JPS58132094A - Detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to laundry in order to improve the detergency and optionally the effectiveness and anti-foaming properties of fluorescent whitening agents. Concerning combinations of surfactants that provide corrosion inhibition. Compositions of this type can be built or unbuilt, granular or liquid, and can contain the usual auxiliary ingredients for compositions of this type Km.

The alkyl monoglucosyl surfactant is described in U.S. Patent No. 3 $598,865, No. 3.721.63.
No. 34+ and No. 3,712,2119. These patents also disclose methods of making alkylpoglycidiP surfactants and PIL F liquid detergent compositions containing these surfactants.

No. 3,219.65g discloses alkyl monoglucosy P and suggests its utility as a foam stabilizer for other surfactants.

The structures of various polyglycosi-P surfactants and their production methods are described in U.S. Patent No. 3.640.998, No. 3,
839,318 specification, 3.314,936 specification, 3,346.558 specification, 4,011,3
No. 89, No. 4,223,129.

SUMMARY OF THE INVENTION The present invention relates to the discovery of a species combination of surfactants that provides very good cleaning power on a variety of fabrics, especially in cold water. In particular, the present invention relates to (1) formula % () [wherein R is alkyl, k-hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl or a mixture thereof (the alkyl group is carbon from about 8 to about 18); each 81 has from 2 to about 4 carbon atoms
preferably an ethoxy group, a propoxy group, or a glyceryl group, and y is from 0 to about 12; and each 2 is an alkyl polysaccharide having a moiety derived from a reducing sugar having 5 or 6 carbon atoms ( Alkyl polysaccharide sa, Karai P) Detergent surfactant 1-~about beauty, (-nonionic detergent surfactant 1-~fishing bacteria-1 and (3) detergent pilder〇-~about (a)- ((1) vs. (2
)) in a ratio of from about 1:10 to about 1O:1, preferably from about 3:1 to about 1=3.

A very, very preferred variation also contains an anionic fluorescent brightener (optical brightener) from about 0.01 to about 2.0.

In another highly preferred variant, the non-ionic detergent surfactant is selected from the group consisting of aneoxyr detergent surfactants, anP detergent surfactants and mixtures thereof, and the composition has a carbon number of about About 1 q of unsaturated soap with n from 16! 1 to about 1091, and preferably a synthetic anionic detergent surfactant of about 1 to about 10.

Surprisingly, it has been found that co-surfactants interact with the alkyl polysaccharide surfactants of the present invention to provide good laundering detergency to a wide variety of fabrics. The alkyl polysaccharide has about 6 to about (1) carbon atoms, preferably about 1 carbon number.
0 to about 16 hydrophobic groups and most preferably about 1.6
A polysaccharide having a parent group of ˜2.7, such as a polyglycosylated P parent group.

Any reducing sugar having 6 carbon atoms can be used,
For example, glucose moieties, galactose moieties and galactosyl moieties can be used in place of glucosyl moieties (in some cases the hydrophobic groups are attached at the 2-position, 3-position, 4-position etc., thus making glucose as opposed to glucoside or galactoside or give galactose)
. The sugar linkage can be, for example, between one position of the additional sugar unit and the 2nd, 3rd, 4th and (i or) 6th position on the previous sugar unit.

Optionally, and less preferably, there can be a polyalkoxy chain attached to the hydrophobic and polysaccharide moieties. Preferred alkoxide is ethyleneoxy P
It is. Typical hydrophobic groups include, for example, about 8 to about 18 carbon atoms.
, preferably a saturated or unsaturated branched alkyl group having 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 the polyalkoxy r-chain can contain up to about 10 alkoxy P moieties, preferably less than 5, and most preferably 0.

Suitable alkyl polysaccharides include octyl, nonyldecyl, undecyl P-decyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, he! Tadecyl, and octadecyl di-, sily-, tetra-, penta-1 and hexaglucosides 1-galactoside, lactosi-P1 glucose, fructosi-P1 frutatose, and/or galactose. Suitable mixtures are, for example, coconut alkyl-, tri-, tetra-1 and penta-glucosides and tallow alkyl-tetra-, penta-1 and hexadarkosi-P.

Preferred alkyl polyglycosides are selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group has about 10 carbon atoms. to about 18, preferably about 12 to about 14); n is 2 or 3, preferably 2; t is θ to
About lO1 preferably about 3 at 0, preferably about 1.6
~2.7]. Glycodyl is preferably derived from glucose. To produce a compound,
The alcohol or alkyl polyethoxy alcohol is first produced and then reacted with glucose or a source of glucose to produce glucosy-P (bonded at the 1-position). Additional glycosyl units in their 1st and 2nd positions of the previous glycosyl unit
3, 4, and (i) 6, preferably primarily 2.

Preferably the content of alkyl monoglycosylation P is low, preferably less than about 6011, more preferably about 50
Less than 91.

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. , is very effective when an alkyl 4-glycosiP surfactant is present. For brightener effectiveness, the ratio of alkyl-4-glycosi-P detergent surfactant to non-ionic detergent surfactant should be greater than about 1:4, preferably greater than about 1:3. , most preferably greater than about 1:1.

Nonionic surfactants, such as those having an HLB of about 5 to about 170, are well known in the cleaning art.

Nonionic surfactants are incorporated into the compositions of the present invention, for example, together with the alkyl I-glycosi-P surfactants.

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 U.S. Pat. No. 3,332,88.
It is described in the specification of No. 0. 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 with alkyl groups having from 6 to 12 carbon atoms in either a straight-chain or branched configuration with ethylene oxide ( The ethylene oxide is present in an amount equal to 5 to 25 moles per mole of phenol in the alkali), the alkyl substituents in compounds of this type can be derived, for example, from polymerized propylene, diisozotylene, etc. Examples of kerosene compounds c. 9 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: about 15 moles of ethylene oxide per mole of phenol. and diisooctylphenol condensed with about 15 moles of ethylene oxide per 14 moles of phenol. Commercially available nonionic surfactants of this type are, for example, Ig@pal Co-630, marketed by GAF Co., Ltd.
and Triton X-45, X, marketed by Rohm & Haas Company.
-114, X-100 and X-102.

(2) Aliphatic alcohol and ethylene oxide about 1 to about 5
The alkyl chain of the condensate aliphatic alcohol with moles is either linear or branched, primary or secondary, and has a noble number of about 8
~ generally have about n. An example of this type of ethoxylated alcohol is a condensate of monolithyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and about 9 moles of ethyleneoxy P and coconut alcohol (with an alkyl chain length of 10 carbon atoms -14). An example of a commercially available nonionic surfactant of this type is Tergitol (
Tergitol) 15-8-9, Neodol (N
*odol) 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, and Kyro EOB marketed by The Broctor End Company, Yanpur Khan Thani.

(3) condensates of hydrophobic pace produced by condensation of propylene oxide and propylene glycol with ethyleneoxy P; the hydrophobic portion of these compounds has a molecular weight of about 1500-1800 and exhibits water insolubility; Addition of the polyoxyethylene moiety 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 5% of the total weight of the condensate.
0- (corresponding to condensation with up to about 40 moles of ethyleneoxy r). Examples of this type of compound are:
A commercially available class of Zollonik (Plur n1a) surfactants is marketed by Wyandotte Cical Corporation.

(4) Condensation products of products produced from the reaction of propyleneoxy P and ethylenediamine with ethylene oxide.The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and the
It has a molecular weight of 0 to about 3000. This hydrophobic moiety is condensed with ethyleneoxy P to the extent that the condensate contains if IJ oxyethylene from about 40 to about 40% by weight and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include the commercially available types Tetrolie sold by Wyandotte Kencal Corporation.
) is a compound.

(5) Semipolar nonionic detergent surfactants include, for example, one alkyl moiety having 10 to 18 carbon atoms and 1 to about 3 carbon atoms.
a water-soluble amine oxide containing two moieties selected from the group consisting of an alkyl group having a carbon number of lO to 18 and a hydroxyalkyl group; A water-soluble phosphine oxyto containing two moieties selected from the group consisting of alkyl groups: and carbon number lO~18
and one moiety selected from the group consisting of an alkyl moiety having 1 to 3 carbon atoms and a human oxyalkyl moiety.

Preferred semipolar nonionic detergent surfactants have the formula % (where R is an alkyl group, hydroxyalkyl group, or alkylphenyl group having about 8 to about ρ carbon atoms, or a mixture thereof, and R4 is an alkylene group or hydroxyalkylene group having 2 to 3 carbon atoms or a mixture thereof, X is O to about 3, and each R5 is an alkyl group or hydroxyalkyl group having 1 to about 3 carbon atoms or 1 ~ a polyethyleneoxy P group containing about 3 ethylene oxide groups, and the Rs groups can be bonded to each other to form a ring structure, e.g. through an oxygen or nitrogen atom). be.

Preferred Ann-O-Meishi P detergent surfactants are C10-1
8 Alkyl dimethylamine oxide, C18 alkyl dihydroxyethyl amine oxy P1 Oyohi C,,,□8
AlkoxyethyldihyPoxyethyla27oxyP.

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 % (formula %), where R is from about 8 to about n carbon atoms, preferably about 10 ~ about + primary or secondary alkyl chain, and r1
11 average about 2 to about 12, especially about 2 to about 9). The nonionic surfactant has an HLB (ill aqueous lipophilicity 77 lance) of about 5 to about 17, preferably about 6 to about 15. HLB is a nonionic surfactant by M.G.
(page 13). Among preferred nonionic surfactants, the number is 3 to 7. (primary linear alcohol ethoxylates) (e.g., alcohol ethoxylates produced from organic alcohols containing the 2-methyl branched isomer 20-, commercially available under the trade name Neodol from Schieruke Jiancal Kanno Zhenyi) ) is preferred from a performance standpoint.

Particularly preferred non-ionic surfactants for use in the compositions of the invention are, for example, the condensate of C1G alcohol and 3 moles of ethyleneoxy P; the condensate of tallow alcohol and 9 moles of ethylene oxide; Sconut alcohol Condensate of P and 5 moles of ethylene oxide: C; Condensate of nut alcohol and 6 moles of ethylene oxy P; C12
Condensate of alcohol and 5 moles of ethyleneoxy P; C
18-1° alcohol and 6.5 moles of ethyleneoxy P
and the same condensate stripped to remove substantially all the lower ethoxylated and non-ethoxylated 7-lactones; a condensate of C5z-as alcohol with 2.3 moles of ethyleneoxy P, substantially The same condensate stripped to remove all lower ethoxylated products and non-ethoxylated 7-lactones; condensate of C alcohol with 9 moles 12-13 of ethylene oxide; C14-Jl alcohol-
A condensate of C alcohol and 2.25 moles of ethylene oxide; a condensate of C alcohol and 4 moles of ethyleneoxy 14-15 P; a condensate of C alcohol and 7 moles of ethylene oxy P; and 014% It is a condensate of 15 alcohol and 9 moles of ethyleneoxy P.

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 oil nonionic surfactant. Specific examples of surfactant mixtures useful in the present invention having the ratio(s) of 1=1 to about 5=1 include CI4-1. alcohol and 3
Condensate with mol of ethyleneoxy P (Neodol 45-
3) and a condensate of C alcohol and 9 moles of 14 to tS of ethyleneoxy P (Neodol 45-9
) in a ratio of 1:1 to about 3:1 of a lower ethoxylate nonionic surfactant to a higher ethoxylate nonionic surfactant; a condensate of a C1o alcohol and 3 moles of ethyleneoxy P; Secondary C, alcohol and 9
Condensation product with mol of ethyleneoxy P (tergitol 15
-8-9) Ratio of lower ethoxylate nonionic surfactant to higher ethoxylate nonionic surfactant 1:
1 to about 4=1 mixture; 1:1 to about 3:1 ratio of lower ethoxylate nonionic surfactant to higher ethoxylate nonionic surfactant of Neodol 45-3 and Tergitol 15-8-9 a mixture of; and Neodol 4
5-3 and a condensate of lysyl alcohol and 10 moles of ethylene oxide in a 1:1 to about 3:1 ratio of lower to higher ethoxylates.

Preferred nonionic surfactant mixtures can also contain alkyl glyceryl ether compounds along with the preferred alcohol ethoxylate surfactants.

Formula % Formula % (wherein R'' has about 8 to about 18 carbon atoms, preferably about 8 to about 18 carbon atoms)
12 alkyl groups or alkenyl groups or alkaryl groups having about 5 to 14 carbons in the alkyl chain, and n is from O to about 6) and the preferred alkyl ethoxylates described above. Ratio of alcohol ethoxylate to glyceryl ether with 1:
Preference is given to mixtures of 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 polyglycosylated detergent surfactant to nonionic detergent surfactant is from about 10:1 to about 1:10, preferably from about 3:1 to about 1=3.

In addition, the detergent composition of the present invention has a detergent pill/-〇- to about 9
0%, preferably from about 5% to about 50%, more preferably from about 10% to about 35%. Builders of this type may be used, for example, with the formula % formula % (wherein 2 and y are at least about 6, the molar ratio of y to about 1.0 is from about 1.0 to about 0.5, and X is about 10
~about 264. ) is a crystalline aluminosilicate ion exchange material.

The amorphous aqueous aluminosilicate materials useful in the present invention have the empirical formula % (%), where % is sodium, potassium, ammonium, and 9 is substituted ammonium; , and y is 1), and the substance has C
aCO5 hardness has a magnesium ion exchange capacity of at least about 50 tons.

When the aluminosilicate ion-exchange material is in a water-use form and is crystalline, it has a water content of about 1θ to about 100% by weight.
and, when amorphous, commonly contain even larger amounts of water. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water within their crystalline matrix. Preferred crystalline aluminosilicate ion exchange materials have a crystalline aluminosilicate ion exchange material of about 0.1 to about 10
It is further characterized by grain size. #lI shaped materials are often even smaller, e.g., less than about 0.01 microns; more preferred ion exchange materials have particle sizes of about 0.2 microns to about 4 microns. The term refers to the average particle size of a given ion exchange material as determined by microscopic measurements using conventional analytical techniques, such as scanning electron microscopy. The crystalline aluminosilicate ion exchange material has a CaCO3 water hardness of at least about 200 mg equivalent per aluminosilicate, calculated on an anhydrous basis, to 9, generally about 300 m
g, + eq/g to about 352 mg...i, where the aluminosilicate ion exchange material has a calcium ion exchange capacity of at least about 2 g/Ca"/g/min/ Z/Iron aluminosilicate (anhydrous basis), generally within the range of about 2 g/gal/min/g/gal to about 6 g/gal/min/g/#ron based on calcium ion hardness The aluminosilicate of choice for builders exhibits a calcium ion exchange rate of at least about 4 Darens/gal/min/g/gal.

The amorphous alkinosilicate ion exchange material typically contains at least about 50mg-5q Ca0037g (12mg M
g+ng) and a Mg++ exchange rate of at least about 1 grain/gal/min/t/e a. Amorphous substances are Cu irradiated (1,54 A units)
No observable diffraction pattern is shown in the 9 cases examined by .

Arunnosilicate ion exchange materials useful in the practice of the present invention are commercially available.6 Aluminosilicates useful in the present invention can be crystalline or amorphous in structure, and are naturally occurring aluminosilicates. or synthetically derived.

A method for making arunnosilicate ion exchange materials is disclosed in US Pat. No. 3,985,669.

A preferred synthetic crystalline alkinosilicate ion exchange material useful in the present invention is named Zeolide) A% Zeolide P(B).
, and Zeolide X.

In particularly preferred embodiments, the crystalline alkinosilicate ion exchange material has the formula %, where X is about γ from about 1% to about I1%.

Other examples of detergent capilders are water-soluble neutral or alkaline salts.

Other useful water-soluble salts are, for example, compounds commonly known as detergent builder substances. Builders are generally various water-soluble alkali metal, ammonium or substituted ammonium phosphates, I-lyphosphates, phosphonates, di-lyphosphonates, carbonates, silicates, borates, I-lyhydroxysulfonates. , polyacetates, carboxylates, and polycarboxylates. Preference is given to the alkali metal salts of said substances, especially the sodium salts.

Specific examples of inorganic phosphates include sodium and potassium tripolyphosphates, pyrophosphates, about 6 to 21
These are polymeric metaphosphates and orthophosphates with a degree of polymerization of . ? Examples of the lyphosphonates pirgu are the sodium and potassium salts of ethylene-1,1-diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the ethane-1,
Sodium and potassium salts of 1,2-triphosphonic acid. Other phosphorus builder compounds are described in U.S. Patent No. 3.1.
59.581 specification, 3.213,030 specification, 3.422.021 specification, 3.422.13
Specification No. 7, Specification No. 3,400,176 and No. 3
．． No. 400,148.

Examples of phosphorus-free inorganic pilates are sodium and potassium carbonates, bicarbonates, sesquicarbonates, tetraborate hydrates, and StO, a molar ratio of 0 to alkali metal oxides.
．． 5 to about 4.0, preferably about 1.0 to about 2.4.

Water-soluble phosphorus-free organic builders useful in the present invention are, for example, alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, I-recarboxylate and 4-hydro-tetra-oxysulfonates. Examples of I-acetate builders and I-recarboxylic acid salts include sodium, potassium, lithium, and ammonium salts of ethylene cyano-tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene precarboxylic acid, and citric acid. salts and substituted ammonium salts.

A highly preferred I recarboxylate builder in the present invention is rice I! I patent 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 include sodium-cyclopentanetetracarboxylate, phloroglucinol trisulfonate, water-soluble polyacrylates (e.g.
000 to about 200,000), and copolymer salts of maleic anhydride and vinyl methyl ether or ethylene.

Other telicarboxylic acid salts suitable for use in the present invention include:
Polyacetal carboxylic acid salts as described in U.S. Pat. No. 4,144.226 and U.S. 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 1177 cetal carboxylic acid 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 surface-active. Add to the agent.

Another detersive capilder material useful in the present invention is "11 Pilgoo" disclosed in Belly Patent No. 798.8f1.
It is a composition. A specific example of a seed pill I-mixture of this type is:
3:1wt1ll metal of sodium carbonate and calcium carbonate with a particle size of 5 microns; 2:2 of sodium sesquicarbonate and calcium carbonate with a particle size of O,S
．． A 7:1 wt mixture and a 3:3:1 wt mixture of sodium carbonate, sodium aruninate and calcium oxide with a particle size of 5t Kron.

In addition to the above-mentioned essential detergent surfactants, the detergent compositions of the present invention may contain anionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof. from about 1 to about 15 organic surfactants selected from the group consisting of:
11, preferably about 2 to about 8 liters. Surfactants useful in the present invention include U.S. Pat.
and US Pat. No. 3,919,678. Also useful cationic surfactants are those described, for example, in US 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.

This is an alkali metal soap, e.g. about 8 to about 8 carbon atoms.
Sodium, potassium, ammonium, and alkylerammonium salts of higher fatty acids, preferably having from about 12 to about 18 carbon atoms, are produced by direct saponification of fats and oils or by neutralization of free fatty acids. can be done. Sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow soaps and coconut soaps, are particularly useful in combination with 0% semipolar or aty nonionic detergent surfactants. The preferred soaps mentioned above and below are at least partially unsaturated.

Unsaturated Soaps The unsaturated fatty acid soaps of the present invention preferably have from about 16 to about ρ 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 have cations that make them water soluble and dispersible as well as other anionic detergents and other anionic materials within the detergent compositions of the present invention. Suitable cations are, for example, sodium, potassium, ammonium, monoethanolammonium, jetanolammonium, triethanolammonium, tetramethylammonium and the like. Sodium ions are preferred, but ammonium and triethanolammonium cations are useful in liquid formulations.

An amount of at least about I% of unsaturated fatty acid soap is desirable to provide a significant reduction in sudsing and corrosion; preferred amounts of unsaturated fatty acid soap are from about 1 to about 151 G, preferably from about 1 to about 10-1 Most preferably from about 2 to about 5
It is 1G. Unsaturated fatty acid soaps can be added to cleaning solutions from about 15 ppm to about 200 ppm at recommended U.S. usage levels.
m, preferably in an amount of about 25 ppm to about 125 ppm, and then about 30 ppm for soda/liquid usage levels.
ppm to about 11000 ppm, preferably about 50 ppm
It is preferably present in an amount that will provide ˜500 ppm.

Since mono-, di-, and tri-unsaturated fatty acids are all essentially equivalent, a preferred source of unsaturated fatty acids is preferably to use primarily mono-unsaturated soaps to minimize the risk of malodor. For example, Bayley's Industrimorkai Oil eEnP Fats Q Pro! Shoes, 3rd shoe, Swarn, Interscience No! See Ritscher (1964).

Preferably the amount of saturated soap is kept as low as possible, preferably less than about 60, preferably about 5091, of gold soap.
Less than 20% is saturated soap. However, small amounts of saturated soap can be used. Tallow soap and gum oil can be used.

Useful synthetic anionic surfactants include, for example, water-soluble salts of organic sulfuric acid reaction products having in their molecular structure an alkyl group having from about 10 carbon atoms and a sulfonic acid ester group, preferably a sulfuric acid ester group. are alkali metal salts, ammonium salts and alkylolammonium salts "t'"
Al.

Synthetic anionic detergent surfactants of this type are desirable in amounts of about 1- to about 10- to increase the 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 of the Jin group include sodium alkyl sulfates and potassium alkyl sulfates, especially higher alcohols (
carbon number Cs""ts), for example those obtained by sulfating K produced by reducing the glycerides of tallow or coconut oil; and the alkyl groups in a straight-chain or branched configuration. Sodium and potassium alkylbenzene sulfonates having from about 9 to about 15 carbon atoms, such as U.S. Pat.
．． No. 220.099 and No. 2.477.383
It is of the type described in the specification. A linear straight-chain alkylbenzene sulfonate having an average number of carbon atoms in the alkyl group of about 11 to 13, abbreviated as C11-1. Li2 is particularly valuable.

Preferred anionic detergent surfactants are alkyl olethoxylate nalphates, especially those in which the alkyl has from about 10 carbon atoms to
about η, preferably about 12 to about 18, and the polyethoxylate chain contains about 1 to about 15 ethoxylate moieties, preferably about 1 to about 3 ethoxylate moieties. These anionic detergent surfactants are highly desirable in formulating heavy duty liquid laundry detergent compositions.

Other anionic surfactants are sodium alkylglyceride ether sulfonates, especially ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride P sulfonate and coconut oil fatty acid monoglyceride P sulfate. Sodium; sodium or potassium salt of alkylphenol ethyleneoxy P ether sulfate containing about 1 to about lθ units of ethyleneoxy P per molecule and having an alkyl group of about 8 to about 12 carbon atoms; Sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from 1 to about 1θ units of ethylene oxy r and in which the alkyl group has a carbon number of from 10 to about 10.

Other anionic surfactants useful in the present invention include, for example, water-soluble salts of esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester group; 2-acyloxy- having 2 to 9 carbon atoms in the group and about 9 to about 9 carbon atoms in the alkane moiety;
Water-soluble salt of alkane-1-sulfonic acid: Alkyl ether sulfate having about 10 to 10 carbon atoms and about 1 to 30 moles of ethyleneoxy P in the alkyl group; Water-soluble salt of olefin sulfonic acid having 12 to U carbon atoms and having 1 to 3 carbon atoms in the alkyl group and 8 to 2 carbon atoms in the alkane moiety! -alkyloxyalkanesulfonate.

Amphoteric surfactants are, for example, in which the aliphatic moiety is linear or branched and one of the aliphatic substituents has 8 to 1 carbon atoms.
derivatives of aliphatic secondary and tertiary amines or aliphatic heterocyclic secondary and tertiary amines having 8 and at least one aliphatic substituent containing an anionic water-solubilizing group Derivative amphoteric surfactants are, for example, derivatives of aliphatic quaternary ammonium compounds, phosphonium compounds, and sulfonium compounds in which one of the aliphatic substituents has a carbon number of 8 to 18.

Particularly preferred auxiliary surfactants in the present invention include, for example, linear alkylpenzene sulfonate having 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfate; coconut alkyl glyceryl ether sulfonate; an alkyl ether sulfate having a target of 14 to 18 and an average degree of ethoxylation of about 1 to 4;
Olefinsulfonates or ninefinsulfonates having 14 to 16 carbon atoms; and alkyldimethylammonium zolo/dansulfonates and alkyldimethylammonium and Pp xypronononesulfonates whose alkyl group has 14 to 18 carbon atoms.

Particular surfactants preferred for use in the present invention include, for example, C alkylderethoxylate, sodium sulfate, CI and 0. Alkyl? Liethoxylate potassium sulfate, C14-1. Alki l~
3 Ru I riethoxylate 1.3 monoethanolammonium sulfate, C alkyl I riethoxylate 14-15 t, ~3 jetanol ammonium sulfate and C14~
1. Alkyl polyethoxylate □~3 triethanolammonium sulfate; linear C11~, 3-alkylbenzenesulfonate sodium cl 1% 1 B alkyl 4
Tallow alcohol and evening drink 4
Sodium salt of sulfated condensate with moles of ethyleneoxy P; 3-(N.

N--) If Ru N- Coconut alkyl ammonio)
-2-7) jll okishi! Lenone-1-sulfone)
= s - () J e N-dimethyl-N-coconut alkyl ammonio)zolonon-1-sulfonate; 6-(N-)'decylbenzyl-N,N-dimethyl ammonio)-hequinanoate; and coconut It is tualkyldimethylamine oxide.

Technically established normal usage amount (i.e. θ ~ about 90 inches)
Other auxiliary components that can be incorporated into the compositions of the invention include, for example, solvents, bleaches, bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, fungicides. , PH adjusters (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), enzymes, enzyme stabilizers, perfumes, fabric softening ingredients, static electricity control agents, etc.

Fatty acid additive detergent surfactants useful in the present invention are, for example, those having the formula 11-NR72 [wherein R6 has a carbon number of about 7 to about 21 (preferably about 9 to about 21]).
about 17), and each R7 consists of hydrogen, C alkyl, 01-4 and sial 1-4 and -(02H40)xH, where X is about 1 to about 3 selected from the group].

Preferred ands are C ammonia and, 8-2G monoethanolammonicum, diethanola, and isozolo delta nora.

The special properties of the detergent surfactant combination of the present invention are:
Excellent compatibility with anionic fluorescent brighteners or optical brighteners. Nonionic surfactants, especially ethoxylated nonionic detergent surfactants, usually reduce the effectiveness of this type of brightener. When adding an alkyl I glycosi P surfactant, the effectiveness of the brightener against K11K is dramatically improved. Optical brightening rigidity: 0.01 to about 2-1, preferably about 0
% 1 to about 1- can be used.

Suitable brighteners include, for example:

Formula [where y is preferably Na, but compatible cations such as potassium, ammonium, substituted ammonium,
Examples include evamonoethanolammonium, jetanolammonium, and triethanolammonium! ! ; xa (wherein Ka is selected from H1 phenyl, 01-4 alkyl, or 08-4 hydroxyalkyl) can be morpholino, EP roxy; or mixtures thereof; and l is I
In the above structural formula, R and X are as follows.

King R -NHCH,CH5# -NHCI'l2C)10Hc)I.

-■C,H40He -N(CH3)CI(2CI(,OH#-NHC1H,
OCR.

=NHC2H,OH# -NHC,H40CH8# 0H ()IOCH convex), N-C) -NaQ/1O-NH-〇- Tomoichi's brightener is 4.4'-bis[(4"- Screw(
2”'-HiP4xethyl) a de no 6’ -(3””
-sulfenyl)amino-1',3',5'-)riazin-2N-yl)amino)-2,2'-stilbendisulfonic acid tetrasodium;
'ez' td)) lyazol-2-yl)-t-Xf disodium rupenesulfonate; 4.4'-bis((4'
-(2"'-Hyroxyethyla])-61-anilino-x't3't5'-triazin-2N-yl)amino)-ze2'-stylindisulfonic acid disodium; 4.4'-bis( <4'-(x"'-kl'tetraxyethoxy)-6'-anilino-1't3'e5#-triazin-2'-yl)amino) -L2'-Xf disodium lupendisulfonate a 4, 41 m bis(
4-phenyl-1t2t3-triazole-2-
4-(211-naphtho[1,tomi]triazol-2-yl)st,II+/disodium pen-2-2-sulfonate; disodium-4 ,4'-k"su(2-sulfostyryl)piphenyl; 4-(2H-6-sulfona7)
(1t2-d:l) lyazol-2-yl)stilbene-2-sulfonic acid disodium; and disodium-3,7-bis(2,4-dimethoxybenzazP)-
2,8-dibenzothiophene disulfonate-5,5-
It is dioxyr.

Other suitable brighteners are disclosed in US Pat. No. 3,537,993 and US Pat. No. 3,953,380.

The compositions of the invention can be prepared and used in various forms, such as solids, powders, granules, pastes, and liquids. Compositionally in water from 0.011 to about 1-1, preferably from about 0.05 to about 0.596, most preferably about O,
The composition can be used in modern laundry methods by preparing an aqueous solution containing OS*~0.25 and stirring the soiled fabric in the aqueous solution. The fabric is then rinsed and dried. When using this method,
Preferred compositions of the invention exhibit very good detergency on a variety of fabrics.

In a preferred embodiment, the laundry detergent, preferably an aqueous heavy duty liquid, is an alkyl-4! Ricoside detergent surfactant: 1% to about 20 g (preferably about 4 g)
(b) Adenoxy P detergent surfactant from about 1 to about 10% (preferably from about 2 to about 61
1); (e) water-soluble columnar soap of unsaturated fatty acids having carbon numbers from about 16 to about n;
(.) a water-soluble synthetic anionic detergent surfactant selected from the group consisting of IJ acetate, and mixtures thereof; Ots ~ about 10- (preferably about 09
! 1 to about S*); and preferably (f) balance water.

This type of detergent composition provides excellent cleaning power, does not unacceptably damage the washing machine, and by varying the amount and type of synthetic anionic detergent surfactant and the amount of unsaturated soap. Can be formulated to provide different lathers and leans.

Preferably, such formulations do not contain more than about 50% of conventional ethoxylated nonionic surfactants, preferably sodium, potassium, ammonium, and alkanol ammonium cations.

All -1 parts and proportions are by weight unless otherwise specified.

The following examples illustrate the compositions and methods of the invention.

Example ■ 500 - 9.415.4 2.9400 100
6.415.5 4.6300 200 6.317
．． 1 7.1200 300 4.417.6 7.1
100 400 2.716.3 7.1- 500-
0.315.6 6.8 Test Conditions: 95°F (approx.
．． (0°C) water and mini-washing machine As can be seen from the above results, alkyl polyglycoside surfactants have unexpected problems in cleaning I-reesters.

General K.

Alkyl polyglycosides are considered an alternative to non-ionic surfactants, but surprisingly they are particularly suited for cleaning/cleaning relatively hydrophobic surfaces. Use in conjunction with to achieve the best washing results. The alkyl polyglycosides in these examples were derived from glucose. Other alkyl glycosylation P as mentioned above
Similar results are obtained when .

Example 1 (Non-built mixed metal) 300 ppm OPP theory 10240 ppm
60 ppm 20180 ppm
120 PPDI 270 ppm
300 ppm 17 Same conditions as Example I - As shown from the data above, alkyl polyglycoside surfactants generally give poor results when cleaning relatively hydrophobic surfaces; Mixtures of P and nonionic surfactants provide a synergistic effect.

Example■ Maintenance of whiteness (redeposition test) 300ppm 0 73 68 362
40ppm 60 74 70 391
80ppm 120 79 73 406
0ppm 240 73 73 390
The 300 71 73 39 solution was unbuilt and used under the same conditions as Examples 1 and 1. The grade is the average of the two types of stains.

The above data indicate that there is a synergistic improvement in cotton re-deposition for the one surfactant mixture.

Example ■ C12~15 Cl2-v13 / 7 from ricotton Ruki) b $ 1) Ahecapori
Removal of menstrual blood stains 300 ppm
0 50240 ppm
60'60'180pp
m 120 6360 p
pm+ 240 700
PP! 11 300 63
Same test conditions as in the previous example for the non-built solution As can be seen from the data above, the unexpectedly poor ipotency of the alkyl polyglycosides against this stain can be improved by the addition of a nonionic surfactant, depending on the ratio used. improvement and/or synergistic improvement.

Example■ CI2~15A "Ki"Polygri""Todo-3" 12,7 21,2 26
．． 3C11-I m alkyl I ethoxylate6. .

Ratio 1:1” 4 to Nitri I Sodium Lyphosphate (STP) 251G
and 109 g of sodium carbonate as a builder, and the total composition was used in an amount of 1200 ppm.

Test conditions: 60″F (approximately 1s
, 6° C.) water and lx washer.As can be seen from the data above, the mixed surfactant system of the present invention is also less effective across a variety of fabrics than conventional anionic surfactants. gives excellent clay removal properties.

Example■ Glycoside Ethoxyle 2-3 Luaquinoxyl dimethylamine Pmine oxide polyester 59,0 55.
2 Removal rate (Feed dirt 9 Motor oil 3o37 Chiyocolate syrup 9393 Gras + s) 67
73 Bacon Grease 5753 Menstrual Blood Stains 8373 Snow Arms 5067 T Shirt
7877 Polyester 8685 Polyester 4639 The surfactant mixture was prepared at 13 of the formulation, and the builder was sodium nitrilotriacetate (18%), and the test conditions were 2100 ppm of the composition, 95〒 (approximately 33
．． 0'C) and a mixed hardness of 6 grains.

Pan P8U is a panel score unit (Pan@18eor
・Units), and professional graders specify numerical values on the basis of 0 for no difference; 1 for a difference; 2 for a clear difference.

Examples ■ Non-built HDL performance Inventive non-built commercial heavy duty liquid detergent composition (HDL) Dirty motor oil +0.3 +0.4 Bacon grease +1.0 +0.8 Gravy +1.4 +0.2 Getsty sauce +0.3 +0.
9 glasses +1.7 +1.5
Ch M': Root Syrup -0.4+0.6 Test Conditions: 450 ppm of active ingredient, 95'F water and mini washing machine with a mixed hardness of 6 grains Composition of the Invention: Ratio 1:1 Ctz~1. Alkyl I
Liethoxylate S/C 1% 15 alkyl polyglycosylation P)-3 Example ■ Part C12-0. Alkyl polyglycoside 2~. 1
3.3012-13 alkyl polyester F xylate. ,s
13.3 Sodium tri-I lyphosphate
12.0Na2Co313.3 Polyacetaldehyde Detergent Pill/-28,8 Anionic Brightener” 1.0 Bone:♂S(anilino-hydroxyethylmethyla5notriaferamino)stilbene disulfonate (sodium salt) CI )-1K alkyl polyglycosy et al./Neodo 79 111 22 g7
-Le 23-6.5 Technically significant difference: HVI/U = 2; Soler 2A = 2
; and F=1 Example ■ @ T-shirt redeposition and brightness/whitening test The following results obtained using a non-built mixture of surfactants demonstrate that anion enhancement in the presence of nonionic surfactants It clearly shows the effectiveness of alkyl polyglycosylation P in improving the effectiveness of whitening agents. The data clearly show that at least about φ- of the surfactant system should be alkylpolyglycosy P; a HWU of 5-6 is a substantial improvement.

Non-r light 1 100 0 120 110 1080
20 122 113 960
40 118 109
920 80 119 92
270 100 118 91
27 Dish: Testing the effect of brightener Conditions: Mini washing machine, mixed hardness 6 grains, 100″F (approx. 37.8°C), 1 cycle, total surfactant 300ppm
, Example ■ Brightener 15 ppm Example

100 0 25.9 2.8 1.2
80 20 27.0 3.3 2.5
60 40 28.8 5.2 s,
a20 80 29.1 5.0 4.
20 100 28.1 2.2 2.
1 condition: mini washing machine, non-built, mixed hardness 6 grains, t
oo'F (approximately 37.8°C), total component 300 ppm
As can be seen from the above data, the mixture is clearly superior. An IWU of 1-2 is a substantial difference in this test.

Example: Rich alkyl polygluco 7P improves the performance of oil-soluble (low HLB) nonionic detergent surfactants.

(HWU,) (PSU) 100 0 23.9 0.8 0.2
802024゜9 -0.1 0.560
40 24.6-11.9 0.620
80 8.8-21.0 -0.40 10
0 -0.8-27.8 -0.9 Conditions: Mini washer, unbuilt, mixed hardness 6 grains, 100'F (approximately 3
7.8℃), 300 ppm (LSD for clay)
-1,2HWU, LSD for faciml 5 oil, s=0
．． 4 PSU) Clearly, the above results show an improvement from mixing conventional (Etkinized) nonionic detergent surfactants with alkylpolyglycosy P, the mixture giving a substantial improvement in detergency.

Example 1 The combination of alkyl 4liglucosiP with a semipolar nonionic and (1 or Fi)a detergent surfactant is compatible with unsaturated soaps (eo groanatlbl), but not with saturated soaps. do not.

Formulation 234B Sodium mutarate -2,2--Sodium stearate--4,4--U^ Coconut dietano 0.13 0,13 0.25
0.130.26-Lua nitrilotriacetic acid 1B, 2 18,2 18.2
18.2 18.2 Triku^ Sodium Arashi L8 2.8 2.8 2.8
L8 Toluenesulfonic acid 2 2. 2 2
2 Sodium Ethyl Alcohol 33333 Water Residual Remaining Remaining Remaining! ll1
It foamed less than 11 compositions 1-3 and Company 5 formulation 4, and was compatible with washing machine surfaces (less corrosion). Composition 3 formed unsightly soap scum in the rinse water despite the presence of substances known to inhibit sawm formation.

It is clear that Composition 3 produces a viscous gel rather than a free-flowing clear liquid, and that there should be no substantial excess of saturated soap compared to unsaturated soap.0 Soap is unsaturated soap. Must be at least about 4016.

The performance of these compositions if the total free fatty alcohols having about 8 to about 9 carbon atoms is less than about 511, preferably less than about 2, and most preferably less than about 1. I hope that it will be improved! has been discovered.

Claims (1)

[Scope of Claims] 1. Solidified RO (RO), (Z) has a carbon number of about 8 to about 18'
each R1 has 2 to about 4 carbon atoms, and y is 0 to about 12; and %2 has 5 carbon atoms or i
alkyl polysaccharide detergent surfactants of from about 1 to about 904, (Machii ionic detergent surfactants from about 1 to about 10) 904, and tcJ washability builder 0 to about 90 (LAJ vs. (BJ)
from about 1=lO to about 10:l). 2. The component factor is the formula R0(CnH2,O), (glycosyl)(in the formula, cod s
-rlkyl, alkylphenyl, hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof, t is from 0 to about 5, the glycosyl moiety is derived from glucose, and X is about 1-z
3). 3. The composition of claim 2*, wherein the nonionic surfactant has an HLB Y of about 5 to about 17. 4. The nonionic surfactant has the formula % formula % (where R is a primary or secondary alkyl chain of about 8 to about 8 carbon atoms, and n is an average of about 2 to about 12 carbon atoms) )
A composition according to claim 3 having a composition comprising: 5. The composition of claim 4, wherein the ratio of LAJ to BJ is from about 1:3 to about 3=1. 6. The nonionic surfactant has an HLB of from about 5 to about 17. A composition according to claim 1'g4. 7. The nonionic surfactant has the formula %, where R is a primary or secondary alkyl chain of about 8 to about 1 carbon atoms, and 1 has an average of about 2 to about 12 carbon atoms. A composition according to claim 6. 8. x is about 1! - to about 3. 9. Hydrated zeolides A, A patent selected from the group consisting of ammonium tripolyphosphates, pyrophosphates, carbonates, silicates, borates, molecular metaphosphates, nitrilotriacetates, citrates, and polyacetal carboxylates A composition according to claim 1. 10. Mixed hydrophobic and hydrophilic fabric Y, tAl2RO (
R'0) (Z) (wherein R is alkyl, hydroxyalkyl, alkylphenyl, hydroxyalkylphenyl, alkylbenzyl, or a mixture thereof, wherein the alkyl group has about 8 to about 18 carbon atoms) ];
Each R1 has 2 to about 4 carbon atoms, and y is 0 to about 12
and each 2 is a moiety derived from a reducing sugar having 5 or 6 carbon atoms, and X is about 1Σ~fJlO
] Alkyl polysaccharide detergent surfactant from about 1 to about 90
96, (BJ non-ionic detergent surfactant from about 11 to about 100% and 10 from detergent surfactant to about 904 (from tBJ
a ratio of from about 1:1 O to about 10:1).