JPH0959699A - Production of nonionic detergent granule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain nonionic detergent granules having a high bulk density and improved flow characteristics of a powder and caking resistance by granulating a detergent material mixture contg. a nonionic surfactant as the main base material under heating and rolling. SOLUTION: A mixture is prepd. by compunding an org. or inorg. powdery builder which comprises at least one compd. selected from among tripolyphosphates, carbonates, etc., has an average granule size of 500μm or lower, and gives an aq. soln. or dispersion of a concn. of 1g/l having a pH of 8 or higher at 20 deg.C and/or a porous alkaline oil-absorbing carrier with a nonionic surfactant which is a polyoxyethylene alkyl ether formed by the addition reaction of, on average, 5-15mol of ethylene oxide to a 10-20C linear or branched prim. or sec. alcohol and/or an acidic precursor of an anonic surfactant capable of forming a lamella orientation with an aq. soln. of the nonionic surfactant. The mixture is heated to a temp. high enough to enable the neutralization of at least the acidic precursor compounded and then is granulated under rolling, thus giving nonionic degergent granules having a bulk density of 0.6-1.2g/ml.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing nonionic detergent particles. More specifically, it relates to a method for producing nonionic detergent particles having a high degree of freedom of composition, a high bulk density, excellent powder flowability and non-caking property, and no spotting, and a nonionic surfactant as a main base. .

[0002]

2. Description of the Related Art As a method for producing a granular detergent composition containing a nonionic activator, there has been proposed a method for producing a granular detergent composition by blending a nonionic activator with a detergent slurry and spray-drying the mixture. There is. However, with this method,
The equipment cost is high, consumes a lot of energy, and the nonionic activator is decomposed by hot air during drying, which causes problems such as generation of pollutants, reduction of nonionic activator content, and change of activator properties. there is a possibility. In order to solve these problems, the kind and amount of the nonionic activator are limited (JP-A-61-85499), and an additive which does not contribute to cleaning is blended (JP-A-56-22).
No. 394).

Japanese Patent Publication No. 60-21200 proposes a production method in which base beads of a builder are prepared by spray drying and the base beads are loaded with a nonionic activator. However, since this method uses an anhydrous phosphate builder salt as a base material, it is limited to only phosphorus-based detergents, and phosphorus-free detergents cannot be produced. Further, the operation of producing the base material beads having the porous outer surface and the skeleton internal structure is complicated.

In Japanese Patent Publication No. 61-21997,
By using an agglomerator or the like, the washing active salt is hydrated and moistened, and then this is stirred in a closed container, then impregnated with a nonionic activator, an anion activator, etc., and dried,
A continuous method for producing a granular detergent that does not cause caking even after long-term storage has been proposed. However, in this method, a drying step is necessary after the granulation in order to impregnate the agglomerates of the hydrated and moistened cleaning active salt with the active agent, and the steps are not simple. Further, the proportion of the nonionic activator that can be blended is affected by the properties of the agglomerate particles, and therefore, when increasing the proportion of the nonionic activator, it is necessary to prepare highly oil-absorptive agglomerate particles, which does not hydrate. It is not preferable if the amount of salt is increased,
That is, the degree of freedom of the composition as detergent particles is low. Further, there is a problem that the operation (hydration condition, drying condition) in the production is complicated.

In JP-A-3-26795, a zeolite agglomerate is produced from a zeolite and a filler by a binder containing water by using an agglomerate forming device, and further a detergent containing the agglomerate and a surfactant. A method for producing a granular detergent having good fluidity, solubility and dispersibility by forming a detergent agglomerate of components and drying it has been proposed. However, in order to obtain a detergent agglomerate, it is necessary to perform at least 5 steps and the operation in the production is complicated, and it is essential to form an agglomerate (agglomerate) containing zeolite as a main component. There is a problem that the degree of freedom of composition of particles is small.

JP-A-62-263299 proposes a production method in which a nonionic activator and a builder are uniformly kneaded to form a solid detergent and then crushed to obtain a granular detergent composition. However, it is difficult to obtain non-ionic detergent particles having good fluidity by this method, and an undesirably large amount of fine powder is produced. Furthermore, the total amount of zeolite and light sodium carbonate is 50 to 80% by weight,
There is little flexibility in the composition of the nonionic detergent particles.
Further, in JP-A-61-89300, after mixing a water-soluble powder and a silica powder, a nonionic activator is sprayed onto this mixture, and then zeolite or calcium carbonate powder is added to contain the nonionic activator. A method for producing a granulate is described. However, in this method, since the rolling granulation is performed by the drum type granulator in which the drum rotates, it is not possible to manufacture a granulated product containing a nonionic activator having a high bulk density.

Further, in Japanese Unexamined Patent Publication (Kokai) No. 5-209200, a mixture of detergent raw materials containing a nonionic activator as a main base has a stirring shaft equipped with stirring blades at the center, and when the stirring blades rotate. By stirring and mixing with a stirring type mixer that forms a clearance between the stirring blade and the vessel wall,
It describes a method for producing a nonionic activator-containing granulated product by forming an adhering layer of a detergent raw material on the wall of a stirring mixer and granulating the detergent raw material while increasing the bulk density of the detergent raw material. However, in this method, since the nonion is supported by the capillary force and surface adsorption of the powder raw material, the supporting force is weak, and the nonion-containing powder adheres to the equipment in the transport system and the paper box container. When filled in, it is not sufficient to prevent spots from appearing. Further, Japanese Patent Laid-Open No. 4-227700 describes a powder detergent in which spray dried particles containing an anion activator and soap are sprayed with nonion, but a large amount of nonion cannot be blended and stains easily occur. Become.

Further, JP-B-52-30962 is characterized in that a fatty acid or a fatty acid in which a nonionic activator is dissolved is neutralized with water-containing powdery sodium carbonate having a water content of 20% or less at a melting point or higher to 100 ° C. A method of making a heavy powder detergent is described. However, there is not a large amount of nonion, and it is not a method for producing detergent particles having nonion as a main ingredient, and in this method, it is not possible to obtain detergent particles of high bulk density, and since there is no builder or the like, detergent composition There is no degree of freedom. In addition, Japanese Patent Publication No. 6-507197 describes that polyethylene glycol, a copolymer of maleic anhydride and ethylene, a nonionic activator, glycerol ether, a fatty acid and the like can be used as a binder for the granular composition. However, this is only a description that these components can be simply used, and there is no description that an alkaline agent and a fatty acid (acid precursor of an anionic surfactant capable of lamellar orientation) and a nonionic agent are used in combination, There is no suggestion or description regarding the formation of a gelation product with a nonionic activator and its effect.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing nonionic detergent particles, which has a nonionic activator as a main base and which has a high bulk density and is excellent in the powder flow properties and non-caking properties. To provide.

[0010]

Means for Solving the Problems As a result of earnest studies, the present inventors have found that an acid precursor of an anionic surfactant capable of lamellar orientation with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant is alkaline. By neutralizing the acid precursor by blending a builder and an alkaline agent that is a porous oil-absorbing carrier, a gelled product containing a nonionic activator is formed, and this is used as a binder for a detergent with a stirring mixer. The inventors have found that a method for producing nonionic detergent particles by granulating while increasing the bulk density while rolling a mixture of raw materials can solve the above problems, and have completed the present invention.

That is, the gist of the present invention is: (1) The bulk density is 0.6 to 1.2 by the following steps.
A method for producing nonionic detergent particles, characterized in that g / ml nonionic detergent particles are obtained, and step (1): a nonionic activator and / or nonion is added to a builder exhibiting alkalinity and / or a porous oil absorbing carrier exhibiting alkalinity. A step of blending an aqueous solution of an active agent and an acid precursor of an anionic surfactant capable of lamellar orientation to prepare a mixture of detergent raw materials having a nonionic surfactant as a main base, and step (2): step (1 The step of preparing a granulated product by elevating the temperature of the mixture obtained in 1) to a temperature at which the acid precursor can be neutralized with a stirrer mixer and granulating while increasing the bulk density while rolling. (2) The nonionic activator is a polyoxyethylene alkyl ether having 10 to 20 carbon atoms and a linear or branched primary or secondary alcohol having an average ethylene oxide addition mole number of 5 to 15 (1) (3) The nonionic activator aqueous solution has 10 to 20 carbon atoms.
A linear or branched primary or secondary alcohol of
The production method according to (1) above, which is an aqueous solution of polyoxyethylene alkyl ether having an average added mole number of ethylene oxide of 5 to 15, and a water content of 15% by weight or less.

(4) The acid precursor of the anionic surfactant capable of lamellar orientation is a saturated or unsaturated fatty acid having 10 to 22 carbon atoms, an alkylsulfuric acid having 10 to 22 carbon atoms, and an α having 10 to 22 carbon atoms. -Sulfonated fatty acids, and polyoxyethylene alkyl ether sulfuric acid having 10 to 22 carbon atoms (provided that the average number of moles of ethylene oxide added is 0.2 to
2.0), which is selected from the group consisting of (1) to
(3) The production method according to any one of (5), wherein the amount of the acid precursor of the anionic surfactant capable of lamellar orientation is 5 to 100 parts by weight of the nonionic surfactant and / or the aqueous nonionic surfactant solution. The production method according to any one of (1) to (4), which is 100 parts by weight, (6) The builder exhibiting an alkalinity has a pH of 8 or more when it is a 1 g / liter 20 ° C. aqueous solution or dispersion. The production method according to (1) above, which is one or more organic or inorganic powder builders, (7) The builder exhibiting alkalinity is tripolyphosphate, carbonate, bicarbonate, sulfite, or silicate. , Crystalline aluminosilicate, citrate, polyacrylate,
Acrylic acid-maleic acid copolymer salt, and a mixture of one or more compounds selected from the group consisting of polyglyoxylate salts, having an average particle size of 500 μm.
The production method according to (6) above, which is less than or equal to m.

(8) The alkaline oil-absorbing carrier exhibiting an alkalinity has a pH of 8 or more when it is used as a 1 g / liter 20 ° C. aqueous solution or dispersion, and has a pore volume of 100 to 600 cm ³ / 100 g, specific surface area by BET method is 20 to 700 m ² / g, JIS K 510
The oil absorption amount in 1 is 100 ml / 100 g or more, and the production method according to (1) above, which is a porous oil absorption carrier having an average particle diameter or an average particle diameter of primary particles of 10 μm or less, (9) porosity exhibiting alkalinity (8) above, wherein the oil absorbing carrier is a mixture of one or more compounds selected from the group consisting of amorphous aluminosilicate and calcium silicate, and the average particle size of primary particles is 10 μm or less. (10) The porous oil-absorbing carrier exhibiting alkalinity is an amorphous aluminosilicate having a water content of 15 to 30% by weight, and the average particle diameter of primary particles is 0.1 μm or less,
(9) The production method according to the above (9), wherein the aggregate has an average particle size of 50 μm or less, (11) An acid precursor of an anionic surfactant capable of lamellar orientation with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant. The production method according to (1) above, wherein the step (1) is performed using a mixed solution obtained by mixing the bodies, and then the step (2) is performed by raising the temperature to a temperature equal to or higher than the melting point of the mixed solution.

(12) Nonionic activator and / or aqueous solution of nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation are individually added to carry out step (1), and then the melting point of these compounds is added. Among them, the production method according to (1), wherein the step (2) is performed by elevating the temperature to a temperature higher than the highest melting point, (13) In step (1), a builder and / or spray-drying exhibiting more neutrality or acidity. (14) The production method according to (1) above, wherein the builder exhibiting neutrality or acidity is 1
(13) The method according to (13) above, which is one or more organic or inorganic powder builders exhibiting a pH of less than 8 when made into a 20 ° C aqueous solution or dispersion of g / liter. Alternatively, the builder exhibiting acidity is a salt of mirabilite, citric acid, polyacrylic acid, a partially neutralized product of polyacrylic acid, an acid of a copolymer of acrylic acid-maleic acid, and a partially neutralized product of an acid of a copolymer of acrylic acid-maleic acid. (14) The production method according to (14) above, which is a mixture of one or more compounds selected from the group consisting of: (16) The spray-dried particles contain one or more organic or inorganic builders. The production method according to (13) above, which is particles obtained by spray-drying an aqueous slurry.

(17) The spray-dried particles are carbonate, crystalline aluminosilicate, citrate, mirabilite, sulfite,
1 selected from the group consisting of polyacrylates, salts of acrylic acid-maleic acid copolymers, polyglyoxylates, anionic activators, nonionic activators, and fluorescent dyes 1
(16) The production method according to the above (16), which is particles obtained by spray-drying a slurry containing one kind or a mixture of two or more compounds, and (18) the blending amount of the detergent raw material in the step (1) is
The production method according to (1) or (13) above, which is selected from the following (a) or (b): (a) An anionic surfactant capable of lamellar orientation with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant. The total amount of the acid precursor compounded is 10
60 parts by weight, 40-90 parts by weight of a builder exhibiting alkalinity and / or a porous oil absorbing carrier exhibiting alkalinity, and 0-10 a builder exhibiting neutrality or acidity
10 parts by weight of (b) a nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation, a total of 10 to 60 parts by weight, a builder exhibiting alkalinity and / or an alkalinity. 10 to 80 parts by weight of a porous oil-absorbing carrier exhibiting the following, 0 to 10 parts by weight of a builder exhibiting neutrality or acidity, and 10 to 80 parts by weight of spray-dried particles. (19) A method of performing the step (2) by using a stirring type mixer equipped with a jacket capable of flowing hot water or the like, wherein the temperature of the hot water or the like flown into the jacket is the following (A).
Alternatively, the temperature is higher than the temperature shown in (B), (1),
(11) or (12) the production method, (A) using a mixed solution obtained by mixing a nonionic surfactant and / or an aqueous solution of a nonionic surfactant with an acid precursor of an anionic surfactant capable of lamellar orientation In the case of carrying out the step (1) by the step (B), the nonionic surfactant and / or the aqueous solution of the nonionic surfactant and the acid precursor of the anionic surfactant capable of lamellar orientation are individually added. When performing 1), the higher melting point of these compounds

(20) The production method according to the above (19), wherein the granulation in the step (2) is carried out by a stirring type mixer having a stirring shaft at the center of a horizontal cylinder and stirring blades on the stirring shaft. (21) The production method according to the above (20), wherein the Froude number based on the rotation of the stirring blade of the stirring mixer used in the step (2) is granulated under the condition of (20), (22) the step (2) (19) The manufacturing method according to any one of (19) to (21), wherein granulation is performed in a granulation time of 2 to 20 minutes, (23) The step (1) and the step (2) are performed in the same apparatus (1). (24) The method according to (1) to (23), further comprising a step of mixing the granulated product obtained in step (2) with a fine powder and coating the surface of the granulated product with the fine powder. (25) The average particle diameter of the primary particles of the fine powder is 10 μm or less, and the amount of the fine powder used is The production method according to (24) above, wherein the content is 0.5 to 20 parts by weight relative to 100 parts by weight of the granulated product, (26) The fine powder is a group consisting of crystalline or amorphous aluminosilicate, and calcium silicate. (25) The production method according to the above (25), which is a mixture of one or more compounds selected from the group consisting of:
The production method according to (1) above, wherein the particle size is 250 to 800 μm.
The production according to (1) above, wherein the flow time is 10 seconds or less when evaluated by the time (flow time) required for 100 ml of the particles to flow out from the hopper for measuring bulk density defined by IS K 3362. The method, and (29) the production method according to the above (1), wherein the nonionic detergent particles obtained have a caking property of 90% or more.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Regarding the step (1), the nonionic activator used in the present invention is not particularly limited, but a nonionic activator which is liquid or pasty at 40 ° C. and has an HLB in the range of 9.0 to 16.0 is removed by soiling and foaming. ,
It is excellent in removing bubbles and is suitable. The HLB here is defined in the following document. That is, W.
C. Griffin in Kirk-Oth-mer Encyclopedia of Chemica
l Technology 3rd ed. (M. Grayson ed.) vol 8 Weily
Obtained from that defined by Interscience, New York 1979 pp 900-930.

Specific examples of the nonionic activator include, as the main nonionic activator, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and C10-20, preferably 10-15, and more preferably 12-14. Straight or branched chain, primary or secondary alcohol ethylene oxide average addition mole number 5 to 15,
It is desirable to use preferably 6 to 12, more preferably 6 to 10 polyoxyethylene alkyl ether. In addition, the polyoxyethylene alkyl ether generally contains a large amount of an alkyl ether having a small number of moles of ethylene oxide to be added. It is desirable to use. Others, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine , Glycerin fatty acid ester, higher fatty acid alkanolamide, alkylglycoside, alkylamine oxide and the like may be blended.

The above-mentioned nonionic activator may be compounded in a liquid state at room temperature as it is, or may be compounded in an aqueous solution (that is, an aqueous solution of nonionic activator).
Further, both may be mixed. The use of an aqueous solution has an effect of accelerating the neutralization reaction of the acid precursor of the builder exhibiting alkalinity and / or the porous oil absorbing carrier exhibiting alkalinity and the anionic surfactant capable of forming lamellar orientation. The same substances as described above can be used for the nonionic activator used when blended as an aqueous solution. That is, a suitable nonionic activator aqueous solution is an ethylene oxide average addition of a linear or branched primary or secondary alcohol having 10 to 20 carbon atoms, preferably 10 to 15 carbon atoms, and particularly preferably 12 to 14 carbon atoms. 5 to 15 moles, preferably 6 to 1
2, particularly preferably an aqueous solution of 6 to 10 polyoxyethylene alkyl ethers.

The water content of the nonionic activator aqueous solution is 15% by weight or less, preferably 10% by weight or less, particularly preferably 8% by weight or less. The water content is preferably 15% by weight or less from the viewpoint of suppressing liquid crystallinity and high viscosity of the mixture.

The acid precursor of the anionic surfactant capable of lamellar orientation has, for example, the following properties (a) or (b). (A) Anionic surface active agent such that a mixture obtained by mixing with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant and neutralizing the mixture with sodium carbonate shows anisotropy when observed by a polarizing microscope. Acid precursor of the agent. The method for confirming the anisotropy will be described below. 80 parts by weight of the nonionic surfactant, 20 parts by weight of the acid precursor, and sodium carbonate powder having an amount of neutralization of the acid precursor that is equal to or higher than the melting point of the acid precursor of the anionic surfactant used for the confirmation (average particle diameter of about 5 μm) is sufficiently mixed and neutralized using a high-speed shear mixer (homogenizer). A part of the mixture is heated to the melting point of the acid precursor, cooled and kept at 40 ° C. under a polarization microscope (Niko).
It observes using n company make, OPTIPHOT-POL).

(B) A mixture obtained by mixing with a nonionic activator and / or an aqueous solution of nonionic activator and neutralizing it with sodium carbonate shows a lamellar orientation peak when analyzed by X-ray diffraction. Acid precursors of such anionic surfactants. The measuring method is described below. A sample ([nonionic activator and / or aqueous solution of nonionic activator] / acid precursor of anionic surfactant = 80/20 to 20/80 (weight ratio)) is measured using a Rigaku RAD system. (X
Radiation source Cu (Kα; λ = 1.5405), measurement range; 2θ
= 2 ° to 30 °)

The acid precursor of the anionic surfactant capable of lamellar orientation used in the present invention is not particularly limited, but for example, saturated or unsaturated fatty acid having 10 to 22 carbon atoms, preferably carbon number. 12-18 saturated or unsaturated fatty acid, alkyl sulfuric acid having 10-22 carbon atoms, preferably alkyl sulfuric acid having 12-14 carbon atoms, α-sulfonated fatty acid having 10-22 carbon atoms, preferably 14-16 carbon atoms α-sulfonated fatty acid and polyoxyethylene alkyl ether sulfuric acid having 10 to 22 carbon atoms and ethylene oxide average addition mole number of 0.2 to 2.0, preferably 1 carbon atom
2 to 14, ethylene oxide average addition mole number 0.5 to
1.5 polyoxyethylene alkyl ether sulfuric acid and the like. The carbon number of the compound is preferably 10 or more from the viewpoint of detergency and odor, and 22 or less from the viewpoint of detergency and solubility.

As the above-mentioned acid precursor used in the present invention,
Preferably, fatty acids, specifically, capric acid, lauric acid, myristic acid, palmitic acid, saturated acids such as stearic acid, and a mixture of one or more selected from the group consisting of unsaturated acids such as oleic acid. Can be mentioned. In particular, myristic acid (Lunack MY-98, manufactured by Kao Corporation, etc.), palmitic acid (Lunack P-95, Kao Corporation)
(E.g. manufactured) and the like are preferably used.

Further, the amount of the acid precursor of the anionic surfactant capable of lamellar orientation is such that the nonionic surfactant and / or
Or 5 to 100 parts by weight of the nonionic activator aqueous solution
100 parts by weight, preferably 10 to 60 parts by weight, particularly preferably 15 to 50 parts by weight. The amount of the acid precursor is preferably 5 parts by weight or more from the viewpoint of generating a gelled substance, and is preferably 100 parts by weight or less from the viewpoint of suppressing deterioration of solubility.

In the present invention, as the alkali agent, a builder exhibiting alkalinity and / or a porous oil absorbing carrier exhibiting alkalinity is used. Here, the builder exhibiting alkalinity has a pH of 8 or more when it is a 1 g / liter 20 ° C. aqueous solution or dispersion.
One or more organic or inorganic powder builders can be used.

The alkaline organic builder is preferably a citrate, a polyacrylate, a salt of an acrylic acid-maleic acid copolymer, or a polyglyoxylate. Particularly preferred are trisodium citrate, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, and sodium polyglyoxylate having an average particle diameter of 500 μm or less. These may be used alone or as a mixture of two or more. The average particle size is measured when the average particle size of the builder is 100 μm or more.
After shaking for 5 minutes using a JIS Z8801 standard sieve, it is measured from the weight fraction based on the size of the sieve.
When it is less than 100 μm, the average particle diameter can be measured by a method utilizing light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.).

Next, as inorganic builders exhibiting alkalinity, carbonates, bicarbonates, sulfites, silicates, tripolyphosphates, other phosphates, crystalline aluminosilicates, amorphous aluminosilicates, etc. Specifically, alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate (JIS No. 1 or No. 2 sodium silicate, etc.), 100 CaCO ₃ mg / Crystalline silicate compounds having ion exchange capacity of g or more, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phytates and other phosphates (alkali metal salts such as sodium and potassium) ), As well as crystalline, amorphous sodium aluminosilicate.

Among these inorganic powder builders exhibiting alkalinity, sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sodium sulfite, crystalline sodium aluminosilicate, and crystalline silicate having an ion exchange capacity of 100 CaCO ₃ mg / g or more. A mixture of one or more compounds selected from the group consisting of compounds, more preferably having an average particle size of 500 μm or less, particularly preferably 350 μm or less. The average particle size of the inorganic powder builder can be measured by the same method as the above-described method of measuring the average particle size of the organic powder builder. In addition, these organic builders and inorganic builders can be used in combination.

The alkaline oil-absorbing carrier exhibiting an alkalinity in the present invention has a pH of 8 or more in the case of a 1 g / liter aqueous solution or dispersion at 20 ° C., and has a pore volume of 100 to 600 cm ³ by mercury porosimetry. / 100g, BET
Specific surface area by the method of ²⁰ to 700 m ² / g, JIS K
An oil having an oil absorption of 5101 of 100 ml / 100 g or more, preferably 150 ml / 100 g or more, and an average particle diameter or primary particles having an average particle diameter of 10 μm or less is used. The average particle size can be measured by the same method as in the case of the builder described above. Examples of such a porous oil absorbing carrier are as follows.

1) Amorphous aluminosilicate As the main component of amorphous aluminosilicate,
AluminumSilicate P manufactured by Degussa
820, TIXOLEX 25 manufactured by Han France Chemical Co., and the like, and those represented by the following general formula can also be preferably used. Further, these are characterized in that they have ion exchange ability.

X (M ₂ O) · Al ₂ O ₃ · y (Si
O ₂ ) · w (H ₂ O) (where M represents an alkali metal atom such as sodium and potassium, and x, y, and w represent the number of moles of each component within the following numerical ranges. .2 ≦ x ≦ 2.0 0.5 ≦ y ≦ 10.0 w is any positive number including 0)

X (MeO) · y (M ₂ O) · Al ₂
O ₃ .z (SiO ₂ ) .w (H ₂ O) (Me in the formula represents an alkaline earth metal atom such as calcium and magnesium, M represents an alkali metal atom such as sodium and potassium, x, y , Z, and w represent the number of moles of each component within the range of the following numerical values: 0.001 ≦ x ≦ 0.1 0.2 ≦ y ≦ 2.0 0.5 ≦ z ≦ 10.0 w is Any positive number including 0)

2) Calcium silicate Fluorite R manufactured by Tokuyama Soda Co., Ltd., H manufactured by Huber
UBERSORB ^R 600, and the like. Among these porous oil-absorbing carriers, particularly amorphous aluminosilicates having a water content of 15 to 30% by weight are preferable because they are rich in neutralization reaction with fatty acids. In addition, the average particle size of the primary particles is 0.1 μm or less, and the average particle size of the aggregates is preferably 50 μm or less.

Further, in the step (1), builder and / or spray-dried particles exhibiting neutrality or acidity may be further added. Thereby, effects such as improvement in solubility and cleaning performance can be expected. Furthermore, the purpose of using spray-dried particles is to control bulk density,
This is an improvement in the oil absorption of the builder.

As the neutral or acidic builder, one or more organic or inorganic powder builders exhibiting a pH of less than 8 when a 1 g / liter 20 ° C. aqueous solution or dispersion is used. Can be used. Specifically, mirabilite, sodium chloride, citric acid, polyacrylic acid or a partially neutralized product thereof, an acid of a copolymer of acrylic acid-maleic acid or a partially neutralized product thereof, polyethylene glycol, polyvinyl alcohol,
Polyvinylpyrrolidone, carboxymethylcellulose,
A mixture of one or two or more compounds selected from the group consisting of non-dissociated polymers such as cold water-soluble urethanized polyvinyl alcohol, having an average particle size of 500 μm or less is more preferable, and 350 μm or less is particularly preferable. preferable. Among these, one or a mixture of two or more compounds selected from the group consisting of Glauber's salt, citric acid, polyacrylic acid or a partially neutralized product thereof, and an acid of a copolymer of acrylic acid-maleic acid or a partially neutralized product thereof. Is particularly preferable.

As the spray-dried particles, particles obtained by spray-drying an aqueous slurry containing one or more kinds of the above-mentioned organic or inorganic builders by a known method can be used. Of the aforementioned builders, tripolyphosphate, carbonate, crystalline or amorphous aluminosilicate,
Non-citrate, mirabilite, sulfite, polyacrylate, acrylic acid-maleic acid copolymer salt, polyglyoxylate, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, cold water soluble urethane alcohol, etc. A mixture of one or more compounds selected from the group consisting of dissociative polymers, anionic activators, nonionic activators, and fluorescent dyes is more preferable, and carbonates such as sodium carbonate, crystalline aluminosilicates and Acid salts, sodium sulfate, sulfite salts such as sodium sulfite, polyacrylic acid salts such as sodium polyacrylate, acrylic acid-maleic acid copolymer salts such as sodium salt of acrylic acid-maleic acid copolymer, sodium polyglyoxylate, etc. Polyglyoxy Le salts, anionic surfactants, nonionic active agents, and one or a mixture of two or more spray-dried a slurry containing particles of a compound selected from the group consisting of fluorescent dyes are particularly preferred. The average particle size is 1
It is preferably 100 to 600 μm, and 150 to 400 μm
m are particularly preferred.

The water content of the aqueous slurry is preferably from 30 to 80% by weight, more preferably from 35 to 60% by weight. In the production of the spray-dried particles, one or more kinds of anion, cation or nonionic activator are added to the spray-dried particles in an amount of 40% by weight or less and other additives of 5% by weight or less are added, if necessary. May be.

By mixing the components in step (1) as shown in (a) or (b) below, a mixture of detergent raw materials containing a nonionic activator as a main base can be prepared. (A) The total amount of the nonionic surfactant and / or the aqueous solution of the nonionic surfactant and the acid precursor of the anionic surfactant capable of lamella orientation is 10 to 60 parts by weight, preferably 15 to
50 parts by weight, particularly preferably 20 to 40 parts by weight; 40 to 90 parts by weight, preferably 50 to 90 parts by weight, and a builder exhibiting alkalinity and / or a porous oil-absorbing carrier exhibiting alkalinity.
85 parts by weight, particularly preferably 60 to 80 parts by weight; and 0 to 10 parts by weight, preferably 0 to 5 parts by weight of neutral or acidic builders.

(B) A total of 10 to 60 parts by weight, preferably 15 to 50 parts by weight, of the nonionic surfactant and / or the aqueous solution of the nonionic surfactant and the acid precursor of the anionic surfactant capable of lamellar orientation. Particularly preferably 20 to 40 parts by weight; 10 to 80 parts by weight, preferably 15 to 70 parts by weight, and particularly preferably 20 to 60 parts by weight; builder that exhibits alkalinity and / or porous oil absorbing carrier that exhibits alkalinity; neutral or acidic. 0-10 parts by weight, preferably 0-5 parts by weight; and spray-dried particles 10
-80 parts by weight, preferably 15-70 parts by weight, particularly preferably 20-60 parts by weight.

The mixing method in the step (1) is not particularly limited. When the present invention is carried out batchwise, various methods such as the following (A) to (C) can be adopted. In the following description of the mixing method in the step (1), regarding a builder exhibiting alkalinity, and / or a porous oil absorbing carrier exhibiting alkalinity, a builder exhibiting neutrality or acidity, and / or spray-dried particles, Abbreviated as "builder, etc."

(A) A mixed solution of a nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation is prepared in advance, and
A method of mixing with a builder or the like by various methods such as. At this time, it is more preferable to raise the temperature in the mixer to the melting point of the mixed liquid or higher to perform the mixing. First of all, a builder, etc. in a mixing machine (each component is not mixed)
The method of adding and mixing a nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation after charging. A method in which a mixture of builders and the like is previously charged into a mixer, and then a mixed solution of a nonionic surfactant and / or an aqueous solution of a nonionic surfactant and an acid precursor of an anionic surfactant capable of lamellar orientation is added and mixed. A method in which a builder, etc. (each component is not mixed), a nonionic activator and / or an aqueous solution of a nonionic activator, and a mixed solution of an acid precursor of an anionic surfactant capable of lamellar orientation are simultaneously charged in small amounts in a mixer. .

Builder, etc. (each component is not mixed)
Anionic surfactant capable of forming a lamellar orientation with other non-ionic surfactants and / or nonionic surfactant aqueous solution after charging some of the components in a mixer to the other builder etc. (each component is not mixed) A method in which the mixed solution of the acid precursor of (1) and (2) are simultaneously charged into the mixer little by little. In the above, first, a builder or the like (each component is not mixed) is charged into a mixer, and then an acid precursor of an anionic surfactant capable of forming a lamellar orientation with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant. The method of adding and mixing the mixed solution of is preferable. The mixer and mixing method for preparing a mixed solution of a nonionic surfactant and / or an aqueous solution of a nonionic surfactant and an acid precursor of an anionic surfactant capable of lamellar orientation are not particularly limited. ,
Any general mixer and mixing method may be used. At this time,
A mixed solution is prepared by elevating the temperature above the melting point of the nonionic activator and the above acid precursor.

(B) The following methods (1) to (4) in which the nonionic activator and / or the aqueous solution of the nonionic activator are premixed with the builder and the above acid precursor is added and mixed. At this time, it is more preferable to raise the temperature in the mixer to a temperature higher than the melting point of the nonionic activator or the acid precursor, whichever is higher, to carry out the mixing. First of all, a builder, etc. in a mixing machine (each component is not mixed)
A method of adding and mixing a nonionic activator and / or an aqueous solution of a nonionic activator after adding, and then adding and mixing the above acid precursor. A method in which a mixture of builders and the like is previously charged into a mixer, then a nonionic activator and / or an aqueous solution of a nonionic activator is added and mixed, and then the above acid precursor is added and mixed. A method in which a builder and the like (each component is not mixed) and a nonionic activator and / or an aqueous solution of a nonionic activator are simultaneously charged into a mixer little by little, and then the above acid precursor is added and mixed. After charging a part of the components of the builder, etc. (the components are not mixed) into the mixer, the components of the builder, etc. (the components are not mixed) and the nonionic activator and / or nonionic activator aqueous solution And a small amount of the acid precursor are simultaneously charged into a mixer, and then the above acid precursor is added and mixed.

(C) The following methods (1) to (5) in which the nonionic activator and / or the aqueous solution of the nonionic activator and the above acid precursor are simultaneously added to and mixed with the builder. At this time, it is more preferable to raise the temperature in the mixer to a temperature higher than the melting point of the nonionic activator or the acid precursor, whichever is higher, to carry out the mixing. First of all, a builder, etc. in a mixing machine (each component is not mixed)
And a nonionic activator and / or an aqueous solution of a nonionic activator and the above-mentioned acid precursor are simultaneously added and mixed. A method in which a mixture of builders and the like is charged into a mixer, and then the nonionic activator and / or the aqueous solution of the nonionic activator and the above acid precursor are simultaneously added and mixed. A method in which a builder and the like (each component is not mixed), a nonionic activator and / or an aqueous solution of a nonionic activator, and the above-mentioned acid precursor are simultaneously charged in small amounts in a mixer. After charging a part of the components of the builder, etc. (the components are not mixed) into the mixer, the components of the builder, etc. (the components are not mixed) and the nonionic activator and / or nonionic activator aqueous solution And a method in which the above-mentioned acid precursor is charged into the mixer at the same time little by little.

When the present invention is carried out continuously, first, the detergent raw materials are continuously mixed or simultaneously mixed and granulated, but the method for supplying the detergent raw materials is not particularly limited. For example, the following various methods can be used. A method of continuously and independently supplying each component of the detergent raw material. With a pre-mixed builder etc. in the detergent raw material,
A method of continuously supplying a nonionic surfactant and / or a nonionic surfactant aqueous solution and a mixed liquid of an acid precursor of an anionic surfactant capable of lamellar orientation. With a pre-mixed builder etc. in the detergent raw material,
A method of continuously supplying a nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation. A mixture of two or more components constituting a builder or the like in a detergent raw material, a component constituting the remaining builder, a nonionic activator and / or an aqueous solution of a nonionic activator, and an anion capable of lamellar orientation. A method of continuously supplying a mixed solution of an acid precursor of a surfactant. A mixture of two or more components constituting a builder or the like in a detergent raw material in advance, a component constituting the remaining builder, a nonionic activator and / or an aqueous solution of a nonionic activator, and a shade capable of lamellar orientation. A method of continuously supplying an acid precursor of an ionic surfactant. Among these, the methods (1) to (4) are useful when using a builder or the like having poor powder properties such as fluidity and caking property.

In the present invention, when continuously granulating the detergent raw material, as another embodiment, a nonionic surfactant and / or an aqueous solution of a nonionic surfactant, an acid of an anionic surfactant capable of lamellar orientation are used. It is also possible that all of the precursor, the builder, and the like are mixed in advance by a batch method, and the mixture is continuously supplied to the granulation step. Further, in any of the batch type and continuous type liquid components, that is, a nonionic surfactant and / or an aqueous solution of a nonionic surfactant, an acid precursor of an anionic surfactant capable of lamellar orientation, and a nonionic surfactant and It is preferable to spray and supply a mixed solution of an aqueous solution of a nonionic surfactant and / or an acid precursor of an anionic surfactant capable of lamellar orientation.

The following are examples of the apparatus preferably used in the step (1) of the present invention. In the case of performing a batch process, those of (1) to (4) are preferable. (1) This type of mixer has a mixing tank having a stirring shaft inside, and a stirring blade attached to the shaft to mix powder.
For example, Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
), A high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powrex Co., Ltd.), etc., and particularly preferably a horizontal mixing tank having a stirring shaft at the center of a cylinder. For example, there are a Redige mixer (made by Matsuzaka Giken Co., Ltd.) and a pro-share mixer (made by Taiheiyo Kiko Co., Ltd.). (2) There is a mixer in which mixing is performed by rotating a V-shaped mixing tank, for example, a V-type mixer (manufactured by Fuji Paudal Co., Ltd.). (3) There is a mixer of a type in which mixing is performed by rotating a ribbon-shaped blade forming a spiral in a fixed semi-cylindrical container, for example, a ribbon mixer (manufactured by Fuji Paudal Co., Ltd.). (4) A mixer of a type in which a screw is rotated and revolved around an axis parallel to the wall of the container along a conical container to perform mixing by mixing, for example, a Nauta mixer (manufactured by Hosokawa Micron Corporation), an SV mixer ( Shinko Pantech Co., Ltd.).

As the apparatus for the continuous system, the following (1) to (3) are preferably used. (1) Consisting of a vertical cylinder with a powder inlet and a main shaft with a mixing blade, the main shaft is supported by an upper bearing and the discharge side is free, such as a flexomix type mixer. (Powrex). (2) A raw material is put into the upper part of a disk having a stirring pin, the disk is rotated at a high speed, and a continuous mixer of a type of mixing by shearing action, for example, a flow jet mixer (manufactured by Koken Pautex Co., Ltd.) And a spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.). (3) It is a continuous mixer of a type in which a mixing tank has a stirring shaft inside and a stirring blade is attached to this shaft to mix powder. For example, there is a continuous Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). Further, a device such as a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.) or a vertical granulator (manufactured by Powrex Co., Ltd.) may be used as a continuous device.
Preferably having a stirring shaft at the center of the cylinder in a horizontal mixing tank,
This type of mixer is a continuous type mixer in which a stirring blade is attached to this shaft to mix powder, and examples thereof include a Ladyge mixer (Matsuzaka Giken Co., Ltd.) and a pro-share mixer (Taikai Kiko Co., Ltd.). .

Step (2) Step (2) is a step of preparing a granulated product using the mixture obtained in step (1). In the step (2), the temperature of the mixture obtained in the step (1) is set so that at least the acid precursor of the anionic surfactant capable of lamellar orientation can be neutralized, that is, the nonionic surfactant and the acid precursor. It suffices to set the temperature at which both become liquids. This is for efficiently reacting the builder exhibiting alkalinity and / or the porous oil absorbing carrier exhibiting alkalinity with the acid precursor to form a gelled product. More specifically, in the step (1), A) in the case where the nonionic activator and / or the aqueous solution of the nonionic activator and the above acid precursor are mixed in advance, the melting point of the resulting mixed solution or higher, and B) when added separately, Whichever is higher, whichever is higher
The temperature may be raised to.

Here, the temperature for raising the temperature may be higher than the melting point shown in A) or B) in order to accelerate the reaction, but in a practical range, it is 0 to 50 higher than the melting point.
A temperature higher by 0 ° C is preferable, and a temperature higher by 10-30 ° C is more preferable. In order to promote this reaction, water may be appropriately added in the step (1) or (2), or an alkaline aqueous solution (for example, an aqueous sodium silicate solution, an aqueous sodium hydroxide solution, an aqueous sodium hydroxide solution) may be added to the step ( In 1) or 2), the acid precursor may be added in an amount equal to or less than the neutralization equivalent.

When this reaction occurs, the gelled product carrying the nonionic activator is formed on the surface of the alkaline powder (builder or oil absorbing carrier), which plays a role of a binder in the granulation in the step (2). At the same time, it is considered that the supporting force of the nonionic activator on the surface of the powder is improved, and that it plays a role of suppressing the generation of spots. The temperature of the granulated product at the end of the step (2) is not particularly limited, but the melting point (nonionic surfactant and acid precursor of an anionic surfactant capable of lamellar orientation) shown in A) or B) above may be used. It may be higher than the melting temperature) by 10 ° C. or higher, preferably 20 ° C. or higher. Naturally, the higher the temperature, the more the reaction is promoted, but it is desirable to select an industrially suitable temperature. If the amount is less than this range, the reaction is not promoted, so that a gelled product is not formed and a desired granulated product cannot be obtained.

Since it is necessary to raise the temperature of the mixer in the step of granulating in step (2), it is preferable to use a mixer whose temperature can be adjusted. For example, in a mixer provided with a jacket capable of flowing hot water or the like, the nonionic surfactant and the acid precursor of an anionic surfactant capable of lamellar orientation are melted at the temperature of the hot water or the like flowing in the jacket. Setting the temperature higher than the temperature is preferable because the temperature can be easily adjusted. Needless to say, the jacket temperature is appropriately controlled in order to raise the temperature of the granulated product at the end of the above step (2).

A stirring type mixing machine having a stirring shaft equipped with stirring blades at the center thereof is preferable as a mixing machine from the viewpoint of efficiently rolling granulation using the above-mentioned gel material as a binder. As a stirring type mixer having such a structure,
For example, Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
There is a device such as a high speed mixer (manufactured by Fukae Industry Co., Ltd.), a vertical granulator (manufactured by Paulec Co., Ltd.), etc., and particularly preferably a horizontal mixing tank having a stirring shaft at the center of the cylinder, This type of mixer is a type in which a stirring blade is attached to this shaft to mix powders, and for example, there are a Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd.) and a proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.). In this case, it is preferable to granulate at a Froude number of 1 to 4 defined by the following formula based on the rotation of the stirring blade of the stirring type mixer, and 1.2 to 3
Is more preferable. If it exceeds this range, the stirring force tends to be too strong, and the particle size of the granulated product tends to be broad, and if it is less than this range, the mixing efficiency tends to be poor and the particle size of the granulated product tends to become broad.

Here, the Froude number is defined as follows. Fr = V ² / (R × g) (where Fr is the Froude number, V is the peripheral speed (m / s) at the tip of the stirring blade, R is the rotation radius (m) of the stirring blade, g
Represents gravitational acceleration (m / s ² ). )

In step (2), the granulation time in batch granulation and the average residence time in continuous granulation for obtaining a suitable granulated product are not particularly limited, but 2 It is preferably -20 minutes, more preferably 3-10 minutes. From the viewpoint of promoting the neutralization reaction, the granulation time and the average residence time are preferably 2 minutes or longer, and from the viewpoint of productivity, 20 minutes or shorter is preferable.

Surface coating step The present invention further includes a surface coating step of adding fine powder as a surface coating agent in order to coat the surface of the granulated product after the granulation in step (2). Good. Since coating the surface of the granulated product tends to improve the fluidity and non-caking property of the granulated product, addition of fine powder is preferred. When the surface coating agent is added in the initial or middle stage of granulation, it is taken into the inside of the granulated material and does not contribute to the improvement of the fluidity and the non-caking property of the granulated material. The term "after granulation" as used herein means that the average particle size of the granulated product is 250 to 1000.
It is the time when granulation is carried out to a desired average particle size within the range of μm. The fine powder preferably has an average primary particle diameter of 10 μm or less. This means that when the fine powder is coated on the surface of the granulated material, it may be 10 μm or less. For example, an aggregate of fine powder of 20 to 30 μm is crushed during the coating process and coated. It may be. If the average particle size exceeds 10 μm, the coverage of the surface of the granulated product decreases, and desired nonionic detergent particles cannot be obtained. The average particle size of the fine powder is measured by a method using light scattering, for example, by a particle analyzer (manufactured by HORIBA, Ltd.) or by a measurement using a microscope.

As the surface coating agent, an aluminosilicate acts as a calcium ion scavenger at the time of washing, which is desirable, and an aluminosilicate having an average primary particle diameter of 10 μm or less is particularly desirable. The aluminosilicate may be either crystalline or amorphous. In addition to aluminosilicates, inorganic fine powders such as calcium silicate having an average primary particle size of 10 μm or less, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and silicate compounds such as crystalline silicate compounds are also preferable. . Specific examples of the aluminosilicate include the substances exemplified as the inorganic builder and the porous oil-absorbing carrier. Further, metal soap having an average primary particle size of 10 μm or less can be used in the same manner.

Among the above substances, crystalline or amorphous aluminosilicate, calcium silicate, 100CaCO ₃ m
A mixture of one or more compounds selected from the group consisting of crystalline silicate compounds having an ion exchange capacity of g / g or more is preferable, and crystalline or amorphous aluminosilicate, calcium silicate and the like are particularly preferable.

The amount of the fine powder used is as follows:
0.5 to 20 parts by weight to 0 parts by weight is preferable,
15 parts by weight is more preferable, and 2 to 10 parts by weight is particularly preferable. If the amount of the fine powder used exceeds this range, the fluidity tends to decrease, and dust tends to be generated, which may impair the usability for consumers. Further, if it is less than this range, it tends to be difficult to obtain a powder having good fluidity. The apparatus used in the surface coating step is not particularly limited, and a known mixer can be used, but the mixer exemplified in the above steps (1) and (2) is preferable. Particularly, the mixer of the step (2) is suitably used.

The nonionic detergent particles according to the present invention are produced by the above steps (1) and (2), preferably steps (1), (2) and the surface coating step. With the apparatus described above, the step (2) and the surface coating step can be carried out batchwise. When the step (2) and the surface coating step are performed in a continuous manner, a device having a structure capable of continuously supplying the raw material and discharging the granulated material may be used in these apparatuses. When the present invention is carried out batchwise, step (2)
Steps (1) and (2) by the stirring type mixer used in
Alternatively, the steps (1) and (2) and the surface coating step can be performed by the same apparatus. Partial granulation proceeds in the step (1), and after the step (1) is finished, the granulation is further progressed by continuously stirring and mixing. When the steps (1) and (2) and the surface coating step are performed by the same apparatus, a stirring type mixing tank having a horizontal stirring axis at the center of a horizontal cylindrical mixing tank is particularly preferable.

When the present invention is carried out continuously, the step (1) and the step (2) can be simultaneously carried out by the same apparatus by the stirring type mixer used in the step (2). In addition, if the mixing tank of the stirring mixer of the type having a horizontal stirring shaft at the center of the horizontal cylindrical mixing tank has a structure (for example, a partition plate is inserted) capable of dividing the mixing tank in the axial direction, the step ( 1) and step (2), step (2) and surface coating step, and step (1) and step (2) and surface coating step can be continuously performed by the same apparatus.

The amount of the above-mentioned various detergent raw materials to be charged into the mixer is preferably 70% by volume or less of the total volume in both the batch system and the continuous system in all the steps, and more preferably. It is 15 to 40% by volume. If it exceeds this range, the mixing efficiency of the detergent raw material in the mixer tends to decrease, which is not preferable.

Further, in the present invention, the following additives can be used in the steps (1) and (2) or after the surface coating step. (1) Bleaching agent For example, sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct and the like can be mentioned. (2) Enzymes There is no particular limitation as long as they are used in detergents, but particularly preferred are protease, cellulase, amylase, lipase and the like. (3) Surfactant powder For example, alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfonated fatty acid salt or ester salt, alkyl or alkenyl ether carvone. Examples thereof include powders of anion activators such as acid salts and soaps, powders of amphoteric activators such as carbobetaine and sulfobetaine, and powders of cation activators such as dilong-chain quaternary ammonium salts. (4) Others Other additives include a bluing agent, an anti-caking agent, an antioxidant, a fluorescent dye, a light-activated bleach, a fragrance, a re-staining agent, and the like. There is no particular limitation as long as it is used for detergents.

If the granulation method of the present invention is used,
Powder material and nonionic activity are not affected by (1) composition restrictions in granulation utilizing hydration of washing active salt and (2) composition restrictions for establishing stable operability in solidification / crushing method. It is possible to make the detergent raw material composed of the agent into an arbitrary ratio, and there is an advantage that the composition is hardly restricted. Further, a detergent granular composition containing an anion as a main base, which is produced by the following production method (for example, JP-A-61-698).
97, JP-A-60-72999, JP-A-3.
-33199 gazette, Unexamined-Japanese-Patent No. 3-146599,
JP-A-5-86400, JP-A-61-76597
Japanese Patent Laid-Open No. 60-96698, Japanese Patent Laid-Open No. 3-1
15400 gazette, JP-A-2-29500, JP-A-6-506720, JP-A-4-81500, JP-A-61-272300, JP-A-1-31.
No. 1200, No. 6-502212, etc.) can be added to the composition at any ratio.

The following are suitable as the physical properties of the nonionic detergent particles obtained in the present invention. (1) Bulk density: 0.6 to 1.2 g / ml, preferably 0.7 to 1.0 g / ml. If it exceeds this range, the solubility tends to deteriorate. (2) Average particle size: 250 to 800 μm, preferably 30
0-600 μm. The average particle size is determined by the method described below. If it exceeds this range, the solubility tends to deteriorate,
If it is less than this range, dust tends to be generated. (3) Fluidity: The flow time is 10 seconds or less, preferably 8 seconds or less. The flow time is the time required for 100 ml of powder to flow out from the hopper for measuring bulk density defined by JIS K3362. If it exceeds this range, the handleability of the detergent tends to deteriorate. (4) Caking property: The sieve passing rate is 90% or more, preferably 95% or more. The sieve passing rate is determined by the method described below. Below this range, caking tends to occur during storage, which is not preferable. (5) Stainability: visual evaluation described in Examples described later was 2
Rank or higher, preferably 1 rank. Below this rank, the nonionic activator-containing powder is apt to adhere to the equipment in the transport system, and it is necessary to devise a technique for preventing stain formation on the container.

[0067]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Further, in the following Examples and the like, dense ash, zeolite 4A type is manufactured by Tosoh Corporation, and crushed light ash is light ash manufactured by Tosoh Corporation using a atomizer made by Fuji Paudal. As the amorphous aluminosilicate, one manufactured by Kao Corporation was used. Further, the pH of the builder and the porous oil-absorbing carrier used in the following Examples and the like at 20 ° C. of a 1 g / liter aqueous solution or dispersion is as follows. Density ash: 11.1, light ash: 11.1, crushed light ash: 11.0, zeolite 4A type: 9.8, amorphous aluminosilicate: 10.4, mirabilite: 7.1.

Example 1 25 parts by weight of the nonionic activator shown in Table 1 and 10 parts by weight of fatty acid were heated and mixed at 70 ° C. to prepare a mixed solution. Next, 35 parts by weight of dense ash, 10 parts by weight of zeolite 4A type and 20 parts by weight of amorphous aluminosilicate were charged into a Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, with a jacket), and a spindle (150 rpm). ) And chopper (4000 rpm) were started to be stirred. Note that warm water at 75 ° C. was flowed through the jacket at 10 liter / minute. The mixed solution was put therein for 4 minutes, then stirred for 6 minutes and discharged. Incidentally, the total charged amount was 4 kg. The bulk density, average particle size, fluidity, caking property, and stain release property of the nonionic detergent particles thus obtained were measured. Table 3 shows the results.

Here, the bulk density was measured by the method specified in JIS K3362. The average particle size is JIS Z
After vibrating for 5 minutes using a standard sieve of 8801, the weight fraction was measured according to the size of the sieve mesh. The fluidity of the powder was evaluated by the time required for 100 ml of the powder to flow out from the hopper for measuring bulk density defined in JIS K3362.

The test method for caking property is as follows. Caking test method Filter paper (Toyo filter paper No. 2) length 10.2 cm x width 6.2 c
Make a box without top of mx 4 cm, and staple the four corners. Put 50g of sample in this box, and the total weight of acrylic resin plate and lead plate (or iron plate) is 15g + 2
Place 50g. This is left in a thermo-hygrostat having a temperature of 30 ° C. and a humidity of 80%, and after 7 days, the caking state is judged. The judgment was made by obtaining the pass rate as follows. <Passage rate> The sample after the test is wire mesh (or sieve, mesh 5 mm
(* 5 mm) gently, and the powder that has passed through the wire net is weighed to determine the passing rate for the sample after the test.

[0071]

[Equation 1]

Further, the test method for the stain release property is as follows. The stain generation state of the mixed liquid of the nonionic activator and the fatty acid on the bottom portion (the surface not in contact with the powder) of the filter paper on which the caking test was performed was visually evaluated. The evaluation of the appearance of spots was determined by the wet area of the bottom, and was ranked 1 to 5. The status of each rank is as follows. Rank 1: Not wet. 2: About 1/4 surface is wet. 3: About 1/2 surface is wet. The surface is about 4: 3/4 wet. 5: The entire surface is wet.

Example 2 The raw materials shown in Table 1 were charged by the same granulation method as in Example 1,
Nonionic detergent particles were produced, and then, in the same Ledige mixer, 8 parts by weight of zeolite 4A type was added as a surface coating agent, and the mixture was stirred for 1.5 minutes and discharged. The nonionic detergent particles thus obtained were evaluated in the same manner as in Example 1.

Example 3 40 parts by weight of dense ash shown in Table 1, 10 parts by weight of zeolite 4A type and 20 parts by weight of amorphous aluminosilicate were added to a Ledige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, with jacket). Parts were added and stirring was started. 25 parts by weight of the nonionic activator and 5 parts by weight of fatty acid heated to 75 ° C. were respectively added thereto without premixing in 3 minutes at the same time, and then stirred for 6 minutes. In addition, stirring is performed on the main shaft (150 r.p.
m.) and a chopper (4000 rpm), and the jacket was flushed with warm water at 75 ° C. at 10 liters / minute. next,
8 parts by weight of zeolite 4A type was added as a surface coating agent,
The mixture was stirred for 1.5 minutes and discharged. The nonionic detergent particles thus obtained were evaluated in the same manner as in Example 1.

Example 4 25 parts by weight of the nonionic activator shown in Table 1 and 10 parts by weight of alkylsulfuric acid were heated and mixed at 30 ° C. to prepare a mixed solution. Next, in the same manner as in Example 1, 40 parts by weight of dense ash, 5 parts by weight of zeolite 4A type and 20 parts by weight of amorphous aluminosilicate were added to a Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, with jacket). Was charged and stirring was started. Hot water at 40 ° C. was flown through the jacket at 10 liters / minute. The mixed solution was added thereto for 4 minutes and then stirred for 6 minutes. Next, 8 parts by weight of zeolite type 4A was charged as a surface coating agent, stirred for 1.5 minutes, and discharged. The nonionic detergent particles thus obtained were evaluated in the same manner as in Example 1.

Examples 5 to 9 The raw materials shown in Tables 1 and 2 were charged by the same granulation method and surface coating method as in Example 2 to prepare nonionic detergent particles, and the same evaluation as in Example 1 was carried out. . The composition and evaluation results are shown in Table 1.
~ 3.

Comparative Example 1 Nonionic detergent particles were prepared by charging the raw materials shown in Table 2 by the same granulation method and surface coating method as in Example 2, and the same evaluation as in Example 1 was performed. Composition and evaluation results are shown in Table 2 and Table 3.
Shown in In addition, cold water at 10 ° C. was flown through the jacket at 10 liters / minute. The stirring time after the addition of the nonionic activator was 6 minutes. The stirring time for coating the surface is 1.5
It was a minute.

Comparative Example 2 Nauta mixer (manufactured by Hosokawa Micron Co., Ltd., capacity 3)
The powder raw material shown in Table 2 was put into 0 liter, with a jacket), and stirring (20 rpm) was started. Note that warm water at 75 ° C. was flowed through the jacket at 10 liter / minute. The mixed solution was put therein for 4 minutes, and then stirred for 20 minutes. Next, 8 parts by weight of zeolite 4A type was added as a surface coating agent, stirred for 1.5 minutes, and then discharged. The total amount charged was 5 kg. The physical properties of the nonionic detergent particles thus obtained were evaluated in the same manner as in Example 1. Table 3 shows the results.

Comparative Example 3 Nonionic detergent particles were prepared by charging the raw materials shown in Table 2 by the same granulation method and surface coating method as in Example 2, and the same evaluation as in Example 1 was performed. Composition and evaluation results are shown in Table 2 and Table 3.
Shown in

Comparative Example 4 Nonionic detergent particles were prepared by charging the raw materials shown in Table 2 by the same granulation method and surface coating method as in Example 1, and the same evaluation as in Example 1 was performed. Composition and evaluation results are shown in Table 2 and Table 3.
Shown in

[0081]

[Table 1]

[0082]

[Table 2]

[0083]

[Table 3]

Example 10 A slurry having a water content of 50% by weight was spray-dried to obtain spray-dried particles having the following composition. Zeolite 4A type 12.9 parts by weight Glauber's salt 5.0 parts by weight Sodium stearate 1.0 parts by weight Carboxymethyl cellulose Na salt 0.1 parts by weight Water 1.0 parts by weight Using the spray-dried particles obtained, Example 2 The raw materials shown in Tables 4 and 5 were charged by the same granulation method and surface coating method as above to prepare nonionic detergent particles, and the same evaluation as in Example 1 was performed. The composition and evaluation results are shown in Tables 4, 5 and 6.

Example 11 A slurry having a water content of 50% by weight was spray-dried to obtain spray-dried particles having the following composition. Zeolite 4A type 13.9 parts by weight Glauber's salt 5.0 parts by weight Carboxymethyl cellulose Na salt 0.1 parts by weight Water 1.0 parts by weight Using the obtained spray-dried particles, the same granulation method and surface as in Example 2 were used. The raw materials shown in Tables 4 and 5 were charged by the coating method to prepare nonionic detergent particles, and the same evaluation as in Example 1 was performed. The composition and evaluation results are shown in Tables 4, 5 and 6.

[0086]

[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

Example 12 25 parts by weight of a nonionic activator and 5 parts by weight of the fatty acids shown in Table 4 were heated and mixed at 70 ° C. to prepare a mixed solution.
Next, 30 parts by weight of this mixed solution, 40 parts by weight of dense ash, 10 parts by weight of zeolite 4A type and amorphous aluminosilicate 2
0 part by weight was continuously charged into a Flexomix 160 type (manufactured by Paulec Co., Ltd.) and mixed. At this time, the total charged amount was 250 kg / hr, the number of revolutions of the main shaft was 3000 rpm, and the mixed liquid was supplied to one fluid nozzle (pressure 2 k
g / cm ² ) and sprayed in the machine. Next, this mixed detergent raw material is continuously fed into a Loedige mixer KM-
150D (manufactured by Matsuzaka Giken Co., Ltd., with a jacket) was charged and granulated. The rotation speed of the main shaft at this time is 105 rpm,
The rotation speed of the chopper is 3440 rpm, and the jacket has 7
Warm water of 5 ° C. was flowed at 10 liter / min. Incidentally, the average residence time was 6.1 minutes.

Next, 100 parts by weight of the above granulated detergent raw material and 8 parts by weight of zeolite 4A type were continuously mixed with the same structure as the above-mentioned Loedige mixer [internal volume 40 liters, Kao ( Co., Ltd.] and mixed. At this time, the rotation speed of the main shaft was 130 rpm, the rotation speed of the chopper was 4000 rpm, and hot water at 75 ° C. was flowed through the jacket at 10 liter / min. The average residence time was 1.5 minutes. Evaluation of the nonionic detergent particles thus obtained was performed in the same manner as in Example 1. The composition and evaluation results are shown in Tables 4, 5 and 6.

Example 13 The same detergent raw material as in Example 12 was continuously charged into a Ledige mixer KM-150D (manufactured by Matsuzaka Giken Co., Ltd., with a jacket) to perform mixing and granulation at the same time. At this time, the total charged amount is 250 kg / hr, and the rotation speed of the main shaft is 1
05 rpm, the rotation number of the chopper was 3440 rpm, and hot water at 75 ° C. was flowed through the jacket at 10 liter / minute.
Incidentally, the average residence time was 6.0 minutes. Further, the mixed liquid was sprayed using a one-fluid nozzle (pressure 2 kg / cm ² ) toward an area where the chopper was rotating. The step of coating the surface of the granulated product is the same as in Example 12,
The nonionic detergent particles were evaluated in the same manner as in Example 1. The composition and evaluation results are shown in Tables 4, 5 and 6.

As is clear from the above results, the nonionic detergent particles obtained in Examples 1 to 13 obtained by the production method of the present invention have high bulk density, good fluidity and good non-caking property, and exhibit no spots. The particles were excellent. On the other hand, by carrying out the granulation at a temperature as low as 10 ° C., detergent particles having poor fluidity and stain generation were obtained (Comparative Example 1). Further, detergent particles obtained without adding an acid precursor (fatty acid) of an anionic surfactant capable of lamellar orientation (Comparative Example 2), an acid precursor of anionic surfactant not having lamellar orientation (straight chain) Detergent particles obtained by blending (alkylbenzene sulfonic acid) (Comparative Example 3) and detergent particles obtained by blending soap in place of the acid precursor (Comparative Example 4)
Had poor fluidity, caking properties, and stain release properties.

[0093]

EFFECTS OF THE INVENTION By using the method for producing nonionic detergent particles of the present invention, the composition is not limited to a specific substance, the degree of freedom of composition is high, the bulk density is high, and the content of the nonionic activator is high. It has become possible to obtain nonionic detergent particles which are high and have excellent powder flow characteristics and non-caking properties and which are free from stains.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Yamada 1334 Minato Wakayama City Kao Co., Ltd. (72) Inventor Teruo Kubota 1334 Minato Wakayama City Kao Co., Ltd. (72) Inventor Ogurisu Hiroshi Wakayama City Minato 1334 Kao Research Institute

Claims (29)

[Claims] 1. The method according to claim 1, wherein the bulk density is 0.6 to
A method for producing nonionic detergent particles, characterized in that 1.2 g / ml of nonionic detergent particles are obtained. Step (1): A nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation are blended with a builder exhibiting alkalinity and / or a porous oil absorbing carrier exhibiting alkalinity. A step of preparing a mixture of detergent raw materials having a nonionic activator as a main base, and step (2): a temperature of at least a temperature at which the mixture obtained in step (1) can be neutralized with a stirring mixer. A step of preparing a granulated product by raising the temperature and rolling to increase the bulk density while granulating. 2. The nonionic activator is a polyoxyethylene alkyl ether having an average number of moles of ethylene oxide added of 5 to 15 of a linear or branched primary or secondary alcohol having 10 to 20 carbon atoms. Item 2. The manufacturing method according to Item 1. 3. The nonionic activator aqueous solution has 10 to 10 carbon atoms.
An aqueous solution of 20 straight chain or branched chain primary or secondary alcohols and polyoxyethylene alkyl ether having an average ethylene oxide addition mole number of 5 to 15,
The method according to claim 1, wherein the water content is 15% by weight or less. 4. An acid precursor of an anionic surfactant capable of lamellar orientation is a saturated or unsaturated fatty acid having 10 to 22 carbon atoms, an alkylsulfuric acid having 10 to 22 carbon atoms, or 10 carbon atoms.
.Alpha.-sulfonated fatty acid of .about.22 and carbon number of 10
2 polyoxyethylene alkyl ether sulfuric acid (however,
The average number of moles of ethylene oxide added is 0.2 to 2.0)
The manufacturing method according to any one of claims 1 to 3, which is selected from the group consisting of: 5. The amount of the acid precursor of the anionic surfactant capable of lamellar orientation is 5 to 10 relative to 100 parts by weight of the nonionic surfactant and / or the aqueous nonionic surfactant solution.
It is 0 weight part, The manufacturing method in any one of Claims 1-4. 6. The builder exhibiting alkalinity is 1 g /
P when using liter of 20 ° C. aqueous solution or dispersion
The method according to claim 1, wherein the H is 8 or more, and is one or more organic or inorganic powder builders. 7. A builder exhibiting alkalinity is tripolyphosphate, carbonate, bicarbonate, sulfite, silicate,
It is a mixture of one or more compounds selected from the group consisting of crystalline aluminosilicates, citrates, polyacrylates, salts of acrylic acid-maleic acid copolymers, and polyglyoxylates. Particle size is 50
The manufacturing method according to claim 6, which is 0 μm or less. 8. A porous oil-absorbing carrier exhibiting alkalinity,
It shows a pH of 8 or more in the case of a 1 g / liter aqueous solution or dispersion at 20 ° C., and has a pore volume of 1 in a mercury intrusion method.
00~600cm ³ / 100g, a specific surface area of 20~700m ² / g in the BET method, and the oil absorption of at JIS K 5101 is 100 ml / 100 g or more, an average particle diameter or average primary particle size of less 10μm The production method according to claim 1, which is a porous oil-absorbing carrier. 9. A porous oil-absorbing carrier exhibiting alkalinity,
9. The production method according to claim 8, which is a mixture of one or more compounds selected from the group consisting of amorphous aluminosilicate and calcium silicate, and has an average primary particle size of 10 μm or less. 10. The porous oil-absorbing carrier exhibiting alkalinity is an amorphous aluminosilicate having a water content of 15 to 30% by weight, the average particle diameter of primary particles is 0.1 μm or less, and an aggregate thereof. 10. The production method according to claim 9, wherein the average particle size of is 50 μm or less. 11. The step (1) is carried out using a mixed solution obtained by mixing a nonionic activator and / or an aqueous solution of a nonionic activator with an acid precursor of an anionic surfactant capable of lamellar orientation, and then performing the step (1). The manufacturing method according to claim 1, wherein the step (2) is performed by raising the temperature to a temperature equal to or higher than the melting point of the mixed liquid. 12. A nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation are individually added to carry out step (1), and then the melting point of these compounds is adjusted. The manufacturing method according to claim 1, wherein the step (2) is performed by raising the temperature to a temperature higher than the highest melting point. 13. The production method according to claim 1, wherein in step (1), builder and / or spray-dried particles exhibiting neutrality or acidity are further added. 14. The neutral or acidic builder is one or more organic or inorganic powder builders which show a pH of less than 8 when a 1 g / liter 20 ° C. aqueous solution or dispersion is used. The manufacturing method according to claim 13. 15. A builder exhibiting neutrality or acidity is selected from the group consisting of Glauber's salt, citric acid, polyacrylic acid, partially neutralized polyacrylic acid, acrylic acid-maleic acid copolymer acid, and acrylic acid-maleic acid copolymer. 15. The method according to claim 14, which is a mixture of one or two or more compounds selected from the group consisting of partially neutralized products of the acid. 16. The method according to claim 13, wherein the spray-dried particles are particles obtained by spray-drying an aqueous slurry containing one or more kinds of organic or inorganic builders. 17. The spray-dried particles are carbonates, crystalline aluminosilicates, citrates, mirabilite, sulfites, polyacrylates, salts of acrylic acid-maleic acid copolymers,
The production method according to claim 16, which is particles obtained by spray-drying a slurry containing a mixture of one or more compounds selected from the group consisting of polyglyoxylate salts, anionic activators, nonionic activators, and fluorescent dyes. . 18. The production method according to claim 1 or 13, wherein the blending amount of the detergent raw material in the step (1) is selected from the following (a) or (b). (A) A total of 10 to 60 parts by weight of a nonionic activator and / or an aqueous solution of a nonionic activator and an acid precursor of an anionic surfactant capable of lamellar orientation, a builder exhibiting alkalinity and / or a porous exhibiting alkalinity. 40-90 parts by weight of a water-soluble oil-absorbing carrier, and 0-10 parts by weight of a builder exhibiting neutrality or acidity, (b) an acid precursor of an anionic surfactant capable of forming a lamellar orientation with a nonionic surfactant and / or an aqueous solution of a nonionic surfactant. 10-60 parts by weight of the total amount of the body, builder exhibiting alkalinity and / or porous oil-absorbing carrier 10-8 exhibiting alkalinity
0 parts by weight, neutral or acidic builders 0-10
Parts by weight, and 10 to 80 parts by weight of spray-dried particles. 19. A method of performing step (2) using a stirring type mixer equipped with a jacket capable of flowing hot water or the like, wherein the temperature of the hot water or the like to be flown to the jacket is as follows: Alternatively, the manufacturing method according to claim 1, 11 or 12, wherein the temperature is higher than the temperature shown in (B). (A) When step (1) is carried out using a mixed solution obtained by mixing a nonionic activator and / or an aqueous solution of a nonionic activator with an acid precursor of an anionic surfactant capable of lamellar orientation, the mixed liquid (B) When the step (1) is carried out by separately adding the nonionic surfactant and / or the aqueous solution of the nonionic surfactant and the acid precursor of the anionic surfactant capable of lamellar orientation, the melting point of these compounds Whichever is higher, melting point 20. The production method according to claim 19, wherein the granulation in the step (2) is performed by a stirring type mixer having a stirring shaft at the center of a horizontal cylinder and a stirring blade on the stirring shaft. 21. The method according to claim 20, wherein the granulation is performed under the condition that the Froude number is 1 to 4 based on the rotation of the stirring blade of the stirring type mixer used in the step (2). 22. The production method according to claim 19, wherein the granulation in the step (2) is carried out for a granulation time of 2 to 20 minutes. 23. The manufacturing method according to claim 1, wherein the step (1) and the step (2) are performed in the same apparatus. 24. The production method according to claim 1, further comprising the step of mixing the granulated product obtained in step (2) with a fine powder and coating the surface of the granulated product with the fine powder. . 25. The average particle diameter of primary particles of fine powder is 10 μm.
25. The method according to claim 24, wherein the amount of fine powder is 0.5 to 20 parts by weight with respect to 100 parts by weight of the granulated product. 26. The method according to claim 25, wherein the fine powder is a mixture of one or more compounds selected from the group consisting of crystalline or amorphous aluminosilicates and calcium silicate. 27. The method according to claim 1, wherein the nonionic detergent particles obtained have an average particle size of 250 to 800 μm. 28. When the fluidity of the resulting nonionic detergent particles is evaluated by the time (fluid time) required for 100 ml of the particles to flow out from a hopper for measuring bulk density defined by JIS K 3362, Flow time 1
The manufacturing method according to claim 1, which is 0 seconds or less. 29. The production method according to claim 1, wherein the nonionic detergent particles obtained have a caking property of 90% or more on a sieve passing rate.