EP0737738B1 - Bleichmitteltabletten - Google Patents

Bleichmitteltabletten Download PDF

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Publication number
EP0737738B1
EP0737738B1 EP19960610014 EP96610014A EP0737738B1 EP 0737738 B1 EP0737738 B1 EP 0737738B1 EP 19960610014 EP19960610014 EP 19960610014 EP 96610014 A EP96610014 A EP 96610014A EP 0737738 B1 EP0737738 B1 EP 0737738B1
Authority
EP
European Patent Office
Prior art keywords
weight
bleach
tablets
bleach tablets
sodium
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 - Lifetime
Application number
EP19960610014
Other languages
English (en)
French (fr)
Other versions
EP0737738A3 (de
EP0737738A2 (de
Inventor
Erik Schmidt
Anders Bjerre Kristensen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cleantabs AS
Original Assignee
Cleantabs AS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cleantabs AS filed Critical Cleantabs AS
Publication of EP0737738A2 publication Critical patent/EP0737738A2/de
Publication of EP0737738A3 publication Critical patent/EP0737738A3/de
Application granted granted Critical
Publication of EP0737738B1 publication Critical patent/EP0737738B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to bleach tablets intended to be used together with usual textile detergent compositions so as to obtain an improved washing effect and stain removal of bleach-sensitive stains.
  • oxygen-based bleaches such as sodium perborate
  • An increasing awareness of the potential environmental hazard of these boron-containing bleaches has, however, intensified the interest in other oxygen-based bleaches.
  • potassium peroxomonosulphates and alkali metal perhydrates such as sodium percarbonate which are dissolved quickly in water and which in addition to their bleaching effect also have an alkaline effect supporting and intensifying the washing effect.
  • a drawback of sodium percarbonate is, however, its poor stability which presents a limiting factor for its use in detergent compositions.
  • Factors adversely affecting the stability are especially the presence of moisture, temperatures exceeding 28°C to 30°C, as well as the presence of metal ions, such as iron, manganese etc.
  • sodium percarbonate is particularly difficult with respect to the formulation of the tablets because the compression pressure necessary for the tabletting results in heat development which in turn implies that the tablets reach critical temperatures initiating the decomposition of sodium percarbonate.
  • EP publication No. 0 481 792 discloses bleach tablets comprising a bleach activator having a pseudo - first order perhydrolysis rate constant (K obs ) of from 1.5 x 10 -4 to 350 x 10 -4 sec -1 as well as a percarbonate being protected against decomposition by means of an inorganic salt, especially sodium carbonate.
  • K obs pseudo - first order perhydrolysis rate constant
  • Example 4 of the publication describes a bleach tablet composition containing 12.5 parts by weight of sodium percarbonate, 10.25 parts by weight of spray-dried sodium carbonate containing a small amount of polymer, and 2.25 parts by weight of TAED.
  • the very high amount of carbonate in these bleach tablets may, however, cause problems of formation of incrustations in the laundry.
  • the bleach tablets known from EP publication No. 0 481 792 have a very long rate of dissolution, and when used in the short washing programmes increasingly for environmental reason, this very long rate of dissolution may have the result that the tablets are not dissolved before the main washing is terminated. As a result, the cleaning and bleaching effect is considerably reduced. In addition, the tablets may be caught in a pocket, thereby causing a miscolouring due to the long contact period.
  • bleach tablets according to the invention which are characterised in that in addition to optional, usual adjuvants and additives they comprise coated percarbonate 45 to 85 % by weight bleach activator, calculated as TAED 0 to 20 % by weight layered silicate and/or alkali metal silicate 1 to 50 % by weight sodium/potassium carbonate 0 to 25 % by weight sodium/potassium bicarbonate 0 to 25 % by weight polyfunctional carboxylic acid, calculated as citric acid 5 to 35 % by weight complex-binder 0 to 5 % by weight paraffin oil 0 to 2 % by weight disintegrating agent 0 to 5 % by weight enzymes 0 to 10 % by weight polymer 0 to 10 % by weight
  • the bleach tablets are intended for use in ordinary household washing machines together with conventional detergent compositions so as to obtain an improved washing effect and stain removal of bleach-sensitive stains, such as juice, wine, tea as well as some protein-based stains.
  • bleach-sensitive stains such as juice, wine, tea
  • some protein-based stains such as juice, wine, tea
  • an improved washing effect is also obtained at low temperatures, such as at 40°C and therebelow.
  • the bleach tablets are highly practical, as the use thereof can be adapted to the washing habits prevailing in both Europe and in Asia without any problems.
  • the bleach tablets according to the invention are advantageous in possessing a surprisingly good storage stability.
  • the particular composition of the tablets has the effect that the coated percarbonate is not seriously deteriorated during the tabletting, and that the heat generated during said tabletting does not initiate the decomposition of the percarbonate to a harmful degree as is the case in conventional bleach-containing tablets.
  • the amount of layered silicate and/or alkali metal silicate is in the range of from 1 to 50 % by weight, preferably from 1 to 25 % by weight, more preferred from 2 to 10 % by weight, and most preferred from 4 to 8 % by weight.
  • the layered silicate is commercially available under the trade name SKS-6 supplied by Hoechst AG, Frankfurt, Germany.
  • coated percarbonate being an ingredient of the bleach tablets according to the invention is of a completely conventional nature.
  • An alkali metal percarbonate is advantageously used as it is easily soluble in water and in addition to the bleaching effect has an alkaline effect supporting and intensifying the washing effect.
  • suitable coated percarbonates are two commercially available products, viz. sodium percarbonate coated-Q10 (which is coated with a boron containing coating) supplied by DEGUSSA AG, Frankfurt, Germany, and PCS-C Sodium Carbonate Peroxyhydrate (coating based on a sulphate and sodium carbonate supplied by Solway Interox GmbH, Pullach, Germany.
  • the coated percarbonate is used in an amount of from 45 to 85 % by weight, such as from 50 to 65 % by weight.
  • a small amount of a further bleach such as potassium peroxomonosulphate, may optionally be incorporated.
  • the bleach tablets may furthermore, if desired, comprise a bleach activator.
  • bleach activators are tetraacetylmethylenediamine, TAED (tetraacetylethylenediamine), TAGU (tetraacetyl glycoluril), PAGE (pentaacetyl glucose), p-hydroxybenzene sulphonates, NOBS (sodium nonanoyloxybenzene sulphonate) and sodium octanoyloxybenzene sulphonate.
  • TAED tetraacetylmethylenediamine
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetyl glycoluril
  • PAGE pentaacetyl glucose
  • NOBS sodium nonanoyloxybenzene sulphonate
  • sodium octanoyloxybenzene sulphonate Most preferred is TAED, which may optionally be present in coated form
  • the bleach tablets contain a coated percarbonate and a bleach activator, calculated as TAED, in a weight ratio ranging from 2:1 to 20:1, such as from 3:1 to 15:1, e.g. from 3.5:1 to 12:1.
  • the bleach tablets contain, furthermore, a polyfunctional carboxylic acid.
  • polyfunctional carboxylic acids can be defined as such acids which in addition to the one obligatory carboxylic acid group also contain at least one further functional group selected from carboxyl and hydroxy. Furthermore, the polyfunctional acids can also contain nitrogen.
  • Non-limiting examples of such polyfunctional carboxylic acids are citric acid, nitrilotriacetic acid (NTA), EDTA and isoserine diacetic acid, of which preference is given to citric acid.
  • the polyfunctional carboxylic acid forms part of the bleach tablets in an amount of from 5 to 35 % by weight, preferably from 14 to 22 % by weight, such as from 19 to 21 % by weight, calculated as citric acid.
  • ingredients advantageously forming part of the bleach tablets according to the invention are for instance sodium/potassium carbonate and sodium/potassium bicarbonate which in combination with citric acid improve the solubility.
  • a binder may advantageously be incorporated, such as polyethylene glycol, e.g. polyethylene glycol of a molecular weight of from 200 to 8,000.
  • a complex-binder and a precipitation inhibitor may advantageously be incorporated, such as a phosphonate, i.e. a phosphonic acid or a salt thereof.
  • a phosphonate i.e. a phosphonic acid or a salt thereof.
  • suitable phosphonates and phosphonic acids are for instance ethane-1-hydroxy-1,1-diphosphonicacid (HEDP), ethylene diamine-tetra(methylene phosphonic acid) (EDTMP), diethylene triaminepenta(methylene phosphonic acid) (DETPMP), aminotrismethylene phosphonic acid (ATMP) as well as salts thereof.
  • HEDP ethane-1-hydroxy-1,1-diphosphonicacid
  • ETMP ethylene diamine-tetra(methylene phosphonic acid)
  • DETPMP diethylene triaminepenta(methylene phosphonic acid)
  • ATMP aminotrismethylene phosphonic acid
  • disodium and the tetrasodium salt
  • Sequion 10 Na PDR supplied by G. Bozzetto S.p.A., Bergamo, Italy, and which is the disodium salt of ethane-1-hydroxy-1,1-diphosphonic acid.
  • EDTA ethylenediaminetetraacetic acid
  • DETPA diethylenetriaminepentaacetic acid
  • HEEDTA hydroxyethylethylenediaminetriacetic acid
  • ISDA isoserinediacetic acid
  • enzymes may advantageously form part of the bleach tablets according to the invention.
  • examples thereof are for instance mixtures of specifically acting types, such as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases.
  • Esperase®, Savinase® and Alcalase® proteolytic enzymes
  • Termamyl® asmylolytic enzymes
  • Lipolase lipolytic enzymes
  • Celluzyme celluzyme
  • polymers may form part of the bleach tablets.
  • such polymers may be selected among all conventional polymers utilized within the detergent industry, such as the polyanionic polymers as described in US patent Nos. 3,308,067, 3,723,322, 4,144,226 and 4,146,495 and in GB patent No. 1.596.756. Among these homo- or copolymeric carboxylic acids and sodium and potassium salts thereof are preferred. If polymers are incorporated, the amount hereof typically ranges from 1 to 10 % by weight.
  • Examples of further conventional laundry detergent ingredients are agents preventing the running of colour, antiagglutinants, dyes, deodorising agents, antioxidants, solvents, foam inhibitors, perfume, optical brighteners, antistatics, nonionic tensides, bactericides, fungicides, hydrotropic agents, wetting agents and fillers.
  • the nonionic tensides used can in principle be selected from all conventional nonionic tensides usually prepared by condensation of a hydrophilic alkylene oxide with a hydrophobic compound.
  • suitable nonionic tensides are alkoxylated nonionic surfactants, where the alkoxy moiety contains an ethylene oxide, propylene oxide and/or butylene oxide as well as mixtures thereof.
  • Suitable hydrophobic compounds are alcohols, thioalcohols, dioles, fatty acids, fatty acid amides, alkanesulphone amides, alkyl amines as well as alkyl phenols.
  • nonionic tensides especially ethoxylated compounds of primary and secondary fatty alcohols are preferred.
  • Plurafac LF 403 is a fatty alcohol alkoxylate supplied by BASF, Ludwigshafen, Germany.
  • the tenside component may also include other tensides of a non-anionic nature, such as all known types of amphoteric, ampholytic and zwitterionic surfactants.
  • conventional tabletting adjuvants are usually incorporated, such as starch, magnesium stearate, magnesium silicates, glycerol, glucose, paraffin oil, polyethylene glycol and disintegrating agents, such as polyvinyl pyrrolidone (PVP), polyvinyl polypyrrolidone (PVPP) and cellulose-based or cellulose-modified compounds.
  • PVP polyvinyl pyrrolidone
  • PVPP polyvinyl polypyrrolidone
  • cellulose-based or cellulose-modified compounds such as starch, magnesium stearate, magnesium silicates, glycerol, glucose, paraffin oil, polyethylene glycol and disintegrating agents, such as polyvinyl pyrrolidone (PVP), polyvinyl polypyrrolidone (PVPP) and cellulose-based or cellulose-modified compounds.
  • Paraffin oil functions as a lubricant and facilitates the tabletting, and it is advantageously included in the bleach tablets according to the invention.
  • corresponding compounds having the same or a similar function such as for instance glycerol.
  • the formulation of a washing-intensifying bleach tablet requires fulfilment of a wide range of parameters in order to obtain the desired functional and performance characteristics.
  • the tablet is to be placed directly in the drum of the washing machine and may not be resident in fabric creases, pockets etc. or in the washing machine window/sealing ring for a long period of time. Consequently, the rate of dissolution should be as short as possible, preferably of no more than 30 to 180 sec.
  • rate of dissolution Apart from a minor acceptable increase of the rate of dissolution compared to the initial rate of dissolution measured within 5 to 24 hours after the preparation, said rate of dissolution must not, of course, be increased appreciably when stored for a long period of time.
  • the tablet strength presents a vital parameter for the processes following the tabletting, i.e. the packaging and transport, and in order to obtain a good durability this parameter must not be noticeably reduced over time.
  • the bleach tablets are also very advantageous in being environmentally desirable and by displaying good tablet-technical properties, such as a fast rate of dissolution and a high tablet strength, and these properties do not change to a noticeable extent during storage. In addition to ensuring the correct function and performance of the tablets, such properties are also important for the durability of the tablets.
  • bleach tablets were prepared having a weight of 30 g, a diameter of 40 mm and a height of 17 mm.
  • the present accelerated aging tests were performed in order to illustrate the good stability and tablet-technical properties of the tablets.
  • the tablets were stored at 40°C and a relative humidity of 75%.
  • the bleach tablets according to the invention show a good stability.
  • the volume is not noticeably increased after storage for 4 weeks under accelerated aging conditions. It should be noted that for tablets of such a size, a volume increase of up to 15% is acceptable under the stated conditions.
  • the bleach tablets have a satisfactory rate of dissolution which is not increased considerably during storage.
  • the bleach tablets display a satisfactory tablet strength which is not reduced considerably during storage. It should be noted that compared to the initially values measured within 5 to 24 hours after the preparation, the said storage under extreme conditions causes the rate of dissolution as well as the tablet strength to increase due to the curing of the tablets.
  • Example 2 As described above in Example 2, accelerated aging test were performed to illustrate the good stability and tablet-technical properties of the tablets stated in Example 3.
  • the cleaning effect is calculated as the percentage increase of the reflectance value compared to an untreated test cloth.
  • the cleaning index is calculated on the basis of the cleaning effect, the highest value of the cleaning effect (Ariel Color + 1 x 30 g recipe E on soil of the type BC1PC-Tea on blend fibres, 25) being set to 100.
  • the bleach tablets according to the invention show an improved bleaching effect over the bleach tablets known from EP publication No. 0 481 792.
  • the bleach tablets according to the invention clearly display a superior rate of dissolution in relation to the bleach tablets known from EP publication No. 0 481 792.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Bleichtabletten, dadurch gekennzeichnet, dass sie zusätzlich zu fakultativen üblichen Hilfsstoffen und Additiven umfassen: beschichtetes Percarbonat 45 bis 85 Gew.-% Bleichaktivator, berechnet als TAED 0 bis 20 Gew.-% Schichtsilikat und/oder Alkalimetallsilikat 1 bis 50 Gew.-% Natrium/Kaliumcarbonat 0 bis 25 Gew.-% Natrium/Kaliumbicarbonat 0 bis 25 Gew.-% polyfunktionelle Carbonsäure, berechnet
    als Zitronensäure     5 bis 35 Gew.-%     Polyethylenglykol 0 bis 8 Gew.-% Komplexbindemittel 0 bis 5 Gew.-% Paraffinöl 0 bis 2 Gew.-% Desintegrationsmittel 0 bis 5 Gew.-% Enzyme 0 bis 10 Gew.-% Polymer 0 bis 10 Gew.-%
  2. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass das beschichtete Percarbonat ein Alkalimetallpercarbonat ist.
  3. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass sie als Bleichaktivator TAED in einer Menge von 4 bis 15 Gew.-% enthalten.
  4. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass sie als Bleichaktivator TAED in einer Menge von 4 bis 10 Gew.-% enthalten.
  5. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass das Alkalimetallsilikat Natriumdisilikat ist.
  6. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass sie als polyfunktionelle Carbonsäure Zitronensäure enthalten.
  7. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass das Polyethylenglykol ein Molekulargewicht von 200 bis 8.000 hat.
  8. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass das Desintegrationsmittel eine Verbindung modifizierter Cellulose oder auf Basis von Cellulose ist.
  9. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass sie zusätzlich zu fakultativen üblichen Hilfsstoffen und Additiven umfassen: beschichtetes Natriumpercarbonat 55 bis 65 Gew.-% TAED 4 bis 12 Gew.-% Schichtsilikat 3 bis 6 Gew.-% Natriumcarbonat 3 bis 6 Gew.-% Zitronensäure 18 bis 22 Gew.-% Polyethylenglykol 2 bis 5 Gew.-% Paraffinöl 0,1 bis 1,0 Gew.-% Desintegrationsmittel 0 bis 4 Gew.-% Polymer 0 bis 10 Gew.-%
  10. Bleichtabletten nach Anspruch 1, dadurch gekennzeichnet, dass sie zusätzlich zu fakultativen üblichen Hilfsstoffen und Additiven umfassen: beschichtetes Natriumpercarbonat 55 bis 65 Gew.-% TAED 4 bis 12 Gew.-% Schichtsilikat 3 bis 6 Gew.-% Zitronensäure 18 bis 22 Gew.-% Polyethylenglykol 2 bis 5 Gew.-% Paraffinöl 0,1 bis 1,0 Gew.-% Desintegrationsmittel 0 bis 4 Gew.-% Polymer 0 bis 10 Gew.-%
EP19960610014 1995-04-12 1996-04-11 Bleichmitteltabletten Expired - Lifetime EP0737738B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DK44695 1995-04-12
DK44695 1995-04-12
DK446/95 1995-04-12

Publications (3)

Publication Number Publication Date
EP0737738A2 EP0737738A2 (de) 1996-10-16
EP0737738A3 EP0737738A3 (de) 1998-04-01
EP0737738B1 true EP0737738B1 (de) 2003-06-25

Family

ID=8093639

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960610014 Expired - Lifetime EP0737738B1 (de) 1995-04-12 1996-04-11 Bleichmitteltabletten

Country Status (4)

Country Link
EP (1) EP0737738B1 (de)
DE (1) DE69628784T2 (de)
DK (1) DK0737738T3 (de)
ES (1) ES2201162T3 (de)

Cited By (1)

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US11659838B2 (en) 2021-04-01 2023-05-30 Sterilex, Llc Quat-free powdered disinfectant/sanitizer

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DK0737738T3 (da) 2003-10-20
ES2201162T3 (es) 2004-03-16
EP0737738A3 (de) 1998-04-01
EP0737738A2 (de) 1996-10-16
DE69628784T2 (de) 2004-02-12

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