JP2003238998A - Method for producing granular detergent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compression molded detergent which controls the surface adhesive force of detergent particles. <P>SOLUTION: The method for producing a detergent has a means to measure the adhesive force of the granulates of detergent particles, a means to adjust the amount of an adhesive force-reducing agent for the granulates to be added and/or a means to adjust the amount of a liquid binder for increasing the adhesive force to be added, and comprises controlling the amount of the adhesive force-reducing agent and/or the liquid binder to be added in accordance with the measured adhesive force of the granulates. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Stabilizes granular detergents for processing into compression molded detergents, etc.
The present invention relates to a manufacturing method for efficiently obtaining the same. [0002] 2. Description of the Related Art Conventionally, high detergents represented by compact detergents have been used.
Bulk density granular detergents are widely used as laundry detergents for home use
Has been used as a detergent product in recent years.
In addition to tablet detergents and briquette detergents,
It is also used as an intermediate for detergents. In particular, compression
When used as an intermediate material for molding detergents, the particle surface adheres
Force is a physical property that directly reflects the compressibility of particles.
Is an important factor affecting the quality of compression-molded detergents.
You. However, in the conventional method for producing a granular detergent,
Was controlled for particle size and solubility
However, particle surface adhesion is controlled.
Due to fluctuations in environmental factors such as temperature and humidity.
The particle surface adhesion tends to vary, and the desired particle surface
It is difficult to produce a granular detergent with surface adhesion.
Was. For example, Japanese Patent Application Laid-Open No. 2000-84391
In, the high bulk density granular detergent to control the average particle size
A manufacturing method is disclosed in Japanese Patent Application Laid-Open No. 2000-14419.
No. 8 discloses production of a high bulk density granular detergent for controlling solubility.
A method has been disclosed and further disclosed in JP-A-11-34999.
No. 8 discloses a high bulk density granular detergent by a kneading and crushing granulation method.
In the production of the product, such as adhesion of equipment with a continuous kneader or extrusion granulator
A control method at the time of granulation to eliminate trouble has been disclosed
I have. However, these methods do not include detergent particles.
No technique for controlling surface adhesion has been suggested.
There was a problem in producing a constant quality detergent. [0004] SUMMARY OF THE INVENTION The present invention
To solve the problems in
Target. That is, the present invention is applicable to the production of detergents for compression molding.
Suppress variations in surface adhesion of granular detergent particles used for processing
In addition, use a granular detergent for processing that has a certain particle surface adhesion.
Provide a production method for constant and efficient production
That is the purpose. [0005] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to solve the problem, we
Means for measuring the adhesive force of the granulated material during granulation;
And / or granulation for adjusting the amount of adhesion reducing agent added
Means for adjusting the amount of liquid binder added at the time,
Depending on the measured adhesion of the granules, the adhesion of the granules is low.
Controls the amount of liquid binder added when reducing and / or granulating
And a method for producing a granular detergent. [0006] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.
Will be described. The detergent particles used in the present invention are generally
It contains a surfactant compound and a builder. (1) Surfactant (A) anionic surfactant Preferred anionic surfactants include, for example,
Linear or branched alkyl having 8 to 16 alkyl groups
Lebenzenesulfonate, alkyl having 10 to 20 carbon atoms
Sulfuric acid (AS) salt or alkenyl sulfate, having 10 to 2 carbon atoms
Α-olefin sulfonic acid (AOS) salt of 0, carbon number 1
Alkanesulfonic acid salt of 0-20, having 10-20 carbon atoms
Has a linear or branched alkyl or alkenyl group
Ethylene oxide having an average addition mole number of 10 moles or less.
, Propylene oxide, butylene oxide or
Alkyl ether sulfuric acid (AE
S) Salt or alkenyl ether sulfate, having 10 to 10 carbon atoms
20 linear or branched alkyl or alkenyl groups
Group having an average addition mole number of 10 moles or less.
Oxide, propylene oxide, butylene oxide
Or an alkyl ether compound to which a mixture thereof is added
Rubonate or alkenyl ether carboxylate, carbon
Alkyl glyceryl ether sulfonic acid of several 10 to 20
Alkyl polyhydric alcohol ether sulfates, such as carbon
Higher fatty acid salts of several 10 to 20, saturated or 8 to 20 carbon atoms
Is an unsaturated α-sulfofatty acid (α-SF) salt or its methyl
Anion interface such as propyl ester
Activators, or mixtures thereof can be used
You. Particularly preferred anionic surfactants include, for example,
For example, the linear alkylbenzene sulfonic acid (LAS)
Potassium metal salt (eg, sodium or potassium salt)
And alkali metal salts of AOS, α-SF and AES (for example,
Sodium or potassium salts, etc.)
Potassium metal salts (eg, sodium or potassium salts)
And so on. (B) Nonionic surfactant Preferred nonionic surfactants include, for example,
Things can be mentioned. (I) an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms;
An average of 3 to 2 alkylene oxides having 2 to 4 carbon atoms
Polyoxy with an addition of up to 30 mol, preferably 5 to 20 mol
Sialkylene alkyl (or alkenyl) ether. This
Among them, polyoxyethylene alkyl (or alkenyl)
Le) ether, polyoxyethylene polyoxypropyl
Alkyl (or alkenyl) ethers are preferred.
The aliphatic alcohol used here is a primary alcohol.
The alcohol and the secondary alcohol are used. Also,
May have a branched chain. preferable
Primary alcohols are used as aliphatic alcohols.
It is. (Ii) polyoxyethylene alkyl (or alkenyl)
Le) phenyl ether. (Iii) Ester bond of long-chain fatty acid alkyl ester
An alkylene oxide is added in between, for example, by the following formula
The fatty acid alkyl ester alkoxylates shown. R₁CO (OA)_nOR₂ (R₁CO has 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
Represents a fatty acid residue. OA is ethylene oxide,
C2-4, preferably C2-3, such as pyrene oxide
Represents an additional unit of an alkylene oxide. n is alk
Indicates the average number of moles of added lenoxide, generally 3 to 3
It is a number of 0, preferably 5-20. R₂Is carbon number 1
Represents a lower alkyl group which may have 1 to 3 substituents. ) (Iv) Polyoxyethylene sorbitan fatty acid ester
Le. (V) Polyoxyethylene sorbite fatty acid ester. (Vi) Polyoxyethylene fatty acid esters. (Vii) Polyoxyethylene hydrogenated castor oil. (Viii) glycerin fatty acid esters. Among the nonionic surfactants, the melting point is 40 ° C. or less.
With an HLB of 9 to 16 polyoxyethylene alkyl (or
Is alkenyl) ether, polyoxyethylenepolyoxy
Cypropylene alkyl (or alkenyl) ether, fat
Fatty acid with ethylene oxide added to fatty acid methyl ester
Acid methyl ester ethoxylate, fatty acid methyl ester
Ethylene oxide and propylene oxide
Fatty acid methyl ester ethoxypropoxylate
It is suitably used. In addition, these nonionic surfactants
The agents may be used as a mixture. (C) Amphoteric surfactant Preferred amphoteric surfactants include, for example, imidazoly
And amphoteric surfactants such as amidobetaine
be able to. Particularly preferred amphoteric surfactants include
For example, 2-alkyl-N-carboxymethyl-N-h
Droxyethyl imidazolinium betaine, laurin
Acid amide propyl betaine; The interface
The activator is usually from 10 to 60, based on the weight of the detergent granules.
% By weight, preferably 15 to 50% by weight, particularly preferably
Is contained in an amount of 20 to 45% by weight. (2) Detergent builder Builders used in the present invention include inorganic and organic
Rudder. As the inorganic builder,
For example, sodium carbonate, potassium carbonate, sodium bicarbonate
, Sodium sulfite, sodium sesquicarbonate, sodium silicate
Thorium, crystalline layered sodium silicate, amorphous layered silica
Alkaline salts such as sodium acid, sodium sulfate, etc.
Neutral salt, orthophosphate, pyrophosphate, tripolyline
Acid salt, metaphosphate, hexametaphosphate, phytic acid
Phosphates such as salts, General formula: x¹(M₂O) · Al₂O₃・ Y¹(Si
O₂) ・ W¹(H₂O) (where M is sodium, potassium
Alkali metal atom such as um, x¹, Y¹And w¹Is each
Indicates the number of moles of the component, generally x¹Is 0.7 ~
Number 1.5, y¹Is a number from 0.8 to 6, w¹Is any positive number
Crystalline aluminosilicate represented by: General formula: x²(M₂O) · Al₂O₃・ Y²(Si
O₂) ・ W²(H₂O) (where M is sodium, potassium
Alkali metal atom such as um, x², Y²And w²Is each
Indicates the number of moles of the component, generally x²Is 0.7 ~
1.2 number, y²Is a number from 1.6 to 2.8, w²Is 0 or
Represents any positive number) amorphous aluminosilicate represented by
salt, General formula: x³(M₂O) · Al₂O₃・ Y³(Si
O₂) .Z³(P₂O₅) ・ W³(H₂O) (Where M is an alkali metal source such as sodium, potassium, etc.)
Child, x³, Y³, Z³And w³Indicates the number of moles of each component
And in general, x³Is a number from 0.2 to 1.1, y³Is
A number from 0.2 to 4.0, z³Is 0.001-0.8, w³
Is 0 or any positive number).
Silicates and the like. Among the inorganic builders,
Sodium carbonate, potassium carbonate, sodium silicate, bird
Sodium polyphosphate and sodium aluminosilicate are preferred
New As the organic builder, for example,
Trilotriacetate, ethylenediaminetetraacetate, β
-Alanine diacetate, aspartate diacetate, methyl
Aminocars such as glycine diacetate and iminodisuccinate
Bonate; serine diacetate, hydroxyiminodisuccinate
Acid salt, hydroxyethyl ethylenediamine triacetate, di
Hydroxyaminocarb such as hydroxyethylglycine salt
Bonate; hydroxyacetate, tartrate, citrate,
Hydroxycarboxylates such as gluconate;
Toluate, benzopolycarboxylate, cyclopentanedetate
Cyclocarboxylates such as lacarboxylates;
Tiltartronate, carboxymethyloxysuccine
Salt, oxydisuccinate, tartaric acid mono or disac
Ether carboxylate such as sinate; polyacrylic acid;
Acrylic acid-allyl alcohol copolymer, acrylic acid-
Maleic acid copolymer, hydroxyacrylic acid polymer,
Acrylic acid polymers such as saccharide-acrylic acid copolymers and
Copolymer; maleic acid, itaconic acid, fumaric acid, tetra
Methylene 1,2-dicarboxylic acid, succinic acid, asparagine
Polymers or copolymers such as acid; starch, cellulose
, Amylose, pectin, etc.
Polysaccharides such as cimethylcellulose; polyethylene glycol
, Polyvinyl alcohol, polyvinyl pyrrolidone, etc.
Non-dissociated polymer compounds and the like. These organic buildings
Citrate, aminocarboxylate, poly
Acrylate and acrylic acid-maleic acid copolymer
Body is preferred. The builder is usually used alone or in combination of two types.
These are used in combination. The amount of the builder is sufficient
In detergent granules, it is preferable to provide 1
5 to 40% by weight, particularly preferably 20 to 30% by weight
It is desirable to mix them. (3) Oil-absorbing carrier As the oil-absorbing carrier used in the present invention, preferably,
Oil absorption of 80m as specified by JIS-K5101 test method
1/100 g or more, preferably 150 to 600 ml / 1
An oil-absorbing substance of 00 g is preferably used. This
Such oil-absorbing carriers include, for example, silicate compounds.
, Tokusil N [manufactured by Tokuyama Corporation, oil absorption 280m
1/100 g], Nip Seal NS-K [Nippon Silica
Oil absorption 320ml / 100g], Sylysia
# 310 [manufactured by Fuji Silysia Chemical Ltd., oil absorption 340 m
l / 100 g], etc.
Kusu H-52 [Asahi Glass Co., Ltd., oil absorption 260ml / 1
00g] etc., spherical porous hydrous amorphous silicic acid, Aerosil
# 300 [Nippon Aerosil Co., Ltd., oil absorption 350ml
/ 100g], amorphous anhydrous silicic acid such as
To R [manufactured by Tokuyama Corporation, oil absorption 600ml / 100
g] such as petal-like hydrated amorphous calcium silicate, Zonotra
[Ube Chemical Co., Ltd., oil absorption 220ml / 100
g], etc.
Minosilicate [Mizusawa Chemical Co., Ltd., oil absorption 170ml / 1
00g], magnesium silicate [oil absorption 180ml / 10
0g]. In addition, as a carbonate compound,
Gnesium [manufactured by Tokuyama Corporation, oil absorption 150ml / 1
00g], calcium carbonate [manufactured by Shiraishi Industry Co., Ltd., oil absorption
110ml / 100g], and other compounds
Particle spinel [Sumitomo Cement Co., Ltd. oil absorption 600m
l / 100 g], ultra fine particle cordierite [Sumitomo Seme
Oil absorption 600ml / 100g], ultra fine particles
Mullite [Sumitomo Cement Co., Ltd., oil absorption 560ml
/ 100g], modified starch pine flow S [Matsuya Chemical
Oil absorption 130ml / 100g].
You. These oil absorbing carriers may be used as a mixture.
No. Oil-absorbing carriers are usually based on detergent granular weight,
0.1 to 25% by weight, preferably 0.5 to 20% by weight
%, Particularly preferably 1 to 15% by weight. (4) Clay mineral As the clay mineral used as the detergent component of the present invention,
In particular, it belongs to the smectite group and its crystal structure is
Hedral type three-layer structure or trioctahedral type three-layer structure
Is preferred. Preferred as a detergent component of the present invention
The clay mineral that can be used preferably has an oil absorption of 80 ml.
/ 100g, more preferably 30-70ml / 10
0 g, the bulk density is preferably 0.1 g / ml or more, especially
Preferably it is 0.2-1.5 g / ml. this
Specific examples of such clay minerals include, for example, dioctahedra
Montmorillonite as a clay mineral with a three-layer structure
(Oil absorption: 50 ml / 100 g, bulk density: 0.3 g / m
l), nontronite (oil absorption: 40 ml / 100 g,
Bulk density: 0.5 g / ml), Beiderite (oil absorption: 6)
2ml / 100g, bulk density: 0.55g / ml), pie
Lophylite (oil absorption: 70 ml / 100 g, bulk density:
0.63 g / ml).
Saponite is a clay mineral with a three-layered hedral structure.
(Oil absorption: 73 ml / 100 g, bulk density: 0.15 g /
ml), hectorite (oil absorption: 72 ml / 100 g,
Bulk density: 0.7g / ml), Stephen site (oil absorption)
Amount: 30 ml / 100 g, bulk density 1.2 g / ml),
Luc (oil absorption: 70 ml / 100 g, bulk density: 0.1 g)
/ Ml). Clay minerals, detergent granular weight
0.1 to 30% by weight, preferably based on the amount, preferably
0.5 to 20% by weight, particularly preferably 1 to 10% by weight
Have. The raw material components of the above (1) to (4) are converted into a slurry.
After blending, it may be spray-dried to obtain a dry powder. (5) Dissolution accelerator As the dissolution promoter used in the present invention, for example, carbonic acid
Potassium, ammonium sulfate, ammonium chloride, etc.
Inorganic ammonium salt, sodium benzoate, benzene
Sodium sulfonate, sodium p-toluenesulfonate
, Sodium xylene sulfonate, sodium chloride,
Water-soluble substances such as citric acid, D-glucose, urea, and sucrose
Is mentioned. In addition, swellable water-insoluble substances are also preferred.
Good. Specifically, powdered cellulose, crystalline cellulose
Carboxymethylcellulose with low etherification degree,
Bridge-type carboxymethylcellulose, carboxymethylcellulose
Lulose calcium, hydroxypropyl cellulose, etc.
Cellulose derivatives, starches such as corn starch,
Starch derivatives such as droxypropyl starch, cross-linked
Polyvinyl pyrrolidone, polyvinyl ether with low degree of etherification
And the like. Ingredients of components to be incorporated in other detergent particles
The following are shown as examples. (6) Fluorescent agent: bis (triazinylamino) stilbene
Disulfonic acid derivative, bis (sulfostyryl) biphenyl
Salt (Tinopearl CBS) and the like. (7) Antistatic agent: dialkyl type quaternary ammonium salt
Which cationic surfactant etc. (8) Anti-redeposition agent: carboxymethyl cellulose, etc.
Cellulose derivatives and the like. (9) Extender: sodium sulfate, potassium sulfate, sodium hydrochloride
Thorium and the like. (10) Reducing agent: sodium sulfite, potassium sulfite
etc. In the present invention, an agent for reducing the adhesion of granules and
A liquid binder for granulation and / or granulation is essential.
These components are included in the components of the detergent particles described above. Granulation
As an agent for reducing the adhesive force of a substance, a non-
Machine builder, oil-absorbing carrier, viscosity minerals, etc.
Zeolite, talc, montmorillonite, etc.
Appropriately available. In addition, as an adhesive force increasing agent, liquid during granulation
Nonionic surfactants, anions
Surfactant, cationic surfactant, amphoteric surfactant, high
Molecular builder, water, etc.
Surfactants, anionic surfactants, amphoteric surfactants and
Aqueous solution, polyethylene glycol, acrylic acid
An aqueous solution of a maleic acid copolymer, water, etc. can be more suitably used.
You. The detergent particles used in the present invention are the aforementioned surfactants.
Contains compounds and polymer builders and other components, average
It is preferable that the particle size is 200 to 1500 µm. So
The reason for using granular detergent as compression molding detergent
In the case, sufficient water penetration into the compression detergent and more
Particles must adhere to each other to obtain sufficient strength at low molding pressure
It is important to engage without
Needs a particle size larger than the size of the granules, while dissolving the granules themselves
This is because there is an upper limit of the particle size in order to ensure the properties. Follow
The detergent particles used in the present invention are more preferably
Uniform particle size of 200 to 1500 µm and 150 µm or less
The particle size ratio is less than 10%. Particularly preferred in the present invention
The detergent particles used have an average particle size of 500 to 1000.
μm and the particle size ratio of 150 μm or less is less than 5%
is there. In the present invention, any granulation method is usually used.
Granular detergent may be manufactured by the following method.
It is preferred to obtain a particulate detergent. They are detergent components
Raw material powder and binder component (surfactant, water, liquid
After kneading and kneading body polymer components, extrude and granulate
After extrusion granulation, kneading and kneading, the obtained solid
Kneading and crushing granulation method to crush and granulate detergent
Add a binder component and stir with stirring blades to granulate
Agitation granulation method and binder forming while rolling raw material powder
Tumbling granulation method, etc., in which the mixture is sprayed and granulated. Below,
Explains how to make granular detergent by each granulation method
I do. The raw material powder is the raw material powder of each component.
It may be directly subjected to granulation operation, or the raw material powder of each component may be bound.
Dissolves like a slurry with surfactant, water, liquid polymer components, etc.
After disintegrating, processing into dry powder spray-dried and then granulation
May be served. 1. Extrusion granulation In the extrusion granulation method, any type of kneading and extruding machine
Can be used, any type of kneader and extruder
It may be used in combination with a machine. Kneading / extruding machine
For example, Extrude O Mix
(Manufactured by Hosokawa Micron Corp.) Twin screw kneading extruder
(Manufactured by Kurimoto Tekkosho Co., Ltd.).
And KRC Kneader (made by Kurimoto Iron Works Ltd.)
Agitator (made by Dalton Co., Ltd.), Nautamixer (Hosoka
Extruder).
Is Twin Dome Gran (made by Fuji Paudal Co., Ltd.)
Letter Double (Fuji Paudal Co., Ltd.), Fine
Luiser (made by Fuji Paudal Co., Ltd.) and the like. 1-1. Adjust the amount of the adhesion reducing agent
Means to control The granulated material obtained by the extrusion granulation method is granulated and then rolled.
It is coated with an adhesion reducing agent by a dynamic coating operation or the like. this
In this case, the rolling coater is the same as the rolling granulator described later.
Can be used. Adhesion reducer rolls with granulation
It is put into a dynamic coating device, and the adhesive force added at this time is reduced.
The addition amount of the agent is electromagnetic feeder, table feeder, etc.
Adjustment and control by feeding using various supply devices
It is possible. 1-2. Addition amount of liquid binder during granulation
Means to control In extrusion granulation, the liquid binder is supplied to the granulator in advance.
Premix the powdered raw material to be supplied in advance or
Or granulate simultaneously with the powder raw material from the addition port of the powder raw material
Added to equipment. The liquid binder added at this time
Gear pump, spiral pump, piston pump
Adjustment by feeding using various supply devices such as
It can be controlled. 2. Kneading and crushing granulation method In the kneading and crushing granulation method, any type of kneader and crusher can be used.
Combination, if necessary any type of kneader, pressing
Can be used in combination with unloader and crusher
You. As a kneading machine, KRC Kneader (Kurimoto Iron Works Co., Ltd.)
Seikosha), continuous kneader (Fuji Paudal Co., Ltd.),
Continuous kneading machine (made by Powrex Co., Ltd.), universal mixing and stirring
Machine (Dalton Co., Ltd.), Nauta mixer (Hosoka
Wakmicron Co., Ltd.). These kneading machines
The kneaded material obtained in this step may be ground as it is,
Pelletized with an extruder for ease
Thus, the pulverization efficiency can be increased. This push
Pellet Double (Fuji Paudal Co., Ltd.)
), Twin Dome Gran (Fuji Paudal Co., Ltd.)
Manufactured by Fuji Paudal Co., Ltd.)
and so on. Kneading extrusion that simultaneously performs kneading and extrusion
Machine, Extruded Omics (Hosokawa Micro
Twin screw extruder (Kurimoto Iron Works Co., Ltd.)
) Can also be used. Crush the kneaded material
A crusher with a classification screen and rotating blades
Models are preferred. As this crusher, Fitzmill (Ho
Sokawa Micron Corporation), New Speed Mill (Oka
Co., Ltd. (manufactured by Taseiko Co., Ltd.)
Feather Mill (Hosokawa Micron Corporation)
Company). When further crushing,
The use can be efficiently pulverized. This
Inorganic powder having an average particle size of 30 μm or less is used as a grinding aid.
Preferably, for example, type A zeolite, finely divided sodium carbonate, e
Wite carbon, talc, etc. are used, and the amount
0.5 to 15 parts by weight per 100 parts by weight of the ingredients to be crushed
It is more preferably 2 to 10 parts by weight. Also crushed
It is also possible to pulverize while cooling by flowing cold air in the machine.
Classify cold air and crushed product with cyclone, then classify fine powder
It is also possible. Preferably, multi-stage pulverization
This makes the particle size distribution sharper. Crusher shake
15 to 90 m / s is preferable as the tip peripheral speed of the cable.
No. More preferably 20 to 80 m / s, even more preferably
Is 25 to 70 m / s. If the speed is less than 15m / s
The force decreases and the productivity drops, and at 90 m / s or more,
It becomes easy to over-crush. 2-1. Adjust the amount of the adhesion reducing agent
Means to control After granulation by the kneading and crushing granulation method,
It is coated with an adhesion reducing agent by a rolling coating operation or the like. This
In this case, the rolling coating device is the same as the rolling granulation device described later.
Can be used. Adhesion reducer with granulated material
It is introduced into the rolling coating device, but the adhesive force added at this time is low.
Additive amount of reducer is electromagnetic feeder, table feeder
Adjustment by feeding using various supply devices such as
It can be controlled. 2-2. Addition amount of liquid binder during granulation
Means to control In kneading and crushing and granulation, the liquid binder is
Premixed with the powder raw material supplied to
Alternatively, it can be manufactured simultaneously with the powder material from the powder material addition port.
Added to the granulator. Liquid binder added at this time
Gear pump, spiral pump, piston pump
Adjustment by adding using various feeding devices
It can be controlled. 3. Agitation granulation method In the stirring granulation method, any type of stirring granulator can be used.
Can be. Among them, a stirring shaft equipped with stirring blades
At the center of the section, when the stirring blades rotate,
It is preferable that the structure be such that a clearance is formed between it and the wall.
Good. Clearance is preferably 1-30mm
And 3 to 10 mm is more preferable. Less than 1mm adheres
The beds tend to overpower the mixer. Over 30mm
In this case, the compaction efficiency decreases and the particle size distribution broadens.
In addition, the granulation time is prolonged, and the productivity is reduced. this
Stirring granulators with similar structures include, for example, Hensche
Mixer (Mitsui Miike Kakoki Co., Ltd.), high speed
Mixer [Fukae Kogyo Co., Ltd.], Vertical Granule
Equipment (made by Powrex Co., Ltd.).
Preferably, it is a horizontal mixing tank with a stirring shaft at the center of the cylinder.
Mixer that mixes powder by attaching stirring blades to the shaft of
Sir, for example, Redige Mixer [Matsubo Co., Ltd.
Blowshare Mixer [manufactured by Taiheiyo Kiko Co., Ltd.]
You. The preferable granulation conditions in the stirring granulation method are as follows.
It is shown below. (1) Fluid number (Fr number) In the stirring granulation method, a fluid defined by the following formula
Is preferably 1 to 16, more preferably 2 to 9.
New When the Froude number is 1 or less, consolidation is promoted.
On the other hand, if it exceeds 16, the particle size distribution is broad.
It may be. Fr = V²/ (R × g) V: Peripheral speed at the tip of the stirring blade [m / s] R: radius of rotation of the stirring blade [m] g: Gravitational acceleration [m / s²  ] (2) Chopper rotation speed In the stirring granulation method, the stirring granulator used includes:
High-speed rotation to promote the compaction of granulated materials and the disintegration of coarse powder
Is equipped with a chopper. Rotation of the chopper
The speed is 20-30 in chopper tip speed (peripheral speed)
m / s is preferred, and 22 to 28 m / s is more preferred. (3) Granulation time In the stirring granulation method, the number of times for obtaining a suitable granulated material is increased.
For granulation time in grammatical granulation and continuous granulation
The average residence time is preferably 0.5 to 20 minutes, and 3 to
10 minutes is more preferred. Granulation time (average residence time)
However, if the time is less than 0.5 minutes, the time is too short,
It is difficult to control granulation to obtain a proper average particle size and bulk density.
20 minutes while the particle size distribution may be broad
Exceeds this time, productivity may decrease due to too long a time.
You. (4) Filling rate of detergent raw material In the stirring granulation method, the filling rate of the detergent raw material into the granulator
70% by volume of the total internal volume of the mixer
The following is preferable, and 15 to 40% by volume is more preferable. Previous
When the filling rate (prepared amount) exceeds 70% by volume, the mixing machine
Mixing efficiency of detergent raw material in the inside is reduced, and granulation is performed appropriately
You may not be able to do it. 3-1. Adjust the amount of the adhesion reducing agent
Means to control The granulated product obtained by the stirring granulation method is used after granulation.
Perform the stirring operation using the granulator
Or coated with an adhesion reducing agent by a rolling coating operation, etc.
You. When performing the rolling coating operation, the rolling coating device will be described later.
The same thing as a tumbling granulator can be used. Adhesion
The force reducing agent is agitation granulator or rolling coating device with the granulated material.
The amount of the adhesion reducing agent added at this time
Are various feeders such as electromagnetic feeders and table feeders.
Can be adjusted and controlled by
You. 3-2. Addition amount of liquid binder during granulation
Means to control The liquid binder used in the stirring granulation is previously formed.
Premix with the powder raw material supplied to the granulator
Granulate simultaneously with powder raw material from the addition port of powder raw material
Added to the equipment or during the granulation operation of the powder raw material
Are added sequentially. The liquid binder added at this time
Gear pump, spiral pump, piston pump
Adjustment by adding using various feeding devices
It can be controlled. 4. Rolling granulation method In rolling granulation, any type of rolling granulator can be used.
Can be. Among them, the drum-shaped cylinder rotates and processes
It is preferable to provide a baffle plate of any shape.
Are preferred. Water as the above drum type granulator
In addition to the flat cylinder type granulator, edited by the Japan Powder Technology Association,
Conical drum type granulator described in the first edition of the bookbook, 1st printing, multi-stage
Conical drum type granulator, drum type granulator with stirring blade, etc.
I can do it. Preferred granulation conditions in the above-mentioned tumbling granulation method are as follows.
It is shown below. (1) Processing time Processing time for high bulk density in batch type or continuous
The average residence time, defined by the following equation:
Minutes, preferably 10 to 90 minutes, particularly preferably 10 to 4 minutes.
0 minutes. If the time is less than 5 minutes, the bulk density is sufficient
Although it may not be able to rise, production will take more than 120 minutes
Deterioration of detergent properties or disintegration of detergent granules may occur.
You. Tm = (m / Q) × 60 Tm: average residence time (min) m: Detergent granule retention amount in the container rotary mixer (kg) Q: Capacity in continuous operation (kg / hr) (2) Froude number (Fr) The Froude number defined by the following equation is 0.01 to
It is preferable to select a condition that results in 0.8. The conditions
Is preferably from 0.05 to 0.7, more preferably from 0.1 to 0.
65 is more preferred. The Froude number is less than 0.01
If it is, uniform and high bulk density detergent particles cannot be obtained.
On the other hand, if it exceeds 0.8, the drum type mixer
In the event of agitation, the detergent granules will scatter and normal shear mixing will occur.
May not happen. Fr = V²/ (R × g) V: Peripheral speed (m / s) at the outermost periphery of the container rotary mixer R: radius from the center of rotation of the outermost periphery of the container rotary mixer
(M) g: Gravitational acceleration (m / s²) (3) Volume filling rate The volume filling rate defined by the following equation is 15 to 50%.
Select the conditions to be used. Preferably 20-45%, more preferably
Preferably, it is 25 to 40%. From the viewpoint of productivity,
The filling rate is preferably 15% or more, and good shear mixing is not caused.
It is preferably 50% or less from the viewpoint of performing the treatment. Volume filling rate = (M / ρ) / V × 100 M: Amount of detergent granule particles charged to the container rotary mixer
(G) ρ: bulk density (g / L) of detergent granule particles V: Volume (L) of the container rotary mixer 4-1. Adjust the amount of the adhesion reducing agent
Means to control The granulated product obtained by the tumbling granulation method is used after granulation.
Rolling operation using the same granulation device used,
Alternatively, coat with an adhesion reducing agent using another rolling coating device
Is done. The rolling coating device is similar to the rolling granulation device described above.
Can be used. Adhesion reducer and granulated material
Into the rolling coater, the adhesive force added at this time
The amount of reducing agent added is electromagnetic feeder, table feeder
Adjustment by feeding using various supply devices such as
It can be controlled. 4-2. Addition amount of liquid binder during granulation
Means to control In the tumbling granulation, the liquid binder is granulated powder raw material.
Sprayed sequentially during operation. Liquid vine added at this time
The addition amount of the mixer is gear pump, spiral pump, piston pump
Pumps, etc.
It can be adjusted and controlled. The detergent particles granulated by the above method are necessary
And use only detergent particles of the desired particle size in the product
You can also. Want to be generally known as a classifier
Such a classifier can also be used, and a sieve is particularly suitable.
Can be used. Among them, gyroscopic sieves, flat sieves and vibrating sieves are preferred.
Suitable. Gyro-type sieves are suitable for slightly inclined flat sieves.
It is a sieve that gives horizontal circular motion. The plane sieve is slightly inclined
With a sieve that gives reciprocating motion almost parallel to the surface on the inclined plane sieve
is there. The vibrating sieve applies rapid vibration to the sieve surface in a direction
It is a sieve. The time for sieving should be 5 seconds or more
Desirable, and to improve sieving efficiency, tapping
It is also preferable to use a ball. Of such a sieve
A specific example is Gyro Shifter (Tokuju Kosaku Co., Ltd.)
Place), RO-TEX SCREENER (Seishin K.K.)
Industry), Dalton vibration sieve (Dalton Co., Ltd.)
I can do it. Vibration by a sieve is 60 to 3000 times / min.
Preferably 100 to 2500 times / minute, more preferably 15 times
It is given with a vibration of 0 to 2000 times / min. Vibration of the sieve
If the number is less than 60 times / minute, the classification effect may be deteriorated.
On the other hand, if it exceeds 3000 times / minute, dust generation may increase.
There is. In the present invention, the granulation method
With means for measuring the surface adhesion of the resulting detergent particles
Is essential. The measurement principle of particle surface adhesion
The detergent particles under certain conditions (speed, direction, load)
And pull the molded product under a certain condition (speed, direction).
Measure the maximum force required to divide the molded product into two parts.
Is generally used as the surface adhesive force. This principle
Hosokawa Micron Co., Ltd.
Agu robot, Sankyo Piotech Co., Ltd., powder
Bed testers are examples. As a numerical value indicating the adhesive force,
Measured using Agrobot, manufactured by Hosokawa Micron Corporation
The typical value of the tensile rupture stress [Pa]
can give. The specific method of measuring the tensile rupture stress is shown below.
You. Measuring method of tensile rupture stress: Hosokawa Micron Corporation
Made of metal, which can be divided into two parts using an Agu robot
Detergent granules in cell (cell inner diameter 25mm x height 37mm)
15g, temperature 20 ℃, maximum compression force 980N
(Maximum compression pressure 2.0MPa), holding time 0 seconds, compression speed
Compressed under the condition of degree 1.0mm / sec, and tension spring wire diameter
1.2 mm, tensile speed 0.4 mm / sec, 20 ° C strip
Only the upper cell was pulled and the cell broke up and down
The maximum tensile stress at this time is defined as a tensile rupture stress [Pa]. The surface of the detergent particles is obtained by using the tensile breaking stress.
Generally speaking, the adhesive force is 100 Pa to 100,000 Pa.
But the tensile rupture stress of the granular detergent that becomes the product as it is
Is usually 100 to 70000 Pa, and the
Tensile rupture stress of granular detergent used as intermediate material is usually 3
000 to 100,000 Pa. As a method for measuring the surface adhesion of other detergent particles,
Is a tablet with constant weight, size and molding pressure
The tablet hardness [N] is measured and the tablet hardness is measured.
A method is known in which the degree is defined as the adhesive force of detergent particles. this
The measurement principle is the same as the measurement of tensile rupture stress.
However, there is an advantage that the operation is simple. less than
An example of this method will be described. Simple adhesion measurement method 38g of detergent particles in a φ45mm semi-circular cylindrical tablet mold
Filling, Mikado Technos Co., Ltd., Mikado Air Press
Forming thrust 2450N using MKP-100S type, maximum
Compression molding under the conditions of compression speed setting and compression holding time of 1 second
To obtain tablets of detergent particles. Then the hardness of the tablet
[N] is a digital tablet hardness tester TS- manufactured by Okada Seiko Co., Ltd.
Pressing arm at a speed of 0.3 mm / s using 75NL
To apply force in the diametric direction from the cylindrical side of the tablet,
Measures the maximum thrust required to divide the agent into two in the direct line direction
The value is referred to as a simple adhesive force [N]. This simple attachment
The figure between the force [N] and the tensile rupture stress [Pa] mentioned above
As shown in FIG. 1, a linear correlation exists.
The method is also suitable as a method for measuring the surface adhesion of detergent particles.
You. In the present invention, the measurement is performed in this manner.
Adhesive force of granulated material according to the surface adhesive force of the detergent particles
Amount of reducing agent added and / or liquid binder during granulation
Control the amount added. Each control method is as follows
is there. (A) Addition amount of adhesion reducing agent for granulated material Adhesion reducer covers the surface of detergent particles and adheres to detergent particles
Table of measured detergent particles, because it is a force-reducing agent
If the surface adhesion is greater than the desired value, increase the addition amount.
However, if it is smaller than the desired value, reduce the amount added.
And bring the surface adhesion of the detergent particles closer to the desired value.
It is possible to go. (B) Addition amount of liquid binder during granulation The liquid binder is a binder of the powder raw material that forms the granulated material.
As the agent works as
Easy to bond the adhesion reducing agent coated from the surface to the granulated material
There is a tendency to break. Therefore, as a result, the liquid binder
Increases the surface adhesion of the detergent particles.
Will be done. That is, the surface of the measured detergent particles
If the adhesion is greater than the desired value, increase the amount added,
If it is less than the desired value, reduce the amount
Therefore, the surface adhesion of the detergent particles can be set to a desired value.
It is possible. The detergent particles produced according to the present invention are
Compression molding washing of sheet type, briquette type, sheet type, rod, etc.
Process, but before that, blend various additives
It is also suitable. (1) Fluorescent agent granules The optical brightener used in the present invention is added as independent granules
If so, for example, granular sodium carbonate, fine powder type A
Rolls optical brightener powder with zeolite and binder
Alternatively, stir granulation, or mix clay mineral and optical brightener powder
After mixing, add water, extrude, dry in a fluidized bed, etc.
After that, it can be added. Optical brightener granules
The particle size is preferably from 250 to 1000 μm,
0 to 750 μm is particularly preferred. Compression molded detergent of the present invention
In the composition, the optical brightener is 0.05 to 2% by weight as a pure component.
%, More preferably 0.1 to 1% by weight.
You. (2) Enzyme granules The enzyme used in the present invention is currently used in granular clothing detergents.
Use commercially available enzyme granules as they are
Can be done. Specifically, Sabinase 18T, cannase
12T, Lipolase Ultra 50T, Evalase 8T
(Above, Novo Nordisk), Maxacal 45G, Ma
Xapem 30G, Properase 1000E
Nenkoa). 150μ for these enzyme granules
m or less is substantially absent. Compression molding of the present invention
In the detergent composition, the amount of the enzyme granules is preferably 0.1 to 5% by weight.
And more preferably 0.3 to 2% by weight. (3) Dye The fluorescent agent granules, enzyme granules or detergent particles have a surface
It can be used after coloring with a dye or pigment. On this occasion
Dyes and pigments used for coloring cause dyeing on clothes during washing.
Use the one that does not. Group of such dyes and pigments
Blue, Coranil Green CG-130 (CI number: 7
4260), Food Color Red No. 102, Acid Dye Acid
Yellow 141 and the like. These dyes and pigments
Is used as an aqueous solution or dispersion, and then used as a granulator for detergent particles.
Stir and roll the above granules in various stirring granulators and rolling granulators
While adding, it can be colored. Ma
In addition, while transferring the granules on a belt conveyor,
The dispersion can also be colored by spraying on the granules. versus
0.01% to 1% is preferable as the amount of coloring per granule
No. (4) Bleaching agent Sodium percarbonate is preferably used as bleach
Can be. Use sodium percarbonate coated
Can be This coated sodium percarbonate
Boric acid aqueous solution and alkali silicate on sodium percarbonate particles
Can be sprayed separately with metal salt to dry and granulate
You. At this time, separately and simultaneously from two or more spray nozzles
Or you may spray sequentially. Boric acid solution and alkali silicate
Solvents for metal salts are water-soluble in terms of solubility, safety and price.
preferable. Boric acid as a coating agent, orthoboric acid, meta
Boric acid, tetraboric acid and the like are used. Alkali silicate
Remetal salts include sodium metasilicate and orthosilicate.
Sodium, water glass No. 1, No. 2, and No. 3 sodium
1 such as salt, potassium metasilicate, potassium orthosilicate, etc.
Species or two or more species can be used. Among them,
Water glass No.1, No.2 and No.3 are liquid and convenient for use
It is preferable from the viewpoint of properties. In addition to the coating agent,
May be used in combination with a coating agent.
No. The particle size of the coated sodium percarbonate particles is
In view of the stability and solubility of the sodium acid particles, 100
To 2000 μm, more preferably 200 to
1000 μm. In the compression molded detergent composition of the present invention,
Sodium percarbonate is preferably 1 to 30% by weight, more preferably
Preferably it is 2 to 20% by weight. (5) Bleaching activator The bleach activator used in the present invention is tetraacetyl ether.
Tylenediamine, alkanoyloxy having 8 to 12 carbon atoms
Benzenesulfonic acid, carboxylic acid or their salts
can give. Among them, the following general formula (I) Embedded image or (II) Those represented by the following formulas are preferred. [0049] Embedded image [0050] Embedded image (Wherein, R1 and R2 each independently have 7 or more carbon atoms)
Represents an alkyl or alkenyl group, and Ph represents a phenyl group.
And M is a salt-forming cation or hydrogen. ) In the formula, an alkyl group having 7 to 17 carbon atoms or alk
A kenyl group, particularly a straight-chain alkyl group, is preferred, and more preferred.
Or a linear alkyl group having 9 to 15 carbon atoms, R2
Is an alkyl or alkenyl group having 7 to 17 carbon atoms, particularly
A straight-chain alkyl group is preferred, and more preferred is a C 9 -carbon group.
To 15 linear alkyl groups. M is water
Alkali metals such as elemental, sodium and potassium, and ammonia
Amines such as ammonium and alkanolamines
You. Of these, hydrogen and alkali metals are preferred. Where S
O3M and COOM groups can be in the ortho, meta or para position.
However, the para position is preferred. In the present invention, one or more of these bleaching activators may be used.
Can be used as a mixture of two or more. these
The bleach activator of the present invention can be used in an amount of about 100-1
It can be obtained as plate-like crystals of 000 μm,
Method, so that the average particle size is less than 800 μm,
Preferably, pulverize to about 250 to 750 μm.
You. Furthermore, to improve storage stability and solubility, P
Solid at room temperature, such as EG # 3000 to # 20,000
Bleaching activator while heating and melting polyethylene glycol
After dispersion, extrude it into a noodle-like drift of about 1 mm in diameter.
Manufacture white activator granules, then length about 1-3mm
May be used after crushed lightly. At this time, 150 μm or less
The lower fines should be substantially absent. Compression of the present invention
In the detergent composition, the bleaching activator is 0.5 to 15% by weight.
And more preferably 1 to 10% by weight.
is there. (6) Fragrance Perfume, detergent particles alone, or mixed with various additives
The mixture may be flavored. The fragrance used is fat
Aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons, etc.
Hydrocarbons, aliphatic alcohols, terpene alcohols,
Alcohols such as aromatic alcohols, aliphatic ethers,
Ethers such as aromatic ethers, aliphatic oxides,
Oxides such as oxides of lupenes, aliphatic alde
Hyd, terpene aldehyde, hydrogenated aromatic aldehyde
Aldehydes such as thioaldehyde and aromatic aldehyde
, Aliphatic ketone, terpene ketone, hydrogenated aromatic keto
, Aliphatic cyclic ketone, non-benzene aromatic ketone, aromatic
Ketones such as aromatic ketones, acetals, ketals,
Phenols, phenol ethers, fatty acids, terpe
Carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids
Acids such as boric acid, acid amides, aliphatic lactones, macrocycles
Lactone, terpene lactone, hydrogenated aromatic lactone
Lactones such as aromatic lactones, aliphatic esters,
Furan carboxylic esters, aliphatic cyclic carboxylic acids
Ester, cyclohexylcarboxylic acid ester, ter
Pen-based carboxylic acid esters, aromatic carboxylic acid esters
Such as esters, nitromsks, nitriles, amines,
Including pyridines, quinolines, pyrrole, indole, etc.
Synthetic fragrances such as nitrogen compounds and natural scents from animals and plants
Fragrances containing fragrances, natural fragrances and / or synthetic fragrances
Alternatively, two or more kinds can be mixed and used. example
For example, "Synthetic fragrance" written by Motoichi Indo published in 1996 by the Chemical Daily
Chemistry and Product Knowledge ”, 1969 MONTCLAIR,
N. J. Published by Steffen Arctander “P”
erfume and Flavor Chemica
ls "and the like can be used.
Is shown. Aldehydes C6-C12, anisaldehyde
C, Acetal R, Acetophenone, Acetyl Cedre
, Adoxal, allyl amyl glycolate, allyl
Cyclohexane propionate, alpha damascon,
Beta damascon, delta damascon, ambrette
, Ambroxane, amylcinnamic aldehyde
De, amylcinamic aldehyde dimethyl acetate
, Amyl valerianate, amyl salicylate, iso
Amyl acetate, isoamyl salicylate, uranium
Thiol, acetyl-jugenol, bacdanol, benji
Ruacetate, benzyl alcohol, benzyl salicile
, Bergamyl acetate, bornyl acetate,
Butyl butyrate, paratertiary butyl cyclohexyl
Sanol, para-tert-butyl cyclohexyl ace
Tate, ortho tertiary butyl cyclohexano
Le, ortho-tertiary butyl cyclohexyl acetate
, Benzaldehyde, benzyl formate, potassium
Offylene, Kashmelan, Carbon, Sedroamba
ー, Cedrill acetate, Cedrol, Celestrite
Do, cinnamic alcohol, cinnamic aldehyde
De, cis jasmon, citral, citral dimethyl
Acetal, Citrasar, Citronellal, Citronet
Roll, citronellyl acetate, citronellyl pho
Mate, citronellyl nitrile, cycla set, cycla
Menaldehyde, cyclaprop, caron, Kumari
, Cinnamyl acetate, delta C6-C13 lacto
Dimethylbenzylcarbinol, dihydrojasmo
, Dihydrolinalool, dihydromyrcenol,
Toll, dimyrcetol, diphenyl oxide, ethyl
Lwanirin, jugenol, fluitate, fentyl
Alcohol, phenylethyl phenylacetate, glass
Kisolid, gamma C6-13 lactone, α-pine
, Β-pinene, limonene, myrcene, β-karyophy
Ren, geraniol, geranyl acetate, geranylf
Formate, geranyl nitrile, hedion, heriona
, Heliotropin, cis-3-hexenol, cis
-3-hexenyl acetate, cis-3-hexenyl
Lusalicylate, tripral, hexylcinnamic
Aldehyde, hexyl salicylate, hyacinth dimethi
Luacetal, hydrotropic alcohol, hydro
Xixitronellal, indole, ionone, isobol
Nyl acetate, isocyclocitral, iso-E super
ー, isoyugenol, isononyl acetate, isobutyrate
Luquinoline, Jasmar, Jasmolactone, Jas
Mofiran, koabon, rigstral, lilial,
Lime oxide, linalool, linalool oxide
De, linalyl acetate, liral, manzanate, ma
Iyol, Mensanil acetate, Mensonate,
Chillanthranilate, methyl yugenol, menthol
, Alpha methyl ionone, beta methyl ionone,
Gamma methyl ionone, methyl isoeugenol, methyl
Lavender ketone, methyl salicylate, mugeal
Dehid, Mugor, Musk TM-II, Musk 781,
Musk C14, Muscon, Cibeton, Cyclopentadeca
Non, cyclohexadecenone, cyclopentadecanol
, Ambrettolide, cyclohexadecanolide, 10
-Oxahexadecanolide, 11-oxahexadecanolide
, 12-oxahexadecanolide, ethylene brasserie
G, ethylene dodecandioate, oxahexadecene
-2-one, 14-methyl-hexadecenolide, 14-
Methyl-hexadecanolide, musk ketone, musk tibe
Chin, nopyr alcohol, nopyr acetate, nerylua
Acetate, nerol, methylphenyl acetate, mira
Cookaldehyde, neobergamate, oak moss No,
1. Oribbon, oxyphenylone, paracresyl meth
Ruether, Pentalid, Phenylethyl alcohol
, Phenylethyl acetate, alpha pinene, Luba
Furan, damacenone, raspberry ketone, dimethylben
Zircal vinyl acetate, jasma cyclen, meth
Lunaphthyl ketone, rose phenone, rose oxai
Do, Sandaloa, Sandera, Santa Rex, Stillir
Acetate, styryl propionate, tarpi
Neol, terpinyl acetate, tetrahydrolina
Roll, tetrahydrolinalyl acetate, tetra
Hydrogeraniol, tetrahydrogeranyl acetate
Tate, tonalid, traseolide, tripral,
Timor, crocodile, belldox, yarayara, anise
Oil, bay oil, boad rose oil, cananga oil, cardamom
Oil, cassia oil, cedarwood oil, orange oil, mandali
Oil, tangerine oil, basil oil, nutmeg oil, citro
Nera oil, clove oil, coriander oil, elemi oil, you
Potash oil, fennel oil, galvanum oil, geranium oil,
Hiba oil, Cypress oil, Jasmine oil, Lavandin oil, Lavender
-Oil, lemon oil, lemongrass oil, lime oil, neroli
Oil, oak moss oil, okotia oil, patchouli oil, peppermi
Oil, perilla oil, petitgren oil, pine oil, rose
Oil, rosemary oil, cerebral oil, fragrance oil, Clarysay
Di oil, sandalwood oil, spearmint oil, spiky
Vendor oil, star anise oil, thyme oil, tonka bean chin
Ki, turpentine oil, crocodile bean tincture, vetiver oil, Iran
Iran oil, grapefruit oil, citron oil, benzoin,
Peruvian sam, tolubal sam, tuberose oil, o
Kumos Absolute, Farbal Sam, Mustin
Ki, Castorium tincture, Civet tincture, Amberg
List tincture. In addition, as a solvent for fragrance or
Luphthalate, dipropylene glycol, benzylben
Zoate, isopropyl myristate, herculin,
Some people use isopentane, orange terpene, etc.
come. [0054] Next, the present invention will be described with reference to examples.
The invention is not limited by these examples. Embodiment 1 The kneading and crushing granulation method is used based on the manufacturing flow shown in FIG.
By controlling the amount of the adhesive force reducing agent added to the granulated detergent particles,
Target particle surface adhesion 25000-45000 Pa (tensile
(Break stress) was produced. (1-1) Granulation of detergent particles Nonionic surface activity among the detergent particle compositions shown in Table 1 below
Ingredients, excluding enzyme granules and some A-type zeolites
After preparing a slurry dissolved or dispersed in
Spray drying using a hot spray drying tower at a hot air temperature of 300 ° C
After drying, spray-dried particles having a water content of 3% were obtained. With these dry particles
Both are continuous kneaders with nonionic surfactant and water
(Kurimoto Iron Works Co., Ltd., KRC-S4 type)
Kneading under conditions of a total capacity of 120 kg / h and a temperature of 70 ° C.
A fixed solid detergent was obtained. This irregular shaped solid detergent has a hole diameter of 10m.
Pelletter double equipped with m dice (Fuji Paudal
Extrusion using EXDFJS-100 (manufactured by Corporation).
While cutting with a cutter (cutter peripheral speed is 5m / s)
A pelleted solid detergent having a thickness of about 5 to 30 mm was obtained. Next
In the obtained solid detergent, granular A-type
Olite (average particle size 180 μm) 3.0% equivalent
To form three stages in series in the presence of cold air (10 ° C, 15m / s).
Fitzmill (Hosokawa Micron Corporation, D
KA-3) so that the average particle diameter becomes 800 μm.
To obtain a granulated product (screen hole diameter: first stage / 2
Stage / 3rd stage = 8mm / 6mm / 3mm, rotation speed: all stages
3290 rpm). (1-2) Addition of adhesion reducing agent The obtained granulated product is transferred to a horizontal cylindrical type tumbling mixer (cylinder diameter 58
5 mm, 490 mm cylindrical length, 131.7 L container
Clearance between internal wall and internal wall 20mm, height
30% filling rate)
At a rotation speed of 22 rpm and 25 ° C.
Rolling started. Immediately after rolling starts
Add A-type zeolite powder equivalent to 0.7% and roll for 1 minute
To give detergent particles. (1-3) Measurement of Surface Adhesion of Detergent Particles Sampling a small amount of detergent particles after adding the adhesion reducing agent,
The surface adhesion (tensile rupture stress) of detergent particles is determined by the following method
As a result of the measurement, it was 21000 Pa. Tensile breaking stress
Measurement method of [Pa]: Hosokawa Micron Corporation, Ag
Using a robot, a metal cell (cell
(Internal diameter 25mm x height 37mm)
Fill 15g, temperature 20 ℃, maximum compression force 980N (maximum)
High compression pressure 2.0MPa), holding time 0 seconds, compression speed
Compressed under the condition of 1.0 mm / sec, and the tension spring wire diameter was 1.
Under the conditions of 2mm, tensile speed 0.4mm / sec, 20 ° C
Pulling only the upper cell, when the cell breaks up and down
The maximum tensile stress was defined as tensile rupture stress [Pa]. (1-4) Adjustment of the amount of adhesion reducing agent added Since the tensile rupture stress was lower than the target value,
Fine powder type A zeolite to be added in the coating process of the adhesion reducing agent
Was reduced to the equivalent of 0.5%, and the other conditions were "(1-
2) Addition of adhesion reducing agent "
Cover to obtain detergent particles. The surface adhesion of these detergent particles
Measured in the same manner as “(1-3) Measurement of surface adhesion of detergent particles”.
It was determined to be 32000 Pa, and the target surface adhesion
Detergent particles having power could be obtained. (1-5) Screening of detergent particles The detergent particles are classified using a sieve having a mesh size of 425 μm.
Detergent particles having an average particle size of 900 μm which do not pass through the sieve
(88% in detergent granules). In addition, opening 425 μm
Fine powder (12% in the detergent granules) that has passed through the sieve is continuously continuous
It was supplied to the kneader and reused. (1-6) Coloring of detergent particles To color a part of the obtained detergent particles, the detergent particles are
While transporting at a speed of 0.5 m / s on a belt conveyor
Detergent particle layer height 30 mm, width 300 m on the conveyor
m) The surface is coated with a blue dye solution for 0.0% of detergent particles.
It was sprayed to be 35%. (1-7) Addition of enzyme granules Enzyme granules in detergent particles partially colored in the amount shown in Table 1.
And a horizontal cylindrical tumbling mixer (cylinder diameter 585 mm,
Drum inner wall of cylindrical length 490mm, container 131.7L
20mm clearance with internal wall surface, 45mm height
With two baffles), filling rate 30%, rotation speed
Mix at 22 rpm and 25 ° C, detergent particles and enzyme
A mixture of granules was obtained, which was used as a granular detergent for compression molding. [0062] [Table 1] Embodiment 2 Based on the manufacturing flow shown in FIG.
By controlling the amount of the adhesive force reducing agent added to the granulated detergent particles,
Target particle surface adhesion of 90-130N (simple adhesion)
A granular detergent was produced. (2-1) Granulation of detergent particles Detergent particles with the composition shown in Table 1 are kneaded and crushed and granulated.
Granulation was carried out as in Example 1. (2-2) Addition of adhesion reducing agent In the same manner as in Example 1, the granulated product was finely powdered with 0.1% type A zeolite.
The surface was coated with light to obtain detergent particles. (2-3) Measurement of Surface Adhesive Force of Detergent Particles Sampling a small amount of detergent particles after adding the adhesion reducing agent,
The surface adhesion (simple adhesion) of detergent particles is determined by the following method
As a result of measurement, it was 154 N. Simple adhesion measurement
Method: Detergent particles 3 in φ45 mm Sumi square cylindrical tablet mold
8 g, Mikado Technos Co., Ltd., Mikado Airp
Powder temperature 25 ° C, molding thrust using MKP-100S
2450N, maximum compression speed setting, compression retention time 1 second
To obtain tablets of detergent particles. Then this
The tablet hardness [N] was measured by Okada Seiko Co., Ltd.
At a speed of 0.3 mm / s using a TS-75NL meter
Move the pressurizing arm to apply diametrical force from the cylindrical side of the tablet
, The maximum amount of time required to divide the tablet into two
The force is measured, and the value is defined as a simple adhesive force [N]. (2-4) Adjustment of the amount of adhesion reducing agent Since the simple adhesive force was higher than the target value,
Fine powder type A zeolite to be added in the coating process of the adhesion reducing agent
Was increased to the equivalent of 0.4%, and the other conditions were “(2-
2) Addition of adhesion reducing agent "
Cover to obtain detergent particles. The surface adhesion of these detergent particles
Measured in the same manner as in “(2-3) Measurement of surface adhesion of detergent particles”.
As a result, it was 119 N, and the target surface adhesion was
Was obtained. (2-5) Sieving of detergent particles The detergent particles are classified using a sieve having a mesh size of 425 μm.
Detergent particles having an average particle size of 920 μm which do not pass through the sieve
(85% in detergent granules). In addition, opening 425 μm
Fine powder (15% in the detergent granules) that has passed through the sieve is continuously continuous
It was supplied to the kneader and reused. (2-6) Coloring of detergent particles In order to color a part of the obtained detergent particles, the detergent particles
Partly Ledige mixer (Matsubo Co., Ltd., M20
Mold) (filling rate 50%) and the main spindle (200 rpm)
And chopper (3000 rpm) stirring was started. Disturbance
Immediately after the start of stirring, apply the pink dye solution to the detergent particles.
Add 0.1% equivalent and stir for 30 seconds after the addition.
A granular detergent was obtained. This colored granule detergent is uncolored granules
Reduced by 2% to detergent. (2-7) Addition of enzyme granules Add enzyme granules in the same manner as in Example 1 for adding enzyme granules
This was used as a granular detergent for compression molding. Embodiment 3 Based on the manufacturing flow shown in FIG.
By controlling the amount of liquid binder added during granulation, the target particle
Use a granular detergent with a surface adhesion of 90 to 130N (simple adhesion)
Manufactured. (3-1) Granulation of detergent particles Impregnated detergent particles with the composition shown in Table 2 by kneading and crushing granulation
Granulation was carried out as in Example 1. (3-2) Addition of adhesion reducing agent In the same manner as in Example 1, the granulated product was finely powdered with 0.5% type A zeo.
The surface was coated with light to obtain detergent particles. (3-3) Measurement of Surface Adhesive Force of Detergent Particles Surface adhesion of detergent particles (simple
As a result of measuring (adhesive force), it was 84 N. (3-4) Amount of liquid binder added during granulation
Adjustment of Since the simple adhesion was lower than the target value, the next batch was kneaded.
The amount of water added as a liquid binder to be added during the sum
Reduce the water content of the detergent to 10.0%
(1.5% water reduction was replaced with sodium carbonate),
Others are granulated in the same manner as “(3-1) Granulation of detergent particles”.
And fine powder A as in “(3-2) Addition of adhesion reducing agent”.
The surface was coated with a zeolite to obtain detergent particles. This detergent
The surface adhesion of particles is referred to as “(3-3) Surface adhesion of detergent particles.
Is 107 N.
Detergent particles having the target surface adhesion were obtained. (3-5) Sieving of detergent particles The detergent particles are classified using a sieve having a mesh size of 425 μm.
And detergent particles having an average particle size of 1050 μm which do not pass through the sieve
A child (90% in detergent granules) was obtained. In addition, the aperture 425μ
The fine powder (10% in the detergent granules) that has passed through the m
It was supplied to the kneader and reused. (3-6) Coloring of detergent particles As in Example 1, partially colored detergent particles were obtained. (3-7) Addition of enzyme granules In the same manner as in the method for adding the enzyme granules of Example 1, the arrangement shown in Table 2 was used.
The combined amount of enzyme granules was added. [0077] [Table 2] Embodiment 4 The kneading and crushing granulation method is used based on the manufacturing flow shown in FIG.
Addition amount of liquid binder at the time of granulation and addition of adhesion reducing agent
By controlling the amount, the target particle surface adhesion is 80 to 120 N (simple
(Easy adhesion). (4-1) Detergent granules
Kneading and crushing of detergent particles having the composition shown in Table 3
The kneading temperature is 55 ° C by the method and the introduced cold air temperature at the time of grinding is 10 ° C.
The other conditions were the same as in Example 1 and granulated. (4-2) Addition of adhesion reducing agent A granulated material was prepared in the same manner as in Example 1 except that 1.0% of fine powder type A zeo was used.
The surface was coated with light to obtain detergent particles. (4-3) Measurement of Surface Adhesive Force of Detergent Particles Surface adhesion of detergent particles (simple
As a result of measuring (adhesive force), it was 135 N. (4-4) Amount of liquid binder added during granulation
Adjustment of Since the simple adhesive force was higher than the target value,
Nonionic surface activity as a liquid binder added at the time of summation
Increase the amount of sexual agent B to 4.5% (increase 0.5%
Adjust the amount by reducing the amount of sodium carbonate).
Granulate in the same manner as “(4-1) Granulation of detergent particles”
Obtained. (4-5) Adjustment of Addition of Adhesion-Reducing Agent This granulated product is the same as “(4-2) Addition of adhesion reducing agent”
Coating with 1.5% fine type A zeolite and washing
Agent particles were obtained. The surface adhesion of the detergent particles is expressed as "(5-
3) Measurement of Surface Adhesive Force of Detergent Particles ”
Roller, 83N, detergent particles with target surface adhesion
Particles (average particle size: 850 μm) were obtained. (4-6) Coloring of detergent particles As in Example 1, partially colored detergent particles were obtained. (4-7) Addition of enzyme granules In the same manner as in the method for adding the enzyme granules of Example 1, the arrangement shown in Table 2 was used.
The combined amount of enzyme granules was added. [0085] [Table 3] Embodiment 5 Granulated by the stirring granulation method based on the production flow shown in FIG.
Controlling the amount of the adhesion reducing agent added to the detergent particles
Child surface adhesion 10,000 to 25000 Pa (tensile fracture
(G) A granular detergent was produced. (5-1) Granulation of detergent particles A nonionic surfactant and
Reedige mixer for all ingredients except enzyme granules
(M20, manufactured by Matsubo Corporation) (filling rate: 50
%), The main shaft (200 rpm) and the chopper (6000
rpm). 30 seconds after the start of stirring
On-surfactant and water are added in 5 minutes and the temperature is 35 ° C.
Continue stirring granulation until the average particle size becomes about 800μm
Then, a granulated product was obtained. (5-2) Addition of adhesion reducing agent In the same manner as in Example 1, the granulated material was used as a surface coating agent
The surface was coated at 3.0% to obtain detergent particles. (5-3) Measurement of Surface Adhesive Force of Detergent Particles Surface adhesion of detergent particles (tensile rupture) in the same manner as in Example 1.
As a result of measuring (stress), it was 8000 Pa. (5-4) Adjustment of the amount of adhesion reducing agent added Since the tensile rupture stress was lower than the target value,
The talc to be added is 2.0%
Immediately changed (1.0% talc reduction was sodium carbonate
The other conditions are “(5-2) Adhesive strength is low.
Add granules to the surface in the same manner as in
Got a child. The surface adhesion of the detergent particles was determined as “(5-3)
Measurement of the Surface Adhesive Force of Agent Particles "
Detergent with a target surface adhesion of 19000 Pa
Particles could be obtained. (5-5) Screening of detergent particles The detergent particles are passed through a sieve having an opening of 2000 μm and an opening of 425.
Classify using a sieve of μm and pass through a sieve of 2000 μm mesh.
Having an average particle size of 8 that does not pass through a sieve having an aperture of 425 μm.
00 μm detergent particles (73% in detergent granules) were obtained.
Coarse powder that did not pass through a 2000 μm sieve (detergent granulation)
(3% of the material) is a fitting with a screen with a hole diameter of 3 mm.
4 with Tsumir (manufactured by Hosokawa Micron Corporation, DKA-3)
Crushed at 700 rpm, sieve with mesh size of 425 μm
Fine powder (20% in detergent granules) that has passed through
In this state, it was again supplied to the stirring granulator and reused. (5-6) Coloring of detergent particles As in Example 1, partially colored detergent particles were obtained. (5-7) Addition of enzyme granules In the same manner as in the method for adding the enzyme granules of Example 1, the arrangement shown in Table 4 was used.
The combined amount of enzyme granules was added. [0094] [Table 4]Raw materials used ○ α-SF-Na: C obtained by the following production method
Alpha sulfo fatty acid nato having a 14-16 alkyl chain
Lithium (65.6% pure and other, methyl sulfate
3.28%, sodium sulfate 1.31%, alpha sul
3.08% of sodium salt of fatty acid sodium, methanol 1.
51%, unreacted methyl ester 1.21%, water 24.0
1%), provided that the sodium alpha sulfo fatty acid is
7% equivalent in the detergent composition manufacturing process, and more detergent composition
25% equivalent of alpha sulfo in long term storage
May be converted to sodium salt of fatty acid sodium. (Production method) Thin-film reactor (single tube, inner diameter = 10 m)
m, reactor length = 2.5 m)
Methyl myristate (Lion Oreo Chemical Co., Ltd.)
Manufactured by Pastel M-14) and methyl palmitate (Rio)
(Noreo Chemical Co., Ltd., pastel M-16)
Fatty acid methyl ester mixed at a ratio of 2: 8 (iodine value
0.40, molecular weight 264), SO3 gas system equipment
As liquid SO₃Using nitrogen gas as the dilution gas
To 8% SO3 containing inert gas, and the reaction molar ratio (S
O₃/ Methyl ester) = 1.2 and gas absorption reaction is thin film
Performed in a reaction system, gas-liquid separation, aging at 80 ° C for 60 minutes
The reaction was carried out to obtain a sulfonic acid having a conversion of 97%. Next
20% by weight methanol to sulfonic acid, 35% peroxide
Add water (2% pure hydrogen peroxide to sulfonic acid)
After addition and uniform mixing, a bleaching reaction was performed at 80 ° C. for 180 minutes.
Next, a neutralization reaction is performed with an aqueous sodium hydroxide solution.
A neutralized product with a concentration of 47% (surfactant concentration) was obtained and recycled.
Methanol by flash flash concentration
65.6% concentration (surfactant)
(Concentration). Color tone (5% by weight ethanol
The solution was passed through a 40 mm optical path length, no. 42 blue filter
(Measured with a Kret photoelectric meter). ○ LAS-K: Lipon LH-200 (Lion Corporation)
Made) potassium salt ○ LAS-Na: Lipon LH-200 (Lion
Sodium salt AOS-K: carbon obtained by the following production method
Α-Olefi of the number 14: 16: 18 = 15: 50: 35
Potassium sulfonate and hydroxyalkylsulfonic acid
Mixture of potassium (pure content 70%, α-olefin sulfone
Potassium acid: Potassium hydroxyalkyl sulfonate
The ratio is 7: 3, the remainder is unreacted α-olefin, sodium sulfate
Lium, sultone, sodium hydroxide, water, etc.) (Production method) α-olefin (Dialen 14 at 25 ° C.)
8, Mitsubishi Chemical Corporation) at a capacity of 970 kg / hr
Successively, TO reactor (TO-500, Lion Corporation)
, Film type reactor)₃gas
At about 35 ° C.
α-olefin sulfonic acid and impurities (mainly sultone)
The resulting sulfonate was obtained. This sulfonated product 1370k
g / hr, 630 kg / hr of caustic potash (moisture 52%
Aqueous solution) to perform a neutralization reaction,
Potassium olefin sulfonate was obtained. In this impurity
Shell and tube type to hydrolyze sultone
Heat the temperature to 140 ° C through a heat exchanger, and further react
Keep it at 170 ° C through 1.4MPa steam in a coiled tube.
That is, hydrolysis was promoted. Then, at pressure of 1MPa
Rush concentration and dehydration were performed to reduce the water content to about 27%. This
The pure content of AOS-K thus obtained is usually 66-74%
And the main component is potassium α-olefin sulfonate (about 7
0%) and potassium hydroxyalkyl sulfonate (about 3%).
0%), and the color is (10% solution LK value) 70,
1.8% of free alkali (KOH) (AOS-K pure
Minute). ○ Soap: Sodium fatty acid by the following production method (Production method) Fatty acid methyl ester (P
Stele MC-O *, manufactured by Lion Oreo Chemical Co., Ltd.)
1576 kg / h, 48% NaOH aqueous solution at 40-60 ° C
Liquid 445 kg / h, water (Lion Chiba Plant Nakasui) 336
kg / h to the mixing pump continuously
110-130 ° C with & tube type heat pre-heater and pre-heater
The saponification reaction was allowed to proceed for 9 to 10 minutes while maintaining (reaction
Rate 99.5 to 99.8%). Then, the overhead pressure is 0.2 to 0.1.
Flash steam with 6 kPa and tower temperature of 98-100 ° C
The reaction product is introduced into the
The ethanol was evaporated. Finally removed the methanol
Soap is introduced into a stirring tank with paddle-type stirring blades and retained
80 ° C while maintaining at 98 ° C with stirring for 140 minutes
Add water and concentrate to a soap concentration of 66-67%.
The degree was adjusted. The soap thus obtained has a pure content of 66.
~ 67%, as impurities about 0.01% fat
Acid, about 0.2% unreacted fatty acid ester, about 0.2%
NaOH, containing about 0.4% methanol. ○ Nonion A: Diadol 13 by the following production method
(Mitsubishi Chemical Corporation) 25 mol ethylene oxide adduct (Production method) 4 liter autoclave (pressure-resistant glass
Diamond Doll 13 (Mitsubishi Chemical Corporation)
400 g) and 2.3 g of a 30% NaOH aqueous solution.
Charge, replace the inside of the autoclave with nitrogen, and stir
The temperature was raised (while dehydrating at 100 ° C for 30 minutes)
). Next, the temperature was set to 180 ° C and the pressure was set to 300 kPa.
While maintaining ethylene oxide (EO: Mitsubishi Chemical
2200 g (average number of moles added: 25 mole phases)
For the time being, and reacts diamond doll 13 with EO.
Was. Finally aging for 30 minutes to obtain nonionic surfactant
Was. The impurity in the nonionic surfactant was about 2.0 PEG.
%, About 0.4% of unreacted alcohol. ○ Nonion B: Diadol 13 by the following production method
15M ethylene oxide adduct of Mitsubishi Chemical Corporation (Production method) 4 liter autoclave (pressure-resistant glass
13 (Mitsubishi Chemical Corporation)
400 g) and 2.3 g of a 30% NaOH aqueous solution.
And replace the inside of the autoclave with nitrogen,
It was warmed (dehydration was performed at a temperature of 100 ° C. for 30 minutes).
Next, while maintaining the temperature at 180 ° C. and the pressure at 3 atm.
Ethylene oxide (EO: manufactured by Mitsubishi Chemical Corporation) 13
20 g (average number of moles added: equivalent to 15 moles) was introduced,
Reaction of Diamond Doll 13 with EO was performed. Finally 30
After aging, a nonionic surfactant was obtained. Nonionic surface activity
Impurity in the active agent is about 2.0% PEG, unreacted alcohol
It was about 0.7%. ○ A-type zeolite (4A-type zeolite): Shilton B
(Mizusawa Chemical Co., Ltd.) (80% pure) ○ Acrylic acid / maleic acid copolymer salt: Aquaric
TL-300 (manufactured by Nippon Shokubai Co., Ltd.) (40% pure water solution)
liquid) ○ Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)
Made) ○ Sodium carbonate: Light ash (made by Asahi Glass Co., Ltd.) ○ Sodium sulfite: Anhydrous sodium sulfite (Shinshu Chemical Co., Ltd.)
Made) ○ Sodium silicate: JIS No. 1 sodium silicate (purity 4
5% aqueous solution) ○ Layered sodium silicate: SKS-6 (manufactured by Hoechst) ○ Talc: Nippon Talc Co., Ltd., Micro Ace LG ○ Fluorescent agent: Tinopearl CBS-X (Ciba Specialty)
Chemicals) ○ Enzyme: Sabinase 18T (Novo Nordisque Bio
Industry) [0096] According to the present invention, a raw material such as a compression molded detergent is produced.
In Surface Adhesion of Granular Detergent Particles for Processing
Granular detergent for processing with low particle adhesion and constant particle surface adhesion
A production method for stable and efficient production of
can do. [0097] FIG.[0098] FIG. 2 [0099] FIG. 3[0100] FIG. 4[0101] FIG. 5 [0102] FIG. 6

Claims (1)

Claims: 1. A means for measuring the adhesive force of a granulated material and a means for adjusting the amount of an adhesive force reducing agent added to a granulated material when producing a granular detergent. Means for adjusting the addition amount of the liquid binder at the time of granulation, and, according to the measured adhesion of the granulated material, the addition amount of the adhesion reducing agent for the granulated material and / or the amount of the liquid binder at the time of granulation. A method for producing a granular detergent, comprising controlling.