ES2420761T3 - Single Core Detergent Particle Production Procedure - Google Patents

Abstract

A method of producing single core detergent particles having an average particle size of 150 µm or more and a particle growth rate of 1.5 or less comprising the steps of: step A) preparing a surfactant composition comprising : a) an anionic surfactant represented by any one of the following formulas (1) to (3): RO-SO3M (1) in which R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms; and M is an alkali metal atom or an amine, R-O(CH2CH2O)n-SO3M (2) where R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms; n is an average number of moles added from 0.1 to 3.0; and M is an alkali metal atom, or an ammonium or an organic amine and wherein R is an alkyl group or an alkenyl group having 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M, and b) water in an amount of 25 to 65 parts by weight based on 100 parts by weight of said component a); step B): mixing the surfactant composition obtained in step A) and base particles having a bearing capacity of 20 ml/100 g or more and comprising a water-soluble inorganic salt produced by spray-drying, while basically maintaining the shape of the particles. base particles; and step C): modifying the surface of the mixture obtained in step B) with a fine powder in which the detergent particles additionally comprise c) a nonionic surfactant having a melting point of 30 °C or lower in a range of a 1 to 20% by weight of the detergent particles, component c) being mixed with the base particles rather than with the surfactant composition prepared in step A).

Description

Single Core Detergent Particle Production Procedure

Technical field

The present invention relates to a method of producing single core detergent particles containing, as an anionic surfactant, a compound represented by any of formulas (1) to (3):

R-O-SO3M (1) in which R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms; and M is an alkali metal atom or an amine,

R-O (CH2CH2O) n-SO3M (2) in which R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms; n is an average number of moles added from 0.1 to 3.0; and M is an alkali metal atom, or an ammonium or an organic amine, and

wherein R is an alkyl group or an alkenyl group having from 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M.

Prior art

One of the methods of producing detergent particles includes a production process that includes the step of mixing a powdered substance and a liquid surfactant composition. Among them, there are to date various disclosures of powdered detergents in which an anionic surfactant represented by the aforementioned formula (1) is formulated as a detergent surfactant in order to improve the high detergent activation capacity, the ability to avoid redeposition, compatibility with the environment, and solvency through a combination of surfactants, and the like.

For example, a process for producing a granular detergent composition is disclosed using a liquid surfactant composition composed of an anionic surfactant represented by the aforementioned formula (1), a non-ionic surfactant, and water (Patent Publication 1); and a production process that includes the step of formulating an anionic surfactant represented by the formula (1) mentioned above in a detergent suspension (Patent Publication 2), or the step of adding an anionic surfactant represented by the aforementioned formula (1) formerly to an intermediate extrusion molding product (Patent Publication 3).

However, when detergent particles are produced by the procedure of Patent Publication 1, it is necessary to previously neutralize alkyl sulfate having poor stability compared to LAS or the like in a non-ionic surfactant, so that it still exists Concern about the stability aspect of the anionic surfactant represented by the formula (1) mentioned above.

In addition, while the production procedures of Patent Publications 2 and 3 do not present any problem in the aspect of the stability of the anionic surfactant represented by the formula (1) mentioned above, the solubility still remains unsatisfied because in both the The resulting detergent particles undergo a compactness treatment.

In addition, Patent Publication 4 discloses a method of producing a granular detergent composition that includes the steps of absorbing in oil a paste of the anionic surfactant represented by the formula (2) mentioned above in silica or silicate, granulating the mixture, and Dry the granules. The production process described above has the advantage that the anionic surfactant can be formulated in a high content. On the other hand, to facilitate the production of the granular detergent composition described above, an oil absorption vehicle such as silica or silicate is necessary, and in addition a drying stage is needed after the granulation stage to remove the water contained in the paste mentioned above.

In addition, Patent Publication 5 discloses a method of producing a detergent composition that includes the step of mixing a surfactant composition containing an anionic surfactant represented by the aforementioned formula (2), a non-ionic surfactant, and water, with an adsorbent powder. However, in this production process, it is impossible to prepare a free flowing powder detergent in high yield by the process that includes the step of mixing the surfactant composition in a

similar to a paste with water soluble powder detergent particles.

In addition, a process for producing a high density density detergent composition is disclosed, which includes the steps of manufacturing an anionic surfactant represented by the aforementioned formula (3) in the form of a powder, mixing the anionic surfactant with a constituent powder alkaline add to

5 this simultaneously a binder containing water, and granulate the mixture (Patent Publication 6); and a method of producing a high density bulk detergent that includes the steps of concentrating an anionic surfactant represented by the aforementioned formula (3), and directly formulating the concentrate in a kneading stage (Patent Publication 7).

However, when detergent particles are produced according to the production process of

10 Patent Publications 6 or 7, the solubility still remains unsatisfied because in both the resulting detergent particles undergo a compactness treatment

Patent Publication 1: JP-A-Hei-6-17098 Patent Publication 2: JP-A-Hei-6-220499 Patent Publication 3: JP-A-Hei-8-504458

15 Patent Publication 4: WO 0031223 Patent Publication 5: JP-A-Hei-03-62899 Patent Publication 6: JP-A-Hei-4-359098 Patent Publication 7: JP-A-Hei -9-143500

EP 0 969 082 A1 describes a method of preparing detergent particles which

20 comprises a step of preparing a suspension containing a water insoluble inorganic compound, a water soluble polymer and a water soluble salt; a step of spray drying the suspension to prepare base particles and a step of adding a surfactant to the base particles.

Disclosure of the invention

Problems to be solved by the invention

Therefore, an objective of the present intention is to provide a method of producing single core detergent particles which includes the step of formulating the anionic surfactant represented by any of the formulas (1) to (3) mentioned above, in that the process of producing the detergent particles ensures the stability of the anionic surfactant represented by the formulas (1) to (3) mentioned above, and provides excellent solubility.

30 means to solve problems

Specifically, the essence of the present invention relates to a method of producing single core detergent particles having an average particle size of 150 µm or greater and a particle growth rate of 1.5 or less, including stages of:

step A): prepare a surfactant composition containing:

A) an anionic surfactant represented by any of the following formulas (1) to (3):

R-O-SO3M (1)

wherein R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms; and M is an alkali metal atom or an amine,

R-O (CH2CH2O) n-SO3M (2)

Wherein R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms; n is an average number of moles added from 0.1 to 3.0; and M is an alkali metal atom, or an ammonium or an organic amine, and

wherein R is an alkyl group or an alkenyl group having from 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M, and b) water in an amount of 25 to 65 parts by weight based on 100 parts by weight of component a) mentioned above;

stage B): mixing the surfactant composition obtained in stage A) and base particles having a

support capacity of 20 ml / 100 g or greater and containing a water-soluble inorganic salt produced by spray drying, while basically maintaining the shape of the base particles; and stage C): modify the surface of the mixture obtained in stage B) with a fine powder,

wherein the detergent particles additionally comprise c) a non-ionic surfactant having a point of melting of 30 ° C or less in a range of 1 to 20% by weight of the detergent particles, component c) being mixed with the base particles rather than with the surfactant composition prepared in the stage A).

Effects of the invention

By using the method of producing single core detergent particles of the present invention, it is exhibited as an effect of single core detergent particles containing an anionic surfactant represented by the formulas (1) to (3) mentioned above, which is generally very low in skin irritability and favorable in biodegradability, and single core detergent particles can be produced that have inhibitory particle growth, and a defined particle size distribution with high yield, without the need for a drying stage to remove the water after the granulation stage. By providing a defined particle size distribution, a detergent can be obtained that not only improves its external appearance, but is also favorable in free fluidity, and excellent in solubility.

Best way to carry out the invention

One of the great features of the single core detergent particle production process of the present invention (hereinafter referred to as the production process of the present invention) is that the process, as described above, It includes the stages of:

step A): preparing a surfactant composition containing a) the anionic surfactant represented by the formulas (1) to (3) mentioned above, and b) water in an amount of 25 to 65 parts by weight based on 100 parts by weight of the component a) mentioned above; stage B): mixing the surfactant composition obtained in stage A) and base particles that have a support capacity of 20 ml / 100 g or greater and that contain a water-soluble inorganic salt produced by spray drying, while basically maintaining the shape of the base particles; and stage C): modify the surface of the mixture obtained in stage B) with a fine powder.

Through the use of the production process of the present invention having the characteristic mentioned above, it is exhibited as an effect of the detergent particles containing the anionic surfactant represented by the formulas (1) to (3) mentioned above, which is generally very low in skin irritability and favorable in biodegradability, and single core detergent particles can be produced that have inhibitory particle growth, and a defined particle size distribution, without the need for a drying step to remove water after the granulation stage.

In the production process of the present invention, it is considered a mechanism to exhibit the effect of not needing a drying stage for the removal of water after the granulation stage because in stage B), when the surfactant composition that contains an anionic surfactant represented by the formulas

(1) to (3) and the water contact the base particles containing a water-soluble inorganic salt, the water-soluble inorganic salt removes water from the surfactant composition, and the anionic surfactant composition represented by the formulas (1 ) to (3) loses free fluidity, so that spraying can be done without adding the drying stage.

The production process of the present invention will be described more specifically hereinafter.

[Stage A)]

In the production process of the present invention, step A) is a step of preparing a surfactant composition containing a) an anionic surfactant represented by the formulas (1) to (3) mentioned above, and b) water in an amount 25 to 65 parts by weight based on 100 parts by weight of component a) mentioned above.

[Components of the surfactant composition]

As for component a), in formula (1), R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms, and preferably from 12 to 16 carbon atoms. M is preferably an alkali metal atom such as Na or K, or an amine such as monoethanolamine or diethanolamine, and especially preferably Na or K from the viewpoint of an improvement in the detergency of the detergent composition.

In addition, in the formula (2), R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms, and preferably from 12 to 16 carbon atoms. The average number of moles added n is 0.1 to 3.0, and

preferably from 0.1 to 2.0. M is preferably an alkali metal atom such as Na or K, an ammonium or an organic amine such as monoethanolamine or diethanolamine, and Na or K is especially preferred from the viewpoint of an improvement in the detergency of the detergent composition.

In addition, in the formula (3), R is an alkyl group or an alkenyl group having from 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M.

[Physical properties of the surfactant composition]

It is desirable that the surfactant composition has a temperature range in which the viscosity of the surfactant composition is 10 Pa · s or less, and preferably 5 Pa · s or less in an operable temperature range of the surfactant composition, from the point of view of production manipulation. It is preferred that the temperature range mentioned above preferably exists in a range of up to 70 ° C, and more preferably in a range of up to 60 ° C, from the viewpoint of the stability of the surfactant composition. Here, the viscosity is determined with a coaxial double cylindrical rotary viscometer (manufactured by HAAKE; sensor: SV-DIN) with a shear rate of 50 l / s.

The viscosity of the surfactant composition prepared in step A) varies greatly depending on its water content. It is preferred that a surfactant composition having a desired water content, i.e. a desired viscosity, be prepared by adjusting with the amount of water of an alkaline compound that is used in the preparation of the surfactant composition by neutralizing a precursor acid of component a) with the alkaline component. It is generally known that when the surfactant composition contains component a) and water in an amount of 25 to 65 parts by weight (the water content of the surfactant composition is 20 to 40%) based on 100 parts by weight of component a), the viscosity decreases, which makes its handling easy. It is preferred that the water of the surfactant composition be adjusted within this range in the present invention.

In addition, since the acid precursor of component a) is very unstable and is most likely to degrade, it is preferred that an adjustment be made so as to avoid degradation. The adjustment procedure is not particularly limited, and a known procedure can be used. For example, the process can be performed by removing the heat of neutralization with a heat exchanger or the like using a circulation reactor while carefully controlling the temperature of the acid precursor of component a) and of the surfactant composition. A temperature range during production includes a temperature of 30 ° C to 60 ° C, and a temperature range for storage after production includes a temperature of 60 ° C or lower. In addition, the surfactant composition can be used by optionally raising the temperature after use.

When the anionic surfactant composition represented by the formula (1) or (2) is used, it is preferred that the surfactant composition has an excess of alkalinity from the viewpoint of preventing degradation. On the other hand, when the anionic surfactant composition represented by the formula (3) is used, a pH of 4 to 9 is preferred, and a pH of 5 to 8 is more preferred.

In addition, the adjusted surfactant composition may contain an unreacted alcohol or a polyoxyethylene alkyl ether that has not reacted after the production of the acid precursor of compound a), sodium sulfate, which is a by-product of the neutralization reaction, or a pH buffering agent, which can be added during the neutralization reaction, a bleaching agent, or the like.

In addition, the surfactant composition used for the present invention may contain a known component commonly used in detergents, for example, a known surfactant in the field of laundry detergents; a redeposition prevention agent such as acrylic acid polymer, acrylic acid-maleic acid copolymer, and carboxymethyl cellulose; a reducing agent such as a sulphite; a fluorescent bleach, or the like.

On the other hand, component a) is preferably contained in an amount within the range of 5 to 30% by weight, and more preferably 10 to 30% by weight of the single core detergent particles that are obtained. in the present invention, from the point of view of an improvement in detergency.

Component b) is water contained in an amount of 25 to 65 parts by weight, and preferably 30 to 50 parts by weight of the surfactant composition, based on 100 parts by weight of component a) mentioned above.

[Stage B)]

In the present invention, step B) is a mixing step of the surfactant composition obtained in step A) and base particles having a support capacity of 20 ml / 100 g or greater and containing a water-soluble inorganic salt produced by spray drying, while basically maintaining the shape of the base particles.

In the present invention, a feature is that stage B) is performed. In step B), by mixing the surfactant composition and the base particles containing the water-soluble inorganic salt in contact with each other, the loss of free fluidity of the surfactant composition exhibiting by withdrawal of the water from the water can be used. the surfactant composition by means of the water-soluble inorganic salt.

[Base particles containing a water soluble inorganic salt]

The base particles used in step B) have a support capacity of 20 ml / 100 g or greater and contain a water-soluble inorganic salt produced by spray drying.

The base particles mentioned above are prepared by spray drying a suspension containing the water-soluble inorganic salt. The water soluble inorganic salt is not limited in particular. For example, among the above-mentioned constituents generally used in laundry detergents, sodium carbonate, potassium carbonate, sodium sulfate, or the like is preferred.

As for the base particles, a powder obtained by spray drying of an aqueous suspension suitably formulated with, for example, a constituent generally used in laundry detergents which includes, for example, one or more kinds of capture agents is preferred. metal ions such as zeolite, citrates, and sodium tripolyphosphate; an alkalizing agent such as sodium carbonate or potassium carbonate; one or more kinds of base materials that exhibit both the ability to capture metal ions and the alkalizing capacity such as a crystalline silicate; and the like; and / or other base material agents that are generally used in detergent compositions that include, for example, a surfactant known in the field of laundry detergents, a redeposition prevention agent such as an acrylic acid polymer, a copolymer of acrylic acid-maleic acid or carboxymethyl cellulose, an inorganic powder such as sodium sulfate or a sulphite, a fluorescent bleach, or the like. In addition, the alkalizing agent can be removed from the base particles when the base particles contain an agent of base material or the like that is degraded by contact with an alkali or added in step B), from the viewpoint of preventing degradation. of the base material agents.

Among them, it is preferred that zeolite be used in combination with the water-soluble inorganic salt mentioned above. When the zeolite is formulated, the amount of water contained in the base particles after spray drying is preferably 5% by weight or less, and more preferably 3% by weight.

or lower of the base particles, from the point of view of an increase in the action of water absorption in the zeolite.

The base particles in which the water-soluble inorganic salt and zeolite are formulated, which are preferably contained in the base particles, in an amount of 60% by weight or greater in total are favorable for removing water from the surfactant composition. .

The conditions of spray drying of the suspension for the preparation of the aforementioned base particles (temperature, spray drying apparatus, spraying process, drying process, or the like) are not particularly limited, and a known procedure The physical properties of the base particles used in the present invention are offered below.

[Physical properties of base particles]

The base particles have a support capacity of 20 ml / 100 g or more, and preferably 30 ml / 100 g or more. Within this range, the aggregation of the base particles with themselves is avoided, which makes it favorable to maintain the unique core possessed by the particles in the detergent particles.

The procedure for determining support capacity is as follows. A cylindrical mixing vessel with an internal diameter of approximately 5 cm and a height of approximately 15 cm that is equipped with stirring impellers on the inside thereof is loaded with 100 g of a sample. While stirring with the stirring impellers at 350 r / min, flaxseed oil is supplied in the mixing vessel at 25 ° C at a rate of approximately 10 ml / min. The bearing capacity is defined as the amount of flaxseed oil supplied when the stirring torque reaches the highest level.

The base particles preferably have an apparent density of 200 to 1000 g / l, more preferably 300 to 1000 g / l, even more preferably 400 to 1000 g / l, and especially preferably 500 to 800 g / l. Bulk density is measured by a procedure in accordance with JIS K 3362.

The base particles preferably have an average particle size of 150 to 500 µm, and more preferably 180 to 350 µm. The average particle size is calculated by vibrating the sample using standard sieves in accordance with JIS Z 8801 (sieve opening 2000 to 125 µm) for 5 minutes, and after that determining the average particle size from the percentage by weight depending on the opening sizes of the sieves.

[Mixing procedure]

It is preferred that the mixer for the mixture of the surfactant composition and the base particles used in step B) is, for example, a mixer equipped with a nozzle for the addition of the surfactant composition or a jacket for the control of the temperature inside the mixer.

As the mixing conditions of step B), the mixing conditions are selected so that the base particles basically maintain their shapes, that is, the base particles do not experience disintegration. For example, when a mixer equipped with stirring impellers is used, in the case of a mixer equipped with mixing impellers having a rowing shape for the stirring impellers, the stirring impellers preferably have a Froude number of 0.5 to 8, more preferably from 0.5 to 4, and even more preferably from 0.5 to 2, from the point of view of preventing the disintegration of the water-soluble inorganic salt and the mixing efficiency. In addition, in the case where the mixing impellers are screw-shaped, the stirring impellers preferably have a Froude number of 0.1 to 4, and more preferably 0.15 to

2. In addition, in the case where the mixing impellers are tape-shaped, the stirring impellers preferably have a Froude number of 0.05 to 4, and more preferably 0.1 to 2.

In addition, a mixer equipped with agitation impellers and disintegration impellers can also be used. When the base particles and the surfactant are mixed using the mixer, the disintegration impellers are conventionally subjected to high speed rotation, from the point of view of the acceleration of the mixture. However, in the present invention, it is preferred not to basically rotate the disintegration impellers, from the point of view of preventing the disintegration of the base particles. The term "do not basically rotate the disintegration impellers" refers to a state in which the disintegration impellers do not rotate at all, or the disintegration impellers rotate within a range so that the base particles do not experience disintegration, considering the shapes, sizes, and the like of the disintegration impellers, in order to avoid the retention of various starting materials near the disintegration impellers. Specifically, in the case where the disintegration impellers rotate continuously, the Froude number is preferably 200 or less, and more preferably 100 or less, and in the case in which the disintegration impellers rotate intermittently. , the Froude number is not limited in particular. The mixture can be obtained without basically experiencing disintegration of the base particles by mixing under the conditions described above.

The expression "the base particles basically maintain their forms, that is, the base particles do not undergo disintegration," as used herein, refers to a state in which 70% in number or greater of the base particles of The mixture maintains its forms. A method for confirming them includes, for example, a procedure for observing the particles obtained after extracting a soluble component of the resulting mixture with an organic solvent.

In addition, the Froude number as defined in this specification is calculated by the following formula:

Froude number = V2 / (R x g)

where V is the peripheral velocity [m / s] of the end portion of the agitator impeller tip or of the disintegration impeller; R is the radius of rotation [m] of the stirrer impeller or the decay impeller; Y g is the acceleration of gravity [m / s2]

In step B), a powder starting material other than the base particles may be formulated if desired. The amount of the starting powder material is preferably 30 parts by weight or less, based on 100 parts by weight of the base particles, from the standpoint of solubility.

The term "powder starting material other than base particles" as used herein means a detergency builder or an oil absorbing agent that is in powder form at room temperature. In particular, powdered starting materials include base material agents that exhibit metal ion capture capacity such as zeolite and citrates; base material agents exhibiting alkalizing capacity such as sodium carbonate and potassium carbonate; base material agents exhibiting both metal ion capture capacity and alkalizing capacity such as crystalline silicates; Amorphous silica and amorphous aluminosilicates that exhibit low metal ion capture capacity but high oil absorption capacity, and the like. By using the above powdered starting materials in combination with the base particles if desired, the amount of the formulated surfactant composition can be increased and the deposition of the mixture within the mixer can be reduced, and it can also be achieved an increase in detergency.

The detergent particles produced in accordance with the present invention contain c) a non-ionic surfactant having a melting point of 30 ° C or less. In that case, component c) is added to the base particles in step B). Component c) is added before the surfactant composition prepared in step A), to control the structure of the liquid crystals and / or the crystals of the surfactant composition, thereby increasing the effect of

avoid diffusion of component c).

Component c) has a melting point of 30 ° C or less, preferably 25 ° C or less, and more preferably 22 ° C or less. As for component c), for example, a polyoxyethylene polyoxypropylene block polymer such as a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenyl ether, an alkyl (polyoxyalkylene) polyglycoside, an ester of polyoxyalkylene sorbitan fatty acid, an ester of polyoxyalkylene glycol fatty acid, a polyoxyethylene-polyoxypropylene-polyoxyethylene alkyl ether (hereinafter abbreviated as non-ionic EPE), or a polyoxyalkylene alkylol (fatty acid) amide.

Among them, a polyoxyalkylene alkyl ether in which alkylene oxide in an amount of 4 to 12 moles (preferably 6 to 10 moles) is added to an alcohol having 10 to 14 carbon atoms. Here, alkylene oxide includes ethylene oxide, propylene oxide, or the like, and is preferably ethylene oxide.

In addition, a compound is preferred in which ethylene oxide and propylene oxide are subjected, and also optionally ethylene oxide, to block polymerization or random polymerization with the above alcohol, from the standpoint of solubility, especially Low temperature solubility. Among them, non-ionic EPE is preferred.

These components c) can be used alone or in a mixture of two or more kinds. In addition, the nonionic surfactant can be used in the form of an aqueous solution.

Here, the melting point of component c) is determined with Mettler FP81 of FP800 Thermo System (manufactured by Mettler Instrument AG) at a heating rate of 0.2 ° C / min.

Component c) is preferably contained in an amount within the range of 1 to 20% by weight, and more preferably 5 to 15% by weight of the single core detergent particles, from the viewpoint of an improvement in detergency, an increase in anti-caking capacity, and the suppression of obstruction after becoming dust.

In addition, when the single core detergent particles produced in accordance with the present invention contain component c), component c) may contain, for example, salts of fatty acids, polyethylene glycols, or the like (with a molecular weight of 3,000 to 30,000) as disclosed in JP-B3161710, to prevent the generation of diffusion in component c) and the deterioration of the anti-caking capacity. These components are preferably formulated in an amount of 2 to 40 parts by weight, and more preferably 2 to 30 parts by weight, based on 100 parts by weight of component c).

On the other hand, in the present invention, the water contained in the surfactant composition is removed by the water-soluble inorganic salt, and the free fluidity of the surfactant composition is lost, allowing the suppression of diffusion of component c) and an improvement in the anti-caking ability even if component c) does not contain the salts of fatty acids, polyethylene glycols, or the like above. However, it may contain the salts of fatty acids, polyethylene glycols, or the like above to make more effective the suppression of diffusion of component c) and the improvement of the anti-caking ability.

In addition, like other surfactants, a surfactant that is known in the field of laundry detergents can be added. When an acid precursor such as a linear alkylbenzenesulfonic acid is added, the process of adding the acid precursor such as a linear alkylbenzenesulfonic acid is preferred over the surfactant composition to prevent disintegration of the surfactant composition.

After mixing the surfactant composition or other surfactant, with the base particles, it is preferred that polyethylene glycol (PEG) and / or a fatty acid, and / or soapy water is added in an amount of 1 to 10 parts by weight, based on 100 parts by weight of the base particles to coat the surface of the base particles, because the coating improves the anti-caking ability. In addition, the addition of PEG and / or a fatty acid and / or soapy water is preferred because the addition allows the suppression of aggregation and increased dispersibility, which improves the solubility, after dissolution of the particles of Detergent.

In addition, the temperature inside the mixer during mixing is preferably a temperature that allows the effective mixing of the surfactant composition and the base particles while basically preventing the disintegration of the base particles. For example, a temperature greater than or equal to the runoff point of the surfactant composition to be mixed is preferred, more preferably a temperature greater than the runoff point at 10 ° C or higher, and especially preferably a higher temperature. than the runoff point at 20 ° C or higher. In addition, the mixing time is preferably 2 to 10 minutes or the like. Temperature control within the mixer can be performed by allowing cold or warm water to flow through a jacket or the like. Therefore, the mixer used for mixing is preferably a mixer having a construction equipped with a jacket.

The process for mixing the surfactant composition of the base particles can be a batch process or a continuous process. In the case where the mixing is carried out in a batch process, it is preferred that the base particles be supplied previously to the mixer, and then added to

this the surfactant composition. The temperature at which the surfactant composition is fed is preferably 70 ° C or less, and more preferably 60 ° C or less, from the viewpoint of the stability of the surfactant composition.

In the case where the mixing is carried out in a batch process, the mixer is not limited in particular, provided that a mixer that is commonly used for mixing in a batch process is used. For example, as a mixer in which the mixing impellers have a rowing shape, (1) a mixer in which the mixing of the powders is carried out by arranging a stirring shaft in the inner part of the mixing vessel and coupling the impellers of agitation to the agitation shaft: for example, Henschel Mixer (manufactured by Mitsui Miike Machinery Co., Ltd.), High Speed Mixer (manufactured by Fukae Powtec Corp.), Vertical Granulator (manufactured by Powrex Corp.), Lödige Mixer ( manufactured by MATSUBO CORPORATION), PLOUGH SHARE mixer (manufactured by PACIFIC MACHINERY & ENGINEERING Co., LTD.), TSK-MTI mixer (manufactured by Tsukishima Kikai CO., LTD.) and a mixing machine described in JP-A documents -Hei-10-296064 or JP-A-Hei10-296065, or the like; As a mixer in which the mixing impellers are in the form of a tape type, (2) a mixer in which the mixing is carried out by spirally rotating the impellers in a non-rotating container that is cylindrical, semi-cylindrical, or conical for example, Ribbon Mixer (manufactured by Nichiwa Kikai Kogyo KK), Discontinuous Kneader (manufactured by Satake Kagaku Kikai Kogyo KK), Conical Ribbon Mixers / Dryers (manufactured by Okawara MFG. CO., LTD.), Julia Mixer (manufactured by TOKUJU CORPORATION), or the like; as a mixer in which the mixing impellers are screw-shaped, (3) a mixer in which the mixing is done by rotating a screw along a conical container, centering the self-centering around an axis of rotation that is arranged parallel to the vessel wall: for example, Nauta Mixer (manufactured by Hosokawa Micron Corp.), SV Mixer (manufactured by Shinko Pantec Co., Ltd.), or the like.

In addition, in the case where the mixing is carried out in a continuous process, the mixer is not limited in particular, provided that a continuous mixer is used that is usually used for mixing in a continuous process. For example, the base particles and the surfactant composition can be mixed using a continuous type mixer between the aforementioned mixers.

[Stage C)]

Stage C) is a surface modification stage of the mixture obtained in stage B) with a fine powder. By performing this step C), detergent particles can be obtained that have an improvement in free fluidity and anti-caking ability.

As a fine powder, a fine powder is preferred in which the main particles have an average particle size of 20 µm or less, from the point of view of improving the coating ratio of the dust particles, and of the improvement of the free fluidity and the anti-caking capacity of dust particles. The average particle size is determined by a method that uses light scattering, for example a particle analyzer (manufactured by HORIBA, LTD.), Or by microscopic observation.

As a fine powder, an aluminosilicate is desirable, and an inorganic fine powder such as calcium silicate, silicon dioxide, bentonite, sodium tripolyphosphate, talc, clay, an amorphous silica derivative, or a silicate compound such as a crystalline silicate compound, or a metallic soap in which the main particles have a size of 20 µm or less.

In addition, it is preferred that the fine powder has a high ion exchange capacity and alkalizing capacity, from the point of view of detergency.

The amount of the fine powder used is preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the mixture obtained in step B) from the viewpoint of Free fluency and sense of use.

As mixing conditions in step C), mixing conditions can be selected in which the shape of the base particles containing the surfactant composition is basically maintained. Preferred mixing conditions are the use of a mixer equipped with both stirring impellers and disintegration impellers. When a mixer is used as mentioned above, the stirring impellers equipped in the mixer preferably have a Froude number of 10 or less, and more preferably 7 or less, from the viewpoint of preventing the disintegration of the particles. base. The stirring impellers preferably have a Froude number of 2 or more, and even more preferably 3 or more, from the point of view of the effectiveness of the mixture with the fine powder and the dispersion of the fine powder. In addition, the disintegration impellers preferably have a Froude number of 8000 or less, and more preferably 5000 or less, from the viewpoint of mixing efficiency with the fine powder and dispersion of the fine powder. When the Froude number is within this range, single core detergent particles having excellent free fluidity can be obtained.

Preferred mixers include mixers equipped with both stirring impellers and disintegration impellers between the mixers used in step B). Also, using mixers

separated for stage B) and stage C), the temperature control of the mixture is facilitated. For example, when a component that is not heat resistant such as perfume or an enzyme is added during the course or after the conclusion of step C), it is preferred that the temperature of the mixture is controlled in step C). The temperature can be controlled by placing a temperature or aeration jacket. For efficient transport of the mixture obtained in stage B) to the mixer of stage C), it is also a preferred embodiment to add a part of fine powder to the conclusion of stage B).

[Single core detergent particles]

Single core detergent particles are obtained in the manner described above. Among them, as single core detergent particles, those containing from 20 to 80% by weight of the base particles, from 5 to 30% by weight of component a), a fine powder are preferred as the modification, and detergent components added separately (for example, a fluorescent agent, an enzyme, a perfume, an antifoaming agent, a bleaching agent, a bleaching activator, or the like).

[Physical properties of single core detergent particles]

In the present invention, the term "single core detergent particle" refers to the detergent composition that is produced in which the base particle is used as the core, which is a detergent particle in which an individual detergent particle It basically has a base particle as its core.

As an index to express the unique core property of detergent particles, the degree of particle growth defined by the following formula can be used. The single core detergent particles referred to herein have a particle growth rate of 1.5 or less, preferably 1.4 or less, and more preferably 1.3 or less. Although the lower limit is not particularly limited, the degree of particle growth is preferably 1.0 or higher.

In the above single core detergent particle, since intraparticle aggregation is avoided, there are some advantages, such as that particles (aggregate particles) having sizes outside the desired particle size range are less likely, and that The particle size distribution is defined.

The single core detergent particles have an average particle size of 150 µm or larger, preferably 150 to 500 µm, and more preferably 180 to 350 µm.

The single core detergent particles preferably have an apparent density of 300 to 1000 g / l, more preferably 500 to 1000 g / l, even more preferably 600 to 1000 g / l, and especially preferably 650 to 850 g / l

In the case where the bulk density is low as desired in the present invention, a method may be employed that includes the step of, for example, adding a surfactant or similar to a spray dried suspension, thereby reducing the apparent density of the base particle; formulating a powder starting material having an apparent density less than the base particle as a powder starting material other than the base particle in step B); reduce the amount of surfactant composition that is mixed with the base particle; or similar.

The single core detergent particles preferably have a free fluidity, in terms of flow time, of 10 seconds or less, and more preferably 8 seconds or less. The flow time refers to the period of time required to cascade 100 ml of powder from the hopper used in the measurement of bulk density as defined according to JIS K 3362.

The yield of the single core detergent particles is calculated by dividing the sample weight that passes through a sieve having an aperture of 1180 µm by the weight of the entire sample. The yield is preferably 90% or more, and more preferably 95% or more.

The single core detergent particles that are obtained by the production process having the constitution described above have, as mentioned above, a suppression in particle growth, and a defined particle size distribution, and they have an improvement in appearance

external and a favorable free fluidity, whereby detergent particles can be obtained that have excellent solubility with high yield.

As an index for solubility in the present invention, a 60 second dissolution ratio of the detergent particles can be used. The dissolution ratio is preferably 80% or more, and more preferably 90% or more.

The dissolution ratio at 60 seconds of the detergent particles is calculated by the procedure described below. A 1 l beaker (with a cylindrical shape having an internal diameter of 105 mm and a height of 150 mm, for example, a beaker made by Iwaki Glass Co., Ltd.) is loaded with 1 l of hard water cooled to 5 ° C and having a water hardness corresponding to 71.2 mg of CaCO3 / l (with a molar ratio of Ca / Mg: 7/3). Keeping the water temperature constant at 5 ° C with a water bath, the water is stirred with an agitator [length: 35 mm and diameter: 8 mm, for example, the "TEFLON SA" model (MARUGATA-HOSOGATA), manufactured by ADVANTEC] with a rotation speed (800 r / min), so that the depth of the eddy with respect to the depth of water is approximately 1/3. The detergent particles that are reduced to the sample are supplied and weighed exactly so that their weight is 1,0000 g ∀ 0.0010 g and dispersed in the water with stirring, and stirring is continued. After 60 seconds of the delivery of the particles, the liquid dispersion of the detergent particles from the beaker is filtered with a standard sieve (diameter: 100 mm) of a known weight having a sieve opening of 74 µm as defined by JIS Z 8801. After this, the detergent particles containing water that remain in the sieve are collected in an open container of a known weight together with the sieve. On the other hand, the operating time from the beginning of the filtration to the sieve collection is adjusted to 10 s ∀ 2 s. The insoluble remnant of the collected detergent particles is dried for one hour in an electric dryer heated to 105 ° C. After this, the dry insoluble remnant is cooled by keeping it in a desiccator with silica gel (25 ° C) for 30 minutes. After cooling the insoluble remnant, the total weight of the dry insoluble detergent remnant, the sieve and the collection vessel is measured, and the dissolution ratio (%) of the detergent particles is calculated by the formula (2):

Dissolution ratio (%) = {1 - (T / S)} x 100 (2)

wherein S is the weight (g) of the detergent particles supplied; and T is the dry weight (g) of the insoluble remnant of the detergent particles that remains in the sieve when the aqueous solution prepared under the conditions of agitation mentioned above is filtered with the sieve (drying conditions: keep at a temperature of 105 ° C for 1 hour, and thereafter keep for 30 minutes in a desiccator (25 ° C) containing silica gel).

In addition, the detergent particles of the present invention are excellent in the diffusion prevention property of the non-ionic surfactant. The diffusion property of the non-ionic surfactant is evaluated as follows.

A box is made with the top open that has dimensions of 10.2 cm in length, 6.2 cm in width, and 4 cm in height, with filter paper (No. 2, manufactured by ADVANTEC) stapling the paper Four corner filter. Two lines that cross each other are drawn with an oil-based marker, along the diagonals of the part that corresponds to the bottom of the box. The box is loaded with a 200 ml sample, and sealed with an acrylic cover. The sample is allowed to stand in a thermostat at a temperature of 30 ° C for 7 days, and the diffusion property of the non-ionic surfactant is evaluated.

The trial is carried out by visual examination of the degree of diffusion of the oil-based marker drawn on the bottom of the box after the sample is unloaded. The evaluation is carried out according to categories 1 to 5, and the status of each category is as follows.

Category 1: there is no broadcast at all; Category 2: the diffusion is generated in a part of the lines, as a state in which cilia grow; Category 3: diffusion is generated almost on a whole line, the average thickness of the marker line being less than 2.0 times; Category 4: the diffusion is generated in a whole line, the average thickness of the marker line 2.0 being times or higher and less than 3.0 times; Y Category 5: the diffusion is generated in a whole line, the average thickness of the marker line being 3.0 times or higher

In the present invention, acceptable products are those that have an evaluation of the degree of diffusion mentioned above according to category 1 to 2.

Examples

The present invention will be further described hereinbelow by the Examples given below.

Example 1

The base particles used in Reference Examples 1-1, 1-2, 1-4, 1-5 and in Examples 1-3 and 1-6 to 1-8 were produced by the following procedures. An amount of 460 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 120 kg of sodium sulfate, 140 kg of sodium carbonate and 5 kg of sodium sulphite were added thereto. After stirring the mixture for 10 minutes, 170 kg of a 40% by weight aqueous solution of sodium polyacrylate was added thereto. After stirring the mixture for an additional period of 10 minutes, 40 kg of sodium chloride and 140 kg of zeolite were added thereto, and the resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 58 ° C.

This suspension was sprayed with a spray pressure of 25 kg / cm2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 225 ° C from the bottom of the tower and escaped at a temperature of 105 ° C from the top of the tower. The water content of the base particles was 1.6%.

The resulting base particles had physical properties such that the base particles had an average particle size of 281 µm, an apparent density of 506 g / l, a free fluidity of 5.8 seconds, and a support capacity of 45 ml / 100 g

The base particles used in Examples 1-10 and Reference Example 1-9 were produced by the following procedures. An amount of 430 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 160 kg of sodium sulfate was added thereto. After stirring the mixture for 5 minutes, 100 kg of sodium silicate (effective ingredient: 40%) and 10 kg of carboxymethyl cellulose were added thereto. After stirring the mixture for 5 minutes, 60 kg of sodium tripolyphosphate and 130 kg of sodium carbonate were added thereto. After stirring the mixture for 15 minutes, 60 kg of a 40% by weight solution of sodium polyacrylate was added thereto. The resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 60 ° C.

This suspension was sprayed with a spray pressure of 40 kg / cm 2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 235 ° C from the bottom of the tower and escaped at a temperature of 115 ° C from the top of the tower. The water content of the base particles was 2.0%.

The resulting base particles had physical properties such that the base particles had an average particle size of 203 µm, an apparent density of 420 g / l, a free fluidity of 6.4 seconds, and a support capacity of 32 ml / 100 g

The base particles used in Reference Example 1-11 were produced by the following procedures. An amount of 413 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 135 kg of sodium sulfate was added thereto. After stirring the mixture for 5 minutes, 60 kg of sodium silicate (effective ingredient: 40%) and 12 kg of carboxymethyl cellulose were added thereto. After stirring the mixture for 5 minutes, 50 kg of sodium tripolyphosphate and 150 kg of sodium carbonate were added thereto. After stirring the mixture for 15 minutes, 130 kg of a 40% by weight solution of sodium polyacrylate was added thereto. After stirring the resulting mixture for an additional period of 10 minutes, 50 kg of sodium chloride was added thereto, and the resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 60 ° C.

This suspension was sprayed with a spray pressure of 35 kg / cm2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 235 ° C from the bottom of the tower and escaped at a temperature of 112 ° C from the top of the tower. The water content of the base particles was 1.2%.

The resulting base particles had physical properties such that the base particles had an average particle size of 240 µm, an apparent density of 374 g / l, a free fluidity of 6.0 seconds, and a support capacity of 30 ml / 100 g

In addition, the components of the surfactant composition used in Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1-11, in Examples 1-3, 1-6, 1 -7, 1-8 and 1-10 and in Comparative Examples 1-1 to 1-2 are those listed in Table 1.

Reference Example 1-1

100 parts by weight of base particles previously heated at 50 ° C and powdered starting materials in the amounts in parts by weight listed in Table 2 were supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 l, equipped with a jacket), and the rotation of the main shaft 5 (rotation speed of the main shaft: 80 r / min, Froude number of the stirring impellers: 1.07) was started. At this point, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 44 parts by weight of a surfactant composition were supplied at 60 ° C for 2 minutes, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 5.3 parts by weight of a crystalline silicate listed in Table 2 were supplied to the mixer. Rotations of the main shaft (rotational speed: 150 r / min, Froude number of the impellers stirring: 3.8) and the shredder (shredder rotation speed: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and the rotation was performed only with the main axis for an additional period of 15 15 seconds. The rotation was temporarily stopped, and 13 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main axis for a period

20 additional 30 seconds, and then the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 2.

On the other hand, in Table 2, in addition to the average particle size (whole particles) of the detergent particles, the average particle size of the detergent particles that passed through the sieve having a screen is also listed next to them. 1180 µm aperture used in performance calculation. They were determined and / or

25 evaluated the free fluidity, bulk density, and dissolution ratio of the detergent particles, and the diffusion property of component c) using the detergent particles that were passed through the sieve mentioned above to exclude aggregate particles or thick:

[Table 1] Reference Example * [Table 2] Reference Example *

Ex.

Ex. Comp.

1-1 *

1-2 * 1-3 1-4 * 1-5 * 1-6 1-7 1-8 1-9 * 1-10 1-11 * 1-1 1-2

Tensioactive Composition * 1

a) R-OSO3 Na (C12 / 14/16 = 67/27/6)

100 - 100 100 100 100 100 100 100 100 - 100 100

a) R-OSO3 Na (C14 = 100)

- 100 - - - - - - - - - - -

b) Water

38.9 42.9 38.9 38.9 38.9 38.9 38.9 38.9 39 39 42.9 38.9 38.9

Viscosity [Pa.s] of the surfactant composition at 60 ° C

4.2 3.7 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 3.7 4.2 4.2

* 1: parts by weight

Composition of detergent particles (parts by weight)

Ex. Ex. Comp.

1-1 *

1-2 * 1-3 1-4 * 1-5 * 1-6 1-7 1-8 1-9 * 1-10 1-11 * 1-1 1-2

Tensioactive Composition

44 Four. Five 31 31 31 47 fifteen 31 31 22 3. 4 44 44

c) Polyoxyethylene alkyl ether

- - 22 22 22 eleven 32 22 0 16 - - -

Polyethylene glycol

- - - - - - - 2.0 - 1.5 one - -

Fatty acid

- - - - - - - - - - - - -

Base particles

100 100 100 100 100 100 100 100 100 100 100 - -

Base particle substitute powder

- - - - - - - - - - - 100 100

Starting material powder

Sodium carbonate

3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 - 3.2 3.2

Crystalline silicate

14 14 14 14 14 14 14 14 14 14 - 14 14

Fine powder

Crystalline silicate

5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 - 5.3 5.3

Zeolite

13 13 13 13 13 13 13 13 13 0 3. 4 85 64

Sodium tripolyphosphate

- - - - - - - - - twenty - - -

Average particle size of detergent particles [! M] (whole particles)

351 363 334 311 326 329 322 3. 4. 5 246 223 265 898 886

Performance [%]

91 91 97 98.6 97 93 99 97 94 99 98 57 58

Degree of particle growth [-]

1,249 1.2918 1.19 1,1068 1,1643 1.17 1.15 1,2278 1.21 1.1 1.1 - -

Average particle size of the detergent particles [! M] (those with sieve pitch sizes of 1180 µm)

312 318 306 308 303 304 318 322 229 220 264 591 553

Free fluidity of detergent particles [s]

6.1 6.3 6.6 6.6 6.5 6.7 6.7 6.5 6.9 6.8 7 7.3 8.6

Apparent density of detergent particles [g / l]

580 612 644 677 652 641 681 643 551 585 468 815 862

Dissolution ratio of detergent particles [%]

81.1 81 96 97 94 91 99 95 84 98 99 61.3 62.6

Dissemination property of component c)

- - one 2 2 one 2 one - one - - -

In Tables 1 and 2, the following components were used. Sodium carbonate: manufactured by Central Glass Co., Ltd. with the trade name of DENSE ASH, average size of particle: 290 µm, bulk density: 980 g / l; Crystalline silicate: manufactured by K.K. Tokuyama Siltex with the trade name of Prefeed N (powdered powder up to an average particle size of 18 µm); Zeolite: manufactured by Zeobuilder with the trade name of Zeobuilder (type 4A zeolite, average size of 3.5 µm particle); Sodium tripolyphosphate: manufactured by SHIMONOSEKI MITSUI CHEMICALS, INC. with the trade name of sodium tripolyphosphate (powder sprayed to a size with an average particle size of 15 µm); Polyoxyethylene alkyl ether: manufactured by Kao Corporation under the trade name of EMULGEN 108KM (number moles of ethylene oxide added: 8.5, number of carbon atoms of the alkyl moiety: 12-14), point of melting: 18 ° C); Polyethylene glycol: manufactured by Kao Corporation under the trade name of K-PEG6000LA (average molecular weight: 8500, melting point: 60 ° C); Y Fatty acid: manufactured by Kao Corporation under the trade name of LUNAC P-95.

Component b) of the surfactant composition listed in Table 1 was 39 parts by weight, based at 100 parts by weight of component a), and the viscosity of the surfactant composition was 4.2 Pa · s (60 ° C)

Reference Example 1-2

Detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2. The physical properties of the resulting detergent particles are shown in Table 2.

Here, as component a) of the surfactant composition used in Reference Example 1-2, one having an alkyl chain length of 14 was used. The components and viscosity are as shown in Table 1.

Example 1-3

100 parts by weight of base particles previously heated at 50 ° C and powdered starting materials in the amounts in parts by weight listed in Table 2 were supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the main shaft rotation was started (main shaft rotation speed: 80 r / min, Froude number of stirring impellers: 1.07). At this point, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring with the rotation of the main shaft for 1 minute, 22 parts by weight of the polyoxyethylene alkyl ether were supplied at 60 ° C for 1 minute, and then 31 parts by weight of a surfactant composition were supplied at 60 ° C for 1 minute , and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 5.3 parts by weight of a crystalline silicate listed in Table 2 were supplied to the mixer. Rotations of the main shaft (rotation speed: 150 r / min, Froude number of the impellers of agitation: 3.8) and the shredder (shredder rotation speed: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main axis for an additional period of 15 seconds. The rotation was temporarily stopped, and 13 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 2.

Here, in Example 1-3, as the surfactant composition, the same as used in Reference Example 1 was used

1. The components and viscosity are as shown in Table 1.

Reference Example 1-4

The detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, with the proviso that the polyoxyethylene alkyl ether and the surfactant composition were pre-mixed and then added for 2 minutes The physical properties of the resulting detergent particles are shown in Table 2.

Here, the surfactant composition used in Reference Example 1-4 was the same as that used in Reference Example 1-1. The components and viscosity are as shown in Table 1.

Reference Example 1-5

The detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, except that the surfactant composition was supplied for 1 minute, and after that the polyoxyethylene alkyl ether was supplied for 1 minute The physical properties of the resulting detergent particles are shown in Table 2.

Here, the surfactant composition used in Reference Example 1-5 was the same as that used in Reference Example 1-1. The components and viscosity are as shown in Table 1.

Examples 1-6 and 1-7

The detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, except for the amounts of the polyoxyethylene alkyl ether and the surfactant composition. The physical properties of the resulting detergent particles are shown in Table 2.

Here, the surfactant compositions used in Examples 1-6 and 1-7 were the same as that used in Reference Example 1-1. The components and viscosity are as shown in Table 1.

Example 1-8

The polyoxyethylene alkyl ether was supplied and then the surfactant composition was supplied in the same manner as in Example 1-3 with the components listed in Table 2, with the proviso that 2.0 parts by weight of the mixture were previously mixed. polyethylene glycol with the polyoxyethylene alkyl ether, and then the mixture was added. After mixing the components for 4 minutes, 3.6 parts by weight of the fatty acid were added thereto for 1 minute, then the mixing was performed for 1 minute, and the rotations were temporarily stopped. Subsequent procedures were performed in the same manner as in Example 1-3. The physical properties of the resulting detergent particles are shown in Table 2.

Here, the surfactant composition used in Example 1-8 was the same as that used in Reference Example 1-1. The components and viscosity are as shown in Table 1.

It can be seen that in all Reference Examples 1-4, 1-5 and Examples 1-3, 1-6 to 1-8 in which polyoxyethylene alkyl ether was added to component c) component diffusion was prevented C). Among them, diffusion can also be avoided by mixing the component c) with the base particles before mixing with the surfactant composition. In addition, it can be seen that similar effects are caused by mixing polyethylene glycol with component c). In addition, the detergent particles to which component c) was added did not give the sensation of obstruction after handling.

Reference Example 1-9

The detergent particles were obtained in the same manner as in Example 1-1 with the components listed in Table 2. The physical properties of the resulting detergent particles are shown in Table 2.

Example 1-10

The detergent particles were obtained in the same manner as in Example 1-8 with the components listed in Table 2. Here, as a fine powder, sodium tripolyphosphate was used. The physical properties of the resulting detergent particles are shown in Table 2.

Reference Example 1-11

The powdered starting material consisting of 100 parts by weight of the base particles previously heated at 50 ° C was supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and rotation began of the main axis (speed of rotation of the main axis: 80 r / min, Froude number of the stirring impellers: 1.07). On the other hand, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 1.0 part by weight of the polyethylene glycol was supplied at 60 ° C for 1 minute, and then 34 parts by weight of a surfactant composition were supplied at 60 ° C for 2 minutes, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 34 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 2.

On the other hand, in Table 2, in addition to the average particle size (whole particles) of the detergent particles, the average particle size of the detergent particles that passed through the sieve having a screen is also listed next to them. 1180 µm aperture used in performance calculation. The free fluidity, bulk density, and dissolution ratio of the detergent particles, and the diffusion property of component c) were determined and / or evaluated using the detergent particles that were passed through the sieve mentioned above. to exclude aggregate or thick particles.

Comparative Example 1-1

The detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2, using a base particle substitute powder instead of the base particles. Here, in Comparative Example 1-1, as a base particle replacement powder, a powder produced by dry mixing the components was used so that it had the ratio of the mixed starting material in the base particles in a given compositional relationship. The physical properties of the resulting detergent particles are shown in Table 2. Detergent particles having excellent free fluidity were obtained in the same manner as in Reference Examples 1-1, 1-2, 1-4, 1 -5, 1-9, 1-11 and in Examples 1-3, 1-6, 1-7, 1-8 and 1-10; however, the amount of fine powder of modifying agent (zeolite) that was necessary to obtain a detergent having excellent free fluidity increased dramatically compared to that of Reference Examples 1-1, 1-2, 1-4 , 1-5, 1-9, 1-11 and Examples 1-3, 1-6, 1-7, 1-8 and 1

10. In addition, particle aggregation and coarse particle formation took place, thereby dramatically decreasing performance. In addition, the dissolution ratio decreased. The amount and yield of fine powder added on this occasion, and the average particle size, free fluidity, bulk density, and dissolution ratio of detergent particles are shown in Table 2.

Here, the surfactant composition used in Comparative Example 1-1 was the same as that used in Reference Example 1-1. The components and water content and viscosity are those shown in Table 1.

Comparative Example 1-2

Detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2, using a base particle replacement powder in the same manner as in Comparative Example 1-1. Here, in Comparative Example 1-2, as a base particle replacement powder, a powder produced by dry blending sodium bicarbonate and LIGHT ASH in a proportion of sodium bicarbonate / LIGHT ASH = 2/1 was used. The physical properties of the resulting detergent particles are shown in Table 2.

The amount of fine powder modifying agent (zeolite) that was needed to improve free fluidity increased dramatically compared to Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1 -11 and Examples 1-3, 1-6, 1-7, 1-8 and 1-10. In addition, particle aggregation and coarse particle formation took place, thereby dramatically decreasing performance.

The amount and yield of fine powder (zeolite) added on this occasion, and the average particle size, free fluidity, bulk density, and dissolution ratio of detergent particles are shown in the Table

2.

Here, the surfactant composition used in Comparative Example 1-2 was the same as that used in Reference Example 1-1.

It can be seen from the results in Table 2 that all detergent particles obtained in Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1-11 and in the Examples 1-3, 1-6, 1-7, 1-8 and 1-10 are excellent in free fluidity, dissolution ratio, and yield, compared to those in Comparative Examples 1-1 and 1-2.

Example 2

The base particles used in Reference Examples 2-1, 2-2, 2-4, 2-5 and in Examples 2-3 and 2-6 were produced by the following procedures. An amount of 460 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 120 kg of sodium sulfate, 140 kg of sodium carbonate and 5 kg of sodium sulphite were added thereto. After stirring the mixture for 10 minutes, 170 kg of a 40% by weight solution of sodium polyacrylate was added thereto. After stirring the mixture for an additional period of 10 minutes, 40 kg of sodium chloride and 140 kg of zeolite were added thereto, and the resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 58 ° C.

This suspension was sprayed with a spray pressure of 25 kg / cm2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 225 ° C from the bottom of the tower and escaped at a temperature of 105 ° C from the top of the tower. The water content of the base particles

It was 1.6%.

The resulting base particles had physical properties such that the base particles had an average particle size of 281 µm, an apparent density of 506 g / l, a free fluidity of 5.8 seconds, and a support capacity of 45 ml / 100 g

The base particles used in Reference Example 2-7 and in Example 2-8 were produced by the following procedures. An amount of 430 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 160 kg of sodium sulfate was added thereto. After stirring the mixture for 5 minutes, 100 kg of sodium silicate (effective ingredient: 40%) and 10 kg of carboxymethyl cellulose were added thereto. After stirring the mixture for 5 minutes, 60 kg of sodium tripolyphosphate and 130 kg of sodium carbonate were added thereto. After stirring the mixture for 15 minutes, 60 kg of a 40% by weight solution of sodium polyacrylate was added thereto. The resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 60 ° C.

This suspension was sprayed with a spray pressure of 40 kg / cm 2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 235 ° C from the bottom of the tower and escaped at a temperature of 115 ° C from the top of the tower. The water content of the base particles was 2.0%.

The resulting base particles had physical properties such that the base particles had an average particle size of 203 µm, an apparent density of 420 g / l, a free fluidity of 6.4 seconds, and a support capacity of 32 ml / 100 g

The base particles used in Reference Example 2-9 were produced by the following procedures. An amount of 413 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 135 kg of sodium sulfate was added thereto. After stirring the mixture for 5 minutes, 60 kg of sodium silicate (effective ingredient: 40%) and 12 kg of carboxymethyl cellulose were added thereto. After stirring the mixture for 5 minutes, 50 kg of sodium tripolyphosphate and 150 kg of sodium carbonate were added thereto. After stirring the mixture for 15 minutes, 130 kg of a 40% by weight solution of sodium polyacrylate was added thereto. After stirring the resulting mixture for an additional period of 10 minutes, 50 kg of sodium chloride was added thereto, and the resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 60 ° C.

This suspension was sprayed with a spray pressure of 35 kg / cm2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 235 ° C from the bottom of the tower and escaped at a temperature of 112 ° C from the top of the tower. The water content of the base particles was 1.2%.

The resulting base particles had physical properties such that the base particles had an average particle size of 240 µm, an apparent density of 374 g / l, a free fluidity of 6.0 seconds, and a support capacity of 30 ml / 100 g

In addition, the components of the surfactant composition used in Reference Examples 2-1, 2-2, 2-4, 2-5, 2-7, 2-9, in Examples 2-3, 2-6, 2 -8 and Comparative Examples 2-1 to 2-2 are those listed in Table 3.

Reference Example 2-1

100 parts by weight of base particles previously heated at 50 ° C and powdered starting materials in the amounts in parts by weight listed in Table 4 were supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the main shaft rotation was started (main shaft rotation speed: 80 r / min, Froude number of stirring impellers: 1.07). At this point, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 64 parts by weight of a surfactant composition were supplied at 60 ° C for 2 minutes, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 5.3 parts by weight of a crystalline silicate listed in Table 4 were supplied to the mixer. Rotations of the main shaft (rotational speed: 150 r / min, Froude number of the impellers of agitation: 3.8) and the shredder (shredder rotation speed: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main axis for an additional period of 15 seconds. The rotation was temporarily stopped, and 42 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number

of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and then the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 4.

5 On the other hand, in Table 4, in addition to the average particle size (whole particles) of the detergent particles, the average particle size of the detergent particles that passed through the sieve having an aperture of 1180 µm used in the calculation of performance. The free fluidity, bulk density, and dissolution ratio of detergent particles, and diffusion property of component c) were determined and / or evaluated using detergent particles that were passed through

10 sieve mentioned above to exclude aggregate or coarse particles.

[Table 3] Reference Example * [Table 4] Reference Example *

Ex.

Ex. Comp.

2-1 *

2-2 * 2-3 2-4 * 2-5 * 2-6 2-7 * 2-8 2-9 * 2-1 2-2

Tensioactive Composition

a) R-O- (CH2 CH2 O) 1 SO3 Na (C12 / 14 = 72/28)

100 - 100 100 100 100 100 100 - 100 100

a) R-O- (CH2 CH2 O) 2 SO3 Na

- 100 - - - - - - 100 - -

b) Water

43 41 43 43 43 43 43 43 41 43 43

Viscosity [Pa.s] of the surfactant composition at 60 ° C

3.1 2.8 3.1 3.1 3.1 3.1 3.1 3.1 2.8 3.1 3.1

Composition of detergent particles (parts by weight)

Ex. Ex. Comp.

2-1 *

2-2 * 2-3 2-4 * 2-5 * 2-6 2-7 * 2-8 2-9 * 2-1 2-2

Tensioactive Composition

64 63 32 32 32 32 Four. Five 26 3. 4 64 64

c) Polyoxyethylene alkyl ether

- - 22 22 22 22 - 16 - - -

Polyethylene glycol

- - - - - 2 - - one - -

Fatty acid

- - - - - 3.6 - - - - -

Base particles

100 100 100 100 100 100 100 100 100 - -

Base particle substitute powder

- - - - - - - - - 100 100

Starting material powder

Sodium carbonate

3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 - 3.2 3.2

Crystalline silicate

14 14 14 14 14 14 14 14 - 14 14

Fine powder

Crystalline silicate

5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 - 5.3 5.3

Zeolite

42 3. 4 eleven eleven eleven eleven 40 - 3. 4 85 59

Sodium tripolyphosphate

- - - - - - - - - - -

Average particle size of detergent particles [! M] (whole particles)

396 377 296 300 303 286 254 228 262 881 927

Performance [%]

93 99 99 98.6 99 99 96 99 99 64 57.8

Degree of particle growth [-]

1.4 1.3 1,053 1,068 1,078 1.3 1.1 1.1 1.1 - -

Average particle size of the detergent particles [! M] (those with sieve pitch sizes of 1180 µm)

319 317 295 300 302 286 253 227 261 535 327

Free fluidity of detergent particles [s]

6.3 5.6 5.8 7.1 6.4 6.5 6 6.2 6.8 6.6 8.6

Apparent density of detergent particles [g / l]

747 769 769 741 751 752 740 730 489 923 853

Dissolution ratio of detergent particles [%]

94 96 99 99 99 98 98 98 99 70 89

Dissemination property of component c)

- - one 2 2 one - one - - -

In Tables 3 and 4, the following components were used. Sodium carbonate: manufactured by Central Glass Co., Ltd. with the trade name of DENSE ASH, average size of particle: 290 µm, bulk density: 980 g / l; Crystalline silicate: manufactured by K.K. Tokuyama Siltex with the trade name of Prefeed N (powdered powder up to an average particle size of 18 µm); Zeolite: manufactured by Zeobuilder with the trade name of Zeobuilder (type 4A zeolite, average size of 3.5 µm particle); Sodium tripolyphosphate: manufactured by SHIMONOSEKI MITSUI CHEMICALS, INC. with the trade name of sodium tripolyphosphate (powder sprayed to a size with an average particle size of 15 µm); Polyoxyethylene alkyl ether: manufactured by Kao Corporation under the trade name of EMULGEN 108KM (number moles of ethylene oxide added: 8.5, number of carbon atoms of the alkyl moiety: 12-14), point of melting: 18 ° C); Polyethylene glycol: manufactured by Kao Corporation under the trade name of K-PEG6000LA (average molecular weight: 8500, melting point: 60 ° C); Y Fatty acid: manufactured by Kao Corporation under the trade name of LUNAC P-95.

Component b) of the surfactant composition listed in Table 3 was in 43 parts by weight, in based on 100 parts by weight of component a), and the viscosity of the surfactant composition was 3.1 Pa · s (60 ° C).

Reference Example 2-2

The detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4. The physical properties of the resulting detergent particles are shown in Table 4.

Here, the surfactant composition used in Reference Example 2-2 is a commercially available product with the trade name EMAL270J (average number of moles of EO = 2) (manufactured by Kao Corporation), and its components and viscosity they are those shown in Table 3.

Example 2-3

100 parts by weight of base particles previously heated at 50 ° C and powdered starting materials in the amounts in parts by weight listed in Table 4 were supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the main shaft rotation was started (main shaft rotation speed: 80 r / min, Froude number of stirring impellers: 1.07). At this point, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring with the rotation of the main shaft for 1 minute, 22 parts by weight of the polyoxyethylene alkyl ether were supplied at 60 ° C for 1 minute, and then 32 parts by weight of a surfactant composition were supplied at 60 ° C for 1 minute , and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 5.3 parts by weight of a crystalline silicate listed in Table 4 were supplied to the mixer. Rotations of the main shaft (rotational speed: 150 r / min, Froude number of the impellers of agitation: 3.8) and the shredder (shredder rotation speed: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main axis for an additional period of 15 seconds. The rotation was temporarily stopped, and 11 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 4.

Here, in Example 2-3, as the surfactant composition, the same as used in Reference Example 2 was used

1. The components and viscosity are as shown in Table 3.

Reference Example 2-4

The detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4, with the proviso that the polyoxyethylene alkyl ether and the surfactant composition were pre-mixed and then added for 2 minutes The physical properties of the resulting detergent particles are shown in Table 4.

Here, the surfactant composition used in Reference Example 2-4 was the same as that used in Reference Example 2-1. The components and viscosity are as shown in Table 3.

Reference Example 2-5

The detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4, except that the surfactant composition was supplied for 1 minute, and after that the polyoxyethylene alkyl ether was supplied for 1 minute The physical properties of the resulting detergent particles are shown in Table 4.

Here, the surfactant composition used in Reference Example 2-5 was the same as that used in Reference Example 2-1. The components and viscosity are as shown in Table 3.

Example 2-6

The polyoxyethylene alkyl ether was supplied and then the surfactant composition was supplied in the same manner as in Example 2-3 with the components listed in Table 4, with the proviso that 2.0 parts by weight of the mixture were previously mixed. polyethylene glycol with the polyoxyethylene alkyl ether, and then added to the mixture. The physical properties of the resulting detergent particles are shown in the Table

4. After mixing the components for 4 minutes, 3.6 parts by weight of the fatty acid were added thereto for 1 minute, the mixing was subsequently carried out for 1 minute, and the rotations were temporarily stopped. Subsequent procedures were performed in the same manner as in Example 2-3.

Here, the surfactant composition used in Example 2-6 was the same as that used in Reference Example 2-1. The components and viscosity are as shown in Table 3.

It can be seen that in all Examples 2-3, 2-6 and Reference Examples 2-4 and 2-5 in which polyoxyethylene alkyl ether was added to component c) diffusion of component c) was avoided. Among them, diffusion can also be avoided by mixing the component c) with the base particles before mixing with the surfactant composition. In addition, it can be seen that similar effects are caused by mixing polyethylene glycol with component c).

Reference Example 2-7

The detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4. The physical properties of the resulting detergent particles are shown in Table 4.

Example 2-8

The detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4. Here, as a fine powder, sodium tripolyphosphate was used. The physical properties of the resulting detergent particles are shown in Table 4.

Reference Example 2-9

The powdered starting material consisting of 100 parts by weight of the base particles previously heated at 50 ° C was supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and rotation began of the main axis (speed of rotation of the main axis: 80 r / min, Froude number of the stirring impellers: 1.07). On the other hand, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 1.0 part by weight of the polyethylene glycol was supplied at 60 ° C for 1 minute, and then 34 parts by weight of a surfactant composition were supplied at 60 ° C for 2 minutes, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 34 parts by weight of a fine powder (zeolite) were supplied thereto. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 4.

On the other hand, in Table 4, in addition to the average particle size (whole particles) of the detergent particles, the average particle size of the detergent particles that passed through the sieve having a screen is also listed next to them. 1180 µm aperture used in performance calculation. The free fluidity, bulk density, and dissolution ratio of the detergent particles, and the diffusion property of component c) were determined and / or evaluated using the detergent particles that were passed through the sieve mentioned above. to exclude aggregate or thick particles.

Comparative Example 2-1

The detergent particles were obtained in the same manner as in Reference Example 2-1 with the

components listed in Table 4, using a base particle replacement powder instead of the base particles. Here, in Comparative Reference Example 2-1, as a base particle substitute powder, a powder produced by dry mixing the components was used so that it had the ratio of the mixed starting material in the base particles in A certain compositional relationship. The physical properties of the resulting detergent particles are shown in Table 4. Detergent particles having excellent free fluidity were obtained in the same manner as in Reference Examples 2-1, 2-2, 2-4, 2 -5, 2-7, 2-9, and in Examples 2-3, 2-6 and 2-8; however, the amount of fine powder of modifying agent (zeolite) that was necessary to obtain a detergent having excellent free fluidity increased dramatically compared to those in Reference Examples 2-1, 2-2, 2-4 , 2-5, 2-7, 2-9, and Examples 2-3, 2-6 and 2-8. In addition, particle aggregation and coarse particle formation took place, thereby dramatically decreasing performance. In addition, the dissolution ratio decreased.

The amount and yield of fine powder (zeolite) added on this occasion, and the average particle size, free fluidity, bulk density, and dissolution ratio of detergent particles are shown in the Table

Four.

Here, the surfactant composition used in Comparative Example 2-1 was the same as that used in Reference Example 2-1. The components and water content and viscosity are those shown in Table 3.

Comparative Example 2-2

Detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4, using a base particle replacement powder in the same manner as in Comparative Example 2-1. Here, in Comparative Example 2-2, as a base particle substitute powder, a powder produced by dry blending sodium bicarbonate and LIGHT ASH in a proportion of sodium bicarbonate / LIGHT ASH = 2/1 was used. The physical properties of the resulting detergent particles are shown in Table 4. The amount of fine powder of modifying agent (zeolite) that was necessary to improve free flow increased dramatically compared to that of Reference Examples 2-1 , 2-2, 2-4, 2-5, 2-7, 2-9, and Examples 2-3, 2-6 and 2-8. In addition, particle aggregation and coarse particle formation took place, thereby dramatically decreasing performance. The amount and yield of fine powder added on this occasion, and the average particle size, free fluidity, bulk density, and dissolution ratio of detergent particles are shown in Table 4.

Here, the surfactant composition used in Comparative Example 2-2 was the same as that used in Reference Example 2-1.

It can be seen from the results of Table 2 that all detergent particles obtained in Reference Examples 2-1, 2-2, 2-4, 2-5, 2-7, 2-9, and in Examples 2-3, 2-6 and 2-8 are excellent in free fluidity, dissolution ratio, and yield, compared to those in Comparative Examples 2-1 and 2-2.

Example 3

The base particles used in Examples 3-1 and 3-2 were produced by the following procedures. An amount of 495 kg of water was added to a 1 m3 mixing vessel that has stirring impellers. After the water temperature reached 55 ° C, 218 kg of sodium sulfate were added thereto. After stirring the mixture for 10 minutes, 168 kg of a 40% by weight solution of sodium polyacrylate was added thereto. After stirring the mixture for an additional period of 10 minutes, 45 kg of sodium chloride and 220 kg of zeolite were added thereto, and the resulting mixture was stirred for 30 minutes, to obtain a homogeneous suspension. The final temperature of this suspension was 58 ° C.

This suspension was sprayed with a spray pressure of 25 kg / cm2 from a pressure spray nozzle disposed near the top of a spray drying tower. The high temperature gas that feeds the spray drying tower was supplied at a temperature of 225 ° C from the bottom of the tower and escaped at a temperature of 105 ° C from the top of the tower. The water content of the base particles was 2.5%.

The resulting base particles had physical properties such that the base particles had an average particle size of 192 µm, an apparent density of 536 g / l, a free fluidity of 5.2 seconds, and a support capacity of 45 ml / 100 g

In addition, the components of the surfactant composition used in Examples 3-1 to 3-2 are those listed in Table 5.

Example 3-1

The powder starting material consisting of 100 parts by weight of the base particles previously heated at 50 ° C was supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 l, equipped

with a jacket), and the main shaft rotation was started (main shaft rotation speed: 80 r / min, Froude number of stirring impellers: 1.07). On the other hand, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 22 parts by weight of the polyoxyethylene alkyl ether were supplied at 60 ° C for 1 minute, and then 31 parts by weight of a surfactant composition were supplied at 60 ° C for 1 minute, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 20 parts by weight of a fine powder (zeolite) were supplied to the mixer. Rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (shredder rotation speed: 3600 r / min,

10 Froude number of the decay impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The physical properties of the resulting detergent particles were those listed in Table 6.

On the other hand, in Table 6, in addition to the average particle size (whole particles) of the particles of

15 detergent, the average particle size of the detergent particles that passed through the sieve having an aperture of 1180 µm used in the calculation of yield is also listed next to them. The free fluidity, bulk density, and dissolution ratio of the detergent particles, and the diffusion property of component c) were determined and / or evaluated using the detergent particles that were passed through the sieve mentioned above. to exclude aggregate or thick particles.

20 [Table 5]

Surfactant composition (parts by weight) Ex.

3-1

3-2 **

to)

100 100

(R: C14 / 16 = 65:35) b) Water

41 41

Viscosity [Pa.s] of the surfactant composition at 60 ° C

5 5

** Reference Example

[Table 6]

Components of detergent particles

Ex.

3-1

3-2 **

Surfactant composition

31 3. 4

c) Polyoxyethylene alkyl ether

22

Polyethylene glycol

Fatty acid

Base particles

100 100

Substitute for base particles

Starting material powder

Sodium carbonate

Crystalline silicate

Fine powder

Crystalline silicate

Zeolite

twenty 3. 4

Sodium tripolyphosphate

(continuation)

Components of detergent particles

Ex.

3-1

3-2 **

Average particle size of detergent particles [! M] (whole particles)

225 211

Performance [%]

98 99

Degrees of particle growth [-]

1.17 1.05

Average particle size of detergent particles [! M] *

223 210

Free fluidity of detergent particles [s]

6.2 6.1

Apparent density of detergent particles [g / l]

694 651

Dissolution ratio of detergent particles [%]

95 97

Dissemination property of component c)

2 -

* (those with sizes that passed through the 1180 µm sieve) ** Reference

In Tables 5 and 6, the following components were used. Zeolite: manufactured by Zeobuilder with the trade name of Zeobuilder (type 4A zeolite, average particle size 3.5 µm); and Polyoxyethylene alkyl ether: manufactured by Kao Corporation under the trade name of 108KM (average number of moles of ethylene oxide: 8.5, number

5 of carbon atoms in the alkyl moiety: 12-14), melting point: 18 ° C).

Example 3-2

The powder starting material consisting of 100 parts by weight of the base particles previously heated at 50 ° C was supplied to a Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 l, equipped with a jacket), and rotation began of the main shaft (speed of rotation of the main shaft: 80 r / min, 10 Froude number of stirring impellers: 1.07) On the other hand, hot water at 80 ° C was allowed to flow through the jacket at 10 l / minute, without shredder rotation (equipped with disintegration impellers). After stirring the components with the rotation of the main shaft for 1 minute, 34 parts by weight of a surfactant composition were supplied at 60 ° C for 1 minute, and the components were then mixed for 6 minutes. The rotations were temporarily stopped, and 34 parts by weight of a fine powder (zeolite) were supplied to the mixer. The rotations of the main shaft (rotation speed: 150 r / min, Froude number of the stirring impellers: 3.8) and the shredder (speed of shredder rotation: 3600 r / min, Froude number of the disintegration impellers: 1010) were activated for 15 seconds. After 15 seconds, the shredder rotation was stopped, and rotation was performed only with the main shaft for an additional period of 30 seconds, and the resulting detergent particles were discharged. The properties

20 physics of the resulting detergent particles were those listed in Table 6.

Here, the surfactant composition used in Example 3-2 was the same as that used in Example 3-2. The components and water content and viscosity are those shown in Table 5.

Industrial applicability

The single core detergent particles of the present invention can be suitably used, for example, for the production of a laundry detergent, a dishwashing detergent, or the like.

Claims (7)

1. A method of producing single core detergent particles having an average particle size of 150 µm or greater and a particle growth rate of 1.5 or less comprising the steps of: step A) preparing a composition surfactant comprising: a) an anionic surfactant represented by any of the following formulas (1) to (3): R-O-SO3M (1) in which R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms; and M is an alkali metal atom or an amine, R-O (CH2CH2O) n-SO3M (2) in which R is an alkyl group or an alkenyl group having from 10 to 18 carbon atoms; n is an average number of moles added from 0.1 to 3.0; and M is an alkali metal atom, or an ammonium or an organic amine and wherein R is an alkyl group or an alkenyl group having from 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M, and b) water in an amount of 25 to 65 parts by weight based on 100 parts by weight of said component a); stage B): mixing the surfactant composition obtained in stage A) and base particles that have a support capacity of 20 ml / 100 g or greater and that comprise a water-soluble inorganic salt produced by spray drying, while basically maintaining the shape of the base particles; Y stage C): modify the surface of the mixture obtained in stage B) with a fine powder wherein the detergent particles additionally comprise c) a non-ionic surfactant having a melting point of 30 ° C or less in a range of 1 to 20% by weight of the detergent particles, the component c) being mixed with the base particles rather than with the surfactant composition prepared in step A).

2.

 The method of producing single core detergent particles according to claim 1, wherein component a) is contained in an amount of 5 to 30% by weight of the detergent particles.

3.

 The method of producing single core detergent particles according to claim or 2 wherein the amount of c) the nonionic surfactant having a melting point of 30 ° C or less in the detergent particles is in the range of 5 to 15% by weight of the detergent particles.

Four.

 The method of producing single core detergent particles according to any one of claims 1 to 3, wherein the water soluble inorganic salt is at least one selected from the group consisting of sodium carbonate, potassium carbonate, and sodium sulfate

5.

 The method of producing single core detergent particles according to any one of claims 1 to 4, wherein the bulk density of the base particles is 200 to 1000 g / l.

6.

 The method of producing single core detergent particles according to any one of claims 1 to 5, wherein the fine powder is an aluminosilicate.

7.

 The method of producing single core detergent particles according to any one of claims 1 to 6, wherein the amount of fine powder is 0.5 to 40 parts by weight, based on 100 parts by weight of the mixture obtained in stage B).