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Publication numberUS3784476 A
Publication typeGrant
Publication dateJan 8, 1974
Filing dateDec 17, 1971
Priority dateNov 29, 1966
Also published asDE1617232A1, DE1617232C2
Publication numberUS 3784476 A, US 3784476A, US-A-3784476, US3784476 A, US3784476A
InventorsVan Kampen D, Weenen J
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent composition
US 3784476 A
Abstract  available in
Images(4)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent "ice Claims priority, applicatigr;I 6lau xembourg, Oct. 16, 1967,

Int. Cl. Clld 7/42 US. Cl. 252-409 4 Claims ABSTRACT OF THE DISCLOSURE A particulate enzyme-containing detergent composition contains. a detergent surface-active agent, a water-soluble builder salt and discrete, shaped inorganic solids containing proteolytic or amylolytic enzymes.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a continuation-in-part of our earlier application .Ser. No. 161,970, filed July 12, 1971, now abandoned, which" in turn is a continuation application of ourearlier application Ser. No.7'67,511, filed Oct. 14, 1968,. now abandoned.

BACKGROUND OFTII-IEINVENTION Field of the invention k The present invention relates to a particulate detergent composition comprising enzymes. More specifically the presentinvention relates to a particulate detergent com' position which essentially consists of from 2 to 20% by weight of an anionic detergent surface-active agent, from 1 to 10% by weight of a nonionic detergent surface-active agent, from 1 to 10% by weight of an alkali-metal soap of fatty acids, from 20 to 50% by weight of a water-soluble alkali-metal builder salt, from 0 to 45% by weight of an oxygen-liberating bleaching agent and from ,0.5 to 15% by weight of mechanically worked discrete, shaped inorganic solids whichcontain enzymes homogeneously distributed therein, said discrete, shaped inorganic solids con-t sisting essentially of: v I

(a) A solid inorganic material selected from the group consisting of sodium and potassium sulphate, sodium and potassium carbonate, sodium bicarbonate, sodium and potassium ortho-,' pyroand tripolyphosphate, sodium borate, ammonium carbonate and BicarbOnateQammQnium v chloride, acid sodium" and potassium orthoand pyrophosphate, and boric' acid, and I (b) Amylolytic or proteolytic enzymes, in avweight 1 ratio of (a) to(b) of 1':100't o 100:1, saiddi'screte, shaped inorganic solids weighing between 0.05 mg. and 100 mg. and being present in the detergent composition in such an amount that the final detergent composition has an amylolytic activity of 10 -10 maltose unit s perkg'or a proteolytic activity of -20 Anson units per kg.

Description of the prior art 3,784,476 Patented Jan. 8, 1974 the handling of these enzyme powders and the dosing thereof into the powder, as Well as the homogeneous mixing of these enzyme powders with the detergent powder, often present problems because it is not so easy to control the'homogeneity of the powder.

It has already been proposed in US. patent specification 3,519,570 to overcome some of the above-mentioned drawbacks by producing enzymatic detergent compositions in a special way. According to this disclosure, the surfaces of detergent base granules are rendered glutinous with a low-melting, ordinarily solid nonionic surface-active agent, after which said glutinous surfaces are conglutinated with powdered enzymes. This process however requires careful control of process conditions, and caking of the enzyme granules so obtained with particles of the detergent powder is not always prevented.

In British patent specification 265,024 the use of enzymes, in particular tryptic enzymes, in soap is disclosed, whereby the enzymes are dehydrated to a water content not exceeding 10% to improve their storage stability. However, these dehydrated enzymes must be protected from moisture to prevent the injurious influence thereof.

SUMMARY OF THE INVENTION In accordance with this invention it has been found that the above-mentioned disadvantages can be significantly reduced if the enzymes are incorporated in the particulate detergent composition in the form of discrete, shaped inorganic solids wherein the enzymes are homogeneously distributed by mechanical Working. These shaped solids are easily produced, and dosing of them is a simple operation. The storage stability of the enzymes when present in discrete, shaped solids in a detergent composition is significantly improved.

DESCRIPTION OF THE INVENTION The detergent composition of the invention consists vessentially of:

"(a) from 2 to 20% by weight of an anionic detergent carbon atoms in the alkyl group, alkali-metal alkyl sulphonates with 10 to 24 carbon atoms in the alkyl group, alkali-metal olefin sulphonates with 10 to 20 carbon atomsand alkali-metal alkyl sulphates with 10 to 24 carbon atoms in the alkyl group;

(b) from 1 to 10% by weight of a nonionic detergent surface-active agent selected from the group consisting of the condensation products of ethylene oxide or pro- ,pylene oxide with monohydric alcohols having from 12 to 24 carbon atoms in their alkyl group, with alkylphenols having from 8 to18 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;

(c) from 1 to 10% by weight of an alkali-metal soap of C C fatty acids;

(d) from 20 to 50% by weight of a water-soluble alkalimetal builder salt selected from the group consisting of orthophosphates, pyrophosphates, tripolyphosphate, aminopolycarboxylates, carbonates and silicates;

(e) from 0 to 45 by weight of an oxygen-liberating bleaching agent; and 3 (f) from 0.5 to 15 by weight of mechanically worked discrete, shaped inorganic solids which contain enzymes homogeneously distributed therein, said discrete, shaped inorganic solids consisting essentially of:

(a) a solid inorganic material selected from the group consisting of sodium and potassium sulphate, sodium and potassium carbonate, sodium bicarbonate, sodium and potassium ortho-, pyrophate, and boric acid, and

(b) amylolytic or proteolytic enzymes, in a weight ratio of (a) to (b) of 1:100 to 100:1, said discrete shaped inorganic solids weighing between 0.05 mg. and 100 mg. and being present in the detergent composition in such an amount that the final detergent composition has an amylolytic activity of 10 maltose units per kg. or a proteolytic activity of 5-20 Anson units per kg.

Examples of suitable anionic detergent surface-active agents are alkali-metal salts of alkylbenzene sulphonates with 12 to 18 carbon atoms in the alkyl group; of C -C alkyl sulphates and sulphonates; of C -C olefin sulphonates which are sulphonation products of C -C olefins, particularly OL-OIefiHS, which have been neutralized and hydrolyzed. Further suitable examples of anionic detergent surface-active agents can be found in Schwartz, Perry and Berch Surface-active Agents and Detergents, vol. II, 1958 under the heading Anionic Surfactants, which is hereby incorporated by way of reference.

Examples of suitable nonionic detergent surface-active agents are ethylene oxide or propylene oxide condensation products with primary or secondary monohydric C -C alcohols, with 0 -0 alkylphenols, with C -C fatty acid amides, with polyalkylene glycols and mixed alkylene oxide condensation products. Further suitable examples can be found in the above-mentioned reference Schwartz, Perry and Berch under the heading Nonionic Surfactants.

Examples of suitable soaps are the alkali-metal salts of 0 -0 fatty acids such as coconut oil, palm oil, fish oil, and tallow fatty acids. The fatty acids may be natural or synthetic fatty acids. Further examples can be found in the reference Schwartz, Perry and Berch under the heading Soaps.

The detergent composition furthermore comprises a water-soluble alkali-metal builder salt. This is a salt which increases the level of detergency attainable by a detergent surface-active agent. Suitable examples of watersoluble alkali-metal builder salts are alkali-metal ortho phosphates, pyrophosphates, tripolyphosphates, aminopolycarboxylates like ethylenediaminetetraacetate and 'nitrilotriacetates, alkali-metal carbonates and silicates. Mixtures of the above builder salts may also be used.

The detergent composition may furthermore comprise an oxygen-liberating bleaching agent. Suitable examples thereof are persalts, like alkali-metal percarbonates and perborates.

The detergent composition may furthermore comprise the normal detergent adjuvants such as lather boosters like coconut ethanolamide; soil-suspending agents like sodium carboxymethyl cellulose; hydrotropes like sodium toluene sulphonate; activators for the bleaching agent like tetraacetylethylenediamine; perfumes, coloring agents, anti-corrosion agents, fabric damage inhibitors, anti-soil redeposition agents and so on. The particulate detergent composition is obtained by normal processes like spraydrying an aqueous slurry of the constituents, dry-mixing and so on.

The detergent composition furthermore comprises discrete, shaped inorganic solids which contain enzymes homogeneously distributed therein by mechanical working. The material from which these discrete, shaped solids are formed is an inorganic material which is readily soluble or dispersible in normal tap water of 20 C. Examples of these inorganic materials are sodium and potassium sulphate, sodium and potassium carbonate, sodium bicarbonate, sodium and potassium ortho-, pyroand tripolyphosphate, sodium borate, ammonium carbonate and bicarbonate, ammonium chloride, acid sodium and potassium orthoand pyrophosphate, and boric acid.

and tripolyphosphate, sodium borate, ammonium 1 carbonate and bicarbonate, ammonium chloride, acid sodium and potassium orthoand pyropho's Furthermore, combinations of compounds which evolve a gas when brought into an aqueous solution, so-called effervescent substances, may be'u'sedtoadvantage in the present invention, thereby accelerating the disintegration of the shaped solid body in the aqueous solution. Such combinations are, for example, combinations of acid salts or weak acids with carbonates or bicarbonates, etc.

The enzymes which are incorporated in the discrete, shaped inorganic solids may be proteolytic or amylolytic enzymes and mixtures thereof. In particular, proteolytic enzymes may be used, preferably of bacterial origin. The preferred proteolytic enzymes are those produced by micro-organisms, such as the proteases produced by Bacillus subtilis. Such proteases are commercially available under the trade names Alcalase (produced by NOVO Industrie A/S, Copenhagen) and Maxatase (produced by Royal Dutch Fermentation Industries, Delft, Holland).

Amylolytic enzymes which can be used in the present invention are also preferably of bacterial origin, e.g.

from a strain of Bacillus subtilis. Such amylases are commercially available under the trade name Maxamyl (produced by the Royal Dutch Fermentation Industries, Delft, Holland).

The amount of enzymes to be incorporated in the detergent composition is dependent upon the enzymatic activity of the particular enzyme used. In general, enzymecontaining discrete, shaped inorganic solids are incorporated in the particular detergent composition in such an amount that the final product has an activity of 10 10 maltose units per kilogram of final product when amylolytic enzymes are used, and of 520 Anson units per kilogram of final product when proteolytic enzymes are used. a

The weight ratio in which the enzymes and the inorganic material are mixed in the preparation of the discrete, shaped solids lies between 1:100 and :1.

The discrete, shaped inorganic solids should have a physical form which is suitable for mixing with a particulate detergent composition. Suitable forms are ribbons, flakes, threads, small spheres, noodles, small tablets, pellets, granules, etc. The shaped solids are prepared by mechanically working the mixture of enzymes and inorganic material in any suitable shaping process, such as milling, pelleting, extruding,'stamping, pressing, granu lation, etc. In general, the maximum dimension of a discrete, shaped inorganic solid should be not more than 15 mm., and the minimum dimension should be not more than 2.5 mm. The discrete, shaped inorganic solids preferably weigh between 0.05 and 100 mg., particularly preferably between 2 and 20 mg.

For example, noodles with a length of 15 mm. and a width of 0.5 mm., small tablets having a cross section of 2.5 mm. and a thickness of 1.5 mm., flakes of 4 mm. length and a thickness of 0.2 mm., and pellets having a cross section of 2.5 mm. are examples .of suitable discrete, shaped inorganic solids for use according to the invention.

Noodles and small tablets having a weight of about 20 mg. are particularly suitable. Small tablets in which the inorganic material consists of a mixture of a weak acid or an acid salt with an alkali(bi)-carbonate are in particular suitable.

In general, the discrete, shaped inorganic solids should dissolve or disperse or disintegrate in normal tap water at about 20 C. "within 10 minutes, preferably within 2 minutes. The pH of the shaped solid body should preferably be the optimum pH for the enzyme used. In many cases the use of acid salts as exemplified before has a beneficial effect upon the stability of the enzymes.

The discrete, shaped inorganic solids may further contain other ingredients which are desirable in detergent compositions, provided they do not affect the enzymes adversely. 'Ihey may e.g. contain compounds'which stabilize or activate the enzymes. The discrete shaped inorganic solids may also be colored with a coloring agent, the

discrete, inorganic shaped solid being colored on the surface or througband-through, whereby a commercially attractive so-called speckled detergent is obtained. The

should be sufliciently soluble or dispersible in normal tap water at a temperature of about 20 C. Examples of suitable coating material are nonionics, film-forming agents such as shellac, etc. By proper selection of the ingredients of the shaped solid readily water-soluble or -dispers ible solids can be obtained. Water-solubility may be increased by incorporating a hydrotrope in the shaped solid.

In the case of sodium dihydrogen phosphate as inorganic material it has been found advantageous to use shellac as a coating material, since sodium dihydrogen orthophosphate may be converted in an alkaline detergent powder into disodium monohydrogen orthophosphate, which has a low melting point (about 30 C.) and which may cause caking of the powder. Coating the sodium dihydrogen phosphate granules with shellac, dissolved in alcohol, prevents this.

The detergent compositions of the invention show an improved enzyme stability during storage, and do not show a significant segregation of the discrete, inorganic shaped solids in the composition during transport or storage.

The present invention will now he further illustrated by way of examples.

EXAMPLE I Small tablets having a diameter of 2.5 mm., a thickness of 1 mm. and weighing 7 mg. were prepared by compressing 80% of an equimolecular mixture of sodium dihydrogen phosphate and sodium bicarbonate with 20% of a proteolytic enzyme (1.6 Anson units/g.), known under the trade name Alcalase.

The rate of solubility of these tablets 20 C. was 10 seconds.

A detergent powder containing 5% by weight of these tablets did not show any significant segregation of the tablets in the composition. The loss of enzymatic activity during storage of the composition was significantly reduced. The detergent powder had the following composition.

in tap water of Percent Sodium salt of straight-chain C alkylbenzene sulphonate Sodium soap of commercial stearic acid Nonylphenol condensed with 14 moles of ethylene oxide Sodium silicate Sodium sulphate Sodium carboxymethyl cellulose 1.0 Sodium tripolyphosphate 36.0 Sodium perborate 30 Water, perfume etc. Rest same conditions.

EXAMPLE II Spherical granules having a diameter of 0.15 mm. and Weighing less than 0.5 mg. were prepared on a rotating bowl from 75% of potassium dihydrogen phosphate, 20% of a proteolytic enzyme having a proteolytic activity of 1.6 Anson units/g. and 5% of a nonionic surfaceactive agent having a melting point below 20 C. The nonionic surface-active agent was nonylphenol condensed with 14 moles of ethylene oxide.

EXAMPLE III Example II was repeated using as inorganic material sodium acid pyrophosphate, sodium dihydrogen orthophosphate and sodium tri-phosphate.

The rate of solubility in tap water at 20 C. was less than 1 minute in all cases.

Incorporation of the discrete, shaped inorganic solids of Examples II and III in a detergent composition as in Example I produced enzymatic detergent compositions with a significantly improved storage stability.

What is claimed is:

1. A detergent composition consisting essentially of:

(a) from 2 to 20 percent by weight of an anionic detergent surface-active agent selected from the group consisting of alkali-metal alkylbenzene sulphonates with 12 to 18 carbon atoms in the alkyl group, alkalimetal alkylsulphonates with 10 to 24 carbon atoms in the alkyl group, alkali-metal olefin sulphonates with 10 to 20 carbon atoms and alkali-metal alkyl sulphates with 10 to 24 carbon atoms in the alkyl p; (b) from 1 to 10 percent by weight of a nonionic detergent surface-active agent selectedfrom the group consisting of the condensation products of ethylene oxide or propylene oxide with monohydric alcohols having from 12 to 24 carbon atoms in their alkyl group, with alkylphenols having from 8 to 18 carbon atoms in the alkyl group and with fatty acid amides with a C -C fatty acid residue;

(c) from 1 to 10 percent by weight of an alkali-metal soap of O -C fatty acids;

(d) from 20 to 50 percent by weight of a water-soluble alkali-metal builder salt selected from the group consisting of orthophosphates, pyrophosphates, tripolyphosphates, nitrilotriacetates, ethylenediaminetetraacetates, carbonates and silicates;

(e) from 0 to 45 percent by weight of an oxygenliberating bleaching agent selected from the group consisting of alkali-metal percarbonates and perborates; and

(f) from 0.5 to 15 percent by weight of mechanically iworked discrete, shaped inorganic solids which contain enzymes homogeneously distributed therein, said discrete, shaped inorganic solids consisting essen tially of (a) a solid inorganic material selected from the group consisting of sodium and potassium sulphate, sodium and potassium ortho-, pyro-, and tripolyphosphate, sodium borate, ammonium carbonate and bicarbonate, ammonium chloride, acid sodium and potassium orthoand pyrophosphate, and boric acid, and;

(b) amylolytic or proteolytic enzymes, in a weight ratio of (a) to (b) of 1:100 to :1, said discrete, shaped inorganic solids weighing between 0.05 mg. and 100 mg. and being present in the detergent composition in such an amount that the final detergent composition has an amylolytic activity of 10 -10 maltose units per kg. or a proteolytic activity of 5-20 Anson units per kg.

2. A detergent composition according to claim 1, in which the discrete, shaped inorganic solids weigh between 2 and 20 mg.

3. A detergent composition according to claim 1, in which the discrete, shaped inorganic solids are further coated with a coating material, selected from the group consisting of a nonionic surfactant having a melting point below 20 C. and shellac.

4. A detergent composition according to claim 1, in which the inorganic material of the discrete, shaped solids 7 8 consists of an equimolecular mixture of sodium dihydro- FOREIGN PATENTS gen phosphate and sodium bicarbonate. 265,024 u 2/1927 Great Britain, References Cited I I 9622,3121 =vGroat Bliltflln 195-63 UNITED STATES PATENTS IW'IL L'I ME'. SCHULZ PTim y xa ner 3,181,998 5/1965 Kanig 19 3w 'U.S. Cl. X.R.

3,519,570 7/1970 McCarty 252Dig. 13 I 3,600,319 8/1971 Gedge et a1 252Dig. 13 f

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3922197 *Jan 28, 1974Nov 25, 1975Cpc International IncProcess for converting granular starch to dextrose
US4082684 *Apr 28, 1976Apr 4, 1978Lever Brothers CompanyLiquid detergent
US4115292 *Apr 20, 1977Sep 19, 1978The Procter & Gamble CompanyEnzyme-containing detergent articles
US4176079 *Apr 20, 1977Nov 27, 1979The Procter & Gamble CompanyWater-soluble enzyme-containing article
US4404128 *May 29, 1981Sep 13, 1983The Procter & Gamble CompanyEnzyme detergent composition
US4417994 *Jan 20, 1982Nov 29, 1983The Procter & Gamble CompanyParticulate detergent additive compositions
US4568476 *Aug 6, 1984Feb 4, 1986Lever Brothers CompanyEnzymatic machine-dishwashing compositions
US4707287 *Jun 28, 1985Nov 17, 1987The Procter & Gamble CompanyDry bleach stable enzyme composition
US4874537 *Sep 28, 1988Oct 17, 1989The Clorox CompanyStable liquid nonaqueous detergent compositions
US4919834 *Sep 28, 1988Apr 24, 1990The Clorox CompanyPackage for controlling the stability of a liquid nonaqueous detergent
US5589448 *Jun 7, 1995Dec 31, 1996The Clorox CompanyHigh water liquid enzyme prewash composition
US5783545 *Dec 14, 1994Jul 21, 1998Henkel Kommanditgesellschaft Auf AktienEnzyme preparation containing a silver corrosion inhibitor
US5789364 *Jun 13, 1996Aug 4, 1998The Clorox CompanyHigh water liquid enzyme prewash composition
US5972668 *Jun 19, 1995Oct 26, 1999Henkel Kommanditgesellschaft Auf AktienProduction of multi-enzyme granules
US6350728Dec 2, 1997Feb 26, 2002Henkel Kommanditgesellschaft Auf Aktien (Kgaa)Coated enzyme preparation with an improved solubility
US6380140Apr 12, 1997Apr 30, 2002Henkel Komm.Nditgesellschaft Auf AktienEnzyme granules containing phosphated starch
US6409770Nov 29, 1996Jun 25, 2002Henkel Kommanditgesellschaft Auf AktienBleaching and washing agents with enzyme bleaching system
US6979669Mar 1, 2004Dec 27, 2005Henkel Kommanditgesellschaft Auf AktienEncapsulated active ingredient preparation for use in particulate detergents and cleaning agents
US20040198629 *Mar 1, 2004Oct 7, 2004Wilfried RaehseEncapsulated active ingredient preparation for use in particulate detergents and cleaning agents
WO2001059056A1 *Feb 9, 2001Aug 16, 2001Carbonell EnricDetergent composition in tablet form
WO2001059058A1 *Feb 9, 2001Aug 16, 2001Carbonell EnricDetergent composition in tablet form
Classifications
U.S. Classification510/374, 510/305, 510/441, 510/484, 510/320, 510/306, 435/187, 510/392, 510/530, 510/438
International ClassificationC11D3/42, C11D3/386, C11D1/00, C11D3/40, C11D17/00, C11D11/00, C11D3/50, C11D3/48, C11D17/06, C11D3/38
Cooperative ClassificationC11D3/48, C11D3/38672, C11D17/0039, C11D17/06, C11D1/00, C11D3/38627, C11D11/00, C11D3/38609, C11D3/50, C11D3/42
European ClassificationC11D3/48, C11D3/386M, C11D3/42, C11D17/00D, C11D11/00, C11D17/06, C11D3/386D, C11D3/386A, C11D3/50, C11D1/00