CN1230213A - Detergent composition - Google Patents

Abstract

Detergent composition comprising a peroxygen bleach, a bleach activator, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions comprising a peroxygen bleach, a bleach catalyst, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Background

The formulation of laundry detergents and other cleaning compositions presents serious challenges because modern compositions require removal of all sorts of soils from a wide variety of substrates. Accordingly, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashing machines all require the proper selection and combination of various components in order to function effectively. Generally, these detergent compositions will contain one or more types of surfactants to loosen or remove different types of soils and stains. Although a summary of the literature appears to indicate that a wide variety of surfactants and combinations thereof are available for selection by detergent manufacturers, the reality is that many of these components are specialty chemicals that are not suitable for use in low unit price items such as household laundry detergents. The fact is that most of these household products, such as laundry detergents, still contain predominantly one or more conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and the need to formulate compositions that perform reasonably well on a wide variety of fabrics and a wide variety of soils and stains.

The rapid and efficient removal of different types of soils and stains, such as body soils, grease/oil soils and certain food stains, can be problematic. These soils are notoriously difficult to remove becausethey include hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and mixtures of proteinaceous materials. Often leaving a low level of hydrophobic soils and residual stain on the fabric surface after laundering. The end result of successive washes and donning, coupled with limited removal of hydrophobic soils in the wash, is the accumulation of residual soils and stains, which further entrap particulate soils, resulting in fabric yellowing. The resulting fabric has a dull appearance that the consumer may find it uncomfortable to wear and discard.

Various nitrogen-containing cationic surfactants have been proposed in the literature as being useful in a wide variety of cleaning compositions. These materials are usually present in the form of amino, amido or quaternary ammonium or imidazolinium salts and are commonly used for special purposes. For example, various amino and quaternary ammonium type surfactants have been proposed for use in shampoo compositions which are said to have a cosmetic effect on the hair. Other nitrogen-containing surfactants are used in certain laundry detergents to provide fabric softening and antistatic effects. However, commercial use of such materials is most likely limited by the difficulties encountered in large scale manufacture of such compounds. Another limitation is that the anionic active components of the detergent composition may precipitate due to ionic interaction with the cationic surfactant. The nonionic and anionic surfactants mentioned above remain the major surfactant components in present day laundry compositions.

It has now been found that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in a variety of detergent compositions to enhance cleaning performance over a wide variety of soils and stains, especially hydrophobic soils, of the type commonly encountered. Unexpectedly, it has now been found that compositions comprising bis-AQAsurfactants, peroxygen bleach and a metal-containing bleach catalyst provide superior cleaning and whitening performance as compared to products containing only the single agents.

The bis-AQA surfactants of the present invention provide significant advantages to the formulator over previously known cationic surfactants. For example, the bis-AQA surfactants used in the present invention provide significant improvements in cleaning of "everyday" greasy/oily hydrophobic soils frequently encountered. Additionally, the compatibility of bis-AQA surfactants with anionic surfactants commonly used in detergent compositions, such as alkyl sulfates and alkyl benzene sulfonates, while the incompatibility with the anionic component of the detergent composition has heretofore often been a limiting factor in the use of cationic surfactants. The beneficial effects described herein can be produced with low levels (as low as 3ppm in the laundry detergent) of bis-AQA surfactant. The bis-AQA surfactants can be formulated over a wide pH range of 5 to 12. The bis-AQA surfactants can be formulated as pumpable 30% by weight solutions and are therefore easily transported in the factory. bis-AQA surfactants having a degree of ethoxylation above 5 are sometimes present in liquid form and may therefore be provided as 100% pure materials. In addition to their advantageous delivery properties, the presence of bis-AQA surfactants as highly concentrated solutions provides a significant economic advantage in terms of transportation costs. The bis-AQA surfactants are also compatible with various perfume ingredients, unlike certain cationic surfactants known in the art.

The bleach catalyst (characterized by the presence of at least one transition metal atom) interacts with the peroxygen bleach to form a powerful hydrophilic bleach. These bleaches are useful for eliminating colored hydrophilic stains and hydrophilic everyday soils (i.e., sock soils). Historically, difficulties havebeen encountered with the use of bleach catalysts due to concerns about fabric damage. It has now been found that the inclusion of bis-AQA cationic surfactants in detergent compositions is greatly reduced by fabric damage caused by the use of dimanganese catalysts which are known to cause fabric damage. It is believed that these cationic surfactants adsorb on the fabric, alter the surface charge of the fabric and may undergo ionic pairing with the activated catalyst, thereby reducing or preventing fabric damage.

It is believed that bis-AQA effectively stabilizes greasy/oily soils, thereby allowing access of hydrophilic bleach catalysts to colour bodies (e.g. entrapped pigments) within the soil, resulting in improved soil fading. The compositions of the present invention provide superior cleaning and whiteness maintenance benefits in cleaning both hydrophilic and hydrophobic soils.

Background

United states patent 5,441,541 issued to a.mehretcab and f.j.lopast at 8/15 of 1995 relates to anionic/cationic surfactant mixtures. British patent 2,040,990 issued on 3.9.1980 to a.p.murphy, r.j.m.smith and m.p.brooks relates to ethoxylated cationic surfactants in laundry detergents.

Summary of The Invention

The present invention provides a composition comprising or prepared from a peroxygen bleach, a bleach catalyst, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl, ether or alditol based ether moieties, R²Is a C₁-C₃Alkyl radical, R³And R⁴Independently variable, selected from hydrogen, methyl and ethyl, X is an anion, A and A' independently variable, each being C₁-C₄Alkoxy, p and q can vary independently and are integers from 1 to 30.

Detailed DescriptionPeroxygen bleaching agent

The detergent compositions of the present invention comprise a peroxygen bleach. Such bleaching agents are generally present at levels of from 1 to 30%, more usually from 5 to 20% of the detergent composition, especially for fabric laundering.

Preferred peroxygen bleaching agents are perhydrate bleaches. The perhydrate bleach is normally incorporated in the form of the perhydrate salt (especially the sodium salt) at a level of from 1 to 40%, more preferably from 2 to 30%, most preferably from 5 to 25% by weight of the composition.

Although the perhydrate bleach itself has some bleaching power, the peracid formed by the reaction of the hydrogen peroxide released from the perhydrate with the bleach activator is a more advantageous bleach. Preformed peracids are also preferred as hydrogen peroxide bleaches.

Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. Preferred perhydrate salts are typically alkali metal salts. The perhydrate salt may be added as a crystalline solid without additional protection. However, for some perhydrate salts, it is preferred that such granular compositions are in a coated form which provides better storage stability of the perhydrate salt in the granular product.

Sodium perborate may be of the nominal formula NaBO₂H₂O₂NaBO monohydrate or tetrahydrate₂H₂O₂·3H₂The form of O exists.

Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the invention. The chemical formula of sodium percarbonate is 2Na₂CO₃·3H₂O₂The addition compounds of (a) are commercially available in the form of crystalline solids. As a hydrogen peroxide addition compound, sodium percarbonate releases hydrogen peroxide quite rapidly on dissolution, which increases the tendency of local high bleach concentrations to rise. The percarbonate is preferably incorporated into the composition in a coated form which provides in-product stability.

Suitable coating materials that provide in-product stability include water-soluble mixed salts of alkali metal sulfates and carbonates. Such coatings and coating methods are described in GB-1,466,799 to Interox (9/3 1977). The weight ratio of mixed salt coating material to percarbonate is in the range 1: 200 to 1: 4, preferably 1: 99 to 1: 9, most preferably 1: 49 to 1: 19. The mixed salt is preferably composed of sodium sulfate and sodium carbonate, and its formula is Na₂SO₄·n·Na₂CO₃Wherein n is 0.1 to 3, preferably n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

Other coatings, including silicates (alone or with borates or boric acid or other minerals), waxes, oils, fatty soaps may also be advantageously used within the present invention.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range 500-1000 microns, not more than 10% by weight of the particles being less than 200 microns and not more than 10% by weight of the particles being more than 1250 microns.

Another suitable bleaching agent that may be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. Pat. No. 4,483,781(Hartman, 20.11.1984), U.S. patent application 740,446(Burns et al, filed 3.6.1985), European patent application 0,133,354(Banks et al, published 20.2.1985) and U.S. Pat. No. 4,412,934(Chung et al, 1.11.1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxyhexanoic acid as described in U.S. Pat. No. 4,634,551 (6.1.6.1987, Burns et al). Potassium monopersulfate is another inorganic perhydrate that may be used in the compositions of the present invention.

Mixtures of bleaching agents may also be used.Bleaching catalyst

The detergent compositions described herein contain a bleach catalyst as an essential component. The yield of catalyst in the product is usually very low, preferably from 0.001 to 5% by weight, more preferably from 0.01 to 2% and most preferably from 0.05 to 1%. The bleach catalyst is preferably a metal-containing, more preferably a transition metal-containing bleach catalyst. Preferred transition metal-containing bleach catalysts are manganese-or cobalt-containing bleach catalysts.

One suitable class of bleach catalysts comprises a heavy metal cation of defined bleach catalytic activity (e.g. copper, iron cations), an auxiliary metal cation of low or no bleach catalytic activity (e.g. zinc or aluminium cations), and a sequestrant having defined stability constants for the catalytic or auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are described in U.S. Pat. No. 4,430,243.

Preferred classes of bleach catalysts include manganese-based complexes disclosed in U.S. Pat. Nos. 5,246,621 and 5,244,594. Preferred examples of these catalysts include M_n ^IV ₂(u-O)₃(1, 4, 7-trimethyl-1, 4, 7-trisAzacyclononane)₂-(PF₆)₂，M_n ^III ₂(u-O)₁(u-OAc)₂(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(ClO₄)₂，M_n ^IV ₄(u-O)₆(1, 4, 7-triazacyclononane)₄-(ClO₄)₂，M_n ^IIIM_n ^IV ₄(u-O)₁(u-OAc)₂- (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(ClO₄)₃And mixtures thereof. Other examples are described in european patent application publication No. 549,272. Other ligands suitable for use in the present invention include 1,5, 9-trimethyl-1, 5, 9-triazacyclononane, 2-methyl-1, 4, 7-triazacyclononane, 1,2, 4, 7-tetramethyl-1, 4, 7-triazacyclononane, and mixtures thereof.

Bleach catalysts suitable for use in the present invention may also be selected for use in the compositions. Examples of suitable bleach catalysts are found in U.S. Pat. Nos. 4,246,612 and 5,227,084. See also U.S. Pat. No. 5,194,416, for mononuclear manganese (IV) complexes mentioned therein, e.g. M_n(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) (OCH₃)₃-(PF₆)。

Another class of bleach catalysts as disclosed in U.S. Pat. No. 5,114,606 is a water-soluble complex of manganese (III) and/or (IV) with a ligand which is a non-carboxylic acid based polyol having at least three adjacent C-OH groups. Preferred ligands include sorbitol, iditol, galactitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

Us patent 5,114,611 mentions bleach catalysts comprising complexes of transition metals (including Mn, Co, Fe or Cu)with a non- (macro) -cyclic ligand. The ligand has the following chemical formula:

R²R³

R¹-N＝C-B-C＝N-R⁴wherein R is¹、R²、R³And R⁴Each selected from H, substituted alkyl and aryl, such that each R is¹-N＝C-R²And R³-C＝N-R⁴Forming a 5 or 6 membered ring. The ring may be further substituted. B is selected from O, S, CR⁵R⁶、NR⁷And C ═ O, where R is⁵、R⁶And R⁷Each can be H, alkyl, or aryl, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the ring may be substituted with substituents such as alkyl, aryl, alkoxy, halogen, and nitro. A particularly preferred ligand is 2, 2' -bipyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe-bipyridylmethane and bipyridylamido complexes. Highly preferred catalysts include cobalt (2, 2 ' -bipyridinium) dichloride, cobalt (II) bis (isothiocyanate) bipyridinium amide, cobalt (II) perchlorate tris (II) terpyridinium amide, cobalt (2, 2 ' -bipyridinium) perchlorate, copper (II) bis (2, 2 ' -bipyridinium) perchlorate, iron (II) tris (bis-2-pyridinamine) perchlorate, and mixtures thereof.

Preferred examples include binuclear M_nComplexes with tetra-N-ligands and di-N-ligands, including N₄M_n ^III(u-O)₂M_n ^IVN₄)⁺And [ (bipyridine)₂M_n ^III(u-O)₂M_n ^IV(bipyridine)₂]-(ClO₄)₃。

Although the structure of the bleach-catalysing manganese complexes of the invention has not been elucidated, it is speculated that theycontain chelates or other hydrated coordination complexes formed by the interaction of a carboxyl group with a nitrogen atom on a ligand bearing a manganese cation. Similarly, the oxidation state of the manganese cation during catalysis is not fully understood and may be in the (+ II), (+ III), (+ IV) or (+ V) valence state. Since the ligand has six possible sites for attachment to the manganese cation, it is reasonable to speculate that polynuclear forms and/or "cage" structures may be present in the aqueous bleaching medium. Regardless of the actual form in which the active Mn ligand is present, it acts in an apparently catalytic manner, enhancing bleaching efficacy against stubborn stains such as those of tea, tomato paste, coffee, wine and fruit juices.

Other bleach catalysts are described in, for example, the following patents: european patent application 408,131 (cobalt complex catalyzed), european patent applications 384,503 and 306,089 (metalloporphyrin catalyzed), us patent 4,728,455 (manganese/polydentate ligand catalyzed), us patent 4,711,748 and european patent application 224,952 (manganese absorbed on aluminosilicate catalyst), us patent 4,601,845 (aluminosilicate support loaded with manganese and zinc or magnesium salts), us patent 4,626,373 (manganese/ligand catalyst), us patent 4,119,557 (iron complex catalyst), german patent specification 2,054,019 (cobalt chelator catalyst), canadian patent 866,191 (transition metal containing salt), us patent 4,430,243 (chelator with manganese cations and non-catalytic metal cations) and us patent 4,728,455 (manganese gluconate catalyst).

Other preferred examples include cobalt (III) catalysts of the formula:

Co[(NH₃)_nM′_mB′_bT′_tQ_qP_p]Y_ywherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5, mostpreferably 5); m' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, most preferably 1); b' represents a bidentate ligand; b is an integer of 0 to 2; t' represents a tridentate ligand; t is 0 or 1; q is a tetradentate ligand; q is 0 or 1; p is a pentadentate ligand; p is 0 or 1; n + m +2b +3t +4q +5p ═ 6; y is one or more suitably selected counterions of the number Y, wherein Y is an integer from 1 to 3 (preferably 2 to 3; when Y is a-1 valent anion, preferably Y is 2) to provide a charge-balanced salt, preferably Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, or combinations thereof; and wherein at least one of the co-bonded co-ordination positions is not under the conditions of use of the automatic dishwashing machineThe stable, remaining coordination sites stabilize the cobalt under conditions of use of the automatic dishwashing machine, such that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) relative to a normal hydrogen electrode.

Preferred such cobalt catalysts have the formula:

[C_o(NH₃)_n(M′)_m]Y_ywherein n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); m' is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and combinations thereof (when M is greater than 1); m is an integer of 1 to 3 (preferably 1 or 2, more preferably 1); m + n is 6; y isAre suitably selected counterions, the number of which is Y, which is an integer from 1 to 3 (preferably from 2 to 3, most preferably 2 when Y is a-1 valent anion), to give charge-balanced salts.

A preferred such cobalt catalyst suitable for use in the present invention is of the formula [ C_o(NH₃)₅Cl]Y_yIn particular [ C_o(NH₃)₅Cl]Cl₂Pentaammine cobalt chloride salt of (1).

More preferred are compositions of the present invention using a cobalt (III) bleach catalyst of the formula:

[C_o(NH₃)_n(M)_m(B)_b]T_ywherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); m is one or more ligands coordinated with cobalt at one position; m is 0,1 or 2 (preferably 1); b is a ligand coordinated to the cobalt in two positions; b is 0 or 1 (preferably 0), and when b is 0, then m + n is 6, and when b is 1, then m is 0 and n is 4; t is one or more suitably selected counterions in the number y, where y is an integer to obtain a charge-balanced salt (y is preferably 1-3, and when T is a-1 valent anion, y is preferably 2); wherein the catalyst has a base hydrolysis rate constant of less than 0.23M^-1S^-1(25℃)。

Preferably T is selected from chloride, iodide, I₃ ^-Formate, nitrate, nitrite, sulfate, sulfite, citrateCitrate, acetate, carbonate, bromide, PF₆ ^-、BF₄ ^-、B(Ph)₄ ^-Phosphate, phosphite, silicate, tosylate, mesylate, and mixtures thereof.

Optionally, if there is more than one anionic group in T, e.g. HPO₄ ^2-、HCO₃ ^-、H₂PO₄ ^-Etc., then T may be protonated. In addition, T may be selected from unconventional inorganic anions, such AS anionic surfactants (e.g., Linear Alkylbenzene Sulfonate (LAS), Alkyl Sulfate (AS), Alkyl Ethoxy Sulfonate (AES), etc.) and/or anionic polymers (e.g., polyacrylate, polymethacrylate, etc.).

M moieties include, but are not limited to F^-、SO₄ ^2-、NCS^-、SCN^-、S₂O₃ ^-、NH₃、PO₄ ^3-And carboxylic acid groups (preferably monocarboxylic acid groups, but more than one carboxylic acid group may be present in M, provided that each M is bound to the cobalt via only one carboxylic acid group, in which case the other carboxylic acid groups in M may be protonated or take the form of a salt thereof). Optionally, if more than one anionic group is present in M (e.g. HPO)₄ ^2-、HCO₃ ^-、H₂PO₄ ^-、HOC(O)CH₂C(O)O^-Etc.), then M may be protonated. Preferred M are substituted and unsubstituted C of the formula₁-C₃₀Carboxylic acid:

RC (O) O-wherein R is preferably selected from hydrogen and C₁-C₃₀(preferably C)₁-C₁₈) Unsubstituted and substituted alkyl, C₆-C₃₀(preferably C)₆-C₁₈) Unsubstituted and substituted aryl, and C₃-C₃₀(preferably C)₅-C₁₈) Unsubstituted and substituted heteroaryl, wherein the substituents are selected from NR'₃、-NR′₄ ⁺、-C(O)OR′、-OR′、-C(O)NR′₂Wherein R' is selected from hydrogen andC₁-C₆a group. Such substituted R thus includes- (CH)₂)_nOH and- (CH)₂)_nNR′₄ ⁺Wherein n is an integer from 1 to 16, preferably from 2 to 10, most preferably from 2 to 5.

Most preferred M is a carboxylic acid having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched chain C₄-C₁₂Alkyl, and benzyl. Most preferably R is methyl. Preferred carboxylic acid M moieties include formic acid, benzoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, malonic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenic acid, oleic acid, palmitic acid, trifluoromethanesulfonic acid, tartaric acid, stearic acid, butyric acid, citric acid, acrylic acid, aspartic acid, fumaric acid, lauric acid, linoleic acid, lactic acid, malic acid, and especially acetic acid.

Part B includes carbonate, dicarboxylic acid groups or higher carboxylic acid groups (e.g., oxalate, malonate, malate, succinate, maleate), picolinic acid, and α -and β -amino acids (e.g., glycine, alanine, β -alanine, phenylalanine).

Cobalt bleach catalysts suitable for use in the present invention are known in the text "alkaline hydrolysis of transition metal complexes" of m.l. tobeInorganic and bio-inorganic mechanism progression(Adv.Inorg.Bioinorg.Mech.)1983，21-94 along with their rate of alkaline hydrolysis. For example, the base hydrolysis rate (with k) of pentaaminecobalt catalyst complexed with the following is provided in table 1, table 17_OHRepresents): oxalate (k)_OH＝2.5×10^-4M^-1S^-1(25℃))，NCS^-(k_OH＝5.0×10^-4M^-1S^-1(25 ℃ C.)), formate (k)_OH＝5.8×10^-4M^-1S^-1(25 ℃ C.)) and acetate (k)_OH＝9.6×10^-4M^-1S^-1(25 ℃ C.)). The most preferred cobalt catalyst suitable for use in the present invention is of the formula [ C_o(NH₃)₅OAc]T_yIn which OAc represents acetate, especially chloroacetate pentaammineCobalt [ C]_o(NH₃)₅OAc]Cl₂(ii) a And [ C_o(NH₃)₅OAc](OAc)₂，[C_o(NH₃)₅OAc](PF₆)₂，[C_o(NH₃)₅OAc](SO₄)，[C_o(NH₃)₅OAc](BF₄)₂And [ C_o(NH₃)₅OAc](NO₃)₂(herein "PAC").

These cobalt catalysts are readily prepared by known methods, see for example the following: the aforementioned article by Tobe and the references cited therein; U.S. Pat. No. 4,810,410 (3/7/1989, Diakun et al); journal of chemical education (j.chem.ed.), 1989,66(12)，1043-45, a first step of; synthesis and characterization of Inorganic Compounds (The Synthesis and Characterisionof Inorganic Compounds), W.L.Jolly (Prentice-Hall, 1970), pp.461-3; inorganic chemistry (Inorg, Chem.),181497-1502 (1979); inorganic chemistry (Inorg, Chem.),212881-2885 (1982); inorganic chemistry (Inorg, Chem.),182023-2025 (1979); inorganic synthesis (inorg. synthesis), 173- "176 (1960); and Journal of physical chemistry (Journal of physical chemistry),5622-25 (1952); as well as the examples provided below.

In practice, but not by way of limitation, the automatic dishwashing composition and cleaning method may be adjusted to provide on the order of at least 0.01ppm active bleach catalyst in the aqueous wash medium, preferably from about 0.01 to about 25ppm, more preferably from about 0.05 to about 10ppm, and most preferably from about 0.1 to about 5ppm bleach catalyst. To achieve this level in the wash liquor of an automatic dishwashing process, a typical automatic dishwashing composition of the present invention will contain from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, by weight of the cleaning composition, of a bleach catalyst, especially a manganese or cobalt catalyst.Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants

A third essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:

wherein R is¹Is a straight, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether, alditol based ether moiety containing from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms; r²Is an alkyl group having 1 to 3 carbon atoms, preferably methyl; r³And R⁴Can vary independently, selected from hydrogen (preferably) methyl and ethyl; x^-Is an anion sufficient to provide charge neutrality, e.g., chloride, bromide, methylsulfate, sulfate. A and A' may vary independently and are each selected from C₁-C₄Alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is 1 to 30, preferably 1 to 15, more preferably 1 to 8, most preferably 1 to 4; q is 1 to 30, preferably 1 to 15, more preferably 1 to 8, most preferably 1 to 4. Preferably, both p and q are 1.

Wherein the hydrocarbyl substituent R¹Is C₈-C₁₂In particular C₈-C₁₀The bis-AQA compounds have improved dissolution rates of laundry particles, especially in the cold, compared to longer carbon chain materialsUnder water conditions. Thus, C₈-C₁₂bis-AQA surfactants may be preferred by some formulators. The levels of AQA surfactants used in formulated laundry detergent compositions may range from 0.1 to 5% by weight, usually from 0.45 to 2.5% by weight. The weight ratio of bis-AQA to sodium percarbonate bleach is from 1: 100 to 5: 1, preferably from 1: 60 to 2: 1, most preferably from 1: 20 to 1: 1.

The present invention employs an "effective amount" of a bis-AQA surfactant to improve the performance of cleaning compositions containing other optional ingredients. By "effective amount" of the bis-AQA surfactants herein is meant an amount sufficient to directionally or significantly improve the efficacy of the cleaning compositions to remove at least some of the target soils and stains with a 90% confidence level. Thus, in compositions wherein the target comprises certain food stains, the formulator will use sufficient bis-AQA to at least directionally improve cleaning efficacy against such stains. Also, in compositions where the target comprises soil, the formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such soil.

Such bis-AQA surfactants can be used in detergent compositions with other detersive surfactants at levels effective to achieve at least directional improvement in cleaning performance. In the case of fabric washing compositions, this "dosage level" can vary not only with the type and severity of the stain, but also with the wash water temperature, wash water volume and type of washing machine.

For example, in a top-loading, vertical axis American-type automatic washing machine, 45 to 83 liters of water are used in the wash bath for a wash cycle time of 10 to 14 minutes at a wash water temperature of 10 to 50 deg.C, where the wash liquor preferably contains 2 to 50ppm, preferably 5 to 25ppm, of the bis-AQA surfactant. This corresponds to a bis-AQA surfactant concentration by weight in the product of from 0.1 to 3.2%, preferably from 0.3 to 1.5%, for high performance liquid laundry detergents, calculated as 50 to 150 ml per wash load. For compact ("compacted") type granular laundry detergents (densities above 650g/l) this corresponds to a weight concentration of the bis-AQA surfactant in the product of from 0.2 to 5.0%, preferably from 0.5 to 2.5%, calculated as 60 to 95 grams per wash load. For spray dried granules (i.e. "loose" having a density below 650g/l), this corresponds to an in-product concentration of the bis-AQA surfactant of from 0.1 to 3.5%, preferably from 0.3 to 1.5%, calculated as an amount of 80 to 100 grams per wash load.

For example, in a front-loading horizontal axis European automatic washing machine, 8-15 liters of water are used in the wash bath for a wash cycle of 10-60 minutes at a wash water temperature of 30-95 deg.C, where the wash liquor preferably contains 13-900ppm, preferably 16-390ppm, of the bis-AQA surfactant. For high performance liquid laundry detergents this corresponds to a product internal concentration (by weight) of the bis-AQA surfactant of from 0.4 to 2.64%, preferably from 0.55 to 1.1%, calculated as 45 to 270ml per wash load. For compact ("compacted") type granular laundry detergents (densities above 650g/l), this corresponds to a product internal weight concentration of the bis-AQA surfactant of from 0.5 to 3.5%, preferably from 0.7 to 1.5%, calculated as 40 to 210 grams per wash load. For spray dried granules (i.e., "loose" having a density of less than 650g/l), this corresponds to a product internal weight concentration of the bis-AQA surfactant of from 0.13 to 1.8%, preferably from 0.18 to 0.76%, calculated as 140-400 g per wash load.

For example, in a top-loading, vertical axis, Japanese-type automatic washing machine, 26-52 liters of water are used in the wash bath, with a wash cycle time of 8-15 minutes and a wash water temperature of 5-25 deg.C, where the wash liquor preferably contains 1.67-66.67ppm, preferably 3-6ppm, of the bis-AQA surfactant. For high performance liquid laundry detergents, the bis-AQA surfactant has a product internal concentration of 0.25 to 10%, preferably 1.5 to 2%, by weight per wash load of 20 to 30 ml. For compact ("compacted") type granular laundry detergents (densities above 650g/l), this corresponds to a product internal weight concentration of bis-AQA of 0.25 to 10%, preferably 0.5 to 1.0%, calculated as 18 to 35 grams per wash load. For spray dried granules (i.e. "loose", densities below 650g/l), this corresponds to a product internal concentration of bis-AQA of 0.25 to 10%, preferably 0.5 to 1%, by weight, calculated as 30 to 40 grams per wash load.

As can be seen from the above, the amount of bis-AQA surfactant used in mechanical laundry can vary depending on the habits and practices of the user, the type of washing machine, etc. In this regard, however, one previously unappreciated advantage of bis-AQA surfactants is their ability to at least qualitatively improve cleaning performance over a wide variety of soils and stains when used at lower levels than other surfactants (typically anionic or mixed anionic/nonionic) in the finished composition. This is in contrast to other compositions in the art in which various cationic surfactants are used with anionic surfactants at or near stoichiometric levels. In general, in the practice of the present invention, the weight ratio of bis-AQA to anionic surfactant in the laundry composition is from 1: 70 to 1: 2, preferably from 1: 40 to 1: 6, more preferably from 1: 30 to 1: 6, most preferably from 1: 15 to 1: 8. In laundry compositions containing both anionic and nonionic surfactants, the weight ratio of bis-AQA to mixed anionic/nonionic surfactant is from 1: 80 to 1: 2, preferably from 1: 50 to 1: 8.

Various other cleaning compositions containing anionic surfactants, optionally nonionic surfactants, and specialty surfactants (e.g., betaines, sultaines, amine oxides, etc.) may also be formulated in the manner of this invention with an effective amount of a bis-AQA surfactant. These compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cleansing bars, laundry blocks, and the like. Because of minor variations in the habits and practices of the users of such compositions, it is desirable to include from 0.25% to 5%, preferably from 0.45% to 2%, by weight of the AQA surfactant in such compositions. As in the case of granular and liquid laundry compositions, the weight ratio of bis-AQA surfactant to other surfactants in these compositions is also low, i.e. sub-stoichiometric in the case of anionic surfactants. Preferably, such cleaning compositions contain the same bis-AQA/surfactant ratio as that of the mechanical laundry compositions mentioned immediately above.

The bis-alkoxylated cationic surfactants of the present invention are sufficiently soluble compared to other cationic surfactants known in the art that they can be used with mixed surfactant systems having low levels of, for example, alkyl sulfate surfactants, but non-ionic surfactants. This is a significant consideration for formulators of detergent compositions designed for top-loading automatic washing machines in general, and washing machines of the type used in north american and japanese use conditions in particular. Generally, these compositions contain anionic to nonionic surfactant in a weight ratio in the range of about 25: 1 to 1: 25, preferably about 20: 1 to 3: 1. This is in contrast to European-type formulations which contain anionic to nonionic surfactant ratios of from about 10: 1 to 1: 10, preferably from about 5: 1 to 1: 1.

Preferred ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the tradename ETHOQUAD. Alternatively, various reaction schemes can be used as shown below (where "EO" represents-CH)₂CH₂O-units) were synthesized.Scheme 1

Scheme 2 Scheme 3

Scheme 4

An economical reaction scheme is as follows.Scheme 5

The following parameters summarize the optional and preferred reaction conditions of scheme 5. Step 1 of the reaction is preferably carried out in an aqueous medium, the reaction temperature generally being 140 ℃ to 200 ℃. The reaction pressure is 50-1000 psig. A base catalyst, preferably sodium hydroxide, may be used. Amine alkyl sulfates in a molar ratio of reactants of from 2: 1 to 1: 1. The reaction is preferably carried out with C₈-C₁₄Sodium alkyl sulfate. The ethoxylation and quaternization steps are carried out using conventional conditions and reactants.

In some cases the product formed in reaction scheme 5 is sufficiently soluble in the aqueous-based reaction medium that a gel may form. While the desired product may be recovered from the gel, the latter alternative two-step synthesis scheme 6 may be more desirable in some commercial situations. The first step in scheme 6 is performed as in scheme 5. The second (ethoxylation) step is preferably carried out with ethylene oxide and an acid such as HCl to form a quaternary surfactant. Chlorohydrins (i.e., chlorohydrin) may also be reacted to form the desired bis-hydroxyethyl derivative, as shown below.

For reaction scheme 6, the following parameters summarize optional and preferred reaction conditions for the first step reaction. The first step is preferably carried out in an aqueous medium, typically at a temperature of 100 ℃ and 230 ℃ and a reaction pressure of 50 to 1000 psig. A base, preferably sodium hydroxide, may be used with the HSO formed in the reaction₄ ^-Alternatively, an excess of amine may be used to react with the acid. The molar ratio of amine to alkyl sulfate is generally from 10: 1 to 1: 1.5, preferably from 5: 1 to 1: 1.1More preferably from 2: 1 to 1: 1. In the product recovery step, the desired substituted amine is simply separated as anotherphase from the aqueous reaction medium in which it is insoluble. The second step of the process is carried out under conventional reaction conditions. The further ethoxylation and quaternization to form the bis-AQA surfactant is carried out under standard reaction conditions.

Scheme 7 can optionally be carried out with ethylene oxide under standard ethoxylation conditions, but without the addition of a catalyst, to achieve mono-ethoxylation.

These additional reaction schemes are illustrated in the following examples, where "EO" represents-CH₂CH₂An O-unit. Neutralization of HSO produced in a reaction using an inorganic base, an organic base or an excess of an amine reactant₄。Scheme 6

Scheme 7

Several of the above reactions are further described below for the convenience of the formulator, and not for the purpose of limitation.Synthesis A Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To the autoclave glass liner was added 19.96 grams of sodium dodecyl sulfate (0.06921 moles), 14.55 grams of diethanolamine (0.1384 moles), 7.6 grams of 50% strength by weight NaOH solution (0.095 moles), and 72 grams of distilled water. The glass liner was sealed in a 500ml stainless steel shaking autoclave and heated at 160 ℃. times.180 ℃ for 3-4 hours under 300-. The mixture was cooled to room temperature and the liquid in the glass liner was poured into a 250 ml separatory funnel along with 80 ml chloroform. The funnel was shaken well for a few minutes and then the mixture was allowed to separate. The lower chloroform layer was drained off and the product was obtained after evaporation of the chloroform.Synthesis of B Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

1 mol of sodium dodecyl sulfate was reacted with 1 mol of ethanolamine in the presence of a base in the manner described in Synthesis A. Recovering the 2-hydroxyethyldodecylamine formed and reacting it with 1-chloroethanolTo prepare the title compound.Synthesis C Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To the glass liner of the autoclave were added 19.96 g of sodium dodecyl sulfate (0.06921 mol), 21.37 g of ethanolamine (0.3460 mol), 7.6 g of 50% strength by weight NaOH solution (0.095 mol) and 72 g of distilled water. The glass liner was sealed in a 500ml stainless steel shaking autoclave and heated at 160 ℃ -. The mixture was cooled to room temperature and the liquid in the glass liner was poured into a 250 ml separatory funnel along with 80 ml chloroform. The funnel was shaken well for a few minutes and then the mixture was allowed to separate. The lower chloroform layer was drained off and the chloroform was evaporated to give the product. This product was subsequently reacted with 1 molar equivalent of ethylene oxide at 120-130 ℃ without the addition of a base catalyst to give the desired final product.

The disubstituted amines prepared in the above synthesis may be further ethoxylated in standard manner. The quaternization with alkyl halides to form the bis-AQA surfactants is a conventional reaction.

In light of the foregoing, the following are non-limiting specific examples of bis-AQA surfactants useful herein. It will be appreciated that the degree of ethoxylation of the bis-AQA surfactants referred to herein is reported as an average according to conventional practice for the ethoxylation of nonionic surfactants. This is because ethoxylation generally produces a mixture of materials having different degrees of ethoxylation. Thus, it is notuncommon to report total EO values other than integers, e.g., "EO 2.5", "EO 3.5", etc.Code number R ¹ R ² ApR ³ A′qR ⁴bis-AQA-1C₁₂-C₁₄CH₃EO (also known as Cocoyl methyl EO)₂) bis-AQA-2C₁₂-C₁₆CH₃(EO)₂EO bis-AQA-3C₁₂-C₁₄CH₃(EO)₂(EO)₂(Cococoylmethyl EO)₄) bis-AQA-4C₁₂CH₃EO bis-AQA-5C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-6C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-7C₈-C₁₈CH₃(EO)₃(EO)₂bis-AQA-8C₁₂-C₁₄CH₃(EO)₄(EO)₄bis-AQA-9C₁₂-C₁₄C₂H₅(EO)₃(EO)₃bis-AQA-10C₁₂-C₁₈C₃H₇(EO)₃(EO)₄bis-AQA-11C₁₂-C₁₈CH₃(propoxy) (EO)₃bis-AQA-12C₁₀-C₁₈C₂H₅(Isopropoxy)₂(EO)₃bis-AQA-13C₁₀-C₁₈CH₃(EO/PO)₂(EO)₃bis-AQA-14C₈-C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*bis-AQA-15C₁₀CH₃EO bis-AQA-16C₈-C₁₂CH₃EO bis-AQA-17C₉-C₁₁CH₃-EO 3.5 Pingmean-bis-AQA-18C₁₂CH₃-EO 3.5 mean-bis-AQA-19C₈-C₁₄CH₃(EO)₁₀(EO)₁₀bis-AQA-20C₁₀C₂H₅(EO)₂(EO)₃bis-AQA-21C₁₂-C₁₄C₂H₅(EO)₅(EO)₃bis-AQA-22C₁₂-C₁₈C₃H₇Butyl (EO)₂

^*Ethoxy, optionally capped with methyl or ethyl.

Highly preferred bis-AQA compounds have the formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl and mixtures thereof, preferably C₈、C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof. X is any suitable anion that provides charge balance, preferably chlorine. With respect to the general structure of the bis-AQAs described above, because in preferred compounds R¹Prepared from coconut oil (C)₁₂-C₁₄Alkyl) fraction derived from fatty acids, R²Is methyl, ApR³And A' qR⁴Each is a monoethoxy group, so such preferred compounds are referred to in the above tables as "coconut MeEO₂"or" bis-AQA-1 ".

Other bis-AQA surfactants useful herein include compounds of the formula:wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄An alkyl group; p and q are independently 1-3; r²Is C₁-C₃Alkyl, preferably methyl; x is an anion, especially chlorine or bromine.

Other compounds of the above type include ethoxy groups therein(CH₂CH₂O) units (EO) substituted by butoxy (Bu), isopropoxy [ CH (CH)₃)CH₂O]And [ CH₂CH(CH₃O)]Compounds substituted with units (i-Pr) or with n-propoxy units (Pr), orwith mixtures of EO and/or Pr and/or i-Pr units.non-AQA detersive surfactants

In addition to the bis-AQA surfactant, the compositions of the present invention preferably also contain a non-AQA surfactant. The non-AQA surfactants can include essentially any anionic or nonionic surfactant.Anionic surfactants

Anionic surfactants suitable for use in the present invention are generally used in amounts of 1 to 55% by weight, non-limiting examples of which include conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and C₁₀-C₂₀Primary alkyl ("AS"), branched alkyl, and random alkyl sulfates of (a); chemical formula is CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2, 3) alkyl sulfates wherein x and (y +1) are integers of at least 7, preferably at least 9, and M is a water-soluble cation, especially sodium; unsaturated sulfates, such as oleyl sulfate; c₁₂-C₁₈α sulfonated fatty acid ester, C₁₀-C₁₈A sulfated polyglycoside; c₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS', especially EO 1-7 ethoxy sulfate); and C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO 1-5 ethoxy carboxylates). C may be contained in the total composition₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxide. C₁₀-C₂₀Conventional soaps may also be used. If multivesicular is desired, branched C may be used₁₀-C₁₆Soap. Other commonly used surfactants are listed in standard texts.Nonionic surfactant

Nonionic surfactants suitable for use in the present invention are generally used in amounts of 1-55% by weight, non-limiting examples of which include alkoxylated Alcohols (AE) and alkylphenols, Polyhydroxy Fatty Acid Amides (PFAA), Alkylpolyglycosides (APG), C₁₀-C₁₈A glycerol ether.

More specifically, the condensation products (AE) of primary aliphatic alcohols with secondary alcohols and 1 to 25 moles of ethylene oxide are suitable for use in the present invention as nonionic surfactants. The alkyl chain of the aliphatic alcohol may be linear or branched primary or secondary and typically contains from 8 to 22 carbon atoms. Preferably a product obtained by condensing an alcohol having an alkyl group of 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, with 1 to 10 moles, preferably 2 to 7 moles, most preferably 2 to 5 moles, of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include: tergitol^TM15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide) and Tergitol^TM24-L-6NMW(C₁₂-C₁₄Condensation products of primary alcohols with 6 moles of ethylene oxide, with a narrow molecular weight distribution), both of which are products of the Union Carbide Corporation; neodol^TM45-9(C₁₄-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Neodol^TM23-3(C₁₂-C₁₃Condensation products of linear alcohols with 3 moles of ethylene oxide), Neodol^TM45-7(C₁₄-C₁₅Condensation products of linear alcohols with 7 moles of ethylene oxide) and Neodol^TM45-5(C₁₄-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), products of the Shell chemical company; procter&Product Kyro of Gamble Company^TMEOB(C₁₃-C₁₅Condensation products of alcohols with 5 moles of ethylene oxide); and GenapolLA 030or 050 from Hoechst (C)₁₂-C₁₅Condensation products of alcohols with 3 or 5 moles of ethylene oxide). The preferred HLB range for these AE nonionic surfactants is from 8 to 11, most preferably from 8 to 10. Condensates with propylene oxide and butylene oxide may also be used.

Another preferred class of nonionic surfactants for use in the present invention are polyhydroxy fatty acid amide surfactants of the formula or alkoxylated derivatives thereofWherein R is¹Is H, or C_1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R²Is C_5-31Z is a polyhydroxyhydrocarbyl having a straight-chain hydrocarbyl group with at least 3 hydroxyls directly attached to the hydrocarbyl chain. Preferably, R is¹Is methyl, R²Is straight chain C_11-15Alkyl or C_15-17Alkyl or alkenyl groups such as cocoalkyl, or Z compounds thereof; z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction. Typical examples include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamide. See us 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides may also be used, seeNational patent 5,489,393.

Also suitable for use as nonionic surfactants in the present invention are alkyl polysaccharides, such as those disclosed in U.S. Pat. No. 4,565,647 to Llenado at 21.1.1986, which have a hydrophobic group containing 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a polysaccharide (e.g., polyglycoside) hydrophilic group containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms, such as glucose, galactose, can be used, and galactosyl can be substituted for glucosyl (the hydrophobic group can optionally be attached at 2-,3-, 4-, etc. positions, thereby yielding a glucose or galactose as opposed to a glucoside or galactoside). The sugar linkage may be, for example, between one position of the additional sugar unit and the 2-, 3-, 4-, and/or 6-position of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula:

R²O(C_nH_2nO)_t(sugar base)_xWherein R is²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; x is 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably glucoseAnd (4) derivative formation. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed and then reacted with glucose or a source of glucose to form the glucoside (attachment at the 1-position). Additional glycosyl units can then be attached between their 1-position and the 2-, 3-, 4-and/or 6-position (predominantly preferably the 2-position) of the preceding glycosyl units.

Polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols are also suitable as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in a straight or branched chain configuration with alkylene oxides. In a preferred embodiment, the amount of ethylene oxide used is equal to 2 to 25 moles, more preferably 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Such commercially available nonionic surfactants include Igepal sold by the GAF Corporation^TMCO-630, and Rohm&Triton soldby the Hoas Company^TMX-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic backbone formed by the condensation of propylene oxide and propylene glycol are also suitable for use in the present invention as auxiliary nonionic surfactants. Phobic of these compoundsThe molecular weight of the water fraction is preferably 1500-. The addition of a polyoxyethylene moiety to this hydrophobic moiety increases the water solubility of the molecule as a whole and the product remains liquid until the polyoxyethylene content reaches 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of such compounds include certain commercial products Pluronic marketed by BASF^TMA surfactant.

The condensation products of ethylene oxide with the products formed by the reaction of propylene oxide and ethylenediamine are also suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and has a molecular weight of typically 2500-3000. The hydrophobic layerThe portion is condensed with ethylene oxide to such an extent that the condensation product contains 40 to 80% by weight of polyoxyethylene and has a molecular weight of 5,000-11,000. Examples of such nonionic surfactants include Tetronic, a commercial product sold by BASF^TMA compound is provided.Auxiliary cationic surfactants

Suitable cationic surfactants are preferably water-dispersible compounds having surfactant properties comprising at least one ester (i.e., -COO-) linkage and at least one positively charged group.

Other suitable cationic surfactants include those selected from mono-C₆-C₁₆Preferably mono C₆-C₁₀N-alkyl or alkenyl ammonium quaternary ammonium surfactants in which the remaining N position is substituted with methyl, hydroxyethyl or hydroxypropyl. Other suitable cationic ester surfactants, including choline ester surfactants, are disclosed as examples in U.S. patent nos. 4,228,042, 4,239,660, and 4,260,529.Optionally added detergent ingredients

Various other optional added components that may be used in the compositions of the present invention are illustrated below, but are not intended to be limiting thereof.Auxiliary bleaching agent

The detergent compositions of the present invention may contain an auxiliary bleaching agent. Such bleaches are typically present at levels of from 1 to 20%, more typically from 3 to 15% of the detergent composition, especially for fabric laundering.

Other suitable bleaching agents include chlorine and photoactivated bleaching agents including sulfonated zinc and/or aluminum phthalocyanines. See U.S. Pat. No. 4,033,718 to Holcomb et al, 7/5/1977. If used, detergent compositions will generally contain from 0.025 to 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.Bleach activators

A preferred component of the compositions of the present invention is a bleach activator. The bleach activator is typically present in an amount of from 0.1 to 60%, more typically from 0.5 to 40% of the bleach composition comprising bleach plus bleach activator.

Peroxygen bleaches, perborates, and the like, are preferably used in combination with bleach activators, which result in the in situ generation (i.e., during washing) of the peroxyacid or peracid corresponding to the bleach activator in aqueous solution. Various non-limiting examples of activators are disclosed in U.S. Pat. No. 4,915,854 and U.S. Pat. No. 4,412,934, both issued to Mao et al on 4/10 of 1990. Nonoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are representative, and mixtures thereof may also be used. Other typical bleaching agents and activators suitable for use in the present invention can also be found in U.S. Pat. No. 4,634,551.

In another preferred case, the preformed peracid is added directly to the composition. It is also contemplated that the composition contains a mixture of a hydrogen peroxide source and a bleach activator, and a preformed peracid.

Highly preferred amido-derived bleach activators are compounds of the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl radical having 6 to 12 carbon atoms, R²Is alkylene having 1 to 6 carbon atoms, R⁵Is H or an alkyl, aryl or alkaryl group of 1 to 10 carbon atoms and L is any suitable leaving group. A leaving group is any group displaced from the bleach activator due to the nucleophilic attack of the perhydrolytic anion on the bleach activator. One preferred leaving group is a phenylsulphonic group.

Examples of preferred bleach activators of the above formula include (6-octanoylaminohexanoyl) oxybenzene sulfonate, (6-nonanoylaminocaproyl) oxybenzene sulfonate, (6-decanoylaminohexanoyl) oxybenzene sulfonate and mixtures thereof, see U.S. Pat. No. 4,634,551, which is incorporated herein by reference.

Another class of bleach activators includes the benzoxazine-type activators disclosed in U.S. Pat. No. 4,966,723(Hodge et al, 1990, 10/30), which is incorporated herein by reference. One highly preferred benzoxazine-type activator is:

yet another preferred class of bleach activators comprises acyllactamsAmine activators, especially acyl caprolactams and acyl valerolactams of the formula:wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group having from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, capryl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, caprylyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam, and mixtures thereof. See also U.S. patent 4,545,784 to Sanderson, 10/8/1985, which discloses adsorption of acyl caprolactams, including benzoyl caprolactam, into sodium perborate.Builder

Detergent builders may optionally, but preferably, be included in the compositions of the present invention to assist in controlling the hardness of minerals (especially Ca and/or Mg) in the wash water or to facilitate removal of particulate soils from surfaces. Builders can act by a variety of mechanisms, including by ion exchange and by providing a surface that favors the precipitation of hardness ions over the surface of the article being cleaned, forming soluble or insoluble complexes with hardness ions. Builder levels can vary widely depending on the end use and physical form of the composition. Builder detergents typically contain at least 1% builder. Liquid formulations typically contain from 5 to 50%, more usually from 3 to 35% builder. Granular formulations typically contain 10-80%, more usually 15-50% builder by weight of the detergent composition. Lower or higher levels of builder are not excluded. For example, certain detergent additives or high surfactant formulations may be free of builders.

Suitable builders may be selected from phosphates and polyphosphates, especially sodium salts; silicates including water-soluble and hydrated solid types, and including silicates having chain, layered or three-dimensional structures and amorphous solid or liquid-free types; carbonates, bicarbonates, sesquicarbonates, and other carbonate minerals other than sodium carbonate or sodium sesquicarbonate; an aluminosilicate; organic mono-, di-, tri-and tetracarboxylic acid salts, especially water-soluble non-surfactant carboxylates in the form of the acid, sodium, potassium or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic; and phytic acid. They may be supplemented with borates to buffer the pH, or with sulfates (especially sodium sulfate) and any fillers or carriers that may be important in the construction of stable surfactant and/or builder-containing detergent compositions.

Builder mixtures, sometimes referred to as "builder systems", may be used, typically containing two or more conventional builders, optionally supplemented with chelating agents, pH buffers or fillers, but these are generally calculated separately later when describing the amounts of each material in the present invention. Preferred adjunct systems are generally formulated in a surfactant to builder weight ratio in the range of from 60: 1 to 1: 80 in view of the relative amounts of surfactant to builder in the detergent of the present invention. In certain preferred laundry detergents this ratio is from 0.90: 1.0 to 4.0: 1.0, more preferably from 0.95: 1.0 to 3.0: 1.0.

Phosphorus-containing detergent builders that are often preferred for use in legally permissible locations include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, examples of which are the tripolyphosphates, pyrophosphates,glassy polymetaphosphates and phosphonates.

Suitable silicate builders include alkali metal silicates, especially SiO₂∶Na₂Liquid and solid silicates having an O ratio in the range of 1.6: 1 to 3.2: 1, including (especially for use in automatic dishwashing machines) PQ Corp, Britisil^_Sold solid hydrated silicates of ratio 2, e.g. BRITESSIL H₂O; and layered silicates such as those described in us patent 4,664,839 (12/5 1987, h.p. rieck). NaSKS-6 (sometimes abbreviated as "SKS-6") is a crystalline, layered, aluminum-free silicate sold by Hoechst having a delta-Na structure₂SiO₅Form is shown. Particularly preferred for use in granular laundry detergents. The preparation method is as followsDE-A-3,417,649 and DE-A-3,742,043. Other phyllosilicates, e.g. of the formula NaMSi_xO_2x+1·yH₂Silicates of O, where 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, are also useful in the present invention, the layered silicates of Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, which are layered silicates in the α, β and γ forms, respectively.

Also suitable for use in the present invention are synthetic crystalline ion exchange materials or hydrates thereof, which have a chain structure and whose composition in anhydrous form can be represented by the general formula:_xM₂O·_ySiO₂·_zm 'O, where M is Na and/or k, M' is Ca and/or Mg, y/x is 0.5-2.0, and z/x is 0.005-1.0, as described in U.S. Pat. No. 5,427,711(Sakaguchi et al, 27.6.1995).

Suitable carbonate builders include the alkaline earth and alkali metal carbonates as described in German patent application 2,321,001 (published 1973, 11/15), but sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as natural soda or any suitable multiple salt of sodium carbonate with calcium carbonate, for example 2Na when anhydrous₂CO₃、CaCO₃Those salts of (a), even calcium carbonates, including calcite, aragonite and nepheline, especially those forms having a surface area ratio up to that of calcite, may be used as seed particles or in synthetic detergent bars.

Aluminosilicate builders are particularly useful in granular detergents, but may also be incorporated into liquids, pastes or gels. Suitable for the present invention are compounds of the empirical formula [ M_z(AlO₂)_z(SiO₂)_v]·_xH₂O, wherein z and v are integers of at least 6, the molar ratio of z to v is from 1.0 to 0.5, and x is an integer from 15 to 264. The aluminosilicate may be crystalline or amorphous, naturally occurring or syntheticAnd (4) preparing. A process for the preparation of aluminosilicates is described in U.S. Pat. No.3,985,669 (Krummel et al, 12/10 1976). Preferred synthetic crystalline aluminosilicate ion exchange materials are commercially available as Zeolite A, Zeolite P (B), Zeolite X, and so-called Zeolite MAP which differs to some extent from Zeolite P. Natural types including clinoptilolite may also be used. Zeolite A has the chemical formula Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O, where x is from 20 to 30, especially 27. Dehydrated zeolites (x ═ 0 to 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1 to 10 microns.

Suitable organic builders include polycarboxylate compounds, including water-soluble non-surfactant di-and tri-carboxylates. More typically, the polycarboxylate builder has a plurality of carboxyl groups, preferably at least 3 carboxyl groups. Carboxylate builders can be formulated in a variety of forms which are acidic, partially neutral, neutral or overbased. When in salt form, alkali metal salts, such as sodium, potassium and lithium salts, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinate, as described in U.S. Pat. No.3,128,287 (Berg, 1964, 4-7) and U.S. Pat. No.3,635,830 (1972, 1-18, Lamberti); U.S. Pat. No. 4,663,071(Bush et al, 5.5.1987) to "TMS/TDS" builders; and other ether carboxylates, including cyclic and alicyclic compounds, such as those disclosed in U.S. patents 3,923,679, 3,835,163, 4,158,635, 4,120,874, and 4,102,903.

Other suitable builders are ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid; carboxymethoxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3, 5-tricarboxylic acid, carboxymethoxysuccinic acid, and soluble salts thereof.

Citrates, such as citric acid and soluble salts thereof, are important carboxylate builders for, for example, high performance liquid detergents due to their availability from renewable sources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolites and/or layered silicates. Oxodisuccinates are also particularly useful in such compositions or combinations.

Where permitted for use, especially in the case of soap bars formulated for hand washing, alkali metal phosphates such as sodium tripolyphosphate, pyrophosphate and phosphate may be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates, such as those in U.S. Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137, may also be used and may have desirable antifouling properties.

Some detersive surfactants or short chain homologues thereof also have a builder effect. For formulation clarity, these materials are added to the detersive surfactant if they have surfactant power. Examples of preferred types having a builder function are: 3, 3-dicarboxy-4-oxa-1, 6-adipate and related compounds disclosed in U.S. patent 4,566,984(Bush, 28/1 1986). The butanedioic acid builder comprises C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. The butanedioic acid builder also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Lauryl succinate is described in european patent applications 86200690, 5/0,200,263 (published on 5.11.1986). Fatty acids, e.g. C₁₂-C₁₈Monocarboxylic acids, either alone or together with the above-mentioned builders (especially citrate and/or succinate builders), may be added to the composition as surfactant/builder materials to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226(Crutchfield et al, 3.13.1979) and U.S. Pat. No.3,308,067 (Diehl, 3.7.1967). See also U.S. patent 3,723,322 to Diehl.

Other types of inorganic builder materials that can be used are of the formula (M)_x)_iCa_y(CO₃)_zWhereinx and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_iAre cationic, at least one of which is water-soluble and satisfies the equation ∑_i1-5(Xi times M)_iThe valence of) +2y ═ 2z, so that there is a neutral or "balanced" charge in the formula.These builders are referred to herein as "mineral builders". Water of hydration or anions other than carbonate may be added as long as the overall charge remains balanced or neutral. The charge or valence shadow response of these anions is added to the right of the above equation. Preferably there is present a water soluble cation selected from the group consisting of hydrogen, water soluble metals, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, most preferably sodium and potassium. Non-limiting examples of non-carbonate anions include anions selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. Preferred builders of this type are in their simplest form selected from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And mixtures thereof. A particularly preferred material for the builders described herein is Na in any crystalline modification₂Ca(CO₃)₂. Examples of the classes of suitable builders defined above also include any of the following minerals or combinations thereof, in natural or synthetic form: afghantianite, natrii calcium, kainite Y, bismuthate carbonate, colemanite, strontianite, kalkovite, cancrinite, cerite, canasite, kacrinite, strontite, potasite, Ferrisurte, kakakainite, merrisnite, kaempferite, nobilenite, lepersonite, pinochite, Girvasite, ilmenite, canasite, Kamphaugite Y, bismuthate, Khannesite, Lepersonnite GD, eucryptite, barite Y, microcarprite, tellite, nycite, nystolite, nerchinarete, Remonditecete, savatite, uraninite, canadensite, cancrinite, etc,Aluminosilphite, synusite, sylvite, sepiolite, cancrinite and Zemkorite. Preferred mineral forms include nerolides, canasite and canasite.Enzyme

The detergent compositions of the present invention may contain enzymes for a variety of purposes including removal of protein, carbohydrate or triglyceride based stains from substrates, prevention of dye transfer from fabric washing, and for fabric refreshment. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, for example of plant, animal, bacterial, fungal or yeast origin. The optimum choice is influenced by factors such as pH-activity and/or stability optima, thermostability and stability towards active detergents, builders. Bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred in this regard.

As used herein, "detersive enzyme" refers to any enzyme that has a cleaning, stain-removing or other beneficial effect in laundry, hard surface cleaning or personal care detergent compositions. Preferred detersive enzymes are hydrolases, such as proteases, amylases, and lipases. Preferred enzymes for laundry use include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred enzymes for use in automatic dishwashing machines are amylases and/or proteases.

Enzymes are typically incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" means any amount that produces a cleaning, stain removing, whitening, deodorizing or refreshing effect on a substrate such as fabric, dishware, etc. In practice, typical amounts are up to 5 mg, more usually 0.01 mg to 3 mg, of active enzyme per gram of detergent composition for current commercial preparations. In other words, the compositions of the invention generally comprise from 0.001 to 5%, preferably from 0.01 to 1%, by weight of the commercial enzyme preparation. The protease enzyme is typically present in such commercial preparations in an amount sufficient to provide 0.005 to 0.1 Anson Units (AU) of activity per gram of composition. For certain detergents, such as those in automatic dishwashing machines, it may be desirable to increase the active enzyme content in commercial formulations in order to reduce the total amount of non-catalytically active material, thereby improving spotting/filming or other end effects. Higher active levels may also be desirable in high concentration detergent formulations.

Suitable examples of proteases are subtilisins derived from specific strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from Bacillus, has maximum activity over the entire pH range of 8-12, is developed by Novo Industries A/S (hereinafter "Novo") of Denmark and is used as ESPERASE^_And (5) selling. The preparation of this and similar enzymes is described in British patent 1,243,784 (Novo). Other suitable proteases include ALCALASE by Novo^_And SAVINASE^_And MAXATASE from International Bio-Synthesis, Inc. (the Netherlands)^_(ii) a And the proteases A disclosed in EP130,756A (9/1/1985) and the proteases B disclosed in EP 303,761A (28/4/1987) and EP130,756A (9/1/1985). See also the high pH protease from Bacillus NCIMB 40338 described in WO 9318140A (Novo). In WO 9203529A (Novo) enzyme-containing detergents are mentioned which contain a protease, one or more other enzymes, and a reversible protease inhibitor. Other preferred proteases include WO 9510591A (Procter)&Gamble). If desired, an apparatus such as WO 9507791 (Procter)&Gamble) and increased hydrolysis may be used. A protease of the recombinant trypsin type suitable for use in the detergents of the invention is described in WO 9425583 (Novo).

In more detail, a particularly preferred Protease referred to as "Protease D" is a carbonyl hydrolase having an amino acid sequence not found in nature, as described in A.Baeck et al, U.S. patent application 08/322,676 entitled "Protease-containing cleaning compositions", and C.Ghosh et al, U.S. patent application 08/322,677 entitled "Protease-containing bleaching compositions" (both filed 13.10.1994), which enzyme is a precursor carbonyl hydrolase having a different amino acid substituted for the equivalent of position +76 in the carbonyl hydrolase, and preferably also encoded as +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +204, + 32, +218, and/L., +265, and/or +274 at one or more amino acid residue positions.

Amylases suitable for the present invention, especially but not exclusively for automatic dishwashing machines, include, for example, the α -amylase mentioned in British patent 1,296,839(Novo), the RAPIDASE of International Bio-Synthesis, Inc^_TERMAMYL OF NOVO^_. FUNGAMYL of Novo^_It is particularly suitable. Enzyme engineering for improving stability (e.g., oxidative stability) is known. See, for example, journal of biochemistry (j. biological Chem.),260(11) 6 months 1985, 6518 and 6521. Certain preferred embodiments of the compositions of the present invention may use TERMAMYL marketed in 1993 in detergents such as automatic dishwashing detergents^_These preferred amylases are characterized by "increased stability", as measured against the reference amylase identified above, as being measurably improved in at least one or more of oxidative stability, e.g., hydrogen peroxide/tetraacetylethylenediamine, in a buffer at pH 9-10, thermal stability, e.g., at common washing temperatures such as 60 ℃, or alkaline stability, e.g., at pH 8-11. stability can be measured using any of the technical tests disclosed in the art, e.g., see the references disclosed in WO 9402597The enzyme comprises (a) an amylase of WO 9402597(Novo, 2.3.1994) cited above, a further example being the substitution of the amylase located in Bacillus licheniformis α (named TERMAMYL) with alanine or threonine (preferably threonine)^_) A mutant which forms themethionine residue at position 197, or a homologous positional variation of a similar parent amylase (e.g., a Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearothermophilus amylase); (b) amylases with improved stability, e.g. GenencorInternational is described in an article entitled "antioxidative α -Amylase" by C.Mitchinson at the annual meeting of the American chemical society of 207 (13-17 months of 1994). it is mentioned in this document that α -amylase is inactivated by bleach in automatic dishwashing detergents, but the Genencor company has produced an amylase with improved oxidative stability from Bacillus licheniformis NCIB 8061. methionine (Met) is identified as the most likely group to be modified.Met is substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438 to give specific variants, particularly important being M197L and M197T, M197T being the most stable expression variant^_And SUNLIGHT^_Is determined in (a); (c) particularly preferred amylases of the invention include amylase variants additionally modified in the direct parent as described in WO 9510603A, available as DURAMYL from Novo corporation, assignee^_And (4) obtaining the product. Other particularly preferred stability-enhancing amylases include those mentioned in WO 9418314(Genencor International) and WO 9402597 (Novo). Any other amylase with improved oxidative stability may be used, e.g., an amylase derived by site-directed mutagenesis from a known chimeric, hybrid or simple mutant parent form of a commercially available amylase. Other preferred amylase modification modifications are also achievable, see WO 9509909 (Novo).

Other amylases include those mentioned in WO 95/26397 and co-pending application PCT/DK 96/00056 to Novo Nordisk. Specific amylases useful in the detergent compositions of the invention include the use of Phadebas at a temperature in the range of 25-55 ℃ and a pH in the range of 8-10^_α -Amylase Activity test shows higher specific activity than Termamyl^_At least 25% α -amylase (Phadebas, supra)^_α -amylase activity test is described on pages 9-10 of WO 95/26397.) the compositions also include α -amylases which are at least 80% homologous to the amino acid sequences listed in the tables of SEQ ID in the references, these enzymes are preferably incorporated into laundry detergent compositions at a level of from 0.00018 to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024 to 0.048% pure enzyme by weight of the total composition.

Cellulases usable in the present invention include bacterial type and fungal type, preferably having a pH optimum of 5 to 9.5. U.S. Pat. No. 4,435,307 (Barbesgord et al, 3/6 1984) discloses suitable fungal cellulases from Pythium anomaly or Pythium strain DSM 1800 or a fungus belonging to the genus Aeromonas which produces cellulase 212, and cellulases extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME^_And CELLUZYME^_(Novo) is particularly suitable. See also WO 9117243 (Novo).

Lipases suitable for use in detergents include those prepared from microorganisms of the Pseudomonas family, for example Pseudomonas stutzeri ATCC 19,154, as described in GB 1,372,034. See also lipase in Japanese patent application (published 24.2.1978). This Lipase is available from Amano Pharmaceutical co.ltd (Nagoya) in japan under the trade name Lipase P "Amano" or "Amano-P". Other suitable lipases include Amano-CES, which is a lipid ester obtained from Chromobacterium viscosum, e.g., the lipolytic variant of Chromobacterium viscosum, commercially available from Toyo Jozo Co. (Tagata) of Japan; U.S. biochemical Corp. (usa) and Disoynth Co. (netherlands), and lipases from pseudomonasgladioli. Lipolase from Humicola lanuginosa sold by Novo Inc^_The enzyme (see EP 341,947) is a preferred lipase for use in the present invention. Lipase and amylase variants stabilized against peroxidase are described in WO 9414951 (Novo). See also WO 9205249 and RD 94359044.

Despite the extensive literature on lipases, a large number have been described so farOnly lipases derived from Humicola lanuginosa and prepared in Aspergillus oryzae as host have found widespread use as additives for fabric washing products. As mentioned above, it can be prepared by Novo Nordisk as Lipolase^TMThe trade name of (1) was purchased. To optimize the antiplaque properties of Lipolase, Novo Nordisk has made many variations. As described in WO 92/05249, the D96L variant of native Humicola lanuginosa lipase increased the antiplaque efficacy of 4.4 fold over the wild type lipase (compare enzymes in amounts ranging from 0.075 to 2.5 mg protein per liter). The study report published by Novo Nordisk, 3.10.1994, No.35944, indicates that the lipase variant (D96L) can be added in an amount corresponding to 0.001-100 mg per liter of wash liquor (5-500,000 LU/liter). An advantage of the present invention is that whiteness maintenance of fabrics in detergent compositions containing AQA surfactants is improved with low levels of D96L variants in the manner disclosed herein, especially where D96L is used at 50-8500 LU per liter wash liquor.

Cutinases suitable for use in the present invention are described in WO 8809367A (Genencor).

Peroxidases can be used in conjunction with a source of oxygen (e.g., percarbonate, perborate, hydrogen peroxide, etc.) to "solution bleach" or to prevent transfer of dyes or pigments removed from the carrier during washing to other carriers present in the wash liquor. Known peroxidases include horseradish peroxidase, ligninases and haloperoxidases such as chlorine or bromine peroxidase. Detergent compositions containing peroxidase are disclosed in WO 89099813A (19.10.1989, Novo) and WO 8909813A (Novo).

In WO 9307263A and WO 9307260(Genancor International), WO8908694A (Novo) and US 3,553,139(1971, 5.1, McCarty et al) also disclose a number of enzymatic materials and methods for their incorporation into synthetic detergent compositions. Various enzymes are also disclosed in US4,101,457(Place et al, 18/7 1978) and US4,507,219 (Hughes, 26/3 1985). Enzyme materials suitable for use in liquid detergent formulations and their incorporation in such formulations are disclosed in US4,261,868 (Hora et al, 4/14 1981)And (4) adding method. Enzymes for detergents can be stabilized in various ways. Enzyme stabilization methods are disclosed and exemplified in U.S. Pat. No.3,600,319 (8/17/1971, Gedge et al), EP 199,405 and EP 200,586 (10/29/1986, Venegas). Enzyme stabilization systems are also described in U.S. Pat. No.3,519,570. WO 9401532A (Novo) describes a Bacillus strain AC13 which can be used to produce proteases, xylanases and cellulases.Enzyme stabilizing system

The enzyme-containing compositions of the present invention may optionally contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, and most preferably from about 0.01% to about 6%, by weight of the enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with detersive enzymes. Such stabilizing systems may be inherently provided by other formulation actives or may be added in addition, for example by the formulator or by the manufacturer of the detergent ready-to-use enzyme. Such stabilizing systems may contain, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, alkyl boric acids, and mixtures thereof, and are designed to address different stabilization issues depending on the type and physical form of the detergent composition.

One method of stabilization is to use water soluble sources of calcium and/or magnesium ions in the finished composition to provide these ions to the enzyme. Calcium ions are generally more effective than magnesium ions, and calcium is preferred if only one type of cation is used. Typical detergent compositions, especially liquid compositions, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished product, but may vary depending on a variety of factors, including the multiplicity, type and amount of enzyme added. Preferably, water-soluble calcium or magnesium salts are used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the calcium salts listed can be used. It is of course useful to further increase the calcium and/or magnesium content, for example to promote the grease-dissolving action of certain types of surfactants.

Another method of stabilization is the use of borates. See U.S. Pat. No. 4,537,706 to Severson. When borate stabilizers are used, they are used in amounts of up to 10% or more by weight of the composition, but more commonly, boric acid or other borate compounds (e.g., borax or orthoborate) in amounts of up to about 3% by weight are suitable for use in liquid detergents. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid and the like may be used in place of boric acid, and the total boron content of the detergent composition may be reduced by using these substituted boron derivatives.

Stabilizing systems for certain cleaning compositions, such as automatic dishwashing compositions, may also contain from 0 to about 10%, preferably from about 0.01 to 6%, by weight, of chlorine bleach scavengers toprevent chlorine bleach species in many water sources from attacking and inactivating the enzymes, especially under alkaline conditions. Although the chlorine content of water may be small, typically about 0.5-1.75ppm, the chlorine present in the total water volume that is contacted with the enzyme during, for example, dishwashing or fabric laundering can be substantial; therefore, the stability of the enzyme to chlorine may be problematic in use. Since perborates or percarbonates are capable of reacting with chlorine bleaches, it is no longer necessary in most cases to additionally use stabilizers against chlorine, but improved results are possible as a result of their use. Suitable chlorine scavenger anions are generally known and readily available and, if used, may be ammonium cation-containing sulfites, bisulfites, thiosulfites, thiosulfates, iodide salts, and the like. Antioxidants such as carbamates, ascorbates, and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof may also be used. Furthermore, specific enzyme inhibition systems may be incorporated to maximize the compatibility of the different enzymes. Other conventional scavengers, such as bisulfates, nitrates, chlorides, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof, may be used if desired. In general, because the chlorine scavenger function can be performed by other components (e.g., hydrogen peroxide sources) listed under the more well known functional names, it is not necessary to add additional chlorine scavenger except in the context of the present inventionCompounds that exert this function to the desired degree are not present in enzyme-containing embodiments; even in the latter case, the addition of a scavenger is only provided for optimum effect. In addition, the formulator should employ the ordinary skill of a chemist to avoid the use of any enzyme scavenger or stabilizer that is not substantially compatible with the other active ingredients at the time of formulation. In the case of the use of ammonium salts, such salts may simply be mixed with the detergent composition, but tend to adsorb water and/or give off ammonia on storage. Thus, if present, such materials are preferably protected within the particles as described in U.S. Pat. No. 4,652,392(Baginski et al).Polymer scale remover

Known polymeric soil release agents (hereinafter "SRA") may optionally be used in the detergent compositions of the present invention. When used, the SRA will generally comprise from 0.01 to 10.0%, usually from 0.1 to 5%, preferably from 0.2 to 3.0% by weight of the composition.

Preferred SRAs generally have a hydrophilic segment that hydrophilizes the surface of hydrophobic fibers such as polyesters and nylons, and a hydrophobic segment that deposits on the hydrophobic fibers and remains adhered thereto throughout washing and rinsing, thereby anchoring the hydrophilic segment. This makes stains occurring after treatment with SRA more easily washed away in later washing processes.

SRAs can include many charged, such as anionic or even cationic (see us patent 4,956,447), as well as uncharged monomeric units, the structure of which can be linear, branched, or even star-shaped. They may include end-capping moieties that are particularly effective in controlling molecular weight or altering physical or surface active properties. The structure and charge distribution can be designed for different fiber or textile types and for different detergent or detergent additive products.

Preferred SRAs include oligomeric terephthalates, which are generally prepared by at least one transesterification/oligomerization process, often using a metal catalyst such as a titanium (IV) alkoxide. Other monomers that can be incorporated into the ester structure via one, two, three, four or more positions can be used in the preparation of such esters, certainly without forming a densely crosslinked overall structure.

Suitable SRAs include: sulfonated products of substantially linear ester oligomers consisting of an oligomeric ester backbone of terephthaloyl and oxyalkylene repeat units and sulfonate end groups derived from allyl groups covalently bonded to the backbone, as described, for example, in U.S. patent 4,968,451(1990 11/6, j.j.scheibel and e.p.gosselink). Such ester oligomers can be prepared by the following method: (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") in a two-step transesterification/oligomerization step, and (c) reacting the product of (b) with sodium metabisulfite in water; the non-ionically end-capped 1, 2-propanediol terephthalate/polyoxyethylene ester polyesters of U.S. Pat. No. 4,711,730 (12/8/1987, Gosselink et al), such as those made by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) ("PEG"); some or all of the anionic-terminated oligoesters of U.S. Pat. No. 4,721,580 (Gosselink, 26.1.1988), such as oligomers formed from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate; non-ionic end-capped block polyester oligomers of U.S. Pat. No. 4,702,857 (Gosselnk, 27.10.1987), prepared, for example, from DMT, Me-capped PEG and EG and/or PG, or DMT, EG and/or PG, Me-capped PEG and dimethyl 5-sulfoisophthalate sodium salt; and anion (especially sulfoaroyl) terminated terephthalates in U.S. Pat. No. 4,877,896 (31/10/1989, Maldonado, Gosselink et al); the latter are typical SRAs used in both laundry and fabric finishing products, examples of which are ester compositions made from monosodium salt of m-sulfobenzoic acid, PG and DMT, and optionally, but preferably, PEG (e.g., PEG 3400).

SRA also includes simple block copolymers of ethylene terephthalate or propylene terephthalate with polyoxyethylene or polyoxypropylene terephthalates, as described in U.S. patent 3,959,230(Hays, 25.5.1976) and U.S. patent 3,893,929 (basedur, 8.7.1975); cellulose derivatives such as the hydroxyether cellulose polymers sold under the trade name METHOCEL by Dow; andC₁-C₄alkyl celluloses and C₄Hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093(1976, 12/28, Nicol, et al). Suitable SRA's characterized by a poly (vinyl ester) hydrophobic segment include poly (vinyl esters), such as C₁-C₆Vinyl esters, preferably poly (vinyl acetate), graft copolymers formed on polyoxyalkylene backbones. See European patent application 0219048 to Kud et al, 4/22, 1987. Examples of commercial products include SOKALAN SRA, such as SOKALAN HP-22, available from BASF (Germany). Other SRAs are polyesters containing 10-15% by weight of ethylene terephthalate and 90-80% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol having an average molecular weight of 300-5000. Commercial examples include ZELCON 5126 from Dupont and mileas from ICI.

Another preferred SRA is of the empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁The oligomer of (a) contains terephthaloyl (T), Sulfonated Isophthaloyl (SIP), oxyethylene and oxy-1, 2-propylene (EG/PG) units, and is preferably terminated with a capping group (CAP), and is most preferably terminated with a modified isethionate group, such as one sulfonated isophthaloyl unit, 5 terephthaloyl units, a proportion of oxyethylene and oxy-1, 2-propyleneoxy units (preferably about 0.5: 1 to about 10: 1), and two end-capping units derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate in one oligomer. TheSRA preferably also contains from 0.5% to 20% by weight of the oligomer of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzene sulphonate or a compound selected from the group consisting of xylene, cumene and toluene sulphonate or mixtures thereof, which stabilizers or regulators are added to the synthesis vessel, as described in U.S. Pat. No. 5,415,807 to Gosselnk, Pan, Kallett and Hall, 5/16.1995. Suitable monomers for the above SRA include sodium 2- (2-hydroxyethoxy) ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG, and PG.

Yet another preferred class of SRA are oligomeric esters comprising (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxy sulfonate esters, polyhydroxy sulfonate esters, a unit that is at least trifunctional thereby forming ester linkages and producing a branched oligomer backbone, and mixtures thereof; (b) at least one terephthaloyl unit; and (c) at least one unsulfonated 1, 2-oxyalkylene oxy unit; and (2) one or more end capping units selected from nonionic end capping units, anionic end capping units such as alkoxylated (preferably ethoxylated) isethionate, alkoxylated propanesulfonic, alkoxylated propanedialkanoyl, alkoxylated phenolsulfonic, sulfoaroyl derivatives thereof and mixtures thereof. Preferred such esters have the empirical formula:

{ (CAP) x (EG/PG) y ' (DEG) y ' (PEG) y _ (T) z (SIP) z ' (SEG) q (B) m } wherein CAP, EG/PG, PEG, T and SIP are as defined above. (DEG) represents a di (oxyethylene) oxy unit; (SEG) represents units derived from the sulfoethyl ether of glycerol and related units; (B) represents a branching unit which is at least trifunctional, whereby ester bonds are formed, resulting in a branched oligomer backbone; x is about 1 to 12; y' is about 0.5 to 25; y "is 0 to about 12; y _ is 0 to about 10; the sum of y' + y "+ y _ is about 0.5 to 25; z is about 1.5 to 25; z' is 0 to about 12; the sum of z + z' is about 1.5 to 25; q is about 0.05 to 12; m is about 0.01 to 10; x, y ', z', q and m represent the average number of moles of the corresponding units per mole of ester having a molecular weight of about 500 to 5000.

Preferred SEG and CAP monomers for the above esters include sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3"), and homologs and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol. Such preferred SRA esters include the products of the transesterification and oligomerization of sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate and/or sodium 2- [ 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG, and PG using suitable Ti (IV) catalysts, as represented by (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is (Na +)^-O₃S-[CH₂CH₂O]3.5) -, B is a unit derived from glycerol, in total waterAfter decomposition the EG/PG molar ratio, as determined by gas chromatography, was about 17: 1.

Other types of SRAs include: (I) nonionic terephthalates formed by linking polymeric ester structures using diisocyanate coupling agents, see U.S. Pat. No. 4,201,804(Violland et al) and U.S. Pat. No. 4,240,918(Lagasse et al); and (II) SRAs with carboxylate end groups formed by adding trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate. By proper selection of the catalyst, trimellitic anhydride forms a chain bond with the polymer terminus through its isolated acid ester rather than by opening the anhydride linkage. Either nonionic or anionic SRA can be used as the starting material, so long as it isThey have esterifiable hydroxyl end groups. See U.S. patent 4,525,524(Tung et al); (III) urethane-linked anionic terephthalate-based SRAs, see U.S. Pat. No.4,201,824(Violland et al); (IV) poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including nonionic and cationic polymers, see U.S. Pat. No. 4,579,681(Ruppert et al); (V) graft copolymers formed by grafting acrylic monomers on sulfonated polyesters, in addition to the SOKALAN type from BASF corporation, these SRAs are said to have similar soil release and anti-redeposition activity to known cellulose ethers, as described in EP 279,134A (Rhone-Poulenc Chemie) in 1988; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on proteins such as casein, see EP 457,205A (BASF, 1991); and (VII) polyester-polyamide SRA made by condensation of adipic acid, caprolactam and polyethylene glycol, which is particularly useful for treating polyamide fabrics, see Beven et al, DE 2,335,044(Unilever N.V., 1974). Other suitable SRAs are described in us patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.Soil scale removal/anti-redeposition agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having soil release and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from 0.01 to 10.0% by weight of a water-soluble ethoxylated amine; liquid detergents generally contain 0.01 to 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. patent 4,597,898 issued to Vander Meer on 7/1 of 1986. Another preferred class of soil release/anti-redeposition agents are the cationic compounds disclosed in european patent application 111,965(Oh and Gosselink, published 1984 on 27.6.4). Other soil release/anti-redeposition agents that may be used include ethoxylated amine polymers disclosed in european patent application 111,984(Gosselink, published 1984 on 27.6); zwitterionic polymers disclosed in European patent application 112,592(Gosselink, published 7/4/1984); and amine oxides disclosed in U.S. patent 4,548,744(Connor, 22/10/1985). Other soil release and/or anti-redeposition agents known in the art may also be used in the compositions of the present invention. See us4,891,160 (Vander Meer, 1990, 1/2) and WO 95/32272(1995, 11/30). Another preferred class of antiredeposition agents includes carboxymethyl cellulose (CMC) materials. These materials are well known in the art.Polymeric dispersants

Polymeric dispersants may advantageously be used in the compositions of the present invention, especially in the presence of zeolite and/or layered silicate builders, in amounts of from 0.1 to 7% by weight. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other materials known in the art may also be used. While not wanting to be limited by theory, it is believed that the polymeric dispersants, when used with other builders (including lower molecular weight polycarboxylates), enhance the overall effectiveness of the detergency builder by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in their 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. The presence of monomer segments which are free of carboxylic acid groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polycarboxylates of the invention is suitable provided that these segments do not exceed 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid based polymers suitable for use in the present invention are water soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in the acid form is preferably 2000-10000, more preferably 4000-7000, and most preferably 4000-5000. Water-soluble salts of such acrylic polymers may include alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known substances. The use of such polyacrylates in detergent compositions has been disclosed, for example, in us patent 3,308,067(Diehl, 3.7.1967).

Acrylic acid/maleic acid based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably 2000-100000, more preferably 5000-75000, most preferably 7000-65000. The ratio of acrylic acid groups to maleic acid group segments is generally from 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylic acid/maleic acid copolymers of this type are known and are described in European patent application 66915 (published 12.15.1982) and EP 193,360 (published 9.3.1986), which also describes polymers of this type which contain hydroxypropyl acrylate. Another class of suitable dispersants includes maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360 and include 45/45/10 terpolymers of acrylic acid/maleic acid/vinyl alcohol.

Yet another class of polymers that may be included are polyethylene glycols (PEGs). PEG can exhibit dispersant properties and function as a soil removal/anti-redeposition agent. The molecular weight of the polymer for this purpose is generally 500-100000, preferably 1000-50000, more preferably 1500-10000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in combination with zeolite-type buildersThe preparation is used. Dispersants such as polyaspartate are preferred to have an average molecular weight of 10000.Whitening agent

Any fluorescent whitening agent or other brightening or whitening agent known in the art may be incorporated into the detergent compositions of the present invention at levels typically from 0.01 to 1.2% by weight. Commercial optical brighteners useful in the present invention can be divided into several subclasses, which include, but are not necessarily limited to: stilbene derivatives, pyrazolines, coumarins, carboxylic acids, methines, dibenzothiophene-5, 5-dioxides, pyrroles, 5-and 6-membered heterocycles and other miscellaneous agents. Examples of such brighteners are disclosed in The "manufacture and use of fluorescent whitening Agents" (The Production and Application of fluorescent whitening Agents) book (M.Zahradnik, published by John Wiley&Sons, New York, 1982).

Specific examples of fluorescent whitening agents that may be used in the compositions of the present invention are those identified in U.S. Pat. No. 4,790,856 (12/13/1988, Wixon). These include the PHORWHITE series of brighteners from Verona. Other whitening agents disclosed in this document include: tinopal UNPA, Tinopal CBS and Tinopal5BM, marketed by Ciba-Geigy; artic White CC and Artic White CWD, 2- (4-styrylphenyl) -2H-naphtho [1, 2-d]A triazole; 4, 4' -bis- (1, 2, 3-triazol-2-yl) stilbene; 4, 4' -bis (styryl) biphenyl; and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin, 1, 2-bis (benzimidazol-2-yl) ethene, 1, 3-diphenylpyrazoline, 2, 5-bis (benzoxazol-2-yl) thiophene, 2-styrylnaphtho [1, 2-d]]Oxazole, and 2- (stilben-4-yl) -2H-naphtho [1, 2-d]A triazole. See also U.S. Pat. No.3,646,015 (29/2 1972, Hamilton).Dye transfer inhibitors

The compositions of the present invention may also contain one or more substances effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents will generally comprise from 0.01 to 10%, preferably from 0.01 to 5%, more preferably from 0.05 to 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferably used in the present invention contain the following nodulesA unit of formula (I): R-A_x-P, wherein P is a polymerizable unit to which an N-O group may be attached, or an N-O group may form part of this polymerizable unit or be attached to both units; a is one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N ═ O; x is 0 or 1; r is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the N-O group may be attached or which is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine or derivatives thereof.

The N-O group can be represented by the following general structural formula:wherein R is₁、R₂And R₃Is an aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof; x, y and z are 0 or 1; the N of the N-O group may be attached to or form part of any of the groups described above. The amine oxide units of the polyamine N-oxide have a pKa of<10, preferablya pKa of<7, more preferably a pKa of<6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are vinyl polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymer typically has an amine to amine N-oxide ratio of from 10: 1 to 1: 1000000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Generally, the average molecular weight is 500-1,000,000, more preferably 1,000-500,000, and most preferably 5,000-100,000. Such preferred materials may be referred to as "PVNO".

The most preferred polyamine N-oxide for use in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole (known as "PVPVI" as a class) are also preferred for use in the present invention. Preferably the average molecular weight of PVPVPVI is 5000-. The molar ratio of N-vinylimidazole to N-vinylpyrrolidone in the PVPVPVI copolymer is generally from 1: 1 to 02: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers may be linear or branched.

The compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000-400,000, preferably 5,000-200,000, more preferably 5,000-50,000. PVP is familiar to those skilled in the art of detergents, see for example EP-A-262,897 and EP-A-256,696, which are incorporated herein by reference. The PVP containing composition may also contain polyethylene glycol ("PEG") having an average molecular weight of 500-100,000, preferably 1,000-10,000. The ratio of PEG to PVP is from 2: 1 to 50: 1, more preferably from 3: 1 to 10: 1, calculated as ppm released in the wash solution.

The detergent compositions of the invention may optionally also contain from 0.005 to 5% by weight of certain types of hydrophilic optical brighteners which also have a dye transfer inhibiting effect. If used, the compositions preferably contain from 0.01 to 1% by weight of such optical brighteners.

Hydrophilic fluorescent whitening agents useful in the present invention have the following structural formula:

wherein R is₁Selected from anilino, N-2-hydroxyethyl and NH-2-hydroxyethyl; r₂Is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; m is a salt-forming cation, such as sodium or potassium.

When R in the above formula₁Is anilino, R₂When N-2-dihydroxyethyl is used and M is a cation such as sodium, the whitening agent is 4,4 '-bis [ (4-anilino-6- (N-2-dihydroxyethyl) -S-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acid and the disodium salt. This particular brightener species is sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy. Tinopal-UNPA-GX is a preferred hydrophilic group for use in detergent compositions of the present inventionAnd (3) an optical brightener.

When R in the above formula₁Is anilino, R₂Is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4 '-bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -S-triazin-2-yl) amino]-2, 2' -stilbene disulfonic acid disodium salt. This particular brightener species is sold under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When R in the above formula₁Is anilino, R₂Is morpholino and M is a cation such as sodium, the brightener is 4,4 '-bis [ (4-anilino-6-morpholino-S-triazin-2-yl) amino]2, 2' -stilbenedisulfonic acid, sodium salt. This particular brightener species is sold under the trade name Tinopal AMS-GX by Ciba Geigy corporation.

The particular fluorescent whitening agents selected for use in the present invention provide particularly effective dye transfer inhibition when used in conjunction with the selected polymeric dye transfer inhibiting agents described above. The combination of such selected polymers (e.g., PVNO and/or PVPVI) with selected fluorescent whitening agents (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in a wash liquor than either of the two detergent composition components when used alone. Without being deeply discussed in theory, it is believed that this effect of such optical brighteners is due to their high affinity for fabrics in the wash liquor, which deposits on these fabrics rather quickly. The extent to which the brightener deposits on the fabric in the wash solution is determined by a parameter known as the "exhaustion coefficient". The exhaustion coefficient is generally the ratio of a) the brightener species deposited on the fabric to b) the initial brightener concentration in the wash liquor. For the purposes of the present invention, brighteners having a high exhaustion coefficient are most suitable for inhibiting dye transfer.

It will of course be appreciated that other conventional types of optical brighteners may optionally be employed in the compositions of the present invention to provide a conventional fabric "whitening" effect rather than a true dye transfer inhibition effect. Such uses are conventional and are well known in the art of detergent formulation.Chelating agents

The detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. These chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without wishing to be bound by theory, it is believed that the effect of these materials is due in part to their unexpected ability to remove iron and manganese ions from the wash solution by forming soluble chelates.

Aminocarboxylates suitable as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate and ethanoldiglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable chelating agents in the compositions of the present invention when they allow at least low levels of total phosphorus in the detergent composition, and include ethylenediamine tetra (methylene phosphonate), known as DEQUEST. These aminophosphonates are preferably alkyl or alkenyl groups which do not contain more than 6 carbon atoms.

Polyfunctional substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See U.S. Pat. No.3,812,044 to Connor et al, 5, 21, 1974. Preferred compounds of this type are dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

The biodegradable chelating agents preferred for use in the present invention are ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomers as described in us patent 4,704,233 (11/3/1987, Hartman and Perkins).

The compositions of the present invention may also contain a water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) which may act as a sequestrant or co-builder used with insoluble builders such as zeolites, layered silicates and the like.

If used, these chelants typically comprise from 0.1% to 15% by weight of the detergent composition. More preferably, the chelating agent, if used, comprises 0.1 to 3.0% by weight of the composition.Suds suppressor

Compounds for reducing or inhibiting foam formation may be added to the compositions of the present invention. Suds suppression may be particularly important in "high intensity washing" and in the previously loaded european style washing machines as described in us patent 4,489,455 and 4,489,574.

A wide variety of materials may be used as suds suppressors, which are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of chemical technology, third edition, Vol.7, pp.430-477 (John Wiley&Sons, Inc., 1979). One particularly important class of suds suppressors comprises monocarboxylic fatty acids and soluble salts thereof. See U.S. patent 2,954,347 to Wayne st.john, 9,27, 1960. Monocarboxylic fatty acids and their salts used as suds suppressors typically have hydrocarbon chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts (e.g., sodium, potassium and lithium salts) and ammonium and alkanolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant suds suppressors. This includes, for example: high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀Ketones (e.g., stearyl ketone), and the like. Other suds suppressors include N-alkanesAcylated aminotriazines, e.g. chlorotriazines of tri-to hexaalkylmelamines or di-to tetraalkyldiamines as cyanuric chloride with 2 to 3 three moles of a primary or secondary amine having 1 to 24 carbon atoms, propylene oxide and monostearyl phosphate, e.g. monostearyl alcohol phosphate and monostearyl phosphateStearyl dialkali metal (e.g., K, Na and Li) phosphates and esters. Hydrocarbons such as paraffins and halogenated paraffins may be used in liquid form. The liquid hydrocarbon is liquid at room temperature and normal pressure, has a pour point of between-40 ℃ and 50 ℃, and a minimum boiling point of not lower than 110 ℃ (normal pressure). It is also known to use waxy hydrocarbons, preferably having a melting point below 100 ℃. Hydrocarbons constitute a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described in U.S. Pat. No. 4,265,779 (5.5.1981, Gandolfo et al). These hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having 12 to 70 carbon atoms. The term "paraffin" as referred to in the discussion of suds suppressors includes mixtures of true paraffins with cyclic hydrocarbons.

Another preferred class of non-surfactant type suds suppressors comprises silicone suds suppressors. Such suds suppressors include the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations thereof formed by chemisorption or fusion of polyorganosiloxane onto silica particles. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Pat. No. 4,265,779 (5.5.1981, Gandolfo et al) and European patent application 89307851.9 (published by 1990, 2.7.1, Starch, M.S.).

Other silicone suds suppressors are disclosed in U.S. Pat. No.3,455,839, which relates to compositions and methods for defoaming by adding small amounts of polydimethylsiloxane fluid to aqueous solutions.

Mixtures of polysiloxanes and silanized silicas are described in the German patent application DOS 2,124,526. U.S. Pat. No.3,933,672 (Bartolotta et al) and U.S. Pat. No. 4,652,392(Baginski et al, 3.24.1987) disclose silicone antifoams and foam control agents in granular detergent compositions.

An example of a silicone-based suds suppressor for use in the present invention is a suds suppressing amount of a suds controlling agent consisting essentially of:

(i) a polydimethylsiloxane fluid having a viscosity of about 20 to 1,500 centistokes at 25 ℃;

(ii) per 100 weight portions(ii) about 5-50 parts of a silicone resin Consisting of (CH) in a ratio of about 0.6: 1 to about 1.2: 1₃)₃SiO_1/2Unit and SiO₂The unit composition; and

(iii) about 1 to 20 parts of solid silica gel per 100 parts by weight of (i).

In the preferred silicone suds suppressors for use herein, the solvent of the continuous phase is comprised of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred) or polypropylene glycols. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.

To further illustrate this point, typical liquid laundry detergent compositions having controlled suds optionally contain from about 0.001% to about 1%, preferably from about 0.01% to about 0.7%, most preferably from about 0.05% to about 0.5%, by weight, of a silicone suds suppressor which comprises (1) a non-aqueous emulsion of a primary antifoam agent which is a mixture of: (a) a polyorganosiloxane, (b) a resinous siloxane or polysiloxane compound which produces a polysiloxane resin, (c) finely divided filler, and (d) a catalyst to promote reaction of mixture components (a), (b) and (c) to form a silanolate; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or polyethylene/polypropylene glycol copolymers having a solubility in water of greater than about 2% by weight at room temperature; no polypropylene glycol was included. Similar amounts can be used in granular compositions, gels, and the like. See also us4,978,471 (Starch, 18.12.1990) and 4,983,316(Starch, 8.1.1991), 5,288,431(Huber et al, 22.2.1994) and us4,639,489 and 4,749,740(Aizawa et al) from column 46 to column 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol and polyethylene/polypropylene glycol copolymers each having an average molecular weight of less than about 1000, preferably about 100-800. The solubility of polyethylene glycol and polyethylene/polypropylene glycol copolymers of the present invention in water at room temperature is greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents are polyethylene glycol having an average molecular weight of less than about 1000, more preferably about 100-. The weight ratio of polyethylene glycol to polyethylene glycol/polypropylene glycol copolymer is preferably from about 1: 1 to 1: 10, most preferably between 1: 3 and 1: 6.

Preferred silicone suds suppressors for use herein are free of polypropylene glycol, especially those having a molecular weight of 4000. And preferably are free of block copolymers of ethylene oxide and propylene oxide, such as PLURONICL 101.

Other suds suppressors useful herein include secondary alcohols (e.g., 2-alkyl alkanols) and mixtures thereof with silicone oils such as the polysiloxanes disclosed in U.S. Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. Such secondary alcohols include C₁-C₁₆C of carbon chain₆-C₁₆An alkyl alcohol. One preferred alcohol is 2-butyloctanol, available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trade name ISALCHEM 123. Mixed suds suppressors typically comprise a mixture of alcohol and silicone in a weight ratio of from 1: 5 to 5: 1.

For any detergent composition to be used in an automatic washing machine or a dishwashing machine, suds should not form to the extent that they overflow the washing machine or adversely affect the washing machine of the dishwashing machine. When used, suds suppressors are preferably used in an "suds suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition can select an amount of such suds controlling agent which is sufficient to control suds, resulting in a low sudsing laundry or dishwashing detergent for use in an automatic washing machine or a dishwashing machine.

The compositions of the present invention typically contain from 0% to about 10% of suds suppressors. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof are generally used in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of the aliphatic monocarboxylic acid salt suds suppressor is used. Silicone suds suppressors are generally used in amounts up to about 2% by weight of the detergent composition, although higher levels may also be used. This upper limit is practical in nature, primarily for cost reduction considerations and lower amounts to effectively control foamingEfficiency. Preferably, about 0.01% to about 1% of a silicone suds suppressor is used, more preferably about 0.25% to about 0.5%. These weight percent values used in the present invention include any silica that may be used in combination with the polyorganosiloxane, as well as any optional materials that may be used. Monostearyl phosphate suds suppressors are generally used in amounts of about 0.1 to 2% by weight of the composition. Hydrocarbon suds suppressors are generally used in amounts of about 0.01 to 5.0%, although higher amounts may also be used. Alcohol suds suppressors are generally used in amounts of 0.2 to 3% by weight of the finished composition.Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable for use in the present invention to provide additional grease removal performance. These substances are described on page 4 and later in WO 91/08281 and PCT 90/01815, which are incorporated herein by reference. Chemically, these materials include polyacrylates having one ethoxy branch per 7-8 acrylic acid based units. The chemical formula of these branches is- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. These branches are ester-linked to a polyacrylic acid "backbone" to form a "comb" polymer structure. The molecular weight may vary, but is typically in the range of 2000-50,000. These alkoxylated polycarboxylates may range from 0.05 to 10% by weight of the composition.Fabric softener

Various fabric softeners which are added during laundering, particularly the particulate smectites in U.S. Pat. No. 4,062,647 (12/13 1977, Storm and Nirschl) and other clay softeners known in the art, can optionally be used in the compositions of the present invention at levels typically between 0.5 and 10% by weight to perform the fabric softener function while cleaning the fabric. Clay softeners may be used with amines and cationic softeners as described in U.S. patent 4,375,416(Crisp et al, 3/1 1983) and U.S. patent 4,291,071(Harris et al, 9/22 1981).Perfume

The fragrance andflavor components useful in the compositions and methods of the present invention include a wide variety of natural and synthetic chemical components including, but not limited to, aldehydes, ketones, and esters. Also included are various natural extracts and essences, which may contain complex mixtures of multiple components, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam, sandalwood oil, pine oil, cedar oil. Finished perfumes can contain extremely complex mixtures of these components. Finished perfumes typically comprise from 0.01 to 2% by weight of the detergent composition, while individual perfume components may comprise from 0.0001 to 90% of the finished perfume composition.

Non-limiting examples of fragrance ingredients useful in the present invention include 7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene, methyl ionone, gamma-methyl ionone, methyl cedryl ketone, methyl dihydrojasmonate, methyl 1, 6, 10-trimethyl-2, 5, 9-cyclododecatrien-1-yl ketone, 7-acetyl-1, 1,3, 4,4, 6-hexamethyl-1, 2,3, 4-tetrahydronaphthalene, 4-acetyl-6-tert-butyl-1, 1-dimethylindane, p-hydroxyphenyl butanone, benzophenone, methyl β -naphthyl ketone, 6-acetyl-1, 1,2, 3,3, 5-hexamethylindane, 5-acetyl-3-isopropyl-1, 1,2, 6-tetramethylindane, 1-dodecylindane, 4- (4-hydroxy-4-methylpentyl) -3-hexamethylcinnamyl-1, 3, 5-hexamethyl indene, 5-acetyl-3-isopropyl-1, 1,2, 6-tetramethylindane, 1-dodecylbenzaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-hexamethylindane, 7-tetramethylcumylcinnamyl aldehyde, 7-ethylcumenyl-1, 7-1, 6-tetrahydronaphthyl ketone, 4-1, 4-cyclohexyl-1, 6-1, 4-hexahydro-1, 4-1, 6-tetrahydronaphthalene, 4-1, 6-dimethylvaleryl-1, 6-tetrahydronaphthalene, 4-tert-cyclohexyl-1, 6-hexadecyl-1, 6-tert-butyl-methyl-hexadecyl-1, 6-tert-pentyl-1, 7-pentyl-1, 7-pentyl-1, 4-pentyl-1, 7-pentyl-1, 4-pentyl-1, 4-1, 7-1, 4-pentyl.

Particularly preferred perfume materials are those whichprovide the greatest odor improvements in finished cellulase-containing compositions, including, but not limited to, hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) propanal, 7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1, 1,3, 4,4, 6-hexamethyl-1, 2,3, 4-tetrahydronaphthalene, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β -naphthol methyl ether, methyl β -naphthyl ketone, 2-methyl-2- (p-isopropylphenyl) propanal, 1,3, 4,6, 7, 8-hexahydro-4, 6,7, 8, 8-hexamethylcyclopenta-gamma-2-benzopyran, dodecahydro-3 a, 6,6, 9 a-tetramethylnaphtho [2, 1b]furan, anisic aldehyde, vanillin, pentacyclopentenyl decanoate, tricyclodecenyldecanoate, and tricyclodecenyldecanoic acid.

Other fragrance materials include essential oils, resinoids, and resins obtained from various sources including, but not limited to: peru balsam, frankincense balsam, storax, rosa resin, nutmeg, Chinese cinnamon oil, benzoin resin, coriander and lavandula angustifolia. Other fragrance chemicals also include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1, 1-dimethylethyl) cyclohexanol acetate, benzyl acetate, and eugenol. A carrier, such as diethyl phthalate, may be used in the finished fragrance composition.Other Components

A wide variety of other components suitable for use in detergent compositions may be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, and the like. If foaming is desired, a foam booster such as C may be added to the composition₁₀-C₁₆Alkanolamides, generally from 1 to 10%. C₁₀-C₁₄Monoethanol and diethanolamide are typical of such suds boosters. With the above-mentioned vesiculated optional surfactants (e.g., amine oxides, betaines and sulfobetaines)The use of such foam boosters is also advantageous. If desired, water-soluble magnesium and/or calcium salts, such as MgCl, can be added in amounts of usually 0.1-2%₂、MgSO₄、CaCl₂、CaSO₄Etc. to increase foaming and improve the effectiveness of the ester removal.

The various detersive ingredients used in the compositions of the present invention can optionally be further stabilized by absorbing said ingredients into a porous hydrophobic carrier and coating the carrier with a hydrophobic coating. Preferably, the detersive ingredient is first mixed with a surfactant and then absorbed into the porous carrier. In use the detersive component is released from the carrier into the wash liquor and performs its intended detersive function.

To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) was mixed with 3% -5% C_13-15A protease solution of ethoxylated alcohol (EO7) nonionic surfactant was mixed. Typically, the enzyme/surfactant solution is 2.5 times the weight of the silica. The powder formed was dispersed with stirring in a silicone oil (various silicone oils with a viscosity of 500-12,500 can be used). The silicone oil dispersion formed is emulsified or added to the final detergent base. By this method, enzymes, bleaches such as those described above can be addedComponents such as agents, bleach activators, bleach catalysts, photoactivators, dyes, optical brighteners, fabric finishes, and hydrolyzable surfactants are "protected" for use in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. For stabilizing the surfactant, a monohydric alcohol is preferred, but polyols, for example, those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, such as 1, 3-propanediol, ethylene glycol, propylene glycol and 1, 2-propanediol, may also be used. The composition may contain 5-90%, usually 10-50% of such a carrier.

The detergent compositions of the present invention are preferably formulated such that the pH of the wash water during use in the aqueous washing operation is between 6.5 and 11, preferably between 7.5 and 10.5.The liquid dishwashing product preferably has a pH of 6.8-9.0. Laundry products are typically pH 9-11. Methods of controlling the pH within the suggested range include the use of buffers, bases, acids, and the like, as is well known to those skilled in the art.Preparation of granules

The bis-alkoxylated cationic surfactant of the present invention is added to the crutcher for mixing, followed by conventional spray drying to help remove any residual, potentially odorous short chain amine contaminants. If the formulator wishes to prepare mixable particles containing alkoxylated cationic surfactants for use in high density granular detergents, the alkalinity of the particulate composition is preferably not high. A process for preparing high density (greater than 650g/l) granules is described in U.S. Pat. No. 5,366,652. These particles can be formulated to have an effective pH of 9 or less to avoid the odor of the contaminating amine when used. This can be done by adding a small amount of an acid source (e.g. boric acid, citric acid, etc.) or a suitable pH buffer to the particles. Alternatively, perfumes as disclosed herein can be used to mask problems expected with amine odors.

Examples

The following examples are illustrative of the present invention and are not meant to limit or define its scope. All parts, percentages and ratios used herein are by weight unless otherwise indicated.

In the following examples, the abbreviated component symbols have the following meanings:

and (3) LAS: straight chain C₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C45AS：C₁₄-C₁₅Linear alkyl sodium sulfate

CxyEzS: c condensed with z moles of ethylene oxide_1x-C_1yBranched alkyl sodium sulfate

C45E 7: c condensed with an average of 7 moles of ethylene oxide_14-15Substantially linear primary alcohols

C25E 3: is and flatC condensed with 3 mol each of ethylene oxide_12-15Branched primary alcohols

C25E 5: c condensed with an average of 5 moles of ethylene oxide_12-15Branched primary alcohols

Coconut oil based EO: r₁.N⁺(CH₃)(C₂H₄OH)₂，R₁＝C₁₂-C₁₄

Soap: sodium linear alkylcarboxylates derived from a tallow/coconut oil mixture of 80/20

TFAA：C₁₆-C₁₈Alkyl N-methylglucamides

TPKFA：C₁₂-C₁₄Topped whole fraction fatty acids

STPP: anhydrous sodium tripolyphosphate

Zeolite a: has a chemical formula of Na₁₂(AlO₂SiO₂)₁₂·27H₂Hydrated sodium aluminosilicate of O, primary particle size 0.1-10 microns

NaSKS-6: chemical formula delta-Na₂Si₂O₅Of crystalline layered silicate

Citric acid: anhydrous citric acid

Carbonate salt: anhydrous sodium carbonate with particle size of 200-900 micron

Bicarbonate salt: anhydrous sodium bicarbonate with particle size of 400-1200 micron

Silicate salt: anhydrous sodium Silicate (SiO)₂∶Na₂O＝2.0)

Sodium sulfate: anhydrous sodium sulfate

Citrate salt: trisodium citrate dihydrate content of 86.4%, particle size distribution between 425 and 850 microns

MA/AA: 1: 4 maleic acid/acrylic acid copolymer, average molecular weight 70,000

CMC: sodium carboxymethylcellulose

Protease: a proteolytic enzyme having an activity of 4KNPU/g, product NOVO Industries A/S, under the trade name Savinase.

Alcalase: the protein hydrolase sold by NOVO Industries A/S has an activity of 3AU/g

Cellulase: NoVO Industries A/S sells a cellulose hydrolase with an activity of 1000 CEVU/g, under the trade name Carezyme

Amylase: NOVO Industries A/S sells starch hydrolyzing enzymes with an activity of 60 KNU/g, under the trade name Termamyl 60T

Lipase: the lipolytic enzyme sold by NOVO Industries A/S with an activity of 100 KLU/g, under the trade name Lipolase

Endosase: endoglucanase sold by NOVO Industries A/S with an activity of 3000 EVU/g

PB 4: nominal chemical formula of NaBO₂·3H₂O·H₂O₂Sodium perborate tetrahydrate

PB 1: nominal molecular formula of NaBO₂·H₂O₂Anhydrous sodium perborate bleach

Percarbonate salts: nominal formula of 2Na₂CO₃·3H₂O₂Sodium percarbonate of (2)

NOBS: nonanoyloxybenzenesulfonate in the form of the sodium salt

TAED: tetra acetyl ethylene diamine

NACA-OBS: (6-Nonoylaminohexanoyl) oxybenzenesulfonate

DTPMP: diethylene triamine penta (methylene phosphonate), product of Monsanto, trade name Dequest 2060

Co catalyst: acetic acid pentaammine cobalt (III) salt

Mn catalyst: m_n ^IV ₂(m-O)₃(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(PF₆)₂As described in U.S. Pat. Nos. 5,246,621 and 5,244,594

Light activated bleaching agents: sulfonated zinc phthalocyanines encapsulated in dextrin-soluble polymers as bleaches

Whitening agent 1: 4, 4' -bis (2-sulfostyryl) biphenyl disodium salt

Whitening agent 2: disodium (4, 4 '-bis (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) amino) stilbene-2, 2' -disulfonate

HEDP: 1, 1-hydroxyethane diphosphonic acid

PVNO: polyvinylpyridine N-oxides

PVPVI: copolymers of polyvinylpyrrolidone and vinylimidazole

SRA 1: esters having an oxyethyleneoxy and terephthaloyl backbone and end-capped with sulfobenzoyl groups

SRA 2: diethoxylated poly (1, 2-trimethylene terephthalate) short block polymers

Polysiloxane antifoaming agent: a polydimethylsiloxane foam control agent having a siloxane-alkylene oxide copolymer as a dispersant, the ratio of the foam control agent to the dispersant being from 10: 1 to 100: 1.

In the following examples, all amounts are by weight of the composition.

Example I

Detergent formulations were prepared according to the invention wherein a and C were phosphorus containing detergent compositions and B was a zeolite containing detergent composition.

A B CSprayed powder

STPP 24.0 - 24.0

Zeolite A-24.0-

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 - -

Coconut oil based MEEO2^*1.5 1.0 2.0

Silicate 7.03.03.0

CMC 1.0 1.0 0.5

Whitening agent 20.20.20.2

Soap 1.01.01.0

DTPMP 0.40.40.2 spray coating

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Silicone antifoaming agent 0.30.30.3

Dry additive of spice 0.30.30.3

Carbonate 6.013.015.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.01.0

Catalyst 0.30.050.4

Photoactivated bleaching agent 0.020.020.02

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.250.300.15 Dry Mixed sodium sulfate 3.03.05.0

The balance (moisture and impurities) to: 100.0100.0100.0 Density (g/l) 630670670

^*bis-AQA-1 (coco MEEO) in the examples₂) The surfactant may be replaced with an equivalent amount of any one of the surfactants bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants.

Example II

The following detergent formulations were prepared according to the invention:

G H Isprayed powder

Zeolite 30.022.06.0

Sodium sulfate 19.05.07.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

Coconut oil based MEEO2^*1.0 1.0 1.0

Mn catalyst 0.90.70.05

Silicate-1.05.0

Soap-2.0

Whitening agent 10.20.20.2

Carbonate 8.016.020.0

DTPMP-0.40.4 spray coating

C45E71.01.01.0 Dry additives

PVPVI/PVNO 0.5 0.5 0.5

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.10.10.1

Cellulase 0.10.10.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium sulfate-6.0-balance (water and miscellaneous) to: 100100100

^*bis-AQA-1 (coco MEEO) in this example₂) The surfactant may be replaced with an equivalent amount of any of the surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.

Example III

The following high-density bleach-containing detergent formulations were prepared according to the present invention:

J K Lspray powder

Zeolite A15.015.015.0

Sodium sulfate 0.05.00.0

LAS 3.0 3.0 3.0

Coconut oil based MEEO2^*1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.02.02.0 agglomerate

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.03.04.0

Zeolite A8.08.08.0

Carbonate 8.08.04.0 spray

Fragrance 0.30.30.3

C45E7 2.0 2.0 2.0

C25E32.0 Dry additive

Citrate 5.0-2.0

Bicarbonate-3.0-

Carbonate 8.015.010.0

TAED 6.0 2.0 5.0

PB1 13.0 7.0 10.0

Mn catalyst 0.020.40.1

Polyoxyethylene-0.2 with molecular weight of 5,000,000

Bentonite-10.0

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.60.606

Cellulase 0.60.60.6

Silicone defoamer 5.05.05.0 dry additive

Sodium sulfate 0.03.00.0

The balance (moisture and impurities) to: 100.0100.0100.0 Density (g/l) 850850850^*bis-AQA-1 (coco MEEO) in this example₂) The surfactant may be replaced with an equivalent amount of any one of the surfactants bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants herein.

Example IV

The following high density detergent formulations were prepared according to the present invention.

M NSpray powder

Zeolite A2.52.5

Sodium sulfate 1.01.0

AQA-11.51.5 agglomerates

C45AS 11.0 14.0

Zeolite A15.06.0

Sodium carbonate 4.08.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.40.4 spray coating

C25E5 5.0 5.0

Dry additive of spice 0.50.5

HEDP 0.5 0.3

SKS6 13.0 10.0

Citrate salt 3.010

TAED 5.0 7.0

Percarbonate 15.015.0

Mn catalyst 0.031.4

SRA1 0.3 0.3

Protease 1.41.4

Lipase 0.40.4

Cellulase 0.60.6

Amylase 0.60.6

Silicone antifoaming agent 5.05.0

Whitening agent 10.20.2

Whitening agent 20.2-

The balance (moisture and impurities) to: 100100 Density (g/L) 850850^*bis-AQA-1 (coco MEEO) in this example₂) The surfactant may be replaced with an equivalent amount of any one of the surfactants bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants herein.

Any of the granular detergent compositions provided herein can be compressed to form a detergent tablet using known tabletting processes.

Modern automatic dishwashing detergents may contain bleaching agents such as hypochlorite sources; perborate, percarbonate, or persulfate bleaches; enzymes, such as proteases, lipases and amylases, or mixtures thereof; rinse aids, especially nonionic surfactants; builders, including zeolites and phosphate builders; low foaming detersive surfactants, especially ethylene oxide/propylene oxide condensates. Such compositions are typically in granular or gel form.

The following examples A and B further illustrate the invention with respect to phosphate-containing granular automatic dishwashing detergents.

Example V

Weight% of activeComponents A BSTPP (waterless)¹3126 sodium carbonate 2232Silicate (% SiO)₂) 97 surfactant (nonionic) 31.5 NaDCC bleaching agent²2-bis-AQA-1^*0.51.0 sodium perborate 7.795 TAED- -1.5 Co catalyst 0.20.2 Savinase (Au/g) - -0.04 Termamyl (Amu/g) 425 sulfate 2525 fragrance/trace to 100%¹Sodium tripolyphosphate²Sodium dichlorocyanurate^*The bis-AQA-1 surfactants may be replaced by bis-AQA-2 to bis-AQA-22.

Example VI

The following examples illustrate bis-AQA surfactant mixtures that can be substituted for the bis-AQA surfactants listed in any of the examples above. As noted above, such mixtures can be used to provide cleaning compositions having various performance improvements and/or which are suitable for use in a variety of conditions of use. The bis-AQA surfactants in these mixtures preferably differ in the respective total EO unit numbers by at least 1.5, preferably from 2.5 to 20. The ratio of the mixture is generally in the range from 10: 1 to 1: 10 by weight. Non-limiting examples of such mixtures are as follows.

Components Ratio (weight)bis-AQA-1 + bis-AQA-51: 1 bis-AQA-1 + bis-AQA-101: 1 bis-AQA-1 + bis-AQA-151: 2 bis-AQA-1 + bis-AQA-5 + bis-AQA-201: 1 bis-AQA-2 + bis-AQA-53: 1 bis-AQA-5 + bis-AQA-151.5: 1 bis-AQA-1 + bis-AQA-201: 3

Mixtures of the bis-AQA surfactants of the present invention with corresponding cationic surfactants containing only a single ethoxylated chain may also be used. For example, compounds of the formulaR¹N⁺CH₃[CO]_x[EO]_yX^-And R¹N⁺(CH₃)₂[EO]_zX^-In which R is a salt of a nonionic surfactant, in which R is a salt of a nonionic surfactant¹And X is as defined above, and wherein one of the cationic surfactants has an (X + y) or z of 1 to 5, preferably 1 to 2, and the other has an (X + y) or z of 3 to 100, preferably 1 to 20, most preferably 14 to 16. Such compositions advantageously provide improved wash performance (especially in fabric laundering) over a wider range of water hardness than when a single cationic surfactant is used. It has been found that short EO chain cationic surfactants (e.g., EO2) improve the cleaning performance of anionic surfactants in soft water, while long EO chain cationic surfactants (e.g., EO 15) improve the hardness tolerance of anionic surfactants, thereby improving the cleaning performance of anionic surfactants in hard water. General knowledge in the detergent art indicates that builders can optimize the "use window" of anionic surfactant performance, but previouslyIt is not possible to widen this window to the extent that substantially all water hardness conditions are included.

Example VII

The following examples illustrate conventional, but not limiting, non-AQA surfactant mixtures that can be used in combination with the bis-AQA surfactants of any of the above examples. The proportion of non-AQA surfactants in the mixture is expressed in parts by weight of the surfactant mixture.

Mixtures A to C

Components Ratio of

AS^*/LAS 1∶1

AS/LAS 10: 1 (preferably 4: 1)

AS/LAS 1: 10 (preferably 1: 4)^*The substantially linear primary AS surfactants described above may be replaced with equivalent amounts of secondary or branched AS, oleyl sulfate and/or mixtures thereof (including mixtures with the linear primary AS described above). An AS of "tallow" chain length is particularly suitable under hot water conditions up to boiling. The "coco" AS is then preferably used for colder washing temperatures.

The alkyl sulfate/anionic surfactant mixture described above is modified by the addition of a nonionic, non-AQA surfactant, wherein the weight ratio of total anionic surfactant to nonionic surfactant is from 25: 1 to 1: 5. The nonionic surfactant may comprise any conventional type of ethoxylated alcohol or alkyl phenol, alkyl polyglycoside or polyhydroxy fatty acid amide (less desirable if LAS is present), or mixtures thereof, such as those disclosed above.

Mixtures D to F

AS^*/AES 1∶1

AS/AES 10: 1 (preferably 4: 1)

AS/AES 1: 10 (preferably 1: 4)^*Secondary, branched or oil-based AS described above may be substituted.

The above AS/AES mixture may be modified by addition of LAS, wherein the weight ratio of AS/AES (total amount) to LAS is from 1: 10 to 10: 1.

AS/AES or their AS/AES/LAS mixtures may also be combined with the nonionic surfactants indicated above for mixtures A-C, the total amount of anionic surfactant(s) and nonionic surfactant(s) being from 25: 1 to 1: 5.

Any of the above mixtures may be modified by the addition thereto of an amine oxide surfactant, wherein the amine oxide comprises from 1 to 50% of the total surfactant mixture.

Highly preferred mixtures of the above non-AQA surfactants will comprise from 3 to 60% by weight of the total finished detergent composition. The finished composition preferably contains 0.25 to 3.5% by weight of the bis-AQA surfactant.

Example VIII

This example illustrates a perfume formulation (a-C) prepared according to the present invention for incorporation into any of the above-described bis-AQA-containing detergent compositions. The components and amounts are listed below.

(wt%) Perfume component A B CHexyl cinnamic aldehyde 10.0-5.02-methyl-3- (p-tert-butylphenyl) propanal 5.05.0-7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene 5.010.010.0 benzyl salicylate5.0-7-acetyl-1, 1,3, 4,4, 6-hexamethyl-1, 2,3, 4-tetrahydronaphthalene 10.05.010.0 p- (tert-butyl) cyclohexyl hexanoate 5.05.0-methyl dihydrojasmonate-5.0- β -naphthol methyl ether-0.5-methyl β -naphthalenyl ketone-0.5-2-methyl-2- (p-isopropylphenyl) propanal-2.0-1,3, 4,6, 7, 8-hexahydro-4, 6,6, 7,8, 8-hexamethylcyclopenta-gamma-2-benzopyran-9.5-dodecahydro-3 a, 6,6, 9 a-tetramethylnaphtho [2, 1b]]Furan-0.1 anisaldehyde-0.5 coumarin-5.0 cedrol-0.5 vanillin-5.0 cyclopentadecanolide 3.0-10.0 tricyclodecenyl acetate-2.0 rosa multiflora resin-2.0 tricyclodecenyl propionate-2.0 phenethyl alcohol20.010.027.9 terpineol 10.05.0-linalool 10.010.05.0 linalyl acetate 5.0-5.0 geraniol 5.0-nerol-5.0-2- (1, 1-dimethylethyl) cyclohexyl acetate 5.0-orange oil, cold press-5.0-benzyl acetate 2.02.0-orange terpene-10.0-eugenol-1.0-diethyl phthalate-9.5-lemon oil, cold press-10.0 Total 100.0100.0100.0

The above perfume compositions are mixed or sprayed (typically in an amount of about 2% by weight of the total cleaning composition) into any of the cleaning (including bleaching) compositions disclosed herein containing the bis-AQA surfactants to ensure improved deposition and/or retention of the perfume or individual components thereof on the surface to be cleaned (or bleached).

Claims (16)

1. A detergent composition comprisingOr a combination of a peroxygen bleach, a bleach catalyst, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl, ether or alditol based ether moieties, R²Is C₁-C₃Alkyl radical, R³And R⁴Independently variable, selected from hydrogen, methyl and ethyl, X is an anion, A and A' independently variable, each selected from C₁-C₄Alkoxy, p and q can vary independently and are each an integer from 1 to 30.

2. A composition according to claim 1 wherein the peroxygen bleach is selected from perborate, percarbonate, perphosphate, persilicate or persulfate salts, or is a preformed peracid.

3. A composition according to claim 1 or 2 wherein the bleach catalyst is a manganese or cobalt containing bleach catalyst.

4. A composition according to any of claims1 to 3 which is prepared by combining the non-AQA surfactant and the bis-AQA surfactant.

5. A composition according to any of claims 1 to 4 wherein the non-AQA surfactant is an anionic surfactant.

6. A composition according to any of claims 1 to 5 wherein the ratio of bis-AQA to non-AQA surfactant is from 1: 15 to 1: 8.

7. A composition according to any of claims 1 to 6 wherein the bis-AQA surfactant has the formula R¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy and p and q are each from 1 to 8An integer number.

8. A composition according to any of claims 1 to 7 wherein the bis-AQA surfactant has the formula R¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy, and p and q are each integers from 1 to 4.

9. A composition according to any of claims 1 to 8 comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

10. A composition according to any of claims 1 to 9 comprising a mixture of two or more non-AQA surfactants and two or more bis-AQA surfactants.

11. A composition according to any one of claims 1 to 10 in the form of granules, tablets, non-aqueous liquids or tablets.

12. A method of removing soils and stains by contacting the soils and stains with a detergent composition according to claims 1 to 11 or an aqueous medium containing said detergent composition.

13. A method according to claim 12 for removing bleach sensitive soils from fabrics.

14. A method according to claim 12 or 13, which is carried out in an automatic washing machine.

15. A method for enhancing the deposition or substantivity of perfumes or perfume ingredients onto fabrics or other surfaces, which comprises contacting said surfaces with a perfume or perfume ingredient in the presence of a bis-AQA surfactant.

16. A method according to claim 15 which is conducted in combination with a detergent composition comprising a bis-AQA, with a perfume or perfume ingredient.