EP0514422B1 - Liquid bleach composition - Google Patents

Liquid bleach composition Download PDF

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Publication number
EP0514422B1
EP0514422B1 EP91903330A EP91903330A EP0514422B1 EP 0514422 B1 EP0514422 B1 EP 0514422B1 EP 91903330 A EP91903330 A EP 91903330A EP 91903330 A EP91903330 A EP 91903330A EP 0514422 B1 EP0514422 B1 EP 0514422B1
Authority
EP
European Patent Office
Prior art keywords
bleach
weight
alkali metal
compositions
preferred
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.)
Revoked
Application number
EP91903330A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0514422A1 (en
Inventor
Johannes Cornelis Van De Pas
Theresia Maria Olsthoorn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Priority claimed from EP90200290A external-priority patent/EP0385522B1/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0514422A1 publication Critical patent/EP0514422A1/en
Application granted granted Critical
Publication of EP0514422B1 publication Critical patent/EP0514422B1/en
Anticipated expiration legal-status Critical
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising an aqueous base, detergent active materials and a bleach material.
  • EP-A-0,368,575 discloses aqueous liquid detergent compositions comprising low active levels, solid peroxygen bleach particles and alkali metal silicate, obtained by mixing a detergent composition with a bleach composition. These diluted compositions show high oxygen loss upon storage.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising an aqueous base containing from 10-30% by weight of detergent active materials, from 1-40% by weight of a peroxygen bleach material, partially being present as solid peroxygen particles and from 0.4 to 5 % by weight of alkali metal silicate material, preferably a disilicate material.
  • compositions according to the present invention comprise a bleach material, which is preferably a peroxygen bleach.
  • This bleach component may be partially present in the system in dissolved form, the remaining part preferably being present as solid peroxygen particles which are suspended in the system.
  • bleach compounds include the perborates, persulfates, peroxy disulfates, per- phosphates and the crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea or alkali metal carbonate.
  • encapsulated bleaches may be used. Preferred bleaches are only partially soluble in the system. Especially preferred is the use of perborate or percarbonate bleaches.
  • the bleach component is preferably added in an amount corresponding to 0.1 to 15% by weight of active oxygen, more preferred from 0.5 to 10% active oxygen, typically from 1.0 to 5.0% active oxygen.
  • the amount of bleach will be between 1 and 40 % by weight of the aqueous composition, more preferred from 7 to 30%, especially preferred from 10 to 25 % by weight of the composition.
  • compositions of the invention also comprise an alkali metal silicate material.
  • Suitable silicate materials are for example sodium and potassium silicates, for example sodium metasilicate and sodium disilicates. The use of alkali metal disilicates is preferred.
  • the alkali metal silicate material can have two functions, firstly it prevents the solubilisation of the bleach material, therewith minimizing the amount of instable dissolved bleach and secondly it retards the decomposition of the dissolved bleach materials.
  • the level of alkali metal silicate material is from 0.4 to 5 %.
  • compositions of the present invention also comprise detergent active materials.
  • detergent active materials Surprisingly it has been found that a combination of bleach materials and alkali metal silicate materials is suitable for use in ready to use aqueous liquid detergent compositions.
  • the detergent active materials in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • they may be chosen from any of the classes, subclasses and specific materials described in "Surface Active Agents” Vol. I, by Schwartz & Perry, Interscience 1949 and “Surface Active Agents” Vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents” published by the McCutcheon division of Manufacturing Confectioners Company or in Tensid-Taschenburch", H. Stache, 2nd Edn., Carl Hanser Verlag, Munchen & Wien, 1981.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C, 8 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • salting out resistant active materials such as for example described in EP 328 177
  • alkyl poly glycoside surfactants such as for example disclosed in EP 70 074.
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C s -C 2o ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and acid esters of higher (C 8 -C l8 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as
  • an alkali metal soap of a fatty acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, alkylsuccinic acid, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the total detergent active material will be present at from 10% to 30% by weight of the total composition.
  • compositions of the invention may be un-structured (isotropic) or structured.
  • Structured liquids of the invention may be internally structured whereby the structure is formed by the detergent active materials in the composition or externally structured, whereby the structure is provided by an external structurant.
  • compositions of the invention are internally structured.
  • lamellar droplets are called "spherulites".
  • the presence and identity of a surfactant structuring system in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
  • the aqueous continuous phase contains dissolved electrolyte.
  • electrolyte means any ionic water soluble material.
  • the electrolytes may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase.
  • Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g.
  • salts includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
  • compositions where the detergent active material comprises blends of different surfactant types.
  • Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
  • the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646, that is salting-out electrolytes have a lyotropic number of less than 9.5.
  • some salting-in electrolyte (as defined in the latter specification) may also be included, provided it is of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
  • Some or all of the electrolyte may have detergency builder properties.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
  • the salting-out electrolyte comprises citrate.
  • Examples of phosphorus-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and zeolites.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes
  • potassium salts to promote the solubility of sodium salts.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, CMOS, TMS, TDS, melitic acid, benzene polycarboxylic acids and citric acid.
  • the level of non-soap builder material is from 0-50% by weight of the composition, more preferred from 5-40%, most preferred 10-35%.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6000; said second polymer having a molecular weight of at least 1000.
  • Use of such polymers is generally described in our EP 301,883. Typical levels are from 0.5 to 4.5% by weight.
  • compositions according to the present is preferably less than 1,500 mPa.s, more preferred less than 1,000 mPa.s, especially preferred between 30 and 900 mPa.s at 21 s -1 .
  • One way of regulating the viscosity and stability of compositions according to the present invention is to include viscosity regulating polymeric materials.
  • Viscosity and/or stability regulating polymers which are preferred for incorporation in compositions according to the invention include deflocculating polymers having a hydrophilic backbone and at least one hydrophobic side chain. Such polymers are for instance described in our copending European application EP 89201530.6 (EP 346 995).
  • Deflocculation polymers for use in detergent formulations according to the present invention may be of anionic, nonionic or cationic nature. Anionic deflocculating polymers are preferred.
  • the hydrophilic backbone of the polymer is typically a homo-, co- or ter-polymer containing carboxylic acid groups (or more preferably) salt forms thereof), e.g. maleate or acrylate polymers or co-polymers of these together or with other monomer units such as vinyl ethers, styrene etc.
  • the hydrophobic chain or chains typically are selected from saturated and unsaturated alkyl chains, e.g. having from 5 to 24 carbon atoms and are optionally bonded to the backbone via an alkoxylene or polyalkoxylene linkage, for example a polyethoxy, polypropoxy or butyloxy (or mixtures of same) linkage having from 1 to 50 alkoxylene groups.
  • the side chain(s) will essentially have the character of a nonionic surfactant.
  • Preferred anionic polymers are disclosed in our copending European patent application EP 89201530.6 (EP 346 995).
  • the amount of viscosity regulating polymer is from 0.1 to 5% by weight of the total composition, more preferred from 0.2 to 2%.
  • compositions of the invention may also comprise materials for adjusting the pH.
  • weak acids especially the use of organic acids is preferred, more preferred is the use of C 1-8 carboxylic acids, most preferred is the use of citric acid.
  • the use of these pH lowering agents is especially preferred when the compositions of the invention contain enzymes such as amylases, proteases and lipolases.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex Novo).
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • lather depressants such as inorganic salts such as sodium sulphate
  • fluorescent agents such as fluorescent agents, perfumes, germicides colourants and enzymes such as proteases, cellulases, amylases and lipases (including Lipolase (Trade Mark) ex
  • protease enzymes are Savinase@ (ex Novo), Maxacal@ (Gist-Brocades), Opticlean® (ex MKC) or AP122@ (ex Showa Denko), Alcalase@, Maxatase@, Esperase@, Optimase@, proteinase K and subtilisin BPN.
  • Suitable lipases are for example Lipolase@ (ex Novo), Amano lipases, Meito lipases, Lipozym@, SP 225, SP 285, Toyo Jozo lipase.
  • Suitable amylases are for example Termamyl@ (TM of Novo) and Maxamyl@.
  • Suitable cellulases include Celluzym@ (ex Novo).
  • compositions of the invention preferably comprise from 10 -80 % by weight of water, more preferably from 15-60%, most preferably from 20-50 %.
  • Liquid detergent compositions according to the invention are preferably physically stable in that they show less than 2% by volume phase separation upon storage for 21 days after preparation at 25 ° C.
  • Liquid detergent compositions according to the invention are preferably volume stable in that they show less than 25% preferably less than 10%, more preferably less than 5% volume increase during storage at a temperature between 20 and 37 ° C for a period of three months after preparation.
  • the compositions according to the present invention also comprise a second stabilising agent for the bleach component.
  • Suitable stabilisers are well-known in art and include EDTA, Magnesium silicates and phosphonates such as for instance the Dequest@ range ex Monsanto and Naphthol@ ex Merck.
  • the amount of these stabilising agents is from 0.05 to 5 % by weight of the composition, more preferred from 0.05 to 1% of the composition.
  • compositions of the present invention may comprise one or more bleach precursor agents.
  • a well-known example of such an agent is TAED.
  • the bleach precursor agent is present in the system in at least partly undissolved form.
  • One way of ensuring that the precursor is present in undissolved form is to increase the amount of electrolyte in the composition, therewith reducing the solubility of the precursor in the system.
  • Suitable electrolytes for this purpose are for instance the at least partially water soluble carbonate, sulphate and halogenide salts.
  • the detergent compositions of the inventention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
  • concentration of liquid detergent composition in the wash liquor is preferably from 0.05 to 10 %, more preferred from 0.1 to 3% by weight.
  • the liquid detergent compositions preferably are alkaline, and it is preferred that they should provide a pH within the range of about 7.0 to 12, preferably about 8 to about 11, when used in aqueous solutions of the composition at the recommended concentration.
  • the undiluted liquid composition should preferably be of a pH above 7, for example about pH 8.0 to about 12.5. It should be noted that an excessively high pH, e.g. over about pH 13, is less desirable for domestic safety.
  • the pH is generally from 7.5 to 10.5, preferably 8 to 10, and especially 8.5 to 10, to ensure the combined effect of good detergency and good physical and chemical stability.
  • the ingredients in any such highly alkaline detergent composition should, of course, be chosen for alkaline stability, especially for pH-sensitive materials such as enzymes, and a particularly suitable proteolytic enzyme.
  • the pH may be adjusted by addition of a suitable alkaline or acid material.
  • compositions according to the invention may be prepared by any method for the preparation of liquid detergent compositions.
  • a preferred method involves the addition of the alkali metal silicate to water, which optionally comprises one or more of the other ingredients of the formulation.
  • the bleach materials are preferably added as a pre-dispersion .
  • composition was prepared by adding the ingredients in the listed order to water:
  • Composition A had a pH of about 11 and contained about 1.9 % by weight of the bleach material in solubilised form, the half-life time of the bleach at 37 ° C was 35 days.
  • Composition B had a pH of about 9.8 and contained about 2.1 % by weight of the bleach material in solubilised form. The half-life time of the dissolved bleach was significantly less than 1 day.
  • liquid detergent compositions may be formulated by adding the ingredients to water in the listed order:
  • compositions were made by adding the electrolyte together with the minor ingredients except for the perfume and the enzymes to water of elevated temperature, followed by the addition of the deflocculating polymer and then the detergent active materials as a pre-mix under stirring and thereafter cooling the mixture and adding the enzymes and the perfumes.
  • the perborate was added as a 65 % predispersion in water (Proxsol@ ex ICI), the polymer was a deflocculating polymer described as A44 in EP 346 995, the pH was adjusted, if necessary, with citric acid.
  • the viscosity of the products was measured in mPa.s at 21 s-1 ; the volume stability was determined by measuring the maximum volume increase during storage of three months at ambient temperature; the physical stability was determined by checking the phase separation and solid sedimentation upon storage; the Bleach stability indicates the percentage of bleach left after storage of 4 weeks at 37 ° C. The following results were obtained:

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP91903330A 1990-02-08 1991-02-07 Liquid bleach composition Revoked EP0514422B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP90200290A EP0385522B1 (en) 1989-02-27 1990-02-08 Liquid detergent composition
EP90200290 1990-02-08
EP90202309 1990-08-28
EP90202309 1990-08-28
PCT/EP1991/000258 WO1991012307A2 (en) 1990-02-08 1991-02-07 Liquid bleach composition

Publications (2)

Publication Number Publication Date
EP0514422A1 EP0514422A1 (en) 1992-11-25
EP0514422B1 true EP0514422B1 (en) 1995-04-26

Family

ID=26125737

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91903330A Revoked EP0514422B1 (en) 1990-02-08 1991-02-07 Liquid bleach composition

Country Status (8)

Country Link
EP (1) EP0514422B1 (ja)
JP (1) JPH0768542B2 (ja)
AU (1) AU646018B2 (ja)
BR (1) BR9105999A (ja)
CA (1) CA2073445A1 (ja)
DE (1) DE69109273T2 (ja)
ES (1) ES2072601T3 (ja)
WO (1) WO1991012307A2 (ja)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN185580B (ja) * 1991-08-30 2001-03-03 Albright & Wilson Uk Ltd
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
GB9315761D0 (en) * 1993-07-30 1993-09-15 Unilever Plc Bleach compositions
WO1996002624A1 (en) * 1994-07-13 1996-02-01 So-Safe Specialty Products Pty. Ltd. A cleaning kit and a cleaning composition and methods of use
US6187221B1 (en) 1999-05-12 2001-02-13 National Starch And Chemical Investment Holding Corporation Controlled release bleach thickening composition having enhanced viscosity stability at elevated temperatures
CN108136448A (zh) * 2015-02-21 2018-06-08 吉欧科技聚合物有限责任公司 从聚对苯二甲酸乙二醇酯热敏打印膜除去涂层
US20160244624A1 (en) * 2015-02-21 2016-08-25 Geo-Tech Polymers, Llc Coating Removal from Biaxially-Oriented Polypropylene Films for Food Packaging

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482274A1 (en) * 1989-01-10 1992-04-29 The Procter & Gamble Company Liquid detergent compositions containing a suspended peroxygen bleach

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2396114A1 (fr) * 1977-06-29 1979-01-26 Protex Manuf Prod Chimiq Perfectionnements aux procedes de blanchiment oxydant
GB8602327D0 (en) * 1986-01-30 1986-03-05 Unilever Plc Liquid detergent compositions
GB8710690D0 (en) * 1987-05-06 1987-06-10 Unilever Plc Detergent bleach composition
CA1335646C (en) * 1988-06-13 1995-05-23 Guido Clemens Van Den Brom Liquid detergent compositions
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
GB8821763D0 (en) * 1988-09-16 1988-10-19 Unilever Plc Liquid detergents
GB8826458D0 (en) * 1988-11-11 1988-12-14 Ici Plc Bleach formulation & aqueous detergent compositions
DE3842007A1 (de) * 1988-12-14 1990-06-21 Henkel Kgaa Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
GB8916094D0 (en) * 1989-07-13 1989-08-31 Unilever Plc Liquid bleach composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482274A1 (en) * 1989-01-10 1992-04-29 The Procter & Gamble Company Liquid detergent compositions containing a suspended peroxygen bleach

Also Published As

Publication number Publication date
DE69109273D1 (de) 1995-06-01
BR9105999A (pt) 1992-10-20
CA2073445A1 (en) 1991-08-09
WO1991012307A3 (en) 1991-10-03
JPH0768542B2 (ja) 1995-07-26
AU646018B2 (en) 1994-02-03
WO1991012307A2 (en) 1991-08-22
DE69109273T2 (de) 1995-08-24
ES2072601T3 (es) 1995-07-16
EP0514422A1 (en) 1992-11-25
JPH05502908A (ja) 1993-05-20
AU7210991A (en) 1991-09-03

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NLR2 Nl: decision of opposition