JPH0277499A - Detergent composition for use in automatic dishwasher - Google Patents

Abstract

PURPOSE:To provide the title detergent excellent in cleaning power for oil stain and giving high performance even in coexistence of yolk stain, containing a nonionic surfactant, alkali builder and alkali lipase. CONSTITUTION:The objective composition containing (A) 1-15 (pref. 3-10)wt.% of a nonionic surfactant <=35 deg.C (pref. <=30 deg.C) in the cloud point of a 1wt.% aqueous solution thereof, (B) 20-70 (pref. 30-60)wt.% of an alkali builder comprising (meta)silicate and (bi)carbonate, and (C) an alkali lipase with its lipase activity at pH9 >=30 (pref. >=50)% of that at pH7.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an automatic dishwasher detergent composition containing lipase as an enzyme.

From summer to summer Automatic dishwashers simplify cleaning up after meals.

Due to the good finish of the tableware and the fact that it does not cause roughness during washing, it is becoming more and more commonly used in households.

Attempts to use enzymes in detergents for automatic dishwashers have been made for a long time, and Japanese Patent Publication No. 47-20235 discloses a detergent composition containing amylase, protease, and lipase.

However, cleaning agents for automatic dishwashers containing lipase among these enzymes have not yet been put into practical use. This is because while lipase is effective in decomposing oily stains remaining on tableware, conventional lipases have the disadvantage that they are deactivated in alkaline environments and cannot exhibit their effectiveness.

In addition, when egg yolk stains coexist, commercially available cleaning agents foam, which has the drawback of reducing cleaning power and causing pump failure due to the foam.

The objective of the present invention is to provide a cleaning agent for automatic dishwashing that has excellent oil stain cleaning ability and also exhibits excellent performance even when egg yolk stains coexist.

The present invention is characterized by containing the following components (a), (b), and (c).

(a) Nonionic surfactant having a cloud point of 35° C. or less in a 1% by weight aqueous solution: 1 to 15% by weight.

(b) 20-70% by weight of alkali builder.

(c) An alkaline lipase whose lipase activity at pH=9 is 30% or more of the lipase activity at pH=7.

The present invention will be explained in more detail below.

The nonionic surfactant used as component (a) in the present invention has a cloud point of 35° C. or lower, preferably 30° C. or lower in a 1% by weight aqueous solution. Such a nonionic surfactant can be appropriately selected from conventionally known nonionic surfactants, but it is generally preferable to select it from the following types.

(1) A block polymer of polyoxyethylene and polyoxypropylene having a molecular weight of 1,000 to about 10,000. It was first developed by the American Wyandotte Company under the trade name Pluronic, and is generally known as "
It's called "Pluronic."

(2) A polyoxyethylene and polyoxypropylene adduct of ethylenediamine having a molecular weight of 1,000 to about 10,000. It was first developed by the American company Wyandotte, and is commonly referred to as Tetronic.

(3) Ethylene oxide (EO) and propylene oxide (PO) adduct of alcohol represented by the following - Shipman (1).

R, -CH○(C,H40), (C,H,○), )i
・-(s) (wherein R□ and R2 represent an alkyl group or alkenyl group of C□ to cis, and R□+R2
The total number of carbon atoms is 7 to 19. Also, m is 5 to 15
is a positive number, n is a positive number from 3 to 15, and m/n
The ratio is in the range 3/1-1/2. The order and form of addition of ethylene oxide and propylene oxide may be interstitial, random addition, or block addition. ) The content of the nonionic surfactant used in the present invention is
It ranges from 1 to 15% by weight in the detergent composition, preferably from 3 to 10% by weight. If the content of the nonionic surfactant is less than 1% by weight, good cleaning performance cannot be obtained, and if it exceeds 15% by weight, foam control becomes difficult, which is not preferable. 35
Even better cleaning performance can be obtained by using one that exhibits a cloud point lower than °C.

As the alkali bilter used as component (b) in the present invention, metasilicates, silicates, carbonates, hydrogen carbonates, and the like can be used alone or in combination. These are usually preferably alkali metal salts such as sodium and potassium.

The content of alkali virgo used in the present invention is in the range of 20 to 70% by weight, preferably 30 to 60% by weight in the cleaning composition. If the content of alkaline bilgu is less than 20% by weight, good cleaning performance cannot be obtained;
Even if it exceeds the weight percentage, it is not preferable because no significant improvement in performance can be expected.

The alkaline lipase used as component (C) in the present invention has a lipase activity at pl(=9) of 30% or more, preferably 50% or more of the lipase activity at pl+=7.The lipase activity at pH 7 and ρ119 is , is measured as follows.

Lipase "Z" Using olive oil as a substrate, the fatty acids liberated by lipase action are quantified by alkaline titration, and the lipase activity is determined from this value.

One enzyme unit is an enzyme that releases 1 μM fatty acid per minute from the substrate olive oil at 37°C.

4mQ of olive oil and 0.1M phosphate buffer (pH 7.0)
) Accurately place 4 m Q and 50 ra Q volume in a stoppered Erlenmeyer flask, mix well, and use a constant temperature water bath at 37°C for 10 min.
Preheat for a minute. Add exactly 1 mQ of sample solution to this, mix well, and after exactly 20 minutes pour in acetone/ethanol mixed solution 20+*Ω, then phenolphthalene test solution 5
Using the drop as an indicator, titrate with 0.05N sodium hydroxide test solution.

Separately, add 5fflQ of olive oil and 0.1M phosphate buffer (
Accurately place 4 ts Q (pH 7,0) into a 50 m Q volume stoppered Erlenmeyer flask, heat at 37°C for 30 minutes, then pour in 20 m Q of the acetone/ethanol mixture, then add exactly 1++ A of purified water, and add phethanol phthalene. Using 5 drops of the test solution as an indicator, titrate with 0.05N sodium hydroxide test solution and use as a control solution.

Calculation of enzyme unit Lipase titer (unit/g) = (sample solution titration value - control solution titration value) When measuring at pH = 9, use 0.2M Tris buffer to set pH = 9. , and others were carried out in accordance with the above method.

As alkaline lipase suitable for the present invention, Candi
da cylindracea, 1luIIlico
la lanuginosa.

1'sudomonas, Mucor sp., C
hromobacterium viscosulI 1%
There are lipases derived from microorganisms such as Rh1zopus japonics, including lipase MY and lipase OF.

Candida cylindra, manufactured by Tetrasaccharide Industry ■
cea), Lipase P, Lipase CBS (manufactured by Ohno Pharmaceutical ■, Origin @ Pseudomonas), Lipase SP (manufactured by Novo Co., Ltd., Origin Mucor sp), Lipase (manufactured by Toyo Jozo ■, Origin Chron+obacteriu)
m viscosum), Lipase LPL (Oriental Yeast-12), Olivase (Osaka Bacteria Research Institute type, origin Rh1zopus japonics), Lipase B
(Made by Sara Polo Beer, origin Pseudomonas)
It is commercially available as. In addition, special public service 53-453
Publication No. 94 discloses that a lipase-producing filamentous fungus belonging to the Humicola genus (including the Thermomyces genus) is cultivated, and lipase is collected from the culture; strain (Keikoken Bibori No. 1045) has been reported, and such lipases are also suitable.

Furthermore, lipases produced from genetically modified microorganisms can also be used. As an example of this, JP-A-62-27
In No. 2988, Aspergillus oryza (Aspergillus oryzae)
gillus oryzae) as a host, and the recombinant DNA
It has been reported that lipase can be produced by transforming cells using the A technique and culturing them in a culture medium.

(c) Component alkaline lipase is 1 kg per 1 kg of cleaning agent.
It is suitable to blend in an amount of 10,000 to 1,000,000 lipase units (LU).

In addition to the above-mentioned essential components, various optional components can be added to the cleaning composition of the present invention as needed. Optional ingredients include surfactants other than component (a) such as anionic surfactants, nonionic surfactants, and cationic surfactants, zeolite, water-soluble phosphate-free calcium-trapping chelate builders, and other components other than component (c). enzymes, hypochlorite,
Bleaching agents such as percarbonates, reducing agents such as sulfites.

Anti-recontamination agents such as carboxymethylcellulose recall, antifoaming agents such as silicone, inorganic substances such as white carbon, bulking agents such as Glauber's salt, fragrances,
Examples include additives such as pigments.

Among surfactants other than component (a), examples of anionic surfactants include the following.

- Straight-chain alkylbenzene sulfonate having an alkyl group having 9 to 18 carbon atoms.

- Olefin sulfonate having an alkyl group having 8 to 24 carbon atoms.

- Alkyl sulfate having an alkyl group having 8 to 16 carbon atoms.

- An α-sulfo fatty acid ester salt or fatty acid salt having a fatty acid residue having 8 to 22 carbon atoms.

- Ethoxylated primary or secondary alcohol sulfate having 8 to 18 carbon atoms.

As a calcium-trapping chelate builder.

For example, aminopolyacetates such as nitrilotriacetate and ethylenediaminetetraacetate; polyhydric carboxylates such as citrate and succinate; polyacrylates, hydroxypolyacrylates, polyacetal carboxylates, and acrylic acids. Salts of copolymers with maleic anhydride, salts of copolymers with maleic anhydride and methyl vinyl ether, salts of copolymers with maleic anhydride and olefins, salts of copolymers with acrylic acid and methacrylic acid Examples include polymer electrolytes such as.

The above chelate builders may be used alone or in combination of two or more.

In addition to the alkaline lipase of the present invention, other enzymes such as protease, cellulase, amylase, etc. can be added as enzymes.

The form of the cleaning composition of the present invention is preferably powder or granules. As for its manufacturing method, a nonionic surfactant is impregnated into an alkali builder or the like and mixed. Alternatively, a method may be mentioned in which they are granulated and further mixed with enzyme particles.

According to the cleaning composition of the present invention, the alkali builder contains
When dishes are washed in an automatic dishwasher by combining a nonionic surfactant with specific properties and a specific lipase, it has excellent oil stain cleaning power, and when egg yolk stains coexist. It also has low foaming properties and can prevent problems caused by foaming.

Hereinafter, the present invention will be described in more detail with reference to Examples. Prior to this, the evaluation method employed in the Examples will be explained.

1L of dirt removed: 4 plates evenly coated with 5 g of butter and 4 plates coated evenly with 5 g of salad oil were used.

Washing conditions: Using a National automatic dishwasher NP-600, washing was performed using a standard course. The tableware to be washed is the 8 dishes mentioned above.

Judgment criteria: After washing, take out the 8 plates and visually evaluate them on a 5-point scale (5 indicates that the dirt is completely removed, and 1 indicates that no dirt is removed at all).

The average score is taken as the cleaning power.

Apply 20 g of half-boiled egg yolk to one 20 cm plate and place it in a dishwasher together with 3 clean plates and 4 bowls. The washing machine used is National NP-600, and the washing was carried out in a standard course. After the cleaning start IO minutes have elapsed, open the door of the washer and set the height from the water surface to 81'J.

The cleaning agent components shown in Example Table 1 were mixed in a V-type mixer to prepare one granular cleaning agent (cleaning agent N11l-4).

5 g of each of the obtained granular detergents was collected, granular enzyme was added to a predetermined amount, and the mixture was subjected to a test. The test results compared with the enzyme-free system are shown in Table 2.

Here, lipase is the DN of Humicola langinosa.
Lipase produced from A recombinant bacteria [activity ratio = 7
0% (pH=9/pH=7)) was used.

Table-1: Particulate detergent composition amount 20%, cloud point 27°C in 1 wt% aqueous solution, Asahi Denka ■×2) Pluronic L92; average molecular weight 3500.
Cloud point of 1% by weight aqueous solution: 26°C, manufactured by Asahi Denka@

Claims (1)

[Claims] 1. (a) Nonionic surfactant whose cloud point is 35°C or less in a 1% by weight aqueous solution: 1 to 15% by weight, (b) Alkali builder: 20 to 70% by weight, ( c) An alkaline lipase whose lipase activity at pH=9 is 30% or more of the lipase activity at pH=7. A detergent composition for an automatic dishwasher, comprising: