JP2003129095A - Solid cleaning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid cleaning agent having excellent characteristics in odor deterioration, solubility, appearance of products and productivity. SOLUTION: This solid cleaning agent is characterized in that, after raw materials of the cleaning agent are briquetted, obtained briquete is coated with a coating material containing an inorganic powder.

Description

Description: TECHNICAL FIELD [0001] The present invention relates to a solid detergent.
You. 2. Description of the Related Art
The detergent can be in the form of a liquid type or a granular type.
Ip's are known. At present, granular detergents are particularly widespread.
Used well. However, granular detergents are
Has the problem of scattering of detergent particles.
For convenience, detergent particles have recently been added to tablets (tablets).
And briquettes).
You. As such tableting technology, for example,
In Japanese Unexamined Patent Publication No. 10-88198, a roll press method is used.
After producing a briquette detergent with burrs,
Briquette by rolling briquette detergent
By removing the burrs of the detergent,
A method for producing a detergent is disclosed. However, in this technique, a roll
Fabricating briquettes directly from detergent particles
The briquettes are connected by a connection
So that individual briquettes are ejected without
Large pressurization is applied to
Briquettes are tightly compressed and soluble in water
There was not enough problem. On the other hand, loosen the detergent particles
When roll pressed under moderate pressure, briquettes
In the united state connected by the joint,
It is discharged from between the rolls as a primary compact.
To roll individual objects into individual briquettes,
It requires time rolling operation, which reduces productivity.
In addition, in rolling, the briquette deburring effect is sufficient
Not so try to get briquette without burr
And a long period of rolling is required, resulting in
Rickett surface smoothness is high, that is, surface porosity
And the solubility of the polymer is reduced. To solve this problem, Japanese Patent Laid-Open No. 2000-2000
No. 160198 discloses that detergent particles are compressed to form a plurality of particles.
Primary molding where briquettes are connected via connecting parts
The body is formed first, and the individual molded
A method for obtaining a briquette detergent by separating a bracket portion is disclosed.
Have been. Briquette washing with excellent solubility by this method
It is possible to produce an agent. However, this method has poor solubility.
Avoid prolonged rolling operations to prevent rolling
Therefore, the smoothness of the briquette surface is low,
The problem of deterioration remains. Besides, briquette
When producing detergents, a pair of briquetting
To form briquettes present on the roll
Frequent misalignment often results in product appearance
Further deterioration is common to all manufacturing methods.
This was an important issue. Like a briquette detergent
Another important problem commonly encountered in solid detergents
The deterioration of the product appearance due to discoloration that occurs during long-term storage
This problem of odor deterioration has not yet been solved.
won. Simply have a moderate size and a beautiful spherical shape
Stirring granulation method and tumbling granulation method
The method of granulating for a long time is generally known,
In these methods, a solid detergent having a desired size is granulated.
It was slight in the product and had a problem in terms of productivity. others
Solid with excellent odor deterioration, solubility, product appearance and productivity
Detergent was eagerly needed. SUMMARY OF THE INVENTION Accordingly, the present invention provides an odor
Providing solid detergent with excellent deterioration, solubility, product appearance and productivity
Offer. [0007] The present invention provides a method for cleaning detergent materials.
After ricketing, the resulting briquettes are
A solid detergent characterized by being coated with a coating agent containing
And its manufacturing method. By this manufacturing method, inorganic
Briquette with porous layer formed by fine powder
Coverable, odor degradation, solubility, product appearance, productivity
It has become possible to provide an excellent solid detergent. DETAILED DESCRIPTION OF THE INVENTION 1) Detergent raw materials As detergent raw materials for briquetting,
Surgery Society Edition, Granulation Handbook First Edition, First Printing (March 1991)
, Published by Ohmsha on March 10)
It is also preferable to use detergent particles granulated by
Or a mixture of detergent ingredients commonly used in detergents.
Briquetting is also suitable. However, yellowtail
Make sure the powder has good flowability when performing
It is preferable to use
Surface modification of the particles using fine powder such as zeolite
It is also preferable to carry out thirteen. (1) Surfactant (a) Anionic surfactant Preferred anionic surfactants include, for example, those having carbon atoms
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
0.5 to 8 moles of ethylene oxide and propylene
Len oxide, butylene oxide or ethylene oxide
Side / propylene oxide = 0.1 / 9.9-9.
Alkyl ether sulfate (AE) added at a ratio of 9 / 0.1
S) Salt or alkenyl ether sulfate, having 10 to 10 carbon atoms
20 linear or branched alkyl or alkenyl groups
Having an average of 0.5 to 8 moles of ethylene oxide,
Propylene oxide, butylene oxide or ethylene
Oxide / propylene oxide = 0.1 / 9.9
Alkyl ethers added at a ratio of ~ 9.9 / 0.1
Bonate or alkenyl ether carboxylate, carbon number
10 to 20 alkyl glyceryl ether sulfonic acids
Alkyl polyhydric alcohol ether sulfates, such as carbon number
10-20 higher fatty acid salts, saturated with 8-20 carbon atoms or
Unsaturated α-sulfofatty acid (α-SF) salt or methyl ester thereof
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, the following:
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) polyoxyethylalkyl (or alkenyl)
Phenyl ether. (Iii) Long-chain fatty acid alkyls
Alkylene oxide is added between the ester bonds of the ter
Also, for example, a fatty acid alkyl ester represented by the following formula:
Alkoxylate. R ₁ CO (OA) _n OR _Two (R ₁ CO 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. R _Two Is 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 above 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 surfactants Preferred amphoteric surfactants include, for example, imidazolyl
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 above 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. The above surfactant
Is usually 10 to 60 weight based on the weight of detergent granules
%, Preferably 15 to 50% by weight, particularly preferably
20 to 45% by weight is contained. (2) Detergent builder The builder used in the present invention includes 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: x ¹ (M _Two O) · Al _Two O _Three ・ Y ¹ (SiO _Two ) ・ W
¹ (H _Two O) (where M is an alkali metal source such as sodium, potassium, etc.)
Child, x ¹ , Y ¹ And w ¹ Indicates the number of moles of each component.
Typically, x ¹ Is a number from 0.7 to 1.5, y ¹ Is 0.8-6
The number of w ¹ Is an arbitrary positive number)
Minosilicate, general formula: x ^Two (M _Two O) · Al _Two O _Three ・ Y ^Two (SiO _Two ) ・ W
^Two (H _Two O) (where M is an alkali metal source such as sodium, potassium, etc.)
Child, x ^Two , Y ^Two And w ^Two Indicates the number of moles of each component.
Typically, x ^Two Is a number from 0.7 to 1.2, y ^Two Is 1.6 ~
2.8 number, w ^Two Represents 0 or any positive number)
Amorphous aluminosilicate, general formula: x ^Three (M _Two O) · Al _Two O _Three ・ Y ^Three (SiO _Two ) .Z
^Three (P _Two O _Five ) ・ W ^Three (H _Two O) (where M is an alkali metal source such as sodium, potassium, etc.)
Child, x ^Three , Y ^Three , Z ^Three And w ^Three Represents the number of moles of each component,
In general, x ^Three Is a number from 0.2 to 1.1, y ^Three Is 0.2
The number of ~ 4.0, z ^Three Is 0.001-0.8, w ^Three Is 0 or
Represents any positive number) amorphous aluminosilicate represented by
And the like. Among the inorganic builders, sodium carbonate
Lium, potassium carbonate, sodium silicate, tripolyline
Sodium silicate and sodium aluminosilicate are preferred. 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
Or oxydisuccinate, mono- or di-succinate tartaric acid
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 The oil-absorbing carrier used in the present invention is 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
1/100 g], amorphous hydrous amorphous silicic acid,
Kusu H-52 [made by Asahi Glass Co., Ltd., oil absorption 260ml / 1
00g] etc., spherical porous hydrous amorphous silicic acid, Aerosil
# 300 [Nippon Aerosil Co., Ltd., oil absorption 350m1
/ 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 220m1 / 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
1/100 g], ultra fine particle cordierite [Sumitomo Seme
Oil absorption 600ml / 100g], ultra fine particles
Mullite [Sumitomo Cement Co., Ltd., oil absorption 560m1
/ 100g], modified starch Pineflow-S [Matsuya Chemical
Oil absorption 130m1 / 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 The clay mineral used as a detergent component of the present invention includes:
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: 50m1 / 100g, bulk density: 0.3g / m
l), nontronite (oil absorption: 40 m1 / 100 g,
Bulk density: 0.5 g / ml), Beiderite (oil absorption: 6)
2m1 / 100g, bulk density: 0.55g / ml), pie
Lophyllite (oil absorption: 70m1 / 100g, bulk density:
0.63 g / ml).
Saponite is a clay mineral with a three-layered hedral structure.
(Oil absorption: 73m1 / 100g, bulk density: 0.15g /
ml), hectorite (oil absorption: 72 m1 / 100 g,
Bulk density: 0.7g / ml), Stephen site (oil absorption)
Amount: 30m1 / 100g, bulk density 1.2g / ml),
Luc (oil absorption: 70m1 / 100g, bulk density: 0.1g)
/ 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) Disintegration / dissolution accelerator The disintegration / dissolution accelerator used in the present invention includes, for example,
For example, potassium carbonate, ammonium sulfate, ammonium chloride
Inorganic ammonium salts such as sodium, sodium benzoate,
Sodium sulfonic acid, p-toluenesulfonic acid
Sodium, sodium xylene sulfonate, sodium chloride
Water such as lium, citric acid, D-glucose, urea, and sucrose
Soluble substances. In addition, there are also swellable, water-insoluble
Materials are also preferred. Specifically, powdered cellulose, crystalline
Cellulose, carboxymethyl cellulose with low degree of etherification
Carboxymethylcellulose, carboxy
Methylcellulose calcium, hydroxypropyl cell
Cellulose derivatives such as loin, dens such as corn starch
Starch induction such as starch and hydroxypropyl starch
, Crosslinked polyvinylpyrrolidone, low etherification degree
And vinyl alcohol. Preferred disintegration / dissolution
Examples of the dissolution accelerator include JP-A-7-286199,
JP-A-2000-192098, JP-A-2001-17
2694, JP-A-2001-171765, etc.
Can be appropriately used. This
These are also preferably granulated in advance in granules,
Those having a diameter of 200 to 1500 μm are particularly preferred.
Disintegration / dissolution accelerators are based on the weight of detergent granules before compression molding.
Therefore, it is usually 1 to 50% by weight, preferably 5 to 30% by weight.
Suitably, it is in an amount of% by weight. In the present invention
Before compressing detergent granules, the briquette after compression molding
Disintegration / dissolution accelerator that promotes disintegration and solubility of
It is preferable to mix a granular disintegration / dissolution accelerator
No. Specific examples of components incorporated in other detergents
The following are shown. (6) Fluorescent agent: bis (triazinylamino) stilbene
Disulfonic acid derivative, bis (sulfostyryl) biphenyl
Salt (Tinopearl CBS) and the like. (7) Enzymes: lipase, protease, cellulase,
Millase and the like. (8) Bleaching agents: percarbonates, perborates, etc. (9) Antistatic agent: dialkyl type quaternary ammonium salt
Which cationic surfactant etc. (10) Surface modifier: fine calcium carbonate, fine zeola
And polyethylene glycol. (11) Anti-redeposition agent: carboxymethylcellulose
Which cellulose derivatives and the like. (12) Extender: sodium sulfate, potassium sulfate, hydrochloric acid
Sodium and the like. (13) Reducing agent: sodium sulfite, potassium sulfite
etc. (14) Fragrances (15) Pigments (16) Softener The enzymes, bleaches and softeners are usually in the form of particles.
Used as a state. 2) Method for producing detergent particles In the present invention, a detergent raw material to be subjected to briquetting and
If detergent particles are used,
Particles can be obtained. Detergent ingredient powder and bi
After kneading and kneading the under ingredients, extrude and granulate
After extrusion granulation or kneading and kneading, the resulting solid
Kneading and crushing granulation method to crush and granulate detergent, raw material powder
Add binder component to the mixture and stir with stirring blades to granulate
Stir granulation method or binder while rolling raw material powder
-Rolling granulation method of spraying and granulating the component.
Examples of the raw material powder include powdered surfactants and detergents.
Can be used in combination, and if necessary
Water to some or all of the detergent components
Prepared and spray-dried to dry powder according to standard methods
May be used. Further, as the binder component, 0
At ~ 100 ° C, liquid detergent raw materials can be used.
Water, surfactant, water-soluble polymer, etc. are preferred as examples
It is listed. 1. Extrusion granulation method 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. 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 kneading 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 grinding, use a grinding aid
Thereby, it can be efficiently crushed. This crush
As the auxiliary agent, an inorganic powder having an average particle size of 30 μm or less is preferable.
A type zeolite, fine powder of sodium carbonate, white carb
The amount is 100 parts by weight of the ingredients to be ground.
0.5 to 15 parts by weight, preferably 2 to 10 parts by weight
Parts by weight are more preferred. In addition, the primary particle size is 30 μm or less.
Use particles with good fluidity made by granulating inorganic powder
Can also. Also, cool air is passed through the pulverizer to cool the powder.
It can also be crushed. Classify cold air and crushed products with cyclone
At that time, it is also possible to classify the fine powder. Preferably
By multi-stage pulverization, sharper particle size distribution
Become. The peripheral speed of the tip of the crusher blade is 15 to 9
0 m / s is preferred. Low capacity if less than 15m / s
And the productivity is reduced.
It is not good, it is not good. More preferably, 20 to 80 m
/ S, most preferably 25 to 70 m / s. The present invention
According to the production method of the preferred particle size for the above-mentioned particle size
It can be manufactured without classifying equipment such as sieves for distribution and productivity.
Can be raised. However, the particle size distribution is
Classify the crushed product with a sieve to use it
Is also possible. This crushed product was coated with fine particles
Blended with the aforementioned detergent ingredients such as fragrances and enzymes
Alternatively, a nonionic surfactant or the like can be sprayed. 3. Agitation granulation method In the agitation granulation method, any type of agitation granulation device can be used.
Can be. Among them, a preferred stirring granulator is a stirring blade.
A stirring shaft with a root is located at the center of the inside, and the stirring blade rotates.
A clearance between the stirring blade and the vessel wall
It is important that the structure is appropriate. Average clearance is 1
Is preferably 30 to 30 mm, more preferably 3 to 10 mm.
is there. If it is less than 1 mm, the mixing machine may be overpowered due to the adhesion layer.
Easy to be. If it exceeds 30 mm, the efficiency of consolidation decreases.
Therefore, the particle size distribution becomes broad. Also the granulation time is long
Productivity decreases. Agitation granulator having such a structure
For example, Henschel mixer [Mitsui Miike Kakoki
Co., Ltd.), high-speed mixer [Fukae Industry Co., Ltd.]
Vertical granulator [Powrex Co., Ltd.]
, Etc.), and particularly preferably a horizontal mixing tank.
It has a stirring shaft in the center of the cylinder, and the stirring blade is attached to this shaft.
A mixer that mixes powder, for example, ready
Ge mixer (Matsubo Co., Ltd.), Blowshare mixer
[Made by Taiheiyo Kiko Co., Ltd.]. Preferred granulation conditions in the stirring granulation method are as follows.
Shown in (1) Froude number (Fr number) The Froude number defined by the following equation is 1 to 16.
And more preferably 1.5 to 9. Flew
If the number is less than 1, compaction is not promoted, which is not preferable. Ma
If it exceeds 16, the particle size distribution is undesirably widened. Fr = V ^Two / (R × g) V: Peripheral speed [m / s] of tip of stirring blade R: Rotation radius [m] of stirring blade g: Gravitational acceleration [m / s] ^Two (2) The chopper rotation speed agitation granulator is required to promote the compaction of the granulated material and the promotion of coarse powder crushing.
It is equipped with a chopper that rotates at high speed. Like
The rotation speed of the new chopper is
Speed) is 20 to 30 m / s, more preferably 2 to 30 m / s.
It is 2-28 m / s. (3) Granulation time At the time of granulation in palindrome-type granulation to obtain a suitable granulated product
Average, and average residence time in continuous granulation is 0.5
To 20 minutes, more preferably 3 to 10 minutes.
You. In addition, if less than 0.5 minutes, the granulation time is too short,
It is difficult to control granulation to obtain average particle size and bulk density.
And the particle size distribution becomes broad. After 20 minutes
The granulation time is too long and the productivity decreases. (4) Detergent raw material filling rate The detergent raw material filling rate (prepared amount) in the granulator depends on the mixing machine.
It is preferably 70% by volume or less of the total internal volume, more preferably
15 to 40% by volume. If it exceeds 70% by volume,
Since the mixing efficiency of the detergent raw materials in the
Can not do the grain. (5) The temperature granulator preferably has a structure with a jacket.
The temperature of the medium passing through the tray is preferably 5 to 40 ° C,
More preferably, it is 10 to 20 ° C. In this temperature range
By doing so, the granulation time for obtaining a suitable granulated product is short.
It improves productivity and sharpens the particle size distribution. Ma
Of detergent materials, powder materials are at room temperature and liquid materials are molten.
The temperature inside the mixer should be particularly controlled.
No need to control. The temperature of the granulated material is the temperature of the feedstock.
The temperature is usually 30 to 60 ° C. depending on the degree and heat of stirring. Kana
No. (6) Additive Add binder to promote granulation during granulation
Is also good. Examples of binders include carboxymethyl
Lulose, polyethylene glycol, polyacrylate
Water-soluble polymer solutions such as polycarboxylates,
Polyoxyethylene alkyl ether, fatty acid monoeta
Nonions such as nolamide and fatty acid diethanolamide
Substances, fatty acids, aqueous sodium silicate solution, water, etc.
Can be. The amount of the binder to be mixed or granulated 10
0.1 to 10 parts by weight relative to 0 parts by weight is preferable,
Particularly, 0.5 to 5 parts by weight is preferable. 4. Rolling granulation In rolling granulation, granulation is performed by the following method and equipment.
It is possible. (1) Batch method The method of charging the ingredients to the granulator is not particularly limited.
Not. In the case of batch type, for example,
Various methods can be employed. First, a builder of organic or inorganic powder is injected into the granulator.
One selected from atomized particles and other powder components or
After charging two or more types, liquids such as surfactants and water
Add the ingredients and mix. Organic or inorganic powder builders, spray-dried particles and
And two or more selected from other powder components in advance
After charging the granulated product into a granulator, a liquid such as a surfactant or water
Add and mix body components. Organic or inorganic powder builders, spray-dried particles and
One or more selected from other powder components
And a small amount of liquid components such as surfactants and water into a granulator.
Prepare each one. Organic or inorganic powder builders, spray-dried particles and
One or more selected from other powder components
After charging part of the mixture into the granulator, the remaining organic or
Choose from machine builders, spray-dried particles and other powder components
One or two or more surfactants, water, etc.
And a small amount of the liquid component is charged into a granulator. Organic or inorganic powder builders, spray-dried particles and
One or more selected from other powder components
Pre-mixed with a liquid component such as a surfactant or water
Is charged into a granulator. Of these, first organic or
Inorganic powder builders, spray-dried particles and other powder components
One or two or more selected from
After adding, surfactant and water are added and mixed.
Preferred. (2) Continuous method In the case of a continuous method, first, the detergent raw materials are continuously mixed.
However, the method of supplying the detergent raw material is not particularly limited.
No. For example, it is possible to take various methods such as
it can. Supply the components of detergent raw materials independently and continuously
You. In the detergent raw materials and the powder raw materials pre-mixed,
A liquid component such as a surfactant or water is continuously supplied. A mixture of two or more powdered raw materials in advance among detergent raw materials
And the remaining powdery raw materials and liquid components such as surfactants and water
Are supplied continuously. Liquid components such as surfactants and water and other powdered raw materials
All are mixed in advance in a batch system, and the mixture is
Feed continuously to the granulation process. Preferred granulation conditions in the tumbling granulation method are as follows.
Shown in (1) Processing time The processing time for increasing the bulk density in a batch system or the continuous system
The average residence time, defined by the following equation:
Minutes, preferably 10 to 90 minutes, particularly preferably 10 to 4 minutes.
0 minutes. From the viewpoint of sufficiently increasing the bulk density,
The average or average residence time is preferably 5 minutes or more, and the productivity is low.
120 minutes from the viewpoint of preventing the disintegration of the particles under or under the detergent granules
The following is preferred. Tm = (m / Q) × 60 Tm: Average retention time (min) m: Detergent granulation retention amount (kg) in container rotary mixer Q: Capacity in continuous operation (kg / hr) (2) Froude number (Fr) The Froude number defined by the following equation is 0.01 to 0.8.
Select the condition that satisfies More preferably, 0.0
5 to 0.7, more preferably 0.1 to 0.65.
You. From the viewpoint of obtaining uniform and high bulk density detergent particles,
The Ludo number is preferably 0.01 or more.
In the case of a combined machine, the detergent granules are turned over without scattering.
0.8 or less from the viewpoint of generating normal shear mixing to be obtained.
preferable. Fr = V ^Two / (R × g) V: Peripheral speed of outermost periphery of container rotary mixer (m / s) R: Radius from rotation center of outermost peripheral of container rotary mixer
(M) g: Gravitational acceleration (m / s) ^Two (3) Volume filling ratio The volume filling ratio defined by the following equation becomes 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 of detergent granule particles (g / L) V: volume of container rotary mixer (L) 3) Classification of detergent particles Detergent particles granulated by the above method are necessary. Classification according to
It is possible to use only detergent particles of the desired particle size in products.
Wear. Any classifier generally known as a classifier
A screen can also be used, but a sieve can be suitably used. During ~
However, suitable sieves include gyroscopic sieves, flat sieves and vibrating sieves
Is preferred. Gyro-type sieve is a slightly inclined plane sieve
On the other hand, it is a sieve that gives a horizontal circular motion. The plane sieve is slightly
A sieve that gives a reciprocating motion almost parallel to the surface on an inclined plane sieve
It is. Vibrating sieves vibrate rapidly in a direction almost perpendicular to the screen surface.
The sieve to give. Sieving time should be at least 5 seconds
Is desirable. Also, to improve the sieving efficiency
It is also preferable to use a tapping ball. like this
As a specific example of a sieve, gyro shifter (Tokuju
Works), Lotex Screener (Seisin Co., Ltd.)
Companies), Dalton vibration sieve (Dalton Co., Ltd.)
No. Vibration by a sieve is 60 to 3000 times / minute,
Preferably 100 to 2500 times / minute, more preferably 1
It is given with a vibration of 50 to 2000 times / min. Sieve frequency
Is less than 60 times / minute, the classification effect is deteriorated. on the other hand,
If it exceeds 3000 times / minute, dust generation increases. The detergent particles granulated by the above method have an average
Preferably, the particle size is between 200 and 2000 μm.
More preferred detergent particles have an average particle size of 300 to 1
It is 500 μm. Briquette with an average particle size of less than 200 μm
The gap formed between the particles when
It is not preferable because it is too hard to disintegrate. Also average
If the particle size exceeds 2000 μm, the solubility of the particles themselves is poor.
Is undesirable. 4) Method for Producing Solid Detergent (1) Roll Pressing Step In the present invention, the above detergent particles are roll-pressed.
Multiple briquettes are connected via the connection
Compression molded into a primary detergent compact. Roll press method
Are already known and are used in the method.
Ketting machines are also known and are readily available or available to those skilled in the art.
Is available. Briquetting machines generally have a corresponding row.
Form a briquette part of the desired shape
A predetermined recess is formed that can be
It has a pair of rolls that rotate in reverse in degrees. Also, that low
The detergent composition to the clearance formed between the
With hopper and feed screw for
Briquetting machines with a dough are particularly suitable. feeder
When using a briquetting machine with a
Through the feed screw,
Detergent composition from the entrance of the clearance
Insert the primary detergent molded body from the outlet opposite to the feeder side.
Discharge. In the present invention, a predetermined screw is provided between a pair of rolls.
Provide an alance to keep the pressure lower than before
By connecting multiple briquettes via the connecting part
Into a compacted primary molded body (eg, sheet)
This improves the solubility of the resulting briquettes
It is. The temperature of the pair of rolls is usually 70 ° C. or less.
Under, preferably, 50 ° C. or less is appropriate, but particularly,
When an enzyme is contained in the agent composition, the enzyme
It is important to keep the temperature so that it is hardly deactivated during pressing.
is there. The rotation speed of the roll is, for example, the roll surface
As a peripheral speed of 0.01 to 1.5 m / s, preferably
Is suitably 0.05 to 0.8 m / s. Primary detergent composition
In the configuration, the connection has a substantially uniform thickness, and
Briquettes formed by the shape of a pair of roll depressions
Parts are connected in one-dimensional direction or two-dimensional direction (planar)
You. The primary compact is usually discharged in the form of a sheet,
It varies depending on the size of
Tens to hundreds of briquettes per line
Are in the form of sheets connected to each other by connecting parts
However, in some cases, the
May be connected for a long time. The shape of the briquette part is optional,
Is determined in consideration of the convenience of handling by the user. Briquette
As the shape of the cut portion, for example, a spherical shape or an elliptical spherical shape
Or the vertical projection image of the sheet surface is circular or elliptical
However, the projected image on the sheet surface in the horizontal direction is
Flat sphere or flat ellipsoid sphere, or
The vertical projection image of the sheet surface is square or rectangular,
The horizontal projection image on the plate surface is cylindrical or circular
Means that the projected image in the vertical direction of the sheet surface is square or rectangular
However, the horizontal projection image on the sheet surface is elliptical or almond-shaped.
Flat cylindrical shape. Throw perpendicular to the sheet surface
If the image is circular or elliptical, for example, its diameter
(The major axis in the elliptical shape) is 2 to 40 mm, preferably 3 to
20 mm is preferred. Also, the seat surface vertical direction
For example, if the projected image is square or rectangular,
The side (long side in a rectangle) is 2 to 40 mm, preferably 3
To 20 mm. The briquette section
The thickness (the length of the briquette section in the direction perpendicular to the sheet surface) is an example.
For example, 2 to 40 mm, preferably 3 to 20 mm
You. The clearance between a pair of rolls is, for example,
For example, 0.05 to 2 mm, preferably 0.1 to 1 mm
Appropriate. In this case, the thickness of the connecting part is usually clear
The thickness is the same as the lance width, but during roll pressing
The roll retracts according to the molding pressure to increase the clearance.
Ip's briquetting machine can also be suitably used.
This is not the case. In addition, the shortest
The distance is, for example, 0.05 to 5 mm, usually 0.1 to 3
mm. (2) Crushing step The primary detergent molded product obtained by the above roll press method is:
Next, it is subjected to a crushing step. Here, “crushing” means
Primary cleaning of briquettes by applying external force to the joints
And separately from the molded product, and preferably
This is an operation for substantially removing burrs on the ricket portion.
In the crushing process, the briquettes are separated from the primary detergent
As long as it is separated and deburred,
The type of crusher used in the process is not particularly limited.
No. A preferred crusher is a crusher equipped with rotating blades.
Crusher, especially a hammer mill type
You. As such a crusher, for example, Fitzmill
(Manufactured by Hosokawa Micron Corp.), Fezamil (Hosokawa
Speed Micro (Okada Manufacturing Co., Ltd.)
Manufactured by Fuji Paudal Co., Ltd.)
Suitable. In these crushers, a blade is used.
In general, the tip peripheral speed is preferably 0.4 to 15 m / s,
A preferred range is 1 to 10 m / s. Tip circumference
If the speed exceeds 15m / s, the briquette part is easily broken
Is not preferred. On the other hand, when the tip peripheral speed is 0.4
If it is less than m / s, the briquette part is separated from the primary molded body.
Again, it is not preferable. In the crushing process
Crushing, for example, 70 ° C. or less, preferably 50 ° C.
The following are suitable, but especially when the detergent composition contains an enzyme:
The enzyme is almost inactive during the disintegration process
It is important to keep the temperature. Average residence time in the crusher
The time is, for example, 20 seconds or less, preferably 10 seconds or less.
It is appropriate to do. (3) Rolling operation step (burr of briquette part)
Removal) In order to further improve the appearance of briquette detergent products
The burrs in the briquette remaining after crushing
May be removed. As long as sufficient rolling operation is possible,
Any rolling operating device can be used, but
The rolling operation device is a marmelizer (Fuji Paudal
Rolling and sizing machine having a rotating disk such as
You. However, the processing time is based on the table for the resulting briquette detergent.
It is preferable to perform this operation in a minimum time so that the surface is not smooth.
Good. [0034] In addition, in these rolling sizing machines,
The type with a grid (grooves on the surface of the rotating disk)
It is preferable to have a rotating disk of
Is generally 0.5 to 15 mm, preferably 1 to 10 mm
is there. Even if the gap is less than 0.5mm, it exceeds 15mm
However, the sizing efficiency is undesirably reduced. Rotating rotating disk
The peripheral speed is generally 2 to 80 m / s, preferably 5 to 80 m / s.
50 m / s. If less than 2m / s, the shearing force is too weak
Grain efficiency decreases, which is not preferable.
Because the briquettes are concentrated too close to the wall due to mental strength,
The effective use area of the rotating disk is reduced, which is not preferable. Also,
The processing time for preventing the surface from becoming too smooth
Generally, it is 3 minutes or less, preferably 2 minutes or less. (4) Removal of crushed residue In the crushing step, a briquette portion and crushed residue are generated.
Therefore, the crushed residue is removed using a classifier (such as a sieve),
Collect the briquettes as briquette detergent. In addition,
The crushed residue is recovered and used in the detergent composition in the method of the present invention.
Reused as raw material. Obtained in this way
Briquette detergent has a bulk density of 0.7 to 1.6 g / ml,
It is always 0.8 to 1.4 g / ml. (5) Coating step The briquettes obtained after crushing are left as they are or
After removing burrs in a minimum amount of time,
Coated with a covering agent. As long as the coating agent used in the present invention contains inorganic powder,
Although not limited, preferred inorganic powders described in the text
Inorganic powder detergent builders, oil-absorbing carriers, clay minerals, etc.
I can do it. Specifically, zeolite, sodium carbonate, charcoal
Potassium silicate, crystalline silicate, silica fine powder, montmoly
Lonite, talc and the like are preferably used. Its average particle
Generally, the diameter is preferably 300 μm or less, and the odor is deteriorated.
From the viewpoint of prevention, it is more preferably 100 μm or less. Coating
When the average particle size exceeds 300 μm, the product appearance deteriorates
This is not preferred because of the tendency. General addition amount
5 to 80%, preferably 10 to 60%. Less than 5%
Can improve the product appearance and prevent odor deterioration
It is not preferable, and if it exceeds 80%, the coating agent will increase.
Cleaning performance
No. Of the coating layer when the coating agent is coated on the briquette surface
The thickness is generally 5 to 2000 μm, preferably 10 to 2000 μm.
〜1500 μm. If less than 5 μm, the effect of improving product appearance
It is difficult to obtain the effect of preventing fruit and odor deterioration, which is not preferable.
If it exceeds 2000 μm, the solubility may be deteriorated.
Is not preferred. In addition, these coating agents are
Coating with a liquid binder to fix the surface.
Is preferred. Liquid binder The liquid binder used in the present invention is a liquid binder itself.
Nonionic surfactant with detergency and amphoteric surfactant
Agent, liquid surfactant such as alcohol ethoxylate
It is preferable to use a water-soluble polymer,
Etc. can also be suitably used. The viscosity of the liquid binder
0.0001 to 100 Pa · s at 0 to 100 ° C
It is preferable that Less than 0.0001Pa · s
It is not preferable because the effect as an indder cannot be obtained.
If it exceeds Pa · s, handling is difficult and not preferable.
The amount of liquid binder added is generally the maximum oil absorption of the coating
(Oil absorption per mL of coating agent [mL / g] x addition of coating agent
70 to 100% of the total amount [g]). 70
%, There are many coatings that do not settle on the briquette surface.
Therefore, it is not preferable.
Excessive, the fluidity of the solid detergent after surface coating deteriorated
It is not preferable because it is easily solidified. The inorganic powder coating device used in the present invention
Use any type of agitation granulator or tumbling granulator.
Can be used. When using a stirring granulator,
As a device, for example, it has a stirring shaft inside,
Equipped with a mixing blade and a stirring blade for crushing.
Clear run of 30 mm or less between the wing and the inner wall of the granulator
Stirrer-type granulation device with
With wings attached, for example, Lödige mixer [Ltd.
Matsubo), Plowshare mixer
Co., Ltd.), high-speed mixer [Fukae Industry Co., Ltd.]
And the like are particularly preferred. Good performance when using a stirring granulator
Suitable coating conditions are shown below. (1) Froude number (Fr number) The Froude number defined by the following equation is 1 to 16.
And more preferably 1.5 to 9. Flew
When the number of layers is less than 1, the consolidation of the coating layer is not promoted, which is preferable.
Absent. Also, when it exceeds 16, the particle size distribution is widened, which is preferable.
Absent. Fr = V ^Two / (R × g) V: Peripheral speed [m / s] of tip of stirring blade R: Rotation radius [m] of stirring blade g: Gravitational acceleration [m / s] ^Two (2) The chopper rotation speed agitation granulator is required to promote the compaction of the granulated material and the promotion of coarse powder crushing.
Is equipped with a chopper that rotates at high speed.
Prevent briquette breakage during the ricket coating process
Stop or run at low speed to stop
Is preferred. The preferred rotation speed of the chopper is
The tip speed (peripheral speed) of the upper part is 20 m / s or less,
More preferably, it is 10 m / s or less. (3) Coating time At the time of coating in batch type granulation to obtain a suitable granulated product
Mean, and the average residence time in the continuous coating process,
0.5 to 10 minutes is preferable, and more preferably 1 to 5 minutes.
is there. In addition, less than 0.5 minutes is suitable because the coating time is too short.
It is difficult to control the formation of a simple coating layer.
Beyond 0 minutes, briquette is likely to break
And productivity is reduced. (4) Volume filling ratio of briquette and coating agent Volume filling ratio of briquette and coating agent to agitation granulator
(Prepared amount) is 70% by volume or less of the total internal volume of the granulator
And more preferably 15 to 40% by volume.
If the content exceeds 70% by volume, mixing of the detergent raw materials in the mixer will occur.
It is not possible to perform a suitable coating operation due to reduced efficiency.
No. Volume filling rate = (M / ρ) / V × 100 M: Charge of detergent granule particles into stirring granulator (g) ρ: Bulk density of detergent granule particles (g / L) V: Stirring (5) Temperature coating step is performed at a temperature at which the liquid binder is molten.
It is preferable to use heat-sensitive materials such as enzymes in briquettes.
May need to be heated more than necessary
There is no. Due to the heat of the enzyme during briquetting,
When using a stirring granulator equipped with a
Temperature during the coating process, which is preferably heated or cooled
Is generally from 0 to 100 ° C and from 10 to 80 ° C
Is preferred. (6) Addition order The addition order of the coating agent and the liquid binder is the final addition amount.
Is not particularly limited as long as the briquettes are stirred.
Powder coating after spraying (or dripping) binder
The coating operation should be performed in the order of
Is preferred. It is also a good idea to repeat this operation
No. If the fluidity of the obtained solid detergent is poor,
Adjusts fluidity by coating with fine powder such as zeolite
It is also preferable to do so. On the other hand, when a tumbling granulator is used,
The device that rotates and processes the drum-shaped cylinder
Preferred, especially equipped with baffles of any shape
Is preferred. As the drum type granulator, horizontal cylindrical type
In addition to the granulator, edited by the Japan Powder Industry Association,
First edition first printing (Omsha, March 10, 1991)
Line) described conical drum type granulator, multi-stage conical drum type granulator
Machine, drum type granulator with stirring blades, etc.
It can be suitably used. Preferred granulation conditions in the tumbling granulation method are as follows.
Shown in (1) Froude number (Fr) The Froude number defined by the following equation is 0.01 to 0.8.
Select the condition that satisfies More preferably, 0.0
5 to 0.7, more preferably 0.1 to 0.65.
You. From the viewpoint of obtaining uniform and high bulk density detergent particles,
The Ludo number is preferably 0.01 or more.
Briquette can flip without splashing
0.8 or less is preferable from the viewpoint of generating normal shear mixing.
New Fr = V ^Two / (R × g) V: Peripheral speed of outermost periphery of container rotary mixer (m / s) R: Radius from rotation center of outermost peripheral of container rotary mixer
(M) g: Gravitational acceleration (m / s) ^Two (2) Coating time When coating in batch-type granulation to obtain suitable granules
The average residence time during and during the continuous coating process is 1
To 20 minutes, more preferably 2 to 10 minutes.
You. In addition, if the coating time is less than 1 minute, the coating time is too short and a suitable coating layer is formed.
It is difficult to control to form
Is more likely to break briquettes and increase productivity
Decreases. (3) Volume filling rate of briquette and coating agent Volume filling of briquette and coating agent in a tumbling granulator
Rate (prepared amount) is 10 to 50%, preferably 20
To 45%, more preferably 25 to 40%. production
From the viewpoint of performance, the volume filling ratio is preferably 15% or more, and is good.
50% or less is preferred from the viewpoint of causing
No. Volume filling rate = (M / ρ) / V × 100 M: Amount of detergent granule particles charged to the container rotary mixer
(G) ρ: Bulk density of detergent granule particles (g / L) V: Volume of container rotary mixer (L) (4) The temperature coating step is performed at a temperature at which the liquid binder is molten.
Is preferable, but is vulnerable to heat such as enzymes during briquetting.
Substances may be contained, so it is necessary to heat
No need. Because of the heat of enzymes during briquetting,
If using an agitation granulator equipped with a
Temperature during the coating process, which is preferably heated or cooled
The temperature is generally between 0 and 100 ° C and between 10 and 80 ° C.
Is preferred. (5) Addition order The addition order of the coating agent and the liquid binder is the final addition amount.
Is not particularly limited as long as the briquettes are stirred.
Powder coating after spraying (or dripping) binder
The coating operation should be performed in the order of
Is preferred. It is also a good idea to repeat this operation
No. If the fluidity of the obtained solid detergent is poor,
Adjusts fluidity by coating with fine powder such as zeolite
It is also preferable to do so. EXAMPLES Hereinafter, the present invention will be described with reference to Examples, Comparative Examples and
Although described in more detail by way of prescription examples, the scope of the present invention,
It is not limited in any way by these examples. [Brimet-linked sheet-shaped primary molded body A]
Preparation Example 1] (Kneading / crushing granulation method) Of the compositions shown in Table 1 below, 6.5% A-type zeolite
250L of ingredients except for nonionic surfactant A and enzyme
Water, fluorescent agent, LAS-K (LAS-K
Linear alkylbenzene sulfonic acid and potassium hydroxide
Neutralized and produced by the system) Sodium silicate, stone
Soap, acrylic acid / maleic acid copolymer salt, type A Zeola
, Sodium carbonate, sodium sulfite, sodium chloride
, And a total of 200 kg was added. Slurry is moisture
The specific gravity was 38%, the specific gravity was 1.1 kg / L, and the pH was 11. Preparation
The slurry was counter-flowed, tower diameter 2.0m, effective length 5.0m
400 kg / hr using a pressure nozzle in the drying tower
Feeding and spraying were performed with force to obtain a dry powder. Nozzle
-75786 as described in Example 2
Spraying was performed at a mist pressure of 0.25 MPa. Also, finer than the tower
Blow in cold air accompanied by 3.0% of zeolite A
At the same time as lowering the powder temperature, dry powder coating
became. (After this, dry the zeolite coated
The dried powder is referred to as spray-dried particles). Drying tower at this time
Hot air temperature is 280 ° C, exhaust air temperature is 100 ° C,
The temperature of the obtained dried powder was 40 ° C. Spray dried particles
Means average particle size 250 μm, bulk specific gravity 0.28 kg / L, dried
Immediately after, the angle of repose was 40 ° and the average moisture was 4.0%. Get
Nonionic surfactant and water along with the spray-dried particles
Continuous Kneader (Kurimoto Iron Works Co., Ltd., S4KRC Knee)
And the kneading capacity is 120 kg / h and the temperature is 60 ° C.
The mixture was kneaded under the conditions to obtain an amorphous solid detergent. This amorphous solid
Pellet dub equipped with a 10 mm hole diameter die
(Fuji Paudal Co., Ltd., EXDFJS-100 type)
While extruding with a cutter, cut with a cutter to a length of 5-30
A pelleted solid detergent of about mm was obtained. Then the obtained
Granulated zeolite 3.0 as a grinding aid in solid detergent
%, And in the presence of cold air (10 ° C, 15m / s)
Fitzmill (Hosokawa Micron)
The average particle diameter is 800 μ using DKA-3) manufactured by Co., Ltd.
m (screen hole diameter: first stage / 2
Stage / 3rd stage = 8mm / 6mm / 3mm, rotation speed: all stages
3290 rpm). The obtained granules are mixed with a horizontal cylinder
Machine (cylinder diameter 585mm, cylinder length 490mm, container
Clearer with inner wall on 131.7L drum inner wall
With two baffles of 20 mm in height and 45 mm in height
), Filling rate 30%, rotation speed 22 rpm, 25
Under the condition of ° C, 0.5% of fine powder zeolite is added,
Roll for a minute to coat, then add enzyme
Mix for 30 seconds. This detergent composition has an aperture of 1400 μm
Using a 500μm sieve and a 500μm sieve
Permeate through a 1400μm sieve and open with a 500μm sieve
Particles that did not pass through. Detergent composition particles after this classification
Cellulose granules (Arbo)
cel-TF-30-HG) so as to be 10% by mass.
Add and mix homogeneously. This mixture is
Supply to Shin (CS-25 type manufactured by Hosokawa Micron Corporation)
Then, a 4.5mm high, 6mm diameter briquette is connected
A briquette-connected sheet-shaped primary molded body A was obtained. Yellowtail
The operating condition of the ketting machine is that the roll rotation speed is 30r.
pm, product capacity 170kg / h, 25 ° C, roll clear
The lance was 0.1 mm. In addition, opening 1400μm
Particles that have not passed through the sieve of
The particles that have passed through are reduced to the kneading step and reused. LAS-K 20.6% by mass AOS-K 15.5 Soap 0.3 Zeolite * 17.9 Sodium carbonate 3.66 Potassium carbonate 14.5 Sodium sulfite 1.8 Sodium silicate 4.0 Fluorescent agent 0.05 Nonionic surfactant A 4.5 (compounded at the time of kneading) Enzyme 0.15 Water 9.0 Other small components Balance * Of these, 3.0% is dry powder coating, 3.0% is The grinding aid, 0.5%, was used for coating the granules. [Brimet-linked sheet-shaped primary molded body B]
Preparation Example 2] (Stirring granulation method) Nonionic surface activity so as to have the composition shown in Table 2 below
All raw materials except for Agent B and 5% of zeolite
-Dige Mixer (M20, manufactured by Matsubo Corporation)
(Filling rate 50%), and the spindle (200 rpm)
Stirring of par (6000 rpm) was started (jacket
Temperature 25 ° C). Nonionic surface activity 30 seconds after the start of stirring
The entire amount of the agent was added in 5 minutes, after which the average particle size was 80
The stirring granulation was continued until the thickness became 0 μm. Finally, Zeory
5% of the detergent composition and stirred for 30 seconds.
Got. This detergent composition is sieved with a sieve having an aperture of 1400 μm.
Classify using a 500 μm sieve with an opening of 1400
through a 500 μm sieve and through a 500 μm mesh sieve
No particles obtained. Disintegrate into the detergent composition particles after this classification.
30% of sodium citrate as dissolution promoter
And uniformly mixed. Briquette this mixture
Machine (CS-25 type manufactured by Hosokawa Micron Corporation)
And a briquette with a height of 4.5 mm and a diameter of 6 mm
A connected sheet B was obtained. Briquetting machine
The operating conditions were as follows: roll rotation speed 30 rpm, product capacity 170
kg / h, 25 ° C, roll clearance is 0.1mm
there were. In addition, it does not pass through a sieve with an opening of 1400 μm.
The particles were made by Fitzmill (manufactured by Hosokawa Micron Corporation, D
KA-3) (screen hole diameter: 2 mm,
(Rotation speed: 4700 rpm), sieve with openings of 500 μm
It is reduced together with the permeated particles to the agitation granulation process and reused.
Was. Nonionic surfactant B 25.0% by mass Sodium carbonate 23.0 Potassium carbonate 3.0 Zeolite 20.0 Copolymer salt of acrylic acid and maleic acid 4.0 White carbon 4.0 Montmorillonite 6. 0 Sodium sulfite 0.2 Fluorescent agent 0.3 Water 7.0 Other minor components Balance [Brimet-linked primary molded article C
Preparation Example 3] (Kneading / crushing granulation method) Of the compositions shown in Table 3 below, 6.5% of A-type zeolite
250 L of ingredients except for nonionic surfactant B and enzyme
Water, fluorescent agent, AOS-K, LAS-K, LAS
-Na (LAS-K and LAS-Na
Chain alkylbenzene sulfonic acid and potassium hydroxide or
Soap produced by neutralization with sodium hydroxide)
Acrylic acid / maleic acid copolymer, zeolite A,
Potassium carbonate, sodium carbonate, sodium sulfite, α
200 kg in total in the order of -SF-Na. slurry
Is water 38%, specific gravity 1.1-1.2 kg / L, pH 11
１11.5. The prepared slurry is counter-current type, tower diameter
2.0m, 5.0m effective length drying tower using pressure nozzle
Feed and spray at a capacity of 400 kg / hr
Got. The nozzle is described in Example 2 of JP-A-9-75786.
Spray at the spray pressure of 0.25MPa using the same
Was. Also, 3.0% of fine powdered A zeolite is entrained from the bottom of the tower.
Blown cold air to lower the powder temperature and
Coating was also performed. (After this, zeolite
The coated dry powder is called spray-dried particles.
). At this time, the hot air temperature in the drying tower is 280 ° C, and the exhaust air temperature is
The temperature is 100 ° C and the temperature of the obtained dry powder is 40 ° C.
there were. Spray-dried particles have an average particle size of 250 μm, bulk specific gravity
0.28 kg / L, angle of repose 40 ° immediately after drying, average moisture
It was 4.0%. Along with the spray-dried particles obtained,
Continuous surfactant and water are continuously kneaded by Kurimoto
S4KRC kneader) and kneading capacity 120k
g / h at a temperature of 60 ° C.
Obtained. This irregular shaped solid detergent is mounted on a die with a hole diameter of 10 mm.
Equipped pelleter double (Fuji Powdal Co., Ltd., EX
DFJS-100) while extruding using a cutter
And pelletized solid detergent about 5-30 mm in length
Obtained. Next, the obtained solid detergent was treated with a condyle as a grinding aid.
3.2% equivalent of granular zeolite was added, and cold air (10
Fitz arranged in 3 stages in series in the presence of 15m / s)
Using a mill (manufactured by Hosokawa Micron Corporation, DKA-3)
And pulverized so that the average particle diameter becomes 800 μm.
Lean hole diameter: 1st stage / 2nd stage / 3rd stage = 8mm / 4mm
/2.5 mm, number of rotations: first stage / second stage / third stage = 32
90 rpm / 3055 rpm / 2820 rpm). Get
The granulated material is transferred to a horizontal cylindrical tumbling mixer (cylinder diameter 585m).
m, cylinder length 490mm, in a drum of 131.7L container
Clearance between internal wall and internal wall 20mm, height 45
with two baffles having a thickness of 30 mm).
%, Rotation speed 22 rpm, 25 ° C
Add 1.5% equivalent and roll for 1 minute to coat
Then, the enzyme was further added and mixed for 30 seconds. This detergent
The composition is screened with a sieve having an aperture of 1400 μm and an aperture of 500 μm
Classify using a sieve and pass through a sieve with an aperture of 1400μm
Then, particles that do not pass through a sieve having an opening of 500 μm were obtained.
A disintegration / dissolution accelerator is added to the detergent composition particles after this classification.
And cellulose granules (Arbocel-TF-30-H)
G) was added and uniformly mixed to 10%. This mix
Compound briquetting machine (Hosokawa Micron
(Model Co., Ltd. CS-25 type), height 4.5mm,
Briquette connection sea with brimming of 6mm diameter
A primary molded article C was obtained. Luck of briquetting machine
Rolling conditions: Roll speed 30 rpm, product capacity 170 k
g / h, 25 ° C, roll clearance 0.1 mm
Was. In addition, it did not permeate through the sieve with an aperture of 1400 μm.
The particles and the particles that have passed through a sieve
By re-dissolving in the
Was. [Table 3] α-SF-Na 11.0% by mass LAS-K 4.9 LAS-K 2.1 AOS-K 1.0 Soap 7.8 Zeolite * 21.5 Sodium carbonate 19.67 Carbonic acid Potassium 9.17 Sodium sulfite 1.4 Acrylic acid / maleic acid copolymer salt 3.6 Fluorescent agent 0.14 Nonionic surfactant B 5.0 (mixed during kneading) Enzyme 0.72 Water 8.1 Other minor components ( Impurities, etc.) Balance * Of these, 1.1% was used for coating dry powder, 4.2% was used for grinding aid, and 1.5% was used for coating granules. [Example 1 of Briquette Adjustment]
The screen-shaped primary molded body A is equipped with a screen having a hole diameter of 10 mmφ.
Fezamil (FM-1) manufactured by Hosokawa Micron Inc.
(S type) with rotation speed 600rpm (tip peripheral speed 8.17m /
s) Crushing at 25 ° C, removing burrs at the same time,
A ket A-1 was obtained. [Example 2 of Briquette Adjustment]
The screen-shaped primary molded body A is equipped with a screen having a hole diameter of 10 mmφ.
Fezamil (FM-1) manufactured by Hosokawa Micron Inc.
(S type) with rotation speed 600rpm (tip peripheral speed 8.17m /
s) Crushing at 25 ° C, removing burrs at the same time, crushing
After the briquette is placed in a grid-like groove (3 mm
Fuji Paudal Co., Ltd.'s quince with intervals
(QJ-400 type) and rotating speed 1000 rpm, 2
Roll at 5 ° C for 1 minute to further remove burrs,
A-2 was obtained. [Example 3 of Briquette Adjustment]
Same as Briquette Preparation Example 2 using a sheet-shaped primary molded body B
To obtain briquette B-1. [Example 4 of Briquette Adjustment]
Without grinding the sheet-shaped primary compact A,
Fuji Paudal Co., Ltd. with grooved grooves (3mm intervals)
Rotation speed 1
Roll at 000 rpm, 25 ° C for 5 minutes to remove burrs
Then, briquette A-3 was obtained. [Example 5 of Briquette Adjustment]
Same as Briquette Preparation Example 2 using a sheet-shaped primary molded body C
To obtain briquette C-1. [Example 6 of Briquette Adjustment]
Same as Briquette Adjustment Example 4 using a sheet-shaped primary molded body C
The briquette C-2 was obtained. In addition, crushing and burr of Briquette Preparation Examples 1 to 6
Residues such as burrs generated in the
Examples of Preparation of Rickett-Connected Sheet Primary Moldings A to C
By re-dissolving in the slurry blending process
And reused. (Examples 1 to 60) Briquettes A obtained
-1, A-2, A-3, B-1, C-1, C-2 are shown below.
According to the coating operation method A or the coating operation method B, Table 4 was used.
The surface was coated so as to have the composition shown in Tables 1 to 7, and the solid detergent was
Obtained. This solid detergent is passed through a 9.5 mm sieve and a sieve.
Classify using a 4.75 mm sieve.
Permeate through sieve, not through 4.75 mm sieve
The product was a product. In addition, it passes through a sieve with an opening of 9.5 mm.
Through the unwashed solid detergent and a 4.75 mm sieve.
The excess solid detergent is re-dissolved in the slurry compounding process.
More reduced and reused. [Coating operation method A]
Rickett was mixed with Redigue Mixer (Matsubo Co., Ltd., M
20 type) (filling rate 20%), and the main spindle (120 rpm)
m) was started (jacket temperature 25 ° C,
Par stopped). Add liquid binder immediately after starting stirring
Was started and the entire amount was added in 5 minutes. After the addition is complete,
, And stirring was continued for 2 minutes. Finally last
Add the whole amount of the surface coating agent, stir for 30 seconds, and further prepare
Stir for 30 seconds while perfuming 0.16% of perfume,
A solid detergent was obtained. [Coating operation method B] The amount of coating shown in Tables 4 to 7
Each briquette is transferred to a horizontal cylindrical rolling granulator (cylinder diameter 585).
mm, cylinder length 490mm, volume of 131.7L
Clearance between internal wall and internal wall 20mm, height
(With two 45 mm baffles) (filling rate 15
%), And the rolling operation was started at 20 rpm. Rolling operation open
Immediately after the start, start spraying the liquid binder.
Sprayed. After the spraying is completed, the entire amount of the coating component is charged and 4
The rolling operation was continued for one minute. Finally, the total amount of the final surface coating
And rolled for 30 seconds, equivalent to 0.16% of the product
Rolled for 30 seconds while perfuming the perfume, to obtain a solid detergent. (Comparative Examples 1 to 6) Each of the obtained briquettes was
Use 9.5mm sieve and 4.75mm sieve
And then classify, pass through a 9.5 mm sieve and open
A product that did not pass through a 4.75 mm sieve was used as a product. Comparative Example 7 The composition shown in Table 8 was obtained.
To remove nonionic surfactant B and zeolite equivalent to 5%
Horizontal cylindrical rolling granulation using almost all raw materials in Example 2
Into the machine (filling rate 15%) and perform rolling operation at 20 rpm
Started. One minute after the start of the rolling operation, a nonionic surfactant
Spraying of B was started, and the whole amount was sprayed in 10 minutes. End of addition
Thereafter, the rolling operation is continued until the average particle size of the granulated product becomes 6 mm.
And finally add 2% equivalent of zeolite and mix,
A solid detergent was obtained. This solid detergent is passed through a sieve having an opening of 9.5 mm.
Classify using a 4.75mm sieve
Permeate through 9.5mm sieve, 4.75mm sieve
A product that does not transmit light was used as the product. [Evaluation of Product Appearance] The appearance of the solid detergent was evaluated as follows.
The evaluation was made according to criteria. ◎: Extremely beautiful で: Beautiful △: Not beautiful, but acceptable level x: Rough appearance [Solubility test] Placed in 3000 ml beaker
Add constant temperature tap water and add 25 g of briquette detergent composition.
Charged and stirred for 10 minutes. Next, undissolved detergent particles
Is taken out on a nylon cloth and dried at 105 ° C. for 2 hours.
Calculate the dissolution residue represented by the following formula and evaluate based on the following criteria
did. Formula 1 dissolution residue (%) = [(dissolution residue at 105 ° C. for 2 hours, dried product (g) / 25 g)] × 100 ：: 0% ≦ dissolution residue <1% ○: 1% ≦ dissolution residue <5% △ : 5% ≦ dissolution residue <10% ×: 10% ≦ dissolution residue [Product yield] The product yield is calculated by the following formula.
(80% or more is an acceptable level). Formula 2 Product yield [%] = (amount of solid detergent as product after classification operation [kg]) / (amount of total solid detergent discharged from granulator [kg]) × 100 [Odor deterioration] Coated cardboard from outside
(Basic weight: 350 g / m ^Two ), Wax sand paper (basis weight:
30g / m ^Two ), Kraft pulp paper (70 g / m ^Two 3)
Using paper consisting of layers, length 15cm x width 9.3cm x
A box having a height of 18.5 cm was prepared. Sample 1.2 in this box
kg and put in a constant temperature and humidity room at 50 ° C and 85% RH.
Storage for days, compare the odor before and after storage, and
The evaluation was performed according to the standard. ：: Almost no odor deterioration. Δ: Odor slightly deteriorated. ×: There is considerable odor deterioration. [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 SO _Three Using nitrogen gas as the dilution gas
To 8% SO3 containing inert gas, and the reaction molar ratio (S
O _Three / 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)
Salt LAS-Na: Lipon LH-200 (Lion)
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
(Production method) α-olefin (Dialen 14 at 25 ° C.)
8, Mitsubishi Chemical Corporation) at a capacity of 970 kg / hr
Successive TO reactors (TO-500, Lion Corporation)
, Film type reactor) _Three gas
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). ○ AS-Na: Sannolu DL-1130 (Lion
○ Soap: Fatty acid sodium by the following production method (Production method) Fatty acid methyl ester (Pa)
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. ○ Nonionic surfactant A: Die by the following production method
Doll 13 (made by Mitsubishi Chemical Corporation)
4 liter autoclave (pressure-resistant glass works)
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. ○ Nonionic surfactant B: Die by the following production method
Doll 13 (made by Mitsubishi Chemical Corporation)
4 liter autoclave (pressure-resistant glass works)
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%. ○ Nonionic surfactant C: Die by the following production method
Doll 13 (made by Mitsubishi Chemical Corporation)
4-liter autoclave (pressure-resistant glasswork)
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 (corresponding to an average addition mole number of 15 moles) were introduced,
The reaction between iador 13 and EO is carried out, and the mixture is aged for 30 minutes.
Was. Thereafter, the reaction solution was cooled to a temperature of 120 ° C.
Propylene oxide while maintaining 0 ° C pressure 3atm
(PO: manufactured by Mitsubishi Chemical Corporation) 350 g (average added mole number)
(Equivalent to 3 moles) was introduced to carry out the reaction. 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%. ○ Nonionic surfactant D: Paste by the following production method
Acid of M-181 (manufactured by Lion Oreo Chemical Co., Ltd.)
4-mol autoclave (pressure-resistant glass)
M-181 (Lion)
400g) and catalyst (magnesium aluminum)
Nitride and manganese composite hydroxide in nitrogen atmosphere 800
Aged at 3 ° C for 3 hours to form a composite oxide of Mg / Al / Mn.
1.2g and 40% KOH aqueous solution 0.12g
And the inside of the autoclave is replaced with nitrogen.
(While dehydrating at 100 ° C for 30 minutes)
). Next, maintain the temperature at 180 ° C and the pressure at 3 atm
While ethylene oxide (EO: Mitsubishi Chemical Corporation)
899 g (equivalent to an average added mole number of 15 moles)
And pastel M-181 (Lion Oreo Chemical
And EO. Finally ripened for 30 minutes
To obtain a nonionic surfactant. Nonionic surfactant
Approximately 2.0% of PEG and approximately unreacted alcohol
0.7%. ○ Cationic surfactant: Esocard C / 12 (Lion
・ Akzo Corporation ○ Amphoteric surfactant: Enazicol L-30B (Lion
○ Zeolite (4A type zeolite): Shilton B (Mizusawa)
(Manufactured by 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.)
○ Sodium carbonate: light ash (manufactured by Asahi Glass Co., Ltd.) ○ Sodium sulfite: anhydrous sodium sulfite (Shinshu Chemical Co., Ltd.)
○ Sodium silicate: JIS No. 1 sodium silicate (purity 4
5% aqueous solution) ○ Sodium sulfate: Neutral anhydrous sodium sulfate RBK-13 (Nippon Kagaku)
Gaku Kogyo Co., Ltd.) ○ White carbon: Toksil N (amorphous silica)
(Manufactured by Tokuyama Corporation) ○ Montmorillonite: Bentonite BPW-00 made in China
9 (Mitsubishi Corporation) ○ Sodium percarbonate: SPC-D (Mitsubishi Gas Chemical Co., Ltd.)
○ OBC: 4-decanoyloxybenzoic acid (Mitsui Chemicals)
○ Fluorescent agent: Tinopearl CBS-X (Ciba Specialty)
Chemicals) PEG600: PEG # 600 (Lion Chemical Co., Ltd.)
○ PEG200: PEG # 200 (Lion Chemical Co., Ltd.)
○ Cellulose granules: Arbocel-TF-30-HG
(Manufactured by Rettenmeier) (average particle diameter 700 to 800)
μm) ○ Sodium citrate: trisodium citrate dihydrate
(First grade reagent) (Junsei Chemical Co., Ltd.) (Average particle size 400
μm) ○ Sucrose: Saccharose (first grade reagent) (Junsei Chemical Co., Ltd.)
(Average particle diameter 300 μm) ○ Enzyme: Sabinase 18T (Novo Nordisc Bio)
Industry) ○ Fragrance: 0.5% by mass of decanal (below%), Ok
0.3% tanal, hexylcinnamitaldehyde
10.0%, dimethylbenzylcarbinyl acetate
G 8.0%, Lemon oil 3.0%, Liliar
6.0%, Lillal 2.0%, Linalool 5.
0%, Phenylethyl alcohol 7.5%, Tona
2.0% lid, o-tert-butylcyclohexyl
Luacetate 3.0%, Galaxolide 50 BB
2.0%, Linascol 2.5%, Geranio
Le 1.0%, Citronellol 2.0%, Jas
Morangi 2.0%, Methyldihydrojasmonate
5.0%, terpineol 1.0%, methylyo
Non 3.0%, Acetyl Cedrene 5.0%, Remo
Nitrile 1.0%, Fluitate 1.0%, E
Ribbon 1.5 Benzoin 1.0%, cis-3-f
Xenon 0.5%, Coumarin 2.0%, Dama
Senon 0.2%, Damascon 0.3%, Helio
Nal 1.5%, Heliotropin 1.5%, Ani
2.5% sualdehyde, gamma-undecalactone
0.8%, Bagdanol 1.2%, Triplar
Le 0.5%, Styrilyl acetate 1.5%,
Caron 0.1%, Pentalide 3.0%, Oxa
2.9% hexadecene-2-one, ethylene brush
Rate 6.2%, Note: BB means benzyl benzoate. [Prescription Examples] Other prescription examples in the present invention are shown below.
It is shown in FIG. [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9]

Claims (1)

Claims: 1. A solid detergent, comprising: briquetting detergent raw materials; and coating the resulting briquettes with a coating material containing inorganic powder.