Source: https://patents.google.com/patent/US6113655A/en
Timestamp: 2018-07-23 09:24:58
Document Index: 602800871

Matched Legal Cases: ['application No. 91202879', 'Application No. 91870207', 'application No 94870206', 'Application No. 92870181', 'application No. 95201943', 'Application No. 0']

US6113655A - Detergent compositions comprising a pectinesterase enzyme - Google Patents
Detergent compositions comprising a pectinesterase enzyme Download PDF
US6113655A
US6113655A US09230814 US23081499A US6113655A US 6113655 A US6113655 A US 6113655A US 09230814 US09230814 US 09230814 US 23081499 A US23081499 A US 23081499A US 6113655 A US6113655 A US 6113655A
US09230814
Shuichi Tsunetsugu
Rosa Laura Moese
Andre Cesar Baeck
Ivan Maurice Alfons Jan Herbots
The present invention relates to detergent compositions comprising a pectinesterase, including dishwashing, hard surface cleaning, and laundry compositions. The compositions are useful for significant overall cleaning performance and stain/soil removal benefits. In particular, the compositions are useful for removal of body, plant, fruit juice, and vegetable juice soils and stains.
The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions comprising a pectinesterase enzyme substantially free of other pectic enzymes.
The overall performance of a detergent product for use in washing or cleaning method such as laundry, dishwashing or hard surface cleaning, is judged by a number of factors, including the ability to remove soils and the ability to prevent redeposition of the soils, or the breakdown products of the soils on the articles in the wash.
Removal of stains stemming from plants, wood, mould-clay based soil and fruits is one of today's toughest cleaning task; in particular with the trends to move to low wash temperatures. These stains typically contain complex mixtures of fibrous material based mainly on carbohydrates and their derivatives: fibres and cell wall components. Plant based soils are additionally accompanied with amylose, sugars and their derivatives.
Food soils are often difficult to remove effectively from a soiled substrate. Highly coloured or "dried-on" soils derived from fruit and/or vegetable juices are particularly challenging to remove. Specific examples of such soils would include orange juice, tomato juice, banana, mango or broccoli soils. The substrates can be fabrics, dishware or hard surfaces.
Pectic substances are found in, for example, fruit juices. The pectic substances act to hold dispersed particulates in suspension in such fruit juices, which will tend to be viscous and opaque in nature. Pectic enzymes are commonly used in the fruit/vegetable juice processing industry in the clarification of juices by breakdown of the pectic substances therein (depectinisation).
Benefits for the specific use of pectinesterase enzymes which are substantially free from other pectic enzymes in detergent formulations, particularly for use in laundry, dishwashing and household cleaning operations have not been recognised.
DE 36 35 427 is directed to phosphate-free detergents for cleaning clothes, containing enzymes with pectinase activity, which is said to include such enzymes as polygalacturonase, pectin lyase and/or pectinesterase. However, aside from the general teaching therein related to mixtures of these pectinase enzymes for the removal of inorganic soilings from clothes, the only specific teaching regarding an individual pectinase enzyme is found in example 3, where the enzyme (designated "Enzyme D") is characterised as containing a large quantity of pectin lyase. Table III provides the results of the evaluation of this Enzyme D in a detergent formulation, indicating that this high pectin lyase mixture has the highest % pectinase activity (10%) and one of the higher detergency values (83%) in combination with water-soluble high molecular compound, by comparison to the other enzyme compositions reported.
It is an object of the present invention to provide laundry, dishwashing or household detergent compositions which provide soil/stain removal benefits when used in washing and cleaning operations.
According to the present invention, it has now been surprisingly found that the pectinesterase enzymes substantially free of other pectic enzymes and especially the alkaline pectinesterase enzyme substantially free of other pectic enzymes, provide significant removal of broad range of body, plant and fruit based stains and enhance the realistic item cleaning profile of the detergent compositions.
Indeed, the inclusion of pectinesterase enzyme substantially free of other pectic enzymes and especially the alkaline type, provides in particular improved removal of body soils, dried-on fruit and vegetables juice soils/stains.
In addition, it has been found that the alkaline pectinesterase enzyme substantially free of other pectic enzymes presents improved compatibility and enhanced activity in the wash solution thereby providing improved removal of body, dried-on fruit and vegetables juice soils/stains, especially when stemming from heavy duty laundry or dishwashing compositions. It has also been found that the alkaline pectinesterase enzyme substantially free of other pectic enzymes demonstrates a better compatibility with detergent matrix, e.g. during product process and shelf life.
Furthermore, it has also been surprisingly been found that the inclusion of dispersants, particularly organic polymer dispersants, is of great value in detergent compositions containing pectinesterase enzymes. The dispersants aid dispersion of the breakdown products of the enzymatic soil degradation, thus preventing their redeposition on articles on the wash.
Improved cleaning performance has been also observed when the pectinesterase enzymes are combined with other detergent enzyme. Enzymatic bleaching system or conventional activated bleach system together with pectinesterases provides enhanced performance benefits on a wider range of stains.
Furthermore, polymers providing dye transfer inhibition combined with pectinesterase enzymes results in improved whiteness maintenance and/or soil release properties.
The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions comprising a pectinesterase enzyme substantially free of other pectic enzymes providing overall cleaning performance and stain/soil removal benefits and in particular improved removal of body, plant, dried-on fruit and vegetables juice soils/stains.
In a preferred embodiment of the present invention, the detergent composition comprises an alkaline pectinesterase enzyme substantially free of other pectic enzymes.
The pectinesterase enzyme
An essential component of the detergent compositions of the invention is pectinesterase enzyme substantially free of other pectic enzymes and especially an alkaline pectinesterase enzyme substantially free of other pectic enzymes. The term "alkaline" is intended to cover pectinesterase enzyme having an enzymatic activity of at least 10%, preferably 25%, more preferably 40% of its optimum activity, at a pH ranging from 7 to 11 and to cover pectinesterase having an optimum activity at a pH ranging from 7 to 11. The enzymatic activity is measured according to the "Assay of pectinesterase activity" as described by K. Horikoshi in Agr. Biol. Chem, Vol 36(2), 286.
The term "pectinesterase" is intended to encompass the EC classification 3.2.1.11.
As used herein, "substantially free of other pectic enzymes" means pectinesterase enzyme-containing compositions which contains at least 50% by weight of pectic enzymes which are not pectic esterase enzymes, preferably less than 25%, more preferably less than 10% and most preferably less than 5%. Such pectic enzymes include, for example, the pectin methyl esterases which hydrolyse the pectin methyl ester linkages, and the pectin treanselimiases or lyases which acts on the pectic acids to bring about non-hydrolytic cleavage of α-1→4 glycosidic linkages to form unsaturated derivatives of galacturonic acid.
By pectinesterase enzyme it is meant herein any enzyme which acts to break down pectic substances by cleaving down the ester bonds in pectin forming methanol and demethylated polygalacturonic acid. Pectic substances may be found in plant tissues, and are common constituents of fruit juices such as orange, tomato and grape juices.
Pectic substances include pectins and pectic acids. Pectins are, in general, polymers made up of chains of galacturonic acids joined by α-1→4 glycosidic linkages. Typically, in natural pectins approximately two-third of the carboxylic acid groups are esterified with methanol. Partial hydrolysis of these methyl esters gives low methoxyl pectins, which tend to form gels with calcium ions. Complete ester hydrolysis gives pectic acids.
Moreover and without wishing to be bound by any theory, it is believed that high molecular weight pectin-like substrates are present on fabric fibers from fibers' finish or from post-treatment. These high molecular weight pectin-like substrates entrap body soils/stains and their removal enhances the removal of the entrapped body soils/stains from the fabric.
Pectinesterase enzyme substantially free of other pectic enzymes can be produced by the so called wild-type organism or by any host organism in which the gene responsible for the production of the pectin enzyme, has been cloned and expressed.
Pectinesterase enzymes are produced by alkalophilic microorganisms e.g. bacterial, fungal and yeast microorganisms such as Bacillus species. Pectinesterase can be produced by the Erwinia species. Preferred are E. chrysanthemi, E. carotovora, E. amylovora, E. herbicola, E. dissolvens as described in JP 59066588, JP 63042988 and in World J. Microbiol. Microbiotechnol. (8, 2, 115-120) 1992. Purified pectinesterase can be obtained by purification and/or fractionation of pectin degrading enzymes mixtures via techniques well known in the art as described by K. Horikoshi in Agr. Biol. Chem, Vol 36(2), 288; by V. Shevchik et al. in World Journal of Microbiology and Biotechnology, Vol 8, (1992), 116 and by E. Harris et al. (1989), in "Protein purification methods, a practical approach" Ed IRL Press, Oxford, England.
Pectinesterase enzyme is incorporated into the compositions in accordance with the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.5%, most preferred from 0.001% to 0.1% pure enzyme by weight of the total composition.
Nowadays, it is common practice to modify wild-type enzymes via protein/genetic engineering techniques in order to optimise their performance efficiency in the detergent compositions of the invention. For example, the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the variant may be designed such that the optimal pH, bleach stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular cleaning application.
In particular, attention should be focused on amino acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric 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 bridges and enforcing calcium binding sites to increase chelant stability.
It has also been surprisingly been found that the inclusion of dispersants, particularly organic polymer dispersants, is of great value in detergent compositions containing pectinesterase enzymes substantially free of other pectic enzymes, especially alkaline pectinesterases. The dispersants aid dispersion of the breakdown products of the enzymatic soil degradation, thus preventing their redeposition on articles on the wash.
Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the cleaning compositions of the present invention.
The compositions of the invention may contain a lime soap peptiser compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.
A numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H. C. Borghetty and C. A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to, for example, in the following review articles; W. N. Linfield, Surfactant science Series, Volume 7, page 3; W. N. Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water of 333 ppm CaCo3 (Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with the present invention include C16 -C18 dimethyl amine oxide, C12 -C18 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C12 -C15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3 (LSDP=4), and the C14 -C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.
Polymeric lime soap peptisers suitable for use herein are described in the article by M. K. Nagarajan, W. F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic/hydrophobic bleach formulations can also be used as lime soap peptisers compounds.
Improved removal of a broad range of plant and fruit based stains is achieved with a combination of pectinesterase enzyme substantially free of other pectic enzymes and especially the alkaline pectinesterase, with other detergent enzymes.
Synergistic effects are observed from detergent compositions comprising a pectinesterase enzyme substantially free of other pectic enzymes and especially the alkaline pectinesterase and a cellulase, xylanase and/or protease.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. 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. 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 WO91/17243.
Suitable xylanases include the commercial available xylanases like Pulpzyme HB and SP431 (Novo Nordisk), Lyxasan (Gist-Brocades), Optipulp and Xylanase (Solvay).
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 International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28, 1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Other preferred proteases include those of WO 95/10591 A to Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, 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, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 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 for the present invention are proteases described in patent applications EP 251 446 and WO91/06637 and the protease BLAP® described in WO91/02792.
Improved body, plant and fruit stains/soils removal is observed with detergent compositions of the present invention further comprising starch-, sugar- and their derivatives-degrading enzymes such as amylase, gluco amylase, dextranase, pullulanase, invertase, laccase insulinase.
Suitable amylases (α and/or β) to be included in the detergent compositions of the present invention are: WO94/02597, Novo Nordisk A/S published Feb. 3, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO94/18314, Genencor, published Aug. 18, 1994; WO95/10603, Novo Nordisk A/S, published Apr. 20, 1995 and WO96/02792, genencor, published Feb. 22, 1996. Other amylases known for use in cleaning 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/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylase are stability-enhanced amylases including Purafact Ox AmR described in WO 94/18314, published Aug. 18, 1994 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Examples of commercial α-amylases products are Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S 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. 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.
Other carbohydrases combined with pectinesterase substantially free of other pectic enzymes--especially alkaline pectinesterase--enzymes show synergistic performance benefits, such as β-glucanase (lichenase, laminarase) and exo-glucanase (lignase, tannase, pentosanase, malanase and hemi-cellulase)
Finally, combinations of enzymes hydrolysing fat and waxes such as lipases, cutinases and wax esterases and pectinesterase enzyme substantially free of other pectic enzymes and especially the alkaline pectinesterase provide synergistic body, plant and fruit stains/soils removal
Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 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". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lidases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active 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).
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on Jan. 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
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 systems 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.
It has been found that a wider range of plant and/or fruit based stains/soils removal is achieved with detergent compositions comprising an enzymatic bleaching system or conventional activated bleach system in addition to the pectinesterase enzyme substantially free of other pectic enzymes and especially the alkaline pectinesterase.
Bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400-800 microns. 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 bleaching agent component for use herein can be any of the bleaching agents useful for cleaning compositions including oxygen bleaches as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
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.
Useful bleaching agents, including peroxyacids and bleaching systems 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.
Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "stain and 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. Another oxidase to be included in the detergent composition of the present invention is laccase.
Preferred enhancers are substituted phenothiazine 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.
Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Metal-containing catalysts for use in bleach compositions, include cobalt-containing catalysts such as Pentaamine acetate cobalt(III) salts and manganese-containing catalysts such as those described in EPA 549 271; EPA 549 272; EPA 458 397; U.S. Pat. No. 5,246,621; EPA 458 398; U.S. Pat. No. 5,194,416 and U.S. Pat. No. 5,114,611. Bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.
Dye transfer inhibition
Enhanced whiteness maintenance and/or soil release properties have been observed when the detergent compositions of the present invention include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
The detergent compositions according to the present invention also comprise from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into cleaning compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
The polyamine N-oxide polymers suitable for use contain units having the following structure formula: ##STR1## wherein P is a polymerisable unit, whereto the R--N--O group can be attached to or wherein the R--N--O group forms part of the polymerisable unit or a combination of both. ##STR2## A is NC, CO, C, --O--,--S--, --N--; x is 0 or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N--O group can be attached or wherein the nitrogen of the N--O group is part of these groups.
The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa<10, preferably PKa<7, more preferred PKa<6. The polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 5,000-200,000.
The average molecular weight range was determined by light scattering as described in Barth H. G. and Mays J. W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.
The detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, N.Y. and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
f) Cross-linked polymers
Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-pending patent application 94870213.9
The cleaning compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
The cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms. Granular compositions can also be in "compact" form, the liquid compositions can also be in a "concentrated" form.
The compositions of the invention may for example, be formulated as hand and machine dishwashing compositions, hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions, and compositions for use in general household hard surface cleaning operations.
Such compositions containing a pectinesterase can provide fabric cleaning, stain removal, whiteness maintenance, softening, color appearance and dye transfer inhibition when formulated as laundry detergent compositions.
When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.
The compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/liter, preferably 600 to 950 g/liter of composition measured at 20° C.
The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in 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 in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides.
A preferred filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
Typically the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
The cleaning compositions according to the present invention comprise a surfactant system wherein the surfactant can be selected from 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 0.1% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of cleaning compositions in accord with the invention.
Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
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 systems 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 alcohols 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 030 or 050 (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 as the nonionic surfactan of the surfactant systems 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 surfactant systems 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.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula. ##STR4## wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 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.
Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of C8 -C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula: ##STR5## wherein R3 is a C8 -C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1 -C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C10 -C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C10 -C16 alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3 M 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 quaternary 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.).
Other 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 triethanolamine salts) of soap, C8 -C22 primary of secondary alkanesulfonates, C8 -C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C8 -C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12 -C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6 -C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2 CH2 O)k --CH2 COO--M+ wherein R is a C8 -C22 alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.
The cleaning compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
Cationic detersive surfactants suitable for use in 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 alkyltrimethylammonium halogenides, and those surfactants having the formula:
[R.sup.2 (OR.sup.3).sub.y ][R.sup.4 (OR.sup.3).sub.y ].sub.2 R.sup.5 N+X--
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 --CH2 CH2 --, --CH2 CH (CH3)--, --CH2 CH (CH2 OH)--, --CH2 CH2 CH2 --, 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, --CH2 CHOH--CHOHCOR6 CHOHCH2 OH 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.
Quaternary ammonium surfactant suitable for the present invention has the formula (I): ##STR6## whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II): ##STR7## y is 2-4, preferably 3. whereby R2 is H or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
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,
whereby X-- is a counterion, preferably a halide, e.g. chloride or methylsulfate. ##STR8## R6 is C1 -C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as defined in formula I whereby
R1 is C8, C10 or mixtures thereof, x=o, R3, R4 =CH3 and R5 =CH2 CH2 OH.
R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.-            (i)
choline esters (compounds of formula (i) wherein R1 is ##STR9## alkyl and R2 R3 R4 are methyl). di-alkyl imidazolines [compounds of formula (i)].
Typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softening actives, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
Preferred cationic softeners among these include the following:
1) ditallow dimethylammonium chloride (DTDMAC);
2) dihydrogenated tallow dimethylammonium chloride;
3) dihydrogenated tallow dimethylammonium methylsulfate;
4) distearyl dimethylammonium chloride;
5) dioleyl dimethylammonium chloride;
6) dipalmityl hydroxyethyl methylammonium chloride;
7) stearyl benzyl dimethylammonium chloride;
8) tallow trimethylammonium chloride;
9) hydrogenated tallow trimethylammonium chloride;
10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;
11) C12-18 alkyl dihydroxyethyl methylammonium chloride;
12) di(stearoyloxyethyl) dimethylammonium chloride (DSOEDMAC);
13) di(tallowoyloxyethyl) dimethylammonium chloride;
14) ditallow imidazolinium methylsulfate;
15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium methylsulfate.
Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary 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 quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below: ##STR10## wherein Q is selected from --O--C(O)--, --C(O)--O--, --O--C(O)--O--, --NR4 --C(O)--, --C(O)--NR4 --;
R1 is (CH2)n --Q--T2 or T3 ;
R2 is (CH2)m --Q--T4 or T5 or R3 ;
R3 is C1 -C4 alkyl or C1 -C4 hydroxyalkyl or H;
R4 is H or C1 -C4 alkyl or C1 -C4 hydroxyalkyl;
T1, T2, T3, T4, T5 are independently C11 -C22 alkyl or alkenyl;
n and m are integers from 1 to 4; and
X- is a softener-compatible anion.
Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain may be straight or branched.
Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material. The compounds wherein T1, T2, T3, T4, T5 represents the mixture of long chain materials typical for tallow are particularly preferred.
Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include:
1) N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;
3) N,N-di(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
4) N,N-di(2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
5) N-(2-tallowyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(2-tallowyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammonium chloride; and
8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the cleaning compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. 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-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in cleaning 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, quaternary 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.
When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula ##STR11## wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 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 R5 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 R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
When included therein, the cleaning compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
The cleaning 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 R1 NH2 wherein R1 is a C6 -C12, preferably C6 -C10 alkyl chain or R4 X(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.
Suitable tertiary amines for use herein include tertiary amines having the formula R1 R2 R3 N wherein R1 and R2 are C1 -C8 alkylchains or ##STR12## R3 is either a C6 -C12, preferably C6 -C10 alkyl chain, or R3 is R4 X(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.
Preferred tertiary amines are R1 R2 R3 N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or ##STR13## where R5 is H or CH3 and x=1-2. Also preferred are the amidoamines of the formula: ##STR14## wherein R1 is C6 -C12 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1 -C4
Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine,C8-10oxypropylamine, 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 amidopropyldimethylamine. The most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
Color care benefits
Technologies which provide a type of color care benefit can also be included. Examples of these technologies are metallo catalysts for color maintenance. Such metallo catalysts are described in copending European Patent Application No. 92870181.2.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system 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. SKS-6 (Hoechst) SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2 Si2 O5).
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in the liquid compositions of the present invention are soaps and polycarboxylates.
Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
Detergency builder salts are normally included in amounts of from 5% 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 system 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 system are described in Copending European Patent application N 92870174.7 filed Nov. 10, 1992.
Especially preferred silicone suds controlling agents are described in Copending European Patent application N°92201649.8. Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.
Other components used in cleaning compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.
Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, -4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-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-tri-azin-6 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 U.S. 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 ##STR15## where PEG is --(OC2 H4)O--,PO is (OC3 H6 O) and T is (pcOC6 H4 CO).
Is is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the carbohydrase. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed Jan. 31, 1992.
Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula --(CH2 CH2 O)m (CH2)n CH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.
Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
The compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.
The process of the invention is conveniently carried out in the course of the cleaning process. The method of cleaning is preferably carried out at 5° C. to 95° C., especially between 10° C. and 60° C. The pH of the treatment solution is preferably from 7 to 11.
A preferred machine dishwashing method comprises treating soiled articles with an aqueous liquid having dissolved or dispensed therein an effective amount of the machine diswashing or rinsing composition. A conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-10 liters.
According to a manual dishwashing method, soiled dishes are contacted with an effective amount of the diswashing composition, typically from 0.5-20 g (per 25 dishes being treated). Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.
In the detergent compositions, 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. The abbreviated component identifications therein have the following meanings:
______________________________________LAS         Sodium linear C.sub.12 alkyl benzene       sulphonateTAS         Sodium tallow alkyl sulphateCXYAS       Sodium C.sub.1X -C.sub.1Y alkyl sulfate25EY        A C.sub.12 -C.sub.15 predominantly linear primary       alcohol condensed with an average of Y       moles of ethylene oxideCXYEZ       A C.sub.1X -C.sub.1Y predominantly linear       primary alcohol condensed with an       average of Z moles of ethylene oxideXYEZS       C.sub.1X -C.sub.1Y sodium alkyl sulfate       condensed with an average of Z moles of       ethylene oxide per moleQAS         R.sub.2.N.sup.+  (CH.sub.3).sub.2 (C.sub.2 H.sub.4 OH) with       R2 = C.sub.12 -C.sub.14Soap        Sodium linear alkyl carboxylate derived       from a 80/20 mixture of tallow and       coconut oils.Nonionic    C.sub.13 -C.sub.15 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 LF404 by       BASF Gmbh.CFAA        C.sub.12 -C.sub.14 alkyl N-methyl glucamideTFAA        C.sub.16 -C.sub.18 alkyl N-methyl glucamide.TPKFA       C12-C14 topped whole cut fatty acids.DEQA        Di-(tallow-oxy-ethyl) dimethyl ammonium       chloride.SDASA       1:2 ratio of stearyldimethyl       amine: triple-pressed stearic acid.Neodol 45-13       C14-C15 linear primary alcohol       ethoxylate, sold by Shell Chemical CO.Silicate    Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O       ratio = 2.0)NaSKS-6     Crystalline layered silicate of formula       δ-Na.sub.2 Si.sub.2 O.sub.5.Carbonate   Anhydrous sodium carbonate with a       particle size between 200 μm and 900 μm.Bicarbonate Anhydrous sodium bicarbonate with a       particle size between 400 μm and 1200 μm.STPP        Anhydrous sodium tripolyphosphateMA/AA       Copolymer of 1:4 maleic/acrylic acid,       average molecular weight about 80,000PA30        Polyacrylic acid of average molecular       weight of approximately 8,000.Terpolymer  Terpolymer of average molecular weight       approx. 7,000, comprising       acrylic:maleic:ethylacrylic acid       monomer units at a weight ratio of       60:20:20480N        Random copolymer of 3:7       acrylic/methacrylic acid, average       molecular weight about 3,500.Polyacrylate       Polyacrylate homopolymer with an       average molecular weight of 8,000 sold       under the tradename PA30 by BASF GmbHZeolite A   Hydrated Sodium Aluminosilicate of       formula Na.sub.12 (A1O.sub.2 SiO.sub.2).sub.12. 27H.sub.2 O       having       a primary particle size in the range       from 0.1 to 10 micrometersCitrate     Tri-sodium citrate dihydrate of       activity 86, 4% with a particle size       distribution between 425 μm and 850 μm.Citric      Anhydrous citric acidPB1         Anhydrous sodium perborate monohydrate       bleach, empirical formula NaBO.sub.2.H.sub.2 O.sub.2PB4         Anhydrous sodium perborate tetrahydratePercarbonate       Anhydrous sodium percarbonate bleach of       empirical formula 2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2TAED        Tetraacetyl ethylene diamine.NOBS        Nonanoyloxybenzene sulfonate in the       form of the sodium salt.Photoactivated       Sulfonated zinc phtlocyanineBleach      encapsulated in dextrin soluble       polymer.PAAC        Pentaamine acetate cobalt (III) salt.Paraffin    Paraffin oil sold under the tradename       Winog 70 by Wintershall.BzP         Benzoyl Peroxide.Pectinesterase       Pectinesterase P0764, P1889 or P54000       from Orange peel, available from Sigma;       P6763 from Tomato, available from Sigma       or pectinesterase described in DE 30 44       455.Protease    Proteolytic enzyme sold under the       tradename Savinase, Alcalase, Durazym       by Novo Nordisk A/S, Maxacal, Maxapem       sold by Gist-Brocades and proteases       described in patents WO91/06637 and/or       WO95/10591 and/or EP 251 446.Amylase     Amylolytic enzyme sold under the       tradename Purafact Ox Am.sup.R described in       WO 94/18314, sold by Genencor; Termamyl ®,       Fungamyl ® and Duramyl ®, all available       from Novo Nordisk A/S and those       described in WO95/26397.Lipase      Lipolytic enzyme sold under the       tradename Lipolase, Lipolase Ultra by       Novo Nordisk A/SCellulase   Cellulytic enzyme sold under the       tradename Carezyme, Celluzyme and/or       Endolase by Novo Nordisk A/S.CMC         Sodium carboxymethyl cellulose.HEDP        1,1-hydroxyethane diphosphonic acid.DETPMP      Diethylene triamine penta (methylene       phosphonic acid), marketed by Monsanto       under the Trade name Dequest 2060.PVNO        Poly(4-vinylpyridine)-N-Oxide.PVPVI       Poly (4-vinylpyridine)-N-       oxide/copolymer of vinyl-imidazole and       vinyl-pyrrolidone.Brightener 1       Disodium 4,4'-bis(2-       sulphostyryl)biphenyl.Brightener 2       Disodium 4,4'-bis(4-anilino-6-       morpholino-1.3.5-triazin-2-yl)       stilbene-2:2'-disulfonate.Silicone    Polydimethylsiloxane foam controllerantifoam    with siloxane-oxyalkylene copolymer as       dispersing agent with a ratio of said       foam controller to said dispersing       agent of 10:1 to 100:1.Granular Suds       12% Silicone/silica, 18% stearylSuppressor  alcohol, 70% starch in granular formSRP 1       Sulfobenzoyl end capped esters with       oxyethylene oxy and terephtaloyl       backbone.SRP 2       Diethoxylated poly (1,2 propylene       terephtalate) short block polymer.Sulphate    Anhydrous sodium sulphate.HMWPEO      High molecular weight polyethylene       oxidePEG         Polyethylene glycol.BTA         BenzotriazoleBismuth nitrate       Bismuth nitrate saltNaDCC       Sodium dichloroisocyanurateEncapsulated       Insoluble fragrance delivery technologyperfume     utilising zeolite 13x, perfume and aparticles   dextrose/glycerin agglomerating binder.KOH         100% Active solution of Potassium       HydroxidepH          Measured as a 1% solution in distilled       water at 20° C.______________________________________
The following laundry detergent compositions were prepared in accord with the invention:
______________________________________  I     II      III     IV    V     VI______________________________________LAS      8.0     8.0     8.0   8.0   8.0   8.0C25E3    3.4     3.4     3.4   3.4   3.4   3.4QAS      --      0.8     0.8   --    0.8   0.8Zeolite A    18.1    18.1    18.1  18.1  18.1  18.1Carbonate    13.0    13.0    13.0  27.0  27.0  27.0Silicate 1.4     1.4     1.4   3.0   3.0   3.0Sulfate  26.1    26.1    26.1  26.1  26.1  26.1PB4      9.0     9.0     9.0   9.0   9.0   9.0TAED     1.5     1.5.    1.5   1.5   1.5   1.5DETPMP   0.25    0.25    0.25  0.25  0.25  0.25HEDP     0.3     0.3     0.3   0.3   0.3   0.3Pectinesterase    0.005   0.01    0.05  0.01  0.02  0.08Protease 0.0026  0.0026  0.0026                          0.0026                                0.0026                                      0.0026Lipase   0.003   0.003   0.003 0.003 0.003 0.003Amylase  0.0009  0.0009  0.0009                          0.0009                                0.0009                                      0.0009MA/AA    0.3     0.3     0.3   0.3   0.3   0.3CMC      0.2     0.2     0.2   0.2   0.2   0.2Photoactivated    15      15      15    15    15    15bleach (ppm)Brightener 1    0.09    0.09    0.09  0.09  0.09  0.09Perfume  0.3     0.3     0.3   0.3   0.3   0.3Silicone 0.5     0.5     0.5   0.5   0.5   0.5antifoamMisc/minorsto 100%Density in    850     850     850   850   850   850g/liter______________________________________
The following granular laundry detergent compositions of bulk density 750 g/liter were prepared in accord with the invention:
______________________________________       I        II      III______________________________________LAS           5.25       5.61    4.76TAS           1.25       1.86    1.57C45AS         --          2.24   3.89C25AE3S       --         0.76    1.18C45E7         3.25       --      5.0C25E3         --         5.5     --QAS           0.8        2.0     2.0STPP          19.7       --      --Zeolite A     --         19.5    19.5NaSKS-6/citric acid         --         10.6    10.6(79:21)Carbonate     6.1        21.4    21.4Bicarbonate   --         2.0     2.0Silicate      6.8        --      --Sodium sulfate         39.8       --      14.3PB4           5.0        12.7    --TAED          0.5        3.1     --DETPMP        0.25       0.2     0.2HEDP          --         0.3     0.3Pectinesterase         0.001      0.02    0.005Protease      0.0026     0.0085  0.045Lipase        0.003      0.003   0.003Cellulase     0.0006     0.0006  0.0006Amylase       0.0009     0.0009  0.0009MA/AA         0.8        1.6     1.6CMC           0.2        0.4     0.4Photoactivated         15 ppm     27 ppm  27 ppmbleach (ppm)Brightener 1  0.08       0.19    0.19Brightener 2  --         0.04    0.04Encapsulated perfume         0.3        0.3     0.3particlesSilicone antifoam         0.5        2.4     2.4Minors/misc to 100%______________________________________
The following detergent formulations, according to the present invention were prepared, where I is a phosphorus-containing detergent composition, II is a zeolite-containing detergent composition and III is a compact detergent composition:
______________________________________       I        II      III______________________________________Blown PowderSTPP          24.0       --       24.0Zeolite A     --         24.0    --C45AS         9.0        6.0     13.0MA/AA         2.0        4.0     2.0LAS           6.0        8.0     11.0TAS           2.0        --      --Silicate      7.0        3.0     3.0CMC           1.0        1.0     0.5Brightener 2  0.2        0.2     0.2Soap          1.0        1.0     1.0DETPMP        0.4        0.4     0.2Spray OnC45E7         2.5        2.5     2.0C25E3         2.5        2.5     2.0Silicone antifoam         0.3        0.3     0.3Perfume       0.3        0.3     0.3Dry additivesCarbonate     6.0        13.0    15.0PB4           18.0       18.0    10.0PB1           4.0        4.0     0TAED          3.0        3.0     1.0Photoactivated         0.02       0.02    0.02bleachPectinesterase         0.05       0.05    0.01Protease      0.01       0.01    0.01Lipase        0.009      0.009   0.009Amylase       0.002      0.003   0.001Dry mixed sodium         3.0        3.0     5.0sulfateBalance (Moisture &         100.0      100.0   100.0Miscellaneous)Density (g/liter)         630        670     670______________________________________
The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing, according to the present invention were prepared:
______________________________________       I        II      III______________________________________Blown PowderZeolite A     15.0       15.0    --Sodium sulfate         0.0        5.0     --LAS           3.0        3.0     --DETPMP        0.4        0.5     --CMC           0.4        0.4     --MA/AA         4.0        4.0     --AgglomeratesC45AS         --         --      11. 0LAS           6.0        5.0     --TAS           3.0        2.0     --Silicate      4.0        4.0     --Zeolite A     10.0       15.0    13.0CMC           --         --      0.5MA/AA         --         --      2.0Carbonate     9.0        7.0     7.0Spray OnPerfume       0.3        0.3     0.5C45E7         4.0        4.0     4.0C25E3         2.0        2.0     2.0Dry additivesMA/AA         --         --      3.0NaSKS-6       --         --      12.0Citrate       10.0       --      8.0Bicarbonate   7.0        3.0     5.0Carbonate     8.0        5.0     7.0PVPVI/PVNO    0.5        0.5     0.5Pectinesterase         0.05       0.005   0.02Protease      0.026      0.016   0.047Lipase        0.009      0.009   0.009Amylase       0.005      0.005   0.005Cellulase     0.006      0.006   0.006Silicone antifoam         5.0        5.0     5.0Dry additivesSodium sulfate         0.0        9.0     0.0Balance (Moisture and         100.0      100.0   100.0Miscellaneous)Density (g/liter)         700        700     700______________________________________
The following detergent formulations, according to the present invention were prepared:
______________________________________    I      II         III     IV______________________________________LAS        20.0     14.0       24.0  22.0QAS        0.7      1.0        --     0.7TFAA       --       1.0        --    --C25E5/C45E7      --       2.0        --    0.5C45E3S     --       2.5        --    --STPP       30.0     18.0       30.0  22.0Silicate   9.0      5.0        10.0  8.0Carbonate  13.0     7.5        --    5.0Bicarbonate      --       7.5        --    --DETPMP     0.7      1.0        --    --SRP 1      0.3      0.2        --    0.1MA/AA      2.0      1.5        2.0   1.0CMC        0.8      0.4        0.4   0.2Pectinesterase      0.08     0.04       0.05  0.01Protease   0.008    0.01       0.026 0.026Amylase    0.007    0.004      --    0.002Lipase     0.004    0.002      0.004 0.002Cellulase  0.0015   0.0005     --    --Photoactivated      70 ppm   45 ppm     --    10 ppmbleach (ppm)Brightener 1      0.2      0.2        0.08  0.2PB1        6.0      2.0        --    --NOBS       2.0      1.0        --    --Balance    100      100        100   100(Moisture andMiscellaneous)______________________________________
______________________________________     I      II        III      IV______________________________________Blown PowderZeolite A   30.0     22.0      6.0    6.7Na SkS-6    --        --       --     3.3Polycarboxylate       --       --        --     7.1Sodium sulfate       19.0     5.0       7.0    --MA/AA       3.0      3.0       6.0    --LAS         14.0     12.0      22.0   21.5C45AS       8.0      7.0       7.0    5.5Cationic    --       --        --     1.0Silicate    --       1.0       5.0    11.4Soap        --       --        2.0    --Brightener 1       0.2      0.2       0.2    --Carbonate   8.0      16.0      20.0   10.0DETPMP      --       0.4       0.4    --Spray OnC45E7       1.0      1.0       1.0    3.2Dry additivesPVPVI/PVNO  0.5      0.5       0.5    --Pectinesterase       0.005    0.01      0.01   0.005Protease    0.052    0.01      0.01   0.01Lipase      0.009    0.009     0.009  0.009Amylase     0.001    0.001     0.001  0.001Cellulase   0.0002   0.0002    0.0002 0.0002NOBS        --       6.1       4.5    3.2PB1         1.0      5.0       6.0    3.9Sodium sulfate       --       6.0       --     to                                 balanceBalance (Moisture       100      100       100and Miscellaneous)______________________________________
The following high density and bleach-containing detergent formulations, according to the present invention were prepared:
______________________________________         I       II      III______________________________________Blown PowderZeolite A       15.0      15.0    15.0Sodium sulfate  0.0       5.0     0.0LAS             3.0       3.0     3.0QAS             --         1.5    1.5DETPMP          0.4       0.4     0.4CMC             0.4       0.4     0.4MA/AA           4.0       2.0     2.0AgglomeratesLAS             5.0       5.0     5.0TAS             2.0       2.0     1.0Silicate        3.0       3.0     4.0Zeolite A       8.0       8.0     8.0Carbonate       8.0       8.0     4.0Spray OnPerfume         0.3       0.3     0.3C45E7           2.0       2.0     2.0C25E3           2.0       --      --Dry additivesCitrate         5.0       --      2.0Bicarbonate     --        3.0     --Carbonate       8.0       15.0    10.0TAED            6.0       2.0     5.0PB1             14.0      7.0     10.0Polyethylene oxide of MW           --        --      0.25,000,000Bentonite clay  --        --      10.0Pectinesterase  0.005     0.01    0.08Protease        0.01      0.01    0.01Lipase          0.009     0.009   0.009Amylase         0.005     0.005   0.005Cellulase       0.002     0.002   0.002Silicone antifoam           5.0       5.0     5.0Dry additivesSodium sulfate  0.00      3.0     0.0Balance (Moisture and           100.0     100.0   100.0Miscellaneous)Density (g/liter)           850       850     850______________________________________
The following high density detergent formulations, according to the present invention were prepared:
______________________________________            I     II______________________________________AgglomerateC45AS              11.0    14.0Zeolite A          15.0    6.0Carbonate          4.0     8.0MA/AA              4.0     2.0CMC                0.5     0.5DETPMP             0.4     0.4Spray OnC25E5              5.0     5.0Perfume            0.5     0.5Dry AddsHEDP               0.5     0.3SKS 6              13.0    10.0Citrate            3.0     1.0TAED               5.0     7.0Percarbonate       20.0    20.0SRP 1              0.3     0.3Pectinesterase      0.02    0.05Protease            0.014   0.014Lipase              0.009   0.009Cellulase           0.004   0.004Amylase             0.005   0.005Silicone antifoam  5.0     5.0Brightener 1       0.2     0.2Brightener 2       0.2     --Balance (Moisture and              100     100Miscellaneous)Density (g/liter)  850     850______________________________________
The following granular detergent formulations, according to the present invention were prepared:
______________________________________      I     II      III     IV    V______________________________________LAS          21.0    25.0    18.0  18.0  --Coco C12-14 AS        --      --      --    --    21.9AE3S         --      --      1.5   1.5   2.3Decyl dimethyl        --      0.4     0.7   0.7   0.8hydroxyethyl NH4 + ClNonionic     1.2     --      0.9   0.5   --Coco C12-14 Fatty        --      --      --    --    1.0AlcoholSTPP         44.0    25.0    22.5  22.5  22.5Zeolite A    7.0     10.0    --    --    8.0MA/AA        --      --      0.9   0.9   --SRP1         0.3     0.15    0.2   0.1   0.2CMC          0.3     2.0     0.75  0.4   1.0Carbonate    17.5    29.3    5.0   13.0  15.0Silicate     2.0     --      7.6   7.9   --Pectinesterase        0.005   0.01    0.007 0.01  0.01Protease     0.007   0.007   0.007 0.007 0.007Amylase      --      0.004   0.004 0.004 0.004Lipase       0.003   0.003   0.003 --    --Cellulase    --      0.001   0.001 0.001 0.001NOBS         --      --      --    1.2   1.0PB1          --      --      --    2.4   1.2Diethylene triamine        --      --      --    0.7   1.0penta acetic acidDiethylene triamine        --      --      0.6   --    --penta methylphosphonic acidMg Sulfate   --      --      0.8   --    --Photoactivated bleach        45      50      15    45    42        ppm     ppm     ppm   ppm   ppmBrightener 1 0.05    --      0.04  0.04  0.04Brightener 2 0.01    0.3     0.05  0.13  0.13Water and Minors        up to 100%______________________________________
The following liquid detergent formulations, according to the present invention were prepared:
______________________________________  I    II     III    IV   V    VI   VII  VIII______________________________________LAS      10.0   13.0   9.0  --   25.0 --   --   --C25AS    4.0    1.0    2.0  10.0 --   13.0 18.0 15.0C25E3S   1.0    --     --   3.0  --   2.0  2.0  4.0C25E7    6.0    8.0    13.0 2.5  --   --   4.0  4.0TFAA     --     --     --   4.5  --   6.0  8.0  8.0QAS      --     --     --   --   3.0  1.0  --   --TPKFA    2.0    --     13.0 2.0  --   15.0 7.0  7.0Rapeseed --     --     --   5.0  --   --   4.0  4.0fatty acidsCitric   2.0    3.0    1.0  1.5  1.0  1.0  1.0  1.0Dodecenyl/    12.0   10.0   --   --   15.0 --   --   --tetradecenylsuccinic acidOleic acid    4.0    2.0    1.0  --   1.0  --   --   --Ethanol  4.0    4.0    7.0  2.0  7.0  2.0  3.0  2.01,2      4.0    4.0    2.0  7.0  6.0  8.0  10.0 13.-PropanediolMono Ethanol    --     --     --   5.0  --   --   9.0  9.0AmineTri Ethanol    --     --     8    --   --   --   --   --AmineNaOH (pH)    8.0    8.0    7.6  7.7  8.0  7.5  8.0  8.2Ethoxylated    0.5    --     0.5  0.2  --   --   0.4  0.3tetraethylenepentamineDETPMP   1.0    1.0    0.5  1.0  2.0  1.2  1.0  --SRP 2    0.3    --     0.3  0.1  --   --   0.2  0.1PVNO     --     --     --   --   --   --   --   0.10Pectinesterase    .005   .005   .005 .005 0.05 0.07 0.02 0.01______________________________________
Granular fabric cleaning compositions which provide "softening through the wash" capability were prepared in accord with the present invention:
______________________________________             I     II______________________________________45AS                --      10.0LAS                 7.6     --68AS                1.3     --45E7                4.0     --25E3                --      5.0Coco-alkyl-dimethyl hydroxy-               1.4     1.0ethyl ammonium chlorideCitrate             5.0     3.0Na-SKS-6            --      11.0Zeolite A           15.0    15.0MA/AA               4.0     4.0DETPMP              0.4     0.4PB1                 15.0    --Percarbonate        --      15.0TAED                5.0     5.0Smectite clay       10.0    10.0HMWPEO              --      0.1Pectinesterase      0.01    0.01Protease            0.02    0.1Lipase              0.02    0.01Amylase             0.03    0.005Cellulase           0.001   --Silicate            3.0     5.0Carbonate           10.0    10.0Granular suds suppressor               1.0     4.0CMC                 0.2     0.1Water/minors      Up to 100%______________________________________
The following rinse added fabric softener composition was prepared in accord with the present invention:
______________________________________Softener active          20.0Pectinesterase 0.01Amylase         0.001Cellulase       0.001HCL            0.03Antifoam agent 0.01Blue dye       25 ppmCaCl.sub.2     0.20Perfume        0.90Water/minors   Up to 100%______________________________________
The following fabric softener composition was prepared in accord with the present invention:
______________________________________       I        II       III______________________________________DEQA          2.6        19.0     --SDASA         --         --       70.0Stearic acid of IV = 0         0.3        --       --Neodol 45-13  --         --       13.0Hydrochloride acid          0.02      0.02     --Ethanol       --         --       1.0PEG           --         0.6      --Pectinesterase          0.005     0.05     0.01Perfume       1.0        1.0      0.75Digeranyl Succinate         --         --       0.38Silicone antifoam          0.01      0.01     --Electrolyte   --         600 ppm  --Dye           100 ppm    50 ppm   0.01Water and minors         100%       100%______________________________________
Syndet bar fabric cleaning compositions were prepared in accord with the present invention:
______________________________________          I    II       III    IV______________________________________C26 AS           20.00  20.00    20.00                                 20.00CFAA             5.0    5.0      5.0  5.0LAS (C11-13)     10.0   10.0     10.0 10.0Sodium carbonate 25.0   25.0     25.0 25.0Sodium pyrophosphate            7.0    7.0      7.0  7.0STPP             7.0    7.0      7.0  7.0Zeolite A        5.0    5.0      5.0  5.0CMC              0.2    0.2      0.2  0.2Polyacrylate (MW 1400)            0.2    0.2      0.2  0.2Coconut monethanolamide            5.0    5.0      5.0  5.0Pectinesterase   0.1    0.1       0.15                                 0.2Amylase           0.01   0.02     0.01                                  0.01Protease         0.3    --       0.5   0.05Brightener, perfume            0.2    0.2      0.2  0.2CaSO4            1.0    1.0      1.0  1.0MgSO4            1.0    1.0      1.0  1.0Water            4.0    4.0      4.0  4.0Filler*: balance to 100%______________________________________ *Can be selected from convenient materials such as CaCO3, talc, clay (Kaolinite, Smectite), silicates, and the like.
The following compact high density (0.96 Kg/l) dishwashing detergent compositions I to VI were prepared in accord with the present invention:
______________________________________   I     II      III     IV    V    VI______________________________________STPP      --      --      49.0  38.0  --   --Citrate   33.0    17.5    --    --    54.0 25.4Carbonate --      17.5    --    20.0  14.0 25.4Silicate  33.0    14.8    20.4  14.8  14.8 --Metasilicate     --      2.5     2.5   --    --   --PB1       1.9     9.7     7.8   14.3  7.8  --PB4       8.6     --      --    --    --   --Percarbonate     --      --      --    --    --   6.7Nonionic  1.5     2.0     1.5   1.5   1.5  2.6TAED      4.8     2.4     2.4   --    2.4  4.0HEDP      0.8     1.0     0.5   --    --   --DETPMP    0.6     0.6     --    --    --   --PAAC      --      --      --    0.2   --   --BzP       --      --      --    4.4   --   --Paraffin  0.5     0.5     0.5   0.5   0.5  0.2Pectinesterase     0.07    0.05    0.1   0.1   0.08 0.01Protease  0.075   0.05    0.10  0.10  0.08 0.01Lipase    --      0.001   --    0.005 --   --Amylase   0.01    0.005   0.015 0.015 0.01 0.0025BTA       0.3     0.3     0.3   0.3   0.3  --Bismuth Nitrate     --      0.3     --    --    --   --PA30      4.0     --      --    --    --   --Terpolymer     --      --      --    4.0   --   --480N      --      6.0     2.8   --    --   --Sulphate  7.1     20.8    8.4   --    0.5  1.0pH (1% solution)     10.8    11.0    10.9  10.8  10.9 9.6______________________________________
The following granular dishwashing detergent compositions examples I to IV of bulk density 1.02 Kg/L were prepared in accord with the present invention:
______________________________________   I     II      III      IV   V    VI______________________________________STPP      30.0    30.0    30.0   27.9 34.5 26.7Carbonate 30.5    30.5    30.5   23.0 30.5 2.80Silicate  7.4     7.4     7.4    12.0 8.0  20.3PB1       4.4     4.4     4.4    --    4.4 --NaDCC     --      --      --     2.0  --   1.5Nonionic  0.75    0.75    0.75   1.9  1.2  0.5TAED      1.0     1.0     --     --   1.0  --PAAC      --      --      0.004  --   --   --BzP       --      1.4     --     --   --   --Paraffin  0.25    0.25    0.25   --   --   --Pectinesterase     0.01    0.01    0.01   0.05 0.01 0.05Protease  0.05    0.05    0.05   --   0.1  --Lipase    0.005   --      0.001  --   --   --Amylase   0.003   0.001   0.01   0.02 0.01 0.015BTA       0.15    --      0.15   --   --   --Sulphate  23.9    23.9    23.9   31.4 17.4 --pH (1% solution)     10.8    10.8    10.8   10.7 10.7 12.3______________________________________
The following detergent composition tablets of 25 g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13 KN/cm2 using a standard 12 head rotary press:
______________________________________     I         II      III______________________________________STPP        --          48.8    47.5Citrate     26.4        --      --Carbonate   --          5.0     --Silicate    26.4        14.8    25.0Pectinesterase        0.007       0.01    0.05Protease     0.03        0.075   0.01Lipase       0.005      --      --Amylase      0.01        0.005    0.001PB1         1.6         7.8     --PB4         6.9         --      11.4Nonionic    1.2         2.0      1.1TAED        4.3         2.4      0.8HEDP        0.7         --      --DETPMP       0.65       --      --Paraffin    0.4         0.5     --BTA         0.2         0.3     --PA30        3.2         --      --Sulphate    25.0        14.7     3.2pH (1% solution)       10.6        10.6    11.0______________________________________
The following liquid dishwashing detergent compositions were prepared in accord with the present invention I to II, of density 1.40 Kg/L:
______________________________________          I     II______________________________________STPP             33.3    20.0Carbonate        2.7     2.0Silicate         --      4.4NaDCC            1.1     1.15Nonionic         2.5     1.0Paraffin         2.2     --Pectinesterase    0.005  0.05Protease          0.03   0.02Amylase           0.005   0.0025480N              0.50   4.00KOH              --      6.00Sulphate         1.6     --pH (1% solution) 9.1     10.0______________________________________
The following liquid hard surface cleaning compositions were prepared in accord with the present invention:
______________________________________   I     II      III     IV   V     VI______________________________________Pectinesterase      0.005  0.01    0.02  0.02  0.005                                       0.005Amylase   0.01     0.002   0.005                           0.02  0.001                                       0.005Protease  0.05    0.01    0.02  0.03  0.005                                       0.005EDTA*     --      --      2.90  2.90 --    --Citrate   --      --      --    --   2.90  2.90LAS       1.95    --      1.95  --   1.95  --C12 AS    --      2.20    --    2.20 --    2.20NaC12 (ethoxy)     --      2.20    --    2.20 --    2.20**sulfateC12       --      0.50    --    0.50 --    0.50DimethylamineoxideSCS       1.30    --      1.30  --   1.30  --Hexyl Carbitol**     6.30    6.30    6.30  6.30 6.30  6.30Water     Balance to 100%______________________________________ *Na4 ethylenediamine diacetic acid **Diethylene glycol monohexyl ether ***All formulas adjusted to pH 7
The the following spray composition for cleaning of hard surfaces and removing household mildew was prepared in accord with the present invention:
______________________________________           I______________________________________Pectinesterase    0.01Amylase           0.01Protease          0.01Sodium octyl sulfate             2.00Sodium dodecyl sulfate             4.00Sodium hydroxide  0.80Silicate (Na)     0.04Perfume           0.35Water/minors      up to 100%______________________________________
1. A detergent composition comprising an alkaline pectinesterase, less than 25%. by weight of the pectinesterase, of other pectic enzymes, and one or more components selected from the group consisting of bleaching agents, builders, optical brighteners, bactericides, abrasives, tarnish inhibitors, perfumes, coloring agents, dye transfer inhibiting agents, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, suds suppressors, soil suspension agents, anti-redeposition agents, and smectite clays.
2. A detergent composition according to claim 1 wherein said pectinesterase is present at a level from 0.0001% to 2%, pure enzyme by weight of total composition.
3. A detergent composition according to claim 1 further comprising a dispersant.
4. A detergent composition according to claim 1 further comprising another detergent enzyme.
5. A detergent composition according to claim 4 wherein said detergent enzyme is selected from amylases, proteases, lipases, cellulase and mixtures thereof.
6. A detergent composition according to claim 1 further comprising an enzymatic bleach system.
7. A detergent composition according to claim 1 further comprising a conventional activated bleach system with a Mn-based bleach catalyst.
8. A detergent composition according to claim 1 further comprising a dye transfer inhibiting polymer.
9. A detergent composition according to claim 1 which is selected from the group consisting of liquids, pastes, gels, bars, tablets, powders, and granules.
10. A detergent composition according to claim 1 comprising less than 10% by weight of the pectinesterase enzyme, of other pectic enzymes.
11. A detergent composition according to claim 10 comprising less than 5% by weight of the pectinesterase enzyme, of other pectic enzymes.
12. A detergent composition according to claim 2 wherein said pectinesterase is present at a level from 0.0005% to 0.5% pure enzyme by weight of total composition.
13. A detergent composition according to claim 12 wherein said pectinesterase is present at a level from 0.001% to 0.1% pure enzyme by weight of total composition.
14. A detergent composition according to claim 1 further comprising an enzyme selected from the group consisting of cellulases, xylanases, proteases, amylases, carbohydrases, and lipases.
15. A method of removing a fabric stain comprising incorporating the detergent composition according to claim 1 and a fabric into a wash system.
16. A method of maintaining fabric whiteness comprising incorporating the detergent composition according to claim 1 and a fabric into a wash system.
17. A method of softening a fabric comprising incorporating the detergent composition according to claim 1 and a fabric into a wash system.
18. A method of cleaning a hard surface comprising incorporating the detergent composition according to claim 1 into a wash system and applying the wash system to the hard surface.
US09230814 1996-08-09 1996-08-09 Detergent compositions comprising a pectinesterase enzyme Expired - Fee Related US6113655A (en)
PCT/US1996/012960 WO1998006806A1 (en) 1996-08-09 1996-08-09 Detergent compositions comprising a pectinesterase enzyme
US09230814 US6113655A (en) 1996-08-09 1996-08-09 Detergent compositions comprising a pectinesterase enzyme
US6113655A true US6113655A (en) 2000-09-05
ID=22255578
US09230814 Expired - Fee Related US6113655A (en) 1996-08-09 1996-08-09 Detergent compositions comprising a pectinesterase enzyme
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EP (1) EP0925344A1 (en)
JP (1) JP2000507638A (en)
CA (1) CA2263326A1 (en)
WO (1) WO1998006806A1 (en)
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HERBOTS, IVAN MAURICE ALFONS JAN;BAECK, ANDRE CESAR;MOESE, LAURA ROSA;REEL/FRAME:009964/0451;SIGNING DATES FROM 19980320 TO 19990320
2004-09-07 LAPS Lapse for failure to pay maintenance fees