JP4785405B2 - Detergent particles - Google Patents

Description

  The present invention relates to detergent particles, a method for producing detergent particles, and a detergent composition containing the detergent particles.

In powder detergents, detergent particles bind to each other during long-term storage and cause caking that becomes a solid state. The cause is the storage (storage) temperature and external conditions such as moisture and carbon dioxide during storage. Absorption of ingredients is the main factor. Moisture absorption causes liquid cross-linking between the detergent particles or partially dissolves the components on the surface of the detergent particles, thereby forming sticky sites on the surface of the detergent particles and causing caking. Also, the absorption of carbon dioxide gas reacts with alkali components and moisture in the detergent, and generates needle-like crystals such as sodium hydrogencarbonate and sodium sesquicarbonate in the shape of a chestnut on the surface of the detergent particles. The acicular crystals are entangled with the acicular crystals on the surface of the adjacent chestnut-shaped detergent particles to cause caking.
The caking that occurs due to the above causes a problem that the usability of the detergent is remarkably impaired, for example, not only the appearance is remarkably impaired but also accurate measurement is not possible.

  Many studies have been made to solve this problem. For example, Non-Patent Document 1 describes a technique in which detergent particles are coated with water-insoluble inorganic powders such as calcium stearate, magnesium carbonate, and aluminosilicate. Adhesiveness between the surface modifier and the surface modifier is not sufficient, and the surface modifier is peeled off due to the stress applied to the detergent particles during transportation of the manufacturing process, etc., and sufficient effects cannot be obtained during actual use. There is a problem.

  Patent Document 1 discloses a technique for obtaining free-flowing properties by mixing a granular detergent composition and a liquid binder substance and then coating with zeolite X. In this technique as well, as described above, it is also disclosed during transportation. Since the zeolite X, which is the coating powder, peels off due to the above stress, there is a problem that a sufficient effect cannot be obtained, and that if the amount of the binder is large, the solubility is lowered.

  Patent Document 2 discloses a technique for improving caking resistance by forming a base layer on the surface of the detergent particles and then coating the surface with a surface modifier. In terms of suppression, it was not enough in some cases.

Further, Patent Document 3 discloses that a surfactant is supported on a surfactant-supporting base granule, and then the surface is coated with a mixture of fine powder and an anionic surfactant acid precursor. Although a technique for improving the suppression of spotting such as an activator has been disclosed, it has not been sufficient in some cases in terms of caking resistance and fluidity.
Japanese Patent No. 2965905 JP 2004-143394 A Japanese Patent No. 3444817 Gazette of the Japan Patent Office, a collection of known and commonly used technologies (powder detergent for clothing) [issued on March 26, 1998]

  An object of the present invention is to provide detergent particles having excellent resistance to caking, such as caking resistance, fluidity, and surfactant, a method for producing the detergent particles, and a detergent composition containing the detergent particles. It is in.

That is, the gist of the present invention is as follows.
[1] A step of neutralizing the surface of the base detergent particles (B) with an acid precursor of an anionic surfactant [step (II)],
A step of adding a base treatment liquid (C) containing a binder to the particles obtained in step (II) to form a base layer on the particle surface [step (III)],
A step of adding a surface modifier to the particles obtained in the step (III) and covering the particles [step (IV)]
Detergent particles obtained by a process comprising
[2] Base detergent having 20 to 100 parts by weight of surfactant supported on 100 parts by weight of surfactant-supporting base granules (A) having an average particle size of 150 to 500 μm and a bulk density of 400 g / L or more Step of obtaining particles (B) [Step (I ′)],
Step of neutralizing with 0.5 to 6 parts by weight of an acid precursor of an anionic surfactant with respect to 100 parts by weight of the base detergent particles (B) obtained in step (I ′) [step (II ′)],
With respect to 100 parts by weight of the particles obtained in the step (II ′), 0.5 to 5 parts by weight of a ground treatment liquid (C) in which fine powder having an average particle size of 0.1 to 5 μm is dispersed in a binder is added. A step of forming an underlayer on the particle surface [step (III ')],
A step of adding 1 to 25 parts by weight of a surface modifier having an average particle size of 10 μm or less to 100 parts by weight of the particles obtained in the step (III ′) [Step (IV ′)]
Detergent particles obtained by a process comprising
[3] A detergent composition containing the detergent particles according to [1] or [2],
[4] The method for producing detergent particles according to [1] or [2].

  The detergent particles of the present invention are excellent in anti-caking property, fluidity, and suppression of stains such as surfactants. Moreover, according to the manufacturing method of the detergent particle of this invention, the effect that the detergent particle excellent in the anti-caking property, fluidity | liquidity, and a stain | polishing_out | leading-out of surfactant etc. is obtained.

<Base detergent particles (B)>
The base detergent particles (B) used in the present invention are particles used in ordinary powder detergents. For example, a surface modifying agent comprising a surfactant, an alkali agent, and other detergent components as necessary is applied. The particles before being processed are mentioned. The base detergent particles may be agglomerated by stirring and granulating the above ingredients in a slurry state, tumbling granulation, kneading / mixing granulation, or a dry neutralization method or a dry blend method, What is obtained by carrying | supporting 1 or more types of surfactant mixed liquid to the base granule (A) for carrying | supporting a surfactant mentioned later has favorable solubility, and is preferable from the effect of this invention becoming remarkable.

  As the surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be blended as necessary. Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or alkyls thereof. Examples thereof include ester salts and fatty acid salts. Particularly preferred are linear alkylbenzene sulfonates having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, and α-sulfo fatty acid alkyl ester salts having 10 to 20 carbon atoms.

  Examples of the nonionic surfactant include ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. In particular, an EO 1 to 10 mol adduct of an alcohol having 10 to 16 carbon atoms is preferable in terms of removal of sebum soil, hard water resistance, biodegradability, and compatibility with linear alkylbenzene sulfonate.

  Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid aminopropyl betaines, and examples of cationic surfactants include mono (or di) long chain alkyl quaternary ammonium salts.

  As the alkaline agent, water-soluble inorganic salts such as carbonates, hydrogen carbonates, and silicates, poorly water-soluble inorganic substances such as crystalline silicates, and the like can be blended. Other detergent components include water-soluble inorganic salts such as sulfate, sulfite, hydrogen sulfate, hydrochloride and phosphate, water-soluble organic acid salts such as citrate and fumarate, crystalline Alternatively, a poorly water-soluble inorganic substance such as amorphous aluminosilicate and a water-soluble polymer can be blended.

  Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Among these, a carboxylic acid polymer having a weight average molecular weight of several thousand to 100,000 is preferable in terms of sequestering ability, dispersibility of solid dirt / particle dirt, and ability to prevent recontamination. Particularly preferred are salts of acrylic acid-maleic acid copolymers and polyacrylates. Examples of the water-soluble salts include those used as the alkali agent and other detergent components.

  Moreover, base detergent particle | grains (B) can also include the mixture with other particle | grains, such as salts, as another detergent component other than the said particle | grain. For example, when heavy sodium carbonate (dense ash) is mixed with the particles, the adhesion of the surface modifier to the surface of heavy sodium carbonate can be improved, and the caking resistance that is the effect of the present invention is improved. There is an advantage of being.

The amount of the surfactant in the base detergent particles (B) is preferably 15 to 50% by weight. The upper limit of the amount is preferably 50% by weight or less, more preferably 40% by weight or less, and the lower limit of the amount is preferably 15% by weight or more, more preferably 20% by weight or more.
The amount of the alkali agent is preferably 10 to 50% by weight. The lower limit of the amount is preferably 10% by weight or more, more preferably 15% by weight or more, and the upper limit of the amount is preferably 50% by weight or less, more preferably 40% by weight.
Further, the amount of other cleaning components is preferably 20 to 60% by weight. The lower limit of the amount is preferably 20% by weight or more, more preferably 30% by weight or more, and the upper limit of the amount is preferably 60% by weight or less, more preferably 50% by weight or less.

  The particle diameter of the base detergent particles (B) is 200 μm or more, preferably 250 μm or more, more preferably 270 μm or more from the viewpoint of free flow of the detergent, and 550 μm or less, preferably from the viewpoint of avoiding a decrease in solubility. It is preferably adjusted to 500 μm or less, more preferably 480 μm or less.

  As the base detergent particles (B), granules capable of supporting a surfactant (hereinafter referred to as surfactant-supporting base granules (A)) from the viewpoint that a large amount of a liquid activator can be used. Further, it is preferable to carry a surfactant.

<Base granule for supporting surfactant (A)>
The surfactant-supporting base granule (A) used in the present invention preferably has an average particle size of 150 to 500 μm, more preferably 180 to 350 μm, in that a detergent particle group having excellent solubility and fluidity can be obtained. Moreover, 400 g / L or more is preferable from a compact point and a soluble point, 400-1500 g / L is more preferable, 500-1200 g / L or less is further more preferable.

  The surfactant-supporting base granule (A) preferably has a higher ability to support a liquid component (supporting ability). The carrying capacity is preferably 20 mL / 100 g or more, more preferably 40 mL / 100 g or more. If the carrying ability is within this range, aggregation of the surfactant-supporting base granules (A) is suppressed, which is preferable from the viewpoint of suppressing aggregation of particles in the detergent particle group.

Further, from the viewpoint of preventing the surfactant-supporting base granule (A) from collapsing during mixing in the steps (I), (II) and (III) described later, the surfactant-supporting base granule (A ) Is preferably harder. Specifically, in terms of particle strength, the surfactant-supporting base granule (A) is preferably at least 100 kg / cm ^2, more preferably at least 200 kg / cm ² .

  The average particle size of the surfactant-supporting base granule (A) is measured from the weight fraction according to the size of the mesh after the sample is vibrated for 5 minutes using a standard sieve defined in JIS Z8801. The bulk density of the surfactant-supporting base granule (A) is measured by a method defined by JIS K 3362.

  The measurement of the supporting ability of the surfactant-supporting base granule (A) is as follows. 100 g of a sample is put into a cylindrical mixing tank having an inner diameter of 5 cm and a height of 15 cm and equipped with a stirring blade inside. While stirring the stirring blade at 350 rpm, linseed oil at 25 ° C. is introduced into the tank at a rate of 10 mL / min. The loading capacity is defined as the amount of linseed oil input when the power required for stirring is highest.

  The method for measuring the particle strength is as follows. 20 g of sample is put in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikenki Co., Ltd., TVP1 type tapping type densely packed bulk density measuring device, tapping condition; period 36 times / min, 60 mm Free fall from the height. The sample height immediately after the end of the tapping operation is measured and set as the initial sample height. Thereafter, the entire upper end surface of the sample held in the container by a pressure tester is pressurized at a speed of 10 mm / min, and a load-displacement curve is measured. The initial sample height is multiplied by the slope of the straight line when the displacement rate in the curve is 5% or less, and the value obtained by dividing the obtained value by the pressurized area is defined as the particle strength.

  The surfactant-supporting base granule (A) can be obtained, for example, by drying a slurry containing a detergent builder or the like. Among these, particles obtained by spray-drying the slurry are preferable from the viewpoint of obtaining desired physical property values.

  Such a surfactant-supporting base granule (A) includes, for example, 20 to 90% by weight, 2 to 30% by weight and 5% by weight of a water-insoluble inorganic substance, a water-soluble polymer and a water-soluble salt, respectively, based on the solid content in the slurry. A slurry comprising ˜78% by weight can be obtained by spray drying. By adjusting the drying method and drying conditions within the above composition range, the average particle diameter, bulk density, supporting ability, and particle strength can be controlled. The contents of the water-insoluble inorganic substance, the water-soluble polymer, and the water-soluble salt in the slurry are more preferably in the range of 30 to 75% by weight, 3 to 20% by weight, and 10 to 67% by weight, respectively, based on the solid content in the slurry. The range of 40 to 70% by weight, 5 to 20% by weight, and 20 to 55% by weight is particularly preferable. In addition to the water-insoluble inorganic substance, the water-soluble polymer and the water-soluble salt, auxiliary substances such as a surfactant and a dye suitable for the final detergent composition may be contained in the surfactant-supporting base granule (A). The amount of the auxiliary component is preferably 10% by weight or less.

  Here, examples of the water-insoluble inorganic substance include aluminosilicates; clay compounds such as silicon dioxide, hydrated silicate compounds, perlite, bentonite, and the like. Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Examples of water-soluble salts include water-soluble salts represented by alkali metal salts, ammonium salts, and amine salts each having carbonate, hydrogen carbonate, sulfate, sulfite, hydrogen sulfate, hydrochloric acid, or phosphate. Examples thereof include inorganic salts, and low-molecular weight water-soluble organic salts such as citric acid and fumarate.

The surfactant-supporting base granule (A) preferably has the following structure (1) and / or (2) from the viewpoint of solubility of the detergent particles.
Structure (1): When detergent particles are dissolved in water, the particle size of the detergent particles is preferably 1/10 or more, more preferably 1/5 or more, still more preferably 1/4 or more, and particularly preferably 1/3 or more. It is preferable to have pores capable of releasing bubbles having a diameter of.
Structure (2): a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt, and an uneven distribution in which more water-soluble polymers and / or water-soluble salts (hereinafter referred to as water-soluble polymers) exist near the surface than inside It is preferable to have properties.

  When the detergent-carrying base granule (A) has the structure (1), when a small amount of water enters the particle in the process of dissolving the detergent particle in water, the particle has a predetermined size from the inside of the particle. When bubbles are released, and then a large amount of water enters the inside of the particles, the particles themselves collapse (self-disintegration). The particles have fast solubility.

  This bubble emission phenomenon can be confirmed with a digital microscope or an optical microscope, and the bubble diameter (equivalent circle diameter) can be measured. The pore diameter of the surfactant-supporting base granule (A) is preferably 1/10 to 4/5, more preferably 1/5 to 4/5 of the particle diameter. preferable. The pore diameter can be measured as follows. In order not to break the surfactant-carrying base granule (A), cut with a scalpel etc. at the surface containing the maximum particle diameter, observe the cut surface with a scanning electron microscope, and the equivalent circle diameter (γ μm) of the cut surface of the cut particles ) And the presence of pores inside the particles, the equivalent circle diameter (δ μm) of the pores is measured. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore is δ μm. Then, the ratio of pore diameter to particle diameter (δ / γ) is obtained.

  In addition, since the surfactant-supporting base granule (A) has the structure (2), water-soluble components near the surface dissolve faster in water, and the disintegration of the detergent particles from the particle surface is promoted. By exhibiting the dissolution behavior, high-speed solubility can be expressed. The most preferable mode for exhibiting high-speed solubility is that the surfactant-supporting base granule (A) has both the structure (1) and the structure (2).

The uneven distribution of the water-soluble polymer can be confirmed by the following method. First, the surfactant-carrying base granule (A) to be measured and the surfactant-carrying base granule (A) are sufficiently pulverized in an agate mortar or the like to make the surfactant-carrying base granule uniform. (A) Prepare a pulverized product. Then, under the condition that information from the surface of the crushed product of the surfactant-carrying base granule (A) and the surfactant-carrying base granule (A) can be obtained, each of them is subjected to Fourier transform infrared spectroscopy (FT). -IR) and photoacoustic spectroscopy (PAS) in combination (hereinafter referred to as “FT-IR / PAS”). When the amount of the former water-soluble polymer or the like is larger than that of the latter, the surfactant-supporting base granule (A) to be measured has a structure in which more water-soluble polymer or the like is present in the vicinity of the surface than the inside. Is. The measurement conditions for obtaining information from the surface of the crushed product of the surfactant-carrying base granule (A) and the surfactant-carrying base granule (A) to about 10 μm are, for example, a resolution of 8 cm ⁻¹ , a scan speed of 0. A condition of 63 cm / s and a total of 128 times can be given. Examples of the apparatus used include an FTS-60A / 896 type infrared spectrophotometer manufactured by Bio-Rad Laboratories as an infrared spectrophotometer, and a 300 type photoacoustic detector manufactured by MTEC as a PAS cell. FT-IR / PAS is described in APPLIED SPECTROSCOPY vol.47 1311-1316 (1993).

  The surfactant to be supported on the surfactant-supporting base granule (A) is at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant. A composition. The composition is preferably in a liquid state when mixed with the surfactant-supporting base granule (A), and the nonionic surfactant (A) and 0 to 300 weights per 100 parts by weight of the nonionic surfactant. 1 to 100 parts by weight of the anionic surfactant (b) having a sulfuric acid group or a sulfonic acid group and 100 parts by weight of the nonionic surfactant (c) It is more preferable that the composition contains. In the composition, the amount of (b) is more preferably 20 to 200 parts by weight, particularly preferably 30 to 180 parts by weight. In the composition, the amount of (c) is more preferably 5 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight. When this surfactant composition is used, the solubility and flow characteristics of the detergent particles are improved, the surfactant-supporting base granules (A) are prevented from collapsing during mixing, and the surfactant composition during storage (at room temperature) This is particularly preferable because it can suppress the appearance of stains. Among these, the addition of an anionic surfactant having a sulfuric acid group or a sulfonic acid group is further advantageous for improving the flow characteristics of the detergent particles and for suppressing the bleeding of the surfactant composition during storage (at room temperature).

  In the present specification, (c) a nonionic surfactant immobilizing agent is a hardness in a state where the fluidity of a nonionic surfactant that is liquid at room temperature is suppressed and the surfactant composition loses fluidity. Means a base capable of significantly increasing Examples of the immobilizing agent include fatty acid salts, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic type nonionic surfactants.

  The compounding amount of the surfactant composition is 20 to 100 parts by weight, preferably 25 to 80 parts by weight based on 100 parts by weight of the surfactant-supporting base granule (A) from the viewpoint of exerting detergency. Preferably it is 30-70 weight part. In this range, detergent particles having excellent solubility and flow characteristics can be obtained.

<Acid precursor of anionic surfactant>
In the present invention, the surface of the base detergent particles (B) is neutralized with an acid precursor of an anionic surfactant (step (II) described later).
Specific examples of the acid precursor of the anionic surfactant include a saturated or unsaturated fatty acid having 10 to 22 carbon atoms, an alkyl sulfuric acid having 10 to 22 carbon atoms, an α-sulfonated fatty acid having 10 to 22 carbon atoms, and carbon. 1 or more types chosen from the group which consists of several 10-22 polyoxyethylene alkyl ether sulfuric acid are mentioned. Preferably, at least one selected from the group consisting of fatty acids, specifically saturated acids such as capric acid, lauric acid, myristic acid, palmitic acid and stearic acid, and unsaturated acids such as oleic acid. In particular, lauric acid (Lunac L-98, manufactured by Kao Corporation, etc.), myristic acid (Lunac MY-98, manufactured by Kao Corporation, etc.), palmitic acid (Lunac L-98, manufactured by Kao Corporation, etc.) Preferably used.

  The compounding amount of the acid precursor of the anionic surfactant is preferably 0.5 parts by weight or more and 1 part by weight or more with respect to 100 parts by weight of the base detergent particles (B) from the viewpoint of surface coating efficiency. Further, from the viewpoint of solubility, it is preferably 6 parts by weight or less, preferably 4 parts by weight or less, and more preferably 3 parts by weight or less.

  In the present invention, by using the acid precursor of the anionic surfactant, a surface of the particle can be coated with a neutralized product of this compound, so that the surfactant, particularly the liquid surfactant, is exuded. There is an advantage that it can be prevented.

<Pretreatment liquid (C)>
In the present invention, a base layer containing a binder is formed on the surface of the base detergent particles (B) neutralized with the acid precursor of the anionic surfactant.
The underlayer is formed by adding an undercoat solution (C) to the particles obtained in step (II) to form an underlayer on the particle surface [step (III) described later], and the next step (IV The surface coating with the surface modifier can be performed more firmly.

  The ground treatment liquid (C) is 0.5% based on 100 parts by weight of the particles obtained in the step of neutralizing the surface of the base detergent particles (B) with an acid precursor of an anionic surfactant (step (II)). It is preferable to add so that it may become -5 weight part. The lower limit of the amount is preferably 0.5 parts by weight or more, more preferably 1 part per 100 parts by weight of the particles obtained in the step (II) in order to sufficiently treat the surface of the particles obtained in the step (II). The upper limit of the amount is preferably 5 parts by weight or less, more preferably 100 parts by weight with respect to 100 parts by weight of the particles obtained in the step (II), from the viewpoint of avoiding a decrease in solubility due to the coating of the binder component. 4 parts by weight or less.

  The ground treatment liquid (C) used in the present invention contains a binder. Moreover, it is preferable that the ground treatment liquid (C) further contains fine powder in that the coating with the surface modifier in the next step (IV) is more firmly performed.

  The ground treatment liquid (C) can contain water and other components as necessary at the time of preparation. For example, even when water is contained in the binder to reduce the viscosity in order to improve the handling property of the surface treatment liquid (C), the surface treatment liquid (C) after coating with the surface modifier in the next step (IV) In the case where the binder has adhesiveness due to movement of water in the base detergent particles (B) due to hydration of water-soluble salts contained in the base detergent particles (B), the next step (IV ) Can be more firmly coated with the surface modifier.

  In the case where the ground treatment liquid (C) contains a binder and fine powder, the ground treatment liquid (C), for example, uniformly disperses particles as a raw material of the fine powder in the binder and performs wet pulverization to a desired particle size. It can be obtained by doing. A suitable wet pulverizer is T.K. K. Homomic line mill (trade name) and Willy A.・ Bacofen AG machinen fabric ・ Switzerland (Willen AG Machinechinfabrik Switzerland), a mill of the media mill type represented by Dyno-Mill (trade name), such a media mill type The pulverizer is particularly suitable because of its high pulverization efficiency.

  For example, when a high load is applied to the media mill due to the viscosity of the binder, it may be processed twice or more in the media mill. The particles to be dispersed may be uniformly dispersed, wet pulverized by a suitable pulverizer such as a media mill, and the fine powder may be dispersed in a binder so as to be a predetermined amount. In this case, it is necessary to adjust the addition amount of the low viscosity liquid so that the film forming property of the binder is not impaired.

  Two or more treatments with a pulverizer are preferable because the particle size distribution of the fine powder can be made sharper and the underlayer can be more stably formed.

In the case of the wet pulverization, it is preferable that at least 1 part by weight of water is contained with respect to 100 parts by weight of the base treatment liquid (C), more preferably 5 parts by weight or more, and further preferably 10 parts by weight or more. In addition, moisture is 100 parts by weight of component (C).
400 parts by weight or less is preferable, and 200 parts by weight or less is more preferable.

  The weight ratio between the fine powder and the binder in the ground treatment liquid (C) is sufficient to obtain the effects of the present invention, and the fine irregularities on the surface of the particles obtained in step (II), and the ground treatment liquid. From the viewpoint of handling properties derived from the viscosity of (C), it is preferably from 1/40 to 1/10, more preferably from 1/35 to 1/15.

<Binder>
The binder used in the present invention is preferably a liquid substance exhibiting solidification properties, film-forming properties, and viscosity. Since the binder has such properties, the coating with the surface modifier in the next step (IV) can be more firmly performed.

  Examples of the binder include polyethylene glycol, (meth) acrylic acid polymer, cellulose derivatives, and aqueous solutions thereof. The polyethylene glycol preferably has a weight average molecular weight of 4000 to 50000 from the viewpoint of solidification at a temperature at which the detergent is usually used (˜40 ° C.) and solubility after the surface treatment. The lower limit of the weight average molecular weight is preferably 4000 or more, more preferably 6000 or more, and the upper limit thereof is preferably 50000 or less, more preferably 30000 or less, and further preferably 15000 or less. Examples of the (meth) acrylic acid polymer include an acrylic acid homopolymer and an acrylic acid maleic acid copolymer. Examples of the cellulose derivative include carboxymethylcellulose (CMC), methylcellulose, hydroxypropylmethylcellulose and the like. Among these binders, a melt of polyethylene glycol having a weight average molecular weight of 4,000 to 20,000 and an aqueous solution thereof are particularly preferable. These binders may be used alone or in admixture of two or more.

<Fine powder>
The fine powder used for the ground treatment liquid (C) is preferably one having an average particle diameter of 0.1 to 5 μm. The lower limit of the average particle diameter is preferably 0.1 μm or more from the viewpoint of forming unevenness due to the base layer on the surface of the base detergent particles (B) and more strongly coating with the surface modifier in the subsequent step. The upper limit is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, particularly preferably 1 μm or less, from the viewpoint of non-peelability of the formed underlying layer. Most preferably, it is 0.8 μm or less.

  As the fine powder, the powder used for general surface modifiers and the like described in the JPO Gazette of Known and Conventional Techniques (Clothing detergent for clothing) (issued on March 26, 1998) is used. it can. For example, crystalline or amorphous aluminosilicate, calcium silicate, silicon dioxide, clay mineral, talc, layered compound, amorphous silica derivative, crystalline silicate compound, metal soap and the like can be suitably used. From the viewpoint of detergency, crystalline aluminosilicate (zeolite) having hardness component capturing ability is preferable.

  In addition, when it is required to pulverize the fine powder efficiently and quickly to the target particle size, it is preferable to use a clay mineral for a part or all, and a lamellar clay mineral is particularly preferable. Representative examples of layered clay minerals are kaolin mineral, mica clay mineral, and smectite (montmorillonite). Among the layered clay minerals, bentonite whose volume is increased by water absorption and whose main component is montmorillonite is most preferable. There is no problem even if it is used in a surface treatment solution that does not contain water, but layered clay minerals have the property that they swell and peel easily when used in water, and as a result, the grindability is further improved. It is preferable to use in a ground treatment solution containing water.

  These fine powders can be used alone or in admixture of two or more.

  As the fine powder, in addition to the fine powder, if desired, other powder components such as a pigment component and a fluorescent dye can be used. For example, as a component difficult to be blended by the conventional production method, a water-insoluble dimorpholino-type fluorescent dye is dispersed in the base treatment liquid and sprayed onto the base detergent particles (B) without blending into the spray-dried slurry. It can be easily added.

  The fine powder is a build-up method in which fine powder having a desired particle size is synthesized in advance by a known gas phase synthesis method, liquid phase synthesis method, or the like, or a fine powder having a desired particle size by pulverizing existing powder particles. Is obtained by a breakdown method. The build-up method is a method of controlling the particle size by controlling the reaction rate or the condensation rate, but it requires a high degree of control and high cost, so there are special cases where special high purity is required. Except for this, the breakdown method is preferred.

  Breakdown methods include dry pulverization and wet pulverization. For dry pulverization, pulverizers such as a ball mill and a hammer mill are suitable. For wet pulverization, pulverizers such as a line mill and media melt are suitable. In view of the target particle size and grinding efficiency, wet grinding is more preferable.

<Surface modifier>
In the present invention, as described above, the particles having the underlayer formed on the surface are coated with a surface modifier on the surface.
The surface modifier used in the present invention preferably has an average primary particle size of 10 μm or less, more preferably 0.1 μm or more and 10 μm or less. When the average particle size is 10 μm or less, the adhesion of the surface modifier to the surface of the ground particle is improved. The average particle diameter of the surface modifying agent is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba Seisakusho) or a measurement by microscopic observation. Moreover, it is preferable from a washing | cleaning surface that this surface modifier has high ion-exchange ability and high alkali ability. The surface modifier is preferably an aluminosilicate, and may be crystalline or amorphous. Other than aluminosilicates, fine powders such as silicate compounds such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and crystalline silicate compounds are also preferred. Further, a metal soap having a primary particle size of 0.1 μm or more and 10 μm or less, a powdered surfactant (for example, alkyl sulfate) and a water-soluble organic salt can be used in the same manner. When a crystalline silicate compound is used, it is preferably used by mixing with a fine powder other than the crystalline silicate compound for the purpose of preventing deterioration due to moisture absorption or aggregation of the crystalline silicate due to carbon dioxide gas.

<Method for producing detergent particles>
The method for producing the detergent particles of the present invention comprises:
A step of neutralizing the surface of the base detergent particles (B) with an anionic surfactant acid precursor [step (II)],
A step of adding a base treatment liquid (C) containing a binder to the particles obtained in step (II) to form a base layer on the particle surface [step (III)],
A step including a step of adding a surface modifier to the particles obtained in step (III) and covering the particles [step (IV)];
In particular, from the viewpoint of solubility, it is preferable to have a step [step (I)] in which the surfactant is supported on the surfactant-supporting base granule (A) to obtain the base detergent particles (B).

<Process (I)>
This step is a step of mixing the surfactant-supporting base granules (A) and the surfactant to obtain base detergent particles (B). By this step, the surfactant is supported on the surfactant-supporting base granule (A). As preferable mixing conditions, the temperature of the mixture at the time of mixing is set to be higher than the pour point of the surfactant from the viewpoint of suppressing the disintegration of the base particle (A) for supporting the surfactant and promoting the loading of the surfactant. In the range in which the components can be mixed, mixing is performed with as little stirring force as possible.

  The surfactant-supporting base granule (A) preferably has an average particle size of 150 to 500 μm and a bulk density of 400 g / L or more.

  When mixing in a batch system, there is no particular limitation as long as a mixer that satisfies the above conditions is used. For example, (1) a mixing tank has a stirring shaft inside, and a stirring blade is attached to this shaft and powdered. Mixer of the type that performs mixing: Henschel mixer (Mitsui Miike Chemical Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator (Powrec Co., Ltd.), Redige mixer (Matsuzaka) Such as Giken Co., Ltd.) and Pro-Share Mixer (manufactured by Taiheiyo Kiko Co., Ltd.). (2) A mixer of a type in which mixing is performed by rotating a ribbon-like blade that forms a spiral in a cylindrical or semi-cylindrical fixed container: for example, a ribbon mixer (manufactured by Nihon Kikai Kogyo Co., Ltd.), Batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), etc. (3) A mixer that mixes by rotating along a conical container while the screw revolves around an axis parallel to the container wall, For example, there is a Nauter mixer (manufactured by Hosokawa Micron Corporation).

  Particularly preferred among the above mixers is a horizontal mixing tank having a stirring shaft at the center of a cylinder, and a mixer of a type in which a stirring blade is attached to this shaft to mix powder, and a Redige mixer (Matsuzaka Giken ( Co., Ltd.) and Pro-Share Mixer (manufactured by Taiheiyo Kiko Co., Ltd.).

  Moreover, when mixing by a continuous type, although it does not specifically limit, For example, you may mix base granule for surfactant support (A) and surfactant using a continuous type apparatus among said mixer. .

  In this step, the preferred mixing time (in the case of a batch system) and the average residence time (in the case of a continuous system) of the component (A) and the surfactant are preferably 1 to 20 minutes, particularly 2 to 10 minutes. Is preferred.

<Process (II)>
This step is a step of neutralizing the surface of the base detergent particles (B) by mixing the base detergent particles (B) and the acid precursor of the anionic surfactant. The amount of the acid precursor used as the anionic surfactant is preferably 0.5 to 6 parts by weight with respect to 100 parts by weight of the base detergent particles (B) obtained in step (I), for example. In this step, the acid precursor of the anionic surfactant can neutralize the surface of the base detergent particles (B) to obtain detergent particles having excellent flow characteristics. By adding the acid precursor of the anionic surfactant, in addition to neutralizing the surface of the base detergent particles (B), the fine particles can be aggregated, and the fine powder rate of the finally obtained detergent particles can be reduced. .

  A preferable mixing condition is to use a mixer equipped with both a stirrer and a crushing blade, and the operating conditions (such as the number of rotations) of the stirring blade and the crushing blade should be appropriately set so as not to collapse the base detergent particles (B) as much as possible. Good. Moreover, it is necessary to mix under the temperature conditions in which the neutralization reaction of the acid precursor of the anionic surfactant is efficiently performed. In addition, as this temperature condition, 40-95 degreeC is preferable and 50-90 degreeC is more preferable.

As a preferable mixing device, among the mixers exemplified in the step (I), a device provided with both a stirring blade and a crushing blade can be mentioned. When such a mixer is used, the steps (I) and (II) can be performed using the same apparatus, which is preferable from the viewpoint of simplification of equipment. (Matsuzaka Giken Co., Ltd.), Proshare Mixer (manufactured by Taiheiyo Kiko Co., Ltd.) and the like.
The mixing time is preferably about 0.5 to 3 minutes.

<Process (III)>
This step is a step of adding a base treatment liquid (C) containing a binder and, if necessary, a fine powder to the particles obtained in step (II) to form a base layer on the particle surface.

  The amount of the ground treatment liquid (C) used is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the particles surface-coated with the acid precursor of the anionic surfactant obtained in the step (II). By treating the particle surface obtained in the step (II) with the base treatment liquid (C), the surface layer is formed on the particle surface, thereby suppressing the release of the surface modifier added in the subsequent step. As a result, the effect of improving adhesion is exhibited. In particular, when fine powder is used, the fine irregularities generated are preferable because the effect of further suppressing the peelability of the surface modifier added in the subsequent step and improving the adhesion as a result is exhibited. When stress is applied to the detergent particles at the time of formulation, etc., the surface modifier layer is displaced and scraped off in the case of a smooth surface, whereas when an underlayer like the present invention exists, The deviation of the surface modifier can be suppressed. In particular, when a fine powder is used, the fine irregularities are preferable as a three-dimensional support. Here, the adhesion means that the surface modifier is easily adhered and is not easily peeled off.

  Such processing can be performed using a mixer. As a mixer, when batch-type mixing is performed, for example, (1) a mixer that has a stirring shaft in the mixing tank and is equipped with a stirring blade on this shaft to mix powders: for example, a Henschel mixer (Mitsui Mitsui) Kako Koki Co., Ltd.), High Speed Mixer (Fukae Kogyo Co., Ltd.), Vertical Granulator (Powrec Co., Ltd.), Redige Mixer (Matsuzaka Giken Co., Ltd.), Proshare Mixer (Pacific Kiko Co., Ltd.) And a mixing apparatus described in JP-A-10-2960645. (2) A mixer of a type in which mixing is performed by rotating a ribbon-like blade that forms a spiral in a cylindrical or semi-cylindrical fixed container: for example, a ribbon mixer (manufactured by Nihon Kikai Kogyo Co., Ltd.), Batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), etc. (3) A mixer that mixes by rotating along a conical container while the screw revolves around an axis parallel to the container wall, For example, there are a Nauter mixer (manufactured by Hosokawa Micron Corporation), a ribocorn (manufactured by Okawara Seisakusho), and the like.

  Moreover, you may use the continuous apparatus of said mixer. Moreover, the following (1)-(3) are used as a continuous type apparatus of a mixer other than the above. However, it is necessary to select the mixing conditions such as the main shaft rotational speed so that the base detergent particles (B) do not collapse. (1) Consisting of a vertical cylinder with a powder inlet and a main shaft with a mixing blade, the main shaft is supported by an upper bearing and the discharge side is free. (Made by Paulec). (2) A continuous mixer in which raw materials are put into the upper part of a disk having a stirring pin and this disk is rotated and mixed by a shearing action. (3) A horizontal mixing tank having a stirring shaft at the center of a cylinder. There is a turbulizer (manufactured by Hosokawa Micron Co., Ltd.), etc., which is a mixer of a type in which a stirring blade is attached to this shaft to mix powder.

  As a preferable mixing device, among the mixers exemplified in the step (I), a device provided with both a stirring blade and a crushing blade can be mentioned. When such a mixer is used, steps (I) to (III) can be performed using the same apparatus, which is preferable from the viewpoint of simplification of equipment. (Matsuzaka Giken Co., Ltd.), Proshare Mixer (manufactured by Taiheiyo Kiko Co., Ltd.) and the like.

  The treatment temperature is preferably 40 to 100 ° C, the lower limit is more preferably 50 ° C or higher, and the upper limit is more preferably 90 ° C or lower. The processing time may be about 1 to 10 minutes. The method for adding the ground treatment liquid (C) to the mixer is not particularly limited, but it is preferable to add the ground treatment liquid (C) by spraying.

  By this treatment method, an underlayer is formed on the surface of the particles obtained in step (II). The undercoat layer is preferably formed uniformly on the entire surface of the particles obtained in the step (II), but also has an effect of suppressing the peelability due to interference between the surface modifiers that are coated in the subsequent step. For this reason, it is not necessary that all surface modifier bases have been treated, and the base layer is preferably formed on a surface of 30% or more of the particle surface obtained in step (II). Similar effects can be obtained. In addition, formation of the base layer of the particle | grain surface obtained by this process (II) can be confirmed by cleaving particle | grains and enlarging and observing the detergent particle surface vicinity using an electron microscope etc.

<Process (IV)>
This step is a step of coating the particles obtained in step (III) by adding a surface modifier.
The amount of the surface modifier used is preferably 1 to 25 parts by weight with respect to 100 parts by weight of the particles obtained in step (III).
A preferable mixing condition is to use a mixer equipped with both a stirrer and a crushing blade, and the operating conditions (such as the number of rotations) of the stirring blade and the crushing blade should be appropriately set so as not to collapse the base detergent particles (B) as much as possible. Good.

As a preferable mixing device, among the mixers exemplified in the step (I), a device provided with both a stirring blade and a crushing blade can be mentioned. When such a mixer is used, steps (I) to (IV) can be performed using the same apparatus, which is preferable from the viewpoint of simplification of equipment. (Matsuzaka Giken Co., Ltd.), Proshare Mixer (manufactured by Taiheiyo Kiko Co., Ltd.) and the like.
The mixing time is preferably about 0.5 to 3 minutes.

<Detergent particles>
The bulk density of the detergent particles obtained as described above is preferably 500 g / L or more, more preferably 500 to 1000 g / L, still more preferably 600 to 1000 g / L, and particularly preferably 650 to 850 g / L. . The average particle diameter of the detergent particle group is preferably 150 to 500 μm, more preferably 180 to 350 μm.

The most preferred form of the detergent particles produced in the present invention is detergent particles produced using the surfactant-supporting base granule (A) as a core, and the particle growth degree defined by the following formula is preferably 1. It is 5 or less, more preferably 1.3 or less, and still more preferably 1.2 or less.
Particle growth rate = (average particle size of detergent particles obtained in step (IV)) / (average particle size of surfactant-supporting base granule (A))

  The detergent particles obtained by the production method of the present invention have excellent flow characteristics. “Excellent fluidity” means having the following particle fall velocity dispersion (V). The particle fall speed dispersion (V) of the detergent particles is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.0 or less, particularly preferably 0.8 or less, and further preferably 0. .6 or less.

The granular material falling speed dispersion V is measured by the method described in Japanese Patent No. 3444817, specifically, using a “powder particle flow characteristic measuring apparatus” as shown in FIG.
The granular material flow characteristic measuring device 1 measures the flow characteristic of the granular material 3 held by the holding member 2. The supporting mechanism 4, the tilting device 5, the tilt measuring device 6, and the weight of the holding member 2. A measuring device 7 and an arithmetic device 8 are provided. The support mechanism 4 includes a rotating member 13 that is rotatably supported about a horizontal axis by a support column 12 provided on the base 11, and the holding member 2 is attached to the tip of the rotating member 13. As shown in FIGS. 2 (1) and 2 (2), the holding member 2 is a container having an opening at the top, characterized in that the side surface is a fan shape, and the opening is an outflow portion of the granular material 3. 2a. An output device 9 is connected to the arithmetic device 8.

  The tilting device 5 transmits the rotation of the motor 16 provided on the base 11 to the rotation member 13 via the electric mechanism 17 and the speed reduction mechanism 18 and rotates the rotation member 13, thereby supporting the support. The holding member 2 supported by the mechanism 4 can be gradually inclined at a set speed. Due to the inclination, the granular material 3 held by the holding member 2 can be dropped from the outflow portion 2a. The motor 16 is connected to a non-illustrated speed adjusting device, and the inclination speed of the holding member 2 can be adjusted by changing the rotation speed.

  As a specific operation, the holding member 2 is provided so that the outflow portion 2a is 20 cm high with respect to the tray portion 20 of the weight measuring device 7, and the angle θ of the holding member 2 is set to 0 °. Next, a sufficient amount of the measurement sample is injected into the outflow portion 2a from a height of 10 cm above the outflow portion 2a using a funnel, and then the sample protruding from the outflow portion 2a is scraped off and removed. The holding member 2 is rotated at an angular velocity of 6.0 ° per second, and is rotated until the angle θ of the holding member 2 is changed from 0 ° to 180 ° (FIGS. 2 (1) and (2)). In the meantime, the weight of the sample is measured every 1/80 second by the weight measuring device, and the θ and the weight at that time are sequentially recorded.

  The differential value of the drop rate at the inclination angle θ of the holding member 2 is defined as the drop speed (% / deg.) At the angle θ, and this is defined as v (θ). However, in order to reduce noise, the following data processing is performed to define the drop rate and the drop speed with respect to the inclination θ of the holding member. The drop rate at the angle θ is the angle with respect to the total weight of the measurement sample, where the average value of the measured values of the drop weight for a total of 40 points from the angle (θ-2.925) ° to the angle θ is the drop weight at the angle θ The ratio of fall weight at θ is defined as the drop rate (%) at angle θ. For the drop speed at the angle θ, plot the angle on the horizontal axis and the drop rate (%) on the vertical axis for a total of 19 points from the angle (θ−0.675) ° to (θ + 0.675) °. It is defined as the value (% / deg.) Of the slope of the straight line obtained using the multiplication method. Further, the value of the slope of the least square approximation line can be obtained according to JIS Z 8901.

Here, the falling speed v (θ) (% / deg.) Of the sample powder is measured with respect to the inclination angle θ (°) of the holding member 2, and the falling rate Y (θ) of the sample powder is 1% to 99. The dispersion of the value of v (θ) with respect to θ that is between% is calculated by the following formula, and is determined as the powder particle fall velocity dispersion V. That is, V = (nΣ (v (θ)) ² − (Σv (θ)) ² ) / n ² (n is the total number of data in which Y (θ) is between 1% and 99%).

  The flow time of the detergent particles is preferably 7 seconds or less, and more preferably 6.5 seconds or less. The flow time is the time required for 100 mL of powder to flow out from the hopper for measuring bulk density defined by JIS K 3362.

  The caking resistance of the detergent particles is preferably 90% or more, more preferably 95% or more in terms of passing through a sieve. The test method for caking property is 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. An acrylic resin plate (15 g) and a lead plate (250 g) are placed on the box containing the sample 50 g. This is carried out by obtaining the following passage rate for the caking state after leaving for 2 weeks in an atmosphere of 35 ° C. and 40% humidity.

<Passing rate>
The sample after the test is gently opened on a sieve (mesh opening 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the passage rate (%) with respect to the sample after the test is obtained.

  If the stain resistance of the detergent particles is evaluated by the following test method, preferably 2 ranks or more, and more preferably 1 rank, adhesion of nonionic surfactant-containing powder to equipment in the transport system is prevented. This is preferable because it is not necessary to devise an anti-smudge effect.

Test method for spotting property: The condition of spotting at the bottom of the filter paper container subjected to the caking resistance test (non-contact surface with the powder) is visually evaluated. Evaluation is determined by the wetted area of the bottom, and the following 1 to 5 ranks are used.
Rank 1: not wet. Rank 2: The surface of about 1/4 is wet. Rank 3: about 1/2 surface is wet. Rank 4: The surface of about 3/4 is wet. Rank 5: The entire surface is wet.

The dissolution rate of the detergent particles is preferably 90% by weight or more, more preferably 95% by weight or more. The method for measuring the dissolution rate is as follows.
1 L beaker (Ca / Mg molar ratio 7/3) equivalent to 71.2 mg CaCO ₃ / L cooled to 5 ° C. in a 1 L beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, 1 L glass beaker manufactured by Iwaki Glass Co., Ltd.) In a state where the water temperature of 5 ° C. is kept constant in a water bath, the swirl with respect to the water depth is made with a stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, Teflon round thin type) Stir at a rotational speed (800 rpm) at which the depth is approximately 1/3. The detergent particles reduced and weighed to 1.000 ± 0.0010 g are charged and dispersed in water with stirring, and stirring is continued. 60 seconds after the addition, the detergent particle dispersion in the beaker was filtered through a standard sieve (diameter: 100 mm) with a known opening of 74 μm according to JIS Z 8801 (corresponding to ASTM No. 200), and the water content remaining on the sieve Of detergent particles together with a sieve are collected in an open container of known weight. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The collected residue of detergent particles is dried in an electric dryer heated to 105 ° C. for 1 hour, and then kept in a desiccator (25 ° C.) containing silica gel for 30 minutes for cooling. After cooling, the total weight of the dry detergent residue, sieve and collection container is measured, and the dissolution rate (% by weight) of the detergent particles is calculated by the following formula. The weight is measured using a precision balance.
Dissolution rate (% by weight) = {1- (T / S)} × 100
[S: input weight of detergent particles (g); T: dry weight of residue of detergent particles remaining on the sieve when the aqueous solution obtained under the above stirring conditions is applied to the sieve (drying conditions: (After holding at 105 ° C. for 1 hour, hold in a desiccator (25 ° C.) containing silica gel for 30 minutes) (g)].

<Detergent composition>
The detergent particles of the present invention are, for example, known detergent bases such as surfactants and builders, bleaching agents (percarbonate, perborate, bleaching activator, etc.), anti-staining agents (carboxymethylcellulose, etc.) It can also be used as a detergent composition by mixing with a softening agent, a reducing agent (sulfite, etc.), a fluorescent whitening agent, an antifoaming agent (silicone, etc.), an enzyme such as cellulase or protease, and a fragrance.

  The detergent composition using the detergent particles of the present invention can be applied to various uses. For example, it can be used as a detergent for clothes, a bleach for clothes, a detergent for hard surfaces such as detergent for automatic dishwashers, a pipe cleaner and the like.

Moreover, the following are mentioned as a preferable aspect of this invention.
[Aspect 1] 20 to 100 parts by weight of a surfactant is supported on 100 parts by weight of a surfactant-supporting base granule (A) having an average particle size of 150 to 500 μm and a bulk density of 400 g / L or more. Step of obtaining detergent particles (B) [Step (I ′)],
A step of neutralizing with 0.5 to 6 parts by weight of an acid precursor of an anionic surfactant with respect to 100 parts by weight of the base detergent particles (B) obtained in the step (I ′) [step (II ′)],
With respect to 100 parts by weight of the particles obtained in the step (II ′), 0.5 to 5 parts by weight of a ground treatment liquid (C) in which fine powder having an average particle size of 0.1 to 5 μm is dispersed in a binder is added. A step of forming an underlayer on the particle surface [step (III ')],
A step of adding 1 to 25 parts by weight of a surface modifier having an average particle size of 10 μm or less to 100 parts by weight of the particles obtained in the step (III ′) [Step (IV ′)]
The manufacturing method of detergent particle | grains including the process of containing.
[Aspect 2] 20 to 100 parts by weight of a surfactant is supported on 100 parts by weight of a base granule (A) for supporting a surfactant having an average particle size of 150 to 500 μm and a bulk density of 400 g / L or more. Step of obtaining detergent particles (B) [Step (I ′)],
Step of neutralizing with 0.5 to 6 parts by weight of an acid precursor of an anionic surfactant with respect to 100 parts by weight of the base detergent particles (B) obtained in step (I ′) [step (II ′)],
Crystalline or amorphous to a binder which is one or more selected from the group consisting of polyethylene glycol, (meth) acrylic acid polymer, cellulose derivative and aqueous solution thereof with respect to 100 parts by weight of the particles obtained in the step (II ′) Average particle size of 0.1 or more selected from the group consisting of high quality aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound and metal soap A 5 μm fine powder is treated with 0.5 to 5 parts by weight of a ground treatment liquid (C) in which the fine powder / binder weight ratio is 1/40 or more and 1/10 or less, and the process (II ′) After the step of forming an underlayer containing fine powder on the particle surface obtained in [Step (III ″)],
A bulk density of 500, comprising a step of coating with 1 to 25 parts by weight of a surface modifier having an average particle size of 10 μm or less with respect to 100 parts by weight of the particles obtained in the step (III ″). The manufacturing method of the detergent particle | grains which are -1000g / L, the average particle diameter of 150-500 micrometers, and a particle growth degree of 1.5 or less.
[Aspect 3] A detergent composition for clothing containing detergent particles obtained by the production method according to Aspect 1 or 2.

Example 1
A surfactant-supporting base granule (A) was prepared by the following method.
480 kg of water was added to a 1 m ³ mixing tank having a stirring blade, and after the water temperature reached 50 ° C., 120 kg of sodium sulfate and 150 kg of sodium carbonate were added. After stirring for 15 minutes, 40 kg of a 40% by weight sodium polyacrylate aqueous solution (average molecular weight 10,000, manufactured by Kao Corporation) was added. After further stirring for 15 minutes, 252 kg of zeolite (Zeobuilder, Type 4A, average particle size: 3.5 μm) was added and stirred for 30 minutes to obtain a homogeneous slurry. The final temperature of this slurry was 53 ° C. This slurry was subjected to spray drying, and the obtained spray-dried particles were used as a base granule group. This base granule group has an average particle size of 260 μm, a bulk density of 590 g / L, a supporting capacity of 52 mL / 100 g, a particle strength of 280 kg / cm ² , and a composition (weight ratio): zeolite / polyacrylic acid Na / carbonate carbonate / sodium sulfate / water. = 42/8/25/20/5.

Next, using the obtained surfactant-supporting base granules (A), base detergent particles (B) were prepared by the method shown below [step (I)].
The surfactant mixture (polyoxyethylene alkyl ether / polyethylene glycol / sodium dodecylbenzenesulfonate / water = 21/4/21/4 (weight ratio)) was brought to 80 ° C. Next, 100 parts by weight of the surfactant-supporting base granule (A) was put into a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), and the main shaft (rotation speed: 60 rpm, peripheral speed: 1. 6 m / s) was started. In addition, 80 degreeC warm water was poured by the jacket at 10 L / min. Thereto, 50 parts by weight of the surfactant mixture was added over 2 minutes, and then stirred for 5 minutes to obtain base detergent particles (B).
Here, as polyoxyethylene alkyl ether, Emulgen 108KM manufactured by Kao Corporation (trade name, ethylene oxide average added mole number: 8.5, carbon number of alkyl chain: 12 to 14) was used. As polyethylene glycol, K-PEG6000 (trade name, average molecular weight: 8500) manufactured by Kao Corporation was used.

Next, the surface of the obtained base detergent particles (B) was neutralized with an acid precursor of an anionic surfactant by the method shown below [step (II)].
2 parts by weight of lauric acid was added to 100 parts by weight of the base detergent particles (B) in the above-mentioned Redige mixer, and the main shaft (rotation speed: 120 rpm) was rotated for 1 minute to coat the surface. In addition, 80 degreeC warm water was poured by the jacket at 10 L / min.

Next, an underlayer was formed on the surface of the particles obtained in step (II) by the method shown below [step (III)].
1 part by weight of a 60% by weight pure polyethylene glycol (average molecular weight 13000) aqueous solution (primary treatment liquid) as a binder with respect to 100 parts by weight of the particles obtained in step (II) in the above-mentioned Redige mixer. It sprayed and thrown in, and the main axis | shaft (rotation speed: 120 rpm) was rotated for 1 minute, and the base layer was formed. In addition, 80 degreeC warm water was poured by the jacket at 10 L / min.

Next, the particles obtained in step (III) were coated with a surface modifier by the method shown below [step (IV)].
10 parts by weight of zeolite (Zeobuilder, 4A type, average particle size: 3.5 μm) as a surface modifier is added to 100 parts by weight of the particles obtained in step (III) in the above-mentioned Redige mixer. Then, the main shaft (rotation speed: 120 rpm) was rotated for 1 minute to coat the surface to obtain detergent particles.

  Thereafter, with respect to 100 parts by weight of the obtained detergent particles, 0.6 parts by weight of an enzyme (Novozymes, trade name: Cannase 24T) and 0.4 part by weight of a fragrance are blended using a rotary kiln to obtain a detergent composition. I got a thing.

Example 2
Detergent particles and detergent composition in the same manner as in Example 1 except that in the step (II), 4 parts by weight of palm kernel oil fatty acid was used instead of 2 parts by weight of lauric acid as the acid precursor of the anionic surfactant. Got.

Example 3 (However, it is a reference example.)
In step (II), detergent particles and a detergent composition were obtained in the same manner as in Example 1 except that dodecylbenzenesulfonic acid was used instead of lauric acid as the acid precursor of the anionic surfactant.

Example 4
In step (III) , instead of a 60% by weight pure polyethylene glycol (average molecular weight 13000) aqueous solution as a binder, a 40% by weight pure sodium acrylate homopolymer (manufactured by Kao Corporation, average molecular weight 10,000) is used. A detergent particle and a detergent composition were obtained in the same manner as in Example 1 except that.

Example 5
In the step (III) , the detergent particles and the detergent composition were the same as in Example 1 except that a 60 wt% pure polyethylene glycol (average molecular weight 13000) aqueous solution was used as a binder and the following ground treatment solution was used. Got.
As a binder, 5 parts by weight of fine zeolite (Zeobuilder, average particle size 3.5 μm) is added to 100 parts by weight of a pure polyethylene glycol (average molecular weight 13000) aqueous solution of 60% by weight, and dyno mill KD-45 type. [Product Name, Willy A. -Wet pulverization was performed using Bacofen AG machinen fabric-Switzerland (manufactured by Willy A. Bachofen AG Machinenfabrik Switzerland) to obtain a base treatment solution. The media used for the dyno mill were YTZ zirconia beads φ0.5 mm (trade name, manufactured by Nikkato Co., Ltd.), the filling rate was 85%, and the peripheral speed of the grinding blade was 16 m / s. The average particle diameter of the crushed zeolite was measured using LA-920 (trade name, manufactured by Horiba Seisakusho). A treatment amount of the treatment liquid to the dyno mill, specifically, a flow rate of the dyno mill and a rotation speed of the stirrer were controlled to obtain 0.5 μm.

Example 6
Detergent particles and detergent composition in the same manner as in Example 5 except that a base treatment solution was prepared using 1% by weight pure CMC sodium (trade name: F20LC, degree of etherification: 0.6) as a binder. I got a thing. The average particle size of the fine powder (zeolite) was 0.5 μm.

Example 7
As a binder, 5 parts by weight of fine bentonite (trade name: FULASOFT-1, SUD-CHEMIE PERU SA) was added to 100 parts by weight of a pure polyethylene glycol (average molecular weight 13000) aqueous solution of 60% by weight. A detergent particle and a detergent composition were obtained in the same manner as in Example 5 except that wet grinding was performed using a dyno mill KD-45 type and a base treatment liquid having an bentonite average particle size adjusted to 0.3 μm was used. .

Example 8
Detergent particles and a detergent composition were obtained in the same manner as in Example 5 except that 5 parts by weight of a dimorpholino type (stilbene type) fluorescent dye (Macthesim Corp., trade name: BRY-10) was further added to the base treatment solution.

Example 9
As base detergent particles (B), the same procedure as in Example 1 was used except that granulated particles before surface coating with zeolite described in Example 1 of paragraph [0058] of JP-A-2001-003094 were used. Detergent particles and a detergent composition were obtained.

Comparative Example 1
Detergent particles and a detergent composition were obtained in the same manner as in Example 1, except that step (II) was omitted.

  In Comparative Example 1, as a result of omitting the neutralization step (II) with the acid precursor of the anionic surfactant, the fluidity was slightly lowered as compared with Examples 1-8. Moreover, the sieve passing rate, which is an index of caking resistance, was 65%, and the stain removal rank was 3. From this result, it can be seen that the contribution to the improvement of storage stability in the step (II) is very large.

Comparative Example 2
Detergent particles and a detergent composition were obtained in the same manner as in Example 1, except that step (III) was omitted.
In Comparative Example 2, as a result of omitting the step (III), the sieve passing rate was 82%. From this result, it can be seen that the contribution to the storage stability of the step (III) is large.
The results of Examples and Comparative Examples are shown in Table 1.

  From the results in Table 1, the neutralization step (II) with an acid precursor of an anionic surfactant and the treatment step (III) with a base treatment containing a binder improve the storage stability, and the step (II) It can be seen that the storage stability of the detergent particles can be remarkably enhanced by applying the steps (III) and (III) together.

  The detergent composition using the detergent particles of the present invention can be applied to various uses. For example, it can be used as a detergent for clothes, a bleach for clothes, a detergent for hard surfaces such as detergent for automatic dishwashers, a pipe cleaner and the like.

FIG. 1 is a front view of the flow characteristic measuring apparatus. (1) of FIG. 2 is a partial side view of the flow characteristic measuring apparatus, and (2) of FIG. 2 is a perspective view of the holding member.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flow characteristic measuring apparatus 2 Holding member 2a Outflow part 3 Powder body 4 Support mechanism 5 Inclination apparatus 6 Inclination measuring apparatus 7 Weight measuring apparatus 8 Arithmetic apparatus 9 Output apparatus 11 Base 12 Support | pillar 13 Rotating member 16 Motor 17 Electric mechanism 18 Deceleration mechanism 20 saucer part

Claims (8)

A base detergent particle (B) containing 15 to 50% by weight of a surfactant and 10 to 50% by weight of sodium carbonate as an alkaline agent is prepared by supporting the surfactant on the base particle (A) for supporting the surfactant. Obtaining step [step (I)],
The surface of the base detergent particles (B) containing sodium carbonate obtained in the step (I) is 0.5 to 6 parts by weight of 10 to 22 carbon atoms with respect to 100 parts by weight of the base detergent particles (B). Step of neutralizing with saturated or unsaturated fatty acid (step (II)),
A step of adding 0.5 to 5 parts by weight of a base treatment liquid (C) containing a binder to 100 parts by weight of the particles obtained in the step (II) to form a base layer on the particle surface [step (III) ],
A step of adding 1 to 25 parts by weight of a surface modifier to coat 100 parts by weight of the particles obtained in the step (III) [Step (IV)]
Detergent particles obtained by a process comprising Undercoating liquid (C) is, the detergent particles of claim 1 Symbol mounting further contains fine powder having an average particle diameter of 0.1 to 5 [mu] m. With respect to 100 parts by weight of the surfactant-supporting base granule (A) having an average particle size of 150 to 500 μm and a bulk density of 400 g / L or more, 20 to 100 parts by weight of the surfactant is supported , A step of obtaining base detergent particles (B) containing 15 to 50% by weight and 10 to 50% by weight of sodium carbonate as an alkaline agent [step (I ′)],
Obtained in the step (I '), the surface of the base detergent granules containing sodium carbonate (B), the base detergent particles (B) with respect to 100 parts by weight 0. A step of neutralizing with 5 to 6 parts by weight of a saturated or unsaturated fatty acid having 10 to 22 carbon atoms [step (II ′)],
To 100 parts by weight of the particles obtained in the step (II ′), 0.5 to 5 parts by weight of a ground treatment liquid (C) in which fine powder having an average particle size of 0.1 to 5 μm is dispersed in a binder is added. A step of forming an underlayer on the particle surface (step (III ')),
A step of adding 1 to 25 parts by weight of a surface modifier having an average particle size of 10 μm or less to 100 parts by weight of the particles obtained in the step (III ′) [Step (IV ′)]
Detergent particles obtained by a process comprising The detergent particles according to claim 2 or 3, wherein the weight ratio of fine powder / binder in the ground treatment liquid (C) is from 1/40 to 1/10. The detergent particle according to any one of claims 1 to 4 , wherein the binder contains one or more selected from the group consisting of polyethylene glycol, (meth) acrylic acid polymers, cellulose derivatives, and aqueous solutions thereof. The detergent particles according to any one of claims 2 to 5 , wherein the fine powder is a crystalline or amorphous aluminosilicate. Claim 1-6 detergent compositions containing detergent particles according to any one. The manufacturing method of the detergent particle in any one of Claims 1-6 .

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