JPH10183199A - Tablet type detergent and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tablet type detergent that has high mechanical strength in the dryness and readily disintegrates in the wetness. SOLUTION: This tablet type detergent is produced by compression-molding a detergent composition combining the detergent particles composed of a detergent compound with a builder and has a macro porosity of >=18%. This production process for this tablet type detergent with a macro porosity comprises the compression molding of a detergent composition containing the detergent particles composed of a detergent compound and of a builder as well as a binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a tablet detergent and a method for producing the same. More specifically, the present invention relates to a tablet detergent that can be suitably used for washing laundry and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Tablet detergents are easy to handle because they do not need to be weighed, and they are not bulky.
It has the advantage of being compact and requiring little storage space.

[0003] Conventionally, tablet detergents are produced by compressing or densifying detergent powder.

[0004] However, conventional tablet detergents are disclosed in EP-A-522,766 (19).
93), it does not have sufficient mechanical strength in a dry state, and has the disadvantage that it is difficult to dissolve and dissolve even when wet.

[0005] Therefore, the above specification proposes a tablet-type detergent which is coated with a disintegrating agent which disintegrates at least a part of the detergent particles when immersed in water and is compacted.

However, when the tablet type detergent comes into contact with water, the active agent is gelled or pasted on the surface thereof, and the gelled or pasted active agent is prevented from penetrating water into the inside. There is a drawback that solubility deteriorates because of inhibition. Such drawbacks are particularly noticeable at lower water temperatures.

In order to solve the above-mentioned drawbacks, the tablet has a high porosity at a low compression molding pressure so that the surface is not gelled in water, or even if it is gelled, it is easily disintegrated and dissolved. When molded in such a manner, the resulting tablet detergent has the disadvantage of insufficient mechanical strength and poor handling properties.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a tablet type detergent having excellent mechanical strength in a dry state and easily disintegrating in a wet state. The purpose is to:

[0009]

The present invention comprises (1) a detergent composition containing a detergent particle containing a detergent active compound and a builder and a binder, and a macroporosity of 18% or more. And a tablet-type detergent comprising (2) a detergent composition containing a detergent active compound and a builder, and a binder, and a macroporosity of 18%, characterized by being compression-molded. The present invention relates to a method for producing a tablet detergent having the above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the tablet detergent of the present invention is obtained by compression-molding a detergent composition containing a detergent particle containing a detergent active compound and a builder, and a binder. It is characterized by having a macro porosity of 18% or more and using the binder.

The tablet-type detergent of the present invention exhibits a property of being extremely excellent in solubility in water by having a macroporosity of 18% or more.

In general, simply adjusting the macro porosity of the tablet detergent to be 18% or more,
Certainly, a porous tablet detergent having a high porosity can be obtained, but it is difficult to handle the tablet detergent because the mechanical strength of the tablet detergent is reduced. Therefore, when compression molding is performed at a high pressure in order to increase the mechanical strength, the solubility of the tablet detergent in water decreases.

On the other hand, in the present invention, the macro porosity is adjusted so as to be 18% or more. However, the detergent composition constituting the tablet detergent contains a binder. Accordingly, the tablet detergent of the present invention has excellent mechanical strength in a dry state while maintaining excellent solubility in water.

Here, the macro porosity referred to in the present specification refers to the ratio of the space between the detergent particles contained in the tablet detergent to the total volume of the tablet detergent. The method for measuring the macro porosity will be described later.

The detergent particles used in the present invention, as described above, contain a detergent active compound and a builder.

The above-mentioned detergent active compounds include nonionic activators, cationic activators, anionic activators and amphoteric activators.

Specific examples of the detergent active compound include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, and polyoxyethylene. Nonionic activators such as polyoxypropylene alkyl ether, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glycoside, alkylamine oxide; alkylbenzene sulfonate , Alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-
Anionic activators such as olefin sulfonates, α-sulfofatty acid salts, α-sulfofatty acid ester salts, alkyl ether carboxylates, alkenyl ether carboxylates, soaps; amphoteric activators such as carbobetaine and sulfobetaine; Examples include cationic surfactants such as chain-type quaternary ammonium salts, but the present invention is not limited only to such examples. In addition, such detergent active compounds can be generally used alone or in combination of two or more.

The detergent active compound preferably has an HLB (value determined by the Griffin method) of 5 to 17, preferably 8 to 14, from the viewpoint of excellent detergency.

The nonionic activator has a linear or branched chain having 10 to 20, preferably 10 to 15 and more preferably 12 to 14 carbon atoms, and has an average ethylene oxide mole number of addition. 5 to 15, preferably 6
To 12, more preferably 6 to 10, polyoxyethylene alkyl ether.

The polyoxyethylene alkyl ether generally contains a large amount of an alkyl ether having a low addition mole number of ethylene oxide, but the amount of the 0 to 3 mole addition product is 35% by weight or less, preferably 25% by weight or less. It is desirable that

The amount of the above-mentioned detergent active compound is desirably adjusted so as to be contained in the detergent particles in an amount of 3% by weight or more, preferably 5% by weight or more in order to impart sufficient detergency. In order to impart the property, it is desirable that the content is adjusted so as to be 65% by weight or less, preferably 60% by weight or less in the detergent particles.

The builder used in the present invention includes an inorganic builder and an organic builder.

Examples of the inorganic builder include sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, and an ion exchange capacity of 100 (CaCO ₃ mg / g) or more.
A silicate compound having preferably 100 to 500 (CaCO ₃ mg / g), specifically, an alkaline salt such as SKS-6, a product of Hoechst-Tokuyama, a neutral salt such as sodium sulfate, an orthophosphate EP-A-550,048, such as phosphates such as pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate, and alkali metal salts such as sodium and potassium salts ( 1993) and Tokubo Sho64
Silicate compounds described in JP -41116, the general _{^{formula: x 1 (M 2 O)}} · Al 2 O 3 · y 1 (SiO 2) · w 1 (H
₂ O) (wherein, M is sodium, an alkali metal atom such as potassium, x ^1, y ¹ and w ¹ represents the number of moles of each component, in general, x ¹ is 0.7 to 1.5 the number of, y ¹ is 0.8
6 The number of crystalline aluminosilicate represented by w ¹ represents any positive number), the general _{^{formula: x 2 (M 2 O)}} · Al 2 O 3 · y 2 (SiO 2) · w
² (H ₂ O) (wherein M is a sodium or potassium atom,
x ² , y ² and w ² indicate the number of moles of each component, and generally, x ² is a number from 0.7 to 1.2, and y ² is 1.6 to ² .
8 Number of, w ² is 0 or other amorphous aluminosilicates represented by any showing a positive number), the general _{^{formula: x 3 (M 2 O)}} · Al 2 O 3 · y 3 (SiO 2) · z ³ (P ₂ O
₅ ) · w ³ (H ₂ O) (where M is a sodium or potassium atom, x ³ , y
^3, z ³ and w ³ represents the number of moles of each component, x ³ is the number of from 0.20 to 1.10, y ³ is the number of .20-4.00, z ³ is 0.001 to 0 the number of .80, w ³ is amorphous aluminosilicate and the like represented by 0 or show any positive number) and the like. Among the crystalline aluminosilicates, in particular, the general formula: Na ₂ O.Al ₂ O ₃ .y ⁴ (SiO ₂ ) .w ⁴ H ₂ O (where y ⁴ and w ⁴ are moles of each component) Indicates the number, y ⁴
The number of 1.8 to 3.0, w ⁴ crystalline aluminosilicate preferably represented by indicating) the number of 1-6.

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

Examples of the organic builder include ethane-1,1-diphosphonic acid and ethane-1,2-
Triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-
Phosphonates such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid; 2-phosphonobutane-1,2
Phosphonocarboxylic acid salts such as dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid; amino acid salts such as aspartic acid and glutamic acid; nitrilotriacetic acid salt and ethylenediaminetetraacetic acid salt And aminopolyacetates such as diethylenediaminepentaacetic acid; polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, and sulfonation Polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-ethylene crosslinked copolymer , Maleic anhydride-vinyl acetate copolymer Copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylate copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, derived from 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, Vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2,
3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, polyester having a quaternary ammonium group, polyaldehyde carboxylic acid, cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide ], Poly (oxycarboxylic acid), starch succinate, maleate, terephthalate, starch phosphate, dicarboxystarch,
Polymer electrolytes such as dicarboxymethyl starch, carboxymethyl cellulose and succinate; non-dissociated polymer compounds such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and cold water soluble urethanized polyvinyl alcohol; diglycolic acid, oxydisuccinic acid, carboxymethyloxy Succinic acid (CMOS),
Cyclopentane-1,2,3,4-tetracarboxylic acid,
Carboxymethylated products such as tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, raffinose, and pentaerythritol Carboxymethylates, carboxymethylates of gluconic acid, condensates of polyhydric alcohols or saccharides with maleic anhydride or succinic anhydride, condensates of oxycarboxylic acids with maleic anhydride or succinic anhydride, and melitic acid Benzene polycarboxylic acid,
Ethane-1,1,2,2-tetracarboxylic acid, ethene
1,1,2,2-tetracarboxylic acid, butane-1,2,2
3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulfitacon Acids, malic acid, oxydisuccinic acid, gluconic acid, and organic acid salts of Monsanto Industrial Chemicals Company, Inc., trade name: Builder M and the like. Among these organic builders, citrates, polyacrylates and polyethylene glycols are preferred. Among these organic builders, particularly preferable are trisodium citrate, sodium polyacrylate and polyethylene having a weight average molecular weight (calculated from a hydroxyl value measured according to JIS K 1557 6.4) of 2700 to 19000. Glycols. The builders are usually used alone or in combination of two or more.

The average particle size of the builder is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of exhibiting granulation properties and effective ion exchange ability during use (when dispersed in water). It is preferably 500 μm or less, especially preferably 400 μm or less.

The amount of the builder is desirably adjusted so as to be contained in the detergent particles in an amount of 35% by weight or more, preferably 40% by weight or more in order to impart sufficient detergency. In order to provide, it is desirable to adjust so as to contain 97% by weight or less, preferably 95% by weight or less.

The detergent particles used in the present invention contain the above-mentioned detergent active compound and builder. If necessary, a surface coating agent such as an enzyme or zeolite may be coated on the detergent particles.

The detergent particles used in the present invention may be a mixture of particles of each component constituting the detergent particles, or may be obtained by granulating a mixture containing a detergent active compound and a builder. Particles may be used.

The detergent particles have an average particle size of 150 μm.
The above is a main component, and the particle diameter is 150
The content of the particles having a particle size of less than μm is preferably 5% by weight or less in order to increase the macroporosity of the tablet detergent of the present invention. The average particle diameter of the detergent particles is 20 in order to improve the moldability of the tablet detergent and to improve the mechanical strength of the obtained tablet detergent.
It is preferably at most 00 μm, more preferably at most 1500 μm.

In the present invention, it is not necessary that all of the detergent particles have a uniform particle size, but the particle size distribution of the detergent particles is sharp, in other words, the distribution width of the particle size distribution is small. However, it is preferable because the voids between the detergent particles can be easily made uniform, and the control of the macroporosity of the obtained tablet type detergent becomes easy. When the particle size distribution of the detergent particles is, for example, a lognormal distribution, the standard deviation when the particle size distribution of the detergent particles is plotted by volume using a rosin Lambert graph is preferably 2.0 or less.

The standard deviation is calculated by the formula: [standard deviation] = (84.3% by weight particle size) / (50% by weight)
Particle size).

The bulk density of the detergent particles is 0.5 g / cm ³ or more, preferably 0.1 g / cm ³ , in order to prevent the obtained tablet type detergent from becoming bulky and to enhance compactness.
It is desirable that it be 7 g / cm ³ or more.

In the present invention, when the tablet-type detergent of the present invention is put into water, even if the surface of the tablet-type detergent gels, the water sufficiently penetrates into the inside thereof to enhance the solubility. Therefore, it is necessary to secure a water intrusion route. For this purpose, in the present invention, the tablet-type detergent is provided with macro voids (voids between detergent particles), and a binder is used to secure such macro voids.

As the binder, in order to dissolve and disintegrate the tablet detergent of the present invention when immersed in water, the binder is solid or powdery at room temperature (about 20 ° C.) and has water solubility. Those having a melting point of 40 to 100 ° C. are preferred.

A typical example of the binder is a water-soluble polymer.

Specific examples of the water-soluble polymer include, for example, polyethylene glycol, polyvinylpyrrolidone, water-soluble polyacrylate, polyvinyl alcohol and the like. Among these, polyethylene glycol can be suitably used in the present invention.
Among such polyethylene glycols, JIS K 1557
Weight average molecular weight 1300-2 calculated from the hydroxyl value measured by the pyridine phthalic anhydride method according to 6.4
Those having 0000 are particularly preferred. The polyethylene glycol having a weight-average molecular weight of 1300 to 20,000 has a melting point of 4 when measured by a freezing point measurement method described in JIS K8001 “General rules for reagent test methods”.
0-100 ° C.

Further, in the present invention, the binder is
It may be heated and melted in advance or dissolved in water, and then added to the detergent particles by spraying. In this case, the surface of the detergent particles is coated with the binder, but the distance from the center of the detergent particles in contact with each other to the center becomes short, the density of the obtained tablet type detergent becomes high, and the macro voids become large. Although the ratio tends to be small, there is an advantage that the mechanical strength of such a tablet detergent can be improved.

There are no particular restrictions on the method of adding a binder to the detergent particles or the method of mixing the binder with the detergent particles.
The dispersion state of the binder contained in the tablet detergent may be uniform or non-uniform.

The weight ratio of the detergent particles to the binder (detergent particles / binder) is 99/1 or less, preferably 97/3 or less, in order to sufficiently improve the mechanical strength of the obtained tablet detergent. Is desirable, and in order to impart sufficient macro voids to the obtained tablet detergent,
It is desirable that the ratio be 85/15 or more, preferably 90/10 or more, and more preferably 95/5 or more.

Next, a method for producing the tablet detergent of the present invention will be described.

The method for producing the binder is different depending on whether the binder is a powder or a liquid.

When the binder is a powder, for example, the binder and the detergent particles are dry-blended, and the resulting detergent composition is compression-molded by, for example, tableting while adjusting the macroporosity. Then, the binder is melted by heating, then cooled, and the binder is bound to the detergent particles to produce a tablet detergent.

When the binder and the detergent particles are dry-blended, as a powder mixer, for example, a high-speed mixer, a Loedige mixer, a Henschel mixer, a ribbon mixer, a Nauta mixer or the like is usually used. Can be used.

The pressure at the time of compression molding by tablet molding or the like is preferably 1 kgf / cm ² or more in order to impart suitable mechanical strength to the obtained tablet-type detergent. In order to prevent this and secure a predetermined macroporosity, it is preferable that the pressure is 30 kgf / cm ² or less, and preferably 20 kgf / cm ² or less. In the present invention, by adjusting the pressure, the macroporosity of the obtained tablet detergent can be adjusted to a predetermined value.

Therefore, in the present invention, it is preferable that the relationship between the pressure at the time of compression molding and the macro porosity is previously calibrated by a method such as a mercury intrusion method.

At this time, since the micro porosity may change at the same time, it is preferable to measure it.

Here, the above-mentioned micro porosity means the ratio of fine voids contained in the detergent particles themselves before compression molding to the detergent particles or contained in the detergent particles themselves in the obtained tablet type detergent. The ratio of the fine voids occupied in the tablet detergent.

Specifically, assuming that the volume of the fine voids in the detergent particles is dV, the volume of the detergent particles is Vp, and the volume of the tablet type detergent is Vt, the microporosity of the detergent particles is d.
It is expressed as V / Vp, and the microporosity of the tablet detergent is expressed as dV / Vt.

In the present invention, unless otherwise specified, the micro porosity refers to the micro porosity in a tablet detergent.

When a detergent composition containing a detergent particle containing a detergent active compound and a builder, and a binder is compression-molded, the pressure at the time of the compression molding causes micro-pores (the pores of the detergent particles themselves) before the compression-molding. The fine pore diameter changes slightly, so that the micro porosity changes. Therefore, it is preferable to newly measure the microporosity of the tablet detergent.

The average pore diameter of the micropores measured by the mercury intrusion method is usually 10 μm or less.

The macro porosity is usually represented by the difference between the total porosity of the tablet detergent and the micro porosity.

If the pressure at the time of compression molding is too high, the detergent particles are crushed, so that it becomes impossible to distinguish between macro voids (voids between detergent particles) and micro voids in the obtained tablet type detergent. However, when the pressure at the time of compression molding is 30 kgf / cm ² or less, the detergent particles do not collapse, and macro voids are formed in the tablet detergent.

The average pore diameter of the macro voids is usually about 1 to 200 μm as measured by a mercury intrusion method.

The temperature at which the molded product obtained by compression molding by tableting or the like is heated is determined by adjusting the temperature of the binder to increase the mechanical strength of the tablet-type detergent obtained by binding the detergent particles. The melting point is preferably not lower than the melting point, and is preferably not higher than 105 ° C. in order to prevent deterioration due to heating.

In the above method, compression molding is performed by tableting or the like so that the macro porosity has a predetermined value, and then the binder is heated and melted. There is an advantage that it can be easily adjusted so that

When the above method is employed, a large amount of the binder is required as compared with a method of heating before molding described later, and it is obtained when the detergent particles and the binder are not sufficiently mixed. The mechanical strength of the tablet detergent may be locally reduced.

In the present invention, the detergent particles are mixed in advance with a binder by using a conventional powder mixer such as a high-speed mixer, a Loedige mixer, a Henschel mixer or the like. May be coated with a binder. In this case, after the binder is heated and melted in advance, such a binder may be sprayed on the detergent particles, or the binder may be added in a powder state and heated and melted while mixing to coat. .

When such a method is adopted, not only the mixing of the binder and the detergent particles and the melting of the binder can be performed at the same time, but also in comparison with the case of heating after molding. There is an advantage that the mechanical strength of the obtained tablet detergent is increased.

However, when such a method is adopted,
When compression molding by tableting etc. with the binder melted, the binder flows and fills the macro voids,
The adjustment error of the macro porosity increases. Therefore, when the above method is employed, it is preferable that the detergent particles are coated with a binder, then cooled once, and then subjected to compression molding such as tablet molding as described above. In this case, two heating steps, heating during coating and heating during compression molding such as tablet molding, are required.
Manufacturing efficiency is not so high.

In the case where the binder is dissolved in a solvent such as water and used as a liquid (solution), for example, a solution of the binder is sprayed onto the detergent particles while rolling the particles with a powder mixer or the like. , A coating method and the like can be adopted.

Examples of the powder mixer used for rolling the detergent particles include a high-speed mixer, a Loedige mixer, a Henschel mixer, a ribbon mixer,
Commonly used ones such as a Nauta mixer can be used.

After the detergent particles are sprayed with a binder solution and coated, the particles are dried to remove the solvent contained in the binder, and the binder is solidified. Can be bound together.

After drying, compression molding may be performed by tableting or the like in the same manner as in the case where the binder is a powder.

When a binder that loses its tackiness when solidified, such as polyvinyl alcohol, is used as the binder, after coating, the pressure at the time of molding is adjusted to adjust the macro porosity quickly. And compression-molded by tableting or the like, and at that time, the solvent can be removed by drying. When such an operation is employed, there is an advantage that the mechanical strength of the obtained tablet-type detergent can be improved, and at the same time, the desired macroporosity can be adjusted.

The shape and the like of the tablet detergent thus obtained are not particularly limited. Examples of the shape include a columnar shape and a cubic shape, and a description of JIS K8841 “Granulated material strength test method” “Table 1”
Shapes and Names of Granulated Material ".

One tablet-type detergent may contain an amount of the cleaning active compound required for the average laundry, or may contain a smaller amount of the cleaning active compound than that required for the average laundry. The detergent active compound may be included and several tablet detergents may be used to achieve the amount required for average laundry. Usually, the weight of one tablet detergent is suitably 5 to 60 g, preferably 10 to 30 g.

The tablet detergent of the present invention has a macroporosity of 18% or more, preferably 20% or more, and has excellent mechanical strength in a dry state and easily disintegrates in a wet state. For example, it can be suitably used for washing laundry and the like. The macro porosity is 40% or less, preferably 35% or less so that the detergent particles having a bulk density of 0.5 g / cm ³ or more have sufficient mechanical strength even when they are compression-molded. It is desirable that

In the present invention, the total porosity expressed as the sum of the macro porosity and the micro porosity requires a certain amount of micro porosity in order to ensure the solubility of the detergent particles themselves. 20% or more, preferably 2
5% or more, and the bulk density is 0.5 g
In order to have sufficient mechanical strength even when detergent particles having a particle size of / cm ³ or more are compression-molded, the content is desirably 50% or less, preferably 40% or less.

[0071]

Next, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited to only these Examples.

Production Example 1 (Production of Detergent Particles) A Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, clearance between stirring blades and vessel wall: 5.0 mm)
Zeolite 4A type as builder (average primary particle size: 3μ)
m) 20 parts by weight of sodium carbonate (average primary particle size: 29
0 μm) 36 parts by weight and crystalline silicate (manufactured by Hoechst, SKS-6) 4 parts by weight, an amorphous aluminosilicate (0.8Na ₂ O · Al ₂ O ₃ 6.5SiO ₂ ) as an oil absorbing agent, pore volume 31
0 cm ^3/100 g, a specific surface area of 153m ² / g, oil absorption 245 ml / 100 g) 10 parts by weight were charged, the main shaft (2
00 rpm) and the chopper (4000 rpm) stirring was started.

Next, a nonionic activator (polyoxyethylene dodecyl ether, average addition mole number of ethylene oxide:
8, melting point: 15 ° C.) 30 parts by weight over 1 minute,
After 4 minutes, the stirring was stopped, 15 parts by weight of zeolite type 4A (average primary particle size: 3 μm) was added as a surface coating agent, the mixture was stirred for 30 seconds, and then discharged from the Loedige mixer to remove the detergent particles. I got

The total amount charged in the Loedige mixer was 4 kg.

Next, the bulk density and average particle size of the obtained detergent particles were measured by the method specified in JIS K 3362, and their micro porosity was checked according to the method shown below. I asked. As a result, the bulk density of the obtained detergent particles was 0.85 g / ml, and the average particle size was 420 μm.
m and the microporosity was 12%.

(Microporosity in Detergent Particles) The true density of detergent particles can be measured by partially changing measurement conditions in accordance with JIS M 8717 “Method of measuring iron ore density 5. Air comparison method”. it can. At this time, since the detergent particles serving as a sample originally contain moisture, the JIS “5.
There is no need to dry as specified in "3 Samples".

The volume of the detergent particles can be measured by partially changing the measurement conditions according to JIS M 8719 “Iron ore pellets—Volume measuring method 5. Mercury method”. At this time, since the detergent particles serving as the sample originally contain moisture, there is no need to perform drying as specified in the above-mentioned "5.3 sample" of JIS. In addition, the mass of the sample was determined by JIS M 8717 “Iron ore density
5. It is preferably 60 g as in the "air comparison method".

Further, using these true density and volume values,
The porosity in the detergent particles is calculated according to "JIS M 8716 Iron Ore Pellets-Calculation Method of Apparent Density and Porosity". The porosity measured and calculated in this way is the micro porosity in the detergent particles.

Production Example 2 (Production of Detergent Particles) A Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 liters, clearance between stirring blades and vessel wall: 5.0 mm)
Zeolite 4A type as builder (average primary particle size: 3μ)
m) 20 parts by weight of sodium carbonate (average primary particle size: 29)
0 .mu.m) 10 parts by weight, the amorphous aluminosilicate as oil absorbent _{(0.8Na 2 O · Al 2 O} 3 6.5SiO 2, pore volume 310 cm ³
/ 100g, specific surface area 153m ² / g, oil absorption 245m
1/100 g) 10 parts by weight and zeolite 4A type (average 1
Secondary particle size: 3 μm) 25.8 parts by weight, sodium carbonate 10
Spray-dried particles consisting of 2 parts by weight of sodium fatty acid having an average carbon number of 18, 18 parts by weight of sodium salt of carboxymethylcellulose and 1 part by weight of water (bulk density: 0.43 g / ml, average particle size: 220 μm) 25 parts by weight were charged, and stirring of the main shaft (200 rpm) and the chopper (4000 rpm) was started.

Next, a nonionic activator (polyoxyethylene dodecyl ether, ethylene oxide average addition mole number:
8, melting point: 15 ° C.) 10 parts by weight are added over 1 minute,
After 4 minutes, the stirring was stopped, 15 parts by weight of zeolite type 4A (average primary particle size: 3 μm) was added as a surface coating agent, and the mixture was stirred for 30 seconds, and then discharged from the Loedige mixer to remove the detergent particles. I got The total amount charged to the Loedige mixer was 4 kg.

Next, the bulk density, average particle size and micro porosity of the obtained detergent particles were examined in the same manner as in Production Example 1. As a result, the bulk density of the obtained detergent particles was 0.57 g.
/ Ml, average particle size is 440 μm, and micro porosity is 2
It was 0%.

Examples 1-2 and Comparative Example 1 Detergent particles obtained in Production Example 1 (used in Examples 1-2) or detergent particles obtained in Production Example 2 (used in Comparative Example 1)
And a weight average molecular weight of 7300 to 9300 as a binder.
Of polyethylene glycol (manufactured by Kao Corporation) in a ratio shown in Table 1 into a 10-liter high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and mixed at room temperature for 3 minutes with a main shaft of 200 rpm and a chopper of 600 rpm. A detergent composition was obtained.

Next, the obtained detergent composition was pressured at 10 k.
gf / cm ² (Example 1) or 15 kgf / cm
² Compression molding at 105 ° C (Example 2 and Comparative Example 1)
And then allowed to cool for 30 minutes to obtain a tablet detergent (diameter: 30 mm, thickness: 10 mm).

As physical properties of the obtained tablet detergent,
The micro porosity, macro porosity, compressive strength and dissolution time of the tablet detergent were examined according to the following methods. Table 1 shows the results.

(1) Microporosity of Tablet Detergent The tablet detergent is carefully loosened to carefully separate the detergent particles constituting the tablet detergent one by one. Since the detergent particles are compression-molded at a pressure of 30 kgf / cm ² or less, the degree of deformation is small and the detergent particles are easily distinguished. At this time, the binder and the like contained in the particles other than the detergent particles may be broken down, but they are similarly separated without leaving the fine powder.

The detergent particles and fine powder thus loosened are referred to as constituent particles. The micro porosity in the constituent particles is the micro porosity of the tablet detergent.

The true density of the constituent particles can be measured by partially changing the measurement conditions in accordance with JIS M 8717 “Method of measuring iron ore density 5. Air comparison method”. At this time, since the constituent particles serving as the sample originally contain moisture, there is no need to dry the constituent particles as described in “5.3 Sample” of JIS.

The volume of the constituent particles can be measured by partially changing measurement conditions in accordance with JIS M 8719 “Iron ore pellets—Volume measuring method 5. Mercury method”. At this time, since the constituent particles serving as the sample originally contain moisture, there is no need to perform the drying as described in “5.3 Sample” of JIS. Further, the mass of the sample is preferably 60 g in the same manner as JIS M 8717 “Method of measuring iron ore density 5. Air comparison method” from the viewpoint of measurement accuracy.

Using these true density and volume values,
The porosity in the constituent particles is calculated according to JIS M 8716 “Iron ore pellets—Method of calculating apparent density and porosity”. This operation is performed for five samples, the maximum value and the minimum value are discarded, and the average value of the remaining three values is defined as the micro porosity in the constituent particles. This value is the microporosity of the tablet detergent.

The total porosity of the tablet detergent is measured as follows.

The true density of the tablet detergent is JIS M 8717
It can be measured by partially changing the measurement conditions according to “Iron ore density measurement method 5. Air comparison method”. At this time, since the tablet-type detergent serving as a sample originally contains moisture, it is not necessary to dry the tablet-type detergent as described in "5.3 Sample" of JIS.

The volume of the tablet detergent is JIS M 8719
It can be measured by partially changing the measurement conditions in accordance with “Iron ore pellet-volume measurement method 5. Mercury method”. At this time, the tablet detergent used as the sample is
Since it originally contains water, there is no need to perform drying as described in the above “5.3 Samples” of JIS. The sample used for the measurement is one tablet detergent.

Further, using these values of the true density and the volume, the porosity of the tablet type detergent is calculated according to JISM 8716 “Iron ore pellets—calculation method of apparent density and porosity”.

The porosity measured and calculated in this manner is the total porosity of the tablet detergent.

(2) Macro porosity The macro porosity of the tablet detergent is calculated as the difference between the total porosity of the tablet detergent and the micro porosity of the tablet detergent.

(3) Compressive strength The crush strength in the diameter direction of the tablet detergent is measured according to JIS Z 8841 “Test method for granulated material strength 3.1 Test method for crush strength”.

(4) Dissolution time 15 g of the obtained tablet detergent was previously added to 20 ° C.
-Tank washing machine containing 30 liters of tap water (made by Toshiba Corporation, trade name: Ginga 3.6 VH-360S)
(I type). Stirring intensity is "standard" and stirring is 2
The electrical conductivity is measured while performing for 0 minutes.

The measurement of the electric conductivity was performed by Toa Denpa Kogyo Co., Ltd.
And trade name: TOA ConductivityMeter CM-60SWO. The saturation value (end point) of the electric conductivity is measured when the electric conductivity is measured every 30 seconds after the stirring is started and the rate of change of the measured value at that time is less than 1% as compared with the previous measured value. The electrical conductivity of However, the measurement of the electric conductivity is performed for at least 5 minutes. The dissolution rate is calculated by the formula:

[0099]

(Equation 1)

Is obtained based on The evaluation of solubility is represented by the elapsed time until the dissolution rate becomes 90%. The time is preferably within 300 seconds.

Examples 3 to 6 and Comparative Examples 2 to 4 The detergent particles obtained in Production Example 1 and polyethylene glycol having a weight average molecular weight of 7,300 to 9,300 as a binder were mixed in a ratio of 10 liters as shown in Table 1. Put into high-speed mixer, spindle 200rpm, chopper 600
The mixture was mixed at room temperature for 3 minutes at rpm to obtain a detergent composition. Next, the obtained detergent composition was molded at the pressure shown in the table, heated at a temperature of 105 ° C. for 10 minutes, and then allowed to cool for 30 minutes to obtain a tablet-type detergent (diameter: 30 mm, thickness: 10 mm). .

As physical properties of the obtained tablet detergent,
The micro porosity, macro porosity, compressive strength and dissolution time of the tablet detergent were examined in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 5 The detergent particles obtained in Production Example 1 were molded under the pressures shown in Table 1, and a tablet detergent (diameter: 30 mm, thickness: 10 m)
m).

As physical properties of the obtained tablet detergent,
The micro porosity, macro porosity, compressive strength and dissolution time of the tablet detergent were examined in the same manner as in Example 1. Table 1 shows the results.

[0105]

[Table 1]

From the results shown in Table 1, it can be understood that the tablet detergents obtained in Examples 1 to 6 have a short dissolution time and are excellent in solubility.

Next, the relationship between the macro porosity and the dissolution time of the obtained tablet detergent was examined. Figure 1 shows the results.
Shown in

From the results shown in FIG. 1, it can be seen that when the macroporosity of the tablet detergent is 18% or more, the dissolution time is about 300 seconds or less, and the solubility is stably improved.

[0109]

The tablet detergent of the present invention has excellent properties such as excellent mechanical strength in a dry state and easy disintegration in a wet state. Further, according to the production method of the present invention, a tablet-type detergent having a macroporosity of 18% or more can be suitably produced.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the macroporosity and dissolution time of the tablet detergents obtained in Examples 1 to 6 and Comparative Examples 1 to 5.

Claims (13)

[Claims] 1. A tablet-type detergent obtained by compression-molding a detergent composition containing a detergent particle containing a detergent active compound and a builder, and a binder, and having a macroporosity of 18% or more. 2. The tablet detergent according to claim 1, which has a total porosity of 20% or more. 3. The tablet detergent according to claim 1, wherein the binder has a melting point of 40 to 100 ° C. 4. The method according to claim 1, wherein the binder is a water-soluble polymer.
4. The tablet detergent according to any one of claims 1 to 3. 5. The binder has a weight average molecular weight of 1300 to 20.
2. Polyethylene glycol having a molecular weight of 1,000.
5. The tablet-type detergent according to any one of items 4 to 4. 6. The weight ratio of detergent particles to binder (detergent particles / binder) is from 85/15 to 99/1.
The tablet detergent according to any one of the above. 7. A method for producing a tablet-type detergent having a macro porosity of 18% or more, which comprises compression-molding a detergent composition containing a detergent particle containing a detergent active compound and a builder, and a binder. 8. The method according to claim 7, which has a total porosity of 20% or more. 9. The method for producing a tablet detergent according to claim 7, wherein the binder has a melting point of 40 to 100 ° C. 10. The method for producing a tablet detergent according to claim 7, wherein the binder is a water-soluble polymer. 11. The binder has a weight average molecular weight of 1300 to 2
The method for producing a tablet detergent according to any one of claims 7 to 10, which is a polyethylene glycol having 0000. 12. The method for producing a tablet-type detergent according to claim 7, wherein the pressure during compression molding of the detergent composition is 1 to 30 kgf / cm ² . 13. The weight ratio of detergent particles to binder (detergent particles / binder) is from 85/15 to 99/1.
13. The method for producing a tablet detergent according to any of 12.