccharides in water-soluble form, for example carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, proteins such as casein or caseinate, soy proteins or gelatin. Particularly preferred are partially hydrolyzed polyvinyl alcohols having a degree of hydrolysis of from 80 to 95 mol%.

In a preferred embodiment, the compound containing epoxy groups is the same as polymer P and is a copolymer having covalently attached epoxy groups.

Such polymers may be prepared by free radical polymerization of at least one monomer bearing an epoxy group. Such monomers are preferably selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and mixtures thereof.

In addition to the monomers bearing epoxy groups, the polymers preferably contain further monomers, in particular from the group consisting of styrene, ethylene, butadiene, acrylates, vinyl chloride, vinylidene chloride, vinyl acetate and mixtures thereof.

Polymers containing covalently bound epoxy groups can particularly preferably be prepared by free-radical copolymerization of styrene, alkyl acrylates, in particular butyl acrylate, and glycidyl methacrylate.

The polymers P having covalently bound epoxide groups are preferably prepared by free-radical dispersion polymerization in water, optionally in the presence of emulsifiers and/or water-soluble protective colloids. The polymer dispersion obtained in this way is preferably spray-dried to obtain a powder comprising the polymer P. Inert inorganic carrier materials and/or protective colloids can optionally be added before, during or after spray drying.

The polymers P having covalently bonded epoxide groups preferably have an epoxide number per g of polymer P of from 0.5 to 3.0, more preferably from 0.8 to 2.5, particularly preferably from 1.0 to 2.0mmol of epoxide groups.

The polymers P having covalently bonded epoxide groups are preferably present as water-redispersible powders and have a minimum film-forming temperature (MFT) of 25 ℃ or less, more preferably 19 ℃ or less.

The polymers with film-forming properties and covalently bound epoxide groups can be cured surprisingly well by conventional amine-type curing agents and improve the durability, in particular the strength and chemical resistance and the water impermeability of the mortar

In another preferred embodiment, the compound containing epoxy groups is not identical to the polymer P and is an epoxy resin.

Any epoxy resin is suitable as long as it is capable of being emulsified or dispersed in water and can be reacted with conventional amine curing agents at ambient temperature, particularly at temperatures of 5 to 35 ℃.

The epoxy resin is preferably a liquid epoxy resin.

Preferred are epoxy resins having a glass transition temperature of 25 ℃ or less.

Particularly preferred are epoxy resins based on bisphenol A-diglycidyl ether or bisphenol F-diglycidyl ether or bisphenol A/F-diglycidyl ether.

The epoxy resin may additionally contain at least one reactive diluent, in particular a glycidyl ether of a monohydric or polyhydric phenol or an aliphatic or cycloaliphatic alcohol.

The epoxy resins may additionally contain emulsifiers, in particular nonionic emulsifiers. This improves the emulsifiability of the composition during processing.

The compositions preferably contain from 0.1 to 7, more preferably from 0.5 to 5, particularly preferably from 0.7 to 2.5,% by weight, based on 100% by weight of the dry composition, of epoxy resin.

It has surprisingly been found that by combining an epoxy resin with a polymer P, the epoxy resin is incorporated into the composition in a migration-resistant and storage-stable manner.

The epoxy resin is preferably present in intimate admixture with the polymer P. The mixture preferably additionally contains an inorganic carrier material and/or a water-soluble protective colloid.

When polymer P is present in admixture with the epoxy resin, polymer P preferably does not contain any covalently attached epoxy groups. Preferably the polymer P is present as a powder and is redispersible in water and has a minimum film-forming temperature (MFT) of 25 ℃ or less, more preferably 19 ℃.

These mixtures can be easily dispersed upon contact with water. The polymers P surprisingly lead here to particularly good storage stability of the compositions and make possible particularly good adhesive properties and strength, particularly fast coatability, high water impermeability and particularly high chemical resistance.

The weight ratio of epoxy resin to polymer P is preferably from 1:1 to 1:10, particularly preferably from 1:3 to 1: 8.

The mixture of epoxy resin and polymer P preferably has an epoxy value of from 0.5 to 3.0, more preferably from 0.8 to 2.5, particularly preferably from 0.8 to 1.5mmol of epoxy groups per g of polymer P.

This mixture is in particular a redispersible powder and is preferably present in the composition in an amount of from 0.6 to 20, more preferably from 4 to 16% by weight, based on 100% by weight of the dry composition.

The intimate mixture of epoxy resin and polymer P can be prepared by mixing the powder comprising polymer P with the epoxy resin, optionally together with a carrier material and/or a protective colloid, in a suitable mixer.

The intimate mixture of epoxy resin and polymer P is preferably obtained by mixing an aqueous dispersion containing polymer P with the epoxy resin and subsequently spray drying. Such mixtures are particularly storage-stable.

The inert inorganic carrier material and/or the protective colloid can optionally be mixed before, during or after spray drying. The inorganic carrier material is preferably present in an amount of up to 50 parts by weight, more preferably up to 30 parts by weight, even more preferably up to 20 parts by weight, based on 100 parts by weight of the anhydrous mixture of epoxy resin and polymer P.

In this amount, the inorganic support material leads to particularly good storage stability of the composition.

Advantageously, a premix containing the epoxy resin and the powder comprising the polymer P is prepared and then added to the composition. The premix preferably does not contain compounds that can react with the epoxy resin as curing agents.

The mixtures prepared in this way can be dispersed particularly easily in water and are particularly storage-stable in the compositions without caking.

After reacting the composition with water, the amine having at least three amine hydrogens reactive with epoxide groups acts as a curing agent for the epoxide group containing compound in the composition.

The term amine hydrogen refers to a hydrogen atom that is directly attached to an amine nitrogen atom and that can react with an epoxy group. The at least three active amine hydrogens are preferably present in the form of free amines, in particular they are not present in the form of salts of organic or inorganic acids.

The salts of the amines release acid once the cement-containing composition is mixed with water. This may lead to undesirable side effects such as poor processability or curing delay.

The amine having at least three amine hydrogens reactive with epoxide groups is preferably a component of a water-dilutable amine or a water-dilutable amine mixture.

Suitable water-dilutable amine mixtures comprise in particular mixtures of (i) diamines or polyamines, (ii) polyalkyleneamines and (iii) amine-functionalized adducts of amines with epoxides.

The term "water dilutable" means that the liquid forms a homogeneous mixture without phase separation when it is mixed with water.

The composition preferably contains a water-dilutable amine mixture comprising at least one amine-epoxide adduct having at least three amine hydrogens.

The composition preferably contains 0.05 to 6 wt%, more preferably 0.3 to 4 wt%, most preferably 0.5 to 3.5 wt% of the amine based on 100 wt% of the dry composition.

A particularly preferred water-dilutable amine mixture comprises

-at least one amine-epoxide adduct of formula (I),

-at least one amine-epoxide adduct of formula (II),

at least one amine-epoxide adduct of the formula (III) and

at least one amine having two primary amino groups and being free of further amino groups and ether groups,

wherein

a is an integer of 0 to 10, b is an integer of 1 to 10, n is an integer of 5 to 50 and the sum of (a + b) is an integer of 1 to 10,

p is 0 or 1 and q is 0, 1, 2 or 3,

e is a diepoxide group after removal of two epoxy groups,

R¹is a monovalent organic radical having a molecular weight of from 15 to 150g/mol, in particular pent-3-en-2-one-4-yl or hex-4-en-2-one-5-yl or benzyl,

R²is a monovalent organic radical having a molecular weight of 100-280g/mol, in particular octyl, 2-ethylhexyl, nonyl, decyl, C₁₂To C₁₈-alkyl or C₁₂To C₁₈-an alkyl amino propyl group,

and

a is a divalent organic group having a molecular weight of 28 to 500g/mol, in particular a polyoxypropylene group having a molecular weight of 180-500 g/mol.

This water-dilutable amine mixture, after mixing with water, is particularly suitable for curing compositions comprising cement, inorganic filler, powder comprising at least one polymer P and at least one compound comprising epoxide groups.

The amine or amine mixture can be introduced directly into the composition by spraying or mixing.

In a preferred embodiment, the amine is applied to an inorganic support material. The support material is preferably a fine inorganic powder as described above, in particular a silicate, silica or a mixture thereof.

The amine or amine mixture can be applied to the support material in any manner, in particular by spraying or mixing.

The amine or amine mixture can be brought into contact with the support material, in particular in a concentrated solution of water or solvent, and the mixture can subsequently be dried completely or partially.

The amine or amine mixture is present in particular as a powder after application to the support material and is therefore particularly suitable for incorporation into compositions.

The mixture of amine and support material is preferably contacted with a liquid or viscous hydrophobic polymer. Mixtures of amines with hydrophobic polymers can also be applied to the support material. The polymer is preferably of low molecular weight. Preferred polymers are homopolymers or copolymers of polybutadiene or styrene-butadiene-styrene block copolymers. Most preferred are liquid homopolymers or copolymers of butadiene.

The amine curing agent for epoxy compounds remains unexpectedly stable in the composition and has only minimal amine odor after it is applied to an inert carrier material and treated with a hydrophobic polymer.

In a preferred embodiment, the amine is premixed with the carrier material and optionally the hydrophobic polymer and then added to the composition.

Such a premix is preferably a storage-stable powder. The powder preferably comprises from 20 to 80 wt%, more preferably from 30 to 40 wt%, of the inorganic carrier material, based on 100 wt% of the premix. Especially preferred premixes comprise from 20 to 80, preferably from 30 to 40, weight percent of the amine, from 0 to 50, preferably from 30 to 40, weight percent of the hydrophobic polymer, especially liquid polybutadiene, and from 20 to 80, preferably from 30 to 40, weight percent of the carrier material, especially amorphous silica, based on 100 weight percent of the premix. Such a premix preferably has an amine number of from 100 to 500mg KOH/g.

The ratio of epoxy groups to reactive amine hydrogens in the composition is preferably in the range of 1.5:1 to 1: 1.5. Such a ratio makes it possible to cure the epoxy resin well with the aid of the amine curing agent.

The composition may contain other additives. In particular, agents to reduce shrinkage may be added. Particularly suitable agents for reducing shrinkage are calcium sulphoaluminate and/or neopentyl glycol. Other optional ingredients are plasticizers, thickeners, thixotropic agents, emulsifiers, defoamers, pore formers, fibers, chromate reducing agents, dyes, pigments, water retention agents, hydrophobing agents, regulators, accelerators and/or retarders. In addition to these additives, all other additives known in mortar and concrete technology are possible additives.

In a preferred embodiment, the composition comprises

11-45 wt% of cement, based on the total weight of the cement,

40-85 wt% of an inorganic filler,

0.5 to 20% by weight of a powder comprising at least one polymer P,

0.1 to 7 wt% of an epoxy resin,

0.05 to 6 wt.% of an amine and

0 to 10 wt.% of other additives,

based on 100 wt% of the dry composition.

In a particularly preferred embodiment, the composition comprises

18-40% by weight of cement,

40-85 wt% of an inorganic filler,

2.5 to 18% by weight of a powder comprising at least one polymer P,

0.8 to 5 wt% of an epoxy resin,

0.5-3.5 wt.% of an amine and

1-10 wt% of additives selected from the group consisting of plasticizers, shrinkage reducers, chromate reducers, pigments, defoamers, accelerators, thickeners, protective colloids and emulsifiers, based on 100 wt% of the dry composition.

In another preferred embodiment, the composition comprises

11-45 wt% of cement, based on the total weight of the cement,

40-85 wt% of an inorganic filler,

0.5-20 wt% of a powder comprising at least one polymer P, wherein the polymer P contains covalently linked epoxy groups,

0.05 to 6% by weight of an amine, and

0 to 10 wt% of an additive,

based on 100 wt% of the dry composition.

The inorganic support material which is optionally present and has been incorporated into the composition together with the amine and/or the powder comprising the polymer P is counted as inorganic filler.

The compositions are storage stable free-flowing powders and/or granules at room temperature.

The composition is preferably prepared by mixing the individual components in a dry mixer.

Preferably, separate powdered premixes are prepared.

It is particularly preferred to prepare the first premix of the epoxy group-containing compound and the second premix of the amine separately. These premixes are preferably mixed separately from the other ingredients of the composition.

Preferred premixes contain a powder comprising a polymer P having covalently attached epoxy groups and optionally a carrier material and/or a protective colloid.

Further preferred premixes contain a powder comprising polymer P, an epoxy resin and optionally an inorganic carrier material and/or a protective colloid.

Such a premix is particularly preferably provided by spray drying an aqueous dispersion comprising a polymer P having covalently linked epoxy groups or by spray drying an aqueous dispersion comprising a polymer P and an epoxy resin.

The amine-containing premix preferably additionally comprises an inorganic carrier material onto which the amine has been applied and optionally a hydrophobic polymer as described above.

A preferred method of preparing the composition comprises the steps of:

a) providing a premix by spray drying an aqueous dispersion comprising

At least one polymer P and

-at least one compound containing epoxy groups,

wherein at least one compound containing epoxide groups is identical to or different from the polymer P,

b) by applying an amine having at least three amine hydrogens reactive with epoxide groups, optionally in the form of a water-dilutable amine mixture, to a powdery inorganic support material to provide an amine-containing powder,

c) the epoxy group-containing powder and the amine-containing powder are mixed with the other ingredients of the composition.

Additionally, the amine-containing powder can be mixed with a hydrophobic polymer.

The inorganic filler, cement and optionally further additives are preferably first mixed here, and the epoxy group-containing premix from step a) and the amine-containing powder from step b) are subsequently mixed separately from one another in any desired order.

The aqueous dispersion comprising the polymer P and the epoxy resin is preferably obtained by mixing an aqueous dispersion containing the polymer P with at least one epoxy resin.

Surprisingly, such compositions have good storage stability. This means that the properties of the powder in the composition do not change even after prolonged storage. Preferably, the composition after storage for one month, preferably 3 months, even more preferably 6 months or more at 21 ℃, after mixing with water, has processability and final properties comparable to those of the composition fresh after preparation. Most preferably the composition meets this requirement after 1 month, preferably after 3 months of storage at 35 ℃.

Preferred containers for storing the composition are bags, in particular paper bags with built-in plastic films, wherein the composition packaged in paper or paperboard must be protected from liquid water during storage, in particular from rain.

For processing, the composition according to the invention is mixed with water. The amount of water is preferably 0.30 to 0.50, preferably 0.35 to 0.45, corresponding to W/Z (weight ratio of water to cement).

The invention further provides a polymer-modified mortar comprising the composition and water.

Upon mixing with water, the ingredients of the composition solidify to form a solid. In the curing of the composition, cement reacts with water in a complex reaction to form cement hydrates, compounds having epoxide groups react with amines to form at least partially crosslinked polymers, and the particles of polymer P form an at least partially coherent polymer film.

The combination of cement, epoxy compound, amine and polymer gives the resulting polymer-modified mortar good final properties, such as in particular high strength, high water impermeability, high chemical resistance, good adhesion and rapid coatability.

Surprisingly, the compositions of the invention, after mixing with water and curing, have good processing and final properties similar to the three-component comparative compositions according to the prior art.

The polymer-modified mortar is preferably used as masonry mortar, plastering mortar, repair mortar, troweling filler, screed, coating, corrosion protection coating or self-leveling floor-levelling material for subsequent floor coverings.

Mortars made by mixing the composition with water are easy to process and have good compressive strength and adhesive properties when applied to a substrate such as concrete. The compressive strength after curing at 21 ℃ and 65% relative air humidity for 24 hours is advantageously greater than 10 MPa. This allows loading of the coating, for example by stepping on, without damaging the coating.

The adhesive strength, measured according to EN 1542, is advantageously greater than 2MPa, preferably greater than 2.5MPa, after storage at 21 ℃ and 65% relative air humidity for 7 days.

After mixing with water and application to a substrate such as concrete, the composition rapidly, preferably for up to 24 hours, more preferably 21 hours, achieves a surface moisture content of less than 4% by weight water. The waiting time until the application of the cover layer (for example sealing with an epoxy or polyurethane based coating) can thus be significantly reduced. Such a sealing layer or coating adheres well to the applied mortar.

Thus, preferred are polymer-modified mortars: when it is applied to dry concrete in a layer thickness of 1.5 to 3mm and subsequently degassed by means of a spike roller and then stored at 21 ℃ and 65% relative air humidity, the concrete moisture meter using the Tramex CME4 has a surface moisture content of less than 4% by weight of water, as an average of 6 measurements, after a maximum of 24 hours, preferably after a maximum of 21 hours.

Such surfaces are particularly suitable for further coating with epoxy or polyurethane based coatings. Preferred polymer-modified mortars which, after application to dry concrete as described above and curing for 24 hours at 21 ℃ and 65% relative air humidity, are coated with epoxy-or polyurethane-based coatings and have an adhesive strength of more than 1.5MPa, preferably more than 2MPa, after storage for 14 days at 21 ℃ and 65% relative humidity.

The composition can be used in a process for coating, refurbishing or protecting a component using the one-component composition according to the invention as described above after mixing with water, wherein the process comprises the following process steps:

a) the composition is mixed with water and the mixture is stirred,

b) the mixture obtained is processed as follows

b1) Applying the mixture to the surface of one or more components to coat,

b2) the mixture is introduced into the cavities or irregularities of the component to fill or smooth,

b3) applying the mixture as corrosion protection to the steel reinforcement of the component,

c) optionally smoothing and/or degassing the applied or introduced mixture, and

d) the mixture is cured.

The processing and curing of the mixture can in particular be carried out at temperatures of from 5 to 35 ℃.

The element for coating can be a substrate made of any material, in particular a material commonly used in construction, such as concrete, stone, masonry, plaster, glass or metal.

The component is preferably a floor, for example made of concrete, mortar, screed or stone, wherein the coating consisting of the composition according to the invention forms a floor covering. Particularly preferably, this is a self-levelling floor covering. The floor may be provided with a primer. Furthermore, a cover layer can be applied as a seal to the applied cured mixture.

The one-component compositions according to the invention can be used in a conventional manner, for example as mortars or repair mortars, for introducing the mixture into cavities or irregularities of components to be filled.

As corrosion protection, the one-component compositions according to the invention can be applied in a conventional manner, for example by brushing or spraying, to the reinforcing bars.

The invention further relates to the use of a water-dilutable amine mixture comprising the following components as a constituent of a pulverulent or granular composition comprising cement, an inorganic filler and a powder comprising at least one polymer P and at least one compound comprising epoxide groups:

-at least one amine-epoxide adduct of formula (I),

-at least one amine-epoxide adduct of formula (II),

at least one amine-epoxide adduct of the formula (III) and

at least one amine having two primary amino groups and being free of further amino groups and ether groups,

wherein

a is an integer of 0 to 10, b is an integer of 1 to 10, n is an integer of 5 to 50 and the sum of (a + b) is an integer of 1 to 10,

p is 0 or 1 and q is 0, 1, 2 or 3,

e is a diepoxide group after removal of two epoxy groups,

R¹is a monovalent organic radical having a molecular weight of from 15 to 150g/mol, in particular pent-3-en-2-one-4-yl or hex-4-en-2-one-5-yl or benzyl,

R²is a monovalent organic radical having a molecular weight of 100-280g/mol, in particular octyl, 2-ethylhexyl, nonyl, decyl, C₁₂To C₁₈-alkyl or C₁₂To C₁₈-alkylaminopropyl, and

a is a divalent organic group having a molecular weight of 28 to 500g/mol, in particular a polyoxypropylene group having a molecular weight of 180-500 g/mol.

This composition cures after mixing with water, as described above.

Examples

The following description is intended to further illustrate the described embodiments of the invention. It goes without saying that the invention is not limited to the embodiments described.

1. Description of the test methods

The adhesive strength of the test mortar was determined according to EN 1542 after applying the test mortar on sandblasted garden boards made of concrete and curing it.

The adhesion strength of epoxy or polyurethane based coatings on test mortars was determined according to EN 1542.

The surface moisture content of 1.5 to 3mm thick coatings applied on sandblasted garden boards made from concrete was determined by a TRAMEX CME4 concrete moisture meter (TRAMEX Ltd. (de), germany). The moisture content is determined here by electronic impedance measurement. Measurements were taken at six different points on the applied coating at regular intervals. The average of six measurements was determined as the moisture content. The time from the application of the coating until a moisture content of less than 4 wt.% is reached is determined in this way.

2. Materials used

A premix A1 consisting of 14% by weight of bisphenol F diglycidyl ether, 71% by weight of a redispersible powder based on styrene-acrylate copolymers and 15% by weight of a carrier material consisting of calcium carbonate and silicate is provided in the form of a free-flowing powder having an epoxy value of 0.86 mmol/g.

Prepolymer B1, consisting of amine, polybutadiene and about 34 wt% fumed silica, was provided as a free-flowing powder with an amine number of 220mg KOH.

Premix C1 was provided, consisting of 62.5% by weight of quartz sand with a particle size of 0.1-2.2mm, 34% by weight of Portland cement CEM I52.5, 2.0% by weight of calcium carbonate and 1.5% by weight of a mixture of plasticizer, defoamer, shrinkage-reducing agent and chromate reducing agent.

For reference, use

-81

A cement-based epoxy modified three-component flow coating is composed of a waterborne epoxy-containing binder component, a waterborne amine-containing curing agent component, and a powder mixture.

3. Preparation of the compositions according to the invention and of the comparative mixtures

Composition Z1

40g of premix A1 and 10g of premix B1 were thoroughly mixed in succession into 1kg of premix C1.

Composition Z2

80g of premix A1 and 20g of premix B1 were thoroughly mixed in succession into 1kg of premix C1.

Composition Z3

160g of premix A1 and 40g of premix B1 were thoroughly mixed in succession into 1kg of premix C1.

Comparative mixture V1

36.5g of a mixture of bisphenol-A/F-diglycidyl ether, alkyl glycidyl ether and dispersant which had been heated to 40 ℃ were sprayed and mixed well into 1kg of premix C1, giving a free-flowing powder.

4. Storage stability

Samples of composition Z2 and comparative mixture V1 were stored in a closed plastic tub at 21 ℃ and 65% relative humidity and 35 ℃ and 65% relative humidity, respectively, for one month.

After one month of storage, 5kg of composition Z2 were mixed with 800g of water in a Hobart mixer for 3 minutes.

Two mortars, one made of composition Z2 stored at 21 ℃ and the other made of composition Z2 stored at 35 ℃, can be handled easily without problems.

Comparative blend V1 was also tested after storage. For this purpose, 5kg of comparative mixture V1 and 735g of aqueous amine-containing curing agent component were mixed in each case in a Hobart mixer-81

And 112.5g of water for 3 minutes.

The mortar obtained from comparative mixture V1, which had been stored for one month at 21 ℃, could be handled without problems.

The mortar obtained from comparative mixture V1, which had been stored for one month at 35℃, could no longer be processed correctly because of its viscosity and consistency.

5. Use of a composition and preparation of a mortar

In each case 5000g of the compositions according to the invention Z1, Z2 and Z3 or premix C1 were mixed with 800g of water in a Hobart mixer for three minutes.

Will be provided with-81

Used as reference mixture 1. The binder component containing the epoxy resin and the curing agent component containing the amine are mixed with each other in a mixing vessel of a Hobart mixer. The powdered components were then added with stirring and the mixture was mixed for an additional 3 minutes until a homogeneous mixture was formed.

Sandblasted garden slabs made of concrete were coated with mortar having a layer thickness of 1.5 to 3mm and the fresh coating was degassed with a spike roller. The coated garden boards were stored at 21 ℃ and 65% relative air humidity. The surface moisture content was measured every hour, starting 10 hours after the application of the coating. The adhesion strength of the coating was determined after 2 and 28 days.

The properties of the fresh mortar and the coating are reported in Table 1

TABLE 1

n.g. not measured

6. Adhesion of sealing layer to mortar coating

Dry sandblasted garden boards made of concrete were coated with fresh mortar with a layer thickness of 1.5 to 3mm, the fresh coating was degassed with a spike roller, and the coated garden boards were stored at 21 ℃ and 65% relative air humidity for 24 hours. Subsequent application of

160 EP (epoxy coating, from Sika) or

359 PU (polyurethane coating from Sika) as coating. After 14 days of storage at 21 ℃ and 65% relative air humidity, the adhesion of the applied coating on the mortar substrate was determined. The results are reported in tables 2 and 3.

TABLE 2 after 14 days

160 EP adhesive strength.

	Reference example 2	Reference example 3	Example 3	Example 4
					Mortar foundation	3-component System	Premix C1	Composition Z2	Composition Z3
Adhesive strength [ MPa ]]	3.6	Non-adhesion	2.2	3.1

TABLE 3 after 14 days

359 PU adhesion Strength

	Reference example 4	Reference example 5	Example 5	Example 6
					Mortar foundation	3-component System	Premix C1	Composition Z2	Composition Z3
Adhesive strength [ MPa ]]	3.1	Non-adhesion	2.8	3.0