US 3640877 A
Description (OCR text may contain errors)
AU 165 Ex Una-ow vwwwv 3,640,877 DETERGENT Michael R. R. Gobert, 1 his, Rue de la Sabliere, 92 Courbevoie, France No Drawing. Filed Apr. 17, 1969, Ser. Nam
Int. Cl. Clld 7/18 US. Cl. 252-99 10 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a detergent preparation containing a precursor of hydrogen peroxide. More particularly the precursor is a system selected from the group consisting of glucose-glucose oxidase and starch-amyloglucosidase-glucose oxidase. The detergent also includes a hydroxylamine. The detergent is prepared in solid form, generally as powder, and in use is dissolved in water in the presence of oxygen or air.
Detergent preparations containing bleaching components, such as per-compounds, have been used to remove stains from laundry, textiles and linen. The per-compounds have, however, had certain disadvantages, such as diminished activity upon storage due to degradation of the per-compound and lack of stability of the detergent composition. Thus, per-compounds in detergent compositions may not be highly effective when not freshly added.
It is an object of this invention to provide a stable detergent preparation in which the bleach-active compound, hydrogen peroxide, is formed during washing. Other objects of the invention will be apparent from the following description.
In accordance with certain of its aspects this invention relates to a detergent preparation comprising a detergent material selected from the group consisting of an organic surface active agent, a builder salt and mixtures thereof; a hydrogen peroxide precursor selected from the group consisting of (A) about -30% by weight of said detergent preparation of glucose, and about 0.5- by weight of said detergent composition of a glucose oxidase and (B) about 530% by weight of said detergent preparation of starch and about 0.5-10% by weight of said detergent preparation of amyloglucosidase and about 0.5-10% of glucose oxidase; and about 0.5-5 by weight of said detergent preparation of a hydroxylamine; said detergent preparation having a pH of about 5-7.5 upon dilution in water at a concentration of about 0.2-1% by weight.
The detergent material employed in accordance with this invention may be an organic surface active agent, a builder salt or mixtures thereof.
The surface active agent which may be employed may be any commonly used compound having surface active or detergent properties. Most preferred are those watersoluble 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 water-soluble salts of higher fatty acids or rosin acids, which may be derived from fats, oils and waxes of animal, vegetable or marine origin e.g., the sodium eat 0 3,640,877 Patented Feb. 8, i972 ice 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 about 12 to 22 carbon atoms to the molecule.
As examples of suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 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 naphthalene sul fonate; 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 hydroxy-ethyl 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 8-25 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 m0nosulfate; and the hydroxy sulfonated higher fatty acid esters such as the higher fatty acid esters of low molecular weight alkylol sulfonic acid 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 products of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with up to about. 50 ethylene oxide units; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate sorbitol monooleate and mannitan monopalmitate 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 RNHCJ-LNH, 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 RCONHC ILNH wherein R is an alkyl group of about 12 to 18 carbon atoms, such as N-amino ethyl-stearly 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 nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including such 1 to 3 carbon alkyl group bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. Typical quaternary ammonium detergents are ethyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethylstearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dirnethyl-ethyl lauryl 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 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 builder which may be employed in accordance with this invention may be any of the water-soluble 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 salts may be suitable alkali metal, alkaline earth metal, or heavy metal salt or combinations thereof. Ammonium or an ethanolammonium salt in a suitable amount may be added also, but generally the sodium and potassium salts are preferred. Examples are the water-soluble sodium and potassium phosphates, silicates, carbonates, bicarbonates, borates, sulfates and chlorides. Particularly preferred builder salts are the alkaline builder salts such as 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 3: 1.
Both Phase I and Phase M 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 in the amount of about 5-94% by weight of the total detergent preparation. Typically, when a mixture of the organic surface active agent and the builder salt is employed, the preparation contains about -25% by weight of the surface active agent and about 45-74% by weight of the builder.
It is a feature of this invention that glucose and glucose-oxide enzyme or starch, amyloglucosidase enzyme which hydrolyzes starch to glucose and glucose oxidase enzyme are employed to form hydrogen peroxide in water during washing.
The glucose-glucose oxidase reaction is characterized by the following equation:
glucose oxidase 3 Glucwe 20, 21(10 2 gluuoule said H70;
In this equation starch and amyloglucosidase may replace glucose. Glucose oxidase has a potency of 1300 to 1500 units per gram measured in accordance with the procedure in the Journal of Agricultural and Food Chemistry, 1953, page 1727, glucose oxidase typically is an impure enzyme and is mixed with catalase, an enzyme effective upon hydrogen peroxide to immediately decompose the peroxide to water and oxygen in accordance with the following equation:
Therefore, in order to permit glucose and glucose oxidase or starch, amyloglucosidase and glucose oxidase to be used to form bleach effective hydrogen peroxide, it is also necessary to prevent catalase breakdown of hydrogen peroxide.
In accordance with the instant invention it was found that a hydroxylamine such as hydroxylamine free base and salts of hydroxylamine such as hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine fiuosilicate, and hydroxylamine halides including hydroxylamine chloride and hydroxylamine bromide prevent the breakdown of hydrogen peroxide by catalase and are compatible with other components of the detergent preparation. Thus, when a hydroxylamine is employed in the preparation, glucose and glucose oxidase can form hydrogen peroxide in water and the peroxide formed is present during washing and is highly effective at the moment of bleach. The preferred hydroxylamine is hydroxylamine sulfate.
The detergent preparations of the instant invention contain about 5-30% by weight, preferably about 15-30%, of glucose or starch; about 05-10% by weight preferably about 2.5-5% of amyloglucosidase when starch is used; about 05-10% by weight preferably about 2.5-5 of glucose oxidase; and about 0.5-5 by weight, preferably 1-3%, of the hydroxylamine salt.
It is also desirable that upon dilution in water at typical detergent use concentrations, say about 0.2-1% by weight of the detergent preparation in water that the detergent solution be from lightly acid to weakly basic, that is in the pH range of about 5-7.5. It is noteworthy that as the pH gets more strongly basic than about 7.5, the activity of the enzyme is decreased.
The detergent preparation may also contain additive such as carboxymethylcellulose or polyvinylpyrrolidone. These additives may be present in amount of about 0.1- 5% by weight of the detergent composition. The detergent composition may also include minor amounts of optical brighteners, perfumes and preservatives. Activators such as N-benzoyl succinimide may also be present.
The detergent preparation of the invention may be prepared by adding glucose, glucose oxidase and hydroxylamine salt or starch, amyloglucosidase, glucose oxidase and hydroxylamine salt to detergent material. Typicall the detergent material is first prepared by spray drying. it hydroxylamine free base is employed, it is preferabl added to the detergent material before spray drying. 'l" he preparation may also be prepared by dry blending.
In use, the detergent preparation is dissolved in water in a washing machine such as a drum or agitator washing machine in amount of about 2 grams to 10 grams, preferably about 5 grams, per liter of water to provide a solution having a lightly acid to weakly basic pH of about 5 to 7.5. The action of the washing machine provides sufficient contact with air and water to form hydrogen peroxide from glucose oxidase or from starch, amyloglucosidase and glucose oxidase during washing. The formation of hydrogen peroxide in the preparation is not adversely affected at temperatures ranging from ambient temperature to about 55 C. During washing the temperature may then be raised to affect bleaching.
The following examples are set forth in order to illustrate the invention. All amounts recited are by wei ht unless otherwise specified.
EXAMPLE I The following preparation is formulated:
Percent Glucose oxidase Glucose Hydroxylamine sulfate 1.5 Na HPO -KH PO mixture To 100 The theoretical maximum H 0 concentration which could be obtained with this composition is 3.55 X 10- m./l. at C., 120 grams of the composition is dissolved in 24 liters of water resulting in a pH of 5.8 and agitated in the presence of air. The concentration of hydrogen peroxide after various periods of time is determined as follows:
Time in minutes: Concentration H 0 m./l. 10 1X 10- 20 1.7 10-' 23x10- 2.8)(10' 60 3.5X10- Thus, effective amounts, up to almost 100% of the theoretical amount, of hydrogen peroxide are formed, and decomposition of hydrogen peroxide is inhibited in the presence of the hydroxylamine salt. Similar results are obtained if glucose is replaced by 20% starch and 10% amyloglucosidase and the amount of phosphate mixture reduced accordingly.
EXAMPLE II The effect of pH on the amount of hydrogen peroxide which is formed from the glucose-glucose oxidase formulation of Example I, in solution in water in the presence of air and upon agitation at 25 C. is determined.
The amount of hydrogen peroxide formed after 60 minutes at various pH values is indicated below:
Percent hydrogen peroxide pH: in relation to theory 5 5.8 99 7 72 Thus, at lightly acid to weakly basic pH values between about 5 and 7.5 there was desirable formulation of hydrogen peroxide without an undesirable amount of decomposition into water and oxygen. Similar results are obtained with the starch-amyloglucosidase formulation.
EXAMPLE III The following preparations are formulated:
In the test described below 32x10" moles of hydrogen peroxide per liter of solution is added to preparation A. Each preparation also contained a small amount of sulfuric acid in sufficient amount to obtain a pH of 7 upon dilution in water.
Preparation B is dissolved in cold water (20 C.) in an agitator washing machine at a dilution of 5 g./l. Fabric squares tinted with Immedial black are immersed in the solution. Preparation B remains in cold water for 50 minutes during which time 3.2 10- ml]. of hydrogen peroxide is formed which corresponds to the amount of hydrogen peroxide in Preparation A. The temperature is 6 then raised to the boil. Preparation A is used shortly after addition of hydrogen peroxide to the preparation. It is dis solved to water at the same concentration as Preparation B and the temperature is raised to the boil in an agitator washing machine. Fabric squares tinted with Immedial black are also immersed in this solution.
The efi'icacy of bleaching of the fabric squares with Preparation B in which hydrogen peroxide is formed from glucose and glucose oxidase in the presence of the hydroxylamine salt is compared with Preparation A which contained freshly added hydrogen peroxide. The efiicacy of bleaching is determined as the increase in reflectance of the fabric squares (A).
After two tests with preparation B, A is found to be 7 and 7. After two tests with preparation A, A is found to be 7.65 and 7.85.
Thus, the preparation in which hydrogen peroxide was formed from glucose and glucose oxidase and prevented from decomposing by the hydroxylamine salt was practically equivalent in bleaching efiicacy to a preparation which contained freshly added hydrogen peroxide.
Similar effective bleaching can be obtained when hydroxylamine freee base, hydroxylamine chloride, hydroxylamine nitrate and hydroxylamine fiuosilicate are substituted for hydroxylamine sulfate in preparation B and/or when 20% starch and 10% amyloglucosidase are substituted for glucose in Preparation B (the amount of sodium sulfate being reduced accordingly).
Furthermore, similar effective bleaching can be obtained when Preparation B is modified to replace the condensate of C -C fatty alcohol with 23 moles of ethylene oxide with the condensate of C -C fatty alcohol with 50 moles of ethylene oxide or to omit the nonionic surface active agent altogether.
EXAMPLE IV The following detergent composition is formulated:
Parts Sodium tallow soap 6 Sodium dodecyl benzene sulfonate 3 C -C fatty alcohol condensate with 50 moles of ethylene oxide 6 Sodium carboxymethyl cellulose 0.8
Ethylene diamine tetraacetic acid, tetrasodium salt 0.14 Sodium tripolyphosphate 35.0 Brighteners and perfume 0.413 Glucose a. 20 Glucose oxidase 5 Hydroxylamine sulfate 1.6 Sodium sulfate and impurities Q.s. to
This preparation is permitted to remain in water adjusted at pH 7 with sulfuric acid, at 40 C. at a dilution of 5 g./l. The moles of hydrogen peroxide per milliliter formed after various periods is determined to be:
23 minutes=0.'.i1 10" 31 minutes=0.48 x16" 38 minutes=0.73 X 10"- 45 minutes=0.94 10" 56 minutes=1.16 x10 oxidase, and (B) about 5-30% by weight of said detergent preparation of starch, about 05-10% by weight of said detergent preparation of amyloglucosidase and about 05-10% by weight of said detergent preparation of glucose oxidase; and about 0.55% by weight of said detergent preparation of hydroxylamine free base or water soluble salt thereof; said detergent preparation having a pH of about 5-7.5 upon dilution in water at a concentration of about 0.2-1% by weight.
2. The detergent preparation claimed in claim 1 wherein hydroxylamine salt is present.
3. The detergent preparation claimed in claim 1 wherein said hydrogen peroxide precursor is glucose and glucose oxidase.
4. The detergent preparation claimed in claim 3 wherein said glucose is present in amount of about 15- 30%, said glucose oxidase is present in amount of about 2.5-5% and said hydroxylamine or salt thereof is present in amount of about 13%.
5. The detergent preparation claimed in claim 1 wherein said hydrogen peroxide precursor is starch, amyloglucosidase and glucose oxidase.
6. The detergent preparation claimed in claim 5 wherein said starch is present in amount of about 15- 30%, said amyloglucosidase is present in amount of about 2.5-5% and said glucose oxidase is present in amount of about 2.55% and said hydroxylarnine or salt thereof is present in amount of about l3%t 7. The detergent preparation claimed in claim 2 wherein said hydroxylamine salt is selected from the group consisting of hydroxylamine sulfate, hydroxylamine nitrate, hydroxylamine fluosilicate, and a hydroxylamine halide.
8. The detergent preparation claimed in claim 7 5 wherein said hydroxylarnine salt is hydroxylamine sulfate 9. The detergent preparation claimed in claim 1 wherein said detergent material includes an organic synthetic anionic surface active agent.
10. The detergent preparation claimed in claim 1 wherein said hydroxylamine is selected from the group consisting of hydroxylarnine sulfate, hydroxylamine nitrate, hydroxylamine fiuosilicate, and a hydroxylamine halide, said builder salt including an inorganic phosphate builder salt is present.
25 MAYER WEINBLA'I'T, Primary Examiner US. Cl. XR.
8-111; 195-163; 252-DIG. l2