DE19847498A1 - Detergents and their use - Google Patents

Abstract

Detergent comprises (a) 0.1-30 wt.% ether-carboxylate(s) (I), (b) 0.1-40 wt.% alk(en)yl- or phenyl-ethoxylate terminated with alk(en)yl or phenyl glyceryl ether (II) and (c) 0.01-20 wt.% N-alkylpyrrolidone(s) (III), with an (un)saturated, linear or branched 6-18 C alkyl group, in aqueous solution. Detergent comprises (a) 0.1-30 wt.% ether-carboxylate(s) of formula (I), (b) 0.1-40 wt.% alk(en)yl- or phenyl-ethoxylate terminated with alk(en)yl or phenyl glyceryl ether of formula (II) and (c) 0.01-20 wt.% N-alkylpyrrolidone(s) (III), with an (un)saturated, linear or branched 6-18 carbon (C) alkyl group, in aqueous solution; R<1)<O-CH2-CH2-)k-OCH2COOM (I) R<2)<O-CH2-CH2-)m-CH2-CH(OH)-CH2-RO<3> (II) k = 0-12; m = 1-40; R<1> = (un)saturated, linear or branched 4-18 C alkyl or 10-18 C phenylalkyl; M = a mono-, di- or trivalent metal cation and/or a proton (H<+>); R<2>, R<3> = (un)saturated, linear or branched 3-18 C alkyl or 10-18 C phenylalkyl. An Independent claim is also included for application solutions of the detergent in aqueous or aqueous-alcoholic solution.

Description

The invention relates to compositions comprising ether carboxylates, nonio African surfactants and N-alkylpyrrolidones and other auxiliaries. The together Settlements are characterized by a particular low foam level and at the same time lower Surface tension and high cleaning activity. The composition gen do not contain cumene sulfonate as a solubilizer and can be used if necessary can also be formulated without solvents. The agents according to the invention become mechanical and manual cleaning of hard surfaces, especially of medical devices, surgical instruments, rigid and flexible Endoscopes, inventory and other inanimate surfaces are used.

State of the art

Surgical instruments are increasingly being machined today prepared special cleaning and disinfection machines. A key The cleaning and disinfectants used play a role in this. taking into account the procedure, meeting specific requirements have to. The cleaning step is particularly sensitive because it is residue-free Cleaning blood, secretion and protein contaminants prevents incrustation residual contamination from the subsequent thermal or ther mixed chemical disinfection step. How difficult a mechanical return Steady cleaning is actually done mostly on microsurgical Instruments and flexible endoscopes clearly, which is a complicated system of sometimes extremely narrow channels, branches and bulky cavities form. On the other hand, the use of sensitive materials, e.g. B. complicated optics, special adhesives, light guides, more sensitive to corrosion Metals and highly elastic plastics a particularly gentle treatment, the functionality of the sometimes very expensive devices even after many Processing cycles not to be affected.  

Since high turbulence occurs in automatic cleaning processes the cleaning agents used have special requirements with regard to the Foam behavior posed.

Alkaline cleaners attempt this task by adding active chlorine or to meet active oxygen compounds, which also without the Zu set of surfactants can solve protein soiling from surfaces. The disadvantage here is the high pH and the associated poor quality Material compatibility, especially compared to anodized aluminum, but also Nonferrous metals or special alloys. Therefore, in recent times, have increased mildly alkaline and pH neutral cleaners are suggested based on low-foam non-ionic and / or anionic surfactants are built up and Support of the cleaning effect ent proteolytic enzymes can hold.

So that the enzymes work even in hard-to-reach places the tensioactivity of such cleaning agents is particularly important Criteria.

EP-A-0 268 227 describes a cleaning agent which contains at least one non-ionic low-foaming surfactant, complexing agents, proteolytic enzymes see above how to contain other detergent ingredients. As nonionic surfactants who the adducts of ethylene oxide and optionally propylene oxide saturated fatty alcohols claimed in which the terminal hydroxyl groups can be etherified, esterified or acetalized with an aliphatic alcohol.

Comparable cleaning agents on this basis make themselves low Use the cloud point of the surfactants used. Such a detergent Solution is usually clear at lower temperatures to warm up tarnish. This partial separation from the aqueous phase means that Surfactants mostly at temperatures above 25-30 ° C as foam inhibitors, see above that even mechanical cleaning processes with high turbulence without problems can be carried out. At the same time, there are also several pros  cream to day. On the one hand, the aqueous phase is surface in this way Chenactive substance withdrawn, so that especially at higher temperatures 45 ° C increased wetting problems occur on the surfaces to be cleaned can and the cleaning effect of such a solution on the mechanical The strength of the solution remains limited. Provided the temperature of the cleaning solution but is still below the cloud point, can be in washing and disinfecting automatic foaming occur, which in the case of cleaning from flexible endoscopes to automatic system shutdown and thus an interruption of the cleaning process due to pressure loss Can cause foaming.

Such a problem can always occur when the water supply to the Cleaning machines are carried out over cold softened tap water, the Reini detergent is added immediately after the softening phase and then the cleaning program begins. For this reason the marketable cleaning and disinfection machines via a program option in which the inlet water is preheated to temperatures of up to 35 ° C and only then the detergent is added. At the same time it is known that in particular blood contamination preferably with cleaning solutions from lower temperatures are to be eliminated while at higher temperatures the onset of denaturation or the progressive blood coagulation effective cleaning can complicate.

One solution to the problem would be to use non-ionic low-foam surfactants use with a particularly low cloud point, so that in extreme cases a water inlet temperature of 10 ° C still a foam-free job by Reini solution is made possible. A whole range of Reini on the market Means for mechanical instrument reprocessing are on this Para meter optimized. However, here too there are serious disadvantages Days. The thermal stability of such mixtures often leaves something to be desired, sometimes a gradual segregation occurs even at temperatures from 35 ° C the wording.  

The storage stability of cleaning agents even at higher temperatures ensure, or their homogeneity in the formulation guarantee, sometimes have to put a lot of effort into the manufacture of such products quantities of special solubilizers or assembly aids, for example Cumene sulfonate or xylene sulfonate can be used. Because the solution broker apart from clarifying the wording, there are no other tasks the benefit of using such solubilizers is rather small if one is thinks that the wastewater is additionally polluted.

DE-A-196 07 530 describes a cleaner which, in addition to enzymes, complexing agents and other conventional constituents, contains an anionic surfactant of the short-chain C ₅ -C ₁₀ alkyl sulfate salt type as a surfactant base. It is known that anionic surfactants have a good cleaning-supporting effect, surfactants with hydrophobic residues from 10 carbon atoms tend to form a lot of foam. If, as described in DE-A-196 07 530, surfactants with short-chain branched hydrophobic radicals are used, it is possible to produce formulations whose dilute solutions are characterized by a constant low foam formation in the entire temperature range, but in their wetting ability and cleaning activity leave much to be desired.

An attempt was therefore made to develop a cleaning agent which can be found in all Temperature ranges only a constant little or none at all Should develop foam. The foam behavior should also be in the presence of protein remain consistently low. On the use of biologically difficult or not degradable foam damper, such as B. EO-PO block polymers, silicone derivatives and Paraffin oil should be avoided if possible, as well as the addition of solubilizers of the cumene sulfonate or xylene sulfonate type. At the same time, the agent should also be used at temperatures above 40 ° C maintain its storage stability. Essential for the agent should be a pronounced good wetting and cleaning ability, especially against blood and protein soiling, even in places that are particularly difficult to access. Here the surfactant base should have good biodegradability and should be used for ver  Improved wetting ability no biologically hard fluorosurfactants are used come. In addition, the agent and its working solutions should preferably pH be neutral to slightly acidic to ensure optimal tolerance of the product and its solution compared to the usual flexible ones used in medicine Ensure plastic materials and metallic materials.

When solving the problem, it was assumed that the means in addition to the possible use of enzymes preferably based on anionic tensio active ingredients should be built to achieve an optimal cleaning effect achieve.

The class of alkyl polyglycol ether carboxylates is known for its good Cleanability with a relatively low to moderate tendency to foam. Com These products are commercially available from KAO Corporation at Collective name Akypo® LF. First attempts at formulation with However, octyl ether carboxylates showed that those made therefrom Cleaning solutions tended to foam too much. Try the foam by using a blend with the particularly short-chain butyl ether carboxylate curb did not bring the hoped-for success, since the foam is now disintegrated faster, but the initial foam height at time 0 was almost unchanged stayed. Therefore, further attempts were made to check the foaming behavior by means of additives of alkyl polyalkylene glycol ethers or of terminal with alkyl radicals to minimize sealed fatty alcohol EO / PO adducts. The result showed that clear formulations were obtained either at room temperature, whose application solutions foamed strongly or weakly foaming Application solutions for formulations unstable at room temperature could be traced back only through substantial additions Cumene sulfonate or solvent, e.g. B. ethylene glycol monomethyl ether with respect their storage behavior had to be stabilized.

Surprisingly, it has now been found that low-foam, storage-stable formulation Manufacture solutions that meet the requirements mentioned at the beginning if the mixtures contain at least one ether carboxylate, at least one  contain nonionic surfactant and at least one N-alkylpyrrolidone. This too composition can be present as a concentrate, which is in aqueous or aq rig-alcoholic solution can be used (application solution).

Accordingly, the present invention relates to a detergent comprising in aqueous solution as a concentrate

• (a) 0.1-30% by weight of at least one ether carboxylate of the formula I.
  R ¹ (O-CH ₂ -CH ₂ ) _k -OCH ₂ COOM k = 0-12
• (b) 0.1-40% by weight of at least one nonionic surfactant of the formula II
  
• (c) 0.01-20% of at least one N-alkyl pyrrolidone

wherein
R ¹

a saturated or unsaturated, linear or branched alkyl radical with 4-18 carbon atoms or a phenylalkyl radical with 10-18 carbon atoms,
M is a monovalent, divalent, trivalent metal cation and / or a proton (H ⁺

),
R ²

and R ³

each represent a saturated or unsaturated, linear or branched alkyl radical having 3-18 carbon atoms or a phenylalkyl radical having 10-18 carbon atoms, which may have saturated or unsaturated, linear or branched alkyl radicals of alkylpyrrolidone between 6 and 18 carbon atoms
and the weight percentages are based on the total amount of the aqueous solution.

The composition according to the invention is in a special embodiment free of difficult or non-degradable foam dampers, such as EO PO block polymers, silicone derivatives and / or paraffin oil and solubilizer learn how especially cumene or xylene sulfonates.

The ether carboxylates of the formula I are in the cleaning according to the invention medium preferably in a total concentration of 0.1-10 wt .-%, especially preferably in a concentration of 0.1-7% by weight, based on the total amount of concentrate included.

The mono-, di- and trivalent metal ions can be, for example Act alkali and / or alkaline earth metal ions.

The alkyl radical R ¹ preferably contains 4-13, particularly preferably 4-10 carbon atoms. K preferably takes an integer between 0 and 9, particularly preferably between 5 and 9.

A preferred ether carboxylate is sodium C ₈ alkyl ether carboxylate (6 EO) (sodium capryleth (6) carboxylate).

The nonionic surfactants of formula II are in the agent according to the invention preferably in a concentration of 0.1-30% by weight, particularly preferably in a concentration of 0.1-15 wt .-%, based on the total amount of Concentrate. M preferably takes an integer between 3 and 20 on.

The particularly preferred nonionic surfactants are one Octyl ethoxylate with 6-10 EO, terminally sealed with an octyl glyceryl ether such as e.g. B. from HACOBA AG (Basel) under the trade name TN 55 ether surfactant is offered.

The N-alkylpyrrolidones in the agent according to the invention are preferably in a concentration of 0.01-15% by weight, particularly preferably in a concentration  tration of 0.01-5 wt .-%, based on the total amount of the concentrate ent hold. N-Octylpyrrolidone, N-Decylpyrrolidone and are particularly preferred N-lauryl pyrrolidone.

In a preferred embodiment, the aqueous solution comprises a total of we at least 1.0% by weight of components (a), (b) and (c), based on the Total amount of solution.

The 100% by weight missing part can be replaced by the optio nal components and water can be added.

So the cleaning agent can additionally 0.1-30 wt .-%, preferably 0.5-20 Wt .-% contain complexing agents and water hardness stabilizers, with salts organic acids, e.g. B. salts of citric acid, gluconic acid, nitrilotriacetic acid acid, EDTA, aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, Phosphonobutane tricarboxylic acid, but also polymers, e.g. B. polyacrylates, polycar boxylates, maleic acid / acrylic acid copolymers or mixtures thereof for Can come into play.

Furthermore, the agent can contain up to 20% by weight, preferably 1 to 20% by weight. contain proteolytic enzymes in the form of their commercially available solutions, wherein the agent according to the invention, if it contains enzymes, for enzyme stabilization tion up to 50 wt .-% monohydric and / or polyhydric alcohols with 2-6 Koh lenstoffatomen and 1-6 hydroxyl groups can be added. Prefers are polyhydric alcohols, especially propylene glycol, glycerin, sorbitol as well as mixtures of these alcohols.

In addition, the agent according to the invention can inhibit corrosion by up to 5% by weight gates, preservatives, dyes and odor corrections.

Furthermore, the agent according to the invention can still contain up to 20% by weight, preferably 0.1 to 5 wt .-% of other nonionic surfactants that do not fall under the Formula II fall and which are selected from the group of alkyl alkoxylates,  Alkylphenol alkoxylates, alkyl polyglucosides, alkyldimethylamine oxides, alkyl fat acid amides and amide ether carboxylates, the terminal hydroxyl groups the alkyl alkoxylates and alkylphenol alkoxylates can also be etherified. The The alkyl group has the usual range of 6 for such surfactants up to 18 carbon atoms.

In addition, the agent according to the invention can additionally contain up to 20% by weight, preferably 0.01 to 7% by weight, of further anionic and / or amphoteric surfactants which are selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl ether sulfates and alkyl -C ₆ -C ₁₈ -arylsulfonates, alkylbetaines, alkyliminodipropionates, alkylamidopropylbetaines, the essential requirement being that the foam behavior of the agent according to the invention and of the application solution is not impaired by the additives. The alkyl group in each case has the range from 6 to 18, preferably 6 to 12, carbon atoms customary for such surfactants.

It may be desirable in certain cases for technical reasons be worth the agent according to the invention up to 10 wt .-%, preferably up to 6% by weight of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or their To add mixtures, the saturated linear or branched alkyl radical 1- Has 6 carbon atoms.

The pH of the agent is preferably between 4.0 and 13.0 between 4.0 and 9.0 and preferred in the case of an enzyme-containing version Values set between 4.0 and 8.5. The pH is regulated expediently with sodium hydroxide, potassium hydroxide and / or organic alkanolamines, e.g. B. triethanolamine or triisopropanolamine or with the organic acids described above.

The cleaning agent can be used as the concentrate or used as an aqueous or aqueous / alcoholic solution (application solution)  become. An Al. Is preferably used in the aqueous / alcoholic application solution alcohol used with two or three carbon atoms.

The application solutions contain the cleaning agent (concentrate) in one Proportion from 0.1 to 10% by volume, preferably from 0.1 to 2% by volume.

The cleaning agents and application solutions according to the invention can be used for Cleaning inanimate surfaces, especially medical ones Equipment, surgical instruments, anesthetic materials, rigid and flexible endoscopes are used. They are particularly suitable Cleaning agents according to the invention and application solutions for cleaning of surgical instruments, rigid and flexible endoscopes in Reini automatic and disinfection machines. Here, after the cleaning step thermal or chemical-thermal disinfection with the usual for this Disinfectants can be used. The invention Cleaning agents and the application solutions can also be used without any problems Cleaning of other inanimate surfaces can be used, such as especially for cleaning bed frames, floors and inventory as well as for Bedpan cleaning.

The present invention is illustrated by the following examples wrote without being limited to this.

Examples

In the following examples, unless otherwise stated, Ge important parts for the description of the composition, which is% by weight corresponds.

The surface tension was determined in a process known to the person skilled in the art using a commercially available tensiometer from Krüss determined a platinum-iridium ring, the sample vessel was thermostated.  

The foam values were determined in a swivel foam test. This was done in 50 ml of solution are placed in a 100 ml measuring cylinder, thermostated, 30 times Rotated 180 ° C and then immediately read the foam volume in ml.

Two recipes were made. Recipe 1 was formulated without enzymes, while recipe 2 contains enzymes.

The pH of the formulations according to the invention was in each case with sodium hydroxide solution and citric acid set to 6.0. In addition, the Re recipes each with 0.1% methyl paraben to protect them against microbial To protect spoilage.

In order to make a well-founded statement about the basic suitability of the formulations according to the invention for the intended areas of use, a number of physicochemical parameters were determined, the following exemplary selection of the commercially available cleaning agents being used for comparison purposes:

Unless otherwise stated, the tests were performed with the 0.5% Ge usage solutions carried out.

The results obtained are listed in Table 1 below:

Table 1

It can be seen from the values that recipes 1 and 2 according to the invention have a significantly higher cloud point than the commercial products A and B. This statement is not insignificant when you consider that in the warmer climates may reach temperatures of 40 ° C and higher can be. In contrast, commercial product C has due to its Zu  composition, as expected, no cloud point. As soon as the tempera The application solutions shows a temperature of 10 ° C and lower edge increase in the initial foam height in the case of commercial products A and B, wuh rend in the case of recipes 1 and 2 according to the invention and the commercial pro product C the foam height remains unchanged.

The disadvantages of the commercial product C come to light under albumin pollution uses an unusually strong foam formation. This behavior suggests conclude that purely anionic formulations are not unrestricted for the ma rapid instrument reprocessing, especially for the automatic cleaning of Channels of flexible endoscopes are suitable because the detached protein-containing Soiling would itself act as a foam booster. In contrast formulations 1 and 2 according to the invention show a balanced low Foaming.

The cleaning activity of the formulations according to the invention was determined using a plausible experimental model. For this purpose, stainless steel screws were used contaminated sheep blood, dried for 1 hour at 30 ° C and on closing always 3 contaminated screws in one with 200 ml each 0.5% detergent solution.

During the exposure times, the cleaning solutions were each with the same Ge agitation in order to achieve a defined turbulence, but without removing the contamination mechanically. As ver same medium, water with a set hardness of 5 ° dH was used, The respective cleaning solutions were also produced with this water quality poses. After the exposure time, the cleaned screws were removed. The Cleaning effect was visualized based on the rest of the screws pollution determined and subjected to an evaluation system. The grade 1 stands for "complete cleaning success" while the grade 5 "no cleaning effect "means. The experiments were repeated three times. The results (Mean values) are shown in Table 2.  

Table 2

In summary, it can be stated that the inventive Recipes through a constant low temperature independent Foam formation with a particularly low surface tension, high turbidity training point and a particularly good cleaning ability. In Further tests were carried out to ensure good material compatibility with instruments steel, anodized aluminum, copper, brass and flexible materials such as Neoprene, soft PVC, polyethylene, rubber, silicone elastomers and latex determined. Tests for the mechanical processing of commercially available Gastroscopes in various cleaning and disinfection machines confirm the advantageous suitability of the agents according to the invention for the described application.

The good compatibility of an embodiment of the Agent according to the invention over acrylic glass, the acrylic glass in several cleaning cycles at a temperature of 60 ° C.

Claims (18)

1. Detergent, comprising in aqueous solution

• a) 0.1-30% by weight of at least one ether carboxylate of the formula I.
  R ¹ (O-CH ₂ -CH ₂ ) _k -OCH ₂ COOM k = 0-12
• b) 0.1-40% by weight of at least one nonionic surfactant of the formula II
  
• c) 0.01-20% of at least one N-alkylpyrrolidone

wherein
R ^{1 is} a saturated or unsaturated, linear or branched alkyl radical having 4-18 carbon atoms or a phenylalkyl radical having 10-18 carbon atoms,
M is a monovalent, divalent, trivalent metal cation and / or a proton (H ⁺ ),
R ² and R ³ each represent a saturated or unsaturated, linear or branched alkyl radical having 3-18 carbon atoms or a phenylalkyl radical having 10-18 carbon atoms, which may have saturated or unsaturated, linear or branched alkyl radicals of alkylpyrrolidone between 6 and 18 carbon atoms
and the weight percentages are based on the total amount of the aqueous solution. 2. Cleaning agent according to claim 1, characterized in that the aqueous solution in total at least 1% by weight of components (a), (b) and (c).   3. Cleaning agent according to claim 1 or 2, characterized in that it additionally 0.1-30% by weight of complexing agents and water hardness stabilizers contains. 4. Cleaning agent according to one or more of claims 1-3, characterized characterized in that it is additionally up to 20 wt .-% proteolytic Contains enzymes. 5. Cleaning agent according to one or more of claims 1-4, characterized characterized in that it is additionally up to in an enzyme-containing version 50% by weight of monohydric and / or polyhydric alcohols with 2-6 carbons contains atoms and 1-6 hydroxyl groups. 6. Cleaning agent according to one or more of claims 1-5, characterized characterized in that it additionally contains up to 5% by weight of corrosion inhibitors, Contains preservatives, odor correctors and dyes. 7. Cleaning agent according to one or more of claims 1-6, characterized characterized in that it additionally contains up to 30% by weight of nonionic ten contains side, not from the group defined by formula II are choosing. 8. Cleaning agent according to one or more of claims 1-7, characterized characterized in that it is additionally up to 20 wt .-% anionic and / or contains amphoteric surfactants. 9. Cleaning agent according to one or more of claims 1-8, characterized characterized in that it is additionally up to in an enzyme-containing version 10% by weight of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether or their Contains mixtures, the saturated linear or branched alkyl radical Has 1-6 carbon atoms.   10. Cleaning agent according to one or more of claims 1-9, characterized characterized in that it has a pH of 4.0-13.0, in the case of an en zym containing version has a pH of 4.0-8.5. 11. Application solution comprising the detergent as in any of claims 1-10 defined in aqueous or aqueous / alcoholic Lö solution. 12. Application solution according to claim 11, characterized in that in the aqueous / alcoholic solution is a monohydric alcohol with two or three Carbon atoms is used. 13. Application solution according to claim 11 or 12, characterized in that that the detergent according to any one of claims 1-10 in has a proportion of 0.1-10% by volume. 14. Use of the cleaning agent according to any one of claims 1- 10 and the application solution according to any of claims 11-13 for cleaning medical devices, surgical instruments, Anesthesia materials, rigid and flexible endoscopes. 15. Use according to claim 14 for cleaning surgical instru mentarium, rigid and flexible endoscopes in cleaning and desin automatic cutters. 16. Use according to claim 15 for cleaning surgical instru mentarium, rigid and flexible endoscopes in cleaning and disinfection tion automat, whereby after the cleaning step a thermal or chemical-thermal disinfection with the usual for these purposes settable disinfectants can take place. 17. Use according to any one of claims 14 to 16 in an application temperature between 5 ° C and 95 ° C.   18. Use of the cleaning agent according to any one of claims 1- 10 and its ready-to-use application solution according to the claims Chen 11-13 for cleaning bed frames, floors, inventory and white other inanimate surfaces.