EP0773281A2 - Preparations for production of stabilized coolantiubricants - Google Patents

Abstract

An additive mixt. (A) for cold lubricant products contains (a) an N-(cyclo)alkyl-isothiazolone of formula (I), (b) a stabiliser for preventing chemical decomposition of (I) and (c) at least one solubiliser selected from phenoxyethanol, phenoxypropanols, phenoxybutanols, dipropylene glycol, 1-methoxypropan-2-ol and butyl diglycol. Y = 1-18C alkyl or 3-12C cycloalkyl (both opt. substd. by one or more of OH, halogen, CN, mono- or dialkylamino, aryl, NH2, COOH, alkoxycarbonyl, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoyloxy and isothiazolonyl); 2-8C alkenyl or 2-8C alkynyl (both opt. substd. by one or more halogen); 7-10C aralkyl (opt. substd. by one or more halogen or by one or more of 1-4C alkyl and 1-4C alkoxy); or aryl (opt. substd. by one or more of halogen, NO2, 1-4C alkyl, (1-4C)alkyl-acrylamino, (1-4C)alkoxycarbonyl and sulphamoyl); R,R1 = H, halogen, 1-4C alkyl or 4-8C cycloalkyl, or together form a fused benzene ring. Also claimed are a cold lubricant prod. contg. (A), together with conventional components; and the use of (A) for prepn. of cold lubricants.

Description

The present invention relates to additive mixtures for cooling lubricant products and cooling lubricant products which contain an isothiazolone and a stabilizer which is effective against chemical decomposition of the isothiazolone.

Isothiazolone compounds are known to be effective bactericidal and / or fungicidal active ingredients in cooling lubricants for metalworking. However, certain components in metalworking fluids tend to destroy the isothiazolones and thus eliminate their microbiological protective activity. This is particularly the case when the metalworking fluids are in a concentrated form.

Other microbicides that are present in combination with isothiazolones can also attack isothiazolones. An example of this is the sodium salt of 2-mercapto-pyridine-N-oxide (sodium omadine) that 5-chloro-2-methyl-isothiazolone decomposes in any system in which both are present together.

Therefore, possibilities were sought to improve the stability of isothiazolone solutions.

From US-A-3 870 795 and US-A-4 067 878 it is known that isothiazolones can be stabilized against chemical decomposition by adding a metal nitrite or a metal nitrate. It is further disclosed that other common salts, including carbonates, sulfates, chlorates, perchlorates and chlorides, are not effective in stabilizing isothiazolone solutions.

EP-A-0 425 143, US-A-4 150 026 and US-A-4 241 214 disclose that metal salt complexes of isothiazolones are useful because of their improved thermal stability while maintaining biological activity.

Furthermore, the use of certain organic stabilizers for isothiazolones is known, for example from EP-A-0 375 367 and EP-A-0 530 986. These are generally used where metal salts have problems such as corrosion, coagulation of latices and insolubility in non-aqueous media, cause interaction with the substrate to be stabilized and the like.

For example, in US-A-4 165 318 and US-A-4 129 448 formaldehyde or formaldehyde releasing chemicals are disclosed as stabilizers. Orthoesters are known from EP-A-0 315 464 and epoxides are known as stabilizers from EP-A-0 342 852.

Also known from EP-B-0 443 821 are additive mixtures for cooling lubricant products which, according to the preamble of claim 1, contain an isothiazolone and a stabilizer which is effective against chemical decomposition of the isothiazolone. To stabilize the isothiazolones there is disclosed the use of sulfur-containing compounds or salts thereof, which with the Isothiazolone can reversibly form an adduct, especially compounds in which a sulfur atom is attached to an aromatic ring containing nitrogen. Suitable compounds are (in EP-B-0 443 821) 4-mercaptopyridine, the sodium salt of 2-mercaptopyridine, 2-mercaptobenzothiazole and 4-methyl-4-H-1,2,4-triazole-3-thiol . Other compounds mentioned are 2-methylthiobenzothiazole, 2-thiohydantoin, methylene bisthiocyanate, L-cystine and 4-R (thiazolidene-thione-4-carboxylic acid). According to EP-B-0 443 821, the ratio of stabilizer to isothiazolone effective for stabilization is at least 0.1: 1, in particular between 0.5: 1 and 1.5: 1.

The compositions of isothiazolone and stabilizer known from EP-B-0 443 821 can additionally contain solvents. Preferred solvents are so-called "capped polyols", e.g. Triethylene glycol dimethyl ether.

However, when trying to formulate ready-to-use preparations according to the prior art, mostly inhomogeneous or unstable solutions are obtained, especially after short storage times. These inhomogeneities make accurate dosing of the isothiazolone / stabilizer compositions difficult or impossible. A separate addition of active ingredient and stabilizer is possible, but in practice not desirable and too prone to errors.

Accordingly, it is the object of the present invention to provide additive mixtures for cooling lubricant products which contain isothiazolones as bactericidal and / or fungicidal active ingredients, which protect cooling lubricant concentrates or cooling lubricants produced therefrom from microbial attack and improve the durability and service life of the cooling lubricant products. The additive mixtures according to the invention should themselves be sufficiently stable and storable and durable under practical conditions.

It is also an object of the present invention to formulate compositions containing isothiazolone and stabilizer in such a way that they can be metered easily into commercially available cooling lubricants, for example by adding a liquid preparation. The metering should be possible in a coolant concentrate or in a coolant, preferably a water-mixed coolant.

It is also an object of the present invention to provide effective cooling lubricant products which are distinguished from the prior art in that they have increased stability and improved effectiveness.

The objects are solved by the characterizing features of claims 1 and 14. According to claim 1, a solubilizer is additionally provided in the additive mixtures, which is selected from phenoxyethanol, phenoxypropanols, phenoxybutanols, dipropylene glycol, 1-methoxypropanol-2, butyl diglycol and mixtures thereof. The solubilizer is preferably phenoxyethanol, phenoxypropanol or 1-methoxypropanol-2. The solubilizer is, for example, in an amount of 30 to 91.7% by weight, for example 30 to 75, preferably 40 to 70% by weight, more preferably 50 to 65% by weight and in particular approximately 58% by weight Additive mixture included.

In addition to the usual constituents, the cooling lubricant products contain an additive mixture according to the invention. The cooling lubricant products can be present as a cooling lubricant concentrate or contain the cooling lubricant concentrate. Accordingly, the additives according to the invention can be introduced into cooling lubricant concentrates, which are subsequently diluted to cooling lubricants. The cooling lubricant products can be in the form of a solution or an emulsion. Water-mixed cooling lubricants are preferably produced.

wiedergegeben werden, in der
Y eine (C₁-C₁₈)-Alkyl- oder (C₃-C₁₂)-Cycloalkylgruppe ist, die mit einer oder mehreren Hydroxy-, Halogen-, Cyano-, Alkylamino-, Dialkylamino-, Aryl-, Amino-, Carboxy-, Carbalkoxy-, Alkoxy-, Aryloxy-, Alkylthio-, Arylthio-, Halogenalkoxy-, Cycloalkylamino-, Carbamoxy- oder Isothiazolonylgruppen substituiert sein kann, eine unsubstituierte oder mit Halogen substituierte (C₂-C₈)-Alkenyl- oder -Alkinylgruppe, eine (C₇-C₁₀)-Aralkylgruppe, die mit einem oder mehreren Halogenatomen oder einer oder mehreren (C₁-C₄)-Alkyl- oder (C₁-C₄)-Alkoxygruppen substituiert sein kann, oder eine Arylgruppe ist, die mit einer oder mehreren Halogenatomen, Nitro-, (C₁-C₄)-Alkyl-, (C₁-C₄)-Alkyl-acrylamino-, Carb(C₁-C₄)-alkoxy- oder Sulfamylgruppen substituiert sein kann, und
R und R¹ jeweils unabhängig Wasserstoff, Halogen, eine (C₁-C₄)-Alkylgruppe, eine (C₄-C₈)-Cycloalkylgruppe sind oder miteinander unter Ausbildung einer Benzoisothiazolonylgruppe verbunden sind, wobei halogenfreie Isothiazolone und insbesondere N-Oktyl-Isothiazolon bevorzugt sind.The isothiazolones used in the additive mixture according to the invention include those which are known from EP-B-0 443 821. In particular, there are those by the formula

are reproduced in the
Y is a (C ₁ -C ₁₈ ) alkyl or (C ₃ -C ₁₂ ) cycloalkyl group which is linked to one or more hydroxyl, halogen, cyano, alkylamino, dialkylamino, aryl, amino, Carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy or isothiazolonyl groups, an unsubstituted or halogen-substituted (C ₂ -C ₈ ) alkenyl or - Alkynyl group, a (C ₇ -C ₁₀ ) aralkyl group which may be substituted with one or more halogen atoms or one or more (C ₁ -C ₄ ) alkyl or (C ₁ -C ₄ ) alkoxy groups, or an aryl group is substituted with one or more halogen atoms, nitro, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkyl acrylamino, carb (C ₁ -C ₄ ) alkoxy or sulfamyl groups can be and
R and R ^{1 are} each independently hydrogen, halogen, a (C ₁ -C ₄ ) alkyl group, a (C ₄ -C ₈ ) cycloalkyl group or are linked together to form a benzoisothiazolonyl group, halogen-free isothiazolones and in particular N-octyl- Isothiazolone are preferred.

Suitable stabilizers or stabilizer mixtures for the isothiazolone compounds are the compounds known from the prior art, and in particular sulfur-containing compounds or salts thereof, which are reversible with the isothiazolone Can form an adduct. Heterocyclic sulfur-nitrogen compounds such as 2-mercaptopyridine-N-oxide and corresponding salts, preferably alkali metal or ammonium salts such as pyrion-Na (40% aqueous solution of 2-mercaptorpyridine-N-oxide sodium salt) are particularly suitable. , 2-mercaptopyridine-N-oxide metal salt complexes such as zinc-pyrithione (e.g. as a 48% aqueous dispersion), 2,2'-dithiobis (pyridine-N-oxide) (pyrion disulfide), 2-mercaptobenzothiazole, 2- ( Thiocyanatomethyl) thio-benzothiazole (TCMTB) and mixtures thereof. In particular, pyrion-Na, zinc pyrithione, pyrion disulfide and 2-mercaptobenzothiazole are preferred. In addition, mild oxidizing agents such as iodopropynyl butyl carbamate, hydrogen peroxide, t-butyl hydroperoxide, sodium bromate and Cu (II) salts are also suitable as stabilizers or co-stabilizers according to the invention, sodium bromate, hydrogen peroxide, 2-tert-butyl-6-methylphenol and pyrion disulfidals Co-stabilizers are preferred.

• a. 5 bis 45 Gew.-%, beispielseise 15 bis 45 Gew.-%, vorzugsweise 20 bis 30 Gew.-% und insbesondere etwa 24,5 Gew.-% einer 45%igen n-Octylisothiazolon-Lösung in 1,2-Propylenglykol (Kathon 893),
• b. 3,3 bis 25 Gew.-%, beispielsweise 10 bis 25 Gew.-%, vorzugseise 15 bis 20 Gew.-% und insbesondere etwa 17,5 Gew.-% einer 40%igen wäßrigen 2-Mercaptopyridin-N-oxid-Natriumsalz-Lösung (Pyrion-Na) und
• c. 30 bis 91,7 Gew.-%, beispielsweise 30 bis 75 Gew.-%, vorzusweise 50 bis 65 Gew.-% und insbesondere etwa 58 Gew.-% Phenoxyethanol, Phenoxypropanol oder 1-Methoxypropanol-2.

Preparations which comprise the following components are particularly suitable:

• a. 5 to 45% by weight, for example 15 to 45% by weight, preferably 20 to 30% by weight and in particular approximately 24.5% by weight of a 45% n-octylisothiazolone solution in 1,2-propylene glycol (Kathon 893),
• b. 3.3 to 25% by weight, for example 10 to 25% by weight, preferably 15 to 20% by weight and in particular approximately 17.5% by weight of a 40% aqueous 2-mercaptopyridine-N-oxide Sodium salt solution (Pyrion-Na) and
• c. 30 to 91.7% by weight, for example 30 to 75% by weight, preferably 50 to 65% by weight and in particular approximately 58% by weight of phenoxyethanol, phenoxypropanol or 1-methoxypropanol-2.

Accordingly, the isothiazolone content in the additive mixture can be 2.25 to 20.25% by weight, for example 6.75 to 20.25% by weight, preferably 9 to 13.5% by weight and in particular approximately 11 % By weight.

The stabilizer content in the additive mixture can be approximately 1.3 to 10% by weight, for example 4 to 10% by weight, preferably 6 to 8% by weight and in particular approximately 7% by weight, with for example also 0.05 up to 1.0, preferably 0.5 to 0.1% by weight, in particular 0.2% by weight, of cocatalyst can be present.

The molar ratio of isothiazolone compound: stabilizer is, for example, at least 10: 1, preferably between 1.5: 1 and 1: 1.5 and in particular about 1: 1, such as between 1.1: 1 and 1: 1.27.

The additive mixtures are preferably incorporated into commercially available coolant concentrates, from which dilutions with water are then made, e.g. 4% dilutions.

The liquid preparations can optionally contain further additives which support the functional properties of the cooling lubricant or cooling lubricant additive.

According to the invention, the active ingredient (isothiazolone) and the stabilizer (for example Pyrion-Na) are present as a liquid, stable preparation in a one-component system. The preparation is easy to dose and can be stored and stored even under practical conditions. The ease of handling of the preparation is also advantageous compared to the storage, preparation and metering of active ingredients and stabilizers present in two-component systems.

The additive mixtures according to the invention can be added effectively to cooling lubricant concentrates, so that their durability and the service life of the finished cooling lubricant products are improved compared to known systems. The increased stability of the preparations according to the invention is particularly evident in the lower tendency to form sediments.

Surprisingly, it was found that the combination of isothiazolone, stabilizer and special solubilizer not only facilitates the handling and dosage of the agent, it also improves the stability and in particular the effectiveness of the biocide mixture.

The synergistic effect achieved when using an additive mixture according to the invention in cooling lubricant products is illustrated by the examples below.

Examples

In the following examples, Kathon RH 893 denotes a 45% n-octylisothiazolone solution in 1,2-propylene glycol and Pyrion-Na a 40% aqueous 2-mercaptopyridine-N-oxide sodium salt solution.

Example 1 : Stabilization of N-octylisothiazolone in cooling lubricants

In a series of tests, the stability of Kathon RH 893 in a cooling lubricant (Shell Dromus B) was followed with and without the addition of a stabilizer by means of an active ingredient determination. For this purpose, 0.28% Kathon 893 (corresponding to 0.1275% N-octylisothiazolone, NOITZ) and stabilizers in different molar ratios were incorporated into 60 g Shell Dromus B. Shortly before the HPLC determination of the isothiazolone content, 5% emulsions with completely deionized (demineralized) water were prepared from these concentrates. The concentrates were stored in clear glass at room temperature or 40 ° C. stabilizer Mole ratio NOITZ: Staff. Appearance of the concentrate NOITZ content of the emulsion Zero value: n.6d at RT (40 ° C) n.20d at RT (40 ° C) without clear, reddish brown 0.13% 0.13% (0.09%) 0.11% (0.03%) 0.0233% Na pyrion (40%) 10: 1 clear, very dark 0.13% 0.13% (0.12%) 0.12% (0.07%) 0.2233% Na pyrion (40%) 1: 1 clear, very dark 0.14% 0.13% (0.13%) 0.13% (0.13%) 0.015% pyrion disulfide (96%) 10: 1 clear, reddish brown 0.13% 0.12% (0.12%) 0.12% (0.09%) 0.1572% pyrion disulfide (96%) 1: 1 cloudy, reddish brown 0.13% 0.13% (0.12% *) 0.12% * (0.12%) * strong sediment in the concentrate

This experiment shows that by adding the stabilizers, a considerable stabilization of the NOITZ in cooling lubricant concentrates is achieved. However, this experiment also shows that the addition of Na pyrion or pyrion disulfide leads to deep discoloration of the solutions and cloudiness or sediments.

Example 2 : N-Octylisothiazolone Stabilization - Compatibility of Kathon 893 with Pyrion-Na

The tolerance and stability of preparations based on 2 parts of Kathon 893 and 0.5 to 4.0 parts of Pyrion-Na (40%), in 0.5% concentration steps, without the addition of other solubilizers, was found after storage in clear glass at room temperature checked. The initially clear, yellow solutions (zero value or after 18 days) were in part two-phase after 3 months or showed minor precipitations.

Preparations based on Kathon 893 and Pyrion-Na in a molar ratio of 1: 1 to 1: 5 (without the addition of other solubilizers) were inhomogeneous after five months of storage at room temperature. The stability tended to decrease with increasing pyrion Na content.

Example 3 : N-Octylisothiazolone Stabilization - Compatibility of Kathon 893 with Pyrion-Na (MV 1: 1.27) in the presence of solubilizers

The compatibility and stability of preparations based on 40 parts Kathon 893 and 40 parts Pyrion-Na (40%) in various solubilizers was tested in clear glass at room temperature (molar ratio N-octylisothiazolone: 2-mercaptopyridine-N-oxide-Na = 1: 1.27). The initially clear, homogeneous yellow to orange-yellow solutions (zero values) tended to form (yellow) precipitation depending on the time. After 6 months, sediments appeared with hexylene glycol, dipropylene glycol, 1,2-propylene glycol and phenoxyethanol, somewhat less with butyl diglycol and 1-methoxypropanol-2 and practically none with phenoxypropanol. The Solutions had no unpleasant smell of sulfur and were practically unchanged colored yellow-orange.

Example 4 : N-Octylisothiazolone Stabilization - Compatibility of Kathon 893 with Pyrion-Na (MV 1: 0.9) in the presence of solubilizers

The compatibility and stability of preparations based on 35 parts Kathon 893 and 25 parts Pyrion-Na (40%) in various solubilizers was tested in clear glass at room temperature (molar ratio N-octylisothiazolone: 2-mercaptopyridine-N-oxide-Na = 1: 0.9). The initially clear, homogeneous yellow to yellow-red solutions (zero values) tended to form (yellow) precipitation depending on the time and changed color depending on the solvent. The tendency to form sediments was less than in the test series with an N-octylisothiazolone / 2-mercaptopyridine-Na-oxide-Na ratio of 1: 1.27. The preparation with butyl diglycol was particularly intensely colored, samples with hexylene glycol or dipropylene glycol were slightly less dark, samples with 1-methoxypropanol-2 and 1,2-propylene glycol were only slightly colored orange, while preparations with phenoxyethanol or phenoxypropanol were practically unchanged colored yellow. With hexylene glycol and phenoxypropanol, only little precipitation occurs after 6 months at room temperature, solutions with phenoxyethanol were practically free of precipitation. The solutions had no unpleasant smell of sulfur.

Example 5 : N-octylisothiazolone stabilization - stability of preparations

Formulations based on Kathon 893 and Pyrion-Na (40%) were dissolved in a molar ratio of 1: 1 to 1: 5 in various solubilizers and examined for compatibility and stability. The total active substance content (sum of N-octylisothiazolone and 2-mercaptopyridine-N-oxide-Na salt) was approx. 18%.

After 6 months of storage at room temperature in clear glass, the following results were obtained:

With increasing Kathon 893 content, the initially clear, yellow solutions turned slightly darker or deep dark red. Preparations with the solubilizers 1,2-propylene glycol, phenoxypropanol and phenoxyethanol in all tested molar ratios were little changed in color. Solutions with 1-methoxypropanol-2 and dipropylene glycol were somewhat darker and solutions with hexylene glycol and especially butyl diglycol were deep dark red.

The formation of precipitation and inhomogeneities was not primarily dependent on the molar ratio of the active ingredients, but rather on the solubilizer. Comparatively little precipitation occurred in solutions with a phenoxyethanol, phenoxypropanol or 1-methoxypropanol-2 content.

Comparatively voluminous sediments, on the other hand, were formed in solutions with butyl diglycol. With the other solution brokers, there were also some precipitations.

The investigations show that the stability and compatibility of Kathon 893 with Pyrion-Na is partly strongly dependent on the type of solubilizer and the molar ratio of the active ingredients.

Example 6 : Stabilization of N-octylisothiazolone in cooling lubricants

In a series of experiments, the stability of Kathon 893 in cooling lubricant concentrates without and with stabilizer addition was monitored via the degradation of the active ingredient after storage. In this series of experiments, the concentrates were stored in clear glass at 40 ° C.

A

Kombination aus 24,5 Gew.-% Kathon 893, 17,5 Gew.-% Pyrion-Na und 58 Gew.-% 1-Methoxypropanol-2

B

Kombination aus 24,5 Gew.-% Kathon 893, 17,5 Gew.-% Pyrion-Na und 58 Gew.-% Phenoxyethanol

C

Kombination aus 24,5 Gew.-% Kathon 893, 17,5 Gew.-% Pyrion-Na und 58 Gew.-% Phenoxypropanol

oder eine Kombination aus Kathon 893 und Pyrion-Na ohne Lösungsvermittler eingearbeitet. Der Kathon 893-Gehalt ist in allen untersuchten Präparaten gleich. Die Proben wurden bei 40°C bzw. Raumtemperatur in Klarglas gelagert und täglich ca. 7 bis 8 Stunden gerührt. Aus den optisch stabilen Konzentraten wurden mit VE-Wasser 4%ige Lösungen bzw. Emulsionen hergestellt, deren NOITZ-Gehalt mittels HPLC bestimmt wurde. Nullwerte wurden nicht ermittelt.0.28% Kathon 893 (corresponds to 0.126% NOITZ) and the test products were added to the concentrates:

A

Combination of 24.5% by weight Kathon 893, 17.5% by weight Pyrion-Na and 58% by weight 1-methoxypropanol-2

B

Combination of 24.5% by weight Kathon 893, 17.5% by weight Pyrion-Na and 58% by weight phenoxyethanol

C.

Combination of 24.5% by weight Kathon 893, 17.5% by weight Pyrion-Na and 58% by weight phenoxypropanol

or a combination of Kathon 893 and Pyrion-Na without a solubilizer. The Kathon 893 content is the same in all preparations examined. The samples were stored in clear glass at 40 ° C. or room temperature and stirred for about 7 to 8 hours daily. 4% solutions or emulsions were prepared from the optically stable concentrates with demineralized water, the NOITZ content of which was determined by HPLC. Zero values were not determined.

Results:

N-octylisothiazolone content after storage:
Coolant concentrate: SA 2146 After 3 14 22 28 days at 40 ° C Kathon 893 0.01% <0.01% <0.01% A 0.12% 0.10% <0.01% B 0.12% 0.09% <0.01% C. 0.13% 0.10% 0.09% <0.01% Kathon 893 + Pyrion-Na 0.14% 0.12% <0.01% N-octylisothiazolone content after storage:
Coolant concentrate: SA 2146 After 28 days at RT Kathon 893 <0.01% A 0.11% B 0.11% C. 0.12% Kathon 893 + Pyrion-Na 0.12% N-octylisothiazolone content after storage:
Coolant concentrate: Kutwell 40 after 3 14 22 28 35 days at 40 ° C Kathon 893 0.13% 0.11% 0.11% 0.11% 0.11% A 0.13% 0.11% 0.11% 0.10% 0.11% B 0.13% 0.11% 0.11% 0.11% 0.11% C. 0.13% 0.11% 0.10% 0.11% 0.11% Kathon 893 + Pyrion-Na 0.13% 0.14% 0.11% 0.10% 0.11%

The concentrates and emulsions plus additives were practically unchanged, even after storage. With regard to the extent of stabilization, the concentrates differed significantly in part due to the different compositions. Products A to C did not differ significantly with regard to the stabilizing effect of isothiazolone - with the exception of C for cooling lubricant concentrate SA 2146 - not even compared to the separate addition of Kathon 893 and Pyrion-Na.

Example 7 : Bactericide / fungicide for cooling lubricants Stabilization of N-octylisothiazolone with Na-Pyrion, Boko tests

A Boko and Lager Boko test (10 days storage of the cooling lubricant concentrate at 40 ° C) was carried out using the samples A, B, C from Example 6 (preparations based on Kathon 893, Pyrion-Na and solubilizers), the individual active ingredients and a combination of the active ingredients NOITZ (Kathon 893 was used) and Na-Pyrion. The preparations or active ingredients were incorporated into the concentrates, from which 4% dilutions were then made in Norderstedter city water.

Boko result:

preparation Use conc. Survived vaccination cycles (inoculation with fungal suspension) unsupported coolant Shell Dromus BX stored coolant Shell Dromus BX A 0.1% > 12 > 12 0.075% > 12 > 5 0.05% 3rd 1 0.025% 0 0 B 0.1% > 12 > 12 0.075% > 12 > 12 0.05% 10th > 6 0.025% 0 0 C. 0.1% > 12 > 12 0.075% > 11 > 12 0.05% > 11 > 12 0.025% 4th 3rd Use conc. Survived vaccination cycles (inoculation with fungal suspension) Kathon 893 Pyrion Na (40%) unsupported coolant Shell Dromus BX stored coolant Shell Dromus BX 0.025% > 12 8th 0.018% 9 3rd 0.012% 9 2nd 0.006% 0 1 0.0175% 0 0 0.013% 0 0 0.0087% 0 0 0.004% 0 0 0.025% 0.0175% > 12 > 12 0.018% 0.013% > 12 > 5 0.012% 0.0087% > 12 2nd 0.006% 0.004% 0 0

The freshly prepared concentrates and the 4% dilutions showed no visual differences to the respective blank value (cooling lubricant without active ingredient). After 10 days of storage at 40 ° C, the active ingredient-containing Shell Dromus BX concentrates and dilutions also showed no visual difference to the blank value. As expected, the stored samples showed a drop in activity, which was, however, comparatively small for products B and C. In the unstored samples, preparation C was the most effective or roughly comparable to the effectiveness of the combination Kathon 893 and Pyrion-Na (without solvent). In the stored samples, C clearly showed the best before B and A Effect that was roughly comparable to the effectiveness of the combination Kathon 893 and Pyrion-Na (without solvent).

Pyrion-Na improved the effectiveness of Kathon 893 in the Boko test. By combining this active substance mixture with a solution mediator according to the invention (in particular phenoxypropanol or phenoxyethanol), the effectiveness in the Boko test could also be maintained under practical conditions (e.g. storage at elevated temperature, which is equivalent to prolonging storage at room temperature).

The combination: Kathon 893, Pyrion-Na and the solubilizer according to the invention not only facilitated the handling and metering of the agent, it also improved the stability and the effectiveness of the biocide mixture.

Claims (19)

Additive mixture for cooling lubricant products, which is an isothiazolone of the formula

in the Y is a (C ₁ -C ₁₈ ) alkyl or (C ₃ -C ₁₂ ) cycloalkyl group which is linked to one or more hydroxyl, halogen, cyano, alkylamino, dialkylamino, aryl, amino, Carboxy, carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy, cycloalkylamino, carbamoxy or isothiazolonyl groups, an unsubstituted or halogen-substituted (C ₂ -C ₈ ) alkenyl or - Alkynyl group, a (C ₇ -C ₁₀ ) aralkyl group which may be substituted with one or more halogen atoms or one or more (C ₁ -C ₄ ) alkyl or (C ₁ -C ₄ ) alkoxy groups, or an aryl group is with one or more halogen atoms, nitro, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkyl acrylamino, carb (C ₁ -C ₄ ) alkoxy or sulfamyl groups can be substituted, and R and R ^{1 are} each independently hydrogen, halogen, a (C ₁ -C ₄ ) alkyl group, a (C ₄ -C ₈ ) cycloalkyl group or are linked together to form a benzoisothiazolonyl group, and comprises a stabilizer effective against chemical decomposition of the isothiazolone and optionally a co-stabilizer, characterized in that it additionally contains a solubilizer which is selected from phenoxyethanol, phenoxypropanols, phenoxybutanols, dipropylene glycol, 1-methoxypropanol-2, butyl diglycol and mixtures thereof. Additive mixture according to claim 1, characterized in that the solubilizer is phenoxyethanol, phenoxypropanol or 1-methoxypropanol-2. Additive mixture according to claim 1 or 2, characterized in that the solubilizer is contained in an amount of 30 to 91.7 wt .-%, based on the additive mixture. Additive mixture according to claim 3, characterized in that the solubilizer is contained in an amount of 30 to 75 wt .-%, based on the additive mixture. Additive mixture according to claim 4, characterized in that the solubilizer is contained in an amount of 50 to 65 wt .-%, based on the additive mixture. Additive mixture according to one of the preceding claims, characterized in that the stabilizer is a sulfur-containing compound or a salt thereof which can form an adduct reversibly with the isothiazolone. Additive mixture according to claim 6, characterized in that the sulfur-containing compound or the salt thereof is selected from 2-mercaptopyridine-N-oxide, metal or ammonium salts of 2-mercaptopyridine-N-oxide, metal salt complexes of 2-mercaptopyridine-N- oxide, 2,2'-dithiobis (pyridine-N-oxide), 2-mercaptobenzothiazole and mixtures thereof. Additive mixture according to one of claims 1 to 5, characterized in that the stabilizer and / or co-stabilizer is a mild oxidizing agent. Additive mixture according to one of claims 1 to 5 and claim 8, characterized in that the stabilizer / co-stabilizer is selected from iodopropynyl butyl carbamate, hydrogen peroxide, t-butyl peroxide, sodium bromate, Cu (II) salts, 2-tert-butyl-6 -methylphenol and pyrion disulfide. Additive mixture according to one of Claims 1 to 7, which, based on the mixture, comprises the following components: a. 2.25 to 20.25% by weight of N-octylisothiazolone, b. about 1.3 to 10% by weight mercaptopyridine-N-oxide sodium salt and c. 30 to 91.7% by weight of 2-phenoxyethanol, 2-phenoxypropanol or 1-methoxypropanol-2. Additive mixture according to claim 10, which comprises, based on the mixture, the following components: a. 6.75 to 20.25% by weight of N-octylisothiazolone, b. 4 to 10 wt .-% mercaptopyridine-N-oxide sodium salt and c. 30 to 75% by weight of 2-phenoxyethanol, 2-phenoxypropanol or 1-methoxypropanol-2. Additive mixture according to claim 11, which comprises, based on the mixture, the following components: a. 9 to 13.5% by weight of N-octylisothiazolone, b. 6 to 8 wt .-% mercaptopyridine-N-oxide sodium salt and c. 50 to 65% by weight 2-phenoxyethanol, 2-phenoxypropanol or 1-methoxypropano1-2. Additive mixture according to claim 12, which comprises, based on the mixture, the following components: a. about 11% by weight of N-octylisothiazolone, b. about 7% by weight mercaptopyridine-N-oxide sodium salt and c. about 58% by weight 2-phenoxyethanol, 2-phenoxypropanol or 1-methoxypropanol-2. Cooling lubricant products, characterized in that, in addition to the usual constituents, they contain an additive mixture according to one of Claims 1 to 13. Cooling lubricant products according to claim 14, characterized in that they are present as cooling lubricant concentrates or ready for use. Cooling lubricant products according to claim 14 or 15, characterized in that they are present as a solution or as an emulsion. Use of an additive mixture according to one of claims 1 to 13 for the production of cooling lubricant products. Use according to claim 17, characterized in that a cooling lubricant concentrate is produced. Use according to claim 17, characterized in that a water-mixed cooling lubricant is produced.