JPH1088199A - Production of tablet or briquette-formed detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tablet or briquette-formed detergent composition having excellent solubility. SOLUTION: The objective tablet or briquette-formed detergent composition having a bulk density of 1.0-2.0g/ml, is produced by mixing a detergent raw material containing a nonionic surfactant having a melting point of <=40 deg.C, an oilabsorbing agent for occluding the nonionic surfactant and a crystalline silicate as essential components, granulating the mixture to obtain detergent particles having an average particle diameter of 150-1,500μm and a bulk density of 0.6-1.2g/ml and tableting or briquetting the obtained detergent particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a tablet-type or briquette-type cleaning composition having a nonionic surfactant as a main base and having excellent solubility.

[0002]

2. Description of the Related Art There are two types of cleaning agents commonly used, a liquid type and a granular type. In particular, powdery materials are mainly used at present. However, the powdered detergent has a drawback that the powder may be scattered at the time of use, which causes discomfort to the user. In order to solve this problem, a number of attempts for tableting a powder detergent have been proposed.

[0003] These are mainly tablet-type detergents containing an ionic surfactant as a main cleaning surfactant, but tablet-type detergents using a nonionic surfactant as a main cleaning surfactant are also disclosed in, for example, US Pat. No. 3231506, U.S. Pat.No. 3,247,123, U.S. Pat.No. 3,331,780
No. 3,334,076 and the like.

[0004] These tablet-type detergents have the advantage that they do not scatter powder and are easy to use as compared with the above-mentioned liquid-type or granular-type detergents, but have strength enough to withstand during handling and transportation. In addition, properties such as rapid dissolution at the time of use are required. Generally, when the molding pressure is increased to increase the strength of the tablet, there is a disadvantage that the solubility in water is reduced.

Many proposals have been made to overcome such disadvantages. Among them, for example, after mixing and shaping a decomposition or volatile substance, a method of making it porous by applying a heat treatment, blending a carbonate and a solid acid, and generating carbon dioxide in water A method of accelerating dissolution, a method of blending a disintegrant widely used in the field of medicines to make tablets easily disintegrate in water (Japanese Patent Publication No. 44-17745).
No. 47-27208).

However, in these methods, although the solubility in water is improved to some extent, they are not sufficiently satisfactory for practical use. The reason is that
In tablets containing a large amount of a surfactant such as a detergent, since the surfactant hydrates in water and takes on a highly viscous property, it becomes difficult for water to enter the inside of the tablet,
It is considered that the dissolution promoting effect is not sufficiently exhibited.

On the other hand, it is known that briquettes are used in addition to tablet-type detergent compositions. While the tablet is tablet-formed by irregularities, the briquette-type detergent composition rotates the rolls dug into the surface of the pocket to be prepared for the briquette so as to bite each other, and the raw material is used for the bite. And compressed.

Therefore, since the forming surface of the roll into which the briquette mold is dug is a curved surface, the briquette mold does not completely close, and an air passage for releasing air from the raw material during compression is always secured. As a result, the internal structure of the molded article is uniform and dense, and there is an advantage that air hardly remains.

Several compositions of briquette-type detergents have been proposed so far (JP-A-44-14681, WO9423010).
). However, these compositions have eliminated the scattering of powdery detergent powder, but have not sufficiently studied the improvement of the solubility, and the solubility was not sufficient.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have made a liquid or paste-like nonionic activator as a main base, mixed a detergent raw material containing a crystalline silicate, The mixture is granulated to a specific bulk density and particle size, and the resulting detergent granules are tabletted or briquetted to obtain a tablet-type or briquette-type detergent composition having excellent solubility. To be able to
The present invention has been completed.

That is, the present invention provides the following (1), (2) and
It is intended to provide a method for producing a tablet type or briquette type detergent composition comprising the step (3). Process (1)…
A step of mixing a nonionic activator having a melting point of 40 ° C. or lower, an oil absorbing agent for occluding the nonionic activator, and a detergent raw material containing a crystalline silicate as essential components. Process (2)… Process
Granulate the mixture obtained in (1), average particle size 150 ~ 1500
Step of obtaining detergent particles having a μm and a bulk density of 0.6 to 1.2 g / ml. Step (3): a step of compressing the detergent particles obtained in Step (2) to obtain tablets or briquettes having a bulk density of 1.0 to 2.0 g / ml.

Examples of preferred embodiments of the present invention are as shown in the following 2 to 18.

2. The oil absorbing agent is a silica derivative and / or spray-dried particles. The oil absorbing agent as referred to in the present invention refers to porous particles capable of occluding a liquid substance, particularly preferably spray-dried particles obtained by spray-drying a slurry comprising a detergent component and water, and / or silica derivatives. .

3. The detergent raw material is any one selected from the following (a), (b) and (c). (a) 20 to 89 parts by weight of a builder (including a crystalline silicate), 1 to 20 parts by weight of a silica derivative, and 10 to 60 parts by weight of a nonionic activator (b) Builder (including a crystalline silicate) / spray Dry particles = 75/95 parts by weight of a mixture of 5 / 95-95 / 5 (weight ratio) and 5-25 parts by weight of nonionic activator (c) Builder (including crystalline silicate) / spray-dried particles = 5 / 20-89 parts by weight of a mixture of 95-95 / 5 (weight ratio), 1-20 parts by weight of a silica derivative and 10-60 parts of a nonionic activator
Parts by weight Here, the builder, the spray-dried particles and the silica derivative have the following properties. ·builder:
Crystalline silicate and at least one or more organic or inorganic powder builder and spray-dried particles: particles obtained by spray-drying a water slurry containing at least one or more organic or inorganic builder. Silica derivative: mercury pore volume in the penetration method 100~600cm ³ / 100g, a specific surface area by the BET method is 20~700m ² / g, an oil absorption of 100 ml / 100 in JIS K 5101
g silica derivative.

4. During or after the step (2), a surface coating agent is further mixed and the surface of the detergent particles is coated with the surface coating agent, and then the step (3) is performed.

5. In the above item 4, the surface coating agent is mixed with 0.5 to 30 parts by weight based on 100 parts by weight of the detergent particles.

6. Crystalline silicate is present in the total composition from 1 to 30
The production method according to any one of the above 1 to 5 which contains 1% by weight.

[7] After step (2), the average particle size is 100 to 10
A monocarboxylic acid or a polycarboxylic acid having 6 carbon atoms or less of 00 μm or a salt thereof is blended in a weight ratio of [carboxylic acid (salt)] / [detergent particles] = 1/99 to 30/70 with respect to the detergent particles, After mixing with the detergent particles, the step (3) is performed.

8. After the surface of the detergent particles is coated with a surface coating agent, a mono- or polycarboxylic acid having an average particle diameter of 100 to 1000 μm and a carbon number of 6 or less or a salt thereof is added in a weight ratio of [carboxylic acid ( Salt)] / (coated detergent particles) = 1/99 to 30/70, mixed with the coated detergent particles, and then performing step (3).

9. The above 7 or 8 wherein the mono- or polycarboxylic acid or a salt thereof is one or a mixture of two or more selected from acetic acid (salt), succinic acid (salt), maleic acid (salt), and citric acid (salt). Manufacturing method.

10. The nonionic activator is a polyoxyethylene alkyl ether having an average ethylene oxide mole number of 5 to 15 of a linear or branched, primary or secondary alcohol having 10 to 20 carbon atoms.

11. As a builder other than the crystalline silicate, one or a mixture of two or more selected from sodium tripolyphosphate, sodium carbonate, aluminosilicate, citrate, polyacrylate, and polyethylene glycol is used.

12. The spray-dried particles are particles obtained by spray-drying a water slurry containing one or a mixture of two or more selected from sodium tripolyphosphate, sodium carbonate, aluminosilicate, citrate, polyacrylate, and polyethylene glycol. .

13. The silica derivative is an amorphous aluminosilicate.

14. The average particle size of the primary particles of the surface coating agent is 10
14. The production method according to the above 4, 5, or 8, which is not more than μm. The surface coating agent having an average primary particle size of 10 μm or less is one or a mixture of two or more selected from silicate compounds such as aluminosilicates and amorphous silica derivatives.
16 manufacturing methods.

16. The average particle size of the nonionic detergent particles obtained in step (2) is 250 to 800 μm.

17. 17. The method according to any one of 1 to 16, wherein the detergent composition is a briquette-type detergent composition, and the absolute maximum length of a vertical projection image of the briquette-type detergent composition is 10 mm or less.

18. 17. The production method according to any one of 1 to 16, wherein the detergent composition is a tablet-type detergent composition, and the absolute maximum length of the tablet-type detergent composition is 50 mm or less.

The following describes the manufacturing method of the present invention. [Step (1)] Step (1) in the production method of the present invention
Is a step of mixing a detergent raw material containing a nonionic activator having a melting point of 40 ° C. or lower, an oil absorbing agent for storing the nonionic activator, and a crystalline silicate as essential components.

In carrying out the step (1), the method of charging the components of the detergent into the mixer is not particularly limited. After charging the components of the inorganic powder builder, the oil absorbing agent, the crystalline silicate, and the optional component which are preferably blended first into a mixer, a nonionic activator is added,
The method of mixing is particularly preferred.

The mixing in the step (1) and the granulation in the step (2) can be performed by a continuous apparatus. In this case, the detergent raw materials are continuously mixed or the mixing and the granulation are performed simultaneously. The method for supplying the detergent raw material is not particularly limited. In the present invention, when the detergent raw materials are continuously mixed and granulated, all of the nonionic activator and other powder raw materials are mixed in advance in a batch system, and the mixture is continuously mixed in the granulation step. May be supplied. Further, in either the batch method or the continuous method, it is preferable that the nonionic activator is supplied by spraying.

Apparatuses suitably used in the step (1) of the present invention include the following apparatuses. First, the following (1) to (4) are suitably used as the apparatus for the batch operation. (1) This type of mixer has a stirring shaft inside a mixing tank, and a stirring blade is attached to the shaft to mix powder. For example, Henschel mixer [manufactured by Mitsui Miike Kakoki Co., Ltd.], high speed mixer [Fukae Industry Co., Ltd.]
And vertical granulators [manufactured by Powrex Corporation], etc., but it is particularly preferable to use a horizontal mixing tank having a stirring shaft at the center of the cylinder, and mixing the powder by attaching stirring blades to this shaft. For example, there are a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd.) and a blow shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.). (2) There is a mixer of a type in which mixing is performed by rotating a V-shaped mixing tank, for example, a V-type mixer (manufactured by Fuji Paudal Co., Ltd.). (3) There is a mixer of a type in which mixing is performed by rotating ribbon-shaped blades forming a spiral in a fixed semi-cylindrical container, for example, a ribbon mixer (manufactured by Fuji Paudal Co., Ltd.). (4) A mixer of the type that performs mixing by revolving around the axis parallel to the container wall while the screw rotates along the conical container, such as a Nauta mixer (manufactured by Hosokawa Micron Corporation), an SV mixer [ Shinko Vantec Co., Ltd.].

In the case of the continuous operation,
The following (1) to (3) are preferably used. (1) Consisting of a vertical cylinder with a powder inlet and a main shaft with a mixing blade, the main shaft is supported by an upper bearing, and a continuous mixer with a structure in which the discharge side is free, for example, a flexomix type ( Manufactured by Powrex Corporation]. (2) A raw material is charged into the upper part of a disk having a stirring bottle, the disk is rotated at a high speed, and a continuous mixer of a type of mixing by shearing action, for example, a flow jet mixer [manufactured by Koken Bautex Co., Ltd.] And a spiral bin mixer (manufactured by Taiheiyo Kiko Co., Ltd.). (3) It is a continuous mixer of the type in which a mixing tank has a stirring shaft inside and a stirring blade is attached to this shaft to mix powder. For example, there is a continuous Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). High-speed mixer (Fukae Kogyo Co., Ltd.)
An apparatus such as a vertical granulator (manufactured by Powrex Corporation) may be used as a continuous apparatus. It is preferably a horizontal type mixing tank having a stirring shaft at the center of the cylinder and a stirring blade attached to the shaft to mix powders, and is a continuous mixer such as a Loedige mixer [Matsuzaka Giken Co., Ltd. )), Blowshare Mixer [Taikai Kiko Co., Ltd.
Made).

[Step (2)] In the step (2) in the production method of the present invention, the mixture obtained in the step (1) is granulated to have an average particle diameter of 150 to 1500 μm and a bulk density of 0.6 to 1.2 g / ml. This is a step of obtaining nonionic detergent particles of

As the granulation method in the step (2) of the present invention, a generally known detergent granulation method can be used, and a general apparatus used at this time is an extrusion granulator, A fluidized granulator, a tumbling granulator, a stirring tumbling granulator and the like are preferably used. Examples of the fluidized granulator include spiral flow (manufactured by Freund Corporation) and multiprocessor (manufactured by Powrex). As an example of a rolling granulator, a marmelizer [Fuji Powder Co., Ltd.]
Co., Ltd.), CF Granulator [Freund Sangyo Co., Ltd.
Manufactured). Examples of the agitating tumbling granulator include a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powrex Co., Ltd.) and the like. .

In addition, the granulating apparatus used in the step (2) of the present invention has a stirring shaft provided with a stirring blade at the center of the inside thereof, and when the stirring blade rotates, the stirring blade, the vessel wall and A stirring mixer having a structure in which a clearance is formed between them can also be used. As a stirring type mixer having such a structure, for example, Henschel mixer [Mitsui Miike Kakoki Co., Ltd.
), A high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), a vertical granulator (manufactured by Powrex), and the like. Particularly preferred is a horizontal mixing tank having a stirring shaft at the center of a cylinder. This type of mixer is a type of mixing powder by attaching stirring blades to a shaft, and can be granulated by, for example, a Loedige mixer (manufactured by Matsuzaka Giken Co., Ltd.) or a blow shear mixer (manufactured by Taiheiyo Kiko Co., Ltd.).

In step (2), any of the above apparatuses may be used, but the detergent particles obtained in step (2) have an average particle size of 150 to 1500 μm, preferably 150 to 1000 μm, more preferably 250-800 μm and bulk density 0.6-1.2g
/ Ml, preferably 0.7-1.0 g / ml. When detergent granules having an average particle diameter and a bulk density out of such ranges are used, the effects of the present invention cannot be obtained.

[Step (3)] In the step (3) in the production method of the present invention, the detergent particles obtained in the step (2) have a bulk density of 1.0 to 1.0.
In this step, tablets are compressed to 2.0 g / ml and have a volume of at least 1.0 cm ³ or more.

The apparatus for compression used in the step (3) of the present invention is not limited as long as tablets or briquettes can be obtained, and known tableting machines and briquetting machines can be used. A tableting machine is a device that fills a granule into a die and compresses and forms the material between a lower punch and an upper punch.
The tableting machine is a single-shot tableting machine in which a pair of upper and lower punches move up and down in one die and compress it. The dies are embedded at equal intervals around the outer periphery of a horizontally rotating turntable. There is a rotary tableting machine in which a series of operations of filling, compressing, and discharging are continuously performed while rotating. In the briquetting machine, two rolls, each of which is formed with a pocket serving as a matrix of a desired compact on the outer periphery, bite each other, supply granules between the rolls rotating at the same speed, and continuously press-mold. Device.

In the present invention, an advantage of performing the compression in the step (3) after the step (2) is that a nonionic activator or a binder is exuded from the detergent granules during the compression. This becomes an appropriate binder of the detergent and can have excellent binding properties, that is, strength. In addition, the detergent granules retain their shape even during compression, and exhibit excellent properties in disintegration and dissolution in water. However, when compression is performed without using the granulated detergent particles, or when compression is performed using detergent particles having a bulk density of 0.6 g / ml or less, the nonionic activator or binder spreads over the entire compressed product, It will have very strong connectivity. That is, it leads to a decrease in disintegration and even solubility in water.

[0041]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, detergent raw materials used in the method for producing a tablet or briquette type detergent composition of the present invention will be described.

In the present invention, the detergent raw material has a melting point of 40 ° C.
The following nonionic activator, an oil absorbing agent for storing the nonionic activator, and a crystalline silicate are included as essential,
Other than these, optional components of a usual tablet-type or briquette-type cleaning composition can be blended. Particularly preferred detergent raw materials include those shown in the following (a) to (c). (a) 20 to 89 parts by weight of a builder (including a crystalline silicate), 1 to 20 parts by weight of a silica derivative, and 10 to 60 parts of a nonionic activator
Parts by weight (hereinafter referred to as detergent raw material (a)) (b) Builder (including crystalline silicate) / spray-dried particles = 5/95 to 95/5
75 to 95 parts by weight of the mixture (weight ratio) and the nonionic activator 5
25 parts by weight (hereinafter referred to as detergent raw material (b)) (c) Builder (including crystalline silicate) / spray-dried particles = 5/95 to 95
20 to 89 parts by weight of a mixture of / 5 (weight ratio), 1 to 20 parts by weight of a silica derivative, and 10 to 60 parts by weight of a nonionic activator (hereinafter referred to as detergent raw material (c)). The dry particles and the silica derivative have the following properties. -Builder: at least one organic or inorganic powder builder-Spray-dried particles: particles obtained by spray-drying a water slurry containing at least one organic or inorganic builder-Silica derivative: Pore volume of 1 by mercury intrusion method
00-600cm ³ / 100g, specific surface area 20-700m ² / by BET method
g, silica derivatives having an oil absorption of 100 ml / 100 g or more in JIS K 5101. The purpose of using the spray-dried particles in the above detergent raw materials (c) and (d) is (1) control of bulk density, (2) This is an improvement in the oil absorption of the builder.

The spray-dried particles are obtained by drying an aqueous slurry of an organic or inorganic builder by a known spray-drying method. In this case, the organic or inorganic builder is incorporated in the spray-dried particles in an amount of 50% by weight or more, preferably 70% by weight or more. The water content of the aqueous slurry is preferably 30 to 80% by weight.

In the production of the spray-dried particles, if necessary, one or more anionic, cationic or nonionic activators can be incorporated into the spray-dried particles.
It is not preferable to mix the powder in an amount of not less than% by weight because the oil absorbing ability of the spray-dried particles is reduced. 5% by weight of other additives
The following may be added. Here, as other additives,
Examples include a fluorescent dye, an antioxidant, and a binder such as a carboxymethyl cellulose salt.

Among the builders used for the spray-dried particles, citrate, polyacrylate, polyethylene glycol and the like are preferable as organic builders, and sodium tripolyphosphate, sodium carbonate and aluminosilicate are preferable as inorganic builders. In the present invention, synthetic zeolites generally used in detergents are particularly preferred.

The average particle size of the spray-dried particles is 100 to 600.
μm is preferred, and more preferably 150 to 400 μm. The average particle size is measured from the weight fraction based on the size of the sieve after vibrating for 5 minutes using a standard sieve of JIS Z 8801.

The spray-dried particles as the oil-absorbing agent according to the present invention may be those obtained by spray-drying porous builder particles, or may have irregularities formed on the surface by spray-drying, and may be porous. It may be manufactured by selecting such a builder.

The detergent raw materials (b) and (c) of the present invention
In the above, an organic or inorganic powder builder (including a crystalline silicate) and the spray-dried particles are in a weight ratio of (builder) / (spray-dried particles) = 5/95 to 95/5, preferably
It is used at a ratio of 20/80 to 90/10, more preferably 60/40 to 90/10.

Next, among the oil absorbing agents used in the present invention,
In the present invention, the silica derivative refers to an inorganic compound containing silica, and an amorphous compound is particularly preferable because it exhibits excellent oil absorbing ability. The properties, pore volume in the mercury porosimetry 100 to 600 cm ^3/100 g, a specific surface area of the BET method 20
Those having an oil absorption of 700 m ² / g and JIS K 5101 of 100 ml / 100 g or more are preferred. This oil absorption indicates the amount of linseed oil absorbed by the silica derivative based on the method described in JIS K 5101. The average particle size of the silica derivative is preferably from 0.5 to 500 μm, more preferably from 1 to 200 μm, as aggregated particles. This average particle size is measured in the same manner as in the case of the builder described above.

As the silica derivative, a compound containing Al ₂ O ₃ , M ₂ O (where M is an alkali metal), MeO (where Me is an alkaline earth metal) or the like as the second component is preferable. Further, not only two elements but also three elements, four elements, and the like are preferably used. Specifically, the following substances (i) to (iii) are exemplified. (i) As a material containing silica as a main component, Tokusil NR, PR, AL-1, manufactured by Tokuyama Soda Co., Ltd.
Nip Seal NS, Nip Seal NA made by Nippon Silica Co., Ltd.
-R, Nip Seal ES, Degussa's SIPERNAT 22, SI
PERNAT 50, DUROSIL, ZEOSIL 45, TI manufactured by Hanwha Chemical Co., Ltd.
XOSIL 38, Carplex 100 manufactured by Shionogi Pharmaceutical Co., Ltd.
Is mentioned. (ii) Examples of those containing calcium silicate as a main component include HUBERSORB (registered trademark) 600 manufactured by Huber. (iii) As those having aluminosilicate as a main component, AluminumSilicat manufactured by Degussa
e P820, TIXOLEX 25 manufactured by Korea-French Chemical Company. Among the above, as the main component containing the aluminosilicate of (iii), those represented by the following general formula are particularly preferable. Further, these are characterized in that they have ion exchange ability.

(1) x (M ₂ O) · Al ₂ O ₃ · y (SiO ₂ ) · w (H
₂ O) (wherein M represents an alkali metal such as sodium or potassium, and x, y, and w represent the number of moles of each component within the following numerical range. 0.2 ≦ x ≦ 2.00.5 ≦ y ≤10.0
w: any positive number including 0) (2) x (MeO) · y (M ₂ O) · Al
₂ O ₃ .z (SiO ₂ ) .w (H ₂ O) (Me in the formula represents an alkaline earth metal such as calcium or magnesium, M represents an alkali metal such as sodium or potassium, x, y, z,
w represents the number of moles of each component within the following numerical range.
0.001 ≤ x ≤ 0.10.2 ≤ y ≤ 2.00.5 ≤ z ≤ 10.0 w:
Any positive number including 0) In the present invention, as the silica derivative,
Particularly, an amorphous aluminosilicate is preferable.

In addition, a compound having an oil absorbing ability other than the following silica derivatives may be used in a small amount. 1) Calcium silicate Florite R manufactured by Tokuyama Soda Co., Ltd. 2) Callite KT manufactured by Calcium Carbonate Shiroishi Industry Co., Ltd.
Is mentioned. 3) Magnesium carbonate Magnesium carbonate TT manufactured by Tokuyama Soda Co., Ltd. 4) Pearlite 4159 manufactured by Daikarite Orient Co., Ltd.
Is mentioned.

Incidentally, as the silica derivative of the present invention, a clay substance such as smectite is not preferred because it tends to decrease the solubility of tablets or briquettes.

Examples of the builder which can be used for producing the nonionic detergent particles according to the present invention include the following. In the present invention, the crystalline silicate is treated as a builder. Further, other organic or inorganic powder builders refer to substances that can be handled as powder in the following builders. Further, among these organic or inorganic builders, a hydrateable builder and water may be mixed and used as a hydrated salt. Further, it may be the same as the builder used for producing the spray-dried particles described above.

As inorganic builders, sodium carbonate,
Potassium carbonate, sodium bicarbonate, sodium sulfite,
Sodium sesquicarbonate, alkaline salts such as amorphous sodium silicate as exemplified in JIS Nos. 1, 2 and 3, neutral salts such as sodium sulfate, orthophosphate, pyrophosphate, tripolyphosphate , Metaphosphate, hexametaphosphate, phytate and other phosphates (alkali metal salts such as sodium and potassium), and the following aluminosilicates.

No. 1 Crystalline aluminosilicate x '(M ₂ O) .Al ₂ O ₃ .y' (SiO ₂ ) .w '(H ₂ O) represented by the following formula (where M is sodium , Potassium and other alkali metal atoms, x ', y', w '
Represents the number of moles of each component, and generally, 0.7 ≦ x ′ ≦ 1.
5, 0.8 ≦ y ′ ≦ 6, w ′ are arbitrary constants. Among them, those represented by the following general formula are particularly preferred. Na ₂ O
_{· Al 2 O 3 · ySiO 2} · wH 2 O ( wherein, y is 1.8 to 3.0, w is a number of 1-6.).

No. 2 Amorphous aluminosilicate x (M ₂ O) .Al ₂ O ₃ .y (SiO ₂ ) .w (H ₂ O) represented by the following formula:
Represents a sodium and / or potassium atom, x,
y and w represent the number of moles of each component within the following numerical range. 0.7 ≦ x ≦ 1.21.6 ≦ y ≦ 2.8w: any positive number including 0).

No. 3 Amorphous aluminosilicate x (M ₂ O) .Al ₂ O ₃ .y (SiO ₂ ) .z (P ₂ O ₅ ) .w
(H ₂ O) (wherein M is a sodium or potassium atom,
x, y, z, and w represent the number of moles of each component within the following numerical ranges. 0.20 ≤ x ≤ 1.100.20 ≤ y ≤ 4.000.001
≦ z ≦ 0.80w: any integer including 0).

Among these inorganic builders, sodium tripolyphosphate, sodium carbonate, aluminosilicate, and silicate compounds having an ion exchange capacity of 100 (CaCO ₃ mg / g) or more are more preferable.

The following substances are exemplified as the organic builder.

1) ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy-1,
1-diphosphonic acid and its derivatives, ethanehydroxy-
Salts of phosphonic acids such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid 2) 2-phosphonobutane-1,2-dicarboxylic acid, 1- Phosphonobtan-2,3,4-tricarboxylic acid, salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid 3) Salts of amino acids such as aspartic acid and glutamic acid 4) Nitrilotriacetate, ethylenediaminetetraacetate, diamine Aminopolyacetates such as ethylenediaminepentaacetate
5) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene Polymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer Coalescein, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylate copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, maleic anhydride and carbon monoxide. Poly-β-ketocarboxylic acid, itaconic acid, Ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer, itaconic acid-fumaric acid copolymer,
Ethylene glycol-ethylene terephthalate copolymer, vinyl pyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid having a quaternary ammonium group Acid, cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), densuccinic acid or maleic acid or terephthalic acid ester,
Polymer electrolytes such as starch phosphate, dicarboxystarch, dicarboxymethyl starch, carboxymethylcellulose, succinate, etc.6) High non-dissociation of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, cold water soluble urethanized polyvinyl alcohol Molecule 7) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2 Carboxymethylated products such as 5,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, and raffinose; carboxymethylated products of pentaerythritol; carboxymethylated products of gluconic acid; There condensates of sugars with maleic or succinic anhydride, condensates of hydroxycarboxylic acids with maleic acid or succinic anhydride, benzene polycarboxylic acids represented by trimellitic acid,
Ethane-1,1,2,2-tetracarboxylic acid, ethene-1,1,2,
2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-
Organic acid salts such as 1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulhuitaconic acid, malic acid, oxydisuccinic acid, gluconic acid, CMOS, Builder M, etc. Among the organic builders, citrate, polyacrylate and polyethylene glycol are more preferable. Particularly preferred are trisodium citrate, sodium polyacrylate, and polyethylene glycol having a molecular weight of 4,000 to 20,000.

The nonionic activator used in the present invention is not particularly limited, but must have a melting point of 40 ° C. or less, that is, a liquid or paste at 40 ° C.
A nonionic activator having a melting point of 40 ° C. or more becomes a strong binder between particles when pressure is applied during tableting or briquetting, and the solubility is significantly reduced.

Specific examples of the nonionic activator include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester,
Polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine,
Examples include glycerin fatty acid esters, higher fatty acid alkanolamides, alkyl glycosides, and alkylamine oxides.

In particular, the main nonionic activator has 10 to 10 carbon atoms.
20, preferably 10 to 15, more preferably 12 to 14 linear or branched, primary or secondary alcohols, the average addition number of ethylene oxide moles of 5 to 15, preferably 6 to 12, more preferably 6 It is desirable to use ~ 10 polyoxyethylene alkyl ethers. Further, the polyoxyethylene alkyl ether generally contains a large amount of an alkyl ether having a low addition mole number of ethylene oxide,
0 to 3 mol adduct is 35% by weight or less, preferably 25% by weight
It is desirable to use:

The amount of the nonionic activator varies depending on the detergent raw material. That is, the amount of the nonionic activator contained in the detergent raw materials (a) and (c) in the present invention is 5 to 25% by weight, preferably 10 to 25% by weight. When nonionic detergent particles are produced using the detergent raw materials (a) or (c), if the nonionic surfactant is less than 5% by weight, the concentration of the effective component is too low, which is not preferable. On the other hand, if the content of the nonionic activator exceeds 25% by weight, the powder properties, especially the fluidity, are undesirably reduced. The amount of the nonionic activator contained in the detergent raw materials (b) and (d) in the present invention is 10 to 60% by weight, preferably 15 to 50% by weight. When a nonionic detergent is produced using the detergent raw materials (b) or (d), the amount of the nonionic activator can be increased by using a porous oil-absorbing carrier. If it exceeds, the powder properties, especially the fluidity, are undesirably reduced.

In the present invention, a binder may be added at the time of mixing in the step (1) or at the time of the granulation of the step (2) in order to promote granulation during the granulation. You may mix and add. Examples of the binder that can be used during mixing or granulation in the present invention include carboxymethyl cellulose, polyethylene glycol, a water-soluble polymer solution such as a polycarboxylate such as sodium polyacrylate, polyoxyethylene alkyl ether, fatty acid monoethanolamide, Examples include nonionic substances such as fatty acid diethanolamide, fatty acids, aqueous sodium silicate solution, water and the like. The amount of the binder is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the mixture of the detergent raw materials or the granulated detergent particles.

Most of the crystalline silicate salt powder is present in a state of being dispersed inside the final detergent particles, and is substantially not exposed on the surface of the final detergent particles. It is preferable in order to prevent a decrease in cleaning performance due to amorphization due to amorphization and a decrease in alkali buffering capacity due to carbon dioxide gas, and also to suppress insolubilization and insolubilization involving surrounding components occurring after the amorphization. It is preferable that they are dispersed. Hereinafter, the crystalline silicate used in the present invention will be specifically described. The crystalline silicate used in the present invention has a pH of 11 or more in a 0.1% by weight dispersion and exhibits excellent alkalinity. After adding 0.1 g of crystalline silicate to 1 liter of ion-exchanged water, stirring was performed for 3 minutes, and the pH of the solution after sufficiently dissolving or dispersing the silicate was 11 or more. Add 0.
It shows an alkaline buffering capacity such that the amount of 1N hydrochloric acid added until the pH reaches 10 is at least 3 ml or more. The crystalline silicate used in the present invention has crystalline and water-soluble properties, and is distinguished from aluminosilicate generally called zeolite.

The crystalline silicate used in the present invention is preferably an alkali metal silicate, particularly SiO ₂ / M ₂
O (where M represents an alkali metal) of 1.5 to 2.6 is used. On the other hand, the crystalline silicate used in JP-A-60-227895 has an SiO ₂ / Na ₂ O ratio (S / N ratio) of 1.9 to 4.0.
Silicates with a / N ratio of more than 2.6 have reduced detergency and
In the case of 5 or less, the physical properties of the powder may be reduced and caution is required.

The crystalline silicate used in the present invention preferably has the following composition.
_{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O
(1) (where M is an element of Group Ia of the periodic table, and Me is II
a, IIb, IIIa, IVa or one or more combinations selected from the group VIII elements, wherein y / x = 1.5 to
2.6, z / x = 0.01-1.0, n / m = 0.5-2.0, w =
It is 0-20. ) M ₂ O.x'SiO ₂ .y'H ₂ O
(2) (where M represents an alkali metal, x ′ = 1.5 to 2.6, y ′ = 0 to 20) First, the crystalline silicate having the above composition will be described. In the general formula (1), M is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is II in the periodic table
a, IIb, IIIa, IVa or VIII group element;
g, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. Further, it may be mixed alone, or two or more kinds, for example MgO, may constitute the Me _m O _n component by mixing and CaO. In addition, the crystalline silicate of the present invention may be a hydrate, and the hydration amount in this case is in the range of w = 0 to 20.

In the general formula, y / x is 1.5 to 2.6, preferably 1.5 to 2.2. When y / x is less than 1.5, the powder properties of the detergent composition such as caking properties are adversely affected. When y / x exceeds 2.6, the detergency decreases. z / x is 0.01 to 1.0, preferably 0.02
0.9. If z / x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the ion exchange capacity is lowered and the ion exchanger is insufficient. x, y, z are the above y /
The relationship is not particularly limited as long as the relationship is represented by x and z / x. When xM ₂ O is, for example, x ′ Na ₂ O · x ″ K ₂ O, x is x ′
+ X becomes ". This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. Further, n / m = 0.5 ~2.0 is coordinated to the element Indicates the number of oxygen ions, and is substantially 0.5, 1.0, 1.5
, 2.0.

The crystalline silicate having the composition according to the present invention may have M ₂ O, SiO ₂ ,
It has become than the three components of Me _m O _n. Therefore, in order to produce the crystalline silicate of the present invention, each component is required as a raw material, but in the present invention, a known compound is appropriately used without any particular limitation. For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, M ₂ O
The raw materials of the components include NaOH, KOH, Na ₂ CO ₃ ,
_{K 2 CO 3, Na 2 SO} 4 and the like, as a material of Me _m O _{n component, CaCO 3, MgCO 3, Ca} (OH) 2, Mg (O
H) ₂ , MgO, ZrO ₂ , dolomite and the like.
As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

The method for preparing the crystalline silicate having the composition according to the present invention is as follows.
A method in which the above-mentioned raw material components are mixed in a predetermined quantitative ratio so as to have a value of, and usually, calcined and crystallized in a range of 300 to 1500 ° C, preferably 500 to 1000 ° C, and more preferably 600 to 900 ° C. Is exemplified. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is poor, and if it exceeds 1500 ° C., coarse particles are formed and the ion exchange ability is reduced. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The crystalline silicate of the composition according to the invention has an ion exchange capacity of at least 100 CaCO ₃ mg
/ G, preferably 200-600 CaCO ₃ mg / g.

The amount of Si eluted in water is usually 110 mg / g or less in terms of SiO ₂ , and is substantially insoluble in water.
In the present invention, the term “substantially insoluble in water” means that the amount of Si eluted when 2 g of a sample is added to 100 g of ion-exchanged water and stirred at 25 ° C. for 30 minutes is usually 110% in terms of SiO _2.
less than mg / g, but in the present invention,
Those having 0 mg / g or less are more preferable for satisfying the present effect.

Next, the crystalline silicate having the above composition will be described. This crystalline silicate has the general formula (2) M
₂ O.x'SiO ₂ .y'H ₂ O (2)
(Wherein, M represents an alkali metal, x ′ = 1.5 to 2.6, y ′
= 0 to 20. Wherein x ′ and y ′ in the general formula (2) are preferably 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and the cation exchange capacity is 100 to 400 CaCO ₃ mg. /
g can be used and is one of the substances having an ion trapping ability in the present invention.

Such a crystalline silicate is disclosed in JP-A-60-2278.
No. 95 describes the production method, and is generally obtained by firing amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Krista
llogr., 129 , 396-404 (1969). The crystalline silicate is available in powder or granule form, for example, from Hoechst under the trade name "Na-SKS-6" (δ-Na ₂ Si ₂ O ₅ ). In the present invention, the crystalline silicates of the above and the above compositions may be used alone or in combination with each other.
More than one species can be used in combination.

In the practice of the present invention, a surface coating agent is preferably added during or after the granulation in the step (2) to coat the surface of the detergent particles. The surface coating of the detergent particles eliminates unnecessary adhesion between the particles. The term “between and after granulation” as used herein refers to the timing at which the surface of the detergent particles is coated with the surface coating agent, and the detergent particles are granulated within a range of approximately 150 to 1500 μm of the target average particle size. However, some granulation may occur after the addition.

In the present invention, the amount of the surface coating agent for coating the surface of the detergent particles is preferably 0.5 to 30 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the detergent particles.
~ 25 parts by weight. The surface coating agent is preferably a fine powder having an average primary particle size of 10 μm or less. As this surface coating agent, an aluminosilicate is desirable because it acts as a calcium ion scavenger at the time of washing, and in particular, an aluminosilicate having an average primary particle size of 10 μm or less is desirable. As the aluminosilicate, either crystalline or amorphous can be used. In addition to aluminosilicate, silicon dioxide having an average primary particle size of 10 μm or less, bentonite,
Also preferred are inorganic fine powders such as silicate compounds such as talc, clay and amorphous silica derivatives. Aluminosilicate,
Specific examples of the silicate compound such as an amorphous silica derivative include the substances exemplified as the inorganic builder and the porous oil-absorbing carrier. The average particle size of the primary particles is 10 μm
The following metal soaps can be used as well. The average particle size of the fine particles having an average particle size of the primary particles of 10 μm or less is measured by a method utilizing light scattering, for example, by a particle analyzer (manufactured by Horiba, Ltd.) or by a measurement using a microscope.

In the present invention, before the compression for tableting or briquetting in step (3) is carried out, the detergent particles obtained in step (2) or after the step (2) are coated with the above-mentioned surface coating agent. By adding a crystalline and water-soluble inorganic salt to the obtained detergent particles, the solubility is further improved.
Examples of the crystalline and water-soluble inorganic salts other than the silicates of the present invention include carbonates, sulfates, and phosphates. In the present invention, at least one selected from carbonates and sulfates is used. Is good. In particular, among these, alkali metal salts are preferable, and in the present invention, potassium carbonate, sodium sulfite, potassium sulfite, potassium nitrate, sodium chloride,
It is preferred to use sodium hydrogen sulfate. The crystalline and water-soluble inorganic salt is (inorganic salt) /
(Detergent particles or coated detergent particles) = 1/99 to 30/70 by weight. If the weight ratio is less than 1/99, the solubility will not change much. If the weight ratio is more than 30/70, not only will the solubility be reduced, but also the flexibility of blending will be impaired.

Further, by blending a mono- or polycarboxylic acid having an average particle diameter of 100 to 1500 μm and having 6 or less carbon atoms or a salt thereof, the solubility becomes better. Preferred mono- or polycarboxylic acids (salts) are
Acetic acid (salt), succinic acid (salt), maleic acid (salt), and citric acid (salt) are preferred, and sodium acetate and sodium citrate are particularly preferred. Mono or poly carboxylic acid (salt) having 6 or less carbon atoms is [mono or poly carboxylic acid (salt)] / [detergent particle or coated detergent particle] =
It is blended in a weight ratio of 1/99 to 30/70.

In the present invention, the following additives can be used in the steps (1) and (2) or before the step (3). (1) Bleaching agent Sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, etc. (2) Enzymes (enzymes that essentially perform the enzymatic action during the washing process) Classified by enzyme reactivity , Hydrolases, hydrolases, oxidoreductases, desmolases, transferases and isomerases, all of which are applicable to the present invention. Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases. Specific examples of proteases include:
Pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sputilin, BPN
, Papain, promerin, carboxypeptidase A
And B, aminopeptidase, aspergillopeptidase A and B. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases. Specific examples of carbohydrase include cellulase, maltase, saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase. (3) Blue tinting agent Various blue tinting agents can be added as needed. For example, the expression
Those having the structures of (I) and (II) are recommended.

[0082]

Embedded image

(Wherein D ₁ represents a blue-violet monoazo, disazo or anthraquinone dye residue, and X ₁ and
Y ₁ is a hydroxyl group; an amino group, a hydroxyl group, a sulfonic acid group, an aliphatic amino group which may be substituted with a carboxylic acid group or an alkoxy group; a halogen atom, a hydroxyl group, a sulfonic acid group;
It represents an aromatic amino group or a cycloaliphatic amino group which may be substituted with a carboxylic acid group, a lower alkyl group or a lower alkoxy group, and R represents a hydrogen atom or a lower alkyl group. However, when R ₁ represents a hydrogen atom, and X ₁ and Y ₁ simultaneously represent a hydroxyl group or an alkanolamino group, and _one of X ₁ and Y ₁ is a hydroxyl group, and the other is an alkanolamino group. Except in some cases. n represents an integer of 2 or more. )

[0084]

Embedded image

(Wherein, D ₂ represents a blue to purple azo or anthraquinone dye residue, R represents a hydrogen atom or a lower alkyl group, and X ₂ and Y ₂ represent the same or different alkanolamino groups or hydroxyl groups. (4) Anti-caking agent paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, calcium-silicate (e.g. JohnsMan)
vill's microcell etc.), magnesium oxide etc. (5)
Antioxidants tert-butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl-4-
Antioxidants such as methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis- (4-hydroxyphenyl) cyclohexane, etc. (6) Fluorescent dye 4,
4'-bis- (2-sulfostyryl) -biphenyl salt, 4,
4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative, bis (triazinyl) One or two or more amino) stilbene disulfonic acid derivatives are contained in the composition in an amount of 0%.
１1% by weight. (7) One or two kinds of photoactivated bleaching agents sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine are added to the composition in an amount of 0 to 0.2.
% By weight. (8) Fragrance (9) Redeposition inhibitor One or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose and the like can be contained in the composition in an amount of 0.1 to 5%. (10) Surfactants such as alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, alkyl or alkenyl ether carboxylate, soap and the like Anionic surfactants, amphoteric surfactants such as carbobetaine and sulfobetaine, and cationic surfactants such as dilong-chain quaternary ammonium salts can be contained, and the weight of the nonionic surfactant is 3/4. And preferably 好 ま し く or less. When it exceeds 3/4, the binding force between the particles is increased, so that the solubility tends to decrease.

[0086]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 20 and Comparative Examples 1 to 5 Production examples 1 to 4 of detergent particles [Steps (1) and (2)] Ladyge mixer (manufactured by Matsuzaka Giken Co., Ltd., 20 liter capacity, stirring blade) a container wall and clearance 5.0 mm) to the zeolite 4A-type sodium and amorphous aluminosilicate carbonate composition shown in Table 1 _{(0.8Na 2 O · Al 2 O} 3 · 6.5SiO 2, pore volume 310 cm ^3/100 g ,
A specific surface area of 153 m ² / g, an oil absorption of 245 ml / 100 g) and a crystalline silicate (SKS-6, manufactured by Hoechst) are charged, and the main shaft (200 rpm)
And stirring of the chopper (4000 rpm) was started. Thereto, 30 parts by weight of the nonionic activator was added for 1 minute, and the stirring was stopped after 4 minutes. Next, zeolite type 4A was charged as a surface coating agent, stirred for 30 seconds and discharged. The total charge was 4 kg. The bulk density and average particle size of the nonionic detergent particles thus obtained were measured by the method specified in JIS K 3362, and the bulk density and average particle size are shown in Table 1.

[0088]

[Table 1]

Preparation Examples 5-8 of Detergent Particles [Step (1) and Step (2)] The water content of each component for the spray-dried particles shown in Table 2
The weight percent slurry was spray dried to give spray dried particles.
The spray-dried particles obtained and the amount of zeolite 4 shown in Table 2
Type A and amorphous aluminosilicate (0.8Na ₂ O ・ Al ₂ O ₃・ 6.
5SiO ₂ ), sodium carbonate and crystalline silicate (SKS-
6, Hoechst Co., excluding Production Example 8) was charged into a Loedige mixer (Matsuzaka Giken Co., Ltd., capacity 20 liter, clearance 5.0 mm between the stirring blade and the vessel wall), and the main shaft (200 r.
pm) and stirring of the chopper (4000 rpm) was started. There, the amount of the nonionic activator shown in Table 2 was added in one minute,
After 4 minutes, stirring was stopped. Next, zeolite type 4A was charged as a surface coating agent, stirred for 30 seconds and discharged. still,
The total charge capacity was 4 kg. The bulk density and average particle size of the nonionic detergent particles thus obtained were measured by the methods specified in JIS K 3362, and the results are shown in Table 2. In addition,
Production Example 8 is a comparative production example.

[0090]

[Table 2]

The nonionic detergent particles obtained in Production Examples 1 to 8 were mixed with the inorganic salts or carboxylate salts shown in Tables 3 and 4 in Tables 3 and 4.
And detergent particles were obtained.

(Step 3) The detergent particles obtained above were supplied to a briquetting machine (model BSS-501 manufactured by Shinto Kogyo Co., Ltd.), and a height of 3.1 mm and a diameter of 4.8 mm [JIS Z 8841 Briquettes listed in Table 1, "Shape and name of granulated material", vertical projection image in the axial direction, almond shape, diameter 4.8 mm
(Average) circle, diametric thickness 3.1 mm, thickness 0.2 mm due to central clearance. And an elliptical spherical briquette having a pressure density of 1.7 with respect to the bulk density of the detergent particles before the treatment was obtained. The operating conditions of the briquetting machine are as follows: roll rotation speed 30 rpm, detergent particle feed rate 100 kg / hr, roll clearance 0.2 mm, the opening of the deburring sieve is 7.4 m above
m, 2.38 mm in the lower tier, which passed through the upper tier but did not pass through the lower tier was designated as the final product. However, the detergent particles of Production Example 8 were formed into cylindrical tablets having a diameter of 3 cm, a thickness of 10 mm, and a mass of 7.5 g per piece under a pressure of 50 kgf / cm ² . The briquette-type detergent thus obtained was visually evaluated for the ease of scattering of the powder, and the solubility was evaluated under the following conditions.
The results are shown in Tables 3 and 4.

<Method of Testing Solubility> 15 g of the briquette-type detergent obtained as described above is put into a two-tub washing machine (Toshiba) previously filled with 30 liters of tap water at 20 ° C.
The electric conductivity was measured while stirring was performed for 15 minutes with the stirring intensity being “standard”. The used electrical conductivity measuring device is TOA Denpa Kogyo Co., Ltd. (TOA Conductivity Meter CM-60S). The saturation value (end point) of the electric conductivity was a value at which the change in the electric conductivity after 5 minutes from the stirring was less than 1%. The dissolution rate was determined by the following equation.

[0094]

(Equation 1)

The solubility was evaluated at the time when the above-mentioned dissolution rate was 90%. The results are shown in Tables 3 and 4. In this test method, the time at which the dissolution rate becomes 90% is preferably 5 minutes or less.

[0096]

[Table 3]

[0097]

[Table 4]

(Note) Example 21: Detergent particles obtained by adding potassium carbonate to the detergent particles of Production Example 5 were pressed at a pressure of 50 kgf / cm ² at a diameter of 3 cm and a thickness of 3 cm.
Prepared in a tablet detergent of 10 mm and weighing 15 g.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiki Nishi 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (11)

[Claims] 1. A method for producing a tablet type or briquette type detergent composition comprising the following steps (1), (2) and (3). Step (1): a step of mixing a nonionic activator having a melting point of 40 ° C. or lower, an oil absorbing agent for occluding the nonionic activator, and a detergent raw material containing a crystalline silicate as essential components. Step (2): a step of granulating the mixture obtained in Step (1) to obtain detergent particles having an average particle diameter of 150 to 1500 μm and a bulk density of 0.6 to 1.2 g / ml. Step (3): a step of compressing the detergent particles obtained in Step (2) to obtain tablets or briquettes having a bulk density of 1.0 to 2.0 g / ml. 2. The method according to claim 1, wherein the oil absorbing agent is a silica derivative and / or a spray-dried particle. 3. The method for producing a tablet-type or briquette-type detergent composition according to claim 2, wherein the detergent raw material is selected from the following (a), (b) and (c). (a) 20 to 89 parts by weight of a builder (including a crystalline silicate), 1 to 20 parts by weight of a silica derivative, and 10 to 60 parts by weight of a nonionic activator (b) Builder (including a crystalline silicate) / spray Dry particles = 5 / 95-
75 to 95 parts by weight of a 95/5 (weight ratio) mixture and 5 to 25 parts by weight of a nonionic activator (c) Builder (including crystalline silicate)
/ Spray-dried particles = mixture 20 of 5/95 to 95/5 (weight ratio)
~ 89 parts by weight, silica derivative 1 ~ 20 parts by weight and nonionic activator 10 ~ 60 parts by weight 4. The method according to claim 1, wherein a surface coating agent is further mixed during or after the step (2) to coat the surface of the detergent particles with the surface coating agent, and then the step (3) is performed. A method for producing the tablet-type or briquette-type cleaning composition according to claim 1. 5. The method for producing a tablet-type or briquette-type cleaning composition according to claim 4, wherein the surface coating agent is mixed in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the detergent particles. 6. The method for producing a tablet type or briquette type cleaning composition according to claim 1, wherein the crystalline silicate is contained in an amount of 1 to 30% by weight in the whole composition. 7. After the step (2), an average particle diameter of 100 to 1500 is further added.
A mono or polycarboxylic acid having 6 μm or less carbon atoms or a salt thereof or a salt thereof is blended in a weight ratio of [carboxylic acid (salt)] / [detergent particles] = 1/99 to 30/70 with respect to detergent particles, After mixing with the detergent particles, the step (3) is performed.
The method for producing a tablet-type or briquette-type cleaning composition according to any one of claims 3 to 7. 8. After the surface of the detergent particles is coated with a surface coating agent, a mono- or polycarboxylic acid having 6 or less carbon atoms or a salt thereof having an average particle diameter of 100 to 1500 μm or a salt thereof is added to the detergent particles after coating by weight ratio. The tablet type or briquette according to claim 7, wherein the step (3) is carried out after the step (3) is carried out by mixing [carboxylic acid (salt)] / [detergent particles] = 1/99 to 30/70 and mixing with the coated detergent particles. A method for producing a mold cleaning composition. 9. The mono- or polycarboxylic acid or a salt thereof is one or a mixture of two or more selected from acetic acid (salt), succinic acid (salt), maleic acid (salt) and citric acid (salt). The method for producing a tablet-type or briquette-type cleaning composition according to claim 7 or 8, wherein 10. The cleaning composition according to claim 1, wherein the cleaning composition is a briquette-type cleaning composition, and the absolute maximum length of a vertical projection image of the briquette-type cleaning composition is 10 mm or less. The production method according to claim 1. 11. The cleaning composition according to claim 1, wherein the cleaning composition is a tablet-type cleaning composition, and the absolute maximum length of the tablet-type cleaning composition is 50 mm or less. The manufacturing method as described.