JP2009185203A - Powdered detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powdered detergent composition excellent in flowability in a high yield; and to provide a method for producing the powdered detergent composition. <P>SOLUTION: The powdered detergent composition is provided by a method which comprises a step of mixing a particulate solid water-soluble alkali inorganic matter of which the amount is not less than that required by neutralization of a liquid composition containing an acid precursor of an anion surfactant with the liquid composition containing the acid precursor of the anion surfactant, followed by adding an aqueous alkyl sulfate solution. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a powder detergent composition, and more particularly to a powder detergent composition having a high yield and excellent fluidity, and further relates to a method for producing the powder detergent composition.

  The detergent composition is used for washing clothes and the like, and is granular or powdery. Conventionally, it has been produced by a spray drying method, but there are problems such as a large amount of petroleum fuel consumed during production. In recent years, as in Patent Document 1 and Patent Document 2, a liquid acid precursor of alkylbenzene sulfonate is used. A method of dry neutralization with a water-soluble inorganic solid material such as sodium carbonate has come to be used.

  Moreover, although the manufacturing method of adding a liquid surfactant paste to zeolite or sodium carbonate is also disclosed, Patent Document 3 has a problem that the amount of petroleum fuel consumed during production is large because a fluidized bed is used. In Patent Document 4 and Patent Document 5, the particle size cannot be controlled and there are many coarse particles, so that there is a problem that the incidental equipment for pulverizing the coarse particles becomes large. These are all technologies for granulating inorganic powder with a small particle size of several hundreds of μm or less with a surfactant paste, and all feature a large change in particle size before and after addition of the surfactant paste. It is.

In addition, in order to improve productivity, detergents with high fluidity have been demanded. Here, the fluidity is the time required for 100 ml of powder to flow down in the bulk density measuring apparatus defined in JIS K3362. If the fluidity is high, the time required for filling the detergent can be shortened, so that the productivity is improved.
Since the conventional manufacturing method has poor fluidity, it takes time to fill the detergent, and an excessive investment is required for the filling equipment.

Furthermore, if the yield (ratio of passing through a sieve having a certain opening) is high in order to improve productivity, investment in ancillary equipment for pulverizing coarse particles can be suppressed. In order to achieve this, it is desirable that granulation is not required when a desired particle size is obtained.
JP-A-10-152700 Japanese Patent No. 3313372 US Pat. No. 5,516,447 European Patent No. 510746 International Publication No. 1995/010595 Pamphlet

  An object of the present invention is to provide a powder detergent composition having a high yield and excellent fluidity, and a method for producing the powder detergent composition.

The present inventors have found that a powder detergent composition having a high yield and improved fluidity can be easily obtained by blending an alkyl sulfate aqueous solution at the time of production of the powder detergent composition.
That is, the gist of the present invention is as follows.
[1] A particulate solid water-soluble alkali inorganic substance and an anionic surfactant acid precursor in an amount more than necessary to neutralize the liquid composition containing the anionic surfactant acid precursor. A powder detergent composition obtained by a method comprising a step of adding an aqueous alkyl sulfate solution after mixing a liquid composition,
[2] (A) Particulate solid water-soluble alkaline inorganic substance and anionic surfactant acid precursor in an amount more than necessary to neutralize the liquid composition containing the acid precursor of the anionic surfactant Mixing a liquid composition containing
(B) It is related with the manufacturing method of the powder detergent composition including the process of adding the alkyl sulfate aqueous solution to the mixture obtained at the process (A).

  According to the present invention, a powder detergent composition having a high yield and excellent fluidity is provided, and a production method capable of easily producing the powder detergent composition is provided.

(Powder detergent composition)
The powder detergent composition of the present invention comprises an anionic surfactant added to a particulate solid water-soluble alkaline inorganic material in an amount more than necessary to neutralize a liquid composition containing an acid precursor of an anionic surfactant. It is obtained by a method including a step of adding an alkyl sulfate aqueous solution after mixing a liquid composition containing an acid precursor.
In the present invention, “powder” is a concept including powder, granules and the like.

  Examples of the particles of the water-soluble alkali inorganic substance (hereinafter sometimes referred to as particulate solid water-soluble alkali inorganic substance for convenience) include those usually used as an alkali agent in a detergent composition, such as sodium carbonate, sodium hydrogen carbonate, Examples include sodium silicate and potassium carbonate. These may be used alone or in combination of two or more. Among the particulate solid water-soluble alkali inorganic substances, sodium carbonate is a preferred embodiment, and sodium carbonate can function as a detergent builder and an alkali agent in the final detergent composition.

  The average particle diameter of the particulate solid water-soluble alkali inorganic substance is preferably 10 μm or more, more preferably 40 to 200 μm, and particularly preferably 50 to 100 μm. In order to obtain a desired fluidity, 10 μm or more is preferable, and in order to obtain a desired yield, 200 μm or less is preferable.

  Here, the measurement of the average particle diameter of the substance added to a powder detergent composition is performed by the average particle diameter measuring method (JIS Z8801-1) mentioned later.

  The compounding amount of the particulate solid water-soluble alkali inorganic substance in the powder detergent composition is not less than the amount necessary for neutralizing the liquid composition containing the acid precursor of the anionic surfactant (neutralization equivalent). Yes, for example, preferably 1 to 20 times the neutralization equivalent, more preferably 2 to 15 times, and even more preferably 3 to 10 times.

  In the present invention, the acid precursor of the anionic surfactant is used as a liquid composition containing it. Although it does not specifically limit as an acid precursor of the anionic surfactant used, A linear alkyl (C10-C16) benzenesulfonic acid is preferable.

  The compounding amount of the acid precursor of the anionic surfactant is preferably 10 to 50% by weight, more preferably 12 to 45% by weight, and further preferably 15 to 40% by weight.

  In the production of the powder detergent composition of the present invention, an aqueous alkyl sulfate solution is used separately from the acid precursor of the anionic surfactant. Commercially available products can be used as the alkyl sulfate aqueous solution, but the alkyl sulfate preferably has 10 to 16 carbon atoms, and the cation constituting the alkyl sulfate is preferably sodium or potassium.

  In the present invention, the alkyl sulfate aqueous solution is mainly used as a surface modifier for detergent particles.

  The concentration of the alkyl sulfate aqueous solution is preferably 60 to 90% by weight, more preferably 70 to 80% by weight, and particularly preferably 72 to 77% by weight. From the viewpoint of handling properties, it is preferably 60% by weight or more and 90% by weight or less.

  The alkyl sulfate aqueous solution has a blending ratio as an alkyl sulfate in the powder detergent composition of preferably 1 to 6% by weight, more preferably 2 to 5% by weight, particularly preferably 2.5 to 5% by weight. It is added and used. If it is less than 1% by weight, the desired surface modification effect is hardly obtained, which is not preferable. If it exceeds 6% by weight, particle coalescence, that is, granulation occurs, and fluidity tends to decrease, which is not preferable. That is, one characteristic is that the variation of the average particle diameter is small within the range of 1 to 6% by weight.

  Examples of the surfactant used in the powder detergent composition of the present invention include the following.

  Examples of the anionic surfactant include alkyl (preferably C10-16) benzenesulfonate, alkyl or alkenyl ether (preferably C10-18) sulfate, alkyl or alkenyl (preferably C10). -16) Sulfate, α-olefin (preferably C10-18) sulfonate, alkane (preferably C10-18) sulfonate, fatty acid (preferably C10-18) salt, alkyl or Examples thereof include alkenyl ether (preferably having 10 to 18 carbon atoms) carboxylate, alkyl or alkenyl (preferably having 10 to 18 carbon atoms) phosphoric acid ester or a salt thereof. In these, the alkyl (C10-C16) benzenesulfonate or C10-C16 alkyl sulfate is preferable. The counter ion is preferably sodium, potassium or ammonium, particularly preferably potassium or sodium. The alkylbenzene sulfonate and alkyl sulfate as the surfactant are added separately from the acid precursor of the anionic surfactant and the alkyl sulfate aqueous solution described above.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether (preferably having a carbon number of 10 to 18), higher fatty acid alkanol (preferably having a carbon number of 10 to 18) amide, or any of the above alkylenes (preferably C2-C3) oxide adduct, sucrose fatty acid (preferably fatty acid having 10 to 18 carbon atoms) ester, alkyl (preferably C10 to 18) glucoside, fatty acid (preferably C10 to 18) glycerin monoester , Alkyl (preferably having 10 to 18 carbon atoms) amine oxide, and the like. Among these, polyoxyalkylene alkyls or alkenyl ethers having a total carbon number of 10 to 18 and an ethylene oxide addition mole number of 5 to 15 are preferred from the viewpoint of oil stain detergency.
The HLB value (calculated by the Griffin method) of these nonionic surfactants is preferably 10.5 to 15.0, more preferably 11.0 to 14.5. In addition, when using 2 or more types of nonionic surfactants, it is preferable that the value of average HLB is the above-mentioned range.

  Examples of amphoteric surfactants include betaine-type amphoteric surfactants such as alkyl (preferably 8-20 carbon atoms) betaines, imidazolinium betaines, and sulfonic acid-type amphoteric surfactants. And quaternary mono-long-chain alkyl ammonium salts and di-long-chain alkyl ammonium salts having a long-chain alkyl group having 8 to 18 carbon atoms.

  Among these surfactants, alkyl sulfates and alkylbenzene sulfonates are preferable as the surfactant used in the powder detergent composition of the present invention.

  The bleaching agent contained in the powder detergent composition of the present invention is preferably an oxygen-based bleaching agent composed of an inorganic peroxide such as percarbonates such as sodium percarbonate or perborate such as sodium perborate. When percarbonate is used in a powder detergent composition containing zeolite, for example, a percoate coated with one or more selected from paraffin, borate, perborate, ethylene oxide adduct of alcohol, polyethylene glycol, and silicate compound. It is preferred to use carbonates.

  The powder detergent composition of the present invention can contain a bleach activator in order to supplement the bleaching power of the oxygen bleach. The bleach activator is not particularly limited, and examples thereof include tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycolyl, alkanoyl or alkenoyl (preferably having 8 to 14 carbon atoms) oxybenzenecarboxylic acid or a salt thereof, alkanoyl or alkenoyl (preferably Is a C8-14) oxybenzene sulfonate. In particular, decanoyloxybenzenecarboxylic acid or a sodium salt thereof, and dodecanoyloxybenzenesulfonic acid sodium salt are preferred.

  In addition to those described above, the powder detergent composition of the present invention is a known detergent component, for example, an inorganic builder such as crystalline aluminosilicate, orthophosphate, pyrophosphate, tripolyphosphate; nitrilotriacetate, Organic builders such as ethylenediaminetetraacetate, citrate, isocitrate; alkaline agents such as silicate, carbonate, sesquicarbonate; polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, polyacrylate, acrylic acid-maleic acid An anti-staining agent such as an acid copolymer or a salt thereof can be blended, and an anti-caking agent, a fluorescent agent, a bluing agent, a photo-activated bleach, a fragrance, and the like can also be blended.

  From the viewpoint of cleaning performance and solubility, the powder detergent composition of the present invention is preferably 10 to 60% by weight of surfactant, more preferably 10 to 40% by weight, and more preferably 1 to 50% by weight of builder. Preferably 5 to 40% by weight, alkaline agent is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, bleaching agent is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, bleaching activity The agent is preferably 0 to 20% by weight, more preferably 1 to 10% by weight, the anti-staining agent is preferably 0 to 10% by weight, more preferably 0.1 to 5% by weight, and the fluorescent agent is preferably 0%. 10 to 10% by weight, more preferably 1 to 5% by weight, and perfume is preferably 0 to 5% by weight, more preferably 0.01 to 3% by weight. Although there is no restriction | limiting in particular in content in the powder detergent composition of this invention other than the above-mentioned well-known detergent component, In order to achieve desired fluidity | liquidity, these each component is 0-30 weight%. It is preferable to include.

The average particle diameter of the powder detergent composition of the present invention is preferably 150 to 1100 μm, more preferably 190 to 700 μm, still more preferably 190 to 650 μm, and particularly preferably 190, from the viewpoints of prevention of pasting during dissolution and solubility. ˜450 μm.
In addition, the above-mentioned average particle diameter is a value calculated | required from the weight fraction by the size of a sieve mesh, after vibrating for 5 minutes using the standard sieve of JISZ8801-1 (2000). More specifically, using a 9-stage sieve and a tray with a mesh opening of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm, the top of the top is stacked in order from the small sieve. Add 100g of powder detergent composition from above 2000μm sieve, cover and attach to low-tap type sieve shaker (manufactured by HEIKO, tapping 156 times / minute, rolling: 290 times / minute) and shake for 5 minutes Then, the weight of the powder detergent composition remaining on each sieve and the saucer was measured, and the weight ratio (%) of the powder detergent composition on each sieve was calculated. The average particle size was determined by accumulating the weight ratio of the particles on the sieve having small openings in order from the saucer to give a total of 50%.

  The powder detergent composition of the present invention can be suitably used as a powder detergent composition for clothing, an automatic dishwasher, or a house. Moreover, the powder detergent composition of this invention can also be used as a fiber pretreatment agent.

(Production method of powder detergent composition)
The method for producing the powder detergent composition of the present invention comprises:
(A) A particulate solid water-soluble alkali inorganic substance and an anionic surfactant acid precursor in an amount more than necessary to neutralize the liquid composition containing the anionic surfactant acid precursor. Mixing the liquid composition;
(B) A step of adding an aqueous alkyl sulfate solution to the mixture obtained in step (A) is included. Hereinafter, an example of the manufacturing method of the present invention will be described in more detail.

  The production method can be preferably divided into 1) a mixing step, 2) a dry neutralization step, 3) an alkyl sulfate aqueous solution addition step, and 4) other optional steps. Next, each step will be described.

1) Mixing step This step is a step of mixing a linear alkylbenzene sulfonic acid acid precursor (LAS-S) and sulfuric acid in advance, which is a preferred example of an anionic surfactant acid precursor, prior to dry neutralization. is there.

Some LAS-S used in the present invention contains residual sulfuric acid depending on the production method.
The linear alkylbenzene sulfonic acid is generally produced by the following two typical methods.
(1) Oleum (fuming sulfuric acid) sulfonation method
(2) SO ₃ gas sulfonation method

  (1) is a classic method for producing a linear alkylbenzene sulfonic acid, and the product may contain about 0.3 mol of sulfuric acid per mol of the linear alkylbenzene sulfonic acid. In (2), the purity of the linear alkylbenzene sulfonic acid in the product is high and the amount of residual sulfuric acid is relatively low. Usually, the residual sulfuric acid is 0.2 mol or less per 1 mol of linear alkylbenzene sulfonic acid. It is. Currently, from the viewpoint of quality and productivity, the production method (2) is mainly used as a method for producing high-purity linear alkylbenzene sulfonic acid. In the present invention, the linear alkylbenzene produced by (2) is used. Sulfonic acid is preferably used.

  Thus, sulfuric acid may already exist in LAS-S. The amount of such sulfuric acid, that is, the amount of sulfuric acid preliminarily present in LAS-S is not particularly limited, but from the viewpoint of the hue of the resulting powder detergent composition, the amount of LAS-S is 1 mol. 0.09 mol or less is preferable, and 0.06 mol or less is more preferable. In addition, as for carbon number of the alkyl group in LAS-S, 10-16 are preferable.

  The amount of sulfuric acid to be present in this step is preferably 0.1 to 1.0 mol with respect to 1 mol of LAS-S, more preferably 0.1 to 0.8 mol with respect to 1 mol of LAS-S. And particularly preferably 0.15 to 0.65 mol. From the viewpoint of suppressing the coarsening of the powder detergent composition, the amount of sulfuric acid is preferably 0.1 mol or more, and 1.0 mol or less from the viewpoint of ensuring the degree of freedom of the composition of the powder detergent composition. Is preferred.

  In addition, even when the amount of sulfuric acid preexisting in LAS-S is less than the above range, or even if the amount of sulfuric acid preexisting in LAS-S is within the above range, a smaller powder detergent composition When it is desired to obtain a product, it is preferable to intentionally add sulfuric acid to raw material components such as LAS-S. Therefore, in this production method, the mixing step is an optional step.

  The mixer used in this step is not particularly limited, and examples thereof include a liquid mixing tank equipped with a stirrer. Further, the degree of mixing may be such that each component is uniformly mixed. Other conditions for mixing (temperature, nitrogen substitution in the head space portion of the stirrer, etc.) are not particularly limited.

2) Dry-type neutralization step This step mixes LAS-S that has not undergone the mixing step or a mixture of LAS-S and sulfuric acid obtained in the mixing step and a particulate solid water-soluble alkali-inorganic substance. This is a process of dry neutralization. In this step, neutralization reaction and granulation occur simultaneously in combination with the particulate solid water-soluble alkaline inorganic substance, and neutralized particles are formed.

This step preferably includes the following steps (a) and (b).
That is,
Step (a): A step of mixing a particulate solid water-soluble alkali-inorganic substance and optionally a known substance generally used in detergent compositions (wherein the amount of the particulate solid water-soluble alkali-inorganic substance is LAS-S Or more than the amount necessary to neutralize the mixture of LAS-S and sulfuric acid obtained in the aforementioned mixing step, ie, more than the neutralization equivalent);
Step (b): While adding the LAS-S or the mixture of LAS-S and sulfuric acid obtained in 1) the mixing step to the mixture obtained in the step (a), the resulting mixture is maintained in a granular form. A step of performing a neutralization reaction,
It is.

About a process (a) The above-mentioned thing can be used preferably as a particulate solid water-soluble alkali inorganic substance. Preferably, the amount of particulate solid water-soluble alkali required to neutralize LAS-S or the mixture of LAS-S and sulfuric acid plus the amount necessary for functioning as a detergent builder and alkaline agent Inorganic materials are used to mix LAS-S or a mixture of LAS-S and sulfuric acid. Thereby, neutralization reaction can be performed favorably and the powder detergent composition which maintains the above-mentioned function can be produced.

  That is, the amount of the particulate solid water-soluble alkali inorganic substance is preferably the amount as described above.

  Further, in this step, known substances generally used in detergent compositions may be added and mixed. Such materials include tripolyphosphates, crystalline or amorphous alkali metal aluminosilicates, crystalline silicates, calcium carbonate, sodium sulfate, fluorescent agents, pigments, antifouling agents (polycarboxylate polymers, sodium carboxy Methyl cellulose, etc.), particulate surfactants (fatty acids or salts thereof, alkyl sulfates, etc.), spray dried powder, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfite and the like. Such a substance is arbitrarily used depending on its use.

  Also, tripolyphosphate, crystalline or amorphous alkali metal aluminosilicate, crystalline silicate, calcium carbonate, sodium sulfate, fluorescent agent, pigment, recontamination inhibitor, particulate surfactant, spray-dried powder, The amount of diatomaceous earth, calcite, kaolin, bentonite, sodium sulfite, etc. is not particularly limited.

  Although it does not specifically limit as a mixer for mixing the above-mentioned each component used in a process (a), A stirring granulator is used suitably. The stirring granulator is not particularly limited, but a stirring granulator having a stirring blade and a crushing / dispersing chopper (or a functionally equivalent one) is preferable.

  Specific examples of the agitation granulator used in the present invention include a batch granulator, a vertical granulator (manufactured by POWREC Co., Ltd.), a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and a redige mixer ((stock ) Matsubo), Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), Garycke mixer (manufactured by Meiji Kikai Co., Ltd.), and the like. Particularly preferred are Redige mixers and Proshare mixers. As a continuous type, continuous-type Redige mixer (medium speed mixer: relatively long residence time), CB recycler (manufactured by Loedige), turbulizer (Hosokawa Micron Corporation) )), Shugi mixer (manufactured by Powrec Co., Ltd.), flow jet mixer (manufactured by Powder Research Co., Ltd.), and the like. In the present invention, the aforementioned mixers may be used in appropriate combination.

  Further, the stirring granulator is more preferably equipped with a jacket for adjusting the internal temperature or equipped with a nozzle for performing a gas blowing operation.

  The degree of mixing in step (a) is not particularly limited as long as each component is uniformly mixed. For example, when an agitation granulator is used, the operating condition of the agitation granulator is preferably, for example, a mixing time of 5 minutes or less. The spindle stirring speed and crushing / dispersing chopper speed can be appropriately set depending on the model. For example, in the case of a batch type, the spindle stirring peripheral speed is 2 to 15 m / s from the viewpoint of mixing efficiency and machine durability. Preferably, the crushing / dispersing chopper peripheral speed is preferably 20 to 60 m / s from the viewpoints of crushing / dispersing efficiency and mechanical durability.

About Step (b) In Step (b), in order to dry-neutralize LAS-S, LAS-S or a mixture of LAS-S and sulfuric acid is gradually added to the mixture obtained in Step (a). It is preferable to do this. The time required for the addition of LAS-S or the above-mentioned mixture depends on the amount to be added and cannot be generally stated. However, in the case of a batch type, it is preferably 1 minute or more, more preferably 1 to 10 minutes, still more preferably 2 ~ 7 minutes. Here, if LAS-S or the above-mentioned mixture is added in a remarkably short time, unreacted LAS-S tends to accumulate and cause excessive aggregation.

  Moreover, as an addition method of this LAS-S or the above-mentioned mixture, you may carry out continuously or divided | segmenting into multiple times, and you may provide multiple addition means.

  In addition, although it does not specifically limit as a mixer which can be used in a process (b), The stirring granulator illustrated in the above-mentioned process (a) is suitable.

  Further, after the addition of LAS-S or the aforementioned mixture, the stirring granulator may be further operated for 30 seconds or more, more preferably for 1 minute or more. By performing such an operation, the neutralization reaction and the granulation operation can be completed, which is preferable.

In the step (b), it is preferable to perform neutralization while blowing gas. This is for the purpose of preventing the particulate matter from becoming a large lump by evaporating excess water generated by the neutralization reaction and cooling the particulate matter using gas. Examples of such gas include N ₂ gas and air. The amount of gas blown in (aeration amount) is not particularly limited, but is preferably 0.2 parts by weight or more per 100 parts by weight of particulate matter and 2 weights per minute from the viewpoint of efficiency for sufficiently removing excess water. Part or more is more preferable.

  Moreover, when soap (fatty acid sodium) is contained in the composition of a desired powder detergent composition, you may add a fatty acid arbitrarily in a process (b) and may perform dry neutralization of a fatty acid. As the order of addition, it is desirable to add the fatty acid after the addition of LAS-S or the mixture of LAS-S and sulfuric acid, and further, after adding the LAS-S or the mixture of LAS-S and sulfuric acid, the stirring granulator is turned on for 30 seconds. As described above, it is more desirable to add the fatty acid after operating for 1 minute or more. This is because when the neutralization of LAS-S or sulfuric acid is not completed, LAS-S or sulfuric acid may react with a fatty acid to produce a colored product, thereby deteriorating the appearance of the product. In addition, you may add soap in the arbitrary processes after adding the mixture of LAS-S or LAS-S, and a sulfuric acid instead of adding a fatty acid.

3) Alkyl sulfate aqueous solution addition process This process is a process of performing surface modification by adding an alkyl sulfate aqueous solution after dry neutralization. Here, the alkyl sulfate aqueous solution described above is preferably used.

The aqueous alkyl sulfate solution used in the present invention is preferably produced by the following representative method. That is, alcohol having 10 to 16 carbon atoms is sulfated with SO ₃ gas, and then neutralized with an aqueous solution of sodium hydroxide or potassium hydroxide. The viscosity of the alkyl sulfate aqueous solution varies greatly depending on its concentration, and the industrially handleable alkyl sulfate aqueous solution concentrations are 0 to 40% by weight and 60 to 90% by weight. When the concentration of the alkyl sulfate in the aqueous solution is 40% by weight or less, the amount of moisture brought in at the time of addition increases. In order to maintain stability, the pH is desirably 8 or more. Examples of the buffering agent for maintaining the pH include hydrogen phosphate, and the addition amount is preferably 2% by weight or less in the aqueous alkyl sulfate solution. Further, unreacted alcohol or sodium sulfate may be present in the alkyl sulfate aqueous solution. A hydrotrope such as carbitol or a co-solvent may be added to the aqueous alkyl sulfate solution for the purpose of adjusting the viscosity (Surfactants: Chemistry, Interfacial Properties, Applications, V. B. Fainerman, ELSEVIER (2001), page 36, lines 11-12).

  The amount of the alkyl sulfate aqueous solution used in this step is preferably the amount described above in the section of the powder detergent composition as the alkyl sulfate.

  The aqueous alkyl sulfate solution is desirably added at a temperature of 50 to 80 ° C. When the temperature is 50 ° C. or higher, the handling is good, and when the temperature is 80 ° C. or lower, the stability of the compound is good.

  The alkyl sulfate aqueous solution is added to the agitation granulator described above after 2) the dry neutralization step.

  The time required for the addition of the alkyl sulfate aqueous solution depends on the amount to be added and cannot be generally stated. However, in the case of a batch type, it is preferably 1 minute or more, more preferably 1 to 10 minutes, and further preferably 2 to 7 minutes. It is. Here, when the alkyl sulfate aqueous solution is added in a remarkably short time, it tends to cause excessive aggregation, so that it is preferably added in 1 minute or more.

  Moreover, as an addition method of this alkyl sulfate aqueous solution, you may carry out continuously or divided | segmenting into multiple times, and you may provide multiple addition means. Since the alkyl sulfate aqueous solution has a high viscosity, it is desirable to provide a relatively large opening without using a spray nozzle as in a normal liquid raw material.

  In addition, although it does not specifically limit as a mixer which can be used in this process, The stirring granulator illustrated in the above-mentioned 2) dry-type neutralization process is suitable.

  Further, after the addition of the alkyl sulfate aqueous solution, the stirring granulator may be operated for 30 seconds or longer, more preferably for 1 minute or longer. Such an operation is preferable because the surface modification operation can be completed.

  As described above, the alkyl sulfate aqueous solution adding step is completed. By this step, the powder detergent composition is surface-modified and the fluidity is improved.

4) Other optional steps The powder detergent composition obtained by the production method of the present invention described above may be further subjected to surface modification. That is, the method for producing a powder detergent composition of the present invention may further include, for example, a step of adding a flow aid after the addition of the alkyl sulfate aqueous solution. By adding a flow aid, it is possible to further improve the fluidity and storage stability of the resulting powder detergent composition.

  As the flow aid, commonly known ones can be used, and crystalline or non-crystalline alkali metal aluminosilicate (zeolite), calcite, diatomaceous earth, silica and the like are preferably used. Such an aluminosilicate is more preferably one having an average particle size of 10 μm or less in order to obtain a desired covering property. Further, the amount is preferably 5 to 50% by weight, more preferably 7 to 40% by weight of the final powder detergent composition from the viewpoints of coatability and fluidity. The average particle size of the flow aid is calculated on a volume basis and is a value measured using a laser diffraction particle size distribution analyzer: LA-500 (manufactured by Horiba, Ltd.).

  The operation time of the agitation granulator in the step of adding the flow aid is not particularly limited, but is preferably 1 to 5 minutes in order to be able to be sufficiently coated and to ensure productivity. In addition, although it does not specifically limit as a mixer which can be used in the process of adding a flow aid, The stirring granulator illustrated in the above-mentioned 2) dry-type neutralization process is suitable. .

  In addition, in this manufacturing method, a desired liquid component can be added (liquid component addition process) with the composition of the powder detergent composition to be obtained. The addition timing of the liquid component is not particularly limited, but is preferably before the addition of the flow aid. If the resulting powder detergent composition has good flowability and / or good storage stability after the addition of the liquid component, it is not necessary to add a flow aid.

  Examples of the liquid component include any liquid component in commercially available detergent compositions such as nonionic surfactants, water-soluble polymers (polyethylene glycol, maleic acrylate copolymer, etc.) and water. As the liquid component, only one component may be used, or two or more components may be used in combination. The amount of each liquid component is preferably 20% by weight or less, more preferably 15% by weight or less of the powder detergent composition as the final product, from the viewpoint of suppressing aggregation of the powder detergent composition.

  In addition, the operation time of the agitation granulator when the liquid component is added before the addition of the flow aid is not particularly limited, but is 0.5 to 8 minutes in order to sufficiently mix and ensure productivity. preferable. In addition, although it does not specifically limit as a mixer which can be used in the process of adding a liquid component, The stirring granulator illustrated in the above-mentioned 2) dry-type neutralization process is suitable.

  Furthermore, in this invention, you may add and mix the well-known substance generally used for the detergent composition after the dry-type neutralization process. For example, it may be added before the liquid component addition step and / or before the flow aid addition step. Such materials include tripolyphosphates, crystalline or amorphous alkali metal aluminosilicates, crystalline silicates, calcium carbonate, fluorescent agents, pigments, anti-staining agents (polycarboxylate polymers, sodium carboxymethylcellulose, etc.) , Particulate surfactants (fatty acids or salts thereof, alkyl sulfates, etc.), spray dried powder, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfite, soaps and the like. Such a substance is arbitrarily used depending on its application. Although there is no restriction | limiting in particular in the quantity of this substance, In order to achieve desired fluidity | liquidity, it is preferable to contain 0-30 weight% of these each component. In addition, although it does not specifically limit as a mixer which can be used in the process of adding this substance, The stirring granulator illustrated in the above-mentioned 2) dry-type neutralization process is suitable.

From the above, as a method for producing the powder detergent composition of the present invention,
(1): an embodiment having a step of further adding a liquid component after the step of dry neutralization and addition of an aqueous alkyl sulfate solution,
(2): an embodiment having a step of further adding a flow aid after the step of adding the liquid component in the embodiment of (1),
Is also cited as a preferred embodiment.

  The hue of the powder detergent composition to which the flow aid is added as described above is not particularly limited. For example, the average particle size of the powder detergent composition to which the flow aid is added is 350 to 500 μm. When the powder detergent composition is aligned and measured with a photoelectric colorimeter, the L value of the Hunter Lab color system is preferably 90 or more.

  In the present invention, other optional components may be added. The step of adding such an optional component is not particularly limited, but 3) it is preferably after the step of adding an aqueous alkyl sulfate solution. Such optional components may be added simultaneously with the flow aid. Examples of such optional components include enzymes, fragrances, bleaches, and dyes. Although there is no restriction | limiting in particular in the compounding quantity of this arbitrary component in a powder detergent composition, In order to achieve desired fluidity | liquidity, it is preferable to contain 0-30 weight% of each of these components. Such optional components are preferably blended by mixing with the powder detergent composition obtained by the production method of the present invention using a mixer such as a rotating drum.

  Embodiments in the present invention are not limited to the above-described method.

Examples 1-4 and Comparative Examples 1-2
The powder detergent composition of Examples 1-4 and Comparative Examples 1-2 was prepared as follows, and the physical property and quality were evaluated. Table 1 shows the components, powder physical properties, and quality evaluation used in the preparation of each powder detergent composition.
[Preparation of powder detergent composition]
As a raw material, linear alkylbenzene sulfonic acid (LAS-S) (Neoperex GS manufactured by Kao Corporation: average carbon number of alkyl group: 12 to 13) 17.5 to 27.5% by weight as an effective component of sodium salt, 4A-type zeolite (Zeobuilder, average particle size 2.9 μm) 22.00% by weight, sodium carbonate (Central Glass Co., Ltd.) 36.76-39.30% by weight, sodium sulfate (Shikoku Kasei Co., Ltd.) Manufactured by the same company) 2.73 to 4.29% by weight, polyethylene glycol aqueous solution (manufactured by Mitsui Chemicals, Inc., PEG 13000-L60) 1.0% by weight as an effective component, sodium salt of acrylic acid-maleic acid copolymer (BASF) Manufactured by Sokaran CP-5) 1.0% by weight as an effective component, sodium alkyl sulfate aqueous solution (AS) (Emal 10P manufactured by Kao Corporation dissolved in water) 75% by weight product) (average carbon number of alkyl group: 12 to 14) 0 to 10% by weight as an effective component, [Tinopearl CBS-X / Tinopal AMS-GX (manufactured by Ciba Specialty Chemicals)] weight ratio 1 / 1 mixture (fluorescent agent) 0.3 wt%, enzyme 0.5 wt%, bleach (sodium perborate monohydrate, manufactured by Degussa) 2 wt%, perfume 0.20 wt%, and moisture A powder detergent composition was prepared. In Comparative Example 2, 5% by weight of sodium alkyl sulfate (AS) powder (manufactured by Kao Corporation, Emar 10P) was used.

Hereinafter, the preparation process will be described in detail using Example 1 as an example.
Using a Redige mixer FKM-130D (manufactured by Matsubo Co., Ltd.) high-speed mixer, a powder detergent composition having the composition shown in Table 1 was produced in units of 35 kg. This mixer is equipped with a shearing machine corresponding to a stirring blade and a crushing / dispersing chopper.

The operation was performed as follows.
1) Mixing step 8.19 parts by weight of LAS-S and 0.85 part by weight of 98% sulfuric acid were mixed in another liquid mixing tank.

2-a) Dry neutralization step Step a)
A solid component, sodium carbonate (light ash: manufactured by Central Glass Co., Ltd., average particle size 56.1 μm) 15.69 parts by weight and 0.11 part by weight of a fluorescent agent were mixed with a Redige mixer using a stirring blade rotation speed. The mixture was mixed for 1 minute under the conditions of 130 rpm (circumferential speed 3.4 m / s) and shearing machine rotation speed 2850 rpm (circumferential speed 27 m / s).

2-b) Dry neutralization step Step b)
While operating the mixer under the same conditions as described above, 9.04 parts by weight of the previously mixed LAS-S sulfuric acid mixture was added over 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. At this stage, the temperature reached a maximum of 80 ° C. Throughout this stage, the reaction mixture was granular. The above LAS has been produced by SO ₃ gas sulfonation method, it was those containing 0.13 parts by weight of sulfuric acid. That is, 0.05 mol of sulfuric acid was contained in 1 mol of LAS-S. The ratio of LAS-S and sulfuric acid during neutralization was 0.39 mol of sulfuric acid per 1 mol of LAS-S. Sodium carbonate was 6.57 times the amount required for neutralization of LAS-S and sulfuric acid. Thereafter, the mixer was operated for 1 minute under the same conditions to complete the neutralization reaction and granulation operation.

  Further, aeration (300 L / min) was performed immediately after the start of LAS-S addition until the completion of the neutralization reaction. The total weight of the granular material (sodium carbonate and fluorescent agent) at this time is 15.80 kg, and the weight of air (25 ° C.) is 355 g / min. 2 parts by weight. The average particle size after this step was 192 μm.

3) Alkyl sulfate aqueous solution addition step 1.17 parts by weight of sodium alkyl sulfate aqueous solution (AS) (75% by weight product) were added and mixed for 1 minute. The average particle size after this step was 201 μm.

4) Other optional steps 0.58 parts by weight of an aqueous polyethylene glycol solution and 0.88 parts by weight of an aqueous maleic acid acrylate copolymer solution are added to a mixer and mixed for 1 minute and 30 seconds, followed by addition of zeolite (7.70 parts by weight). The mixer was turned on for an additional 2 minutes. The zeolite contained 1.54 parts by weight of crystal water. Using a rotating drum, the enzyme (0.18 parts by weight), the bleaching agent (0.70 parts by weight) and the detergent composition obtained above are mixed, and further the fragrance (0.07 parts by weight) is sprayed. A final powder of the detergent composition was obtained.

  The particles of the obtained powder detergent composition had a 1200 µm pass yield of 91%, an average particle size of 201 µm, and a fluidity of 5.9 seconds.

  The method for measuring the average particle diameter is as described above. The 1200 μm yield is the weight percentage of the powder passing through a sieve having an opening of 1200 μm, and the fluidity is the time (seconds) required for 100 ml of powder to flow down in the bulk density measuring device defined in JIS K3362. is there.

From Example 1 and Example 2, the powder detergent composition of the present invention had a small change in average particle size before and after the addition of the alkyl sulfate aqueous solution, a very good 1200 μm yield, and a very good fluidity. I know that.
From Example 3 and Example 4, the powder detergent composition of the present invention had a slightly larger average particle size, but had a good 1200 μm yield and good fluidity.
From Comparative Example 1, it can be seen that when the alkyl sulfate aqueous solution was not added, the average particle size was very large, and the 1200 μm yield was remarkably low. Therefore, in commercial production, ancillary facilities for pulverizing coarse particles may be excessive.
From the comparative example 2, when the alkyl sulfate powder was used instead of the alkyl sulfate aqueous solution, the fluidity was inferior so that it could not be measured.

By blending the alkyl sulfate aqueous solution into the powder detergent composition, a powder detergent composition having a high yield and improved fluidity can be obtained.

Claims (7)

  Liquid composition containing particulate solid water-soluble alkali inorganic substance and anionic surfactant acid precursor in an amount more than necessary to neutralize the liquid composition containing an anionic surfactant acid precursor A powder detergent composition obtained by a method comprising a step of adding an aqueous alkyl sulfate solution after mixing.   The powder detergent composition according to claim 1, wherein the alkyl sulfate has 10 to 16 carbon atoms.   The powder detergent composition according to claim 1 or 2, wherein the cation constituting the alkyl sulfate is sodium or potassium.   The powder detergent composition according to any one of claims 1 to 3, wherein the concentration of the alkyl sulfate aqueous solution is 60 to 90% by weight.   The powder detergent composition according to any one of claims 1 to 4, wherein an aqueous solution of an alkyl sulfate is added so that the blending ratio of the alkyl sulfate is 1 to 6% by weight.   The powder detergent composition in any one of Claims 1-5 whose acid precursor of an anionic surfactant is alkylbenzenesulfonic acid. (A) A particulate solid water-soluble alkali inorganic substance and an anionic surfactant acid precursor in an amount more than necessary to neutralize the liquid composition containing the anionic surfactant acid precursor. Mixing the liquid composition;
(B) A method for producing a powder detergent composition comprising a step of adding an aqueous alkyl sulfate solution to the mixture obtained in step (A).