JPH06501736A - Polyhydroxy fatty acid amides in detergents with polycarboxylate builders - Google Patents

Abstract

Disclosed are detergent compositions containing polycarboxylate builders and one or more anionic, nonionic, or cationic detersive surfactants, or mixtures thereof, improved by the inclusion of certain polyhydroxy fatty acid amide surfactants. The compositions comprise at least 1 % by weight of polycarboxylate builder, and at least 1 % by weight of a polyhydroxy fatty acid amide of formula (I) wherein R<1> is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; and R<2> is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Description

[Detailed description of the invention] Polyhydroxy fatty acid amides in detergents with polycarboxylate builders Technical field The performance of detergent compositions containing polycarboxylate builders is based on polyhydroxy fatty acids. Amide surfactants provide a variety of builder substances for use in detergent compositions. ,Proposed. Such materials can be used for hardness sequestration, pebutization, pl+ control, etc. It is useful for various functions including. For many years, sodium tripolyphosphate has been the choice. builder, but recent developments in the field include zeolites, various polycarbonate Including builder substances such as Boxylet 1.

Currently, many fully formulated detergent compositions are made from polycarboxylate builder. Contains or various types of polylubogi: /1 No!・Bilgoo containing builder Contains a mixture (7C).

The development of high-performance laundry detergent compositions of Phosphe-1 and 7 is a major industrial challenge. be. From a performance standpoint, even the best polycarboxylate builders are For example, in hard water, an "under-built" situation may occur. It's set. Furthermore, simply increasing the usage of builders would unduly increase costs. In particular, anionic washing during use under relatively high water hardness conditions may cause Agents can pose solubility problems for surfactants. Alkyl ethoxylate etc. Conventional nonionic surfactants do not suffer from solubility problems, whereas typically Gives excellent overall cleaning at low to medium wash temperatures do not have. Also, common nonionic surfactants are used in formulating granular and liquid detergent formulations. It may be difficult to

Therefore, heavy-duty detergent formulators are forced to consider other performance-enhancing products. I have relied on means. In order to enhance the cleaning performance of such compositions, sophisticated formulations Manufacturers have formulated various cleaning aids. Detergent enzymes, stain-releasing polymers, bleach To enhance the performance of detergent compositions containing carboxylate builders, substances such as It is commonly used. This indicates that a large amount of the builder is alkyl sulfate-1-, Addition of various anionic surfactants such as kill ester sulfonates to formulations This is especially true in liquid detergent formulations, as they can cause solubility.

Simply stated, the invention results from the use of polycarboxylate builders. improved detergent surfactant systems to help compensate for deficiencies in cleaning performance. use. By practicing the present invention, the polyhydroxy fatty acid amide comprising Used as a detergent with polycarboxylate builders to provide superior cleaning performance be done. Furthermore, these polyhydroxy fatty acid amides contain large amounts of builders and Facilitates the formulation of granular detergents and especially liquid detergents with anionic surfactants.

Various polyhydroxy fatty acid amides have been described in the art. For example, N- Anru-N-methylglucamide, J.W., Gutsupai, M.A., Marcus, E. Chin, and P.L., Finn, “The thermotoplasty of some straight-chain carbohydrate amphiphiles. "Lopic Liquid Crystal", ■, 1quid Crystals 51988, Volume 3 , No. 11, pp. 1569-1581, and A. Muller-Farnala. ,■.

Zabel, M., Stauffer, and R. Hilgenfeld, “Nonionic Detergents Molecular structure and crystal structure of nonanoyl-N-methylglucamide J J, Ch ew, Soc, Chew.

Commun, 19'86, pp. 1573-1574. Ru. The use of N-alkyl polyhydroxyamide surfactants has recently gained momentum in biochemistry. For example, it may be of substantial interest for use in biofilm degradation. It has become. For example, in J.E., a journal article by Hildreth, “Membrane Biogenesis Academic grade N-D-glucose N-methyl-alkanamide compound, a new kind of non-ionic Detergent J, Blochea, J. (1982), Volume 207, Page 363 -See pages 366.

The use of N-acylated lucamines in detergent compositions has also been discussed. E,R , U.S. Patent No. 2,965,576 issued December 20, 1960 to Wilson. Specification and published on February 18, 1959, Thomas Hedley end car. British Patent No. 809,060, assigned to Company Ltd. Amide surfactant (this is added as a low temperature foaming agent) (which may include tilglucamide). These compounds Examples include N-acyl groups of higher straight chain fatty acids having 10 to 14 carbon atoms. Ru. These compositions contain alkali metal phosphates, alkali metal silicates, sulfur Auxiliary substances such as ates, carbonates, etc. may also be included. Also, it is generally desirable Additional ingredients that impart desirable properties to the composition, such as fluorescent dyes, bleaching agents, fragrances, etc. It has been pointed out that it can be incorporated into compositions.

U.S. Patent No. 2.703,79 issued March 8, 1955 to A. M. Schwartz. Specification No. 8 describes a condensation reaction between N-alkylglucamine and aliphatic ester of fatty acid. The present invention relates to an aqueous detergent composition containing the product. The product of this reaction requires further purification. It is said that it can be used in aqueous detergent compositions. 195 to A.M. Schwartz. As disclosed in U.S. Pat. No. 2,717,894, issued September 13, It is also known to produce sulfate esters of sylated glucamine.

PCT International Application No. 83 by J. Hildreth, published December 22, 1983 No. 104412 applies to cosmetics, medicines, shampoos, lotions, and eye ointments. as a surfactant, as a medical emulsifier and dispensing agent, and as a membrane, whole cell or has other uses in biochemistry for solubilizing tissue samples and producing liposomes. Polyhydroxyl aliphatic groups are said to be useful for a variety of purposes, including Contains an amphipathic compound. This disclosure includes the formula R'CON (R)CH 2R' and R' CON (R) R' (wherein R is hydrogen or an organic atomic group , R' is an aliphatic hydrocarbon group having at least 3 carbon atoms, and Rj is aldose (which is a residue of) is included.

European Patent No. 0285 of H. Kerkenberg et al. published on October 12, 1988 No. 768 discloses that N-polyhydroxyalkyl fatty acid amide is enriched in an aqueous detergent system. Concerning use as a sticky agent. formula RC(0)N (X)R2 (wherein R1 is C1 to C17 (preferably C-C) and R2 is hydrogen, C-C (preferably C-C6) alkyl or 18 l (X is polyhydroxyalkyl having 4 to 7 carbon atoms) Amides of, for example, N-methyl coconut fatty acid glucamide. aqueous The surfactant system may contain other anionic surfactants, such as alkylaryl sulfonates. olefin sulfonates, sulfosuccinic acid half ester salts, and fatty alcohols. ether sulfonates, and nonionic surfactants such as fatty alcohols. polyglycol ether, alkylphenol polyglycol ether, fat Acid polyglycol ester, polypropylene oxide-polyethylene oxide blend It can contain polymers, etc., but the thickening properties of amides are lower than those containing paraffinsulfonate. It has been pointed out that it has particular use in liquid surfactant systems with. paraffin Ruphonate/N-methyl coconut fatty acid glucamide/Nonionic surfactant shampoo A pump formulation is exemplified.

In addition to thickening properties, N-polyhydroxyalkyl fatty acid amides have excellent skin tolerability. It is said to have tolerant properties.

No. 2,982,737 issued May 2, 1961 to Boettner et al. The specifications include urea, sodium lauryl sulfate anionic surfactant, and N-methyl- N-Sorbityllaurinamide and N-methyl-N-sorbityl myristamide A detergent solid containing an N-alkyl glucamide nonionic surfactant selected from Regarding shapes.

Other glucamide surfactants may be used, e.g. (In the formula, R is C1-C3 alkyl, R2 is C1°-C22 alkyl, , n is 3 or 4). selected from one or more surfactants and polymeric phosphates. Detergent compositions containing builder salts, sequestering agents and detergent alkalis DT No. 2゜226. of H, W, Elacart, etc. announced on December 20, 1973. No. 872. N-acylpolyhydroxyalkylamine is , added as a dirt-settling agent.

U.S. Patent No. 3,654,16 issued April 4, 1972 to H.W., Elakart et al. Specification No. 6 describes anionic surfactants, zwitterionic surfactants and nonionic surfactants. Formula R as at least one surfactant selected from the group and fabric softener N (Z)C(0)R2 (in the formula, ■ R is c-c alkyl, R is 07-C21a1 to 222 R and R2 have a total of 23 to 39 carbon atoms, and Z is -CH(CHOH) CH20H (in the formula, m is 3 or 2) is a polyhydroxyalkyl which can be 4) - A detergent composition containing an N-alkyl polyhydroxyalkyl compound.

No. 4,021,539 issued May 3, 1977 to H. Mellor et al. The calligraphy is the expression RN　(R)CH(CHOH)　R(In the formula, R1 is Hll　■　2 lower alkyl, hydroxy lower alkyl, or aminoalkyl, as well as heterocycles of the formula aminoalkyl, R is the same as R1, but both can be H. and R is CHOH or C00E). The present invention relates to skin treatment cosmetic compositions containing sialkylamines.

Buddhist Patent No. 1,36 assigned to Commercial Trubenz Corporation Specification No. 0,018 (April 26, 1963) is based on the formula RC(0) N (R,) G (wherein R is a carboxylic acid having at least 7 carbon atoms is functional, R1 is hydrogen or a lower alkyl group, and G has at least a carbon number of Form stabilized against polymerization by adding an amide of 5 (glycidol group) Concerning solutions of aldehydes.

No. 1,261,861 (February 29, 1968, Hines, A.) ) is the expression N(R)(R')(R2)C In the formula, R is a sugar residue of glucamine, and R is C-C alkyl group and R2 is a C1-C5 acyl group) as a wetting agent/dispersing agent This invention relates to useful glucamine derivatives.

Announced on February 15, 1956 and transferred to Atlas Powder Company. British Patent No. 745,036 describes chemical intermediates, emulsifiers, wetting agents/dispersing agents, Heterocyclic amides, which are said to be useful as detergents, fabric softeners, etc. Regarding these carboxylic acid esters.

The compound is 2N(R)(R1)C(0)R2 (wherein R is anhydrous hexane is a residue of nithol or its carboxylic acid ester, and R1 is a monovalent hydrocarbon group. (-C(0)R2 is an acyl group of a carboxylic acid having 2 to 25 carbon atoms) It is expressed as

U.S. Patent No. 3.312.627 issued April 4, 1967 to D. T. Hooker. The specification essentially consists of an anionic detergent and an alkaline builder substance. Lithium soap of fatty acids, consisting of propylene oxide-ethylenediamine-ethylene Oxide condensate, propylene oxide propylene glycol-ethylene oxy Contains a nonionic surfactant selected from polycondensates and polymerized ethylene glycols. and also has the formula RC(0)NR(R2) (in the formula, RC(0) is about 10 to about 14 carbon atoms, R and R2 are each H or a C-C alkyl group, and the alkyl group has Lugyl groups have a total number of carbon atoms of 2 to about 7 and a total number of 1-substituted hydroxyl groups of 2 It also includes a nonionic foaming component, which can include a polyhydroxyamide having a A solid cosmetic solid having the following properties is disclosed. Substantially similar disclosures include D. T. Hooker. No. 3,312,626, issued April 4, 1967. Ru.

Demonstration of invention Improved detergent compositions containing polycarboxylate builders consist of polyhydroxy sialic fatty acid amide surfactant and preferably one or more anionic detergent surfactants , nonionic detergent surfactants or cationic detergent surfactants or mixtures thereof provided by a formulation of Therefore, the composition of the present invention comprises polycarboxylate at least 1% by weight of builder, and formula [Wherein, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydro xypropyl, or mixtures thereof, preferably Ci-C4 alkyl, Preferably C or C2 alkyl, most preferably c1 alkyl (i.e. methyl ); R2 is C5-C31 hydrocarbyl, preferably linear C7-C19 a alkyl or alkenyl, more preferably straight chain C9-c17 alkyl or alkenyl kenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or a mixture thereof; Z is at least three hydroxyls directly linked to the chain; or polyhydroxyhydrocarbyl having a linear hydrocarpyl chain with is an alkoxylated derivative (preferably ethoxylated or propoxylated) of Contains at least 1% by weight of polyhydroxy fatty acid amide. Z is preferably reduced will be derived from reducing sugars in the amination reaction; more preferably Z will be derived from reducing sugars; It's lyshityl. Suitable reducing sugars include glucose, fructose, and maltose. and lactose, galactose, mannose, and xylose.

Ingredients: high dextrose corn syrup, high fructose corn syrup , and high maltose corn syrup are available as well as the individual sugars listed above.

These corn syrups may be used to prepare the Z sugar component mix.

It should be understood that no intention is intended to exclude other suitable raw materials. Thus , Z is preferably -CH2-(CHOH)n-CH20H.

-CH(CHOH)-(CHOH) CHOH.

2 n-12 -CH-(CHOH) 2(CHOR')(CHOH)-CH20H.

(In the formula, n is an integer from 3 to 5, and R/ is H or a cyclic or aliphatic monosaccharide. ), and alkoxylated derivatives thereof.

Glycythyl where n is 4, especially -CH2-(CHOH)4-CH20H is most preferred.

Preferably, a pair of polycarboxylate builders of a polyhydroxy fatty acid amide, The weight ratio is from about 1:10 to about 10:1, more preferably from about 1:5 to about 7:1, Most preferably within the range of about 1:1 to about 7=1. The present invention provides liquid detergent compositions including, but not limited to, both detergent compositions and granular detergent compositions.

The present invention has improved builder effectiveness and therefore is particularly suitable for grease/oil cleaners. Polycarboxylic compounds that can also have improved cleaning performance in the field of cleaning A detergent composition containing a rate builder is provided.

- Furthermore, the present invention provides that the weight ratio of polycarboxylate to amide surfactant is about 1: The polyhydroxy fatty acid amide interface in the composition is from 10 to about 10:1. By blending active agents, anionic surfactants, nonionic surfactants and and/or detergents containing cationic surfactants and polycarboxylate builders. Provided are methods for improving the performance of agents.

Furthermore, the present invention provides a method for treating substrates such as fibers, fabrics, hard surfaces, skin, etc. with water, water-miscible solvents ( one or more anions in the presence of a solvent such as, for example, primary and secondary alcohols). on surfactant, nonionic surfactant or cationic surfactant, polycarboxylic At least about 1% sylate builder, and less polyhydroxy fatty acid amide A detergent composition containing 1% of both polycarboxylate builder and polycarboxylate builder. The weight ratio of the droxy fatty acid amide surfactant is from about 1:10 to about 10:1) A method is provided for cleaning a substrate by contacting it with a substrate.

Agitation is preferably provided to enhance cleaning.

Suitable means for providing agitation include hand rubbing or preferably a brush. Scrub by hand with the help of a scrubber, sponge, mop or other cleaning device. Examples include automatic washing machines, automatic dishwashers, etc.

In the method, a more preferable polycarboxylate builder is a pair of polyhydrocarbons. The weight ratio of oxyfatty acid amide is from about 1=5 to about 7=1, most preferably about 1=1. about 7:1 from polyhydroxy fatty acid amide and polycarboxylate Preferred amounts and types of ts are as described herein.

The composition herein includes all of the polyhydroxy fatty acid amide surfactants listed below. also about 1%, typically about 3% to about 50%, preferably about 3% to about 30%. Yes.

The polyhydroxy fatty acid amide surfactant component of the present invention has the structural formula: [Wherein, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydro xypropyl, or mixtures thereof, preferably C1-C4 alkyl, more preferably Preferably C or C2 alkyl, most preferably C1a,2 is less carbyl (i.e. methyl) and R is C-C31 human 0 carbyl, preferably straight Chain C7, to C19 alkyl or alkenyl, more preferably straight chain C9 to C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixtures thereof; Z is at least Polyhydroxyhydride with linear hydrocarpyl chain with 3 hydroxyls locarbyl or its alkoxylated derivatives (preferably ethoxylated or proponent) It consists of a compound which is (oxylated). Z is preferably in the reductive amination reaction. Z may be derived from a reducing sugar; more preferably Z is glycityl. good Suitable reducing sugars include glucose, fructose, maltose, lactose, and Includes lactose, mannose, and xylose. High strength as a raw material Straws Corn Syrup, High Maltose Corn Syrup, and High Maltose Corn syrup can be used as well as the individual sugars mentioned above. These corn syrup The company may prepare a mix of sugar ingredients for Z. Never exclude other suitable raw materials. It should be understood that we are not trying to eliminate Z is preferably -CH-(CH OH) -CH20H1n -CH(CI(0H)-(CHOH) CHOH.

2 n-12 -CH-(CHOH) (CHOR')(CHOH)-CH20H.

(where n is an integer from 3 to 5, and R' is H or a cyclic or aliphatic monosaccharide. ), and alkoxylated derivatives thereof. n is 4, glycityl, especially -CH-(CHOH)4-CH20H is most preferred.

In formula (1), R1 is, for example, N-methyl, N-ethyl, N-propyl, N-i sopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxy It can be cipropyl.

R2-Co-N< is, for example, cocoa amide, stearamide, oleamide, la Urinamide, myristamide, caprinamide, palmitamide, tallowamide It can be, for example, de.

Z is 1-deoxygludityl, 2-deoxyfructityl, 1-deoxymal Tityl, 1-deoxyglutyl, 1-deoxygalactityl, 1-deoxyglutyl Dityl, 1-deoxymaltotriothytyl, and the like.

Methods for making polyhydroxy fatty acid amides are known in the art. Generally, they are Alkylamines are reacted with reducing sugars in a reductive amination reaction to form the corresponding N-alkylamines. N-alkylpolyhydroxyamine and then N-alkylpolyhydroxyamine is reacted with aliphatic ester or triglyceride in the condensation/amidation step. to produce an N-alkyl-N-polyhydroxy fatty acid amide product. It can be manufactured by The method for producing a composition containing polyhydroxy fatty acid amide is as follows: For example, 195 by Thomas Headley End Company Ltd. British Patent No. 809.060 published February 18, 1999, E. R. Wilson No. 2,965,576, issued December 20, 1960, and Andrew M. Schwartz U.S. Patent No. 2, issued March 8, 1955. No. 703.798 and U.S. Pat. No. 1985.424 (each of which is incorporated herein by reference) has been disclosed.

The glycityl component is derived from glucose and is N-alkyl or N-hydroxya N-methyl, N-ethyl, N-propyl, N-butyl, N-hydro N-alkyl or N-hydroxy, which is loxethyl or N-hydroxypropyl In one method for producing droxyalkyl-N-deoxyglycityl fatty acid amide , the product lyses N-alkyl- or N-hydroxyalkyl-glucamine. Trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate Lithium, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, hydroxide potassium chloride, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate , disodium tartrate, dipotassium tartrate, potassium sodium tartrate, citric acid trisodium acid, tripotassium citrate, basic sodium silicate, basic silicic acid Potassium, basic sodium aluminosilicate, and basic potassium aluminosilicate fatty methyl in the presence of a catalyst selected from the group consisting of fatty acid esters selected from esters, fatty ethyl esters and fatty triglycerides; It is produced by reacting with stell. The amount of catalyst is preferably N-alkyl from about 0.5 mol % to about 5 mol % or N-hydroxyalkyl-glucamine on a mole basis. 0 mol%, more preferably about 2.0 mol% to about 10 mol%. The reaction is favorable 1. <> is typically carried out at about 1-38°C to about 170°C for about 20 to about 90 minutes. to When utilizing liglycerides in the reaction mixture as a source of fatty acid esters, the reaction is Preferably from about 1 to about]-0% by weight of the total reaction mixture, calculated on a % basis, saturated. Fatty alcohol polyethoxylates, alkyl polyglycosides, linear glucamides This is carried out using a phase transfer agent selected from surfactants and mixtures thereof.

Preferably, the illegality is carried out as follows: (a) Preheat the fatty acid ester to about 38°C to about 170°C; (b) Fat heated with N~alkyl or N-hydroxyalkylglucamine Add the acid ester and mix to the extent necessary to prepare the two-phase liquid-liquid mixture; ( c) incorporating a catalyst into the reaction mixture; (d) Stir for a predetermined reaction time.

Also preferably, if the fatty acid ester is a triglyceride, about 2 ~20% by weight of preformed linear N-alkyl/N-hydroxyalkyl- The N-linear glucosyl fatty acid amide product is added to the reaction mixture as a phase transfer agent. Ru. This accelerates the reaction and thereby increases the reaction rate. detailed experiments The method is given below in the experiment.

The polyhydroxy "fatty acid" amide materials used herein are also wholly or primarily natural. Detergent formulators benefit from manufacturing from natural, renewable, non-petrochemical feedstocks provided and degradable. They also exhibit low toxicity to aquatic organisms.

Used together with polyhydroxy fatty acid amides of formula (I) to produce them The method also typically involves adding an amount of ester amide, cyclic polyhydroxy fatty acid It should be recognized that non-volatile by-products such as mido may also be produced. this The amount of these byproducts will vary depending on the specific reactants and process conditions. . Preferably, the polyhydroxy fatty acid amide blended into the detergent composition herein is polyhydroxy fatty acid amide-containing composition or cyclic polyhydroxy fatty acid added to the agent provided in such a form that it contains less than about 10% amide, preferably less than about 4°6 Will. The preferred method described above contains rather small amounts of such cyclic amide by-products. Since only the by-products of are produced, what is the sequence?

polycarboxylate builder The compositions herein will include at least about 1% polycarboxylate builder. cormorant.

The amount of polycarboxylate builder will depend on the end use of the composition and the desired physical form. Can vary widely depending on. Liquid formulations typically contain about 5 to about 5 detergent builders. 0.2% by weight, more typically from about 5 to about 30%. Granular formulations typically is from about 10 to about 80% by weight detergency builder, more typically from about 15 to about 50% by weight. including. However, less or more amount of builders means eliminating do not. Preferably, polyhydroxy fatty acid amide versus polycarboxylate building The weight ratio of goo is about 1:10 to about 1021, more preferably about 1:5 to about 7. =1, most preferably from about 1=1 to about 7=1.

A variety of polycarboxylate compounds can be utilized in the present compositions. used here The “polycarboxylate” used has multiple carboxylate groups, preferably a few carboxylate groups. It refers to compounds with at least 3 carboxylates.

Polycarboxylate builders generally can be added to the composition in acid form, but It can also be added in the form of salt. When used in salt form, sodium salt, potassium salt, Alkali metal salts such as tium salts, especially sodium salts, or ammonium salts and Bi-substituted ammonium salts (eg alkanol ammonium salts) are preferred.

Polycarboxylate builders include various categories of useful materials.

One important category of polycarboxylate builders is the ether polycarboxylate builder. Includes boxylate. Numerous ether polymers used as detergent builders Boxylate is disclosed.

Examples of useful ether polycarboxylates include Berub U.S. Pat. No. 3.1.28°287 and January 18, 1972 No. 3,635,830, issued by Lamberke et al. xydisuccinate (both incorporated herein by reference).

Certain types of ether polycarboxylates useful as builders in the present invention include is the general formula % formula %)() (wherein A is H or OH: B is H or -0-CH(COOX)-CH 2(COOX) and X is H or a salt-forming cation) Examples include those having the following. For example, in the general formula above, both A and B are H. If present, the compound is oxydisuccinic acid and its water-soluble salts. A is 0H If SB is H, the compound is tartrate monosuccinic acid (TMS) and It is its water-soluble salt. A is I(, B is 10-CM (COOX)-CH2(CO OX), the compound is tartrate disuccinic acid (TDS) and its It is a water-soluble salt. Mixtures of these builders are particularly preferred for use here. stomach. TMS to TDS weight ratio of about 97:23 to about 20:80 A mixture with is particularly preferred. These builders were published on May 5, 1987. No. 4,663,071 issued to Shu et al.

In addition, suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds. compounds, e.g., U.S. Pat. No. 3,923,679, No. 3,835,16 Specification No. 3, Specification No. 4,158,635, Specification No. 4.120.874 and and No. 4,102,903, all of which are incorporated herein by reference. Examples include those listed in (1).

Other useful detergency builders include the structure HO-rc (R) (COOM) -C(R) (COOM) -0co -H [where M is hydrogen or ' is a cation ( The resulting salts are water soluble), preferably alkali metal, ammonium or substituted ammonium monium cation, and n is about 2 to about 15 (preferably n is about 2 to about 10, more preferably n is on average about 2 to about 4), each R is the same or different, hydrogen , 1-4 selected from C alkyl or C-substituted alkyl 1-4 (preferably R is hydrogen)] Examples include polycarboxylates.

Other ether polycarboxylates include maleic anhydride and ethylene or or copolymer with vinyl methyl ether, 1,3.5-)lyhydroxybenzene -2゜4.6-trisulfonic acid and carboxymethyloxysuccinic acid are mentioned. It will be done.

As organic polycarboxylate builders, various alkali metal salts of polyacetic acid are used. , ammonium salts, substituted ammonium salts, and other polyacetates. Po Examples of lyacetic acid builder salts are ethylenediaminetetraacetic acid and nitrilotriacetic acid builder salts. Lithium salts, potassium salts, lithium salts, ammonium salts and substituted ammonium salts It is.

Also, mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-trical Polymers such as bonic acid, benzenepentacarboxylic acid, and carboxymethyloxysuccinic acid Also included are recarboxylates and their soluble salts.

Citric acid-based builders, such as citric acid and its soluble salts, are - A polycarboxylate builder of particular importance in liquid detergent formulations. However, granular compositions can also be used. Suitable salts include metal salts, e.g. ammonium salts, lithium salts and potassium salts, and ammonium salts and substituted ammonium salts. Examples include nium salts.

Other carboxylate builders include Deal, published March 28, 1973; No. 3,723,322 (incorporated herein by reference) carboxylated carbohydrates.

Also, Bushu U.S. Pat. No. 4,566.984, issued January 28, 1986. 3,3-dicarboxy-4-oxy as disclosed in the specification (herein incorporated by reference) Sar-1,6-hexanedioate and related compounds are preferred in detergent compositions of the present invention. suitable. Useful succinic acid builders include 05-C2o alkyl succinic acids and and their salts. Particularly preferred compounds of this type are It is citric acid. Alkyl succinic acids typically have the general formula R-CH(COOH) CH2(COOH), i.e. it is a derivative of succinic acid (wherein R is a hydrocarbon For example, C1o=020 alkyl or alkenyl, preferably 012- C16, or R is hydroxyl, sulfo, sulfo, as described in said patent. optionally substituted with oxy or sulfone substituents).

Succinate builders are preferably sodium salts, potassium salts, ammonium salts, etc. It is used in the form of water-soluble salts, including ammonium salts and alkali, nolammonium salts.

Specific examples of succinate builders include lauryl succinate and myristic succinate. Balmityl succinate, 2-dodecenyl succinate (preferred), 2-succinate Examples include pentadecenyl. Lauryl succinate is the preferred building block of this group. European Patent Application Box 86200690.5 published on November 5, 1986 No. 10,200.263.

Also, examples of useful builders include sodium and potassium carboxymers. Tyloxymalonate, carboxymethyloxysuccinate, cis-cyclohe Xanehexacarboxylate, cis-cyclopentanetetracarboxylate, water soluble polyacrylates (these polyacrylates have a molecular weight greater than about 2,000) acrylates can also be effectively used as dispersants), and maleic anhydride and vinyl Mention may be made of salts of copolymers with methyl ether or ethylene.

Other suitable polycarboxylates include Krutschfi, published March 13, 1979. U.S. Pat. No. 4,144,226 to Old et al., incorporated herein by reference. ) is a polyacetal carboxylate disclosed in . These polyacetal lacquer Ruboxylates can be produced as follows. Glyoxylic acid ester and a polymerization initiator together under polymerization conditions. Next, the obtained polyacetal pigment By bonding carboxylic acid esters to chemically stable terminal groups, polyacetal carboxyl Stabilizes the sylate against rapid depolymerization in alkaline solutions and converts it to the corresponding salt. Chemical formula 17, add to surfactant.

Polycarboxylate builders are listed in Deal's U.S. special edition published March 7, 1967. Also disclosed in Patent No. 3,308,067 (incorporated herein as a reference) There is.

Such substances include maleic acid, itaconic acid, mesaconic acid, fumaric acid, and aconic acid. Homopolymers of aliphatic carboxylic acids such as citrate acid, citraconic acid, and methylenemalonic acid and water-soluble salts of copolymers.

other builders The composition here includes, in addition to the polycarboxylate builder, auxiliary builders, e.g. For example, both organic and inorganic builders can additionally be included. auxiliary builder Typical amounts of from about 5% to about 2[]O by weight of the polycarboxy I/-1-builder %.

Inorganic detergent builders include, without limitation, silicic acid, carbonic acid (bicarbonate and sesquicarbonate), (including carbonic acid), sulfuric acid, and alkali metal salts of aluminosilicate, ammonium salts and alkanol ammonium salts. Borate builder and washing Contains borate-forming substances that can form borates under storage or cleaning conditions Builders (collectively "borate builders" below) may also be used. Preferably , non-borate builders are used under wash conditions below about 50°C, especially below about 40°C. It is used in the composition of the present invention.

Examples of silicate builders are alkali metal silicates, especially S10:Na2O ratios. 1.6:1 to 3.2:1 and layered silicates, such as H,P , U.S. Patent No. 4.664.839 issued May 12, 1987 to Ritte. (incorporated herein as a reference). However However, other silicates, such as magnesium silicate, may also be used; is used in granular formulations as a burr imparting agent, as a stabilizer for oxygen bleaches, and as a control agent. It can serve as an ingredient in foam systems.

Examples of carbonate builders are sodium carbonate and sodium sesquicarbonate. and those patent application No. 2,321,001 published on November 15, 1973. Ultra-fine carbonate carbonate as disclosed in the No. 1 specification (the disclosure of which is incorporated herein by reference) In carbonates of alkaline earth metals and alkali metals, including mixtures with lucium. be.

Aluminosilicate builders include polycarboxylate builders in the present invention. It is particularly useful for use in concentrates. Aluminosilicate builders are the most It is of great importance in heavy-duty granular detergent compositions currently on the market and It can also be a significant builder ingredient in liquid detergent compositions. aluminosilike As a chart builder, the experimental formula %formula%) (where M is sodium, potassium, ammonium or substituted ammonium) , 2 is about 0.5 to about 2; y is ]) This substance has Ca per gram of anhydrous aluminosilicate. COa hardness has a magnesium ion exchange capacity of at least 50 equivalents. Like The new aluminosilicate has the formula %formula% (wherein 2 and y are integers of at least 6, and the molar ratio of 2 to y is from 1.0 to about 0.5 and X is an integer from about 15 to about 264) It is a zeolite builder with

Useful aluminosilicate ion exchange materials are commercially available. these aluminum Nosilicates can be crystalline or amorphous in structure and are naturally occurring aluminum It can be a silicic acid or can be synthetically derived.

The method of manufacturing aluminosilicate ion exchange materials is described in the published October 12, 1976 No. 3,985,669 to Rumel et al. (incorporated herein by reference). ) is disclosed. Preferred synthetic crystalline aluminosilicate ions useful herein The exchange material is known as zeolite and has the designation zeolite A, zeolite Available as P (B) and Zeolite X. In a particularly preferred embodiment , a crystalline aluminosilicate ion exchange material has the formula %formula% (wherein X is about 20 to about 30, especially about 27). This zeolite , known as zeolite A. Preferably the aluminosilicate is 0.1 It has a particle size in the range of ~10μ.

Phosphate and phosphonate builders are generally combined with polycarboxylates or Phosphates and phosphonates, although it is desirable to replace them with other builders. Builders can be added. Thus, if present, they are preferably present in small amounts Mix only. Preferably, the phosphate builder accounts for all building blocks in the composition. most preferably accounts for less than about 10%, more preferably less than about 5%, by weight of the present invention. Qualitatively non-existent. Specific examples of polyphosphates are alkali metal tripolyphosphates , sodium, potassium and ammonium pyrophosphate, sodium, potassium um and ammonium pyrophosphate, sodium and potassium orthophosphate phosphate, sodium polymetaphosphate having a degree of polymerization of about 6 to about 21, and phyti It is a salt of acid.

An example of a phosphonate builder salt is ethane-1-hydroxy-1,1-diphosphone. Water-soluble salts of acids, especially sodium and potassium salts, methylene diphosphonic acid in water Soluble salts, such as trisodium and tripotassium salts and substituted methylene diphosphates Water-soluble salts of sulfonic acids, such as trisodium and tripotassium ethylidene, Sopropylidene benzylmethylidene and halomethylidene diphosphonate . Phosphonate builder salts of the above type were manufactured by Diehl on December 1, 1964 and and U.S. Pat. No. 3,159,581, issued October 19, 1965, and No. 3,213,030, U.S. Patent No. 3,213,030, issued January 14, 1969 to Roy. No. 3,422,021 and Finby September 3, 1968 and 19 U.S. Patent Nos. 3,400,148 and 3,4 issued January 14, 1969 No. 22,137, the disclosure of which is incorporated herein by reference. ).

Preferred bilgoux systems for granular compositions include zeolites (preferably zeolite A) about 5% to about 50% and citrate (preferably sodium citrate) about 5% to about 5%. 0% (the percentages are calculated on a weight basis based on the total bilgo in the mixture). (based on).

Other organic builders known in the art can also be used. For example, long chain hydrocarbyl Monocarboxylic acids and their soluble salts are available. As these , substances commonly referred to as "soaps". CI(1”20 chain length is standard) It is typically used. Hydrocarbyls can be saturated or unsaturated .

Detergent surfactant system In addition to polyhydroxy fatty acid amides and polycarboxylate builders, this The composition may contain anionic surfactants, cationic surfactants or nonionic surfactants. Contains one or more additional surfactants, which can be sex agents. Typically, In addition to the polyhydroxy fatty acid amide, the surfactant system contains one or more anionic fields. Surfactants and/or nonionic surfactants may be included.

The amount of additional detergent surfactant present typically comprises at least 1% by weight of the detergent composition. %, preferably from about 3 to about 40%, more preferably from about 5 to about 30% by weight. . Anionic surfactants, e.g. anionic sulfate or sulfonate interfaces The use of active agents or mixtures thereof is specifically contemplated. A suitable surfactant, It is described below.

Alkyl ester sulfonate surfactant here Alkyl ester sulfonate As a surfactant, ``The Journal of the American Oil Chemistry'' Sutsu Society J, 52 (1975), pp.

C8-C2o carbons sulfonated with gaseous SO3 according to 323-329 Included are linear esters of acids (ie fatty acids). Suitable starting materials include Ta Natural fatty substances such as those derived from raw, balm oils and the like may be mentioned.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications have the structural formula (wherein R3 is C-C hydrocarbyl, preferably alkyl, or a group thereof) and R4 is 01-C6 hydrocarbyl, preferably alkyl, or is the combination thereof, and M is the alkyl ester sulfonate and the water-soluble salt. consisting of an alkyl ester sulfonate surfactant (which is a cation that forms) .

Suitable salt-forming cations include metals such as sodium, potassium and phosphorus. thium, and substituted or unsubstituted ammonium cations, e.g. methyl-, di- Methyl-, trimethyl- and quaternary ammonium cations, e.g. Thyl-ammonium and dimethylpiperidinium, and alkanolamines , e.g. monoethanolamine, jetanolamine, and triethanol Examples include cations derived from amines.

Preferably R is Cl0=016 alkyl and R is methyl, ethyl or It is isopropyl. Methyl ester sulfonate in which R is 014-016 alkyl Particularly preferred are nates.

Alkyl sulfate surfactant The alkyl sulfate surfactant herein has the formula RO5OMC, where R is preferably has a C10-C24 hydrocarbyl, preferably a C1o-C2o alkyl moiety. alkyl or hydroxyalkyl, more preferably CI2-C18 alkyl or hydroxyalkyl, M is H or a cation, e.g. alkali Metal cations (e.g. sodium, potassium, lithium), substituted or unsubstituted Ammonium cations, such as methyl-, dimethyl-1 and trimethylammonium monium and quaternary ammonium cations, e.g. tetramethyl-ammonium um and dimethylpiperidinium, and ethanolamine, jetanol Cations derived from alkanolamines such as amine, triethanolamine, etc. , and mixtures thereof]. Typically, 012-C16 alkyl chains are suitable for lower wash temperatures (e.g., less than about 50°C). Preferably and with C16-18 alkyl chains, higher wash temperatures (e.g. about 50°C (at higher temperatures).

Alkyl alkoxylated sulfate surfactant here Alkyl alkoxylated sulfate Phate surfactants have the formula RO(A) SOM [where R is C10-C24 unsubstituted Cl0 with alkyl component = C24 alkyl or hydroxyalkyl groups, preferably C12-C2o alkyl or hydroxyalkyl, more preferably is 012-018 alkyl or hydroxyalkyl, and A is ethoxy or or propoxy units, where m is greater than O, typically from about 0.5 to about 6, More preferably about 0.5 to about 3, M is H or, for example, a metal cation ( For example, sodium, potassium, lithium, calcium, magnesium, etc.) A cation that can be ammonium or a substituted ammonium cation. water-soluble salts or acids. Alkyl ethoxylated sulfates and alkyl ethoxylated sulfates Propoxylated sulfates are contemplated herein. Substituted ammonium cation Specific examples include methyl-, dimethyl-, trimethyl-ammonium and Quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl-ammonium lupiperidinium and alkanolamines, such as monoethanolamine, Cations derived from jetanolamine and triethanolamine, and mixtures thereof. Exemplary surfactants include 012-018 alkyl polyethoxylate (1,0) sulfate, C12-C18 alkyl polyester Toxylate (2,25) sulfate, c12-C alkyl polyethoxylate (3,0) sulfate, and C12-018 alkyl polyethoxylate (4,0>sulfate (where M is conveniently selected from sodium and potassium) be revealed).

Other anionic surfactants Other anionic surfactants useful for cleaning purposes can also be included in the compositions herein. this These include soap salts (e.g., sodium salts, potassium salts, ammonium salts, and substituted ammonium salts, such as monoethanolamine salts, jetanolamine salts, (including amine salts and triethanolamine salts), 09-C2o linear alkyl bases C-C22 primary or secondary alkanesulfonate, C 8-C24 olefin sulfonates, e.g. British Patent No. 1.082,179 Sulfonation of pyrolysis products of alkaline earth metal citrates as described in the specification. Sulfonated polycarboxylic acid, alkylglycerol sulfone produced by fatty acylglycerol sulfonate, fatty oleylglycerol sulfonate ate, alkylphenol ethylene oxide ether sulfate, paraffin acyl sulfonates, alkyl phosphates, isethionates, e.g. Thionate, N-acyl taurate, methyl tauride fatty acid amide, alkyl Sufucinamate and sulfosuccinate, monoester of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinates Diesters (especially saturated and unsaturated 06-C14 diesters), N-acylsal Cosinates, sulfates of alkyl polysaccharides, e.g. alkyl polyglucosides sulfates (non-ionic non-sulfated compounds are listed below), secondary alkyl sulfates, and alkyl polyethoxy carboxylates, e.g. RO(CHCH20) k-CH2COO-M” (wherein, R is 08 to C22 k is an integer from 0 to 10, and M is a soluble salt-forming cation) and fats esterified with isethionic acid and neutralized with sodium hydroxide. Examples include fatty acids. Resin acids and hydrogenated resin acids, e.g. rosin, hydrogenated resin resin, and resin acids present in or derived from tall oil and hydrogenation. Resinated acids are also suitable. Yet another example is “surfactants and detergents” (Schwa Ruth, Berry and Birch, Volumes 1 and 2). Various Such surfactants are commonly used in Rollin et al., published December 30, 1975, Patent No. 3,929,678, column 23, line 58 to column 29, line 23 (here (incorporated as a reference).

Suitable nonionic detergent surfactants are generally described in Law, published December 30, 1975. No. 3,929,678 to Lin et al., column 13, lines 14 to 16. 6 (incorporated herein as a reference). Useful nonionic surfactants Exemplary non-limiting types of agents are described below.

1゜ Polyethylene oxide condensate of alkylphenol, polypropylene oxide Sid condensates and polybutylene oxide condensates. Generally polyethylene oxide Condensates are preferred. These compounds may have either a linear or branched configuration. Alkylphenol having an alkyl group having from about 6 to about 12 carbon atoms and alkylene oxide. In a preferred embodiment, ethi Ren oxide in an amount equal to about 5 to about 25 moles per mole of alkylphenol. exists in Commercially available nonionic surfactants of this type include GAF Corporation Igepal” CO-630, commercially available from Trit, which is commercially available from Ham & Hearth Company. onTM) X-45, X-114, X-100, and X-102. . These surfactants are typically alkylphenol alkoxylates, e.g. , called alkylphenol ethoxylate.

2. Condensate of aliphatic alcohol and about 1 to about 25 moles of ethylene oxide. fat The alkyl chain of the group alcohol can be straight chain or branched primary or secondary. and generally have about 8 to about 22 carbon atoms. A of about 10 to about 20 carbon atoms Alcohols having alkyl groups and about 2 to about 18 moles of ethyl alcohol per mole of alcohol. Particularly preferred are condensates with ren oxide. This kind of commercially available nonionic surfactants An example of this is the one marketed by Union Carbide Corporation. TergitolTM 15-S-9 (C-C linear second condensation product of alcohol and about 9 moles of ethylene oxide), Tergitol TM24 -L-6NMW (CI2 to C14 with narrow molecular weight distribution and Delcol) condensate with 6 moles of ethylene oxide) by Shell Chemical Company Commercially available Neodol 45-9 (C14-C15 line) condensate of alcohol and 9 moles of ethylene oxide), Neodol TM23-6 ．． 5 (condensate of C-C linear alcohol and 6.5 mol of ethylene oxide), Neodol TM45-7 (C-C linear alcohol and 7 moles of ethylene oxide) condensate), Neodol TM45-4 (C14-015 linear alcohol and ethylene condensate with 4 moles of oxide), and The Brocter End Gamble Ka KiM marketed by Mouth (Kyro) EOB (C13-C15 alcohol and ethylene oxide 9 condensates with moles). These surfactants are often It is called toxylate.

3. Loose gas produced by condensation of propylene oxide and propylene glycol Condensation product of aqueous base and ethylene oxide. The hydrophobic portion of these compounds is Preferably, it has a molecular weight of about 1,500 to about 1,800 and is water-insoluble. This hydrophobic part The addition of polyoxyethylene moieties to the molecule tends to increase the water solubility of the molecule as a whole. The liquid properties of the product are such that the polyoxyethylene content is approximately equal to the total weight of the condensate. 50% (corresponding to condensation with up to about 40 moles of ethylene oxide) be done. Examples of compounds of this type include the purpuric acid commercially available from BAS F. PIuronIc™ surfactants.

4. Products resulting from the reaction of propylene oxide and ethylenediamine and ethylene Condensate with oxide. The hydrophobic portion of these products is ethylenediamine and excess with propylene oxide and generally has a molecular weight of about 2,500 to about It has 3000. This hydrophobic part has a condensate of polyoxyethylene of about 40 to about 8 0% by weight and has a molecular weight of about 5.000 to about 11,000. Condenses with tyrene oxide. Examples of this type of nonionic surfactant include BAS Tetronic (Tetronic) compound marketed by F. I can name some things.

5. Semipolar nonionic surfactants are a special category of nonionic surfactants. Examples include one alkyl moiety having about 10 to about 18 carbon atoms and one alkyl moiety having about 10 to about 18 carbon atoms. a moiety selected from the group consisting of 1 to about 3 alkyl groups and hydroxyalkyl groups; Water-soluble amine oxide containing 2: alkyl moieties of about 10 to about 18 carbon atoms 1 a group consisting of alkyl groups and hydroxyalkyl groups having about 1 to about 3 carbon atoms a water-soluble phosphine oxyto containing 2 moieties selected from; and about 1 carbon number; 1 alkyl moiety of 0 to about 18 and alkyl of about 1 to about 3 carbon atoms and hydro Water-soluble sulfoxy containing one moiety selected from the group consisting of xyalkyl moieties One example is de.

As a semipolar nonionic detergent surfactant, the formula (where R3 has a carbon number of about 8 to about 22 an alkyl, hydroxyalkyl, or alkylphenyl group or a mixture thereof. compound; R4 is alkylene or hydroxyalkylene having about 2 to about 3 carbon atoms; or mixtures thereof: X is 0 to about 3; each R5 has about 1 to about 3 carbon atoms; 3 alkyl or hydroxyalkyl groups or about 1 to about 3 ethyleneoxy polyethylene oxide group containing a do group) Examples include amine oxide surfactants having the following. The R5 group may be, for example, oxygen or can be bonded to each other through nitrogen atoms to form a ring structure.

These amine oxide surfactants include, in particular, C-C alkyl dimethyl amines. oxide and C8-C alkoxyethyldihydroxydiethylamine oxide can be mentioned.

6. A hydrophobic group having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2. 198 with a polysaccharide (e.g. polyglycoside) parent group containing 7 sugar units No. 4,565,647 to Lenado, issued January 21, 2006. Alkyl polysaccharide. Any reducing sugar having 5 or 6 carbon atoms can be used, e.g. Glucose, galactose and galactosyl moieties replace the lucosyl moiety, (In some cases, hydrophobic groups are bonded at positions 2, 3, 4, etc.) glucose or galactose as opposed to coside or galactoside give). The sugar bond is, for example, the 1st position of the additional sugar unit and the 2nd position on the previous sugar unit, It can be between 3rd, 4th and/or 6th place.

In some cases, less desirable, polyalcohols linking the hydrophobic and polysaccharide moieties are used. There can be xylene oxide chains. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups have about 8 to about 18 carbon atoms, preferably about From 10 to about 16 saturated or unsaturated branched or unbranched alkyl groups are included. good Preferably, the alkyl group is a straight chain saturated alkyl group. Approximately 3 or more alkyl groups can contain hydroxy groups and/or polyalkylene oxide chains may contain up to about 10, preferably less than 5 alkylene oxide moieties. I can do it. Preferred alkyl polysaccharides are octyl, nonyldecyl, undecyl Decyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecy and octadecyl, g, tri, tetra, penta, and hexag. rucoside, galactoside, lactocyto, glucose, fructocyto, fructo and/or galactose. A suitable mixture is coconut tsual. Kyl, di, tri, tetra-1 and pentaglucosides and tallowalkyl Includes tetra-, penta-, and hexa-glucosides.

Preferred alkyl polyglycosides have the formula (wherein R2 is alkyl, alkyl hydroxyl, hydroxyalkyl, hydroxyalkylphenyl, and their from about 10 to about 18 alkyl groups, preferably from about 10 to about 18 alkyl groups; has about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; X is from about 1.3 to about 10. Preferably about 1 ．． 3 to about 3, most preferably about 1.3 to about 2.7) has. Glycodyl is preferably derived from glucose. these compounds To produce alcohol, first, alcohol or alkyl polyethoxy alcohol is produced. and then reacted with glucose or a glucose source to form the glucoside (1-position ). Additional glycosyl units are then added to their first position and the previous group. 2nd, 3rd, 4th and/or 6th position of the lycodyl unit, preferably primarily the 2nd position Can be combined between

7. Fatty acid amide surfactant having the following formula [wherein R6 has a carbon number of about 7 to about 2] 1 (preferably about 9 to about 17) alkyl groups, each R7 being hydrogen, C-C4 alkyl group; 01-C4 hydroxyalkyl, and -(C2H40) xH (in the formula , X is selected from the group consisting of about 1 to about 3)] Preferred amides are C8-C2o ammonia amide, monoethanolamide, di- ethanolamide, and isopropanolamide.

Non-ionized generally preferred for use in addition to polyhydroxy fatty acid amides Compounds include alkyl ethoxylates, alkyl polyglyconides, and alkyl ethoxylates. Examples include kylphenol ethquinate. These include the anions present in the composition. Can be added to surfactants.

Cationic surfactant Cationic detergent surfactants can also be included in the detergent compositions of the present invention. Cation surface activity Ammonium surfactants, such as alkyldimethylammonium Muhalogenide and formula %formula% [wherein R2 is an alkyl group having about 8 to about 18 carbon atoms in the alkyl chain] or an alkylbenzyl group, and each R3 is -CHCH-1-CHCH(CH) -1-CH2CH(CH20H)-1 selected from the group consisting of CH2CH2CH2- and mixtures thereof; each R4 is C -C alkyl, C to C hydroxyalkyl, benzyl, connects two R4 groups a ring structure formed by 00) and hydrogen (when y is not 0) selected from the group: R5 is the same as R4 or is an alkyl chain, R+R5 carbon atom The total number of children is about 18 or less; each y- is from O to about 10, and the sum of the y values is from 0 to about 15; X is a compatible anion].

Other cationic surfactants useful here also include In U.S. Pat. No. 4,228°044 to Bure (incorporated herein by reference), The amphoteric surfactants described can be incorporated into the detergent compositions herein.

These surfactants are secondary surfactants in which the aliphatic groups can be linear or branched. or aliphatic derivatives of tertiary amines, or heterocyclic secondary and tertiary amines It can be broadly described as an aliphatic derivative of One of the aliphatic substituents has at least 8 carbons have elementary atoms, typically about 8 to about 18 carbon atoms, and at least one is anionic. Contains water-solubilizing groups such as carboxy, sulfonate, sulfate.

For examples of amphoteric surfactants, see Rollin et al., December 30, 1975. U.S. Patent No. 3,929.678, column 19, lines 18 to 35 (see here) (incorporated as a reference).

Zwitterionic surfactants can also be included in the detergent compositions herein.

These surfactants include derivatives of secondary and tertiary amines, heterocyclic secondary and and derivatives of tertiary amines, or quaternary ammonium, quaternary phosphonium or It can be broadly described as a derivative of a tertiary sulfonium compound or a tertiary sulfonium compound. Examples of zwitterionic surfactants With respect to U.S. Patent No. 3.9 to Rollin et al., issued December 30, 1975, No. 29,678, column 19, line 38 to column 22, line 48 (references here) (incorporated).

Amphoteric and zwitterionic surfactants generally contain one or more anionic surfactants. and/or nonionic surfactants.

enzyme Detergent enzymes e.g. protein-based stains, carbohydrate-based Removal of stains or triglyceride-based stains and prevention of fugitive dye migration It can be incorporated into detergent formulations for a variety of purposes, including detergent. The enzymes that should be mixed include rotease, amylase, lipase, cellulase, and peroxidase, and mixtures thereof. Other enzymes may be additionally added. that may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. may have.

However, their selection depends on several factors, such as pH activity and/or Supported by stability optima, thermal stability, stability against active detergents, builders, etc. will be arranged.

In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.

Suitable examples of proteases include Bacillus subtilis and Bacillus licheniformus (B, L It is a subtilisin obtained from a specific strain of B. ichinifor S. another Suitable proteases are those developed and registered by Novo Industries A/S. A pH of 8 to 12 sold under the trade name Esperase O Obtained from strains of Bacillus with maximum activity across the range. This enzyme and similar enzyme preparations are described in Novo UK Patent No. 1,243,784. has been done. Commercially available proteins suitable for removing protein-based stains As a chlorine-degrading enzyme, Novoφ Industries A/S (Denmark) Product names: Alcalase (ALCALASETM) and Savinase (SAVINA) SETM) and International Biosynthesis Maxatase (M Examples include those sold by AXATASETM).

The enzymes herein referred to as protease A and protease B are particularly useful in liquid detergent compositions. I'm interested in the category of proteolytic enzymes because of things. protease A and The manufacturing method is described in European Patent Application No. 130.756 published on January 9, 1985. (Incorporated here as a reference). Protease B is an amino acid Protease A has a leucine instead of tyrosine at position 217 in the sequence. They are different proteolytic enzymes. Protease B was filed on April 28, 1987. European Patent Application No. 87303761.8 (herein incorporated by reference) It is described in. In addition, the manufacturing method for protease B is published on January 9, 1985. Pott et al. 0 European Patent Application No. 130.756 (herein incorporated by reference) ) is disclosed.

Amylases include, for example, British Patent No. 1, previously incorporated herein by reference. , No. 296,839 (Novo). Examples include α-amylase obtained from special strains of bacteria.

Examples of starch degrading proteins include International Biosyn Ravidase (1?APIDAsETM) manufactured by Cetics Inc. ), and TERMAMYL” manufactured by Novo Industries. Can be mentioned.

Cellulases that can be used in the present invention include bacterial cellulases and fungal cellulases. Both can be mentioned. Preferably they have a pH optimum of 5 to 9.5. Will. A suitable cellulase is Humicola insolens. 1984 disclosing a fungal cellulase produced from U.S. Pat. No. 4,435,307 to Barbesgaard et al., issued March 6 (incorporated by reference). Also suitable cellulases are Patent No. 2.075.028, British Patent No. 2,095.275 and and DE-O5 No. 2,247.832.

An example of such a cellulase is Humicola insolens [Humicola grisea]. Pal thermoidea (Humicola grisea var, the rIIoidea)], especially Humicola strain DSM1800. cellulase, and fungi of Bacillus N belonging to the genus Aeromonas or Cellulases produced by cellulase 212-producing fungi, and marine molluscs [Dolabella Auricul] It is a cellulase extracted from the hepatopancreas of A.

Lipase enzymes suitable for use in detergents include British Patent No. 1.372,034. Pseudomonas stuzeri (P. seudomonas 5 tutzeri) AT CC19, 154, etc. Examples include those produced by microorganisms of the Pseudomonas group. suitable ripper The microorganism Pseudomonas fluorescens (Pseudomonas fluorescens) Antibody to lipase produced by S. fluorescens) IAM1057 Examples include those that show positive immunological cross-reactivity with This river is listed.

This lipase is commercially available from Amanor Pharmaceutical Co., Ltd. of Nagoya, Japan. Product name Lipase P "Amano (A-ano)" Available at J (hereinafter "Amano P") ). The Gagaru lipase of the present invention is a standard, well-known immune system related to ophthalmology. Diffusion method (Acta, Med, 5can,.

133.76-79 (1950)) with Amanor P antibody. It should show a differential response. These lipases and their immunization with Amanor P Methods for cross-reactivity are also described in US Pat. No. 4, Tom et al., issued November 17, 1987. , 707, 291 (incorporated herein as a reference). So Typical examples of these are Amanor P lipase ~ Lipase eX PSeudOIOnaS fragiFERM Pl, 339 (available under the product name Amanor B), Ripper Zeex Pseudomonas n1troreducens var.

1ipolyt, Ieu-F E RM P 1338 (Product name Amanor CE S), lipase ex Chromobactervlscosu+w , for example, commercially available from the Toyo-Jossey Company of Enkata, Japan. Chroobactervlscosum var, l1polyticu s NRRL B 3673; and U.S. Biochemical Corp. ration and further Chro from the Dutch Disoint Company mobacter viseosus lipase, and lipase exPseud It is of the order o*onas gladioles.

Peroxidase enzymes contain oxygen sources such as belcarbonate, belborate, Used in combination with versulfate, hydrogen peroxide, etc. They are used for "solution bleaching" i.e. dyes or pigments removed from the substrate during the cleaning operation are combined with other dyes or pigments in the cleaning solution. Used to prevent migration to the substrate. peroxidase enzyme technology known above, e.g. horseradish peroxidase, ligninase , and haloperoxidases, such as chloroperoxidase and bromo Examples include peroxidase. Peroxidase-containing detergent compositions include, for example: O, Car transferred to Novo Industries A/S announced on October 19, 1989. PCT International Application No. WO 891099813 (herein incorporated by reference) (incorporated).

A wide range of enzyme substances and methods of incorporation into synthetic detergent granules were also described by McCarty et al. U.S. Pat. No. 3,553,139, issued January 5, 1971 (references herein (incorporated as ). Enzymes are further described in the publication published on July 18, 1978. U.S. Patent No. 4,101°457 to Race et al. and March 26, 1985 No. 4,507,219 issued by Hughes, both herein incorporated by reference. (incorporated as a document). Enzymatic materials useful in liquid detergent formulations and Methods for incorporating such formulations are described in U.S. Pat. No. 261,868 (incorporated herein by reference).

The enzyme usually contains up to 5 mg active enzymatically per gram of composition, more typically about 0. ．． 0.5 mg to about 3 cm.

In the case of granular detergents, the enzymes are preferably coated with enzyme-inert additives or Lyllation to minimize dust formation and improve storage stability. accomplished this Techniques for doing so are well known in the art. In liquid formulations, the enzyme stabilization system Preferably used. Enzyme stabilization technology for aqueous detergent compositions is well known in the art. Ru. For example, one enzyme stabilization technique in aqueous solution is calcium acetate, calcium formate, Use of free calcium ions from sources such as calcium, calcium propionate, etc. include. Calcium ions can be combined with short chain carboxylates, preferably formates. Wear. For example, U.S. Pat. No. 4,318 to Retton et al., issued March 9, 1982; See specification No. 818 (incorporated herein by reference). Also, glycerol, sol It has also been proposed to use polyols such as Vitol.

Alkoxy-alcohols, dialkyl glycoethers, polyhydric alcohols and polyfunctional Aliphatic amines (e.g. jetanolamine, triethanolamine, diisopropylene) alkanolamines such as ropatoolamine), and boric acid or Alkali metal borates. Enzyme stabilization techniques were additionally described in Horn et al. No. 4,261,868, issued May 14, 1971 to Gedge et al. No. 3,600,319, issued Aug. 17, both incorporated herein by reference. (incorporated as a document) and Venegas' European patent publication published on October 29, 1986. Application Publication No. 0 199 405 Specification, Application No. 86200586.5 Specification Disclosed and illustrated. Stabilizers that are not boric acid and borates are preferred. stomach.

Enzyme stability systems are also described, for example, in U.S. Pat. No. 4,261°868, No. No. 600,319 and No. 3,519,570 .

Bleaching compounds - bleaching agents and bleach activators The detergent composition herein includes a bleaching agent, or a bleaching agent and one or more bleach activators. It may also contain a bleaching composition. When present, the bleaching compound typically present in an amount of about 1% to about 20% of the detergent composition, more typically about 1% to about 20%. There will be. Generally, bleaching compounds are optionally used in non-liquid formulations, e.g. granular detergents. It is an ingredient.

If present, the amount of bleach activator typically ranges from about 0.1% of the bleach composition to about 60%, more typically about 0.5% to about 40%.

The bleach used here is suitable for fabric cleaning, hard surface cleaning, or and of bleaching agents useful in detergent compositions for other cleaning purposes that are or become known. It can be either. These include oxygen bleach as well as other bleaches. can be lost. For cleaning conditions below about 50"C, especially below about 40"C, this composition borates or detergents that can generate borates in situ under storage or cleaning conditions. It is preferable not to contain any substances that produce borate (ie, borate-forming substances). Thus, this Under such conditions, non-borate non-borate producing bleaches are preferably used. . Preferably, detergents to be used at these temperatures are free of borates and borate-forming Virtually free of substances. “Borates and borate-forming substances” used here "Quality free" means that the composition contains approximately 2 weight borate-containing substances and borate-forming substances. % or less, preferably 1% by weight or less, more preferably 0%. There will be.

One category of bleaches that can be used is belucarboxylic acid bleaches and their salts. include. A suitable example of this type of bleach is Monoperoxyphthalate Magnesium. Siium hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino- Mention may be made of 4-oxoperoxybutyric acid and diperoxide dodecanedioic acid.

Gagaru bleach is disclosed in Hartman's U.S. Patent No. 4,4, issued November 20, 1984. No. 83,781, U.S. patent application Ser. No. 83,781 filed June 3, 1985. 740,446, published on February 20, 1985, by Banks et al. Application No. 0.133,354, issued on November 11, 1983 by Chung et al. No. 4,412°934, all of which are incorporated herein by reference. (incorporated). Highly preferred bleaching agents include Buns et al. U.S. Pat. No. 4,634,551, issued January 6, 1987 (referenced herein) 6-nonyl-amino-6-oxoperoxycabronic acid described in Can be mentioned.

Another category of bleaches that can be used includes halogen bleaches. Hypohara Examples of acid bleaches include, for example, trichloroisocyanuric acid and dichloroisocyanuric acid. Sodium isocyanurate and potassium dichloroisocyanurate and N-chloro and N-bromoalkanesulfonamides. Such substances are usually , 0.5-10%, preferably 1-5% by weight of the finished product.

Peroxygen bleaches other than perboron compounds can also be used.

Suitable peroxygen bleaching compounds include sodium carbonate peroxide, birophosphoric acid Sodium peroxide, urea peroxide, and sodium peroxide are listed. can be lost.

The peroxygen bleach is preferably combined with a bleach activator, which means that the bleach activator In situ generation (i.e. during the cleaning process) in aqueous solution of peroxyacids corresponding to bring.

Preferred bleach activators for inclusion in the compositions of the present invention have the general formula (wherein R is an alkyl group having about 1 to about 18 carbon atoms, and a carbonyl carbon The longest linear alkyl chain extending from and including the carbonyl carbon is about 6 to about 10 carbon atoms, L is a leaving group, and the conjugate acid has a pK of about 4 to about 13. do) has. These bleach activators are listed in the US paper published by Mao et al. No. 4,915,854 (incorporated herein by reference) and U.S. Pat. As described in the patent specification No. 4゜412.934 (previously incorporated herein as a reference document) ing.

Bleaching agents other than oxygen bleach are also known in the art and available herein. specific interest One type of non-oxygen bleach that is flavored is a light-activated bleach, such as a sulfonate bleach. zinc phthalocyanine and/or aluminum phthalocyanine. Ru. These substances can be deposited on the substrate during the cleaning process. dry in the sun Zinc sulfonyl heptaide upon irradiation with light in the presence of oxygen by hanging the cloth for The phthalocyanine is activated and the substrate is therefore bleached. Preferred zinc lid Russianine and photoactivated bleaching methods are described in Holcombe et al., published July 5, 1977. As described in U.S. Pat. No. 4,033,718 (incorporated herein by reference) It is. Typically, the detergent composition will contain about 0.0 sulfonated zinc phthalocyanine. It will contain from 25 to about 1.25% by weight.

Polymer stain release agent Any polymeric soil release agent known to those skilled in the art can be used in the practice of this invention. Takamin The soil release agent makes the surface of hydrophobic fibers such as polyester and nylon hydrophilic. Hydrophilic segments for adhesion onto hydrophobic fibers and washing and rinsing cycles remains adhered throughout the completion of the module, thus serving as a foil for the hydrophilic segment. It is characterized by having both a hydrophobic segment and a hydrophobic segment. this This means that the stains that form after treatment with a soil release agent are more easily cleaned up by subsequent cleaning methods. can be made possible.

Add polymeric soil release agents to any of the detergent compositions herein, especially for cleaning grease from hydrophobic surfaces. Use in compositions used in laundry or other applications where oil/grease removal is required. may be beneficial in detergent compositions that also contain anionic surfactants. The presence of polyhydroxy fatty acid amides indicates that the more commonly used types of polymers Many performances of soil release agents can be enhanced. Anionic surfactants are hydrophobic It interferes with the ability of the soil release agent to adhere and adhere to the surface. These polymers Soil release agents are non-ionic hydrophilic segments that are anionic surfactant-interactive or have a hydrophobic segment.

Improved polymeric soil release agent performance due to use of polyhydroxy fatty acid amide The composition here that can be obtained is anionic surfactant system, anionic surfactant Interactive soil release agents and soil release agent enhancing amounts of polyhydroxy fatty acid amides ( PFA) [(I) The soil release agent and anion interface of the detergent composition. Anionic surfactant interactions with the active agent system (A) in the absence of other detergent components "Control" measuring the adhesion of soil release agent (SR,A) of detergent composition in aqueous solution of ” run and (B) the same type and amount of anionic surfactant utilized in the detergent composition. The surfactant system is water-soluble with SRA at the same weight ratio of SRA to anionic surfactant system in the detergent composition. Hydrophobicity in aqueous solution between rSRA/Anionic surfactant test By comparing the amount of soil release agent (SRA) deposited onto fibers (e.g. polyester). It can be shown that the reduced adhesion of (B) compared to (A) indicates an anionic surfactant interaction: and (II) the detergent composition is a soil release agent. Whether or not it contains an increasing amount of polyhydroxy fatty acid amide depends on the SRA/anime of (B). SRA adhesion of on-surfactant test and (C) port of the same type and amount of detergent composition. lyhydroxy fatty acid amide corresponding to the SRA/anionic surfactant test run described above. rSRA/anionic surfactant combined with soil release agent and anionic surfactant system This can be determined by comparing the soil release agent deposition during the "PFA test run" and Thus, the improvement in soil release agent in test run (C) compared to test run (B). The fouling deposits indicate the presence of soil release agent-enhancing amounts of polyhydroxy fatty acid amide. vinegar〕. For our purposes here, the test here is based on the critical micelle concentration of anionic surfactants (C anionic surfactant concentration in the aqueous solution higher than MC), preferably about 100 pp Anionic surfactant concentrations higher than 11 should be used. Polymer stain release agent concentration The concentration should be at least 1'5 ppm. Polyester fabric sample should be used as a source of hydrophobic fibers. Identical swatches were used for each test run. Immerse and stir in an aqueous solution at 35°C for 12 minutes, then remove and analyze. polymer stain The soil release agent coverage is determined by radiolabeling the soil release agent prior to processing according to techniques known in the art. After identifying the amount, it can be measured by radiochemical analysis.

As an alternative to the radiochemical analysis method, soil release agent deposition is performed according to techniques well known in the art. , the test run (i.e. test run) is determined by measuring the ultraviolet (UV) absorbance of the test solution. A1B and C) or can be measured. In the test solution after removal of hydrophobic fiber material The decreased UV absorbance of corresponds to increased SRA deposition. by those skilled in the art As will be appreciated, UV analysis may be of any type or type that produces excessive UV absorbance interference. and amounts of substances, such as large amounts of surfactants with aromatic groups (e.g. alkyl Benzene sulfonate, etc.) should not be used in test solutions that contain gold.

Thus, as mentioned above, the polyhydroxy fatty acid amide of the "stain release agent enhancing amount" The amount of such surfactant, or or enhanced grease/oil cleaning performance during subsequent cleaning operations. It means the amount that can be obtained in the case of fabrics washed with this detergent composition.

The amount of polyhydroxy fatty acid amide required to enhance adhesion is selected The anionic surfactant, the amount of anionic surfactant, the particular soil release agent selected, and the specific polyhydroxy fatty acid amide. Generally, group The composition contains from about 0.01 to about 10% by weight of a polymeric soil release agent, typically from about 0.1 to about 5% by weight and about 4 to about 50% by weight anionic surfactant, more typically about 5 to about 50% by weight. It will contain about 30% by weight. Although not necessarily intended to be limiting, such compositions generally contains at least 1% by weight, preferably less than 1% by weight of polyhydroxy fatty acid amide. It should contain at least about 3% by weight.

Performance enhanced by polyhydroxy fatty acid amides in the presence of anionic surfactants The polymeric soil release agents used include (a) essentially (i) a degree of polymerization of at least 2; polyoxyethylene segment or (11) oxypropylene or polymerization polyoxypropylene segments with degrees of 2 to 10 (each by ether linkage) Hydrophilic segments are oxypropylene unless attached at the end to an adjacent moiety. ) or (fil) oxyethylene and 1 to about 30 oxyethylenes. A mixture of oxyalkylene units consisting of propylene units (the mixture is a hydrophilic component) However, when the stain release agent is deposited on the surface of ordinary polyester synthetic fibers, hydrophilicity large enough to increase the hydrophilicity of the synthetic fiber surface. the hydrophilic segment preferably contains a sufficient amount of oxyethylene units; At least 25% tyrene units, more preferably especially about 20 to 30 oxypro In the case of such components having pyrene units, at least about 50 oxyethylene units %); or (b) (i) one or more nonionic hydrophilic components consisting of xyalkylene terephthalate segment (hydrophobic component is oxyethylene terephthalate segment) If tallate is also included, oxyethylene terephthalate versus C3 oxyalkylene The ratio of terephthalate units is about 2:1 or less), (11) C4 ~C6 alkylene or oxyC4-C6 alkylene segments or their (11i) a poly(vinyl ester) segment having a degree of polymerization of at least 2; (iv) CL-C4 alkyl ester, preferably poly(vinyl acetate), or (iv) CL-C4 alkyl ether ether or C4 hydroxyalkyl ether substituents or mixtures thereof (previously The substituent is 01-C4 alkyl ether or C4 hydroxyalkyl ether present in the form of cellulose derivatives or mixtures thereof and such cellulose derivatives; The body is amphipathic, thereby containing sufficient amounts of C-C4 alkyl ether and /or ordinary polyester having C4 hydroxyalkyl ether units Adheres to the surface of synthetic fibers and retains a sufficient amount of hydroxyl, once applied When attached to the surface of synthetic fibers, it increases the hydrophilicity of the fiber surface. Soil release agents having a hydrophobic component or a combination of (a) and (b) are mentioned. It will be done.

Typically, levels higher than 200% can be used; The ethylene segment has a degree of polymerization of 2 to about 200, preferably 3 to about 150, more preferably or 6 to about 100. Preferred oxyC4-C6 alkylene hydrophobic The gender segment includes, without limitation, Bosselin, Rini, January 26, 1988. No. 4,721,580 (incorporated herein by reference). as shown MO5(CH2)nOCH2CH20- (where M is sodium and n is 4 end-capping of polymeric soil release agents such as (an integer between 6 and 6).

Polymeric soil release agents useful in the present invention include hydroxyether cellulose-based polymers. Cellulose derivatives such as ethylene terephthalate or propylene terephthalate Phthalate and polyethylene oxide terephthalate or polypropylene oxy Examples include copolymer blocks with doterephthalate.

Cellulose-based derivatives that function as soil release agents are commercially available; For example, cellulose hydroxyesters such as Methocel® (Dow) -tel is mentioned.

Cellulosic soil release agents for use herein include methyl cellulose, Chylcellulose, Hydroxypropylmethylcellulose, Hydroxybutylmethythyl C-C alkyl and C4 hydroxyalkylcelluloses such as cellulose Also included are those selected from the group consisting of: Various types of cells useful as soil release polymers Lulose derivatives are described in U.S. Pat. No. 000,093 (incorporated herein by reference).

Soil release agents characterized by poly(vinyl ester) hydrophobic segments and For example, grafting of poly(vinyl ester), e.g. C-06 vinyl ester. Copolymers, preferably polyalkylene oxides such as polyethylene oxide backbones Examples include poly(vinyl acetate) grafted onto the main chain. Such substances are technically European patent application box 0 known and published on April 22, 1987 by Hood et al. It is described in the specification of No. 219048. Suitable commercial soil release agents of this kind and Soka IanTM type substances, such as BASF ( One example is Tsukaran TMHP-22 available from West Germany.

One type of preferred soil release agent is ethylene terephthalate and polyethylene olefin. Copolymer with random block with oxide (P　E　O) terephthalate be. More specifically, these polymers contain ethylene terephthalate units versus PEO Ethylene terephthalate with a molar ratio of terephthalate units of about 25 nia 5 to about 35.65 consisting of a repeating unit of rate and PEO terephthalate (the PEO terephthalate The unit contains polyethylene oxide having a molecular weight of about 300 to about 2000. ).

The molecular weight of the polymeric soil release agent ranges from about 25,000 to about 55,000. be. No. 3,959,230 to Hayes, issued May 25, 1976. See the detailed booklet (incorporated here as a reference). 197 disclosing similar copolymers U.S. Patent No. 3,893,929 to Vasdar, issued July 8, See also (incorporated as a document).

Another preferred polymeric soil release agent is polyoxygenate having an average molecular weight of 300 to 5,000. Polyoxyethylene terephthalate units derived from ethylene glycol 90-8 Ethylene containing 10-15% by weight of ethylene terephthalate units together with 0% by weight is a polyester with repeating units of lenterephthalate units, and is a polymer Ethylene terephthalate units versus polyoxyethylene terephthalate units in the compound The molar ratio between the two positions is from 2:1 to 6:1.

An example of this polymer is the commercially available material Zelcon® 5126. (manufactured by DuPont) and Millise (Milease R) T (manufactured by ICI) Can be mentioned. These polymers and their manufacturing methods were published in Gosselink in October 1987. No. 4,702,857, issued May 27, 2013 (incorporation).

Another preferred polymeric soil release agent is terephthaloyl and oxyalkylene oxide. from the oligomeric ester backbone of the repeat unit and the terminal portion covalently bonded to the backbone. is the sulfonated product of a substantially linear ester oligomer (the soil release The agents are allyl alcohol ethoxylate, dimethyl terephthalate, and 1.2 - derived from propylene diol; after sulfonation, the terminal portion of each oligomer is on average having a total of about 1 to about 4 sulfonate groups). These stain release agents are Published November 6, 1990 in J. J. Siebel and E. P. Gosselinck. U.S. Pat. No. 4,968.451, filed January 29, 1990. As detailed in patent application box 07/474.709 (incorporated herein by reference). It is.

Other suitable polymeric soil release agents include Gosselinck et al., December 8, 1987; Ethyl- or methyl-blocked 1 of issued U.S. Pat. No. 4,711°730 ．． 2-Propylene terephthalate-polyoxyethylene terephthalate polyester No. 4,721. issued January 26, 1988 to Tell, Gosselinck et al. ．． No. 580, the anionic end-capped oligomer ester (anionic end-capped is Made from sulfo-polyethoxy groups derived from polyethylene glycol (PEG) ), formula X-(OCH2CH2)n-(wherein, n is 12 to about 43, and X is C""' C4 alkyl or preferably methyl) with polyethoxy end capping U.S. Patent No. 4,702.857 issued October 27, 1987 to Gosselink block polyester oligomer compounds (all of these patents are hereby incorporated by reference). (Incorporated as a reference here).

Additional polymeric fouling release agents include anionic, especially sulfaroyl end-capped telecontaminants. Published October 31, 1989 to Martonato et al. disclosing phthalate esters. No. 4,877,896, incorporated herein by reference. ) stain release agents. Terephthalate esters are asymmetrically substituted oxy- Contains 1,1-fulkyleneoxy units. U.S. Patent No. 4.877゜896 The stain-releasing polymer of the booklet contains a polyoxyethylene hydrophilic component or (b) (i). ) within the hydrophobic components of 03 oxyalkylene terephthalate (propylene terephthalate) phthalate) repeating unit.

Special effects from the formulation of polyhydroxy fatty acid amide here in the presence of anionic surfactants. Those who benefit from high It is a molecular stain release agent.

If utilized, the soil release agent generally comprises from about 0.01 to about 10.0% by weight, typically about 0.1 to about 5%, preferably about 0.2 to about 3% ．． It will account for 0% by weight.

chelating agent The detergent compositions of the present invention also optionally contain one or more iron/manganese chelating agents. It may also be contained as a builder auxiliary substance. Such chelating agents are described below. Aminocarboxylate, aminophosphonate, polyfunctionally substituted aromatic as defined Can be selected from the group consisting of chelating agents and mixtures thereof. controlled by theory Without trying to limit the benefits of these substances, it is possible that the benefits of these substances are due, in part, to the formation of soluble chelates. Therefore, it is believed that this is due to its exceptional ability to remove iron and manganese ions from the cleaning solution. It will be done.

Aminocarboxylates useful as optional chelating agents in the compositions of the invention include 1 or more (preferably at least 2) units of substructure (5ubst ructure) e) H2 [Formula, where M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. (e.g., ethanolamine), and X is 1 to about 3, preferably 1. It is possible to have. Preferably, these aminocarboxylates are about 6 Contains no alkyl or alkenyl groups having more than 1 carbon atoms. use Possible amine carboxylates include ethylenediaminetetraacetate, N-Hydroxyethylethylenediamine triacetate, nitrilotriacetate , ethylenediaminetetrapropionate, triethylenetetraamine hexa Acetate, diethylenetriamine pentaacetate and ethanol diglycyl salts, their alkali metal salts, ammonium salts, substituted ammonium salts and and mixtures thereof.

Aminophosphonates also allow at least a small amount of total phosphorus in detergent compositions. It is suitable for use as a chelating agent in the compositions of the present invention. 1 or more (preferably at least 2) unit substructures (wherein M is hydrogen, an alkali metal, ammonium or substituted ammonium, and X is 1 to about 3, preferably 1. ) Compounds having ethylenediaminetetrakis ( methylene phosphonate), nitrilotris (methylene phosphonate) and Ethylene triamine pentakis (methylene phosphonate) is mentioned. preferred Preferably, these aminophosphonates are alkaline phosphonates having more than about 6 carbon atoms. Contains no kyl or alkenyl groups. Alkylene groups are shared by substructures can.

Polyfunctionally substituted aromatic chelators are also useful in the present compositions. these substances is the general formula (wherein at least one R is -5O3H or -COOH) or their soluble salts and mixtures thereof. Wear. U.S. Patent No. 3,812.044 issued May 21, 1974 to Connor et al. The specification (incorporated herein by reference) describes polyfunctionally substituted aromatic chelation/metallic On sequestering agents are disclosed. A preferred compound of this type in acid form is 1,2-dihydro Dihydroxydisulfobenzene such as Roxy-3゜5-disulfobenzene . Alkaline detergent compositions combine these substances with alkali metal salts, ammonium salts or or in the form of substituted ammonium salts (e.g. mono- or triethanolamine salts) It can be contained in

If utilized, these chelating agents generally make up about 0% of the detergent compositions of the present invention. ．． It will account for 1 to about 10% by weight. More preferably, the chelating agent from about 0.1 to about 3.0% by weight of the composition.

Clay stain removal/redeposition prevention agent The compositions of the invention optionally have clay stain removal and anti-redeposition properties. Water-soluble ethoxylated amines may also be included. Granular detergent compositions containing these compounds The product typically contains from about 0.01 to about 10% by weight of a water-soluble ethoxylated amine. Ru. Liquid detergent compositions typically contain from about 0.01 to about 5 water-soluble ethoxylated amines. % by weight. These compounds are preferably from the group consisting of: To be elected.

Ethoxylated monoamine with X　X　X or Ethoxylated diamine with Ethoxylated polyamine with (4) General formula and (5) mixtures thereof [wherein A1 teeth or 10-; R is H or C1-C4 alkyl or hydroxyalkyl R1 is 02-C12 alkylene, hydroxyalkylene, alkenyl Ren, arylene or alkarylene, or 2 to about 20 oxyalkylene is a C2-C3 oxyalkylene moiety having an O-N bond. not: each R2 is C-C4 or hydroxyalkyl, moiety -L-X, The two R2 together form the moiety -(CH), r -A2- (CH)- (wherein A2 is 10- or S -CH2-1r forms 1 or 2, S forms 1 or 2, r+s forms 3 or 4) ; X is a nonionic group, an anionic group or a mixture thereof; R3 is a substitution site Substituted 03-C12 alkyl group, hydroxyalkylene group, alkenylene having group, aryl group, or alkaryl group; R4 is C-C alkylene, hydro Roxyalki t12 Ren, alkenylene, arylene or alkarylene, or from 2 to about 20 A C2-C3 oxyalkylene moiety having oxyalkylene units, with the proviso that 0 -0 bond or O-N bond is not formed; L is polyoxyalkylene moiety -[(RO) (CH2CH20). ]−(In the formula, ■ R is 03-C4 alkylene or hydroxyalkylene, m and n are minutes -(CHCH20). - is at least about 50 times the polyoxyalkylene moiety; %); m is from 0 to about 4 and n is at least about 12; m is from 0 to about 3, and n is R1 is C2-C3 alkylene, hydroxyalkylene, When it is alkylene or alkenylene, at least about 6, R1 is 02 to C3 When it is other than alkylene, hydroxyalkylene or alkenylene, less and in the case of the polyamines and amine polymers, m is from 0 to about 1. 0, n is at least about 3; p is 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; W is 1 or 0; is 0; x+y+z is at least 2; 3'+Z is at least 2 ] The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylene pentamine. It is. Exemplary ethoxylated amines include Pandelmir, published July 1, 1986; No. 4,597,898 (incorporated herein by reference) Are listed. Another group of preferred clay stain removers/anti-redeposition agents is the 1984 O and Gosselink European Patent Application No. 111°965 published on June 27th It is a cationic compound disclosed in the specification (herein incorporated by reference). can be used Other clay stain removal/redeposition prevention agents include Gosse, published on June 27, 1984. Ethoxylated amine polymerization disclosed in Link European Patent Application No. 111,984 Gosselink European Patent Application No. 112.592 published on July 4, 1984 The zwitterpolymers disclosed in the specification; and Conner, U.S.A., published October 22, 1985. Examples include amine oxides disclosed in Patent No. 4.548.744 (which (all of which are incorporated herein by reference).

Other clay stain removers and/or anti-redeposition agents known in the art may also be incorporated into the compositions herein. Available at Another type of preferred anti-redeposition agent is carboxymethyl Examples include lulose (CMC) substances. These materials are well known in the art.

Polymer dispersant Polymeric dispersants are advantageously utilized in the compositions herein. These substances Si and magnesium can aid hardness control. Other known in the art also used However, suitable polymeric dispersants include polymeric polycarboxylates and polymers. Examples include lyethylene glycol.

Polycarboxylate materials that can be used as polymeric dispersants have the general formula (In the formula, X1Y and Z are hydrogen, methyl, carboxy, carboxymethyl, selected from the group consisting of hydroxy and hydroxymethyl; salt-forming cations and and n is about 30 to about 400) These polymers or copolymers contain at least about 60% by weight of segments having It is a polymer. Preferably, X is hydrogen or hydroxy and Y is hydrogen or carboxylic. xy, Z is hydrogen, M is hydrogen, alkali metal, ammonia or substituted ammonium It is.

High molecular weight polycarboxylate materials of this type are made of suitable unsaturated monomers (preferably It can be produced by polymerizing or copolymerizing (acid form). Suitable polymer polymer Unsaturated monomeric acids that can be polymerized to form boxylates include acrylic acid , maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid , mesaconic acid, citraconic acid and methylenemalonic acid.

Non-carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc. The monomer segment containing It is preferred that such segments constitute no more than about 40% by weight. It is.

A particularly suitable polymeric polycarboxylate can be derived from acrylic acid. here Such acrylic acid-based polymers that are useful include polymerized acrylic acid It is a water-soluble salt. The average molecular weight of such polymers in acid form is approximately 2.000 to 10.0 00, more preferably about 4,000 to 7,000. Most preferably about 4,000 ~5,000. Examples of such water-soluble salts of acrylic acid polymers include alkali metal salts, ammonium salts and substituted ammonium salts. this species soluble polymers are known substances. This kind of polyacrylate is used in detergent compositions For example, Diehl, U.S. Pat. No. 3, issued March 7, 1967, , 308.067. Reference this patent here Transfer.

Acrylic acid/maleic acid based copolymers are also preferred components of dispersants. You may also use it. Such substances include copolymers of acrylic acid and maleic acid. Examples include water-soluble salts of The average molecular weight of such copolymers in acid form is preferably about 2.000 to 100,000, more preferably about 5,000 to 75,000, most Also preferably about 7,000 to 65,000. Acrylic in such copolymers The ratio of malenate segments to malenate segments is generally from about 30; 1 to about 1 =1, more preferably about 10:] to about 2=1. Such acrylic acid/ma Examples of water-soluble salts of leic acid copolymer include alkali metal salts and ammonium salts. salts and substituted ammonium salts. This type of soluble acrylate/male The ate copolymer is disclosed in European Patent Application No. 66915 published on December 15, 1982. It is a known substance as described in the specification (this publication is incorporated herein by reference).

Another polymeric material that can be included is polyethylene glycol (PEG). P.E. G can exhibit dispersant performance as well as act as a clay stain remover/anti-redeposition agent. . Typical molecular weight ranges for these purposes are from about 500 to about 100,000, preferably preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about No known optical brighteners or other brighteners or whitening agents are included in the detergent compositions herein. Can be mixed.

The selection of brighteners for use in detergent compositions depends on the type of detergent, the amount present in the detergent composition. The properties of other components, the temperature of the cleaning water, the degree of agitation, the ratio of the object to be cleaned to the size of the tub, etc. It will depend on a number of factors.

Brightener selection also depends on the type of material to be cleaned, e.g. cotton, synthetic, etc. Exists. Most laundry detergent products are used to clean a variety of fabrics. So the detergent composition should contain a mixture of brighteners that will be effective on a variety of fabrics. be. Of course, the individual components of such brightener mixtures need to be compatible. Ru.

Commercially available optical brighteners that may be useful in the present invention can be divided into subgroups and Examples include, but are not limited to, stilbenes, pyrazolines, coumarins, and carboxylic acids. , methinecyanine, dibenzotifen-5,5-dioxide, azole, 5-membered ring and derivatives of six-membered heterocyclic compounds, and other miscellaneous drugs. mosquito Examples of such brighteners include "Production and Application of Optical Brighteners", J.M., Deradnik, Ni. Published by John Wiley & Sons, New York (1,982) (disclosure thereof) (incorporated herein by reference).

Stilbene derivatives that may be useful in the present invention include, but are not limited to: , bis(triazinyl)amino-stilbene derivative bisacyl of nistilbene Amino derivatives; triazole derivatives of stilbene oxadiazole of stilbene oxazole derivatives of stilbenes; and styryl derivatives of stilbenes My body is raised.

Derivatives of bis(triazinyl)aminostilbenes that may be useful in the present invention The conductor is made from 4,4'-diamine-stilbene-2,2'-disulfonic acid. You may.

Coumarin derivatives that may be useful in the present invention include, but are not necessarily limited to: Examples include derivatives substituted at the 3-position, the 7-position, and the 3- and 7-positions.

Carboxylic acid derivatives that may be useful in the present invention include, but are not limited to: , fumaric acid derivative; benzoic acid a-conductor; Body: naphthalene dicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives can be mentioned.

Cinnamic acid derivatives that may be useful in the present invention can be further subdivided into several groups. , these groups are not necessarily limited to, but are described on page 77 of Deradnik's literature. Cinnamic acid derivatives, styryl azole, styryl benzofuran, styryl as shown Ruoxadiazole, styryl triazole, and styryl polyphenyl are mentioned. can be lost.

Styryl azole is a styryl azole as disclosed on page 78 of the Deradnik literature. Further down to benzoxazole, styryl imidazole and styryl thiazole. Can be classified by rank. These three aforementioned subclasses subclassify styrylazole. It is understood that this may not necessarily reflect an exhaustive list of subgroups that may be used. It will be.

Another class of optical brighteners that may be useful in the present invention - Willie End Sun ・Incorporated, 1962) (the disclosure of which is incorporated herein by reference) of dibenzothiophene-5,5-dioxide disclosed on pages 741 to 749 of derivative and 3,7-riamitudibenzothiophene-2,8-disulfonic acid Examples include 5,5 dioxide.

Another class of optical brighteners that may be useful in the present invention are five-membered heterocyclic compounds. It is an azole that is a derivative of These are further added to monoazoles and diazoles. Can be placed in a lower range. Examples of monoazoles and diazoles are the Kirk-Othmer Disclosed in the literature.

Another class of brighteners that may be useful in the present invention is described in the Kirk-Othmer reference. It is a derivative of the disclosed six-membered heterocyclic compound. Examples of such compounds include pyra Whitening agents derived from ginsine and derivatives derived from 4-aminonaphthalamide are mentioned. can be lost.

In addition to the brighteners already mentioned, miscellaneous agents may also be useful as brighteners. mosquito Examples of such miscellaneous drugs are disclosed on pages 93-95 of the Deradnik article. and 1-hydroxy-3,6,8-pyrene trisulfonic acid: 2,4-dimethyl Toxy-1,3,5-)riazin-6-yl-pyrene; 4,5-di-phenyl and pyrazoline-quinoline derivatives.

Other specific examples of optical brighteners that may be useful in the present invention include U.S. Pat. No. 4,790.856 issued to Wixon on September 3 (Incorporated here as 7 bibliography). These whitening agents include Examples include the PhorvhiteTM family of brighteners from Rona. . Other brighteners disclosed in this document include Chinova, available from Chill Geigy. Tinopal U N P A, Tinopal CBS and Nanopal Le 58M. Arctiti available from Hilton-Davis located in Italy. Arctic White CC and Arctic White Ito CWD, 2-(4-styrylphenyl)-2H-naphthol C1,2- d)) Riazole, 4,4'-bis-(1,2,3-triazol-2-yl )-stilbene; 4,4'-bis(styryl)bisphenyl; and y-amino Examples include coumarin. Specific examples of these brighteners include 4-methyl-7-di Nithylaminocoumarin; 1,2-bis(benzimidazol-2-yl)-ethyl Ren; 1,3-diphenylfraziline; 2,5-bis(benzoxazole-2 -yl)-thiophene; 2-styryl-naphtho-(1,2-d)-oxazole ; and 2-(stilben-4-yl)-2H-naphtho[1°2-d) thoria Examples include sol.

Other optical brighteners that may be useful in the present invention include Hamilton, 1972; U.S. Pat. No. 3,646.015, issued February 29, 2008, the disclosure of which (incorporated as a reference).

Foam suppressant Known or becoming known compounds for reducing or inhibiting foam formation are included in the present invention. Can be incorporated into compositions. This polyhydroxy fatty acid amide surfactant is used in detergent composition. The inclusion of such substances (hereinafter referred to as "foam suppressants") is desirable because they can increase the foam stability of the product. There is something interesting. Foam control is achieved by using a polyhydroxy fatty acid amide surfactant in the detergent composition. is of particular importance when including comparatively high foaming surfactants in combination with Sometimes. Foam control is especially important for compositions intended for use in front-load automatic washing machines. desirable. These washing machines typically have a horizontal axis and rotational movement around this axis. Characterized by having a drum for containing washing/washing water having a purpose It will be done. This type of agitation produces high foam formation and therefore reduced cleaning performance. I sometimes cheat. The use of foam suppressants is recommended under hot water washing conditions and high surfactant concentration conditions. It may also have a particular significance below.

A variety of materials may be used as suds suppressants in the compositions herein. Foam suppressants can be determined by those skilled in the art. It is well known. They are generally, for example, Kirk-Othmer Ency clopedia of Chemical Technology, 3rd edition, 3rd edition Volume 7, pp. 430-447 (John Wiley & Sons, Inc.) Hollated, 1979). One category of specific interest Foam suppressants include monocarboxylic fatty acids and soluble salts thereof. these The substance is disclosed in U.S. Patent No. 2 issued September 27, 1960 to Uniin St. John. , No. 954,347 (which patent is incorporated herein by reference). There is. Monocarboxylic fatty acids and their salts for use as foam suppressants are typically Typical hydrocarpyls having from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Has a chain. Suitable salts include alkali metal salts such as sodium salts, potassium salts, ammonium salts, and lithium salts, and ammonium salts and alkanol ammonium salts. Examples include um salt. These materials are a preferred category of suds suppressors in detergent compositions. It is a drug.

The detergent composition may also contain non-surfactant suds suppressants. These include: For example, high molecular weight hydrocarbons, e.g. paraffins, fatty acid esters (e.g. fats) fatty acid triglycerides), fatty acid esters of -hydric alcohols, aliphatic C18~”4 0 ketones (eg, stearone) and the like. Other foam suppressants include N- Alkylated aminotriazines, e.g. primary or secondary aminotriazines having 1 to 24 carbon atoms. Trialkylmethane formed as a product of 2 or 3 moles of amine and cyanuric chloride From lamin to hexaalkyl melamine or dialkyl diamine chlortri From Azine to Tetraalkyldiamine Chlortriazine, Propylene Oxide , and monostearyl phosphates, e.g. monostearyl alcohol phosphorus acid esters and monostearyl dialkali metal (e.g. Na5LiSK) Sphates and phosphoric acid esters may be mentioned. paraffin, haloparaffin Which hydrocarbons are available in liquid form. Liquid hydrocarbons are liquids at room temperature and atmospheric pressure. It has a pour point of about -40°C to about 5°C and a minimum boiling point of about 110°C or more (large atmospheric pressure). Also waxy hydrocarbons, preferably with a melting point below about 100°C It is known to utilize a device having a Hydrocarbons are preferred in detergent compositions Comprises the category foam suppressants. Hydrocarbon foam suppressants include, for example, Gandolho et al. U.S. Pat. No. 4,265.779, issued May 5, 981 (references herein (incorporated as a dedication). As a hydrocarbon, the number of carbon atoms is thus approximately 12 to Approximately 70 aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons are listed. can be lost. The term “paraffin” used in this foam suppressor discussion refers to true paraffin. and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors consists of silicone suds suppressants.

This category includes polyorganosiloxane oils such as polydimethylsiloxane. , dispersions or emulsions of polyorganosiloxane oils or resins, and polyorganosiloxane oils or resins; Combination of xane oil and silica particles (polyorganosiloxane is chemisorbed onto silica) Examples include the use of Silicone foam suppressants are well known in the art. See, for example, U.S. Patent No. 4,265. issued May 5, 1981 to Gandolho et al. No. 779 and the European patent publication published February 7, 1990 by M.S. Starch. Patent Application No. 89307851.9 (both incorporated herein by reference) has been disclosed.

Other silicone suds suppressors can be used to water the composition and small amounts of polydimethylsiloxane fluids. U.S. Patent No. 3 for a method for defoaming an aqueous solution by incorporating it into a solution , 455.839.

Mixtures of silicone and silanized silica can be used, for example, in patent application DO8 No. 2, No. 124.526. Silicone in granular detergent compositions Defoamers and antifoam agents are described in U.S. Pat. No. 3,933,672 to Paltrotsuta et al. No. 4,652 to Panginski et al., issued March 24, 1987. ．． No. 392.

Exemplary silicone-based foam suppressants for use herein are essentially (i) Polydimethylsiloxane having a viscosity of about 20 cs to about 1500 cs at 25°C. sun fluid; (it) (i) from about 5 to about 50 parts per 100 parts by weight of (CH) SiO units; (CH) SioOL with a ratio of 2 units of Sio from about 0.6:1 to about 1.2:1 siloxane resin consisting of /2 units and S iO2; and (ii+) (i) 10 from about 1 to about 20 parts solid silica gel per 0 parts by weight It is an antifoam agent with a foam suppressing amount consisting of:

In case of detergent compositions that should be used in automatic washing machines, the foam will overflow the washing machine It should not be formed to the extent that it does. Foam suppressants, when utilized, are preferably “ It exists in the amount of foam suppression. “Suds control” is the amount that the formular of the composition uses in an automatic washing machine. This foam control agent will control the foam sufficiently to produce a low-foaming laundry detergent. This means that the amount of agent can be selected. The degree of foam control depends on the detergent surfactant selected. It will change accordingly. For example, in the case of high foaming surfactants, relatively large amounts foam control agents are used to achieve the desired foam control than are the case with low-foaming surfactants. It will be done. Generally, a sufficient amount of suds suppressor is present during the wash cycle of an automatic washing machine (i.e. The foam that forms during agitation of detergent in an aqueous solution under washing temperature and concentration conditions during washing Preferably, the foam does not exceed about 75% of the void volume of the storage drum of the machine; (void The volume is determined as the difference between the total volume of the storage drum and the volume of water plus laundry ).

The compositions herein will generally contain from 0% to about 5% suds suppressor. Used as a foam suppressant When used, monocarboxylic fatty acids and their salts are typically added to detergent compositions. It may be present in an amount up to about 5% by weight of the product. Preferably fatty monocarboxylic A rate of 0.5% to about 3% suds suppressor is utilized. Large amounts may be used, but Silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition. It will be done. This upper limit is primarily intended to keep costs to a minimum and to effectively control foam. Due to concerns regarding effectiveness in quantity it is practical in nature. Preferably silicone 0.01% to 1% to about 1% and preferably about 0.25% to about 0.5% of the foam suppressant is used. used. These weight percent values used here are for use with polyorganosiloxanes. silica, which may be used, as well as auxiliary materials, which may be utilized. monostearylphos Fate suds suppressors are generally utilized in amounts of about 0.1% to about 2% by weight of the composition.

Although higher amounts can be used, hydrocarbon suds suppressants typically range from about 0.01% to about 5.0%. It is used in the amount of %.

other ingredients Various other ingredients useful in detergent compositions, such as other active ingredients, carriers, hydrotroin additives, processing aids, dyes or pigments, solvents for liquid formulations, etc. Can be combined.

Generally a combination of polycarboxylate builder and polyhydroxy fatty acid amide In addition to the improved built detergent compositions resulting from the By blending sialic acid amide, anionic surfactant and polycarboxylate liquid heavy-duty detergent compositions with a builder can be formulated more easily This is a particularly important benefit of the present invention. Thus, the present invention provides that one or more anions surfactants, polycarboxylate builders, polyhydroxy fatty acid amides, and a liquid carrier. These liquid detergent compositions A relatively large amount of anionic surfactant and polycarboxylate resin were added to this product. can have a ruler. The large amount of polycarboxylate building used here The detergent composition contains more than about 10%, especially more than about 15% by weight of the detergent composition. means.

Liquid detergent compositions can contain water and other solvents as carriers. methanol, Low molecular weight exemplified by tanol, propatool, and isopropatool Primary or secondary alcohols are preferred. -hydric alcohol acts as a surfactant Preferred for solubilization are polyols, such as those having about 2 to about 6 carbon atoms and and those containing about 2 to about 6 hydroxy groups (e.g., propylene glycol , ethylene glycol, glycerin, and 1,2-propanediol) are also used. Can be used.

The detergent compositions herein preferably contain wash water when used in aqueous cleaning operations. is formulated to have a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. will. Liquid product formulations (measured at standard 10% dilution levels) are preferably , a pH of about 7.5 to about 9.5, more preferably about 7.5 to about 9.0. High video In the case of ruder-containing liquids, the pH can be higher, preferably around pH 8. ．． It can be between 5 and 10.5. Technology to control pH to recommended usage levels These include the use of buffers, alkalis, acids, etc. and are well known to those skilled in the art. .

Additionally, the present invention provides that the weight ratio of polycarboxylate to amide surfactant is about 1=1. The polyhydroxy fatty acid amide surfactant in the composition such that from 0 to about 10= Anionic surfactants, nonionic surfactants and/or or detergents containing cationic surfactants and polycarboxylate builders Provides a method for improving the performance of.

Furthermore, the present invention provides a method for treating substrates such as fibers, fabrics, hard surfaces, skin, etc. with water, water-miscible solvents ( one or more anions in the presence of a solvent such as, for example, primary and secondary alcohols). on surfactant, nonionic surfactant or cationic surfactant, polycarboxylic At least about 1% sylate builder, and less polyhydroxy fatty acid amide Detergent compositions containing 1% of both polycarboxylate builder and amide (the weight ratio of surfactants is from about 1:10 to about 10:1). A method for cleaning a substrate is provided. The agitation is preferably done using a cream Give to increase the ning. The preferred method for providing agitation is to rub by hand. or preferably with the help of a brush or other cleaning device. Examples include scrubbing by hand, automatic washing machines, and automatic dishwashers.

In the method, a more preferable polycarboxylate builder is a pair of polyhydrocarbons. The weight ratio of oxyfatty acid amide is from about 1=5 to about 7:1, most preferably about 1=1. about 7=1, and polyhydroxy fatty acid amide and polycarboxylate Preferred amounts and types of ts are as described herein.

Sadness! This is the N-methyl-1-deoxygludityllaurin aliquot for use here. A method for producing a mido surfactant will be exemplified. A skilled chemist can change the shape of the equipment, but this One device suitable for use here is a heated It consists of a 3g 4-day flask equipped with a thermometer and a motor-driven paddle stirrer. Hula The other two ports on the Sco (which is important for very rapid methanol generation), which requires efficiency. A collection cooler and a vacuum outlet are connected. The latter is a nitrogen bleed/vacuum gate. and then to an aspirator and a trap. reaction mixture Variable transformer temperature controller used to heat things [Varia c) 500W heating mantle with J) further controls the temperature of the reaction mixture. placed on the love-jack so that it can be easily raised and lowered to

N-Methylglucamine (195g, 1.0mol, Aldrich, M4700-0 ) and methyl laurate (Brocter-End-Gamble CE1270°2 20.9 g, 1.0 mol) into the flask. Add nitrogen to the solid/liquid mixture under stirring. Prepare the melt by heating under elementary sweep (approximately 25 minutes). Melting temperature reaches 145℃ catalyst (anhydrous powdered sodium carbonate, 10.5 g).

Add 0.1 mol, J, T, Baker). Stop nitrogen sweep and aspirator and adjust the nitrogen bleed to provide a vacuum of 5 inches (5/31 atm) Hg.

From this point on, the reaction temperature can be adjusted by adjusting the barrier and/or The temperature is maintained at 150°C by increasing or decreasing the torque.

Within 7 minutes, the first methanol bubble is seen at the meniscus of the reaction mixture. Intense A reaction quickly accompanies it.

Methanol is distilled until the rate decreases. Adjust the vacuum to about 10 inches H Apply a vacuum of g (10/31 atm). Increase the vacuum approximately as follows (by a predetermined amount) Inch Hg): 3 at 10; 7 at 2o; 1o at 25° Start of methanol generation? After 11 minutes, heating and stirring are stopped (slight foaming occurs at the same time). product Cool and solidify.

The following examples are intended to illustrate compositions of the invention, but do not limit the scope of the invention. However, it is not necessarily meant to specify otherwise, and the scope is determined according to the claims set forth below.

Examples 1-12 Examples of these are polyhydroxy fatty acid amides and polycarboxylate builders. 1 shows a heavy duty granular detergent composition containing.

Base granules 1 2 3 CI4-15 alkyl sulfate 16.9 1B, 9 5.6N-methyl N- 1-Deoxygludityl cocoamide 5.6 5.8 5.8 Zeolite AIg ,818.8 Sodium citrate 30.1 11.3 '11.3 Thorium carbonate 18. 9 1B, 9 16.9 Sodium silicate 5.6 5.6 5.8 Sodium sulfate Umu 15.1 15.1 15.1 Sodium polyacrylate (MW4500 ) 1.1 1.1 1.1 Polyethylene glycol (MW8000) ■, 1 11 1.1 Tallow fatty acid 1.1 1.1 1.1 Brightener 0.2’ 0 ．． 2 0.2 Mix and spray on CI6-18 methyl ester sulfone 1-11.3 protease (1,4% Active enzyme) 0.9 0.9 0.9 Fragrance 0.3 0.3 04 CI2-13 alkyl ethoxylate (6.5 mol) L, L L, 1 1.1 Water and miscellaneous components 3.8 3.8 3.8 too, o 100. OLOG, 0 Examples 1-3 are about 14σ0pp11 (based on wash water weight) for temperatures below about 50°C. ) is a formulation for the preferred use. In the above example, the base granulate component was slurried. and spray drying to approximately 4-8% residual water. Residue The dry ingredients are mixed with the spray-dried granules in granular or powder form in a rotating mixing drum. , spray on the liquid ingredients (nonionic surfactant and fragrance).

Base granular material 45 Linear C12 alkylbenzene sulfonate 7.7014-15 alkyl sulfate 14.7 N-Methyl N-1-deoxygludityl cocoamide 3.0 Zeola Light A' 13.8 16.8 Polyacrylate MW4500 3.8 3J Citric acid 6.0 S')'T-h (S i○2/Na20-1.6) 2.0 2.0 Brightener 0.3 0.3 Polyethylene glycol (MW8000) 1.7 1.7 Sodium carbonate 1 8.3 18.3 Sodium sulfate 10.4 10.4 Water 5.4 5.4 Silicone oil 0.1 0.1 Miscellaneous components 2.9 4.8 Mix and spray on N-Methyl N-1~deoxygludityl cocoamide 3.0 3.0 Sodium citrate Thorium 8.0 Protease (194% active enzyme) 2.2 2.2012-13 Alkyletho Xylate (6.5 mol) 1.5 1.0 Miscellaneous components 1.5 1.5 Total 100.0 100.0 Examples 4 and 5 are preferably utilized at about 101,000 pp wash water basis) and about Figure 2 illustrates a concentrated granular detergent composition intended for temperatures below 50°C. These are Spray dry the powdered or granular dry mixture to approximately 5-8% moisture. The mixture is prepared by combining and spraying on the liquid mixture components.

TMS/TDS (80:20) ★ 7.0 7.0 polyacrylate (MW4 500) 3.3 3.3 Polyethylene glycol (MW8000) 1.3 1.3 Sodium carbonate 10.7 10.7 Sodium sulfate 5.8 5.0 Sodium silicate (S 102 / N a 20-2) 11.8 11.0 Sodium diethylenetriaminepentaacetate 0.7 0.7 Brightener 0.5 0. 5 mixture Zeolite 5.8 5.0 Foam inhibitor flakes ★★ 0.3 0.3 Sodium percarbonate 12.8 12.0 nonanoyloxybenzene sulfonate 5. ON-methyl N-1-deoxygludityl cocoamide 8.4 B, 4CI 8-18 Methyl ester sulfonate 19.1 CI2-3 alkyl ethoxy (6.5 mol) 2.8 2.0 Fragrance 0.5 0.5 Water and miscellaneous components 8.2 8.2 Total too, o ioo.

★TMS/TDS is tartrate monosuccinate/tartrate disuccinate It is.

★★Foam suppressor flakes are a matrix of polyethylene glycol (MW8000) Silica/silicone oil dispersion encapsulated in (approximately 5% active foam suppressor) .

The compositions of Examples 6 and 7 were prepared by slurrying and spray drying the base particulate ingredients to reduce the moisture content to approximately 5% and by incorporating additional dry ingredients. represent. The resulting mixture is side-layered by spraying on the liquid ingredients . The product should be used at a concentration of approximately 1000 ppm at a cleaning temperature below approximately 30°C. I try to sleep.

C1B~18 alkyl ethoxylate (11 mol) 1.11.1 Zeolite 2 1.3 214 Acrylate/maleate copolymer (MW60000) 4J 4.3 diethyl Triamine pentamethylene phosphonate 0.2 0.2 Brightener 0.2 0 ．． 2 Zinc phthalocyanine sulfonate 0.3 0.3 Water and miscellaneous components 9.4 9 ．． 4 mixture N-methyphot-l-deoxygludityl cocoamide 7.0 tomethyl N-1-deo Xygurdityltallow fatty amide 4.0C1B~18methino is stealth sulfone 4.8 Sodium citrate 10 8.0 Sodium carbonate 17.5 17.5 Sodium silicate Ot rate 1.6) 3.5 3.5 Sodium perborate H20 12,512,5 carboxymethyl cellulose 0.5 0.5 tetraacetyl Ethylenediamine 5.0 5.0 Protease (2.1% active enzyme) 1.4 1.4 ioo, o ioo,.

★72 AU/g of active enzyme at 1,5 AU/g The compositions of Examples 8 and 9 are preferably is used at a temperature of about 30 to 95°C at a concentration of about 6000 ppm (based on the weight of washing water). It will be done. These compositions are prepared by slurrying and spray drying the base particulate ingredients to reduce the water content. It can be prepared by setting the target to 9%. Remaining dry ingredients in granular or powdered form In addition, the final liquid components are added by spray-on after mixing in a rotating mixing drum.

Examples 10-20 Examples include polyhydroxy fatty acid amide and polycarboxylate builder. The heavy-duty detergent composition shown in FIG.

Linear C12 alkylbenzene sulfonate 12.8 12.8 CI2-14a Lukyl sulfate 1.8 1.8 12.9 12.9 CI2~14 Alki ethoxylate (7 mol) 1. [l　1.8N-Methyl N-1-deoxyglyceride Ludityl Cocoamide 8.4 8.4N-Methyl N-1-deoxygludityl Cocoamide Leoamide 8.4 8.4 Oleic acid 1.8 1.8 1.8 1.8 Que Dodecenyl succinic acid 4.1 4.1 4.1 4.1 Dodecenyl succinic acid 11.1 11. 1 11.1 11.1 Miscellaneous components (solvent, enzyme, brightener, stabilizer, buffer) 14 ．． 5 14.5 14.5 14.5 Water 45.5 45.5 45.5 45 ．． 5ioo, o too, o too, o too,.

Linear C12 alkylbenzene sulfonate 1O8OC12-14 alkyl sal Phate 9.0 11.5 N-methyl N-1-deoxygludityl cocoamide 6.5 8.4 N-methyl N-1-deoxygludityl oleamide 6.5 Oleic acid 4.0 3.5 2.0 Citric acid 9.0 10.0 9゜0 Dodecenyl succinic acid 5.0 4.8 5.0 Miscellaneous components (solvent, enzyme, brightener, stabilizer) Fixing agent, buffering agent, etc. > 15.8 15.2 16.3 Water 4g, 1 48J 4 8.3 100.0 100.0 100.0 Examples 10-16 are preferably about 12,000 ppm (based on wash water weight) and 30-9 Used at a temperature of 5°C. These are prepared as follows. Non-aqueous solvent, aqueous interface Activator paste or solution, molten fatty acids, polycarboxylate builders and Aqueous solutions of other salts, aqueous ethoxylated tetraethylenepentamine, buffers, caustics, and remaining water. Citric acid aqueous solution or sodium hydroxide aqueous solution Adjust the pH to approximately pH 8.5. After pH adjustment, dirt release agent, Add final ingredients such as enzymes, colorants, and fragrances and stir the mixture until a single phase is achieved. Stir.

N-Methyl N-1-deoxygludityl cocoamide 4.2 3.1 3.1 11.5CI4-15 alkyl ethoxylate (2.25 mol) sulfate L2.8 9.3 L5C12-18 alkyl ethoxylate (2.5 mol) Ruphate 6,2C12-14 alkyl sulfate 3. IC16~18a Rukylethoxylate 3.4 2.5 Dodecyltrimethylammonium chloride 0.5 0.2 Dodecenyl succinate 5.0 Site rate 3.4 15.0 5. OTMS/TDS (80/20)★ a, tCl. ~14 fatty acids 3.0 3.0 Oxydisuccinate 20.0 Ethoxylated tetraethylene pentamine 1.5 2.0 polyacrylate (MW 4500) 1.5 1.5 Miscellaneous ingredients (enzymes, brighteners, stain release agents, stabilizers, etc.) 15.3 14.9 14.9 18.3 Wednesday 52.7 51.2 51.2 54.0100.0100.0100.0100.0★TMS/TDS is Tal Trate monosuccinate/tartrate disuccinate.

Examples 18-20 are preferably less than about 50° C. at about 2000 In (based on wash water weight). Used at high cleaning temperatures.

These are prepared as follows. Non-aqueous solvents, aqueous surfactant pastes or solutions , molten fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethos Combine oxygenated tetraethylenepentamine, buffer, caustic, and remaining water. . Adjust the pH using either citric acid or sodium hydroxide. Adjust pH to approximately 8.5. In the case of examples 18 and 19 with high builder content The pH can optionally be adjusted to about pH 10.5. After pH adjustment, remove dirt. Add final ingredients such as solvents, enzymes, colorants, and fragrances and mix until a single phase is achieved. Another method for producing polyhydroxy fatty acid amide using a stirring device is as follows. Ru. Fatty acid methyl esters (source: Brocter & Gamble methyl esters) CE1270) and N-methyl-D-glucamine (source: Aldori) Chemical Company M4700-0) 75g and sodium methoxide ( Source: Aldrich Chemical Company 16,499-2) 1.04g and A reaction mixture consisting of 68.51 g of chill alcohol is used. Keep the reaction vessel dry. Equipped with standard reflux equipment with drying tube, condenser and stirring bar. In this method Combine N-methylglucamine with methanol under argon with stirring and mix well. Start heating while stirring (stir bar: reflux). After 15-20 minutes, the solution reaches the desired temperature. When the temperature is reached, add the ester and sodium methoxide catalyst. Sample regularly The solution is completely clear after 63.5 minutes. It is recognized that The reaction is, in fact, judged to be almost complete at this point. Ru. The reaction mixture is kept under reflux for 4 hours. Crude raw material recovered after methanol removal The product weighs 156.16 g. After vacuum drying and purification, the purified product 106.9 A total yield of 2g is collected. However, regulation over the course of the reaction Yields are not calculated on this basis because regular sampling makes the overall yield value meaningless. Not possible. The reaction is carried out at a reactant concentration of 80% and 80% for a period of up to 6 hours to produce product. and 90% (with very little by-product formation).

The following, without seeking to limit the invention, include polyhydroxy fatty acid amides: Techniques that can be considered by formulators in the preparation of various detergent compositions using It is merely intended to further illustrate additional aspects of the logic.

Polyhydroxy fatty acid amide can be used under highly basic or highly acidic conditions due to the amide bond. It will be readily appreciated that it is susceptible to some instability under conditions. some Although degradation is acceptable, these materials cannot be exposed to pH above about 11 for unreasonably long periods of time. Preferably no pl higher than 10 and no pH lower than about 3 is preferred.

The final product pH (liquid) is typically 7.0-9.0.

During the production of polyhydroxy fatty acid amides, typically It may be necessary to at least partially neutralize the base catalyst used for this purpose. squid Acids can also be used for this purpose, but detergent formulators may It is simply convenient to use acids that provide useful and desirable anions when They will recognize that this is a serious matter. For example, citric acid is used for neutralizing purposes The citrate ions (about 1%) that can and are obtained are about 40% polyhydroxy fat. Allows the acid amide slurry to remain with the slurry and be added to a later manufacturing step in the entire detergent formulation. supply the pump. Substances in acid form, e.g. oxydisuccinate, nitrilotria acetate, ethylenediaminetetraacetate, tartrate/succinate, etc. can be used similarly.

Polyhydroxy derived from coconut alkyl fatty acids (mainly 012-C14) Siamic acid amides are more flexible than their tallow alkyl (mainly 016-Cl8) equivalents. Soluble.

Therefore, C1°~014 materials are slightly easier to formulate into liquid compositions. and is soluble in cold water wash baths. However, CI6 to C18 substances also This is particularly useful in situations where warm to hot wash water is used. Fact, C- C substances may be better detergent surfactants than their C1°-C14 equivalents. Ru. Therefore, formulators must specify the specific polyhydroxy fatty acids for use in a given formulation. When choosing an amide, you may want to balance ease of manufacture vs. performance. .

In addition, the solubility of polyhydroxy fatty acid amide is determined by the unsaturation point in the fatty acid moiety and It will be appreciated that this can be increased by having/or chain separation techniques.

Thus, polyhydroxy fatty acid amines derived from oleic acid and isostearic acid Substances such as midos are more soluble than their n-alkyl equivalents.

Similarly, the solubility of polyhydroxy fatty acid amides produced from trisaccharides, trisaccharides, etc. , typically will be greater than the solubility of monosaccharide-derived equivalents. This high solubility Certain aids can be had in formulating liquid compositions.

Furthermore, polyhydroxy fatty acid amide whose polyhydroxy group is derived from maltose is , used in combination with regular alkylbenzenesulfonate (rLAsJ) surfactants It sometimes seems to work particularly well as a detergent. I don't try to limit it by theory, but , polyhydroxy fatty acid amide derived from higher sugars such as maltose and LAS. The combination produces a substantial and unexpected decrease in interfacial tension in aqueous media, which Therefore, it seems to improve the net cleaning performance (polyhydroxy fat derived from maltose) The production of fatty acid amides will be described later).

Polyhydroxy fatty acid amide can not only be produced from refined sugar, but also by hydrolysis. Starch, e.g. corn starch, potato starch, or by formulator Also from starches derived from other favorable plants containing the desired monosaccharides, trisaccharides, etc. Can be manufactured. This has particular importance from an economic point of view. Thus, ``high guru'' ``coast'' corn syrup, ``high maltose'' corn syrup, etc. It can be used economically. Delignified hydrolyzed cellulose valves are also It can provide a raw material source for sialic acid amide.

As mentioned above, polyhydroxides derived from higher sugars such as maltose and lactose Syria fatty acid amides are more soluble than their glucose equivalents. Furthermore, more Soluble polyhydroxy fatty acid amides can be prepared by various treatments of their less soluble equivalents. It seems that it can promote solubilization. Therefore, prescribers, e.g. - You may decide to use ingredients that include scone syrup, but with a small amount of malt Optionally, syrups containing a certain amount of sugar (eg, 1% or more) may be selected. polyhydroxy The resulting mixture of fatty acids is generally a "pure" glucose-derived polyhydroxy Shows more favorable solubility over a wide range of temperatures and concentrations than fatty acid amides Will. Thus, the economics of using sugar mixtures rather than pure sugar reactants In addition to their physical benefits, polyhydroxy fatty acid amides made from mixed sugars offer performance and/or may offer very substantial advantages in terms of ease of formulation. but However, in some cases, a slight loss in grease removal performance (dishwashing) is approximately 25 % of fatty acid maltamide and a slight loss of foaming properties. Loss may be observed in amounts greater than about 33% (said percentage is the amount of Maltese in the mixture). Mido-derived polyhydroxy fatty acid amide ■S glucose-derived polyhydroxy fatty acid % of amide). This can vary slightly depending on the chain length of the fatty acid moiety. typical In general, and formulators who decide to use such mixtures, monosaccharides (e.g. (e.g., glucose) to trisaccharides/higher sugars (e.g., maltose) from 4:1 to about It is advantageous to choose a polyhydroxy fatty acid amide mixture containing 99=1 You can find out things.

Preferred acyclic polyhydroxy from fatty esters and N-alkyl polyols The fatty acid amide is produced in an alcoholic solvent at a temperature of about 30°C to 90°C, preferably about 5°C. It can be carried out at a temperature of 0°C to 80°C. Glycol solvents are not used in finished detergent formulations. It is not necessary to completely remove the reaction product before use, e.g. drug formulators to perform such processes in a 1,2-propylene glycol solvent. It has now been confirmed that it is convenient.

Similarly, for example, formulators of solid detergent compositions, typically granular detergent compositions, Ethoxylation of processes (EO3-8) Ethoxylation of C12-CI4 alcohols, etc. Alcohol, for example also available as Neodol 23EO6,5 (shell) We have found it convenient to carry out the process at 30°C to 90°C in a solvent consisting of can be done. When such ethoxylates are used, they contain substantial amounts of Contains no non-ethoxylated alcohols and most preferably contains substantial amounts of monoethoxylated alcohols. Preferably, it does not contain alcohol (designation "T").

Although the method for producing the polyhydroxy fatty acid amide itself does not form part of the present invention, The manufacturer also accepts other methods of synthesizing polyhydroxy fatty acid amides, such as those described below. can be done.

Typically, the preferred acyclic polyhydroxy fatty acid is reacted with hydrogen in the presence of a N-alkylpolyhydroxyamine derivatives are obtained from the desired sugar or sugar mixture by After producing the conductor, Step 2: The polyhydroxyamine is preferably treated with a fatty acid ester. It consists of reacting with ester to form an amide bond. Useful in step 2 of reaction sequence Various N-alkyl polyhydroxyamines can be prepared by various methods disclosed in the art. However, the following method is a convenient and economical raw material for producing sugar syrup. use. For best results when using such syrup ingredients, manufacturers is a syrup that is completely pale in color or preferably almost colorless (“aqueous-white”). You should understand that you should choose.

Production of N-alkyl polyhydroxyamines from plant-derived sugar syrups (2) Adduct formation - The following is a standard method. In this standard method, gar 420 g of approximately 55% glucose solution with donor color less than 1 (corn syrup - Approximately 231 g of glucose (approximately 1.28 mol) was mixed with approximately 50% methylamine 59.5 g - 1.92 mol) of an aqueous solution. Methylamine ( Purge the MMA) solution, blanket with N2, and cool to below about 10°C.

Purge the corn syrup and blanket with N2 at a temperature of about 10-20°C. Ko Slowly add the syrup to the MMA solution at the indicated reaction temperature. Gar Measure the donor color at the approximate time indicated (in minutes).

Table 1 Time (minutes) 10 30 GO120180240 As seen from the above data , the Gardner color of the adduct decreases as the temperature increases above about 30°C. Much worse, and at about 50°C, when the adduct has a Gardner color of less than 7 The time is only about 30 minutes. For longer reactions and/or retention times, The temperature should be less than about 20°C. Gardner color is a good color glucami should be less than about 7, preferably less than about 4 for

When low temperatures are used to form the adduct, a substantial equilibrium concentration of the adduct is reached. The time for decontamination is reduced by using a higher ratio of amine to sugar. Attention For a molar ratio of amine to sugar of 1.5:1, equilibrium is at a reaction temperature of about 30°C. Achieved in 2 hours. At a molar ratio of 1.2:1, under the same conditions, the time is less. At least about 3 hours. For good color, the amine:sugar ratio and reaction temperature In combination with reaction time, substantially equilibrium conversion, e.g., about 90% or more for sugar , more preferably about 95% or more, even more preferably about 99% or more, and the adduct. achieve a color that is less than about 7 in some cases, preferably less than about 4, more preferably less than about 1. chosen to do.

Using the process with a reaction temperature below about 20° C. and using different guards as indicated Using corn syrup that has a neutral color, the MMA adduct color (substantially at equilibrium after reaching at least about 2 hours) as indicated.

Table 2 Gardner color (approximate) Corn syrup 1111+000+ Additive 3 415 7/8 7/8 1 2 1 As can be seen from the above , the starting sugar material should be adjusted so that it consistently has adducts that are acceptable. Must be colorless. When the sugar has a Gardner color of about 1, the adduct is sometimes Sometimes acceptable, sometimes unacceptable.

When the Gardner color is greater than 1, the resulting adduct is unacceptable. The beginning of sugar The better the initial color, the better the color of the adduct.

■, Hydrogen reaction - adducts from the above with a Gardner color of 1 or less are as follows: Hydrogenate according to the method.

Additive 539g in water and United C Approximately 23.1 g of G 49 B N i catalyst was added to the autoclave of Add to the tube and purge twice with 200 psiH at about 20°C. H2 pressure approx. Increase the temperature to 1400 psf and raise the temperature to approximately 50°C. Then increase the pressure to about 160 Raise to 0 pslg and maintain temperature at about 50-55°C for about 3 hours. The product is At this point, about 95% hydrogen is added. The temperature is then raised to about 85°C for about 30 minutes, The reaction mixture is decanted and the catalyst is filtered off. The product is obtained by removing water and MMA by evaporation. After removal, it is about 95% N-methylglucamine, a white powder.

Repeat the above method using approximately 23.1 g of Raney Ni catalyst with the following changes: . The catalyst was washed three times and the reactor (catalyst is in the reactor) was heated to 200 ps f g Purge twice with H2 and pressurize the reactor with N2 at 1600 pslg for 2 hours. The pressure was then released for 1 hour and the reactor was repressurized to 1600 pslg. then , the adduct was pumped into the reactor at 200 psig and 20°C, and the reactor was Purge with 200 ps 1gH2 etc. as shown below.

The resulting product in each case is greater than about 95% N-methylglucamine. Ni: about 10 p1) less than 11 for glucamine: and Gardner about 2 has a solution color of less than

Crude N-methylglucamine is color stable to short exposure times of about 140°C.

Low barrel 11' (less than about 5%, preferably less than about 1%) and good color (guard (less than about 7, preferably less than about 4, more preferably less than about 1) It is important to have appendages.

In another reaction, the adduct is produced from about 159 g of about 50% methylamine in water. Prepare by venting, purging and shielding with N2 at about 10-20°C. Approximately 70% About 330 g of syrup (water - almost white) was degassed with N2 at about 50°C, Add slowly to the methylamine solution at a temperature below about 20°C. Approximately 3 liters of solution Mix for 0 minutes to give approximately 95% adduct, which is a very pale yellow solution.

Approximately 190 g of adduct in water and United Catalyst G49B Ni catalyst Add about 9g to a 200ml autoclave and purify with N2 three times at about 20℃. page.

Increase the N2 pressure to about 200 psi and the temperature to about 50°C. Pressure 250 psi and maintain temperature at about 50-55°C for about 3 hours. The product is then About 95% hydrogen was added at the point, and then the temperature was raised to about 85°C for about 30 minutes. After removing water and evaporating, the product is approximately 95% N-methylglucamine, a white powder. be.

N2 pressure is approximately 1000 psig to minimize Ni content in glucamine. It is also important to minimize contact between the adduct and the catalyst when the . The nickel content in N-methylglucamine in this reaction is the same as that in the previous reaction. approximately 1 oopp- compared to less than 10 ppm.

The following reaction with N2 is performed for direct comparison of reaction temperature effects.

Typical methods similar to those described above can be used to generate adducts and carry out hydrogen reactions at various temperatures. A 200 ml autoclave reactor is used.

The adduct used to produce glucamine is approximately 55% glucose (corn syrup). 420 g (glucose 231 g; 1.28 mol) (solution is The solution is less than 7 Gardner. color) and about 119 g of 50% methylamine (59.5 g of MMA; 1. 92 mol) (manufactured by Air Products).

The reaction method is as follows.

1. Add about 119 g of 5096 methylamine solution to a reactor purged with N2, and 2 and cool to below about 10°C.

2. Degas the 55% corn syrup solution with N2 at 10-20℃ and/or or purge to remove oxygen from the solution.

3. Slowly add the corn syrup solution to the methylamine solution and bring the temperature to about 20℃. Keep below.

4. Once all the corn syrup has been added, stir for about 1-2 hours.

The adducts are either used in hydrogen reactions immediately after production or are dehydrated to prevent further degradation. Store at room temperature.

The glucamine adduct hydrogen reaction is as follows.

1. Adduct (color less than Gardner 1) about 134g and G49B Ni about 5. Add 8g to a 200ml autoclave.

2. Heat the reaction mixture at about 20-30°C and about 200 ps! Purge twice with H2 Ru.

3. Pressurize to about 400 psi with N2 and raise the temperature to about 50°C.

4. Increase the pressure to about 500 psi and react for about 3 hours. Temperature about 50-5 Keep at 5℃. Take sample 1.

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

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

The conditions for the isothermal reaction are as follows.

1. Add about 134 g of adduct and about 5.8 g of G49B Ni to 200 ml of autoclave. Add to toclave.

2. Purge twice with approximately 200 ps i H2 at low temperature.

3. Apply pressure to about 400 ps with N2 and raise the temperature to about 50°C.

4. Increase the pressure to about 500 psi and react for about 3.5 hours. pointed out the temperature temperature.

~55°C; Sample 4 is for approximately 75°C; Sample 5 is for approximately 85°C. (reaction time at about 85° C. is about 45 minutes).

All runs gave similar purity of N-methylglucamine (approximately 94%); The Gardner color is similar to that immediately after reaction, but only the two-step heat treatment provides good color stability. A run at 85°C gives a slight color immediately after the reaction.

Example 22 N-methylmaltamine tallow (cured) for use in detergent compositions according to the invention ) The method for producing fatty acid amide is as follows.

Step 1 - Reactant: Maltose monohydrate (Aldrich, lot 01318KW ); Methylamine (40% by weight in water) (Aldrich, lot 03325T M); Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot 12921LW).

Add the reactants to the glass liner (250 g maltose.

428 g of methylamine solution, 100 g of catalyst slurry - 50 g of Ranney Ni), 3 jl rocking autoclave, and the autoclave was flushed with nitrogen (3X 500 psig) and hydrogen (2X 500 psig) under H2. Rock over the weekend at a temperature of 28°C to 50°C at room temperature. crude reaction mixture Vacuum filter twice through a glass microfiber filter with silica gel plugs. . Concentrate the filtrate to a viscous mass. The final trace of water is obtained by dissolving the viscous substance in methanol and then and azeotroped by removing methanol/water on a rotary evaporator. final drying Drying is carried out under high vacuum. The crude product was dissolved in refluxing methanol, filtered, cooled and reconstituted. Crystallize, filter and dry the filter cake under vacuum at 35°C. This is cool This is point #1. Concentrate the filtrate and store it in the refrigerator overnight until a precipitate begins to form. do. Filter the solid and dry under vacuum. This is cut #2. Re-filtrate Concentrate to half the volume and achieve recrystallization. Almost no precipitate forms. small amount Add ethanol and leave the solution in the freezer over the weekend. solid substance Filter and dry under vacuum. The combined solid is the N-methane used in step 2 of the total synthesis. Consisting of tilmartamine.

Step 2 - Reactant 2N-methylmaltamine (from step 1); cured tallow methyl ester Sodium methoxide (25% in methanol); Anhydrous methanol (solvent) : Amine:ester molar ratio 1:1; initial crystal amount 10 mol% (w/r Malta (min), increased to 20 mol%; solvent amount 50% (by weight).

In a sealed bottle, heat 20.36 g of tallow methyl ester to melting point. (water bath), placed in a 250 ml 30 round bottom flask under mechanical stirring. flask to about 70° C. to prevent the ester from coagulating.

Separately, 25.0 g of N-methylmaltamine was combined with 45.36 g of methanol; Add the resulting slurry to the tallow ester with good mixing. 2 in methanol Add 1.51 g of 5% sodium methoxide. After 4 hours, the reaction mixture was clear. , therefore an additional 10 mol % of crystals (20 mol % total) was added and the reaction started. It is allowed to continue overnight (approximately 68° C.), after which time the mixture is clear. Then, the reaction tube Fix the lasco for distillation. Increase temperature to 110°C. Distillation at atmospheric pressure Continue for 60 minutes.

High vacuum distillation is then started and continued for 14 minutes, at which point the product is very thick.

The product is allowed to remain in the reaction flask for 60 minutes at 110°C (external temperature). Frass the product Scrape it off and rub it in ethyl ether over the weekend.

The ether was removed on a rotary evaporator and the product was stored in an oven overnight and reduced to a powder. Smash. Remove remaining N-methylmaltamine from the product using silica gel. leave

Charge the silica gel slurry in 100% methanol to the funnel and add 100% methanol to the funnel. Wash several times with water. A concentrated sample of the product (2 in 100 ml of 100% methanol) 0 g) onto silica gel and several times using vacuum and several methanol washes. Elute twice. The collected eluate is evaporated to dryness (rotary evaporator). remaining taroe The stellate is removed by trituration in ethyl acetate overnight, then filtered. filtration case Vacuum dry the wood overnight. The product is tallow alkyl N-methyl maltamide. Ru.

In another form, step 1 of the reaction sequence comprises glucose or glucose. Use commercially available corn syrup, typically a mixture with 5% or more maltose You can do what you want. The obtained polyhydroxy fatty acid amide and mixture are Any of the detergent compositions of the invention can be used.

In yet another embodiment, step 2 of the reaction sequence comprises 1,2-propylene glyco It can be carried out in mol or neodol. At the discretion of the prescriber, propylene Recall or Neodol is a reactive product that is used to formulate detergent compositions. It is not necessary to remove it from the composition. Again, per the prescriber's request, methoxy The cid catalyst can be neutralized by citric acid to give sodium citrate; Sodium enoate can remain in the polyhydroxy fatty acid amide.

Depending on the wishes of the formulator, the compositions can contain more or less of each type of antifoam agent. typical Typically, in the case of dishwashing, high foaming is desirable and therefore antifoaming agents are not used. Probably not. For fabric washing in top-loading washers, some control of foam A significant degree of foam control may be desirable and in the case of front charging machines. There are some good things. Various antifoam agents are known in the art and for use herein. can be habitually selected. In fact, antifoam agents or mixtures of antifoam agents for certain detergent compositions The choice of products depends on the presence and amount of polyhydroxy fatty acid amide used therein. It will also depend on the other surfactants present in the formulation. death However, when used in combination with polyhydroxy fatty acid amide, various silicones Foam-based antifoam agents appear to be more efficient than various other types of antifoam agents. (i.e. smaller amounts can be used). X2-3419 and Q2-3302 (da Particularly useful are silicone antifoam agents available as U.S. Corning.

Formulators of fabric laundry compositions that can advantageously contain soil release agents have a variety of existing materials to choose from. (e.g., U.S. Pat. No. 3,962.152, No. 4,1) No. 16゜885, No. 4,238.531, No. 4゜702.857 Specification No. 4,721,580 and Specification No. 4,877.896 reference). Additional soil release materials useful herein include 01-C4 alkoxy-terminated Polytechnoxy unit source (e.g. CII [0CR2CH2]1BOH), Teleph Taloyl monosawara (e.g. dimethyl terephthalate); poly(oxyethylene) Oxy unit source (e.g. polyethylene glycol 150'0); oxyisopropylene Pyreneoxy unit source (e.g. 1,2-propylene glycol): and oxy Non-ionizing of reaction mixtures containing sources of ethyleneoxy units (e.g. ethylene glycol) on-oligomer esterification products (especially oxyethyleneoxy units versus oxyiso the molar ratio of propyleneoxy units is at least about 0.5:1). . Such non-ionic soil release agents have the general formula (wherein R1 is lower (e.g. C-C) alkyl, especially methyl; each y is 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 oxyethyleneoxy vs. H and CH3 to provide a molar ratio of sopropyleneoxy of at least about 0.5:1. is a mixture of both) has.

Another preferred class of soil release agents useful herein is that such agents are of the HOROH type (formula (in which R is propylene or higher alkyl) is substantially toothless. Other than the conditions described in U.S. Pat. No. 4,877,896, It has a main type. (The stain release agent of U.S. Pat. No. 4,877,896 is , for example, dimethyl terephthalate, ethylene glycol, and 1,2-propylene Can consist of the reaction product of glycol and 3-sodiosulfobenzoic acid On the other hand, these additional soil release agents include, for example, dimethyl terephthalate and ethylene. glycol, 5-sodiosulfoisophthalate, and 3-sodiosulfoisophthalate It can consist of a reaction product with an acid. Such agents should not be used in granular laundry detergents. preferred for

Formulators also recommend non-berborate bleaching, especially in heavy-duty granular laundry detergents. It may prove advantageous to include agents. Various peroxygen bleaches are commercially available and can be used here; among these, bell carbonate is convenient and economical. Thus, the composition may contain 3 to 20% by weight of the composition. %, more preferably 5-18% by weight, most preferably 8-15% by weight. may contain solid bell carbonate bleach (usually in the form of the sodium salt).

Sodium percarbonate is an addition compound with the formula corresponding to 2NaCOψ3H202 It is commercially available as a crystalline solid. Most commercially available substances are A small amount of EDTA, 1-hydroxyethylidene 1,1-di Heavy metal ion sequestering agents such as phosphonic acid (HEDP) and aminophosphonates are listed. can be lost.

For use herein, bell carbonate must be added to detergent compositions without additional protection. Although a preferred embodiment of the invention utilizes a stable form of material (FMC), . Various coatings can be used, but are applied as an aqueous solution and to provide a silicate solids content of 2 to 10% (usually 3 to 5%) by weight of the Sea urchin dried SiO:Na20 ratio 1.6:1 to 2.8:1, preferably or 2.0:1 sodium silicate is the most economical. Magnesium silicate A chelating agent such as one of those mentioned above can also be used in the coating. Can be mixed.

The particle size range of crystalline bell carbonate is 350 μm to 450 μm (average 400 μm μm). When coating, the crystals have a size within the range of 400-600 μm. has.

The heavy metals present in the sodium carbonate used to produce Belcarbonate are , which can be controlled by the incorporation of sequestrants into the reaction mixture; The product still requires protection from heavy metals present as impurities in other components of the product. Essential. The total amount of iron, copper, and manganese ions in the product is 25 ppm to avoid unacceptable negative effects on carbonate stability It has been found that the It was done.

Modern concentrated laundry detergent granules are:

Example 23 C14-15 alkyl alcohol sulfonic acid 13014-15 alkyl polyester Toxy(2,25)sulfonic acid 5.60C12-13 alkyl polyethoxylate (6,5) 1.45CI2-14 fatty acid N-methylglucamide 2.50 Sodium aluminosilicate (hydrated zeolite A 25.2 citric acid 1060 Sodium carbonate Washing water Adjust pH to -9.90 Sodium polyacrylate (molecular Amount 2000-4500) 3.2 Diethylenetriaminepentaacetic acid 0.45 Sabina -ze 2 0.70 6-nonaraylamino-6-oxo-beroxy 7.40 caproic acid Sodium perborate monohydrate 2.10 nonanoyloxybenzenesulfonic acid 5.00 Brightener 0.10 Single-layer silicate builders are known in the art. Layered sodium silicate is preferred stomach. See, for example, U.S. Patent No. 4.66 issued May 12, 1987 to H.P. Ritte. 4゜859 (herein incorporated by reference) layered sodium silicate building See Dar. A suitable layered silicate builder is available from Hoechst as 5KS-6. can.

2 Available from Novo Nordisk A/S in Kovengagen.

Highly preferred granules of the type described above contain from about 0.0001 to about 2% by weight of active enzyme. and at least about 1% by weight of said polyhydroxy fatty acid amide (up to Also preferably the anionic surfactant is an alkylbenzene sulfonate surfactant. (No)

The following are preferred methods for making liquid bee duty-laundry detergents according to the present invention: related. The stability of enzymes in such compositions is considerably lower than in granular detergents. That will be recognized. However, typical By using enzyme stabilizers, lipase and cellulase enzymes can be It can be protected from degradation by the enzyme Aase. However, lipase stability In the presence of killbenzene sulfonate (rLASJ) surfactant still relatively It is defective. Apparently, LAS partially denatures lipase and further denatures Lipases appear to be more susceptible to attack by proteases.

In view of the aforementioned considerations, which can be particularly troublesome with liquid compositions, liquid detergent compositions containing together enzymes such as protease, protease and cellulase. It is a challenge to do so. Stable liquid wash with effective blend of detergent surfactants Providing such ternary enzyme systems in pharmaceutical agents is a particular challenge. Additionally, Pero Stably incorporating oxidase and/or amylase enzymes into such compositions It is difficult.

Various types of lipase, protease, cellulase, amylase, and peroxidase A mixture of suitable in the presence of a non-alkylbenzenesulfonate surfactant system consisting of Stable and therefore effective for heavy duty – even solid and liquid detergents It has now been confirmed that this can be done. In fact, the formulation of a stable liquid enzyme-containing detergent composition is , which constitute highly advantageous preferred embodiments afforded by the technology of the present invention. Ru.

In particular, prior art liquid detergent compositions typically include LAS or LAS and the R O(A) mixture with SO3M type (rAESJ') surfactant, i.e. LAS /AES mixture. In contrast, the liquid detergents of the present invention preferably contain AE S and a polyhydroxy fatty acid amide of the type disclosed herein. . A minimal amount of LAS can be present, but the stability of the enzyme may be thereby reduced. It will be recognized that there will be. Therefore, the liquid composition substantially contains LAS. Preferably no (i.e. less than about 10%, preferably less than about 5%, more preferably less than about 5%) or less than about 1%, most preferably 0%).

(a) about 1% to about 50% anionic surfactant, preferably about 4% to about 40%; (b) Active detergent enzyme about 0.0001% to about 2%; (C) Formula (In the formula, R is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, roxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon building and Z is a line with at least 3 hydroxyls directly connected to the chain Polyhydroxyhydrocarbyl or alkoxy thereof having a hydrocarpyl chain of the enzyme performance increasing amount (preferably about 0.5% to about 12%) of Contains a hydroxy fatty acid amide substance, the composition is an alkylbenzene sulfonate Provided is a liquid detergent composition that is characterized in that it is substantially free of.

The water-soluble anionic surfactant of the present invention is preferably RO(A) SO3M translation (wherein R is unsubstituted Cl0=024 alkyl or hydroxyalkyl (C1 o-C24) group, A is an ethoxy or propoxy unit, m is from O is also a large integer and M is hydrogen or a cation) (rAEsJ). Preferably, R is an unsubstituted 01□-018 alkyl group, A is an ethoxy unit, m is about 0.5 to about 6, and M is a cation. Cations are good Preferably, metal cations [e.g., sodium (preferred), potassium, lithium ammonium, calcium, magnesium, etc.] or ammonium or substituted ammonium It is a mu cation.

The ratio of the surfactant (rAEsJ) to the polyhydroxy fatty acid amide of the present invention is , about 2 to about 8:1, preferably about 1:1 to about 5:1, most preferably about Preferably from 1:1 to about 4=1.

The liquid composition of the present invention alternatively comprises polyhydroxy fatty acid amide, AES, and C-C22 (preferably C1° to C2o) linear alcohol and alcohol per mole condensate with about 1 to about 25, preferably about 2 to about 18, moles of ethylene oxide. 0.5% to about 5%.

As mentioned above, the liquid composition of the invention is preferably a 10% solution in water at 20°C. middle p)! from about 6.5 to about 11.0, preferably from about 7.0 to about 8.5.

The composition preferably further comprises from about 0.1% to about 50% detersive builder. child These compositions preferably contain from 0.1% to about 20% of citric acid or its water-soluble salt. %, and water-soluble succinate tartrate, especially its sodium salt and that from about 0.1% to about 20% of a mixture of from about 0.1% to about 20% by weight of the builder. alkenyl succinate 0.1% to 50% can also be used.

Preferred liquid compositions of the invention have an active content of about 0.0001% to about 2%, preferably about 0.0001% to about 2%, on an active basis. or about 0.0001% to about 1%, most preferably about 0.001% to about 0.5%. Contains detergent enzymes. These enzymes are preferably proteases (preferred), lipase (preferred), amylase, cellulase, peroxidase, and selected from the group consisting of mixtures thereof. Compositions containing two or more enzymes are preferred. and most preferably one is a protease.

Although various descriptions of detergent proteases, cellulases, etc. are available in the literature, detergent proteases, cellulases, etc. Pase is somewhat less well known. Therefore, to help prescribers, there is interest in Some lipases include Amano AKG and Bacillis Sp lipase [ For example, Solvay enzyme]. Also, November 1990 Specification of EP A 0399 681 published on April 28, 1987, published on April 15, 1987. Publication EP A No. 0 218 272 and Publication No. 18 May 1989 PCT/D K No. 88100177 (all incorporated herein by reference) See lipase described in (incorporated).

Suitable fungal lipases include Hu*fcola Ianuginosa and The following are those that can be produced by Thermomyces Ianuginosus. can be lost. European Patent Application No. 0 258 068 (herein incorporated by reference) The gene from Hui+1cola lanuginosa as described in and express the gene in Aspergillus oryzae. In particular, the obtained lipase (trade name Ribolase (LIPOI, ASE)) ] is the most preferred.

from about 2 to about 20,000, preferably from about 10 to about 6,000 lipa per micron of product. One unit of lipase (LU/g) can be used in these compositions. lipase mono The pH stat (1) H is 7. C1 temperature is 30℃, substrate is emulsion tributyl of Ca”+ and NaCl in phosphate in It is the amount of lipase in the presence that produces 1 μmol of titratable butyric acid per minute.

The example below is (a) Enzymes or preferred enzymes selected from proteases, cellulases and lipases or a mixture thereof (the amount used is determined by the effective Jjl (i.e., the amount of dirt removed) of the enzyme or or enzyme mixtures, but typically from about 0.01 to about 20% by weight of the total composition); (b) a polyhydroxy fatty acid amine surfactant of the type disclosed herein (typically at least about 2%, more typically from about 3 to about 15%, preferably by weight of the composition. accounts for about 7 to about 14% by weight); (c) RO(A) type 503M, preferably RO(CIC) as disclosed herein; HO) 503M [in the formula, 2 2 ts R is 014 to C15 (average), m is 2 to 3 (average), and M is H or a water-soluble salt-forming cation, e.g. Na+] (the surfactant is (d) optionally comprising about 5% to about 25% by weight of the composition; RO5OM [preferably, in the formula, R is C1□ to C14 (on average)] as disclosed in a surfactant (the surfactant preferably comprises from about 1% to about 10% by weight of the composition) (e) a liquid carrier, especially water or a water-alcohol mixture; (f) optionally Thus, but most preferably an effective amount of enzyme stabilizer (typically from about 1 to 10% of the composition) (g) water-soluble polycarboxylate builder (typically composition (about 4% to about 25% by weight): (h) In some cases, the various detergent adjuvants, brighteners, etc. mentioned above (typically, from about 1% to about 10% by weight of the composition) contains and (i) The composition is a preferred heavy-duty liquid detergent composition that does not substantially contain LAS. Examples of products are shown below.

Example 24 C14-15 alkyl polyethoxylate (2,25) sulfonic acid 21.00 C12-14 fatty acid N-methylglucamide 17-00 tartrate mono- and Sodium disuccinate 4.00 (80:20 mixture) Citric acid 3.80 C1゜~14 fatty acids 3.00 Tetraethylene pentamine ethoxylate (15-18) 1.50 polyethylene Ren-polypropylene terephthalate polysulfone 0.20 acid Etkynolysis polymer Protease B (34g/j)) 20.68 Lipase (100KLU/g )” 0.47 Cellulase (5000cevu/g)’ 0.14 Brightener 36” Q, 15 Ethanol 5.20 Monoethanolamine 2.00 Sodium formate 0.32 1.2-Propanediol 8.00 Sodium hydroxide 3.10 Silicone foam suppressor 0.0375 Boric acid 2.00 Water/miscellaneous ingredients balance (assumed to be 100) 1 Prepared as above 2 Protease B is European Patent Application No. 87 3037 filed on April 28, 1987. 61, particularly pages 17, 24 and 98. It is a protease.

3 The lipase used here is as described in European Patent Application No. 0258068. The gene from the sea urchin Hu+*lcolalanuginosa was cloned and obtained by expressing the gene in Aspergillus oryzae. It is a lipase [commercially available under the trade name LIPOLASE (Denmark)]. from Nordisk A/S, Copenhagen)].

4 The cellulase used here is sold under the trademark CAREZYME. (Novo Nordisk A/S, Copenhagen, Denmark).

5 Brightener 36 is commercially available as Tinopal TAS36.

The brightener is a whitening agent (4,5%), monoethanolamine (60%) and water (35,5%). 5%) to the composition as a separately prepared premix.

Example 25 The following is a product prepared by mixing the indicated ingredients in a mixing drum. Figure 1 illustrates a bright velborate bleach/bleach activator detergent composition.

In the example, zeolite A contains 20% fishing rod and has an average particle size of 1 to 10, preferably or hydrated crystalline zeolite A having a diameter of 2 to 5μ; 12.3 Sodium killbenzene sulfonate, AS is C14-C15 alkyl sulfonate. means sodium acid; non-ionic compound is about 6.5 moles per mole of alcohol alcohols and monoethoxylated and unethoxylated with ethylene oxide of Coconut alcohol from which alcohol has been removed is meaningfully called CnAE6.5T. (also abbreviation); DTPA is a granular material based on sodium diethylenetriaminepentaacetate. 151.97 100.00AS 9.44 111.18 LAS 2.92 5.82 Moisture 4.47 8.80 Sodium silicate (ratio 1.6) 1.35 2.6 (1 Sodium sulfate 6. 47 12.45 Sodium polyacrylate (Decoy 4500) 2.61 5.0 2PEG8000 1.18 2.27 Nonionic compound 0.48 0.89 Sodium carbonate L3.29 25.57 Brightener 0.20 0.311 Sodium aluminosilicate 9.11 17.53DTPA O, 270, 52 Fragrance 0.20 0.38 NApAA granules 2 [1,09100,0ONAPAA 2.86 46.96 L A S Q, 30 4.93 Sulfate and miscellaneous components 2.93 48.11 No. B Sm-like substance 33.8 8 100.0ON OB S 3.15 gl, 19 LAS　O,123,09 P E G 8000 Q, 19 4.90 Miscellaneous components 0.42 10.82 Zeolite granules' 12.00 100.00 Sodium aluminosilicate 7 ．． 39 B1.58P E G 8000 1.50 12.47 Nonionic compound Things 1.16 9.70 Moisture 1.66 13.83 Miscellaneous components 0.29 2.42 mixture 5KS-6 layered sodium silicate 15.84 protease (0,078■/g Live white 0.52 Sodium perborate monohydrate 1.33 Citric acid 6.79 C12-Cl4N-methylglucamide 1.58 Total final composition 100.0 0 1-base granules are prepared by spray drying an aqueous clarification mixture of the indicated ingredients. Prepare.

2 Freshly prepared samples of PAPAA wet cake [typically about 60% water, peroxy Approximately 2% of silicic acid available oxygen (AvO) (corresponding to approximately 36% of NAPAA) and the balance ( 4%) consisting of unreacted starting material] is obtained. This wet cake is NAAA It is a crude reaction product of (monononylamide of adipic acid), sulfuric acid, and hydrogen peroxide. The crude reaction product is then quenched by addition to water, filtered and distilled. Wash with water, phosphate buffer, and final suction filtration. Collect the ku. A portion of the wet cake is air-dried at room temperature, typically to about 5% AvO. (corresponding to approximately 90% NAPAA) and 10% unreacted starting material. obtain. When dry, the sample pH is approximately 4.5.

NAPAA granules are dried NAPAA wet cake (containing about 10% unreacted material). ) approx. 51.7 parts, C-line 12.3 Sodium alkylbenzenesulfonate (LAS) base (45% active content) approx. 11.1 parts, about 43.3 parts of sodium sulfate, and 30 parts of honcho ( Cυ1sINAl? T) Prepared by mixing in a mixer. After drying , the granules (containing about 47% NAPAA) passed through a magnetic 14 Tyler mesh sieve, By retaining all particles that do not pass through the NcL65 Tyler mesh Size the grains. The average amidoperoxyacid particle size (agglomerates) is approximately 5-40μ and The Dian particle size is about 10-20 microns as determined by Malvern particle size analysis.

3NOBS (nonanoyloxybenzene sulfonate) granules in 19913 Pauling U.S. Pat. No. 4,997,596, issued May 5th (incorporated as a reference).

4 Zeolite granules having the following composition are zeolite A mixed with Eirich RO8 energy. PEG3000 and CnAE6.5T in a energy-intensive mixer. Prepared by

Zeolite A (contains bound water) 7 (1,0 (176,99P E G 8000 10. go 12.49CnAE6. sT 8.40 9.72 Free water 1o , 80 0.80 PEG 8000 is in aqueous form containing 50% water and approximately 55″F (12, 8°C).

CnAE6.5T is in liquid state and kept at approximately 90″F′ (32,2°C) . The two liquids are pumped through a 12-element static mixer. Match it. The resulting binder material has an exit temperature of approximately 75″F (23,9°C) and a viscosity of about 5000 cps. PEG30 through static mixer The ratio of 00 and CnAE6.5T is 72:28, respectively.

The Eirich RO8 energy intensive mixer is operated in batch mode. First of all, Weigh and feed 34.1 kg of powdered zeolite A into the mixer pan. The mixer is , first rotate the pan counterclockwise at about 75 revolutions per minute (rpi), then -Start by rotating the blade clockwise at 1800 rpyz.

The binder material is then transferred from a static mixer to an Eirich containing zeolite A. Pump directly to RO8 energy intensive mixer. Binder material supply The speed is approximately 2 minutes.

The mixer continues mixing for an additional minute (approximately 3 minutes total batch time). Then, The batch is discharged and collected in a fiber drum.

The batch process is repeated until 225 kg of wet product has been collected. Next, this The discharge product of do. The drying step removes most of the i1M water and changes the composition as described above. . The total energy manpower by the mixer to the product in batch form is approximately 2.18 The speed of X109 kg/--S is approximately 1.31xlO12 kg/kg.

The resulting free-flowing agglomerates have an average particle size of about 450-500μ.

Example 26 Relatively high concentrations common in front-loading automatic washing machines over a wide range of temperatures, especially in Europe Liquid laundry detergent compositions suitable for use in water are as follows.

Ingredients Weight% Coconut alkyl (C12) N-methylglucamide 14CI4~15EO (2,25) Sulfate, Na salt 10,0 anhydrous CI2-14 alkenylcono ・Hyric acid' 4.0 Citric acid (anhydrous) 4.6 Protease (enzyme) 2 0.37 Termamil (enzyme, 3 0.12 Lipolase (enzyme) 0.38 Karezyme (enzyme) 5 0.12 Duquest 206OS6 1.0 NaOH (pH to 7.6) 5.5 1.2-Propanediol 4.7 Ethanol 4.0 Sodium metaborate 4.0 Ca C12G, 014 Ethoxylated tetraethylenepentamine 70.4 Brightener 8 0.13 Silane 9 0.04 Soil release polymer 10 0.2 Silicone (foam control) ii o, a Silicone dispersant 12 o, 2 Water and trace ingredients balance ’　Symbrax (5YNPRAX) 3 from ICI or from Monsando As a DTSA.

21.989 No. 0342177 of 15 November 989 % at 40g/fl as A, -ZeB.

Amylase from 3 Novo; % at 300 KNU/g.

Lipase from 4 Novo; % in 100 KLU/g.

Cellulase from 5 novo; % at 5000 CEvU/g.

6 Available from Monsanto.

From 7BASF as Rutinsol P6105.

8 Bayer Blanco Hall CPG766゜9 Union Carbide to A11 30 or Dynasylan φtriamino (DYNASYLAN TRI) from Hills Silane corrosion inhibitor available as AMINO).

10 Polyesters of U.S. Pat. No. 4,711,730.

11 Silicone antifoam agent available from Dow Corning as 02-3302 12 Silicone foam control agent available from Dow Corning as DC-3225C Dispersant for use.

★Preferred fatty acids are 12% oleic acid and each of stearic acid and linoleic acid. Freon containing 2% topped over a wide range of temperatures, especially in Europe. Granular laundry detergent composition suitable for use in relatively high concentrations common in load-loading automatic washing machines The items are as follows.

Ingredients Weight% Tsukaran CP5 (active bone as Na salt 3.52100%) 1 Duquest 2066 (100% as acid) 0.45 Zeolite A' (anhydrous , 2-5μ) 17.92CMC (100% active bone)' 0.47 Layered silica To S K S -612,9 tallow alkyl sulfate 2.82 (active bone 100%-Na salt) CI4-C15 alkyl sulfate 3.5 (100% active bone; Na salt) C-C alkyl EO(3) sulfate 1.76C16-018N-methylg Lucamide 4.1 Dopanol C12-C15EO (3) 3.54 Lipolase ( 100,0OOLU/g) 5 0.42 Savinase (4,0KNPU) 6 1.65 stearyl alcohol 0.35 Sodium percarbonate (coated) 22.3 Tetraacetylene diamine (TAED) 5.9 Zinc phthalocyanine 0.02 Water (from zeolite) remainder 1 Tsukaran is polyacrylic acid/sodium maleate available from Hoechst. be.

Monsando brand of 2-pentaphosphonomethyldiethylenetriamine.

3 Optical brightener available from Ciba Geigy.

4. Product name FIIJNFIX available from Metasaliton.

Noriporase lipolytic enzyme from 5 Novo.

Savinase protease enzyme from 6 Novo.

7X2-3419 is a silicone suds suppressor available from Dow Corning.

The method for producing granules consists of various tower drying, agglomeration, dry addition, etc. as follows. %teeth, For the finished composition.

A. Using standard techniques for clutching and blowing through the column, the following components are clapped: Crutch and dry in a tower.

Tsukaran CP5 3.52% Duquest 2066 0.45% Chino Pearl DMS 0.28% Magnesium sulfate 0.49% Zeolite A as anhydride 7.1% - Agglomeration of st - tallow alkyl sulfate 50% active paste of salt and 70% of C12-C15EO(3) sulfate % paste is flocculated with zeolite A and sodium carbonate according to the following recipe ( (contributes to detergent formulation after drying of aggregates).

Tallow alkyl sulfate 2.82% C12-15EO (3) sulfate 1.18% Zeolite A 5.3% Sodium carbonate 4.5% B2. - Sei Yoni B Uni Domu Tomoe 4 Jiku Otsu - 2" hi mini-j ヱ Satji upper ji 14ヱ2 1] Two" ≧ Ko25 Takekoichi (Uni P Yo1 & Yu2 and!Muuc Uni5 YoNYu f2L!ru Coaseamide aggregate - 016~01g glucose amide nonionic substance in methyl ether Dopanol CEO (3) present during the reaction of ster with N-methylglucamine Synthesize.

12-15 C12-15EO(3) reacts without producing undesirable cyclic glucose amides. 1. a melting point depressant that enables the reaction to take place; It works.

Dopanol C12-15EO(3) 20% and CI6-C18N-, Methyl Gluco - A surfactant mixture with 80% of samide was obtained and simultaneously with 10% of sodium carbonate. aggregate.

Second, the particles are then treated with sodium salt of 014-C15 alkyl sulfate and CE O(3) sulfate and ze12-15 Simultaneous coagulation with high activity paste (70%) of Olide A and excess sodium carbonate do. The particles were found in cold water containing C113-C18N-methylglucoseamide. Shows good dispersibility.

The total formulation of this particle (contributing to the detergent formulation after drying of the aggregates) is as follows.

Sodium carbonate 4.94% Zeolite A5.3% 014-C15 alkyl sodium sulfate 3.5%c 12-15E o (3 ) Sodium sulfate 0.59% C1 dry additive Add the following ingredients.

Bell carbonate 22.3% TAED (Tetraacetylethylenediamine) 5.9% Hoechst layered silica TOTO S K S-612, 90% citric acid 3.5% Lipolase 0.42% 1 (10,00[ILυ/g Sabinase 4, OK N P U 1.85% zinc phthalocyanine (photobleach ) 0.01% D, spray-on Dopanol CI2-15EO (3) 2.8Q% Fragrance 0.53% E. Foam suppressant Dow Corning Silicone Foam Inhibitor X2-3419 (High Molecular Weight Linear Silico 95% to 97% hydrophobic silica) to zeolite A (size 2 to 5%) μ), co-agglomerates with starch and stearyl alcohol binder. this grain The child has the following prescription:

Zeolite A O, 22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% For detergent formulations, for example, 85g of detergent in an AEG brand washing machine? 30℃, 40℃, 60”C OJ: and 90”C? i’) Used in /l/ and used in European washing machines. It exhibits excellent solubility, excellent performance and excellent foam control when used.

Example 28 In any of the foregoing examples, the fatty acid glucamide surfactant contains an equivalent amount of maltamide. Depends on surfactants or glucamide/maltamide surfactants derived from plant sugar sources. It can be changed. In the composition, the use of ethanolamide It seems to promote the cold and temperature stability of things.

Additionally, the use of sulfobetaine (also known as "sultaine") surfactant provides superior foaming. Give sex.

In cases where particularly high foaming compositions are desired, fatty acids of 014 or higher may be used to suppress foaming properties. less than about 5%, more preferably about 2% fatty acids of 014 or higher. It is preferred that there be less than, most preferably substantially no.

Therefore, formulators of high-foaming compositions desirably include such fatty acids with foam-inhibiting amounts. Avoiding the introduction of rehydroxy fatty acid amides into high foaming compositions and/or or will avoid the formation of 014 or higher fatty acids during storage of the finished composition. 1 One simple approach is to prepare the polyhydroxy fatty acid amides of the present invention. 2 ester reactants are used. Fortunately, amine oxide or The use of sulfobetaine surfactants avoids the negative foaming effects caused by fatty acids. can overcome some of the

Anionic optical brighteners with relatively high concentrations (e.g. 10% or more) of anionic surfactants agents or polyanionic surfactants, such as polycarboxylate builders. Formulators who wish to add brighteners to liquid detergents that contain water and polyhydroxy fatty acids It may be useful to premix with the amide and then add the premix to the final composition. You can find out something.

Polyglutamic acid or polyaspartic acid dispersant with zeolite builder Can be used usefully with detergents. AEE Fluid or Flake and DC-544 (Dow Corning) is another example of another antifoam agent useful herein.

Polyhydroxy fatty acid amide using trisaccharides and higher sugars, e.g. maltose In the production of 2, the linear substituent 2 is "capped" by a polyhydroxy ring structure. It will be recognized by those skilled in the art that this will result in the formation of polyhydroxy fatty acid amides. will be done. Such materials are fully intended and disclosed for use herein. Without departing from the spirit and scope of the invention as defined and claimed.

Submission of translation of written amendment (Article 184-8 of the Patent Law) 1. Display of patent application PCT/US 91107031 , name of invention 3. Patent applicant Address: One, Broctor, End, Cincinnati, Ohio, United States Gamble, Plaza (no street address) Name: The, Broctor, End, Gamble , Company 4, Agent (Postal code 100) 2-3 Marunouchi Otsu-chome, Chiyoda-ku, Tokyo 5. Date of submission of amendment September 1, 1992 6. List of attached documents The scope of the claims 1. Anionic detergent surfactant with IN or higher, nonionic detergent surfactant or cationic detergent surfactant detergent surfactants, or mixtures thereof, and any detergent adjuvants. A detergent composition comprising: (a) At least 1 weight of cytrate detergent builder (b) Formula (In the formula, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, oxypropyl, or a mixture thereof, and R2 is C-C hydrocarbyl. and Z is a linear hydrocarbon with at least 3 hydroxyls directly linked to the chain. Polyhydroxyhydrocarbyl having a carpyl chain or its alkoxylated derivative body) characterized by containing at least 1% by weight in the polyhydroxy fatty acid amide substance of A detergent composition containing a builder.

2. Is the ratio of citrate builder to polyhydroxy fatty acid amide 1:10? 10:1, preferably from 7:1 to 1:5.

3. The composition comprises at least 5% by weight of the cytrate builder and the Detergent according to claim 2, comprising at least 3% by weight in polyhydroxy fatty acid amide. Composition.

4. Regarding the polyhydroxy fatty acid amide, 'R1 is methyl and R is C11-C17 alkyl or alkenyl, and Z is -CH(CHOH) CH20H, where n is 3 to 5n 4. The composition of claim 3, wherein the composition is an integer of .

5. The composition according to claim 1, which is in liquid form and comprises a liquid carrier.

6. Alkyl sulfate, alkyl ester sulfonate, preferably methyl Ester sulfonates, alkyl ethoxylated sulfates, and alkylbenes one or more anionic sulfates selected from the group consisting of zenesulfonates or 6. The detergent composition of claim 5, further comprising a sulfonate surfactant.

7. The wash according to claim 6, comprising more than 10% by weight of cytrate builder. agent composition.

8. It is in granular form and contains solid zeolite builder in addition to the citrate builder. 2. A composition according to claim 1, characterized in that the composition is made of aluminum.

9. Polycarboxylate resin in hard water resulting in builder deficiency conditions. In order to improve the fabric cleaning performance of detergent compositions containing detergent, The formula for the composition (In the formula, R1 is H, C-C hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, oxypropyl, or a mixture thereof, and R2 is C-C hydrocarbyl. , Z has a linear hydrocarpyl chain with at least 3 hydroxyls Polyhydroxyhydrocarbyl, preferably C-CN-methylglucamide, C1 1~CN-Methyl maltamide, 011~Cl7N-methylph 1 At least 1% by weight of lucutamide or a mixture thereof) is added to the fabric. An improved method characterized by washing by a conventional method.

10, the R2 moiety in the polyhydroxy fatty acid amide is 015-C17 10. The method of claim 9, wherein the method is alkyl, alkenyl, or mixtures thereof.

11. The carboxylate builder preferably comprises at least one of the detergent compositions. 10. The method of claim 9, wherein both are citrate builder at a concentration of 5% by weight.

international search report ,,,Continuation of PCT/LIS 91107031 front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A ( BF, BJ, CF, CG, CI, CM, GA, GN, NiL, ~iR, SN , TD, TG), AT, AU, BB, BG, BR, CA, CH , C3, DE, DK.

ES, FI, GB, HU, JP, KP, KR, LK, LU, MC, MG, MN, MW, NL, No, PL, RO, SD, SE, SU

Claims (14)

[Claims] 1. One or more anionic detergent surfactants, nonionic detergent surfactants or cationic detergent surfactants detergent surfactants, or mixtures thereof, any detergent adjuvants, and any supplements. A polycarboxylate builder detergent composition comprising an auxiliary builder, (a) at least 1% by weight polycarboxylate detersive builder; and (b) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon. and Z has at least 3 hydroxyls directly linked to the chain. Polyhydroxyhydrocarbyl or its alkyl having linear hydrocarbyl chains (oxylated derivative) characterized by containing at least 1% by weight of a polyhydroxy fatty acid amide substance of A detergent composition containing a polycarboxylate builder. 2. The ratio of polycarboxylate builder to polyhydroxy fatty acid amide is 1 2. The composition of claim 1, wherein: 10:1 to 10:1. 3. The composition contains at least 3% by weight of the polycarboxylate builder and and said polyhydroxy fatty acid amide at least 3% by weight. detergent composition. 4. Polycarboxylate builders are ether polycarboxylates, ether hydropolycarboxylate, preferably oxydisuccinate, tartrae tomonosuccinate, or tartrate disuccinate, cytrate, poly selected from the group consisting of acetate, and succinate, and mixtures thereof. The detergent composition according to claim 1. 5. Regarding the polyhydroxy fatty acid amide, R1 is methyl and R2 is C 11-C17 alkyl or alkenyl, and Z is -CH2(CHOH)nCH2OH, and n is an integer from 3 to 5, Claim 3 The composition described in . 6. Regarding the polyhydroxy fatty acid amide, Z is derived from maltose, The composition according to claim 1. 7. Regarding the polyhydroxy fatty acid amide, Z is a monosaccharide, a disaccharide, and optionally and higher saccharides (the mixture comprises at least one disaccharide, preferably a malt). 2. The composition of claim 1, wherein the composition comprises at least 1% of 8. 2. The composition of claim 1 in liquid form and comprising a liquid carrier. 9. The weight ratio of polycarboxylate to polyhydroxy fatty acid amide is 7:1. 1:5, preferably within the range of 7:1 to 1:1. thing. 10. Alkyl sulfates, alkyl ester sulfonates, preferably methyl ester sulfonates, alkyl ethoxylated sulfates, and alkyl bases. one or more anionic sulfates selected from the group consisting of 2. The detergent composition of claim 1, comprising a surfactant or a sulfonate surfactant. 11. Claim 10 comprising more than 10% by weight of polycarboxylate builder. The detergent composition described in . 12. One or more anionic surfactants, nonionic surfactants or cationic interfaces Active agents, or mixtures thereof, polycarboxylate builders, any detergent supplements. Modifying the fabric cleaning performance of detergent compositions containing adjuvants and optional auxiliary builders In order to improve the detergent composition, the formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or a mixture thereof, and R2 is a C5-C31 hydrocarbon. and Z is a linear hydrocarbyl having at least 3 hydroxyls. polyhydroxyhydrocarbyl having a chain, preferably C11-C17N-methylene luglucamide, C11-C17N-methylmalutamide, or the above glucamide; polyhydrocarbons (in mixtures with maltamide or their alkoxylated derivatives) Contains at least 1% by weight of oxyfatty acid amide substance (polycarboxylate building block) (ratio of polyhydroxy fatty acid amide to polyhydroxy fatty acid amide is from 1:10 to 10:1), cloth An improved method characterized by washing the cloth in a conventional manner. 13. The Z moiety in the polyhydroxy fatty acid amide is obtainable from a vegetable source. 13. The method according to claim 12, wherein the method is derived from mixed monosaccharides, disaccharides and polysaccharides. 14. The R2 moiety in the polyhydroxy fatty acid amide is a C15 to C17 atom. 13. The method of claim 12, wherein the method is alkyl, alkenyl, or a mixture thereof.