JPH06501041A - Polyhydroxy fatty acid amides in zeolite/layered silicate built detergents - Google Patents

Abstract

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

Description

[Detailed description of the invention] Zeolite/Laminated Silicate Built Detergent polyhydroxy fatty acid amide in field of invention Zeolite also i! to support detergent formulations. Laminated silicate detergent builder or a mixture thereof is combined with IJ hydroxy fatty acid amide.

Background of the invention A variety of builder substances have been proposed for use in detergent compositions. Various functions such as substance ct, hardness, metal ion sequestering effect, peptizing effect, pH control, etc. Perform Noh. For many years, Tribo 1) 1 non-acid sodium 1 noumka (special number; preferred) As a new builder, recent developments in this field have led to zeolite and builder substances such as various polyJ carboxylates. Currently fully distributed Combined washed eggs j jt Zeolite builder or carboxylate builder is a mixture thereof Including things.

Development of high-performance detergent compositions that do not contain phosphates is a challenge for the egg washing industry. there were. Performance Perspective Forces λ and ζ, even the best zeolite builders are resistant to hard water. tl puts it in an "underbuilt" state. Furthermore, ordinary zeolite builder is The power to treat lucium hardness (and magnesium hardness) is not particularly effective. Laminated silicate builders have recently been discovered for use as agent builders.

However, laminated silicates handle magnesium hardness but do not control calcium hardness. It is somewhat inappropriate for

Currently, almost all phosphate-free be-duty granular detergents are made of zeolite-based detergents. Contains der. Zeolite built laundry detergent is widely available on the market, but its drawbacks is known to the formulator. Performance of zeolite or layered silicate builder compositions In order to improve A combining device is required. Detergent enzymes are commonly used to improve the performance of built-in detergent compositions. Substances such as bleach, mud removal polymers, bleaches and bleach activators are used.

Furthermore, for many years detergent formulators have found that detergent formulators can substitute equally effective alternatives to phosphate-built detergents. Efforts have been made to produce effective phosphate-free detergents, but petroleum or other non-renewable sources Increasing interest in detergent formulations that are less dependent on source-derived surfactants It shows.

According to the present invention, a few polyhydroxy fatty acid amide detergent compositions are All commonly used petroleum-derived surfactants, including killbenzene sulfonates. It has now been discovered that partial replacements can be used to produce superior overall cleaning performance. child These polyhydroxy fatty acid amides are primarily or entirely derived from natural, renewable sources. It is also degradable and has low toxicity to aquatic organisms. this Their polyhydroxy fatty acid amides are used as surfactants and adjuvants during use in detergent compositions. It can enhance the solubility and dissolution of builder salts. Even more surprising, these Polyhydroxy fatty acid amide of zeolite under underbuilt washing conditions and can improve the performance of laminated silicate builder detergents.

Briefly stated, the present invention comprises a zeolite and/or a layered silicate builder. Provided is an improved detersive surfactant having the following properties. According to the present invention, polyhydroxy fat Fatty acid amides are used in zeolite and/or layered silicate builder detergents. to improve detergent performance.

prior art Various polyhydroxy fatty acid amides are known in the art.

For example, N-acyl, N-methylglucoamide is J.

S., Gutsubai, M. A. Marcus, E. Chin, and P. L. By the fin ``The Thermotroptc Liquid-Crystalli'' ne Properties of’ SoIIe Straight Cha inCarbohydrate AIlphiphiles”, LIQUID 　CRYSTALS. 198g.

Volume 3, No. 11, l) described on p1569-1581, or A.

Müller whānau, ■. Zabel, M., Staif 7 and R. Hilgenfeld. by -Molecuira and Crystal Structure e of’ a Nonionic Detergent: Nonanoyl- N-sethylglucamide,-no. CheI1. Soc. Chea .

Co++uuun. , 198B. pp. 1573-1574 Ru. Recently, in biochemistry, for example, N-alkyl polyhydramblasts are used for the dissociation of physiological membranes. There has been substantial interest in using droxyamide surfactants. example For example, a journal article, N-D-Gluco-N-methyl-alkanamide e Compounds. a NewClass of Non-1onic Detergents for Membrane Bioche-mist ry,” Biochem. J. (1982), Vol. 207.pp 3 63-366 (J.E., Hildreth).

The use of N-alkyl glucoamides in detergent compositions has been discussed. rice National Patent No. 2,065,576 and British Patent No. 809,060 disclose that anion Contains a surfactant and a few amide surfactants, and N as a low-temperature foaming enhancer. - Detergent compositions to which methylglucoamide has been added. These transformations The compound contains N-acyl groups of higher straight chain fatty acids having 10-14 carbon atoms. Ma These compositions include alkali metal phosphates, alkali metal silicates, sulfates, and auxiliary substances such as carbonates. It also commonly uses fluorescent dyes, bleaches, fragrances, etc. Additional ingredients can be included in the composition that impart desired properties to the composition, such as is instructed.

U.S. Pat. No. 3,703,798 discloses that N-alkyl glucoamines and fatty acids The present invention relates to an aqueous detergent composition containing a condensation reaction product with an aliphatic ester.

The products of this reaction can be used in aqueous detergent compositions without further purification. It is said that Acylated groups as described in U.S. Pat. No. 2,717,894 It is also known to produce sulfurized esters of lucoamine.

PCT International Patent Application WO33104412 discloses that both polyhydroxy aliphatic group-containing These compounds are used in cosmetics, drugs, shampoos, etc. , as a surfactant in lotions and eye drops, as an emulsifier and formulation ingredient in pharmaceuticals. , and in biochemistry for the solubilization and solubilization of membranes, whole cells, or other tissue samples. It is said to be useful for the preparation of liposomes and liposomes. Within this disclosure, the formula R 'C0N(1?)C)121? "and R" CON (R) R' is written. , where R is hydrogen or an organic group, and R is an aliphatic hydrocarbon of at least 3 carbon atoms. The group, also R'', is the residue of an aldose.

European Patent 0.285,768 describes N-polyhydrin as a thickening agent in aqueous detergent systems. The present invention relates to the use of droxyalkyl fatty acid amides. Formula RIC(0)N( X) An amide of R2 is included. Here, R1 is C1-C17 (preferably C7-C 17) Alkyl, R2 is hydrogen, (, L-CL[l (preferably C1-CB)) a alkylene or alkylene oxide, and X is polyhydrocarbon having 4 to 7 carbon atoms. xyalkyl, such as N-methyl, coconut fatty acid glucoamide. This a The thickening properties of Mido can be applied to liquid surfactant systems containing paraffin sulfonates. This aqueous surfactant system has been described as being particularly effective in Rukylaryl sulfonate, olefin sulfonate, sulfosuccinic acid semi-ester Other anionic interfaces such as ter salts and fatty alcohol ether sulfonates Activator and fatty alcohol polygelcol ether, alkylphenol polyglyceride Recall ether, fatty acid polyglycol ester, polypropylene oxide-polymer Can contain nonionic surfactants such as polyethylene oxide mixed polymers. Ru. - As an example, paraffin sulfonate/N-methyl coconut fatty acid glucoa Mido/non-ionic surfactant shampoo formulations can be fried.

N-polyhydroxyalkyl fatty acid amide has a thickening effect as well as excellent skin tolerance. It is said to have certain characteristics.

The bar detergent described in U.S. Pat. No. 2,982,737 contains urea, sodium lauryl sulfate, Lithium anionic surfactant, and N-methyl, N-trubutyl laurylamide and N-alkyl selected from N-methyl, N-tulbutyl myristylamide Contains glucoamide nonionic surfactant.

Other glucoamide surfactants are described, for example, in DT 2,226°872, which The patent relates to detergent compositions containing one or more surfactants and polymeric phosphates. RxC N-acylpolyhydro of (0)N(R2)C)+2(C)IOH)ncH2DH improved by the addition of xy-alkyl-amine, where: R1 is a C1-C3 chain. alkyl, R2 is Clo-C22 alkyl, and n is 3 or 4. dirt suspension N-acylpolyhydroxyalkylamine is added as an agent.

The detergent compositions described in U.S. Pat. No. 3,654,166 contain anionic, at least one selected from the group consisting of ionic and nonionic surfactants; Surfactants and the formula RIN (Z)C(0)R2 as textile softeners N-acyl, N-alkyl, and polyhydroxalkyl compounds. This formula In, R1 is CLO-C227 RuF-ru, R2 is c7-C21 Furkyl, R1 and R2 have a total of 29 to 39 carbon atoms, and Z is polyhydroxyalkyl. So, this can be -CH2(CHOH)mcH20)1, where m is 3 or 4.

The related skin treatment cosmetic composition of U.S. Pat. No. 4,021,539 is contains a hydroxyalkylamine, which has the formula RIN(R)CH(C)IO H) Contains IIR2, where R1 is H1 lower alkyl, hydroxy-lower alkyl , or aminoalkyl and heterocyclic aminoalkyl, and R1, t R1 and Similarly, both cannot be H, and R2 i, tcH20H*f :, is C0OH.

The formaldehyde solution associated with French Patent No. 1.360,018 is I? C Stabilized against polymerization by the addition of an amide of (0)v(1?1)G, where R is a carboxylic acid functional group having at least 7 carbon atoms and R1 is hydrogen or A lower alkyl group, or G, is a glycidol group having at least 5 carbon atoms.

The glucoamine derivatives associated with German Patent No. 1,261,861 are used as wetting agents and and has the formula N(R) (R1) (R2), where R is Sugar residue of glucoamine, R1 is c10-C20 furkyl group, R2 is C1-C57 It is a syl group.

Heterocyclic amides or carboxylic acid esters thereof related to British Patent No. 745,036 Chemical intermediates, emulsifiers, wetting agents and dispersants, detergents, textile softeners It is said to be effective as such. This compound is 2N0R) (R1)C(0 )l? 2, where R is anhydrous hexanebentol or its carboxylic acid. R1 is a monovalent hydrocarbon group, and -C(0)R2 is a 2- It is an acyl group of a carboxylic acid having up to 25 carbon atoms.

U.S. Pat. No. 3,312,627 discloses anionic detergents and alkaline builder substances. Discloses a solid bar soap that contains substantially no fatty acids; tium soap and a few propylene oxide-ethylenediamine-ethylene oxide condensations polypropylene oxide-propylene glycol-ethylene oxide condensate, and A nonionic surfactant selected from polymerized ethylene glycol and a nonionic foaming agent. This foaming component contains a polyhydroxyacid of the formula RC(0)NRI(R2). RC(0) contains from about 10 to about 14 carbon atoms, and R1 and R2 are each H or a ci-ca alkyl group, and the alkyl groups have a total of 2 to 7 carbon atoms and a total of 2 to 6 substituted hydroxyl groups. A similar disclosure is No. 3,312,626.

Summary of the invention one or more anionic, nonionic or cationic detersive surfactants or with optional detergent additives and optional auxiliary buildings. In a built detergent composition comprising: Herein, the detergent composition includes: (a) at least 1% by weight of a zeolite or layered silicate detergent builder; or (b) at least 1% by weight of a polyhydroxy fatty acid amide of the formula A built detergent composition comprising: where R1 is HSCf, -C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, preferably is C1-C4 alkyl, more preferably C1 or C2 alkyl, and most preferably Preferably CI alkyl (i.e. methyl); also R2 is C5-C31 hydrocarbon bir, preferably straight chain C7-C19 alkyl or alkenyl, more preferably is straight chain C9-C17 alkyl or alkenyl or most preferably C11 -C17 alkyl or alkenyl or a mixture thereof; and Z is contains a linear hydrocarbyl having at least 3 hydroxyl groups tangentially connected Polyhydroxyhydrocarbyl or its alkoxylated derivative (preferably toxylated or propoxylated derivatives).

Preferably, zeolites, layered silicates or mixtures thereof and polyhydroxy fats are used. The weight ratio with fatty acid amide is about 1=10 to about 20=1, more preferably about 1=5 to about 1=1. from about 15:1, most preferably from about 1=3 to about 10=1.

Detailed description of the invention Polyhydroxy fatty acid amide surfactant detergent compositions typically contain at least about 1% from about 3% to about 50%, preferably from about 3% to about 30%, as described below. Contains droxy fatty acid amide surfactant.

The polyhydroxy fatty acid amide surfactant component of the present invention is a compound having the following structural formula. including, R1 Here, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or mixtures thereof, preferably C1-C4 alkyl, and Preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e. and R2 is C5-C31 hydrocarbyl, preferably linear C7-C 19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or or alkenyl or but also preferably C11-C17 alkyl or alkenyl or mixtures thereof: and Z is at least 3 hydrocarbons directly connected to the molecular chain. Linear hydrocarbyl-containing polyhydroxyhydrocarbyl having xyl groups or its alkoxylated derivatives (preferably ethoxylated or propoxylated derivatives) body).

Z is preferably derived from a reducing sugar in a reductive amination reaction. even more preferable Z is glycityl. Suitable reducing sugars are glucose, fructose, and malt. lactose, galactose, mannose and xylose. raw materials and High dextrose corn syrup, high fructose corn syrup You can also use high maltose corn syrup, as well as those listed above. You can use any sugar. These corn syrups contain sugar components for Z. produces a compound. It should be understood that this does not exclude other suitable ingredients. Z is Preferably, -C)12-(CHOH)n-CH20)! , -CH(CH20H)-(CH OH)n-1-CI20H.

-CH2-(C)10)1)2(CHOR')(CHOH)-CH201(and and its alkoxylated derivatives, where n is 3 to 5. and Ro is H or a cyclic or aliphatic monosaccharide. most favorable Preferred is n-4 glycityl, especially -CH2(CHOH)4-CH It is 20H.

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

R2-Co-N< is, for example, cocoaamide, stearamide, oleamide, lauro Amide, myristamide, cabricoamide, palmitamide, tallowamide, etc. It is.

Z is 1-dioxyglycityl, 2-deoxyfructityl, 1-deoxymulti Chil, 1-deoxymaltityl, N-1-dioxygalactityl, N-1-deo It can be ximanityl, 1-dioxymaltotriothytyl, etc.

Methods for producing polyhydroxy fatty acid amides are known in the industry. Generally, this amide is In a reductive amination reaction, an alkylamine is reacted with a reducing sugar to form the corresponding N-alkylamine. N-alkyl polyhydroxyamine is formed and then N-alkyl polyhydroxyamine is formed in the condensation amidation step. Reacting kill polyhydroxyamines with fatty acid esters or triglycerides of fats to form an N-alkyl, N-polyhydroxy fatty acid amide product. Therefore, it is manufactured. Production of various compositions containing polyhydroxy fatty acid amides The law has been disclosed. For example, British Patent No. 809,060, US Patent No. 2.96 5.576 and U.S. Patent No. 2,703,798, and U.S. Patent No. 1,9 No. 85,424 is cited as an example.

N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid In the production process of Mido, the glycityl component is derived from glucose and N- The alkyl or N-hydroxyl functionality is N-methyl, N-ethyl, N-propylene N-butyl, N-hydroxyethyl or N-hydroxypropyl; Trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate um, pentapotassium tripolyphosphate, lithium hexaoxide, sodium hydroxide, potassium hydroxide Lithium, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, alcohol Disodium tartrate, dipotassium tartrate, potassium sodium tartrate, tricitrate Sodium, tripotassium citrate, basic sodium silicate, basic potassium silicate um, basic sodium aluminosilicate and basic potassium aluminosilicate. In the presence of a catalyst selected from the group consisting of mixtures thereof, fatty methyl esters fatty esters selected from fatty acids, fatty ethyl esters and fatty triglycerides and N-alkyl- or N-hydroxyalkylglucoamine. The product is obtained by The amount of catalyst is preferably N-alkyl or N-hydro. Roxyalkyl-glucoamine molar basis, preferably from about 0.5 mol% to about 50 mol%, more preferably about 2.0 mol% to about 10 mol%. The reaction is Preferably, it is carried out at about 138°C to about 180°C for about 20 minutes to about 90 minutes.

If glycerides are used as a source of fatty esters in the reaction mixture, this reaction using from about 1 to about 10% by weight of the phase transfer agent, based on the weight of the total reaction mixture. Preferably, the phase transfer agent is a saturated fatty alcohol polyethoxy esters, alkyl polyglycosides, linear glycoamide surfactants and mixtures thereof Selected from things.

Preferably the method is carried out as follows.

(a) preheating the fatty ester to about 138°C to about 170°C; (b) N-alkyl or N-hydroxyl for heated fatty acid ester Add Lucyl Glucoamine and mix to the extent necessary to form a two-phase liquid/liquid mixture. and the step of (c) mixing the catalyst into the reaction mixture; and (d) stirring for a specified reaction time. stage.

When the fatty ester is a triglyceride, the weight of the reactant is from about 2% to about 20% of the preformed linear N-aluminum/N-hydroxyamate. The lukyl, N-linear glucosyl fatty acid amide product is added to the reaction mixture. this matures the reaction and increases the reaction rate. Detailed experimental procedures are shown below.

The polyhydroxy "fatty acid" amide material used in this method is or is manufactured primarily from natural, renewable, non-petroleum materials and is degradable. It provides formulators with additional benefits. These substances also have low toxicity to aquatic organisms. .

The method used to produce the polyhydroxy fatty acid amide of formula (1) Ester amides and cyclic polyhydroxy fatty acids along with droxy fatty acid amides Care must be taken that large amounts of non-volatile by-products such as amides are produced.

The levels of these byproducts will vary depending on the particular reactants and processing conditions. preferably The polyhydroxy fatty acid amide that is incorporated into the detergent composition is About 10% or less of the added polyhydroxy fatty acid amide-containing composition, preferably Provided in a form containing no more than about 4% cyclic polyhydroquine fatty acid amide . The preferred method as described above produces low levels of by-products, including this cyclic amide by-product. It is an advantage to produce things.

Zeolite and laminated silicate builder detergent compositions are made from zeolite or laminated silicates. Contains an acid salt builder, or a mixture thereof.

The level of zeolite and/or laminated silicate builder is determined by the final use of the detergent composition. varies widely depending on the location and its physical form. The detergent composition is at least about 1% Contains such builders. Liquid formulations typically contain from about 5% to about 50% 96, more preferably 5% to about 30% by weight builder. Granular formulation The product typically contains about 10% to about 80%, preferably about 15% to about 50% by weight. Contains builders. However, higher or lower builder levels are also excluded. shall not be allowed.

Preferably zeolite or layered silicate builders or mixtures thereof and The weight ratio with droxy fatty acid amide is about 1:10 to about 20=1, preferably about 1 =5 to about 15:1, most preferably about 3 to 10:1.

Zeolite builder is a type of aluminosilicate building material, and today's hebide It has gained importance in utility detergents, especially in granular formulations. used in this invention The zeolites produced may have a crystalline or amorphous structure and may be natural products or synthetically derived. be guided. Methods for making zeolite materials are known in the art. For example, U.S. Patent No. 3.9 See No. 85,669. This patent is cited as a reference. Preferred synthesis used in the invention Zeolite ion exchange resins are trademarked Zeolite A, Zeolite P (B ), and Zeolite X. Generally, zeolite builders are It has the following formula: Na2[:(A102)z　(Si02)yl　・xH2O where 2 and y are small an integer of at least 6, the molar ratio of 2 and Y is in the range of 1.0 to about 0.5, and X is about 15 an integer from about 264 to about 264, and the material contains Ca per gram of anhydrous aluminosilicate. Has a magnesium ion exchange capacity of at least about 50 milligrams of CO3 hardness. do. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange resin is It has the following formula: Na12[(A102)12(Si02)12 ・xH2O where X is approx. 30 to about 30, especially about 27. This material is known as Zeolite A.

Laminated silicate builders are also known in the art. Laminated sodium silicate is preferred. example See, for example, the layered sodium silicate builder of U.S. Pat. No. 4,644.839.

Use this as an example.

Preferably, detergents used at temperatures below about 50°C, particularly below about 40°C, are substantially free of borosilicate. Contains no acid-containing builders or boric acid-forming builders. In this case, "virtually "Contains no boric acid-containing builder or boric acid-forming builder" means 2% or more, preferably or more than 1%, more preferably about 0.5% or more boric acid-containing builder and boric acid. This means that it does not contain any acid-forming builder, and most preferably contains 0%.

Detergent surfactant system The detergent composition includes polyhydroxy fatty acid amide and zeolite builder, as well as one or contain multiple additional surfactants, which may be anionic, cationic or non-ionic. It can be used as a surfactant. Typically, this surfactant system is In addition to the hydroxy fatty acid amide, one or more anions and/or non- Contains ionic surfactant. For proactive overall cleaning with a wide range of cleaning conditions preferably contains an anionic surfactant. In particular, if the detergent composition sulfates, alkyl ester sulfonates (e.g. methyl ester sulfonates) alkyl alkoxylated sulfonates (e.g. (tersulfonates), alkyl alkoxylated sulfonates (e.g. alkyl ethoxylated sulfonates), and alkylbenzene sulfonates hardness-sensitive surfactants such as esters (e.g. linear alkylbenzenesulfonates). The advantages of the present invention are particularly realized when containing a sex agent. Ordinary nonionic surfactants , of alkyl ethoxylates or alkyl polyglycosides, e.g. Inclusion is also desirable.

Typically, the amount of additional detersive surfactant will range from about 1% to about 50% by weight of the detergent composition. %, preferably from about 3 to about 40% by weight, more preferably from about 5 to about 30% Weight%. Suitable surfactants are described below.

Alkyl ester sulfonate surfactant Alkyl used in the present invention Ester sulfonate surfactants are described in the Journal of the Ame rican Oil Chemists 5ocity-52 (1975), C sulfonated by S03 gas as described in pp. 323-329 Contains linear esters of 8-C20 carboxylic acids (e.g. fatty acids). Suitable raw materials are Contains natural fatty substances derived from tallow, palm oil and coconut oil.

Preferred alkyl ester sulfonate surfactants, particularly for use in detergents, are: This includes an alkyl ester sulfonate surfactant having the structural formula:

S　O3M where R3 is Cl11-C20 hydrocarbyl, preferably alkyl or combination, R4 is C1-C8 hydrocarbyl, preferably alkyl or its combination, or M forms a water-soluble salt with the alkyl ester sulfonate. It's on. Suitable salts include gold salts such as sodium, potassium and lithium salts. salts, and methyl-, dimethyl-, trimethyl and quaternary ammonium cations. Substituted or unsubstituted ammonium salts such as and dimethylpiperidinium, and alkanolamines, e.g. derived from nolamine, jetanolamine and triethanolamine Contains cations. Preferably R3 is C10-C16 alkyl, R4 is methyl, Chil or isopropyl. Particularly preferred is R3 of 014-〇lG. A certain sulfonic acid methyl ester.

Alkyl sulfate surfactant Alkyl sulfate surfactants are water-soluble salts or acids of the formula ROS03M; In the formula, R is C10-C24 hydrocarbyl, preferably C10-C24 alkyl. Alkyl or hydroxyalkyl having a kill moiety, more preferably C12 -C18 alkyl or hydroxyalkyl, M is H or a cation, e.g. For example, alkali metal cations (e.g. sodium, potassium, lithium cations) , and methyl-, dimethyl-, trimethyl and quaternary ammonium cations. Any substituted or unsubstituted ammonium cation, e.g. tetramethyl-ammonium and dimethylpiperidinium, and alkanolamines, e.g. Nolamine, jetanolamine, triethanolamine and mixtures thereof Contains cations derived from Typically, low temperature washing (e.g. below about 50°C) is preferably a C12-C16 alkyl molecular chain, and is preferably washed at high temperatures (e.g., about 50°C or higher). Above) is preferably a C1lli-C18 alkyl molecular chain.

Alkyl alkoxylated sulfate surfactant Alkyl alkoxylated sulfuric acid Salt surfactants are water-soluble salts or acids of the formula RO(A)ms03M, where R is substituted CLO-C24 alkyl, or C10-C24 alkyl moiety, preferably or C12-C20 alkyl and segmental hydroxyalkyl, more preferably is C12-C1g alkyl or hydroxyalkyl, A is ethoxy or pro- poxy units, m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or a cation, such as Metal cations (e.g., sodium, potassium, lithium, calcium, (such as sium), or ammonium or substituted ammonium cations. child In the case of alkyl ethoxylated sulfates as well as alkyl propoxylate sulfates salt or considered. Examples of substituted ammonium cations are methyl-, dimethyl-, tri- Methyl-ammonium cation, tetramethyl-ammonium and dimethylpi from quaternary ammonium cations such as peridinium, and alkanolamines. Derivative cations such as monoethanolamine, jetanolamine and Contains triethanolamine, as well as mixtures thereof. Examples of surfactants are CL2- CIll alkyl polyethoxylate (1,0) sulfate, C12-C1g alkyl Kylboriethoxyle-1(2,25) sulfate, C12-C187 alkyl polyeth xylate (3,0) sulfate, and C12-C[1 alkyl polyethoxylate (4,0) sulfate, where M is selected from sodium and potassium; Other anionic surfactants that can be used for mold cleaning purposes may also be included in the compositions of the present invention. It can be contained in These surfactants include soap salts (e.g. mono-, di- - Sodium, potassium, ammonium and salts such as triethanolamine ammonium salt), C9-C20 linear alkylbenzene sulfonate, C l1-C22 primary and secondary alkanesulfonates, C8-C24 olefins sulfonates, such as those described in British Patent No. 1.082.179; Sulfonate produced by sulfonation of pyrolysis products of lithium metal citric acid polycarboxylic acids, alkylglycerol sulfonates, fatty acylglycerides Rolesulfonate, fatty oleylglycerol sulfate, alkylphenol Ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphorus acid salts, isethionates such as N-acyl isethionate, acyl tartrate, meth Lutauride fatty acid amides, alkylsufucinamates and sulfosuccinates , diesters of sulfosuccinates (especially saturated and unsaturated C12-C18 diesters) esters), N-alkyl phosphates, and sulfates of alkyl polyglycosides. sulfate of lukyl polysaccharide (non-ionic non-sulfate compounds are listed below), branched primary alkyl sulfate, Formula 1? o(CH2CH20)kcH2cOO-M+(here(this R is C8-C22 alkyl, k is an integer from O to 10, and M is a soluble salt-forming cation) alkyl polyethoxy carboxylates such as those, and isethionic acid. Contains fatty acids that have been sterilized and neutralized with sodium hydroxide.

Resin acids and hydrogenated resin acids are also suitable. For example, rosin, hydrogenated rosin, and Resin acids present in or derived from oils and hydrogenated resin acids are also suitable.

Other examples are “5urrace Active Agents and De targets-(Vol, I and II by 5chva, rts, Perry and Berch). Also various surfactants No. 3,929,678 (column 23, line 58 to column 29, line 23) (This is used as an example).

Nonionic detergent surfactant Suitable nonionic detergents carboxymethyl are generally described in U.S. Pat. No. 3,929,67. No. 8, column 13, line 14 to column 16, line 6, and this is cited as an example. A valid non- Non-limiting examples of surfactants are listed below.

1. Alkylphenol oxidation polyethylene, polypropylene and polybutylene Preferred are polyethylene condensates, generally oxidized polyethylene condensates. These compounds are directly Alkyl containing alkyl having about 6 to about 12 carbon atoms in chain or branched chain form Contains the condensation product of phenol and alkylene oxide. Preferred embodiment The amount of ethylene oxide is about 5 to about 25 moles per mole of alkylphenol. Exist in proportion. A commercially available nonionic surfactant of this type is marketed by GAF. IgepalTMc.

-630 and TritonTM marketed by Rohm and Haas Including X-45, X-114, X-100, and X-102. These surfactants are Generally alkylphenol alkoxylates, e.g. alkylphenol ethoxylates called sylate.

2. Condensation products of aliphatic alcohols and about 1 to about 25 moles of ethylene oxide. fat The alkyl molecular chain of the aliphatic alcohol may be a straight chain or a branched chain, and the first or second and generally contain about 8 to about 22 carbon atoms. Particularly preferred is from about 10 to about Alcohols with alkyl containing 20 carbon atoms and per mole of alcohol It is a condensation product with 2 to about 18 moles of ethylene oxide. This type of commercially available non-ionic Examples of surfactants include Ter, both commercially available from Union Carbide. gi tolT old 5-3-9 (C11, -C15 linear secondary alcohol and 9 mol of condensation product with ethylene oxide), and TergitolTM24-L-8NM v (C12-CI4 primary alcohol with narrow molecular weight distribution and 6 moles of oxidized ether) (condensation product with tyrene); NeodolTM, marketed by Shell Chemical Co. 45-9 (Condensation of C14, -C15 linear alcohol with 9 moles of ethylene oxide) product), NeodolTM23-6.5 (C12-CI3 linear alcohol and Condensation product with 6.5 moles of ethylene oxide, NeodolTM45-7 (C1 4-CI5i-like alcohol and 7 mol of ethylene oxide condensation product), Ne odolTM45-4 (C14-C15 linear alcohol and 4 moles of ethylene oxide) (condensation product with P&G) and KyroTMEOB ( It is a condensation product of a C13-C15 alcohol and 9 moles of ethylene oxide). child These surfactants are commonly referred to as alkyl ethoxylates.

3. Hydrophobicity formed by condensation of propylene oxide and propylene glycol Condensation product of ethylene oxide with a base. The hydrophobic portion of these compounds is preferably It has a molecular weight of about 1500 to about 1800 and is water-insoluble. This hydrophobic part On the other hand, adding polyoxyethylene moiety increases the water solubility of the molecule as a whole. until the polyoxyethylene content is approximately 5096 of the total weight of the condensation product. , the liquid character of the product is retained, and this state is due to condensation with about 40 moles of ethylene oxide. corresponds to An example of this type of compound is Pluro, marketed by BAS F. Contains a few of the nicTM surfactants.

4. Ethyl oxide with the product resulting from the reaction of propylene oxide and ethylenediamine condensation product of ren. The hydrophobic moieties of these products are similar to that of ethylenediamine. of the reaction product with propylene oxide, generally from about 2,500 to about 300 It has a molecular weight of 0. This hydrophobic moiety is condensed with ethylene oxide and the condensation product is The composition contains about 40% to about 80% by weight polyoxyethylene and about 5,000% to about 80% by weight polyoxyethylene. It has a molecular weight of about 11,000.

An example of this type of non-ionic surfactant is Tetroni, marketed by BASF. Contains a few cTM compounds.

5. Semipolar nonionic surfactants are a special category of nonionic surfactants. , which has one alkyl moiety of about 10 to 18 carbon atoms and an alkyl group or and a hydroxyalkyl group of about 1 to 3 carbon atoms. a water-soluble amine oxide containing two moieties; one of about 10 to 18 carbon atoms; Alkyl moieties, alkyl groups and hydroxyalkyl moieties of about 1 to 3 carbon atoms. a water-soluble oxidized phosphide comprising two moieties selected from the group consisting of a kill group and a kill group; one alkyl moiety of about 10 to 18 carbon atoms; and a hydroxyalkyl group of about 1 to 3 carbon atoms. and a water-soluble sulfoxide containing two moieties.

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

where R3 is an alkyl group containing about 8 to about 22 carbon atoms, hydroxyalkyl group or alkylphenyl group or mixtures thereof, R4 has about 2 to about 3 carbon atoms. alkylene group or hydroxyalkylene group or a mixture thereof; X is O to about 3: and each R5 is an alkyl group or a hydroxyl group containing about 1 to about 3 carbon atoms. is a polyethylene oxide group containing a lukyl group or about 1 to about 3 ethylene oxide groups. . The R5 groups are bonded to each other via an oxygen or nitrogen atom to form a cyclic structure I can do things.

These amine oxide surfactants are particularly suitable for C10-C18 alkyl dimethyl amines. Mine oxide and C8-C12 alkoxyethyldihydroxydiethylamine Contains oxide.

6. Hydrophobic containing about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms U.S. Patent No. 4 with

565, 647, and from about 1,3 to about 1 0, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 Polysaccharides with hydrophilic groups containing saccharide units, e.g. polyglyco Sid. Any reduced saccharide containing 5 or 6 carbon atoms can be used, e.g. Glucosyl moieties include glucose, galactose and galactosyl moieties. (Optionally, hydrophobic groups can be placed in the 2nd and 3rd positions.) , the glucose opposite the glucoside or galactoside, attached at position 4, etc. or galactose). One place of additional Satsukarid unit and preceding Satsu There are inter-saccharid connections between the 2nd, 3rd, 4th and/or 6th positions of the carid unit. There may be cases where

Optionally, a port linking the hydrophobic moiety and the polysaccharide moiety. Real kylene oxide is present, but this is undesirable. Preferred Alkire Ethylene oxide is ethylene oxide. Representative hydrophobic groups range from about 8 to about 18, preferably preferably saturated or unsaturated, branched or unsaturated, containing from about 10 to about 16 carbon atoms. Contains branched alkyl groups. Preferably, the alkyl group is a straight chain saturated alkyl group. Ru. Alkyl can contain up to about 3 hydroxyl groups and/or poly The alkylene oxide molecular chain has up to about 10, preferably up to 5 alkylene oxide chains. Can contain cytomoieties. A suitable alkyl polysaccharide is octyl , nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl hexadecyl, heptadecyl, and octadecyl, g, tri, tetra -, penta- and hexa-glucoside, galactoside, lactocyto, glucose , fructocyto, fructose and/or galactose. proper mixture Things are coconut alkyl, di, tri, tetra-1 and pentaglucoside, and tallow alkyl tetra-1 and pentaglucoside, and tallow alkyl Includes tetra-, penta-, and hexa-glucosides.

Preferred alkyl polyglucosides have the formula:

Here, R2 is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkyl. selected from the group consisting of rukylphenyl and mixtures thereof, in which the alkyl group is about 10 to about 18, preferably about 12 to about 14 carbon atoms, where n is 2 or is 3, preferably 2; t is 0 to about 10, preferably O; and X is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2. It is 7. Glycodyl is preferably derived from glucose. these compounds To produce the alcohol or alkyl polyethoxy alcohol is first formed This is then reacted with glucose or a glucose source to form glucosides. (bond at position 1). Next, the 1st place and the 2nd place of the preceding glycosyl unit. Additional glycosyl unit between the 53-14- and/or 6-position, preferably the 2-position Combine the cuts.

7. Fatty acid amine surfactant having the following formula 20 where R6 is an atom containing about 7 to about 21 (preferably about 9 to about 17) carbon atoms; alkyl group, and each R7 is hydrogen, CL-C4 alkyl, CL-C4 hydroxyalkyl group, and each R7 is hydrogen, CL-C4 alkyl, CL-C4 hydroxyalkyl selected from the group consisting of kill and =(C2H40)xH, in this formula X is 1 to 3.

Preferred amides are C8-C20 ammonia amide monoethanolamide, Jeta These are nolamide and isopropaturamide.

cationic surfactant Cationic detersive surfactants can be included in the detergent compositions of the present invention. Catio The surfactant is ammonia such as alkyl dimethyl ammonium halide. These surfactants have the formula: where R2 is an alkyl alkyl or alkylbenzene having about 8 to about 18 carbon atoms in the molecular chain; group, each R3 is -CHCHO, -CH2Cl (CH3)-1-CHC1 ((C )I201()-, -CH,, CH2Cl,, - and mixtures thereof each R4 is C1-C4 alkyl, C1-C4 hydroxyalkyl; Kyl, benzyl, a cyclic formula formed by combining two R4 groups ○hexose or hexose polymer having a molecular weight of OO or less) and y is selected from the group consisting of hydrogen when non-zero; R5 is the same as R4, or R 2 plus R5 is an alkyl chain having a total of about 18 or less carbon atoms; each y is O to about 10, and the sum of y is 0 to about 15, and X is any compatible anion. It is.

Other cationic surfactants that can be used in the present invention are U.S. Pat. No. 44, this is incorporated into the detergent composition of Kawasui's invention. can be done. These surfactants are aliphatic derivatives of secondary or tertiary amines or or aliphatic groups in aliphatic derivatives of heterocyclic nodes 2 and tertiary amines It can be explained as a difference in technique. One of the aliphatic derivatives is at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one Contains anionic water-soluble groups such as carboxy, sulfonate, sulfate.

For examples of amphoteric surfactants, see U.S. Pat. example).

Furthermore, a Zvitter ionic surfactant can be incorporated into the detergent composition of the present invention. Ru. This class of surfactants broadly includes derivatives of secondary and tertiary amines, heterocyclic Section 2 and derivatives of tertiary amines, or quaternary ammoniums, quaternary phosphoniums or Alternatively, it can be explained as a derivative of a tertiary sulfonium compound. Zvitta ion For examples of surfactants, see U.S. Pat. No. 3,929,678 (which is incorporated by reference). do).

Amphoteric surfactants and Zwitterionic surfactants generally contain one or more Used with ionic and/or nonionic surfactants.

auxiliary builder The detergent compositions of the present invention provide inorganic and organic detergent solutions to aid in mineral hardness control. It can contain auxiliary builders including Lugu. A typical amount of auxiliary builder is From about 5% to about 200% of the weight of the olite/layered silicate bilgoux.

Inorganic detergent builders include alkali metal salts of phosphates, ammonium salts and alkaline nolammonium salts (e.g. tripolyphosphate, birophosphate and glass polymer metaphosphates), phosphonates, phytates, silicates, carbonates ( (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates It is not limited to this. boric acid builder, and during storage or washing conditions of detergents. Builders containing boric acid-forming substances that can form borates in You can also use boric acid builder (also called boric acid builder). Preferably below about 50℃ , particularly in compositions of the invention for use at wash temperatures below about 40°C. Use boric acid builder.

Examples of silicates are alkali metal silicates, especially 1.6+1 to 3.221 It has a 5i02:Na2O ratio of 5i02:Na2O. However, magnesium silicate etc. Other silicates can also be used. These are crystals in granular formulations. As a bunning agent, as a stabilizer in oxygen bleaches, and as a component in foam control systems. useful as.

Aluminosilicates other than zeolites can also be used. Generally, aluminoke The icate salt has the empirical formula MZ(zA102.ysI02), where M is sodium , potassium, ammonium or substituted ammonium, and 2 is about 0.5 to about 2, and y is 1, but it does not necessarily have to be within the range of the formula of the zeolite. stomach.

Examples of carbonate bilgo are alkaline earth metal and alkali metal carbonates, including carbonates. acid sodium and sesquicarbonate and as described in German Patent Application No. 2,321,001. Contains a mixture with ultra-fine calcium carbonate such as This patent is cited as a reference.

Phosphate builders and phosphonate builders can be used, but generally Instead of these builders, zeolite/layered silicate building blocks and Therefore, it is desirable to use other auxiliary builders and detergent additives. Therefore these builder is included at a low level even if it exists. Preferably the phosphate builder is 10% or less of the total amount of builder in the composition, more preferably about 5% or less, most preferably Preferably, it is contained at 0%.

Examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium and and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium Thorium polymetaphosphate with a degree of polymerization of about 6 to about 21, and It is a tinate salt.

Examples of phosphonates are the salts of ethane 1-hydroxy-1,1-diphosphonic acid, especially Sodium and potassium salts, water-soluble salts of methylene diphosphonates, e.g. trisodium and tripotassium salts and water-soluble salts of tylene diphosphonic acid, e.g. Ethylidene isopropylidene, benzylmethylidene and helomethylidene phosphate trisodium and tripotassium. Phosphate bilgoux salts of the type mentioned above are Nos. 3,159,581 and 3.213.030, U.S. Patent No. 3,42 No. 2,021, and U.S. Patent Nos. 3,400,148 and 3°422.1. No. 37 and cites these patents.

Organic detergent builders suitable for use in the present invention include various polycarboxylic acid compounds. Including, but not limited to (Xo In this case, "polycarboxylic acid" refers to a plurality of preferred or t) a compound having at least 3 carboxylate groups.

Polycarboxylate builders are generally added to the composition in acid form, but It can also be added in the form of a water-soluble salt. Alkali metals when used in salt form (e.g. sodium, potassium and lithium or alkanol ammonium salt) is preferred.

Polycarboxylate builders include various categories of useful substances . One important category of polycarboxylate builders is ether polycarboxylic bokin rate is disclosed for use as a detergent builder.

Examples of useful ether polycarboxylates are described in U.S. Pat. No. 3,128,287. and U.S. Pat. No. 3,635.

830, including oxydico/X-phosphate salts. These patents Use as an example.

Types of ether polycarboxylates useful as builders of the present invention C++ (A) (COOX)-CH (COOX)-0-CH (COOX )-CH (COOX) (B) Here, A is H or OH. B is H or - 0-CH(COOX)-C)+2(COOX), X is H or salt-forming cation It is. For example, in the above formula, if A and B are both H, then the compound is oxydisuccinic acid and its water-soluble salts. If A or OH and B is H, then chemical The compound is tartaric monosuccinic acid (TMS) and its water-soluble salts. A is H and B is -0-CH(COOX)-CH2(COOX) If the compound is dicotartrate Huccinic acid (TDS) and its water-soluble salts. A mixture of these builders is Particularly suitable for use in the light. Particularly preferred are TMS and TDS. The mixture has a weight ratio of about 97=3 to about 20:80. These bits Luder is described in US Pat. No. 4,663,071.

Suitable ether polycarboxylates are cyclic compounds, particularly those described in U.S. Pat. No. 3,923 , No. 679, No. 3,835.

No. 163, No. 4.158.35, No. 4.120,874, and No. 4.10. 2,903.

Another effective detergent builder is the ether hydropolymer represented by the structural formula below. Contains recarboxylate.

HO-EC(R) (COOM)-C(R>(COOM)-0]n-H here M is hydrogen or a cation, preferably an alkali metal, in which the salt obtained is water-soluble , ammonium or substituted ammonium cation: n is 2 to about 15 (preferably is 2 to 10, more preferably 2 to 4), and each R is the same or different. selected from hydrogen, CL-4 alkyl or Cl-4 substituted alkyl (preferably hydrogen).

Still other ether polycarboxylates are maleic anhydride and ethylene or is a copolymer with vinyl methyl ether, 1.3.5-trihydroxybenzene- Contains 2°4.6-dolisulfonic acid and carboxymethyloxysuccinic acid.

In addition, organic polycarboxylate builders can be Including ammonium and substituted ammonium salts. An example is ethylene diamine tet Sodium, potassium, lithium and ammonium in triacetic acid and nitrilotriacetic acid ammonium salts and substituted ammonium salts.

Also, mellitic acid, succinic acid, polymaleic acid, benzene 1,3.5-chilic acid polycarbonate such as carboxylic acid, carboxymethyloxysuccinic acid and its water-soluble salts. Contains boxylate.

Citrates, such as citric acid and its water-soluble salts (especially the sodium salt), are heavy is a particularly important polycarboxylate builder for liquid detergent compositions. However, it can also be used in granular compositions.

Other carboxylate builders include the carboxylate builders described in U.S. Pat. No. 3,723.322. Contains boxylate hydrocarbons.

This patent is cited as a reference.

Further, in the detergent composition of the present invention, the detergent composition described in U.S. Pat. 3,3-dicarboxy-4-oxy-1,6-hexanedioate and related compounds things are appropriate. This patent is cited as a reference. A useful succinic acid builder is C5-20 Contains alkyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl It is uccinic acid.

Alkyl succinic acid typically has the general formula 1? -CH(COOH)CH2(C0OH ), i.e. in succinic acid derivatives as described in the above-mentioned patent, R is carbon Hydrogenides, such as C10-20 alkyl or alkenyl, preferably C12-1 6, or R is hydroxyl, sulfo, sulfoxy or sulfone It is replaced by the replacement part.

Succinic acid builders include their sodium, potassium, ammonium and It is used in the form of water-soluble salts such as lukanol ammonium salt.

Examples of succinate building blocks are lauryl succinate, myristyl succinate, and palmityl. Succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl Contains succinate, etc. Lauryl succinic acid is the preferred builder of this group. Therefore, it is described in European Patent Application No. 86200690.510,200,263. There is.

Also examples of useful builders are carboxymethyloxymalonic acid, carboxymethyl Oxysuccinic acid, ciscyclohexane-hexacarboxylic acid, ciscyclopentane - Sodium and potassium salts of tetracarboxylic acids and water-soluble polyacrylic acids salt and a copolymer of maleic anhydride and vinyl methyl ether or ethylene. (Polyacrylates with a molecular weight of about 2,000 or more are effective as dispersants. available).

Other suitable polycarboxylates are those described in U.S. Pat. No. 4,144,226. It is a lyacetal carboxylate. This patent is cited as a reference. These polyas Cetal carboxylate is an ester of glyoxylic acid under polymerization conditions. It is produced by reacting with a polymerization initiator. The resulting polyacetal cal Rapid decomposition in alkaline solutions by attaching boxylate esters to chemically stable end groups and then converted to the corresponding salt and added to the surfactant.

Polycarboxylate builders are also described in U.S. Patent No. 3,308,067. It is. This patent is cited as a reference. These substances are maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Contains water-soluble salts of homo- or copolymers of any aliphatic carboxylic acid.

Other organic builders known in the art can be used.

For example, using monocarboxylic acids with long chain hydrocarbyl and their water-soluble salts I can do that. These include substances commonly referred to as "soaps". Typically, (chain lengths of , 10-20 are used. The hydrocarbyl can be saturated or unsaturated. .

enzyme For example, removal of stains of protein groups, carbohydrate groups or tylglyceride groups; Enzymes may be incorporated into detergent compositions for various purposes, such as preventing dye transfer. Contains. Enzymes included include protease, amylase, lipase, and cellular peroxidases, and peroxidases, as well as mixtures thereof. Also, enzymes can be can be of plant, animal, bacterial, fungal and yeast origin. Wear. However, the choice depends on pH activity and/or optimal stability, thermal stability, It is governed by various factors such as stability to detergents and builders.

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

Suitable examples of proteases are B, 5ubtilis and B, lichenif It is a subtilisin obtained from a specific bacterial species of Orms. Other suitable proteases is obtained from Bacillus sp., has maximum activity within the pH range of 8-12, and Novo It is commercially available under the trademark Esperase R from Industries A/S. Ru. Novo's British Patent No. 1,243,78 discloses a method for producing the second enzyme and similar enzymes. It is stated in No. 4. Commercial proteolysis suitable for removing protein-based stains The enzyme is sold to Novo Industries A/S (Denmark) by Yotte Sho I. I will sell SAVINASETM to LACALSETM. and International Blo-3 synthetic s.

Inc. (Netherlands) under the trademark MAXATASE. nothing.

Among the category of proteolytic enzymes are those of particular interest for liquid detergent compositions. The enzymes referred to herein are protease A and protease B. protea -se A and its manufacturing method are described in European Patent Application No. 130.756, which is cited as a reference. do. Protease B replaces tyrosine at position 217 of its amino acid sequence. It is a proteolytic enzyme that differs from protease A in that it has leucine in the . Protease B is described in European Patent Application No. 8703761.8, which is cited as a reference. do. The method for producing protease B is also described in European Patent Application No. 130.756. Use this as an example.

Amylases are described in detail, for example, in the aforementioned British Patent No. 1,296°839. α-Amylase derived from special B, ljcheni forms including. Starch hydrolase is, for example, International Blo- 8ynthetics RAPIDASETM Oyohi N0VOINDLISGT Including RIES' TERMAMYL.

The cellulases used in the present invention are bacterial cellulases or fungal cellulases. Contains both laases. Preferably, these enzymes have an optimum pH of 5 to 9.5. do.

Suitable cellulases are described in U.S. Pat. No. 4,435,307, which is incorporated by reference. However, this cellulase is produced from 1 uo + 1 colajnsolens Fungal cellulases are disclosed. A suitable cellulase is GB-^-2,07 5,028° CB-A-2,095,275 and DE-O8-2,247,8 It is described in 32.

Examples of these cellulases are Humicola insolens (Humicola insolens). ola grisea var, thermoidea), especially Hum icola Cellulase produced by bacterial species DSM 1800, Bacillus N Cellulase 212-producing bacterial species belonging to the species or genus Aerosonas cellulases produced from marine molluse (Dolab ella Auricula Solander) hepatopancre This is cellulase extracted from as.

The lipase that can be used in the detergent composition of the present invention is disclosed in British Patent No. 1.372.034. Pseudomonas stutzeri ATCC19,154 etc. described in is produced by microorganisms of the genus Pseudomonas, and cites this patent. shall be. Suitable lipases include the microorganism PseudoIlonas fluoresc. ens IAM 1057, positive immunological cross-reaction with lipase antibody Including those indicating. This lipase and its manufacturing method are disclosed in Japanese Patent Application No. 53-20487. It is described in. This lipase is AIIano pharmaceutical + Co, Ltd.

It is commercially available from Nagoya under the trademark Lipase P″A11anO″, which is shown below. It is called ``Amanor P''. These lipases are activated by 0υchterlony. The known standard immunodiffusion method (Acta, Med, 5can, 133.pp7B) -79 (1950)) to show positive immunological cross-reactivity with Amanor P antibodies. Must be.

The immunological cross-reaction method between these lipases and Amanor P is described in U.S. Patent Nos. 4 and 7. No. 07,291, which is cited as a reference. Representative examples of these lipases is Amanor P lipase, lipase ex Pseudoionas f’rag iFERN P 1339 (commercially available under the trademark Amano-B), Lipase ex P seudoaonas n1troreducens var, l1polyt icua FERMP1338 (commercially available under the trademark Amano-CES), lipase e x Chroiobacter viscosum % e.g. Chroioba cterviscosum var, Iipolytjcum NRRLB 3673 (commercially available from Toyo Jojosha, Tagata, Japan), and U, S, A, Bio cheo+1calCorp, USA and Disoynth Co, Ola ChrotAobacter viscosui l1paSe commercially available from S, and 1ipases ex Pseudomonas gladioli It is.

peroxygen with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. An oxidase enzyme is used.

These enzymes are used as "solution bleaches". i.e. removed from the substrate during washing. Used to prevent removed dyes or pigments from migrating to other substrates in the wash solution. used. Peroxidase enzymes are known in the industry and include, for example, horseradish. Peroxidases, ligninases and chloro- and promoperoxiders haloperoxidase such as ze. Peroxidase-containing detergent compositions include, for example: It is described in PCT patent application WO391099813, which is cited as a reference.

A wide variety of enzyme materials and means of incorporating them into synthetic detergent particles are disclosed in U.S. Pat. No. 553,139 (this patent is cited as a reference). More US patents Other enzymes are described in No. 4.101.457 and U.S. Pat. No. 4,507,219. and cites these patents.

Enzyme materials and methods for their incorporation for use in liquid detergent formulations are disclosed in U.S. Pat. No. 4,261. , No. 868, and the enzyme is, in principle, about 5 times per duram composition. mg of active enzyme, more typically from about 0.05 g to about 3 mg. Enough levels are combined.

For granular detergents, fermentation is used to minimize dust formation and increase storage stability. It is preferred to coat the enzyme with an additive that is inert to the enzyme. The technology is business It is well known in the world. For liquid formulations, enzyme stabilization systems are used. Water-based detergent set Enzyme stabilization techniques for products are well known in the art. Stabilizing enzymes in aqueous solutions1 Three technologies include calcium acetate, calcium formate and calcium propionate. Free calcium ions from any source are used. Calcium ions are short It can be used with chain carboxylates, preferably formates. For example, US patent See No. 4.318,818. Use this as an example.

Methods using polyols such as glycerol and sorbitol have also been proposed. There is. Also alkoxy alcohols, gelkyl glycoethers, polyhydric alcohols and polyfunctional aliphatic amines (e.g. jetanolamine, triethanolamine, diethanolamine) mixtures with alkanolamines (such as isopropanolamine), and boric acid and or alkali metal borates can be used. Furthermore, enzyme stabilization technology The technique is described in U.S. Patent Nos. 4,261.868 and 3.600.319. , both of which are cited, and European Patent Publication No. 0.199,405, European Special No. See No. 86200586.5. Non-boric acid and borate stabilizers are preferred. Ma U.S. Pat. Nos. 4,261°868, 3,600,319, and 3,5 No. 19.570 describes an enzyme stabilization system.

Bleaching compounds - bleaching agents and bleach activators The detergent compositions of the present invention may include a bleaching agent, or a bleaching agent and one or more bleaching agents. Bleach compositions containing several bleach activators can be included. This bleaching compound is used If used, it will be about 1% to about 20% of the detergent composition, more preferably about 1%. present at levels of from about 10% to about 10%.

Bleaching compounds are generally optional ingredients in non-liquid formulations, such as granular detergents. Ru. The amount of bleach activator, if present, can range from about 1% to about 60% of the detergent composition, and It typically ranges from about 0.5% to about 40%.

The bleach used may be used on textiles, hard surfaces or other selected purposes. Any bleaching agent presently known or to be known in detergent compositions may be used. can be used. These bleaches include oxygen bleach as well as other bleaches. . For washing conditions below about 50°C, particularly below about 40"C, the laundry composition Contains no acid salts or does not contain borates in situ during storage or washing conditions. It is preferable not to contain a substance that forms boric acid (boric acid forming substance). Therefore, something like this In some conditions, it is preferable to use non-borate bleaches or non-borate-forming bleaches. Yes. Preferably the detergents used at these temperatures are borates and boric acids. Substantially free of salt-forming substances. In this case, ``borates and borate-forming substances'' "Substantially free of" means that the composition contains 2% or more of borate-containing substances and Contains no acid-forming substances, preferably does not contain more than 1%, more preferably or 0%.

One category of bleaching agents used in the compositions of the invention are percarboxylic acids and and its salts. An example of this class of bleach is hexahydrate monoperoxyphthalic acid Magnesium, meta-chloroberbenzoic acid, 4-nonylamino-4-oxoper Contains magnesium salts of oxybutyric acid and diperoxidedecanedioic acid . Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781 and U.S. Pat. No. 46, European Special No. 0.133,354 and U.S. Patent No. 4,412.934 No. 1, and all of these are incorporated by reference. A highly preferred bleaching agent is US 6-nonylamino-6-oxoper as described in Patent No. 4,634,551. Contains oxycaproic acid. This patent is cited as a reference.

Another category of bleaching agents that can be used in the present invention is halogen bleaching agents. C Examples of ipohalide bleaches are trichloroisocyanuric acid, dichloroisocyanuric acid, Sodium and potassium neurate, N-chloro and N-promoalcanth Contains sulfonamide. Such materials account for 0.59-10% by weight of the finished product; Preferably 1-5% by weight is added.

Peroxy bleach can also be used. A suitable peroxy bleach is sodium carbonate. Umperoxy/\idole, sodium birophosphate peroxyno\idole urea peroxyhydrate and sodium peroxide.

The peroxy bleach is preferably combined with a bleach activator, thereby increasing the bleach activity. In-situ production of peracids corresponding to sexifiers in aqueous solution (i.e. during washing) do.

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

-C-L where R is an alkyl group containing 1 to about 18 carbon atoms, and a carbonyl carbon The longest linear alkyl chain extending from and containing this carbonyl carbon has about 6 to about 10 carbon atoms. and L = Biing group, the conjugate acid of which is in the range of about 4 to about 13. It has a pKa of These bleach activators are described in U.S. Pat. No. 4,915,854. , and 4°412.934, incorporated herein by reference.

Bleach agents other than oxygen bleach are also known in the industry and can be used in the present invention. Ru. Particularly useful types of non-oxygen bleaches are photoactivated bleaches, such as sulfonated zinc and and phthalocyanine aluminum. These substances are precipitated onto the substrate during washing. You can do it. If exposed to light in the presence of oxygen, e.g. When dried until dry, the sulfonated zinc phthalocyanine is activated and the substrate is Bleached. The preferred photoactivated bleaching method using zinc phthalocyanine is covered by a U.S. patent. No. 4,033,718, which is incorporated by reference. Typically, detergent composition The product contains about 0.025% to about 1.25% by weight zinc sulfonated phthalocyanine. have

polymer stain remover Any polymeric stain remover known in the art may be used in the practice of this invention. Ru. Polymeric stain removers are suitable for cleaning the surfaces of hydrophobic fibers such as polyester and nylon. A hydrophilic segment to make the surface hydrophilic and a hydrophobic segment to precipitate on the hydrophobic fibers and wash them. During washing and rinsing, it sticks to these fibers and acts as an anchor for the hydrophilic segment. It is characterized by having a hydrophobic segment that is useful for Remove dirt in this way Stains that occur after treatment with the agent can be easily removed during subsequent washing.

In any of the detergent compositions of the present invention, particularly for removing grease and oil from hydrophobic surfaces, polymeric stain removers in compositions used in laundry and other applications that require It is advisable to use anionic surfactants or When present in detergent compositions, lyhydroxy fatty acid amides can be used in many commonly used can enhance the performance of polymeric stain removers. Anionic surfactants are It interferes with the ability of a few stain removers to precipitate and stick on hydrophobic surfaces. these The polymeric stain remover consists of a nonionic hydrophilic separator that interacts with an anionic surfactant. segment or hydrophobic segment.

The use of polyhydroxy fatty acid amide improves the performance of polymeric stain removers. Detergent compositions include anionic surfactant systems and interactions with anionic surfactants. A working stain remover and an amount of polyhydroxy fatty acids that enhances the performance of the stain remover. A detergent composition containing amide (PFA), in this case, (1) In the absence of other detergent components, the stain remover (S "Control test" (A) to measure precipitation of RA) and SRA and anionic surfactant The same type and the same amount of anionic field used in the detergent composition, in the same weight ratio with the agent. "rSRA/Anionic Surfactant" test where surfactant binds to SRA in aqueous solution (B), SR on a hydrophobic fiber (e.g. polyester) in an aqueous solution. Comparing the precipitation level of A, it was found that the precipitation in (B) was lower than that in (A). By exhibiting the action of anionic surfactants, stain removers and anionic surfactants in detergent compositions Anionic surfactant interactions between the surfactant system and (II) Amide PFA of the same type and level is used in the above-mentioned SRA and anion field. "SRA/Anionic surfactant/PFA test" combined with surfactant system Compare the SRA precipitation in (C) with the SRA precipitation in the test (B) above. Therefore, the improvement in SRA precipitation in test (C) compared to test (B) is due to the amount of SRA activation. By indicating the presence of PFA in the detergent composition, it is possible to Determine whether or not the liquid contains fatty acid amide (PFA). So in this case The test is performed at a temperature above the critical micelle concentration (CMC) of the anionic surfactant, preferably must be carried out at a surfactant concentration in the aqueous solution of about 1100 ppm or higher. . The concentration of polymeric soil remover should be at least 15 ppm or higher.

For hydrophobic fiber sources, polyester fiber swatches must be used.

For each test, a sample of the same type was immersed in a 35°C aqueous solution for 12 minutes. Stir, then remove and analyze. Treat stain remover using industry-known technology Prior to radio-tagging and then radiochemical analysis, polymer stain remover levels were determined. It is possible to determine the

As an alternative to the radiochemical analysis method described above, the tests described above (i.e. tests A, B and and C) measure the ultraviolet (UV) absorption of the test solution by techniques known in the art. By doing this, the stain remover precipitate can be measured. After removal of hydrophobic fiber material The phenomenon of UV absorption in the test solution corresponds to an increase in SRA precipitation. It is clear to those skilled in the art Similarly, high levels of surfactants with aromatic groups (e.g. alkylbenzenes) Tests containing types of materials that cause excessive UV absorption interference, such as sulfonates, etc. Do not use UV analysis for liquid solutions.

As mentioned above, the "stain remover function activation amount" of polyhydroxy fatty acid amide is The amount of surfactant that enhances the precipitation of soil remover on hydrophobic fibers or the next wash. Grease/ It refers to the amount of surfactant that improves oil cleaning performance.

The amount of polyhydroxy fatty acid amide needed to enhance the precipitation of the stain remover is determined by anionic surfactant, the amount of this surfactant, and the specific oil removal selected. and the selected polyhydroxy fatty acid amide. generally detergent The composition contains about 0.01% to about 10% by weight, typically about 0.1% to about 5%. rimer stain remover and from about 4% to about 50%, more typically from about 5% to about 30%. % anionic surfactant. The composition also generally contains at least about 1%, preferably Preferably, it should not contain at least about 3% by weight of polyhydroxy fatty acid amide. However, it is not limited to this.

By the presence of polyhydroxy fatty acid amide in the presence of anionic surfactant Polymer stain remover with enhanced functionality (a) (i) a polyoxyethylene segment having a degree of polymerization of at least 2; (ii) oxypropylene or polyoxylene having a degree of polymerization of 2 to 10; In the propylene segment, this hydrophilic segment has an ether at each end. oxypropylene moieties unless they are connected to adjacent moieties by link bonds Segments that do not contain a lene unit, or (ii) oxyethylene containing oxyalkylene units and 1 to about 30 oxypropylene units. In the mixture, the mixture is used for stain removal on the surface of ordinary polyester synthetic fibers. a sufficient amount of oxyethylene unit to increase the hydrophilicity of this surface as the agent is deposited. The hydrophilic segment preferably contains at least about 25% oxyethyl. having tyrene units, especially about 20 to 30 oxypropylene units As for the ingredients, to have at least about 50% oxyethylene units one or more nonionic hydrophilic components consisting of a mixture made up of ), (i) C3 oxyalkylene terephthalate segment, wherein the hydrophobic If the sexual component is also oxyethylene terephthalate, it is oxyethylene terephthalate. The ratio of carbon to C3 oxyalkylene terephthalate units is about 2:1 or less. (ii) a C4-C6 alkylene or oxyC4-C 6 alkylene segments or mixtures thereof; and (iii) at least 2 certain Poly(vinyl ester) segments with a degree of polymerization, preferably poly(vinyl acetate) segment) or a mixture thereof, wherein the substituent is a Cl-C4 alkaline segment. Kyl ether or C4 hydroxyalkyl ether cellulose derivative or its The cellulose derivatives are amphoteric and therefore usually Precipitates on the polyester synthetic fiber surface and simultaneously deposits on this surface. Sufficient levels of C to retain sufficient hydroxyl levels to increase hydrophilicity l-C4 alkyl ether and/or C4 hydroxyalkyl ether one or more hydrophobic components configured to have a Or it includes a stain remover having a combination of the components (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have from 2 to about 200 The degree of polymerization has a degree of polymerization, but higher levels can be used, preferably from 3 to about 150, more preferably 6 to about 100. suitable oxyC4 -C6 alkylene hydrophobic segment is M03Si(CH2)nOcH2cH2 including, but not limited to, end caps of polymeric stain removers such as 0- In this formula, M is sodium and n is an integer from 4 to 6.

No. 4,721,580, which is incorporated by reference.

Polymer stain removers are cellulose, such as hydroxyether cellulose polymers. Derivatives, ethylene terephthalate or ethylene terephthalate or terephthalic acid Collage of propylene and polyethylene oxide or polypropylene terephthalate oxide Including polymer blocks and the like.

Cellulose derivatives that function as stain removers are commercially available, such as Methoce Contains cellulose hydroxy ethers such as IR (Dow).

The cellulose stain remover used in the present invention includes methylcellulose, ethyl Cellulose, hydroxypropyl, methylcellulose and hydroxybutyl C1-4 alkyl and C4 hydroxyalkyl cellulose, such as methylcellulose including those selected from a group consisting of: Useful as a stain remover polymer Various cellulose derivatives for use are described in U.S. Pat. No. 4.00'0.093, Use this as an example.

Stain removers featuring poly(vinyl ester) hydrophobic segments are vinyl esters), such as C1-6 vinyl esters, preferably poly(vinyl acetate) ) on a polyalkylene sub-backbone such as an oxidized polyethylene backbone Contains grafted copolymers.

Such substances are known in the art and are described in European Special No. 0.219.048. ing. A suitable commercial stain remover of this type is available from BASF (West Germany). SokT)1 alanTM type materials, such as 5okalan HP-22.

One type of preferred stain remover is ethylene tylphthalate and tylphthalic acid. It is a copolymer with random blocks of modified polyethylene (POE). Sara (In detail, these polymers are ethylene tylphthalate and PEO tylphthalate. repeating units in a molar ratio of about 25:75 to about 35:65; The PEO tylphthalate unit is a polyethylene oxide with a molecular weight of about 300 to about 2000. Contains Ren. The polymeric stain remover has a molecular weight of about 25,000 to about 55 ．． Within the range of 000. See U.S. Pat. No. 3,959,230, incorporated herein by reference. do.

US Pat. No. 3,893,929 also discloses similar copolymers.

Another preferred polymeric stain remover is 10-15% by weight ethylene tylphthalate. unit and 90-80% by weight of polyoxyethylene tylphthalate. Uniform molecular weight ffi 300-5, derived from OOO polyoxyethylene glycol polyester with repeating units of ethylene tylphthalate units. Therefore, ethylene tylphthalate and polyoxyethylene tylphthalate in this polymer The molar ratio between 2:1 and 6:1. An example of this polymer is the commercially available Ze lconR512B (DuPont Donnemours) and Mflease"T (ICI). These polymers and their method of preparation are described in U.S. Pat. No. 4,702. , No. 857, which is cited as a reference.

Other preferred polymeric soil removers include substantially linear ester oligomer sulfates. The phonation product in which the pre-J oligomer is tylphthaloyl Conjugated to backbone, with oxyalkylene oxy repeat uni, soto, with tsukbone The stain remover consists of a terminal moiety bonded to an allyl alcohol alcohol. toxylate, dimethyl tylphthalate and 1,2-propylene diol. The terminal moiety of each oligomer averages a total of about 1 to about 4 sulfones. It has a to group. These stain removers are fully described in U.S. Pat. No. 4,968,451. This will be used as a reference.

Other suitable poly stain removers include ethyl or Methylca sovdo 1,2-brobylene terphthalate-polyoxyethylene Terphthalate polyester, the polyester described in U.S. Pat. No. 4,721,580 Contains sulfopolyethyne groups derived from ethylene glycol (PEG) Oligomeric esters with anionic end caps and U.S. Pat. 02,857 of the formula X-(OCH2CH2)n- a block polyester oligomer compound having a cap, where n in the above formula is 1 2 to 43, and X is C1-4 alkyl or preferably methyl, include. These patents are cited as examples.

Polymer pond stain removers include the stain remover of U.S. Patent No. 4,877.896. , this patent applies to anions, especially sulfuryl, end-capped terephthalate. and this patent is incorporated by reference. Telegerapite Futale mentioned above esters are asymmetrically substituted oxy-1,2-alkyleneoxy units. Including.

In the stain remover of U.S. Pat. No. 4,877,896, there are Polyoxyethylene hydrophilic component or C3 oxyalkylene within the aqueous component Substances with repeating units of terephthalate (propylene terephthalate) Ru. This shows that polyhydroxy fatty acid amides in the absence of anionic surfactants Polymer stains characterized by either or both of these benefits resulting from the presence of It is a remover.

If a stain remover is used, it will account for about 0.01 to 10% of the detergent composition; Typically from about 0.1 to about 5% by weight, preferably from about 0.2 to about 3.0% by weight. Contained within the range.

chelating agent The detergent composition of the invention may further optionally contain one as a builder additive. or containing multiple iron and manganese chelators. Such chelation The agent is an aminocarboxylate, an aminophosphate, a polyester, as defined below. Selected from functionally substituted aromatic chelating agents and mixtures thereof. to theory Without intending to be bound by this, the advantages of these materials are, in part, their soluble Removes iron and manganese ions from laundry solutions by forming chelates This seems to be due to the unique abilities of these substances.

Aminocarbohydrates Used as Optional Chelating Agents in Compositions of the Invention The xylate has one or more, preferably at least two, uni- You can have: Here, M is hydrogen, alkyl metal, ammonium or substituted ammonium (e.g. (e.g. ethanolamine), and X is 1 to 3, preferably 1. Preferably this These aminocarboxylates are alkyl or alkyl having about 6 or more carbons. Contains no kenyl groups. Aminocarboxylate that can be used is ethylene diamide N-tetraacetate, N-hydroxyethyl-ethylene diamine 1-noacetate Nitrilotriacetate, Ethylenediaminetetraprobionate, Torie Tylenetetraamine hexaacetate, diethylenetriaminepentaacetate , and ethanolamines, their alkali metals, ammonium, and substituted amines. Including ammonium salts and mixtures thereof.

The present invention provides at least a low level of total 1-Non in detergent compositions, if permitted. Aminophosphonates can be used as chelating agents in the compositions.

Compounds having one or more, preferably at least two, of the following structural units: where M is hydrogen, alkali metal, ammonium or substituted atom. Ammonium and X are 1 to 3, preferably 1. These compounds Endiaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetriaminepentakis (methylene phosphonate) )including. Preferably these aminophosphonates contain about 6 or more carbon atoms. Contains no alkyl or alkenyl groups. The alkylene group is separated by the replacement bone. be possessed.

Polyfunctionally substituted aromatic chelating agents may also be used in the compositions of the present invention. can. These substances can include compounds of the formula: Here, at least one R is -8O3H or -COOH or a soluble salt thereof and mixtures thereof. U.S. Patent No. 3,812,044, cited herein: Discloses polyfunctionally substituted aromatic chelating and sequestering agents . Preferred compounds in the acid form of this type are dihydroxydisulfobenzenes, e.g. ．． 2-dihydroxy-3,5-disulfobenzene. Alkaline detergent composition may be used to replace these substances with alkali metals, ammonium or substituted ammonium (e.g. , mono- or triethanolamine) salts.

When used, these chelating agents generally make up about 0.1% to about 0.1% of the detergent composition. Contains 10% by weight. More preferably, the chelating agent is about 0% of the detergent composition. ．． It is contained in an amount of 1 to about 3.0% by weight.

Clay stain removal/re-sedimentation prevention agent The detergent compositions of the present invention optionally have clay stain removal and anti-resettling properties. It can contain a water-soluble ethoxylated amine with these compounds The granular detergent composition typically contains from about 0.01 to about 10,0ftfi9° of water-soluble ethoxylated amines. Liquid detergent compositions typically contain about 0 ．． 01 - Contains approximately 5 MIk%. These compounds preferably belong to the following groups: Selected from: (1) Ethoxylated monoamine of the following formula: (2) Ethoxylated monoamine of the following formula Diamine: (3) Ethoxylated polyamine of the following formula: (4) Ethoxylate of the following formula Sylated amine polymers and (5) The mixture: Here A1 is RRR-R-R or -〇-; R is H or C1-4 alkyl or hydroxyalkyl ;R1 is C2-12 alkylene, hydroxyalkylene, alkenylene, aryl Ren, or alkaline lene, or 2 to 20 if no O-N bond is formed. C2-3 oxyalkylene moiety having an oxyalkylene unit; each R 2 is C1-4 or hydroxyalkyl, -L-X moiety, or two R 2 or together Moiety (CH2)r, -A2-(CH2)s-, Uni to A2 is 10- or -CH2-1" is 1 or 2, S is 1 or 2, and r + s is 3 or 4: X is a nonionic group, anionic group or a mixture thereof, R3 is a substituted C3 -12 alkyl, hydroxyalkyl, alkenyl, aryl or alkali or alkaryl group having a substituted position; R4 is CL-12 alkylene, hydrogen droxyalkylene, alkenylene, arylene or alkarylene, or 2 to about 20 oxyalkylene unless a 0-O bond or an O-N bond is formed C2-3 oxyalkylene moiety with unit; L is polyoxyalkylene moiety; Hydrophilic m containing renmoiete (-[(R50)mK(CH2CH20)nl-wo, Here, R5 is C3-4 alkylene or hydroxyalkylene, and m and n are Moiety (CH2CH20) n- of the polyoxyalkyl moiety such that it constitutes at least about 50% by weight; for said monoamines, m is from 0 to to about 4, and n is at least about 12; for the diamines, m is from 0 to about 3; and n is R1 is C2-3 alkylene, hydroxyalkylene or alkenylene at least about 6 when R1 is C2-3 alkylene, hydroxyalkylene or at least about 3 when other than alkenylene, and the polyamine and amino For polymers, m is 0 to about 10%; n is at least about 3; p is 3 to about 10%; to 8; q is 1 or Oat is 1 or 0, but when q is 1, t is 1; W is 1 or O: x+y+z is at least 2; and y+z is at least 2.

The most preferred soil remover/settling agent is ethoxylated tetraethylene pentaalysate. It's Min. Examples of ethoxylated amines are further described in U.S. Pat. No. 4,597,89 It is stated in No. 8 and is cited as an example. Other groups of preferred clay stain removal/removal Suspension inhibitors are cationic compounds described in European Special No. 111,965. other Clay stain removal/resettling prevention agent is Etokki described in European Special No. 111.984. amine polymer; Zvitterio as described in European Special No. 112,592; amine polymers; and amine oxides as described in U.S. Pat. No. 4,548,744. It is. All these patents are cited.

In the detergent composition of the present invention, clay stain removal/re-sedimentation prevention other than those mentioned above may be used. agent can be used. Other types of clay stain removers/anti-resettling agents include carboxymer Contains chilled cellulose (CMC) material. These materials are known in the art.

polymer dispersant In the detergent compositions of the invention it is preferred to use polymeric dispersants. these The substances help control calcium and magnesium hardness. Appropriate polymer content The powder contains the polymer polycarboxylate and polyethylene glycol, but Other materials known in the industry may also be used. I don't intend to be bound by theory, but Polymeric dispersants can be used with other builders (including low molecular weight polycarboxylates). When used for inhibiting crystal growth, preventing veptization of granular dirt and reprecipitation. The effect is believed to increase overall detergent builder performance.

The polymeric dispersant comprises about 0.5% to about 5% by weight of the detergent composition, more typically about It is used at levels of 1.0 to about 2.0% by weight.

The polycarboxylate material used in the present invention as a polymeric dispersant is A polymer or copolymer containing at least about 60% by weight of segments of the general formula: is: Here, X, Y and Z are hydrogen, methyl, carboxy, carboxymethyl, hydro each selected from the group consisting of oxy and hydroxymethyl; M is the salt form The forming cation, n, is about 30 to about 400. Preferably, X is hydrogen or hydrogen. Roxy, Y is hydrogen or carboxy, Z is hydrogen or M is hydrogen, alkyl metal, alkyl metal ammonium or substituted ammonium.

Polymeric polycarboxylate materials of this type preferably contain suitable unsaturated monomers. can be produced by polymerizing or copolymerizing it into its acid form. suitable port Unsaturated monomers that can be polymerized to form remer polycarboxylates -Acids include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, and itacon. acids, including aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.

This polymer polycarboxylate contains vinyl ethyl ether, styrene, The presence of monomer segments that do not contain carboxylate groups such as ethylene I can. However, such segments shall not constitute more than approximately 40% by weight. stomach.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. . Such acrylic acid-based polymers used in the present invention are polymerized acrylic It is a water-soluble salt of acid. The average molecular weight of such polymers in acid form is preferably About 2,000 to 10,000, more preferably about 4,000 to 7,000 , most preferably in the range of about 4,000 to 5,000.

Such water-soluble salts of acrylic acid polymers include, for example, alkali metal salts, ammonium salts, etc. ammonium salts and substituted ammonium salts. This type of water-soluble polymer is a known substance. be.

The use of polyacrylates of this type in detergent compositions has been described, for example, in US Pat. No. 3,308.067. This patent is cited as a reference.

Acrylic/maleic acid based copolymer as a preferred component of the dispersion/anti-resettling agent. You can use a rimmer.

This material contains a water-soluble salt of a copolymer of acrylic acid and maleic acid. acid form The average molecular weight of such copolymers is 2,000-100,000, preferably preferably about 5,000-75,000, most preferably about 7,000-65,000 The range is 00. The acrylic acid segment and male in such copolymers The ratio with inic acid segments is generally from about 30:1 to about 1:1, more preferably The ratio should be approximately 10=1 to 2:1. Such acrylic acid/maleic acid copolymer Examples of water-soluble salts of mer include alkali metal salts, ammonium salts and substituted ammonium salts. It can contain um salt. This type of water-soluble acrylic acid/maleic acid copolymer is publicly available. It is a known substance and is described in European Special No. 66915, which is cited as a reference.

Other polymeric materials that can be included in the compositions of the invention include polyethylene glycol. (PEG). PEG exhibits the performance of a dispersant and is also a clay stain remover/resettling agent. Acts as an anti-sludge agent. A typical molecular weight range for these purposes is about 50 0 to about 100.00, preferably about 1,000 to about 50,000, more preferably Preferably, it is about 1.500 to about 10.000.

brightener Brighteners or other brighteners or whitening agents known in the art may be present in the detergent compositions of the present invention. Agents can be combined.

The choice of brightener used will depend on the type of detergent used, other ingredients present in the detergent composition. Many factors such as the nature of the wash water, the temperature of the wash water, the degree of agitation and the ratio of laundry to tub size. Depends on the factor.

The choice of brightener also depends on the type of laundry, eg cotton, synthetic, etc. many Since detergent compositions are used to wash a wide variety of fabrics, detergent compositions The composition must contain a brightener mixture that is effective for each type of fabric. stomach. Of course each component of such a brightener mixture must be mutually compatible. .

Commercially available brighteners that can be used in the present invention include stilbene, pyrazoline, coumarin , carboxylic acid, methinecyanine, dibenzotifen-5-5 dioxide, azo subgroups including derivatives of rings, 5- and 6-membered heterocycles and other materials. Although it is classified as a group, it is not limited to this group. Examples of such brighteners include “The Process and Application or Fluor essent Brightening Agents-, M.

Zahradnik, John Wiley & 5ons, New Year K (1982), the disclosure of which is incorporated by reference.

The stilbene derivative used in the present invention is bis(triazinyl)amino-stilbene derivative. Ben derivatives; bisacylamino derivatives of stilbene, triazoles of stilbene Derivative; Oxadiazole derivative of stilbene; Oxazole derivative of stilbene and styryl derivatives of stilbenes.

A few derivatives of bis(triazinyl)aminostilbene used in the present invention The conductor is manufactured from 4.4゛゛　-diaminstilbene-2,2　-disulfonic acid. can be done.

Coumarin derivatives that can be used in the present invention are located at positions 3, 7, and 3 and 7. including, but not limited to, modified derivatives.

Carboxylic acid derivatives that can be used in the present invention are fumaric acid derivatives; benzoic acid derivatives ; p-phenylene-bis-acrylic acid derivative; naphthalene dicarboxylic acid derivative; including, but not limited to, heterocyclic acid derivatives; and cinnamic acid derivatives.

The cinnamic acid derivatives used in the present invention are disclosed on page 77 of the Zahradnfk reference. such as, cinnamic acid derivatives, styryl azole, styryl benzofuran, styryl Contains luoxadiazole, styryl triazole and styryl polyphenyl Although classified into groups, it is not limited to this.

Styryl azole is a styryl azole as described on page 78 of the Zahradnik reference cited above. Tyrylbenzoxazole, styryl imidazole and styrylthiazole It can be classified. These subclasses are not necessarily subgroups of styrylazole. This is not a complete list of loops.

Other classes of brighteners that can be used in the present invention include The Kirk -Othmer　Encyclopedia　or　ChelcalTechn ology, Volume 3. pages 737-750 (John Viley & Son, Inc., 19B2), pages 741-749. dibenzothiophene-5,5-dioxide according to Contains benzothiophene-2,8-disulfonic acid-5,5-dioxide.

Yet another class of brighteners that can be used in the present invention includes azoles, which are five-membered ring is a heterocyclic derivative of This compound is further classified into monoazole and bisazoles. It is divided into Examples of monoazoles and bisazoles are Kjrk-Othmer It is stated in the citation.

Yet another class of brighteners that can be used in the present invention is described in Klrk-Othmer ref. It is a derivative of the six-membered heterocyclic ring described above. An example of such a compound is derived from pyrazine. and brighteners derived from 4-amitnaphthalamide.

In addition to the brighteners mentioned above, various compounds can be used as brighteners. this Examples of various such compounds are described on pages 93-95 of the Zahradnik citation. , 1-hydroxy-3,6,8-pyrene-trisulfonic acid; sulfonic acid; and and pyrazoline-quinoline derivatives.

Other examples of brighteners that can be used in the present invention are described in U.S. Pat. No. 4,790,856. , and its disclosure is cited as a reference. These brighteners are from Verona Garaichi Includes the Pho rwh it eTM brightener series. Open to this reference Other brighteners shown include: Tinopa, commercially available from Ciba-Geigy; l LINPA, Tjnopal CBS and Tinopal 5BM; Arctic White C commercially available from Hilton Davis, Italy C and Arctic Vhfte CWD.

2-(4-styryl-phenyl)-2H-naphthol [1,2-63 triazole 4,4°-bis-(1°2,3-triazol-2-yl)-stilbene; Contains 4゜4'-bis(styryl)bis-phenyl; and y-aminocoumarin . Examples of these brighteners are 4-methyl-7-cyacylaminocoumarin; 1,2 -bis-(benzimidazol-2-yl)ethylene; 1,3-diphenylfura Dirine; 2.5-bis-(benzoxazol-2-yl)thiophene: 2- styryl-naphtho-[1,2-d]oxazole; and 2-(stilbene-4 -yl)-2H-naphtho-[1,2-d cotriazole.

Other brighteners used in the present invention are described in U.S. Pat. No. 3,646.015 and Use this as an example.

Foam suppressant For reducing or suppressing the formation of foam, the invention Can be incorporated into compositions. It is desirable to combine this substance with a "foaming suppressant". Inoha has demonstrated that the polyhydroxy fatty acid amide of the composition of the present invention improves the foaming stability of detergent compositions. This is because it increases the quality. The suds suppressant is the polyhydroxide composition of the present invention. When containing a surfactant that produces relatively high foaming together with a sialic acid amide surfactant is particularly important. Foam in the case of compositions for front-loading automatic washing machines Standing restraint is particularly desirable. These machines are designed to accommodate laundry and washing water. , has a drum that has a horizontal axis and rotates about this axis. This type of stirring resulting in high foam formation and thus reducing cleaning efficiency. hot washing water and the use of foam suppressants in conditions where high concentrations of surfactants are used. is particularly important.

A variety of materials can be used in the compositions of the invention. Foam suppressants are a It is well known in the world. Foam suppressants include, for example, Kirk 0thier Encyclo. pedia of Chemical Technology, third E dition, Volume 7. pages 430-447 (Joh n.Viley & 5ons, Inc., 1979). It is. A category of suds suppressants of particular interest is monocarboxylic fats. Acids and their water-soluble salts. These materials are described in U.S. Patent No. 2,954,347. , and this is cited as an example. Monocarboxylic fat used as a foam suppressant The fatty acids and their salts are hydrocarbons of 1 to about 24, preferably 12 to 18 carbon atoms. It has a rubile molecular chain. Suitable salts include sodium, potassium and lithium salts. In which alkali metal salts and ammonium salts and alkanol ammonium salts be. These substances are a preferred category of suds suppressants for detergent compositions. be.

The detergent composition can also include non-surfactant suds control agents. These foaming suppressors Agents include, for example, the list below: paraffins, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of -hydric alcohols, aliphatic C18-40 keto high molecular weight hydrocarbons (e.g. stearone). Other foam suppressants include 1 to Contains 2 or 3 moles of primary or secondary amines having 24 carbon atoms Tri- to hexa-alkyl melami formed as a product of cyanuric chloride N-alkyl diamine or di- or tetra-alkyldiamine, such as chlortriazine Chelated aminotriazines, propylene oxide, and stearyl alcohol phosphoric acid esters and monostearyl di-alkali metals (e.g. Na, LL, ) containing monostearyl phosphates such as phosphoric acid esters and phosphonic acid esters. nothing. Hydrocarbons such as paraffins and haloparaffins can be used in liquid form. Ru. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, and in the range of about -40℃ to about 5℃. and a minimum boiling point of about 110°C (atmospheric pressure) or higher. Good again It is also known to use a wax hydrocarbon having a melting point of approximately 100°C or less. be. Hydrocarbons constitute a preferred category of suds suppressants in detergent compositions. Carbonization Hydrogen suds suppressants are described, for example, in U.S. Pat. No. 4,265,779, which Use as an example. These hydrocarbons include aliphatic, having about 12 to about 70 carbon atoms; Includes cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons. This foaming control The term "paraffin" used by agents refers to true paraffins and cyclic carbonized It shall contain hydrogen.

A preferred category of non-surfactant suds control agents includes silicone suds control agents. . This category includes polydimethylsiloxane, polyorganosiloxane oil or are resin dispersions or emulsions, and polyorganosiloxane and silica particles. Polyorganosiloxane is fused onto silica in combination with silica. Use polyorganosiloxane oil. Silicone foam suppressants are known in the industry. For example, US Pat. No. 4,265,779, European Special No. 89307851 ．． No. 9, and both of these are cited as references.

Other silicone suds control agents are described in U.S. Pat. No. 3,445.839, which patent describes the defoaming of an aqueous solution by adding a small amount of polydimethylsiloxane solution. The present invention relates to compositions and methods for doing so.

Mixtures of silicone and silanate silica may be used, for example, in German special DOS 2,124 , No. 526.

Silicone antifoam agents and antifoam agents in granular detergent compositions are disclosed in U.S. Patent No. 3.9'3 No. 3,672 and No. 4,652°392.

An example of a silicone-based foam suppressor used in the present invention consists of the following ingredients: Including foam suppression amount of foam suppressant: (i) Polydimethane having a viscosity of about 20 cs to about 1500 cs at 25°C. luciloxane fluid; (ii) from about 5 to about 50 parts by weight per 100 parts by weight of the compound of (i); Parts by weight of siloxane resin. The siloxane resin is about 0.6:1 to about 1.2:1 It consists of (CH3) 3SiOI/2 units and 5i02 units with a ratio of .

(i) about 1 to 20 parts by weight of solids per 110 parts by weight of compound (i); silica gel.

For any detergent composition used in an automatic washing machine, the suds may overflow from the washing machine. must not be formed at the same time.

If a foam suppressant is used, it is preferably present in a "foam suppressing amount". . "Foaming suppression amount" refers to the amount of detergent that produces low foaming when used in automatic washing machines. It means the amount of foam suppressant that can control foaming so that foaming is controlled. Foaming suppression The amount will vary with the detergent surfactant selected. For example, highly foaming surfactants When using a foaming surfactant with lower foaming properties, Use relatively large amounts of anti-foaming agent. Generally, during a wash cycle (i.e. (formed during agitation of detergent in aqueous solution at desired washing temperature and concentration conditions) The foam should not exceed about 75%, preferably about 50%, of the void space of the laundry container. A sufficient amount of suds suppressant is incorporated into the low suds detergent composition to Must be. In this case, the washing machine void is the total volume of the washing machine container plus the water pump. This is the difference between the volume of lath laundry.

Compositions of the present invention generally contain from 0% to about 5% suds suppressant. anti-foaming agent and When used as It is present up to %. Preferably about 0.5% to 3% fatty monocarboxylate Foam suppressants are used. Silicone suds suppressants are typically used in detergent formulations. It is used in amounts up to about 2.0% by weight of the product. However, using a larger amount You can also do it. Small amount of foaming to minimize cost and effective foaming control This upper limit is practical due to the use of inhibitors. In reality, about 0.01% or About 1% 1 preferably about 0.25% to about 0.5% silicone suds suppressant. It is preferable to use it.

In this case these weight percentages are silica used with polyorganosiloxane; and any other adjuncts. Monostearyl phosphate is one Generally used from about 0.1% to about 2% of the composition.

Hydrocarbon suds suppressants are typically used in amounts ranging from about 0.01% to about 5.0%. used, but higher levels can also be used.

other ingredients Various other ingredients useful in detergent compositions can be included. For example, other Active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, liquid formulation solutions. It can include media, etc.

Liquid detergent compositions can contain water and other solvents as carriers. meta Low molecular weight primary compounds such as alcohol, ethanol, propatool and inpropatool Alternatively, a secondary alcohol is suitable. Monohydric alcohol to dissolve the surfactant Polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups are preferred; (e.g. propylene glycol, ethylene glycol, glycerin and , 2-propanediol) can be used.

When the detergent composition of the present invention is used for washing, the washing water content is preferably about 6.5 to about 11. More preferably, it is blended to have a pH of about 7.5 to about 10°5.

The washing water preferably has a molecular weight of about 7.5 to about 9.5, more preferably about 7.5 to about 9. ．． It has a pa of 0. Techniques for controlling pI (to the desired usage level) include buffers, The use of alkalis, acids, etc. is well known to those skilled in the art.

The present invention also provides anionic, nonionic and/or cationic surfactants and Detergent compositions or mixtures thereof containing olites or layered silicate builders The polyhydroxy fatty acid amide surfactant is added to the zeolite and/or or the weight ratio of the layered silicate and the polyhydroxy fatty acid amide surfactant is approximately 1:10 to about 20:1 to form the mixture. It concerns how to

The present invention also provides one or more anionic, nonionic or cationic surfactants. , zeolite or layered silicate builders or mixtures thereof and polyhydroxy fatty acid amides, water or water-miscible solvents (e.g. primary alcohols and The builder: polyhydroxy fat in the presence of a solvent such as a secondary alcohol) Contained so that the weight ratio with the acid amide surfactant is about 1:10 to about 20=1. contacting the detergent composition with substrates such as fibers, fabrics, hard surfaces, and skin. Thus, a method is provided for purifying said substrate. Preferably to further facilitate purification Stirring is performed for this purpose. Appropriate stirring means include manual stirring, brushes, and sponges. Cleaning devices such as jigs and motupu, automatic dishwashers, and laundry machines for textiles (e.g. clothes). Including dynamic washing machines.

In said method, said zeolite and/or layered silicate builder: A more preferred weight ratio of polyhydroxy fatty acid amide is from about 1=5 to about 15=1. , most preferably from about 1=3 to about 10=1.

experiment This experiment was performed on the N-methyl, 1-deoxygludityl group used in the present invention. This is an example of a method for producing uric acid amide. The experimenter varied the shape of the device used. A suitable device that can be used in this case is a motor-driven paddle stirrer. 3 liter 4 with a thermometer of sufficient length to contact the reaction medium. 0 flask. The other two necks of the flask are for nitrogen scavenging and the wide pore side. Arm (Note: This side arm is important in case of very rapid methanol generation) ) with an efficient collection condenser and vacuum evacuation hand for this side arm. The stages are connected. Said vacuum evacuation means is connected to a nitrogen extractor and a vacuum gauge. connected to the suction device and trap. Transformer temperature control to heat the reaction A 500 watt heating mantle with a The reactor is attached to the reactor so that it can be moved up and down to control the reaction temperature.

N-Methylglucoamine (195g, 1.0mol, Aldrich, M470 0-) and methyl laurate (P&G CE1270.220.9g, , 1. 0 mol) is placed in the flask. This solid/liquid mixture was Heat under the apparatus with stirring to form a melt (approximately 25 minutes). melt temperature When the temperature reached 145°C, the catalyst (powdered anhydrous sodium carbonate, 10.5g, 0.5g) was added. 1 mol, J, T, Baker) is added. Close off nitrogen scavenging and remove suction device and nitrogen extraction device. Adjust the position to produce 5 inches Hg, vacuum (5/31 stm). From this point on, The reaction temperature was maintained at 150℃ by adjusting the Variac and raising and lowering the mantle. hold

Within 7 minutes, the first methanol bubbles are visible in the meniscus of the reaction mixture. intense A reaction immediately ensues.

This is distilled until the proportion of methyl is reduced. Approximately 10 inches Hg, (10/3 1 atm) Adjust the vacuum to create a vacuum. The vacuum can be increased approximately as follows: 10Ng inches in 23 minutes and 20Ng inches in 7 minutes.

25Ng inch in 10 minutes. A certain amount of foaming occurred 11 minutes after the start of methanol generation. Stop heating and stirring at the same time.

The product is cooled and solidified.

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

Example 1-12 Examples of these are polyhydroxy fatty acid amides and zeolites and/or laminated cages. 1 shows a heavy duty granular detergent composition containing an icate builder.

Basic particles 1 2 3 4 C14-15 Furkyl Sulfate 1B, 9 10.1 11.3014-15 Al Kill ethoxy (2,25) sulfate 5.6C12-18 alkyl sulfate IB, 9-linear C12 alkylbenzene sulfonate 10.1N-methyl N-deoxy Sigurdityl Cocoamide 5.8 2.4 5.8 5.8 Zeolite A 3 0.1 Li2 184 30.1 Sodium citrate e, a e, a Sodium carbonate 1B, 9 21.9 21.9 16.9 Sodium silicate 5.8 5.6 5.6 5.8 Sodium sulfate 15.0 15.0 1 5.1 15.1 Sodium polyacrylate (4500MW) 1.1 1.1 11 1.1 Polyethylene! J Call (8000MW) 1.1 1.1 1.1 1.1 Tallow fatty acids t, i, ti, li, as brighteners 0.2 0.2 0.2 0.2 Additives and spray-on Protease (1.4% i-enzyme > 0.9 0.9 0.9 0.9 Fragrance 0 ．． 3 0.3 0.3 0.3 CI2-13 alkyl ethoxylate (6,5 mole Le> 1.1 1.1 1.1 1.1 Water 3.8 3.8 3.8 3.8 100.0 100.0 100.0 100.0 Example 1-4 The formulation is suitable for use at temperatures below approximately 1400 ppi (based on wash water). . The above formulations are formulated by blending the base particle components as a slurry and containing approximately 4-8% residual moisture. It is manufactured by spray drying. Add remaining dry ingredients in granular or powdered form. In a rotating mixing drum, the above spray-dried particles are mixed and then the liquid component (non-ionic surfactants and fragrances) are sprayed onto it.

Basic particles 5 6 7 Linear C12 alkylbenzene sulfonate 8.8C14-15 alkyl sulfuric acid Salt 12,6C16-18 fatty acid 2.2 2.2 Zeolite 7.0 7.0 20.4 Sodium polyacrylate (4500M W) 3.3 3.3 3.5 Polyethylene IJ: l-ru (8000Mv) 1.3 1.3 1.5 Sodium carbonate Lo, 7 10.7 Sodium sulfate 5.0 5.0 5.0 Sodium silicate (Sj02/Na2 M) 5.0 5.0 3.0 Others 7.1 7.1 7.9 Additive Zeolite 5.0 5.0 5. O N-methyl N-1-deoxygludityl cocoa amide 6.4 B, 4 3.2 C1B (8 methyl ester sulfate 19.1 ('12-18 alkyl sulfate 19.1 Others (bleach, builder, salt, filler salt, etc.) 17.2 17.2 20.4 Spray-on 012-137/L, Ki/L4 toxylate (8.5 mol) 2.0 2.8 2.0 Fragrance 0.5 0.5 0.5 Total too, o ioo, o ioo.

The compositions of Examples 5-7 were prepared by slurrying the base particulate ingredients and spraying to approximately 5% moisture. Condensate prepared by drying and mixing additional granular or powdered dry ingredients It is a granular formulation. Dedusting is achieved by spraying the powder onto the liquid component. this The product is for use at a concentration of about 11,050 ppm at wash temperatures below about 50"C. It is something.

Linear C12 alkylbenzene sulfonate 6.8CI4-15 alkyl sulfate Salt 4.8 7.8 7.8cie-ig alkyl sulfate 2.4 2.4 2 ．． 4 2.2 C1ef-Ill alkyl ethoxylate (11 monoly 1.1 1.1 1.1 Zeolite 22.0 24.7 21! 13.0 acrylic /maleic acid copoly7- (80000MIf) 4.3 5.8 4.3 Polyacrylate (4500Mv) 5.0 Water and optional ingredients 9.4 9 ．． 2 10.1 1Q, 2 boxes missing N-Methyl N-1-deoxygludityl cocoamide 7.0 4. ON-methyl N-todeoxyglucityl tallow fat amide 4.0 [1,0 sodium citrate M 8.0 Sodium carbonate 17.5 17.3 17.5 17.0 Sodium silicate 3.5 3.0 3.5 3.0 Laminated silicate 11.0 Others (bleach, salt, fillers, etc.) 27.3 24.1 19.4 24.8 Silicone fluid 0.5 0.5 0.5 0.5 Total 100.0 100. 0 100.0 100.0 The compositions of Examples 8-10 preferably have a It is preferably used at a temperature of 95°C and at a concentration of about 8000 ppm based on the weight of the washing water. Delicious. These compositions are produced by slurrying the base particle components, This is spray dried to approximately 9% moisture. Add remaining dry ingredients and mixer with rotating mixer. The final liquid components are then mixed in a C12 alkyl benzene sulfur tube. phonate 5.9 5.9N-methicyto1-deoxygludityl laurate Mido 5.9C14-15 alkyl sulfate 5.9 cie-tg alkyl sulfate 2.5 2.5 2.5 zeolite 23.5 14.0 20.5 Polyac 1 route (4500M'1lI) 3.9 3.9 3.9 Sodium citrate 6.0 Sodium carbonate 12.7 1B, 0 12.7 Water and optional ingredients 8, 18°28,7 additives and spray-on N-Methyl N-1-deoxygludityl Cocoamide 5,9 Tomethyl N-1- Deoxygludityl fatty acid amide 5.6 Others (bleach, bilgoux salt, filling agents, etc.) 37.5 37.9 39.9 Total 100.0 100.0 10 0.0 Examples 12-14 have a wash water temperature of 30-95°C and a wash water weight basis of approximately A standard density granular detergent composition used at a concentration of 8000 ppm is shown. This composition The product is spray-dried with a slurry of base particle components to about 10-13% moisture and bleached. Addition of additional dry powder ingredients such as agents, active agents and other additives, fragrances, non-ionic It is produced by spraying onto a liquid such as a carbonizing agent or a foam suppressant fluid.

Example 15 Another method for producing the polyhydroxy fatty acid amide used in the present invention is shown below. 84 ．． 87g fatty acid methyl ester (raw material: P&G methyl ester CE127 0) and 75 g of N-methyl-D-glucoamine (Aldrich Chemi calCompany M4700-0) and 1.04g of sodium methoxy (Aldrich Che+++1cal Company 16,499- A reaction mixture consisting of 2), H and 51 g of methyl alcohol is used.

The reaction vessel contains a standard reflux apparatus equipped with a drying tube, condenser and stir bar. this In the method, mix with methanol with stirring under argon gas and mix thoroughly. Mix and begin heating (stir bar; reflux). After 15-20 minutes, the solution When the desired temperature is reached, the ester and sodium methoxide catalyst are added. Reaction Samples are taken periodically to monitor the process, and the solution is complete after 63.5 minutes. Please note that it is completely transparent. At this point, the reaction is practically complete. It is thought that he did. The reaction mixture is kept at reflux for 4 hours. After removal of methanol The raw product recovered was 156.18 g. After vacuum drying and purification, the whole Yield IH, 92 g of purified product is recovered.

However, percent yield is not calculated on this basis.

Regular sampling during the reaction renders the overall percent yield value meaningless. It is. Reactions were carried out at 80% and 90% reactant concentrations for up to 6 hours and were extremely can produce products with small amounts of by-product formation.

The following description does not limit the present invention, but merely describes the polyhydroquine fatty acid amide. Other aspects of the technology taken into account when producing various detergent compositions using This is an explanation of the current situation.

Polyhydroxy fatty acid amides are highly basic or highly It is understood that it becomes unstable under acidic conditions. Some degree of disassembly is allowed However, if these substances are present for an unreasonably long period of time, Or preferably, it does not experience a pH below about 3. The pH of the final product (liquid) is Officially, it is 7.0-9.0.

When producing polyhydroxy fatty acid amide, an amide bond is generally formed. It is necessary to at least partially neutralize the basic catalyst used for this purpose. any Detergent formulators are wondering if acids can be used for this purpose. It is easy and convenient to use acids that yield useful and desirable anions in compounds. You will understand something. For example, citric acid can be used for this purpose of neutralization. The resulting citrate ions (approximately 1%) are converted into approximately 40% polyhydroxy fatty acids. remain with the amide slurry and pump to later processing stages of the entire detergent manufacturing process. I can send it. Oxydisuccinate, nitrilotriacetate, ethylenediamide Acidic substances such as tetraacetates, tartrates/succinates can be used as well. Ru.

Polyhydroxy fat derived from coconut alkyl fatty acids (C12-C14) Acid amides are more aqueous than those derived from resin alkyls (mainly C1B-C1B). Soluble. .

Therefore, C12-C14 substances are easy to incorporate into liquid compositions and can be placed in cold water washing tubs. Easy to melt. However, C1B-C18 substances are also harmful, especially when using warm to hot wash water. It is extremely effective in the situations in which it is used. In fact, C1B-C1g substances are compatible It is a more dispersive surfactant than the C12-C14 material.

Therefore, detergent formulators must carefully consider the polyhydroxy fatty acid amines used in a given formulation. Ease of manufacture and performance can be balanced when choosing a board.

The water solubility of polyhydroxy fatty acid amides is determined by the presence of unsaturation points and It will be appreciated that this can be augmented by having branch points and/or branch points. Therefore , polyhydroxy fatty acid amide derived from oleic acid and isostearic acid These materials are more water soluble than their n-alkylated counterparts.

Similarly, polyhydroxy fatty acids produced from disaccharides and trisaccharides The solubility of midos is generally higher than that derived from monosaccharides. like this The high water solubility is particularly effective when formulating liquid compositions. In addition, also polyhydro Polyhydroxy fatty acid amides whose xy groups are derived from maltose are especially Excellent when used with alkylbenzene sulfonate (LAS) surfactants It is thought that it exhibits good cleaning properties. While not intending to be bound by theory, LAS and , polyhydroxy fatty acid amides derived from higher saccharides such as maltose The bonding with Therefore, it seems to enhance the net detergent performance (polymerization derived from maltose). The method for producing hydroxy fatty acid amide is explained below).

Polyhydroxy fatty acid amides are produced not only from refined sugar but also from hydrolyzed starch. corn starch containing saccharides, such as mono-, di-, etc., as desired by the formulator. It can be made from starch, potato starch, or any other vegetable starch. Ru. This is particularly important from an economic point of view. i.e. "high glucose" corn Easy and economical use of syrups, "high maltose" corn syrup, etc. I can do things. Cellulose bulbs from which lignin has been removed and hydrolyzed are also polyhydrocarbons. It can be used as a raw material for oxyfatty acid amide.

As mentioned above, pores derived from higher saccharides such as maltose and lactose Lihydroxy fatty acid amides are more water soluble than those derived from glucose.

In addition, highly water-soluble polyhydroxy fatty acid amides have a corresponding low water solubility. It seems that the water solubility of droxy fatty acid amide can be promoted to some extent. follow This allows formulators to use ingredients containing corn syrup with high glucose content. However, syrups containing small amounts of maltose (e.g. 1% or more) You can choose.

The resulting polyhydroxy fatty acid amide mixture is generally a "pure" glucose-derived More favorable over a wider range of temperatures and concentrations than polyhydroxy fatty acid amides Shows good water solubility. Therefore, when using sugar mixtures rather than pure sugar reactants, Not only is it economically advantageous, but polyhydroxy fatty acid amines produced from mixed sugars are Mido has much more advantages in terms of performance and/or ease of formulation. but In a few cases, the fatty acid maltose amide level is about 25% or higher. A certain degree of loss in grease removal performance (dishwashing performance) was observed, and at approximately 33% or more, A loss in foaming performance is observed (the above percentage is due to maltose induction in the mixture). Polyhydroxy fatty acid amide versus glucose-derived polyhydroxy fatty acid amide - cents). This varies to some extent depending on the chain length of the fatty acid moiety. . Typically, formulators who choose to use such formulations in this case will use approximately 4: 1 to about 99=1 monosaccharides (e.g. glucose) and higher sugars A polyhydroxy fatty acid amide mixture containing a proportion of caridos (e.g. maltose) It is preferable to choose.

Acyclic polyhydroxy fatty acids from fatty esters and N-alkyl polyols The amide is prepared in an alcoholic solvent at a temperature of about 30°C to 90°C, preferably about 5°C. It can be carried out at temperatures of 0-80°C. For example, for liquid detergent formulators, It is preferable to carry out the process in 1,2-propylene glycol solvent. This was confirmed. Glycol solvents are used at %N in finished detergent formulations. This is because it is not necessary to completely remove it from the reaction product beforehand. Similarly, solid Formulators of granular detergent compositions typically include ethoxylated alcohols, e.g. NEODOL 23 Ethoxylate sold as EO6,5 (shell) (E○3-8) React at 30-90℃ in a solvent containing C12-C14 alcohol. Such ethoxylation (such as If the ethoxylate contains substantially non-ethoxylate alcohol, Most preferably, it does not contain substantially monoethoxylated alcohol (r It is preferable not to substantially contain TJ).

The process for producing polyhydroxy fatty acid amide itself does not form part of the present invention. However, formulators may consider other methods of synthesizing polyhydroxy fatty acid amides as described below. You can be careful.

Typically, the preferred acyclic polyhydroxy fatty acid amides are produced on an industrial scale. The reaction sequence includes the following steps.

Step 1 - From the desired sugar or sugar mixture, prepare the N-alkylamine and sugar adduct. Steps for producing N-alkyl polyhydroxyamine derivatives by forming Step 2 - The above polyhydroxyamine is preferably reacted with a fatty ester to produce an amine forming a linkage, the N-alkyl polyhydrogen used in the second step above. Droxyamine can be produced by various methods known in the industry, but the following method The method is simple and economical sugar syrup can be used as a raw material.

For best results using such syrup ingredients, manufacturers must You must choose a syrup that is completely bright in color, mostly colorless (water white). No.

from plant derived sugar syrup Performance of N-alkyl polyhydroxyamine 1, adduct formation according to the standard method below. about 420 g of about 55 percent gluco with a Gardna color of 1 or less. about 11 g of glucose solution (corn syrup - about 231 g glucose - about 1.28 mol) 9 g of approximately 50% aqueous methylamine solution (59.5 g of methylamine-1,92 mole) ). Methylamine solution (MMA) was purged and shielded with N2, Cool to about 10°C or below. Scavenge the corn syrup and evacuate it with N2 for about 10 minutes. Shield at -20°C. M. corn syrup at the reaction temperature shown in the table below. Add slowly to MA solution.

Measure the Gardner color at a given time (minutes).

rainbow Time (minutes) 10 30 60 120 180 240 It is clear from the above data As can be seen, when the reaction temperature is about 30°C or higher, the Gardna color of the adduct becomes much stronger. At about 50°C, the adduct has a Gardner color of 7 or less. is only about 30 minutes. In order to generate further reactions and/or obtain retention times, For this purpose, the temperature should be below about 20°C. Gardna color is a good color For glycoamines it should be about 7 or less, preferably about 4 or less.

When using lower temperatures to form the adduct, a substantial equilibrium concentration of the adduct is reached. This time can be shortened by increasing the ratio of amine to sugar. Amines and sugars 1. For a 5=1 molar ratio, equilibrium is reached in about 2 hours at a reaction temperature of about 30°C. same Under conditions of a 1.2:1 molar ratio, the time is at least about 3 hours. against sugar Substantially about 90% or more, preferably about 95% or more, more preferably about 99% or more equilibrium conversion of about 7 or less, preferably about 4 or less, more preferably about 4 or less for the adduct. amine:sugar ratio, reaction temperature and reaction time to obtain a color of about 1 or less. Select a combination of

In the above method, at a reaction temperature of about 20°C or less, various Gardners shown in the table below can be used. Using colored corn syrup, substantial equilibration is achieved in at least about 2 hours. The MMA adduct colors are shown in the table below.

Table 2 Corn syrup 1 1 1 1 + 0 0 0 ÷ adduct 3 415 7/8 7/8 1 2 1 As is clear from the above, in order to always obtain acceptable adducts, For this purpose, the raw sugar substance used must be very close to colorless. sugar is approx. If it has a Gardner color of 1, the adduct may be acceptable in some cases, but in some cases Therefore, it is not acceptable. If the Gardner color is 1 or more, the resulting adduct is acceptable. Can not. The better the initial color of the sugar, the better the color of the adduct.

Il, Hydrogen reaction The above adduct with 1 or less than 1 Gardna color is Hydrogenate by the method of

About 539 g of adduct in water and about 23.1 g of catalyst G49B Nl catalyst Add medium to 1 liter of autoclave and incubate twice at 200 pst at approximately 20°C. Sweep with N2 of g. N2 pressure approximately 14001)! Increase the temperature to Ii. Increase the temperature to 50°C. The pressure is then increased to approximately 1600 psig, then the temperature is The temperature is maintained at about 50-55°C for about 3 hours. At this point the product is about 95% Hydrogenated. Next, the temperature was raised to about 85°C for about 30 minutes and the reaction mixture was decanted. , filter out the catalyst. The product obtained after evaporating water and MMA and filtering is approx. It is a white powder of 95% N-methyl glucoamine.

The above method was repeated using approximately 23.1 g of Raney Ni catalyst with the following modifications. Go back. The catalyst was washed three times and the reactor was flushed with 200 psig N2 with the catalyst in it. The reactor was purged twice with N2 for 2 hours at 1600 psLg. Pressure is removed for 1 hour and the reactor is again pressurized to 1600 psig. So The adduct was then pumped into a reactor at 200 ps i g at 20°C and Sweep the reactor with 200 psig of N2.

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

The raw material N-methylglucoamine is color stable at temperatures up to about 140°C for short periods of time. It is fixed.

Low sugar content (about 5% or less, preferably about 1% or less) and excellent color (about 7% or less) (lower, preferably about 4 or less, more preferably about 1 or less Gardner color) It is important to have additives that will

In other reactions, the adduct is prepared by adding about 90% or more of about 159 g. It will be done. About 330 g of about 70% corn syrup was degassed with N2 at about 50°C to about 2 Add slowly to the methylamine solution at a temperature below 0°C. Apply this solution for about 30 minutes. Mix to obtain approximately 95% adduct.

This is a very bright yellow solution.

Approximately 190 g of adduct aqueous solution and approximately 9 g of υn1teaCatalyst G49B Add Nf catalyst to a 200ml autoclave, add and evaporate with N2 three times. and scavenge at about 20℃. Increase the N2 pressure to approximately 200 psi and increase the temperature to approximately 5 psi. Raise to 0°C. The pressure was increased to 250 psi and the temperature was increased for approximately 3 hours to approximately Maintain at 50-55°C.

The product is about 95% hydrogenated at this point and then heated to a temperature of about 85°C for about 30 minutes. After removal of water and evaporation, a white powder of approximately 95% N-methylglucoamine is obtained. becomes.

In addition, in order to minimize the Ni content in glucoamine, the N2 pressure must be approximately 1100 It is important to minimize contact between the adduct and the catalyst below 0 psi.

The nickel content in N-methylglucoamine in this reaction is It is about 1100 ppm compared to 10 ppm.

To directly compare the reaction temperature effects, the following reaction with N2 is carried out.

To prepare adducts and carry out hydrogen reactions at various temperatures, representative methods similar to those described above can be used. A 2001 autoclave is used according to the process.

Approximately 420 g of approximately 55% glucose (corn syrup) solution (2: (Lg Gluco (1.28 mol) (This solution is a 99DE cone silicone manufactured by CarGl 11. 119 or less) and has a Gardner color of less than or equal to 1 g of 50% methylamine (59.5g MMA; 1.92 mol) (Ai By combining with glucoamine (Products), Manufacture additives.

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

2. Degas and/or N 55% corn syrup solution at 10-20°C 2 to remove oxygen from the solution.

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

4. Stir for about 1-2 hours when all of the corn syrup solution has been added.

The adducts are used in hydrogen reactions immediately after production or are dehydrated to prevent further deterioration. Stored warm.

The glucoamine adduct hydrogen reaction is as follows: 1. Approximately 134 g of adduct (Gardana) - color 1 or less) and approximately 5.8 g of G49B Ni in a 2001 autoclave. Add to.

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

3. Pressurize with hydrogen to about 400 psi 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- Hold at 55°C. Take sample 1.

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

6. Filter and remove the Ni catalyst by decanting. Take sample 2.

Conditions for constant temperature reaction: 1. Approximately 134g of adduct and approximately 5.8g of G49B Ni were placed in a 200ml oven. Add to toclave.

2. Scavenge twice at low temperature with about 200ps+ hydrogen.

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

4. Increase pressure to about 500 psi and react for about 5 hours. Show temperatureTemperature to hold.

5. Filter out the N1 catalyst by decanting. Sample 3 at about 50-55°C, about 75°C Sample 4 is taken at about 85°C, and sample 5 is taken at about 85°C. (Reaction time at about 85℃ (approximately 45 minutes) All tests gave similar purity of N-methylglucoamine. (approximately 94%). The Gardner colors of these tests are similar immediately after the reaction. However, only the two-step heat treatment provides excellent color stability. Also, the 85℃ test Gives limit color immediately after reaction.

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

Step 1 - Reactant Neyhydrated Maltose (Aldrich).

lot 01318KW); Methylamine (40% by weight in water) (Aldri ch lot 03325TM); Raney nickel, 50% slurry (UA D52073D, Aldrich lot 1292LLW).

The formulation was added to a glass liner (250g maltose, 428g methylamine solution, 1 00g catalyst slurry (50g Ranney Ni) in a 3L rocking autoclave. Place nitrogen (3 x 500 psig) and hydrogen (2 x 500 psig) Sweeping with water and rocking under hydrogen at temperatures of 28-50°C over the weekend.

Pass the crude reaction mixture through a glass microfiber filter with a silica gel plug. and vacuum filtrate twice. Concentrate the filtrate to a viscous material. the obtained substance water by dissolving it in methanol and removing the methanol/water on a rotary evaporator. azeotropically remove the last traces of. Final drying is carried out under high vacuum. Return the crude product Dissolve in flowing methanol, filter, cool to crystallize, filter, and the resulting filtrate Dry the ruta cake at 35° C. under vacuum.

This is cut 1. Concentrate the filtrate until a precipitate begins to form and place in a freezer. Store overnight. Filter the solid and dry under vacuum. This is cut 2. filtrate is concentrated again to half its volume and crystallization is carried out. Very little precipitate It is formed. Add a small amount of ethanol and leave the solution in the freezer over the weekend. solid Filter the body material and vacuum dry. The bound solid contains N-methylmaltoamine. This is used in step 2 of the entire synthesis.

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

In a sealed flask, 20.38 g of tallow methyl ester was heated to its melting point. (hot water bath) into a 2501 round bottom flask equipped with a mechanical stirrer. centre Heat the lask to about 70°C to prevent solidification of the ester. Separately 25.0g N-methylmaltoamine was combined with 45.36 g of methanol and the resulting slurry Stir well and add to the tallow ester. Sodium in 25% methanol solution Add 1, 5+, g of mumethoxide. The reaction mixture should become clear after 4 hours. An additional 10 mol % of catalyst (total 20 mol %) was added and the reaction was continued overnight. The mixture is allowed to continue to cool down (approximately 68° C.) and after this time the mixture becomes clear. Then react for distillation Change flask. Increase temperature to 110°C. Distillation continues for 60 minutes at atmospheric pressure do. High vacuum distillation was then started and continued for 14 minutes, at which point the product was very concentrated. It becomes thick.

The product remains in the reaction flask at 110° C. for 60 minutes. Put the product in a flask Scrape and triturate in ethyl ether over the weekend. Rotary evaporation of ether The product is stored in an oven overnight and then ground. from the product Remove residual N-methylmaltoamine using licagel. 100% methano Place the silica gel slurry in the funnel into the funnel and wash it several times with 100% methanol. Purify. Concentrated sample of product (20g in 100ml 100% methanol) is loaded onto silica gel and eluted several times by vacuum and methanol washes. captured The eluate is evaporated to dryness (rotary evaporator). Remove remaining tallow ester overnight Remove by trituration in ethyl acetate and then filter. Vacuum dry the filter cake overnight. dry The product is tallow alkyl N-methylmaltoamine.

In other embodiments, glucose or a glucose mixture and typically 5 Performed using commercially available corn syrup containing % or more maltose I can do that. The obtained polyhydroxy fatty acid amide and its mixture were It can be used in any detergent composition.

In still other embodiments, step 2 of the reaction sequence comprises 1,2-propylene glycol. It can be implemented within a call or NEODOL. At the discretion of the compounder Therefore, before using the propyl glycol for formulating detergent compositions, the reaction product is It may not be removed from the product. Again, if the formulator so desires, methoxide The catalyst can be neutralized with citric acid to form sodium citrate, which is It can remain in the rehydroxy fatty acid amide.

If desired by the formulator, the compositions of the present invention may employ more or less suds control agents. I can do things. Typically, foaming is desirable for washing dishes, so foaming control is No agents are used. For washing fabrics in top-loading washing machines A certain degree of foam control is desirable, and in the case of a front-loading type, it is equivalent to Foaming control is preferred. Various foam control agents are known in the industry and may be used in the present invention. You can select these based on In fact, foam control for certain detergent compositions The choice of the preparation or its mixture depends on the polyhydroxy fatty acid amide used therein. Depends not only on the presence and amount of surfactants present in the formulation, but also on the other surfactants present in the formulation. is also dependent. However, when using polyhydroxy fatty acid amide, various silicone-based foam control agents are more efficient than other types of foam control agents ( In other words, it can be used at a low level). X2-3419 and Q2-33 02 (Dow Corning), a silicone foam control agent commercially available from this invention. This is particularly useful in light.

For fabric detergent compositions where it is desirable to include stain removers, formulators should Can be selected from known substances of various species (for example, U.S. Patent No. 3.962.152). No. 4,116,885, No. 4,238.531, No. 4.702. '85 No. 7, No. 4.721,580, and No. 4,877.896). used in the present invention The additional soil remover used is a source of C1-4 alkoxy-terminated polyethoxy units ( For example, CH3[0CH2CH2]160H), terephthaloyl unit source ( For example, dimethyl terephthalate), poly(oxyethylene) oxy unit source (e.g. polyethylene glycol 1500), oxyiso-propyleneoxy unit source (e.g. 1,2-propylene glycol), and oxyethylene Oxyethylene oxy in the oxy unit source (e.g. ethylene glycol) units; the molar ratio of oxyiso-propyleneoxy units is at least about 0. The nonionic oligomer esterification product of the reaction mixture containing sources that is 5:1 include.

Such non-ionic stain removers include the following general formula: where R1 is CL-4) Alkyl, especially methyl: X and y are each an integer of about 6 to about 100 : m is an integer of about 0.75 to about 30; n is an integer of about 0.25 to about 20; and R 2 is a mixture of H and CH3, at least about 0.5:1 oxyethylene Oxy unit: gives the molar ratio of oxyiso-propylene oxy unit It is.

Other preferred stain removers include the general animate solution described in U.S. Pat. No. 4,877,896. Although it is of the HOROH type, such stain removers are essentially HOROH type monomers. -, where R is propylene or higher alkyl. Hence the US patent No. 4,877.896 stain removers include, for example, dimethyl terephthalate, ethyl Ren glycol, 1,2-propylene glycol and 3-sodiosulfoamine These additional stain removers include, for example, dimethyl terephthalate, which contains reaction products of zoic acid. tallate, ethylene glycol, 5-sodiosulfophthalate and 3-sodiosulfophthalate It can contain reaction products of diosulfobenzoic acid. Stain remover like this is suitable for use in granular laundry detergents.

Formulators also recommend non-perborate bleach packages, especially in heavy-duty granular laundry detergents. It will be understood that it is desirable to contain Various peroxide bleaches are commercially available. can be used in this case, but among these, percarbonate is convenient and It is economical. Accordingly, the compositions of the present invention preferably contain 3-20% by weight of the composition. solid percarbonate bleach, preferably in the form of 5-18% by weight, most preferably 8-15% by weight. It can contain.

Sodium percarbonate is an additional ingredient in the form of 2Na2CO3.3H202 It is commercially available as a crystalline solid. Most commercially available materials contain low levels of heavy metal ions. sequestering agents such as EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP) or aminophosphates, which are incorporated during the manufacturing process. Ru. In the case of the present invention, percarbonate is incorporated into the detergent composition without additional protection, but A preferred embodiment of the invention uses a stable form of material (FMC). Various coatings can be used, but the most economical is 1.6:1 to 2.8:1, preferably Preferably sodium silicate with a 5i02:Na2O ratio of 12.021; It is applied as an aqueous solution and contains a 2-10% (usually 3-5%) level by weight of percarbonate. yields a Bell's silicate solid. Magnesium silicate can also be used and Any of the following chelating agents can be included in the coating.

The particle size range of crystalline percarbonate is 350μm to 450μm, with an average of 400μm. It is m. When coated, the crystals have a particle size range of 400 to 600 μm.

The heavy metals present in the sodium carbonate used to make percarbonate react This can be controlled by including a sequestering agent in the mixture, but percarbonate requires protection from heavy metals present as impurities in other components in the product. Ru. In order to avoid unacceptable negative effects on percarbonate stability, The total level of iron, copper and manganese should not exceed 25 ppm, preferably Must be less than 20 ppm.

An example of the ingredients of modern condensed laundry detergent particles is as follows.

Implementation fFIJ17 Component Wt, % Cl4-15 alkyl alcohol sulfonic acid ■3C1,4-15 alkyl alcohol Liethoxy(2,25)sulfonic acid 5.80CI2-13 alkyl polyethate Xylate (8,5) 1.45C12-14 fatty acid N-methylglucoamide 2.5゜Sodium aluminosilicate (hydrated zeolite A) 25.2 Crystal laminated case Ilate builder (1) 23.3 Citric acid 10.0 Sodium carbonate Sodium polyacrylate lJ'7m (m , v, 2000-4500) 3.2 diethylenetriamine pentaacetic acid o, 45S a v i n a s e (2) 0.706-nonaraylamino -6-beroxycabronic acid 7.401 Sodium perborate hydrate 2.10 Nonanoyloxybenzene sulfonic acid 5.00 Brightener 0.10 (1) Laminated silicate builders are known in the art. Laminated sodium silicate is preferred Yes. For example, the layered sodium silicate builder of U.S. Pat. No. 4,664.859 See.

Use this as an example. A suitable layered silicate builder is 5KS-6 from Hoechst. It is obtained by

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

Highly preferred granular products of the type described above contain from about 0.0001% to about 2% by weight of active and at least about 1% by weight of the polyhydroxy fatty acid amide, Most preferably the anionic surfactant is an alkylbenzene sulfonate surfactant. It is a product that is not an agent.

Example 18 The following is made by mixing the ingredients in the table below in a mixing drum. The perborate bleach plus bleach activated detergent composition of the present invention is illustrated.

In this example, zeolite A contains about 20% water and has an average particle size of 1 to 1. 0, preferably 3 to 5 microns hydrated crystalline zeolite A; LAS means C 12,3 linear alkylbenzenesulfonate sodium, AS is CI4- 15 Sodium alkyl sulfate, non-ionic means coconut alcohol Condenses with about 6.5 moles of ethylene oxide per mole of alcohol, non-ethoxylated Alcohol and monoethoxylated alcohol removed, abbreviated as Cn AE6.5T and DTPA is sodium diethylenetriaminepentaacetate. It means um.

A S 9.44 18.16 L A S 2.92 5. G2 Moisture 4.47 8.60 Sodium silicate (1,6 ratio) IJ5 2.60 Sodium sulfate [1,47 12,45 Sodium polyacrylate (4500MW) 2.61 5.02P EG8000 1.18 2.27 Nonionic (1,4S (1,89 Sodium carbonate 13.29 25.57 Brightener 0.20 0.38 Sodium aluminosilicate 9.11 17.53DTPA O, 270, 52 Fragrance 0.20 0.38 NAPAA particles (2) 6.09 100.0ONAPAA 2.89 4[i , 96 LAS　O,304,93 Sulfates and other 2.93 48.11 NOBS particles (3) 3.88 100 ．． 0ON OB S 3.15 81.19 LAS　O,123,09 PEG8000 0.19 4.90 Others 0.42 10.82 Zeolite particles (4) 12.00 100.00 Titrium aluminosilicate 7.39 B1.58 PEG8C100t, 5o 12.47 Nonionic 1.1 8 9.70 Moisture 1.138 13.83 Others 0.29 2.42 Additive 5KS-6 layered sodium silicate 15.84 protease (0,078mg/ g activity > 0.521 Eiwa sodium perborate 1.33 Citric acid 6.79 C12-14N-methylglucoamide l, 58 final composition total 100.00 (1) By spray-drying the aqueous clarification mix of the above ingredients, basic particles are formed. is manufactured.

(2) Newly made sample of NAPAA wet cake. This is typically , oxygen (AvO) obtained from approximately 60% water and approximately 2% peracid (approx. (equivalent to 36%) and the remainder (approximately 4%) of unreacted raw materials.

This wet cake consists of NAAA (monononylamide of adipic acid) and sulfuric acid. The crude reaction product with hydrogen peroxide is quenched by placing it in water, then filtered and evaporated. Wet cake is removed by distilled water washing, phosphate buffer washing and final suction filtration. It can be obtained by A portion of this wet cake is air-dried at room temperature to dry The dry sample typically contains about 5% AvO (NAPAA (corresponding to about 90% of the raw material) and about 10% of unreacted raw materials. When dried, sa The sample pH is approximately 4.5.

The NAPAA particles are approximately 51.7 parts by weight of dried NAPAA wet cake ( (contains about 10% unreacted material) and about 11.1 parts by weight of CI2.3 linear alkyl base. sodium benzene sulfonate (LAS) paste (45% active) and approx. Parts by weight of sodium sulfate and about 30 parts by weight of water were mixed in a CUISI~ART mixer. It is made by mixing in After drying, the particles (containing approximately 47% NAPAA) Passed through 14 tie sieves, No.

65 By retaining all particles that did not pass through the ing. According to Malvern particle size analysis, the average amide peracid particles (agglomerates) The average particle size is about 10-20 microns. be.

(3) NOBS (nonanoyloxybenzene sulfonate) particles are US Pat. ,997. '596, which is incorporated by reference.

(4) Zeolite particles having the following composition are zeolite A mixed with PEG3000 and and CnAE6.5T together with EirichRO8 strong mixer. Zeolite A (contains bound water) 70.00 7B, 99P E G 8 000 10JO12,49CnAE6. 5T 8.40 9.72 Free water 10.80 0.80 PEG 8000 is a water-containing form of 5096 and has a temperature of approximately 55°F (12.8°C). ) is the temperature. CnAE6.5T is liquid and approximately 90°F (32.2°C) is maintained. These two liquids are pumped through a 12-element static mixer. It is mixed by doing. The resulting binder material is approximately 75°F (23.9°C) and a viscosity of about 5000 cps. PEG passing through this mixer The ratio of 3000 and CnAE6,5T is 72:28.

The Ei r i ch RO8 strong mixer is operated in batch mode. first Place 34.1 kg of powdered zeolite A into the mixer pan. mixer Start and first rotate the pan counterclockwise at a speed of approximately 75 revolutions per minute, then Rotate the blade clockwise at 1800 rpm. Next, zeolite A was contained Add the binder from the static mixer into the Eirich RO8 high energy mixer. Pump directly. The binder feed rate is approximately 2 minutes. This mixer is about 3 Continue mixing for an additional minute for a total batch time of minutes. Then drain the batch and Collect in a drum.

Repeat the batch step until approximately 225 kg of wet product has been collected. . This discharged product is transferred to a fluidized bed at 240-270@F (116-132°C). dry inside. This drying step removes most of the free water and removes the composition as described above. change. added by the mixer to the product in batch mode Total energy manpower is approximately 1.31X1012e rg/kg, approximately 2.18X10 The ratio is 9 e rg/kg-s.

The resulting flowable agglomerate has an average particle size of about 4500-500 microns. Ru.

Example 19 Relatively expensive, common among front-loading automatic washing machines, especially in Europe The composition of granular laundry detergent compositions suitable for use at concentrations and over a wide temperature range is as follows: Ride 5KOKALAN CPS (Na salt as toou tongue ffi (1) 3.52DEQUE9206B (acid 100%/lff1 (2) 0. 45TINOPAL DMS (3) 0.28Mg S 04 0.49 Zeolite A (anhydrous 1-5μ) 17.92CMCaouou tongue 1 (4) 0. 47Na2 CO39,44 Citric acid 3.5 Laminated silicate 5KS-612,9 Tallow alkyl sulfate (100ν tongue; N19 2.82C14-15 alkyl sulfate Acid acid (100%; lingual; NafjL) 3.5C12-15 alkyl EO (3) Sulfate 1,76CIO-18N-methylglucoamide 4. ■DOBANOL C12-15EO (3) 3.54 LIPOLASE (100,000t, U/g) (5) 0.42SAVINASE (4, OK) IP[j) (6) 1.65 fragrance 0.53 X2-3419 (7) 0.22 Starch 1.08 Stearyl alcohol 0,35 Sodium percarbonate (coated) 22J tetraacetylethylenediamine (TAED) 5.9 Phthalocyanine Zinc B, 02 Water (from zeolite) remaining amount (1) SOKALA! J is polyacrylic acid/malley commercially available from Hoechst It is sodium chloride.

(2) Monsanto trademark pentaphosphonomethyl diethylenetriamine.

(3) Ciba Geigy's brightener.

(4) FINNFIX, a trademark of Metasaliton.

(5) Lipophilic (I1polytic) enzyme LIPOLAE from NOVO (13) Pro5-7-ase enzyme SAV I NASE (7)X2 from NOVO -3419 is a foam suppressant from Dow Corning.

Particle manufacturing methods include various tower drying, agglomeration, dry addition, etc. as shown below. including the stages of Nokuichicent is based on finished composition.

A. Using standard techniques for clutching and blowing through the tower, Crutch the ingredients and tower dry.

5OKALAN CPS 3.52% DEQtlEST 20 [i6 0.45% TlN0PAL DMS 0.28 % Magnesium sulfate 0.49% Anhydrous zeolite A7.1% CMCO, 47% and 70% paste of Cl2-15 EO(3) sodium sulfate salt into zeolite. A agglomeration treatment with A and sodium carbonate in the following proportions (agglomeration Contribution of Romelate to detergent formulation after drying).

Tallow alkyl sulfate 2.82% C12-15EO(3) Sulfate 1.18% Zeolite A5.3% Sodium carbonate 4.5% B2. C14-15 alkyl sulfate, C12-15 alkyl ethquin sulfate, D OBA~OL C12-15EO (3) and C1B-18 amide nonionic substance DO present during the reaction of methyl ester and N-methylglucoamine Combine with BANOL C12-15EO (3”). DOBANOL C12- 15EO(3) acts as a melting point depressor, thereby removing unwanted cyclic The reaction can be carried out without forming glucose amide.

20% DOBANOL C12-15EO (3) and 80% C1B-18N- A surfactant mixture with methyl glucose amide was obtained, which was mixed with 10% sodium carbonate. Co-agglomerate treatment with thorium.

Next, the particles were combined with C14-15 alkyl sulfate and C1,2-15E O( 3) Sodium salt of sulfate, zeolite A and excess sodium carbonate Perform romeration processing. This particle is C1G~18N-methylglucose amino It shows excellent dispersibility in cold water.

The overall composition of these particles (contribution to the detergent composition after drying of agglomerate) is as follows: Here is the record: C16-18 N-methylglucoseamide 4.1% DOBANOL 012 -15 EO (3) 0.94% Sodium Carbonate 4.94% Zeolite A5.3% C14-15 alkyl sulfate Na salt 3.5% C12-15EO (3) sulfate Na salt 0,59% C1 dry additive Add the following ingredients Percarbonate 22.3% TAED (Tetraacetylethylenediamine) 5.9% Hoechst's laminated silicone Acid acid 5K5612.90% citric acid 3.5% Lipolase 0.42% 100.000 LU/g SAVO)4ASE 4. OKNPU 1.85% Zinc Phthalocyanine (Photobleached ) 0.02% D, spray-on DOBANOL C12-15EO (3) 2.60% Fragrance 0.53% E. Foaming inhibitor Silicone Foam Suppressant X2-3419 (95%-97% High Molecular Weight Linear Silicone Zeolite A (particle size 2-5%) (Dow Corning) μ), co-agglomeration treatment with starch and stearyl alcohol binder do. The particles have the following formulation: Zeolite A O, 22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% This detergent is used in European washing machines, for example in AEG-brand washing machines. cycled at 30°C, 40°C, 60°C and 90°C using 85g detergent. It showed excellent solubility, performance and foam control when used.

Example 20 In any of the above examples, instead of the fatty acid glucoamide surfactant, Equal amounts of maltamide or glucoamide/maltamide surfactant from runt Mixtures of agents can be used. If you use ethanolamide in your composition, It is believed to promote low temperature stability of the finished formulation. Additionally, amine oxides and /Also it sulfopetaine (akar saltaine J) The use of surfactants produces excellent foaming.

If particularly high foaming compositions are desired, less than about 5%, more preferably about 2% %, and preferably substantially zero C14 or higher fatty acids. It is preferable to have a car with a lot of power. This is because these can suppress foaming. Therefore, high foaming The formulator of the composition may include this along with the polyhydroxy fatty acid amide in the high lather composition. Avoid introducing foam-inhibiting amounts of higher fatty acids such as (1 is composition It is desirable to avoid the formation of C14 and higher fatty acids during storage. easy means The CI2 ester reaction was carried out to produce the polyhydroxy fatty acid amide of the present invention. It's about using things. Fortunately, the use of amine oxides or +1 sulfopetaine can overcome to some extent the undesirable foaming effect caused by fatty acids. .

Relatively high concentrations (e.g. 10% or more) of anions or polyanions For example, for liquid detergents containing polycarboxylate builders, anionic Formulators who wish to add brighteners should combine brighteners with water and polyhydroxy fatty acids. It may be desirable to premix with the amide and then add the premix to the final composition. cormorant.

For zeolite built detergents, polyglutamic acid or polyaspartic acid It is effective to use it. AE fluid or flakes and DC-544 (Dowco foaming) are other examples of effective suds control agents.

As will be apparent to those skilled in the art, the use of enzymes such as maltose and higher saccharides In the production of polyhydroxy fatty acid amide, linear substitution Z is added to the polyhydroxy ring structure. Thus forming a "capped" polyhydroxy fatty acid amide. like this Any material may be fully used in the present invention and is within the scope of the invention.

Submission of translation of written amendment (Article 184-8 of the Patent Law) March 26, 1993 Mortar”

Claims (15)

[Claims] 1. Single or multiple anionic, nonionic or cationic detersive surfactants or the mixture, optional detergent additives, and optional aids. A zeolite-built detergent composition comprising a builder, wherein said detergent composition teeth, (a) at least 1% by weight of a zeolite or layered silicate detergent builder; or (b) at least 1% by weight of a polyhydroxy fatty acid amide of the formula including ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ Here, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, roxypropyl or mixtures thereof; R2 is C5-C31 hydrocarbyl; and Z is a linear hydrogen having at least 3 hydroxyl groups directly attached to the molecular chain. Polyhydroxyhydrocarbyl or its alkoxylated derivatives, including dorocarbyl A zeolite-built detergent composition characterized by being a conductor. 2. According to claim 1, the zeolite builder is zeolite A. The granular detergent composition described. 3. Z of the polyhydroxy fatty acid amide substance is derived from reducing sugar, and R1 is methyl , and a claim characterized in that R2 is C9-17 alkyl or alkenyl. Item 1. The composition according to item 1. 4. Claim 3, characterized in that Z includes -CH2(CHOH)4CH2OH Compositions as described. 5. In the polyhydroxy fatty acid amide, Z is derived from maltose. A composition according to claim 1, characterized in that: 6. In the polyhydroxy fatty acid amide, Z is monosaccharide, disaccharide derived from a mixture of lidos and optionally higher saccharides, said mixture contains at least 1% of at least one disaccharide, preferably maltose. The composition according to claim 1, characterized in that it has the following characteristics: 7. The zeolite:polyhydroxy fatty acid amide ratio is preferably 1:10 to 20:1. or 1:5 to 15:1, most preferably 1:3 to 10:1. The salt composition according to claim 1, characterized in that 8. Alkyl sulfate, alkyl ethoxylate sulfate, alkyl ester sulfate phonates, preferably methyl ester sulfonates and alkylbenzenes one or more anionic surfactants selected from the group consisting of sulfonates; The detergent composition according to claim 1, characterized in that it contains a sex agent. 9. Furthermore, alkyl ethoxylate or alkyl polyglycoside nonionic interfaces 9. Detergent composition according to claim 8, characterized in that it comprises an active agent or a mixture thereof. 10. Claim 1 further comprising a polycarboxylate builder. Detergent compositions as described. 11. Single or multiple anionic, nonionic or cationic detersive surfactants or or with mixtures thereof; with zeolite or layered silicate builders or mixtures thereof; ; includes optional detergent additives; and optional auxiliary builders. In a method for enhancing the fabric cleaning performance of a detergent composition comprising: The method comprises adding at least 1% by weight of a polyhydroxide of the formula: ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ Here, R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydrocarbyl, droxypropyl, or mixtures thereof, R2 is C5-C31 hydrocarbyl, or Z is a linear chain having at least 3 hydroxyl groups bonded directly to the molecular chain. Polyhydroxyhydrocarbyl containing hydrocarbyl, preferably C11-17 N-methylglucoamide, C11-17N-methylmaltoamide, or a mixture of lucoamide and maltamide, or an alkoxylated derivative thereof; The ratio of the zeolite to polyhydroxy fatty acid amide is 1:10 to 20:1. washing the fabric in a normal manner using only the detergent composition. rinsing. 12. The detergent composition may contain one or more anionic surfactants. 12. The method of claim 11. 13. The Z moiety in the polyhydroxy fatty acid amide is extracted from the plant. derived from a mixture of monosaccharides, disaccharides and polysaccharides 12. The method according to claim 11. 14. The R2 moiety in the polyhydroxy fatty acid amide is C15-17 Claim 11, characterized in that it is alkyl, alkenyl, or a mixture thereof. Method described. 15. The anionic surfactant is an alkylbenzene sulfonate surfactant. 12. The method of claim 11, characterized in that: