WO2010121606A2

WO2010121606A2 - Method, formulas, and product for biocidal treatment of a cooling lubricant

Info

Publication number: WO2010121606A2
Application number: PCT/DE2010/000466
Authority: WO
Inventors: Klaus Mandery
Original assignee: Chemische Werke Kluthe Gmbh
Priority date: 2009-04-24
Filing date: 2010-04-23
Publication date: 2010-10-28
Also published as: WO2010121606A3; DE102010018312A1; DE102010018311A1

Abstract

The invention relates to a method for biocidal treatment of a cooling lubricant, particularly a water-based cooling lubricant, particularly wherein the cooling lubricant can be provided in a circuit within a machine for lubricating and/or cooling during a machining step, further developed and designed such that, with regard to a simple, safe, permanent, and harmless preservation of cooling lubricants, a biocide or biocide mixture within a formula is added to the cooling lubricant, emitting the biocide content present therein under delay into the cooling lubricant. A biocide formulation is further proposed, comprising a water-soluble and/or dispersible carrier substance and a biocide, or enclosing a biocide or a biocide solution in a semi permeable and/or merely somewhat permeable membrane or film. A ready-to-use product for biocidal treatment of a cooling lubricant is ultimately proposed, comprising a formulation in which a biocide or a biocide solution is present in encapsulated form, and comprising a bag receiving the formulation and made of filter material.

Description

PROCESS, FORMULATIONS AND PRODUCT FOR THE

BIOZIDE TREATMENT OF A REFRIGERANT

The invention relates to a process for the biocidal treatment of a cooling lubricant, in particular of a water-mixed cooling lubricant, in particular wherein the cooling lubricant can be provided in a circuit within a machine for lubricating and / or cooling during a processing step.

Furthermore, the present invention relates to formulations, i. Preparations in a specific application or dosage form, which are suitable for the biocidal treatment of a cooling lubricant, and are particularly suitable for use in carrying out a method according to the invention. These formulations are also referred to below as biocide formulations.

Furthermore, the present invention relates to a ready-to-use product for the biocidal treatment of a cooling lubricant, in particular a water-mixed cooling lubricant, which is particularly suitable for use in a method according to the invention.

Cooling lubricants or cooling lubricants are used in manufacturing technology in a number of processing steps, especially when milling, drilling, cutting, forming and much more, for heat dissipation and / or by forming a lubricating film to reduce the friction between the tool and the workpiece. In addition, they are used in the machining of workpieces to remove the chips by flushing away from the work area. Another positive side effect of cooling lubricants is the corrosion-protective effect on the machined workpiece.

However, the primary purpose of coolants is to reduce friction during machining, thereby reducing tool wear and energy requirements. On the other hand, an undesirable heating of both the tool as Also prevents the workpiece, whereby a structural change and thus an undesirable deformation is omitted.

In practice, a distinction is made between water-miscible or water-mixed and water-immiscible cooling lubricants. Non-water-miscible coolants are generally unalloyed or alloyed oils. Non-water-miscible cooling lubricants are mostly used when a high lubricating effect is required. Their disadvantage is the higher purchase and disposal costs. Furthermore, they can not provide a cooling effect by an evaporating water content.

Water-mixed cooling lubricants, on the other hand, contain a high proportion of water, generally approx. 95%. They are obtained on site from water-mixable concentrates or are already supplied as ready-to-use emulsions. The non-aqueous component consists mostly of oils, possibly of mineral origin, and possibly emulsifiers and / or additives. Water-mixed cooling lubricants provide good heat dissipation, but have a lower lubricating effect than non-water-mixed cooling lubricants. Due to the high water content, water-mixed cooling lubricants are less expensive, both in terms of procurement and disposal, than non-water-mixed cooling lubricants.

In Germany, about 28,000 t of water-miscible cooling lubricants (concentrate) are processed each year. Based on an approximately 5% concentration of these starting materials in the ready-to-use emulsion, this results in an annual volume of approx. 560,000 m ^{3 of} water-mixed cooling lubricants.

The organic substances contained in water-mixed cooling lubricants in addition to water are generally readily biodegradable, at least for the most part. As a result, a water-mixed coolant is a nearly ideal substrate for microorganisms. Therefore, it is known to control the infestation of water-mixed cooling lubricants by bacteria and fungi and their growth or multiplication by the treatment with biocides.

In this case, a one-time treatment of a coolant supply with a biocide ensures only a stability of the emulsion of a few weeks. To At this time, the biocide is mostly consumed. In order to be able to continue to use the cooling lubricant, it must be mixed again with biocides. If the term "biocide" or "biocides" is used below, the terms "biocide mixture" or "biocide mixtures" are expressly included here.

Water-mixed cooling lubricants are provided either in central systems (up to approx. 200 m ³ coolant lubricant content) or in the individually filled processing machines (lubricant content approx. 200 l to approx. 5,000 l). A central system can supply a large number of processing machines in each case via a circuit with cooling lubricant. The monitoring and aftertreatment of the coolant supply usually causes little problems with such central systems.

More problematic, however, is the situation with individually filled processing machines. Due to the usually large number of processing machines in one operation, emulsion samples from each individual machine must first be examined for corresponding infestation with microorganisms. Thereafter, the supply of lubricant in each individual machine must be re-preserved by biocide addition, depending on the particular microbial contamination detected.

On the one hand, this is very time-consuming, on the other hand, mistakes and incidents are increasingly occurring in practice. Due to the comparatively small amount of lubricant in individually filled processing machines, the amount of biocide to be added is often not determined and / or measured with sufficient accuracy. The consequence is an over or under dosage of the biocide.

It should also be noted that the biocides used are corrosive, irritating and generally hazardous to health. The entrusted with the operation of the processing machines staff, which usually also performs the Nachkonservierung, is generally not sufficiently trained in dealing with such hazardous materials. The consequences are health problems or even serious accidents.

A particular disadvantage of the known re-preservation of lubricant stocks is that the amount of biocide immediately after the post-consumer - A -

is particularly high, but then steadily drops. Finally, the biocide content is too low to prevent the emergence of a renewed microbial contamination. Both the high biocide content at the beginning and the increasing microbial contamination at the end of the post-preservation period exposes people in the vicinity of the processing machine to serious health risks.

After all, after a period of about three to six months, another re-preservation has to be carried out in each case, which binds personnel and causes costs. If the emulsion is so contaminated that re-preservation is no longer possible, it must be disposed of costly. There are costs of about EUR 100 / m ³ .

The present invention is therefore based on the object, a method - and in this context, biocide formulations and products - to specify the biocidal treatment of a coolant, with a simple, safe, durable and healthy preservation of cooling lubricants can be realized.

According to the invention, this object is initially achieved with regard to a method for the biocidal treatment of a cooling lubricant with the features of claim 1. Accordingly, a method mentioned at the outset is characterized in that a biocide or a biocide mixture is added to the cooling lubricant within a formulation which delays the amount of biocide contained in the cooling lubricant.

Advantageous embodiments and further developments of the method according to the invention can be taken from the subordinate claims.

According to the invention, it has been recognized that a biocide treatment optimized in accordance with the invention can be achieved if the biocide or the biocide mixture is continuously added to the cooling lubricant to be preserved. Thus, the coolant supply can always be supplied with the correct amount of biocide per unit time in order to maintain a minimum concentration of the biocide in the cooling lubricant. By turning away from previously known preservation methods, a constant concentration can be achieved while hitherto an initially too high and at the end too low a biocide concentration in the cooling lubricant has been found.

It is further provided according to the invention to add the biocide or the biocide mixture to the cooling lubricant within a biocide formulation. Costly and error-prone metering devices can be dispensed with here. A formulation or biocidal formulation is understood to mean a preparation, dosage form or application form which provides the biocide or biocide mixture chemically or physically bound in such a way that, when wetting with and especially when the formulation is submerged in the cooling lubricant supply, a delayed release of the contained biocide amount in the cooling lubricant takes place.

In other words, the biocidal formulation can be simply added to the coolant supply in a suitable form and quantity, for example in the form of a tablet or in the manner of a known "block." The automatic release of the optimum amount of biocide per unit of time is then carried out automatically and without further intervention operators.

Due to the constant biocide concentration can be achieved in accordance with the invention even in small processing machines cooling lubricant service life, which have been known only from central systems, namely up to two years or longer.

The inventive method is easy to use and ensures permanent conservation. Furthermore, no direct contact of the operator with the biocide in pure form is required. In addition, the adverse health effects of a very high biocide concentration immediately after conventional re-preservation are eliminated.

As a result, with the method according to the invention for the biocidal treatment of a cooling lubricant, a simple, safe, lasting and harmless preservation of cooling lubricants can be realized. With regard to an effective and permanent preservation of a cooling lubricant, the use of a formulation is preferred which gives the biocide continuously in terms of time, in particular in a substantially constant dosage as needed in the cooling lubricant. As a result, a constant biocide concentration can be set in the cooling lubricant over a long period of time, so that an optimal preservation result can be achieved.

As the biocide formulation, a granule, a capsule, a tablet, a stone or the like can be used. In particular, in the method according to the invention a formulation in the form of a large tablet or in the manner of a known "Klosteins" can be used, which can be added in a simple manner to the cooling lubricant supply of the respective processing machine.

It is preferred that the formulation is the cooling lubricant, in particular in a system or reservoir for the cooling lubricant added. In other words, the formulation can be immersed in or inserted into the cooling lubricant reservoir. The formulation can simply be thrown into the system or storage container for the cooling lubricant.

In this regard, an embodiment of the method is proposed in which the formulation is exposed to the cooling lubricant in a liquid-permeable container, preferably a wire basket or the like. The formulation, for example, a tablet or a stone, can be introduced into a liquid-permeable container and can be immersed together with this under the liquid level of the cooling lubricant. A drop in the formulation to the bottom of the lubricant container is avoided. The container can be removed at any time from the liquid, namely, to check whether any remains of the formulation are present, or whether it must be replaced.

In a particularly preferred development of the method according to the invention, a formulation is used which has at least one water-miscible and / or water-soluble carrier substance and at least one biocide. The biocide is dispersed within the vehicle. Dissolves the carrier Gradually, the biocide is delayed to a corresponding extent and preferably continuously discharged into the cooling lubricant.

Alternatively or additionally, the use of a formulation has proven to be particularly advantageous in which a semi-permeable and / or limited permeable membrane or film includes a biocide or a biocide solution and delays the amount of biocide contained in the cooling lubricant when it is wetted with the cooling lubricant. Here, a semipermeable membrane may include a substantially liquid biocide or a biocide solution. This membrane may be designed to allow passage of the biocide into the cooling lubricant, but not to penetrate the coolant into the formulation. The result is a desired delayed and essentially continuous release of active ingredient in the cooling lubricant. Furthermore, a formulation can be used in which a liquid or solid biocide or biocide mixture is surrounded by a film which has one or more small openings (holes). This also makes it possible in a simple manner to give off a delayed and essentially continuous active ingredient in the cooling lubricant. Whether or not penetration of the cooling lubricant into the formulation is allowed or not, the person skilled in the art will decide on the basis of the aggregate state of the biocide within the formulation and the desired amount and duration of the release of the active substance.

According to claim 8 it is provided to use a formulation in which a biocide or a biocide solution is encapsulated. Such a formulation is understood to mean granules, tablets or capsules in which the biocide to be delivered is encapsulated by a cover layer, in particular a lubricant-resistant coating. In this case, the cover layer is in turn suitable for providing a time-delayed passage of the biocide through the cover layer into the cooling lubricant. In other words, the required biocide, biocide mixture or solution is provided encapsulated such that when wetted with, and particularly when the encapsulated formulation is submerged in the coolant supply, a delayed release of the contained biocide amount into the coolant automatically occurs. Appropriately suitable formulations which contain a biocide encapsulated or are suitable for the capsule-like uptake of a biocide and processes for the preparation of such formulations are described in WO 2004/000953 A1, EP 1 108 824 A1, EP 0 758 633 B1, US Pat. No. 4,089,800, WO 2008 / 000796 A2, WO 2008/000797 A2, DE 10 2006 030 705 A1 and DE 10 2006 061 890 A1.

In the context of the present invention, it has surprisingly been found that such formulations are not only suitable for delayed biocide release in purely aqueous or dry environments, but can also provide with excellent results a permanent preservation of cooling lubricants.

The use of a formulation which releases the contained biocide merely by emptying the capsules, but does not dissolve the top layer or capsule wall, is particularly preferred. The biocide or the biocide mixture can be provided in pure form, ie not mixed with or dispersed in other types. In this case, it is advantageous that in view of existing legal regulations by dispensing with mixing or dispersing with other components, no "new" biocidal active substance is formed, which would otherwise have to undergo an authorization procedure. Rather, it is possible to use proven and approved biocides or the like be resorted to.

Particularly preferred is an embodiment of the method described by claim 8, in which biocidal microcapsules are added as formulation, as they are known, for example, from WO 2004/000953 A1, DE 10 2006 030 705 A1 or WO 2008/000797 A2. With such microcapsules, surprisingly excellent long-term preservation can also be achieved by cooling lubricants.

Moreover, according to claim 15, the use of such biocidal microcapsules for the biocidal treatment of a cooling lubricant is proposed.

It proves to be a further embodiment of the method described by claim 8 according to claim 8 as appropriate, in which a granulate is added as a formulation. A particularly advantageous is the addition of a formulation in which the biocide or the biocide solution is surrounded by a cool lubricant-resistant cover layer, in particular a polymer, a polymer mixture, rubber, rubber, or a mixture thereof, like a capsule. In other words, this is the use of an application form in which the solid or liquid biocide or a corresponding mixture or solution is surrounded by a cover layer, which does not dissolve when wetted with the cooling lubricant. These cover layer materials provide a particularly advantageous time-delayed, yet substantially constant drug delivery. By varying the thickness of the cover layer, for example the granules or the tablets, practically any release regime can be preset here.

Since the latter forms of application, for example as granules, do not dissolve during use in the cooling lubricant but merely empty the individual granules or tablets (leaving the cover layer or shell), it is particularly expedient to use such formulations within a container which is permeable to liquids , in particular a fabric or fabric bag, to introduce into the cooling lubricant. In other words, the formulation of the invention can be particularly easily and conveniently suspended in the manner of a "tea bag" in the cooling lubricant supply and disposed of after emptying of the drug simply.

A particularly effective release of biocides with substantially constant concentration is achievable if the formulation is exposed to the coolant in a bag of filter material. In particular, the use of a bag or a bag made of paper filter material has proved to be particularly advantageous.

According to a further embodiment of the method described by claim 8, a formulation is added which is a fungicide, in particular IPBC (3-iodo-2-propynyl-butylcarbamate) and / or OIT (octyl-isothiazolinone), and / or a bactericide, in particular BIT (Benzisothiazolinone). Accordingly, already mentioned formulations are expressly also suitable for the encapsulation and controlled release of bactericides. Furthermore, the object mentioned above with regard to a formulation for the biocidal treatment of a cooling lubricant having the features of claim 16 is achieved. Thus, a formulation is given which has a water-miscible and / or water-soluble carrier substance and a biocide.

Advantageous embodiments and further developments of the formulation according to the invention can be taken from the subordinate claims in this regard.

With regard to advantages of this formulation according to the invention, reference is made to the remarks relating to the method according to the invention in order to avoid repetition.

An expedient development of the formulation according to the invention is characterized in that the formulation is surrounded by a removable before use film. It is expressly not a semi-permeable or limited-permeability film as mentioned above. Rather, in this context, a film is meant, which surrounds the formulation as a tight package. Thus, the formulation according to the invention can be handled easily without persons coming into direct contact with the biocide. If the formulation is to be used, the film is removed - comparable to known dishwasher tablets. Thereafter, the formulation may, for example, simply be added to the system or storage container for the cooling lubricant within a processing machine.

Particularly preferred is an embodiment of the formulation according to the invention, in which the carrier substance has a water-miscible and / or water-soluble plastic, in particular polyethylene glycol (PEG), and in particular PEG having an average molecular weight of about 35,000 g / mol. In the context of the present invention, it has been found that biocides commonly used for the preservation of cooling lubricants are readily dispersible in polyethylene glycol. The biocide-doped solid can then be pressed, for example, in tablet form, and can then be used in one of the aforementioned species for biocidal treatment. With a view to achieving a comparatively slower dissolution of the formulation according to the invention, an embodiment is proposed in which the carrier substance has a water-miscible and / or water-soluble wax, in particular an emulsifier-containing wax. A formulation with a carrier formed from wax dissolves more slowly than an aforementioned formulation with the carrier PEG.

Thus, selection of the vehicle, biocide content selection, and size of tablet or stone size will provide the practitioner with an almost unlimited number of options for adjusting the duration and amount of biocide release into the coolant. In this context, an embodiment is particularly preferred in which the carrier substance comprises a mixture of a water-miscible and / or water-soluble plastic, in particular PEG, and a water-miscible and / or water-soluble, in particular emulsifier-containing wax. Thus, virtually any dissolution behavior can be achieved.

Further, the above object is achieved with respect to a formulation for the biocidal treatment of a cooling lubricant with the features of claim 20. Thereafter, a formulation according to the invention comprises a semi-permeable and / or only partially permeable membrane or film which includes a biocide or a biocide solution, wherein the amount of biocide contained is released into the formulation when the formulation is wetted with the cooling lubricant.

Here too, reference is made to the statements relating to the method with regard to advantages and effects according to the invention.

This formulation according to the invention is particularly advantageous in view of the possibility of providing the biocide or the biocide mixture in pure form, ie not mixed with or dispersed in other substances. Thus, said membrane or film may directly contain the liquid biocide or liquid biocide mixture. Again, with regard to existing legal regulations by dispensing with mixing or dispersing with other components, no "new" biocidal active substance, which possibly only one Pass through the authorization procedure. Rather, proven and approved biocides or the like mixtures can be used.

The above object is finally achieved with respect to a ready-to-use product for the biocidal treatment of a cooling lubricant with the features of claim 21. Accordingly, it is proposed a ready-to-use product for the biocidal treatment of a cooling lubricant, in particular a water-mixed cooling lubricant, with a formulation in which a biocide or a biocide solution is encapsulated, and a bag of filter material, in particular of paper filter material, which receives the formulation.

A particularly expedient embodiment of the ready-to-use product is characterized by the fact that the bag of filter material is additionally surrounded by an envelope made of perforated plastic film, in particular polyamide. As a result, the bag made of filter material, in particular if it is made of paper filter material, can additionally stabilize without hindering the release of the biocide from the formulation contained therein. Disintegration of the filter material is effectively prevented.

It should be emphasized that the use of the last-described formulations or of the ready-to-use product or its advantageous developments expressly also specifies further advantageous embodiments of the method according to the invention, while advantageous embodiments of the formulations according to the invention or of the ready-to-use product have been described with reference to the method.

Finally, it should be emphasized that the exemplary embodiments described above discuss the claimed teaching, but do not restrict it to the exemplary embodiments.

Claims

1. A method for the biocidal treatment of a cooling lubricant, in particular a water-mixed cooling lubricant, in particular wherein the cooling lubricant is provided in a circuit within a machine for lubricating and / or cooling during a processing step, characterized in that the cooling lubricant is added to a biocide or a biocide mixture within a formulation which delays the amount of biocide contained in the cooling lubricant.

2. The method according to claim 1, characterized in that a formulation is used which delivers the biocide continuously in terms of time, in particular in a substantially constant dosage, as needed in the cooling lubricant.

3. The method according to claim 1 or 2, characterized in that the formulation is a granule, a capsule, a tablet, a stone or the like is used.

4. The method according to any one of claims 1 to 3, characterized in that the formulation is added to the cooling lubricant, in particular in a system or reservoir for the cooling lubricant.

5. The method according to claim 4, characterized in that the formulation is exposed to the cooling lubricant in a liquid-permeable container, preferably a wire basket or the like.

6. The method according to any one of claims 1 to 5, characterized in that a formulation is used which comprises at least one water-miscible and / or water-soluble carrier substance and at least one biocide.

7. The method according to any one of claims 1 to 6, characterized in that a formulation is used, in which a semi-permeable and / or only limited permeable membrane or foil a biocide or a biocide solution a closes, and when wetting with the cooling lubricant delays the amount of biocide contained in the cooling lubricant.

8. The method according to claim 1, characterized in that the cooling lubricant is added a formulation in which a biocide or a biocide solution is encapsulated, wherein the formulation releases the amount of biocide delayed in the cooling lubricant.

9. The method according to claim 8, characterized in that biocidal microcapsules are added as a formulation.

10. The method according to claim 8 or 9, characterized in that as a granulate formulation is added.

11. The method according to any one of claims 8 to 10, characterized in that a formulation is added, in which the biocide or the biocide solution of a cool lubricant-resistant cover layer, in particular of a polymer, a polymer mixture, rubber, rubber, or a mixture thereof, capsule-like is surrounded.

12. The method according to any one of claims 8 to 11, characterized in that the formulation is exposed to the cooling lubricant in a fabric or fabric bag.

13. The method according to any one of claims 8 to 12, characterized in that the formulation is exposed to the cooling lubricant in a bag of filter material.

14. The method according to any one of claims 8 to 13, characterized in that a formulation is added, which has a fungicide, in particular IPBC and / or OIT, and / or a bactericide, in particular BIT.

15. Use of biocidal microcapsules for the biocidal treatment of a cooling lubricant.

16. A formulation for the biocidal treatment of a cooling lubricant, in particular for carrying out a method according to any one of claims 1 to 7, wherein the formulation comprises a water-miscible and / or water-soluble carrier substance and a biocide.

17. A formulation according to claim 16, characterized in that the formulation is surrounded by a removable before use film.

18. A formulation according to claim 16 or 17, characterized in that the carrier substance is a water-miscible and / or water-soluble plastic, in particular polyethylene glycol (PEG), and in particular PEG having an average molecular weight of about 35000 g / mol.

19. A formulation according to any one of claims 16 to 18, characterized in that the carrier substance comprises a water-miscible and / or water-soluble wax, in particular an emulsifier-containing wax.

20. Formulation for the biocidal treatment of a cooling lubricant, in particular for carrying out a method according to any one of claims 1 to 7, wherein the formulation comprises a semi-permeable and / or only limited permeable membrane or film, which includes a biocide or a biocide solution, wherein the contained Biocide amount when wetting the formulation with the cooling lubricant is delayed in these delivered.

21. A ready-to-use product for the biocidal treatment of a cooling lubricant, in particular a water-mixed cooling lubricant, in particular for carrying out a method according to one of claims 8 to 14, with a formulation in which a biocide or a biocide solution is encapsulated, and a bag of filter material receiving the formulation , in particular of paper filter material.

22. Ready-to-use product according to claim 21, characterized in that the bag of filter material is additionally surrounded by a sheath of perforated plastic film, in particular of polyamide.