EP0773281A2 - Preparations for production of stabilized coolantiubricants - Google Patents
Preparations for production of stabilized coolantiubricants Download PDFInfo
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- EP0773281A2 EP0773281A2 EP96250190A EP96250190A EP0773281A2 EP 0773281 A2 EP0773281 A2 EP 0773281A2 EP 96250190 A EP96250190 A EP 96250190A EP 96250190 A EP96250190 A EP 96250190A EP 0773281 A2 EP0773281 A2 EP 0773281A2
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- European Patent Office
- Prior art keywords
- additive mixture
- weight
- mixture according
- alkyl
- cooling lubricant
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/16—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/18—Ammonia
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
Definitions
- 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.
- 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.
- 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.
- 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.
- 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.
- an isothiazolone and a stabilizer which is effective against chemical decomposition of the isothiazolone.
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the isothiazolones used in the additive mixture according to the invention include those which are known from EP-B-0 443 821.
- 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 (
- 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.
- TCMTB Thiocyanatomethyl thio-benzothiazole
- pyrion-Na, zinc pyrithione, pyrion disulfide and 2-mercaptobenzothiazole are preferred.
- 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.
- 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.
- the active ingredient isothiazolone
- the stabilizer for example Pyrion-Na
- 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.
- 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.
- 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%.
- 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.
- 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.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Lubricants (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft Additivmischungen für Kühlschmiermittelprodukte sowie Kühlschmiermittelprodukte, die ein Isothiazolon und einen gegen chemische Zersetzung des Isothiazolons wirksamen Stabilisator enthalten.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.
Isothiazolon-Verbindungen sind als wirksame bakterizide und/oder fungizide Wirkstoffe in Kühlschmiermitteln für die Metallverarbeitung bekannt. Allerdings neigen bestimmte Komponenten in Metallverarbeitungsfluiden zur Zerstörung der Isothiazolone und beseitigen somit ihre mikrobiologische Schutzaktivität. Dies ist insbesondere der Fall, wenn die Metallverarbeitungsfluide in konzentrierter Form vorliegen.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.
Auch andere Mikrobizide, die in Kombination mit Isothiazolonen vorhanden sind, können Isothiazolone angreifen. Ein Beispiel dafür ist das Natriumsalz von 2-Mercapto-pyridin-N-oxid (Natriumomadin), daß 5-Chloro-2-methyl-isothiazolon in jedem System zersetzt, in dem beide gemeinsam vorhanden sind.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.
Es wurde daher nach Möglichkeiten gesucht, die Stabilität von Isothiazolon-Lösungen zu verbessern.Therefore, possibilities were sought to improve the stability of isothiazolone solutions.
Aus den US-A-3 870 795 und US-A-4 067 878 ist bekannt, daß Isothiazolone durch Addition eines Metallnitrits oder eines Metallnitrats gegen chemische Zersetzung stabilisiert werden können. Weiterhin wird offenbart, daß andere gewöhnliche Salze, einschließlich Carbonate, Sulfate, Chlorate, Perchlorate und Chloride zur Stabilisierung von Isothiazolon-Lösungen nicht effektiv sind.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.
Die EP-A-0 425 143, US-A-4 150 026 und US-A-4 241 214 offenbaren, daß Metallsalz-Komplexe von Isothiazolonen aufgrund ihrer verbesserten thermischen Stabilität verwendbar sind, während die biologische Aktivität beibehalten wird.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.
Weiterhin ist die Verwendung von bestimmten organischen Stabilisatoren für Isothiazolone bekannt, beispielsweise aus der EP-A-0 375 367 und der EP-A-0 530 986. Diese werden im allgemeinen dort eingesetzt, wo Metallsalze Probleme wie Korrosion, Koagulation von Latices, Unlöslichkeit in nicht-wäßrigen Medien, Wechselwirkung mit dem zu stabilisierenden Substrat und dergleichen hervorrufen.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.
In den US-A-4 165 318 und US-A-4 129 448 werden beispielsweise Formaldehyd oder Formaldehyd freisetzende Chemikalien als Stabilisatoren offenbart. Aus der EP-A-0 315 464 sind Orthoester und aus der EP-A-0 342 852 sind Epoxide als Stabilisierungsmittel bekannt.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.
Auch aus der EP-B-0 443 821 sind Additivmischungen für Kühlschmiermittelprodukte bekannt, die gemäß Oberbegriff von Patentanspruch 1 ein Isothiazolon und einen gegen chemische Zersetzung des Isothiazolons wirksamen Stabilisator enthalten. Zur Stabilisierung der Isothiazolone wird dort die Verwendung schwefelhaltiger Verbindungen oder Salze derselben offenbart, die mit dem Isothiazolon reversibel ein Addukt bilden können, inbesondere Verbindungen, bei denen ein Schwefelatom an einen Stickstoffenthaltenden, aromatischen Ring gebunden ist. Als geeignete Verbindungen werden (in der EP-B-0 443 821) 4-Mercaptopyridin, das Natriumsalz von 2-Mercaptopyridin, 2-Mercaptobenzothiazol und 4-Methyl-4-H-1,2,4-triazol-3-thiol genannt. Andere genannte Verbindungen sind 2-Methylthiobenzothiazol, 2-Thiohydantoin, Methylenbisthiocyanat, L-Cystin und 4-R(Thiazoliden-thion-4-carbonsäure). Das zur Stabilisierung effektive Verhältnis von Stabilisator zu Isothiazolon ist gemäß der EP-B-0 443 821 mindestens 0,1 : 1, insbesondere zwischen 0,5 : 1 bis 1,5 : 1.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.
Die aus der EP-B-0 443 821 bekannten Zusammensetzungen aus Isothiazolon und Stabilisator können zusätzlich Lösungsmittel enthalten. Bevorzugte Lösungsmittel sind sogenannte "capped polyols", wie z.B. Triethylenglykoldimethylether.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.
Bei dem Versuch, einsatzfähige Zubereitungen gemäß dem Stand der Technik zu formulieren, erhält man aber meist inhomogene oder instabile Lösungen, insbesondere nach kurzen Lagerzeiten. Diese Inhomogenitäten erschweren eine genaue Dosierung der Isothiazolon/Stabilisator-Zusammensetzungen oder machen diese unmöglich. Eine getrennte Zugabe von Wirkstoff und Stabilisator ist zwar möglich, in der Praxis aber nicht erwünscht und zu fehleranfällig.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.
Demgemäß liegt der vorliegenden Erfindung die Aufgabe zugrunde, Additivmischungen für Kühlschmiermittelprodukte zur Verfügung zu stellen, welche Isothiazolone als bakterizide und/oder fungizide Wirkstoffe enthalten, die Kühlschmiermittelkonzentrate bzw. daraus hergestellte Kühlschmiermittel vor mikrobiellem Angriff schützen und die Haltbarkeit und Standzeit der Kühlschmiermittelprodukte verbessern. Die erfindungsgemäßen Additivmischungen sollen selbst hinreichend stabil und unter Praxisbedingungen lagerfähig und haltbar sein.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.
Aufgabe der vorliegenden Erfindung ist es ferner, Isothiazolon und Stabilisator enthaltende Zusammensetzungen so zu formulieren, daß sie einfach zu handelsüblichen Kühlschmiermitteln, zum Beispiel durch Zugabe einer flüssigen Zubereitung dosiert werden können. Die Zudosierung soll in ein Kühlschmiermittelkonzentrat oder in ein Kühlschmiermittel, vorzugsweise ein wassergemischtes Kühlschmiermittel, erfolgen können.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.
Aufgabe der vorliegenden Erfindung ist es auch, wirksame Kühlschmiermittelprodukte zur Verfügung zu stellen, die sich gegenüber dem Stand der Technik dadurch auszeichnen, daß sie eine erhöhte Stabilität und eine verbesserte Wirksamkeit aufweisen.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.
Die Aufgaben werden durch die kennzeichnenden Merkmale der Patentansprüche 1 und 14 gelöst. Gemäß Patentanspruch 1 ist in den Additivmischungen zusätzlich ein Lösungsvermittler vorgesehen, der aus Phenoxyethanol, Phenoxypropanolen, Phenoxybutanolen, Dipropylenglykol, 1-Methoxypropanol-2, Butyldiglykol und Mischungen derselben ausgewählt ist. Vorzugsweise ist der Lösungsvermittler Phenoxyethanol, Phenoxypropanol oder 1-Methoxypropanol-2. Der Lösungsvermittler ist beispielsweise in einer Menge von 30 bis 91,7 Gew.-%, beispielsweise 30 bis 75, vorzugsweise 40 bis 70 Gew.-%, bevorzugter 50 bis 65 Gew.-% und insbesondere etwa 58 Gew.-% in der Additivmischung, enthalten.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.
Die Kühlschmiermittelprodukte enthalten neben den üblichen Bestandteilen eine erfindungsgemäße Additivmischung. Die Kühlschmiermittelprodukte können als Kühlschmiermittelkonzentrat vorliegen oder das Kühlschmiermittelkonzentrat enthalten. Demgemäß können die erfindungsgemäßen Additive in Kühlschmiermittelkonzentrate eingebracht werden, die anschließend zu Kühlschmiermitteln verdünnt werden. Die Kühlschmiermittelprodukte können als Lösung oder als Emulsion vorliegen. Vorzugsweise werden wassergemischte Kühlschmiermittel hergestellt.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.
Die in der erfindungsgemäßen Additivmischung verwendeten Isothiazolone schließen solche ein, die aus der EP-B-0 443 821 bekannt sind. Insbesondere sind es solche, die durch die Formel
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
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.
Als Stabilisatoren oder Stabilisatorgemische für die Isothiazolon-Verbindungen sind die aus dem Stand der Technik bekannten Verbindungen, und insbesondere schwefelhaltige Verbindungen oder Salze derselben geeignet, die mit dem Isothiazolon reversibel ein Adukt bilden können. Insbesondere eignen sich heterocyclische Schwefel-Stickstoff-Verbindungen wie 2-Mercaptopyridin-N-oxid sowie entsprechende Salze, bevorzugt Alkalimetall- oder Ammoniumsalze wie z.B. Pyrion-Na (40%ige wäßrige Lösung von 2-Mercaptorpyridin-N-oxid-natrium-Salz), 2-Mercaptopyridin-N-oxid-Metallsalz-Komplexe wie Zink-Pyrithion (z.B. als 48%ige wäßrige Dispersion), 2,2'-Dithiobis(pyridin-N-oxid) (Pyriondisulfid), 2-Mercaptobenzothiazol, 2-(Thiocyanatomethyl)-thio-benzothiazol (TCMTB) sowie Mischungen derselben. Insbesondere sind Pyrion-Na, Zinkpyrithion, Pyriondisulfid und 2-Mercaptobenzothiazol bevorzugt. Darüber hinaus sind erfindungsgemäß auch milde Oxidationsmittel wie Jodpropinylbutylcarbamat, Wasserstoffperoxid, t-Butylhydroperoxid, Natriumbromat und Cu-(II)-Salze als Stabilisatoren oder Co-Stabilisatoren geeignet, wobei Natriumbromat, Wasserstoffperoxid, 2-tert.-Butyl-6-methylphenol und Pyriondisulfidals Co-Stabilisatoren bevorzugt sind.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.
Besonders geeignet sind Zubereitungen, die folgende Komponenten umfassen:
- 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.
- 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.
Demgemäß kann der Isothiazolon-Gehalt in der Additiv-Mischung 2,25 bis 20,25 Gew.-%, beispielsweise 6,75 bis 20,25 Gew.-%, vorzugsweise 9 bis 13,5 Gew.-% und insbesondere etwa 11 Gew.-% betragen.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.
Der Stabilisatorgehalt in der Additivmischung kann etwa 1,3 bis 10 Gew.-%, beispielsweise 4 bis 10 Gew.-%, vorzugsweise 6 bis 8 Gew.-% und insbesondere etwa 7 Gew.-% betragen, wobei beispielsweise auch 0,05 bis 1,0 vorzugsweise 0.5 bis 0,1 Gew.%, insbesondere 0,2 Gew.-% Co-Katalysator vorhanden sein können.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.
Das Molverhältnis Isothiazolon-Verbindung:Stabilisator ist beispielsweise mindestens 10:1, vorzugsweise zwischen 1,5:1 und 1:1,5 und insbesondere etwa 1:1, wie zwischen 1,1:1 und 1:1,27.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.
Die Additiv-Mischungen werden vorzugsweise in handelsübliche Kühlschmiermittelkonzentrate eingearbeitet, aus denen dann Verdünnungen mit Wasser angesetzt werden, z.B. 4%ige Verdünnungen.The additive mixtures are preferably incorporated into commercially available coolant concentrates, from which dilutions with water are then made, e.g. 4% dilutions.
Die flüssigen Zubereitungen können gegebenenfalls weitere Additive enthalten, die die funktionellen Eigenschaften des Kühlschmiermittels oder Kühlschmiermitteladditivs unterstützen.The liquid preparations can optionally contain further additives which support the functional properties of the cooling lubricant or cooling lubricant additive.
Erfindungsgemäß liegen der Wirkstoff (Isothiazolon) und der Stabilisator (zum Beispiel Pyrion-Na) als flüssige, stabile Zubereitung in einem Ein-Komponenten-System vor. Die Zubereitung ist gut dosierbar und auch unter Praxisbedingungen lagerfähig und haltbar. Vorteilhaft ist auch die gute Handhabbarkeit der Zubereitung, verglichen mit der Lagerung, Vorbereitung und Zudosierung von in Zwei-Komponenten-Systemen vorliegenden Wirkstoffen und Stabilisatoren.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.
Die erfindungsgemäßen Additivmischungen können Kühlschmiermittel-Konzentraten wirkungsvoll zugesetzt werden, so daß deren Haltbarkeit und die Standzeit der fertigen Kühlschmiermittelprodukte, im Vergleich zu bekannten Systemen verbessert wird. Die erhöhte Stabilität der erfindungsgemäßen Zubereitungen zeigt sich insbesondere in der geringeren Neigung zur Bildung von Bodensätzen.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.
Überraschenderweise wurde dabei gefunden, daß die erfindungsgemäße Kombination von Isothiazolon, Stabilisator und speziellem Lösungsvermittler nicht nur die Handhabbarkeit und Dosierung des Mittels erleichert, es verbessert zusätzlich die Stabilität und insbesondere die Wirksamkeit der Biozidmischung.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.
Der erzielte synergistische Effekt bei der Verwendung einer erfindungsgemäßen Additivmischung in Kühlschmiermittelprodukten wird durch die nachfolgenden Beispiele verdeutlicht.The synergistic effect achieved when using an additive mixture according to the invention in cooling lubricant products is illustrated by the examples below.
In den folgenden Beispielen bezeichnet Kathon RH 893 eine 45%ige n-Octylisothiazolon-Lösung in 1,2-Propylenglykol und Pyrion-Na eine 40%ige wäßrige 2-Mercaptopyridin-N-oxid-Natriumsalz-Lösung.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.
In einer Versuchsreihe wurde die Stabilität von Kathon RH 893 in einem Kühlschmiermittel (Shell Dromus B) ohne und mit Stabilisator-Zusatz über eine Wirkstoffbestimmung verfolgt. Dazu wurden 0,28% Kathon 893 (entsprechen 0,1275 % N-Octylisothiazolon, NOITZ) sowie Stabilisatoren in unterschiedlichen Mol-Verhältnissen in 60 g Shell Dromus B eingearbeitet. Aus diesen Konzentraten wurden jeweils kurz vor der HPLC-Bestimmung des Isothiazolon-Gehaltes 5%ige Emulsionen mit vollentsalztem (VE-)Wasser angesetzt. Die Konzentrate wurden bei Raumtemperatur bzw. 40°C im Klarglas gelagert.
Dieser Versuch zeigt, daß durch Zusatz der Stabilisatoren eine beachtliche Stabilisierung des NOITZ in Kühlschmiermittelkonzentraten erreicht wird. Dieser Versuch zeigt aber auch, daß der Zusatz von Na-Pyrion oder Pyriondisulfid zu tiefen Verfärbungen der Lösungen und Trübungen oder Bodensätzen führt.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.
Die Verträglichkeit und Stabilität von Zubereitungen auf Basis von 2 Teilen Kathon 893 und 0,5 bis 4,0 Teilen Pyrion-Na (40%ig), in 0,5%-Konzentrationsstufen, ohne Zusatz weiterer Lösungsvermittler wurde nach Lagerung in Klarglas bei Raumtemperatur geprüft. Die zunächst klaren, gelben Lösungen (Nullwert bzw. nach 18 Tagen) waren nach 3 Monaten zum Teil zweiphasig bzw. wiesen geringe Ausfällungen auf.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.
Zubereitungen auf Basis von Kathon 893 und Pyrion-Na im Mol-Verhältnis 1 : 1 bis 1 : 5 (ohne Zusatz weiterer Lösungsvermittler) waren nach fünfmonatiger Lagerung bei Raumtemperatur inhomogen. Tendenziell nahm die Stabilität mit zunehmendem Pyrion-Na-Gehalt eher ab.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.
Die Verträglichkeit und Stabilität von Zubereitungen auf Basis von 40 Teilen Kathon 893 und 40 Teilen Pyrion-Na (40 %) in diversen Lösungsvermittlern wurde in Klarglas bei Raumtemperatur geprüft (Mol-Verhältnis N-Octylisothiazolon : 2-Mercaptopyridin-N-oxid-Na = 1 : 1,27). Die zunächst klaren, homogenen gelben bis orange-gelben Lösungen (Nullwerte) neigten zeitabhängig zur Bildung von (gelben) Niederschlägen. Mit Hexylenglykol, Dipropylenglykol, 1,2-Propylenglykol und Phenoxyethanol traten nach 6 Monaten Bodensätze auf, etwas weniger mit Butyldiglykol und 1-Methoxypropanol-2 und praktisch keine mit Phenoxypropanol. Die Lösungen wiesen keinen unangenehmen Schwefel-Geruch auf und waren praktisch unverändert gelb-orange gefärbt.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.
Die Verträglichkeit und Stabilität von Zubereitungen auf Basis von 35 Teilen Kathon 893 und 25 Teilen Pyrion-Na (40%) in diversen Lösungsvermittlern wurde in Klarglas bei Raumtemperatur geprüft (Mol-Verhältnis N-Octylisothiazolon : 2-Mercaptopyridin-N-oxid-Na = 1 : 0,9). Die zunächst klaren, homogenen gelben bis gelb-roten Lösungen (Nullwerte) neigten zeitabhängig zur Bildung von (gelben) Niederschlägen und verfärbten sich je nach Lösungsmittel unterschiedlich stark. Die Neigung zur Bildung von Bodensätzen war geringer als in der Versuchsreihe mit einem N-Octylisothiazolon/2-Mercaptopyridin-Na-oxid-Na-Verhältnis von 1 : 1,27. Besonders intensiv dunkel gefärbt war die Zubereitung mit Butyldiglykol, etwas weniger dunkel gefärbt waren Muster mit Hexylenglykol bzw. Dipropylenglykol, nur schwach orange-gelb gefärbt waren Muster mit 1-Methoxypropanol-2 und 1,2-Propylenglykol, während Zubereitungen mit Phenoxyethanol bzw. Phenoxypropanol praktisch unverändert gelb gefärbt waren. Mit Hexylenglykol und Phenoxypropanol treten nach 6 Monaten bei Raumtemperatur nur geringe Niederschläge auf, Lösungen mit Phenoxyethanol waren praktisch niederschlagsfrei. Die Lösungen wiesen keinen unangenehmen Schwefel-Geruch auf.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.
Formulierungen auf der Basis Kathon 893 und Pyrion-Na (40 %) wurden im Mol-Verhältnis 1 : 1 bis 1 : 5 in verschiedenen Lösungsvermittlern gelöst und auf Verträglichkeit und Stabilität untersucht. Der Gesamt-Wirkstoffgehalt (Summe aus N-Octylisothiazolon und 2-Mercaptopyridin-N-oxid-Na-Salz) betrug ca. 18 %.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%.
Nach 6 Monaten Lagerung bei Raumtemperatur in Klarglas wurden folgende Ergebnisse erhalten:After 6 months of storage at room temperature in clear glass, the following results were obtained:
Mit zunehmendem Kathon 893-Gehalt verfärbten sich die zunächst klaren, gelben Lösungen etwas dunkler bzw. tief dunkel-rot. Farblich wenig verändert waren Zubereitungen mit den Lösungsvermittlern 1,2-Propylenglykol, Phenoxypropanol und Phenoxyethanol in allen geprüften Mol-Verhältnissen. Etwas dunkler waren Lösungen mit 1-Methoxypropanol-2 und Dipropylenglykol und tief dunkel-rot waren Lösungen mit Hexylenglykol und insbesondere Butyldiglykol.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.
Die Bildung von Niederschlägen und Inhomogenitäten war nicht primär vom Molverhältnis der Wirkstoffe sondern eher vom Lösungsvermittler abhängig. Vergleichsweise wenig Niederschlag trat bei Lösungen mit einem Phenoxyethanol-, Phenoxypropanol- oder 1-Methoxypropanol-2-Gehalt auf.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.
Vergleichsweise voluminöse Bodensätze bildeten sich dagegen in Lösungen mit Butyldiglykol-Gehalt. Mit den übrigen Lösungsvermittlern kam es zum Teil ebenfalls zu Ausfällungen.Comparatively voluminous sediments, on the other hand, were formed in solutions with butyl diglycol. With the other solution brokers, there were also some precipitations.
Die Untersuchungen zeigen, daß die Stabilität und Verträglichkeit von Kathon 893 mit Pyrion-Na zum Teil stark von der Art des Lösungsvermittlers und dem Molverhältnis der Wirkstoffe abhängig ist.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.
In einer Versuchsreihe wurde die Stabilität von Kathon 893 in Kühlschmiermittel-Konzentraten ohne und mit Stabilisator-Zusatz über den Wirkstoffabbau nach Lagerung verfolgt. In dieser Versuchsreihe wurden die Konzentrate bei 40°C in Klarglas gelagert.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.
In die Konzentrate wurden jeweils 0,28% Kathon 893 (entsprechen 0,126% NOITZ) bzw. die Testprodukte:
- 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
- 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
Kühlschmiermittel-Konzentrat: SA 2146 N-octylisothiazolone content after storage:
Coolant concentrate: SA 2146
Kühlschmiermittel-Konzentrat: SA 2146 N-octylisothiazolone content after storage:
Coolant concentrate: SA 2146
Kühlschmiermittel-Konzentrat: Kutwell 40 N-octylisothiazolone content after storage:
Coolant concentrate: Kutwell 40
Die Konzentrate und Emulsionen plus Additive waren optisch praktisch unverändert, auch nach Lagerung. Hinsichtlich des Ausmaßes der Stabilisierung unterschieden sich die Konzentrate aufgrund unterschiedlicher Zusammensetzungen zum Teil deutlich. Die Produkte A bis C unterschieden sich bezüglich der stabilisierenden Wirkung von Isothiazolon - mit Ausnahme von C bei Kühlschmiermittelkonzentrat SA 2146 - nicht signifikant, auch nicht gegenüber einer getrennten Zugabe von Kathon 893 und Pyrion-Na.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.
Ein Boko- und Lager-Boko-Test (10 Tage Lagerung des Kühlschmiermittelkonzentrates bei 40°C) wurde mit den Mustern A, B, C von Beispiel 6 (Zuhereitungen auf der Basis Kathon 893, Pyrion-Na und Lösungsvermittler), den Einzelwirkstoffen sowie einer Kombination der Wirkstoffe NOITZ (eingesetzt wurde Kathon 893) und Na-Pyrion durchgeführt. Die Präparate bzw. Wirkstoffe wurden jeweils in die Konzentrate eingearbeitet, aus denen dann 4%ige Verdünnungen in Norderstedter Stadtwasser angesetzt wurden.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.
Die frisch hergestellten Konzentrate und die 4%igen Verdünnungen zeigten optisch keine Unterschiede zum jeweiligen Blindwert (Kühlschmiermittel ohne Wirkstoff). Nach 10 Tagen Lagerung bei 40°C wiesen die wirkstoffhaltigen Shell Dromus BX-Konzentrate und Verdünnungen optisch ebenfalls keinen Unterschied zum Blindwert auf. Bei den gelagerten Proben trat erwartungsgemäß ein Wirkungsabfall ein, der allerdings für Produkte B und C vergleichsweise gering ausfiel. Bei den ungelagerten Mustern war das Präparat C am wirksamsten bzw. in etwa vergleichbar mit der Wirksamkeit der Kombination Kathon 893 und Pyrion-Na (ohne Lösungsmittel). Bei den gelagerten Mustern zeigte eindeutig C vor B und A die beste Wirkung, welches in etwa vergleichbar mit der Wirksamkeit der Kombination Kathon 893 und Pyrion-Na (ohne Lösungsmittel) war.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 verbesserte die Wirksamkeit von Kathon 893 im Boko-Test. Durch die Kombination dieses Wirkstoffgemisches mit einem erfindungsgemäßen Losungsvermittler (insbesondere Phenoxypropanol bzw. Phenoxyethanol) ließ sich die Wirksamkeit im Boko-Test auch unter praxisnahen Bedingungen (z B. Lagerung bei erhöhter Temperatur, was einer Verlängerung der Lagerung bei Raumtemperatur gleich kommt) aufrechterhalten.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).
Die Kombination: Kathon 893, Pyrion-Na und erfindungsgemäßer Lösungsvermittler erleichterte nicht nur die Handhabbarkeit und Dosierung des Mittels, es verbesserte zusätzlich die Stabilität und die Wirksamkeit der Biozid-Mischung.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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19534532A DE19534532C2 (en) | 1995-09-08 | 1995-09-08 | Additive mixtures for cooling lubricant products and their use |
DE19534532 | 1995-09-08 |
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EP0773281A2 true EP0773281A2 (en) | 1997-05-14 |
EP0773281A3 EP0773281A3 (en) | 1998-05-13 |
EP0773281B1 EP0773281B1 (en) | 2005-10-19 |
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EP96250190A Expired - Lifetime EP0773281B1 (en) | 1995-09-08 | 1996-09-05 | Preparations for production of stabilized coolantiubricants |
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EP (1) | EP0773281B1 (en) |
DE (2) | DE19534532C2 (en) |
ES (1) | ES2247597T3 (en) |
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US6211213B1 (en) * | 1999-04-16 | 2001-04-03 | Rohm And Haas Company | Stable microbicide formulation |
WO2002067685A1 (en) * | 2001-02-26 | 2002-09-06 | Lonza Inc. | Stable preservative formulations comprising halopropynyl compounds and butoxydiglycol solvent |
EP1332675A2 (en) * | 2002-01-31 | 2003-08-06 | Rohm and Haas | Synergistic microbicidal combinations |
US6607738B2 (en) | 1997-04-24 | 2003-08-19 | Nipa Laboratories, Ltd. | Chemical composition |
EP1514473A1 (en) * | 2003-09-04 | 2005-03-16 | Air Liquide Santé (International) | Low-salt or salt-free microbicidal composition based on isothiazolone derivatives and pyrion disulphide |
US9034905B2 (en) | 2003-02-05 | 2015-05-19 | Rohm And Haas Company | Synergistic microbicidal combinations |
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GB2320026B (en) * | 1996-12-05 | 2000-01-26 | Sunkyong Ind Ltd | Stabilized isothiazolone solution |
DE19961621C2 (en) * | 1999-12-13 | 2002-11-14 | Schuelke & Mayr Gmbh | Bactericidal and fungicidal liquid preparations for technical products |
DE102004052878A1 (en) | 2004-11-02 | 2006-05-04 | Schülke & Mayr GmbH | Isothiazolone-containing preservatives with improved stability |
DE102006045066B4 (en) * | 2006-09-21 | 2010-07-01 | Schülke & Mayr GmbH | Microbicidal preparation based on 1,2-benzisothiazolin-3-one with an aromatic alcohol content |
DE102009048189A1 (en) | 2009-10-02 | 2011-04-07 | Schülke & Mayr GmbH | Storage-stable microbicidal concentrates and their use as preservatives |
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Also Published As
Publication number | Publication date |
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ES2247597T3 (en) | 2006-03-01 |
DE59611282D1 (en) | 2006-03-02 |
DE19534532C2 (en) | 1999-04-08 |
DE19534532A1 (en) | 1997-03-20 |
EP0773281A3 (en) | 1998-05-13 |
EP0773281B1 (en) | 2005-10-19 |
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