JP3046069B2 - Polyhydroxy fatty acid amide in zeolite / laminated silicate built-in detergent - Google Patents

Description

Description: FIELD OF THE INVENTION To support detergent formulations, zeolites or layered silicate detergent builders or mixtures thereof are combined with polyhydroxy fatty acid amides.

BACKGROUND OF THE INVENTION Various builder substances have been proposed for use in detergent compositions. Such a substance performs various functions such as a hardness sequestering action, a peptizing action, and a pH control. Although sodium tripolyphosphate has been a particularly preferred builder for many years, recent developments in this field include builder substances such as zeolites, various polycarboxylates, and the like. At present, fully formulated detergents include zeolite builders or carboxylate builders or mixtures thereof.

The development of phosphate-free high performance detergent compositions has been a challenge for the detergent industry. From a performance point of view, even the best zeolite builders are "under-built" in hard water. Furthermore, ordinary zeolite builders treat calcium hardness, but are not particularly effective against magnesium hardness. Laminated silicate builders have recently been discovered for use as detergent builders. However, laminated silicates treat magnesium hardness, but are somewhat unsuitable for controlling calcium hardness.

Currently, almost all phosphate-free heavy-duty granular detergents contain a zeolite builder. Although zeolite-built laundry detergents are widely marketed, their disadvantages are known to formulators. Improving the performance of zeolite or laminated silicate builder compositions requires complex compounding equipment to incorporate various detergent additives into the detergent composition. Materials such as cleaning enzymes, mud removal polymers, bleaches and bleach activators are commonly used to enhance the performance of the built detergent compositions.

In addition, for many years, detergent formulators have been striving to obtain comparable and effective phosphate-free detergents in place of built-in phosphate detergents, but have relied on surfactants derived from petroleum or other non-renewable resources. They are more and more interested in formulating less detergents.

In accordance with the present invention, a few polyhydroxy fatty acid amide detergent compositions provide excellent overall cleaning by completely or partially replacing commonly used petroleum derived surfactants, such as linear alkyl benzene sulfonates. It has been discovered that performance can occur. These polyhydroxy fatty acid amides are obtained predominantly or entirely from natural renewable raw materials, are also degradable, and show low toxicity to aquatic organisms. These polyhydroxy fatty acid amides can enhance the solubility and dissolution of surfactants and auxiliary builder salts during use of the detergent composition. Even more surprising,
These polyhydroxy fatty acid amides can enhance the performance of zeolite and laminated silicate builder detergents under under-built cleaning conditions.

Briefly, the present invention provides an improved detersive surfactant containing a zeolite and / or a laminated silicate builder. According to the present invention, polyhydroxy fatty acid amides are used in zeolite and / or laminated silicate builder detergents to enhance detergent performance.

Prior art Various polyhydroxy fatty acid amides are known in the art. For example, N-acyl, N-methylglucoamide is
JS Goodbye, MA Marcus, E. Ching, and PL Finn, “Thermotropic Liquid-Crystalli
ne Properties of Some Straight Chain Carbohydrate
Amphiphiles ", LIQUID CRYSTALS, 1988, Volume 3, No.11, p
p 1569-1581, and also A. Müller Fanau,
"Moleculara and Crystal Structure of a Noni" by V. Zabel, M. Stafa and R. Hilgenfeld
onic Detergent: Nonanoyl-N-methylglucamide, "J.Ch
em.Soc.Chem.Commun., 1986, pp.1573-1574. Recently, the use of N-alkyl polyhydroxyamide surfactants in biochemistry, for example for dissociation of physiological membranes, has become of substantial interest. For example, a journal article, "ND-Gluco-N-methyl-alkanam"
ide Compounds, a New Class of Non-Ionic Detergents
for Membrane Biochemistry, "Biochem. J. (1982), Vo
See l.207, pp 363-366 (JEK Hilldress).

The use of N-alkyl glucoamides in detergent compositions has been discussed. U.S. Pat. No. 2,065,576 and British Patent No. 809,060 relate to detergent compositions containing an anionic surfactant and a few amide surfactants, with N-methylglucoamide added as a low temperature foaming enhancer. It is. These compounds contain the N-acyl group of higher linear fatty acids having 10-14 carbon atoms. These compositions also include auxiliary substances such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates.
It is also generally indicated that the composition may contain additional components that impart the desired properties to the composition, for example, fluorescent dyes, bleaches, fragrances, and the like.

U.S. Pat. No. 3,703,798 relates to an aqueous detergent composition comprising a condensation reaction product of an N-alkyl glucoamine and an aliphatic ester of a fatty acid. The product of this reaction is said to be usable in aqueous detergent compositions without further purification. It is also known to produce sulfurized esters of acylated glucoamines as described in US Pat. No. 2,717,894.

PCT International Patent Application WO 83/04412 relates to amphoteric compounds containing polyhydroxyaliphatic groups, these compounds being used as surfactants in cosmetics, drugs, shampoos, lotions and eye drops, emulsifiers and preparations for pharmaceuticals It is said to be useful as a component and also in biochemistry for the solubilization of membranes, whole cells or other tissue samples and for the preparation of liposomes. Within this disclosure, the formulas R'CON (R) CH2R "and R" CON (R) R 'are described, where R is hydrogen or an organic group and R' is at least 3
An aliphatic hydrocarbon group of carbon atoms, and R ″ is the residue of an aldose.

European Patent 0,285,768 relates to the use of N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. Includes amides of the formula R1C (O) N (X) R2. Where R1 is C1-C17 (preferably C7-C17)
Alkyl, R2 is hydrogen, C1-C18 (preferably C1-C6) alkyl or alkylene oxide, and X is a polyhydroxyalkyl having 4 to 7 carbon atoms, such as N-methyl, coconut fatty acid glucoamide. Although the thickening properties of this amide are stated to be particularly effective in liquid surfactant systems containing paraffin sulfonates, the aqueous surfactant systems include alkylaryl sulfonates, olefin sulfonates, Other anionic surfactants such as sulfosuccinic acid half ester salt and fatty alcohol ether sulfonate, and fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymer And other nonionic surfactants. As an example, a paraffin sulfonate / N-methyl coconut fatty acid glucoamide / nonionic surfactant shampoo formulation can be fried. N-polyhydroxyalkyl fatty acid amides are said to have excellent skin tolerance properties in addition to thickening action.

The bar detergent described in U.S. Pat.No. 2,982,737 is urea,
Sodium lauryl sulfate anionic surfactant, and N
N-methyl, N-solbutyl laurylamide and N-methyl, N-solbutylmyristylamide
-Contains an alkylglucoamide nonionic surfactant.

Other glucoamide surfactants are described, for example, in DT2,226,872, and the detergent composition in connection with this patent is a detergent composition selected from one or more surfactants and polymeric phosphates, a sequestering agent and a detergent. An alkali and improved by the addition of an N-acylpolyhydroxy-alkyl-amine of R1C (O) N (R2) CH2 (CHOH) nCH2OH, where R1 is C1-C3 alkyl, R2 is C10-C22 alkyl, N is 3 or 4. N- as a soil suspending agent
Acyl polyhydroxyalkylamine is added.

The detergent composition described in U.S. Pat. No. 3,654,166 comprises at least one surfactant selected from the group consisting of anionic, zwitterionic and nonionic surfactants and the formula R1N (Z) C as a textile softener.
(O) R2 N-acyl, N-alkyl polyhydroxyalkyl compounds. In this formula, R1 is C10-C
22 alkyl, R2 is C7-C21 alkyl, R1 and R2 are 29 in total
~ 39 carbon atoms and Z is a polyhydroxyalkyl, which can be -CH2 (CHOH) mCH2OH, where m is 3 or 4.

The related skin treatment cosmetic composition of U.S. Pat. No. 4,021,539 comprises an N-polyhydroxyalkylamine, which comprises the formula R1N (R) CH (CHOH) mR2, wherein R1
Is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl and heterocyclic aminoalkyl;
Same as R1, but both cannot be H, and
R2 is CH2OH or COOH.

The formaldehyde solution related to French Patent 1,360,018 is stabilized against polymerization by the addition of an amide of RC (0) N (R1) G, where R is a carboxylic acid function having at least 7 carbon atoms. , R1 is hydrogen or a lower alkyl group, and G is a glycitol group having at least 5 carbon atoms.

The glucoamine derivatives related to DE 1,261,861 are effective as wetting and dispersing agents and have the formula N
(R) (R1) (R2), where R is a glucoamine sugar residue, R1 is a C10-C20 alkyl group, and R2 is a C1-C5 acyl group.

Heterocyclic amides or their carboxylic esters according to GB 745,036 are said to be effective as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners and the like. This compound has the formula N (R) (R1)
Represented by C (O) (R2), where R is the residue of anhydrous hexanepentol or its carboxylic acid ester, R1 is a monovalent hydrocarbon group, and -C (O) R2 is 2 to 25
It is an acyl group of a carboxylic acid having a carbon atom.

U.S. Pat.No. 3,312,627 discloses a solid bar soap that is substantially free of anionic detergents and alkali builder substances, the bar soap comprising a few fatty acid lithium soaps and a few propylene oxide-ethylenediamine- A nonionic surfactant selected from ethylene oxide condensate, polypropylene oxide-propylene glycol-ethylene oxide condensate, and polymerized ethylene glycol, and a nonionic lathering component, wherein the lathering component has the formula RC (O) NR1 ( R
2) wherein the RC (O) contains from about 10 to about 14 carbon atoms, R1 and R2 are each H or a C1-C6 alkyl group, said alkyl group comprising a total of 2
From 7 to 7 carbon atoms and a total of 2 to 6 substituted hydroxyl groups. A similar disclosure is described in U.S. Pat. No. 3,312,626.

SUMMARY OF THE INVENTION A built-in detergent composition comprising one or more anionic, nonionic or cationic detersive surfactant or mixture thereof, an optional detersive adduct, and an optional auxiliary builder, wherein the detergent A composition comprising: (a) at least 1% by weight of a zeolite or a laminated silicate detergent builder or mixture thereof; and (b) at least 1% by weight of a polyhydroxy fatty acid amide of the formula: Wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof,
Preferably C1-C4 alkyl, more preferably C1 or
C2 alkyl, most preferably C1 alkyl (ie methyl); and R2 is C5-C31 hydrocarbyl, preferably linear C7-C19 alkyl or alkenyl, more preferably linear C9-C17 alkyl or alkenyl or most preferably C11-C17. Alkyl or alkenyl or a mixture thereof; and Z is a polyhydroxyhydrocarbyl containing a linear hydrocarbyl having at least three hydroxyl groups directly connected to the molecular chain or an alkoxylated derivative thereof (preferably an ethoxylated or propoxylated derivative); I do.

Preferably, the weight ratio of zeolite, phyllosilicate or mixture thereof to polyhydroxyfatty acid amide is about 1: 1.
10 to about 20: 1, more preferably about 1: 5 to about 15: 1, and most preferably about 1: 3 to about 10: 1.

DETAILED DESCRIPTION OF THE INVENTION Polyhydroxy fatty acid amide surfactant The detergent composition comprises at least about 1%, typically from about 3% to about 50%, preferably from about 3% to about 30%, of a polyhydroxy fatty acid described below. Contains amide surfactant.

The polyhydroxy fatty acid amide surfactant component of the present invention comprises a compound of the following structural formula, 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 (ie methyl) R2 is also C5-C31 hydrocarbyl, preferably linear C7-C19 alkyl or alkenyl, more preferably linear C9-C17 alkyl or alkenyl or most preferably C11-C17 alkyl or alkenyl or a mixture thereof; and Z is a molecular chain. Is a linear hydrocarbyl-containing polyhydroxyhydrocarbyl having at least 3 hydroxyl groups directly connected to an alkoxylated derivative thereof (preferably an ethoxylated or propoxylated derivative). Z is preferably derived from a reducing sugar in a reductive amination reaction. More preferably, Z is glycityl. A suitable reducing sugar is 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, and the above-mentioned respective sugars can be used. These corn syrups produce a sugar component mixture for Z. It should be understood that this does not exclude other suitable ingredients. Z is preferably -CH2
-(CHOH) n-CH2OH, -CH (CH2OH)-(CHOH) n-1
-CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2O
H is selected from the group consisting of H and its alkoxylated derivatives, where n is an integer from 3 to 5, and R 'is H or a cyclic or aliphatic monosaccharide. Most preferred is glycityl with n = 4, especially -CH2 (C
HOH) 4-CH2OH.

In the formula (I), R1 is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl,
It can be -2-hydroxyethyl or N-2-hydroxyethyl or N-2-hydroxypropyl.

R 2 —CO—N <is, for example, cocoamide, stearoamide,
Oleamide, lauroamide, myristamide, capricamide, palmitoamide, tallowamide and the like.

Z is 1-dioxyglycityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactyl, N-1-dioxygalacticyl, N-1-deoxymantyl, 1-dioxy It can be maltotriochityl or the like.

Methods for producing polyhydroxy fatty acid amides are well known in the art. Generally, the amide is obtained by reacting an alkylamine with a reducing sugar to form the corresponding N-alkyl polyhydroxyamine in a reductive amination reaction and then converting the N-alkyl polyhydroxyamine to a fatty acid ester of a fatty in a condensation amidation step. Or by reacting with triglyceride to give N
-Alkyl, produced by forming N-polyhydroxy fatty acid amide products. Various methods of making compositions containing polyhydroxy fatty acid amides have been disclosed. For example, UK Patent No. 809,060, U.S. Patent No. 2,965,576
And U.S. Pat.No. 2,703,798 and U.S. Pat.
No. 85,424 is cited as a reference.

In the process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides, the glycityl component is derived from glucose and the N-alkyl or N-hydroxyl functionality is N-methyl, N-
-Ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl; trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, hexaoxide Lithium, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, potassium sodium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicate Fats selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of basic potassium silicate, basic sodium aluminosilicate and basic potassium aluminosilicate and mixtures thereof. Beauty treatment If, N- alkyl - or products by reacting an N- hydroxyalkyl glucosides amine. The amount of catalyst is preferably from about 0.5 mol% to about 50 mol%, more preferably from about 2.0 mol% to about 10 mol%, on a molar basis of N-alkyl or N-hydroxyalkyl-glucoamine. The reaction is preferably performed at about 138 ° C to about 180 ° C for about 20 minutes to about 90 minutes. If glyceride is used as a fatty ester source in the reaction mixture, the reaction is preferably carried out using from about 1 to about 10% by weight of a phase transfer agent, based on the weight of the total reaction mixture. Are selected from saturated fatty alcohol polyethoxylates, alkyl polyglycosides, linear glycoamide surfactants and mixtures thereof.

 Preferably, the method is performed as follows.

(A) preheating the fatty ester to about 138 ° C to about 170 ° C; (b) adding an N-alkyl or N-hydroxyalkylglucoamine to the heated fatty acid ester;
Mixing to the extent necessary to form a two-phase liquid / liquid mixture; (c) mixing the catalyst into the reaction mixture; and (d) stirring for a specified reaction time.

When the fatty ester is a triglyceride, about 2% to about 20% by weight of the reactants of the preformed linear N-alkyl / N-hydroxyalkyl as a phase transfer agent;
The N-linear glucosyl fatty acid amide product is added to the reaction mixture. This matures the reaction and increases the reaction rate.
Detailed experimental procedures are shown below.

The polyhydroxy "fatty acid" amide material used in this method offers the formulator the advantage that the material is made entirely or primarily from natural, renewable, non-petroleum feedstocks and is degradable. These materials also provide low toxicity to aqueous organisms.

Note that the method used to produce the polyhydroxy fatty acid amides of formula (I) produces large amounts of non-volatile by-products such as ester amides and cyclic polyhydroxy fatty acid amides with the polyhydroxy fatty acid amide. Must. The levels of these by-products will vary with the particular reactants and processing conditions. Preferably, the polyhydroxyfatty acid amide incorporated into the detergent composition is less than about 10%, preferably less than about 4%, of the polyhydroxyfatty acid amide-containing composition added to the detergent composition. It is provided in such a form as to contain an amide. The preferred method as described above has the advantage of producing low levels of by-products, including this cyclic amide by-product.

Zeolite and Laminated Silicate Builder The detergent composition contains a zeolite or a laminated silicate builder, or a mixture thereof.

The level of zeolite and / or layered silicate builder varies greatly depending on the end use of the detergent composition and its physical form. The detergent composition contains at least about 1% of such a builder. Liquid formulations typically contain from about 5% to about 50%, more preferably from 5% to about 30% by weight of the builder. Granular formulations are typically about
It contains 10% to about 80%, preferably about 15% to about 50% by weight of builder. However, higher or lower builder levels are not excluded. Preferably, the weight ratio of zeolite or layered silicate builder or mixture thereof to polyhydroxy fatty acid amide is about 1:10 to about 20: 1, preferably about 1: 5 to about 15: 1, most preferably about 1: 1. : 3 to 10: 1.

Zeolite builders are a class of aluminosilicate builders and have gained importance in today's heavy duty detergents, especially in particulate formulations. The zeolite used in the present invention has a crystal structure or an amorphous structure, is a natural product, or is synthetically derived. Methods for producing zeolitic materials are well known in the art. See, for example, U.S. Pat. No. 3,985,669. This patent is cited as a reference. Preferred synthetic zeolite ion exchange resins used in the present invention are trade names Zeolite A, Z
Obtained as eolite P (B) and Zeolite X. In general, the zeolite builder has 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 and y is
X is an integer from about 15 to about 264;
This substance also contains Ca per gram of anhydrous aluminosilicate
It has a magnesium ion exchange capacity of at least about 50 milligram equivalents of CO3 hardness. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange resin has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O where x is from about 30 to about 30, especially It is about 27. This material is known as zeolite A.

Laminated silicate builders are also known in the art. Laminated sodium silicate is preferred. See, for example, Laminated Sodium Silicate Builder in U.S. Pat. No. 4,644,839. This is a reference.

Preferably, detergents used below about 50 ° C., especially below about 40 ° C., are substantially free of boric acid containing builders and boric acid forming builders. In this case, "substantially does not contain a boric acid-containing builder and a boric acid-forming builder"
2% or more, preferably 1% or more, more preferably about 0.
It does not contain 5% or more of boric acid-containing builder and boric acid-forming builder, and most preferably contains 0%.

Detersive Surfactant System The detergent composition contains, in addition to the polyhydroxyfatty acid amide and the zeolite builder, one or more additional surfactants, which can be anionic, cationic or nonionic surfactants. . Typically, this surfactant system, in addition to polyhydroxy fatty acid amide,
Contains one or more anionic and / or nonionic surfactants. In order to achieve effective overall cleaning under a wide range of cleaning conditions, it is preferable to include an anionic surfactant. In particular, the detergent composition may be an alkyl sulfate, an alkyl ester sulfonate (eg, a methyl ester sulfonate), an alkyl alkoxylated sulfonate (eg, a methyl ester sulfonate), an alkyl alkoxylated sulfonate (eg, an alkyl ethoxylated sulfonate). ), And the hardness-sensitive surfactants such as alkylbenzenesulfonates (eg, linear alkylbenzenesulfonates), the advantages of the present invention are particularly realized. It may also be desirable to include conventional nonionic surfactants such as alkyl ethoxylates or alkyl polyglycosides as described below. Typically, the amount of additional detersive surfactant will be from about 1% to about 50% by weight of the detergent composition, preferably from about 3 to about 40%.
%, More preferably or about 5 to about 30% by weight. Suitable surfactants are described below.

Alkyl ester sulfonate surfactant The alkyl ester sulfonate surfactant used in the present invention is described in Journal of the American Oil Chloride.
Emists Society "52 (1975), pp. 323-329, including linear esters of C8-C20 carboxylic acids (eg, fatty acids) sulfonated with SO3 gas. Suitable raw materials are tallow, palm oil and coconut. Contains natural fatty substances derived from oils.

Particularly preferred alkyl ester sulfonate surfactants used in detergents include alkyl ester sulfonate surfactants of the following structural formula:

Wherein R3 is C8-C20 hydrocarbyl, preferably alkyl or a combination thereof, R4 is C1-C6 hydrocarbyl,
Preferably, alkyl or a combination thereof, and M is a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable salts are metal salts such as sodium, potassium and lithium salts, and substituted or unsubstituted ammonium salts such as methyl-, dimethyl-, trimethyl and quaternary ammonium cations, for example, tetramethyl-ammonium and dimethylpiperidinium. And cations derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Preferably R3 is C10-C16
Alkyl, R4 is methyl, ethyl or isopropyl. Particularly preferred are sulfonic acid methyl esters wherein R3 is C14-C16.

Alkyl Sulphate Surfactants Alkyl sulphate surfactants are water-soluble salts or acids of the formula ROSO3M, wherein R is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C24 alkyl component, More preferably C12
-C18 alkyl or hydroxyalkyl, where M is H or a cation, such as an alkali metal cation (e.g., sodium, potassium, lithium cation), and a substituted or unsubstituted ammonium cation such as methyl-, dimethyl-, trimethyl and quaternary ammonium cations For example, cations derived from tetramethyl-ammonium and dimethylpiperidinium, and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and mixtures thereof. Typically, C12-C16 alkyl molecular chains are preferred for low temperature washing (eg, below about 50 ° C.) and C16-C18 alkyl molecular chains are preferred for high temperature washing (eg, about 50 ° C. or above).

Alkyl alkoxylated sulphate surfactant The alkyl alkoxylated sulphate surfactant has the formula
RO (A) is a water-soluble salt or acid of mSO3 M, where R
Is a substituted C10-C24 alkyl, or C10-C24 alkyl moiety, preferably C12-C20 alkyl and area hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, representative Specifically, about 0.5 to about 6, more preferably about 0.5 to about 3, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), or ammonium or It is a substituted ammonium cation. In this case, alkyl ethoxylated sulfates as well as alkyl propoxylate sulfates are considered. Examples of substituted ammonium cations are methyl-, dimethyl-, trimethyl-ammonium cations,
Includes quaternary ammonium cations such as tetramethyl-ammonium and dimethylpiperidinium, and cations derived from alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine, and mixtures thereof. Examples of surfactants are
C12-C18 alkyl polyethoxylate (1.0) sulfate, C
12-C18 alkyl polyethoxylate (2.25) sulfate, C
12-C18 alkyl polyethoxylate (3.0) sulfate and C12-C18 alkyl polyethoxylate (4.0) sulfate, wherein M is preferably selected from sodium and potassium.

Other Anionic Surfactants Other anionic surfactants that can be used for cleaning purposes can also be included in the compositions of the present invention. These surfactants include salts of soaps (eg, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolamine), C9-C20 linear alkyl benzene sulfonates, C8-C22 primary And a second alkane sulfonate, a C8-C24 olefin sulfonate, such as a sulfonated polycarboxylic acid prepared by sulfonation of the pyrolysis product of an alkaline earth metal citric acid as described in GB 1,082,179. , Alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate,
Alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, N
-Isethionates such as acyl isethionates, acyl tartrate, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, diesters of sulfosuccinates (especially saturated and unsaturated C12-C18
Diesters), sulfates of alkyl polysaccharides such as N-acyl sarcosinates and sulfates of alkyl polyglycosides (nonionic non-sulfate compounds are described below), branched primary alkyl sulfates, formula RO (CH2CH2O) kCH2COO -M
+ (Where R is a C8-C22 alkyl, k is an integer from 0 to 10 and M is a soluble salt forming cation), and sodium polyhydroxide esterified with isethionic acid and sodium hydroxide Contains fatty acids neutralized by: Fatty acids and hydrogenated resin acids are also suitable. For example, resin acids and hydrogenated resin acids present or derived in rosin, hydrogenated rosin, and tall oil are also suitable. Another example is “Surface Active
Agents and Detergents "(Vol.I and II by Schwarts,
Perry and Berch). Various surfactants are disclosed in U.S. Pat. No. 3,929,678 (column 23, line 58 to column 29, line 23).
Lines) (this is a reference).

Nonionic Detergent Surfactants Suitable nonionic detergent carboxymethyl is described in U.S. Pat. No. 3,929,678, column 13, line 14 to column 16, line 6, which is incorporated by reference. Non-limiting examples of useful nonionic surfactants are listed below.

1. Condensates of alkyl phenol with polyethylene oxide, polypropylene and polybutylene, generally polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols, including alkyls having about 6 to about 12 carbon atoms in a straight or branched chain. In a preferred embodiment, ethylene oxide is present in a ratio of about 5 to about 25 moles per mole of alkylphenol. Commercially available nonionic surfactants of this type are IgepalTM CO-630 marketed by GAF and TritonTMX marketed by Rohm and Haas
-45, X-114, X-100, X-102. These surfactants are commonly referred to as alkylphenol alkoxylates, for example, 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 may be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred is about
It is a condensation product of an alcohol having an alkyl containing from 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type are the Tergitol ™ 15-S-9 (condensation product of C11-C15 linear secondary alcohol and 9 moles of ethylene oxide, all marketed by Union Carbide). ), And Tergitol ™ 24-L-6NMW (condensation product of C12-C14 primary alcohol with 6 moles of ethylene oxide having a narrow molecular weight distribution); Neodol ™ 45-9 (C14-C15 line, marketed by Shell Chemical Company) Condensation product of neat alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (C
Condensation product of 12-C13 linear alcohol with 6.5 mol of ethylene oxide, NeodolTM45-7 (condensation product of C14-C15 linear alcohol with 7 mol of ethylene oxide), NeodolTM45-
4 (condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide) and Kyro marketed by P & G
TMEOB (condensation product of C13-C15 alcohol and 9 moles of ethylene oxide). 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 water insoluble. Addition of a polyoxyethylene moiety to this hydrophobic moiety increases the overall water solubility of the molecule and the liquid content of the product until the polyoxyethylene content is approximately 50% of the total weight of the condensation product. Properties are retained, which corresponds to condensation with about 40 moles of ethylene oxide. Examples of compounds of this type are
Includes a few of the Pluronic ™ surfactants marketed by BASF.

4. Condensation products of ethylene oxide with products resulting from the reaction of propylene oxide with ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylene diamine with an excess of propylene oxide and generally has a molecular weight of about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide such that the condensation product contains from about 40 to about 80% by weight polyoxyethylene and from about 5,000 to about 11,000.
With a molecular weight of Examples of this type of nonionic surfactant are two of the TetronicTM compounds marketed by BASF.
Including three things.

5. Semi-polar non-ionic surfactants are a special category of non-ionic surfactants, which contain about 10 to 18 carbon atoms.
A water-soluble amine oxide comprising two alkyl moieties, and two moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group of about 1-3 carbon atoms; and one alkyl of about 10-18 carbon atoms. A water-soluble phosphine oxide comprising a moiety and two moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group of about 1 to 3 carbon atoms; and one alkyl moiety of about 10 to 18 carbon atoms. And 2 moieties selected from the group consisting of an alkyl group and a hydroxyalkyl group of about 1-3 carbon atoms.

Semipolar nonionic detergent surfactants include amine oxide surfactants of the formula:

Wherein R3 is an alkyl group containing from about 8 to about 22 carbon atoms;
R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or a mixture thereof; x
Is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
The R5 groups can be linked to each other via an oxygen or nitrogen atom to form a cyclic structure.

These amine oxide surfactants include in particular C10-C18 alkyldimethylamine oxide and C8-C12 alkoxyethyldihydroxyethylamine oxide.

6.Alkyl polysaccharides described in U.S. Patent No. 4,565,647 having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and from about 1.3 to about 1
0, preferably about 1.3 to about 3, most preferably about 1.
Polysaccharides having hydrophilic groups containing from 3 to about 2.7 saccharide units, such as polyglycosides. 5 or 6
Any reduced saccharide containing carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be used in place of glucosyl moieties (optionally, the hydrophobic group can be in the 2-position, 3-
At positions 4, 4 etc. to yield glucose or galactose as opposed to glucoside or galactoside). There may be an intersaccharide linkage between one position of the additional saccharide unit and positions 2, 3, 4, and / or 6 of the preceding saccharide unit.

Optionally, a polyalkylene oxide linking the hydrophobic moiety and the polysaccharide moiety may be present, but this is undesirable. The preferred alkylene oxide is ethylene oxide. A typical hydrophobic group is
It includes saturated or unsaturated, branched or unbranched alkyl groups containing about 8 to about 18, preferably about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl can contain up to about 3 hydroxyl groups and / or the polyalkylene oxide molecular chain can contain up to about 10, preferably up to 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-,
Tri-, tetra-, penta- and hexaglucosides,
Galactoside, lactoside, glucose, fructoside, fructose and / or galactose.
Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucoside, and tallow alkyl tetra-, and pentaglucoside, and tallow alkyl tetra, penta-, and hexaglucoside.

Preferred alkyl polyglucosides have the formula:

^{_{R 2 O (C n H 2n}} O) t (glcosyl) x Here R2 is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and glue made from the mixture - is selected from the pull, the alkyl group is from about 10 to about
18, preferably containing from about 12 to about 14 carbon atoms; n is 2
Or 3, preferably 2; t is from 0 to about 10, preferably 0;
Or x is about 1.3 to about 10, preferably about 1.3 to about 3,
Most preferably from about 1.3 to about 2.7. Glycosyl is preferably derived from glucose. To make these compounds, an alcohol or an alkylpolyethoxy alcohol is first formed, which is then reacted with glucose or a glucose source to form a glucoside (linkage at position 1). Next, position 1 and positions 2-, 3-, 4- and / or 6 of the preceding glycosyl unit,
Preferably, an additional glycosyl unit is bound between the 2-position.

7. A fatty acid amine surfactant having the formula: Wherein R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms, and each R7 is hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl and-(C2H4O) x
Selected from the group consisting of H, where x is 1
To 3.

Preferred amides are C8-C20 ammonia amide monoethanolamide, diethanolamide and isopropanolamide.

Cationic Surfactant The detergent composition of the present invention can include a cationic detersive surfactant. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides, which have the following formula:

[R ² (OR ³ ) _y ] R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ^— where R 2 is an alkyl or alkyl benzyl group having about 8 to about 18 carbon atoms in the alkyl molecular chain; R3 is-
_{CH 2 CH 2 O, -CH 2} CH (CH 3) -, - CH 2 CH (CH 2 OH) -, - CH
Selected from the group consisting of ₂ CH ₂ CH ₂ — and mixtures thereof; each R 4 is a cyclic structure formed by linking C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, and two R 4 groups -CH2CHOH-CHOHCOR6CHOHCH2OH (here
R6 is selected from a group consisting of hexose or hexose polymer having a molecular weight of less than about 1,000) and hydrogen when y is non-zero; R5 is the same as R4, or R2 plus an alkyl having less than about 18 carbon atoms in total R5. A molecular chain; each y is 0 to about 10, the sum of y is 0 to about 15, and X is any compatible anion.

Other cationic surfactants that can be used in the present invention are described in U.S. Patent No. 4,228,044, which is incorporated by reference.

Other Surfactants An amphoteric surfactant can be incorporated into the detergent composition of the present invention. These surfactants can be described as those in which the aliphatic group in the aliphatic derivative of a secondary or tertiary amine or the aliphatic derivative of a heterocyclic secondary and tertiary amine is linear or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains an anionic water-soluble group, such as carboxy, sulfonate, sulfate.
See U.S. Patent No. 3,929,678 for examples of amphoteric surfactants.

Further, a zwitter ionic surfactant can be incorporated into the detergent composition of the present invention. Surfactants of this type are broadly defined as derivatives of secondary and tertiary amines, heterocyclic secondary
And tertiary amine derivatives or quaternary ammonium,
It can be described as a derivative of the fourth phosphonium or third sulfonium compound. For examples of zwitterionic surfactants, see U.S. Pat. No. 3,929,678 (which is hereby incorporated by reference).

Amphoteric and zwitterionic surfactants are generally used with one or more anionic and / or nonionic surfactants.

Auxiliary Builders The detergent compositions of the present invention can contain auxiliary builders, including inorganic and organic detergent builders, to help control inorganic hardness. Typical amounts of auxiliary builders are from about 5% to about 200% by weight of the zeolite / layered silicate builder.
%.

Inorganic detergent builders include alkali metal, ammonium and alkanolammonium salts of phosphates (eg, tripolyphosphate, pyrophosphate and glassy polymeric metaphosphate), phosphonates, phytates,
Includes, but is not limited to, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. It is also possible to use boric acid builders and builders containing boric acid-forming substances capable of forming borates during storage of the detergent or under laundry conditions (hereinafter referred to as "boric acid builders"). Preferably about 50
Non-borate builders are used in the compositions of the present invention for use at laundering temperatures of less than or equal to about 40 ° C, especially about 40 ° C or less.

Examples of silicate builders are alkali metal silicic acids, especially
It has an SiO2: Na2O ratio of 1.6: 1 to 3.2: 1. However, other silicates such as magnesium silicate can be used. They serve as crispening agents in granular formulations, as stabilizers for oxygen bleaches, and as components of foam control systems.

Aluminosilicates other than zeolites can also be used. In general, the aluminosilicate is of the empirical formula MZ (zAlO2
SiO2), where M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2, and y is 1, but need not be within the zeolite formula. .

Examples of carbonate builders are alkaline earth metals and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures with ultrafine calcium carbonate as described in German Patent Application No. 2,321,001. This patent is cited as a reference.

Phosphate builders and phosphonate builders can be used, but it is generally desirable to replace these builders with zeolite / laminated silicate builders and optionally other auxiliary builders and detergent additives. . Therefore, the presence of these builders, if any, is included at low levels. Preferably, the phosphate builder comprises no more than 10% of the total builder in the composition, more preferably no more than about 5%, and most preferably 0%.

Examples of polyphosphates include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphates having a degree of polymerization of about 6 to about 21.
And phytate.

An example of a phosphonate is ethane 1-hydroxy-1,1-
Salts of diphosphonic acids, especially sodium and potassium salts, water-soluble salts of methylene diphosphonates, such as trisodium and tripotassium salts of substituted methylene diphosphonic acids and water-soluble salts, such as ethylideneisopropylidene, benzylmethylidene and halo Trisodium and tripotassium methylidene phosphate. Phosphate builder salts of the type described above are described in U.S. Pat. Nos. 3,159,581 and 3,213,030, U.S. Pat. No. 3,422,021, and U.S. Pat. Nos. 3,400,148 and 3,422,137, which are incorporated by reference.

Organic detergent builders suitable for use in the present invention include, but are not limited to, various polycarboxylic acid compounds. In this case, "polycarboxylic acid" refers to a compound having a plurality of, preferably at least three, carboxylate groups.

The polycarboxylate builder is generally added to the composition in the form of an acid, but can also be added in the form of a neutralized water-soluble salt. When used in salt form, alkali metals (eg, sodium, potassium and lithium or alkanolammonium salts) are preferred.

Among the polycarboxylate builders, various categories of useful substances are included. One important category of polycarboxylate builders includes ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergent builders.
Examples of useful ether polycarboxylates include oxydisuccinates as disclosed in US Pat. Nos. 3,128,287 and 3,635,830. These patents are cited as references.

Ether polycarboxylates of the type useful as builders in the present invention include those corresponding to the following general formula: CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) ( B) where A is H or OH; B is H or -O-CH (COOX)
-CH2 (COOX), X is H or a salt-forming cation.
For example, in the above formula, if A and B are both H, then the compound is oxydisuccinic acid and its water-soluble salts. If A is OH and B is H, the compound is monosuccinic acid tartrate (TMS) and its water-soluble salts. If A is H and B is -O-CH (COOX) -CH2 (COOX), the compound is tartaric acid disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are particularly suitable for use in the present invention. Particularly preferred is a mixture of TMS and TDS in a weight ratio of about 97: 3 to about 20:80.
These builders are described in U.S. Pat. No. 4,663,071.

Suitable ether polycarboxylates are cyclic compounds,
In particular U.S. Pat.Nos. 3,923,679, 3,835,163, 4,158,
No. 35, 4,120,874, and 4,102,903.

Other useful detergent builders include ether hydropolycarboxylates represented by the following structural formula:

HO- [C (R) (COOM) -C (R) (COOM) -O] n-H wherein M is hydrogen or a cation in which the resulting salt is water-soluble, preferably an alkali metal, ammonium or substituted Ammonium cation; n is from 2 to about 15 (preferably 2
To 10, more preferably 2 to 4), and each R is the same or different and is selected from hydrogen, C1-4 alkyl or C1-4 substituted alkyl (preferably hydrogen).

Still other ether polycarboxylates include copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid .

In addition, organic polycarboxylate builders include various alkali metal, ammonium and substituted ammonium salts of polyacetic acid. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Also included are polycarboxylates such as melitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tercarboxylic acid, carboxymethyloxysuccinic acid and water-soluble salts thereof.

Citrate salts, such as citric acid and its water-soluble salts (especially sodium salts), are particularly important polycarboxylate builders for heavy duty liquid detergent compositions,
It can also be used in granular compositions.

Other carboxylate builders are disclosed in U.S. Pat.
The carboxylate hydrocarbon described in No. 2 is included. This patent is cited as a reference.

Further, in the detergent composition of the present invention, U.S. Pat.
No. 6,984, 3,3-dicarboxy-4-oxy-1,6
Hexane diate and related compounds are suitable. This patent is cited as a reference. A useful succinic acid builder is C5-20
Including alkylsuccinic acid and its salts. A particularly preferred compound of this type is dodecenyl succinic acid. Alkyl succinic acids typically have the general formula R—CH (COOH) CH 2 (COOH), ie, in the succinic acid derivatives as described in the aforementioned patents, where R is a hydrocarbon such as C 10-20 alkyl or alkenyl. , Preferably C12-16, or R is substituted by a hydroxyl, sulfo, sulfoxy or sulfone substituent.

Succinic acid builder is used in the form of its water-soluble salts, such as its sodium, potassium, ammonium and alkanolammonium salts.

Examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinic acid is a preferred builder of this group and is described in European Patent Application No. 86200690.5 / 0.2.
No. 00,263.

Examples of useful builders are also sodium and potassium salts of carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, ciscyclohexane-hexacarboxylic acid, ciscyclopentane-tetracarboxylic acid and water-soluble polyacrylic acid and maleic anhydride. Including copolymers with vinyl methyl ether or ethylene (about 20
Polyacrylates having a molecular weight of 00 or more can be used effectively as dispersants).

Other suitable polycarboxylates are described in U.S. Pat.
No. 226, a polyacetal carboxylate. This patent is cited as a reference. These polyacetal carboxylates are produced by reacting a glyoxylic acid ester with a polymerization initiator under polymerization conditions. The resulting polyacetal carboxylate ester is attached to chemically stable end groups and stabilized against rapid degradation in alkaline solution, then converted to the corresponding salt and added to the surfactant.

Also, polycarboxylate builders are described in U.S. Pat. No. 3,308,067. This patent is cited as a reference. These substances include maleic acid, itaconic acid, mesaconic acid,
Includes water-soluble salts of homo- or copolymers of aliphatic carboxylic acids such as fumaric, aconitic, citraconic and methylenemalonic acids.

Other organic builders known in the art can be used.
For example, a monocarboxylic acid having a long-chain hydrocarbyl and a water-soluble salt thereof can be used. These include substances commonly referred to as "soaps". Typically C10-2
A chain length of 0 is used. Hydrocarbyls are saturated or unsaturated.

Enzymes Enzymes are included in detergent compositions for a variety of purposes, such as removing stains on protein, carbohydrate or terglyceride groups, and preventing the transfer of refuge dyes. The enzymes contained are protease, amylase, lipase, cellulase, and peroxidase,
As well as mixtures thereof. The enzyme can be of any origin,
For example, it can be of plant, animal, bacterial, fungal and yeast origin. However, the choice is governed by various factors such as pH activity and / or optimal stability, thermal stability, stability to active detergents and builders. In this regard, bacterial or fungal enzymes such as bacterial amylase and protease,
And bacterial cellulases are preferred.

Suitable examples of proteases are B.subtilis and B.lich
Subtilisin obtained from a specific strain of eniforms.
Other suitable proteases are obtained from Bacillus sp.
It has maximum activity within the pH range of −12,
It is commercially available from S under the trademark Esperase R. The preparation of this and similar enzymes is described in Novo UK Patent 1,243,784. Commercially available proteolytic enzymes suitable for removing protein stains are those sold under the trademarks LACALSE ^™ and SAVINASE ^™ by Novo Industries A / S (Denmark), and International Bio-Synthetic.
s, Inc. (Netherlands) under the trademark MAXATASE ^™ .

Of particular interest in the category of proteolytic enzymes for liquid detergent compositions are the protease A
And an enzyme called protease B. Protease A and its production method are described in European Patent Application No. 130,756,
This is a reference. Protease B is a proteolytic enzyme that differs from protease A in that it has leucine instead of tyrosine at position 217 of its amino acid sequence. Protease B is described in European Patent Application No. 8703761.8, the disclosure of which is incorporated by reference. The method for producing Protease B is also described in European Patent Application No. 130,756, which is cited as a reference.

Amylases include, for example, α-amylases derived from the specialized B. licheniforms described in detail in the aforementioned British Patent No. 1,296,839. Starch hydrolases are available, for example, from International Bio-Synthetics' RAPIDASE ^™ and N
Including OVO INDUSGTRIES 'TERMAMYL ^TM .

Cellulases used in the present invention include both bacterial and fungal cellulases. Preferably, these enzymes have a pH optimum between 5 and 9.5. Suitable cellulases are described in U.S. Patent No. 4,435,307,
Taking this as a reference, this cellulase discloses a fungal cellulase produced from Humicolainsolens. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,27
5 and DE-OS-2,247,832.

Examples of these cellulases are Humicola insolens (Hum
icola grisea var.thermoidea), especially Humicola
Bacillu, a cellulase produced by strain DSM 1800
cellulase 21 belonging to sN strain or genus Aeromonas
2 Cellulase and marine mo
hepusepancre of lluse (Dolabella Auricula Solander)
It is a cellulase extracted from as.

The lipase which can be used in the detergent composition of the present invention is Pseudomonas stutzeri ATC described in British Patent No. 1,372,034.
It is produced by a microorganism of the genus Pseudomonas such as C 19.154 and is cited in this patent. Suitable lipases include those produced from the microorganism Pseudomonas fluorescens IAM 1057 and those that show a positive immune cross-reactivity with antibodies to the lipase. This lipase and its production method are described in Japanese Patent Application No. 53
No. -20487. This lipase is Amano Pha
rmaceutical Co. Ltd. Trademark Lipase P “Amano” from Nagoya
And is referred to below as "Amano-P". These lipases are prepared according to the standard immunodiffusion method known from Ouchterlony (Acta. Med. Scan., 133, pp76-79 (195).
0)) must be used to demonstrate positive immune cross-reactivity with Amano-P antibodies. The immunocross-reactivity of these lipases with their Amano-P is described in U.S. Pat. No. 4,707,291, which is hereby incorporated by reference. Representative examples of these lipases are Amano-P lipase, lipase ex Pseudom
onas fragi FERM P 1339 (commercially available under the trademark Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum
FERM P 1338 (commercially available under the trademark Amano-CES), lipase ex C
hromobacter viscosum, e.g. Chromobacter viscosum
var.lipolyticum NRRLB 3673 (commercially available from Toyo Brewing Co., Ltd., Tagata, Japan), and Chromobacter vi commercially available from USA Biochemical Corp., USA and Disoiynth Co., The Netherlands
scosum lipases, and lipases ex Pseudomonas gladi
oli.

Peroxidase enzymes are used with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide and the like. These enzymes are used as "solution bleach".
That is, it is used to prevent dyes or pigments removed from the substrate being washed from migrating to other substrates in the washing solution. Peroxidase enzymes are known in the art and are, for example, horseradish peroxidase, ligninase and haloperoxidases such as chloro- and bromo-peroxidase. The peroxidase-containing detergent composition is described in, for example, PCT Patent Application No. WO 89/099813, which is cited as a reference.

A wide variety of enzyme materials and means for incorporating them into detergent particles are described in U.S. Pat. No. 3,553,139, which is hereby incorporated by reference. U.S. Pat.No. 4,101,45
No. 7, and U.S. Pat. No. 4,507,219 describe other enzymes, and reference is made to these patents. U.S. Pat.No. 4,261,86 enzymatic materials used in liquid detergent formulations and methods for their combination
This is described in No. 8 and is cited as a reference.

Enzyme, in principle, about 5 mg per gram of composition
Up to levels sufficient to contain more typically from about 0.05 mg to about 3 mg of active enzyme.

In the case of granular detergents, it is preferred to coat the enzyme with additives that are inert to the enzyme in order to minimize dust formation and enhance storage stability. The technique is well known in the art. For liquid formulations, an enzyme stabilization system is used. Techniques for enzyme stabilization of aqueous detergent compositions are well known in the art. One technique for stabilizing enzymes in aqueous solutions consists in using free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions can be used with short-chain carboxylate, preferably formate. See, for example, U.S. Patent No. 4,318,818. This is a reference. Methods using polyols such as glycerol and sorbitol have also been proposed. Alkoxy alcohol-
Use of dialkyl glycol ethers, mixtures of polyalkyl alcohols with polyfunctional aliphatic amines (eg, alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine), and boric acid and / or alkali metal borates You can do it. Further, enzyme stabilization techniques are disclosed in U.S. Pat.Nos. 4,261,868 and 3,600,3
No. 19, both of which are cited as references, see also European Patent Publication No. 0,199,405 and European Patent Application No. 86200586.5. Non-boric acid and borate stabilizers are preferred. Also, U.S. Patent Nos. 4,261,868, 3,600,319, and 3,519,570 describe enzyme stabilization systems.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The detergent compositions of the present invention can include a bleaching agent or can include a bleaching composition containing a bleaching agent and one or more bleaching activators. When the bleaching compound is used, it is present at a level of from about 1% to about 20%, more preferably from about 1% to about 10% of the detergent composition. Generally, bleaching compounds are an optional ingredient in non-liquid formulations, such as granular detergents. If present, the amount of bleach activator may range from about 1% to about 60% of the detergent composition, more typically about
The range is 0.5% to about 40%.

The bleaching agent used can be any bleaching agent of currently known or about to be known detergent compositions used for textile, hard surface or other optional purposes. These bleaches include oxygen bleaches as well as other bleaches. For laundering conditions of about 50 ° C. or less, especially about 40 ° C. or less, the laundry composition should be free of borate or a substance that forms borate in situ during storage or under laundering conditions (borate-forming substance). ) Is preferably not contained. Therefore, in such conditions, it is preferred to use a non-borate bleach or a non-borate forming bleach. Preferably, the detergent used at these temperatures is substantially free of borates and borate-forming substances. In this case, “substantially free of borate and borate-forming substance” means that the composition does not contain 2% or more of borate-containing substance and borate-forming substance, preferably 1% or more. Not containing, more preferably containing 0%.

One category of bleach used in the compositions of the present invention includes percarboxylic acids and salts thereof. Examples of this class of bleaches include the magnesium salts of hexahydrated magnesium monoperoxyphthalate, meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxide decandioic acid. Such bleaching agents are disclosed in U.S. Pat.No. 4,483,781, U.S. Pat.
No., European Patent Application No. 0,133,354 and U.S. Patent No. 4,412,934
All of which are incorporated by reference. Highly preferred bleaches include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4,634,551. This patent is cited as a reference.

Another category of bleaches that can be used in the present invention are halogen bleaches. Examples of hypohalite bleach are
Trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, N-chloro and N
-Bromoalkanesulfonamide. Such materials comprise 0.59-10% by weight of the finished product, preferably 1-5%
% By weight.

Peroxy bleach can also be used. Suitable peroxy bleaching agents are sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

The peroxy bleach is preferably combined with a bleach activator to produce the peracid corresponding to the bleach activator in aqueous solution (ie, during laundering).

Preferred bleach activators incorporated into the detergent compositions of the present invention have the following general formula:

Wherein R is an alkyl group containing from 1 to about 18 carbon atoms, wherein the longest linear alkyl chain extending from and containing the carbonyl carbon contains from about 6 to about 10 carbon atoms;
L is a leaving group whose conjugate acid has a pKa in the range of about 4 to about 13. These bleach activators are described in U.S. Pat. Nos. 4,915,854 and 4,412,934, which are incorporated by reference.

Bleaches other than oxygen bleaches are well known in the art and can be used in the present invention. Particularly useful types of non-oxygen bleaches are light-activated bleaches, such as zinc sulfonates and aluminum phthalocyanine. These substances can precipitate on the substrate during washing. When irradiated with light in the presence of oxygen, for example, when the fabric is dried to dryness during the day, the sulfonated zinc phthalocyanine is activated,
Thus, the substrate is bleached. A preferred photoactivated bleaching method using zinc phthalocyanine is described in US Pat. No. 4,033,718, which is incorporated by reference. Typically, the detergent compositions contain from about 0.025% to about 1.25% by weight zinc sulfonated phthalocyanine.

Polymer Stain Remover Any of the polymer stain removers known in the art can be used in the practice of the present invention. Polymer stain remover
A hydrophilic segment for hydrophilizing the surface of a hydrophobic fiber such as polyester and nylon; and an anchor for the hydrophilic segment which precipitates on the hydrophobic fiber and is fixed to the fiber during washing and rinsing. And a hydrophobic segment serving as a In this way, stains generated after the treatment with the stain remover can be easily removed during subsequent washing.

Although it is desirable to use a polymeric soil remover in any of the detergent compositions of the present invention, especially in laundry and other applications where grease and oil must be removed from hydrophobic surfaces, anionic surfactants The presence of polyhydroxy fatty acid amides in detergent compositions containing the agent can enhance the performance of many commonly used polymeric soil removers. Anionic surfactants interfere with the ability of a few soil removers to precipitate and adhere on hydrophobic surfaces. These polymeric soil removers have nonionic hydrophilic or hydrophobic segments that interact with anionic surfactants.

Detergent compositions in which the performance of polymeric soil removers is improved through the use of polyhydroxy fatty acid amides enhances the performance of anionic surfactant systems, soil removers that interact with anionic surfactants, and soil removers A detergent composition comprising an amount of polyhydroxyfatty acid amide (PFA), wherein (I) the precipitation of the soil-removing agent (SRA) of the detergent composition in aqueous solution in the absence of other detergent components. "A control test" (A) and the same type and amount of anionic surfactant used in the detergent composition in the same weight ratio of SRA and anionic surfactant and SRA in aqueous solution Combine "SRA /
By comparing the level of precipitation of SRA on hydrophobic fibers (eg, polyester) in aqueous solution between the "anionic surfactant" test (B), it was found that the precipitation in (B) was lower than in (A). Demonstrating the action of the anionic surfactant indicates anionic surfactant interaction between the soil remover and the anionic surfactant system in the detergent composition, and (II) the same type and the same level of amide SRA precipitation in "SRA / Anionic Surfactant / PFA Test" (C), where PFA binds to the SRA and anionic surfactant system described above;
Compared to the SRA precipitation in test (B), the improvement in the precipitation of SRA in test (C) compared to test (B)
By indicating the presence of an activating amount of PFA, the detergent composition
Determine whether or not it contains RA-activating amounts of polyhydroxy fatty acid amide (PFA). Therefore, the test in this case must be carried out at a surfactant concentration in an aqueous solution above the critical micelle concentration (CMC) of the anionic surfactant, preferably above about 100 ppm. The concentration of the polymeric soil remover must be at least 15 ppm or higher. For a hydrophobic fiber source, a sample of polyester fiber must be used. For each test, 12 minutes of the same type of sample are immersed in a 35 ° C. aqueous solution, stirred, then removed and analyzed. The level of polymeric soil remover can be determined by radio-tagging the stain remover prior to processing and then radiochemically analyzing by techniques known in the art.

As an alternative to the radiochemical analysis method described above, measuring the soil remover precipitate by measuring the ultraviolet (UV) absorption of the test solution by techniques known in the art in the tests (ie, tests A, B and C). it can. The phenomenon of UV absorption in test solution after removal of hydrophobic fiber material is SRA
Corresponds to an increase in precipitation. As will be apparent to those skilled in the art, for test solutions containing types of materials that cause excessive UV absorption interference, such as high levels of surfactants with aromatic groups (eg, alkylbenzene sulfonates), UV analysis Must not be used.

The "stain remover function activating amount" of the polyhydroxy fatty acid amide refers to the amount of the surfactant which promotes the precipitation of the stain remover on the hydrophobic fiber as described above, or the amount of the surfactant in the detergent composition during the next washing operation. Means the amount of surfactant that enhances grease / oil cleaning performance for the fabric being cleaned.

The amount of polyhydroxy fatty acid amide required to enhance the settling of the soil remover depends on the selected anionic surfactant,
The amount of this surfactant, the specific oil remover selected,
As well as with the selected polyhydroxy fatty acid amide. Generally, the detergent composition comprises from about 0.01% to about 10% by weight,
Typically from about 0.1% to about 5% of a polymeric soil remover, and from about 4% to about 50%, more typically from about 5% to about 5%.
Contains 30% anionic surfactant. The composition should also generally include, but is not limited to, at least about 1%, preferably at least about 3%, by weight of the polyhydroxy fatty acid amide.

Polymeric soil removers that are enhanced in the presence of polyhydroxy fatty acid amides in the presence of anionic surfactants include: (a) (i) a polyoxyethylene segment having a degree of polymerization of at least 2; An oxypropylene or polyoxylene propylene segment having a degree of polymerization, a segment that does not include an oxypropylene unit, or (iii) oxyethylene, unless the hydrophilic segment is linked at each end to an adjacent moiety by an ether link bond. A mixture of oxyalkylene units comprising from 1 to about 30 oxypropylene units, wherein the mixture is sufficient to increase the hydrophilicity of the surface of the conventional polyester synthetic fiber when the soil remover is deposited on the surface. Quantity of oxyethylene And the hydrophilic segment preferably has at least about 25% oxyethylene units, especially for components having about 20-30 oxypropylene units, having at least about 50% oxyethylene units. Or (b), (i) a C3 oxyalkylene terephthalate segment, wherein said hydrophobic component is also oxyethylene terephthalate, and oxyethylene terephthalate. A hydrophobic component having a ratio of: C3 oxyalkylene terephthalate units of about 2: 1 or less;
i) a C4-C6 alkylene or oxy C4-C6 alkylene segment or a mixture thereof, and (iii) a poly (vinyl ester) segment having at least a certain degree of polymerization, preferably a poly (vinyl acetate) segment or a mixture thereof. Wherein said substituent is present in the form of a C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivative or a mixture thereof, and said cellulose derivative is amphoteric and therefore usually precipitates on the surface of polyester synthetic fibers. At the same time as settling on this surface,
One or more hydrophobic components adapted to have sufficient levels of C1-C4 alkyl ether and / or C4 hydroxy alkyl ether units to maintain sufficient hydroxyl levels to increase the hydrophilicity of the fiber surface Or a stain remover having a combination of the components (a) and (b).

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150,
More preferably, it has a degree of polymerization of from 6 to about 100. A suitable oxy C4-C6 alkylene hydrophobic segment is MO3S
Including, but not limited to, end caps of polymeric soil removers such as (CH2) nOCH2CH2O-, where M is sodium and n is an integer of 4-6. U.S. Patent No.
No. 4,721,580, which is incorporated herein by reference.

Polymeric soil removers include cellulose derivatives, such as hydroxyether cellulose polymers, ethylene terephthalate or ethylene terephthalate or propylene terephthalate, and copolymer blocks of polyethylene oxide or terephthalate oxidized polypropylene and the like.

Cellulose derivatives that function as stain removing agents are commercially available, including cellulose hydroxy ethers, such as Methocel ^R (Dow).

Cellulose soil remover used in the present invention,
Includes those selected from the group consisting of C1-4 alkyl and C4 hydroxyalkyl celluloses, such as methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxybutyl methyl cellulose. Various cellulose derivatives useful as soil remover polymers are described in U.S. Pat. No. 4,000,093, which is incorporated by reference.

Stain removers featuring poly (vinyl ester) hydrophobic segments include poly (vinyl esters), such as C1-
It includes copolymers of 6 vinyl esters, preferably poly (vinyl acetate), grafted onto a polyalkylene sub-backbone, such as an oxidized polyethylene backbone.
Such substances are known in the art and are described in European Patent Application 0,219,04
It is described in No. 8. Suitable commercially available soil removers of this type include materials of the Sokalan ^™ type obtained from BASF (West Germany), such as Sokalan ^™ HP-22.

One type of preferred soil remover is a copolymer having random blocks of ethylene terephthalate and polyethylene terephthalate (POE). More specifically, these polymers are ethylene terephthalate and PEO
The repeating unit of terephthalic acid comprises a molar ratio of about 25:75 to about 35:65, and the PEO terephthalic acid unit contains polyethylene oxide having a molecular weight of about 300 to about 2000. The molecular weight of the polymeric soil remover ranges from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230, which is incorporated by reference. U.S. Pat. No. 3,893,929 also discloses similar copolymers.

Other preferred polymeric soil removers contain 10-15% by weight of ethylene terephthalate units and 90-80% by weight of polyoxyethylene terephthalate and have an average molecular weight of 300.
A polyester having repeating units of ethylene terephthalate units derived from -5,000 polyoxyethylene glycol, wherein the molar ratio of ethylene terephthalate to polyoxyethylene terephthalate in the polymer is from 2: 1 to 6: 1. Between. Examples of this polymer, commercially available Zelcon ^R 5126 (Dupont de Nemours) and Mil
ease ^R T (ICI). These polymers and their preparation are described in US Pat. No. 4,702,857, the disclosure of which is incorporated by reference.

Another preferred polymeric soil remover is the sulfonation product of a substantially linear ester oligomer, wherein the oligomer is conjugated to the terephthaloyl oligomeric ester backbone, the oxyalkyleneoxy repeat unit, and the backbone. A terminal moiety, wherein the stain remover comprises allyl alcohol ethoxylate, dimethyl terephthalate and 1,2-propylene diol, and the terminal moiety of each oligomer has an average of from about 1 to about 4 sulfonate groups in total.
These soil removers are fully described in U.S. Pat. No. 4,968,451, the disclosure of which is incorporated by reference.

Other suitable polystain removers are described in U.S. Pat.
No. ethyl or methyl capped 1,2-propylene terephthalate-polyoxyethylene terephthalate
Polyesters, oligomeric esters with anionic endcaps containing sulfo-polyethoxy groups derived from polyethylene glycol (PEG) as described in U.S. Pat. No. 4,721,580, and formula X- (OCH2CH2) n- as described in U.S. Pat. No. 4,702,857. Wherein n is 12 to 43, and X is C1-4 alkyl or preferably methyl. These patents are cited as references.

Other polymeric soil removers include the soil removers of U.S. Patent No. 4,877,896, which discloses anions, especially sulfoaroyl, end-capped terephthalate esters, and is incorporated herein by reference. The telegraphite phthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units. U.S. Patent No.
Among the stain removers of 4,877,896, (b) (i)
There are substances having a polyoxyethylene hydrophilic component or a C3 oxyalkylene terephthalate (propylene terephthalate) repeating unit within the hydrophobic component range.
This is a polymeric soil remover characterized by either or both of these benefits resulting from the presence of the polyhydroxy fatty acid amide in the absence of an anionic surfactant.

If a stain remover is used, this is about the amount of the detergent composition.
0.01 to 10% by weight, typically about 0.1 to about 5% by weight,
Preferably, it is contained in the range of about 0.2 to about 3.0% by weight.

Chelators The detergent compositions of the present invention optionally further comprise one or more iron and manganese chelators as builder additives. Such chelators are selected from aminocarboxylates, aminophosphates, multifunctionally substituted aromatic chelators and mixtures thereof, 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 unique ability of these materials to remove iron and manganese ions from laundry solutions by forming soluble chelates. It is.

The aminocarboxylate used as an optional chelating agent in the composition of the present invention can have one or more, preferably at least two units of the following structure: Where M is hydrogen, an alkyl metal, ammonium or substituted ammonium (eg, ethanolamine), and x
Is 1 to 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having about 6 or more carbons. Aminocarboxylates that can be used include ethylenediaminetetraacetate, N-hydroxyethyl-ethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, its alkali metals,
Ammonium and substituted ammonium salts and mixtures thereof.

If at least a low level of total phosphorus is allowed in the detergent composition, aminophosphonates can be used as chelating agents in the compositions of the present invention.

Useful are compounds having one or more, preferably at least two, structural units: Here, M is hydrogen, an alkali metal, ammonium or substituted ammonium, and x is 1 to 3, preferably 1. These compounds include toluenediaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetriamine pentakis (methylene phosphonate). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups containing about 6 or more carbon atoms. Alkylene groups are shared by substitutions.

Polyfunctionally substituted aromatic chelators can also be used in the compositions of the present invention. These substances can include compounds of the formula: Here, at least one R is -SO3H or -COOH or a soluble salt thereof and a mixture thereof. U.S. Pat. No. 3,812,044, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelators and sequestering agents. A preferred compound in this form of the acid form is dihydroxydisulfobenzene, for example 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions can contain these substances in the form of alkali metal, ammonium or substituted ammonium (eg, mono- or triethanolamine) salts.

When used, these chelating agents generally comprise from about 0.1% to about 10% by weight of the detergent composition. More preferably, the chelating agent is present in the detergent composition from about 0.1 to about
3.0% by weight is contained.

Clay Smear Removal / Reprecipitation Inhibitor The detergent compositions of the present invention can optionally include a water soluble ethoxylated amine having clay stain removal and reprecipitation prevention 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. Liquid detergent compositions typically contain from about 0.01 to about 5% by weight.
These compounds are preferably selected from the following groups: (1) the following formula ethoxylated monoamines: (X-L -) - N- (R 2) 2 (2) formula ethoxylated diamine: Or _{(X-L-) 2 -N-} R 1 -N- (R 2) 2 (3) formula of ethoxylated polyamines: (4) Ethoxylated amine polymer of the following formula: (5) The mixture: Or -O-; R is H or C 1-4 alkyl or hydroxyalkyl; R 1 is C 2-12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene, or 2-20 if an ON bond is not formed. C2-3 oxyalkylene moieties with oxyalkylene units; each R2 is C1-4 or hydroxyalkyl, -LX moiety, or two R2 are moieties-(CH2) r, -A2- (CH2) s together -, Wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, r + s is 3 or 4, X is a nonionic group, an anionic group or a mixture thereof; R3 is a substituted C3 -12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl, or a substituted alkaryl group; R is C
-12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units unless an OO or ON bond is formed; Alkylene moieties
A hydrophilic chain containing [(R50) mK (CH2CH2O) n]-, wherein
R5 is C3-4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety-(CH2CH2O) n- makes up at least about 50% by weight of the polyoxyalkyl moiety; for the monoamine, m is 0 And about 4 and n is at least about 12; for the diamine, m is 0 to about 3; and n is at least about 6 when R1 is C2-3 alkylene, hydroxyalkylene or alkenylene, and R1 is C2-3 alkylene; At least about 3 other than hydroxyalkylene or alkenylene,
For the polyamines and amine polymers, m is from 0 to about 10, n is at least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that when 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 removal / precipitation inhibitor is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. Pat.
No. 597,898, which is incorporated herein by reference. Another group of preferred clay soil removal / resettling inhibitors is European Patent Application No.
No. 111,965. Other clay soil removal / reprecipitation inhibitors are ethoxylate amine polymers described in European Patent Application No. 111,984; European Patent Application No. 112,59.
Zwitter ionic polymer described in No. 2; and amine oxide described in US Pat. No. 4,548,744. All these patents are cited.

In the detergent composition of the present invention, other clay dirt removal / reprecipitation inhibitors known in the art other than those described above can be used. Other types of clay soil removal / reprecipitation inhibitors include carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymer Dispersant In the detergent composition of the present invention, it is preferable to use a polymer dispersant. These substances help control the hardness of calcium and magnesium. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other art-known ones can be used. Without wishing to be bound by theory, polymeric dispersants, when used with other builders (including low molecular weight polycarboxylates), exhibit detergent builder performance due to crystal growth inhibition, peptization of particulate soil, and anti-recipitation effects. Seems to increase as a whole.

Polymeric dispersants are used at levels from about 0.5 to about 5%, more usually from about 1.0 to about 2.0%, by weight of the detergent composition.

The polycarboxylate material as the polymer dispersant used in the present invention is a polymer or copolymer containing at least about 60% by weight of a segment of 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. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen or M is hydrogen, an alkyl metal, ammonia or substituted ammonium.

This type of polymeric polycarboxylate material can be prepared by polymerizing and copolymerizing a suitable unsaturated monomer, preferably in its acid form. 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 methylenemalon. Contains acids. In the polymer polycarboxylate, monomer segments containing no carboxylate group, such as vinyl ethyl ether, styrene, and ethylene, can be present. However, such a segment is about 40
It should not constitute more than weight%.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers used in the present invention are water soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from 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 salts, ammonium salts and substituted ammonium salts. This type of water-soluble polymer is a known substance. The use of this type of polyacrylate in detergent compositions is described, for example, in U.S. Pat.
No. 8,067. This patent is cited as a reference.

As a preferred component of the dispersing / reprecipitating agent, an acrylic / maleic acid-based copolymer can be used. This material includes a water-soluble salt of a copolymer of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is 2,000-100,000, preferably about 5,000-75,
000, most preferably in the range of about 7,000-65,000. The ratio of acrylic acid segments to maleic acid segments in such copolymers generally ranges from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1.
Such water-soluble salts of acrylic / maleic copolymers can include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. This type of water-soluble acrylic acid / maleic acid copolymer is a known substance and is described in European Patent Application No. 66915, which is incorporated herein by reference.

Another polymeric substance that can be included in the compositions of the present invention is polyethylene glycol (PEG). PEG exhibits the performance of a dispersant and acts as a clay soil remover / reprecipitation inhibitor. Typical molecular weight ranges for these purposes are from about 500 to about 100,00, preferably from about 1,000 to about 5
0,000, more preferably from about 1,500 to about 10,000.

Brightener In the detergent composition of the present invention, a known brightener or other brightener or whitening agent can be incorporated.
The choice of brightener used depends on many factors, such as the type of detergent used, the nature of the other ingredients present in the detergent composition, the temperature of the wash water, the degree of agitation and the ratio of the wash to the tub size. I do.

The choice of brightener also depends on the type of laundry, for example, cotton, synthetic fibers and the like. Since many detergent compositions are used for laundering a wide variety of fabrics, the detergent compositions must contain effective brightener mixtures for the various fabrics. Of course, the components of such a brightener mixture must be mutually compatible.

Commercially available brighteners that can be used in the present invention include stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiphene-5-5 dioxide, azoles, 5- and 6-membered heterocycles and derivatives of other materials. However, the present invention is not limited to this. Examples of such brighteners are “The Production
and Application of Fluorescent Brightening Agent
s ", M.Zahradnik, John Wiley & Sons, New York (1982)
And this disclosure is incorporated by reference.

The stilbene derivatives used in the present invention include bis (triazinyl) amino-stilbene derivatives; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene. However, it is not limited to this.

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

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

Carboxylic acid derivatives that can be used in the present invention include, but are not limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; .

The cinnamic acid derivative used in the present invention is a group comprising a cinnamic acid derivative, styrylazole, styrylbenzofuran, styryloxadiazole, styryltriazole and styrylpolyphenyl, as disclosed on page 77 of Zahradnik reference. But is not limited to this.

Styrilazole can be classified into styrylbenzoxazole, styrylimidazole and styrylthiazole as described on page 78 of the aforementioned Zahradnik reference. These subclasses are not necessarily a complete list of styrylazole subgroups.

Another class of brighteners that can be used in the present invention is the Kirk-Othmer Encyclopedia of Chemical, referenced herein.
Technology, Volume 3, pages 737-750 (John Wiley &
Son, Inc., 1962), pages 741-749, wherein 3,7-diaminodibenzothiophene-2,8-disulfonate-5,5-dioxide is used. Including.

Yet another class of brighteners that can be used in the present invention includes azoles, which are derivatives of 5-membered heterocycles. This compound is further divided into monoazoles and bisazoles. Examples of monoazoles and bisazoles are Kirk-
It is described in the Othmer reference.

Yet another class of brighteners that can be used in the present invention is Kirk
-Othmer is a derivative of a 6-membered heterocyclic ring described in the reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.

In addition to the above-mentioned brighteners, various compounds can be used as brighteners. Examples of such various compounds are
1-Hydroxy-3,6,8-pyrene-trisulfonic acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5 -Di-phenylimidazolone-disulphonic acid; and pyrazoline-quinoline derivatives.

Other examples of brighteners that can be used in the present invention are U.S. Pat.
No. 790,856, the disclosure of which is cited. These brighteners are available from Phorwhite, available from Verona.
Including TM brightener series. Other brighteners disclosed in this reference include: Tino commercially available from Ciba Geigy
pal UNPA, Tinopal CBS and Tinopal 5BM; Arctic White CC and Arctic White CWD, commercially available from Hilton Divis, Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazole; 4, Four'
-Bis- (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (styryl) bis-phenyl; and y-aminocoumarin. Examples of these brighteners are 4-
Methyl-7-diethyl-amino coumarin; 1,2-bis-
(Benzimidazol-2-yl) ethylene; 1,3-diphenylfurazoline; 2,5-bis- (benzoxazole-
2-yl) thiophene; 2-styryl-naphtho- [1,2-
d] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole.

Other brighteners used in the present invention are U.S. Pat.
It is described in No. 5, and this is cited as a reference.

Foam Inhibitors To reduce or inhibit the formation of foam, they can be incorporated into known or known compositions of the present invention. The combination of this substance, a "foam inhibitor", is desirable because the polyhydroxyfatty acid amide of the composition of the present invention increases the foaming stability of the detergent composition. Foam inhibitors are especially important when the compositions of the present invention include a surfactant that produces relatively high foaming with the polyhydroxy fatty acid amide surfactant. In the case of a composition for a front-loading type automatic washing machine, suppression of foaming is particularly desirable. These machines have a drum that has a horizontal axis and rotates about this axis for storing laundry and washing water. This type of agitation results in high foam formation, thus reducing cleaning efficiency. The use of suds suppressors is especially important in conditions where hot wash water is used and where high concentrations of surfactants are used.

Various substances can be used in the composition of the present invention. Foam inhibitors are known in the art. Foaming inhibitors are, for example, Kirk Othmer Encyclopedia of Chemical Techn
ology, third Edition, Volume 7, pages 430-447 (John
Wiley & Sons, Inc., 1979). A category of foaming inhibitors of particular interest is monocarboxylic fatty acids and their water-soluble salts. These materials are described in U.S. Pat. No. 2,954,347, which is incorporated by reference. The monocarboxylic fatty acids and salts thereof used in suds suppressors have a hydrocarbyl molecular chain of from 10 to about 24, preferably 12 to 18, carbon atoms. A suitable salt is
Alkali metal and ammonium salts such as sodium, potassium and lithium salts and alkanolammonium salts. These substances are a preferred category of suds suppressors for detergent compositions.

The detergent composition can also include a non-surfactant suds suppressor. These suds suppressors include, for example, the following lists: paraffins, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols, high molecular weight hydrocarbons of aliphatic C18-40 ketones (eg, stearone), and the like. Other suds suppressors include tri- to hexa-alkyl melamines or di- to hexa-alkyl melamines formed as products of cyanuric chloride containing 2 or 3 moles of primary or secondary amines having 1 to 24 carbon atoms. N-alkylated aminotriazines such as tetra-alkyldiamine chlorotriazine, propylene oxide, and stearyl alcohol phosphates and monostearyl di-alkali metal (eg, Na, K, Li) phosphates and phosphonates Contains monostearyl phosphate. Hydrocarbons such as paraffins and haloparaffins can be used in liquid form. The liquid hydrocarbon should be liquid at room temperature and atmospheric pressure and have a pour point in the range of about -40 ° C to about 5 ° C and a minimum boiling point of about 110 ° C (atmospheric pressure) or higher. It is also known to use wax hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbons form a preferred category of foam control agents in detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat.
No. 265,779, which is incorporated herein by reference. These hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term "paraffin" as used by this suds suppressor is intended to include true paraffins and cyclic hydrocarbons.

A preferred category of non-surfactant suds suppressors includes silicone suds suppressors. This category uses polyorganosiloxane oils, such as polydimethylsiloxanes, polyorganosiloxane oils or resin dispersions or emulsions, and polyorganosiloxanes fused to silica in a combination of polyorganosiloxanes and silica particles I do. Silicone suds suppressors are known in the art, for example, U.S. Patent No. 4,265,779,
It is described in European Patent Application No. 89307851.9, both of which are cited.

Other silicone suds suppressors are disclosed in U.S. Patent 3,445,839
This patent relates to compositions and methods for defoaming aqueous solutions by adding a small amount of a polydimethylsiloxane liquid.

Mixtures of silicone and silanated silica are described, for example, in German Patent Application DOS 2,124,526. Silicone defoamers and defoamers in granular detergent compositions are described in U.S. Pat. Nos. 3,933,672 and 4,652,392.

One example of a silicone-based suds suppressor used in the present invention comprises a suds suppressor amount of a suds suppressor comprising the following components: (i) a polydimethylsiloxane fluid having a viscosity of about 20 cs to about 1500 cs at 25 ° C; ii) about 5 to about 50 parts by weight of the siloxane resin per 100 parts by weight of the compound of (i). This siloxane resin is about 0.6: 1
(CH3) 3 SiO1 / 2 units and SiO2 in a ratio of about 1.2: 1
It consists of a unit.

(Iii) about 1 to 20 parts by weight of solid silica gel per 110 parts by weight of the compound of (i).

For any detergent composition used in an automatic washing machine, the foam must not form to the extent that it overflows the washing machine. If a foam control agent is used, it is preferably present in a "foam control amount". The “foaming suppression amount”
It refers to the amount of suds suppressor that can control sudsing to produce a low sudsing detergent when used in an automatic washing machine. The amount of foam control will vary with the detergent surfactant selected. For example, when using a highly lathering surfactant, a relatively higher amount of lather inhibitor is used than when using a lower lathering surfactant. Generally, the foam formed during the wash cycle (i.e., when stirring the detergent in the aqueous solution at the desired wash temperature and concentration conditions) does not exceed about 75% of the voids of the washing container, and preferably does not exceed about 50%. A sufficient amount of the suds suppressor must be incorporated into the low sudsing detergent composition to ensure that it does not. In this case, the gap of the washing machine is the difference between the total volume of the container of the washing machine and the volume of water plus the laundry.

The compositions of the present invention generally contain from 0% to about 5% of a suds suppressor. When used as a suds suppressor, monocarboxy fatty acids and their salts comprise about 5% by weight of the detergent composition.
Exist up to. Preferably, about 0.5% to 3% of a fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition. However, larger amounts can be used. This upper limit is practical because it minimizes cost and uses small amounts of suds suppressors for effective suds suppression. In practice, it is preferred to use from about 0.01% to about 1%, preferably from about 0.25% to about 0.5%, of a silicone suds suppressor. In this case, these weight percentages shall include the silica used with the polyorganosiloxane, as well as any other adjuncts. Monostearyl phosphate is generally present in about 0.1% of the composition.
% To about 2%.

Hydrocarbon suds suppressors are typically from about 0.01% to about 5.
Amounts in the range of 0% are used, but higher levels can be used.

Other Ingredients Various other ingredients useful in detergent compositions can be included. For example, it can contain other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulation, and the like.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for dissolving the surfactant, but polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (eg, propylene glycol, ethylene glycol, glycerin and 1,2-propanediol) are used. You can do it.

The detergent composition of the present invention is preferably formulated such that when used for washing, the wash water has a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. The wash water preferably has a pH of about 7.5 to about 9.5, more preferably about 7.5 to about 9.0.
Having. Techniques for controlling the pH to the desired use level involve the use of buffers, alkalis, acids, etc., and are known to those skilled in the art.

The present invention also provides the above-mentioned polyhydroxyfatty acid amide surfactant in a detergent composition or a mixture thereof comprising an anionic, nonionic and / or cationic surfactant and zeolite or a laminated silicate builder.
The present invention relates to a method of forming the mixture by combining zeolite and / or laminated silicate and the polyhydroxy fatty acid amide surfactant in a weight ratio of about 1:10 to about 20: 1.

The invention also comprises one or more anionic, nonionic or cationic surfactants, zeolites or laminated silicate builders or mixtures thereof, and a polyhydroxyfatty acid amide, wherein the water or water-miscible solvent (e.g. Fiber, fabric comprising a detergent composition containing the builder: polyhydroxyfatty acid amide surfactant in a weight ratio of about 1:10 to about 20: 1 in the presence of a solvent such as an alcohol and a secondary alcohol). A method for purifying said substrate by contacting it with a substrate such as hard, hard or skin. Preferably, agitation is performed to further facilitate purification. Suitable agitation means include manual agitation, cleaning devices such as brushes, sponges, mops, automatic dishwashers, automatic washing machines for textile (eg, clothing) washing.

In the above method, a more preferred weight ratio of the zeolite and / or laminated silicate builder: polyhydroxyfatty acid amide is from about 1: 5 to about 15: 1, most preferably from about 1: 3 to about 10: 1. is there.

Experiment This experiment was performed using the N-methyl,
-It is an example of a method for producing deoxyglucityl lauric amide. The experimenter can vary the shape of the device used, but suitable devices that can be used in this case are a motor driven paddle stirrer and a thermometer long enough to contact the reaction medium. 3 liter four-necked flask equipped with The other two necks of the flask are equipped with a nitrogen scavenging and wide-bore side arm (note: in the case of very rapid methanol evolution, this side arm is important)
An efficient collection condenser and vacuum exhaust means are connected to this side arm. The vacuum exhaust means is connected to a nitrogen extraction device and a vacuum gauge, and is connected to a suction device and a trap. A 500 watt heating mantle equipped with a transformer temperature controller ("Variac") to heat the reaction is mounted on a lab jack movably up and down to control the reaction temperature.

N-methylglucoamine (195 g., 1.0 mol, Aldrich, M
4700-) and methyl laurate (P & G CE1270,22
0.9 g., 1.0 mol) is placed in the flask. The solid / liquid mixture is heated with stirring under a nitrogen apparatus to form a melt (about 25 minutes). When the melt temperature reaches 145 ° C., a catalyst (powdered anhydrous sodium carbonate, 10.5 g., 0.1 mol, JT Baker) is added. Shut off the nitrogen scavenging, adjust the suction device and the nitrogen extraction device and adjust the vacuum to 5 inches Hg. (5 / 31at.
m). From this point, the reaction temperature is maintained at 150 ° C. by adjusting Variac and raising and lowering the mantle.

Within 7 minutes, the first methanol foam is seen on the meniscus of the reaction mixture. A violent reaction follows immediately.
It is distilled until the proportion of methyl has dropped. Adjust the vacuum to produce a vacuum of about 10 inches Hg. (10/31 atm). Increase the vacuum approximately as follows: 10 Hg in 3 minutes
Inch, 20Hg inch in 7 minutes, 25Hg inch in 10 minutes. 11 minutes after the start of methanol generation, stop heating and stirring with some foaming. The product cools and solidifies.

Hereinafter, the present invention will be described in detail with reference to embodiments shown in the drawings, but the present invention is not limited thereto.

Examples 1-12 These examples show heavy duty particulate detergent compositions containing polyhydroxy fatty acid amides and zeolites and / or laminated silicate builders.

Examples 1-4 are formulations suitable for use at about 1400 ppm (wash water base) at temperatures below about 50 ° C. The above-mentioned composition is prepared by blending a base particle component as a slurry to form about 4-
Manufactured by spray drying to 8% residual moisture.
The remaining dry ingredients are mixed in granulated or powdered form with the above-mentioned spray-dried particles in a rotating mixing drum, then the liquid ingredients (nonionic surfactants and perfumes) are sprayed thereon.

The compositions of Examples 5-7 are condensed granular formulations prepared by slurrying the base particulate component, spray drying to about 5% moisture, and mixing the additional particulate or powdered dry component. Dedusting by spraying the powder onto the liquid component. This product has a wash temperature of less than
For use at a concentration of 1050 ppm.

The compositions of Examples 8-10 are preferably used at a temperature of about 30-95 ° C and a concentration of about 6000 ppm on a wash water weight basis. These compositions are made by slurrying the base particle component, which is spray dried to about 9% moisture. The remaining dry ingredients are added, mixed in a rotating mixer drum, and then the final liquid ingredients are sprayed on.

Examples 12-14 show a standard density granular detergent composition used at a wash water temperature of 30-95 ° C and a concentration of about 8000 ppm on a wash water weight basis. The composition spray-drys the slurry of the base particle component to about 10-13% moisture, adds additional dry powder components such as bleach, activators and other additives, and provides perfume, non-ionizing or foam control. It is manufactured by spraying on a liquid such as an agent fluid.

Example 15 Another method for producing the polyhydroxy fatty acid amide used in the present invention is shown below. 84.87 g of fatty acid methyl ester (raw material: P & G methyl ester CE1270) and 75 g of N-
Methyl-D-glucoamine (Aldrich Chemical Company)
M4700-0) and 1.04 g of sodium methoxide (Aldri
Ch. Chemical Company 16,499-2) and 68.51 g of methyl alcohol are used. The reaction vessel includes a standard reflux apparatus equipped with a drying tube, condenser and stir bar. In this method, the mixture is mixed with methanol while stirring under argon gas, mixed well, and heating is started (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Take samples periodically to monitor the reaction process, but note that the solution becomes completely clear after 63.5 minutes. At this point, the reaction is considered to be virtually complete. The reaction mixture is kept at reflux for 4 hours. After removal of methanol, the recovered raw product is 156.16 g. After vacuum drying and purification,
An overall yield of 106.92 g of purified product is recovered. But,
Yield percentages are not calculated on this basis. Regular sampling during the reaction renders the overall yield percentage value meaningless. The reaction is performed at 80% and 90% reactant concentrations for up to 6 hours and can produce products with very little by-product formation.

The following description is not intended to limit the invention, but merely to describe other aspects of the technology considered in making various detergent compositions using polyhydroxyfatty acid amides.

It will be appreciated that polyhydroxy fatty acid amides are unstable under highly basic or highly acidic conditions because of their amide linkages. Although some degradation is acceptable, it is preferred that these materials do not undergo a pH of 11 or more, especially 10 or more, or about 3 or less for an unreasonably long period. The pH of the final product (liquid) is typically 7.0-9.0
It is.

In the production of polyhydroxy fatty acid amides, it is generally necessary to at least partially neutralize the basic catalyst used to form the amide bond. Although any acid can be used for this purpose, detergent formulators will appreciate that it is simple and convenient to use an acid that produces a useful and desirable anion in the finished detergent product. There will be. For example, citric acid can be used for the purpose of neutralization, and the resulting citrate ion (about 1
%) With about 40% of the polyhydroxy fatty acid amide slurry and can be pumped to a later processing stage throughout the detergent manufacturing process. Acidic substances such as oxysuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate and the like can be used as well.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (C12-C14)
It is more water soluble than that derived from C16-C18). . Therefore, the C12-C14 material is easily incorporated into the liquid composition and easily melts in the cold water washing tub. However, C16-C18 materials are also very effective, especially in situations where warm to hot wash water is used. Actually C16-C18 substance is the corresponding C1
A surfactant that is more dispersible than 2-C14 substances. Therefore,
Detergent formulators can balance ease of manufacture with performance when selecting a polyhydroxy fatty acid amide to be used in a given formulation.

It will be appreciated that the water solubility of the polyhydroxy fatty acid amide is increased by having unsaturation and / or branch points in the fatty acid moiety. Thus, materials such as polyhydroxy fatty acid amides derived from oleic acid and isostearic acid are more water soluble than those derived from the corresponding n-alkylation.

Similarly, the solubility of polyhydroxyfatty acid amides made from disaccharides, trisaccharides is generally higher than those derived from monosaccharides. Such water solubility is particularly effective when formulating a liquid composition. In addition, polyhydroxy fatty acid amides in which the polyhydroxy groups are derived from maltose also appear to exhibit excellent detergency, especially when used with conventional alkylbenzene sulfonate (LAS) surfactants. While not intending to be bound by theory, the association of LAS with polyhydroxyfatty acid amides derived from higher saccharides such as maltose causes a substantial and unexpected decrease in interfacial tension in aqueous media, which results in a net decrease in interfacial tension. It appears to enhance detergent performance (the process for making polyhydroxy fatty acid amides derived from maltose is described below).

Polyhydroxy fatty acid amides are produced not only from refined sugars but also from hydrolyzed starches, such as corn starch, potato starch or any other vegetable starch containing saccharides such as mono-, di-, etc. desired by the formulator. Can do things. This is especially important from an economic point of view. That is, "high glucose" corn syrup, "high maltose" corn syrup and the like can be used simply and economically. Lignin removed and hydrolyzed cellulose pulp can also be a raw material for polyhydroxy fatty acid amide.

As mentioned above, polyhydroxy fatty acid amides derived from higher saccharides such as maltose and lactose are more water soluble than those derived from glucose. Furthermore, it seems that a polyhydroxy fatty acid amide having high water solubility can promote the water solubility of a corresponding polyhydroxy fatty acid amide having low water solubility to some extent. Thus, formulators can use raw materials that contain corn syrup with high glucose content, but can choose syrups that contain small amounts of maltose (eg, 1% or more).
The resulting polyhydroxyfatty acid amide mixtures generally exhibit more favorable water solubility over a wider range of temperatures and concentrations than "pure" glucose-derived polyhydroxyfatty acid amides. Thus, not only is it economically advantageous when using a sugar mixture than a pure sugar reactant, polyhydroxy fatty acid amides made from mixed sugars have much advantages with respect to performance and / or ease of formulation. It is. However, in a few cases, some loss of grease removal performance (dishwashing performance) is seen at fatty acid maltose amide levels of about 25% or more, and foaming performance is lost at about 33% or more (see above). The percentage is the percentage of maltose-derived polyhydroxy fatty acid amide to glucose-derived polyhydroxy fatty acid amide in the mixture). This varies to some extent depending on the chain length of the fatty acid moiety. Typically, formulators who choose to use such formulations in this case will have a ratio of monosaccharide (eg, glucose): di- and higher saccharides (eg, maltose) of from about 4: 1 to about 99: 1. It is desirable to select a polyhydroxy fatty acid amide mixture containing

The preparation of the acyclic polyhydroxy fatty acid amide from the fatty ester and the N-alkyl polyol can be carried out in an alcohol solvent at a temperature of about 30C to 90C, preferably about 50-80C. For example, it has been determined that it is desirable for a liquid detergent formulator to perform such a process in a 1,2-propylene glycol solvent. The glycol solvent does not need to be completely removed from the reaction product prior to use in the finished detergent formulation. Similarly, formulators of solid, typically granular detergent compositions may use ethoxylated alcohols such as NEODOL 2
3 In a solvent containing ethoxylated (EO3-8) C12-C14 alcohol sold as EO6.5 (shell)
It may be desirable to carry out the reaction at 0-90 ° C. If such an ethoxylate is used, the ethoxylate should be substantially free of non-ethoxylated alcohol, most preferably substantially monoethoxylated alcohol ("T"). It is preferable not to contain it.

Although the method of making the polyhydroxy fatty acid amide per se does not form part of the present invention, the formulator may be aware of other methods of synthesizing the polyhydroxy fatty acid amide as described below.

Typically, an industrial scale reaction sequence to produce the preferred acyclic polyhydroxy fatty acid amide comprises the following steps.

Step 1—Step of preparing an N-alkyl polyhydroxyamine derivative by forming an N-alkylamine and a sugar adduct from the desired sugar or sugar mixture; Step 2- And N-alkylpolyhydroxyamine used in the second step can be produced by various methods known in the art, but the following method is simple and the raw materials Can be used economical sugar syrup. To obtain the best results using such syrup ingredients, the manufacturer must choose a completely light-colored, almost colorless (water white) syrup.

Performance of N-alkyl polyhydroxyamines from plant-derived sugar syrups 1. Adduct formation In the standard method described below, about 420 g of a about 55 percent glucose solution having a Gardner color of 1 or less (corn syrup-about 231 g glucose-about 1.28 mol) is reacted with about 119 g of an about 50% aqueous methylamine solution (59.5 g of methylamine-1.92 mol). Scavenge the methylamine solution (MMA), shield with N2, and cool to about 10 ° C or less. Scavenge the corn syrup and shield with N2 at about 10-20 ° C. The corn syrup is slowly added to the MMA solution at the reaction temperatures shown in the table below. The Gardner color is measured at a predetermined time (minute).

As is clear from the above data, the reaction temperature was about 30 ° C.
At this point, the adduct has a much worse Gardner color, and at about 50 ° C., the adduct has a Gardner color of 7 or less for only about 30 minutes. In order to allow further reaction and / or to obtain a retention time, the
It must be below ° C. The Gardner color should be no more than about 7, and preferably no more than about 4, for a good color glycoamine.

When using lower temperatures to form the adduct, the time to reach a substantial equilibrium concentration of the adduct is reduced by increasing the amine to sugar ratio. For a 1.5: 1 molar ratio of amine to sugar, equilibrium is reached in about 2 hours at a reaction temperature of about 30 ° C. At the same conditions and a molar ratio of 1.2: 1, the time is at least about 3 hours. A substantial equilibrium conversion of about 90% or more, preferably about 95% or more, more preferably about 99% or more, based on the sugar, and about 7 or less, preferably about 4
In the following, the combination of amine: sugar ratio, reaction temperature and reaction time is selected so as to obtain a color more preferably about 1 or less.

The above method uses various Gardner color corn syrups as shown in the table below at a reaction temperature of about 20 ° C. or less and after a substantial equilibrium has been obtained in at least about 2 hours.
The MMA adduct colors are shown in the table below.

As is evident from the above, the raw sugar material used must be very close to colorless in order to always obtain an acceptable adduct. If the sugar has a Gardner color of about 1, the adduct may be acceptable but not acceptable. If the Gardner color is 1 or more,
The resulting adduct is unacceptable. The better the first color of the sugar, the better the color of the adduct.

II. Hydrogen reaction The adduct having one or less than one Gardner color is hydrogenated by the following method.

About 539 g of underwater adduct and about 23.1 g of Catalyst G49B Ni
Add the catalyst to a 1 liter autoclave and add 2
Scavenge twice with 200 psig H2 at about 20 ° C. H2 pressure about 1
Raise to 400 psi and raise temperature to 50 ° C. Then increase the pressure to about 1600 psig, then raise the temperature for about 3 hours
Keep at 50-55 ° C. At this point the product is about 95%
Hydrogenated. The temperature is then raised to about 85 ° C. in about 30 minutes, the reaction mixture is decanted and the catalyst is filtered off. The product obtained after evaporating water and MMA and filtering is a white powder of about 95% N-methyl glucoamine.

The above procedure is repeated using about 23.1 g of Rani-Ni catalyst, with the following modifications. The catalyst was washed three times, the reactor was purged with the catalyst therein twice with 200 psig H2, then the reactor was pressurized with H2 at 1600 psig for 2 hours, the pressure was removed in 1 hour and the reactor was To 1600 psig. The adduct is then pumped into a 200 psig, 20 ° C. reactor and purged with 200 psig H2 as described above.

In each case, the product is obtained with an N-methyl glucoamine yield of about 95% or more and about 10% on a glucoamine basis.
It contains less than ppm Ni and has a solution Gardner color of less than about 2.

The raw N-methylglucoamine is color stable on short exposure up to about 140 ° C.

Low sugar content (less than about 5%, preferably less than about 1%)
It is important to have an adjunct with excellent color (less than about 7, preferably less than about 4, more preferably less than about 1).

In another reaction, the adduct is prepared by scavenging about 159 g of an about 50% aqueous methylene solution at about 10-20 ° C. with N 2 and shielding. About 330g of about 70% corn syrup
Degas with N2 at 50 ° C and slowly add to the methylamine solution at a temperature below about 20 ° C. Mix this solution for about 30 minutes,
About 95% of the adduct is obtained. This is a very bright yellow solution.

About 190 g of adduct solution and about 9 g of United Catalyst G49B
Ni catalyst and 200 ml autoclave, add, 3
Once, scavenge with H2 at about 20 ° C. The H2 pressure is increased to about 200 psi and the temperature is increased to about 50 ° C. Pressure 25
Raise to 0 psi and hold the temperature at about 50-55 ° C for about 3 hours. The product is now about 95% hydrogenated, then raised to a temperature of about 85 ° C. for about 30 minutes, resulting in a white powder of about 95% N-methylglucoamine after water removal and evaporation. .

In order to minimize the Ni content in the glucoamine, it is important to minimize the contact between the adduct and the catalyst when the H2 pressure is about 1000 psig or less. The nickel content in the N-methylglucoamine in this reaction is about 100 ppm relative to 10 ppm in the above reaction.

To directly compare the effect of the reaction temperature, the following reaction with H2 is performed.

To make the adduct and carry out the hydrogen reaction at different temperatures, a 200 ml autoclave is used according to the same representative process as described above.

About 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 mol) (this solution is made using CarGill's 99DE corn syrup and has a Gardner color of 1 or less) and about 119 g of An adduct for glucoamine production is prepared by combining 50% methylamine (59.5 g MMA; 1.92 mol) (from Air Products).

The reaction process is as follows: 1. Add about 119 g of a 50% methylamine solution to the N2 scavenged reactor, purge with N2 and cool to below about 10 ° C.

2. Degas and / or purge with N2 the 55% corn syrup solution at 10-20 <0> C to remove oxygen in the solution.

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

4. When all of the corn syrup solution has been added,
Stir for hours.

The adduct is used for the hydrogen reaction immediately after production or stored cold to prevent subsequent degradation.

The glucoamine adduct hydrogen reaction is as follows: 1. About 134 g of adduct (Gardner color 1 or less) and about 5.8 g
Of G49B Ni to a 200 ml autoclave.

2. Scavenge the reaction mixture at about 20-30 ° C. with about 200 psi of hydrogen.

3.Pressurize to about 400psi with hydrogen and raise temperature to about 50 ℃
To rise.

4. Raise pressure to about 500 psi and react for about 3 hours.
Maintain the temperature at about 50-55 ° C. Take sample 1.

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

6. Decant and filter out the Ni catalyst. Take sample 2.

Conditions for constant temperature reaction: 1. About 134 g of the adduct and about 5.8 g of G49B Ni are added to a 200 ml autoclave.

2. Scavenge twice at low temperature with about 200 psi of hydrogen.

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

4. Raise pressure to about 500 psi and react for about 5 hours.
Maintain the temperature at the indicated temperature.

5. Decant and filter out the Ni catalyst. Sample 3 is collected at about 50-55 ° C, sample 4 at about 75 ° C, and sample 5 at about 85 ° C. All tests (reaction time at about 85 ° C. are about 45 minutes) give similar purity of N-methylglucoamine (about 94%). The Gardner colors in these tests are similar immediately after the reaction, but only a two-step heat treatment gives good color stability. The 85 ° C test also gives a marginal color immediately after the reaction.

Example 16 A method for producing a resin (cured) fatty acid amide of N-methylmaltoamine used in the detergent composition of the present invention is as follows.

Step 1-Reaction: monohydrate maltose (Aldrich, lot
01318KW); Methylamine (40% by weight in water) (Aldrich l
ot 03325TM); Raney nickel, 50% slurry (UAD 5207)
3D, Aldrich lot 12921LW).

Add the formulation to a glass liner (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry-50 g Raney Ni), place in a 3 L rocking autoclave, and add nitrogen (3 x 50
0 psig) and hydrogen (2 x 500 psig) and rock under hydrogen at a temperature of 28-50 ° C over the weekend. The crude reaction mixture is vacuum filtered twice through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous substance. The last traces of water are azeotropically removed by dissolving the resulting material in methanol and 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, crystallized on cooling, filtered and the filter cake obtained is dried at 35 ° C. under vacuum. This is cut 1. The filtrate is concentrated until a precipitate begins to form and stored overnight in a freezer. The solid is filtered and dried under vacuum. This is cut 2. The filtrate is again concentrated to half its volume and crystallization is performed. Very little precipitate is formed. Add a small amount of ethanol and leave the solution in the freezer over the weekend. The solid material is filtered and dried under vacuum. The bound solid contains N-methylmaltoamine, which is used in step 2 of the overall synthesis.

Step 2—Reactant: N-methylmaltoamine (from step 1); hardened tallow methyl ester; sodium methoxide (25% in methanol); absolute methanol (solvent); molar ratio 1: 1 amine: ester; initial catalyst level 10 mol% (w
/ r maltamine) to 20 mol%; solvent level 50%
(Wt.).

In a sealed flask, 20.36 g of tallow methyl ester is heated to its melting point (water bath) and placed in a 250 ml round bottom flask equipped with a mechanical stirrer. About 70 flasks
Heat to 0 ° C to prevent solidification of the ester. 25.0 separately
g of N-methylmaltoamine are combined with 45.36 g of methanol and the resulting slurry is added to the tallow ester with good stirring. Add 1.51 g of sodium methoxide in a 25% methanol solution. After 4 hours, the reaction mixture did not clear, so an additional 10 mole% of the catalyst (20 mole% total) was added and the reaction was allowed to continue overnight (about 68 ° C), after which time the mixture became clear. Then change the reaction flask for distillation. Increase temperature to 110 ° C. 60 atmospheric distillation
Continue for minutes. Then start high vacuum distillation, continue for 14 minutes,
At this point the product becomes very thick. The product is left in the reaction flask at 110 ° C. for 60 minutes. The product is scraped from the flask and triturated in ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is stored in a heating oven overnight and then ground. The product is stripped of residual N-methylmaltoamine using silica gel. Charge the silica gel slurry in 100% methanol into the funnel and wash several times with 100% methanol. Concentrated sample of the product (20 g in 100 ml of 100% methanol)
Is loaded onto silica gel and eluted several times by vacuum and washing with methanol. The collected eluate is evaporated to dryness (rotary evaporator). The residual tallow ester is removed overnight by trituration in ethyl acetate and then filtered. The filter cake is vacuum dried overnight. The product is a tallow alkyl N-methylmaltoamine.

In another embodiment, it can be performed using commercially available corn syrup containing glucose or a glucose mixture and typically 5% or more maltose. The resulting polyhydroxy fatty acid amides and mixtures thereof can be used in any of the detergent compositions of the present invention.

In yet another embodiment, step 2 of the above reaction sequence.
Can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, the propyl glycol may not have to be removed from the reaction product before use for formulating the detergent composition. Again, if desired by the formulator, the methoxide catalyst can be neutralized with citric acid to sodium citrate, which can remain in the polyhydroxy fatty acid amide.

If desired by the formulator, the compositions of the present invention may employ more or less various foam control agents. Typically, no lather control agent is used because lather is desirable for dishwashing. To wash the fabric of a top-loading washing machine, some foam control is desirable, and for the front-loading type, considerable foam control is preferred. Various foam control agents are known in the art and can be selected in the present invention. In fact, the choice of foam control agent or mixture thereof for a particular detergent composition will not only depend on the presence and amount of polyhydroxy fatty acid amide used therein, but also on other surfactants present in the formulation. It also depends on the agent. However, it appears that various silicone-based foam control agents are more efficient (ie, can be used at lower levels) than other types of foam control agents when using polyhydroxy fatty acid amides. Silicone foam control agents commercially available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful in the present invention.

For fabric detergent compositions which desirably contain a stain remover, the formulator can select from a variety of known materials (eg, US Pat. Nos. 3,962,152, 4,116,8).
No. 85, No. 4,238,531, No. 4,702,857, No. 4,721,580
No. 4,877,896). Additional soil removers used in the present invention include C1-4 alkoxy terminated polyethoxy unit sources (eg, CH3 [OCH2 CH2] 16 OH), terephthaloyl unit sources (eg, dimethyl terephthalate), poly (oxyethylene) oxy unit sources. (Eg, polyethylene glycol 1500), oxyiso-propyleneoxy unit source (eg, 1,2-propylene glycol), and oxyethyleneoxy unit: oxyiso-propyleneoxy unit molar ratio in the oxyethyleneoxy unit source (eg, ethylene glycol). Comprises a nonionic oligomeric esterification product of a reaction mixture containing a source of at least about 0.5: 1. Such nonionic soil removers include the general formula: Wherein R 1 is low (eg C 1-4) alkyl, especially methyl; x and y are each an integer from about 6 to about 100; m is an integer from about 0.75 to about 30; n is an integer from about 0.25 to about 20; R2 is H
A mixture with CH3 that provides a molar ratio of oxyethyleneoxy units: oxyiso-propyleneoxy units of at least about 0.5: 1.

Other preferred soil removers are of the general anionic type described in U.S. Pat. No. 4,877,896, but such soil removers are substantially free of monomers of the HOROH type, wherein R is propylene or higher Alkyl. Thus, the stain removers of U.S. Pat.No. 4,877,896 include, for example, the reaction products of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid, although these additional stain removers are, for example, dimethyl terephthalate. It can include the reaction products of terephthalate, ethylene glycol, 5-sodiosulfophthalate and 3-sodiosulfobenzoic acid. Such soil removers are suitable for use in granular laundry detergents.

The formulator will also appreciate that it is desirable to include a non-perboric acid bleach, especially in heavy duty particulate laundry detergents. Various peroxide bleaching agents are commercially available and can be used in this case, of which percarbonate is convenient and economical. Thus, the compositions of the present invention may contain 3-20%, more preferably 5-18%, most preferably 8-15% by weight of the composition of solid percarbonate bleach.

Sodium percarbonate is an additional component in the form of 2Na2CO3.3H2O2 and is commercially available as a crystalline solid. The most commercially available materials have low levels of heavy metal sequestrants, such as
Contains EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP) or aminophosphate, which are incorporated during the manufacturing process. In the case of the present invention, the percarbonate is incorporated into the detergent composition without additional protection, but the preferred embodiment of the present invention uses a stable form of the substance (FMC).
Various coatings can be used, but the most economical is sodium silicate with a SiO2: Na2O ratio of 1.6: 1 to 2.8: 1, preferably 12.0: 1, which is applied as an aqueous solution. To yield silicate solids at levels of 2-10% (usually 3-5%) by weight of percarbonate. Magnesium silicate can also be used, and any of the above chelating agents can be included in the coating.

The particle size range of the crystalline percarbonate is 350 μm to 450 μm, with an average of about 400 μm. When coated, the crystal has 400
It has a particle size range of ~ 600 μm.

The heavy metals present in the sodium carbonate used to produce percarbonate can be controlled by including a sequestering agent in the reaction mixture, while percarbonate is
Require protection from heavy metals present as impurities in other components in the product. To avoid unacceptable adverse effects on percarbonate stability, the total level of iron, copper and manganese in the product should not exceed 25 ppm, and preferably should not exceed 20 ppm.

 An example of a component of a recent condensation laundry detergent particle is as follows.

Example 17 Component Wt.% C14-15 alkyl alcohol sulfonic acid 13 C14-15 alkyl polyethoxy (2.25) sulfonic acid 5.60 C12-13 alkyl polyethoxylate (6.5) 1.45 C12-14 fatty acid N-methylglucoamide 2.50 Sodium aluminosilicate (hydrated zeolite A) 25.2 Crystal layered silicate builder (1) 23.3 Citric acid 10.0 Sodium carbonate Laundry solution up to pH 9.90 Sodium polyacrylate (mw 2000-4500) 3.2 Diethylenetriamine pentaacetic acid 0.45 Savinase (2) 0.70 6-nonanoylamino-6-peroxycaproic acid 7.40 monohydrated sodium perborate 2.10 nonanoyloxybenzene sulfonic acid 5.00 brightener 0.10 (1) Layered silicate builders are well known in the art. Laminated sodium silicate is preferred. For example, U.S. Pat.
See 859 Laminated Sodium Silicate Builder. This is a reference. A suitable laminated silicate builder is available from Hoechst as SKS-6.

(2) Obtained from Novo Nordisk A / S, Copenhagen.

A highly preferred granular product of the type described above comprises about 0.0001%
From about 2% to about 2% by weight of the active enzyme and at least about 1% by weight of the polyhydroxyfatty acid amide, most preferably the product wherein the anionic surfactant is not an alkylbenzene sulfonate surfactant.

Example 18 The following describes a perborate bleach plus bleach-activated detergent composition of the present invention made by mixing the ingredients in the following table into a mixing drum.

In this example, zeolite A refers to hydrated crystalline zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 3 to 5 microns, and LAS is C12.3 linear sodium alkyl benzene sulfonate. Means AS is C14
-15 means sodium alkyl sulfate, and non-ionic means
Coconut alcohol is condensed with about 6.5 moles of ethylene oxide per mole of alcohol to remove non-ethoxylated and monoethoxylated alcohols, abbreviation CnAE6.5T, DTPA means sodium diethylenetriaminepentapentaacetate.

(1) Basic particles are produced by spray drying an aqueous clutcher mix of the above components.

(2) Newly made sample of NAPAA wet cake. This typically involves about 60% of water, about 2% of oxygen (AvO) obtained from peracid (equivalent to about 36% of NAPAA), and the remainder (about 4%) of unreacted feedstock. Consists of The wet cake is quenched by placing the crude reaction product of NAAA (monononylamide of adipic acid), sulfuric acid and hydrogen peroxide in water, followed by filtration, washing with distilled water, and phosphate buffer. It is obtained by washing and making a wet cake by final suction filtration. A portion of this wet cake is air dried at room temperature to form a dried sample, which is typically about 5% AvO (corresponding to about 90% of NAPAA).
And about 10% of unreacted raw materials. When dried,
The sample pH is about 4.5.

NAPAA particles consist of about 51.7 parts by weight of dried NAPAA wet cake (containing about 10% unreacted material) and about 11.1 parts by weight of sodium C12.3 linear alkylbenzene sulfonate (L
AS) It is made by mixing a paste (45% active), about 43.3 parts by weight of sodium sulfate and about 30 parts by weight of water in a CUISINART mixer. After drying, the particles (about 47
(With% NAPAA) is passed through a No. 14 Tyla mesh sieve and sized by retaining all particles that have not passed through a No. 65 Tyla mesh. According to Malvern particle size analysis, average amide peracid particles (agglomerate)
Has a particle size of about 5-40 microns and an average particle size of about 10-20.
Micron.

(3) NOBS (nonanoyloxybenzene sulfonate) particles are manufactured according to U.S. Pat. No. 4,997,596, the disclosure of which is incorporated by reference.

(4) Zeolite particles having the following composition are made by mixing zeolite A with PEG8000 and CnAE6.5T in an Eirich RO8 high intensity mixer.

PEG8000 is a form containing 50% water, about 55 ゜ F
(12.8 ° C). CnAE 6.5T is liquid and about
Maintained at 90 ° F (32.2 ° C). These two liquids are 12
Mixed by pumping through the element's static mixer. The resulting binder material is approximately 75 ° F (23.9 ° C)
And a viscosity of about 5000 cps. The ratio of PEG8000 and CnAE6.5T through this mixer is 72:28.

The EirichRO8 high intensity mixer is operated in batch mode. First, 34.1 kg of powdered zeolite A are placed in a mixer pan. The mixer is started, first rotating the pan counterclockwise at a speed of about 75 revolutions per minute, and then rotating the rotor blades clockwise at 1800 rpm. Next, zeolite A
In the Eirich RO8 strong energy mixer containing
The binder is pumped directly from the static mixer. The binder feed rate is about 2 minutes. The mixer continues mixing for an additional 1 minute for a total batch time of about 3 minutes. The batch is then discharged and collected in a fiber drum.

Until about 225 kg of wet product has been collected
Repeat the batch stage. 240-2
Dry in a fluidized bed at 70 ° F (116-132 ° C). This drying step removes most of the free water and changes the composition as described above. The total energy input applied by the mixer to the product in batch mode is about 1.31X1
0 12 erg / kg, about 2.18 × 10 9 erg / kg-s.

The resulting flowable agglomerates have an average particle size of about 4500-500 microns.

Example 19 The composition of a granular laundry detergent composition suitable for use at a relatively high concentration and over a wide temperature range, particularly common in front-loading automatic washing machines in Europe, is as follows.

(1) SOKALAN is a polyacrylic acid / sodium maleate commercially available from Hoechst.

(2) Monsanto trademark pentaphosphonomethyl diethylenetriamine.

(3) Ciba Geigy's brightener.

(4) Metasaliton's trademark FINNFIX.

(5) Lipolytic enzyme from NOVO LIPOLASE (6) Protease enzyme from NOVO SAVINASE (7) X2-3419 is a foam inhibitor from Dow Corning.

The particle manufacturing method includes various steps such as tower drying, agglomeration, and dry addition as described below. Percentages are based on the finished composition.

A. Clutching and blowing through the tower Using standard technology, clutch the following ingredients,
Dry the tower.

SOKALAN CPS 3.52% DEQUEST 2066 0.45% TINOPAL DMS 0.28% Magnesium sulfate 0.49% Anhydrous zeolite A 7.1% CMC 0.47% B. Surfactant agglomerate B1. Tallow alkyl sulfate sodium salt and C12-15 EO (3)
Agglomeration of sulphate sodium salt paste-Tallow alkyl sulphate 50% active paste and C12-1
5 Agglomerate a 70% paste of sodium EO (3) sulfate with zeolite A and sodium carbonate in the following ratio (contribution of agglomerate to detergent after drying).

Tallow alkyl sulfate 2.82% C12-15 EO (3) sulfate 1.18% Zeolite A 5.3% Sodium carbonate 4.5% B2. C14-15 alkyl sulfate, C12-15 alkyl ethoxy sulfate, DOBANOL C12-15 EO (3) And C16−18 N−
Methylglucose amide-C16-18 glucose amide nonionics are converted to the DOBANOL C12-15 EO present during the reaction of the methyl ester with N-methylglucoamine.
Combine with (3). DOBANOL C12-15 EO (3) acts as a melting point depressor, which allows the reaction to be carried out without forming undesirable cyclic glucose amides.

20% DOBANOL C12-15 EO (3) and 80% C16-18 N
A surfactant mixture with methylglucoseamide is obtained, which is co-agglomerated with 10% sodium carbonate.

Next, the particles are treated with a C14-15 alkyl sulfate and C12
-15 Co-agglomeration with sodium salt of EO (3) sulfate, zeolite A and excess sodium carbonate. These particles show excellent dispersibility of C16-18 N-methylglucose amide in cold water.

The overall formulation of this particle (the contribution of the agglomerate to the detergent formulation after drying) is as follows: C16-18 N-methylglucose amide 4.1% DOBANOL C12-15 EO (3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% C14-15 alkyl sulfate sodium salt 3.5% C12-15 EO (3) sodium sulfate 0.59% C. Dry additive Add the following components: percarbonate 22.3% TAED (tetraacetylethylenediamine) 5.9% Laminated Hoechst Silicate SKS6 12.90% Citric acid 3.5% Lipolase 0.42% 100,000 LU / g SAVOMASE 4.0 KNPU 1.65% Zinc phthalocyanine (photobleaching) 0.02% D. Spray-on DOBANOL C12-15 EO (3) 2.60% Fragrance 0.53% E. Foaming Inhibitor Silicone foaming inhibitor X2-3419 (95% -97% high molecular weight linear silicone; 3% -5% hydrophobic silica) (Dow Corning) was converted to zeolite A (particle size 2-5μ), starch and steer. Co-agglomerate with a ril alcohol binder. The particles have the following formulation: Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% This detergent is used in European washing machines, for example AEG
30 ° C, 85g detergent in a brand washing machine, 4
It showed good solubility, performance and foam control when used at 0 ° C, 60 ° C and 90 ° C cycles.

Example 20 In any of the above examples, instead of the fatty acid glucoamide surfactant, an equal amount of maltoamide or a glucoamide / maltoamide surfactant mixture from the plant can be used. The use of ethanolamide in the composition would promote low temperature stability of the finished formulation. In addition, the use of amine oxide and / or sulfobetaine (aka "saltein") surfactants produces excellent foaming.

If a particularly high foaming composition is desired, it is preferred to use no more than about 5%, more preferably no more than about 2%, and most preferably substantially zero C14 or higher fatty acids. This is because foaming can be suppressed. Accordingly, formulators of the high foaming compositions may avoid introducing such foaming inhibiting amounts of higher fatty acids with polyhydroxy fatty acid amides into the high foaming compositions and / or during storage of the composition. It is desirable to avoid the formation of higher fatty acids. A simple approach consists in using a C12 ester reactant to produce the polyhydroxy fatty acid amides of the present invention. Fortunately, the use of amine oxides or sulfobetaines can partially overcome the undesirable foaming effects caused by fatty acids.

Formulators who wish to add anionic brighteners to liquid detergents containing relatively high concentrations (eg, 10% or more) of anionic or polyanionic substituents, such as polycarboxylate builders, require that brighteners be added to water and polyanions. It may be desirable to premix with the hydroxy fatty acid amide and then add the premix to the final composition.

For zeolite built detergents, it is effective to use polyglutamic acid or polyaspartic acid. AE
Fluid or flake and DC-544 (Dow Corning)
Are other examples of effective foam control agents.

As will be apparent to those skilled in the art, the production of polyhydroxy fatty acid amides using di- and higher saccharides such as maltose forms a polyhydroxy fatty acid amide in which the linear substitution Z is "capped" by a polyhydroxy ring structure. . Such materials can be used satisfactorily in the present invention and are within the spirit of the present invention.

────────────────────────────────────────────────── (5) References JP-A-64-20298 (JP, A) JP-A-1-182398 (JP, A) US Patent 3,676,340 (US, A) (58) Fields studied (Int .Cl. ⁷ , DB name) C11D 1/52 C11D 3/08 C11D 3/12

Claims (15)

(57) [Claims] A built-in detergent composition comprising one or more anionic, nonionic or cationic detersive surfactants or mixtures thereof, an optional detersive adduct, and an optional auxiliary builder, The detergent composition comprises: (a) at least 1% by weight of a zeolite or a laminated silicate detergent builder or a mixture thereof; and (b) at least 1% by weight of a polyhydroxy fatty acid amide of 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 at least 3 hydroxyl directly bonded to the molecular chain. A built-in detergent composition comprising a polyhydroxyhydrocarbyl containing a linear hydrocarbyl having a group or an alkoxylated derivative thereof. 2. The method according to claim 1, wherein the zeolite builder is zeolite A.
The composition of claim 1, wherein 3. The composition according to claim 1, wherein Z of the polyhydroxy fatty acid amide material is derived from a reducing sugar, R ¹ is methyl, and R ² is C 9 -C 17 alkyl or alkenyl. Wherein Z comprises _{-CH 2 (CHOH) 4 CH 2} OH, A composition according to claim 3. 5. The composition according to claim 1, wherein in said polyhydroxy fatty acid amide, Z is derived from maltose. 6. The composition of claim 1, wherein in said polyhydroxy fatty acid amide, Z is derived from a mixture of monosaccharides and disaccharides, said mixture containing at least 1% of at least one disaccharide. 7. The composition of claim 1, wherein the zeolite: polyhydroxy fatty acid amide ratio is between 1:10 and 20: 1. 8. The method according to claim 1, comprising one or more anionic surfactants selected from the group consisting of alkyl sulfates, alkyl ethoxylate sulfates, alkyl ester sulfonates and alkyl benzene sulfonates. Composition. 9. The detergent composition according to claim 8, further comprising an alkyl ethoxylate or an alkyl polyglycoside nonionic surfactant or a mixture thereof. 10. The detergent composition according to claim 1, further comprising a polycarboxylate builder. 11. One or more anionic, nonionic or cationic detersive surfactants or mixtures thereof, zeolites or laminated silicate builders or mixtures thereof, optional detersive adducts, and optional components. A method of enhancing the fabric cleaning performance of a detergent composition comprising: an auxiliary builder, the method comprising:
Using a polyhydroxy fatty acid amide of the following formula Wherein R ¹ is H, C ¹ -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof,
R ² is a polyhydroxy hydrocarbyl or alkoxylated derivative thereof comprising a linear hydrocarbyl with at least 3 hydroxyl groups C5-C31 hydrocarbyl, and Z is bonded directly to the molecular chain, wherein the zeolite and polyhydroxy fatty acid amides 1: 10 ~
20. The method of claim 20, comprising washing the fabric with said detergent composition in a conventional manner. 12. The method of claim 11, wherein said detergent composition contains one or more anionic surfactants. 13. The method of claim 11, wherein said Z moiety in said polyhydroxy fatty acid amide is derived from a mixture of plant-derived monosaccharides, disaccharides and polysaccharides. 14. The method of claim 13, wherein R ² moiety in said polyhydroxy fatty acid amide, C15-C17 alkyl, alkenyl or mixtures thereof, The method of claim 11. 15. The method of claim 11, wherein said anionic surfactant is not an alkyl benzene sulfonate surfactant.