TWI441917B - Particles for supporting surfactant - Google Patents

Description

Surfactant loading particle group

The present invention relates to a particle group for supporting a surfactant and a method for producing the same. Further, the present invention relates to a high bulk density detergent particle group using the surfactant-supporting particle group, and a detergent composition comprising the detergent particle group.

One of the methods for obtaining a powder detergent is a method comprising the step of supporting a surfactant-supporting particle group to carry a liquid surfactant. In this method, the surfactant-supporting particle group is required to have a high load carrying capacity for the liquid surfactant. In other words, the load carrying capacity required for the surfactant-supporting particle group includes the following two factors: a large amount of liquid surfactant (supporting capacity) and a liquid interface activity which can be once absorbed. The agent is firmly held inside the granules without oozing out (loading force). The loading capacity is important for formulating the amount of surfactant required to achieve cleaning performance; in addition, the supporting force inhibits the leakage of the liquid surfactant and prevents the fluidity of the powder detergent from being lowered and agglomerated. It is important to prevent the transfer of the liquid surfactant to the container or its surface.

Further, from the viewpoint of productivity, it is also required to rapidly absorb the characteristics (loading speed) of the liquid surfactant for the surfactant-supporting particle group.

Various types of surfactant-supporting particle groups have been studied so far. For example, Patent Document 1 discloses a surfactant-supporting particle group in which a preparation liquid containing a water-soluble polymer and a water-soluble salt is spray-dried. However, spray drying must be carried out when producing the particle group, and from the viewpoint of economy, a production method in which spray drying is not used is sought.

On the other hand, for example, Patent Document 2 discloses a method of drying a hydrated composition comprising an inorganic salt and a polymer organic binder. However, this method is essentially a technique for releasing hydration water by drying, thereby increasing the absorption capacity (corresponding to the carrying capacity of the present invention), and it is extremely difficult to adjust the supporting force or the carrying speed. Therefore, it is desired to use a surfactant-supporting particle group which is excellent in all of the supporting capacity, the supporting force, and the supporting speed.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-244644, Patent Document 2: Japanese Patent Application Publication No. 2002-541267

Therefore, an object of the present invention is to produce a surfactant-supporting particle group excellent in a supporting capacity/supporting force/loading speed of a liquid surfactant composition without using a spray drying method. Moreover, the present invention provides a high bulk density detergent particle group obtained by using the surfactant-supporting particle group, and a detergent composition containing the detergent particle group.

That is, the gist of the present invention relates to the following: [1] A method for producing a surfactant-supporting particle group for producing a surfactant-supporting particle having a bulk density of 550 g/l or less The group includes the following steps 1(a) to 2: Step 1(a): a step of mixing a clay mineral powder and a powder material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral;

Step 2: adding water or a binder aqueous solution to the mixed powder obtained in the step 1 (a), and performing a granulation step using a low shear granulator; [2] manufacturing a particle group for surfactant loading The method is used for producing a particle carrier particle group having a bulk density of 550 g/l or less, and comprises the following steps 1(b) to 2: Step 1 (b): oil absorption ability other than clay minerals a step of mixing a powder material of 0.4 ml/g or more; and

Step 2: adding a water or a binder aqueous solution to the mixed powder obtained in the step 1 (b), and performing a granulation step using a low shear granulator; [3] a surfactant-supporting particle group, It has a bulk density of 550 g/l or less and contains the following components: powder materials with an oil absorption capacity of 0.4 ml/g or more other than clay minerals: 40 to 95% by weight

Clay mineral powder: 0~45wt%

Adhesive: 0~35wt%

Water: 0 to 15% by weight; [4] A high-bulk-density detergent particle group containing the surfactant-supporting particle group produced by the above-described production method of [1] or [2] or the above [3] The particle group of the surfactant-supporting particle group is loaded with a surfactant composition; and

[5] A detergent composition comprising the detergent particle group of the above [4].

According to the present invention, it is possible to obtain a surfactant-supporting particle group excellent in the supporting capacity/supporting force/loading speed of the liquid surfactant composition without using a spray drying method. Further, it is effective in obtaining a detergent particle group having excellent cleaning performance, quality, and the like by supporting the liquid surfactant composition in the surfactant-supporting particle group.

In the present invention, the surfactant-supporting particles mean particles containing at least a powder raw material having an oil absorption capacity of 0.4 ml/g or more and a water or an aqueous binder solution in addition to the clay mineral. It is preferred to add a water or an aqueous binder solution to a mixed powder containing at least a powder raw material having an oil absorption capacity of 0.4 ml/g or more in addition to the clay mineral, and to obtain particles by granulation using a low shear granulator. And the particles are used to carry a liquid surfactant composition. The aggregate of the particles is referred to as a surfactant-supporting particle group. The detergent particles are particles containing a surfactant, a builder, etc., which are obtained by supporting a surfactant-supporting particle-supporting surfactant composition, and the detergent particle group means the detergent. Aggregates of particles. The detergent composition refers to a detergent component containing a detergent particle group and optionally containing a detergent particle group (for example, a builder particle, a fluorescent dye, an enzyme, a fragrance, an antifoaming agent). A composition of a bleaching agent, a bleach activator, and the like.

The term "water-soluble" means that the solubility in water at 25 ° C is 0.5 g / 100 g or more, and the so-called water-insoluble means that the solubility in water at 25 ° C is less than 0.5 g / 100 g.

The liquid surfactant composition refers to a composition containing a surfactant in a liquid or slurry form when supported on a surfactant-supporting particle group.

<Composition of Particle Group for Surfactant Loading> 1. Powder materials with an oil absorption capacity of 0.4 ml/g or more other than clay minerals

As an essential component of the present invention, a powder raw material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral can be cited. The oil absorption capacity refers to a value determined by the method described in the quality evaluation method described later. The powder raw material having an oil absorption capacity of 0.4 ml/g or more in addition to the clay mineral is a substance which is porous in the fine pores of 10 μm or less in the powder and is in the pores thereof. A substance that can carry a surfactant. The upper limit of the oil absorption capacity is not particularly limited, and for example, it is preferably 1.0 ml/g or less.

From the viewpoint of granulation, the average particle diameter of the powder raw material is preferably from 50 to 250 μm, more preferably from 50 to 200 μm, particularly preferably from 80 to 200 μm.

Further, from the viewpoint of solubility, a water-soluble substance is preferred. Examples of the powder raw material include a light soda ash produced by firing sodium hydrogencarbonate or a porous powder obtained by drying a hydrate of soda ash, thenardite or sodium tripolyphosphate. A light soda ash is particularly preferred from the viewpoints of ease of handling and ease of availability.

When light soda ash is used as a powder raw material, the carrier loading ability can be further improved by adjusting the temperature at the time of calcination of sodium hydrogencarbonate. From the viewpoint of the supporting ability, the calcination temperature is preferably from 120 ° C to 250 ° C, more preferably from 150 to 220 ° C, particularly preferably from 150 to 200 ° C.

The content of the powder raw material is preferably from 40 to 95% by weight, more preferably from 45 to 90% by weight, particularly preferably from 45 to 90% by weight, from the viewpoint of the supporting ability. 50 to 85% by weight, particularly preferably 50 to 80% by weight. Further, when the composition is adjusted by the drying step, the particle group before the drying step is preferably contained in an amount of 25 to 80% by weight, more preferably 30 to 77% by weight, particularly preferably 32. ~77% by weight, particularly preferably 32 to 73% by weight.

2. Adhesive

The surfactant-supporting particle group of the present invention is obtained by granulating a mixture of powder raw materials by adding a water or a binder aqueous solution using a low-shear granulator. When a clay mineral is used, the mixture of the clay mineral and the powder material is granulated. When water is used, the adhesion of the powdery material or the adhesion of the clay mineral, which is partially dissolved in water, is granulated. When an aqueous binder solution is used, the adhesiveness of the adhesive can be further utilized, and granulation is easier.

Further, when the drying step is included, the use of water is accompanied by drying, and there is a concern that the particle strength is lowered. However, when a binder aqueous solution is used, the effect of the binder can be expected after drying. Therefore, it is preferred to use an aqueous binder solution.

The binder is not particularly limited as long as it has the ability to bind the components constituting the particles in the powder raw material to each other and has a property of rapidly dissolving and/or dispersing in water. For example, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and such derivatives, polyvinyl alcohol and its derivatives, and water-soluble cellulose derivatives (as such derivatives, ether compounds) are mentioned. An organic polymer such as a carboxylic acid polymer, a starch or a saccharide, or an inorganic polymer such as an amorphous phthalate.

From the viewpoint of adhesion and cleaning power, water-soluble cellulose derivatives, saccharides, and carboxylic acid-based polymers are preferred, and salts of acrylic acid-maleic acid copolymers and polyacrylates are more preferred. As the salt, a sodium salt, a potassium salt or an ammonium salt is preferred. Further, the weight average molecular weight of the carboxylic acid-based polymer is preferably from 1,000 to 100,000, more preferably from 2,000 to 80,000.

The content of the binder in the surfactant-supporting particle group is preferably from 0 to 35% by weight, more preferably from 0 to 35% by weight in the surfactant-supporting particle group, from the viewpoint of the adhesiveness and the oil absorption ability. 5 to 30% by weight, particularly preferably 8 to 20% by weight, particularly preferably 10 to 20% by weight. Further, when the composition is adjusted by the drying step, the particle group before the drying step is preferably 0 to 30% by weight, more preferably 3 to 25% by weight, particularly preferably 5~. 17% by weight, particularly preferably 7 to 17% by weight.

The concentration of the aqueous solution of the binder is not particularly limited, but the particle diameter at the time of granulation is largely affected by the volume of the aqueous solution of the binder, and therefore the concentration may be determined depending on the desired amount of the binder and the desired particle diameter.

3. Clay minerals

Clay minerals have a layered structure and can carry a liquid surfactant between their layers. Therefore, the loading capacity of the liquid surfactant can be increased by blending the clay minerals while increasing the load capacity.

Further, since the clay mineral exhibits adhesiveness by containing water, it is also possible to control the particle size of the surfactant-supporting particles by adjusting the blending amount.

From the viewpoint of load carrying capacity and particle size control, clay minerals may be added as a component for increasing the load capacity/loading power.

Examples of such a clay mineral include talc, pyrophyllite, bentonite (saponite, lithium bentonite, zinc bentonite, strontite, montmorillonite, aluminum bentonite, iron bentonite, etc.), vermiculite. , mica (phlogopite, biotite, iron lithium mica, muscovite, orange sapphire glass, squama, sea green stone, etc.), chlorite (oblique chlorite, chlorite, nickel chlorite, manganese) Aluminum chlorite, aluminum chlorite, bismuth aluminite, etc., crisp mica (green crisp mica, pearl mica, etc.), manganese zoisite, serpentine mineral (leaf serpentine, lizard serpentine, serpentine, Magnesium-aluminum serpentine, green cone stone, magnetic chlorite, iron serpentine, dark nickel serpentine, etc.), kaolin minerals (kaolinite, dick stone, pearl clay, He Leshi, etc.). Among them, in terms of softness, talc, bentonite, swellable mica, vermiculite, serpentine, kaolin mineral, etc. are preferred, and bentonite is preferred, and montmorillonite is particularly preferred. These may be used singly or in combination of two or more kinds as appropriate.

Further, from the viewpoint of the surfactant carrying ability, it is preferred to have the following general formula (I): [Si ₈ (Mg _a Al _b )O ₂₀ (OH) ₄ ] ^x- . The clay mineral represented by Me ^x+ (I) is the main component of clay minerals. Here, a, b, and x is 0 <a ≦ 6,0 <b ≦ 4, x = 12-2a-3b, Me is selected from Na, K, Li, Ca1 / 2, Mg1 / 2 , and the NH ₄ At least one of the ions.

As the clay mineral represented by the above formula (I), S "Laundrosil DGA212", "Laundrosil PR414", "Laundrosil DG214", "Laundrosil DGA Powder", "EXM0242", "Frasoft-1 Powder" manufactured by d-Chemie, "Detersoft GIS" manufactured by Laviosa, "Detersoft GIB""DetersoftGISW", pure bentonite (Pure Bentonite), standard bentonite (Standard Bentonite), premium bentonite (Premium Bentonite) manufactured by CSM. In the case of the above-mentioned clay mineral, there is also a particle type in which a binder component is added and granulated, and the binder component may be added as long as the effect of the present invention is not impaired.

When the above-mentioned clay mineral is used in the present invention, it is preferred that the form is powdery from the viewpoint of granulation, and if it is granulated, it is preferred to perform chopping in advance until appropriate. granularity. Examples of the pulverizer that can be used for shredding include an impact crusher such as a hammer mill, an impact pulverizer such as an atomizer or a pin mill, and a shear coarse crusher such as a quick pulverizer. These may be one-stage operations, or may be multi-stage operations of the same or different types of pulverizers.

The average particle diameter of the clay mineral powder is preferably 100 μm or less, more preferably 50 μm or less, and particularly preferably 30 μm or less.

In addition, in the clay mineral represented by the general formula (I), the total of alkali metal ions (Na ions, K ions, and Li ions) and alkaline earth metal ions (Ca ions, Mg) in terms of the supporting force and the solubility. The molar ratio [(Na+K+Li)/(Ca+Mg)]) of the total of the ions is preferably 1.0 or more, more preferably 1.5 or more, and particularly preferably 2.0 or more.

As for the clay mineral having a high ratio of alkali metal ions, if it is a natural product, the origin can be selected, and when the clay granule is produced, an alkali metal salt can also be added for preparation. Moreover, if it is a synthetic product, it can prepare arbitrarily by a well-known method.

4. Moisture

The surfactant-supporting particle group of the present invention contains an appropriate amount of water used in the production step. From the viewpoint of increasing the supporting capacity of the liquid surfactant composition of the particle group, the amount of water measured by the infrared moisture meter is preferably as small as possible, preferably 15% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less.

5. Other ingredients

Further, the surfactant-supporting particle group of the present invention may be appropriately blended with substances other than those listed in the above 1 to 4 as needed. However, from the viewpoint of the supporting ability, the amount of the substances is preferably 20% by weight or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less. For example, the materials that can be formulated are as follows.

. Chelating agent

In order to suppress the blocking action caused by metal ions, a chelating agent can be formulated. The water-soluble chelating agent is not particularly limited as long as it retains metal ion chelating ability, and crystalline citrate, tripolyphosphate, orthophosphate, pyrophosphate or the like can be used. Among them, crystalline citrate and tripolyphosphate are preferred. As for the water-insoluble chelating agent, from the viewpoint of dispersibility in water, it is preferred that the average particle diameter of the particles is 0.1 to 20 μm. Examples of a suitable water-insoluble chelating agent include crystalline aluminosilicates such as zeolite A, P-type zeolite, and zeolite X. In terms of metal ion chelation ability and economy, A is preferred. Zeolite.

. Water soluble inorganic salt

In order to improve the ionic strength of the washing liquid and to improve the sebum stain cleaning effect, it is preferred to add a water-soluble inorganic salt.

There is no particular requirement as long as it is a substance which has good solubility and does not adversely affect the cleaning power. For example, an alkali metal salt of a sulfate, a sulfite, an ammonium salt, etc. are mentioned.

Among them, it is preferred to use sodium sulfate, sodium sulfite, and potassium sulfate having a high degree of ionic dissociation as an excipient. Further, from the viewpoint of increasing the dissolution rate, it is also preferred to use it in combination with magnesium sulfate.

. Water insoluble excipient

There is no particular requirement as long as it is a substance which has good dispersibility in water and does not adversely affect the cleaning power. For example, crystalline or amorphous aluminosilicate, cerium oxide, hydrated citric acid compound, etc. are mentioned. From the viewpoint of dispersibility in water, it is preferred that the average particle diameter of the primary particles is 0.1 to 20 μm.

. Other auxiliary ingredients

For example, fluorescent dyes, pigments, dyes, and the like can be mentioned.

Further, the measurement of the average particle diameter of the above components can be carried out by the method described in the physical property measuring method described later.

<Method for Producing Particle Group for Surfactant Loading>

The surfactant-supporting particle group of the present invention can be produced by the following method: the method does not include a spray drying step, and at least comprises stirring a powder raw material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral. Or a step of mixing, and adding a water or an aqueous binder solution to the obtained mixed powder, and performing a granulation step using a low shear granulator.

1. Step 1 (a)

In the step of mixing the clay mineral powder with a powder raw material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral, any method may be employed as long as the materials can be substantially uniformly mixed. For example, the mixing may be carried out using the low shear granulator used in the step 2, or may be previously mixed using another mixer and then transferred to a low shear granulator. Examples of the other mixer that can be used for powder mixing include a drum type mixer, a pan type mixer, a belt type mixer, a conical spiral mixer, a SCHUGI (company name) mixer, and a LODIGE (company). Name) Mixer, high speed mixer, etc.

Here, the content of the clay mineral is preferably from 1 to 45% by weight, more preferably from 2 to 40% by weight in the surfactant-supporting particle group, from the viewpoint of the supporting ability and the particle diameter control. %, particularly preferably 3 to 40% by weight, further preferably 3 to 35% by weight, particularly preferably 4 to 30% by weight. Further, after granulation, if necessary, drying may be carried out, and when the composition is adjusted to the above composition by the drying step, the particle group before the drying step preferably contains 1 to 40% by weight, more preferably It is 2 to 35% by weight, particularly preferably 3 to 30% by weight, and further preferably 3 to 25% by weight, particularly preferably 6 to 25% by weight.

Moreover, the weight ratio of the clay mineral to the powder raw material (clay mineral/powder raw material) is preferably from 1/1 to 1/30, more preferably from 1/1 to 1/20, particularly preferably 1/2~ 1/20.

2. Step 1 (b)

In the step of stirring or mixing the powder raw materials having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral, any method may be employed as long as the materials can be substantially uniformly mixed. For example, the mixing may be carried out using the low shear granulator used in the step 2, or may be previously mixed using the above mixer and then transferred to a low shear granulator.

Further, the powder raw material other than the clay mineral in the present specification means a powder raw material which does not substantially contain the clay mineral, but may also contain 0 to 1.2% by weight of the clay mineral in the powder raw material. The content of the clay mineral is more preferably 0 to 1.0% by weight, particularly preferably 0 to 0.8% by weight, particularly preferably 0 to 0.6% by weight, based on the powder raw material.

From the viewpoint of the particle size of the surfactant-supporting particle group and the detergent particle group in which the particle group is loaded with the surfactant composition, the content of the clay mineral is used for the surfactant loading. The particle group is preferably 0 to 1% by weight, more preferably 0 to 0.8% by weight, particularly preferably 0 to 0.6% by weight, particularly preferably 0 to 0.5% by weight. Further, after granulation, it may be dried as needed, and when it is adjusted to the above composition by such a drying step, it is preferably 0 to 0.9% by weight, more preferably 0 to 0.9% by weight, before the drying step. It is 0 to 0.7% by weight, particularly preferably 0 to 0.5% by weight, particularly preferably 0 to 0.4% by weight.

3. Step 2

Step 2 is a step of adding water or an aqueous binder solution to the mixed powder obtained in the step 1 (a) or the step 1 (b), and granulating using a low shear granulator. In this step, particles of a structure in which the powder raw material is slowly aggregated are produced.

Further, step 1 (a) or step 1 (b) and step 2 may be simultaneously performed.

The low-shear granulator used in this step is not particularly limited as long as it does not impart strong shear to the granules. For example, a vertical or horizontal granulator having a main wing and a chopped wing that can impart high shear force can be used to suppress compaction by setting the number of revolutions and the number of pours described below to be low. For the manufacture of the particles of the invention. That is, the low-shear granulator of the present specification also includes a granulator which can be operated by reducing the shearing force by setting operating conditions or the like even in a granulator which can impart high shear force to the granules. machine.

As a low-shear granulator, a disc type granulator or a drum type granulation which is granulated by the rotation of the main body portion is preferable from the viewpoint of easiness of granulation and improvement of the load-carrying ability. machine. These devices can also be used in either batch or continuous processes. Further, in terms of powder mixing property and solid-liquid mixing property, it is preferred to provide a separator for auxiliary mixing on a disk or a drum.

Further, in order to use it as a low-shear granulator, it is preferable to set the number of Phines of the granulator defined by the following formula to 1.0 or less, and more preferably to 0.8. In the following, it is particularly preferable to set it to 0.6 or less, and it is particularly preferable to set it to 0.4 or less.

Flow number: Fr=V ² /(R×g)

V: circumferential speed [m/s], R: radius from the center of rotation to the circumference of the rotating object [m], g: gravitational acceleration [m/s ² ]

Further, from the viewpoint of uniformly adding water or a binder aqueous solution to the mixed powder, it is preferred to set the number of the granulators to 0.005 or more', more preferably 0.01 or more.

Further, in a vertical or horizontal granulator having a main wing and a chopped wing, V and R use the value of the main shaft; a disc type granulator or a drum type granulation which is granulated by the rotation of the main body portion of the main body In the machine, V and R use the value of the main body of the body. Further, in a disc type granulator having shredded wings, V and R use the value of the shredded wings.

In the present invention, the focus is on granulation by low shear to obtain a structure having a slowly agglomerated structure, but there is a problem that water or a binder aqueous solution is difficult to uniformly disperse at the time of low shear. Therefore, it is preferred to uniformly disperse the binder by a liquid addition method. As a method of uniformly dispersing the binder, a method of refining the binder by using a multi-fluid nozzle such as a one-fluid nozzle or a two-fluid nozzle is used.

The multi-fluid nozzle means that the binder and the gas for atomization (air, nitrogen, etc.) flow through the independent flow path to the vicinity of the nozzle tip end and are mixed. For the micronized nozzle, a 2-fluid nozzle or a 3-fluid nozzle, a 4-fluid nozzle, or the like can be used. Further, the mixing portion of the binder and the gas for atomization may be either an internal mixing type that is mixed in the nozzle tip end portion or an external mixing type that is mixed outside the nozzle tip end portion.

It is particularly preferable to use a multi-fluid nozzle such as a two-fluid nozzle to perform fine dropletization and then add it. As such a multi-fluid nozzle, for example, a wide-angle circular two-fluid nozzle (manufactured by Spraying Systems-Japan) or a four-fluid nozzle (manufactured by Fujisaki Electric Co., Ltd.) or the like can be used.

Further, in order to increase the rate of addition of the binder, it is also effective to use a plurality of such fluids or other fluid nozzles to increase the rate of addition while maintaining the fineness of the droplets.

By such a method, it is possible to obtain a surfactant-supporting particle group which can be uniformly dispersed in a high-viscosity binder aqueous solution, and the yield is improved, and the particle size distribution is narrow.

4. Step 3

Step 3 is any step of drying the granules obtained in Step 2. By removing moisture, the voids in the particles can be increased, and the carrying capacity can be increased.

From the viewpoint of suppressing a decrease in the load capacity caused by the disintegration of the particles, it is preferred to apply a drying method which does not give a strong shear force as much as possible. For example, in the case of a batch type, a method of drying in an electric dryer or a hot air dryer, a method of drying by a batch type fluidized layer, and the like may be mentioned; in the continuous type, a vibration fluid layer or a rotary drying method may be mentioned. Machine, steam tube dryer, etc.

The drying temperature is preferably 80 ° C or higher, more preferably 120 ° C or higher, particularly preferably 150 ° C or higher, and particularly preferably 180 ° C or higher, from the viewpoint of the drying speed. Further, when an organic binder is used as the binder, from the viewpoint of suppressing decomposition of the binder, it is preferably 300 ° C or lower, more preferably 250 ° C or lower, and particularly preferably 220 ° C or lower.

<Physical properties of particle group for surfactant loading>

The surfactant-supporting particle group of the present invention is a particle group having a structure in which a powdery material having an oil absorption capacity of at least 0.4 ml/g or more is agglomerated at least in addition to the clay mineral. Therefore, there are two supporting positions of (1) a large gap between the powder raw materials and (2) a small gap (for example, a gap of 10 μm or less) in the powder raw material. Among them, both (1) and (2) have a great influence on the load capacity and the load capacity, and (1) have a large influence on the load speed, and by adjusting the two load positions, it is possible to obtain the required A particle group for supporting a carrier for carrying capacity.

Further, when the clay mineral is blended, the liquid surfactant composition can be carried between the layers, and therefore it is expected that the supporting force can be improved.

The surfactant-supporting particle group of the present invention from the viewpoint of ensuring the supporting capacity of the liquid surfactant composition and ensuring a high bulk density after supporting the liquid surfactant composition The bulk density is 550 g/l or less, preferably 400 to 550 g/l, more preferably 400 to 500 g/l. It is considered that the lower bulk density of the supported particle group of the present invention can be achieved by granulation by the above-described low shear granulator.

Moreover, from the viewpoint of dusting property and solubility in a detergent composition containing a detergent particle group in which a surfactant-supporting particle group is supported by a surfactant-supporting particle group, The average particle diameter of the particle group for carrying is preferably from 140 to 600 μm, more preferably from 200 to 500 μm, particularly preferably from 200 to 400 μm.

The liquid surfactant composition of the surfactant-supporting particle group preferably has an oil absorbing ability of 0.4 ml/g or more, from the viewpoint of increasing the allowable range of the amount of the liquid surfactant composition. Preferably, it is 0.45 ml/g or more, and particularly preferably 0.5 ml/g or more. It is considered that the higher oil absorption capacity of the supported particle group of the present invention can be achieved by granulation by the above-described low shear granulator.

From the viewpoint of increasing the supporting capacity of the liquid surfactant composition of the particle group, the amount of water measured by the infrared moisture meter of the surfactant-supporting particle group is preferably as small as possible, and preferably 15 The weight % or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less.

The specific composition of the surfactant-supporting particle group of the present invention is, for example, a powder having a bulk density of 550 g/l or less and having an oil absorption capacity of 0.4 ml/g or more in addition to the clay mineral. 40 to 95% by weight, clay mineral powder is 0 to 45% by weight, binder is 0 to 35% by weight, and water is 0 to 15% by weight.

Further, the bulk density, the average particle diameter, the oil absorbing ability of the liquid surfactant composition, and the moisture content can be measured by the method described in the measurement method of the physical property described later.

<Composition and physical properties of detergent particles>

The detergent particle group of the present invention is a surfactant-supporting particle group of the present invention (that is, the surfactant-supporting particle group obtained by the production method of the present invention and the above-described surfactant of the present invention) A high bulk density detergent particle group in which a surfactant group is supported by a particle group.

Further, as long as the detergent particle group of the present invention contains the surfactant-supporting particle group of the present invention, it may be used singly or in combination with a surfactant-supporting particle group obtained by another method such as spray drying. . Further, when used in combination, a mixture of the particle group of the present invention and a particle group of another method such as spray drying may be treated as a surfactant-supporting particle group.

In the surfactant composition, for example, an anionic surfactant and a nonionic surfactant may be used alone, but it is more preferable to use them after mixing them. In particular, when a nonionic surfactant having a melting point of 30 ° C or less is used, it is preferred to use a melting point of 45 to 100 ° C and a molecular weight of 10,000 to 30,000 in order to increase the melting point of the surfactant. A water-soluble nonionic organic compound (hereinafter referred to as a melting point increasing agent) or an aqueous solution thereof. In addition, examples of the melting point-increasing agent which can be used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and a Pluronic-type nonionic surfactant. Further, an amphoteric surfactant or a cationic surfactant may be used in combination with the purpose. Further, from the viewpoint of improving the dispersibility of the detergent particle group in the low-temperature water, an anionic property such as an alkylbenzenesulfonate of preferably 5 to 25% by weight may be blended in the detergent particle group. Surfactant.

As the surfactant composition, for example, one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. As the anionic surfactant, an alkylbenzenesulfonate, an alkyl or alkenyl ether sulfate, an α-olefinsulfonate, an α-sulfofatty acid salt or an ester thereof, an alkyl or alkenyl ether carboxylate can be exemplified. An acid salt, an amino acid type surfactant, an N-mercapto amino acid type surfactant, and the like. Particularly preferred is a linear alkylbenzenesulfonate, an alkylsulfate or an alkylether sulfate. Preferred examples of the counterion are alkali metals such as sodium and potassium, and amines such as monoethanolamine and diethanolamine.

Further, in order to obtain a defoaming effect, a fatty acid salt can be used in combination.

As the nonionic surfactant, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl or alkenylphenyl ether, polyoxyethylene polyoxypropylene alkyl or alkenyl ether, and trademark Prang are mentioned. Nickel is represented by polyoxyethylene polyoxypropylene diol, polyoxyethylene alkylamine, higher fatty acid alkanolamine, alkyl glycoside, alkyl glucoside, alkyl amine oxide and the like. Among them, those having higher hydrophilicity and having a lower liquid crystal forming ability when mixed with water or having no liquid crystal are preferable, and a polyoxyalkylene alkyl group or an alkenyl ether is particularly preferable. Preferred are ethylene oxide (hereinafter referred to as EO (ethylene oxide)) adduct, EO adduct of another alcohol, and propylene oxide (hereinafter PO (propylene oxide)) adduct. As the order of addition, it is preferred to use addition EO and then add PO, add PO and then add EO, or randomly add EO and PO; as a particularly good addition order, After the block is added to EO, the block is added to PO, and the block is added to EO to obtain the following formula: RO-(EO) _X -(PO) _Y -(EO) _Z -H [formula Wherein R is a hydrocarbon group, preferably an alkyl group or an alkenyl group, EO is an oxyethylene group, PO is an oxypropylene group, and X, Y and Z represent an average addition molar number, respectively.

Among them, regarding the relationship of the best average addition molar number, X>0, Z>0, X+Y+Z=6~14, X+Z=5~12, Y=1~4.

The cationic surfactant may, for example, be a quaternary ammonium salt such as an alkyltrimethylammonium salt.

Examples of the amphoteric surfactant include those of the carbonyl betaine type and the sulfobetaine type.

The amount of the anionic surfactant in the surfactant composition is preferably from 0 to 300 parts by weight, more preferably from 20 to 200 parts by weight, based on 100 parts by weight of the nonionic surfactant. It is 30 to 180 parts by weight. The amount of the melting point-increasing agent of the nonionic surfactant is preferably from 1 to 100 parts by weight, more preferably from 5 to 50 parts by weight, per 100 parts by weight of the nonionic surfactant. Within this range, the composition has a viscosity of 10 Pa at a temperature above the pour point of the composition. s below, better is 5 Pa. s below, especially good is 2 Pa. The temperature range below s, and having a temperature lower than the pour point of the composition and higher than the melting point of the nonionic surfactant, the entry hardness of the composition is preferably 10 kPa or more, more preferably It is a temperature range of 30 kPa or more, particularly preferably 50 kPa or more, whereby the handling property of the composition and the detergent particle group is good, and the nonionic surfactant can be suppressed when the detergent particle group is stored. It oozes out and is therefore more suitable.

The physical property value of the surfactant composition can be determined by the following method. The flow point can be measured by the method of JIS K 2269. The melting point of the FP800 Thermo System, "Mettler FP81" (manufactured by Mettler Instrumente AG), was measured at a temperature increase rate of 0.2 ° C / min. The viscosity can be determined by measuring the conditions using a B-type viscometer ("DVM-B type" manufactured by TOKYO KEIKI Co., Ltd.) and rotor No. 3, 60 r/min. Also, the measured value under this condition exceeds 2 Pa. When it was impossible to measure s, it was measured by the conditions of rotor No. 3 and 12 r/min. Into the hardness system, a rheometer ("NRM-3002D", manufactured by Immobility Co., Ltd.) and a circular adapter (No. 3, 8Φ) with a diameter of 8 mm and a bottom area of 0.5 cm ² were used. The value obtained by dividing the load at 20 mm/min into the interior of the surfactant composition by 20 mm divided by the bottom area of the circular adapter.

The amount of the surfactant composition added is preferably from 10 to 100 parts by weight, more preferably from 20 to 100 parts by weight, based on 100 parts by weight of the surfactant-supporting particle group, from the viewpoint of the cleaning property and the solubility. The range of ~80 parts by weight is particularly preferably in the range of 30 to 60 parts by weight.

When the surfactant composition and the surfactant-supporting particle group are mixed, if necessary, a powder material other than the powder material may be added, and the amount of addition is preferably 100 parts by weight based on the particle group. It is 0 to 150 parts by weight. As the raw material of the powder, for example, an aluminosilicate or a crystalline citrate such as PURIFEED (manufactured by Tokuyama Siltech Co., Ltd.) can be mentioned.

Preferred physical properties of the detergent particle group of the present invention are as follows.

The bulk density is preferably from 500 to 1000 g/l, more preferably from 600 to 1000 g/l, particularly preferably from 650 to 900 g/l. The average particle diameter is preferably from 150 to 500 μm, more preferably from 180 to 400 μm.

In addition, the above-mentioned bulk density and average particle diameter can be measured by the method described in the measuring method of the physical property mentioned later.

<Preparation method of detergent particle group>

A suitable method for obtaining a detergent particle group comprises the following step (I), and optionally, step (II).

Step (I): the surfactant composition and the particle group containing the surfactant-supporting particle group obtained by the production method of the present invention are carried out under the conditions that the surfactant composition is in the form of a liquid or a slurry. The step of mixing.

Step (II): a step of mixing the mixture obtained in the step (I) with a surface coating agent, and coating the surface of the obtained detergent particle group with the surface coating agent. Among them, step (II) can also be chopped at the same time.

1. Step (I)

As a method of supporting the surfactant composition in the particle group for supporting, for example, a method of mixing a particle group for supporting and a surfactant composition using a batch type or a continuous type mixer can be mentioned. Here, when it is carried out in a batch mode, as a method of being introduced into a mixer, the following method may be employed: (1) First, a carrier particle group is added to a mixer, and then a surfactant composition is added together; (2) repeatedly adding the supporting particle group and the surfactant composition to the mixer one by one; (3) putting one of the supporting particle groups into the mixer, and then repeatedly The remaining particle group for loading and the surfactant composition are added.

In the surfactant composition, even if it is heated to a temperature within a practical temperature range, for example, 50 to 90 ° C, it may exist as a solid or a slurry, and the dispersion or dissolution may be previously made to a low viscosity. A non-ionic surfactant, a nonionic surfactant aqueous solution or water is used to prepare a mixed solution or an aqueous solution of the surfactant composition, and is added to the supporting particle group in the form of the mixed solution or the aqueous solution. . By this method, a surfactant composition which exists in a solid or slurry form can also be easily added to the particle group for supporting. The mixing ratio of the less viscous surfactant composition or water, and the solid or slurry-like surfactant composition is preferably as long as it is a range in which the obtained mixed solution or aqueous solution can be sprayed.

As for the preparation method of the above mixed liquid, for example, a method of adding a solid or slurry-like surfactant composition to a surfactant having a low viscosity or water, or mixing the same; or a interface having a low viscosity In the active agent or in water, an acid precursor of the surfactant, for example, an acid precursor of an anionic surfactant, is neutralized with an alkaline agent (for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide) to prepare an interface. A method of mixing a mixture of active agents.

Further, in this step, an anionic property may be added before the addition of the surfactant composition, at the same time as the addition of the surfactant composition, during the addition of the surfactant composition, or after the addition of the surfactant composition. The acid precursor of the surfactant. By adding an acid precursor of an anionic surfactant, the surfactant can be highly formulated, the loading capacity of the supporting particle group, the loading capacity control, and the nonionic interfacial activity of the detergent particle group can be improved. The physical properties and quality of the agent such as bleed out inhibition and fluidity.

Examples of the acid precursor which can be used in the anionic surfactant of the present invention include alkylbenzenesulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefinsulfonic acid, and α-sulfonate. Fatty acid, alkyl or alkenyl ether carboxylic acid, fatty acid, and the like. From the viewpoint of improving the fluidity of the detergent particle group, it is particularly preferable to add a fatty acid after adding a surfactant.

The amount of the acid precursor of the anionic surfactant is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight, particularly preferably from 1 to 100 parts by weight based on 100 parts by weight of the supported particle group. 10 parts by weight, particularly preferably 1 to 5 parts by weight. Further, as a method of adding the acid precursor of the anionic surfactant, it is preferably supplied as a liquid at a normal temperature in the form of a spray, or may be added as a solid at a normal temperature in a powder form, or may be melted after being melted. Spray supply. Among them, when the powder is added, it is preferred to raise the temperature of the detergent particle group in the mixer to a temperature at which the powder is melted.

Specific examples of the preferred mixing device include the following devices. When it is carried out in batch mode, it is preferably the following (1) to (3). (1) Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), high-speed mixer (manufactured by Shenjiang Industrial Co., Ltd.), vertical granulator (manufactured by POWREX), and LODIGE mixer (manufactured by the Japanese Patent Laid-Open No. Hei 10-296064), a mixing device described in Japanese Laid-Open Patent Publication No. Hei 10-296065 (2) Belt mixer (manufactured by Rihe Machinery Industry Co., Ltd.), batch kneading machine (manufactured by Satake Chemical Industry Co., Ltd.), Ribocone (manufactured by Okawara Seisakusho Co., Ltd.), (3) Cone A screw mixer (manufactured by HOSOKAWAMICRON Co., Ltd.), an SV mixer (manufactured by Shinko Pantec Co., Ltd.), and the like. In the above-mentioned mixer, a mixing device described in Japanese Laid-Open Patent Publication No. Hei 10-296064, and a mixing device described in Japanese Laid-Open Patent Publication No. Hei 10-296065, and the like can be used. Step (II) described later is carried out, so that it is preferable in terms of simplification of the apparatus. In the mixing device described in Japanese Laid-Open Patent Publication No. Hei 10-296064, the mixing device described in Japanese Laid-Open Patent Publication No. Hei No. H10-296065 can adjust the moisture absorption or temperature of the mixture by ventilation, thereby suppressing the surfactant. It is preferred to carry out the disintegration of the particle group. Further, in terms of suppressing the disintegration of the surfactant-supporting particle group, it is also preferable to use a conical spiral mixer or SV which can mix a powder and a liquid without imparting a strong shearing force. Mixing devices such as mixers and belt mixers.

Further, the carrier particle group and the surfactant composition may be mixed using a continuous apparatus. Further, examples of the continuous type device include a Flexo Mix type (manufactured by POWREX) and a TURBULIZER (manufactured by HOSOKAWAMICRON).

Further, when a nonionic surfactant is used in this step, it is preferred to be added to the surfactant composition before the addition of the surfactant composition, or to the addition of the surfactant composition, or After the surfactant composition is added, or in the surfactant composition, a water-soluble nonionic having a melting point of 45 to 100 ° C and a molecular weight of 10,000 to 30,000 is added in advance to increase the melting point of the surfactant. An organic compound (hereinafter referred to as a melting point increasing agent) or an aqueous solution thereof. By adding a melting point increasing agent, the agglomeration of the detergent particle group and the exudation property of the surfactant in the detergent particle group can be suppressed. Further, as the above-mentioned melting point-increasing agent, a melting point-increasing agent similar to those exemplified as the melting point-increasing agent of the composition of the above-mentioned detergent particle group can be used. The amount of the melting point-increasing agent to be used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, most preferably 1 to 3 parts by weight, per 100 parts by weight of the supported particle group. The above range is preferable in terms of suppressing aggregation between particles of the detergent particles contained in the detergent particle group, achieving high-speed solubility, and suppressing exudation or agglomeration. As a method of adding a melting point-increasing agent, a method of mixing with a surfactant in advance by any method, or adding a melting point-increasing agent after addition of a surfactant, is used to suppress exudation or agglomeration of the detergent particle group. Sex is more favorable.

It is more preferable if the temperature in the mixer of this step is raised to a point above the flow point of the surfactant composition and then mixed. Further, the pour point of the surfactant composition can be measured by the method specified in JIS K 2269. Here, the temperature to be heated may be higher than the flow point of the surfactant composition added to promote the loading of the surfactant composition, and if it is a practical range, it is preferable to exceed the flow. The temperature is 50 ° C above the pour point, and more preferably 10 ° C to 30 ° C above the pour point. Further, when an acid precursor of an anionic surfactant is added in this step, it is more preferable to increase the temperature to a temperature at which the acid precursor of the anionic surfactant can react and then mix.

The batch mixing time for obtaining a suitable detergent particle group and the average residence time in the continuous mixing are preferably from 1 to 20 minutes, more preferably from 2 to 10 minutes.

Further, when an aqueous solution of a surfactant or a water-soluble nonionic organic compound aqueous solution is added as a surfactant composition, the remaining water may be dried after mixing and/or mixing.

The powdered surfactant and/or powder builder may also be added before, during, or after the addition of the surfactant composition. By adding a powder builder, the particle size of the detergent particle group can be controlled, and the cleaning power can be improved. In particular, when an acid precursor of an anionic surfactant is added, it is effective to add a powder builder which exhibits alkalinity before the addition of the acid precursor from the viewpoint of promoting the neutralization reaction. In addition, the term "powder builder" as used herein refers to a cleaning power enhancer for a powder other than a surfactant, and specifically refers to a base exhibiting metal ion chelating ability such as zeolite or citrate, or carbonic acid. Sodium, potassium carbonate and the like exhibit base properties, base metal chelating ability such as crystalline citrate. The base has a basic ability, and other bases such as sodium sulfate which improve the ionic strength.

Here, as the crystalline powder builder, the following materials can be used as the preferred powder builder: Japanese Patent Laid-Open No. Hei 5-279013, column 3, line 17 (particularly, at 500 to 1000 ° C) Japanese Patent Laid-Open No. Hei 7-89712, No. 2, line 45, Japanese Patent Laid-Open No. 60-227895, page 2, right lower column, line 18 (excellent is the first The crystalline bismuth salt described in Table 2, citrate). Here, the SiO ₂ /M ₂ O (wherein M represents an alkali metal) of the alkali metal ruthenate can be preferably used in an amount of from 0.5 to 3.2, preferably from 1.5 to 2.6.

The amount of the powder builder used is preferably from 0.5 to 12 parts by weight, more preferably from 1 to 6 parts by weight, per 100 parts by weight of the particle group for supporting. When the powder builder for the detergent is in this range, the solubility is good.

Further, it is preferred to add a step (II) of surface modification of the detergent particle group after the step (I).

2. Step (II)

In the present invention, in order to modify the surface of the particles of the detergent particle group carrying the surfactant by the step (I), one or more steps may be added as the following in the form of addition (1). Step (II) of various surface coating agents such as fine powder and (2) liquid.

When the surface of the particles of the detergent particle group of the present invention is coated, the fluidity and the blocking resistance of the detergent particle group tend to be improved. Therefore, it is preferred to provide a surface modification step. The apparatus used in the step (II) is, for example, preferably a device having both a stirring blade and a chopping wing in the mixer exemplified in the step (I). The surface coating agents are separately described below.

(1) Micropowder

As the fine powder, it is preferred that the primary particles have an average particle diameter of 10 μm or less, more preferably 0.1 to 10 μm. When the average particle diameter is within this range, the coverage of the surface of the particles of the detergent particle group is improved, and it is suitable from the viewpoint of improving the fluidity and blocking resistance of the detergent particle group. The average particle diameter of the fine powder can be measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba Seisakusho Co., Ltd.), or a measurement using a microscope. Further, in terms of the cleaning power, it is preferred that the fine powder has a high ion exchange capacity and a high basic ability.

As the fine powder, an aluminosilicate is preferable, and both crystalline and amorphous may be used. In addition to aluminosilicates, fine powders such as sodium sulfate, calcium citrate, cerium oxide, bentonite, talc, clay, amorphous cerium oxide derivatives, and crystalline silicates are also preferred. Further, a metal soap having a primary particle diameter of 0.1 to 10 μm, a powder surfactant (for example, an alkyl sulfate or the like), or a water-soluble organic salt may be used in the same manner. When the crystalline decanoate is used, it is preferably mixed with the fine powder other than the crystalline citrate, for the purpose of preventing deterioration due to aggregation or the like due to moisture absorption or carbon dioxide absorption of the crystalline citrate. Use it.

The amount of the fine powder to be used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 2 to 20 parts by weight, per 100 parts by weight of the detergent particles. When the amount of the fine powder used is within this range, the fluidity can be improved, and a good feeling of use can be brought to the consumer.

(2) liquid

The liquid material may, for example, be a water-soluble polymer or a fatty acid, and may be added in an aqueous solution or in a molten state.

(2-1) Water soluble polymer

Examples of the water-soluble polymer include carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, a copolymer of acrylic acid and maleic acid, and a polycarboxylate such as a salt thereof. The amount of the water-soluble polymer to be used is preferably from 0.5 to 10 parts by weight, more preferably from 1 to 8 parts by weight, particularly preferably from 2 to 6 parts by weight, per 100 parts by weight of the detergent particles. . When the amount of the water-soluble polymer used is within this range, a detergent particle group exhibiting good solubility, good fluidity, and blocking resistance can be obtained.

(2-2) fatty acids

The fatty acid may, for example, be a fatty acid having 10 to 22 carbon atoms. The amount of the fatty acid used is preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the detergent particles. When it is solid at normal temperature, it is preferred to carry out the spray supply after heating to a temperature at which fluidity is exhibited.

<detergent composition>

The detergent composition of the present invention contains the above-mentioned detergent particle group composition, and further contains a detergent component (for example, builder particles and fluorescent light) added in addition to the detergent particle group. A composition of dyes, enzymes, perfumes, antifoaming agents, bleaching agents, bleach activators, and the like.

In terms of cleaning power, the content of the detergent particle group in the detergent composition is preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more, particularly preferably It is 80% by weight or more and 100% by weight or less.

The content of the detergent component other than the detergent particle group in the detergent composition is preferably 50% by weight or less, more preferably 40% by weight or less, particularly preferably 30% by weight or less, particularly preferably It is 20% by weight or less.

<Preparation method of detergent composition>

The method for preparing the detergent composition is not particularly limited, and examples thereof include a method of mixing the detergent particles and the detergent component added. Since the detergent composition thus obtained contains the detergent particles having a large carrier capacity of the surfactant, a sufficient cleaning effect can be exhibited even in a small amount. The use of the detergent composition is not particularly limited as long as it is used as a powder detergent, and examples thereof include a powder detergent for clothing, a detergent for automatic tableware, and the like.

<Method for measuring physical properties> Bulk density

The bulk density can be measured by the method specified in JIS K 3362.

2. Average particle size

The average particle diameter can be measured by the following two methods.

(1) For an average particle diameter of 80 μm or more, a standard sieve (mesh 2000 to 125 μm) of JIS K 8801 was used to vibrate for 5 minutes, and then the median diameter was calculated from the weight fraction of the mesh size. In more detail, use a sieve with a mesh of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm and a tray, on the tray from the mesh The small sieve was stacked in order, and 100 g of particles were added to the top 2000 μm sieve and capped, and mounted on a rotary tapping sieve shaker (manufactured by HEIKO Co., Ltd., tapping 156 times/min) , rolling: 290 times / minute), after vibrating for 5 minutes, the weight of the particles remaining on each sieve and tray was measured, and the weight ratio (%) of the particles on each sieve was calculated. . The weight ratio of the particles on the sieve having a smaller mesh size was sequentially accumulated from the tray, and a total particle diameter of 50% was taken as the average particle diameter.

In addition, for those with an average particle size of 125 μm or less, mesh 45 μm, 63 μm, 90 μm, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 are used. The average particle size was calculated by performing the same measurement on the 12-mesh sieve of μm and the tray.

(2) For those having an average particle diameter of less than 80 μm, the laser diffraction/scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) is used to disperse the above particles in a solvent which does not dissolve the particles. The median diameter determined was taken as the average particle diameter. Further, regarding (2), it is also possible to measure 150 μm or less.

3. Moisture

The moisture measurement of the particle group can be carried out by an infrared moisture meter method. That is, 3 g of the sample was weighed and collected in a test dish having a known weight, and heated at 200 ° C using an infrared moisture meter (FD-240 manufactured by Kett Electric Laboratory) for 30 seconds. The point at which the weight does not change is regarded as the end of drying. Further, the amount of moisture is calculated from the weight after drying and the weight before drying.

4. Liquidity

The flow time is the time required to discharge 100 mL of the powder from the bulk density measuring funnel specified in JIS K 3362. The flow time is preferably 10 seconds or less, more preferably 8 seconds or less, and particularly preferably 7 seconds or less.

<Quality evaluation method> 1. Oil absorption capacity

A powder of 30 to 35 g was placed in an absorption measuring device (S410 manufactured by Asahisouken Co., Ltd.) to rotate the driving blade at 200 r.p.m. A liquid nonionic (EMULGEN 108 manufactured by Kao) was added dropwise at a liquid supply rate of 4 ml/min to discriminate the point at which the maximum torque was reached. The amount of liquid added at the torque point of 70% of the point at which the maximum torque is reached is divided by the amount of powder input as the oil absorption capacity.

2. Particle size distribution

The detergent particle group passing through a sieve of 1410 μm was fitted, and the Rosin-Rammler number was calculated and used as an index of the particle size distribution. The following formula can be used to calculate the Rosin-Rammler number.

Log(log(100/R(Dp)))=nlog(Dp/De)

R(Dp): cumulative rate of powder with a particle size above Dp μm [%]

Dp: particle size [μm]

De: average particle size [μm]

n: Rosin-Rammler number

The higher the Rosin-Rammler number n, the narrower the particle size distribution. As n, it is preferably 1.0 or more, more preferably 1.5 or more.

3. Solubility

As the solubility index of the present invention, a 60-second dissolution rate of the detergent particle group described below can be used. The dissolution rate is preferably 90% or more, more preferably 95% or more. Further, the detergent composition can also be evaluated in the same manner.

The 60 second dissolution rate of the detergent particle group was calculated by the following method.

1L hard water (Ca/Mg molar ratio 7/3) cooled to 5 °C with a hardness of 71.2 mg CaCO ₃ /L is filled with a 1 L beaker (cylinder with an inner diameter of 105 mm and a height of 150 mm, for example, Yancheng Glass) In the 1L glass beaker manufactured by the company, the water temperature of 5 °C is kept fixed in a water bath, and a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) SA) is used. (Circular type)), the vortex depth was stirred at a rotation speed (800 rpm) of approximately 1/3 of the water depth. Under stirring, it will be reduced. The amount of detergent particles that have reached 1.0000±0.0010g is put into the pile. Disperse in water and continue to stir. After 60 seconds from the input, the detergent particle group dispersion in the beaker was filtered using a standard sieve (diameter 100 mm) of a mesh size of 7 μm as defined by JIS Z 8801, which is known to have a water content remaining on the sieve. The detergent particle population is recovered with the sieve into an open container of known weight. Further, the operation time from the start of filtration until the recovery of the sieve was 10 ± 2 seconds. The dissolved residue of the collected detergent particles was dried by an electric dryer heated to 105 ° C for 1 hour, and then cooled in a desiccator (25 ° C) charged with silicone for 30 minutes. After cooling, the total weight of the dissolved detergent, the sieve, and the recovery container was measured, and the dissolution rate (%) of the detergent particle group was calculated by the formula (1).

Solubility (%) = {1 - (T / S)} × 100 (1) S: input weight of the detergent particle group (g) T: when the aqueous solution obtained under the above stirring conditions is supplied to the above sieve, Dry weight (g) of the residue of the detergent particle group remaining on the sieve (drying conditions: after holding at a temperature of 105 ° C for 1 hour, holding in a desiccator (25 ° C) charged with silicone for 30 minutes )

4. Particle yield

The particle yield of the present invention is determined by the ratio of particles of a particular particle size range in all of the particles. For example, the particle yield of 125-1000 μm refers to the ratio of particles of 125 μm or more and 1000 μm or less in all the particles.

5. Detergent yield

The detergent yield of the present invention refers to a ratio of particles of 1180 μm or less in the detergent composition obtained by mixing the detergent particle group and the detergent component additionally added.

Example

In the present examples, the following raw materials were used unless otherwise specified.

Light soda ash 1: average particle size 100 μm (manufactured by CENTRAL GLASS, oil absorption capacity 0.45 ml/g)

Light soda ash 2: average particle size 175 μm (manufactured by CENTRAL GLASS, oil absorption capacity 0.69 ml/g)

Clay mineral: Laundrosil DGA Powder(S Made by d-Chemie)

Sodium polyacrylate: weight average molecular weight 10,000 (made by Kao)

Heavy soda ash: average particle size 290 μm (manufactured by CENTRAL GLASS)

Sodium sulfate: anhydrous neutral thenardite (made by Shikoku Chemical Co., Ltd.)

Example 1

Mixing clay mineral 2.1 kg with light soda ash 1 in a 70 L drum type granulator with separator (Φ 40 cm × L60 cm / speed 32 rpm / Phlox 0.23) (clay mineral / powder raw material = 3 /7). After mixing for 2 minutes, a 1 fluid nozzle (manufactured by Spraying Systems-Japan: a spray pressure of 0.4 MPa) was used, and 2.5 kg of water was added over 3 minutes. After the addition, after granulation for 3 minutes, it was discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.1% by weight.

The obtained particle group 1 was a particle group having an average particle diameter of 204 μm and a bulk density of 490 g/l, and the oil absorption capacity was 0.52 ml/g. Further, the particle yield of 125-1000 μm was 56%, and the Rosin-Rammler number was 1.0.

Example 2

Mixing clay mineral 2.1 kg with light soda ash 1 in a 70 L drum granulator with a separator (Φ40 cm × L60 cm / speed 32 rpm / Phlox 0.23) (clay mineral / powder raw material = 1) /2). After mixing for 2 minutes, a 2 fluid nozzle (manufactured by Spraying Systems-Japan: a spray pressure of 0.15 MPa / a spray of 0.3 MPa for atomization air) was used, and 3.8 kg of a 25% sodium polyacrylate aqueous solution was added over 5 minutes. After the addition, after granulation for 3 minutes, it was discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.3% by weight.

The obtained particle group 2 was a particle group having an average particle diameter of 320 μm and a bulk density of 495 g/l, and the oil absorption capacity was 0.51 ml/g. Further, the particle yield of 125-1000 μm was 56%, and the Rosin-Rammler number was 1.6.

Example 3

Mixing clay mineral 2.1 kg with light soda ash 2 in a 70 L drum granulator with a separator (Φ40 cm × L60 cm / speed 32 rpm / Phlox 0.23) (clay mineral / powder raw material = 1) /2). After mixing for 2 minutes, a 25% sodium polyacrylate aqueous solution of 3.8 kg was added using a 2 fluid nozzle for 5 minutes. After the addition, after granulation for 3 minutes, it was discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 0.9% by weight.

The obtained particle group 3 was a particle group having an average particle diameter of 390 μm and a bulk density of 430 g/l, and the oil absorption capacity was 0.58 ml/g. Further, the particle yield of 125-1000 μm was 93%, and the Rosin-Rammler number was 2.5.

Manufacturing example 1

375 parts by weight of water was added to the mixing tank, and after the water temperature reached 35 ° C, 127 parts by weight of sodium sulfate, 5 parts by weight of sodium sulfite, and 1 part by weight of a fluorescent dye were added, and the mixture was stirred for 10 minutes. 127 parts by weight of sodium carbonate was added, 75 parts by weight of a 40% by weight aqueous solution of sodium polyacrylate was added, and the mixture was stirred for 10 minutes to prepare a first preparation liquid. 24 parts by weight of sodium chloride as a fine crystal precipitation agent was added to the first preparation liquid, and stirred for 10 minutes. Further, 266 parts by weight of zeolite was added and stirred for 30 minutes to obtain a homogeneous second preparation liquid (the slurry moisture content was 42% by weight).

The second preparation liquid was supplied to a spray drying tower (convection type) by a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle provided near the top of the tower. The high-temperature gas supplied to the spray drying tower was supplied from the lower portion of the tower at a temperature of 200 ° C and discharged at 90 ° C from the top of the tower. The moisture of the obtained particle group 4 was 4% by weight. The obtained particle group was a particle group having an average particle diameter of 285 μm and a bulk density of 476 g/l.

Example 5

100 parts by weight of light soda ash 1 and 0.6 parts by weight of clay mineral in a 70 L drum type granulator with a separator (Φ 40 cm × L60 cm / rotation speed 32 rpm / Phlox number 0.23), using a 2-fluid nozzle 55.9 parts by weight of a 35% sodium polyacrylate aqueous solution was added over 5.5 minutes. After the addition, after granulation for 3 minutes, it was discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.0% by weight.

The obtained particle group 5 was a particle group having an average particle diameter of 317 μm and a bulk density of 489 g/l, and the oil absorption capacity was 0.51 ml/g. Further, the particle yield of 125-1000 μm was 97%, and the Rosin-Rammler number was 2.9.

Example 6

100 parts by weight of light soda ash 1 in a 70 L drum type granulator with a separator (Φ 40 cm × L60 cm / rotation speed 32 rpm / Phlox number 0.23) 'Add 35% polymerization in 5.5 minutes using a 2-fluid nozzle The aqueous sodium acrylate solution was 55.6 parts by weight. After the addition, after granulation for 3 minutes, it was discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 0.9% by weight.

The obtained particle group 6 was a particle group having an average particle diameter of 328 μm and a bulk density of 448 g/l, and the oil absorption capacity was 0.61 ml/g. Further, the particle yield of 125-1000 μm was 95.2%, and the Rosin-Rammler number was 2.5.

Example 8

The surfactant composition (polyoxyethylene alkyl ether/polyethylene glycol/sodium alkylbenzenesulfonate/water = 42/8/42/8 (weight ratio)) was adjusted to 80 °C. Then, 100 parts by weight of the obtained surfactant-supporting particle group 3 was charged into the LODIGE Mixer (manufactured by Matsusaka Techno Co., Ltd., capacity: 130 L, with a casing), and the spindle was started (stirring blade, rotation speed: 60 rpm) , circumferential speed: 1.6 m / s). Further, warm water of 80 ° C was allowed to flow to the casing at 10 L/min. 50 parts by weight of the above surfactant composition was added thereto over 2 minutes, followed by stirring for 5 minutes. Further, 6 parts by weight of amorphous aluminosilicate was charged, and a spindle (rotation speed: 120 rpm, peripheral speed: 3.1 m/s) and a chopper were rotated for 1 minute (rotation speed: 3600 rpm, peripheral speed: 28 m/ The mixture of s) is discharged, and the detergent particle group 1 is discharged.

The obtained detergent particle group 1 was a particle group having an average particle diameter of 481 μm, a bulk density of 800 g/l, and a fluidity of 5.8 s.

Example 9

Using the surfactant-supporting particle group 3 produced in Example 3 and the surfactant-supporting particle group 4 obtained by spray drying in Production Example 1, a detergent was produced by the method described below. Particle swarm 2.

The surfactant composition (polyoxyethylene alkyl ether/polyethylene glycol/sodium alkylbenzenesulfonate/water = 42/8/42/8 (weight ratio)) was adjusted to 80 °C. Then, 50 parts by weight of the obtained surfactant-supporting particle group 3, 50 parts by weight of the surfactant carrier for the LODIGE Mixer (manufactured by Matsusaka Techno Co., Ltd., 130 L, jacketed) was charged. Particle group 4, and stirring of the spindle (stirring wing, rotation speed: 60 rpm, peripheral speed: 1.6 m/s) was started. Further, warm water of 80 ° C was allowed to flow to the casing at 10 L/min. 50 parts by weight of the above surfactant composition was added thereto over 2 minutes, followed by stirring for 5 minutes. Further, 6 parts by weight of amorphous aluminosilicate was charged, and a spindle (rotation speed: 120 rpm, peripheral speed: 3.1 m/s) and a chopper were rotated for 1 minute (rotation speed: 3600 rpm, peripheral speed: 28 m/ The mixture of s) is discharged to discharge the detergent particle group 2.

The obtained detergent particle group 2 was a particle group having an average particle diameter of 342 μm and a bulk density of 807 g/l. Further, the dissolution rate was 93%, and the fluidity was 6.2 s.

Example 10

Then, the detergent particle group 3 was produced in the same manner as in Example 8 except that 100 parts by weight of the surfactant-supporting particle group 5 was used instead of the surfactant-supporting particle group 3 .

The obtained detergent particle group 3 was a particle group having an average particle diameter of 356 μm, a bulk density of 768 g/l, and a fluidity of 6.0 s.

Example 11

The detergent particle group 4 was discharged in the same manner as in Example 8 except that 100 parts by weight of the surfactant-supporting particle group 6 was used instead of the surfactant-supporting particle group 3 .

The obtained detergent particle group 4 was a particle group having an average particle diameter of 315 μm, a bulk density of 808 g/l, and a fluidity of 5.9 s.

Comparative example 1

Mixing 1.5 kg of clay mineral with 3.5 kg of light soda ash in a 10,000-horsepower machine (02 VAC manufactured by EIRICH; disc rotation speed 44 rpm; cutting wing speed 1650 rpm/Pota number 213) (clay mineral/powder raw material = 3 /7). After mixing for 2 minutes, 1.25 kg of water was added using 1 fluid nozzle for 1 minute. After the addition, after granulation for 3 minutes, it was discharged from a 10,000 horsepower machine, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.0% by weight.

The obtained particle group 9 was a particle group having an average particle diameter of 352 μm and a bulk density of 715 g/l, and the oil absorption capacity was 0.16 ml/g. Further, the particle yield of 125-1000 μm was 92%, and the Rosin-Rammler number was 2.0.

Comparative example 2

Mix 100 parts by weight of light soda ash 1 with clay mineral in a 10 L high speed mixer (manufactured by Fukae Powtec; stirrer speed 200 rpm / valgus number 8.94; chopped wing speed 3600 rpm / Phloe number 398) 42.9 parts by weight (clay mineral/powder material = 3/7). 45.3 parts by weight of a 35% sodium polyacrylate aqueous solution was added in 1 minute using a 1-fluid nozzle. After the addition, after granulation for 4 minutes, it was discharged from a granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.0% by weight.

The obtained particle group 10 was a particle group having an average particle diameter of 362 μm and a bulk density of 736 g/l, and the oil absorption capacity was 0.30 ml/g. Further, the particle yield of 125-1000 μm was 55%, and the Rosin-Rammler number was 1.5.

Comparative example 3

The detergent particle group 6 was produced in the same manner as in Example 8 except that 100 parts by weight of the surfactant-supporting particle group 10 produced in Comparative Example 2 was used instead of the surfactant-carrying particle group 3.

The obtained detergent particle group 6 is a particle group having an average particle diameter of 876 μm, a bulk density of 830 g/l, and a fluidity of 6.5 s.

Comparative example 4

Washing was carried out in the same manner as in Example 9 except that the light soda ash 1 was changed to 35 parts by weight, and the clay mineral was changed to 15 parts by weight in place of 50 parts by weight of the surfactant-supporting particle group 3; Cleaner particle group 7.

The obtained detergent particle group 7 is a particle group having an average particle diameter of 424 μm, a bulk density of 835 g/l, and a fluidity of 6.1 s.

The conditions of the above examples and the like are shown in the following table.

[Table 1] [Table 2]

According to the comparison between Example 1 and Comparative Example 1 and Comparative Example 2, it is preferable to carry out low shear granulation by performing low shear granulation, and it is preferred to obtain low shear granulation having a Phlox number of 1.0 or less. A group of particles with bulk density and oil absorption capacity.

Further, according to the second, third, fifth and sixth embodiments, according to the production method of the present invention, a particle group exhibiting desired physical properties can be obtained regardless of the content of the clay mineral, and it can be known from Examples 8 to 11 The detergent particle group of the particle group also exhibits substantially the same physical properties and quality as the particle group which becomes the corresponding raw material.

On the other hand, according to Comparative Example 3, when a particle group produced by a high shear mixer, specifically, a mixer having a Phlox number of more than 1.0 is used, it is formed in terms of quality and productivity. A detergent particle group having a poor detergent particle group of a particle group produced by a low shear mixer.

Further, according to the comparison between Example 9 and Comparative Example 4, it is understood that the detergent particle group containing the non-granulated raw material in place of the surfactant-supporting particle group of the present invention does not exhibit a good dissolution rate and contains The detergent particle group of the supported particle group of the present invention is inferior in quality. According to this result, it is shown that the granulation by low shear granulation is important for the quality of the detergent particles.

Industrial availability

According to the present invention, the surfactant-supporting particle group excellent in the supporting capacity/supporting force/loading speed of the liquid surfactant composition can be obtained without using a spray drying method.

Claims (16)

A method for producing a surfactant-supporting particle group for producing a surfactant-supporting particle group having a bulk density of 550 g/l or less, comprising the following steps 1(a) to 2: Step 1 (a) ): a step of mixing a clay mineral powder and a powder raw material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral; and Step 2: adding water or bonding to the mixed powder obtained in the step 1 (a) The aqueous solution of the agent is subjected to a granulation step using a low shear granulator having a Phlox number of 1.0 or less. A method for producing a surfactant-supporting particle group for producing a surfactant-supporting particle group having a bulk density of 550 g/l or less, comprising the following steps 1 (b) to 2: Step 1 (b) a step of mixing a powder raw material having an oil absorption capacity of 0.4 ml/g or more other than the clay mineral; and a step 2: adding water or an aqueous binder solution to the mixed powder obtained in the step 1 (b), using Fu The step of granulating a low shear granulator having a number of moles of 1.0 or less. The method for producing a surfactant-supporting particle group according to claim 1 or 2, which further comprises the step of: drying the particles obtained in the step 2; The method for producing a surfactant-supporting particle group according to claim 1 or 2, wherein a water or a binder aqueous solution is added using a multi-fluid nozzle. The method for producing a surfactant-supporting particle group according to claim 3, wherein a water or a binder aqueous solution is added using a multi-fluid nozzle. The method for producing a surfactant-supporting particle group according to claim 4, wherein the multi-fluid nozzle is a 2-fluid nozzle. The method for producing a surfactant-supporting particle group according to claim 5, wherein the multi-fluid nozzle is a 2-fluid nozzle. The method for producing a surfactant-supporting particle group according to claim 1 or 2, wherein the powder raw material comprises light soda ash. The method for producing a surfactant-supporting particle group according to claim 3, wherein the powder raw material comprises light soda ash. The method for producing a surfactant-supporting particle group according to claim 4, wherein the powder raw material comprises light soda ash. The method for producing a particle group for surfactant-supporting agent according to claim 5, wherein the powder raw material comprises light soda ash. The method for producing a particle group for surfactant-supporting according to claim 6, wherein the powder material comprises light soda ash. The method for producing a surfactant-supporting particle group according to claim 7, wherein the powder raw material comprises light soda ash. A particle carrier-supporting particle group produced by the production method according to any one of claims 1 to 13, which has a bulk density of 550 g/l or less, and contains the following components: oil absorption ability other than clay minerals Powder material of 0.4 ml/g or more: 40 to 95% by weight of clay mineral powder: 0 to 45% by weight of binder: 0 to 35% by weight of water: 0 to 15% by weight. A high bulk density detergent particle group containing the surfactant-supporting particle group produced by the production method according to any one of claims 1 to 13 or the surfactant-supporting particle of claim 14. The particle group of the group is supported by a surfactant composition. A detergent composition comprising the detergent particle group of claim 15.