JPH02227500A - Enzymatic liquid detergent composition - Google Patents

Abstract

PURPOSE: To provide a compsn. containing a nonionic surfactant, lipase, a lower aliphatic alcohol and proteinase in a specific ratio and markedly enhanced in storage stability of lipase.

CONSTITUTION: The objective compsn. contains 10-90% of a surfactant (A) containing 50% or more of a nonionic surfactant, fungous lipase (B) capable of being obtained from Humicola lanuginosa and/or Thermomyces lanuginosa and contained in such an amt. that the fat decomposition activity of the final compsn. becomes 0.005-100 LU/mg, 1-10% of 1-4C aliphatic alcohol (C), 0.1-5% of a water-soluble salt of 1-3C aliphatic carboxylic acid (D) and proteinase (E) contained in such an amt. that protein decomposition activity of the final compsn. becomes 0.1-50 GU/mg.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an enzyme-based liquid detergent containing a lipolytic enzyme and a protease derived from Humicola 1anu 1nosa or Thera+o-μ2iriyu and 1' and Shiriichi. Concerning the composition.

Nine Mountains” 1 coin Enzyme-based liquid detergent compositions are well known to those skilled in the art.

However, the majority of compositions of this type according to the prior art are enzymatic liquid detergent compositions containing a proteolytic enzyme component or a mixture of said component and an amylolytic enzyme.

One of the problems that arise when using enzymes in liquid detergent compositions
One is the stability of enzymes in liquid detergent compositions. Various proposals have been made in the art to increase enzyme stability in liquid detergent compositions, particularly with respect to proteolytic and/or starch-degrading enzymes. For example, European Patent Specification Box 28,865 and No. 28,866 discloses a method for stabilizing enzymes in liquid detergent compositions by introducing appropriate amounts of enzyme-accessible calcium and short-chain carboxylic acids or salts thereof, such as sodium formate. Some prior art uses proteolytic enzymes as the preferred enzymes, and is therefore not concerned with lipolytic enzymes in liquid detergent compositions; more recently, for example, US Pat. No. 4,707,291 (
Although it has been proposed to include lipases in detergent compositions, as described in Thom et al., these lipases are primarily considered for inclusion in granular detergent compositions. In European Patent Application No. 0258.068, Humi
It has been proposed to include certain lipases derived from cola 1anu 1nosa as detergent additives in liquid detergent compositions. This prior patent improves the stability of the lipase in liquid systems with 1,2-propanediol and calcium salts, and the stabilizing effect of sorbitol is slight.

The present invention particularly relates to lipases derived from the above-mentioned Humicola.
11um ico Ia (4m) origin (t 6
)! It is called J Bar Set.

Since these lipases are proteins like all enzymes, they are subject to decomposition by proteolytic enzymes.

Therefore, the stability of these lipases is further reduced in compositions that also contain proteolytic enzymes.

One of the objects of the present invention is the use of Humicola emetic 1 or -+ in liquid detergent compositions which also contain proteolytic enzymes.
The purpose of the present invention is to improve the storage stability of lipolytic enzymes derived from C.

The present inventor has discovered that when a lower aliphatic alcohol and a salt of a lower carboxylic acid are included in a proteolytic enzyme-containing liquid detergent composition that includes a cleaning action system mainly consisting of a nonionic detergent, the proteolytic enzymes are activated. Humicola Ia LLLQ9 a in liquid detergent compositions even in the presence of
It has been discovered that the storage stability of lipolytic enzymes derived from

Therefore, in a broad sense, the present invention is a proteolytic enzyme-containing liquid detergent composition comprising a detersive action system mainly consisting of a nonionic detergent,
The present invention relates to a detergent composition containing a lipolytic enzyme derived from No. 7, a lower aliphatic alcohol, and a salt of a lower carboxylic acid as main components.

The first major component of the liquid detergent composition of the present invention is a nonionic detergent. Nonionic detergents are well known to those skilled in the art. Detergents of this type are usually produced by reacting alkylene oxides, especially ethylene oxide, alone or together with propylene oxide, with compounds having hydrophobic groups and reactive hydrogen atoms, such as aliphatic alcohols, acids, amides or alkylphenols. It is a substance that has Typical examples of suitable non-ionic detergents include alkyl (C6-C22) phenol-ethylene oxide condensation products, linear or branched chain fatty acids, usually containing from 5 to 25 moles of ethylene oxide per mole of alkylphenol. Mention may be made of the condensation products of the group C=-C+s primary or secondary alcohols and usually 5 to 40 mol of ethylene oxide, as well as the condensation products of ethylene oxide and propylene oxide with ethylenediamine. Other nonionic detergents include block copolymers of ethylene oxide and propylene oxide, alkyl polyglycosides, tertiary amine oxides, and dialkyl sulfoxides. A preferred nonionic detergent is a condensation product of alcohol and ethylene oxide.

In the present invention, the above-mentioned nonionic detergents may be used alone or in combination. These one or more types of nonionic detergents are
Used as the sole cleaning action system of the liquid detergent composition of the invention, or provided that this non-ionic detergent constitutes the main part of the cleaning action system, another detersive action compound, e.g. anionic, cationic. It can be used in combination with ionic, zwitterionic or amphoteric detersive compounds.

The content of non-ionic detergent is 50% by weight of the cleaning action system.
or more, usually 60% by weight or more, preferably [7 or 70% by weight]
Do more than that. The total amount of cleansing compounds in the composition of the present invention is 1
0 to 90% by weight, usually 15 to 70% by weight.

The second major component of the composition of the invention is a lipolytic enzyme. This lipolytic enzyme
Look at the work and U Lenny! Fungal lipase (funFlal 1ipasc) that can be produced by
It is.

Specific examples of the fungal lipase include 1 as described in the aforementioned European Patent Application No. 0258,068 (NOVO).
In addition to lipase derived from L. 1umicola, Hu
S engineering JLLL who cloned the gene of Nicola 7 and brewed this gene! kl = lipase formed by expressing it in the liver.

This lipase is commercially available from NOVO Industry^/S under the trade name "Li polase"(E'). This Lipotase is one of the preferred lipases suitable for use in the present invention.

The lipase content of the liquid detergent composition of the present invention is such that the lipolytic enzyme activity of the final composition is 100 to 0 per 6 g of the composition.
．． 005 LU, preferably 25 to 0.05 LU.

1 lipase unit (LU) is Tris buffer y 5 mmo
13 mmol in l/l. C of Q', 2+ and 20mmo
Using an emulsion of 3.3% by weight olive oil and 3.3% by weight gum arabic as substrate in the presence of 1/1 NaCI at a temperature of 30° C. and p) 19.0:
p) is the amount of lipase that generates 1 pmol of titratable fatty acids per minute in the lstat.

Of course, these lipases can also be used in combination with each other. These lipases may also be used in unpurified or purified form, eg purified by known adsorption methods such as phenyl-Sepharose adsorption.

The third main component of the present invention is a lower aliphatic alcohol. The alcohol may be methanol, ethanol, propatool and isopropanol, or a mixture thereof. The preferred alcohol is ethanol.

The amount of lower aliphatic alcohol used in the present invention depends on the composition of the liquid detergent, but is usually 1 to 1 in the final composition.
10% by weight, preferably 2-8% by weight.

The fourth main component of the present invention is a salt of a lower aliphatic carboxylic acid. The acids include lower aliphatic carboxylic acids having 1 to 3 carbon atoms, such as formic acid, acetic acid and propionic acid. This component is introduced into the liquid detergent composition in the form of an acid and the salt of this acid is formed by metathesis. It may be formed in situ or introduced into the liquid detergent composition in the form of an acid salt. Suitable salts are water-soluble salts of alkali metals and mono-, di- and triethanolamines. Particularly preferred is sodium formate. The amount of lower aliphatic carboxylic acid salt used in the present invention is usually from 0.1 to 5%, preferably from 0.5 to 3.5% by weight of the final composition. Of course, these lower aliphatic carboxylic acid salts can also be used in combination with each other.

The fifth major component of the present invention is a proteolytic enzyme.

The enzyme may be of plant, animal or microbial origin. Preferred are enzymes derived from microorganisms such as yeasts, fungi, molds and bacteria. Particularly preferred enzymes are, for example, certain B.

5ubtilis and B.licheniformi
It is a bacterial "subtilisin" type protease obtained from the S strain.

Examples of suitable commercially available proteases include:
Novo Industry＾/S company's 81 calas
e■, 5avi-na s e@, Esperase
(!'; G15t-Brocades Maxat
asJ and Maxaeal”; Showa Denk
Kazusase@ from Company O; BPN and BPN' proteases, etc. The amount of protease in the composition is 0.1 to 5 ocu per final composition. Of course, these proteolytic enzymes can also be used in combination with each other.

GIJ is glycine units and corresponds to the amount of protein tradease that generates an amount of terminal NH2 groups equal to 1 μg per 1 glycine under standard incubation conditions.

The liquid detergent compositions of the present invention may also include one or more optional ingredients. These optional ingredients include, for example:
Fragrances and colorants, including deodorants,
Opacifiers (opacifiers), stain suspending agents, stain release agents, solvents such as propylene glycol, hydrotropes such as cumene, toluene or sodium xylene sulfonate and urea, alkalinities such as monodi- or triethanolamine. The liquid detergent compositions of the present invention may be builder-free or builder-free and may be aqueous or non-aqueous. If a liquid detergent composition containing a builder is required, from 1 to 60% by weight of one or more organic and/or inorganic builders.
, preferably 5 to 30% by weight, is included in the composition. Typical builders include alkali metal ortho-,
Billow and tripolyphosphates, alkali metal carbonates alone or mixed with calcite, alkali metal citrates, alkali metal nitrilotriacetates, carboxylmethyloxysuccinates, zeolites, polyacetal carboxylates, and the like.

In order to further increase the stability of the enzyme, it may also be advantageous to introduce Wi amounts of calcium salts. A typical example of a suitable calcium salt is calcium chloride. This added amount of calcium salt is accessible to the enzyme (e
nzyme-accessible) free calcium (
That is, it is determined that any component of the composition, such as calcium which is not subjected to sequestration by the builder, occurs in a proportion of 0.1 to 2 mmol per kg of final composition.

The compositions of the present invention may further include foam enhancers, antifoam agents, corrosion inhibitors, chelating agents, soil redeposition agents, bleaching agents, other enzyme stabilizers, bleach activators, etc. Compositions of the invention may also contain enzymes other than proteases and lipases, such as amylases, oxidases and cellulases. The content of these other enzymes is usually between 0.01 and 1 in the composition.
It can be 0% by weight.

When the liquid detergent composition of the present invention is an aqueous composition, an aqueous medium is also included in the composition in addition to the above-mentioned components. In the case of non-aqueous compositions, the above-mentioned components and main components constitute the entire composition.

The present invention will be explained in more detail with reference to non-limiting examples below.

The stability of Lipolase C) in various aqueous systems when stored at 37° C. for 27 days was investigated. All aqueous systems used were NoVO's proteolytic enzyme 5avinase 16. The system contained OL in an amount equal to 3011:U per ml. These aqueous systems consist of 4.9% ethanol or 2.7% sodium formate, 16.5% non-ionic detergent, or 4.9% ethanol and 2.7% sodium formate plus the non-ionic detergent. It contained a mixture of 16.5% ionic detergent. The non-ionic detergent is a mixture of CI2 to CI5 linear primary alcohols condensed with 9 moles of ethylene oxide. The results of this stability test are shown in the attached drawings. As is clear from this figure, the use of a ternary mixture of ethanol/sodium formate/nonionic detergent unexpectedly increased the stability of lipolytic enzymes compared to the use of these components alone. .

Using the same system as in Example I, the half-life of Lipolase was measured using various combinations of ingredients. The results are shown in the table below.

The following liquid detergent composition was tested to determine the amount of L contained therein.
The stability of ipolase was investigated.

! JLfL!ヱThe same amount of Lipol as in Example 3 was added to the following liquid detergent composition.
Ase and 5avinase were used.

Condensed with 9 moles of ethylene oxide 22.6 Coconut alcohol Sodium diethylene glycol ether sulfate 5.3 Coconut alcohol Sodium Tafli 3.5 Sodium formate 1.9 Ethanol
6.2 water
In addition to the above-mentioned components, the composition also contains Lipolase and 5avinase in such amounts that they exhibit an activity of 15 LU/ml and 30 (:U/ml), respectively, when the composition is used at a dose of 2 g per 11 wash liquors. It was.

The half-life of Lipolase at 37°C was 7 days.

When increasing the amount of sodium formate to 2.7%, Lipol
The half-life of ase exceeded 1.5 months.

16.5 Sodium dodecylbenzenesulfonate 3.5 Polyethylene glycol ester 0.6 Sodium formate
2,7 ethanol
4.9 water
The half-life of the remaining Lipolase at 37°C was over 1.5 months.

[Brief explanation of the drawing]

The accompanying figure is a graph showing the results of various enzyme stability tests.

Claims (6)

[Claims] (1)a) One or more nonionic detergent compounds are 5
Contains 10 to 90% of the cleaning action system that accounts for 0% or more, b) ￥Humicola￥ ￥lanuginosa￥
or ￥Thermomyces￥￥lanuginos
c) containing one or more lipases selected from fungal lipases obtainable from US$ in an amount such that the lipolytic activity of the final composition is from 0.005 to 100 LU/mg; c) containing from 1 to 1 carbon atoms; 1 to 1 lower aliphatic alcohol of 4
d) 0.1 to 5% by weight of a water-soluble salt of a lower aliphatic carboxylic acid having 1 to 3 carbon atoms; .1 to 50 GU/mg of an enzyme-based liquid detergent composition. (2) containing 15 to 70% by weight of detergent action system a);
Contains 0.05-25 LU/mg of lipase b), 2-8% by weight of lower aliphatic alcohol c), and water-soluble salt d)
The composition according to claim 1, containing 0.5 to 3.5% by weight. (3) the lower aliphatic alcohol is ethanol, the water-soluble salt of the lower aliphatic carboxylic acid is sodium formate,
Nonionic detergent compound is ethoxylated C_8~C_
The composition of claim 1, wherein the composition is a 1_8 primary linear alcohol. (4) Lipase is ￥Humicola￥ ￥lanug
Claim 1: The lipase is produced by cloning the gene of Aspergillus inosa and expressing this gene in Aspergillus oryzae.
The composition described in. (5) The composition according to claim 1, wherein the proteolytic enzyme is bacterial subtilisin. 6. A composition according to claim 1, which also contains a calcium salt in an amount such that the composition contains 0.1 to 2 mmol per kg of final product of enzyme-accessible free calcium.