US3759834A - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
US3759834A
US3759834A US00149796A US3759834DA US3759834A US 3759834 A US3759834 A US 3759834A US 00149796 A US00149796 A US 00149796A US 3759834D A US3759834D A US 3759834DA US 3759834 A US3759834 A US 3759834A
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Prior art keywords
sodium
flake
detergent
alpha
weight
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Expired - Lifetime
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US00149796A
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English (en)
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J Parke
R Wilde
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Lever Brothers Co
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Lever Brothers Co
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    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols

Definitions

  • a translucent, non-brittle detergent flake having improved properties contains from 70 to 95 percent by weight of an alkali-metal C -C preferably C to C alpha-olefin sulphonate and from 5 to 11 percent by weight of water.
  • the flake can optionally contain minor amounts of other non-soap detergent active agents, soaps, and detergency builders, particularly trisodium nitrilotriacetate.
  • This invention relates to detergent flakes containing a major amount of non-soap detergent active agents.
  • Soap flakes are very well known and are reasonably easy to manufacture, but satisfactory detergent flakes are diflicult to make. Even when a detergent flake can be milled sufliciently thinly, the flakes so obtained tend to be opaque and brittle and have unsatisfactory lathering properties. These problems are particularly acute if the detergent flake contains a detergency builder such as sodium tripolyphosphate.
  • Soap flakes and detergent flakes can vary in size, but to be satisfactory in use they must be less than 0.02 cm. thick, preferably less than 0.01 cm. thick, and although they can be up to 1 cm. square, they are normally about 0.4 cm. square.
  • alpha-olefin sulphonate is herein understood to mean the mixture of anionic detergent active agents obtained when the products of the sulphonation of ice alpha-olefins are neutralised and hydrolysed completely or almost completely.
  • a detergent flake according to the invention consists essentially of:
  • an inorganic detergency builder selected from the group consisting of sodium silicate, sodium metasilicate, sodium tripolyphosphate, sodium pyrophosphate, trisodium orthophosphatfe', sodium hexametaphosphate, sodium carbonate and sodium bicarbonate;
  • an organic detergency builder selected from the group consisting of sodium nitrilotriacetate, sodium ethylene diamine tetraacetate, and polyelectrolytes and their partial or total alkali-metal salts;
  • non-soap detergent active agent other than an olefin sulphonate, selected from the group consisting of anionic, nonionic, cationic and zwitterionic detergent active agents.
  • the alpha-olefin sulphonates suitable for use in flakes according to the invention are derived from the sulphonation of C -C alpha-olefins.
  • the olefins should contain between 12 and 20 carbon atoms, 'and particularly preferably from 14 to 16 carbon atoms.
  • the olefin should preferably consist almost entirely of mono-uns-atunated straight-chain alpha-olefins.
  • alpha-olefins are generally derived from the cracked-wax process, in which the olefins are extracted from a cracked par-aifin distillate, or by the Ziegler process, in which the olefins are synthesized by polymerisation of a low molecular weight unsaturated hydrocarbon, such as ethylene, with the aid of a Ziegler or similar catalyst.
  • olefins may be prepared by the dehydration of primary alcohols formed, for example, by hyldrogenating esters of naturally-occurring fatty acids such as those derived by the saponification of animal and vegetable oils and fats, or olefins may be prepared by the dehydrogenation of paraflins, although this latter process is not preferred.
  • olefin sulphonates derived from Ziegler olefins should be used for the purposes of this invention, as Ziegler olefins usually comprise about 90% by weight of alphaolefins and contain only an insignificant amount of branched-chain material.
  • cracked-wax olefins are also suitable, as these generally contain between and by weight of alpha-olefins together with minor amounts of internal olefins and diolefins.
  • the olefins used to prepare the olefin sulphonates for use in the invention should contain as high a proportion of linear alpha-olefins as possible, and if supplies of alpha-olefin were available at present, these would be ideal. However, present technology is unable to produce such material.
  • alpha-olefin sulphonate is used to describe the mixtures of olefin sulphonates derived from the sulphonation of commercially available supplies of alpha-olefins,
  • Alpha-olefin sulphonates are mixtures of various compounds, including various hydroxyalkane sulphonates as well as disulphonates and a major proportion of alkene sulphonate.
  • the proportion of Z-hydroxylalkane sulphonate in the mixture should be kept as low as possible,
  • alpha-olefin sulphonate will be derived, as explained above, from alpha-olefins, it will be appreciated that when alpha-olefins are allowed to stand in the presence of acidic products, as they will do in batch sulphonation processes, some isomerisation will occur and olefins in which the double bond is not terminal will be formed. It will be appreciated that products containing minor proportions of olefin sulphonates derived from non-terminal double bond olefins are still Within the scope of this invention.
  • the olefin can be sulphonated in many different ways, such as in stirred-tank reactors or in falling-film reactors.
  • the preferred sulphonating agent is a sulphur trioxide/ air mixture, although other agents, such as oleum, can be used.
  • the alpha-olefin sulphonate is preferably a sodium salt, although potassium and lithium salts can be used if desired.
  • a flake according to the invention can, if desired, contain up to 25% by weight of one or more additional ingredients.
  • these additional ingredients should not comprise more than about by weight of the flake, and particularly preferably they should constitute not more than about 5% by weight of the flake.
  • These additional ingredients can be, for instance, soaps, non-soap detergent active agents other than alpha-olefin sulphonates, detergency builders, perfumes, colourants, enzymes, germicides, fluorescers and antiredeposition agents.
  • the soaps that can be incorporated into a detergent flake according to the invention can be any of the watersoluble soaps commonly employed in the detergent composition art.
  • Such soaps are alkali-metal salts of longchain fatty acids, the fatty acids being derived either from the saponification of natural fats or oils, or by synthetic means.
  • the sodium salts of such acids are generally preferred, although potassium and lithium salts can be used if desired.
  • the alkyl chain length of the fatty acids will generally be in the range of from 8 to 22 carbon atoms. Examples of natural fats and oils from which such fatty acids can be derived are tallows, coconut oil, palm kernel oil, groundnut oil, tall oil and palm oil.
  • Soaps derived from such natural sources are made up of complex mixtures of fatty acids of differing chain lengths. Examples of these acids are lauric, myristic, oleic, palmitic, capric, caprylic and stearic acids. Synthetic fatty acids will also generally comprise mixtures of these and other fatty acids. Soaps derived from one single fatty acid could be used if desired, but for economic reasons it will generally be preferable to use one of the more readily obtainable natural or synthetic mixtures. The use of distilled fatty acids, whether natural or synthetic, is particularly preferred.
  • a detergent flake according to the invention can comprise up to 25 by weight of non-soap detergent active agents in addition to the essential olefin sulphonate.
  • Such other detergent active agents can be any of the anionic, nonionic, cationic and zwitterionic detergent active agents commonly employed in the detergent composition art. Examples of these are:
  • Anionic detergent active agents alkali-metal salts of organic sulphuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulphonic acid and sulphuric acid ester radicals (included in the term alkyl is the alkyl portion of higher acyl radicals) such as sodium or potassium alkyl sulphates, preferably those obtained by sulphating the higher alcohols (Cy-C13 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene-sulphonates in which the alkyl group contains from about 9 to about 20 carbon atoms and in which the alkyl group is attached to the benzene ringe in either the 1 position or at the secondary positions, such as in sodium linear alkyl (C C secondary benzene sulphonate, 2-phenyl-dodecanesulphon
  • tallow or coconut oil alcohols and about 1 to 6 moles of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 18 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl taurine in which the fatty acids, for example, are derived from coconut; and others known in the art.
  • Nonionic synthetic detergent active agents compounds formed by condensing ethylene oxide with an hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the polyethylene oxide condensates of alkyl-phenols, e.g.
  • alkyl-phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal of 5 to 25 moles of ethylene oxide per mole of alkylphenols (the alkyl substituent in such compounds may be derived from polymerised propylene, diisobutylene, octene, dodecene, or nonene, for example); those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, such as compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said hydrophobic base having a molecular weight of the order of 2,500 to 3,000; the condensation product of aliphatic alcohols having from 8
  • R R R N O long chain tertiary amine oxides corresponding to the following general formula, R R R N O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms and R and R are each methyl, ethyl or hydroxy ethyl radicals, such as dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide and dimethylhexadecylamine oxide, N-bis(hydroxyethyl)dodecylamine oxide; long chain tertiary phosphine oxides corresponding to the following formula RR'RP 0 wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R' and R are each alkyl
  • Ampholytic synthetic detergent active agents which are derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, such as sodium- 3 dodecylaminopropionate, sodium-3-dodecylaminopropanesulphonate and sodium N-2-hydroxydodecyl-N-methyl-taurate.
  • Zwitterionic synthetic detergent active agents namely derivatives of aliphatic quaternary ammonium compounds, sulphonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, such as 3 (N,N-dimethyl-N-hexadecylammonio) propane-l-sulphonate, 3 (N,N dimethyl-N-hexadecylammonia)-2-hydroxypropane-l-sulphonate, 3-(dodecylmethylsulphonium) propane sulphonate, and 3 cetylmethylphosphonium) ethane sulphonate.
  • anionic water solubilizing group such as 3 (N,N-dimethyl-N-hexadecylammonio) propane-l-sulphonate, 3 (N,N dimethyl-N-he
  • non-soap detergent active agents commonly used in the art are given in Surface Active Agents, volume 1, by Schwartz and Perry (Interscience 1949) and Surface Active Agents, volume 2, by Schwartz, Perry and Berch (Interscience 1958).
  • a detergent flake according to the invention can contain one or more detergency builders if this is desired.
  • Such detergency builders can be either inorganic or organic in nature.
  • inorganic detergency builders examples include sodium silicate, sodium metasilicate, sodium carbonate, sodium bicarbonate, sodium tripolyphosphate, trisodium orthophosphate, sodium pyrophosphate and sodium hexametaphosphate.
  • organic detergency builders that can be used are sodium and potassium nitrilotriacetate, sodium and potassium ethylene diamine tetraacetate and polyelectrolytes, i.e. polycarboxylic acids derived from the polymerization of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid and the anhydrides of these acids, and also from the copolymerisation of the above acids and anhydrides with minor amounts of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene.
  • polycarboxylic acids derived from the polymerization of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, such as maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid and the anhydrides
  • Each of the above acids and anhydrides can also be made to copolymerise with a minor amount of one of the other acids and anhydrides named above.
  • These polyelectrolyte detergency builders are generally incorporated in detergent compositions as their alkali-metal salts. Their sodium salts are preferred, although their potassium salts can also be used.
  • a particularly preferred aspect of the invention is a detergent flake containing up to 25%, preferably about 15%, by weight of trisodium nitrilotriacetate.
  • a flake in accordance with the invention can contain up up 25% of organic, relatively non-crystalline components in addition to the alpha-olefin sulphonate, but a flake can contain no more than about 15% of inorganic crystalline components.
  • inorganic detergency builders such as those named above, then an upper limit of about 15% by weight is imposed on the amount of inorganic builder that can be incorporated into the flake.
  • the detergent flakes according to the invention have been found to have outstanding physical properties and excellent lathering and detergency properties.
  • the good lathering properties of these flakes is particularly noticeable when they are compared with conventional soap flakes, especially if the flakes are used in hard water at low concentrations.
  • Exceptionally good lathering properties are obtained from flakes containing a C -C alpha-ole fin sulphonate. Wash liquor containing detergent flakes of the invention is also found to be exceedingly mild.
  • EXAMPLE I 100 g. batches of drum-dried sodium alpha-olefin sulphonate (C -C were mixed with different weights of water and then were milled into diamond flakes on a bench-scale mill with rolls 20 cm. long and 7.5 cm. diameter. Observations were made on the relative ease with which the mix could be flaked and on the physical characteristics (stickiness, appearance) of the flakes.
  • compositions 1 to 7 are Wellformed, are relatively non-brittle and have a satisfactory degree of surface-lustre. These compositions could be milled to a thickness of 0.005 to 0.0075 cms.
  • compositions 8 to 19 can only be milled to a thickness of 0.0125 to 0.015 cms. and are brittle and have a poor appearance and lustre.
  • compositions 20 and 21 which contain sodium nitrilotriacetate instead of sodium tripolyphosphate, can be milled to a thickness of 0.005 to 0.0075 cms.
  • the soap flake had the following formulation:
  • the non-soap detergent powder had the following formulation:
  • a isual assessment is made of the lather generated in a reciprocating paddle machine after times of:
  • EXAMPLE VI The compositions 1 to 16, 20 and 21, from Table IV were compared with the soap flake and the non-soap detergent powder given in Example IV for lather and cleansing in a paddle washing machine. Seven pound loads of normally-soiled articles including standard test cloths were washed for 10 minutes in 24 H. water at 40 C. 7
  • a etergent flake consisting essentially of:
  • alkali-metal C -C substantially linear alpha-olefin sulphonate said alkali-metal being selected from the group consisting of sodium, potassium and lithium;
  • soap from 0 to 25 percent by weight of soap selected from the group consisting of sodium, potassium and lithium soaps;
  • an inorganic detergency builder selected from the group consist ing of sodium silicate, sodium metasilicate, sodium carbonate, sodium bicarbonate, sodium tripolyphosphate, trisodium orthophosphate, sodium pyrophosphate and sodium metaphosphate;
  • an organic detergency builder selected from the group consisting of sodium nitrilotriacetate, potassium nitrilotriacctate, sodium ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, and sodium and potassium salts of polycarboxylic acids derived from the polymerisation of unsaturated polycarboxylic acids and unsaturated polycarboxylic acid anhydrides selected from the group consisting of maleic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid and the anhydrides of these acids, and from the copolymerisation of said unsaturated polycarboxylic acids and unsaturated polycarboxylic acid anhydrides with monomers selected from the group consisting of vinyl acetate, vinyl chloride, methyl methacrylate, methyl acrylate and styrene; and
  • a detergent active agent other than an alpha-olefin sulphonate, selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic detergent active agents.

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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)
US00149796A 1967-02-17 1971-06-03 Detergent composition Expired - Lifetime US3759834A (en)

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GB7712/67A GB1216474A (en) 1967-02-17 1967-02-17 Detergent composition

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US (1) US3759834A (en)van)
AT (1) AT286474B (en)van)
BE (1) BE710920A (en)van)
CH (1) CH499616A (en)van)
DE (1) DE1692028B2 (en)van)
DK (2) DK127072B (en)van)
ES (1) ES350533A1 (en)van)
FI (1) FI48360C (en)van)
FR (1) FR1554427A (en)van)
GB (1) GB1216474A (en)van)
LU (1) LU55495A1 (en)van)
NL (1) NL6802211A (en)van)
SE (1) SE348489B (en)van)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003857A (en) * 1973-12-17 1977-01-18 Ethyl Corporation Concentrated aqueous olefins sulfonates containing carboxylic acid salt anti-gelling agents
US4111853A (en) * 1976-03-08 1978-09-05 Stepan Chemical Company Particulate composition of sodium alpha olefin sulfonate and sodium silicate
US5929011A (en) * 1996-10-30 1999-07-27 Sunburst Chemicals, Inc. Solid cast chlorinated cleaning composition
US6395703B2 (en) 1995-05-17 2002-05-28 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
US6475969B2 (en) 2000-03-16 2002-11-05 Sunburst Chemicals, Inc. Solid cast chlorinated composition
US6777383B1 (en) 1995-05-17 2004-08-17 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2243778T3 (en) * 2008-01-30 2014-11-17 Nippon Zoki Pharmaceutical Co piperidine

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003857A (en) * 1973-12-17 1977-01-18 Ethyl Corporation Concentrated aqueous olefins sulfonates containing carboxylic acid salt anti-gelling agents
US4111853A (en) * 1976-03-08 1978-09-05 Stepan Chemical Company Particulate composition of sodium alpha olefin sulfonate and sodium silicate
US6395703B2 (en) 1995-05-17 2002-05-28 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
US6395702B2 (en) 1995-05-17 2002-05-28 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
US6777383B1 (en) 1995-05-17 2004-08-17 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
US5929011A (en) * 1996-10-30 1999-07-27 Sunburst Chemicals, Inc. Solid cast chlorinated cleaning composition
US6475969B2 (en) 2000-03-16 2002-11-05 Sunburst Chemicals, Inc. Solid cast chlorinated composition

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Publication number Publication date
BE710920A (en)van) 1968-08-16
NL6802211A (en)van) 1968-08-19
CH499616A (de) 1970-11-30
FR1554427A (en)van) 1969-01-17
DE1692028A1 (de) 1971-07-22
SE348489B (en)van) 1972-09-04
FI48360C (fi) 1974-09-10
DE1692028B2 (de) 1976-03-04
DK127072B (da) 1973-09-17
AT286474B (de) 1970-12-10
DK127072A (en)van)
FI48360B (en)van) 1974-05-31
ES350533A1 (es) 1969-11-01
GB1216474A (en) 1970-12-23
LU55495A1 (en)van) 1968-10-14

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