TWI592481B - Solid detergent composition - Google Patents

Description

Solid detergent composition

The present invention relates to a granulated product which can be preferably used for a solid detergent composition, a solid detergent composition containing the granulated material and preferably used in an automatic tableware cleaning machine, and the solid detergent composition The manufacturing method, the use of the solid detergent composition, and the coloring suppression method of the solid detergent composition.

Previously, a large amount of surfactant has been formulated in a powder detergent composition, but in recent years, it has been found that the amount of surfactant used is reduced by blending more organic chelating agents having good biodegradability from the viewpoint of environmental awareness. The trend. Examples of the organic chelating agent having good biodegradability include glycine-N,N-diacetic acid derivatives (hereinafter also referred to as "GDA"). This GDA is an excellent cleaning base which is excellent in biodegradability and has high chelating property, and therefore has attracted attention as a material for reducing the amount of use of the surfactant.

For example, Patent Document 1 discloses a mixed powder or mixed particles which contains (a) GDA 5 to 95% by mass and (b) selected from a nonionic interface activity in order to improve the fluidity of the powder or particles. A mixture of 5 to 95% by mass of the polymer in the agent or the like.

Further, Patent Document 2 describes a multiphase tablet type detergent which contains i) a polymer polycarboxylate in an amount of about 0.1 to 60% by mass, and ii) an inorganic salt, for the purpose of improving the solubility and strength of the tablet. The inorganic carrier is from about 40 to 99.9%, and iii) is from 0 to 50% by mass of the organic auxiliary agent selected from the group consisting of a chelating agent, a surfactant, and the like.

Further, Patent Document 3 discloses a solidified matrix containing (a) a biodegradable aminocarboxylic acid ester, (b) sodium carbonate, and (c) for improving the dimensional stability of the solidified substrate. Water, and (d) the solidified matrix is a solid of hydrate.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-505236

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-538270

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-508821

The present invention relates to an extrusion granulated product comprising a compound represented by the following formula (1) (component A) in an amount of 25 to 90% by mass, and containing a reactive unsaturated group derived from a carbon number of 3 to 6 The polymer (component B) of the structural unit of the carboxylic acid or a salt thereof is 3 to 50% by mass, and the total content of the A component and the B component in the granulated product is 28 to 95% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

Fig. 1 is an image showing an extruded granulated product of granulating A in the examples.

Fig. 2 is an image showing the granulated extrusion of granulated B in the examples.

Fig. 3 is a view showing an image of an extruded granule of granulated C in the examples.

In the above-mentioned Patent Document 1, although a particle containing a nonionic surfactant and an organic chelating agent such as GDA is described, the fluidity is not sufficient, and the fine powder ratio is high. Therefore, it is expected to lower the fine powder ratio.

In Patent Documents 2 and 3, it is not a large number of organic chelating agents such as GDA, and there is no description about the problem that occurs when a large amount of an organic chelating agent such as GDA is formulated.

The present invention provides an extruded granulated product having a low micronose ratio and a low breaking load even when the content of GDA is large, that is, a viscosity is small, and fluidity is excellent, and a method for producing the same.

Further, the present invention provides a solid detergent composition, a use of the solid detergent composition, and a coloring inhibiting method of the solid detergent composition, the solid detergent composition containing the granulated material, and even in the long term It also inhibits discoloration after storage, and has excellent storage stability.

In order to solve the above problems, the inventors of the present invention have studied the granulation property of granules using GDA, and found that the above problems can be solved by extrusion granulation of GDA and a specific polymer.

Further, the inventors of the present invention have found that the discoloration of GDA is promoted by the presence of an oxygen-based bleaching agent. However, the oxygen-based bleaching agent is a base having excellent cleaning performance, and the solid detergent composition not containing an oxygen-based bleaching agent is drastically reduced in cleaning performance.

Therefore, the inventors of the present invention have further studied the technique for suppressing the discoloration of GDA in the presence of an oxygen-based bleaching agent, and as a result, it has been found that the granules formulated with a specific amount of GDA and the above specific polymer are included in the solid cleaning. The discoloration of GDA can be suppressed in the composition of the agent, and GDA can be formulated in a high concentration in the solid detergent composition.

That is, the present invention relates to the following [1] to [5].

[1] An extrusion granulated product comprising a compound (GDA) represented by the following formula (1) (component A) in an amount of 25 to 90% by mass, and containing a reactivity derived from a carbon number of 3 to 6 The polymer (component B) of the structural unit of the unsaturated carboxylic acid or a salt thereof is 3 to 50% by mass, and the total content of the A component and the B component in the granulated product is 28 to 95% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

[2] A solid detergent composition comprising the above-mentioned extruded granules and an oxygen-based bleach (component D).

[3] Use of the above solid detergent composition for an automatic tableware cleaning machine.

[4] A method for producing the above extruded granulated product, which comprises extruding and granulating a mixture comprising the component A and the component B.

[5] A coloring inhibiting method for a solid detergent composition, which comprises mixing the above-mentioned extruded granules with an oxygen bleach (component D).

According to the present invention, it is possible to provide an extruded granulated product having a low fine powder ratio and a low breaking load even when the content of GDA is large, that is, an adhesive granule having a small viscosity and excellent fluidity, and a method for producing the same.

Moreover, according to the present invention, it is possible to provide a solid detergent composition which contains the granulated material and which does not cause discoloration after long-term storage, and which has excellent storage stability, the use of the solid detergent composition, and the suppression of the composition of the solid detergent. The color suppression method of the color of the object.

[Extrusion granulation]

The extrusion granulated product of the present invention contains 25 to 90% by mass of the compound (component A) represented by the following formula (1), and contains a carboxylic acid having a reactive unsaturated group derived from carbon atoms 3 to 6. The polymer (component B) of the structural unit of the salt thereof is 3 to 50% by mass, and the total content of the A component and the B component in the granulated product is 28 to 95% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

In the present invention, polymerization of a compound represented by the above formula (1) and a specific polymer, that is, a structural unit containing a carboxylic acid having a reactive unsaturated group derived from carbon atoms 3 to 6 or a salt thereof Since the material (hereinafter, also referred to as "B component") is subjected to extrusion granulation, even when the content of GDA is large, the fine powder ratio is low, and the breaking load is low, that is, the viscosity is small. Granules with excellent fluidity.

In the present specification, the term "granulated matter" refers to a method in which fine particles are aggregated and fine particles are granulated.

<Component A>

The component A is a compound represented by the following formula (1) (hereinafter also referred to as "GDA").

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

The hydrocarbon group represented by R in the above formula (1) is preferably an alkyl group or an alkenyl group. The carbon number of the above R is from 1 to 12, preferably from 1 to 6, more preferably from 1 to 3, from the viewpoint of biodegradability and cleansing power of the component A.

Specific examples of the preferred alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, etc., among which, the biodegradation of the component A is improved. From the viewpoint of sex and cleansing power, a methyl group is preferred. The term "various" as used herein refers to various isomers including positive, third, and different.

Further, specific examples of the preferred alkenyl group include a vinyl group, an allyl group, a 2-butenyl group, and a 2-methyl-2-propenyl group.

M ¹ , M ² and M ³ in the above formula (1) may each independently represent a hydrogen atom, an alkali metal such as sodium or potassium, or ammonium, an alkanolammonium or an alkylammonium. Among these, from the viewpoint of availability, and reduction in production cost, a hydrogen atom or an alkali metal is preferred, and sodium is particularly preferred.

The component A used in the present invention may be either a liquid or a solid, but the viewpoint of efficiently producing a solid detergent composition, the viewpoint of biodegradability, and the viewpoint of physical properties (operability) The component A is preferably a solid.

<B ingredient>

In the present invention, in view of obtaining a viewpoint of good cleaning performance, fluidity, and fine powder ratio, thereby destroying a granulated product having a low load and suppressing the coloration of GDA, the use includes a carbon number of 3 to 6, preferably. It is a polymer of a structural unit of a carboxylic acid having a reactive unsaturated group or a salt thereof having 3 to 5 carbon atoms. Further, the carbon number 3 to 6 is the total carbon number of the carboxylic acid.

The color of GDA can be suppressed by including the component B together with GDA in the granulated product.

The component B is a polymer containing a structural unit derived from a carboxylic acid having a reactive unsaturated group or a salt (B-1 component) having a carbon number of 3 to 6, preferably 3 to 5 carbon atoms, but obtained From the viewpoints of good cleaning performance, fine powder ratio, and destruction of granules having a low load, it is more preferable to include a structural unit derived from the above B-1 component and an olefin derived from carbon number 2 to 12 (B-2 component) a copolymer of structural units.

(B-1 component)

Examples of the component B-1 include maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, and citraconic acid, and the like. It can also be an acid anhydride.

From the viewpoint of obtaining a granulated product which improves cleaning performance, fluidity, and fine powder rate and which destroys a low load, the structural unit derived from the B-1 component is preferably derived from a component selected from the group consisting of propylene. a structural unit of one or more monomers of the group consisting of an acid or a salt thereof, maleic acid or a salt thereof, and maleic anhydride, and more preferably derived from acrylic acid and cis-butyl A monomer of a olefinic acid or a salt thereof, or a structural unit comprising a monomer of acrylic acid and maleic anhydride.

Examples of the salt include a sodium salt, a potassium salt, an alkanolamine salt, and an ammonium salt.

Further, the salt of the copolymer may be formed by using a salt type compound as a monomer, or may be formed by neutralization after copolymerization.

The total ratio of the acrylic acid to the maleic acid in the above component B-1 is preferably from 90 to 100 mol%, more preferably from 95 to 100 mol%, still more preferably from 98 to 100 mol%, still more preferably substantially 100 mol%. .

The acrylic acid derived from the structural unit derived from the B-1 component is superior to the maleic acid of maleic acid in terms of obtaining a granulated product having good cleaning performance, fluidity and fine powder ratio and impairing a low load. It is 0.6 to 9, more preferably 1 to 4, and further preferably 1.5 to 3. Further, the molar ratio of acrylic acid to maleic acid can be determined by detecting the thermal decomposition product of the copolymer by thermal decomposition gas chromatography (PGC).

(B-2 ingredient)

Examples of the component B-2 include an olefin having 2 to 12 carbon atoms, an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, and styrene, but obtaining cleanability, fluidity, and fine powder. From the viewpoint of a good rate and destruction of granules having a low load, an olefin having 2 to 12 carbon atoms is preferred.

As the olefin having 2 to 12 carbon atoms, one or two or more selected from the group consisting of ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene can be used, and preferably butene, isobutylene, and diisobutylene are used. , pentene, and hexene are more preferably diisobutylene. The olefin has a carbon number of 2 to 12, preferably 4 to 6, from the viewpoint of obtaining a granulated product having a high cleaning performance, a good fluidity and a fine powder ratio, and a low load.

The molar ratio of the B-1 component to the B-2 component in the B component from the viewpoint of obtaining a granule having a good fluidity and a fine powder ratio and destroying a low load (B-1 component/B- 2 ingredients) It is preferably 0.1 to 10, more preferably 0.2 to 5, and still more preferably 0.3 to 3.

Further, from the viewpoint of obtaining a granulated product having high cleaning performance, good fluidity and fine powder ratio, and low damage load, the total content of the B-1 component and the B-2 component in the B component is preferably 90. It is preferably from 100 to 100 mol%, more preferably from 95 to 100 mol%, still more preferably from 98 to 100 mol%, and is preferably a copolymer consisting essentially only of the components B-1 and B-2.

Further, the component B may be a salt, and examples thereof include a sodium salt, a potassium salt, and an ammonium salt.

The weight average molecular weight of the above-mentioned component B is preferably from 1,000 to 100,000, more preferably from 5,000 to 90,000, and still more preferably 10,000, in terms of obtaining a granulated material having a good fluidity and a fine powder ratio and a lower load. 80,000.

Further, the polymer of the component B-1, for example, a copolymer of acrylic acid and maleic acid or a salt thereof, has a weight average molecular weight of a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent, and is infiltrated by a gel. The chromatographic method uses polyethylene glycol as a standard substance to obtain a value.

Further, the weight average molecular weight of the copolymer of the B-1 component and the B-2 component, for example, the diisobutylene-maleic acid copolymer is a mixture of acetonitrile and a 0.1 M aqueous sodium chloride solution (acetonitrile: aqueous sodium chloride solution) (volume ratio) = 30: 70) The value obtained by using gel permeation chromatography using polyethylene glycol as a standard substance as a developing solvent.

The B component is preferably in the form of a powder from the viewpoint of obtaining a granule having a good fluidity and a fine powder ratio and destroying a low load.

From the viewpoint of workability, the average particle diameter of the component B is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 10 μm or more, still more preferably 30 μm or more, and still more preferably 50 μm or more, and granulation is carried out. The average particle diameter of the component B is preferably 2,000 μm or less, more preferably 1,000 μm or less, still more preferably 600 μm or less, still more preferably 500 μm or less, still more preferably 400 μm or less, and still more preferably 300 μm. Hereinafter, it is more preferably 200 μm or less. Further, the average particle diameter was measured by the method described in the examples.

The component B is preferably one or more selected from the group consisting of an acrylic acid-maleic acid copolymer and a diisobutylene-maleic acid copolymer, and is more preferable from the viewpoint of cleaning performance. The diisobutylene-maleic acid copolymer is more preferably an acrylic acid-maleic acid copolymer from the viewpoint of suppressing the coloring of the solid detergent composition. Two or more kinds of the above copolymers may be used in combination as the component B.

<Content and mass ratio of component A and component B>

The content of the component A in the granulated product is 25% by mass or more, preferably 30% by mass or more, more preferably from the viewpoint of improving the cleaning performance and the degree of freedom in formulating the solid detergent composition. It is 35% by mass or more, and more preferably 40% by mass or more, and the granulation property is good, the fluidity and the fine powder ratio are good, and the granulated material having a low load is broken, and the composition of the solid detergent is suppressed. The content of the component A in the granules is 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. Furthermore, it is more preferably 70% by mass or less, still more preferably 65% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, and still more preferably 50% by mass or less. The content of the above A component in the granule is preferably from 30 to 90% by mass, more preferably from 30 to 85% by mass, still more preferably from 35 to 80% by mass, still more preferably from 35 to 75% by mass, and further preferably It is 40 to 70% by mass, more preferably 40 to 65% by mass, still more preferably 40 to 60% by mass, still more preferably 40 to 55% by mass, and still more preferably 40 to 50% by mass.

In addition, the content of the component B in the granulated product is preferably 3% by mass or more, from the viewpoint of obtaining a granulated product having a good fluidity and a fine powder ratio, and a lower load, and a granulation property. 5% by mass or more, preferably 10% by mass or more, more preferably 17% by mass or more, in terms of production cost and solubility of granules, and good cleanability, in granules The content of the component B is 50% by mass or less, preferably 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less. The content of the component B in the granules is preferably from 5 to 50% by mass, more preferably from 5 to 40% by mass, still more preferably from 10 to 35% by mass, still more preferably from 17 to 30% by mass.

Obtaining the view of granules that reduce the bulk density and the fine powder rate is good, and the load is lower. In the granulated material, the mass ratio of the component B to the component A (component B/component A) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and still more preferably 0.4 or more. The mass ratio (component B/component A) is preferably 0.8 or less, more preferably 0.7 or less, and further preferably from the viewpoint of the production cost and the solubility of the granulated product to improve the cleanability. It is 0.65 or less, and more preferably 0.6 or less. The mass ratio of the component B to the component A (component B/component A) in the granule is preferably from 0.1 to 0.8, more preferably from 0.2 to 0.7, still more preferably from 0.2 to 0.65, still more preferably from 0.3 to 0.6. More preferably, it is 0.4 to 0.6.

In the viewpoint of producing a granule which contains a component A at a high concentration but has a low powder ratio or a low load, and has excellent fluidity, and a degree of freedom in formulating a solid detergent composition, The total content of the component A and the component B is 28% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, and it is borrowed. The total content of the component A and the component B in the granules is 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably from the viewpoint of obtaining the granulated material from the binder. It is 80% by mass or less, and more preferably 75% by mass or less. The total content of the A component and the B component in the granule is preferably from 30 to 95% by mass, more preferably from 40 to 95% by mass, still more preferably from 50 to 90% by mass, still more preferably from 55 to 85% by mass, and further preferably More preferably, it is 55 to 75 mass%.

<C component>

The extrusion granulated product of the present invention preferably contains a component C containing at least one of an organic acid having a carbon number of 4 to 8 (component C-1) and an alkali metal citrate (component C-2). . By containing the above components, the bulk density can be lowered, the solubility of the granules can be improved, and the fluidity of the granules can be improved, thereby suppressing the coloration of the component A.

(C-1 component: organic acid having a carbon number of 4 to 8)

The component C-1 is preferably one or more selected from the group consisting of organic acids having a carbon number of 4 to 8, preferably 4 to 6 carbon atoms, more preferably selected from the group consisting of gluconic acid, malic acid, tartaric acid, citric acid, and succinic acid. One or more of maleic acid and fumaric acid, among which, it is suppressed to be solid. In view of the coloring of the component A in the case of the detergent composition, it is more preferably one or more selected from the group consisting of succinic acid, fumaric acid, and citric acid. The organic acid having 4 to 8 carbon atoms is preferably a powder, and preferably has a carboxyl group.

From the viewpoint of operability, the average particle diameter of the organic acid having 4 to 8 carbon atoms is preferably 10 μm or more, more preferably 30 μm or more, further preferably 50 μm or more, and from the viewpoint of granulation property, It is preferably 500 μm or less, more preferably 250 μm or less, still more preferably 150 μm or less. The measurement of the average particle diameter can be carried out by the method described in the examples.

Preferably, component B or component C is pre-crushed to a suitable particle size. Examples of the pulverizer that can be used for crushing include an impact crusher such as a hammer mill, an impact pulverizer such as an atomizer or a pin mill, and a shear coarse crusher such as a rapid pulverizer. The above operation may be one operation, or may be multiple operations of the same type or different types of pulverizers.

The content of the organic acid (C-1 component) having 4 to 8 carbon atoms in the extrusion granulation is preferably 0.1 to 15 by mass in terms of reducing the bulk density, improving the fluidity, and suppressing the coloring of the component A. % is more preferably 0.2 to 10% by mass, still more preferably 0.3 to 5% by mass.

(C-2 component: alkali metal citrate)

The alkali metal ruthenate is preferably a crystalline alkali metal ruthenate, and is particularly useful as an additive as the above-mentioned detergent and has an excellent alkalinity from the viewpoint of suppressing the formation of a water-insoluble component at the time of storage. More preferably, it is a crystalline layered alkali metal ruthenate. As such a crystalline layered niobate, "Purifeed" which is commercially available from Tokuyama Siltech Co., Ltd. is preferable. As the salt, a sodium salt or a potassium salt is preferred.

The content of the alkali metal ruthenate in the extrusion granulation is preferably from 0.1 to 25% by mass, more preferably from 1 to 20, from the viewpoint of reducing the bulk density, improving the fluidity, and suppressing the coloration of the component A. % is further preferably from 1 to 15% by mass, and still more preferably from 3 to 15% by mass.

<Binder>

In the above extrusion granulation, in order to improve granulation property, it is preferred to prepare a binder. As the binder, at least 1 containing a nonionic surfactant and a nonionic polymer is preferred. The nonionic surfactant is preferably a nonionic surfactant from the viewpoint of cleanability and reduction in bulk density, and is preferably a nonionic polymer from the viewpoint of reducing the breaking load. From the viewpoint of granulation, the melting point of the binder is preferably 25 ° C or higher, more preferably 40 ° C or higher, and from the viewpoint of cleanability, it is preferably 80 ° C or lower, more preferably 70 ° C or lower. .

As the nonionic surfactant, for example, it is preferably selected from the group consisting of glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and sucrose fats. Acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyethylene One or more of the group consisting of an alcohol fatty acid ester, a polyoxyethylene castor oil, and a polyoxyethylene hardened castor oil. Among these, a glycerin fatty acid ester is preferable from the viewpoint of improving the solubility of the granulated product.

The nonionic surfactant is preferably a solid at normal temperature (25 ° C) from the viewpoint of granulation.

The nonionic polymer is preferably polypropylene glycol, polyethylene glycol or polyoxyethylene polyoxypropylene diol. More preferably, at least one of polyethylene glycol and polypropylene glycol is used, and a fine powder ratio is low. From the viewpoint of granules having a low bulk density, it is further preferred to include both polyethylene glycol and polypropylene glycol.

In the case of using polypropylene glycol, the number average molecular weight thereof is preferably from 600 to 20,000, more preferably from 2,000 to 12,000, still more preferably from 5,000 to 12,000, and still more preferably from 8,000 to 1,2000. In the case of using polyethylene glycol, the number average molecular weight thereof is preferably from 4,000 to 20,000, more preferably from 6,000 to 13,000, still more preferably from 7,000 to 9,000. Polyethylene glycol is preferred in terms of good handleability and easy granulation. Further, the number average molecular weight of polypropylene glycol and polyethylene glycol can be determined from the hydroxyl value. As the binder, one type of the above compounds may be used alone or two or more types may be used in combination.

When the binder granules contain a binder, the total content thereof is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 15% by mass. The mass% or more is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 27% by mass or less, and further preferably 3 to 40% by mass. More preferably, it is 5 to 35 mass%, further preferably 10 to 30 mass%, and more preferably 15 to 27 mass%.

Further, polypropylene glycol can also be used as an antifoaming agent from the viewpoint of improving the defoaming property in the case where the granulated product is used as a solid detergent composition.

When the polypropylene granules are contained in the extruded granules, the content thereof is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, still more preferably from 3 to 12% by mass, and even more preferably from 6 to 6% by mass. 12% by mass.

<Method for Producing Extrusion Granulated Materials>

The method for producing the extruded granulated product is not limited, and is preferably produced by a method for producing an extruded granulated product of the present invention comprising extrusion-granulation of a mixture comprising the above-mentioned A component and the above-mentioned component B.

According to the production method of the present invention, by using the component B, extrusion granulation can be efficiently performed even when the content of the component A is increased.

Examples of the method for producing the granulated product include a Henschel mixer (NIPPON COKE & ENGINEERING), a high-speed mixer (manufactured by FUKAE POWTEC), and a cone mixer (manufactured by Hosokawa Micron). , belt type mixer (made by Deshou Work Co., Ltd.), V type blender (made by DALTON), desktop kneading machine (made by Jinjiang Chamber of Commerce), and rotary mixer (Shanshan Heavy Industry Co., Ltd.) In a well-known mixer, at least the above-mentioned component A and component B are mixed, and they are co-granulated by an extrusion granulator.

The mixing temperature at the time of obtaining the mixture of the components in the production of the granulated product is not limited, and is preferably 100 ° C or less, more preferably 95 ° C or less, and further preferably from the viewpoint of suppressing discoloration and energy saving of the component A. The mixing temperature is preferably 10 ° C or higher, more preferably 30 ° C or higher, more preferably 50 ° C or higher, and still more preferably 60 ° C or higher from the viewpoint of mixing efficiency and dissolving the binder at 90 ° C or lower.

Examples of the extrusion granulator include a biaxial granulator, a wet extrusion granulator, a pan granulator (manufactured by DALTON Co., Ltd.), and a basket granulator (manufactured by Kikusui Seisakusho Co., Ltd.). A known extrusion granulator such as a horizontal extrusion type spiral extrusion granulator (manufactured by Okawara Seisakusho Co., Ltd.) described in Japanese Patent Laid-Open No. Hei 10-192688.

Further, a kneading extruder such as Extrud-O-Mix (manufactured by Hosokawa Micron Co., Ltd.) can also be used. The diameter of the extruded screen is preferably from 0.3 to 12 mm, more preferably from 0.3 to 5 mm, further preferably from 0.3 to 2.0 mm, more preferably from 0.5 to 2.0 mm, and still more preferably from 0.5 to 1.0 mm. The diameter of the screen is the diameter of the circle when it is circular, and the length of the diagonal when it is square. The granules can be extruded into a cylindrical shape or a prismatic shape according to the shape of the pores.

It is preferable that the obtained extruded granules are cooled in order to suppress integration or lumping of the compression molded product, and it is necessary to perform granulation in order to make the shape (length, etc.) uniform. The machine used for the whole granulation is not limited, and a well-known pulverizer (or crusher) can be used. The extruded granules obtained by the production method of the present invention are excellent in granulation property, and thus can be easily sized. Cylindrical or prismatic granules which can be made into a spherical shape or have a uniform length of the column portion by the granules.

Examples of such a device include a high-speed mixer (manufactured by FUKAE POWTEC Co., Ltd.), a spherical granulator (manufactured by DALTON Co., Ltd.), SPIR-A-FLOW (manufactured by Freund Corporation), and Fitzmill (FITZPATRICK). Made by the company), Power mill (manufactured by DALTON), Comil (manufactured by Quadro), etc.

<The shape, size and physical properties of granules>

The extruded granules of the present invention may be spherical, cylindrical or prismatic as described above. When the extruded granules are spherical, the average particle diameter is preferably 0.2 mm or more, more preferably 0.3 mm or more, further preferably 12 mm or less, more preferably 10 mm or less, still more preferably 5 mm or less. More preferably, it is 2 mm or less. Further, it is preferably 0.2 to 12 mm, more preferably 0.3 to 10 mm, still more preferably 0.3 to 5 mm, and still more preferably 0.3 to 2 mm. Average particle size The maximum diameter of the particles was measured and found as the average of the number of 50 particles.

When the extruded granules are in the form of a column or a column, the length of the average diameter (cylindrical shape) or the diagonal line (corner shape) is preferably 0.2 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5. Mm or more, more preferably 10 mm or less, more preferably 5 mm or less, further preferably 2 mm or less, further preferably 1 mm or less, further preferably 0.2 to 10 mm, more preferably 0.3 to 10 mm, and further preferably It is 0.3 to 5 mm, more preferably 0.5 to 2 mm, and still more preferably 0.5 to 1 mm.

The average length of the column is preferably 0.3 mm or more, more preferably 0.5 mm or more, further preferably 0.8 mm or more, further preferably 10 mm or less, more preferably 8 mm or less, further preferably 5 mm or less, and further preferably It is 3 mm or less, and more preferably 1.5 mm or less. Further, the average length is preferably from 0.3 to 10 mm, more preferably from 0.5 to 8 mm, still more preferably from 0.8 to 5 mm, still more preferably from 0.8 to 3 mm, and still more preferably from 0.8 to 1.5 mm. The average diameter is measured in the presence of a long diameter and a short diameter. The length of the diagonal is the maximum length measured. The average length is the maximum length of the column portion. These can be obtained by the average of the number of 50 particles.

The fine powder ratio of the extruded granulated product of the present invention is preferably 12% or less, more preferably 10% or less, still more preferably 8% or less, and further preferably 8% or less from the viewpoint of improving the granulation property and improving the yield. The amount is preferably 5% or less, more preferably 3% or less, and further preferably 0.5% or more, and more preferably 1% or more from the viewpoint of productivity.

The breaking load (gf) of the extruded granulated product of the present invention is preferably 150 or less, more preferably 100 or less, still more preferably 80 or less, from the viewpoint of suppressing aggregation due to viscosity of the particles, and furthermore The ratio is preferably 70 or less, and more preferably 5 or more, and still more preferably 10 or more from the viewpoint of productivity.

The bulk density (g/L) of the extruded granulated product of the present invention is preferably 750 or less, more preferably 700 or less, still more preferably 650 or less, from the viewpoint of the solubility of the granulated product, and furthermore Preferably, it is 600 or less, and more preferably 530 or less. From the viewpoint of operability, it is preferably 350. The above is more preferably 400 or more, and still more preferably 450 or more.

The micronized rate, the breaking load, and the bulk density can be determined by the method described in the examples.

The granulated product of the present invention has excellent physical properties as described above, and is considered to be because the shearing force at the time of extrusion granulation is passed through the extrusion screen to uniformly disperse the component A and the component B. And make the two components in close contact.

[Solid Cleaner Composition]

The solid detergent composition of the present invention contains the granulated product and the oxygen-based bleach (component D), and the granulated product contains the compound represented by the above formula (1) (component A) and contains carbon-derived carbon. A polymer (component B) having a structural unit of a carboxylic acid having a reactive unsaturated group or a salt thereof in the range of 3 to 6.

The content of the component A in the solid detergent composition of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more from the viewpoint of obtaining a sufficient chelation effect. Furthermore, it is preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35, from the viewpoint of blending other components such as a bleaching agent in the solid detergent composition. The mass% or less is more preferably 30% by mass or less, more preferably 3 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 40% by mass, still more preferably 10 to 35% by mass, More preferably, it is 15 to 30% by mass.

Further, in the solid detergent composition of the present invention, the component A may be contained in the granules, but from the viewpoint of suppressing the coloration of the component A, it is preferably 90% by mass of the above-mentioned component A. The above is included in the granules, and it is preferred that substantially all of the amount is contained in the granules.

The content of the component B in the solid detergent composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of granulating the component A and suppressing coloration. Further, from the viewpoint of the production cost and the improvement of the cleanability, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, more preferably 1 to 30% by mass, even more preferably 3 to 20% by mass, and more preferably 5 to 15% by mass.

Further, in the solid detergent composition, the mass ratio of the component B to the component A (the component B/component A) and the mass ratio of the component B to the component A in the granule (B/A) are preferably in the preferred range. And the same reason.

The content of the organic acid (C-1 component) having 4 to 8 carbon atoms in the solid detergent composition is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more from the viewpoint of suppressing the coloration of the component A. Further, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2% by mass or less, and further, C-1. The content of the component is preferably from 0.01 to 10% by mass, preferably from 0.05 to 5% by mass, more preferably from 0.1 to 2% by mass.

Moreover, the content of the alkali metal silicate (C-2 component) in the solid detergent composition is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more from the viewpoint of suppressing the coloration of the component A. Further, it is preferably 1% by mass or more, more preferably 15% by mass or less, still more preferably 10% by mass or less, further preferably 7% by mass or less, and further preferably the content of the C-2 component is 0.1 to 15% by mass. % is more preferably 0.5 to 10% by mass, still more preferably 1 to 7% by mass.

The organic acid having an carbon number of 4 to 8 and the alkali metal silicate are preferably contained in the granulated material from the viewpoints of lowering the bulk density to improve the solubility of the granulated material and improving the fluidity of the granulated product. However, the component A and the component B may be co-granulated together, and then mixed with the obtained granules to prepare a solid detergent composition.

<D ingredient>

In the solid detergent composition of the present invention, an oxygen bleach is used in order to improve the cleanability as the original purpose. In the present invention, since the component A and the component B are co-granulated as described above, the influence of the oxygen-based bleach on the component A can be suppressed, and as a result, the coloration of the component A can be suppressed for a long period of time.

Examples of the oxygen-based bleaching agent used in the present invention include an organic peracid such as magnesium monoperoxyphthalate or a salt thereof, an alkali metal perborate (monohydrate or tetrahydrate), and a percarbonate. Persulfate and perrhenate are equal to peroxides which generate hydrogen peroxide in an aqueous solution. Among these, it is more preferably one or more inorganic peroxides selected from the group consisting of sodium persulfate, sodium percarbonate, and sodium perborate.

Further, the oxygen-based bleaching agent is preferably coated with a coating material. When the coated material is coated, the generation of an oxidizing agent such as hydrogen peroxide is suppressed during storage, so that the coloring of the component A can be further suppressed. Examples of the coating material include a water-insoluble organic compound such as citric acid, boric acid, and the like, a soda ash, a paraffin wax, and a wax.

The content of the component D in the solid detergent composition of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5, from the viewpoint of improving the bleaching property of the solid detergent composition. The mass% or more is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and more preferably 1 to 30%, from the viewpoint of the production cost or the suppression of the coloring of the component A. % is more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass.

Further, the mass ratio (B/D) of the component B to the component D in the solid detergent composition is preferably 0.2 or more, and more preferably 0.3 or more from the viewpoint of suppressing the influence of discoloration caused by the component D. Further, it is preferably 0.5 or more, and is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, more preferably 0.2 to 5, still more preferably 0.3 to 3, more preferably from the viewpoint of production cost. It is 0.5~2.

<Other ingredients>

In the above solid detergent composition, it is also possible to formulate a component which is usually used for a detergent. For example, an alkali agent, a metal ion blocker, a surfactant, a bleach activator, an enzyme, an oil-absorbing powder, an extender or a diluent, an enzyme stabilizer such as a calcium salt or a formic acid, a fragrance, an antibacterial/anti-proof agent Mildew, and pigments.

(alkaline agent)

An alkali agent can be used from the viewpoint of improving the cleanliness of the solid detergent composition.

The solid detergent composition of the present invention preferably contains one or more alkali agents selected from the group consisting of alkali metal carbonates, alkali metal silicates, and amine compounds, and more preferably contains alkali gold. Is a carbonate.

The alkali metal carbonate is preferably one or more selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate. Further, an anhydrous salt of sodium carbonate which is well known as soda ash can also be used.

As the alkali metal ruthenate, a crystalline layered sodium citrate (manufactured by Tokuyama Siltech Co., Ltd., trade name "Purifeed") or the like can be used. Further, an amorphous one can also be used. Further, the alkali metal ruthenate is also effective for the oxidation resistance of the tableware.

The amine compound may, for example, be an alkanolamine, and specific examples thereof include monoethanolamine. Among these alkaline agents, alkali metal carbonates are preferred.

The alkaline agent can be used in the form of powder or granules. The granules can be used by appropriately adjusting the particle size or bulk density by granulation treatment or the like.

The content of the alkali agent in the solid detergent composition is preferably 20% by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and still more preferably 35% by mass. % or more is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, still more preferably 65% by mass or less, and further preferably from the viewpoint of blending the granules. It is 60% by mass or less, and more preferably 55% by mass or less.

The preferred range of the alkali metal carbonate content in the solid detergent composition is also the same as described above.

(metal ion blocker)

As the metal ion blocking agent, a phosphate such as sodium tripolyphosphate can be used. When the solid detergent composition is not phosphorus-containing, as the metal ion blocking agent, citric acid, malic acid, tartaric acid, succinic acid, L-glutamic acid diacetic acid, or hydroxyethyl imino group can be used. Diacetic acid, ethylenediamine disuccinic acid, nitrogen triacetic acid, 1,3-propanediamine triacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylene A polycarboxylic acid such as amine tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexaacetic acid, dihydroxyethylglycine, or hydroxyethylethylenediamine dicarboxymethylglutamic acid or a salt thereof. Among these, citric acid, succinic acid and ethylene are preferred. Aminetetraacetic acid, dihydroxyethylglycine and hydroxyethylethylenediamine dicarboxymethylglutamic acid and the alkali metal salts thereof.

(surfactant)

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant. Among these, a nonionic surfactant is preferred.

Examples of the nonionic surfactant include polyoxyethylene monoalkyl or monoalkenyl ether, polyoxyethylene alkylphenyl ether, polyoxypropylene monoalkyl or monoalkenyl ether, and polyoxybutylene monoalkyl. Or a monoalkenyl ether, a nonionic surfactant mixture containing an alkylene oxide addition monoalkyl or monoalkenyl group, a sucrose fatty acid ester, an aliphatic alkanolamine, a fatty acid monoglyceride, an ethylene oxide condensation type interface Active agents, alkyl glyceryl ethers, alkyl glycosides, and the like. Among these, a polyoxyalkylene alkyl ether is preferred, and specifically, a polyoxyethylene monoalkyl or monoalkenyl ether, and an average carbon number of an alkyl group or an alkenyl group are preferred. It is 4~12, and the average molar addition of ethylene oxide is 1~20 moles. These nonionic surfactants may be used alone or in combination of two or more.

In the present invention, a bleach activator, an enzyme or the like which is usually formulated as a detergent for an automatic dishwashing machine can be blended as a cleaning auxiliary component for further improving the cleaning power.

(bleach activator)

The bleach activator is used in combination with the above-mentioned bleaching agent, and is a substance which reacts with hydrogen peroxide released from the bleaching agent to form an organic peracid having a higher redox potential. Specific examples thereof include tetraethylenesulfonylethylenediamine, alkylnonoxybenzenecarboxylic acid or a salt thereof, or an alkoxybenzenesulfonate.

(enzyme)

As the enzyme, a protease, an amylase, a lipase, a cellulase, an esterase, a peroxidase or the like is preferably used, and a granulated product which is a commercially available product can be used. The above enzymes may be appropriately selected in consideration of storage stability of other components and the like. These enzymes can be used alone 1 Two or more kinds may be used in combination.

Among the above enzymes, amylase is preferred because the amylase acts on gelatinized starch which is difficult to remove with other detergents. Further, protease is also preferred because the protease exerts a remarkable effect on a modified protein which is difficult to remove by using a surfactant or the like.

(oil-absorbing powder)

As the oil absorbing powder, amorphous ceria, dextrin, thenardite or the like can be used, and amorphous ceria is more preferable.

Specific examples of the amorphous ceria are exemplified by Japanese Patent Laid-Open No. 62-191417, page 2, right lower column, line 19 to page 5, upper left column, line 17, Japanese Patent Laid-Open No. 62 No. 191,419, an amorphous ceria produced by the production method described in the lower right column, line 20 to page 5, the upper left column, and the like.

The commercial product of the amorphous ceria is, for example, Tokusil NR, Florite (manufactured by Tokuyama Chemical Co., Ltd.), TIXOLEX 25 (manufactured by Kofran Chemical Co., Ltd.), and Sylopure (manufactured by Fuji Silysia Co., Ltd.).

Examples of the dextrin include those obtained by hydrolyzing starch derived from various cereals using an acid or an amylase. Various decomposition products exist depending on the degree of hydrolysis or the structure, and examples thereof include starch dextrin (soluble starch), red dextrin, leuco dextrin, maltodextrin, and cyclodextrin. Among them, the DE value (starch decomposition rate = glucose equivalent mass / total solid matter component mass × 100) is preferably 0.1 to 10, more preferably 0.1 to 5. Further, it is preferred that the DE value is preferably from 0.1 to 3 from the viewpoint of alkali resistance even if it is rapidly dissolved in cold water or warm water.

As a mirabilite, a commercial item such as "A6 Glauber's salt" manufactured by Shikoku Chemical Industries Co., Ltd. can be used. The Glauber's salt which can be used in the present invention is preferably 90% or more of the total particle diameter of 20 μm or less from the viewpoint of solubility.

Among the above oil-absorbing powders, amorphous ceria is preferred. The oil absorbing powder may be used singly or in combination of two or more.

(extender, thinner)

Examples of the extender or diluent include sulfates such as sodium sulfate and magnesium sulfate. When a bulking agent or a diluent is blended, it can be dispersed in an appropriate concentration by diluting each component, and it is also suitable for use, and it is effective also in maintaining the stability of each component.

[Manufacturing method of solid detergent composition]

The solid detergent composition of the present invention comprises an extruded granule and a component D containing the components A and B, and the production method is not limited, and is preferably produced by the following production method, that is, by extrusion. In the granulation method, a mixture of the component A and the component B is co-granulated, and the granulated product is mixed with the component D. The preferred content (% by mass) of each component in the mixture is the same as the preferred content (% by mass) of each component in the above granulated product.

The solid detergent composition of the present invention may be in the form of a powder, but may be further compression-molded using a briquetting press or a tablet press to form a compact or a tablet. In addition, the term "powder" means particles and particles which are solid at normal temperature (20 ° C).

[Use of solid detergent composition]

The solid detergent composition of the present invention produced in the above manner can be preferably used as a cleaning agent for tableware, clothing, residential, etc., and can be used for an automatic tableware cleaning machine.

[Coloring inhibition method of solid detergent composition]

The coloring inhibiting method of the solid detergent composition of the present invention is a method of mixing the above-mentioned extruded granules with an oxygen-based bleaching agent (component D). The preferred content (% by mass) of each component of the granulated product is as described above. According to the present invention, by using the extruded granules containing the components A and B, even when mixed with the oxygen bleach (component D), the coloring of the component A is effectively suppressed, and as a result, the coloring of the solid detergent composition can be suppressed. .

In the above embodiment, the present invention further discloses the following extrusion granulated product, a method for producing the same, a solid detergent composition, and a method for suppressing coloration of the solid detergent composition.

[1] An extrusion granulated product comprising a compound (component A) represented by the following formula (1) in an amount of 25 to 90% by mass and containing a reactive unsaturated group derived from a carbon number of 3 to 6 It The polymer (component B) of the structural unit of the carboxylic acid or a salt thereof is 3 to 50% by mass, and the total content of the A component and the B component is 28 to 95% by mass.

(wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium)

[2] The extrusion granulated material according to the above [1], wherein the total content of the A component and the B component in the granulated material is 28% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass. The above is more preferably 50% by mass or more, further preferably 55% by mass or more, and 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass. More preferably, it is more preferably 75% by mass or less, further preferably 30 to 95% by mass, more preferably 40 to 95% by mass, still more preferably 50 to 90% by mass, still more preferably 55 to 85% by mass. More preferably, it is 55 to 80% by mass, and more preferably 55 to 75% by mass.

[3] The extrusion granulated material according to the above [1] or [2], wherein a mass ratio [(B)/(A)] of the component B to the component A is preferably 0.1 or more, more preferably 0.2. The above is more preferably 0.3 or more, still more preferably 0.4 or more, and is preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.65 or less, still more preferably 0.6 or less, and further preferably 0.1 to 0.1. 0.8 is more preferably 0.2 to 0.7, further preferably 0.2 to 0.65, still more preferably 0.3 to 0.6, and still more preferably 0.4 to 0.6.

[4] The extruded granule according to any one of the above [1] to [3] wherein the hydrocarbon group represented by R in the above formula (1) is preferably selected from the group consisting of methyl, ethyl and n-propyl. One or two or more kinds of a group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups are more preferably a methyl group.

[5] The extrusion granulated material according to any one of the above [1] to [4] wherein, in the above formula (1), M ¹ , M ² and M ^{3 are} preferably sodium.

[6] The extrusion granulated material according to any one of the above [1] to [5] wherein the component B contains a reactivity which is not derived from a carbon number of 3 to 6, preferably a carbon number of 3 to 5. The polymer of the structural unit of the saturated carboxylic acid or a salt thereof (component B-1) preferably contains a carboxy group having a reactive unsaturated group derived from a carbon number of 3 to 6, preferably having a carbon number of 3 to 5. A copolymer of a structural unit of an acid or a salt thereof (component B-1) and a structural unit derived from an olefin having 2 to 12 carbon atoms (component B-2).

[7] The extruded granule according to any one of the above [1] to [6] wherein the above B-1 component is preferably selected from the group consisting of maleic acid, maleic anhydride, acrylic acid, and methyl group. One or more selected from the group consisting of acrylic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, and the like, and more preferably selected from the group consisting of acrylic acid or its salt, and One or two or more of the group consisting of a diacid or a salt thereof and maleic anhydride.

[8] The extrusion granulated material according to any one of the above [1] to [7] wherein the total ratio of the acrylic acid to the maleic acid in the B-1 component is preferably from 90 to 100 mol%, more preferably It is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, and substantially 100 mol%.

[9] The extruded granule according to the above [8], wherein the acrylic acid derived from the structural unit of the above B-1 component is preferably from 0.6 to 9, more preferably 1 to the mole of maleic acid. ~4, and more preferably 1.5~3.

[10] The extruded granule according to any one of [6] to [9] wherein the component B-2 is preferably selected from the group consisting of ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and One or two or more kinds of hexene are more preferably one or more selected from the group consisting of butene, isobutylene, diisobutylene, pentene, and hexene, and more preferably diisobutylene.

[11] The extrusion granulated material according to any one of the above [6] to [10] wherein a ratio of the above B-1 component to the above B-2 component is a molar ratio (B-1 component / B-2 component) It is preferably 0.1 to 10, more preferably 0.2 to 5, and still more preferably 0.3 to 3.

[12] The extrusion granulated material according to any one of the above [6] to [11] wherein the total content of the B-1 component and the B-2 component in the component B is preferably from 90 to 100 mol%, more Good for 95~100 The mol% is further preferably 98 to 100 mol%, and more preferably substantially 100 mol%.

[13] The extrusion granulated material according to any one of the above [1] to [12] wherein the weight average molecular weight of the component B is preferably from 1,000 to 100,000, more preferably from 5,000 to 90,000, still more preferably from 10,000. ~80,000.

[14] The extruded granule according to any one of [1] to [13] wherein the component B is selected from the group consisting of an acrylic acid-maleic acid copolymer and a diisobutylene-maleic acid copolymer. One or more of the group consisting of.

[15] The extrusion granulated material according to any one of the above [1] to [14], which further preferably contains an organic acid selected from the group consisting of carbon number 4 to 8, more preferably carbon number 4 to 6 (C) One or more of the -1 component) is preferably a C component, and more preferably one selected from the group consisting of gluconic acid, malic acid, tartaric acid, citric acid, succinic acid, maleic acid, and fumaric acid. Further, as the component C, it is more preferable to contain one or more selected from the group consisting of succinic acid, fumaric acid, and citric acid as the component C.

[16] The extrusion granulated material according to any one of the above [1] to [15], which further preferably contains an alkali metal silicate (component C-2) as a component C, more preferably a crystal granule. The alkali metal ruthenate is preferably a C component as a component C, and further preferably contains a crystalline layered alkali metal ruthenate as a component C.

[17] The extrusion granulated material according to any one of the above [1] to [16] wherein the content of the compound (component A) represented by the above formula (1) is 25% by mass or more, preferably 30%. The mass% or more is more preferably 35 mass% or more, further preferably 40 mass% or more, and is 90 mass% or less, preferably 85 mass% or less, more preferably 80 mass% or less, and still more preferably 75 mass%. % or less is more preferably 70% by mass or less, still more preferably 65% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, still more preferably 50% by mass or less, more preferably 50% by mass or less. It is 30 to 90% by mass, more preferably 30 to 85% by mass, still more preferably 35 to 80% by mass, still more preferably 35 to 75% by mass, still more preferably 40 to 70% by mass, and even more preferably 40. ~65 mass%, more preferably 40 to 60 mass%, still more preferably 40 to 55 mass%, and still more preferably 40 to 50 mass%.

[18] The extruded granulated material according to any one of the above [1] to [17], which contains the carbon number derived from 3 The content of the polymer (component B) of the structural unit of the carboxylic acid having a reactive unsaturated group or a salt thereof is 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further It is preferably 17% by mass or more, and is 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, and further preferably 5 to 50% by mass. Preferably, it is 5 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 17 to 30% by mass.

[19] The extrusion granulated material according to any one of [15] to [18] wherein the content of the C-1 component is preferably from 0.1 to 15% by mass, more preferably from 0.2 to 10% by mass, and further Good is 0.3~5 mass%.

[20] The extrusion granulated material according to any one of the above [16] to [19] wherein the content of the C-2 component is preferably from 0.1 to 25% by mass, more preferably from 1 to 20% by mass, and further Preferably, it is 1 to 15% by mass, and more preferably 3 to 15% by mass.

[21] The extrusion granulated material according to any one of the above [1] to [20] further comprising a binder.

[22] The extruded granule according to the above [21], wherein the content of the binder is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass, and still more preferably 15% by mass. % or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 27% by mass or less, still more preferably 3 to 40% by mass, more preferably It is preferably 5 to 35 mass%, more preferably 10 to 30 mass%, and still more preferably 15 to 27 mass%.

[23] The extrusion granulated material according to the above [21] or [22] wherein the binder contains at least one of a nonionic surfactant and a nonionic polymer.

[24] The extruded granule according to the above [23], wherein the nonionic surfactant contains a glycerin fatty acid ester, a polyglycerin fatty acid ester, a propylene glycol fatty acid ester, a sorbitan fatty acid ester, a polyoxygen Ethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxygen One or more of ethylene polyoxypropylene alkenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, and polyoxyethylene hardened castor oil.

[25] The extrusion granulated material according to [23] or [24] above, wherein the nonionic polymer contains at least one of polypropylene glycol and polyethylene glycol, and more preferably contains polyethylene glycol and polypropylene glycol. In both cases, the content of the polypropylene glycol in the case of using polypropylene glycol is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, still more preferably from 3 to 12% by mass, and even more preferably from 6 to 12% by mass. %.

[26] The extrusion granulated material according to any one of the above [1] to [25], wherein the fine powder ratio is preferably 12% or less, more preferably 10% or less, further preferably 8% or less, and furthermore It is preferably 5% or less, more preferably 3% or less, and is preferably 0.5% or more, and more preferably 1% or more.

[27] The extrusion granulated material according to any one of the above [1] to [26], wherein the breaking load (gf) is preferably 150 or less, more preferably 100 or less, still more preferably 80 or less, and furthermore It is preferably 70 or less, and more preferably 5 or more, and still more preferably 10 or more.

[28] The extrusion granulated material according to any one of the above [1] to [27], wherein the bulk density (g/L) is preferably 350 or more, more preferably 400 or more, and still more preferably 450 or more. It is preferably 750 or less, more preferably 700 or less, further preferably 650 or less, further preferably 600 or less, and still more preferably 530 or less.

[29] The extrusion granulated material according to any one of the above [1] to [28] wherein, in the case where the extruded granules are spherical, the average particle diameter is preferably 0.2 mm or more, more preferably 0.3. Mm or more, and preferably 12 mm or less, more preferably 10 mm or less, further preferably 5 mm or less, more preferably 2 mm or less, and in the case of a columnar or prismatic column, the average diameter is preferably 0.2 mm or more. It is preferably 0.3 mm or more, more preferably 0.5 mm or more, and is preferably 10 mm or less, more preferably 5 mm or less, further preferably 2 mm or less, further preferably 1 mm or less, and an average length of preferably 0.3 mm or more. More preferably, it is 0.5 mm or more, further preferably 0.8 mm or more, and is preferably 10 mm or less, more preferably 8 mm or less, further preferably 5 mm or less, further preferably 3 mm or less, and still more preferably 1.5 mm or less.

[30] A solid detergent composition comprising the extrusion granules according to any one of the above [1] to [29] and an oxygen bleach (component D).

[31] The solid detergent composition according to [30] above, wherein the solid detergent composition is The content of the component A is 3 to 50% by mass, the content of the component B is 1 to 30% by mass, and the content of the component D is 1 to 30% by mass.

[32] The solid detergent composition according to the above [30] or [31], wherein the content of the above-mentioned A component in the solid detergent composition is preferably 3% by mass or more, more preferably 5% by mass or more, more preferably It is 10% by mass or more, more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and still more preferably 30% by mass or less. Further, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 10 to 35% by mass, still more preferably 15 to 30% by mass.

[33] The solid detergent composition according to any one of the above [30], wherein the content of the component B in the solid detergent composition is preferably 1% by mass or more, more preferably 3% by mass or more. Furthermore, it is more preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and more preferably 5 to 15% by mass.

[34] The solid detergent composition according to any one of the above [30], wherein the content of the component D in the solid detergent composition is preferably 1% by mass or more, more preferably 3% by mass or more. Further, it is preferably 5% by mass or more, more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 1 to 30% by mass, still more preferably 3 to 20% by mass, and more preferably 5 to 15% by mass.

[35] The solid detergent composition according to any one of [30] to [34] wherein the mass ratio of the above-mentioned B component to the above-mentioned D component in the solid detergent composition [(B)/(D) It is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and further preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and further preferably 0.2 to 5, more preferably Preferably, it is 0.3 to 3, and more preferably 0.5 to 2.

[36] The solid detergent composition according to any one of [30] to [35], wherein a mass ratio of the component B to the component A (component B/component A) in the solid detergent composition is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, and still more preferably 0.4 or more, and It is preferably 0.8 or less, more preferably 0.7 or less, further preferably 0.65 or less, further preferably 0.6 or less, further preferably 0.1 to 0.8, more preferably 0.2 to 0.7, still more preferably 0.2 to 0.65. More preferably, it is 0.3 to 0.6, and more preferably 0.4 to 0.6.

[37] The solid detergent composition according to any one of the above [30] to [36] wherein the content of the above-mentioned organic acid (C-1 component) having 4 to 8 carbon atoms in the solid detergent composition is preferably It is 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.2% by mass or more, more preferably 10% by mass or less, still more preferably 5% by mass or less, and further It is preferably 2% by mass or less.

[38] The solid detergent composition according to any one of [30] to [37] wherein the content of the alkali metal citrate (C-2 component) in the solid detergent composition is preferably 0.1 mass. It is more preferably 0.5% by mass or more, further preferably 1% by mass or more, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably 7% by mass or less.

[39] The solid detergent composition according to any one of [30] to [38] wherein the content of the alkali agent in the solid detergent composition is preferably 20% by mass or more, more preferably 25% by mass or more. Further, it is preferably 30% by mass or more, more preferably 35% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 65% by mass or more. The mass% or less is more preferably 60% by mass or less, and still more preferably 55% by mass or less.

[40] The solid detergent composition according to the above [39], wherein the alkali agent preferably contains at least one selected from the group consisting of alkali metal carbonates, alkali metal silicates, and amine compounds, and more preferably alkali metal. The carbonate further preferably contains one or more selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate, and more preferably contains sodium carbonate.

[41] The solid detergent composition according to any one of [30] to [40] wherein the solid detergent composition is a powder detergent composition.

[42] The use of the solid detergent composition according to any one of the above [30] to [41], which is for use in an automatic tableware cleaning machine.

[43] The method for producing an extruded granulated product according to any one of the above [1] to [29] wherein the mixture comprising the component A and the component B is subjected to extrusion granulation.

[44] The method for producing an extruded granule according to the above [43], which comprises a mixture of the component A and the component B, preferably 10 ° C or higher, more preferably 30 ° C or higher, and still more preferably 50 ° C or more, more preferably 60 ° C or more, and preferably 100 ° C or less, more preferably 95 ° C or less, and further preferably extrusion granulation at a temperature of 90 ° C or lower.

[45] A method for inhibiting the coloring of a solid detergent composition, which comprises mixing the extruded granules according to any one of the above [1] to [29] with an oxygen bleach (component D).

The materials and apparatuses used in the examples and comparative examples are as follows.

<Materials>

A component: "Trilon M Powder" (MGDA) manufactured by BASF

(Active ingredient 87%) (methylglycine diacetate trisodium salt)

Component B "Acusol 460ND" manufactured by Rohm and Hass

Diisobutylene-maleic acid copolymer, active ingredient 92%

Copolymerization ratio: diisobutylene / maleic acid (mole ratio) = 1.0

Weight average molecular weight: 10,000

Average particle size: 134μm

"Sokalan CP45", manufactured by BASF

Partial sodium salt of acrylic acid/maleic acid copolymer, Active ingredient 92% by mass

Copolymerization ratio: acrylic acid/maleic acid (Morby ratio) = 2

Weight average molecular weight: about 70,000

Average particle size: 64μm

"Sokalan CP12S", manufactured by BASF

Acrylic acid/maleic acid copolymer, active ingredient 50% by mass

Copolymerization ratio: acrylic acid/maleic acid (weight ratio)=1

Weight average molecular weight: about 3000

Viscosity: 130mPa‧s

C component

C-1 component: "Succinic acid" manufactured by Kawasaki Chemical Industry Co., Ltd.

Average particle size: 103μm

C-2 component: "Purifeed" manufactured by Tokuyama Siltech Co., Ltd.

(crystalline layered sodium citrate)

D component: "KCPZ-S" manufactured by Nippon Peroxide

(sodium percarbonate)

<Binder>

"K-PEG6000LA": Kao (stock) manufacturing

Polyethylene glycol (PEG)

Number average molecular weight: about 8,500

"PREMINOL S4011": manufactured by Asahi Glass Urethane Polypropylene glycol (PPG)

Number average molecular weight: about 10,000

"RHEODOL MS-165V": manufactured by Kao (stock), glyceryl stearate

"EXCEL VS-95": Made by Kao (share), Palmitic acid/stearic acid monoglyceride

<Other ingredients>

Alkaline agent: sodium carbonate (Manufactured by CENTRAL GLASS, soda ash)

Modifier: amorphous cerium oxide (manufactured by Tokuyama Chemical Co., Ltd., Tokusil NP)

Enzyme: Mixture of Duramyl 120T (manufactured by Novo Nordisk Bioindustry Co., Ltd.) and Savinase 18T-B (manufactured by Novo Nordisk Bioindustry Co., Ltd.) (mixing mass ratio 1:2)

<device>

Mixer: Cone mixer (manufactured by Hosokawa Micron)

Extrusion granulator: two-axis granulator (manufactured by DALTON)

Granulator: Power mill (made by DALTON)

<Evaluation method> (loose density)

The granules were placed in a cylindrical container (diameter: 4 cm) having a volume of 100 mL of a predetermined mass, and the granules were scraped in the upper portion of the container, and the mass was measured by using a funnel for measuring the bulk density specified in JIS K3362:2008. Determine the bulk density (g/L). Those with lower bulk density indicate easy dissolution.

(fluidity)

Using a funnel, the granulated stream was placed in a cylindrical container used for the measurement of bulk density, and the granulated product was scraped off in the upper portion of the container, and the granulated product was discharged from the bulk measuring funnel specified in JIS K3362:2008. The flow begins until the end of the flow. Those with shorter time indicate excellent fluidity.

(The average particle size)

The particles were dispersed in a solvent in which the particles were not dissolved, and were measured by a laser diffraction/scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) to obtain a median diameter, and the median diameter was obtained. Set to the average particle size. Further, acetone was used as a solvent for the measurement of the average particle diameter of succinic acid, and ethanol was used as a solvent in the measurement of the average particle diameter of the polymer.

(micronized rate)

After vibrating for 5 minutes using "mesh 2000 to 125 μm", the fine powder ratio was calculated from the mass fraction based on the size of the screen.

More specifically, a 9-segment standard sieve and a tray of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm defined by a metal mesh screen described in JIS K8801-1:2006 are used in the tray. The sieves from the smaller mesh are sequentially stacked, and 100 g of particles are added from the top of the 2000 μm sieve. The lid was attached and mounted on a Rotapu vibrating machine (manufactured by HEIKO Co., Ltd., pp 156 times/min, vibration: 290 times/min), and after vibrating for 5 minutes, the mass of the particles remaining on each sieve and tray was measured. The total mass ratio (%) of the particles from the tray to the 250 μm sieve was calculated and set as the fine powder ratio. The smaller powder ratio indicates excellent granulation.

(damage load)

15 g of the granulated product was packed in an assembly unit having a diameter of 38.5 cm, and the joint No. 3 was attached to a rheometer (manufactured by RHEOTECH Co., Ltd.), and a load of 2 kg was applied for 3 minutes. The unit was removed, and the load required to break the compacted powder was measured by a rheometer (manufactured by RHEOTECH Co., Ltd.).

Destruction of the viscosity of the load-bearing powder. The greater the load, the more sticky the powder.

(granulation)

The state of the granules which were just extruded from the extrusion granulator was compared with the state of FIGS. 1-3 and evaluated.

A: As shown in Fig. 1, substantially no larger block was observed, and the granulating machine can be easily pulverized.

B: A larger block can be seen as shown in Fig. 2, but it can be pulverized by a granulator.

C: As shown in Fig. 3, a large number of larger blocks can be seen, and it takes time to use the granulator of the granulator.

<Examples 1 to 14 and Comparative Example 2>

According to the blending amount shown in Table 1, the component A, the component B, the component C, and the PPG were placed in a conical mixer, and the jacket temperature was set to 90 ° C and mixed for 20 minutes.

At this time, the binder component other than the previously melted PPG was charged and further mixed for 20 minutes, and then the mixture was taken out.

Then, the obtained mixture was extruded through a sieve having a pore size of 0.7 mm by an extrusion granulator (manufactured by a biaxial granulator EXR-100 type, manufactured by DALTON Co., Ltd.) to obtain a granulated product. Further, after the granules are cooled, they are pulverized by a granulator to obtain a component A and a component B. Co-granulated cylindrical granules. The obtained granules had an average diameter of 0.7 mm and an average length of 1.2 mm.

The bulk density, the pulverization amount, and the breaking load of the obtained granules were measured. Further, the granulation property of the obtained granules was evaluated. The results are shown in Table 1.

<Comparative Example 1>

Comparative Example 1 was not a granulated product, and the same evaluation as in Example 1 was carried out without granulating Trilon M Powder. The results are shown in Table 1.

<Comparative Example 3>

According to the blending amount described in Table 1, the component A, the component B, and water were mixed with a dispersion wing (manufactured by Ashizawa-Niro Atomizer Co., Ltd., model: HS-P3) to obtain a solid content of 30.8% and a viscosity of 30 mPa·s. Water slurry. Further, the preparation of the aqueous slurry is carried out by first introducing the component B into the mixing tank, and then introducing the component A, followed by adding water and mixing.

The obtained aqueous slurry was spray-dried at a blowing temperature of 150 ° C to obtain particles having an average particle diameter of 207 μm.

The obtained pellets were subjected to the same evaluation as in Example 1.

According to the results of Examples 1 to 4 of Table 1, when the mass ratio of B/A was increased, the granulated product was excellent in the breaking load and the bulk density was low. Further, as a result of the results of Examples 5 to 8, it was found that by containing the component C, the bulk density was lowered and the fluidity was also improved.

Further, according to the comparison between Examples 4 and 9, it was found that the granulated material using Acusol 460ND as the amphiphilic polymer was superior to the granulated material using Sokalan CP45, and the bulk density and the fine powder ratio were excellent, and the bulk density was also changed. low.

On the other hand, in Comparative Example 2 in which the component B was not used, the breaking load, the fine powder ratio, and the fluidity were inferior, and the granulation property was also poor. In Comparative Example 3 using the spray drying method, the breaking load and the fine powder ratio were inferior, and there was no fluidity, so the time could not be measured.

<Examples 15 to 21, Comparative Example 4>

The extruded granules, the D component, and the alkaline agent, modifier, enzyme, and fragrance obtained as the other optional components in Examples 1, 4 to 9 and Comparative Example 2 of Table 1 were prepared as shown in Table 2. The amount was added to a cone mixer and mixed for 10 minutes, whereby the solid detergent compositions of Examples 15 to 21 and Comparative Example 4 were obtained.

<Example 22>

According to the blending amount shown in Table 2, 30 parts of component A, 15 parts of component B, 1 part of succinic acid, and 5 parts of PREMINOL S4011 (polypropylene glycol) were added to a cone mixer, and the tube temperature was set to 90 ° C, and mixed. 20 minutes.

At this time, 8 parts of RHEODOL MS165V previously melted and 3 parts of K-PEG6000LA (polyethylene glycol) were charged, and further mixed for 20 minutes, and then the mixture of the powder temperature of 80 ° C was taken out.

Then, the obtained mixture was extruded through a sieve having a pore size of 0.7 mm by an extrusion granulator to obtain a granulated product. Further, after the granules were cooled, they were pulverized by a granulator to obtain cylindrical granules. The average diameter is 0.7 mm and the average length is 1.2 mm.

The pellet was mixed with 10 parts of sodium percarbonate, 26 parts of sodium carbonate, and 2 parts of an enzyme in a cone mixer, and mixed for 10 minutes, whereby a solid detergent composition was obtained.

The solid detergent composition was evaluated by the following procedure.

(1) Tone before preservation

The solid detergent composition immediately after manufacture was filled in a sealed container, and the color tone was measured using a spectrophotometer manufactured by Konica Minolta Co., Ltd. At the time of evaluation, the b value expressed in the Lab color system was set as the standard of discoloration.

(2) Toned after preservation

The solid detergent composition was filled in a sealed container, and stored in an environment of 30° C./70% Rh, and the difference between the value measured after 30 days and the value measured in the above (1) was calculated. △b value. The results are shown in Table 2.

The difference between the value stored for 60 days, stored for 180 days, and the value before storage was determined in the same manner. The results are shown in Table 2. Further, an increase in the b value indicates that the solid detergent composition is discolored to yellow, and "x" in Table 2 indicates that the Δb value exceeds 20.

(3) Cleaning evaluation (for the cleanliness of dry semi-cooked egg yolk stains)

‧Test tableware production

Make test tableware according to the following steps.

(1) Break the eggs (5 pieces) and use the egg yolk separator to remove the protein and separate the egg yolk.

(2) Five egg yolks were added to the screw cap sample bottle (No. 8), and heated in a water bath (73 to 75 ° C) for 10 minutes.

(3) The screw cap sample bottle was taken out from the water bath, and allowed to stand at 25 ° C for 1 hour, and the semi-cooked egg yolk was placed on the tea strain net for screen filtration.

(4) Filter the semi-cooked egg yolk with a sieve, and mix and mix the lower part of the self-filtering tea net, then take 3.5g and apply it evenly to the ramen bowl with a brush (all kinds of ramen big wrist (green) [capacity 900mL], SINANO Made by INTERNATIONAL COMMERCE CO., LTD.).

(5) The semi-cooked egg yolk coated on the ramen bowl was dried at 25 ° C for a day and night to prepare test dishes.

‧ cleaning test

The cleaning agent composition for an automatic dishwashing machine prepared in the above-mentioned Examples and Comparative Examples was put into a dish cleaning and drying machine (Panasonic), model "NP-TR3" (the concentration of the cleaning liquid was 0.1% by mass). In the special detergent tank of the tabletop)) (use of tap water: 3L).

In the place where the tableware is placed on the right side of the basket under the tableware cleaning and drying machine, the test tableware is erected and cleaned in a standard process by placing two bowls in the groove of the vertical tableware. Further, the test tableware was erected with the stain adhered to the inner side. Further, the cleaning test was repeated under the same conditions, and the total of the four bowls obtained were evaluated.

‧Test method for cleanliness

The amount of dry, semi-cooked egg yolk remaining on the surface of the test dish was evaluated by visual inspection on a scale of 0 to 5. The evaluation was performed by evaluation by 5 people and calculation of the average value. In other words, the five evaluators evaluated the above four bowls, and calculated the average value, thereby performing evaluation. The results are shown in Table 2.

(judgment basis)

5: Completely clean.

4: Although some stains remain, they are almost clean.

3: Although most of it is clean, there are stains left. Or the stain remains on the whole lighter.

2: Slightly clean, but most of the stain remains.

1: Almost unclean.

0: Not clean at all.

As can be seen from Table 2, in Examples 15 to 22, almost no discoloration occurred even after 30 days of storage. On the other hand, Comparative Example 4 in which the component B was not used was markedly colored. Further, it can be seen that, after storage for 60 days, although Examples 15 and 16 have some discoloration, Examples 17 to 20 and 22 in which citrate or succinic acid co-granulation were carried out, and Example 21 in which Sokalan CP45 cogranulated was not produced. Discoloration, even after 180 days of storage, almost no discoloration occurred.

Further, according to Table 2, in Example 15, 16 in which Acusol 460ND was blended as the component B, the cleaning performance was high, and the cleaning performance of Example 16 in which the amount of Acusol 460ND was large was particularly high.

According to the above results, the solid detergent composition of the present invention does not cause discoloration during storage, and is excellent in storage stability and high in cleaning performance.

Claims (12)

An extrusion granulated product containing 25 to 90% by mass of a compound represented by the following formula (1) (component A) and containing a carboxylic acid having a reactive unsaturated group derived from carbon atoms 3 to 6. The polymer (component B) of the structural unit of the salt thereof is 3 to 50% by mass, and the total content of the A component and the B component in the granulated product is 28 to 95% by mass. (wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, ammonium, an alkanolammonium, and an alkylammonium), The component B is a copolymer comprising a structural unit derived from a carboxylic acid having a reactive unsaturated group of 3 to 6 or a salt thereof and a structural unit derived from an olefin having 2 to 12 carbon atoms. An extrusion granulated product containing 25 to 90% by mass of a compound represented by the following formula (1) (component A) and containing a carboxylic acid having a reactive unsaturated group derived from carbon atoms 3 to 6. The polymer (component B) of the structural unit of the salt thereof is 3 to 50% by mass, and the total content of the A component and the B component in the granulated product is 28 to 95% by mass. (wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, and M ¹ , M ² and M ³ each independently represent one selected from the group consisting of a hydrogen atom, an alkali metal, an ammonium, an alkanolammonium, and an alkylammonium), and The extrusion granulated product further contains one or more selected from the group consisting of organic acids (C-1 components) having 4 to 8 carbon atoms as the C component. The extrusion granulated material of claim 1 further contains one or more selected from the group consisting of organic acids (C-1 components) having 4 to 8 carbon atoms as the C component. The extruded granulated material according to any one of claims 1 to 3, which further contains a binder. The extrusion granulated material according to any one of claims 1 to 3, wherein a mass ratio [(B)/(A)] of the component B to the component A is 0.1 to 0.8. The extrusion granulated material according to any one of claims 1 to 3, which further contains an alkali metal silicate (component C-2) as a component C. A solid detergent composition comprising the extruded granules and the oxygen-based bleach (component D) according to any one of claims 1 to 6 containing the component A and the component B described above. The solid detergent composition according to claim 7, wherein the content of the component A is from 3 to 50% by mass, the content of the component B is from 1 to 30% by mass, and the content of the component D is from 1 to 30% by mass. The solid detergent composition according to claim 7 or 8, wherein the mass ratio [(B)/(D)] of the component B to the component D is 0.2 to 5. A use of the solid detergent composition according to any one of claims 7 to 9 for use in an automatic tableware cleaner. A method for producing an extruded granulated product according to any one of claims 1 to 6, wherein the mixture comprising the component A and the component B is subjected to extrusion granulation. A method for inhibiting the coloring of a solid detergent composition, which comprises mixing the extruded granules according to any one of claims 1 to 6 with an oxygen bleach (component D).