JP2003508591A - Aqueous liquid detergent composition containing a polymer stabilizing system - Google Patents

Abstract

  (57) [Summary] The present invention relates to aqueous liquid detergent compositions and methods of using such compositions to wash fabrics. More particularly, the present invention relates to aqueous liquid detergent compositions comprising one or more particulate solids, for example, peroxycarboxylic acids, and a polymer stabilizing system.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION

The present invention relates to aqueous liquid detergent compositions and methods of using such compositions for laundering fabrics. More specifically, the present invention relates to an aqueous liquid detergent composition comprising one or more particulate solids such as peroxycarboxylic acid ("peracid"), and a polymer stabilizing system.

[0002]

BACKGROUND OF THE INVENTION

Suspension systems for suspending solid particulates in liquid compositions have been used in the past in special types of cleaning and personal care compositions. For example, suspension systems comprising a surfactant phase and / or a surfactant building liquid have been incorporated into liquid detergent compositions.

An example of such a surfactant-based suspension system is EP 442549 B1, US 4,
828,747, EP160342B2, EP386566A1, US5,39
1,324, EP 668903 and 5,409,632, all of which deal with the suspension of preformed sparingly water-soluble peracids using a surfactant phase. Such a surfactant phase uses (i) one or more nonionic surfactants (low electrolyte) or (ii) a combination of anionic and / or nonionic surfactants with fatty acids and / or electrolytes. Is formed.

GB2279660 describes the use of xanthan gum as a suspending agent for solid particles in liquid detergent products. More specifically, GB2279660 is a peroxyacid-containing suspension that has a special pH for cleaning performance and product bleach stability.
Disclosed is a stable flowable, aqueous liquid laundry detergent composition containing xanthan gum (a polysaccharide polymer) for phase stabilization with a jump system. This has been done without the use of stability-enhancing polymers, which are copolymers of hydrophobic and hydrophilic monomers.

Issued February 12, 1991 and December 17, 1991, respectively,
US Pat. Nos. 4,992,194 and 5,073,285, both to Liberti et al.
Aqueous structured heavy duty liquid detergent formulations containing a pH adjusting system and a selected decoupling polymer are described.

US Pat. No. 4,879,0 issued to Dankowski et al. Issued Nov. 7, 1989
57 discloses an aqueous bleaching suspension containing a peroxycarboxylic acid suspended in a carrier liquid in the presence of an organic thickener and an acidifying agent. The suspension contains agar or xanthan polysaccharide as a thickening agent and a hydrate-forming neutral salt.

Aqueous liquid laundry detergent products containing suspended solids, such as solid, substantially water-insoluble peroxyacids, and especially over various environmental temperatures to which such products are exposed,
It is well known that phase stability problems can occur. Another issue is product and wash pH, because an alkaline wash pH is advantageous for cleaning and bleaching efficacy while a low product pH is required for bleach stability (Cockrell US Patent). 4, 259, 201). In addition, when product detergent surfactant levels are increased with such compositions for good cleaning and bleaching performance, product viscosity often increases to unacceptable levels. Finally, solid particulates, especially suspensions of peroxycarboxylic acids, are often plagued by eye irritation problems.

However, in order to stabilize solid particles, such as peroxycarboxylic acids, which are substantially water-insoluble, and / or to reduce the eye irritation of the composition, in an aqueous liquid detergent composition the present invention is used. The use of the polymer-stabilized systems of US Pat. Thus, one or more particulate solids such as peroxycarboxylic acid (“peracid”).
), And an aqueous liquid detergent composition comprising a polymer stabilizing system, and methods for laundering fabrics using such compositions.

[0009]

[Summary of Invention]

The present invention is directed to one or more particulate solids such as peroxycarboxylic acid ("peracid").
, And a polymer stabilizing system to provide an aqueous liquid detergent composition that meets the above need.

Many aqueous liquid detergent compositions include water-insoluble or partially water-insoluble solid particulates,
For example, it comprises a bleaching agent. The use of polymer stabilizing systems in such aqueous liquid detergent compositions prevents the viscosity of the composition from increasing to unacceptable levels during the useful life of the liquid laundry detergent product containing the composition. Moreover, it was surprisingly found that the composition as a whole sufficiently stabilizes. In other words, the polymer stabilization system as a whole stabilizes the composition so that the viscosity of the composition does not become too viscous for consumer use as a flowable liquid detergent product during the useful life of the product. Preferably, the composition has a viscosity of 2000 cps or less (viscosity of Br at 60 rpm).
ookfield viscosity), more preferably the composition has a viscosity of 1500 cps or less, even more preferably the composition has a viscosity of 1000 cps or less, and most preferably the composition has a viscosity of 800 cps or less.

In one aspect of the invention, there is provided an aqueous liquid detergent composition comprising one or more particulate solids, such as peroxycarboxylic acid (“peracid”), and a polymer stabilizing system. In another aspect of the invention, there is provided an aqueous liquid detergent composition comprising a surfactant, one or more particulate solids such as peroxycarboxylic acid (“peracid”), and a polymer stabilizing system. . In yet another aspect of the invention, one or more particulate solids such as peroxycarboxylic acid (“peracid”) and an ethoxylated nonionic polymer, anionic polyterephthalate polymer, ethoxylated nonionic surfactant, An aqueous liquid detergent composition comprising a polymer stabilizing system comprising a polymer compound selected from the group consisting of polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl N-oxide, polycarboxylates and mixtures thereof. In yet another aspect of the invention, there is provided a method for laundering a fabric in need of washing, which comprises contacting the fabric with an aqueous liquid detergent composition of the invention. Thus, the present invention provides an aqueous liquid detergent composition comprising a polymer stabilizing system,
And a method for laundering a fabric in need of washing, which comprises contacting the fabric with an aqueous liquid detergent composition of the present invention. These and other aspects, objects, features and advantages will be apparent from the following specific description, examples and appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise noted. All references cited herein are incorporated herein by reference.

[0012]

[Detailed Description] Aqueous liquid detergent composition "Aqueous liquid detergent composition" as used herein means a heavy liquid laundry detergent composition, a light liquid detergent composition (liquid dishwashing composition), a liquid cloth softening agent. Agents, liquid fabric conditioners, liquid hard surface cleaning compositions.

Granular solids The term "granular solids" as used herein means solids (ie granules, powders, flakes, chips,
Any detergent component in the form of (for example, particles) or substantially water-insoluble. Preferably, the particulate solid has a particle size of 1-2000 microns.
Preferably, the particulate solid is a peroxycarboxylic acid (peracid).

Peroxycarboxylic acid --Any suitable preformed peroxycarboxylic acid known in the art (hereinafter referred to as peracid and / or peroxyacid) is used in the composition of the present invention as a particulate solid. You may The preformed peracid used herein can be any convenient compound that is stable and forms an effective amount of perate anion under conditions of consumer use. The preformed peracid compound is preferably selected from the group consisting of percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof.

Examples of suitable peracids include, but are not limited to, organic peroxycarboxylic acids having the general formula:

[Chemical 1] In the above formula, R is an alkylene or substituted alkylene group having 1 to about 22 carbon atoms, or a phenylene or substituted phenylene group, and Y is hydrogen, halogen,
Alkyl, aryl, -C (O) OH or -C (O) OOH.

Such organic peroxyacids suitable for use in the present invention can have one or two peroxy groups and can be aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:

[Chemical 2] In the above formula, Y is, for example, H, CH ₃ , CH ₂ Cl, C (O) OH or C (O) OO.
H and n is an integer of 0-20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:

[Chemical 3] In the above formula, Y is, for example, hydrogen, alkyl, alkylhalogen, halogen, C (O)
OH or C (O) OOH.

Typical monoperoxy acids useful herein include alkyl and aryl peroxy acids such as: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium Salt hexahydrate) and o-carboxybenzamide peroxyhexanoic acid (sodium salt); (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycapron Acid (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP); (iii) amidoperoxy acid such as peroxysuccinic acid ( NAPS ) Or monononylamide of peroxyadipic acid (NAPAA); there is.

Typical diperoxy acids useful herein include alkyl and aryl diperoxy acids such as (iv) 1,12-diperoxidedecanedioic acid; (v) 1,9-diperoxyazelaic acid; (vi) diperoxybrassic acid, diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyldiperoxybutane-1,4-dioic acid; (viii) 4,4'-sulfonylbisperoxybenzoic acid; is there.

Such a peroxycarboxylic acid was published on November 20, 1984.
Hartman US Patent 4,483,781, Burns et al US Patent 4,634,551
, European Patent Application 0,133,3 of Banks et al., Published February 20, 1985.
54, and US Patent 4,41 to Chung et al., Issued Nov. 1, 1983.
2, 934. Its source includes 6- as described in detail in Burns et al., US Pat. No. 4,634,551 issued Jan. 6, 1987.
There is also nonylamino-6-oxoperoxycaproic acid. EIDu Pont de
Persulfate compounds such as OXONE manufactured by Nemours of Wilmington, DE may also be used as a suitable source of peroxymonosulfate.

[0020]   Preferred peracids for use in the compositions of the invention are those having the general formula:

[Chemical 4] In the above formula, R is C _1-4 alkyl and n is an integer of 1-5. Particularly preferred peracids have the formula where R is CH ₂ and n is 5, ie US Pat.
87,818,5,310,934,5,246,620,5,279,757
And phthaloylaminoperoxycaproic acid (PAP) as described in 5,132,431. PAP is commercially available from Ausimont SpA under the trade name Euroco.

The peracid used herein is preferably about 10 to about 10,000 ppm, more preferably about 20 to about 5000 ppm, and even more preferably about 30 to about 1500 p.
pm, even more preferably about 50 to about 1000 ppm, most preferably about 5
It has a solubility in the aqueous liquid composition of 0 to about 800 ppm measured at 20 ° C. In a particularly preferred embodiment of the invention, the peracid has an average particle size of 100 microns or less, more preferably 80 microns or less, even more preferably 60 microns or less. Most preferably, when the peracid is PAP, it has an average particle size of about 20 to about 50 microns. The peracid is preferably about 0.1 to about 25%, more preferably about 0.1 to about 20%.
, Even more preferably at a level of about 1 to about 10%, most preferably about 2 to about 4%. On the other hand, the peracid may be present at significantly higher levels, for example 10-40%, more preferably 15-30%, most preferably 15-25%.

Polymer Stabilization System In addition to one or more particulate solids, the composition of the present invention comprises a polymer stabilization system. The polymer stabilizing system of the present invention comprises a polymer compound (including an oligomer compound). As used herein, "polymeric compound" includes oligomeric compounds,
By polymeric and / or oligomeric compounds are meant that are characterized by having both hydrophilic and hydrophobic components.

The polymeric compounds useful in the compositions of the present invention can contain a variety of charges, such as anions or cations (see US Pat. No. 4,956,447), and uncharged monomer units, the structure of which is linear, There are branches or even star shapes. They may also contain cap moieties that are particularly effective in controlling molecular weight or altering physical or surfactant properties. The structure and charge distribution can be tailored for specific applications of various detergents or detergent additive products.

[0024]   Many of the suitable polymeric compounds are interactive with anionic surfactants,
Characterized by having a nonionic hydrophilic or hydrophobic segment
Be done.   Examples of polymeric compounds suitable for use in the compositions of the present invention include polymers having the following:
-Compounds include, but are not limited to: (A) one or more nonionic hydrophilic components consisting essentially of:   (I) a polyoxyethylene segment having a degree of polymerization of at least 2, or   (Ii) Oxypropylene or polyoxypropylene seg having a degree of polymerization of 2 to 10
Ment (the hydrophilic segment of which it is adjacent to each end by an ether bond
Does not contain any oxypropylene units unless attached to), or   (iii) Oki consisting of oxyethylene and 1 to about 30 oxypropylene units
A mixture of sialkylene units; or (B) one or more hydrophobic components consisting of:   (I) C_ThreeOxyalkylene terephthalate segment (when its hydrophobic component is
If xyethylene terephthalate is also included, oxyethylene terephthalate: C _Three The ratio of oxyalkylene terephthalate units is about 2: 1 or less
), And / or   (Ii) C_Four-C₆Alkylene or oxy C_Four-C₆Alkylene segment,
Or a mixture thereof, and / or   (iii) a poly (vinyl ester) segment having a degree of polymerization of at least 2, preferably
Preferably poly (vinyl acetate), and / or   (Iv) C₁-C_FourAlkyl ether or C_FourHydroxyalkyl ether storage
A substituent, or a mixture thereof (wherein the substituent is C₁-C_FourAlkyl ether or
C_FourForm of hydroxyalkyl ether cellulose derivative, or mixture thereof
And such cellulose derivatives are amphoteric); or (C) A combination of (a) and (b).

[0025]   Typically, the (a) (i) polyoxyethylene segment is 2 to about 200 (
Higher levels may also be used), preferably 3 to about 150, more preferably
Has a degree of polymerization of 6 to about 100. Suitable Oxy C_Four-C₆Alkylene hydrophobic
Gumento was issued January 26, 1988, incorporated herein by reference.
Disclosed in Gosselink US Pat. No. 4,721,580, MO_ThreeS (CH
_Two)_nOCH_TwoCH_TwoO- (M is sodium, n is an integer of 4-6)
Polymeric compound end caps, but are not limited thereto.

[0026] Other polymeric compounds useful in the compositions of the present invention, (commercially available as METHOCEL ^R from Dow) cellulose derivatives such as hydroxyethyl ether cellulose polymer; ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide Copolymer blocks with terephthalate (examples are US Patent 3,959,230 to Hays, 3,893,92 to Basadur
9)); C ₁ -C ₄ alkylcellulose and C ₄ hydroxyalkylcellulose, such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose; but are not limited thereto. Examples of various cellulosic polymer compounds are Nico
U.S. Pat. No. 4,000,093.

Other polymeric compounds characterized by a poly (vinyl ester) hydrophobic segment include grafted copolymers of poly (vinyl ester), eg, C ₁ -C ₆ vinyl esters, preferably grafted onto a polyalkylene oxide backbone. Poly (
Vinyl acetate). See Kud et al., European Patent Application 0,219,048, published 22 April 1987. Commercially available examples are SOKALAN compounds such as SOKALAN HP-22 available from BASF, Germany. Other polymeric compounds are derived from polyoxyethylene glycols with an average molecular weight of 300-5000, 9
10-15% by weight with 0-80% by weight polyoxyethylene terephthalate
Is a polyester having repeating units containing ethylene terephthalate. Commercially available examples are ZONCON 5126 from duPont and MILEASE T from ICI.

Other suitable polymeric compounds include Gossel, published December 8, 1987.
Ink et al. US Pat. No. 4,711,730 ethyl or methyl capped 1,2-
Propylene terephthalate-polyoxyethylene terephthalate polyester;
Gosselink US Pat. No. 4,721,580 issued Jan. 26, 1988
Anionic end-capped oligomeric ester of
Comprising a sulfopolyethoxy group derived from polyethylene glycol (PEG); having a polyethoxy end cap of the formula X- (OCH ₂ CH ₂ ) _n- (n is 12 to about 43, X is C ₁ --C ₄ alkyl, preferably methyl), Gosselink US Pat. No. 4,702, issued Oct. 27, 1987.
There are 857 block polyester oligomeric compounds, all of which are incorporated herein by reference.

Additional polymeric compounds that may be used herein include certain polymeric compounds of US Pat. No. 4,877,896 to Maldonado et al., Issued Oct. 31, 1989, wherein anionic, especially sulfoaroyl, is used. Disclosed are end-capped terephthalate esters, the patents of which are incorporated herein by reference. Terephthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units. Among the polymer compounds of US Pat. No. 4,877,896 are C ₃ oxyalkylene terephthalate (propylene terephthalate) repeating units belonging to the polyoxyethylene hydrophilic component or the hydrophobic component of (b) (i) above. Includes substances that have.

Additional polymeric compounds include (I) nonionic terephthalates (Violland) using a diisocyanate coupling agent to link the polymer ester structure.
Et al., US 4,201,824 and Lagasse et al., US 4,240,918).
(II) There is a polymer compound having a carboxylate end group produced by adding trimellitic anhydride to a known polymer compound to convert a terminal hydroxyl group into a trimellitate ester. With the proper choice of catalyst, trimellitic anhydride forms a link to the end of the polymer via the ester of the carboxylic acid of the remote trimellitic anhydride rather than ring opening of the anhydride bond. Nonionic or anionic polymeric compounds may be used as starting materials as long as they have hydroxyl end groups which are esterified. See Tung et al., US 4,525,524. Other classes include: (III) Urethane-bonded species anionic terephthalate-based polymer compounds (see US Pat. No. 4,201,824 to Violland et al.); (IV) Poly (vinylcaprolactam), including both nonionic and cationic polymers. ), And related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethylmethacrylate (see US Pat. No. 4,579,681 to Ruppert et al.).
(V) In addition to SOKALAN type manufactured by BASF, a graft copolymer (Rhone-Poulen) made by grafting an acrylic monomer onto a sulfonated polyester.
Chemie, 1988 EP 279,134A); (VI) Grafting vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as casein (
(See EP 457,205A of BASF (1991)); (VII) Polyester-polyamide polymer compounds prepared by condensing adipic acid, caprolactam and polyethylene glycol, especially for treating polyamide fabrics (Beva
DE et al., DE 2,335,044, Unilever NV, 1974). Other useful polymeric compounds are US Pat. Nos. 4,240,918, 4,787,989, 4,5
25,524 and 4,877,896.

Yet another class of polymeric compounds useful in the compositions of the present invention includes polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, polyvinyl acetate. There are polymers and their mixtures, examples of which are:
Miracle et al., US Pat. No. 5,817,614. If used, these polymeric compounds typically comprise about 0.01 to about 10% by weight of the composition, preferably about 0.01 to about 5%, more preferably about 0.05 to about 2%. is there.

Polymeric polycarboxylate materials may also be used as polymeric compounds according to the present invention. Such polycarboxylate materials may be prepared by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. There is. The presence of monomer segments containing no carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the present polymeric polycarboxylates is suitable provided that such segments are up to about 40% by weight.

A particularly suitable polymeric polycarboxylate may be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2000.
10,000, more preferably about 4000-7000, most preferably about 400
It is in the range of 0 to 5000. Water-soluble salts of such acrylic acid polymers include
For example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known substances. The use of this type of polyacrylate in detergent compositions is described, for example, in Diehl US Pat.
It is disclosed in Japanese Patent No. 3,308,067.

Acrylic acid / maleic acid based copolymers may also be used as preferred polymer compounds in the polycarboxylate class. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably from about 2000 to 100,000, more preferably from about 5000 to 75,000 and most preferably from about 7000 to 65,000. The ratio of acrylate to maleate segment in such copolymers is usually about 30: 1 to about 1: 1 and more preferably about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known substances described in European patent application 66915 published on Dec. 15, 1982 and also hydroxypropyl in EP 193,360 published on Sep. 3, 1986. Such polymers containing acrylates are described. Still other useful polymeric compounds of this class are maleic acid / acrylic acid / vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, acrylic acid / maleic acid / vinyl alcohol 45/45/10 terpolymers. Another polymeric compound that is included is polyethylene glycol (PEG).

Yet another class of polymeric compounds useful in the compositions of the present invention are nonionic surfactants having a high degree of ethoxylation, preferably about 9 to 30 moles of ethyleneoxy units. If a nonionic surfactant is used as the polymeric compound according to the present invention, preferably the nonionic surfactant is present in the composition of the present invention at a level of up to 1% by weight of the composition.

One preferred polymeric compound is an oligomeric terephthalate, typically made by a process involving at least one transesterification / oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. Esters include, but are not limited to. Such esters are of course made by incorporating additional monomers in the ester structure at 1, 2, 3, 4 or more positions without forming a tightly crosslinked overall structure.

Another type of preferred polymeric compound is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More particularly, these polymers are composed of repeating units of ethylene terephthalate and PEO terephthalate in a preferred molar ratio of ethylene terephthalate units to PEO terephthalate units of about 25:75 to about 35:65, wherein the PEO terephthalate units are about. It includes polyethylene oxide having a molecular weight of 300 to about 2000. The molecular weight of this polymeric compound is preferably in the range of about 25,000 to about 55,000. For examples of such polymeric compounds, see US Patent 3,959,230 to Hays and 3,893 to Basadur.
See 929.

Yet another preferred polymeric compound has an average molecular weight of about 300 to about 5000.
A polyester consisting of repeating units of ethylene terephthalate units, containing about 10 to 15% by weight of ethylene terephthalate units together with about 90 to 80% by weight of polyoxyethylene terephthalate units, derived from polyoxyethylene glycol of The molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound is preferably about 2: 1 to about 6: 1. Examples of this type of polymer compounds are commercially available materials ZELCON ^R and ICI made MILEASE ^R made DuPont. These polymeric compounds and their method of preparation are described in more detail in US Pat. No. 4,702,857 to Gosselink.

Another class of preferred polymeric compounds is, for example, JJ dated November 6, 1990, JJ
Consists of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and an allyl-derived sulfonated end moiety covalently attached to the backbone, as described in Scheibel and EP Gosselink, US Pat. No. 4,968,451. , A sulfonation product of a substantially linear ester oligomer (such ester oligomer is (a) ethoxylated allyl alcohol and (b) the product of (a) in a two-step transesterification / oligomerization operation. Reacting with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”),
And (c) may be prepared by reacting the products of (b) with sodium metabisulfite in water); Gosselink et al., US 4,711, December 8, 1987.
730 nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyesters, eg prepared by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) (“PEG”) Partially and fully anionic end-capped oligomeric esters of Gosselink US Pat. No. 4,721,580 dated 26 January 1988, eg ethylene glycol (“EG”), PG, DMT and 3,6.
-Oligomers of Na-dioxa-8-hydroxyoctane sulfonate; 198
Gosselink US 4,702,857 Nonionic Capped Block Polyester Oligomer Compounds, Oct. 27, 1995, eg DMT, Me Capped PE
G and EG and / or PG, or DMT, EG and / or PG, M
Made from a combination of e-capped PEG and Na dimethyl-5-sulfoisophthalate; Maldonado, Gosselink et al., US 4,8, Oct. 31, 1989.
There are, but are not limited to, 77,896 anionic, especially sulfoaroyl end-capped terephthalate esters; the latter being representative of polymeric compounds useful in both laundry and fabric conditioning products, including m-sulfo. An ester composition made from benzoic acid monosodium salt, PG and DMT, but optionally but preferably PEG is added, eg PEG3400.

Another preferred polymeric compound is one sulfoisophthaloyl unit, 5
Two terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a predetermined ratio, preferably about 0.5: 1 to about 10: 1, and 2-
The empirical formula (CAP) ₂ (EG / P is similar to that of an oligomer consisting of two endcap units derived from sodium (2-hydroxyethoxy) ethanesulfonate.
G) ₅ (T) ₅ (SIP) ₁ , an oligomer having terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units. End cap (CA
P), preferably modified isethionate. The polymer compound is preferably 0.5 to 20% by weight of oligomer of a crystal reduction stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate, or xylene-, cumene- and toluene-. Further comprising a member selected from sulphonates or mixtures thereof, these stabilizers or modifiers are all disclosed by Gosselink, Pan, Kellett and Hal published May 16, 1995.
Introduced into a synthesis vessel as disclosed in US Pat. No. 5,415,807. Suitable monomers for the above polymer compounds include 2- (2-hydroxyethoxy)
Ethanesulfonic acid Na, DMT, dimethyl-5-sulfoisophthalate Na, E
There are G and PG.

Yet another group of preferred polymeric compounds are: (1) (a) dihydroxy sulfonates, polyhydroxy sulfonates, units that are at least trifunctional so that ester bonds are formed with the branched oligomer backbone, and At least one unit selected from the group consisting of combinations thereof; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one non-sulfonated 1,2-oxyalkyleneoxy moiety. A main chain of units, and (2) nonionic cap units, anionic cap units such as alkoxylated, preferably ethoxylated isethionates, alkoxylated propane sulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfoaroyl derivatives An oligomeric ester comprising one or more cap units selected from conductors and mixtures thereof. Among such esters, the following empirical formulas are preferred: [(CAP) x (EG / PG) y '(DEG) y "(PEG) y"'"(T) z (SIP) z '(SEG). ) Q (B) m] In the above formula, CAP, EG / PG, PEG, T and SIP are as described above;
(DEG) represents a di (oxyethylene) oxy unit; (SEG) represents a unit derived from sulfoethyl ether of glycerin and related moieties;
B) represents a branching unit that is at least trifunctional so that ester bonds are formed resulting in a branched oligomeric backbone; x is from about 1 to about 12; y'is about 0.5.
To about 25; y ″ is 0 to about 12; y ″ ″ is 0 to about 10; y ′
+ Y ″ + y ″ ″ is about 0.5 to about 25 in total; z is about 1.5 to about 25; z ′ is 0 to about 12; z + z ′ is about 1.5 in total. To about 25; q is about 0.05 to about 12; m is about 0.01 to about 10; x, y ', y ",
y ″ ″, z, z ′, q and m represent the average number of moles of the corresponding unit per mole of the ester, the ester having a molecular weight of about 500 to about 5000.

Preferred SEG and CAP monomers for the above ester include 2- (2,3-dihydroxypropoxy) ethanesulfonic acid Na (“SEG”), 2- [2- (2
-Hydroxyethoxy) ethoxy] ethanesulfonic acid Na ("SE3") and its homologs, and mixtures thereof, as well as the ethoxylated and sulfonated products of allyl alcohol. Preferred polymeric compound esters of this class include sodium 2- [2- (2- (2-hydroxyethoxy) ethoxy] ethoxy] ethanesulfonate and / or 2- [2- [2- (2 -Hydroxyethoxy) ethoxy] ethoxy] ethanesulfonic acid sodium salt, DMT
2- (2,3-dihydroxypropoxy) ethanesulfonic acid sodium salt, EG
And the product of transesterification and oligomerization of PG, labeled as (CAP) ₂ (T) ₅ (EG / PG) _1.4 (SEG) _2.5 (B) _0.13 , where CAP is [Na ⁺ -O ₃ S (CH ₂ CH ₂ O) _3.5 ]-,
B is a unit from glycerin and the EG / PG molar ratio is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.

Yet another preferred class of polymeric compounds for use in the compositions of the present invention are oligomeric and substantially linear sulfonated polyethoxy / propoxy endcapped esters, examples and methods of preparation of which are described in Gosselink et al. US Patent 5,415,80
7 are described. The ester consists of oxyethyleneoxy units and terephthaloyl units. Preferred esters further comprise oxy-1,2-propyleneoxy, sulfoisophthalate, and optionally poly (oxyethylene) oxy units (degree of polymerization of 2-4). The ester has a relatively low molecular weight, typically about 500 to about 8000. In their broadest sense, polymeric compounds of this type comprise an oligomeric ester "backbone" that is endcapped with the requisite endcapping units at one or preferably both ends of the backbone.

The requisite end cap unit is an anionic hydrophilic moiety derived from a sulfonated polyethoxy / propoxy group and attached to the ester with an ester bond. Preferred end cap units of the formula _{(MO 3 S) (CH 2} ) m (CH 2 CH 2 O) (RO
) _N- (M is a salt-forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or mixtures thereof, n is 0-2) and mixtures thereof. Certain uncharged hydrophobic aryldicarbonyl units are essential to the backbone units of the present oligoesters. Preferably, these are exclusively terephthaloyl units.

A preferred ester of this type comprises, per mole of the ester: i) of the formula (MO ₃ S) (CH ₂ ) _m (CH ₂ CH ₂ O) (RO) _n- . Sulfonated polyethoxy / propoxy endcap units (M is a salt-forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or mixtures thereof, n is 0-2) and mixtures thereof About 1 to about 2 moles; ii) units selected from the group consisting of about 0.5 to about 66 moles: a) oxyethyleneoxy units; b) oxyethyleneoxy and oxy-1,2-propyleneoxy units. Mixtures (wherein the oxyethyleneoxy units are present in an oxyethyleneoxy to oxy-1,2-propyleneoxy molar ratio of 0.5: 1 to about 10: 1). ); And c) a mixture of a) or b) with poly (oxyethylene) oxy units, the poly (oxyethylene) oxy units having a degree of polymerization of 2 to 4; When the oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) oxy units to all group ii) units is from 0: 1 to about 0.33: 1.
When the poly (oxyethylene) oxy units have a degree of polymerization of 3, the molar ratio of poly (oxyethylene) oxy units to all group ii) units is from 0: 1
About 0.22: 1; when the poly (oxyethylene) oxy units have a degree of polymerization of 4, the molar ratio of poly (oxyethylene) oxy units to all group ii) units is from 0: 1 to about 0.14: 1 is); iii) terephthaloyl units from about 1.5 to about 40 mol; and iv) formula _{- (O) C (C 6} H 3) (SO 3 M) C (O) - 5 of -Sulfoisophthaloyl units (M is a salt-forming cation such as an alkali metal or tetraalkylammonium ion) 0 to about 26 moles.

More preferably, the polymeric compound useful in the composition of the present invention is U of Gosselink.
Selected from the group of polymeric compounds and mixtures thereof described in S. Pat. No. 4,702,857, Scheibel et al. Most preferably, the polymeric compounds useful in the compositions of the present invention are those of Scheibel et al.
The polymer compounds described in S Patent 4,968,451.

As described herein, in addition to providing stabilization of the composition of the present invention, the polymer stabilization system also provides acceptable eye irritation properties for the composition. In other words, the presence of the polymer stabilizing system within the composition of the present invention is the result of the TNO Nutrit of the Netherlands.
It results in lower eye irritation as compared to compositions lacking a polymer stabilizing system as measured using the Chicken Ex Vivo Eye Test performed at the Ion and Food Research Institute. A preferred polymer stabilizing system for this purpose is Scheibel et al., US Pat.
Comprising the polymer compound described in 8,451.

Generally, the composition of the present invention will be from about 0.01 to about 10% by weight, typically from about 0.1.
Containing about 5%, preferably about 0.02 to about 3.0% polymeric compound.

Aqueous Liquid Detergent Compositions The present invention relates to aqueous based liquid detergent compositions. The aqueous liquid detergent composition preferably comprises from about 10 to about 98% by weight, preferably from about 30 to about 95%, of an aqueous liquid carrier, preferably water, in addition to the particulate solids and polymer stabilizing system described above. It consists of The aqueous liquid detergent composition of the present invention preferably also comprises one or more cleaning additive substances. The term "cleaning additive" as used herein is preferably compatible with the other ingredients present in the aqueous liquid detergent composition of the present invention,
It means any liquid, solid or gaseous substance selected for an aqueous liquid detergent composition.

The specific choice of cleaning additive material is readily made by considering the surface, article or fabric to be cleaned. Examples of suitable cleaning additives include US Pat. No. 5,705,464, 5,710,115,5,698,
504, 5,695,679, 5,686,014 and 5,646,101, surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, chelants. , Optical brightener, stain release polymer, dye transfer agent, dispersant, foam control agent, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescent agent, fabric conditioner, fabric softener, water Degradable surfactants, preservatives, antioxidants, anti-shrinkage agents, anti-wrinkle agents, fungicides, fungicides, color speckles, silver care agents, rust and / or corrosion inhibitors, alkalis Sources, solubilizers, carriers, processing aids, pigments and pH control agents include, but are not limited to. Specific cleaning additives are exemplified in detail below.

If the cleaning additive is not compatible with the other ingredients present in the aqueous liquid detergent composition of the present invention, the incompatible cleaning additive and other ingredients are allowed to separate until the two components are adequately mixed. Any suitable method of keeping (not contacting each other) can be used. Suitable methods include any method known in the art such as gelcap, encapsulation, tablets, physical separation and the like.

The aqueous liquid detergent composition of the present invention comprises: (a) one or more particulate solids, preferably a peracid; (b) a polymer stabilizing system; (c) optionally but preferably a surfactant. And (d) optionally, but preferably, one or more cleaning additives. The aqueous liquid detergent composition may contain the cleaning additive in about 1 to about 99.9% by weight of the composition.

As used herein, "fabric laundry composition" includes hand and machine laundry including a laundry additive composition and a composition suitable for dipping and / or pretreatment of stained fabrics. There is a detergent composition. When the aqueous liquid detergent composition of the present invention is formulated as a composition suitable for washing machine washing methods, the composition of the present invention preferably comprises both a surfactant and a builder compound, and preferably an organic compound. Contains one or more cleaning additives selected from polymeric compounds, bleaching agents, additional enzymes, foam control agents, dispersants, lime soap dispersants, soil suspension and anti-redeposition agents, and corrosion inhibitors. There is. The laundry composition may also contain a softener as an additional cleaning additive. The aqueous liquid detergent composition of the present invention may be used in a liquid form as a detergent additive product.
Such additive products are present to enhance or enhance the performance of conventional detergent compositions and may be added at any stage of the laundry process.

If desired, the laundry detergent composition has a density of 4 as measured at 20 ° C.
It is from 00 to 1200 g / L, preferably from 500 to 950 g / L. The aqueous liquid detergent composition according to the present invention may be in “concentrated form”, in which case
The aqueous liquid detergent composition according to the present invention contains a small amount of water compared to conventional liquid detergents. Typically, the water content of the concentrated aqueous liquid detergent composition is preferably 40% or less by weight of the composition, more preferably 30% or less, most preferably 20% or less. Further, the aqueous liquid detergent composition according to the present invention may be an isotropic liquid, an aqueous gel and a colored liquid composition.

Preferred Cleaning Additives Surfactants The aqueous liquid detergent compositions of the present invention preferably comprise a surfactant system which preferably comprises one or more cleaning cosurfactants. The cosurfactant may be selected from nonionic detersive surfactants, anionic detersive surfactants, bipolar detersive surfactants, amine oxide detersive surfactants, biodegradable branched surfactants and mixtures thereof. The surfactant system is typically about 5 to about 70% by weight of the detergent composition, preferably about 15 to about 30%.

[0056] i. Anionic Surfactant Anionic surfactant includes C ₁₁ -C ₁₈ alkylbenzene sulfonate (
LAS), primary, branched and random C ₁₀ -C ₂₀ alkyl sulphates (
AS), the formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) CH 3 and _CH 3 (C
^{_{H 2) y (CHOSO 3 -}} M +) C of _CH 2 _{CH 3} 10 _{-C 18} secondary (2,3)
Alkyl sulphates (x and (y + 1) are integers of at least about 7, preferably at least about 9 and M is a water-soluble cation, especially sodium), unsaturated sulphates such as oleyl sulphate, C ₁₀ -C ₁₈ Alkylalkoxy sulphates (“AExS”; especially EO1-7 ethoxysulfates), C ₁₀ -C ₁₈ alkylalkoxycarboxylates (especially EO1-5 ethoxycarboxylates), C ₁₀ -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polys. glycosides and their corresponding sulfated polyglycosides, and there is a _C 12 _{-C 1 8 α-} sulfonated fatty acid esters.

Generally speaking, anionic surfactants useful herein are described in 25 August 1981.
Barrat et al., US Patent 4,285,841 and 1975 12
It is disclosed in US Pat. No. 3,919,678 issued to Laughlin et al. Useful anionic surfactants include water-soluble salts of organic sulfuric acid reaction products having an alkyl group of about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group in the molecular structure, especially alkali metal, ammonium and There are alkylol ammonium (eg, monoethanol ammonium or triethanol ammonium) salts (the term "alkyl" also includes the alkyl portion of aryl groups). Examples of synthetic surfactants in this group are alkyl sulphates, especially those obtained by sulfating higher alcohols (C ₈ -C ₁₈ carbon atoms) such as those made by reducing the glycerides of tallow or coconut oil.

Other anionic surfactants herein are water-soluble salts of alkylphenol ethylene oxide ether sulphates having from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group. . Other useful anionic surfactants herein include water-soluble salts of esters of α-sulfonated fatty acids having about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; acyl. Water-soluble salts of 2-acyloxyalkane-1-sulfonic acids having about 2 to 9 carbon atoms in the group and about 9 to about 23 carbon atoms in the alkane moiety; about 1
A water-soluble salt of an olefin sulfonate having 2 to 24 carbon atoms; and β- having about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane moiety.
There is an alkyloxy alkane sulfonate.

[0059] Here, a particularly preferred anionic surfactants are the alkyl sulfates, especially alkyl polyethoxylate sulfates of the _{formula: RO (C 2 H 4 O} ) x SO 3 - M + ( in the above formulas R is a saturated or unsaturated Is an alkyl group saturated from about 10 to about 22 carbon atoms, M is a cation which renders the compound water soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x is on average from about 1 to about 15. ),
Non-ethoxylated C _12-15 primary and secondary alkyl sulphates. Preferably, a mixture of such ethoxylated and non-ethoxylated alkyl sulphates is present under cold water wash conditions, i.e. below about 65 ° F (18.3 ° C).

Fatty acids useful in the invention as anionic surfactants include saturated and / or unsaturated fatty acids obtained or synthesized from natural sources. Examples of suitable fatty acids include, but are not limited to, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid. Other fatty acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid and ricinoleic acid.

Examples of suitable anionic surfactants are “Surface Active Agents and Detergent”.
s "(Vol. I and II by Schwartz, Perry and Berch).
It is also generally disclosed in column 23, line 58 to column 29, line 23 of S Patent 3,929,678.

Ii. Nonionic Surfactants Suitable nonionic detergent surfactants were published on December 30, 1975.
It is generally disclosed in US Pat. No. 3,929,678 to Laughlin et al. And US Pat. No. 4,285,841 issued to Barrat et al. On Aug. 25, 1981. Useful nonionic Illustrative non-limiting species of the surfactant, the so-called narrow peak EO about 1-22, including alkyl ethoxylates of C ₈ -C ₁₈ alkyl ethoxylates (
_{"AE"), C 6 -C} 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), alkyl dialkyl amine oxide, there is alkanoyl glucose amides, and mixtures thereof.

If nonionic surfactants are used, the compositions of the present invention preferably contain within about 10% by weight, preferably 0 to about 5%, more preferably 0 to about 3% of nonionic surfactants. Contains. Ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC ₂ H ₄ ) _n OH are preferred, where R is from about 8 to about 1.
An aliphatic hydrocarbon group having 5 carbon atoms, and an alkyl group selected from the group consisting of an alkylphenyl group having about 8 to about 12 carbon atoms, the average value of n is about 5
Is about 15. These surfactants were published by Le on August 18, 1981.
Further details are provided in US Pat. No. 4,284,532 to ikhim et al. Ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of about 6 to about 12 moles of ethylene oxide per mole of alcohol are especially preferred.

Other nonionic surfactants useful herein include, but are not limited to: polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols having an alkyl group of about 6 to about 12 carbon atoms in a linear or branched configuration with an alkylene oxide. In a preferred embodiment, ethylene oxide is present in an amount corresponding to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type, Igepal ^R CO-630, all marketed by the GAF Corporation
Triton ^R X-45, X-114, X-100 and X-1 sold by Rohm & Haas Company
There is 02. These compounds are commonly referred to as alkylphenol alkoxylates (eg alkylphenol ethoxylates).

Condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. Alkyl chains of aliphatic alcohols are linear or branched, primary or secondary, usually about 8
Has about 22 carbon atoms. Particularly preferred is the condensation product of an alcohol having an alkyl group of about 10 to about 20 carbon atoms and about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^R 15-S-9 (both sold by Union Carbide Corporation.
Condensation product of C ₁₁ -C ₁₅ straight chain alcohol and 9 moles of ethylene oxide), Terg
tol ^R 24-L-6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohol and 6 moles of ethylene oxide with narrow molecular weight distribution); sold by Shell Chemical Company
Neodol ^R 45-9 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 9 moles of ethylene oxide), Neodol ^R 23-6.5 (condensation product of C ₁₂ -C ₁₃ straight chain alcohol and 6.5 moles of ethylene oxide), Neodol ^R 45-7 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 7 moles of ethylene oxide), Neodol ^R 45-4 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 4 moles of ethylene oxide); The Procter & Gamble Compa
There are Kyro ^R EOB sold _(C 13 _{-C 15} condensation products of alcohols with 9 moles ethylene oxide) from ny. Other commercially available nonionic surfactants include Shell Ch
there is Genapol UD-080 ^R sold by Dobanol 91-8 ^R and Hoechst sold by emical Co.. Nonionic surfactants in this category are commonly referred to as "alkyl ethoxylates".

A condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is water insoluble. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the overall water solubility of the molecule,
The liquid nature of the product is retained up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to condensation with ethylene oxide within about 40 moles. Examples of compounds of this type are available from BASF, there are certain commercially available Pluronic ^R surfactants.

A condensation product of ethylene oxide with the product obtained from the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and usually has a molecular weight of about 2500 to about 3000. The hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to about 80 weight percent polyoxyethylene and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant include B
Sold by ASF, there are certain commercially available Tetronic ^R compound.

The semipolar nonionic surfactant comprises two moieties selected from the group consisting of one alkyl moiety having from about 10 to about 18 carbon atoms, an alkyl group having from about 1 to about 3 carbon atoms and a hydroxyalkyl group. Having water-soluble amine oxide; about 10 to about 1 carbon atom
A water-soluble phosphine oxide having one alkyl moiety of eight, two moieties selected from the group consisting of an alkyl group of about 1 to about 3 carbon atoms and a hydroxyalkyl group; one alkyl of about 10 to about 18 carbon atoms A special category of nonionic surfactants, including water soluble sulfoxides having moieties, moieties selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms.

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

[Chemical 5] Wherein R ³ is an alkyl, hydroxyalkyl, alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene having from about 2 to about 3 carbon atoms, a hydroxyalkylene group or A mixture thereof;
x is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having about 1 to about 3 ethylene oxide groups. The R ⁵ groups may be joined together, for example via an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

Hydrophobic groups having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about. 1.3 ~
A polysaccharide having about 2.7 sugar units, eg with hydrophilic groups of polyglycosides, 19
Alkyl polysaccharides disclosed in Llenado US Pat. No. 4,565,647, issued Jan. 21, 1986. Reducing sugars having 5 or 6 carbon atoms may also be used, eg glucose, galactose and galactosyl moieties may be used in place of the glucosyl moiety (optionally a hydrophobic group attached at the 2, 3, 4 position etc.). , Yields glucose or galactose rather than glucoside or galactoside). For example, there may be an intersugar linkage between one position of the additional sugar unit and the 2, 3, 4 and / or 6 position of the preceding sugar unit.

Optionally, though less desirable, there may be a polyalkylene oxide chain linking the hydrophobic and polysaccharide moieties. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include about 8 to about 18, preferably about 10
There are saturated or unsaturated, branched or unbranched alkyl groups having about 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group contains no more than about 3 hydroxy groups, and / or the polyalkylene oxide chain has about 1
It can contain up to 0, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides include octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactoside, lactoside, glucose, fructoside. , Fructose and / or galactose. Suitable mixtures include coconut alkyl di-, tri-, tetra-
And pentaglucoside, and tallow alkyl tetra-, penta- and hexaglucoside.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and Is selected from the group consisting of a mixture of :, wherein the alkyl group has from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2
Or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to About 2.
7 Glycosyl is preferably derived from glucose. To produce these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to produce glucoside (
Bond at position 1). Additional glycosyl units may also be attached between their 1-position and the preceding glycosyl units at the 2, 3, 4 and / or 6-positions, preferably predominantly the 2-position.

[0073]   Fatty acid amide surfactant having the formula:

[Chemical 6] In the above formula, R ⁶ is an alkyl group having about 7 to about 21 (preferably about 9 to about 17) carbon atoms, and each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl. and _{- (C 2 H 4 O)} x H (x is from about 1 to about 3) is selected from the group consisting of.

Preferred amides are C ₈ -C ₂₀ ammonia amides, monoethanolamides,
Diethanolamide and isopropanolamide. Conventional nonionic and amphoteric surfactants include C ₁₂ -C ₁₈ alkyl ethoxylates (AE), including so-called narrow peak alkyl ethoxylates, C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxylates). / Propoxy). It may also be used C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides. A typical example is C ₁₂ -C ₁₈ N-methylglucamide. WO9,206
, 154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamide may be used for low foaming properties. It may also be used C ₁₀ -C ₂₀ conventional soaps. Branched chain C ₁₀ -C ₁₆ soaps may also be used if high foamability is desired. Examples of nonionic surfactants are 1981
US Pat. No. 4,285,841 issued to Barrat et al.

Preferred examples of these surfactants are ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC ₂ H ₄ ) _n OH, where R is a fatty acid having from about 8 to about 15 carbon atoms. Group hydrocarbon groups, and alkyl groups selected from the group consisting of alkylphenyl groups having from about 8 to about 12 carbon atoms, with an average value of n from about 5 to about 15. These surfactants were issued on August 18, 1981
Further details are given in US Pat. No. 4,284,532 to Leikhim et al. Ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of about 6 to about 12 moles of ethylene oxide per mole of alcohol are especially preferred. Mixtures of anionic and nonionic surfactants are especially useful. Including C ₁₂ -C ₁₈ betaines and sulfobetaines (sultaines), other conventional useful surfactants are listed in standard texts.

Iii. Amine Oxide Surfactant The composition also contains an amine oxide surfactant of the formula: R ¹ (EO) _x (PO) _y (BO) _z N (O) (CH ₂ R ′) ₂ · qH ₂ O (I) In general, structure (I) has one long chain moiety R ¹ (EO) _x (PO) _y (BO) _z and two short chain moieties CH ₂ R ′. I understand. R 'is preferably selected from hydrogen, methyl and _-CH 2 OH. Generally, R ¹ is a saturated or unsaturated primary or branched hydrocarbyl moiety, preferably R ¹ is a primary alkyl moiety. When x + y + z = 0, R ¹ is a hydrocarbyl moiety having a chain length of about 8 to about 18. When x + y + z is other than 0, R ¹ may be slightly longer,
It has a chain length in the C ₁₂ -C ₂₄ range. The general formula is x + y + z = 0, R ¹ =
_{C 8 -C 18, R '=} H and q = 0 to 2, preferably also encompasses amine oxides is 2. These amine oxides are incorporated herein by reference U
S Patents 5,075,501 and 5,071,594,
Examples are C _12-14 alkyldimethylamine oxide, hexadecyldimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrate.

[0077]   In the present invention, x + y + z is other than 0, in particular x + y + z is about 1 to about 10, and R ¹ A primary alkyl having from 8 to about 24 carbon atoms, preferably from about 12 to about 16 carbon atoms.
Also included are amine oxides, which are nucleoside groups; in these embodiments, y + z is preferably
Preferably, 0 and x are preferably from about 1 to about 6, more preferably from about 2 to about 4, and E
O represents ethyleneoxy, PO represents propyleneoxy, and BO represents butylene.
Noxy. Such amine oxides can be prepared, for example, by conventional synthetic methods.
Reaction of alkyl ethoxy sulphate with dimethylamine, then hydrogen peroxide
It can be prepared by oxidation of an ethoxylated amine with.

Highly preferred amine oxides here are solids at ambient temperature, more preferably they have a melting point in the range 30 to 90 ° C. Amine oxides suitable for use herein are commercially produced by several suppliers including Akzo Chemie, Ethyl Corp. and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternative amine oxide manufacturers. Preferred commercial amine oxides are solid dihydrate ADMOX 16, ADMOX 18, ADMOX 12, especially ADMOX 14 from Ethyl Corp.

Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris (ethyleneoxy) dimethylamine oxide, tetradecyldimethylamine oxide dihydrate. There are aquatic products and their mixtures. In one preferred embodiment, R '= H, but there is some latitude in that R'may be slightly larger than H. In particular, in the present invention, such as hexadecyl bis (2-hydroxyethyl) amine oxide, tallow bis (2-hydroxyethyl) amine oxide, stearyl bis (2-hydroxyethyl) amine oxide and oleyl bis (2-hydroxyethyl) amine oxide. And R ′ = CH ₂ OH.

Iv. Biodegradable Branched Surfactant In the present invention, at least one biodegradable branched and / or crystalline disintegration and / or
Or there is an important aspect comprising a medium chain branched surfactant or a mixture of surfactants. The term "biodegradable branching" and / or "crystalline disintegration" and / or "medium chain branching" (the acronym "MCB" is used below) refers to such surfactants or surfactants. The mixture is characterized by the presence of surfactant molecules with moderately non-linear hydrophobes, and more particularly, the surfactant hydrophobes are not completely linear and, on the other hand, have unacceptable biodegradability. It shows that it is not branched to the extent that it brings it. Preferred biodegradable branched surfactants, whether branched or unbranched, differ from the known types of commercially available LAS, ABS, Exxal, Lial and the like. The biodegradable branching material has a few branches at certain positions on the hydrophob, for example from about 1 to about 3 methyl and / or ethyl and / or propyl and / or butyl branches, which branches are: It is preferably present in the middle of the hydrophob, away from the surfactant head group. Typically,
One to three such branches are present in a single hydrophob, preferably only one. Such biodegradable branched surfactants may have exclusively linear aliphatic hydrophobes, or the hydrophobes may have cycloaliphatic or aromatic substitution. Highly preferred are the MCB analogs of conventional straight chain alkyl sulphates, straight chain alkyl poly (alkoxylates) and straight chain alkyl benzene sulphonates, the above mentioned surfactants being suitable for the medium chain C ₁ -C. _4- branched C ₈ -C ₁₈ alkyl sulphate, medium chain C ₁ -C ₄ branched C ₈ -C ₁₈ alkyl ethoxylated, propoxylated or butoxylated alcohol, medium chain C ₁ -C ₄ branched C ₈ -C ₁₈ alkylethoxy It is selected from sulphates, medium chain C ₁ -C ₄ branched C ₈ -C ₁₆ alkylbenzene sulphonates and mixtures thereof. When anionic, the surfactant is usually an acid or salt, such as sodium, potassium, ammonium or substituted ammonium forms. Biodegradable branched surfactants provide a substantial improvement in cleaning performance and / or usefulness in cold water and / or water hardness resistance and / or economy of use. Such surfactants generally belong to any known class of surfactants, such as anionic, nonionic, cationic or zwitterionic. Biodegradable branched surfactant is Pr
It is synthesized by the process of octer & Gamble, Shell and Sasol. These surfactants include WO98 / 23712A published on 06/04/98; WO97 / 38957A published on 10/23/97; WO97 / 38956A published on 10/23/97;
WO97 / 39091A published on October 23/97; WO published on October 23/97
97 / 39089A; 10/23/97 published WO 97 / 39088A; 10 /
23/97 published WO97 / 39087A1; 10/23/97 published WO97
/ 38972A; 06/04/98 published Shell's WO98 / 23566A; Sasol
Further details are disclosed in the following pending patent applications assigned to Procter & Gamble.

Preferred biodegradable branched surfactants here are more particularly MCB surfactants as disclosed in the following documents: WO98 / 23712A published 06/04/98 includes MCB of the following formula (1).
There are disclosures of MCB nonionic surfactants including primary alkyl polyoxyalkylenes: CH ₃ CH ₂ (CH ₂ ) _w C (R) H (CH ₂ ) _x C (R ¹ ) H (CH ₂ ) _y C (R ² ) H (CH ₂ ) _z (EO / PO) _m OH (1) Total number of carbon atoms in the branched primary alkyl moiety of this formula (including R, R ¹ and R ² branches, but EO / PO alkoxy moieties). Is preferably 14 to 20; and for this surfactant mixture, the average total number of carbon atoms in the MCB primary alkylhydrophobe moiety is preferably 14.5-17.5.
, More preferably 15-17; R, R ¹ and R ² are each independently selected from hydrogen and 1-3C alkyl, preferably methyl, provided that R, R ¹ and R ² are all hydrogen. And z is 1, at least R or R ¹ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is 0 to 13 Is an integer; z is an integer of at least 1; w + x + y + z is 8-14; EO / PO is preferably an alkoxy moiety selected from ethoxy, propoxy and mixed ethoxy / propoxy groups; m is at least With 1,
It is preferably 3 to 30, more preferably 5 to 20, and most preferably 5 to 15. Such MCB nonionic systems may additionally have a butylene oxide derived moiety and the -OH moiety may be replaced with any of the well known endcapping moieties used in conventional nonionic surfactants.

[0082]   In WO97 / 38957A published on October 23/97, Formula R-CH₂CH₂CH (Me) CH-R¹-CH₂OH (I) and   HOCH₂-R-CH₂CH₂-CH (Me) -R '(II) intermediate to nearly intermediate chain branching
There is a disclosure of alcohol, which has the formula (A) RCH = CH_TwoAnd R¹CH = CH _Two Of α-olefin of the formula R (CH₂)₂-C (R¹) = CH_TwoAnd R¹(
CH₂)₂-C (R) = CH₂(B) (i) different olefins
Activating and reacting them with carbon monoxide / hydrogen under oxo conditions, or (i
i) CO / H under oxo conditions with olefin from step (A)_TwoReact directly with
Get In the above formula, R, R¹= 3-7C straight chain alkyl. WO97 / 389
57A also has MCB alkyl sulphate obtained by sulfation of (i) (I) or (II)
Preparation of surfactant; (ii) ethoxylation followed by (I) or (II) sulphate
The production of MCB alkyl ethoxy sulphate comprising the following: (iii) (I) or (
II) or MCB alkylcapsules comprising oxidizing the aldehyde intermediates thereof
Production of ruboxylate surfactant; and (iv) branched alkyl carboxy as raw material
MCB acyl taurate, MCB acyl isethionate, MC using silate
B acyl sarcosinate or MCB acyl N-methylglucamide surfactant
Discloses manufacturing.

WO 97 / 38956A published 10/23/97 prepares a mixture of (a) carbon monoxide and hydrogen, and (b) this mixture in the presence of a catalyst under Fischer-Tropsch conditions. Disclosed is a process for producing a mixture of hydrocarbons containing the described olefins, and (c) separating the olefins from the mixture of hydrocarbons to produce an intermediate to near intermediate chain branched alpha-olefin. WO97 / 3
8956A is a description olefin by reaction with CO / H ₂ oxo conditions are further also disclosed intermediate and approximately intermediate chain branched alcohol process. These alcohols are (1)
Sulfate surfactant; (2) MCB alkyl ethoxy sulphate by ethoxylating and then sulphating an alcohol; or (3) Producing a branched alkyl carboxylate surfactant by oxidizing an alcohol or an aldehyde intermediate thereof. Can be used for The formed branched carboxylate can be used as a raw material for producing a branched acyl taurate, an acyl isethionate, an acyl sarcosinate or an acyl N-methylglucamide surfactant.

WO 97 / 39091A published Oct. 23/97 contains at least 0.
5 (especially 5, more especially 10, especially especially 20) wt% of long-chain alkyl of the formula (
There is a disclosure of a detergent surfactant composition comprising I) MCB surfactant. AX-
In B (I), A is (i) the longest C straight chain attached to the XB portion of the 8-21C atom; (ii) the 1-3C alkyl moiety branched from this longest straight chain; (iii) CH ₂ B
Having at least one branched alkyl moiety directly attached to the longest C straight chain C at a position within the 2C position, counting from the C1 to ω-2 carbons (terminal C-2C) attached to the moiety, 9-22 (especially 12-18) C MCB alkyl hydrophob; (iv) the surfactant composition comprises 14.5 to 17.5 (especially 15 to 17) C carbon atoms in the AX moiety. It has an average total content; B is preferably sulfate, sulfonate, polyoxyalkylene (especially polyoxyethylene or polyoxypropylene), alkoxylated sulfate, polyhydroxy moiety, phosphate ester, glycerol sulfonate, polygluconate. , Polyphosphate ester, phosphonate, sulfosuccinate, polyalkoxylated carboxylate, glucamide, Taurates, sarcosinates, glycinates, isethionates, mono / dialkanolamides, monoalkanolamide sulphates, diglycolamides and their sulphates, glyceryl esters and their sulphates, glycerol ethers and their sulphates, polyglycerol ethers and their sulphates, sorbitans Ester, polyalkoxylated sorbitan ester, ammonioalkane sulfonate, amidopropyl betaine, alkylated quaternary, alkylated / polyhydroxyalkylated (oxypropyl) quaternized, imidazolines, 2-ylsuccinate, sulfonated alkyl is hydrophilic (surfactant head group) moieties selected from esters and sulfonated fatty acids; X- is -CH ₂ Or -C (O) -. WO9
7 / 39091A also discloses laundry detergents or other cleaning compositions comprising (a) 0.001 to 99% of cleaning surfactant (I) and (b) 1 to 99.999% of additive components. .

WO 97 / 39089A published 10/23/97 describes (a) 0.1-50 (particularly 1-40) wt% of the intermediate of formula (I) as part of a surfactant system. Chain branching surfactant; (b) 0.1-50 wt% cosurfactant as the other part of the surfactant system; (c) 1-99.7 wt% solvent; and (d) 0.1-75 wt. There is a disclosure of a liquid cleaning composition comprising% additive ingredients. Formula (I) is A-CH ₂ -B
Where A is (i) the longest C straight chain attached to the XB portion of the 8-21C atom;
ii) 1-3C alkyl moiety branched from this longest straight chain; (iii) 2C position range counting from the 1st carbon bonded to the CH ₂ B moiety to the ω-2 carbon (terminal C-2C). A 9-22 (particularly 12-18) C MCB alkylhydrophob having at least one branched alkyl moiety directly attached to the longest C straight-chain C at an internal position; (iv) surfactant The agent composition is AX of 14.5-17.5 (especially 15-17)
It has an average total number of C carbons in the moiety; B is a hydrophilic moiety selected from sulfates, polyoxyalkylenes (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulfates.

[0086]   WO97 / 39088A published on Oct. 23/97 has the following formula (I)
Containing 0.001-100% of MCB primary alkylalkoxylated sulphate of
There are disclosures of surfactant compositions:     CH₃CH₂(CH)_wCHR (CH₂)_xCHR¹(CH₂)_yCHR²(CH₂)_zOSO₃M (I) In the above, R, R¹And R^TwoTotal number of C atoms in compound (1) including
Is preferably 14 to 20; the total number of C atoms in the branched alkyl moiety is preferably
The average is 14.5-17.5 (especially 15-17); R, R¹And R ^Two Is selected from H and 1-3C alkyl (especially Me), provided that R, R¹Oh
And R^TwoAre not all H; at least R or R when z = 1¹Is
Not H; M is Na, K, Ca, Mg, formula N⁺R^ThreeR^FourR⁵R⁶(II) Class A
Is a cation particularly selected from rukylammonium; M is especially Na and / or
Or K; R^Three, R^Four, R⁵, R⁶Is H, 1-22C alkylene, 4-2
2C branched alkylene, 1-6C alkanol, 1-22C alkenylene and /
Or selected from 4-22C branched alkenylene; x, y, z = 0-13; z
Is at least 1; w + x + y + z = 8-14. In WO97 / 39088A
, (1) consisting of a mixture of branched primary alkyl sulphates of formula (I) as described above.
Surfactant composition (M is a water-soluble cation; R^TwoIs 1-3C alkyl
The ratio of surfactants with z = 1 to surfactants with z = 2 or more is preferably low.
At least 1: 1 (especially 1: 100); (2) (a) the following formula (III)
And / or (IV) MCB primary alkylalkoxylated sulphate 0.00
1-99%:     CH₃(CH₂)_aCH (CH₃) (CH₂)_bCH₂OSO₃M (III)     CH₃(CH₂)_dCH (CH₃) (CH₂)_eCH (CH₃) CH₂OSO₃M (IV) (In the above, a, b, d and e are integers, preferably a + b = 10
16, d + e = 8 to 14; when a + b = 10, a = 2 to 9 and b = 1 to 8;
When a + b = 11, a = 2 to 10 and b = 1 to 9; when a + b = 12, a
= 2-11 and b = 1-10; when a + b = 13, a = 2-12 and b =
1 to 11; when a + b = 14, a = 2 to 13 and b = 1 to 12; a + b = 1
A = 2 to 14 and b = 1 to 13 when 5; a = 2-1 when a + b = 16
4 and b = 1 to 14; d + e = 8, d = 2 to 7 and e = 1 to 6; d +
When e = 9, d = 2 to 8 and e = 1 to 7; when d + e = 10, d = 2 to 9
And e = 1 to 8; when d + e = 11, d = 2 to 10 and e = 1 to 9; d +
When e = 12, d = 2 to 11 and e = 1 to 10; when d + e = 13, d =
2-12 and e = 1-11; when d + e = 14, d = 2-13 and e = 1
To 12) and (b) a detergent additive of 1 to 99.99 wt%; (3)
) Intermediate-chain branched primary alkyl sulphate surfactant of the following formula (V): CH₃CH₂(CH₂)_xCHR¹(CH₂)_yCHR²(CH₂)_zOSO₃M (V) (In the above, x, y = 0 to 12; z is at least 2; x + y + z = 11
~ 14; R¹And R^TwoAre not both H; R¹Or R^TwoOut of
X + y + z is not 12 or 13 when one is H and the other is Me; R ¹ Is H and R^TwoIs Me, and if z = 3, then x + y is not 11, but z
= 5, x + y is not 9); (4) a and b are integers, and a = b = 1
2 or 13, a = 2-11, b = 1-10 and M is Na, K and, where
An alkylsulfate of formula (III) which is a more substituted ammonium; (5)
d and e are integers, d = e = 10 or 11, and when d = e = 10, d =
2-9 and e = 1-8, and when d = e = 11, d = 2-10 and e = 1
~ 9 and M is Na, K, optionally substituted ammonium (especially Na)
An alkyl sulfate of formula (IV); (6) 3-, 4-, 5-, 6-, 7-,
8-, 9-, 10-, 11-, 12- or 13-methylpentadecanol monkey
Fate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12
-, 13- or 14-methylhexadecanol sulfate; 2,3-, 2,
4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,
11-, 2,12-Methyltetradecanol sulfate; 2,3-, 2,4-
, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11
-, 2,12- or 2,13-methylpentadecanol sulfate and / or
Or a methyl-branched primary alkyl sulphate selected from mixtures of these compounds
Also disclosed.

WO 97 / 39087A published 10/23/97 discloses a surfactant composition comprising 0.001 to 100% of mid-chain branched primary alkylalkoxylated sulphate of formula (I). , Where the total number of C atoms in compound (I) (
R, R ¹ and R ³ are included but not the C atoms of the EO / PO alkoxy moiety) are 14 to 20; the total number of C atoms in the branched alkyl moiety is 14.
5 to 17.5 (especially 15 to 17); R, R ¹ and R ² are H or 1-3
C alkyl (especially Me) and R, R ¹ and R ² are not all H; when z = 1, at least R or R ¹ is not H; M is Na, K, Ca,
Mg, a cation especially selected from the quaternary alkylamines of formula (II) (M is especially Na and / or K); R ³ , R ⁴ , R ⁵ , R ⁶ = H, 1-22C alkylene 4-22C branched alkylene, 1-6C alkanol, 1-22C alkenylene and / or 4-22C branched alkenylene; w, x, y = 0 to 13;
z is at least 1; w + x + y + z = 8-14; EO / PO is an alkoxy moiety, in particular ethoxy and / or propoxy; m is at least 0.01, in particular 0.1-30, even more particularly 0. 5-10, especially 1-5. (1)
A surfactant composition consisting of a mixture of branched primary alkylalkoxylated sulphates of formula (I) (R ² = 1-3C alkyl; the ratio of surfactants of z = 2 or higher to surfactants of z = 1 is small. 1: 1, especially 1.5: 1, especially 3: 1 and especially 4: 1); (2) (a) intermediate chain branched primary alkyl of formula (III) and / or (IV) Alkoxylated sulphate 0.001-99% (M is as described above; a, b, d and e are integers, a + b = 10-16, d + e =
8 to 14; a + b = 10, a = 2 to 9 and b = 1 to 8; a + b = 11, a = 2 to 10 and b = 1 to 9; a + b = 12, a = 2 to 11 and b = 1 to 10; a + b = 13, a = 2 to 12 and b = 1 to 11; a +
When b = 14, a = 2 to 13 and b = 1 to 12; when a + b = 15, a =
2-14 and b = 1-13; when a + b = 16, a = 2-14 and b = 1
˜14; when d + e = 8, d = 2 to 7 and e = 1 to 6; when d + e = 9,
d = 2-8 and e = 1-7; when d + e = 10, d = 2-9 and e = 1-
8; d + e = 11, d = 2-10 and e = 1-9; d + e = 12, d = 2-11 and e = 1-10; d + e = 13, d = 2-12 and e = 1 to 11; d + e = 14, d = 2 to 13 and e = 1 to 12), and (b) a detergent composition comprising 1 to 99.99 wt% of detergent additive; (3) Formula (V) MC
B primary alkyl alkoxylated sulphate surfactant (R ¹ , R ² , M, EO
/ PO, m are as described above; x, y = 0-12; z is at least 2;
x + y + z = 11 to 14); (4) Intermediate chain branched alkylalkoxylated sulfate of the formula (III) (a = 2 to 11, b = 1 to 10; a + b = 12 or 13; M,
EO / PO and m are as described above); (5) Intermediate chain branched alkylalkoxylated sulphate of formula (IV) (d + e = 10 or 11; when d + e = 10, d = 2-9 and e = 1- 8 and when d + e = 11, d = 2 to 10 and e
= 1-9; M is as described above (especially Na); EO / PO and m are as described above); and (6) 3-, 4-, 5-, 6-, 7- , 8-, 9
-, 10-, 11-, 12- or 13-methylpentadecanol ethoxylated sulfate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-,
12-, 13- or 14-methylhexadecanol ethoxylated sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9- ,
2,10-, 2,11-, 2,12-Methyltetradecanol ethoxylated sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8 -2
Also disclosed are methyl-branched primary alkyl ethoxylated sulphates selected from, 9,9-, 2,10-, 2,11-, 2,12- or 2,13-methylpentadecanol ethoxylated sulphates and / or mixtures of these compounds. Has been done.
The compounds are ethoxylated with an average degree of ethoxylation of 0.1-10.

[0088]   In WO97 / 38972A published on October 23/97, (a) is preferable.
The average carbon chain length of at least 14.5-17.5 in the Kuha flow film reactor.
A long-chain fatty alcohol mixture with_ThreeSulfate with (alcohol
The mixture is at least 10%, preferably at least 25%, more preferably at least
50%, even more preferably at least 75%, most preferably at least 95%
Contains an MCB fatty alcohol having formula (I); wherein R, R¹, R ^Two = H or 1-3C alkyl, preferably methyl, provided that R, R¹And R^TwoBut
Not all H; at least R or R when z = 1¹Is not H
X, y, z = integer 0 to 13; z = integer of at least 1; w + x + y + z = 8 to 1
4; R, R¹And R^TwoIn the branched primary alkyl moiety of formula (1) including branching
The total number of carbon atoms is 14 to 20; further for alcohol mixtures, formula (1)
The average total number of carbon atoms in the branched primary alkyl moiety having is> 14.5-17
． 5, preferably> 15-17); and (b) preferably KOH, Na
OH, ammonia, monoethanolamine, triethanolamine and these
With a base selected from a mixture of
A long-chain alkyl sulphate surfactant mixture consisting of neutralizing the sulphate acid.
There is a disclosure of a method for making a compound composition. Specific long chain aliphatic alco
The mixture of the polyols is alkoxylated and the resulting polyoxyalkylene alcohol is converted to S
O_ThreeSulfate with and neutralize the resulting alkylalkoxylate acid
Of a long-chain alkylalkoxylated sulphate surfactant mixture composition comprising
Manufacturing methods are also disclosed. On the other hand, the alkyl alkoxylated sulfate is
O_ThreeSulfate with and neutralize to give polyoxyalkylene alcohol.
It may be manufactured directly from the resin.

In WO98 / 23566A of Shell published with 06/04/98, 8-
Disclosed are branched primary alcohol compositions having 36 C atoms, an average number of branches of 0.7 to 3 per mole, ethyl and methyl branches. (1) A branched primary alkoxylate composition that can be produced by reacting a branched primary alcohol composition as described above with an oxirane compound; (2) A branched primary alkoxy compound that can be produced by sulfating the primary alcohol composition as described above. (3) A branched alkoxylated primary alcohol sulfate that can be produced by alkoxylating and sulphating a branched alcohol composition as described above; (4) Produced by oxidizing a branched primary alcohol composition as described above Uru-branched primary alcohol carboxylate; (5) (
a) a surfactant selected from branched primary alcohol alkoxylates such as (1), branched primary alcohol sulfates like (2) and branched alkoxylated primary alcohol sulfates like (3), (b) builders and Also disclosed is (c) a detergent composition optionally comprising an additive selected from foam regulators, enzymes, bleaches, bleach activators, optical brighteners, cobuilders, hydrotropes and stabilizers. The primary alcohol compositions and the sulfates, alkoxylates, alkoxysulfates and carboxylates produced therefrom show good cold water washability and biodegradability.

Biodegradable branched surfactants useful herein also include modified alkyl aromatic, especially modified alkyl benzene sulfonate surfactants described in co-pending, commonly assigned patent applications (P & G Case Nos. 7303P, 7304P). . More specifically, these surfactants include those of the formula (B-Ar- at about 10 to about 100% by weight of the surfactant system).
D) Two or more crystalline collapsed alkylaryl sulfonate surfactants of _a (M ^{q +} ) _b (D is SO ₃ ⁻ ; M is a cation or mixture of cations; q is the valence of the cations; a and b are numbers selected such that the composition is electrically neutral; Ar is selected from benzene, toluene and combinations thereof; B is at least one having from 5 to 20 carbon atoms (P & G Case 6766P) Alkylaryl comprising a primary hydrocarbyl moiety and an assembly of one or more crystalline disintegration moieties, wherein the crystalline disintegration moiety is mediated by or branched from the above hydrocarbyl moiety. There is a sulfonate surfactant system, and the alkylaryl sulfonate surfactant system has a sodium critical solution temperature measured by CST test. It has crystal-disintegrating properties at a temperature of about 40 ° C. or lower, and the above alkylaryl sulfonate surfactant system has at least one of the following properties: tetrapropylene benzene sulfonate as measured by the modified SCAS test. A biodegradation rate of greater than 1 and a weight ratio of non-quaternary to quaternary carbon atoms in B of at least about 5: 1.

Such compositions may comprise (a) about 60 to about 95% by weight (preferably about 65 to about 9).
0%, more preferably about 70 to about 85%) of a mixture of branched alkylbenzene sulfonates having the formula (I):

[Chemical 7] [In the above formula, L is an acyclic group consisting of carbon and hydrogen having two methyl ends.
An aliphatic moiety; the above mixture of branched alkyl benzene sulfonates has the formula
Two or more (preferably at least three) different molecular weights of the anions of (I),
Depending on the above) the above compounds are contained; branched alkylbenzene sulphone
The above mixture of salts comprises from about 10.0 to about 14.0 carbon atoms (preferably about 11.0 carbon atoms).
To about 13.0, more preferably about 11.5 to about 12.5) average carbon content.
The average carbon content is R¹, L and R^TwoBased on the sum of carbon atoms in
(Preferably R¹, L and R^TwoThe total number of carbon atoms in is 9 to 15
, More preferably 10 to 14); L is A, R¹And R^TwoSubstituents other than
Does not have; M has a valence of q (typically 1-2, preferably 1) (preferably
Selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably
Selected from H, Na, K and mixtures thereof, and even more preferably H,
A cation or a mixture of cations (selected from Na and mixtures thereof)
A and b are integers selected such that the above compounds are electrically neutral
(A is typically 1 or 2, preferably 1, and b is 1); R¹Is C ₁ -C_ThreeAlkyl (preferably C₁-C_TwoAlkyl, more preferably methyl)
Yes; R^TwoIs H and C₁-C_ThreeSelected from alkyl (preferably H and
C₁-C_TwoAlkyl, more preferably H and methyl, more preferably H and
Methyl; provided with the above branched alkylbenzene sulfonate R^TwoAt least about 0.5,
More preferably 0.7, more preferably 0.9 to 1.0 mole fraction is H
A) is a benzene moiety (typically A is a moiety-C)₆H_Four-And
SO of formula (I)_ThreeThe part is in the para position with respect to the L part, but some ratio, usually about 5
SO or less by weight, preferably 0-5%_ThreePart is ortho to L))
And (b) about 5 to about 60% by weight (preferably about 10 to about 35%, more preferably
Or about 15 to about 30%) of unbranched alkylbenzene sulphone having the following formula (II)
Mixtures of sheets:

[Chemical 8] [Where a, b, M, A and q are as described above; Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl ends; Y is about 10.0 to about 14.0 (preferably about 11.0 to about 13.0, more preferably 1
The above mixture of unbranched alkylbenzene sulfonates having an average carbon content of 1.5 to 12.5 carbon atoms) is preferably 9 to 15 carbon atoms in Y,
More preferably further characterized by 10 to 14))) is included (preferably consisting essentially of).
0 to about 10,000 (preferably about 400 to about 1200, more preferably about 50)
Further characterized by a 2 / 3-phenyl index of 0 to about 700) (and preferably the surfactant mixture is less than about 0.3, preferably less than about 0.2, more preferably about 0.1. Less than, and even more preferably has a 2-methyl-2-phenyl index of 0-0.05).

[0092]   Alkylbenzene-derived type intermediate chain branched surfactant
Alkylation with the killing mixture, sulfonation of the product of (I) and conversion of the product of (II)
A surfactant mixture consisting of the product of a process consisting of neutralizing steps is also conceivable.
The above alkylation mixture comprises (a) about 1 to about 99.9% by weight of branched C.₇-C ₂₀ Mono-olefin (the branched mono-olefin is represented by the formula R¹LR^TwoBranched paraffin
Has a structure consistent with the case of branched monoolefins formed by dehydrogenation of
Where L is an acyclic group consisting of carbon and hydrogen with two terminal methyls.
Formula is an aliphatic moiety; R¹Is C₁-C_ThreeIs alkyl; R^TwoIs H and C₁-
C_ThreeSelected from alkyl); and (b) from about 0.1 to about 85% by weight C.₇-
C₂₀Linear aliphatic olefins (the above-mentioned alkylation mixture is the above-mentioned C₇-C₂₀Example
Above branched C having at least two different carbon numbers₇-C₂₀Mono olfi
It has an average carbon content of about 9.5 to about 14.5 carbon atoms).
The components (a) and (b) are in a weight ratio of at least about 15:85.
is there.

[0093] v. Amphoteric surfactants- Amphoteric surfactants may also be included in the detergent composition. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic groups may be straight chain or It may be a branched chain. One of the aliphatic substituents has at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one is an anionic water-soluble group such as carboxy, sulfonic acid, sulfuric acid. Has a group. For examples of amphoteric surfactants, see Laughlin et al., U., published Dec. 30, 1975.
See S Patent 3,929,678 at column 19, lines 18-35. Preferred amphoterics include C ₁₂ -C ₁₈ alkyl ethoxylates (“AE”), including so-called narrow peak alkyl ethoxylates, C ₆ -C ₁₂ alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ( _{"sultaines"),} there is a C 10 _{-C 18} amine oxides, and mixtures thereof.

Vi. Polyhydroxy fatty acid amide surfactant- The detergent composition may also contain a polyhydroxy fatty acid amide surfactant. The polyhydroxy fatty acid amide surfactant component consists of compounds of the following structural formulas:

[Chemical 9] In the above formula: R¹Is H, C₁-C_FourHydrocarbyl, 2-hydroxyethyl, 2-
Hydroxypropyl or mixtures thereof, preferably C₁-C_FourAlkyl, further
Is preferably C₁Or C_TwoAlkyl, most preferably C₁Alkyl (i.e.
Chill); R^TwoIs C₅-C₃₁Hydrocarbyl, preferably linear C₇-C_{1 9} Alkyl or alkenyl, more preferably straight chain C₉-C₁₇Alkyl or
Alkenyl, most preferably straight chain C₁₁-C₁₅Alkyl or alkenyl,
Or a mixture thereof; Z is a linear hydrocarbyl chain and a direct bond to the chain.
Having at least three hydroxyl groups
, Or its alkoxylated (ethoxylated or propoxylated) derivatives
is there. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably
Z is glycityl. Suitable reducing sugars include glucose, fructose, malt
There are glucose, lactose, galactose, mannose and xylose. Raw materials and
In addition to the individual sugars mentioned above, high dextrose corn syrup and high flour
Lactose corn syrup and high maltose corn syrup are also available. This
These corn syrups produce a mix of sugar components for Z. Other suitable ingredients
It should be understood that does not mean to exclude. Z is preferably -CH _Two -(CHOH)_n-CH_TwoOH, -CH (CH_TwoOH)-(CHOH)_n-1-
CH_TwoOH, -CH_Two-(CHOH)_Two(CHOR ') (CHOH) -CH_TwoO
Selected from the group consisting of H and their alkoxylated derivatives, where n is 3
Is an integer of ˜5 and R ′ is H or a cyclic or aliphatic monosaccharide. n is 4
Glycytyl, especially -CH_Two-(CHOH)_Four-CH_TwoOH is most preferred.

R ¹ is, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R ² —CO—N <includes, for example, cocamide, stearamide, oleamide, lauramide, myristoamide, capricamide, palmitoamide, tallowamide and the like. Z is 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymultityl, 1-deoxylactytyl, 1-deoxygalactyl, 1-deoxymannityl, 1-deoxymaltotriotyl, etc. There is.

Methods of making polyhydroxy fatty acid amides are known in the art. Typically,
They react alkylamines with reducing sugars in a reductive amination reaction to give the corresponding N-
The alkyl polyhydroxyamine is formed, followed by N / N in the condensation / amidation step.
-Prepared by reacting an alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride to form an N-alkyl, N-polyhydroxy fatty acid amide product. A method for producing a composition containing a polyhydroxy fatty acid amide is described in, for example, Thomas Hedley & Co., Ltd. published on February 18, 1959.
GB Patent Specification 809,060, ER, issued December 20, 1960
Wilson US Patent 2,965,576, Anth, issued March 8, 1955
ony M. Schwartz, US Patent 2,703,798 and Piggott, US Patent 1,985,424, issued December 25, 1934, each of which is incorporated herein by reference.

[0097]   vii. Cationic surfactant-A cationic detersive solution suitable for use in the composition of the invention.
Surfactants are those that have one long chain hydrocarbyl group. Such a tick
Examples of on-type surfactants include ammonium surfactants such as alkyl trimethyl.
There are lumonium halogenides, and surfactants having the formula:   [R²(OR³)_y] [R^Four(OR³)_y]₂R^FiveN⁺X^- R in the above formula^TwoIs an alkyl having from about 8 to about 18 carbon atoms in the alkyl chain or
An alkylbenzyl group; each R^ThreeIs -CH_TwoCH_Two‐ 、 ‐ CH_TwoCH (CH_Three )-,-CH_TwoCH (CH_TwoOH)-,-CH_TwoCH_TwoCH_Two-And those
Selected from the group consisting of mixtures; each R^FourIs C₁-C_FourAlkyl, C₁-C_FourHi
Droxyalkyl, two R^FourA benzyl ring structure formed by linking groups, -C
H_TwoCHOH-CHOCOR⁶CHOHCH_TwoOH (R⁶Is less than about 1000
A hexose or hexose polymer having a molecular weight), and y is 0
When not present, selected from the group consisting of hydrogen; R⁵Is R^FourSimilar to or R ^Two + R⁵Is an alkyl chain having a total number of carbon atoms of about 18 or less; each y is 0 to about
10, the sum of y values is 0 to about 15; X is any compatible anio.
It is

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds useful in the composition having the formula (i): R ₁ R ₂ R ₃ R ₄ N ⁺ X ^-the above formula. Wherein R ₁ is C ₈ -C ₁₆ alkyl and each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and-
A _{(C 2 H 40) x H} (x has a value of 2 to 5), X is an anion.
No more than 1 of R ₂ , R ₃ or R ₄ must be benzyl. The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthetically derived by olefin build-up or oxoalcohol synthesis. To be done. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X is selected from halide, methosulfate, acetic acid and phosphate ions.

Examples of quaternary ammonium compounds of formula (i) suitable for use herein include coconut trimethylammonium chloride or bromide, coconut methyldihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride, decyldimethylhydroxyethylammonium chloride. Or bromide,
C _12-15 dimethylhydroxyethylammonium chloride or bromide, coconut dimethylhydroxyethylammonium chloride or bromide, myristyltrimethylammonium methylsulfate, lauryldimethylbenzylammonium chloride or bromide, lauryldimethyl (ethenoxy) ₄ ammonium chloride or bromide, choline ester (R ₁ is _CH 2 _-CH 2 -O-C
(= O) -C _12-14 alkyl and R ₂ , R ₃ and R ₄ are methyl, a formula (i
A compound)) and a dialkylimidazoline [(i)], but are not limited thereto.

Other cationic surfactants useful herein are Cambre, US Pat. No. 4,228,044 and European Patent Application EP000,2, issued Oct. 14, 1980.
24 is also described. When included herein, the compositions of the invention will typically contain about 0.2% by weight, preferably about 1% to about 25%, preferably about 8% of such cationic surfactants. .

Viii. Dipolar Surfactants- Dipolar surfactants are also suitable for use in the compositions of the present invention, examples of which are described in US Pat. No. 3,929,678. When included herein, the compositions of the invention will typically contain about 0.2% by weight, preferably about 1% to about 15%, preferably about 10% of such zwitterionic surfactants.

Ix. Diamine Surfactants-A particularly preferred class of surfactants for use in the liquid dishwashing compositions of the present invention are diamines. Preferably, the diamines, when present, are present in the composition at a level such that the anionic surfactant to diamine ratio present is from about 40: 1 to about 2: 1. Diamines enhance the removal of fats and fat-like foods while maintaining adequate frothing levels.

[0103]   Suitable diamines for use in the compositions of the present invention have the formula:

[Chemical 10] Each R in the above formula²⁰Independently hydrogen, C₁-C_FourLinear or branched alkyl, the following formula
Selected from the group consisting of alkyleneoxy having:                   ‐ (R^{twenty one}O)_yR^{twenty two} R in the above formula²¹Is C_Two-C_FourLinear or branched alkyl and mixtures thereof
R;²²Is hydrogen, C₁-C_FourAlkyl and mixtures thereof; y is 1 to
Is about 10; X is a unit selected from:   i) C_Three-C₁₀Straight chain alkylene, C_Three-C₁₀Branched alkylene, C_Three-C_{1 0} Cyclic alkylene, C_Three-C₁₀Branched alkylene, alkyle having the formula:
Oxyalkylene:                   ‐ (R^{twenty one}O)_yR^{twenty one}- R in the above formula²¹And y are as defined above;   ii) C_Three-C₁₀Straight chain, C_Three-C₁₀Branched straight chain, C_Three-C₁₀Cyclic, C_Three-C ₁₀ Branched cyclic alkylene, C₆-C₁₀Arylene (The above unit is the above diamine
Including one or more electron-donating or electron-withdrawing moieties that adjust the pKa of about 8 or more.
); And   iii) a mixture of (i) and (ii); However, the amine has a pKa of at least about 8.

Preferred diamines of the present invention are in the range of about 8 to about 11.5, preferably about 8
． 4 to about 11, more preferably each in the range of about 8.6 to about 10.75, p
It has K ₁ and pK ₂ . For purposes of the present invention, the term "pKa" refers to the terms "pK ₁ " and "pK ₂ " separately or inclusively. As used herein, the term pKa is used throughout the specification as it is used by those skilled in the art. The pKa value is a standard document, for example, "Critical Stability Constants: Volume 2, Amines" by Smith and Mar.
Easily available from tel, Plenum Press, NY and London, 1975.

As applied herein, the pKa value of diamines is about 0.
Specified by measuring with an aqueous solution having an ionic strength of 1 to about 0.5M. Since the pKa used here is an equilibrium constant that depends on temperature and ionic strength, the values reported in the literature without being measured by the above method may not completely match the values and ranges according to the present invention. . To eliminate ambiguity, relevant conditions and / or references used for the pKa of the present invention can be found here or in the "Critical Stability Cons."
tants: Volume 2, Amines ". One typical measurement method is potentiometric titration of acid with sodium hydroxide and" The Chemist's Ready Ref.
erence Handbook "by Shugar and Dean, McGraw Hill, NY, 1990, pKa determination by a suitable method as described and cited.

Preferred diamines in terms of performance and supply are 1,3-bis (methylamino) cyclohexane and 1,3-diaminopropane (pK ₁ = 10.5; pK ₂ =
8.8), 1,6-diaminohexane (pK ₁ = 11; pK ₂ = 10), 1,3
-Diaminopentane (Dytek EP) (pK ₁ = 10.5; pK ₂ = 8.9) 2-Methyl-1,5-diaminopentane (Dytek A) (pK ₁ = 11.2; pK ₂ = 1)
0.0). Other preferred materials are the primary / primary diamines with alkylene spacers C ₄ -C _8. In general, primary diamines are preferred over secondary and tertiary diamines.

[0107]   The following are non-limiting examples of diamines suitable for use in the present invention. 1-N, N-dimethylamino-3-aminopropane having the formula:

[Chemical 11] 1,6-diaminohexane having the formula:

[Chemical 12] 1,3-diaminopropane having the formula:

[Chemical 13] 2-Methyl-1,5-diaminopentane having the formula:

[Chemical 14] 1,3-diaminopentane having the formula below, marketed under the trade name Dytec EP:

[Chemical 15] 1,3-diaminobutane having the formula:

[Chemical 16] A diamine having an alkyleneoxy backbone, having the formula: Jeffamine EDR148:

[Chemical 17] 3-Methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophoronediamine) having the formula:

[Chemical 18] 1,3-bis (methylamino) cyclohexane having the formula:

[Chemical 19]

Suspending Agent The compositions of the present invention may, and preferably do, include a suspending agent. The suspension is
An ingredient specifically added to the compositions of the present invention to suspend the particulate solids component of the composition.

Suitable suspending agents are known in the art. Examples of suspending agents are gum type polymers (eg xanthan gum), polyvinyl alcohol and its derivatives, cellulose and its derivatives, and polycarboxylate polymers such as, but not limited to, tamarind gum (preferably xyloglucan). Polymers), guar gum, locust bean gum (preferably galactomannan polymers) and other industrial gums, and polymers such as, but not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seeds. , Quince seeds, xanthan, gellan, welan, rhamsan, dextran, curdlan, pullulan, scleroglucan, sizofiran, chitin, hydroxyalkyl cellulose, arabinan (preferably derived from sugar beet), debranched arabinan (preferably Sugar beet), arabinoxylan (preferably rye and wheat flour), galactan (preferably rubinus and potato), pectingalactan (preferably potato), galactomannan (preferably carob, both low and high viscosity products) , Glucomannan, lichenan (preferably derived from Iceland moss), mannan (preferably derived from elephant palm), pakiman,
Rhamnogalacturonan, gum arabic, agar, alginate, carrageenan, chitosan, clavane, hyaluronic acid, heparin, inulin, cellodextrin, carboxymethylcellulose (CMC), dextran, dextrin, ethylhydroxyethylcellulose (EHEC), guar, hydroxyethylcellulose. (
HEC), hydroxypropyl cellulose (HPC), hydroxybutyl cellulose (HBC), karaya, larch, methyl cellulose (MC), tamarind,
Scleroglucan, xanthan, carboxymethyl hydroxyethyl cellulose (CMHEC), methoxypropyl methyl cellulose (MPMC), hexyl carboxymethyl cellulose, C ₁₂ -C ₂₀ alkyl carboxymethyl cellulose, methyl hydroxyethyl cellulose (MHEC), methyl hydroxypropyl cellulose (MHPC), hydroxy Ethyl methyl cellulose (HEMC),
There are hydroxypropyl methylcellulose (HPMC), hydroxybutyl methylcellulose (HBMC) and mixtures thereof.

In a particularly preferred embodiment of the present invention the suspending agent is selected from gum type polymers or polycarboxylate polymers. Gum-type polymers include polysaccharide hydrocolloids, xanthan gum, guar gum,
It is selected from the group consisting of succinoglucan gum, cellulose, derivatives of any of these and mixtures thereof. In a preferred aspect of the invention, the gum type polymer is xanthan gum or its derivatives. The gum-type polymer, when present, is preferably present at levels of 0.01-10%, most preferably 0.1-3%.

Polycarboxylate polymers are homo or copolymers of monomer units selected from acrylic acid, methacrylic acid, maleic acid, malic acid, maleic anhydride. A preferred polycarboxylate polymer is Carbopol from BF Goodrich
Is. Suitable polymers have molecular weights in the range 10,000 to 100,000,000, most preferably 1,000,000 to 10,000,000. The crosslinked polycarboxylate polymer, when present, is preferably from 0.01 to
It is present at a level of 2%, more preferably 0.01-1%, most preferably 0.1-0.8%.

In another embodiment, the suspending agent consists of a combination of at least two polymers. In this embodiment, the first polymer is a gum type polymer and the second is a crosslinked polycarboxylate polymer. The composition may also include other polymers. The ratio of gum type polymer to crosslinked polycarboxylate polymer is 100: 1.
˜1: 100, most preferably 1:10 to 10: 1.

Optional Cleaning Additives The aqueous liquid detergent compositions of the present invention as described above, in addition to one or more of the particulate solids, polymer stabilizing system, and preferably the preferred cleaning additives described above, Optionally containing one or more optional cleaning additives of

Bleaching System The aqueous liquid detergent compositions of the present invention may include a bleaching system in addition to the preformed peracid compound described above. Bleaching systems typically comprise a "bleaching agent" (hydrogen peroxide source) and an "initiator" or "catalyst". Bleach, when present, is typically at a level of about 1% by weight of the composition, preferably about 5% to about 30%, preferably about 20%. The amount of bleach activator, if present, is typically about 0.1% by weight of the bleaching composition consisting of bleach + bleach activator, preferably about 0.
5% to about 60%, preferably about 40%.

Bleach- Hydrogen Peroxide Source is Incorporated Here Kirk Othmer's Encyclopedia of
Chemical Technology, 4th Ed. (1992, John Wiley & Sons), Vol.4, pp.271-300 "Bl
There are various forms of sodium perborate and sodium percarbonate, including various coatings and modified forms, as described in detail in "eaching Agents (Survey)".

The preferred hydrogen peroxide source used herein may be any convenient source, including hydrogen peroxide itself. For example, perborate, such as sodium perborate (any hydrate, but preferably mono or tetrahydrate), sodium carbonate peroxyhydrate or the corresponding percarbonate salt, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or peroxide. Sodium can be used here. Persulfate Bleach (eg DuPont
Effective oxygen sources such as OXONE) are also useful. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Any convenient mixture of hydrogen peroxide sources may be used.

A preferred percarbonate bleach consists of dry particles having a mean particle size in the range of about 500 to about 1000 μm, with less than about 10% by weight of the particles being less than about 200 μm, and less than about 10% by weight of the particles being about 10% by weight. It is larger than 1250 μm. Optionally, the percarbonate may be coated with silicates, borates or water-soluble surfactants. Percarbonates are commercially available from various sources such as FMC, Solvay and Tokai Denka.

The compositions of the present invention may also include chlorine-type bleaching agents as bleaching agents. Such agents are well known in the art and include, for example, sodium dichloroisocyanurate ("Na
DCC "). However, chlorine-type bleaching is less preferred in enzyme-containing compositions.

(A) Bleach Activator- Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present at a level of about 0.01% by weight of the composition, preferably about 0.5%, more preferably about 1% to about 15%, preferably about 10%, more preferably about 8%. . A preferred activator is tetraacetylethylenediamine (TAED)
, Benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C _{1). 0-} OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C ₈ -OBS), perhydrolysable esters and mixtures thereof, most preferably selected from the group consisting of benzoylcaprolactam and benzoylvalerolactam. . Particularly preferred bleach activators in the pH range of about 8 to about 9.5 are selected from those having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include nonanoyloxybenzene sulfonate (NOBS), 4- [N- (nonanoyl) aminohexanoyloxy]
Benzenesulfonate sodium salt (NACA-OBS) (example is US Patent 5
, 523, 434), lauroyloxybenzenesulfonate (LOBS or C ₁₂ -OBS), 10-undecenoyloxybenzenesulfonate (unsaturated UDOBS or C ₁₁ -OBS at the 10-position) and decanoyloxy. There is, but is not limited to, benzoic acid (DOBA).

A preferred bleach activator was issued December 16, 1997.
Christie et al., US 5,698,504, Ch, published December 9, 1997.
ristie et al., US 5,695,679, Wi, issued November 11, 1997
Lley et al., US Pat. No. 5,686,401, Hart issued Nov. 11, 1997.
Wille Shorn et al., US 5,686,014, published April 11, 1995.
y et al US 5,405,412, Willey et al US 5,405,413 issued April 11, 1995, Mitchel et al US 5,130,045 and July 1983 issued July 14,1992. Chung et al., US 4,412,934, and co-pending patent application USSN 08 / 709,07, issued January 1,
2, 08 / 064,564, all of which are incorporated herein by reference.

The molar ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention is usually at least 1: 1, preferably about 20: 1, more preferably about 10: 1 to about 1: 1. It is preferably in the range of about 3: 1.

Quaternary substituted bleach activators may also be included. The bleaching composition is preferably a quaternary substituted bleach activator (QSBA) or quaternary substituted peracid (QSP).
), And more preferably the former. The preferred QSBA structure is 1997 1
Willey et al., US 5,686,015 issued Jan. 11, Taylor et al., US 5,654,421 issued Aug. 5, 1997, Oct. 24, 1995.
US Pat. No. 5,460,747, Gosselink et al., Issued December 1, 1996.
US Pat. No. 5,584,888 to Miracle et al.
It is further described in US Pat. No. 5,578,136 issued to Taylor et al., Dated March 26, all of which are incorporated herein by reference.

Highly preferred breach activators useful herein are US 5,698,504, US 5,695,679 and US 5,686, each of which are cited above.
Amide substituted as described in 014. Preferred examples of such bleach activators include (6-octanamidocaproyl) oxybenzene sulfonate, (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate and their There is a mixture.

US Pat. No. 5,698,504, US Pat. No. 5,695,679, each cited above,
Hodge, US 5,686,014, and October 30, 1990
Other useful activators disclosed in US Pat.
There are benzoxazine-type activators such as the C ₆ H ₄ ring fused with the moiety —C (O) OC (R ¹ ) ═N— at the 1,2-position.

Depending on the activator and the application itself, good bleaching results of about 6 to about 13,
It is preferably obtained from a bleaching system having an in-use pH of about 9.0 to about 10.5. Typically, for example, activators with electron withdrawing moieties are used in the near neutral or near neutral pH range. Alkali and buffers can be used to ensure such a pH.

Acyl lactam activators such as those described in US 5,698,504, US 5,695,679 and US 5,686,014, each of which are cited above, especially acyl caprolactam (see eg WO 94-28102A) and Acylvalerolactam (see Willey et al. US Pat. No. 5,503,639, published Apr. 2, 1996, incorporated herein by reference) is very useful herein.

(B) Organic peroxides, especially diacyl peroxides -these are Kirk Othmer,
Encyclopedia of Chemical Technology, Vol.17, John Wiley and Sons, 1982, pp.2
7-90, especially pp.63-72, all incorporated herein by reference. When diacyl peroxides are used, those which minimize the adverse effects of smearing / filming are preferred.

(C) Metal-Containing Bleach Catalysts- The compositions and methods of the present invention may utilize metal-containing bleach catalysts that are effective for use in bleaching compositions. Bleach catalysts containing manganese and cobalt are preferred. One type of metal-containing bleach catalyst is a transition metal cation of a given bleach catalytic activity, such as a copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cation, an auxiliary metal cation with little or no bleach catalytic activity, such as zinc. Or an ion sequestrant having a predetermined stability constant for aluminum cations, catalysts and auxiliary metal cations, especially ethylenediaminetetraacetic acid,
A catalyst system comprising ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such a catalyst is disclosed in Br 2 dated February 2, 1982.
It is disclosed in agg US 4,430,243.

[0130]     Manganese metal complex-If desired, the composition may be catalyzed by manganese compounds.
Can be Such compounds and levels of use are well known in the art and are described, for example, in US
Patents 5,576,282, 5,246,621, 5,244,594, 5,19
4,416 and 5,114,606; European Patent Application Publication 549,271A1,
549,272A1, 544,440A2 and 544,490A1.
There are manganese-based catalysts. Preferred examples of these catalysts include Mn^IV _Two(U-O
)_Three(1,4,7-Trimethyl-1,4,7-triazacyclononane)_Two(PF ₆ )_Two, Mn^III _Two(U-O)₁(U-OAc)_Two(1,4,7-trimethyl-
1,4,7-triazacyclononane)_Two(ClO_Four)_Two, Mn^IV _Four(U-O)₆ (1,4,7-Triazacyclononane)_Four(ClO_Four)_Four, Mn^IIIMn^IV _Four(
u-O)₁(U-OAc)_Two(1,4,7-Trimethyl-1,4,7-triaza
Cyclononane)_Two(ClO_Four)_Three, Mn^IV(1,4,7-Trimethyl-1,4
7-triazacyclononane) (OCH_Three)_Three(PF₆) And their mixtures
is there. Other metal-based bleach catalysts include US 4,430,243 and US 5
, 114, 611. Various with manganese to enhance bleaching
The use with various complex ligands is also described in the following US Patents 4,728,455, 5,284,94
4, 5,246,612, 5,256,779, 5,280, 117, 5,27
4, 147, 5,153, 161 and 5,227,084.

[0131]     Cobalt metal complex-Cobalt bleach catalysts useful here are known,
For example, US Patents 5,597,936, 5,595,967 and 5,703,03.
0; and M.L. Tobe, "Base Hydrolysis of Transition-Metal Complexes",Adv.I norg.Bioinorg.Mech. , (1983), 2, pages 1-94. Useful here
Also preferred cobalt catalysts are those of the formula [Co (NH_Three)₅OAc] T_y("OAc" is
Represents the acetate portion, "T_y"Is an anion)"
Amine acetate, especially cobalt pentaamine acetic acid chloride [Co (NH_Three)₅OA
c] Cl_Two, And [Co (NH_Three)₅OAc] (OAc)_Two, [Co (NH_Three )₅OAc] (PF₆)_Two, [Co (NH_Three)₅OAc] (SO_Four), [Co (
NH_Three)₅OAc] (BF_Four)_TwoAnd [Co (NH_Three)₅OAc] (NO_Three) _Two (Hereinafter “PAC”).   These cobalt catalysts are described, for example, in US Patents 5,597,936, 5,595.
, 967 and 5,703, 030; Tobe's article and references cited therein;
US Patent 4,810,410;J. Chem. Ed.(1989),66(12), 1043-45 ； The Synthes
is and Characterization of Inorganic Compounds, W.L.Jolly (Prentice-Hall; 1
970), pp.461-3;Inorg.Chem.,18, 1497-1502 (1979);Inorg.Chem.,twenty one, 2881-2885 (
1982);Inorg.Chem.,18, 2023-2025 (1979);Inorg.Synthesis, 173-176 (1960);
AndJournal of Physical Chemistry,56, 22-25 (1952),
It is easily manufactured by a known operation.

Macropolycyclic Rigid Ligand Transition Metal Complexes -The present compositions may also suitably contain macropolycyclic rigid ligand transition metal complexes as bleach catalysts. The phrase "macropolycyclic rigid ligand" is sometimes abbreviated below as "MRL". The amount used is
A catalytically effective amount, suitably about 1 ppb or more, for example about 99.9% or less, more typically about 0.001 ppm or more, preferably about 0.05 to about 500 ppm ("
ppb "stands for parts / billion by weight and" ppm "stands for parts / million by weight).

Suitable transition metals, such as Mn, are described below. "Large polycyclic" means M
It is meant that the RL is both macrocycle and polycyclic. "Polycyclic" means at least bicyclic. As used herein, the term "rigid" includes "having a superstructure" and "crosslinked.""Hard" is defined as the opposite of soft:. DHBusch, which is incorporated by reference, Chemical Re views, (1993) , 93, see 847-860. More specifically, the "hard" used here
Are identical to macrocycles (having the same ring size and type and number of atoms in the main ring) but lacking the superstructure (particularly the linking moiety, or preferably the bridging moiety) found in MRL. It means that the MRL must be stiffer than the "parent macrocycle"). In investigating the relative hardness of macrocycles with and without superstructure, the practitioner used the free form (not the metal bonded form).
Use a macro cycle. Hardness is well known to be useful in comparing macrocycles; suitable techniques for determining, measuring or comparing hardness include computer methods (eg, Zimmer, Chemical Reviews , (1995 ), 95 (38), 2629-264
8 or Hancock et al., Inorganica Chimica Acta , (1989), 164, 73-84). Preferred MRLs here are crosslinked, specific types of ultra-hard ligands. "Crosslinking" is described in non-limiting manner in Section 1.11. In 1.11, the bridge is-
CH ₂ CH ₂ - is a moiety. It bridges N ¹ and N ⁸ in the exemplary structure. For comparison, an "ipsilateral" bridge is not sufficient to build a "crosslink" and is therefore not preferred if it is introduced at N ¹ and N ¹² , eg at 1.11.

Suitable metals for hard ligand complexes include Mn (II), Mn (III), Mn (IV), Mn (V
), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni
(I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II),
Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), M
o (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (I
I), Ru (III) and Ru (IV). Preferred transition metals for the present transition metal bleach catalysts are manganese, iron and chromium.

More generally, the MRLs (and corresponding transition metal catalysts) are suitably: (a) at least one macrocycle main ring having 4 or more heteroatoms, and (b) ) Preferably, the macrocycle hardness can be increased, selected from (i) a bridging superstructure such as a linking moiety, (ii) a bridging superstructure such as a bridging linking moiety, and (iii) a combination thereof. It is composed of covalently bonded non-metallic superstructures. The term "superstructure" is also used here, as defined in the article by Busch et al. (See, for example, the article by Busch, "Chemical Reviews").

The preferred superstructures here are not only to increase the hardness of the parent macrocycle, but are also preferred for the folding of the macrocycle to coordinate with the metal in the form of crevices. A suitable superstructure may be remarkably simple, for example connecting parts may be used as shown in FIGS. 1 and 2 below:

[Chemical 20] Where n is an integer, for example 2-8, preferably less than 6, typically 2-4; or

[Chemical 21] Where m and n are integers of about 1-8, more preferably 1-3; Z is N or CH; T is a compatible substituent such as H, alkyl, trialkylammonium, halogen, nitro. , Sulfonate and the like. The aromatic ring of 1.10 may be replaced by a saturated ring, in which case the atom of Z attached in the ring may be N, O, S or C.

[0137]   Suitable MRLs are further shown, without limitation, with the following compounds:

[Chemical formula 22] This is an MRL according to the invention which is a highly preferred bridged methyl substituted (all tertiary nitrogen atom) derivative of cyclam. Officially, this ligand is expanded von Ba
Using the eyer system, it is called 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane. "A Guide to IUPAC Nomenclature o
f Orgnic Compounds: Recommendations 1993 ", R. Panico, WH Powell & JCRich
er (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially Section R-2.4.2.1.

Macrocyclic rigid ligand transition metal bleach catalysts suitable for use in the compositions of the present invention generally include known compounds consistent with the definitions herein, and more preferably the laundry. Or there are a number of novel compounds specifically designed for cleaning and illustrated non-limitingly below: Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
． 6.2] Hexadecanemanganese (II) diako-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.
6.2] Hexadecane manganese (II) hexafluorophosphate aco-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) hexafluorophosphate diaco- 5,12-Dimethyl-1,5,8,12-tetraazabicyclo [6.
6.2] Hexadecanemanganese (II) tetrafluoroborate dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
． 6.2] Hexadecane manganese (III) hexafluorophosphate dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5 , 12-Dibenzyl-1,5,8,12-tetraazabicyclo [
6.6.2] Hexadecane manganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5- n-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12 -Tetraazabicyclo [6.6.2] hexadecane manganese (II)

As a matter of fact, and not by way of example, the present compositions and laundry processes are tailored to provide active bleach catalyst species in aqueous wash media at least as low as 0.01 ppm, and preferably in the wash liquor at about 0. 01 to about 25 ppm, more preferably about 0.0
Provide 5 to about 10 ppm, most preferably about 0.1 to about 5 ppm of bleach catalyst species. In order to achieve such levels in the wash liquor of an automated wash process, a typical composition of the invention is from about 0.0005 to about 0.2% by weight of the cleaning composition, more preferably from about 0.004 to about 0. Includes 0.08% bleach catalyst, especially manganese or cobalt catalyst.

(D) Other Bleach Catalysts -The composition may include one or more other bleach catalysts. A preferred bleach catalyst is US Pat. No. 5,576,282 (especially 3- (3,3
4-dihydroisoquinolinium) propane sulfonate) and 5,817,6
14 is the bipolar bleach catalyst described in 14. Other bleach catalysts include US Pat. Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,
826, 5,482, 515, 5,550, 256, and WO95 / 1335
1, WO 95/13352 and WO 95/13353, there are cationic bleach catalysts.

Enzyme The detergent composition of the present invention may further contain one or more enzymes that exert a cleaning performance effect. The enzyme includes cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, There is an enzyme selected from arabinosidase, mannanase, xyloglucanase or mixtures thereof. A preferred combination is a detergent composition with a cocktail of conventional enzymes such as proteases, amylases, lipases, cutinases, mannanases, xyloglucanases and / or cellulases. The enzyme, when present in the composition, is about 0.00 of the detergent composition.
The active enzyme level is from 01 to about 5% by weight.

Proteases useful in the present detergent compositions include, but are not limited to, trypsin, subtilisin, chymotrypsin and elastase-type proteases. Preferred for use herein are subtilisin-type proteolytic enzymes. Particularly preferred are bacterial serine proteolytic enzymes obtained from Bacillus subtilis and / or Bacillus lichenif ormis .

[0143]   Suitable proteolytic enzymes include Novo Industri A / S Alcalase^R(preferable
), Esperase^R, Savinase^R(Copenhagen, Denmark), Gat-brocade Maxatase ^R , Maxacal^RAnd Maxapem 15^R(Protein engineering Maxacal^R) (Delft, Ne
therlands), commercially available subtilisin BPN and BPN '(preferred)
There is. European Patent 251,446B (patented on December 28, 1994)
, Pages 17, 24 and 98), in which "protease B"
Made by Genencor International, Inc. (San Francisco, California)
Modified bacterial serine proteases such as are also preferred proteolytic enzymes.
Venegas US Pat. No. 5,030,378, issued July 9, 1991,
There, a modified bacterial serine called "Protease A" (same as BPN ')
Protein-degrading enzyme (Genencor International). In particular, protease A
For a complete description, including the amino acid sequences of variants thereof and variants thereof, see US Pat.
See columns 2 and 3 of 30,378. Other proteases are trade names: Primase, D
Available on urazym, Opticlean and Optimase. Preferred proteolysis
The enzyme is Alcalase^R(Novo Industri A / S), BPN ', Protease A and
Selected from the group consisting of Protease B (Genencor), and mixtures thereof
. Protease B is most preferred.

Of particular interest here for use are the proteases described in US Pat. No. 5,470,733. The proteases described in our co-pending application USSN 08 / 136,797 can also be included in the detergent compositions of the present invention.

Another preferred protease, designated "Protease D," is a carbonyl hydrolase variant with an amino acid sequence that is not found in nature, published by Genencor International, WO 95/10615, published Apr. 20, 1995. (A.
Baeck et al., USSN 08 / 322,67, filed October 13, 1994.
According to the numbering of Bacillus amyloliquefaciens subtilisin, as described in "Protease-containing cleaning composition" having 6), preferably +99, +101, +103, +104, +107, +123, +27.
, +105, +109, +126, +128, +135, +156, +166,
+195, +197, +204, +206, +210, +216, +217, +
218, +222, +260, +265 and / or +274, together with one or more amino acid residue positions corresponding to those selected from the group consisting of, at the position corresponding to position +76, a plurality of amino acid residues in the above carbonyl hydrolase. Derived from the precursor carbonyl hydrolase by using different amino acids for

Useful proteases are described by PCT Publication: The Procter & Gamble Company 1
WO95 / 30010, published on November 9, 995; The Procter & Gamb
WO95 / 30011 published by Le Company on November 9, 1995;
The WO published by The Procter & Gamble Company on November 9, 1995
95/29979.

Other particularly useful proteases are Bacillus amyloliquefaciens subtilisin 1,3,4,8,9,10,12,13,16,17,18,19,20,21.
, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58
, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89
, 97, 98, 99, 101, 102, 104, 106, 107, 109, 11
1, 114, 116, 117, 119, 121, 123, 126, 128, 13
0, 131, 133, 134, 137, 140, 141, 142, 146, 14
7, 158, 159, 160, 166, 167, 170, 173, 174, 17
7, 181, 182, 183, 184, 185, 188, 192, 194, 19
8, 203, 204, 205, 206, 209, 210, 211, 212, 21
3, 214, 215, 216, 217, 218, 222, 224, 227, 22
8, 230, 232, 236, 237, 238, 240, 242, 243, 24
4, 245, 246, 247, 248, 249, 251, 252, 253, 25
4, 255, 256, 257, 258, 259, 260, 261, 262, 26
Position 103 of Bacillus amyloliquefaciens subtilisin along with substitution of amino acid residues with other natural amino acid residues at one or more amino acid residue positions corresponding to positions 3, 265, 268, 269, 270, 271, 272, 274 and 275. Is a polysubstituted protease variant which has been substituted with another natural amino acid residue at the amino acid residue position corresponding to
When an amino acid residue is substituted at the position corresponding to position, Bacillus amyloliqu
efaciens subtilisin 27, 99, 101, 104, 107, 109, 123
, 128, 166, 204, 206, 210, 216, 217, 218, 222
There are also amino acid residue substitutions at one or more amino acid residue positions other than the amino acid residue positions corresponding to positions 260, 265 or 274; and / or all The Pr
Oct. & Gamble Company's PCT publication application No. WO99 / 20727, WO9
Bacillus, as described in 9/20726 and WO 99/20723.
There are also polysubstituted protease variants that have been substituted with amino acid residues by another natural amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of amyloliquefaciens subtilisin.

[0148] Protease described in patent application EP251446 and WO91 / 06637, Protease described in WO91 / 02792 BLAP ^R, and WO95
Those variants described in / 23221 are also suitable for the invention. See also the high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93 / 18140A. Enzymatic detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 from Novo.
A is described. If desired, proteases with reduced adsorptivity and increased hydrolyzability are commercially available as described in WO 95/07791 by Procter & Gamble. A suitable recombinant trypsin-like protease for detergents is
Novo WO 94/25583. Other suitable proteases are Un
ilever EP 516200.

[0149]   All commercially available proteases useful in the present invention are Novo Nordisk A / S from Denmark.
Et ESPERASE^R, ALCALASE^R, DURAZYM^R, SAVINASE^R, EVERLASE^RAnd KANNASE ^R As well as all Genencor International (formerly Gist-Brocades of The
 Netherlands) to MAXATASE^R, MAXACAL^R, PROPERASE^RAnd MAXAPEM^Rage
Is known.

The protease enzyme may be incorporated into the composition according to the invention at a pure enzyme level of from about 0.0001 to about 2% by weight of the composition.

Bleach / Amylase / Protease Combination (EP755,999A, EP7
56,001A, EP756,000A) are also useful. In connection with the enzymes herein, the enzymes and inhibitors directly linked to them,
Proteases linked by peptide chains and their inhibitors, as described for example in WO98 / 13483A, are also useful in combination with the present hybrid builders. Enzymes and their unligated inhibitors used in the combinations selected herein include WO98 / 13461A, WO98 / 13460A, WO98.
/ 13458A, proteases and protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO98 / 13387A.

Amylases may be combined with amylase antibodies as disclosed in WO98 / 07818A and WO98 / 07822A and lipases WO98 / 078.
17A and may be used in combination with a lipase antibody as disclosed in WO98 / 06810A and the protease is WO98 / 07819A and WO98 / 068.
The protease may be used in combination with a protease antibody as disclosed in 11A, and the cellulase may be used in combination with a cellulase antibody as disclosed in WO98 / 07823A and WO98 / 07821A. More generally, the enzyme is, for example, WO98.
/ 07820A or WO98 / 06812A, may be used in combination with similar or dissimilar enzyme-related antibodies.

The enzymes preferred herein may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The preferred choice is dictated by factors such as pH activity and / or optimal stability, thermal stability, and stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes such as bacterial amylases and proteases and fungal cellulases are preferred.

Amylases (α and / or β) may be included for the removal of carbohydrate-based soils. WO94 / 02597 describes a laundry composition incorporating a mutant amylase. See also WO95 / 10603. Other amylases known for laundry compositions include both α- and β-amylases. α-Amylase is known in the art and is described in US Pat. No. 5,003,257, EP252,666, WO
91/00353, FR2, 676, 456, EP285, 123, EP525
, 610, EP 368,341 and British patent specification 1,296,839 (Novo
) Have been disclosed in. Other suitable amylases are WO94 / 1 from Genencor
8314 and the stability-enhancing amylases described in WO 96/05295, and the Novo Nordisk A / S amylase variants with additional modifications in the immediate parentage disclosed in WO 95/10603. Amylases described in EP277216 are also suitable.

[0155] Examples of commercial α- amylases products, Purafect of Genencor Ox Am ^R, all Novo N
ordisk A / S TERMAMYL ^R , BAN ^R , FUNGAMYL ^R and D commercially available from Denmark
It is URAMYL ^R. WO95 / 26397, the other suitable amylases: as measured by Phadebas ^R alpha-amylase activity assay, temperature and 8 of 25 to 55 ° C.
At pH values 10 range, describes characterized is α- amylase by having at least 25% higher specific activity than the specific activity of TERMAMYL ^R. WO96 / 23
Variants of the above enzymes described in 873 (Novo Nordisk) are suitable. Other amylolytic enzymes having improved properties in terms of activity level and combination of thermostability and high activity level are described in WO 95/35382.

The compositions of the present invention may also include a mannanase enzyme. Preferably, the mannanase is three mannan degrading enzymes: EC3.2.1.25: β-mannosidase, EC3.2.1.78.
: Endo-1,4-β-mannosidase (hereinafter referred to as “mannanase”),
EC 3.2.1.100: selected from the group consisting of 1,4-β-mannobiosidase and mixtures thereof (IUPAC Classification-Enzyme nomenclature, 1992, I
SBN 0-12-227165-3, Academic Press).

More specifically, the composition of the invention comprises β-1,4-mannosidase (EC 3.2.1.78), which is referred to as mannanase when mannanase is present.
The term "mannanase" or "galactomannanase" is publicly referred to as mannan endo-1,4-β-mannosidase, with the alternative names β-mannanase and endo-1,4-mannanase, for the reaction of : 1,4-β in mannan, galactomannan, glucomannan and galactoglucomannan
-Represents a mannanase enzyme, defined according to the art as catalyzing the random hydrolysis of D-mannoside bonds.

In particular, mannanase (EC 3.2.1.78) belongs to the group of polysaccharases that degrade mannan, which is capable of cleaving polyose chains with mannose units.
That is, it represents an enzyme capable of cleaving the glycosidic bond of mannan, glucomannan, galactomannan and galactoglucomannan. Mannan is β-1,4-
Glucomannan is a polysaccharide having a main chain composed of linked mannose, and glucomannan is a polysaccharide having β-1,4-linked mannose and glucose alternating in the main chain or more or less regularly. Mannan is α
Mannan and glucomannan with -1,6-linked galactose side chains. These compounds may be acetylated.

Degradation of galactomannans and galactoglucomannans is facilitated by total or partial removal of galactose side chains. Furthermore, the degradation of acetylated mannan, glucomannan, galactomannan and galactoglucomannan is promoted by total or partial deacetylation. The acetyl group can be removed by alkali or mannan acetyl esterase. Oligomers released from mannanase or by the combination of mannanase with α-galactosidase and / or mannan acetylesterase can be further degraded by β-mannosidase and / or β-glucosidase to release free maltose.

Mannanases have been identified in several Bacillus organisms. For example, Talbot e
t al., Appl. Environ. Microbiol., Vol. 56, No. 11, pp. 3505-3510 (1990), 162.
Bacillus in dimeric form with a molecular weight of kDa and an optimum pH of 5.5-7.5.
Describes β-mannanase from us stearothermophilus. Mendoza
et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994), 38.
A β-mannanase from Bacillus subtilis having a molecular weight of kDa, optimal activity at pH 5.0 and 55 ° C. and a pl of 4.8 is described. JP
-03047076 has a molecular weight of 373 kDa as measured by gel filtration, 8 to
Β-from Bacillus sp. With an optimum pH of 10 and a pl of 5.3-5.4
A mannanase is disclosed. JP-63056289 describes the production of alkaline, thermostable β-mannanase, which hydrolyzes, for example, β-1,4-D-mannopyranoside bonds of mannan to produce manno-oligosaccharides. JP-63063774 relates to a Bacillus microorganism FERM P-8856 that produces β-mannanase and β-mannosidase at alkaline pH. JP-08051975 discloses alkaline β-mannanase from alkalophilic Bacillus sp. AM-001. A purified mannanase from Bacillus amyloliquefaciens useful for bleaching pulp and paper, and a method for its production are disclosed in WO 97/11164. WO91 / 18974 is an extreme p
Hemicellulases such as glucanases, xylanases or mannanases active at H and temperature are described. WO94 / 25576 Aspergillus showing mannanase activity useful for the degradation or modification of plant or algal cell wall material.
An enzyme from aculeatus CBS 101.43 is disclosed. WO93 / 24622
Disclose a mannanase isolated from Trichoderma reseei useful for bleaching lignocellulosic pulp. Hemicellulases capable of degrading mannan-containing hemicelluloses are described in WO 91/18974, Bacillus
Purified mannanase from amyloliquefaciens is described in WO 97/11164.

Preferably, the mannanase enzyme is an alkaline mannanase as described below, more preferably a mannanase derived from a bacterial source. In particular, the laundry detergent composition of the invention comprises a mannanase from Bacillus agaradhaerens strain NICMB 40482; Bacillus su
btilis strain 168, a gene yght-derived mannanase; an alkaline mannanase selected from Bacillus sp. I633-derived mannanase and / or Bacillus sp. AAI12-derived mannanase. The most preferred mannanase for inclusion in the detergent composition of the present invention is co-pending Danish Patent Application PA 1998.
The mannanase enzyme from Bacillus sp. I633 as described in 01340. The term "alkaline mannanase enzyme" refers to 7-12, preferably 7.5.
It is meant to include an enzyme having an enzyme activity of at least 10%, preferably at least 25%, and more preferably at least 40% of its maximum activity at a predetermined pH of ˜10.5.

Alkaline mannanases from Bacillus agaradhaerens NICMB 40482 are described in co-pending US patent application 09 / 111,256. More specifically, this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens NICMB 40482 ii) a SEQ ID as shown in US patent application 09 / 111,256
A polypeptide comprising an amino acid sequence as set forth at positions 32-343 of NO: 2, or iii) at least 70% homologous to the above polypeptide or substitution of one or several amino acids , A derivative of the polypeptide defined in i) or ii), which has been derived from said polypeptide by deletion or addition or which is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

In addition: (a) a mannanase activity comprising a sequence of nucleotides as set forth in nucleotide 97-nucleotide 1029 of SEQ ID NO: 1 as shown in US patent application 09 / 111,256. (B) a species homologue of (a); (c) an amino acid residue with SEQ ID NO: 2 as shown in US patent application 09 / 111,256. A polynucleotide molecule encoding a polypeptide having mannanase activity, which is at least 70% identical to the amino acid sequence of the group 32-amino acid residue 343; (d) (a), (b) or (c) A complementary molecule; and (e) selected from the group consisting of the degenerate nucleotide sequence of (a), (b), (c) or (d) To a corresponding isolated polypeptide having mannanase activity.

Polynucleotide molecule (DNA sequence) encoding the above mannanase
The plasmid pSJ1678 containing E. coli was integrated into a strain of Escherichia coli and transformed into Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Maschero.
der Web 1b, D-38124 Braunschweig, Federal Republic of Germany, deposited by the present inventors under the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, on May 18, 1998 under Deposit No. DSM12180. It was

A second more preferred enzyme is the mannanase from Bacillus subtilis strain 168 described in co-pending US patent application 09 / 095,163. More particularly, this mannanase is: i) encoded by the coding portion of the DNA sequence set forth in SEQ ID NO: 5 shown in US patent application 09 / 095,163 or an analogue of that sequence, and / or Or ii) a polypeptide comprising an amino acid sequence as set forth in SEQ ID NO: 6 shown in US patent application 09 / 095,163, or iii) with at least 70% homology to the above polypeptide Has been derived from said polypeptide by the substitution, deletion or addition of one or several amino acids,
Alternatively, it is an analog of the polypeptide defined in ii), which is immunoreactive with a polyclonal antibody against the above-mentioned polypeptide in a purified form.

Further: (a) a polypeptide having mannanase activity comprising a sequence of nucleotides as set forth in SEQ ID NO: 5 as set forth in US patent application 09 / 095,163. (B) a seed homolog of (a); (c) at least 70% of the amino acid sequence of SEQ ID NO: 6 as shown in US patent application 09 / 095,163. A polynucleotide molecule which is identical and encodes a polypeptide having mannanase activity; (d) a molecule complementary to (a), (b) or (c); and (e) (a), (b) ), (C) or (d) a degenerate nucleotide sequence, the corresponding isolated polypeptide having mannanase activity.

A third more preferred mannanase is co-pending Danish Patent Application PA199.
8 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. I633 ii) a SEQ as shown in Danish Application PA 1998 01340
A polypeptide comprising an amino acid sequence as set forth at positions 33-340 of ID NO: 2, or iii) one or several amino acid substitutions that are at least 65% homologous to said polypeptide, An analog of a polypeptide as defined in i) or ii), which is derived from said polypeptide by deletion or addition or is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

In addition: (a) had mannanase activity, comprising a sequence of nucleotides as shown in nucleotide 317-nucleotide 1243 of SEQ ID NO: 1 as shown in Danish application PA 1998 01340. (B) a species homologue of (a); (c) amino acid residue 33-amino acid residue 340 with SEQ ID NO: 2 as shown in Danish Application PA 1998 01340. A polynucleotide molecule encoding a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of: (d) a molecule complementary to (a), (b) or (c); and e) consists of a degenerate nucleotide sequence of (a), (b), (c) or (d) Also relates to isolated polynucleotide molecules that correspond selected from the group.

The plasmid pBXM3, which comprises the polynucleotide molecule (DNA sequence) coding for the mannanase of the invention, has been integrated into a strain of Escherichia coli and used to transform Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode.
r Web 1b, D-38124 Braunschweig, Federal Republic of Germany, in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, May 1998.
It was deposited by the present inventors on March 29th under the deposit number DSM12197.

A fourth more preferred mannanase is co-pending Danish Patent Application PA199.
No. 8 01341. More particularly, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI12 ii) a SEQ as shown in Danish Application PA 1998 01341
A polypeptide comprising an amino acid sequence as set forth at positions 25-362 of ID NO: 2, or iii) one or several amino acid substitutions that are at least 65% homologous to the above polypeptide, An analog of a polypeptide as defined in i) or ii), which is derived from said polypeptide by deletion or addition or is immunoreactive with a polyclonal antibody against said polypeptide in purified form.

In addition: (a) had mannanase activity, comprising a sequence of nucleotides as shown in nucleotides 225 to 1236 of SEQ ID NO: 1 as shown in Danish Application PA 1998 01341. (B) a species homologue of (a); (c) amino acid residue 25-amino acid residue 362 with SEQ ID NO: 2 as shown in Danish Application PA 1998 01341. A polynucleotide molecule encoding a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of: (d) a molecule complementary to (a), (b) or (c); and e) consists of a degenerate nucleotide sequence of (a), (b), (c) or (d) Also relates to isolated polynucleotide molecules that correspond selected from the group.

The plasmid pBXM1 comprising the polynucleotide molecule (DNA sequence) coding for the mannanase of the present invention was integrated into a strain of Escherichia coli and transformed into Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascherode.
r Web 1b, D-38124 Braunschweig, Federal Republic of Germany in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Patent Applications, 1998
It was deposited by the present inventors under the deposit number DSM 12433 on 7th October.

The mannanase, when present, is preferably 0.0001-2% by weight of the composition, more preferably 0.0005-0.1%, most preferably 0.001-0.
． The pure enzyme level of 02% is incorporated into the composition of the present invention.

The compositions of the present invention may also include a xyloglucanase enzyme. The xyloglucanase suitable for the purposes of the present invention is preferably a xyloglucan-specific endonuclease at a level of about 0.001 to about 1% by weight of the composition, more preferably about 0.01 to about 0.5%. It is an enzyme that exhibits glucanase activity. The term "endoglucanase activity" as used herein refers to 1,4-β-present in cellulosic materials such as cellulose, cellulose derivatives, lichenin, β-D-glucan or xyloglucan.
By the ability of an enzyme to hydrolyze D-glycosidic bonds. Endoglucanase activity was determined according to methods known in the art, examples of which are described in WO 94/14953 and below. 1 unit of endoglucanase activity (eg CMC
U, AVIU, XGU or BGU) is defined as the production of 1 μmol reducing sugar / min from a glucan substrate, such as CMC (CMCU), acid swelling Avicel.
l (AVIU), xyloglucan (XGU) or cereal β-glucan (BGU)
Is. Reducing sugars are examined as described in WO 94/14953 and below. The specific activity of endoglucanase on the substrate is defined as units / mg protein.

Enzymes that exhibit XGU endoglucanase activity as maximal activity (hereinafter “xyloglucan specific”) are suitable, which enzymes: i) comprise at least one of the following subsequences: Or the DNA sequence contained therein:

[Chemical formula 23] Alternatively, Aspergillus aculeatu encoded by a sequence homologous to a xyloglucan-specific polypeptide having endoglucanase activity and encoded by a DNA sequence defined in ii) i).
It is immunoreactive with an antibody to the highly purified endoglucanase from s CBS 101.43 and is specific to xyloglucan.

More specifically, the term “xyloglucan-specific” as used herein means that the endoglucanase enzyme exhibits its maximal endoglucanase activity on a xyloglucan substrate, such as other cellulose-containing substrates, eg Carboxymethyl cellulose, cellulose or other glucans are meant to exhibit preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity. Preferably, the specificity of endoglucanase for xyloglucan is
It is further defined as the relative activity obtained as a result of incubation of the enzyme with the xyloglucan and other substrates tested and as the release of reducing sugars under optimal conditions. For example, its specificity is xyloglucan to β-glucan activity (XGU / BGU), xyloglucan to carboxymethylcellulose activity (XG / BGU).
U / CMCU), or xyloglucan vs. acid swollen Avicell activity (XGU / AVI)
U), which is preferably about 50 or more, eg 75, 90 or 1
00.

As used herein, the term “derived from” refers to an endoglucanase produced by strain CBS101.43 as well as a DNA sequence isolated from strain CBS101.43, It also relates to an endoglucanase produced in the transformed host organism. As used herein, the term “homologue” (eg, presoaked in 5 × SSC, 5 × SSC, 5 × Denhardt's solution and 50 μg of denatured sonicated calf thymus DNA at −40 ° C. Prehybridize over time, then hybridize in the same solution supplemented with 50 μCi ³² P-dCTP labeled probe for 18 hours at −40 ° C., then in 2 × SSC, 0.2% SDS at 40 ° C. for 30 minutes. Wash 3 times)
Figure 2 shows a polypeptide encoded by a DNA that hybridizes with a probe similar to the DNA encoding for an endoglucanase enzyme specific for xyloglucan under certain conditions. More specifically, the term includes any of the above sequences encoding for an endoglucanase specific for xyloglucan and at least 75%, at least 80%, at least 85%, at least 90% or more of said sequence. Relates to DNA sequences which are at least 70% homologous, including at least 95%. The term refers to a host into which a DNA construct containing any of the above DNA sequences has been introduced without modification of any of the above DNA sequences, for example, without producing an amino acid sequence different from the polypeptide encoded by that sequence. Nucleotide substitutions corresponding to the codon usage of the organism, or different amino acid sequences, and thus possibly different amino acid sequences which may give rise to endoglucanase variants with different properties than the natural enzyme, and thus possibly different protein structures. The meaning includes substitution. Other examples of possible modifications include insertion of one or more nucleotides into the sequence, addition of one or more nucleotides to the end of the sequence, or 1 at or at the end of the sequence.
It is the deletion of the above nucleotides.

Xyloglucan-specific endoglucanases useful in the present invention include 50 or more, such as 75, 90 or 100 XGU / BGU, XGU (as described above).
/ CMU and / or XGU / AVIU ratio. Furthermore, the xyloglucan-specific endoglucanase is preferably substantially devoid of activity against β-glucan when the activity against xyloglucan is 100%, and / or carboxymethylcellulose and / or
It exhibits an activity against Avicells of at most 25%, eg at most 10% or about 5%.
In addition, the xyloglucan-specific endoglucanases of the invention are preferably substantially devoid of transferase activity, ie the activity observed with most endoglucanases specific to plant-sourced xyloglucan.

Xyloglucan-specific endoglucanases are also obtained from the fungal species A. aculeatus, as described in WO94 / 14953. Microbial endoglucanases specific for xyloglucan have also been described in WO94 / 14953.
An endoglucanase specific for xyloglucan from plants has also been described,
These enzymes have transferase activity and should therefore be regarded as inferior to xyloglucan-specific microbial endoglucanases whenever exhaustive degradation of xyloglucan is desired. An additional advantage of microbial enzymes is that they are generally produced in microbial hosts in higher amounts than enzymes of other origin.

Xyloglucanase, when present, preferably comprises 0.0001 of the composition.
˜2% by weight, more preferably 0.0005 to 0.1%, most preferably 0.00
Pure enzyme levels of 1-0.02% are incorporated into the compositions of the present invention.

The enzyme may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The origin may further be mesophilic or extreme (eg, psychrophilic, eutrophic, thermophilic, pressure-sensitive, alkalophilic, acidophilic, halophilic). Purified or unpurified forms of these enzymes may also be used. It is now customary to modify the wild-type enzyme by protein / genetic engineering techniques to maximize performance efficacy in the laundry detergent and / or fabric care compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the conventional ingredients of such compositions. on the other hand,
Variants may be designed such that the optimum pH, bleach or chelant stability, catalytic activity, etc. of the enzyme variant is adjusted to suit a particular laundry application.

Particular attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of detergent compatibility. The isoelectric point of such enzymes may be modified by substituting some charged amino acids, for example increasing the isoelectric point helps improve compatibility with anionic surfactants. Enzyme stability is further enhanced by, for example, forming additional salt bridges and strengthening calcium binding sites to increase cherant stability.

Another suitable cleaning additive that may be added is an enzymatic oxidation scavenger.
An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

A variety of enzyme materials are available from Genencor International, WO 93/07263 and W.
O93 / 07260, WO89 / 088694, and McCa dated January 5, 1971.
Also disclosed in US Pat. No. 3,553,139 to rty et al. The enzyme is US 4,101,
457 and US 4,507,219. Enzymatic substances that are particularly useful in liquid detergent formulations and their incorporation in such formulations is described in US Pat.
61,868.

Various carbohydrase enzymes that impart antibacterial activity may also be included in the present invention.
Such enzymes include US Patents 5,041,236, 5,395,541, 5,
There are endoglycosidases, type II endoglycosidases and glucosidases such as those disclosed in 238,843 and 5,356,803, the disclosures of which are incorporated herein by reference. Of course, other enzymes having antibacterial activity may also be used, including peroxidases, oxidases and various other enzymes. It is also possible to include an enzyme stabilization system in the composition of the present invention when the enzyme is present in the composition.

Enzyme Stabilizers Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also described, for example, in US 3,519,570. Useful to provide proteases, xylanases and cellulases
Bacillus sp. AC13 is described in WO9401532. The enzyme used herein can be stabilized in the final composition by the presence of a water-soluble source of calcium and / or magnesium ions, which provides such ions to the enzyme. Suitable enzyme stabilizers and levels of use are described in US Pat. No. 5,705,464,5,7.
10, 115 and 5,576, 282.

Builders The detergent and laundry compositions described herein preferably comprise one or more detergent builders or builder systems. When present, the composition typically comprises at least about 1% by weight, preferably about 5%, more preferably about 10% to about 80%, preferably about 50%, more preferably about 30%. Including detergent builders. However, it does not mean that lower or higher levels of builders are excluded.

Builders preferred for use in the detergent and laundry compositions described herein, particularly the dishwashing compositions, include US Pat. Nos. 5,695,679, 5,705,464 and 5,7.
Water-soluble builder compounds such as those described in 10,115 (eg, polycarboxylates), but are not limited thereto. Other suitable polycarboxylates are disclosed in US Pat. Nos. 4,144,226, 3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates having up to 3 carboxyl groups per molecule, more particularly tartrate.

Inorganic or P-containing detergent builders include polyphosphates (exemplified by tripolyphosphate, pyrophosphate and glassy polymer metaphosphate).
, Phosphonates (eg US Pat. No. 3,159,581, 3,213,030,
3,422,021, 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates of alkali metal, ammonium and alkanol ammonium salts. There is, but is not limited to, those. However, non-phosphate builders are also required in some areas. It is important to note that even in the presence of so-called "weak" builders such as citrate (compared to phosphates) or even in the so-called "underbuilt" situations that can occur with zeolites or laminated silicate builders. The composition works surprisingly well.

Suitable silicates include water soluble sodium silicates having a SiO ₂ : Na ₂ O ratio of about 1.0 to 2.8, with a ratio of about 1.6 to 2.4 being preferred and about 2 ．
The 0 ratio is the most preferable. The silicate may take the form of anhydrous salt or hydrated salt. 2.0
Most preferred is sodium silicate with a SiO ₂ : Na ₂ O ratio of. The silicate, when present, is preferably present in the detergent and laundry compositions described herein at a level of from about 5 to about 50% by weight of the composition, more preferably from about 10 to about 40%.

Partially soluble or insoluble builder compounds suitable for use in detergent and laundry compositions, especially granular detergent compositions, include crystalline layered silicates, preferably as described in US Pat. No. 4,664,839. Crystalline laminated sodium silicate (partially water-soluble), and sodium aluminosilicate (water-insoluble), but are not limited thereto. When present in detergent and laundry compositions, these builders are typically present at levels of about 1-80% by weight of the composition, preferably about 10-70%, most preferably about 20-60%. Exists.

The general formula NaMSi _x O _{2x + 1} · yH ₂ O (M is sodium or hydrogen, x
Is a number of about 1.9 to about 4, preferably about 2 to about 4, most preferably 2 and y is a number of about 0 to about 20, preferably about 0. Can also be used in the compositions described herein. This type of crystalline layered sodium silicate is disclosed in EP-A-0164514 and their method of manufacture is disclosed in DE-A-3417649 and DE-A-3742043.
The most preferred material is δ-Na ₂ SiO ₅ commercially available from Hoechst AG as NaSKS-6 (usually abbreviated as “SKS-6”). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has the δ-Na ₂ SiO ₅ morphology of laminated silicates.
Although SKS-6 is a highly preferred laminated silicate for use in the compositions described herein, other such laminated silicates, such as the general formula NaMSi _x O _{2x + 1.}
those having yH ₂ O (M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0), It may be used in the composition described. Various other laminated silicates from Hoechst include α
, NaSKS-5, NaSKS-7 and NaSKS-11 as β and γ forms
There is. As noted above, δ-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred herein for use. Other silicates such as magnesium silicates are also useful, which can serve as a crispening agent in granule formulations, as a stabilizer for oxygen bleaching, and as a component of a foam control system. The crystalline layered sodium silicate material is preferably present in the granular detergent composition as granules intimately mixed with a solid, water soluble, ionizable material. The solid, water-soluble, ionizable substance is preferably selected from organic acids, organic and inorganic acid salts, and mixtures thereof.

Aluminosilicate builders are very important in most currently marketed heavy granular detergent compositions and are also important builder ingredients in liquid detergent formulations. The aluminosilicate builder has the empirical formula: [M _z (AlO ₂ ) _y ] xH ₂ O where z and y are at least integers of 6 and the molar ratio z to y is 1. 0 to about 0
． 5 and x is an integer from about 15 to about 264. Preferably, the aluminosilicate builder is an aluminosilicate zeolite having the following unit cell formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] .xH ₂ O wherein z and y are at least 6 And the molar ratio of z to y is 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264.
Is. The aluminosilicate builders are preferably in the hydrated form, preferably in the bound form, crystals containing about 10 to about 28%, more preferably about 18 to about 22% water.

These aluminosilicate ion exchange materials may be crystalline or amorphous in structure, natural aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in US 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are commercially available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP and Zeolite HS, and mixtures thereof. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O, wherein x is from about 20 to about 30, especially It is about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Zeolite X has the formula: Na _{86 [(AlO 2) 86 (SiO 2} ) 106 ] · 276 h ₂ O

Citrate builders, such as citric acid and its soluble salts (particularly the sodium salt), are particularly important polycarboxylates in heavy duty liquid detergent formulations due to their availability from renewable sources and their biodegradability. A rate builder. Citrate may also be used in the granular composition, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinate is also particularly useful in such compositions and combinations.

The detergent compositions described herein include those disclosed in US 4,566,984.
Also suitable are 3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds. Useful succinic acid builders, C ₅ -C ₂₀ alkyl and alkenyl succinic acid, and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Lauryl succinate is the preferred builder of this group and is described in European patent application 86200690.5 / 0,200,263 published Nov. 5, 1986.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be incorporated into the composition, either alone or in combination with said builders to provide additional builder activity, especially citrate and / or succinate builders. This should be considered by the artisan as such use of fatty acids usually results in reduced foaming.

Dispersants One or more suitable polyalkyleneimine dispersants may also be incorporated into the laundry compositions of the present invention. Examples of such suitable dispersants are described in European patent application 111,965,1.
11,984 and 112,592; US Patents 4,597,898, 4,548.
, 744 and 5,565,145. However, any suitable soil / soil dispersant or anti-redeposition agent may be used in the laundry compositions of the present invention.

In addition, polymeric dispersants including polymeric polycarboxylates and polyethylene glycols are also suitable for use in the present invention. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. There is. A particularly suitable polymeric polycarboxylate may be derived from acrylic acid. Such acrylic acid-based polymers useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably from about 2000 to 10,000, more preferably about 4.
000-7000, most preferably about 4000-5000. Water-soluble salts of such acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known substances. The use of this type of polyacrylate in detergent compositions is described, for example, in US Pat.
No. 3,308,067.

Acrylic acid / maleic acid based copolymers may also be used as a preferred component of the dispersion / anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such a copolymer in acid form is
Preferably about 2000 to 100,000, more preferably about 5000 to 750,000.
00, most preferably in the range of about 7,000 to 65,000. The ratio of acrylate to maleate segment in such copolymers is usually about 30:
It is in the range of 1 to about 1: 1 and more preferably about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. This type of soluble acrylate /
Maleate copolymers are known substances described in European patent application 66915 published on Dec. 15, 1982, and E published on Sep. 3, 1986.
P193,360 also describes such polymers containing hydroxypropyl acrylate. Still other useful dispersants are maleic acid / acrylic acid / vinyl alcohol terpolymers. Such materials also include E, including, for example, acrylic acid / maleic acid / vinyl alcohol 45/45/10 terpolymers.
It is disclosed in P193, 360.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG not only acts as a soil stain removal-redeposition inhibitor, but also exhibits dispersant performance. Typical molecular weight ranges for these purposes are about 500 to about 100,
000, preferably about 1000 to about 50,000, more preferably about 1500 to
Within the range of about 10,000. Polyaspartate and polyglutamate dispersants may also be used, especially in combination with zeolite builders. A dispersant such as polyaspartate is preferably about 1
It has a molecular weight (average) of 10,000.

Soil Release Agents The compositions according to the invention may optionally contain one or more soil release agents in addition to the polymeric compounds of the polymer stabilizing system described above, including anti-redeposition agents. If utilized, the soil release agent is typically about 0.01% by weight of the composition, preferably about 0.
． 1%, more preferably about 0.2% to about 10%, preferably about 5%, more preferably about 3%.

The following describes a soil release polymer suitable for use in the present invention, all incorporated herein by reference. U of Hays, issued May 25, 1976
S3,959,230; Basadur US3, issued July 8, 1975.
893,929; Nicol et al., US 4,0, issued December 28, 1976.
00,093; Gosselink US Pat. No. 4, issued Oct. 27, 1987.
, 702, 857; Scheibel et al., US 4,968,4, issued on 6 November.
51; Gosselink, US 4,702,8, issued October 27, 1987.
57; Gosselink et al., US 4,711,7 published December 8, 1987.
30; Gosselink US Pat. No. 4,721,58 issued Jan. 26, 1988.
0; Maldonado et al., US 4,877,8, published October 31, 1989.
96; Gosselink et al., US 4,956,4, issued September 11, 1990.
47; Gosselink et al., US 5,415,8 issued May 16, 1995.
07; European patent application 0,21 published on April 22, 1987 by Kud et al.
9,048.

Other suitable soil release agents are Violland et al. US 4,201,824; Lagasse et al. US 4,240,918; Tung et al. US 4,525,524; Ruppert et al U.
S4,579,681; US4,240,918; US4,787,989; U
S4, 525, 524; 1988 Rhone-Poulenc Chemie EP 279,134.
A; BASF (1991) EP 457, 205A; and 1974 Unilever.
NV DE 2,335,044, all incorporated herein by reference. Commercially available stain release agents are METOLOSE SM100 and METOLOSE SM2 manufactured by Shin-Etsu Chemical KK.
00, BASF (Germany) commercially available SOKALAN type substances, eg SOKALAN HP-22, ZE
There are LCON 5126 (Dupont) and MILEASE T (ICI).

A preferred SRA is a hydrophilic segment that hydrophilizes the surface of hydrophobic fibers, such as polyester and nylon, and attaches onto the hydrophobic fiber and continues to adhere to it until the end of the wash and rinse cycle, thus It typically has a hydrophobic segment that acts as an anchor for the segment. This makes it possible to more easily wash off stains generated after the SRA treatment in the subsequent washing operation.

Chelating Agents The compositions of the present invention may also optionally include chelating agents that act to form chelates with metal ions and metal impurities that tend to deactivate the bleaching agent. Useful chelating agents include those known to those skilled in the art, such as aminocarboxylates, phosphonates, aminophosphonates, polyfunctional substituted aromatic chelating agents and mixtures thereof. Another example and level of use of suitable chelating agents is US Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,57.
6, 282. The presence of the chelating agent contributes to further increase the chemical stability of the composition. Chelating agents are also desirable in the compositions of the present invention as they improve the ionic strength of the composition and thus the stain removal and bleaching performance on various surfaces.

Phosphonate chelators suitable for use herein include the alkali metal ethane 1-
Hydroxydiphosphonate (HEDP), alkylene poly (alkylenephosphonate) and aminophosphonate compounds such as aminoaminotri (methylenephosphonic acid) (ATMP), nitrilotrimethylenephosphonate (NTP), ethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate (DTPMP). There is. The phosphonate compounds may exist in their acid form or as salts of cations that differ in some or all of their acid functional groups. Preferred phosphonate chelating agents used herein are diethylenetriaminepentamethylenephosphonate (DTPMP), and ethane 1-
Hydroxydiphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST ^R.

Polyfunctional substituted aromatic chelating agents are also useful in the present compositions. See Connor et al., US Pat. No. 3,812,044, issued May 21, 1974. A preferred compound of this type is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene when in the acid form.

Preferred biodegradable chelating agents for use herein are ethylenediamine N, N′-
Disuccinic acid, its alkali metal, alkaline earth, ammonium or substituted ammonium salts, or mixtures thereof. Ethylenediamine N, N'-disuccinic acid, especially the (S, S) isomer, is described in detail in Hartman and Perkins, US Pat. Ethylenediamine N, N
′ -Disuccinic acid is commercially available, for example, from Palmer Research Laboratories under the tradename ssEDD.
It is commercially available in S ^R.

Suitable aminocarboxylates used herein include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropion, all in the acid form. There are acids, triethylene tetraamine hexaacetic acid, ethanol diglycine, propylene diamine tetraacetic acid (PDTA) and methylglycine diacetic acid (MGDA), or their alkali metal, ammonium and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine pentaacetic acid, propylenediamine tetraacetic acid (PDTA) (e.g., trade name from BASF Trilon FS sold by ^R) and methyl glycine diacetic acid (MGDA). Another carboxylate chelating agent used herein is salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

[0211]   Another chelating agent for use herein is of the formula:

[Chemical formula 24] In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently -H, alkyl, alkoxy,
Aryl, _{aryloxy, -Cl, -Br, -NO 2,} -C (O) ' is selected from the group consisting of and _-SO 2 R "(R' R is -H, -OH, alkyl, alkoxy, aryl And aryloxy; R ″ is selected from the group consisting of alkyl, alkoxy, aryl and aryloxy)
R ₅ , R ₆ , R ₇ and R ₈ are independently selected from the group consisting of —H and alkyl. Particularly preferred chelating agents used herein are aminoaminotri (methylenephosphonic acid), diethylenetriaminepentaacetic acid, diethylenetriaminepentamethylenephosphonate, 1-hydroxyethanediphosphonate, ethylenediamineN.
, N'-disuccinic acid and mixtures thereof. Typically, the composition according to the invention is within about 15% by weight of the total composition, more preferably within about 5%, preferably 0.01 to 1.5% by weight, more preferably 0.01.
˜0.5% chelating agent or mixtures thereof.

Radical Scavengers The compositions of the present invention may include radical scavengers or mixtures thereof. Radical scavengers suitable for use herein include the well-known substituted mono- and dihydroxybenzenes and their analogs, alkyl- and arylcarboxylates, and mixtures thereof. Preferred radical scavengers for use herein include di-tert-butylhydroxytoluene (BHT), hydroquinone, di-tert-butylhydroquinone, mono-tert-butylhydroquinone, tert-butylhydroxyanisole, benzoic acid, toluic acid. , Catechol, t-butylcatechol, benzylamine, 1,1,3-tris (2-methyl-4-hydroxy-
There is 5-t-butylphenyl) butane, n-propyl gallate or mixtures thereof, highly preferred is di-tert-butylhydroxytoluene. Such radical scavengers, such as n-propyl gallate, are commercially available from Nipa Laborat.
It is marketed under the trade name Nipanox S1 ^R by ories. Radical scavengers, when used, are typically present here in amounts of up to about 10% by weight of the total composition, preferably from about 0.001 to about 0.5% by weight. The presence of the radical scavenger contributes not only to the safety of the composition of the invention, but also to the chemical stability of the bleaching composition of the invention.

Foam Inhibitor Another optional ingredient is a foam suppressant exemplified by silicones and silica-silicone mixtures. Examples of suitable suds suppressors are found in US Pat. No. 5,707,950.
And 5,728,671. These suds suppressors are typically used at levels of about 0.001 to about 2% by weight of the composition, preferably about 0.01 to about 1%.

[0214]Foam enhancer   If high foamability is desired, C₁₀-C₁₆Occurrences like alkanolamides
A foam booster may be included in the composition, typically at a level of about 1-10%. C₁₀-C ₁₄ Monoethanol and diethanolamide are typical of such suds boosters
It is a kind. Such foam enhancers and the aforementioned amine oxides, betaines and sutures.
Use in combination with a highly foaming additive surfactant such as lutein is also advantageous. If desired
, MgCl_Two, MgSO_FourSoluble magnesium salts such as
To increase fat removal performance, for example at levels of 0.1-2%.
Yes.   Other suitable examples of suds boosters, both published on June 3, 1999,
Both are WO99 / 27058 and WO99 from The Procter & Gamble Company
/ 27057.

Brighteners Any optical brighteners, fluorescent whitening agents or other brightening or whitening agents known in the art are included in the composition as they are designed for fabric treatment or laundering. When typically about 0.05 to about 1.2 of the detergent composition.
It can be compounded at a level of wt%. Commercially available optical brighteners useful in the invention include, but are not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, as derivatives.
Methocyanins, dibenzothiophene-5,5-dioxide, azoles, 5
And subgroups including 6-membered heterocyclic brighteners, but this list is exemplary and non-limiting. An example of such a brightener is "The Production
and Application of Fluorescent Brightening Agents ", M.Zahradnik, John Wile
Published by y & Sons, New York (1982).

Specific examples of optical brighteners useful in the composition are described in Wixon on Dec. 13, 1988.
U.S. Pat. No. 4,790,856. These brighteners include Verona's PHORWHITE series of brighteners. Other brighteners disclosed in this document include Tinopal UNPA, Tinopal, commercially available from Ciba-Geigy.
CBS, Tinopal 5BM and Tinopal PLC; Artic White CC and Artic White CWD available from Hilton-Davis, Italy; 2- (4-styrylphenyl)-
2H-naphthol [1,2-d] triazoles; 4,4'-bis (1,2,3)
-Triazol-2-yl) stilbenes; 4,4'-bis (styryl) bisphenyls; and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin and 1,2-bis (benzimidazol-2-
Yl) ethylene, 2,5-bis (benzoxazol-2-yl) thiophene,
2-styrylnaphtho [1,2-d] oxazole and 2- (stilbene-4-
Il) -2H-naphtho [1,2-d] triazole. February 29, 1972
See also Hamilton US Pat. No. 3,646,015 issued dated. Anionic brighteners are typically preferred here.

[0217]Softener   Fabric softeners may also be incorporated into the laundry detergent composition according to the present invention. Inorganic softener is G
SMEC disclosed in BA-1,400,898 and US Pat. No. 5,019,292
Illustrated by tight clay. For organic softeners, GB-A1,514,276
And water-insoluble tertiary amines as disclosed in EP-B 0,011,340,
Mono C disclosed in EP-B-026,527 and EP-B-026,528 ₁₂ -C₁₄Their combination with quaternary ammonium salts, and EP-B-0,2
There are di-long chain amides as disclosed in 42,919. Other useful fabric softening systems
Suitable organic compounds include EP-A-0,299,575 and 0,313,146.
There are high molecular weight polyethylene oxide materials as shown.   Particularly suitable fabric softeners are US Pat. Nos. 5,707,950 and 5,728,6.
73.

The level of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
%, The material is added to the rest of the formulation as a dry mix ingredient. Organic fabric softeners such as water-insoluble tertiary amines or dilong chain amide materials are 0
． 5 to 5% by weight, usually 1 to 3% by weight, and the high molecular weight polyethylene oxide substance and water-soluble cationic substance are 0.1 to 2% by weight, usually 0.15% by weight.
Added at a level of 1.5%. These materials are usually added to the spray-dried part of the composition, but in some cases they were added as dry mix granules or sprayed as a molten liquid onto other solid components of the composition. It is more convenient. Biodegradable quaternary ammonium compounds, such as those described in EP-A-040,562 and EP-A-239,910, are used as alternatives to traditionally used di-long chain alkyl ammonium chlorides and methyl sulphates. Proposed. Non-limiting examples of softener compatible anions for quaternary ammonium compounds and amine precursors are chloride or methylsulfate.

Dye Inhibition The detergent composition of the present invention is a compound for inhibiting the dye transfer from one fabric with dissolved and suspended dyes to the other that occurs during fabric laundering and conditioning operations involving colored fabrics. Can also be included.

I. Polymer Transfer Inhibitor The detergent composition according to the present invention comprises 0.001-10% by weight, preferably 0.01-.
It may also contain 2%, more preferably 0.05 to 1% of a polymer transfer inhibitor. The polymeric dye transfer inhibitors described above are commonly incorporated into detergent compositions to prevent dye migration from the colored fabric onto the washed fabric. These polymers have the ability to complex with or adsorb free dye washed off from colored fabrics before the dye has the opportunity to become attached to other articles in the wash liquor. Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. Examples of such dye transfer inhibitors are described in US Pat. No. 5,707,
950 and 5,707,951.

Additional suitable dye transfer inhibitors include, but are not limited to, crosslinked polymers. A crosslinked polymer is a polymer in which the main chains are linked to some extent, and these linkages may be of chemical or physical nature, possibly the active groups may be on the main chain or on the side chains, and the crosslinked polymer may be the Journal. of Polymer Science, volume 22, pages 1
It is described in 035-1039. In one aspect, the cross-linked polymer is made to form a three-dimensional rigid structure and is capable of entrapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer swells to capture the dye. Such crosslinked polymers are described in co-pending European patent application 94870213.9. The addition of such polymers also enhances the performance of the enzyme according to the invention.

Effervescent Systems The compositions of the present invention are described in US provisional patent application 60, filed June 28, 1999.
/ 141,340 (Attorney Docket No. "7638P") may optionally be included.

PH and Buffer Variations Many of the detergent and laundry compositions described herein are buffered, that is they are relatively resistant to pH reduction in the presence of acidic soil. However, other compositions may have exceptionally low buffer capacity or be substantially unbuffered. Techniques for controlling or changing pH at recommended use levels include:
More generally, as well as buffers, the use of additional alkalis, acids, pH jump systems, dual compartment vessels, etc., are well known to those skilled in the art.

Other Materials The cleaning ingredients or additives optionally included in the composition may include laundering performance, to assist or enhance the treatment of the substrate being cleaned, or to enhance the aesthetics of the composition. There are also one or more substances designed to improve. Additives that may be included in the compositions of the present invention at conventional industry-established use levels (usually, the total amount of additive material is from about 30 to about 99.9% by weight of the composition, preferably from about 70 to about 95%). U.S. Pat. No. 5,705,464, 5,710,115, 5,698,504, 5
, 695,679, 5,686,014 and 5,646,101, non-phosphate builders, color speckles, silver care agents, rust and / or corrosion inhibitors, There are other active ingredients such as dyes, fillers, bactericides, alkalinity sources, hydrotropes, antioxidants, fragrances, stabilizers, carriers, processing aids, pigments and pH adjusting agents.

[0225] described washing method herein, in addition to fabric laundering methods, the present invention also comprises laundering pretreatment process for fabrics with a dirty or stain, such fabrics using customary aqueous wash Prior to washing, comprises directly contacting the stains and / or soils described above with the laundry composition in a highly concentrated form. Preferably, the laundry composition is left in contact with the soil / stain for about 30 seconds to 24 hours before routinely cleaning the soiled / stained substrate to be pretreated. More preferably, the pretreatment time is about 1
~ 180 minutes.

Product with Instructions for Use The present invention also includes a description of the use of the aqueous liquid detergent composition of the present invention in a package containing the composition, or other form of advertising associated with the sale or use of the composition. The description is typically used by consumer product manufacturers or suppliers,
It can be included in any method. By way of example, a label attached to the container containing the composition; a sheet attached to the container or attached to it at the time of purchase; or an advertisement, an advertisement, and / or other document accompanying the purchase or use of the composition or Add explanation in the oral explanation. In particular, the instructions include instructions for use of the composition, eg, recommended amount of composition used in the washing machine to clean the fabric; recommendations for composition applied to the fabric if dipping or rubbing is appropriate. Will include the quantity.

The composition of the present invention is preferably contained in a product. The product preferably comprises an aqueous liquid detergent composition comprising a polymer stabilizing system, and optionally one or more cleaning additives, further requiring cleaning to ensure that the composition cleans the fabric. Comprising contacting the fabric with an effective amount of the composition to wash the fabric with the product.

While particular embodiments of the present invention have been described, it will be apparent to those skilled in the art that various changes and modifications of the invention can be made without departing from the spirit and scope of the invention. For all such modifications that fall within the scope of the invention, the appended claims are considered to be covered.

[0229] The aqueous liquid bleaching composition for use as Formulation Examples Example 1 additive is prepared as follows: peracids 22 Citric acid 5 NaOH 1.3 suspending agent ¹ 0.45 polymer stabilizing system ² 0. The 5 water 70.75 ¹ suspension may be any of the above suspensions, preferably xanthan gum. ^{The two} polymer stabilization system can be any of the polymer stabilization systems described above, preferably the polymer stabilization system comprises the polymers described in US Pat. No. 4,968,451.

Example 2 A heavy aqueous liquid bleaching composition in a dual compartment bottle is prepared as follows: Compartment 1 Citric Acid 2.80 C12-16 Soap 3.20 Ethanol 2.01 MEA 2.00 Propylene Glycol 7.40 Ca formate 0.05 Borax 2.50 NaOH 2.90 Ethoxylated tetraethylenepentaimine 0.60 PE20 1.20 Protease 0.88 Cellulase 0.050 Amylase 0.070 Mannanase 0.0033 FWA-150 .125 NaLAS 2.40 C12-13AE9 (Neodol 23.9) 2.40 C14-15AE1.00S ^* Na 18.00 C10APA 1.20 Red HP 0.00225 Perfume 0.50 NaHCO ₃ 2.00 Water 49.89 Compartment 2 Peracid 22 Citric acid 5 NaOH 1.3 Suspension ¹ 0.45 Polymer stabilizing system ² 0.5 Water 70.75 ¹ suspensions may the be any suspension, preferably xanthan gum. ^{The two} polymer stabilization system can be any of the polymer stabilization systems described above, preferably the polymer stabilization system comprises the polymers described in US Pat. No. 4,968,451.

The compositions of the present invention may be suitably manufactured by any process selected by the practitioner, a non-limiting example of which is US Pat.
, 1979, 584, US5 by Nassano et al., Issued November 11, 1997.
, 692, 297, published on November 12, 1996 by Welch et al., US 5,
574,005, US5 by Dinniwell et al., Issued October 29, 1996.
, 569, 645, US of Del Greco et al., Published October 15, 1996.
5,565,422, US 5, issued to Capeci et al., May 14, 1996.
516,448, US Pat. No. 5,489 of Capeci et al., Issued February 6, 1996.
, 392, US Pat. No. 5,486,3 of Capeci et al., Issued January 23, 1996.
03, all of which are incorporated herein by reference.

In addition to the above examples, the compositions of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are Baeck et al., US Pat. 679, 630, Watson et al., US 5,565,145 issued October 15, 1996, Fredj et al. U, December 26, 1995.
S5, 478, 489, US of Fredj et al., Issued November 28, 1995.
5,470,507, U of Panandiker et al., Issued November 14, 1995.
S 5,466,802, Fredj et al., US, issued October 24, 1995.
5,460,752, US5 by Fredj et al., Issued October 17, 1995.
, 458, 810, US 5, Fredj et al., Issued October 17, 1995.
458,809, US Pat. No. 5,28, Huber et al., Issued February 22, 1994.
8, 431, all of which are incorporated herein by reference.

Although the present invention has been described in detail by listing preferred embodiments and examples, various changes and modifications can be made without departing from the scope of the present invention and the present invention as described herein. It will be apparent to those skilled in the art that it is not limited.

[Sequence list]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, K E, LS, MW, MZ, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, BZ, C A, CH, CN, CR, CU, CZ, DE, DK, DM , DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, K E, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, RO, R U, SD, SE, SG, SI, SK, SL, TJ, TM , TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Karel, Joseph, Maria, Depute             Belgium-Bee-8790, Waregem, Bourg             Zlaan, 9 (72) Inventor Francesco, Debutza Carrini             B-2870, Breendonk, Belgium             Coningin, Astrid Lane, 5 (72) Inventor Rob, log band             B-2900, Belgium, Shorten, Ah             Le. W. buoy. Hubble Learn,             195/6 F-term (reference) 4H003 AB02 AB19 AB31 AC06 AC08                       BA12 DA01 DA03 DA05 DA17                       DC02 EA16 EA21 EB07 EB08                       EB09 EB10 EB14 EB28 EB30                       EB32 EB33 EB34 EB45 EC01                       EC02 EC03 ED02 ED28 EE06                       FA08

Claims (19)

[Claims] 1.   (A) one or more granular solids; and   (B) Polymer stabilization system An aqueous liquid detergent composition comprising: 2.   The composition of claim 1, wherein the one or more particulate solids contain a peracid. 3. The composition according to claim 2, wherein the peracid is phthaloylaminoperoxycaproic acid. 4. A polymer stabilizing system comprising ethoxylated nonionic polymers, anionic polyterephthalate polymers, ethoxylated nonionic surfactants, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl N-oxides, polycarboxylates and mixtures thereof. The composition of claim 1 comprising a polymeric compound selected from the group consisting of: 5. The composition of claim 4, wherein the polymeric compound is selected from the group consisting of ethoxylated nonionic polymers, anionic polyterephthalate polymers. 6. The composition of claim 1, wherein one or more particulate solids are present in the composition at a level of 0.1 to 25% by weight of the composition. 7. The composition of claim 1, wherein the polymer stabilizing system is present in the composition at a level of 0.01 to 10% by weight of the composition. 8.   The composition of claim 1, wherein the composition further comprises a suspending agent. 9.   The composition of claim 8, wherein the suspending agent is xanthan gum. 10.   The composition of claim 1, wherein the composition further comprises a surfactant. 11. The composition according to claim 10, wherein the surfactant is selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic surfactants and mixtures thereof. 12. A composition comprising a surfactant, a builder, a bleach, a bleach activator, a bleach catalyst, an enzyme, an enzyme stabilizing system, a chelant, an optical brightener, a soil release polymer, a dye transfer agent, a dispersant, and an initiator. Suds suppressor, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescent agent, fabric conditioner, fabric softener, hydrolyzable surfactant, preservative, antioxidant, anti-shrink agent, wrinkle Inhibitors, fungicides, fungicides, color spectrum, silver care agents, rust and / or corrosion inhibitors,
The composition of claim 1 further comprising one or more cleaning additive materials selected from the group consisting of alkalinity sources, solubilizers, carriers, processing aids, pigments and pH control agents. 13. A method of contacting a cloth with the aqueous liquid detergent composition according to claim 1.
A method for laundering fabric in need of laundering. 14. A liquid composition comprising (a) one or more particulate solids; (b) comprising one or more particulate solids comprising the addition of a polymer stabilizing system. A method for reducing eye irritation of a liquid composition. 15.   15. The method of claim 14, wherein the liquid composition is an aqueous liquid composition. 16.   15. The method of claim 14, wherein the one or more particulate solids contain peracid. 17. The method of claim 16, wherein the peracid is phthaloylaminoperoxycaproic acid. 18. A polymer stabilizing system comprising ethoxylated nonionic polymers, anionic polyterephthalate polymers, ethoxylated nonionic surfactants, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl N-oxides, polycarboxylates and mixtures thereof. 15. The method of claim 14, comprising a polymeric compound selected from the group consisting of: 19. The method of claim 18, wherein the polymeric compound is selected from the group consisting of ethoxylated nonionic polymers, anionic polyterephthalate polymers.