CN1200757A - Detergent composition with bleach system stabilized by enzymes - Google Patents

Abstract

The present invention relates to a laundry detergent bar composition comprising: (a) from about 10 % to about 60 % detergent surfactant, wherein anionic surfactant comprises at least about 10 % of the total amount of surfactant; (b) from about 0.10 % to about 60 % bleach agent; and (c) from about 0.0011 mg to about 2.2 mg of active enzyme selected from the group consisting of protease, amylase, cellulase, lipase, peroxidase, and mixtures thereof, per gram of the composition. The addition of enzymes stabilizes the bleach agent and preserves the effectiveness of the bleach in laundry detergent bar compositions.

Description

Detergent composition containing an enzyme stabilized bleach system

Background of the Invention

Field of Invention

The present invention relates to a laundry detergent composition. The present invention also relates to a laundry detergent bar. More specifically, it relates to a laundry detergent bar containing a bleaching system.

Description of related technologies

In many communities, especially those where mechanical washing machines are widespread, laundry is washed using synthetic detergent granules and detergent compositions in liquid form.

The prior art generally discloses granular detergent compositions comprising bleach systems. Furthermore, the prior art discloses granular detergent compositions comprising bleach systems and enzymes. The following references are hereby incorporated by reference: British Publication No. 1275301, Desforges, published May 24, 1972, British Publication No. 2139260, Oakes, published May 2, 1984, authorized to Cornelissen et al., August 29, 1989 U.S. Patent 4,861,509 issued September 6, 1988 to Cornelissen et al., European Publication No. 365,103-A2 issued April 25, 1990 to Uchiyama et al., Donker published May 2, 1991 European Publication No. 425214-A2 by et al.

In communities where mechanical washing machines are not prevalent, laundry detergent bars comprising synthetic organic surfactants and detergency builders are used to wash clothes. Technological developments in the field of laundry detergent bars relate to formulated bars that are effective in washing clothes; that have acceptable sudsing characteristics in warm and cold water, as well as hard and soft water; that have acceptable in-use wear rates, hardness, durability and It has a hand feel; it has low smearability; and it has a pleasant smell and appearance. Methods of making laundry detergent bars are also well known in the art. Prior art disclosing laundry detergent bars and methods of making laundry bars include: Okenfuss, US Patent 3,178,370, issued April 13, 1995; and Anderson, Philippine Patent 13,778, issued September 23, 1980.

The prior art generally discloses laundry detergent bars containing a bleaching system. Furthermore, the prior art discloses laundry bars containing sodium perborate monohydrate as the preferred bleaching agent. Such prior art includes Finch's British Publication 2172300, published September 17, 1986 (equivalent to Philippine Patent 21708).

Without being bound by theory, it is believed that catalase enzymes found in body soils worn through clothing break down perborate and other bleaches in laundry detergent compositions. The time for enzymes and bleach to interact with catalase is only when the granules are dissolved in dilute wash liquor, a problem unique to soap bars compared to granules. After the bar has been used by the consumer, the bar with the washing liquid remains wet, and the washing liquid soaks into the inside of the bar - which brings the catalase enzyme that breaks down the bleach - so that the next time it is used, the The bleaching effect of the soap bar is reduced. Because consumers use the same bar over multiple washes, maintaining the effectiveness of the bleach in the bar is important.

It has now been found that enzymes, preferably proteases, cellulases, or combinations thereof, are capable of degrading catalase, thereby preventing it from breaking down bleach, and maintaining the effectiveness of the bleach in laundry detergent bar compositions.

Summary of Invention

The present invention relates to a laundry detergent bar composition comprising:

(a) from about 10% to about 60% of a detersive surfactant, wherein the anionic surfactant comprises at least about 10% of the total surfactant;

(b) from about 0.10% to about 60% bleach; and

(c) from about 0.0011 milligrams to about 2.2 milligrams per gram of composition an active enzyme selected from the group consisting of proteases, amylases, cellulases, lipases, peroxidases, and mixtures thereof.

Preferred soap bar compositions include:

(a) about 1% to 50%, preferably about 1% to 20%, peroxygen bleach, preferably sodium perborate monohydrate (PB1);

(b) from about 0.0055 milligrams to about 0.022 milligrams of protease per gram of composition; and

(c) from about 0.002 milligrams to about 0.04 milligrams of cellulase per gram of composition.

Optionally, the composition also includes from about 0.1% to 5%, preferably from about 0.3% to 1.5%, most preferably about 0.9%, of a perborate system stabilizing phosphonate chelating agent. A preferred chelating agent is diethylenetriaminepenta(methylenephosphonic acid). Bleach activators may also optionally be included.

All documents referred to in this application are incorporated herein by reference.

Detailed description of the invention

While the specification concludes with claims which point out and particularly claim what is believed to be the invention, it is believed that the invention will be better understood from the following detailed description of the invention. In this specification, unless otherwise specified, all percentages are percentages by weight, all temperatures are expressed in degrees Celsius, molecular weights are expressed as weight averages, and decimal points are indicated by dots (.).

Surfactants for Detergents

Detergent surfactants are preferably present at levels of from about 10% to 60% by weight, more preferably from about 15% to about 40%, and most preferably from about 20% to about 35%.

Preferred surfactants are anionic surfactants, and anionic surfactants comprise at least about 10% of the total surfactants in the bar. Anionic surfactants may be selected from:

(a) have C8-20 alkyl chain, preferably C10-18 alkyl chain, and most preferably C12-16 alkyl chain linear or branched alkylbenzene sulfonate;

(b) Alkyl sulfate with C8-20 alkyl chain, preferably C14-18 alkyl chain, most preferably C12-16 alkyl chain;

(c) Alkyl ether sulfates of formula R-En-SO ₃ M, wherein:

(i) R is C8-20, and preferably C12-18 alkyl chain;

(ii) E is an ethoxy unit;

(iii) n is 0-20; and

(iv) M is a suitable cation, preferably a sodium ion; or an α-sulfonated fatty acid alkyl ether surfactant with the chemical formula R'-C(SO ₃ )HC(O)-OR", wherein R' is C8- 20, most preferably a C18-18 alkyl chain, and R" is a C1-4 alkyl, preferably methyl; and

(d) mixtures thereof.

Also can use weight ratio alkylbenzene sulfonate: alkyl sulfate is about 90:10～5:95, preferably about 30:70～0:100 linear or branched chain alkylbenzene sulfonate and alkyl A mixture of sulfates. The corresponding molar ratio of alkylbenzenesulfonate to alkylsulfate is about 20:80 to 10:90, preferably about 18:82 to 12:88, and most preferably about 16:84 to 13:87.

Other useful anionic surfactants include water-soluble 2-acyloxy-alkane-1 sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkyl moiety. Salts; water-soluble salts of olefin sulfonic acids containing about 12 to 24 carbon atoms; and beta-alkoxy chains having about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkyl moiety Alkylsulfonates.

Water-soluble salts of higher fatty acids, "soaps", are also useful anionic surfactants in the present invention. Soaps can be made by direct saponification of fats and oils or by neutralization of free fatty acids. Examples of soaps are the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, ie sodium or potassium tallow and coconut soap.

Other anionic surfactants useful in the present invention include:

Sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil;

Sodium coconut fatty acid monoglyceride sulfonate and sodium coconut fatty acid monoglyceride sulfate;

Sodium or potassium alkylphenol oxirane ether sulfates, and sodium or potassium salts of methyl esters of the formula R-CH(SO ₃ M)-COOR′, where R is C ₈ -C ₂₂ alkyl or alkenyl , R' is C ₁ -C ₄ alkyl, and M is a counterion, preferably sodium or potassium, as disclosed in WO-93-05013 published March 18, 1992;

Secondary alkyl sulfates having an alkyl chain of 10 to 20 carbon atoms;

Alkane comprising a C ₆ -C ₁₈ alkyl moiety and an alkoxy moiety comprising an average of about 0.5 to about 20 moles of alkoxy, preferably ethoxy units, more preferably about 0.5 to about 5 moles of ethoxy units base alkoxy sulfate; and

Alkyl ethoxy carboxylates of the formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , wherein R is a C ₆ to C ₁₈ alkyl group; x is 0 to 10; and the ethoxylate is The weight basis is distributed such that when x is 0, the amount of material is less than 20%, when x is greater than 7, the amount of material is less than 25%, and wherein when R is C ₁₃ or lower on average, x is on average 2 to 4, and when R is greater than C ₁₃ on average, x is 3-6 on average; and M is an alkali metal, alkaline earth metal, ammonium, mono-, di-, and triethanolammonium.

Optional detersive surfactants can be included at levels up to about 10%, more preferably from about 1% to about 5%, of the total surfactant in the composition. Types of detersive surfactants which may be used as optional surfactants include cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof.

Useful optional surfactants can be nonionic, and include:

Alkylpolysaccharides, alkylpolyglycosides, as described in US Patent 4,565,647 to Llenado.

The chemical formula is the polyhydroxy fatty acid amides of RC(O)-N(R')-Z, wherein R is C ₅ -C ₃₁ hydrocarbon group, preferably C ₁₁ -C ₁₇ alkyl or alkenyl; R' is H, C ₁ -C _Hydrocarbyl , 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, preferably methyl, and Z is a polyhydroxyl (linear) hydrocarbyl chain with at least 3 hydroxyl groups directly attached to the chain, preferably - _CH2- (CHOH) ₄ - _CH2OH , as described in European Patent 550,652.

Semi-polar nonionic surfactants, such as water-soluble amine oxides, water-soluble phosphine oxides, and water-soluble sulfoxide surfactants; and

Broadly defined as water-soluble nonionic synthetic surfactants of compounds obtained by condensation of oxirane groups (hydrophilic) with organic hydrophobic compounds which may be aliphatic or alkylaromatic in nature. The length of the polyoxyethylene group condensed with any particular hydrophobic group can be readily adjusted to obtain a water-soluble compound with the desired degree of balance between the hydrophilic and hydrophobic moieties.

Cationic surfactants may also be used in the detergent compositions of the present invention, suitable quaternary ammonium surfactants are selected from mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants , wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl.

Amphoteric surfactants are also useful in the detergent compositions of the present invention and include aliphatic derivatives of heterocyclic secondary and tertiary amines; zwitterionic surfactants including derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds; Water-soluble salts of alpha-sulfonated fatty acid esters; betaines of the formula (R(R ¹ ) ₂ N ⁺ R ² COO ^- , wherein R is C ₆ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₆ alkyl or C ₁₀ -C ₁₆ amidoalkyl, each R' is generally C ₁ -C ₃ alkyl, preferably methyl and R ₂ is C ₁ -C ₅ hydrocarbon, preferably C ₁ -C ₃ alkylene, more preferably C ₁ -C ₂ alkylene. Examples of suitable betaines include cocamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C ₁₂ -C ₁₄ amidopropyl betaine, C ₈ -C ₁₄ amidohexyl diethyl betaine, 4[C _14-16 acylmethylamidodiethylammonium]-1-carboxybutane, C _16-18 amidodimethyl betaine, C ₁₂ - C ₁₆ amidopentane diethyl betaine and C _12-16 acylmethyl amido dimethyl betaine. Preferred betaines are C _12-18 dimethylammoniohexanoate and C _10-18 Amidopropane (or ethane) dimethyl (or diethyl) betaines; and sultaines of formula (R(R ¹ ) ₂ N ⁺ R ² SO ₃ ^- , where R is C ₆ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₆ alkyl, more preferably C ₁₂ -C ₁₃ alkyl, each R ¹ is generally C ₁ -C ₃ alkyl, preferably methyl, and R ² is C ₁ -C ₆ hydrocarbyl , preferably C ₁ -C ₃ alkylene, or preferably hydroxyalkylene. Examples of suitable sultaines include C ₁₂ -C ₁₄ dimethylammonium-2-hydroxypropyl sulfonate, C ₁₂ - C ₁₄ amidopropylammonium-2-hydroxypropyl sultaine, C ₁₂ -C ₁₄ dihydroxyethylammonium propane sulfonate and C _16-18 dimethylammonium hexyl sulfonate, C _12-14 Amidopropylammonio-2-hydroxypropyl sultaine is preferred.

In addition to the surfactants mentioned above, laundry detergent bars may contain hydrotropes or mixtures of hydrotropes. Preferred hydrotropes include the alkali metal, preferably sodium, toluenesulfonic, xylenesulfonic, cumenesulfonic, sulfosuccinic acid salts and mixtures thereof. The substantially anhydrous acid or salt form of the hydrotrope is added to the acid form of the anionic surfactant, preferably prior to neutralization. Hydrotropes are preferably present at from about 0.5% to about 5% of the laundry detergent bar.

bleach

Bleaching agents are preferably present in detergent compositions at a level of from about 0.10% to about 60%, more preferably from about 1% to about 50%, most preferably from about 1% to about 20%, by weight. The bleaching agent useful in the present invention can be any oxygen bleaching agent useful in detergent compositions for fabric cleaning, hard surface cleaning or other cleaning purposes now known or to become known. Bleach mixtures can also be used.

Preferred bleaching agents for use herein are those peroxygen bleaching compounds capable of generating hydrogen peroxide in aqueous solution. These compounds are well known in the art and include hydrogen peroxide and alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds such as alkali metal perborates, percarbonates Salt, superphosphate, etc. Mixtures of two or more such bleaching compounds can also be used if desired.

Preferred peroxygen bleaching compounds for use herein include sodium perborate, commercially available as the mono- and tetrahydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and peroxy sodium. Particular preference is given to sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is more preferred because it is very stable in storage and yet dissolves rapidly in bleach solutions.

Persulfate bleach (eg, OXONE by DuPont Industries) may also be used.

Useful percarbonate bleaches include dry particles having an average particle size of from about 500 microns to about 1,000 microns, with no more than about 10% by weight of said particles smaller than about 200 microns, and no more than 10% ( The particles by weight) are greater than about 1250 microns. Optionally, the percarbonate may be coated with silicate, borate or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Another type of effective bleaching agent that can be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salts of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781 to Hartman, issued November 20, 1984; U.S. Patent Application 740,446 to Burns et al., filed June 3, 1985; In patent application 0,133,354 and in US Patent 4,412,934 issued November 1, 1983 to Chung et al. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid described in US Patent Application 4,634,551, issued January 6, 1987 to Burns et al.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the present invention. A particularly important class of non-oxygen bleaches includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US Patent 4,033,718, issued July 5, 1977 to Holeombe et al. If used, detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

enzyme

The level of enzyme in the detergent composition is preferably about 0.0011 mg to about 2.2 mg of active enzyme per gram of detergent composition, more preferably about 0.0011 mg to about 1.1 mg per gram of composition, and most preferably about 0.0011 mg to about 0.55 mg of active enzyme. Enzymes incorporated include proteases, amylases, lipases, cellulases, and peroxidases, and mixtures thereof.

Various enzyme materials and methods of incorporation into synthetic detergent compositions are disclosed in US Patent 3,553,139, issued January 5,1971 to McCarty et al. Enzymes are also disclosed in US Patent 4,101,457, Place et al., issued July 18, 1978, and US Patent 4,507,219, Hughes, issued March 26, 1985. Enzyme materials for use in liquid detergent formulations and methods for their incorporation into such formulations are disclosed in US Patent 4,261,868, issued April 14,1981 to Hora et al. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US Patent 3,600,319, issued August 17, 1971 to Gedge et al., and European Patent Application Publication No. 0,199,405, Application No. 86200586.5, published October 29, 1986 for Venegas. Enzyme stabilization systems are also described, for example, in US Patent No. 3,519,570.

Suitable examples of proteases are subtilisins obtained from specific strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a Bacillus strain having maximum activity in the pH range of 8-12, developed by Novo Industries A/S of Denmark, hereinafter "Novo", and sold as ESPERASE ^(TM) . Preparations of this and similar enzymes are described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE ^™ and SAVINASE ^™ from Novo and MAXATASE ^™ from International Biosynthesis, The Netherlands; Protease B in EP 303,761A dated 9 January 1985 and EP 130,765A dated 9 January 1985. See also the high pH protease of Bacillus sp. NCIMB 40338 described in WO9318140A from Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those in WO9510591A to Procter & Gamble. When desired, proteases with low adsorption and high hydrolytic properties are available as described in WO9507791 by Procter & Gamble. Recombinant trypsin-like proteases suitable for the detergents of the present invention are described in WO9425583 to Novo.

In more detail, a particularly preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant having a virtually unfound amino acid sequence, which is derived from a precursor carbonyl hydrolase in the following manner; The carbonyl hydrolase is equivalent to various amino acid residues at position +76, preferably, according to the numbering of Bacillus amyloliquefaciens subtilisin, it is also equivalent to the amino acid residues selected from +99, +101, +103, +104 , +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, + One or more amino acid residues at positions 217, +218, +222, +260, +265, and/or +274 are substituted with different amino acids, as described in A. Baeck et al. titled "Protease-containing cleaning Compositions (Protease-Containing Cleaning Compositions)" U.S. Patent Application Serial No. 08/322676 and U.S. Patent Application Serial No. entitled "Bleaching Compositions Comprising Protease Enzymes" in C. Ghosh et al. 08/322677, both filed October 13, 1994.

Proteases are generally present at levels of from about 0.0055 mg to about 0.022 mg of active enzyme per gram of composition. Proteases of such commercial formulations are generally present in amounts sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, their optimum pH is between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307 to Barbesgoard et al., issued March 6, 1984, which discloses the production of cellulase 212 from Humicolainsolens and Humicola sp. Fungal cellulase produced by molds, and cellulase extracted from the hepatopancreas of marine molluscs (DolabellaAuricula Solander). Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME ^™ (Novo) is especially suitable.

Cellulases are typically present at levels of from about 0.002 mg to about 0.04 mg of active enzyme per gram of composition. Preferred is Carezyme ^(TM) having an activity of 5000 CEVU per gram. Most preferred is Carezyme ^(TM) having an activity of 1000 CEVU per gram.

A preferred bar composition includes an enzyme blend:

(1) the composition contains from about 0.0055 mg to about 0.022 mg of protease per gram; and

(2) The composition contains about 0.002 mg to about 0.04 mg of cellulase per gram.

In the present invention, amylases that are particularly suitable for automatic dishwashing purposes but are not limited thereto include, for example, the amylases described in Novo's GB1,296,839; RAPIDASE ^™ from International Biosynthesis Corporation and TERMAMYL ^™ from Novo. Novo's FUNGAMYL( ^TM) is particularly suitable. Enzyme engineering for increased stability, eg oxidative stability, is known. See, eg, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present compositions enable the use of amylases with improved stability, especially improved oxidative stability, in e.g. automatic dishwashing type detergents, with TERMAYL ^™ commercially available in 1993 as a reference point Measurement. These preferred amylases in the present invention are characterized as "stability-enhanced" amylases characterized by measurable improvements in stability as determined by at least one or more of the following compared to the amylase designated above as the reference point: For example, oxidation stability to hydrogen peroxide/tetraacetylethylenediamine in a buffer of pH 9-10; for example, thermal stability at conventional detergent temperatures, such as about 60° C.; or a base with a pH of about 8 to about 11 stability. Stability can be measured using any of the technical test methods disclosed in the art. See for example references disclosed in WO9402597. Stability-enhanced amylases can be obtained from Novo or Genencor International. A class of highly preferred amylases herein has the commonality of being derived from one or more Bacillus subtilis amylases, especially Bacillus subtilis alpha-amylases, using site-directed mutagenesis, with one, two or more amylases It is irrelevant whether the strain is an intermediate precursor or not. Amylases having enhanced oxidative stability compared to the above-identified reference amylases are preferred for use in detergent compositions according to the invention, especially in detergent compositions for bleaching, more preferably oxygen bleaching which differs significantly from chlorine bleaching. Such preferred amylases include (a) amylases according to above incorporated WO9402597, Novo, 3 February 1994, as further illustrated by mutants, wherein alanine or threonine is used, preferably threonine , substituting the methionine residue at position 197 of the Bacillus licheniformis alpha-amylase known as TERMAMYL ^TM , or the homologous position of a similar parental amylase, e.g. Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus Variety; (b) as Genencor International is in by C.Mitchinson on March 13th-17th, 1994, submits on the 207th American Chemical Society National Meeting (207th American Chemical Society National Meeting) entitled "Oxidation-resistant α Stability-enhanced amylases described in the article "Oxidatively Resistant α-Amylases". It is mentioned that bleach in automatic dishwashing detergents inactivates alpha-amylases, but amylases with improved oxidative stability are made by Genecor from Bacillus licheniformis NCIB8061. Methionine (Met) was considered the most likely residue to be modified. Substitution of Met one at a time at 8, 15, 197, 256, 304, 366 and 438 resulted in specific mutants, particularly important M197L and M197T, the M197T variant being the most stably expressed variant. Stability was determined in CASCADE ^™ and SUNLIGHT ^™ ; (c) particularly preferred amylases herein are amylase variants with additional modifications in the intermediate parent as described in WO9510603A and available as DURAMYL ^™ from the assignee Novo . Other particularly preferred oxidative stability-enhanced amylases include those described in WO9418314 and WO9402597 to Novo. Any other oxidative stability-enhanced amylase may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parental forms of available amylases. Other preferred enzyme variants may be used. See WO9509909A to Novo.

Other amylases include those described in WO95/26397 and Novo Nordisk's co-pending application PCT/DK96/00056. Specific amylases for use in the detergent compositions of the present invention include starches characterized by having a specific activity at least 25% higher than that of Termamyl ^™ at a temperature of 25°C to 55°C and a pH of 8 to 10 Enzyme, the specific activity of which was measured by Phadebas ^™ Amylase Activity Assay. (This Phadebas ^(TM) amylase activity detection method is described on pages 9-10 of WO95/26397). The invention also includes amylases having at least 80% homology to the amino acid sequences listed in the SEQ ID table of this reference.

Amylases are generally present at levels of from about 0.0045 mg to about 0.45 mg of active enzyme per gram of composition.

Suitable lipases for detergent use include those produced by Pseudomonas-based microorganisms such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. See also lipases in Japanese Patent Application No. 53,20487, laid open February 24,1978. Lipases under the trademark Lipase P "Amano" or "Amano-P" are available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan. Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscoum, e.g. Chromobacter viscosum var.lipolyticum NRRLB3673, the Chromobacter viscoum lipase of American Biochemical Company and Netherlands Disoynth Company, and the lipase from Pseudomonas Gladiolis.The lipase derived from Humicola lanuginosa and commercially obtained from Novo is preferred for use in Lipases in the present invention, see also EP341,947. Lipase and amylase variants having stability to peroxidases are described in WO9414951A to Novo. See also WO9205249 and RD94359044.

Lipase activity is expressed in lipase units (LU) at a ^stable pH at The amount of lipase that produces 1 μmol of titratable fatty acid per minute under the conditions: temperature 30° C., pH 9.0, substrate is an emulsion of 3.3% (weight) olive oil and 3.3% gum arabic.

Lipase is generally present at levels of from about 0.0022 mg to about 1.1 mg of active enzyme per gram of composition.

Peroxidases may be used in conjunction with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used in "solution bleaching", that is, in washing operations to prevent the transfer of dyes or pigments removed from wash items to other wash items in the wash liquor. Peroxidases are known in the art and include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidases. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.

Other types of enzymes may also be included. They are of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH activity and/or stability optima, thermostability, stability to active detergents, builders, and the like. In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.

Optional components

detergent builder

The laundry bars of the present invention contain from about 5% to about 60% by weight of detergent builder, preferably the laundry bars contain from about 5% to about 30% by weight of the builder, most preferably from about 5% to About 15%.

These detergent builders can be, for example, the water-soluble alkali metal salts of phosphoric acid, pyrophosphoric acid, orthophosphoric acid, tripolyphosphoric acid, higher polyphosphoric acids and mixtures thereof. The builder can also be a non-phosphate detergent builder. Specific examples of non-phosphorous inorganic detergency builders include water-soluble inorganic carbonates and bicarbonates. Carbonates, bicarbonates and silicates of alkali metals such as sodium and potassium are especially suitable for use in the present invention.

Aluminosilicate ion exchange materials are also useful. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring or synthetically derived. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the designations Zeolite A and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ ·(SiO ₂ ) ₁₂ ].xH ₂ O

wherein x is about 20 to about 30, especially about 27.

Water-soluble organic detergency builders such as the alkali metal, ammonium and substituted ammonium salts of polycarboxylic acids are also useful herein. Specific examples of useful polycarboxylate builders include ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acid, polyacrylic acid, polymaleic acid, acrylic maleic acid, Acid copolymers, polyaspartic acid, sodium, potassium, ammonium and substituted ammonium salts of citric acid or the acid itself. Other useful polycarboxylate detergency builders are the materials described in US Patent 3,308,067, issued March 7,1967 to Diehl. Detergent builder mixtures are useful herein.

bleach activator

The detergent compositions of the present invention may optionally contain one or more bleach activators. Bleach activators, if used, preferably comprise from about 0.05% to about 10%; more preferably from about 0.05% to about 5% by weight.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably used in combination with bleach activators which result in the in situ generation of peroxyacids corresponding to the bleach activators in aqueous solution (ie during the wash). Various non-limiting examples of activators are disclosed in US Patent 4,915,854 and US Patent 4,412,934, issued April 10, 1990 to Mao et al. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof can also be used. See also US Patent 4,634,551 for other typical bleaches and activators useful in the present invention.

Highly preferred amido-derived bleach activators are those of the formula

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L

wherein ^R1 is an alkyl group containing about 6 to about 12 carbon atoms, ^R2 is an alkylene group containing 1 to about 6 carbon atoms, ^R5 is H or an alkyl group containing about 1 to about 10 carbon atoms , aryl or alkaryl, and L is any suitable leaving group. A leaving group is any group which leaves the bleach activator as a result of nucleophilic attack of the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonate, ( 6-Decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other types of bleach activators include the benzoxazine-type activators disclosed in US Patent 4,966,723, issued October 30,1990 to Hodge et al. Highly preferred benzoxazine type activators are:

Another class of preferred bleach activators includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:

wherein R is H or an ^alkyl , aryl, alkoxyaryl or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Amides, octanoyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US Patent 4,545,784, issued October 8, 1985 to Sanderson, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed onto sodium perborate.

bleach catalyst

The laundry bar compositions of the present invention optionally include a bleach catalyst. The catalyst is included in the laundry bar at a level of from about 0.002% to about 14%, and preferably from about 0.02% to 10%.

Bleach compounds can be catalyzed by manganese compounds if desired. Such compounds are well known in the art and include, for example, manganese as disclosed in U.S. Patent 5,246,621, U.S. Patent 5,244,594, U.S. Patent 5,194,416, U.S. Patent 5,114,606 and European Patent Application Publication Nos. base catalyst. Preferable examples of these catalysts include Mn ^IV ₂ (uO) ₃ (-1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (-1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1, 4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (-1,4,7-trimethyl-1,4,7 -Triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal-based bleach catalysts include those disclosed in US Patent 4,430,243 and US Patent 5,114,611. The use of manganese with various complex ligands to enhance the bleaching effect is also reported in the following US patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;

As a matter of fact and not limitation, the compositions and methods of the present invention can be adjusted to provide about at least one part per million active bleach catalyst species in the wash solution, and preferably about 0.1 ppm to From about 700 ppm, more preferably from about 1 ppm to about 500 ppm of catalyst species.

Chelating agent for detergent

The laundry bar compositions of the present invention optionally include a detergent chelating agent. Detergent chelating agents are included in the laundry bars at a level of from about 0.1% to about 5.0%, preferably from about 0.3% to about 1.5%, most preferably at 0.9%.

Chelating agents are capable of sequestering and chelating alkali cations (such as sodium, lithium, and potassium), alkaline earth metal cations (such as magnesium and calcium), and most preferably heavy metal cations such as iron, manganese, zinc, and aluminum. Preferred cations include sodium, magnesium, zinc and mixtures thereof. The use of such a detergent chelating agent component is beneficial in enhancing the performance of the surfactants in the laundry bars of the present invention, meaning that compared to similar laundry bars containing high levels of anionic surfactant but no detergent chelating agent, Comparable sudsing and cleaning performance can be obtained for a given level of anionic surfactant and a given level of detergent chelating agent.

Chelating agents for detergents are preferably phosphonate chelating agents, especially selected from diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) and mixtures thereof and salts thereof and Phosphonate chelating agents of their complexes, and acetate chelating agents, especially those selected from the group consisting of diethylenetriaminepenta(acetic acid), ethylenediaminetetra(acetic acid), and mixtures and salts and complexes thereof. salt chelating agent. Particularly preferred are the sodium, zinc, magnesium and aluminum salts of diethylenetriaminepenta(methylenephosphonic acid), diethylenetriaminepenta(acetic acid) and complexes thereof, and mixtures thereof.

Preferably, such salts or complexes have a molar ratio of metal ions to chelating agent molecules of at least 1:1, preferably at least 2:1.

Chelating agents for detergents can be used in the form of granules or granules, or in aqueous or solvent solutions. Methods for the preparation of such salts and complexes are well known and described in US Patent 4,259,200, issued 3/31/81. The preferred form is granules or granules. Such granular or granular detergent chelating agents can be formed using organic or inorganic binders. Suitable organic binders are, for example, nonionic surfactants. Suitable inorganic binders include sodium tripolyphosphate, sodium carbonate, magnesium sulfate, and the like. Any granulation technique known in the art may be employed, such as by spraying molten nonionic surfactant onto a moving bed of dried metal complex, fluid bed drying, and the like.

Other optional components

The detergent bars of the present invention contain up to about 80% by weight of other optional ingredients typically used in detergent products. The following is representative of such material, but is not intended to be limiting.

Another useful optional component of the laundry detergent bars of the present invention are silicates, especially sodium silicates. Sodium silicate can be used in amounts up to about 15% silicate solids having a weight ratio of _SiO2 to _Na2O of about 1.0:1 to about 3.4:1.

Another preferred additional component is layered sodium silicate, most preferably the commercially available SKS-6 ( _Na2Si2O5 ), available from Hoechst and _published March 12 _, 1987 in US Patent 4,664,839. Another preferred phyllosilicate is disclosed in European Patent Publication 550,048, July 7, 1993 (Kao), which discloses a synthetic phyllosilicate having a chain structure and having the following chemical formula in anhydrous form: Composition of crystalline substances:

xM ₂ O.ySiO ₂ .zM′O

Wherein M represents sodium and/or potassium; M' represents calcium and/or magnesium; y/x is 0.5～2.0; And z/x is 0.005～1.0, said chain structure in Raman spectrum is in 900～1200cm At least 970 ± 2 cm ^-1 in the ^-1 range appeared as the main scattering peak. Such layered silicate material is particularly preferred because of its ability to provide alkalinity and calcium chelating or builder functionality.

Another preferred additional component for laundry bars is a fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms. Fatty alcohols are very effective in reducing the wear rate and smear (paste) of the laundry bars of the present invention. Preferred fatty alcohols have alkyl chains mainly containing 16-18 carbon atoms, so-called "high cut fatty alcohols", which are capable of exhibiting a lower fatty alcohol undertone relative to broad cut fatty alcohols. Typically, the level of fatty alcohol in the laundry bar is up to 10%, more preferably from about 0.75% to about 6%, most preferably from about 2% to about 5%. Fatty alcohols are usually added to the formulations of the present invention in the form of free fatty alcohols. But low levels of fatty alcohols are introduced into the laundry bars as impurities or unreacted raw materials. For example, coconut fatty alkyl sulfate based laundry bars contain 0.1 to 3.5%, more preferably 2% to 3%, by weight of free coconut fatty alcohol as unreacted raw material, based on coconut fatty alkyl sulfate.

Free fatty alcohols also act as foam boosters to strengthen and prolong foam production and life. For promoting suds, preferred fatty alcohols have alkyl chains containing primarily 12 to 14 carbon atoms and are present in the composition at levels of about 0.5% to 3%. Preferably, the amount of narrow-cut _C12 alkyl alcohol is 0.5% to 2%.

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

Preferred SRAs have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fiber and remains bound throughout the wash and rinse cycle, thereby acting as an anchor for the hydrophilic portion kick in. This can make stains that have been treated with SRA easier to remove in subsequent washes.

SRA includes a variety of charged, such as anionic or even cationic substances, see US Patent 4,956,447 issued to Gosselink et al. on September 11, 1990, and uncharged monomer units, and their structures can be linear or branched Or even star-shaped. They may include capping moieties that are particularly effective in controlling molecular weight or modifying physical or surface active properties. The structure and charge distribution can be determined by different fiber or fabric types and different detergents or detergent additives applied.

Preferred SRAs include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization, often using a metal catalyst such as titanium (IV) alkoxide. Of course, the ability to make such esters by incorporating additional monomers into the ester structure at one, two, three, four, or more positions may be used without the formation of all tightly cross-linked structures.

Suitable SRAs include the sulfonation products of substantially linear ester oligomers consisting of a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and covalently attached to the backbone. Allyl-derived sulfonated terminal moiety compositions such as those described in US Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate ("DMT") and 1,2- Propylene glycol ("PG") is reacted in a two-stage transesterification/oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730 issued December 8, 1987 to Gosselink et al., for example by poly(ethylene glycol) Those prepared by transesterification/oligomerization of methyl ether, DMT, PG and poly(ethylene glycol) ("PEG"). Other examples of SRAs include: partially and fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6- Oligomers made from sodium dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomers in U.S. Patent 4,702,875 issued October 27, 1987 to Gosselink, such as DMT, Products made from combinations of methyl (Me)-terminated PEG and EG and/or PG, or DMT, EG and/or PG, methyl-terminated PEG and sodium dimethyl 5-sulfoisophthalate; and the anions in U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado, Gosselink et al., particularly sulfoaroyl-terminated terephthalates, the latter being typical for laundry and fabric conditioning products SRA, an example is an ester composition made from monosodium m-sulfobenzoate, PG and DMT, optionally but preferably also including added PEG, such as PEG 3400.

SRA also includes: simple copolymeric blocks of ethylene or propylene terephthalate with polyethylene oxide or polyoxypropylene terephthalate, see 1976 US Patent 3,959,230, Hays, March 25 and US Patent 3,893,929, Basadur, July 8, 1975; cellulose derivatives such as hydroxyether cellulose polymers available from Dow under the designation METHOCEL; C ₁ -C ₄ Alkyl cellulose and C ₄ hydroxyalkyl cellulose, see U.S. Patent 4,000,093 of Nicol et al., December 28, 1976; and have an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a methyl cellulose ether having a solution viscosity of about 80 to about 120 centipoise measured at 20°C when it is a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers produced by Shinetsu Kagaku Kogyo KK.

Suitable SRAs characterized by poly(vinyl ester) hydrophobic moieties include graft copolymers of polyvinyl esters, such as C ₁ -C ₆ vinyl esters grafted onto a polyalkylene oxide backbone, preferably polyvinyl acetate . See European Patent Application 0219048, published April 22, 1987, by Kud et al. Commercially available examples include SOKALAN SRA, such as SOKALAN HP-22 available from BASF, Germany. Other SRA is polyethylene terephthalate containing 10 to 15% by weight and 80 to 90% by weight of polyoxyethylene glycol with an average molecular weight of 300 to 5,000. Dicarboxylic acid oxyethylene glycol ester repeat unit polyester. Commercial examples include Dupont's ZELCON 5126 and ICI's MILEASE T.

Another preferred SRA is an oligomer having the empirical formula (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ which includes terephthaloyl (T), sulfoisophthaloyl Acyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and their preferably capped with a capping group (CAP), preferably with a modified isethionate , such as oxyethyleneoxy and oxy-1,2-propyleneoxy comprising one sulfoisophthaloyl unit, five terephthaloyl units, and a defined ratio of preferably about 0.5:1 to about 10:1 base unit and 2 oligomers of capping units derived from 2-(2-hydroxyethoxy)-sodium ethanesulfonate. Said SRA preferably also includes 0.5% to 30% of crystallinity-reducing stabilizers based on oligomer weight, such as anionic surfactants such as linear sodium dodecylbenzene sulfonate or selected from xylene, isopropyl Anionic surfactants of benzene and tosylate or mixtures thereof, these stabilizers or modifiers added to synthesis vessels, all disclosed in Gosselink, Pan, Kellett and Hall, U.S.A., granted May 16, 1995 Patent 5,415,807. Suitable monomers for the above SRA include sodium 2-(2-hydroxyethoxy)ethanesulfonate, DMT, sodium dimethyl 5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRAs are oligoesters comprising: (1) a backbone comprising (a) at least one group selected from dihydroxysulfonate, polyhydroxysulfonate, at least trifunctional, thereby forming Ester linkages to form branched oligomer backbone units, and combinations thereof; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one unit that is a 1,2-oxyalkylene oxide moiety unsulfonated units; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated units, isethionate , alkoxylated propylsulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are esters with 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 in the present invention, (DEG) represents a di(oxyethylene)oxy unit, and (SEG) represents a compound derived from glycerol sulfoethyl ester and related moiety units. From the unit, (B) represents at least trifunctional, thereby forming an ester bond to form a branched oligomer backbone unit, x is about 1 to about 12, y' is about 0.5 to about 25, y" is 0 to about 12, y' is 0 to about 10, the sum of y'+y"+y' is about 0.5 to about 25, z is about 1.5 to about 25, z' is about 0 to about 12, z+z ' is 1.5 to about 25, q is about 0.05 to about 12, m is about 0.01 to about 10, and x, y', y", y', z, z', q and m represent per mole of said The average number of moles of corresponding units of the ester and the molecular weight of said ester is from about 500 to about 5,000.

For the above esters, preferred SEG and CAP monomers include sodium 2-(2-,3-dihydroxypropoxy)ethanesulfonate (“SEG”), 2-{2-(2-hydroxyethoxy) Sodium ethoxylated}ethanesulfonate ("SE3") and its homologues and mixtures thereof, and products of ethoxylated and sulfonated allyl alcohol. Preferred SRA esters of this class include transesterification and oligomerization of sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or 2-[2 - products of sodium {2-(2-hydroxyethoxy)ethoxy}ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate, EG and PG , and its chemical formula is (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where _CAP is (Na ⁺ _-O3S [ _CH2CH2O ]3.5)- and B is a unit derived from glycerol and has an EG/PG molar ratio of about 1.7:1 after complete hydrolysis as measured by conventional gas chromatography.

Other types of SRAs include: (1) nonionic terephthalates using diisocyanate coupling reagents to link polyester structures, see U.S. Patent 4,201,824 to Violland et al. and U.S. Patent 4,240,918 to Lagasse et al.; and ( II) SRA with carboxylate end groups prepared by adding trimellitic anhydride to known SRA thereby converting the terminal hydroxyl groups to trimellitic esters. With the appropriate choice of catalyst, the trimellitic anhydride bonds to the terminal end of the polymer through the ester of the isolated carboxylic acid of the trimellitic anhydride rather than by opening the anhydride linkage. Nonionic or anionic SRAs can be used as raw materials as long as they have esterifiable hydroxyl end groups. See US Patent 4,525,524 to Tung et al. Other types include: (III) anionic terephthalate-based SRAs of urethane-linked variants, see U.S. Patent 4,201,824 to Violland et al; (IV) poly(vinylcaprolactam) and , such as vinylpyrrolidone and/or related copolymers of dimethylaminoethyl methacrylate, which include nonionic and anionic polymers, see U.S. Patent 4,579,681 to Ruppert et al; (V) In addition to BASF's SOKALAN types, A graft copolymer obtained by grafting acrylic acid monomers onto sulfonated polyesters. These SRAs no doubt possess similar soil release and antiredeposition activity to the known cellulose ethers, see European Patent 279,134A, Rhone Poulenc Chemie, published 1988. Other types include: (VI) grafting of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as casein, see BASF European Patent 457,205A (1991); Polyester-polyamide SRAs obtained by condensation of diacids, caprolactam and polyethylene glycol are particularly suitable for treating polyamide fabrics, see DE 2,335,044, Unilever N.V., 1974, Bevan et al. Other useful SRAs are described in US Patents 4,240,918, 4,787,989 and 4,525,524.

Another preferred optional component in laundry bars is a dye transfer inhibiting (DTI) component that prevents loss of color fidelity and intensity in fabrics. Preferred DTI components include polymeric DTI materials capable of binding fugitive dyes thereby preventing their deposition on fabrics; and decolorizing DTI materials capable of decolorizing fugitive dyes by oxidation. Examples of decolorizing DTIs are hydrogen peroxide or a source of hydrogen peroxide such as percarbonate or perborate. Non-limiting examples of polymeric DTI materials include polyvinylpyridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymers, and mixtures thereof.

More specifically, preferred polyamine N-oxide polymers for use in the present invention comprise units having the formula: RA _x -P; wherein P is a polymerizable unit to which an NO group can be attached or the NO group can be Form part of a polymerizable unit, or the NO group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O- , -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, hetero Cyclic or alicyclic groups or any combination thereof. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The NO group is represented by the general structural formula below:

wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen in the NO group can be attached to any of the above groups group or form part of any of the above groups. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

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

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPI") are also preferred for use in the present invention. The average molecular weight of PVPI is preferably 5,000 to 1,000,000, more preferably 5,000 to 200,000, and most preferably 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis, Vol. 113, "Modern Methods for the Characterization of Polymers"). The molar ratio of N-vinylimidazole to N-vinylpyrrolidone in the PVPI copolymer is generally 1:1-0.2:1, more preferably 0.8:1-0.3:1, most preferably 0.6:1-0.4:1. These polymers can be linear or branched.

The compositions of the present invention may also optionally comprise polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000 and more preferably from about 5,000 to about 50,000. Examples of PVP are disclosed in eg EP-A-262,897 and EP-A-256,696. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the weight ratio of PEG to PVP is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.

One or more polymeric DTI materials may also be used in combination with one or more decolorized DTI materials. The DTI material is beneficially present in the laundry bar at up to about 10%, preferably from about 0.05% to 5%, more preferably from about 0.2% to about 2%.

Another preferred optional component in laundry bars is a fabric softener component. Preferred fabric softener components include softening clays such as montmorillonite, bentonite and hectorite clays, and acid treated bentonites or other softening clays. Examples of such clays are disclosed in US Patent 3,959,155, issued May 25, 1976, and US Patent 5,019,292, issued May 28, 1991. The fabric softener component is added to the laundry bar at levels up to 20%, preferably from about 2% to about 15%.

Sodium sulfate is a known filler compatible with the compositions of the present invention. It can be a by-product of the surfactant sulfation and sulfonation process, or it can be added separately.

Calcium carbonate (also known as Calcarb) is also well known and often used as a laundry bar ingredient. Typical levels of such materials are up to 40%, preferably from about 5% to about 25%.

Dissolvable forms of adhesives, including natural and synthetic starches, gums, thickeners, and mixtures thereof, that hold the laundry bars together may also be used. Some binders also function as soil suspending agents, and these include, for example, carboxymethylcellulose and the water-soluble salts of carboxymethylcellulose.

A preferred soil suspending agent which may optionally be used is an acrylic/maleic acid copolymer, commercially available as Sokolan ^(TM) from BASF Corporation. Other soil suspending agents include polyethylene glycols and ethoxylated mono- and polyamines and quaternary ammonium salts thereof having a molecular weight of about 400 to 10,000. Dyes, pigments, optical brighteners, fungicides and fragrances may also be added to the stick composition.

Craftsmanship

The detergent laundry bars of the present invention can be produced using conventional soap or detergent bar manufacturing equipment with some or all of the following key devices: blender/mixer, milling or refining plodder, two-stage vacuum plodder, logo printer/ Cutting machines, cooling tunnels and packaging machines. In a typical process, where the surfactant system includes a mixture of alkylbenzene sulfonates and alkyl sulfates, the materials are mixed in a blender. The alkylbenzene sulfonic acid is added to the mixture of basic inorganic salts and the resulting partially neutralized mixture is mechanically processed to homogenize and completely neutralize the mixture. Once the neutralization reaction is complete, the alkyl sulfate surfactant is added, followed by the remainder of the other component materials. The mixing time is 1 minute to 1 hour, usually 2 to 20 minutes. Drain the blender mixture into a surge tank. The product is transported from the buffer tank to the milling or refining plodder via a multi-stage transfer conveyor.

After milling or preliminary ploding, the product is then conveyed to a secondary vacuum plodder operating under a vacuum of, for example, 600-740 mmHg to remove entrained air. The product is extruded and cut to the desired strip length, and printed with the brand name of the product. The printed strips are cooled, for example in cooling tunnels, before they are packaged, boxed and sent for storage.

Example

The invention is illustrated by the following non-limiting examples. All parts and percentages herein are by weight unless otherwise specified.

Various bar compositions (Examples A-E) can be prepared using the methods described above.

A B C

(weight percent) linear alkylbenzene sulfonate 6.75 6.75 6.75 alkyl sulfate 15.75 15.75 15.75 fatty alkyl alcohol 1.00 1.00 1.00 tetrasodium pyrophosphate 5.00 5.00 5.00 sodium tripolyphosphate 5.00 5.00 5.00 sodium aluminum silicate 0.975 0.975 0.975 Sodium Carbonate 15.00 15.00 15.00 Calcium Carbonate 33.15 32.90 33.07 Perborate Hydrate 2.25 2.25 2.25 Carezyme 1000 CEVU/g 0.25 0.25 0.0 Savinase 4T 0.08 0.0 0.08 Diethylene Triamine Penta 0.7 0.7 0.2 Fluorescent Agent 2 0.4 Substituted methyl cellulose 0.72 0.72 0.72 Organic polymer 0.50 0.50 0.50 TiO ₂ 1.00 1.00 1.00 Fragrance 0.35 0.35 0.35 Other conventional components Balance Balance Balance Balance

D D E E

(weight percent) linear alkylbenzene sulfonate 6.46 6.46 soda ash 17.86 17.86 C12-18 alkyl sodium sulfate 8.96 8.96 C12 free CFA 1.00 1.00 sodium tripolyphosphate 10.00 10.00 zeolite A 1.25 1.25 sulfuric acid (98%) 2.50 2.50 calcium carbonate 39.10 36.56 Glycerin 1.00 1.00 Fluorescent Agent 0.20 0.20 CMC ^* 0.50 0.50 Acrylic/Maleic Acid Copolymer 0.455 0.455 Polyvinylpyridine N-oxide Polymer 0.40 0.40 Soil Release Polymer 0.30 0.30TiO ₂ 1.00 1.00 Diethylene Triamine Penta Sodium 2.80 2.80 Spice 0.35 0.35 Savinase 4T 0.08 0.12 Carezyme 1000CEVU/g 0.25 0.50 Perborate-hydrate 2.25 4.50 Other conventional components Balance Balance

^* Substituted cellulosic material

Claims (10)

1. detergent for washing clothes bar composition comprises by weight:

(a) about detergent use tensio-active agent of 10%～about 60%, wherein anion surfactant account for the tensio-active agent total amount at least about 10%;

(b) about oxygen bleaching agent of 0.10%～about 60%; With

(c) about 0.0011 milligram～about 2.2 milligrams of organized enzymes that are selected from proteolytic enzyme, amylase, cellulase, lipase, peroxidase and its mixture of every gram composition.

2. according to the composition of claim 1, wherein oxygen bleaching agent is about 1%～about 50% the perborate bleach of content.

3. composition according to claim 2, wherein perborate bleach is the Sodium peroxoborate monohydrate.

4. composition according to claim 2, wherein enzyme is the mixture of the cellulase of the proteolytic enzyme of the about 0.0055mg of every gram composition～about 0.022mg and the about 0.002～about 0.04mg of every gram composition.

5. the composition according to claim 4 also comprises about detergent builders that is selected from tripoly phosphate sodium STPP, tetrasodium pyrophosphate, crystal aluminosilicate and its mixture of 5%～about 60%.

6. the composition according to claim 5 also comprises about phosphine acid salt chelator of 0.1～about 5.0%.

7. the composition according to claim 6 also comprises about 0.05%～about 10% the bleach-activating agent that is selected from nonanoyl oxygen base benzene sulfonate, tetra acetyl ethylene diamine and its mixture.

8. detergent for washing clothes bar comprises by weight:

(a) about 15%～about 40% be selected from the alkyl-sulphate with 10～20 carbon atom alkyl chains, linear alkylbenzene sulfonate (LAS), branch-alkylbenzene sulfonate (ABS) and the anion surfactant of its mixture with 10～22 carbon atom alkyl chains with 10～22 carbon atom alkyl chains.

(b) cellulase of the proteolytic enzyme of the about 0.0055mg of every gram composition～about 0.022mg and the about 0.002～about 0.04mg of every gram composition.

(c) about detergent builders that is selected from tripoly phosphate sodium STPP, tetrasodium pyrophosphate, crystal aluminosilicate and its mixture of 5%～about 30%; With

(d) about perborate bleach of 1%～about 20%.

9. composition according to Claim 8, wherein perborate bleach is the Sodium peroxoborate monohydrate.

10. the composition according to claim 9 also comprises about phosphine acid salt chelator of 0.3%～about 1.5%.