JP6027877B2 - Detergent composition for automatic dishwasher - Google Patents

Description

  The present invention relates to a cleaning composition for an automatic dishwasher, and a dishwashing method using the same.

Dirt from rice or tea astringents adheres strongly to the tableware, making it difficult to wash with an automatic dishwasher. Therefore, when washing such stains with an automatic dishwasher, pretreatment such as pre-immersing the dishes in water or lightly washing the hands is necessary, which is troublesome.
Then, development of the cleaning composition for automatic dishwashers which can remove dirt without performing such a pretreatment which requires such a labor is desired.

  In recent years, a lot of organic chelating agents with good biodegradability have been blended in detergents for automatic dishwashers from the viewpoint of environmental considerations. Examples of the organic chelating agent include glycine-N, N-diacetic acid derivatives (hereinafter also referred to as “GDA”).

Patent Document 1 discloses a mixture of a hydrophobically modified polycarboxylate and a hydrophilically modified polycarboxylate, a complexing agent, a low-foaming nonionic surfactant, a bleach, and a builder. Cleaning preparations containing enzymes, etc. are described, and GDA is described as one type of complexing agent.
Patent Document 2 describes a cleaning composition containing a protease and exemplifies a composition example using GDA together.
Patent Document 3 describes a dishwasher detergent composition containing a metal catalyst, a peroxide, and a nonionic surfactant, and exemplifies a composition example containing 1% by mass of GDA.
Patent Document 4 describes a granular detergent composition for a dishwasher containing GDA, a maleic acid / acrylic acid copolymer and / or a salt thereof, a lipase, a nonionic surfactant having a specific structure, and an inorganic peroxide. There is.

Special table 2011-500878 gazette Special table 2012-503710 gazette JP 2008-037885 A JP 2012-144656 A

The cleaning agent described in Patent Document 1 is intended to suppress the formation of water spots, and no study has been made on the cleaning power against dirt caused by rice or tea astringency.
Patent Document 2 only describes GDA as one type of complexing agent, and the relationship between GDA and detergency and the blending amount thereof have not been sufficiently studied. Furthermore, Patent Document 2 describes the removal of protein stains and the removal of cooked, oven-baked, and burnt stains. Has not been considered.
In Patent Document 3, there is a description that the detergent composition for a dishwasher containing a metal catalyst has a detergency against oil stains, starch stains and tea astringent stains. Since the detergency is not sufficient, further improvement of the detergency is desired.
Patent Document 4 also describes that oil / fouling and re-contamination of soap scum can be suppressed, contamination on the inner surface of the drainage hose of the dishwasher can be suppressed, and unpleasant fatty acid odor in the automatic dishwasher can be reduced. There are no studies on the contamination of rice and tea astringents.
The present invention provides a cleaning composition for an automatic dishwasher that exhibits excellent cleaning performance against dirt caused by rice or tea astringents, and a dishwashing method using the same.

That is, the present invention provides the compound (A) represented by the following general formula (1) in an amount of 10 to 25% by mass,
1% by mass or more and less than 10% by mass of percarbonate (B),
0.05 to 3% by mass of protease (C),
0.05 to 3% by mass of amylase (D) and 5 to 20% by mass of polycarboxylic acid type polymer compound (E),
Provided is a detergent composition for an automatic dishwasher having a mass ratio [(A) / (B)] of more than 1 and 10 or less.

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for tableware which shows the outstanding cleaning performance with respect to the stain | pollution | contamination by rice or tea astringent, and the washing | cleaning method of the tableware using the same can be provided.

[Cleaning composition for automatic dishwashers]
The cleaning composition for an automatic dishwashing machine of the present invention is 10 to 25% by mass of the compound (A) represented by the following general formula (1), and 1% by mass or more and 10% by mass of the percarbonate (B). Less than, 0.05-3 mass% of protease (C), 0.05-3 mass% of amylase (D), and 5-20 mass% of polycarboxylic acid type polymer compound (E), mass ratio [(A) / (B)] is more than 1 and 10 or less.

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)

<(A) component>
The component (A) is a compound represented by the following general formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)

The hydrocarbon group represented by R in the general formula (1) is preferably an alkyl group or an alkenyl group. In this invention, carbon number of an alkyl group is 1-12, 1-6 are preferable and 1-3 are more preferable. Moreover, carbon number of an alkenyl group is 2-12, 2-6 are preferable and 2-3 are more preferable. If carbon number is in the said range, the biodegradability and cleaning power of the cleaning composition for automatic dishwashers obtained will become favorable.
Specific examples of the preferable alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, and the like. Among these, a methyl group is preferable. . Here, “various” means various isomers including n-, sec-, tert-, and iso-.
Specific examples of preferred alkenyl groups include vinyl, allyl, 2-butenyl, 2-methyl-2-propenyl and the like.

M in the general formula (1) is one selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. In these, a hydrogen atom and an alkali metal are preferable from a viewpoint of availability and a manufacturing cost reduction, and especially sodium is preferable.
The component (A) may be either liquid or solid, but it is preferable to use the solid (A) component from the viewpoint of efficient production and handling.

10-25 mass% of said (A) component is contained in the cleaning composition for automatic dishwashers. When the content of the component (A) is 10% by mass or more, an effect as an organic chelating agent can be sufficiently obtained, and when it is 25% by mass or less, raw material costs can be suppressed and the production can be efficiently performed.
The content of the component (A) in the cleaning composition for an automatic dishwasher is preferably 10.5% by mass or more from the viewpoint of sufficiently obtaining the effect as an organic chelating agent and the cost. 8 mass% or more is more preferable, 11 mass% or more is further preferable, and 23 mass% or less is preferable, 22 mass% or less is more preferable, 20 mass% or less is further preferable, and 18 mass% or less is more preferable, Specifically, 10.5-23 mass% is preferable, 10.8-22 mass% is more preferable, 11-20 mass% is still more preferable, and 11-18 mass% is still more preferable.

<(B) component>
The cleaning composition for an automatic dishwasher of the present invention contains 1% by mass or more and less than 10% by mass of percarbonate. In the present invention, the content of percarbonate refers to the amount converted by the effective component concentration.
When the content of the percarbonate is 1% by mass or more and less than 10% by mass, excellent cleaning ability can be obtained while suppressing the production cost.
The content of percarbonate is preferably 1.6% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, still more preferably 6% by mass or more, and 9% by mass or less. Preferably, it is 8 mass% or less, more preferably 7.8 mass% or less, and even more preferably 7.5 mass% or less.
The specific percarbonate content is preferably 1.6 to 9% by mass, more preferably 4 to 8% by mass, still more preferably 5 to 7.8% by mass, and more preferably 6 to 7.5% by mass. Further preferred.
Examples of the percarbonate include sodium percarbonate and potassium percarbonate. Among these, sodium percarbonate is more preferable.

When the percarbonate is a granulated product, the effective concentration of the percarbonate in the percarbonate granulated product is preferably 50% by mass or more and less than 95% by mass. From the viewpoint of cleaning performance, it is preferably not less than the lower limit, and by making it not more than the upper limit, the production cost can be reduced and the storage stability of the percarbonate can be improved.
The effective concentration of percarbonate in the percarbonate granulated product is more preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and still more preferably 80% by mass or more, And 90 mass% or less is more preferable, and 85 mass% or less is still more preferable.
The specific effective component concentration of the percarbonate in the percarbonate granule is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, more preferably 70 to 85% by mass, and 75 to 85% by mass. % Is more preferable, and 80 to 85% by mass is even more preferable.
In the present specification, the “granulated product” refers to agglomerated fine particles and agglomerated fine particles.

  The effective concentration of sodium percarbonate can be measured using the potassium permanganate titration method described in JP-A-6-316700. Moreover, it can also obtain | require by measuring an effective oxygen concentration from the iodometry method of Unexamined-Japanese-Patent No. 2006-187276.

As the percarbonate, it is preferable to use a percarbonate coated from the viewpoint of storage stability.
The coated percarbonate is preferably one coated with a water-soluble polymer or inorganic salt. As coating methods, Japanese Patent Publication No. 47-32200, Japanese Patent Publication No. 53-15717, US Pat. No. 4,131,562, US Pat. No. 4,120,812, German Patent No. 2712139, German Patent No. 2800916, European Patent No. 30759, Examples thereof include methods described in Japanese Utility Model Laid-Open Nos. 58-217599, 59-196399, and 4-31498.

<(C) component>
The detergent composition for an automatic dishwasher of the present invention contains 0.05 to 3% by mass of protease because it exhibits a remarkable effect on denatured proteins that are difficult to remove with a surfactant or the like. When the content of the protease is 0.05% by mass or more, the cleaning performance can be sufficiently improved, and when it is 3% by mass or less, the production cost can be kept low.
From the viewpoint of improving the washing performance and reducing the production cost, the protease content is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, still more preferably 1.0% by mass or more, and 2.8 mass% or less is preferable, 2.5 mass% or less is more preferable, and 2.2 mass% or less is still more preferable.
The specific protease content is preferably 0.5 to 2.8% by mass, more preferably 0.8 to 2.5% by mass, and still more preferably 1.0 to 2.2% by mass.

Protease is preferably used as a granulated product with a binder, a coating agent and the like based on a normal granulation method from the viewpoint of stability and solubility in water.
When using protease as a granulated product, the protease content in the granulated product is preferably 0.1 to 10% by mass as the amount of enzyme protein.

In the present invention, the α-keratin degradation activity at 10 ° C. described in JP-A No. 2000-328097 is less than 0.09 × 10 ⁻³ μg / mPU · min, particularly 0.01 × 10 ^{−3 to} 0.07 ×. 10 ⁻³ μg / mPU · min, preferably α-keratin degradation activity at 30 ° C. is less than 0.40 × 10 ⁻³ μg / mPU · min, more preferably 0.05 × 10 ^{−3 to} 0.35 × 10 ⁻³ μg / mPU · min, more preferably 0.05 × 10 ^{−3 to} 0.30 × 10 ⁻³ μg / mPU · min, particularly preferably 0.05 × 10 ^{−3 to} 0.20 × 10 ^−. It is preferable to use ³ μg / mPU · min protease.

  Examples of commercially available protease products include alcalase, sabinase, everase, cannase, esperase (Novozymes Japan Co., Ltd.), ovozyme, platin, properase, and platinum OX (Danisco).

<(D) component>
The cleaning composition for an automatic dishwasher of the present invention contains 0.05 to 3% by mass of amylase. When the content of amylase is 0.05% by mass or more, it is possible to sufficiently improve the cleaning performance, particularly the performance of removing gelatinized starch, and when it is 3% by mass or less, the production cost can be kept low. .
From the viewpoint of improving the cleaning performance and reducing the production cost, the content of amylase is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.6% by mass or more, and 2.5 mass% or less is preferable, 2 mass% or less is more preferable, and 1.5 mass% or less is still more preferable.
The specific amylase content is preferably 0.2 to 2.5% by mass, more preferably 0.4 to 2% by mass, and still more preferably 0.6 to 1.5% by mass.

The optimum temperature of the amylase used in the present invention is preferably 30 ° C to 75 ° C, more preferably 35 ° C to 75 ° C, more preferably 40 ° C to 70 ° C, further preferably 45 ° C to 65 ° C, and more preferably 50 ° C to 60 ° C. ° C is even more preferred. The optimum pH of amylase is preferably 6.5 to 10, more preferably 7 to 9.5, more preferably 7.5 to 9, and still more preferably 8 to 9. Specifically, it is preferable to use an amylase having an optimum temperature of 30 ° C. to 75 ° C. and an optimum pH of 6.5 to 10 as the component (D).
The optimum pH of amylase is various buffer solutions (acetate buffer (pH 4.5 to 6.0), potassium phosphate buffer (pH 6.0 to 8.0), glycine sodium hydroxide buffer having a final concentration of 50 mM. Solution (pH 9.0 to 10.5) and carbonate buffer solution (pH 10.0 to 12.0)], and the activity of the target enzyme is measured by the amylase activity measurement method, and the pH indicates the maximum activity. Moreover, the optimal temperature of amylase can be calculated | required by changing temperature on the conditions of pH 9.0 about an object enzyme, and measuring activity.

Amylase is preferably used as a granulated product with a binder, a coating agent and the like based on a normal granulation method from the viewpoint of stability and solubility in water.
When amylase is used as a granulated product, the amylase content in the granulated product is preferably 0.1 to 10% by mass as the amount of enzyme protein.
The activity of amylase is preferably 100 IU to 50 million IU, more preferably 10,000 IU or more, further preferably 100,000 IU or more, and even more preferably 150,000 IU or more from the viewpoint of improving detergency. The activity of amylase can be determined by the phadebas method described in JP-A-2006-187276.

  From the viewpoint of improving detergency, amylase is preferably α-amylase, and commercially available products include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novozymes Japan Co., Ltd.), Plaster ST, Plaster OxAm ( Danisco).

  The detergent composition for an automatic dishwasher of the present invention can provide a high cleaning effect by using a protease (C) and an amylase (D) in combination. The mass ratio of component (C) / component (D) is preferably 1/3 to 5/1, more preferably 1/2 to 4/1, and still more preferably 1/1 to 3/1.

<(E) component>
In this invention, 5-20 mass% of polycarboxylic acid type high molecular compounds (E) are contained from a viewpoint of improving the washing | cleaning performance of the cleaning composition for automatic dishwashers.
When the content of the polycarboxylic acid type polymer compound is 5% by mass or more, the cleaning performance is improved, and when it is 20% by mass or less, the solubility in water is improved.
From the viewpoint of improving washing performance and solubility in water, the content of the polycarboxylic acid type polymer compound is preferably 5.5% by mass or more, more preferably 6.0% by mass or more, and 18
% By mass or less is preferable, and 16% by mass or less is more preferable.
The content of the specific polycarboxylic acid type polymer compound is preferably 5.5 to 18% by mass, and more preferably 6 to 16% by mass.
Examples of the polycarboxylic acid type polymer compound include a structural unit derived from a carboxylic acid having 3 to 6 carbon atoms having a reactive unsaturated group or a salt thereof (e-1), and an olefin having 2 to 12 carbon atoms (e-2). A polymer containing at least one kind of structural unit derived from), a polymer containing only the structural unit derived from (e-1), or a structural unit derived from (e-1) and a structure derived from (e-2). More preferred are copolymers containing units.

Examples of the carboxylic acid having 3 to 6 carbon atoms having a reactive unsaturated group or a salt thereof (hereinafter also referred to as (e-1) component) include maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, and itacone. One or more selected from acids, crotonic acid, citraconic acid and salts thereof are preferable, and acid anhydrides thereof may be used. The component (e-1) may be either a monocarboxylic acid or a dicarboxylic acid, but dicarboxylic acid is preferred from the viewpoint of improving detergency.
As the olefin having 2 to 12 carbon atoms (hereinafter also referred to as component (e-2)), one or more selected from ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene are preferable. As carbon number of the said olefin, 4-12 are more preferable, and 6-10 are still more preferable.
As the polymer composed only of the structural unit derived from (e-1), a copolymer of acrylic acid and maleic acid or a salt thereof is preferable, and the structural unit derived from (e-1) and derived from (e-2) As the copolymer containing the structural unit, a copolymer obtained by combining maleic acid and diisobutylene or a salt thereof is preferable.

  The polymer composed only of the structural unit derived from (e-1) is preferably a polymer containing maleic acid or a salt thereof and a structural unit derived from (e-1) or a salt other than maleic acid, and maleic acid or a salt thereof. The salt content is preferably 10 mol% or more, more preferably 15 mol% or more, and still more preferably 20 mol% or more.

  In the copolymer containing the structural unit derived from (e-1) and the structural unit derived from (e-2), the molar ratio of the (e-1) component to the (e-2) component [(e-1) component / (E-2) component] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. Specifically, specifically, 0.1 to 10 is preferable, 0.2 to 5 is more preferable, and 0.3 to 3 is still more preferable.

  As constituent monomers other than the components (e-1) and (e-2), acrylamide, methacrylamide, t-butylacrylamide, vinyl acetate, styrene, hydroxyethyl methacrylate, methyl methacrylate, butyl acrylate, methacrylic acid One or more selected from stearyl, styrene sulfonic acid and its salt, acrylamido-2-methylpropane sulfonic acid and its salt, 2 (methacryloyloxy) ethane sulfonic acid and its salt can be used.

The total content of the component (e-1) and the component (e-2) in the copolymer containing the structural unit derived from (e-1) and the structural unit derived from (e-2) is 90 mol% or more. Is preferable, 95 mol% or more is more preferable, 98 mol% or more is further preferable, and 100 mol% or less is preferable. That is, it is preferable that the copolymer (E) in this invention is a copolymer which consists only of (e-1) component and (e-2) component substantially.
In addition, a salt may be sufficient as (E) component, for example, sodium salt, potassium salt, ammonium salt, etc. are mentioned.

The weight average molecular weight of the component (E) is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, and preferably 100,000 or less. 90,000 or less is more preferable, 80,000 or less is more preferable, and 75,000 or less is still more preferable.
The weight average molecular weight of the component (E) in this specification is 60 mmol / L phosphoric acid and 50 mmol / L lithium bromide in dimethylformamide solution as a developing solvent, and the column is composed of two TSKgel α-M linked together. This is a value obtained by gel permeation chromatography using polystyrene as a standard substance.

If the average particle size of the component (E) is 10 μm or more, it has a caking-inhibiting effect, and if it is 500 μm or less, the solubility is improved, so 10-500 μm is preferable, 30-400 μm is more preferable, 50- 300 μm is more preferable.
The average particle diameter can be calculated from the weight fraction based on the size of the sieve mesh after vibrating for 5 minutes using a standard sieve of JIS K 8801 (mesh opening 2000 to 45 μm).
More specifically, using a 12-stage sieve having a mesh size of 45 μm, 63 μm, 90 μm, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm, a small sieve on the saucer Stack in order, add 100 g of particles from the top of the top 2000 μm sieve, cover and attach to a low-tap sieve shaker (made by HEIKO, tapping 156 times / minute, rolling: 290 times / minute) After vibrating for 5 minutes, the mass of the particles remaining on each sieve and the saucer can be measured, and the mass ratio (%) of the particles on each sieve can be calculated. After plotting this value on logarithmic probability paper {horizontal axis is sieve opening (particle diameter), vertical axis is mass ratio}, a line connecting each point is drawn, and the particle diameter corresponding to 50 mass% is drawn. Average particle diameter.

<(F) component>
In this invention, it is preferable to contain 0.1-15 mass% of fatty acid ester type nonionic surfactants (F) from a viewpoint of improving the cleaning performance of the cleaning composition for automatic dishwashers.
Fatty acid ester type nonionic surfactants include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester And one or more selected from polyglycerin fatty acid esters are preferred.
Moreover, as the surfactant of the component (F), those derived from fatty acids having 16 to 18 carbon atoms are preferable. Specifically, glyceryl palmitate, glyceryl margalate, glyceryl stearate, glyceryl oleate , Palm kernel oil composition fatty acid monoglyceride, sorbitan monopalmitate, sorbitan monomalgarate, sorbitan monostearate, sorbitan monooleate, polyethylene glycol monopalmitate, polyethylene glycol monomalgarate, polyethylene glycol monostearate, polyethylene glycol monooleate Ate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monomalgarate, polyoxyethylene sorbitan monostearate, sucrose monopalmitate , Sucrose mono- Marga rate, sucrose monostearate, and one or more can be mentioned are selected from sucrose monooleate.
Among these, glycerin fatty acid ester and sorbitan fatty acid ester are preferable, and glyceryl monostearate, glyceryl monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, and palm kernel oil composition fatty acid monoglyceride are preferable.

<Combination ratio>
The mass ratio [(A) / (B)] of the component (A) to (B) in the cleaning composition for an automatic dishwasher is more than 1 and 10 or less. When the mass ratio [(A) / (B)] is within the above range, the cleaning performance is further improved. From the viewpoint of improving the cleaning performance, the mass ratio [(A) / (B)] is preferably 1.1 to 8, more preferably 1.15 to 6, and still more preferably 1.2 to 4.

The mass ratio ((A) / [(C) + (D)]) of the component (A) with respect to the sum of the components (C) and (D) in the detergent composition for automatic dishwashers is tea astringent stain. And from a viewpoint of improving the cleaning performance with respect to rice stains, 3 to 10 is preferable.
The mass ratio is preferably 3 or more, more preferably 3.4 or more, still more preferably 4 or more, and is preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less from the viewpoint of reducing raw material costs.
The mass ratio ((A) / (E)) of the component (A) to the component (E) in the cleaning composition for automatic dishwashers is 0.1 to 4 from the viewpoint of improving the cleaning performance against dirt. 0.0 is preferred.
The mass ratio is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0.7 or more, and is preferably 3.5 or less from the viewpoint of improving oil reattachment prevention performance, The following is more preferable, and 2.5 or less is still more preferable.

  The total content of the component (A), the component (B), the component (C), the component (D), and the component (E) in the cleaning composition for an automatic dishwasher is a viewpoint for obtaining excellent cleaning performance. Therefore, 15 mass% or more is preferable, 18 mass% or more is more preferable, 20 mass% or more is more preferable, 60 mass% or less is preferable, and 50 mass% or less is more preferable.

  The pH at 25 ° C. of the 0.1% by weight aqueous solution of the cleaning composition for automatic dishwashers is preferably 8 or more, more preferably 9 or more, still more preferably 9.5 or more, from the viewpoint of detergency. From the viewpoint of the stability of the cleaning composition, it is preferably 13 or less, more preferably 12 or less, and still more preferably 11.5 or less.

<Other ingredients>
In the detergent composition for an automatic dishwasher, other components that can be used in ordinary detergents can be blended. For example, enzymes other than (C) and (D), alkaline agents, sequestering agents other than (A) components, surfactants other than (F) components, bleaches other than (B) components, bleach activation Examples include agents, oil-absorbing powders, extenders or diluents, binders, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial / antifungal agents, and dyes.

(enzyme)
The detergent composition for an automatic dishwasher of the present invention contains protease (C) and amylase (D), but may contain other enzymes. As the other enzyme, one or more selected from lipase, cellulase, esterase, and peroxidase are preferable, and a commercially available product can be used. Any enzyme may be appropriately selected in consideration of storage stability with other components.

(Alkaline agent)
As the alkali agent, alkali metal carbonates, alkali metal silicates, amine compounds and the like can be used.
The alkali metal carbonate is preferably one or more selected from sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Moreover, you may use the anhydrous salt of sodium carbonate known as soda ash.
As the alkali metal silicate, crystalline layered sodium silicate (manufactured by Tokuyama Siltech Co., Ltd., “Prefeed”) or the like can be used. An amorphous material may be used. Alkali metal silicate is also effective as an antioxidant for tableware.
An alkanolamine can be mentioned as an amine compound. In the present invention, primary alkanolamines are particularly preferred, and specific examples include monoethanolamine. Of these alkali agents, alkali metal carbonates are preferred.
As the alkaline agent, powdery or granular materials can be used. Granules can be used by appropriately adjusting the particle diameter and bulk specific gravity by granulation treatment or the like.
0-70 mass% is preferable, as for content of the alkaline agent in the cleaning composition for automatic dishwashers, 10-60 mass% is more preferable, 15-55 mass% is still more preferable.

(Metal sequestering agent)
As the sequestering agent other than the component (A), a phosphate such as sodium tripolyphosphate can be used. When the detergent composition for an automatic dishwasher does not contain phosphorus, as a sequestering agent other than the component (A), citric acid, malic acid, tartaric acid, succinic acid, L-glutamic acid diacetic acid, Hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid Polycarboxylic acids such as triethylenetetraamine hexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid or salts thereof can be used.
Among these, citric acid, succinic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethylglutamic acid, and alkali metal salts thereof are preferable.

(Surfactant)
Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants.
The content of the surfactant other than (F) is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less in the detergent composition for an automatic dishwasher. 1 mass% or less is still more preferable, 0.1 mass% or less is still more preferable, and it is preferable not to contain substantially.
The mass ratio of the surfactant other than the component (F) to the component (F) [surfactant other than the component (F) / component (F)] is preferably 0.5 or less, and 0.3 or less. More preferred is 0.1 or less. By setting it as the above range, the effects of the component (A), the component (B), the component (C), and the component (D) are not inhibited, and the anionic surfactant has foaming properties. The effect of the present invention is not inhibited.

In the present invention, bleaching agents, bleach activators, and the like that are generally blended as cleaning agents for automatic dishwashers may be blended as cleaning auxiliary components that further improve detergency.
(bleach)
In the present invention, a bleaching agent other than the component (B) may be used. Specific bleaching agents include organic hydrochloric acid such as magnesium monoperoxyphthalate or its salt, alkali metal perborate (monohydrate or tetrahydrate), persulfate, persilicate. One or more selected from peroxides that generate hydrogen peroxide in an aqueous solution are preferred. Among these, inorganic peroxides such as sodium persulfate and sodium perborate are more preferable.

(Bleaching activator)
In this invention, you may mix | blend the bleach activator generally mix | blended as a cleaning agent for automatic dishwashers as a washing | cleaning auxiliary | assistance component which further improves the detergency and the smell reduction effect after completion | finish of washing | cleaning.
A bleaching activator is used in combination with a bleaching agent and reacts with hydrogen peroxide released from the bleaching agent to produce an organic peracid having a higher redox potential. For example, a compound having at least one of N-acyl group, O-acyl group and benzoyl group, for example, a compound having a substituent such as anhydride, ester, imide, acylated imidazole and oxime. Specifically, tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylhexylenediamine (TAHD), tetraacetylglycoluril (TAGU), N-acylimide, such as N-nonanoyl succinimide (NOSI) Alkanoyloxybenzene carboxylic acids or salts thereof, alkanoyloxybenzene sulfonates such as n-nonanoyl or iso-nonanoyloxybenzene sulfonate (n- or iso-NOBS), lauroyloxybenzene sulfonate (LOBS), octanoyloxy Benzoic acid (salt), decanoyloxybenzoic acid (salt), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-tria Down (DADHT) or N- carboxyl anthranilic acid anhydride one or more selected from (ISA) is preferred.
In the present invention, it is preferable to add a hydrophilic bleach activator from the viewpoint of the effect of reducing odor after completion of washing. Examples of the hydrophilic bleach activator include tetraacetylmethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), and tetraacetylglycoluril (TAGU). Tetraacetylmethylenediamine (TAED), tetraacetylmethylenediamine ( TAMD) is preferable, and tetraacetylethylenediamine (TAED) is particularly effective.

(Oil-absorbing powder)
As the oil-absorbing powder, amorphous silica, dextrin and the like can be used.
Commercially available amorphous silica includes Toxeal NR, Toxeal NP (manufactured by Oriental Silicons Corporation), Florite (manufactured by Tomita Pharmaceutical Co., Ltd.), TIXOLEX 25 (manufactured by Han France Chemical Co., Ltd.), Silo Pure (Fuji Silysia Co., Ltd.) Manufactured) and the like.

Examples of the dextrin include those obtained by hydrolyzing starch derived from various grains with acid or amylase. There are various degradation products depending on the degree and structure of hydrolysis, and examples include amylodextrin (soluble starch), erythrodextrin, acrodextrin, maltodextrin, and cyclodextrin. Among these, the DE value (decomposition rate of starch = glucose equivalent mass / total solid content mass × 100) is preferably 0.1 to 10, and more preferably 0.1 to 5. Moreover, what melt | dissolves rapidly also in cold water or warm water is preferable, and a DE value is 0.1-3 from a viewpoint of alkali resistance.
Among the oil-absorbing powders, amorphous silica is preferable. The oil-absorbing powder may be used alone or in combination of two or more.

(Bulking agent, diluent)
When the detergent composition for an automatic dishwasher is used as a powdery or granular detergent, it is preferable to contain a sulfate such as sodium sulfate or magnesium sulfate as a filler or diluent. If a filler or diluent is added, each component can be diluted and dispersed at an appropriate concentration, so that it can be designed in an amount suitable for use, and also to maintain the stability of each component. It is valid.
As sodium sulfate, commercially available products such as “A6 Bow Show” manufactured by Shikoku Chemicals Co., Ltd. can be used. As the bowshoes that can be used in the present invention, those having a particle size of 20 μm or less account for 90% by mass or more of the whole from the viewpoint of solubility.
The total content of the extender and diluent in the detergent composition for automatic dishwashers is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and 50 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable. When the total content of the extender and the diluent is 1% by mass or more, the stability of each component can be improved, and when the total content is 50% by mass or less, the detergent composition can be easily carried. .

<Form of detergent composition for automatic dishwasher>
The cleaning composition for an automatic dishwasher may be used as a powdery cleaning agent, or may be used as a solution cleaning agent dissolved in water, an organic solvent, etc. The granulated product may be used as a cleaning agent.

Solvents that can be used in the case of a solution detergent include water, ethanol, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, One or more selected from propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol are used. be able to.
When used as a solvent for a solution-like cleaning agent, the amount of the solvent in the cleaning composition for an automatic dishwasher is preferably 3% by mass or more, and preferably 5% by mass or more from the viewpoint of improving the stability of the composition. More preferably, 10% by mass or more is further preferable, and from the viewpoint of inexpensive production, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is more preferable.

  In the case of using a powdery or granular detergent, as a method of mixing the detergent composition for an automatic dishwasher, the above components can be mixed with Henschel mixer (Nihon Coke Industries Co., Ltd.), high-speed mixer (Fukae Pautech Co., Ltd.). )), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), ribbon type mixer (manufactured by Tokuju Kogyo Co., Ltd.), V-type blender (manufactured by Dalton Co., Ltd.), bench kneader (manufactured by Irie Shokai Co., Ltd.) The method of mixing using well-known mixers, such as these, can be mentioned, It is preferable to use the Nauta mixer which does not require much shearing force at the time of stirring. Moreover, after mixing a part or all of each said component, you may co-granulate with a granulator.

  Examples of the granulation method include extrusion granulation method, rolling granulation method, pulverization granulation method, fluidized bed granulation method, spray granulation method, crushing granulation method, etc. A granulation method and a rolling granulation method are more preferable.

(binder)
When granulating the detergent composition for an automatic dishwasher, a binder such as a nonionic surfactant or a polymer may be used for the purpose of improving the physical strength of the granulated product.
As the polymer, polypropylene glycol, polyethylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene phenol ether are preferable, and polyethylene glycol and polypropylene glycol are more preferable.

As the binder, one kind of the above compounds may be used alone, or two or more kinds may be mixed and used. In addition, polypropylene glycol can also be used as an antifoaming agent from a viewpoint of improving the antifoaming property when it is set as a powdery cleaning composition.
When polypropylene glycol is contained in the granulated product, the content is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 12% by mass.
When polyethylene glycol is contained in the granulated product, the content is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass.

The bulk specific gravity when used as a powdery cleaning agent is preferably 0.7 to 0.9 g / cm ³ , from the viewpoint of ease of production and improvement in solubility, and preferably 0.75 to 0.85 g / cm ^3. Is more preferable.

  Since the cleaning composition for an automatic dishwasher of the present invention has a higher cleaning performance than a conventional cleaning composition for an automatic dishwasher, the amount of use can be reduced. Further, since the amount of use can be reduced, the container can be made compact, and the amount of packaging material used can be reduced.

[How to wash dishes]
The tableware cleaning method of the present invention is a method in which cleaning water having a concentration of the cleaning composition for an automatic dishwasher of 0.02 to 0.4% by mass is brought into contact with an object to be cleaned attached to the tableware. . The total concentration of the components (A), (B), (C), (D) and (E) in the washing water is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and 0 0.07% by mass or more is more preferable, 0.09% by mass or more is more preferable, 0.4% by mass or less is preferable, 0.3% by mass or less is more preferable, and 0.2% by mass or less is more preferable. 0.15 mass% or less is still more preferable, and 0.12 mass% or less is still more preferable. When the concentration is not less than the lower limit, the cleaning power is improved, and when the concentration is not more than the upper limit, it is excellent in economic efficiency and can be made into a detergent having a small capacity and convenient to carry.

  The time for contacting the cleaning composition for the automatic dishwasher with the article to be cleaned is preferably 5 minutes or more, more preferably 10 minutes or more, further preferably 12 minutes or more, still more preferably 16 minutes or more, and 45 Minutes or less are preferred, 35 minutes or less are more preferred, 25 minutes or less are more preferred, and 20 minutes or less are even more preferred. If the said time is more than a lower limit, the more outstanding cleaning effect can be acquired, and if it is below an upper limit, housework can be completed in a short time.

  The temperature at which the cleaning composition for an automatic dishwasher is brought into contact with the article to be cleaned is preferably 5 ° C or higher, more preferably 10 ° C or higher, still more preferably 20 ° C or higher, still more preferably 25 ° C or higher, and 80 ° C or lower is preferable, 70 ° C or lower is more preferable, 60 ° C or lower is further preferable, 50 ° C or lower is further preferable, and 40 ° C or lower is even more preferable. If the said temperature is more than a lower limit, cleaning power will improve, and if it is below an upper limit, the energy required for heating washing water, such as electricity and gas, can be saved.

  Moreover, the washing | cleaning method of the tableware of this invention is 10-25 mass% of compounds (A) represented by following General formula (1), 1 mass% or more of percarbonate (B), less than 10 mass%, protease 0.5 to 3% by mass of (C), 0.5 to 3% by mass of amylase (D), and 5 to 20% by mass of polycarboxylic acid type polymer compound (E), and the mass ratio [(A ) / (B)] is a dish washing method in which a solution containing a detergent composition for an automatic dishwasher having a ratio of 1 to 10 is brought into contact with the dish.

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)

Example 1
The cleaning composition for an automatic dishwasher of Example 1 was prepared according to the following procedures (1) to (4) according to the ratios shown in Table 1. In each example and comparative example, each component was blended so as to be 3 g, and a detergent composition for an automatic dishwasher was produced.
(1) 30 L Nauter mixer (manufactured by Hosokawa Micron Corporation, screw rotation: 110
(A) component, sodium sulfate, sodium carbonate, and sodium silicate were mixed with (r / min, screw revolution: 4 r / min) to prepare a first mixture.
(2) The first mixture was mixed with polypropylene glycol and a fragrance to prepare a second mixture.
(3) Component (B), tetraacetylethylenediamine, component (C), and component (D) were mixed with the second mixture to prepare a third mixture.
(4) A 10% by mass aqueous solution of component (E) was prepared, and this solution was mixed with the third mixture to prepare a detergent composition for an automatic dishwasher.

Examples 2, 6, 7 and Comparative Examples 3, 4
Automatic tableware in the same procedure as in Example 1 except that it was blended in the proportions shown in Tables 1 and 2, and a 10 mass% ethanol solution of component (F) was mixed with a third mixture together with an aqueous solution of component (E). A cleaning composition for a cleaning machine was prepared.

Examples 3 to 5, Comparative Examples 1 and 2
A detergent composition for an automatic dishwasher was prepared in the same procedure as in Example 1 except that it was blended at the ratio shown in Table 1.
In addition, about the solution which diluted each cleaning composition prepared by the above-mentioned method to 0.1 mass% with deionized water, pH was measured by the following method. The results are shown in Tables 1 and 2.
<PH measurement>
The pH value at 25 ° C. was measured according to JIS Z-8802: 2011 using a pH meter (manufactured by Horiba, Ltd., model number “F-52”, pH electrode 6367-10D).

<Evaluation of detergency>
≪Cleanability for tea astringent≫
(I) Creation of tea astringent stain A test tableware was prepared according to the following procedure.
(1) Commercially available tea tea bags ("Nitto Tea DAY & DAY Tea Bags" manufactured by Mitsui Norin Co., Ltd.)
Three bags were prepared for 1 L of hot water.
(2) A tea bag was put in boiling water and the tea liquid was boiled for 10 minutes.
(3) The tea bag was taken out and the tea liquid was stirred to make it uniform.
(4) Porcelain cup (Sazanka Nagayu cup [diameter 64 mm, height 78 mm]; purchased from Kamada Shoten Co., Ltd.), Melamine cup (Tumbler, small MN-17 [diameter 74 mm, height 80 mm], 200 mL from DAIWA (Purchase), 100 g each of the tea liquid was taken (excluding foam), allowed to stand for 1 hour, and then the tea liquid was removed.
(5) The test tableware was dried as it was at 25 ° C. for a whole day and night.

(Ii) Cleaning test The dishwasher (Panasonic Corporation, model number “NP”) was prepared so that the cleaning composition for the automatic dishwasher prepared in the examples and comparative examples had a concentration of 0.1% by mass in the cleaning liquid. -TR3 "(desktop type)) was put into a dedicated detergent container (amount of tap water used: 3L). In addition, the said density | concentration is a sum total density | concentration of each component described in Table 1, 2, and the water and ethanol used in order to dissolve (B) component and (C) component are cleaning composition for automatic dishwashers. It is not calculated as the concentration of objects. The same amount of ethanol was used in each of the examples and comparative examples.
The test tableware was washed in a standard course by placing three pots made of ceramics and three cups made of melamine in the upper basket of the dishwasher.

(Iii) Evaluation method The amount of tea astringent remaining on the surface of the test tableware was visually observed and evaluated in 6 stages of 0-5. The results are shown in Tables 1 and 2.
(Criteria)
5: Completely washed.
4: Slight dirt remains, but it is almost cleaned (within the allowable range).
3: Mostly cleaned, but dirt remains. Or it remains thin (out of tolerance).
2: Although it has been washed a little, most of the dirt remains.
1: Almost no washing.
0: Not washed at all.
In addition, it can be said that the cleaning composition for automatic dishwashers of 4 or more by the above-mentioned criteria has sufficient cleaning performance as a cleaning composition for automatic dishwashers.

≪Deterability against rice stains≫
(I) Creation of rice stain A test sample was prepared according to the following procedure.
(1) Cooked commercial rice (Itami Sangyo Co., Ltd. “Koshihikari from Niigata Prefecture”).
(2) Rice grains were spread on a slide glass and 0.15 g was placed.
(3) The sample was dried at 25 ° C. for a whole day and night to obtain a test sample.

(Ii) Cleaning test (1) 3 L of tap water heated to 50 ° C. so that the concentration in the cleaning liquid of the cleaning composition for an automatic dishwasher prepared in the above examples and comparative examples was 0.1% by mass. The mixture was stirred and dissolved for 1 minute. In addition, the said density | concentration is the total density | concentration of each component described in Table 1, 2, and the water and ethanol used in order to dissolve (B) component and (C) component are cleaning composition for automatic dishwashers. It is not calculated as the concentration of objects. Further, the same amount of ethanol was used in each of Examples and Comparative Examples.
(2) The slide glass was immersed for 10 minutes and then rinsed with water for 10 seconds.
(3) The slide glass was dried with an electric dryer at 50 ° C. for 30 minutes.

(Iii) Evaluation method The amount of rice remaining on the surface of the test sample was visually observed and evaluated in four stages of ◎ to × <Evaluation criteria>
◎: No dirt remains on the rice ○: Some dirt on the rice remains △: Some dirt on the rice is clearly left ×: Not cleaned

Details of the compounds described in the table are as follows. In addition, the unit of content described in the table | surface is the mass%, and is a value which does not consider the density | concentration of an effective part.
* 1: “Trilon M Powder” manufactured by BASF Japan
(Trisodium methylglycine diacetate), effective content 87% by mass
* 2: Nippon peroxide Co., Ltd., model number “KCPZ”, effective content 82% by mass
(Sodium percarbonate whose surface is coated with sodium metaborate),
* 3: “Sabinase 18T” manufactured by Novozymes Japan K.K.
* 4: “Duramil 120T” manufactured by Novozymes Japan K.K.
* 5: “Steinzyme Plus Evity 12T” manufactured by Novozymes Japan K.K.
* 6: “Acusol 460ND”, manufactured by Rohm and Haas Japan
Weight average molecular weight = 10,000, average particle size = 134 μm, effective content 92% by mass
Maleic acid / diisobutylene = 1/1 (molar ratio)
* 7: “SOKARAN CP45 Granule” manufactured by BASF Japan Ltd.
30% by weight partially neutralized acrylic acid / maleic acid copolymer Weight average molecular weight = 70,000
92% by mass of effective component, acrylic acid / maleic acid = 7/3 (molar ratio)
* 8: “Exel VS-95” manufactured by Kao Corporation, 100% by mass effective
* 9: Wako Pure Chemical Industries, Ltd. * 10: Wako Pure Chemical Industries, Ltd. * 11: Tokyo Chemical Industry Co., Ltd. * 12: Tokuyama Silktech Co., Ltd., “Pre-Feed Granules”
* 13: “Toxeal NP” manufactured by Oriental Silicas Corporation
* 14: “Preminol S4011” manufactured by Asahi Glass Co., Ltd.
Number average molecular weight = 10,000

  From the results of Tables 1 and 2, it can be seen that the cleaning composition for an automatic dishwasher of the present invention exhibits excellent cleaning performance against dirt caused by rice or tea astringency.

Claims (9)

10 to 25% by mass of the compound (A) represented by the following general formula (1),
1 to 8% by mass of percarbonate (B),
0.05 to 3% by mass of protease (C),
0.05 to 3% by mass of amylase (D) and 5 to 20% by mass of polycarboxylic acid type polymer compound (E),
The mass ratio [(A) / (B) ] is Ri der 10 or less than 1,
The mass ratio ((A) / [(C ) + (D)]) 3 to 8 der Ru automatic dishwashing detergent composition.

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)   The component (E) is derived from a structural unit derived from a carboxylic acid having 3 to 6 carbon atoms having a reactive unsaturated group or a salt thereof (e-1), and an olefin having 2 to 12 carbon atoms (e-2). The cleaning composition for an automatic dishwasher according to claim 1, which is a copolymer containing a structural unit.   The cleaning composition for an automatic dishwasher according to claim 1 or 2, wherein the component (E) is a diisobutylene-maleic acid copolymer or a salt thereof.   Furthermore, the detergent composition for automatic dishwashers in any one of Claims 1-3 which contains 0.1-15 mass% of fatty acid ester type nonionic surfactants (F).   The cleaning composition for automatic dishwashers according to claim 4, wherein the component (F) is at least one selected from glycerin fatty acid esters and sorbitan fatty acid esters.   The cleaning composition for an automatic dishwasher according to claim 4 or 5, wherein the content of the surfactant other than the component (F) in the cleaning composition for an automatic dishwasher is 0.1% by mass or less. . The detergent composition for automatic dishwashers in any one of Claims 1-6 whose pH in 25 degreeC of the 0.1 mass% aqueous solution of the detergent composition for automatic dishwashers is 9-13. Billing concentration of automatic dishwashing detergent composition according to any one of claim 1-7 is brought into contact with the object to be cleaned adhered wash water is 0.02 to 0.4 wt% in tableware, tableware Cleaning method. The compound (A) represented by the following general formula (1) is 10 to 25% by mass, the percarbonate (B) is 1 to 8% by mass , and the protease (C) is 0.05 to 3% by mass. The amylase (D) is contained in an amount of 0.05 to 3% by mass and the polycarboxylic acid type polymer compound (E) is contained in an amount of 5 to 20% by mass, and the mass ratio [(A) / (B)] is more than 1 and 10 Ri der hereinafter, the mass ratio ((a) / [(C ) + (D)]) of tableware contacting the solution with tableware comprising Ru der 3 to 8 automatic dishwashing detergent composition Cleaning method.

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² , and M ³ are each independently selected from a hydrogen atom, an alkali metal, ammonium, an alkanolamine, and an alkylamine. Is shown.)