EP0223306B1 - Ein binäres System von anionischen, oberflächenaktivenen Stoffen enthaltendes flüssiges Reinigungsmittel - Google Patents

Ein binäres System von anionischen, oberflächenaktivenen Stoffen enthaltendes flüssiges Reinigungsmittel Download PDF

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Publication number
EP0223306B1
EP0223306B1 EP86202001A EP86202001A EP0223306B1 EP 0223306 B1 EP0223306 B1 EP 0223306B1 EP 86202001 A EP86202001 A EP 86202001A EP 86202001 A EP86202001 A EP 86202001A EP 0223306 B1 EP0223306 B1 EP 0223306B1
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Prior art keywords
composition
alkyl
carbon atoms
anionic surfactant
accordance
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EP86202001A
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English (en)
French (fr)
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EP0223306A3 (en
EP0223306A2 (de
Inventor
Jean Pol Boutique
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Priority to AT86202001T priority Critical patent/ATE74377T1/de
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Publication of EP0223306A3 publication Critical patent/EP0223306A3/en
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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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates

Definitions

  • the present invention relates to homogeneous, concentrated, liquid detergent compositions containing a binary anionic surfactant system, together with desirable detergent ingredients.
  • the binary anionic surfactant system is represented by a mixture, in well-defined ratios, of an alk(en)yl succinate and a specific class of sulfonated surface-active agents, said sulfonated surface-active agents having a critical micellar concentration in the range of from 10 ⁇ 5 to 10 ⁇ 3 mole/l.
  • Preferred sulfonated surface-active agents for use in the binary system of the invention are linear alkyl arene sulfonates, containing from 13 to 17 carbon atoms in their alkyl group, and dialkyl sulfosuccinates, having from 9 to 12 carbon atoms in each alkyl group.
  • compositions of the invention exhibit excellent cleaning properties on all types of stains.
  • the succinate ingredient is well-known in the detergent art and has been disclosed in combination with all kinds of detergent executions.
  • Succinate derivatives have been used for several purposes as surfactants in U.S. Patent 2.283.214, as builders in U.S. Patent 2.562.758, as suds-boosters in U.K. Patent 1.293.753, and as ingredients of liquid cleaners in U.S. Patent 4.277.378.
  • EP-A-0 028 850 discloses nonionic-rich liquid detergent compositions containing mono-alkyl or alkenyl succinates as hydrotropes and small levels of C10 ⁇ 15 alkyl benzene sulfonates.
  • Linear alkyl-arene sulfonates such as linear ortho-xylene sulfonates
  • surfactants mainly for Enhanced Oil Recovery Applications.
  • European Patent 0 111 354 their use in detergents is mentioned.
  • Dialkyl sulfosuccinates are also known as surfactants; they have been disclosed frequently in high-foaming dishwashing compositions: U.K. Patents 2.130.235 and 2.130.238, disclose combination of dialkyl sulfosuccinates with linear alkyl sulfonates and ethoxylated nonionic surfactants.
  • EP.A. 0200263 discloses liquid detergent compositions containing a ternary surfactant system of succinates, anionic surface-active agents and nonionic surface-active agents.
  • EP.A. 0212723 to liquid detergent compositions containing a mixture of citrates and succinates as detergency builders.
  • the present invention relates to homogeneous concentrated aqueous liquid detergent compositions containing less than 50% by weight of water, and a binary anionic surfactant system, together with conventional additives, characterized in that,
  • Preferred sulfonated surface-active agents are:
  • the anionic surfactant binary mixture amounts to from 12% to 50% preferably from 15% to 35% of the total composition and is represented by a binary composition of:
  • the critical micellar concentration (hereinafter referred to as cmc) of a compound is the concentration above which the molecules of the compound begin to aggregate to form micelles.
  • the method used in the context of the present invention is the surface-tension-log concentration plot method, which can be found e.g. in "Critical Micelle Concentrations of Aqueous Surfactant Systems", by P. Mukerjee and K.J. Mysels, published by the United States Department of Commerce.
  • the cmc is determined with the aid of solutions in distilled water. The temperature of measurement is superior to the Kraft temperature.
  • sulfonated surface-active agents inclusive of:
  • the sulfonate component can be represented by individual sulfonates having the specified cmc's or by mixtures of sulfonate surfactants provided the sulfonate mixture has a cmc within the claimed range. It is possible that specific sulfonate mixtures meet the cmc requirement even though the individual sulfonates of the mixture can have cmc's which are outside of the claimed range.
  • conventional sulfonate surface-active agents such as water-soluble salts of alkylbenzene sulfonic acid containing from 10 to 18 carbon atoms in the alkyl groups can be present in the above mixtures.
  • the weight ratio of sulfonate to succinate surfactant in the binary mixture is in the range from 2:1 to 1:4.
  • compositions therein can contain, as an optional but preferred ingredient, a nonionic surface-active agent.
  • the nonionic surfactant can be present at levels of from 3% to 35%, preferably from 8% to 20% of the total composition.
  • the nonionic surfactant component contains a hydrophobic organic radical condensed with an ethylene oxide hydrophilic moiety.
  • All ethoxylated nonionic surfactants which are known to be suitable for use in detergent application can be used in the compositions of this invention.
  • Preferred nonionic species herein are polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms, and having a HLB (hydrophilic lipophilic balance) in the range from 8 to 15. These preferred ethoxylates frequently contain from 2 to 14 moles of ethylene oxide per mole of hydrophobic moiety.
  • the hydrocarbyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.
  • a preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from 4 to 10 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable species of this class of ethoxylates include: the condensation product of C12-C15 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of C13 ⁇ 15 oxoalcohols and 5 moles of ethylene oxide; the condensation product of narrow cut C14-C15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo)alcohol; the condensation product of a narrow cut C12-C13 fatty (oxo)alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and the condensation products of a C10-C14 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range
  • the fatty oxo alcohols while mainly linear can have, depending upon the processing conditions and raw material olefins, a certain degree of branching, particularly short chain such as methyl branching.
  • a degree of branching in the range from 15% to 50% (weight %) is frequently found in commercial oxo-alcohols.
  • Nonionic ethoxylated components can also be represented by a mixture of 2 separately ethoxylated nonionic surfactants having a different degree of ethoxylation.
  • compositions herein contain less than 50%, usually from 15% to 40% water.
  • the claimed compositions have a pH, measured in 1% aqueous solution at 20°C, in the range from 7 to 9.
  • This pH range implies that the anionic surfactant component, i.e., the binary mixture of sulfonate and succinate, particularly the succinate, is substantially completely (i.e., more than 90%) neutralized in the claimed composition as is.
  • compositions herein frequently contain a series of optional ingredients which are used for their known functionality in conventional quantities.
  • optional ingredients can include fatty acids, saturated and/or unsaturated, and the corresponding soaps, synthetic anionic surfactants which are different from sulfonates (non-sulfonate anionics), water-insoluble solvents, enzymes, enzyme stabilizers, polyacids, polyaminopolyalkylene ethoxylate polymers, suds regulants, brighteners, perfumes, dyes, antioxidants, bactericides, corrosion inhibitors, fabric-softening agents, phase regulants and the like.
  • Suitable fatty acids saturated or unsaturated, have from 10 to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid.
  • the corresponding soaps can equally be used.
  • the optional fatty acid/soaps are used in levels up to 10%, preferably from 1% to 8%, (of the composition).
  • the fatty acids/soaps among others, act as suds modifiers/regulants.
  • Synthetic non-sulfonate anionics can also be used in the composition in relatively minor levels.
  • suitable non-sulfonate anionics include the salts of sulfated fatty alcohols having from 12 to 20 carbon atoms in the alcohol chain.
  • Water-insoluble solvents such as terpenes, phthalic acid esters and liquid paraffins can also be used in levels generally below 5%.
  • Detergent enzymes generally aid and augment the removal of specific stains.
  • Suitable enzymes can be represented by proteases, amylases, lipases, glucose-oxidases, or mixtures thereof.
  • Proteases and amylases are preferred in the claimed liquid concentrated compositions. They are frequently employed in a level from 0.01% to 1%.
  • Suitable stabilizing systems include short C1 ⁇ 4 chain carboxylic acid, particularly formic acid in combination with low level of calcium, boric acid and the water-soluble salts thereof possibly in combination with polyols.
  • polyacid or mixture of polyacids in an amount from 0.05% to 4%.
  • Suitable polyacids are those having one pK value of at least 5.
  • Preferred polyacid species for use herein can be represented by citric acid, and organo-phosphonic acids, particularly alkylene-polyamino-polyalkylene phosphonic acids such as ethylene diamine tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid or the salts thereof.
  • Suitable polyamino-polyalkylene ethoxylate polymers disclosed in published European Patent Application N o 112 593, are present at levels of from 0.2 to 1.2%.
  • Non-fatty acid detergent suds regulants can also be used.
  • Preferred species include alkylated polysiloxanes such as dimethylpolysiloxane also frequently termed silicone.
  • the silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% to 0.2%.
  • compositions herein can also contain known antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.01% to 0.25% (by reference to total composition). These antioxidants are frequently introduced in conjunction with unsaturated organic acids. While many suitable antioxidants are readily known and available for that purpose, especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole. Other suitable antioxidants are: 4,4'thiobis(6-ter-butyl-mcresol) and 2-methyl-4,6-dinonyl phenol.
  • Soil release polymers can also be incorporated in the compositions herein. Suitable species of such release polymers are described in U.S. copending Patent Application Serial Number 684.511, filed December 21, 1984.
  • phase regulant is a further optional ingredient in the compositions herein.
  • This component together with water can constitute the solvent matrix for the claimed concentrated liquid compositions.
  • Suitable ingredient classes include lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethyleneglycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms.
  • Specific examples of phase regulants are: ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; monomethyl-, ethyl-, propyl-, and monobutyl ethers of di-ethylene glycol.
  • Concentrated liquid detergent compositions are prepared by mixing the individual ingredients listed hereinafter in the stated proportions.
  • compositions were used for comparative laundry tests.
  • a MIELE® W423 washing machine was used thereby selecting a main-wash step.
  • Cotton and polyester/cotton (polycotton) strips stained as indicated below were used to measure the comparative performance. Additional testing parameters were, temperature 60°C, product usage 180 g/18 l. of city water having an average water hardness of about 3 mmoles/l.; laundering treatment in presence of 3 kgs soiled clothes (no-pretreatment on test strips); stains : greasy type, i.e., make-up, lipstick, and dirty motor oil (DMO).
  • DMO dirty motor oil
  • composition A a commercial heavy duty liquid
  • composition B a succinate containing liquid detergent
  • compositions of Example 1 and 2 On other types of stains (bleachable, enzymatic, particulate) the performance of the compositions of Example 1 and 2 is at least as good as the performance of composition B, with composition A as a reference.

Claims (8)

  1. Homogene konzentrierte wäßrige flüssige Detergenszusammensetzung, enthaltend weniger als 50 Gew.-% Wasser,und ein binäres anionisches grenzflächenaktives System, gemeinsam mit herkömmlichen Zusatzstoffen, dadur gekennzeichnet, daß
    (a) das binäre anionische grenzflächenaktive System 12 Gew.-% bis 50 Gew.-% der Zusammensetzung darstellt;
    (b) das anionische grenzflächenaktive System durch ein Gemisch aus
    (1) einem Alk(en)ylsuccinat der Formel
    Figure imgb0007
     worin R₁ ein Alk(en)ylrest mit 10 bis 20 Kohlenstoffatomen ist und R₂ Wasserstoff oder C₁-C₄-Alkyl bedeutet; und
    (2) einem sulfonierten grenzflächenaktiven Mittel mit einer kritischen Mizellenkonzentration im Bereich von 10⁻³ bis 10⁻⁵ Mol/l dargestellt wird;
    wobei das Gewichtsverhältnis von Sulfonat zu Succinat im Bereich von 2:1 bis 1:4 beträgt.
  2. Zusammensetzung nach Anspruch 1, worin das sulfonierte grenzflächenaktive Mittel unter linearen Alkylxylolsulfonaten mit 13 bis 17 Kohlenstoffatomen in der Alkylgruppe, linearen Alkyltoluolsulfonaten mit 13 bis 17 Kohlenstoffatomen in der Alkylgruppe und Dialkylsulfosuccinaten mit 9 bis 12 Kohlenstoffatomen in jeder Alkylgruppe und Gemischen hievon ausgewählt ist.
  3. Zusammensetzung nach Anspruch 2, worin das sulfonierte grenzflächenaktive Mittel unter linearen C₁₃₋₁₄-Orthoxylolsulfonaten und Di-C₁₀-alkylsulfosuccinaten ausgewählt ist.
  4. Zusammensetzung nach Anspruch 1, worin das binäre anionishe grenzflächenaktive System 15 Gew.-% bis 35 Gew.-% der Gesamtzusammensetzung darstellt.
  5. Zusammensetzung nach Anspruch 1, welche zusätzlich 3 Gew.-% bis 35 Gew.-% eines nichtionischen grenzflächenaktiven Mittels enthält.
  6. Zusammensetzung nach Anspruch 1, welche zusätzlich 1 Gew.-% bis 8 Gew.-% einer Fettsäure mit 10 bis 18 Kohlenstoffatomen in der Alkylkette enthält.
  7. Zusammensetzung nach Anspruch 1, worin das Alkenylsuccinat 12 bis 16 Kohlenstoffatome im Alkenylrest besitzt und R₂ Wasserstoff bedeutet.
  8. Zusammensetzung nach Anspruch 6, worin die Fettsäure Ölsäure ist.
EP86202001A 1985-11-20 1986-11-14 Ein binäres System von anionischen, oberflächenaktivenen Stoffen enthaltendes flüssiges Reinigungsmittel Expired - Lifetime EP0223306B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86202001T ATE74377T1 (de) 1985-11-20 1986-11-14 Ein binaeres system von anionischen, oberflaechenaktivenen stoffen enthaltendes fluessiges reinigungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB858528521A GB8528521D0 (en) 1985-11-20 1985-11-20 Liquid detergent compositions
GB8528521 1985-11-20

Publications (3)

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EP0223306A2 EP0223306A2 (de) 1987-05-27
EP0223306A3 EP0223306A3 (en) 1989-05-03
EP0223306B1 true EP0223306B1 (de) 1992-04-01

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EP (1) EP0223306B1 (de)
JP (1) JPH0739591B2 (de)
AT (1) ATE74377T1 (de)
CA (1) CA1334571C (de)
DE (1) DE3684668D1 (de)
GB (1) GB8528521D0 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2245000B (en) * 1987-09-17 1992-06-03 Colgate Palmolive Co Liquid detergent composition
JPH01287017A (ja) * 1988-05-11 1989-11-17 Kao Corp 低刺激性洗顔料
JPH02113100A (ja) * 1988-10-21 1990-04-25 Kao Corp 液体洗浄剤組成物
EP0430330A3 (en) * 1989-11-24 1991-12-18 The Procter & Gamble Company Suspending liquid detergent compositions
JPH04189637A (ja) * 1990-06-19 1992-07-08 Teikoku Kuromu Kk トラツク用荷締めべルト
FR2780732B1 (fr) * 1998-07-06 2000-09-08 Ceca Sa Compositions detergentes non moussantes pour milieux alcalins concentres
JP7124658B2 (ja) * 2018-11-15 2022-08-24 日油株式会社 難水溶性物用洗浄剤組成物
US20240060005A1 (en) 2020-12-25 2024-02-22 Kao Corporation Method for treating textile product

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2642400A (en) * 1950-05-10 1953-06-16 Monsanto Chemicals Surface-active composition
US3579453A (en) * 1968-11-12 1971-05-18 Rohm & Haas Alkali-soluble surfactant consisting of substituted succinic acid-nonionic ethoxylate blends
NZ206209A (en) * 1982-11-16 1986-01-24 Unilever Plc Foaming liquid detergents containing sulphosuccinic acid esters and polyethoxy sulphates
NZ206212A (en) * 1982-11-16 1986-04-11 Unilever Plc Foaming liquid detergent compositions containing sulphosuccinic acid esters and alkyl ether sulphates

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Publication number Publication date
GB8528521D0 (en) 1985-12-24
EP0223306A3 (en) 1989-05-03
EP0223306A2 (de) 1987-05-27
ATE74377T1 (de) 1992-04-15
DE3684668D1 (de) 1992-05-07
JPS62195096A (ja) 1987-08-27
CA1334571C (en) 1995-02-28
JPH0739591B2 (ja) 1995-05-01

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