US3726814A - Liquid laundry detergents and a process for preparing same - Google Patents

Liquid laundry detergents and a process for preparing same Download PDF

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Publication number
US3726814A
US3726814A US00124601A US3726814DA US3726814A US 3726814 A US3726814 A US 3726814A US 00124601 A US00124601 A US 00124601A US 3726814D A US3726814D A US 3726814DA US 3726814 A US3726814 A US 3726814A
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US
United States
Prior art keywords
sodium
ethylene glycol
stilbene
brightener
benzene
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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
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US00124601A
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English (en)
Inventor
A Lancz
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
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Publication of US3726814A publication Critical patent/US3726814A/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3418Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents

Definitions

  • the subject invention is directed to clear liquid laundry detergents which include therein a stilbene brightener system.
  • the subject invention is also directed to a process for producing a stilbene brightener system which is readily incorporated into liquid laundry detergents.
  • Liquid detergent compositions in general, and liquid detergent compositions containing chemical bleaching and/or brightening agents, in specific, are well known in the art.
  • Such compositions have in the past comprised a surfactant material in combination with a brightening or bleaching agent which was dispersed therein. It is noted, however, that such dispersion resulted in numerous difliculties with regard to uniform distribution and, further, with uniform concentration of the optical brightener contained in such compositions.
  • the application to the fabric of a suitable fluorescent compound which, by virtue of its bluish fluorescence, counteracts the dull, yellowish cast of the fabric, is a logical solution to the problem of improving the whiteness and brightness of the fabric.
  • the fluorescent compound must be compatible with and non-injurious to the fabric and must impart adequate fluorescence. It must be compatible with the cleansing detergents employed as the washing medium. It must have an afiinity for the fabric and must be applied in a solution which either does not inhibit such aflinity or preferably enhances such aflinity.
  • the fluorescent compound When applied to the fabric, the fluorescent compound must be evenly and uniformly distributed since, otherwise, the appearance of the treated fabric is spotty and non-uniform.
  • Another object of the instant invention is to provide a clear liquid detergent composition containing an effective amount of optical brighteners.
  • Yet another object of the instant invention is to provide a process for incorporating optical brighteners into a liquid detergent system.
  • a still further object of the instant invention is to provide a process for incorporating optical brighteners into a detergent system which includes an anionic surfactant, which process comprises solubilizing optical brighteners with a solvent therefor.
  • optical brighteners are generally classified as anionic fluorescent dyes which serve to impart increased fluorescence and/or optical brightness to both hydrophilic and hydrophobic fibers.
  • Typical representative examples thereof include:
  • the subject clear liquid laundry detergents also include anionic and/or nonionic type surfactants.
  • Suitable anionic detergents include materials such as alkylbenzenesulfonic acid and its salts, and compounds of the formula alkyl-phenyl-SOg-M, wherein alkyl is an alkyl radical of a fatty acid and M is hydrogen or an alkali metal, which compounds comprise a well-known class of anionic detergents and include sodium dodecylbenzene sultfonate, potassium dodecylbenzene sulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate.
  • alkali metal salts of the higher alkylsulfonic acids and the alkali metal dialkyl sulfosuccinates e.g., sodium dioctyluslfosuccinate; and sodium dihexylsulfosuccinate; sodium sulfoethylpthalate; sodium oleyl-p-am'sidinesulfonate; sodium tetradecanesulr fonate; sodium diisopropylnaphthalenesulfonate; sodium octylphenoxyethoxyethylsulfate, etc.; and the alkali metal alkyl sulfates, e.g., sodium lauryl sulfate and the like.
  • alkylbenzene-sulfonic acid acid and salts thereof included those which are biodegradable and which are particularly characterized by a linear alkyl substituent of from C to C and preferably from C to C
  • the carbon chain length represents, in general, an average chain length since the method for producing such products usually employs alkylating reagents of mixed chain length.
  • substantially pure olefins as Well as alkylating compounds used in other techniques can and do give alkylated benzene sulfonates wherein the alkyl moiety is substantially (i.e.
  • linear alkyl benzene sulfonates are [further characterized by the position of the benzene ring in the linear alkyl chain, with any of the position isomers (i.e. alpha to omega) being operable and contemplated.
  • the linear alkyl benzene sulfonates are generally and conveniently prepared by sulfonating the corresponding alkyl benzene hydrocarbons which in turn may be prepared by alkylating benzene with a linear alkyl halide, a l-alkene or a linear primary or secondary alcohol.
  • Pure isomers (of the l-phenyl isomer) are prepared by reduction of the acylated benzene (alkyl phenyl ketone) using a modification of the Wolif-Keshner reaction.
  • the 2- phenyl isomer is obtained from n-undecyl phenyl ketone and methyl magnesium bromide to form the tertiary alcohol which is dehydrated to the alkene and then hydrogneated.
  • the S-phenyl isomer is obtained similarly from a n-heptyl phenyl ketone and n-butyl magnesium bromide.
  • the other isomers are obtained in a similar manner from the appropriate n-alkyl phenyl ketone and n-alkyl magnesium bromide.
  • benzene sulfonates employ the lower alkyl (C to C analogs of benzene such as toluene, xylene, the trimethyl benzenes, ethyl benzene, isopropyl benzene and the like.
  • the sulfonates are generally employed in the water soluble salt form which include as the cation, the alkali metals, ammonium, and lower amine and alkanolamine.
  • sullfonates may, of course, also be used with mixtures which may include compounds wherein the linear alkyl chain is smaller or larger than indicated herein provided that the average chain length in the mixture conforms to the specific requirements of C to C
  • the linear parafiin sulfonates are also a well-known group of compounds and include water soluble salts (alkali metal, amine, alkanolamine, and ammonium) of:
  • linear alkyl sulfates which are contemplated in this invention comprise the range of C to C Specific examples include sodium -decyl sulfate; sodium n-dodecyl sulfate; sodium n-hexadecyl sulfate; sodium n-heptadecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (1 to moles ethylene oxide) derivatives; and, of course, the other water-soluble salt-forming cations mentioned above.
  • nonionic detergents such as alkaryl polyglycol detergents such as alkyl-phenol-ethylene oxide condensates (2 200 moles ethylene oxide), e.g., p-isooctyl phenol-polyethylene oxide (10 ethylene oxide units), long chain alcohol-ethylene oxide condensation products (2-200 moles ethylene oxide), e.g., dodecyl alcohol-polyethylene oxides having 4 to 16 ethylene oxide units per molecule, polyglycerol monolaurate, glycol dioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquioleate, the condensation products of ethylene oxide with sorbitan esters of long chain fatty acids (Tweens), alkylolamides, amine oxides, phosphine oxides, etc.
  • alkaryl polyglycol detergents such as alkyl-phenol-ethylene oxide condensates (2 200 mo
  • composition of the instant invention may also include, in addition to the fabric softening compounds and conventional anionic, cationic, and nonionic detergent compositions, builders, brighteners, hydrotropes, germicides, soil suspending agents, anti-redeposition agents, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes, water-soluble alcohols, foam boosters, non-detergent alkali metal benzene sulfonates, etc.
  • the subject composition may, in addition, include a builder material.
  • the builder material is a water-soluble salt of an amino carboxylic acid such as, for example, nitrilo triacetic acid.
  • the trisodium salt thereof is the sole builder in connection with the instant composition.
  • hydrotropes include such compounds as, sodium xylene sulfonate, potassium xylene sulfonate, sodium and potassium toluene sulfonates, in the position isomers thereof, and ethyl benzene sulfonate.
  • the subject invention is also directed to a process for incorporating the above-noted optical brighteners into a liquid detergent composition comprising the other materials discussed above so as to provide a clear liquid laundry detergent having brightening characteristics.
  • the brightening materials are first incorporated into a solvent therefor, such as an ethylene glycol ether or dimethyl sulfoxide.
  • ethylene glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropylether, diethylene glycol monoethyl ether, ethylene glycol with dialkyl ethers, ethylene glycol trialkyl ethers, and the like.
  • ethoxylated fatty alcohols which may be utilized in connection with the instant invention, include in addition to those noted above the following fatty alcohols containing from about 2 to about 200 moles of ethylene oxide, such as, for example, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, and the like.
  • the said brightener system may then be incorporated into the remaining ingredients so as provide a clear liquid laundry detergent formulation.
  • one employs from about 0.01% to about 0.5% brightener based on the weight of the total active ingredients in the final detergent formulation. While the proportions of the remaining ingredients are not critical to the instant invention, it is noted that generally one may employ from about 1 to about 40% total surfactant ingredient, from 1 to about 50% builder, from about 1 to about 40% hydrotrope, from about 1 to about 20% ethoxylated fatty alcohol, with the remaining proportions being made up of additive materials such as perfumes, dyes, and the like, and water.
  • a clear liquid detergent composition comprising:
  • the above composition was prepared by first mixing the stilbene brighteners with the ethoxylated fatty alcohol and the ethylene glycol monobutyl ether. The resulting mixture was then heated to 120 F. for fifteen minutes and subsequently added to a mixture of deionized water, nitrilotriacetic acid trisodium salt, and ammonium cemene sulfonate. The remaining ingredients were then added and the product which resulted was found to be a clear liquid detergent composition.
  • Example 2 The composition of Example 1 was again prepared, substituting sodium xylene sulfonate for the ammonium cumene sulfonate therein. The composition was prepared as in Example 1 and found to produce a stable clear liquid detergent composition containing brightener materials.
  • Example 3 The composition of Example 1 was again prepared, substituting 2% by weight dimethylsulfoxide for the ethylene glycol monobutyl ether employed therein. Once again, the composition which resulted was found to be a clear liquid.
  • EXAMPLE 4 As is readily apparent from the foregoing, the subject invention provides a process whereby stilbene type brighteners are readily solu-bilized and incorporated into a clear liquid detergent composition for use in the washing and brightening of fabrics.
  • a clear liquid brightener detergent composition consisting essentially of from about 1% to about 40% of a water-soluble anionic organic detergent, from about 1% to about 50% of a water-soluble salt of an amino carboxylic acid, from about 1% to about 40% of a hydrotrope selected from the group consisting of the sodium, potassium and ammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethyl benzene sulfonic acid and cumene sulfonic acid from about 1% to about 20% of an ethoxylated fatty alcohol having from about, 8 to about 15 carbon atoms, from about 0.01% to about 5% of an anionic stilbene optical brightener and from about 1% to about 20% of a compound selected from the group consisting of ethylene glycol ethers and dimethyl sulfoxide, said ethylene glycol ethers selected from the group consisting of ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers
  • composition of claim 1 wherein the watersoluble salt of an amino carboxylic acid is the trisodium salt of nitrilotriacetic acid.
  • composition of claim 1 wherein the ethylene glycol ether is ethylene glycol monobutyl ether.
  • a process for preparing a clear liquid brightener detergent composition which comprises mixing from about 0.01% to about 0.5% of an anionic stilbene brightener with from about 1% to about 20% of a compound selected from the group consisting of ethylene glycol ethers and dimethyl sulfoxide, said ethylene glycol ethers selected from the group consisting of ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers and ethylene glycol trialkyl ethers, said ethers having an alkyl group of from about 1 to 4 carbon atoms and from about 1% to about 20% of an ethoxylated fatty alcohol having from about 8 to 15 carbon atoms, heating the mixture to a temperature of from about to about F. for a period of time sufi'icient to solubilize the brightener in the liquid composition and subsequently mixing the solub-ilized brighteners with from about 1% to about 40% of an anionic water-soluble detergent and water.

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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)
US00124601A 1971-03-15 1971-03-15 Liquid laundry detergents and a process for preparing same Expired - Lifetime US3726814A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12460171A 1971-03-15 1971-03-15

Publications (1)

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US3726814A true US3726814A (en) 1973-04-10

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US (1) US3726814A (it)
AT (1) ATA170872A (it)
AU (1) AU456770B2 (it)
BE (1) BE780048A (it)
CA (1) CA973310A (it)
CH (1) CH571061A5 (it)
DE (1) DE2209200B2 (it)
DK (1) DK143411C (it)
ES (1) ES400498A1 (it)
FI (1) FI55350C (it)
FR (1) FR2130106B1 (it)
GB (1) GB1380107A (it)
IT (1) IT961281B (it)
NL (1) NL179830B (it)
NO (1) NO144243C (it)
SE (1) SE394290B (it)
ZA (1) ZA72922B (it)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998750A (en) * 1975-06-30 1976-12-21 The Procter & Gamble Company Liquid detergent composition
US4263176A (en) * 1978-11-21 1981-04-21 Hoechst Aktiengesellschaft Color-stable brighteners for detergents
US4645623A (en) * 1984-12-17 1987-02-24 Monsanto Company Alkylaryl sulfonate compositions
US4687593A (en) * 1984-12-17 1987-08-18 Monsanto Company Alkylaryl sulfonate compositions
US5024786A (en) * 1987-10-30 1991-06-18 Sandoz Ltd. Detergent compositions containing an anionic surfactant and a 4,4'-bis(triazinylamino)-stilbene disulphonic acid optical brightener
US5174927A (en) * 1990-09-28 1992-12-29 The Procter & Gamble Company Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
WO1995034621A1 (en) * 1994-06-10 1995-12-21 The Procter & Gamble Company Aqueous emulsions containing a hydrophobic brightener, a hydrophilic surfactant and a hydrophobic surfactant
US20080146482A1 (en) * 2006-12-06 2008-06-19 The Procter & Gamble Company Liquid laundry detergent having improved brightener stability

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2326467B2 (de) * 1972-06-01 1979-02-22 Colgate-Palmolive Co., New York, N.Y. (V.St.A.) Flüssiges Grobwaschmittel
DE2609752A1 (de) * 1976-03-09 1977-09-22 Henkel & Cie Gmbh Fluessiges, kaeltestabiles waschmittelkonzentrat
GR76287B (it) * 1981-09-28 1984-08-04 Procter & Gamble
US4753750A (en) * 1984-12-31 1988-06-28 Delaware Liquid laundry detergent composition and method of use
GB2187749B (en) * 1986-03-11 1990-08-08 Procter & Gamble Stable liquid detergent composition hydrophobic brightener
GB9408940D0 (en) * 1994-05-05 1994-06-22 Procter & Gamble Manual dishwashing compositions
GB9801082D0 (en) * 1998-01-19 1998-03-18 Unilever Plc Improvements relating to hard surface cleaners

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2838504A (en) * 1955-04-21 1958-06-10 Sterling Drug Inc Benzimidazolylstilbene whitening and brightening agents
BE553563A (it) * 1955-12-20
GB1084061A (it) * 1965-12-09
AT281242B (de) * 1966-09-22 1970-05-11 Procter & Gamble Flüssiges Waschmittel
DK130311A (it) * 1967-11-06
DE1816348A1 (de) * 1968-12-21 1970-06-25 Henkel & Cie Gmbh Wasch-,Bleich- und Reinigungsmittel

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998750A (en) * 1975-06-30 1976-12-21 The Procter & Gamble Company Liquid detergent composition
US4263176A (en) * 1978-11-21 1981-04-21 Hoechst Aktiengesellschaft Color-stable brighteners for detergents
US4645623A (en) * 1984-12-17 1987-02-24 Monsanto Company Alkylaryl sulfonate compositions
US4687593A (en) * 1984-12-17 1987-08-18 Monsanto Company Alkylaryl sulfonate compositions
US5024786A (en) * 1987-10-30 1991-06-18 Sandoz Ltd. Detergent compositions containing an anionic surfactant and a 4,4'-bis(triazinylamino)-stilbene disulphonic acid optical brightener
US5174927A (en) * 1990-09-28 1992-12-29 The Procter & Gamble Company Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines
WO1995034621A1 (en) * 1994-06-10 1995-12-21 The Procter & Gamble Company Aqueous emulsions containing a hydrophobic brightener, a hydrophilic surfactant and a hydrophobic surfactant
US20080146482A1 (en) * 2006-12-06 2008-06-19 The Procter & Gamble Company Liquid laundry detergent having improved brightener stability

Also Published As

Publication number Publication date
GB1380107A (en) 1975-01-08
NL179830B (nl) 1986-06-16
SE394290B (sv) 1977-06-20
ATA170872A (de) 1975-08-15
ES400498A1 (es) 1975-07-16
BE780048A (fr) 1972-07-17
CH571061A5 (it) 1975-12-31
FR2130106B1 (it) 1975-08-29
IT961281B (it) 1973-12-10
DK143411B (da) 1981-08-17
FI55350B (fi) 1979-03-30
FR2130106A1 (it) 1972-11-03
CA973310A (en) 1975-08-26
DK143411C (da) 1981-12-21
AU456770B2 (en) 1974-12-10
NO144243B (no) 1981-04-13
DE2209200B2 (de) 1981-01-22
NO144243C (no) 1981-07-22
ZA72922B (en) 1973-09-26
AU3953172A (en) 1973-09-06
DE2209200A1 (de) 1972-09-21
NL7203455A (it) 1972-09-19
FI55350C (fi) 1979-07-10

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