Source: https://patents.google.com/patent/US6790822B1/en
Timestamp: 2019-03-18 22:33:08
Document Index: 377554341

Matched Legal Cases: ['application No. 91202879', 'Application No. 92870181', 'Application No. 96870140', 'Application No. 91870207', 'application No. 95201943', 'Application No. 0']

US6790822B1 - Detergent compositions having an anionically modified cellulose polymer - Google Patents
Detergent compositions having an anionically modified cellulose polymer Download PDF
US6790822B1
US6790822B1 US09/889,252 US88925201A US6790822B1 US 6790822 B1 US6790822 B1 US 6790822B1 US 88925201 A US88925201 A US 88925201A US 6790822 B1 US6790822 B1 US 6790822B1
US09/889,252
1999-01-13 Priority to PCT/US1999/000145 priority Critical patent/WO2000042144A1/en
2001-01-13 Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
2004-09-14 Publication of US6790822B1 publication Critical patent/US6790822B1/en
2007-02-02 Assigned to PROCTER & GAMBLE COMPANY, THE reassignment PROCTER & GAMBLE COMPANY, THE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WANG, JIPING NMN, MURATA, SUSUMU NMN, BABA, HAJIME NMN
2008-09-25 First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22271936&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US6790822(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
In detergent compositions containing anionic surfactants, if some cationic metal ions are added, it may neutralize the charge of the anionic surfactant in the washing solution because anionic surfactants also hold a negative charge. If the level of cationic metal ion becomes high, the anionic surfactant may not perform well because the anionic surfactant is precipitated by the cationic metal ion. Thus, the addition of AMC with a cationic metal ion in a detergent composition may also prevent a negative affect on anionic surfactant performance.
In the present invention, the AMC and the cationic metal ion can be added into the composition separately or, preferably added as a pre-mixture to have more strong interaction between AMC and cationic ions. If a pre-mixture of AMC and cationic metal ion is first made, the AMC and cationic metal ion may have more strong interaction. It leads to more effective AMC deposition on fabrics and less interaction with other detergent ingredients, such as anionic surfactant.
A fabric substantially coated with AMC may also prevent the redeposition of removed stains onto the fabric from the wash water.
1. Anionically Modified Cellulose
The composition of the present invention contains an anionically modified cellulose (AMC), wherein the cellulose has at least one anionically modified group substitution. A monomer of the cellulose is illustrated below,
wherein n=10 to 10000, preferably, n=50 to 5000, more preferably, n=100 to 3000. At least one of R1, R2, and R3 are substituted with an anionically modified group selected from the group consisting of carboxyl, sulphonyl, or phosphonyl group. The remaining R1, R2 and R3 are substituted from the group consisting of carboxyl, sulphonyl, phosphonyl, acetyl, ether, ester, hydrogen, alkyl, hydroxyl or amido groups.
The degrees of substitution (DS) for Formula I of the anionically modified group is preferably from about 0.2 to about 1.2, more preferably, from about 0.3 to about 0.7.
Preferable AMC is selected from the group consisting of ether modified carboxymethyl cellulose, ether modified carboxyethyl cellulose, ether modified carboxymethylethyl cellulose, ester modified carboxymethyl cellulose, ester modified carboxy ethylcellulose, ester modified carboxymethylethyl cellulose, amido modified carboxymethyl cellulose, amido modified carboxyethyl cellulose, amido modifed carboxymethylethyl cellulose, and mixtures thereof.
More preferable AMC are shown as the following:
The composition of the present invention contains an AMC by weight percent of the total detergent composition, preferably from about 0.1% to about 20%, more preferably, from about 0.5% to about 10%, even more preferably from about 2% to about 5%.
Although the AMC can be used in any available physical form, such as a powder form or liquid form, the AMC is preferably in a powder form. The mean particle size of the AMC is preferably from about 5 microns to about 10000 microns, and preferably, from about 80 microns to about 8000 microns. The moisture of a powder form of AMC is preferably from about 3% to about 20%, preferably from about 7% to 13%, by weight of the AMC.
2. Cationic Metal Ion
The compositions of the present invention also contain a cationic metal ion. A cationic metal ion means a positively charged metal ion. The cationic metal ion can be added to the present composition in the metal ion form or added in the salt form. A preferred cationic metal ion is selected from the group consisting of alkaline metal ion, alkaline earth metal ion, aluminium, and mixtures thereof. A more preferred cationic metal ion is selected from the group consisting of magnesium, calcium, aluminium, and mixtures thereof. A preferred cationic metal salt is selected from the group consisting of chloride, sulphate, nitrate, succinate, phosphate and mixtures thereof. A more preferred metal salt is selected from the group consisting of chloride, sulphate, nitrate, and mixtures thereof.
A preferred cationic metal ion salt is selected from the group consisting of magnesium chloride, magnesium sulphate, magnesium nitrate, calcium chloride, calcium sulphate, calcium nitrate and mixtures thereof.
The composition of the present invention contains a cationic metal ion by weight percent of the total detergent composition, preferably from about 0.1% to about 20%, more preferably, from about 0.25% to about 5%, and even more preferably from about 0.5% to about 3%.
The cationic metal ion may preferably be in any available physical form, such as a powder form or liquid form.
Additional Components Detersive Surfactant
The detergent compositions of the present invention may further include surfactants wherein the surfactant can be selected from the group consisting of nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
The surfactant is typically present at a level of from 0.01% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of detergent compositions in accord with the invention.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal™ CO-630, marketed by the GAF Corporation; and Triton™ X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The condensation products of primary 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 s of the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohol having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, Kyro™ EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O5O (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.
Also useful nonionic surfactants of the present invention are the alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 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 polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.
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 detersive surfactant of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Plurafac™ LF404 and Pluronic™ surfactants, marketed by BASF.
Preferred for use as the nonionic surfactant of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C8-C18 alcohol ethoxylates (preferably C10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cr5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11-15 alkyl or C16-18 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
Other suitable anionic surfactants include the 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 C10-C20 alkyl component, more preferably a C12-C18 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. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quatemary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of C12-C16 are preferred for lower wash temperatures (e.g. below about 50° C.) and C16-18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50° C.).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 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 cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quatemary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (C12-C18E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (C12-C18E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (C12-C18E(4.0)M), wherein M is conveniently selected from sodium and potassium.
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of —CH2CH2—, —CH2CH(CH3)—, —CH2CH(CH2OH)—, —CH2CH2CH2—, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, CH2CHOH—CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Quatemary ammonium surfactant suitable for the present invention has the formula (I):
R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II):
y is 24, preferably 3.
whereby 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,
Preferred quaternary ammonium surfactants are those as defined in formula I whereby
wherein R1 is C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and —(C2H40)xH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl. The preferred alkyl chain length for R1 is C12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quatemary ammonium compounds of formulae (i) for use herein are:
Typical cationic fabric softening components include the water-insoluble quatemary-ammonium fabric softening actives or thei corresponding amine precursor, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quatemary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
The quatemary ammonium compounds and amine precursors herein have the formula (I) or (II), below:
X− is a softener-compatible anion. Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quatemary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
The detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines. Suitable primary amines for use herein include amines according to the formula R1NH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X is —O—, —C(O)NH— or —NH—, R4 is a C6-C12 alkyl chain n is between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties. Preferred amines according to the formula herein above are n-alkyl amines. Suitable amines for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.
R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n, whereby X is —O—, —C(O)NH— or —NH— R4 is a C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-C2 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.
Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8-10 oxypropylamine, N coco 1-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyidimethylamine.
The detergent compositions may optionally further contain one or more enzymes which provide cleaning performance, fabric care and/or sanitisation benefits.
Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a −43 kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801, Genencor, published Sep. 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed Nov. 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471.
Peroxidase enzymes are used in 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 during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on Nov. 6, 1991 and EP No. 96870013.8, filed Feb. 20, 1996. Also suitable is the laccase enzyme.
Enhancers are generally comprised at a level of from 0.1% to 5% by weight of total composition. Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A88/09367 (Genencor); WO 90/09446 (Plant Genetic) and WO 94/14963 and WO 94/14964 (Unilever).
Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin 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 described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed Apr. 28, 1987 (particularly pages 17, 24 and 98), and which is called herein “Protease B”, and in European Patent Application 199,404, Venegas, published Oct. 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called “Protease A” herein. Suitable is the protease called herein “Protease C”, which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
A preferred protease referred to as “Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +280, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95110591 and in the patent application of C. Ghosh, et al, “Bleaching Compositions Comprising Protease Enzymes” having U.S. Ser. No. 08/322,677, filed Oct. 13, 1994. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/10591, having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in 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, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally-occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending patent application U.S. Ser. No. 60/048,550, filed Jun. 04, 1997).
Also suitable for the present invention are protease described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
The proteolytic enzymes are incorporated in the detergent compositions of the present invention at 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 (α and/or β) can be included for removal of carbohydrate-based stains. WO94/02597, Novo Nordisk A/S published Feb. 03, 1994, describes detergent compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published Apr. 20, 1995. Other amylases known for use in detergent compositions include both α- and β-amylases. α-Amylases are known in the art and include those disclosed in U.S. Pat. No. 5,003,257; EP 252,666; WO/191/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94/18314, published Aug. 18, 1994 and WO96/05295, Genencor, published Feb. 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
Examples of commercial α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban®,Fungamyl® and Duramyl®, all available from Novo Nordisk ANS Denmark. WO95/26397 describes other suitable amylases: α-amylases characterised 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® α-amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873(Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of pure enzyme by weight of the detergent composition. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. . . . containing one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates).
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr. 14, 1981. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP 199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilisation s are also described, for example, in U.S. Pat. No. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
Technologies which provide a type of color care benefit can optionally also be included in the composition. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in copending European Patent Application No. 92870181.2. Dye fixing agents, polyolefin dispersion for anti-wrinkles and improved water absorbancy, perfume and amino-functional polymer for color care treatment and perfume substantivity are further examples of color care/fabric care technologies and are described in the co-pending Patent Application No. 96870140.9, filed Nov. 07, 1996.
Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GBA-1 400 898 and in U.S. Pat. No. 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12-C14 quatemary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening s include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
Additional optional detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents.
Preferred peroxygen bleaching agents include those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like.
Preferred peroxygen bleaching agents include peroxygen bleach selected from the group consisting of perborates, percarbonates, peroxyhydrates, peroxides, persulfates, and mixtures thereof. Specific preferred examples include: sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution.
These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1% to about 25%.
The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in U.S. Pat. No. 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as disclosed in Copending European Patent Application No. 91870207.7 and unsymetrical acyclic imide bleach activator of the following formula as disclosed in the Procter & Gamble co-pending patent applications U.S. Ser. No. 60/022,786 (filed Jul. 30, 1996) and No. 60/028,122 (filed Oct. 15, 1996):
Useful bleaching agents, including peroxyacids and bleaching s comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co-pending applications U.S. Ser. No. 08/136,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
The hydrogen peroxide may also be present by adding an enzymatic (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic s are disclosed in EP Patent Application 91202655.6 filed Oct. 9, 1991.
Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Pat. No. 4,033,718. Typically, detergent compositions will contain about 0.025% to about 1.25%. by weight, of sulfonated zinc phthalocyanine.
The compositions according to the present invention may further contain a builder. Any conventional builder is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Phosphate builders can also be used herein.
Another suitable inorganic builder material is layered silicate, e.g. SKS6 (Hoechst). SKS6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2O5).
Preferred builders for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS6), and a water-soluble carboxylate chelating agent such as citric acid. Other preferred builders include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid. Preferred builders for use in liquid detergent compositions of the present invention are soaps and polycarboxylates.
Other builder materials that can form part of the builder for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
Detergency builder salts are normally included in amounts of from 3% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.
A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Pat. No. 3 933 672. Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published Apr. 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl alkanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
Such suds suppressor are described in Copending European Patent application N 92870174.7 filed 10 Nov., 1992.
Especially suitable encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616. Other suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in U.S. Pat. No. 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
Preferred optical brighteners are anionic in character, examples of which are disodium 4,4′-bis(2-diethanolamino-4-anilino-s-triazin6-ylamino)stilbene-2:2′disulphonate, disodium 4, -4′-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2′-disulphonate, disodium 4,4′-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2′-disulphonate, monosodium 4′,4″-bis-(2,4-dianilino-s-triazin ylamino)stilbene-2-sulphonate, disodium 4,4′-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2′-disulphonate, di-sodium 4,4′-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene-2,2′disulphonate, di-so-dium 4,4′bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylami-no)stilbene-2,2′disulphonate, sodium 2(stilbyl-4″-(naphtho-1′,2′:4,5)-1,2,3-triazole-2″-sulphonate and 4,4′-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the specific brighteners of copending European Patent application No. 95201943.8.
Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Pat. Nos. 4,116,885 and 4,711,730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate groups, “primarily”, in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
The detergent compositions according to the present invention can be in any physical form, such as a liquid, paste or granular form. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
In the detergent compositions of Example, the enzymes levels are expressed by pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed by weight of the total compositions.
Amylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Termamyl 120T Brightener 1: Disodium 4,4′-bis(2-sulphostyryl)biphenyl
QEA: bis((C2H5O)(C2H4O)n)(CH3) —N+—C6H12—N+—(CH3) bis((C2H5O)-(C2H4O))n, wherein n=from 20 to 30
LAS 8.0 8.0 8.0 2.0 6.0
TAS — 0.5 — 0.5 1.0
C46(S)AS 2.0 2.5 — — —
C25AS — — — 7.0 4.5
C68AS 2.0 5.0 7.0 — —
C25E5 10.0 10.0 3.4 10.0 4.6
C25E7 — — 1.0 — —
C25E3S — — — 2.0 5.0
QAS — 0.8 — — —
QAS (I) — — — 0.8 0.5
Zeolite A 18.1 18.0 14.1 18.1 20.0
Citric acid — — — 2.5 —
Carbonate 13.0 13.0 27.0 20.0 10.0
Silicate 1.4 1.4 3.0 0.3 0.5
Citrate — 1.0 — 3.0 —
MA/AA 0.3 0.3 0.3 4.0 1.0
PB4 9.0 9.0 5.0 — —
Percarbonate — — — — 18.0
TAED 1.5 0.4 1.5 — 3.9
NAC-OBS — 2.0 1.0 — —
DTPMP 0.25 0.25 0.25 0.25 —
SRP I — — — 0.2 —
EDDS — 0.25 0.4 — 0.5
CFAA — 1.0 — 2.0 —
HEDP 0.3 0.3 0.3 0.3 0.4
QEA — — — 0.2 —
Protease I — — 0.26 1.0 —
Protease 0.26 0.26 — — 1.5
Cellulase 0.3 — — 0.3 0.3
Amylase 0.1 0.1 0.1 0.4 0.5
Lipase (1) 0.3 — — 0.5 0.5
Photactivated 15 15 15 — 20
bleach (ppm) ppm ppm ppm ppm
PVNO/PVPVI — — — 0.1 —
Brightener 1 0.09 0.09 0.09 — 0.09
Perfume 0.3 0.3 0.3 0.4 0.4
Silicone antifoam 0.5 0.5 0.5 — 0.3
Carboxymethyl — — 1.0 — 1.0
Carboxyethyl — — 1.0 — —
Carboxyethylmethyl — — — 1.0 —
Ester Modified 3.0 3.0 1.5 2.0 2.0
Ether Modified — — 1.5 2.0 —
MgCl2 1.5 — 2.0 2.0 10.0
CaCl2 — 1.5 0.5 1.0 —
MgSO4 — — 0.25 — —
Mg(NO3)2 — — 0.25 — —
Misc/minors to balance balance balance balance balance
LAS 11.5 8.8 — 3.9
C25E2.5S — 3.0 18.0 —
C45E2.25S 11.5 3.0 — 15.7
Sodium 5.8 2.0 3.5 3.7
Monoethanol 3.0 1.5 1.3 2.5
Silicone 0.04 0.02 0.1 0.1
Carboxymethyl — — 0.5 1.0
Carboxyethyl — — 0.5 —
Carboxymethylethyl — — 0.5 —
Ester Modified 3.0 3.0 0.5 2.0
Ether Modified — 2.0 1.0 —
MgCl2 1.0 1.0 2.0 5.0
CaCl2 0.5 1.0 3.0 2.0
MgSO4 — 0.5 — 1.5
Mg(NO3)2 — 0.5 — 1.5
Water/minors to balance balance balance balance
(a) an anionically modified cellulose (AMC) having the following structure:
wherein n=10 to 10,000; at least one of R1, R2 and R3 is substituted with an anionically modified group selected from the group consisting of carboxyl, sulphonyl, or phosphonyl group; and
(b) from about 0.1% to about 20% by weight of said composition of a metal salt which is a member selected from the group consisting of magnesium chloride, magnesium sulphate, calcium chloride, calcium sulphate, calcium nitrate, and mixtures thereof.
2. A laundry detergent composition according to claim 1, wherein the AMC has the following structure:
wherein n=10 to 10000; at least one of R1, R2, and R3 is substituted with an anionically modified group selected from the group consisting of carboxyl, sulphonyl, or phosphonyl group and the remaining R1, R2 and R3 is substituted from the group consisting of carboxyl, sulphonyl, phosphonyl, acetyl, ether, ester, hydrogen, alkyl, hydroxyl or amido groups.
3. The laundry detergent composition according to claim 2, wherein the AMC is selected from the group consisting of ether modified carboxymethyl cellulose, ether modified carboxyethyl cellulose, ether modified carboxymethylethyl cellulose, ester modified carboxymethyl cellulose, ester modified carboxyethyl cellulose, ester modified carboxymethylethyl cellulose, amido modified carboxymethyl cellulose, amino modified carboxyethyl cellulose, amido modified carboxymethylethyl cellulose and mixtures thereof.
(a) from about 0.01% to about 60% by weight of a detersive surfactant;
(b) from about 3% to about 60% by weight of a detergent builder;
(c) from about 0.1% to about 20% by weight of an anionically modified cellulose (AMC) having the following structure:
wherein n=10 to 10,000; at least one of R1, R2 and P3 is substituted with an anionically modified group selected from the group consisting of sulphonyl, or phosphonyl group; and
(d) from about 0.1% to about 20% by weight of a cationic metal ion, wherein the molar ratio of the anionically modified group of the AMC to the cationic metal ion is from about 50:1 to about 1:50.
5. The laundry detergent composition according to claim 4, wherein the surfactant is selected from the group consisting of anionic, cationic, amphoteric, nonionic, and mixtures thereof; and the detergent builder is selected from the group consisting of pyrophosphates, orthophosphates, tripolyphosphates, higher phosphates, alkali metal carbonates and bicarbonates, alkali silicates, aluminosilicates, polycarboxylates, and mixtures thereof.
US09/889,252 1999-01-13 2001-01-13 Detergent compositions having an anionically modified cellulose polymer Expired - Fee Related US6790822B1 (en)
PCT/US1999/000145 WO2000042144A1 (en) 1999-01-13 1999-01-13 Detergent compositions having a cellulose polymer
US6790822B1 true US6790822B1 (en) 2004-09-14
ID=22271936
US09/889,252 Expired - Fee Related US6790822B1 (en) 1999-01-13 2001-01-13 Detergent compositions having an anionically modified cellulose polymer
US (1) US6790822B1 (en)
EP (1) EP1141194B1 (en)
JP (1) JP2002534592A (en)
CN (1) CN100430462C (en)
AT (1) AT382079T (en)
AU (1) AU2310099A (en)
CA (1) CA2357045C (en)
DE (1) DE69937841T2 (en)
WO (1) WO2000042144A1 (en)
US20060248657A1 (en) * 2004-05-05 2006-11-09 Jiping Wang Textile benefit compositions
US6835707B1 (en) 1998-10-13 2004-12-28 The Procter & Gamble Company Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose
GB0007661D0 (en) * 2000-03-29 2000-05-17 Unilever Plc Laundry treatment granule and detergent composition containing laundry treatment granule
DE10226088A1 (en) 2002-06-12 2004-03-04 Elotex Ag Additive for hydraulically setting systems, hydraulically setting mixtures, and their use
DE10230416A1 (en) * 2002-07-06 2004-02-12 Henkel Kgaa Detergent with fabric care component based on cellulose
US2579381A (en) 1949-10-05 1951-12-18 Du Pont Cellulose derivative composition of improved solubility
WO2000022078A1 (en) 1998-10-13 2000-04-20 The Procter & Gamble Company Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose
US6251846B1 (en) 1997-09-15 2001-06-26 The Procter & Gamble Company Laundry detergent compositions with cyclic amine based polymers to provide appearance and integrity benefits to fabrics laundered therewith
SU883168A1 (en) * 1980-03-28 1981-11-23 Всесоюзный научно-исследовательский и проектный институт химической промышленности Detergent for laundering
1999-01-13 JP JP2000593701A patent/JP2002534592A/en active Pending
1999-01-13 CA CA 2357045 patent/CA2357045C/en not_active Expired - Fee Related
1999-01-13 EP EP19990902973 patent/EP1141194B1/en not_active Revoked
1999-01-13 DE DE1999637841 patent/DE69937841T2/en not_active Expired - Lifetime
1999-01-13 CN CN 99816395 patent/CN100430462C/en not_active IP Right Cessation
1999-01-13 WO PCT/US1999/000145 patent/WO2000042144A1/en active IP Right Grant
1999-01-13 AT AT99902973T patent/AT382079T/en not_active IP Right Cessation
1999-01-13 AU AU23100/99A patent/AU2310099A/en not_active Abandoned
2001-01-13 US US09/889,252 patent/US6790822B1/en not_active Expired - Fee Related
Derwent Abstract XP-002114949, Derwent Publications, Ltd., London, GB Section Ch, Week 8239 (Nov. 23, 1981).
WO2014172902A1 (en) * 2013-04-26 2014-10-30 The Procter & Gamble Company Detergent granules with a water-swellable component
AU2310099A (en) 2000-08-01
EP1141194A1 (en) 2001-10-10
CN1337993A (en) 2002-02-27
AT382079T (en) 2008-01-15
CA2357045C (en) 2007-08-14
EP1141194B1 (en) 2007-12-26
WO2000042144A1 (en) 2000-07-20
DE69937841D1 (en) 2008-02-07
DE69937841T2 (en) 2008-12-11
CN100430462C (en) 2008-11-05
CA2357045A1 (en) 2000-07-20
JP2002534592A (en) 2002-10-15
DE69835214T2 (en) 2007-06-21 Detergent compositions containing mannanase and a dirt-repellent polymer
EP0581753A1 (en) 1994-02-02 Dye transfer inhibiting compositions comprising polymeric dispersing agents
CN1172498A (en) 1998-02-04 Detergent compositions containing lipase and protease
JP3795067B2 (en) 2006-07-12 Detergent composition comprising an inhibiting fabric softening clays dye transfer
WO2009140481A1 (en) 2009-11-19 Liquid detergent compositions
EP0635566B1 (en) 1998-06-17 Detergent compositions inhibiting dye transfer
CN1168691A (en) 1997-12-24 Detergent compositions containing amines and steatolysis enzyme
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BABA, HAJIME NMN;MURATA, SUSUMU NMN;WANG, JIPING NMN;REEL/FRAME:018847/0505;SIGNING DATES FROM 19990726 TO 19990817