JPH07500861A - Detergent composition containing glyceryl ethers - Google Patents

Abstract

A detergent composition comprises (a) one or more glyceryl ethers of a C12-C18 alkyl or alkenyl primary or secondary alcohol, at least 50 mole percent of the glyceryl ether being diglyceryl ether and not more than 25 mole percent of the glyceryl being monoglyceryl ether, and (b) an anionic detersive surfactant. The compositions, which may be in granular or liquid form, may also contain other conventional ingredients, e.g. other detersive surfactants, detergency building compounds, enzymes and bleaches.

Description

[Detailed description of the invention] FIELD OF THE INVENTION Detergent compositions comprising glyceryl ethers The present invention uses one or more glyceryl ethers as a nonionic detersive surfactant. Regarding detergent compositions, especially heavy duty compositions containing Ru.

Background of the invention Strong detergents, regardless of particles or liquids, generally have an anion of 11 to 13. Sodium (linear alkyl)benzene sulfate, or sodium alkyl sulfate, e.g. For example, sodium alkyl sulfates obtained by sulfating C8-C18 alkanols Contains thorium. Performance of such detergent compositions against oil stains and soils Non-ionic detersive surfactants, typically (C-C15 condensation of phenol or 08-C22 alkanol with ethylene oxide It is common to compound the products. A preferred condensate is alkylphenol 1 3 to 12 moles of ethylene oxide per mole or ethylene per mole of alkanol It contains 4 to 8 moles of carbon oxide. Particularly preferred nonionic surfactants It is a condensate with 7 moles of lyethylene oxide.

The ethylene oxide used in the preparation of the nonionic surfactants described above is However, it is derived from petroleum, and furthermore, care should be taken to avoid the risk of explosion as much as possible. It needs to be treated in depth. For these reasons, it is important to consider both economic efficiency and safety, as well as other aspects. Considering environmental aspects, it is desired to find alternative nonionic surfactants.

Summary of the invention The present invention provides detergent compositions with the general formula % formula % (1) (In the formula, R represents an alkyl or alkenyl group having 12 to 18 carbon atoms, and C3H60 2 removes hydrogen from a hydroxyl group and another hydroxyl group from glycerol. and n is an integer) The above glyceryl ethers, especially 50 to 100 mol% are diglyceryl ethers (n=2), and 0 to 25 mol% is monoglyceryl ether (n=1). The remainder (if any) consists of triglyceryl ethers (n = 3) and / or glyceryl ethers composed of higher analogues (n>3) Regarding the use of classes.

According to one aspect of the present invention, (a) one or more groups represented by the above general formula (1); Detergent set comprising lyceryl ethers and (b) anionic detersive surfactant products are provided.

Description of specific embodiments Glyceryl ethers represented by the general formula (1) defined above are nonionic cleaning agents. It is useful as a surfactant. In the detergent composition of the present invention, at least 50 mol %, preferably less than 60 mol % of the glyceryl ethers contained in the mol% is composed of diglyceryl ether and is less than 25 mol%, preferably 20 The mole percent or less must be composed of monoglyceryl ether. Guri The remainder (if any) of the seryl ether component (a) is a triglyceryl ether and/or higher analogues.

Generally, the diglyceryl ether content of the glyceryl ether component (a) is large. It turned out that the better.

Diglyceryl ether constitutes 80 mol% or more of the glyceryl ether component Preferably, the glyceryl ether component of the composition of the invention is substantially completely di-glyceryl. It is particularly preferable that it is composed only of ceryl ether.

Diglyceryl ethers are homogeneous polyglycerol dodecyl ether nonionic Solution properties of surfactants Ogeneous polyglycer’oldodecyl ether H-Sagitani (H, Sagitani) et al., J.A.O.C.

SL, Vol. 66, No. 1 (January 1989), pp. 146-152. It can be prepared by certain methods. Specifically, Sagitani etc. are exposed to sodium chloride in a nitrogen atmosphere. Add um to anhydrous glycerol and heat the solution at 130 °C for 1 hour to obtain 1 of glycidyl dodecyl ether to sodium glycerate at 180°C. the mixture was stirred for 8 hours and the product was can be generated on a silica gel column using lum/methanol (98:2). discloses the preparation of diglyceryl dodecyl ether by the following methods. Sagita D et al. expressed the above production method using the following reaction scheme.

RO(CHCHCH,,O) 2H ship CH (In the formula, R12 represents a dodecyl group).

The applicant believes that the above production method applies not only to the R12 compound but also to the above general formula (1). Applies to compounds having any group within the meaning defined for R in I found out what I can do. R is usually derived from a primary or secondary alcohol.

Furthermore, the method taught by Sagitani et al. purifies by chromatography. However, the free radicals present in the main by-products, glycerol cyclic dimer and epoxide, Fatty alcohols can also be used in a method that appears to be new in this regard, namely a simple It was found that it could be sufficiently removed by distillation. That is, using simple vacuum distillation, e.g. For example, at a pot temperature of about 200°C, no significant decolorization and decomposition (, cyclic by-products 2 % and less than 2% free fatty alcohols. It has been proven that ethers can be obtained. This is especially true for Takai shi et al. in US-A-4,465,866 (column 3, lines 10-14) , distillation in the production method of polyol ethers is laborious and industrially difficult. It is surprising that it is not available.

The glyceryl ether product obtained by the above method is a diglyceryl ether product. If the mole % is less than required and/or the monoglyceryl ether is specified However, the diglyceryl ether content is and isolation techniques.

Also, the expression % formula % (2) In addition to the diglyceryl ether represented by the formula Diglyceryl ethers are also commonly formed.

Typically, about 1 mole of diglyceryl ether (2) is produced per 4 moles of diglyceryl ether (2). Glyceryl ether (3) is formed.

A mixture of positional isomers of formulas (2) and (3) or a mixture comprising them is a new It seems to be a rule. The above-mentioned Sagitani etc. are diastereomers (glycerol Discloses only the possibility of optical isomerism (a concept of optical isomerism) due to the fact that ing. When preparing a mixture containing isomer (3), the primary alcohol group Since the content of isomer is higher, this isomer is more abundant on the silica gel side and is easily removed. Silica gel chromatography should be avoided because of the expected It is thought that there is no.

Mixtures of positional isomers (2) and (3) have better cleaning properties than single isomers alone Sometimes.

Generally, the group R will be attached to the first position of the first glycerol moiety. Second Glycero As a rule, the glycerol binds to the second site of the first glycerol. however, In fact, less than 10 mol % of diglyceride ethers are attached to the second site. It was generally found that the For example, glyceryl ethers are natural When obtained from fatty alcohols ROH, R is alkyl and/or alkyl. It may also be a mixture of nyl groups. - As an example, mainly C12, C14 and C16 saturated alkaline Coconut alcohol 1 containing kill groups and small amounts of C8, C and 018 alkenyl groups 〇 There is one ru. R is preferably cocoyl, especially mainly n-dodecyl (C) and n - so-called "topped and tailed" which is tetradecyl (C14) and It is a "narrow range" cocoil. Glycidyl alkyl (or alkenyl) ethers are known compounds, some of which are industrially obtainable or in principle known. It can be prepared by the following method. 1, for example, a useful starting material is Brochter's Aluminum is available under the trade name rEpoxide No. 8J from the Quil glycidyl ether. Note that the alkyl group in this epoxide is The range is cocoil.

Furthermore, diglyceryl ether is also used in US-A-4,465,866 (Takai shi etc.) by methods known in principle. This U.S. patent The diglyceryl ether of the above formula (2) can be prepared by (or alkenyl) glycidyl ether and glycerol acetal or digit 1,3-dioxolane is obtained by reacting with a diol derivative, and then hydrolyzed. It teaches that it can be prepared by

In addition, Taka i sh i et al. have reported on the preparation of the above-mentioned diglyceryl ethers. Previous proposals, in particular (i) the reaction of a linear dimer of glycerol with an alkali, forming an alkali metal alcoholade and then reacting with an alkyl halide; and (ii) obtained after reacting alcohol and a 1,3-dioxolane type cyclic compound. (Journal of park).

Chemie, Bands, Vol. 316, 1974, pp. 325-336) It is also mentioned.

The glyceryl ether component (a) is usually added to the composition of the present invention in an amount of 0.5 to 30% by weight, Preferably it is present in an amount of 3 to 15% by weight, more preferably 5 to 10% by weight.

The detergent composition of the present invention, which may be liquid or granular, has at least one anionic detergent. Contains surfactant. Optionally, the composition also includes at least one other Detergent surfactants, preferably cationic, amphoteric and zwitterionic detersive surfactants as well as at least one other detersive surfactant selected from Ingredients commonly used in the field, such as builders, enzymes, bleaching agents, bleaching activities agent, polymer stain release agent, chelating agent, mud stain removal/redeposition prevention agent, polymer dispersion It may also contain agents, brighteners, suds suppressants, pH buffers, dyes or pigments.

Any of the above ingredients, whether essential or optional, may be added as needed. It is understood that it can be composed of a mixture of two or more compounds with appropriate properties. It would be around.

Detergent surfactants typically have a total amount of 0-50% by weight, preferably 1-30% by weight. %, more preferably 5 to 20% by weight.

Although the present invention is particularly useful for heavy-duty or general-purpose laundry detergent compositions, The term ``products'' refers to dishwashing compositions, hard surface and other household cleaners, and shampoos. Also includes personal care products such as -. Possible anionic detersive surfactants and species Examples of each optional component include the following.

anionic surfactant In addition to the nonionic surfactant system of the present invention, the detergent composition of the present invention includes one or more of the following: As alkyl ester sulfonate surfactants containing anionic surfactants of , rThe Journal of the American Oil Che mistsSocietyJ, 52 (1975), pp. 323-329 08-C2o carboxylic acid (i.e. fatty acid) line sulfonated with gaseous S03 Contains esters. Suitable raw materials include natural products derived from beef tallow, palm oil, etc. Contains fatty substances.

Preferred alkyl ester sulfonate surfactants, especially alkyl ester sulfonate surfactants for laundry applications. ester sulfonate surfactant has the structural formula (wherein R is C-C hydrocarbyl, preferably alkyl or a combination thereof and R4 is cI-C6 hydrocarbyl, preferably alkyl or their combination, and M forms a water-soluble salt with the alkyl ester sulfonate containing an alkyl ester sulfonate surfactant represented by That's what happens. Suitable salt-forming cations include sodium, potassium and lithium. Metals and monoethanolamine, jetanolamine and triethanolamine Substituted or unsubstituted ammonium cations such as ions are included. Preferably R+;! CIG-' CI5 alkyl, R4 is methyl, ethyl or isopropyl It is. In particular, methyl ester sulfonates in which R3 is C-C alkyl preferable.

Alkyl sulfonate surfactant Alkyl sulfate surfactants are water-soluble salts or acids represented by the formula RO803M. It is a kind. In the formula, R is preferably 010"" C24 hydrocarbyl, preferably is an alkyl or hydroxyalkyl having a clo-C20 alkyl component, and more Preferably CI2-CI8 alkyl or hydroxyalkyl, M is H or Cations, such as alkali metal cations (e.g., sodium, potassium, or ammonium or substituted ammonium (e.g. methyl-, dimethyl- thyl- and trimethylammonium cations and tetramethylammonium and Quaternary ammonium cations such as dimethylpiperidinium cations and ethyl Alkylars such as amines, diethylamine, triethylamine and mixtures thereof quaternary ammonium cations derived from amines, etc.). Preferably carbon number It is an alkyl chain having 12 to 16 carbon atoms, more preferably 14 to 15 carbon atoms.

Alkyl alkoxylated sulfate surfactant Alkyl alkoxylated sulfate The ate surfactant is a water-soluble salt or acid represented by the formula RO(A) 803M. be. In the formula, R has an unsubstituted C-C alkyl or 010-C24 alkyl moiety hydroxyalkyl group, preferably 012-C2o alkyl or hydroxyalkyl alkyl, more preferably an alkyl having 12 to 18 carbon atoms, especially an alkyl having 12 to 15 carbon atoms. is a group.

A is an ethoxy or propoxy unit and m is greater than zero, typically about 0.5 to about 6, more preferably 0.5 to about 3, and M is H or, e.g., a metal Cations (e.g., sodium, potassium, lithium, calcium, magnesium (e.g.), ammonium or substituted ammonium cations. It is.

In the present invention, not only alkyl ethoxylated sulfates but also alkyl propoxylates can be used. Silated sulfates are also suitable. As a specific example of a substituted ammonium cation is a methyl-, dimethyl-, trimethyl-ammonium cation as well as a tetramethyl-ammonium cation. Quaternary ammoniums such as thyl-ammonium and dimethylpiperidinium cations Cations and ethylamine, diethylamine, triethylamine, and mixtures thereof. Examples include those derived from alkylamines such as compounds.

A preferred surfactant is 012-C15 alkylbolythoxyleh (3,0 ) sulfate (012-C15E(3,0)M). Other typical surfactants As a sex agent, 012-C18 alkyl polyethoxylate (1,0) sulfate (CI2-C,8E (1,0)M), C,2-C18 alkyl polyethoxylate Sylate (2,25) sulfate (C-CE (2,25)M), C12~ C18 alkyl polyethoxylate (3,0') sulfate (CI2-C,8 E (3,0)M) and C12-C18 alkyl polyethoxylate (4,0) Sulfate (C12-Cl8E(4,0)M) (where M is sodium and carbon (appropriately selected from Rium).

Other anionic surfactants Other surfactants useful for cleaning purposes can also be included in the detergent compositions of the present invention.

These surfactants include soaps, 09-C20 linear alkylbenzene sulfonants, nates, C-C22 secondary or secondary alkanesulfonates, C8-C24 ole Finsulfonates, such as those described in British Patent No. 1.082.179 Prepared by sulfonation of pyrolysis products of alkaline earth metal citrates sulfonated polycarboxylic acids, C”” C24 alkyl polyglyceate Salts of rusulphates (containing 10 moles or less of ethylene oxide) (e.g., sodium potassium, ammonium and mono-, di- and triethanolamine salts (including substituted ammonium salts such as); alkylglycerol sulfonates, fats Acylglycerol sulfonates, fatty oleylglycerol sulfates , alkylphenol ethylene oxide ether sulfates, paraffins Isethiolytes such as sulfonates, alkyl phosphates, acylisethionates, etc. nates, N-acyltaurates, alkylsufucinamates and sulfosc cynates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12-CI8 monoesters) and diesters of sulfosuccinate (Toriwa saturated and unsaturated C-Cl2 diesters), acyl sarcosinates, alkaline sulfate of gyl polyglucoside (a non-ionic non-sulfated compound is discussed below) ) and other alkyl polysaccharide sulfates, branched chain primary alkyl sulfates, + Formula RO(CHCHO) CH3COO-M (in the formula, 2k R is 08-C22 argyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation It includes alkyl polyethoxy carboxylates such as those represented by . Resin acids present in or derived from rosin, hydrogenated rosin and tall oil Resin acids and hydrogenated resin acids such as and hydrogenated resin acids are also suitable. A further example is [ Surfactants and detergents (Surface Active Agents and D etergents) J, Schwartz.

Perry and Berch, Volumes 1 and 1I. Ma In addition, a variety of such surfactants are generally L a u g h l i n U.S. Pat. No. 3,929.678, No. 23, issued December 30, 1975, by et al. Column, line 58 to column 29, line 23 (incorporated by reference to this disclosure) ) is disclosed.

Preferred anionic surfactant systems for use in detergent compositions of the present invention include alkaline surfactants. Contains no killbenzene sulfonate. Highly favorable systems account for the major proportion CI4-C15 quaternary-alkylsulfate and a small proportion of alkyl ethoxy CI2-C15 alkyl with an average of 3 ethoxy groups per mole of sulfate ethoxy sulfate. The detergent compositions of the present invention are typically Typically, the anionic surfactant is added in an amount of about 1 to about 20% by weight, preferably about 3 to about 15% by weight. % by weight, most preferably from 5 to 10% by weight.

Other surfactants The detergent composition of the present invention also has cationic, amphoteric, zwitterionic and semipolar surfactants. agents as well as further nonionic surfactants. Detergent composition according to the present invention Suitable cationic detersive surfactants for use in It has a building group. Examples of such cationic surfactants include: Ammonium surfactants such as alkyldimethylammonium halogenides and Examples include surfactants represented by the formula.

[R(OR3)　[R'(OR3)　]　R”N　+X-Y　y2 In the formula, R2 is an alkyl or alkylben where the alkyl has about 8 to about 18 carbon atoms. is a zyl group, and each R3 is -CHCH-1-CH2CH(CH3)-1-Cf-f Consisting of 2CH(CH7OH)-1-CH2CH2CH2- and mixtures thereof selected from the group: each R4 is C-C alkyl, C-C hydroxyalkyl; A benzyl ring structure formed by combining two R4 groups of Kinope, -CHCHOH-CHOHCOR6CHOHCHOH (wherein R6 is hexose or a hexose polymer having a molecular weight of less than about 1000 and when y is not 0 is hydrogen); R5 is the same as R4, or the total number of carbon atoms of R2 and R5 is an alkyl chain in which the number is 18 or less; each y is from 0 to about 10, and the sum of the y values is 0 to about 15: and X is a compatible anion.

Also, other cationic surfactants useful in the present invention are No. 4,228,044 to Cambre (The content disclosed herein is incorporated herein by reference.) (considered part of the disclosure).

When incorporating such surfactants, the detergent compositions of the present invention typically contain Contains 0 to about 25% by weight, preferably about 3 to about 15% by weight of such surfactants. It will be done.

Amphoteric surfactants are also suitable for use in the detergent compositions of the present invention. this In a broad sense, these surfactants are secondary or secondary surfactants in which the aliphatic group may be linear or branched. Regarded as aliphatic derivatives of triamines or aliphatic derivatives of heterocyclic secondary and tertiary amines It can be done. One of the aliphatic substituents has at least 8 carbon atoms, typically carbon number is about 8 to about 18, and at least one is an anionic water soluble Contains chemical groups such as carboxy, sulfonate, sulfate. bisexual world For examples of surfactants, see Lughlin et al., published December 30, 1975. No. 3,929.678, column 19, lines 18-35 (by reference) (which is hereby incorporated by reference).

When incorporating such an amphoteric surfactant, the detergent composition of the present invention typically 0 to about 15% by weight, preferably about 1 to about 10% by weight of such amphoteric surfactants. % content.

Zwitterionic surfactants are also suitable for use in the detergent compositions of the present invention. . These surfactants are broadly defined as secondary and tertiary amine derivatives, heterocyclic secondary amines, etc. and derivatives of tertiary amines or quaternary ammonium, quaternary phosphonium or quaternary amines. It can be considered a derivative of trisulfonium compounds. of zwitterionic surfactants For example, see Laughlin et al., US Special Edition, December 30, 1975. No. 3,929,678, column 19, line 38 to column 22, line 48 (please quote) (herein incorporated by reference).

When blending such a zwitterionic surfactant, the detergent composition of the present invention: Typically such zwitterionic surfactants are present in an amount of 0 to about 15% by weight, preferably about It contains 1 to about 10% by weight.

Semi-polar nonionic surfactants contain one alkyl component having about 10 to about 18 carbon atoms. and a group consisting of an alkyl group and a hydroxyalkyl group having about 1 to about 3 carbon atoms. Water-soluble amine oxides containing two components selected from 11 alkyl components having about 18 carbon atoms and an alkyl group having about 1 to about 3 carbon atoms; A water-soluble phosphor containing two components selected from the group consisting of hydroxyalkyl groups. Finoxytes; and one alkyl component having about 10 to about 18 carbon atoms; , a group consisting of alkyl and hydroxyalkyl components having about 1 to about 3 carbon atoms. A nonionic surfactant containing a water-soluble sulfoxide containing a component selected from This is a special category of

Semipolar nonionic surfactants include amine oxide surfactants represented by the formula below. be caught.

In the formula, R3 is alkyl, hydroxyalkyl or alkyl having about 8 to about 22 carbon atoms. is a kylphenyl group or a mixture thereof: R4 is an alkylphenyl group having about 2 to about 3 carbon atoms; or a hydroxyalkylene group, or a mixture thereof; X is from 0 to about 3; Yes: and each R5 is alkyl or hydroxyalkyl having about 1 to about 3 carbon atoms or a polyethylene oxide group having about 1 to about 3 ethylene oxide groups . The R5 groups are, for example, bonded to each other via oxygen or nitrogen atoms to form a ring structure. may be completed. These amine oxide surfactants include, among others, C10""cI 11 Alkyldimethylamine oxides and 08-c12 alkoxyethyldihyde Contains dolokidiethylamine oxides.

When incorporating such a semipolar surfactant, the detergent composition of the present invention typically Typically, the amount of such semipolar surfactant is 0 to about 15% by weight, preferably about 1 to about 1% by weight. It contains 0% by weight.

nonionic surfactant In addition to the glyceryl ether component described in Section 2, the detergent composition of the present invention contains non-ionic It may also contain a surfactant.

Suitable nonionic surfactants include alkylphenols such as polyethylene oxide; Condensate, e.g. 1 to 12 moles of ethylene oxide per mole of alkylphenol. Alkylphenol having a straight chain or branched alkyl group having 6 to 8 carbon atoms Condensation products of the following types are included.

Suitable nonionic surfactants include carbon atoms of 8 to 22, preferably carbon atoms of 12 to 22. -18 linear or branched aliphatic alcohols and ethyl alcohol per mole of alcohol. Also included are condensation products with 2 to 12 moles of tyrene oxide, preferably 3 to 7 moles. .

Suitable nonionic surfactants also include carbohydrates, glycosides, and amino acids. Fatty acyl or alkyl condensation products of the oxy type and their derivatives such as polyols Also includes products. For example, cocoalkyl polyglucosides and tallow-acyl- Examples include N-methyl-glucamides.

If additional nonionic surfactants are used, not more than 15% by weight of the composition; Usually present in an amount of 1 to 6% by weight, the detergent composition of the present invention facilitates mineral hardness control. Inorganic or organic detergent builders may be included to improve the detergent properties.

Builder levels vary widely depending on the end use of the composition and the desired physical form. can be done.

Liquid formulations typically contain at least about 1% detergent builder, more typically about 1% by weight detergent builder. 5 to about 50%, preferably about 5 to about 30% by weight.

Granular formulations typically contain less detergent builder (about 1% by weight, more typically about 1% by weight). 10 to about 80%, preferably about 15 to about 50% by weight. however , does not preclude lower or higher level builders.

Inorganic detergent Bilgoo contains polyphosphates (tripolyphosphates, pyrophosphates, (examples include glassy polymer metaphosphates), phonates, phytic acid, silicates, carbonates (bicarbonates and (including sesquicarbonates), sulfates and aluminosilicates. Includes alkali metal, ammonium and alkanol ammonium salts; They are not limited to these. Baud rate builders as well as detergent storage or cleaning conditions A builder containing a baud rate forming substance capable of generating a baud rate under conditions - can also be used, but is preferred under cleaning conditions below about 50°C, especially below about 40°C. Not good. Preferred Bilgoo systems also do not contain phosphates. Silike As a base builder, for example, alkali metal silicates, especially SiO:Na ,,0 ratio is 1. a:i ~3.2:1 and according to H, P, Rfeck No. 4,664.839, issued May 12, 1987, disclosed herein. The content herein is incorporated by reference). There are layered silicates such as layered sodium silicate. However, for example , with a crispening agent in the granular formulation. can serve as a stabilizer for oxygen bleaches and as a component of foam control systems Other silicates such as magnesium silicate are also useful.

As a carbonate builder, for example, Germany published on November 15, 1973 Patent Application No. 2,321゜001 (The content disclosed herein may be cited. (herein incorporated by reference) Alkaline earth metal carbonates and alkali metal carbonates, including sodium carbonate There is a mixture of them with ultra-fine calcium carbonate.

Aluminosilicate builders are useful in the present invention.

Aluminosilicate Builder is one of the most powerful granular detergents currently on the market. It is also used as an important builder ingredient in liquid detergent compositions. It can also be used.

Aluminosilicate builders include those represented by the following empirical formula.

M (zAIO-ySiO2) where M is sodium, potassium, ammonium or substituted ammonium: 2 is about 0.5 to about 2; and y is 1. This material is anhydrous aluminium Ca per gram of lysate, CO3 hardness equivalent to at least about 50 mg Has sium ion exchange capacity. Preferred aluminosilicates are represented by the following formula: It is zeolite virgoo.

Na [(AIO) (SiO)] ・xH20r 2! 2y where 2 and y are integers of at least 6 and the z:y ratio is from 1.0 to about 0.5 or an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. these aluminum Silicates may have a crystalline or amorphous structure, and are natural aluminosilicates. or synthetic aluminosilicates. Aluminosilicate ion exchanger The quality manufacturing method is described in the US patent by Krummel et al., October 12, 1976. It is disclosed in Japanese Patent Application No. 3°985.669. The content disclosed herein is It is incorporated by reference into this disclosure. Preferred syntheses useful in the present invention Crystalline alkaline ion exchange materials include zeolite A1 zeolite I-P (B) and zeolite It is available under the name Light-X. In particularly preferred embodiments, crystalline aluminosilicate The silicate ion exchange material is represented by the following formula.

Na　[(A102)12(SiO2)B]　・x, H20 In the formula, X is about 20~ about 30, especially about 27. This material is known as zeolite A. ing. Preferably, the aluminosilicate has a diameter of about 0.1 to 10 microns. It has a particle size of

Specific examples of polyphosphates include alkali metal tripolyphosphates, Sodium, Potassium and Ammonium Pyrophosphate, Sodium and Botadi sodium orthophosphate, sodium volimeta having a degree of polymerization ranging from about 6 to about 21 Mention may be made of phosphates as well as salts of phytic acid.

Examples of phosphate builder salts include ethane 1-hydroxy-1,1-di Water-soluble salts of phosphonates, especially their sodium and potassium salts, methylene diphosphorus Water-soluble salts of acids, such as their trisodium and tripotassium salts and trisodium and trypotassium ethylidene, isopyropylidene benzylmethylidene and Examples include water-soluble salts of substituted methylene diphosphate such as lomethylidene phosphonates. . Phosphonate builder salts of the type described above are described by Diehl, 1964, 12 No. 3,159°581, issued October 1, 1965; No. 3.213.030; U.S. Patent No. 3.213.030 issued January 14, 1969 by Ray. No. 3,422゜021; and Qujmby, September 3, 1968 and 1 No. 3,400,148 and 3,422, issued January 14, 1996. No. 137. The contents disclosed in these documents may be referred to by citation. and are hereby incorporated by reference. Polycarboxylate builders are generally It can be added to the composition in acid form, but also in neutral salt form. When used in salt form and alkali metal salts such as sodium, potassium and lithium salts, especially sodium ammonium salts or ammonium and substituted ammoniums (e.g. alkanol ammonium um) salt is preferred.

Polycarboxylate builders include a variety of useful materials. important species One of the polycarboxylate builders in the class is ether polycarboxylates. There is. Numerous ether polycarboxylates disclosed as detergent builders has been done. Useful ether polycarboxylates include 19 by Berg U.S. Patent No. 3,128,287 issued April 7, 1964 and Lambe r t Disclosed in U.S. Patent No. 3,635,830, issued January 18, 1972 by i. Oxydisuccinates, such as those listed above, are included. disclosed to both of these The contents herein are incorporated by reference.

Specific ether polycarboxylates useful as builders in the present invention includes those represented by the following general formula.

CH(A)　(COOX)　-CH(COOX)　-〇-CH(COOX)-C H (COOX) (B) In the formula, A is H or OH: B is H or -0-CH(COOX)-CH, ( COOX); and X is H or a salt-forming cation. For example, the above general In the formula, if both A and B are H, the compound is oxynicosuccinic acid and its water-soluble salts.

If A is OH and B is H, then the compound is tartrate-succinic acid ( TMS) and its water-soluble salts. If A is H and B is -0-C) ((COOX)-C) f2 (COOX), then the compound is , tartrate nicosuccinic acid (TDS) and its water-soluble salts. These builders Particularly preferred for use in the present invention are mixtures of -. Particularly preferable (7) C. TMS and TDS with a TMS:TDS weight ratio of about 97:3 to about 20°80 It is a mixture of These builders are described by Bush et al., May 5, 1987. No. 4,663,071 issued.

Suitable ether polycarboxylates also include cyclic compounds, especially U.S. Pat. No. 3,923,679; No. 3,835.163; No. 4,158,635; No. 4.120.874: and as described in No. 4.102,903. Contains aliphatic compounds. The contents disclosed in these documents may be referred to by citation. The disclosure is incorporated herein by reference.

Other useful detergent building blocks include ether hydroxides with the structural formula shown below. Includes cypolycarboxylates.

HO-[C(R)　(COOM)　-C(R)　(COOM)　-0co　-H formula where M is hydrogen or a cation in which the resulting salt is water-soluble, preferably an alkali metal; , ammonium or substituted ammonium cation, and n is about 2 to about 15. (Preferably n is about 2 to about 10, more preferably n is about 2 to about 4 on average. ), and each R is the same or different and is hydrogen, CI~4alkyl or 01~4substituted Alkyl (preferably R is hydrogen).

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

In addition, organic polycarboxylate building blocks contain various alkali metals of polyacetic acids. , ammonium and substituted ammonium salts. As polyacetic virgoux salt , for example, sodium, potassium, ethylenediaminetetraacetic acid and nitrilotriacetic acid , lithium, ammonium and substituted ammonium salts. Also, the benefits toric acid, succinic acid, polymaleic acid, benzene L 3,5-tricarboxylic acid, benzene pentacarboxylic acid and carboxymethyloxysuccinic acid and their soluble salts Also included are polycarboxylates such as. Citric acid builders, e.g. citric acid and their soluble salts are polycarboxylates of particular importance in heavy liquid detergent formulations. Although it is a builder, it can also be used in granular compositions. Suitable salts include sodium, Metal salts such as lithium and potassium, as well as ammonium and substituted ammonium Also includes mucilage salt. Other carboxylate virgoos include No. 3,723,322 (disclosed herein) by D. The contents of the disclosure are hereby incorporated by reference. Contains carboxylated carbohydrates. The detergent composition of the present invention also contains 1 Bush, U.S. Pat. No. 4.566.984, issued January 28, 1986. The contents disclosed herein are incorporated by reference into this specification. ) 3,3-dicarboxy-4-oxa-1,6-hexanedio Etes and related compounds are also suitable. Useful succinic acid virgools include 05-C Includes 2o alkyl succinic acids and their salts. Particularly preferred for this type of compound A new compound is dodecenylsuccinic acid.

Alkyl succinic acids typically have the general formula % formula % That is, it is a succinic acid derivative. In the formula, R is a hydrocarbon, for example, Cjo-02o alkyl or alkenyl, preferably CI2-C16 alkyl or alkenyl. Ru. Furthermore, R is a hydroxy, sulfo, sulfoxy or sulfone substituent (these may be replaced by (as described in the above-mentioned patents).

Succinate builders include sodium, potassium, ammonium and alkano Preferably, it is used in the form of water-soluble salts, including ammonium salts.

Specific examples of succinate builders include lauryl succinate and myristyl succinate. ate, palmityl succinate, 2-dodecenyl succinate (preferred), Includes 2-pentadecenyl succinate and the like. Lauryl succinates are The group's preferred builder, published on November 5, 1986 in Europe It is described in patent application number 86200690.510,200,263.

Useful builders include, for example, sodium and bodium carboxymethyl oxide. Ximalonate, carboxymethyloxysuccinate, cis-cyclo-hexa -hexacarboxylate, cis-cyclopentane-tetracarboxylate , water-soluble polyacrylates (these polyacrylates have a molecular weight of more than about 2000) Acrylates can also be effectively used as dispersants) and maleic anhydride. and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are Crdtc, published March 13, 1979. No. 4,144,226 (not disclosed herein) by H.F. The contents herein are incorporated by reference). These are polyacetal carboxylates. These polyacetal carboxy Sylates are produced by mixing glyoxylic acid and a polymerization initiator under polymerization conditions. It can be prepared more easily. The resulting polyacetal carboxylate ester is then chemically Alkaline soluble polyacetal carboxylates are bonded to chemically stable end groups. Stabilized against rapid depolymerization in liquids, converted to corresponding salts and surfactants Added.

Polycarboxylate builders are also available from Diehl, published on March 7, 1967. U.S. Pat. No. 3,308,067 (the material disclosed herein is (herein incorporated by reference). like this Substances include maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, Water of mono and copolymers of aliphatic carboxylic acids such as traconic acid and methylenemalonic acid Contains soluble salts.

Other organic builders known in the art can also be used. For example, long chain hydrogen Monocarboxylic acids with locarbyls and their soluble salts can be utilized. child These include substances commonly referred to as U soaps.

Long chains of C1o-C2o are typically utilized. Hydrocarbyls, even when saturated May be unsaturated.

enzyme For example, does the detergent enzyme have protein as its main component or carbohydrate as its main component? , including removal of triglyceride-based stains and prevention of pigment transfer. They can be included in the detergent compositions of the present invention for a variety of reasons. The enzyme to be included is protea. as well as amylase, lipase, cellulase and peroxidase. It includes a mixture of

The above enzymes may be of plant, animal, bacterial, fungal or yeast origin. Anything is fine. However, these selections may not be suitable for optimal pH activity and/or stability. , thermal stability, and the relationship between stability and active detergents, builders, etc. be controlled. In this regard, bacterial amylases and proteases as well as fungal cell Bacterial or fungal enzymes such as enzymes are preferred.

Examples of suitable proteases include Bacillus subtilis and Bacillus lysiae-1-7t lumis (B. , licbeniforms).

Another suitable protease is N ova Industries A/S has developed and sold a pH range of 8 to 12. It is obtained from a strain of Bacillus that exhibits maximum activity throughout the period. This enzyme and similar enzymes The preparation of is described in British Patent No. 1,243.784 by Novo. Ru. Commercially available proteolytic enzyme suitable for removing protein-based stains. Initially, Novo Industries A/S (Denmark) developed Alcalase (AL). Products sold under the product name CALASE (trademark) and international Bio-Synthetics (Netherlands) has released SAVINASE (commercial product). Includes products sold under the trade name (trade name).

Among the types of proteolytic enzymes for liquid detergent compositions, Enzymes termed tease A and protease B are important. Protease A and its manufacturing method are described in European Patent Application No. 130.7 published on January 9, 1985. It is described in No. 56. The material disclosed herein is incorporated herein by reference. shall be made part of the disclosure of the specification. Protease B is located at position 217 of the amino acid sequence. A protein that differs from protease A in that it has leucine instead of tyrosine in the protein. It is a protein-degrading enzyme. Protease B is a European patent application filed on April 28, 1987. It is described in Patent Application No. 87303761.8. disclosed here The contents are incorporated by reference into this disclosure. of protease B The manufacturing method is described in the European patent application by Bott et al. published on January 9, 1985. No. 130.756. The content disclosed here is quoted The disclosure herein is hereby incorporated by reference. Amylases include, for example, British Patent No. 1.296,839 (Novo) Contains α-amylase obtained from a proprietary strain of Silas riciformis . Starch hydrolyzable proteins include, for example, International B io-5ynthetics rapidase (IIAPIDASE) (commercial) ] and TERMAMYL (trademark) manufactured by Novo Industries, Inc. is included. Cellulases that can be used in the present invention include bacterial cellulases and fungal cellulases. This includes both Preferably, the optimum pH of cellulase is between 5 and 9.5. Ru. A suitable cellulase is published in Barbesgoa, March 6, 1984. No. 4,435,307 to R.D. et al.

That is, this patent includes Humicola insolens. discloses a fungal cellulase produced from Lens. disclosed here The contents herein are incorporated by reference. Also, cellular Suitable enzymes include GB-A-2,075,028 and GB-A-2,095. , 275 and DE-OS-2,247,832.

Such cellulases include, for example, Humicola insolens (Humicola insolens). Humicola grisea vari.

thermodidea)), especially Humicola strain DSM 1800. Cellulase produced by Bacillus N fungus or Aeromonas cellulase Cellulases produced by Ze212-producing fungi and marine molluscs (Traveler O. - Dolabella Auricula Soland There is a cellulase extracted from the liver and pancreas of er). .

Lipase enzymes suitable for use in detergents include British Patent No. 1,372,034. Pseudomonas stabberi ATCC19,154 etc. as disclosed in Includes those produced by microorganisms of the Pseudomonas group. Disclosed in the above patent The contents herein are incorporated by reference. Ripper For suitable species, Pseudomonas fluorescens IAMI057 Includes those showing positive immunological cross-reactivity with antibodies of the lipase produced. This resource Pase and its purification method are described in Japanese Patent Application Publication No. 53-204, published on February 24, 1978. It is described in No. 87. This lipase has the trade name Lipase P “Amano” (hereinafter referred to as “Amano”). (hereinafter referred to as "Amanor P") from Ohno Pharmaceutical Co., Ltd., Nagoya, Japan.

Such lipases of the invention include Ou c b, t e r I o n y (Acta, Med, 5can,), pp. 133.76-79 (], 950) A positive immunocrossover with Amanor P antibodies was performed using standard and well-known immunodiffusion methods according to You have to show a reaction. The relationship between these lipases and their Amanor P The epidemiological cross-reaction method is described in US Pat. It is also described in No. 4,707.291. The content disclosed in this patent is The content of the present invention is incorporated by reference. A typical example of the above lipase is Amanor P Lipase, Pseudomonas f ragi Lipase derived from FERM P 1339 (available under the trade name Amanor B), Pseudomonas nitroreducens mutant strain Pseudomonas polychicum nasnitroreducens var.

1ipolyticum) FERM P 1338-derived lipase (trade name Amano -available at CES), Chromobacter virus manufactured by Toyo Jozo Co., Ltd. in Tagata, Japan. Chromobacter viscosum, e.g. Chromobacter viscosum Liper derived from S. viscosum mutant strain Suboriticum N RRL B 3673 and furthermore, U.S., Biochemica 1, and Dutch Dis. Chromobacter viscosum lipase and Pseudomonas gula manufactured by oynth Geoli (Pseuclomonas gladtoli)-derived lipase. Peruo The oxidase enzyme uses oxygen sources such as percarbonate, Used in combination with sulphate, hydrogen peroxide, etc. These are "solution bleaching" , i.e., the dyes or pigments removed from the substrate during the cleaning operation are transferred to other substrates in the cleaning solution. Used to prevent movement. Peroxidase enzymes are in the art For example, horseradish peroxidase, lignin -ase and haloperoxidases such as chloro- and promo-peroxidases. included. Peroxidase-containing detergent compositions include, for example, Novo Indus October 19, 1989 by 08 Kirk transferred to A/S It is disclosed in published PCT International Application No. WO 391099813. This international The content disclosed in the application is incorporated herein by reference.

A wide range of enzyme substances and means of their incorporation into synthetic detergent particles are described in McCarty et al. Also disclosed in U.S. Pat. No. 3,553,139, issued January 5, 1971, There is.

The disclosures in this U.S. patent are incorporated herein by reference. Department. Enzymes are further described by Place et al., published July 18, 1978. National Patent No. 4,101,457 and Hughes, issued March 26, 1985. No. 4,507,21.9. both of these us The content disclosed in the patent is incorporated herein by reference. . Enzyme materials useful in liquid detergent formulations and the placement of these enzyme materials in liquid detergent formulations. No. 4,2 U.S. Patent No. 4,2 by Hora et al., issued April 14, 1981 No. 61,868. The content disclosed in this U.S. patent is also cited and is hereby incorporated by reference as part of the disclosure herein.

The enzyme usually contains about 5 mg or less of active enzyme per gram of composition, more typically is present at a level sufficient to provide about 0.5 mg to about 3 mg.

In the case of granular detergents, enzymes are applied with additives that are preferably inert to the enzyme. or prill to minimize dust formation and improve storage stability. let

Techniques for achieving this are known in the art. into liquid formulations In this case, it is preferable to utilize an enzyme stabilization system. Fermentation of detergent composition aqueous solution Elementary stabilization methods are known in the art. For example, fermentation in aqueous solution Calcium acetate, calcium formate, and calcium propionate are one method of stabilizing the element. Free calcium from sources such as calcium may be used. calcium ions, Can be used in combination with short chain carboxylates, preferably formates. For example, 19 U.S. Pat. No. 4,318 to Letton et al., issued March 9, 1982. No. 818 Please refer to The material disclosed in this U.S. patent is incorporated herein by reference. It shall be part of the disclosure in the specification. Also, polio drugs such as glycerol and sorbitol It was also proposed to use tools. Alkoxy-alcohols, dialkyl groups lycoethers, polyhydric alcohols and polyfunctional aliphatic amines (e.g. alkanoamines such as triethanolamine, di-isopropanolamine, etc. amines) and boric acid or alkali metal borates. enzyme stabilization The technique is further described in U.S. Pat. No. 261.868, U.S. Pat. No. 3,600,319 (the disclosures in both of these U.S. patents are incorporated herein by reference). (herein incorporated by reference) and 19 by Venegas. European Patent Application Publication No. 0 199 405 (published on October 29, 1986) Application No. 86200586.5).

Non-oxalic acid and borate stabilizers are preferred. Enzyme stabilization systems are described in e.g. No. 4,261. ．． No. 868, No. 3゜600.391 and No. 3,519,570 It is also listed in the number.

Bleach compounds - bleaching agents and bleach activators The detergent composition of the present invention contains a bleaching agent, or a bleaching agent or one or more bleach activators. It may also contain a bleaching composition. When formulating this bleaching compound, Typically comprises from about 1 to about 20%, more typically from about 1 to about 10% of the laundry detergent composition. let Generally, bleaching compounds are optional in non-liquid formulations, e.g. granular detergents. It is an ingredient.

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

The bleaching agents used in the present invention are currently known or hereafter known, Any bleach useful in detergent compositions for textile cleaning, hard surface cleaning or other cleaning purposes. It may also be a whitening agent. These bleaches include oxygen bleach as well as other bleaches. Also included. For cleaning conditions below about 50°C, especially below about 40°C, this set The composition forms a baud note in situ under baud rate or detergent storage or cleaning conditions. Preferably, it does not contain notes (i.e., note-forming substances). Therefore Therefore, under these conditions, non-baud, non-baud forming bleaches should not be used. is preferable. Preferably, detergents used at these temperatures have substantially no Contains no baud or baud rate forming substances. The expression used here is ``substantially ``contains no rate- or baud-rate-forming substances'' refers to any borate in the composition. The content of -rate-containing and baud-rate forming substances is also about 2% by weight or less, preferably This means 1% or less, more preferably 0%.

One type of bleach that can be used is percarboxylic acid bleaches and their salts.

A suitable example of this type of bleach is magnesium monoperoxyphthalate hex. Hydrate, meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid acid and ciba-oxidodecanedioic acid. Such bleaching agents are 19 U.S. Patent No. 4,48 by H.A.R.T.M.A.N., issued November 20, 1984. No. 3.781, U.S. Patent Application No. 7 by Burns et al., filed June 3, 1985. 40,446, published on February 20, 1985, by Banks et al. Application No. 0.133,354 and Chung et al., published November 1, 1983. Disclosed in U.S. Pat. No. 4,412.934. disclosed to all of these The contents herein are incorporated by reference into the present invention. 19 by Burns et al. 6-node described in U.S. Patent No. 4,634°551, issued January 6, 1987. Nylamino-6-oxoperoxycaproic acid is also a highly preferred bleaching agent. . The disclosures in this patent are incorporated herein by reference. shall be.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate Peroxynoidole, Sodium pyrophosphate salt, urea peroxyhydrate, sodium peroxide, and the cleaning conditions listed above. Sodium perphosphate hydrate and tetrahydrate are included, subject to certain restrictions.

Peroxygen bleach is a peroxyacid that corresponds to a bleach activator in an aqueous solution (i.e., in a cleaning process). Preferably, it is combined with a bleach activator generated in situ during the process). wide range bleaching Active agents can be used, examples of which include US Pat. No. 4,179 by Padini et al. No. 390. Preferred bleach activators include tetraacetyl alkylene diamines, especially tetraacetylethylenediamine (TAED) and tetra Contains laacetylglycolyl (TACU).

-C-L where R is the carbon of the longest linear alkyl chain extending from and including the carbonyl carbon. an alkyl group having about 1 to about 18 carbon atoms, with a number of about 6 to about 10, and L is a degrouping, and the pKa of its conjugate acid is about 4-13. These bleach activators are U.S. Pat. No. 4,915.854, issued April 10, 1990, by Mao et al. The material disclosed herein is incorporated by reference into this disclosure. Ru. ) and in the above-mentioned US Pat. No. 4,412.934.

Bleaches other than oxygen bleach are also known in the art and can be used in the present invention. Ru. One class of non-oxygen bleaches specifically contemplated include sulfonated zinc and/or There are photoactivated bleaches such as luminium phthalocyanines. These substances should be washed It can be attached to the substrate during the process. By hanging your clothes to dry in the sun. Sulfonated zinc phthalocyanine is activated when exposed to light in the presence of oxygen such as The result is bleaching of the substrate. Preferred zinc phthalocyanines and photoactivated bleaches Regarding the white process, the US special edition published on July 5, 1977 by Holcombe et al. No. 4,033.71.8. What this patent says is incorporated into the present invention by reference. Typically, detergent compositions include sulfonate from about 0.025 to about 1.25% by weight of zinc phthalocyanine.

Polymer stain release agent Any polymeric soil release agent known in the art may be used in the detergent compositions of the present invention. It can be used for. Polymeric soil release agents are suitable for use with loose materials such as polyester and nylon. A hydrophilic segment that makes the surface of aqueous fibers hydrophilic and a hydrophilic segment that attaches to hydrophobic fibers for cleaning and remains attached to it throughout the rinse cycle and therefore the hydrophilic segment It is characterized by having both a hydrophobic segment that acts as an anchor for the Ru. This ensures that any stains that occur following treatment with a stain release agent will be removed during subsequent cleaning steps. Easy to clean. Polymeric soil release agents include hydroxyether cellulose Polymer, ethylene terephthalate or propylene terephthalate and polyethylene Copolymer blocks with oxide or polypropylene oxide terephthalate, etc. Includes lulose derivatives. Cellulose derivatives that serve as soil release agents Cells such as Methocel (trademark) (manufactured by Dow) are commercially available. There are hydroxy ethers of loose.

Cellulosic soil release agents include methylcellulose, ethylcellulose, and hydroxycellulose. c1~ such as cypropyl methylcellulose and hydroxybutyl methylcellulose selected from the group consisting of C4 alkyl and C4 hydroxylalkylcellulose It also includes things that are. Various cellulose derivatives useful as soil release polymers include N U.S. Patent No. 4.000.093 issued December 28, 1976 to 1coi et al. Disclosed in the issue. The material disclosed in this patent is incorporated herein by reference. It shall be part of the disclosure in the specification.

Soil release agents characterized by poly(vinyl ester) hydrophobic segments include , grafting of poly(vinyl esters) (e.g. C,-C6 vinyl esters) A copolymer, preferably poly(vinyl acetate) with a polyethylene oxide backbone This includes those grafted onto the main chain of polyalkylene oxide such as. something like this The quality is known in the art and is published by Kud et al., April 22, 1987. European Patent Application No. 0.219°048. This kind of city A suitable commercial soil release agent is Tuka, available from BASF (West Germany). Sokalan(TM) type materials, such as Sokalan(TM) HP-22 is included. One type of preferred soil release agent is ethylene terephthalate and polymers. Copolymer with random blocks of polyethylene oxide (PEO) terephthalate There is a union. More specifically, these polymers include ethylene terephthalate and P It contains repeating units of EO terephthalate. At this time, use ethylene terephthalate The molar ratio of rate units to PEO terephthalate units is about 25:75 to about 35:65, and the PEO terephthalate unit has a molecular weight of about 300 to about Contains 2000 polyethylene oxide. Molecular weight of this polymeric stain release agent ranges from about 25,000 to about 55,000. Regarding this, in 1976 Referenced U.S. Pat. No. 3,959,230 by Hays, issued May 25th. stomach. The content disclosed in this patent is incorporated herein by reference. It is considered as a department. Also, B published on July 8, 1975, which discloses similar copolymers. U.S. Pat. No. 3,893,929 to a5adur (incorporated by reference See also (which is considered part of the specification disclosure).

Another preferred polymeric soil release agent is from 10 to 15 ethylene terephthalate units by weight. % from polyoxyethylene glycol with an average molecular weight of 300 to 5.000. Contains 90 to 80% by weight of polyoxyethylene terephthalate units. is a polyester with repeating units of ethylene terephthalate units. . In polymer compounds, polyoxyethylene terephthalate units are The molar ratio to phthalate units is between 2.1 and 6:1. As this polymer For example, the commercially available substances Zelcon™ 5126 (manufactured by DuPont) and M i1ease (trademark) (manufactured by ICI) is mentioned.

These polymers and their production methods are described in Gossellink, 1987. U.S. Pat. No. 4,702.857, issued Oct. 27, which includes (which are hereby incorporated by reference). It is. Another preferred polymeric soil release agent is terephthaloyl and oxyalene. The oligomer ester main chain of the oxy repeating unit and the terminal component covalently bonded to the main chain The sulfonation product of a substantially linear ester oligomer comprising: Before Stain release agents include allyl alcohol ethoxylate, dimethyl terephthalate and and 1,2-propylene diol. Here, the terminal end of each oligomer is On average, the sulfonate groups have a total of about 1 to about 4 sulfonate groups. These dirt releases No. 4, issued Nov. 6, 1990, by J. ．． No. 968.451 and E, P filed on January 29, 1990.

Described in detail in U.S. patent application Ser. No. 07/474°709 by Gossellink has been done. The contents disclosed in these documents are incorporated herein by reference. The content shall be as shown. Other suitable polymeric soil release agents include Gosselink et al. Described in U.S. Patent No. 4.711.730, issued December 8, 1987 Thiro- or methyl-capped 1,2-propylene terephthalate-polyoxygen C-ethylene terephthalate polyesters, 198 by Gossellink The anionic end cap described in U.S. Pat. No. 4,721.580, issued Jan. Cap is a sulfo-polyethoxy group derived from polyethylene glycol (PEG) Anionic end-capped oligomeric esters comprising Gosselin No. 4,702.8.57, issued October 27, 1987, by Formula X-(OCH2CH2)TI- (wherein n is from 12 to about 43 and X is C -04 alkyl or preferably methyl) Block polyester oligomer compounds having a all of these The content disclosed in the patent is incorporated herein by reference. .

Additional soil-releasing polymers include Maldonado et al., October 3, 1989. The soil-releasing polymers described in U.S. Pat. No. 4,877,896, issued on included. This patent includes anion, specifically sulfaroyl end-capped terminals. Discloses phthalate esters, and the disclosed content may be cited. This is the disclosure content of this specification. Terephthalate esters are asymmetrically substituted esters. Contains xy-1,2-alkyleneoxy units.

If a soil release agent is utilized, typically about 0.01% of the laundry detergent composition of the present invention to about 10.0% by weight, preferably about 0.1 to about 5.0% by weight, more preferably about It accounts for 0.2 to about 3.0% by weight.

chelating agent The detergent compositions of the present invention also contain one or more iron and manganese chelating agents. - May be included as an additive. Such a keynote agent is an aminocarboxylic Xylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and the like and mixtures thereof. All of these chelating agents are defined below. Without wishing to be bound by the following theory, these substances Part of the advantage lies in the removal of iron and manganese ions from the cleaning solution through the formation of soluble chelates. This seems to be due to its very good ability to remove particles.

An amino acid useful as a cleaning agent as an optional ingredient in the composition of the present invention. Ruboxylates contain one or more substructure units of the following formula, preferably at least It can have two types.

where M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and X is 1 to about 3, preferably 1. Preferably this The aminocarboxylate of Contains no group. Amine carboxylates that can be used include ethylenediamine Tetraacetates, N-hydroxyethylethylenediamine triacetates , nitrilotriacetates, ethylenediaminetetrapropionates, Ethylenetetraamine hexaacetates, diethylenetriaminepentaacetate and ethanol diglycines, their alkyl metals, ammonium and Included are substituted ammonium salts as well as mixtures thereof.

Also, when at least low levels of total phosphorus are tolerated in the detergent composition, In the detergent composition of the present invention, Ki! Aminophosphonates are also suitable as curing agents. That's true.

A compound having one or more, preferably a small number (both two types) of substructure units of the following formula It is for use.

In the formula, M is hydrogen, an alkali metal, ammonium or substituted ammonium, and is from 1 to about 3, preferably 1. The above compound is ethylenediaminetetra Kiss (methylene phosphonate), Nitrilotris (methylene phosphonate) and Contains diethylenetriaminepentakis (methylene phosphonate). preferred In particular, these aminophosphonates are alkyl or aryl having more than about 6 carbon atoms. Contains no lekenyl group. Alkylene groups can be shared by substructures. multifunctional position Replaced aromatic chelators are also useful in the compositions of the present invention. These substances are: It comprises a compound represented by the general formula.

H In the formula, at least -R is -3O3H or -COOH or a salt thereof and It is a mixture of them.

U.S. Patent No. 3,812,0 issued May 21, 1974 to C0nn0r et al. No. 44 (The content disclosed herein is incorporated herein by reference. ) discloses polyfunctionally substituted aromatic chelating agents and sequestering agents. Ru. A preferred compound of this kind in acid form is 1,2-dihydroxy-3,5-disulfide. These are dihydroxydisulfobenzenes such as hobenzene. alkaline detergent composition may be used to treat these substances with alkali metals, ammonium or substituted ammonium (e.g. , mono- or triethanolamine).

If these chelating agents are utilized, they are commonly used in the laundry detergent compositions of the present invention. It is contained in an amount of about 0.1 to about 10% by weight. More preferably, the chelating agent is from about 0.1 to about 3.0% by weight in such compositions.

Mud stain removal/redeposition prevention agent Stain removal/anti-redeposition agents useful in detergent compositions of the present invention include dirt removal and anti-redeposition agents. polyethylene glycols and water-soluble ethoxylated alcohols with anti-redeposition properties. Contains mins. Polyethylene glycols useful in detergent compositions of the invention The compound typically has a molecular weight of about 400 to about 100,000, preferably about 1,000 to about 1,000,000. 00 to about 20,000, more preferably about 2,000 to about 12,000, most preferably Preferably, it is in the range of about 4,000 to about 8,000. Such compounds are not commercially available. Union Carbide Company in Danbury, Connecticut It is sold under the trade name of Ca+bovax.

The water-soluble ethoxylated amines shall be selected from the group consisting of the following amines: is preferred.

(1) Ethoxylated monoamines represented by the following formula: Vl+ (1-M water?-T ? l+MVl-)r~,7. Full book 9 Vke (2) Ethoxylation expressed by the following formula Diamines = (3), ethoxylated polyamines represented by the following formula; (4) the following Ethoxylated amine heavy compound represented by the general formula (5) Mixtures thereof. In the above formula, AI is nee-ta h-mae! -4-ノ 7 ； ・ No Kaya UL Item K -N ~ Hatake HQFJ 1″-U-(Nosu; K 1! n included 1a’-a 1”-* 4 / /1 / d/l/ +4 hydroxyalkyl; R1 is C'=CI2al Kylene, hydroxyalkylene, alkynylene, arylene or alkali having from 2 to about 20 oxyalkylene units unless a lene or O-N bond is formed. is a 02-C oxyalkylene component; each R is Ct-C4 or hydro xyalkyl, component -L-X or two R2 together component is -〇- or -CH2-, r is 1 or 2, S is 1 or 2, and and r+s is 3 or 4; X is a nonionic group, an anionic group, or a mixture thereof and R3 is substituted C-C1□alkyl having a substitution site, human 0xyalkyl, is alkenyl, aryl or alkaryl; R4 is C"" CI 2 alkyl Ren, Hydroxia■ alkylene, alkenylene, arylene or alkarylene or O-0 or has from 2 to about 20 oxyalkylene units unless it forms an O-N bond. 2-C3 oxyalkylene component; L is polyoxyalkylene component -((R O) (CHCH20) 11)-(wherein, R5 is C-C alkylene or hydro xyalkylene, m and n are the components -CHCH20)I1- are comprising at least about 50% by weight of the sialkylene component) The hydrophilic chain n is such that R1 is C-C alkylene, hydroxyalkylene or alkylene. When it is nylene, it is at least about 6, and R1 is C-C alkylene, hydroxy Alkylene or ethoxy as disclosed in European Patent Application No. 111,984 amine polymer; Zwitterionic polymers disclosed in Roppa Patent Application No. 112.592; and U.S. Pat. No. 4,548,74 to Connor, issued October 22, 1985. The amine oxides disclosed in No. 4 are included. All of the above patent applications and patents The contents disclosed in the above are incorporated herein by reference.

The most preferred soil release agent and anti-redeposition agent is ethoxylated tetraethylene pen. tamin and polyethylene glycol having a molecular weight ranging from about 4,000 to about 8,000. It's a call type.

Granular detergent compositions containing such compounds typically contain about 0.0% dirt remover. 01 to about 10.0% by weight, and in liquid detergent compositions typically about 0.0% by weight. It contains 1 to about 5.0% by weight.

Polymer dispersant Polymeric polycarboxylate dispersants are advantageously utilized in the detergent compositions of the present invention. It is. These materials help with calcium and magnesium hardness control. the above A builder additive similar to the polycarboxylate described in the builder description for In addition to its role as an adjunct, although it is not intended to be bound by the following theory, , these high molecular weight dispersants are compatible with other buildings containing low molecular weight polycarboxylates. When used in combination with a duster, it is free from granular dirt due to its thawing effect and prevention of redeposition. Improving overall detergent builder performance by inhibiting crystal growth It seems possible.

Polycarboxylate that can be used as a polymeric polycarboxylate dispersant The substrate material contains at least about 60% by weight of segments having the following general formula: It is a polymer or copolymer.

In the formula, X1Y and Z are hydrogen, methyl, carboxy, carboxymethyl, hydride, respectively. selected from the group consisting of on and n are about 30 to about 400. Preferably, X is hydrogen or hydroxy , Y is hydrogen or carboxy, Z is hydrogen, M is hydrogen, alkali metal genus, ammonia or substituted ammonium. This kind of polymer polycarboxylic The substrate material can be polymerized or copolymerized with suitable unsaturated monomers (preferably in acid form). It can be manufactured by

into unsaturated monomeric acids that can polymerize to form suitable polymeric polycarboxylates. are acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, Includes aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. B Contains no carboxylate groups such as nyl methyl ether, styrene, ethylene, etc. Suitably, the monomer segments are present in the polymeric polycarboxylate.

However, such segments should not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. here Such acrylic acid-based polymers are useful in water-soluble polymerized acrylic acid. It is natural salt. The average molecular weight of such polymers in acid form is approximately 2,000 to 10,0 00, more preferably about 4,000 to 7,000, most preferably about 4,000 ~5,000. Such water-soluble salts of acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Solubility of this kind Polymers are official seal materials. The use of polyacrylate analogs in detergent compositions For example, U.S. Patent No. 3.30 issued March 7, 1967 by Dieh+ No. 8.067. The content disclosed in this patent may not be cited. This is the disclosure content of this specification.

In addition, a copolymer mainly composed of acrylic acid/maleic acid is a preferred component of the dispersant. It can also be used as a minute. Such substances include copolymers of acrylic acid and 71-fluoric acid. Contains water-soluble salts. The average molecular weight of such an acid type copolymer is about 5, 000 to 1.00.000, preferably about 6.000 to 60,000, more preferably or about 7,000 to 60,000. In such copolymers The ratio of acrylate to maleate generally ranges from about 30.1 to about 1:1, and more. Preferably it is in the range of about 10:1 to 2.1. Such acrylic acid/maleic acid Water-soluble salts of acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. It may also be a nium salt. This type of soluble acrylate/maleate copolymer is , a known substance, European Patent Application No. 669 published on December 15, 1982 It is described in No. 1.5.

The content disclosed in this application is incorporated herein by reference. Ru.

If a polymeric dispersant is utilized, it will generally be about 0.2 to about 10% % by weight, preferably about 1 to about 5% by weight.

brightener Optical brighteners or other brightening or whitening agents known in the art may be used in the present invention. It can be incorporated into laundry detergent compositions. However, the selection of brighteners depends on the type of detergent, the nature of other ingredients present in the detergent composition, the temperature of the wash article, the degree of agitation and the wash substance; depends on a number of factors, such as the ratio of

The choice of brightener also depends on the type of material to be cleaned, e.g. cotton, synthetic, etc. do. Most selection detergent products are used to clean a variety of fabrics. The detergent composition must contain a mixture of brighteners that are effective on a variety of fabrics. stomach. Of course, the individual components of such brightener mixtures need to be compatible. Ru.

Commercially available optical brighteners include stilbenes, pyrazolines, coumarins, carboxylic acids, and methine. Cyanines, dibenzotiphene-5,5-dioxide, azoles, 5- and 6-dioxide -Including, but not necessarily limited to, membered heterocycles and other brighteners Can be classified into subgroups. Such brighteners include, for example, New York M, Z published in 1982 by J hon Wiley and 5ons Manufacture and Applications of Optical Brighteners (The Produclio) by Ahrarinik n and Application of Fluo+e+centBrig Htening Agents) J. disclosed here The contents are incorporated herein by reference.

Stilbene derivatives include derivatives of stilbene; trizol derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and Includes, but is not necessarily limited to, stilbene styryl.

Certain derivatives of bis(triazinyl)aminostilbene are 4,4°-diamin It can be prepared from stilbene-2,2'-disulfonic acid. Coumarin derivatives includes substitutions at the 3-position, substitutions at the 7-position, and derivatives substituted at the 3- and 7-positions, but this is not necessarily the case. They are not limited to these.

Carboxylic acid derivatives include fumaric acid derivatives; benzoic acid derivatives; acrylic acid derivatives; naphthalene dicarboxylic acid derivatives; heterocyclic acid derivatives; and and cinnamic acid derivatives, but are not necessarily limited to these.

Cinnamic acid derivatives are further disclosed on page 77 of the document Zahradnik. cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryl Contains xadiazoles, styryl triazoles and styryl polyphenyls can be classified into groups that are not necessarily limited to these.

Styrylazoles are further disclosed on page 78 of Zahradnik. styrylbenzoxazoles, styryl imidazoles and styryl thiazoles It can be classified into two categories. These three subclasses mentioned above do not necessarily include styryl azo. It is understood that the categories do not represent an exhaustive list of possible subdivisions. It would be cool.

Other optical brighteners include those listed in The Kirk-Othmer Encyclopedia of Mikal Technology (The i+ -0) hme+ Enc7clipped ia of Chemical Technology 7) S Volume 3, No. 737 ~750 pages (1,962 1hon Wile7 and 5OO1) No. of dibenzothiophene-5,5-dioxide disclosed on pages 741-749. There are derivatives. The content disclosed herein is incorporated herein by reference. become. The optical brighteners described in this document include 3,7-diamitudibenzothiophene. -2,8-disulfonic acid 5,5-dioxide.

Other optical brighteners include azoles, which are derivatives of six-membered heterocycles. these are , and can be further subclassified into monoazoles and bisazoles. Monoazoles and bisazoles are disclosed, for example, in Kirk-Othmer. difference In addition, other optical brighteners include the six-membered ring compound disclosed in Kirk-Othmer. There are derivatives of elementary rings. Such compounds include, for example, those derived from pyrazine. and brighteners derived from 4-amitnaphthalamide.

In addition to the brightening agents mentioned above, other agents may also be useful as brightening agents. this Examples of other agents such as , they include 1-hydroxy-3,6,8-pyrene trisulfonic acid: 2,4- Dimethoxy-1,3,5-)riazin-6-yl-pyrene: 4,5-diphenyl Includes derivatives of imidasilone disulfonic acid: and pyrazolinequinoline.

Other specific examples of optical brighteners include Wixo, published on December 13, 1988. No. 4,790°856 by N. Open to this patent The content shown is incorporated herein by reference. these The optical brightener is the whitening agent Pho rwh i made by Verona. (trademark) series. Other brighteners disclosed in the above patents These include Chinopar UNPA, Chinopar CBS and Chinopar manufactured by Ciba Geigy. Le 5BM; Hilton-Davis Company (Hi1ton-Davis in Italy) ) manufactured by Artic White CC and Archiic Ho Wight CWD; 2-(4-styrylphenyl)-2H-naphthol (1, 2-d)) Liazoles; 4゜4゛-bis-(L　2.3-triazole-2- yl)-stilbene, 4,4'-bis(styryl)biphenyls; and y-a Contains minocumarins. Specific examples of these brighteners include 4-methyl-7 -diethylaminocoumarin; 1,2-bis(benzimidazol-2-yl)-e Thyrenes; 1,3-diphenylfrazilins; 2,5-bis(benzoxazole- 2-yl)-thiophene; 2-styryl-naphtho-(1,2-cl)-oxazo and 2-(stilben-4-yl)-2H-naphtho(1,2-d)tri Examples include azoles.

Still other optical brighteners include: Hamilton, published February 29, 1972; No. 3,646,015. This patent The contents disclosed in the above are incorporated herein by reference.

If an optical brightener is utilized, the laundry detergent composition will generally have a C1 of about 0. 05 to about 2.0% by weight, preferably about 0.1 to about 1.0% by weight.

foam suppressant Chemicals that are or will be known to reduce or inhibit foam formation Compounds can be incorporated into the detergent compositions of the present invention. polyhydroxy fatty acid a Because midosurfactants can increase the foam stability of detergent compositions, such The inclusion of substances (hereinafter referred to as "foam suppressants") may be desirable. Foam suppression is The detergent composition has a relatively high foam-forming surfactant and polyhydroxy fatty acid amide interface. This is particularly important when it is comprised in combination with a surfactant. Foam suppression is Particularly desirable in constant loading automatic washing machine compositions. These washing machines are typically has a horizontal axis for holding the laundry and washing water, and exhibits a rotating action around this axis. It is characterized by having a drum. This type of agitation is highly foam-forming. , as a result, cleaning performance may be reduced. The use of foam suppressants requires warm water washing conditions It is also particularly important under low and high surfactant concentration conditions.

A wide variety of substances can be used as foam suppressants. Foam suppressants are well known in the art. It is well known. Foam suppressants are commonly used, for example, in the Kirk-Othmer Cyclopedia of Chemical Technology, 3rd Edition, Volume 7, No. 43 Written on pages 0 to 447 (published by Jhon WilB and 5ons in 1979). It is listed. One of the most important types of foam suppressants is monocarboxylic fatty acids and fatty acids. and their soluble salts. These substances were described by Wayne St. John. No. 2,954,347, issued September 27, 1960. Ru. The disclosures in this patent are incorporated herein by reference. shall be. Monocarboxylic fatty acids and their salts for use as foam suppressants , typically having from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. It has a chain. Suitable salts include alkaline salts such as sodium, potassium and lithium salts. Includes potassium metal salts as well as alkanol ammonium salts. These substances is a preferred type of foam suppressant for agent compositions.

The detergent compositions of the present invention may also contain non-surfactant suds suppressants. these For example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. , fatty acids), liglyalides), fatty acid esters of -hydric alcohols, aliphatic CI8-04Q ketones (eg, stearone), etc. are included. to other foam suppressants is the reaction product of cyanuric chloride and 2 to 3 moles of a primary or secondary amine having 1 to 24 carbon atoms. tri-hexa-alkylmelamines or di-tetra- N-alkylated aminotriazines such as alkyldiamine chlortriazines; Propylene oxide and monostearyl alcohol phosphate ester and molybdenum Nostearyl di-alkali metal (e.g. sodium, potassium, lithium) Monostearyl phosphates such as sulfates and phosphate esters included. Hydrocarbons such as paraffin and helobaraffin are available in liquid form. . Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, and have a pour point of 0°C to about 5°C. range, with a minimum boiling point of approximately 100"C (atmospheric pressure) or higher. Utilizing hydrogen hydrides, preferably wax repurchased hydrogen hydrides having a melting point below about 100'C. It is also known that Hydrocarbons are a preferred class of suds suppressants in detergent compositions. Ru. Hydrocarbon foam suppressants have been described, for example, by Gando et al. in 1981. No. 4,265,779, issued May 5th. to this patent The content disclosed is incorporated herein by reference. That is, hydrocarbon Elements include aliphatic, cycloaliphatic, aromatic and heterocyclic groups having about 12 to about 70 carbon atoms. Includes saturated or unsaturated hydrocarbons. The term “ The term "paraffin" also includes mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressants comprises silicone suds suppressants. . This type of foam suppressant includes polyorganosiloxanes such as polymethylsiloxane. Dispersions or emulsions of oils, polyorganosiloxane oils or resins and polio Polyorganosiloxane in which luganosiloxane is chemically adsorbed and fused to silica. Also included is the use in combination with silica particles. Silicone foam suppressants are available in the art Well known in the field, for example, in 1981 by Gondo lfo et al. U.S. Pat. No. 4,265.779 issued May 5 and 5tarch M.

European Patent Application No. 89307851 published on February 7, 990 by S. ．． It is stated in No. 9. What is disclosed in both these patents and patent applications: The contents herein are incorporated by reference.

Other silicone suds suppressants are disclosed in U.S. Pat. No. 3,455°839. . This patent describes the creation of an aqueous solution by blending a small amount of polydimethylsiloxane liquid. The present invention relates to compositions and methods for defoaming. Mixture of silicone and silanized silica is described, for example, in German Patent Application No. 2,124,526.

Silicone defoamers and foam control agents in granular detergent compositions are manufactured by Bartolot U.S. Patent No. 3,933°672 by A et al. No. 4,652,392 to Aginski et al.

Typical silicone-based foam suppressants used in the present invention include: (i) Polydimethylsiloxa having a viscosity of about 20 cs to about 1500 cs at 25°C with liquid; (ii) about 5 to about 50 parts per 100 parts by weight of (i) (CH) SiO and S t It consists of O2, and the ratio of (CH) SiO to S iO2 is about 0.6+1 to about 1.2+1 of the siloxane resin; (i i 1) about 1 to 100 parts by weight; about 20 parts of (i) solid silica gel; a foam control agent in an amount effective to suppress foam consisting essentially of:

When a suds suppressant is utilized, the suds suppressant is present in a "foam suppressing effective amount."

"Amount effective for foam control" means that the formulator of the composition is able to control foam to the desired degree. This means that the amount of foam control agent can be selected. The amount of foam control depends on the detergent selected. different. For example, in the case of a high foam-forming surfactant, the However, a relatively large amount of foam control agent is used to achieve the desired foam control.

Detergent compositions of the present invention generally comprise from 0 to about 5% suds suppressant. foam suppressant Monocarboxylic fatty acids and their salts are typically is present in an amount up to about 5% by weight of the detergent composition. Preferably from about 0.5 to Approximately 3% fatty monocarboxylate foam suppressor is utilized. silicone foam suppressor are typically utilized in amounts up to about 2.0% by weight of the detergent composition; You may use a larger amount than that. This upper limit is primarily intended to minimize costs and It is practical in terms of its effectiveness in effectively controlling foam with a small amount. Preferably, The silicone suds suppressant is present at a concentration of from about 0.01 to about 1%, more preferably from about 0.25 to about 0. ．． 5% used. Here, the weight percent values above include only the polyorganosiloxane. Any silica that can be used in combination with any additives that are available without included.

The monostearyl phosphates will generally be present in an amount of about 0.1 to about 2% by weight of the composition. Used in amounts ranging from % to %.

Hydrocarbon suds suppressants are typically utilized in amounts ranging from about 0.01% to about 5.0%. However, there are a wide variety of other ingredients that can be used at higher levels and incorporated into the detergent compositions of the present invention. may contain other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments. , solvents for liquid formulations.

Liquid detergent compositions can contain water and other solvents as carriers.

Low-grade chemicals such as methanol, ethanol, propatool, and isoproptool High molecular weight primary or secondary alcohols are suitable. Monovalent to solubilize surfactants Alcohols are preferred, having about 2 to about 6 carbon atoms and about 2 to about 6 hydroxy groups. (e.g. propylene glycol, ethylene glycol, glycerin and Polyols such as 1,3-propanediol) can also be used.

The detergent composition of the present invention has a pH of about 6.5 to 1 of the wash water used in an aqueous wash operation. 1, preferably about 7.5 to about 10.5. liquid The pH of the product formulation is from about 7.5 to about 9.5, more preferably from about 7.5 to about 9.0. It is. Methods to control pH at recommended usage levels include buffers, alkalis, acids, etc. The methods of use are well known in the art.

Furthermore, the present invention provides a method for treating substrates such as fibers, textiles, hard surfaces, skin, etc. with glyceryl ether. A detergent composition containing a detergent component (a) and an anionic detersive surfactant component (b) the presence of a solvent such as water or a water-miscible solvent (e.g. a primary or secondary alcohol) A method of cleaning the substrate by contacting the substrate with the substrate is provided. Improved cleanability Therefore, it is preferable to provide stirring. Suitable means for imparting agitation include manual scrubbing, preferably with the aid of a brush, or other cleaning equipment, automatic cleaning. Includes washing machines, automatic dishwashers, etc.

As mentioned above, the compositions of the present invention contain conventional polyethoxylate nonionic surfactants. Although it is possible to incorporate agents, it is generally not preferred to do so. actual The advantage of glyceryl ethers used as component (a) is that polyethoxy Excellent cleaning properties can be obtained by using it in place of non-ionic surfactants. However, the use of ethylene oxide can be made unnecessary.

That is, the glyceryl ethers of formula (1) are extremely effective against oil stains. On the other hand, it does not show significant weakness to other stains, such as particulate stains. In addition, Lyceryl ethers show satisfactory performance with respect to soil redeposition. moreover, Glyceryl ethers offer additional benefits, such as enzyme stability in heavy detergent solutions. It shows the standardization.

In addition, glyceryl ethers have relatively low melting points, making them difficult to use as flocculants. It is being considered.

The present invention will be explained below with reference to Examples.

Example 1 Sagitanis, J.O., using the following reagents:

The method described in A, C, S, Vol. 66, No. 1 (January 1989), p. 146 Cocoyl diglyceryl ether was prepared by a similar method.

Distilled dodecyl epoxide No. 8 (manufactured by Brocter & Gamble) 30 grams (0,124 mol) sodium 0.14 (6,2X10-3 mol) anhydrous Glycerol 57g (0.62 mol) ・Glycerol and glyceryl together, The reaction was allowed to proceed for 1 hour at 130° C. under nitrogen. Add 1 epoxide to the reaction mixture at 180°C. Added over time. The mixture was then stirred at the same temperature for 8 hours. reaction mixture Sodium was neutralized by dissolving in ethanol and treating with carbon dioxide pellets. B - After removing ethanol from the mixture using a tally evaporator, distillation (1, 75 mm Hg (233 Pa; head temperature 140°C), glycerol dimer (gas liquid (confirmed by chromatography) was removed.

The produced dodecyl diglyceryl ether contains 92% diglyceryl ethers and molybdenum. Contains 1.5% of glyceryl ethers and 2% of triglyceryl ethers. It was a solid with a low melting point (44-46°C).

Nglyceryl ether has the general formula (3) per mole of “branched” ether It contained about 4 moles of the "linear" ether of (2).

The above synthesis also adds a small amount of borohydride to improve the color of the final product. Row 5 can also be achieved using epoxide N008.

Example 2 US-A-4,465,866 by Takaishis using the following reagents: Cocoyl diglyceryl ether was prepared by the method described in the issue.

Acetone glycerol ketal (＾ld+ich　From Che+aicx1 company `` Solketal (available under the trade name Solketal) 74.5g (0,5625 mol) Tetramethyldiaminohexane 3.2g (0,018 mole) Epoxide No. 8 (manufactured by Brocter & Gamble) 45g (0, 18 moles) Mix acetone glycerol ketal and tetramethyldiaminohexane together , heated at 100°C. While maintaining the temperature between 100 and 110℃, the epoxide is The mixture was added dropwise over 30 minutes. Next, the resulting mixture was heated at the same temperature for 6 hours.

The product was distilled (1 mmHg (133 Pa); head temperature 52°C) to remove excess The acetone glycerol ketal was removed and further vacuum distillation (4.5 mmHg) 600 Pa); head temperature 230°C) to collect the product (dioxolane intermediate body).

Dissolve 34.8 g (0.09 mol) of dioxolane intermediate in 75 ml of ethanol. 4.6 g (0,046 mol) of concentrated sulfuric acid was dissolved in 100 ml of water. and the resulting mixture was heated under reflux for 4 hours. Then cool the solution and add water It was neutralized with 3.6 g (0.09 mol) of sodium oxide. The product is converted into diethyl ether. Extracted using gel, dried over sodium sulfate, and evaporated using a rotary evaporator. After drying, a golden paste was obtained.

Example 3 A series of heavy duty liquid detergent compositions (A-C) were prepared. These compositions are in the table below It has the surfactant component shown. In the table below, the amount of each ingredient is It is shown in weight%.

NaCnAS 12.9 1.2.9 12.9 Nat, NI EO78,4 --- Nat, NI EO58,4- CnDGE --8,4 The surfactants in Table 1 above are as follows.

NaCnAS=Sodium Coconut Alkylsulfate Nat, NI EO7 = natural fatty alcohol and 7 moles of ethylene oxide per mole Condensate with oxide Nat, NI EO5 - 5 per mole with natural fatty alcohol condensate with moles of ethylene oxide CnDGE = coconut alkyl diglyceride ether (prepared as in Example 1 above) The above compositions were tested against various soils. The test uses contaminants and compositions. It was washed in a small washing machine at 60° C. using tap water (total hardness 5 mol) at a volume of 1%. dirt The dyed material is prepared by staining cotton or polyester/cotton (PC) cloth pieces in the usual way. did.

The decontamination performance was determined by an expert panel using a known method. Composition A Using the results obtained using the standard (0, O) as the standard, the results were converted to the Schetzfue scale It was recorded in panel score units (psu). The results below Shown in the table below.

Ura dirt: +0.4/+0.7 +1.4/+1. ．． 0 make up +0.6 /+0.5 +1.8/+0.90 Red +0.5/+1.2 +2.3/+1. 7 spaghetti +0.2/+0.4 +0.5/+0.3DMO+0.7/+ 0.6 +1.0/+0.9 Bleaching -0,2/+0.2 +1.1/+0.9 Enzymatic -0,110,0+0.310.0 Granular -0,1/-0,6+0.2 /+1.1 Note: “Enzyme-based” refers to stains that can be removed with proteolytic enzymes. Ru.

DMO = dirty motor oil As can be seen from Table 2, the composition C according to the invention is especially useful for oil stains and particulate stains. 7.25% by weight of linear alkylbenzene sulfonate provides excellent cleaning performance against , coconut alkyl sulfate 1.75%, citric acid builder 9%, other vitamins. 7 moles of ethylene oxide per mole of fatty alkyl alcohol and 7 moles of ethylene oxide. A standard composition in the form of a heavy detergent solution containing 10% condensate with

Next, test compositions were prepared. The test composition contains the fatty alkyl alcohol/ethyl alcohol. 6% tyrene oxide condensate, coconut alkyl diglyceryl ether (above) (prepared as in Example 1) was substantially the same as the standard composition except for 4% .

The composition was tested against a variety of stains. The test method and evaluation method are described in Example 3. The method was similar to that described above. Standard set for contaminated knitted fabrics and contaminated polyester/cotton fabrics The results for the test composition (psu) for the product results (0,0) are as follows: It is shown in the table below.

Ura dirt +0. 7 +0. 8 Bleaching property -0,1-0,1 Enzymatic -0,2+0. 1 Granular +0.3 -0. 3 BMIempa +0.1 +0.1 Note: BMIempa is a polyester-cotton substrate coated with blood, milk and ink. It is a standardized pollution caused by contamination, and it is located in St. Gallen, Switzerland. Manufactured by EMPA In5 titute.

For standard compositions (typical conventional heavy duty detergent liquid formulations), The tested compositions showed improved performance against oil stains and showed improved performance against other stains. It showed performance comparable to conventional formulations.

Although the present invention has been completely explained by way of examples above, the details may be modified within the scope of the present invention. Of course, it is understood that what can be done is possible.

Handbook Supplementary Book Director General of the Property Permit Agency ■ Incident display PCT/US 92109386 2 Name of the invention Detergent composition containing glyceryl ethers 3 Person making the amendment Relationship to the incident: Patent applicant 5 Date of amendment order Shipping date: Month, Day, Heisei 6 Target of correction Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN, TD, TG), AU, BB, BG, BR, CA, C3, F I, HU.

JP, KP, KR, LK, MG, MN, MW, N09PL, RO, RU, SD , U.S.

Claims (10)

[Claims] 1. (a) General formula RO-(C3H6O2)nH(1) (In the formula, R represents an alkyl or alkenyl group having 12 to 18 carbon atoms, C3H6O2 is the hydroxyl group from glycerol and the remaining hydroxyl group represents a divalent group formed by removing a hydrogen atom, and n is an integer), the component ( At least 50 mol% of component (a) is composed of diglyceryl ether; Component (a) in which 25 mol% or less is composed of monoglyceryl ether; (b) Anionic detersive surfactant A detergent composition comprising. 2. At least 60 mol% of component (a) is composed of diglyceryl ether; Claim 1, wherein not more than 20 mol% of component (a) is composed of monoglyceryl ether. Compositions as described. 3. The diglyceryl ether of component (1) is a diglyceryl ether represented by the following one-stage formula. The composition according to claim 1 or 2, which is a mixture comprising R- OCH2CHOHCH2・OCH2CHOHCH2・OH (2); and ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ 4. The ethers represented by formulas (2) and (3) are present in a molar ratio of about 4:1, A composition according to claim 3. 5. Claims 1 to 4, wherein component (a) consists essentially of diglyceryl ether. Composition according to any one of the above. 6. The composition according to any one of claims 1 to 5, wherein R is a coconut alkyl group. thing. 7. Cationic, amphoteric, zwitterionic and semipolar detersive surfactants and detergent building blocks at least one further selected from agents, enzymes, bleaching agents and chelating agents. 7. A composition according to any one of claims 1 to 6, comprising the ingredients. 8. According to any one of claims 1 to 7, which is in the form of a strong detergent liquid or a strong detergent granule. Compositions as described. 9. Single stage ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (wherein R has the meaning as defined in claim 1), a base react with glycerol and/or react with glycerate in the presence of In the formula (1) according to claim 1, the method comprises removing impurities in the product by distillation. A method for producing the diglyceryl ethers or mixtures of these ethers. 10. Diglyceryl ethers represented by formula (1) according to claim 1 or them Use of mixtures of ethers as detersive surfactants.