WO1994000549A1 - Perfectionnements apportes aux compositions de blanchissage - Google Patents
Perfectionnements apportes aux compositions de blanchissage Download PDFInfo
- Publication number
- WO1994000549A1 WO1994000549A1 PCT/EP1993/001496 EP9301496W WO9400549A1 WO 1994000549 A1 WO1994000549 A1 WO 1994000549A1 EP 9301496 W EP9301496 W EP 9301496W WO 9400549 A1 WO9400549 A1 WO 9400549A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hypochlorite
- chloride
- chlorine
- available chlorine
- surfactant
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 54
- 238000004061 bleaching Methods 0.000 title description 4
- 230000006872 improvement Effects 0.000 title description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 149
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000460 chlorine Substances 0.000 claims abstract description 65
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 65
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- -1 hypochlorite ions Chemical class 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007844 bleaching agent Substances 0.000 claims description 8
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 27
- 239000002253 acid Substances 0.000 abstract description 20
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 6
- 150000007513 acids Chemical class 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 231100000518 lethal Toxicity 0.000 abstract description 3
- 230000001665 lethal effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 230000000750 progressive effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 230000001154 acute effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 28
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011780 sodium chloride Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011012 sanitization Methods 0.000 description 3
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- 241000282412 Homo Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000004133 Sodium thiosulphate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PCBOWMZAEDDKNH-HOTGVXAUSA-N [4-(trifluoromethoxy)phenyl]methyl (3as,6as)-2-(3-fluoro-4-sulfamoylbenzoyl)-1,3,3a,4,6,6a-hexahydropyrrolo[3,4-c]pyrrole-5-carboxylate Chemical compound C1=C(F)C(S(=O)(=O)N)=CC=C1C(=O)N1C[C@H]2CN(C(=O)OCC=3C=CC(OC(F)(F)F)=CC=3)C[C@@H]2C1 PCBOWMZAEDDKNH-HOTGVXAUSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 231100000636 lethal dose Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
Definitions
- the present invention relates to improvements to aqueous, hypochlorite containing compositions, suitable for use in the cleaning and/or sanitization of hard surfaces and the bleaching of stains on said surfaces.
- Acidic products comprise a variety of aqueous acids, including sulphuric, hydrochloric, phosphoric, formic, citric, acetic and sulphamic acids.
- Hypochlorite based products generally contain aqueous sodium hypochlorite and are commonly known as 'hypochlorite bleaches' even when the level of hypochlorite in said compositions is insufficient to bleach stains. At low levels hypochlorite is ineffective as a bleach but is still effective as a hygiene/sanitization agent.
- hypochlorite solutions are manufactured by reaction of chlorine gas with sodium hydroxide, by passing the chlorine gas through the alkali in aqueous solution.
- the reaction produces sodium chloride and sodium hypochlorite in almost equimolar quantities at a typical final concentration of about 13%wt sodium chloride, 15% available chlorine.
- a portion of the sodium chloride may be removed by partial crystallisation at depressed temperature and subsequent filtration, typically to reduce the sodium chloride level to about 3%wt.
- This low salt solution may be concentrated to a higher hypochlorite level for shipping.
- the bulk of the hypochlorite produced on an industrial scale comprises about 13% sodium chloride, 15% available chlorine, some 30% hypochlorite solution with relatively low salt levels is produced for use in the organic chemistry industry in halogenation reactions.
- Electrolyte solutions sold as 'bleaches' comprise moderately high levels of electrolyte.
- the electrolyte is commonly sodium chloride as produced in the above-mentioned process.
- T SHEET In commercial products, levels of electrolyte (as sodium chloride) are typically around 4-10%wt depending on the surfactant system and the level of hypochlorite. Typical levels of hypochlorite are equivalent to 1-9% available chlorine. With some surfactant systems it has been considered necessary to dose additional salt into the product so as to achieve the desired viscosity of the final composition. Generally the ratio of sodium chloride to sodium hypochlorite is around 1:1. Moreover, where concentrated hypochlorite solution is used as a raw material in the preparation of commercial bleaches, it is commonplace to dilute the solutions with a salt solution, or otherwise add salt, to reach typical salt levels at which the desired viscosity in the presence of a suitable surfactant is achieved.
- hypochlorite is both unstable on storage and corrosive to metals. Consequently extreme care must be taken in the handling of hypochlorite bleaches both during manufacture and storage. Moreover, the shelf life of hypochlorite bleaches is limited due to the progressive decomposition of the hypochlorite ion. Analysis of commercially available products indicates that the hypochlorite half-life of the products may be as short as six weeks.
- hypochlorite solutions are safe when used in accordance with the manufacturers instructions, it is well known that when acids are added to hypochlorite bleaches in amounts such that the pH falls below 4, chlorine gas is evolved into the environment. It is very well known that even low concentrations of
- SUBSTITUTE SHEET chlorine gas can present a serious and potentially lethal hazard to health.
- Acid solutions may be inadvertently mixed with hypochlorite solutions when acidic hard-surface cleaners and hypochlorite-based hard-surface cleaners are used simultaneously or sequentially in cleaning operations. Similar accidents may occur when acidic brick cleaners or acidic de-scaling agents are mixed with hypochlorite solutions. For these reasons, much effort has been expended in finding alternative bleaching agents and the use of materials such as hydrogen peroxide has met with some success.
- hypochlorite based cleaning and sanitizing compositions have suffered from disadvantages either of high or prohibitive cost or reduced antimicrobial activity as compared with hypochlorite solutions.
- hypochlorite solutions in which the level of chloride ions in the electrolyte is low are more stable than solutions comprising higher levels of chloride ions.
- the present invention provides for the use of an essentially chloride free electrolyte as a stabilizer in an aqueous hypochlorite bleach.
- a first aspect of the present invention provides an aqueous hypochlorite solution comprising at least
- products according to the present invention comprise in addition to an aqueous hypochlorite solution, an electrolyte wherein the level of chloride ions is less than about lwt%, more preferably in the range l-0.001wt%, levels of chloride of around l-0.5wt% being particularly preferred.
- products according to the present invention comprise 0.15-15wt% available chlorine as hypochlorite.
- Preferred levels of available chlorine range from l-10wt%
- ratio of available chlorine to chloride is greater than 1.5:1 It is particularly desirable to reduce the levels of chlorine released or to retard the release of chlorine from products which comprise relatively high levels of chlorine. At higher available chlorine levels it is preferred to maintain a ratio of chlorine to chloride of greater than 3, more preferably of 10 or more. Ratios of up to 30 have been reached in practical embodiments of the invention.
- compositions comprise:
- ratio of available chlorine to chloride is greater than 1.5:1
- Suitable surfactants are those which are stable in the presence of hypochlorite.
- surfactant is present to promote effective cleaning.
- surfactant is present as a thickener.
- hypochlorite bleaches comprise 1-2% of an amine oxide of the general formula:
- R is straight or branched C 8 to C 18 alkyl
- R x is C x to C 3 alkyl or d to C 3 hydroxyalkyl
- R 2 is d to C 3 alkyl or d to C 3 hydroxyalkyl
- R comprises at least 25% w/w, preferably at least 50%w/w C 16 - C 18 alkyl.
- R comprises at least 25%, preferably at least 50% C 16 -C 18 linear alkyl.
- R x and R 2 are methyl groups.
- compositions according to the present invention is above 11, more preferably in the range 12-13.
- This pH can be achieved by the addition of a suitable alkali, such as an alkali metal hydroxide.
- the composition can include a colouring agent selected from the group comprising the copper phthalocyanides and mixtures thereof.
- compositions according to the present invention can also comprise perfumes, sequestering agents and mixtures thereof.
- FIGURE 1 shows selected results from Tables 1A-1B below, to illustrate the effect of chlorine:chloride ratio of the proportion of available chlorine released
- FIGURE 2 shows a graph of available chlorine decay with time in products according to the present invention and comparative products
- FIGURE 3 shows a graph of product viscosity changes with time in products according to the present invention and comparative products
- Chlorine gas release was evaluated in a German-type 'shelf WC plumbed into a toilet cubicle having width
- Ml 15cm above the shelf of the toilet. Represents the chlorine exposure if the head is placed within the toilet bowl, i.e. assuming a worst case scenario involving collapse of a person shortly after mixing acid and hypochlorite product.
- M2 5-10 cm from the edge of the bowl. Represents the chlorine exposure assuming collapse of a person onto the floor at the side of the WC.
- M3 35-40cm above the rim of the bowl. Represents the chlorine exposure if a person mixed the acid and hypochlorite products while cleaning the toilet and kneeling.
- M4 100cm above the rim of the bowl. Represents the chlorine exposure if a person mixed the acid and hypochlorite products while cleaning the toilet in an upright position.
- compositions tested Concentrations of salt in the compositions tested are given in wt%. Available chlorine in the products was determined by titration against sodium thiosulphate solution. The compositions were dosed into the toilet bowl in quantities of lOOg. It should be noted that consumers generally dose around 80g of hypochlorite formulations into the toilet bowl although the sporadic use of excessive quantities is not unknown.
- the acid toilet cleaner was dosed into the toilet bowl in quantities of lOOg, except in the case of the sulphuric acid 'SU' which was dosed at a 50g level.
- hypochlorite compositions are identified by the available chlorine as measured (AC) given as a percentage: i.e. 'AC9' in example 1.1 refers to 9% available chlorine.
- hypochlorite bleach composition comprising a standard level of salt evolved some chlorine gas when mixed with a commercially available Belgian lavatory cleaner based on formic acid.
- the compositions according to the present invention showed a slightly reduced and retarded chlorine release, although the quantities of chlorine released from this product did not constitute a particularly serious hazard.
- Figure 1 shows the chlorine release data in terms of the ratio of available chlorine to chloride (as sodium chloride) in the compositions plotted against the ratio of M2 to total available chlorine. The ratios are calculated as follows: - 17
- compositions according to the present invention have a ratio of AvCl 2 /NaCl greater than 1.5.
- Aromox DMB-W [RTM: Akzo Chemicals] is an amine oxide having a chain length distribution of 54% C 12 , 24% C 14 ,
- Long Chain AO is amine oxide having a chain length distribution of 35% C 12 , 15% C 14 , 18% C 16 and 32% C 18
- Alkaline silicate (100 degrees TW) was obtained from the Crossfield chemical company.
- Sodium Chloride is expressed as total sodium chloride on product .
- Sodium Hypochlorite is expressed as the wt% of a solution having 15.4% available chorine, free of sodium chloride.
- compositions 2A, 2B and 2C were prepared with formulations as given in Table 2 below, all figures being given in wt%:
- Examples 2A is a comparative example: 2A being essentially identical to a commercially available aqueous hypochlorite bleaching composition available in the marketplace, whereas 2B has a reduced salt content and employs a modified amine oxide thickener.
- Example 2C is an embodiment of the present invention and is identical to 2B except that the salt level has been further reduced. Formulations were made up by heating the water to circa. 80°C, adding the lauric acid, neutralising the product obtained, subsequently adding the amine oxide and cooling to circa. 50°C before adding perfume and all ingredients except hypochlorite. Hypochlorite was added at circa. 30°C after further cooling.
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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)
- Detergent Compositions (AREA)
Abstract
L'une des difficultés associées aux taux élevés d'électrolyte dans les solutions d'hypochlorite est la cristallisation de l'électrolyte sous forme de sel solide autour des bouchons des récipients. Plus gravement, l'hypochlorite est à la fois instable au stockage et corrosif pour les métaux, ce qui signifie que sa durée de conservation est limitée à cause de la décomposition progressive de l'ion d'hypochlorite. Plus gravement encore, lorsqu'on ajoute aux hypochlorites des quantités d'acide telles que le pH tombe au-dessous de 4, du gaz chloré se dégage dans le milieu ambiant. Il est bien connu que même les faibles concentrations de gaz chloré élémentaire représentent une menace grave et potentiellement mortelle pour la santé, ainsi qu'une menace pour l'environnement à plus long terme. De façon surprenante, il s'avère que, en l'absence d'ions de chlorure ou en présence de taux réduits de ceux-ci, l'on obtient une amélioration très sensible de la stabilité des ions d'hypochlorite aqueux dans des conditions acides. En outre, il s'avère que la présence de taux réduits d'ions de chlorure permet d'améliorer la stabilité des décolorants à l'hypochlorite dans des conditions neutres ou alcalines. Par conséquent, on a mis au point une solution aqueuse d'hypochlorite comportant au moins 0,01 % en poids de tensioactif, le rapport entre le chlore disponible et le chlorure (en tant que sel de métal alcalin) est supérieur à 1,5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU43256/93A AU4325693A (en) | 1992-06-26 | 1993-06-14 | Improvements to bleaching compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929213578A GB9213578D0 (en) | 1992-06-26 | 1992-06-26 | Improvements to bleaching compositions |
| GB9213578.9 | 1992-06-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994000549A1 true WO1994000549A1 (fr) | 1994-01-06 |
Family
ID=10717771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1993/001496 WO1994000549A1 (fr) | 1992-06-26 | 1993-06-14 | Perfectionnements apportes aux compositions de blanchissage |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU4325693A (fr) |
| GB (1) | GB9213578D0 (fr) |
| WO (1) | WO1994000549A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040021213A (ko) * | 2002-09-03 | 2004-03-10 | 한국과학기술연구원 | 천이금속계 자기변형 복합체 제조방법 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2253826A1 (fr) * | 1973-12-11 | 1975-07-04 | Kao Corp | |
| US4057505A (en) * | 1975-07-14 | 1977-11-08 | Kao Soap Co., Ltd. | Liquid cleaning and bleaching composition |
| US4174289A (en) * | 1977-07-27 | 1979-11-13 | Basf Wyandotte Corporation | Liquid detergent-bleach concentrates having high alkalinity |
| EP0030401A1 (fr) * | 1979-12-05 | 1981-06-17 | Unilever N.V. | Composition chlorée liquide et épaissie de blanchiment |
| US4287079A (en) * | 1980-06-02 | 1981-09-01 | Purex Corporation | Liquid cleanser formula |
| EP0079697A1 (fr) * | 1981-11-07 | 1983-05-25 | THE PROCTER & GAMBLE COMPANY | Compositions de nettoyage |
| EP0145084A2 (fr) * | 1983-12-02 | 1985-06-19 | Unilever N.V. | Composition pour le blanchiment |
| EP0147943A2 (fr) * | 1983-12-15 | 1985-07-10 | Imperial Chemical Industries Plc | Composition de blanchissement |
| EP0256638A1 (fr) * | 1986-08-07 | 1988-02-24 | The Clorox Company | Composition d'hypochlorite épaississante et son utilisation |
| EP0311175A2 (fr) * | 1987-10-08 | 1989-04-12 | Unilever N.V. | Agent assainissant |
| EP0447261A1 (fr) * | 1990-03-15 | 1991-09-18 | Unilever Plc | Composition blanchissante |
-
1992
- 1992-06-26 GB GB929213578A patent/GB9213578D0/en active Pending
-
1993
- 1993-06-14 WO PCT/EP1993/001496 patent/WO1994000549A1/fr active Application Filing
- 1993-06-14 AU AU43256/93A patent/AU4325693A/en not_active Abandoned
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2253826A1 (fr) * | 1973-12-11 | 1975-07-04 | Kao Corp | |
| US4057505A (en) * | 1975-07-14 | 1977-11-08 | Kao Soap Co., Ltd. | Liquid cleaning and bleaching composition |
| US4174289A (en) * | 1977-07-27 | 1979-11-13 | Basf Wyandotte Corporation | Liquid detergent-bleach concentrates having high alkalinity |
| EP0030401A1 (fr) * | 1979-12-05 | 1981-06-17 | Unilever N.V. | Composition chlorée liquide et épaissie de blanchiment |
| US4287079A (en) * | 1980-06-02 | 1981-09-01 | Purex Corporation | Liquid cleanser formula |
| EP0079697A1 (fr) * | 1981-11-07 | 1983-05-25 | THE PROCTER & GAMBLE COMPANY | Compositions de nettoyage |
| EP0145084A2 (fr) * | 1983-12-02 | 1985-06-19 | Unilever N.V. | Composition pour le blanchiment |
| EP0147943A2 (fr) * | 1983-12-15 | 1985-07-10 | Imperial Chemical Industries Plc | Composition de blanchissement |
| EP0256638A1 (fr) * | 1986-08-07 | 1988-02-24 | The Clorox Company | Composition d'hypochlorite épaississante et son utilisation |
| EP0311175A2 (fr) * | 1987-10-08 | 1989-04-12 | Unilever N.V. | Agent assainissant |
| EP0447261A1 (fr) * | 1990-03-15 | 1991-09-18 | Unilever Plc | Composition blanchissante |
Non-Patent Citations (1)
| Title |
|---|
| DATABASE WPI Section Ch Week 14, Derwent World Patents Index; Class D25, AN 73-19563U [14] * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040021213A (ko) * | 2002-09-03 | 2004-03-10 | 한국과학기술연구원 | 천이금속계 자기변형 복합체 제조방법 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4325693A (en) | 1994-01-24 |
| GB9213578D0 (en) | 1992-08-12 |
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