CA2016062A1 - Liquid disinfectant concentrate - Google Patents
Liquid disinfectant concentrateInfo
- Publication number
- CA2016062A1 CA2016062A1 CA002016062A CA2016062A CA2016062A1 CA 2016062 A1 CA2016062 A1 CA 2016062A1 CA 002016062 A CA002016062 A CA 002016062A CA 2016062 A CA2016062 A CA 2016062A CA 2016062 A1 CA2016062 A1 CA 2016062A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- liquid disinfectant
- weight
- concentrate
- disinfectant concentrate
- 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.)
- Abandoned
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Classifications
-
- 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
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/04—Oxygen or sulfur attached to an aliphatic side-chain of a carbocyclic ring system
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Pulleys (AREA)
- Jet Pumps And Other Pumps (AREA)
Abstract
A B S T R A C T
The invention relates to a liquid disinfectant concentrate which comprises as active-oxygen component peroxymonosulfuric acid and/or its salts. The concentrate comprises as the surfactant component predominantly or exclusively i) primary or secondary alkylsulfonic acids containing a linear, branched or cyclic alkyl group of 6 to 18 carbon atoms, and/or ii) aromatic sulfonic acids of the formula in which R is a branched or linear alkyl radical of 8 to 18 carbon atoms and m and n are in each case 0 or 1, with the proviso that the total of m + n is either 1 or 2, and/or iii) salts of these sulfonic acids.
The concentrate furthermore comprises water and, if desired, stabilizers, agents for enhancing fungicidal potency and other customary additives.
The invention relates to a liquid disinfectant concentrate which comprises as active-oxygen component peroxymonosulfuric acid and/or its salts. The concentrate comprises as the surfactant component predominantly or exclusively i) primary or secondary alkylsulfonic acids containing a linear, branched or cyclic alkyl group of 6 to 18 carbon atoms, and/or ii) aromatic sulfonic acids of the formula in which R is a branched or linear alkyl radical of 8 to 18 carbon atoms and m and n are in each case 0 or 1, with the proviso that the total of m + n is either 1 or 2, and/or iii) salts of these sulfonic acids.
The concentrate furthermore comprises water and, if desired, stabilizers, agents for enhancing fungicidal potency and other customary additives.
Description
me invention relates to a liquid disinfectant concentrate.
The biocidal acti~-ity of peroxymonosulfuric acid (Caro's acid) and its salts is known.
U.S. Patents Nos. 3,873,696 and 3,584l119 disclose bactericidal and fungicidal agents containing salts of Caro's acid.
U.S. Patent 4,404,191 discloses the use of salts of peroxymonosulfuric acid (Caro's acid) as a virucidal agent and that in formulating the peroxymonosulfate salts, either in aqueous media or as dry mixtures, it is preferable to add one or more surfactants, especially of the class of nonionic surfactants such a~ ethoxylated fatty alcohols and/or anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates and fatty acid ethionates. Two specific formulations are exemplified, both dry mixtures adapted for use in aqueous media. one of the exemplified formulations includes inter alia 12.0 weight-percent commercial potas ium peroxymonosulfate (contains 45~wt S KHSO5) and 5.0 weight percent sodium alkane sulfonate and a 20% use-dilution thereof is - disclosed. 20 Weight percent fatty acid ethionate sodium salt is also included, which these represents the predominant surfactant present.
:
~:
0~6~
In the meantime such pulverulent disinfectant preparations are commercially available. To prepare ready-for-use disinfectant solutions from these, the user dissolves them in water immediately prior to use.
In the application concentration which is many times lower than the concentration of a liquid disinfectant concentrate, the incompatibil:ity in solution between Caro's acid and the anionic surfactant, described above, plays a very much lesser role.
The known pulverulent preparations have a number of drawbacks. The metering of the required amount, for example by means of a measuring cup, is tedious. The particularly practical liquid metering devices are unsuitable.
For reasons of technical requirements, pulverulent preparations contain builders or inert components which make no contribution to tha actual application, i.e. disinfection, and may even cause interference. In many cases they also create residues in use. In addition, inert components increase the salt content of effluents.
The preparation and the use of pulverulent preparations are connected with the undesirable presence of dust. The dust can irritate ~ucous membranes, ~ -especially mucous membranes in the nose. For this reason such preparations are objectionable from the point of view of industrial medicine.
Pulverulent diæinfection preparations have the further drawback that often considerable time is required for complete dissolution in water. In addition, the energy input for the preparation of pulverulent products is higher than that for the preparation of liquid products.
The larger the container, the more difficult it is to control the thermal processes of solids containing active oxygen, which can laad to uncontrolled decomposition reactions.
- : :
Finally, inert substances which must~ X
inevitably be present in pulverul~nt preparations, may impair the biocidal potency. The choice of formulation components and their amount relstricted in the case o~
solid prepara~ions.
EP-A-188,025 (published European application) discloses aqueous, thickened cLeansing agents which contain peroxymonosulfuric acid or its salts, a strong acid and the surfactants amine oxides, amines or cationic compounds having a thickening effect. It is expressly stated that anionic surfactants such as linear alkyl sulfates, alkyl sulfonates and alkylbenzene-sulfonates may only be added in small amounts (cf. EP-A-188,025, column 3, lines 61-65).
No liquid, stable disinfectant concentrates based on peroxymonosulfuric acid and/or its salts have so far appeared on the market. This points to the fact that problems regarding stability and technical application have so far not been satisfactorily solved for such liquid formulations.
It is the ob~ect of the invention to provide a liquid disinfectant concentrate with a long shelf life which contains as active-oxygen component peroxymonosulfuric acid and/or its salts and has a 25 stability which is adequate for a commercial product as well as satisfactory technical application ~haracteristics. ~ ;
The ob~ect is achieved by a liquid disinfectant concentrate which comprises A) as the active-oxygen component peroxymonosulfuric acid and~or its salts, B) as the surfactant component predominantly or exclusively i) primary or secondary alkylsulfonic acids containing a linear, branched or cyclic alkyl group of 6 to 18 carbon atoms, and/or ii) aromatic sulfonic acids of the formula o R
(S03H)m (S03H~n in which R is a branched or linaar alkyl radical of 8 to 18 carbon atoms and m and n are in each case O or 1, with the proviso that the total of m + n is eith~r 1 or 2, and/or iii) salts of these sulfonic acids as well as water and, if desired, stabilizers, agents for enhancing the fungicidal potency and other customary additives.
The disinfectant concentrate according to the invention is chemically and physically stable. On th-one hand the active-oxygen content is retained in the concentrate over a long period of time. On the other hand no phase separation takes place; no precipi~ates form; the components are mutually compatible and remain in clear solution over a long period of time.~The surfactants used according to the invention support the disinfection and cleansing action and reinforce these to the extent of a synergistic rise of activity.
Surprisingly, in contrast to the claim of EP-A-188,025 re~erred to above, it is precisely the selected, special anionic surfactants which should be used according to the present invention for the preparation of liquid formulations of peroxymonosulfuric acid and its salts with a long shelf life.
The overwhelming majority of commercially ~
available surfactants are unsuitable for the preparation of disinfectant concentrat-s based on peroxy~onosulfuric acid and its salts. Formulations consisting of 10 ~ by weight of caroate, 2.5 % by~weight of surfactant and 87.5 ~ by weight of water normally exhibit incompatibility between the components, as demonstrated by phase separation, precipitation, non-homogeneity and destabilization of the active-oxygen compound. In view 2g~6~
of the large number of unsuitable surfactants it is surprising that it was possible to find special surfactants which do not exhibit these incompatibilities.
It is preferred according to the invention that the active-oxygen component A) is present in the disinfectant concentrate in the form of the mixture (triple salt) designated as Caro-like, and contains approximately 45 % by weight RHS05, 30 ~ by weight K2S04 and 25 ~ by weight KHS04.
The concentration of the active-oxygen component A) in the disinfectant concentrate is usually between 1 % by weight up to the point of maximum solubility. The concentration of the active-oxygen component A) is preferably 5 to 15 ~ by weight.
The primary or secondary alkylsulfonic acids used as the surfactant component B) i) contain 8 to 16 carbon atoms in the alkyl group.
Regarding the aromatic sulfonic acids of the formula ' \~R
(S03H)m (S03~)n used as the surfactant component ~) ii), it is preferred that the group R is a linear alkyl radical of 10 to 16 carbon atoms.
It is further preferred that in the formula of the aromatic sulfonic acid B) ii) the total of m ~ n = 2.
It i5 also preferred that in the formula of the aromatic sulfonic acid B) ii) the alkyl radicals R
are in the para position to the ether oxygen bridge.
Regarding the sulfonic acid salts B) iiij, it is preferred that they are alkali metal salts, alkaline earth metal salts and~or ammonium salts.
- 6 ~
In the disinfectant concentrate according to the invention the surfactant component B) is usually present in an amount from 0.1 to 200 %, preferably 1 to 100 % and particularly preferably 5 to 50 %, based on the weight of the active-oxygen component A).
To ensure good stability of the disinfectant concentrate according to the invention, it is very important that the chloride content in the liquid concentrate does not exceed an upper limit. The lo disinfectant concentrate according to the invention preferably contains less than 0.5 % by weight of chloride. On the other hand, very small amounts of chloride can have a stabilizing action. It~is therefore particularly preferred that the chloride content of the~
concentrate according to the invention is in the region from 0.005 to 0.5 % by weight.
It may be expedient to add stabilizers to the disinfectant concentrate according to the invention.
Certain phosphonic acids, especially l-hydroxyethane-l,l-diphosphonic acid, morpholinomethane-diphosphonic acid or amino-tris-methylenephosphonic acid, are suitable for this purpose. Pyridinecarboxylic acids, especially pyridine-2,6-dicarboxylic acid, are likewise suitable stabilizers. Finally it is also possible to use for thi~ purpose pyrrolidone acids, especially~2-pyrrolidone-5-carboxylic acid. The said stabilizers may also be employed in the form of their salts or in combination with their salts. It is preferred that the stabilizer are present in the disinfectant concentrate according to the invention in a concentration from 0.01 to 2 % by weight.
For some applications it may be desirable that the disinfectant concentrate according to the invention contains an agent for~enhancing fungicidal potency~ The agents prefsrred for this purpose are N-octylisodiazol-3-one and/or benzoic acids and/or salts of these~
compounds. Theee agents for enhancing fungicidal - 7 ~ X
potency are preferably present in the disinfectant concentrate accordinq to the invention in a concentration from 0.1 to 3 % by weight.
The typical watQr cont~nt of the disinfectant concentrate according to the invention is in the rQgion from 40 to g9 % by weight, prefera~ly 60 to 95 % by weight and most preferably 80 to 90 % by weight.
The pH of the disin~ectant concentrate according to the invention is normally 0 to 6, lo preferably 0.5 to 2.5.
The invention also relates to the use of the liquid disinfectant concentrate for the preparation o~ a ready-for-use disinfectant solution by dilution with water. The concentrate according to the invention is normally diluted for this purpose with water to a 20 to 400 fold volume. The diluted, ready-for-use disinfectant solution prepared in this manner has a typical pH in the region from 2 to 4. It is suitable for carrying out disinfection in the greatest variety of fields. Examples are surfaces, equipment, instruments, materials for use in the medical, industrial and commercial sectors (for example in breweries, dairies, abattoirs, pharmaceutical sector, foodstuff sector), in the house and kitchen, and in the sanitary and veterinary sectors. The ready-for-use disinfectant may be used inter alia in the following manners: spraying, wiping, pouring, dipping, insertion, by a high-pressure method, moist fabrics. The disinfectants may be employed for cleansing,~cleansing with a disinfectant action, disinfection and reduction of microorganism~
count. The disinfectant~may be used in combination with suitable cleansing agent~ or other disinfectants. The disinfectant solutions according to the invention~have a wide spectrum of activity, for example against bacterià, molds, yeast~, mycobacteria, viruses with and without ~ ;
envelopes, and both vegetative microorganisms as well as their permanent forms.
Dyes, odorants and corrosion inhibitors may be additionally added to the disinfectant concentrate according to the invantion.
The examples below elucidate the invention in greater detail.
~xample 1 87.5 % by weight of water, FD (fully demineraliZQd) lO % ~y weight of caroate ("Caro-likel' above) lo 2.5 % by weight of a 45 % by weight solution of the sodium salt B) iii) of the aromatic sulfonic acid Dowfax 3B2 (Clo linear alkylated sodium diphenyloxide disulphonate~
A clear, faintly yellowish and virtually odorless concentrate which was visually unchanged even after one month, was obtained. The KHS05 content immediately after the preparation was 4.3 ~ by weight.
After one month a content of 4.3 % by weight was det~rmined. After 4 months the content was 4.0 ~ by 20 weight.
Example 2 87.3 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of a 45 % by weight solution of Dowfax 3B2 0.2 % by weigh$ of amino-tris-methylenephosphonic acid.
A clear, yellowish~and virtually odorless concentrate was obtained which was visually unchanged after one month. Immediately after the preparation a KHS05 content of 4.4 % by weight was determined. After one month and after 4 months the content in each case~
was 4.0 % by weiqht.
Exampie 3 87.3 % by weight of water, FD
lO % by weight of caroate 2.5 % by weight of a 45 % by weight solution - 9 - ~ o:~
of Dowfax 3B2 O.1 % by weight of pyridine-2,6-dicarboxylic acid 0.1 % by weight of amino-tris-methylenephosphonic acid.
A clear, yellowish and virtually odarless concentrate was obtained which was visually unchanged after one month. Immediately after the preparation a KHSO5 content of 4.3 S by weight was determined. After one month the content was 4.2 % by weight, after 4 months at room temperature the content was 3.9 % by weight.~
Example 4 87.5 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of alkylsulfonic acid as its sodium ~alt B) iii) = Nergolat W-93 (Bayer A.G.), C10-Cl8 linear a}kyl sodium alkyl sulfonate) The above components gave rise to a clear, almost colorless and odorless concentrate which was visually unchanged after one month. Immediately after the preparation the KHS05 content was 4.0 % by weight.
After one month a content of 3.9 % by weight was determined, after 4 months the content was 3.7 % by weight.
Example 5 87.3 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of Mergolat W-93 0.2 % by weiqht of amino-tris- ;~
methylenephosphonic acid.
A clear, almost oolorless and virtually odorless concentrate which was visually unchanged even after one month, was obtained. Immediately after the preparation the KHS05 content was 4.0 % by weight.
After one month a content o~ 3.9 % by weight was determined. After 4 ~onths the content was 3.7 % by weight.
Example 6 87.3 % by weight of water, ~D
10 % by weight of caroate 2.5 % by weiyht of Mergolat W-93 O.1 % by weight of pyridine-2,6-dicarboxylic acid 0.1 ~ by weight of amino-tris-methylenephosphonic acid.
A clear, almost colorless and virtually odorless concentrate which wàs visually unchanged after one month, was obtained. Immediately aft~er the preparation a KHS05 content of 4.0 % by wleight wa determined. After one ~onth the content ~as 3.8 % by weight, after 4 months the content was 3.4 % by weight.
The above Examples l to 6 illustrate the good stability of the disinfectant concentrate according to the invention. The examples below illustrate the application of the disinfectant concentrates to the invention for the preparation of ready-for-use solutions which are good disinfectants.
Example 7 85.3 % by weight of water, FD
12.0 % by weight of caroate 2.5 % by weight of a 45 % by weight solution of Dowfax 3B2 0.2 ~ by weight of amino-tris-methylenephosphonic acid.
The above components gave rise to a clear, faintly yellowish and virtually odorless disinfectant concentrate. Ready-for-use solutions, containing 3.00, 2.00, 1.00, 0.50 and 0.25 % by volume of the concentrate, were prepared from this concentrate by dilution with water. (It is of course possible, if d~sired, to use a higher concentration, for exa~ple with a higher degree of soiling or for resistant micro-.
organisms.) These ready-for-use solutions of different dilution were used for suspension tests in accordance with the guidelines for the te'sting of chemical disinfectants, issued by the G,erman Society for Veterinary Nedicine, produced by the committee "Disinfection in veterinary medicine", new edition 1984.
The tests were carried out both with albumin and without albumin, once using 10 % bovine serum and once using 20 % bovine serum. The results are given in Table I below.
The figures in the table indicate in each case the time required for killing the micro-organisms.
The table illustrates th~ good disinfectant action of the ready-for-use solutions prepared according to the invention.
a~ dP
~ a~ 3 U~ 3 Ul .1 OO C~
D ~D ~ D ~D ~D ~D ~D ~D ~ D
A 1~ ~ ~ A A
u~ ~oo~ oooo D ~D lD ~ D
Ia C~ U A A A ~ A A A A
~
.~
,8 U~utOo U~U~OO
O ~11~ Ir) It~ D U~ D ~D
A A
_~a~
OU~ ~ o o o o o o o D ~ D ~D ~D
p~ ~ A A ~ A A
a. ~
ooo oooo h ~ D ~D U~
U~ ~ A A ~ A A
o 0 0 0 0 0 0 0 0 D ~ D ~D ~D
v~ a A A ~ A A A
S~ ~
~a oOoou~ oOoou~ oO
11~ O O O Y~ N O O O U~ N O O O 11 0 0 ~ 0 0 1~ ~ _1 0 Example 8 80.8 % by weight of water, FD
12.0 % by weight of caroate 5.0 % by weight of a 45 ~ by weight solution of Dowfax 3B~
0.2 % by weight of amino-tris-methylene~phosphonic acid.
0.2 ~ by weight of benzoic acid 2.0 % by weight of a mixture of 45 parts by lo weight of N-octylisothiazolone and 55 parts hy weight of 1,2-propylene glyc~
The above components gave rise to a clear disinfectant concentrate. Ready-for-use solutions containing 3, 2 and 1 ~ hy volume of the concentrate, were prepared from the concentrate by dilution with water.
The ready-for-use solutions of different dilution were subjected to a suspension test according to the "Guide-lines for the testing and evaluation o~
chemical disinfection processes" of the German society for Hygiene and Microbiology (cf. Zentralblatt fl~r Bakteriologie, Mikrobiologie und Hygiene, Series B:
Hygiene, environmental hygiene, hospital hygiene, industrial hygiene, preventive medicine; volume 172, No.
6 (1981)).
The tests were carried out with Candida albicans and Aspergillus niger. They were carried out with and without albumin, the latter tests with 10 %
bovine serum.
The results are given in Table II below. It is clear from the table that this di~infectant had an improved fungicidal potency.
Table II
Concentration Candida Aspergillus used [~] albicans niger without 2 5 5 serum 1 5 5 with 2 5 30 10% serum 1 :30 30 Examples 9 to 13 Disinfectant concentrates were prepared having compositions as stated in Table III. Virtually odorless concentrates were obtained; their appearance immediately after the preparation is described in Table III.
Samples of these concentrates were retained for 9 months at room temperature (RT) and at a slightly elavated temperature (40). Table III shows the change of the KHSO5 content in relation to storage temperature and time. In addition, the appearance after 9 months is listed.
Examples 9 to 13 indicate that a small amount of chloride in the concentrate has a favorable influence on stability.
- 15 ~ L~
O -- L ~ O O
_ ~ 1 0 0 _ ~ L L
O ~ _ ~t ~ O
_ ~;5 _ t~l O O O ~-- L L
L~ i!l L ~ ~ O
_ a~N s~i o o o y , L L
~1 o~ cl ~ r> o _ 0 O, U- Co~l o~J o ~ ~ L ~ D _ D ~
O U P~ C~ O
a~ ~ o o' I l_ u U
U J
e ~ . a ~ i 8 ; ~ u _ ~ ~,~ o ~ C o " ~ ~ , ~ ~j L L L
The biocidal acti~-ity of peroxymonosulfuric acid (Caro's acid) and its salts is known.
U.S. Patents Nos. 3,873,696 and 3,584l119 disclose bactericidal and fungicidal agents containing salts of Caro's acid.
U.S. Patent 4,404,191 discloses the use of salts of peroxymonosulfuric acid (Caro's acid) as a virucidal agent and that in formulating the peroxymonosulfate salts, either in aqueous media or as dry mixtures, it is preferable to add one or more surfactants, especially of the class of nonionic surfactants such a~ ethoxylated fatty alcohols and/or anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates and fatty acid ethionates. Two specific formulations are exemplified, both dry mixtures adapted for use in aqueous media. one of the exemplified formulations includes inter alia 12.0 weight-percent commercial potas ium peroxymonosulfate (contains 45~wt S KHSO5) and 5.0 weight percent sodium alkane sulfonate and a 20% use-dilution thereof is - disclosed. 20 Weight percent fatty acid ethionate sodium salt is also included, which these represents the predominant surfactant present.
:
~:
0~6~
In the meantime such pulverulent disinfectant preparations are commercially available. To prepare ready-for-use disinfectant solutions from these, the user dissolves them in water immediately prior to use.
In the application concentration which is many times lower than the concentration of a liquid disinfectant concentrate, the incompatibil:ity in solution between Caro's acid and the anionic surfactant, described above, plays a very much lesser role.
The known pulverulent preparations have a number of drawbacks. The metering of the required amount, for example by means of a measuring cup, is tedious. The particularly practical liquid metering devices are unsuitable.
For reasons of technical requirements, pulverulent preparations contain builders or inert components which make no contribution to tha actual application, i.e. disinfection, and may even cause interference. In many cases they also create residues in use. In addition, inert components increase the salt content of effluents.
The preparation and the use of pulverulent preparations are connected with the undesirable presence of dust. The dust can irritate ~ucous membranes, ~ -especially mucous membranes in the nose. For this reason such preparations are objectionable from the point of view of industrial medicine.
Pulverulent diæinfection preparations have the further drawback that often considerable time is required for complete dissolution in water. In addition, the energy input for the preparation of pulverulent products is higher than that for the preparation of liquid products.
The larger the container, the more difficult it is to control the thermal processes of solids containing active oxygen, which can laad to uncontrolled decomposition reactions.
- : :
Finally, inert substances which must~ X
inevitably be present in pulverul~nt preparations, may impair the biocidal potency. The choice of formulation components and their amount relstricted in the case o~
solid prepara~ions.
EP-A-188,025 (published European application) discloses aqueous, thickened cLeansing agents which contain peroxymonosulfuric acid or its salts, a strong acid and the surfactants amine oxides, amines or cationic compounds having a thickening effect. It is expressly stated that anionic surfactants such as linear alkyl sulfates, alkyl sulfonates and alkylbenzene-sulfonates may only be added in small amounts (cf. EP-A-188,025, column 3, lines 61-65).
No liquid, stable disinfectant concentrates based on peroxymonosulfuric acid and/or its salts have so far appeared on the market. This points to the fact that problems regarding stability and technical application have so far not been satisfactorily solved for such liquid formulations.
It is the ob~ect of the invention to provide a liquid disinfectant concentrate with a long shelf life which contains as active-oxygen component peroxymonosulfuric acid and/or its salts and has a 25 stability which is adequate for a commercial product as well as satisfactory technical application ~haracteristics. ~ ;
The ob~ect is achieved by a liquid disinfectant concentrate which comprises A) as the active-oxygen component peroxymonosulfuric acid and~or its salts, B) as the surfactant component predominantly or exclusively i) primary or secondary alkylsulfonic acids containing a linear, branched or cyclic alkyl group of 6 to 18 carbon atoms, and/or ii) aromatic sulfonic acids of the formula o R
(S03H)m (S03H~n in which R is a branched or linaar alkyl radical of 8 to 18 carbon atoms and m and n are in each case O or 1, with the proviso that the total of m + n is eith~r 1 or 2, and/or iii) salts of these sulfonic acids as well as water and, if desired, stabilizers, agents for enhancing the fungicidal potency and other customary additives.
The disinfectant concentrate according to the invention is chemically and physically stable. On th-one hand the active-oxygen content is retained in the concentrate over a long period of time. On the other hand no phase separation takes place; no precipi~ates form; the components are mutually compatible and remain in clear solution over a long period of time.~The surfactants used according to the invention support the disinfection and cleansing action and reinforce these to the extent of a synergistic rise of activity.
Surprisingly, in contrast to the claim of EP-A-188,025 re~erred to above, it is precisely the selected, special anionic surfactants which should be used according to the present invention for the preparation of liquid formulations of peroxymonosulfuric acid and its salts with a long shelf life.
The overwhelming majority of commercially ~
available surfactants are unsuitable for the preparation of disinfectant concentrat-s based on peroxy~onosulfuric acid and its salts. Formulations consisting of 10 ~ by weight of caroate, 2.5 % by~weight of surfactant and 87.5 ~ by weight of water normally exhibit incompatibility between the components, as demonstrated by phase separation, precipitation, non-homogeneity and destabilization of the active-oxygen compound. In view 2g~6~
of the large number of unsuitable surfactants it is surprising that it was possible to find special surfactants which do not exhibit these incompatibilities.
It is preferred according to the invention that the active-oxygen component A) is present in the disinfectant concentrate in the form of the mixture (triple salt) designated as Caro-like, and contains approximately 45 % by weight RHS05, 30 ~ by weight K2S04 and 25 ~ by weight KHS04.
The concentration of the active-oxygen component A) in the disinfectant concentrate is usually between 1 % by weight up to the point of maximum solubility. The concentration of the active-oxygen component A) is preferably 5 to 15 ~ by weight.
The primary or secondary alkylsulfonic acids used as the surfactant component B) i) contain 8 to 16 carbon atoms in the alkyl group.
Regarding the aromatic sulfonic acids of the formula ' \~R
(S03H)m (S03~)n used as the surfactant component ~) ii), it is preferred that the group R is a linear alkyl radical of 10 to 16 carbon atoms.
It is further preferred that in the formula of the aromatic sulfonic acid B) ii) the total of m ~ n = 2.
It i5 also preferred that in the formula of the aromatic sulfonic acid B) ii) the alkyl radicals R
are in the para position to the ether oxygen bridge.
Regarding the sulfonic acid salts B) iiij, it is preferred that they are alkali metal salts, alkaline earth metal salts and~or ammonium salts.
- 6 ~
In the disinfectant concentrate according to the invention the surfactant component B) is usually present in an amount from 0.1 to 200 %, preferably 1 to 100 % and particularly preferably 5 to 50 %, based on the weight of the active-oxygen component A).
To ensure good stability of the disinfectant concentrate according to the invention, it is very important that the chloride content in the liquid concentrate does not exceed an upper limit. The lo disinfectant concentrate according to the invention preferably contains less than 0.5 % by weight of chloride. On the other hand, very small amounts of chloride can have a stabilizing action. It~is therefore particularly preferred that the chloride content of the~
concentrate according to the invention is in the region from 0.005 to 0.5 % by weight.
It may be expedient to add stabilizers to the disinfectant concentrate according to the invention.
Certain phosphonic acids, especially l-hydroxyethane-l,l-diphosphonic acid, morpholinomethane-diphosphonic acid or amino-tris-methylenephosphonic acid, are suitable for this purpose. Pyridinecarboxylic acids, especially pyridine-2,6-dicarboxylic acid, are likewise suitable stabilizers. Finally it is also possible to use for thi~ purpose pyrrolidone acids, especially~2-pyrrolidone-5-carboxylic acid. The said stabilizers may also be employed in the form of their salts or in combination with their salts. It is preferred that the stabilizer are present in the disinfectant concentrate according to the invention in a concentration from 0.01 to 2 % by weight.
For some applications it may be desirable that the disinfectant concentrate according to the invention contains an agent for~enhancing fungicidal potency~ The agents prefsrred for this purpose are N-octylisodiazol-3-one and/or benzoic acids and/or salts of these~
compounds. Theee agents for enhancing fungicidal - 7 ~ X
potency are preferably present in the disinfectant concentrate accordinq to the invention in a concentration from 0.1 to 3 % by weight.
The typical watQr cont~nt of the disinfectant concentrate according to the invention is in the rQgion from 40 to g9 % by weight, prefera~ly 60 to 95 % by weight and most preferably 80 to 90 % by weight.
The pH of the disin~ectant concentrate according to the invention is normally 0 to 6, lo preferably 0.5 to 2.5.
The invention also relates to the use of the liquid disinfectant concentrate for the preparation o~ a ready-for-use disinfectant solution by dilution with water. The concentrate according to the invention is normally diluted for this purpose with water to a 20 to 400 fold volume. The diluted, ready-for-use disinfectant solution prepared in this manner has a typical pH in the region from 2 to 4. It is suitable for carrying out disinfection in the greatest variety of fields. Examples are surfaces, equipment, instruments, materials for use in the medical, industrial and commercial sectors (for example in breweries, dairies, abattoirs, pharmaceutical sector, foodstuff sector), in the house and kitchen, and in the sanitary and veterinary sectors. The ready-for-use disinfectant may be used inter alia in the following manners: spraying, wiping, pouring, dipping, insertion, by a high-pressure method, moist fabrics. The disinfectants may be employed for cleansing,~cleansing with a disinfectant action, disinfection and reduction of microorganism~
count. The disinfectant~may be used in combination with suitable cleansing agent~ or other disinfectants. The disinfectant solutions according to the invention~have a wide spectrum of activity, for example against bacterià, molds, yeast~, mycobacteria, viruses with and without ~ ;
envelopes, and both vegetative microorganisms as well as their permanent forms.
Dyes, odorants and corrosion inhibitors may be additionally added to the disinfectant concentrate according to the invantion.
The examples below elucidate the invention in greater detail.
~xample 1 87.5 % by weight of water, FD (fully demineraliZQd) lO % ~y weight of caroate ("Caro-likel' above) lo 2.5 % by weight of a 45 % by weight solution of the sodium salt B) iii) of the aromatic sulfonic acid Dowfax 3B2 (Clo linear alkylated sodium diphenyloxide disulphonate~
A clear, faintly yellowish and virtually odorless concentrate which was visually unchanged even after one month, was obtained. The KHS05 content immediately after the preparation was 4.3 ~ by weight.
After one month a content of 4.3 % by weight was det~rmined. After 4 months the content was 4.0 ~ by 20 weight.
Example 2 87.3 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of a 45 % by weight solution of Dowfax 3B2 0.2 % by weigh$ of amino-tris-methylenephosphonic acid.
A clear, yellowish~and virtually odorless concentrate was obtained which was visually unchanged after one month. Immediately after the preparation a KHS05 content of 4.4 % by weight was determined. After one month and after 4 months the content in each case~
was 4.0 % by weiqht.
Exampie 3 87.3 % by weight of water, FD
lO % by weight of caroate 2.5 % by weight of a 45 % by weight solution - 9 - ~ o:~
of Dowfax 3B2 O.1 % by weight of pyridine-2,6-dicarboxylic acid 0.1 % by weight of amino-tris-methylenephosphonic acid.
A clear, yellowish and virtually odarless concentrate was obtained which was visually unchanged after one month. Immediately after the preparation a KHSO5 content of 4.3 S by weight was determined. After one month the content was 4.2 % by weight, after 4 months at room temperature the content was 3.9 % by weight.~
Example 4 87.5 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of alkylsulfonic acid as its sodium ~alt B) iii) = Nergolat W-93 (Bayer A.G.), C10-Cl8 linear a}kyl sodium alkyl sulfonate) The above components gave rise to a clear, almost colorless and odorless concentrate which was visually unchanged after one month. Immediately after the preparation the KHS05 content was 4.0 % by weight.
After one month a content of 3.9 % by weight was determined, after 4 months the content was 3.7 % by weight.
Example 5 87.3 % by weight of water, FD
10 % by weight of caroate 2.5 % by weight of Mergolat W-93 0.2 % by weiqht of amino-tris- ;~
methylenephosphonic acid.
A clear, almost oolorless and virtually odorless concentrate which was visually unchanged even after one month, was obtained. Immediately after the preparation the KHS05 content was 4.0 % by weight.
After one month a content o~ 3.9 % by weight was determined. After 4 ~onths the content was 3.7 % by weight.
Example 6 87.3 % by weight of water, ~D
10 % by weight of caroate 2.5 % by weiyht of Mergolat W-93 O.1 % by weight of pyridine-2,6-dicarboxylic acid 0.1 ~ by weight of amino-tris-methylenephosphonic acid.
A clear, almost colorless and virtually odorless concentrate which wàs visually unchanged after one month, was obtained. Immediately aft~er the preparation a KHS05 content of 4.0 % by wleight wa determined. After one ~onth the content ~as 3.8 % by weight, after 4 months the content was 3.4 % by weight.
The above Examples l to 6 illustrate the good stability of the disinfectant concentrate according to the invention. The examples below illustrate the application of the disinfectant concentrates to the invention for the preparation of ready-for-use solutions which are good disinfectants.
Example 7 85.3 % by weight of water, FD
12.0 % by weight of caroate 2.5 % by weight of a 45 % by weight solution of Dowfax 3B2 0.2 ~ by weight of amino-tris-methylenephosphonic acid.
The above components gave rise to a clear, faintly yellowish and virtually odorless disinfectant concentrate. Ready-for-use solutions, containing 3.00, 2.00, 1.00, 0.50 and 0.25 % by volume of the concentrate, were prepared from this concentrate by dilution with water. (It is of course possible, if d~sired, to use a higher concentration, for exa~ple with a higher degree of soiling or for resistant micro-.
organisms.) These ready-for-use solutions of different dilution were used for suspension tests in accordance with the guidelines for the te'sting of chemical disinfectants, issued by the G,erman Society for Veterinary Nedicine, produced by the committee "Disinfection in veterinary medicine", new edition 1984.
The tests were carried out both with albumin and without albumin, once using 10 % bovine serum and once using 20 % bovine serum. The results are given in Table I below.
The figures in the table indicate in each case the time required for killing the micro-organisms.
The table illustrates th~ good disinfectant action of the ready-for-use solutions prepared according to the invention.
a~ dP
~ a~ 3 U~ 3 Ul .1 OO C~
D ~D ~ D ~D ~D ~D ~D ~D ~ D
A 1~ ~ ~ A A
u~ ~oo~ oooo D ~D lD ~ D
Ia C~ U A A A ~ A A A A
~
.~
,8 U~utOo U~U~OO
O ~11~ Ir) It~ D U~ D ~D
A A
_~a~
OU~ ~ o o o o o o o D ~ D ~D ~D
p~ ~ A A ~ A A
a. ~
ooo oooo h ~ D ~D U~
U~ ~ A A ~ A A
o 0 0 0 0 0 0 0 0 D ~ D ~D ~D
v~ a A A ~ A A A
S~ ~
~a oOoou~ oOoou~ oO
11~ O O O Y~ N O O O U~ N O O O 11 0 0 ~ 0 0 1~ ~ _1 0 Example 8 80.8 % by weight of water, FD
12.0 % by weight of caroate 5.0 % by weight of a 45 ~ by weight solution of Dowfax 3B~
0.2 % by weight of amino-tris-methylene~phosphonic acid.
0.2 ~ by weight of benzoic acid 2.0 % by weight of a mixture of 45 parts by lo weight of N-octylisothiazolone and 55 parts hy weight of 1,2-propylene glyc~
The above components gave rise to a clear disinfectant concentrate. Ready-for-use solutions containing 3, 2 and 1 ~ hy volume of the concentrate, were prepared from the concentrate by dilution with water.
The ready-for-use solutions of different dilution were subjected to a suspension test according to the "Guide-lines for the testing and evaluation o~
chemical disinfection processes" of the German society for Hygiene and Microbiology (cf. Zentralblatt fl~r Bakteriologie, Mikrobiologie und Hygiene, Series B:
Hygiene, environmental hygiene, hospital hygiene, industrial hygiene, preventive medicine; volume 172, No.
6 (1981)).
The tests were carried out with Candida albicans and Aspergillus niger. They were carried out with and without albumin, the latter tests with 10 %
bovine serum.
The results are given in Table II below. It is clear from the table that this di~infectant had an improved fungicidal potency.
Table II
Concentration Candida Aspergillus used [~] albicans niger without 2 5 5 serum 1 5 5 with 2 5 30 10% serum 1 :30 30 Examples 9 to 13 Disinfectant concentrates were prepared having compositions as stated in Table III. Virtually odorless concentrates were obtained; their appearance immediately after the preparation is described in Table III.
Samples of these concentrates were retained for 9 months at room temperature (RT) and at a slightly elavated temperature (40). Table III shows the change of the KHSO5 content in relation to storage temperature and time. In addition, the appearance after 9 months is listed.
Examples 9 to 13 indicate that a small amount of chloride in the concentrate has a favorable influence on stability.
- 15 ~ L~
O -- L ~ O O
_ ~ 1 0 0 _ ~ L L
O ~ _ ~t ~ O
_ ~;5 _ t~l O O O ~-- L L
L~ i!l L ~ ~ O
_ a~N s~i o o o y , L L
~1 o~ cl ~ r> o _ 0 O, U- Co~l o~J o ~ ~ L ~ D _ D ~
O U P~ C~ O
a~ ~ o o' I l_ u U
U J
e ~ . a ~ i 8 ; ~ u _ ~ ~,~ o ~ C o " ~ ~ , ~ ~j L L L
Claims (21)
1. A liquid disinfectant concentrate which comprises A) as the active-oxygen component peroxymonosulfuric acid and/or a salt thereof, B) as the surfactant component predominantly or exclusively i) a primary or secondary alkylsulfonic acid containing a linear, branched or cyclic alkyl group of 6 to 18 carbon atoms, and/or ii) a aromatic sulfonic acid of the formula in which R is a branched or linear alkyl radical of 8 to 18 carbon atoms and m and n are in each case 0 or 1, with the proviso that the total of m + n is either 1 or 2, and/or iii) a salt of these sulfonic acids as well as water and, if desired, a stabilizer, agent for enhancing the fungicidal potency or other customary additive.
2. A liquid disinfectant concentrate according to claim 1, in which the active-oxygen component A) is present in the form of a mixture of KHSO5, K2SO4 and KHSO4 (caroate).
3. A liquid disinfectant concentrate as claimed in claim 1, in which the concentration of the active-oxygen component A) is between 1% by weight of the concentrate up to the point of maximum solubility.
4. A liquid disinfectant concentrate as claimed in claim 3, in which the concentration of the active-oxygen component A) is 5 to 15% by weight.
5. A liquid disinfect;mt concentrate as claimed in any of the preceding claims, in which the primary or secondary alkylsulfonic acid B) i) contains 8 to 16 carbon atoms in the alkyl group.
6. A liquid disinfectant concentrate as claimed in any of claims 1-4, in which the group R in the formula of the aromatic sulfonic acid B) ii) is a linear alkyl radical of 10 to 16 carbon atoms.
7. A liquid disinfectant concentrate as claimed in any of claims 1-4, in which in the formula of the aromatic sulfonic acid B) ii) the total of m + n = 2.
8. A liquid disinfectant concentrate as claimed in any of claims 1-4, in which in the formula of the aromatic sulfonic acid B) ii) the alkyl radicals R are in the para position to the ether oxygen bridge.
9. A liquid disinfectant concentrate as claimed in any of claims 1-4, in which the sulfonic acid salt B) iii) is an alkali metal salt, alkaline earth metal salt and/or an ammonium salt.
10. A liquid disinfectant concentrate as claimed in any of claims 1-4, in which the surfactant component B) is present in an amount from 0.1 to 200%, based on the weight of the active-oxygen component A).
11. A liquid disinfectant concentrate as claimed in any of claims 1-4, which comprises not more than 0.5% by weight of chloride.
12. A liquid disinfectant concentrate as claimed in claim 11, in which the chloride content is 0.005 to 0.5% by weight.
13. A liquid disinfectant concentrate as claimed in any of claims 1-4, which comprises 40 to 90% by weight of water.
14. A liquid disinfectant concentrate as claimed in any of claims 1-4, which comprises a phosphonic acid, a pyridinecarboxylic acid, a pyrrolidonecarboxylic acid, and/or a salt thereof as a stabilizer.
15. A liquid disinfectant according to claim 14, in which the phosphonic acid is 1-hydroxyethane-1,1-diphosphonic acid, morpholinomethane-diphosphonic acid or amino -tris-methylenephosphonic acid, the pyridine carboxylic acid is pyridine-2,6-dicarboxylic acid, and the pyrrolidonecarboxylic acid is 2-pyrrolidonle-5-carboxylic acid.
16. A liquid disinfectant concentrate as claimed in any of claims 1-4, which comprises stablizers in a concentration from 0.01 to 2% by weight.
17. A liquid disinfectant concentrate as claimed in any of claims 1-4, which comprises N-octyliso-diazol-3-one and/or benzoic acid and/or a salt of these compounds as an agent for enhancing fungicidal potency.
18. A liquid disinfectant concentrate as claimed in claim 17, which comprises the agent for enhancing fungicidal potency in a concentration from 0.1 to 3% by weight.
19. A liquid disinfectant concentrate as claimed in any of claims 1-4, which has a pH from 0.5 to 2.5.
20. A liquid disinfectant concentrate as claimed in any of claims 1-4, diluted with water as a ready-for-use disinfectant solution.
21. A diluted disinfectant concentrate according to claim 20, in which the liquid disinfectant concentrate is diluted 20 to 400 fold.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3914827A DE3914827C2 (en) | 1989-05-05 | 1989-05-05 | Liquid disinfectant concentrate |
| DEP3914827.0 | 1989-05-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2016062A1 true CA2016062A1 (en) | 1990-11-05 |
Family
ID=6380147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002016062A Abandoned CA2016062A1 (en) | 1989-05-05 | 1990-05-04 | Liquid disinfectant concentrate |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0395902B1 (en) |
| JP (1) | JPH0327304A (en) |
| KR (1) | KR900017471A (en) |
| AT (1) | ATE163837T1 (en) |
| AU (1) | AU5473890A (en) |
| BR (1) | BR9002093A (en) |
| CA (1) | CA2016062A1 (en) |
| DE (1) | DE3914827C2 (en) |
| DK (1) | DK111790A (en) |
| FI (1) | FI902255A7 (en) |
| MX (1) | MX171351B (en) |
| NO (1) | NO901972L (en) |
| PT (1) | PT93960A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12096768B2 (en) | 2019-08-07 | 2024-09-24 | Ecolab Usa Inc. | Polymeric and solid-supported chelators for stabilization of peracid-containing compositions |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818142B2 (en) | 2003-03-31 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Potassium hydrogen peroxymonosulfate solutions |
| FR2923735A1 (en) † | 2007-11-15 | 2009-05-22 | Arkema France | PROCESS FOR ACID CLEANING IN THE BRASSICOLE INDUSTRY |
| US12203056B2 (en) | 2008-03-28 | 2025-01-21 | 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 |
| US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
| BRPI0907918B1 (en) | 2008-03-28 | 2018-07-24 | Ecolab Inc. | SULFOPEROXIC CARBOXYLIC ACIDS, THEIR PREPARATION AND METHODS OF USE AS AN ANTIMICROBYANES |
| US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
| CA2867565C (en) | 2012-03-30 | 2021-01-19 | Victor KEASLER | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
| 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 |
| US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
| US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
| EP3841059A1 (en) | 2018-08-22 | 2021-06-30 | Ecolab USA Inc. | Hydrogen peroxide and peracid stabilization with molecules based on a pyridine carboxylic acid at c-3, -4 or -5 |
| US11628185B2 (en) | 2021-02-17 | 2023-04-18 | Oxion Dental, Llc | Stabilized active oxygen-generating antiseptic compositions, irrigation solutions, and articles |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234140A (en) * | 1964-06-05 | 1966-02-08 | Monsanto Co | Stabilization of peroxy solutions |
| GB1162754A (en) * | 1967-02-21 | 1969-08-27 | Richardson Merrell Ltd | Disinfecting Composition |
| US3584119A (en) * | 1967-06-12 | 1971-06-08 | Langyn Lab Inc | Vaginal douche composition |
| US3873696A (en) * | 1972-01-31 | 1975-03-25 | Allergan Pharma | Cleaning and sterilizing soft contact lens |
| DE2654164C2 (en) * | 1976-11-30 | 1978-08-10 | Schuelke & Mayr Gmbh, 2000 Norderstedt | Aqueous perglutaric acid solution and its use |
| DE3046769C3 (en) * | 1980-12-12 | 1993-12-02 | Schuelke & Mayr Gmbh | The use of caroat as a virucidal agent |
| DE3211677A1 (en) * | 1982-03-30 | 1983-10-06 | Hoechst Ag | LIQUID OXIDATIVE DETOXIFICANT AND METHOD FOR OXIDATIVE DECOXIFYING |
| US4477438A (en) * | 1982-11-12 | 1984-10-16 | Surgikos, Inc. | Hydrogen peroxide composition |
| GB2164851B (en) * | 1984-10-01 | 1987-12-31 | Auchincloss Thomas R | Dry, water soluble biocidal compositions |
| GB8500116D0 (en) * | 1985-01-03 | 1985-02-13 | Unilever Plc | Liquid bleaching compositions |
| GB8508010D0 (en) * | 1985-03-27 | 1985-05-01 | Unilever Plc | Liquid bleaching compositions |
| JPS63502662A (en) * | 1986-03-01 | 1988-10-06 | オ−チンクロス，ト−マス，ラルフ | Biocides, especially virucidal compositions |
| US4804491A (en) * | 1986-11-03 | 1989-02-14 | The Clorox Company | Aqueous based acidic hard surface cleaner |
| US4822511A (en) * | 1988-05-06 | 1989-04-18 | Rohm And Haas Company | Preservative compositions comprising a synergistic mixture of isothiagolones |
-
1989
- 1989-05-05 DE DE3914827A patent/DE3914827C2/en not_active Expired - Lifetime
-
1990
- 1990-04-04 EP EP90106464A patent/EP0395902B1/en not_active Expired - Lifetime
- 1990-04-04 AT AT90106464T patent/ATE163837T1/en not_active IP Right Cessation
- 1990-05-03 NO NO90901972A patent/NO901972L/en unknown
- 1990-05-03 AU AU54738/90A patent/AU5473890A/en not_active Abandoned
- 1990-05-04 FI FI902255A patent/FI902255A7/en not_active Application Discontinuation
- 1990-05-04 MX MX020596A patent/MX171351B/en unknown
- 1990-05-04 CA CA002016062A patent/CA2016062A1/en not_active Abandoned
- 1990-05-04 PT PT93960A patent/PT93960A/en not_active Application Discontinuation
- 1990-05-04 DK DK111790A patent/DK111790A/en unknown
- 1990-05-04 KR KR1019900006348A patent/KR900017471A/en not_active Withdrawn
- 1990-05-04 BR BR909002093A patent/BR9002093A/en unknown
- 1990-05-07 JP JP2117278A patent/JPH0327304A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12096768B2 (en) | 2019-08-07 | 2024-09-24 | Ecolab Usa Inc. | Polymeric and solid-supported chelators for stabilization of peracid-containing compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| AU5473890A (en) | 1990-11-08 |
| JPH0327304A (en) | 1991-02-05 |
| KR900017471A (en) | 1990-12-19 |
| BR9002093A (en) | 1991-08-13 |
| FI902255A0 (en) | 1990-05-04 |
| ATE163837T1 (en) | 1998-03-15 |
| MX171351B (en) | 1993-10-20 |
| DK111790A (en) | 1990-11-06 |
| EP0395902A3 (en) | 1992-04-22 |
| EP0395902A2 (en) | 1990-11-07 |
| PT93960A (en) | 1991-02-08 |
| DE3914827C2 (en) | 1995-06-14 |
| DE3914827A1 (en) | 1990-11-08 |
| FI902255A7 (en) | 1990-11-06 |
| NO901972L (en) | 1990-11-06 |
| DK111790D0 (en) | 1990-05-04 |
| NO901972D0 (en) | 1990-05-03 |
| EP0395902B1 (en) | 1998-03-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |