JPS6126960B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to detergent compositions particularly suitable as automatic dishwasher detergents. Currently used automatic dishwasher detergent compositions are highly alkaline compositions that generally include chlorine-containing bleaches having a solution pH of greater than 11.5. Although this conventional detergent composition has very good cleaning properties, it has significant drawbacks in other respects. That is, although highly alkaline compositions are dangerous and have sufficient soil removal power due to the presence of chlorine bleach, some of the components of this composition are Special care is required during preparation and storage. That is, some components are susceptible to deterioration when they come into direct contact with active chlorine, so special care must be taken to protect these components. The stability of the chlorine bleach is also a critical condition and is also one of the factors that makes the preparation and storage of the composition difficult. Another drawback is that it is difficult to incorporate dyes and fragrances into this composition because they are unstable to chlorine. The object of the present invention is to provide a detergent composition which has a cleaning effect at least as good as the above-mentioned known detergents and which does not have the above-mentioned disadvantages or which has improved these disadvantages to at least a substantial degree. It is. The detergent composition of the present invention comprises a starch hydrolase (amylolytic enzyme).
It is a mildly alkaline composition containing a peroxygen bleach and a solution pH of about 9.3-10.8. "Solution PH" herein means the PH value measured in a solution prepared by dissolving the composition in distilled water at a rate of 3 g/ml. The upper limit of the PH value range (PH=about 10.8) is a condition established to ensure that the composition is made as a mildly alkaline composition with a solution PH of 11.0 or less. Previously, various enzyme-containing detergent compositions for dishwashers have been developed by various researchers in this field, but none of them have reached the commercial stage. Difficulties in manufacturing such detergent compositions include the instability of enzymes under highly alkaline conditions and/or
Or, the enzyme and bleach are immiscible with each other. Various proposals have been made to solve these problems, but so far none have been successful. U.S. Pat. No. 3,799,879 discloses a dishwashing detergent composition containing sodium perborate, a starch hydrolase, and optionally a protein hydrolase, and having a solution pH of 7-9. However, this composition does not have good cleaning power due to its extremely low alkalinity, ie its performance is unsatisfactory. U.S. Patent No. 4162987 states that the pH during use is 8.5−
Enzyme-containing detergent compositions for automatic dishwashers having a particle size of 11.5, preferably 9.5-10.5 are disclosed. However, this composition does not contain bleach, but instead contains a relatively large amount of nonionic surfactant, probably because the large amount was added to compensate for the lack of bleach. It appears to be. However, this composition was also far from ideal, as it should have performance as good as that of highly alkaline chlorine bleach-containing compositions. When creating automatic dishwasher detergent compositions that are effective, stable, mildly alkaline, and contain enzymes, enzyme activity, builder/ It is important to select and use each component appropriately so that a proper balance is maintained between buffering capacity, bleaching action, and surfactant content. Accordingly, the present invention provides an effective and stable enzyme-containing detergent composition suitable for use in an automatic dishwasher containing a starch hydrolase and a peroxygen bleach, comprising: (a) Contains 0.2-5% by weight of starch hydrolase,
Thereby, the composition has a starch hydrolysis activity of 10 ³ -10 ⁶ maltose units/Kg in the final composition stage, (b) contains 25-50% by weight of sodium triphosphate, (c ) Sodium carbonate and/or borax 7.5−
40% by weight, preferably 10-35%, and (d) 2-15% by weight of sodium silicate, with a SiO ₂ :Na ₂ O ratio of 1:1 to 4:1, preferably 1.5:1 to 3:1. (e) a solid peracid and its salts, and a mixture of a solid hydrogen peroxide adduct and an activating agent, wherein the weight ratio of said hydrogen peroxide adduct to activating agent is from 8:1 to 1. :1 preferably 4:1
(f) 0.05-1% by weight of a stabilizer for said bleach;
and optionally contains the following components (g)-(i), namely: (g) 0.2-5% by weight of protein hydrolase, whereby the composition is suitable for the final composition stage. has a protein hydrolase activity of 10 ⁶ -10 ⁸ glycine units/Kg, and/or (h) contains a low-foaming to non-foaming nonionic surfactant.
0.1-5% by weight and/or (i) fatty acids having a chain length of about 12-18 carbon atoms;
Contains 0.5-5% by weight, provided that the amounts of components (a), (c) and (d) are 9.3-10.8
The present invention relates to a detergent composition that is adjusted to obtain a composition having a builder and buffer capacity sufficient to maintain a solution pH of preferably 9.5-10.5. Preferred builder/buffer mixtures include sodium triphosphate, calcium carbonate and sodium silicate, where the SiO ₂ :Na ₂ O ratio is 2:1 to 2.5:1.
is). Starch hydrolase used in the present invention [ingredients]
(a)] may be derived from a fungus. Suitable starch hydrolases are Bacillus licheniformis strains NCIB8061, NCIB8059,
ATCC6334, ATCC6598, ATCC11945,
Starch hydrolase obtained from ATCC8480 and ATCC9945A. A particularly preferred starch hydrolase is Novo, Copenhagen, Denmark.
It is a starch hydrolase commercially available from Industri A/S under the name "SP-95" or "Termamyl" (registered trademark). These starch hydrolases are generally supplied in granular form and have an enzymatic activity of about 2-10 maltose units/mg. Enzyme activity is determined by “Method of
Enzymology”, Vol. (1955), p. 149. As a solid peracid [component (e)],
Various organic peracids described in publications such as No. 0027146 and No. 0027693 can be used. A preferred solid organic peracid is monoperoxyphthalic acid, which can be used in the form of the magnesium salt of the formula: Another type of solid peracid compound is an inorganic persulfate, a typical example of which is potassium monopersulfate. Examples of solid hydrogen peroxide adducts that can be used with activators in the present invention include alkali metal perborates (monohydrate or tetrahydrate), percarbonates, and persilicates. . Preferred hydrogen peroxide adducts are sodium perborate and sodium percarbonate. Activators for the peroxygen compounds used in the present invention are organic compounds that can react with hydrogen peroxide adducts in solution to produce organic peracids, which are effective bleaching agents. It is. Activators of this type are often referred to as "bleach precursors" or "peracid precursors," and many specific examples thereof are already known in the art. Activators which can be advantageously used in the present invention are tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), glycose-pentaacetic acid (GPA) and xylose-tetraacetic acid (XTA). Other suitable activators or peracid precursors are, for example, British Patent Nos. 836988, 855735;
No. 907356; U.S. Patent No. 1246339, No. 3332882;
No. 4128494; Canadian Patent No. 844481; Magazine “Detergent Age” June 1967 issue, pages 18-20
Page, July 1967 issue, pages 30-33 and 8, 1967
Published on pages 26, 27 and 67 of the month
It is described in Allan H. Gilbert's paper, etc. Stabilizers [component (f)] that can be used in the present invention are ethylenediaminetetraacetic acid (EDTA) and the compounds described in European Patent No. 0037146. A preferred stabilizer is ethylenediaminetetra-
(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), or a water-soluble salt thereof. It can be added in its pure form or in the form of its calcium, magnesium, aluminum or zinc complexes (US Pat. No. 4,259,200). In particular, calcium complexes are very suitable. As mentioned above, the composition of the present invention may preferably further contain a protein hydrolase [ingredient (g)]. Examples of suitable protein hydrolases include B. subtilis and B.
These include subtilisins obtained from certain strains of the licheniformis bacterium. Examples of commercially available subtilisins include "Maxatase®", commercially available from Gist-Brocades, Delft, Netherlands; and "Maxatase", commercially available from Novo Industri A/S, Copenhagen, Denmark. “Alcalase” (registered trademark) is mentioned.
Particularly suitable are proteases which exhibit maximum activity at a pH in the range of 8-12, which are obtained from certain strains of Bacillus, and which are
It is commercially available from Industri A/S under the trade names "Esperase" and "Savinase" (registered trademark). The preparation of these and similar enzymes is described in British Patent No. 1243784. These enzymes are commonly found in particulates (e.g. particulates in the form of marum, prill, T-granulate).
The enzymatic activity is generally around 500-
1700 glycine units/mg. Its proteolytic activity was reported in ML Anson's paper [“Journal of
General Physiology”, Vol. 22 (1938) p. 79]
It can be measured by the method described in . The following relationship exists between the Anson unit and the glycine unit. 1 Anson unit/g = 733 glycine units/mg A small amount of low-foaming to non-foaming nonionic surfactant is used to suppress excessive foaming caused by certain protein-based dirt and improve cleaning performance. Preferably, such surfactants include alkoxylated nonionic surfactants, where the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide, and mixtures thereof. ) can be given. However, the use of excessive amounts of nonionic surfactants should be avoided. Examples of low-foam to non-foam nonionic surfactants suitable for use in the present invention include commercially available ethoxylated-linear alcohols, specific examples of which include the Eurane Company
“Plurafac® RA30” and “Plurafac RA40” from BASF Company; “Letensol® LF403” and “Lutensol LF1300” from BASF Company; and Rohm & Haas
One example is "Triton (registered trademark) DF12" manufactured by Company. It is preferred to use fatty acids when producing compositions with relatively low PH values of the order of 9.3-10. Low PH compositions have a different tendency to rust silver than high PH compositions. An effective solution to this problem is the addition of small amounts of fatty acids with a chain length of _C12 - _C18 . In addition to or instead of this fatty acid, it is also possible to use corrosion inhibitors, such as benzotriazoles, which inhibit the development of silver rust. Furthermore, it may be necessary to add inert fillers to complete the composition. A preferred filler is sodium sulfate. The detergent compositions of the present invention can generally be prepared in the form of dry powder granular products. This means that the powdered or granular components are dry mixed according to conventional manufacturing techniques, and if liquid components (e.g. nonionic surfactants) are also to be incorporated, this is then added to the mixture. It can be produced by spraying on. EXAMPLES In order to specifically illustrate the present invention, examples are shown below. EXAMPLE - The following compositions were prepared in accordance with the present invention by dry mixing the components in the predetermined proportions. However, the liquid nonionic surfactant was added to the above-mentioned powder mixture as a final additive component. After addition of the nonionic surfactant, the product was mixed for an additional 3 minutes, during which time the product was exposed to ambient air.

[Table] Note: R○ in the table represents a registered trademark.
These products were sealed in 1 kg carton packs and stored for 2 months at a temperature of 20-22°C and a relative humidity of 50-60°C. No substantial deterioration of the activities of the main components amylase and protein hydrolase, nor of the activator, perborate, and stabilizer was observed. EXAMPLE The composition of the invention described in the example was tested in two dishwashers. As a comparative sample, a standard highly alkaline dishwashing composition containing chlorine bleach (commercially available) having the following composition was used. Sodium triphosphate 36 (%) Sodium metaphosphate 61 Potassium dichlorocyanurate (KDCCA)
2.0 Nonionic Surfactants 1.0 Test Summary This test was conducted under normal cleaning conditions using normal amounts of detergent. In each machine, in addition to the monitor, there was an item soiled with everyday food debris. Dishwasher: “Indesite” (registered trademark) “Philips” (registered trademark) Operation method Normal operation method for “Indesite” [Pre-wash 1
Main wash (65℃); Intermediate wash 2 times; Final wash 4 times
(65℃) once]; Water supply amount: 11.5-12 (for main cleaning). Normal operation method of “Philips” [Main cleaning (65
℃); 1 intermediate wash; 1 final wash (65℃);
Water supply amount 11.7-11.9 (for main cleaning). Hardness of water in the dishwasher “Indesit”: 22° during main washing (French hardness) 26° during final washing (French hardness) “Philips”: 15° during main washing (French hardness) Cleaning aid: 2ml Number of repetitions: “Philips” 6 times; “Indesit” 4 times Detergent usage: Composition ()...30ml Commercially available composition (S)...30ml PH measurement of washing liquid for main cleaning PH measurement value is It was as follows. Composition ()...9.8-9.9 Commercial product (S)...11.4-11.5 The test results after one washing test and six washings are shown in the following table.

【table】

[Table] As is clear from the above results, under the above test conditions, in substantially all respects, the composition of the present invention () was superior to the standard highly alkaline chlorine bleaching control sample. agent-containing compositions were found to be far superior to commercially available compositions.

Claims (1)

[Scope of Claims] 1. A detergent composition suitable for use in an automatic dishwasher containing a starch hydrolase and a peroxygen compound bleach, comprising (a) 0.2-5% by weight of a starch hydrolase;
Thereby, the composition has a starch hydrolysis activity of 10 ³ -10 ⁶ maltose units/Kg in the final composition stage; (b) contains 25-50% by weight of sodium triphosphate; (c) 7.5− sodium carbonate and/or borax
(d) 2-15% by weight of sodium silicate with a _SiO2 : _Na2O ratio of 1:1 to 4:1; (e) solid peracids and their salts; A peroxygen compound system selected from the group consisting of a mixture of a solid hydrogen peroxide adduct and an activating agent, wherein the weight ratio of said hydrogen peroxide adduct to activating agent is from 8:1 to 1:1. 5- bleach
(f) 0.05-1% by weight of a stabilizer for said bleaching agent;
Contains, provided that the amounts of components (a), (c) and (d) are 9.3−10.8
A detergent composition characterized in that the detergent composition is adjusted to obtain a composition having a sufficient builder and buffer capacity to maintain the solution pH of the detergent composition. 2. Claims characterized in that the composition further contains 0.2-5% by weight of protein hydrolase, so that the composition has a protein hydrolyzing activity of 10 ⁶ -10 ⁸ glycine units/Kg in the final composition stage. The detergent composition according to item 1. 3. The detergent composition according to claim 1, further comprising 0.1-5% by weight of a low-foaming to non-foaming nonionic surfactant. 4. A detergent composition according to claim 1, 2 or 3, further comprising 0.5-5% by weight of a fatty acid having a chain length of about 12-18 carbon atoms. . 5 Sodium carbonate and/or borax at 10-35
% by weight of the detergent composition according to any one of claims 1 to 4. 6. The detergent composition according to claim 2, wherein the protein hydrolase is a protease obtained from a strain of Bacillus that exhibits maximum activity over a pH range of 8-12. thing. 7. The activator is selected from the group consisting of tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), glucose-pentaacetic acid (GPA) and xylose-tetraacetic acid (XTA) and mixtures thereof. The detergent composition according to any one of claims 1 to 6, characterized by: 8. The bleach stabilizer is selected from the group consisting of ethylenediaminetetra (methylenesulfonic acid), diethylenetriaminepenta (methylenephosphonic acid), and their water-soluble salts, and their complexes with calcium, magnesium, aluminum or zinc. A detergent composition characterized in that: 9. A detergent composition according to any one of claims 1 to 8, characterized in that it has a solution pH of 9.5 to 10.5.