US3793215A - Soap bars - Google Patents

Soap bars Download PDF

Info

Publication number
US3793215A
US3793215A US00285318A US3793215DA US3793215A US 3793215 A US3793215 A US 3793215A US 00285318 A US00285318 A US 00285318A US 3793215D A US3793215D A US 3793215DA US 3793215 A US3793215 A US 3793215A
Authority
US
United States
Prior art keywords
soap
percent
bar
oil
bars
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
US00285318A
Other languages
English (en)
Inventor
B Smith
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive 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 Colgate Palmolive Co filed Critical Colgate Palmolive Co
Application granted granted Critical
Publication of US3793215A publication Critical patent/US3793215A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/04—Protein or carboxylic compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/05—Organic amine, amide, or n-base containing

Definitions

  • soap and a synthetic detergent having lime soap dispersing properties be combined in bar form to prevent the formation of the very undesirable lime soap curds.
  • the use of large amounts of synthetic detergent in combination with soap generally results in the impairment or elimination of desirable soap properties such as lathering performance, firmness and non-tackiness.
  • the inclusion of large amounts of synthetic detergent in soap bars usually results in manufacturing difficulties and a substantially increased cost.
  • a new synthetic detergent which when combined with soap in predetermined amounts produces a combination bar exhibiting a substantially reduced tendency to form lime soap curds when used in hard water. Additionally, the new combination bars retain good lathering performance, are non-tacky and pleasant to use.
  • the kind of soap used in preparing the improved combination soap-detergent bar is not critical and should not be considered a limitation of the invention. Any of the water-soluble soaps, derived from animal or vegetable fatty acids, and formulated for industrial, household and toilet use may be employed. Watersoluble soaps such as the sodium, potassium and other suitable alkali metal or ammonium soap or soaps of nitrogen bases, such as triethanolamine, derived from fats and oils such as cottonseed oil, soybean oil, corn oil, olive oil, palm oil, palm kernel, lard, greases, fish oils and the like, as well as their hydrogenated derivatives; and mixtures thereof, that are properly blended to yield the desired soap quality may be used in formulating the soap portion of the new combination bars.
  • Watersoluble soaps such as the sodium, potassium and other suitable alkali metal or ammonium soap or soaps of nitrogen bases, such as triethanolamine, derived from fats and oils such as cottonseed oil, soybean oil, corn oil, olive oil, palm oil, palm kernel, lard, greases,
  • the new detergent bar includes a synthetic detergent component of up to about 30 percent by weight. More specifically the synthetic detergent component of the improved bar includes fatty ester amides of sulphosuccinic acid having the following alternative structures:
  • M is chosen from those positive metals, and groups which produce water-soluble salts of the sulfosuccinate amide, including the alkali metals sodium and potassium, hydrogen, ammonium or organic bases such as ethanolamine, alkaloid, etc.
  • R is hydrogen or a C to C saturated or unsaturated fatty chain
  • R is a C, to C aliphatic chain
  • R is hydrogen or a C,, to C,,, saturated or unsaturated fatty chain
  • R, and R cannot both be hydrogen.
  • the monoester derivative is preferred in practicing the invention, i.e., wherein R, is hydrogen; significant quantities of the diester as well as free alcohol and free alcohol amide can be present.
  • sperm oil monoalkylolamide sulphosuccinate is used as the synthetic detergent ingredient of the new bars.
  • Sperm oil monoethanolamide sulphosuccinate which is a mixture of components of the above described structure wherein M is sodium, R, is H, C H or C,,;H plus minor amounts of other fatty chains; R iS C2H4- and R3 is C15H29, C17H33 OI C19H37 plus minor amounts of other aliphatic chains is preferred.
  • the foregoing sperm oil derivatives are mainly monoester but significant quantities of di-ester, free alcohol and free alkyl ethanolamide would be expected as well.
  • sperm oil monoalkylolamide sulphosuccinates can be synthesized from sperm oil, which is R COOR, wherein R, is a C to C saturated or unsaturated fatty chain (mainly C,,,H,;, and C,,,H and R is a C to C saturated or unsaturated fatty chain (mainly C, H C I-I and C l'l as follows sperm oil is reacted with an alkylolamine of the general formula HOR -NH wherein R is C H C H or C.,H to give a fatty alkylolamide of the formula R CONHR Ol-l and a fatty alcohol, R,Ol-l. The'fatty alkylolamide and fatty alcohol mixture is reacted with maleic anhydride to give sperm oil monoalkylolamide maleate, which has the following structure:
  • the caustic used to saponify the fat charge is prefera- -bly sodium hydroxide but it may be replaced in part by potassium hydroxide, e.g., up to about 15 percent if desired.
  • preservatives and/or a sequestrant in the soap to prevent the rancification of the free fatty acids.
  • suitable preservatives and sequestrants are the following: 2-6 ditertiary butyl pcresol, tertiary butyl hydroxyanisole, Sopanox, triphenyl phosphite, stannic chloride magnesium silicate, Benztriazole and the alkali salts of ethylene diamine tetraacetic acid, hydroxyethylethylene diamine triacetic acid, diethylene triamine pentacetic acid and dihydroxyethyl glycine.
  • the usual steps for converting kettle soap into milled toilet bar form may be used for making the bars of the present invention which include crutching the neat soap phase with the predetermined proportion of synthetic detergent and other desired additives then drying the soap to a moisture content within the range of about 8 to 15 percent, preferably about 9 to 10 percent, mixing the dried soap in the form of dried ribbons, granules, or the like, in an amalagamator with other desired additives such as colors, perfumes, glycerine, lanolin, cold cream, etc., milling the mixture, plodding the milled chips to form a long, continuous bar, cutting the bar into tablet or cake lengths and pressing or stamping the tablet or cake which may then be wrapped or not, as desired.
  • Suitable soap making processes that may be used to prepare soap for use in the present process include the usual kettle soap making process, continuous saponification processes in which saponification is effected with aqueous alkali and heat, the resultant mixture being washed and fitted to obtain a neat soap either continuously or by use of a kettle for the fitting and optionally one or more washing stages, and neutralization processes for fatty acids derived by hydrolysis of fats and oils.
  • a typical kettle process includes the following stages:
  • the fatty material chosen for the particular soap to be produced e.g., fats and oils which are glyceryl esters of fatty acids
  • aqueous caustic solution to effect substantial conversion of the fatty material to glycerine and fatty acid salts of the alkali metal or metals present in the caustic solution.
  • sodium soaps are generally preferred, but in some cases caustic potash may be used with caustic solution.
  • Potassium soaps are softer than sodium soaps of the same fatty acid content and, therfore, the content of potassium fatty acid salts is somewhat limited in proportion to the sodium fatty acids salts in order to have a soap that works up well into bar form in conventional soap-making machinery.
  • the caustic solution used in the killing stage is obtained in whole or in part from the change stage of another batch.
  • the extent of saponification in the killing stage is not critical and may vary from as low as about 80 percent to almost complete saponification.
  • salt is added to the reaction mixture in sufiicient concentration to effect precipitation of the soap from the solution.
  • the salt used may be fresh salt or salt recovered from the purification of the glycerine, or a mixture of both.
  • boiling is continued for a short time after addition of the salt and if the saponification is incomplete in the killing stage caustic may be included with the salt to complete the saponification during this boil.
  • the mass is then settled, during which the less dense soap rises to the top and the spent lye containing the bulk of the glycerine and electrolyte sinks to the bottom. When the settling is complete the lye is drawn off and sent to the glycerine plant for recovery of the glycerine, salt, etc.
  • the washing stage has as its object the more complete removal of glycerine, which may be as much as 0.5 percent of the weight of the soap layer left after drawing off the lye, and the complete saponification of the fat charge.
  • a washing operation consists of closing the soap by adding water and boiling vigorously, usually with open steam, and then adding salt and/or caustic to grain the soap and permit settling agains into an aqueous lower layer and an upper grained soap layer. Where caustic is used in the washing operation, it is sometimes called a strengthening change and the lye settled is not fully spent and may be used as the caustic solution in the killing stage of another batch of fatty material.
  • the washing operation also removes further amounts of impurities that may have been present in the original charge.
  • the fitting or pitching stage has for its objective the separation of a neat soap phase from a nigre phase and it is effected by again closing the soap by the addition of water and boiling.
  • the water addition is carefully done so as to reach a final stage where the electrolyte content of the mixture is sufficient to dissolve part of the soap but not all of it.
  • the dissolved soap sinks to the bottom and forms the nigre while the undissolved soap rises to the top as neat soap.
  • the neat soap may then be pumped from the kettle for further processing.
  • a typical composition of the withdrawn neat soap is approximately'63 percent total fatty acids, with a maximum of about 0.14 percent caustic calculated as Na O and a maximum of about 0.6 percent sodium chloride, with water at about the 30-32 percent level.
  • the water content is typically reduced to approximately 10 percent during further processing.
  • Soap of similar composition may be obtained by other soap making processes, such as the continuous and neutralization process referred to above. These processes are also well known to workers of ordinary skill in this art and need not be further described.
  • the new combination bars comprise a major portion of soap and a minor portion of synthetic detergent by weight.
  • a combination of up to about 30 percent by weight synthetic detergent and not less than about percent by weight soap is preferred.
  • minor amounts of materials such as pigments, perfumes, sequestrants, etc., that are commonly employed in toilet soap bars may also be included in the new combination bars.
  • Combination bars formulated with these materials and within these limits provide excellent lime soap dispersing characteristics without adversely affecting the lathering performance and feel of the final bar.
  • Suitable combination bars in accordance with the invention can be prepared as follows (all percentages are by weight):
  • sperm oil monoethanolamide sulphosuccinate containing about 40 percent of active ingredient is mixed with a soap base containing about 63 percent total fatty acids and 32 percent moisture, in the following proportions.
  • the soap base also includes small amounts of preservatives and sequestrants in accordance with principles well known in the art.
  • Example number 1 2 3 4 5 Soap base Sperm oil Monoethanolamide sulphosuccinate (40%) The soap base-synthetic detergent mixtures are then dried to about a percent moisture content. The dried mixtures have the following approximate compositions:
  • the dried, soap base-synthetic detergent mixtures are then process by conventional soap making techniques into bar form.
  • a small amount of titanium dioxide, about 0.2 percent, and perfumes and colorants may also be added during the processing of the soap base-synthetic detergent mass into bars.
  • the soap base-synthetic detergent combination bars of the foregoing Examples l-5 exhibit lathering characteristics, soil removal properties, mildness and tackiness, not significantly different from similar soap bars formulated without the sperm oil monoethanolamide additive.
  • the new combination bars exhibit a very marked reduction in the amount of lime soap curd formed when the bar is used in calcium and magnesium hard water.
  • Variation of the amount of synthetic detergent in the new bar from nil to about 30 percent results in progressively greater lime soap dispersing properties without any significant effect on the lather, soil removing, mildness and other desirable characteristics of the soap portion of the bar.
  • An improved detergent bar consisting essentially of:
  • H COOR MHCOR wherein m is chosen from the group consisting of sodium, potassium hydrogen, ammonium and ethanolamine, R is chosen from the group consisting of hydrogen and C to C saturated and unsaturated fatty chains, R is chosen from the group consisting of C to C aliphatic hydrocarbon chains, and R is chosen from the group consisting of C to C saturated and unsaturated fatty chains, said lime soap is dispersing agent being present in an amount ranging from a finite quantity sufficient to impart lime soap dispersing properties to the detergent bar composition up to about 30 percent by weight of said bar.
  • the improved detergent bar of claim 1 wherein the water soluble soap is a sodium soap of fatty acids derived from a mixture containing 50 to percent tallow and 30 to 50 percent coconut or palm kernel oil.
  • the improved detergent bar claim 1 having a water content of 10 percent by weight of the bar.

Landscapes

  • 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)
US00285318A 1971-08-24 1972-08-31 Soap bars Expired - Lifetime US3793215A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB3966071A GB1402265A (en) 1971-08-24 1971-08-24 Soap-synthetic detergent combination bars
US28531872A 1972-08-31 1972-08-31

Publications (1)

Publication Number Publication Date
US3793215A true US3793215A (en) 1974-02-19

Family

ID=26264197

Family Applications (1)

Application Number Title Priority Date Filing Date
US00285318A Expired - Lifetime US3793215A (en) 1971-08-24 1972-08-31 Soap bars

Country Status (8)

Country Link
US (1) US3793215A (enExample)
AU (1) AU461568B2 (enExample)
CA (1) CA983340A (enExample)
DE (1) DE2241151A1 (enExample)
FR (1) FR2150391B1 (enExample)
GB (1) GB1402265A (enExample)
NL (1) NL7211522A (enExample)
SE (1) SE387129B (enExample)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2438033A1 (fr) * 1974-08-14 1980-04-30 Witco Chemical Corp Ester sulfosucciniques et procede de leur preparation
US4335025A (en) * 1980-02-19 1982-06-15 Witco Chemical Corporation Process for the preparation of synthetic detergent bars, and products produced thereby
US4878150A (en) * 1987-02-20 1989-10-31 Colgate-Palmolive Co. Polarizable material having a liquid crystal microstructure and electrical components produced therefrom
US5038249A (en) * 1987-02-20 1991-08-06 Colgate-Palmolive Co. Nonisotropic solution polarizable material and electrical components produced therefrom
EP0441652A1 (en) * 1990-02-09 1991-08-14 Unilever Plc Detergent composition
US5206797A (en) * 1987-02-20 1993-04-27 Colgate-Palmolive Company Nonisotropic solution polarizable material and electrical components produced therefrom
US5372751A (en) * 1990-02-09 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Acyl isethionate skin cleaning compositions containing betaines, amido sulfosuccinates or combinations of the two
US5435933A (en) * 1993-08-25 1995-07-25 Colgate-Palmolive Company Composition of synthetic detergents
US5543072A (en) * 1992-10-05 1996-08-06 Mona Industries, Inc. Synthetic detergent bars and method of making the same
US20170340525A1 (en) * 2014-12-04 2017-11-30 Colgate-Palmolive Company Method of Reclaiming Formula Components of Antiperspirant Compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19544422A1 (de) * 1995-11-29 1997-06-05 Hoechst Ag Sulfonsuccinate von Polyhydroxyamiden

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976209A (en) * 1956-08-27 1961-03-21 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
US3076766A (en) * 1959-08-12 1963-02-05 Colgate Palmolive Co Detergent bar
US3247121A (en) * 1962-04-30 1966-04-19 Procter & Gamble Washing composition
GB1077470A (en) * 1965-01-13 1967-07-26 Rewo Chem Fab G M B H Novel salts of sulphosuccinic acid half-esters
US3640882A (en) * 1969-05-01 1972-02-08 Continental Oil Co Sulfosuccinate half ester lime soap dispersing agents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2976209A (en) * 1956-08-27 1961-03-21 Witco Chemical Corp Dispersant compositions and toxicant concentrates containing the same
US3076766A (en) * 1959-08-12 1963-02-05 Colgate Palmolive Co Detergent bar
US3247121A (en) * 1962-04-30 1966-04-19 Procter & Gamble Washing composition
GB1077470A (en) * 1965-01-13 1967-07-26 Rewo Chem Fab G M B H Novel salts of sulphosuccinic acid half-esters
US3640882A (en) * 1969-05-01 1972-02-08 Continental Oil Co Sulfosuccinate half ester lime soap dispersing agents

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2453146A1 (fr) * 1974-08-14 1980-10-31 Witco Chemical Corp Esters sulfosucciniques et leur procede de preparation
FR2438033A1 (fr) * 1974-08-14 1980-04-30 Witco Chemical Corp Ester sulfosucciniques et procede de leur preparation
US4335025A (en) * 1980-02-19 1982-06-15 Witco Chemical Corporation Process for the preparation of synthetic detergent bars, and products produced thereby
US5206797A (en) * 1987-02-20 1993-04-27 Colgate-Palmolive Company Nonisotropic solution polarizable material and electrical components produced therefrom
US4878150A (en) * 1987-02-20 1989-10-31 Colgate-Palmolive Co. Polarizable material having a liquid crystal microstructure and electrical components produced therefrom
US4974118A (en) * 1987-02-20 1990-11-27 Colgate-Palmolive Company Nonisotropic solution polarizable material and electrical components produced therefrom
US5038249A (en) * 1987-02-20 1991-08-06 Colgate-Palmolive Co. Nonisotropic solution polarizable material and electrical components produced therefrom
EP0441652A1 (en) * 1990-02-09 1991-08-14 Unilever Plc Detergent composition
US5372751A (en) * 1990-02-09 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Acyl isethionate skin cleaning compositions containing betaines, amido sulfosuccinates or combinations of the two
US5543072A (en) * 1992-10-05 1996-08-06 Mona Industries, Inc. Synthetic detergent bars and method of making the same
US5435933A (en) * 1993-08-25 1995-07-25 Colgate-Palmolive Company Composition of synthetic detergents
US20170340525A1 (en) * 2014-12-04 2017-11-30 Colgate-Palmolive Company Method of Reclaiming Formula Components of Antiperspirant Compositions
US10987285B2 (en) * 2014-12-04 2021-04-27 Colgate-Palmolive Company Method of reclaiming formula components of antiperspirant compositions

Also Published As

Publication number Publication date
AU461568B2 (en) 1975-05-29
DE2241151A1 (de) 1973-03-01
FR2150391A1 (enExample) 1973-04-06
NL7211522A (enExample) 1973-02-27
GB1402265A (en) 1975-08-06
CA983340A (en) 1976-02-10
FR2150391B1 (enExample) 1977-03-04
SE387129B (sv) 1976-08-30
AU4504272A (en) 1974-01-31

Similar Documents

Publication Publication Date Title
AU605750B2 (en) Toilet soap composition
US3376229A (en) Synthetic detergent bar
CA1332907C (en) Toilet compositions
US4180470A (en) Method for improved acyl isethionate detergent bars
US4704224A (en) Soap bar composition containing guar gum
US2781321A (en) All purpose detergent bar
EP0548204A1 (en) BAR SOAP COMPOSITIONS CONTAINING SUCROSE.
DE2161768A1 (de) Gerüststoffmischungen
US3793215A (en) Soap bars
DE2355983A1 (de) Granulierte spruehgetrocknete waschund reinigungsmittel
US3344174A (en) Vicinal acylamido sulfonate compounds
CH626396A5 (enExample)
US2867586A (en) Synthetic detergent bar compositions
US5013486A (en) Detergent bar with improved stain removing and antibacterial properties
US3694367A (en) Superfatted soap
US3926829A (en) Superfatted soap and process of producing it
AU665032B2 (en) Toilet soap bars
US2175285A (en) Detergent for toilet use containing incompletely esterified polyhydric alcohol
EP0707631A1 (en) IMPROVEMENTS OF SOAP PIECES
US3291744A (en) Detergent bar
US2527077A (en) Detergent composition
US2527075A (en) Detergent composition
EP0266124A2 (en) process for making a toilet bar
US5021183A (en) Soap composition
US20060089286A1 (en) Detergent composition