JPH0364560B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to enzyme detergent compositions with improved enzyme storage stability. More particularly, the present invention relates to detergent compositions containing an enzyme and a bleaching agent and having improved enzyme storage stability. It is well known in the detergent art that the inclusion of enzymes and bleaching agents in detergent compositions can lead to enzyme stability problems. If preventive measures are not taken, enzymes will be negatively affected by bleach and enzyme activity will decrease. In the past, a number of proposals have already been made for stabilizing enzymes in such bleach-containing detergents. For example, coating the enzyme and/or bleaching agent with a protective layer or adding certain stabilizers to the composition. Recently, German patent application No. 3321082, published on December 15, 1983, proposed to improve the storage stability of sodium percarbonate in detergent compositions by coating it with a film. are doing. The coating contains borates such as sodium tetraborate (anhydrous or various hydrated salts), sodium octaborate, sodium pentaborate, and sodium metaborate. Preferred are the dihydrate and tetrahydrate salts of sodium metaborate. These compositions may contain enzymes, and such enzyme-containing detergent compositions have been shown to have improved enzyme storage stability. Here, we have surprisingly discovered that enzyme storage stability in detergent compositions containing other peroxy-type bleaches can be improved by including sodium metaborate in such compositions. did. In the above references, sodium perborate is described and shown to be very stable compared to uncoated sodium percarbonate, and as stable as coated sodium percarbonate; It is not expected that addition of the inventive sodium metaborate to other peroxy-type bleaches would further increase enzyme stability. Furthermore, although the above references support the use of various borates, we have found that only alkali metal metaborate salts are effective as enzyme storage stability improvers in the compositions of the present invention. . Therefore, the present invention provides an enzyme detergent composition that is composed of a peroxy type bleach that is not an alkali metal percarbonate and an enzyme, and that has improved enzyme storage stability by containing an alkali metal metaborate in the composition. relating to things. Below, the invention will be discussed in more detail. The first essential ingredient is a peroxy type bleach other than an alkali metal percarbonate. Typical examples of these peroxy-type bleaches are alkali metal persulfates, perphosphates, perborates, perphthalates, organic peracids such as mono- or diperoxyazelaic acid, peroxyacetic acid, diperdodecanedioic acid, etc. are alkali metal and alkaline earth metal salts. Peroxy-type bleaches are preferably those that have better storage stability in terms of enzyme availability than percarbonates under the same storage conditions. A particularly preferred bleaching agent is sodium perborate in the tetrahydrate and monohydrate forms. Generally, the amount of peroxy-type bleach in the composition of the invention is from 1 to 40% by weight, preferably 3% by weight.
~35% by weight, particularly preferably 5-30% by weight. In this regard, the compositions of the present invention may contain bleach precursors such as tetraacetyl ethylene diamine, tetraacetyl glycoluril, glycol pentaacetate, and the like to provide peroxy-type bleaches in low temperature bleach detergent compositions. The amount of these bleach precursors usually ranges from 0.5 to 20% by weight. The second essential ingredient is an alkali metal metaborate. Typical preferred examples are sodium metaborate and potassium metaborate, both in anhydrous form and in various hydrated salt forms such as potassium metaborate hemihydrate,
It may also be sodium metaborate dihydrate and tetrahydrate. The alkali metal metaborate can be added to the composition of the invention as a powder, or can be deposited on the surface of the peroxy bleach when the peroxy bleach is in granular form. In this regard, it has been discovered that the storage stability of the enzyme is improved even further if the granular peroxy bleach is first treated with a potassium salt, which has a lower equilibrium humidity than the granular peroxy bleach, and then treated with sodium metaborate. A typical example of a suitable potassium salt is potassium metaborate. Both the potassium salt and the sodium metaborate are applied to the granular peroxy bleach in dry powder form. Metaborate can also be formed in situ on the peroxy bleach surface by adding a metaborate forming substance that reacts with the peroxy bleach, such as dimethyl sulfoxide. In general, the amount of alkali metal metaborate present in the compositions of the invention is from 0.1% to 50% by weight, preferably from 0.2 to 30% by weight, particularly preferably from 0.5 to 20% by weight. The third essential component of the composition of the invention is an enzyme.
Typical examples of enzymes that can be used in the present invention are proteases, amylases and cellulases, such as those commonly proposed for inclusion in detergent compositions in the detergent field. A suitable example of a proteolytic enzyme is commercially available Maxatse [Gist-
Brocades) NV Delft, Netherlands]
and subtilisins obtained from specific strains of B. subtilis and B. licheniformis , such as Alcalase [Novo Industri A/S, Copenhagen, Denmark]. be. It was developed by Novo Industri A/S and is commercially available under the trademarks Esperase and Savinase. Particularly preferred are proteases obtained from strains of Bacillus that have maximum activity at pH 8-12. The preparation of such enzymes is described in GB 1243784. A suitable example of a starch-degrading enzyme is Maxamyl [Gist-
commercially available amylases such as Termamyl (Novo Industri A/S) and Termamyl (Novo Industri A/S). UK patent no.
Also suitable is the amylase described in US Pat. No. 1,296,839. Typical examples of commercially available lipolytic enzymes include Lipase YL. Amano CE. Wallerstein AW. Lipase.
A typical example of a cellulolytic enzyme is the cellulase from Humiscola insolens described in German Patent Application No. 3117250. The advantages of the invention are particularly pronounced with amylase-containing formulations. The amount of enzyme present in the composition of the invention depends on the activity of the enzyme preparation used. The higher the activity, the lower the amount of enzyme required. Generally, this amount will be between 0.001 and 10% by weight of the composition, and for most practical purposes between 0.1 and 5%. The compositions of the present invention may further contain other ingredients normally included in bleaching detergent compositions. Thus, the compositions of the invention may contain one or more surfactants such as soaps, anionic, nonionic, cationic and/or amphoteric synthetic detergents in amounts up to 60%. Furthermore, it may contain amounts of up to 60% by weight of one or more inorganic and/or organic builder salts such as condensed phosphates, silicates, carbonates, nitrilotriacetates, etc. In this regard, it has been discovered that the advantages of the present invention are particularly pronounced in formulations containing phosphate builder salts. Additionally, other optional ingredients include soil suspending agents.
suspending agents), solubilizers, preservatives, dyes,
Fragrances, optical brighteners,
Antifoaming agent, bactericidal agent, anti-tarnishing agent
agents), other enzyme stabilizers, softeners, sequestering agents such as aminopolyphosphonic acids, clays, etc. A typical formula for mechanical dishwashing is 20-50% sodium tripolyphosphate, 2-20% sodium silicate.
%, sodium carbonate 0-50%, sodium perborate 5-25%, amylase and protease 4%
up to 10% TAED, and up to 1% aminopolyphosphonic acid. The compositions of the present invention can be prepared in any suitable particulate form, such as powder, granules, tablets, flakes, ribbons, noodles, etc., for laundry washing, hard surface cleaning, dishwashing and general purpose cleaning. Can be used for The invention will be further illustrated by examples. Example 1 The following dry mix formulation was prepared.

[Table] Termamyl is a British patent no.
No. 1296839 and is commercially available from Novo Industri AS. These products were stored under the conditions shown in the table below, and residual enzyme activity (REA) was measured at the end of the storage period.
The results were as follows.

【table】 Example 2

[Table] SP227 is a cellulase described in German Patent Application No. 3117250 and manufactured by Novo Industri AS. Savinase is a protease described in British Patent No. 1243784 and manufactured by Novo Industri AS. Store these formulations in closed cups at 37°C;
Residual enzyme activity (%) was measured after the storage period described below. The following results were obtained.

【table】 Example 3 The following formulations were prepared by dry blending.

【table】 After storage in an open container at 37℃/70%RH for 2.7 days, G 16.9% H 14.9% The residual enzyme activity was measured. Example 4 The following compositions were prepared by dry mixing.

[Table] These products were stored in an open container at 37°C/70% RH and in a closed container at 37°C for × days. The residual enzyme activities were as follows.

Table: Example 5 A composition was prepared consisting of 2.1% Termamyl, 10% sodium perborate tetrahydrate, alkali metal metaborates specified in the table below, and up to 100% sodium tripolyphosphate. . The residual enzyme activity after storage in an open container at 37° C./70% RH for × days was as follows.

[Table] Example 6 Inside the Lodige mixer,
Granular Sodium Perborate (73.92Kg) at 20℃
and powdered potassium metaborate 1.5H ₂ O (2.94Kg)
and mixed for 1 hour. The metaborate melts within the surface of the perborate granules, forming a flowing surface. Then, powdered anhydrous sodium metaborate (7.14Kg) was added to the mixer. This adhered to the flowing surface and restored the free-flowing properties of the granules. After sieving and collecting particles with a diameter of more than 230 μm, 79.5 Kg of granules containing up to 87.3% sodium perborate were obtained. Formulations were made to the granules with or without the separate addition of anhydrous sodium disilicate. These formulations were compared to the same formulations minus the metaborate. The formulation contained the following composition:

[Table] The residual enzyme activity after storage for X days at 30°C/60-65% PH in an open container was as follows. ×= 0 8 14 A 96 54 34 B 98 74 65 C 98 61 48 D 99 81 69

Claims (1)

[Scope of Claims] 1. An enzyme detergent whitener composition comprising an enzyme, a peroxy bleach other than an alkali metal percarbonate, and an enzyme storage stability improving agent, the enzyme storage stability improving agent is an alkali metal metaborate. 2. The composition according to claim 1, wherein an alkali metal metaborate is attached to the surface of the granular peroxy bleach. 3. The composition according to claim 2, wherein sodium metaborate is attached to the surface of a granular peroxy bleach that has been first treated with potassium metaborate. 4. The composition according to any one of claims 1 to 3, wherein the enzyme is amylase and the peroxy bleach is sodium perborate.