US3753915A - Biological cleaning preparation - Google Patents

Abstract

A BIOLOGICAL CLEANING PREPARATION CONTAINING A PROTEOLYTIC ENZYME AND A SALT OF AN ORRGANIC HYDROPEROXIDDE.

Description

United States Patent O ABSTRACT THE DISCLOSURE A biological cleaning preparation containing a'proteolytic enzymeand a salt of an organic hydroperoxide.

This invention relates to a biological enzyme preparation or composition containing a proteolytic enzyme and an oxidizing agent. The preparation is a powdery solid and is destined for washing linen and similar products.

3 Claims Cleaning preparations including enzymes have been' used with oxidizing agents. Sodium perborate has generally beenused. Other oxidizing agents have beensuggested but these generally lack stability or have poorer cleaning capability than sodium perborate.

It is an advantage of this invention to provide a biological cleaning preparation containing a stable organic oxidizing agent which is a superior biOlOgical detergent in cleaning capability, particularly in the cleaning of proteinic blood stains.

Other advantages will be apparent from consideration of the specification.

In accordance with certain of itsaspects, this invention relates to a biological cleaning preparation containing a proteolytic enzyme and an alkali salt of a hydroperoxide having the formula:

BA OM in which R R and R are each hydrogen or'a hydrocarbon radical, R R and R not being all simultaneously hydrogen'and two'of R R and R capable of being 'part of the same cyclic hydrocarbon group and M isan alkali metal, such assodium or potassium or ammonium.

v The proteolytic enzymes which are employed in the instant invention are active upon protein matter and catalyze digestion or degradation of such matter when present as in linen or fabric stain in a hydrolysis reaction. The enzymespare effective at a pH range of 4-12, such as usually prevails in detergent cleaning procedures. Moreover,jthey may be effective at moderately high temperatures solong asthe temperature does not degrade them. Some proteolytic enzymes are effective at up to 70 C. and higher. They are also effective at ambient temperature and lower to about 20 C. Particular examples of I proteolytic enzymes which may be used in the instant invention include pepsin, trypsin, chymotrypsimpapain, bromelin, ,colleginase, keratinase, carboxylase, amino pepidasle, elastase, subtilisin and aspergillopepidase A and B. Preferred enzymes aresubtilisin enzymes manufactured and cultivated from special strains of spore forming bacteria,,particularly Bacillus subtilis. Furthermore, it preferred that the enzyme be substantially free from sulfhydryl groups or disulfide bonds which may inhibit some of the active oxygen of the oxidizing agent. I

l fIhednature of hydrocarbon radicals R1, R jand R is not lciiticaltan d they can be therefore chosen among the straight or branched chain alkyl radicals, especially alkyl radicals having 1 to 12 carbon atoms, the aryl' alkyl radicals, ..the cycloalkyl, alkyl-cycloalkyl and arylcycloalkyl radicals, the, unsaturated homologues of these alkyl and cycloalkyl radicals, and the aromatic radicals, especially phenyl, alkyl phenyl, naphthyl, alkylnaphthyl and anthracenyl. Y

These hydrocarbon radicals can be by other-means '1 3,753,915 Patented Aug. 21, 1973 Tertiary amyl Methyl cyclohexane Tertiary butyl Indanyl Propyl dimethyl methane Pinene Propyl diethyl methane p-Methane Propyl butyl ethyl methane Benzyl Propyl ethyl ethane Cumene Propyl butyl ethane Sulfocumene Octyl Butyl benzene Decyl Dibutyl benzene Undecyl' p-cymene 2-ethyl-hexyl Pentamethyl ethyl l-methyl cyclohexyl l-ethyl cyclohexyl Phenyl cyclohexyl Phenyl cyclohexane Methyl cyclopentane As other examples can be also cited salts of sodium, potassium, and ammonium of hydroperoxides obtained by autooxidation of tetralin, of octahydroanthracene, etc.

The non-salified hydroperoxides are not ntilizable as bleaching agents in washing compositions, for generally they are liquids, insoluble in water and often present a strong odor difficult to conceal.

The alkali metal (including ammonium) salts of hydroperoxide, utilized in the instant invention are soluble in water, do not produce an undesirable odor and possess desirable bleaching properties.

In accordance with the instant invention it is preferred to employ as the hydroperoxide salt, the sodium salt of cumene hydroperoxide usually available as the tetrahydrate. Other desirable hydroperoxide salts are the sodium salts of paramenthane hydroperoxide andof tertiobutyl hydroperoxide.

The active oxygen content of the hydroperoxide salt, varies with the particular salt. In the sodium salt of cumene hydroperoxide tetrahydrate the active oxygen content is about 6.25%-6.5% by weight.

In accordance with certain aspectsof the instant invention, a preferred amount of hydroperoxide salt provides an active oxygen concentration of about 1-50 p.p.m., preferably 3-25 p.p.m., of active oxygen to wash water. The proportions of salt can, therefore, be readily calculated if it is known how much of the total formulation is to be added to wash water. Detergent formulations may be designed for use in proportions of about (ll-0.5% for soaking in water or about 0.1-'-0.2 or 0.3-1% for washing in water.

The enzyme concentration can be varied widely. Typically, an enzyme having a proteolytic activity of about 1.5 Anson units per gram is present in amount which provides about 1 to 40 p.p.m., more preferably about 28 p.p.m., of the enzyme in the wash water. The optimum proportionate amount of enzyme to be used in a detergent composition containing the hydroperoxide salt will of course, depend upon the effective enzyme content of the enzyme preparation. As with the hydroperoxide salt, the quantity of enzyme to be used for stains susceptible to enzyme action will be dependent upon a number of factors, particularly time, temperature'and amount of active oxygen provided by the hydroperoxide salt. v

The enzyme and the hydroperoxide salt may be used together as in the water used for a prerinse of soiled t-butyl dimethyl benzene 2-phenyl propyl Diphenyl methane Phenyl propyl methane Di-isopropyl benzene Isopropyl chlorobenzene, and Isopropyl naphthalene clothes, without any surface active agent being present. It is preferable, however, to mix these ingredients into a surface active detergent composition such as a heavyduty built granular detergent composition or more preferably in a soaking detergent composition.

The surface active agent which may be employed may be any commonly used compound having surface active or detergent properties. Most preferably are those water-soluble surface active compounds having anionic or nonionic properties. Anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, and phosphate. Examples of suitable anionic detergents which fall within the scope of the invention include the soaps, such as the watersoluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably 12 to 22, carbon atoms to the molecule.

As examples of suitable synthetic anionic detegents there may be cited the higher alkyl mononuclear aro matic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naph thalene sulfonate; sulfated aliphatic alcohols such as sodium lauryl and hexadecyl sulfates, triethanolamine lauryl sulfate, and sodium oleyl sulfate; sulfated alcohol ethers, such as lauryl, tridecyl, or tetradecyl sulfates including 2-4 ethylene oxide moieties; sulfated and sulfonated fatty oils, acids or esters such as the sodium salts of sulfonated castor oil and sulfated red oil; sulfated hydroxyamides such as sulfated hydroxylethyl lauramide; sodium salt of lauryl sulfoacetate; sodium salt of dioctyl sulfosuccinate; and the sodium salt of oleyl methyl tauride.

Other anionic surface active agents which may be employed in the practice of this invention include olefin sulfonates, typically containing 825- carbon atoms.

Also included within the ambit of the invention are the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate, tallow diglyceride monosulfate; and the hydroxy sulfonated higher fatty acid esters such as the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic acid ester of isethionic acid.

Nonionic surface active agents are those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.

As examples of nonionic surface active agents there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide a'ddends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan mono-- palmitate and the condensation products of polypropylene glycol with ethylene oxide.

Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents, there may be noted the diamines such as those of the type RNHC H NH wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-aminoethyl stearyl amine and N-aminoethyl myristyl amine; amide-linked amines such as those of the type R'CONHC H NH wherein R' is an alkyl group of about 12 to 18 carbon atoms, such as N-amino ethyl-stearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nigrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including such 1 to 3 carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate and monosulfate, Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trirnethyl-cetyl ammonium bromide, methyl-ethyl-dilauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.

The surface active compounds which are used in the most preferred aspects of this invention are those having anionic or nonionic properties. The most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates. The particular salt will be suitably selected depending upon the particular formulation and the proportions therein.

The surface active agent is typically present in an amount of about 595% by Weight of the detergent composition, preferably 10-25% by weight.

The enzyme may be present in powdered form admixed into the deteregnt formulation.

In addition to the materials described above, the detergent composition of the invention may include a builder for the detergent. The builder may be any of the watersoluble inorganic builder salts commonly known in the art, or it may be a water-soluble organic sequestering agent such as sodium nitrilotriacetate, or mixtures thereof.

The water-soluble inorganic builder salt may be suitable alkali metal, alkaline earth metal, or heavy metal salt of combinations thereof. Ammonium or an ethanolammonium salt in a suitable amount may be added also, but generally the sodium and potassium phosphates, silicates, carbonates, bicarbonates, borates, sulfates, and chlorides. Particularly preferred builder salts are polyphosphates, silicates and borates.

In the Water-soluble inorganic builder salt mixtures used in the detergent compositions, it is often preferred to have present a mixture of sodium tripolyphosphate and sodium or potassium bicarbonate, such as a combination or mixture of salts wherein the bicarbonate to tripolyphosphate ratio is selected from the range of about 1:1 to about 3:1.

Both Phase I and Phase II sodium tripolyphosphate and mixtures thereof may be successfully used in the compositions. The usual commercial tripolyphosphate consists mainly of the Phase II material. The commercial tripolyphosphate material is usually essentially tripolyphosphate, e.g. 87-95%, with small amounts, e.g. 4-13% of other phosphates, e.g. pyrophosphate and orthophosphate. Sodium tripolyphosphate in its hydrated form may be used also. Trisodium orthophosphate may be used in the amounts indicated.

The sodium or potassium bicarbonate is an effective pH buffer. The bicarbonate may be incorporated directly as anhydrous bicarbonate or in the form of sesquicarbonate, a hydrate containing both bicarbonate and carbonate.

Other suitable builder salts which may be present include the water-soluble sodium and potassium silicates, carbonates, borates, chlorides and sulfates.

Generally, when present, the builder salt is employed in amount in the range of about -90%, preferably at least (eg 35 to 80%) of the detergent composition.

The composition may also contain polymeric additives such as sodium carboxymethylcellulose or polyvinyl alcohol (e.g. in amount of of about 0.1-5%) or other polymeric additives to inhibit redeposition of soil. Minor amounts of optical brighteners may be present, as in proportions in the range of about 0.01 to 0.15%; examples of such brighteners are the stilbene brighteners such as sodium-2-sulfo-4-(Z-naptho 1,2 triazole) stilbene; disodium 4,4 -bis (4-(am'lino-6-m0rpholino s triazin-2-ylamino) stilbene disulfonate or disodium 4,4 -bis(4,6-dianilino-s-triazin-Z-yl-amino) stilbene disulfonate; and the oxazole brighteners, having for example a 1-phenyl-2- benzoxazole ethylene structure. Perfumes, coloring agents and preservatives may also be included.

The enzyme and hydroperoxide salt may be added in powdered form to the detergent composition and mixed in therewith as in dry blending. To improve the stability of the compositions, one or more of these ingredients may be protected from the atmosphere or from contact with the others. It is within the scope of the invention to supply separate packets (e.g. a moisture-proof wrapping) of these ingredients for addition to the wash water.

The compositions of this invention may be used for washing for short periods, e.g. 5 to 45 minutes, in cool water, e.g. at 20-40 C., or in warm or hot Water e.g. at 50, 60 or 70 C. or even at or near the boil. They may also, if desired, be used for long periods soaking at room temperature or in hot water, for example, for several hours or overnight.

The following examples are given to further illustrate this invention. In these examples, as in the rest of the application, all proportions are by weight unless otherwise indicated.

EXAMPLE I A detergent composition having the following formula.

is prepared.

Component: Parts Sodium dodecyl benzene sulfonate 28 Pentasodium tripolyphosphate 30 Sodium silicate (SiO /Na O-2/ 1) 6 Sodium carboxymethyl cellulose 0.8 Tetraanilino stilbene brightener 0.2 Perfume 0.2

Sodium sulfate and moisture, balance to 100.0

0.7% subtilison enzyme (Alcalase) having a proteolytic activity of 1.5 Anson units per gram and various amounts of sodium perborate and of sodium hydroperoxide are added to the detergent to provide active oxygen in amounts indicated in table below.

Two standard EMPA swatched stained with non-fixed blood are washed by soaking overnight at room temperature in one liter of solution containing 5 g. of soaking detergent containing the enzyme and varying amounts of the active oxygen compound. The differences in reflectance readings before and after soaking (ARd) and the benefit from the addition of active oxygen compound are indicated in the following table:

It is apparent from the data set forth in the table above that the composition of the invention containing proteolytic enzyme and organic hydroperoxide salt is superior in removing blood stains in comparison with compositions containing the same enzyme and sodium perborate tetrahydrate.

The subtilisin enzyme Alcalase used in the foregoing example is characterized as having its maximum proteolytic activity at a pH of 8-9. This activity as measured on the commercial enzyme available from Novo Industri A/S, Copenhagen, Denmark is about 1.5 Anson units per gram of the enzyme. The commercial enzyme is a raw extract of Bacillus subtilis culture.

EXAMPLE II Compositions containing Alcalase and sodium cumene hydroperoxide as in Example I which are added to detergents having the formulation indicated below also produce superior increases in cleaning capability when stained fabrics are washed with such detergents for one-half hour at 50 C. in a solution containing 0.5% of the detergent.

In the above examples other alkali metal and ammonium salt of organic hydroperoxide are substituted for sodium cumene hydroperoxide in amounts which provide 5 p.p.m. of active oxygen in the bath. These salts include sodium paramenthane hydroperoxide and sodium terbiobutyl hydroperoxide.

It will be apparent to one skilled in the art that various modifications of the above examples may be made thereto.

I claim:

1. A biological cleaning preparation consisting essentially of a proteolytic subtilisin enzyme in amount such that when said preparation is dissolved in water, about 1-40 p.p.m. of said enzyme are present and a salt of an organic hydroperoxide having the formula:

128 wherein R R and R are each selected from the group consisting of hydrogen, straight or branched chain alkyl containing 1-12 carbon atoms, cycloalkyl and aromatic radicals, R R and R not being all simultaneously hydrogen and two of R R and R capable of being part of the same cyclic hydrocarbon group and M is an alkali metal, said organic hydroperoxide being present in amount such that when said preparation is dissolved in water, about 1-50 p.p.m. of active oxygen are provided.

2. The biological cleaning preparation of claim 1 wherein said preparation also includes a surface-active agent and about 20-90% by weight a Water soluble inorganic builder salt.

3. The biological cleaning preparation of claim 1 wherein the salt of said hydroperoxide is the sodium salt of cumene hydroperoxide.

References Cited UNITED STATES PATENTS 3,574,519 4/1971 Lincoln 25299 3,519,379 7/1970 Blomeyer et al 25299 X 2,715,611 8/1955 Weeks 252186X MAYER WEINBLATT, Primary Examiner US. Cl. X.R.

8--111; 25299, 186, Dig. 12; 260610