WO2010073752A1 - Process for production of amine oxide powder or granule - Google Patents

Abstract

Disclosed is a process for efficiently producing an amine oxide powder or granule having excellent solubility, which comprises mixing 5 to 80 mass% of (a) an aqueous solution, a suspension or a paste containing 50 to 95 mass% of an amine oxide represented by general formula (1) with 95 to 20 mass% of (b) a powder comprising a polymeric compound which contains a constituent unit derived from a compound having a carboxylic acid group and/or a carboxylic anhydride residue and a constituent unit derived from an aliphatic hydrocarbon having 3 to 10 carbon atoms and having a polymerizable unsaturated bond in a total amount of 80 mol% or more relative to the total amount of all constituent units.  Also disclosed is a detergent composition for an automatic dishwasher, which comprises the amine oxide powder or granule. [In the formula, R¹ represents a hydrocarbon group having 3 to 8 carbon atoms; R² and R³ independently represent an alkyl group having 1 to 3 carbon atoms, or the like; R⁴ represents an alkanediyl group having 2 to 3 carbon atoms; X represents an amide group or an ether group; and n represents a number of 0 or 1.]

Description

Method for producing amine oxide powder or granule

The present invention relates to a method for producing amine oxide powder or granules, and a detergent composition for an automatic dishwasher containing amine oxide powders or granules.

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 shaking. However, amine oxides are usually handled in an aqueous solution, and when mixed in a large amount in a powder type detergent, there are problems such as deterioration of powder physical properties and storage characteristics.
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, 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.

On the other hand, as the development of automatic dishwashers by home appliance manufacturers progresses, more and more devices are being washed at once, and the amount of tableware filling can be greatly improved by orderly arranging the dishes in the washing machine. It is possible. In fact, the tableware filling amount of the automatic dishwasher released by Matsushita Electric Industrial Co., Ltd. has increased from 21 in 1996 to 60 in 2005. Everyone should be able to enjoy these benefits if they can place the right shaped tableware in the right place, but unfortunately, the tableware arrangement proposed by home appliance manufacturers is rarely reproduced in the home. It is. In fact, when the arrangement of tableware at home is observed, it is common that adjacent tableware overlap and the distance between the tableware is very narrow. This is due to the great variety of shapes and sizes of tableware used at home. Fixing pins are arranged at regular intervals in the tableware basket, but since these do not adapt to all tableware shapes and tableware sizes, it is almost impossible to reproduce the ideal tableware arrangement. When the distance between the dishes is reduced, the water flow from the spray arm is shielded so that the cleaning liquid does not reach the dirt, and the mechanical force is very little. Therefore, the detergency is unavoidable.

Japanese Examined Patent Publication No. 39-14983 Japanese Examined Patent Publication No. 39-14983 Japanese Patent Publication No.49-1443 Japanese Examined Patent Publication No. 1-14644 JP-T-2001-523755

From the above situation, there has been a demand for a method for producing an amine oxide powder or granule excellent in solubility without suppressing energy consumption and impairing the stability of the amine oxide. In addition, there has been a demand for a cleaning composition for an automatic dishwasher that satisfies both excellent soil removal properties and low foaming properties even under non-ideal conditions in which the distance between adjacent tableware is narrowed.
An object of the present invention is to provide an efficient method for producing an amine oxide powder or granule excellent in solubility, and a cleaning composition for an automatic dishwasher containing the amine oxide powder or granule.

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. In addition, by mixing or mixing and granulating a specific amphiphilic polymer in a specific ratio with a specific amine oxide having a medium chain alkyl group, and by using the amine oxide powder or granule, I found that it could be solved.
That is, the present invention provides the following [1] to [3].
[1] An aqueous solution, suspension or paste (a) containing 50 to 95% by mass of an amine oxide represented by the following general formula (1):
A structural unit derived from a compound having a carboxylic acid group and / or a carboxylic acid anhydride residue, and a structural unit derived from an aliphatic hydrocarbon having 3 to 10 carbon atoms having a polymerizable unsaturated bond in all the structural units. A method for producing an amine oxide powder, comprising mixing 95 to 20% by mass of a powder (b) comprising a polymer compound containing 80 mol% or more in total.

(Wherein R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ each independently represents 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] A method for producing amine oxide granules, wherein 5 to 80% by mass of the component (a) and 95 to 20% by mass of the component (b) are mixed or simultaneously granulated.
[3] An aqueous solution, suspension or paste (a) containing 50 to 95% by mass of the amine oxide represented by the general formula (1) (a) and a powder (b) comprising the polymer compound A cleaning agent for automatic dishwashers containing 95 to 20% by weight of amine oxide powder or granules obtained by mixing or granulating simultaneously with mixing, and (e) an alkaline agent and / or sequestering agent Composition.

BEST MODE FOR CARRYING OUT THE INVENTION

<Method for producing amine oxide powder or granule>
A first aspect of the method of the present invention (first invention: method for producing powder) is an aqueous solution, suspension or paste (a) 5 containing 50 to 95% by mass of an amine oxide represented by the following general formula (1): It is characterized by mixing ˜80% by mass and 95-20% by mass of the powder (b) comprising the polymer compound.
In the second aspect of the method of the present invention (second invention: method for producing granules), after mixing 5 to 80% by mass of the component (a) and 95 to 20% by mass of the component (b), or after mixing It is characterized by granulating at the same time.
In the present invention, “powder” means a form that is solid particles at normal temperature, and usually means that the average particle size is 0.1 μm or more and less than 300 μm. “Granule” means a form that is a solid granule at normal temperature, and is usually a particle having an average particle size of 0.3 to 10 mm, or a diameter of 0.3 to 10 mm, and a length of 0.3 to 10 mm. It means that it is in the form of pellets. The shape of the particles or granules is not particularly limited, and may be any of spherical, indeterminate, cylindrical and the like.

<Amine oxide represented by general formula (1)>
The amine oxide used in the present invention is represented by the following general formula (1).

(Wherein R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ each independently represents 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 added to a detergent for an automatic dishwasher containing 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. However, preferably 6 to 8 can suppress foaming and can be used with no trouble in an automatic dishwasher or the like, and an excellent detergency 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 from the viewpoint of solubility in water and cleaning performance. In particular, when blended into a cleaning composition for an automatic dishwasher, if the total number of carbon atoms of R ¹ to R ^{4 in} the general formula (1) is 12 or less, the solubility in water is good, It is preferable from the viewpoint that the active ingredient can easily reach the gap between the overlapping dishes without impairing the wetting and spreading property of the cleaning liquid on the tableware surface, 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.
Of these, octyldimethylamine oxide, 2-ethylhexyldimethylamine oxide, hexyldimethylamine oxide, and octylamidopropyldimethylamine oxide are more preferable.

<Amine oxide aqueous solution, suspension or paste (a)>
The amine oxide aqueous solution, suspension or paste (a) [hereinafter also referred to as component (a)] used in the present invention contains 50 to 95% by mass of the amine oxide represented by the general formula (1). An aqueous solution, suspension or paste. The concentration of the amine oxide in the aqueous solution, suspension or paste is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, from the viewpoint of appropriately promoting powdering.

<Powder made of polymer compound (b)>
The polymer compound used in the present invention is an amphiphilic polymer having both a hydrophobic group and a hydrophilic group, and a compound having a carboxylic acid group and / or a carboxylic acid anhydride residue [hereinafter, monomer (I) The structural unit (I) derived from) and the 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)). It is a polymer compound containing 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more in total [structural unit (I) + structural unit (II)] in the structural unit. The polymer compound is most preferably one in which the total of the structural unit (I) derived from the monomer (I) and the structural unit (II) derived from the monomer (II) 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 (b) composed of a polymer compound (hereinafter also referred to as the component (b)) may be a powder composed solely of the polymer compound or a powder composed of the polymer compound and water. In this case, water can be contained within a range where the function as a powder is not impaired, and the content of water in the powder is usually 0.1 to 30% by mass, preferably 0.1 to 20% by mass. It is.

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 or its salt, maleic acid or 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 (b) can be copolymerized with the monomers (I) and (II). It may have a structural unit (III) derived from other monomer [hereinafter also referred to as monomer (III)].
Monomers (III) include 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.
Preferred examples of the polymer compound (b) are selected from structural units derived from one or more monomers (I) selected from acrylic acid, maleic acid, and maleic anhydride, and pentene, octene, isobutene, and diisobutene. And a polymer containing at least one structural unit derived from the monomer (II). A diisobutylene / maleic acid copolymer and an isobutylene / maleic anhydride copolymer are particularly preferable.

The polymer compound (b) used in the present invention 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 from 0.01 to 0.5 MPa, more preferably from 0.05 to 0.2 MPa. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen.
Polymerization initiators include persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate, azo compounds such as azobis-2-methylpropionamidine hydrochloride, azoisobutyronitrile, benzoyl peroxide, lauroyl peroxide, etc. Peroxides and the like can be used.
As the polymerization solvent, water is preferable, but from the viewpoint of uniformly dissolving the plurality of monomers, it is 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, and ketones such as acetone and methyl ethyl ketone. Etc.

In the polymer compound, the molar ratio of the monomer structural unit (I) to the monomer structural unit (II) [monomer structural unit (I) / monomer structural unit (II)] is preferably from the viewpoint of solubility and cleaning performance. 20/80 to 90/10, more preferably 30/70 to 90/10, 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 polymer compound has a mass average molecular weight of 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.

In the method for producing an amine oxide powder of the present invention, the component (a) is mixed in an amount of 5 to 80% by mass, the component (b) is mixed in an amount of 95 to 20% by mass, preferably the component (a) is mixed in an amount of 10 to 80% by mass, 90 to 20% by mass of component (b) is mixed, more preferably 15 to 80% by mass of component (a), and 85 to 20% by mass of component (b), more preferably (a). 20 to 75% by mass of component and 80 to 25% by mass of component (b), more preferably 25 to 45% by mass of component (a) and 75 to 55% by mass of component (b) Mix with.
In this case, the mass ratio of [component (a) / component (b)] is 4 or less, preferably 2 or less, more preferably 1 or less, from the viewpoint of amine oxide powderization.

<Oil-absorbing powder (c)>
In the production method of the present invention, the oil-absorbing powder (c) can be mixed from the viewpoint of more easily promoting amine oxide powder or granulation. As the oil-absorbing powder (c), one or more selected from amorphous silica, dextrin, soda ash, bouche and the like can be used. For extrusion granulation, amorphous silica, vacuum rolling granulation, Soda ash is more preferable for rolling granulation.
Specific examples of the amorphous silica include, for example, JP-A-62-191417, page 2, lower right column, line 19 to page 5, upper-left column, line 17, JP-A-62-119119, page 2, lower right. Column 20 line to page 5 upper left column line 11 and disclosed in JP-A-9-132794, JP-A-7-10526, JP-A-6-227811, and JP-A-8-119622. Amorphous silica etc. are mentioned.
Commercially available amorphous silica includes Tokuseal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210 to 270 mL / 100 g), Florite (manufactured by Tokuyama Corporation, oil absorption capacity: 400 to 600 mL / 100 g), TIXOLEX 25 (Korean / France) And the like, manufactured by Kagaku Co., Ltd., oil absorption capacity: 220 to 270 mL / 100 g), and Silo Pure (manufactured by Fuji Silysia Co., Ltd., oil absorption capacity: 240 to 280 mL / 100 g).
Examples of commercially available soda ash include dense ash (manufactured by Central Glass Co., Ltd., oil absorption capacity 15 ml / 100 g), light ash (manufactured by Central Glass Co., Ltd., oil absorption capacity 50 ml / 100 g), and the like.

Examples of the dextrin include those obtained by hydrolyzing starch derived from various grains with acid or amylase. There are various degradation products depending on the degree and structure of hydrolysis, and examples include amylodextrin (soluble starch), erythrodextrin, acrodextrin, maltodextrin, and cyclodextrin. Among these, DE values (starch degradation rate = glucose equivalent mass / total solid content mass × 100) are preferably 0.1 to 10, and more preferably 2 to 5. Further, those that dissolve rapidly even in cold water or hot water are preferred, and those having a DE value of 0.1 to 3 are preferred from the viewpoint of alkali resistance.
As the bow show, commercially available products such as A6 bow show manufactured by Shikoku Kasei Co., Ltd. can be used. Among them, those having a particle diameter of 20 μm or less are preferably 90% or more from the viewpoint of solubility.
The mixing amount of the oil-absorbing powder (c) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and still more preferably with respect to 100 parts by weight of the total amount of the components (a) and (b). Is 30 to 80 parts by mass.

<Binder (d)>
In the present invention, the binder (d) can be mixed from the viewpoint of improving the strength of the amine oxide powder or granule.
Although it does not specifically limit as a binder (d), A thermoplastic water-soluble binder is preferable. As the thermoplastic water-soluble binder, one or more selected from polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether and the like can be used.
The number average molecular weight of the binder (d) such as polyethylene glycol is a GPC method using polystyrene (solvent: water / ethanol) as a standard from the viewpoint of viscosity adjustment when powdering or granulating, preferably 4,000. 20,000 to 20,000, more preferably 6,000 to 13,000, and still more preferably 7,000 to 9,000.
The mixing amount of the binder (d) is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, and still more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). 80 parts by mass.

<Other optional components>
In the method for producing an amine oxide powder of the present invention, in addition to the components (a) to (d), other optional components that can be used in ordinary cleaning agents can be blended. Examples of other optional components include antifoaming agents, extenders or diluents, surface modifiers, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial / antifungal agents, and dyes.
As the antifoaming agent, polypropylene glycol having a mass average molecular weight of preferably 600 to 20,000, more preferably 2,000 to 12,000 is preferable from the viewpoint of 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.
Examples of the extender or diluent include sulfates such as sodium sulfate and magnesium sulfate. If a filler or diluent is added, each component can be diluted and dispersed at an appropriate concentration, so that it can be designed in an amount suitable for use, and also to maintain the stability of each component. It is valid.
Examples of the surface modifier include bentonite and zeolite. In addition, amorphous silica which is one type of oil-absorbing powder (c) (manufactured by Tokuyama Corporation, trade name: Tokuseal, etc.) can also be used as a surface modifier.

<Production of amine oxide powder>
The amine oxide powder of the present invention is obtained by mixing the components (a) and (b), the components (a) to (c), or the components (a) to (d), and other optional components. Obtainable.
As the component (a), an aqueous solution or suspension containing 10 to 60% by mass of amine oxide is concentrated in advance, and 50 to 95% by mass of amine oxide, preferably 60 to 95% by mass, more preferably 70 to 95% by mass. It is possible to facilitate the production of amine oxide powders and granules by preparing an aqueous solution, suspension or paste having a concentration as high as possible. Moreover, if a high concentration (a) component is used, the powder and granule physical property obtained after mixing with (b) component will be improved.
When the component (a) previously concentrated to a desired water content is used, the components (a) and (b), the components (a) to (c), the components (a) to (d), and others By mixing these optional components, an amine oxide powder can be easily obtained.

When the component (a) is used without prior concentration as described above, the component (a) is the component (b), the components (b) to (c), the components (b) to (d), and other optional components. A method of removing moisture from the component (a) while adding to the component, the components (a) and (b), the components (a) to (c), or the components (a) to (d), and The method of removing the water | moisture content of (a) component at the time of mixing other arbitrary components is preferable. There is no particular limitation on the method for removing moisture, and examples include a method for removing moisture by heating, a method for removing moisture under reduced pressure, and a method for removing moisture under ventilation conditions.
For example, when mixing with a Nauter mixer, a method of removing moisture by heat transfer from the jacket warm water of the Nauter mixer, a method of removing moisture by passing dry air through the Nauter mixer, etc. are effective. When dry air is used, the temperature of the dry air is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and most preferably 100 ° C. or lower from the viewpoints of energy cost and environmental load. On the other hand, from the viewpoint of moisture removal efficiency, the temperature of the dry air is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and most preferably 90 ° C. or higher. From the viewpoint of moisture removal efficiency, it is preferable to use dry air having a humidity of 0% as the dry air.
The blending order of each component is not particularly limited, but from the viewpoint of powder physical properties, a method of mixing the component (a) and the component (b) and then mixing with the other components is preferable. Here, when the component (d) is a solid, a part or all of the component (d) may be melted in advance, or may be mixed as a solid and melted inside the mixer. Moreover, you may improve a powder physical property using a surface modifier during mixing and / or after mixing.
Although the temperature at the time of mixing each component of this invention is not specifically limited, 100 degreeC or less is preferable from a viewpoint of stability and energy saving of (a) component, and 90 degreeC or less is more preferable.

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.) and the like can be used.

<Manufacture of amine oxide granules>
The amine oxide granule according to the present invention comprises the component (a) and the component (b), the components (a) to (c), the components (a) to (d), and other optional components. It can be obtained by granulating after mixing with a machine or simultaneously with mixing. Moreover, it can also shape | mold into a tablet shape using a tableting machine etc.
As the component (a), an aqueous solution or suspension containing 10 to 60% by mass of amine oxide is concentrated in advance, and 50 to 95% by mass of amine oxide, preferably 60 to 95% by mass, more preferably 70 to 95% by mass. It is possible to facilitate the production of amine oxide powders and granules by keeping them as high concentration aqueous solution, suspension or paste as possible, and the powder and granule properties after mixing with the component (b) are improved. The

When the component (a) previously concentrated to a desired water content is used, the components (a) and (b), the components (a) to (c), the components (a) to (d), and others Amine oxide granules can be easily obtained by mixing these optional components or by granulating simultaneously with the mixing.
When the component (a) is used without prior concentration as described above, the component (a) is the component (b), the components (b) to (c), the components (b) to (d), and other optional components. A method of removing moisture from the component (a) while adding to the component, the components (a) and (b), the components (a) to (c), or the components (a) to (d), and The method of removing the water | moisture content of (a) component is preferable, mixing other arbitrary components or granulating simultaneously with mixing.

Examples of the granulation method include extrusion granulation method, rolling granulation method, vacuum rolling granulation method, crushing granulation method, fluidized bed granulation method, spray granulation method, crushing granulation method and the like. The extrusion granulation method, the rolling granulation method, and the vacuum rolling granulation method are more preferable.
When the component (a) is concentrated in advance, amine oxide granules having good powder properties can be obtained by any of the above granulation methods.
When the component (a) is used without concentrating as described above, amine oxide granules having good powder properties can be obtained by extrusion granulation method, rolling granulation method, and vacuum rolling granulation method.

(Extrusion granulation method)
In the case of the extrusion granulation method, it is preferable to remove moisture of the component (a) in the mixing step before granulation. There is no particular limitation on the method for removing moisture, and examples include a method for removing moisture by heating, a method for removing moisture under reduced pressure, and a method for removing moisture under ventilation conditions.
For example, when mixing with a Nauter mixer, a method of removing moisture by heat transfer from the warm water of the Nauter mixer jacket, a method of removing moisture by reducing the pressure in the Nauter mixer to facilitate moisture evaporation, Nauter A method of removing moisture by passing dry air through a mixer is effective. When dry air is used, the temperature of the dry air is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 100 ° C. or lower from the viewpoints of energy cost and environmental load. On the other hand, from the viewpoint of moisture removal efficiency, the temperature of the dry air is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and most preferably 90 ° C. or higher. From the viewpoint of moisture removal efficiency, it is preferable to use dry air having a humidity of 0% as the dry air. In the case of removing water with the Nauta mixer under reduced pressure conditions, the reduced pressure conditions will be described in detail in the column of the vacuum rolling granulation method.
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 diameter of the extrusion screen is preferably 0.3 to 2.0 mm, more preferably 0.5 to 2.0 mm, and still more preferably 0.5 to 1.0 mm, and forms such as a cylindrical or noodle-shaped granule Can be extruded.

(Rolling granulation method)
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. Also in the case of rolling granulation, if moisture removal is necessary, a method of removing moisture by heat transfer from the jacket warm water, a method of removing moisture by reducing the pressure in the stirring rolling granulator to facilitate moisture evaporation For example, a method of removing moisture by passing dry air through a stirring tumbling granulator is effective.
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.

(Vacuum rolling granulation method)
In the case of the vacuum rolling granulation method, for example, when using a high speed mixer attached with a vacuum unit, the temperature and pressure in the vacuum rolling machine can evaporate water in the component (a) at the moment when the component (a) is added. It is desirable to make it a condition.
Further, as a method of adding the component (a), spraying is performed for the purpose of facilitating evaporation, and the component (b), the components (b) to (c), or the components (b) to (d) are added. It is effective to mix or granulate at the same time as mixing while adding to the component and other optional components. The removal of water from component (a) may be carried out in any step during spraying of component (a), mixing, or granulation.
The pressure in the vacuum rolling machine is preferably 20 kPa or less, more preferably 10 kPa or less, more preferably 5 kPa or less, and even more preferably 3 kPa or less from the viewpoint of facilitating the evaporation of moisture. The temperature in the vacuum rolling machine is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher from the viewpoint of facilitating moisture evaporation. Moreover, from a viewpoint of stability of component (a) and energy saving, 100 degrees C or less is preferable, 90 degrees C or less is more preferable, and 70 degrees C or less is still more preferable. Moreover, you may improve a powder physical property using a surface modifier during mixing and / or after mixing.

Further, 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).

<Cleaning composition for automatic dishwasher>
The amine oxide powder or granule produced by the method of the present invention is useful as a component of a cleaning composition, and the cleaning composition containing this is used as a cleaning agent for tableware, clothing, dwelling, etc. It can be used preferably, and is particularly suitable as a cleaning composition for an automatic dishwasher.
The cleaning composition for an automatic dishwasher of the present invention comprises an aqueous solution, suspension or paste (a) containing 50 to 95% by mass of the amine oxide represented by the general formula (1), and 5 to 80% by mass. And an amine oxide powder or granule obtained by mixing 95% to 20% by mass of the powder (b) comprising the polymer compound, and (e) an alkali agent and / or a sequestering agent. And
In the detergent composition for an automatic dishwasher of the present invention, as the component (e), an alkali agent (hereinafter also referred to as (e-1) component) and / or a sequestering agent (hereinafter also referred to as component (e-2)). ], The effect of the amine oxide powder or granule which consists of (a) component and (b) component can fully be exhibited.

<(E) Alkaline agent and / or sequestering agent>
(E-1) Examples of the alkaline agent include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, alkali metal silicate, crystalline layered sodium silicate (trade name, manufactured by Tokuyama Siltec Co., Ltd. : Pre-feed) and the like, and an amorphous material can be used. The alkaline agent is preferably a powder, but may be one having a particle diameter or bulk density adjusted by a granulation process or the like. In these, an alkali metal carbonate is preferable and sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate are more preferable.
Moreover, an amine compound can also be used as an alkali agent. As the amine compound, alkanolamine is preferable, primary alkanolamine is more preferable, and monoethanolamine is more preferable.

(E-2) The sequestering agent is preferably a phosphate such as sodium tripolyphosphate. When used as 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, 1, 3 -Propanediaminetriacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethyl A polycarboxylic acid such as glutamic acid or a salt thereof is used. Among these, citric acid, succinic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamine, and alkali metal salts thereof are preferable.
The component (e) preferably contains both the component (e-1) and the component (e-2). In this case, the mass ratio of [(e-1) / (e-2)] is preferably 0.1 to 100, more preferably 0.2 to 20, and still more preferably 0.2 to 10.

<(F) Surfactant>
The detergent composition for an automatic dishwasher of the present invention may contain (f) a surfactant other than the component (a) [hereinafter also referred to as the component (f)]. Examples of the component (f) include nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants, and nonionic surfactants are particularly preferable. The anionic surfactant is preferably not contained because it tends to increase the foamability and inhibit the effects of the present invention from the relationship with the component (a).
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 Group or monoalkenyl group-containing nonionic surfactant mixture, ethylene oxide condensed surfactant, alkyl glyceryl ether, alkyl glycoside and the like. Among these, polyoxyalkylene alkyl ether is preferable, polyoxyethylene monoalkyl or monoalkenyl ether, wherein the average number of carbon atoms of the alkyl group or alkenyl group is 4 to 12, and the average number of moles of ethylene oxide added is Those having 1 to 20 moles are preferred.

<Other cleaning auxiliary ingredients>
The cleaning composition for an automatic dishwashing machine of the present invention can contain a known cleaning auxiliary component such as a bleaching agent, a bleaching activator, an enzyme, and a polymer other than the component (b).
The bleaching agent is preferably a solid substance that generates hydrogen peroxide or peracid species by dissolution, and includes sodium percarbonate, sodium perborate granules, etc., and the bleach activator includes tetraacetylethylenediamine. Alkanoyloxybenzenecarboxylic acid or a salt thereof, alkanoyloxybenzenesulfonate, and the like.
Examples of the enzyme include granulated substances such as protease, amylase, lipase, cellulase, esterase and peroxidase. Amylase is preferable because it has an action on gelatinized starch and protease has an action on denatured proteins and the like.
As the polymer other than the component (b), polyalkylene glycol, particularly polypropylene glycol, an amphoteric polymer containing a monomer constituent unit having a cationic group and a monomer constituent unit having an anionic group, Examples include crosslinked polyacrylic acid. Among these, polypropylene glycol having a weight average molecular weight of 600 to 20000, preferably 2000 to 12000 is preferable from the viewpoint of cleaning effect and low foamability.
In addition, extenders or diluents, organic solvents such as glycerin and ethanol, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial / antifungal agents, dyes, and the like can be added.

The content of each component in the cleaning composition for an automatic dishwasher of the present invention is as follows from the viewpoint of detergency and the like.
The content of the amine oxide powder or granule is preferably 1.0 to 90% by mass, more preferably 2.0 to 80% by mass, and still more preferably 5.0 to 70% by mass.
The content of the (e-1) alkali agent is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and the content of the (e-2) sequestering agent is preferably 1 to 50% by mass. More preferably, it is 1 to 30% by mass.
The content of (f) surfactant is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, and still more preferably 0.2 to 5% by mass. The mass ratio of the component (a) to the component (f) [component (a) / component (f)] is preferably 0.3 to 10, more preferably 0.5 to 6, and further preferably 1 to 5. It is.
The content of the bleaching agent is preferably 0 to 40% by mass, the content of the bleach activator is preferably 0 to 5% by mass, and the content of the enzyme is preferably 0 to 2% by mass. Further, the content of the polymer other than the component (b) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and further preferably 1 to 5% by mass.

The cleaning composition for an automatic dishwashing machine of the present invention may be either liquid or solid. The liquid includes a fluid state such as a gel, and the solid includes a granular or tablet shape.
Examples of the solid composition include (e-1) 10 to 50% by mass of an alkali agent such as sodium carbonate and sodium metasilicate, and (e-2) 5 to 30% by mass of a sequestering agent such as citrate. In addition, 0 to 40% by mass of bleaching agents such as sodium percarbonate, 0 to 5% by mass of bleach activators such as TAED, 0 to 2% by mass of enzymes such as protease and amylase, and high molecular polymers such as polypropylene glycol 0 to Examples include 5% by mass, a composition containing a necessary amount of a filler or diluent such as sodium sulfate, and a fragrance. In the case of a solid composition, the pH (20 ° C.) of the 0.2 mass% aqueous solution is preferably 8.0 to 12.0, and more preferably 8.5 to 12.0.
Examples of the liquid composition include (e-1) 1 to 10% by mass of an alkaline agent such as monoethanolamine, (e-2) 1 to 20% by mass of a sequestering agent such as citric acid and EDTA, protease and amylase. Enzymes such as 0 to 2% by mass, other organic solvents such as glycerin and ethanol, 5 to 50% by mass, enzyme stabilizers such as calcium chloride, 0 to 2% by mass, bulking agents such as water, and necessary amounts The composition contained in is mentioned. In the case of a liquid composition, the balance is usually water, and the pH (20 ° C.) is preferably 7.0 to 12.0, more preferably 8.0 to 12.0.

In the following Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.
The particle strength, water-insoluble matter, and breaking load, bulk density, fluidity, and productivity of the obtained particles were measured, calculated, or evaluated by the following methods. Moreover, the washing | cleaning performance and low-foaming property evaluation of the cleaning composition for automatic dishwashers were performed as follows.

(1) Particle Strength The particle strength of each particle was measured in a 25 ° C. environment using “PARTICLE HARDNESS TESTER GRANO” manufactured by Okada Seiko Co., Ltd.
(2) Water-insoluble matter 1 L of 40 ° C. 3.5 ° hard water was poured into a beaker, 0.4 g of amine oxide powder was added while stirring with a magnetic stirrer, and the mixture was stirred for 10 minutes. Next, the undissolved amine oxide particles are collected with a 200 μm mesh wire mesh, dried at 105 ° C. for 1 hour, the mass of the undissolved amine oxide particles is measured, and the water insoluble content (%) is obtained by the following formula. Calculated.
Water insoluble content (%) = [mass of undissolved amine oxide particles after drying (g) /0.4] × 100
(3) Breaking load Attach an adapter with a diameter of 30 mm to a rheometer (manufactured by Rheotech Co., Ltd.), set 30 g of amine oxide powder or granules in a metal cylindrical container, and apply a load of 1 kg / cm 2 (9800 mN) at 25 ° C. Compress for 3 minutes. 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.

(4) Bulk density The bulk density is measured by a method defined in JIS K 3362.
(5) Fluidity The fluidity is measured as follows. The time required for 100 mL of amine oxide powder or granules to flow out of the bulk density measurement hopper defined by JIS K 3362.
(6) Productivity Productivity was evaluated according to the following criteria.
(Double-circle): The physical property of the obtained amine oxide powder or granulated material is stable. It is very stable without any trouble during production.
○: The physical properties of the obtained amine oxide powder or granulated product are stable. Production is also stable.
(Triangle | delta): The physical property of the obtained amine oxide powder or granulated material is unstable. There are many troubles in production and stable operation is not possible.
X: Production is impossible.

(7) Protein stain cleaning performance Contaminated dishes were cleaned with an automatic dishwasher under the following cleaning conditions.
This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of the type that is dried after being warmed).
Three contaminated dishes were used and arranged vertically on the upper plate of the dish washer. At that time, the interval between the first and second sheets was 13 mm, and the interval between the second and third sheets was 5 mm. Further, five dishes (obstruction dishes) with a diameter of 230 mm were arranged at equal intervals of 25 mm on the lower stage of the tableware receiver. In addition, the space | interval of a dish here is the distance from the bottom part of the outer surface (back surface) of one dish to the edge of the other inner surface (surface).
This test assumes a non-ideal condition in which the distance between adjacent dishes is reduced, and at the same time assumes a situation in which it is difficult for water to flow due to the installation of obstacle dishes.
For the contaminated dish, measure the mass of the dish before contamination (M1), the weight of the dish before washing (M2), and the weight of the dish after washing (M3), and calculate the protein stain washing rate by the following formula. The average value of the cleaning rate of the first contamination dish was determined.
Protein stain washing rate (%) = (M2-M3) / (M2-M1) × 100
(Cleaning conditions)
Contaminated dish: 0.7 g of egg yolk was applied as uniformly as possible to a ceramic dish with a diameter of 103 mm and denatured at 115 ° C. for 1 hour. Water used: 3.5 ° DH water Washing machine: Automatic dishwashing made by Matsushita Electric Industrial Co., Ltd. Machine (model NP-60SS5)
Cleaning course: Standard course Amount of cleaning composition added: 6 g per 2.2 liters of water

(8) Evaluation of low foaming property Using an automatic dishwasher (model NP-C10) manufactured by Matsushita Electric Industrial Co., Ltd., a detergent composition to be used for evaluation and 5 g of egg yolk were put in and operated on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of a type that dries after warming and rinsing).
After 1 minute, 4 minutes, 9 minutes, 14 minutes, and 19 minutes from the start of operation, the number of revolutions of the spray nozzle (spray arm) was counted while applying light from the upper part of the washing machine. The higher the number of rotations, the more the foam composition becomes an indicator of low foaming properties.

Example 1
80% of an aqueous solution (a) of lauryldimethylamine oxide having a concentration of 50% (in the general formula (1), R ¹ is an n-octyl group, R ² and R ³ are methyl groups), diisobutylene / maleic acid copolymer Combined powder (b) (diisobutylene / maleic acid (molar ratio) = 50/50, manufactured by Rohm and Haas, trade name: ACUSOL460ND, mass average molecular weight 15,000, effective content 84%) 20% and high The mixture was charged into a speed mixer (trade name: LFS-2 (total volume: 2 L), manufactured by Fukae Powtech Co., Ltd.) and mixed for 1 minute under the conditions of an agitator rotation speed of 850 rpm and a chopper rotation speed of 1350 rpm to obtain a powder.
Example 2
Example 1 was the same as Example 1 except that the aqueous solution (a) of lauryldimethylamine oxide was 60% and the powder (b) of diisobutylene / maleic acid copolymer (trade name: ACUSOL460ND) was 40%. Was performed.
Example 3
Example 1 was the same as Example 1 except that the aqueous solution (a) of lauryldimethylamine oxide was 50% and the powder (b) of diisobutylene / maleic acid copolymer (trade name: ACUSOL460ND) was 50%. Was performed.
Example 4
Example 1 was the same as Example 1 except that the aqueous solution (a) of lauryldimethylamine oxide was 30%, and the powder (b) of diisobutylene / maleic acid copolymer (trade name: ACUSOL460ND) was 70%. Was performed.

Example 5
50% aqueous solution of lauryldimethylamine oxide (a) 20%, diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL460ND) 25%, and amorphous silica (c) (Tokuyama Corporation) (Product name: Tokusir NR) 27% was charged into a Nauta mixer (Hosokawa Micron Corporation) and mixed at a jacket temperature of 90 ° C. for 20 minutes. Here, 28% of polyethylene glycol (d) melted in advance (trade name: K-PEG6000LA, manufactured by Kao Corporation) was added and further mixed for 20 minutes, and then the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm using an extrusion granulator (Dalton Co., Ltd .: Pelleter Double EXD-100 type) to obtain a granulated product. Further, the granulated product was cooled and then pulverized with a granulator (Pauleck Co., Ltd .: Power Mill) to obtain granules.
Example 6
In Example 5, 20% aqueous solution of lauryldimethylamine oxide (a), 25% diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL460ND), 24% amorphous silica (c) The same operation as in Example 5 was carried out except that 23% of polyethylene glycol (d) and 8% of polypropylene glycol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: Preminol S4011) were used as optional components.
Example 7
In Example 6, 26% of aqueous solution (a) of lauryldimethylamine oxide, 26% of powder (b) of diisobutylene / maleic acid copolymer (trade name: ACUSOL460ND), 20% of amorphous silica (c) The same operation as in Example 6 was carried out except that 20% of polyethylene glycol (d) and 8% of polypropylene glycol (trade name: Preminol S4011) were used as optional components.

Example 8
Diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL 460ND) 17%, (c) sodium carbonate (product name: Dens ash) 62% Nauta mixer (manufactured by Hosokawa Micron) The jacket temperature was 90 ° C. and mixed for 5 minutes. Here, 5% of polypropylene glycol (trade name: Preminol S4011) as an optional component was added and mixed for 20 minutes. Next, using a continuous thin film dryer (trade name: Hi-U Brusher, manufactured by Kansai Chemical Machinery Co., Ltd.), an aqueous solution of lauryldimethylamine oxide having a concentration of 50% was concentrated to a concentration of 78%. Then, after further mixing for 20 minutes, 7% of amorphous silica (trade name: Toxeal NR, manufactured by Tokuyama Corporation) was added as a surface modifier and mixed for 5 minutes to obtain an amine oxide powder.

Example 9
Diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL 460ND) 15%, (c) sodium carbonate (manufactured by Central Glass Co., Ltd., trade name: dense ash) 62% high speed mixer (Fukae Powtech Co., Ltd.) And the jacket temperature was 65 ° C. and mixed for 5 minutes. Here, 5% of polypropylene glycol (trade name: Preminol S4011) as an optional component was added and mixed for 5 minutes. Next, using a continuous thin film dryer (trade name: Hi-U Blusher), an aqueous solution of lauryl dimethylamine oxide having a concentration of 50% is concentrated to 74% concentration of paste (a) 9.5% over 30 minutes. After mixing and granulating while adding, 8% of amorphous silica (trade name: Toxeal NR) was added as a surface modifier and mixed for 5 minutes to obtain amine oxide granules.

Example 10
Paste (a) 13%, diisobutylene / maleic acid obtained by concentrating an aqueous solution of lauryldimethylamine oxide having a concentration of 50% to a concentration of 77% using a continuous thin film dryer (Hi-U blusher manufactured by Kansai Chemical Machinery Co., Ltd.) Copolymer powder (b) (trade name: ACUSOL 460ND) 25%, amorphous silica (c) (trade name: Toxeal NR) 33%, and polypropylene glycol (trade name: Preminol S4011) 8% as an optional component Was placed in a Nauta mixer (Hosokawa Micron Corporation) and mixed at a jacket temperature of 90 ° C. for 20 minutes. Here, 21% of pre-melted polyethylene glycol (d) (trade name: K-PEG6000LA) was added and further mixed for 20 minutes, and then the mixture was extracted. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm using an extrusion granulator (Dalton Co., Ltd .: Pelleter Double EXD-100 type) to obtain a granulated product. Further, the granulated product was cooled and then pulverized with a granulator (Pauleck Co., Ltd .: Power Mill) to obtain granules.

Example 11
High-speed mixer with 15% diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL 460ND) and (c) 62% sodium carbonate (trade name: dense ash), with vacuum unit (Fukae Powtech Co., Ltd.) was charged and mixed at a jacket temperature of 65 ° C. and a vacuum of 3 kPa for 5 minutes. Here, 5% of polypropylene glycol (manufactured by Asahi Glass Urethane Co., Ltd., trade name: Preminol S4011), which is an optional component, was added and mixed for 5 minutes. Next, 14% of an aqueous solution of lauryldimethylamine oxide (a) having a concentration of 50% was mixed and granulated while charging over 40 minutes, and then amorphous silica (trade name: manufactured by Tokuyama Corporation) as a surface modifier. After adding 8% of Toxeal NR) and mixing for 5 minutes, amine oxide granules were obtained. By vacuum rolling granulation, 36% of the total water content of component (a) was evaporated.

Example 12
20% aqueous solution of lauryldimethylamine oxide (a) having a concentration of 50%, amorphous silica (c) (trade name: Toxeal NR) 33%, and polypropylene glycol (trade name: Preminol S4011) 8% as an optional component The mixture was charged into a termixer (Hosokawa Micron Co., Ltd.), the jacket temperature was 90 ° C., and the mixture was mixed for 360 minutes while flowing 90 ° C. dry air from the top of the Nauter mixer at 10 m ³ / min. Next, 25% of diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL460ND) was added and mixed for 5 minutes, and then melted in advance to polyethylene glycol (d) (trade name: K- PEG6000LA) was added at 21%, and further mixed for 20 minutes, and then the mixture was extracted. By passing dry air, 70% of the total water content of component (a) was evaporated. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm using an extrusion granulator (Dalton Co., Ltd .: Pelleter Double EXD-100 type) to obtain a granulated product. Further, the granulated product was cooled and then pulverized with a granulator (Pauleck Co., Ltd .: Power Mill) to obtain granules.

Comparative Example 1
An aqueous solution of lauryldimethylamine oxide with a concentration of 50% (a), 85% diisobutylene / maleic acid copolymer powder (b) (trade name: ACUSOL460ND) and a high-speed mixer (Fukae Powtech Co., Ltd., product) Name: LFS-2 (total volume: 2 L)) and mixed under the conditions of an agitator rotation speed of 850 rpm and a chopper rotation speed of 1350 rpm, but became a slurry and did not become powder.
Comparative Example 2
Except for using 80% of an aqueous solution of lauryldimethylamine oxide having a concentration of 5% (referred to as (a ′)) and 20% of powder (b) of diisobutylene / maleic acid copolymer (trade name: ACUSOL460ND), The same operation as in Comparative Example 1 was performed, but the slurry was not powdered.

Comparative Example 3
30% aqueous solution (a) of 50% lauryl dimethylamine oxide and 70% zeolite (trade name: Toyo Builder (4A type, average particle size: 3.5 μm) manufactured by Tosoh Corporation) at high speed The mixture was charged into a mixer (manufactured by Fukae Powtech Co., Ltd.) and mixed for 1 minute under the conditions of an agitator rotation speed of 850 rpm and a chopper rotation speed of 1350 rpm to obtain a powder. The obtained powder had poor solubility, and a large amount of water-insoluble matter was detected.
Comparative Example 4
In Comparative Example 3, Comparative Example 3 except that 30% of the aqueous solution (a) of lauryldimethylamine oxide and 70% of silicate (made by Tokuyama Siltec Co., Ltd., crystalline silicate, trade name: Prefeed) were used. The same operation was performed to obtain a powder.

Table 1 shows that according to the method of the present invention, amine oxide powders or granules having excellent solubility can be efficiently produced.

Example 13
In order to examine the difference in effect due to the difference in carbon number of amine oxide, 2% by mass of linear alkyldimethylamine oxide having different carbon number of the alkyl group shown in Table 2 and 5% by mass of isobutylene / maleic anhydride copolymer , 7% by weight of sodium carbonate, 20% by weight of sodium citrate, 5% by weight of silicate, 20% by weight of sodium percarbonate, 0.5% by weight of amylase, 1% by weight of protease, and the rest of the anhydrous dishwashing powder. A machine cleaning composition was obtained. The cleaning performance of these cleaning compositions was examined by the evaluation method. The results are shown in Table 2.
The isobutylene / maleic anhydride copolymer has an isobutylene / maleic anhydride molar ratio of 50/50 and a weight average molecular weight of 6000 (manufactured by Kuraray Co., Ltd., Isoban 600L), and silicate is a crystalline silicate (pre-polymer). Feed (trade name), manufactured by Tokuyama Siltech Co., Ltd., sodium percarbonate coated with sodium metaborate, amylase with Duramil 120T (trade name) (Novo Nordisk Bio Industry Co., Ltd.) having an average particle size of 600 μm, As the protease, sabinase 18.0T (trade name) (Novo Nordisk Bio Industry Co., Ltd.) having an average particle diameter of 600 μm was used.

For tableware placed with the distance between the dishes narrow, amine oxides having 4 to 8 carbon atoms in the alkyl group, particularly amine oxides having 6 or 8 carbon atoms, showed a remarkable detergency.

Examples 14 to 25 and Comparative Examples 5 to 10
Cleaning agents for automatic dishwashers having the compositions shown in Tables 3 and 4 were evaluated.
In manufacturing the cleaning composition, among the components shown in Tables 3 and 4, first, powder components other than enzyme components are mixed, and liquid components such as amine oxide and nonionic surfactant are added thereto and mixing is continued. Finally, the enzyme component was added.

Details of the components in Tables 3 and 4 are as follows.
Isobutylene / maleic anhydride copolymer: isobutylene / maleic anhydride = 50/50 (molar ratio), weight average molecular weight = 6000, Kuraray Co., Ltd. Isoban 600L
Diisobutylene / maleic acid copolymer: diisobutylene / maleic acid = 50/50 (molar ratio), weight average molecular weight = 12000, Sokalan CP9 manufactured by BASF
-Acrylic acid / maleic acid copolymer: acrylic acid / maleic acid = 70/30 (molar ratio), weight average molecular weight = 70,000, Socaran CP45 manufactured by BASF
Styrene / maleic acid copolymer: styrene / maleic acid = 50/50 (molar ratio), weight average molecular weight = 7000
・ Silicate: Crystalline silicate (Prefeed (trade name), manufactured by Tokuyama Siltech Co., Ltd.)
・ Nonionic surfactant (1): Nonionic surfactant obtained by adding an average of 4 moles of ethylene oxide to a linear primary alcohol having 12 carbon atoms. ・ Nonionic surfactant (2): Linear chain having 8 carbon atoms. Nonionic surfactant with 3 moles of ethylene oxide added to primary alcohol on average. Sodium percarbonate: Sodium percarbonate whose surface is coated with sodium metaborate. Average particle size 700μm
Protease: Sabinase 18.0T (trade name) (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm
Amylase: Duramil 120T (trade name) (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm

Tables 3 and 4 show that the cleaning composition of the present invention exhibits sufficient cleaning power even under non-ideal conditions where the distance between dishes is short.

Examples 26-36
The formulation examples shown in Table 5 show cleaning compositions in which optional components are further added in order to further improve the detergency. Manufacturing of the cleaning composition of Table 5 was performed based on the above-described production method, but after adding liquid components other than the fragrance, amorphous silica was added and mixed, and then the fragrance was added. And an enzyme and then a bleaching agent were added, and the powdery cleaning composition of Table 5 was obtained.

The components in Table 5 used the above components and the following.
Amorphous silica: Toxeal NR (trade name) (oil absorption capacity: 210 to 270 mL / 100 g, primary particle diameter of about 20 nm, manufactured by Tokuyama Corporation)
The cleaning compositions in Table 5 also showed excellent cleaning performance even when the dishwashing was packed in an automatic dishwashing machine.

According to the method of the present invention, it is possible to provide an efficient method for producing an amine oxide powder or granule excellent in solubility, and a cleaning composition for an automatic dishwasher containing the amine oxide powder or granule.
Since the production method of the present invention does not require a large amount of heat energy, it is advantageous in industrial production and has excellent solubility from the viewpoint of the stability, production cost and environmental load of the resulting amine oxide powder or granule. .
The cleaning composition for an automatic dishwasher of the present invention satisfies both excellent stain removal properties and low foaming properties at the same time. Therefore, the composition of the present invention has excellent detergency even under non-ideal conditions such as when tableware is excessively stored in an automatic dishwasher or when tableware is stacked and stored. Indicates.

Claims (18)

1. An aqueous solution, suspension or paste (a) containing 50 to 95% by mass of an amine oxide represented by the following general formula (1):
   A structural unit derived from a compound having a carboxylic acid group and / or a carboxylic acid anhydride residue, and a structural unit derived from an aliphatic hydrocarbon having 3 to 10 carbon atoms having a polymerizable unsaturated bond in all the structural units. A method for producing an amine oxide powder, comprising mixing 95 to 20% by mass of a powder (b) comprising a polymer compound containing 80 mol% or more in total.
   

   

   (Wherein R ¹ represents a hydrocarbon group having 3 to 8 carbon atoms, and R ² and R ³ each independently represents 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 aqueous solution or suspension containing 10 to 60% by mass of the amine oxide represented by the general formula (1) is concentrated in advance, and an aqueous solution, suspension or paste containing 50 to 95% by mass of amine oxide (a) The method for producing an amine oxide powder according to claim 1, wherein the amine oxide powder is mixed with the powder (b).
3. While adding the aqueous solution, suspension or paste (a) to the powder (b) and / or mixing the aqueous solution, suspension or paste (a) and the powder (b), the aqueous solution, The manufacturing method of the amine oxide powder of Claim 1 which removes the water | moisture content of suspension or paste (a).
4. The method for producing an amine oxide powder according to any one of claims 1 to 3, wherein the mass ratio of [the component (a) / the component (b)] is 4 or less.
5. In the polymer compound, the compound having a carboxylic acid group and / or a carboxylic acid anhydride residue is one or more compounds selected from acrylic acid and salts thereof, maleic acid and salts thereof, and maleic anhydride. The method for producing an amine oxide powder according to any one of claims 1 to 4.
6. 6. The amine oxide according to claim 1, wherein in the polymer compound, the aliphatic hydrocarbon having 3 to 10 carbon atoms is one or more hydrocarbons selected from pentene, octene, isobutene, and diisobutene. Powder manufacturing method.
7. The oil absorbing powder (c) is further mixed at a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). A method for producing the amine oxide powder according to claim 1.
8. The binder (d) is further mixed at a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). A method for producing an amine oxide powder.
9. A method for producing amine oxide granules, in which 5 to 80% by mass of the component (a) and 95 to 20% by mass of the component (b) are mixed or simultaneously granulated.
10. An aqueous solution or suspension containing 10 to 60% by mass of amine oxide was concentrated in advance to obtain an aqueous solution, suspension or paste (a) containing 50 to 95% by mass of amine oxide and mixed with the powder (b). The method for producing amine oxide granules according to claim 9, wherein granulation is performed after or simultaneously with mixing.
11. While adding the aqueous solution, suspension or paste (a) to the powder (b) and / or mixing the aqueous solution, suspension or paste (a) and the powder (b), or simultaneously with mixing. The manufacturing method of the amine oxide granule of Claim 10 which removes the water | moisture content of the said aqueous solution, suspension, or paste (a), granulating.
12. The method for producing amine oxide granules according to claim 9 to 11, wherein a mass ratio of [the component (a) / the component (b)] is 4 or less.
13. The oil-absorbing powder (c) is further granulated after being mixed at a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The method for producing amine oxide granules according to 9 to 12.
14. The binder (d) is further granulated after being mixed at a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (a) and the component (b). The manufacturing method of the amine oxide granule in any one of.
15. The two components (a) to (b), the three components (a) to (c), or the four components (a) to (d) are mixed at 100 ° C. or lower. The manufacturing method of the amine oxide powder or granule in any one.
16. An aqueous solution, suspension or paste (a) containing 50 to 95% by mass of the amine oxide represented by the general formula (1) (a) 5 to 80% by mass, and a powder (b) 95 to 20 comprising the polymer compound A detergent composition for an automatic dishwasher comprising an amine oxide powder or granules obtained by mixing with a mass%, and (e) an alkali agent and / or a sequestering agent.
17. The detergent composition for an automatic dishwasher according to claim 16, further comprising (f) 0.1 to 10% by mass of a surfactant.
18. The cleaning composition for an automatic dishwasher according to claim 16 or 17, wherein [(a) component / (f) component] is 0.3 to 10 in terms of mass ratio.