CA1221291A - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- CA1221291A CA1221291A CA000443562A CA443562A CA1221291A CA 1221291 A CA1221291 A CA 1221291A CA 000443562 A CA000443562 A CA 000443562A CA 443562 A CA443562 A CA 443562A CA 1221291 A CA1221291 A CA 1221291A
- Authority
- CA
- Canada
- Prior art keywords
- manganese
- weight
- alkalimetal
- sodium
- compound
- 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
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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
- 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
- C11D3/3932—Inorganic compounds or complexes
Abstract
ABSTRACT OF THE DISCLOSURE
Alkaline built detergent bleach compositions are dis-closed comprising a surface-active agent; a peroxide compound bleach; a manganese compound which delivers manganese (II) ions in aqueous solution (e.g. manganous sulphate or manganous chloride); and a builder mixture comprising a water-insoluble aluminosilicate ion-ex-change material and an alkalimetal orthophosphate and/
or an alkalimetal silicate. The composition is particu-larly effective for washing fabrics at lower tempera-tures, e.g. from 20 to 60°C, but is also usable at higher temperature 8.
Alkaline built detergent bleach compositions are dis-closed comprising a surface-active agent; a peroxide compound bleach; a manganese compound which delivers manganese (II) ions in aqueous solution (e.g. manganous sulphate or manganous chloride); and a builder mixture comprising a water-insoluble aluminosilicate ion-ex-change material and an alkalimetal orthophosphate and/
or an alkalimetal silicate. The composition is particu-larly effective for washing fabrics at lower tempera-tures, e.g. from 20 to 60°C, but is also usable at higher temperature 8.
Description
~Z21~9~ C 819 ~R) DETERGE~T COMPOSITIONS
This invention relates to detergent compositions com-prising a peroxide compound bleach suitable for the bleaching and cleaning of fabrics. The peroxide com-pound bleach used herein includes hydrogen peroxide and hydrogen peroxide adducts, e.g. inorganic persalts, which liberate hydrogen peroxide in aqueous solutions such as the water-soluble perborate~, percarbonates, perphosphates, persilicates and the like.
Detergent compositions comprising said peroxide com--pounds are Xnown in the art. Since sald peroxide com-pounds are relatively ineffective at lower tempera-tures, i.e. up to 70~C, these compositions have to be used at near boiling temperatures in order to achieve a satisfactory bleach.
Various proposals have been made to activate peroxide compounds so as to make them usable bleaches at lower temperatures. One proposed route is the use of so-called organic activators - usually organic compounds having one or more reactive acyl residues - which in solution react with the peroxide compound, e.g. sodium perborate, to orm an organic peroxy-acid e.g. peroxy-acetic acid, which i8 a more effective bleach at lower temperatures. Such bleach activators are de~cribed for example in a series of articles by Allan H.Gilbert in "Detergent Age", June 1967, pages 18-20, ~uly 1967, August 1967, pages 26, 27 and 67.
Another approach is the use of heavy metal ions of the transition series which catalyse peroxide decomposi-tion, together with a special type of chelating agen~
for said heavy metal.
~r, ~,~
- , ' ~.,.: ; . . I
: . . ..
C 819 (R) Z9~
US Patent 3 156 654 discloses that only by a proper choice of the heavy metal and of the chelating agent, not only with respect to each other but also in regard of the adsorption power of the material to be bleach-ed i.e. fabric~, relative to the complexing strengthof the chelating agent, an improved bleaching can be obtained. The chelating agent, according to this US
Patent, must be one which is not a stronger complexing agent for the heavy metal ions present than the mate-rial to be bleached is. No further concrete examplesof metaltchelating agent combinations are given, ex-~cept for cobalt and copper salts used in conjunction with pyridine carboxylic acid chelating agents, prefer-preferabl~y as a preformed complex.
US Patent 3 532 634 discloses bleaching compositions comprising a persalt, an organic activator and a tran-sition metal, together with specially selected che-lating agents. The transition metal~ applicable ac-cording to this US patent have atomic numbers of from2~ to 29.
British Patent 984,459 suggested the use of a copper salt in combination with a sequestering agent which 2S is methylaminodiacetic acid, aminotriacetic acid or hydroxyethylaminod~acetic acid.
US Patent 4,119,557 suggested the u~e of a preformed ferric ion complex with a polycarboxyamine type che-lating agent.
US Patent 3 372 125 discloses the use of metal-cyano complexes, particularly Fe-cyano complexes, in denture cleansing compo~itions comprising dipotassium persul-3S phate, sodium perborate, sodium carbonate and triso-dium phosphate.
.
~2~L~l C 819 (R) Still the main problem with heavy metal catalysis is that the results are often inconsistent and/or unsatis-factory, particularly if used for washing fabrics at lower temperatures.
It is an object of the invention to provide an im-proved detergent bleach composition which is effec-tive at lower temperatures, e.g. from 20 to 60C, with-out the use of organic peracids or organic activators forming peroxy acids as the bleaching species.
European Patent Application No. 82563 (published 29 June 1983) describe~ the use of manganese/carbonate mixtures.
It has now surprisingly been found that mangane~e has out~tanding properties with respect to con~istently improving the bleach performance of peroxide compounds at substantially all temperatures, e.g. from 20 to 95C, particularly at lower temperatures, e.g. from 20 to 60C, if used in the presence of a builder system comprising a water-in~oluble aluminosilicate cation-exchange material and an alkalimetal orthophosphate and/or an alkalimetal silicate.
The manganese used according to the present invention can be derived from any manganese (II) salt, such as manganous sulphate and manganous chloride, or from any other manganese compound which delivers manganese ~II) ions in aqueous solution.
Accordingly the invention provides a built detergent bleach composition comprising a peroxide compound and a heavy metal compound, characterized in that it com-prises a mangane~e compound which delivers manganese(II) ions in aquaous solution and a builder system comprising a water-insoluble aluminosilicate cation-.
C 819 (R) ~22~
exchange material and an alkalimetal orthophosphateand/or an alkalimetal silicate.
The optimum level of manganese (II) ions - Mn2~ _ in the wash/bleach solution is dependent upon the formulation in which the manganese as bleach catalyst is applied. In terms of parts per million (ppm) of manganese (II) ions in the wa~h/bleach solution a suitable range will generally be from 0.1 to 50 ppm, preferably from 0.5 - 25 ppm.
These correspond roughly to a manganese (II) metal con-tent in a bleach or detergent composition of about 0.005 - 2.5~ by weight, preferably from 0.025 - 1.0% by weight of the composition.
The level of peroxide compound bleach in the composi-tion of the invention will normally be within the range of about 4 to about 50~ by weight, preferably from 10 to 35% by weight of the total composition.
A preferred peroxide compound is alkalimetal perborate, particularly sodium perborate, which may be in it8 tetrahydrate or its lower hydrate form.
The alumino-silicate cation exchange material is a crystalline or amorphous material having the general formula:
(Cat2/nO)x-Al2o.3 (si2)y-ZH2 wherein Cat is a cation having valency n that is ex-changeable with calcium (e.g. ~a+ or K+); x is a num-ber from 0.7 - l.S; y i8 a number from 1.3 - 4; and z is such that the bound water content is from 10~ to
This invention relates to detergent compositions com-prising a peroxide compound bleach suitable for the bleaching and cleaning of fabrics. The peroxide com-pound bleach used herein includes hydrogen peroxide and hydrogen peroxide adducts, e.g. inorganic persalts, which liberate hydrogen peroxide in aqueous solutions such as the water-soluble perborate~, percarbonates, perphosphates, persilicates and the like.
Detergent compositions comprising said peroxide com--pounds are Xnown in the art. Since sald peroxide com-pounds are relatively ineffective at lower tempera-tures, i.e. up to 70~C, these compositions have to be used at near boiling temperatures in order to achieve a satisfactory bleach.
Various proposals have been made to activate peroxide compounds so as to make them usable bleaches at lower temperatures. One proposed route is the use of so-called organic activators - usually organic compounds having one or more reactive acyl residues - which in solution react with the peroxide compound, e.g. sodium perborate, to orm an organic peroxy-acid e.g. peroxy-acetic acid, which i8 a more effective bleach at lower temperatures. Such bleach activators are de~cribed for example in a series of articles by Allan H.Gilbert in "Detergent Age", June 1967, pages 18-20, ~uly 1967, August 1967, pages 26, 27 and 67.
Another approach is the use of heavy metal ions of the transition series which catalyse peroxide decomposi-tion, together with a special type of chelating agen~
for said heavy metal.
~r, ~,~
- , ' ~.,.: ; . . I
: . . ..
C 819 (R) Z9~
US Patent 3 156 654 discloses that only by a proper choice of the heavy metal and of the chelating agent, not only with respect to each other but also in regard of the adsorption power of the material to be bleach-ed i.e. fabric~, relative to the complexing strengthof the chelating agent, an improved bleaching can be obtained. The chelating agent, according to this US
Patent, must be one which is not a stronger complexing agent for the heavy metal ions present than the mate-rial to be bleached is. No further concrete examplesof metaltchelating agent combinations are given, ex-~cept for cobalt and copper salts used in conjunction with pyridine carboxylic acid chelating agents, prefer-preferabl~y as a preformed complex.
US Patent 3 532 634 discloses bleaching compositions comprising a persalt, an organic activator and a tran-sition metal, together with specially selected che-lating agents. The transition metal~ applicable ac-cording to this US patent have atomic numbers of from2~ to 29.
British Patent 984,459 suggested the use of a copper salt in combination with a sequestering agent which 2S is methylaminodiacetic acid, aminotriacetic acid or hydroxyethylaminod~acetic acid.
US Patent 4,119,557 suggested the u~e of a preformed ferric ion complex with a polycarboxyamine type che-lating agent.
US Patent 3 372 125 discloses the use of metal-cyano complexes, particularly Fe-cyano complexes, in denture cleansing compo~itions comprising dipotassium persul-3S phate, sodium perborate, sodium carbonate and triso-dium phosphate.
.
~2~L~l C 819 (R) Still the main problem with heavy metal catalysis is that the results are often inconsistent and/or unsatis-factory, particularly if used for washing fabrics at lower temperatures.
It is an object of the invention to provide an im-proved detergent bleach composition which is effec-tive at lower temperatures, e.g. from 20 to 60C, with-out the use of organic peracids or organic activators forming peroxy acids as the bleaching species.
European Patent Application No. 82563 (published 29 June 1983) describe~ the use of manganese/carbonate mixtures.
It has now surprisingly been found that mangane~e has out~tanding properties with respect to con~istently improving the bleach performance of peroxide compounds at substantially all temperatures, e.g. from 20 to 95C, particularly at lower temperatures, e.g. from 20 to 60C, if used in the presence of a builder system comprising a water-in~oluble aluminosilicate cation-exchange material and an alkalimetal orthophosphate and/or an alkalimetal silicate.
The manganese used according to the present invention can be derived from any manganese (II) salt, such as manganous sulphate and manganous chloride, or from any other manganese compound which delivers manganese ~II) ions in aqueous solution.
Accordingly the invention provides a built detergent bleach composition comprising a peroxide compound and a heavy metal compound, characterized in that it com-prises a mangane~e compound which delivers manganese(II) ions in aquaous solution and a builder system comprising a water-insoluble aluminosilicate cation-.
C 819 (R) ~22~
exchange material and an alkalimetal orthophosphateand/or an alkalimetal silicate.
The optimum level of manganese (II) ions - Mn2~ _ in the wash/bleach solution is dependent upon the formulation in which the manganese as bleach catalyst is applied. In terms of parts per million (ppm) of manganese (II) ions in the wa~h/bleach solution a suitable range will generally be from 0.1 to 50 ppm, preferably from 0.5 - 25 ppm.
These correspond roughly to a manganese (II) metal con-tent in a bleach or detergent composition of about 0.005 - 2.5~ by weight, preferably from 0.025 - 1.0% by weight of the composition.
The level of peroxide compound bleach in the composi-tion of the invention will normally be within the range of about 4 to about 50~ by weight, preferably from 10 to 35% by weight of the total composition.
A preferred peroxide compound is alkalimetal perborate, particularly sodium perborate, which may be in it8 tetrahydrate or its lower hydrate form.
The alumino-silicate cation exchange material is a crystalline or amorphous material having the general formula:
(Cat2/nO)x-Al2o.3 (si2)y-ZH2 wherein Cat is a cation having valency n that is ex-changeable with calcium (e.g. ~a+ or K+); x is a num-ber from 0.7 - l.S; y i8 a number from 1.3 - 4; and z is such that the bound water content is from 10~ to
2~% by weight.
Preferably a crystalline material is used which can be described by the unit cel content:
.,; ~
~2Z~ C 819 (R) s Nax~Al02 ) x ( SiO2 ) y~ ZH20 wherein x and y are integers of at least 6, the ratio of x to y being in the range of 1 : 1 to 1 : 2; and z is such that the bound water content is from 10% to 28% by weight.
1~e aLumino-silicate preferably has a particle size of from 0.1 to 100 micrometers, ideally between 0.1 and 10 micrometers, and an ion exchan~e capacity of at least 200 mg CaC03 per gram of alumino-silicate (anhydrous basis).
In a preferred embodiment, the water-insoluble alumino-silicate is a crystalline material having the formula described by the unit cell content:
Nal 2 ~ Alo2 ) l 2 ( sio2 ) l 2 zH2o wherein z is from 20 to 30, preferably about 27 An example of this material is the commercially avail-able product known as Zeolite type A, which is typi-cally:
~a20.A1203 2siO2 4 5 H20 and is also described by the unit cell content:
Na12 EA1O2)12 (SiO2)12~ 27 H20 Such aluminosilicates are described in for example British Patent Specifications 1 470 250 and 1 429 143.
Preferred alkalimetal orthophosphate is sodium ortho-phosphate.
Preferred alkalimetal silicate is ~odium silicate of which the ~a20:SiO2 ratio may vary from 1:3.5 to 2:1, preferably from 1:2.6 to 1:1. Examples of suitable so-dium silicate are sodium or~hosilicate, sodium disili cate and the various alkaline sodium ~ilicates.
C 819 (R) 2~3~
The al~inosilicate cation-exchange material and the alkalimetal orthophosphate and/or the alkalimetal 8ili-cate may be used a8 the sole builders in the compo~i-tion of the invention, or they can be used in admixture with other principal or non-principal builders known in the art in minor amounts to the main builder mixture of the invention.
Consequently the total amount of aluminosilicate and orthophosphate in the composition of the invention can be varied as de~ired for providing the required builder capacity of the composition with or without the presence of other builders.
~, Preferably the composition of the invention comprises from 10 to 50~, particularly from 15 to 45~ by weight of a water-insoluble alumino-silicate cation-exchange material.~
The alkalimetal orthophosphate may be present in an amount of from 3 to 50~, preferably from 5 to 25% by weight of the composition. The alkalimetal silicate may be present in an amount of from 1 to 20%, preferably from 3 to lS~ by weight of the composition.
The composition of the invention is alXaline in nature and should preferably have a pH within the range of be-tween 9.5 and 11Ø
Any manganese (II) salt can in principle be employed, ~uch a~ for example manganous sulphate (MnS04), either in its anhydrous form or a~ hydrated ~alt, manganou~
chloride~MnC12), anhydrous or hydrated, and the like.
Generally, the detergent bleach compositions of the invention will include at least one organic soap or i synthetic detergent-active material. Preferably, from ~2Z~9~ C 81'~
about 2% to 50% by weight of an organic, anionic, non~
ionic, amphoteric or ~.witterionic detergent compound, soap or mixtures thereof are included. Many ~uitable detergent-active compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I
and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic com-pounds. The first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphon-ates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alXyl portion of higher aryl radicals.
Examples of suitable anionic detergent compounds are sodium and potassi~.~ alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols pro-duced .for example from tallow or coconut oil; sodium and potassium al~yl (Cg-C20) benzene sulphonates, par-ticularly sodium linear secondary alkyl (C10-ClO-Cl5) benzene sulphonates; sodium alkyl glyceryl ether sul-phates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alco-25 hols derived from petroleum; sodium coconut oil fattyacid monoglyceride sulphates and sulphonates; sodium and potassium salts o sulphuric acid esters of higher (Cg-Cl8) fatty alcohol-alkylene oxide, particularly ethylene oxide reaction products; the reaction proa-ucts of fatty acids such as coconut fatty acids ester-ified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphate and those derived by reacting parafins with S02 and C12 and then hydrolyzing with a base to produce a random sulphonate; olefin sulphon-' .
: . .
, c 819 (R) ~;~Z~Z'99L
ates, which term is u~ed to describe the material madeby reacting olefins, particularly C10-C20 alpha-olefins, with S03 and then neutrali~ing and hydrolyzing the reaction product; and alkali metal salts of long-chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rape-seed oil fatty acids or mixtures thereof. The preferred anionic detergent compound~ are sodium (Cll-C15) alkyl benzene sulphona~es and sodium (C16-C18) alkyl sul-phate 8 .
Examples of ~uitable nonionic detergent compounds whichmay be used include the reaction product~ of alkylene oxides, usually ethylene oxide, with alkyl (C6-C~2) phenols, generally 5 to 25 EO, i.e. 5 to 25 unit~ of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic deter-gent compounds include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sul-phoxides.
Mixtures of detergent-active compounds, for example mixed anionic or mixed anionic and nonionic compounds, may be used in the detergent compositions, particu-larly in the latter case to provide controlled low sudsing properties. This is beneficial for composi-tions intended for use in suds-intolerant automatic washing machines.
Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compo~ition~ of the invention, but this is not normally desired owing to their relatively high co~t. If any amphoteric or ~wit-, ^:
:
C 81~3 (R) terionic detergent-active compound~ are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anion and/or nonionic detergent-active compounds.
The composition of the present invention is prefer-ably substantially free of other inorganic phosphate builders. However, if desired, the composition may contain said other inorganic phosphate such as the alkali metal (preferably sodium) trip~osphate, pyro-phosphate or polymer phosphate, preferably at a level of up to about 25% by weight based on the total com-position.
Apart from the components already mentioned, the com-position of the invention can contain any of the con-ventional additives in the amounts in which such mate-rials are normally employed in fabric-washing deter-gent compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids; lather depressants such as alkyl p}losphates and silicones; anti~redeposition agents such as sodium carboxymethylcellulose, poly-vinyl pyrrolidone and the cellulose ethers such aRmethyl cellulose and ethyl hydroxyethyl cellulose;
stabilizers such as ethylenediamine tetra-acetic acid, ethylenediamine tetramethylene phosphonate and dieth-ylenetriamine pentamethylene phosphonate; fabric-softening agents; inorganic salts such as sodium 8ul-phate and - usually present in very minor amounts -fluorescent agents, perfumes, germicides and colour-ants.
It is desirable to include one or more antideposition agents in the cleaning composition of the invention, to decrease a tendency to form inorganic deposits on C 819 (R) washed fabrics. The amount of any such antideposition agent is normally from about O.l~ to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the compo~ition. The preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic pho~phonates.
Other non-phosphate detergency builders may be incor-porated as well if desired, at a level preerably up to about 25~ by weight of the composition.
The detergent bleach composition of the invention is preferably presented in free-flowing particulate e.g.
powdered or granular form, and can be produced by any lS of the techniques commonly employed in the manufacture of such detergent compo~itions, but preferably by slurry-making and spray-drying processes to form a de-tergent base powder to which the heat-~ensitive ingre-dients, e.g. the peroxide compound and optionally some other ingredients as de~ired, are added. It is prefer-- red that the procesa used to form the compo~ition should result in a product having a moisture content of not more than about 12%, more preferably from about 4% to about 10% by weight.
The manganese compound may be added to the composition a6 part of the aqueous slurry, which is then dried to a particle detergent powder, or preferably as a dry substance mixed in with the detergent base powder.
One major advantage of the present invention is that effective bleach improvement at substantially all tempera~ure is independent of ~pecially ~elected chelating agents.
Furthermore the manganese (II) ~ixed builder system of the invention is an effec~ive s11-te~perature csta1yst ~: ~
' :.
C 819 (R) Z~L2~
for peroxide compounds, showing minimal wasteful 801u-tion decompo3ition.
Exam~
-The following particulate detergent composition was prepared by spray-drying an aqueous detergent slurry forming a base powder to which there was added by dry-mixing sodium perborate. To this powder manganous sul-phate was added in varying amounts.
Composit _ % by weight (A) (B) Sodium C12-alkylbenzenesulphonate 7.0 7.0 Fatty alcohol - 7 ethylene oxide 3.5 3.5 Sodium C16-C20 fatty acid soap 4.0 4~0 Zeolite HA~ A 40 (aluminosilicate ex Degussa) 21.0 Sodium orthophosphate 11.6 Sodium triphosphate - 25.0 Sodium sulphate 15.0 15.0 Alkaline sodium silicate (1:2) - 7.0 Sodium perborate tetrahydrate 30.0 30.0 Water + minor ingredients up to 100~.
The compositions (A) were tested at a dosage of 5 g/l in a 30 minutes isothermal wash at 40C in 24H water and compared with compositions (8) outside the inven-tion.
The bleaching results obtained on tea-stained test cloths measured as ~ R (reflectance) were as follows:
-, , ": ' ., , ' .' . :
:
C Bl9 (R) ~ZZ~L29~
TABLE I
Mn2~
_ _ _ ~R ~ R
ppm in solution % in product (A) (B) _ ~
0.5 O.Ol 3.2 2.8 1.0 0.02 3.5 2.9 2.0 0.04 5.0 2.9 5.0 0.10 6.7 2.9 7.0 0.14 7.0 2.9 lo.~ L 0.20 6.4 2.9 l From the above results it i8 clear that manganese is substan-tially non-effective in the conventionally built detergent compositions (B). The manganese effect in the Zeolite/orthophosphate built detergent composi-~ion~ (A) on peroxide bleaching i8 evident.
Example II
The following alkaline particulate detergent composi-tions,were prepared:
2S % by weight Sodium C12 alkylbenzene sulphonate 15 Aluminosilicate (Zeolite HAB A 40 ex Degussa 25 Alkaline sodium silicate 4 Sodium perborate tetrahydrate 25 Sodium ~ulphate 23 Water ~ alXaline agent 8 To this powder manganous sulphate was added in varying amounts and the compositions were tested at a dosage of 5 g/l in a 30 minutes' isothermal wash at 40C in 24H water.
: .
. . :
:,: - '. . . :
- ~ Z Z'lZ 9 1 C 819 ~R) The bleaching results obtained on tea-stained test cloths, measured a~ ~R (reflectance) were as follows:
Mn2+
_ in product ppm in solution ~ R
_ 0 0 3.55 0.01 0.5 5.28 0.014 0.7 10.21 0.017 0.85 11.22 0.0~ 1.0 10.30 0.04 2.0 6.~0 ***
- ~ .
:., ; ''
Preferably a crystalline material is used which can be described by the unit cel content:
.,; ~
~2Z~ C 819 (R) s Nax~Al02 ) x ( SiO2 ) y~ ZH20 wherein x and y are integers of at least 6, the ratio of x to y being in the range of 1 : 1 to 1 : 2; and z is such that the bound water content is from 10% to 28% by weight.
1~e aLumino-silicate preferably has a particle size of from 0.1 to 100 micrometers, ideally between 0.1 and 10 micrometers, and an ion exchan~e capacity of at least 200 mg CaC03 per gram of alumino-silicate (anhydrous basis).
In a preferred embodiment, the water-insoluble alumino-silicate is a crystalline material having the formula described by the unit cell content:
Nal 2 ~ Alo2 ) l 2 ( sio2 ) l 2 zH2o wherein z is from 20 to 30, preferably about 27 An example of this material is the commercially avail-able product known as Zeolite type A, which is typi-cally:
~a20.A1203 2siO2 4 5 H20 and is also described by the unit cell content:
Na12 EA1O2)12 (SiO2)12~ 27 H20 Such aluminosilicates are described in for example British Patent Specifications 1 470 250 and 1 429 143.
Preferred alkalimetal orthophosphate is sodium ortho-phosphate.
Preferred alkalimetal silicate is ~odium silicate of which the ~a20:SiO2 ratio may vary from 1:3.5 to 2:1, preferably from 1:2.6 to 1:1. Examples of suitable so-dium silicate are sodium or~hosilicate, sodium disili cate and the various alkaline sodium ~ilicates.
C 819 (R) 2~3~
The al~inosilicate cation-exchange material and the alkalimetal orthophosphate and/or the alkalimetal 8ili-cate may be used a8 the sole builders in the compo~i-tion of the invention, or they can be used in admixture with other principal or non-principal builders known in the art in minor amounts to the main builder mixture of the invention.
Consequently the total amount of aluminosilicate and orthophosphate in the composition of the invention can be varied as de~ired for providing the required builder capacity of the composition with or without the presence of other builders.
~, Preferably the composition of the invention comprises from 10 to 50~, particularly from 15 to 45~ by weight of a water-insoluble alumino-silicate cation-exchange material.~
The alkalimetal orthophosphate may be present in an amount of from 3 to 50~, preferably from 5 to 25% by weight of the composition. The alkalimetal silicate may be present in an amount of from 1 to 20%, preferably from 3 to lS~ by weight of the composition.
The composition of the invention is alXaline in nature and should preferably have a pH within the range of be-tween 9.5 and 11Ø
Any manganese (II) salt can in principle be employed, ~uch a~ for example manganous sulphate (MnS04), either in its anhydrous form or a~ hydrated ~alt, manganou~
chloride~MnC12), anhydrous or hydrated, and the like.
Generally, the detergent bleach compositions of the invention will include at least one organic soap or i synthetic detergent-active material. Preferably, from ~2Z~9~ C 81'~
about 2% to 50% by weight of an organic, anionic, non~
ionic, amphoteric or ~.witterionic detergent compound, soap or mixtures thereof are included. Many ~uitable detergent-active compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I
and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds which can be used are synthetic anionic, soap and nonionic com-pounds. The first-mentioned are usually water-soluble alkali metal salts of organic sulphates and sulphon-ates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alXyl portion of higher aryl radicals.
Examples of suitable anionic detergent compounds are sodium and potassi~.~ alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols pro-duced .for example from tallow or coconut oil; sodium and potassium al~yl (Cg-C20) benzene sulphonates, par-ticularly sodium linear secondary alkyl (C10-ClO-Cl5) benzene sulphonates; sodium alkyl glyceryl ether sul-phates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alco-25 hols derived from petroleum; sodium coconut oil fattyacid monoglyceride sulphates and sulphonates; sodium and potassium salts o sulphuric acid esters of higher (Cg-Cl8) fatty alcohol-alkylene oxide, particularly ethylene oxide reaction products; the reaction proa-ucts of fatty acids such as coconut fatty acids ester-ified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphate and those derived by reacting parafins with S02 and C12 and then hydrolyzing with a base to produce a random sulphonate; olefin sulphon-' .
: . .
, c 819 (R) ~;~Z~Z'99L
ates, which term is u~ed to describe the material madeby reacting olefins, particularly C10-C20 alpha-olefins, with S03 and then neutrali~ing and hydrolyzing the reaction product; and alkali metal salts of long-chain C8-C22 fatty acids such as the sodium soaps of tallow, coconut oil, palmkernel oil, palm oil or hardened rape-seed oil fatty acids or mixtures thereof. The preferred anionic detergent compound~ are sodium (Cll-C15) alkyl benzene sulphona~es and sodium (C16-C18) alkyl sul-phate 8 .
Examples of ~uitable nonionic detergent compounds whichmay be used include the reaction product~ of alkylene oxides, usually ethylene oxide, with alkyl (C6-C~2) phenols, generally 5 to 25 EO, i.e. 5 to 25 unit~ of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic deter-gent compounds include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sul-phoxides.
Mixtures of detergent-active compounds, for example mixed anionic or mixed anionic and nonionic compounds, may be used in the detergent compositions, particu-larly in the latter case to provide controlled low sudsing properties. This is beneficial for composi-tions intended for use in suds-intolerant automatic washing machines.
Amounts of amphoteric or zwitterionic detergent-active compounds can also be used in the compo~ition~ of the invention, but this is not normally desired owing to their relatively high co~t. If any amphoteric or ~wit-, ^:
:
C 81~3 (R) terionic detergent-active compound~ are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anion and/or nonionic detergent-active compounds.
The composition of the present invention is prefer-ably substantially free of other inorganic phosphate builders. However, if desired, the composition may contain said other inorganic phosphate such as the alkali metal (preferably sodium) trip~osphate, pyro-phosphate or polymer phosphate, preferably at a level of up to about 25% by weight based on the total com-position.
Apart from the components already mentioned, the com-position of the invention can contain any of the con-ventional additives in the amounts in which such mate-rials are normally employed in fabric-washing deter-gent compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids; lather depressants such as alkyl p}losphates and silicones; anti~redeposition agents such as sodium carboxymethylcellulose, poly-vinyl pyrrolidone and the cellulose ethers such aRmethyl cellulose and ethyl hydroxyethyl cellulose;
stabilizers such as ethylenediamine tetra-acetic acid, ethylenediamine tetramethylene phosphonate and dieth-ylenetriamine pentamethylene phosphonate; fabric-softening agents; inorganic salts such as sodium 8ul-phate and - usually present in very minor amounts -fluorescent agents, perfumes, germicides and colour-ants.
It is desirable to include one or more antideposition agents in the cleaning composition of the invention, to decrease a tendency to form inorganic deposits on C 819 (R) washed fabrics. The amount of any such antideposition agent is normally from about O.l~ to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the compo~ition. The preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic pho~phonates.
Other non-phosphate detergency builders may be incor-porated as well if desired, at a level preerably up to about 25~ by weight of the composition.
The detergent bleach composition of the invention is preferably presented in free-flowing particulate e.g.
powdered or granular form, and can be produced by any lS of the techniques commonly employed in the manufacture of such detergent compo~itions, but preferably by slurry-making and spray-drying processes to form a de-tergent base powder to which the heat-~ensitive ingre-dients, e.g. the peroxide compound and optionally some other ingredients as de~ired, are added. It is prefer-- red that the procesa used to form the compo~ition should result in a product having a moisture content of not more than about 12%, more preferably from about 4% to about 10% by weight.
The manganese compound may be added to the composition a6 part of the aqueous slurry, which is then dried to a particle detergent powder, or preferably as a dry substance mixed in with the detergent base powder.
One major advantage of the present invention is that effective bleach improvement at substantially all tempera~ure is independent of ~pecially ~elected chelating agents.
Furthermore the manganese (II) ~ixed builder system of the invention is an effec~ive s11-te~perature csta1yst ~: ~
' :.
C 819 (R) Z~L2~
for peroxide compounds, showing minimal wasteful 801u-tion decompo3ition.
Exam~
-The following particulate detergent composition was prepared by spray-drying an aqueous detergent slurry forming a base powder to which there was added by dry-mixing sodium perborate. To this powder manganous sul-phate was added in varying amounts.
Composit _ % by weight (A) (B) Sodium C12-alkylbenzenesulphonate 7.0 7.0 Fatty alcohol - 7 ethylene oxide 3.5 3.5 Sodium C16-C20 fatty acid soap 4.0 4~0 Zeolite HA~ A 40 (aluminosilicate ex Degussa) 21.0 Sodium orthophosphate 11.6 Sodium triphosphate - 25.0 Sodium sulphate 15.0 15.0 Alkaline sodium silicate (1:2) - 7.0 Sodium perborate tetrahydrate 30.0 30.0 Water + minor ingredients up to 100~.
The compositions (A) were tested at a dosage of 5 g/l in a 30 minutes isothermal wash at 40C in 24H water and compared with compositions (8) outside the inven-tion.
The bleaching results obtained on tea-stained test cloths measured as ~ R (reflectance) were as follows:
-, , ": ' ., , ' .' . :
:
C Bl9 (R) ~ZZ~L29~
TABLE I
Mn2~
_ _ _ ~R ~ R
ppm in solution % in product (A) (B) _ ~
0.5 O.Ol 3.2 2.8 1.0 0.02 3.5 2.9 2.0 0.04 5.0 2.9 5.0 0.10 6.7 2.9 7.0 0.14 7.0 2.9 lo.~ L 0.20 6.4 2.9 l From the above results it i8 clear that manganese is substan-tially non-effective in the conventionally built detergent compositions (B). The manganese effect in the Zeolite/orthophosphate built detergent composi-~ion~ (A) on peroxide bleaching i8 evident.
Example II
The following alkaline particulate detergent composi-tions,were prepared:
2S % by weight Sodium C12 alkylbenzene sulphonate 15 Aluminosilicate (Zeolite HAB A 40 ex Degussa 25 Alkaline sodium silicate 4 Sodium perborate tetrahydrate 25 Sodium ~ulphate 23 Water ~ alXaline agent 8 To this powder manganous sulphate was added in varying amounts and the compositions were tested at a dosage of 5 g/l in a 30 minutes' isothermal wash at 40C in 24H water.
: .
. . :
:,: - '. . . :
- ~ Z Z'lZ 9 1 C 819 ~R) The bleaching results obtained on tea-stained test cloths, measured a~ ~R (reflectance) were as follows:
Mn2+
_ in product ppm in solution ~ R
_ 0 0 3.55 0.01 0.5 5.28 0.014 0.7 10.21 0.017 0.85 11.22 0.0~ 1.0 10.30 0.04 2.0 6.~0 ***
- ~ .
:., ; ''
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A built detergent bleach composition comprising a peroxide compound and a heavy metal compound, characterized in that it comprises a peroxide compound in an amount of from 4 to 50% by weight, a manganese compound which delivers man-ganese (II) ions in aqueous solution in an amount of 0.005 to 2.5% by weight as manganese (II) metal, and a builder system comprising a water-insoluble alumino-silicate cation-exchange material and an alkalimetal orthophosphate and/or an alkalimetal silicate.
2. A composition according to claim 1, characterized in that said manganese compound is a manganese (II) salt.
3. A composition according to claim 2, characterized in that said manganese salt is selected from manganous sul-phate and manganous chloride.
4. A composition according to claim 1, characterized in that it contains 0.025 to 1.0% by weight of manganese (II) metal.
5. A composition according to claim 1, characterized in that it contains 10-50% by weight of water-insoluble alum-ino silicate cation-exchange material.
6. A composition according to claim 1, characterized in that it contains 3-50% by weight of an alkalimetal ortho-phospate and/or 1-20% by weight of alkalimetal silicate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8236005 | 1982-12-17 | ||
| GB8236005 | 1982-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221291A true CA1221291A (en) | 1987-05-05 |
Family
ID=10535061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000443562A Expired CA1221291A (en) | 1982-12-17 | 1983-12-16 | Detergent compositions |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4478733A (en) |
| EP (1) | EP0111963B1 (en) |
| JP (1) | JPS59120699A (en) |
| AT (1) | ATE37560T1 (en) |
| AU (1) | AU561035B2 (en) |
| BR (1) | BR8306940A (en) |
| CA (1) | CA1221291A (en) |
| DE (1) | DE3378127D1 (en) |
| DK (1) | DK580983A (en) |
| FI (1) | FI834561A (en) |
| GB (1) | GB2132656B (en) |
| GR (1) | GR79448B (en) |
| IN (1) | IN158636B (en) |
| KE (1) | KE3654A (en) |
| MY (1) | MY8600670A (en) |
| NO (1) | NO159804C (en) |
| NZ (1) | NZ206553A (en) |
| PH (1) | PH19248A (en) |
| PT (1) | PT77835B (en) |
| ZA (1) | ZA839299B (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8316760D0 (en) * | 1983-06-20 | 1983-07-20 | Unilever Plc | Detergent bleach compositions |
| GB8329761D0 (en) * | 1983-11-08 | 1983-12-14 | Unilever Plc | Metal adjuncts |
| NZ210397A (en) * | 1983-12-06 | 1986-11-12 | Unilever Plc | Alkaline built detergent bleach composition containing a peroxide compound and a manganese compound |
| NZ210398A (en) * | 1983-12-06 | 1986-11-12 | Unilever Plc | Detergent bleach composition containing a peroxide compound and a manganese compound |
| US4536183A (en) * | 1984-04-09 | 1985-08-20 | Lever Brothers Company | Manganese bleach activators |
| US4623357A (en) * | 1985-04-02 | 1986-11-18 | Lever Brothers Company | Bleach compositions |
| US4601845A (en) * | 1985-04-02 | 1986-07-22 | Lever Brothers Company | Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials |
| US4711748A (en) * | 1985-12-06 | 1987-12-08 | Lever Brothers Company | Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation |
| US4655782A (en) * | 1985-12-06 | 1987-04-07 | Lever Brothers Company | Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween |
| US4728455A (en) * | 1986-03-07 | 1988-03-01 | Lever Brothers Company | Detergent bleach compositions, bleaching agents and bleach activators |
| GB8618635D0 (en) * | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
| GB8619152D0 (en) * | 1986-08-06 | 1986-09-17 | Unilever Plc | Conditioning fabrics |
| GB8619153D0 (en) * | 1986-08-06 | 1986-09-17 | Unilever Plc | Fabric conditioning composition |
| US4954292A (en) * | 1986-10-01 | 1990-09-04 | Lever Brothers Co. | Detergent composition containing PVP and process of using same |
| US4731196A (en) * | 1986-10-28 | 1988-03-15 | Ethyl Corporation | Process for making bleach activator |
| ES2016465A6 (en) * | 1989-06-14 | 1990-11-01 | Camp Jabones | Textile bleaching compositions effective at low temperatures. |
| US5686014A (en) * | 1994-04-07 | 1997-11-11 | The Procter & Gamble Company | Bleach compositions comprising manganese-containing bleach catalysts |
| DE69504489T2 (en) * | 1994-04-07 | 1999-05-20 | Procter & Gamble | BLEACHING AGENTS CONTAINING METAL BLEACHING CATALYSTS AND ANTIOXIDANTS |
| US5560748A (en) * | 1994-06-10 | 1996-10-01 | The Procter & Gamble Company | Detergent compositions comprising large pore size redox catalysts |
| ES2221665T3 (en) | 1994-07-21 | 2005-01-01 | Ciba Specialty Chemicals Holding Inc. | COMPOSITION OF WHITENING OF FABRICS. |
| US5720897A (en) * | 1995-01-25 | 1998-02-24 | University Of Florida | Transition metal bleach activators for bleaching agents and detergent-bleach compositions |
| ATE209245T1 (en) * | 1995-02-02 | 2001-12-15 | Procter & Gamble | METHOD FOR REMOVAL OF TEA STAINS IN DISHWASHERS HAVING COMPOSITIONS CONTAINING COBALT (III) CATALYST |
| US5968881A (en) * | 1995-02-02 | 1999-10-19 | The Procter & Gamble Company | Phosphate built automatic dishwashing compositions comprising catalysts |
| DE69608541T2 (en) * | 1995-02-02 | 2001-01-18 | Procter & Gamble | MACHINE DISHWASHER COMPOSITIONS WITH COBALT CHELATE CATALYSTS |
| BR9609384A (en) * | 1995-06-16 | 1999-05-18 | Procter & Gamble | Bleaching compositions comprising cobalt catalysts |
| ATE203051T1 (en) * | 1995-06-16 | 2001-07-15 | Procter & Gamble | MACHINE DISHWASHING DETERGENT CONTAINING COBALT CATALYSTS |
| US5703034A (en) * | 1995-10-30 | 1997-12-30 | The Procter & Gamble Company | Bleach catalyst particles |
| DE19600159A1 (en) | 1996-01-04 | 1997-07-10 | Hoechst Ag | Bleaching agent systems containing bis- and tris (mu-oxo) -di-manganese complex salts |
| DE19606343A1 (en) | 1996-02-21 | 1997-08-28 | Hoechst Ag | Bleach |
| KR100462465B1 (en) * | 2003-11-20 | 2004-12-23 | 정천수 | A charging battery case having uni-jack, and a jack plug for the case |
| US20060147394A1 (en) * | 2004-12-30 | 2006-07-06 | Ramachandra Shastry | Tooth whitening composition containing cross-linked polymer-peroxides |
| US10196592B2 (en) | 2014-06-13 | 2019-02-05 | Ecolab Usa Inc. | Enhanced catalyst stability for alkaline detergent formulations |
| US9624119B2 (en) | 2014-06-13 | 2017-04-18 | Ecolab Usa Inc. | Enhanced catalyst stability in activated peroxygen and/or alkaline detergent formulations |
| US9783766B2 (en) | 2015-04-03 | 2017-10-10 | Ecolab Usa Inc. | Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid |
| US10280386B2 (en) | 2015-04-03 | 2019-05-07 | Ecolab Usa Inc. | Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid |
| US11225631B2 (en) | 2018-03-19 | 2022-01-18 | Ecolab Usa Inc. | Acidic liquid detergent compositions containing bleach catalyst and free of anionic surfactant |
| US10870818B2 (en) | 2018-06-15 | 2020-12-22 | Ecolab Usa Inc. | Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL276367A (en) * | 1961-03-24 | |||
| US3156654A (en) * | 1961-06-19 | 1964-11-10 | Shell Oil Co | Bleaching |
| GB1120944A (en) * | 1964-07-24 | 1968-07-24 | Unilever Ltd | Catalysts |
| US3372125A (en) * | 1965-11-15 | 1968-03-05 | Peter Strong & Company Inc | Denture cleanser |
| GB1182143A (en) * | 1966-03-01 | 1970-02-25 | United States Borax Chem | Bleaching Compositions and Methods. |
| GB1565807A (en) * | 1975-12-18 | 1980-04-23 | Uilever Ltd | Process and compositions for cleaning fabrics |
| US4303556A (en) * | 1977-11-02 | 1981-12-01 | The Procter & Gamble Company | Spray-dried detergent compositions |
| DE2902236A1 (en) * | 1978-01-25 | 1979-07-26 | Kao Corp | BLEACHING AGENT |
| EP0025608A2 (en) * | 1979-09-18 | 1981-03-25 | Süd-Chemie Ag | Catalyst for the controlled decomposition of peroxide compounds, its preparation and use; washing or bleaching agent and process for producing a washing or bleaching agent that contains peroxide compounds |
| FI822428L (en) * | 1981-07-15 | 1983-01-16 | Unilever Nv | RENGOERINGSBLANDNING |
| US4481129A (en) * | 1981-12-23 | 1984-11-06 | Lever Brothers Company | Bleach compositions |
-
1983
- 1983-12-08 US US06/559,593 patent/US4478733A/en not_active Expired - Fee Related
- 1983-12-09 AT AT83201742T patent/ATE37560T1/en not_active IP Right Cessation
- 1983-12-09 EP EP83201742A patent/EP0111963B1/en not_active Expired
- 1983-12-09 DE DE8383201742T patent/DE3378127D1/en not_active Expired
- 1983-12-12 NZ NZ206553A patent/NZ206553A/en unknown
- 1983-12-13 FI FI834561A patent/FI834561A/en not_active Application Discontinuation
- 1983-12-13 AU AU22362/83A patent/AU561035B2/en not_active Ceased
- 1983-12-13 GR GR73233A patent/GR79448B/el unknown
- 1983-12-14 ZA ZA839299A patent/ZA839299B/en unknown
- 1983-12-15 GB GB08333397A patent/GB2132656B/en not_active Expired
- 1983-12-16 JP JP58237753A patent/JPS59120699A/en active Granted
- 1983-12-16 CA CA000443562A patent/CA1221291A/en not_active Expired
- 1983-12-16 BR BR8306940A patent/BR8306940A/en not_active IP Right Cessation
- 1983-12-16 IN IN396/BOM/83A patent/IN158636B/en unknown
- 1983-12-16 PT PT77835A patent/PT77835B/en unknown
- 1983-12-16 PH PH29992A patent/PH19248A/en unknown
- 1983-12-16 NO NO834653A patent/NO159804C/en unknown
- 1983-12-16 DK DK580983A patent/DK580983A/en not_active Application Discontinuation
-
1986
- 1986-07-24 KE KE3654A patent/KE3654A/en unknown
- 1986-12-30 MY MY670/86A patent/MY8600670A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK580983A (en) | 1984-06-18 |
| GB2132656B (en) | 1986-05-21 |
| FI834561A0 (en) | 1983-12-13 |
| IN158636B (en) | 1986-12-27 |
| DE3378127D1 (en) | 1988-11-03 |
| NO159804B (en) | 1988-10-31 |
| KE3654A (en) | 1986-09-12 |
| EP0111963B1 (en) | 1988-09-28 |
| FI834561A (en) | 1984-06-18 |
| EP0111963A2 (en) | 1984-06-27 |
| DK580983D0 (en) | 1983-12-16 |
| MY8600670A (en) | 1986-12-31 |
| JPS59120699A (en) | 1984-07-12 |
| ZA839299B (en) | 1985-07-31 |
| GR79448B (en) | 1984-10-30 |
| NO834653L (en) | 1984-06-18 |
| PT77835B (en) | 1986-09-15 |
| EP0111963A3 (en) | 1986-11-20 |
| AU561035B2 (en) | 1987-04-30 |
| GB2132656A (en) | 1984-07-11 |
| BR8306940A (en) | 1984-07-24 |
| NO159804C (en) | 1989-02-08 |
| JPS6125759B2 (en) | 1986-06-17 |
| NZ206553A (en) | 1986-05-09 |
| AU2236283A (en) | 1984-06-21 |
| US4478733A (en) | 1984-10-23 |
| PH19248A (en) | 1986-02-14 |
| PT77835A (en) | 1984-01-01 |
| ATE37560T1 (en) | 1988-10-15 |
| GB8333397D0 (en) | 1984-01-25 |
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