DE19526151A1 - Solvent free, low viscosity primer, used for e.g. outdoor surfaces - comprises bisphenol A or F based epoxy! resin dil. with polyfunctional aliphatic epoxy! cpd. thinner and di- or poly:amine curing agent - Google Patents

Abstract

Solvent-free, low viscosity epoxy resin (R) comprising: (A) aa reactive-dil. epoxy resin with high solubility in water, based on bisphenol A and/or bisphenol F, opt. pre-dil. with monofunctional thinner contg. an epoxy gp., and a polyfunctional aliphatic thinner contg. two or more epoxy end gps.; (B) a curing agent chosen from aliphatic polyamines, cycloaliphatic diamines or aromatic diamines or mixts. of these; and (C) opt. upto 15 % water. Also claimed are (i) a method for the prepn. of coatings, covers and/or fillings on mineral and/or wood substrates using (R), (ii) a method for filling in pores, cracks, spaces and/or holes using (R), and (iii) component (A). Pref. the monofunctional thinner is a cpd. contg. one glycidyl ether end gp., pref. phenyl glycidyl ether, o-cresyl glycidyl ether, p-tert.-butyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 12-14C glycidyl ether and/or neodecanoic acid glycidyl ether. The polyfunctional thinner comprises an aliphatic cpd. contg. two or more glycidyl end gps., pref butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerine triglycidyl ether, pentaerythritol polyglycidyl ether and/or polypropylene glycol diglycidyl ether. (C) comprises at least one aliphatic polyamine (pref. dipropylene triamine, tripropylene tetraamine, diethylene triamine, triethylene tetraanubem butylene diamine, hexane diamine, trimethylhexamethylene diamine and/or polyether diamine), at least one aromatic diamine (pref. 2,4- or 4,4'-diaminodiphenyl methane, or o-, m- or p-xylylene diamine, or mixts. of these).

Description

The present invention relates to a formulation of a solvent-free, low-viscosity epoxy resin composition, which essentially comprises two components for manufacture a permanently strong adhesive bond on mineral and / or woody substrates and as a filling for injections and Impregnations. The present invention particularly relates to a Formulation of a solvent free, low viscosity Epoxy resin composition with which it is possible to wet and oily mineral and / or wood-like substrates sealing protective layers for further surface protection systems to apply or as porous injection or impregnation material, To fill cracks, voids and / or voids for manufacture one that is resistant to tensile, compressive and moisture-sensitive Filling or coating with a high adhesive bond.

The present invention also relates to a method for Production of a tensile and pressure resistant as well as moisture insensitive filling or coating with high adhesive bond using the formulation according to the invention.  

It is generally known that in applications on wet, damp and oily surfaces or in water-damp Crack areas not conventional epoxy resin coatings can be used because the components used have hydrophobic properties or with water hydrates and Form carbamates. Loss of adhesion, blistering and sticky Coatings with a short lifespan or insufficient Usage properties are the result. The use of systems containing solvents were therefore often the only ones Possibility to process such surfaces.

To solve such problems, has been used with primers worked that contain a mixture of solvents to the Diffusion of the epoxy in the porous structure of the sub reason, while at the same time mixing in residual moisture enable. Such a primer is, for example, from the DD-1 60 277 known. Although this primer is for application Use on wet surfaces or in water-moist crack areas is suitable, is due to the solvent component effective proportion of active ingredient (epoxy resin and hardener) considerably decreased. However, the solvents result in a increased fire hazard and health hazard at the Processing.

In the course of the constantly growing environmental and health awareness solvent-free systems are increasingly in demand. The Necessity arises all the more when such applications are in closed rooms, cellars or cisterns, without sufficient drying or processing conditions can be achieved.

One solution to this problem is the use of hydantoin Epoxy resins that have a certain water solubility. These have the disadvantage that they are usually not as large Adhesive bond had and therefore not usable applications led.  

Because of the increased viscosity that is usually in the range from 200 to 300 mPa · s or higher, these are epoxy resins also no longer for injection systems for filling small (less than 0.2 mm) crack widths suitable.

Accordingly, the object of the present invention is the formulation an epoxy resin composition capable of dry, wet, damp, oily and / or greasy mineral and / or wood-like substrates coatings to generate and achieved a very high adhesive bond. The Formulation is also intended to be used as a non-pressurized filling water-bearing pores, cracks, voids and / or voids be suitable, in particular very fine (less than 0.2 mm) could be. The wording is also intended to be the Feuerge dangerousness and health hazard during processing belittle.

Another object of the invention is a method for Production of a tensile and pressure resistant as well as moisture and Oil-insensitive filling or coating with a high adhesive bond to provide.

The object is achieved by a formulation according to claim 1 and solved by a method according to claims 12 or 17.

The formulation according to the invention essentially comprises two Components.

Component A is a reactive diluted epoxy resin mixture high water solubility. The starting materials for component A are: an epoxy resin based on bisphenol A and / or bisphenol F, if necessary with a monofunctional thinner terminal epoxy group is prediluted, and a polyfunction Light, aliphatic thinner with two or more terminal ends Epoxy groups.  

Suitable epoxy resins are bisphenol A resins, bisphenol F resins and bisphenol A / F resin blends. The epoxy resin becomes 20 to 95% by weight, preferably 40 to 60% by weight, in the A component used.

Suitable monofunctional thinners are compounds that have a have terminal glycidyl ether groups, such as phenylglycidyl ether, o-cresyl glycidyl ether, p-tert-butyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C₁₂-C₁₄ glycidyl ether, neodecane acid glycidyl ether or mixtures thereof.

Suitable polyfunctional, aliphatic thinners are Ver Aliphatic structure bonds that have two or more ends have permanent glycidyl ether groups, such as 1,4-butanediol diglycide ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, Glycerol triglycidyl ether, pentaerythritol polyglycidyl ether and / or Polypropylene glycol diglycidyl ether. The reactive thinner becomes too 5 to 80 wt .-%, preferably 40 to 60 wt .-%, in the A-Kom component used. In addition to the dilution effect, this also helps Raw material for elasticization, diffusion ability and water absorption take part.

Component B comprises a hardener selected from aliphatic Polyamines, aromatic diamines, cycloaliphatic and / or alicyclic amines and mixtures thereof. Taking cycloalipha table and / or alicyclic amines in the sense of the present Invention are compounds with at least one amine function understand,

• 1. in which the amine function directly or via an alkylene group with an aliphatic ring or ring system ver is bound, or
• 2. where the amine function is part of other functional Is like in acid amides, imides, or carbamides Carbamates, or  
• 3. in which the amine function along with other functional Groups such as carbonyl functions, acid amides, imides, Carbamides or carbamates is contained, or
• 4. in which the amine function in N- and / or N, O-heterocycli is contained, as in pyrrolidine, 2- Pyrroline, 3-pyrroline, 1,2-oxazolidine, 1,3-oxazolidine, Piperidine, morpholine or higher-membered heterocycles.

Connections that have at least one are also possible Contain amine function and combinations of the in 1., 2., 3. and / or 4.

The hardener preferably consists of at least one aliphati 's polyamine, at least one aromatic diamine and at least one cycloaliphatic and / or alicyclic amine.

Suitable aliphatic polyamines are dipropylenetriamine, Tripropylenetetraamine, diethylenetriamine, triethylenetetraamine, Butylene diamine, hexane diamine, trimethyl hexamethylene diamine, poly ether diamine and mixtures thereof. The aliphatic polyamines are 10 to 90 wt .-%, preferably 40 to 60 wt .-%, in the B component used.

Suitable aromatic diamines include 2,4- and 4,4'-diaminodi phenylmethane, o-, m- and p-xylylenediamines (2-, 3- and 4- (amino atoms thyl) benzylamine) and mixtures thereof. You will be in one Amount of 5 to 50 wt .-%, preferably 20 to 30 wt .-%, in the B component used.

Suitable cycloaliphatic and / or alicyclic amines are Cyclohexanediamine, isophoronediamine and its modifications, Hydantoin and its modifications, 1,3-oxazolidine and its Modifications, Morpholine and its Modifications, Com combinations of oxazolidines such as urethane bisoxazolidine and / or Hydantoin diamine. The cycloaliphatic diamine becomes 5 to  50% by weight, preferably 20 to 30% by weight, in the B component used.

The mixing ratio of components A to B is 100:10 to 100: 50, preferably 100: 25 to 100: 35 parts by weight.

If necessary, to adjust the viscosity and Curing time up to 15 wt .-% water in the mixture of Components A and B are mixed in.

Due to the special selection of ingredients, a low mixed viscosity reached. The epoxy resin composition has a mixed viscosity at room temperature in the range of 20 to 200 mPa · s, preferably 50 to 150 mPa · s, in particular 80 to 140 mPa · s and most preferably 100 to 120 mPa · s. The system responds quickly within 20 minutes and solves that Pore water (up to 15% by weight). In doing so, this water almost due to chemical integration in the epoxy matrix completely demobilized. This was only possible because by using the polyfunctional, aliphatic thinners with terminal epoxy groups selected hydrophilic constituents that can mix in water before curing, after which Solidifying this water while converting it to one but no longer release the hydrophobic system. Similar processes find with hydrocarbon mixtures of oil or fat type Structure instead, which is integrated into this coating system without being able to migrate later and liability follows reduce gender coatings.

In contrast to previous epoxy systems for which the property water is a critical framework this epoxy resin designed so that not only the interference succeeded by water, but by the smallest amounts of water a significant acceleration effect occurs, however Products with a high adhesive bond are created. With that, formulation according to the invention the positive properties of water-stopping polyurethane injection systems with water  stopping properties even against pressureless ascending Water and oil.

Due to the low viscosity and very hydrophilic properties, d. H. Water absorption up to 15% clear and emulsion-free, penetrates the applied formulation according to the invention in dry, moist or mineral or woody sub saturated with water set up, anchored by a quick reaction and hardens film-forming and tough and elastic in the desired layer strengthen. Because of the possibility of mixing in water but also application on very dry substrates possible. This results in a shorter curing time.

The primer obtained can be used for various purposes be used. An area of application of the invention Formulation represents the application for surface treatment or - Solidification on damp, wet, oily, greasy mineral and / or wood-like substrates, which with the previous coating systems only inadequate and under Loss of quality could be processed. This also includes that processing is possible on substrates that have a high degree of destruction. In particular, they are loose Particles, destroyed concrete, cement sludge, cracks, joints, Cracks and water-filled caverns, in which also rising Water and rising oil are included, as well as other concretes or subsoil with greatly reduced strength.

If the epoxy resin composition according to the invention as Grundie a subsequent final coating can be used problematic "wet on wet" applied to this primer will. Because both epoxy and Polyurethane epoxy systems can be used further design of the redevelopment area, using the usual methods, no limits.

Another area of application of the formulation according to the invention are filling systems as injection and impregnation material for pores,  Cracks, voids and / or voids. The backfilling can be done at damp, pressureless water-carrying, greasy or oily Interfaces of the pores, cracks, voids and / or voids respectively. Due to the low viscosity, pores and Cracks in the range of 0.2 mm and less can be filled easily will. The formulation of the invention can be like any normal Injection system are applied, for. B. by impregnation, Borehole or packer injection.

The formulation according to the invention has various advantages compared to the previously known epoxy resin systems.

The systems based on hydantoin bind the accumulation and Pore water does not become irreversible, so it is under certain Conditions that are typical for buildings are released again and damage to the subsequent coatings and the Lead underground, especially at high temperatures rates and sun exposure. In contrast to the hydantoin systems the trapped water only becomes even at 70 ° C to a very small extent. In addition, the formulation according to the invention has a lower viscosity, the optionally adjusted by mixing in water can be, so that these systems also in larger underground areas surface can penetrate and pore formation and cracking in the range of 0.2 to 0.3 mm still well filled.

Compared to epoxy-containing systems that contain solvents, the advantages of the formulation according to the invention are in one higher active substance content, with a lack of solution at the same time means that pose a risk to health and environmental technology represent from a technical point of view. In addition, the processing at relative humidity over 90% allows and still all conditions for testing coating systems moisture penetration is observed.

In contrast to the polyurethane injection systems, this results a considerable processing advantage since this invention  Primer can also be applied from the outside instead of just to be injected. However, the formulation according to the invention is nevertheless well suited for injection systems. In the invention According to the formulation, the water in the epoxy dressing included, while with the polyurethane systems traces of water inevitably lead to undesirable foaming.

The following example explains the invention Formulation:

Component A

50% monofunctional reactive diluted epoxy resin
50% difunctional, aliphatic thinner with terminal epoxy groups.

Component B

50% aliphatic polyamine, e.g. B. triemethylhexamethylene diamine
25% cycloaliphatic diamine, e.g. B. Isophorone diamine modification products
25% aromatic diamine, e.g. B. Xylylenediamine.

The mixing ratio of components A to B is 100:25 up to 100: 35 parts by weight.

From this a product is obtained that with low mixing viscosity has a pot life in the range of 40 to 60 minutes and has the described properties.

The pot life can be mixed with up to 15% water to 20 Minutes and less can be reduced.

Different test areas were created with the formulation coated and the tear resistance on the surfaces ZTV-SIB 90 tested.  

Tester: Proceq 8708-204
Glue: eagle owl stuck immediately; Two-component epoxy resin
Test area: ⌀ 50 mm, 1962.5 mm²; the test area is obtained by cutting an annular groove.

Test area 1

The surface to be coated consisted of very porous concrete flooring those with residues of cement slurry and loose granular Components. The area was partially wet and oiled. After Eliminating pools of water could quickly rise from Water can be observed.

The application was carried out by pouring and then Distribution by means of a lambskin roll in a layer thickness up to 1 mm. When applying the primer, the wetting was good Surface and floating water and cement slurries from to recognize the interface. The coated test area was dry. After the demolition, moisture immediately rose through the porous concrete to the surface.  

Measurement results

Test area 2

The area to be coated did not consist of caked-up areas hardened sludge. It was constantly soaked and partially oiled. Oil gets through the back moisture pressed to the surface. The application was done by even casting in a layer thickness of approx. 1 mm and caused the surface to close.

The coated surface was dry. Piercing the Layer to create an annular groove or defined test area and the sticking of test stamps was due to the firm, dry surface possible. After the demolition, moisture increased to the surface.

Test area 3

The surface to be coated was dry to slightly damp Concrete base. It was cleaned by hot steam blasting. Low Oiling was visible before coating. The application was done by rolling up with a lambskin roller until saturation the absorbent and porous concrete surface.  

Measurement results

Test area 4

The test area consisted of fine-grained, wet concrete different qualities. Partial expression of this light, loose, sand-like and partly blue-green, firm Surface areas. For this reason, comparisons are the Measurement results of coated and uncoated surfaces are not possible. The concrete surface was by hot steam blasting cleaned. Oily parts were visible.

The application was carried out by pouring, the even Distribution with a sheepskin roller was achieved. In the Application was based on a good distribution and mixing of the Surface water and loose surface particles with the Respected primer.  

Measurement results

For all adhesive tensile tests on the coated test surfaces the fracture occurred in the concrete or at the interface with the adhesive. The tensile tests on non-coated comparison areas showed the same results. The determined traction values, confirmed despite the low surface strength of the surfaces  the application of the formulation according to the invention to wet, damp or dry and for different degrees of oil Contaminated mineral substrates as a primer for wide areas re coating or sealing. Even with strong back low moisture content, the application resulted in a well-adhering, film-forming surface coating or surface hardening.

Claims (27)

1. Formulation of a solvent-free, low-viscosity epoxy resin composition which comprises the following components:

• A. a reactive diluted epoxy resin mixture with high water solubility, which consists of an epoxy resin based on bisphenol A and / or bisphenol F, which is optionally prediluted with monofunctional thinner with a terminal epoxy group, and a polyfunctional, aliphatic thinner with two or more terminal epoxy groups is composed,
• B. a hardener selected from aliphatic polyamines, cycloaliphatic diamines, aromatic diamines and mixtures thereof,
• C. optionally up to 15% water.

2. Formulation according to claim 1, characterized in that the hardener made from at least one aliphatic polyamine, at least one aromatic diamine and at least one cycloaliphatic and / or alicyclic amine. 3. Formulation according to claim 1 or 2, characterized in that the monofunctional thinner is a compound that has a terminal glycidyl ether group. 4. Formulation according to claim 3, characterized in that the monofunctional thinner phenylglycidyl ether, o-cresyl glycidyl ether, p-tert-butylglycidyl ether, n-butylglycidyl ether, 2-ethylhexyl glycidyl ether, C₁₂-C₁₄ glycidyl ether and / or Neode canoic acid glycidyl ether.   5. Formulation according to one of the preceding claims, characterized in that the polyfunctional aliphati thinner a compound with an aliphatic structure is the two or more terminal glycidyl ether groups having. 6. Formulation according to claim 5, characterized in that the polyfunctional, aliphatic thinner 1,4-butanediol diglycidether, 1,6-hexanediol diglycidether, neopentylglycol diglycidether, glyceroltriglycidether, pentaerythritolpolygly is cidether and / or polypropylene glycol diglycidether. 7. Formulation according to one of the preceding claims, characterized in that the aliphatic polyamine Dipropylenetriamine, tripropylenetetraamine, diethylenetriamine, Triethylenetetraamine, butylenediamine, hexanediamine, trimethyl is hexamethylene diamine and / or polyether diamine. 8. Formulation according to one of the preceding claims, characterized in that the aromatic diamine out chooses from the group consisting of 2,4- and 4,4′- Diaminodiphenylmethane, o-, m-, p-xylylenediamines and Mixtures of the same. 9. formulation according to one of the preceding claims, characterized in that the cycloaliphatic and / or alicyclic amine is selected from the group consisting of from cyclohexanediamine, isophoronediamine and its modifi ornaments, hydantoin and its modifications, 1,3- Oxazolidine and its modifications, morpholine and its Modifications, combinations of oxazolidines, hydanthoin diamine and mixtures thereof. 10. A formulation according to any one of the preceding claims comprising:

• A. 1. 20 to 95% by weight, based on component A, of optionally with a monofunctional thinner with prediluted epoxy resin,
• 2. 5 to 80% by weight, based on component A, of the polyfunctional, aliphatic thinner with terminal epoxy groups;
• B. 1. 10 to 90 wt .-%, based on component B, of the aliphatic polyamine,
• 2. 5 to 50% by weight, based on component B, of the cycloaliphatic diamine,
• 3. 5 to 50 wt .-%, based on component B, of the aromatic diamine.

11. The formulation of claim 10 comprising:

• A. 1. 40 to 60% by weight, based on component A, of the epoxy resin which may have been prediluted with a monofunctional thinner,
• 2. 40 to 60% by weight, based on component A, of the polyfunctional, aliphatic thinner with terminal epoxy groups;
• B. 1. 40 to 60 wt .-%, based on component B, of the aliphatic polyamine,
• 2. 20 to 30% by weight, based on component B, of the cycloaliphatic diamine,
• 3. 20 to 30% by weight, based on component B, of the aromatic diamine.

12. Process for the production of coatings, coverings and / or fillings on mineral and / or wood-like Substrates, characterized in that a formulation according to one of claims 1 to 11 is used.   13. The method according to claim 12, characterized in that the Coatings, coverings and / or fillings on concrete, wall work or wood. 14. The method according to any one of claims 12 or 13, characterized characterized in that the coatings, coverings and / or Fillings on damp, wet or dry and given otherwise oiled or greasy mineral and / or woody substrates are applied. 15. The method according to any one of claims 12 to 14, characterized characterized that on the formulation as a primer at least one further coating is applied. 16. The method according to claim 15, characterized in that as at least one further coating or an epoxy resin Polyurethane is used. 17. Process for filling pores, cracks, voids and / or cavities, characterized in that a Formulation according to one of claims 1 to 11 used becomes. 18. The method according to claim 17, characterized in that Pores, cracks, voids and / or voids filled their interfaces are oily and / or unpressurized water are leaders. 19. The method according to any one of claims 12 to 18, characterized characterized in that the two components of the epoxy resin composition mixed and applied immediately or be injected. 20. The method according to any one of claims 12 to 19, characterized characterized in that the components A and B in one Ratio of 100: 10 to 100: 50 parts by weight mixed will.   21. The method according to claim 20, characterized in that the Components A and B in a ratio of 100: 25 to 100: 35 parts by weight can be mixed. 22. The method according to any one of claims 20 or 21, characterized characterized in that the mixture of components A and B up to 15% water can be mixed in. 23. The method according to any one of claims 12 to 22, characterized characterized in that the components are mixed so that the epoxy resin composition immediately after mixing has a viscosity of 20 to 200 mPa · s. 24. The method according to claim 23, characterized in that the Components are mixed so that the epoxy resin together immediately after mixing a viscosity of 50 to 150 mPa · s. 25. The method according to claim 24, characterized in that the Components are mixed so that the epoxy resin together immediately after mixing a viscosity of 80 to 140 mPa · s. 26. The method according to claim 25, characterized in that the Components are mixed so that the epoxy resin together immediately after mixing a viscosity of 100 to 120 mPa · s. 27. Reactively diluted epoxy resin mixture with high water solubility made from an epoxy resin on bisphenol A and / or bisphenol-F base, optionally with a monofunctional thinner with terminal epoxy group is prediluted, and a polyfunctional, aliphatic Thinner with two or more terminal epoxy groups is composed for use in a formulation according to one of claims 1 to 11 and / or a method according to one of claims 12 to 26.