US3655568A - Enzyme containing detergent composition having improved physical and stability characteristics - Google Patents

Enzyme containing detergent composition having improved physical and stability characteristics Download PDF

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US3655568A
US3655568A US797A US3655568DA US3655568A US 3655568 A US3655568 A US 3655568A US 797 A US797 A US 797A US 3655568D A US3655568D A US 3655568DA US 3655568 A US3655568 A US 3655568A
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sodium
copolymer
percent
enzyme
water
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Wahib Nassif Zaki
Jean Marie Louis Coulomb
Peter Lovgren
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/04—Evaporators with horizontal tubes

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  • ABSTRACT An enzyme containing granular detergent composition having [30] Fomgn Application Pnomy Data improved physical and stability characteristics which is mm Jan. 10, l969 France ..6900346 ri d of a water-soluble inorganic or organic builder, an enzyme and water-soluble alkali metal salt, ester, or C alkylor Cl 2/DlG.
  • the present invention pertains to a granular or powdered free flowing detergent composition containing enzymes, and optionally hydrogen peroxide addition compounds; and, to an improved process for manufacturing the same.
  • Storage stability i.e., color, thermal and hygroscopic stability is lacking in many granular or powdered detergent compositions. Stability in color, etc., is particularly necessary for granuluar or powdered detergent compositions subjected to different environmental conditions, due to prolonged storage, and for granular or powdered detergent compositions to be distributed in countries having climatologically different areas.
  • Stickiness or caking of a granular or powdered detergent composition is mainly influenced by the concentration of the surface-active agent incorporated in said detergent composition.
  • suds depressants for example, water-soluble nonionic alkylene oxide adducts
  • the concentration of surface-active agent has to be lowered, to avoid stickiness and caking. This entails decrease in detergency power of the granular or powdered detergent compositions but does not always solve the stickiness or caking problem.
  • many attempts to avoid caking and stickiness, or to increase stability of a granular or powdered detergent composition impaired or adversely affected other desirable properties.
  • ethylenediaminetetraacetic acid or the salts thereof added into a granular detergent composition to improve its detergency, adversely affects the bleaching capacity of sodium perborate present in such a detergent composition.
  • Enzymes highly desirable in an all-purpose detergent composition, are usually in a concentrated fine powdered form. Such fine powders are difficult to handle, to measure, to formulate, and tend to segregate. Moisture, i.e., water, added to bind said enzyme powders, tends to cause the enzymes to degrade themselves. Consequently, when incorporated in a detergent composition, the composition is charged with impurities instead of active enzymes.
  • a maleic anhydride-vinyl methyl ether copolymer when mixed as such with a granular or powdered detergent composition for improving whiteness maintenance, decreases the activity of the enzymes substantially, and when mixed with detergent compositions containing perborates, to improve the bleaching activity of the latter, also causes severe discoloration and caking.
  • a granular or powdered detergent composition comprising a surface-active agent selected from the group consisting of water-soluble organic, anionic, non-ionic, amphoteric, or zwitterionic detergents, and mixtures thereof (or an non-ionic" detergent); a water-soluble inorganic builder salt and optionally an organic builder salt; an enzyme product, i.e., pure enzyrng plus carrier; preferably hydrogen peroxide bleaching compoundi'a'nd, if desired, the usual additives, can be made stable, free flowing, without affecting adversely any other property, by incorporating from about 0.1% to about 8% by weight, calculated on a finished product basis, of an alkali-metal salt, ester, or C alkyl or alkylolamide of a copolymer of maleic anhydride and a vinyl compound of the formula RCH HCR, wherein one R represents a hydrogen atom, while the other R represents a C,-, alkyl ether
  • the present invention consequently pertains to a granular or powdered, free flowing detergent composition
  • a surface active agent LII selected from the group consisting of an organic water-soluble anionic, non-ionic, amphoteric, or zwitterionic detergent or mixtures thereof; from about 10% to about by weight of a water-soluble, inorganic builder salt, or mixtures thereof, alone, or in combination with a water-soluble organic builder salt, or mixtures thereof; from about 0.1% to about 8% by weight of a water-soluble alkali-metal salt, ester, or C -3 alkylor alkylolamide of a copolymer of a maleic anhydride and a vinyl compound of the formula RCH HCR, wherein one R represents a hydrogen atom, while the other R represents a C alkyl ether radical or a hydrogen atom; from about 0.01% to about 5% by weight of an enzyme product; and, optionally, from about 5% to about 50% by weight of an enzyme product; and, optionally
  • a water-soluble non-cationic detergent preferably the sodium salts of C alkyl-benzene sulfonates or the sodium salts of higher fatty alcohol sulfates
  • the invention comprises the use of a water-soluble alkali-metal salt, ester, or c, alkylor alkyl-or alkylolamide of a maleic anhydride-ethylene or vinyl C,-, alkyl ether copolymer.
  • the degree of polymerization of said copolymer adequately soluble under regular use conditions is difficult to establish.
  • the specific viscosity of the anhydride form of the maleic anhydride-vinyl C alkyl ether copolymer preferably varies between 0.1 and 6.0, most preferably between 0.2 and 5.0; the specific viscosity is defined by measuring the viscosity of the solution of lg. of the anhydride-copolymer in cc. methylethylketone in a Cannon-Fenske (Series 100) viscosity meter at 25 C.
  • the viscosity of the maleic anhydride-ethylene copolymer varies preferably between 1.2 and 10 centipoises when measured as an aqueos solution containing 2 percent of the copolymer in a Brookfield RTV viscosity meter at 10 r.p.m., at 25 C., whereby the solution is adjusted to have a pH of 10.
  • the copolymer which is used in the composition of the invention is preferably the sodium and potassium salt.
  • Another valuable copolymer is the primary or secondary C alkyl amide or C alkylolamide and especially the monoand diethanolamide.
  • the ester derivative of the copolymer is either the C and preferably the C,-, aliphatic alcohol reaction product, or the reaction product of the copolymer and a water-soluble organic compound having at least one reactive hydroxyl radical, for example, the water-soluble condensation product of 6 to 25 moles of ethylene oxide with a C aliphatic alcohol, with a C alkylsubstituted phenol, with condensated propylene oxide, or with the reaction product of propylene oxide and ethylene diamine.
  • the carboxylic acid radicals of the copolymer are esterified or reacted with a C,-, alkylor alkylolamine.
  • the ratio of the monomers in the copolymers may vary from 2:1 to 1:2, but is preferably 1:1.
  • the enzyme product to be used according to the present invention contains catalytically active protein materials, which degrade or alter one or more types of soil or stains encountered in soaking and laundering situations, so as to remove the soil or stains from the fabric being soaked and/or laundered, or make the soil or stains removable in a subsequent laundering step, and an inert vehicle.
  • Said enzyme products preferably in a dry powdered form, contain from 2 to 80 percent, preferably from 6% to about 40% of active material.
  • Components A B by wt. by wt. sodium alkylbenzene sulfonate 14.00% 950% (average C: ll.9) tallow alcohol-ethylene oxide condensate (avenge oxide units: 9-12) 3.00 2.00 fatty acids (derived from fish oil) 4.50 3.00 enzyme product 1.00 0.60 sodium tripolyphosphate 45.00 30.00 sodium silicate 8.00 5.00 sodium sulfate 8.00 6.00 carboxymethylcellulose L L00 sodium perborate-tetrahydrate 32.00 copolymer X 2.00 1.50 miscellaneous (perfume, brightener) 3.00 2.00 moisture balance balance enzyme product: ALCALASl-I," a proteolytic enzyme product. made by Novo lndustri AIS, Copenhagen, Denmark, containing 6% active enzyme.
  • ALCALASl-I a proteolytic enzyme product. made by Novo lndustri AIS, Copenhagen, Denmark, containing 6% active enzyme.
  • compositions were prepared by mixing the surface-active agent, fatty acid, builder salt, electrolyte, and carboxymethylcellulose in a crutcher, spray-drying the crutcher mixture, and admixing the copolymer, enzyme product, perfume, and sodium perborate-tetrahydrate.
  • compositions A and B contained the following copolymer:
  • the specific viscosity of the malaic anhydride-vinyl methyl ether use is 0.4, and the ratio of monomers 1:1; the viscosity of the maleic anhydride-ethylene copolymer is 2 c.p.s., and the ratio of monomers 1:].
  • the "compression test requires a cylinder (diameter length -l :3 which is filled with the granules and is tapped to settle the latter. Said granules are compressed by a piston of approximately the same diameter as the inner diameter of said cylinder, and having the same weight in each test. The change in length of each column of granules is measured after 5 minutes (compression). The compression is measured in percentage calculated on the initial length, 0 percent of compression indicating a perfect granular composition and over 12 percent indicating an unacceptable product.
  • the cake-strength test is applied to the same compositions as used in the compression test, whereby the column of granules compressed during the compression test, is freed from the piston and the cylinder, and the force needed to break the compressed column is measured (cake strength).
  • the cake strength is graded from 0 to 7, 0 being perfect, i.e., strong granules which do not stick together, and 7 being unacceptable.
  • the cleaning capacity of a detergent composition can be increased.
  • the amount of surface-active agents that can be incorporated in a free-flowing granular or powdered composition is limited due to the stickiness and concentration of the surface-active agent.
  • the stickiness of a given detergent composition can be decreased substantially. Consequently, by the present invention the concentration of surface-active agent in a granular or powdered detergent composition can be increased without affeeting its pourability.
  • the detergent composition of the present invention can be manufactured by dry-mixing the different components, or by slurrying the components, followed by drying.
  • the detergent composition can be prepared batch by batch, or continuously.
  • the copolymer is preferably added in the slurry in its salt, ester, or amide form, but can be added in its anhydride form. If the latter occurs, the anhydride is to be converted into its salt, ester, or amide fonn in the slurry, by adding the necessary alkali metals, alcohols or amines.
  • the salt, ester, or amide derivative of the copolymer decreases the viscosity of the slurry. This entails that less energy is required to mix the slurry thoroughly, or that the capacity of the device, wherein the slurry is prepared, is increased. Further, due to said decreased viscosity, the blowing rate of the spray-tower, when said slurry is to be spray-dried, is increased too. Consequently, a preferred process for preparing a stable, freefiowing granulated detergent composition of the present invention is by slurrying the components followed by drying at low temperatures. The most preferred process is, however, slurrying the detergent, copolymer, builder, electrolyte and other non-heat sensitive compounds, spray-drying the slurry,
  • Suitable enzymes to be used according to the present invention are those active at a pH range of from 4 to 12, preferably from 7 to l l, and at a temperature of from 10 to 85 C., preferably from 25 to 75 C.
  • Said suitable enzymes can be grouped into five major classes:
  • hydrolyzing enzymes such as hydrolases, e.g., proteases
  • hydrating enzymes e.g., hydrases
  • oxido-reductases e.g., alcohol dehydrogenases, xanthine oxidases, amino acid oxidases
  • transferases e.g., transglycodases, transphosphorylases and -phosphormutases, transaminases, transmethylases and transacetylases;
  • lV those which split or form bounds without group transfer or desmolases, e.g., ligases and lyases, and
  • V those which isomerize and chemically alter a soil such as lipid and carbohydrate soil isomerases, e.g., racemases and epimerases, cis-trans-isomerases, intramolecular transferases and oxido-reductases. in a few cases a single enzyme may fit more than one of these classes.
  • lipid and carbohydrate soil isomerases e.g., racemases and epimerases, cis-trans-isomerases, intramolecular transferases and oxido-reductases. in a few cases a single enzyme may fit more than one of these classes.
  • hydrolases in summary the hydrolases, hydrases, oxidoreductases and desmolases degrade soil to remove it or make it more removable and the transferases and isomerases alter soil so as to make it more removable.
  • hydrolases and particularly the proteases, esterases, carbohydrases and nucleases, with the proteases having the broadest range of soil degradation capability are preferred. Mixtures of the enzymes may be used if desired.
  • proteases suitable for use in this invention are pepsin, trypsin, chymotrupsin, collagenase, keratinase, elastase, subtilisin, papain, bromelin, carboxy peptidase A and B, amino peptidase, aspergillopeptidase A and aspergillopeptidase B.
  • Preferred proteases are serine proteases which are active in the neutral to alkaline pH range and one produced from microorganisms such as bacteria, fungi or mold.
  • the serine proteases which are procured by mammalian systems, e.g., pancreatin, are useful in acid situations.
  • esterases are gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases.
  • carbohydrases are maltase, saccharase, amylases, cellulase, pectinase, lysozyme, aglycosidase and B-glycasidase.
  • nucleases Two specific examples of nucleases are ribonuclease and desoxyribonuclease.
  • the enzyme products utilized in this invention are generally obtained and stored in a dry, powdered form. They can be mixed as such with the components forming the detergent composition or adsorbed on a carrier, together with nonionie compounds, or slurried in water.
  • the dry, powdered form is most easily handled and generally is more stable than enzymes in a water slurry.
  • the commercial powdered enzyme products are generally dry powdered products comprising 2 to percent active enzymes in combination with an inert powdered vehicle such as sodium or calcium sulfate or sodium chloride, clay or starch as the remaining 98-20 percent.
  • Active enzyme content of a commercial product is a result of manufacturing methods employed and is not critical herein so long as the laundry product has the desired enzymatic activity.
  • Many of these commercial products contain the preferred proteases as the active enzyme product.
  • a subtilisin comprises the major portion of the proteases; other examples of hydrolase generally included in commercial products are lipases, carbohydrases, esterases and nucleases.
  • Pronase-P Pronase-AS and Pronase-AF, all of which are manufactured by Kaken Chemical Company, Japan
  • Rapidase P-2000 Rapidase, Seclin, France
  • proteolytic enzyme products proteolytic enzyme products (particle size 1 mm.
  • CRD Protease (also known as Monsanto DA-IO) is a useful powdered enzyme product.
  • CRD-Protease is reported to be obtained by mutation of a Bacillus Subtilis organism. It is about 80 percent neutral protease and 20 percent alkaline protease.
  • the neutral protease has a molecular weight of about 44,000 and contains from one to two atoms of zinc per molecule. its particle size ranges predominantly from 0.03 mm. to 0.1 mm.
  • the CRD-Protease can be used in an aqueous system having a pH ranging from about 5.4 to about 8.9. It can be prepared to range in active enzyme content from 20 to 75 percent.
  • the presence of CaCl in the enzyme powder increases the pH range over which the enzyme can be utilized.
  • This enzyme can be utilized in the composition of this invention with excellent results in washing solutions at temperatures ranging from about 10 to about 66 C., and at lower pHs suitable for prewash soaking or higher pHs for detergency purposes.
  • Pronase-P, Pronase-As and Pronase-AF are powdered en- I zyme products which can also be used to advantage in this invention. These enzymes are produced from the culture broth of Streptomyces griseus used for streptomycin manufacture.
  • the major component of the pronase is a neutral protease named as Streptomyces griseus protease.
  • This enzyme product contains a calcium stabilizer salt and is fairly stable over a wide pH range, e.g., 4 to 10, and is fairly stable over a temperature range of 10 to 66 C.
  • Another enzyme product preferred for use in the detergent compositions of this invention is a proteolytic enzymes, a serine protease, manufactured by Novo lndustri A/S, Copenhagen, Denmark, and sold under the trade name of Alcalase.
  • Alcalase is described, in a trade bulletin bearing that name which was published by Novo lndustri A/S, as a proteolytic enzyme preparation manufactured by submerged fermentation of a special strain of Bacillus Subtilis.
  • the primary enzyme component of Alcalase is subtilisin.
  • Alcalase exhibits other forms of desirable enzymatic activity.
  • Alcalase is a fine grayish powder having a crystalline active enzyme content of about 6 percent and a particle size ranging from 1.2 mm. to 0.01 mm. and smaller, about 75 percent passing through a 100 mesh Tyler screen. The remainder of the powder is comprised primarily of sodium chloride, calcium sulfate and various inert organic vehicle materials. Alcalase has unusually stable propenies in solution. For example, Alcalase can withstand a pH of about 9 at relatively high temperatures, i.e., 66-77 C., for a short time. At 49 C., the activity of Alcalase is virtually unchanged in a 24-hour period when held at this pH. Alcalase can be advantageously used with soap and detergent compositions of this invention.
  • the particular enzyme product chosen for use in the products and process of this invention depends on the conditions of final utility, including carrier pH, composition pH, use pH, use temperature and soil types to be degraded or altered.
  • the enzyme can be chosen to provide optimum activity and/or stability for any given set of usage conditions.
  • the powdered enzyme product can be attached to a granular carrier in the detergent composition and process of this invention to provide from about 0.001 percent to about 3 preferably 0.01 to 1.5 percent of pure enzyme, calculated on the total weight of enzyme powder and carrier.
  • the enzyme product concentration usually ranges from 0.01 to percent, generally 0.1 to 3 percent of the detergent composition.
  • the amount of enzyme products (enzyme vehicle) attached to the granular carrier can range up to 40 percent, preferably to 20 percent, of the total weight of enzyme products plus carrier.
  • the enzyme products can also be dissolved in water, and sprayed onto the finished detergent composition, or to one or more components of said composition to provide from 0.01% to about 5%, preferably 0.1-3 percent of the total detergent composition.
  • the water-soluble surface-active agent which can be utilized in the composition of this invention are soap and anionic, nonionic, ampholytic and switterionic synthetic detergents and mixtures thereof. These suitable surface-active agents are enumerated below.
  • Water-soluble soap the sodium, potassium, ammonium and alkanol ammonium (e.g., triethanolammonium) salts of higher fatty acids containing from to 22 carbon atoms.
  • anionic synthetic non-soap detergents can be broadly described as the water-soluble salts, particularly the alkali-metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from eight to 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical (included in the term alkyl is the alkyl portion of higher acyl radicals).
  • alkyl is the alkyl portion of higher acyl radicals.
  • sodium coconut oil fatty acid monoglyoeride sulfates and sulfonates sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and l to 6 moles of ethylene oxide, sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from eight to 12 carbon atoms; the reaction product of C fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, and others known in the art.
  • a higher fatty alcohol e.g., tallow or coconut oil alcohols
  • Nonionic synthetic detergents broadly defined as 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.
  • Preferred classes of nonionic synthetic detergents are as follows:
  • Nonionic synthetic detergents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine For example, compounds containing from 40 to percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide; said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
  • condensation product of aliphatic alcohols having from eight to 22 carbon atoms with ethylene oxide e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
  • R is an alkyl radical of from about eight to about 24 carbon atoms
  • R and R are each methyl, ethyl, or hydroxyethyl radicals
  • R is ethylene
  • n is 0 or an integer of up to 10.
  • amine oxide detergents include: dimethyl dodecyl amine oxide; acetyl dirnethyl amine oxide; bis-(2-hydroxyethyl) dodecyl amine oxide; bis- (Z-hydroxyethyl) 3-dodecoxy-l-hydroxypropyl amine oxide.
  • R is an alkyl radical containing from 10 to 28 carbon atoms, from to ether linkages and from 0 to 2 hydroxyl substituents, at least one moiety of R being an alkyl radical containing no ether linkages and containing from to 18 carbon atoms, and wherein R is an alkyl radical containing from one to three carbon atoms and from 1 to 2 hydroxyl groups.
  • Specific examples of these sulfoxides are: 3-methoxy tridecyl methyl sulfoxide: 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, wherein one of the aliphatic substituents contains from eight to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulpho, sulphato, phosphate or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3-dodecylamino-propane sulfonate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds, wherein one of the aliphatic substituents contains from eight to 18 carbon atoms arid one contains an anionic water solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato, or phosphono.
  • Examples of compounds falling within this definition are 3-(N,N- dimethyl-N-hexadecylammonio) propane-l-sulfonate and 3- (N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-lsulfonate which are especially preferred for their excellent cool water detergency characteristics. See, for example, British Pat. No. 987,795.
  • a suitable, water-soluble inorganic builder salt or mixtures thereof, used alone or in combination with a water-soluble organic builder salt, or mixtures thereof, is an alkali-metal phosphate, polyphosphate, carbonate, borate, bicarbonate and silicate (an ammonium and substituted ammonium salt can also be used).
  • an inorganic builder salt sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate and the corresponding potassium salts, sodium hexametaphosphate, sodium sesquicarbonate and sodium monoand di-orthophosphate.
  • a suitable organic, water-soluble builder salt examples include alkali-metal, ammonium or substituted ammonium polycarboxyl-ates, e.g., sodium and potassium ethylenediaminetetraacetates or nitriloacetates, and the sodium and potassium lower alkyl di-phosphonates such as trisodiurn ethylene l -hydroxy-l l -diphosphonate.
  • a suitable hydrogen peroxide addition compound examples include the perborates, e.g., the sodium perborate monoand tetrahydrate, further the potassium perborates ZKBO H, O, the carbonate peroxyhydrates, e.g., 2Na CO 31b0,, and the phosphate peroxyhydrates preferably the sodium pyrophosphate peroxyhydrate Na,P O .2l-l,O,.
  • the most suitable organic hydrogen peroxide addition compound is the urea peroxide CO(Nl-! .l-i O
  • Sodium carboxymethylcellulose can be added in minor amounts to inhibit soil redeposition.
  • a tarnish inhibitor such as benzotriazole or ethylenethiourea can also be added in amounts up to about 2 percent. Fluorescers, perfumes and dyes, while not essential in the composition of the invention, can be added in small amounts. An alkaline material or alkali such as sodium hydroxide or potassium hydroxide can be added in minor amounts as supplementary pH adjustors. There might also be mentioned as suitable additives: bacteriostats, sodium sulfate, sodium carbonate and bactericides. Corrosion inhibitors generally are also added. Soluble silicates are highly effective inhibitors and can be added to certain composition of this invention at levels of from about The following examples serve to illustrate, but not to limit the novel compositions of the present invention. All percentages in the examples are by weight. The enzymes mentioned, are commercial powdered enzyme products, containing 6-8 percent active material.
  • a stable, free flowing detergent composition which can be stored under different climatological conditions for a long period of time, is preferred by slurrying in a crutcher the surface active agents, builders, electrolytes, carboxymethyl cellulose, toluene sulfonate, sodium sulfate, brightener and water; spray-drying the slurry; dry-mixing the perborate and copolymer with the spray dried granules; and atomizing the perfume onto the agglomerates.
  • the end product consisting of:
  • toluene sulfonate 1.50% sodium salt of the maleic anhydride-vinyl methyl ether copolymer. (Specific viscosity of anhydride 0.4), qpp 13.20% sodium sulfate,
  • the copolymer may be replaced by the sodium salt of maleic anhydride-ethylene, or by the ethanolamide derivative of the maleic anhydride-vinyl methyl ether copolymer.
  • EXAMPLE 1V 7.00% sodium-3-(N,N-dimeghyl-N-tetradecylammonio)-2- hydroxypropane-l-sulfonate,
  • a granular, free flowing detergent composition consisting essentially of, calculated on a finished product basis:
  • a water-soluble inorganic builder salt from 10% to about by weight of a water-soluble inorganic builder salt, a water-soluble organic builder salt, or mixtures thereof; from about 0.01% to about 5% by weight of an enzyme product; from about 0.1% to about 8% by weight of a water-soluble alkali-metal salt, ester, or C alkylor alkylolamide of a copolymer of maleic anhydride and a vinyl compound of the formula RCH HCR. wherein one R renresents a hydrogen atom while the other R represents a C alkyl ether radical, or a hydrogen atom.
  • the ratio of the maleic anhydride and vinyl compound in the copolymer is from 2:1 to l :2 and wherein the specific viscosity of the anhydride form of the copolymer where R represents a C alkyl ether radical is between 0.1 and 60 and the viscosity of the anhydride form of the copolymer when R represents a hy rogen atom is between 1.2 centipoises and 10 centipoises; and
  • an organic, water-soluble surface-active agent selected from the group consisting of anionic, nonionic, amphoteric, and zwitterionic detergents and mixtures thereof.
  • a composition of claim 1 which also contains from 5% to about 50% by weight of a hydrogen peroxide addition compound.
  • a granular free flowing detergent composition consisting essentially of:
  • a composition of claim 3 wherein the hydrogen peroxide addition compound is sodium perborate tetrahydrate.
  • a composition of claim 4 wherein the copolymer derivative is the sodium or potassium salt of the aleic anhydridevinyl methyl ether copolymer.
  • composition of claim 4 wherein the copolymer derivative is a diethanolamide.
  • alkylolomide should read alkylolamide-. Col. 1, line 60, "an should be a. C01. 2, line 30, delete last two words in the line “alkyl-or” Col. 3, line 8, "as” should be is--; line 15, first item under Component B reads "950%” it should be 9. 50%-; line 41, "X 32 sodium” should read -X sodium--;
  • Col. 10, line 27, 3.401% should be 3.400%--; between lines- 28 & 29, add -6. 20% sodium silicate-; delete line 48 which reads "65% sodium tripolyphosphate” delete line 55 which reads "200% sodium salt of maleic anhydride vinyl methyl ether” 7 line 66, after "atoms” delete Claim line 2, "aleic” should be t-maleic'-.
  • alkylolomide should read alkylol amide-- Col. 1, line 60, "an” should be a. C01. 2, line 30, delete last two words in the line “alkyl-or” Col. 3, line 8, "as” should be ---is-; line l5, first item under Component B reads "95O% it should be 9. 50%-,- line 41, "X 32 sodium” should read X sodiumline 45, "use” should be used--. Col. 5, line 2, frees flowing” should be --freeflowing--. Col. 7, line 9, "enzymes” should be enzyme;
  • Col. 10, line 27, "3.401%” should be 3 .40Os--: between lines 28 & 29, add 6.20% sodium silicate-; delete line 48 which reads 65% sodium tripolyphosphate” delete line 55 which reads "200% sodium salt of maleic anhydride vinyl methyl ether” 7 line 66, after "atoms” delete Claim line 2, "aleic” should be -,maleic'.

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US797A 1969-01-10 1970-01-05 Enzyme containing detergent composition having improved physical and stability characteristics Expired - Lifetime US3655568A (en)

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AT (1) AT305475B (enrdf_load_stackoverflow)
BE (1) BE744225A (enrdf_load_stackoverflow)
CA (1) CA945922A (enrdf_load_stackoverflow)
CH (1) CH555402A (enrdf_load_stackoverflow)
DE (1) DE2000790A1 (enrdf_load_stackoverflow)
DK (2) DK132037C (enrdf_load_stackoverflow)
ES (1) ES375248A1 (enrdf_load_stackoverflow)
FI (1) FI51713C (enrdf_load_stackoverflow)
FR (1) FR2029123A5 (enrdf_load_stackoverflow)
GB (1) GB1280802A (enrdf_load_stackoverflow)
IE (1) IE33936B1 (enrdf_load_stackoverflow)
NL (1) NL148934B (enrdf_load_stackoverflow)
NO (1) NO130013C (enrdf_load_stackoverflow)
SE (1) SE349057B (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950277A (en) * 1973-07-25 1976-04-13 The Procter & Gamble Company Laundry pre-soak compositions
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
WO1999055817A1 (en) * 1998-04-29 1999-11-04 The Procter & Gamble Company Laundry detergent and/or fabric care compositions comprising a transferase
US20040082490A1 (en) * 2000-12-05 2004-04-29 Kazuyoshi Arai Method of laundering clothes and detergent composition therefor
US20090119847A1 (en) * 2005-07-01 2009-05-14 Miz Co., Ltd. Clothes washing method and detergent composition used for the same

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Publication number Priority date Publication date Assignee Title
LU68380A1 (enrdf_load_stackoverflow) * 1973-09-07 1975-05-21
US7828907B2 (en) 2007-05-09 2010-11-09 Ecolab Inc. Detergent component for preventing precipitation of water hardness and providing soil removal properties

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US2702277A (en) * 1955-02-15 Detergent composition
US3485762A (en) * 1966-05-24 1969-12-23 Sinclair Research Inc Laundry detergents containing ammonium salt of styrenemaleic anhydride copolymer and non-ionic,hydroxyl-containing surfactant

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DE697945C (de) * 1934-11-11 1940-10-28 I G Farbenindustrie Akt Ges Verfahren zum Waschen von Textilgut
DE1617188A1 (de) * 1966-04-25 1971-02-25 Procter & Gamble Enzyme enthaltende Waschmittel und ein Verfahren zum Aufkleistern von Enzymen auf Detergenszusammensetzungen
DE1617190A1 (de) * 1966-04-25 1971-02-18 Procter & Gamble Europ Koerniges,Enzyme enthaltendes Waschmittel

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US2702277A (en) * 1955-02-15 Detergent composition
US3485762A (en) * 1966-05-24 1969-12-23 Sinclair Research Inc Laundry detergents containing ammonium salt of styrenemaleic anhydride copolymer and non-ionic,hydroxyl-containing surfactant

Non-Patent Citations (1)

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Title
Gantrez AW, General Aniline & Film Corp., N.Y., N.Y. 1961, pages 1, 22 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3950277A (en) * 1973-07-25 1976-04-13 The Procter & Gamble Company Laundry pre-soak compositions
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
WO1999055817A1 (en) * 1998-04-29 1999-11-04 The Procter & Gamble Company Laundry detergent and/or fabric care compositions comprising a transferase
US20040082490A1 (en) * 2000-12-05 2004-04-29 Kazuyoshi Arai Method of laundering clothes and detergent composition therefor
US7407924B2 (en) * 2000-12-05 2008-08-05 Miz Co., Ltd. Surfactant-free detergent composition comprising an anti-soil redeposition agent
US20080280804A1 (en) * 2000-12-05 2008-11-13 Miz Co., Ltd. Method of laundering clothing and detergent composition for the same
US7553807B2 (en) * 2000-12-05 2009-06-30 Miz Co., Ltd. Surfactant-free detergent composition comprising an anti-soil redeposition agent
US20090119847A1 (en) * 2005-07-01 2009-05-14 Miz Co., Ltd. Clothes washing method and detergent composition used for the same
US8389460B2 (en) * 2005-07-01 2013-03-05 Miz Co., Ltd. Clothes washing method and surfactant-free detergent composition used for the same

Also Published As

Publication number Publication date
SE349057B (enrdf_load_stackoverflow) 1972-09-18
JPS4820402B1 (enrdf_load_stackoverflow) 1973-06-21
ES375248A1 (es) 1972-04-16
FI51713B (enrdf_load_stackoverflow) 1976-11-30
DE2000790A1 (de) 1971-04-08
CH555402A (de) 1974-10-31
NL148934B (nl) 1976-03-15
FI51713C (fi) 1977-03-10
BE744225A (nl) 1970-07-09
DK132037B (da) 1975-10-13
GB1280802A (en) 1972-07-05
NO130013B (enrdf_load_stackoverflow) 1974-06-24
IE33936L (en) 1970-07-10
IE33936B1 (en) 1974-12-11
DK132037A (enrdf_load_stackoverflow)
CA945922A (en) 1974-04-23
AT305475B (de) 1973-02-26
NO130013C (no) 1979-05-23
DK132037C (da) 1981-02-23
NL7000234A (enrdf_load_stackoverflow) 1970-07-14
FR2029123A5 (enrdf_load_stackoverflow) 1970-10-16

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