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EP0724012A1 - Composition détergente contenant un agent de blanchiment et un agent d'azurage - Google Patents

Composition détergente contenant un agent de blanchiment et un agent d'azurage Download PDF

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Publication number
EP0724012A1
EP0724012A1 EP95300502A EP95300502A EP0724012A1 EP 0724012 A1 EP0724012 A1 EP 0724012A1 EP 95300502 A EP95300502 A EP 95300502A EP 95300502 A EP95300502 A EP 95300502A EP 0724012 A1 EP0724012 A1 EP 0724012A1
Authority
EP
European Patent Office
Prior art keywords
brightener
biphenyl
bis
stilbene
detergent composition
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.)
Withdrawn
Application number
EP95300502A
Other languages
German (de)
English (en)
Inventor
Jean-Luc Philippe Bettiol
Paul Amaat Raymond Gerard France
David John Roberts
Carole Patricia Denise Wilkinson
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP95300502A priority Critical patent/EP0724012A1/fr
Priority to JP1155196A priority patent/JPH0920899A/ja
Publication of EP0724012A1 publication Critical patent/EP0724012A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention relates to granular detergent compositions comprising a particulate bleaching agent and a particulate brightening agent, wherein the particulate brightening agent comprises (a) stilbene brightener and (b) biphenyl or bis(benzoxazole) brightener.
  • Stilbene brighteners whilst being preferred for good product performance, readily degrade if processed and/or subsequently stored in proximity to bleach, certain bleach activators or free moisture.
  • EP-A 364027 published on 18th April, 1990, identifies a problem of stilbene brightener stability in the presence of bleaching agents including percarbonate.
  • Detergent compositions comprising either stilbene and biphenyl brighteners are disclosed in the examples. The problem is addressed by using a brightener which is a specific biphenyl brightener.
  • EP-A 577557 published on 5th January 1994, identifies certain hydrated biphenyl brighteners as having good storage stability.
  • biphenyl brighteners are known to be more stable, but they are also more expensive than stilbene brighteners.
  • Tinopal-CDX® supplied by Ciba-Geigy has a stilbene to biphenyl brightener ratio of about 2.2:1.
  • stilbene brighteners co-granulated with low levels of biphenyl or bis(benzoxazole) brighteners overcome problems of brightener stability and rate of solubility.
  • a granular detergent composition comprising a particulate bleaching agent and a particulate brightening agent, wherein the particulate brightening agent comprises (a) stilbene brightener and (b) biphenyl or bis(benzoxazole) brightener and wherein the ratio of stilbene brightener to biphenyl/benzoxazole brightener is at least 4:1, preferably at least 5:1, and most preferably at least 6:1.
  • the stability of the brightener is still further improved by ensuring low moisture levels in the particulate brightening agent itself, and/or in the granular detergent composition as a whole.
  • the particulate brightening agent comprises less than 5% by weight of water and/or the equilibrium relative humidity (eRH) of the finished composition is less than 5%.
  • the detergent composition further comprises zeolite
  • the zeolite is dried to a moisture level of less than 15% by weight, preferably less than 10% by weight, before it is incorporated into the composition.
  • the particulate brightening agents of the present invention comprise at least one stilbene brightener and at least one biphenyl or bis(benzoxazole) brightener.
  • Suitable stilbene brighteners for use in the present invention are derived from bis(4,4'-triazinylamino)stilbene-2,2'-disulphonic acid, preferably derived from : Disodium 4,4'-bis[(4-anilino-6-R-1,3,5 triazin-2-yl)amino]-2,2'-stilbenedisulphonate or Tetrasodium 4,4'-bis[(4-sulfoanilino-6-R-1,3,5 triazin-2-yl)amino]-2,2'-stilbenedisulphonate.
  • Suitable biphenyl and benzoxazole brighteners for use in the present invention are derived from distyrylbiphenyl, bis(benzo[b]furan-2-yl)biphenyl and bis(benzoxazole) according to the Ullmann's Encyclopedia of Industrial Chemistry, 1991, Vol A 18 page 157-163) : Preferred examples include those derived from: Disodium 4,4'-bis (2-sulphostyryl) biphenyl Disodium 4,4-bis (4-chloro-3-sulphostyryl) biphenyl Disodium 4,4'-bis(sulfobenzo[b]furan-2-yl)biphenyl 2,5-bis(benzoxazole-2-yl)thiophene and mixtures thereof Of these the most preferred is disodium 4,4'-bis (2-sulphostyryl) biphenyl (also known as Colour Index No 351 according according to the Society of Dyers and Colorists and the American Association of Textile Chemists and Color
  • the granular compositions of the present invention further comprise a granular component comprising a bleaching agent chosen from the group comprising alkalimetal percarbonate, peroxyacid, perimidic acid or combinations of these.
  • a bleaching agent chosen from the group comprising alkalimetal percarbonate, peroxyacid, perimidic acid or combinations of these.
  • This component is described hereinafter as the "bleaching component"
  • Percarbonate will generally be solid and granular in nature. It may be added to granular detergent compositions without additional protection. However, such granular compositions may utilise a coated form of the material which provides better storage stability for the percarbonate in the granular product.
  • the sodium salt of percarbonate is preferred for use in the present invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • the percarbonate may be incorporated into detergent compositions without additional protection, but preferred embodiments of the invention utilise a coated form of the material. Suitable coating materials include the alkali and alkaline earth metal carbonates and sulphates or chlorides.
  • the most preferred coating material comprises a mixed salt of alkali metal sulphate and carbonate.
  • a mixed salt of alkali metal sulphate and carbonate Such coatings together with coating processes have previously been described in GB 1 466 799, granted to Interox on 9th March, 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:200 to 1:4, more preferably from 1:100 to 1:10, and most preferably from 1:50 to 1:20.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material is sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of less than 2% of silicate solids by weight of percarbonate.
  • Magnesium silicate can also be included in the coating.
  • compositions of the invention may contain bleaching agents more suited to low temperature bleaching.
  • bleaching agents more suited to low temperature bleaching.
  • These will include, for example, preformed organic peracids and perimidic acids.
  • preformed peroxy acids or perimidic acids which are useful in the present invention:
  • a highly preferred component of the compositions of the present invention is zeolite. Most preferably some or all of the zeolite used is dried to a moisture level of less than 15% by weight, preferably less than 10% by weight, before it is incorporated into the composition.
  • Suitable zeolites include crystalline aluminosilicate ion exchange material of the formula: Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least about 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite M, Zeolite P and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
  • compositions of the present invention are also useful in the compositions of the present invention.
  • Surfactants include, but are not limited to C11-C18 alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulphates ("AS”), the secondary (2,3) alkyl sulphates, the C10-C18 alkyl alkoxy sulphates ("AExS”; especially EO 1-7 ethoxy sulphates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates) the C10-C18 glycerol ethers, the C10-C18 alkyl poyglycosides and their corresponding sulphated polyglycosides, and C12-C18 alpha-sulphonated fatty acid esters.
  • LAS C11-C18 alkyl benzene sulphonates
  • AS primary, branched-chain and random C10-C20 alkyl sulphates
  • AS secondary (2,3)
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates, C12-C18 betaines and sulphobetaines ("sultaines”), C10-C18 amine oxides, and the like, can also be included in the overall composition.
  • AE C12-C18 alkyl ethoxylates
  • sulphobetaines C10-C18 amine oxides, and the like
  • Detergent builders include, but are not limited to, alkali metal, ammonium and alkyanolammonium salts of polyphosphates, (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acids, silicates (including crystalline layered silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and aluminosilicates (mentioned above).
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, polyacetic salts such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof, citric acid and soluble salts thereof
  • Useful minors include, but are not limited to enzymes, enzyme stabilisers, soil release agents, chelating agents, clay soil / antiredeposition agents, dispersing agents, suds suppressor, fabric softening including smectite clay, dye transfer agents, perfume etc.
  • a mixture of granular raw materials were prepared according to the following compositions : Table 1 Example 1 Comparative Example A Anionic surfactant agglomerate * 30 30 Layered silicate compacted granule (supplied by Hoechst under trade name SKS-6®) 18 18 Percarbonate (supplied by Interox)** 25 25 TAED agglomerate 9 9 Suds suppressor agglomerate 3.5 3.5 Perfume encapsulate 0.2 0.2 Granular dense soda ash 6.7 6.7 Granular acrylic-maleic copolymer 3.2 3.2 Enzymes 3.6 3.6 Granular soil release polymer 0.6 0.6 Brightener granule (6.7/1 ratio of stilbene/biphenyl) supplied by Ciba Geigy) 0.3 - Brightener granule (2.2/1 ratio of stilbene/biphenyl) (supplied by Ciba Geigy) - 0.3 100 ⁇ 100 ⁇ Partially hydrated zeolite A (8%
  • the paste was agglomerated with a powder mixture according to the process described in EPA510746.
  • the resulting anionic surfactant granule had a composition of 30% C45AS, 7.5% C35AE3S, 24% zeolite, 20% carbonate, 2.5% CMC, 12% acrylic-maleic co-polymer, and the balance of moisture. ** Percarbonate coated with 2.5% carbonate/sulphate with mean particle size of 500 microns.
  • the mixture of granular ingredients listed above was placed inside a 140 litre rotating drum that operates at 25 rpm. While operating the drum a mixture of nonionic surfactants (C25E3/polyhydroxy fatty acid amide in a 70/30 ratio) were sprayed onto the granular mixture to a level of 7% by weight of the granular components. The spraying time was about 1-2 minutes. Immediately afterwards, perfume was sprayed on, at a level of 0.5% by weight of the granular components, while rotating the drum. Then, without stopping the rotation of the drum, a flow aid (by 8 % of weight) was slowly added to the mixer, taking about 30 seconds. Once the addition of flow aid was finished, the mixer was allowed to rotate for about 1 minute and was then stopped. The finished product was then removed from the rotating drum. The flow aid used was partially hydrated zeolite A (8 % moisture).
  • example 1 was repeated using the components listed in table 1.
  • the flow aid used was zeolite A (20 % moisture).
  • Example 2 The following laundry detergent composition (by % weight) was prepared:
  • Example 2 Comparative Examples B C Surfactant agglomerate zeolite MAP 20 20 20 carbonate 10 10 10 C24AS 10 10 10 (Alkyl sulfate) C24E3 alcohol 10 10 10 ethoxylate moisture 5 5 5 5 Brightener (2.2/1 ratio of stilbene/biphenyl) - 0.2 0.2 Dry mixing Percarbonate* 18 18 18 TAED 5 5 5 5 Bleach Cata-lyst (ppm) 100 100 100 100 Sodium carbonate 5 5 5 5 Sodium Silicate 2R 5 5 5 5 5 5 5 5 5 5 Chelant 0.5 0.5 0.5 Enzyme 3 3 3 Antifoam 3 3 3 Brightener granule (6.7/1 ratio of stilbene/biphenyl) 0.2 - - Spray-on Perfume 0.3 0.3 0.3 Coating Zeolite A (20 % moisture) - 5 - Zeolite A (8% moisture) 5 - 5 * coated with
  • Example 3 Comparative Example D Extrudate LAS 10 10 C24E5 alcohol ethoxylate 5 5 Zeolite A 25 30 Carbonate 15 15 Monohydrate Perborate 15 15 Brightener (2.2/1 ratio of stilbene/biphenyl) - 0.2 Chelant 0.5 0.5 Moisture 5 5 Dry mixing TAED 5 5 Enzyme 3 3 Antifoam 3 3 Brightener (6.7/1 ratio of stilbene/ biphenyl) 0.2 - Zeolite A (8 % moisture) 5 - Balance with minors to 100%

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP95300502A 1995-01-27 1995-01-27 Composition détergente contenant un agent de blanchiment et un agent d'azurage Withdrawn EP0724012A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95300502A EP0724012A1 (fr) 1995-01-27 1995-01-27 Composition détergente contenant un agent de blanchiment et un agent d'azurage
JP1155196A JPH0920899A (ja) 1995-01-27 1996-01-26 漂白剤と増白剤とを含む洗剤組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95300502A EP0724012A1 (fr) 1995-01-27 1995-01-27 Composition détergente contenant un agent de blanchiment et un agent d'azurage

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EP0724012A1 true EP0724012A1 (fr) 1996-07-31

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998023720A1 (fr) * 1996-11-26 1998-06-04 The Procter & Gamble Company Compositions detergentes pour la lessive contenant une combinaison de tensioactifs et d'azurants optiques
EP1065264A1 (fr) * 1999-06-29 2001-01-03 The Procter & Gamble Company Compositions de blanchiment
WO2003093565A3 (fr) * 2002-05-03 2004-03-04 Basf Ag Procede pour azurer des materiaux textiles
EP2993222A1 (fr) 2014-09-03 2016-03-09 Tim Bast Composition détergente comprenant un métal de terres rares et un agent de blanchiment optique contenant de stilbène
EP1693441B2 (fr) † 2005-02-21 2019-11-06 The Procter & Gamble Company Composition détergente lessivielle particulaire comprenant un agent détersif tensio-actif, du carbonate et un agent de blanchiment fluorescent

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0317979A2 (fr) * 1987-11-26 1989-05-31 Ciba-Geigy Ag Détergents stables contenant des azurants optiques
EP0322564A2 (fr) * 1987-12-23 1989-07-05 Ciba-Geigy Ag Détergents stables contenant des azurants optiques
EP0395333A2 (fr) * 1989-04-24 1990-10-31 Unilever Plc Compositions détergentes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0317979A2 (fr) * 1987-11-26 1989-05-31 Ciba-Geigy Ag Détergents stables contenant des azurants optiques
EP0322564A2 (fr) * 1987-12-23 1989-07-05 Ciba-Geigy Ag Détergents stables contenant des azurants optiques
EP0395333A2 (fr) * 1989-04-24 1990-10-31 Unilever Plc Compositions détergentes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998023720A1 (fr) * 1996-11-26 1998-06-04 The Procter & Gamble Company Compositions detergentes pour la lessive contenant une combinaison de tensioactifs et d'azurants optiques
EP1065264A1 (fr) * 1999-06-29 2001-01-03 The Procter & Gamble Company Compositions de blanchiment
WO2001000773A1 (fr) * 1999-06-29 2001-01-04 The Procter & Gamble Company Compositions de blanchiment
WO2003093565A3 (fr) * 2002-05-03 2004-03-04 Basf Ag Procede pour azurer des materiaux textiles
CN1333129C (zh) * 2002-05-03 2007-08-22 巴斯福股份公司 纺织材料的增白方法
KR100973535B1 (ko) * 2002-05-03 2010-08-03 바스프 에스이 섬유 재료를 광택 처리하는 방법
EP1693441B2 (fr) † 2005-02-21 2019-11-06 The Procter & Gamble Company Composition détergente lessivielle particulaire comprenant un agent détersif tensio-actif, du carbonate et un agent de blanchiment fluorescent
EP2993222A1 (fr) 2014-09-03 2016-03-09 Tim Bast Composition détergente comprenant un métal de terres rares et un agent de blanchiment optique contenant de stilbène
WO2016034651A1 (fr) 2014-09-03 2016-03-10 Tim Bast Composition détergente comprenant un métal de terres rares et un agent d'azurage à base de stilbène

Also Published As

Publication number Publication date
JPH0920899A (ja) 1997-01-21

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