JP2013010819A - Powder detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder detergent composition that includes glycine-N,N-diacetic acid derivative (GDA), wherein discoloration is not caused even after long-term storage, and the storage stability is excellent.SOLUTION: The powder detergent composition includes: a granule that co-granulates a glycine-N,N-diacetic acid derivative (A component) shown by General formula (1), and a reducing agent (B component); and an oxygen based bleaching agent (C component) to meet the following conditions. A component: 1-50 mass%; B component: 0.01-10 mass%; and C component: 1-25 mass%. In the formula, M-Meach independently denote a hydrogen atom or a cation component, and R denotes a 1-18C alkyl group or alkenyl group.

Description

  The present invention relates to a powder detergent composition that can be suitably used in an automatic dishwasher, and a method for producing the same.

  Conventionally, a large amount of surfactant has been added to the powder cleaning composition, but in recent years, from the viewpoint of environmental consideration, the amount of surfactant used can be increased by adding more organic chelating agent with good biodegradability. There is a movement to reduce this. Examples of the organic chelating agent having good biodegradability include glycine-N, N-diacetic acid derivatives (hereinafter sometimes abbreviated 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.

Examples of the detergent composition containing an organic chelating agent having good biodegradability include, for example, GDA, percarbonate or perborate, a bleach precursor, a nonionic surfactant, and the like at a specific ratio. A bleach-containing detergent composition to be contained has been proposed (see Patent Document 1).
Further, a method for washing clothes using a detergent composition containing a salt of an aminocarboxylic acid-based organic chelating agent such as GDA as an essential component and further containing a recontamination preventing agent has been disclosed (see Patent Document 2). ).
Patent Documents 1 and 2 describe a detergent composition containing GDA or the like as described above, but do not describe any discoloration of GDA.

Japanese Patent Laid-Open No. 11-35978 JP 2009-132934 A

The inventors of the present invention have made research in developing the powder cleaning composition containing GDA, and faced a new problem that GDA in the GDA-containing powder cleaning composition is discolored during long-term storage.
The present invention provides a powder cleaning composition containing glycine-N, N-diacetic acid derivative (GDA), which does not change color even after long-term storage and has excellent storage stability. Let it be an issue.

In order to solve the above-mentioned problems, the present inventors have examined GDA discoloration and found that GDA discoloration is promoted by the presence of an oxygen bleach. However, oxygen-based bleaches are bases with excellent cleaning performance, and powder cleaning compositions that do not contain oxygen-based bleaching agents have a significant decrease in cleaning performance.
Therefore, as a result of further investigations on the technology for suppressing the discoloration of GDA in the presence of an oxygen-based bleach, the present inventors have incorporated GDA and a reducing agent as granules into the powder detergent composition. It has been found that GDA discoloration can be suppressed.

（式中、Ｍ¹〜Ｍ³は、それぞれ独立に水素原子又はカチオン成分を示し、Ｒは、炭素数１〜１８のアルキル基又はアルケニル基を示す。）
［２］Ａ成分とＢ成分とを共造粒した後に、得られた造粒物とＣ成分とを混合する前記粉末洗浄剤組成物の製造方法。 That is, the present invention provides the following [1] and [2].
[1] A granule containing a glycine-N, N-diacetic acid derivative (component A) and a reducing agent (component B) represented by the following general formula (1), and an oxygen bleach (component C) A powder detergent composition containing the following conditions.
A component: 1-50 mass%
B component: 0.01-10 mass%
C component: 1 to 25% by mass

(Wherein, M ¹ ~M ³ each independently represent a hydrogen atom or a cation component, R represents an alkyl or alkenyl group having 1 to 18 carbon atoms.)
[2] The method for producing a powder cleaning composition, comprising co-granulating the A component and the B component, and then mixing the obtained granulated product and the C component.

  In a powder cleaning composition containing a glycine-N, N-diacetic acid derivative (GDA), no discoloration occurs even after long-term storage, and a powder cleaning composition having excellent storage stability can be provided.

[Powder cleaning composition]
The powder detergent composition of the present invention comprises a specific blend of granules containing a glycine-N, N-diacetic acid derivative (component A) and a reducing agent (component B) and an oxygen bleach (component C). It is contained in an amount.
In this specification, “granule” refers to agglomerated fine particles and agglomerated fine particles, and “powder” refers to solid particles at room temperature (20 ° C.), and Refers to a granule.

<Granule>
The granule used in the powder detergent composition of the present invention may be composed of at least an A component and a B component, but may contain polypropylene glycol as an antifoaming agent and polyethylene glycol as a binder. .

(Component A: Glycine-N, N-diacetic acid derivative)
The glycine-N, N-diacetic acid derivative (GDA) used in the present invention is represented by the following general formula (1).

（式中、Ｍ¹〜Ｍ³は、それぞれ独立に水素原子又はカチオン成分を示し、Ｒは、炭素数１〜１８のアルキル基又はアルケニル基を示す。）

(Wherein, M ¹ ~M ³ each independently represent a hydrogen atom or a cation component, R represents an alkyl or alkenyl group having 1 to 18 carbon atoms.)

1-18 are preferable, as for carbon number of the alkyl group or alkenyl group which R in the said General formula (1) shows, 1-12 are more preferable, 1-6 are more preferable, and 1-3 are still more preferable. If carbon number is in the said range, the biodegradability and detergency of the powder cleaning composition obtained will become favorable.
Specific examples of the preferable alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, and the like. Among these, a methyl group is preferable. . Here, “various” means various isomers including n-, tert-, and iso-.
Specific examples of preferred alkenyl groups include vinyl, allyl, 2-butenyl, 2-methyl-2-propenyl and the like.

  M in the general formula (1) represents a hydrogen atom or a cation component, and examples of the cation component include alkali metals such as sodium and potassium, ammonium, alkanolamine, and alkylamine. In these, a hydrogen atom and an alkali metal are preferable from a viewpoint of availability and a viewpoint of manufacturing cost reduction.

The component A used in the present invention may be either liquid or solid, but it is solid from the viewpoint of efficiently producing the powder detergent composition, from the viewpoint of biodegradability, and from the viewpoint of physical properties (handleability). Is preferred.
In this invention, 1-50 mass% is preferable, as for content of A component in a powder cleaning composition, 5-40 mass% is more preferable, 10-35 mass% is still more preferable, 15-30 mass% is Even more preferred. When the content of the component A is less than 1% by mass or exceeds 50% by mass, a sufficient chelating effect cannot be obtained and the cleaning ability may be deteriorated.
In addition, in this invention, it is preferable that the said A component is contained in the whole quantity in the granule.

(B component: reducing agent)
In the present invention, a reducing agent is used for the purpose of suppressing yellowing of GDA constituting the A component. That is, the yellowing of GDA is caused by the influence of H ₂ O _{2 and the} like generated from oxygen bleaching agent. Therefore, the inclusion of a reducing agent together with GDA in the granule minimizes the influence of the oxidizing agent on GDA. Can be suppressed.
Examples of the reducing agent used in the present invention include sulfites such as sodium sulfite, sodium hydrogen sulfite, and potassium sulfite, and nitrites such as sodium nitrite. Among these, sodium sulfite and sodium nitrite include preferable. With these reducing agents, yellowing of GDA caused by the oxidizing agent generated in the powder cleaning composition can be effectively suppressed. These reducing agents may be used individually by 1 type, and may use 2 or more types together.

The average particle diameter of the reducing agent used as the component B is preferably 10 to 500 μm, more preferably 30 to 400 μm, and still more preferably 50 to 300 μm from the viewpoint of handleability.
The average particle diameter can be obtained by observing arbitrary 100 granules with an optical microscope and calculating the number average thereof. When the granule has a major axis and a minor axis, the major axis is adopted for calculating the average particle diameter.

Content of B component in a powder cleaning composition is 0.01-10 mass%, 0.1-5 mass% is more preferable, 0.1-3 mass% is still more preferable. When the content of the B component is less than 0.01% by mass, it is difficult to suppress GDA coloring, and when the content exceeds 10% by mass, the cost increases unnecessarily.
In addition, from the viewpoint of effectively suppressing discoloration of the A component, the amount of the B component with respect to 100 parts by mass of the A component in the powder cleaning composition is preferably 0.3 to 50 parts by mass, and 0.5 to 30 masses. Part is preferable, and 1 to 10 parts by mass is more preferable.

(Polypropylene glycol)
In the present invention, it is preferable to use polypropylene glycol as the antifoaming agent from the viewpoint of improving the antifoaming property of the powder cleaning composition. The number average molecular weight of this polypropylene glycol is preferably 600 to 20,000, and more preferably 2,000 to 12,000.

  1-6 mass% is preferable, as for content of the polypropylene glycol in a powder cleaning composition, 1.5-5 mass% is more preferable, and 2-4 mass% is still more preferable. Polypropylene glycol may be blended in a granule composed of the A component and the B component, or after preparing a granule composed of the A component and the B component, it may be mixed together with the C component.

(Polyethylene glycol)
In the present invention, polyethylene glycol may be used as a binder for the purpose of improving the physical strength of the granules composed of the A component and the B component.
The number average molecular weight of polyethylene glycol used as the binder is preferably 4,000 to 20,000, more preferably 6,000 to 13,000, and still more preferably 7,000 to 9,000. If the number average molecular weight of polyethylene glycol is within the above range, it is easy to granulate because the handleability is good.
The number average molecular weights of polypropylene glycol and polyethylene glycol can be determined from the hydroxyl value.

  10-100 mass% is preferable with respect to the total amount of A component and B component, and, as for the usage-amount of polyethyleneglycol, 10-50 mass% is more preferable, and 15-40 mass% is still more preferable. If the amount of polyethylene glycol used is within the above range, granules having excellent strength can be produced, and since the granules are less likely to be destroyed, the GDA coloring suppression effect can be obtained over a long period of time.

(Production method of granules)
Although there is no restriction | limiting in the manufacturing method of the granule containing each said component, It can obtain by mixing arbitrary components, such as A component, B component, polypropylene glycol, polyethyleneglycol, and co-granulating. A detailed method for producing the granules will be described later.

(Granule shape and size)
The granules in the present invention may be spherical, cylindrical or pellet-shaped. When the granule is spherical, the average particle size is preferably 0.2 to 12 mm, more preferably 0.3 to 10 mm. When it is a columnar shape or a pellet shape, the average diameter is preferably 0.3 to 10 mm, and the average length is preferably 0.3 to 10 mm. In addition, an average particle diameter, an average diameter, and an average length can be calculated | required by observing arbitrary 100 granules with an optical microscope, and calculating the average. When the granule has a major axis and a minor axis, the major axis is employed for calculating the average particle diameter and the average diameter, respectively.
The content of the A component in the granule is preferably 50 to 95% by mass, more preferably 60 to 90% by mass. The content of the B component in the granule is 0.1% from the viewpoint of suppressing GDA coloring. 10 mass% is preferable, and 0.3-5 mass% is more preferable. The amount of the B component with respect to 100 parts by mass of the A component in the granule is the same as the preferred range in the powder detergent composition from the viewpoint of effectively suppressing the discoloration of the A component.
The content of polyethylene glycol in the granules is preferably 3 to 30% by mass, and more preferably 5 to 25% by mass from the viewpoint of maintaining the strength of the granules.

<Ingredients other than granules>
(C component: oxygen bleach)
In the powder detergent composition of the present invention, an oxygen bleach is used in order to improve the cleanability which is the original purpose. In the present invention, as described above, since GDA and a reducing agent are contained in the granules, GDA is hardly affected by the oxygen-based bleaching agent, and as a result, GDA coloring can be suppressed over a long period of time. It becomes possible.
Examples of the oxygen bleach used in the present invention include organic hydrochloric acid such as magnesium monoperoxyphthalate or a salt thereof, alkali metal perborate (monohydrate or tetrahydrate), percarbonate, persulfate. Examples thereof include peroxides that generate hydrogen peroxide in aqueous solutions of salts and persilicates. Among these, inorganic peroxides such as sodium persulfate, sodium percarbonate, and sodium perborate are more preferable.

  Further, 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.

Content of C component in the powder cleaning composition in this invention is 1-25 mass%, 3-20 mass% is more preferable, and 5-15 mass% is still more preferable. When the content is less than 1% by mass, the cleaning ability of the powder detergent composition decreases, and when the content exceeds 25% by mass, the amount of H ₂ O ₂ or the like that causes GDA coloring increases. Therefore, the storage stability of the powder detergent composition is lowered.
Moreover, from a viewpoint of suppressing the influence of the discoloration by C component, 0.5-50 mass parts is preferable with respect to 100 mass parts of C components, 0.8-30 mass parts is more preferable, 1-20 Part by mass is more preferable.

(Alkaline agent)
In the powder detergent composition of the present invention, it is preferable to use an alkaline agent in order to improve the washability.
As the alkali agent, alkali metal carbonates, alkali metal silicates, amine compounds and the like can be used.
Examples of the alkali metal carbonate include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and the like. 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 silicates are also effective in preventing tableware oxidation.
Examples of the amine compound include alkanolamine. In the present invention, primary alkanolamines are particularly preferred, and specific examples include monoethanolamine.
Of these alkali agents, alkali metal carbonates are preferred.
As the alkaline agent, powdery or granular materials can be used. Granules can be used by appropriately adjusting the particle diameter and bulk density by granulation treatment or the like.
20-80 mass% is preferable from a viewpoint of detergency, and, as for content of the alkaline agent in the powder cleaning composition in this invention, 30-70 mass% is preferable, and 35-65 mass% is more preferable.

(Optional component)
In the powder cleaning composition of this invention, you may mix | blend the arbitrary components which can be used for a normal cleaning agent. For example, sequestering agents other than component A, surfactants, bleach activators, enzymes, oil-absorbing powders, extenders or diluents, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial / antibacterial agents A glaze, a pigment | dye, etc. can be mentioned.
[Metal ion sequestering agent]
In the powder cleaning composition of this invention, you may mix | blend metal ion sequestering agents other than A component. As the sequestering agent other than the component A, phosphates such as sodium tripolyphosphate can be used. When the powder detergent composition does not contain phosphorus, as a sequestering agent, citric acid, malic acid, tartaric acid, succinic acid, L-glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid Nitrilotriacetic acid, methylglycine triacetic acid, 1,3-propanediamine triacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraamine Polycarboxylic acids such as hexaacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethylglutamic acid, or salts thereof can be used. Of these, citric acid, succinic acid and ethylenediaminetetraacetic acid, dihydroxyethylglycine and hydroxyethylethylenediaminedicarboxymethylglutamic acid and their alkali metal salts are preferred.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants. Among these, nonionic surfactants are preferable.
Nonionic surfactants include polyoxyethylene monoalkyl or monoalkenyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene monoalkyl or monoalkenyl ether, polyoxybutylene monoalkyl or monoalkenyl ether, alkylene oxide-added monoalkyl And non-ionic surfactant mixture containing a group or a monoalkenyl group, sucrose fatty acid ester, aliphatic alkanolamide, fatty acid glycerin monoester, ethylene oxide condensed surfactant, alkyl glyceryl ether and alkyl glycoside. Among these, polyoxyalkylene alkyl ether is preferable, specifically, polyoxyethylene monoalkyl or monoalkenyl ether, wherein the average carbon number of the alkyl group or alkenyl group is 4 to 12, and the ethylene oxide addition mole Those having an average number of 1 to 20 moles are preferred. These nonionic surfactants may be used alone or in combination of two or more.

  In the present invention, a bleaching activator, an enzyme or the like that is generally blended as a detergent for an automatic dishwasher may be blended as a cleaning auxiliary component that further improves the cleaning power.

[Bleaching activator]
A bleaching activator is used in combination with the bleaching agent, and is a substance that reacts with hydrogen peroxide released from the bleaching agent to produce an organic peracid having a higher redox potential. Specific examples include tetraacetylethylenediamine, alkanoyloxybenzenecarboxylic acid or a salt thereof, and alkanoyloxybenzenesulfonate.

〔enzyme〕
As the enzyme, protease, amylase, lipase, cellulase, esterase, peroxidase and the like are preferably used, and commercially available products that are granulated can be used. Any enzyme may be appropriately selected in consideration of storage stability with other components. These enzymes may be used individually by 1 type, and may use 2 or more types together.
Among the enzymes, amylase which is expected to act on gelatinized starch which is difficult to remove with other detergents is preferable. A protease is also preferable because it exhibits a remarkable effect on a denatured protein that is difficult to remove with a surfactant or the like.

[Oil-absorbing powder]
As the oil-absorbing powder, amorphous silica, dextrin, bow show, etc. can be used.
As specific examples of amorphous silica, JP-A-62-1191417, page 2, lower right column, line 19 to page 5, upper-left column, line 17, JP-A-62-119119, page 2, lower right. Examples include amorphous silica produced by the production method described in column 20th line to page 5 upper left column 11th line.
Examples of commercially available amorphous silica include Toxeal NR, Florite (manufactured by Tokuyama Co., Ltd.), TIXOLEX 25 (manufactured by Han France Chemicals), Silo Pure (manufactured by Fuji Silysia Co., Ltd.), and the like.

Examples of the dextrin include those obtained by hydrolyzing starch derived from various grains with acid or amylase. There are various degradation products depending on the degree and structure of hydrolysis, and examples include amylodextrin (soluble starch), erythrodextrin, acrodextrin, maltodextrin, and cyclodextrin. Among these, the DE value (decomposition rate of starch = glucose equivalent mass / total solid content mass × 100) is preferably 0.1 to 10, and more preferably 0.1 to 5. Moreover, what melt | dissolves rapidly also in cold water or warm water is preferable, and a DE value is 0.1-3 from a viewpoint of alkali resistance.
Commercial products such as “A6 Bow Show” manufactured by Shikoku Kasei Kogyo Co., Ltd. can be used as the bow show. As the bow show that can be used in the present invention, those having a particle size of 20 μm or less account for 90% or more of the total from the viewpoint of solubility.
Among the oil-absorbing powders, amorphous silica is preferable. The oil-absorbing powder may be used alone or in combination of two or more.

[Bulking agent, diluent]
Examples of the extender or diluent include sulfates such as sodium sulfate and magnesium sulfate. If a filler or diluent is added, each component can be diluted and dispersed at an appropriate concentration, so that it can be designed in an amount suitable for use, and also to maintain the stability of each component. It is valid.

[Production Method of Powder Cleaning Composition]
As described above, the powder cleaning composition of the present invention includes granules containing the A component and the B component, and the production method is not limited, but the A component and the B component are co-produced together. After granulation, it is preferable to produce efficiently by the production method of the present invention in which the granulated product obtained is mixed with the C component.

As the method for producing the granule, at least the A component and the B component are combined with a Henschel mixer (manufactured by Nihon Coke Industries Co., Ltd.), a high speed mixer (manufactured by Fukae Powtech Co., Ltd.), and a nauter mixer (manufactured by Hosokawa Micron Co., Ltd.). ), Ribbon type mixer (manufactured by Tokuju Kogaku Co., Ltd.), V-type blender (manufactured by Dalton Co., Ltd.), bench kneader (manufactured by Irie Shokai Co., Ltd.) and the like. A method of co-granulating with a granulator.
Although there is no restriction | limiting in the mixing temperature of each component at the time of manufacturing the said granule, 100 degreeC or less is preferable from a discoloration suppression and energy saving viewpoint of A component, and 90 degreeC or less is more preferable.

Examples of the granulation method include extrusion granulation method, rolling granulation method, pulverization granulation method, fluidized bed granulation method, spray granulation method, crushing granulation method, etc. A granulation method and a rolling granulation method are more preferable.
Extruder granulators include pelleter double, twin dome gran, disk pelleter (manufactured by Dalton), basket type granulator (manufactured by Kikusui Seisakusho), granulator (manufactured by Hosokawa Micron), Publicly known extrusion granulators such as a lateral extrusion screw type extrusion granulator (manufactured by Okawara Seisakusho Co., Ltd.) described in JP-A-10-192688 can be mentioned.
Further, a kneading and extruding apparatus such as Extrude Ohmics (manufactured by Hosokawa Micron Corporation) can also be used. The extrusion screen diameter is preferably 0.3 to 2.0 mm, more preferably 0.5 to 2.0 mm, and still more preferably 0.5 to 1.0 mm. By using such a shape, a cylindrical or noodle-shaped granulated product can be extruded.

Among the rolling granulation methods, the stirring rolling granulation method is particularly preferable from the viewpoint of granulation yield and the like.
Examples of the agitating rolling granulator include a main agitation shaft provided with an agitation blade at the center of the inside, and further an auxiliary agitation shaft for assisting mixing to suppress generation of coarse particles. it can. The auxiliary stirring shaft generally has a structure that protrudes from the wall surface in a direction perpendicular to the main stirring shaft.
Specific equipment includes a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.), a high speed mixer (manufactured by Fukae Powtech Co., Ltd.), and a vertical granulator (Co., Ltd.). Paulek) and the like. Examples of the main agitation shaft installed horizontally include a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd.), a pro shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.), and the like.

The obtained granulated product is preferably cooled in order to suppress coalescence and agglomeration of the compression molded product, and thereafter, it is preferable to perform granulation as necessary. There is no restriction | limiting in the apparatus used when sizing, A well-known grinder (or crusher) can be used.
Examples of such devices include a high speed mixer (Fukae Powtech Co., Ltd.), Malmerizer (manufactured by Dalton Co., Ltd.), Spiler Flow (manufactured by Freund Sangyo Co., Ltd.), Fitzmill (manufactured by Dalton Co., Ltd.) ), Power mill (manufactured by Paulek Co., Ltd.), combil (manufactured by Quadro), and the like.

The powder cleaning composition of the present invention can be obtained by appropriately mixing the granule containing the A component and the B component with the C component, preferably an alkaline agent and other optional components, using the above-described mixing apparatus. it can.
The powder detergent composition of the present invention produced as described above can be suitably used as a detergent for tableware, clothing, residential use, etc., and is particularly useful for an automatic dishwasher.

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: “Trilon M Powder” manufactured by BASF (effective 87%)
(Methylglycine diacetic acid trisodium salt)
Component B: sodium sulfite (Mitsui Chemicals, Inc .: average particle size 190 μm)
: Sodium nitrite (manufactured by Ube Industries, Ltd .: average particle size 220 μm)
C component: Sodium percarbonate (KCPZ-S manufactured by Nippon Peroxide Co., Ltd.)
Polypropylene glycol: “Preminol S4011” manufactured by Asahi Glass Urethane Co., Ltd.
Number average molecular weight: about 10,000
Polyethylene glycol: “K-PEG6000LA” manufactured by Kao Corporation
Number average molecular weight: about 8500
Soda ash: made by Central Glass Co., Ltd.

<Device>
Nauter mixer: Hosokawa Micron Co., Ltd. extrusion granulator: Pelleter Double EXD-100 (manufactured by Dalton Co., Ltd.)
Sizing machine: Power mill (Powrec Co., Ltd.)

Example 1
20 parts of component A, 0.3 part of sodium sulfite as component B, and 3 parts of polypropylene glycol were charged into a Nauter mixer and mixed at a jacket temperature of 90 ° C. for 20 minutes.
Here, 5 parts of pre-melted polyethylene glycol was added, and further mixed for 20 minutes, and then the 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 cylindrical granule in which the A component and the B component were co-granulated. The average diameter was 0.7 mm and the average length was 1.2 mm.
This granule, 10 parts of the above-mentioned C component, and 59.2 parts of soda ash which are other optional components, 2 parts of enzyme, and 0.5 part of fragrance are charged into a Nauta mixer and mixed for 10 minutes to obtain a powder detergent composition. Obtained.

Example 2
A powder cleaning composition was obtained in the same manner as in Example 1 except that 30 parts of the A component, 1.5 parts of the B component, and 48 parts of soda ash were used.

Example 3
A powder cleaning composition was obtained in the same manner as in Example 1 except that sodium nitrite was used as the B component.

Comparative Example 1
Twenty parts of component A were charged into a Nauta mixer and mixed at a jacket temperature of 90 ° C. for 20 minutes. Here, 5 parts of pre-melted polyethylene glycol was added, and further mixed for 20 minutes, and then the 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. Further, this granulated product was cooled and then pulverized with a granulator to obtain the same cylindrical granules as described above.
This granule, 10 parts of the above C component, 3 parts of polypropylene glycol and 59.5 parts of soda ash which are other optional components, 2 parts of enzyme, and 0.5 part of fragrance are charged into a Nauter mixer and mixed for 10 minutes to prepare a powder detergent composition I got a thing.

Comparative Example 2
Twenty parts of component A were charged into a Nauta mixer and mixed at a jacket temperature of 90 ° C. for 20 minutes. Here, 5 parts of pre-melted polyethylene glycol was added, and further mixed for 20 minutes, and then the 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. Further, the granulated product was cooled and then pulverized with a granulator to obtain the same cylindrical granules as described above.
This granule, 0.05 part of B component (sodium sulfite) and 10 parts of C component, 3 parts of polypropylene glycol and 59.45 parts of soda ash which are other optional components, 2 parts of enzyme and 0.5 part of fragrance are added to a Nauter mixer. The mixture was charged for 10 minutes and mixed to obtain a powder cleaning composition.

Comparative Example 3
In Comparative Example 2, the same operation as in Comparative Example 2 was carried out except that B component (sodium sulfite) was 0.3 part and soda ash was 59.2 part to obtain a powder cleaning composition.

Comparative Example 4
In Comparative Example 2, the same operation as in Comparative Example 2 was carried out except that A component was 30 parts, B component (sodium sulfite) was 1.5 parts, and soda ash was 48 parts. Obtained.

Comparative Example 5
A powder cleaning composition was obtained by performing the same operation as in Comparative Example 3 except that sodium nitrite was used as the B component.

The color tone of the powder detergent compositions of Examples and Comparative Examples obtained by the above-described methods was measured by the following method.
(1) Color tone immediately after production The powder detergent composition was filled in an airtight container, and the color tone was measured using a spectrocolorimeter manufactured by Konica Minolta. In evaluation, the b value expressed in the Lab color system was used as a measure of discoloration. Note that an increase in the b value means that the color changed to yellow. The results are shown in Table 1.

(2) Color tone after storage The powder detergent composition is filled in a sealed container and stored in an environment at 30 ° C., and the color tone after 2 weeks and the color tone after storage for 1 month are the above (1). It measured by the method similar to the method of above. The results are shown in Table 1.

  From Table 1, it can be seen that in Examples 1 to 3, in which the A component and the B component were co-granulated, discoloration hardly occurred even after storage for 1 month. On the other hand, in Comparative Example 1 in which the B component was not used, the coloring progressed remarkably. Further, Comparative Examples 2 to 5 in which the A component and the B component are not co-granulated and are simply mixed as a composition do not provide the effect of suppressing the coloring of the A component by the B component, and are colored in proportion to the storage period. Progressed. From the above results, it can be seen that the powder detergent composition of the present invention does not cause discoloration during storage and is extremely excellent in storage stability.

Claims (8)

A granule containing a glycine-N, N-diacetic acid derivative (component A) and a reducing agent (component B) represented by the following general formula (1) and an oxygen bleach (component C) under the following conditions: A powder detergent composition containing to fill.
A component: 1-50 mass%
B component: 0.01-10 mass%
C component: 1 to 25% by mass

(Wherein, M ¹ ~M ³ each independently represent a hydrogen atom or a cation component, R represents an alkyl or alkenyl group having 1 to 18 carbon atoms.)   The powder cleaning composition according to claim 1, wherein the component B is one or more selected from the group consisting of sodium sulfite, sodium hydrogen sulfite, potassium sulfite, and sodium nitrite.   The powder cleaning composition according to claim 1 or 2, wherein the component C is one or more selected from the group consisting of sodium persulfate, sodium percarbonate, and sodium perborate.   The amount of B component with respect to 100 mass parts of A component is 0.3-50 mass parts, The powder cleaning composition in any one of Claims 1-3.   The amount of B component with respect to 100 mass parts of C component is 0.5-50 mass parts, The powder cleaning composition in any one of Claims 1-4.   The powder cleaning composition according to any one of claims 1 to 5, wherein the granule is obtained by co-granulating at least an A component and a B component.   The powder cleaning composition according to any one of claims 1 to 6, wherein the powder cleaning composition is a powder cleaning composition for an automatic dishwasher.   The manufacturing method of the powder cleaning composition in any one of Claims 1-7 which mixes the obtained granulated material and C component after co-granulating A component and B component.