JPH0440399B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to surfactants which provide good detergency and optionally good fluorescent brightener effectiveness and/or antifoam and/or corrosion inhibition in connection with laundry. Regarding the combination of Compositions of this type can be built or unbuilt, particulate or liquid, and can contain the usual auxiliary ingredients customary for compositions of this type. Description of the prior art Alkyl polyglycosides, which are surfactants, are
Disclosed in US Pat. No. 3,598,865, US Pat. No. 3,721,633 and US Pat. No. 3,772,269. These patents also disclose methods of making alkyl polyglycoside surfactants and built liquid detergent compositions containing these surfactants. US Pat. No. 3,219,656 discloses alkyl monoglucozides and suggests utility as foam stabilizers for other surfactants. The structures of various polyglycoside surfactants and their production methods are described in U.S. Pat.
It was started in specification No. 4011389 and specification No. 4223129. SUMMARY OF THE INVENTION The present invention relates to the discovery of certain combinations of surfactants that give very good cleaning power on a variety of fabrics, especially in cold water. Generally speaking, the present invention relates to (1) a compound of the formula RO(R ¹ O)y(Z)x [wherein R is alkyl, hydroxyalkyl,
alkylphenyl, hydroxyalkylphenyl, alkylbenzyl or mixtures thereof, wherein the alkyl group has from about 8 to about 18 carbon atoms; each R ¹ is ethylene, propylene or -
_CH2 -CH(OH) _-CH2- group, and y
is from 0 to about 12; and each Z is a moiety derived from a reducing sugar having 5 or 6 carbon atoms;
and x is a number from about 1 1/2 to about 10]
from about 1% to about 90% detergent surfactant, (2) from about 1% to about 90% nonionic detergent surfactant, and (3) from 0% to about 90% detergent builder ((1) vs. (2) The ratio is about 1:10 to about 10:1, preferably about 3:1.
(approximately 1:3). In particular, in the present invention, about 1 to 7% of an amine oxide detergent surfactant is selected as the nonionic detergent surfactant used in combination with the alkyl polysaccharide detergent surfactant, and an unsaturated soap having a carbon number of about 16 to about 22 is selected. Detergent compositions are provided that contain from about 1% to about 15% water-soluble fatty acid soap containing at least about 40% to provide suds control and corrosion control. DESCRIPTION OF PREFERRED EMBODIMENTS Alkyl Polysaccharide Surfactants It has surprisingly been found that co-surfactants interact with the alkyl polysaccharide surfactants of the present invention to provide good laundering detergency on a wide range of fabrics. It is. Alkyl polysaccharides have carbon numbers of about 6 to about
30, preferably about 1 1/2 to about 10, preferably about 1 hydrophobic group and sugar unit having from about 10 to about 16 carbon atoms
Polysaccharides, such as polyglycosides, having a hydrophilic group of 1/2 to about 3, most preferably about 1.6 to about 2.7. Any reducing sugar having 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl moieties can be used in place of the glucosyl moiety (if the hydrophobic group is attached at the 2-, 3-, 4-, etc.-position). and thus give glucose or galactose as opposed to glucosides or galactosides). Intersugar linkages can be, for example, between one position of the additional sugar unit and the 2nd, 3rd, 4th and/or 6th position on the previous sugar unit. In some cases, and less preferably,
There can be polyalkoxide chains attached to the hydrophobic and polysaccharide moieties. A preferred alkoxide is ethylene oxide. Typical hydrophobic groups are, for example, saturated or unsaturated branched or unbranched alkyl groups having from about 8 to about 18 carbon atoms, preferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxyl groups and/or
The polyalkoxide chain can contain up to about 10 alkoxide moieties, preferably less than 5, and most preferably 0. Suitable alkyl polysaccharides include octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl,
tri-, tetra-, penta-, and hexa-glucosides, galactosides, lactosides, glucose, fructosides, fructose, and/or galactose. Suitable mixtures are, for example, coconut alkyl di-, tri-, tetra-, and penta-glucosides and tallow alkyl tetra-, penta-, and hexa-glucosides. Preferred alkyl polyglycosides have the formula ^R2O ( _CnH2nO )t(glycosyl)x, where ^R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof. (the alkyl group has about 10 to about 18 carbon atoms, preferably about 12 to about 14 carbon atoms); n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0
and x is from 1 1/2 to about 10, preferably from about 1 1/2 to about 3, and most preferably from about 1.6 to about 2.7. Glycosyl is preferably derived from glucose. To produce the compound, the alcohol or alkyl polyethoxy alcohol is first produced and then reacted with glucose or a source of glucose to produce the glucoside (bonded at the 1-position). Additional glycosyl units are attached between their 1-position and the 2-, 3-, 4- and/or 6-position, preferably primarily the 2-position, of the previous glycosyl unit. Preferably the content of alkyl monoglycosides is low, preferably less than about 60%, more preferably less than about 50%. Surprisingly, anionic fluorescent brighteners are usually relatively ineffective even in large amounts in the presence of conventional ethoxylated nonionic detergent surfactants and in the absence of substantial amounts of anionic detergent surfactants. , are very effective when alkyl polyglycoside surfactants are present. For brightener effectiveness, the ratio of alkyl polyglycoside detergent surfactant to nonionic detergent surfactant should be greater than about 1:4, preferably greater than about 1:3; Most preferably greater than about 1:1. Nonionic detergent surfactants Nonionic surfactants Nonionic surfactants, e.g.
Those with HLB are well known in the cleaning art. Nonionic surfactants are incorporated into the compositions of the invention, for example, together with the alkyl polyglycoside surfactants described above. Nonionic surfactants can be used alone or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants described below to prepare nonionic surfactant mixtures useful in combination with alkyl polyglycosides. An example of this type of surfactant is U.S. Pat.
No. 3,717,630 and US Pat. No. 3,332,880. Non-limiting examples of suitable nonionic surfactants that can be used in the present invention are as follows. (1) Polyethylene oxide condensates of alkylphenols These compounds are, for example, condensates of alkylphenols having an alkyl group having about 6 to 12 carbon atoms in either a straight or branched configuration with ethylene oxide. (The ethylene oxide is 5% per mole of alkylphenol)
present in an amount equal to ~25 mol). Alkyl substituents in compounds of this type may be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type are nonylphenol condensed with about 9.5 moles of ethylene oxide per mole of nonylphenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; and dodecylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. and diisooctylphenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include, for example, Igepal CO-630, marketed by GAF Corporation, and Loam End.
Triton X-45, X-114, X-100 marketed by Haas Company
and X-102. (2) Aliphatic alcohol and ethylene oxide approximately 1~
Condensate with about 25 moles The alkyl chain of the aliphatic alcohol is either straight or branched, primary or secondary, and generally has from about 8 to about 22 carbon atoms.
Examples of ethoxylated alcohols of this type are the condensation of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation of myristyl alcohol with about 9 moles of ethylene oxide and coconut alcohol (a fatty alcohol with an alkyl chain length of 10 to 14 carbon atoms). It is a condensate with a mixture of Examples of commercially available nonionic surfactants of this type are Tergitol 15-S-9, marketed by Union Carbide Corporation;
Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, marketed by The Procter & Gambling Company; (Kyro)
It is EOB. (3) A condensate of ethylene oxide and a hydrophobic base produced by the condensation of propylene oxide and propylene glycol The hydrophobic portion of these compounds is approximately 1500 to 1800
It has a molecular weight of , and is water-insoluble. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid properties of the product are such that the polyoxyethylene content is approximately 50% of the total weight of the condensate. point (corresponding to condensation with up to about 40 mol of ethylene oxide). An example of this type of compound is certain commercially available Pluronic surfactants marketed by Wyndt Chemical Corporation. (4) Condensates of ethylene oxide and the product formed from the reaction of propylene oxide and ethylene diamine The hydrophobic portion of these products consists of the reaction product of ethylene diamine and excess propylene oxide, and contains about 2,500 to about 3,000 It has a molecular weight.
This hydrophobic portion contains about 40% to about 80% by weight polyoxyethylene and about 5000% to about 500% polyoxyethylene.
It is condensed with ethylene oxide to the extent that it has a molecular weight of 11,000. An example of this type of nonionic surfactant is certain commercially available Tetronic compounds marketed by Wyndt Chemical Corporation. (5) Semipolar nonionic detergent surfactants include, for example, one alkyl moiety having about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to about 3 carbon atoms. Water-soluble amine oxide containing approximately 10 carbon atoms
1 ~18 alkyl moiety and about 1 to 3 carbon atoms
a water-soluble phosphine oxide containing two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having a carbon number of about
1 alkyl moiety of 10-18 and about 1 to carbon number
3, a water-soluble sulfoxide containing one moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties. Preferred semipolar nonionic detergent surfactants have the formula (In the formula, R ³ is an alkyl group, hydroxyalkyl group, or alkylphenyl group having about 8 to about 22 carbon atoms, or a mixture thereof, and R ⁴ is an alkylene group or hydroxyalkylene group having 2 to 3 carbon atoms. group or a mixture thereof, x
is 0 to about 3, and each R ⁵ is an alkyl or hydroxyalkyl group having 1 to about 3 carbon atoms or a polyethylene oxide group containing 1 to about 3 ethylene oxide groups, and
The R ⁵ groups can be bonded to each other to form a ring structure, for example through an oxygen or nitrogen atom). Preferred amine oxide detergent surfactants are C _10-18 alkyl dimethyl amine oxides,
_C8-18 alkyldihydroxyethylamine oxide, and _C8-12 alkoxyethyldihydroxyethylamine oxide. Nonionic detergent surfactants (1) to (4) are conventional ethoxylated nonionic detergent surfactants. Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the invention are biodegradable and have the formula ^R8 ( _OC2H4 )nOH, where ^R8 has from ₈ to about 22 carbon atoms; Preferably about 10~
about 20 primary or secondary alkyl chains, and n averages from about 2 to about 12, especially from about 2 to about 9). The nonionic surfactant has an HLB (hydrophilic-lipophilic balance) of about 5 to about 17, preferably about 6 to about 15. HLB is a nonionic surfactant described by M.G.S.C. (Marcel Detzker, Inc., 1966, p. 606).
(page 613). In preferred nonionic surfactants, n is 3-7. Primary linear alcohol ethoxylates (e.g., approximately 20% 2-methyl branched isomer, commercially available from Shell Chemical Company under the trade name Neodol)
(alcohol ethoxylates produced from organic alcohols containing) are preferred from a performance standpoint. Particularly preferred nonionic surfactants for use in the compositions of the invention include, for example, C ₁₀ alcohols and
Condensate with 9 moles of ethylene oxide; Condensate with tallow alcohol and 9 moles of ethylene oxide;
Condensation product of coconut alcohol and 5 mol of ethylene oxide; Condensation product of coconut alcohol and 6 mol of ethylene oxide; Condensation product of C ₁₂ alcohol and 5 mol of ethylene oxide; Condensation product of C _12-13 alcohol and 6.5 mol of ethylene oxide and the same condensate stripped to remove substantially all the lower ethoxylated and non-ethoxylated fractions; a condensate of a C _12-13 alcohol with 2.3 moles of ethylene oxide, substantially all the lower ethoxylated and the same condensate stripped to remove the non-ethoxylated fraction; a condensate of a _C12-13 alcohol with 9 moles of ethylene oxide; a condensate of a _C12-13 alcohol with 9 moles of ethylene oxide;
Condensate with 2.25 mol of ethylene oxide; C _14-15
A condensate of an alcohol with 4 moles of ethylene oxide; a condensate of a _C14-15 alcohol with 7 moles of ethylene oxide; and a condensate of a _C14-15 alcohol with 9 moles of ethylene oxide. The compositions of the present invention can contain mixtures of the preferred alcohol ethoxylate nonionic surfactants and other types of nonionic surfactants. One of the preferred nonionic surfactant mixtures contains at least one of the preferred alcohol ethoxylate nonionic surfactants, and the preferred alcohol ethoxylate surfactant(s) versus the other nonionic surfactant. the ratio(s) of from about 1:1 to about 5:1. Particular examples of surfactant mixtures useful in the present invention are a condensate of a _C14-15 alcohol and 3 moles of ethylene oxide (Neodol 45-3) and a condensate of a _C14-15 alcohol and 9 moles of ethylene oxide. Things (Neodoll 45−
9) a mixture of a lower ethoxylate nonionic surfactant to a higher ethoxylate nonionic surfactant in a ratio of about 1:1 to about 3:1; a condensate of ₁₀ alcohols and 3 moles of ethylene oxide; class
Ratio of lower ethoxylate nonionic surfactant to higher ethoxylate nonionic surfactant with condensate of _C15 alcohol and 9 moles of ethylene oxide (Tarditol 15-S-9) from about 1:1 to about 4 : a mixture of Neodol 45-3 and Tergitol 15-S-9 in a ratio of lower ethoxylate nonionic surfactant to higher ethoxylate nonionic surfactant from about 1:1 to about 3:1; and Neodol 45-3, myristyl alcohol and 10
Ratio of lower ethoxylates to higher ethoxylates with moles of ethylene oxide condensate about 1:1
It is a mixture of approximately 3:1. Preferred nonionic surfactant mixtures can also contain alkyl glyceryl ether compounds along with the preferred alcohol ethoxylate surfactants. formula (wherein ^R9 is an alkyl or alkenyl group having about 8 to about 18 carbon atoms, preferably about 8 to 12 carbon atoms, or an alkaryl group having about 5 to 14 carbons in the alkyl chain, and n is 0 to Particularly preferred are mixtures of glyceryl ethers having an alcohol ethoxylate of about 6) and the above-mentioned preferred alcohol ethoxylates in an alcohol ethoxylate to glyceryl ether ratio of about 1:1 to about 4:1, especially about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in US Pat. No. 4,098,713. The ratio of alkyl polyglycoside detersive surfactant to nonionic detergent surfactant is about 10:1 to about 1:10, preferably about 3:1 to about 1:3. Detergent builder The detergent composition of the present invention also has detergent builder 0
% to about 90%, preferably about 5% to about 50%, more preferably about 10% to about 35%. This type of builder may be used, for example, with the formula Na _z [AlO ₂ ) _z ·(SiO ₂ ) _y ]·xH ₂ O, where z and y are at least about 6, and z
The molar ratio of y to y is about 1.0 to about 0.5, and x is about 10 to about 264. ) is a crystalline aluminosilicate ion exchange material. Amorphous hydrated aluminosilicate materials useful in the present invention have the empirical formula M _z (zAlO ₂ .ySiO ₂ ), where M is sodium, potassium, ammonium, or substituted ammonium, and z is about 0.5 to
2 and y is 1), and the material has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO ₃ hardness per gram of anhydrous aluminosilicate. The aluminosilicate ion exchange builder material is in hydrated form and when crystalline contains about 10
~28% by weight, and in the amorphous form, it contains significantly more water. Highly preferred crystalline aluminosilicate ion exchange materials contain about 18% to about 22% water within their crystalline matrix. Preferred crystalline aluminosilicate ion exchange materials are further characterized by a particle size of about 0.1 microns to about 10 microns. Amorphous materials are often even smaller, for example smaller than about 0.01 microns. More preferred ion exchange materials are about
It has a particle size of 0.2 microns to about 4 microns. As used herein, the term "particle size" refers to the average particle size of a given ion exchange material as determined by conventional analytical techniques, such as microscopic measurements using scanning electron microscopy. The crystalline aluminosilicate ion exchange material has a water hardness of at least about 200 mg of CaCO ₃ per gram of aluminosilicate calculated on an anhydrous basis.
equivalent, generally about 300 mg・eq/g to about 352
It is usually further characterized by a calcium ion exchange capacity which is in the range of mg·eq/g. The aluminosilicate ion exchange material is at least about 2 grains Ca ⁺⁺ /gal/min/g/gal aluminosilicate (anhydrous basis) and generally about 2 grains/gal/min/g/gal on a calcium ion hardness basis.
It is still further characterized by a calcium ion exchange rate that is within the range of g/gal to about 6 grains/gal/min/g/gal. The best aluminosilicates for builders are at least about 4 grains/
Calcium ion exchange rate in gallons/minute/g/gallon is shown. Amorphous aluminosilicate ion exchange materials typically contain at least about 50 mg·eqCaCO ₃ /g (12 mgMg ⁺⁺ /
g Mg ⁺⁺ exchange capacity and a Mg ⁺⁺ exchange rate of at least about 1 grain/gal/min/g/gal. The amorphous material does not exhibit an observable diffraction pattern when examined by Cu irradiation (1.54 Å units). Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available. Aluminosilicates useful in the present invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived. A method for making aluminosilicate ion exchange materials is disclosed in US Pat. No. 3,985,669.
Preferred synthetic crystalline alkinosilicate ion exchange materials useful in the present invention are available under the names Zeolite A, Zeolite P(B), and Zeolite X. In particularly preferred embodiments, the crystalline aluminosilicate ion exchange material has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O, where x is from about 20 to about 30, especially about 27 ). Other examples of detergency builders are water-soluble neutral or alkaline salts. Other useful water-soluble salts are, for example, compounds commonly known as detergent builder substances. Builders generally include various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates,
selected from silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates. Preference is given to the alkali metal salts of said substances, especially the sodium salts. Particular examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, pyrophosphates, polymeric metaphosphates with a degree of polymerization of about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are sodium and potassium salts of ethylene-1,1-diphosphonic acid, sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and ethane-1,
Sodium and potassium salts of 1,2-triphosphonic acid. Other phosphorus builder compounds are described in U.S. Pat.
Specification No. 3422021, Specification No. 3422137, No.
It is disclosed in specification No. 3400176 and specification No. 3400148. Examples of non-phosphorus inorganic builders are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate decahydrate, and molar ratios of _SiO2 to alkali metal oxides of about 0.5 to about 4.0, preferably Approximately 1.0~
It is a silicate with a value of about 2.4. Water-soluble phosphorus-free organic builders useful in the present invention include:
For example, various alkali metals, ammonium and substituted ammonium polyacetates, carboxylates,
Polycarboxylate and polyhydroxysulfonate. Examples of polyacetate and polycarboxylate builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and sodium, potassium, lithium, ammonium, and substituted ammonium salts of citric acid. It's salt. A highly preferred polycarboxylate builder for the present invention is described in US Pat. No. 3,308,067. Substances of this type are, for example, water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Other builders are, for example, the carboxylated hydrocarbons of US Pat. No. 3,723,322. Other builders useful in the present invention are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis
- cyclohexanehexagalboxylate cis-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, water-soluble polyacrylates (e.g. having a molecular weight of about 2000 to about 200000), and maleic anhydride and vinyl methyl It is a copolymer salt with ether or ethylene. Other polycarboxylic acid salts suitable for use in the present invention are the polyacetal carboxylic acid salts described in US Pat. No. 4,144,226 and US Pat. No. 4,246,495. These polyacetal carboxylates can be produced as follows. The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylic ester is then coupled with chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solutions, converted to the corresponding salt, and surfactant Add to. Other detergency builder materials useful in the present invention are the "seed builder" compositions disclosed in Belgian Patent No. 798,856. Specific examples of seed builder mixtures of this type are: a 3:1 wt mixture of sodium carbonate and calcium carbonate with a particle size of 5 microns; a 2.1:1 wt mixture of sodium sesquicarbonate and calcium carbonate with a particle size of 0.5 microns; A 20:1 wt mixture of sodium sesquicarbonate and calcium hydroxide with a particle size of 0.01 microns; and a 3:3:1 wt mixture of sodium carbonate, sodium aluminate and calcium oxide with a particle size of 5 microns. Other Ingredients In addition to the essential detergent surfactants mentioned above, the detergent compositions of the present invention may be comprised of anionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof. from about 1% to about 15%, preferably about 2%, of an organic surfactant selected from the group consisting of:
~8%. Surfactants useful in the present invention are described in US Pat. No. 3,664,961 and US Pat. No. 3,919,678. Also,
Useful cationic surfactants are described, for example, in U.S. Pat.
No. 4,222,905 and US Pat. No. 4,239,659. The following are representative examples of surfactants useful in the present compositions. Water-soluble salts of higher fatty acids, or "soaps", are useful anionic surfactants in the compositions of the present invention. These are alkali metal soaps, such as sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms. Soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, ie, sodium or potassium tallow soaps and coconut soaps. The preferred soaps mentioned above and below, especially in combination with semipolar or amide nonionic detergent surfactants, are at least partially unsaturated. Unsaturated Soaps The unsaturated fatty acid soaps of the present invention preferably have from about 16 to about 22 carbon atoms in a linear configuration. Preferably, the number of carbon atoms in the unsaturated fatty acid soap is about 16 to about 18. Unsaturated soaps, as well as other anionic detergents and other anionic substances within the detergent compositions of the present invention,
It has cations that make the soap water soluble and/or dispersible. Suitable cations are, for example, sodium, potassium, ammonium, monoethanolammonium, diethanolammonium,
These are cations such as triethanolammonium and tetramethylammonium. Sodium ions are preferred, but ammonium and triethanolammonium cations are useful in liquid formulations. Amounts of at least about 1% unsaturated fatty acid soap are desirable to provide significant reductions in sudsing and corrosion. The preferred amount of unsaturated fatty acid soap is about 1
% to about 15%, preferably about 1% to about 10%, most preferably about 2% to about 5%. Unsaturated fatty acid soaps should contain about 15 ppm to about 200 ppm, preferably about 25 ppm, in cleaning solutions at recommended U.S. usage levels.
It is preferably present in an amount that will provide from about 125 ppm to about 125 ppm, and for European usage levels from about 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 500 ppm. Since mono-, di-, and triunsaturated fatty acids are all essentially equivalent, it is preferred to use primarily monounsaturated soaps to minimize the risk of malodor. Suitable sources of unsaturated fatty acids are well known. See, for example, Bailey, Industrial Oil and Fat Products, 3rd edition, Swarn, Interscience Publishers (1964). Preferably the amount of saturated soap is kept as low as possible, preferably less than about 60%, preferably less than about 50% of the total soap is saturated soap. However, small amounts of saturated soap can be used. Tallow soap and palm oil can be used. Useful synthetic anionic surfactants include, for example, water-soluble salts of organic sulfuric acid reaction products having alkyl groups of about 10 to about 20 carbon atoms and sulfonate or sulfate ester groups in their molecular structure, preferably alkali metal salts, ammonium salts and alkylol ammonium salts. This type of synthetic anionic detergent surfactant can be used in amounts ranging from about 1% to about 10% to increase overall cleaning effectiveness and, if desired, to increase the amount of suds.
(the term "alkyl" includes the alkyl portion of an acyl group).
Examples of synthetic surfactants in this group are sodium alkyl sulfates and potassium alkyl sulfates, especially those produced by reducing the glycerides of higher alcohols (carbon number _C8-18 ), such as tallow or coconut _oil . and sodium and potassium alkylbenzenesulfonates in which the alkyl group has from about 9 to about 15 carbon atoms in a straight-chain or branched configuration, e.g., U.S. Pat. No. 2,220,099 and of the type described in Specification No. 2477383. The average number of carbon atoms in the alkyl group is approximately 11~
Of particular value are linear straight-chain alkylbenzene sulfonates, abbreviated C _11-13 LAS, which are 13. Preferred anionic detergent surfactants are alkyl polyethoxylate sulfates, particularly those in which the alkyl has about 10 to about 22 carbon atoms, preferably about 12 to about 18 carbon atoms, and the polyethoxylate chain has about 1 to about 15 ethoxy ethoxylate moieties, preferably from about 1 to about 3 ethoxylate moieties. These anionic detergent surfactants are particularly desirable for formulating heavy duty liquid laundry detergent compositions. Other anionic surfactants are sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonate and sodium coconut oil fatty acid monoglyceride sulfate; 1 molecule Sodium or potassium salts of alkylphenol ethylene oxide ether sulfuric acid containing about 1 to about 10 units of ethylene oxide per molecule and having an alkyl group of about 8 to about 12 carbon atoms; and about 1 to about 10 units of ethylene oxide per molecule; Contains and has an alkyl group with approximately carbon number
10 to about 20 alkyl ethylene oxide ether sulfuric acid salts. Other anionic surfactants useful in the invention include, for example, water-soluble salts of esters of alpha-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; About 2 to 9 carbon atoms in the acyl group and about 9 to about 9 carbon atoms in the alkane moiety
Water-soluble salt of 2-acyloxy-alkane-1-sulfonic acid having 23; about 10 carbon atoms in the alkyl group
~20 and alkyl ether sulfates with about 1 to 30 moles of ethylene oxide; about 12 carbon atoms
A water-soluble salt of olefin sulfonic acid having ~24;
and β-alkyloxyalkane sulfonates having about 1 to 3 carbon atoms in the alkyl group and about 8 to 28 carbon atoms in the alkane moiety. Amphoteric surfactants are, for example, those in which the aliphatic moiety is linear or branched, one of the aliphatic substituents has about 8 to 18 carbon atoms, and at least one aliphatic substituent is anionically water-solubilizing. derivatives of aliphatic secondary and tertiary amines containing groups or aliphatic derivatives of heterocyclic secondary and tertiary aminos. Zwitterionic surfactants are, for example, derivatives of aliphatic quaternary ammonium compounds, phosphonium compounds, and sulfonium compounds in which one of the aliphatic substituents has about 8 to 18 carbon atoms. Particularly preferred co-surfactants in the present invention include, for example, linear alkylbenzene sulfonates having about 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconut alkyl glyceryl ether sulfonates;
18 and an average degree of ethoxylation of about 1 to 4; carbon number of about 14 to 16
and an alkyl group having about 14 carbon atoms;
-18 alkyl dimethyl ammonium propane sulfonate and alkyl dimethyl ammonium hydroxypropane sulfonate. Particular surfactants preferred for use in the present invention include, for example, _C14-15 alkyl polyethoxylates.
_1-3 sodium sulfate, C _14-15 alkyl polyethoxylate _1-3 potassium sulfate, C _14-15 alkyl polyethoxylate _1-3 monoethanol ammonium sulfate,
C _14-15 alkyl polyethoxylate _1-3 diethanolammonium sulfate and C _14-15 alkyl polyethoxylate _1-3 triethanolammonium sulfate; linear C _11-13 alkylbenzenesulfonate sodium; C _11-13 alkylbenzenesulfonate tri Ethanolamine; Sodium tallow alkyl sulfate; Sodium coconut alkyl glyceryl ether sulfonate; Sodium salt of a sulfated condensate of tallow alcohol and about 4 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconut alkyl ammonium) e)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-
N-coconut alkyl ammonio)propane-
1-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)-hexanoate; and coconut alkyldimethylamine oxide. Technically established normal usage amounts (i.e., 0 to approx.
Other auxiliary ingredients which can be incorporated into the compositions of the invention at 90%) are, for example, solvents, bleaches, bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, These include disinfectants, PH regulators (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme stabilizers, fragrances, fabric softening ingredients, static electricity control agents, etc. Fatty acid amide detergent surfactants useful in the present invention include, for example, the formula [In the formula, R ⁶ has a carbon number of about 7 to about 21 (preferably about 9
~ about 17), and each
^R7 is selected from the group consisting of hydrogen, _C1-4 alkyl, _C1-4 hydroxyalkyl, and -( _C2H4O )xH, where x _is about 1 to about 3. It is. Preferred amides are _C8-20 ammonia amide,
Monoethanolammonium, diethanolamide and isopropanolamide. A particular advantage of the detergent surfactant combinations of the invention is their excellent compatibility with anionic fluorescent or optical brighteners. nonionic surfactant,
In particular, ethoxylated nonionic detergent surfactants usually reduce the effectiveness of this type of brightener. When adding alkyl polyglycoside surfactants, the effectiveness of brighteners, especially on cotton, is dramatically improved. Optical brighteners from about 0.01% to about 2%, preferably from about 0.1% to about 1%, can be used. Suitable brighteners include, for example: formula [wherein M is preferably Na, but can be a compatible cation such as potassium, ammonium, substituted ammonium such as monoethanolammonium, diethanolammonium, and triethanolammonium; (wherein ^R2 is selected from H, phenyl, _C1-4 alkyl, or _C1-4 hydroxyalkyl) morpholino, hydroxy; or a mixture thereof; and R can be H or SO ₃ M] Bisanilino(R) triazinylaminostilbene sulfonate having the above structural formula, R and X are as follows.

【table】

[Table] Another brightener is 4,4′-bis[(4″-bis(2
-hydroxyethyl)amino-6″-(3′′′′-
sulfenyl)amino-1″,3″,5″-triazine-
2″-yl)amino]-2,2′-stilbenedisulfonic acid tetrasodium; 4-(6′-sulfonaphtho[1′,2′,d]triazol-2-yl)-2-stilbenesulfonic acid disodium; 4,4′-bis[(4″-(2-hydroxylethylamino)-6″-
anilino-1″, 3″, 5″-triazin-2″-yl)
Disodium amino]-2,2'-stilbenzylsulfonate;4,4'-bis[(4''-(2-hydroxyethoxy)-6''-anilino-1'',3'',5''-triazine-2 ″-yl)amino]-2,2′-stilbenedisulfonic acid disodium; 4,4′-bis(4-phenyl-1,2,3-triazole-2
-yl)-2,2'-stilbenzylsulfonate disodium; 4-(2H-naphtho[1,2- d ]triazol-2-yl)stilbene-2-sulfonate; disodium-4,4' -Bis-
(2-sulfostyryl)biphenyl; 4-(2H-
6-Sulfonaphtho[1,2- d ]triazole-
2-yl)stilbene-2-sulfonic acid disodium; and disodium-3,7-bis(2,
4-dimethoxybenzamide)-2,8-dibenzothiophene disulfonate-5,5-dioxide. Other suitable brighteners are disclosed in US Pat. Nos. 3,537,993 and 3,953,380. The compositions of the invention may be in various forms, such as solids,
It can be prepared and used in powders, granules, pastes, and liquids. Composition approximately 0.01% in water
The composition is prepared by preparing an aqueous solution containing ~1%, preferably about 0.05% to about 0.5%, most preferably about 0.05% to about 0.25%, and stirring the soiled fabric in the aqueous solution. can be used in current washing methods. The fabric is then rinsed and dried. When used in this manner, preferred compositions of the invention exhibit very good cleaning power on a variety of fabrics. In a preferred embodiment, the laundry detergent, preferably an aqueous heavy duty liquid, contains (a) about 1% to about 20% (preferably about 4% to about 10%) alkyl polyglycoside detergent surfactant; (b) Amine oxide detergent surfactant from about 1% to about 10% (preferably about 2%)
(c) 1% to about 10% (preferably about 1% to about 6%) of a water-soluble soap of unsaturated fatty acids having about 16 to about 22 carbon atoms; (d) Preferably pyrophosphoric acid salt,
0% water-soluble detergency builder selected from the group consisting of nitrilotriacetates, and mixtures thereof.
~about 40% (preferably about 10% to about 30%}; (e) water-soluble synthetic anionic detergent surfactant about 0% to about 10%
(preferably about 0% to about 5%); and preferably
(f) The remainder contains water. This kind of detergent composition gives excellent cleaning power,
It does not unacceptably damage the washing machine and can be formulated to provide different suds patterns by varying the amount and type of synthetic anionic detergent surfactant and the amount of unsaturated soap.
Preferably, such formulations do not contain more than about 5% of conventional ethoxylated nonionic surfactants. Sodium, potassium, ammonium, and alkanol ammonium cations are preferred. All percentages, parts, and ratios are by weight unless otherwise specified. The following example may be given as an illustration. However, the examples are examples of the invention and the examples are given for comparison.

Table: The surfactant mixture is 13% of the formulation, and the builder is sodium nitrilotriacetate (18
%). Test conditions are composition 2100ppm, 95〓
(approximately 35.0°C), and the mixed hardness was 6 grains. *PSU is a panel score unit.
Units), and professional graders specify numerical values on the basis of 0 for no difference; 1 for difference; 2 for clear difference. Example Combinations of alkyl polyglucosides and semipolar nonionic and/or amide detergent surfactants are compatible with unsaturated soaps.
However, it is incompatible with saturated soap.

【table】

Table: Compositions 1-3 and 5 produced less suds than Formulation 4 and were compatible with washing machine surfaces (less corrosion). Composition 3 formed an unsightly soap scum in the rinse water despite the presence of substances known to inhibit scum formation. Also, Composition 3 produced a viscous gel rather than a free-flowing clear liquid. It is clear that there should be no substantial excess of saturated soap over unsaturated soap. Soap is unsaturated soap at least approx.
Must be 40%. Total free fatty alcohols having from about 8 to about 20 carbon atoms are less than about 5%, preferably about 2%
It has further been discovered that the performance of these compositions is improved if less than 1%, most preferably less than about 1%.

Claims (1)

[Claims] 1 (A) Formula RO(R ¹ O) _y (Z) _x [In the formula, R is alkyl,
hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl,
or mixtures thereof (wherein the alkyl group has about 8 to about 18 carbon atoms); each R ¹ is ethylene, propylene or -CH ₂ -CH(OH)-CH ₂
- group, and y is from 0 to about 12; and each Z is a moiety derived from a reducing sugar having 5 or 6 carbon atoms, and x is from about 1 1/2 to about
(B) an amine oxide detergent surfactant of about 1% to about 7;
%, (C) about 1% to about 15% of a water-soluble fatty acid soap containing at least about 40% of an unsaturated soap having about 16 to about 22 carbon atoms. 2. The composition of claim 1 in the form of a concentrated aqueous heavy duty liquid containing less than about 5% of a conventional ethoxylated nonionic detergent surfactant. 3 Amine oxide detergent surfactant formula (wherein R is an alkyl group, hydroxyalkyl group, or alkylphenyl group having about 10 to about 18 carbon atoms, or a mixture thereof, and R' is an alkylene group or hydroxyalkylene group having 2 to 3 carbon atoms. or a mixture thereof, x
is from 0 to about 2, and each R'' is an alkyl or hydroxyalkyl group having from 1 to about 3 carbon atoms or a polyethylene oxide group containing from 1 to about 3 ethylene oxide groups, and
4. The composition according to claim 2, wherein the R'' groups can be bonded to each other through an oxygen atom or a nitrogen atom to form a ring structure. 4. In the alkyl polyglycoside detergent surfactant, R has about 10 carbon atoms. 4. The composition of claim 3, wherein the cations of the unsaturated fatty acid soap include sodium, potassium, ammonium, 5. The composition of claim 4, wherein R is selected from the group consisting of , monoethanol ammonium, diethanol ammonium, triethanol ammonium, and mixtures thereof. 10 to about 14, and x is about 1.6 to about 2.7. 7. The composition of claim 2, wherein the cations of the unsaturated fatty acid soap include sodium, potassium, ammonium, mono The composition of claim 6 selected from the group consisting of ethanolammonium, diethanolammonium, triethanolammonium, and mixtures thereof. 8. Claim 6 wherein the unsaturated fatty acid soap is an oleate salt. A composition according to paragraph 3, paragraph 4, or paragraph 7. 9. A composition comprising at least 35% by weight of the composition a water-soluble detergent builder, at least 7% by weight of the composition a water-soluble synthetic anionic detergent surfactant. at least of things
A composition according to claim 1 further comprising at least one substance selected from the group consisting of 80% by weight water. 10. The composition of claim 9 in the form of a concentrated aqueous heavy duty liquid containing less than about 5% of a conventional ethoxylated nonionic detergent surfactant. 11 Amine oxide detergent surfactant formula (wherein R is an alkyl group, hydroxyalkyl group, or alkylphenyl group having about 10 to about 18 carbon atoms, or a mixture thereof, and R' is an alkylene group or hydroxyalkylene group having 2 to 3 carbon atoms. or a mixture thereof, x
is from 0 to about 2, and each R'' is an alkyl or hydroxyalkyl group having from 1 to about 3 carbon atoms or a polyethylene oxide group containing from 1 to about 3 ethylene oxide groups, and
R'' groups can be bonded to each other through oxygen or nitrogen atoms to form a ring structure. 12. Pyrophosphate, nitrilotriacetate, citrate, polymer. Approximately 10% detergency builder selected from the group consisting of polycarboxylate and carbonate
12. The composition of claim 11 containing up to about 30%. 13. The composition of claim 11, wherein R is an alkyl group having about 10 to about 16 carbon atoms in the alkyl polyglycoside detergent surfactant, and x is about 1 1/2 to about 3. . 14 from about 10% to about 30% detergency builder selected from the group consisting of pyrophosphates, nitrilotriacetates, citrates, polycarboxylates, and carbonates
14. A composition according to claim 13 containing %. 15. The composition of claim 13, wherein the cations of the unsaturated fatty acid soap are selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, and mixtures thereof. 16. The composition of claim 10, wherein R is an alkyl group having from about 10 to about 14 carbon atoms in the alkyl polyglycoside detergent surfactant and x is from about 1.6 to about 2.7. 17 about 5% to about 35 detergency builders selected from the group consisting of pyrophosphates, nitrilotriacetates, citrates, polycarboxylates, and carbonates
17. The composition of claim 16 containing %. 18. The composition of claim 16, wherein the cations of the unsaturated fatty acid soap are selected from the group consisting of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, and mixtures thereof. 19 Claim 11, 13, or 1 in which the unsaturated fatty acid soap is an oleate salt
Composition according to item 8. 20. The composition of claim 1, wherein R is alkyl, hydroxyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof, and said alkyl group has from about 12 to about 18 carbon atoms.