CA2121340C - Compositions and uses thereof - Google Patents
Compositions and uses thereofInfo
- Publication number
- CA2121340C CA2121340C CA002121340A CA2121340A CA2121340C CA 2121340 C CA2121340 C CA 2121340C CA 002121340 A CA002121340 A CA 002121340A CA 2121340 A CA2121340 A CA 2121340A CA 2121340 C CA2121340 C CA 2121340C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- stabilizer
- aqueous solution
- peracid
- pack system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
- A61L2/186—Peroxide solutions
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/10—Apparatus features
- A61L2202/18—Aseptic storing means
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/20—Targets to be treated
- A61L2202/24—Medical instruments, e.g. endoscopes, catheters, sharps
Abstract
An aqueous composition comprising a lower aliphatic peracid, a corrosion inhibit or and a peroxide stabilizer and/or peracid stabilizer is useful for disinfecting medical equipment, particularly me tal components of such equipment.
Description
WO 93/07909 21 213 ~ O PCr/GB92/01830 Compositlons and uses thereof This invention concerns compositions, processes for the preparation of such compositions, ~wo-pack systems for preparing such con positions and S uses of such compositions. More particularly the present inven~ion concerns compositions comprising dilute aqueous solutions o~ lower aliphatic peracids and their us~ as disinfectant compositions.
The lower aliphatic peracids are effective wide-spectrum bac~ericides which have the particular advantage, in use, of leaving as residues only the 20 corr~sponding lower aliphatic acids and ther~fore being particularly suitablefor applicatiQns which require a non-environm~n~ally-polluting disinfectant.
While the lower aliphatic peracids in general are contemplated herein, for example those corresponding to carboxylic aliphatic acids containing 2 to 9 carbsn atoms, peracetic acid is particularly envisaged since it is already a 2s commercially important peracid for disinfectant purposes. Where the following description relates to peracetic acid it is to be understood that the other peracids may be read in substitution therefor provided that the technical context allows it.
Aqueous solutions of peracetic acid containing up to about 45% by 30 weight of peracetic acid are commercially available. Such solutions may be produced by reacting appropriately concentrat~d hydrogen peroxide and acetic acid in an a~ueous medium in the presence of an acid catalyst which is usually sulphuric acid or other strong min~ral acid. The acid catalyst may be present in from about 0.1% to 3bout 5% by weight of the reaction 3s mixture.
Aqueous solutions of peracetic acid represent equilibrium mixtures of the reactants and the reaction products and, under relatively forcing reaction conditions, for example when using one or rnore of a substantial 4uantity of WO 93/07909 PCI'/~B92/01830 :~
21213'10 2 '.
catalyst, an elevated reaction temperature and a concen~rated reaction mixture, equilibrium may be substantialiy reached in a relatively short time.
When using the strong acid catalyst in from 2% to 5% of the reaction mixture, a temperature of from 30~C to 50~C and a concentration of acid s above about 20% by weight the reaction mixture may come to equilibrium within hours. For some applications. or where long storage is envisaged, it -~;
may not be desirable for there to be catalyst residues in a peracid product particularly, for example, dilute products intended for personal or domestic hygiene use. For many applications dilute solutions of peracetic acid, for lO example below 5% by weight but often below 2%, for example from 0.1%
to 2% by weight, are required. Concentrations of peracetic acid above 0.5% by weight for example from 0.5% to 1% by weight, are particularly effective bactericidally in, for example, toilet cleansing applications. Such dilute peracetic acid solutions may be produced directly by reacting acetic 5 acid and hydrogen peroxide in a suitably diiute reaction medium but equilibrium can take an extremely long time to reach, particularly at the more extreme dilutions envisaged. At peracid concentrations below 1% by weight equilibrium may take a month or more to reach if the rsaction is not acid catalysed or a week or more even if the reaction is acid catalysed. This 20 entails a very heavy utilisation of plant and equipment on a large production scale.
If a concentrated equilibrium solution of peracetic acid is diluted with water the equilibrium point of the system is progressively altered, as dilution progresses, in favour of the regeneration of the original reactants. The 25 ageing time taken to attain the new equilibrium point, after dilution, is of a similar order to that required to produce such a dilute solution directly from suitable reactants. Such a diluted soiution may be used directly although it is not at equilibrium and is therefore of variable composition in storage.
Such non-equilibrium diluted solutions also have a composition dictated by 30 the equilibrium point applying at the original concentration, which may not be desired in some applications.
In 1956 Greenspan et al.l Proc. 42nd Ann. Mtg. Chem. Spec. Man. Ass.
Dec. 1955), disclose~ that stable dilute peracetic acid solutions can be prepared by the use of peracid stabilisers in conjunction with proper 35 adjustment of the relative concentrations of the components of the dilute peracid solution, that is to say that, if the prepared dilute solution is not fully at equilibrium, adjustment of the balance of the componen~s can achieve stability, Ths solutions in question may be prepared by dilution of WO 93/07909 PCI'/GB92/01830 21213~
commercial, e.g. fully equilibrated peracetic acid which has been produced by the use of small amounts of a mineral acid catalyst.
United States Patent No 4297298 describes the production of an aqueous solution of a lower aliphatic peracid by preparing in a first process step a s concentrated solution of the peracid from the corresponding carboxylic acid or anhydride and concentrated hydrogen peroxide in the presence of a small quantity of a strong acid catalyst and diluting the solution with a solution containing at least one of the reagents from the first process step so as to bring the concentration of the aliphatic peracid to the rated concentration of 10 the mixture the concentration of the dlluent reagent or reagents being chosen N50 that once dilution has been brought about, the system is no longer at equilibrium, but tends ~o move in the direction of forming further allphatic peracid at a very slow rate." The process specifically described in United States Paten~ No. 4297298 produces a non-equilibrium composition 15 which contains an extremely high concentration of hydrogen peroxide, e.g.
from 28% to 46%. Such a concentration on contact with the user would cause skin bleaching and pain.
United States Patent No. 4743447 describes the production of solutions having a hydrogen peroxide base for disinfecting contac~ lenses, the 20 solution having from 0.005% to 0.1% by weight of peracetic acid, 1% to 8% by weight of hydrogen peroxide and sufficient acetic acid for the system to reach equilibrium. Such a solution may be prepared by direct reaction using a very dilute reaction mixture with lengthy equilibration or from a stable commercial solution having a "weak concentration" of 2s peracetic acid to which the other constituents of the composition are added.
This teaching does not therefore avoid the separate initial step of producing a stable weak solution of peracetic acid from which to produce in turn the final product.
EP-A-0357238 (Steris Corp) discioses an anti-microbial composition 30 comprising a strong oxidant, a copper and brass corrosion inhibitor, a buffering agent, at least one anti-corrosive agent which exhibits corrosion inhibition in at least aluminium, carbon steel and stainless steel, and a wetting agent. The corrosion inhibitors specifically disclosed for brass and aluminium comprise triazoles and molybdates, which are known to have 3s unfavourable toxicity, and which therefore renders undesirable their use in a medical environment.
It is an object of the present invention to provide a disinfectant composition, based on a dilute solu~ion of peracid, which may be used on ~;,," - , , ,, ~ .", , ~ ",,~ " ,, , , ; -" ~ ~ ~
WO 93/07909 ~ 12 ~L 3 4 O PCI'/GB92~1)1830 medical equipment comprising metal components to be disinfected.
In accordance with the present invention there is provided a process for the preparation of an aqueous disinfectant composition characterised in that the process comprises mixing a first aqueous solution comprising a lower s aliphatic peracid with a second aqueous solution comprising a corrosion inhibitor and a hydrogen peroxide stabilizer and/or peracid stabilizer.
In another aspect, the present invention provi~es a disinfectant composition obtainable by a process comprising mixing a first aqueous solution comprising a lower aliphatic peracid wi~h a seoond aqueous solu~is)n o comprising a corrosion inhibitor and a hydrogen peroxide st~bili~er and/or peracid stabilizer. It is to bs understood that the peracid composition of the present invention is not in equilibrium and comprises a relatively higher concentration of stabilizer(s) than a skilled person would expect to find in a composition which is in equilibrium and comprises a similar concentration of S peracid In yet another aspect, the present invention pro~ides a two-pack system for the preparation of a disinfectanl composition, characterised in that one pack comprises a first aqueous solution comprisin~ a lower aliphatic peracid, and the other pack comprises a second aqueous solution comprising a 20 corrosion inhibitor and a hydrogen peroxide stabilizer and/or peracid s~abilizer.
The firs~ aqueous solution preferably comprises a lower aliphatic peracid, such as peracetic acid, in an amount of from 2% to 10%, more preferably from 3% to 7%, by weight of the solution. The first aqueous solution may 25 additionally comprise stabilizer(s) for the hydrogen peroxide and/or the peracid in the equilibrium solution, each relevant stabilizer being present in apreferred amount of from 20 to tO,000 ppm. Preferably both the peroxide and peracid are stabilized in the solution, giving a preferred combined stabilizer concentration of frorn 3000 to 6000 ppm. A suitable peracid 30 stabilizer is dipicolinic acid and suitable peroxide stabilizers include phosphonic acids and salts thereof, e.g. the products sold by Monsan~o under the trade mark "Dequest" such as hydroxyethylidenediphosphonate, diethylen0triaminepentamethylene phosphonate and ethylenediaminetetramethylene phosphonate and those stabilizers claimed in 35 European pa~ent application 0426949, especially cyclohexane-1,2-diaminotetramethylenephosphonic acid and salts ~hereof (CDTMP). It should be understood that the first solution is usualiy an equilibrium mixture of the relevant reactants and reaction products, as generally described in the P~T16B ~ 2 / O t 8 2 :12 1 3 ~ 0 2 0 S~P~~PYIB~R ~99~
paragraph bridging page 1 and page 2 above, and that the above specified amount of peracid indicates the amount of peracid per se in the solution. A
preferred process for the preparation of dilute solutions of lower aiiphatic peracids useful in the present invention is disclosed in PCT Patent 5 Application No. WO'91/13058.
The second aques)us solution preferably comprises from 0.1% to 5%, rnore preferably from 0.1% to 1%, by weight of the solution of a corrosion inhibitor. Preferably, the corrosion inhibitor is an alkali metal phosphate, mos~ preferably a potassium phosphate. Dipotassium hydrogen 10 orthophosphate (K2HP04) is the most preferred corrosion inhibitor.
The second aqueous solution preferably comprises from 0.1% to 2%, often 0.1% to 1%, more preferably from 0.2% to 0.7% or 0.7%
to 1%, by weight of the solution of hydrogen peroxide stabilizer and/or peracid stabilizer, such as abou~ 0.5% or about 1% stabilizer.
15 Preferably a hydrogen peroxide stabilizer is used. The preferred peroxide stabilizers are phosphonic acids and salts thereof, for example, those described hereinabove as suitable for the first aqueous solution. A suitable peracid stabilizer is dipicolinic acid.
Mixing of the first and second solutions give a disinfectant composition 20 immediately after mixing comprising at least 0.05% and generally not greater than 1% by weight peracid. In many embodiments, the mixture of the two solutions immediately after mixing comprises from 0.1 % to 0.25% or from 0.25% to 0.5% by weight peracid. The mixture also desirably comprises from 0.1% to 25 5% corrosion inhibitor and from 0.1% to 1% peroxide stabilizer andlor peracid s~abilizer. Such mixtures can often be obtained conveniently by selecting a volume ratio of the first solution to the second solution which is often at least 1: 5 and not usually greater than 1: 50, preferably from 1 10 to 1: 30, taking into account the concentration of 3() the corriponents in each solution.
One or both of the aqueous solutions may contain other components useful in disinf~ctant compositions, e.g. a triazole corrosion inhibitor andlor a wetting agent, though the presence of these components is not ~ssential to obtain the advantages of the invention (indeed, such components may be 35 sli~htly detrimental~, One or both of the solutions may contain an indicator which undergoes a colour change to indicate that the two solutions have been mixed together.
It will be appreciated that the compositions provided by the process of .e~n~ t10~ P - t~ ~ IJ ~ r ~ ~
WO 93/0790~ . , ' PCl'JGB92/01830 21213~0 the present invention are not in equilibrium and that in the natural course of events the peracid component of the composition will tend towards equilibrium. For example, the composition described in the paragraph immediately above this paragraph will begin to chanae within a relatively 5 short period of time from mixing the first and second solutions together and that as time passes the peracid concentration in the solution will reduce as it tends towards equillbrium. Normal equilibrium could be expected to be reached after about two days, assuming the peracid andtor peroxide does not decompose in that period.
o The compositions of the present invention are particularly suitable for use as medical disinfectants. Preferably, the compositions are used to disinfect medical equipment which has metal, e.g. aluminium, brass, copper and especially steel, components required to be disinfected. For example, the composition is particularly useful ~or disinfection of endoscopes. The S present invention rnay have a further advantage over the prior art compositions of Steris. The selected components of the invention composition interact to protect metal components, especially steel components, with regard to localised corrosion, eg pitting, as well as, if not be~ter than, if molybdate, triazole and/or we~ting agent were present. This is 20 most surprising in light of the disclosure on page 4, lines ~ to 9, of Steris.
The present invention has the advantage of providing a dilute composition comprising a relatively high concentration of peracid. Furthermore, the process of the present invention enables a relatively longer shelf life for the separate aqueous solution than would be achieved if the composition was 25 supplied per se.
The invention will now be further described, without limitation, with reference to the following examples:
ExamDle 1. PreDaration of ComDosition accordinq to the Present Invention 30 A two-pack system was prepared. One pack contained 250 ml of an aqueous peracetic acid, 5% (active1 by weight, solution. The other pack contained 101 of an aqueous solution comprising 0.6% by weight dipotassium hydrogen ortho phosphate and 0.5% by weight CDTMP. The two packs were then mixed together to form a composition of the present 35 invention.
ExamDle 2. PreDaration of ComDosition accordina to the Present Invention A solution of 5% w/w peracetic acid, 20% w/w hydrogen peroxide, 8%
WO g3/07909 2 1 2 1 3 ~ O p~r/GB92/ol83o 7 - ~
wlw acetic acid was diluted 14 times with a solution containing 1% w/w CDTMP and 0.8% dipotassium hydrogen orthophosphate to form a solution containing 3,500ppm peracetic acid.
ExamDle 3 and ComDarison A. Corrosion Trials for Disinfectant Com~ositions Duplicate coupons of mild steel and stainless steel 316 were immersed for 72 hours at room temperature l15-25~C) in disinfectant solutions. In Example 3, the disinfectant solution was prepared according to the method o of Example 2 after a dilution by 25 tirnes to produce a solution containing 2000ppm peracetic aoid. In Comparison A, the disinfectant solu~ion was prepared according to the example given in the first table, page 6, lines 1 to 18 of European Patent Application No 0 357 238. The solutions were completely replaced daily with fresh solutions. Examina~ion of the coupons S with both the naked eye and an optical microscope on completion of the trial showed that for both of the metals in the composition according to the Steris Application, th~re was significant loc~lised corrosion and pitting on the metal but for the metals in the disinfectant solution according to the present invention there was only very slight localised corrosion.
20 The significant r0duction in localised corrosion achieved wi~h compositions accordiny to the present invention i~ surprising given the disclosure on page 4, lines 7 to 9 of the Steris Application, and is particularly advantageous because the results were achieved without the use of any toxic molybdate and triazole.
,~
The lower aliphatic peracids are effective wide-spectrum bac~ericides which have the particular advantage, in use, of leaving as residues only the 20 corr~sponding lower aliphatic acids and ther~fore being particularly suitablefor applicatiQns which require a non-environm~n~ally-polluting disinfectant.
While the lower aliphatic peracids in general are contemplated herein, for example those corresponding to carboxylic aliphatic acids containing 2 to 9 carbsn atoms, peracetic acid is particularly envisaged since it is already a 2s commercially important peracid for disinfectant purposes. Where the following description relates to peracetic acid it is to be understood that the other peracids may be read in substitution therefor provided that the technical context allows it.
Aqueous solutions of peracetic acid containing up to about 45% by 30 weight of peracetic acid are commercially available. Such solutions may be produced by reacting appropriately concentrat~d hydrogen peroxide and acetic acid in an a~ueous medium in the presence of an acid catalyst which is usually sulphuric acid or other strong min~ral acid. The acid catalyst may be present in from about 0.1% to 3bout 5% by weight of the reaction 3s mixture.
Aqueous solutions of peracetic acid represent equilibrium mixtures of the reactants and the reaction products and, under relatively forcing reaction conditions, for example when using one or rnore of a substantial 4uantity of WO 93/07909 PCI'/~B92/01830 :~
21213'10 2 '.
catalyst, an elevated reaction temperature and a concen~rated reaction mixture, equilibrium may be substantialiy reached in a relatively short time.
When using the strong acid catalyst in from 2% to 5% of the reaction mixture, a temperature of from 30~C to 50~C and a concentration of acid s above about 20% by weight the reaction mixture may come to equilibrium within hours. For some applications. or where long storage is envisaged, it -~;
may not be desirable for there to be catalyst residues in a peracid product particularly, for example, dilute products intended for personal or domestic hygiene use. For many applications dilute solutions of peracetic acid, for lO example below 5% by weight but often below 2%, for example from 0.1%
to 2% by weight, are required. Concentrations of peracetic acid above 0.5% by weight for example from 0.5% to 1% by weight, are particularly effective bactericidally in, for example, toilet cleansing applications. Such dilute peracetic acid solutions may be produced directly by reacting acetic 5 acid and hydrogen peroxide in a suitably diiute reaction medium but equilibrium can take an extremely long time to reach, particularly at the more extreme dilutions envisaged. At peracid concentrations below 1% by weight equilibrium may take a month or more to reach if the rsaction is not acid catalysed or a week or more even if the reaction is acid catalysed. This 20 entails a very heavy utilisation of plant and equipment on a large production scale.
If a concentrated equilibrium solution of peracetic acid is diluted with water the equilibrium point of the system is progressively altered, as dilution progresses, in favour of the regeneration of the original reactants. The 25 ageing time taken to attain the new equilibrium point, after dilution, is of a similar order to that required to produce such a dilute solution directly from suitable reactants. Such a diluted soiution may be used directly although it is not at equilibrium and is therefore of variable composition in storage.
Such non-equilibrium diluted solutions also have a composition dictated by 30 the equilibrium point applying at the original concentration, which may not be desired in some applications.
In 1956 Greenspan et al.l Proc. 42nd Ann. Mtg. Chem. Spec. Man. Ass.
Dec. 1955), disclose~ that stable dilute peracetic acid solutions can be prepared by the use of peracid stabilisers in conjunction with proper 35 adjustment of the relative concentrations of the components of the dilute peracid solution, that is to say that, if the prepared dilute solution is not fully at equilibrium, adjustment of the balance of the componen~s can achieve stability, Ths solutions in question may be prepared by dilution of WO 93/07909 PCI'/GB92/01830 21213~
commercial, e.g. fully equilibrated peracetic acid which has been produced by the use of small amounts of a mineral acid catalyst.
United States Patent No 4297298 describes the production of an aqueous solution of a lower aliphatic peracid by preparing in a first process step a s concentrated solution of the peracid from the corresponding carboxylic acid or anhydride and concentrated hydrogen peroxide in the presence of a small quantity of a strong acid catalyst and diluting the solution with a solution containing at least one of the reagents from the first process step so as to bring the concentration of the aliphatic peracid to the rated concentration of 10 the mixture the concentration of the dlluent reagent or reagents being chosen N50 that once dilution has been brought about, the system is no longer at equilibrium, but tends ~o move in the direction of forming further allphatic peracid at a very slow rate." The process specifically described in United States Paten~ No. 4297298 produces a non-equilibrium composition 15 which contains an extremely high concentration of hydrogen peroxide, e.g.
from 28% to 46%. Such a concentration on contact with the user would cause skin bleaching and pain.
United States Patent No. 4743447 describes the production of solutions having a hydrogen peroxide base for disinfecting contac~ lenses, the 20 solution having from 0.005% to 0.1% by weight of peracetic acid, 1% to 8% by weight of hydrogen peroxide and sufficient acetic acid for the system to reach equilibrium. Such a solution may be prepared by direct reaction using a very dilute reaction mixture with lengthy equilibration or from a stable commercial solution having a "weak concentration" of 2s peracetic acid to which the other constituents of the composition are added.
This teaching does not therefore avoid the separate initial step of producing a stable weak solution of peracetic acid from which to produce in turn the final product.
EP-A-0357238 (Steris Corp) discioses an anti-microbial composition 30 comprising a strong oxidant, a copper and brass corrosion inhibitor, a buffering agent, at least one anti-corrosive agent which exhibits corrosion inhibition in at least aluminium, carbon steel and stainless steel, and a wetting agent. The corrosion inhibitors specifically disclosed for brass and aluminium comprise triazoles and molybdates, which are known to have 3s unfavourable toxicity, and which therefore renders undesirable their use in a medical environment.
It is an object of the present invention to provide a disinfectant composition, based on a dilute solu~ion of peracid, which may be used on ~;,," - , , ,, ~ .", , ~ ",,~ " ,, , , ; -" ~ ~ ~
WO 93/07909 ~ 12 ~L 3 4 O PCI'/GB92~1)1830 medical equipment comprising metal components to be disinfected.
In accordance with the present invention there is provided a process for the preparation of an aqueous disinfectant composition characterised in that the process comprises mixing a first aqueous solution comprising a lower s aliphatic peracid with a second aqueous solution comprising a corrosion inhibitor and a hydrogen peroxide stabilizer and/or peracid stabilizer.
In another aspect, the present invention provi~es a disinfectant composition obtainable by a process comprising mixing a first aqueous solution comprising a lower aliphatic peracid wi~h a seoond aqueous solu~is)n o comprising a corrosion inhibitor and a hydrogen peroxide st~bili~er and/or peracid stabilizer. It is to bs understood that the peracid composition of the present invention is not in equilibrium and comprises a relatively higher concentration of stabilizer(s) than a skilled person would expect to find in a composition which is in equilibrium and comprises a similar concentration of S peracid In yet another aspect, the present invention pro~ides a two-pack system for the preparation of a disinfectanl composition, characterised in that one pack comprises a first aqueous solution comprisin~ a lower aliphatic peracid, and the other pack comprises a second aqueous solution comprising a 20 corrosion inhibitor and a hydrogen peroxide stabilizer and/or peracid s~abilizer.
The firs~ aqueous solution preferably comprises a lower aliphatic peracid, such as peracetic acid, in an amount of from 2% to 10%, more preferably from 3% to 7%, by weight of the solution. The first aqueous solution may 25 additionally comprise stabilizer(s) for the hydrogen peroxide and/or the peracid in the equilibrium solution, each relevant stabilizer being present in apreferred amount of from 20 to tO,000 ppm. Preferably both the peroxide and peracid are stabilized in the solution, giving a preferred combined stabilizer concentration of frorn 3000 to 6000 ppm. A suitable peracid 30 stabilizer is dipicolinic acid and suitable peroxide stabilizers include phosphonic acids and salts thereof, e.g. the products sold by Monsan~o under the trade mark "Dequest" such as hydroxyethylidenediphosphonate, diethylen0triaminepentamethylene phosphonate and ethylenediaminetetramethylene phosphonate and those stabilizers claimed in 35 European pa~ent application 0426949, especially cyclohexane-1,2-diaminotetramethylenephosphonic acid and salts ~hereof (CDTMP). It should be understood that the first solution is usualiy an equilibrium mixture of the relevant reactants and reaction products, as generally described in the P~T16B ~ 2 / O t 8 2 :12 1 3 ~ 0 2 0 S~P~~PYIB~R ~99~
paragraph bridging page 1 and page 2 above, and that the above specified amount of peracid indicates the amount of peracid per se in the solution. A
preferred process for the preparation of dilute solutions of lower aiiphatic peracids useful in the present invention is disclosed in PCT Patent 5 Application No. WO'91/13058.
The second aques)us solution preferably comprises from 0.1% to 5%, rnore preferably from 0.1% to 1%, by weight of the solution of a corrosion inhibitor. Preferably, the corrosion inhibitor is an alkali metal phosphate, mos~ preferably a potassium phosphate. Dipotassium hydrogen 10 orthophosphate (K2HP04) is the most preferred corrosion inhibitor.
The second aqueous solution preferably comprises from 0.1% to 2%, often 0.1% to 1%, more preferably from 0.2% to 0.7% or 0.7%
to 1%, by weight of the solution of hydrogen peroxide stabilizer and/or peracid stabilizer, such as abou~ 0.5% or about 1% stabilizer.
15 Preferably a hydrogen peroxide stabilizer is used. The preferred peroxide stabilizers are phosphonic acids and salts thereof, for example, those described hereinabove as suitable for the first aqueous solution. A suitable peracid stabilizer is dipicolinic acid.
Mixing of the first and second solutions give a disinfectant composition 20 immediately after mixing comprising at least 0.05% and generally not greater than 1% by weight peracid. In many embodiments, the mixture of the two solutions immediately after mixing comprises from 0.1 % to 0.25% or from 0.25% to 0.5% by weight peracid. The mixture also desirably comprises from 0.1% to 25 5% corrosion inhibitor and from 0.1% to 1% peroxide stabilizer andlor peracid s~abilizer. Such mixtures can often be obtained conveniently by selecting a volume ratio of the first solution to the second solution which is often at least 1: 5 and not usually greater than 1: 50, preferably from 1 10 to 1: 30, taking into account the concentration of 3() the corriponents in each solution.
One or both of the aqueous solutions may contain other components useful in disinf~ctant compositions, e.g. a triazole corrosion inhibitor andlor a wetting agent, though the presence of these components is not ~ssential to obtain the advantages of the invention (indeed, such components may be 35 sli~htly detrimental~, One or both of the solutions may contain an indicator which undergoes a colour change to indicate that the two solutions have been mixed together.
It will be appreciated that the compositions provided by the process of .e~n~ t10~ P - t~ ~ IJ ~ r ~ ~
WO 93/0790~ . , ' PCl'JGB92/01830 21213~0 the present invention are not in equilibrium and that in the natural course of events the peracid component of the composition will tend towards equilibrium. For example, the composition described in the paragraph immediately above this paragraph will begin to chanae within a relatively 5 short period of time from mixing the first and second solutions together and that as time passes the peracid concentration in the solution will reduce as it tends towards equillbrium. Normal equilibrium could be expected to be reached after about two days, assuming the peracid andtor peroxide does not decompose in that period.
o The compositions of the present invention are particularly suitable for use as medical disinfectants. Preferably, the compositions are used to disinfect medical equipment which has metal, e.g. aluminium, brass, copper and especially steel, components required to be disinfected. For example, the composition is particularly useful ~or disinfection of endoscopes. The S present invention rnay have a further advantage over the prior art compositions of Steris. The selected components of the invention composition interact to protect metal components, especially steel components, with regard to localised corrosion, eg pitting, as well as, if not be~ter than, if molybdate, triazole and/or we~ting agent were present. This is 20 most surprising in light of the disclosure on page 4, lines ~ to 9, of Steris.
The present invention has the advantage of providing a dilute composition comprising a relatively high concentration of peracid. Furthermore, the process of the present invention enables a relatively longer shelf life for the separate aqueous solution than would be achieved if the composition was 25 supplied per se.
The invention will now be further described, without limitation, with reference to the following examples:
ExamDle 1. PreDaration of ComDosition accordinq to the Present Invention 30 A two-pack system was prepared. One pack contained 250 ml of an aqueous peracetic acid, 5% (active1 by weight, solution. The other pack contained 101 of an aqueous solution comprising 0.6% by weight dipotassium hydrogen ortho phosphate and 0.5% by weight CDTMP. The two packs were then mixed together to form a composition of the present 35 invention.
ExamDle 2. PreDaration of ComDosition accordina to the Present Invention A solution of 5% w/w peracetic acid, 20% w/w hydrogen peroxide, 8%
WO g3/07909 2 1 2 1 3 ~ O p~r/GB92/ol83o 7 - ~
wlw acetic acid was diluted 14 times with a solution containing 1% w/w CDTMP and 0.8% dipotassium hydrogen orthophosphate to form a solution containing 3,500ppm peracetic acid.
ExamDle 3 and ComDarison A. Corrosion Trials for Disinfectant Com~ositions Duplicate coupons of mild steel and stainless steel 316 were immersed for 72 hours at room temperature l15-25~C) in disinfectant solutions. In Example 3, the disinfectant solution was prepared according to the method o of Example 2 after a dilution by 25 tirnes to produce a solution containing 2000ppm peracetic aoid. In Comparison A, the disinfectant solu~ion was prepared according to the example given in the first table, page 6, lines 1 to 18 of European Patent Application No 0 357 238. The solutions were completely replaced daily with fresh solutions. Examina~ion of the coupons S with both the naked eye and an optical microscope on completion of the trial showed that for both of the metals in the composition according to the Steris Application, th~re was significant loc~lised corrosion and pitting on the metal but for the metals in the disinfectant solution according to the present invention there was only very slight localised corrosion.
20 The significant r0duction in localised corrosion achieved wi~h compositions accordiny to the present invention i~ surprising given the disclosure on page 4, lines 7 to 9 of the Steris Application, and is particularly advantageous because the results were achieved without the use of any toxic molybdate and triazole.
,~
Claims (25)
1. A process for the preparation of an aqueous disinfectant composition characterised in that the process comprises mixing a first aqueous solution comprising a loweraliphatic peracid with a second aqueous solution comprising a corrosion inhibitor and a stabilizer, wherein the stabilizer is at least one stabilizer selected from peroxide stabilizers and peracid stabilizers.
2. A disinfectant composition obtainable by a process comprising mixing a first aqueous solution comprising a lower aliphatic peracid with a second aqueous solution comprising a corrosion inhibitor and a stabilizer, wherein the stabilizer is at least one stabilizer selected from peroxide stabilizers and peracid stabilizers.
3. A two-pack system for the preparation of a disinfectant composition, characterised in than one pack comprises a first aqueous solution comprising a lower aliphaticperacid, and the other pack comprises a second aqueous solution comprising a corrosion inhibitor and a stabilizer, wherein the stabilizer is at least one stabilizer selected from peroxide stabilizers and peracid stabilizers.
4. A process, composition or two-pack system as claimed in claims 1, 2 or 3, respectively, characterised in that the first aqueous solution comprises a (C2-C9) aliphatic peracid in an amount of from 2% to 10% by weight of the solution.
5. A process, composition or two-pack system as claimed in claim 4, characterised in that the first aqueous solution comprises a (C2-C9) aliphatic peracid in an amount of from 3% to 7% by weight of the solution.
6. A process, composition or two-pack system as claimed in claim 4 or 5, characterised in that the first aqueous solution comprises peracetic acid.
7. A process, composition or two-pack system as claimed in claims 1, 2 or 3, respectively, or claim 4, 5 or 6, characterised in that the second aqueoussolution comprises from 0.1% to 5% by weight of the solution of a corrosion inhibitor.
8. A process, composition or two-pack system as claimed in claim 7, characterised in that the second aqueous solution comprises from 0.1% to 1% by weight of the solution of a corrosion inhibitor.
9. A process, composition or two-pack system as claimed in claim 7 or 8, characterised in that the corrosion inhibitor is an alkali metal phosphate.
10. A process, composition or two-pack system as claimed in claim 9, characterised in that the corrosion inhibitor is dipotassium hydrogen orthophosphate.
11. A process, composition or two-pack system as claimed in any one of claims 1 to 10, characterised in that the second aqueous solution comprises from 0.1% to 2% by weight of the solution of the stabilizer.
12. A process, composition or two-pack system as claimed in claim 11, characterised in that the second aqueous solution comprises from 0.2% to 0.7% or 0.7% to 1% by weight of the solution of the stabilizer.
13. A process, composition or two-pack system as claimed in claim 11 or 12, characterised in that only a hydrogen peroxide stabilizer is used.
14. A process, composition or two-pack system as claimed in claim 11, 12 or 13, characterised in that the stabilizer(s) is/are phosphonic acids or salts thereof.
15. A process, composition or two-pack system as claimed in claim 14, characterised in that the hydrogen peroxide stabilizer is cyclohexane-1,2-diaminotetramethylenephosphonic acid or salts thereof.
16. A process, composition or two-pack system as claimed in any one of claims 1 to 15, characterised in that the ratio of the volume of the first aqueous solution to the volume of the second aqueous solution is 1: 5 to 1: 50.
17. A process, composition or two-pack system as claimed in claim 16, characterised in that the ratio of the volume of the first aqueous solution to the volume of the second aqueous solution is 1: 10 to 1: 30.
18. A disinfectant composition, suitable for disinfecting medical equipment having metal components to be disinfected, characterised in that it comprises at least 0.05%
to 1% by weight lower aliphatic peracid, from 0.1 % to 5 % corrosion inhibitor and from 0.1% to 1% stabilizer, wherein the stabilizer is at least one stabilizer selected from peroxide stabilizers and peracid stabilizers and wherein the peracid is not in an equilibrium state.
to 1% by weight lower aliphatic peracid, from 0.1 % to 5 % corrosion inhibitor and from 0.1% to 1% stabilizer, wherein the stabilizer is at least one stabilizer selected from peroxide stabilizers and peracid stabilizers and wherein the peracid is not in an equilibrium state.
19. A disinfectant composition according to claim 18, characterised in that it comprises from 0.1% to 0.25 % or 0.25 % to 0.5 % by weight peracid and that the peracid is not in an equilibrium state.
20. A process, composition or two-pack system as claimed in any one of claims 1 to 17, characterised in that one or both of the two aqueous solutions comprises an indicator which undergoes a colour change when the solutions are mixed together.
21. A process, composition or two pack system according to any one of claims 1 to 17, characterised in that it is suitable for disinfecting steel surfaces.
22. A process, composition or two pack system according to any one of claims 1 to 17, characterised in that it gives reduced localised corrosion and pitting of steel.
23. Use of a composition as claimed in claim 2, or any one of claims 4 to 22, as a disinfectant.
24. Use as claimed in claim 23, characterised in that the disinfectant is suitable for disinfecting metal components of medical equipment.
25. Use as claimed in claim 24, characterised in that the medical equipment is an endoscope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919122048A GB9122048D0 (en) | 1991-10-17 | 1991-10-17 | Compositions and uses thereof |
| GB9122048.3 | 1991-10-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2121340A1 CA2121340A1 (en) | 1993-04-29 |
| CA2121340C true CA2121340C (en) | 1999-03-23 |
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ID=10703085
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002121340A Expired - Fee Related CA2121340C (en) | 1991-10-17 | 1992-10-08 | Compositions and uses thereof |
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| JP (1) | JP2843438B2 (en) |
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| CA (1) | CA2121340C (en) |
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| ES (1) | ES2149179T3 (en) |
| FI (1) | FI110671B (en) |
| GB (1) | GB9122048D0 (en) |
| HU (1) | HU214287B (en) |
| IN (1) | IN174157B (en) |
| MX (1) | MX9205956A (en) |
| MY (1) | MY108233A (en) |
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| RU (1) | RU2122434C1 (en) |
| SK (1) | SK283516B6 (en) |
| WO (1) | WO1993007909A1 (en) |
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Families Citing this family (111)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9300366D0 (en) * | 1993-01-09 | 1993-03-03 | Solvay Interox Ltd | Compositions and uses thereof |
| ES2121399T3 (en) * | 1994-07-01 | 1998-11-16 | Warwick Int Group | BLEACHING COMPOSITIONS. |
| FR2728171B1 (en) | 1994-12-14 | 1997-01-24 | Chemoxal Sa | PRODUCTION OF BIOCIDAL DISINFECTANT FORMULATIONS BASED ON PERACETIC IONS |
| GB2297976A (en) * | 1995-02-01 | 1996-08-21 | Reckitt & Colmann Prod Ltd | Improvements in or relating to a bleaching process |
| US5635195A (en) * | 1995-11-17 | 1997-06-03 | Minntech Corporation | Premix for room temperature sterilant |
| WO1997019594A1 (en) * | 1995-12-01 | 1997-06-05 | Minntech Corporation | Room temperature sterilant for medical devices |
| AUPO371096A0 (en) * | 1996-11-18 | 1996-12-12 | Green, Bruce Phillip | Corrosion inhibiting composition |
| EP0873687B2 (en) * | 1997-04-24 | 2006-04-26 | Chemoxal Sa | Disinfecting and fungicidal composition based on peracetic acid and an amine oxide |
| GB2326826A (en) * | 1997-07-01 | 1999-01-06 | Robert Ashley Simms | Disinfectant peracid composition |
| US6010729A (en) | 1998-08-20 | 2000-01-04 | Ecolab Inc. | Treatment of animal carcasses |
| CA2343772A1 (en) | 1998-10-01 | 2000-04-06 | Bradley K. Onstad | Multi-part anti-microbial sterilization compositions and methods |
| EP1123655B1 (en) * | 1998-10-19 | 2005-10-05 | Saraya Co., Ltd. | Bactericidal/disinfectant peracetic acid composition |
| WO2000030690A1 (en) * | 1998-11-23 | 2000-06-02 | Ecolab Inc. | Non-corrosive sterilant composition |
| KR100363896B1 (en) * | 2000-04-21 | 2002-12-16 | 이진식 | A medical instrument cleaning solution using peracetic acid and the manufacturing method of the above solution |
| US7150884B1 (en) * | 2000-07-12 | 2006-12-19 | Ecolab Inc. | Composition for inhibition of microbial growth |
| US7316824B2 (en) * | 2000-12-15 | 2008-01-08 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US6514556B2 (en) | 2000-12-15 | 2003-02-04 | Ecolab Inc. | Method and composition for washing poultry during processing |
| US6635286B2 (en) * | 2001-06-29 | 2003-10-21 | Ecolab Inc. | Peroxy acid treatment to control pathogenic organisms on growing plants |
| US20030129254A1 (en) * | 2001-07-13 | 2003-07-10 | Saraya Co., Ltd., A Japanese Corporation | Bactericidal/disinfectant peracetic and acid composition |
| ITMI20020327A1 (en) * | 2002-02-19 | 2003-08-19 | Ausimont Spa | PROCESS TO ELIMINATE PNEUMOFILA LEGIONELLA FROM WATER NETWORKS |
| DK1499719T3 (en) * | 2002-04-30 | 2011-02-28 | Bayer Healthcare Llc | Factor VII or VIIa polypeptide variants |
| KR100515929B1 (en) * | 2002-08-28 | 2005-09-20 | 이진식 | A composition for disinfecting and washing medical instruments comprising a surfactant having alcohol groups at the both terminals and a process for the preparation thereof 2 |
| KR100515928B1 (en) * | 2002-08-28 | 2005-09-20 | 이진식 | A composition for disinfecting and washing medical instruments comprising a surfactant having alcohol groups at the both terminals and a process for the preparation thereof 1 |
| US7504123B2 (en) | 2004-01-09 | 2009-03-17 | Ecolab Inc. | Methods for washing poultry during processing with medium chain peroxycarboxylic acid compositions |
| US8999175B2 (en) | 2004-01-09 | 2015-04-07 | Ecolab Usa Inc. | Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions |
| US20050161636A1 (en) * | 2004-01-09 | 2005-07-28 | Ecolab Inc. | Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions |
| US7887641B2 (en) | 2004-01-09 | 2011-02-15 | Ecolab Usa Inc. | Neutral or alkaline medium chain peroxycarboxylic acid compositions and methods employing them |
| JP2007520479A (en) | 2004-01-09 | 2007-07-26 | イーコラブ インコーポレイティド | Medium chain peroxycarboxylic acid composition |
| US7507429B2 (en) | 2004-01-09 | 2009-03-24 | Ecolab Inc. | Methods for washing carcasses, meat, or meat products with medium chain peroxycarboxylic acid compositions |
| US7771737B2 (en) | 2004-01-09 | 2010-08-10 | Ecolab Inc. | Medium chain peroxycarboxylic acid compositions |
| CA2593822C (en) * | 2005-01-11 | 2012-08-07 | Clean Earth Technologies, Llc | Peracid/ peroxide composition and use thereof as an anti-microbial and a photosensitizer |
| US7550420B2 (en) * | 2005-04-29 | 2009-06-23 | E. I. Dupont De Nemours And Company | Enzymatic production of peracids using perhydrolytic enzymes |
| EP1877566B1 (en) * | 2005-04-29 | 2009-02-18 | E.I. Du Pont De Nemours And Company | Enzymatic production of peracids using perhydrolytic enzymes |
| US7754670B2 (en) | 2005-07-06 | 2010-07-13 | Ecolab Inc. | Surfactant peroxycarboxylic acid compositions |
| US7964378B2 (en) * | 2005-12-13 | 2011-06-21 | E.I. Du Pont De Nemours And Company | Production of peracids using an enzyme having perhydrolysis activity |
| US8288136B2 (en) | 2005-12-13 | 2012-10-16 | E. I. Du Pont De Nemours And Company | Production of peracids using an enzyme having perhydrolysis activity |
| US7951566B2 (en) * | 2005-12-13 | 2011-05-31 | E.I. Du Pont De Nemours And Company | Production of peracids using an enzyme having perhydrolysis activity |
| US7723083B2 (en) * | 2005-12-13 | 2010-05-25 | E.I. Du Pont De Nemours And Company | Production of peracids using an enzyme having perhydrolysis activity |
| US8518675B2 (en) | 2005-12-13 | 2013-08-27 | E. I. Du Pont De Nemours And Company | Production of peracids using an enzyme having perhydrolysis activity |
| JP5478074B2 (en) * | 2006-02-23 | 2014-04-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Removable antimicrobial coating composition and method of use |
| US8075857B2 (en) | 2006-10-18 | 2011-12-13 | Ecolab Usa Inc. | Apparatus and method for making a peroxycarboxylic acid |
| US7547421B2 (en) | 2006-10-18 | 2009-06-16 | Ecolab Inc. | Apparatus and method for making a peroxycarboxylic acid |
| ES2534471T3 (en) | 2006-10-27 | 2015-04-23 | E.I. Du Pont De Nemours And Company | Prion Decontamination Method |
| FI119800B (en) * | 2006-11-09 | 2009-03-31 | Kemira Oyj | Procedures for preventing the growth of microorganisms and combinations that prevent the growth of microorganisms |
| US7473658B2 (en) * | 2006-11-13 | 2009-01-06 | E. I. Du Pont Nemours And Company | Partially fluorinated amino acid derivatives as gelling and surface active agents |
| WO2008138817A2 (en) * | 2007-05-11 | 2008-11-20 | Basf Se | Method and composition for disinfecting delicate surfaces |
| US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
| EP2271616B1 (en) | 2008-03-28 | 2020-11-11 | Ecolab USA Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| CA2731047A1 (en) * | 2008-07-24 | 2010-01-28 | Fmc Corporation | Dilute aqueous peracid solutions and stabilization method |
| JP5504268B2 (en) * | 2008-08-13 | 2014-05-28 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Control of enzymatic peracid production |
| US8337905B2 (en) | 2008-10-03 | 2012-12-25 | E. I. Du Pont De Nemours And Company | Multi-component peracid generation system |
| US8034759B2 (en) | 2008-10-31 | 2011-10-11 | Ecolab Usa Inc. | Enhanced stability peracid compositions |
| WO2010095231A1 (en) * | 2009-02-19 | 2010-08-26 | サラヤ株式会社 | Acidic oxidant-containing composition having aluminum corrosion-suppressing effect and use thereof |
| US20110177148A1 (en) * | 2009-07-27 | 2011-07-21 | E. I. Du Pont De Nemours And Company | Enzymatic in situ preparation of peracid-based removable antimicrobial coating compositions and methods of use |
| JP5730306B2 (en) | 2009-07-27 | 2015-06-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Enzymatic in situ preparation and use of peracid-based removable antimicrobial coating compositions |
| US20110182959A1 (en) * | 2009-07-27 | 2011-07-28 | E.I. Du Pont De Nemours And Company. | Removable antimicrobial coating compositions containing acid-activated rheology agent and methods of use |
| US20110177146A1 (en) | 2009-07-27 | 2011-07-21 | E. I. Du Pont De Nemours And Company | Removable antimicrobial coating compositions containing cationic rheology agent and methods of use |
| US20110177145A1 (en) | 2009-07-27 | 2011-07-21 | E.I. Du Pont De Nemours And Company | In situ preparation of peracid-based removable antimicrobial coating compositions and methods of use |
| US8222012B2 (en) * | 2009-10-01 | 2012-07-17 | E. I. Du Pont De Nemours And Company | Perhydrolase for enzymatic peracid production |
| US7923233B1 (en) | 2009-12-07 | 2011-04-12 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| US7927854B1 (en) | 2009-12-07 | 2011-04-19 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| US7932072B1 (en) | 2009-12-07 | 2011-04-26 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| US7910347B1 (en) | 2009-12-07 | 2011-03-22 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| US7960528B1 (en) | 2009-12-07 | 2011-06-14 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| US20110217204A1 (en) * | 2010-03-05 | 2011-09-08 | Franciskovich Phillip P | Sterilization composition |
| US8389255B2 (en) * | 2010-03-26 | 2013-03-05 | E.I. De Pont De Nemours And Company | Perhydrolase providing improved specific activity |
| US8445242B2 (en) * | 2010-03-26 | 2013-05-21 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved specific activity |
| WO2011119703A1 (en) | 2010-03-26 | 2011-09-29 | E.I. Dupont De Nemours And Company | Process for the purification of proteins |
| US8450091B2 (en) * | 2010-03-26 | 2013-05-28 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved specific activity |
| US20130005889A1 (en) * | 2010-03-26 | 2013-01-03 | Joachim C Ritter | Polyarylene sulfide-containing polymer melt |
| WO2011119706A1 (en) | 2010-03-26 | 2011-09-29 | E.I. Dupont De Nemours And Company | Perhydrolase providing improved specific activity |
| US8663616B2 (en) | 2010-12-20 | 2014-03-04 | E I Du Pont De Nemours And Company | Enzymatic peracid generation for use in oral care products |
| KR20140114269A (en) | 2010-12-20 | 2014-09-26 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Targeted perhydrolases |
| US8389256B2 (en) | 2010-12-21 | 2013-03-05 | E.I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8394616B2 (en) | 2010-12-21 | 2013-03-12 | E.I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8389259B2 (en) | 2010-12-21 | 2013-03-05 | E.I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8394617B2 (en) | 2010-12-21 | 2013-03-12 | E.I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| WO2012087788A1 (en) | 2010-12-21 | 2012-06-28 | E.I. Dupont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8389258B2 (en) | 2010-12-21 | 2013-03-05 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| WO2012087785A1 (en) | 2010-12-21 | 2012-06-28 | E.I. Dupont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| WO2012087792A1 (en) | 2010-12-21 | 2012-06-28 | E.I. Dupont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8906963B2 (en) | 2011-07-14 | 2014-12-09 | Ecolab Usa Inc | Deodorization of peracids |
| US8883848B2 (en) | 2011-07-14 | 2014-11-11 | Ecolab Usa Inc. | Enhanced microbial peracid compositions and methods of use at reduced temperatures in aseptic cleaning |
| US8546120B2 (en) | 2011-10-25 | 2013-10-01 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8735125B2 (en) | 2011-10-25 | 2014-05-27 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| WO2013062885A1 (en) | 2011-10-25 | 2013-05-02 | E.I. Dupont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8501447B2 (en) | 2011-10-25 | 2013-08-06 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8956843B2 (en) | 2011-10-25 | 2015-02-17 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8962294B2 (en) | 2011-10-25 | 2015-02-24 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8486679B2 (en) | 2011-10-25 | 2013-07-16 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8809030B2 (en) | 2011-10-25 | 2014-08-19 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| US8557556B2 (en) | 2011-10-25 | 2013-10-15 | E. I. Du Pont De Nemours And Company | Perhydrolase variant providing improved specific activity |
| WO2013096045A1 (en) | 2011-12-19 | 2013-06-27 | E. I. Du Pont De Nemours And Company | Perhydrolase variants providing improved specific activity in the presence of surfactant |
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| US8865436B2 (en) | 2012-03-30 | 2014-10-21 | E. I. Du Pont De Nemours And Company | Enzymes useful for peracid production |
| WO2013148184A1 (en) | 2012-03-30 | 2013-10-03 | E. I. Du Pont De Nemours And Company | Enzymes useful for peracid production |
| BR112014020748B1 (en) | 2012-03-30 | 2021-02-23 | Ecolab Usa Inc. | water treatment method, water source treatment method and aqueous water treatment composition with antimicrobial activity |
| CN104350154B (en) | 2012-03-30 | 2020-12-29 | 纳幕尔杜邦公司 | Enzymes useful for peracid production |
| WO2013148188A1 (en) | 2012-03-30 | 2013-10-03 | E. I. Du Pont De Nemours And Company | Enzymes useful for peracid production |
| EP2831253B1 (en) | 2012-03-30 | 2021-11-24 | DuPont US Holding, LLC | Enzymes useful for peracid production |
| US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
| US20140308162A1 (en) | 2013-04-15 | 2014-10-16 | Ecolab Usa Inc. | Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
| US10750749B2 (en) * | 2014-04-28 | 2020-08-25 | American Sterilizer Company | Process and composition for killing spores |
| AU2019222696B2 (en) | 2018-02-14 | 2024-02-29 | Ecolab Usa Inc. | Compositions and methods for the reduction of biofilm and spores from membranes |
| KR102034095B1 (en) | 2018-07-02 | 2019-10-18 | 남일 | Sterilization disinfection composition, method for producing the same and it’s metal corrosion prevention and stabilizing method |
| CN110982119B (en) * | 2019-12-20 | 2021-06-04 | 杭州本松新材料技术股份有限公司 | Use of triazole compound as thermoplastic resin material additive for low-voltage electric appliance shell |
| KR102520527B1 (en) | 2020-12-24 | 2023-04-11 | 군산대학교산학협력단 | Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE551904C (en) * | 1931-05-04 | 1932-06-07 | Leopold Fleischacker & Co | Method and device for the production of the edge reinforcements of paper carpet webs |
| US3759594A (en) * | 1971-12-02 | 1973-09-18 | J Cobb | Method and apparatus for storing cutting implements |
| JPS5238009B2 (en) * | 1973-11-02 | 1977-09-27 | ||
| NL7608266A (en) * | 1975-08-16 | 1977-02-18 | Henkel & Cie Gmbh | CONCENTRATES OF MICROBICIDE AGENTS. |
| DE2657193A1 (en) * | 1976-12-17 | 1978-06-29 | Henkel Kgaa | NEW PRODUCTS FOR PRODUCTS OF EPSILON -CAPROLACTAM AND BETA-HYDROXYALKYLAMINES, AND THEIR AETHYLENE OXIDE ADDUCTS, THEIR PRODUCTION AND USE AS ANTIMICROBIAL AGENTS |
| CA1146851A (en) * | 1978-05-01 | 1983-05-24 | Donald F. Greene | Hydrogen peroxide disinfecting and sterilizing compositions |
| US4276263A (en) * | 1978-07-12 | 1981-06-30 | Anprosol Incorporated | Sterilization system |
| FR2462425A1 (en) * | 1979-08-01 | 1981-02-13 | Air Liquide | METHOD FOR MANUFACTURING STABLE DILUTED SOLUTIONS OF ALIPHATIC CARBOXYLIC PERACIDS |
| DE3205318A1 (en) * | 1982-02-15 | 1983-08-18 | Henkel KGaA, 4000 Düsseldorf | DISINFECTANT CONCENTRATE |
| US5037623A (en) * | 1986-02-06 | 1991-08-06 | Steris Corporation | Sterilant concentrate injection system |
| US5077008A (en) * | 1986-02-06 | 1991-12-31 | Steris Corporation | Anti-microbial composition |
| ES2091204T3 (en) * | 1988-08-04 | 1996-11-01 | Ciba Geigy Ag | METHOD AND COMPOSITIONS TO PRESERVE OPHTHALMIC SOLUTIONS. |
| CA1321137C (en) * | 1988-08-08 | 1993-08-10 | Raymond C. Kralovic | Anti-microbial composition |
| GB8925376D0 (en) * | 1989-11-09 | 1989-12-28 | Interox Chemicals Ltd | Stabilisation of concentrated hydrogen peroxide solutions |
| ES2155824T3 (en) * | 1991-07-15 | 2001-06-01 | Minntech Corp | STERILIZING AGENT OF THE PERACETIC / PEROXIDE, STABLE AND ANTI-CORROSIVE TYPE. |
-
1991
- 1991-10-17 GB GB919122048A patent/GB9122048D0/en active Pending
-
1992
- 1992-10-02 MY MYPI92001793A patent/MY108233A/en unknown
- 1992-10-08 SK SK445-94A patent/SK283516B6/en unknown
- 1992-10-08 WO PCT/GB1992/001830 patent/WO1993007909A1/en active IP Right Grant
- 1992-10-08 ES ES92920844T patent/ES2149179T3/en not_active Expired - Lifetime
- 1992-10-08 AT AT92920844T patent/ATE193831T1/en active
- 1992-10-08 BR BR9206639A patent/BR9206639A/en not_active IP Right Cessation
- 1992-10-08 KR KR1019940701105A patent/KR100245405B1/en not_active IP Right Cessation
- 1992-10-08 PL PL92303102A patent/PL175272B1/en not_active IP Right Cessation
- 1992-10-08 HU HU9401098A patent/HU214287B/en unknown
- 1992-10-08 EP EP92920844A patent/EP0609266B1/en not_active Expired - Lifetime
- 1992-10-08 US US08/211,659 patent/US5545343A/en not_active Expired - Fee Related
- 1992-10-08 AU AU26806/92A patent/AU670540B2/en not_active Ceased
- 1992-10-08 CA CA002121340A patent/CA2121340C/en not_active Expired - Fee Related
- 1992-10-08 CZ CZ1994923A patent/CZ288552B6/en not_active IP Right Cessation
- 1992-10-08 IN IN625MA1992 patent/IN174157B/en unknown
- 1992-10-08 DE DE69231180T patent/DE69231180T2/en not_active Expired - Lifetime
- 1992-10-08 RU RU94028891/14A patent/RU2122434C1/en not_active IP Right Cessation
- 1992-10-08 JP JP5507512A patent/JP2843438B2/en not_active Expired - Fee Related
- 1992-10-14 PT PT100958A patent/PT100958B/en not_active IP Right Cessation
- 1992-10-15 NZ NZ244750A patent/NZ244750A/en unknown
- 1992-10-16 MX MX9205956A patent/MX9205956A/en not_active IP Right Cessation
- 1992-10-16 ZA ZA928002A patent/ZA928002B/en unknown
-
1994
- 1994-04-15 NO NO941368A patent/NO308397B1/en not_active IP Right Cessation
- 1994-04-15 FI FI941747A patent/FI110671B/en active
-
1995
- 1995-06-02 US US08/458,902 patent/US5624634A/en not_active Expired - Fee Related
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| MKLA | Lapsed |