JP4401768B2 - Manufacturing method of detergent particles - Google Patents

Description

  The present invention relates to a method for producing detergent particles obtained by dry neutralizing an acid precursor of a non-soap anionic surfactant with base granules.

  Many detergents based on non-soap anionic surfactants such as alkylbenzene sulfonates have been produced. As a method for producing such detergent particles, instead of directly adding a surfactant, the acid precursor of the non-soap anionic surfactant is used in place by a water-soluble solid alkaline inorganic material such as sodium carbonate. There is a dry neutralization method.

  For example, in a high speed mixer / granulator, after dry neutralization at a temperature of 55 ° C. or less, a method for producing a detergent composition granulated by adding a liquid binder (Patent Document 1), in a high speed mixer / granulator, 55 A method for producing a detergent composition that is granulated by adding a liquid binder after dry neutralization at a temperature of ℃ or higher (Patent Document 2), followed by dry neutralization with a continuous high-speed mixer, followed by high bulk density with a medium-speed mixer, followed by cooling And the manufacturing method (patent document 3) of the detergent composition granulated by drying is disclosed.

  However, when detergent particles are produced by these methods, in order to prevent the particles from agglomerating / coarse due to the adhesiveness of the non-soap anionic surfactant produced by neutralization, it is necessary to understand the mixing mechanism. It is necessary to operate the cutting mechanism for crushing / dispersing at a high speed and to maintain it in the form of particles. In this case, it is possible to produce detergent particles having a desired small particle size by optimizing the stirring / cutting conditions, but it is difficult to obtain a good yield, and the particle size distribution of the obtained particles is also It will be wide. In addition, with respect to solubility, in the conventional method as described above, there are relatively many agglomerated particles of the starting material in which the non-soap anionic surfactant serves as a binder, and it is not easy to improve the solubility. Absent.

  As a method for solving these problems, by containing an inorganic acid in the acid precursor, the adhesiveness of the non-soap anionic surfactant is suppressed, and the content of the anionic surfactant is increased. Has been disclosed, and a production method for obtaining detergent particles having a small particle size with high yield is disclosed (Patent Document 4). Further, a production method is disclosed in which water is added as a reaction initiator and a reaction accelerator during neutralization so that unreacted acid precursor does not function as a binder and suppresses the formation of dumplings (Patent Document). 1). However, the situation is similar in the case where the aggregate is crushed to a small particle size by stirring / cutting, and there is room for improvement in terms of yield, sharpening of the particle size distribution, and solubility.

  As described above, the method by dry neutralization is a method suitable for easily producing a detergent particle group mainly composed of an anionic surfactant, but it is possible to granulate while agglomerating raw materials. Basically, when the anionic surfactant is blended in a high amount, due to its strong binder power, agglomeration proceeds, making it difficult to reduce the particle size and reducing the granulation yield. Even if a relatively small particle size range is obtained by crushing, it is difficult to obtain a detergent particle group having a sharp particle size distribution and excellent solubility with a high yield.

On the other hand, Patent Documents 5 and 6 describe that a surfactant may be added to improve the drying efficiency. As an example, 2 to 4% by weight of sodium dodecylbenzenesulfonate is blended. Yes. However, in Patent Documents 7 and 8, by adding a surfactant, a coating tends to be formed on the surface of the resulting granule group, and the absorption rate for the liquid surfactant composition tends to decrease. It is said that it is preferable not to contain substantially. When no surfactant is blended, an amorphous coating composed of a water-soluble polymer and a water-soluble inorganic salt is formed on the surface of the granules obtained unless a coating formation inhibitor or the like is blended.
JP-A-3-33199 JP-A-4-363398 JP-A-3-146599 International Publication No. 98/10052 pamphlet WO99 / 29830 pamphlet International Publication No. 00/077160 Pamphlet International Publication No. 00/077148 Pamphlet International Publication No. 00/077158 Pamphlet

Therefore, as a result of various studies on the above points, the present inventors have a merit of improving fluidity in addition to improving the appearance by sharpening the particle size distribution in the detergent, Non-soap anionic surfactant-based detergents are often used in hand-washing laundry, and we have discovered that there is an unexpected synergistic effect that there is a merit to improve usability by improving solubility did.
Furthermore, by adding a very small amount of a specific surfactant to the slurry before spray drying and performing spray drying, it is surprisingly suitable for dry neutralization in which the coating film is defective or the surface is rough. It was found that a large base granule group was obtained, and a high content of an anionic surfactant could be obtained.

  Accordingly, an object of the present invention is to provide a mononuclear detergent having a sufficient bulk density for use in a compact detergent and having a high blend of an anionic surfactant by dry neutralization and excellent fluidity and solubility. The object is to provide a method for producing particles.

That is, the gist of the present invention is as follows.
Step (I): containing a water-soluble polymer, a water-soluble inorganic salt and 0.0005 to 1% by weight of an anionic surfactant [component (a)] having a sulfate group or a sulfonate group, and a crystalline aluminosilicate Preparing a slurry of 10% by weight or less,
Step (II): a step of preparing the base granule group [component (b)] by spray drying the slurry obtained in the step (I),
Step (III): Step of dry neutralizing component (b) with 30-60 parts by weight of non-soap anionic surfactant acid precursor [component (c)] with respect to 100 parts by weight of component (b) And Step (IV): a step of surface modification by adding a flow aid [component (d)] to the mixture obtained in Step (III), the particle growth degree is 1.6 or less, bulk The present invention relates to a method for producing detergent particles having a density of 500 g / L or more.

  According to the method for producing detergent particles of the present invention, a large amount of anionic surfactant can be blended by dry neutralization, and a mononuclear detergent particle group excellent in cleaning performance, solubility and caking property can be obtained with high yield. An effect is produced.

  As described above, the base granule group used in the present invention contains a water-soluble polymer, a water-soluble salt, and 0.0005 to 1 part by weight of an anionic surfactant having a sulfate group or a sulfonate group, and a crystalline alumino It is obtained by spray-drying a slurry having a silicate content of 10% by weight or less. By having such a structure, the slurry has a bulk density sufficient for use in a compact detergent, and has a non-soapy shade. A group of base granules suitable for dry neutralization of acid precursors of ionic surfactants is obtained. As a result, mononuclearity with excellent fluidity and solubility with high blending of non-soap anionic surfactants The effect that the detergent particle group of this is obtained is show | played.

1. Composition of base granule group [component (b)] Examples of water-soluble polymers include organic polymers and inorganic polymers. Examples of organic polymers include carboxylic acid polymers, carboxymethylcellulose, soluble starch, Examples of inorganic polymers such as saccharides and polyethylene glycol include amorphous silicates, among which carboxylic acid polymers are preferable, and among these carboxylic acid polymers, acrylic acid- Maleic acid copolymer salts and polyacrylates (counter ions: sodium ion, potassium ion, ammonium ion, etc.) are particularly excellent. The molecular weight of these carboxylic acid-based polymers is preferably 1000 to 8000, more preferably 2000 or more and 10 or more carboxyl groups. The amount of the organic polymer is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight in the base granule group.

  From the viewpoint of improving the particle strength, it is preferable to use an organic polymer and an inorganic polymer such as amorphous silicate in combination, and particularly No. 2 sodium silicate. Combined with organic polymer and inorganic polymer from the viewpoint of easily maintaining high particle strength of the base granule group even when the anionic surfactant having a sulfate group or sulfonate group is added to the slurry. It is preferable to do. The amount of these inorganic polymers is preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably 8% by weight or less in the base granule group from the viewpoint of solubility, and further improves the particle strength. From the viewpoint, the content is preferably 2% by weight or more in the base granule group, and more preferably 5% by weight or more.

  Water-soluble salts include carbonates, hydrogen carbonates, sulfates, sulfites, hydrogen sulfates, hydrochloric acid or phosphates, etc., water-soluble inorganic salts represented by ammonium salts or amine salts, There are low molecular weight water-soluble organic salts having a molecular weight of less than 2000, such as citrate and fumarate. Of these, hydrated inorganic salts such as sodium carbonate, sodium sulfate, and sodium tripolyphosphate are preferred from the viewpoint of crystallization promotion. The amount of the water-soluble inorganic salt is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and still more preferably 20 to 60% by weight in the base granule group from the viewpoint of ionic strength.

  The anionic surfactant having a sulfuric acid group or a sulfonic acid group as the component (a) includes an alkylbenzene sulfonate having 10 to 18 carbon atoms, a linear alkylbenzene sulfonate, an alkyl sulfate having 12 to 18 carbon atoms, and poly Oxyethylene alkyl sulfates (ethylene oxide average added mole number of 0.1 to 3) are preferable, and alkali metal salts such as sodium and potassium, and amine salts such as monoethanolamine and diethanolamine are particularly preferable. Among these, a linear alkylbenzene sulfonate sodium having 12 to 14 carbon atoms is preferable because a base granule group suitable for dry neutralization in which a small amount of the coating film of the base granule group is lost or the surface is rough is obtained.

In addition, the fact that the slurry in the step (I) contains 0.0005 to 1% by weight of the component (a) is one major feature of the present invention, but the amount of the component (a) is more than 1% by weight. In some cases, a coating of the anionic surfactant as the component (a) tends to be formed on the surface of the obtained base granule group. Moreover, when not mix | blending (a) component, there exists a tendency for the film which consists of a water-soluble polymer and a water-soluble inorganic salt to be formed in the surface of the base granule group obtained if a film formation inhibitor etc. are not mix | blended.
Therefore, from the viewpoint of suppressing the film formation of the component (a), the content of the component (a) in the slurry (based on the solid content) is 1% by weight or less, preferably 0.5% by weight or less, more preferably Is 0.2% by weight or less, more preferably 0.1% by weight or less. Further, from the viewpoint of expressing the effect of generating defects in the surface coating or roughening the surface, 0.0005% by weight or more, preferably 0.001% by weight or more, more preferably 0.002% by weight or more, More preferably, it is 0.003 weight% or more. That is, the content is 0.0005 to 1 wt%, preferably 0.001 to 0.5 wt%, more preferably 0.002 to 0.2 wt%, and still more preferably 0.005 to 1 wt% in the base granule group. 003 to 0.1% by weight.

  The base granule group preferably further contains a water-insoluble inorganic substance from the viewpoint of particle strength and cleaning performance.

  Examples of water-insoluble inorganic substances include aluminosilicates, silicon dioxide, hydrated silicate compounds, perlite, and clay compounds represented by bentonite. Of these, crystalline aluminosilicates such as zeolite are preferable because they act as sequestering agents in the detergent composition.

  However, care should be taken regarding the use of zeolite because it involves dry neutralization using an anionic surfactant acid precursor. The amount of the zeolite blended may be decomposed during the dry neutralization reaction if it is blended in a large amount, and is 10% by weight or less, preferably 5% by weight or less, more preferably substantially not blended in the base granule group. . In addition, for the purpose of inhibiting decomposition, the amount can be increased by using a water-soluble alkaline agent having high solubility such as sodium hydroxide and high alkali strength.

  The average particle diameter of the primary particles of the water-insoluble inorganic substance used here can be measured with a scanning electron microscope (SEM) or the like. The average particle size is preferably about 0.1 to 20 μm, and an aggregate of primary particles can be used. The content of the water-insoluble inorganic substance is preferably 50% by weight or less and more preferably 30% by weight or less in the base granule group from the viewpoints of economy and dispersibility.

  The base granule group may also contain auxiliary components such as fluorescent dyes, pigments, and dyes that are suitable when the final detergent composition is prepared from the base granule group.

  The amount of the base granule group in the detergent particle group is not particularly limited, but is preferably 30% by weight or more, more preferably 40% by weight or more, and 50% by weight from the viewpoint of suppressing particle growth and improving solubility. % Or more is more preferable. On the other hand, from the viewpoint of the degree of freedom of blending, 85% by weight or less is preferable, and 75% by weight or less is more preferable.

2. Method for producing base granule group The base granule group includes the following steps (I) and (II):
Step (I): containing a water-soluble polymer, a water-soluble inorganic salt and 0.0005 to 1% by weight of an anionic surfactant [component (a)] having a sulfate group or a sulfonate group, and a crystalline aluminosilicate Preparing a slurry of 10% by weight or less,
Step (II): A step of preparing the base granule group [component (b)] by spray drying the slurry obtained in the step (I).
It is prepared by.

[Step (I) (Slurry Preparation Step)]
Step (I) is a step of preparing a slurry for preparing the base granule group. The slurry is mainly composed of the water-soluble polymer, water-soluble inorganic salt, 0.0005 to 1% by weight (in terms of solid content in the slurry) anionic surfactant having 10% by weight (in the slurry). Solid content conversion) It is composed of the following crystalline aluminosilicate and water, and is prepared so that it can be fed by a pump. Preferably, the slurry has a water content of 30 to 70% by weight, more preferably 35 to 60% by weight, and still more preferably 40 to 56% by weight. Moreover, the temperature of a slurry becomes like this. Preferably it is 30-80 degreeC, More preferably, it is 40-70 degreeC. Within this range, the water-soluble polymer and the water-soluble inorganic salt are preferable in terms of the dissolution rate and the viscosity of the slurry, which is preferable.

  The order of adding and mixing the components is not particularly limited, but after adding a water-soluble polymer or a water-soluble inorganic salt, an anionic surfactant having a sulfate group or a sulfonate group such as an alkylbenzene sulfonate. It is preferable from the point that foaming of the slurry can be suppressed by adding an agent. Regarding the addition form, it can be added to the slurry in the form of powder, aqueous solution or acid precursor. When an anionic surfactant having a sulfuric acid group or a sulfonic acid group is added, it is added with an acid precursor and neutralized in a slurry. .

[Step (II) (Step of preparing base granule group)]
Step (II) is a step of preparing the base granule group [component (b)] by spray drying the slurry obtained in step (I).

  The slurry atomization device may be a pressure spray nozzle, a two-fluid spray nozzle, or a rotating disk type. However, since the average particle size of the obtained base granule group is preferably 120 to 400 μm, the pressure spray nozzle is particularly preferable. preferable. From the viewpoint of obtaining the thermal efficiency of the spray-drying tower and good stability during continuous operation, the temperature of the high-temperature gas supplied to the spray-drying tower (hereinafter referred to as the blowing temperature) is preferably 150 to 300 ° C., more Preferably it is 170-250 degreeC. The temperature of the gas discharged from the spray drying tower (hereinafter referred to as exhaust air temperature) is preferably 70 to 125 ° C, more preferably 80 to 115 ° C. As the spray-drying tower, a countercurrent tower is more preferable because thermal efficiency and particle strength of the base granule group are improved.

3. Physical Properties of Base Granule Group The average particle size of the base granule group obtained as described above is preferably 120 to 400 μm, more preferably 150 to 350 μm, from the viewpoint of the solubility of the detergent particle group. The average particle diameter can be adjusted by, for example, the spray nozzle diameter, spray pressure, slurry viscosity, and the like.

  The bulk density of the base granule group is preferably lower from the viewpoint of increasing the reaction area in the base granule group when the base granule group is used for dry neutralization as in the present invention, From the viewpoint of obtaining a compact detergent having a bulk density of 500 g / L or more, 350 g / L or more is preferable, and 400 to 800 g / L is more preferable. The bulk density can be adjusted by the slurry moisture, the amount of component (a) added in the slurry, the amount of inorganic salt, the blowing temperature during drying, and the like.

Particle strength of the base particles, from the viewpoint of the base particles when performing dry neutralization does not disintegrate, preferably 50~1000kgf / cm ^2, more preferably 100~600kgf / cm ^2, more preferably 150~400kgf / Cm ² . The particle strength can be adjusted by the amount of water-soluble polymer, slurry moisture, the amount of component (a) added in the slurry, the amount of inorganic salt, the blowing temperature during drying, and the like. In the present specification, 1 kgf / cm ² = 9.80665 × 10 ⁻² MPa.

  The water content of the base granule group is preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight, from the viewpoint of the handleability of the base granule group. The amount of moisture can be adjusted by the amount of blowing air, the blowing temperature, and the like.

  The surface state of the base granule group obtained by such a method is characterized in that the film is missing or rough. In the present invention, the deficient or rough coating is a highly viscous substance or a paste-like substance added to the inside of the granule from the outside of the granule (a mixture of an anionic surfactant acid precursor and a neutralized product thereof). ) Means that the coating is physically partially damaged to the extent that it can be easily reached. Examples of the form include partial peeling, cracking, and opening of the coating depending on the degree. These can be confirmed by observing at 500 to 2000 times using an electron microscope such as SEM.

The internal structure of the base granule group can be confirmed using a mercury porosimeter as the pore volume distribution. In the distribution of pore volume per pore diameter inside the base granule (hereinafter referred to as pore volume distribution) measured with a mercury porosimeter (for example, “Pore Sizer 9320” manufactured by Shimadzu Corporation), the pore volume is larger. For example, the carrying capacity of the liquid composition increases, and the smaller the pore diameter, the higher the ability (holding power) to hold the liquid composition once absorbed by capillary action. Accordingly, the mode diameter of the pore volume distribution (the pore diameter having the largest pore volume in the obtained pore volume distribution) is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, and 2 μm. The following are particularly preferable.
Regarding the pore volume of the base granule group of the present invention, the pore volume distribution with a pore diameter of 0.01 to 4 μm is preferably 0.2 ml / g or more, more preferably 0.25 ml / g or more, More preferably 0.30 ml / g or more. The pore diameter and pore volume distribution can be adjusted by the slurry moisture, the amount of activator added, the amount of inorganic salt, the blowing temperature during drying, and the like.

In the present invention, using the base granule group obtained as described above, the following steps (III) and (IV):
Step (III): Step of dry neutralizing component (b) with 30-60 parts by weight of non-soap anionic surfactant acid precursor [component (c)] with respect to 100 parts by weight of component (b) ,
Step (IV): A detergent particle group is produced by a step of surface modification by adding a flow aid [component (d)] to the mixture obtained in step (III).

4). (C) Component: Acid precursor of non-soap anionic surfactant (c) The non-soap anionic surfactant acid precursor as component (c) is a precursor of a non-soap anionic surfactant. It shows an acid form, refers to a liquid form, and forms a salt by a neutralization reaction. Therefore, the acid precursor of the non-soap anionic surfactant is not particularly limited as long as it is a known non-soap anionic surfactant precursor and has the above-mentioned properties. (LAS), α-olefin sulfonic acid (AOS), alkyl sulfuric acid (AS), internal olefin sulfonic acid, fatty acid ester sulfonic acid, alkyl ether sulfuric acid, dialkyl sulfosuccinic acid and the like. As such component (c), only one component may be used, or two or more components may be used in combination. Among these, linear alkylbenzene sulfonic acid (LAS) is preferable from the viewpoints of economy, storage stability and foaming.

  The amount of component (c) is 30 parts by weight or more, preferably 35 parts by weight or more, and more preferably 40 parts by weight or more with respect to 100 parts by weight of component (b) from the viewpoint of detergency. On the other hand, from the viewpoint of maintaining the sharpness of the particle size distribution and suppressing the decrease in solubility due to the continuous phase of the neutralized product of the component (c), the amount is 60 parts by weight or less with respect to 100 parts by weight of the component (b). 55 parts by weight or less is preferable, and 50 parts by weight or less is more preferable. That is, the amount of component (c) is 30 to 60 parts by weight, preferably 35 to 55 parts by weight, and more preferably 40 to 50 parts by weight with respect to 100 parts by weight of component (b).

5). (D) Component: Flow aid The detergent particle group of the present invention is preferably subjected to surface modification with a flow aid for the purpose of further improving the flowability and storage stability of the detergent particles.

  As the flow aid, commonly known ones can be used, and sodium tripolyphosphate, crystalline or amorphous aluminosilicate, diatomaceous earth, silica and the like are preferably used. Of these, sodium tripolyphosphate and zeolite having chelating ability are preferable. This is because by performing surface modification with a substance having chelating ability, the chelating ability acts from the initial stage of washing, and the washing ability is improved. Zeolite is more preferable from the viewpoint of flow characteristics, and sodium tripolyphosphate is more preferable from the viewpoint of rinsing properties. In addition, a surfactant in powder form at normal temperature can be used as a flow aid, which is effective in optimizing foam behavior such as foaming power during washing and improving cleaning ability.

  The particles used as the flow aid preferably have an average particle size of 1/10 or less of the average particle size of the detergent particle group from the viewpoint of coatability. Therefore, pulverization using a pulverizer to a desired particle size is also an effective means. The average particle diameter of the fine powder is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.) or a measurement by microscopic observation. Moreover, regarding the order of addition, it is preferable from a viewpoint of fluidity | liquidity to add from the thing with a large particle size.

  Further, the amount of the flow aid is preferably 2 to 50% by weight, more preferably 5 to 40% by weight in the detergent particle group from the viewpoint of maintaining the flow characteristics.

  In addition, when using zeolite as a flow aid, it is preferable to perform surface modification after the neutralization reaction is completed from the viewpoint of suppressing decomposition.

6). (B) Powder raw materials other than components Powder raw materials can be used in combination with the (b) base granule group so that high surfactant content and adhesion in the mixer can be reduced, and detergency can be improved. Can do. The powder raw material referred to here means a detergency enhancer or oil absorbent other than a powder surfactant at room temperature, and specifically, a group showing sequestering ability such as zeolite and citrate. Agents, bases that show alkalinity such as sodium carbonate and potassium carbonate, bases that have both sequestering / alkaline ability such as crystalline silicates, etc. It includes amorphous silica, amorphous aluminosilicate, and the like.

  The blending amount of the powder raw material is preferably 0 to 30 parts by weight, more preferably 1 to 20 parts by weight, and further preferably 3 to 15 parts by weight with respect to 100 parts by weight of the component (b). In this range, detergent particle groups with improved productivity and detergency can be obtained.

7). Manufacturing method of detergent particle group The detergent particle group of this invention is manufactured by process (III) and process (IV) as mentioned above.

7-1. Process (III)
Step (III) is a step of dry neutralizing the component (b) by mixing 30 to 60 parts by weight of the component (c) with respect to 100 parts by weight of the component (b). In step (III), it is preferable to uniformly mix component (c) with component (b). As an addition method, it is preferable to spray by a nozzle and add as uniformly as possible.

  Further, in the step (III), further adding 5 to 60 parts by weight of a nonionic surfactant with respect to 100 parts by weight of the component (b) in the component (b) improves cleaning performance and (c) By suppressing the viscosity of the neutralized product of the components, it is preferable from the viewpoint that particle growth is suppressed and a high blend of non-soap anionic surfactant can be achieved.

  The nonionic surfactant preferably has a melting point of 30 ° C. or less, more preferably 25 ° C. or less from the viewpoint of detergency. Particularly preferred is a polyoxyalkylene alkyl ether obtained by adding 6 to 10 moles of alkylene oxide to an alcohol having 10 to 14 carbon atoms.

  The order of addition of the nonionic surfactant is not particularly limited, but (1): a method of adding the nonionic surfactant after adding the component (c), (2): after adding the nonionic surfactant ( c) Method of adding the component, (3): Method of adding the component (c) and the nonionic surfactant at the same time, (4): Mixing part or all of the nonionic surfactant and the component (c) in advance After that, there is a method of adding the remaining component (c).

  The addition method is appropriately selected depending on the physical properties of the base granule group such as pore volume and pore diameter, the type and amount of nonionic surfactant and acid resistance, or the type and amount of non-soap anionic surfactant. However, by using the addition methods (2), (3), and (4), it is possible to obtain a detergent particle group in which particle growth is further suppressed when the non-soap anionic surfactant is blended in a high amount. .

  The mixing condition of the component (b) and the component (c) in the step (III) may be selected so that the component (b) does not substantially collapse. For example, when a mixer equipped with a stirring blade is used, the fluid number of the stirring blade provided in the machine is preferably 0.5 to 4, more preferably 0.5 to 2, and particularly preferably 0.8 to 1. It is desirable to adjust to 4.

  Furthermore, you may use the mixer which comprises a stirring blade and a crushing blade. In the case of dry neutralization using such a mixer, conventionally, it has been customary to rotate the crushing blade at a high speed in order to promote crushing and mixing of the agglomerates. However, in the present invention, in such a case, it is preferable not to rotate the crushing blade substantially from the viewpoint of suppressing the collapse of the component (b). The fact that the crushing blade is not substantially rotated means that the crushing blade is not rotated at all, or in view of the shape, size, etc. of the crushing blade, various components in the vicinity of the crushing blade within the range in which the component (b) is not substantially collapsed. This means that the crushing blade is rotated for the purpose of preventing the stagnation of raw materials. Specifically, the fluid number is preferably 200 or less, more preferably 100 or less.

  In this step, the state in which the component (a) is not substantially collapsed refers to a state in which 70% or more of the component (b) in the mixture maintains its form. As the confirmation method, for example, there is a method in which particles obtained by extracting a soluble component from a mixture obtained using an organic solvent are observed with an SEM. When the component (b) is not substantially disintegrated, there is an advantage of improving the solubility and fluidity of the detergent particles.

The fluid number defined in the present invention is calculated by the following equation.
Fluid number (Fr) = V ² / (R × g)
Where, V: peripheral speed of the tip of the stirring blade / cracking blade [m / s]
R: Rotating radius of stirring blade and crushing blade [m]
g: Gravity acceleration [m / s ² ]

  The temperature of the mixture during dry neutralization is preferably higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher, in order to suppress thickening due to the neutralization of component (c). Further, from the viewpoint of the thermal stability of the component (c) and the nonionic surfactant, it is preferably 100 ° C. or lower, and more preferably 95 ° C. or lower. By increasing the temperature of the mixture, the viscosity of the neutralized product of component (c) can be suppressed, and the neutralized product can more easily penetrate into component (b). The temperature at the time of neutralization can be adjusted with a jacket or the like, and a structure having a jacket is preferable. It can also be carried out by adjusting the temperature of the input raw material.

  The neutralization time is preferably about 2 to 10 minutes after the addition of component (c), more preferably about 3 to 8 minutes.

  Specific examples of preferable mixing apparatuses include the following. When performing by a batch type, the thing of (i)-(iii) is preferable. (B) Henschel mixer (Mitsui Miike Chemical Co., Ltd.), High Speed Mixer (Fukae Kogyo Co., Ltd.), Vertical Granulator (Powrec Co., Ltd.), Redige Mixer (Matsuzaka Giken Co., Ltd.) , Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), (b) Ribbon mixer (manufactured by Hiwa Machine Industry Co., Ltd.), (c) Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.) Among the above mixers, more preferred are a Redige mixer and a Proshare mixer. Moreover, you may mix a base granule group and surfactant using the continuous apparatus of said mixer. In addition, as a continuous type apparatus of the mixer other than the above, there are a flexo-mix type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.) and the like.

7-2. Process (IV)
Step (IV) is a step of adding a flow aid [component (d)] to the mixture obtained in step (III) to perform surface modification. By performing step (IV), the flow of detergent particles is performed. And resistance to caking can be improved.

As mixing conditions in step (IV), the fluid number of the stirring blades provided in the mixer is preferably 2 or more, more preferably 3 or more, and when the crushing blades are provided, the fluid number of the crushing blades is preferable. Is 200 or more, more preferably 500 or more. When the peripheral speed is within this range, mononuclear detergent particles having excellent fluidity can be obtained.

  Mononuclear detergent particles having excellent flowability by mixing the flow aid [component (d)] with the mixture obtained in step (III) under the above conditions so that the flow aid covers the surface of the base granule. In terms of the order of addition, it is preferable from the viewpoint of improving the fluidity to add from the one having a larger particle size. When the mixture is weakly aggregated due to the adhesive strength of the neutralized product, the flow aid functions as a grinding aid that cuts off the continuous layer in the initial stage of mixing.

  As a preferable mixing apparatus, the mixing apparatus exemplified in the step (III) is preferable. Further, a mixing device having crushing blades such as a chopper in the mixing device is preferable. As such devices, a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd.), a proshear mixer (manufactured by Taiheiyo Kiko Co., Ltd.), high speed There are mixers (Fukae Kogyo Co., Ltd.).

  The mixing time is preferably about 0.5 to 3 minutes. The temperature of the mixture is preferably 40 ° C. or higher and more preferably 50 ° C. or higher from the viewpoint of suppressing the viscosity of the neutralized product. Moreover, 100 degreeC or less is preferable from the point of the thermal stability of (c) component and a nonionic surfactant, and 95 degreeC or less is more preferable.

8). Physical properties of detergent particle group The detergent particle group obtained by the above production method has a particle growth degree of 1.6 or less and a bulk density of 500 g / L.
Among these, preferable physical properties of the detergent particle group according to the present invention are as follows. The average particle diameter is preferably 150 to 650 μm, more preferably 180 to 400 μm. The bulk density is preferably 500 to 1000 g / L, more preferably 600 to 900 g / L, and still more preferably 650 to 850 g / L. The caking resistance is preferably 90% or more, more preferably 95% or more, with a sieve passing rate of 90% or more. The fluidity is preferably 8 seconds or less, more preferably 7 seconds or less.

  Moreover, it is preferable that a detergent particle group is a mononuclear detergent particle group from a viewpoint of improving the solubility of detergent particle | grains and expressing the function of a washing | cleaning component at an early stage. “Mononuclear detergent particle group” means a detergent particle group containing mononuclear detergent particles. “Mononuclear detergent particles” are detergent particles in which a surfactant composition is supported on a group of base granules, and detergent particles having one base granule as a core in one detergent particle. Say.

As a factor expressing mononuclearity, a particle growth rate defined by the following formula can be used, and a preferable particle growth rate is 0.95 to 1.4, more preferably 1.0 to 1.35, and still more preferably. Is 1.05-1.3.
Particle growth degree = (average particle size of final detergent particles) / (average particle size of base granules)
The final detergent particle group refers to the detergent particle group obtained through the steps (I) to (IV).

  As an example of the method for confirming the mononuclearity of the detergent particles, the mononuclearity can be confirmed by at least one of the following methods (a), (b), and (c). (A) Method: A detergent by cutting detergent particles arbitrarily sampled from around the average particle diameter of the detergent particles, and observing the presence / absence and the number of granules in the detergent particles with a scanning electron microscope (SEM) A method of confirming mononuclearity of particles. Method (b): An organic solvent that does not dissolve the water-soluble polymer in the support granules in the detergent particles (for example, polyacrylate as the water-soluble polymer in the support granules, and an anionic surfactant as the surfactant) (In the presence of LAS) or a nonionic surfactant, ethanol can be used preferably), and the organic solvent-soluble component in the detergent particles is extracted, and the subsequent organic solvent-insoluble component is observed by SEM observation. how to. That is, when one supporting granule is present in the organic solvent insoluble matter obtained by treating one detergent particle with the organic solvent, it is understood that the detergent particle is mononuclear. (C) Method: The detergent particles are separated by detecting the two-dimensional element distribution on the cut surface of the detergent particles encapsulated with resin with an energy dispersive X-ray spectrometer (EDS) or an electron beam microanalyzer (EPMA). How to check nuclearity.

  It is preferable that the detergent particle group obtained by the production method of the present invention can realize high-speed solubility. Fast dissolution refers to the property that the detergent particle group dissolution rate calculated by the following method is 90% or more.

1 L hard water (Ca / Mg molar ratio 7/3) corresponding to 71.2 mg CaCO ₃ / L adjusted to 25 ° C. is 1 L beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, 1 L glass beaker manufactured by Iwaki Glass Co., Ltd.) ) And keeping the water temperature at 25 ° C. constant with a water bath, swirl with respect to the water depth with a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon round thin type) Stir at a rotational speed (800 r / min) at which the depth is approximately 1/3. The detergent particles reduced and weighed to 1.000 ± 0.0010 g are charged and dispersed in water with stirring, and stirring is continued. 60 seconds after the addition, the detergent particle dispersion in the beaker was filtered through a standard sieve (diameter: 100 mm) with a known opening of 74 μm according to JIS Z 8801 (corresponding to ASTM No. 200), and the water content remaining on the sieve Of detergent particles together with a sieve are collected in an open container of known weight. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The collected residue of detergent particles is dried in an electric dryer heated to 105 ° C. for 1 hour, and then kept in a desiccator (25 ° C.) containing silica gel for 30 minutes for cooling. After cooling, the total weight of the dissolved residue of the dried detergent particles, the sieve and the collection container is measured, and the dry weight of the detergent particles remaining on the sieve is determined. And the dissolution rate (%) of a detergent particle group is computed by following Formula. The weight is measured using a precision balance.
Dissolution rate (%) = {1- (T / S)} × 100
S: input weight of detergent particles (g)
T: Dry weight (g) of detergent particles remaining on the sieve

10. Method for Measuring Physical Properties of Base Granule Group and Detergent Particle Group Physical property values of the base granule group and the detergent particle group can be measured by the following method.

  1) Average particle diameter: It can be measured from the weight distribution according to the size of each sieve after vibrating for 5 minutes using a standard sieve defined in JIS Z 8801.

  2) Bulk density: It can be measured by the method defined in JIS K 3362.

  3) Particle strength: 20 g of sample was placed in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikagaku Co., Ltd., TVP1 tapping type densely packed bulk density meter, tapping conditions; period 36 The sample height (initial sample height) at that time is measured. Thereafter, the entire upper end surface of the sample held in the container by a pressure tester is pressurized at a speed of 10 mm / min, and a load-displacement curve is measured, and the slope of the linear portion with a displacement rate of 5% or less is obtained. The value obtained by multiplying the initial sample height and dividing by the pressurized area is taken as the particle strength.

  4) Moisture content: The moisture content of the base granule group is measured by the infrared moisture meter method. That is, 3 g of a sample is placed on a sample pan having a known weight, and the sample is heated and dried for 3 minutes by an infrared moisture meter (manufactured by Kett Science Laboratory Co., Ltd. (infrared lamp 185W)). After drying, weigh the sample pan and dry sample. The difference in weight between the container before and after drying obtained by the above operation and the weight of the sample is divided by the amount of the sample weighed and multiplied by 100 to calculate the amount of water in the sample.

5) Caking resistance: length × width × height = 10 cm × 6 cm × 4 cm using two types of filter papers defined in JIS P 3801 (for example, “Qualitative No. 2 filter paper” manufactured by Toyo Roshi Kaisha, Ltd.) Make a container with an open top. 100 g of a sample is put in this box, and a total weight of 15 g + 250 g of an acrylic resin plate and a lead plate (or iron plate) is placed thereon. This is left in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. The determination is performed by obtaining the passage rate as follows. The higher the pass rate, the higher the caking resistance, which is a preferable physical property as a detergent particle group.
<Screen passing rate>
The sample after the test is gently opened on a sieve (mesh opening 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the passage rate (%) with respect to the sample after the test is obtained.

6) Flowability The flow time is the time required for 100 mL of powder to flow out from the bulk density measurement hopper defined by JIS K 3362.

7) Peak pore diameter (mode diameter)
The pore volume distribution of the base granule group used in the present invention can be measured using a mercury porosimeter (“Pore Sizer 9320” manufactured by Shimadzu Corporation).

8) Pore volume distribution The pore volume of the base granule group is measured using “SHIMADZU pore sizer 9320” manufactured by Shimadzu Corporation and based on the instruction manual as follows. That is, the base granule group is put in a cell, and the mercury to be injected is measured by dividing it into a low pressure part (0 to 14.2 psia) and a high pressure part (14.2 to 30000 psia). The measurement data is smoothed by taking a moving average of two pieces of data before and after, and a mode diameter in a range of 0.01 to 4 μm and a pore volume distribution of 0.01 to 4 μm are obtained.

  The Rosin-Rammler number (n) of the detergent particle group indicates that the larger the value, the sharper the particle size distribution. However, n is preferably 2.0 or more, more preferably 2.5 or more, and 3.0. The above is more preferable.

The following formula is used to calculate the Rosin-Rammler number (n).
log (log (100 / R (Dp))) = n log (Dp / De)
R (Dp): Cumulative rate [%] of powder having a particle size of Dp μm or more
Dp: Particle diameter [μm]
De: Average particle diameter [μm]
n: Rosin-Rammler number [-]

  The yield of the detergent particle group is determined from the weight fraction of the sample that passed through the 1000 μm sieve when the average particle size was measured. The yield is preferably 90% or more, more preferably 92% or more, and still more preferably 95% or more.

  The detergent particle group of the present invention having such physical properties can be suitably used in detergent compositions such as garment detergents and automatic dishwasher detergents.

9. Detergent Composition The detergent composition of the present invention is a detergent component added in addition to the detergent particle group (for example, fluorescent dye, enzyme, fragrance, antifoaming agent, bleach, bleach activator, powder activator, etc.) Containing. In this case, the detergent composition preferably contains 50% by weight or more of the detergent particle group in the detergent composition, more preferably 60% by weight or more, and still more preferably 80% by weight or more. Thereby, it is possible to provide a detergent composition having excellent storage stability and solubility and a sharp particle size distribution.

Example 1
Deionized water is added to a mixing tank having a stirring blade, and after the water temperature reaches 60 ° C., sodium sulfate (“neutral anhydrous sodium sulfate”, manufactured by Shikoku Kasei Co., Ltd.), 40% by weight of No. 2 sodium silicate aqueous solution ( Fuji Chemical Co., Ltd.) and sodium tripolyphosphate (Shimonoseki Mitsui Chemical Co., Ltd.) were added in this order and stirred for 10 minutes. Further, sodium carbonate (“Dense ash”, manufactured by Central Glass Co., Ltd.) was added and stirred for 5 minutes. Next, 40% by weight aqueous sodium polyacrylate solution (weight average molecular weight 10,000, manufactured by Kao Corporation) was added and stirred for 10 minutes. After that, 50% by weight of LAS-Na aqueous solution (“Neopelex FS”, aqueous solution of neutralized product manufactured by Kao Corporation) was added and stirred for 10 minutes, and then stirred for 60 minutes while circulating and grinding with a line mill. And a homogeneous slurry was obtained. The final temperature of this slurry was 59 ° C. This slurry was spray-dried to obtain a base granule group. The composition and physical properties of this base granule group are shown in Table 1.
When the surface of the obtained base granule group was observed with SEM, defects were observed on the surface of the granules as shown in FIG. 1 (FIG. 1).

Next, 47 parts by weight of the obtained base granule group, 10 parts by weight of sodium carbonate (“Dense Ash”, manufactured by Central Glass Co., Ltd.) and 3 parts by weight of sodium bicarbonate (manufactured by Tosoh Corporation) The sample was introduced into Matsusaka Giken Co., Ltd. (capacity 20L, with jacket) and stirred for 1 minute while the spindle was 80 r / min (fluid number 1.1) and the chopper was stopped. Subsequently, 20 parts by weight of LAS precursor (“Neopelex FS”, manufactured by Kao Corporation) is added in 2 minutes, and the stirring speed is 6 minutes at a rotation speed of 80 r / min (fluid number: 1.1) and the chopper is stopped. Then, a dry neutralization reaction was performed.
Subsequently, polyethylene glycol (“K-PEG 6000”, weight average molecular weight 8500, manufactured by Kao Corporation) 0 part by weight was added in 20 seconds, and the mixture was stirred and mixed for 2 minutes while rotating at 80 r / min (fluid number 1.1) and stopping the chopper.
Subsequently, 14 parts by weight of the above mixture and crystalline aluminosilicate (manufactured by PQ Chemicals (Thailand), trade name “VALFOR100”) and 5 parts by weight of sodium tripolyphosphate pulverized to 12 μm by a pulverizer were charged. Surface modification was performed for 1 minute at min (fluid number 5.4) and chopper 3600 r / min (fluid number 870) to obtain detergent particles. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having excellent fluidity, small particle growth, and low caking property.

Example 2
A slurry for the base granule group was prepared so as to have the composition shown in Table 1, and the base granule group was prepared in the same manner as in Example 1. Table 1 shows the physical properties of the obtained base granules.
When the surface of the obtained granule group was observed by SEM, defects were observed on the surface of the granules.

Next, 47 parts by weight of the obtained base granule group, 5 parts by weight of sodium carbonate (“Dense Ash”, manufactured by Central Glass Co., Ltd.) and 3 parts by weight of sodium bicarbonate (manufactured by Tosoh Corporation) The product was introduced into NIPPO DAL Co., Ltd. (capacity 90 L, with jacket), and stirred at a rotational speed of 60 r / min (fluid number 0.8) for 1 minute. Subsequently, the following liquid surfactant composition was added in 1 minute, and after stirring for 1 minute at a rotational speed of 60 r / min, 20 parts by weight of LAS precursor (“Neoperex FS”, manufactured by Kao Corporation) ) Was added in 2 minutes, and the mixture was stirred and mixed at a rotational speed of 60 r / min for 6 minutes to perform a dry neutralization reaction.
Subsequently, 14 parts by weight of the above mixture and crystalline aluminosilicate (manufactured by PQ Chemicals (Thailand), trade name “VALFOR100”) and 5 parts by weight of sodium tripolyphosphate pulverized to 12 μm by a pulverizer were charged. Surface modification was performed for 30 seconds with min (fluid number 5.4) and chopper 3600 r / min (fluid number 870) to obtain detergent particles. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having excellent fluidity and low caking property and having smaller particle growth than the detergent particle group of Example 1.

  The liquid surfactant composition is composed of 5 parts by weight of polyoxyethylene alkyl ether (“Emulgen 108KM”, EO 8.5, manufactured by Kao Corporation), polyethylene glycol (“K-PEG 6000”, weight average molecular weight 8500, Kao). 1 part by weight was manufactured by mixing at 60 ° C.

Example 3
A slurry for the base granule group was prepared so as to have the composition shown in Table 1, and Example 1 was used except that AS-Na (“Emar 10 Powder” manufactured by Kao Corporation) was used instead of the LAS-Na aqueous solution. Similarly, base granule groups were prepared. Table 1 shows the physical properties of the obtained base granules.
When the surface of the obtained granule group was observed with SEM, defects were observed on the surface of the granules.

Next, a detergent particle group was obtained in the same manner as in Example 2 except that the obtained base granule group was used. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having excellent fluidity, small particle growth, and low caking property.

Example 4
A slurry for the base granule group is prepared so as to have the composition shown in Table 1, and 30% by weight of ES-Na (“Emar 227-pH11”, manufactured by Kao Corporation) aqueous solution is used instead of the LAS-Na aqueous solution. A base granule group was prepared in the same manner as in Example 1 except that. Table 1 shows the physical properties of the obtained base granules.
When the surface of the obtained granule group was observed with SEM, defects were observed on the surface of the granules.

Next, a detergent particle group was obtained in the same manner as in Example 2 except that the obtained base granule group was used. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having excellent fluidity, small particle growth, and low caking property.

Comparative Example 1
A slurry for a base granule group was prepared so as to have the composition shown in Table 1, and a base granule group was prepared in the same manner as in Example 1 except that LAS-Na was not blended. Table 1 shows the physical properties of the obtained base granules.
When the surface of the obtained base granule group was observed with SEM, no defects were observed on the surface of the granules as shown in FIG.

Next, a detergent particle group was obtained in the same manner as in Example 1 except that the obtained base granule group was used. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having a large degree of particle growth.

Comparative Example 2
A slurry for a base granule group was prepared so as to have the composition shown in Table 1, and sodium palmitate ("Lunac P-95", manufactured by Kao Corporation) was used in place of the LAS-Na aqueous solution. The base granule group was prepared in the same manner as in 1. Table 1 shows the physical properties of the obtained base granules.
When the surface of the obtained granule group was observed with SEM, no defect was found on the surface of the granule.

Next, a detergent particle group was obtained in the same manner as in Example 2 except that the obtained base granule group was used. Table 2 shows the physical properties of the obtained detergent particles.
The obtained detergent particle group was a particle group having a large degree of particle growth.

  From the results of Tables 1 and 2, the detergent particle group obtained using the base granule group obtained in Examples 1 to 4 has a sharp particle size distribution compared to those obtained in Comparative Examples 1 and 2. It is clear that the granulation yield is high and the particle growth rate is small and the fluidity is excellent.

  The detergent particle group obtained by the production method of the present invention is suitably used for a powder detergent for clothing, an automatic dishwashing detergent and the like.

1 shows an SEM image of the surface of the base granule group obtained in Example 1. FIG. FIG. 2 shows an SEM image of the surface of the base granule group obtained in Comparative Example 1.

Claims (5)

Step (I): containing a water-soluble polymer, a water-soluble inorganic salt and 0.0005 to 0.5 % by weight of an anionic surfactant [component (a)] having a sulfate group or a sulfonate group, and a crystalline aluminosilicate Preparing a slurry of 10% by weight or less,
Step (II): a step of preparing the base granule group [component (b)] by spray drying the slurry obtained in the step (I),
Step (III): Step of dry neutralizing component (b) with 30-60 parts by weight of non-soap anionic surfactant acid precursor [component (c)] with respect to 100 parts by weight of component (b) And step (IV): a step of surface modification by adding a flow aid [component (d)] to the mixture obtained in step (III), the particle growth degree is 1.6 or less, bulk A method for producing detergent particles having a density of 500 g / L or more. (B) pore volume distribution having an average particle diameter of 120 to 400 μm, a bulk density of 350 g / L or more, a mode volume diameter of pore volume distribution by a mercury porosimeter of 5 μm or less, and a pore diameter of 0.01 to 4 μm There is a 0.2 ml / g or more, ^{(wherein, 1kgf / cm 2 = 9.80665 ×} 10 -2 MPa) particle strength is 50~1000kgf / cm ² a method according to claim 1, wherein.   The process according to claim 1 or 2, wherein the content of the amorphous silicate in the component (b) is 2 to 15% by weight. The process according to any one of claims 1 to 3 , wherein in step (III), dry neutralization is carried out using a mixer equipped with a stirring blade under a condition where the fluid number of the stirring blade is 0.5 to 4 .   The process according to any one of claims 1 to 4, further comprising a step of adding 5 to 60 parts by weight of a nonionic surfactant to 100 parts by weight of component (b) in step (III).

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