JP2010144045A - Method for producing mononuclear detergent particle cluster - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a detergent particle cluster wherein e.g. a (poly)glyceryl ether represented by general formula (1), which is difficult to compound in a powdery detergent composition, is compounded, as an ingredient of such a detergent composition, particularly as an ingredient of a mononuclear detergent particle cluster having a sharp particle size distribution with particle growth suppressed. <P>SOLUTION: The method for producing the mononuclear detergent particle cluster having an average particle size of 150 &mu;m or larger and a particle growth degree of 1.5 or less includes: the step (A) of preparing a granular cluster for carrying a surfactant thereon; the step (B) of obtaining a mixture by mixing together the granular cluster prepared in the step (A) and a (poly)glyceryl ether (a) represented by the general formula (1): R-O-(C<SB>3</SB>H<SB>6</SB>O<SB>2</SB>)nH; and the step (C) of preparing the objective mononuclear detergent particle cluster by surface modification of the mixture obtained in the step (B). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a mononuclear detergent particle group containing glyceryl ether or polyglyceryl ether (hereinafter also referred to as “(poly) glyceryl ether”) as a nonionic surfactant. Furthermore, this invention relates to the mononuclear detergent particle group obtained by this manufacturing method.

  The glyceryl ether or polyglyceryl ether represented by the general formula (1), that is, (poly) glyceryl ether is drawing attention as a nonionic surfactant. This is because there are advantages such as having a high detergency, less foaming, good biodegradability, and being a carbon neutral component because it is derived from plant materials. Therefore, some detergent compositions using such (poly) glyceryl ether have been developed.

  For example, Patent Document 1 discloses a detergent composition containing glyceryl ethers and an anionic surfactant, and Patent Document 2 discloses a liquid detergent composition containing glyceryl ethers and hydrogen peroxide. Discloses a thickener for detergent and a high viscosity liquid detergent composition containing polyglyceryl ether.

However, the detergent compositions disclosed in these patent documents are all liquid detergent compositions, and there is no specific disclosure regarding powder detergent compositions. This is because (poly) glyceryl ether having the above-mentioned advantages has a very high viscosity, and thus it has been considered difficult to be incorporated into a powder detergent composition.
JP-A-7-500861 JP 2006-169516 A JP 2006-348073 A

  Accordingly, an object of the present invention is to suppress (particularly) particle growth by using (poly) glyceryl ether represented by the general formula (1), which is difficult to be blended in a powder detergent composition, as a component of a powder detergent composition. Another object of the present invention is to provide a method for producing a detergent particle group which is blended as a component of a mononuclear detergent particle group having a sharp particle size distribution.

  Therefore, the present inventors paid attention to the high viscosity of (poly) glyceryl ether and the like, and the specific surfactant-carrying granule group and (poly) glyceryl ether, etc., are loaded with other components in the granule group. It is thought that (poly) glyceryl ether etc. can be stably blended in the powder detergent composition by mixing it prior to mixing and thereby preferentially supporting (poly) glyceryl ether etc. in the granules. The present invention has been completed.

That is, the gist of the present invention is as follows.
[1] Next step:
Step (A): Step of preparing a granule group for supporting a surfactant,
Step (B): General formula (1):
R—O— (C ₃ H ₆ O ₂ ) nH (1)
(Wherein R represents a hydrocarbon group having 6 to 22 carbon atoms, and n represents a number of 1 to 7. Here, n is the degree of condensation of glycerin) (poly) glyceryl ether ( a) mixing the surfactant-carrying granule group prepared in step (A) to obtain a mixture, and step (C): surface-modifying the mixture obtained in step (B) Obtaining mononuclear detergent particles,
And having an average particle size of 150 μm or more,
Particle growth rate = [average particle size of mononuclear detergent particles obtained in step (C)] / [average particle size of particles for supporting surfactant]
A method for producing a mononuclear detergent particle group having a particle growth degree of 1.5 or less determined by
[2] A mononuclear detergent particle group obtained by the production method according to [1].

  The method for producing a mononuclear detergent particle group of the present invention provides a method for producing a detergent particle group containing a specific nonionic surfactant, which has conventionally been difficult to be blended into a powder detergent composition. This is an excellent effect. Moreover, according to the production method of the present invention, it is possible to produce a mononuclear detergent particle group with suppressed particle growth and a sharp particle size distribution with high yield. By suppressing the particle growth of the detergent particle group, that is, by making the detergent particle group mononuclear, it is possible to obtain a detergent particle group having excellent solubility. Further, by sharpening the particle size distribution of the detergent particles, not only the appearance is improved, but also the fluidity is improved, and a detergent having excellent solubility can be obtained. Furthermore, by using the anionic surfactant composition represented by the general formula (2), not only exhibits a high detergency against any dirt, but also contains the surfactant contained in carbon dioxide in the atmosphere. Since it becomes possible to substitute for the surfactant derived from the plant raw material comprised by the carbon neutral component which does not increase, the detergent particle group excellent in environmental performance can be provided.

  In the production method of the present invention, even when the nonionic surfactant [component (a)] represented by the general formula (1) is blended, the particle growth is suppressed and the particle size distribution is sharp. Regarding the mechanism capable of producing the mononuclear detergent particles with good yield, the surfactant-supporting granules prepared in the step (A) are quickly supported with the component (a) in the pores of the granules. This is considered to be because the expression of the binder function by the component (a) that can cause particle growth is suppressed.

<Process (A)>
Step (A) is a step of preparing a granule group for supporting a surfactant.
The surfactant-supporting granule group prepared in this step is not particularly limited. For example, a base granule group obtained by a spray drying method (referred to as “jet drying base granule group”) and spray drying. A group of base granules (referred to as “non-sprayed base granule group”) obtained by a method that does not use the method is mentioned. These granule groups can be prepared, for example, by the following method.

[Preparation of spray-dried base granules]
A preferred spray-dried base granule group is a granule group produced by spray drying and containing a water-soluble inorganic salt, and having a supporting capacity of 20 mL / 100 g or more.

  The spray-dried base granule group is prepared, for example, by spray drying a slurry containing a water-soluble inorganic salt. Although it does not specifically limit as water-soluble inorganic salt, For example, alkaline agents, such as sodium carbonate and potassium carbonate, sodium sulfate, sulfite, sodium chloride, etc. are preferable water-soluble inorganic salts. Such water-soluble inorganic salts can be used singly or in combination.

  In addition to the water-soluble inorganic salt, the following components can be further used. For example, sequestering agents such as zeolite, citrate and sodium tripolyphosphate; base materials having both sequestering ability and alkaline ability such as crystalline silicates; other commonly used in detergent compositions Bases such as surfactants known in the field of garment detergents; recontamination inhibitors such as acrylic acid polymers or acrylic acid maleic acid copolymers and carboxymethyl cellulose; fluorescent whitening agents and the like.

  Among these, it is preferable to use zeolite in combination with a water-soluble inorganic salt. When the zeolite is blended, the water content of the spray-dried base granule group is preferably 5% by weight or less of the spray-dried base granule group, and more preferably 3% by weight or less from the viewpoint of increasing the action of the zeolite to adsorb water. .

  The slurry is preferably a water slurry using water as a medium. The content of the water-soluble inorganic salt in the slurry is preferably 5% by weight or more from the viewpoint of detergency, and more preferably 10% by weight or more. On the other hand, from the viewpoint of increasing the pore diameter of the spray-dried base granule group, it is preferably 30% by weight or less, more preferably 20% by weight or less.

  The total content of the water-soluble inorganic salt and other components in the spray-dried base granule group is preferably 60% by weight or more, more preferably 70% by weight or more, and 80% by weight or more. Is more preferable. From the viewpoint of adsorbing water remaining in the component (a), the total content of such components is preferably 60% by weight or more of the spray-dried base granule group. In addition, when the base etc. which deteriorates in contact with an alkaline substance are contained in the spray-dried base granule group or are added in the step (B), from the viewpoint of suppressing deterioration of the base etc., an alkaline agent is used. It may be excluded from the spray-dried base granule group.

  The conditions (temperature, spray drying apparatus, spraying method, drying method, etc.) for spray drying the slurry for preparing the spray-dried base granule may be known conditions and are not particularly limited.

[Preparation of non-sprayed base granules]
The non-sprayed base granule group is obtained, for example, by adding water or an aqueous binder solution to “a powder raw material having an oil absorption capacity of 40 mL / 100 g or more excluding clay mineral” (referred to as “powder raw material (PM)”). It is a group of granules obtained by a method including steps. The non-sprayed base granule group also includes a granule group obtained by a method including a step of obtaining a granule group by adding water or an aqueous binder solution to a mixture of a powder raw material (PM) and a clay mineral.

  Examples of clay minerals that can be used in the present invention include talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, Chinwald mica, muscovite, paragonite, celadonite, sea chlorite, etc.), Chlorite (clinochlore, chamosite, nimite, penantite, sudite, donbasite, etc.), brittle mica (clinintite, margarite, etc.), sulite, serpentine Minerals (antigolite, lizardite, chrysotile, amesite, cronstedite, burcherin, greenerite, garnierite, etc.), kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.) It is. Of these, talc, smectite, swellable mica, vermiculite, chrysotile, kaolin mineral, and the like are preferable, smectite is more preferable, and montmorillonite is further preferable in terms of flexibility. Bentonite can be suitably used as montmorillonite. These can be used alone or in combination of a plurality of types. For example, a clay mineral having a particle diameter of 10 to 100 μm can be used as the clay mineral powder.

  In the powder raw material (PM) that can be used in the present invention, the supporting ability is a value determined by the following evaluation method.

  That is, 30 to 35 g of a sample (powder material (PM)) was put into an absorption measuring device (S410 manufactured by Asahi Research Institute), and the driving blade was 200 r. p. m. Rotate with A liquid nonion (Emulgen 108 manufactured by Kao Corporation) is dropped at a liquid supply rate of 4 mL / min to determine the point at which the maximum torque is obtained. The liquid addition amount at the point where the torque becomes 70% of the point where the maximum torque is reached is divided by the sample input amount to obtain the carrying capacity.

  The powder raw material (PM) is an essentially porous substance having fine pores of 10 μm or less inside, and a substance capable of supporting a surfactant in the pores. The upper limit of the carrying capacity is not particularly limited, but is preferably 100 mL / 100 g or less, for example.

  From the viewpoint of granulation, the average particle diameter of the powder raw material (PM) is preferably 50 to 250 μm, more preferably 50 to 200 μm, and further preferably 80 to 200 μm. From the viewpoint of solubility, the powder raw material (PM) is preferably a water-soluble substance.

  Examples of the powder raw material (PM) include light ash or soda ash prepared by baking sodium bicarbonate, sodium sulfate, porous powder prepared by drying trihydrate of sodium triphosphate. Light ash is particularly preferable from the viewpoint of easy handling and availability.

  The content of the powder raw material (PM) in the non-sprayed base granule group is preferably 40 to 95% by weight, more preferably 45 to 90% by weight in the non-sprayed base granule group, from the viewpoint of supporting ability. 50 to 85% by weight is more preferable, and 50 to 80% by weight is more preferable. In addition, when adjusting to the said composition by a drying process, 25-80 weight% is preferable in the granule group before performing a drying process, 30-77 weight% is more preferable, 32-77 weight% is further more preferable, 32 to 73% by weight is particularly preferred.

  When clay mineral and powder raw material (PM) are used in combination, the weight ratio of clay mineral to powder raw material (PM) (clay mineral / powder raw material) is preferably 1/1 to 1/30, more preferably It is 1/1 to 1/20, and more preferably 1/2 to 1/20.

  In addition to the clay mineral and the powder raw material (PM), the following other components can be used. Specific examples include builders generally used in laundry detergents, recontamination inhibitors and fluorescent whitening agents mentioned in the description of the spray-dried base granule group.

  Any method may be used for preparing the non-spray-dried base granule group as long as the clay mineral and / or powder raw material (PM) and water or an aqueous binder solution can be mixed substantially uniformly. For example, the mixture may be mixed using a low shear granulator, or after previously mixed using another mixer, the mixture may be transferred to the low shear granulator. Other mixers used for this operation include, for example, a drum-type mixer (manufactured by Nikko Co., Ltd.), a bread-type mixer (manufactured by Fuji Machine Co., Ltd.), and a ribbon mixer (Nichiwa Machine Industry Co., Ltd.). Product), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), Shugi Mixer (manufactured by Paulek), Redige Mixer (manufactured by Matsubo Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and the like.

  Next, water or an aqueous binder solution is added to the resulting mixture to obtain granules. The concentration of the aqueous binder solution is not particularly limited, but the particle size at the time of granulation of the non-spray-dried base granule group is greatly affected by the volume of the aqueous binder solution. Just decide. Specific examples of the binder herein include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether and derivatives thereof, polyvinyl alcohol and derivatives thereof, and water-soluble cellulose derivatives (these derivatives include ether compounds and the like. ), Organic polymers such as carboxylic acid polymers, starches and saccharides, and inorganic polymers such as amorphous silicates. From the viewpoint of caking property and detergency, water-soluble cellulose derivatives, saccharides and carboxylic acid polymers are preferable, and salts of acrylic acid-maleic acid copolymers and polyacrylates are more preferable. The salt is preferably a sodium salt, potassium salt or ammonium salt. In addition, as a weight average molecular weight of a carboxylic acid-type polymer, 1000-100000 are preferable and 2000-80000 are more preferable.

  The content of the binder in the non-sprayed base granule group is preferably 0 to 35% by weight, more preferably 5 to 30% by weight in the non-sprayed base granule group, from the viewpoints of caking and supporting ability. -20% by weight is more preferable, and 10-20% by weight is more preferable.

  Examples of the method for obtaining the granule include a method of granulating each component with a low shear granulator. In this manner, a granule group having a structure in which the powder raw material (PM) is gently aggregated or a granule group having a structure in which the clay mineral and the powder raw material (PM) are gradually aggregated is prepared as a non-jet drying base granule group.

[Physical properties of surfactant-supporting granules]
・ [Physical properties of spray-dried base granules]
The support capacity of the spray-dried base granule group is preferably 20 mL / 100 g or more, and more preferably 30 mL / 100 g or more. Moreover, as a preferable upper limit of carrying ability, it is 70 mL / 100g or less. In this range, aggregation between the spray-dried base granule groups is suppressed, and the mononuclearity of the particles in the mononuclear detergent particle group can be maintained, which is preferable.

  The measuring method of the carrying ability is as follows. A sample (granule group) 100 g is put into a cylindrical mixing vessel having an inner diameter of about 5 cm and a depth of about 15 cm equipped with a stirring blade inside. While stirring the stirring blade at 350 r / min, linseed oil at 25 ° C. is added at a rate of about 10 mL / min, and the change over time in the stirring power is measured. The input amount of linseed oil when the stirring power becomes the highest is defined as the carrying capacity (mL / 100 g).

  The bulk density of the spray-dried base granule group is preferably 200 to 1000 g / L, more preferably 300 to 1000 g / L, further preferably 400 to 1000 g / L, and more preferably 500 to 800 g / L. The bulk density is measured by a method defined in JIS K 3362.

  The average particle size of the spray-dried base granule group is preferably 150 to 500 μm, and more preferably 180 to 300 μm. The average particle diameter is a median diameter calculated from a weight fraction according to the size of the sieve mesh after vibrating for 5 minutes using a standard sieve of JIS Z 8801 (mesh opening 2000 to 125 μm).

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

  In the present specification, the fluidity of the spray-dried base granule group is measured as follows. That is, the fluidity is defined as the time required for 100 mL of spray-dried base granules to flow out from the bulk density measurement hopper defined by JIS K 3362.

  The method for measuring the mode diameter of the pore volume distribution of the spray-dried base granule group is as follows. The pore volume of the spray-dried base granule group is measured using a mercury porosimeter “SHIMADZU pore sizer 9320” based on the instruction manual as follows. That is, 200 mg of spray-dried base granule group is put into a cell, and mercury to be injected is measured by dividing it into a low pressure part (0 to 14.2 psia) and a high pressure part (14.2 to 3000 psia). The average of the two data before and after is averaged to smooth the measurement data, and the mode diameter is obtained.

・ [Physical properties of non-sprayed base granule group]
The non-jet drying base granule group is a granule group having a structure in which the powder raw material (PM) is gently aggregated, or a granule group having a structure in which the clay mineral and the powder raw material (PM) are gradually aggregated. Therefore, it has (1) a large gap between granules, (2) a small gap of 10 μm or less in the powder raw material (PM), and (3) three supporting sites between clay mineral layers. By adjusting the three loading sites, a non-sprayed base granule group having a desired loading ability can be obtained.

  From the viewpoint of increasing the allowable range of the amount of the liquid component to be supported, the non-sprayed base granule supporting ability is preferably 40 mL / 100 g or more, more preferably 45 mL / 100 g or more, more preferably 50 mL / 100 g or more. It is. It is considered that the relatively high carrying ability of the non-sprayed base granule group is achieved by granulating with the low shear granulator. The measuring method of the carrying ability is the same as that of the above-mentioned spray-dried base granule group.

  The bulk density of the non-jet dried base granule group is preferably 550 g / L or less, more preferably 400 to 450 g / L, and particularly preferably 400 to 500 g / L. It is considered that the relatively low bulk density of the non-spray-dried base granule group is achieved by granulating with the low shear granulator. The bulk density is measured by the method defined in JIS K 3362, as in the case of the above-mentioned spray-dried base granule group.

  From the viewpoint of powdering and solubility of the detergent composition when using a detergent composition comprising a detergent particle group in which a liquid surfactant is supported on the non-jet dried base granule group, non-jet dried base granules As an average particle diameter of a group, 140-600 micrometers is preferable, 200-500 micrometers is more preferable, 200-400 micrometers is further more preferable. The average particle diameter is measured by the same method as that for the above-mentioned spray-dried base granule group.

  In this specification, the fluidity | liquidity of a non-jet drying base granule group is measured by the method similar to the fluidity | liquidity of a spray drying base granule group.

  Moreover, in this specification, the mode diameter of the pore volume distribution of the non-jet drying base granule group is measured by the same method as the mode diameter of the pore volume distribution of the spray drying base granule group.

  The method for measuring the moisture in the non-drying base granule group is the same as the method for measuring the moisture in the spraying base granule group.

<Process (B)>
Step (B) is a step of obtaining a mixture by mixing component (a) and the surfactant-supporting granule group prepared in step (A).

[Component (a)]
Component (a) is a kind of nonionic surfactant, and the ether bond is formed by substituting the hydrogen atom of the hydroxy group in polyglycerin, which is glycerin or its condensate, with a hydrocarbon group having 6 to 22 carbon atoms. For example, glyceryl ether or polyglyceryl ether formed. Specifically, the component (a) is represented by the general formula (1):
R—O— (C ₃ H ₆ O ₂ ) nH (1)
(In the formula, R represents a hydrocarbon group having 6 to 22 carbon atoms, and n represents a number of 1 to 7). Here, n is the degree of condensation of glycerin.

  The component (a) may be a single compound represented by the general formula (1) or a combination of a plurality of compounds represented by the general formula (1). Among the compounds represented by component (a), R is an alkyl group having 12 and / or 14 carbon atoms, and the total degree of (poly) glyceryl ether having a condensation degree n of glycerol of 3 to 5 The ratio is preferably 40% by weight or more of the component (a), more preferably 50% by weight or more, more preferably 60% by weight or more, and more preferably 70% by weight or more. More preferably 80% by weight or more. Further, from the viewpoint of washing performance at low temperature, the upper limit of the ratio is preferably 99% by weight or less, more preferably 95% by weight or less, further preferably 90% by weight or less, and more preferably 85% by weight or less. Accordingly, the preferred range of the ratio is preferably 40 to 99% by weight, more preferably 50 to 95% by weight, further preferably 60 to 90% by weight, and more preferably 70 to 85% by weight.

  As the component (a), a plurality of compounds having different degrees of condensation n of glycerin of the general formula (1) may be included. Specifically, from the viewpoint of washing performance at a low temperature, it is preferable to include two or more compounds different from n, and more preferably to include three or more compounds. In component (a), it is preferable that R is an alkyl group having 12 and / or 14 carbon atoms and n is 3 to 5 because very high cleaning performance is exhibited. Here, when the component (a) includes a plurality of compounds having different n, crystallization of the component (a) is suppressed, so that high solubility is exhibited even at a low temperature, and as a result, good cleaning performance is obtained. Therefore, as a component (a), the thing containing 2 or more types of n of 3-5 is preferable, and what contains all 3 types (n = 3, 4, 5) is more preferable. Furthermore, the total ratio of the (poly) glyceryl ether in which R is an alkyl group having 12 and / or 14 carbon atoms and n is 3 to 5 is 99% by weight or less of the component (a). In this case, the solubility at a low temperature is remarkably improved, and as a result, the effect of greatly improving the cleaning performance is obtained. In general, the lower the ratio, the better the solubility at low temperatures, but at the same time the cleaning performance at normal temperature tends to decrease, so an appropriate balance is required.

  In addition, as an addition amount of the component (a) in the step (B), the addition amount of the component (a) is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the surfactant-carrying granule group. The amount is more preferably 15 to 50 parts by weight, and further preferably 20 to 40 parts by weight. From the viewpoint of improving the detergency due to the addition of the component (a), the addition amount is preferably 10 parts by weight or more, and the powder physical properties, oozing property, and anionic surfactant of the mononuclear detergent particle group From the viewpoint of the degree of freedom of the blending amount, the amount added is preferably 60 parts by weight or less.

[Other nonionic surfactants]
In this step, component (a) may be used alone as a nonionic surfactant, but another nonionic surfactant having a melting point at 30 ° C. or lower may be used in combination. Specifically, the component (a) and the other nonionic surfactant may be mixed and added. The melting point of other nonionic surfactants is 30 ° C. or lower, preferably 25 ° C. or lower, more preferably 22 ° C. or lower. In addition, after adding a component (a), in order to improve the oozing-out of a component (a), you may add soap aqueous solution. In that case, it is desirable to add the component (a) after the component (a) is sufficiently supported in the surfactant-supporting granule group.

  Examples of other nonionic surfactants having a melting point of 30 ° C. or less include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, alkyl (polyoxyalkylene) polyglycoside, polyoxyalkylene sorbitan fatty acid ester, Examples include polyoxyethylene polyoxypropylene block polymers such as oxyalkylene glycol fatty acid esters, polyoxyethylene polyoxypropylene polyoxyethylene alkyl ethers (hereinafter abbreviated as EPE nonions), and polyoxyalkylene alkylol (fatty acid) amides. .

  Especially, the polyoxyalkylene alkyl ether which added 4-12 mol (preferably 6-10 mol) of alkylene oxide to C10-C14 alcohol is preferable. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide, and ethylene oxide is preferable.

  Further, from the viewpoint of solubility, particularly solubility at low temperatures, the alcohol may be used in combination with ethylene oxide, propylene oxide, and if necessary, a compound obtained by block polymerization or random polymerization of ethylene oxide. Among these, EPE nonion is preferable.

  Further, in this step, known components usually used in detergents, for example, re-contamination preventive agents such as acrylic acid polymer, acrylic acid maleic acid copolymer and carboxymethyl cellulose; reducing agents such as sulfites; , And may be used together with component (a).

[Mixing method]
In the present invention, it is desirable to perform mixing with as low a share as possible when performing the step (B). Thereby, the particle growth by a highly viscous component (a) functioning as a binder can be suppressed. In order to perform mixing with as low a share as possible, for example, a means that operates the fluid number of the stirring blade in the range of 0.5 to 8.0 and does not rotate the crusher in the mixer equipped with the crushing blade. Use it. Further, as a means for suppressing poor mixing, it is desirable to spray at a high pressure using a nozzle when adding the component (a). If the dispersion state of the component (a) is good, either a one-fluid nozzle or a two-fluid nozzle may be used for spraying.

  As a mixer for mixing the component (a) and the surfactant-supporting granule group used in the step (B), for example, a nozzle for adding the component (a) and a temperature in the mixer are controlled. Therefore, the thing provided with the jacket is preferable.

  As a mixing condition in the step (B), a mixing condition that substantially maintains the form of the particle group for supporting the surfactant, that is, a mixing condition that suppresses the particle growth and does not cause the particle group to collapse or aggregate is selected. Is preferred. For example, when using a mixer equipped with a stirring blade, the shape of the mixing blade of the stirring blade provided in the machine is a paddle type from the viewpoint of suppressing the collapse of the particles for supporting the surfactant and the mixing efficiency The fluid number of the stirring blade is preferably 0.5 to 8.0, more preferably 0.8 to 4.0, and still more preferably 0.5 to 2.0. Moreover, when the shape of the said mixing blade is a screw type, the fluid number of the said stirring blade becomes like this. Preferably it is 0.1-4.0, More preferably, it is 0.15-2.0. Moreover, when the shape of a mixing blade is a ribbon type, the fluid number of the said stirring blade becomes like this. Preferably it is 0.05-4.0, More preferably, it is 0.1-2.0.

  Furthermore, you may use the mixer which comprises a stirring blade and a crushing blade. When mixing the surfactant-carrying granule group and component (a) using such a mixer, conventionally, it has been customary to rotate the crushing blade at a high speed in order to promote mixing. However, in the case of the present invention, it is preferable not to rotate the crushing blade substantially from the viewpoint of suppressing the collapse and aggregation of the surfactant-supporting granules. Here, the fact that the crushing blade is not substantially rotated means that the crushing blade is not rotated at all, or in view of the shape, size, etc. of the crushing blade, within a range in which the surfactant-carrying granule group is not collapsed and aggregated. Rotating the crushing blade for the purpose of preventing stagnation of various raw materials in the vicinity of the crushing blade. Specifically, when the crushing blade is continuously rotated, the fluid number is preferably 200 or less, more preferably 100 or less, and when it is intermittently rotated, the fluid number is not particularly limited. By mixing under such conditions, a mixture can be obtained without substantially disrupting and agglomerating the surfactant-supporting granules.

  In the present specification, the fact that the form of the surfactant-supporting granule group is substantially maintained, that is, it does not cause the surfactant-supporting granule group to collapse is the interface of the mixture obtained in the step (B). 70% or more of the number of granules for supporting an active agent is maintained in the form, and the particle growth is suppressed, that is, the aggregation is not caused. It is. These confirmation methods include, in the former, a method of observing particles after extracting a soluble component using an organic solvent, and in the latter, a method as defined in this specification. It is done.

Further, the fluid number defined in this specification is calculated by the following equation.
Fluid number = V ² / (R × g)
(Where V: peripheral speed [m / s] at the tip of the stirring blade or crushing blade, R: rotation radius [m] of the stirring blade or crushing blade,
g: Gravity acceleration [m / s ² ])

  The in-machine temperature at the time of mixing is preferably a temperature at which the component (a) and the surfactant-carrying granule group can be efficiently mixed while substantially suppressing the collapse / aggregation of the surfactant-carrying granule group. For example, the pour point or higher of the component (a) to be mixed is preferable, the pour point of 10 ° C or higher is more preferable, and the pour point of 20 ° C or higher is particularly preferable. Specifically, the range of 50-80 degreeC is preferable, and the range of 60-70 degreeC is more preferable. The in-machine temperature can be adjusted by flowing cold water or hot water through a jacket or the like. Therefore, the apparatus used for mixing preferably has a structure with a jacket. The mixing time is preferably 1 to 50 minutes, more preferably 5 to 40 minutes, and further preferably 10 to 30 minutes. From the viewpoint of the mixing property between the surfactant-carrying granule group and the component (a), the mixing time is preferably 1 minute or more. From the viewpoint of production efficiency and the suppression of disintegration of the surfactant-carrying granule group, the mixing time is 50 minutes or less is preferable. In the present specification, the pour point of the component (a) is a value obtained by measurement by a method according to JIS K 2269 unless otherwise specified.

  The mixing method in the step (B) may be a batch method or a continuous method. When mixing batchwise, it is preferable to add the component (a) after the surfactant-supporting granule group is previously charged in the mixer. The temperature of the component (a) to be supplied is preferably 70 ° C. or less, more preferably 60 ° C. or less, from the viewpoint of the stability of the component (a).

When mixing in a batch type, there is no particular limitation as long as a mixer generally used for batch type mixing is used. For example, the mixing blade shape is a paddle type mixer. A mixer having a shaft, and mixing the powder by attaching a stirring blade to the shaft: for example, Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granule Rator (Powrec Co., Ltd.), Redige Mixer (Matsubo Co., Ltd.), Proshare Mixer (Pacific Kiko Co., Ltd.), TSK-MTI Mixer (Tsukishima Kikai Co., Ltd.), JP 10-296064 (2) Forming a spiral in a cylindrical, semi-cylindrical, or conical fixed container, such as a mixing device described in Japanese Patent Application Laid-Open No. 10-296065. The Mixer that mixes by rotating bonnet blades: Ribbon mixer (manufactured by Hiyaki Machinery Co., Ltd.), batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), Ribocorn (Daishun Manufacturing Co., Ltd.) ), Julia mixer (manufactured by Tokuju Kogyo Co., Ltd.), etc., as a mixing machine with screw-shaped mixing blades, and (3) along the conical container, with the screw centered on the axis parallel to the container wall There are mixers of the type that perform mixing by revolving while rotating: for example, Nauter mixer (manufactured by Hosokawa Micron Corporation), SV mixer (manufactured by Shinko Pantech Co., Ltd.) and the like.

  Moreover, when mixing by a continuous type, if it uses the continuous mixer generally used for continuous mixing, it will not specifically limit, For example, using a continuous type apparatus among said mixers, a process ( Mixing in B) may be carried out.

[Other ingredients]
In the step (B), powder raw materials other than the surfactant-supporting granule group can be blended if desired. The blending amount is preferably 30 parts by weight or less with respect to 100 parts by weight of the surfactant-supporting granule group from the viewpoint of solubility.

  The powder raw material other than the surfactant-supporting granule group referred to in the present specification means a detergency enhancing agent or an oil absorbing agent for powder at room temperature (25 ° C.). Specifically, bases showing sequestering ability such as zeolite and citrate, bases showing alkaline ability such as sodium carbonate and potassium carbonate, sequestering ability and alkaline ability such as crystalline silicate Examples thereof include bases and the like, and amorphous silica and amorphous aluminosilicate having a low metal ion sequestering ability but high supporting ability. By using this powder raw material in combination with a surfactant-supporting granule group as desired, it is possible to increase the surfactant composition and reduce the adhesion of the mixture into the mixer, and to improve the cleaning power. You can also plan.

  The mononuclear detergent particles produced by the method of the present invention may contain an anionic surfactant composition known in the field of garment detergents. For example, an anionic surfactant can be contained in the mononuclear detergent particle group by adding and mixing the anionic surfactant composition in the step (B). In the case where the anionic surfactant composition is added and mixed in the step (B), the addition amount is preferably 10 to 60 parts by weight in 100 parts by weight of the surfactant-supporting granules. Part by weight is more preferable, and 20 to 50 parts by weight is further preferable. From the viewpoint of improving detergency due to the addition of an anionic surfactant composition, the amount added is preferably 10 parts by weight or more, and the powder physical properties, oozing property and component (a) of the mononuclear detergent particles are blended. From the viewpoint of the degree of freedom of the amount, the amount added is preferably 60 parts by weight or less.

  When the anionic surfactant composition is added and mixed in the step (B), the addition of the surfactant-carrying granules and the component (a) results in a mixture (preliminary mixture). After being obtained, it is preferable to add the anionic surfactant composition into the mixer. By setting it as such an addition time, since the mononuclear detergent particle group by which particle growth was suppressed can be manufactured with a sufficient yield, it is preferable. In this way, the preliminary mixture and the anionic surfactant composition can be mixed to obtain a mixture. In addition, when obtaining a mixture in a process (B), it is not necessary to fractionate a preliminary mixture once, or to stop the operation of a mixer.

  When the component (a) and the anionic surfactant composition are used in combination, the breaking load of the premix obtained by mixing the surfactant-carrying granule group and the component (a) is preferably smaller. Here, the breaking load of the premix can be assumed to be an indicator of the loading state of the component (a), and the smaller the value, the more the component (a) is loaded on the surfactant-carrying granule group, and the surface tackiness Decreases, and the anionic surfactant composition is more smoothly loaded. Specifically, after the breaking load is preferably in the range of 0 to 1500 mN, more preferably in the range of 0 to 700 mN, still more preferably in the range of 0 to 500 mN, more preferably After being in the range of 0 to 300 mN, the premix and the anionic surfactant composition are mixed to obtain a mixture. By obtaining such a mixture in the step (B), it is possible to produce a mononuclear detergent particle group having a sharp particle size distribution with suppressed particle growth with high yield. From the viewpoints of sharpening the particle size distribution of the mononuclear detergent particles, improving the yield, and increasing the amount of the anionic surfactant composition, the breaking load of the premix is 1500 mN or less. It is preferable. In the present specification, the breaking load of the preliminary mixture is a value measured as follows.

[Measurement method of breaking load]
An adapter having a diameter of 30 mm is attached to the rheometer, and the premixed material with a weight [g] obtained by dividing the bulk density [g / L] of the premixed product by 20 is set in a metal cylindrical container, and 9800 mN at 25 ° C. Compress for 3 minutes. Next, the molded body made of the preliminary mixture molded by compression is taken out of the container, the platform is raised at a rising speed of 2 cm / min, and force is applied to the molded body to break the molded body. This value is taken as the breaking load. In the present specification, a rheometer D type manufactured by FUDOH is used as a measuring instrument.

As an anionic surfactant composition used in the step (B), the general formula (2):
_{R 1 -O- (CH 2 CH 2} O) m-SO 3 M (2)
(Wherein R ₁ represents a hydrocarbon group having 10 to 18 carbon atoms, m represents a number of 0 to 3, and M represents an alkali metal atom or an amine), and the component (b) The component (c) containing 25 to 65 parts by weight of water with respect to 100 parts by weight of the component (b) is preferable. The component (c) is more preferably one containing 30 to 50 parts by weight of water with respect to 100 parts by weight of the component (b). From the viewpoint of handling property of the component (c), the content of the water is preferably 25 parts by weight or more, and from the viewpoint of increasing the blending amount of the component (b) in the surfactant-carrying granule group, The amount is preferably 65 parts by weight or less. R ₁ is more preferably a hydrocarbon group having 12 to 16 carbon atoms, further preferably an alkyl group or alkenyl group having 12 to 16 carbon atoms, and more preferably an alkyl group having 12 to 16 carbon atoms. Specific examples of the hydrocarbon group for R ₁ include linear or branched alkyl groups having 12, 14 and 16 carbon atoms, and component (b) has only one kind of such alkyl group. The compound which consists of these, The thing which combined the compound which this alkyl group consists of multiple types may be sufficient. m is the average number of moles of ethylene oxide added and represents a number of 0 to 3, preferably 0 to 2, more preferably 0 to 1, and still more preferably 0. M is preferably an alkali metal atom such as Na or K, or an amine such as ammonium or monoethanolamine or diethanolamine, and particularly preferably an alkali metal atom such as Na or K from the viewpoint of improving the detergency of the detergent composition. Accordingly, specific examples of the preferred component (b) include one or more components selected from the group consisting of sodium lauryl sulfate, sodium myristine sulfate, sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristine ether sulfate. .

[Component (c)]
Component (c) is a composition of an anionic surfactant. From the viewpoint of the stability of the anionic surfactant composition as the component (c), it is preferable to handle at a preferable use temperature of 70 ° C. or less, more preferably 60 ° C. or less. The viscosity of the component (c) in this temperature range is preferably 10 Pa · s or less and more preferably 5 Pa · S or less in the use temperature range of the component (c) from the viewpoint of handling in production. preferable. Here, the viscosity is determined by measuring at a shear rate of 50 [1 / s] with a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN).

  The viscosity of the component (c) varies greatly depending on its water content. For example, the moisture content of the alkali compound used when preparing the component (c) by neutralizing the acid precursor of the anionic surfactant represented by the general formula (2) as the component (b) with an alkali compound It is preferable to prepare component (c) having a desired moisture content, that is, having a desired viscosity. When component (c) contains 25 to 65 parts by weight of water with respect to 100 parts by weight of component (b) and component (b) (the water content of component (c) is 20 to 40 parts), the viscosity In general, it is known that the water content of the component (c) is adjusted within this range.

  Moreover, since the acid precursor of component (b) is very unstable and easily decomposes, it is preferably prepared so that the decomposition can be suppressed. The preparation method is not particularly limited, and a known method can be used. For example, using a loop reactor, heat of neutralization may be removed by a heat exchanger or the like, and the temperature control of the component (b) acid precursor and the component (c) may be performed. As a temperature range at the time of manufacture, 30-60 degreeC and 60 degrees C or less are mentioned as a storage temperature range after manufacture. Moreover, what is necessary is just to heat up as needed at the time of use, and to use a component (c).

  Moreover, it is preferable that the component (c) obtained has excess alkalinity from a viewpoint of suppressing decomposition | disassembly.

  In addition, the prepared component (c) includes unreacted alcohol and unreacted polyoxyethylene alkyl ether when producing the acid precursor of component (b), sodium sulfate as a by-product during neutralization reaction, neutralization A pH buffer, a decoloring agent, and the like that can be added during the reaction may be contained. In that case, the component (a) is added before the component (c), so that the liquid crystal and / or crystal structure in the surfactant is controlled and the effect of suppressing the bleeding of the component (a) is great. Therefore, it is preferable.

  At the time of mixing in the step (B), 1 to 10 parts by weight of polyethylene glycol (PEG) and / or fatty acid and / or soapy water is added to 100 parts by weight of the particles for supporting the surfactant to carry the surfactant. It is preferable to coat the surface of the granule group for use because the caking resistance is improved. Furthermore, the addition of PEG and / or fatty acid and / or soapy water is preferable because the solubility can be improved by suppressing aggregation and increasing dispersibility when the detergent particles are dissolved. The fatty acids and soaps used here are not treated as anionic surfactants.

<Process (C)>
Step (C) is a step of obtaining a mononuclear detergent particle group by subjecting the mixture obtained in step (B) to surface modification, preferably surface modification with a modifier. By performing this step (C), a mononuclear detergent particle group having improved fluidity and caking resistance can be obtained. Specific operations in the step (C) include, for example, an operation of mixing the mixture obtained in the step (B) and the modifier with an appropriate mixer.

  The modifier has an average primary particle size of 20 μm or less from the viewpoint of improving the coverage of the mononuclear detergent particle group and improving the fluidity and caking resistance of the mononuclear detergent particle group. preferable. The average particle diameter is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.) or microscopic observation.

  The modifier is preferably an aluminosilicate, inorganic fine powders such as silicate compounds such as calcium silicate, silicon dioxide, bentonite, sodium tripolyphosphate, talc, clay, amorphous silica derivatives, crystalline silicate compounds, A metal soap having primary particles of 20 μm or less can also be used.

  Moreover, it is preferable in terms of detergency that the modifying agent has high ion exchange ability and alkali ability.

  The amount of the modifier used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the mixture obtained in the step (B) in terms of fluidity and feeling of use. It is.

  As the mixing conditions in the step (C), it is preferable to select mixing conditions that substantially maintain the form of the mixture obtained in the step (B). A preferable mixing condition is to use a mixer equipped with both a stirring blade and a crushing blade. When such a mixer is used, it is provided in the machine from the viewpoint of suppressing the disintegration / aggregation of the particles for supporting the surfactant. The fluid number of the stirring blade is preferably 10 or less, more preferably 7 or less. From the viewpoint of efficiency of mixing with the modifier and dispersion with the modifier, the fluid number is preferably 2 or more, more preferably 3 or more. Furthermore, from the viewpoint of the efficiency of mixing with the modifier and dispersion of the modifier, the crushing blade fluid number is preferably 8000 or less, and more preferably 5000 or less. When the fluid number is within this range, a mononuclear detergent particle group having excellent fluidity can be obtained.

  As a preferable mixer, among the mixers used in the step (B), a mixer having both a stirring blade and a crushing blade can be mentioned. Moreover, temperature control of a mixture becomes easy by using another apparatus for a process (B) and a process (C). For example, when non-heat resistant components such as fragrances and enzymes are added during or after the step (C), it is preferable to adjust the temperature of the mixture in the step (C). The temperature can be adjusted by setting the jacket temperature and venting. In order to efficiently transfer the mixture obtained in the step (B) to the apparatus in the step (C), it is also a preferred form to add a part of the modifier at the end of the step (B).

[Mononuclear detergent particles]
As described above, the mononuclear detergent particle group of the present invention is obtained. Among these, as the mononuclear detergent particle group, 20-80% by weight of the surfactant-supporting granule group, 5-30% by weight of the component (a) and a modifier, or a surfactant 20-80% by weight of granules for loading, 5-30% by weight of component (a), and a modifier and a separately added detergent component (for example, fluorescent dye enzyme, perfume, antifoaming agent, bleaching agent, bleaching activity) And the like are preferred.

[Physical properties of mononuclear detergent particles]
In the present invention, the mononuclear detergent particle is a detergent composition produced using a surfactant-carrying granule as a core, and substantially contains one surfactant particle in one detergent particle. Detergent particles having granules as cores.

In addition, the particle growth degree defined by the following formula can be used as an index representing the mononuclearity of the detergent particles. The mononuclear detergent particles referred to herein have a particle growth rate of 1.5 or less, preferably 1.4 or less, more preferably 1.3 or less. The lower limit is not particularly limited but is preferably 1.0 or more.
Particle growth rate = [average particle size of mononuclear detergent particles obtained in step (C)] / [average particle size of particles for supporting surfactant]

  In addition, as an index indicating the anti-agglomeration property, the sample was vibrated for 5 minutes using a standard sieve of JIS Z 8801 (aperture 2000 to 125 μm), and then the ratio of particles remaining on the sieve having an aperture of 500 μm to 2000 μm was roughly determined. It can be used as the grain ratio. Here, as a preferable coarse particle rate, it is 30 weight% or less, More preferably, it is 20 weight% or less, More preferably, it is 10 weight% or less.

  Such mononuclear detergent particles have the advantage that the particle size distribution is sharp without the formation of particles outside the desired particle size range (aggregated particles) because aggregation between particles is suppressed.

The average particle size of the mononuclear detergent particle group is 150 μm or more, preferably 150 to 500 μm, and more preferably 180 to 350 μm. In the present specification, the average particle diameter of the mononuclear detergent particle group is a value determined as follows. That is, nine stages of sieves and trays having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm in a sieve specified in JIS Z 8801 are prepared. (Tanaka Chemical Machinery Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute). After sieving by shaking a 100 g sample for 10 minutes, the mass frequency under the pan and each sieve is integrated in the order of pan, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm. Go. When the opening of the first sieve with an integrated mass frequency of 50% or more is x _j μm, and the opening of the sieve smaller by one is x _{j + 1} μm, the distance from the tray to the x _j μm sieve When the mass frequency accumulation is Q _j %, and the mass frequency accumulation from the saucer to the x _{j + 1} μm sieve is Q _{j + 1} %, the average particle size x _a is given by the equations (A) and (B). Can be obtained.

  The bulk density of the mononuclear detergent particle group is preferably 300 to 1000 g / L, more preferably 500 to 1000 g / L, still more preferably 600 to 1000 g / L, and particularly preferably 650 to 850 g / L. In the present specification, the bulk density of the mononuclear detergent particle group is a value determined as follows. That is, the mononuclear detergent particles are put into a hopper for measuring bulk density defined by JIS K 3362, and the mononuclear detergent particles in the hopper are dropped into a 100 mL cylindrical container installed under the hopper outlet. The excess mononuclear detergent particles at the top of the cylindrical container are removed, the weight of the mononuclear detergent particles in the cylindrical container is measured, and this value is taken as the bulk density.

  In this specification, the fluidity | liquidity of a mononuclear detergent particle group is measured by the method similar to the fluidity | liquidity of a spray-drying base granule group. As the fluidity of the mononuclear detergent particles in the present specification, it is preferable to show a shorter time. A mononuclear detergent particle group having good flowability is advantageous in terms of handleability during production. Specifically, the fluidity of the mononuclear detergent particle group is preferably 7 seconds or less, and more preferably 6 seconds or less.

  The yield of the mononuclear detergent particles is calculated by dividing the weight of the sample that has passed through a sieve having an opening of 1180 μm by the weight of the entire sample. The yield is preferably 90% or more, and more preferably 95% or more.

  As described above, the mononuclear detergent particle group obtained by the production method of the present invention having the above-described structure has particle growth suppressed, a sharp particle size distribution, and not only an improvement in appearance. Thus, it is possible to obtain a detergent particle group having good fluidity and excellent exudation prevention and solubility, with good yield.

  As the solubility index in the present invention, the 60-second dissolution rate of the mononuclear detergent particles can be used. The dissolution rate is preferably 80% or more, and more preferably 90% or more.

The 60-second dissolution rate of the mononuclear detergent particle group is calculated by the following method.
1 liter of hard water (Ca / Mg molar ratio 7/3) corresponding to 71.2 g CaCO ₃ / liter cooled to 5 ° C. is a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd. 1 In a state where the water temperature of 5 ° C. is kept constant in a water bath, the stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, trade name: Teflon (registered trademark)) In SA (round thin type)), stirring is performed at a rotational speed (800 r / m) at which the spiral depth with respect to the water depth is approximately 1/3. A mononuclear detergent particle group that has been reduced and weighed to 1.000 ± 0.0010 g is added to and dispersed in water under stirring, and stirring is continued. Sixty seconds after the introduction, the mononuclear detergent particle group dispersion in the beaker was filtered through a standard sieve (diameter 100 mm) having a mesh size of 74 μm as defined in JIS Z 8801 of known weight, and the water-containing single particles remaining on the sieve The nuclear detergent particles are collected together with a sieve in an open container of known weight. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The collected residue of the mononuclear detergent particles is dried in an electric dryer heated to 105 ° C. for 1 hour, and then held and cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total weight of the dried residue of mononuclear detergent particles, the sieve, and the collection container is measured, and the dissolution rate (%) of the mononuclear detergent particles is calculated by equation (2).

Dissolution rate (%) = {1- (T / S)} × 100 (2)
S: input weight of mononuclear detergent particles (g)
T: When the aqueous solution obtained under the above stirring conditions is subjected to the sieve, the dry weight of the dissolved residue of the mononuclear detergent particles remaining on the sieve (drying condition: 1 hour at a temperature of 105 ° C.) After holding, hold in a desiccator (25 ° C) containing silica gel for 30 minutes) (g)

  Moreover, the mononuclear detergent particle group of the present invention is also excellent in the anti-bleeding property of the component (a). About the exuding property of a nonionic surfactant, it evaluates as follows.

  Using a filter paper (No. 2 manufactured by ADVANTEC), make a box without a top with a length of 10.2 cm, a width of 6.2 cm, and a height of 4 cm, and fix the four corners with a stapler. In advance, two lines are drawn with an oil-based magic on the diagonal of the bottom portion, and crossed. 200 mL of a sample is put in this box, sealed in an acrylic case, and left in a thermostatic chamber at a temperature of 30 ° C. for 7 days to determine the bleeding property of the component (a).

The determination was made by visually observing the bleeding of the oil-based magic drawn on the bottom after discharging the sample. Evaluation is 1-5 ranks, and the state of each rank is as follows.
Rank 1: There is no blur.
Rank 2: A state in which bleeding occurs in a part of the line and cilia grow.
Rank 3: The entire line is blurred and the average thickness of the magic is less than 2.0 times.
Rank 4: The entire line is blurred and the average thickness of the magic is 2.0 times or more and less than 3.0 times.
Rank 5: The entire line is blurred and the average thickness of the magic is 3.0 times or more.
In addition, in this invention, the said evaluation of a blur condition is a thing of ranks 1 and 2.

  The invention is further illustrated based on the following examples. In addition, the spray-dried base granule group used in Examples 1, 3, 4, and 9 to 13 was produced by the following procedure.

396.9 kg of water was added to a 1 m ³ mixing tank equipped with a stirring blade, and after the water temperature reached 55 ° C., 110.77 kg of sodium sulfate and 120 kg of sodium carbonate were added. After stirring for 10 minutes, 138.46 kg of 40 wt% sodium polyacrylate aqueous solution was added. Further, after stirring for 10 minutes, 36.920 kg of sodium chloride and 120 kg of zeolite were added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C.

This slurry was sprayed at a spray pressure of 25 kg / cm ² from a pressure spray nozzle installed near the top of the spray drying tower. The hot gas supplied to the spray drying tower was supplied at a temperature of 225 ° C. from the bottom of the tower, and was discharged at 105 ° C. from the top of the tower. The water content in the spray-dried base granule group was 0.3%.

  The physical properties of the obtained spray-dried base granule group are as follows: the average particle size is 261 μm, the bulk density is 540 g / L, the fluidity is 5.1 seconds, the mode diameter of the pore volume distribution is 0.4 μm, and the carrying capacity is 45 mL / 100 g.

The spray-dried base granule group used in Example 2 was produced by the following procedure.
409.5 kg of water was added to a 1 m ³ mixing tank having a stirring blade, and after the water temperature reached 55 ° C., 114.29 kg of sodium sulfate and 47.62 kg of sodium carbonate were added. After stirring for 10 minutes, 142.86 kg of 40 wt% sodium polyacrylate aqueous solution was added. Further, after stirring for 10 minutes, 47.62 kg of sodium chloride and 200 kg of zeolite were added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 58 ° C.

This slurry was sprayed at a spray pressure of 25 kg / cm ² from a pressure spray nozzle installed near the top of the spray drying tower. The hot gas supplied to the spray drying tower was supplied at a temperature of 235 ° C. from the bottom of the tower, and was discharged at 115 ° C. from the top of the tower. The water content in the spray-dried base granule group was 2.0% by weight.

  The resulting spray-dried base granule group has physical properties of an average particle diameter of 201 μm, a bulk density of 551 g / L, a fluidity of 5.3 seconds, a mode diameter of the pore volume distribution of 1.2 μm, and a supporting capacity of It was 40 mL / 100 g.

The non-blow-dry base granule group used in Examples 5 to 8 was produced by the following procedure.
70L drum granulator (φ40cm × L60cm / rotation speed 32rpm / fluid number) with baffle plate 2.1kg clay mineral and 4.2kg light ash (clay mineral / powder raw material = 1/2) Mixed in 0.23). After mixing for 2 minutes, 3.8 kg of 25% sodium polyacrylate aqueous solution was used with a two-fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd .: binder spray pressure 0.15 MPa / air spray pressure for atomization 0.3 MPa). For 5 minutes. After the addition, the mixture was granulated for 3 minutes, then discharged from a drum granulator, and dried at 200 ° C. for 3 hours using an electric dryer. The water content after drying was 1.3% by weight.

  The physical properties of the obtained non-spray-dried base granule group were an average particle size of 320 μm, a bulk density of 495 g / L, a fluidity of 5.3 seconds, a pore volume distribution mode diameter of 20 μm, and a loading capacity of 51 mL / 100 g. It was.

  The composition of the surfactant used in Examples and the like is as shown in Tables 1 and 2.

The raw materials used in the examples and the like are as follows.
-Sodium polyacrylate: weight average molecular weight 10,000 (manufactured by Kao Corporation)
・ Zeolite: made by Zeobuilder; trade name: Zeobuilder (Zeolite 4A type, average particle size 3.5 μm)
Component (a): Lauryl (poly) glyceryl monoether (in the general formula (1), the proportion of glycerin having a condensation degree n of 3 to 5 is 55.4% by weight based on the total of 1 to 7 The viscosity at 80 ° C. is 800 mPa · s)
Ingredient (b ¹ ): sodium alkyl ether sulfate (a mixture of alkyl chain lengths of 12, 14, 16 with a mixing ratio of 67% by weight / 28% by weight / 5% by weight)
Component (b ² ): sodium polyoxyethylene alkyl ether sulfate (having an alkyl chain length of 12; the average number of moles of ethylene oxide added is 2)
Component (c ¹ ): Containing 33 parts by weight of water with respect to 100 parts by weight of component (b ¹ ); viscosity at 60 ° C. is 8000 mPa · s
Component (c ² ): Containing 43 parts by weight of water with respect to 100 parts by weight of component (b ² ); viscosity at 60 ° C. is 3100 mPa · s
・ Clay mineral: Round rosyl DGA powder (manufactured by Sud Kemi)

Example 1
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 10 parts by weight of component (a) at 80 ° C. was added over 2 minutes, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

  In addition, in Table 1, in addition to the particle growth degree and average particle diameter (whole grain) of the detergent particle group, the weight% (coarse particle ratio) of particles of 500 μm or more, the detergent particle group having passed through a sieve having an opening of 1180 μm The fluidity, bulk density, dissolution rate, etc. are described. The exuding property of the component (a) was measured / evaluated by a detergent particle group excluding the agglomerated / coarsed particles through the sieve.

As an index of the particle size distribution of the detergent particle group, the detergent particle group that was passed through a 1410 μm sieve was fitted, and the Rosin-Rammler number was calculated and used. The following formula was used to calculate the Rosin-Rammler number.
log (log (100 / R (Dp))) = nlog (Dp / De)
R (Dp): Cumulative rate [%] of powder having a particle size of Dp μm or more
Dp: particle size [μm]
De: Average particle diameter [μm]
n: Rosin-Rammler number (Here, the higher the Rosin-Rammler number n, the sharper the particle size distribution. n is preferably 1.0 or more, more preferably 1.5 or more.)

Example 2
A detergent particle group having the composition shown in Table 1 was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained detergent particles.

Example 3
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, and then mixed for 20 minutes. Subsequently, 15 parts by weight of a component (c ¹ ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Example 4
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 20 parts by weight of the component (a) at 80 ° C. was added over 1 minute, followed by mixing for 20 minutes. Subsequently, 15 parts by weight of a component (c ² ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Example 5
48 parts by weight of non-sprayed base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket) and main shaft (main shaft rotation speed: 80 r / min, stirring blade fluid) Number: 1.07) rotation was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 10 parts by weight of component (a) at 80 ° C. was added over 2 minutes, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Example 6
A detergent particle group having the composition shown in Table 1 was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained detergent particles.

Example 7
48 parts by weight of non-sprayed base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket) and main shaft (main shaft rotation speed: 80 r / min, stirring blade fluid) Number: 1.07) rotation was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, and then mixed for 20 minutes. Subsequently, 15 parts by weight of a component (c ¹ ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Example 8
48 parts by weight of non-sprayed base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket) and main shaft (main shaft rotation speed: 80 r / min, stirring blade fluid) Number: 1.07) rotation was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotation of the main shaft for 1 minute, 20 parts by weight of the component (a) at 80 ° C. was added over 1 minute, followed by mixing for 20 minutes. Subsequently, 15 parts by weight of a component (c ² ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Comparative Example 1
44 parts by weight of sodium carbonate preheated to 50 ° C. was put into a Redige mixer (manufactured by Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotational speed of main shaft: 80 r / min, fluid number of stirring blade: 1. The rotation of 07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotating the main shaft for 1 minute, 10 parts by weight of 40% sodium polyacrylate aqueous solution was added over 2 minutes, and then mixed for 6 minutes. Furthermore, 10 parts by weight of the component (a) at 80 ° C. was added over 2 minutes, and then mixed for 6 minutes. Once the rotation was stopped, 20 parts by weight of a modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1. In addition, the following were used as sodium carbonate.

  Sodium carbonate: manufactured by Central Glass Co., Ltd., trade name: dense ash, average particle size 290 μm, bulk density 980 g / L

Comparative Example 2
A detergent particle group having the composition shown in Table 1 was obtained in the same manner as in Comparative Example 1. Table 1 shows the physical properties of the obtained detergent particles.

Comparative Example 3
44 parts by weight of sodium carbonate preheated to 50 ° C. was put into a Redige mixer (manufactured by Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotational speed of main shaft: 80 r / min, fluid number of stirring blade: 1. The rotation of 07) was started. The chopper (with crushing blades) was not rotated, and 80 ° C. warm water was passed through the jacket at 10 L / min. After stirring by rotating the main shaft for 1 minute, 10 parts by weight of 40% sodium polyacrylate aqueous solution was added over 2 minutes, and then mixed for 6 minutes. Thereafter, 10 parts by weight of the component (a) at 80 ° C. was added over 1 minute, and then mixed for 20 minutes. Subsequently, 15 parts by weight of a component (c ¹ ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 1.

Example 9
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring by rotating the main shaft for 1 minute, 15 parts by weight of 60 ° C. component (c ¹ ) was added over 1 minute, and then mixed for 6 minutes. Subsequently, 10 parts by weight of the component (a) at 80 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 2.

Example 10
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotation of the main shaft, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, and then mixed for 6 minutes. The breaking load of the mixture was measured and found to be 1372 mN. Subsequently, 15 parts by weight of a component (c ¹ ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 2.

Example 11
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotating the main shaft, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, followed by mixing for 20 minutes, and the breaking load of the mixture was measured to be 196 mN. Subsequently, 15 parts by weight of a component (c ¹ ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 2.

Example 12
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotation of the main shaft, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, and then mixed for 6 minutes. The breaking load of the mixture was measured and found to be 1372 mN. Subsequently, 15 parts by weight of a component (c ² ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 2.

Example 13
48 parts by weight of the spray-dried base granule group preheated to 50 ° C. is put into a Redige mixer (Matsubo Co., Ltd., capacity 20 L, with jacket), and the main shaft (rotation speed of main shaft: 80 r / min, fluid number of stirring blade) : The rotation of 1.07) was started. The chopper (with crushing blades) was not rotated, and hot water at 60 ° C. was passed through the jacket at 10 L / min. After stirring for 1 minute by rotating the main shaft, 10 parts by weight of component (a) at 80 ° C. was added over 1 minute, followed by mixing for 20 minutes, and the breaking load of the mixture was measured to be 196 mN. Subsequently, 15 parts by weight of a component (c ² ) at 60 ° C. was added over 1 minute, and then mixed for 6 minutes. Once the rotation was stopped, 12 parts by weight of the modifier (zeolite) was charged into the mixing apparatus, and the main shaft (rotation speed: 150 r / min, stirring blade fluid number: 3.8) and chopper (chopper rotation speed). : 3600 r / min, crushing blade fluid number: 1010) for 15 seconds. After the operation for 15 seconds, the rotation of the chopper was stopped, and only the main shaft was rotated for another 30 seconds, and then discharged. The physical properties of the obtained detergent particles were as shown in Table 2.

  As can be seen from the examples, the surfactant-carrying granule group is a spray-dried base granule group or a non-jet-dried base granule group, and contains the nonionic surfactant of component (a) It was possible to produce a detergent particle group. The detergent particle groups obtained in the examples were all mononuclear and satisfied the basic performance (leachability, solubility) as the detergent particle group. Moreover, looking at the Rosin-Rammler number of the detergent particle group, the detergent particle group in the examples is higher than the detergent particle group in the comparative example, and according to the production method of the present invention, the particle size distribution is very It was found that sharp detergent particles can be produced.

Furthermore, from Example 9 and Example 10, it was found that by adding the component (c ¹ ) after the component (a) was added, the exudation and solubility of the detergent particle group could be further improved. From Example 10 and Example 11 and Example 12 and Example 13, by making the breaking load of the preliminary mixture within a specific range, the degree of particle growth of the detergent particles can be further suppressed, and coarse particles The rate could be further reduced, the solubility could be further improved, and the particle size distribution could be made sharper.

  On the other hand, in the detergent particle group (comparative example) in which the nonionic surfactant of component (a) is blended without using the surfactant-carrying granule group, the basic performance as a detergent particle group (seepage) Property and solubility).

The production method of the present invention can be used for production of a mononuclear detergent particle group in which a nonionic surfactant having a specific structure represented by the general formula (1) is blended.

Claims (8)

Next step:
Step (A): Step of preparing a granule group for supporting a surfactant,
Step (B): General formula (1):
R—O— (C ₃ H ₆ O ₂ ) nH (1)
(Wherein R represents a hydrocarbon group having 6 to 22 carbon atoms, and n represents a number of 1 to 7. Here, n is the degree of condensation of glycerin) (poly) glyceryl ether ( a) mixing the surfactant-carrying granule group prepared in step (A) to obtain a mixture, and step (C): surface-modifying the mixture obtained in step (B) Obtaining mononuclear detergent particles,
And having an average particle size of 150 μm or more,
Particle growth rate = [average particle size of mononuclear detergent particles obtained in step (C)] / [average particle size of particles for supporting surfactant]
A method for producing a mononuclear detergent particle group having a particle growth degree of 1.5 or less determined by 1 above.   The production method according to claim 1, wherein the surfactant-supporting granule group is a spray-dried base granule group or a non-jet-dried base granule group.   The production method according to claim 1 or 2, wherein in step (B), 10 to 60 parts by weight of the component (a) is added to and mixed with 100 parts by weight of the surfactant-supporting granules.   In step (B), 10 to 60 parts by weight of an anionic surfactant composition is further added to and mixed with 100 parts by weight of the surfactant-supporting granules. 2. The production method according to item 1.   In step (B), the surfactant-carrying granule group prepared in step (A) and the component (a) are mixed to obtain a premix, and then the premix and the anionic surfactant composition The production method according to claim 4, wherein the mixture is obtained by mixing with the above. The manufacturing method of Claim 5 whose breaking load measured as follows of the pre-mixture obtained is 0-700 mN:
(An adapter having a diameter of 30 mm was attached to a rheometer, and the premixed mixture with a weight [g] obtained by dividing the bulk density [g / L] of the premixed product by 20 in a metal cylindrical container was set at 25 ° C. The molded product made of the preliminary mixture formed by compression is taken out from the container, and the platform is raised at a rising speed of 2 cm / min. The force when the molded body is broken by applying force is measured, and this value is taken as the breaking load.) The anionic surfactant composition has the general formula (2):
_{R 1 -O- (CH 2 CH 2} O) m-SO 3 M (2)
(Wherein R ₁ represents a hydrocarbon group having 10 to 18 carbon atoms, m represents an average number of added moles, represents a number of 0 to 3, and M represents an alkali metal atom or an amine). The manufacturing method of any one of Claims 4-6 which is a component (c) containing a component (b) and 25-65 weight part water with respect to 100 weight part of this component (b). .   The mononuclear detergent particle group obtained by the manufacturing method of any one of Claims 1-7.