CA1247025A - Enzymatic detergent composition - Google Patents

Enzymatic detergent composition

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Publication number
CA1247025A
CA1247025A CA000491582A CA491582A CA1247025A CA 1247025 A CA1247025 A CA 1247025A CA 000491582 A CA000491582 A CA 000491582A CA 491582 A CA491582 A CA 491582A CA 1247025 A CA1247025 A CA 1247025A
Authority
CA
Canada
Prior art keywords
metaborate
sodium
peroxy
alkali metal
enzymes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000491582A
Other languages
French (fr)
Inventor
Jiri Hora
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Unilever PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC filed Critical Unilever PLC
Application granted granted Critical
Publication of CA1247025A publication Critical patent/CA1247025A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions

Abstract

Abstract of the Disclosure The invention pertains to detergent compositions which comprise a peroxy-type bleaching agent, other than an alkali metal percarbonate, and enzymes. By inclusion of an alkali metal metaborate in such compositions, pre-ferably affixed to the surface of the particulate peroxy-type bleaching agent, the storage stability of the enzymes in the compositions is significantly im-proved.

Description

~ C 7042 (R) ENZYMATIC DETERGENT COMPOSITION

The present invention relates to enzymatic detergent compositions with improved enzyme-storage stability.
More particularly, the invention relates to a detergen-t composition which contains a bleaching agent, in addi-tion to the enzymes, with improved enzyme-storage sta-bility.

It is well-known in the detergent art that the inclusion of enzymes and bleaching agents in a detergent composi-tion may give rise to enzyme-stability problems. With-out precautionary measures, the enzymes may be negatively affected by the bleaching agent, resulting in a decrease of the enzymatic activity. Numerous pro-posals have already been made in the prior art to sta-bilize the enzymes in such bleach-containing detergent compositions, such as coating the enzymes and/or the bleaching agent with a protective coating or adding specific stabilizing agents to the composition.

Recently it has been proposed in German Patent Appli-cation 33 21 082, laid open to public inspection on 15 December 1983, to improve the storage stability of sodium percarbonate in a detergent composition by coating the sodium percarbonate with a coating which contains a borate, such as sodium tetraborate (either the anhydrous salt or the different hydrates thereof), sodium octaborate, sodium pentaborate and sodium meta-borate. The sodium metaborate-dihydrate and -tetrahy-drate are preferred.
These compositions may also contain enzymes and it is stated that such enzyme-containing detergent composi-tions have an improved enzyme-storage stability.
~ t'j~,r~

C 7042 (R) ~Z~70'~5 We have now surprisingly found that the storage stabi-lity of enzymes in detergent compositions which contain other peroxy~type bleaching agents can be improved by inclusion in such compositions oE sodium metaborate.
Whereas in the above discussed reference sodium per-borate is stated and shown to be much more stable than uncoated sodiurn percarbonate and as stable as coated sodium percarbonate, it is unexpected that the addition of sodium metaborate according to our invention to o-ther peroxy-type bleaching agents increases the enzyme stability even rnore.

In addition, whereas the above reference advocates the use of various borates, we have found that in our com-positions only alkali metal metaborates are effectiveas enzyme storage stability improving agents.

The present invention therefore relates to an enzymatic detergent cornposition which comprises a peroxy-type bleaching agent other than an alkali metal percarbonate, and enzymes, the storage stability of which is improved by the inclusion in the composition of an alkali metal metaborate.

The invention will hereafter be discussed in further detail.

The first essential ingredient is a bleaching agent of the peroxy-type other than alkali metal percarbonate.
Typical examples of such peroxy-type bleaching agents are alkali metal persulphates, -perphosphates, -per-borates, alkali metal and alkaline earth metal salts of organic peracids, such as perphthalic acid, mono- and diperoxy azelaic acid, peroxy acetic acid, diperdodecane dioic acid and so on.

C 7042 (R) ~2~

The preferred peroxy-type bleaching agents are those which have, under the same storage conditions, a better storage stability in terms of available oxygen than percarbonate. A partic~larly preferred bleaching agent is sodium perborate, both in its tetrahydrate as well as in its monohydra-te ~orm. In general the amount of peroxy-type bleaching agent in the compositions of the invention ranges from 1-40~, preferably 3-35~, and par-ticularly preferably from 5-30% by weight. The compo-sitions of the invention may in this respect alsocontain bleach precursors, such as tetraacetyl ethylene diamine, tetraacetyl glycoluril, glucose pentaacetate and so on, to provide with the peroxy-type bleaching agen-t for a low tempera-ture bleaching detergent compo-sition. Usually the amount of such a bleach precursorranges Erom 0.5-20% by weight.

The second essential ingredient is the alkali metal metaborate. Typical suitable examples thereof are sodium and potassium metaborate, either anhydrous or in its various hydrate ~orms, e.g. K-metaborate. 1.5 aq, Na-metaborate. 2 aq. and .4 aq.

The alkali metal metaborate can be added in powdered form to the compositions of the invention or can be affixed to the surface of the peroxy-type bleaching agent when the latter is used in a particulate form. In this respect it has been found that even better enzyme storage stability results are obtained if the particu-late peroxy-type bleaching agent is first treated with a potassium salt having a lower equilibrium humidity than the particulate peroxy-type bleaching agent, fol-lowed by a treatment with sodium metaborate. ~ypical examples of a suitable potassium salt is potassium metaborate. Both the potassium salts and the sodium metaborate are affixed to the particulate peroxy-type bleaching agent in the dry, powdered form. It is also C 7042 (R) ~2~

possible to cause formation of the metaborate on the sur~ace of the peroxy-type bleaching agent in situ, e.g. by addition of metaborate-forming substances which react with the peroxy-type bleaching agent, e.g. di-methyl sulfoxide.

In general the alkali metal metaborate is present inthe composition in an amount ranging from 0.1 % to 50 ~, preferably 0.2 to 30~, and particularly prefer-ably 0.5 to 20~ by weight.

The third essential ingredient in the compositions ofthe invention is an enzyme. Typical examples of enzymes which can be used according to the invention are prote-ases, amylases, lipases and cellulases as they areusually proposed in the detergent art for inclusion in detergent compositions.

Suitable examples of proteolytic enzymes are the sub-tilisins which are obtained from particular strains ofB. subtilis and B. licheniformis, such as the com-mercially available Maxatase ~ (ex Gist-Brocades N.V., Delft, Holland) and Alcalase ~ (ex Novo Industri A/S, Copenhagen, Denmark). Particularly suit-able are proteases obtained from a strain of Bacillushaving maximum activity in the pH-range of 8-12, de-veloped and sold by Novo Industri A/S under the regis-- tered trade-names Esperase ~ and Savinase ~. The preparation of such enzymes is described in British -- 30 Patent Specification 1,243,784.

Suitable examples of amylolytic enzymes are comrnercially available amylases, such as Maxamyl ~ (ex Gist-Brocades) and Terrnamyl ~ (ex Novo Industri A/S).
Amylases as described in British Pa-tent Specification 1,296,839 are also suitable.

_ _ C 7042 (R) 7~2~

Typical examples of commercial lipolytic enzymes are e.g. Lipase YL, Amano CE, Wallerstein AW, Lipase MY, and typical examples of cellulolytic en~ymes are cellu-lases ex Humiscola insolens as described in German _ Patent Application 3,117,250.

The benefits of the present invention are especially pronounced in amylase-con-taining formulations. The amount of en~ymes present in the compositions of the invention is dictated by the activity of the enzyme preparation used. The higher this activity, the lower the level of enzymes required. In general the amount will vary between 0.001 and 10% by weight, and for most practical purposes between 0.1 and 5% by weight of the composition.

The compositions of the present invention can further-more contain other ingredients commonly encountered in bleaching and detergent compositions. Thus they may comprise one or more surfactants in an amount of up to 60%, such as soaps, anionic, nonionic, cationic and/or amphoteric synthetic detergents. In addition they may comprise one or more inorganic and/or organic builder salts, such as the condensed phosphates, silicates, carbonates, nitrilotriacetates and so on, in amounts up to 60~ by weight. In this respect it has been found that the benefits of the present inven-tion are parti-cularly pronounced in formula-tions which contain a phosphate builder salt.
Furthermore, other optional ingredients include soil-suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, optical brigh-teners, suds-depressants, germicides, anti-tarnishiny agents, other enzyme sta-bilizers, softening agents, sequestering agents suchas the amino polyphosphonic acids, clays and so on.

~2 ~7~ ~5 Thus, a typical formulation for use in machine dish-washing may contain from 20~50~ of sodium tripolyphos~
phate, 2-20~ sodium silicate, 0-50~ sodium carbonate, 5-25% sodiurn perborate, amylase plus protease up to 4~, TAED up to 10~, and amino polyphosphonic acid up to 1~.

The compositions of the present inven-tion can be pre-paxed in any suitable particulate form, such as powders, granules, tablets, flakes, ribbons, noodles and the like, and they can be used for fabric washing, hard surface cleaning, dishwashing and general purpose cleaning.

The invention will be further illustrated by way of Example.

The following dry-mixed formulations were prepared :
_ .
Particulate Granular Particula~e Texmamyl sodium tri- sodium sodium meta-polyphosphate perborate borate tetrahydrate _% by weight _ ~ by weight _% by weight ~ by weigh-t A 86.4 9.6 0 4 B 81.6 9.6 4.~
C 76.8 9.6 9.6 4 _ _ _ Termamyl is an amylase according to British Patent 1,296,839, sold by Movo Industri AS.

These products were stored under the conditions as given in the Table below and the residual enzymatic activity (REA) was determined at the end of the storage period. The results were as follows :

C 7042 (R) ~Lf2~77~25 REA (expressed as % of initial activity) after 22 days at 30C 2.7 days at 37C/ 5.7 days at 37~C/
in closed con- 70% RH in open 70% RH in open tainer container container A 54.0 19.8 7.7 C 89 5 __ _56.2 32.9 ~ by weight _ _ .
Sodium tri- Sodium per- Sodium En~yme polyphosphate¦ borate metaborate I tetrahydrate tetrahydrate A 88.4 9.6 0 2 SP 227 B 83.6 9.6 4.8 2 SP 227 20 C 90 9.6 0 0.4 Savinas D 85.2 L 9.6 _ 4.8 _ 0.4 Savinas~

SP 227 is a cellulase as described in German Patent Application 3,117,250, manufactured by NOVO Industri AS, and Savinase is a protease as described in British Patent 1,243,784, manufactured by NOVO Industri AS.

These formulations were stored in closed cups at 37C
and the residual enzymatic activity (in ~) was measured after the storage period as indicated below.
The following results were obtained.

~7~ C 7042 (R) REA after x days . _ _ I
x = 12~ = 19 x = 33 The following formulations were prepared by dry mixing:

Sodium tri- Magnesium mono- Metaborate Termamyl polyphoshate peroxy phthalate dihydrate G 88.4 9.6 0 2 H 81.73 9.6 6.67 2 After storage for 2.7 days in open containers at 37C/
70% RH, the following residual en~ymatic activities were measured :
G 16.9 H 41.9%

The following compositions were prepared by dry mixing:
% by weight J _ K L M _ N
Sodium tripolyphosphate 88.4 86.4 83.6 83.6 83.6 Sodium perborate tetrahydrate 9.6 9.6 9.6 9.6 9.6 Termamyl 2 2 2 2 2 Boric acid _ 2 _ _ _ Sodium pentaborate 35 decahydrate _ _ 4.8 _ _ Borax (decahydrate) _ _ _ 4.8 _ Sodium metaborate _ _ _ __ 4.8 ~ C 7042 (R) These products were stored for x days in open containers at 37C/70~ RH and in closed containers at 37C. The residual enzymatic activities were as follows :

_ _ 37C/70~ RH x = 2 5 8 37C 13 28 35 _ _ Compositions were prepared consisting of 2.1% Termamyl, 10~ sodium perborate tetrahydrate, alkali metal meta-borate as specif,ied in the Table below, and sodium tri-polyphosphate up to 100~. The residual enzymatic acti-vity after x days' storage in open containers at 37C/
70~ RH was as follows :

REA
Metaborate x = 3x = 6 o - 16 6 P 1.2% K-metaborate. 1.5 H2O 39 23 Q 0.76~ Na-me-taborate dry 39 19 R 1.11% Na-metaborate. 2 H2O 42 20 30 S 1.5~ Na-metaborate. 4 H2O 36 20 Granulated sodium perborate (73.92 kg) was mixed in a Lodige mixer at 20C for one hour with powdered pot-assium metaborate.l.5 H20 (2.94 kg). The metaborate melted within the surface of the perborate granules, ~4'7~25 C 7042 (~) causing a fluidized surface thereon. Subsequently, powdered dry sodium metaborate (7.14 kg) was added to the mixer, which adhered to the fluidized surface and restored the free-flowing character of the granulate.
After sieving and collecting the particles with a.dia-meter of more than 230 micrometer, 79.5 kg of a granulate containing up to 87.3% sodium perborate were obtained.

Formulations were made with this granulate, with or without separately added dry sodium disilicate, and these formulations were compared with the same formu-lations but without the metaborate. The formulations had the following compositions :

A B C D
, . _ I- __ rermamyl 2 2 2 2 20 Sodium perborate.4H20 9.2 _ 9.6 Sodium perborate ) _ 9.6 _ 9.6 (co-granulate) ) ~lkali metal metaborate ) _ 1.3 _ 1.3 Sodium disilicate _ _ 9.6 9.6 25 Sodi~m tripolyphosphate 88.4 87.1 78.8 77.5 '.` L L ._ __. __ , .
The residual enzymatic activity after x days' storaye at 30C/60-65~ RH in open containers was as follows :

x =0 8 14 .

D_ 99 81 69

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An enzymatic detergent and bleaching com-position comprising from 0.to 60% of one or more surfactants, from 0 to 60% of inorganic or organic builder salts, from 0.001 to 10% of enzymes, from 1 to 40% of peroxy-type bleaching agents other than alkali metal percarbonates, and an effective amount of an enzyme-storage stability improving agent, wherein the enzyme-storage stability improving agent comprises an alkali metal metaborate, all percentages being by weight of the composition.
2. The composition of claim 1, comprising 0.1 to 50% by weight of the alkali metal metaborate.
3. The composition of claim 1, wherein the alkali metal metaborate is affixed to the surface of a par-ticulate form of the peroxy-type bleaching agent.
4. The composition of claim 3, wherein sodium metaborate is affixed to the surface of a particulate form of the peroxy-type bleaching agent which has first been treated with potassiun metaborate.
CA000491582A 1984-10-02 1985-09-26 Enzymatic detergent composition Expired CA1247025A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848424812A GB8424812D0 (en) 1984-10-02 1984-10-02 Enzymatic detergent composition
GB8424812 1984-10-02

Publications (1)

Publication Number Publication Date
CA1247025A true CA1247025A (en) 1988-12-20

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ID=10567535

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Application Number Title Priority Date Filing Date
CA000491582A Expired CA1247025A (en) 1984-10-02 1985-09-26 Enzymatic detergent composition

Country Status (7)

Country Link
EP (1) EP0181651A3 (en)
JP (1) JPS62116696A (en)
AU (1) AU576629B2 (en)
BR (1) BR8504806A (en)
CA (1) CA1247025A (en)
GB (1) GB8424812D0 (en)
ZA (1) ZA857543B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5312749A (en) * 1992-05-12 1994-05-17 The United States Of America As Represented By The Secretary Of Agriculture Industrial alkaline protease from shipworm bacterium

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5318714A (en) * 1988-03-14 1994-06-07 Novo Nordisk A/S Stabilized particulate composition
WO1989008694A1 (en) * 1988-03-14 1989-09-21 Novo-Nordisk A/S Granulate detergent enzyme product, method for production thereof, use thereof, and detergent containing such product
GB8916094D0 (en) * 1989-07-13 1989-08-31 Unilever Plc Liquid bleach composition
GB9323971D0 (en) * 1993-11-22 1994-01-12 Toad Innovations Ltd Cleaning formulation

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1075405A (en) * 1977-03-28 1980-04-15 John F. Goodman Photoactivated bleach-compositions and process
LU76548A1 (en) * 1977-01-10 1978-09-18
DE2857472A1 (en) * 1977-11-29 1980-07-17 Procter & Gamble DETERGENT TABLET WITH A HYDRATED SALT COVER AND METHOD FOR PRODUCING THE TABLET
US4430244A (en) * 1982-03-04 1984-02-07 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
GB2123044B (en) * 1982-06-10 1986-02-05 Kao Corp Bleaching detergent composition
US4529525A (en) * 1982-08-30 1985-07-16 Colgate-Palmolive Co. Stabilized enzyme-containing detergent compositions
GB8312185D0 (en) * 1983-05-04 1983-06-08 Unilever Plc Bleaching and cleaning composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5312749A (en) * 1992-05-12 1994-05-17 The United States Of America As Represented By The Secretary Of Agriculture Industrial alkaline protease from shipworm bacterium
US5474700A (en) * 1992-05-12 1995-12-12 The United States Of America As Represented By The Secretary Of Agriculture Industrial alkaline protease from shipworm bacterium

Also Published As

Publication number Publication date
AU4810785A (en) 1986-04-10
JPH0364560B2 (en) 1991-10-07
AU576629B2 (en) 1988-09-01
ZA857543B (en) 1987-05-27
BR8504806A (en) 1986-07-22
GB8424812D0 (en) 1984-11-07
EP0181651A2 (en) 1986-05-21
JPS62116696A (en) 1987-05-28
EP0181651A3 (en) 1988-02-10

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