WO2004096933A2

WO2004096933A2 - Method for producing a reaction resin mixture

Info

Publication number: WO2004096933A2
Application number: PCT/EP2004/004570
Authority: WO
Inventors: Günter Nosbüsch; Silke Melchers; Uwe Güntert; Peter Grochal
Original assignee: Sto Ag
Priority date: 2003-04-30
Filing date: 2004-04-29
Publication date: 2004-11-11
Also published as: WO2004096933A3; DE10319507A1

Abstract

The invention relates to a method for producing a pourable dry mixture containing at least one reaction constituent of a reaction resin coating substance. According to the invention, at least one of the reaction constituents, separate from the other reaction constituent(s), is, together with at least one pigment, at least one filler and/or with additional constituents of the coating substance, processed in an agglomeration process to form a pourable intermediate product that contains agglomerates, which comprise the reaction constituents, at least one pigment, at least one filler and/or at least one additional constituent of the coating substance.

Description

Process for the preparation of a reaction resin mixture

The invention relates to a method for producing a free-flowing dry mixture comprising at least one reaction component, preferably at least two reaction components, of a reactive resin coating material.

Reactive resin coatings based on epoxy resins, polyurethane resins, methyl methacrylic resins, vinyl ester resins and other polymers have been used with great success for decades. Reaction resin coatings are used in the most common applications to improve the aesthetics, to maintain the function of components, structures, vehicles and their components, as well as electrical and electronic components. The most common form of processing, even today, is the use as multi-component liquids.

However, this poses some problems for the manufacturers of the reactive resin coating compositions and the processors.

• Expensive dangerous goods containers must be used for storage and transport.

• Mixing ratios sometimes have to be set precisely by weighing the individual components.

• Expensive tin packaging with partially sticky wall bonds has to be disposed of at great expense.

Until now, powdered products (powder coatings) have only been used in the industrial use of reactive resin coating materials. The use of powder coatings requires that the object to be coated can be heated so that the meltable reactive resin coating (powder coating), which reacts at elevated temperature, runs and hardens. The usual application temperatures range from + 80 ° C to + 180 ° C.

If the reactive resin coatings can be formed or cured at elevated temperature, higher molecular weight, meltable mixtures consisting of solid resin and solid hardener can be used, as have been successfully used as powder coatings for decades. '' This method of hardening does not apply to the manual processing of reactive resin coatings, since the coated objects cannot usually be heated effectively or the use of elevated temperatures is prohibited for economic reasons. However, since the occupational hygiene protective measures are often critical, especially in manual applications, and personal contact with the liquid reactive resin can hardly be ruled out, it is extremely advantageous for reasons of personal protection and to reduce the well-known health problems for processors, reactive resins as solid to provide non-sticky dry mix.

In addition, the processing companies and the product manufacturers incur costs due to improper dosing of the individual components, which have to be dosed stoichometrically and mixed homogeneously with each other.

The problem-free homogenization of the reaction resin components is also a problem, since the liquid but nevertheless highly viscous individual components are often cast together, but are in no way produced homogeneously with the necessary care, without concentration gradients in the mixture produced.

Numerous damage cases are known in which liquid multicomponent mixtures have been processed and due to insufficient homogeneity of the Reactive resin mixtures have resulted in sticky, unusable coatings that have to be removed again with great effort. The working conditions for handling liquid reactive resin mixtures at the so-called "mixing station" on construction sites are also well known. Containers with sticky, sometimes highly viscous substances are scraped out, dripping containers are stored and removed.

A procedure for the preparation of a reactive resin-cement building material mixture was already described in the document EP 207 473, whereby for the preparation of a storage-stable, dry premix, the coarser parts of at least a part of a coarser and finer part containing aggregate were initially introduced and with the liquid resin or mixed with the liquid hardener in such a way that droplets or films of the resin or hardener can adhere to the surfaces of the coarse-grained aggregate and then the finer fractions of the aggregate are added.

However, this has not proven to be expedient, since the resulting procedure does not lead to construction products that are stable in storage. Another disadvantage is that only compositions with the primary binder cement can be produced, which leads to severely restricted applications.

The same applies to DE 197 01 916, here too a process for producing a polymer-modified cement mortar is described, cement being required as a hydraulic binder or other similar reacting substances, such as latent hydraulic binders. However, it is known that the use of cement in self-leveling or thin-layer coatings induces mechanical tensions in the coating materials, which often lead to late cracking and severely restrict the use of the materials.

Combinations of reactive resin binders, emulsified in water, with cement are known inter alia as ECC (Epoxy Cement Concrete). However, such formulations can only be used as 3-component products. Since cement acts as a co-binder and hardens with the required water in the formulation, cement also fulfills the function as a "water scavenger" in the required thick layers.

One-component reactive resin products that can be used in thick layers have so far always been described with cement as an additive and have the disadvantages mentioned. EP 0 670 352 deals with coating agent granules and processes for their production. However, only dispersions and emulsions of homopolymers and copolymers can be used here, without chemical reactivity under normal conditions, so that the existing problems of the prior art cannot be solved by this invention. The use of reactive resins is excluded and leads to a completely unusable product.

EP 0 894 821 deals with the production of crosslinkable, water-redispersible powder compositions. However, only water-soluble, film-forming, high-molecular polymers are used here, which do not develop sufficient strengths for use in the area of mechanically and chemically stressed floor and wall coatings, since they harden essentially through physical filming and only to a lesser extent through chemical crosslinking ,

In another known coating material (DE 100 32 305), epoxy resins and epoxy resin hardener components are used in the form of a dry mixture which can be mixed with water and, after intensive homogenization, can be processed into a ready-to-use reaction resin mixture. This is as a coating material, reactive resin mortar, casting resin and. Like. Can be used. The result is technically functional protective coatings for industrial floors, storage containers, balcony coatings and architectural paints.

In the case of the granulated epoxy resin binders used for the production of a one-component coating, it has proven disadvantageous that the granules have only a limited storage stability.

The invention has for its object to develop a method with which a dry reactive resin mixture with good storage stability can be created, which is offered in free-flowing form and can be converted into a coating composition by adding the mixing water before processing while eliminating the aforementioned disadvantages , This mass can be applied to various substrates at normal temperature using known processing techniques (knife coating, brushing, spraying, rolling, filling) and hardened at normal temperatures. The invention is also based on the object of providing a product which can be used for producing a coating material. In procedural terms, this object is achieved by a further development of the known method described, for example, in DE 100 32 305 A1, which is essentially characterized in that at least one of the reaction components is separated from the other reaction component (s) together with at least one Pigment, at least one filler and / or further constituents of the coating material are processed in an agglomeration process into a free-flowing intermediate product containing the reaction component and at least one pigment, at least one filler and / or at least one further constituent of the coating material.

This invention is based on the knowledge that the poor properties of the known dry mixtures are due, on the one hand, to the fact that the reaction components react with one another already during the mixing and drying process used to produce the dry mixture and the poor storage stability of, for example, in DE 100 32 305 described dry mixtures is due to the fact that the comparatively low molecular weight reaction monomers and ougomers regularly have an extremely high solvency and dissolve the protective colloids used in conventional granulation processes. This leads to irreversible sticking of the micronized particles, which in turn is to be regarded as the cause of the poor storage stability.

Using methods according to the invention, the first cause of the poor properties of conventional dry mixtures is eliminated by agglomerating at least one of the reaction components separately from the other reaction components. Therefore, no undesirable reactions between the reaction components occur in the corresponding agglomeration process. In the course of the agglomeration process, agglomerates containing the reaction components are produced, and these agglomerates may also contain pigments, fillers and / or other constituents of the coating material in addition to the reaction components. These pigments, fillers and / or other constituents of the coating material form in the agglomerates a protective shell for the reaction component, so that an undesired reaction of this reaction component contained in the dry mixture with further reaction components with the aid of those which are required in any case to maintain the desired properties of the coating material Fillers, pigments / or other constituents of the coating material are effectively suppressed. Overall, a dry mixture suitable for producing a reactive resin coating is obtained with satisfactory storage stability. In a particularly preferred embodiment of the invention, two free-flowing intermediate products each containing one of the reaction components are produced with the aid of corresponding agglomeration processes and then mixed stoichometrically to obtain a dry mixture which is miscible with water.

The advantages of using this process to make dry reaction resin mixtures are obvious. The liquid reaction resins, which are to be assessed physiologically and critically, are immobilized by the method, so that their damaging influences cannot have an effect on storage, transport and handling on the construction sites. Only shortly before use are the agglomerates, which have already been produced by the manufacturing process in the stoichiometrically correct mixing ratio, mobilized by the mixing process with water and the crosslinking process of the reaction resin components made possible.

By using this agglomeration process, the recipe's own fillers and pigments are processed with the recipe's own reactive resin binders in appropriate agglomeration processes. In each case, a dry mixture is generated in two separate processes, which are then mixed with each other stoichometrically in a further process step. The use of the formulation-specific fillers and pigments, which can be carefully selected with regard to their suitability for the granulation process and, moreover, preferably also have favorable properties with regard to use in the agglomeration process mentioned, prevents the introduction of disruptive foreign substances into the coating mass to be produced. In this process, using suitable fillers, optimal structures of the agglomerates can be produced which are mechanically sufficiently stable for transport and storage and which effectively incorporate the liquid reactive resin binders. This prevents the particles from clumping back and undesired migration of the binders, thus preventing a premature reaction.

Reaction resin mixtures produced according to this process, however, can be re-emulsified without any problems on contact with water.

The agglomerates produced disintegrate in water even under the action of low shear forces and release the water-emulsifiable reaction resins, which then react as desired in a crosslinking reaction to give the polymeric binder. The fillers and pigments resulting from the dissolved agglomerates are integrated and the desired mixture is established. By using this method, ideal agglomerates can be generated by the process according to the invention, which lead to homogeneous, ready-to-use mixtures within a few minutes with construction site mixers such as paddle mixers, compulsory mixers, stirring baskets or continuous mixers.

The resulting coating materials according to the flow diagram shown in Fig. 2 and Examples 1-2 eliminate the disadvantages of the prior art, are highly abrasion-resistant, aesthetically sophisticated and can improve the ecological and workplace hygiene conditions during transport, storage and processing.

This process can be used to produce water-dilutable primers, coatings, leveling compounds, leveling compounds, mortars and screeds.

In the context of the invention, the agglomeration process is expediently effected in a fluidized bed. Continuous and discontinuous fluidized bed processes can be used.

A product for the production of a reaction resin coating material produced by a method according to the invention is essentially characterized in that it comprises at least one agglomerate containing reaction components in which the reaction component is surrounded by pigments, fillers and / or other constituents of the coating material. The pigments, fillers and / or other constituents of the coating material in the agglomerates that form a protective shell for the reaction component can be connected to one another via solid bridges.

The invention is explained below with reference to the drawing, to which reference is expressly made with regard to all details that are essential to the invention and that are not detailed in the description.

In the drawing shows

Fig. 1 is a schematic representation of a method according to the invention and

2 is a flow chart illustrating the production of a reactive resin coating material using the method according to the invention. 1, individual particles of the reaction component 10, water droplets 20 and binder particles, pigment particles and other constituents of the coating material are initially present separately from one another in the agglomeration process. In the course of the agglomeration, liquid bridges 32 form between the particles 30, which form solid bridges 34 by drying. The particles 30 connected to one another via solid bridges 34 form a shell for the particles 10 with a “blackberry” structure in the finished agglomerate.

According to FIG. 2, in a preferred embodiment of the invention, intermediate products 1 and 2 are first produced using the raw materials 1.1, 1.2 to 1.n or 2.1 to 2.n with the aid of appropriate agglomeration processes.

These intermediate products are then stoichometrically mixed in a Lödige dry mixer and, if necessary, colored. The dry reaction resin coating material thus formed is finally converted into a liquid or pasty form with mixing water before processing. Examples 1-3 describe the concrete composition of the reaction resin coating materials which, after preparation according to the invention, lead to flawless products without the disadvantages of the prior art having to be accepted.

Example 1: Concrete paint - one component, can be mixed with water

Polyamine approx. 65% in water (H-active equivalent weight (EW) 200 36.40 parts by weight of Ti0 ₂ Tiona RL 568 29.10 parts by weight of heavy spar powder, of course 30.60 parts by weight of dispensing aid based on copolymeric surfactants 0.73 part by weight of Byk Silicone defoamer 0.73 parts by weight of highly disperse silica 2.44 parts by weight

Semi-factory 1 Σ = 100 parts by weight

Epoxy resin bisphenol A diglycidyl ether (EW 190) 92.90 parts by weight

Emulsifier, powdery, based on polyalkylene oxide 1, 96 parts by weight Highly disposable silica 5.14 parts by weight

Semi-finished product 2 Σ = 100 parts by weight

Dry mix consisting of semi-finished product 1 69 parts by weight Semi-finished product 2 31 parts by weight

Farbe Dry paint 100 parts by weight of mixing water 40 parts by weight

Ready-to-use color 140 parts by weight

The properties of the concrete paint resulting from example 1 are:

Processing time at 23 ° C about 2 hours

Dynamic viscosity at 23 ° C (DIN 53018) approx. 3500 mPa s

Specific weight at 23 ° C (DIN 53217) 1.4 kg / liter

Accessibility of the processed coating at 23 ° C and 50% rel. Humidity after about 10 hours

Mechanical full resilience of the processed

Coating at 23 ° C and 50% rel. Humidity after about 7 days

Example 2: Thick-layer leveling mortar for floor coatings, one-component mixable with water

polyamine mixture

Solid approx. 60% (H-active EW 283) 21, 20 parts by weight

Tiß0 ₂ Tiona RL 568 6.20 parts by weight

Heavy spar more, of course 20.10 parts by weight

Quartz flour mixture, natural 0.02-0.2 mm 49.10 parts by weight

Byk silicone defoamer 1, 60 wt

Fumed silica 1.80 parts by weight

Semi-finished product 1 ∑ 100 parts by weight

Epoxy resin bisphenol-A-diglycidyl ether (EW 190) 80.70 parts by weight of emulsifier, powdered, based on polyalkylene oxide 1.70 parts by weight of heavy spar powder, naturally 13.10 parts by weight of highly disperse silica 4.50 parts by weight

Semi-finished product 2 ∑ ^■■ 100 parts by weight

Dry mix consisting of semi-finished product 1 84 parts by weight Semi-finished product 2 16 parts by weight

Farbe Dry paint 100 parts by weight of mixing water 22 parts by weight

Ready-to-use color 122 parts by weight

The properties of the leveling mortar resulting from Example 2 are:

• Processing time at 23 ° C 30-40 minutes Flow time in a DIN cup, 8 mm nozzle (DIN 53211) at 23 ° C approx. 60 seconds specific weight at 23 ° C (DIN 53217) 1.8 kg / liter walkability of the processed leveling mortar at 23 ° C approx. 10 hours compressive strength after 7 days listening at 23 ° C (DIN / EN / ISO 604) approx. 50 MPa

Example 3: leveling compound for horizontal and vertical concrete substrates

polyamine mixture

Solid approx. 60% (H-active EW 283) 21, 20 parts by weight of Ti0 ₂ Tiona RL 568 6.20 parts by weight of heavy spar powder, of course 20.10 parts by weight of quartz powder mixture, natural, 0.02-0.2 mm 47.30 Parts by Byk silicone defoamer 1.60 parts finely divided silica 1.80 parts polyethylene fiber filler 940 parts 1.80 parts

Semi-finished product 1 ∑ = 100 parts by weight

Epoxy resin bisphenol-A-diglycidyl ether (EW) 190 80.70 parts by weight emulsifier, powdery basis polyalkylene oxide 1.70 parts by weight heavy spar powder, naturally 13.10 parts by weight highly disperse silica 4.50 parts by weight

Semi-finished product 2 ∑ = 100 parts by weight

Dry mix consistently

Semi-finished 1 84 parts by weight

Semi-finished product 2 16 parts by weight

∑ dry mortar 100 parts by weight

Mixing water 22 parts by weight

Ready-to-use filler 122 parts by weight

The properties of the filler resulting from Example 3 are. Processing time at 23 ° C 30-40 minutes

Filling consistency, vertical up to 8 mm

Specific weight at 23 ° C (DIN 53217) 1.6 kg / liter

Compressive strength after 7 days

Curing at 23 ° C (DIN / EN / ISO 604) approx. 45 Mpa

The invention is not restricted to the embodiments explained with reference to the drawing and the examples. Rather, the use of processes is also envisaged in which three or more reaction components are fed separately to an agglomeration process. Solvents other than water can also be used to form the agglomerates. Furthermore, the use of reactive resin based on polyurethanes and polyisocyanate and / or free-radically polymerizable resins is envisaged.

Claims

Patent claims:

1. A process for producing a free-flowing dry mixture comprising at least one reaction component of a reaction resin coating material, characterized in that at least one of the reaction components is separated from the other reaction component (s) together with at least one pigment, at least one filler and / or further constituents the coating material is processed in an agglomeration process into a free-flowing intermediate product containing the reaction component and at least one pigment, at least one filler and / or at least one further constituent of the coating material.

2. The method according to claim 1, in which at least two free-flowing intermediate products each containing one of the reaction components are prepared.

3. The method according to claim 2, characterized in that at least two intermediates are mixed stoichometrically to obtain a water-miscible dry mixture.

4. The method according to any one of the preceding claims, characterized in that the agglomeration process is effected in a fluidized bed.

5. The method according to any one of the preceding claims, characterized in that at least one epoxy resin and at least one polyamine hardener are used as reaction components.

6. The method according to any one of the preceding claims, characterized in that at least one polyurethane and at least one polyisocyanate are used as reaction components.

7. The method according to any one of the preceding claims, characterized in that at least one free-radically polymerizable resin is used as the reaction component.

8. The method according to any one of claims 3 to 7, characterized in that further substances are added when mixing the intermediates.

, A process for producing a coating material, in which water is added to a dry mixture produced by a process according to one of Claims 1 to 8 in a continuous mixer.

10. A process for the production of a coating material, in which a dry mixture produced by a process according to one of claims 1 to 8 is pressed into water-soluble moldings, such as flakes, tablets and / or blocks.

11. Free-flowing product with at least one reaction component suitable for producing a reactive resin coating material, produced by a process according to one of claims 1 to 8.

12. Product according to claim 11, characterized by an agglomerate comprising the reaction component, in which the reaction component is surrounded by pigments, fillers and / or other constituents of the coating material. ^'

13. Product according to claim 12, characterized in that the pigments, fillers and / or further constituents of the coating material are connected to one another via solid bridges.