JP2001131596A - Method for producing high-bulk density detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a high-bulk density detergent composition excellent in detergency and having a small average particle diameter. SOLUTION: This method for producing a high-bulk density detergent composition having >=650 g/L bulk density comprises a step (A) for mixing a liquid acid precursor of an anionic surfactant with a water-soluble alkali inorganic substance in an amount required to neutralize the liquid acid precursor of more in the substantial absence of an alkali metal aluminosilicate and neutralizing the liquid acid precursor and a step (B) for adding an inorganic powder and mixing the inorganic powder with the neutralized mixture after the point of time when starting the particle coarsening of the neutralized mixture during the neutralization in the step (A) and the method producing the high-bulk density detergent composition having >=650 g/L bulk density comprises (a) a step for mixing the liquid acid precursor of the anionic surfactant with the water-soluble alkali inorganic substance in an amount required to neutralize the liquid acid precursor or more in the substantial absence of the alkali metal aluminosilicate and neutralizing the liquid acid precursor and (b) a step for adding the alkali metal aluminosilicate to the neutralized mixture obtained in the step (a) and mixing the alkali metal aluminosilicate with the neutralized mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high bulk density detergent composition having excellent detergency and a small average particle size.

[0002]

2. Description of the Related Art Attention has been focused on a method for producing a powder detergent having a relatively high bulk density. JP-A-3-33199 discloses that
A method for producing a detergent composition is disclosed in which a high-speed mixer / granulator is used to dry-neutralize at a temperature of 55 ° C. or less and then granulated by adding a liquid binder. Japanese Patent Application Laid-Open No. 4-363398 discloses a method for producing a detergent composition in which a high-speed mixer / granulator is used to dry-neutralize at a temperature of 55 ° C. or more and then granulate by adding a liquid binder. Have been.

[0003] The production method represented by the above-mentioned publication discloses a technique for neutralizing an acid precursor of an anionic surfactant in the presence of an alkali metal aluminosilicate. However, the present inventors have found that, according to this method, the alkali metal aluminosilicate deteriorates and agglomerates, causing a problem that the detergency decreases.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a high bulk density detergent composition having excellent detergency and a small average particle size.

[0005]

Means for Solving the Problems The present invention provides: [1] Step (A): a liquid acid precursor of an anionic surfactant and a water-soluble precursor in an amount required to neutralize the liquid acid precursor. Mixing an alkali inorganic substance with the alkali metal aluminosilicate substantially in the absence thereof to neutralize the liquid acid precursor; and step (B): neutralizing during the neutralization in step (A) A method for producing a high bulk density detergent composition having a bulk density of 650 g / L or more, including a step of adding and mixing an inorganic powder after the point at which the mixture starts coarsening; [2] step (a) : Mixing a liquid acid precursor of an anionic surfactant and a water-soluble alkali inorganic substance in an amount required to neutralize the liquid acid precursor in the absence of alkali metal aluminosilicate Neutralizing the liquid acid precursor, and step (b): obtained in step (a). The neutralization mixture, a method of manufacturing a bulk density of 650 g / L or more high bulk density detergent composition comprising the steps of mixing by adding an alkali metal aluminosilicate.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method for producing a high bulk density detergent composition of the present invention is roughly classified into the following two embodiments. [Aspect 1] Step (A): An alkali metal aluminosilicate is prepared by mixing a liquid acid precursor of an anionic surfactant and a water-soluble alkali inorganic substance in an amount or more necessary for neutralizing the liquid acid precursor. Mixing in substantially absence to neutralize the liquid acid precursor; and step (B): after the neutralization mixture starts coarsening during the neutralization in step (A). A method for producing a high bulk density detergent composition having a bulk density of 650 g / L or more, comprising the steps of: adding and mixing an inorganic powder. [Aspect 2] Step (a): An alkali metal aluminosilicate is prepared by mixing a liquid acid precursor of an anionic surfactant and a water-soluble alkali inorganic substance in an amount or more necessary for neutralizing the liquid acid precursor. (B) mixing the neutralized mixture obtained in step (a) by adding an alkali metal aluminosilicate to the neutralized mixture obtained in step (a). A method for producing a high bulk density detergent composition having a bulk density of 650 g / L or more, comprising:

[0007] 1. Step (A) or step (a) Step (A) or step (a) is a step in which substantially the same operation is performed. The liquid acid precursor of the anionic surfactant used in the step (A) or the step (a) refers to an acid form of the anionic surfactant which is in a liquid or paste form at room temperature or when heated. A salt is formed by a summation reaction. As the liquid acid precursor of the anionic surfactant, linear alkylbenzene sulfonic acid (LA)
S), 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. The liquid acid precursor may be used in combination of two or more components.

[0008] The amount of the liquid acid precursor of the anionic surfactant can be appropriately set depending on the composition of the desired detergent composition. However, as the anionic surfactant generated by the neutralization reaction, the final high bulk density detergent composition is used. Preferably 5 to 55% by weight of the product,
5% by weight is more preferable, 10 to 40% by weight is more preferable, and 20 to 40% by weight is particularly preferable. The present invention is also effective when the main surfactant in the detergent composition is provided in another form.

The water-soluble alkali inorganic substance used in the step (A) or the step (a) has an alkali property capable of neutralizing the liquid acid precursor of the anionic surfactant. Examples of such a water-soluble alkali inorganic substance include sodium carbonate, sodium hydrogen carbonate, sodium silicate, potassium carbonate, calcium carbonate and the like. More preferred as the water-soluble alkali inorganic substance is sodium carbonate. Sodium carbonate functions as a detergent builder and alkaline agent in the final composition. Therefore, it is preferable that the water-soluble alkali inorganic substance in the step (A) or the step (a) is added in an amount necessary for neutralizing the liquid acid precursor of the anionic surfactant or more. For example, the neutralization equivalent of the liquid acid precursor of the anionic surfactant is preferably 1 to 20 times, more preferably 2 to 15 times, and most preferably 3 to 15 times.

The water-soluble alkali inorganic substance is preferably in the form of particles, and the average particle diameter is preferably 30 μm or more, more preferably 40 to 200 μm, from the viewpoint of improving yield and storage stability.
μm, most preferably 50-100 μm. In addition,
The average particle size of the particulate water-soluble alkali inorganic substance is calculated on a volume basis, and is a value measured using a laser diffraction type particle size distribution analyzer: LA-700 (manufactured by Horiba, Ltd.). .

In the step (A) or the step (a), the mixing operation is performed under the condition that the alkali metal aluminosilicate is substantially absent. Here, “substantially free of alkali metal aluminosilicate” means that the content of alkali metal aluminosilicate in the neutralized mixture in step (A) or step (a) is preferably 5% by weight or less, more preferably It preferably refers to the case of 3% by weight or less. When the alkali metal aluminosilicate is present in a large amount in the step (A) or the step (a), the alkali metal aluminosilicate is deteriorated or agglomerated due to the contact of the anionic surfactant, which is an acid, with the liquid acid precursor, Thereby, the cleaning performance of the obtained detergent composition is reduced. Therefore, such a problem can be solved by performing the mixing operation under a specific condition that the alkali metal aluminosilicate is substantially absent.

However, in the first embodiment, as described below,
In some embodiments, even during the neutralization in the step (A), the addition of the alkali metal aluminosilicate in the step (B) is started at a point in time when the liquid acid precursor of the anionic surfactant exceeds a certain amount. .

In the step (A) or the step (a), some or all of optional components can be added in addition to the water-soluble alkali inorganic substance and the liquid acid precursor of the anionic surfactant. Examples of optional components that can be blended here include a fluorescent agent, a pigment, a redeposition inhibitor (polycarboxylate polymer, sodium carboxymethylcellulose, etc.), a surfactant (fatty acid or a salt thereof, linear alkylbenzene sulfonate, alkyl sulfate). Salt), diatomaceous earth, calcite, kaolin, bentonite, tripolyphosphate, sodium sulfate, sodium sulfite, and the like.

When a detergent composition containing tripolyphosphate as a main builder is obtained, the average particle size of the tripolyphosphate is not particularly limited, but is preferably from 1 to 3.
0 μm, more preferably 5 to 20 μm, particularly preferably 6 to 15 μm. From the viewpoint of suppressing aggregation of the detergent particles, the smaller the average particle size of the tripolyphosphate, the smaller the average particle size of the detergent particles. From the viewpoint of productivity for industrially obtaining small-sized detergent particles, the average particle size is 1
μm or more is preferred, and 3
It is preferably 0 μm or less. The average particle size of the tripolyphosphate referred to in the present specification is calculated on a volume basis, and is measured by a laser diffraction particle size distribution analyzer: LA-700.
(Horiba Seisakusho Co., Ltd.).

The optional component added in the step (A) or the step (a) is preferably in the form of particles or powder, and is obtained by pulverizing a lump or separately granulated. A thing may be used. The particle size is 200 μm
The following is preferred. The optional component may be added as an aqueous solution, a paste, or a slurry. However, in order to prevent excessive coagulation, when water is contained, its amount is preferably adjusted so as not to exceed the water content described below.

When the above-mentioned optional components are added, it is preferable to mix them with a water-soluble alkali inorganic substance before the neutralization in the step (A) or the step (a). The degree of mixing is preferably such that the components are uniformly mixed. For example, when a stirring granulator is used, the operating conditions of the stirring granulator are preferably, for example, a mixing time of 5 minutes or less.

In step (A) or step (a), water may be added to promote the neutralization reaction. The amount of water to be added is 0.2 to 3 parts by weight based on 100 parts by weight of the water-soluble alkaline inorganic substance (and the dry weight thereof, if any) are added in the step (A) or the step (a). And more preferably 0.5 to 1.5 parts by weight. 0.2 parts by weight or more is preferable from the viewpoint of initiating the neutralization reaction,
The amount is preferably 3 parts by weight or less from the viewpoint of suppressing aggregation of the detergent particles. In addition, when the component such as the liquid acid precursor of the anionic surfactant contains water, or when using another aqueous material, or when using a powder material containing water, the water content thereof is taken into consideration. Then, the amount of water to be added may be determined.

As a more preferred embodiment for promoting the neutralization reaction, it is preferable to use an aqueous alkali solution or an alkaline slurry solution (hereinafter abbreviated as an alkaline solution) instead of the above-mentioned water. By using an alkaline solution, not only can the neutralization reaction be further promoted than in the case of water, the particle size of the obtained detergent particles can be reduced, and the bulk density can be increased.

The amount of the alkali solution to be added is preferably 0.05 to 0.5 times, more preferably 0.10 to 0.45 times the neutralization equivalent of the liquid acid precursor of the anionic surfactant.
A 0.10 to 0.40 volume is particularly preferred. From the viewpoint of starting a neutralization reaction and obtaining a desired effect, a neutralization equivalent of 0.0
The amount is preferably 5 times or more, more preferably 0.5 times or less from the viewpoint of suppressing aggregation of the detergent particles. When the concentration of the alkaline solution is low, excess water is supplied to the mixture as a predetermined amount of the alkaline solution is added, and the detergent particles may aggregate. Therefore, the concentration of the alkaline solution is 20 to 50% by weight. %, More preferably 30 to 50% by weight, and 40% by weight.
-50% by weight is particularly preferred.

The type of the alkaline agent used in the alkaline solution is a strong alkaline aqueous solution which easily undergoes a neutralization reaction with a liquid acid precursor of an anionic surfactant such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. Is mentioned. Among these, an aqueous sodium hydroxide solution is preferably used from the viewpoint of cost. Such an alkaline aqueous solution,
More preferably, the pH is 12 or more, and when adding, it is preferable to spray or drip so that the alkaline solution is uniformly dispersed. The alkali solution is preferably added to the mixture with the water-soluble alkali inorganic substance and other optional components before being mixed with the liquid acid precursor of the anionic surfactant.

When the neutralization is performed in the step (A) or the step (a), it is preferable to add an inorganic acid such as sulfuric acid in advance to the liquid acid precursor of the anionic surfactant. Particles obtained by neutralizing a powdery or granular water-soluble alkali inorganic substance using a premixed inorganic acid and the liquid acid precursor are neutralized salts derived from an inorganic acid. Are more present in the vicinity of the particle surface than inside the particles, so that the particles have low tackiness and become small in particle size, making it possible to produce particles having a high surfactant content without causing particle aggregation. . Further, since the particles obtained in this manner have many pores, it is possible to produce particles having a high liquid content such as a nonionic surfactant. The amount of the inorganic acid to be added is as follows: the liquid acid precursor 1 of the anionic surfactant
0.1 to 1.0 mol is preferable, and 0.1 to
0.8 mol is more preferable, 0.15 to 0.75 mol is still more preferable, 0.2 to 0.7 mol is particularly preferable,
0.25 to 0.65 mole is most preferred. With respect to 1 mol of the liquid acid precursor, it is preferably at least 0.1 mol from the viewpoint of suppressing coarsening of detergent particles, and at most 1.0 mol from the viewpoint of securing the degree of freedom of the composition of the concentrated detergent. Preferably it is.

In the step (A) or the step (a), the order of mixing the liquid acid precursor of the anionic surfactant and the water-soluble alkali inorganic substance is not particularly limited. Preferably, a body is added.

The method for adding the liquid acid precursor of the anionic surfactant may be continuous or divided into plural times, and the adding means may be provided plural times.

The neutralization in the step (A) or the step (a) is preferably performed using a stirring granulator. The stirring granulator preferably has a stirring blade and a chopper for crushing / dispersion (or a functional equivalent thereof).

Specific examples of the agitation granulator used in the present invention include a batch type granulator such as a vertical granulator (manufactured by Powrex), a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and a Redige mixer. (Matsuzaka Giken Co., Ltd.), Proshare Mixer (Taikai Kiko Co., Ltd.)
Manufactured by Meiji Kikai Co., Ltd.). Particularly preferred are a Loedige mixer and a pro-share mixer. As a continuous type, a continuous Loedige mixer (medium speed mixer: residence time is relatively long)
Or CB as a high-speed mixer (residence time is relatively short)
Recycler (manufactured by Loedige), Turbulizer (manufactured by Hosokawa Micron Corporation), Sugimixer (manufactured by Powrex), Flow Jet Mixer (manufactured by Koken Co., Ltd.)
And the like. In the present invention, the above mixers may be used in combination as appropriate. For example, the mixing of the water-soluble alkali inorganic substance and other optional components and the neutralization reaction by the addition of the liquid acid precursor of the anionic surfactant may be performed by different stirring granulators.

The agitation granulator used in the present invention is more preferably one having a jacket for adjusting the internal temperature or one having a nozzle for performing a gas blowing operation. Specific examples of such more preferable agitation granulators are disclosed in JP-A-10-296064 and JP-A-10-296064.
The mixer described in Japanese Patent Application Laid-Open No. 0-296065 is exemplified.

In the step (A) or the step (a), it is preferable to perform the neutralization while blowing gas. This is for preventing excess water generated by the neutralization reaction from evaporating and cooling the obtained granular material using gas to prevent the granular material from becoming a large lump. Examples of such a gas include N ₂ gas and air. The gas blowing amount (venting amount) is not particularly limited.
0.002 parts by weight or more per minute based on parts by weight is preferable,
0.02 parts by weight or more per minute is more preferable.

The neutralized product of the anionic surfactant acid precursor obtained in the step (A) or the step (a) (the unneutralized anionic surfactant acid precursor in the step (A)) And a mixture containing the remaining water-soluble alkali-inorganic substance and other optional components (hereinafter abbreviated as a neutralized mixture) are in a powdery or lump form.
In particular, the ratio of surfactant to final detergent composition is 2
In the case of producing a detergent exceeding 0% by weight, it is preferable to provide a crushing step for the purpose of obtaining a granular detergent which is easily coarsened or agglomerated and has a small particle size. Specifically, it is preferable to provide a crushing step when the content of the anionic activator in the neutralized mixture is 30% by weight or more. The crushing method may be carried out following the step (A) or the step (a) in a stirring granulator equipped with a crushing / dispersing chopper, or may be carried out using another crushing machine. Specific examples of the crusher include Fitzmill (manufactured by Hosokawa Micron Corp.) and speed mill (manufactured by Okada Seiko Co., Ltd.).

2. Step (B) or step (b) 2-1. Step (B) In the step (B), at the time of the neutralization in the step (A), the addition of the inorganic powder is started and mixed after the neutralization mixture starts coarsening. By starting the addition of the inorganic powder at this point, the effect of promoting the crushing effect of the neutralized mixture is exhibited.

As for the timing of starting the addition of the inorganic powder, the liquid acid precursor of the anionic surfactant was added in an amount of more than 0.25, preferably more than 0.3 by weight to the water-soluble alkali inorganic substance. It is desirable to start adding the inorganic powder after the time point. This is because the neutralized mixture begins to coarsen at this point. Further, from the viewpoint of suppressing the densification and coarsening of the neutralized mixture due to the progress of granulation after the neutralization, the addition of the inorganic powder is carried out within a short time after the completion of the total addition of the liquid acid precursor, for example, 5 times. It is desirable to do it within minutes. By starting the addition of the inorganic powder within this range, the disintegration of the neutralized mixture can be facilitated.

The inorganic powder used in the step (B) has an average particle diameter of 30 μm or less from the viewpoint of suppressing aggregation of detergent particles.
Preferably it is 20 μm or less. In addition,
The average particle diameter is calculated on a volume basis, and is a value measured using a laser diffraction particle size distribution analyzer: LA-700 (manufactured by Horiba, Ltd.). Examples of inorganic powders include inorganic powder builders and fine particle components generally used in detergent compositions, such as alkali metal aluminosilicates, tripolyphosphates, crystalline silicates, sodium sulfate, calcite, diatomaceous earth, and silica. Is exemplified. Two or more inorganic powders may be used in combination. Among these inorganic powders, alkali metal aluminosilicates are particularly preferred from the viewpoint of crushing efficiency.

The alkali metal aluminosilicate may be either amorphous or crystalline, but preferably has a sequestering ability as a cleaning aid, and is generally referred to as a synthetic zeolite in the detergent industry. Are particularly preferred. The alkali metal aluminosilicate preferably has an average particle size of 1 to 30 μm, more preferably 10 μm or less.

In particular, when the alkali metal aluminosilicate is added in the step (B), after the addition of the entire amount of the liquid acid precursor of the anionic surfactant is completed, the stirring granulator is preferably further operated for 30 seconds. As described above, it is preferable to add the compound at any point within 5 minutes from the completion of the addition after the operation is more preferably performed for 1 minute or more. It is preferable that the neutralization reaction can be completed by operating a stirring granulator after the addition of the acid precursor. As a result, the liquid acid precursor of the anionic surfactant has already been neutralized, so that even when the alkali metal aluminosilicate is added, its deterioration or aggregation does not occur. Therefore, it is possible to suppress a decrease in the cleaning performance of the obtained detergent composition, and to sufficiently exert the effect of the addition of the alkali metal aluminosilicate, that is, the effect of improving the sequestering ability and the carrying ability of the liquid component. Can be.

2-2. Step (b) Step (b) is a step of adding an alkali metal aluminosilicate to the neutralized mixture obtained in step (a) and mixing.

Here, the neutralized mixture obtained in step (a) is a mixture to which the liquid acid precursor of the anionic surfactant has been added in its entirety, and it is preferable that the mixture has been neutralized. The alkali metal aluminosilicate used in step (b) may be the same as that in step (B).

In the step (b), the timing of starting the addition of the alkali metal aluminosilicate is determined from the viewpoint of suppressing the densification and coarsening of the neutralized mixture due to the progress of granulation after completion of the neutralization. Any point within 5 minutes after the completion of the addition of the entire amount of the liquid acid precursor is preferable. In particular, after the addition of the entire amount of the liquid acid precursor of the anionic surfactant is completed, preferably, the stirring granulator is further added for 30 minutes.
It is preferable to add the alkali metal aluminosilicate at any point within 5 minutes from the end of the addition of the entire amount after operating for at least one second, more preferably at least one minute. It is preferable that the neutralization reaction can be completed by operating a stirring granulator after the addition of the acid precursor. As a result, the liquid acid precursor of the anionic surfactant has already been neutralized, so that even when the alkali metal aluminosilicate is added, its deterioration or aggregation does not occur. Therefore, it is possible to suppress a decrease in the cleaning performance of the obtained detergent composition, and to sufficiently exert the effect of the addition of the alkali metal aluminosilicate, that is, the effect of improving the sequestering ability and the carrying ability of the liquid component. Can be.

2-3. Others The amount of the inorganic powder used in the step (B) or the alkali metal aluminosilicate used in the step (b) is preferably 5 to 50% by weight, more preferably 8 to 40% by weight of the high bulk density detergent composition as the final product. % Is more preferable, and 10 to 36% by weight
Is particularly preferred. The content is preferably 5% by weight or more from the viewpoint of suppressing aggregation of the neutralized mixture, and is preferably 50% by weight or less from the viewpoint of ensuring the compositional freedom of the detergent composition.

As the method of adding the inorganic powder or the alkali metal aluminosilicate, the inorganic powder or the alkali metal aluminosilicate may be added all at once or may be added in plural times. Examples of multiple additions include (i) addition to facilitate disintegration of the neutralized mixture obtained in step (A) or step (a) when the mixture is coarsened or agglomerated. Case (addition as a crushing aid),
(ii) when added to adjust the granulation property when adding the liquid binder described below (addition as a granulation modifier), or (iii) before the surface modification of the finally obtained detergent particles (Addition as a surface modifier).

In the step (B) or the step (b), from the viewpoint of reducing the amount of fine powder and improving the detergency or the metal-sealing ability,
It is desirable to incorporate a liquid binder. According to the present invention, the particle size of the neutralized mixture is reduced, and a larger amount of the liquid binder can be blended.

The liquid binder in the present invention refers to one having a property of bringing particles together to increase the bulk density by blending. Examples of the liquid binder include water, a liquid nonionic surfactant, an aqueous solution of a water-soluble polymer (such as polyethylene glycol and maleic acrylate copolymer), and any liquid component in a detergent composition such as a fatty acid. Two or more liquid binders may be used in combination. Examples of this case include (1) adding two or more liquid binders in advance after mixing, (2) simultaneously adding each liquid binder, 3) Each liquid binder is added alternately. In any of the methods, it is preferable to use water in combination from the viewpoint of reducing the production cost. The amount of the liquid binder is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the neutralized mixture from the viewpoint of suppressing aggregation of the detergent composition.

The method of adding the liquid binder may be continuous or divided into a plurality of times. The liquid binder is preferably added to the neutralized mixture obtained in the step (A) or the step (a) before and after the addition of the inorganic powder. Thereby, the adhesiveness of the particle surface due to the binder can be reduced, and the granulation can be suppressed. Also,
In the production method of the present invention, some or all of the optional components can be blended in step (B) or step (b) in addition to step (A) or step (a). In particular, when the above aqueous solution of the water-soluble polymer is used, it is preferable to add it in the step (B) or the step (b) rather than in the step (A) or the step (a) from the viewpoint of granulation. . In this case, the inorganic powder can be dealt with by adding it in a plurality of times as shown in the above (i) to (iii) so that the granulation property is not affected by the moisture brought in from the optional component. .

In the production method of the present invention, it is preferable to provide a surface modification step as described in (iii) above. The surface modification step can also be performed using an inorganic powder such as an alkali metal aluminosilicate. It is added to detergent particles that have been granulated to some extent, and the surface is coated to improve powder properties such as anti-caking properties and fluidity.

The amount of the surface modifier is desirably 2 to 15% by weight, preferably 4 to 12% by weight in the detergent composition after the surface modification.

In the present invention, when other volatile compounds or heat-sensitive optional components are further added,
At least the inorganic powder or alkali metal aluminosilicate of step (B) or step (b) of the present invention was added and added after the particle size was adjusted, or the surface coating agent was finally treated. The particles are after-blended by mixing with a mixer such as a rotating drum.

Further, the high bulk density detergent composition obtained by the production method of the present invention may be used as a component for constituting another detergent composition.

Further, the production method of the present invention can be carried out in a continuous manner. In this case, the step (A) or the step (a) is performed using a high-speed mixer such as a CB recycler,
Subsequently, step (B) or step (b) can be carried out with a medium-speed mixer such as a continuous Loedige mixer.

According to the above production method, the bulk density was 650 g /
A high bulk density detergent composition having a particle size of L or more, having good detergency, and having a small average particle size can be obtained.

More preferably, the high bulk density detergent composition obtained by the production method of the present invention has the following physical properties.

Average particle size: Measured from the weight fraction based on the size of the sieve after shaking the sample for 5 minutes using a standard sieve specified in JIS Z 8801. It is preferably 700 μm or less, more preferably 650 μm or less.

Bulk density: preferably from 650 to 950 g / L, more preferably from 700 to 900 g / L.
In this specification, the bulk density is a value determined by a method specified in JIS K 3362.

Fluidity: The fluidity of the detergent composition in the present specification is indicated by the time required for 100 mL of the powdery detergent composition to flow out of a hopper for measuring bulk density specified in JIS K 3362. The time is preferably 8 seconds or less, more preferably 7 seconds or less.

Detergency: Detergency is indicated by a relative ratio of cleaning rate. The relative washing ratio is preferably 0.95 or more,
Eight or more are more preferable. It is preferable that the relative cleaning ratio is closer to 1 because the influence of the production method on individual components is smaller. In addition, in this specification, the relative cleaning rate ratio of a detergent composition is calculated | required as follows.

First, the detergent composition to be measured is dissolved in water to obtain an aqueous detergent composition solution. This aqueous solution is referred to as “measurement detergent aqueous solution”. Next, an aqueous solution having the same composition as the detergent aqueous solution for measurement is obtained by adding individual components constituting the detergent composition to water and mixing. This aqueous solution is referred to as “control detergent aqueous solution”. The detergency of the measuring detergent aqueous solution and the detergency of the control detergent aqueous solution are determined by the following detergency test. Then, the relative washing rate ratio is obtained as: relative washing rate ratio = (detergency of detergent aqueous solution for measurement) / (detergency of control detergent aqueous solution).

<Test of Detergency> (Preparation of Artificially Contaminated Cloth) An artificially stained cloth is prepared by adhering an artificially contaminated liquid having the composition shown in Table 1 to the cloth. The adhesion of the artificially contaminated liquid to the cloth is performed by printing the artificially contaminated liquid on the cloth using a gravure roll coater according to JP-A-7-270395. The conditions for preparing the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth are as follows.
³ / cm ² , coating speed 1.0 m / min, drying temperature 10
0 ° C., drying time 1 minute. The cloth used is a cotton gold cloth 2003 (manufactured by Tanito Shoten).

[0055]

[Table 1]

(Washing Conditions and Evaluation Method) The above prepared 10 cm × 10 cm was added to 1 L of a measurement or control detergent aqueous solution.
5 pieces of artificially stained cloth of
Wash at r / min. The washing conditions are as follows. That is, cleaning time: 10 minutes, detergent concentration: 0.083% by weight, water hardness: 5 ° DH, water temperature: 20 ° C., rinsing: tap water for 5 minutes. The reflectance at 550 nm of the original cloth before and after the cleaning and the contaminated cloth before and after the cleaning were measured with a self-recording colorimeter (manufactured by Shimadzu Corporation). Is shown as detergency (%).

[0057]

(Equation 1)

[0058]

EXAMPLES In the following examples, zeolite 4A (manufactured by Tosoh Corporation) was used as zeolite, and polyoxyethylene alkyl ether [alkyl carbon 12 to 14 (average 12.8) was used as nonionic surfactant. ) First
(Average of 8 moles of ethylene oxide added to a graded saturated alcohol) (manufactured by Kao Corporation), palmitic acid as a fatty acid, and polyethylene glycol as a maleic acrylate copolymer by a gel permeation method. The weight average molecular weight was 70,000.

Example 1 Using a Lodige mixer FKM-130D (manufactured by Matsubo Co., Ltd.), 35 kg of a detergent composition having the composition shown in Table 2 was used.
Manufactured in units. This mixer is equipped with a stirring blade, a shearing machine corresponding to a crushing / dispersing chopper, and a jacket for controlling the temperature inside the machine. The operation was performed as follows. <Powder mixing> Solid component, sodium carbonate (light ash: manufactured by Central Glass Co., Ltd., average particle size: 56.1 μm)
13.19 parts by weight and 0.11 part by weight of the fluorescent agent were stirred by the above-mentioned Loedige mixer at a stirring blade rotation speed of 130 r / m.
in (peripheral speed 3.4 m / s), shearing machine rotation speed 2850r
/ Min (peripheral speed 27 m / s) for 1 minute.

<Neutralization> The linear alkylbenzene sulfonic acid (LAS:
9.40 parts by weight of molecular weight 322) were added in 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. During the LAS addition, the on-board temperature reached a maximum of 75 ° C. After the addition of the LAS, the mixer was continuously operated under the same conditions for 5 minutes to complete the neutralization reaction and the granulation operation. Also,
Immediately after the start of the LAS addition, the air inside the machine (300 L / mi
n) was performed.

<Addition of alkali metal aluminosilicate>
When the neutralization reaction and the granulation operation were completed, zeolite (5.00 parts by weight) having an average particle size of 4 μm was added while the mixer was operated under the same conditions as above, and mixed for 5 minutes.

<Addition of Liquid Component / Surface Modification> While operating the mixer under the same conditions as described above, a nonionic surfactant (0.98 parts by weight) was added to the mixer and mixed for 1 minute, and then the average particle size was 4 μm. Of zeolite (2.00 parts by weight) was added and mixed for another 5 minutes. Subsequently, an aqueous solution of 40% by weight of acrylic acid-maleic acid copolymer (active content: 1.49 parts by weight) was added and mixed for 1 minute and 30 seconds. Subsequently, zeolite having an average particle size of 4 μm (3.50 parts by weight) was added as a surface modifier. In addition, the surface modification treatment was performed by operating the mixer for 1 minute. The particles of the obtained detergent composition had an average particle diameter of 640 μm, a bulk density of 795 g / L, and a fluidity of 7.1 seconds, and had excellent physical properties. In addition, the relative cleaning ratio was 0.998, and the particles exhibited good detergency.

<After Blend> Using a rotating drum, the enzyme (0.18 parts by weight) and the detergent composition obtained above were mixed, and a fragrance (0.07 parts by weight) was further sprayed to obtain a high bulk density. A final powder of the detergent composition was obtained.

Example 2 Using a Lodige mixer FKM-130D (manufactured by Matsubo Co., Ltd.), 35 kg of a detergent composition having the composition shown in Table 2 was used.
Manufactured in units. The configuration of this Loedige mixer was substantially the same as that of Example 1. The operation was performed as follows. <Powder mixing> 12.88 parts by weight of sodium carbonate (the same light ash as in Example 1), which is a solid component, and 0.1% of a fluorescent agent.
Example 1 was prepared by using 11 parts by weight with the above-mentioned Lodige mixer.
The mixture was mixed for 1 minute under the same conditions as described above.

<Neutralization> While operating the mixer under the same conditions as above, 9.40 parts by weight of LAS and 0.8% of 98% sulfuric acid.
A mixture consisting of 4 parts by weight was added in 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C.
During the addition of the mixture, the on-board temperature reached a maximum of 80 ° C. After the addition of the mixture, the mixer was continuously operated under the same conditions for 5 minutes to complete the neutralization reaction and the granulation operation. Immediately after the start of the addition of the mixture, the inside of the apparatus was ventilated (300 L / min).

<Addition of Alkali Metal Aluminosilicate>
As in Example 1, zeolite having an average particle size of 4 μm (5.
00 parts by weight) and mixed for 5 minutes.

<Addition of Liquid Component and Surface Modification> As in Example 1, a nonionic surfactant (0.98 parts by weight), zeolite having an average particle size of 4 μm (2.00 parts by weight), 40% by weight An aqueous solution of an acrylic acid / maleic acid copolymer (effective content: 1.49 parts by weight) was added and mixed. Subsequently, the same surface modification treatment as in Example 1 was performed. The particles of the resulting detergent composition had an average particle size of 565 μm, a bulk density of 776 g / L, and a fluidity of 7.3 seconds, and had excellent physical properties. In addition, the relative cleaning ratio was 0.988, and the particles exhibited good detergency.

<After Blend> In the same manner as in Example 1, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition.

Example 3 The amount of light ash used was 12.73 parts by weight, and before neutralization, a 48% by weight aqueous NaOH solution was used as a reaction initiator in 0.23 parts by weight.
Parts by weight, a mixture of light ash and a fluorescent agent, and then a detergent composition was prepared by the same composition and operation as in Example 2 except that a step of mixing for 1 minute and 30 seconds was added under the same conditions as the powder mixing step. Obtained. The particles of the obtained detergent composition had an average particle size of 550 μm, a bulk density of 780 g / L, and a fluidity of 7.3 seconds, and were particles having excellent physical properties. Further, the relative cleaning ratio was 0.990, and the particles exhibited good detergency.

<After Blend> In the same manner as in Example 1, enzymes and fragrances were added to obtain a final powder of a high bulk density detergent composition.

Example 4 Using a Loedige mixer FKM-130D (manufactured by Matsubo Co., Ltd.), 35 kg of a detergent composition having the composition shown in Table 2 was used.
Manufactured in units. The configuration of this Loedige mixer was substantially the same as that of Example 1. The operation was performed as follows. <Powder mixing> 12.22 parts by weight of sodium carbonate (light ash same as in Example 1) as a solid component and 0.1% of fluorescent agent
One part by weight was mixed with the above-mentioned Loedige mixer under the same conditions as in Example 1 for 1 minute.

<Neutralization> While operating the mixer under the same conditions as above, 7.39 parts by weight of LAS and 0.8% of 98% sulfuric acid.
A mixture consisting of 7 parts by weight was added in 4 minutes. During this time, water was cooled at 25 ° C. through the mixer jacket. During the addition of the mixture, the on-board temperature reached a maximum of 75 ° C. After the addition of the mixture, the mixer was continuously operated under the same conditions for 5 minutes to complete the neutralization reaction and the granulation operation. Immediately after the start of the addition of the mixture, the inside of the apparatus was ventilated (300 L / min). Subsequently, 0.97 parts by weight of fatty acid was added over 30 seconds, and then mixed for 1 minute.

<Addition of Alkali Metal Aluminosilicate>
As in Example 1, zeolite having an average particle size of 4 μm (6.
05 parts by weight) and mixed for 5 minutes.

<Addition of Liquid Component and Surface Modification> As in Example 1, nonionic surfactant (1.51 parts by weight), zeolite having an average particle size of 4 μm (2.00 parts by weight), 40% by weight An aqueous solution of an acrylic acid / maleic acid copolymer (effective content: 1.49 parts by weight) was added and mixed. Subsequently, the same surface modification treatment as in Example 1 was performed. The particles of the obtained detergent composition had an average particle size of 510 μm, a bulk density of 778 g / L, and a fluidity of 6.5 seconds, and had excellent physical properties. In addition, the relative cleaning ratio was 0.988, and the particles exhibited good detergency.

<After Blend> In the same manner as in Example 1, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition.

Example 5 Using a Lodige mixer FKM-130D (manufactured by Matsubo Corporation), 35 kg of a detergent composition having the composition shown in Table 2 was used.
Manufactured in units. The configuration of this Loedige mixer was substantially the same as that of Example 1. The operation was performed as follows. <Powder mixing> 11.00 parts by weight of sodium carbonate (light ash same as in Example 1) and fluorescent agent 0.1, which are solid components
One part by weight was mixed with the above-mentioned Loedige mixer under the same conditions as in Example 1 for 1 minute.

<Neutralization> While operating the mixer under the same conditions as described above, 11.76 parts by weight of LAS and 98% sulfuric acid.
A mixture consisting of 05 parts by weight was added in 5 minutes. During this time,
Cooling was performed by passing 25 ° C. water through the mixer jacket.
During the addition of the mixture, the on-board temperature reached a maximum of 85 ° C. After the addition of the mixture, the mixer was subsequently operated under the same conditions for 4 minutes to complete the neutralization reaction and the granulation operation. Immediately after the start of the addition of the mixture, the inside of the apparatus was ventilated (300 L / min).

<Addition and Crushing of Alkali Metal Aluminosilicate> While operating the mixer under the same conditions as above, a zeolite (5.00 parts by weight) having an average particle size of 4 μm was added as a crushing aid and mixed for 5 minutes. After that, the mixture was disintegrated using Fitzmill (manufactured by Hosokawa Micron Corporation).

<Addition of Liquid Component / Surface Modification> While stirring the crushed mixture in the Loedige mixer under the same conditions as above, a nonionic surfactant (0.70 parts by weight) was added to the mixer. And then added zeolite with an average particle size of 4 μm (2.00 parts by weight) and mixed for another 5 minutes. Subsequently, an aqueous solution of 40% by weight of acrylic acid / maleic acid copolymer (active ingredient: 1.49 parts by weight) was added, and the mixture was added for 1 minute
After mixing for 2 seconds, the same surface modification treatment as in Example 1 was performed. The particles of the obtained detergent composition have an average particle size of 560 μm.
m, the bulk density is 780 g / L, the fluidity is 7.4 seconds,
The particles had excellent physical properties. Further, the relative washing rate ratio is 0.1.
994, showing particles having good detergency.

<After Blend> In the same manner as in Example 1, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition.

Comparative Example 1 35 kg of a detergent composition having the composition shown in Table 2 was prepared using a Loedige mixer FKM-130D (manufactured by Matsubo Co., Ltd.).
Manufactured in units. The configuration of this Loedige mixer is substantially the same as that of the first embodiment. The operation was performed as follows. <Powder mixing> 13.19 parts by weight of a solid component, sodium carbonate (the same light ash as in Example 1), and an average particle size of 4 μm
7.00 parts by weight of zeolite and 0.11 part by weight of a fluorescent agent were mixed by the above-mentioned Loedige mixer under the same conditions as in Example 1 for 1 minute.

<Neutralization> While operating the mixer under the same conditions as above, 9.40 parts by weight of LAS was added over 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. During the LAS addition, the on-board temperature reached a maximum of 75 ° C. After the addition of LAS, the mixer was continuously operated under the same conditions for 5 minutes to complete the neutralization reaction and the granulation operation. Also, L
Immediately after the start of the addition of AS, the air inside the machine (300 L / mi)
n) was performed.

<Addition of Liquid Component / Surface Modification> While operating the mixer under the same conditions as above, a nonionic surfactant (0.98 parts by weight) was added to the mixer and mixed for 1 minute.
0% by weight acrylic acid-maleic acid copolymer (effective component 1.
An aqueous solution was added and mixed for 1 minute and 30 seconds, and then the same surface modification treatment as in Example 1 was performed. The particles of the obtained detergent composition have an average particle size of 650 μm and a bulk density of 770.
g / L, the fluidity was 6.9 seconds, and the particles were excellent in physical properties. However, the relative washing ratio was 0.902, and the washing property was poor.

<After Blend> In the same manner as in Example 1, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition.

[0085]

[Table 2]

Examples 6 to 8 and Comparative Example 2 Using a Loedige mixer FKM-130D (manufactured by Matsubo Corporation), 35 kg of a detergent composition having the composition shown in Table 3 was used.
Manufactured in units. The configuration of this Loedige mixer was substantially the same as that of Example 1. The operation was carried out as follows (the blending amount of each raw material in each step is shown in Table 4).
Shown). <Powder mixing> Solid component sodium carbonate (light ash: manufactured by Central Glass Co., Ltd., average particle size 56.1 μm)
m), sodium tripolyphosphate (STPP: average particle size 11.2 μm), and a fluorescent agent were stirred by a Loedige mixer at a stirring blade rotation speed of 130 r / min (peripheral speed of 3.4 m).
/ S), shearing machine rotation speed 2850 r / min (peripheral speed 27
m / s) for 1 minute.

<Addition of Reaction Initiator> A 48% by weight aqueous NaOH solution was added as a reaction initiator into a mixer, and mixed for 1 minute and 30 seconds under the same mixing conditions as described above.

<Neutralization> The linear alkylbenzene sulfonic acid (LA) was operated while operating the mixer under the same conditions as described above.
S: molecular weight 322) 9.40 parts by weight and 98% sulfuric acid 0.1%.
A mixture consisting of 84 parts by weight was added in 4 minutes. During this time,
Cooling was performed by passing 25 ° C. water through the mixer jacket.
During the addition of the mixture, the on-board temperature reached a maximum of 75 ° C. Immediately after the start of the addition of the mixture, the air inside the machine (300 L /
min).

<Mixing of Inorganic Powder> To the obtained neutralized mixture, an inorganic powder (1.75 parts by weight) was added, and the mixer was operated under the same conditions for 4 minutes and 30 seconds.

<Addition of Liquid Component / Surface Modification> While operating the mixer under the same conditions as above, a nonionic surfactant (0.98 parts by weight) was added to the mixer and mixed for 1 minute, and then the average particle size was 4 μm. Of zeolite (2.00 parts by weight) was added and mixed for another 5 minutes. Subsequently, a 40% by weight aqueous solution of acrylic acid-maleic acid copolymer was added and mixed for 1 minute and 30 seconds. Subsequently, zeolite (2.20 parts by weight) having an average particle size of 4 μm was added as a surface modifier, and the mixer was operated for 1 minute. Thus, a surface modification treatment was performed.

<After Blend> In the same manner as in Example 1, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition. In Examples 6 and 7, 30 seconds after the end of the addition of LAS, STPP or zeolite (1.75 parts by weight) was added as an inorganic powder. In Example 8, addition of STPP, which was an inorganic powder, was performed during the neutralization step, and mixing was continued for 5 minutes after completion of LAS addition. In addition,
STPP was added when the weight ratio of the added LAS to sodium carbonate was 0.6. In Comparative Example 2, mixing was continued for 5 minutes after the end of the LAS addition without adding the inorganic powder during or immediately after the neutralization step. Table 5 shows the physical properties of the resulting high bulk density detergent composition.

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

From the results shown in Table 5 above, by adding the inorganic powder during or immediately after neutralization, it is possible to suppress the particle growth after the completion of the neutralization, and as a result, only the excellent cleaning property is obtained. However, it can be seen that a high bulk density detergent composition having a small average particle size can be obtained.

Example 9 Using a Loedige mixer FKM130D (Matsubo Co., Ltd.), a detergent composition having the composition shown in Table 3 was produced in units of 35 kg. The configuration of this Loedige mixer was substantially the same as that of Example 1. The operation was performed as follows (the mixing amounts of the respective raw materials in each step are shown in Table 4). <Powder Mixing> The solid components sodium carbonate (the same light ash as in Example 6), sodium tripolyphosphate (the same STPP as in Example 6), and the fluorescent agent were mixed using a Loedige mixer under the same conditions as in Example 6. Mix for minutes.

<Neutralization> A mixture of 9.40 parts by weight of LAS and 0.84 parts by weight of 98% sulfuric acid was added over 4 minutes while operating the mixer under the same conditions as in Example 6. During this time, water was cooled at 25 ° C. through the mixer jacket. During the addition of the mixture, the on-board temperature reached a maximum of 80 ° C.
After the addition of the mixture was completed, the mixer was continuously operated under the same conditions for 30 minutes.
It was operated for 2 seconds to complete the neutralization reaction and the granulation operation. Also, aeration (300 L / mi) was started immediately after the addition of the mixture was started.
n) was performed.

<Addition of alkali metal aluminosilicate>
To the resulting neutralized mixture, 3.75 parts by weight of zeolite was added, and the mixer was subsequently operated under the same conditions for 4 minutes and 30 seconds.

<Addition of Liquid Component / Surface Modification> While operating the mixer under the same conditions as in Example 6, a mixture consisting of a 40% by weight aqueous solution of maleic acrylate copolymer and water was added, and the mixture was mixed for 1 minute and 30 seconds. Subsequently, the same surface modification treatment as in Example 6 was performed.

<After Blend> In the same manner as in Example 6, an enzyme and a fragrance were added to obtain a final powder of a high bulk density detergent composition.

Table 5 shows the physical properties of the resulting high bulk density detergent composition.
The high bulk density detergent composition excellent in detergency and having a small average particle diameter was obtained.

[0102]

According to the production method of the present invention, a high bulk density detergent composition having excellent detergency and a small average particle size can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyuki Yamashita 1334 Minato, Wakayama City, Kao Corporation Research Institute (72) Inventor Hiroshi Sakata 1334 Minato, Wakayama City, Kao Corporation Laboratory F-term (reference) 4H003 AB03 AB19 AC01 BA10 CA20 DA01 EA12 EA16 EA28 EB32 ED02 FA41

Claims (6)

[Claims] Step (A): A liquid acid precursor of an anionic surfactant and a water-soluble alkali-inorganic substance in an amount required to neutralize the liquid acid precursor are mixed with an alkali metal aluminosilicate Is mixed in a substantially absence of the liquid acid precursor to neutralize the liquid acid precursor; and (B): the neutralization mixture starts to coarsen during the neutralization in the step (A). A method for producing a high bulk density detergent composition having a bulk density of 650 g / L or more, comprising a step of adding and mixing an inorganic powder later. 2. In step (B), from the time when the weight ratio of the anionic surfactant to the water-soluble alkali-inorganic substance exceeds 0.25, the total amount of the liquid acid precursor is increased. The production method according to claim 1, wherein the addition of the inorganic powder is started at any time within 5 minutes after the completion of the addition. 3. The method according to claim 1, wherein the average particle size of the inorganic powder is 30 μm or less. 4. The method according to claim 1, wherein the inorganic powder is an alkali metal aluminosilicate. 5. Step (a): a liquid acid precursor of an anionic surfactant and a water-soluble alkali-inorganic substance in an amount required to neutralize the liquid acid precursor are mixed with an alkali metal aluminosilicate Is mixed in a substantially absence to neutralize the liquid acid precursor, and step (b): adding an alkali metal aluminosilicate to the neutralized mixture obtained in step (a). A method for producing a high bulk density detergent composition having a bulk density of 650 g / L or more, comprising a step of mixing. 6. In the step (B) or the step (b), the addition of the alkali metal aluminosilicate starts 5% after the completion of the addition of the liquid acid precursor of the anionic surfactant.
The method according to claim 4 or 5, wherein the time point is within a minute.