JPH0443959B2 - - 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 monoglucosides 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 is disclosed in specification No. 4011389 and specification No. 4223129. SUMMARY OF THE INVENTION The present invention relates to the discovery of a species combination of surfactants that provides very good detergency and good anionic optical brightener effectiveness on a variety of fabrics, especially in cold water. In particular, the present invention provides (1) a compound of the formula RO(R ¹ O) _y ( _Z ) Yes (the alkyl group has about 8 to about 18 carbon atoms); each R ¹ is ethylene, propylene or -CH ₂ -CH(OH)-CH ₂
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 11/2 to about 10
an alkyl polysaccharide detergent surfactant having a number of from about 1% to about
90%, (2) Ethoxylated nonionic detergent surfactant approximately 1% ~
(3) detergency builder from 0% to about 90%, and (4) anionic fluorescent brightener from about 0.01 to about 2.0% (the ratio of (1) to (2) is less than 1:4). (large). Description of Preferred Embodiments Alkyl Polysaccharide Surfactants Surprisingly, it has 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 11/2 to about 10, preferably about 11/2 hydrophobic groups and sugar units having from about 10 to about 16 carbon atoms.
Polysaccharides, such as polyglycosides, having hydrophilic groups of from to about 3, most preferably from 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 bonds may be formed, for example, at one position of the additional sugar unit and at the 2nd, 3rd, 4th and/or position on the previous sugar unit.
It can be between 6th place and 6th place. 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, fucultose, 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 R ² O(C _o H _2o O) _t (glycosyl) _x [wherein R ² is alkyl, alkylphenyl,
selected from the group consisting of hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein said alkyl group has from about 10 to about 18 carbon atoms, preferably from 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 11/2 to about 10, preferably from about 11/2 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 absence of substantial amounts of anionic detergent surfactants in the presence of conventional ethoxylated nonionic detergent surfactants. 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 surfactant Nonionic surfactant Nonionic surfactant, 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 present in an amount equal to 5 to 25 moles per mole of alkylphenol). 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; dinonylphenol 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 are e.g.
Igepal CO-630, marketed by GAF Corporation, and Rohm
Triton X-45, X-114, X- marketed by End Haas Company
100 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). mixture)
It is a condensate of Examples of commercially available nonionic surfactants of this type are Tergitol 15-8-9, marketed by Union Carbide Corporation; Tergitol 15-8-9, marketed by Shell Chemical Company; Neodol 45-9, Neodol 23-6.5,
Neodol 45-7, and Neodol 45-4, and Kyro, marketed by The Procter & Gambling Company.
It is EOB. (3) Condensates of ethylene oxide and hydrophobic bases produced by condensation of propylene oxide and propylene glycol The hydrophobic portion of these compounds has a molecular weight of about 1500-1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole;
The liquid character of the product is then maintained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensate (corresponding to condensation with up to about 40 moles 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 part has a condensation product of polyoxyethylene of about 40 to about
It is condensed with ethylene oxide to an extent containing 80% by weight and having a molecular weight of about 5,000 to about 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. or a mixture thereof;
x is 0 to about 3, and each R ⁵ has 1 to about 3 carbon atoms.
an alkyl or hydroxyalkyl group having about 3 or a polyethylene oxide group containing from 1 to about 3 ethylene oxide groups, and the R ⁵ groups can be bonded to each other, for example through carbon or nitrogen atoms, to form a ring structure. ) is an amine oxide detergent surfactant. Preferred amine oxide detergent surfactants are:
C _10~18 Alkyldimethylamine oxide, C _8~18
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 R ⁸ (OC ₂ H ₄ ) _o OH, where R ⁸ has from about 8 carbon atoms to about 22, preferably about 10 to about 20 primary or secondary alkyl chains, and n averages about 2 to about 12, especially 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 with 5 mol of ethylene oxide; Condensation product of coconut alcohol with 6 mol of ethylene oxide; Condensation product of C ₁₂ alcohol with 5 mol of ethylene oxide; Condensation product of C _12-13 alcohol with 6.5 mol of ethylene oxide condensate,
and the same condensate stripped to remove substantially all the lower ethoxylated and non-ethoxylated flanks; a condensate of a _C12-13 alcohol with a few moles of ethylene oxide, substantially all the lower ethoxylated and The same condensate stripped to remove the non-ethoxylated fraction; a condensate of a C _12-13 alcohol with 9 moles of ethylene oxide; a condensate of a C _14-15 alcohol and
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 surfactants and includes the preferred alcohol ethoxylate surfactant(s) versus the other nonionic surfactant(s). or multiple) ratio of approximately 1:1
~ about 5:1. A particular example of a surfactant mixture useful in the present invention is a condensate of a _C14-15 alcohol with 3 moles of ethylene oxide (Neodol 45-
3) and a condensate of a C _14-15 alcohol with 9 moles of ethylene oxide (Neodol 45-9) in a ratio of lower ethoxylate nonionic surfactant to higher ethoxylate nonionic surfactant from about 1:1. Approximately 3:1 mixture; lower ethoxy of a condensate of a C ₁₀ alcohol with 3 moles of ethylene oxide and a condensate of a secondary C ₁₅ alcohol with 9 moles of ethylene oxide (tergitol 15-S-9) A mixture of rate nonionic surfactants to higher ethoxylate nonionic surfactants in a ratio of about 1:1 to about 4:1; Neodol 45-3 and Tergitol 15-S-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; and Neodol;
45-3 and a condensate of myristyl alcohol and 10 moles of ethylene oxide in a ratio of lower ethoxylates to higher ethoxylates of about 1:1 to about 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, and n is 0 to about alcohol ethoxylate to glyceryl ether ratio of about 1:1 to about 4:
1, especially mixtures of about 7:3 are particularly preferred. 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 have the formula Na _z [(AlO ₂ ) _z ·(SiO ₂ ) _y ]·xH ₂ O, for example, where z and y are at least about 6;
The molar ratio of z 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
~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 0.01 microns. A more preferred ion exchange material is about 0.2
It has a particle size of microns to about 4 microns. As used herein, the term "particle size" is used in common analytical techniques,
It refers to the average particle size of a given ion exchange material as determined by microscopic measurements using, for example, a scanning electron microscope. The crystalline aluminosilicate ion exchange material has at least about 200 mg of CaCO ₃ water hardness equivalent per gram of aluminosilicate, calculated on an anhydrous basis, and generally between about 300 mg·eq/g and about 352 mg·eq/g.
It is usually further characterized by a calcium ion exchange capacity which is in the range of eq/g. The aluminosilicate ion exchange material contains at least about 2 grains.
Ca ⁺⁺ /gal/min/g/gal Aluminosilicate (anhydrous basis), typically 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 gallons to about 6 grains/gallon/minute/g/gallon. Aluminosilicates of choice for builders exhibit calcium ion exchange rates of at least about 4 grains/gal/min/g/gal. Amorphous aluminosilicate ion exchange materials typically contain at least about 50 mg·eqCaCO ₃ /g (12 mgMg ⁺⁺ /
g) and ^{an 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 aluminosilicate 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 _Na12 [( _AlO2 ) _12. ( _SiO2 ) ₁₂ ] _.xH2O , 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 polycarponate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, and citric acid. It is. 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
- cyclohexane hexagalboxylate, cis-cyclobentanetetracarboxylate, phloroglucinol trisulfonate, water-soluble polyacrylate (e.g. having a molecular weight of about 2000 to about 200000),
and copolymers of maleic anhydride and vinyl methyl 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 salt of the reaction, 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 2.7:1 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 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 500 ppm, and for European usage levels. Since mono-, di-, and tri-unsaturated fatty acids are all essentially equivalent, it is preferred to use primarily mono-unsaturated soaps to minimize the risk of malodor. Suitable sources of unsaturated fatty acids are well known. See, eg, 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% of the total soap is saturated soap, preferably less than about 50%. 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 this group of synthetic surfactants are sodium alkyl sulfates and potassium alkyl sulfates, especially those produced by reducing the glycerides of higher alcohols (carbon number _C8 to _C18 ), 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 or branched configuration, e.g., U.S. Pat. No. 2,220,099. It is of the type described in the specification and 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 about 1 to 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 sulfonate; 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 present invention include, for example, water-soluble salts of esters of alpha-sulfonated aliphatics 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 20 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 amines. 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 sodium sulfate, C _14-15 alkyl polyethoxylate _1-3 monoethanol ammonium sulfate, C _14-15 alkyl polyethoxylate _1-3 diethanol ammonium sulfate and C _14-15 alkyl polyethoxylate _1-3 triethanolammonium sulfate; linear C _11-13 alkylbenzenesulfonate sodium; C _11-13 alkylbenzenesulfonate triethanolamine; sodium tallow alkyl sulfate; coconut alkyl glyceryl ether sulfone acid sodium; tallow alcohol and about 4
Sodium salt of sulfated condensate with moles of ethylene oxide; 3-(N,N-dimethyl-N-coconut alkyl ammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N - coconut alkyl ammonio)propane-1-sulfonate; 6-(N-dodecylbenzyl N,N-dimethylammonio)-hexanoate; and coconut alkyl dimethylamine oxide. Technically established normal usage amounts (i.e., 0 to approx.
Other auxiliary components 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.), oxygen, 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 [wherein R ⁶ is an alkyl group having about 7 to about 21 carbon atoms (preferably about 9 to about 17 carbon atoms), and each
R ⁷ is selected from the group consisting of hydrogen, C _1-4 alkyl, C _1-4 hydroxyalkyl, and -(C ₂ H ₄ O) _x H, where x is from about 1 to about 3. It is something. 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; (In the formula, R ² is H, phenyl, C _1-4 alkyl,
or selected from C _1-4 hydroxyalkyl)
Morpholino, hydroxy; or a mixture thereof and can be R or H or SO ₃ M] Bisanilino(R) triazinylaminostilbene sulfonate having the above structural formula, R and X are as follows.

[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-hydroxyethylamino)-6″-anilino-1″,3″,5″-triazin-2″-yl)amino]-2,2′-stilbendisulfone Disodium acid; 4,4′-bis[4(4″-(2-hydroxyethoxy)-6″-anilino-1″,3″,5″-triazin-2″-yl)amino]-2,2 '-Stilbenedisulfonic acid disodium; 4,4'-bis(4
-Phenyl-1,2,3-triazol-2-yl)-2,2'stilbenedisulfonic acid disodium; 4-(2H-naphtho[1,2- d ]triazol-2-yl)stilbene-2-sulfone Sodium acid; Disodium 4,4'-bis-(2-sulfostyryl)biphenyl; Disodium 4-(2H-6-sulfonaphtho[1,2, d ]triazol-2-yl)stilbene-2-sulfonate ;
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 now 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 laundry 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. All percentages, parts, and ratios are by weight unless otherwise specified. The following examples illustrate the compositions and methods of the invention. Example part C _12-15 alkyl polyglycoside _2-3 13.3 C _12-13 alkyl polyethoxylate _6.5 13.3 Sodium tripolyphosphate 12.0 Na ₂ CO ₃ 13.3 Polyacetaldehyde detergency builder 28.8 Anionic brightener _* 1.0 _* : Bis(anilino) -Hydroxyethylmethylaminotriazinylamino)stilbenedisulfonate (sodium salt)

[Table] Example Cotton T-shirt Redeposition and Brightness/Brightening Test The following results obtained using a non-built mixture of surfactants demonstrate the It clearly shows the effectiveness of alkyl polyglycosides in improving efficacy. The data show that at least approximately 40% of the surfactant system
clearly indicates that should be an alkyl polyglycoside. A HWU of 5-6 is a substantial improvement.

【table】

【table】

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, where 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 about 11/2
(B) an ethoxylated nonionic detergent surfactant of about 1% to about 90%;
about 90%, (the ratio of (A) to (B) is greater than about 1:4), and (C) about 0.01% to about 2% anionic optical brightener. thing. 2 Component (A) has the formula R ² O (C _o H _2o O) _t (glucosyl) _x (wherein R ² is alkyl, alkylphenyl,
selected from the group consisting of hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, t is from 0 to about 25, the glucosyl moiety is derived from glucose, n is 2 or 3, and x is about 11/2 3). 3 Ethoxylated nonionic surfactant is about 5 to about 17
and the anionic optical brightener has an HLB of approximately
Claim 2 present in an amount of 0.1 to about 1%
The composition described in Section. 4 The anionic optical brightener has the formula (wherein M is sodium, potassium, ammonium, substituted ammonium, or a mixture thereof; and R and X are 4,4' −Bis [(4″−
Bis(2-hydroxyethyl)amino-6″-
[3″″-sulfenyl)amino-1″,3″,5″-triazin-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-hydroxyethylamino)-6″-anilino-1″,3,5′-triazine-
2″-yl)amino]-2,2′-stilbenedisulfonic acid disodium; 4,4′-bis[4(4″-(2
-hydroxyethoxy)-6″-anilino-1″,
3″,5″-triazin-2″-yl)amino]-2,
2'-stilbenedisulfonic acid disodium; 4,
Disodium 4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'stilbendisulfonate;disodium-4,4'-bis-
(2-sulfostyryl)biphenyl; 4-(2H-
naphtho[1,2- d ]triazol-2-yl)
Sodium stilbene-2-sulfonate; 4-
(2H-6-sulfonaphtho[1,2, d ]triazol-2-yl)stilbene-2-sulfonic acid disodium; and disodium-3,7-bis(2,4-dimethoxybenzamide)-2,8- A composition according to claim 1 selected from the group consisting of dibenzothiophene disulfonate-5,5-dioxide and mixtures thereof. 5. The composition of claim 4, wherein the ratio of (A) to (B) is from about 1:3 to about 3:1. 6. The method according to claim 1, wherein R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof, and said alkyl group contains about 12 to 18 carbon atoms. Composition. 7(A) Formula RO(R ¹ O) _y (Z) _x [wherein R is alkyl, hydroxyalkyl, alkylphenyl,
hydroxyalkylphenyl, alkylbenzyl, or mixtures thereof, where 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 about 11/2
(B) an ethoxylated nonionic detergent surfactant of about 1% to about 90%;
(C) up to about 90% detergency builder (the ratio of (A) to (B) is greater than about 1:4); and (D) from about 0.01% to about 2% anionic optical brightener. A detergent composition comprising: 8 Component (A) has the formula R ² O (C _o H _2o O) _t (glucosyl) _x (wherein R ² is alkyl, alkylphenyl,
selected from the group consisting of hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, t is 0 to about 25, the glucosyl moiety is derived from glucose, n or 2 or 3, and x is about 11/2 9. The composition of claim 7, wherein the composition has a composition of claim 7, wherein the composition has a composition of 1 to about 3. 9 Ethoxylated nonionic surfactant is about 5 to about 17
and the anionic optical brightener has an HLB of approximately
Claim 8 present in an amount of 0.1 to about 1%
The composition described in Section. 10 The anionic optical brightener has the formula (wherein M is sodium, potassium, ammonium, substituted ammonium, or a mixture thereof; and R and X are 4) ,4′-bis [(4″-
Bis(2-hydroxyethyl)amino-6″-
[3″″-sulfenyl)amino-1″,3″,5″-triazin-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-hydroxyethylamino)-6″-anilino-1″,3,5′-triazine-
2″-yl)amino]-2,2′-stilbenedisulfonic acid disodium; 4,4′-bis[4(4″-(2
-hydroxyethoxy)-6″-anilino-1″,
3″,5″-triazin-2″-yl)amino]-2,
2'-stilbenedisulfonic acid disodium; 4,
Disodium 4'-bis(4-phenyl-1,2,3-triazol-2-yl)-2,2'stilbendisulfonate;disodium-4,4'-bis-
(2-sulfostyryl)biphenyl; 4-(2H-
naphtho[1,2- d ]triazol-2-yl)
Sodium stilbene-2-sulfonate; 4-
(2H-6-sulfonaphtho[1,2, d ]triazol-2-yl)stilbene-2-sulfonic acid disodium; and disodium-3,7-bis(2,4-dimethoxybenzamide)-2,8- 8. The composition of claim 7 selected from the group consisting of dibenzothiophene disulfonate-5,5-dioxide and mixtures thereof. 11. The composition of claim 10, wherein the ratio of (A) to (B) is from about 1:3 to about 3:1. 12 Hydrated zeolites A, of the claims selected from the group consisting of salts, pyrophosphates, carbonates, silicates, borates, polymeric metaphosphates, nitrilotriacetates, citrates, and polyacetal carboxylates and mixtures thereof. A composition according to scope item 7. 13 R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof;
8. The composition of claim 7, wherein said alkyl group contains about 12 to 18 carbon atoms. 14 Cotton cloth, (A) formula RO(R ¹ O) _y (Z) _x [wherein 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)-
_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 from about 11/2 to about
(B) an ethoxylated nonionic detergent surfactant of about 1% to about 90%;
from about 0.01% to about 90%; (the ratio of (A) to (B) is greater than about 1:4); and (C) from about 0.01% to about 2% an anionic optical brightener. A method of cleaning in an aqueous detergent solution containing 1%. 15 R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof;
15. The method of claim 14, wherein said alkyl group contains about 12 to 18 carbon atoms. 16 Cotton cloth, (A) formula RO (R ¹ O) _y (Z) _x [wherein 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)-
a _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 from about 11/2 to
from about 1% to about 90% of an alkyl polysaccharide detergent surfactant (with a number of about 10); (B) from about 1% to about an ethoxylated nonionic detergent surfactant;
(C) detergency builder up to about 90% (ratio of (A) to (B) greater than 1:4) and (D) anionic optical brightener from about 0.01% to about 2%. The detergent composition is approx.
A method of cleaning in an aqueous detergent solution containing from 0.01% to about 1%. 17 R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof;
17. The method of claim 16, wherein the alkyl group contains about 12 to 18 carbon atoms.