EP0358474B1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
EP0358474B1
EP0358474B1 EP89309010A EP89309010A EP0358474B1 EP 0358474 B1 EP0358474 B1 EP 0358474B1 EP 89309010 A EP89309010 A EP 89309010A EP 89309010 A EP89309010 A EP 89309010A EP 0358474 B1 EP0358474 B1 EP 0358474B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
weight
nonionic surfactant
surfactant system
vinyl acetate
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 - Lifetime
Application number
EP89309010A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0358474A2 (en
EP0358474A3 (en
Inventor
Jelles Vincent Boscamp
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
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0358474A2 publication Critical patent/EP0358474A2/en
Publication of EP0358474A3 publication Critical patent/EP0358474A3/en
Application granted granted Critical
Publication of EP0358474B1 publication Critical patent/EP0358474B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers

Definitions

  • the present invention relates to fabric washing detergent compositions having improved antiredeposition properties.
  • EP 262 897A discloses detergent compositions containing polyvinylpyrrolidone, an anionic surfactant, and a nonionic surfactant system having a hydrophilic-lipophilic balance (HLB) of not more than 10.5.
  • HLB hydrophilic-lipophilic balance
  • EP 219 048A discloses the use of graft copolymers of polyalkylene oxide with vinyl acetate as greying inhibitors in the washing and post-wash treatment of synthetic textile fabrics.
  • detergent compositions containing a graft copolymer of this type in conjunction with a low-HLB nonionic surfactant system exhibit surprisingly enhanced soil suspension (antiredeposition) properties on polyester/cotton fabrics.
  • the present invention provides a detergent composition comprising:
  • the present invention relates to detergent compositions containing two specified ingredients - a nonionic surfactant system, and a graft copolymer - which may additionally contain any other conventional detergent ingredients, for example, other surfactants, builders, bleach systems, antifoam systems, fluorescers, inorganic salts, and other materials well known to those skilled in formulating detergents.
  • the compositions of the invention may take any suitable form, for example, powders, liquids or bars.
  • the nonionic surfactant system of the present invention exists as a cloudy phase somewhere in the temperature range of 0°C to 40°C, preferably 0°C to 15°C, in distilled water at a concentration of 1%. In practice this means that the system has a cloud point of not more than 40°C, preferably not more than 15°C. Cloud point is a term well known in the art, for example, from "Surface Active Ethylene Oxide Adducts" by N Schonfeldt, Pergamon Press 1969, pages 145 to 154.
  • the cloud point of a surfactant material is the temperature at which association between the surfactant molecules and water molecules through hydrogen bonding breaks down, leading to the separation of surfactant-rich and water-rich phases and a consequent increase in turbidity or cloudiness.
  • the cloud point correlates approximately to the hydrophilic-lipophilic balance (HLB) of the surfactant system and it is therefore preferred that the HLB should be not higher than 10.5 and more preferably not higher than 9.5.
  • the HLB should however preferably be above 6.0, more preferably above 8.0, in order to provide sufficient detergency.
  • Suitable nonionic detergent compounds which may be used 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 (C6 ⁇ 22) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C8 ⁇ 20 primary or secondary 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, tertiary phosphine oxides, and dialkyl sulphoxides.
  • alkylene oxide adducts of fatty materials are used as the nonionic detergent compounds
  • the number of alkylene oxide groups per molecule has a considerable effect upon the cloud point as indicated by the Schonfeldt reference mentioned above.
  • the chain length and nature of the fatty material is also influential, and thus the preferred number of alkylene oxide groups per molecule depends on the nature and chain length of the fatty material.
  • the fatty material is an alcohol having about 12 to 15 carbon atoms
  • the adducts having 3 and 4 ethylene oxide groups per molecule both have cloud points of less than 0°C and are therefore suitable for use in the present invention.
  • the corresponding 5EO and 6EO surfactants have cloud points of about 12°C and about 30°C respectively; both are therefore suitable for use in the present invention, but the 5EO is preferred to the 6EO.
  • the corresponding 7EO surfactant has a cloud point of about 48°C and is therefore unsuitable for use in the present invention, unless in admixture with another surfactant of lower cloud point: for example, a mixture of 1 part by weight of the 7EO material with 3 parts by weight of the 3EO material has a sufficiently low cloud point to be useful in the present invention. Further ethoxylation raises the cloud point still higher: thus the corresponding 11EO material has a cloud point higher than 80°C and is unsuitable for use in the present invention.
  • nonionic surfactants for use in the compositions of the invention are C12 ⁇ 15 aliphatic alcohols having a degree of ethoxylation not exceeding 6, preferably 3 to 5.
  • the nonionic surfactant system of the compositions of the invention may consist of a single nonionic surfactant of appropriate cloud point, although it must be remembered that even a single commercial nonionic surfactant is a mixture of materials of different chain lengths and degrees of ethoxylation: the chain lengths and degrees of ethoxylation quoted in this specification are average values.
  • a nonionic surfactant system of suitable cloud point and HLB value may be obtained by blending two or more nonionic surfactants, as exemplified by the 7EO/3EO mixture mentioned in the previous paragraph.
  • the nonionic surfactant system is preferably present in an amount of from 2 to 20% by weight, more preferably from 3 to 10% by weight, based on the total composition.
  • Optional Ingredients other surfactants, of other ionic types, may also be present if desired, the total amount of surfactant of all ionic types present being within the range of from 2 to 50% by weight, preferably from 5 to 40% by weight, of the final composition.
  • Graft copolymers useful in the compositions of the present invention are described and claimed in EP 219 048A (BASF). They are obtainable by grafting a polyalkylene oxide of molecular weight (number average) 2000 - 100 000 with vinyl acetate, which may be partially saponified, in a weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2 to 1:10.
  • the vinyl acetate may, for example, be saponified to an extent of up to 15%.
  • the polyalkylene oxide may contain units of ethylene oxide, propylene oxide and/or butylene oxide; polyethylene oxide is preferred.
  • the polyalkylene oxide has a number-average molecular weight of from 4000 to 50 000, and the weight ratio of polyalkylene oxide to vinyl acetate is from 1:0.5 to 1:6.
  • a material within this definition based on polyethylene oxide of molecular weight 6000 (equivalent to 136 ethylene oxide units), containing approximately 3 parts by weight of vinyl acetate units per 1 part by weight of polyethylene oxide, and having itself a molecular weight of 24 000, is commercially available from BASF as Sokalan (Trade Mark) HP22.
  • the polymers are present in the compositions of the invention in amounts of from 0.1 to 3% by weight, preferably from 0.3 to 1% by weight.
  • compositions of the invention may contain any other non-interfering ingredients known to be suitable for incorporation into detergent compositions.
  • compositions may usefully contain one or more soap or non-soap anionic, cationic, amphoteric or zwitterionic surfactants, or combinations of these.
  • soap or non-soap anionic, cationic, amphoteric or zwitterionic surfactants or combinations of these.
  • suitable detergent-active compounds are 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 that can be used, in addition to the specified nonionic surfactant system, are soaps and synthetic non-soap anionic surfactants.
  • Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly sodium C12-C15 primary alcohol sulphates; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C8-C15
  • primary and secondary alkyl sulphates particularly sodium C12-C15 primary alcohol sulphates
  • olefin sulphonates alkane sulphonates
  • dialkyl sulphosuccinates and fatty acid ester sulphonates.
  • soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rape seed oil.
  • a preferred type of detergent composition suitable for use in most automatic fabric washing machines contains anionic and nonionic surfactant together in a weight ratio of at least 0.67:1, preferably at least 1:1, and more preferably within the range of from 1:1 to 10:1. Soap may also be present if desired.
  • the total amount of surfactant in the compositions of the invention is from 2 to 50% by weight, and is preferably from 5 to 40% by weight.
  • compositions of the invention will also generally contain one or more detergency builders. These are as well known to the skilled formulator as are the surfactants listed above.
  • Inorganic builders that may be present include alkali metal (generally sodium) ortho-, pyro- and tripolyphosphate, carbonate, and crystalline and amorphous aluminosilicates; while organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and polyacetal carboxylates, and monomeric polycarboxylates such as nitrilotriacetates, citrates and carboxymethyloxysuccinates. This list is not intended to be exhaustive.
  • the total level of detergency builder is generally within the range of from 20 to 80% by weight.
  • compositions contain less than 10% by weight of inorganic phosphate builders, and are more preferably substantially free of inorganic phosphate.
  • the builder system preferably comprises crystalline or amorphous alkali metal aluminosilicate, optionally in conjunction with a supplementary builder.
  • the aluminosilicate is suitably present in an amount of from 10 to 60% by weight.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system Preferred are peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures.
  • peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures.
  • the skilled detergent worker will have no difficulty in applying the normal principles to choose a suitable bleach system.
  • detergent compositions of the invention include sodium silicate, fluorescers, inorganic salts such as sodium sulphate, enzymes, lather control agents or lather boosters as appropriate, pigments, and perfumes. Again, this list is not intended to be exhaustive.
  • Detergent compositions of the invention may be prepared by any suitable method.
  • Detergent powders are suitably prepared by spray-drying a slurry of compatible heat-insensitive components, and then spraying on or postdosing those ingredients unsuitable for processing via the slurry.
  • the skilled detergent formulator will generally have no difficulty in deciding which components should be included in the slurry and which should be postdosed or sprayed on.
  • the graft copolymer is available as a solution having a solids content of 20% which is stable at slurry processing temperatures and can be incorporated in the slurry without problems, provided that the pH is maintained below 12.
  • the nonionic surfactant system is preferably not incorporated via the slurry. If, however, a mixed system is used which includes a relatively highly ethoxylated component, that component may if desired be processed via the slurry while material of lower ethoxylation is sprayed on or postdosed on a solid carrier.
  • compositions prepared contained the following amounts of nonionic surfactants and Sokalan HP22:
  • Example 1 A B C Nonionic surfactant 7EO1 1.0 4.0 4.0 1.0 Nonionic surfactant 3EO2 3.0 - - 3.0 Sokalan HP22 0.5 - 0.5 1 Synperonic (Trade Mark) A7 ex ICI, C 12-15 linear primary alcohol 7EO 2 Synperonic (Trade Mark) A3 ex ICI, C 12-15 linear primary alcohol 3EO
  • composition 1 illustrates the invention while Compositions A to C are comparative.
  • the soil suspension (antiredeposition) properties of the four compositions were compared by means of the following procedure.
  • Two new, clean, unwashed polyester/cotton test cloths were washed together with five soiled cloths in a tergotometer at 60°C in 50° (French) hard water (Ca:Mg ratio 4:1) at a liquor to cloth ratio of about 50:1, the wash liquor containing 4 g/l of the detergent composition under test.
  • the soiled cloths carried a range of different soils such as clay, oil, fat, proteinaceous, and ink.
  • the wash cycle was repeated a further nine times, the soiled cloths being replaced by new soiled cloths (with the same range of soils) for each wash cycle.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP89309010A 1988-09-07 1989-09-06 Detergent compositions Expired - Lifetime EP0358474B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8821035 1988-09-07
GB888821035A GB8821035D0 (en) 1988-09-07 1988-09-07 Detergent compositions

Publications (3)

Publication Number Publication Date
EP0358474A2 EP0358474A2 (en) 1990-03-14
EP0358474A3 EP0358474A3 (en) 1990-10-10
EP0358474B1 true EP0358474B1 (en) 1994-11-17

Family

ID=10643230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89309010A Expired - Lifetime EP0358474B1 (en) 1988-09-07 1989-09-06 Detergent compositions

Country Status (10)

Country Link
EP (1) EP0358474B1 (no)
JP (1) JPH02117999A (no)
AU (1) AU619892B2 (no)
BR (1) BR8904489A (no)
CA (1) CA1328065C (no)
DE (1) DE68919392T2 (no)
ES (1) ES2063139T3 (no)
GB (1) GB8821035D0 (no)
NO (1) NO172854C (no)
ZA (1) ZA896841B (no)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266166A (en) * 1992-05-18 1993-11-30 Betz Paperchem, Inc. Methods for controlling the deposition of organic contaminants in pulp and papermaking processes using a polyalkylene oxide/vinyl acetate graft copolymer
WO1995007968A1 (en) * 1993-09-13 1995-03-23 The Procter & Gamble Company Granular detergent compositions comprising nonionic surfactant and process for making such compositions
GB2304115A (en) * 1995-08-04 1997-03-12 Reckitt & Colman Inc Pine oil hard surface cleaning compositions
US5635554A (en) * 1994-07-14 1997-06-03 Basf Aktiengesellschaft Low viscosity mixtures of amphiphilic nonionic graft copolymers and viscosity-reducing additives
EP0778339A2 (en) 1995-12-06 1997-06-11 Basf Corporation Improved non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide
EP0778340A2 (en) 1995-12-06 1997-06-11 Basf Corporation Improved non-phosphate machine dishwashing compositions containing copolymers of alkylene oxide adducts of allyl alcohol and acrylic acid
US5698510A (en) * 1993-09-13 1997-12-16 The Procter & Gamble Company Process for making granular detergent compositions comprising nonionic surfactant
US5728672A (en) * 1995-08-04 1998-03-17 Reckitt & Colman Inc. Pine oil hard surface cleaning compositions
US6083488A (en) * 1996-12-04 2000-07-04 The Block Drug Company Barrier to plaque formation

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9403155D0 (en) * 1994-02-18 1994-04-06 Unilever Plc Detergent compositions
AU6740496A (en) * 1995-09-04 1997-03-27 Unilever Plc Detergent compositions and process for preparing them
JP3325830B2 (ja) * 1998-03-30 2002-09-17 株式会社日本触媒 漂白剤組成物
JP2002003890A (ja) * 2000-06-20 2002-01-09 Kao Corp 洗浄剤組成物
CN101084298A (zh) 2004-12-17 2007-12-05 宝洁公司 用于改善疏水性污垢清洁效果的亲水改性的多羟基化合物
MX2007007317A (es) 2004-12-17 2007-07-09 Procter & Gamble Polioles hidrofobamente modificados para una limpieza mejorada de la suciedad hidrofoba.
US7465701B2 (en) 2006-05-31 2008-12-16 The Procter & Gamble Company Detergent composition
US8519060B2 (en) † 2006-05-31 2013-08-27 Basf Se Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
BRPI0813289A2 (pt) 2007-06-29 2014-12-30 Procter & Gamble Composições detergentes para lavagem de roupas que compreendem polímeros de enxerto antifílicos à base de óxidos de poliaquileno e ésteres vinílicos.
JP4933487B2 (ja) * 2008-05-21 2012-05-16 旭洋造船株式会社 低燃費型輸送船
JP4873388B2 (ja) * 2008-07-28 2012-02-08 上野 康男 起動装置
US8334250B2 (en) * 2009-12-18 2012-12-18 The Procter & Gamble Company Method of making granular detergent compositions comprising amphiphilic graft copolymers
US20110152161A1 (en) * 2009-12-18 2011-06-23 Rohan Govind Murkunde Granular detergent compositions comprising amphiphilic graft copolymers
CN104160009A (zh) 2012-03-09 2014-11-19 宝洁公司 包含具有广泛极性分布的接枝聚合物的洗涤剂组合物
PL2832842T3 (pl) 2013-07-30 2019-09-30 The Procter & Gamble Company Sposób wytwarzania kompozycji granulowanych detergentów zawierających środki powierzchniowo czynne
EP2832843B1 (en) 2013-07-30 2019-08-21 The Procter & Gamble Company Method of making granular detergent compositions comprising polymers
EP2899259A1 (en) * 2014-01-22 2015-07-29 The Procter and Gamble Company Detergent compositions

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7815052A (nl) * 1977-11-17 1980-01-31 Procter & Gamble Korrelvormige wasmiddelen ter betere verwijdering van vet vuil.
DE3536530A1 (de) * 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
GB8623586D0 (en) * 1986-10-01 1986-11-05 Unilever Plc Detergent composition
GB8821032D0 (en) * 1988-09-07 1988-10-05 Unilever Plc Detergent compositions
GB8821034D0 (en) * 1988-09-07 1988-10-05 Unilever Plc Detergent compositions

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266166A (en) * 1992-05-18 1993-11-30 Betz Paperchem, Inc. Methods for controlling the deposition of organic contaminants in pulp and papermaking processes using a polyalkylene oxide/vinyl acetate graft copolymer
WO1995007968A1 (en) * 1993-09-13 1995-03-23 The Procter & Gamble Company Granular detergent compositions comprising nonionic surfactant and process for making such compositions
US5698510A (en) * 1993-09-13 1997-12-16 The Procter & Gamble Company Process for making granular detergent compositions comprising nonionic surfactant
US5635554A (en) * 1994-07-14 1997-06-03 Basf Aktiengesellschaft Low viscosity mixtures of amphiphilic nonionic graft copolymers and viscosity-reducing additives
GB2304115A (en) * 1995-08-04 1997-03-12 Reckitt & Colman Inc Pine oil hard surface cleaning compositions
US5728672A (en) * 1995-08-04 1998-03-17 Reckitt & Colman Inc. Pine oil hard surface cleaning compositions
GB2304115B (en) * 1995-08-04 1999-08-25 Reckitt & Colman Inc Pine oil hard surface cleaning compositions
EP0778339A2 (en) 1995-12-06 1997-06-11 Basf Corporation Improved non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide
EP0778340A2 (en) 1995-12-06 1997-06-11 Basf Corporation Improved non-phosphate machine dishwashing compositions containing copolymers of alkylene oxide adducts of allyl alcohol and acrylic acid
US5750483A (en) * 1995-12-06 1998-05-12 Basf Corporation Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide
US6083488A (en) * 1996-12-04 2000-07-04 The Block Drug Company Barrier to plaque formation

Also Published As

Publication number Publication date
AU4108089A (en) 1990-03-15
ES2063139T3 (es) 1995-01-01
JPH02117999A (ja) 1990-05-02
NO893535L (no) 1990-03-08
NO172854C (no) 1993-09-15
GB8821035D0 (en) 1988-10-05
NO893535D0 (no) 1989-09-04
BR8904489A (pt) 1990-04-24
DE68919392D1 (de) 1994-12-22
NO172854B (no) 1993-06-07
EP0358474A2 (en) 1990-03-14
CA1328065C (en) 1994-03-29
ZA896841B (en) 1991-05-29
AU619892B2 (en) 1992-02-06
DE68919392T2 (de) 1995-03-30
EP0358474A3 (en) 1990-10-10

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