JP2008037885A - Detergent composition for dish washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for a dish washer, having an excellent cleaning power against soil caused by oil, starch and tea incrustation. <P>SOLUTION: This detergent composition for the dish washer is characterized by containing (A) a metal catalyst containing a ligand expressed by general formula (I) [wherein, Xs are each H, sulfon, amino, nitro, carboxyl or an alkyl of which one part may be substituted; Y is H, an alkali metal or an alkaline earth metal: (p) is 1 or 2 integer; and when the (p) is 2, the Xs may be the same or different] and ≥1 kind of a transition metal selected from Cu and Mn, (B) a peroxide selected from hydrogen peroxide and compounds generating hydrogen peroxide in water, and (C) a nonionic surfactant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a detergent composition for a dishwasher.

A detergent composition for a dishwasher (hereinafter sometimes referred to as a dishwasher) is required to have a high detergency sufficient to clean oil stains, starch stains, and tea astringent stains.
The following Patent Document 1 discloses a food containing a surfactant containing a specific nonionic surfactant, a builder, an enzyme for detergent, a bleaching agent, and a bleaching catalyst such as MnTACN, pentaamine acetate cobalt salt. A washing machine detergent composition is disclosed.
Special Table 2000-502748

However, the conventional detergent composition for dishwashers does not necessarily have sufficient detergency, and has a higher detergency for oil stains, starch stains and tea astringent stains. Things are sought.
This invention is made | formed in view of the said situation, and it aims at providing the cleaning composition for dishwashers which has the outstanding detergency with respect to oil stain | pollution | contamination, starch stain | pollution | contamination, and tea astringent stain | pollution | contamination.

As a result of intensive investigations by the present inventors in order to solve the above problems, a metal catalyst, a peroxide, and a nonionic surfactant formed by combining a ligand having a specific structure and a transition metal are used. Thus, the inventors have found that the above-described problems can be solved, and have completed the present invention.
That is, the detergent composition for a dishwasher of the present invention comprises (A) a metal catalyst comprising a ligand having a structure represented by the following general formula (I), and one or more transition metals selected from Cu and Mn, It contains one or more peroxides selected from (B) hydrogen peroxide and a compound that generates hydrogen peroxide in water, and (C) a nonionic surfactant.

(In the formula, X represents a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxy group, or an alkyl group which may be partially substituted. Y represents a hydrogen atom, an alkali metal, or an alkaline earth. (P represents an integer of 1 or 2, and when p is 2, X may be the same or different.)

The metal catalyst (A) preferably contains a complex in which a ligand having a structure represented by the general formula (I) and Cu are bonded and / or a complex in which the ligand and Mn are bonded.
Alternatively, the metal catalyst is one or more selected from a ligand having the structure represented by the general formula (I), a compound that dissolves in water to generate Cu ions, and a compound that dissolves in water to generate Mn ions. It is preferred to include the transition metal ion sources in a state where they are not in contact with each other.

It is preferable that (A) the metal catalyst and (B) the peroxide are contained in a state where they are not in direct contact.
It is preferable that it is molded into a tablet type containing (A) a metal catalyst and (B) a peroxide in a non-contact state.

  ADVANTAGE OF THE INVENTION According to this invention, the detergent composition for dishwashers which has the outstanding detergency with respect to oil stains, starch stains, and tea astringent stains is obtained.

<(A) component>
The metal catalyst (A) in the present invention contains a ligand having the structure represented by the general formula (I) and one or more transition metals selected from Mn and Cu, and the ligand and the transition metal. May be included in a state where no complex is formed, or the ligand and the transition metal may be included in a state where a complex is formed.
<Ligand>
In the general formula (I), X represents a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxy group, or an alkyl group which may have a substituent. X is most preferably a carboxy group in terms of stable coordination and improved cleaning performance.
P representing the number of X represents an integer of 1 or 2, and is more preferably 1. When p is 2, X may be the same or different from each other.
When p is 1, the bonding position of X to the pyridine ring is preferably 6-position with respect to the nitrogen atom (1-position). Even when p is 2, at least one X is preferably bonded to the 6-position. The remaining X may be bonded to any of the 3rd, 4th, and 5th positions.

Y represents a hydrogen atom, an alkali metal, or an alkaline earth metal. Examples of the alkali metal include Na and K. Examples of the alkaline earth metal include Ca (in this case, “—C (O) O—Y” becomes “—C (O) O—Ca _1/2 )” and the like.
When Y is an alkali metal or an alkaline earth metal, it is represented by the general formula (I) as “—C (O) OM” (M represents an alkali metal or an alkaline earth metal). When a ligand is introduced into a solvent such as water, a part or all of “—C (O) OM” is “—C (O) O ⁻ ” and an alkali metal or alkaline earth metal ion. It becomes. “—C (O) O ⁻ ” forms a complex with the “transition metal ion”.
Therefore, even if Y is an alkali metal or an alkaline earth metal, it can be used as a ligand.

  Examples of the ligand represented by the structural formula (I) include those represented by the following structural formulas (1) to (5), but the present invention is limited to these structures. Instead, it can be selected appropriately according to the purpose, and one or more can be used. As a representative example, Y is represented as a hydrogen atom.

<Transition metal>
In the present invention, Mn and / or Cu is used as a transition metal used in combination with the ligand represented by the general formula (I).
In the present invention, the ligand represented by the general formula (I) and a transition metal may be combined in advance to form a complex (the metal catalyst of the first aspect), and the ligand and the transition may be used. You may mix a metal as a separate compound, respectively (the metal catalyst of a 2nd aspect). The metal catalyst of the first aspect and the metal catalyst of the second aspect may be used in combination.

(Metal catalyst of the first aspect)
The “metal catalyst of the first aspect” is a metal catalyst in which a ligand having a structure represented by the general formula (I) and a transition metal are complexed.
“The ligand having the structure represented by the general formula (I) and the transition metal are previously complexed” means that the ligand and the “transition metal ion” are reacted in advance, It is a complex formed by bonding with a “transition metal ion”.
In addition, in the “metal catalyst of the first aspect”, after forming a complex, a ligand and / or a transition metal ion is added to the complex to adjust the amount of transition metal and the amount of ligand. It can also be used.

  In the production of the “metal catalyst of the first embodiment” (complex), in order to bind the ligand and the “transition metal ion”, it is not necessary to simply mix them in a solvent. It is necessary to dissolve the ligand and the “transition metal ion source” in an organic solvent and to stir the reaction in the presence of an alkali agent.

The “transition metal ion source” is selected from a compound that dissolves in water to generate Cu ions and a compound that dissolves in water to generate Mn ions. Specifically, a water-soluble metal salt is preferable. For example, in the case of manganese, manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, manganese acetylacetonate, etc., in the case of copper, copper nitrate, copper sulfide, copper chloride, copper acetate, citric acid Copper, copper cyanide, copper oxalate, ammonium chloride, copper tartrate, copper perchlorate and the like are preferable.
Examples of the organic solvent include ethanol, methanol, acetonitrile, ethyl acetate, dimethyl sulfoxide and the like, and ethanol is preferable. 10-78 degreeC is preferable and the temperature of an organic solvent has more preferable 15-30 degreeC.
Examples of the alkali agent include triethylamine, sodium hydroxide, sodium carbonate and the like, and triethylamine is particularly preferable. The alkaline agent is preferably used in an amount of about 1 to 10 molar equivalents relative to the ligand. The reaction temperature is preferably room temperature. The reaction time is preferably 1 minute or longer, more preferably 1 minute to 5 hours, and even more preferably 5 minutes to 1 hour.
Specifically, first, an alkali agent is dissolved in an organic solvent, and then the ligand and the transition metal ion source are slowly added with stirring. After stirring for a predetermined reaction time at a predetermined reaction temperature, the mixture is allowed to stand. To produce a precipitate. The standing time is preferably 1 hour to 1 week, more preferably 3 to 24 hours. The target complex is obtained by filtering the produced precipitate. Usually, the obtained precipitate is dried to obtain a powder complex (metal catalyst).

  The ratio of the transition metal ion source and the ligand used in the production of the “metal catalyst of the first embodiment” is used in a proportion corresponding to the complex structure, or one of them is used in excess, and after the complex synthesis Remove the excess. Moreover, even when one is used excessively, it is not always necessary to remove the excess component, and it may be used as it is.

In the case of the “metal catalyst of the first embodiment”, the above-mentioned water-soluble metal salt is preferably used as the transition metal ion source, but an appropriate transition metal ion source such as an organic solvent-soluble salt or potassium permanganate can be used. Good. In the “complex in which a ligand and a transition metal ion are bonded” in the present invention, the number of ligands per transition metal may be one or more, and transitions constituting one molecule complex There may be one or more metals. Therefore, the complex may be mononuclear, binuclear, or cluster. Further, the transition metals constituting the polynuclear complex may be the same or different.
In addition to the ligand represented by the general formula (I), water, a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, a thiol group, a halogen and the like may be coordinated with the transition metal. Examples of the cross-linking species of the polynuclear complex include oxygen, sulfur, and halogen atoms.

In the detergent composition for a dishwasher according to the present invention, when the “metal catalyst of the first aspect” is present in the form of particles, the particle size thereof is an average particle from the viewpoint of the solubility and ease of production of the metal catalyst. The diameter is preferably in the range of 5 to 40 μm, more preferably 5 to 20 μm, and particularly preferably 5 to 15 μm.
An average particle diameter here is the value measured using the particle size distribution measuring apparatus (LDSA-3400A (17ch), Tohnichi Computer Applications Co., Ltd. product), and is a volume-based median diameter.

In the detergent composition for a dishwasher of the present invention, the “metal catalyst of the first aspect” is blended in the form of the complex, and a granulated product containing the complex and (a) a binder compound (hereinafter, It may be blended in the form of metal catalyst particles (X).
When the “metal catalyst of the first embodiment” is blended in the form of metal catalyst particles (X), it is preferable from the viewpoint of improving the storage stability during storage. The content of the “metal catalyst (complex) of the first embodiment” in the metal catalyst particles (X) is preferably 1 to 70% by mass, more preferably 5 to 50% by mass. When the content of the “metal catalyst of the first embodiment” exceeds the above range, the effect of making particles may not be sufficiently obtained, and when the content is less than the above range, the metal catalyst in the detergent composition for dishwashers The particle (X) content is too high, which is not economical.
If necessary, the metal catalyst particles (X) may be blended with (b) a surfactant and / or (c) a water-insoluble or poorly water-soluble fiber powder, and / or (d) a water-soluble inorganic salt. When the (b) surfactant is contained in the metal catalyst particles (X), the solubility of the particles (X) is improved. When the metal catalyst particles (X) contain (c) water-insoluble or poorly water-soluble fiber powder, the productivity of the particles is improved. Furthermore, (d) by containing a water-soluble inorganic salt, the bulk specific gravity of the particles can be controlled, and uneven distribution of the metal catalyst particles (X) in the dishwasher detergent composition during transportation can be suppressed.

(A) As a binder component, the water-soluble compound whose melting | fusing point is 35-70 degreeC is preferable. Specifically, at least one selected from polyethylene glycol, polyacrylic acid having a mass average molecular weight of 1,000 to 1,000,000 or a salt thereof is preferable. Two or more kinds may be combined.
The polyethylene glycol is preferably polyethylene glycol 1,000 to 20,000 (average molecular weight 500 to 25,000), more preferably an average molecular weight 2,600 to 9,300, and an average molecular weight 5,000 to 9,300. Are more preferred.
In addition, the average molecular weight of the polyethylene glycol in this invention shows the average molecular weight of cosmetic raw material reference | standard (2nd edition comment) description. The mass average molecular weight of polyacrylic acid or a salt thereof is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.
The content of the binder component (a) in the particles (X) is preferably 0.5 to 97% by mass, and more preferably 5 to 95% by mass.

  (B) As the surfactant component, polyoxyalkylene alkyl ether, α-olefin sulfonate, alkyl benzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate salt or a mixture thereof is preferable.

The polyoxyalkylene alkyl ether preferably has an alkyl group having 10 to 15 carbon atoms, and is preferably an adduct of ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO). The average addition mole number is preferably 4 to 30, more preferably 5 to 20 in total in any case of EO, PO, or a mixture of EO and PO, and the molar ratio of EO / PO is preferably 5 / 0 to 1/5, more preferably 5/0 to 1/2.
The α-olefin sulfonate is preferably a sodium or potassium salt of an α-olefin sulfonic acid having an alkyl group with 14 to 18 carbon atoms.
The alkylbenzene sulfonate is preferably a sodium or potassium salt of a linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms in the alkyl group.
As the alkyl sulfate ester salt, the alkyl group has 10 to 18 carbon atoms, and an alkali metal salt such as a sodium salt is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable.
As a polyoxyethylene alkyl ether sulfate ester salt, a polyoxyethylene alkyl ether sulfate ester salt having an alkyl group having 10 to 18 carbon atoms is preferable, and a sodium salt is particularly preferable. The average number of moles of ethylene oxide added is preferably 1 to 10, preferably 1 to 5, particularly polyoxyethylene lauryl ether sulfate sodium (POE = 2 to 5), polyoxyethylene myristyl ether sulfate sodium (POE = 2 to 2). 5) is preferred.

(B) A component may be 1 type and may be used 2 or more types.
The content of the (b) surfactant component in the particles (X) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. Exceeding this range is not preferable because the amount of foaming during washing becomes excessive. (B) The lower limit of the content when the surfactant component is contained is not particularly limited, but in order to sufficiently obtain the effect of addition of the (b) surfactant component, 0.1% by mass or more is preferable, 1 mass% or more is more preferable.

(C) A water-insoluble or poorly water-soluble fiber powder is a fiber powder having a solubility in 100 g of 25 ° C. deionized water of less than 0.1 g. The fiber powder is obtained, for example, by pulverizing and crushing fibers, frozen fibers, or fibers dispersed in a solvent using a pulverizer or the like.
(C) Examples of water-insoluble or poorly water-soluble fiber powder include powdered cellulose, silk powder, wool powder, nylon powder, polyurethane powder and the like.
Powdered cellulose consists of softwood, hardwood, and other wood; hemp, mitsumata, kouzo, gumpi, straw, bagasse, bamboo and other leaf fibers, stem fibers, and gin peel fibers; It is obtained from a refined product, a partially hydrolyzed product as required, or a product processed into cotton, hemp, rayon or the like, and has an amorphous part.
As the component (c), powdered cellulose, silk powder and wool powder of natural fibers are particularly preferable, powdered cellulose and silk powder are more preferable, and powdered cellulose is particularly preferable.

The (c) water-insoluble or poorly water-soluble fiber powder to be contained in the metal catalyst particles (X) may be used singly or in combination of two or more at any ratio.
The content of the component (c) in the metal catalyst particles (X) is preferably 50% by mass or less, and more preferably 30% by mass or less. When the above range is exceeded, granulation may be difficult or the strength of the granulated product may be reduced. The lower limit of the content when the component (c) is contained is not particularly limited, but is preferably 1% by mass or more and more preferably 5% by mass or more in order to sufficiently obtain the effect of adding the component (c).

  (D) One kind of water-soluble inorganic salt may be used alone, or two or more kinds thereof may be mixed and used in an arbitrary ratio. Component (d) can be used without particular limitation, and examples thereof include salts of alkali metals and alkaline earth metals with inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and carbonic acid. From the viewpoint of solubility, sodium sulfate, sodium carbonate, sodium chloride, and potassium carbonate are preferably used.

  The content of the component (d) in the metal catalyst particles (X) is preferably 50% by mass or less, and more preferably 30% by mass or less. When the above range is exceeded, granulation may be difficult or the strength of the granulated product may be reduced. The lower limit of the content when the component (d) is contained is not particularly limited, but is preferably 1% by mass or more and more preferably 5% by mass or more in order to sufficiently obtain the effect of adding the component (d).

The method for producing the metal catalyst particles (X) is not particularly limited, and may be granulated using a known granulation method after uniformly mixing the component (a) and other components as required.
For example, it is possible to use a method in which each component is first mixed, (a) the component is mixed until it is heated and melted until uniform, cooled and solidified, and then pulverized and granulated with a pulverizer.
The average particle diameter of the metal catalyst particles (X) is preferably in the range of 50 to 5000 μm, and more preferably in the range of 100 to 1000 μm. If it is this range, while the solubility of particle | grains (X) is favorable, the improvement effect of the storage stability at the time of storage by setting it as the form of particle | grains (X) will be favorably acquired.
Here, the average particle diameter is a mass-based median diameter determined by a measurement method using a classification operation described in detail below.

<Measurement method of average particle diameter>
First, the measuring object (sample) is classified using a 9-stage sieve and a saucer having openings of 1,680 μm, 1,410 μm, 1,190 μm, 1,000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm. went. In the classification operation, first, the 9-stage sieve is stacked above the pan so that the opening is gradually increased upward, and a sample of 100 g / time is put on the top of the sieve having the top opening of 1,680 μm. It was. Next, it was covered and attached to a low-tap type sieve shaker (manufactured by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), and after shaking for 10 minutes, it remained on each sieve and saucer. Samples were collected for each mesh and the sample mass was measured.
When the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is set to a μm, and the opening of the sieve that is one step larger than a μm is set to b μm. The average particle diameter (mass 50%) was calculated from the following formula (i), where c% was the cumulative mass frequency from the sieve to the aμm sieve, and d% was the mass frequency on the aμm sieve.

(Metal catalyst of the second aspect)
The “metal catalyst of the second aspect” is a metal catalyst containing a ligand having a structure represented by the general formula (I) and one or more transition metals selected from Mn and Cu.
In the metal catalyst of this embodiment, “including the ligand having the structure represented by the general formula (I) and one or more transition metals selected from Mn and Cu” means at least the ligand and the transition metal. It means that it is in the state which can form a complex with one part or all.
For example, when a ligand and the transition metal ion source are included in an arbitrary form and put into a solvent such as water, the ligand and the “transition metal ion” form a complex in the solution. It may be formed into a metal catalyst.

  Specifically, the “metal catalyst of the second aspect” is preferably a mixture of a ligand and a transition metal ion source. Further, by mixing them in a solution, a “transition metal ion” generated from a part or all of the transition metal ion source and a ligand may form a complex.

  The addition ratio of the transition metal ion source and the ligand is preferably added so that the amount of the ligand is 0.1 to 30 mol equivalent to the amount of the transition metal, such as 0.5 to 5 mol. The amount is more preferred. When complexing when contacting with water at the time of washing, it is preferable to add an excess molar amount of the ligand to the transition metal, but adding a larger amount than necessary is not economical.

  As a method for producing the “metal catalyst of the second aspect”, a method in which a ligand and a transition metal ion source are introduced into a solvent such as water and mixed can be mentioned. The ligand and transition metal ion source of the “metal catalyst of the second aspect” can be mixed in advance before producing the detergent composition for a dishwasher of the present invention. In the manufacturing process of the cleaning composition for a washing machine, the ligand and the transition metal ion source may be separately added to other materials and solvents such as hydrogen peroxide. In addition, a mixture containing a solid-state ligand and a solid-state transition metal ion source is also included in the metal catalyst of the present invention because it can form a complex and exhibit catalytic ability if it is subsequently introduced into water or the like. Is done.

In the case of the “metal catalyst of the second aspect”, in the detergent composition for a dishwasher of the present invention, the ligand and the transition metal ion source are preferably contained in a state in which they are difficult to contact each other. It is more preferable that it is contained without contact. Thereby, the preservation stability during storage is further improved.
Specifically, either or both of the ligand and the transition metal ion source are washed for a dishwasher in the form of (a) particles granulated together with a binder compound (hereinafter referred to as metal catalyst particles (Y)). It is preferable that it is mix | blended with the agent composition.
The metal catalyst particle (Y) may be a particle (Y1) containing a ligand, a transition metal ion source and (a) a binder compound, and does not contain a transition metal ion source containing a ligand and (a) a binder compound. It may be a particle (Y2), or may be a particle (Y3) containing a transition metal ion source and (a) a binder compound and no ligand. Moreover, you may combine 2 or more types of these arbitrarily.
The “metal catalyst of the second embodiment” may be composed of, for example, particles (Y1), a mixture of particles (Y2) and particles (Y3), or a mixture of particles (Y2) and a transition metal ion source. A mixture of particles (Y3) and a ligand may be used. A more preferable form is a mixture of particles (Y2) and particles (Y3), or particles (Y1).
Further, the particles (X) containing the “metal catalyst of the first embodiment” may be used in combination with the particles (Y2) or the particles (Y3).

1-70 mass% is preferable and, as for the total content of a ligand and a transition metal ion source in particle | grains (Y1), 5-50 mass% is more preferable. If the content exceeds the above range, the effect in the form of particles (Y1) may not be sufficiently obtained, and if the content is less than the above range, the metal catalyst particles (Y1) in the dishwasher cleaning composition. The content is too high and not economical.
1-70 mass% is preferable and, as for content of the ligand in particle | grains (Y2), 5-50 mass% is more preferable. If the content exceeds the above range, the effect in the form of the particles (Y2) may not be sufficiently obtained.
1-70 mass% is preferable and, as for content of the transition metal ion source in particle | grains (Y3), 5-50 mass% is more preferable. If the content exceeds the above range, the effect in the form of particles (Y3) may not be sufficiently obtained. If the content is less than the above range, economical efficiency is poor.

Further, it is more preferable that (b) a surfactant and / or (c) a water-insoluble or hardly water-soluble fiber powder is blended with the metal catalyst particles (Y). When the surfactant (b) is contained in the metal catalyst particles (Y), the solubility of the particles (Y) is improved. When the metal catalyst particles (Y) contain (c) water-insoluble or poorly water-soluble fiber powder, the productivity of the particles is improved. Furthermore, the bulk specific gravity of particle | grains is controlled by containing (d) inorganic salt, and uneven distribution of the metal catalyst particle (Y) in the detergent composition for dishwashers at the time of transportation etc. can be suppressed.
The components (a), (b), (c), and (d) in the metal catalyst particles (Y) are the same as those in the metal catalyst particles (X), including preferred embodiments and preferred amounts thereof. It is.
The metal catalyst particles (Y) can be granulated using a known granulation method in the same manner as the metal catalyst particles (X).
The preferable particle diameter of the metal catalyst particles (Y) is the same as that of the metal catalyst particles (X).

In the cleaning composition for a dishwasher of the present invention, the concentration of the transition metal in the cleaning liquid in contact with the tableware is preferably 0.001 to 300 ppm as a metal, and more preferably 0.005 to 30 ppm. When the amount of the transition metal is 0.001 ppm or less, a sufficient cleaning effect cannot be obtained, and when it is 300 ppm or more, decomposition of hydrogen peroxide is excessively promoted and the effect may be lowered. The amount of the transition metal in the cleaning liquid can be adjusted by the content of the metal catalyst (A) in the dishwasher cleaning composition of the present invention and the amount of the dishwasher cleaning composition used.
The content of the metal catalyst (A) in the dishwasher cleaning composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more from the viewpoint of cleaning performance. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of stability during storage.

<(B) Peroxide>
The component (B) is selected from hydrogen peroxide and a compound that generates hydrogen peroxide in water. When the present invention is formulated as a powder or solid product, a compound that generates hydrogen peroxide when dissolved in water is used. Examples of such substances include alkali metal percarbonates, perborates, perphosphates, persilicates, persulfates, and the like. Among these, sodium perborate, sodium percarbonate, and these The hydrate is preferred.

In the detergent composition for dishwashers of the present invention, it is preferable that (A) the metal catalyst and (B) the peroxide are contained in a state where they are not in direct contact.
For that purpose, (A) the metal catalyst is used in the form of a granulated product, or (B) the component is used in the form of coated particles with a coating agent applied to the surface, or both of these forms may be adopted. preferable. When at least (A) the metal catalyst of the first aspect of the non-granulated metal catalyst, the non-granulated ligand, or the non-granulated transition metal ion source is used, The component B) is preferably used in the form of coated particles.
Alternatively, as will be described later, if the form of the tablet containing the component (A) and the component (B) in a non-contact state is adopted, the non-granulated (A) component and / or the uncoated (B ) Component can be used.

The coated particles of component (B) can be produced by a known production method. It can also be obtained from commercial products.
Examples of the coating agent in the coated particles include boric acid, borate, silicic acid, silicate, magnesium salt, and water-insoluble organic compounds such as paraffin and wax. For example, sodium percarbonate coated with boric acid can be produced by a known method described in JP-A-59-196399.
(B) 200-1000 micrometers is preferable and, as for the average particle diameter of the covering particle | grains of a component, More preferably, it is 300-800 micrometers.
Here, the average particle diameter is a mass-based median diameter obtained by the measurement method using the classification operation described above.

  The content of the peroxide (B) in the dishwasher cleaning composition of the present invention is preferably 2% by mass or more, more preferably 5% by mass or more from the viewpoint of cleaning performance. Further, the upper limit is preferably 75% by mass or less, more preferably 50% by mass or less from the viewpoint of economy because the effect is saturated.

<(C) Nonionic surfactant>
The component (C) is a nonionic surfactant, and is preferably low-foaming due to the characteristics of the use as a detergent for dishwashers, and even when one kind is used alone, two or more kinds are used in combination. Also good. Although it does not specifically limit as (C) component used by this invention, For example, stability in the system in which the polyoxyalkylene type nonionic surfactant shown by the following general formula (II) coexists with (B) component is favorable. And is preferably used.

R ₁ —O— (EO) _n (AO) _m H (II)
However, in the formula, R ₁ is an alkyl group or an alkenyl group having 8 to 20 carbon atoms, preferably 10 to 16 carbon atoms, and may be linear or branched. EO is ethylene oxide and AO is C3-5 alkylene oxide. n and m represent an average added mole number, n is 1-20, m is 1-20.

  The higher alcohol which is the starting material of the general formula (II) includes natural or synthetic primary or secondary alcohols, specifically octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, myristyl alcohol, Examples include, but are not limited to, methyl alcohol, stearyl alcohol, oleyl alcohol, aralkyl alcohol, and the like. These higher alcohols may be used alone or in combination, and may be natural or synthetic. Primary synthetic alcohols such as Dovanox (registered trademark), Diadol (registered trademark), Neodol (registered trademark), and Saffol (registered trademark) And natural alcohols such as coconut oil higher alcohol, and secondary alcohols such as softanol (registered trademark). Among these, primary synthetic alcohols such as dodecyl alcohol, myristyl alcohol, tridecanol, Dovanox (registered trademark), Diadol (registered trademark), Neodol (registered trademark), Saffol (registered trademark), and other natural alcohols such as coconut oil higher alcohol Is preferred.

AO is a C3-5 alkylene oxide, preferably propylene oxide (PO) or butylene oxide (BO). The average added mole number m of AO is preferably 1-20, more preferably 2-10.
Moreover, 1-20 are preferable and, as for the average addition mole number n of ethylene oxide (EO), More preferably, it is 2-10.

  Furthermore, in the polyoxyalkylene alkyl ether of the above general formula (II), ethylene oxide is preferably added to the alcohol with a narrow addition molar distribution. Specifically, polyoxyethylene alkyl ethers having a narrow EO addition molar distribution can be easily obtained by using the methods described in JP-A-1-164437 and JP-A-2000-61304. A nonionic surfactant represented by the above general formula (II) is obtained by addition polymerization of AO in a predetermined amount.

  The polyoxyalkylene type nonionic surfactant represented by the general formula (II) can be obtained from a commercial product. Preferred examples include the Softanol EP series (manufactured by Nippon Shokubai Co., Ltd.), the pull lafuck series (manufactured by BASF), Leox, Leocon, and Lionol series (manufactured by Lion Corporation). However, it is not limited to these.

  0.1-20 mass% is preferable and, as for the total content of (C) component in the cleaning composition for dishwashers of this invention, 0.5-10 mass% is more preferable. If the content of the component (C) is less than 0.1% by mass, the dishwashing finish may be insufficient, and if it exceeds 20% by mass, the effect is saturated, which is not preferable.

<Other ingredients>
The cleaning composition for a dishwasher of the present invention may contain other components other than those described above as long as the effects of the present invention are not hindered. As the other components, known conventional components can be used depending on the application.
For example, as other components, a peracid precursor, a builder, an enzyme, a fragrance, an antifoaming agent, and a metal other than Mn and Cu can be used in combination. In particular, it is preferable to contain a pH adjuster as necessary so that the pH of the cleaning liquid in contact with the tableware is 5 to 12, preferably 6 to 11.

(builder)
There is no restriction | limiting in particular as a builder, It can select suitably as needed in the range which does not impair the effect of this invention. For example, aluminosilicates such as zeolites, alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, tripolyphosphates, silicates, sulfates, carbonate and silicate complexes, etc. Inorganic builder: organic builder such as nitrilotriacetic acid, methylglycine diacetic acid, lactic acid, citric acid, glycolic acid, succinic acid, polycarboxylic acid such as polyacrylic acid, maleic acid acrylic acid copolymer and their salts It is done. These may be used alone or in combination of two or more.

(enzyme)
There is no restriction | limiting in particular as an enzyme, According to the objective, it can select suitably. If classified according to the reactivity of the enzyme, hydrolases, oxidoreductases, lyases, transferases and isomerases can be mentioned, and any of them can be applied to the present invention. Particularly preferred are protease, esterase, lipase, nuclease, cellulase, amylase and pectinase, and these can be used alone or in combination of two or more.

(Fragrance)
There is no restriction | limiting in particular as a fragrance | flavor, According to the objective, what is described in Unexamined-Japanese-Patent No. 2002-146399 can be selected suitably. For example, hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, alcohols such as terpene alcohols, aromatic alcohols, aliphatic ethers, ethers such as aromatic ethers, aliphatic Oxides, oxides such as oxides of terpenes, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, Ketones such as aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids Acids such as acids, acid amides, aliphatic lactones, macrocycles Lactones, terpene lactones, hydrogenated aromatic lactones, aromatic lactones, lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, Synthetic fragrances such as esters such as aromatic carboxylic acid esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc. and natural fragrances from animals and plants, natural fragrances and / or synthesis One or two or more kinds of blended fragrances including fragrances can be mixed and used.

(Defoamer)
The antifoaming agent is not particularly limited and can be appropriately selected according to the purpose, but a silicone / silica type is preferable.

(PH adjuster)
The pH adjuster is not particularly limited and may be appropriately selected depending on the purpose. In addition to the alkali agent described in the builder, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, sodium hydroxide, water Examples of the alkaline agent include potassium oxide. As the acid, in addition to the organic acids described in the builder, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, sulfuric acid, hydrochloric acid, and the like can be used. These may be used alone or in combination of two or more.

(Peracid precursor)
The peracid precursor is not particularly limited as long as it reacts with hydrogen peroxide to produce a peroxo compound, and can be appropriately selected as necessary. For example, decanoyloxybenzoic acid, decanoyloxybenzenesulfonic acid Examples include sodium, sodium dodecanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, tetraacetylethylenediamine, and the like. Among these, 4-decanoyloxybenzoic acid, sodium 4-nonanoyloxybenzenesulfonate, and tetraacetylethylenediamine are preferable from the viewpoint of the bleaching effect.
(Other)
In addition, a plant extract, a tableware surface protective agent (amphoteric metal-containing compounds such as sodium aluminate and zinc sulfate) and the like may be appropriately blended.

  The detergent composition for a dishwasher according to the present invention is preferably in the form of powder or tablet. In the case of a tablet type, the tablet of the form which contains (A) component and (B) component in a non-contact state is preferable. For example, a mixed tablet type in which the component (A) and the component (B) are independently molded, and a multiphase in which the component (A) and the component (B) are contained in separate phases. A tablet type or a multi-chamber tablet type in which the component (A) and the component (B) are integrated in a state of being accommodated in the divided compartments is preferable. If these forms are adopted, the metal composition of the first form not granulated as the component (A), the ligand not granulated, or not granulated in the detergent composition for dishwashers Even if any of the transition metals is contained, good storage stability can be obtained by suppressing direct contact between the component (A) and the component (B).

  A tablet-type cleaning composition can be produced by a method of compression molding a powder raw material composed of the components to be blended. The compression molding method is not particularly limited, and can be performed according to known tableting machines and tableting conditions employed in tablet detergents. Under the present circumstances, you may add the fusion | melting particle | grains described in Unexamined-Japanese-Patent No. 2002-146399 in the range which does not prevent the effect of this invention. The tableting pressure is not particularly limited, but is preferably 5 to 10 kN, particularly 6 to 9 kN. If the tableting pressure is too high, sufficient disintegration property may not be obtained, and if it is too low, strength may be difficult to obtain. For the same reason, a tablet strength meter (product name: TD-50, manufactured by Okada Seiko Co., Ltd.) is used for the tablet immediately after molding, and the pressure arm is moved at a speed of 20 mm / min. When tableting is performed such that the tablet strength immediately after molding is 30 to 70 N, particularly 40 to 60 N, when the maximum stress until collapse is measured as tablet strength.

For example, the mixed tablet-type cleaning composition is formed by molding a tablet containing the component (A) and not containing the component (B), and a tablet containing the component (B) and not containing the component (A). It is obtained by mixing.
The multiphase tablet-type cleaning composition includes, for example, a powder raw material containing the component (A) and not containing the component (B), and a powder raw material containing the component (B) and not containing the component (A). In addition, it may be a two-layer tablet by a method of compression molding in the state of being laminated in order, or a powder raw material containing the component (A) and not containing the component (B), the component (A) and the component (B) It is good also as a three-layer type tablet by the method of carrying out the compression molding in the state which laminated | stacked the powder raw material which does not contain, and the powder raw material which contains (B) component and does not contain (A) component in order.
In the multi-chamber tablet-type cleaning composition, each compartment may be divided by, for example, a film-like member. The material of the film-like member is not particularly limited, but for example, water-soluble polymers such as polyvinyl alcohol and gelatin are preferably used. The method for accommodating the components in each compartment is not particularly limited, and can be carried out by any method as long as the effects of the present invention are not hindered. As a specific manufacturing method, for example, a pocket is formed by thermoforming a film-like member made of the polymer material, and a component to be accommodated in the pocket is filled, and the pocket is made of the same or different film substance. It is possible to employ a method in which an encapsulant is produced by sealing, and the encapsulant is placed in a compression molding machine and compression molded into a tablet. A plurality of enclosures in which different components are sealed are placed in a compression molding machine and collectively compression molded, whereby a tablet in a form in which compartments containing different components are integrated is obtained.
Further, in the manufacture of the enclosure, for example, the pocket is formed in a concave shape having a flange around the opening, and the pocket is filled with components, and then the opening is covered with a seal member, and the pocket flange and A method of heat sealing the sealing member can be used. In addition to heat sealing, other sealing methods such as infrared, high frequency, ultrasonic, laser, solvent, vibration or rotary welding may be used. Adhesives such as water or an aqueous solution of film material may also be used. There are other container manufacturing methods such as, for example, injection molding as disclosed in WO 01/36290. Further details of the manufacturing method of the container can be known from known techniques such as CA-A-1,112,534.

ADVANTAGE OF THE INVENTION According to this invention, the detergent composition for dishwashers which has the outstanding detergency with respect to oil stains, starch stains, and tea astringent stains is obtained. In particular, as shown in the examples described later, by coexisting (A) a metal catalyst and (B) a peroxide, the starch decomposition effect is remarkably improved and a sterilization effect is also obtained. Therefore, according to the present invention, a dishwasher cleaning composition having excellent detergency and also having a sterilizing effect can be obtained.
In particular, when a complex in which a ligand and a transition metal are combined is used as the metal catalyst (A), an excellent detergency is exhibited immediately after the start of cleaning, and cleaning in a substantially short time is possible.
In particular, when (A) a metal catalyst contains a ligand and a transition metal ion source, the reaction with the component (B) before use can be suppressed, and excellent storage stability can be obtained.
Further, by containing (A) a metal catalyst and (B) a peroxide in a state where they are not in direct contact with each other, the storage stability is improved, and an excellent detergency is stably obtained after storage.
In particular, a tablet-type cleaning composition for a dishwasher having excellent storage stability can be obtained by molding into a tablet type containing (A) a metal catalyst and (B) a peroxide in a non-contact state. Moreover, since it is a tablet type, the measurement at the time of use is easy and it is easy to use.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following, “%” is “% by mass” unless otherwise specified.
[Synthesis Example A-1: Synthesis of Manganese Complex of Ligand (1)]
20.0 g (119.7 mmol) of 2,6-pyridinedicarboxylic acid as ligand (1) represented by the following chemical formula and 10.1 g of manganese (II) sulfate monohydrate in 800 ml of ethanol at 65 ° C. 59.8 mmol) was dissolved and 11.0 g (108.7 mmol) of triethylamine was slowly added with stirring. The mixture was stirred at room temperature for 10 minutes and then allowed to stand for 15 hours. The produced precipitate was filtered to obtain 16.9 g (yield 73.2%, metal content 14.5% by mass) of the desired manganese complex of 2,6-pyridinedicarboxylic acid (metal catalyst A-1). .

[Synthesis Example A-2: Synthesis of Copper Complex of Ligand (1)]
In 800 ml of ethanol at 65 ° C., 20.2 g (119.7 mmol) of 2,6-pyridinedicarboxylic acid and 10.0 g (58.7 mmol) of copper (II) chloride dihydrate were dissolved, and 14.6 g (144.144) of triethylamine was dissolved. 3 mmol) was added slowly with stirring. After stirring at room temperature for 10 minutes, the mixture was concentrated until the mixed solution became 300 ml and allowed to stand for 15 hours. The resulting precipitate was filtered, and the target copper complex of 2,6-pyridinedicarboxylic acid (metal catalyst A-2) 18.1 g (yield 77.9%, metal content 15.5% by mass, average particle size) 20 μm) was obtained.

  Thus, the metal catalyst in the present invention can be produced in a high yield by a simple and short process.

[Synthesis Example A-3: Granulated product containing (metal catalyst A-1)]
To 1 g of the 2,6-pyridinedicarboxylic acid manganese complex obtained in Synthesis Example A-1, 1 g of sodium α-olefin sulfonate (manufactured by Lion Corporation, product name: Lipolane PJ-400), cellulose powder (Lettlement Meyer) 1 g of product made by the company, product name: Arbocel FD600 / 30) and 7 g of polyethylene glycol (product name: PEG # 6000, manufactured by Lion Corporation) were added and mixed well, and then heated and melted in a water bath at about 70 ° C. While mixing for 45 minutes. After cooling, the solidified mixture was pulverized and sieved to obtain a desired particle size to obtain the desired product (metal catalyst A-3, metal content 1.5% by mass, average particle size 20 μm).

[Synthesis Example A-4: Granulated product containing ligand and transition metal salt]
After adding 7.42 g of the cellulose powder and 7.42 g of the PEG # 6,000 to 0.87 g of 2,6-pyridinedicarboxylic acid and 0.71 g of manganese (II) sulfate heptahydrate, the mixture was mixed thoroughly. The mixture was mixed in a water bath at 0 ° C. for 30 minutes while being melted by heating. After cooling, the solidified mixture was pulverized and sieved to obtain the desired particle size, thereby obtaining the target product (metal catalyst A-4, metal content 0.14% by mass, average particle size 20 μm).

[Synthesis Example A-5: Granulated product containing a ligand]
6.75 g of PEG # 6,000 was added to 1.75 g of 2,6-pyridinedicarboxylic acid, 1 g of the sodium α-olefin sulfonate, and 1 g of the cellulose powder and mixed well, and then in a water bath at about 70 ° C. The mixture was mixed for about 50 minutes while heating and melting. After cooling, the solidified mixture was pulverized and sieved to obtain the desired particle size (ligand A-5, average particle size 20 μm).

[Synthesis Example A-6: Granulated product containing transition metal ion source]
9.15 g of the PEG # 6,000 was added to 0.85 g of manganese (II) sulfate monohydrate and mixed well, followed by mixing for 45 minutes while heating and melting in a water bath at about 70 ° C. After cooling, the solidified mixture was pulverized and sieved to obtain the desired particle size, thereby obtaining the target product (transition metal salt A-6, metal content 0.28% by mass, average particle size 20 μm).

[Synthesis Example C-1: Nonionic Surfactant]
As solution a, a solution was prepared by dissolving 68.03 g of magnesium nitrate hexahydrate, 47.69 g of aluminum nitrate nonahydrate, and 24.43 g of manganese nitrate hexahydrate in 450 g of deionized water.
As a solution b, a solution in which 13.47 g of sodium carbonate was dissolved in 450 g of deionized water was prepared.
Solution a and solution b were added dropwise to a catalyst preparation tank previously charged with 1800 g of deionized water in 45 minutes while maintaining the pH at 9 with an aqueous NaOH solution and maintaining the temperature at 45 ° C. After aging for 1 hour, it was filtered off, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain 30 g of a composite metal hydroxide. This was calcined at 800 ° C. in a nitrogen atmosphere to obtain 19 g of a composite metal oxide catalyst mainly composed of magnesium oxide.

Next, 120 g of compound name: C12, C13 synthetic higher alcohol, product name: Neodol 23 (C12, 13: manufactured by Shell) and 0.3 g of the composite metal oxide catalyst obtained above were charged into the autoclave, After replacing with nitrogen, the temperature was raised with stirring. Subsequently, 82 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180 ° C. and the pressure at 3 atm. The obtained polyoxyalkylene ether had an average ethylene oxide addition mole number of 3.
Furthermore, 108 g of propylene oxide was introduced and reacted while maintaining the temperature of the autoclave at 180 ° C. and the pressure at 3 atm. The average polypropylene oxide addition mole number of the obtained polyoxyalkylene ether was 3. After the reaction solution was cooled to 80 ° C., the catalyst was filtered off. In this way, a nonionic surfactant (C-1) was obtained.

[Test Example 1: Starch degradation effect]
To the 39.6 mmol / L aqueous solution of sodium carbonate, “corn starch (Starch, Corn) was added to a concentration of 5% by mass. The mixture was heated at 95 ° C. for 60 minutes to swell the starch, and the temperature was lowered to 40 ° C. Thereafter, 17.6 mmol / L of hydrogen peroxide and 0.05 mmol / L of the metal catalyst (A-1) obtained in Synthesis Example A-1 were added to prepare a sample. A sample was prepared by adding the metal catalyst (A-2) obtained in Synthesis Example A-2 in the same manner instead of (A-1).
Each of these samples was kept at 40 ° C., and after 60 minutes from the addition of the metal catalyst, the viscosity was measured using a B-type viscometer BL type manufactured by Tokyo Keiki Co., Ltd., and the state of starch decomposition was examined. The result is shown in FIG.
As blank (1), the result in the same manner except that the metal catalyst is removed from the above composition is shown in FIG.

As shown in the results of FIG. 1, when (A-1) or (A-2) is added, the viscosity is greatly reduced as compared to the blank (1).
Starch is a polymer compound in which α-glucose is polymerized by glycosidic bonds. As shown in Test Example 1, after being dissolved in warm water at 95 ° C., when the temperature is lowered to 40 ° C., the viscosity is very high. Become. On the other hand, when the metal catalyst (A-1) or (A-2) is added, the action on the glycosidic bond portion occurs, and the starch is considered to have decreased in viscosity because it was decomposed into oligosaccharides and the like.
Therefore, according to the cleaning composition for a dishwasher of the present invention containing such a metal complex (manganese complex, copper complex), a high starch decomposition effect can be obtained.

[Test Example 2: Starch decomposition effect]
Corn starch (Starch, Corn) was added to a 39.6 mmol / L aqueous solution of sodium carbonate to a concentration of 5% by mass. After heating at 95 ° C. for 60 minutes to swell the starch and lowering the temperature to 40 ° C., hydrogen peroxide 17.6 mmol / L, 2,6-pyridinedicarboxylic acid 0.1 mmol as ligand (1) / L and 0.05 mmol / L of copper (II) chloride were added. While maintaining the temperature at 40 ° C., the viscosity was measured 60 minutes later using a B-type viscometer BL type manufactured by Tokyo Keiki Co., Ltd., and the state of starch decomposition was examined. The results are shown in FIG.
Moreover, as blank (2), the result at the same time except having remove | excluded the ligand and copper chloride from said composition is shown according to FIG.
As is clear from the results of FIG. 2, it can be seen that even when the ligand and copper chloride are added separately, a high starch decomposition effect can be obtained.

[Test Example 3: Bactericidal effect]
Sodium percarbonate (SPC-G manufactured by Mitsubishi Gas Chemical Co., Inc.) 30 ppm, sodium carbonate (granular ash manufactured by Asahi Glass Co., Ltd.) 30 ppm, metal catalyst obtained in Synthesis Example A-2 (A-2: Ligand) (1) Copper complex) 9.9 ml of a test solution containing 0.3 ppm was prepared. 0.1 mL of Staphylococcus aureus mother liquor (IF012732) adjusted so that the number of bacteria became 10 ⁸ / ml was added there, and it stirred uniformly. Ten minutes later, 1 mL was collected and added to 9 mL of SCDLP medium (Soybean-Casein Digest Broth With Lectin & Polysorbate 80: Wako Pure Chemical Industries, Ltd.) to give a 10-fold dilution.
A 10-fold diluted solution was obtained in the same manner except that 0.1 mL of Escherichia coli mother liquor (IF03972) adjusted so that the number of bacteria was 10 ⁸ cells / ml was added instead of the S. aureus mother liquor.
Collect 1.0 mL from each dilution in a petri dish, add 15 mL of SCDLP agar medium (Soybean-Casein Digest Age with Lectin & Polysorbate 80: Wako Pure Chemical Industries, Ltd.), homogenize, and culture at 37 ° C. for 2 days After that, colonies were counted to determine the number of viable bacteria. The results for S. aureus are shown in FIG. 3, and the results for E. coli are shown in FIG.
As blank (3-1) (3-2), the result at the time of diluting each said microbe mother liquid in ion-exchange water is shown according to FIG. Moreover, as blank (4-1) (4-2), the result at the same time except having remove | excluded the metal catalyst (A-2) from said composition is shown according to FIG.
As is apparent from the results of FIGS. 3 and 4, it can be seen that a high sterilizing effect can be obtained according to the detergent composition for a dishwasher of the present invention containing a metal complex.

[Examples and Comparative Examples]
<Dishwasher detergent composition>
Using each component obtained in the above synthesis example and the following commercially available components, each component was mixed in the formulation shown in Tables 1 and 2 to prepare a powdery detergent composition for a dishwasher. The unit of the blending ratio in Tables 1 and 2 is mass%.
About the obtained cleaning composition for dishwashers, the following method evaluated the cleaning power and storage stability. The results are shown in Tables 1 and 2.

Each component shown in Tables 1 and 2 is as follows.
B-1: Coated sodium percarbonate: manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: SPC-D, sodium percarbonate coated with silicic acid and sodium borate.
B-2: Sodium percarbonate: manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: SPC-G. Without coating.
B-3: Sodium perborate: manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: Perbon. Without coating.

C-2: Polyoxyalkylene alkyl ether, manufactured by BASF Corp., Pullurafac LF403.
C-3: Polyoxyalkylene alkyl ether, Nippon Shokubai Co., Ltd., Softanol EP90100.

AA / MA-1: Acrylic maleic acid copolymer, manufactured by BASF, trade name: Socaran CP5.
AA / MA-2: acrylic acid maleic acid copolymer, manufactured by BASF, trade name: Socaran CP7.
AA: Polyacrylic acid, manufactured by BASF, trade name: Socaran PA50.
Citric acid: trisodium citrate, manufactured by Iwata Chemical Co., Ltd., trade name: sodium citrate.
MGDA: trisodium methylglycine diacetate, manufactured by BASF, trade name: Trilon M.
Carbonate: sodium carbonate, manufactured by Asahi Glass Co., Ltd., trade name: grain ash.
Complex salt: sodium carbonate, sodium silicate complex, manufactured by Rhodia, trade name: Navion 15.
Amylase: Novozymes, trade name: Duramil 120T.
Protease: Novozymes, trade name: Evalase 8.0T.
Plant extract: Rosemary extract manufactured by Toyoda Fragrance Co., Ltd.
Aluminic acid: sodium aluminate, manufactured by Sumitomo Chemical Co., Ltd., NAP-120.
Antifoaming agent: Dow Corning, product name: 2248S.
Fragrance | flavor: The fragrance | flavor composition of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
Silicic anhydride: Tokuseal NP, manufactured by Tokuyama Corporation.
Sulfate: anhydrous sodium sulfate, manufactured by Nippon Kagaku Co., Ltd., anhydrous sodium sulfate K2.

Moreover, the tablet-shaped dishwasher cleaning composition was manufactured on the manufacturing conditions shown in Table 3, and the cleaning power and storage stability were evaluated by the following method. The results are shown in Table 3.
The composition of the components in Examples 15 to 22 shown in Table 3 is the same as that in Example 3, Examples 15 and 16 are the same as those in Example 9, Examples 19 to 21 are the same as those in Example 9. Same as Example 14.
In Example 15, after all the ingredients were mixed uniformly, this was compressed into tablets.
Example 16 is a pocket formed by uniformly mixing all components with a film made of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product name: Claria HH, thickness: 40 μm, hereinafter referred to as PVA film). The tablet was compressed and compressed into a tablet shape covered with a PVA film.
In Example 17, all the raw materials include the A component (metal catalyst) and the C component (nonionic surfactant), the first raw material not including the B component, the B component, the A component and the C component. It was divided into the 2nd raw material which does not contain. The other raw materials other than the components A to C were uniformly mixed and then divided into two equal parts, respectively mixed with the first raw material and the second raw material, and mixed uniformly. And in the state which set the 1st raw material in the tableting machine and laminated | stacked the 2nd raw material on it, it compressed into a tablet collectively, and was set as the tablet of 2 layer type.
In Example 18, the same first raw material and second raw material as in Example 17 were stored in a pocket made of PVA film, stacked and set in a tableting machine, and compressed into a batch. A tablet was formed into a two-layer tablet. Each layer is a compartment divided by a PVA film.
Example 19 was formed into a two-layer tablet in the same manner as Example 17.
In the same manner as in Example 18, Example 20 was formed into a two-layer tablet shape in which each layer is a compartment divided by a PVA film.
In Example 21, each layer was divided by a PVA film in the same manner as in Example 18 except that the first raw material was all components other than the B component and the second raw material was only the B component in Example 18. It was made into the tablet form of the 2 layer type used as a branch room.
In Example 22, the same first raw material and second raw material as in Example 17 were individually compressed and compressed to produce two types of tablets, and these were mixed.

<Detergency evaluation method>
The following model soil was prepared, loaded into an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2”, and standard using 6 g of the dishwasher detergent composition prepared in each example. The course was washed. Sensory evaluation of the finish was performed based on each evaluation standard.
[Cleaning power of tea astringent: Cleaning of tea astringent model dirt]
Three coffee cups (inner diameter 70 mm, height 70 mm) with tea stains left for 1 month at 25 ° C. and 50% RH after drinking and drinking tea were used as model stains.
Evaluation criteria:
(Double-circle): A stain | pollution | contamination does not remain | survive at all and the discomfort, such as roughness, is not felt.
○: Residue of dirt is not visually recognized, but feels uncomfortable, such as roughness.
Δ: Residue of dirt is slightly recognized visually.
X: Dirt is not removed.

[Starch dirt cleaning power: Washing starch model dirt]
3 g of retort porridge made by Ajinomoto Co., Inc. was applied to a teacup and heated for 2 minutes in a microwave oven (500 w) as model dirt.
Evaluation criteria:
(Double-circle): A stain | pollution | contamination does not remain at all and it is not dye | stained with an iodine solution.
○: Residue of dirt is not visually recognized, but is stained with iodine solution.
(Triangle | delta): The residue of dirt is recognized visually and it dye | stains markedly with an iodine solution.
X: Dirt is hardly removed.

[Prevention of oil recontamination: washing oil model dirt]
Beef tallow / lard / butter / salad oil = 3/3/3/1 mixed oil coated dish, retort curry (bon curry gold 21 dry) 3g coated dish, clean polypropylene lunch box (110mm length, 170 mm in width and 35 mm in height) were washed at the same time, and the state of the lunch box after washing was subjected to sensory evaluation.
In the dishwasher, since the cleaning liquid circulates and repeatedly contacts the entire tableware, if the cleaning power of the oil is insufficient, the oil will be in a state where the oil has adhered to the tableware that was not originally contaminated with oil. Recontamination occurs. Therefore, it indicates that the less oil recontamination occurs when the polypropylene tableware to which oil easily adheres is washed in the presence of the oily tableware, the better the detergency of the oil stain is.
Evaluation criteria:
(Double-circle): Oil does not adhere at all and a sense of incongruity is not felt.
○: Oil adhesion is not visually recognized, but feels uncomfortable, such as with a null.
Δ: Some adhesion of oil is visually observed.
X: Oil is sticky.

<Method for evaluating storage stability>
[Peroxide stability]
Put 600g of detergent composition for dishwasher into a container (refillable pouch 2 layer structure, PET / LLDPE = 12μm / 120μm from outside, with pinhole of 0.3mm in diameter), and 45 ° C-25 ° C recycling conditions ( Concentration (mass%) of component (B) (total of B-1, B-2, B-3) after storage for 1 month at 45 ° C and humidity 85% for 8 hours, 25 ° C and humidity 60% for 16 hours Was quantitatively analyzed.
From the concentration value thus obtained, the residual ratio (unit:%) was determined by the following mathematical formula (1) and evaluated based on the following evaluation criteria.
Residual rate (%) = (concentration after storage) / (initial concentration before storage) × 100 (1)
(Peroxide stability evaluation criteria)
A: Residual rate is 80% or more.
○: Residual rate is 60% or more and less than 80%.
Δ: Residual rate is 40% or more and less than 60%.
X: Residual rate is less than 40%.

[Amylase stability and protease stability]
In the same manner as the above-described peroxide stability evaluation method, a detergent composition for a dishwasher is placed in a container and stored for 1 month under recycling conditions at 45 ° C to 25 ° C. Then, the content of amylase and the concentration of protease (% By mass) was quantitatively analyzed.
From the concentration value thus obtained, the residual ratio (unit:%) was obtained by the above mathematical formula (1), and evaluated based on the following evaluation criteria.
(Evaluation criteria for amylase and protease stability)
○: Remaining rate is 60% or more.
Δ: Residual rate is 30% or more and less than 60%.
X: Residual rate is less than 30%.

From the results of Tables 1 and 2, the cleaning compositions of Examples 1 to 14 all had good cleaning power against oil stains, starch stains and tea astringent stains.
On the other hand, in Comparative Examples 1 to 4 and 6, which contain the component (C) and do not contain one or both of the component (A) and the component (B), although the oil stain was good, the starch stain and Detergency against tea astringent stains was insufficient. In particular, Comparative Example 6, which did not contain both the component (A) and the component (B), had significantly inferior cleaning power for starch stains and tea astringent stains.
Further, Comparative Example 5 containing the component (B) and not containing the component (A) and the component (C) had insufficient detergency, and in particular, was poor in detergency against oil stains.
Furthermore, in Examples 6 to 14 using A-3 to A-6 obtained through the step of granulating together with the binder component and the like as the component (A), good storage stability was obtained.
In addition, from the results in Table 3, it was confirmed that good detergency and storage stability can be obtained even in a tablet form.
For the multi-phase tablets, the same results were obtained even if the first phase and the second phase were integrally molded or the tablets were mixed.

It is a figure which shows the result of a test example. It is a figure which shows the result of a test example. It is a figure which shows the result of a test example. It is a figure which shows the result of a test example.

Claims (5)

(A) The following general formula (I)

(In the formula, X represents a hydrogen atom, a sulfone group, an amino group, a hydroxyl group, a nitro group, a carboxy group, or an alkyl group which may be partially substituted. Y represents a hydrogen atom, an alkali metal, or an alkaline earth. (P represents an integer of 1 or 2, and when p is 2, X may be the same or different.)
A metal catalyst comprising a ligand having a structure represented by: and one or more transition metals selected from Cu and Mn,
A dishwasher comprising (B) hydrogen peroxide and one or more peroxides selected from compounds that generate hydrogen peroxide in water, and (C) a nonionic surfactant. Cleaning composition.   The (A) metal catalyst contains a complex in which a ligand having a structure represented by the general formula (I) and Cu are bonded and / or a complex in which the ligand and Mn are bonded. The cleaning composition for dishwashers according to claim 1.   The (A) metal catalyst is selected from a ligand having a structure represented by the general formula (I), a compound that dissolves in water to generate Cu ions, and a compound that dissolves in water to generate Mn ions. The detergent composition for dishwashers according to claim 1, comprising the above transition metal ion source.   The said (A) metal catalyst and (B) peroxide are contained in the state which does not contact directly, The cleaning composition for dishwashers as described in any one of Claims 1-3 characterized by the above-mentioned. The detergent composition for a dishwasher according to claim 1, wherein the detergent composition is molded into a tablet shape containing the metal catalyst (A) and the peroxide (B) in a non-contact state.

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