US3723327A - Granular proteolytic enzyme composition - Google Patents
Granular proteolytic enzyme composition Download PDFInfo
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- US3723327A US3723327A US3723327DA US3723327A US 3723327 A US3723327 A US 3723327A US 3723327D A US3723327D A US 3723327DA US 3723327 A US3723327 A US 3723327A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
Definitions
- ABSTRACT The invention is directed to an improvement in the storage stability of granular proteolytic enzyme compositions.
- the proteolytic enzymes are contained in granules to which an acidic substance has been added.
- the granules will comprise a neutral or alkaline carrier material, for example an alkali metal phosphate; a gluing agent, for example a nonionic surface active agent; a proteolytic enzyme and an acidic material, for example citric acid.
- the present invention relates to granular proteolytic enzyme compositions, adapted to be formulated with a detergent composition, and to detergent compositions containing these granular proteolytic enzyme compositions.
- Enzymic cleaning compositions are old. See, for example, German patent specifications 283,923 (Rohm, 1915) and 329,958 (Rohm, 1920).
- the enzymes aid in cleaning by attacking the soil and stains of the soiled objects to be cleaned. Proteinaceous soil and stains are attacked by proteolytic enzymes.
- proteolytic enzymes suitable for cleaning purposes, are normally found in the form of fine powders. Such fine powders are difficult to handle and difficult to formulate.
- When such fine powders are incorporated in detergent compositions, their stability is often greatly impaired by several ingredients of the detergent composition, and by moisture, which may be taken up by the detergent composition during storage. It is believed that this moisture brings the proteolytic enzymes into contact with the other ingredients of the detergent composition, which are harmful to the proteolytic enzymes.
- the present invention therefore relates to a granular proteolytic enzyme composition, adapted to be formulated with a detergent composition, the granular proteolytic enzyme composition consisting essentially of:
- a core of a non-acidic carrier material 2.
- a coating layer enrobing said core, the coating layer being a nonionic surface-active agent 3.
- proteolytic enzymes attached to said coating layer 4. an acidic substance, dissolved or dispersed in said coating layer.
- the granular proteolytic enzyme composition also contains an outer layer of a nonionic surface-active agent, in which an acidic substance is dissolved or dispersed.
- the granular proteolytic enzyme composition consists essentially of l. a core of non-acidic carrier material 2. a coating layer of a nonionic surface-active agent enrobing said core, said coating layer containing an acidic substance dissolved or dispersed therein 3. proteolytic enzymes.
- Core of non-acidic carrier material The core of the granules consists of a non-acidic carrier material, i.e. a neutral or alkaline carrier material, from which granules can be made.
- the particle size of the carrier material should lie between 0.05 mm and 1.5 mm, preferably between 0.3 and 1.5 mm.
- the carrier material should have a porosity of lying between 0.15 ml/g and l ml/g preferably between 0.15 and 0.50 ml/g, determined by the mercury method.
- This method consists of adding mercury t0 the carrier material under vacuum and measuring the apparent mercury density in an apparatus as described by J.M. Vleeskens in his Thesis of Delft University, Holland 1959, using the equation (AHg/eHg) volume of pores (M/es), where AHg difference in weight of mercury before and after addition to the sample eHg density of mercury M weight of sample of carrier material as density of sample of carrier material
- the carrier material must be sufficiently strong, i.e. must be non-friable, and may not be hygroscopic.
- Crystal water may be present, provided the carrier material does not melt in its own water of crystallization at temperatures below 40-C (as e.g. Na,SO,-l0 aq).
- Suitable examples of neutral and alkaline carrier materials are alkali metal phosphates, such as penta sodium and penta potassium triphosphate, tetrasodium pyrophosphate, sodium or potassium orthophosphate, sodium or potassium sulphate or mixtures thereof, alkalimetal borates and carbonates, alkalimetal silicates, gelatinized starch and starch derivatives.
- those granulatable carrier materials are preferred that are desirable in a detergent composition, e.g. penta sodium or penta potassium tripolyphosphate.
- the coating layer consists of a nonionic surface-active agent that is liquid or semi-paste-like at room temperature.
- a nonionic surface-active agent that is liquid or semi-paste-like at room temperature.
- suitable nonionic surface-active agents are alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, such as nonylphenol condensed with 10 moles of ethylene oxide, C -C monohydric aliphatic alcohols condensed with 8 to 25 moles of ethylene oxide, such as tallow fatty alcohol condensed with 25 moles of ethylene oxide, isotridccyl alcohol condensed with l 1 moles of ethylene oxide secondary C,,C,,, alcohols condensed with 9 moles of ethylene oxide, fatty acid monoand dialkylol amides with 10 to carbon atoms in the fatty acid residue, and ethoxylated derivatives thereof.
- the acidic substances that are used in the present invention should have an acid pH value, preferably between 4 and 6, in a l%-aqueous solution. Any suitable organic and/or inorganic acid substance may be used, provided it does not afi'ect the enzyme negatively. suitable examples are acid salts, such as sodium or potassium acid pyrophosphate, alkali metal acid orthophosphate, inorganic acids such as phosphoric acid, and organic acids like citric acid and the sodium salt thereof, adipic acid and the like.
- acidic substances which are soluble or dispersible in the nonionic surface-active agent, such as citric acid.
- proteolytic enzymes which can be used in the present invention may be of animal and vegetable origin or may be obtained from micro organisms, including bacteria and fungi. Examples of such proteolytic enzymes are pepsin, trypsin, papain, aspergillus peptidase.
- the preferred proteolytic enzymes are those produced by micro organisms, such as the proteases produced by Bacillus subtilis.
- the commercial proteolytic enzymes are normally in the form of a fine powder containing the enzymes and an inert carrier material, such as sodium or calcium sulphate or clay.
- the preferred proteolytic enzymes are of the subtilisine type, commercially available under the trade names Alcalase and Maxatase.
- Alcalase is a serine protease, produced by Novo lndustrie A/S Copenhagen, by submerged fermentation of a special strain of Bacillus subtilis.
- Maxatase is also a protease, produced from Bacillus subri'lis, manufactured by the Royal Dutch Fermentation Industries at Delft, Holland.
- the granular proteolytic enzyme composition of the present invention can be prepared in various ways. It is preferred to incorporate the acidic substance in the nonionic surface-active agent first, admixing this coating material with the granular carrier material and subsequently affixing the proteolytic enzyme powders thereon.
- the granular proteolytic enzyme compositions are usually further coated with a suitable coating material.
- suitable coating materials are those, which are also suitable as coating agents for the core of the granular proteolytic enzyme compositions as described above, but other film-forming agents such as polyvinylalcohol, polyvinylpyrrolidone, shellac, fatty acids, esters, waxes, etc. can be used.
- the outer coating layer thus formed may also comprise the acidic substance, and it constitutes a preferred embodiment of the present invention when the inner and outer layers contain the acidic substance.
- the layer that contains the acidic substance forms, as it were, an acidic barrier against the harmful influences of e.g. particular ingredients of the detergent composition as well as a barrier to moisture present therein.
- the amount of acidic substance required in the present invention is dependent upon the activity of the proteolytic enzymes as well as upon the amount of proteolytic enzyme present.
- the granular proteolytic enzyme composition should contain an amount of acidic substance such that the weight ratio between the proteolytic enzyme, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10. Preferably the weight ratio is 2:1 to 1:2.
- the ratio between the nonionic surfaceactive agent and acidic substance is from 10:1 to 1:1.
- the acidic substance is from 0.5 to 10 percent, preferably from 2 to 8 percent by weight of the granule.
- the ganular proteolytic enzyme composition is adapted to be particularly formulated with a detergent composition.
- a detergent composition may comprise one or more detergent surfactants, such as anionic and nonionic detergent surfactants, soap and mixtures thereof.
- the detergent composition may contain from 2 to 20 percent by weight of an anionid detergent surfactant.
- an anionid detergent surfactant examples thereof are alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphates with 10 to 24 carbon atoms in the alkyl group, olefinsulphonates prepared by sulphonating straight-chain a-olefms with 10 to 20 carbon atoms and subsequently neutralizing and hydrolyzing the sulphonation reaction product, acylisethionates with 12 to 18 carbon atoms in the acyl-group and acyltaurates with 12 to 18 carbon atoms in the acyl group.
- the composition may furthermore contain 1 to 10 percent by weight of a nonionic detergent surfactant.
- a nonionic detergent surfactant examples thereof are the condensation products of alkylene oxide, such as ethylene oxide and propylene oxide with alcohols having from 12 to 24 carbon atoms in the alkyl group, with alkylphenols having from eight to 18 carbon atoms in the alkyl group, with fatty acid amides with a C -C fatty acid residue, with polyalkyleneglycols and mixed alkylene oxide condensation products.
- compositions may also contain as alkali metal soap in an amount of l to 10 percent by weight.
- alkali metal soaps of C -C fatty acids, such as palm oil-, hardened fish oil, coconut oil, and tallow fatty acids.
- the amount of the different detergent surfactants are 8 to 15 percent by weight of the anionic detergent surfactant 1 to 6 percent by weight of the nonionic detergent surfactant 1 to 5 percent by weight of the alkali metal soap whereas for low sudsing compositions the amounts are: 2 to 9 percent by weight of the anionic detergent surfactant 2 to 10 percent by weight of the nonionic detergent surfactant 5 to 10 percent by weight of the alkali metal soap.
- the remaining part of the composition may consist of the normal constituents of a detergent composition. They may contain from 20 to 50 percent of a condensed phosphate, such as pentasodium triphosphate. 1f desirable, part of the condensed phosphate may be replaced by an organic builder, such as trisodium nitrilotriacetate.
- sodium silicate TABLE ll may be present, 0.5 to 3 percent of sodium carbox- 1 ll 1 ther suitable soil-sus endin Penmdmm y y Ce u 056 P 8 triphosphate s 66 70 66 70 74 agent may be present. if des1red, up to 45 percent by Nonyl phenol weight of a bleaching agent, such as sodium perborate 5 moles of ethylene may be added for heavy-duty purposes.
- a bleaching agent such as sodium perborate 5 moles of ethylene may be added for heavy-duty purposes.
- compositions may furthermore contain alkali g y gqg 8 4 8 4 metal salts, such as sodium sulphate, sodium carbonate, gg i f 16 sodium borates, and furthermore other adjuvants, such Alcalase l6 l6 l6 16 1e 16 as tarnish inhibitors, perfumes, germicides, coloring Numb" l 2 3 4 5 Mann agents, lather modifiers, fluorescers, solvents, bleach precursom
- the granules were prepared from granular an-
- the granular proteolytic enzyme compositions of the y pentasodwm mphosphate havmg a invention may be present in an amount of 0.5- per- (50450 cent, preferably 5-10 percent, by weight of the deter- 15 T Rowdfled Pfoteolyuc enzyme Alcalase was gem composition.
- composition of the granules is The residual activity of the proteolytic enzyme was given in Table IV. determined after 7 days storage of the detergent com- Granules nos. 1 and 4 were prepared in the following position with the enzyme granules at 30C and 80 perway. Citric acid was dispersed in tallow fatty alcohol cent R.H.The results are given in Table l. condensed with 25 moles of ethylene oxide, under TABLE 1 Gluing Grenulatable carrier agent,
- Granules nos. 2 and 6 were prepared in an identical way, with the exception that first solely the tallow fatty alcohol condensed with 25 moles of ethylene oxide was sprayed onto the granular pentasodium triphosphate, and after addition of the proteolytic enzyme powders the citric acid nonionic dispersion was sprayed on the granules so obtained.
- Granules nos. 3 and 5 were prepared as follows. On
- the granular pentasodium triphosphate first the tallow fatty alcohol condensed with 25 moles of ethylene oxide was sprayed, followed by the addition of the dry mixture of the proteolytic enzyme powder and citric acid, and subsequently again the nonionic was sprayed upon the granules.
- Granule no. 7 was prepared by spraying the nonionic on the granular pentasodium triphosphate, adding the enzyme powder and again spraying the nonionic thereupon. Granule no. 7 was made for comparison purposes. All the granules contained 5 percent nonionic in the inner and 5 percent nonionic in the outer layer. From each of these granules, 7.5 percent by weight was added to the detergent composition as given in Example I, and the residual proteolytic activity was determined after 7 days' storage of the composition at 30C and 80 percent relative humidity. The results are also given in Table IV.
- a granular proteolytic enzyme composition adapted to be formulated with a detergent composition, the proteolytic enzyme composition consisting essentially of t i. a core of a non-acidic, non-hygroscopic, nonfriable carrier material selected from the group consisting of alkalimetaltripolyphosphates, -pyrophosphates, -orthophosphates, alkalimetalsulphates, -borates, silicates, -carbonates, gelatinized starch and starch derivatives,
- a coating layer enrobing said core consisting of a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C C monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C alcohols condensed with 9 moles of ethylene oxide, fatty acid mono and dialkyiol amides with 10 to carbon atoms in the fatty acid residue, and ethoxylated derivatives thereof,
- a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C C monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C alcohols condensed with 9 moles of ethylene oxide, fatty acid mono and dialkyiol amides with 10 to carbon atom
- an acidic substance dissolved or dispersed in said coating layer, said acidic substance having a pH of 4 to 6 in a Flu-aqueous solution, selected from the group consisting of citric acid, and adipic acid, said acidic substance being present in an amount of 0.5 to 10 percent by weight of the granule, the weight ratio between the nonionic detergent surfactant coating layer and the acidic substance being from 10:1 to 1:1,
- proteolytic enzymes attached to the coating layer of the core, in such an amount that the weight ratio between the proteolytic activity, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10.
- composition according to claim 1 in which the granular proteolytic enzyme composition comprises furthermore an outer coating layer of the nonionic detergent surfactant, in which the acidic substance has been dispersed or dissolved.
- composition according to claim 1 in which the acidic substance is citric acid.
- composition according to claim 1 in which the amount of the acidic substance is from 2 to 8 percent by weight of the granule.
- a detergent composition consisting essentially of a. from 2 to 20 percent by weight of an anionic detergent surfactant selected from the group consisting of alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphonates with 10 to 24 carbon atoms in the alkyl group, olefinesulphonates with 10 to 20 carbon atoms, acylisethionates with 12 to 18 carbon atoms in the acyl group and acyltaurates with 12 to 18 carbon atoms in the acyl group.
- an anionic detergent surfactant selected from the group consisting of alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphonates with 10 to 24 carbon atoms in the alkyl group, olefinesulphonates with 10 to 20 carbon atoms, acylisethionates with 12 to 18 carbon atoms in the acyl group and acyltaurates
- a nonionic detergent surfactant selected from the group consisting of the condensation products of ethylene oxide or propylene oxide with alcohols having from 12 to 24 carbon atoms in the alkyl group, with alkylphenols having from eight to 18 carbon atoms in the alkyl group, with fatty acid amides with a C -C fatty acid residue, with polyalkyleneglycols and with mixed alkylene oxide condensation products,
- a granular proteolytic enzyme composition consisting essentially of i. a core of a non-acidic, non-hygroscopic, non-friable carrier material selected from the group consisting of a1kalimetaltripolyphosphates, pyrophosphates, -orthophosphates, alkalimetalsulphates, -borates, -si1icates, -carbonates, gelatinized starch and starch derivatives,
- a coating layer enrobing said core consisting of a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C,C, monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C -C alcohols condensed with 9 moles of ethylene oxide, fatty acid monoand dialkylol amides in the fatty acid residue, and ethoxylated derivatives thereof,
- the weight ratio between the nonionic detergent surfactant coating layer and the acidic substance being from 10:1 to 1:1.
- proteolytic enzymes attached to the coating layer of the core, in such an amount that the weight ratio between the proteolytic activity, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10.
Abstract
The invention is directed to an improvement in the storage stability of granular proteolytic enzyme compositions. The proteolytic enzymes are contained in granules to which an acidic substance has been added. The granules will comprise a neutral or alkaline carrier material, for example an alkali metal phosphate; a gluing agent, for example a nonionic surface active agent; a proteolytic enzyme and an acidic material, for example citric acid.
Description
AU 165 x United States Patent 11 1 van Kampen et al.
1 51 Mar. 27, 1973 GRANULAR PROTEOLYTIC ENZYME COMPOSITION Inventors: Daniel Marten van Kampen, Vlaardingen; Foscarina Pasztor nee Rozzo, Abcoude, both of Netherlands Assignee: Lever Brothers Company, New
Y0rk,N.Y.
Filed: June 5, 1972 Appl. No.: 259,638
Related U.S. Application Data Continuation-impart of Ser. No. 20,019, March 16, 1970, abandoned.
US. Cl. ..252/110, 195/63, 195/68, 252/89, 252/91, 252/97, 252/100, 252/132, 252/134, 252/136, 252/142, 252/174,
Int.Cl ..Clld 7/08,Cl1d 7/42,C11d 17/06 Field of Search ....195/63, 68; 252/89, 132,135, 252/D1G. 12
References Cited UNITED STATES PATENTS 12 1971 Davisetal ..252 531 Primary Examiner-Leon D. Rosdol Assistant Examiner-Dennis l... Albrecht Attorney-Louis F. Kline, Jr. et al.
[57] ABSTRACT The invention is directed to an improvement in the storage stability of granular proteolytic enzyme compositions. The proteolytic enzymes are contained in granules to which an acidic substance has been added. The granules will comprise a neutral or alkaline carrier material, for example an alkali metal phosphate; a gluing agent, for example a nonionic surface active agent; a proteolytic enzyme and an acidic material, for example citric acid.
5 Claims, No Drawings GRANULAR PROTEOLYTIC ENZYME COMPOSITION Cross-Reference to Related Application This application is a continuation-in-part of our earlier filed application Ser. No. 20, 019, filed 16th Man, 1970 now abandoned.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to granular proteolytic enzyme compositions, adapted to be formulated with a detergent composition, and to detergent compositions containing these granular proteolytic enzyme compositions.
2. Description of the Prior Art Enzymic cleaning compositions are old. See, for example, German patent specifications 283,923 (Rohm, 1915) and 329,958 (Rohm, 1920). The enzymes aid in cleaning by attacking the soil and stains of the soiled objects to be cleaned. Proteinaceous soil and stains are attacked by proteolytic enzymes. Such proteolytic enzymes, suitable for cleaning purposes, are normally found in the form of fine powders. Such fine powders are difficult to handle and difficult to formulate. When such fine powders are incorporated in detergent compositions, their stability is often greatly impaired by several ingredients of the detergent composition, and by moisture, which may be taken up by the detergent composition during storage. It is believed that this moisture brings the proteolytic enzymes into contact with the other ingredients of the detergent composition, which are harmful to the proteolytic enzymes.
It has already been proposed in US. Pat. No. 3,519,570 to enhance the stability of proteolytic enzymes by bringing them in granular form. This is done by rendering the surfaces of base carried detergent granules glutinous with a low-melting, ordinarily solid, water-soluble nonionic surface-active agent which liquet'ies between lF and 200F, and subsequently conglutinating with said glutinous surfaces the proteolytic enzymes in a powdered form. The granules thus obtained may be additionally coated with the nonionic surface-active agent to encapsulate the proteolytic enzymes and to protect them from moisture and other harmful ingredients.
Although such granular proteolytic enzyme compositions are much more stable than the fine, powdered proteolytic enzymes, their stability in detergent compositions is still often not satisfactory for detergent formulation purposes.
Object of the Invention It is therefore an object of the present invention to further improve the storage stability of granular proteolytic enzyme granules. Further objects will become apparent from the detailed description of the invention given hereafter.
SUMMARY OF THE INVENTION It has been found that incorporating an acidic substance in the nonionic layer of the granular proteolytic enzyme compositions of the type as heretofore described, greatly enhances the storage stability of said granular proteolytic enzyme compositions. The present invention therefore relates to a granular proteolytic enzyme composition, adapted to be formulated with a detergent composition, the granular proteolytic enzyme composition consisting essentially of:
l a core of a non-acidic carrier material 2. a coating layer enrobing said core, the coating layer being a nonionic surface-active agent 3. proteolytic enzymes, attached to said coating layer 4. an acidic substance, dissolved or dispersed in said coating layer.
In another aspect of the invention, the granular proteolytic enzyme composition also contains an outer layer of a nonionic surface-active agent, in which an acidic substance is dissolved or dispersed.
DETAILED DESCRIPTION OF INVENTION The granular proteolytic enzyme composition consists essentially of l. a core of non-acidic carrier material 2. a coating layer of a nonionic surface-active agent enrobing said core, said coating layer containing an acidic substance dissolved or dispersed therein 3. proteolytic enzymes. Core of non-acidic carrier material The core of the granules consists of a non-acidic carrier material, i.e. a neutral or alkaline carrier material, from which granules can be made. The particle size of the carrier material should lie between 0.05 mm and 1.5 mm, preferably between 0.3 and 1.5 mm. The carrier material should have a porosity of lying between 0.15 ml/g and l ml/g preferably between 0.15 and 0.50 ml/g, determined by the mercury method. This method consists of adding mercury t0 the carrier material under vacuum and measuring the apparent mercury density in an apparatus as described by J.M. Vleeskens in his Thesis of Delft University, Holland 1959, using the equation (AHg/eHg) volume of pores (M/es), where AHg difference in weight of mercury before and after addition to the sample eHg density of mercury M weight of sample of carrier material as density of sample of carrier material The carrier material must be sufficiently strong, i.e. must be non-friable, and may not be hygroscopic. Crystal water may be present, provided the carrier material does not melt in its own water of crystallization at temperatures below 40-C (as e.g. Na,SO,-l0 aq). Suitable examples of neutral and alkaline carrier materials are alkali metal phosphates, such as penta sodium and penta potassium triphosphate, tetrasodium pyrophosphate, sodium or potassium orthophosphate, sodium or potassium sulphate or mixtures thereof, alkalimetal borates and carbonates, alkalimetal silicates, gelatinized starch and starch derivatives. In general, those granulatable carrier materials are preferred that are desirable in a detergent composition, e.g. penta sodium or penta potassium tripolyphosphate.
Coating Layer The coating layer consists of a nonionic surface-active agent that is liquid or semi-paste-like at room temperature. Higher melting liquefiable nonionic surfaceactive agents may also be used. Examples of suitable nonionic surface-active agents are alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, such as nonylphenol condensed with 10 moles of ethylene oxide, C -C monohydric aliphatic alcohols condensed with 8 to 25 moles of ethylene oxide, such as tallow fatty alcohol condensed with 25 moles of ethylene oxide, isotridccyl alcohol condensed with l 1 moles of ethylene oxide secondary C,,C,,, alcohols condensed with 9 moles of ethylene oxide, fatty acid monoand dialkylol amides with 10 to carbon atoms in the fatty acid residue, and ethoxylated derivatives thereof. Other suitable nonionics can be found in Schick, MJ. Nonionic Surfactants 1967, which is hereby incorporated by way of Reference.
Acidic Substance The acidic substances that are used in the present invention should have an acid pH value, preferably between 4 and 6, in a l%-aqueous solution. Any suitable organic and/or inorganic acid substance may be used, provided it does not afi'ect the enzyme negatively. suitable examples are acid salts, such as sodium or potassium acid pyrophosphate, alkali metal acid orthophosphate, inorganic acids such as phosphoric acid, and organic acids like citric acid and the sodium salt thereof, adipic acid and the like.
Particularly preferred are acidic substances which are soluble or dispersible in the nonionic surface-active agent, such as citric acid.
Proteolytic enzymes The proteolytic enzymes which can be used in the present invention may be of animal and vegetable origin or may be obtained from micro organisms, including bacteria and fungi. Examples of such proteolytic enzymes are pepsin, trypsin, papain, aspergillus peptidase. The preferred proteolytic enzymes are those produced by micro organisms, such as the proteases produced by Bacillus subtilis. The commercial proteolytic enzymes are normally in the form of a fine powder containing the enzymes and an inert carrier material, such as sodium or calcium sulphate or clay. The preferred proteolytic enzymes are of the subtilisine type, commercially available under the trade names Alcalase and Maxatase. Alcalase is a serine protease, produced by Novo lndustrie A/S Copenhagen, by submerged fermentation of a special strain of Bacillus subtilis. Maxatase is also a protease, produced from Bacillus subri'lis, manufactured by the Royal Dutch Fermentation Industries at Delft, Holland.
The granular proteolytic enzyme composition of the present invention can be prepared in various ways. It is preferred to incorporate the acidic substance in the nonionic surface-active agent first, admixing this coating material with the granular carrier material and subsequently affixing the proteolytic enzyme powders thereon.
The granular proteolytic enzyme compositions are usually further coated with a suitable coating material. Suitable coating materials are those, which are also suitable as coating agents for the core of the granular proteolytic enzyme compositions as described above, but other film-forming agents such as polyvinylalcohol, polyvinylpyrrolidone, shellac, fatty acids, esters, waxes, etc. can be used.
The outer coating layer thus formed may also comprise the acidic substance, and it constitutes a preferred embodiment of the present invention when the inner and outer layers contain the acidic substance. The layer that contains the acidic substance forms, as it were, an acidic barrier against the harmful influences of e.g. particular ingredients of the detergent composition as well as a barrier to moisture present therein.
The amount of acidic substance required in the present invention is dependent upon the activity of the proteolytic enzymes as well as upon the amount of proteolytic enzyme present. In general, the granular proteolytic enzyme composition should contain an amount of acidic substance such that the weight ratio between the proteolytic enzyme, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10. Preferably the weight ratio is 2:1 to 1:2. The ratio between the nonionic surfaceactive agent and acidic substance is from 10:1 to 1:1. The acidic substance is from 0.5 to 10 percent, preferably from 2 to 8 percent by weight of the granule. The ganular proteolytic enzyme composition is adapted to be particularly formulated with a detergent composition. Such a detergent composition may comprise one or more detergent surfactants, such as anionic and nonionic detergent surfactants, soap and mixtures thereof.
In general, the detergent composition may contain from 2 to 20 percent by weight of an anionid detergent surfactant. Examples thereof are alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphates with 10 to 24 carbon atoms in the alkyl group, olefinsulphonates prepared by sulphonating straight-chain a-olefms with 10 to 20 carbon atoms and subsequently neutralizing and hydrolyzing the sulphonation reaction product, acylisethionates with 12 to 18 carbon atoms in the acyl-group and acyltaurates with 12 to 18 carbon atoms in the acyl group. The composition may furthermore contain 1 to 10 percent by weight of a nonionic detergent surfactant. Examples thereof are the condensation products of alkylene oxide, such as ethylene oxide and propylene oxide with alcohols having from 12 to 24 carbon atoms in the alkyl group, with alkylphenols having from eight to 18 carbon atoms in the alkyl group, with fatty acid amides with a C -C fatty acid residue, with polyalkyleneglycols and mixed alkylene oxide condensation products.
The compositions may also contain as alkali metal soap in an amount of l to 10 percent by weight. Examples thereof are the alkali metal soaps of C -C fatty acids, such as palm oil-, hardened fish oil, coconut oil, and tallow fatty acids.
For medium sudsing compositions the amount of the different detergent surfactants are 8 to 15 percent by weight of the anionic detergent surfactant 1 to 6 percent by weight of the nonionic detergent surfactant 1 to 5 percent by weight of the alkali metal soap whereas for low sudsing compositions the amounts are: 2 to 9 percent by weight of the anionic detergent surfactant 2 to 10 percent by weight of the nonionic detergent surfactant 5 to 10 percent by weight of the alkali metal soap. The remaining part of the composition may consist of the normal constituents of a detergent composition. They may contain from 20 to 50 percent of a condensed phosphate, such as pentasodium triphosphate. 1f desirable, part of the condensed phosphate may be replaced by an organic builder, such as trisodium nitrilotriacetate.
Furthermore, from 2 to 10 percent of sodium silicate TABLE ll may be present, 0.5 to 3 percent of sodium carbox- 1 ll 1 ther suitable soil-sus endin Penmdmm y y Ce u 056 P 8 triphosphate s 66 70 66 70 74 agent may be present. if des1red, up to 45 percent by Nonyl phenol weight of a bleaching agent, such as sodium perborate 5 moles of ethylene may be added for heavy-duty purposes. made 0 10 10 to 10 The compositions may furthermore contain alkali g y gqg 8 4 8 4 metal salts, such as sodium sulphate, sodium carbonate, gg i f 16 sodium borates, and furthermore other adjuvants, such Alcalase l6 l6 l6 16 1e 16 as tarnish inhibitors, perfumes, germicides, coloring Numb" l 2 3 4 5 Mann agents, lather modifiers, fluorescers, solvents, bleach precursom The granules were prepared from granular an- The granular proteolytic enzyme compositions of the y pentasodwm mphosphate havmg a invention may be present in an amount of 0.5- per- (50450 cent, preferably 5-10 percent, by weight of the deter- 15 T Rowdfled Pfoteolyuc enzyme Alcalase was gem composition. m1xed wlth the ac1d1c substance and subsequently at- Examples of detergent compositions according to the f l to Y F material by means of "iropwlsc invention will now be given by way of illustration only dmon of hqud fmnylphenol condensed 10 moles dm Ji it fi manner. of ethylene mode. The granules thus formed were coated by means of a second layer of the nonionic. EXAMPLE I These granules were sieved with a sieve with apertures Granules of the composition as given in Table I were of mm and add! m an amount of 5 percent to prepared by dry mixing the granular anhydrous carrier the detergent compos1t1on of Example [.gStorage tests materials having a particle size of 50-250 y. with a comwere "3 out f Several weeks f C 80 mercially available powdered proteolytic enzyme, m lanlmated and l f carton manufactured by submerged fermentation with a strain talnem The residual e zym ic activity was deterof Bacillus subtilis known under the trade name Almmedthe results ofwhlch are Shownm Tablem calase (w1th an act1v1ty of 1.5 Anson umtlg), 1n a mlx- TABLE m mg apparatus. Subsequently th1s dry m1xture was 30 granulated by quickly dropwise adding liquid nol r d a a i ity (in granu e nylphenol condensed with 10 moles of ethylene oxide, l week 3 weeks 4 weeks 6 weeks 8 weeks to whlch c1tr1c ac1d had been added first. The granules not not not not not obtained were then sieved with a sieve having apertures l m m l l of 0.5-1 mm andadded in an amount of5 percent to 1 88 59 "1; 47 15 detergent compositlon of the following formula: 2 57 109 12 74 o 19 0 as 0 47 3 5O 96 i0 77 5 72 0 36 0 5O 4 37 i0 54 5 44 0 25 0 l4 sodium salt of straight ehaln 5 35 97 i2 72 4 5i 4 40 0 22 dodecylbenzenesulphonate 5.5 6 26 78 9 56 l 44 0 24 0 9 sodium soap of commercial stearic acid 8.0 40 nonylphenol condensed with l4 moles of ethylene oxide 3.0 EXAMPLE "I 3:2 Several enzyme-containing granules were prepared sodium carboxymethylcellulose 1.0 from granular pentasodium triphosphate which had a gggfi figg gf 33g particle size of 50-250 1; and a powdered proteolytic wamPeHumeem my 45 enzyme from Bacillus subtilis, sold under the trade name Maxatase. The composition of the granules is The residual activity of the proteolytic enzyme was given in Table IV. determined after 7 days storage of the detergent com- Granules nos. 1 and 4 were prepared in the following position with the enzyme granules at 30C and 80 perway. Citric acid was dispersed in tallow fatty alcohol cent R.H.The results are given in Table l. condensed with 25 moles of ethylene oxide, under TABLE 1 Gluing Grenulatable carrier agent,
material nonylphenol Anhydrous Anhydrous condensed Percent pentasodium dlsodium Enzyme, with 10 residual triphosacid pyroalcalase Acidic moles of activity Number phate phosphate (proteolytic substance ethylene alter of granule (powder) (powder) enzyme) citric acid oxide 7 days EXAMPLE ll 5 heating to C in a homogenisator for half an hour. The dispersion was a clear liquid, which became Granules were prepared of the composition as given viscous at lower temperatures. This dispersion was in Table ll. heated up and sprayed on the granular pentasodium triphosphate by means of a two-fluid nozzle. Subsequently the powdered enzymes were added, and on the so-obtained granules again the dispersion of citric acid in the nonionic was sprayed.
Granules nos. 2 and 6 were prepared in an identical way, with the exception that first solely the tallow fatty alcohol condensed with 25 moles of ethylene oxide was sprayed onto the granular pentasodium triphosphate, and after addition of the proteolytic enzyme powders the citric acid nonionic dispersion was sprayed on the granules so obtained.
Granules nos. 3 and 5 were prepared as follows. On
the granular pentasodium triphosphate first the tallow fatty alcohol condensed with 25 moles of ethylene oxide was sprayed, followed by the addition of the dry mixture of the proteolytic enzyme powder and citric acid, and subsequently again the nonionic was sprayed upon the granules.
Granule no. 7 was prepared by spraying the nonionic on the granular pentasodium triphosphate, adding the enzyme powder and again spraying the nonionic thereupon. Granule no. 7 was made for comparison purposes. All the granules contained 5 percent nonionic in the inner and 5 percent nonionic in the outer layer. From each of these granules, 7.5 percent by weight was added to the detergent composition as given in Example I, and the residual proteolytic activity was determined after 7 days' storage of the composition at 30C and 80 percent relative humidity. The results are also given in Table IV.
TAB LE IV Granular carrier Percent material, citric Percent Parcmtt percent acid in citric citric pentainner acid dry acid in lcrcent sodium layer mixed outer residual Granule. trlphos- (5% with 16% layer proteolytic number phate nonionic) enzyme (5%) activity What is claimed is:
l. A granular proteolytic enzyme composition, adapted to be formulated with a detergent composition, the proteolytic enzyme composition consisting essentially of t i. a core of a non-acidic, non-hygroscopic, nonfriable carrier material selected from the group consisting of alkalimetaltripolyphosphates, -pyrophosphates, -orthophosphates, alkalimetalsulphates, -borates, silicates, -carbonates, gelatinized starch and starch derivatives,
. a coating layer enrobing said core, consisting of a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C C monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C alcohols condensed with 9 moles of ethylene oxide, fatty acid mono and dialkyiol amides with 10 to carbon atoms in the fatty acid residue, and ethoxylated derivatives thereof,
iii. an acidic substance, dissolved or dispersed in said coating layer, said acidic substance having a pH of 4 to 6 in a Flu-aqueous solution, selected from the group consisting of citric acid, and adipic acid, said acidic substance being present in an amount of 0.5 to 10 percent by weight of the granule, the weight ratio between the nonionic detergent surfactant coating layer and the acidic substance being from 10:1 to 1:1,
iiii. proteolytic enzymes, attached to the coating layer of the core, in such an amount that the weight ratio between the proteolytic activity, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10.
2. A composition according to claim 1, in which the granular proteolytic enzyme composition comprises furthermore an outer coating layer of the nonionic detergent surfactant, in which the acidic substance has been dispersed or dissolved.
3. A composition according to claim 1, in which the acidic substance is citric acid.
4. A composition according to claim 1, in which the amount of the acidic substance is from 2 to 8 percent by weight of the granule.
5. A detergent composition consisting essentially of a. from 2 to 20 percent by weight of an anionic detergent surfactant selected from the group consisting of alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphonates with 10 to 24 carbon atoms in the alkyl group, olefinesulphonates with 10 to 20 carbon atoms, acylisethionates with 12 to 18 carbon atoms in the acyl group and acyltaurates with 12 to 18 carbon atoms in the acyl group.
. from 1 to 10 percent by weight of a nonionic detergent surfactant selected from the group consisting of the condensation products of ethylene oxide or propylene oxide with alcohols having from 12 to 24 carbon atoms in the alkyl group, with alkylphenols having from eight to 18 carbon atoms in the alkyl group, with fatty acid amides with a C -C fatty acid residue, with polyalkyleneglycols and with mixed alkylene oxide condensation products,
. from 1 to 10 percent by weight of an alkalimetal soap of C,,-C fatty acids,
. from 20 to 50 percent by weight ofa water-soluble alkalimetal builder salt,
. from 0 to 45 percent by weight of a bleaching agent,
f. from 0.5 to 15 percent by weight of a granular proteolytic enzyme composition consisting essentially of i. a core of a non-acidic, non-hygroscopic, non-friable carrier material selected from the group consisting of a1kalimetaltripolyphosphates, pyrophosphates, -orthophosphates, alkalimetalsulphates, -borates, -si1icates, -carbonates, gelatinized starch and starch derivatives,
ii. a coating layer enrobing said core, consisting of a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C,C, monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C -C alcohols condensed with 9 moles of ethylene oxide, fatty acid monoand dialkylol amides in the fatty acid residue, and ethoxylated derivatives thereof,
iii. an acidic substance, dissolved or dispersed in the granule, the weight ratio between the nonionic detergent surfactant coating layer and the acidic substance being from 10:1 to 1:1.
iiii. proteolytic enzymes, attached to the coating layer of the core, in such an amount that the weight ratio between the proteolytic activity, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10.
Claims (4)
- 2. A composition according to claim 1, in which the granular proteolytic enzyme composition comprises furthermore an outer coating layer of the nonionic detergent surfactant, in which the acidic substance has been dispersed or dissolved.
- 3. A composition according to claim 1, in which the acidic substance is citric acid.
- 4. A composition according to claim 1, in which the amount of the acidic substance is from 2 to 8 percent by weight of the granule.
- 5. A detergent composition consisting essentially of a. from 2 to 20 percent by weight of an anionic detergent surfactant selected from the group consisting of alkylbenzenesulphonates with 12 to 18 carbon atoms in the alkyl group, alkylsulphonates with 10 to 24 carbon atoms in the alkyl group, olefinesulphonates with 10 to 20 carbon atoms, acylisethionates with 12 to 18 carbon atoms in the acyl group and acyltaurates with 12 to 18 carbon atoms in the acyl group. b. from 1 to 10 percent by weight of a nonionic detergent surfactant selected from the group consisting of the condensation products of ethylene oxide or propylene oxide with alcohols having from 12 to 24 carbon atoms in the alkyl group, with alkylphenols having from eight to 18 carbon atoms in the alkyl group, with fatty acid amides with a C10-C24 fatty acid residue, with polyalkyleneglycols and with mixed alkylene oxide condensation products, c. from 1 to 10 percent by weight of an alkalimetal soap of C12-C22 fatty acids, d. from 20 to 50 percent by weight of a water-soluble alkalimetal builder salt, e. from 0 to 45 percent by weight of a bleaching agent, f. from 0.5 to 15 percent by weight of a granular proteolytic enzyme composition consisting essentially of i. a core of a non-acidic, non-hygroscopic, non-friable carrier material selected from the group consisting of alkalimetaltripolyphosphates, -pyrophosphates, -orthophosphates, alkalimetalsulphates, -borates, -silicates, -carbonates, gelatinized starch and starch derivatives, ii. a coating layer enrobing said core, consisting of a nonionic detergent surfactant selected from the group of alkyl phenols with eight to 18 carbon atoms in the alkyl chain, and condensed with 8 to 15 moles of ethylene oxide, C8-C20 monohydric aliphatic alcohols condensed with 6 to 25 moles of ethylene oxide, secondary C11-C15 alcohols condensed with 9 moles of ethylene oxide, fatty acid mono- and dialkylol amides in the fatty acid residue, and ethoxylated derivatives thereof, iii. an acidic substance, dissolved or dispersed in said coating layer, said acidic substance having a pH of 4 to 6 in a 1%-aqueous solution, selected from the group consisting of citric acid and adipic acid, said acidic substance being present in an amount of 0.5 to 10 percent by weight of the granule, the weight ratio between the nonionic detergent surfactant coating layer and the acidic substance being from 10:1 to 1:1. iiii. proteolytic enzymes, attached to the coating layer of the core, in such an amount that the weight ratio between the proteolytic activity, calculated to a standard activity of 1.5 Anson unit/g, and the acidic substance is from 10:1 to 1:10.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25963872A | 1972-06-05 | 1972-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3723327A true US3723327A (en) | 1973-03-27 |
Family
ID=22985741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3723327D Expired - Lifetime US3723327A (en) | 1972-06-05 | 1972-06-05 | Granular proteolytic enzyme composition |
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| US (1) | US3723327A (en) |
Cited By (33)
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| US3962149A (en) * | 1973-10-12 | 1976-06-08 | Colgate-Palmolive Company | Non-phosphate spray dried detergents containing dicarboxylic acid salts |
| US3975280A (en) * | 1974-03-21 | 1976-08-17 | Henkel & Cie G.M.B.H. | Storage-stable, readily-soluble detergent additives, coating compositions and process |
| US3997470A (en) * | 1971-10-20 | 1976-12-14 | Mallinckrodt, Inc. | Surfactant containing reagent formulations for assaying biological specimens and methods of preparing same |
| US4016041A (en) * | 1975-02-12 | 1977-04-05 | Lever Brothers Company | Process of making granular enzymes of reduced stickiness |
| FR2369339A1 (en) * | 1976-11-01 | 1978-05-26 | Unilever Nv | NEW LIQUID ENZYMATIC DETERGENT COMPOSITION WITH IMPROVED STORAGE STABILITY |
| US4096870A (en) * | 1977-06-09 | 1978-06-27 | Burton, Parsons And Company, Inc. | Method for cleaning soft hydrophilic gel contact lenses |
| US4106991A (en) * | 1976-07-07 | 1978-08-15 | Novo Industri A/S | Enzyme granulate composition and process for forming enzyme granulates |
| US4113644A (en) * | 1975-02-20 | 1978-09-12 | Ashcraft William R | Protected glassy phosphate detergent additive |
| US4115307A (en) * | 1974-12-13 | 1978-09-19 | Erco Industries Limited | Phosphate composition |
| US4242219A (en) * | 1977-07-20 | 1980-12-30 | Gist-Brocades N.V. | Novel enzyme particles and their preparation |
| US4381247A (en) * | 1980-10-24 | 1983-04-26 | Kao Soap Co., Ltd. | Enzyme-containing bleaching composition |
| US4404128A (en) * | 1981-05-29 | 1983-09-13 | The Procter & Gamble Company | Enzyme detergent composition |
| US4534876A (en) * | 1983-05-10 | 1985-08-13 | Deblauwe Lier B.V. | Method for washing of textiles in hard water and phosphate-free detergent compositions for use therein |
| US4552679A (en) * | 1984-03-16 | 1985-11-12 | Warner-Lambert Company | Method for deodorizing hypochlorite denture cleansing solutions and product containing a delayed release hypochlorite deactivator |
| US4576727A (en) * | 1982-05-12 | 1986-03-18 | Deblaueve Lier B.V. | Phosphate-free detergent composition for washing of textiles in hard water |
| US4671972A (en) * | 1984-03-16 | 1987-06-09 | Warner-Lambert Company | Controlled release encapsulated hypochlorite deactivator for use in denture cleansers |
| US4707287A (en) * | 1985-06-28 | 1987-11-17 | The Procter & Gamble Company | Dry bleach stable enzyme composition |
| US4711739A (en) * | 1986-12-18 | 1987-12-08 | S. C. Johnson & Son, Inc. | Enzyme prespotter composition stabilized with water insoluble polyester or polyether polyol |
| US4767570A (en) * | 1985-07-15 | 1988-08-30 | Rhone-Poulenc Chimie De Base | Sodium tripolyphosphate carrier particles containing a sodium hydrogen ortho on pyro-phosphate |
| US4801544A (en) * | 1984-09-12 | 1989-01-31 | The Clorox Company | Method of improving the storage life of liquid compositions containing enzymes |
| US4874537A (en) * | 1988-09-28 | 1989-10-17 | The Clorox Company | Stable liquid nonaqueous detergent compositions |
| US4919834A (en) * | 1988-09-28 | 1990-04-24 | The Clorox Company | Package for controlling the stability of a liquid nonaqueous detergent |
| US4965012A (en) * | 1987-04-17 | 1990-10-23 | Olson Keith E | Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches |
| US4973417A (en) * | 1986-05-21 | 1990-11-27 | Novo Industri A/S | Enteric coated detergent enzymes |
| US5002687A (en) * | 1989-04-13 | 1991-03-26 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric washing compositions |
| US5336424A (en) * | 1992-12-23 | 1994-08-09 | Eftichios Van Vlahakis | Improved urinal block composition |
| US5468622A (en) * | 1990-04-03 | 1995-11-21 | Immunomatrix, Inc. | Salt stabilization of antibody-enzyme conjugates heat-dried into paper |
| US5733763A (en) * | 1988-08-19 | 1998-03-31 | Novo Nordisk A/S | Enzyme granulate formed of an enzyme-containing core and an enzyme-containing shell |
| US5741693A (en) * | 1992-07-02 | 1998-04-21 | Novo Nordisk A/S | Alkalophilic bacillus SP. AC13 and protease, xylanase, cellulase obtainable therefrom |
| US6136772A (en) * | 1996-04-12 | 2000-10-24 | Novo Nordisk A/S | Enzyme-containing granules and process for the production thereof |
| US20060252667A1 (en) * | 2004-02-13 | 2006-11-09 | Mort Paul R Iii | Active containing delivery particle |
| US20150189900A1 (en) * | 2014-01-07 | 2015-07-09 | Ian Mackay | Process for Producing Protein Concentrate or Isolate and Cellulosic Thermochemical Feedstock From Distillers Grains |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997470A (en) * | 1971-10-20 | 1976-12-14 | Mallinckrodt, Inc. | Surfactant containing reagent formulations for assaying biological specimens and methods of preparing same |
| US3962149A (en) * | 1973-10-12 | 1976-06-08 | Colgate-Palmolive Company | Non-phosphate spray dried detergents containing dicarboxylic acid salts |
| US3975280A (en) * | 1974-03-21 | 1976-08-17 | Henkel & Cie G.M.B.H. | Storage-stable, readily-soluble detergent additives, coating compositions and process |
| US3962107A (en) * | 1974-06-24 | 1976-06-08 | Johnson & Johnson | Enzyme-containing denture cleanser tablet |
| US4115307A (en) * | 1974-12-13 | 1978-09-19 | Erco Industries Limited | Phosphate composition |
| US4016041A (en) * | 1975-02-12 | 1977-04-05 | Lever Brothers Company | Process of making granular enzymes of reduced stickiness |
| US4113644A (en) * | 1975-02-20 | 1978-09-12 | Ashcraft William R | Protected glassy phosphate detergent additive |
| US4106991A (en) * | 1976-07-07 | 1978-08-15 | Novo Industri A/S | Enzyme granulate composition and process for forming enzyme granulates |
| FR2369339A1 (en) * | 1976-11-01 | 1978-05-26 | Unilever Nv | NEW LIQUID ENZYMATIC DETERGENT COMPOSITION WITH IMPROVED STORAGE STABILITY |
| US4096870A (en) * | 1977-06-09 | 1978-06-27 | Burton, Parsons And Company, Inc. | Method for cleaning soft hydrophilic gel contact lenses |
| US4242219A (en) * | 1977-07-20 | 1980-12-30 | Gist-Brocades N.V. | Novel enzyme particles and their preparation |
| US4381247A (en) * | 1980-10-24 | 1983-04-26 | Kao Soap Co., Ltd. | Enzyme-containing bleaching composition |
| US4404128A (en) * | 1981-05-29 | 1983-09-13 | The Procter & Gamble Company | Enzyme detergent composition |
| US4576727A (en) * | 1982-05-12 | 1986-03-18 | Deblaueve Lier B.V. | Phosphate-free detergent composition for washing of textiles in hard water |
| US4534876A (en) * | 1983-05-10 | 1985-08-13 | Deblauwe Lier B.V. | Method for washing of textiles in hard water and phosphate-free detergent compositions for use therein |
| US4552679A (en) * | 1984-03-16 | 1985-11-12 | Warner-Lambert Company | Method for deodorizing hypochlorite denture cleansing solutions and product containing a delayed release hypochlorite deactivator |
| US4671972A (en) * | 1984-03-16 | 1987-06-09 | Warner-Lambert Company | Controlled release encapsulated hypochlorite deactivator for use in denture cleansers |
| US4801544A (en) * | 1984-09-12 | 1989-01-31 | The Clorox Company | Method of improving the storage life of liquid compositions containing enzymes |
| US4707287A (en) * | 1985-06-28 | 1987-11-17 | The Procter & Gamble Company | Dry bleach stable enzyme composition |
| US4767570A (en) * | 1985-07-15 | 1988-08-30 | Rhone-Poulenc Chimie De Base | Sodium tripolyphosphate carrier particles containing a sodium hydrogen ortho on pyro-phosphate |
| US4973417A (en) * | 1986-05-21 | 1990-11-27 | Novo Industri A/S | Enteric coated detergent enzymes |
| US4711739A (en) * | 1986-12-18 | 1987-12-08 | S. C. Johnson & Son, Inc. | Enzyme prespotter composition stabilized with water insoluble polyester or polyether polyol |
| US4965012A (en) * | 1987-04-17 | 1990-10-23 | Olson Keith E | Water insoluble encapsulated enzymes protected against deactivation by halogen bleaches |
| US5733763A (en) * | 1988-08-19 | 1998-03-31 | Novo Nordisk A/S | Enzyme granulate formed of an enzyme-containing core and an enzyme-containing shell |
| US4874537A (en) * | 1988-09-28 | 1989-10-17 | The Clorox Company | Stable liquid nonaqueous detergent compositions |
| US4919834A (en) * | 1988-09-28 | 1990-04-24 | The Clorox Company | Package for controlling the stability of a liquid nonaqueous detergent |
| US5002687A (en) * | 1989-04-13 | 1991-03-26 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric washing compositions |
| US5468622A (en) * | 1990-04-03 | 1995-11-21 | Immunomatrix, Inc. | Salt stabilization of antibody-enzyme conjugates heat-dried into paper |
| US5637468A (en) * | 1990-04-03 | 1997-06-10 | Immunomatrix, Inc. | Salt stabilization of antibody-enzyme conjugates heat-dried into paper |
| US5741693A (en) * | 1992-07-02 | 1998-04-21 | Novo Nordisk A/S | Alkalophilic bacillus SP. AC13 and protease, xylanase, cellulase obtainable therefrom |
| US5489415A (en) * | 1992-12-23 | 1996-02-06 | Eftichios Van Vlahakis | Urinal block dispenser assembly and composition |
| US5336424A (en) * | 1992-12-23 | 1994-08-09 | Eftichios Van Vlahakis | Improved urinal block composition |
| US6136772A (en) * | 1996-04-12 | 2000-10-24 | Novo Nordisk A/S | Enzyme-containing granules and process for the production thereof |
| US6403549B1 (en) | 1996-04-12 | 2002-06-11 | Novozymes A/S | Enzyme-containing granules and process for the production thereof |
| US6589929B2 (en) | 1996-04-12 | 2003-07-08 | Novozymes A/S | Enzyme-containing granules and process for the production thereof |
| US20060252667A1 (en) * | 2004-02-13 | 2006-11-09 | Mort Paul R Iii | Active containing delivery particle |
| US7671005B2 (en) * | 2004-02-13 | 2010-03-02 | The Procter & Gamble Company | Active containing delivery particle |
| US20100113321A1 (en) * | 2004-02-13 | 2010-05-06 | Mort Iii Paul R | Active containing delivery particle |
| US20100267604A1 (en) * | 2004-02-13 | 2010-10-21 | Mort Iii Paul R | Active containing delivery particle |
| US20110067735A1 (en) * | 2004-02-13 | 2011-03-24 | Mort Iii Paul R | Active containing delivery particle |
| US20150189900A1 (en) * | 2014-01-07 | 2015-07-09 | Ian Mackay | Process for Producing Protein Concentrate or Isolate and Cellulosic Thermochemical Feedstock From Distillers Grains |
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