JP2015196701A - solid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid detergent excellent in storage stability without decoloration even after long-term storage and a manufacturing method of the solid detergent.SOLUTION: There is provided a solid detergent containing a compound (A) represented by the general formula (1) and a silicone compound (B) as a co-pelletized granule and the content of the compound (A) is 5 mass% to 70 mass% and the content of the silicone compound (B) is 0.01 mass% to 7 mass%. In the formula (1), R represents a hydrocarbon group having 1 to 12 carbon groups, M, Mand Mrepresent each independently one kind selected from a hydrogen atom, an alkali metal, ammonium, alkanol ammonium and alkylammonium.

Description

  The present invention relates to a solid detergent and a method for producing the same.

  Conventionally, a large amount of a surfactant has been added to the detergent composition. However, in recent years, from the viewpoint of environmental consideration, the use of a surfactant can be increased by adding more organic chelating agents with good biodegradability. Detergent compositions with reduced amounts have been developed. Examples of organic chelating agents with good biodegradability include glycine-N, N-diacetic acid derivatives (hereinafter also referred to as “GDA”). This GDA is attracting attention as a material for reducing the amount of surfactant used because it is an excellent cleaning base having good biodegradability and high chelating performance.

As a detergent composition for tableware which contains an organic chelating agent with good biodegradability and exhibits a high bleaching effect, Patent Document 1 discloses GDA, inorganic peroxide, lipase, maleic acid / acrylic acid copolymer A granular detergent composition for a dishwasher containing coalescence and an optional component such as an antifoaming agent has been proposed.
Patent Document 2 discloses a detergent composition for an automatic dishwasher containing optional components such as GDA, a specific polymer, and a builder.
Further, Patent Document 3 discloses a powder cleaning composition containing GDA, a reducing agent, and an oxygen bleach.

JP 2012-144656 A Special table 2011-516615 gazette JP 2013-10819 A

As a result of researches on a detergent composition containing GDA, the present inventors faced the problem that the GDA in the detergent composition changes color during long-term storage. In general, solid detergents mainly contain white granular components, and the degree of visual recognition increases only when slight yellowing occurs. Therefore, maintaining the white state is a related product in this field. is important.
It is an object of the present invention to provide a solid detergent containing a glycine-N, N-diacetic acid derivative, which does not change color even after long-term storage and has excellent storage stability, and a method for producing the same. To do.

As a result of investigations on the discoloration of GDA, the present inventors have found that the discoloration of GDA is promoted by the presence of ambient moisture, oxygen-based bleach and the like.
Therefore, as a result of further investigations on the technology for suppressing the discoloration of GDA, the present inventors have included GDA and a silicone compound in a specific amount as a solid detergent, thereby containing GDA during long-term storage. It was found that it is possible to suppress discoloration.

（式中、Ｒは炭素数１以上、１２以下の炭化水素基を示し、Ｍ¹、Ｍ²、Ｍ³は、それぞれ独立に水素原子、アルカリ金属、アンモニウム、アルカノールアンモニウム、及びアルキルアンモニウムから選ばれる１種を示す。） The gist of the present invention is the following [1] and [2].
[1] A solid detergent containing a compound (A) represented by the following general formula (1) and a silicone compound (B) as co-granulated granules, and the content of the compound (A) is 5% by mass. As mentioned above, the solid cleaning agent whose content of a silicone compound (B) is 0.01 to 7 mass% below 70 mass%.

(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 alkanol ammonium, and an alkyl ammonium. 1 type is shown.)

[2] The method for producing a solid detergent according to [1], including the following steps.
Step 1: Mixing at least the component (A), the component (B) and a binder to obtain a mixture Step 2: Obtaining a granulated product of the mixture obtained in Step 1 Step 3: Forming obtained in Step 2 The step of mixing the granule with a component other than the component (A) and the component (B)

  According to the present invention, it is possible to provide a solid detergent that does not change color even after long-term storage and has excellent storage stability, and a method for producing the solid detergent.

[Solid detergent]
The solid detergent of the present invention is a solid detergent containing the compound (A) represented by the following general formula (1) and the silicone compound (B) as granules obtained by co-granulation, and contains the compound (A). The amount is 5% by mass or more and 70% by mass or less, and the content of the silicone compound (B) is 0.01% by mass or more and 7% by mass or less. According to the present invention, since a granule obtained by co-granulating GDA and a silicone compound in a specific amount is used, GDA is not easily affected by moisture in the air, and discoloration occurs even after long-term storage. Hard to occur.

<Compound (A)>
The compound (A) is a compound represented by the following general formula (1) (hereinafter also referred to as “component (A)”).

(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 alkanol ammonium, and an alkyl ammonium. 1 type is shown.)

The hydrocarbon group represented by R in the general formula (1) is preferably an alkyl group or an alkenyl group. From the viewpoint of achieving good biodegradability and detergency of the resulting solid detergent, the carbon number of R is 1 or more and 12 or less, preferably 1 or more and 6 or less, more preferably 1 or more. 3 or less.
Specific examples of preferable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Among these, methyl group is preferable. The “various” means various isomers including n-, sec-, tert-, and iso-.
Specific examples of preferred alkenyl groups include vinyl, allyl, 2-butenyl, and 2-methyl-2-propenyl groups.

Examples of M ¹ , M ² , and M ³ in the general formula (1) include a hydrogen atom, an alkali metal such as sodium and potassium, ammonium, an alkanol ammonium, and an alkyl ammonium. 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) used in the present invention may be either a liquid or a solid, but is preferably a solid from the viewpoint of efficiently producing a solid detergent and handling properties.

  The content of the component (A) in the solid detergent of the present invention is 5% by mass or more, preferably 10% by mass or more, more preferably 12% by mass or more, from the viewpoint of improving the cleaning performance. From the viewpoint of blending cost and other components, it is 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, More preferably, it is 20 mass% or less.

<Silicone compound (B)>
The solid detergent of the present invention contains a silicone compound (B) (hereinafter also referred to as “component (B)”) from the viewpoint of suppressing discoloration of the compound (A). Since the solid detergent of the present invention contains the component (B), the influence of the oxygen bleach (C) on GDA is suppressed even when the oxygen bleach (C) described later is used. It is possible to suppress GDA coloring over a long period of time.
As the silicone compound (B), a water-insoluble silicone compound is preferable from the viewpoint of suppressing discoloration of the compound (A). In the present specification, “water-insoluble” means a property in which the amount dissolved in 1 L of ion-exchanged water at 20 ° C. is 1 g or less.
Specific examples of the component (B) include straight silicone compounds such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and modified silicones. In the present specification, “modified silicone” refers to polysiloxane having an organic group introduced at the side chain or terminal.
Modified silicones include long chain alkyl modified silicone, alkyl aralkyl modified silicone, alkyl polyether modified silicone, polyether modified silicone, higher alcohol ester modified silicone, higher fatty acid ester modified silicone, fluoroalkyl modified silicone, amino modified silicone, amide modified. One selected from silicone, amino polyether modified silicone, epoxy modified silicone, carboxyl modified silicone, carbinol modified silicone, phenol modified silicone, methacryl modified silicone, oxazoline modified silicone, polyester modified silicone, hydroxy modified silicone, and alkoxy modified silicone The above can be used.
Among these, at least one selected from dimethylpolysiloxane, methylphenylpolysiloxane, and polyether-modified silicone represented by the following general formulas (B-1) to (B-3c) is preferable.

(B-1) Dimethylpolysiloxane As dimethylpolysiloxane, what is represented, for example by the following general formula (B-1) is preferable.

(In the formula, a represents a number of 3 or more and 20,000 or less, preferably 10 or more and 10,000 or less, more preferably 100 or more and 5,000 or less, and further preferably 500 or more, 1 or less. 1,000 or less.)

(B-2) Methylphenyl polysiloxane As methylphenyl polysiloxane, what is represented, for example by the following general formula (B-2a) or (B-2b) is preferable.

(In the formula, b represents a number of 1 or more and 20,000 or less, preferably 10 or more and 10,000 or less, more preferably 100 or more and 5,000 or less, and further preferably 500 or more, 2 or less. C and d are each a number of 1 or more, and a total number of 2 or more and 500 or less, preferably 5 or more and 300 or less, more preferably 10 or more and 100 or less. And more preferably 30 or more and 80 or less.)

(B-3) Polyether Modified Silicone As the polyether modified silicone, for example, those represented by general formula (B-3a), (B-3b) or (B-3c) are preferable.

Wherein R ⁵ is a group — (CH ₂ ) ₃ —O— (C ₂ H ₄ O) _g — (C ₃ H ₆ O) _h —A [A is a hydrogen atom or a carbon number of 1 or more and 12 or less. An alkyl group, g and h each represent an integer of 0 or more and 50 or less, which is 1 or more in total, preferably 5 or more and 30 or less, more preferably 10 or more and 20 or less.] Represents an integer of 1 or more and 2,000 or less, preferably 10 or more and 1,000 or less, more preferably 50 or more and 500 or less, f represents an integer of 1 or more and 1,000 or less, Preferably they are 10 or more and 500 or less, More preferably, they are 50 or more and 300 or less.

In the present invention, among these silicone compounds, the silicone compound represented by formula (B-1) or (B-3a) is more preferable from the viewpoint of suppressing coloring of the component (A).
The silicone compound (B) in the present invention may be in any form such as an oil type, an emulsion type, and a compound type, and among these, a compound type that is a mixture with an inorganic compound such as silica. Is preferred.

The weight average molecular weight of the component (B) is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 1,000,000 or less, more preferably 800,000 or less, More preferably, it is 600,000 or less.
The viscosity of component (B) at 25 ° C. is preferably 100 mPa · s or more, more preferably 200 mPa · s or more, still more preferably 500 mPa · s or more, and preferably 10,000 mPa · s or less. Preferably it is 5,000 mPa * s or less, More preferably, it is 1,500 mPa * s or less.

  The content of the component (B) in the solid detergent is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1%, from the viewpoint of suppressing coloring of the component (A). % By mass or more, more preferably 0.15% by mass or more, and 7% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less from the viewpoint of blending production cost, cleaning performance and other components. More preferably, it is 1 mass% or less, More preferably, it is 0.7 mass% or less, More preferably, it is 0.6 mass% or less, More preferably, it is 0.5 mass% or less.

The amount of component (B) relative to 100 parts by weight of component (A) is preferably 0.3 parts by weight or more, more preferably 0.6 parts by weight or more, and still more preferably from the viewpoint of suppressing coloring of component (A). From the viewpoint of production cost and cleaning performance, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less.
Further, in the present invention, the (A) component and the (B) component are contained as co-granulated granules, but the content of the (A) component or the (B) component contained in other states is less. Is preferable from the viewpoint of improving storage stability. The ratio of the total content of the (A) component and the (B) component contained as co-granulated granules to the total content of the (A) component and the (B) component contained in the solid detergent is 50 mass. % Or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, still more preferably 90% by weight or more, and most preferably 100% by weight.

<Oxygen bleach (C)>
In the present invention, it is preferable to use an oxygen bleach (C) (hereinafter also referred to as “component (C)”) in order to improve the detergency.
Examples of the oxygen bleach include organic peracids or salts thereof such as magnesium monoperoxyphthalate, alkali metal perborates (monohydrate or tetrahydrate), percarbonates, persulfates, and One or more selected from persilicates can be used.
Among these, one or more selected from sodium persulfate, sodium percarbonate, and sodium perborate can be used from the viewpoint of improving the cleaning performance and minimizing the influence on GDA.

  The oxygen bleach is preferably coated with a coating material. When coated with a coating material, the generation of an oxidizing agent such as hydrogen peroxide is suppressed during storage, so that GDA coloring can be further suppressed. Examples of the coating material include water-insoluble organic compounds such as silicic acid, boric acid and salts thereof, soda ash, paraffin and wax.

The content of the component (C) in the solid detergent is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more from the viewpoint of cleaning performance, and suppresses coloring of GDA. From this viewpoint, the content is preferably 30% by mass or less, more preferably 20% by mass, still more preferably 15% by mass or less, and still more preferably 10% by mass or less.
The amount of the component (B) relative to 100 parts by mass of the component (C) is preferably 0.3 parts by mass or more, preferably 1 part by mass or more, from the viewpoint of suppressing the influence of the component (C) on the GDA. Preferably it is 1.5 parts by mass or more, more preferably 2 parts by mass or more, and from the viewpoint of cleaning performance, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

  The total content of the components (A), (B) and (C) in the solid detergent is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 18% by mass from the viewpoint of cleaning performance. From the viewpoint of blending a binder and an alkali agent, it is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less, and still more preferably 30% by mass or less.

<Organic acid (D)>
In the present invention, from the viewpoint of suppressing coloring of the component (A), it is also referred to as an organic acid (D) having 4 to 8 carbon atoms (hereinafter referred to as “(D) component”). ) Is preferably used. The component (D) is preferably contained in the solid detergent as granules granulated together with the components (A) and (B).
The carbon number of the organic acid (D) is 4 or more from the viewpoint of obtaining a solid detergent, and is 8 or less, more preferably 6 or less, from the viewpoint of suppressing coloring of the component (A).
Specific organic acids include malic acid (carbon number = 4), succinic acid (carbon number = 4), tartaric acid (carbon number = 4), butanoic acid (carbon number = 4), maleic acid (carbon number = 4). ), Fumaric acid (carbon number = 4), pentanoic acid (carbon number = 5), pivalic acid (carbon number = 5), gluconic acid (carbon number = 6), citric acid (carbon number = 6), caproic acid ( One or more selected from carbon number = 6), heptanoic acid (carbon number = 7), and octanoic acid (carbon number = 8) can be used.
Among these, fumaric acid, succinic acid, malic acid, and citric acid are more preferable from the viewpoint of suppressing coloring of component (A), and succinic acid is preferable from the viewpoint of ease of handling (low hygroscopicity) and economy. Acid and fumaric acid are particularly preferred.
The organic acid having 4 to 8 carbon atoms is preferably in the form of powder from the viewpoint of obtaining a solid cleaning agent.

  When the organic acid having 4 or more and 8 or less carbon atoms is a solid, the average particle diameter is preferably 10 μm or more, more preferably 50 μm or more, and further preferably 100 μm or more, from the viewpoint of granulation property, solubility, and handleability. And preferably 500 μm or less, more preferably 250 μm or less, and still more preferably 150 μm or less. In addition, the average particle diameter of organic acid can be measured by the method as described in an Example.

  When the particle size of the organic acid is larger than the above particle size, it is preferable to crush or classify in advance so as to obtain a suitable particle size. Examples of the crusher that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. These may be a single stage operation, or may be a multistage operation of the same kind or different kind of pulverizer. Examples of the classification method include a method using a vibration sieve, an ultrasonic vibration sieve, a centrifugal wind classifier, or the like.

  The content of the component (D) in the solid detergent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.2% by mass, from the viewpoint of suppressing coloring of the component (A). 3% by mass or more, more preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably from the viewpoint of blending production cost, cleaning performance and other components. Is 10% by mass or less, more preferably 7% by mass or less, still more preferably 6% by mass or less, and still more preferably 5% by mass or less.

  The amount of component (D) relative to 100 parts by weight of component (A) is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 3 parts by weight from the viewpoint of suppressing coloring of component (A). Part or more, more preferably 5 parts by weight or more, and from the viewpoint of production cost and cleaning performance, 25 parts by weight or less, preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less. It is.

  The amount of component (D) relative to 100 parts by weight of component (B) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and even more preferably 130 parts by weight or more from the viewpoint of suppressing coloring of component (A). , More preferably 150 parts by mass or more, and preferably 1500 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 500 parts by mass or less, still more preferably 400 parts by mass or less, and still more preferably. 300 parts by mass or less.

<Binder>
The solid detergent preferably contains a binder from the viewpoint of solidifying into a formulation and increasing the strength of the granulated product and improving handling properties. Examples of the binder include nonionic surfactants and nonionic polymers. These binders are preferably thermoplastic from the viewpoint of granulation. Further, the water-soluble binder may or may not be an aqueous solution, but when an aqueous solution is used, it is necessary to evaporate water by drying during granulation in order to suppress coloring of GDA. It is preferable that it is not aqueous solution from a viewpoint of cost and productivity.

Nonionic surfactants include, for example, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, tetraoleic acid polyoxyethylene sorbite, polyoxy 1 selected from ethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, and polyoxyethylene hydrogenated castor oil More than seeds can be used.
Among these, glycerin fatty acid ester or polyglycerin fatty acid ester is preferable from the viewpoint of improving the cleaning performance of the solid detergent.
The nonionic surfactant is preferably solid at room temperature (25 ° C.) from the viewpoint of granulation properties.

As the nonionic polymer, one or more selected from polypropylene glycol, polyethylene glycol, and polyoxyethylene polyoxypropylene glycol can be used. Among these, polyethylene glycol and polypropylene glycol are preferable.
When polypropylene glycol is used, its number average molecular weight is preferably 600 or more, more preferably 2,000 or more, and preferably 20,000 or less, more preferably 12,000 or less.
When polyethylene glycol is used, its number average molecular weight is preferably 4,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and preferably 20,000 or less, more preferably 13 , 000 or less, more preferably 9,000 or less.
Polyethylene glycol is preferable because it is easy to granulate because of its good handleability. The number average molecular weights of polypropylene glycol and polyethylene glycol can be determined from the hydroxyl value. As the binder, one or more selected from the above compounds can be used.

The content of the binder with respect to 100 parts by mass of the total amount of the component (A) and the component (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 from the viewpoint of the strength of the granulated product. From the viewpoint of the solubility of the granulated product, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 65 parts by mass or less.
In addition, polypropylene glycol can be used also as an antifoamer from a viewpoint of improving the defoaming property at the time of using a granulated material as a solid cleaning agent.
When polypropylene glycol is contained in the granulated product, the content of polypropylene glycol in the granulated product is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, and Preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

  In the solid detergent, the content of the binder is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, from the viewpoint of improving granulation properties and strength of the granulated product. More preferably, it is 8% by mass or more, and from the viewpoint of the solubility of the granulated product, it is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass. % Or less, and more preferably 15% by mass or less.

<Other ingredients>
(Carboxy group-containing polymer)
From the viewpoint of further suppressing the coloring of the component (A) and improving the washing performance, the solid detergent of the present invention preferably contains a carboxy group-containing polymer.
Examples of the carboxy group-containing polymer include a polymer of a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms or a salt thereof, a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms, or a compound thereof. One or more selected from copolymers of a salt and an olefin having 2 to 12 carbon atoms can be used.
The carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms is selected from maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid and salts thereof. These acid anhydrides may be used. Among these, acrylic acid-maleic acid copolymer and diisobutylene-maleic acid copolymer are preferable from the viewpoint of further suppressing coloring of component (A) and improving the washing performance, and diisobutylene-maleic acid. An acid copolymer is more preferable.
The average particle size of the carboxy group-containing polymer is preferably 10 μm or more, more preferably 30 μm or more, still more preferably 50 μm or more, still more preferably 80 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less. More preferably, it is 300 micrometers or less, More preferably, it is 150 micrometers or less. In addition, the average particle diameter of a carboxy-group containing polymer can be measured by the method as described in an Example.

(Alkaline agent)
From the viewpoint of enhancing the cleaning performance of the solid cleaning agent, the solid cleaning agent preferably contains an alkaline agent.
As the alkali agent, alkali metal carbonates, alkali metal silicates, amine compounds and the like can be used.
As alkali metal carbonate, 1 or more types chosen from sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate can be used. Moreover, you may use the anhydrous salt of sodium carbonate known as soda ash.
As the alkali metal silicate, crystalline layered sodium silicate (“Prefeed” manufactured by Tokuyama Siltec Co., Ltd.) 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. Among these alkali agents, alkali metal carbonates and alkali metal silicates are preferable.
The content of the alkaline agent is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, from the viewpoint of cleaning performance, and preferably Is 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 60% by mass or less.

  In the solid cleaning agent of the present invention, components that can be used in a normal cleaning agent may be blended. For example, sequestering agents other than GDA, surfactants, bleach activators, enzymes, oil-absorbing powders, extenders or diluents, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial, antifungal 1 or more types chosen from an agent and a pigment | dye can be used.

[Method for producing solid detergent]
Although there is no restriction | limiting in particular in the manufacturing method of the solid cleaning agent of this invention, Manufacturing with the manufacturing method of this invention which has the following processes 1-3 is preferable from a viewpoint of manufacturing efficiency.
Step 1: Mixing at least the component (A), the component (B) and a binder to obtain a mixture Step 2: Obtaining a granulated product of the mixture obtained in Step 1 Step 3: Forming obtained in Step 2 The step of mixing the granule with a component other than the component (A) and the component (B)

<Step 1>
Step 1 is a step of mixing at least the component (A), the component (B), and a binder to obtain a mixture.
As a method of mixing the component (A), the component (B) and the binder in step 1, any method may be used as long as it can be mixed substantially uniformly. For example, V-type blender (manufactured by Paulex Co., Ltd.), double cone mixer (manufactured by Tokuju Kogakusho Co., Ltd.), ribbon blender (manufactured by Hosokawa Micron Co., Ltd.), SV mixer (manufactured by Shinko Bantech Co., Ltd.), etc. Can be used and mixed.
In Step 1, from the viewpoint of more uniform mixing, after mixing the component (A), the component (B) and the liquid binder component, the component (D) and the solid binder component may be mixed. Preferably, when mixing polyethylene glycol having a melting point of room temperature or higher, it is preferable to add and mix the polyethylene glycol at the end of step 1.
That is, in step 1, at least the component (A), the component (B), and the liquid binder are mixed, the organic acid (D) is mixed, and finally, polyethylene glycol having a melting point of 25 ° C. or higher is added to obtain a mixture. It is preferable that it is a process.

In the mixture obtained in Step 1, the content of the component (A) is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more, from the viewpoint of detergency, and the production cost. And from a viewpoint of mix | blending other components, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.
In the mixture obtained in step 1, the content of the component (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably from the viewpoint of suppressing coloring of the component (A). 0.5% by mass or more, more preferably 1% by mass or more, and from the viewpoint of blending production cost, cleaning performance and other components, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably Is 3% by mass or less.
In the mixture obtained in step 1, the content of the binder is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more from the viewpoint of granulation properties. From the viewpoint of the solubility of the granules, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
The amount of the component (B) with respect to 100 parts by mass of the component (A) and the amount of the binder with respect to 100 parts by mass of the total amount of the components (A) and (B) are as described above.

<Step 2>
Step 2 is a step of obtaining a granulated product of the mixture obtained in Step 1.
When obtaining granulated material in this step, well-known such as pelleter double, dome gran, twin dome gran, disk pelleter (manufactured by Dalton), basket type granulator (manufactured by Kikusui Seisakusho) In addition to the extrusion granulator, Henschel mixer (manufactured by Nippon Coke Co., Ltd.), high speed mixer (manufactured by Earth Technica Co., Ltd.), vertical granulator (manufactured by Paulek Co., Ltd.), Redige mixer (Matsusaka Giken Co., Ltd.) )), Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), V-type mixer (manufactured by Fuji Powder Co., Ltd.), ribbon mixer (manufactured by Hosokawa Micron Co., Ltd.), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), A well-known rolling granulator such as an SV mixer (manufactured by Shinko Vantec Co., Ltd.) can be used, but extrusion granulation can be performed using an extrusion granulator. It is preferred.

  The hole diameter of the screen when using an extrusion granulator as the granulator is preferably 0.3 mm or more, more preferably 0.5 mm or more, and still more preferably 0.6 mm or more, from the viewpoint of granulation and solubility. And it is preferably 5.0 mm or less, more preferably 2.0 mm or less, and still more preferably 1.0 mm or less. By using such a screen, a columnar granulated product can be obtained.

  The obtained extruded granulated product is cooled in order to suppress coalescence and agglomeration, and then can be sized in order to adjust the shape (length, etc.) as necessary. As a machine used for sizing, a known crusher (or crusher) can be used. For example, a high speed mixer (manufactured by Earth Technica Co., Ltd.), Malmerizer (manufactured by Dalton Co., Ltd.), Examples include Spirer Flow (manufactured by Freund Sangyo Co., Ltd.), Fitzmill (manufactured by Dalton Co., Ltd.), Power Mill (manufactured by Paulek Co., Ltd.), Comil (manufactured by Quadro), and the like.

  In step 2, in the case of compression molding, from the viewpoint of ease of handling at the time of supply to a compression molding machine, after granulating the mixture obtained in step 1 in advance, the granulated product is compression molded. Is preferred. That is, step 2 is preferably a step of obtaining a granulated product of the mixture obtained in step 1 and then compression molding the granulated product.

  In the case of compression molding, it is not limited as long as briquettes or tablets can be obtained, and well-known briquetting machines and tableting machines can be used. A briquetting machine is a device that continuously compresses and forms a granulated product between two rolls in which two rolls engraved with a pocket as a matrix of a desired compressed product are cut into each other and rotate at the same speed. It is. As a known briquetting machine, a briquetting machine (manufactured by Shinto Kogyo Co., Ltd.) or the like can be used. The tableting machine is an apparatus that fills a granule in a mortar and compresses it between a lower punch and an upper punch to form. A tableting machine is a single-punch tableting machine in which a pair of upper and lower punches move up and down within a single die, and a die is embedded in the outer periphery of a horizontally rotating turntable at equal intervals. There is a rotary tableting machine in which a series of operations of filling, compressing, and discharging are continuously performed while rotating. As a known tableting machine, a single tableting machine can be a tableting machine manufactured by Riken Instruments, and a rotary tableting machine can be a tableting machine manufactured by Kikusui Chemical Co., Ltd.

  From the viewpoint of briquette solubility, the particle size of the briquette when using a briquette machine is preferably 10 mm or less, more preferably 7 mm or less, and even more preferably 5 mm or less. The briquette shape is not particularly limited, but a briquette shape, an almond shape, a pillow shape, a finger shape, a lens shape and the like are preferable.

  When using a tableting machine, the tablet size is preferably 80 mm or less in diameter (in the case of a polygon, the length of one side). The thickness of the tablet is preferably 20 mm or less. The shape of the tablet is not particularly limited, but a columnar shape and a polygonal shape are preferable.

<Step 3>
Step 3 is a step of mixing the granulated product obtained in Step 2 with components other than the component (A) and the component (B).
In the present invention, the component (C) is preferably mixed in the step 3 from the viewpoint of suppressing discoloration.
In this step 3, the amount of other components with respect to 100 parts by mass of the granulated product obtained in step 2 is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, And preferably it is 80 mass parts or less, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less.
In step 3, any method may be used as long as the granulated product obtained in step 2 and other components can be mixed substantially uniformly. For example, it is preferable to mix using the mixer described in Step 1.

<Step 4>
In the manufacturing method of this invention, you may perform the process 4 which makes the solid cleaning agent obtained at the process 3 into the form of a tablet and a briquette further.
The step 4 is preferably a step of obtaining a granulated product of the mixture obtained in the step 3, and is preferably performed under the same conditions as the step 2.

  The solid cleaning agent can be suitably used as a cleaning agent for tableware, clothing, residence, etc., and is particularly useful for an automatic dishwasher. The solid detergent is preferably in the form of a tablet, briquette or powder.

In the following examples and comparative examples, unless otherwise specified, “%” means “% by mass” and “parts” means “parts by mass”.
The raw materials and apparatuses used in Examples and Comparative Examples are as follows.
<Raw material>
[Component (A)]
・ Methylglycine diacetic acid trisodium salt (MGDA): “Trilon M Powder” manufactured by BASF Japan Ltd., effective content 87% by mass
[(B) component]
Silicone: “Xiameter ACP-1500 Antifoam Compound” manufactured by Toray Dow Corning
[Component (C)]
Sodium percarbonate: “KCPZ-S” manufactured by Nippon Peroxide Co., Ltd., average particle size of 748 μm

[Component (D)]
・ Succinic acid: Kawasaki Kasei Kogyo Co., Ltd., average particle size 104 μm
〔binder〕
-Polypropylene glycol: “Preminol S4011” manufactured by Asahi Glass Urethane Co., Ltd.
Number average molecular weight: 10,000
・ Polyethylene glycol: “K-PEG6000LA” manufactured by Kao Corporation
Number average molecular weight: 8,500
Glycerol monostearate: “Excel VS-95” manufactured by Kao Corporation

[Other ingredients]
(Carboxy group-containing polymer)
Diisobutylene-maleic acid copolymer: “Accus 460ND” (average particle size 107 μm) manufactured by Rohm and Hass
・ Acrylic acid-maleic acid copolymer: “Socaran CP45 granule” manufactured by BASF Japan Ltd.
(Alkaline agent)
・ Sodium carbonate: “Soda ash” (average particle size 281 μm) manufactured by Central Glass Co., Ltd.
・ Sodium silicate: “Pre-Feed Granule” manufactured by Tokuyama Silktech Co., Ltd.
(Metal sequestering agent)
・ Tetraacetylethylenediamine; manufactured by Tokyo Chemical Industry Co., Ltd. (enzyme)
・ Enzyme: "Duramil 120T" manufactured by Novozymes Japan

<Measuring method of average particle diameter>
The average particle diameter of diisobutylene-maleic acid copolymer and succinic acid is measured by using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) and dispersing the particles in an insoluble solvent. The median diameter measured in this manner was taken as the average particle diameter. In addition, acetone was used as a solvent for measuring the average particle size of succinic acid, and ethanol was used as a solvent for measuring the average particle size of the polymer.
Moreover, the average particle diameter measurement of sodium percarbonate and sodium carbonate calculated the average particle diameter from the mass fraction by the size of a sieve mesh, after vibrating for 5 minutes using (mesh opening 2000-125 micrometers).
More specifically, nine-stage standard sieves and saucers having openings of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm, which are defined by the metal mesh sieve described in JIS K8801-1: 2006 , Using a sieve, stack in order from a sieve with a small mesh opening, add 100 g of particles from the top of the top 2000 μm sieve, cover and low tap type sieve shaker (manufactured by HEIKO Mfg. Co., Ltd., 156 times) / Min, rolling: 290 times / min), and after shaking for 5 minutes, the mass of the particles remaining on each sieve and the saucer was measured. The median diameter was calculated from the weight fraction depending on the size of the sieve mesh, and was taken as the average particle diameter.

<Device>
Mixer: Nauter mixer, Hosokawa Micron Co., Ltd. extrusion granulator: Pelleter Double EXD-100 type, Dalton granulator: Power mill, Dalton Co.

<Example 1, comparative example 1>
According to the blending amounts shown in Table 1, (A) component, (B) component, (D) component, carboxy group-containing polymer, and polypropylene glycol were charged into a Nauta mixer, and the jacket temperature was 90 ° C. and mixed for 20 minutes.
A binder component other than the previously melted polypropylene glycol was added thereto, and the mixture was further mixed for 20 minutes, and then this mixture was extracted.
Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm by an extrusion granulator to obtain a granulated product. The granulated product was further cooled, and then pulverized by a granulator to obtain a columnar granulated product in which the component (A) and the component (B) were co-granulated. The obtained granulated product had an average diameter of 0.7 mm and an average length of 1.2 mm.
The granulated product, the component (C) and other components were charged into a mixer and mixed for 10 minutes to obtain a solid detergent.
The color tone of the solid detergents of Examples and Comparative Examples obtained by the above methods was evaluated by the following methods.

Color tone after storage After filling 300 g of solid detergent into a box-shaped polypropylene container (length 10 cm x width 12 cm x height 12 cm), the filter paper is folded in half, and a gap of 1 mm is formed between the lid and the container. After being opened and stored for 90 days in an environment of 30 ° C. and 70% RH (relative humidity), the lid was opened and the color tone of the upper part of the powder was evaluated according to the following criteria. The evaluation was performed by visual observation by three panelists.
Filter paper; FILTER-PAPER ADVANTEC ITEM2 (70 x 70 mm)
<Evaluation criteria>
1: Same as before storage, white.
2: Slight change from before storage, but white.
3; Some yellowing is recognized.
4: Obviously yellowing is observed.

From Table 1, Example 1 containing the component (B) maintained a white color even during long-term storage for 90 days, and no problem was recognized as the appearance of the product.
On the other hand, in Comparative Example 1 in which the component (B) was not used, yellowing was observed after long-term storage for 90 days, and the product appearance was impaired.
In addition, the solid detergent of this invention can be suitably implemented also by the formulation example shown in Table 2.

Claims (11)

A solid detergent containing the compound (A) represented by the following general formula (1) and the silicone compound (B) as co-granulated granules, and the content of the compound (A) is 5% by mass or more, 70 Solid cleaning agent whose content of a silicone compound (B) is 0.01 mass% or more and 7 mass% 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 alkanol ammonium, and an alkyl ammonium. 1 type is shown.)   Furthermore, the solid detergent of Claim 1 containing 1 mass% or more and 30 mass% or less of oxygen type bleaching agents (C).   The solid detergent according to claim 2, wherein the oxygen bleach (C) is at least one selected from sodium persulfate, sodium percarbonate, and sodium perborate.   The solid cleaning agent according to claim 2 or 3, wherein the total content of the compound (A), the silicone compound (B), and the oxygen bleach (C) is 10% by mass or more and 80% by mass or less.   The solid cleaning agent in any one of Claims 1-4 whose quantity of the said silicone compound (B) with respect to 100 mass parts of said compounds (A) is 0.3 mass part or more and 10 mass parts or less.   The solid detergent in any one of Claims 2-5 whose quantity of the said silicone compound (B) with respect to 100 mass parts of said oxygen bleach (C) is 0.3 mass part or more and 10 mass parts or less.   The solid cleaning agent according to any one of claims 1 to 6, wherein the silicone compound (B) is at least one compound selected from dimethylpolysiloxane, methylphenylpolysiloxane, and polyether-modified silicone.   The solid cleaning agent according to any one of claims 1 to 7, wherein the solid cleaning agent is for clothing, a house, or an automatic dishwasher. The manufacturing method of the solid cleaning agent in any one of Claims 1-8 including the following process.
Step 1: Mixing at least the component (A), the component (B) and a binder to obtain a mixture Step 2: Obtaining a granulated product of the mixture obtained in Step 1 Step 3: Forming obtained in Step 2 The step of mixing the granule with a component other than the component (A) and the component (B)   The manufacturing method of the solid cleaning agent of Claim 9 which mixes an organic acid (D) in the said process 1 further.   The manufacturing method of the solid cleaning agent of Claim 9 or 10 which mixes the said oxygen type bleaching agent (C) in the said process 3. FIG.