EP0753041A4 - Compositions de detergent granulaire contenant de l'amylase - Google Patents

Compositions de detergent granulaire contenant de l'amylase

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Publication number
EP0753041A4
EP0753041A4 EP19950916432 EP95916432A EP0753041A4 EP 0753041 A4 EP0753041 A4 EP 0753041A4 EP 19950916432 EP19950916432 EP 19950916432 EP 95916432 A EP95916432 A EP 95916432A EP 0753041 A4 EP0753041 A4 EP 0753041A4
Authority
EP
European Patent Office
Prior art keywords
alkyl
molecular weight
group
amylase
detergent compositions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19950916432
Other languages
German (de)
English (en)
Other versions
EP0753041A1 (fr
Inventor
Anju Brooker
Ian Martin Dood
Robin Gibson Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP95916432A priority Critical patent/EP0753041A1/fr
Publication of EP0753041A4 publication Critical patent/EP0753041A4/fr
Publication of EP0753041A1 publication Critical patent/EP0753041A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to granular detergent compositions, exhibiting excellent soil removal properties especially on particulate stains.
  • Polymeric dispersing agents have been commonly used in detergent compositions to assist in removal of particulate soil from textiles.
  • Typically used species are homopolymers of acrylic acid, and copolymers of acrylic acids having an average molecular weight above 1,000, available from BASF under the trade name Sokalan, as well as polyethyleneglycols with a molecular weight above 4,000.
  • copolymers of acrylic and maleic acids having an average MW in the range of 2,000 to 100,000 are the most typically used.
  • dye transfer inhibiting polymers are added to detergent compositions in order to inhibit the transfer from dyes of colored fabrics onto other fabrics washed therewith. These polymers have the ability to complex the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • the presence of such dye transfer inhibition agents in granular detergent compositions can lead to certain negatives in particulate soil removal/suspension, especially if dispersing agents of the above type are not used.
  • the present invention now permits the use of dye- transfer inhibition agents in granular compositions, without the need to use dispersing agents such as described above.
  • compositions of the invention exhibit excellent particular soil removal properties, as well as an optimal biodegradability profile.
  • the present invention provides granular detergent compositions containing an amylase, a polymeric dye transfer inhibition agent, and less than 2% by weight of a dispersing agent being a homopolymer of acrylic acid or a copolymer of maleic and acrylic acid or salt thereof, with an average molecular weight above 1,000, or a polyethylene glycol with a molecular weight above 4,000.
  • composition herein comprise as an essential ingredient an amylase enzyme.
  • Suitable amylases include, for example, -amylases obtained from a special strain of B. licheniforms, described in more detail in GB-1,296,839 (Novo) .
  • Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc. and Termamyl, sold by Novo Nordisk A/S.
  • amylases are fungal species such as Fungamyl ® commercially available from Novo Nordisk A/S.
  • the amylase should be used at levels of from 0.05 to 1.5% by weight of the detergent composition.
  • the level of amylase should be such as to provide an activity typically in the range of 1 to 500 KNU/100 g of detergent composition (Kilo Novo Units) . Examples are so-called Termamyl R 60T and Termamyl R 120T (ex. Novo Nordisk) .
  • the level should be such as to provide an activity in the range of from 1 to 5,000 FAU/lOOg of detergent composition (Fungal Apha Amylase Unit) .
  • the dye transfer inhibition agent is the dye transfer inhibition agent
  • the detergent compositions according to the present invention also comprise from 0.001% to 10 %> , preferably from 0.01% to 2%, more preferably from 0.02% to 1% by weight of a polymeric dye transfer inhibiting agent.
  • a polymeric dye transfer inhibiting agent are polyamine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones, polyvinylimidazoles and cross-linked variants of these polymers, and mixtures thereof.
  • polyamine N-oxide polymers suitable for use contain units having the following structure formula : P
  • P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both.
  • A is NC 0 , 8CO, BC, -0-,-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-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
  • the N-0 group can be represented by the following general structures :
  • RI, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N- oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group.
  • Preferred polyamine N- oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
  • polyamine oxides wherein R groups can be aromatic such as phenyl examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyi ides, polyacrylates and mixtures thereof.
  • 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.
  • 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.
  • 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 average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 20,000- 200, 000.
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N- vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10, 000 to 20, 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".
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
  • 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.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY 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) .
  • PVP K-15 is also available from ISP Corporation.
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP" having an average molecular weight of from PVP"
  • the detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have 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.
  • the detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP" having an average molecular weight of from PVP"
  • the detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average 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.
  • the polymeric dispersing agent is the polymeric dispersing agent
  • conventional polymeric dispersing agents are not essential to achieve good particulate soil removal. Accordingly, such conventional polymers as homopolymers of acrylic acid and copolymers ' of acrylic and maleic acids and salts thereof, with an average molecular weight above 1,000, as well as polyethylene glycols with an average molecular weight above 4,000, can be dispensed of, or their levels minimized in the compositions of the present invention.
  • copolymers of acrylic and maleic acid normally in the form of their water-soluble salts.
  • the average molecular weight of such copolymers in the acid form ranges from about 2,000 to 100,000, more preferably from about 5,000 to about 80,000, most preferably from about 7,000 to 70,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/ aleate copolymers of this type are known materials which are described in European Patent Application No. 66915.
  • the level of the polymeric dispersants above should be kept below 2% by weight of the total detergent composition, and is preferably close to zero.
  • the granular detergent compositions herein are preferably laundry detergent compositions and contain a surfactant and a detergent builder as essential ingredients. Suitable surfactants and builders are described in detail hereinafter:
  • Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a c 10 ⁇ c 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C]_Q-C20 alkyl component, more preferably a C_2 ⁇ C]_8 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 quarternary ammonium cations derived from alkylamines such as ethyla ine, diethylamine, triethylamine, and mixtures thereof, and the like) .
  • alkyl chains of C;i2 _ 16 are preferred for lower wash temperatures (e.g., below about 50°C) and C]_g-]_g alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C) .
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m S ⁇ 3M wherein R is an unsubstituted CIQ -C 24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a c 12" c 20 alkyl or hydroxyalkyl, more preferably Ci2 ⁇ c l8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted CIQ -C 24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component,
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl- , dimethyl-, trimethyl-am onium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethyla ine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C]_2" C 18 alkyl polyethoxylate (1.0) sulfate, C ⁇ -C ⁇ E (1.0)M) , c 12 ⁇ c 18 alkyl polyethoxylate (2.25) sulfate, C 2 ⁇ C]_8E(2.25)M) , C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 1 -C 1 8E(3.0) , and C ⁇ -Ci ⁇ alkyl polyethoxylate (4.0) sulfate C ] _2-C 8 E (4 • 0)M) , wherein M is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent 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, C9-C20 linear alkylbenzenesulphonates, Cs ⁇ c 22 primary or secondary alkanesulphonates, C ⁇ -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C9-C20 linear alkylbenzenesulphonates Cs ⁇ c 22 primary or secondary alkanesulphonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ehtylene oxide) ; alkyl ester sulfonates such as C_4_ 16 methyl ester sulfonates; 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 sulfosuccinate (especially saturated and unsaturated c 12 _c 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg- C]_4 diesters) , acyl sarcosinates, s
  • Preferred surfactants for use in the compositions herein are the alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
  • the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40 %, preferably from about 3 % to about 20 % by weight of such anionic surfactants.
  • the present laundry detergent compositions preferably also comprise a nonionic surfactant. While any nonionic surfactant may be normally employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N- alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactants wherein at least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with an average of up to 25 moles of ethylene oxide per more of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • the nonionic surfactant system herein can also include a polyhydroxy fatty acid amide component.
  • Polyhydroxy fatty acid amides may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N- (RI) -CH2 (CH20H) 4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl glucamine with C12-C20 fatty acid methyl ester.
  • Nonionic surfactant systems and granular detergents made from such systems have been described in WO 92 6160, published on 16th April, 1992.
  • This application describes (example 15) a granular detergent composition prepared by fine dispersion mixing in an Eirich RV02 mixer which comprises N-methyl glucamide (10%), nonionic surfactant (10%) .
  • the polyhydroxy fatty acid amide may be present in compositions of the present invention at a level of from 0% to 50% by weight of the detergent component or composition, preferably from 5% to 40% by weight, even more preferably from 10% to 30% by weight.
  • nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a 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.
  • 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 preferred alkylpolyglycosides have the formula
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantely the 2-position.
  • the laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein, including the semi-polar nonionic amine oxides described below.
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :
  • R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of -CH 2 CH 2 _, -CH 2 CH(CH 3 )-, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 -, and mixtures thereof
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH 2 COH-CHOHCOR 6 CHOHCH 2 OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
  • R ⁇ is the same as R 4 or is an alkyl chain wherein the total number of carbon
  • the laundry detergent compositions of the present invention typically comprise from 0 % to about 25 %, preferably form about " 3 % to about 15 % by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent 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 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. Patent No. 3,929,678 to Laughlin et al. , issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivates of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quarternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at columns 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing form about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of form about 10 to about 18 carbon atoms and 2 moieties selected form the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula : 0
  • the laundry detergent compositions herein contain a builder, preferably non-phosphate detergent builders, although phosphate-containing species are not excluded in the content of the present invention. These can include, but are not restricted to alkali metal carbonates, bicarbonates, silicates, aluminosilicates, carboxylates and mixtures of any of the foregoing.
  • the builder system is present in an amount of from 25% to 80% by weight of the composition, more preferably from 30% to 60% by weight.
  • Suitable silicates are those having an Si ⁇ 2 : Na2 ⁇ ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of Si ⁇ 2 : Na2 ⁇ ratios from 2.0 to 2.8 being preferred.
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2,3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and a preferred example of this formula comprise the form of Na2Si2 ⁇ 5.
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is -Na2Si2 ⁇ 5, NaSKS-6.
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • preferred sodium aluminosilicate zeolites have the unit cell formula
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula
  • M is sodium, potassium, ammonium or substituted ammonium
  • z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO ⁇ hardness per gram of anhydrous aluminosilicate.
  • Hydrated sodium Zeolite A with a particle size of from about 0.01 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • the term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite X, P and MAP, the latter species being described in EPA 384 070.
  • the crystalline aluminosilicate ion exchange material is a Zeolite A having the formula
  • Suitable carboxylate builders containing one carboxy group include lactic acid, glycollic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686 and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1, and the 1,2,2-ethane tetracarboxylates , 1, 1, 3, 3-propane tetracarboxylates and 1, 1,2, 3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439, 000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran -cis- dicarboxylates, 2,2,5,5,- tetrahydrofuran - tetracarboxylates, 1, 2, 3, 4, 5, 6-hexane hexacarboxylates and carbxoymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivates disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the granular detergent compositions herein typically have a pH above 8.5, preferably in the range of from 9 to 11.
  • the present laundry granular compositions are preferably in a compact form, having a bulk density of at least 650 g/1, preferably at least 750g/l, but can also be in a conventional form, with densities in a range of from 200 g/1 to 700 g/1.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N- hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraprionates, triethylenetetraamine-hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorous are permitted in detergent compositons, and include ethylenediaminetetrakis ( ethylenephosphonates) as DEQUEST. Preferred, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3, 5- disulfobenzene.
  • EDDS ethyelediamine disuccinate
  • these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the granular detergent compositions and automatic dishwashing compositions herein have a pH above 8.5, preferably in the range of from 9 to 11.
  • the present laundry granular compositions are preferably in a compact form, having a bulk density of at least 650 g/1, preferably at least 750g/l, but can also be in a conventional form, with densities in a range of from 200 g/1 to 700 g/1.
  • Automatic dishwashing compositions typically contain, in addition to the amylase of the invention, a builder, such as described above, a source of alkalinity, such as silicate or carbonate, and a bleaching agent, preferably percarbonate, those ingredients amounting to up to 70% of the formulation.
  • a builder such as described above
  • a source of alkalinity such as silicate or carbonate
  • a bleaching agent preferably percarbonate
  • Laundry Additive Compositions such compositions preferably contain in addition to the amylase of the invention, a bleaching agent at levels of from 15 to 80% by weight.
  • ingredients which are known for use in detergent compositions may also be used as optional ingredients in the various embodiments of the present invention, such as bleaching agents, bleach activators, polymers, biodegradable dispersing agents, other enzymes, suds suppressing agents, fabric softening agents, in particular fabric softening clay, as well as dyes, fillers, optical brighteners, pH adjusting agents, non builder alkalinity sources, enzyme stability agents, hydrotopes, solvents, perfumes.
  • Such agents may be used in the present composition, as levels ranging from 1 to 6%.
  • dispersants can be mentioned polyvinylalcohols with a molecular weight up to 70,000, polyethyleneglycols with a molecular weight below 4,000, preferable 1 to 3,000, or terpolymers of maleic/acrylic acid and vinyl alcohol having a molecular weight ranging from 3,000 to 70,000, with the percentage of vinyl alcohol being from 5 to 60%.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyasparatate preferably have a molecular weight of about 10,000.
  • Polysuccinimide and acrylic-acrolein and mixtures thereof may also be used in this respect.
  • Enzymatic materials other than the specific amylases herein can be incorporated into the detergent compositions herein. Suitable are proteases, upases, cellulases, peroxidases, other amylases and mixtures thereof.
  • a suitable lipase enzyme is manufactured and sold by
  • the granular laundry detergent compositions herein contain a bleaching agent; however bleach-free granular detergent compositions are also desirable, particular for the treatment of certain fabrics requiring special care; therefore, such bleach-free detergent compositions are also encompassed by the present invention.
  • the bleaching agent if used, is either an inorganic persalt such as perborate, persulfate, percarbonate or a preformaced organic peracid or perimidic acid, such as N,N phtaloylaminoperoxy caproic acid, 2-carboxy- phtaloylaminoperoxy caproic acid, N,N phtaloylaminoperoxy valeric acid, Nonyl amide of peroxy adipic acid, 1,12 diperoxydodecanedoic acid, Peroxybenzoic acid and ring substituted peroxybenzoic acid, Monoperoxyphtalic acid (magnesium salt, hexhydrate) , Diperoxybrassylic acid.
  • the preferred bleaching agent is percarbonate.
  • the bleach-containing laundry detergent herein typically contain from 1% to 40%, preferably from 3% to 30% by weight, most preferably from 5% to 25% by weight of alkali metal percarbonate bleach, in the form of particles having a mean size from 250 to 900 micrometers, preferably 500 to 700 micrometers.
  • the alkali metal percarbonate bleach is usually in the form of the sodium salt.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3 3H2O2 •
  • the percarbonate bleach can be coated with e.g. a further mixed salt of an alkali metal sulphate and carbonate.
  • Such coatings together with coating processes have previously been described in GB-1, 466, 799, granted to Interox on 9th March 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:2000 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S04.n.Na2C03 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Suitable coating materials are sodium silicate, of Si ⁇ 2:Na2 ⁇ ratio from 1.6:1 to 2.8:1, and magnesium silicate.
  • carbonate/sulphate coated percarbonate bleach may include a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1- diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1,1- diphosphonic acid (HEDP) or an aminophosphonate
  • Preferred heavy metal sequestrants for incorporation as described herein above include the organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene dia ine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • Organic phosphonates and amino alkylene poly(alkylene phosphonates) such as the alkali metal ethane 1-hydroxy diphosphonates, the nitrilo trimethylene phosphonates, the ethylene dia ine tetra methylene phosphonates and the diethylene triamine penta methylene phosphonates.
  • the bleach containing detergent compositions preferably contain from 1% to 20% by weight of the composition, preferably from 2% to 15% by weight, most preferably from 3% to 10% by weight of a peroxyacid bleach activator, in addition to the bleaching agent described above.
  • Peroxyacid bleach activators as additional bleaching components in accordance with the invention can be selected from a wide range of class and are preferably those containing one or more N-or O-acyl groups.
  • Suitable classes include anhydrides, esters, amides, and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789.
  • the most preferred classes are esters such as are disclosed in GB-A-836 988, 864,798, 1 147 871 and 2 143 231 and amides such as are disclosed in GB-A-855 735 and 1 246 338.
  • Particularly preferred bleach activator compounds as additional bleaching components in accordance with the invention are the N-,N,N'N" tetra acetylated compounds of the formula
  • x can be 0 or an integer between 1 and 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD Tetraacetyl hexylene diamine
  • peroxyacid bleach compounds are the amide substituted compounds of the following general formulae :
  • R 1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from about 1 to about 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R ⁇ preferably contains from about 6 to 12 carbon atoms.
  • R 2 preferably contains from about 4 to 8 carbon atoms.
  • R-L may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat.
  • Analogous structural variations are permissible for R 2 .
  • the substitution can including for example, tallow fat.
  • Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R 1 and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Another class of bleach activators to use in combination with percarbonate comprises Cg, Cg, and/or C]_Q (6- octanamidocaproyl) oxybenzenesulfonate, 2-phenyl- (4H) 3, 1 benzoxazin-4-one, benzoyllactam preferably benzoylcaprolactam and nonanoyl lactam preferably nonanoyl caprolactam.
  • organic polymers other than the dye transfer exhibiting or dispersants described hereinabove.
  • organic polymers may be mentioned sodium carboxy-lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose.
  • Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • Lipase Lipolase 0.3 0.3 0.3 (100 KLU)
  • Amylase 1 1 (Termamyl 60KNPU Terpolymer*** 4
  • Example 1 and Example 2 showed significantly better clay soil removal properties than the composition A.
  • Comparative cleaning assessment was done by expert judges using a scale of 0 to 4 panel-score-units (PSU) In this scale 0 is given for no difference and 4 is given for maximum difference.
  • PSU panel-score-units
  • PVNO Polyvinyl-N-Oxide 0.3 0 0.5 0.2 0.2 0.4 0.3

Abstract

Composition de détergent granulaire d'une amylase, un agent polymère inhibant le transfert des couleurs et moins de 2 % en poids d'un dispersant pouvant consister en un homopolymère d'acide acrylique, ou un copolymère d'acide maléique et d'acide acrylique, ou un de leurs sels, d'un poids moléculaire moyen supérieur à 1000, ou un polyéthylèneglycol d'un poids moléculaire inférieur à 4000.
EP95916432A 1994-04-22 1995-04-17 Compositions de detergent granulaire contenant de l'amylase Withdrawn EP0753041A1 (fr)

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EP94302880 1994-04-22
EP94302880 1994-04-22
EP95916432A EP0753041A1 (fr) 1994-04-22 1995-04-17 Compositions de detergent granulaire contenant de l'amylase
PCT/US1995/004708 WO1995029222A1 (fr) 1994-04-22 1995-04-17 Compositions de detergent granulaire contenant de l'amylase

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EP0753041A1 EP0753041A1 (fr) 1997-01-15

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MA (1) MA23525A1 (fr)
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DE102008038479A1 (de) * 2008-08-20 2010-02-25 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit gesteigerter Waschkraft

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FR2144721A1 (fr) * 1971-07-02 1973-02-16 Procter Gamble Europ
US4767557A (en) * 1985-06-28 1988-08-30 The Procter & Gamble Company Dry bleach and stable enzyme granular composition
EP0508034A1 (fr) * 1991-04-12 1992-10-14 The Procter & Gamble Company Composition détergente contenant des polyvinylpyrrolidones
WO1994002597A1 (fr) * 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction
WO1994002577A1 (fr) * 1992-07-15 1994-02-03 The Procter & Gamble Company Compositions detergentes enzymatiques inhibant le transfert de colorant
WO1994002578A1 (fr) * 1992-07-15 1994-02-03 The Procter & Gamble Company Compositions inhibant le transfert de teintures, comprenant des dispersants polymeres

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US4006092A (en) * 1971-08-05 1977-02-01 The Procter & Gamble Company Laundering aid
DE3320726A1 (de) * 1983-06-09 1984-12-13 Henkel KGaA, 4000 Düsseldorf Wasch- und reinigungsmittel mit einem gehalt an acylcyanamidsalzen
DE3413292A1 (de) * 1984-04-09 1985-10-17 Henkel KGaA, 4000 Düsseldorf Textil-waschmittel fuer farbige textilien
EP0458398B1 (fr) * 1990-05-21 1997-03-26 Unilever N.V. Activation du blanchiment
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone

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Publication number Priority date Publication date Assignee Title
FR2144721A1 (fr) * 1971-07-02 1973-02-16 Procter Gamble Europ
US4767557A (en) * 1985-06-28 1988-08-30 The Procter & Gamble Company Dry bleach and stable enzyme granular composition
EP0508034A1 (fr) * 1991-04-12 1992-10-14 The Procter & Gamble Company Composition détergente contenant des polyvinylpyrrolidones
WO1994002577A1 (fr) * 1992-07-15 1994-02-03 The Procter & Gamble Company Compositions detergentes enzymatiques inhibant le transfert de colorant
WO1994002578A1 (fr) * 1992-07-15 1994-02-03 The Procter & Gamble Company Compositions inhibant le transfert de teintures, comprenant des dispersants polymeres
WO1994002597A1 (fr) * 1992-07-23 1994-02-03 Novo Nordisk A/S Alpha-amylase mutante, detergent, agent de lavage de vaisselle et de liquefaction

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Title
See also references of WO9529222A1 *

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CA2187518A1 (fr) 1995-11-02
AU2293495A (en) 1995-11-16
JPH09512298A (ja) 1997-12-09
PE6096A1 (es) 1996-03-21
EP0753041A1 (fr) 1997-01-15
CA2187518C (fr) 2000-06-13
WO1995029222A1 (fr) 1995-11-02
MA23525A1 (fr) 1995-12-31

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