WO2000041522A2 - Compositions de nettoyage renfermant un agent multifonctions; methode d'utilisation - Google Patents

Compositions de nettoyage renfermant un agent multifonctions; methode d'utilisation Download PDF

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Publication number
WO2000041522A2
WO2000041522A2 PCT/US2000/000437 US0000437W WO0041522A2 WO 2000041522 A2 WO2000041522 A2 WO 2000041522A2 US 0000437 W US0000437 W US 0000437W WO 0041522 A2 WO0041522 A2 WO 0041522A2
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WO
WIPO (PCT)
Prior art keywords
amylase
cleaning
compressed
compositions
composition
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PCT/US2000/000437
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English (en)
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WO2000041522A3 (fr
Inventor
Jean-Luc Philippe Bettiol
Yong Zhu
Eric Christopher Wells
Michael Stanford Showell
Andre Christian Convents
Christiaan Arthur Jacques Kamiel Thoen
Glenn Steven Ward
Lynda Anne Speed
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU24959/00A priority Critical patent/AU2495900A/en
Publication of WO2000041522A2 publication Critical patent/WO2000041522A2/fr
Publication of WO2000041522A3 publication Critical patent/WO2000041522A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the present invention relates to cleaning compositions comprising a multifunction component capable of hydrolyzmg 1,3- ⁇ -glucans, 1,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans, and methods for cleaning hard surface substrates, especially dishware, cookware, tableware, etc., by applying such cleaning compositions to the substrates. More specifically, the present invention relates to cleaning compositions that provide tough food cleaning, or otherwise removing and/or reducing soils, especially carbohydrate soils, and/or removing and/or reducing spotting and/or films, from hard surface substrates, especially dishware, cookware, tableware, etc.
  • the cleaning compositions of the present invention and methods of using same provide enhanced cleaning and improved tough food cleaning and/or removal and/or reduction of spotting and/or films from hard surface substrates relative to amylase-containmg detergent compositions without such a multifunction component.
  • protease enzymes have long been used in laundry detergents to assist in the removal of certain stams from fab ⁇ cs.
  • Each class of enzyme (amylase, protease, etc ) generally catalyzes a different chemical reaction
  • protease enzymes are known for their ability to hydrolyze (break down a compound into two or more simpler compounds) other proteins. This ability has been taken advantage of through the incorporation of naturally occurring or engineered protease enzymes to laundry detergent compositions.
  • formulators have expe ⁇ enced difficulties m formulating detergents which remove carbohydrate soils such as cereal and gram soils, for example, oatmeal, barley, rye, wheat, and ⁇ ce.
  • carbohydrate soil removal formulators have turned to amylase and hemicellulase enzymes.
  • consumers continue to expe ⁇ ence problems m removing carbohydrate soils.
  • WO 95/35382 to Gist-Brocades discloses the use of hemicellulases, such as xylanases, in dishwashing compositions.
  • the p ⁇ or art fails to teach or suggest the cleaning compositions of the present invention comprising the multi-function component of the present invention.
  • compositions that provide enhanced and improved tough food cleaning, especially of carbohydrate soils; that provide enhanced and improved tough food cleaning under automatic dishwashing conditions; that provide tough food cleaning via cellulase enzymes designed to deliver such benefits; and that provide removal/reduction of spotting and films from hard surfaces.
  • the present invention meets the needs discussed above
  • the present invention provides cleaning compositions that contain a multi-function component capable of hydrolyzing 1,3- ⁇ - glucans, 1 ,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans, and methods for cleaning hard surface substrates, especially dishware, cookware, tableware, etc.. by applying such cleaning compositions to the substrates.
  • cleaning compositions containing the multi-function component of the present invention when applied directly to a surface m need of cleaning, such as a carbohydrate soiled surface, provide significantly better cleaning of the surface relative to amylase-contaming detergent compositions without such a multi-function component.
  • the cleaning compositions descnbed herein provide supe ⁇ or removal and/or reduction of soils, especially carbohydrate soils, such as oatmeal, barley, rye, wheat and ⁇ ce, and/or spotting and films objected to by the consumer from stainless steel and other metals, plastic, ceramic, dishware, cookware, glass, wood, baby bottles, and many other known hard surface substrates, both porous and non-porous.
  • carbohydrate soils such as oatmeal, barley, rye, wheat and ⁇ ce
  • spotting and films objected to by the consumer from stainless steel and other metals, plastic, ceramic, dishware, cookware, glass, wood, baby bottles, and many other known hard surface substrates, both porous and non-porous.
  • multi-function component it is meant a component that exhibits or performs more than one function.
  • the multi-function component is capable of hydrolyzing 1,3- ⁇ -glucans, 1 ,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans.
  • physically linked it is meant that distinct, discrete 1,3- ⁇ -glucans and 1 ,4- ⁇ -glucans are mixed with each other;
  • chemically linked it is meant that 1,3- ⁇ -glucans and 1 ,4- ⁇ -glucans are present in a single molecule (i.e.
  • an enzyme m any amount capable of measurably improving soil removal (especially carbohydrate soils) from the surface, i.e., soiled dishware, cookware, countertop, etc., when it is washed by the consumer, either manually or by an automatic washing machine (laundry or dishwashing). In general, this amount may vary quite widely.
  • soil removal it is meant the ability to clean cooked-on, burned-on, baked-on or d ⁇ ed-on foods. Examples include burned-on, baked-on and d ⁇ ed-on oatmeal.
  • surface m need of cleaning it is meant a surface such as tableware, dishware, cookware and other hard surface substrates including but not limited to va ⁇ eties of stainless steel and other metals, glass, ceramic, baby bottles, wood and plastic that is soiled by any type of soil, preferably a carbohydrate soil, and/or has spots or films.
  • a cleaning composition preferably a detergent composition, comp ⁇ smg the multi-function component of the present invention and one or more cleaning adjunct matenals selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof is provided.
  • a cleaning composition preferably a detergent composition, compnsmg the multi-function component of the present invention, an amylase and one or more cleaning adjunct mate ⁇ als selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof is provided.
  • a fab ⁇ c cleaning composition comp ⁇ sing the multi-function component of the present invention, at least about 5% surfactant and at least about 5% builder, at least one other cleaning adjunct mate ⁇ al selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof, and optionally, a bleaching agent and/or amylase is provided.
  • a dishwashing detergent composition compnsmg: (a) from about 0.0001% to about 10% by weight of the composition of the multifunction component of the present invention
  • (d) optionally, from about 0.0001 % to about 2% by weight of an amylase is provided.
  • an automatic dishwashing composition compnsmg: (a) a tablet body including one or more cleaning adjunct mate ⁇ als; and
  • a method for cleaning a surface in need of cleaning is provided. The method compnses contacting the surface m need of cleaning with an effective amount of a cleaning composition containing the multi-function component of the present invention, and optionally an amylase and/or optionally one or more cleaning adjuncts, such that the cleaning composition cleans (e g., cleans a wide range of soils) the surface.
  • a method for cleaning a dish m need of cleaning compnsmg contacting the dish with a dishwashing cleaning composition descnbed herein is provided.
  • a surface cleaned by the methods of the present invention is provided.
  • Yet another aspect of the present invention is a product comprising a cleaning composition containing the multi-function component of the present invention and a cleaning adjunct matenal selected from the group consisting of low foammmg nonionic surfactants, the product further including instructions for using the cleaning composition to clean surfaces in need of cleaning.
  • Still yet another aspect of the present invention is a product compnsmg a cleaning composition containing the multi-function component of the present invention and an amylase and at least one cleaning adjunct mate ⁇ al selected from the group consisting of low foaming nonionic surfactants, hydrotropes and mixtures thereof, the product further including instructions for using the cleaning composition to clean surfaces need of cleaning.
  • the present invention provides: cleaning compositions that are effective and efficient in cleaning surfaces in need of cleaning; methods of using the cleaning composition to clean such surfaces; surfaces cleaned with the cleaning compositions; and products compnsmg the cleaning compositions. All percentages and proportion herein are by weight, and all references cited herein are hereby incorporated by reference, unless otherwise specifically indicated.
  • Multi-function component - Suitable multi-function components for use in the cleaning compositions of the present invention include multi-function components that hydrolyze 1,3- ⁇ - glucans, 1 ,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1 ,4- ⁇ -glucans.
  • Preferred multi-funcnon components in accordance with the present invention are enzymes. More preferred multi-function components in accordance with the present invention are cellulases. Most preferred multi-function components in accordance with the present invention are endoglucanases (EC 3.2.1.4).
  • Glucan substrates present in the cell wall of cereal meals are very sticky and difficult to remove. The also glue and prevent other soils from being removed. It has been found that the endoglucanase of the present invention can digest glucan polymers that are not degradable by amylases, and further release other soil multi-function components, leading to improved cleaning benefits.
  • Suitable endoglucanases are descnbed m WO 94/14953 as "Endoglucanase Type IV (otherwise known as Endoglucanase IV or EG IV) and are. (1) encoded at least partially by DNA sequences disclosed m WO 94/14953, which is incorporated herein by reference, m the appended SEQ ED No 8 and/or SEQ ID No. 19 or a sequence homologous thereto encoding a polypeptide ("a homologue") with 1,3 and 1,4- ⁇ -D-glucans activity; and/or (2) enzymes that are lmmunologically reactive with an antibody raised against a highly punfied endoglucanase encoded by the DNA sequence SEQ ID No.
  • Endoglucanase IV exhibits a surpnsmgly high specificity and specific activity towards ⁇ - glucan. Endoglucanase IV is descnbed in WO 94/14953 as being capable of degrading cellulose and cellulose de ⁇ vatives like carboxymethylcellulose and hydroxyethylcellulose, and mixed ⁇ - 1,3-1,4 glucans like cereal ⁇ -glucans.
  • endoglucanases for use in the cleaning compositions of the present invention is an endoglucanase (EC 3.2.1.4), which surpnsingly catalyzes hydrolysis of internal 1,3- ⁇ -D- glycosidic linkages in hemicellulose ⁇ -D-glucans, and 1,4- ⁇ -D-glycos ⁇ d ⁇ c linkages in cellulose, chenin, and cereal ⁇ -D-glucans.
  • the endoglucansase (EC 3.2.1.4) exhibits significant activity on both the 1,3 and 1,4- ⁇ -D glycosidic linkages, and does not show substantially greater activity for one over the other.
  • Suitable endoglucanases include, but are not limited to, the endoglucanases (EC 3.2.1.4) descnbed in WO 94/14953 to Novo Nordisk A/S, which is incorporated herein by reference.
  • cellulolytic enzymes covered in W095/02675 which descnbes a detergent composition compnsmg two cellulase multi-function components : a first cellulase multi-function component having a retainmg-type activity and being capable of particulate soil removal and a second cellulase multi-function component having multiple domains comp ⁇ sing at least one non-catalytic domain attached to a catalytic domain and being capable of color cla ⁇ fication wherein at least one of the cellulase multi-function components is a single multifunction component.
  • Said enzymatic detergent composition is capable of providing both sufficient colour cla ⁇ fication and particulate soil removal which, after a limited number of washing cycles, neither damage nor partly degrade the cellulose-containing fabnc.
  • a preferred endoglucanase is an endoglucanase which is immunoreactive with an antibody raised against a highly punfied ⁇ 50kD endoglucanase de ⁇ ved from Humicola insolens, DSM 1800, or which is a homologue or de ⁇ vative of the ⁇ 50kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase has the ammo acid sequence disclosed in PCT Patent Application No.
  • W091/17244 or an endoglucanase which is immunoreactive with an antibody raised against a highly punfied ⁇ 50kD (apparent molecular weight, the am o acid composition corresponds to 45kD with 2n glycosylation sites) endoglucanase de ⁇ ved from Fusanum oxysporum, DSM 2672, or which is a homologue or de ⁇ vative of the ⁇ 50kD endoglucanase exhibiting cellulase activity; another preferred endoglucanase has the ammo acid sequence disclosed in PCT Patent Application No. W091/17244.
  • a preferred multi-function component is a cellulase, more preferably the endoglucanase having the ammo acid sequence disclosed WO95/02675 in the appended SEQ ED N0:3 or in
  • the endoglucanase is produced by Aspergillus oryzae after transformation with a plasmid containing the DNA sequence corresponding to the ammo acid sequence of the SEQ ID NO: 3 descnbed in
  • cellulase de ⁇ ved from Humicola tnsolens, DSM 1800 having an approximate molecular weight of about 50 kDa, an iso-elect ⁇ c point of about 5.5 and containing 415 ammo acids, such as descnbed m WO95/02675 which is an endoglucanase and has the ammo acid sequence disclosed therein in the appended SEQ ED NO:2 or in W091/17244, Fig.
  • va ⁇ ant of said endoglucanase having an ammo acid sequence being at least 60%, preferably at least 70%, more preferably 75%, more preferably at least 80%, more preferably 85%, especially at least 90% homologous with said sequence.
  • Suitable multi-function components include the cellulases that exhibit endo- 1,3(4)- ⁇ -glucanase activity as descnbed in PCT Patent Application No. WO 95/31533.
  • EGi ⁇ cellulases from Tnchoderma longibrachiatum descnbed m W094/21801, Genencor, published September 29, 1994.
  • the endoglucanase may be de ⁇ ved or isolated and punfied from microorganisms which are known to be capable of producing cellulolytic enzymes, e.g. species of Humicola, Bacillus, Trichederma, Fusanum, Myceliophtora, Phanerochaete, Schizophyllum, Pemcillium, Aspergillus and Geotricum.
  • the de ⁇ ved multi-function components may be either homologous or heterologous multi-function components.
  • the multi-function components are homologous.
  • heterologous multi-function component which is immunoreactive with an antibody raised against a highly punfied cellulase multi-function component possessing the desired property or properties and which heterologous multi-function component is de ⁇ ved from a specific microorganism is also preferred.
  • suitable cellulases are the EG Lfrom Trichoderma long ⁇ rachiatum descnbed m WO94/21801, Genencor, published September 29, 1994, and the cellulases that exhibit endo- l,3(4)- ⁇ -glucanase activity descnbed in W097/44361.
  • the term "homologue” is intended to indicate a polypeptide encoded by DNA which hyb ⁇ dizes to the same probe as the DNA coding for the endoglucanase enzyme with this ammo acid sequence under certain specified conditions (such as presoakmg in 5xSSC and prehyb ⁇ dizmg for 1 h at about 40°C in a solution of 20% formamide, 5xDenhardt's solution, 50mM sodium phosphate, pH 6.8, and 50 ⁇ g of denatured sonicated calf thymus DNA, followed by hyb ⁇ dization in the same solution supplemented with 100 ⁇ M ATP for 18 h at about 40°C).
  • certain specified conditions such as presoakmg in 5xSSC and prehyb ⁇ dizmg for 1 h at about 40°C in a solution of 20% formamide, 5xDenhardt's solution, 50mM sodium phosphate, pH 6.8, and 50 ⁇ g of denature
  • the term is intended to include denvatives of the aforementioned sequence obtained by addition of one or more amino acid residues to either or both the C- and N-terminal of the native sequence, substitution of one or more am o acid residues at one ore more sites in the native sequence, deletion of one or more ammo acid residues at either or both ends of the native am o acid sequence or at one or more sites within the native sequence, or insertion of one or more ammo acid residues at one or more sites in the native sequence.
  • the above-mentioned enzymes may be of any suitable o ⁇ gin, such as vegetable, animal, bactenal, fungal and yeast origin.
  • O ⁇ gin can further be mesophi c or extremophi c (psychrophihc, psychrotrophic, thermophihc, barophi c, alkalophihc, acidophihc, halophi c, etc.) Punfied or non-pu ⁇ fied forms of these enzymes may be used.
  • mesophi c or extremophi c psychrophihc, psychrotrophic, thermophihc, barophi c, alkalophihc, acidophihc, halophi c, etc.
  • Punfied or non-pu ⁇ fied forms of these enzymes may be used.
  • the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the va ⁇ ant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme va ⁇ ant is tailored to suit the particular cleaning application.
  • ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility.
  • the isoelect ⁇ c point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase in isoelect ⁇ c point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt b ⁇ dges and enforcing calcium binding sites to increase chelant stability.
  • Amylase - In preferred embodiments of the cleaning compositions of the present invention, an amylase, in addition to the multi-function components descnbed above, is incorporated into the cleaning compositions.
  • a preferred amylase is an ⁇ -amylase.
  • the ⁇ - amylase is an endoglucosidase (EC 3.2.1.1) which catalyzes the hydrolysis of internal ⁇ - glucosidic linkages in starches.
  • a cleaning composition containing the endoglucanase (3.2.1.4) of the present invention and an amylase delivers synergistic performance benefits in dish applications.
  • a cleaning composition containing the endoglucanase (3.2.1.4) of the present invention and the amylase performs significantly better than each single enzyme alone at equal total enzyme levels. Therefore, the combination performs better than the cumulative performance of the enzymes used alone.
  • the endoglucanase (EC 3.2.1.4) of the invention exhibits different substrate specificity from amylase.
  • ⁇ -amylases used in detergent systems is an endoglucosidase (EC 3.2.1.1), which catalyzes hydrolysis of internal ⁇ -glucosidic linkages m starches.
  • an amylase such as the ⁇ -amylases descnbed herein, maximizes and optimizes the specific functions of each enzyme m the wash and delivers synergistic benefits in cleaning performance that normally can not be achieved by each single enzyme.
  • Amylases useful in the present invention include, but are not limited to, the amylases descnbed in WO 95/26397 and WO 96/23873 (Novo). These enzymes are incorporated into cleaning compositions at a level of from about 0.0001%, preferably from about 0.00018%, more preferably from about 0.00024%, most preferably from about 0.05% to about 0.1%, preferably to about 0.060%), more preferably to about 0.048% by weight of the cleaning compositions of pure enzyme.
  • amylases for use in the present invention are preferably selected from the group consisting of ⁇ -amylase vanants.
  • Suitable ⁇ -amylase vanants for use m the present invention include, but are not limited to the following ⁇ -amylases:
  • ⁇ -amylase according to (l) compnsmg the following ammo acid sequence N- terminal: H ⁇ s-H ⁇ s-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-T -Tyr-Leu-Pro-Asn- Asp (SEQ ID No. 4) or an ⁇ -amylase being at least 80% homologous with the ammo acid sequence shown (SEQ ID No. 4) m the N-termmal and/or;
  • ⁇ -amylase according to (v) wherein the amylase is obtainable from any of the strains NCIB 12289, NCTB 12512, NCB 12513 and DSM 935 and/or; (vn) ⁇ -amylase showing positive immunological cross-reactivity with antibodies raised against an ⁇ -amylase having an ammo acid sequence corresponding respectively to SEQ ID No. 2, ID No. 3, or ID No. 4 and/or;
  • (vm) va ⁇ ant of a parent ⁇ -amylase wherein the parent ⁇ -amylase (1) has one of the ammo acid sequences shown m SEQ ID No. 2, ED No. 3, or ED No. 4, respectively, or (2) displays at least 80% homology with one or more of said ammo acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an ⁇ -amylase having one of said amino acid sequences, and/or is encoded by a DNA sequence which hyb ⁇ dizes with the same probe as a DNA sequence encodmg an ⁇ -amylase having one of said amino acid sequences, in which vanants: (A) at least one ammo acid residue of said parent ⁇ -amylase has been deleted; and/or (B) at least one ammo acid residue of said parent ⁇ -amylase has been replaced by a different ammo acid residue; and/or (C) at least one ammo acid residue has been inserted relative to said parent ⁇ -
  • a polypeptide is considered to be X% homologous to the parent amylase if a compa ⁇ son of the respective ammo acid sequences, performed via algonthms, such as the one descnbed by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%.
  • the term "obtainable from” is intended not only to indicate an amylase produced by a Bacillus strain but also an amylase encoded by a DNA sequence isolated from such a Bacillus strain and produced m a host organism transformed with the DNA sequence.
  • the multifunction component and amylase may be present m the cleaning compositions in any ratio.
  • the multi-function component and amylase are present in a ppm ratio of multifunction component to amylase of from about 1.20, more preferably from about 1: 10, most preferably from about 1 : 5 to about 20: 1, more preferably to about 10: 1, most preferably from about 5: 1
  • the multi-function component and amylase are present in a ppm ratio of multi-function component to amylase of from about 1 :3 to about 3: 1.
  • the multi-function component and amylase when present, are preferably present m the cleaning compositions of the present invention at a total enzyme level of from about 0.01 ppm, more preferably from about 0.2 ppm, most preferably from about 0.6 ppm to about 50 ppm, more preferably 10 ppm, even more preferably 7 ppm, most preferably 4 ppm. It is highly desirable that the multi-function component and amylase, when present, are present m the cleaning compositions of the present invention at a total enzyme level of from about 0.6 ppm to about 3.0 ppm.
  • the cleaning compositions of the present invention compnse an effective amount of a multi-function component that is capable of hydrolyzing 1,3- ⁇ -glucans, 1 ,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans.
  • the cleaning compositions further include one or more of the following cleaning ad j unct mate ⁇ als selected from the group consisting of: surfactants, solvents, clay, polycarboxylate thickeners, builders, dispersants, other enzymes, bleaches, bleach activators, bleach catalysts, baking soda, carbonates, phosphates, hydrobenzoic acid, dicarboxyhc acid, siloxanes, perfumes, water and mixtures thereof.
  • the cleaning compositions further include an amylase, preferably an ⁇ -amylase, as discussed herein. It has been found that the cleaning compositions of the present invention provide supe ⁇ or tough food cleaning benefits, especially on carbohydrate soils, than cleaning compositions that contain amylase, a leading carbohydrate soil enzyme, without a multi-function component that is capable of hydrolyzing 1,3- ⁇ -glucans, 1,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans.
  • an amylase preferably an ⁇ -amylase
  • Preferred cleaning compositions in accordance with the present invention compnse from about 0.0001%, more preferably from about 0.001%, most preferably from about 0.02% to about 10%, more preferably 1%, most preferably 0.2% by weight of the compositions of a pure multifunction component (m other words, when the multi-component is an enzyme, the cleaning composition comp ⁇ ses from about 0.0001% by weight of the composition of the pure enzyme) that is capable of hydrolyzing 1,3- ⁇ -glucans, 1 ,4- ⁇ -glucans and combinations of both physically and chemically linked 1,3- ⁇ -glucans and 1,4- ⁇ -glucans.
  • the multi-function component of the present invention is present m the cleaning compositions of the present invention in an amount sufficient to provide from about 0.001 ppm, more preferably 0.01 ppm to about 10 ppm, more preferably 6 ppm, of multi-function component m the wash liquor.
  • the cleaning compositions can be in a vanety of forms including, but not limited to, a liquid, a gel, a foam, a spray, a powder, a particulate, a bar, a granule or a tablet, especially a dimple tablet or multi-layer detergent tablet having both compressed and non-compressed portions.
  • a more preferred multi-layer detergent tablet comp ⁇ ses: 1) a compressed solid body portion having therein at least one mould the compressed solid body portion; and 2) at least one non-compressed, non-encapsulating portion mounted in the at least one mould of the compressed solid body portion, having an area of B, the at least one non-compressed, non- encapsulatmg portion compnsmg at least one detergent active; wherein the surface area of the detergent tablet, excluding areas of the at least one mould, is A; and preferably, wherein the ratio ofB to A is from about l:50 to 4: l, by area.
  • Most preferred cleaning compositions of the present invention compnse the multifunction component of the present invention, an amylase, and one or more cleaning adjunct mate ⁇ als selected from the group consisting of low foaming nonionic surfactants.
  • the cleaning compositions of the present invention may include an enzyme cocktail de ⁇ ved from two or more other enzymes, such as other carbohydrases including but not limited to other cellulases, other amylases, hemicellulases, cell-degrading enzymes, and pectm-degrading enzymes, and also proteases, hpases, bleaching enzymes and phosphohpid/phosphoprotein degrading enzymes.
  • an enzyme cocktail de ⁇ ved from two or more other enzymes such as other carbohydrases including but not limited to other cellulases, other amylases, hemicellulases, cell-degrading enzymes, and pectm-degrading enzymes, and also proteases, hpases, bleaching enzymes and phosphohpid/phosphoprotein degrading enzymes.
  • mate ⁇ al means any liquid, solid or gaseous mate ⁇ al selected for the particular type of cleaning composition desired and the form of the product (e.g., liquid; granule; powder; bar; paste; spray; tablet; gel, foam composition), which mate ⁇ als are also preferably compatible with the protease enzyme used m the composition Granular compositions can also be in "compact” form and the liquid compositions can also be m a "concentrated” form.
  • cleaning adjunct mate ⁇ als are readily made by conside ⁇ ng the surface, item or fab ⁇ c to be cleaned, and the desired form of the composition for the cleaning conditions du ⁇ ng use (e.g., through the wash detergent use).
  • compatible means the cleaning composition matenals do not reduce the proteolytic activity of the protease enzyme to such an extent that the protease is not effective as desired during normal use situations.
  • cleaning adjunct mate ⁇ als include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical b ⁇ ghteners, soil release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabnc conditioners, hydrolyzable surfactants, perservatives, anti-oxidants, anti- sh ⁇ nkage agents, anti-w ⁇ nkle agents, germicides, fungicides, color speckles, silvercare, anti- tarnish and or anti-corrosion agents, alkalinity sources, solubilizing agents, earners, processing aids, pigments and pH control agents as descnbed m U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific cleaning composition mate
  • cleaning adjunct mate ⁇ als are not compatible with the protease va ⁇ ant(s) in the cleaning compositions, then suitable methods of keeping the cleaning adjunct mate ⁇ als and the protease va ⁇ ant(s) separate (not m contact with each other) until combination of the two components is appropnate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc.
  • an effective amount of one or more protease vanants descnbed above are included in compositions useful for cleaning a vanety of surfaces in need of prote aceous stam removal.
  • cleaning compositions include detergent compositions for cleaning hard surfaces, unlimited in form (e.g., liquid and granular); detergent compositions for cleaning fabncs, unlimited m form (e.g., granular, liquid and bar formulations); dishwashing compositions (unlimited m form and including both granular and liquid automatic dishwashing); oral cleaning compositions, unlimited m form (e.g., dentifrice, toothpaste and mouthwash formulations); and denture cleaning compositions, unlimited m form (e.g , liquid, tablet).
  • "effective amount of protease va ⁇ ant” refers to the quantity of protease va ⁇ ant descnbed hereinbefore necessary to achieve the enzymatic activity necessary in the
  • SUBST-TUTE SHEET (RULE 26) specific cleaning composition Such effective amounts are readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular va ⁇ ant used, the cleaning application, the specific composition of the cleaning composition, and whether a liquid or dry (e.g., granular, bar) composition is required, and the like.
  • the cleaning compositions compnse from about 0.0001%, preferably from about 0.001%, more preferably from about 0.01% by weight of the cleaning compositions of one or more protease vanants of the present invention, to about 10%, preferably to about 1%, more preferably to about 0.1%.
  • the protease vanant of the present invention is present m the compositions an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available O2 ("Av ⁇ 2") from any peroxyacid in the wash liquor, referred to herein as the Enzyme to Bleach ratio (E/B ratio), ranging from about 1.1 to about 20: 1.
  • the Enzyme to Bleach ratio E/B ratio
  • the cleaning compositions may include from about 1% to about 99.9% by weight of the composition of the cleaning adjunct matenals.
  • cleaning compositions include hard surface cleaning compositions, dishwashing detergent compositions, oral cleaning compositions, denture cleaning compositions and personal cleansing compositions.
  • compositions of the present invention can also be used as detergent additive products in solid or liquid form.
  • Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process.
  • compositions of the invention When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other cleaning adjunct matenals selected from organic polymenc compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
  • the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 500 to 950 g/htre of composition measured at 20°C.
  • the "compact" form of the cleaning compositions herein is best reflected by density and, m terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions m powder form; m conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts, such as meant m the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides.
  • a prefe ⁇ ed filler salt is sodium sulfate.
  • Liquid cleaning compositions according to the present invention can also be in a
  • liquid cleaning compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the water content of the concentrated liquid cleaning composition is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the cleaning composition.
  • the cleaning compositions especially the dishwashing compositions, compnse phosphate builders and/or bleaching agents.
  • Surfactant System - Detersive surfactants included in the fully-formulated cleaning compositions afforded by the present invention compnse at least about 0.01%, preferably at least about 0.1%, more preferably at least about 1% to preferably about 60%, more preferably to about 35%, most preferably to 30% by weight of cleaning composition depending upon the particular surfactants used and the desired effects.
  • the detersive surfactant can be nonionic, anionic, ampholytic, zwitteno c, cationic, semi-polar nonionic, and mixtures thereof, nonhmitmg examples of which are disclosed m U.S.
  • Preferred cleaning compositions compnse anionic deter- sive surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants.
  • Nonhmitmg examples of surfactants useful herein include the conventional C ⁇ 1 -Ci g alkyl benzene suifonates and p ⁇ mary, secondary and random alkyl sulfates, the Ci Q-Cig alkyl alkoxy sulfates, the Ci Q -Ci g alkyl polyglycosides and their corresponding sulfated polyglyco- sides, C ⁇ -C ⁇ g alpha-sulfonated fatty acid esters, C12-C1 g alkyl and alkyl phenol alkoxylates
  • the surfactant is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • Nonionic Surfactants - Particularly preferred surfactants in the preferred automatic dishwashing compositions (ADD) of the present invention are low foaming nonionic surfactants (LFNI) LFNI may be present in amounts from 0.01% to about 10% by weight, preferably from about 0.1% to about 10%, and most preferably from about 0.25% to about 4%. LFNIs are most typically used in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-si cone, nonphosphate polymenc mate ⁇ als further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
  • Preferred LFNIs include nonionic alkoxylated surfactants, especially ethoxylates de ⁇ ved from p ⁇ mary alcohols, and blends thereof with more sophisticated surfactants, such as the polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers as descnbed U.S. Patent Nos. 5,705,464 and 5,710,115.
  • PO/EO/PO polymer-type surfactants are well-known to have foam suppressing or defoammg action, especially in relation to common food soil ingredients such as egg.
  • Highly preferred ADDs herein wherein the LFNI is present make use of ethoxylated monohydroxy alcohol or alkyl phenol and additionally compnse a polyoxyethylene, polyoxypropylene block polymenc compound as descnbed m U.S. Patent Nos. 5,705,464 and 5,710,115.
  • the invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at about 95°F (35°C), more preferably solid at about 77°F (25°C).
  • a preferred LFNI has a meltmg point between about 77°F (25°C) and about 140°F (60°C), more preferably between about 80°F (26.6°C) and 110°F (43.3°C).
  • the LFNI is an ethoxylated surfactant denved from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • a particularly preferred LFNI is de ⁇ ved from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C 16- ⁇ 20 alcohol), preferably a Ci g alcohol, condensed with an average of from about 6 to about 15 moles, preferably from about 7 to about 12 moles, and most preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic surfactant so de ⁇ ved has a narrow ethoxylate distnbution relative to the average.
  • the LFNI can optionally contain propylene oxide m an amount up to about 15% by weight.
  • Other preferred LFNI surfactants can be prepared by the processes descnbed in U.S.
  • Suitable block polyoxyethylene-polyoxypropylene polymenc compounds that meet the requirements descnbed hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, t ⁇ methylolpropane and ethylenediamme as initiator reactive hydrogen compound.
  • a particularly preferred LFNI contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend compnsmg about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene initiated with t ⁇ methylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of tnmethylolpropane.
  • LFNI LFNI
  • Cloud points of 1% solutions in water are typically below about 32°C and preferably lower, e.g., 10°C, for optimum control of sudsmg throughout a full range of water temperatures.
  • LFNIs which may also be used include those POLY-TERGENT® SLF-18 nonionic surfactants from Olm Corp., and any biodegradable LFNI having the melting point properties discussed hereinabove.
  • nonionic surfactants are well known m the art, being descnbed in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference herein.
  • ADD compositions compnsmg mixed surfactants wherein the sudsmg (absent any silicone suds controlling agent) is less than 2 inches, preferably less than 1 inch, as determined by the disclosure below.
  • the equipment useful for these measurements are: a Whirlpool Dishwasher (model 900) equipped with clear plexiglass door, IBM computer data collection with Labview and Excel Software, proximity sensor (Newark Corp - model 95F5203) using SCXI interface, and a plastic ruler.
  • the data is collected as follows.
  • the proximity sensor is affixed to the bottom dishwasher rack on a metal bracket. The sensor faces downward toward the rotating dishwasher arm on the bottom of the machine (distance approximately 2 cm. from the rotating arm). Each pass of the rotating arm is measured by the proximity sensor and recorded.
  • the pulses recorded by the computer are converted to rotations per mmute (RPM) of the bottom arm by counting pulses over a 30 second interval.
  • the rate of the arm rotation is directly proportional to the amount of suds in the machine and in the dishwasher pump (i.e., the more suds produced, the slower the arm rotation).
  • the plastic ruler is clipped to the bottom rack of the dishwasher and extends to the floor of the machine. At the end of the wash cycle, the height of the suds is measured using the plastic ruler (viewed through the clear door) and recorded as suds height.
  • the water is again adjusted for temperature and hardness, and then the ADD product is added to the bottom of the machine (in the case of separately evaluated surfactants, the ADD base formula is first added to the bottom of the machine then the surfactants are added by placing the surfactant-contammg glass vials inverted on the top rack of the machine).
  • the RPM is then monitored throughout the wash cycle.
  • the suds height is recorded using the plastic ruler.
  • the machine is again filled with water (adjust water for appropnate temperature and hardness) and runs through another nnse cycle. The RPM is monitored throughout this cycle.
  • An average RPM is calculated for the 1st nnse, mam wash, and final nnse.
  • the % RPM efficiency is then calculated by dividing the average RPM for the test surfactants into the average RPM for the control system (base ADD formulation without the nonionic surfactant).
  • the RPM efficiency and suds height measurements are used to dimension the overall suds profile of the surfactant.
  • Nonionic ethoxylated alcohol surfactant The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, pnmary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol
  • End-capped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula.
  • Ri is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms
  • R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms
  • x is an integer having an average value of from 0 5 to 1.5, more preferably 1
  • y is an integer having a value of at least 15, more preferably at least 20.
  • the surfactant of formula I at least 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2].
  • Suitable surfactants of formula I, according to the present invention are
  • Ether-capped ⁇ oly(oxyalkylated) alcohols - Preferred surfactants for use herein include ether- capped poly(oxyalkylated) alcohols having the formula:
  • R 1 and R 2 are lmear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;
  • R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms,
  • x is an mteger having an average value from 1 to 30, wherein when x is 2 or greater R 3 may be the same or different and k and j are integers having an average value of from 1 to 12, and more preferably 1 to 5.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R 3
  • x is an integer having an average value of from 1 to 20, more preferably from 6 to 15.
  • R 3 when, in the preferred embodiments, and x is greater than 2, R 3 may be the same or different That is, R 3 may vary between any of the alklyeneoxy units as descnbed above For instance, if x is 3, R 3 may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO)
  • the integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, multiple (EO) units and a much small number of (PO) units.
  • Particularly preferred surfactants as descnbed above include those that have a low cloud point of less than 20°C. These low cloud point surfactants may then be employed in con j unction with a high cloud point surfactant as descnbed in detail below for supenor grease cleaning benefits.
  • ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is 1 andj is 1 so that the surfactants have the formula:
  • R 2 and R 3 are defined as above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18 Most preferred are surfactants wherein R ⁇ and R 2 range from 9 to 14, R 3 is H forming ethyleneoxy and x ranges
  • the ether-capped poly(oxyalkylated) alcohol surfactants compnse three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
  • the alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.
  • surfactants exhibit significant improvements m spotting and filming charactenstics and removal of greasy soils, when used conjunction with high cloud point surfactants, relative to conventional surfactants.
  • the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention.
  • Examples of methods of prepa ⁇ ng the ether-capped poly(oxyalkylated) alcohol surfactants are descnbed below: A Cp/ii fatty alcohol (100.00 g, 0.515 mol.) and tm
  • Nonionic ethoxylated propoxylated fatty alcohol surfactant The ethoxylated C5-C1 g fatty alcohols and Cg-C j mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C JQ-CI g ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C ⁇ -C j g ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • Nonionic EO/PO condensates with propylene glycol The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • Nonionic EO condensation products with propylene oxide/ethylene diam e adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamme and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetromcTM compounds, marketed by BASF.
  • the detergent tablet compnses a mixed nonionic surfactant system compnsmg at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant.
  • Cloud point is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the “cloud point” (See Kirk Oth er's Encyclopedia of Chemical Technology, 3 Ed. Vol. 22, pp. 360-379).
  • a “low cloud point” nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than 20°C, and most preferably less than 10°C.
  • Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates denved from pnmary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Ohn Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., O n Corporation's Poly-Tergent® SLF18B senes of noniomcs, as descnbed, for example, in WO 94/22800, published October 13, 1994 by Olin Corporat ⁇ on)and the ether- capped poly(oxyalkylated) alcohol surfactants.
  • Nonionic surfactants can optionally contain propylene oxide in an amount up to 15% by weight.
  • Other preferred nonionic surfactants can be prepared by the processes descnbed m U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.
  • Low cloud point nonionic surfactants additionally compnse a polyoxyethylene, polyoxypropylene block polymenc compound.
  • Block polyoxyethylene-polyoxypropylene polymenc compounds mclude those based on ethylene glycol, propylene glycol, glycerol, tnmethylolpropane and ethylenediamme as initiator reactive hydrogen compound.
  • Certain of the block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable m ADD compositions of the invention.
  • Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such surfactants are typically useful herein as low cloud point nonionic surfactants.
  • a "high cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40°C, preferably greater than 50°C, and more preferably greater than 60°C
  • the nonionic surfactant system comp ⁇ ses an ethoxylated surfactant de ⁇ ved from the reaction of a monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD
  • Neodol 91-8 supplied by Shell.
  • the high cloud point nonionic surfactant further have a hydrophile- pophile balance ("HLB", see Kirk Othmer hereinbefore) value withm the range of from 9 to 15, preferably 11 to 15.
  • HLB hydrophile- pophile balance
  • mate ⁇ als include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • Another preferred high cloud point nonionic surfactant is de ⁇ ved from a straight or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon atoms (Cg-
  • high cloud point nonionic surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/11 or CI 1/15 branched alcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic surfactant so denved has a narrow ethoxylate dist ⁇ bution relative to the average.
  • the detergent tablet compnsmg such a mixed surfactant system also comp ⁇ ses an amount of water-soluble salt to provide conductivity m deiomsed water measured at 25°C greater than 3 mil Siemens/cm, preferably greater than 4 milh Siemens/cm, most preferably greater than 4.5 milh Siemens/cm as descnbed in co-pending GB Patent
  • the mixed surfactant system dissolves m water having a hardness of 1.246mmol L m any suitable cold-fill automatic dishwasher to provide a solution
  • the high cloud point and low cloud point surfactants of the mixed surfactant system are separated such that one of either the high cloud point or low cloud point surfactants is present in a first matrix and the other is present in a second matnx as descnbed in co-pending U.S Patent Application (attorney docket number 6252).
  • the first matnx may be a first particulate and the second matrix may be a second particulate.
  • a surfactant may be applied to a particulate by any suitable known method, preferably the surfactant is sprayed onto the particulate.
  • the first matnx is the compressed portion and the second matnx is the non-compressed portion of the detergent tablet of the present invention.
  • the low cloud point surfactant is present in the compressed portion and the high cloud point surfactant is present m the non-compressed portion of the detergent tablet of the present invention.
  • Branched alkyl alkoxylate surfactants are also suitable.
  • These branched nonionic surfactants show, some in applications, improved spotting and filming benefits over conventional linear surfactants.
  • Other Nonionic Surfactants Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • Commercially available nonionic surfactants of this type mclude IgepalTM CO-630, marketed by the GAF
  • alkylphenol alkoxylates e.g., alkyl phenol ethoxylates
  • the condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of Ci 1 - Ci 5 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 1 2-C 1 4 pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight dis t ribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 1 4-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of
  • alkylpolysacchandes especially alkylpolyglycosides, disclosed m U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysacchande
  • the preferred alkylpolyglycosides have the formula
  • R2 ⁇ (C n H 2n O) t (glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18. preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.1.
  • the glycosyl is preferably denved from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position)
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-pos ⁇ t ⁇ on, preferably predominately the 2-pos ⁇ t ⁇ on.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention.
  • Examples of compounds of this type include certain of the commercially-available PlurafacT LF404 and PluronicTM surfactants, marketed by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamme. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF. Polyethylene oxide condensates of alkyl phenols, condensation products of pnmary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysacchandes, and mixtures thereof.
  • R 1 is methyl
  • R 2 is a straight C ⁇ ⁇ .
  • alkyl or C _ ⁇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is denved from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.
  • Anionic Surfactants - Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the Amencan Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting mate ⁇ als would include natural fatty substances as de ⁇ ved from tallow, palm oil, etc.
  • alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci 0-C20 al kyl component, more preferably a C j 2- Cjg alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci 0-C20 al kyl component, more preferably a C j 2- Cjg alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted am
  • alkyl chains of C12-C1 g are preferred for lower wash temperatures (e.g. below about 50°C) and Ci6_ ⁇ g alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
  • anionic surfactants useful for detersive purposes can also be included in the cleaning compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and t ⁇ ethanolamme salts) of soap, Cg-C22 pnmary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxyhc acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as descnbed in B ⁇ tish patent specification No.
  • alkylpolyglycolethersulfates containing up to 10 moles ofethylene oxide
  • alkyl glycerol suifonates fatty acyl glycerol suifonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin suifonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succma ates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C1 g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), acyl sarcosinates, sulfates of alkylpolysaccha ⁇ des such as the sulfates of al
  • the cleaning compositions of the present invention typically compnse from about 1%, preferably from about 3% to about 40%, preferably about 20% by weight of such anionic surfactants.
  • Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S03M wherein R is an unsubstituted C ⁇ Q- C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12- 1 g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
  • substituted ammonium cations include methyl-, dimethyl, t ⁇ methyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl p perdinium cations and those de ⁇ ved from alkylamines such as ethylamme, diethylamine, t ⁇ ethylamme, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C1 g alkyl polyethoxylate (1 0) sulfate (C 12 -C ⁇ E(1.0)M), C ⁇ -Ci alkyl polyethoxylate (2.25) sulfate (C ⁇ 2 -C ⁇ gE(2.25)M), C ⁇ -C j g alkyl polyethoxylate (3.0) sulfate (C ⁇ 2 - E(3.0)M), and C 12-C 1 g alkyl polyethoxylate (4 0) sulfate (C 12-C 1 gE(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • the cleaning compositions of the present invention may also contain cationic, ampholytic, zwittenomc, and semi-polar surfactants, as well as the nonionic and or anionic surfactants other than those already descnbed herein.
  • Cationic detersive surfactants suitable for use m the cleaning compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltnmethylammonium halogenides, and those surfactants having the formula •
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, - CH2CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof
  • each R 4 is selected from the group consisting of C 1 -C4 alkyl, C 1 -C4 hydroxyalkyl, benzyl nng structures formed by j ommg the two R 4 groups, -CH2CHOH-CHOHCOR°CHOHCH2 ⁇ H wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0, R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18; each y is from 0 to about 10 and the
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I)
  • RI is a short chamlength alkyl (C6-C 10) or alkylarmdoalkyl of the formula (II)
  • y is 2-4, preferably 3; wherein R2 is H or a C1-C3 alkyl, wherein x is 0-4, preferably 0-2, most preferably 0, wherein R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,
  • Formula JH R6 is C1 -C4 and z is 1 or 2; wherein X" is a countenon, preferably a halide, e.g. chlonde or methylsulfate.
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula (1):
  • Ri is Cg-Ci g alkyl
  • each of R , R3 and R4 is independently C ⁇ -C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4Q) X H where x has a value from 2 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for Rj is C12- Ci 5 particularly where the alkyl group is a mixture of chain lengths de ⁇ ved from coconut or palm kernel fat or is denved synthetically by olefin build up or OXO alcohols synthesis.
  • R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from hahde, methosulfate, acetate and phosphate.
  • Other cationic surfactants useful herein are also descnbed m U S. Patent 4,228,044, Cambre, issued October 14, 1980 and m European Patent Application EP 000,224.
  • the cleaning compositions of the present invention typically comprise from about 0.2%, preferably from about 1% to about 25%, preferably to about 8% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use m the cleaning compositions of the present invention. These surfactants can be broadly descnbed as aliphatic denvatives of secondary or tertiary amines, or aliphatic denvatives of heterocychc secondary and tertiary amines in which the aliphatic radical can be straight- or branched-cham.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubi zmg group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlm et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
  • the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such ampholytic surfactants.
  • Zwittenomc surfactants are also suitable for use in cleaning compositions. These surfactants can be broadly descnbed as denvatives of secondary and tertiary amines, denvatives of heterocychc secondary and tertiary amines, or denvatives of quaternary ammonium, quaternary phosphomum or tertiary sulfomum compounds. See U.S. Patent No. 3,929,678 to
  • the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such zwittenomc surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amme oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants mclude the am e oxide surfactants having the formula O
  • R 3 (OR 4 ) N(R 5 ) 2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a nng structure.
  • These amme oxide surfactants in particular include C 1 Q-C I g alkyl dimethyl amme oxides and C -Ci2 alkoxy ethyl dihydroxy ethyl amme oxides.
  • the cleaning compositions of the present invention typically compnse from about 0.2%, preferably from about 1% to about 15%, preferably to about 10% by weight of such semi-polar nonionic surfactants.
  • the cleaning compositions of the present invention may further compnse a cosurfactant selected from the group of pnmary or tertiary amines.
  • Suitable pnmary ammes for use herein include amines according to the formula R2-NH2 wherein Rj is a Cg-C ⁇ , preferably Cg-Cjo alkyl chain or R4X(CH2) n , X is -0-,-C(0)NH- or -NH- > R4 is a Cg-C ⁇ alkyl chain n is between 1 to 5, preferably 3.
  • R ⁇ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
  • Preferred am es according to the formula herein above are n-alkyl amines. Suitable ammes for use herein may be selected from 1 -hexylam e, 1-octylamme, 1-decylam ⁇ ne and laurylam e. Other preferred pnmary amines include C8-C10 oxypropylamine, octyloxypropylamme, 2-ethylhexyl-oxypropylamme, lauryl amido propylamine and amido propylamine.
  • Suitable tertiary ammes for use herein include tertiary amines having the formula R1R2R3N wherein RI and R2 are -Cg alky -chains or
  • R3 is either a C ⁇ -C ⁇ preferably Cg-Cjo alkyl chain, or R3 is 4X(CH2) n , whereby X is -0-, - C(0)NH- or -NH- R4 is a C4-C12, n 1S between 1 to 5, preferably 2-3.
  • R5 is H or C ⁇ -C 2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched , R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary ammes are Ri R2R3N where RI is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or R 5
  • R is Cg-C ⁇ alkyl; n is 2-4, preferably n is 3; R2 and R3 is Ci -C4.
  • ammes of the present invention include 1-octylamme, 1 -hexylamme, 1- decylamine, l-dodecylamme,C8-10oxypropylam ⁇ ne, N coco l-3d ⁇ ammopropane, coconutalkyldimethylamme, lauryldimethylamine, lauryl b ⁇ s(hydroxyethyl)amme, coco bis(hydroxyehtyl)amme, lauryl amme 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyi-dimethylamine, C8-10 amidopropyldimethylamme and CIO amidopropyl- dimethylam e.
  • compositions herein are 1 -hexylamme, 1 - octylamme, 1-decylamme, 1-dodecylam ⁇ ne.
  • Bleaching System The cleaning compositions of the present invention preferably compnse a bleaching system.
  • Bleaching systems typically compnse a "bleaching agent” (source of hydrogen peroxide) and an "initiator” or “catalyst".
  • bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition.
  • the amount of bleach activator will typically be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition compnsmg the bleaching agent-plus-bleach activator.
  • Bleaching System - The cleaning compositions of the present invention preferably compnse a bleaching system.
  • Bleaching systems typically compnse a "bleachmg agent” (source of hydrogen peroxide) and an “initiator” or “catalyst".
  • bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically be from about 0.1%), preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition compnsmg the bleaching agent-plus-bleach activator.
  • Bleaching Agents Hydrogen peroxide sources are descnbed in detail m the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including va ⁇ ous coated and modified forms.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a preferred percarbonate bleach compnses dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from va ⁇ ous commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions of the present invention may also compnse as the bleaching agent a chlo ⁇ ne-type bleaching mate ⁇ al.
  • Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC").
  • NaDCC sodium dichloroisocyanurate
  • chlonne-type bleaches are less preferred for compositions which compnse enzymes.
  • the peroxygen bleach component m the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamme (TAED), benzoylcaprolactam (BzCL), 4-n ⁇ trobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C IQ-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
  • TAED tetraacetyl ethylene diamme
  • BzCL benzoylcaprolactam
  • 4-n ⁇ trobenzoylcaprolactam 3-
  • Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group
  • Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is descnbed m U.S. Patent No.
  • Preferred bleach activators are those descnbed in U S. 5,698,504 Christie et al , issued December 16, 1997; U.S. 5,695,679 Ch ⁇ stie et al. issued December 9, 1997; U.S. 5,686,401 Willey et al., issued November 1 1, 1997; U.S. 5,686,014 Hartshorn et al., issued November 1 1, 1997; U.S. 5,405,412 Willey et al., issued Ap ⁇ l 11, 1995, U.S. 5,405,413 Willey et al., issued Apnl 1 1, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1, preferably from about 20: 1, more preferably from about 10.1 to about 1: 1, preferably to about 3:1.
  • Quaternary substituted bleach activators may also be included.
  • the present cleaning compositions preferably compnse a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA structures are further descnbed in U.S. 5,686,015 Willey et al., issued November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselmk et al., issued October 24, 1995; U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al., issued November 26, 1996; all of which are incorporated herein by reference.
  • Highly preferred bleach activators useful herein are amide-substituted as descnbed m
  • bleach activators include: (6-octanam ⁇ docaproyl) oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzenesulfonate, (6-decanam ⁇ docaproyl)oxybenzenesulfonate and mixtures thereof.
  • Other useful activators disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S. 5,686,014 each of which is cited herein above and U.S.
  • bleaching results can be obtained from bleaching systems having with m-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5.
  • activators with electron- withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffenng agents can be used to secure such pH.
  • Acyl lactam activators as descnbed in U.S. 5,698,504, U.S. 5,695,679 and U S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al., issued Apnl 2, 1996 incorporated herein by reference).
  • compositions and methods may utilize metal-containing bleach catalysts that are effective for use in bleaching compositions.
  • metal-containing bleach catalysts that are effective for use in bleaching compositions.
  • Preferred are manganese and cobalt-containing bleach catalysts.
  • One type of metal-contammg bleach catalyst is a catalyst system compnsmg a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zmc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediammetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • Such catalysts are disclosed U.S. 4,430,243 Bragg, issued February 2, 1982.
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known m the art and include, for example, the manganese-based catalysts disclosed m U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn rv ( u -°)3( l A7-tnmethyl- 1 ,4,7-tnazacyclononane) 2 (PF 6 )2, Mn m 2 (u-0) 1 (u-OAc) 2 ( 1 ,4,7- t ⁇ methyl- 1 ,4,7-t ⁇ azacyclononane)2(Cl ⁇ 4)2, Mn r 4(u-0)6( 1 ,4,7-tnazacyclononane)4(Cl ⁇ 4)4, Mn Mn IV 4(u-0) ⁇ (u-0 Ac) 2 .( 1 ,4,7-t ⁇ methyl- 1 ,4,7-tnazacyclononane) 2 (C10 4 ) 3 , Mn w ( 1 ,4,1- t ⁇ methyl-l,4,7-t ⁇ azacyclononane)
  • metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and U.S. 5,114,611.
  • the use of manganese with va ⁇ ous complex ligands to enhance bleach g is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612, 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are descnbed, for example, in U.S. Patent Nos. 5,597,936, 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv Inorg. Bioinorg Mech., (1983), 2, pages 1-94.
  • cobalt pentaamme acetate salts having the formula [Co(NH 3 ) 5 OAc] T y , wherein "OAc” represents an acetate moiety and “T y " is an anion, and especially cobalt pentaamme acetate chlonde, [Co(NH3)5 ⁇ Ac]Cl2; as well as [Co(NH 3 ) 5 OAc](OAc) 2 , [Co(NH 3 ) 5 OAc](PF 6 ) 2 , [Co(NH 3 ) 5 OAc](S0 4 ), [Co- (NH 3 )5 ⁇ Ac](BF 4 )2, and [Co(N ⁇ 3) 5 OAc](N0 3 )2 (herein "PAC").
  • cobalt catalysts are readily prepared by known procedures, such as taught for example m U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and m U.S. Patent 4,810,410, J. Chem Ed. (1989), 66 (12), 1043-45, The Synthesis and Characte ⁇ zation of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3, Inorg. Chem.. 18, 1497-1502 (1979); Inorg Chem.. 21, 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg.
  • Transition Metal Complexes of Macropolycychc Rigid Ligands - Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycychc ngid ligand.
  • the phrase "macropolycychc ⁇ gid ligand” is sometimes abbreviated as "MRL" in discussion below.
  • the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein “ppb” denotes parts per billion by weight and “ppm” denotes parts per million by weight).
  • Suitable transition metals e.g., Mn are illustrated hereinafter.
  • Macropolycychc means a MRL is both a macrocycle and is polycyc c.
  • Polycyc c means at least bicychc.
  • ⁇ gid as used herein herein includes “having a superstructure” and “cross-bndged”. "Rigid” has been defined as the constrained converse of flexibility: see D.H. Busch., Chemical Reviews.. (1993), 93, 847-860, incorporated by reference.
  • ngid means that the MRL must be determinably more ngid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same nng size and type and number of atoms in the mam nng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's.
  • parent macrocycle which is otherwise identical (having the same nng size and type and number of atoms in the mam nng) but lacking a superstructure (especially linking moieties or, preferably cross-b ⁇ dgmg moieties) found m the MRL's.
  • the practitioner will use the free form (not the metal-bound form) of the macrocycles.
  • Rigidity is well-known to be useful in companng macrocycles; suitable tools for determining, measu ⁇ ng or companng ⁇ gidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorgamca Chimica Acta, (1989), 164, 73-84.
  • Preferred MRL's herein are a special type of ultra-ngid ligand which is cross-bndged.
  • a "cross-b ⁇ dge” is nonhmitmgly illustrated m 1.11 here below. In 1.11, the cross-bndge is a -
  • Suitable metals in the ngid ligand complexes include Mn(EI), Mn(IH), Mn(IV), Mn(V), Fe(II), Fe(m), Fe(IV), Co(I), Co(II), Co( ), N ⁇ (I), N ⁇ (II), N ⁇ (m), Cu(I), Cu(II), Cu(m), Cr(II), Cr(ffl), Cr(IV), Cr(V), Cr(VI), V(m), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru( ⁇ ), RU(IH), and Ru(rV).
  • Preferred transition-metals the instant transition- metal bleach catalyst include manganese, iron and chromium.
  • MRL's (and the corresponding transition-metal catalysts) herein suitably compnse:
  • a covalently connected non-metal superstructure capable of increasing the ngidity of the macrocycle, preferably selected from
  • Preferred superstructures herem not only enhance the ⁇ gidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordmates to a metal m a cleft.
  • Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used.
  • n is an mteger, for example from 2 to 8, preferably less than 6, typically 2 to 4, or
  • n and n are integers from about 1 to 8, more preferably from 1 to 3;
  • Z is N or CH; and
  • T is a compatible substituent, for example H, alkyl, tnalkylammonium, halogen, mtro, sulfonate, or the like
  • the aromatic nng in 1.10 can be replaced by a saturated nng, m which the atom in Z connecting into the nng can contain N, O, S or C.
  • MRL's are further nonhmitmgly illustrated by the following compound:
  • This is a MRL m accordance with the invention which is a highly preferred, cross- bndged, methyl-substituted (all nitrogen atoms tertiary) denvative of cyclam.
  • this ligand is named 5,12-d ⁇ methyl-l,5,8,12-tetraazab ⁇ cyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds Recommendations 1993", R. Pamco, W.H. Powell and J-C Richer (Eds ), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1
  • Transition-metal bleach catalysts of Macrocyc c Rigid Ligands which are suitable for use m the invention compositions can in general mclude known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-hmitingly illustrated by any of the following:
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species m the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0 05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will compnse from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions.
  • compositions herein may compnse one or more other bleach catalysts.
  • Preferred bleach catalysts are zwittenomc bleach catalysts, which are descnbed in U.S. Patent No. 5,576,282 (especially 3-(3,4-d ⁇ hydro ⁇ soqumolm ⁇ um) propane sulfonate.
  • Other bleach catalysts include cationic bleach catalysts are descnbed in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.
  • PAP phtha mido-peroxy- caproic acid
  • the detergent tablet may be provided with a way for controlling the rate of release of bleaching agent, particularly oxygen bleach to the wash solution.
  • the controlling of the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution. This could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
  • Suitable ways of controlled release of the bleaching agent can include confining the bleach to either the compressed or non-compressed, non-encapsulating portions. Where more than one non-compressed, non-encapsulating portions are present, the bleach may be confined to the first and or second and/or optional subsequent non-compressed, non-encapsulating portions.
  • Another way for controlling the rate of release of bleach may be by coating the bleach with a coating designed to provide the controlled release. The coating may therefore, for example, compnse a poorly water soluble matenal, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.
  • the coating mate ⁇ al may be applied using vanous methods. Any coating matenal is typically present at a weight ratio of coating mate ⁇ al to bleach of from 1 :99 to 1 :2, preferably from 1:49 to 1:9.
  • Suitable coating mate ⁇ als include t ⁇ glycendes (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglyce ⁇ des, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
  • Other suitable coating mate ⁇ als can compnse the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the Ci 0- 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 pnmary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymenc matenals.
  • Polyvmylpyrrohdones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10 ⁇ preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymenc matenals.
  • Copolymers of maleic anhydnde with ethylene, methylvinyl ether or methacryhc acid, the maleic anhydnde constituting at least 20 mole percent of the polymer are further examples of polymenc matenals useful as binder agents.
  • polymenc mate ⁇ als may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C1Q-C20 mono- and diglycerol ethers and also the C10-C20 fatty acids.
  • Cellulose denvatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polyme ⁇ c polycarboxyhc acids or their salts are other examples of binders suitable for use herein.
  • One method for applying the coating mate ⁇ al involves agglomeration.
  • Preferred agglomeration processes include the use of any of the organic binder mate ⁇ als descnbed heremabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.
  • Additional ways for providing controlled release include the suitable choice of any other components of the detergent composition matnx such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved
  • Optional Detersive Enzymes may also optionally contain one or more types of detergent enzymes. Such enzymes can include other proteases, amylases, cellulases and hpases.
  • Such matenals are known in the art and are commercially available under such trademarks as . They may be incorporated into the non- aqueous liquid detergent compositions herein in the form of suspensions, "marumes” or “pnlls”.
  • Another suitable type of enzyme comp ⁇ ses those m the form of slumes of enzymes m nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP " Suitable enzymes and levels of use are descnbed in U.S. Pat. No 5,576,282, 5,705,464 and 5,710,115.
  • Enzymes added to the compositions herein m the form of conventional enzyme pnlls are especially preferred for use herein. Such pnlls will generally range m size from about 100 to
  • compositions which utilize enzyme pnlls need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
  • enzymes added to the compositions herein may be m the form of granulates, preferably T-granulates.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and hpases.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, hpases and peroxidases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, hpases, phosphohpases, esterases, cutinases, pectmases, keratanases, reductases, oxidases, phenoloxidases, hpoxygenases, gninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabmosidases, hyaluromdase, chondroitmase. laccase, and known amylases. or mixtures thereof. Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282. 5.728,671 and 5,707,950
  • the cellulases useful m the present invention include both bactenal or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola msolens, Tnchoderma, Thielavia and Sporotnchum. EP 739 982 desc ⁇ bes cellulases isolated from novel Bacillus species.
  • Suitable cellulases are also disclosed m GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398. Examples of such cellulases are cellulases produced by a strain of Humicola insolens
  • Humicola g ⁇ sea var. thermoidea particularly the Humicola strain DSM 1800.
  • Other suitable cellulases are cellulases ongmated from Humicola msolens having a molecular weight of about 50KDa, an isoelect ⁇ c point of 5.5 and containing 415 ammo acids; and a ⁇ 43kD endoglucanase de ⁇ ved from Humicola msolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the ammo acid sequence disclosed in WO 91/17243.
  • suitable cellulases are the EG-H cellulases from Tnchoderma longibrachiatum descnbed m WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases descnbed m European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and W091/21801. Other suitable cellulases for fab ⁇ c care and or cleanmg properties are descnbed in WO96/34092, W096/17994 and W095/24471
  • Cellulases when present, are normally incorporated m the cleaning composition at levels from 0.0001%) to 2% of pure enzyme by weight of the cleaning composition.
  • Peroxidase enzymes are used m combination with oxygen sources, e.g percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates dunng wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, hgninase and haloperoxidase such as chloro- and bromo-peroxidase. Suitable peroxidases and peroxidase-contammg detergent compositions are disclosed, for example, m U.S.
  • SUBST ⁇ UTE SHEET (RULE 26) Phenothiazmepropionicacid (PPT), 10-ethylphenoth ⁇ azme-4-carboxyl ⁇ c acid (EPC), 10- phenoxazmepropionic acid (POP) and 10-methylphenoxazme (descnbed in WO 94/12621) and substitued sy ⁇ ngates (C3-C5 substitued alkyl sy ⁇ ngates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • Enzymatic systems may be used as bleaching agents.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or du ⁇ ng the washing and/or nnsmg process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed m EP Patent Application 91202655.6 filed October 9, 1991.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutze ⁇ ATCC 19.154, as disclosed in B ⁇ tish Patent 1,372,034.
  • Suitable hpases m clude those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent JAM 1057.
  • This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano- P".
  • hpases include Amano-CES, hpases ex Chromobacter viscosum. e.g. Chromobacter viscosum var lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum hpases from U.S. Biochemical Corp., U S.A. and Disoynth Co., The Netherlands, and hpases ex Pseudomonas gladioli.
  • hpases are hpases such as Ml which have found to be very effective when used in combination with the compositions of the present invention.
  • hpolytic enzymes descnbed in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutmases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely hpases which do not require interfacial activation. Addition of cutmases to cleaning compositions have been descnbed in e.g WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • Lipases and/or cutmases when present, are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • phosphohpases may be incorporated into the cleaning compositions of the present invention.
  • suitable phosphohpases included: EC 3.1.1.32 Phosphohpase Al; EC 3.1.1.4 Phosphohpase A2: EC 3.1.1.5 Lysophohpase; EC 3.1.4.3 Phosphohpase C, EC 3.1.4.4. Phospohpase D.
  • phosphohpases include LECITASE® from Novo Nordisk A/S of Denmark and Phosphohpase A2 from Sigma.
  • amylases are also included.
  • the combined action of the phosphohpase and amylase provide substantive stain removal, especially on greasy/oily, starchy and highly colored stains and soils.
  • the phosphohpase and amylase when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500:1 and 1:5, more preferably between 50:1 and 1:1.
  • Suitable proteases are the subti sins which are obtained from particular strains of -9. subtilis and B. licheniformis (subtihsm BPN and BPN')
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo".
  • the preparation of this enzyme and analogous enzymes is descnbed m GB 1,243,784 to Novo.
  • Proteolytic enzymes also encompass modified bactenal se ⁇ ne proteases, such as those descnbed in European Patent Application Serial Number 87 303761.8, filed Ap ⁇ l 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bactenal senne protealytic enzyme which is called "Protease A" herein.
  • Protease C is a va ⁇ ant of an alkaline se ⁇ ne protease from Bacillus in which Lysme replaced argimne at position 27, tyrosine replaced valme at position 104, se ⁇ ne replaced asparagme at position 123, and alanine replaced threonme at position 274.
  • Protease C is descnbed EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified vanants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase as descnbed m U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase vanant of the protease descnbed in WO95/1059 I, having an ammo acid sequence derived by replacement of a plurality of ammo acid residues replaced m the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally- occurnng subtihsm from Bacillus amyloliquefaciens or to equivalent ammo acid residues m
  • SUBSTITUTE SHEET (RULE 25) Also suitable for the present invention are proteases descnbed m patent applications EP 251 446 and WO 91/06637, protease BLAP® descnbed in W091/02792 and their vanants descnbed in WO 95/23221.
  • protease from Bacillus sp. NCIMB 40338 descnbed in WO 93/18140 A to Novo.
  • Enzymatic detergents compnsmg protease, one or more other enzymes, and a reversible protease inhibitor are descnbed m WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as descnbed m WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-hke protease for detergents suitable herein is descnbed WO 94/25583 to Novo.
  • Other suitable proteases are descnbed in EP 516 200 by Unilever.
  • proteases are descnbed in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979.
  • Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).
  • proteolytic enzymes when present, are incorporated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • Amylases ( ⁇ and or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO94/02597 descnbes cleaning compositions which incorporate mutant amylases. See also W095/ 10603.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ - amylases.
  • ⁇ -Amylases are known m the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and Bntish Patent specification no. 1,296,839 (Novo).
  • amylases are stability-enhanced amylases descnbed m W094/18314 and WO96/05295, Genencor, and amylase vanants having additional modification in the immediate parent available from Novo Nordisk A S, disclosed in WO 95/10603. Also suitable are amylases descnbed in EP 277 216.
  • ⁇ -amylases examples include Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark.
  • W095/26397 descnbes other suitable amylases : ⁇ -amylases charactensed by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25° C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • Suitable are vanants of the above enzymes, descnbed in W096/23873 (Novo Nordisk).
  • amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are descnbed m W095/35382.
  • Such amylolytic enzymes when present, are incorporated in the cleaning compositions of the present invention a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • the above-mentioned enzymes may be of any suitable o ⁇ gm, such as vegetable, animal, bactenal, fungal and yeast ongin.
  • O ⁇ gm can further be mesophihc or extremophihc
  • the vanants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased.
  • the vanant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme va ⁇ ant is tailored to suit the particular cleaning application.
  • ammo acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility.
  • the isoelect ⁇ c point of such enzymes may be modified by the substitution of some charged ammo acids, e.g. an increase m isoelectnc point may help to improve compatibility with anionic surfactants.
  • the stability of the enzymes may be further enhanced by the creation of e.g. additional salt bndges and enforcing calcium binding sites to increase chelant stability.
  • These optional detersive enzymes, when present, are normally incorporated m the cleaning composition at levels from 0.0001% to 2% of pure enzyme by weight of the cleaning composition.
  • the enzymes can be added as separate single ingredients (pnlls, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme matenals and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, and in U.S. 4,507,219. Enzyme mate ⁇ als useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed m U.S. 4,261,868. Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by va ⁇ ous techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S.
  • Enzyme stabilization systems are also descnbed, for example, in U.S. 3,519,570.
  • a useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is descnbed in WO 9401532.
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and or magnesium ions m the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are descnbed m U.S. Pat. Nos. 5,705,464, 5,710,115 and 5,576,282.
  • the detergent tablet of the present invention may further compnse a disrupting agent.
  • Disrupting agents are typically included m the tablet at levels of from about 5% to about 60%, and more preferably from about 20% to about 50%, by weight.
  • the disrupting agent may be a disintegrating or effervescing agent.
  • Suitable disintegrating agents include agents that swell on contact with water or facilitated water influx and/or efflux by forming channels in compressed and/or non-compressed portions. Any known disintegrating or effervescing agent suitable for use in laundry or dishwashing applications is envisaged for use herein.
  • Suitable disintegrating agent include starch, starch denvatives, alg ates, carboxymethylcellulose (CMC), cellulosic-based polymers, sodium acetate, aluminium oxide.
  • Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervescing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervescing agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids such as citnc or maleic acid.
  • compositions will typically compnse at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%), more preferably to about 30% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Preferred builders for use m the detergent and cleaning compositions, particularly dishwashing compositions, especially automatic dishwashing compositions or detergents ("ADD" or “ADW”) descnbed herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as descnbed in U.S. Patent Nos. 5,695,679,
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.
  • Inorganic or P-contammg detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammomum salts of polyphosphates (exemplified by the t ⁇ polyphosphates, pyrophosphates, and glassy polymenc meta-phosphates), phosphonates (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021, 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosihcates.
  • non-phosphate builders are required some locales.
  • compositions herein function surpnsmgly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • the silicates are water-soluble silicates, more preferably they are any silicates which are soluble to the extent that they do not adversely affect spotting' filming charactenstics of the ADD composition.
  • Suitable silicates include the water-soluble sodium silicates with an S ⁇ 0 .Na 2 0 ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 2.0 ratio being most preferred.
  • the silicates may be m the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an S ⁇ 0 2 .'Na 2 0 ratio of 2.0 is the most preferred.
  • Silicates, when present, are preferably present m the detergent and cleaning compositions descnbed herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.
  • Partially soluble or insoluble builder compounds which are suitable for use the detergent and cleaning compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates
  • Crystalline layered sodium silicates having the general formula NaMS ⁇ x ⁇ 2 x + ⁇ Y ⁇ O wherein M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used m the compositions descnbed herein. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A- 3417649 and DE-A-3742043. The most preferred matenal is delta-Na2S ⁇ 5, available from
  • NaSKS-6 Hoechst AG as NaSKS-6 (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2S ⁇ 5 morphology form of layered silicate. SKS-6 is a highly preferred layered silicate for use m the compositions descnbed herein herein, but other such layered silicates, such as those having the general formula NaMS ⁇ x ⁇ 2 x +i y ⁇ O wherein 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 can be used m the compositions descnbed herein.
  • Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • the delta-Na2S ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a c ⁇ spenmg agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Silicates particularly useful in automatic dishwashing (ADD) applications include granular hydrous 2-rat ⁇ o silicates such as BR--TESIL® H20 from PQ Corp , and the commonly sourced BRITESIL® H24 though liquid grades of vanous silicates can be used when the ADD composition has liquid form.
  • BR--TESIL® H20 from PQ Corp
  • BRITESIL® H24 liquid grades of vanous silicates can be used when the ADD composition has liquid form.
  • sodium metasihcate or sodium hydroxide alone or in combination with other silicates may be used in an ADD context to boost wash pH to a desired level.
  • the crystalline layered sodium silicate mate ⁇ al is preferably present m granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble lomzable mate ⁇ al.
  • the solid, water-soluble lomzable matenal is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • succi c acid builders include the C5-C20 alkyl and alkenyl succimc acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccmic acid.
  • succmate builders include: laurylsuccmate, my ⁇ stylsuccmate, palmitylsuccmate, 2-dodecenylsucc ⁇ nate
  • Laurylsuccinates are the preferred builders of this group, and are descnbed m European Patent Application 86200690.5/0,200,263, published
  • Fatty acids e.g., C ⁇ - monocarboxyhc acids
  • the aforesaid builders especially citrate and/or the succmate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsmg, which should be taken into account by the formulator.
  • Dispersants One or more suitable polyalkyleneimine dispersants may be incorporated into the cleaning compositions of the present invention. Examples of such suitable dispersants can be found m European Patent Application Nos. 111,965, 111,984, and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145.
  • any suitable clay/soil dispersent or anti- redepostion agent can be used in the laundry compositions of the present invention.
  • polymenc dispersing agents which mclude polymenc polycarboxylates and polyethylene glycols, are suitable for use in the present invention.
  • Unsaturated monome ⁇ c acids that can be polymenzed to form suitable polymenc polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumanc acid, itacomc acid, aconitic acid, mesacomc acid, citraconic acid and methylenemalomc acid.
  • Particularly suitable polymenc polycarboxylates can be denved from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water- soluble salts of polymenzed acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known matenals. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in U.S. 3,308,067.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersmg/anti-redeposition agent.
  • Such mate ⁇ als include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers m the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30: 1 to about 1:1, more preferably from about 10:1 to 2: 1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known matenals which are descnbed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also descnbes such polymers compnsmg hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acryhc/vmyl alcohol terpolymers.
  • Such matenals are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acryhc/maleic/vmyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about
  • 100,000 preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions of the present invention herein may also optionally contain a chelating agent which serves to chelate metal ions and metal impu ⁇ ties which would otherwise tend to deactivate the bleaching agent(s).
  • a chelating agent which serves to chelate metal ions and metal impu ⁇ ties which would otherwise tend to deactivate the bleaching agent(s).
  • Useful chelating agents can include ammo carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are descnbed in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like. If utilized, these chelating agents will generally compnse from about 0.1% to about 15%, more preferably from about 0 1% to about 3.0% by weight of the detergent compositions herein.
  • the detergent tablets of the present invention suitable for use in dishwashing methods may contain corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen-contammg corrosion inhibitor compounds and Mn(H) compounds, particularly Mn(H) salts of organic ligands.
  • Organic silver coating agents are descnbed in PCT Publication No. WO94/16047 and copending European application No. EP-A-690122. Nitrogen-containing corrosion inhibitor compounds are disclosed m copending European Application no. EP-A-634,478. Mn(H) compounds for use in corrosion inhibition are descnbed in copending European Application No. EP-A-672 749.
  • Organic silver coating agent when present, may be incorporated at a level of preferably from about 0.05% to about 10%o, more preferably from about 0.1% to about 5% by weight of the total composition.
  • the functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied.
  • the silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.
  • Suitable organic silver coating agents herein include, but are not limited to, fatty esters of mono- or polyhydnc alcohols having from about 1 to about 40 carbon atoms m the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxyhc acids having from about 1 to about 40 carbon atoms the hydrocarbon chain.
  • monocarboxyhc fatty acids include behenic acid, stea ⁇ c acid, oleic acid, palmitic acid, mynstic acid, launc acid, acetic acid, propiomc acid, butync acid, isobuty ⁇ c acid, Vale ⁇ e acid, lactic acid, glycohc acid and ⁇ , ⁇ '- dihydroxyisobuty ⁇ c acid.
  • suitable polycarboxyhc acids include: n-butyl-malomc acid, isocit ⁇ c acid, cit ⁇ c acid, maleic acid, malic acid and succimc acid.
  • the fatty alcohol radical m the fatty ester can be represented by mono- or polyhydnc alcohols having from about 1 to about 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vmyl alcohol, diglycerol, xy tol, sucrose, eryth ⁇ tol, pentaeryth ⁇ tol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct matenal have from about 1 to about 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comp ⁇ ses a species selected from behenic acid, stea ⁇ c acid, oleic acid, palmitic acid or mynstic acid.
  • glycerol esters are also highly preferred. These are the mono-, di- or t ⁇ -esters of glycerol and the fatty acids as defined above.
  • fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl prop ⁇ onate.
  • Some fatty acid esters useful herein include: xyhtol monopalmitate, pentaerythntol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomynstate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herem.
  • Suitable organic silver coating agents include t ⁇ glycendes, mono or diglyce ⁇ des, and wholly or partially hydrogenated denvatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are suitable organic silver coating agents herein.
  • Preferred waxes have a melting point in the range from about 35°C to about 1 10°C and compnse generally from about 12 to about 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-cham saturated hydrocarbon compounds.
  • Alginates and gelatin are suitable organic silver coating agents which can be used in the compositions herem.
  • Dialkyl amme oxides such as about C ⁇ 2 to about C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the about C[2 t0 about C20 methylammo um ha des are also suitable.
  • organic silver coating agents include certain polymenc matenals.
  • Certain perfume mate ⁇ als, particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.
  • Polymenc soil release agents can also be used as an organic silver coating agent.
  • a preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from about 20 to about 50; preferred paraffin oil selected from predominantly branched C25- 5 species with a ratio of cyclic to noncychc hydrocarbons of from about 1.10 to about 2: 1, preferably from about 1 :5 to about 1 : 1.
  • Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and denvatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole denvatives descnbed in Czech Patent No 139, 279 and Bntish Patent GB-A-1,137,741, which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their denvatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Rj, R3, R4 and R5 where Rj is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of Cj-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or NO2.
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzoth ⁇ azole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionahde, morphohne, melamme, distearylamme, stearoyl stearamide, cyanunc acid, ammot ⁇ azole, ammotetrazole and indazole.
  • Nitrogen-containing compounds such as ammes, especially distearylamme and ammonium compounds such as ammonium chlonde, ammonium bromide, ammonium sulphate or diammomum hydrogen citrate are also suitable.
  • the detergent tablets may contain an Mn(U) corrosion inhibitor compound.
  • the Mn(Et) compound is preferably incorporated at a level of from about 0.005% to about 5% by weight, more preferably from about 0.01% to about 1%, most preferably from about 0.02% to about 0 4% by weight of the compositions.
  • the Mn(II) compound is incorporated at a level to provide from about 0.1 ppm to about 250 ppm, more preferably from about 0.5 ppm to about 50 ppm, even more preferably from about 1 ppm to about 20 ppm by weight of Mn(JI) ions in any bleaching solution.
  • the Mn (ET) compound may be an inorganic salt m anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chlonde.
  • the Mn(EI) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with about 4 to about 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionahde and thioanthranol. Also suitable are saturated or unsaturated C10-C20 fatty acids, or their salts, especially aluminium tnstearate. The C12- 20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable. Copolymers of butadiene and maleic acid, particularly those supplied under the trade reference no. 07787 by Polysciences Inc. have been found to be of particular utility as corrosion inhibitor compounds.
  • Another preferred detergent active component for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from about 20 to about 50; preferred hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected from predominantly branched C25--45 species with a ratio of cyclic to noncychc hydrocarbons of from about 1: 10 to about 2:1, preferably from about 1 :5 to about 1 : 1.
  • a preferred hydrocarbon oil is paraffin.
  • the detergent tablets of the present invention suitable for use in dishwashing methods may contain a water-soluble bismuth compound, preferably present at a level of from about 0.005% to about 20%, more preferably from about 0.01% to about 5%, even more preferably from about 0.1 % to about 1% by weight of the compositions.
  • the water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion.
  • Preferred inorganic bismuth salts are selected from the bismuth tnhahdes, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • Colorant - means any substance that absorbs specific wavelengths of light from the visible light spectrum. Such colorants when added to a detergent composition have the effect of changing the visible color and thus the appearance of the detergent composition. Colorants may be for example either dyes or pigments.
  • the colorants are stable m composition in which they are to be incorporated. Thus in a composition of high pH the colorant is preferably alkali stable and m a composition of low pH the colorant is preferably acid stable.
  • the compressed and/or non-compressed, non-encapsulating portions may contain a colorant, a mixture of colorants, colored particles or mixture of colored particles such that the compressed portion and the non-compressed, non-encapsulating portion have different visual appearances.
  • a colorant Preferably one of either the compressed portion or the non-compressed, non-encapsulating portion a colorant.
  • the compressed and/or non-compressed, non-encapsulating portions may also be of one color and contain particles or speckles, of another color.
  • the compressed portion could be white with blue speckles, while the non- compressed, non-encapsulating portion is blue.
  • non-compressed, non-encapsulating portion comp ⁇ ses two or more compositions of detergent active components, preferably at least one of either the first and second and/or subsequent compositions comp ⁇ ses a colorant. Where both the first and second and/or subsequent compositions compnse a colorant it is preferred that the colorants have a different visual appearance.
  • the coating layer preferably compnses a colorant. Where the compressed portion and the coating layer compnse a colorant, it is preferred that the colorants provide a different visual effect.
  • suitable dyes include reactive dyes, direct dyes, azo dyes.
  • Preferred dyes include phthalocyanine dyes, anthraqu one dye, quinohne dyes, monoazo, disazo and polyazo. More preferred dyes include anthraqumone, quinohne and monoazo dyes.
  • Preferred dyes mclude SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename),
  • TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Cla ⁇ ant UK, HEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Pointings, UK, ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFD TURQUISE BLUE EBA (tradename) available from Bayer, USA.
  • the colorant does not cause visible staining to plastic, such as an automatic dishwasher or plastic tableware, after a plurality of cycles, more preferably between 1 and 50 cycles.
  • the colorant may be incorporated into the compressed and/or non-compressed, non- encapsulating portion by any suitable method. Suitable methods include mixing all or selected detergent active components with a colorant in a drum or spraying all or selected detergent active components with the colorant in a rotating drum. Alternatively, the colorants color may be improved by predisolving the colorant in a compatible solvent pnor to addition of the colorant to the composition.
  • Colorant when present as a component of the compressed portion is present at a level of from about 0.001% to about 1.5%, preferably from about 0.01% to about 1.0%, most preferably from about 0.1 % to about 0.3%
  • colorant is generally present at a level of from about 0.001% to about 0.1%, more preferably from about 0.005% to about 0.05%, most preferably from about 0 007% to about 0.02%.
  • colorant is present at a level of from about 0.01% to about 0.5%, more preferably from about 0 02% to about 0 1%, most preferably from about 0.03% to about 0.06%.
  • compositions of the invention can optionally contain an alkyl phosphate ester suds suppressor, a silicone suds suppressor, or combinations thereof.
  • the suds suppressors when present, are silicone and/or si ca- silicone mixtures, as disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671.
  • Levels in general are from 0% to about 10%, preferably, from about 0.001% to about 5%, more preferably from about 0.001%) to 2%, most preferably from about 0.01% to 1% by weight of the cleaning composition.
  • compositions herein do not compnse suds suppressors or compnse suds suppressors only at low levels, e.g., less than about 0.1% of active suds suppressing agent.
  • Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industnal Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herem by reference. See especially the chapters entitled “Foam control m Detergent Products” (Ferch et al) and “Surfactant Antifoams” (Blease et al). See also U.S. Patents 3,933,672 and 4,136,045.
  • Highly preferred silicone suds suppressors are the compounded types known for use laundry detergents such as heavy-duty granules, although types hitherto used only m heavy-duty liquid detergents may also be incorporated m the instant compositions.
  • polydimethylsiloxanes having t ⁇ methylsilyl or alternate endblockmg units may be used as the silicone.
  • These may be compounded with silica and or with surface-active nonsihcon components, as illustrated by a suds suppressor compnsmg 12% sihcone/sihca, 18% stearyl alcohol and 70% starch m granular form.
  • a suitable commercial source of the silicone active compounds is Dow Corning Corp.
  • a phosphate ester suitable compounds are disclosed in U.S. Patent 3,314,891, issued Apnl 18, 1967, to Schmolka et al, incorporated herein by reference.
  • Preferred alkyl phosphate esters contain from 16-20 carbon atoms.
  • Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
  • the detergent compositions herein can be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffenng capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.
  • the preferred compositions herein compnse a pH -adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
  • the pH- ad j ustmg components are selected so that when the composition is dissolved in water at a concentration of 1,000 - 10,000 ppm, the pH remains m the range of above about 8, preferably from about 9.5 to about 11.
  • the preferred nonphosphate pH-adjusting component of the invention is selected from the group consisting of: (l) sodium carbonate or sesquicarbonate; (n) sodium silicate, preferably hydrous sodium silicate having S ⁇ 2:Na2 ⁇ ratio of from about 1 : 1 to about 2: 1, and mixtures thereof with limited quantities of sodium metasi cate;
  • Preferred embodiments contain low levels of silicate (i.e. from about 3% to about 10%
  • the amount of the pH ad j usting component in the instant composition is preferably from about 1%) to about 50%), by weight of the composition.
  • the pH- ad j ustmg component is present in the composition an amount from about 5% to about 40%, preferably from about 10% to about 30%, by weight.
  • the preferred ADD compositions herein compnse a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders as descnbed m U.S. Patent Nos. 5,705,464 and 5,710,115.
  • the preferred ADD compositions may contain one or more matenal care agents which are effective as anti-tarnish aids as descnbed in U S. Patent Nos. 5,705,464,
  • SUBSTrrUTE SHEET (RULE 26)
  • such protecting matenals are preferably incorporated at low levels, e.g., from about 0.01% to about 5% of the ADD composition.
  • Matenals - Detersive ingredients or adjuncts optionally included the instant compositions can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions.
  • Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct matenals compnse, in total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, solubilizing agents, earners, processing aids, and pigments as descnbed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Tablet Form
  • composition of the present invention can be in a tablet form, especially a dimple tablet, which is preferred for use m automatic dishwashing machines.
  • a prefeiTed dimple tablet of the composition of the present invention and means for producing such a dimple tablet follows.
  • the preferred dimple tablet compnses (A) at least one compressed solid body portion (the tablet body) and (B) at least one non-compressed, non-encapsulating portion (the dimple portion).
  • the use of the non-compressed, non-encapsulating port ⁇ on(s) and compressed port ⁇ on(s) provides a supe ⁇ or delivery mechanism for detergent active agents into the domestic wash process.
  • Either of the non-compressed, non-encapsulating port ⁇ on(s) or the compressed port ⁇ on(s) can rapidly dissolve or disperse thereby providing for the earliest possible delivery of detergent active agents into the domestic wash process.
  • the detergent tablet must have a ratio of B to A from about 1 :50 to about 4; 1 , preferably from about 1 :20 to about 1: 1, more preferably about 1 : 10 to about 1 : 1 , by area.
  • Area A is the area of the detergent tablet, but excluding the area of the mould.
  • Area B is the area of the non- compressed, non-encapsulating portion s.
  • the ratio of B to A gives optimal dissolution kinetics to the dimple. Additionally, the non-compressed, non-encapsulating portion s have improved visual noticibihty.
  • the detergent tablet, the mould(s) and non-compressed, non-encapsulating port ⁇ on(s) can be of any conceivable size and shape as long as the ratio of B to A remains from about 1:50 to about 4: 1.
  • the detergent tablet will be of a size suitable to be dispensed from the dispenser.
  • the detergent active components of a detergent tablet previously adversely affected by the compression pressure used to form the tablets may now be included in a detergent tablet. Examples of these components include bleaching agents and enzymes, such as the endolase enzyme of the present invention.
  • these detergent active components may be separated from one another by having one or more compatible components contained in the compressed portion and one or more compatible components contained in the non-compressed, non-encapsulating port ⁇ on(s) of the tablet
  • components that may interact and may therefore require separation include bleaching agents, bleach activators or catalyst and enzymes; bleaching agents and bleach catalysts or activators; bleaching agents and surfactants; alkalinity sources and enzymes. It may be advantageous to provide the compressed and the non-compressed, non- encapsulating port ⁇ on(s) such that they dissolve in the wash water with different dissolution rates.
  • the tablet may also compnse a plurality of moulds in the compressed solid body portion. These plurality of moulds may be overlapping or be distinctly separate.
  • the tablet may also compnse a plurality non-compressed, non-encapsulating portions.
  • a plurality of non-compressed, non-encapsulating portions may be advantageous, enabling a tablet to be produced which has for example, a first and second and optional subsequent portions so that they have different rates of dissolution.
  • Such performance benefits are achieved by selectively dehvenng detergent active components into the wash water at different times.
  • the detergent tablets, of the present invention be free from foul or noxious odors. If present such odors may be masked or removed. This includes the addition of masking agents, perfumes, odor absorbers, such as cyclodextnns, etc.
  • the detergent tablet can be transparent, opaque or any possible shade m between these two extremes.
  • the compressed solid body and the at least one non-compressed, non- encapsulating portion can have the same or different degree of transparency, i.e. ranging from totally transparent to opaque. However, it is preferred that they be different.
  • the detergent tablet it is possible for each of the non-compressed, non-encapsulating portion to have the same or different degree of transparency, i.e. ranging from totally transparent to opaque However, it is preferred that they be different.
  • any gaps between the compressed solid body and the at least one non-compressed, non-encapsulating portion be less than 1 mm, more preferably 0 75 mm, even more preferably 0.5 mm, after one week of storage at ambient conditions.
  • the detergent tablets descnbed herein are preferably between 15g and lOOg in weight, more preferably between 18g and 80g in weight, even more preferably between 20g and 60g weight.
  • the detergent tablet descnbed herein that are suitable for use m automatic dishwashing methods are most preferably between 20g and 40g in weight
  • Detergent tablets suitable for use in fab ⁇ c laundenng methods are most preferably between 40g and lOOg, more preferably between 40g and 80g, most preferably between 40g and 65g m weight.
  • the weight ratio of compressed portion to non-compressed, gel portion is generally greater than 0.5: 1, preferably greater than 1: 1, more preferably greater than 2:1, even more preferably greater than 3: 1 or even 4: 1, most preferably at least 5:1.
  • CBS Child Bite Strength
  • the dissolution rate of the at least one non-compressed, non-encapsulating portion can be greater than the dissolution rate of the compressed portion determined using the SOT AX dissolution test method.
  • the dissolution rate of the compressed portion can be greater than the dissolution rate of the at least one non-compressed, non-encapsulating portion determined using the SOT AX dissolution test method.
  • Dissolution rate is measured using the SOT AX dissolution test method.
  • dissolution of detergent tablets is achieved using a SOT AX (tradename) machine; model number AT7 available from SOT AX.
  • SOTAX Dissolution Test Method The SOTAX machine consists of a temperature controlled waterbath with lid. 7 pots are suspended in the water bath. 7 electric stimng rods are suspended from the underside of the hd, in positions corresponding to the position of the pots in the waterbath. The lid of the waterbath also serves as a lid on the pots.
  • the SOTAX waterbath is filled with water and the temperature gauge set to 50°C Each pot is then filled with 1 litre of deionised water and the stirrer set to revolve at 250rpm The lid of the waterbath is closed, allowing the temperature of the deionised water the pots to equilibrate with the water in the waterbath for 1 hour
  • the compressed portion and non-compressed, non-encapsulating port ⁇ on(s) are weighed and one tablet is placed in each pot, the hd is then closed.
  • the compressed portion and non- compressed, non-encapsulating portion/s is visually monitored until it completely dissolves. The time is noted when the compressed portion and non-compressed, non-encapsulating port ⁇ on(s) has completely dissolved.
  • the dissolution rate of the compressed portion and non-compressed, non-encapsulating port ⁇ on(s) is calculated as the average weight (g) of tablet dissolved in deionized water per minute.
  • the compressed portion of the detergent tablet comp ⁇ ses at least one detergent active component descnbed herein but may compnse a mixture of more than one detergent active components, which are compressed.
  • Any detergent tablet component conventionally used in known detergent tablets is suitable for incorporation into the compressed portion of the detergent tablets of this invention.
  • Detergent active component(s) present in the compressed layer may optionally be prepared in combination with a earner and/or a binder for example polymer (e g. PEG), liquid silicate.
  • the detergent active components are preferably prepared in particulate form (i.e. powder or granular form) and may be prepared by any known method, for example conventional spray drying, granulation or agglomeration.
  • the particulate detergent active component(s) are then compressed using any suitable equipment suitable for forming compressed tablets, blocks, bncks or b ⁇ quettes; descnbed in more detail hereafter.
  • the compressed solid body portion preferably has at least one mould on a surface of the compressed solid body portion.
  • the non-compressed, non-encapsulating port ⁇ on(s) are mounted m to the moulds.
  • the compressed solid body portion may also be provided with a coating of a water- soluble matenal to protect the body portion.
  • the coating layer preferably compnses a matenal that becomes solid on contacting the compressed and or the non-compressed portions within preferably less than 15 minutes, more preferably less than 10 minutes, even more preferably less than 5 minutes, most preferably less than 60 seconds.
  • the coating layer is water- soluble.
  • Preferred coating layers compnse matenals selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinyl pyrro done (PVP), polyacetic acid, polyethylene glycol (PEG) and mixtures thereof.
  • Preferred carboxylic or dicarboxylic acids preferably compnse an even number of carbon atoms.
  • carboxylic or dicarboxylic acids compnse at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms.
  • Preferred dicarboxylic acids mclude adipic acid, subenc acid, azelaic acid, subacic acid, undecanedioic acid, dodecanedioic acid, tndecanedioic and mixtures thereof.
  • Preferred fatty acids are those having a carbon chain length of from C12 to C22, most preferably from C18 to C22.
  • the coating layer may also preferably compnse a disrupting agent. Where present the coating layer generally present at a level of at least 0.05%, preferably at least 0.1%, more preferably at least 1%, most preferably at least 2% or even at least 5% of the detergent tablet.
  • the detergent tablet is an automatic dishwashing composition
  • Non-Compressed. Non-Encapsulating Portion The non-compressed, non-encapsulating portion compnses deteregent active components, preferably the multi-function component of the present invention, and optionally, compnses other detergent active components, preferably other enzymes, more preferably an amylase.
  • the detergent active component(s) may be m any form for example particulate (i.e. powder or granular), gel or liquid form.
  • the non-compressed, non-encapsulating portion in addition to compnsmg an detergent active component, may also optionally compnse a earner component.
  • the detergent active component may be present m the form of a solid, gel or liquid, p ⁇ or to combination with a earner component.
  • the non-compressed, non-encapsulating portion is formulated such that the detergent active ingredient is essentially completely delivered a short penod of time.
  • the gel portion is formulated so that at least about 80% of the detergent active is delivered to the wash of a domestic washing process withm the first 5 minutes, more preferably at least about 90% the first 3 minutes and even more preferably 95% withm the first 2 minutes.
  • the non-compressed, non-encapsulating portion of the detergent tablet may be in solid, gel, liquid or powder form.
  • the detergent tablet of the present invention requires that the non-compressed, non- encapsulating portion be delivered to the compressed portion such that the compressed portion and non-compressed, non-encapsulating portion contact each other.
  • the non-compressed, non- encapsulating portion may be delivered to the compressed portion m solid or flowable form. Where the non-compressed, non-encapsulating portion is in solid form, it is pre-prepared, optionally shaped and then delivered to the compressed portion.
  • the non-compressed, non- encapsulating portion is then affixed to a pre-formed compressed portion, for example by adhesion or by insertion of the non-compressed, non-encapsulating portion to a co-operating surface of the compressed portion.
  • the compressed portion compnses at least one mould into which the non-compressed, non-encapsulating portion/s is/are delivered.
  • the non-compressed, non-encapsulating portion is preferably delivered to the compressed portion m flowable form.
  • the non-compressed, non-encapsulating portion is then affixed to the compressed portion for example by adhesion, by forming a coating over the non- compressed, non-encapsulating layer to secure it to the compressed portion, or by hardening, for example (I) by cooling to below the melting point where the flowable composition becomes a solidified melt; (n) by evaporation of a solvent; (in) by crystallization, (iv) by polyme ⁇ zation of a polymenc component of the flowable non-compressed, non-encapsulating portion, (v) through pseudo-plastic properties where the flowable non-compressed, non-encapsulating portion compnses a polymer and shear forces are applied to the non-compressed, non-encapsulating portion; (vi) combining a binding agent with the flowable non-compressed, non-encapsulating portion.
  • the flowable non-compressed, non-encapsulating portion may be an extrudate that is affixed to the compressed portion by for example any of the mechanism descnbed above or by expansion of the extrudate to the parameters of a mould provided by the compressed portion.
  • the compressed portion comp ⁇ ses at least one mould into which the non-compressed non-encapsulated port ⁇ on(s) is/are delivered.
  • the surface of the compressed portion comp ⁇ ses more than one mould into which the non-compressed, non- encapsulating portion may be delivered.
  • the mould(s) preferably at least partially accommodates one or more non-compressed, non-encapsulating portions.
  • the non-compressed, non-encapsulating port ⁇ on(s) is then delivered into the mould(s) and affixed to the compressed portion as descnbed above.
  • the detergent tablet contains one mould m which there are two non-compressed, non-encapsulating portions.
  • the first non-compressed, non-encapsulating portion could be added as a liquid, which is allowed to set or harden, or as a pre formed gel. These two different non-compressed, non-encapsulatmg portion could have different rates of dissolution.
  • the non-compressed, non-encapsulatmg portion may compnse particulates, such as powders or granules.
  • the particulates may be prepared by any known method, for example conventional spray drying, granulation, encapsulation or agglomeration.
  • Particulates may be affixed to the compressed portion by incorporating a binding agent or by forming a coating layer over the non-compressed, non-encapsulating portion.
  • the first and second and optional subsequent non-compressed, non-encapsulating portion may compnse particulates having substantially different average particle size.
  • substantially different average particle size we mean that the difference between the average particle size of the first and second and/or subsequent compositions is greater than 5%, preferably greater than 10%), more preferably greater than 15% or even 20% of the smaller average particle size.
  • the average particle size of the particulate detergent active components used herein is calculated using a se ⁇ es of Tyler sieves. The senes consists of a number of sieves each having a different aperture size.
  • Samples of a composition of detergent active components are sieved through the senes of sieves (typically 5 sieves). The weight of a sample of composition retained in the sieve is plotted against the aperture size of the sieve. The average particle size of the composition is defined as the aperture size through which 50% by weight of the sample of composition would pass.
  • compositions containing more than one detergent active components can have substantially different density.
  • the difference between the density of the first and second and/or subsequent compositions can be greater than about 5%, more preferably greater than about 10%, even more preferably greater than about 15% or even about 20% of the smaller density.
  • Density of the particulate composition of detergent active components can be measured by any known method suitable for measuring density of particulate matenal.
  • the density of the composition of detergent active components is measured usmg a simple funnel and cup device consisting of a conical funnel moulded ngidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylmdncal cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • a density measurement is taken by hand pouring the composition into the funnel. Once the funnel is filled, the flap valve is opened and powder allowed to run through the funnel, overfilling the cup. The filled cup is removed from the frame and excess powder removed from the cup by passmg a straight edged implement e.g. a knife, across its upper edge The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density m grams/litre. Replicate measurements are made as required.
  • Tablets m which one or more of the non-compressed, non-encapsulating portion compnse particulates and the average particle size and/or density of the first and the subsequent non-compressed, non-encapsulatmg portions are substantially different are preferred where the first and second and optionally subsequent non-compressed, non-encapsulatmg portions are required to have different rates of dissolution.
  • the melt is prepared by heating a composition comp ⁇ sing a detergent active component and optional earner component(s) to above its melting point to form a flowable melt.
  • the flowable melt is then poured into a mould in the surface of the compressed portion and allowed to cool. As the melt cools it becomes solid, taking the shape of the mould at ambient temperature
  • the earner component(s) may be heated to above their melting point, and then an detergent active component may be added.
  • Carner components suitable for prepanng a solidified melt are typically non-active components that can be heated to above melting pomt to form a liquid and cooled to form an mtermolecular matnx that can effectively trap detergent active components.
  • a preferred non-active carher component is an organic polymer that is solid at ambient temperature
  • the non-active detergent component is polyethylene glycol (PEG)
  • PEG polyethylene glycol
  • the flowable non-compressed, non- encapsulat g portion may harden over time to form a solid, semi-solid or highly viscous liquid non-compressed, non-encapsulatmg portion by any of the methods descnbed above.
  • the flowable non-compressed, non-encapsulatmg portion may harden by evaporation of a solvent.
  • Solvents suitable for use herein may include any known solvent in which a binding agent is soluble.
  • Preferred solvents may be polar or non-polar and may include water, alcohol, (for example ethanol, acetone) and alcohol denvatives. In an alternative embodiment more than one solvent may be used.
  • the flowable non-compressed, non-encapsulat g portion may compnse one or more binding agents.
  • Any binding agent that has the effect of causing the composition to become solid, semi-solid or highly viscous over time is envisaged for use herein.
  • mechanisms by which the binding agent causes a non-solid composition to become solid, semi-solid or highly viscous include, chemical reaction (such as chemical cross linking), or interaction between two or more components of the flowable compositions either; chemical or physical interaction of the binding agent with a component of the composition.
  • Preferred binding agents mclude a sugar/gelatme combination, starch, glycerol and organic polymers.
  • the sugar may be any monosaccha ⁇ de ( e.g.
  • Type A gelatine is preferred since it has greater stability m alkaline conditions m compa ⁇ son to type B Preferred gelatine also has a bloom strength of between 65 and 300, most preferably between 75 and 100 Preferred organic polymers include polyethylene glycol (PEG) of molecular weight from 500 to 10,000, preferably from 750 to 8000, most preferably from 1000 to 6000 available from for example from Hoechst.
  • PEG polyethylene glycol
  • TE SHEET RULE 26 a viscous paste.
  • the viscous paste is then extruded using any suitable commonly available extrusion equipment such as for example a single or twin screw extruder available from for example APV Baker, Peterborough. U.K.
  • the extrudate is then cut to size either after delivery to the compressed portion, or p ⁇ or to delivery to the compressed portion of the detergent tablet.
  • the compressed portion of the tablet comp ⁇ ses at least one mould into which the extruded non- compressed, non-encapsulatmg portion is be delivered.
  • the non-compressed, non-encapsulatmg portion is coated with a coating layer.
  • the coating may be used to affix a non-compressed, non-encapsulat g portion to the compressed portion. This may be particularly advantageous where the non-compressed, non-encapsulatmg portion comp ⁇ ses flowable particulates, gels or liquids.
  • the coating layer preferably comp ⁇ ses a matenal that becomes solid on contacting the compressed and or the non-compressed, non-encapsulatmg portions withm preferably less than 15 minutes, more preferably less than 10 minutes, even more preferably less than 5 minutes, most preferably less than 60 seconds.
  • the coating layer is water-soluble.
  • Preferred coating layers compnse matenals selected from the group consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinyl pyrro done (PVP), polyacetic acid, polyethylene glycol (PEG) and mixtures thereof.
  • Preferred carboxylic or dicarboxylic acids preferably compnse an even number of carbon atoms.
  • carboxylic or dicarboxylic acids compnse at least 4, more preferably at least 6, even more preferably at least 8 carbon atoms, most preferably between 8 and 13 carbon atoms.
  • Preferred dicarboxylic acids include adipic acid, sube ⁇ c acid, azelaic acid, subacic acid, undecanedioic acid, dodecandioic acid, t ⁇ decanedioic and mixtures thereof.
  • Preferred fatty acids are those having a carbon chain length of from C 12 to C22, most preferably from C18 to C22.
  • the coating layer may also preferably compnse a disrupting agent.
  • the coating layer generally present at a level of preferably at least about 0.05%, more preferably at least about 0.1%, even more preferably at least about 1%, even more preferably still at least about 2% or even at least about 5% of the detergent tablet.
  • the coating not be a fatty acid.
  • the coating layer may encapsulate the detergent tablet.
  • the coating layer is present at a level of at least about 4%, more preferably at least about 5%, most preferably at least about 10% of the detergent tablet.
  • the compressed and or non-compressed, non-encapsulatmg portions and/or coating layer additionally compnse a disrupting agent.
  • the disrupting agent may be a disintegrating or effervescing agent.
  • Suitable disintegrating agents include agents that swell on contact with water or facilitated water influx and/or efflux by forming channels m compressed and/or non-compressed, non-encapsulating portions . Any known disintegrating or effervescing agent suitable for use m laundry or dishwashing applications is envisaged for use herein.
  • Suitable disintegrating agent include starch, starch denvatives, alg ates, carboxymethylcellulose (CMC), cellulosic-based polymers, sodium acetate, aluminium oxide.
  • Suitable effervescing agents are those that produce a gas on contact with water. Suitable effervescing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples of preferred effervescing agents may be selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic acids such as citnc or maleic acid.
  • An advantage of including a disrupting agent m the detergent tablet of the present invention is the transport, storage and handling benefits that can be achieved by increasing the hardness of the detergent tablet without adversely affecting the cleaning performance.
  • the non-compressed, non-encapsulatmg portion may additionally contain a drying agent. Any, conventional drying agent can be used. See Vogels Text book of Practical Organic
  • drying agents are anhydrous CaS ⁇ 4, anhydrous Na2S ⁇ 4, calcium chlonde, sodium sulfite and MgS ⁇ 4.
  • suitable drying agents may depend on the end use of the tablet.
  • a drying agent for a detergent tablet for an automatic dishwashing composition for low temperatures preferably is sodium sulfite or calcium chlonde, but anhydrous CaS ⁇ 4, may be used for higher use temperatures.
  • drying agents are included in an amount of about 0.1% to about 15%, more preferably from about 0.1% to about 10%, even more preferably from about 0.5% to about 7%, by weight.
  • the non-compressed, non-encapsulatmg portion When the non-compressed, non-encapsulatmg portion is a gel mounted or formed onto the compressed solid body portion of the detergent tablet into a mould formed on the compressed solid body portion, the non-compressed, non-encapsulatmg portion may additionally contain a thickening system m addition to the at least one detergent active agent.
  • the non-compressed, non-encapsulatmg portion When the non-compressed, non-encapsulatmg portion is a gel it may include solid ingredients which are dispersed or suspended within the gel. The solid ingredients aid m the control of the viscosity of the gel formulation in conjunction with the thickening system.
  • the non-compressed, non-encapsulatmg portion typically compnses at least about 15% solid ingredients, more preferably at least about 30% solid ingredients and most preferably at least about 40% solid ingredients.
  • the non-compressed, non-encapsulatmg portion of the present invention typically do not include more than about 90% solid ingredients, when in the form of a gel.
  • Thickening System As noted earlier, the detergent tablet of the present invention compnses thickening system in the non-compressed, non-encapsulatmg portion when it is a gel, to provide the proper viscosity or thickness of the gel portion
  • the thickening system typically compnses a non- aqueous liquid diluent and an organic or polymenc gelling additive a) Liquid Diluent
  • diatomuent is used herein to connote the liquid portion of the thickening system. While some of the essential and/or optional components of the compositions herein may actually dissolve in the “diluenf-contammg phase, other components will be present as particulate mate ⁇ al dispersed withm the "d ⁇ luent"-contam ⁇ ng phase. Thus the term “diluent” is not meant to require that the solvent matenal be capable of actually dissolving all of the detergent composition components added thereto.
  • Suitable types of diluent useful in the non-aqueous thickening systems herein include alkylene glycol mono lower alkyl ethers, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like
  • a preferred type of non-aqueous diluent for use herem compnses the mono-, di-, tn-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • PEGs polyethylene glycols
  • Such matenals are those having molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred.
  • non-aqueous diluent comp ⁇ ses lower molecular weight methyl esters.
  • Such matenals are those of the general formula: Rl-C(0)-OCH3 wherein R ⁇ ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
  • the non-aqueous organic d ⁇ luent(s) employed should, of course, be compatible and non- reactive with other composition components, e.g., enzymes, used in the detergent tablets herein.
  • a diluent component will generally be utilized in an amount of from about 10% to about 60% by weight of the composition. More preferably, the non-aqueous, low-polanty organic diluent will compnse from about 20% to about 50% by weight of the composition, most preferably from about 30% to about 50% by weight of the composition, b) Gelling Additive
  • the organic gelling agent is generally present to the extent of a ratio of diluent to gelling agent in thickening system typically ranging from about 99: 1 to about 1 : 1 More preferably, the ratios range from about 19- 1 to about 4: 1.
  • the preferred gelling agents of the present invention are selected from castor oil denvatives, propylene glycol, polyethylene glycol, sorbitols and related organic thixatropes, organoclays, cellulose and cellulose denvatives, pluronics, stearates and stearate denvatives, sugar/gelatin combination, starches, glycerol, organic acid amides such as N-lauryl-L-glutamic acid di-n-butyl amide and mixtures thereof.
  • the preferred gelling agents are castor oil denvatives.
  • Castor oil is a naturally occumng t ⁇ glyce ⁇ de obtained from the seeds of Ricmus Commums, a plant which grows m most tropical or subtropical areas.
  • the pnmary fatty acid moiety m the castor oil tnglyce ⁇ de is ncmoleic acid (12-hydroxy oleic acid). It accounts for about 90% of the fatty acid moieties.
  • the balance consists of dihydroxysteanc, palmitic, steanc, oleic, hnoleic, hnolenic and eicosanoic moieties.
  • Hydrogenation of the oil e.g., by hydrogen under pressure converts the double bonds m the fatty acid moieties to single bonds, thus "hardening" the oil.
  • the hydroxyl groups are unaffected by this reaction.
  • the resulting hydrogenated castor oil therefore, has an average of about three hydroxyl groups per molecule. It is believed that the presence of these hydroxyl groups accounts in large part for the outstanding structunng properties which are imparted to the non-compressed, non- encapsulating portion compared to similar liquid detergent compositions which do not contain castor oil with hydroxyl groups in their fatty acid chains.
  • the castor oil should be hydrogenated to an iodine value of less than about 20, and preferably less than about 10. Iodme value is a measure of the degree of unsaturation of the oil and is measured by the "Wijis Method," which is well-known in the art. Unhydrogenated castor oil has an iodine value of from about 80 to 90.
  • Hydrogenated castor oil is a commercially available commodity being sold, for example, in vanous grades under the trademark CASTORWAX.RTM. by NL Indust ⁇ es, Inc., Highstown, New Jersey.
  • Other Suitable hydrogenated castor oil denvatives are Thixcm R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, made by Rheox, Laporte. Especially preferred is Thixatrol ST.
  • Polyethylene glycols when employed as gelling agents, rather than solvents, have a molecular weight range of from about 2000 to about 30000, preferably about 4000 to about 12000, more preferably about 6000 to about 10000.
  • Cellulose and cellulose denvatives when employed m the present invention preferably include: I) Cellulose acetate and Cellulose acetate phthalate (CAP); n) Hydroxypropyl Methyl Cellulose (HPMC); ⁇ )Carboxymethylcellulose (CMC); and mixtures thereof.
  • the hydroxypropyl methylcellulose polymer preferably has a number average molecular weight of about 50,000 to 125,000 and a viscosity of a 2 wt. % aqueous solution at 25°C (ADTMD2363) of about 50,000 to about 100,000 cps.
  • An especially preferred hydroxypropyl cellulose polymer is Methocel® J75MS-N wherein a 2.0 wt % aqueous solution at 25°C has a viscosity of about 75,000 cps.
  • the sugar may be any monosaccha ⁇ de (e.g. glucose), disacchande (e.g. sucrose or maltose) or polysacchande.
  • the most preferred sugar is commonly available sucrose.
  • type A or B gelatin may be used, available from for example Sigma.
  • Type A gelatin is preferred since it has greater stability in alkaline conditions in compa ⁇ son to type B.
  • Preferred gelatin also has a bloom strength of between 65 and 300, most preferably between 75 and 100.
  • the non-compressed, non-encapsulatmg portion of the present invention may include a vanety of other ingredients in addition to the thickening agent as herein before descnbed and the detergent active disclosed in more detail below.
  • Ingredients such as perfumes and dyes may be included as well as swelling/adsorbing agents such as carboxymethylcelluloses and starches to aid in adsorption of excess diluent or aid in the dissolution or breakup of the non-compressed, non-encapsulatmg portion m the wash.
  • hardness modifying agents may incorporated into the thickening system to adjust the hardness of the gel if desired.
  • hardness control agents are typically selected from vanous polymers and polyethylene glycol's and when included are typically employed in levels of less than about 20% and more preferably less than about 10% by weight of the solvent m the thickening system.
  • hardening agents such as high molecular weight PEG, preferably of a molecular weight from 10,000 to 20,000 or possibly even higher molecular weight, can be added to decrease the hardening time of the non-compressed, non-encapsulatmg portion.
  • water soluble polymenc mate ⁇ als such as of low molecular weight polyethylene glycols may be added to the mould to form an intermediate barner layer p ⁇ or to addition of the non-compressed, non-encapsulatmg portion when it is a gel.
  • the intermediate layer may act as a bamer to prevent ingredients from the gel mixing or bleeding into the compressed portion.
  • Addition of an alkaline mate ⁇ al can also speed in hardening of the non-compressed, non-encapsulating portion when it is a gel.
  • these alkaline matenals would be added to the mould before the addition of the gel.
  • the alkaline matenal may be added to the gel composition
  • These alkaline matenals also have the advantage of acting as an additional alkalinity source that is discrete and would be slower dissolving and hence have a minimal impact on any effervescence system present m the non-compressed, non-encapsulatmg portion yet provide an alkalinity boost in the wash.
  • the non-compressed, non-encapsulatmg portion of the present invention is formulated so that the gel is a pumpable, flowable gel at slightly elevated temperatures of around 30°C or greater to allow increased flexibility in producing the detergent tablet, but becomes highly viscous or hardens at ambient temperatures so that the gel in maintained in position m the at least one mould in the compressed solid body portion of the detergent tablet through shipping and handling of the detergent tablet.
  • Such hardening of the non-compressed, non-encapsulatmg portion may achieved, for example, by (l) by cooling to below the flowable temperature of the gel; (n) by evaporation of the diluent; or by (in) by polymenzation of the gelling agent.
  • the gel portion is formulated such that the gel hardens to sufficiently so that the maximum force needed to push a probe into the dimple preferably ranges from about 0.5N to about 40N.
  • This force may be characte ⁇ zed by measunng the maximum force needed to push a probe, fitted with a strain gauge, a set distance into the gel.
  • the set distance may be between 40 and 80% of the total gel depth.
  • This force can be measured on a QTS 25 tester, usmg a probe of 5mm diameter. Typical forces measured are in the range of IN to 25N.
  • compositions of detergent active components may contain a lime soap dispersant compound, preferably present at a level of from about 0.1% to about 40% by weight, more preferably about 1% to about 20%> by weight, most preferably from about 2% to about 10%) by weight of the compositions.
  • a lime soap dispersant is a mate ⁇ al that prevents the precipitation of alkali metal, ammonium or amme salts of fatty acids by calcium or magnesium ions.
  • Preferred lime soap dispersant compounds are disclosed in PCT Application No. WO93/08877.
  • Matenal Care Agents - The preferred ADD compositions may contain one or more matenal care agents which are effective as corrosion inhibitors and/or anti-tarmsh aids as descnbed m U.S. Patent Nos. 5,705,464, 5,710,115 and 5,646,101. When present, such protecting matenals are preferably incorporated at low levels, e.g., from about 0.01% to about 5% of the ADD composition.
  • Matenals - Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more matenals for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions.
  • Ad j uncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct mate ⁇ als compnse, in total, from about 30% to about 99 9%, preferably from about 70% to about 95%, by weight of the compositions), include other active ingredients such as non-phosphate builders, chelants, enzymes, suds suppressors, dispersant polymers (e.g., from BASF Corp.
  • ADD compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together m an aqueous environment, it is desirable to keep the free moisture content of the ADDs at a minimum, e.g., 7% or less, preferably 5% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide. Coating measures have been descnbed herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional bamer cartons or boxes are another helpful means of assunng maximum shelf-storage stability.
  • ingredients when ingredients are not highly compatible, it may further be desirable to coat at least one such ingredient with a low-foammg nonionic surfactant for protection.
  • a low-foammg nonionic surfactant for protection.
  • waxy mate ⁇ als which can readily be used to form suitable coated particles of any such otherwise incompatible multi-function components; however, the formulator prefers those mate ⁇ als which do not have a marked tendency to deposit or form films on dishes including those of plastic construction.
  • Product/Instructions - This invention also encompasses the inclusion of instructions on the use of the cleaning compositions descnbed herem with the packages containing the cleaning compositions or with other forms of advertising associated with the sale or use of the cleaning compositions.
  • the instructions may be included in any manner typically used by consumer product manufactunng or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and or other w ⁇ tten or oral instructions which may be connected to the purchase or use of the cleaning compositions. Specifically the instructions will include a descnption of the use of the cleaning composition.
  • the instructions may additionally include information relating to the recommended amount of cleaning composition to apply to the surface, if soaking or rubbing is appropnate to the surface; the recommended amount of water, if any, to apply to the surface before and after treatment; other recommended treatment. ,
  • a product compnsmg a cleaning composition containing a multi-function component capable of hydrolyzing ,3- ⁇ -glucans, 1,4- ⁇ -glucans and combinations, both physically and chemically, of 1,3- ⁇ -glucans and 1 ,4- ⁇ -glucans, as more fully descnbed above, and optionally containing an amylase, the product further including instructions for using the cleaning composition to clean a surface (fab ⁇ c, dish, or other hard surface) in need of cleaning, the instructions including the step of contacting a surface with an effective amount of the cleaning composition such that said cleaning composition cleans said surface Process for Making Tablet
  • the detergent tablets of the present invention are prepared by separately prepanng the composition of detergent active components forming the respective compressed portion and the non-compressed, non-encapsulat g portion/s, forming the compressed soild body portion and dehve ⁇ ng or adhenng the non-compressed, non-encapsulatmg portion s to the mould/s in the compressed portion.
  • the compressed portion is prepared by obtaining at least one detergent active component and optionally premixing with earner components. Any pre-mixmg will be earned out in a suitable mixer; for example a pan mixer, rotary drum, vertical blender or high shear mixer.
  • a suitable mixer for example a pan mixer, rotary drum, vertical blender or high shear mixer.
  • dry particulate components are admixed in a mixer, as descnbed above, and liquid components are applied to the dry particulate components, for example by spraying the liquid components directly onto the dry particulate components.
  • the resulting composition is then formed into a compressed portion in a compression step using any known suitable equipment.
  • the composition is formed into a compressed portion using a tablet press, wherein the tablet is prepared by compression of the composition between an upper and a lower punch.
  • the composition is delivered into a punch cavity of a tablet press and compressed to form a compressed portion using a pressure of preferably greater
  • the compressed portion provides at least one mould to receive the non-compressed, non-encapsulat g portion/s
  • the compressed portion is prepared using a modified tablet press compnsmg modified upper and or lower punches.
  • the upper and lower punches of the modified tablet press are modified such that the compressed portion provides one or more indentations which form the mould(s) to which the one non-compressed, non-encapsulating portion/s is delivered.
  • the compressed portion can be cooled or even frozen before the non-compressed, non- encapsulatmg portion/s are added to the at least one mould. This cooling or freezing is particularly beneficial when the non-compressed, non-encapsulatmg portion is a gel.
  • the non-compressed, non-encapsulatmg portion/s compnses at least one detergent active component.
  • the detergent active component and any other ingredients m the non-compressed, non-encapsulatmg portion s are pre-mixed using any known suitable mixing equipment.
  • the non-compressed, non-encapsulatmg portion comp ⁇ ses at least one detergent active component. Where the non-compressed, non-encapsulatmg portion compnses more than one detergent active component the components are pre-mixed using any known suitable mixing equipment.
  • the non-compressed, non-encapsulatmg portion may optionally compnse a earner with which the detergent active components are combined.
  • the non-compressed, non-encapsulatmg portion may be prepared in solid or flowable form. Once prepared the composition is delivered to the compressed portion.
  • the non-compressed, non-encapsulatmg portion may be delivered to the compressed portion by manual delivery or using a nozzle feeder extruder or by any other suitable means.
  • the non-compressed, non-encapsulatmg portion is preferably delivered to the mould using accurate delivery equipment, for example a nozzle feeder, such as a loss in weight screw feeder available from Optima, Germany or an extruder.
  • the process comp ⁇ ses dehve ⁇ ng a flowable non-compressed, non-encapsulatmg portion to the compressed portion in a delivery step and then coating at least a portion of the non-compressed, non-encapsulatmg portion with a coating layer such that the coating layer has the effect of substantially adhenng the non-compressed portion to the compressed portion.
  • the process compnses a delivery step in which the flowable non-compressed, non-encapsulatmg portion is delivered to the compressed portion and a subsequent conditioning step, wherein the non-compressed, non-encapsulatmg portion hardens.
  • a conditioning step may compnse drying, cooling, binding, polyme ⁇ zation etc. of the non- compressed, non-encapsulating portion , du ⁇ ng which the non-compressed, non-encapsulatmg portion becomes solid, semi-solid or highly viscous.
  • Heat may be used in a drying step. Heat, or exposure to radiation may be used to effect polyme ⁇ zation in a polyme ⁇ zation step.
  • the compressed portion may be prepared having a plurality of moulds.
  • the plurality of moulds are then filled with a non-compressed, non-encapsulatmg portion.
  • each mould can be filled with a different non-compressed, non- encapsulatmg portion or alternatively, each mould can be filled with a plurality of different non- compressed, non-encapsulating portion.
  • the detergent tablets may be employed m any conventional domestic washing process wherein detergent tablets are commonly employed, including but not limited to automatic dishwashing and fab ⁇ c launde ⁇ ng.
  • Methods of Cleaning The surface in need of treatment is preferably selected from the group consisting of stainless steel and other metals, ceramic, plastic, metal, dishware, cookware, baby bottles, wood, glass and mixtures thereof. Such surfaces can be either non-porous or porous.
  • the method herein when employed to remove or reduce soils or stains is highly effective on cooked-on, burned-on, d ⁇ ed-on and baked-on food soils. Additionally, it is highly effective on starch soils such as oatmeal and macaroni soils.
  • the cleaning compositions of the present invention are effective immediately upon contacting the soils and/or stains.
  • the cleaning compositions are preferably in contact with the soils and/or stains for a penod of about 1 to about 120 minutes, more preferably, about 5 to about 60 minutes, most preferably, about 10 to about 30 minutes (the typical wash cycle time for automatic dishwashmg machines).
  • the cleaning compositions of the present invention are suitable for use at any temperature at which the multi-function components that are capable of hydrolyzing both 1-3- ⁇ - D-glucans and 1-4- ⁇ -D-glucans are effective.
  • the cleaning compositions are used at temperatures below about 70°C, more preferably, below about 60°C, most preferably, below about 50°C.
  • Preferred multi-function components that are capable of hydrolyzing both 1-3- ⁇ -D- glucans and 1-4- ⁇ -D-glucans include, but are not limited to, enzymes, more preferably cellulases.
  • the dishwashing methods of the present invention compnse contacting a surface m need of treatment with an effective amount of a cleaning composition containing a multi-function component that is capable of hydrolyzing both 1-3 - ⁇ -D-glucans and 1 -4- ⁇ -D-glucans such that the cleanmg composition treats the surface.
  • the cleaning compositions of the present invention are used in automatic dishwashers.
  • any friction between the surface and the cleanmg composition, such as by scrubbing, etc. will facilitate removal and/or reduction of the soils.
  • the methods and cleaning compositions of the present invention can be employed to assist in cleaning, especially tough food cleaning and/or removing and/or reducing spotting and or films, surfaces m need of treatment for any desired purpose
  • examples of likely uses include one or more of the following: soil removal, soil reduction, spot and or film removal and/or reduction, gnt removal, filter cleaning, stam removal and stam reduction.
  • the soils are carbohydrate soils, such as cellulose, gluon and xylon substrates de ⁇ ved from cereal and gram soils. More preferably, the soils are oatmeal, barley, rye, wheat, nee and mixtures thereof.
  • a preferred machine dishwashing method compnses treating soiled articles selected from crockery, glassware, silverware, metallic items, cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a detergent tablet in accordance with
  • UBST ⁇ UTE SHEET RULE 26 with the invention.
  • an effective amount of the detergent tablet it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • the detergent tablets are from 15g to 40g m weight, more preferably from 20g to 35g in weight.
  • compositions of the present invention are not necessanly meant to limit or otherwise define the scope of the invention.
  • Cleaning Compositions for Hard Surfaces and Dishes Examples are meant to exemplify compositions of the present invention, but are not necessanly meant to limit or otherwise define the scope of the invention.
  • hard surface cleaning composition refers to liquid and granular detergent compositions for cleaning hard surfaces such as floors, walls, bathroom tile, and the like.
  • Hard surface cleaning compositions of the present invention compnse an effective amount of one or more protease enzymes, preferably from about 0.0001%) to about 10%, more preferably from about 0.001% to about 5%, more preferably still from about 0.001% to about 1% by weight of active protease enzyme of the composition.
  • such hard surface cleanmg compositions typically compnse a surfactant and a water- soluble sequestering builder. In certain specialized products such as spray window cleaners, however, the surfactants are sometimes not used since they may produce a filmy/streaky residue on the glass surface. (See U.S. Patent No. 5,679,630 Examples).
  • the surfactant component when present, may compnse as little as 0.1% of the compositions herein, but typically the compositions will contain from about 0.25% to about 10%, more preferably from about 1% to about 5% of surfactant. Typically the compositions will contain from about 0.5% to about 50% of a detergency builder, preferably from about 1% to about 10%.
  • a detergency builder preferably from about 1% to about 10%.
  • the pH should be m the range of about 8 to 12. Conventional pH adjustment agents such as sodium hydroxide, sodium carbonate or hydrochlonc acid can be used if adjustment is necessary.
  • Solvents may be included m the compositions.
  • Useful solvents include, but are not limited to, glycol ethers such as diethyleneglycol monohexyl ether, diethyleneglycol monobutyl ether, ethyleneglycol monobutyl ether, ethyleneglycol monohexyl ether, propyleneglycol monobutyl ether, dipropyleneglycol monobutyl ether, and diols such as 2,2,4-tnmethyl-l,3- pentanediol and 2-ethyl-l,3-hexaned ⁇ ol. When used, such solvents are typically present at levels of from about 0.5% to about 15%, preferably from about 3% to about 11%.
  • volatile solvents such as isopropanol or ethanol can be used in the present compositions to facilitate faster evaporation of the composition from surfaces when the surface is not nnsed after "full strength" application of the composition to the surface.
  • volatile solvents are typically present at levels of from about 2% to about 12% in the compositions.
  • the hard surface cleaning composition embodiment of the present invention is illustrated by the following nonhmitmg examples.
  • Endoglucanase 1 (pure) 0.05 0.05 0.20 0.02 0.03 0.10 0.03
  • Amylase 2 0.36 - - 0.42 - 0.36 -
  • a detergent tablet according to the present invention may be prepared as follows A detergent composition as m Example 2, formulation A is prepared and passed into a conventional rotary press. The press includes one punch shaped so that a mould is formed into one of the tablet surfaces. A gel matnx formulation as disclosed m Example 2, formulation A is then prepared. The proper amount of non-aqueous solvent is provided to a mixer and shear is applied to the solvent at a moderate rate (2,500-5,000 rpm) The proper amount of gelling agent is gradually added to the solvent under shear conditions until the mixture is homogeneous. The shear rate of the mixture is gradually increased to high shear condition of around 10,000 rpm. The temperature of the mixture is increased to between 55°C and 60°C.
  • the shear is then stopped and the mixture is allowed to cool to temperatures between 35°C and 45°C. Using a low shear mixer, the remaining ingredients are then added to the mixture as solids. The final mixture is then metered into the mould on the compressed tablet body and allowed to stand until the gel hardens or is no longer flowable.
  • Endoglucanase having the ammo acid sequence SEQ ED No. 1.
  • Plurafac C 1 3-C15 mixed ethoxylated propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5, sold under the tradename Plurafac by BASF. Alkyl-capped nonionic surfactant.
  • Endoglucanase having the amino acid sequence SEQ ED No. 1.
  • Amylase as described in WO 95/26397 and WO 96/23873.
  • Protease as disclosed in U.S. Patent No. 5,677,272.
  • Termamyl® 2xPCA commercially available from Novo Nordisk A/S. 6
  • White Termamyl® commercially available from Novo Nordisk A S.
  • Example 11 The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Cette invention concerne des compositions de nettoyage renfermant un agent multifonctions capable d'hydrolyser des 1,3-β-glucans, des 1,4-β-glucans et des combinaisons de 1,3-β-glucans et 1,4-β-glucans liés à la fois physiquement et chimiquement, et un ou plusieurs auxiliaires de nettoyage pris dans un groupe composé de tensioactifs peu moussants, d'hydrotropes et de mélanges de ses substances. L'invention concerne également l'emploi de ces compositions à des fins de nettoyage, notamment dans le cas de taches d'aliment difficiles à éliminer, ou bien pour faire disparaître et/ou atténuer des salissures, en particulier des salissures à base d'hydrates de carbone, et/ou pour faire disparaître des taches et des pellicules sur des pièces de vaisselle, des articles de cuisine et autres substrats à surface dure.
PCT/US2000/000437 1999-01-11 2000-01-07 Compositions de nettoyage renfermant un agent multifonctions; methode d'utilisation WO2000041522A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU24959/00A AU2495900A (en) 1999-01-11 2000-01-07 Cleaning compositions containing a multi-function component and method for using

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11537999P 1999-01-11 1999-01-11
US60/115,379 1999-01-11

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WO2000041522A2 true WO2000041522A2 (fr) 2000-07-20
WO2000041522A3 WO2000041522A3 (fr) 2001-09-07

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6956016B2 (en) 2001-05-14 2005-10-18 The Procter & Gamble Company Cleaning product
WO2010019728A1 (fr) * 2008-08-13 2010-02-18 The Procter & Gamble Company Composition particulaire de blanchiment comprenant des enzymes
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
CN108255025A (zh) * 2016-12-28 2018-07-06 安集微电子（上海）有限公司 一种清洗液

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995002675A1 (fr) * 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
WO1995026397A1 (fr) * 1994-03-29 1995-10-05 Novo Nordisk A/S Amylase alcaline issue d'un bacille
WO1996023873A1 (fr) * 1995-02-03 1996-08-08 Novo Nordisk A/S Alleles d'amylase-alpha
WO1999027063A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent a couches multiples comprenant a la fois des parties comprimees et des parties non comprimees

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995002675A1 (fr) * 1993-07-12 1995-01-26 Novo Nordisk A/S Composition detersive comprenant deux cellulases
WO1995026397A1 (fr) * 1994-03-29 1995-10-05 Novo Nordisk A/S Amylase alcaline issue d'un bacille
WO1996023873A1 (fr) * 1995-02-03 1996-08-08 Novo Nordisk A/S Alleles d'amylase-alpha
WO1999027063A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent a couches multiples comprenant a la fois des parties comprimees et des parties non comprimees

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6956016B2 (en) 2001-05-14 2005-10-18 The Procter & Gamble Company Cleaning product
US7078462B2 (en) 2001-05-14 2006-07-18 The Procter & Gamble Company Cleaning product
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US10463420B2 (en) 2005-05-12 2019-11-05 Innovatech Llc Electrosurgical electrode and method of manufacturing same
US11246645B2 (en) 2005-05-12 2022-02-15 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
WO2010019728A1 (fr) * 2008-08-13 2010-02-18 The Procter & Gamble Company Composition particulaire de blanchiment comprenant des enzymes
EP2157162A1 (fr) * 2008-08-13 2010-02-24 The Procter and Gamble Company Composition de blanchiment particulaire comportant des enzymes
US8343907B2 (en) 2008-08-13 2013-01-01 The Procter & Gamble Company Particulate bleaching composition comprising enzymes
CN108255025A (zh) * 2016-12-28 2018-07-06 安集微电子（上海）有限公司 一种清洗液

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WO2000041522A3 (fr) 2001-09-07

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