WO1999021949A1 - Solution de tensioactifs pour composition detergente de blanchissage - Google Patents

Solution de tensioactifs pour composition detergente de blanchissage Download PDF

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Publication number
WO1999021949A1
WO1999021949A1 PCT/US1998/022105 US9822105W WO9921949A1 WO 1999021949 A1 WO1999021949 A1 WO 1999021949A1 US 9822105 W US9822105 W US 9822105W WO 9921949 A1 WO9921949 A1 WO 9921949A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
accordance
laundry detergent
triblock copolymer
laundry
Prior art date
Application number
PCT/US1998/022105
Other languages
English (en)
Inventor
Amjad Farooq
Guy Broze
Anne-Marie Misselyn
Donghui Wu
Ammanuel Mehreteab
Alain Jacques
Jeffrey J. Mastrull
Original Assignee
Colgate-Palmolive Company
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 Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU11028/99A priority Critical patent/AU1102899A/en
Publication of WO1999021949A1 publication Critical patent/WO1999021949A1/fr

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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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/008—Polymeric surface-active 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • This invention relates to improved laundry detergent compositions containing alkyl benzene sulfonate as the principal anionic surfactant and which compositions are effective for the removal of oily and paniculate soils. More particularly, this invention relates to laundry detergent compositions having improved detergency based on the combination of an alkyl benzene sulfonate surfactant and a triblock polymeric co- surfactant comprising ethylene oxide and propyiene oxide groups as herein defined.
  • Block copolymers of ethylene oxide (EO) and propyiene oxide (PO) are extensively described in the patent literature. Among the principal uses disclosed for such copolymers are improved grease removal when incorporated into liquid dishwashing detergent compositions; and as anti-redeposition agents in liquid and powder detergent compositions. These EO/PO type block copolymers are often identified as Pluronic® block copolymers marketed by BASF. U.S.
  • Patent 4,904,359 describes liquid dishwashing detergent compositions containing a combination of a polymeric surfactant comprising a hydrophilic group such as polyethylene oxide and a hydrophobic group such as polypropylene oxide, and an anionic surfactant such as alkyl sulfate or polyethoxylate sulfate. This combination is said to provide superior grease removal from tableware and kitchen utensils as a detergent composition.
  • U.S. Patent 5,167,872 describes a dishwashing liquid detergent composition comprising a polymeric surfactant as described in the aforementioned U.S. Patent 4,904,359 wherein the composition further contains an anionic surfactant and a betaine surfactant.
  • U.S. Patent 4,724,095 there is described a detergent composition for washing textile fabrics comprising one or more principal types of copolymers , one of which is a copolymer of polyoxyethylene and poiyoxyalkylene as an anti-redeposition agent.
  • This type of copolymer is said to be marketed under the trademark "Pluronics"
  • U.S. 5,152,933 discloses the use of block copolymers of ethylene oxide and propyiene oxide as a cosurfactant in detergent formulations containing mixed actives such as a combination of alkyl benzene sulfonate and ethoxylated alcohol.
  • the presence of the block copolymers is said to enhance oily soil removal and clay soil removal from soiled fabrics in an automatic washing machine. Improvements are also said to be observed in formulations that contain only nonionic surfactants.
  • a laundry detergent composition comprising
  • laundering of soiled or stained fabrics is effected by washing the fabrics to be laundered in an aqueous wash solution containing an effective amount of the above-defined laundry detergent composition.
  • the present invention is predicated on the discovery of significantly enhanced detergency attendant to the use of the above-described triblock copolymer in a single anionic surfactant system, namely, an alkyl benzene sulfonate surfactant.
  • the present invention provides unexpected improvement in detergency, and particularly oily soil detergency, for formulations containing a single anionic surfactant in combination with a triblock copolymer in accordance with the invention.
  • detergent compositions of the invention may be formulated to be cost-effective while providing good detergency performance relative to formulations which rely upon higher levels of actives to achieve substantially similar levels of detergency.
  • the laundry detergent compositions of the invention contain a water-soluble salt of alkyl benzene sulfonate as the predominant or sole anionic surfactant.
  • the alkyl benzene sulfonates useful herein contain from about 10 to 16 carbon atoms in the alkyl group in a straight or branched chain such as, for example, the sodium, potassium ammonium or substituted ammonium (such as mono, di and tri ethanolamine) or alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulfonate.
  • the weight percent of anionic surfactant in the laundry composition may vary from about 5 to about 50% and preferably is from about 15% to about 40%.
  • the nonionic water-soluble triblock copolymer of the invention has one of the two structural formulae represented above in (I) or (II). These copolymers are commerically available and are marketed, for example, by BASF Corporation under the trademark Pluronic®. A description of the preparation of these compounds is set forth in U.S. Patent No. 2,674,619, the disclosure of which is incorporated herein by reference.
  • Preferred triblock copolymers for use herein are those wherein the weight of polyethylene oxide is from about 10% to about 80%, and most preferably from about 40%) to about 80%, by weight, of the triblock copolymer.
  • the average molecular weight of the copolymer is most usefully within the range of from about 1,100 to about 8,400.
  • the weight percent of triblock copolymer in the laundry composition is usually from about 0.1% to 10%, and preferably from about 0.2% to about 2%.
  • Builder materials may advantageously be included in the present compositions and may comprise any suitable water soluble or water insoluble builder, either inorganic or organic, providing that it is useful as a builder for the particular detergent compounds that are employed.
  • Such builders are well known to those of skill in the detergent art and include: alkali metal phosphates, such as alkali metal polyphosphates and pyrophosphates, including alkali metal tripolyphosphates; alkali metal silicates, including those of Na 2 ⁇ :Si ⁇ 2 ratio in the range of 1:1.6 to 1:3.0, preferably 1:2.0 to 1:2.8, and more preferably 1:2.35 or 1:2.4; alkali metal carbonates; alkali metal bicarbonates; alkali metal sesquicarbonates (which may be considered to be a mixture of alkali metal carbonates and alkali metal bicarbonates); alkali metal borates, e.g., borox; alkali metal citrates; alkali metal gluconates; alkali metal nitrilotriacetates; zeolites, preferably hydrated zeolites, such as hydrated Zeolite A, Zeolite X and Zeolite Y; and mixtures of individual builders within one or
  • the builders will be sodium salts and will also be inorganic.
  • a highly preferred non-phosphate mixed water soluble and water insoluble builder composition comprises carbonate, bicarbonate and zeolite builders. Phosphate-containing builder systems will usually be based on alkali metal (sodium) tripolyphosphate and silicate builders, with such silicate being in relatively minor proportion.
  • Zeolite A-type aluminosilicate builder usually hydrated, with about 15 to 25% of water of hydration is particularly advantageous for the present invention. Hydrated zeolites X and Y may be useful too, as may be naturally occurring zeolites that can act as detergent builders. Of the various zeolite A products, zeolite 4A, a type of zeolite molecule wherein the pore size is about 4 Angstroms, is often preferred. This type of zeolite is well known in the art and methods for its manufacture are described in the art such as in U.S. Patent 3,114,603.
  • the zeolite builders are generally of the formula
  • the zeolite builder should be a univalent cation exchanging zeolite, i.e., it should be aluminosilicate of a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
  • a zeolite having an alkali metal cation, especially sodium, is most preferred, as is indicated in the formula shown above.
  • the zeolites employed may be characterized as having a high exchange capacity for calcium ion, which is normally from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram of the aluminosilicate, preferably 250 to 350 mg. eg./g., on an anhydrous zeolite basis.
  • suitable fillers may be present in the detergent compositions to improve the properties and in some cases, to act as diluents or fillers.
  • suitable fillers the most preferred is sodium sulfate.
  • suitable adjuvants are enzymes to further promote cleaning of certain hard to remove stains from laundry or hard surfaces.
  • enzymes the proteolytic and amylolytic enzymes are ordinarily most useful.
  • foaming agents such as lauric myristic diethanolamide, when foam is desired, and anti-foams, when desired, such as dimethyl silicone fluids.
  • bleaches such as sodium perborate, which may be accompanied by suitable activator(s) to promote bleaching actions in warm or cold water.
  • Flow promoting agents such as hydrated synthetic calcium silicate, which is sold under the trademark Microcel® C, may be employed in relatively small proportions.
  • Other adjuvants usually present in detergent compositions include fluorescent brighteners, such as stilbene brighteners, colorants such as dyes and pigments and perfume.
  • the linear alkyl benzene sulfonate (LAS) surfactant was a sodium salt of alkyl benzene sulfonic acid having a molecular weight of approx. 375.
  • L64 and F68 are PO EO/PO type copolymers.
  • L64 is a copolymer having an average molecular weight of 2,900; and F68 is a copolymer having an A.M.W. of 8,400.
  • the washing protocol was as follows: a set of soiled swatches (3" x 4") corresponding to either a standard 12 stain set or an oily stain set (as hereinafter described) was washed for 10 minutes in a U.S. Whirlpool washing machine (medium setting) at a temperature of 77°F using water at 100 ppm hardness. The swatches were dried for 5 minutes in a Whirlpool electric dryer (high setting). The reflectance of the dried swatches was then measured by a Pacific Scientific XL800 Reflectometer.
  • the standard 12 stains used in this Example was comprised of 4 principal groups of stains: clays, oxidizables, enzymes and oily: Clays: (1) Piscataway clay (Cotton)
  • Oxidizables (1) Blueberry pie (Cotton)
  • composition of the invention provided approximately the same level of detergency as the Control composition notwithstanding that composition A contained substantially smaller amounts of sodium tripolyphosphate builder relative to the Control as well as being added to the wash at lower dosage levels.
  • Control-2 and Control-3) to measure the effect on detergency of the following variables: a triblock copolymer in accordance with the invention; a lesser amount of tripolyphosphate builder; or a lesser amount of surfactant.
  • the detergent compositions NOT FURNISHED UPON FILING
  • composition D is significantly more effective than Control-2 which is identical thereto except for the absence of the triblock polymer.
  • the 12 stain detergency of composition D is significantly better than that of Control-3.
  • Composition D which contained substantially less anionic surfactant than Control- 1 but contained a triblock copolymer provided equal or better detergency for both the standard stains and the oily stains.
  • Composition D provided significantly improved detergency for both the standard and oily sets of stains.
  • Example 3 A study was conducted to compare the effect on detergency of a Pluronic® triblock copolymer in accordance with the invention in compositions containing respectively, linear alkyl benzene sulfonate (LAS); a combination of LAS and an alcohol ethoxylate (AE); and an alcohol ethoxy sulfate (AEOS).
  • Three test compositions (E, F, and G) containing L64 Pluronic® copolymer were prepared along with three control compositions (in the absence of polymer) as shown in Table 6.
  • the detergent compositions are described in terms of the dosage provided to the wash solution (grams/wash).
  • LAS is a sodium salt of alkyl benzene sulfonic acid having a molecular weight of 375.
  • AE Neodol 25-7 marketed by Shell Chemical Company.
  • AEOS is sodium alcohol ethoxy sulfate (3EO) having a molecular weight of 432.
  • L64 is a Pluronic® copolymer described in Example 1, Table 1, footnote (2).
  • ⁇ L* is the difference in reflectance measured with a Hunter Sphere Spectrophotometer for (Composition E minus Control- 1) or (F minus Control-2) or (G minus Control-3). A value of ⁇ L* greater than 6 is considered significant for the 12 stain set employed in this study.
  • the linear alkyl benzene sulfonate was a sodium salt of alkyl benzene sulfonic acid having a molecular weight of approx. 375.
  • Composition J contained the Pluronic® surfactant (polymer) designated L64, and Composition K contained the Pluronic® surfactant designated F68. Both are described in Table 1 at footnote (2).
  • Example 1 The washing protocol of Example 1 was followed. Detergency was evaluated using the oily stain set described in Example 2. Detergency was measured by comparing the total Rd values. A difference of 12 Rd units is considered significant for this study. The detergency results are shown in Table 8.
  • compositions J and K perform at parity (or better) relative to the Control- 1 which contains a relatively higher level of builder.

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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)

Abstract

On décrit une composition détergente de blanchissage qui comprend a) environ 1 à 60 % en poids d'un tensioactif anionique constitué essentiellement d'un sel d'alkyl benzène sulfonate soluble dans l'eau; et b) une quantité effective d'un tensioactif polymérique triséquencé soluble dans l'eau comprenant des groupes de poly(éthylène oxyde) (PEOX) et de polypropylène (PP), tels qu'un copolymère de type PP/PEOX/PP présentant un poids moléculaire compris entre environ 1000 et 15000. On décrit un procédé de blanchissage utilisant ladite composition détergente.
PCT/US1998/022105 1997-10-28 1998-10-20 Solution de tensioactifs pour composition detergente de blanchissage WO1999021949A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU11028/99A AU1102899A (en) 1997-10-28 1998-10-20 Surfactant system for laundry detergent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US95920797A 1997-10-28 1997-10-28
US08/959,207 1997-10-28

Publications (1)

Publication Number Publication Date
WO1999021949A1 true WO1999021949A1 (fr) 1999-05-06

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PCT/US1998/022105 WO1999021949A1 (fr) 1997-10-28 1998-10-20 Solution de tensioactifs pour composition detergente de blanchissage

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000077136A2 (fr) * 1999-06-14 2000-12-21 Colgate-Palmolive Company Systeme de surfactant superieur destine a une composition detergente de blanchisserie a base d'alkylbenzenesulfonate et d'un copolymere d'oxyde d'ethylene /d'oxyde de propylene
WO2002031093A1 (fr) * 2000-10-10 2002-04-18 Colgate-Palmolive Company Composition de detergent de blanchisserie contenant un copolymere d'oxyde d'ethylene alkyle/oxyde de propylene

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1601652A (en) * 1977-03-16 1981-11-04 Mitsubishi Petrochemical Co Liquid detergents comprising nonionic surfactants
US4889644A (en) * 1987-06-15 1989-12-26 Henkel Kommanditgesellschaft Auf Aktien Machine washing process: detergent paste and automatic dispenser
US5152933A (en) * 1990-08-20 1992-10-06 Basf Corporation Ethylene oxide/propylene oxide copolymers as co-surfactants with detergency boosting properties in compositions also containing alkyl benzene sulfonate and ethoxylated alcohol
US5167872A (en) * 1985-10-31 1992-12-01 The Procter & Gamble Company Comprising anionic surfactant polymeric nonionic surfactant and betaine surfactant
WO1995008389A1 (fr) * 1993-09-21 1995-03-30 Basf Corporation Melanges de copolymeres en masse avec des agents tensioactifs anioniques a vitesses de dissolution ameliorees
WO1998024867A1 (fr) * 1996-12-02 1998-06-11 Kao Corporation Composition tensio-active

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1601652A (en) * 1977-03-16 1981-11-04 Mitsubishi Petrochemical Co Liquid detergents comprising nonionic surfactants
US5167872A (en) * 1985-10-31 1992-12-01 The Procter & Gamble Company Comprising anionic surfactant polymeric nonionic surfactant and betaine surfactant
US4889644A (en) * 1987-06-15 1989-12-26 Henkel Kommanditgesellschaft Auf Aktien Machine washing process: detergent paste and automatic dispenser
US5152933A (en) * 1990-08-20 1992-10-06 Basf Corporation Ethylene oxide/propylene oxide copolymers as co-surfactants with detergency boosting properties in compositions also containing alkyl benzene sulfonate and ethoxylated alcohol
WO1995008389A1 (fr) * 1993-09-21 1995-03-30 Basf Corporation Melanges de copolymeres en masse avec des agents tensioactifs anioniques a vitesses de dissolution ameliorees
WO1998024867A1 (fr) * 1996-12-02 1998-06-11 Kao Corporation Composition tensio-active

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9829, Derwent World Patents Index; Class A25, AN 98-33329 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000077136A2 (fr) * 1999-06-14 2000-12-21 Colgate-Palmolive Company Systeme de surfactant superieur destine a une composition detergente de blanchisserie a base d'alkylbenzenesulfonate et d'un copolymere d'oxyde d'ethylene /d'oxyde de propylene
WO2000077136A3 (fr) * 1999-06-14 2001-04-05 Colgate Palmolive Co Systeme de surfactant superieur destine a une composition detergente de blanchisserie a base d'alkylbenzenesulfonate et d'un copolymere d'oxyde d'ethylene /d'oxyde de propylene
WO2002031093A1 (fr) * 2000-10-10 2002-04-18 Colgate-Palmolive Company Composition de detergent de blanchisserie contenant un copolymere d'oxyde d'ethylene alkyle/oxyde de propylene

Also Published As

Publication number Publication date
AU1102899A (en) 1999-05-17

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