EP0365103A2 - Compositions détergentes à usage universel avec un agent tensioactif non ionique synthétique, organique ayant une action nettoyante modifiée sur le linge contenant de la salissure difficile à éliminer - Google Patents

Compositions détergentes à usage universel avec un agent tensioactif non ionique synthétique, organique ayant une action nettoyante modifiée sur le linge contenant de la salissure difficile à éliminer Download PDF

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Publication number
EP0365103A2
EP0365103A2 EP89202650A EP89202650A EP0365103A2 EP 0365103 A2 EP0365103 A2 EP 0365103A2 EP 89202650 A EP89202650 A EP 89202650A EP 89202650 A EP89202650 A EP 89202650A EP 0365103 A2 EP0365103 A2 EP 0365103A2
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EP
European Patent Office
Prior art keywords
cellulase
ethylene oxide
detergent
sodium
range
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Withdrawn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
EP89202650A
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German (de)
English (en)
Other versions
EP0365103A3 (fr
Inventor
Winston Sei Uchiyama
Jan Edward Shulman
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Colgate Palmolive Co
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Colgate Palmolive Co
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Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0365103A2 publication Critical patent/EP0365103A2/fr
Publication of EP0365103A3 publication Critical patent/EP0365103A3/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Withdrawn legal-status Critical Current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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • This invention relates to laundry detergent composi­tions. More particularly, it relates to heavy duty particulate synthetic organic nonionic detergent compositions in which cellulase enzyme promotes removal of hard-to-remove soils, such as sebum/particulate soils from fibers of the fabrics of laundry being washed despite the facts that the concentration of the cellulase in the wash water is very low and that the concentra­tion of detergent composition is less than normally employed.
  • the particulate detergent composition is what may be termed a concentrated or super-concentrated composition and the charge thereof to a washing machine will be relatively small, often being less than two ounces per tub load of water, such as less than about 0.06% by weight.
  • phosphate and non-phosphate detergent composi­tions as well as bleaching and non-bleaching compositions.
  • Nonionic detergent compositions of the Fresh Start® type have been described in the patent literature and have been successfully marketed.
  • Such particulate detergents include a normally solid nonionic synthetic organic detergent that has been absorbed into the interiors of spray dried base beads of builder components, with some of the nonionic detergent coating the surfaces of the beads.
  • soil release promoting agents such as polyethylene tere­phthalate-polyoxyethylene terephthalate (PET-POET) copolymers, which have been sold under the trade names Alkaril® QCF, Alkaril QCJ and Alkaril SRP-2-F (manufactured by Alkaril Chemical Company).
  • PET-POET polyethylene tere­phthalate-polyoxyethylene terephthalate copolymers
  • Such effectiveness of the described composition is considered to be unexpectedly beneficial, especially in view of the employment of applicants' small proportions of cellulase and because similar concentrations of such cellulase in anionic detergent compositions and in wash waters containing such compositions do not improve removals of such soils.
  • a heavy duty particulate synthetic organic nonionic detergent composi­tion which has significantly improved cleaning action against hard to remove soils in laundry fibers when such laundry is soiled with such types of soils, comprises 4 to 30% of synthetic organic nonionic detergent, 25 to 80% of builder for such nonionic detergent, 0.1 to 2% of protease, 0 to 2% of amylase, 0.2 to 1% of cellulase, and 1 to 15% of water.
  • the invented compositions include both phosphate-built and non-phosphate products, bleaching and non-bleaching detergent compositions, and the invention also includes washing processes in which such compositions or components thereof are employed.
  • compositions also preferably include NRE-­type nonionic detergent, PET-POET copolymer and stilbene-type fluorescent brightener.
  • the enzyme system will include protease, amylase and cellulase, in prilled forms, and it may also be preferable, in many instances, for the cellulase to be derived from fungus.
  • the active detergent constituents of the present compositions and methods is a nonionic detergent, or more accurately, a mixture of such detergents.
  • Anionic synthetic organic detergent compositions are not improved in cleaning action against deeply embedded laundry soils by small propor­tions of fungus-derived cellulase, e.g., 0.5%, whereas in the present detergent compositions, based on nonionic detergents, such improvements have been obtained.
  • small propor­tions of anionic detergents may be employed in essentially nonionic detergent compositions without having objectionably detrimental effects.
  • Amphoteric detergents may be present with nonionic detergents in these compositions but cationic surfac­tants are usually omitted if any anionic detergent is present.
  • nonionic detergents are those which are reaction or condensation products of ethylene oxide and a suitable lipophile or lipophilic material.
  • Higher alcohols usually fatty alcohols of 10 or 12 to 18 carbon atoms per molecule, are the preferred reactants with ethylene oxide to make the desired nonionic detergents for the compositions of this invention but Oxo-type alcohols and C7 ⁇ 10 alkyl substituted phenols, such as nonyl phenols, may also be useful.
  • nonionic detergents such as higher fatty acid esters of ethylene oxide may also be useful in some compositions and for particular applications but preferably a higher fatty alcohol is employed as the source of the lipophile, and very preferably, for best cleaning results, the product is a narrow range ethoxylate nonionic detergent.
  • narrow range ethoxylate is meant a polyethoxylated lipophile, ethoxylated with ethylene oxide so that at least 70% of the ethylene oxide in the nonionic detergent is in polyethoxy groups having n to (n+8) moles of ethylene oxide per mole, wherein n may be from 1 to 10, although it is preferable that n be 3 to 5, more preferably 4.
  • such preferred narrow range ethoxylate (NRE) nonionic detergent has at least 70% of the ethylene oxide thereof in polyethoxy groups of 4 to 12 ethylene oxides. Most preferably, such groups are of 5 to 10 ethoxies and are at least 80 or 85% of the ethoxy content of the NRE's.
  • NRE ethoxylate
  • ethylene oxide in some cases mixtures of ethylene oxide and propylene oxide may be employed in such NRE's, providing that the final product has the desirable and beneficial cleaning properties, in combination with cellulase, as will be described in more detail later in this specification.
  • the polyethoxylates of the NRE's may be within certain ranges of ethoxy contents in the polyethoxy moieties thereof, manufacturing methods usually result in mixtures of polymers, so average ethoxy contents may be specified.
  • the NRE nonionic detergents may be of an average of 4 to 12 or 5 to 10 ethylene oxide groups per mole, e.g., averaging about 6 or 7 EtO's per mole.
  • the preferivelyred lipophile will be that from higher fatty alcohol and therefore the ethylene oxide content of the NRE nonionic detergents will be at least 70% of higher fatty alcohol ethoxylates of 5 to 10 ethylene oxide groups per mole and more preferably, at least 80 or 85% of the ethylene oxide will be in such higher fatty alcohol ethoxylates. This compares with about 50% or less of such polyethoxy groups in BRE (the older and more common broad range ethoxylates).
  • the higher alcohol may be primary or secondary alcohol, but fatty alcohols are preferred.
  • the higher alcohol ethoxylates will preferably be of 12 to 14 carbon atoms, although sometimes the alcohol may be of 10 to 16 or 12 to 16 carbon atoms.
  • Tergitol® Nonionic Surfactant 24-L-60N which is of the formula RO(CH2CH2O) n H, wherein R is a mixture of C12 and C14 linear alcohols and n averages about 7.0.
  • Such product has a cloud point of 60°C. for a 1% aqueous solution and is a narrow range ethoxylate. Its properties are described in a product information bulletin issued by the manufacturer, Union Carbide Corporation, which carries the date of April, 1987.
  • Tergitol Nonionic Surfactant 24-L-60N there may also be employed similar products manufactured by Shell Chemical Company, which have been identified as Shell® 23-7P and Shell 23-7Z.
  • Various builders and combinations thereof which are effective to complement the washing action of the nonionic synthetic organic detergent(s) and to improve such action include both water soluble and water insoluble builders.
  • water soluble builders both inorganic and organic builders may be useful, but the inorganics are preferred, usually as alkali metal salt(s).
  • water soluble inorganic builders those of preference include: various phosphates, usually polyphosphates, such as the tripoly­phosphates and pyrophosphates, more specifically the sodium tripolyphosphates and sodium pyrophosphates, e.g., pentasodium tripolyphosphate, tetrasodium pyrophosphate; sodium carbonate; sodium bicarbonate; sodium silicate; sodium borate or borax; and mixtures thereof.
  • sodium bicarbonate sodium silicate
  • sodium borate or borax sodium borax
  • mixtures thereof instead of a mixture of sodium carbonate and sodium bicarbonate, sodium sesquicarbonate will sometimes be substituted.
  • the alkali metal or sodium silicate employed is normally of M2O:SiO2 or Na2O:SiO2 ratio within the range of 1:1.6 to 1:3, preferably 1:2.0 to 1:2.8, e.g., 1:2.4 (or 1:2.35).
  • water soluble inorganic builder salts when phosphates are not restricted by law or regulation they may be employed, often with a lesser proportion of sodium silicate.
  • carbonates may be employed with bicarbonates,often with a lesser proportion of sodium silicate, and with borates being optional.
  • Silicates will rarely be used alone.
  • mixtures of sodium tripolyphosphate and sodium pyrophosphate in propor­tions within the range of 1:10 to 10:1, preferably 1:5 to 5:1.
  • the various water soluble builder salts may be utilized in hydrated forms, which are some­times preferred, and the water soluble builders, hydrated or anhydrous, will normally be sodium salts, or mixtures of alkali metal salts, but sodium salts are usually preferred.
  • acid forms of the builders may be preferable but normally the salts will either be neutral or basic in nature, and usually a 1% aqueous solution of the detergent composition will be of a pH in the range of 8 to 11.5, e.g., 8 or 9 to 10 or 10.5.
  • Insoluble builders generally of the Zeolite A type, usually hydrated, as with 15 to 25% of water of hydration, may be used advantageously in the compositions of the present inven­tion. Hydrated Zeolites X and Y may be useful too, as may be naturally occurring zeolites and zeolite-like materials and other ion-exchanging insoluble compounds that can act as detergent builders. Of the various Zeolite A products, Zeolite 4A may often be found to be preferred. Such materials are well known in the art and methods for their manufacture need not be described here.
  • Such compounds will be of the formula (Na2O) x ⁇ (Al2O3) y ⁇ (SiO2) z ⁇ w H2O , wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or about 2, and w is from 0 to 9, preferably 2.5 to 6.
  • the zeolite builder should be a univalent cation exchanging zeolite, i.e., it should be an aluminosilicate of a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
  • a univalent cation such as sodium, potassium, lithium (when practicable) or other alkali metal, or ammonium.
  • the univalent cation of the zeolite type mentioned is an alkali metal cation, especially sodium or potassium, and most preferably it is sodium, as was indicated in the preceding formula.
  • the zeolites are capable of reacting sufficiently rapidly with calcium ions in hard water so that, alone or in conjunction with other water softening compounds in the detergent composition, they soften the wash water before adverse reactions of water hardness ions with other components of the synthetic organic detergent composition occur.
  • the zeolites employed may be characterized as having a high exchange capacity for calcium ion, which is normally from about 200 to 400 or more milligram equivalents of calcium carbonate hardness per gram of the aluminosilicate, pre­ferably 250 to 350 mg. eq./g., on an anhydrous zeolite basis.
  • the hydrated zeolites will normally be of a moisture or water of hydration content in the range of 5 to 30%, preferably about 15 to 25% and more preferably 17 to 22%, e.g., about 20%.
  • the zeolites, as charged to a crutcher mix from which base beads may be made, should be in finely divided state, with the ultimate particle diameters being up to 20 microns, e.g., 0.005 to 20 microns, preferably 0.01 to 8 microns mean particle size, e.g., 3 to 7 microns, if crystalline, and 0.01 to 0.1 micron, e.g., 0.01 to 0.05 micron, if amorphous. Although the ultimate particle sizes are much lower, usually the zeolite particles are of sizes within the range of No. 100 to 400 sieve, preferably No. 140 to 325 sieve, as charged to the crutcher for the manufacture of the base beads.
  • tower or non-tower manufacturing processes may be employed.
  • the cellulolytic enzyme, cellulase, which is employed in the present invention is a fungal cellulase, which is producible by a strain of Humicola insolens (Humicola grisea var. thermoidea). Such material, its characteristics, its manufacture and its use in detergent compositions have been described in U.S. patent 4,435,307. Other cellulases are also useful in the practice of this invention but most of the appli­cants' work has been done with the described (and preferred) fungal cellulases, which produce the desired "deep" cleaning of soiled laundry when such cellulases are incorporated into the described compositions.
  • cellulase there are preferably employed other enzymes which coact with the cellulase in the removal of hard to remove soils from laundry substrates.
  • suitable materials include proteolytic, amylolytic and lipolytic enzymes, any or all of which may be employed with the cellulase.
  • proteolytic enzymes are most important in combination with cellulase, and mixed proteolytic/­amylolytic enzymes, in combination, are even more preferred with the cellulase.
  • proteolytic and amylolytic enzymes work to decompose the stain material, making it easier to remove, and the cellulase helps to make the substrate more "approachable” or attackable by the other enzymes, thereby aiding in removing hard to remove and deep down stains during washing operations.
  • useful proteolytic enzymes are those identified by the trademark (Maxatase®, sold by Gist Brocades), while examples of amylolytic enzymes include Termamyl® obtainable from Novo Industri A/S.
  • the copolymers of polyethylene terephthalate and polyoxyethylene terephthalate which are known to be effective as soil release promoters.
  • Such materials are preferably incorporated in the present detergent compositions together with polyacrylate stabilizers for them, and the polyacrylates contribute additional cleaning and suspending properties to the compositions.
  • the PET-POET copolymers and the polyacrylates also coact with the NRE nonionic detergents to promote better cleaning of substrates.
  • the PET-POET copolymers employed will usually be of molecular weights in the range of 15,000 to 50,000, preferably 19,000 to 43,000, e.g., about 30,000 or 40,000, according to molecular weight determinations performed on samples of materials of such types, as described herein. Such molecular weights are weight average molecular weights.
  • the polyoxyethylene will usually be of a molecular weight in the range of about 1,000 to 10,000 and the molar ratio of polyethylene terephthalates to polyoxy­ethylene terephthalate units (considering as such units) will be within the range of 2:1 to 6:1.
  • the proportion of ethylene oxide to phthalic moiety in the polymer will normally be at least 10:1 and often will be 20:1 or more.
  • the polymer may be considered as being essentially a modified ethylene oxide polymer with the phthalic moiety being only a minor component thereof, whether calculated on a molar or weight basis.
  • the described PET-POET copolymer is obtained from Alkaril Chemical Company as Alkaril SRP-2-F, which also contains 5% of polyacrylate stabilizer. Although it is used by appli­cants in accordance with the present invention, and is highly preferred for its desired functions, other PET-POET polymers, such as those described in British Specification 1,088,984 and in U.S. patent 3,962,152 may also be employed and sometimes can be effective soil release promoting agents in the compositions and methods of this invention. However, the soil release promot­ing properties of such materials are usually not as good as those of the preferred polymers.
  • the polyacrylate used to stabilize the PET-POET co­polymer may be a suitable water soluble polyacrylate, such as alkali metal polyacrylate, e.g., sodium polyacrylate,of molecular weight less 50,000, usually being within the range of about 1,000 to 5,000, preferably being in the range of 1,000 to 3,000 and most preferably being between 1,000 and 2,000, e.g., about 2,000.
  • alkali metal polyacrylate e.g., sodium polyacrylate
  • water soluble polyacrylates may sometimes be substituted in part for the described sodium polyacrylate, including some other alkali metal polyacrylates, e.g., potassium polyacrylate, it is preferred that such substitutions, when permitted, be limited to a minor proportion of the material, and preferably the polyacrylate employed will be an unsubsti­tuted sodium polyacrylate.
  • alkali metal polyacrylates e.g., potassium polyacrylate
  • Such materials are available from Alco Chemical Corporation, under the name Alcosperse®.
  • fluorescent brighteners In addition to the stain removing components of the present invention, which cooperate with the cellulase and other enzymes in helping to remove embedded, deep-down or difficult-to-remove stains and soils from laundry substrates, other coacting components of preferred compositions of the invention are fluorescent brighteners.
  • This well-known class of components include various heterocyclic materials, such as are described in British patent 2,094,826, but those which are preferred are the stilbene and distilbene fluorescent or optical brighteners, representative of which are the Tinopals, such as Tinopals® 5BM conc. and RBS, marketed by CIBA-Geigy, and Blancophors®.
  • the fluorescent brighteners coact with the cellulase and other composition components, including the detergent, builder, other enzymes, soil release promoter, and oxygen or per-compound bleach, when present, to make such compositions produce whiter (and less dingy) laundry after repeated soilings and launderings.
  • the cellulase acts on fibrous materials, especially cotton, to modify the fiber structures, and the fluorescent brightener may be better adsorbed by the substrate and therefore can be more effective in improving the white appearance of the laundry, counteracting "dingies" or any "tattletale-gray” appearance thereof.
  • oxygen bleaches may be desired components of the invented compositions.
  • alkali metal perborates especially sodium perborate monohydrate, although the tetrahydrate and other hydrates may also be used.
  • a perborate activator may be employed, such as any of those described in European specifica­tion 0,269,169, including tetraacetyl ethylenediamine (TAED), acyloxy benzene sulfonate, tetraacetyl hexamethylenediamine and tetraacetyl methylenediamine.
  • TAED tetraacetyl ethylenediamine
  • acyloxy benzene sulfonate tetraacetyl hexamethylenediamine and tetraacetyl methylenediamine.
  • compositions including but not limited to: bleach stabilizing agents; suds controlling agents, e.g., sodium higher fatty acid soap; antioxidants; buffers, e.g., sodium propionate; soil suspending agents, e.g., sodium carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetates; dyes; perfumes; enzyme activators, such as cellulase activators, as described in British specification 2,094,826; filler salts, e.g., sodium sulfate; caking inhibitors, such as p-toluene sulfonic acid salts; flow promoters, e.g., magnesium silicate; solubilizers, such as urea; fabric softening agents, such as quaternary ammonium halides and bentonite; gelling inhibitors (when bentonite is present), such as siliconates; and bactericides.
  • bleach stabilizing agents e.g., sodium higher fatty acid soap
  • antioxidants e.
  • compositions made are effective laundry detergents which are especially useful in removing, with repeated washings, embedded particulate oily soils, which tend to give white and colored goods a dingy or tattletale gray appearance.
  • sebum/particulate soil the soiling effects of which are closely mimicked by Spangler test soil, a well-known test soil employed in evaluations of cleaning abilities of detergent compositions.
  • compositions of the present invention improved removals of such soils and other stains, even at such concentrations in wash waters as to result in low concentrations of enzymes, including cellulase, significantly below concentrations recommended in the art and by manufacturers of such enzymes.
  • nonionic detergent in the invented compositions will normally be in the range of 4 to 30%, preferivelyably 8 to 30%, more preferably 15 to 25%, and most preferably will often be about 17 or 20%. Such percentages are for phosphate and non-phosphate detergent compositions, and for bleaching and non-bleaching compositions, too.
  • the proportion of builder for the nonionic detergent will normally be in the range of 25 to 80%, preferably 40, 45 or 50 to 70 or 75%, and more preferably 55 to 65%.
  • phosphate-containing detergent compositions the content of phosphate is normally in the range of 40 to 75%, preferably 50 to 70%, e.g., about 59 or 60%, and usually it will be accompanied by 3 to 10% of sodium silicate, preferably 5 to 9% thereof, e.g., about 7%, which acts as a binder and bead strengthener, for spray dried compositions.
  • the builder components will typically include 20 to 40% of zeolite,15 to 40% of carbonate and 5 to 25% of bicarbonate, preferably 25 to 35% of zeolite, 20 to 30% of sodium carbonate and 5 to 15% of sodium bicarbonate, e.g., about 31% of Zeolite A, about 28% of sodium carbonate, and about 11% of sodium bicarbonate.
  • the proportions of phosphate and silicate will normally be in ranges like those given for the non-bleaching compositions and similarly, for bleachings of non-phosphate compositions the proportions of zeolite, carbonate and bicarbonate will be like those given for the corresponding non-bleaching, non-­phosphate compositions, but percentages will usually be decreased because of the presence of bleaching agent in the formulas, and sometimes zeolite content can even be lowered to 0.5 or 1%, and zeolite may even be eliminated from some formulas.
  • the cellulase contents of the present compositions will normally be in the range of 0.2 to 1% of the cellulase (as supplied, as Celluzyme® 1500T or cellulase of corresponding activity, as measured by CMC units). Preferably such content will be in the range of 0.3 to 0.7%, for example, about 0.5%.
  • the proportions of protease and amylase will each normally be in the range of 0.1 to 2%, preferably 0.1 to 1%, e.g., about 0.3 to 0.5%, but in some instances the amylase may be omitted, which has been done when detergent compositions are of a bleaching type. In such cases therefore, the lower limits on the ranges of contents of amylase will be 0%.
  • non-­cellulase enzymes which may be only protease and amylase
  • the proportions of all enzymes may be increased, sometimes to 2, 3 or even 10 times those given above, with proportions of other components being diminished accordingly.
  • the particulate detergent compositions of this invention are dry to the touch, non-caking and free flow­ing, they do contain some water, which often acts as a hydrat­ing binder and helps to increase particle strengths.
  • the water content will be in the range of 1 to 15%, preferably 7 to 13%, e.g., about 10% for phosphate-containing nonionic detergent compositions of the non-bleaching type, made from spray dried base beads, and will normally be in the 1 to 15% range, preferably 4 to 10%, e.g., about 7%, for corresponding non-­phosphate, non-bleaching products.
  • absorption of nonionic detergent and water is not as effective, and moisture contents may be less, such as within the range of 0.5% or 1 to 5%, preferably 1 to 3%, e.g., about 1%.
  • the proportion of PET-POET when it is in these compositions, will normally be in the range of 0.3 to 4%, preferably 1.0 to 3.0%, e.g., about 1.5% or about 2%, and the content of sodium polyacrylate will usually be in the range of 0.01 to 2%, preferably 0.02 to 0.5%, e.g., about 0.05% or about 0.1%, with the polyacrylate content normally being from 3 to 100% or 4 to 10%, e.g., about 5% of the content of PET-POET copolymer. More SRP may be employed if desired, often up to 3 or 5 times as much, but economic constraints often limit the proportion present because this component is comparatively expensive.
  • the SRP is cost effective and its action in promoting soil release from laundry is satisfactory.
  • the content of fluorescent brightener is normally in the range of 0.2 to 2%, preferably 0.3 to 1.5%, e.g., about 1%, on the basis of the brightener as supplied by the manufacturer, and such content applies to the total amounts of mixed fluorescent brighteners which may be utilized in the compositions.
  • a per-compound oxygen bleach When a per-compound oxygen bleach is present in the invented compositions the proportion thereof will usually be in the range of 10 to 35%, preferably being 10 or 20 to 30%, e.g., about 24%.
  • an activator to promote the release of bleaching oxygen from the per-compound it will normally be in amount from 0.2 to 5%, preferably 1 to 4%, e.g., about 3%, but the proportion thereof will depend on the particular activator or activator system employed.
  • adjuvants may be utilized in different proportions to give the detergent composition certain properties or to improve its properties.
  • the total proportion of adjuvants (excluding fillers) will be in the range of 0.1 to 10%, preferably 0.5 to 5%, and more preferably 0.5 to 3%, it being considered that the lower the content of adjuvants in the present compositions the better, as a normal rule.
  • the content of filler salts, such as sodium sulfate, will also normally be kept as low as feasible, usually being limited to 20%, preferably 10%, and more preferably 5%.
  • the detergent compo­sition is of nonionic detergent, tripolyphosphate, cellulase, protease and amylase, and the filler salt is sodium sulfate, as much as about 50% thereof may be used.
  • compositions in the wash waters will be relative­ly low because the compositions will be highly concentrated.
  • a normal charge of such compositions will be in the range of 0.04 to 0.08%, preferably 0.05 to 0.07%, e.g., about 0.06%.
  • Proportions of individual components will normally be in the range of 0.005 to 0.02% of nonionic detergent, 0.03 to 0.06% of total builders for such nonionic detergent, 0.00005 to 0.0008% of protease, 0 or 0.00005 to 0.0008% of amylase, and 0.0001 to 0.0008% of cellulase.
  • CMC units/liter preferably 3 to 7 CMC units/liter, e.g., about 4.7 or 5 CMC units/liter, may be present in the wash water in typical cases.
  • compositions may be used as a pre-soak, before washing, or as a soaking detergent, and satisfactorily remove various stains, including oily sebum stains, from laundry, especially from cottons and cotton-containing blends.
  • pre-soak or soak tests after the laundry is soaked in the detergent solution it is subjected to a single wash, using the soak solution as a source of detergent composition, and is rinsed and dried.
  • the invented detergent compositions can be manufactured by techniques similar to those employed for making known commercial detergent compositions.
  • Either phosphate or non-phosphate non-­bleaching compositions may be made by spray drying an aqueous crutcher mix of builders to hollow bead form and then applying melted, normally solid nonionic detergent to such beads, while mixing them, so that the nonionic detergent penetrates into the bead interiors, while also at least partially coating external surfaces of the beads.
  • other components of the detergent composition may be included in the melt of nonionic detergent, such as PET-POET copolymer and polyacrylate.
  • Addi­tional components of the detergent compositions may be post-added to the built detergent beads and such post-additions may be utilized to increase the bulk density of the detergent composi­tions, which is intentionally made highly concentrated, often being of a bulk density of at least 0.7 g./ml as in the range of 0.7 to 1.0 g./ml.
  • the enzymes are prilled and are blended with the beads, after which any perfume to be present may be sprayed onto the moving mix, as essentially the last manufacturing operation.
  • the fluorescent brightener will be stable enough to withstand spray drying so it will be included with the builders in the crutcher mix.
  • compositions may also be included in the crutcher mix and those which are unstable in heated aqueous media or cannot withstand the temperature of the spray drying air (usually 200 to 500°C.) may be post-added, either as particulate or liquid materials. Because per-compounds that may be employed as bleaching components in the invented compositions are unstable under such conditions, they will normally be post-added.
  • wash water temperatures may span the range of 10 to 90 or 95°C., often being in the ranges of 10 to 40, 50 or 60°C., for American practice, and even as low as 10 to 30°C., whereas in European practice such range can be from 30 or 40 to 80, 90 or 95°C., and sometimes 40 to 60°C. (in recent years European wash water temperatures have been lowered somewhat to save energy and to allow automatic washing of laundry dyed with more sensitive dyes).
  • fabric softening agents may be applied to the laundry or such may be included in the deter­gent composition or in the wash water, and may be applied during the washing operation.
  • the cellulase in addition to helping to break down some soils derived from vegetable matter, also acts in a subtle manner, in concert with other composition components, to modify the nature of such fiber surfaces. It has been noted that such actions on the cotton fibers remove microscopic sized ragged edges from the fibers, which tend to hold dirt and stains, so that otherwise such soils would not be readily removed by normal washing.
  • the cellulase employed in the past has been bacterial cellulase and was used in anionic detergent compositions at substantially higher concentrations than are employed in accordance with the present invention.
  • the present invention differs from prior art laundry detergent compositions and processes because the cellulase very preferably employed is such as may be derivable from fungi.
  • Good activity of the cellulase is obtained, using the invented compositions, which improve the removal of embedded or ingrained dirt, stains and soils, which are difficult to remove from laundry and which often give it a grayish cast, even after a plurality of washings.
  • Such grayness is significantly diminished, especially after plural washings, despite the alkalinity of the wash water, and such removal of this hard-to-remove soil is even effectable at comparatively low temperatures, such as those in the 10 to 40°C. range.
  • the present compositions appear to be different in properties from what might have been expected from the prior art because the prior art, which related primarily to anionic detergent compositions, indicated that at the higher concentra­tions employed its detergent compositions would both clean and soften, which is not the case for the invented compositions. Thus, it appears that the presence of the unexpectedly benefi­cial cleaning effect and the absence of softening are indicative of unobviousness of the present novel compositions.
  • Reflectometer readings were taken after washings and dryings, often repeated, and changes in white­ness of the swatches were recorded. Statistical analyses of such data established whether the changes were significant or not. From such tests it could be determined whether a formula was effective against certain stains, and its overall effectiveness against a variety of such soils could also be assessed. Although such tests are useful they are very time consuming and labor intensive so efforts were made to develop other tests which would be indicative of long term effects of employing particular detergent compositions to wash and whiten household laundry.
  • the detergent composition of the above formula is made by spray drying an aqueous crutcher mix (50-60% solids content) of sodium tripolyphosphate, sodium silicate and fluorescent brightener in a conventional spray drying tower, with drying air at temperatures in the range of 200 to 450°C., to spray dried hollow beads of moisture content of about 13% and particle sizes in the range of No's. 10-100, U.S. Sieve Series. After cooling of these base beads the nonionic detergent, in molten form, at a temperature in the range of 50 to 60°C., is sprayed onto the beads, is absorbed by them, coats surfaces thereof and solidifies thereon.
  • the phosphate-built nonionic detergent is made by utilizing different proportions of some components, so that the final product comprises 59.2 parts of the sodium polyphosphate, 7.0 parts of the sodium silicate, 20.0 parts of the NRE nonionic detergent, 1.0 part of a co-prilled mixture of about equal proportions of proteolytic and amylolytic enzyme, 2.0 parts of the PET-POET - polyacrylate mix (SRP-2-F), 1 part of the fluorescent brightener, 0.2 part of perfume, 9.1 parts of water and 0.5 part of Celluzyme 1500T.
  • SRP-2-F PET-POET - polyacrylate mix
  • the product is made in essen­tially the same manner as previously described and two further variations and the principal variation formula (1A) are compared to a leading commercial anionic detergent in soaking tests, as previously described, using 40 grams of each product per liter.
  • the variation formulas (1A0) no cellulase was present in the composition and in the other (1A1) the proportion had been increased to 1%.
  • the zero content cellulase formula was measurably inferior to the commercial product in removing Spangler soil from cotton by soak test whereas the 1% cellulase formula was clearly superior to such commercial detergent.
  • composition of Formula 1A was compared to a composition which did not contain cellulase (1A0).
  • the cotton test swatches used had previously been stained with Spangler sebum/particulate soil, liquid make-up, Piscataway (New Jersey) clay and EMPA 101 oily soil.
  • Composition 1A, containing 0.5% of cellulase was significantly superior, on average, to that without cellulase (1A0) in removing such soils from the swatches and such improvements were even more significant with respect to the Spangler, EMPA and make-up soils than with respect to the clay soil, in these experiments.
  • washing machine tests were all run at a concentration of 40 grams of detergent composition per 64 liters of wash water, which is about 0.06%, so that the cellulase concentration for 1A was about 0.0003% or 4.7 CMC units/liter, in the wash water.
  • EXAMPLE 2 Component Percent (by weight) Sodium zeolite (Zeolite A) 30.5 Sodium carbonate 28.0 Sodium bicarbonate 11.0 Narrow range ethoxylate nonionic detergent 20.0 ** Celluzyme 1500T, prilled 0.5 *** Proteolytic enzyme (Alcalase) 0.3 *** Amylolytic enzyme (Termamyl) 0.3 + PET-POET copolymer 1.90 + Sodium polyacrylate 0.10 Distilbene type fluorescent brightener (Tinopal 5BM) 1.0 Water 5.9 Perfume 0.2 Adjuvants q.s. 100.0
  • the product of this example is of spray dried base beads having nonionic detergent absorbed in them.
  • the base beads are made by the spray drying process described in Example 1, with the crutcher mix being of zeolite, carbonate, bicarbonate and distilbene type fluorescent brightener in about a 50% aqueous slurry. Because bicarbonate decomposes to carbonate during spray drying, to the extent of 1/3 to 1/2 of the bicarbonate charged, an appreciable proportion of the carbonate of the formula derives from charged bicarbonate (in the crutcher mix approximately equal proportions of carbonate and bicarbonate are initially present).
  • the spray dried base beads are of the same particle size range as the base beads of Example 1 and are of a moisture content of about 9%.
  • the other components are absorbed by, admixed with or sprayed onto the base beads to form the final free flowing non-phosphate built product.
  • product is tested for cleaning power in multiple washings of laundry items stained with hard to remove or "difficult" soils, which include sebum soil, and is compared to a control composition of the same formula except for the omission of the cellulase, improvements in removals of such soils in washings after the initial wash­ing are noted, indicating that the deep down or internal soil is being washed out of the test pieces, which after such multiple washings, do not appear to the human eye to be as stained as the controls.
  • wash water pH may be in the range of 9 to 9.5, and that the concentrations of the detergent composition and of the contained cellulase are low, on the order of 0.04 to 0.08% for the deter­gent composition and 0.0002 to 0.0004% for the cellulase (as supplied).
  • the cleaning power of the non-phosphate deter­gent composition of this example against hard-to-remove soils, such as clay, grass, liquid make-up, oily soil (EMPA-101) and test fabrics soil, especially in wash water at higher temperatures, such as 49°C., is notable and surprisingly good.
  • the invented compositions are clearly superior to a prior art commercial detergent composition that does contain cellulase, and such results are obtainable even at higher pH's, comparatively low washing temperatures, and at low concentrations of detergent composition and of cellulase in the wash water.
  • the reported results in this example and Example 1 are obtainable when utilizing as a control a com­mercial heavy duty detergent composition such as that sold under the trademark FAB but similar results are obtainable when other competitive particulate heavy duty detergent compositions are compared to the invented products.
  • EXAMPLE 3 Component Percent (by weight) Sodium tripolyphosphate 51.0 Sodium metasilicate 6.0 ° Nonionic detergent 12.0 Sodium perborate monohydrate 22.5 Perborate activator (TAED) 2.5 Stilbene fluorescent brightener (Tinopal 5BM) 0.5 Sodium ethylene diamine tetraacetate (EDTA) 0.4 Sodium carboxymethyl cellulose (CMC) 1.5 Lower alkyl phosphoric ester 1.0 Proteolytic enzyme (Alcalase) 0.5 Cellulase, fungal (1500 CMC units/g.) 0.5 Water 1.0 Zeolite A powder 0.6 100.00 ° C12 ⁇ 15 alcohol (7 EtO) nonionic detergent (BRE type)
  • the above formula is made by mixing components thereof, which are mostly in powder form, and spraying a liquid state nonionic detergent onto such mix. A small proportion of powdered zeolite, usually No. 200 sieve Zeolite 4A, is then added, which has the effect of improving flowability of the grand composition.
  • the above formula is of a bleaching particulate detergent composition intended for European use.
  • phosphates are barred from detergent compositions the phosphate and silicate contents may be replaced by zeolite, carbonate and bicarbonate, in the same proportions employed in the first formula of Example 2.
  • Both the phosphate and non-phosphate bleaching formulas of this example are effective detergent compositions under normal European washing conditions, which were mentioned earlier, and serve to remove deeply embedded soils from laundry, especially cotton items. Additionally, they help to prevent new laundry items from becoming grayed due to soils penetrating to the interiors of fibers thereof during repeated soilings and washing operations. Such results are verifiable by multiple washing tests and by the soak test, as previously described.
  • the cleaning power of this formulation can be improved by replacing the BRE nonionic detergent with the NRE nonionic detergent of Example 1 or by replacing it with comparable Shell Chemical Company NRE nonionic detergents, as mentioned in the specification. If the perborate and per­borate activator are removed from the formulations the desirable oxygen bleaching action thereof is lost but still the presence of the cellulase helps to remove hard to remove soils from test swatches during repeated launderings.
  • Formula 4B Non-Phosphate Nonionic Detergent Composition
  • NRE Nonionic ethoxylated alcohol
  • Formula 4D Non-Phosphate Anionic Detergent Composition
  • Component Percent (by weight) Linear tridecylbenzene sulfonate, sodium salt 17.6 Sodium aluminium silicate (Zeolite A) 25.2 Sodium carbonate 22.7 Sodium sulfate 16.4 Sodium silicate (Na2O:SiO2 1:2.4) 5.3 Tinopal 5BM 0.2 Hydroxypropyl methyl cellulose 0.6 Sodium carboxy
  • Formulas 4A and 4B include 0.5% of Celluzyme 1500T, or 7.5 CMC units per gram.
  • Formulas 4C and 4D include 0.5% of Celluzyme 1500T, or 7.5 CMC units per gram, too. In the described washing tests when such formulas are tested 80 g.
  • Control formulas are identical with the experimental formulas except for the omissions of Celluzyme 1500T and the replacements thereof with sodium sulfate in the anionic formulas, with sodium tripolyphosphate in the control corresponding to Formula 4A, and with Zeolite A in the control corresponding to Formula 4B.
  • the controls are designated 4A0, 4B0, 4C0 and 4D0, respectively.
  • Formula 4C was not statistically better in stain removal than Formula 4C0 and 4D was statistically better than 4D0 only for two stains at five washes at 49°C., much less than the improvement of 48 over 4B0. In soak tests the 4A formula is statistically superior to 4A0 and the 4C formula was no better than 4C0.
  • compositions described in the above working examples may be packaged in normal detergent cartons or may be sealed inside pre-measured, single-use pouches which either dissolve in the wash water or allow the detergent composition to penetrate the walls thereof during the washing operation. If desired, the compositions may be employed as pre-soaks, as has been indicated by the successful reports of results of the soak tests mentioned in the Examples.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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EP19890202650 1988-10-21 1989-10-20 Compositions détergentes à usage universel avec un agent tensioactif non ionique synthétique, organique ayant une action nettoyante modifiée sur le linge contenant de la salissure difficile à éliminer Withdrawn EP0365103A3 (fr)

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US26105188A 1988-10-21 1988-10-21
US261051 1988-10-21

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EP (1) EP0365103A3 (fr)
JP (1) JP2757967B2 (fr)
AU (1) AU628394B2 (fr)
DK (1) DK502589A (fr)
GR (1) GR1000506B (fr)
MX (1) MX170217B (fr)
NO (1) NO894193L (fr)
NZ (1) NZ230842A (fr)
TR (1) TR25108A (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991019794A1 (fr) * 1990-06-14 1991-12-26 Novo Nordisk A/S Activation d'hydrolase de polysaccharide
EP0425214A3 (en) * 1989-10-23 1992-05-06 Unilever Plc Enzyme-containing detergent compositions and their use
ES2048666A1 (es) * 1991-08-16 1994-03-16 Sandoz Ag Un preparado enzimatico estable a base de celulosas y proteasas.
WO1995018208A1 (fr) * 1993-12-24 1995-07-06 Henkel Kommanditgesellschaft Auf Aktien Poudre de lavage et de nettoyage
WO1996001886A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Detergent contenant de la cellulase
US5527483A (en) * 1991-05-31 1996-06-18 Colgate Palmolive Co. Nonaqueous gelled automatic dishwashing composition containing enzymes
EP0694060B1 (fr) * 1993-04-13 1997-12-17 Henkel Kommanditgesellschaft auf Aktien Agent de lavage enzymatique
WO1999002635A1 (fr) * 1997-07-11 1999-01-21 The Procter & Gamble Company Compositions detergentes comportant une cellulase specifique et un zeolite specifique
WO2000018870A1 (fr) * 1998-09-25 2000-04-06 The Procter & Gamble Company Compositions detergentes
WO2000066696A1 (fr) * 1999-04-29 2000-11-09 Genencor International, Inc. Matrice detergente a base de cellulase
WO2000070006A1 (fr) * 1999-05-19 2000-11-23 Colgate-Palmolive Company Compositions detergentes de lessive a forte teneur en protease
US6251144B1 (en) 1992-06-12 2001-06-26 Genencor International, Inc. Enzymatic compositions and methods for producing stonewashed look on indigo-dyed denim fabric and garments
US6630439B1 (en) * 1998-09-25 2003-10-07 The Procter & Gamble Company Solid detergent compositions comprising sesquicarbonate
WO2023144071A1 (fr) * 2022-01-28 2023-08-03 Unilever Ip Holdings B.V. Composition de lessive

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8727081D0 (en) * 1987-11-19 1987-12-23 Procter & Gamble Granular detergent compositions
AU654009B2 (en) * 1991-05-31 1994-10-20 Colgate-Palmolive Company, The Phosphate-containing powder automatic dishwashing composition with enzymes

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
GB1377092A (en) * 1971-01-13 1974-12-11 Unilever Ltd Detergent compositions
US4441881A (en) * 1982-09-07 1984-04-10 Lever Brothers Company Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions
GB8421802D0 (en) * 1984-08-29 1984-10-03 Unilever Plc Detergent composition
US4571303A (en) * 1985-01-23 1986-02-18 Colgate-Palmolive Company Built nonionic detergent composition containing stabilized polyethylene terephthalate-polyoxyethylene terephthalate soil release promoting polymer
JP2787941B2 (ja) * 1986-09-12 1998-08-20 花王株式会社 酵素含有高密度粒状洗剤組成物
GB8627915D0 (en) * 1986-11-21 1986-12-31 Procter & Gamble Detergent compositions
US4822516A (en) * 1986-12-08 1989-04-18 Kao Corporation Detergent composition for clothing incorporating a cellulase
AU616190B2 (en) * 1987-08-10 1991-10-24 Colgate-Palmolive Company, The Nonionic detergent composition of increased soil release promoting properties

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0425214A3 (en) * 1989-10-23 1992-05-06 Unilever Plc Enzyme-containing detergent compositions and their use
WO1991019794A1 (fr) * 1990-06-14 1991-12-26 Novo Nordisk A/S Activation d'hydrolase de polysaccharide
US5527483A (en) * 1991-05-31 1996-06-18 Colgate Palmolive Co. Nonaqueous gelled automatic dishwashing composition containing enzymes
ES2048666A1 (es) * 1991-08-16 1994-03-16 Sandoz Ag Un preparado enzimatico estable a base de celulosas y proteasas.
US6251144B1 (en) 1992-06-12 2001-06-26 Genencor International, Inc. Enzymatic compositions and methods for producing stonewashed look on indigo-dyed denim fabric and garments
EP0694060B1 (fr) * 1993-04-13 1997-12-17 Henkel Kommanditgesellschaft auf Aktien Agent de lavage enzymatique
WO1995018208A1 (fr) * 1993-12-24 1995-07-06 Henkel Kommanditgesellschaft Auf Aktien Poudre de lavage et de nettoyage
WO1996001886A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Detergent contenant de la cellulase
WO1999002635A1 (fr) * 1997-07-11 1999-01-21 The Procter & Gamble Company Compositions detergentes comportant une cellulase specifique et un zeolite specifique
WO2000018870A1 (fr) * 1998-09-25 2000-04-06 The Procter & Gamble Company Compositions detergentes
US6630439B1 (en) * 1998-09-25 2003-10-07 The Procter & Gamble Company Solid detergent compositions comprising sesquicarbonate
WO2000066696A1 (fr) * 1999-04-29 2000-11-09 Genencor International, Inc. Matrice detergente a base de cellulase
US6565613B1 (en) 1999-04-29 2003-05-20 Genencor International, Inc. Cellulase detergent matrix
AU770549B2 (en) * 1999-04-29 2004-02-26 Genencor International, Inc. Cellulase detergent matrix
WO2000070006A1 (fr) * 1999-05-19 2000-11-23 Colgate-Palmolive Company Compositions detergentes de lessive a forte teneur en protease
AU772325B2 (en) * 1999-05-19 2004-04-22 Henkel Ag & Co. Kgaa Laundry detergent composition containing high level of protease enzyme
WO2023144071A1 (fr) * 2022-01-28 2023-08-03 Unilever Ip Holdings B.V. Composition de lessive

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MX170217B (es) 1993-08-11
JP2757967B2 (ja) 1998-05-25
GR1000506B (el) 1992-07-30
TR25108A (tr) 1992-11-01
NO894193L (no) 1990-04-23
AU628394B2 (en) 1992-09-17
AU4254989A (en) 1990-04-26
GR890100672A (en) 1990-11-29
DK502589A (da) 1990-04-22
EP0365103A3 (fr) 1991-04-03
DK502589D0 (da) 1989-10-10
NO894193D0 (no) 1989-10-20
NZ230842A (en) 1992-05-26
JPH02196900A (ja) 1990-08-03

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