EP0373850A1

EP0373850A1 - Enzyme-containing detergent compositions and their use

Info

Publication number: EP0373850A1
Application number: EP19890312893
Authority: EP
Inventors: Graeme Douglas Armstrong
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 1988-12-12
Filing date: 1989-12-11
Publication date: 1990-06-20
Anticipated expiration: 2009-12-11
Also published as: NO173883C; BR8906415A; AU4605489A; GB8828955D0; CA2005022C; EP0373850B1; AU627800B2; DE68919656T2; KR930008482B1; CA2005022A1; NO894964D0; JPH02219900A; NO173883B; ES2064465T3; NO894964L; KR900009948A; ZA899473B; DE68919656D1; PH26768A

Abstract

An enzyme-containing detergent composition for washing fabrics, e.g. in the form of powder, granulate, liquid, bar or paste, the composition containing 1 to 60% by weight of a surfactant or surfactant system comprising a primary alcohol sulphate and further comprising lipase enzyme in an amount in the range 50 to 30,000 (LU) lipase units per gram of the surfactant system or of the detergent composition.

Description

This invention relates to detergent compositions, and to their use, and in particular to compositions containing lipase and to their use.

Prior Art:

Detergent compositions comprising lipase are known. For example GB 1 372 034 (Unilever) discloses lipase from Pseudomonas in specific nonionic-containing detergent compositions for soaking fabrics.
USP 3 950 277 (Procter & Gamble) also describes fabric-soaking compositions: the described compositions comprise lipase and lipase activators and a number of lipases from microorganism and other sources are mentioned: those particularly mentioned as preferred are Amano CE, Amano M-AP, Takeda 1969-4-9, and Meito MY-30 lipases, but no indications are given of the form in which the lipase is to be prepared or used.
USP 4 011 169/NL 74 08763 (Procter & Gamble) describes the use of a similar range of enzymes in the preparation of additives for washing agents (detergent compositions).
Examples of known lipase-containing detergent compositions are provided by EP 0 205 208 and 0 206 390 (Unilever), which relate to lipases related to those from Ps. fluorescens, P gladioli and Chromobacter in detergent compositions.
EP 0 214 761 (Novo) and EP 0 258 068 (Novo), each give detailed description of lipases from certain microorganisms, and also give certain uses in detergent additives and detergent compositions for the enzymes described. EP 0 214 761 gives detailed description of lipases derived from organisms of the species Pseudomonas cepacia, and certain uses therefor. EP 0 258 068 gives detailed description of lipases derived from organisms of the genus Thermomyces/Humicola, and certain uses therefor.
Also believed to be in use in certain areas is a lipase-containing granular detergent composition containing about 37% detergent actives including 5% nonionic detergent and the remainder substantially anionic detergent, about 16% zeolite, about 60 LU/g lipase, plus protease and other normal detergent additives.
Further examples of known lipase-containing detergent compositions are provided by JA 63-078000 (1988) (Lion Corp/K Mukoyama et al) which discloses properties and uses of a Pseudomonas lipase, including use in a lipase-containing system based on 10-40 % surfactant (e.g. sodium C12-C18 alpha-olefin sulphonate), as well as other conventional detergent ingredients.
The prior art also includes EP 0 268 456 (Clorox), which shows in connexion with Table 10(b) an experimental washing solution containing lipase and about 1 microgram/ml sodium dodecyl sulphate.
Also in the prior art is Research Disclosure 29056 of June 1988 which discloses lipase in connexion with the detergents of EP 0 179 533 (Procter & Gamble).

The Present Invention:

One difficulty with prior detergent-formulations containing lipase is that there is a strong tendency for many detergent-active materials to inhibit the action of the lipase.
It is an aim of the present invention to provide detergent formulations in which the activity of added lipase is relatively less inhibited.
According to the present invention there is provided an enzyme-containing detergent composition for washing fabrics, the composition containing 1 to 60% by weight of a surfactant or surfactant system comprising a primary alcohol sulphate, especially for example one or a mixture with chain length in the range C14 to C18, and further comprising lipase enzyme in an amount in the range 50 to 30,000 (LU) lipase units per gram of the surfactant system or of the detergent composition.
In this specification lipase units are defined as they are in EP 0 258 068 (Novo).
In most practical embodiments, the ingredients of the detergent compositions also include e.g. conventional detergent adjuncts such as one or more of those mentioned below.
In several preferred embodiments, especially e.g. certain detergent powder or granulate formulations, the surfactant system in the detergent composition can consist essentially of a major proportion, especially a proportion of 50% or more, of the mentioned primary alcohol sulphate. In certain other useful embodiments, the proportion of the primary alcohol sulphate in the surfactant system can be lower, e.g. from about 25-30% upwards, e.g. from about 33% upwards, e.g. about 40% or more.
It has been found that in these systems lipase enzyme shows surprisingly little inhibition. One reason for surprise at good performance of lipase in this system is that at least one member of the class of primary alcohol sulphates, i.e. sodium dodecyl sulphate, is well-known and used in laboratory investigations as a denaturant for proteins including enzymes. By comparison with a lipase-containing surfactant based on alpha-olefin sulphonate, the compositions of the present invention show stronger detergent action combined with adequately low levels of lipase inhibition.
It is also surprising that the (known) building effect of primary alcohol sulphate and its high calcium affinity by comparison with the highly inhibitory LAS surfactants does not lead to greater degrees of lipase inhibition.
The primary alcohol sulphates used in these compositions can for example be based on coco-primary alcohol sulphates or tallow-primary alcohol sulphates or mixtures of these with each other and/or analogues having alkyl chains derived from other sources.
Also permissible in the compositions are quantities of other surfactant types, especially anionic, nonionic or cationic detergents, in small or minor amounts e.g. up to 10%, possibly up to 20% or up to 35%, sometimes up to 50%, of the surfactant system, e.g. linear alkyl-benzene sulphonates (LAS) or (branched-chain) alkylbenzene sulphonates (ABS), which alone have been found to show unacceptably high degrees of inhibition of lipase.
In certain examples of the compositions of the invention, especially for example those illustrated in Example 11-13 below, the alkylbenzene sulphonates (LAS or ABS) may be present at up to about 66%, or in some cases up to about 70% or even 75%, of the surfactant system including the primary alcohol sulphate.
For example, certain of the formulations may comprise a surfactant system consisting essentially of a mixture of PAS with ABS and/or LAS. Here the proportion of ABS or LAS in such mixture may be for example up to about 75%, e.g. up to about 70%, often somewhat lower as for example about 66% or 60%, by weight.
A preferred surfactant system for use in this invention is based on a mixture (e.g. about 1:1 w/w) of C12-C14 coco-alkyl and C16-C18 tallow-alkyl sulphates.
The lipolytic enzyme can usefully be added in the form of a granular composition of lipolytic enzyme with carrier material.
The added amount of lipolytic enzyme can be chosen within wide limits, for example 50 to 30,000 LU/g of granular detergent composition, e.g. often at least 100 LU/g, very usefully at least 500 LU/g, sometimes preferably above 1000, above 2000 LU/g or above 4000 LU/g or more, thus very often within the range 50-4000 LU/g and possibly within the range 200-1000 LU/g.
The lipolytic enzyme can be chosen from among a wide range of lipases: in particular the lipases described in for example the following patent specifications, EP 0 214 761 (Novo), EP 0 258 068 (Novo) and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Thermomyces lanuginosus ATCC 22070, EP 0 205 208 (Unilever) and EP 0 206 390 (Unilever), and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Chromobacter viscosum var lipolyticum NRRL B-3673, or against lipase from Alcaligenes PL-679, ATCC 31371 and FERM-P 3783, also the lipases described in specifications WO 87/00859 (Gist-Brocades) and EP 0 204 284 (Sapporo Breweries). Suitable in particular are for example the following commercially available lipase preparations: Novo Lipolase, Amano lipases CE, P, B, AP, M-AP, AML, and CES, and Meito lipases MY-30, OF, and PL, also esterase MM, Lipozym, SP225, SP285, Saiken lipase, Enzeco lipase, Toyo Jozo lipase and Diosynth lipase (Trade Marks).
Genetic engineering of the enzymes can be achieved by extraction of an appropriate lipase gene, e.g. the gene for lipase from Thermomyces lanuginosus or from a mutant thereof, and introduction and expression of the gene or derivative thereof in a suitable producer organism such as an Aspergillus. The techniques described in WO 88/02775 (Novo), EP 0 243 338 (Labofina) and EP 0 268 452 (Genencor) may be applied and adapted.

A preferred non-limitative example of a granular or powder-form detergent composition according to the present invention comprises:

Primary alkyl sulphate (50:50 coco/tallow alkyl sulphates)	9%
Sodium sulphate	34.4%
Sodium carbonate	6.7%
Sodium chloride	3.4%
Sodium C-Silicate	6.5%
Zeolite A (anhydrous)	30.2%
Sokolan CP5 (TM)	4.5%
Synperonic A4 (TM) (polyethoxylated alcohol c. C12-E4)	4%
Lipase (Lipolase 30T granulate, Novo)	1%
or lipase from Pseudomonas gladioli.

The detergent compositions may furthermore include the following usual detergent ingredients in the usual amounts. They may be built or unbuilt, and may be of the zero-P type (i.e. not containing any phosphorus-containing builders). Thus the composition may contain from 1-45%, e.g. 5-30% by weight of one or more organic and/or inorganic builders. Typical examples of such builders include alkali metal ortho, pyro, and tripolyphosphates, alkali metal carbonates, either alone or in admixture with calcite, alkali metal citrates, alkali metal nitrilotriacetates, carboxymethyloxysuccinates, zeolites, polyacetalcarboxylates and so on. Furthermore, they may contain from 1-35% of a bleaching agent or a bleach precursor or a system comprising bleaching agent and/or precursor with activator therefor. Further optional ingredients are lather boosters, foam depressors, anticorrosion agents, soil-suspending agents, sequestering agents, anti-soil redeposition agents, perfumes, dyes, stabilising agents for the enzymes and so on. The enzymes other than lipase that may be present include protease, amylase, oxidase and cellulase.
The compositions may be formulated in any desired way, e.g. as powders, bars, pastes, liquids.
The compositions can be used for the washing of textile materials, especially but without limitation cotton and polyester-based textiles and mixtures thereof. Especially suitable are for example washing processes carried out at temperatures of about 60-65 deg C or lower, e.g. about 30-35 deg C or lower.
The invention is further illustrated non-limitatively by the following examples, which also show the performance estimated in terms of reflectance at 460nm of test cloths soiled with lipid and then washed, after 5 washes with a number of different lipase-containing detergent formulations.

Examples 1-5

In each example, a detergent formulation was used to wash cotton test cloths soiled with a fatty mix based on olive oil (up to 10-15% by weight of the test cloths) after three-times prewashing. The detergent formulations used corresponded to the one given in detail above, except for the use of various surfactant systems (each in an amount of 9% by weight) as follows:

Ex 1 Coco-alkyl sulphate (Elfan 280 ex Akzo)
Ex 2 Tallow-alkyl sulphate (Sulphopon T55 ex Henkel)
Ex 3 50:50 coco-alkyl/tallow-alkyl sulphates
Ex 4 25:25:50 coco-alkyl-tallow alkyl-DOB113
Ex 5 DOB113 (linear alkyl benzene sulphonate alone for comparison)

In the above formulation, 'DOB113' refers to the sulphonation product of Shell alkylbenzene DOB113 (TM).
Examples 6-10 correspond to Examples 1-5 except for wash temperature.
In each example, isothermal washes were performed at 30 deg.C. or 60 deg.C. for 30 minutes with and without lipase enzyme, with predissolved detergent compositions used at 4 g/l. Cloth/Liquor ratios were uniformly 10:1 containing 50:50 soiled:unsoiled load.
In each experiment, one of two lipases was used: Lipolase from Novo as specified above, or lipase from Pseudomonas gladioli, used in the form of a conventionally purified culture preparation (600 LU/mg) at equivalent lipase activity to that of the Lipolase.
Results are quoted as average reflectances at 460nm of 5 test pieces after 5 soil/wash cycles.

Examples 1-5 were carried out at 60 deg C, Examples 6-10 were carried out at 30 deg C.

Reflectances (% at 460nm):
Control (no lipase)		Experiments
		(Lipolase)	('gladioli')
Ex 1	68	72	73.4
Ex 2	68.3	73.8	73.9
Ex 3	69.6	72.8	73.5
Ex 4	68.7	74.0	74.2
Ex 5	71.8	71.9	72.8
Ex 6	69	72.3	73.7
Ex 7	69.2	72.1	73.6
Ex 8	70.6	70.9	73.3
Ex 9	69.6	71.9	73.4
Ex 10	70.5	71.2	73.2

The results generally show an incremental benefit due to lipolytic activity. The general trend is to show that lipase in the presence of LAS-type detergent gives substantially less benefit (ex 5,10) than on average in the other examples (primary alcohol sulphates and their mixtures), which are accordingly preferred for use.

Examples 11 to 13

The following detergent bar formulations support well the liplytic action of lipase.

Primary alcohol sulphate (PAS)	28	15.5	12
(e.g. EMAL 10, ex Kao Corp, av. chain length C10)
Alkyl-benzene sulphonate (ABS)	--	15.5	18
(e.g. from Escane F ex Exxon, av. chain length C11)
Sodium pyrophosphate	16	10	10
Soda ash	10	18	18
Calcite	32	31	31
Aluminosilicate	2	2	2
Lipolase	1	1	1
Minors and Water to 100% in each case.

The formulations are compounded in per-se conventional manner for detergent bars.

The present invention is susceptible of modifications and variations, and the present disclosure extends to the use of all combinations and subcombinations of the features described herein, optionally in combination with each of the features of the above-cited published patent specifications, each of which specifically incorporated by reference herein.

Claims

1: An enzyme-containing detergent composition for washing fabrics, the composition comprising 1 to 60% by weight of a surfactant or surfactant system comprising a primary alcohol sulphate, and further comprising lipase enzyme in an amount in the range 50 to 30,000 (LU) lipase units per gram of the surfactant system or of the detergent composition, together with conventional detergent adjuncts.

2: An enzyme-containing detergent composition according to claim 1, wherein the primary alcohol sulphate forms at least 30% of the surfactant system.

3: An enzyme-containing detergent composition according to claim 1, wherein the primary alcohol sulphate forms at least 50% of the surfactant system.

4: An enzyme-containing detergent composition according to claim 1, 2, or 3, wherein said primary alcohol sulphate has a chain length in the range C12 to C18.

5: An enzyme-containing detergent composition according to claim 1, 2, or 3, wherein said primary alcohol sulphate comprises coco-alkyl primary alcohol sulphates or tallow-alkyl primary alcohol sulphates or mixtures of these with each other and/or analogues having alkyl chains derived from other sources.

6: An enzyme-containing detergent composition according to any of claims 1-5, further comprising anionic, nonionic or cationic detergent, as minor constituents (up to 50%) of the surfactant system of the detergent composition.

7: An enzyme-containing detergent composition according to claim 6, in in the form of a granular composition or powder.

8: An enzyme-containing detergent composition according to claim 1, wherein the surfactant system comprises or consists essentially of a mixture of primary alcohol sulphate together with linear or branched alkylbenzenesulphonate, with the proportion of the primary alcohol sulphate being at least 25%, e.g. at least 30% of the weight of the surfactant system.

9: An enzyme-containing detergent composition according to claim 8, in the form of a bar or paste.

10: An enzyme-containing detergent composition according to any of claims 1 to 9, wherein the lipase is a lipase which shows immunological cross-reactivity with antiserum against lipase from Thermomyces lanuginosus ATCC 22070, or shows immunological cross-reactivity with antiserum raised against lipase from Chromobacter viscosum var lipolyticum NRRL B-3673.

11: An enzyme-containing detergent composition according to claim 10, wherein the lipolytic enzyme has been added in the form of a granular composition of lipolytic enzyme with carrier material.

12: An enzyme-containing detergent composition according to any of claims 1 to 11, in the form of a detergent powder or granulate comprising primary alkyl sulphate, zeolite A (anhydrous), sodium sulphate, sodium carbonate, sodium chloride, sodium C-silicate, Sokolan CP5 (TM), Synperonic A4 (TM), and Lipolase (ex Novo).

13: An enzyme-containing detergent composition according to any of claims 1 to 11, in the form of a detergent bar comprising primary alcohol sulphate (PAS) (e.g. EMAL 10, ex Kao Corp, av. chain length C10), alkyl-benzene sulphonate (ABS) (e.g. from Escane F ex Exxon, av. chain length C11), sodium pyrophosphate, soda ash, calcite, aluminosilicate, Lipolase, minors and water.

14: An enzyme-containing detergent composition according to any of claims 1 to 8, containing contain from 1-35% of a bleaching agent or a bleach precursor or a system comprising bleaching agent and/or precursor with activator therefor.