JP5689620B2 - Powder cleaning composition - Google Patents

Description

  The present invention relates to a powder cleaning composition containing an amine oxide and a method for producing the powder cleaning composition.

Amine oxide is widely used in dishwashing detergents and the like because it exhibits excellent cleaning performance as a raw material for cleaning agents and also has an effect of preventing hand shake. However, amine oxide has a high hygroscopic property, and when incorporated in a large amount in a powder type detergent, there is a problem in that powder physical properties and storage characteristics are deteriorated.
Conventionally, methods for pulverizing amine oxides have been studied. For example, a method of freeze-drying (see Patent Document 1), a method of spray-drying (see Patent Document 2), and a method of spray-drying by supporting on a sulfate or the like. (See Patent Document 3) and the like are known. However, since either method consumes a large amount of energy to remove moisture, it is not preferable from the viewpoint of manufacturing cost and environmental load. In spray drying, high-temperature hot air comes into contact with amine oxide, which causes problems such as decomposition, coloring, and odor generation of amine oxide.

Patent Document 4 discloses a method of pulverizing zeolite pores by impregnating with an amine oxide aqueous solution. This method can be pulverized with relatively low energy, but zeolite cannot be used for products that cannot be mixed with zeolite from the viewpoint of solubility and the like because zeolite does not dissolve in water.
Patent Document 5 discloses an aqueous liquid dishwashing composition containing a surfactant such as amine oxide, a hydrotrope, an unsaturated aliphatic terpene alcohol or a derivative thereof, and an amphiphilic polymer. However, since the amine oxide used here has a long-chain alkyl group having 10 or more carbon atoms, the cleaning performance and the like are not sufficiently satisfactory, and this composition is an aqueous liquid composition.
Patent Document 6 discloses a solid composition having a particle shape with suppressed hygroscopicity, which contains a hygroscopic amphoteric surfactant and a fatty acid, and is substantially free of other detergents and / or detergent additives. . However, in the process of producing the solid composition, a step of removing water such as vacuum distillation is necessary. Moreover, although the hygroscopicity of this solid composition is reduced, it has not led to the improvement of the required powder physical properties.

Japanese Examined Patent Publication No. 39-14983 JP-A-8-60187 Japanese Patent Publication No.49-1443 Japanese Examined Patent Publication No. 1-14644 Special table 2001-523755 gazette JP 2001-524582 A

From the above situation, there has been a demand for a powder detergent composition containing an amine oxide which is manufactured while suppressing energy consumption and has good powder properties without impairing the stability of the amine oxide.
An object of the present invention is to provide a powder detergent composition containing an amine oxide having good powder physical properties, a method for producing the same, and a detergent for an automatic dishwasher comprising the powder detergent composition. .

  The present inventors have found that the molecular mobility of the cleaning agent molecule is very important for penetrating and diffusing the cleaning agent component into the soil and enhancing the cleaning effect. It has been found that it is desirable to select a base having a molecular weight as low as possible rather than a base having a high hydrophilic part. Moreover, it discovered that the said subject could be solved by mix | blending a specific fatty acid with a specific ratio with the specific amine oxide which has a medium chain alkyl group, and containing the powder raw material for washing | cleaning.

That is, the present invention provides the following [1] to [3].
[1] A mass ratio of fatty acid (b) to amine oxide (a) containing amine oxide (a), fatty acid (b) and cleaning powder raw material (c) represented by the following general formula (1) [( b) / (a)] is a powder detergent composition of 1/5 to 1/1.

(In the formula, R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl having 1 to 3 carbon atoms. R ⁴ represents an alkanediyl group having 2 to 3 carbon atoms, X represents an amide group or an ether group, and n is 0 or 1.
[2] An automatic dishwasher detergent comprising the powder detergent composition of [1].
[3] The method for producing a powder cleaning composition according to [1], wherein at least a part of the cleaning powder raw material (c) and the amine oxide (a) are mixed, and then the fatty acid (b) is added. A method for producing a powder detergent composition to be mixed.

  The powder detergent composition of the present invention has good powder properties with a low breaking load and excellent fluidity. Therefore, the powder cleaning composition is particularly suitable for use as a detergent for automatic dishwashers.

The powder cleaning composition of the present invention contains a specific amine oxide (a), a fatty acid (b), and a powder raw material for cleaning (c), and the mass ratio of the fatty acid (b) to the amine oxide (a) [(b ) / (A)] is 1/5 to 1/1.
The powder cleaning composition of the present invention contains a specific amount of (b) fatty acid, so that the breaking load of the resulting powder cleaning composition is reduced, the fluidity is improved, and the powder has good powder properties. . The reason is not clear, but the powder detergent composition obtained by combining the fatty acid of component (b) with the amine oxide of component (a) to form string micelles can prevent stickiness. It is considered that the breaking load is lowered and the fluidity is improved.

In the present invention, “powder” means a form that is solid particles at room temperature, and usually means that the particles have an average particle diameter of 0.1 to 2000 μm. The shape of the particle is not particularly limited, and may be any of a spherical shape, an indefinite shape, a cylindrical shape, and the like.
The average particle size of the powder cleaning composition of the present invention is preferably 0.1 to 2000 μm, more preferably 10 to 600 μm, and still more preferably 100 to 400 μm.

<Amine oxide (a) represented by general formula (1)>
The amine oxide (a) (hereinafter also referred to as component (a)) used in the present invention is represented by the following general formula (1).

(In the formula, R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl having 1 to 3 carbon atoms. R ⁴ represents an alkanediyl group having 2 to 3 carbon atoms, X represents an amide group (—NHCO— or —CONH—) or an ether group, and n is 0 or 1.
The amine oxide represented by the general formula (1) may be a mixture of n = 0 and n = 1.
Conventionally, it is known that it can be blended in a detergent for an automatic dishwasher blended with an amine oxide having a long-chain alkyl group. In the present invention, the hydrocarbon group as R ¹ has 3 to 8 carbon atoms. , Preferably 6-8, foaming can be suppressed, it can be used without any trouble in an automatic dishwasher, etc., and excellent cleaning power can be obtained. The hydrocarbon group as R ¹ is preferably an alkyl group or an alkenyl group, and may be linear or branched.
The total number of carbon atoms of R ^{1 to} R ^{4 in} the general formula (1) is preferably 12 or less, more preferably 11 or less, and still more preferably 10 or less, from the viewpoints of solubility in water and cleaning performance. In particular, when the powder detergent composition of the present invention is blended as a detergent for an automatic dishwasher, when the total number of carbon atoms of R ^{1 to} R ^{4 in} the general formula (1) is 12 or less, It is preferable from the viewpoint that the solubility is good, the wetting and spreading properties of the cleaning liquid on the tableware surface are not hindered, and the active ingredient can easily reach the gap between the overlapping dishes, and as a result, good fixed dirt removal ability can be obtained. .

In the general formula (1), preferred examples of the amine oxide when n = 0 are octyldimethylamine oxide, octyldiethylamine oxide, 2-ethylhexyldimethylamine oxide, 2-ethylhexyldiethylamine oxide, hexyldimethylamine oxide, hexyldiethylamine. Examples thereof include oxide, butyldimethylamine oxide, and butyldiethylamine oxide.
In the general formula (1), preferred examples of the amine oxide when n = 1 include octylamidopropyldimethylamine oxide, butyramidepropyldimethylamine oxide, and the like.
Among these, octyldimethylamine oxide, 2-ethylhexyldimethylamine oxide, hexyldimethylamine oxide, and octylamidopropyldimethylamine oxide are more preferable from the viewpoints of solubility in water and washing performance.

(A) A component may be mix | blended in the state of aqueous solution, suspension, or paste. Even if the component (a) contains water, a powder cleaning composition having good powder properties can be obtained by containing the fatty acid (b) and the cleaning powder raw material (c) described later. . The concentration of the component (a) in the aqueous solution, suspension or paste is preferably 45 to 95% by mass, more preferably 50 to 95% by mass, and still more preferably 50 to 90% from the viewpoint of appropriately promoting powdering. % By mass.
In addition, the content of the aqueous solution, suspension or paste containing the component (a) belonging to the above concentration range is preferably 1 to 12% by mass with respect to the total powder cleaning composition from the viewpoint of cleaning performance. Preferably it is 2-10 mass%, More preferably, it is 4-9 mass%.

<Fatty acid (b)>
The fatty acid (b) (hereinafter also referred to as component (b)) used in the present invention is a linear and / or branched saturated or unsaturated fatty acid.
The fatty acid (b) is preferably a fatty acid having 8 to 22 carbon atoms, more preferably selected from oleic acid, linoleic acid, or a mixture thereof from the viewpoint of reducing the breaking load and improving the fluidity. It is a fatty acid. In addition, these fatty acids can be used individually or in combination of 2 or more types.
The mass ratio [(b) / (a)] of the fatty acid (b) to the amine oxide (a) is 1/5 to 1/1 from the viewpoint of reducing the breaking load and improving the fluidity, preferably 1/5 to 2/3, more preferably 1/5 to 3/5. If the mass ratio is less than 1/5, the effect of improving the powder physical properties due to the addition of the component (b) cannot be sufficiently obtained, and if it is greater than 1/1, the powder physical properties deteriorate, such being undesirable. It is considered that the powder physical properties are deteriorated due to, for example, a decrease in the ratio of the powder component to the liquid component due to an excessive amount of the component (b).
The content of the component (b) relative to the total powder cleaning composition is not particularly limited as long as it belongs to the above mass ratio range, but is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. %, More preferably 1 to 3% by mass.

<Powder material for cleaning (c)>
The cleaning powder raw material (c) (hereinafter also referred to as component (c)) used in the present invention means a particulate raw material that improves cleaning performance and powder physical properties, and specifically comprises a polymer compound. Examples thereof include powders, alkali agents, chelating agents, bleaching agents, extenders / diluents, surface modifiers, enzymes, enzyme stabilizers such as calcium salts and formic acid, antibacterial / antifungal agents, and the like. Among these, as the component (c), it is preferable to use a powder comprising a polymer compound and / or an alkali agent.
The total content of these components (c) is preferably 70 to 98% by mass, more preferably 75 to 95% by mass, and still more preferably, based on the total powder detergent composition, from the viewpoint of improving the cleaning performance and powder physical properties. Is 80-93 mass%.
The average particle size of component (c) is preferably 0.1 to 2000 μm, more preferably 1 to 1000 μm, still more preferably 1 to 600 μm, and even more preferably 1 to 300 μm, from the viewpoint of improving powder physical properties. is there.

(Powder made of polymer compound)
The polymer compound used as the component (c) is an amphiphilic polymer having both a hydrophobic group and a hydrophilic group. By containing the amphiphilic polymer, the breaking load of the powder detergent composition can be lowered and the fluidity can be improved. Among these polymer compounds, a structural unit derived from a compound having a polymerizable unsaturated bond and having a carboxylic acid group and / or a carboxylic anhydride residue (hereinafter also referred to as “monomer (I)”) ( A bi-affinity polymer comprising I) and a structural unit (II) derived from an aliphatic hydrocarbon having 3 to 10 carbon atoms having a polymerizable unsaturated bond (hereinafter also referred to as “monomer (II)”) is preferred. The total content of the structural unit (I) and the structural unit (II) is preferably not less than 80 mol%, more preferably not less than 85 mol%, still more preferably not less than 90 mol%, particularly preferably based on all the structural units. Is substantially 100 mol%.
When an acid anhydride is used as the monomer (I), the acid anhydride may be hydrolyzed during the production of the polymer compound or after the production, so that a part of the acid anhydride may become a carboxylic acid group.
Further, the powder composed of the polymer compound is not limited to the powder composed of only the polymer compound, and may be a powder composed of a polymer compound containing water and water within a range not impairing the function as the powder. . The content of water contained is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 15% by mass with respect to the powder.

Monomer (I) is an anionic hydrophilic monomer, (1) a compound having a polymerizable unsaturated bond and having one or two carboxylic acid groups, and (2) polymerizable unsaturated. A compound having a bond and having a carboxylic anhydride residue is preferred. Specific examples include one or more monomers selected from acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, maleic acid, itaconic acid, and salts thereof, and maleic anhydride. The carboxylic acid anhydride residue means a group in which two carboxylic acid groups have an anhydrous structure.
In these, the 1 or more types of monomer chosen from acrylic acid and its salt, maleic acid and its salt, and maleic anhydride is preferable.

  On the other hand, the monomer (II) is a hydrophobic monomer and is a hydrocarbon compound having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, having a polymerizable unsaturated bond. Specific examples include monomers selected from propylene, butene, isobutene, pentene, isopentene, hexene, heptene, octene, diisobutene, nonene, isononene, decene, and isodecene. Among these, one or more monomers selected from pentene, octene, isobutene and diisobutene are preferable.

In addition to the structural unit (I) derived from the monomer (I) and the structural unit (II) derived from the monomer (II), the polymer compound (c) can be copolymerized with the monomers (I) and (II). It may have a structural unit (III) derived from another monomer (hereinafter also referred to as “monomer (III)”).
As the monomer (III), ethylene oxide, propylene oxide, acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethyl Acrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, acrylic acid (or methacrylic acid) alkyl (1 to 5 carbon atoms), acrylic acid (or methacrylic acid) 2- Hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (C1-5), allylamine, N, N-diallylamine, N, N-diallyl-N-alkyl (C1-5) Amines, 2-vinylpyridine, 4-vinylpyridine, sulfur dioxide, etc. That.
As the polymer compound (c), one or more structural units derived from one or more monomers (I) selected from acrylic acid, maleic acid, and maleic anhydride, and one selected from pentene, octene, isobutene, and diisobutene Examples thereof include polymers containing at least the structural unit derived from the monomer (II), and a diisobutylene / maleic acid copolymer and an isobutylene / maleic anhydride copolymer are particularly preferable.

The polymer compound (c) can be obtained by copolymerizing the monomer (I), the monomer (II) and, if necessary, the monomer (III). There is no restriction | limiting in particular in a polymerization method, Although it can carry out by well-known methods, such as suspension polymerization and solution polymerization, a solution polymerization is preferable from a viewpoint of controlling polymerization precisely and performing superposition | polymerization.
The polymerization temperature is preferably 0 to 150 ° C, more preferably 20 to 90 ° C. The reaction pressure is preferably 0.01 to 0.5 MPa, more preferably 0.05 to 0.2 MPa. Moreover, it is preferable to perform reaction in inert gas atmosphere, such as nitrogen.
Examples of polymerization initiators include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, azo compounds such as azobis-2-methylpropionamidine hydrochloride, azoisobutyronitrile, benzoyl peroxide, lauroyl peroxide, and the like. And the like.
As the polymerization solvent, water is preferable. From the viewpoint of uniformly dissolving a plurality of monomers, it is more preferable to use an aqueous solvent containing at least one organic solvent. Examples of the organic solvent include lower alcohols such as methanol, ethanol and isopropanol, aromatic or aliphatic hydrocarbons such as benzene, toluene, cyclohexane and n-heptane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone. And the like.

In the polymer compound of component (c), the molar ratio of the monomer structural unit (I) to the monomer structural unit (II) [monomer structural unit (I) / monomer structural unit (II)] is a viewpoint of solubility and cleaning performance. Therefore, it is preferably 20/80 to 90/10, more preferably 30/70 to 90/10, and still more preferably 40/60 to 80/20. The molar ratio corresponds to the addition ratio of the monomers (I) and (II) during the polymerization of the polymer compound.
The mass average molecular weight of the polymer compound is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and still more preferably 5,000 to 50,000. The mass average molecular weight can be measured by gel permeation chromatography (GPC) method using acetonitrile / 0.1M aqueous sodium chloride solution (30/70) as a developing solvent and polyethylene glycol as a standard substance.
The content of the polymer compound is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, and still more preferably 1 to 30% by mass in the component (c) from the viewpoint of improving cleaning performance and powder physical properties. Yes, preferably 1 to 98% by mass, more preferably 1 to 50% by mass, and still more preferably 1 to 30% by mass with respect to the total powder detergent composition.

(Alkaline agent)
Examples of the alkali agent used as the component (c) include alkali metal carbonates and alkali metal silicates.
Examples of the alkali metal carbonate include sodium carbonate (soda ash), potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like.
Examples of the alkali metal silicate include crystalline layered sodium silicate known by the trade name Prefeed (manufactured by Tokuyama Siltech Co., Ltd.). Amorphous alkali metal silicates can also be used. These alkali metal silicates are also effective for preventing oxidation of tableware.
In addition, the alkali agent may have a particle diameter or a bulk density adjusted by a granulation process or the like. Among these alkali agents, alkali metal carbonates are preferable, and sodium carbonate (soda ash), sodium hydrogen carbonate, potassium carbonate, and potassium hydrogen carbonate are more preferable.
The content of the alkaline agent is preferably 1 to 100% by mass, more preferably 1 to 70% by mass, and still more preferably 1 to 50% by mass in the component (c) from the viewpoint of improving cleaning performance and powder physical properties. The total powder cleaning composition is preferably 1 to 98% by mass, more preferably 1 to 70% by mass, and still more preferably 1 to 50% by mass.

(Chelating agent)
Examples of the chelating agent (sequestering agent) used as the component (c) include phosphates such as sodium tripolyphosphate. In addition, when using a phosphorus-free detergent, citric acid, malic acid, tartaric acid, succinic acid, L-glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, methylglycine triacetic acid, three Acetic acid, 1,3-propanediamine triacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, hydroxy Examples thereof include polycarboxylic acids such as ethylethylenediaminedicarboxymethylglutamic acid or salts thereof. Among these, citric acid, succinic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethylglutamic acid, and alkali metal salts thereof are preferable.

(bleach)
The bleaching agent used as the component (c) is preferably a solid substance that generates hydrogen peroxide or peracid species by dissolution. Specific examples include granular materials such as sodium percarbonate and sodium perborate. A bleaching agent is not an essential component, but is suitable in that it can remove not only detergency but also odor. When it is desired to suppress moisture absorption of the bleaching agent or to improve fluidity, it may be coated with a nonionic surfactant or the like. In particular, the storage stability is improved by coating with alkali metal silicate, boric acid or salt.
A bleaching activator may be used in combination with a bleaching agent. A bleach activator is a substance that reacts with hydrogen peroxide released from a bleach to produce an organic peracid having a higher redox potential. As the bleach activator, tetraacetylethylenediamine is generally known, and other examples include alkanoyloxybenzenecarboxylic acid or a salt thereof, alkanoyloxybenzenesulfonate, and the like.

(Bulking agent, diluent)
Examples of the extender or diluent used as the component (c) include sulfates such as sodium sulfate and magnesium sulfate. These extenders and diluents can be designed in amounts suitable for use by dispersing each component at an appropriate concentration, and are also effective for maintaining the stability of each component.

(Surface modifier)
Examples of the surface modifier used as the component (c) include bentonite, amorphous silica which is a kind of oil-absorbing powder, dextrin, and bowel. Among these, it is preferable to use amorphous silica for extrusion granulation, vacuum rolling granulation, and rolling granulation.
As the amorphous silica, JP-A No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17; JP-A No. 62-191419, page 2, lower right column, line 20; Line to page 5, upper left column, line 11, JP-A-9-132794, JP-A-7-10526, JP-A-6-227811, JP-A-8-119622, and the like. .
Commercially available amorphous silica includes Tokuseal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210-270 mL / 100 g), Fluorite (manufactured by Tokuyama Corporation, oil absorption capacity: 400-600 mL / 100 g), TIXOLEX 25 (Korean / French) Chemical Corporation, oil absorption capacity: 220 to 270 mL / 100 g), Silo Pure (manufactured by Fuji Silysia Co., Ltd., oil absorption capacity: 240 to 280 mL / 100 g) and the like.

(enzyme)
Examples of the enzyme used as the component (c) include protease, amylase, lipase, cellulase, esterase, and peroxidase. In this invention, the granulated commercial item which mix | blends 1 or more types of these enzymes can also be used. Both are selected in consideration of storage stability with other components. For example, amylase can be expected to remove gelatinized starch that is difficult to remove with other detergents, and protease is incorporated because it exhibits a significant removal effect such as denatured proteins that are difficult to remove with surfactants. It is preferable.

<Other optional components>
In the method for producing an amine oxide powder of the present invention, in addition to the components (a) to (c), other optional components can be blended within a range not impairing the effects of the present invention. Examples of such components include surfactants, antifoaming agents, fragrances, and dyes.

Examples of the surfactant include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants, and nonionic surfactants are particularly 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 One or more selected from a nonionic 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 Is preferred. Among these, polyoxyalkylene alkyl ether is preferable, specifically, polyoxyethylene monoalkyl or monoalkenyl ether, wherein the alkyl group or alkenyl group has an average carbon number of 4 to 12, and the number of moles of ethylene oxide added Is more preferably 1 to 20 mol on average.
As the antifoaming agent, a polypropylene glycol having a mass average molecular weight of preferably 600 to 20,000, more preferably 2,000 to 12,000 is preferable in terms of the antifoaming effect. The mass average molecular weight of polypropylene glycol can be measured by a light scattering method using a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.) or the like.

<Production of powder detergent composition>
The powder cleaning composition of this invention is obtained by mixing said (a)-(c) component and another arbitrary component. The amine oxide (a) is preferably mixed in the form of an aqueous solution, suspension or paste having a concentration of 45 to 95% by mass from the viewpoint of handling. The powder cleaning composition of the present invention contains a specific amount of the fatty acid (b) and the powder raw material for cleaning (c), so that the powder cleaning composition is good without undergoing a water removal step such as vacuum distillation or drying treatment. It has powder properties.

As a method of mixing the respective components, (i) (a) to (c) components and other optional components are added simultaneously or separately, and (ii) (c) at least part of the components are ( (a) A method in which component (b) and component (b) are added simultaneously or separately and mixed, and then the remainder of component (c) and other optional components are added and mixed as necessary. A method of adding a mixture of the component (a) and the component (b) to at least a part and mixing, and then adding and mixing the remainder of the component (c) and other optional components as necessary. It is done.
Among them, a method in which at least a part of the component (c) and the components (a) and (b) are simultaneously or separately mixed is preferable, and in particular, at least a part of the component (c) and the component (a) A method of mixing the component (b) after mixing is more preferable. According to this method, since the component (a) is sufficiently adsorbed with the component (c), the raw material mixing property is improved, and a powder cleaning composition having excellent fluidity can be obtained. The component (c) to be mixed with the component (a) is preferably a powder composed of a polymer compound, an alkali agent, or both. In particular, the powder comprising the polymer compound is mixed with the component (a) and sufficiently adsorbed to the component (a), thereby improving the fluidity of the resulting powder cleaning composition and reducing the breaking load. be able to. The remaining component (c) may be added before or after mixing the component (b).

  When mixing each of the above components, Henschel mixer (Mitsui Mining Co., Ltd.), high speed mixer (Fukae Powtech Co., Ltd.), Nauter mixer (Hosokawa Micron Co., Ltd.), ribbon mixer Known mixers such as Kotobuki Kosakusho, V-type blender (Dalton Co., Ltd.), Bench kneader (Irie Shokai Co., Ltd.) can be used.

  The powder detergent composition of the present invention is granulated after the (a) component, the (b) component, the (c) component, and other optional components are mixed using the mixer or simultaneously with the mixing. Can be obtained. Moreover, it can also shape | mold into a tablet shape using a tableting machine etc. Examples of the granulation method include an extrusion granulation method, a rolling granulation method, a pulverization granulation method, a fluidized bed granulation method, a spray granulation method, and a crushing granulation method. The dynamic granulation method is more preferable.

Extruder granulators include pelleter double, twin dome gran, disk pelleter (Dalton Co., Ltd.), basket type granulator (Kikusui Seisakusho Co., Ltd.), granulator (Hosokawa Micron Co., Ltd.), Known extrusion granulators such as the horizontal extrusion screw type extrusion granulator described in No. 192688 are listed.
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, still more preferably 0.5 to 1.0 mm, and forms such as a cylindrical or noodle-shaped granule 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.
As an agitation rolling granulator that can be used, a main agitation shaft having an agitation blade is provided at the center of the inside, and an auxiliary agitation shaft for further assisting mixing and suppressing generation of coarse particles is generally used. May have a structure protruding from the wall surface in a direction perpendicular to the main stirring shaft.
As such a stirring rolling granulator, a Henschel mixer (made by Mitsui Miike Chemical Co., Ltd.), a high speed mixer (made by Fukae Powtech Co., Ltd.), and a vacuum unit are attached as the main stirring shaft is installed vertically. High speed mixers (Fukae Powtech Co., Ltd.), vertical granulators (Fuji Sangyo Co., Ltd.) and the like can be mentioned. Examples of those in which the main stirring shaft is installed horizontally include a Readyge mixer (manufactured by Matsuzaka Giken Co., Ltd.), a pro-share mixer (manufactured by Taiheiyo Kiko Co., Ltd.), and the like.

  The obtained granulated product can be cooled in order to suppress coalescence and agglomeration of the compression molded product, and then can be sized as necessary. There is no limitation in particular in the apparatus used when sizing, A well-known grinder (or crusher) can be used. For example, high speed mixer (Fukae Powtech Co., Ltd.), Malmerizer (Dalton Co., Ltd.), Spiler Flow (Freund Sangyo Co., Ltd.), Fitzmill (Dalton Co., Ltd.), Power Mill (Powrec Co., Ltd.), Comil (Manufactured by Quadro).

  The powder detergent composition obtained as described above has an excellent detergency and a good powder physical property with a low breaking load and excellent fluidity. Therefore, the automatic dishwasher detergent made of the powder cleaning composition is not ideal conditions such as when the dishes are stored excessively in the automatic dishwasher or when the dishes are stored overlappingly. Excellent detergency even below.

  In the following Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified. Further, the breaking load, fluidity, and average particle size of the obtained powder were measured, calculated, or evaluated by the following methods.

(1) Breaking load An adapter with a diameter of 30 mm is attached to a rheometer (manufactured by Rheotech Co., Ltd.), 15 g of powder is set in a metal cylindrical container, and a load of ² kg / cm ² is applied for 3 minutes at 25 ° C. . Next, the amine oxide powder or granule molded by compression is taken out of the container, the ascending speed is adjusted to 2 cm / min, the platform is raised, force is applied to the molded body, and the force when the molded body breaks is measured, This value is the breaking load.
(2) Fluidity The fluidity is measured as follows. The time required for 100 mL of the powder detergent composition to flow out of the bulk density measurement hopper defined by JIS K 3362.
(3) Average particle diameter After vibrating for 5 minutes using a standard sieve (mesh size: 2000 to 125 μm) of JIS K 8801, the median diameter was calculated from the weight fraction depending on the size of the sieve mesh.

Example 1
43.8 parts of soda ash (c) (manufactured by Central Glass Co., Ltd., trade name: Dense ash) was charged into a Nauter mixer (Hosokawa Micron Corporation), and octyldimethylamine oxide (general formula (1), R) ¹ is an n-octyl group, R ² and R ³ are methyl groups, n is 0) A mixture obtained by previously mixing 8 parts of an aqueous solution (a) (effective part 4 parts) and 2 parts of oleic acid (b) And mixed for 20 minutes. Other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than soda ash (c) were added here, and further mixed for 20 minutes to obtain a powder. .
Example 2
33.8 parts of the soda ash (c) and diisobutylene / maleic acid copolymer powder (c) (diisobutylene / maleic acid (molar ratio) = 50/50, weight average molecular weight 15,000, effective 84 %, Manufactured by Rohm and Haas, trade name: ACUSOL460ND) was charged into a Nauter mixer and mixed for 5 minutes. Thereafter, a mixture obtained by previously mixing 8 parts of the octyldimethylamine oxide aqueous solution (a) having the above concentration of 50% (4 parts effective amount) and 2 parts of oleic acid (b) was added and further mixed for 20 minutes. . Other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than soda ash and copolymer powder (c) are added here, and further mixed for 20 minutes. To obtain a powder.
Example 3
A powder was obtained in the same manner as in Example 2 except that “2 parts of oleic acid (b)” was changed to “2 parts of linoleic acid (b)” in Example 2.

Example 4
43.8 parts of the soda ash (c) was charged into a Nauter mixer, 8 parts of the 50% octyldimethylamine oxide aqueous solution (a) (effective part: 4 parts) was blended and mixed for 10 minutes. To this, 2 parts of oleic acid (b) was added and further mixed for 10 minutes. Thereafter, other components such as a bleaching agent, a chelating agent, a surface modifier and an enzyme, and an antifoaming agent other than the soda ash (c) were added, and further mixed for 20 minutes to obtain a powder.
Example 5
33.8 parts of the soda ash (c) and 10 parts of the diisobutylene / maleic acid copolymer powder (c) were charged into a Nauta mixer, and the octyldimethylamine oxide aqueous solution (a) having the above concentration of 50% was added thereto. 8 parts (effective part 4 parts) were blended and mixed for 10 minutes. To this, 2 parts of oleic acid (b) was added and further mixed for 10 minutes. Then, other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than the soda ash and copolymer powder (c) are added and mixed for another 20 minutes. A powder was obtained.
Example 6
A powder was obtained in the same manner as in Example 5 except that “2 parts of oleic acid (b)” was changed to “2 parts of linoleic acid (b)” in Example 5.

Comparative Example 1
35.8 parts of the soda ash (c) and 10 parts of the diisobutylene / maleic acid copolymer powder (c) were charged into a Nauta mixer, and the aqueous solution of octyldimethylamine oxide having a concentration of 50% (a ) 8 parts (effective part 4 parts) was added and mixed for 20 minutes. Then, other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than the soda ash and copolymer powder (c) are added and mixed for another 20 minutes. A powder was obtained.
Comparative Example 2
80 parts of the 50% octyldimethylamine oxide aqueous solution (a) (effective part 40 parts) was charged into a Nauter mixer, and 20 parts of oleic acid (b) was added and mixed for 20 minutes. It was not powdered.
Comparative Example 3
35.3 parts of the soda ash (c) and 10 parts of the diisobutylene / maleic acid copolymer powder (c) were charged into a Nauta mixer and mixed for 5 minutes. Thereafter, a mixture obtained by previously mixing 8 parts of the octyldimethylamine oxide aqueous solution (a) having a concentration of 50% (effective part: 4 parts) and 0.5 part of oleic acid (b) was added, and further added for 20 minutes. Mixed. Other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than soda ash and copolymer powder (c) are added here, and further mixed for 20 minutes. To obtain a powder.
Comparative Example 4
27.8 parts of the soda ash (c) and 10 parts of the diisobutylene / maleic acid copolymer powder (c) were charged into a Nauter mixer and mixed for 5 minutes. Thereafter, a mixture obtained by previously mixing 8 parts of the octyldimethylamine oxide aqueous solution (a) having a concentration of 50% (effective part 4 parts) and 8 parts of oleic acid (b) was added and further mixed for 20 minutes. . Other components such as bleaching agent, chelating agent, surface modifier and enzyme, and antifoaming agent other than soda ash and copolymer powder (c) are added here, and further mixed for 20 minutes. To obtain a powder.

Table 1 shows the powder physical properties obtained by the above-described measurement methods for the powder detergent compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4. In the compositions of Comparative Examples 1 to 4, even when a force of 2000 gf, which is the maximum load of the apparatus used, was applied, the molded body was not broken and the breaking load could not be measured. Also in the measurement of fluidity, the powder did not flow out during the measurement, and the fluidity could not be measured. On the other hand, the composition containing the fatty acid (b) of Example 1 had good results in both breaking load and fluidity as compared with Comparative Example 1. Moreover, the composition containing the powder which consists of a high molecular compound as (c) component of Example 2, 3 further reduced the fracture load, and improved fluidity | liquidity.
Moreover, the fluidity of the composition of Example 4 in which the component (a) and the component (b) were separately added was improved as compared with Example 1. In addition, the compositions of Examples 5 and 6 including the powder composed of the polymer compound as the component (c) not only improve the fluidity but also reduce the breaking load as compared with Examples 2 and 3 having the same composition. did.

  The powder detergent composition of the present invention has excellent detergency and has good powder properties with a low breaking load and excellent fluidity, and thus is particularly suitable for use as a detergent for automatic dishwashers.

Claims (6)

An automatic dishwasher detergent comprising a powder detergent composition,
The powder cleaning composition contains an amine oxide (a) represented by the following general formula (1), a fatty acid (b), and a cleaning powder raw material (c), and the fatty acid (b) relative to the amine oxide (a). the weight ratio of [(b) / (a)] is Ri 1 / 5-1 / 1 der,
The detergent for automatic dishwashers whose content of the fatty acid (b) with respect to the whole powder cleaning composition is 0.1-5 mass% and whose content of the powder raw material (c) for cleaning is 70-98 mass%.

(In the formula, R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl having 1 to 3 carbon atoms. R ⁴ represents an alkanediyl group having 2 to 3 carbon atoms, X represents an amide group or an ether group, and n is 0 or 1. The detergent for automatic dishwashers of Claim 1 whose carbon number of a fatty acid (b) is 8-22. The detergent for automatic dishwashers according to claim 1 or 2, wherein the fatty acid (b) is a fatty acid selected from oleic acid, linoleic acid, or a mixture thereof. The detergent for automatic dishwashers in any one of Claims 1-3 whose average particle diameter is 0.1-2000 micrometers. The detergent for automatic dishwashers in any one of Claims 1-4 in which the powder raw material for washing | cleaning (c) contains an alkaline agent. A method for producing a powder detergent composition comprising:
It contains an amine oxide (a) represented by the following general formula (1), a fatty acid (b), and a cleaning powder raw material (c), and the mass ratio of the fatty acid (b) to the amine oxide (a) [(b) / (A)] is 1/5 to 1/1,
The content of the fatty acid (b) relative to the total powder detergent composition is 0.1 to 5% by mass, the content of the cleaning powder raw material (c) is 70 to 98% by mass,
After mixing at least a part of the cleaning powder raw material (c) and the amine oxide (a) in a state of an aqueous solution, suspension or paste having a concentration of 45 to 95% by mass , the fatty acid (b) is mixed. A method for producing a powder detergent composition.

(In the formula, R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl having 1 to 3 carbon atoms. R ⁴ represents an alkanediyl group having 2 to 3 carbon atoms, X represents an amide group or an ether group, and n is 0 or 1.