EP0176124A2 - Use of peroxycarboxylic acid-containing suspensions as bleaching compositions, novel bleaching compositions and bleaching compositions in the packaged form - Google Patents
Use of peroxycarboxylic acid-containing suspensions as bleaching compositions, novel bleaching compositions and bleaching compositions in the packaged form Download PDFInfo
- Publication number
- EP0176124A2 EP0176124A2 EP85201382A EP85201382A EP0176124A2 EP 0176124 A2 EP0176124 A2 EP 0176124A2 EP 85201382 A EP85201382 A EP 85201382A EP 85201382 A EP85201382 A EP 85201382A EP 0176124 A2 EP0176124 A2 EP 0176124A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching compositions
- composition
- compositions
- acid
- weight
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 238000004061 bleaching Methods 0.000 title claims abstract description 36
- 239000000725 suspension Substances 0.000 title claims abstract description 19
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 title claims description 17
- 239000002253 acid Substances 0.000 claims abstract description 19
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- -1 alkali metal salt Chemical class 0.000 claims abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 5
- 239000001120 potassium sulphate Substances 0.000 claims abstract description 5
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 7
- 150000007513 acids Chemical class 0.000 abstract description 4
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 239000003995 emulsifying agent Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000009172 bursting Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JHUXOSATQXGREM-UHFFFAOYSA-N dodecanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCCCC(=O)OO JHUXOSATQXGREM-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229960004838 phosphoric acid Drugs 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- DUXXGJTXFHUORE-UHFFFAOYSA-M sodium;4-tridecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 DUXXGJTXFHUORE-UHFFFAOYSA-M 0.000 description 1
- NZRSEGYTVSNMCK-UHFFFAOYSA-N sodium;undecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 NZRSEGYTVSNMCK-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic per-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
- C11D3/3947—Liquid compositions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
Definitions
- peroxycarboxylic acid-containing suspensions as bleaching compositions, novel bleaching compositions and bleaching compositions in the packaged form
- the invention relates to the use as pourable bleaching composition of a suspension in water comprising a peroxycarboxylic acid derived from a dicarboxylic acid containing 8 to 13 carbon atoms.
- liquid bleaching compositions over solid bleaching compositions are that in their preparation there is no need for cost- increasing shaping steps, such as drying and granulating, and the fabrics to be treated are rapidly and evenly bleached, so that high concentrations of the bleaching agent in places can be satisfactorily avoided.
- the present bleaching composition does not show this drawback.
- the invention relates to the use of the above type, characterized in that the bleaching composition also comprises an alkali metal salt of an alkyl benzene sulphonic acid.
- An additional advantage to the present composition is that, provided that the proportions of the constituents to be used are properly chosen, it is protected from hazards due to spilling and drying up, as a result of which solid peroxide particles are formed.
- solid peroxide particles Of peroxides in the solid state it is known that they are exposed to explosion, shock and abrasion hazards.
- solid peroxide particles will form that are provided with a coating such that they are desensitized.
- the pourable compositions disclosed in GB 1 535 8 ⁇ 4 are not protected in that way, the amount of thickening agent required for these compositions being so small that in the event of spilling and drying up solid particles are formed that are insufficiently desensitized. From experiments it has moreover been found that this drawback cannot be eliminated by the addition to these suspensions of well-known desensitizing agents such as sodium sulphate, because the properties of these suspensions will be even further deteriorated then.
- composition according to the invention is physically stable, i.e. after storage for 6 weeks at 20°C the peroxycarboxylic acid is well dispersed and the suspension does not display any phase-separation. If precipitation takes place at all, the homogeneity of the dispersion can be readily restored by gently shaking it.
- composition according to the invention is chemically stable, i.e. after storage for 2 weeks at 40°C it still has the same or practically the same active oxygen content.
- composition according to the invention is pourable, by which is to be understood that at 20°C the composition has a viscosity between 1 and 1200 mPa.s, preferably between 50 and 500 mPa.s (Brookfield rotational viscometer [RV type], 20 rpm).
- the invention also relates to those bleaching compositions that are new as such and to the present bleaching compositions in the packaged form.
- the bleaching component in the present composition consists of a peroxycarboxylic acid derived from a dicarboxylic acid containing 8 to 13 carbon atoms.
- Such peroxycarboxylic acids are not, or hardly soluble in water (solubility less than 1% by weight in water at 20°C).
- the present composition should contain diperoxy dicarboxylic acids, such as 1,12-diperoxydodecanedioic acid, 1,13-diperoxy- tridecanedioic acid or suitable mixtures thereof.
- the composition according to the invention contains peroxycarboxylic acid in an amount such that the active oxygen content of the composition is between 0,1 and 4%, preferably between 0,1 and 3%.
- the present composition must contain an alkali metal salt of an alkyl benzene sulphonic acid.
- the alkyl group may be branched or linear and contains 9 to 22 carbon atoms, preferably 9 to 15 carbon atoms, more particularly 11 to 13 carbon atoms.
- these alkyl benzene sulphonates may be mentioned sodium undecyl benzene sulphonate, sodium dodecyl benzene sulphonate and sodium tridecyl benzene sulphonate. Also mixtures of these sulphonates may be used.
- composition according to the invention should contain sodium dodecyl benzene sulphonate.
- the alkali metal salt of an alkyl benzene sulphonic acid should be used in an amount such that the composition is pourable and physically stable.
- the composition will contain alkali metal salt of an alkyl benzene sulphonic acid in an amount of 0,5 to 15% by weight, and preferably 2 to 10% by weight, calculated on the weight of the composition. Use of amounts less than 0,5% by weight will result in compositions that have insufficient physical stability; use of amounts higher than 15% by weight will result in obtaining viscous compositions that are no longer pourable.
- the alkali metal salts of alkyl benzene sulphonic acids commonly used in actual practice as emulsifier are so-called technical products in which as impurity an inorganic salt such as sodium sulphate is contained.
- these technical products can very well be used for preparing the present compositions, a preferred embodiment consists in that also particular inorganic salts are added. It has been found that adding sodium sulphate, potassium sulphate or mixtures thereof has a favourable effect on the physical stability of the compositions, i.e. if there appears to be any precipitation at all upon using a technical emulsifier alone, it can entirely be stopped by the additional use of said inorganic salts.
- compositions with the same properties can be prepared that contain less emulsifier than when no use is made of these inorganic salts.
- This last- mentioned embodiment is preferred in actual practice because of the considerably lower cost price of the inorganic salts as compared with that of the emulsifier to be used.
- a preferred inorganic salt is sodium sulphate.
- the amount of inorganic salt to be used will partly be dependent on the amount of inorganic salt originating from the emulsifier as impurity and should be such that the bleaching composition is pourable and physically stable.
- the bleaching composition according to the invention will contain inorganic salt, including the inorganic salt originating from the emulsifier, in an amount of 0,01 to 20% by weight, preferably 2 to 10% by weight, calculated on the weight of the composition.
- composition according to the invention may still contain other additives, as examples of which may be mentioned:
- the present bleaching compositions may very effectively be used in the pre-bleaching treatment of dirty washing at low temperature (say, about 30°C).
- the treatment of dirty washing with the usually applied heavy and light duty detergents they are also very suitable to be separately added to the wash liquor. Their effect is at least equivalent to that of the bleaching compositions disclosed in GB 1 535 804.
- compositions according to the invention may be prepared by adding the peroxycarboxylic acid, with stirring, to an acidified mixture (preferably pH 3,5-4,5) of water, alkyl benzene sulphonate and any other additives.
- the peroxycarboxylic acid may be used in the form of powder (primary particle size 1-100 microns) or in the form of wet filter cake, as obtained after the peroxycarboxylic acid preparation from the corresponding dicarboxylic acid and hydrogen peroxide.
- the pH of the composition is finally set to a particularly desired value, which should be in the acid range, use being made of, for instance, aqueous sodium hydroxide or hydrochloric acid. It is preferred that the pH should not be higher than 5.
- compositions as mentioned in Table 1 were prepared. Compositions 1-6 are according to the invention. The pH values of these compositions were in the range of 3,5 to 4,5.Composition 7 is according to GB 1 535 804.
- compositions 1,2,4,5, and 6 did not display any phase-separation or precipitation phenomena.
- sample of composition 3 had precipitated, no thick bottom layer had formed and the original homogeneity of the dispersion could be restored by gentle shaking.
- sample of composition 7 had precipitated and a thick bottom layer had formed (phase-separated) which could not very well be re-dispersed.
- compositions 2,3 and 7 were evaporated to dryness by means of an air stream at 25° - 30°C, after which the material thus obtained was subjected to a Pressure Vessel Test.
- This test is described in Vervoer Gevaarlijke stoffen, 23 December 1980, Aanhangsel Al bij bijlage A, pp. 907,908, 915: Wunschsuitgeverij.
- 10 grammes of the material to be tested are heated by a standardized gas flame in a pressure vessel fitted with a bursting disk set to 6 bar.
- a blow-off opening with variable diameter.
- the test procedure implies that such a blow-off opening is found that after decomposition (explosion, combustion) of the peroxide, the bursting disk is still just intact.
- the admissible opening (in mm) is given as PVT value.
- the PVT values found for the material from composition 2 were less than 1 mm, from composition 3 less than 1 mm, and from composition 7 they were 6 mm. (The PVT value for pure diperoxydodecanedioic acid is 7 mm).
- Suspensions were prepared from diperoxydodecanedioic acid (11,65 g of wet filter cake with an active oxygen content of 5,1%), hydroxyethylidene diphosphonic acid (Dequest 2010 * ; 0,25 g), emulsifier and water; the pH of the suspensions was 3,9-4,1.
- suspension 1 is not a composition according to the invention; it contains about 30% of emulsifier and has a viscosity of 1975 mPa.s. It has been found that the effect of emulsifiers on the chemical stability of peroxycarboxylic acid compositions can very well be established when they are used in relatively high concentrations.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Saccharide Compounds (AREA)
Abstract
Description
- Use of peroxycarboxylic acid-containing suspensions as bleaching compositions, novel bleaching compositions and bleaching compositions in the packaged form
- The invention relates to the use as pourable bleaching composition of a suspension in water comprising a peroxycarboxylic acid derived from a dicarboxylic acid containing 8 to 13 carbon atoms.
- Such use is known from British Patent Specification GB 1 535 804. It describes liquid bleach compositions having a viscosity of from 200 to 100 000 mPa.s and containing a peroxide, a thickening agent and water. They are suitable for use in washing machines and automatic clothes dryers.
- The advantages to using liquid bleaching compositions over solid bleaching compositions are that in their preparation there is no need for cost- increasing shaping steps, such as drying and granulating, and the fabrics to be treated are rapidly and evenly bleached, so that high concentrations of the bleaching agent in places can be satisfactorily avoided.
- To the bleaching compositions of GB 1 535 804, at least as far as they are pourable (see below), there is the disadvantage that they are not physically stable, which after prolonged storage results in phase-separated products with a thick bottom layer which is difficult to disperse or homogenize, as a result of which said advantage of even distribution over the fabric to be cleaned may partly be eliminated again.
- The present bleaching composition does not show this drawback.
- The invention relates to the use of the above type, characterized in that the bleaching composition also comprises an alkali metal salt of an alkyl benzene sulphonic acid.
- An additional advantage to the present composition is that, provided that the proportions of the constituents to be used are properly chosen, it is protected from hazards due to spilling and drying up, as a result of which solid peroxide particles are formed. Of peroxides in the solid state it is known that they are exposed to explosion, shock and abrasion hazards. But in the event of spilling and drying up of properly chosen present suspensions solid peroxide particles will form that are provided with a coating such that they are desensitized. The pourable compositions disclosed in GB 1 535 8θ4 are not protected in that way, the amount of thickening agent required for these compositions being so small that in the event of spilling and drying up solid particles are formed that are insufficiently desensitized. From experiments it has moreover been found that this drawback cannot be eliminated by the addition to these suspensions of well-known desensitizing agents such as sodium sulphate, because the properties of these suspensions will be even further deteriorated then.
- It should be noted that the present suspensions, containing a peroxycarboxylic acid and an alkali metal salt of an alkyl benzene sulphonic acid, are disclosed in US 4 126 573. Said patent specification, however, relates to solid, granular bleaching compositions and the present suspensions are merely applied for the preparations of these solid compositions by drying, which is in the light apparently of what is mentioned in the introductory part of US 4 126 573 (column 1, lines 17-20), namely that the liquid bleaching compositions containing peroxyacid materials as the active bleaching agent have the tendency to diminish in bleaching effectiveness over prolonged storage periods.
- Therefore, in view of US 4 126 573, the use of the present suspensions as bleaching composition is not at all obvious. For, if the peroxycarboxylic acid is finely dispersed in the water, the chance of decomposition during storage is great. Moreover, from experiments it has been found that such decomposition occurs in the case of a great many anionic and nonionic emulsifiers. It has been found, however, that the presence of an alkali metal salt of an alkyl benzene sulphonic acid as emulsifier has no or - hardly any detrimental effect on the active oxygen content of the composition.
- The composition according to the invention is physically stable, i.e. after storage for 6 weeks at 20°C the peroxycarboxylic acid is well dispersed and the suspension does not display any phase-separation. If precipitation takes place at all, the homogeneity of the dispersion can be readily restored by gently shaking it.
- Moreover, the composition according to the invention is chemically stable, i.e. after storage for 2 weeks at 40°C it still has the same or practically the same active oxygen content.
- The composition according to the invention is pourable, by which is to be understood that at 20°C the composition has a viscosity between 1 and 1200 mPa.s, preferably between 50 and 500 mPa.s (Brookfield rotational viscometer [RV type], 20 rpm).
- The invention also relates to those bleaching compositions that are new as such and to the present bleaching compositions in the packaged form.
- The bleaching component in the present composition consists of a peroxycarboxylic acid derived from a dicarboxylic acid containing 8 to 13 carbon atoms. Such peroxycarboxylic acids are not, or hardly soluble in water (solubility less than 1% by weight in water at 20°C).
- Also mixtures of these acids may be used.
- It is preferred that the present composition should contain diperoxy dicarboxylic acids, such as 1,12-diperoxydodecanedioic acid, 1,13-diperoxy- tridecanedioic acid or suitable mixtures thereof.
- The preparation of these acids is effected in a known manner by reacting the corresponding dicarboxylic acids with hydrogen peroxide in the presence of sulphuric acid.
- Generally, the composition according to the invention contains peroxycarboxylic acid in an amount such that the active oxygen content of the composition is between 0,1 and 4%, preferably between 0,1 and 3%.
- The present composition must contain an alkali metal salt of an alkyl benzene sulphonic acid. The alkyl group may be branched or linear and contains 9 to 22 carbon atoms, preferably 9 to 15 carbon atoms, more particularly 11 to 13 carbon atoms. As examples of these alkyl benzene sulphonates may be mentioned sodium undecyl benzene sulphonate, sodium dodecyl benzene sulphonate and sodium tridecyl benzene sulphonate. Also mixtures of these sulphonates may be used.
- It is preferred that the composition according to the invention should contain sodium dodecyl benzene sulphonate.
- The alkali metal salt of an alkyl benzene sulphonic acid should be used in an amount such that the composition is pourable and physically stable. Generally, the composition will contain alkali metal salt of an alkyl benzene sulphonic acid in an amount of 0,5 to 15% by weight, and preferably 2 to 10% by weight, calculated on the weight of the composition. Use of amounts less than 0,5% by weight will result in compositions that have insufficient physical stability; use of amounts higher than 15% by weight will result in obtaining viscous compositions that are no longer pourable.
- The alkali metal salts of alkyl benzene sulphonic acids commonly used in actual practice as emulsifier are so-called technical products in which as impurity an inorganic salt such as sodium sulphate is contained. Although these technical products can very well be used for preparing the present compositions, a preferred embodiment consists in that also particular inorganic salts are added. It has been found that adding sodium sulphate, potassium sulphate or mixtures thereof has a favourable effect on the physical stability of the compositions, i.e. if there appears to be any precipitation at all upon using a technical emulsifier alone, it can entirely be stopped by the additional use of said inorganic salts. It has also been found that when use is made of said inorganic salts, compositions with the same properties can be prepared that contain less emulsifier than when no use is made of these inorganic salts. This last- mentioned embodiment is preferred in actual practice because of the considerably lower cost price of the inorganic salts as compared with that of the emulsifier to be used. A preferred inorganic salt is sodium sulphate.
- The amount of inorganic salt to be used will partly be dependent on the amount of inorganic salt originating from the emulsifier as impurity and should be such that the bleaching composition is pourable and physically stable. Generally, the bleaching composition according to the invention will contain inorganic salt, including the inorganic salt originating from the emulsifier, in an amount of 0,01 to 20% by weight, preferably 2 to 10% by weight, calculated on the weight of the composition.
- The composition according to the invention may still contain other additives, as examples of which may be mentioned:
- - thickening agents; examples thereof are described in GB 1 535 804. Thickeners can be used in maximum amounts such that the composition remains pourable;
- - sequestering agents, which serve to bind any metal ions present that may accelerate the decomposition of peroxides. Examples of sequestering agents are ethylene diamine tetra acetate, sodium pyrophosphate, phosphoric acid, dipicolinic acid and hydroxy ethylidene diphosphonic acid. They may be used in amounts of 0,01 to 1% by weight, calculated on the weight of the composition;
- - builders, such as polycarboxylates, and finally optical brighteners, perfumes and organic solvents.
- The present bleaching compositions may very effectively be used in the pre-bleaching treatment of dirty washing at low temperature (say, about 30°C). In the treatment of dirty washing with the usually applied heavy and light duty detergents they are also very suitable to be separately added to the wash liquor. Their effect is at least equivalent to that of the bleaching compositions disclosed in GB 1 535 804.
- The compositions according to the invention may be prepared by adding the peroxycarboxylic acid, with stirring, to an acidified mixture (preferably pH 3,5-4,5) of water, alkyl benzene sulphonate and any other additives. The peroxycarboxylic acid may be used in the form of powder (primary particle size 1-100 microns) or in the form of wet filter cake, as obtained after the peroxycarboxylic acid preparation from the corresponding dicarboxylic acid and hydrogen peroxide. If necessary, the pH of the composition is finally set to a particularly desired value, which should be in the acid range, use being made of, for instance, aqueous sodium hydroxide or hydrochloric acid. It is preferred that the pH should not be higher than 5. Higher values would have a detrimental effect on the chemical stability of the composition. A pH lower than 2, however, should also be avoided. For, due to dilution with water of such composition the resulting insufficiently high final pH would cause the metal parts of the washing machine in which it is used to be subject to corrosion. Particularly preferred are compositions having a pH of 3,5-4,5, more particularly 3,9-4,1.
- The invention will be further described in the following examples. All percentages are by weight.
- Compositions as mentioned in Table 1 were prepared. Compositions 1-6 are according to the invention. The pH values of these compositions were in the range of 3,5 to 4,5.Composition 7 is according to GB 1 535 804.
-
- Moreover, of each composition a sample was stored for the purpose of assessing the physical stability. After 6 weeks at 20°C samples of the compositions 1,2,4,5, and 6 did not display any phase-separation or precipitation phenomena. Although the sample of composition 3 had precipitated, no thick bottom layer had formed and the original homogeneity of the dispersion could be restored by gentle shaking. But the sample of composition 7 had precipitated and a thick bottom layer had formed (phase-separated) which could not very well be re-dispersed.
- For the purpose of assessing the differences in safeguarding against the hazards resulting from spilling and drying up between the compositions according to the invention on the one hand and a composition according to GB 1 535 804 on the other, samples of compositions 2,3 and 7 were evaporated to dryness by means of an air stream at 25° - 30°C, after which the material thus obtained was subjected to a Pressure Vessel Test. This test is described in Vervoer Gevaarlijke stoffen, 23 December 1980, Aanhangsel Al bij bijlage A, pp. 907,908, 915: Staatsuitgeverij. In this test 10 grammes of the material to be tested are heated by a standardized gas flame in a pressure vessel fitted with a bursting disk set to 6 bar. In the side wall of the pressure vessel is a blow-off opening with variable diameter.
- The test procedure implies that such a blow-off opening is found that after decomposition (explosion, combustion) of the peroxide, the bursting disk is still just intact. The smaller the admissible opening, the safer the formulation. The admissible opening (in mm) is given as PVT value. The PVT values found for the material from composition 2 were less than 1 mm, from composition 3 less than 1 mm, and from composition 7 they were 6 mm. (The PVT value for pure diperoxydodecanedioic acid is 7 mm).
- In this example the effect is given of different anionic and nonionic emulsifiers on the chemical stability of peroxycarboxylic acid suspensions.
- Suspensions were prepared from diperoxydodecanedioic acid (11,65 g of wet filter cake with an active oxygen content of 5,1%), hydroxyethylidene diphosphonic acid (Dequest 2010*; 0,25 g), emulsifier and water; the pH of the suspensions was 3,9-4,1.
- The nature of the emulsifiers and the amounts thereof as well as the amounts of water are given in the table below. The data on the chemical stability of the suspensions, i.e. the active oxygen content of the suspensions after storage at 40°C, are mentioned in the lower part of the table.
-
- It should be added that suspension 1 is not a composition according to the invention; it contains about 30% of emulsifier and has a viscosity of 1975 mPa.s. It has been found that the effect of emulsifiers on the chemical stability of peroxycarboxylic acid compositions can very well be established when they are used in relatively high concentrations.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85201382T ATE44763T1 (en) | 1984-09-28 | 1985-09-03 | USE OF SUSPENSIONS CONTAINING PEROXYCARBONIC ACID AS BLEACHES, NEW BLEACHES AND BLEACHES IN PACKAGED FORM. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL8402957 | 1984-09-28 | ||
NL8402957A NL8402957A (en) | 1984-09-28 | 1984-09-28 | USE OF PEROXYCARBONIC ACID CONTAINING SUSPENSIONS AS A BLEACH COMPOSITION. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0176124A2 true EP0176124A2 (en) | 1986-04-02 |
EP0176124A3 EP0176124A3 (en) | 1986-12-03 |
EP0176124B1 EP0176124B1 (en) | 1989-07-19 |
Family
ID=19844528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85201382A Expired EP0176124B1 (en) | 1984-09-28 | 1985-09-03 | Use of peroxycarboxylic acid-containing suspensions as bleaching compositions, novel bleaching compositions and bleaching compositions in the packaged form |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0176124B1 (en) |
JP (1) | JPH0689357B2 (en) |
AT (1) | ATE44763T1 (en) |
DE (1) | DE3571644D1 (en) |
DK (1) | DK163675C (en) |
NL (1) | NL8402957A (en) |
NO (1) | NO166655C (en) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0201958A1 (en) * | 1985-05-07 | 1986-11-20 | Akzo N.V. | Pourable detergent and bleach compositions |
US4642198A (en) * | 1984-05-01 | 1987-02-10 | Lever Brothers Company | Liquid bleaching compositions |
EP0240481A1 (en) * | 1986-03-31 | 1987-10-07 | The Procter & Gamble Company | Stable liquid diperoxyacid bleach |
EP0283791A2 (en) * | 1987-03-21 | 1988-09-28 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
EP0283792A2 (en) * | 1987-03-21 | 1988-09-28 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
US4822510A (en) * | 1988-03-25 | 1989-04-18 | Lever Brothers Company | Stably suspended 4,4'-sulfonylbisperoxybenzoic acid bleach in an aqueous liquid |
US4824592A (en) * | 1988-03-25 | 1989-04-25 | Lever Brothers Company | Suspending system for insoluble peroxy acid bleach |
US4828747A (en) * | 1988-03-25 | 1989-05-09 | Lever Brothers Company | Suspending system for insoluble peroxy acid bleach |
DE3740899A1 (en) * | 1987-12-03 | 1989-06-15 | Degussa | Peroxycarboxylic acid-phosphane oxide complexes, their preparation and use |
EP0337516A2 (en) * | 1988-03-21 | 1989-10-18 | Unilever N.V. | Aqueous bleach compositions |
EP0347988A1 (en) * | 1988-06-22 | 1989-12-27 | Akzo N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
EP0442549A2 (en) * | 1990-02-13 | 1991-08-21 | Unilever N.V. | Aqueous liquid bleach composition |
US5049298A (en) * | 1988-11-25 | 1991-09-17 | Akzo Nv | Process for the preparation of bleaching granules |
EP0461700A1 (en) * | 1990-06-12 | 1991-12-18 | Akzo Nobel N.V. | Aqueous disinfectant compositions, and concentrates for preparing the same |
US5126066A (en) * | 1988-06-22 | 1992-06-30 | Akzo N.V. | Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
EP0504952A1 (en) * | 1991-02-15 | 1992-09-23 | The Procter & Gamble Company | Stable liquid amidoperoxyacid bleach |
US5160655A (en) * | 1989-02-27 | 1992-11-03 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds |
US5234617A (en) * | 1992-04-20 | 1993-08-10 | Kathleen B. Hunter | Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol |
US5296156A (en) * | 1988-11-25 | 1994-03-22 | Akzo N.V. | Bleaching granules |
US5358654A (en) * | 1988-06-22 | 1994-10-25 | Akzo Nobel N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5409632A (en) * | 1992-11-16 | 1995-04-25 | The Procter & Gamble Company | Cleaning and bleaching composition with amidoperoxyacid |
US5453214A (en) * | 1991-10-04 | 1995-09-26 | Akzo Nobel N.V. | Suspension and agglomeration of amidoperoxyacids |
US5536435A (en) * | 1992-10-07 | 1996-07-16 | The Procter & Gamble Company | Process for making peroxyacid containing particles |
US5591706A (en) * | 1989-08-08 | 1997-01-07 | Akzo Nobel N.V. | Aqueous peroxide compositions with improved safety profile |
US5932532A (en) * | 1993-10-14 | 1999-08-03 | Procter & Gamble Company | Bleach compositions comprising protease enzyme |
WO2015162042A1 (en) | 2014-04-24 | 2015-10-29 | Cht R. Beitlich Gmbh | Method for brightening dyed textiles |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8411161D0 (en) * | 1984-05-01 | 1984-06-06 | Unilever Plc | Multiple compartment pack |
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FR1220689A (en) * | 1958-04-21 | 1960-05-27 | Procter & Gamble | Bleaching composition |
GB1002893A (en) * | 1961-03-22 | 1965-09-02 | Henkel & Cie Gmbh | Liquid washing agent concentrates |
GB1049482A (en) * | 1962-04-30 | 1966-11-30 | Laporte Chemical | Improvements in or relating to hydrogen peroxide |
FR2305532A1 (en) * | 1975-03-27 | 1976-10-22 | Procter & Gamble | COMPOSITIONS AND ARTICLES FOR BLEACHING TEXTILES |
DE2737864A1 (en) * | 1976-08-27 | 1978-03-02 | Procter & Gamble | PARTICLES FROM A PEROXIC ACID BLEACHING AGENT, PROCESS FOR THEIR MANUFACTURING AND THIS BLEACHING COMPOSITION |
US4483781A (en) * | 1983-09-02 | 1984-11-20 | The Procter & Gamble Company | Magnesium salts of peroxycarboxylic acids |
EP0160342A2 (en) * | 1984-05-01 | 1985-11-06 | Unilever N.V. | Liquid bleaching compositions |
US4563186A (en) * | 1984-04-05 | 1986-01-07 | Purex Corporation | Multi-functional laundry product and employment of same during fabric laundering |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8411161D0 (en) * | 1984-05-01 | 1984-06-06 | Unilever Plc | Multiple compartment pack |
JPS6142600A (en) * | 1984-08-06 | 1986-03-01 | 花王株式会社 | Fungicidal composition |
-
1984
- 1984-09-28 NL NL8402957A patent/NL8402957A/en not_active Application Discontinuation
-
1985
- 1985-09-03 EP EP85201382A patent/EP0176124B1/en not_active Expired
- 1985-09-03 AT AT85201382T patent/ATE44763T1/en not_active IP Right Cessation
- 1985-09-03 DE DE8585201382T patent/DE3571644D1/en not_active Expired
- 1985-09-27 DK DK438285A patent/DK163675C/en active
- 1985-09-27 NO NO853821A patent/NO166655C/en unknown
- 1985-09-27 JP JP60212738A patent/JPH0689357B2/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1220689A (en) * | 1958-04-21 | 1960-05-27 | Procter & Gamble | Bleaching composition |
GB1002893A (en) * | 1961-03-22 | 1965-09-02 | Henkel & Cie Gmbh | Liquid washing agent concentrates |
GB1049482A (en) * | 1962-04-30 | 1966-11-30 | Laporte Chemical | Improvements in or relating to hydrogen peroxide |
FR2305532A1 (en) * | 1975-03-27 | 1976-10-22 | Procter & Gamble | COMPOSITIONS AND ARTICLES FOR BLEACHING TEXTILES |
DE2737864A1 (en) * | 1976-08-27 | 1978-03-02 | Procter & Gamble | PARTICLES FROM A PEROXIC ACID BLEACHING AGENT, PROCESS FOR THEIR MANUFACTURING AND THIS BLEACHING COMPOSITION |
US4483781A (en) * | 1983-09-02 | 1984-11-20 | The Procter & Gamble Company | Magnesium salts of peroxycarboxylic acids |
US4563186A (en) * | 1984-04-05 | 1986-01-07 | Purex Corporation | Multi-functional laundry product and employment of same during fabric laundering |
EP0160342A2 (en) * | 1984-05-01 | 1985-11-06 | Unilever N.V. | Liquid bleaching compositions |
Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4642198A (en) * | 1984-05-01 | 1987-02-10 | Lever Brothers Company | Liquid bleaching compositions |
EP0201958A1 (en) * | 1985-05-07 | 1986-11-20 | Akzo N.V. | Pourable detergent and bleach compositions |
AU600263B2 (en) * | 1986-03-31 | 1990-08-09 | Procter & Gamble Company, The | Stable liquid diperoxyacid bleach |
EP0240481A1 (en) * | 1986-03-31 | 1987-10-07 | The Procter & Gamble Company | Stable liquid diperoxyacid bleach |
EP0283791A2 (en) * | 1987-03-21 | 1988-09-28 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
US4790949A (en) * | 1987-03-21 | 1988-12-13 | Degussa Aktiengesellschaft | Aqueous bleaching agent suspensions containing peroxycarboxylic acid, method for their preparation and use |
EP0283792A2 (en) * | 1987-03-21 | 1988-09-28 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
EP0283791A3 (en) * | 1987-03-21 | 1989-06-07 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
EP0283792A3 (en) * | 1987-03-21 | 1989-06-07 | Degussa Aktiengesellschaft | Aqueous bleaching suspensions containing peroxycarboxylic acid, their preparation and their use |
DE3740899A1 (en) * | 1987-12-03 | 1989-06-15 | Degussa | Peroxycarboxylic acid-phosphane oxide complexes, their preparation and use |
US4929377A (en) * | 1988-03-01 | 1990-05-29 | Lever Brothers Company | Stable, aqueous bleach compositions containing solid organic peroxy acid |
EP0337516A2 (en) * | 1988-03-21 | 1989-10-18 | Unilever N.V. | Aqueous bleach compositions |
EP0337516A3 (en) * | 1988-03-21 | 1990-05-30 | Unilever N.V. | Aqueous bleach compositions |
EP0334405A3 (en) * | 1988-03-25 | 1990-05-30 | Unilever Nv | Aqueous liquid bleach composition |
US4822510A (en) * | 1988-03-25 | 1989-04-18 | Lever Brothers Company | Stably suspended 4,4'-sulfonylbisperoxybenzoic acid bleach in an aqueous liquid |
EP0334405A2 (en) * | 1988-03-25 | 1989-09-27 | Unilever N.V. | Aqueous liquid bleach composition |
EP0334404A2 (en) * | 1988-03-25 | 1989-09-27 | Unilever N.V. | Aqueous liquid bleach composition |
US4828747A (en) * | 1988-03-25 | 1989-05-09 | Lever Brothers Company | Suspending system for insoluble peroxy acid bleach |
US4824592A (en) * | 1988-03-25 | 1989-04-25 | Lever Brothers Company | Suspending system for insoluble peroxy acid bleach |
EP0334404A3 (en) * | 1988-03-25 | 1990-06-06 | Unilever Nv | Aqueous liquid bleach composition |
US5126066A (en) * | 1988-06-22 | 1992-06-30 | Akzo N.V. | Stable, pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5358654A (en) * | 1988-06-22 | 1994-10-25 | Akzo Nobel N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
EP0347988A1 (en) * | 1988-06-22 | 1989-12-27 | Akzo N.V. | Stable pourable aqueous bleaching compositions comprising solid organic peroxy acids and at least two polymers |
US5049298A (en) * | 1988-11-25 | 1991-09-17 | Akzo Nv | Process for the preparation of bleaching granules |
US5296156A (en) * | 1988-11-25 | 1994-03-22 | Akzo N.V. | Bleaching granules |
US5160655A (en) * | 1989-02-27 | 1992-11-03 | Lever Brothers Company, Division Of Conopco, Inc. | Aqueous structured liquid detergent compositions containing selected peroxygen bleach compounds |
US4992194A (en) * | 1989-06-12 | 1991-02-12 | Lever Brothers Company, Division Of Conopco Inc. | Stably suspended organic peroxy bleach in a structured aqueous liquid |
US5591706A (en) * | 1989-08-08 | 1997-01-07 | Akzo Nobel N.V. | Aqueous peroxide compositions with improved safety profile |
EP0442549A2 (en) * | 1990-02-13 | 1991-08-21 | Unilever N.V. | Aqueous liquid bleach composition |
EP0442549A3 (en) * | 1990-02-13 | 1992-01-08 | Unilever Nv | Aqueous liquid bleach composition |
EP0461700A1 (en) * | 1990-06-12 | 1991-12-18 | Akzo Nobel N.V. | Aqueous disinfectant compositions, and concentrates for preparing the same |
US5431848A (en) * | 1991-02-15 | 1995-07-11 | The Procter & Gamble Company | Stable liquid amidoperoxyacid bleach |
EP0504952A1 (en) * | 1991-02-15 | 1992-09-23 | The Procter & Gamble Company | Stable liquid amidoperoxyacid bleach |
US5453214A (en) * | 1991-10-04 | 1995-09-26 | Akzo Nobel N.V. | Suspension and agglomeration of amidoperoxyacids |
US5234617A (en) * | 1992-04-20 | 1993-08-10 | Kathleen B. Hunter | Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol |
US5536435A (en) * | 1992-10-07 | 1996-07-16 | The Procter & Gamble Company | Process for making peroxyacid containing particles |
US5409632A (en) * | 1992-11-16 | 1995-04-25 | The Procter & Gamble Company | Cleaning and bleaching composition with amidoperoxyacid |
US5932532A (en) * | 1993-10-14 | 1999-08-03 | Procter & Gamble Company | Bleach compositions comprising protease enzyme |
WO2015162042A1 (en) | 2014-04-24 | 2015-10-29 | Cht R. Beitlich Gmbh | Method for brightening dyed textiles |
Also Published As
Publication number | Publication date |
---|---|
DK438285D0 (en) | 1985-09-27 |
EP0176124A3 (en) | 1986-12-03 |
EP0176124B1 (en) | 1989-07-19 |
DK438285A (en) | 1986-03-29 |
DK163675B (en) | 1992-03-23 |
NL8402957A (en) | 1986-04-16 |
NO166655B (en) | 1991-05-13 |
NO166655C (en) | 1991-08-21 |
JPS6189298A (en) | 1986-05-07 |
DE3571644D1 (en) | 1989-08-24 |
DK163675C (en) | 1992-08-17 |
JPH0689357B2 (en) | 1994-11-09 |
ATE44763T1 (en) | 1989-08-15 |
NO853821L (en) | 1986-04-01 |
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