JP3007154B2 - Detergent composition comprising a polyhydroxyfatty acid amide surfactant and a polymeric dispersant - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a detergent composition comprising a detergent for cleaning and a dispersant. In particular, the present invention relates to detergent compositions comprising a detergent surfactant system incorporating a polyhydroxy fatty acid amide surfactant.

BACKGROUND OF THE INVENTION Detergent compositions used for cleaning purposes, such as washing laundry, contain a wide variety of surfactants, auxiliary cleaning components specifically adapted to the type of cleaning required, and processing and / or aesthetics. Other components added for purpose have generally been utilized.

One of the various auxiliary cleaning ingredients commonly added to detergent compositions used in laundry and other textile cleaning applications are polymeric dispersants such as polycarboxylate dispersants and polyethylene glycol dispersants,
This is for assisting the removal of particulate stains from cloth, woven fabric, and the like. These polymeric dispersants are used in combination with detersive surfactants and other desired detergent additives known in the art.

In recent years, many of the most commonly used surfactants have been derived from petroleum-based feedstocks. These include, most notably, surfactants, such as linear alkyl benzene sulfonates, that can provide excellent overall cleaning performance over a wide variety of conditions. Significantly, this linear alkylbenzene sulfonate can provide excellent grease and oil cleaning without the need for high wash temperatures or concentrations, and can be used instead to clean grease and oil Can be at high wash temperatures and / or
Or, it differs from conventional nonionic surfactants that require high wash concentrations. While these surfactants have provided excellent results, it is desirable to reduce the amount of surfactant material in petroleum feed-based compositions while retaining comparable overall cleaning performance. It is.

Also, conventional methods of improving grease and oil cleaning have a negative effect on particulate soil removal and vice versa, so detergent formulators have traditionally removed particulate soil with good grease and oil cleaning capabilities. There is a problem of providing a detergent composition that can be used. Other surfactants that can interfere with particulate soil removal performance include alkyl ethoxylates and alkylphenol ethoxylates.

Certain polyhydroxy fatty acid amide surfactants are
Over a wide range of washing conditions, especially other anionic and / or
It has now been found that when combined with non-ionic surfactants, it can provide excellent overall cleaning performance, including excellent grease and oil cleaning performance. In addition, detergent compositions comprising these polyhydroxy fatty acid amides in combination with one or more polymeric dispersants can also provide excellent particulate mud removal.

The practice of the present invention provides a detergent composition comprising certain polymeric hydroxyfatty acid amides, a desired anionic or other nonionic surfactant, and a polymeric polycarboxylate dispersant.

BACKGROUND ART Various polyhydroxy fatty acid amides have been described in the art. N-acyl and N-methylglucamide are described, for example, in JW Goody, MA Marcus, E. Chin and P.
"The Thermotropic Liquid-Crystalline P" by L. Finn
roperties of Some Straight Chain Carbohydrate Amph
iphiles ", Liquid Crystals, 1988, Volume 3, Issue 11, 156
9-1581, and A. Muller-Fahrnow, V. Zabel, M. Steif
a and R. Hilgenfeld, “Molecular and Crystal Struc
ture of a Nonionic Detergent: Nonanoyl-N-methylglucamide ", J. Chem. Soc. Chem. C
ommun., 1986, 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has recently received considerable attention for use in biochemistry, for example, in the dissociation of biological membranes. For example, EKHildreth, "ND-Cluco
-N-methyl-alkanamide Compounds, a New Class of
Non-Ionic Detergents For Membrane Biochemistry, "B
See iochem. J. (1982), 207, 363-366.

The use of N-alkylglucamides in detergent compositions is also discussed. U.S. Patent No. 2,965,576 issued to ER Wilson on December 20, 1960 and February 18, 1959.
British Patent No. 809,060, issued to Thomas Hedley & Co., Ltd., issued today, adds an anionic surfactant and a foam enhancer at low temperatures. And a certain amide surfactant such as N-methylglucamide. These compounds contain the N-acyl group of higher linear fatty acids having 10 to 14 carbon atoms.
These compositions may also include auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. Also, fluorescent dyes,
It is also generally indicated that additional ingredients, such as bleaches, fragrances, and the like, to impart desirable properties to the composition can be incorporated into the composition.

U.S. Patent No. 2,703,798, issued March 8, 1955 to AM Schwartz, relates to an aqueous detergent composition comprising a condensation reaction product of an N-alkylglucamine and an aliphatic ester of a fatty acid. It is said that the product of this reaction can be used in aqueous detergent compositions without further purification. It is also known to prepare sulfated acylated glucamines as disclosed in U.S. Pat. No. 2,717,894 issued to AM Schwartz on September 13, 1955.

PCT International Application No. The invention relates to amphiphilic compounds containing polyhydroxyaliphatic groups which are said to be useful in biochemistry for solubilizing tissue samples and for the preparation of liposomes, for use in biochemistry as emulsifiers and dispersants. This disclosure includes the formula R'CON
(R) A compound having CH ₂ R ″ and R ″ CON (R) R ′, wherein R is hydrogen or an organic group, and R ′ is an aliphatic hydrocarbon group having at least 3 carbon atoms. ,
R "is an aldose residue.

EP 0285768 published on October 12, 1988 by H. Kelkenberg et al.
It relates to the use of polyhydroxyalkyl fatty acid amides as thickeners. Formula R ₁ C (O) N (X) R ₂ (where R ₁ is C
₁ -C ₁₇ (preferably C ₇ -C ₁₇₎ alkyl, R ₂ is hydrogen, (preferably _{C 1 ~C 6) C 1 ~C} 18 alkyl or alkylene oxide, X is 4-7 amino Amides which are polyhydroxyalkyls having carbon atoms), such as N-methyl, coconut fatty acid glucamide.
The thickening properties of the amides are shown to be particularly useful for liquid surfactant systems containing paraffin sulfonates, while aqueous surfactant systems include alkylaryl sulfonates, olefin sulfonates, sulfosuccinic half ester salts and fatty alcohol ethers. Other anionic surfactants such as sulfonates and nonionic surfactants such as fatty alcohol polyglycol esters, polypropylene oxide-polyethylene oxide mixed polymers and the like can be included. Paraffin sulfonate
A shampoo formulation of / N-methyl coconut oil fatty acid glucamide / nonionic surfactant is exemplified. In addition to the thickening attribute, N-polyhydroxyalkyl fatty acid amides are said to have excellent skin tolerance attributes.

US Patent issued to Boettner et al. On May 2, 1961
No. 2,982,737 discloses urea, sodium lauryl sulfate anionic surfactant, and N-alkylglucamides selected from N-methyl, N-sorbicyl lauramide and N-methyl, N-sorbicyl myristamide. The present invention relates to a detergent bar containing an ionic surfactant.

Other glucamide surfactants are described, for example, in HWEckert et al., German Patent No. 2,226,872, issued December 20, 1973.
Which comprises one or more surfactants and a builder salt selected from a polymeric phosphate, a sequestering agent and a washing alkali, having the formula R ₁ C (O) N (R ₂ ) CH ₂ (CHOH) _n —CH ₂ OH wherein R ₁ is C ₁ -C ₃ alkyl, R ₂ is C ₁₀ -C ₂₂ alkyl, and n is 3 or No. 4).

U.S. Patent No. 3,654,166, issued to HWEckert et al. On April 4, 1972, discloses at least one surfactant selected from the group of anionic, zwitterionic and non-ionic surfactants, Formula R ₁ N as fabric softener
(Z) C (O) R _{2 wherein} R ₁ is C ₁₀ -C ₂₂ alkyl, R ₂ is
A C ₇ -C ₂₁ alkyl, R ₁ and R ₂ has a 23 to 39 carbon atoms in total, Z is polyhydroxyalkyl,
This can be a _{-CH 2 (CHOH) m CH 2} OH, where m
Is 3 or 4), and a N-acyl, N-alkyl polyhydroxyalkyl compound having the formula:

U.S. Pat. No. 4,021,539, issued to H. Moeller et al. On May 3, 1977, describes a compound of the formula R ₁ N (R) CH (CHOH) _m R _{2 where} R ₁ is H, lower alkyl, hydroxy - lower alkyl or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R ₁ except that it is not possible R and R ₁ is H together, R ₂ is CH ₂ OH or COOH The present invention relates to cosmetic compositions for the treatment of skin comprising N-polyhydroxyalkyl-amines, including compounds having the formula:

Commercial Solvents Corporation on April 26, 1963
No. 1,360,018, assigned to
Wherein _{RC (O) N (R 1} ) G ( wherein, R is a carboxylic acid functionality having at least seven carbon atoms, R ₁ is hydrogen or a lower alkyl group, G is at least 5 carbons (Which is glycitol with atoms) is added to form a solution of formaldehyde stabilized against polymerization.

A. Heins, German Patent 1,261,8, issued February 29, 1968
No. 61 discloses a compound of the formula N (R) (R ₁ ) (R ₂ ) wherein R is a sugar residue of glucamine and R ₁ is a C ₁₀ -C ₂₀
An alkyl group and R ₂ is a C ₁ -C ₅ acyl group) and a glucamine derivative useful as a wetting and dispersing agent.

British Patent No. 745,036, issued February 15, 1956 and assigned to Atlas Powder Company, is said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, fabric softeners and the like. Heterocyclic amides and carboxylic acid esters thereof. These compounds have the formula N (R) (R ₁ ) C (O) R _{2 where} R is the residue of anhydrous hexanepentol or a carboxylic acid ester thereof, and R ₁ is a monovalent hydrocarbon And -C (O) R2 is an acyl group of a carboxylic acid having ₂ to 25 carbon atoms.

US Patent issued to DTHooker on April 4, 1967
No. 3,312,627 discloses a lithium soap of a certain fatty acid which is substantially free of anionic detergents and alkaline builder materials, and a certain propylene oxide-ethylenediamine-ethylene oxide condensate, propylene oxide-propylene glycol-ethylene oxide A nonionic surfactant selected from condensates and polymerized ethylene glycol, and having the formula RC (O) NR ¹ (R ² ) wherein RC (O) contains from about 10 to about 14 carbon atoms. Has, R ¹
And R ² are each H or a C ₁ -C ₆ alkyl group, wherein the total number of carbon atoms in said alkyl group is 2 to about 7 and the total number of hydroxyl groups as substituents is 2 to about 6) A solid cosmetic bar also comprising a nonionic foaming component that can include a polyhydroxyamide having the formula: Substantially similar disclosures will be made by DTHook on April 4, 1967.
See also U.S. Pat. No. 3,312,626 issued to er.

SUMMARY OF THE INVENTION The present invention provides a detergent composition, comprising: Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is at least 3 At least about 1% by weight (preferably, about 3% to about 50%) of a polyhydroxyfatty acid amide compound having a linear hydrocarbyl chain having a hydroxyl (which is a polyhydroxyhydrocarbyl) or an alkoxylated derivative thereof; 1 to 50% of a detergent surfactant other than the polyhydroxyfatty acid amide selected from anionic and nonionic detergent surfactants, and (c) a polymer dispersant, The weight ratio of the agent to the polyhydroxy fatty acid amide is from about 10: 1 to about 1:
10. A detergent composition comprising at least about 0.5% and at least about 10%.

The polymeric dispersants herein include polycarboxylates and polyethylene grease polymers.

The present invention further provides for the performance of a detergent comprising a polymeric dispersant and a detersive surfactant by additionally incorporating at least about 1% by weight of the above polyhydroxy fatty acid amide surfactant into the detergent composition. Provide a way to improve.

The present invention further provides a method for treating a substrate, such as fibers, fabrics, hard surfaces, skin, etc., with one or more anionic, non-ionic or cationic surfactants, and at least about 0.5% by weight of a polymeric dispersant. A method is provided for cleaning said substrate by contacting with a detergent composition comprising at least 1% of a polyhydroxy fatty acid amide.

DETAILED DESCRIPTION OF THE INVENTION Polyhydroxyfatty acid amide surfactant The compositions of the present invention comprise at least about 1%, typically about 3% to about 50%, preferably about 3%, of a polyhydroxyfatty acid amide surfactant as described below. From about 3% to about 30%. The polyhydroxy fatty acid amide surfactant of the present invention comprises a compound having a structural formula.

(I) Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or
C ₂ alkyl, most preferably C ₁ alkyl (i.e., methyl), R ² is C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl,
Or a mixture thereof, wherein Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain, wherein at least three hydroxyl groups are directly attached to this chain, or an alkoxylated derivative thereof (preferably ethoxylated). Or a propoxylated derivative]] Z is preferably derived from a reducing sugar in a reductive amination reaction, and more preferably Z is glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used in the same manner as the individual sugars described above. These corn syrups can provide a mixture of the sugar components of Z. It should be understood that this is not intended to exclude other suitable ingredients. Z is preferably -CH ₂ - _{(CHOH) n
-CH 2 OH, -CH (CH 2} OH) - (CHOH) n-1 -CH 2 OH, -CH 2
— (CHOH) ₂ (CHOR ′) (CHOH) —CH ₂ OH, where n is an integer from 3 to 5 and R ′ is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Selected from the group consisting of: Most preferably, glycityls (where, n is 4), particularly -CH ₂ - (CHO
_H) is a 4 -CH ₂ OH.

In the formula (I), R ¹ is, for example, N-methyl, N-
It can be ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² —CO—N <can be, for example, cocoamide, stearamide, oleamide, rauramide, myristamide, capricamide, palmitoamide, tallowamide and the like.

Z is 1-deoxyglycityl, 2-deoxyfrucchityl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotriothytyl, or the like. There can be.

Methods for producing polyhydroxy fatty acid amides are known in the art. Usually, they react an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkylpolyhydroxyamine and then convert the N-alkylpolyhydroxyamine to a fatty acid in a condensation / amidation step. It can be prepared by reacting with an aliphatic ester or triglyceride to form an N-alkyl, N-polyhydroxy fatty acid amide product. Methods for producing compositions containing polyhydroxy fatty acid amides are described, for example, on February 18, 1959, by Thomas Hedle and Company, Limited, Thomas Hedle.
y & Co., Ltd.), UK Patent No. 809,060.
No. 2,965,576 issued to ERWilson on December 20, 1960, and US Pat.
No. 2,703,798 issued to nthony M. Schwartz and U.S. Pat.No. 1,985,424 issued to Piggott on December 25, 1934, which are incorporated herein by reference. It is cited as part of the disclosure of the specification.

Wherein the glycityl moiety is derived from glucose and the N-alkyl or N-hydroxyalkyl function is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl;
In one method of preparing -alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides, the products are trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapolyphosphate, Potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, base N-alkyl- or N-hydroxy-glucamine in the presence of a catalyst selected from the group consisting of basic sodium silicate, basic potassium silicate, basic sodium aluminosilicate and basic potassium aluminosilicate, and mixtures thereof. The fatty acid methyl ester Ether is prepared by reacting a fatty acid ester selected from fatty acid ethyl esters and fatty triglycerides. The amount of catalyst is N-
It is preferably about 0.5 mol% to about 50 mol%, more preferably about 2.0 mol% to about 10 mol%, based on the number of moles of the alkyl or N-hydroxyalkyl-glucamine.
The reaction is preferably at about 138 ° C to about 170 ° C, typically about 20 ° C.
Perform for ~ 90 minutes. When triglycerides are used in the reaction mixture as a source of fatty acid esters, they are selected from saturated fatty alcohol polyethoxylates, alkyl polyglycoside linear glycamide surfactants and mixtures thereof, in terms of weight percent of the total reaction mixture. It is carried out with from about 1 to about 10% by weight of a phase transfer agent.

 Preferably, this step is performed as follows.

(A) preheating the fatty acid ester to about 138 ° C. to about 170 ° C .; (b) adding the N-alkyl or N-hydroxyalkylglucamine to the heated fatty acid ester to form a two-phase liquid / liquid mixture. (C) mixing the catalyst with the reaction mixture, and (d) stirring for a predetermined reaction time.

If the fatty acid ester is triglyceride,
It is also preferred that the preformed linear N-alkyl / N-hydroxyalkyl, N-linear glucosyl fatty acid amide product be added to the reaction mixture as a phase transfer agent by about 2% to about 20% by weight of the reactants. . This gives the reaction a boost, thereby increasing the reaction rate. Detailed experimental procedures are described in the experimental section below.

The polyhydroxy "fatty acid" amide materials used herein also benefit detergent detergents because they can be prepared entirely or initially from natural, renewable, non-petrochemical feedstocks and are degradable. provide. They are also less toxic to aquatic organisms.

It is recognized that the methods used to produce them typically produce large amounts of non-volatile by-products, such as ester amides and cyclic polyhydroxy fatty acid amides, along with the polyhydroxy fatty acid amides of formula (I). Should. The level of these by-products will depend on the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent composition of the present invention comprises:
The polyhydroxyfatty acid amide-containing composition added to the detergent is provided in a form comprising less than about 10%, preferably less than about 4%, of cyclic polyhydroxyfatty acid amide. The above preferred steps are advantageous in that by-products, such as cyclic amide by-products, are purified to a much lower level.

Additional Detergent Surfactants In addition to the polyhydroxy fatty acid amide, the composition can include other detersive surfactants. Typically, the composition will contain from 1% to about 45%, preferably about 5%, of other surfactants.
To about 40%, more typically about 5% to about 25% of other surfactants.
%including. These additional surfactants can include any surfactant useful for cleaning purposes. These include anionic and nonionic surfactants, as well as other surfactants such as cationic, zwitterionic and amphoteric surfactants.

The present invention is particularly advantageous when the detergent composition comprises anionic surfactants such as alkyl benzene sulfonates, alkyl sulfates, alkyl ester sulfonates and alkyl alkoxylated sulfonates that are relatively sensitive to wash water hardness. Other surfactants, especially commonly used ones such as alkyl ethoxylates, alkyl polyglucosides and paraffin sulfonates can also be incorporated. Generally, polyhydroxy fatty acid amides can be used to help formulate detergent compositions containing these surfactants.

Alkyl ester sulfonate surfactant The alkyl ester sulfonate surfactant of the present invention includes "Journal of the American Oil Chemists Societ
y "52 vol (1975), there is a linear esters of C ₈ -C ₂₀ carboxylic acids which are sulfonated with gaseous SO ₃ according to pp. 323-329 (i.e., fatty acids). Suitable starting materials Include natural fatty substances derived from beef tallow, coconut oil, coconut oil, etc. Alkyl ester sulfonate surfactants particularly preferred for laundry applications have the structural formula Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl or a combination thereof,
M is a cation that forms a water-soluble salt with the alkyl ester sulfonate). Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted such as methyl-, dimethyl-, trimethyl- and quaternary ammonium cations, for example, tetramethyl-ammonium and dimethylpiperidinium. There are ammonium cations and cations derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl,
R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates,
R ³ is C ₁₄ -C ₁₆ alkyl.

Alkyl sulfate surfactant The alkyl sulfate surfactant of the present invention has the formula ROSO
During ₃ M [wherein, R is preferably a C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or cations, such as alkali metal cations (eg, sodium, potassium, lithium), substituted or unsubstituted ammonium cations, such as methyl-, dimethyl- and trimethyl-ammonium, and quaternary ammonium cations, such as tetramethyl-ammonium and dimethylpi And cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, etc.]. Typically, _C12-16 alkyl chains are used at low wash temperatures (eg, about 50
C below) and _C16-18 alkyl chains are preferred for high wash temperatures (e.g., above about 50C).

Alkyl alkoxylated sulfate surfactants The alkyl alkoxylated sulfate surfactants of the present invention have the formula RO (A) _m SO ₃ M wherein R is an unsubstituted C ₁₀ -C
Hydroxyalkyl group having ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl component, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is ethoxy or propoxy units And m is greater than 0, typically about
0.5 to about 6, more preferably about 0.5 to about 3,
M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, calcium,
Such as magnesium), ammonium or substituted ammonium cations]. Alkyl ethoxylated sulfates as well as alkyl propoxy sulfates are also contemplated in the present invention. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium, dimethylpiperidinium, and alkanols such as monoethanolamine, diethanolamine and triethanolamine. Cations derived from amines, and mixtures thereof. Typical surfactants, C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, and C _{12 to} C ₁₈
Alkyl polyethoxylate (4.0) sulfate, wherein M is advantageously selected from sodium and potassium.

Other Anionic Surfactants Other anionic surfactants used for detergents can also be incorporated into the compositions of the present invention. These can include salts (e.g., sodium, potassium, ammonium and mono-, - di - and triethanolamine salts), C ₉
Linear alkyl benzene sulphonate -C _20, C ₈ primary or secondary alkane sulfonates of ~C _22, C ₈ ~C ₂₄ olefin sulfonates, UK alkaline earth metal citrates by the method described in Patent No. 1,082,179 Sulfonated polycarboxylic acids, alkyl glycerol sulfonates, aliphatic acyl glycerol sulfates, aliphatic oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, acyl isatio Isethionates such as methacrylates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates (specifically saturated and Beauty C ₁₂ -C ₁₈ monoesters of unsaturated), C ₆ -C ₁₄ diesters of saturated and unsaturated on the sulfosuccinate diester (specifically), N- acyl sarcosinates, sulfates of alkylpolyglucoside alkylpolysaccharides sulfates such as (non-sulfated compound nonionic show later), branched primary alkyl sulfates of the formula _{RO (CH 2 CH 2 O)} k -CH 2 COO - M + ( wherein , R
Is C ₈ -C ₂₂ alkyl, k is an integer of 0,
M is a soluble salt forming cation) and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids derived from or contained in tall oil. Other examples are Surface Active Agents and Deterg
ents "(Volumes I and II, Schwartz, Perry and Berch
Author). Such various surfactants are described in U.S. Pat. No. 3,929,678 issued Dec. 30, 1975 to Laughlin et al., Column 23, line 58 to column 29, line 23 (herein incorporated by reference). (Cited in the specification).

Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are described in U.S. Pat. No. 3,929,678 issued Dec. 30, 1975 to Laughlin et al., Column 13, line 14 to column 16, line 6 (Cited herein as part of that disclosure). Typical non-limiting types of useful nonionic surfactants are shown below.

1. Polyethylene, polypropylene and polybutylene oxide condensation products of alkylphenols. Usually, polyethylene oxide condensation products are preferred. These compounds include linear or branched condensation products of alkylphenols having 6 to about 12 carbon atoms with alkylene oxides. In a preferred embodiment, the ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 from GAF Corporation and Rohm & Haas Comp
Triton ^™ X-45, X-114, X-1 sold by any
00 and X-102. These compounds are commonly called alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

2. Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol is
It can be straight or branched and either primary or secondary and generally has from about 8 to about 22 carbon atoms. Particularly preferred is the condensation product of an alcohol having an alkyl group having about 10 to about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of such commercially available nonionic surfactants include Ter Car from Union Carbide Corporation.
gitol ^™ 15-S-9 (condensation product of a linear secondary alcohol of C _{11 to} C ₁₅ and 9 mol of ethylene oxide), Tergitol
^TM 24-L-6NMW (a condensation product of a primary alcohol with 6 mol of ethylene oxide of C ₁₂ -C _14, the molecular weight distribution is narrow), Neodol has been released from the Shell Chemical Company ^TM 45-9 ( C ₁₄ linear alcohol with condensation products of ethylene oxide 9 mole ~C _15), Neodol ^TM 23-6.5
(C ₁₂ linear alcohol with condensation products of ethylene oxide 6.5 moles of ~C _13), Neodol ^TM 45-7 (the condensation product of linear alcohol with 7 mol ethylene oxide of C ₁₄ ~C _15), Neodol ^TM 45 4 (the condensation product of linear alcohols with ethylene oxide 4 mol of C ₁₄ -C ₁₅₎ and the
Kyro ^TM E released by Procter & Gamble Company
OB (C ₁₃ ~C ₁₅ condensation products of alcohols with 9 moles of ethylene oxide) has. These surfactants are commonly called alkyl ethoxylates.

3. Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is insoluble in water. The addition of polyoxyethylene residues in this hydrophobic moiety increases the water solubility of the molecule as a whole and the liquid properties of the product are such that the polyoxyethylene content is about 50% of the total weight of the condensation product. Is maintained until a point corresponding to condensation with up to about 40 moles of ethylene oxide.
Examples of such compounds include some of the commercially available Pluronic ^™ surfactants sold by BASF.

4. Condensation products of ethylene oxide with products obtained by the reaction of propylene oxide and ethylenediamine. The hydrophobic residues of these products consist of the reaction product of ethylene diamine with an excess of propylene oxide, and usually have a molecular weight of about 2500 to about 3000. This hydrophobic residue is converted to a polyoxyethylene of about 40% by weight.
To about 80% by weight and to a molecular weight of about 5,000 to about 11,000 with ethylene oxide. Examples of this type of nonionic surfactant include some of the commercially available Tetronic ^™ compounds marketed by BASF.

5. Semi-polar nonionic surfactants are a special class of nonionic surfactants, one alkyl residue having about 10 to about 8 carbon atoms and about 1 to about 3 carbon atoms. A water-soluble amine oxide comprising two residues selected from the group consisting of an alkyl group having two carbon atoms and a hydroxyalkyl group, one alkyl residue having about 10 to about 18 carbon atoms and about A water-soluble phosphine oxide comprising two residues selected from the group consisting of alkyl and hydroxyalkyl groups having from 1 to about 3 carbon atoms;
One alkyl residue having about 18 carbon atoms and about 1 to 1
Water-soluble sulfoxides containing one residue selected from the group consisting of alkyl and hydroxyalkyl residues having about 3 carbon atoms.

For semipolar nonionic detergent surfactants, the formula Wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group having about 8 to about 22 carbon atoms, or a mixture thereof, and R ⁴ is an alkylene or hydroxy having about 2 to 3 carbon atoms. An alkylene group or a mixture thereof, wherein x is from 0 to about 3 and each R ⁵ has an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or about 1 to about 3 ethylene oxide groups There are amine oxide surfactants having a polyethylene oxide group). The R ⁵ groups can be linked together, for example, via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants include, in particular, C ₁₀ -C
₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.

6. Llenado U.S. Patent issued on January 21, 1986
No. 4,565,647, wherein about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3
To about 10, preferably about 1.3 to about 3, and most preferably about 1.3
Polysaccharides containing from about 2.7 to about 2.7 saccharide units, such as alkyl polysaccharides having polyglycoside hydrophilic groups. Any reducing saccharide having 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl residues can be used instead of glucosyl residues. (Unlike glucoside or galactoside, if desired,
A hydrophobic group is attached at the 2-, 3-, 4-position, etc., to produce glucose or galactose. ) An intersugar linkage can be formed, for example, between one position of the additional saccharide unit and the 2-, 3-, 4- and / or 6-position of said saccharide unit.

If desired, a polyalkylene oxide chain linking the hydrophobic and polysaccharide residues can be provided, but is less desirable. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, saturated or unsaturated, branched or unbranched, having from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. No. Preferably, the alkyl group is a linear, saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylene chain can contain about 10, preferably less than 5, alkylene oxide residues. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-,
Tri, tetra-, penta- and hexaglucoside, galactoside, lactoside, glucose, fructoside,
Fructose and galactose. Suitable mixtures include coconut oil alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred alkyl polyglycosides are those wherein ^{_{R 2 O (C n H 2n}} O) t ( glycosyl) _{x (formula,} R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxy alkylphenyl, and mixtures thereof Where the alkyl group is about
Has 10 to about 18, preferably about 12 to about 14 carbon atoms,
n is 2 or 3, preferably 2, t is 0 to about 10,
Preferably it is 0 and x is from about 1.3 to about 10, preferably about
1.3 to about 3, most preferably about 1.3 to about 2.7). Glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form a glucoside (bonded at the 1-position). The additional glycosyl unit is then replaced with its 1-position and two of the aforementioned glycosyl units.
The bond is between the-, 3-, 4- and / or 6-position, preferably predominantly the 2-position.

7. Expression Wherein R ⁶ is an alkyl group having about 7 to about 21 (preferably about 9 to about 17) carbon atoms, each R ⁷ is hydrogen, C ₁ -C ₄ hydroxyalkyl, and - a _{(C 2 H 4 O) x} H, where X is a fatty acid amide surfactants having the change) from about 1 to about 3.

Preferred amides are, C ₈ -C ₂₀ ammonia amides, monoethanolamides, diethanolamides, and isopropanol amides.

Cationic surfactant A cationic detergent surfactant can also be incorporated into the detergent composition of the present invention. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides, and the formula [R ² (OR ³ ) y] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ⁻ [formula among, R ² is alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each _{^{R 3 -CH 2 CH 2 -,}} - CH 2 CH (CH 3) -, −CH ₂ CH (C
_{H 2 OH) -, - CH} 2 CH 2 CH 2 - and is selected from the group consisting of mixtures thereof, each of R _⁴ C ₁ ~C ⁴ alkyl, C ₁
-C ₄ hydroxyalkyl, two benzyl ring structures -CH ₂ formed by combining the R ⁴ group of CHOH-CHOHCOR ⁶ CHOHCH ₂ OH (where any hexose or hexose less than R ⁶ are a molecular weight of about 1000 Wherein R ⁵ is the same as R ⁴ or is an alkyl chain, provided that the total number of carbon atoms in R ² and R ⁵ is about 18 or less; Wherein each y is from 0 to about 10, the sum of the values of y is from 0 to about 15, and X is any suitable anion.

Other cationic surfactants used herein include 19
U.S. Pat.No. 4,228,04 issued to Cambre on Oct. 14, 80
No. 4, the disclosure of which is hereby incorporated by reference as part of that disclosure.

Other Surfactants Amphoteric surfactants can be included in the detergent compositions of the present invention. These surfactants are aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group can be linear or branched. Can be described broadly. One of the aliphatic substituents has at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water solubilizing group, such as carboxy, sulfonate. , Sulfates. For examples of amphoteric surfactants, see Laughlin et al., U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, column 19, lines 18-35, which is incorporated herein by reference. Please refer to.

Zwitterionic surfactants can also be included in the detergent compositions of the present invention. These surfactants should be described extensively as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be. For examples of zwitterionic surfactants, see Laughlin et al., U.S. Pat.No. 3,923, issued December 30, 1975.
See column 19, line 38 to column 22, line 48 of US Patent No. 9,678, cited herein as part of its disclosure.

Amphoteric and amphoteric surfactants are usually used in combination with one or more anionic and / or nonionic surfactants.

Polymeric Dispersants Polymeric dispersants can be advantageously used in the compositions of the present invention. These materials can help control calcium and magnesium hardness. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, but others known in the art can also be used. While not intending to be limited by logic, it is believed that the polymeric dispersant enhances overall detergent cleaning performance by suppressing crystal growth and helps to deagglomerate and prevent redeposition of particulate soil.

The composition of the present invention comprises a polymeric dispersant at least about
0.5%, preferably about 1% to about 10%, more preferably about 2% to about 5%.

The polycarboxylate material that can be used as the polymeric dispersant herein has the general formula Wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl, M is a salt-forming cation, and n is from about 30 to about 400. Or a copolymer comprising at least about 60% by weight of monomer units having the formula: Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen, and M is hydrogen, an alkali metal, ammonia or substituted ammonium.

Such polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in its acid form.
Suitable monomeric starting materials include acrylates, maleates, fumarate, itaconate, aconitate, mesaconate, citraconate and methylene-malonate. Corresponding unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, Citraconic acid and methylenemalonic acid. If the polymeric polycarboxylates of the present invention contain monomeric moieties that do not contain carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc., these moieties should not exceed about 40% by weight. Is preferred.

Particularly suitable polymeric polycarboxylates are polymeric polyacrylates, which can preferably be derived from acrylic acid. Such acrylic acid based polymers used in the present invention include water soluble salts of polymerized acrylic acid. The average molecular weight based on the acid form of these polyacrylate polymers is preferably at least about 1,000, and preferably from about 2,000 to 10,000.
, More preferably about 4,000 to 7,000, and most preferably about 4,000 to 5,000. Such water-soluble salts of acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known substances. The use of such polyacrylates in detergent compositions has been described in 1967.
This is disclosed in U.S. Pat. No. 3,308,067 to Diehl, issued March 7, 1998. This patent is incorporated herein by reference as part of its disclosure.

Acrylic / maleic acid based copolymers are also
It can be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably about 2,000
100100,000, more preferably about 5,000-75,000, and most preferably about 7,000-65,000. The ratio of acrylate to maleate in these copolymers is typically from about 30: 1 to about 1: 1 and more preferably about 10: 1.
1-2: 1. Water-soluble salts of these acrylic acid / maleic acid copolymers are, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble acrylate / maleate copolymer is a known substance described in European Patent Application No. 66915 published December 15, 1982, which is incorporated herein by reference. It is cited in the specification.

Another polymeric material that can be compounded is
Polyethylene glycol (PEG). PEG exhibits the performance of a dispersant and can act as a clay soil removal / anti-redeposition agent. Typical molecular weights for these purposes are from about 500 to about 100,000, preferably from about 1,000 to about 50,000
0, more preferably from about 1,500 to about 10,000.

Builder The detergent composition of the present invention may include an inorganic or organic detergent builder to help control the hardness of the inorganic material.

The concentration of the builder can vary widely depending on the end use of the composition and its desired physical form. Liquid formulations typically contain at least about 1%, more typically about 5% to about 50%, preferably about 5% to about 30%, by weight of the detergent builder. The particulate formulation typically comprises at least about 1%, more typically about 10% to about 80%, preferably about 15%, by weight of the detergent builder.
About 50% by weight. However, this does not mean that lower or higher concentrations of builders are excluded.

Inorganic detergent builders include polyphosphates (eg,
Tripolyphosphates, pyrophosphates and glassy polymeric meta-phosphates), phosphonates,
Phytic acid, silicates, carbonates (eg, bicarbonates and sesquicarbonates), sulfates and alkali metal, ammonium and alkanol ammonium salts of aluminosilicates include, but are not limited to. It is also possible to use borate builders, as well as builders that include borate-forming materials capable of producing borate under detergent storage or washing conditions (hereinafter collectively "borate builders"). Preferably, non-borate builders are used in the compositions of the present invention for use in wash conditions of less than about 50 ° C, specifically less than about 40 ° C.

Examples of silicate builders are the alkali metal silicates, particularly SiO _2: Na ₂ O ratio of 1.6: 1 to 3.2: those in the first range, and on May 12, 1987 issued to HPRieck U.S. Patent No. 4,664,839 A laminated silicate, such as the laminated sodium silicate described in US Pat. No. 6,077,098, the aforementioned patent specification being incorporated herein by reference as part of its disclosure. However, other silicates such as magnesium silicate can also be used and can serve as crispening agents in granular formulations, as stabilizers for oxygen bleaches, and as components of foam control systems. .

Examples of carbonate builders are alkaline earth and alkali metal carbonates such as sodium carbonate and sesquicarbonate and the ultrafine carbonates disclosed in German Patent Application No. 2,321,001 published Nov. 15, 1973. A mixture with calcium, the aforementioned patent specification being incorporated herein by reference as part of its disclosure.

Aluminosilicate builders are particularly useful in the present invention. Aluminosilicate builders are crucial to the powerful granular detergent compositions currently on the market,
It can also be an important builder component of liquid detergent formulations. The aluminosilicate builder has an empirical formula M _z (zAlO ₂ .y SiO ₂ ) where M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2,
y is 1), and this material has a magnesium ion exchange capacity of at least about 50 mg equivalent of CaCO ₃ per gram of anhydrous aluminosilicate. Preferred aluminosilicates have the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O, where z and y are integers of at least 6, and the molar ratio of z to y is from 1.0 to about 0.5. Where x is from about 15 to about 26
Which is an integer of 4).

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure, can be naturally occurring aluminosilicates, or can be synthetically derived.
The method of producing aluminosilicate ion exchange material is
Krummel et al., U.S. Patent No. 3,9, issued October 12, 1976
No. 85,669, which is hereby incorporated by reference as part of that disclosure.
Preferred synthetic crystalline aluminosilicate ion exchange materials used herein are sold under the names Zeolite A, Zeolite P (B) and Zeolite X.
In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O, wherein x is from about 20 to about 30, especially about 27). This material is known as zeolite A. Preferably, the particle size of the aluminosilicate is about
0.1 to 10 microns.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, and sodium polymetaphosphate having a polymerization degree of about 6%.
And phytic acid salts.

Examples of phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1,1-diphosphonate, especially the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid, such as the trisodium and tripotassium salts, and substituted methylene salts. Water-soluble salts of diphosphonic acids, such as trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene and halomethylidenephosphonates. Phosphonate builder salts of the above kind were introduced in 1964
U.S. Pat.Nos. 3,159,581 and 3,213,030 issued to Diehl on December 1, and October 19, 1965; U.S. Pat. Quim on September 3, 1968 and January 14, 1969
U.S. Patent Nos. 3,400,148 and 3,422,1 issued to
No. 37, the disclosures of which are incorporated herein by reference.

The polycarboxylate builder can be added to the composition, usually in the form of an acid, but can also be added in the form of a neutralized salt. When used in the form of a salt, alkali metal salts such as sodium, potassium and lithium salts, especially sodium salts, or ammonium and substituted ammonium (eg, alkanol ammonium) salts are preferred.

There are a variety of useful materials for polycarboxylate builders. One important class of polycarboxylate builders includes ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether carboxylate include Berg U.S. Pat. No. 3,128,287 issued Apr. 7, 1964 and Lamberti et al. U.S. Pat. No. 3,635,83 issued Jan. 18, 1972.
There is an oxydisuccinate disclosed in the specification of No. 0, and the above-mentioned patent specification is incorporated herein as a part of the disclosure.

Specific types of ether polycarboxylates useful as builders in the present invention include the general formula CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) Wherein A is H or OH, B is H or -O-CH
(COOX) —CH ₂ (COOX), where X is H or a salt-forming cation. For example, in the above general formula, when A and B are both H, the compound is oxydisuccinic acid and its water-soluble salt. A is
When OH and B is H, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. A
Is H and B is —O—CH (COOX) —CH ₂ (COOX), the compound is tartrate disuccinic acid (TDS)
And its water-soluble salts. Mixtures of these builders are particularly preferred for use in the present invention. Particularly preferred is a mixture of TMS and TDS, wherein the weight ratio of TMS to TDS is from about 97: 3 to about 20:80. These builders are disclosed in U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al.

Suitable ether polycarboxylates include cyclic compounds, particularly U.S. Patent Nos. 3,923,679, 3,835,163, 4,
The alicyclic compounds described in 158,635, 4,120,874 and 4,102,903 are mentioned, and the above-mentioned patent specification is incorporated herein as a part of the disclosure.

Other useful detergent builders include the structure HO- [C (R) (COOM) -C (R) (COOM) -O] _n- H _where M is hydrogen or a cation and the resulting salt Is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, wherein n is about 2 to
About 15 (preferably n is about 2 to about 10, more preferably n is about 2 to about 4), and each R is the same or different and is hydrogen, C _1-4 alkyl, or C
_{Are 1-4} substituted alkyls (preferably R is hydrogen)].

Still other ether polycarboxylates include maleic anhydride and ethylene, vinyl methyl ether, 1,3,5-
Copolymers with trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid are included.

Organic polycarboxy builders also include various alkali metal, ammonium and substituted ammonium salts of polyacetic acid. Examples of polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Meritic acid, succinic acid, polymaleic acid, benzene 1,
Also included are polycarboxylates such as 3,5-tricarboxylic acid, benzenepentacarboxylic acid, carboxymethyloxysuccinic acid and their water-soluble salts.

Citric acid builders, such as citric acid and its soluble salts, are particularly important polycarboxylate builders in strong liquid detergent formulations, but can also be used in particulate compositions. Suitable salts include the sodium, lithium and potassium salts and the ammonium and substituted ammonium salts.

Other carboxylate builders include the carboxylated carbohydrates disclosed in Diehl U.S. Pat. No. 3,723,322, issued Mar. 28, 1973, which is incorporated by reference. It is cited herein as part.

Suitable for the detergent compositions of the present invention include,
3,3-Dicarboxy-4-oxa-l, 6-, disclosed in Bush U.S. Patent No.
There are also hexanedioates and related compounds, the aforementioned patent specification being incorporated herein by reference as part of its disclosure. Useful succinic acid builders, there is a C ₅ -C ₂₀ alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecylsuccinic acid. Alkyl succinic acids typically have the general formula R—CH (COOH) CH ₂ (COO
H), i.e. a derivative of succinic acid, wherein R is a hydrocarbon, for example C ₁₀ -C ₂₀ alkyl or alkenyl, preferably either one is a C ₁₂ -C _16, or R is hydroxyl sulfo, sulfoxy or sulfone Substituents, all of which may be substituted with those described in the above-mentioned patent specification.

The succinate builder is preferably a water-soluble salt thereof,
For example, they are used in the form of sodium, potassium, ammonium and alkanol ammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, (preferably) 2-dodecyl succinate,
And pentadodecyl succinate. Lauryl succinate is a preferred builder in this group,
European Patent Application No. 86200690.5 / 0,200,2 published on May 5
No. 63 is described.

Examples of useful builders include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates having a molecular weight of about 2,000.
These polyacrylates can also be used effectively as dispersants), and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Another suitable polycarboxylate is the polyacetal carboxylate disclosed in US Patent No. 4,144,226 to Crutchfield et al., Issued March 13, 1979, which is incorporated by reference. It is cited herein as a part. These polyacetal carboxylates can be prepared by reacting an ester of glyoxylic acid with a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is then attached to a chemically stable end group to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution and convert to the corresponding salt, Add to surfactant.

Polycarboxylate builders are also disclosed in US Pat. No. 3,308,067 to Diehl, issued Mar. 7, 1967, which is incorporated herein by reference. It is a thing. Such materials include maleic acid, itaconic acid, mesaconic acid, fumaric acid,
There are water soluble salts of homopolymers or copolymers of aliphatic carboxylic acids such as aconitic acid, citraconic acid and methylene malonic acid.

Other organic builders known in the art can also be used. For example, a monocarboxylic acid having a long-chain hydrocarbyl and a soluble salt thereof can be used. These builders have a material commonly referred to as "soap." Those chain length of C ₁₀ -C ₂₀ are typically used. The hydrocarbyl may be saturated or unsaturated.

Enzymes Detergents are used for various purposes, such as removing protein-based, carbohydrate-based or triglyceride-based stains, and for preventing the transfer of floating dyes. It can be added to the formulation. The enzymes to be blended include protease, amylase,
There are lipases, cellulases and peroxidases, and mixtures thereof. They may be of any suitable origin, such as plant, bacterial, fungal and yeasty. However, their choice is governed by pH activity and / or optimal stability, thermal stability, stability to active detergents, builders and the like. In this connection, bacterial and fungal enzymes such as bacterial amylases and proteases, and fungal cellulases are preferred.

Suitable examples of proteases are B. subtilis and B. lich
Subtilisin obtained from a specific strain of eniforms. Another suitable protease is obtained from one strain of Bacillus and has a maximum activity in the pH range of 8-12,
Developed by Novo Industries A / S and registered trademark Esper
Released as ase ^R. The preparation of this and similar enzymes is described in Novo, GB 1243,784. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include:
Novo Industries A / S Alcalase from (Denmark) (ALCALASE) ^TM and Savinase (SAVINASE) _TM trade name and International Bio-Synthetics, Inc. Are those sold by (Netherlands) under the trade name Maxatase ^TE.

Of particular interest in the category of proteolytic enzymes for liquid detergent compositions are the enzymes designated herein as Protease A and Protease B. Protease A and its preparation are described in European Patent Application No. 130,756, published Jan. 9, 1985, which is incorporated herein by reference. It is something. Protease B is a proteolytic enzyme that differs from protease A in having leucine in place of tyrosine at position 217 of its amino acid sequence. Protease B is disclosed in European Patent Application No. 87, filed April 28, 1987.
No. 303761.8, which is incorporated herein by reference as part of its disclosure. The preparation of Protease B is also disclosed in Bott et al., European Patent Application No. 130,756, published Jan. 9, 1985, which is hereby incorporated by reference. It is quoted in.

Amylases include, for example, α-amylases obtained from special strains of B. licheniforms, which are described in more detail in GB 1,296,839 (Novo), which is incorporated by reference. Partially cited herein. Amylose-degradable proteins include, for example, RAPIDASE ^™ (International Bio-Synth
etics Inc.) and TERMAMYL ^™ (NOVO Industries).

Cellulases used in the present invention include both bacterial and fungal cellulases. Preferably their optimal pH
Is 5 to 9.5. Suitable cellulases are disclosed in U.S. Patent No. 4,435,307 to Barbesgoard et al. Humicola insolens
A fungal cellulase produced from is disclosed. Suitable cellulases are GB-A-2,075,075, GB-A-2,09
5,275 and DE-OS-2,247,832 are also disclosed.

Examples of these cellulases are Humicola insolens (Hum
icola grisea var. thermoidea), especially Humicola
Cellulase produced by strain DSM1800, and Bacil
A fungus of lus N or cellulase 212 belonging to the genus Aeromonas
Cellulase produced by producing fungi and marine mullusc (Dolabella Auricula Solander)
Is a cellulase extracted from hepatopancreas.

Lipase enzymes suitable for use in detergents include, for example, Pseud disclosed in GB 1,372,034.
Some are produced by Pseudomonas microorganisms such as omonas stutzeri ATCC 19.154, and the above-mentioned patent specification is incorporated herein by reference. Suitable lipases include the microorganism Pseudomonas fluo
Some, produced by rescens IAM 1057, show a positive immunological cross-reactivity with lipase antibodies. This lipase and its purification method are described in Japanese Patent Application No. 53/20487 published on Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan and Lipase P “Am
ano "(hereinafter referred to as" Amano-P "). These lipases of the present invention are Ouchterlon
y (Acta. Med. Scan., 133, 76-79 (1950), showing positive immunological cross-reactivity with Amano-P antibodies using the standard cyclic immunodiffusion method. These lipases. And their immunological cross-reactivity with Amano-P was described in
It is also described in U.S. Pat. No. 4,707,291 to Thom et al., Issued on May 17, which is incorporated herein by reference. Representative examples of these lipases include Amano-P lipase, lipase ex Pseudomonas fragi FERM P1339 (released under the trade name Amano-B), lipase ex Pseudonomas nitroreduce
ns var. lipolyticum FERM P 1338 (released under the trade name Amano-CES) lipase ex Chromobacter viscosum eg Chromobact commercially available from Toyo Brewery, Taga, Japan
er viscosum var.lipolyticum NRRLB 3673 and USBi
Chromobacterviscosum lipase and lipase ex Pseudomonas gladioli, marketed by ochemical Corp., USA and Disoiynth Co., The Netherlands.

Peroxidase enzymes are used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide or the like. They are used for "solution bleaching", i.e., to prevent the transfer of dyes or pigments removed from a substrate during a washing operation to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO WO published by O. Kirk on Oct. 19, 1989 and assigned to Nov Industries A / S.
No. 89/099813, which is incorporated herein by reference.

A wide variety of enzymatic materials and means for their incorporation into synthetic detergent particles are also described in U.S. Pat. No. 3,553,139, issued to McCarty et al. In the specification. Enzyme, 1978
Place et al., U.S. Patent No. 4,101,457, issued July 18,
And U.S. Patent No. 4,507,219 to Hughs, issued March 26, 1985, which is incorporated herein by reference. It is. Enzymatic materials useful in liquid detergent formulations and the incorporation of enzyme materials into those formulations are described in US Pat.
No. 4,261,868 issued to Hora et al., Which is incorporated by reference herein, which is hereby incorporated by reference.

The enzymes are usually formulated at a concentration sufficient to provide up to about 5 mg, more typically from about 0.05 mg to about 3 mg, of active enzyme per gram of composition.

Preferably, the granular detergent is coated with additives which are inert to the enzyme or shaped into spherules to minimize the formation of fines and improve storage stability. Techniques for doing this are well known in the art. For liquid formulations, an enzyme stabilizing system is preferably used. Enzyme stabilization methods for aqueous detergent compositions are well known in the art. For example,
One approach to stabilizing enzymes in aqueous solutions consists of using free calcium ions from calcium sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions are
It can be used in combination with short-chain carboxylate salts, preferably formate. See, for example, US Patent No. 4,318,818 to Letton et al., Issued March 9, 1982. This patent specification is incorporated herein by reference as part of its disclosure. It has also been proposed to use polyols such as glycerol and sorbitol. Alkoxy-alcohols, dialkyl glycoethers, polyhydric alcohols and polyfunctional aliphatic amides (e.g., diethanolamine, triethanolamine, di-
Alkanolamines such as isopropanolamine) and mixtures with boric acid or alkali metal borates. Enzyme stabilization techniques are described in U.S. Patent No. 4,261,868, issued to Horn et al. On April 14, 1981, and Gedge et al. On August 17, 1971, which are incorporated herein by reference. U.S. Pat.No. 3,600,319 issued to U.S. Pat.
Venegas European Patent Application Publication No. 0 published October 29, 2014
Also disclosed and exemplified in 199405, application 86200586.5. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems, for example, U.S. Pat.No. 4,261,868,
Nos. 3,600,319 and 3,519,570 are also described.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The detergent compositions of the present invention may comprise a bleaching agent or bleaching composition comprising a bleaching agent and one or more bleaching activators. When bleaching compounds are included, they may comprise from about 1% to about 20% of the detergent composition, more typically from about 1% to about 10%.
At a concentration of Typically, the bleaching compound is an optional ingredient in non-liquid formulations, such as granular detergents. When a bleach activator is included, this amount is typically about 0.1% to about 60%, more typically 0.5% to about 40%.

The bleaching agents used herein can be any of the bleaching agents useful for fabric cleaning, hard surface cleaning or other cleaning purposes now known or becoming known. These include oxygen bleaches as well as other bleaches. At cleaning conditions below about 50 ° C., especially below about 40 ° C., the compositions of the present invention include materials capable of borate formation in situ under borate or detergent storage or cleaning conditions (ie, borate forming materials). Preferably not. Therefore, under these conditions, it is preferred to use bleach that is non-borate, ie, does not form borate. Preferably, the detergents used at these temperatures are substantially free of borates and borate-forming materials. As used herein, "substantially free of borate and borate-forming material" means that the composition contains no more than about 2% by weight of any type of borate-containing and borate-forming material,
It preferably means 1% or less, more preferably 0%.

One type of bleach that can be used is percarboxylic acid bleach and its salts. Suitable examples of this type of bleach are magnesium monoperoxyphthalate hexane hydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decandioic acid. These bleaches are described in US Pat. No. 4,483,781 to Hartman, issued Nov. 20, 1984, to Burns, filed Jun. 3, 1985.
U.S. Patent Application No. 740,446, Banks et al. European Patent Application No. 0,133,354 published February 20, 1985, and Chung et al. U.S. Patent No.
No. 12,934, the disclosure of which is incorporated herein by reference. Highly preferred bleaches include Burn on January 6, 1987
There is 6-nonylamino-6-oxoperoxycaproic acid described in U.S. Pat.No. 4,634,551 issued to U.S. Pat. It is something.

Another type of bleach that can be used is the halogen bleach. Hypohalite bleaches include, for example, trichloroisocyanuric acid, and sodium and potassium dichloroisocyanurates, and N-chloro and N-bromoalkanesulfonamides. Such materials are usually 0.5 to 10% by weight of the final product,
Preferably it is added at 1 to 5% by weight.

Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

The peroxygen bleach is preferably used in combination with a bleach activator to generate in situ the peroxylic acid corresponding to the bleach activator in an aqueous solution (ie, during the washing step).

Preferred bleach activators incorporated into the compositions of the present invention include:
General formula Wherein R is an alkyl group having about 1 to about 18 carbon atoms, wherein the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms. in and, L is a leaving group, with its pK _a of the conjugate acid is from about 4 to about 13 range). These bleach activators are disclosed in U.S. Pat.No. 4,915,854, issued to Mao et al. On April 10, 1990, which is incorporated herein by reference, and incorporated herein by reference. It is described in U.S. Pat. No. 4,412,934, which is incorporated herein by reference.

Bleaches other than oxygen bleaches are known in the art and can be used in the present invention. One type of non-oxygen bleach that is of particular interest is zinc sulfonate and / or
Or there is a light activated bleach such as aluminum phthalocyanine. These materials can be deposited on the substrate during the cleaning process. Irradiation with light in the presence of oxygen, such as hanging clothes outdoors and drying in sunlight, activates the sulfonated zinc phthalocyanine, thereby bleaching the substrate. A preferred zinc phthalocyanine and light activated bleaching process is described in
US Patent No. 4,033,718 issued to Holcombe et al.
And the foregoing patent specification is incorporated herein by reference as part of its disclosure. Typically, the detergent composition comprises from about 0.025% to about 1.25% by weight of the sulfonated zinc phthalocyanine.

Polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can be used in the practice of the present invention. The polymeric soil release agent adheres to the hydrophobic fibers, such as polyester and nylon, to render the surface of the fibers hydrophilic, and remains attached until the wash and rinse cycle is completed. And a hydrophobic portion that functions as a fixing medium for the hydrophilic portion. Thereby, the stain existing after the treatment with the stain release agent can be more easily removed by the subsequent washing treatment.

Benefits of using a polymeric soil release agent in any of the detergent compositions of the present invention, particularly those used in laundry or other applications that require the removal of grease and oils from hydrophobic surfaces However, the inclusion of polyhydroxyfatty acid amides in detergent compositions that also include anionic surfactants can enhance the performance of many of the commonly used types of polymeric soil release agents. Anionic surfactants impair the ability of certain soil release agents to attach and bind to the hydrophobic surface. These polymeric soil release agents have a nonionic hydrophilic or hydrophobic moiety that interacts with the anionic surfactant.

Improved performance of polymeric soil release agents can be obtained by using polyhydroxy fatty acid amides. Anionic surfactant systems, soil release agents that interact with anionic surfactants And (I) the interaction of the anionic surfactant between the soil release agent of the detergent composition and the anionic surfactant system. (A) a "control" step of measuring the SRA adhesion of the detergent composition in an aqueous solution in the absence of other detergent components; and (B) an anionic surfactant used in the same type and amount of detergent composition Is combined with SRA in an aqueous solution with an anionic surfactant system of the same weight ratio of SRA to the detergent composition as the "SRA / anionic surfactant" test step. example Can be shown by comparing the extent of adhesion of the soil release agent (SRA) to the (A), thereby reducing the adhesion in (B) versus (A) due to the mutual interaction of the anionic surfactant. (II) determining whether the detergent composition comprises a soil release agent enhancing amount of polyhydroxy fatty acid amide;
(B) SRA adhesion in the SRA / anionic surfactant test step, the same type and concentration of the polyhydroxyfatty acid amide of the detergent composition was applied to a soil release agent corresponding to the SRA / anionic surfactant test step and (C) Combined with an anionic surfactant system and can be determined by comparing the soil release agent deposition in the "SRA / anionic surfactant / PFA test process" where the test process (B) On the other hand, the improvement in the adhesion of the soil release agent in the test step (C) indicates that the soil release agent-enhancing amount of polyhydroxy fatty acid amide is contained. For the purposes of the present invention, these tests should be performed at anionic surfactant concentrations in aqueous solutions above the anionic surfactant's critical micelle concentration (CMC), preferably above about 100 ppm. The concentration of the polymeric soil release agent should be at least 15 ppm. A sample of polyester fabric should be used for the hydrophobic fiber source. The same swatch is immersed in the aqueous solution of each test step at 35 ° C. for 12 minutes, stirred, removed, and analyzed. The degree of adhesion of the polymeric soil release agent is determined by radiolabeling the soil release agent before treatment.
It can be measured by performing radiochemical analysis by a method known in the art.

Instead of the radiochemical analysis method described above, the adhesion of the soil release agent to the test step is determined by measuring the ultraviolet (UV) absorbance of the test solution according to techniques well known in the art (i.e., test step A, It can also be measured in B and C). Of the test solution after removal of the hydrophobic textile material
The decrease in UV absorbance corresponds to the increase in SRA attachment. As will be appreciated by those skilled in the art, UV analysis is a test solution that contains a type and concentration of materials that interfere with UV absorption in the past, such as high concentrations of surfactants having aromatic groups (eg, alkylbenzene sulfonates, etc.). Should not be used.

Thus, "soil release agent enhancing amount" of polyhydroxy fatty acid amide is defined as the amount of surfactant that increases the adhesion of the stain release agent to the hydrophobic fibers as described above, or the detergent of the present invention in the next cleaning operation. Means that can increase the grease / oil cleaning performance of the fabric being washed in the composition.

The amount of polyhydroxy fatty acid amide required to increase adhesion depends on the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent selected, and the particular polyhydroxy fatty acid amide selected. Varies by. Generally, the composition will comprise from about 0.01% to about 10% by weight of the polymeric soil release agent, typically from about 0.1% to about 5%.
%, And from about 1% to about 50% of an anionic surfactant, more typically from about 4% to about 30%. Such compositions should normally contain at least about 1%, preferably at least about 3%, by weight of the polyhydroxy fatty acid amide, but are not necessarily intended to be limited to this range.

Polymeric soil release agents whose performance is enhanced by polyhydroxy fatty acid amides in the presence of an anionic surfactant include (a) (i) a polyoxyethylene moiety having a degree of polymerization of at least 2, or (ii) a degree of polymerization. Is any 2 to 10 oxypropylene or polyoxypropylene moieties, provided that said hydrophilic moieties are not linked to an adjacent residue at each end group by an ether linkage, which includes any oxypropylene units. Or (iii) a mixture of oxyethylene and oxyalkylene units comprising from 1 to about 30 oxypropylene units, wherein said mixture has a sufficient amount of oxyethylene units and the hydrophilic component is usually Soil release agent adheres to the surface of the polyester synthetic fiber, and has sufficient hydrophilicity to increase the hydrophilicity of this surface. The hydrophilic portion preferably has at least about 25% oxyethylene units, more preferably at least about 50%, especially for non-ionic hydrophilic components having about 20-30 oxypropylene units. Or (b) (i) an oxyalkylene terephthalate moiety of C ₃ , wherein one or more of the hydrophobic components comprises: When oxyethylene terephthalate is also included, the ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is about 2: 1 or less, (ii) C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene moiety or Mixtures thereof, (iii) poly (vinyl ester) moieties having a degree of polymerization of at least 2, preferably poly (vinyl acetate), or (iv) C 4 ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents, or a mixture thereof, the form of the substituents C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives, or mixtures thereof, The cellulose derivative is amphiphilic and has a sufficient concentration of C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units to adhere to the surface of conventional polyester synthetic fibers. Once attached to this conventional synthetic fiber surface, one or more hydrophobic components consisting of those that retain a sufficient concentration of hydroxyl to increase the hydrophilicity of the fiber surface, or (a) and ( There are soil release agents having a combination with b).

Typically, the degree of polymerization of the polyoxyethylene moiety of (a) (i) is from 2 to about 200, whereby higher degrees of polymerization can be used, but preferably from 3 to about 150;
More preferably, it is 6 to about 100. Suitable oxy C ₄ -C ₆
Alkylene hydrophobic moieties include Gosselin on January 26, 1988
MO ₃ issued to U.S. Pat.No. 4,721,580, issued to U.S. Pat.
O (CH ₂ ) _n OCH ₂ CH ₂ O- (where M is sodium,
n is an integer from 4 to 6), but is not limited thereto.

Polymeric soil release agents useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.

Cellulose derivatives having a function as a soil release agents are commercially available, hydroxyethyl ethers of cellulose such as Methocel ^R (Dow).

The cellulosic soil release agent used in the present invention includes:
Methylcellulose, ethylcellulose, also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl cellulose such as hydroxypropyl methylcellulose and hydroxybutyl methylcellulose. A variety of cellulose derivatives useful as soil release polymers are described in U.S. Pat.No. 4,804,827, issued Dec. 28, 1976 to Nicol et al. And incorporated herein by reference.
000,093.

Soil release agents featuring poly (vinyl ester) hydrophobic moieties include poly (vinyl esters) grafted to a polyalkylene oxide backbone, such as a polyethylene oxide backbone, such as C ₁ -C ₆ vinyl esters, preferably There is a graft copolymer of poly (vinyl acetate). Such materials are known in the art and are described in European Patent Application No. 0219048, issued April 22, 1987 to Kud et al. Suitable commercially available soil release agents of this type include Sokalan ^™ type materials, such as Sokalan ^™ HP-22 sold by BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers consist of repeating units of ethylene terephthalate and PEO terephthalate, the molar ratio of ethylene terephthalate units to PEO terephthalate units being from about 25:75 to about 35:65, and containing polyethylene oxide. The molecular weight of the PEO terephthalate unit is about 300
~ 2000. The molecular weight of the polymeric soil release agent ranges from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230, issued May 25, 1976 to Hays and incorporated herein by reference. See also U.S. Pat. No. 3,893,929, issued Jul. 8, 1975 to Basadur (cited herein as part of that disclosure), which discloses similar copolymers.

Another preferred polymeric soil release agent is ethylene terephthalate derived from polyoxyethylene glycol having an average molecular weight of 300 to 5,000, containing 10 to 15% by weight of ethylene terephthalate units and 90 to 80% by weight of polyoxyethylene terephthalate units. It is a polyester having a repeating unit, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound is 2: 1 to 6: 1. Examples of polymers, commercially available materials Zelcon ^R 5126 (manufactured by Dupont) and Milease
^{There is R} T (made by ICI). These polymers and their methods of preparation are described in U.S. Pat.No. 4,042,027, issued to Gosselink on Oct. 27, 1987 and incorporated herein by reference.
It is described in more detail in the specification of 702,857.

Another preferred polymeric soil release agent is the sulfonation of a substantially linear ester oligomer comprising an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal residue conjugated to the backbone. Product, said soil release agent being allyl alcohol ethoxylate, dimethyl terephthalate and 1,1
Derived from 2-propylene diol, the end groups of each oligomer after sulfonation average about 1
It has from about 4 sulfonate groups. These soil release agents were disclosed on November 6, 1990 by JJ Scheibel and EP Gosselin.
U.S. Pat.No. 4,968,451, issued to U.S. Pat. .

Other suitable polymeric soil release agents include December 8, 1987
Ethyl- or methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyester in U.S. Pat.No. 4,711,730 issued to Gosselink et al., Issued to Gosselink on Jan. 26, 1988. 4,721,580 Anionic end-capped oligomeric esters wherein the anionic end cap comprises a sulfo-polyethoxy group derived from polyethylene glycol (PEG), 1987
U.S. Patent No. 4,702,8 issued to Gosselink on October 27,
A block polyester oligomeric compounds described 57 Pat formula _{X- (OCH 2 CH 2) n} - (In the formula, n is 12 to about 43, X is C ₁ -C ₄ alkyl or preferably Are methyl), and those patents have a polyethoxy end cap, and these patents are hereby incorporated by reference as part of their disclosure.

Additional polymeric soil release agents include U.S. Pat.No. 4,877,896, issued Oct. 31, 1989 to Maldonado, which discloses anionic, especially end-capped, terephthalate esters of sulfoaroyl. There are soil release agents described therein, and the foregoing patent specification is hereby incorporated by reference as part of its disclosure. Terephthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units. US Patent 4,8
The soil release polymer of 77,896 includes materials having a polyoxyethylene hydrophilic component or a C ₃ oxyalkylene terephthalate (propylene terephthalate) repeat unit within the hydrophobic component of (b) (i) above. is there.
Particularly advantageous by the inclusion of the polyhydroxyfatty acid amides of the present invention in the presence of an anionic surfactant are polymeric soil release agents that feature either or both of these criteria.

When a soil release agent is used, it usually comprises from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0% of the detergent composition of the present invention. It is.

Chelating Agents The detergent compositions of the present invention can also optionally include one or more iron and magnesium chelators as builder additives. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, all as defined below. While not intending to be bound by theory, it is believed that the benefits of these materials are due in part to the unexpected ability to remove iron and magnesium ions from the cleaning solution by forming soluble chelates. Can be

Aminocarboxylates useful as desired chelating agents in the compositions of the present invention have the structure Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eg, ethanolamine), and x is from 1 to about 3, and preferably 1, has one or more, preferably at least two, units be able to.
Preferably, these aminocarboxylates have about 6
Does not include alkyl or alkenyl groups having more than one carbon atom. Amine carboxylates that can be used include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and their ethanoldiglycine , Alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention, at least when low levels of total phosphorus can be present in the detergent composition.

Construction Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1
Compounds having one or more, preferably at least two, units are useful, and include ethylenediaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetrisamine pentakis (methylene phosphonate). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be split by substructure.

Polyfunctionally substituted aromatic chelators are also useful in the compositions of the present invention. These materials have the general formula (Wherein at least one R a is -SO ₃ H or -COOH or soluble salts thereof) can comprise compounds and mixtures thereof having.

U.S. Patent No. 3,812,044, issued May 21, 1974 to Connor et al. And incorporated herein by reference, includes polyfunctionally substituted aromatic chelators and sequestering agents. It has been disclosed. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions can include these materials in the form of alkali metal, ammonium or substituted ammonium (eg, mono- or triethanol-amine) salts.

When these chelating agents are used, they are usually from about 0.1% to about 10% by weight of the detergent compositions of the present invention. More preferably, the chelating agent is from about 0.1% to about 3.0% by weight of these compositions.

Clay Soil Removal / Anti-Redeposition Agent The compositions of the present invention can also optionally include a water-soluble ethoxylated amine having clay soil removal and anti-redeposition properties. Particulate detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of a water-soluble ethoxylated amine, while liquid detergent compositions typically contain from about 0.01% to about 5%. %including. These compounds are (1) (X-L -) - N- ethoxylated monoamines having the (R ²⁾ _2, (2) formula Or an ethoxylated diamine having (XL-) ₂ -N-R ¹ -N (R ² ) ₂ , An ethoxylated polyamine having the general formula (4) Ethoxylated amine polymers having, and (5) is selected preferably from the group consisting of mixtures thereof, A ¹ is Or a -O-, R is H or C ₁ -C ₄ alkyl or hydroxyalkyl, or R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or 2 to about A C ₂ -C ₃ oxyalkylene residue having 20 oxyalkylene units, provided that no O—N bond is formed and each R ²
The C ₁ -C ₄ or hydroxyalkyl, or a residue -L-X, or two R ² together residue - (CH _{2) r,
^{-A 2 - (CH 2) s}} - to form, however, A ² is -O- or -CH ₂ -, r is 1 or 2, s is 1 or 2, r + s is 3 or 4, X is a non-ionic group, an anionic group or a mixture thereof, and R ³ is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having a substitution site. ⁴ C ₁ -C ₁₂ alkylene, hydroxyalkylene,
C ₂ having alkenylene, arylene or alkarylene as or from 2 to about 20 oxyalkylene units
~ C ₃ oxyalkylene residue, provided that OO or O
-N bond is not formed, L is a polyoxyalkylene residue _{^{- [(R 5 O) m}} (CH 2 CH 2) n] - is a hydrophilic chain comprising, R ⁵ is C ₃ -C ₄ alkylene or hydroxy alkylene, m and n are residues _{- (CH 2 CH 2) n} - is a number such that at least approximately 50 wt% of the polyoxyalkylene residues, for said monoamines, m is 0
From about 4 to about 4 and n is at least about 12, and for the diamines described above, m is from 0 to about 3 and n is at least R ¹ is C ₂ -C ₃ alkylene hydroxyalkylene or alkenylene. Sometimes about 6, at least about 3 when R ¹ is other than C ₂ -C ₃ alkylene hydroxyalkylene or alkenylene, and for said polyamines and amine polymers, m is 0 to about 10; , N is at least about 3 and p is 3-8;
q is 1 or 0, t is 1 or 0, provided that q
Is 1, t is 1, w is 1 or 0, x + y + z is at least 2, and y + z is at least 2. The most preferred soil release and anti-redeposition agent is ethoxylated tetrakisethylenepentamine. Exemplary ethoxylated amines are also described in US Pat. No. 4,597,898, issued Jul. 1, 1986, which is incorporated herein by reference. Another class of preferred clay soil removal / anti-redeposition agents is disclosed in Oh and Gosselink European Patent Application No. 111,965, published June 27, 1984, and incorporated herein by reference as part of its disclosure. It is disclosed in the specification. Other clay stain removal / redeposition inhibitors that can be used are June 27, 1984
Ethoxylated amine polymers disclosed in European Patent Application No. 111,984 to Gosselink, published on Jul. 4, 1999, and European Patent Application No. 112,5 to Gosselink, published on July 4, 1984.
No. 92, and the amine oxides disclosed in Connor U.S. Pat.No. 4,548,744 issued Oct. 22, 1985, all of which are incorporated herein by reference. It is cited in the specification.

Clay soil removal and / or anti-redeposition agents known in the art can also be used in the compositions of the present invention. Another type of preferred anti-redeposition agent is a carboxymethyl cellulose (CMC) material.
These materials are well-known in the art.

Brightener Any optical brightener or other brightening or whitening agent known in the art can be incorporated into the detergent compositions of the present invention.

The choice of whitening agent used in the detergent composition depends on the type of detergent, the nature of the components included in the detergent composition, the temperature of the wash water, the degree of agitation, the ratio of the material to be washed to the washing tub. It depends on many factors.

The choice of whitening agent also depends on the type of material to be cleaned, such as cotton, synthetics, and the like. Since most laundry detergent products are used for cleaning a wide variety of fabrics, the detergent composition should include a mixture of brighteners that is effective against a wide variety of fabrics. Of course, it is necessary that the individual components of such brightener mixtures be compatible.

Commercially available optical brighteners that can be used in the present invention include:
They can be divided into subgroups, which include stilbenes, pyrazolines, coumarins, carboxylic acids, methine cyanines, dibenzothiophene-5,5-dioxide, azoles, derivatives of 5- and 6-membered heterocycles, And various other compounds, but are not necessarily limited thereto. Examples of such brighteners are “Th
e Production & Application of Fluorescent Brighte
ning Agents ", published by M. Zqhradnik, John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference.

The stilbene derivatives used in the present invention include bis (triazinyl) amino-stilbene derivatives, stilbene bisacylamino derivatives, stilbene triazole derivatives, stilbene oxadiazole derivatives, stilbene oxazole derivatives and stilbene styryl derivatives. .

Certain derivatives of bis (triazinyl) aminostilbene used in the present invention can be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives used in the present invention include, but are not necessarily limited to, derivatives substituted at the 3-, 7-, and 7-positions.

The carboxylic acid derivatives used in the present invention include fumaric acid derivatives, benzoic acid derivatives, p-phenylene-bis-acrylic acid derivatives, naphthalenedicarboxylic acid derivatives, heterocyclic acid derivatives, and cinnamic acid derivatives. Not limited.

The cinnamic acid derivative used in the present invention is furthermore Zahradnik
Cinnamic acid derivatives, as disclosed on page 77 of
It can be subdivided into groups such as, but not limited to, styryl, styrylbenzofuran, styryloxadiazole, styryltriazole and styrylpolyphenyl.

Styrilazoles can be further subdivided into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles as disclosed on page 78 of the Zahradnik literature. It will be appreciated that these three identified subclasses do not necessarily reflect all of the many subgroups into which styrylazoles are classified.

Another type of chemical brightener used in the present invention is The Kirk-Othmer Encyclopedia of Chemical Tech.
nology Vol. 3, pp. 737-750 (John Wheely and Sons, Inc., 1962), 741-749
Derivatives of dibenzothiophene-5,5-dioxide disclosed on page 3, the disclosure of which is hereby incorporated by reference as part of that disclosure, including 3,7-diaminobenzothiophene- 2,8-disulfonic acid 5,5-dioxide.

Another optical brightener used in the present invention includes 5
And azole which is a derivative of a membered heterocyclic ring.
These can be further classified into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in Kirk-Othmer.

Another type of brightener used in the present invention is Kirk
-A derivative of a 6-membered heterocyclic ring disclosed in the literature of Othmer. Examples of these compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.

In addition to the above whitening agents, various compounds can also be used as whitening agents. These various compounds are
k, p. 93-95, which discloses 1-hydroxy-3,6,8-pyrenetrisulfonic acid, 2,4-dimethoxy-1,
Derivatives of 3,5-triazin-6-yl-pyrene, 4,5-diphenylimidazolone-disulfonic acid and pyrazoline-quinoline.

Another specific example of the optical brightener used in the present invention is 19
U.S. Patent No. 4,790,856 issued to Wixon on December 13, 1988
And the disclosure of which is incorporated herein by reference as part of that disclosure. These brighteners include Verona brightener Phorwhit
e There is a ^TM series. Other brighteners disclosed in this document include tinopal UNP from Ciba-Geigy.
A, Tipanol CBS and Tipanol 5BM, Hilton, Italy
-Arctic White CC and Arct released by Davis
ic White CWD, 2- (4-styryl-phenyl) -2H-
Naphthol [1,2-d] triazole, 4,4'-bis-
(1,2,3-triazol-2-yl) -stilbene, 4,
There are 4'-bis (styryl) bisphenyl, and y-aminocoumarin. Specific examples of these brighteners include 4-
Methyl-7-diethyl-aminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenylfurazoline, 2,5-bis (benzoxazol-2-yl) thiophene, 2-styryl −Naphth− [1,
2-d] oxazole, and 2- (stilbene-4-
Yl) -2H-naphtho [1,2-d] triazole.

Other optical brighteners that can be used in the present invention include:
U.S. Patent No. 3,646, issued to Hamilton on February 29, 1972
No. 015, the disclosure of which is hereby incorporated by reference as part of that disclosure.

Foam Inhibitors Compounds that are known or have become known to reduce or inhibit foam formation can be incorporated into the compositions of the present invention. The incorporation of such materials (hereinafter referred to as "foam suppressants") is desirable because the polyhydroxyfatty acid amide surfactants of the present invention can increase the foam stability of the detergent composition. is there. Foam control is particularly important when the detergent composition includes a relatively high foaming surfactant in combination with a polyhydroxy fatty acid amide surfactant. In compositions used in front-loading automatic washing machines, suppression of foam is particularly desirable. These machines are typically characterized by having a drum for holding the washing and washing water, these machines having a horizontal axis and a rotating action about that axis. As a result of this type of stirring, a large amount of foam is formed,
Cleaning performance may be reduced. The use of suds suppressors can be very important under hot water washing conditions and also under high surfactant concentration conditions.

A wide variety of materials may be used in the compositions of the present invention as suds suppressors. Suds suppressors are well known to those skilled in the art. They are, for example, Kirk Othmer Encycl
opedia of Chemical Technology, Third Edition, Volume 7, 430
-447 (John Wiley & Sons, Inc., 1979). One category of foam suppressors of particular interest is:
Includes monocarboxylic fatty acids and their soluble salts. These materials are described in U.S. Pat. No. 2,954,347 issued to Wayne St. John on Sep. 27, 1960, which is hereby incorporated by reference as one of its disclosures. Is done. The monocarboxylic fatty acids and salts thereof used as suds suppressors typically have a hydrocarbyl chain having from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include sodium,
There are alkali metal salts such as potassium and lithium salts, and ammonium and alkanol ammonium salts. These materials are a preferred class of suds suppressors for detergent compositions.

The detergent composition can also include a non-surfactant suds suppressor. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic
C ₁₈ -C ₄₀ ketones (e.g., stearone), and the like. Other suds suppressors include cyanuric chloride, 1-24
Primary or secondary amines having 2 carbon atoms 2 or 3
Molar, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate, and tri-to- formed as a product with monostearyl di-alkali metal (e.g., sodium, potassium, lithium) phosphate and phosphate esters. There are N-alkylated aminotriazines such as hexa-alkylmelamine or di- to tetra-alkyldiaminechlorotriazines. Hydrocarbons such as paraffins and haloparaffins can be used in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, have a pour point in the range of about -40 ° C to about 5 ° C, and have a minimum boiling point of at least 110 ° C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably those with melting points below about 100 ° C. These hydrocarbons constitute a preferred class of suds suppressors in detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al., Which is hereby incorporated by reference as part of its disclosure. It was done. Hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term "paraffin" as used in describing this suds suppressor is intended to encompass a mixture of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors include silicone suds suppressors. This class includes polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes and silica particles, wherein the polyorganosiloxane is converted to silica. Those that are chemically adsorbed in a molten state are used. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al.
European Patent Application No. 89307851.9 published by rch, MS
As disclosed in US Pat.
It is hereby incorporated by reference as part of its disclosure.

Another silicone suds suppressor is disclosed in U.S. Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of a polydimethylsiloxane fluid.

Mixtures of silicone and silanized silica are described, for example, in German Patent Application DOS 2,124,526. Silicone defoamers and foam control agents in granular detergent compositions are disclosed in Bartolotta et al., U.S. Patent 3,933,672 and Baginski et al., U.S. Patent 4,652,392, issued March 24, 1987. I have.

Examples of silicone-based suds suppressors used herein include: (i) a polydimethylsiloxane fluid having a viscosity at 25 ° C. of about 20 cs to about 1500 cs; (ii) (CH ₃ ) ₃ Consists of SiO _1/2 units and SiO ₂ units, (CH
₃ ) The ratio of ₃ SiO _1/2 units to SiO ₂ units is about 0.6: 1 to about
1.2: 1 siloxane resin (i) about 5 to about 50 parts per 100 parts by weight; and (iii) solid silica gel containing about 1 to 100 parts by weight of (i) 100 parts by weight.
A foam control amount of a foam control agent consisting of about 20 parts.

For any detergent composition used in an automatic washing machine, the foam should not form so much as to overflow from the washing machine. When a foam inhibitor is used, it is preferably contained in the “foam inhibiting amount”. By "foam control amount" is meant that the formulator of the composition can wash the amount of this foam control agent sufficiently to control the foam to produce a low foaming laundry detergent for use in automatic washing machines. I do. The amount of foam control agent will vary depending on the laundry detergent selected. For example, in the case of a high foaming surfactant, a desired foam control is performed by using a larger amount of a foam controlling agent as compared with a low foaming surfactant. Normally, a sufficient amount of suds suppressor is incorporated into the low foaming detergent composition and is added during the washing cycle of the automatic washing machine (when stirring the detergent in the aqueous solution under the given washing temperature and concentration conditions). The foam formed should not exceed about 75% of the porosity of the storage drum of the washing machine, preferably the foam should not exceed about 50% of said porosity. It is determined as the difference between the total volume of the drum and the volume of water and laundry.

The compositions of the present invention typically contain from 0% to about 5% suds suppressor. When used as suds suppressors, monocarboxylic acids and salts thereof are typically included in amounts up to 5% by weight of the detergent composition. Preferably, about 0.5% to about 3% of a fatty acid monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition, but higher amounts can be used. This upper limit is practical, primarily because it involves minimizing cost and retaining a small amount of effectiveness to effectively control foaming. Preferably, about 0.01% to about 1% of a silicone suds suppressor is used, more preferably about 0.25%.
% To about 0.5% is used. These weight percent values as used herein include polyorganosiloxanes and any silica that can be used in combination with any auxiliary materials that can be used. Monostearyl phosphate is typically present in an amount of from about 0.1% to about
Used in an amount of about 2%.

Hydrocarbon suds suppressors typically comprise from about 0.01% to about 5.0%
, But larger amounts can be used.

Other Ingredients A wide variety of other ingredients useful in detergent compositions, such as other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, are incorporated into the compositions of the present invention. be able to.

Liquid detergent compositions can include water and other water-compatible solvents as carriers. Preferred are low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred to solubilize the surfactant, but 2
Polyols having from about 6 to about 6 carbon atoms and having from 2 to about 6 hydroxy groups (eg, propylene glycol, ethylene glycol, glycerin and 1,2-propanediol) can also be used.

The detergent composition of the present invention, during use in aqueous cleaning operations,
It is preferable that the pH of the washing water is about 6.5 to about 11, preferably about 7.5 to about 10.5. PH of liquid product formulation
Is preferably about 7.5 to about 9.5, more preferably about 7.5 to
It is about 9.0. Recommended techniques for adjusting pH include the use of buffers, alkalis, acids, and the like, which are well known to those skilled in the art.

The present invention also provides a detergent composition comprising a polymeric dispersant and a detersive surfactant by additionally incorporating at least about 1% by weight of the polyhydroxyfatty acid amide surfactant into the detergent composition. Methods for improvement are also provided.

The present invention also provides a method for treating a substrate, such as a fiber, fabric, hard surface, skin, etc., with one or more anionic, non-ionic or cationic surfactants, at least about 0.5% of a polymeric dispersant, A method is provided for cleaning this substrate by contacting it with a detergent composition comprising 1% polyhydroxy fatty acid amide.

Preferred surfactants, polymeric dispersants, additive components,
The concentrations of these materials, which are preferred from the compositions of the present invention, are also preferred for the method.

Experiment Here, a method for producing N-methyl, 1-deoxyglucityl lauramide used in the present invention will be exemplified. A skilled chemist can change the shape of the device,
One preferred device for use in the present invention comprises a three liter, four-necked flask equipped with a motor driven paddle stirrer and a thermometer long enough to contact the reaction medium. ing. In the other two ports of the flask,
A nitrogen inlet and a wide-bore sidearm with an efficient condensing cooler and vacuum outlet connected (Note: the wide-bore sidearm is important for very rapid methanol generation) It is attached. The latter is connected to a nitrogen outlet and a vacuum gauge, and then to an aspirator and trap. A 500 watt heating mantle with a variable transformer temperature controller (Variac) used to heat the reactants is placed on the lab-jack, allowing it to be easily raised and lowered to further regulate the temperature of the reactants .

N-methylglucamine (195 g, 1.0 mol, Aldrich, M4
700-0) and methyl laurate (Procter & Gamble),
CE1270, 220.9 g, 1.0 mol) into a flask. The solid / liquid mixture is heated with stirring under a stream of nitrogen to form a melt (about 25 minutes). Melt temperature 14
When 5 ° C. is reached, the catalyst (anhydrous sodium carbonate in powder, 10.5 g, 0.1 mol, JT Baker) is added. Shut off the nitrogen stream and adjust the aspirator and nitrogen outlet to create a 5 inch (5/31 atm) Hg vacuum.
Thereafter, the reaction temperature is maintained at 150 ° C. by adjusting the variac and / or raising and lowering the mantle.

Within 7 minutes, the first methanol foam is observed on the surface of the reaction mixture. Soon the fierce reaction continues. The methanol is distilled completely until the rate subsides. Adjust the vacuum to about 10 inches Hg (10/31 atm) vacuum. Increase the vacuum approximately as follows: 10 inches Hg in 3 minutes, 7
20 inches Hg in minutes, 25 inches Hg in 10 minutes. After 11 minutes from the onset of methanol evolution, stop heating and stirring while some foaming occurs. The product is allowed to cool and solidify.

The following examples are meant to illustrate the compositions of the present invention, but are not necessarily meant to limit or define the scope of the invention, the scope of which is determined by the appended claims .

EXAMPLES The following examples are meant to illustrate the compositions of the present invention, but are not necessarily meant to limit or define the scope of the invention, and the scope of the invention is defined by the following claims. Is determined by the range.

Examples 1 to 4 These examples show a strong granular detergent composition comprising a polyhydroxy fatty acid amide and a polymeric dispersant.

The compositions of Examples 1 to 4 had a weight of about 1400
It is a formulation that is preferably used at a concentration of ppm and at a temperature below about 50 ° C. The above example is made by slurrying the base granule component and spray drying to a moisture content of about 4-8%. The remaining dry ingredients are mixed with the granulated or powdered spray-dried granules in a rotary mixing drum and sprayed with liquid ingredients (non-ionic surfactants and fragrances).

Examples 5 to 10 The following examples show strong liquid compositions comprising a polyhydroxy fatty acid amide and a polymeric dispersant.

Examples 5 to 10 are about 2000 ppm based on the weight of the washing water,
Preferably, a wash temperature of less than about 50 ° C is used. These include non-aqueous solvents, aqueous surfactant pastes or solutions,
Prepared by combining an aqueous solution of molten fatty acids, polycarboxylate builders and other salts, aqueous ethoxylated tetraethylenepentamine, a buffer, caustic and the balance of water. The pH is adjusted with an aqueous citric acid solution or sodium hydroxide solution to a pH of about 8.5. After adjusting the pH, the final ingredients such as soil release agents, enzymes, colorants and fragrances are added and the mixture is stirred until a single phase.

Example 11 Another method for preparing the polyhydroxy fatty acids used herein is as follows. 84.87 g fatty acid methyl ester (available from Procter & Gamble, methyl ester CE1270), 75 g N-methyl-D
Glucamine (available from Aldrich Chemical Company, M4700-0), 1.04 g sodium methoxide (available from Aldrich Chemical Company, 16,4)
A reaction mixture consisting of 99-2) and 68.51 g of methyl alcohol is used. The reaction vessel consisted of a standard reflux unit with a drying tube, a condenser and a stir bar. In this treatment, N-methylglucamine is combined with methanol while stirring under an argon atmosphere, and heating is started with sufficient mixing (stir bar, reflux). 15-20
After a minute, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but the solution is completely clear by 63.5 minutes. The reaction is considered to be virtually complete at this point. The reaction mixture is kept at reflux for 4 hours. After removing the methanol, the amount of recovered crude product is 156.16 g. After vacuum drying and purification, the overall yield is 1
06.92 g of purified product is recovered. However,
Samples are taken periodically during the course of the reaction, and the yield is not calculated on this basis since the overall yield value is meaningless. The reaction is 80 for up to 6 hours.
% And 90% reactant concentrations to obtain the product, with very little by-product formation.

The following description is not intended to limit the invention, but merely to further illustrate the particular aspects of the technology that may be considered by formulators in the manufacture of a wide variety of detergent compositions using polyhydroxy fatty acid amides. Things.

It will be readily appreciated that polyhydroxy fatty acid amides are somewhat unstable under highly basic or highly acidic conditions because of their amide linkages. Although some decomposition is tolerable, it is preferred that these materials not be brought to a pH below about 11, preferably above 10, or below about 3 for too long. The pH of the final product (liquid) is typically between 7.0 and 9.0.

During the production of polyhydroxy fatty acid amides, it is typically required to at least partially neutralize the base catalyst used to form the amide bond. Although any acid may be used for this purpose, cleaning formulators will recognize that it is a simple and convenient way to use an acid that supplies other useful and desired anions in the final detergent composition. There will be. For example, citric acid can be used for the purpose of neutralization, and the citrate ion generated (about 1%) is about
It remains with the 40% polyhydroxyfatty acid amide slurry and is sent to the subsequent manufacturing stages of the overall detergent manufacturing process. Acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate and the like can be used as well.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C ₁₂ -C ₁₄₎ have their tallow alkyl (predominantly C ₁₆ -C ₁₈₎ are more soluble than derivatives. Thus, C ₁₂ -C ₁₄ towards the material is somewhat easier to formulate in the liquid component easily dissolved in cold water washing bath. However, C ₁₆ -C ₁₈ substances are also very useful, especially in an environment using washing water at normal temperature to high temperature. In fact, C
₁₆ -C ₁₈ materials may be better detergent surfactant from C ₁₂ -C ₁₄ derivatives. Therefore, the prescriber
When selecting a particular polyhydroxy fatty acid amide to use in a given formulation, it may be desirable to strike a balance between ease of manufacture and performance.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amide can be increased by having unsaturated fatty acid residues and / or having chain branching. Thus, materials such as polyhydroxy fatty acid amides derived from oleic acid and isostearic acid have
-Higher solubility than alkyl derivatives.

Similarly, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., is usually higher than the corresponding substances derived from monosaccharides. Such increased solubility can be particularly advantageous when formulating liquid compositions. In addition, polyhydroxy fatty acid amides where the polyhydroxy groups are derived from maltose appear to work particularly well as detergents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants. While not intending to be limited by theory, the combined use of LAS and polyhydroxyfatty acid amides derived from polysaccharides such as maltose substantially and significantly reduces interfacial tension in aqueous media, It is believed that the detergency is increased. (The production of polyhydroxyfatty acid amides derived from maltose is described below.) Polyhydroxyfatty acid amides are not only produced from purified sugars, but also hydrolyzed starches, such as corn starch, potato starch or formula. It can also be made from any other convenient plant-derived starch containing the mono-, di-, etc. sugars desired by the individual. This is extremely important from an economic point of view. For example, "high glucose"
Corn syrup, "high maltose" corn syrup and the like can be used conveniently and economically. Lignin removed and hydrolyzed cellulose pulp can also provide a source of polyhydroxy fatty acid amide.
As mentioned above, polyhydroxy fatty acid amides derived from higher sugars such as maltose and lactose are more soluble than those derived from glucose. In addition, more soluble polyhydroxy fatty acid amides can help solubilize less soluble ones to varying degrees. Therefore, except for selecting a syrup containing a small amount of maltose (eg, 1% or more)
One would choose to use a feedstock that contains high glucose corn syrup. The resulting mixture of polyhydroxy fatty acids generally exhibits more favorable dissolution properties over a wider range of temperatures and concentrations than polyhydroxy fatty acid amides derived from "pure" glucose. Thus, in addition to any economic benefits of using a sugar mixture over pure sugar reactants, polyhydroxyfatty acid amides prepared from mixed sugars have very substantial benefits in terms of performance and / or ease of formulation. provide. However, in some cases, some levels of grease removal performance (dishwashing) are lost at fatty acid maltamide levels above about 25%, and lathering is lost above about 33% (this percentage is the percentage of maltamide-derived polyhydroxyl in the mixture). Fatty acid amide to percent of polyhydroxy fatty acid amide from glucose.) This can vary somewhat with the chain length of the fatty acid residues. Typically, the formulator who decides to use such a mixture will have a ratio of monosaccharides (e.g., glucose) to higher sugars of disaccharide or higher (e.g., maltose) of about 4: 1 to about 99: 1. It can be found advantageous to select certain polyhydroxy fatty acid amide mixtures.

The production of polyhydroxy fatty acid amide from a fatty acid ester and an N-alkyl polyol is carried out in an alcohol solvent by about
It can be carried out at a temperature of from 30C to 90C, preferably from about 50C to 80C. For example, for liquid detergent formulators, the above steps can be performed in 1,2-propylene glycol solvent since it is not necessary to completely remove the glycol solvent from the reaction product prior to use in the finished detergent formulation. It may be convenient to do so. Similarly, the formulator of a solid, typically granular detergent composition, for example, may have ethoxylated (EO)
3-8) 30 ° C. to 9 ° C. in a solvent containing an ethoxylated alcohol such as a C ₁₂ -C ₁₄ alcohol, for example a commercial product such as NEODOL 23EO6.5 (Shell).
It can be found convenient to carry out the process at 0 ° C. When using such an ethoxylate,
It is preferred that they contain no substantial amount of non-ethoxylated alcohol and no substantial amount of mono-ethoxylated alcohol ("T" designation).

Although the preparation of the polyhydroxy fatty acid amide itself does not form part of the present invention, the formulator may also focus on other synthetic methods of the polyhydroxy fatty acid amide described below.

Typically, the reaction order on an industrial scale to produce the preferred acyclic polyhydroxyfatty acid amide is as follows: Step 1 From the desired saccharide or saccharide mixture, the formation of an N-alkylamine and an adduct of this saccharide with the N-alkylamine After preparing the alkylpolyhydroxyamine derivative, reacting it with hydrogen in the presence of a catalyst, then step 2 comprising reacting said polyhydroxyamine, preferably with a fatty acid ester, to form an amide bond. I have. Stage 2 of the reaction sequence
The various N-alkyl polyhydroxyamines used in can be prepared by various methods disclosed in the art, but the following methods are advantageous, using economical sugar syrups as raw materials. I have. When using such syrup ingredients, it should be understood that for best results, the manufacturer should choose a syrup that is very bright or preferably nearly colorless ("clear and colorless"). It is.

Preparation of N-Alkyl Polyhydroxyamines from Vegetable Sugar Syrups I. Formation of Adducts The following is a description of an approximately 55% glucose solution with less than 1 Gardner color (corn syrup, approximately 23%).
1 g glucose, about 1.28 mol) about 420 g about 50% aqueous methylamine (methylamine 59.5 g, 1.92 mol) solution about 119 g
This is a standard method characterized by reacting Methylamine (MMA) solution is replaced with N ₂ shield, about 1
Cool to 0 ° C or less. Corn syrup at a temperature of about 10 ° C. to 20 ° C. was replaced with N ₂ shield. Corn syrup,
Add slowly to the MMA solution at the prescribed reaction temperatures described below. The Gardner color is measured at a given time expressed in minutes.

As can be seen from the above data, when the temperature exceeds about 30 ° C, the Gardner color of the additional product is quite bad,
At about 50 ° C., the time for the Gardner color of the adduct to fall below 7 is only about 30 minutes. For longer reaction times and / or longer hold times, the temperature should be less than about 20 ° C. To obtain good color glucamine, the Gardner color is less than about 7, preferably less than about 4.

When forming adducts at low temperatures, the time to reach a substantial equilibrium concentration of the adduct is reduced by increasing the amine to sugar ratio. At a 1.5: 1 molar amine to sugar ratio, the reaction temperature reaches equilibrium at about 30 ° C. in about 2 hours. At a ratio of 1.2: 1 mol under the same conditions, the time is at least about 3 hours. To obtain good color, the combination of amine: sugar ratio, reaction temperature and reaction time is selected to achieve a substantial equilibrium conversion, for example, greater than about 90% for sugar. , Preferably about
It is selected to be greater than 95%, more preferably greater than about 99%, and the color of the adduct is less than about 7, preferably less than about 4, more preferably less than about 1.

The color of the MMA adduct (after reaching a substantial equilibrium in at least about 2 hours) when the reaction temperature is less than about 20 ° C. and the process and corn syrup having various Gardner colors as described above are used. Is as described above.

As can be seen from the above table, the starting sugar material must be nearly colorless to obtain a consistently acceptable adduct. When the sugar has a Gardner color of about 1, the adduct may or may not be acceptable.
When the Gardner color is greater than one, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Hydrogen Reaction The adduct obtained from the above reaction having a Gardner color of 1 or less is hydrogenated by the following procedure.

About 539 g of the adduct dissolved in water and about 23.1 g of G49B Ni catalyst manufactured by United Catalyst
And 1 liter autoclave, 200psi at about 20 ℃
It is replaced twice with gH _2. Increase H ₂ pressure to about 1400 psi and reduce temperature to about
Increase to 50 ° C. The pressure is then increased to about 1600 psig and the temperature is held at about 50-55 ° C for about 3 hours. The product is now about 95% hydrogenated. The temperature is then raised to about 85 ° C. for about 30 minutes, the reaction mixture is decanted and the catalyst is filtered off. water and
The product after distilling off the MMA is a white powder of about 95% N-methylglucamine.

The above procedure is repeated with about 23.1 g of Raney nickel catalyst, except for the following changes. After washing the catalyst three times and putting the catalyst in the reactor,
Was replaced twice with 0PsigH _2, emits a reactor 2 hours pressurized to 1600 psig with H _2, the pressure at 1 hr, 1600 psig and reactor
And repressurized. The adduct was then fed to the reactor at 200 psig and 20 ° C. and the reactor was
Replace with ₂ etc.

The product in each case is greater than about 95% N-methylglucamine, with about 10 ppm Ni to glucamine.
And the color of the solution is less than about 2 in Gardner color.

Crude N-methylglucamine has color stability for short exposures of about 140 ° C.

Low sugar content (less than about 5%, preferably less than about 1%)
And good color (less than about 7, preferably less than about 4,
More preferably, less than about 1 Gardner), it is important to obtain good adducts.

In another reaction, about 159 g of about 50% methylamine
It was dissolved in water, which was replaced with N ₂ at about 10 to 20 ° C., starting from those shielding to prepare an adduct. About 330 g of about 70% corn syrup (almost colorless and transparent) is degassed with N ₂ at about 50 ° C. and slowly added to the methylamine solution at a temperature below about 20 ° C. The solution is mixed for about 30 minutes to give an adduct of about 95% of a very bright yellow solution.

A solution of about 190 g of the adduct in water and about 9 g of G49B Ni catalyst manufactured by United Catalyst are placed in a 200 ml autoclave and replaced with H ₂ at about 20 ° C. three times. H ₂ the pressure about 200psi
To about 50 ° C. Increase the pressure to about 250 psi
Maintain the temperature at about 50-55 ° C for about 3 hours. At this point about 95
The% hydrogenated product is then raised to a temperature of about 85 ° C. for about 30 minutes, and the product after evaporation after removal of water and evaporation contains about 95% N-methylglucamine. Is a white powder.

When H ₂ pressure is less than about 1000psig is to minimize the contact between adduct and catalyst, it is also important to minimize the Ni content in the glucamine. The nickel content of N-methylglucamine in this reaction is about 100 ppm compared to less than 10 ppm in the previous reaction.

The following reaction H ₂ is used is conducted in order to compare the effects of reaction temperature directly.

After performing a typical procedure similar to the one described above, 20
Using a 0 ml autoclave reactor, an adduct is prepared and a hydrogen reaction is performed at various temperatures.

The adduct used to make glucamine was an approximately 55% glucose (corn syrup) solution (231 g glucose, 1.28 mol) (this solution was made using CarGill 99DE corn syrup, and the color of the solution was Gardner 1).
About 420 g and 50% methylamine (59.5 g MMA, 1.
92 mol) (made by Air Products)
Prepared by combining with 119 g.

 The procedure of the reaction is as follows.

1. Place about 119 g of a 50% methylamine solution in a reactor purged with N ₂ and cool to less than about 10 ° C.

2. 55% corn syrup solution degassing and / or replaced with N ₂ at 10 to 20 ° C., to remove oxygen in the solution.

3. Gradually add the corn syrup solution to the methylamine solution and keep the temperature below about 20 ° C.

4. Once all the corn syrup solution has been added,
Stir for 2 hours.

The adduct is used in the hydrogen reaction immediately after it is made, or is stored at a low temperature to prevent degradation.

 The hydrogen reaction of the glucamine adduct is as follows.

1. Approximately 134g of additive (gardner color is less than approximately 1)
And 5.8 g of G49B Ni into a 200 ml autoclave.

2. In about 20 to 30 ° C., to replace twice the reaction mixture at about 200PsiH _2.

3. Pressurize to about 400 psi with H ₂ and raise the temperature to about 50 ° C.

4. Increase pressure to about 500 psi and let react for about 3 hours. Maintain the temperature at about 50-55 ° C. Sample 1 was collected.

5. Raise the temperature to about 85 ° C for about 30 minutes.

6. Decant and filter out the Ni catalyst. Sample 2 was collected.

Isothermal Reaction Conditions 1. About 134 g of the adduct and about 5.8 g of G49BNi are placed in a 200 ml autoclave.

2. Replace twice at about 200 psiH ₂ at low temperature.

3. Pressurize to about 400 psi with H ₂ and raise the temperature to about 50 ° C.

4. Increase the pressure to about 500psi and react for about 3.5 hours. The temperature is maintained at a predetermined temperature.

5. Decant the Ni catalyst and filter off. Sample 3 is about 50-55 ° C
Sample 4 is for about 75 ° C. and Sample 5 is for about 85 ° C. (Approx. 85 ° C
The reaction time for is about 45 minutes. All treatments have similar purity (about 94%) for N-methylglucamine, and the Gardner color for each treatment is the same immediately after the reaction, but the two-step heat treated flea gives good color stability. , 85 ° C treatment produces near limit color immediately after the reaction.

Example 12 The preparation of tallow (cured) fatty acid amide for use in the detergent composition according to the present invention is as follows.

Step 1 Reactant: Maltose monohydrate (Aldrich,
Lot number 01318KW), methylamine (40% by weight aqueous solution) (Aldrich, lot number 03325TM), Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot number 12921LW).

Add reactants to glass liner (250 g maltose, 42 g
8 g methylamine solution, 100 g catalyst slurry-50 g Raney nickel), placed in a 3 liter shaking autoclave,
This is nitrogen (3 × 500psig) and hydrogen (2 × 500psig)
In substituted, with H ₂ atmosphere with nitrogen and shaken over the weekend at a temperature of 28 ° C. to 50 ° C.. The crude reaction mixture is vacuum filtered twice through a glass microfiber filter equipped with a silica gel stopper. Concentrate the filtrate to a viscous material. After dissolving this material in methanol, the last traces of water are azeotropically removed by removing the methanol / water on a rotary evaporator. The final drying is performed under high vacuum. The crude product is dissolved in refluxing methanol, filtered, recrystallized on cooling, filtered and the filter cake is dried at 35 ° C. under vacuum. This is Sample No. 1. The filtrate is concentrated until a precipitate starts to form and stored in the refrigerator overnight. The solid is filtered and dried under vacuum. This is Sample No. 2. The filtrate is again concentrated to half the volume and recrystallized. Very little precipitate forms. A small amount of ethanol is added and the solution is left in the refrigerator over the end. Filter the solid material and dry under vacuum. The consolidated solid consists of N-methylmaltoamine, which is used in step 2 of the total synthesis.

Step 2 Reactants: N-methylmaltoamine (from step 1), cured tallow methyl ester, sodium methoxide (25% methanol solution), anhydrous methanol (solvent), molar ratio 1: 1 = amine: ester, initial catalyst Concentration 10
Mol% (w / r maltoamine), rising to 20 mol%, solvent level 50% (weight).

In a sealed bottle, 20.36 g of tallow methyl ester is heated to its melting point (water bath) and placed in a three-necked round bottom flask equipped with a mechanical stirrer. Heat the flask to about 70 ° C,
Prevents the ester from solidifying. Separately, 25.0 g of N-methylmaltoamine are combined with 45.36 g of methanol and the resulting slurry is added to the tallow ester with thorough mixing. 1.51 g of 25% sodium methoxide dissolved in methanol is added. After 4 hours, the reaction mixture did not become clear, so an additional 10 mole% (20 mole% total) of the catalyst was added and the reaction was continued overnight (about 68 ° C), whereupon the mixture became clear. Next, distillation is performed by modifying the reaction flask. Increase temperature to 110 ° C. 6 distillation at atmospheric pressure
Continue for 0 minutes. Next, distillation under high vacuum was started, and 14
After a period of minutes, the product becomes very viscous. The product
Leave in the reaction flask at 110 ° C. (external temperature) for 60 minutes. The product is removed from the flask and triturated in ethyl ether over the weekend. The ether is distilled off on a rotary evaporator and the product is stored in an oven overnight and ground to a powder. Residual N-methylmaltoamine is removed from the product using silica gel. A slurry of silica gel in 100% methanol is placed in a funnel and washed several times with 100% methanol. Product (20g
/ 100% methanol (100 g) on silica gel and elute several times using vacuum and several methanol washes. The combined eluate is evaporated to dryness (rotary evaporator). The remaining tallow ester is removed by triturating overnight with ethyl acetate and then filtered. Vacuum dry the filter cake overnight. The product is a tallow alkyl N-methylmaltoamide.

In another scheme, step 1 of the reaction sequence comprises glucose or a mixture of glucose and typically 5
% Of maltose in a commercially available corn syrup. The resulting polyhydroxyfatty acid amines and mixtures can be used in any of the detergent compositions of the present invention.

In yet another scheme, Step 2 of the reaction sequence described above.
Can be carried out in 1,2-propylene glycol or neodol. At the discretion of the formulator, it is not necessary to remove propylene glycol or neodol from the reaction product before formulating the detergent composition with the reaction product. Also, if desired by the formulator, the methoxide catalyst can be neutralized with citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.

Depending on the wishes of the formulator, the compositions of the present invention may contain some foam control agents. Typically, no high-foaming agents are used in dishwashing, as no suds suppressors are used. For laundering textiles in a top-loading washing machine, it is desirable to have some foam control, and the front-loading (fr)
In on-loading washing machines, significant levels of suds suppressors may be preferred. A wide variety of suds suppressors are known in the art and can be routinely selected for use in the present invention. In fact, the choice of suds suppressor or suds suppressor mixture for any particular detergent composition will not only depend on the presence and amount of the polyhydroxy fatty acid amide used in the present invention, but will also be included in the formulation. It also depends on the surfactant used. However,
For use with polyhydroxy fatty acid amides, various silicone-based suds suppressors are more efficient (i.e., can be used at lower concentrations) than various other suds suppressors. Silicone foam suppressors X2-3419 and Q2
-3302 (a silicone suds suppressor commercially available as Dow Corning) is particularly useful.

Formulators of fabric detergent compositions that can conveniently include a soil release agent have a wide variety of known materials to choose from (e.g., U.S. Patent Nos. 3,962,152 and 4,116,885).
Nos. 4,238,531, 4,702,857, 4,721,580 and 4,877,896. ) Other soil release agents which can be used in the present invention, C ₁ -C ₄ polyethoxy units sources having alkoxy-terminated (e.g., CH ₃ [O
CH ₂ CH ₂ ] ₁₆ OH), terephthaloyl unit source (eg, dimethyl terephthalate), poly (oxyethylene) oxy unit (eg, polyethylene glycol 1500), oxyiso-propyleneoxy unit source (eg, 1,2-propylene glycol) And a non-ionic oligomeric esterification product of a reaction mixture comprising a source of oxyethyleneoxy units (eg, ethylene glycol), especially where the molar ratio of oxyethyleneoxy units: propyleneoxy units is at least about 0.5: 1. There are things. Such non-ionic soil release agents have the general formula Wherein R ¹ is lower (ie, C ₁ -C ₄ ) alkyl, especially methyl, x and y are each an integer from about 6 to about 100, and m is an integer from about 0.75 to about 30 , N is about 0.25
To about 20 represents an integer of, R ² is an oxyethylene: at least about 0.5 molar ratio of oxyisopropylene propyleneoxy: 1
Which is a mixture of H and CH ₃ for

Another preferred class of soil release agents useful in the present invention is of the general anionic type described in U.S. Pat. No. 4,877,896, but these release agents are substantially of the HOROH type ( (Where R is propylene or higher alkyl). For example, the soil release agents described in U.S. Pat. No. 4,877,896 include dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-
While being the reaction product of sodium sulfobenzoic acid, these additional soil release agents are, for example, the reaction products of dimethyl terephthalate, ethylene glycol, 5-sodium sulfoisophthalate and 3-sodium sulfobenzoic acid. Such compounds are preferred for use in granular laundry detergents.

It is advantageous for the formulator to include the non-perborate bleach, especially in high-granular laundry detergents. Various peroxygen bleaches are commercially available and can be used in the present invention, of which percarbonate is convenient and economical. Accordingly, the compositions of the present invention may contain solid bleach, usually at a level of 3% to 20%, more preferably 5% to 18%, most preferably 8% to 15% by weight of the composition. In the form of a sodium salt.

Sodium percarbonate is an adduct having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Most commercially available materials contain low levels of heavy sequestering agents incorporated during the manufacturing process, such as EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP) or amino-phosphate. For use in the present invention, the percarbonate can be incorporated into the detergent composition without additional protection, but the preferred embodiment of the present invention utilizes a stable form of the material (FMC). A wide variety of coatings can be used, but the most economical is
SiO _2: Na ₂ O ratio of 1.6: 1 to 2.8: 1, preferably 2.0: a 1 sodium silicate, applied as an aqueous solution, dried, the weight of the silicate solid percarbonates Yields concentrations of 2% to 10% (usually 3% to 5%). Magnesium silicate can also be used, and a chelating agent such as one of the above can be included in the coating.

The particle size range of the crystalline percarbonate is 350 μm to 450 μm, with an average value of about 400 μm. Upon coating, the grain size of the crystals is in the range of 400-600 μm.

The heavy metals contained in the sodium carbonate used to make the percarbonate can be adjusted by including a sequestering agent in the reaction mixture, but the percarbonate is still present as an impurity in other components of the product. It must be protected from the heavy metals it contains. The total concentration of iron, copper and manganese ions in the product should not exceed 25 ppm,
It should preferably be less than 20 ppm so as not to unacceptably adversely affect the stability of the percarbonate.

The new concentrated laundry detergent particles are as follows.

Example 13 ¹ laminated silicate builders are known in the art. Preferred is laminated sodium silicate. See, for example, the laminated sodium silicate builder described in U.S. Pat. No. 4,664,859, issued May 12, 1987 to HP Rieck, which is incorporated herein by reference. . A suitable laminated silicate builder is commercially available from Hoechst as SKS-6.

² Nove Nordisk A / S, commercially available from Copenhagen.

Highly preferred granules of the type described above have an active enzyme of about 0.00
Those containing from 01% to about 2% by weight and at least about 1% by weight of the polyhydroxyfatty acid amide, most preferably those in which the anionic surfactant is not an alkylbenzene sulfonate surfactant.

Example 14 The following illustrates a perborate bleach + bleach activator detergent composition of the present invention, prepared by mixing the above ingredients in a mixing drum.

In this example, zeolite A represents hydrated crystalline zeolite A containing about 20% water and having an average particle size of 1-10, preferably 3-5 μm, and LAS is a C _12.3 linear alkylbenzene sulfonic acid. Represents sodium, AS
Represents a C ₁₄ -C ₁₅ sodium alkyl sulfate, and nonionic, coconut alcohol per mole ethyleneoxy engaged about 6.5 moles and condensation, a coconut alcohol were stripped and Monoetokishiru alcohols that are not ethoxylated, Also abbreviated as CnAE6.5T, DTPA
Represents sodium diethylenetriaminepentaacetate.

^One- base granules are obtained by spray-drying of an aqueous crutcher mix of the indicated ingredients.

² Typically consisting of about 60% water, about 2% available oxygen (AvO) of peroxyacid (corresponding to about 36% NAPAA) and the balance (about 4%) of unreacted starting material A sample of a freshly prepared NAPAA wet cake is obtained. This wet cake is a crude reaction product of NAAA (monononyl amide of adipic acid), sulfuric acid and hydrogen peroxide, which is then quenched by adding water and then filtered. , Distilled water and a phosphate buffer washing solution, and finally suction filtration to collect a wet cake. Air-dry a part of this wet cake at room temperature,
A dry sample is obtained, typically consisting of about 5% AvO (corresponding to about 90% NAPAA) and about 10% unreacted starting material. When dried, the pH of the sample is about 4.5.

NAPAA granules are dried NAPAA wet cake (about 10%
About 51.7 times, C _12.3 linear sodium alkylbenzene sulfonate (LAS) paste (45%
Activity) prepared by mixing 11.1 parts, about 43.3 parts of sodium sulfate and about 30 parts of water in a CUISINART mixer. After drying, (about 47
% NAPAA) is sized by passing it through a No. 14 Tyler mesh and retaining all particles that do not pass through a No. 65 Tyler mesh. Malvern
n) the average size of the amidoperoxy acid particles (agglomerates) as determined by particle size analysis is about 5-40 microns;
The median particle size is about 10-20 microns.

³ NOBS (nonanoyloxybenzenesulfonate) granules are disclosed in 1991 as part of that disclosure.
It is prepared by the method of Bowling et al., U.S. Pat.

⁴ Zeolite granules having the following composition are made by mixing zeolite A with PEG8000 and CnAE6.5T in an Eirich ROB energy intense mixer.

PEG8000 is in an aqueous form containing 50% water and has a temperature of about 55 ° F (12.8 ° C). CnAE6.5T is liquid and is maintained at about 90 ° F (32.2 ° C). These two types of liquids are mixed in a 12 element static mixer
To form a compound. The exit temperature of the resulting binder material is about 75 ° F (23.9 ° C) and the clay is about 500 ° C.
It is 0cps. The ratio of PEG8000 to CnAE6.5T in the fixed mixer is 72:28, respectively.

The Erich RO8 energy mixer is operated in a batch mode. First, 34.1 g of powdered zeolite A are weighed into a mixer pan. The mixer is taught by first rotating the pan counterclockwise at about 75 revolutions per minute (rpm) and then rotating the rotor blades clockwise at 1800 rpm. The binder material is then pumped directly from a stationary mixer into an Erich RO8 energy strong mixer containing zeolite A. The feed rate of this binder material is about 2
Minutes. Continue mixing for an additional minute in the mixer, for a total batch time of about 3 minutes. The batch is then emptied and collected on a fiber drum.

Repeat the batch stage until about 225 kg of wet product is collected. Next, the emptied product is transferred to 240-270 ゜
Dry in a fluid bed at F (116-132 ° C). Most of the free water is removed during the drying step, and the composition is changed as described above. The total energy input provided to the product by the mixer in a batch mode is about 1.31 × 10 ¹² ergs / kg at a rate of about 2.18 × 10 ⁹ ergs / kg · s.

The average particle size of the free-flowing agglomerates formed is about 450-500
Micron.

Example 15 Granular laundry detergent compositions suitable for use at relatively high concentrations and a wide range of temperatures, particularly common in European front-loading automatic washing machines, are as follows.

¹ SOKALAN is polyacrylic acid / sodium maleate from Hoechst.

^2. Pentaphosphonomethyldiethylenetriamine manufactured by Monsanto.

³ Ciba-Geigy optical brightener.

⁴ Trade name: FINNNFIX, manufactured by Metasaliton.

⁵ LIPOLASE, a lipolytic enzyme made by Novo.

⁶ SAVINASE, a protease enzyme from Novo.

⁷ X2-3419 is a silicone suds suppressor manufactured by Dow Corning.

The procedure for preparing the granules consists of various tower drying, agglomeration, drying-addition and the like as described below. Percentages are based on the final product.

A. Injection into clutches and towers Using standard techniques, clutch the following components (crut
ched), the tower was dried.

SOKALAN CP5 3.52% DEQUEST 2066 0.45% TINOPAL DMS 0.28% Magnesium sulfate 0.49% Zeolite A, 7.1% as anhydrous CMC 0.47% B. Surfactant aggregates B1. Tallow alkyl sulfate sodium salt and C _12-15 EO (3) Aggregation of sodium salt paste of sulfate 50% active paste of tallow alkyl sulfate and C
Aggregate _12-15 EO (3) sulfate 70% paste with zeolite A and sodium carbonate according to the following recipe (contributing to the detergent formulation after drying of the agglomerates).

Tallow alkyl sulfates _{2.82% C 12~15 EO (3)} 1.18% sulfate Zeolite A 5.3% Sodium carbonate 4.5% B2. C ₁₄ ~C ₁₅ alkyl sulfates, C ₁₂ -C ₁₅ alkyl ethoxy sulfates, Dobanol (DOBANOL) C ₁₂ ~
Aggregates of C ₁₅ EO (3) and C ₁₆ -C ₁₈ N-methylglucose amide C ₁₆ -C ₁₈ glucose amide nonionic material is converted from dovanol C present during the reaction of methyl esters with N-methylglucamine. synthesized using _{12 ~C 15} EO (3). C
_12-15 EO (3) acts as a melting point depressant, which allows the reaction to proceed without forming undesirable cyclic glucose amides.

20% dovanol C _12-15 EO (3) and 80% C ₁₆ -C ₁₈ N-
A surfactant mixture with methylglucose amide is obtained, which is coagulated with 10% sodium carbonate.

Secondly, the particle then C ₁₄ -C ₁₅ alkyl sulfates, sodium salts of highly active paste of (70%) C
Coagulate with _12-15 EO (3) sulfate, zeolite A and pseudonymous sodium carbonate. The particles are C _{16 to} C ₁₈
It shows good dispersibility of N-methylglucose amide in cold water.

The general formulation of the particles (after drying of the agglomerates, which contributes to the detergent formulation) is as follows:

C ₁₆ -C ₁₈ N-methylglucose amide 4.1% Dovanol C _12-15 EO (3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% C ₁₄ -C ₁₅ Sodium alkyl sulfate 3.5% C _12-15 EO (3) Sulfuric acid Sodium 0.59% C. Dry adduct Add the following ingredients:

Percarbonate 22.3% TAED (Tetraacetylethyleneamine) 5.9% Hoechst laminated silicate SK66 12.90% Citric acid 3.5% Lipolase 0.42% 100,000LU / g SAVINASE4.0KNPU 1.65% Zinc phthalocyanine (photobleach) 0.02% D. Spraying Dovananol C _12-15 EO (3) 2.60% Fragrance 0.53% E. Foam Inhibitor Silicone foam inhibitor X2-3419 from Dow Corning (95% to 97% high molecular weight linear silicone; 3% to
5% hydrophobic silicone) with zeolite A (2-5μ)
m), coagulated with starch and stearyl alcohol binder. The particles have the following formula:

Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% Detergent preparations are used in European washing machines, for example AE
When using 85 g of detergent in a G brand washing machine at 30 ° C, 40 ° C, 60 ° C and 90 ° C cycles, it shows excellent solubility, excellent performance and foam control action.

Example 16 In any of the foregoing examples, the fatty acid glucamide surfactant can be replaced with an equivalent amount of a maltamide surfactant or a glucamide / maltoamide mixture derived from a plant sugar source. In these compositions, the use of ethanolamide will aid in the low temperature stability of the finished formulation. In addition, the use of a sulfobetaine (also known as "sultaine") surfactant results in excellent lathering.

If a particularly good foaming composition is desired (for example,
Dishwashing), since there is possible to suppress the C ₁₄ or more fatty acids are foaming, these fatty acids are preferably less than about 5%, more preferably less than about 2%, and most preferably substantially free at all. Therefore, the formulator of the high foaming composition may not introduce such a suds suppressing amount of fatty acid into the high foaming composition comprising polyhydroxy fatty acid amide and / or reduce the C ₁₄ or higher fatty acids during storage of the finished composition. It is desirable not to form any. One simple means is to prepare the polyhydroxy fatty acid amides of the present invention with reference to C ₁₂ ester reactants. Fortunately, the use of an amine oxide or sulfobetaine surfactant can reduce some of the negative foaming effects caused by this fatty acid.

A relatively high concentration of anionic optical brightener (eg,
Formulators who wish to add to liquid detergents containing anionic or polyanionic substituents, such as (10% or more) polycarbonate builder, may premix the brightener with water and polyhydroxyfatty acid amide and then add the premix. It can be found useful to add to the final composition.

Polyglutamic or polyaspartic acid detergent,
It can be used effectively with detergents containing zeolite. AE fluids or flakes and DC-544 (Dow Corning) are other examples of useful foam control agents of the present invention.

If a person skilled in the chemical technical field prepares a polyhydroxyfatty acid amide using a disaccharide or higher saccharide such as maltose, the polyhydroxyfatty acid amide, in which the linear substituent Z has a polyhydroxy ring structure, It will be understood that this results in what is "capped". Such materials are intended for use in the present invention and do not depart from the spirit and scope of the disclosed and claimed invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C11D 1/52 C11D 3/37 C11D 3/32 WPI / L (QUESTEL) EPAT (QUESTEL)

Claims (14)

(57) [Claims] 1. A detergent composition comprising a dispersant, comprising: Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is a linear hydrocarbyl chain. A polyhydroxyhydrocarbyl having at least 3 hydroxyls directly attached to this chain) or an alkoxylated derivative thereof, and (b) anionic and At least 1% of a detergent surfactant other than the polyhydroxyfatty acid amide selected from the group consisting of nonionic detergent surfactants and mixtures thereof; (c) polycarboxylate and polyethylene glycol polymers; A polymeric dispersant selected from the group consisting of A detergent composition comprising at least 0.5% and a weight ratio of (a) :( c) of 1:10 to 10: 1. 2. The method according to claim 1, wherein said polyhydroxy fatty acid amide is 3% to
50% and 5% to 40% of the detergent surfactant (b).
Comprising 0.5% to 10% of the polymeric dispersant,
The detergent composition according to claim 1. 3. The method of claim 2, wherein the polymeric dispersant has the formula Wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl, M is a salt-forming cation, and n is 30-400. 3. The detergent composition according to claim 2, comprising at least 60% by weight of monomer units. 4. The detergent composition according to claim 3, wherein the dispersant comprises polymerized acrylic acid or a soluble salt thereof, and has an average molecular weight of 2,000 to 10,000. 5. The dispersant comprises an acrylate / maleate copolymer, preferably the copolymer has a ratio of acrylate to maleate moieties in the range of 30: 1 to 1: 1 and an average molecular weight of 5,000 to 75,000. A detergent composition according to claim 3. 6. The detergent composition according to claim 2, wherein said polymeric dispersant is polyethylene glycol. 7. R ¹ is methyl, R ² is C ₉ -C ₁₇ alkyl or alkenyl and Z is derived from a reducing sugar, preferably of the formula —CH ₂ (CHOH) _n CH ₂ OH, —CH (CH ₂ OH) -CHO
R'-CHOH-CH ₂ OH or _{-CH (CH 2 OH) - (} CHOH) n-1 -
The detergent composition according to claim 1, wherein CH ₂ OH, wherein R ′ is H or an acyclic or aliphatic monosaccharide, and n is an integer of 3 to 5. 8. Z is —CH ₂ (CHOH) _n CH ₂ OH and n is 4
The detergent composition according to claim 7, which is: 9. The composition according to claim 1, wherein for the polyhydroxy fatty acid amide, Z is derived from maltose. 10. The polyhydroxyfatty acid amide according to claim 10, wherein Z is derived from a mixture of monosaccharides, disaccharides and optionally higher saccharides, said mixture comprising at least one disaccharide, preferably maltose. A composition according to claim 1. 11. The detergent surfactant (b) is an alkyl sulfate, an alkyl ethoxylated sulfate,
2. The composition of claim 1, wherein the composition is an alkyl ester sulfonate, an alkyl benzene sulfonate, an alkyl ethoxylate, an alkyl polyglycoside, an alkyl phenol ethoxylate, a paraffin sulfonate, or a mixture thereof, preferably 5% to 40% of the composition. Detergent composition. 12. A method of washing a cloth in an aqueous solution using a detergent composition comprising one or more anionic or non-ionic detergent surfactants and a polymeric dispersant, The detergent composition has the formula Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is a linear hydrocarbyl chain. poly hydroxyhydrocarbyl at a at least three hydroxyl are those directly attached to the chain, preferably C ₁₁ -C ₁₇ N-methyl glucamide, C ₁₁ -C ₁₇ N-methyl maltoside amide or said to have Which is a mixture of glucamide and maltoamide of the formula (a), or at least 1% by weight of an alkoxylated derivative thereof,
The method wherein the dispersant is selected from the group consisting of polycarboxylate and polyethylene glycol polymers, and mixtures thereof. 13. A mixed monosaccharide, wherein said Z residue in said polyhydroxy fatty acid amide is available from a vegetable source;
13. The method according to claim 12, wherein the method is derived from a disaccharide and a polysaccharide. 14. The method according to claim 12, wherein the R ² residue in the polyhydroxy fatty acid amide is a C ₁₅ -C ₁₇ alkyl, alkenyl, or a mixture thereof.