TW201000626A - Particles for supporting surfactant - Google Patents

Abstract

A method for producing particles for supporting a surfactant having a bulk density of 550 g/l or less, including the following steps 1(a) and 2: Step 1(a): mixing a clay mineral powder and a powder raw material excluding the clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more; and Step 2: adding water or an aqueous binder solution to a mixed powder obtained in the step 1(a), and forming particles with a low-shearing granulator. According to the present invention, particles for supporting a surfactant having excellent supporting capacity/supporting ability/absorbing rate of a liquid surfactant composition can be obtained by a method without employing spray-drying.

Description

201000626 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a surfactant. The particle group is loaded and its manufacturing method. Further, the present invention relates to a glutinous solution detergent particle of a particle group of Μ ^ - °H surfactant carrier and a detergent composition comprising the group of the detergent particles. [Prior Art] As a method of obtaining a powder detergent, there is a demand for a step of allowing a surfactant: a carrier particle group to carry a liquid surfactant: a particle group for supporting an active agent The load capacity of the liquid surfactant + surfactant-supporting particle group includes the following two factors: the supporting capacity (loading capacity), and the m-loaded large reading interface can be lived. The degree and the liquid surfactant are firmly held inside the particles without J-strengthening/contracting (loading force). The loading capacity I is used for the cleaning performance is important to achieve the cleaning performance. 74 The surfactant is more important, and the 'loading capacity' is to inhibit the liquidity of the liquid surfactant and prevent the fluidity of the powder detergent. It is important to transfer the liquid A and the surface of the active agent to the container or its surface. Further, from the viewpoint of productivity, it is also required to rapidly absorb the characteristics (loading speed) of the surfactant liquid carrier for the surfactant-supporting particle group. Regarding such a surfactant, the 哉 丨 丨 丨 r r r r r r r r r r r r r r r r r r τ τ τ For example, Patent Document 1 discloses a particle group for preparation containing a water-soluble polyoctene and a water-soluble salt. However, when the dry agent is used to carry the I k忒 particle group, it is necessary to carry out spray drying. From the viewpoint of economy, it is sought to use a spray drying method. On the other hand, for example, Patent Document 2 discloses that the composition of the water-based organic salt and the polymer organic binder is dry-free, and the method essentially releases the water of hydration by drying; The ability to charge (equivalent to the carrying capacity of the case): It is extremely difficult to adjust the suction speed. _ ^ ] is difficult to carry or bear q(2). Therefore, a shifting force/loading speed is required. All of the fields are supported by the Japanese Patent Application Publication No. JP-A-2002-541267. 】 The problem to be solved by the invention 纟 "The purpose of the month is to use the method of spraying without drying - the loading capacity of the night-like surfactant composition / the supporting capacity / the supporting speed = U of the surfactant loading Use particle groups. Further, the present invention provides a high bulk density washing and granule group obtained by using the surfactant to carry a particle group, and a detergent composition comprising the detergent particle group. Means for Solving the Problems That is, the gist of the present invention relates to the following matters: Π] - a method for producing a surfactant-made granule group, which is used for producing a surfactant having a bulk density of 550 g/1 or less. The group of particles for carrying 'comprises the following steps 1 (a) to 2: ... Step 1 (a): mixing clay mineral powder and powder raw materials having an oil absorption capacity of 〇_4 ml/g or more other than clay minerals Steps, and Step 2: adding water or a solution of 140448.doc 201000626 in an aqueous solution obtained by the step W (4), using a low shear 袢4?rj knife to carry out the granulation step; [2] A method for producing a surfactant group for carrying a rare earth particle group, which is used for producing a particle carrier particle group having a bulk density of 550 w·g / U乂, comprising the following step 1 (b)~ 2 : Step 1 (b): The step of mixing the powdery material other than the clay 4 soil is 〇4 ml/on; and Step 2: In step 1 (b), you are from ^ Add water or a binder solution to the mixed powder that has been passed on to the powder. Use it as low as before! j , the step of granulating the low J cutting granulator; [3] - the kind of interfacial activity 丨 丨 mm mm 1 carrier particle group, which has a bulk density of 550 g / Ι or less, and contains the following components : In addition to clay minerals, mountain At + * Λ a / powder with a force of 0.4 ml / g or more. 40 to 95% by weight Clay mineral powder: 〇 ~ 45 weight 0 / 〇 adhesive: 〇 ~ 35 Weight 〇/〇水: 〇~1 5 wt%; [:]: a bulk density bulk detergent particle group, which is a surfactant-supporting granule containing the enamel method described above. a group or a surfactant group carrying a particle group of a surfactant group to carry an interface activity composition; and [5] a detergent composition comprising the detergent particles of the above [4] Developed. Advantageous Effects of Invention According to the present invention, the following effects can be produced, and the load capacity/loading capacity of the spray-drying surfactant composition can be prevented from being used. A particle group for carrying an active agent. Furthermore, it is effective in obtaining a detergent particle group having excellent cleaning performance, quality, and the like by supporting the liquid surfactant composition in the surfactant-supporting particle group. [Embodiment] In the present invention, the term "particles for supporting a surfactant" means particles containing at least 吸 4 m]/g of an oil-absorbing ability other than a clay mineral, and water or an aqueous solution of a binder. It is preferred to add water or an aqueous binder solution to a mixed powder of at least a powder raw material having an oil absorption capacity of 0.4 or more, other than a clay mineral, and to obtain particles obtained by using a low-shear granulator to perform particle μ, and (4) A material (four) surfactant composition. The pelletized ancestor of the pellet is referred to as a surfactant-supporting particle group. The detergent particles are particles containing a surfactant, a builder, etc., which are obtained by supporting a surfactant (4) (4) a liquid carrier surfactant composition, and the "cleaning and subgroup" means the detergent particles. Poly Chinese body. The detergent composition refers to a detergent particle group containing, if necessary, a detergent component (additional granule, fluorescent dye, enzyme, perfume, medicinal herbicide) added in addition to the detergent particle group. Etc.). 4 foaming agent, bleaching agent, bleaching activation The so-called water solubility means that the solubility in hunger water is 〇5 g / i 〇〇 (four) g / i 〇〇 g. The solubility in the water added to the day is less than =5 = liquid surfactant composition, which refers to the gradation of the liquid or charge-like surfactant when carried on the surfactant s particle group 140448.doc 201000626. <Composition of a particle group for surfactant-supporting particles> 1. A powdery material having an oil absorption capacity of 0 4 ml/ga other than a clay barrier is an essential component of the present invention, and oil absorption ability other than clay mineral is Powder material on 0.4 ml/ga. The oil absorption capacity refers to a value determined by the method described in the quality evaluation method described later. The powder raw material having an oil absorption capacity of 〇4...仏 or more, other than the clay mineral, is a porous substance having a fine pore of 1 〇 or less in the powder, and is in the pores thereof. A substance that can carry a surfactant. The upper limit of the oil absorption capacity is not particularly limited, and for example, it is preferably 1 · 〇 ml / g or less. From the viewpoint of granulation, the average particle diameter of the powder raw material is preferably 50 to 250 μm, more preferably 50 to 2 〇〇 μηι 80 to 200 μη. Particularly preferably, it is preferably a water-soluble substance from the viewpoint of solubility. Examples of the powder raw material include a light-weight test produced by firing sodium hydrogencarbonate or a porous powder of soda ash or a mansile wall. The hydrate of sodium dipolyphosphate is dried and produced. From the viewpoint of easiness of handling and ease of availability, it is particularly preferable that it is a light soda ash. When lightweight (10) is used as the silk raw material, the surfactant loading ability can be further improved by adjusting the temperature at the time of calcination of sodium hydrogencarbonate. From the viewpoint of the supporting ability, the calcination temperature is preferably 12 〇 t: 〜25 (rc, more preferably 150 to 220 ° C ' particularly preferably 150 to 200 ° C. As the raw material of the powder From the viewpoint of the carrying capacity, the interface 140448.doc 201000626 preferably contains 40 to 95% by weight of the active agent-supporting particle group, and is 45 to 90% by weight, particularly preferably 5〇. Going to 曰里里/〇, especially good is reset /.. Again, by the drying step. J set the above composition π ' before the drying step of the particle group, it is better to contain = ~ 80% by weight 'Better than 3 to 77% by weight, particularly preferably η to π% by weight' is particularly preferably 32 to 73% by weight. 2. Adhesive for the surfactant of the present invention is carried by ten private ten,丨 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你 你When water is used, it is produced by using one of the powder raw materials to dissolve in water. Adhesive, bismuth or clay minerals are granulated into the granules. The binder is water-soluble, and the viscosity of the binder is used to make the granulation easier, and the granules are easier to use. Dry, but there is concern about the decrease in particle strength; however, when using the zebra mites, -δ Μ water bath, the effect of the binder can be achieved after drying. Therefore, it is better to use an aqueous binder solution. The agent is not particularly limited as long as it has a property of rapidly dissolving and/or dispersing the components constituting the particles in the powder raw material, and is, for example, polyethylene glycol or poly Two diols, polyoxyethylene ethoxylates _ and 兮·聱+ / street creatures, polyethylene glycols and their derivatives, water gluten cellulose derivatives μ (乍 乍 寻 之 之 bamboo creatures' can be enumerated趟Compounds, etc.), 糸 糸 人 人 人 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In terms of 'better water solubility The vitamin derivative, the saccharide and the carboxylic acid polymer are more preferably a salt of an acrylic acid-cis-succinic acid copolymer or a polyacrylate. The salt is preferably a sodium salt, a potassium salt or an ammonium salt. The weight average molecular weight of the carboxylic acid-based polymer is preferably from 1,000 to 100,000, more preferably from 2,000 to 80,000. From the viewpoint of adhesion and oil absorption ability, 'the surfactant-supporting particle group The content of the binder is preferably from 0 to 35% by weight of the surfactant-supporting particle group, more preferably from 5 to 30% by weight, particularly preferably from 8 to 20% by weight; Particularly preferably, it is 1 to 2% by weight. Further, when it is adjusted to the above composition by the drying step, it is preferably 0 to 30% by weight, more preferably 0 to 30% by weight, more preferably 3 to 25% by weight, particularly preferably 5 to 17% by weight. /. Particularly good is 7 to 17% by weight. The concentration of the aqueous solution of the binder is not particularly limited, but the particle diameter at the time of granulation is largely affected by the volume of the aqueous solution of the binder, so that the desired amount of the binder and the desired particle size determine the concentration. 3. Clay minerals Clay minerals have a layered structure and carry a liquid interface activity between 剜π and between layers. Therefore, by blending clay minerals, it is possible to increase the loading of the hexavalent octagonal surfactant in the valley and improve the load. Moreover, the clay mineral exhibits a mouth by controlling the amount of the surfactant to adjust the amount of the fine particles by adjusting the amount of the water, and it is also possible to control the load capacity and the particle size control. It is a component that increases the load capacity/loading power. ', add clay minerals 140448.doc -10- 201000626 as such clay minerals, such as stone (polylith, lithium turbidite, zinc (four) stone / slagite, swelled stone, iron bentonite, etc.), insects to Stone, bismuth stone, Ming expanded mica, muscovite, orange Xuan';, biotite, iron lithium (sloping chlorite, fine chlorite,), 彔 mudstone, bell 1 Lu chlorite, Ming green mud curtain stone b farm mother (,,, crispy mica, pearl mica, etc.), manganese curtains, ... obstruction (leaf serpentine, progressive serpentine, serpentine serpentine, shovel; Κ 兵^ 'Magnetic, muddy stone, iron serpentine, dark nickel serpentine:), Nanling soil minerals (kaolinite, Dick stone, pearl clay, He Leshi, etc.). Among them, in terms of softness properties, talc, bentonite, swellable mica, worm to stone, serpentine, kaolin mineral, etc., and more preferably bismuth bentonite are particularly preferred as montmorillonite. These may be used singly or in combination of two or more. Further, from the viewpoint of the interface and the loading ability of the lingual agent, it is preferred to use the clay mineral represented by the following general formula (I): '[Si8(MgaAlb)O20(〇H)4]x'Mex+ (1) The main component of clay minerals. Here, a, b and X are 0 < a$6, 〇 < b$4, x = l 2-2a-3b, and Me is selected from Na, K, Li, Cal/2, Mg 1/2 and NH4. At least one of the ions. Examples of the clay mineral represented by the above formula (I) include "Laundrosil DGA212", "Laundrosil PR414", "Laundrosil DG214", "Laundrosil DGA Powder", "EXM0242", and "Frasoft-1" manufactured by Siid_Chemie Co., Ltd. Powder j, "Detersoft GIS", "Detersoft GIB", "Detersoft 140448.doc 201000626 GISW" by Laviosa, ' Pure Bent〇nite, Standard Bentonite, Premium Bentonite (10) Squatting Bentonite) and so on. In the case of the above-mentioned example of the clay mineral, there is also a particle type in which a binder component is added and granulated, and the binder component may be added as long as the effect of the present invention is not impaired. When the above-mentioned clay minerals are used in the present invention, it is preferred that the form is powdery from the viewpoint of granulation, and if it is granulated, it is preferred to perform chopping in advance until appropriate. granularity. As the mashing machine which can be used for shredding, there are mentioned impact crushers such as a key crusher, an impact pulverizer such as an atomizer and a pin mill, and a shear coarse crusher such as a quick pulverizer. These may be multi-stage operations of the same or different types of pulverizers. The average particle diameter at the end of the clay ore (4) is preferably (10) Å or less, more preferably 50 Å or less, and particularly preferably 3 or less. From the viewpoints of the supporting force and the solubility, the total amount of the metal material (Na ion, κ ion ' _ = soil metal ion (Ca ion, Mg ion) is not shown in the formula (1). The ear ratio is preferably 1,0 or more, and more preferably μ or more 'especially better than 2.0. As for obtaining the metal ion (>, the product can be selected, and the clay mineral with a higher μ ratio can be prepared if it is a natural salt. When the soil is granulated, an alkali metal can also be added. Right The synthetic product can be any known method. 4. Moisture The surfactant-supporting particle group of the present invention contains an appropriate amount of water for U0448.doc 201000626 in the production step. In the case of the interface-active sword composition, the load capacity is the same as that of the point, and the amount of water measured by the infrared moisture meter is as small as possible, and it is better that the J is out of the tongue. /rinr, J疋15 weights or less, more preferably 10 °, especially preferably 5 weights / /. 5. Other components, the surfactant loading particles of the present invention are appropriately formulated into the above-mentioned Now, in U 4 (4), the substance of the material is used. From the point of view of ability, the Cicada makeup is now loaded with "the better the weekly dosage is 20% by weight or less. , 牿 榀 榀 from 曰 c to 曰 particularly good 疋 5% by weight or less. Adjustable For example, the chelating agent is used to suppress the complexing agent caused by the metal ion. As the water-soluble chelate = adjustable, it is not necessary to be used to keep the metal ion chelated. Crystallized cuprate, orthophosphate, pyrophosphate, etc. Among them: - hydroxamate and trisphosphonium triphosphate, and, in the viewpoint of crystalline dispersibility, sink in the water. ; good ... the average grain is (M, P is suitable for water-insoluble sounding agent, can be listed as a salt, such as _ zeolite, 曰曰 夕 夕 夕 螯 萨 萨 β β β β β β β β β β β In terms of metal separation, zeolite A is preferred. • Water-soluble inorganic salt In order to improve the ionic strength of the first liquid and improve the cleaning of sebum stains, it is preferred to add a water-soluble inorganic salt. It is a substance which has good solubility and does not adversely affect the main force. I40448.doc 13- 201000626 There is no special regulation for the J JL. For example, an alkali metal salt having a sulfate or a sulfite, an ammonium salt Etc. /, in the middle of the season, the use of high ionic dissociation Sodium sulfate, sulfurous acid t, and potassium sulfate are used as excipients. Further, from the viewpoint of increasing the dissolution rate, 5 is also preferably used in combination with magnesium sulfate. • The water-insoluble excipient is only in the water. Materials & Good, no damage to the cleaning power, but also special measures - ·,,, special regulations. For example, crystallinity or aluminosilicate, or two-emulsified矽, hydrated citric acid compounds, etc. From the viewpoint of dispersibility in water, # "° is preferably the average particle size of primary particles & 0.1~20 μηι. Ding Shuang only Ma • Other auxiliary components can be listed Fluorescent dyes, pigments, dyes, etc. The following article can be used for measurement as described in the method for determining the average particle diameter of the above components. <Preparation method of surfactant-supporting particle group> The surfactant of the present invention can be used for the non-spray drying step by the following method, and at least The oil absorption capacity is 〇.4mI/gw except for the step of mixing or mixing, and the mixing/solution obtained, using a low-shear granulator for granulation (4) oral contact] Step 1 (a). The clay mineral powder is mixed with a powder raw material of 0.4 Å or more in addition to the terracotta mineral. The force is Qi. As long as the 140448.doc 201000626 or the like can be substantially uniformly mixed, any method can be employed. For example, it may be mixed using the low shear granulator used in the step 2, or may be mixed beforehand using another mixer and then transferred to the low shear granulator. As the other mixer which can be used for powder mixing, for example, a barrel type mixer, a pan type mixer, a belt type mixer, a conical spiral mixer: SCHUGI (company name) mixer, L〇 mGE (company name) mixer, high speed mixer, etc. Here, as the content of the clay ore 16 , from the viewpoint of the capacity and particle size control, it is preferable that the amount of the surfactant-supporting particle group is (four)%%, more preferably 2 to 40. The weight %, particularly preferably 3 to 4% by weight, further preferably 3 to 35% by weight, particularly preferably 4 to 3 % by weight. Further, after granulation, it can be dried as needed, and when it is adjusted to the above composition by such a drying step, it is preferable to contain 1 to 40% by weight, more preferably, in the particle group before the drying step. It is 疋W篁%, especially preferably 3 to 30% by weight 'and further preferably 3 to 25% by weight%'. Particularly preferably, it is 6 to 25 weight%. Also, 'Calibe minerals and powder raw materials, Xialibi (clay minerals/powder raw materials)' are preferably 1/1 to 1/30, and better 灵1/1 to 1/20, especially good. 1/2~1/20. 2. Step 1 (b) in the step of stirring or mixing the powder raw materials other than the clay minerals and having an oil enthalpy of 0.4 ml/g or more, as long as the materials can be substantially uniformly For mixing, you can also use the tone m ^ μ- , as in the method. For example, it can be mixed using the low-to-cut granulator used in step 2, 4 Γ before mixing using the above-mentioned mixing, and then transferred to the low-shear granulator. In addition, the powder raw materials other than the clay minerals described in this book are those which do not substantially contain clay minerals, but may also contain 0~i_2% by weight of clay minerals in the powder original 7. The content of the clay mineral is more preferably 〇1% by weight in the powder raw material, particularly preferably 〇~〇.8% by weight, particularly preferably 〇~〇 6% by weight. From the viewpoint of the particle size of the surfactant-supporting particle group and the detergent particle group in which the particle group is used as the surfactant composition, the carrier is supported as a clay mineral. Preferably, the particle group is 0 to 1% by weight, and 1 is preferably 0 to 8% by weight, particularly preferably 〇 to 0.6% by weight, particularly preferably 0 to 5% by weight. Further, after the granulation, drying may be carried out as needed. The granules before the drying step are adjusted to the above-mentioned conditions by the drying step, preferably G to G.9 by weight. /, more preferably 0 to 0.7% by weight, particularly preferably G to Q5% by weight, particularly good. It is 0 to 0.4% by weight. 3. Step 2 Step 2 is a step of adding water or an aqueous binder solution to the mixed powder obtained in the step 1 (4) or the step (8), and granulating using a low shear granulator. The (four) towel, the raw material of the raw material of the raw silk is slowly agglomerated. Moreover, step 1 (4) or step noisy) and step 2 can also be performed simultaneously. The low-shear granulator used in this step can be used as long as the core is strongly compacted by a strong shear. For example, the original high-shear force type with the main wing and the chopped wing type or horizontal granulator, by: 140448.doc -16- 201000626 is set to lower the pressure to suppress the compaction and the following The Flow number setting can also be used to manufacture the particles of the present invention - fr b , < That is to say, the low-shear granulator of the present specification also includes: even if it is a granulator capable of shearing the granules, it can also be owed to the temple by setting the operating conditions. Pelletizing after reducing shear force

As a low-shear granulator, a granulator or a drum type which is granulated by the rotation of the main body portion in terms of the granulation ease and the improvement of the load-carrying ability Granulator. These devices can also be used in batch-to-continuous methods. Further, in terms of powder mixing property and solid-liquid mixing property, it is preferred to provide a separator for assisting mixing on a disk or a drum. Further, in order to use it as a low-cut granulator, it is preferable to set the number of pebbles of the granulator defined by the following formula to 10 or less from the viewpoint of the load-carrying ability. 8ατ, particularly preferably set to 〇6 or less 'Specially good is set to 〇. 4 or less. Flow number: Fr=V2/(Rxg) V: circumferential speed [m/s], R: radius from the center of rotation to the circumference of the rotating object [m], g: gravity acceleration [m/s2] Again, It is preferable to add the water or the aqueous binder solution to the mixed powder, and it is preferable to set the number of the granulators to 0.005 or more, and more preferably to 0.01 or more. In the vertical or horizontal granulator with main wing and chopped, the v and R use the value of the main shaft; in the disc type granulator or the drum type granulator which is granulated by the rotation of the main body portion of the main body , V and R use the value of 140448.doc -17- 201000626 of the main body of the body. Again. In the disc type granulator with chopped wings, V and R use chopped wings in the present invention, focusing on the particles of the agglomerated structure, granulating, to obtain a slow and uniform dispersion problem: due or adhesive It is difficult for the aqueous solution to uniformly disperse the binder. Twenty-two: The method of adding liquid by using a method of using a fluid binder such as a 1-fluid nozzle or a 2-fluid nozzle is a method of miniaturization. Depending on the multi-fluid nozzle, the adhesive is applied to the stomach and multi-fluid, and the gas and the nucleus make the adhesive and the micronized gas (empty: ":") flow through the independent flow path to the nozzle. In the vicinity of the front end portion, the submerged enthalpy is mixed, the micronized nozzle, the four-fluid nozzle, etc., and the two-fluid nozzle or the three-fluid spray can be used to carry out the mixing of the end portion of the mixing portion of the second:: atomization gas in the nozzle tip end portion. Any of the external mixing types - 4 in the nozzle = = = Γ using a multi-fluid nozzle such as a 2 fluid nozzle for fine droplets to add and add. As such a multi-flow round type 2 fluid nozzle (for example, can be used: wide-angle Body nozzle (manufactured by Tengqing 叩加加山卿(股)) or 4 flow angle 1 胜守motor (manufacturing), etc. Fu ^ To increase the speed of adhesive addition, it is also more effective to use 4 1 fluid or Other fluid nozzles—the surface maintains the miniaturization of the droplets—the surface increases the rate of addition. 2 With this method, it can be obtained or evenly dispersed in a high viscosity: in the raw::1 water solution, the yield is improved. Particle size group with a small particle size distribution 140448.doc 201000626 4 ·Step 3: Step 3: Drying the particles obtained in Step 2. By removing moisture, the particle/capacity can be increased. * Further, the loading can be suppressed by the particles. The ancients caused by the disintegration, the 轫姅 《 去 去 去 去 去 去 去 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低 降低The dry side is going to... and using an electric dryer or hot air drying; continuous Γ: a method of drying the batch type fluidized layer... exemplified by a vibrating fluid layer or a dryer, etc. As far as the speed of cognac is concerned,

Above, better is 12 〇 better 疋 80C is good (10). 〇 Above. Also, good 疋 15〇 °c or more, especially to inhibit the decomposition of the adhesive!乍 is sticky, the following wins &amp;, (4) is to increase the following, and the next is particularly good is 220. (The following is the following: <Physical properties of the particle group for surfactant preparation> The composition of the particle group for the interfacial force agent loading in x month to the structure of the earth mineral: Group: The powder material of the above-mentioned powder is slowly aggregated (7) Powder = (1) The larger interstitial space between the powder materials and the more intermediate position in the end of the material. Among them, (2), the gap of κ _ or less), and (1) 桷哉* (2) The impact on the load capacity and the load capacity is better than (the effect on the load speed is better than *, 〃, and the two sets are available.) The two load groups are adjusted. &amp; Particles for supporting surfactant loading 140148.doc 201000626 Further, when a clay mineral is formulated, a liquid surfactant composition may be carried between the layers, and thus it is expected that the supporting force can be improved. The surfactant-supporting particle group of the present invention is from the viewpoint of ensuring the supporting capacity of the liquid surfactant composition and ensuring a high (four) density after carrying the liquid surfactant composition. The bulk density is below HO g/l, preferably from 400 to 55 Torr, more preferably from 4 〇〇 to 5 〇〇 g/丨. It is considered that the lower bulk density of the supported particle group of the present invention can be achieved by granulation by the above-described low shear granulator. Further, from the viewpoint of dusting property and solubility in a detergent composition containing a detergent particle group in which a surfactant-supporting particle group-supporting liquid surfactant composition is used, The average particle diameter of the particle group for carrying is preferably from 140 to 600 μm, more preferably from 2 to 5 μm, and particularly preferably from 200 to 400 μm. From the viewpoint of increasing the allowable range of the amount of the liquid surfactant composition, the liquid-like surfactant composition of the surfactant-supporting particle group has a better oil absorption ability, which is better. It is preferable that Ο"-" is particularly preferably 0.5 ml/g or more. It is generally considered that the oil absorbing ability of the supported particle group of the present invention can be achieved by granulation by the above-described low shear granulator. From the viewpoint of increasing the supporting capacity of the liquid surfactant composition of the particle group, 5, the amount of the moisture of the surfactant-supporting particle group measured by the infrared moisture meter is preferably as small as possible, and preferably 5% by weight, and more preferably 10 parts by weight or less, particularly preferably 5% by weight or less. As a specific composition of the particle group for carrier-loading of the present invention, an example is 140448.doc -20· 201000626 If you can collect -C, 4_, the following composition: the bulk density is 55〇 / 丨 with minerals other than minerals, "and the clay is shown, the oil is 〇. 4 ml / g or more of the powder raw material is 40 ~95 weight: 'Clay mineral powder is 〇~45wt%' binder It is 〇~3 〇, and the water is 〇15% by weight. 物: 2 2 volume density f, average particle size, liquid surfactant Xihong b water 1, can be used in the measurement method of the following physical properties &quot; The method of measuring and controlling the composition of the detergent particle group &t; And the above-mentioned, the active agent rabbit is the surfactant, the loader is loaded with the surfactant, and the granules of the cockroach are used to make the high-volume dense detergent particles. group. 'As long as the detergent particles are contained in the detergent particle group, the interface obtained by the method of the surfactant of the Id soil is used alone; it may be used alone or other such as spray drying.

In the case of L, the mixture of the enthalpy of the present invention and the mixture of particles and other methods such as spray drying can be used as the interfacial activity-particle group. In the surfactant composition, for example, a separate surfactant and a secret surfactant may be used, but it is more preferable: 2 is used after mixing. In particular, the two will use a non-melting point having a melting point of 3 (rc as an ionic surfactant)...the effect of using the surfactant to raise the point of the surfactant (4) is 45~(10). Molecular^ A water-soluble nonionic organic compound ', 〜 30,000 solution. Further, as the melting point rising agent used in the present invention #1) or its water, for example, 140448.doc 201000626 exemplified: polyethylene glycol, poly Propylene glycol, polyoxyethylene alkyl ether, Pluronic mailer type nonionic surfactant, and the like. Further, an amphoteric surfactant or a cationic surfactant may be used in combination with the purpose. Further, from the viewpoint of improving the dispersibility of the detergent particle group in the low-temperature water, it is also possible to formulate an anionic interface such as a benzoic acid salt of 5 to 25% by weight in the detergent particle group. Active agent. As the surfactant composition, for example, one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. As an anionic surfactant, it can be exemplified by an alkylbenzenesulfonate, an alkyl or alkenyl ether sulfate, an α-olefin, an α-transalkyl fatty acid salt or a vinegar, a burnt or a dilute base thereof. Shallow acid salt, amino acid type surfactant, Ν-mercapto amino acid type surfactant, and the like. Particularly preferred are linear alkyl benzene sulfonium complex salts, 15 basic sulfate salts or alkyl ether sulfates s as relative ions, preferably alkali metals such as sodium and potassium, and amines such as monoethanolamine and diethanolamine. Further, in order to obtain a defoaming effect, a fatty acid salt can be used in combination. As the nonionic surfactant, there may be mentioned polyoxyethylene alkyl or cation ether, polyoxyethylene alkyl or dilute phenyl fluorene, polyoxyethylene polyoxypropylene or dilute (four), and trademark Ranike is a representative of polyoxyethylene polyoxypropylene monool 'polyoxyethylene alkylamine, higher fatty acid alkanolamine, alkyl glycoside, alkyl glucoside, alkyl amine oxide and the like. Among them, those having higher hydrophilicity and having a lower liquid crystal forming ability when mixed with water or having no liquid crystal are preferable, and a polyoxyalkylene alkyl group or an alkenyl ether is particularly preferable. Preferably, it is an ethylene oxide of an alcohol (hereinafter referred to as an ethylene(x)) adduct, and another 140448.doc -22- 201000626 &quot; an adduct and a propylene oxide (hereinafter, PO (propylene oxide))

As a additive, it is preferable to use addition EO after adding #P to add P to add PO and then add (10), or random addition to E; as a particularly good addition In the order of the block addition, the block is added to PO, and the block is added to EO to obtain the following formula: R-〇-(EO)x-(P〇)y_(e〇 )zH

Wherein R is a hydrocarbyl group, preferably an alkyl or alkenyl group, and deuterium is ethylene oxide

Base, P〇 is a fluorenated propylene group, and x, Y and Z represent the average addition molar number, respectively. Among them, the relationship between the best average addition moles is χ> 〇, Ζ>0, χ+γ+ζ=6~14, χ+ζ=5~12, γ=ι~4. Examples of the cationic surfactant include a quaternary ammonium salt such as a mercaptotrimethyl ketone salt. Examples thereof include a carbonyl betaine type and a sulfopolysaccharide as an amphoteric surfactant, a causticoid type. The amount of the anionic surfactant in the surfactant composition is preferably (9) parts by weight, more preferably 20 to 200 parts by weight, particularly preferably the nonionic surfactant i (10) parts by weight. It is 3〇~18〇 parts by weight. The compounding amount of the melting point-increasing agent of the nonionic surfactant is preferably (1) (10) parts by weight, more preferably 5 to 50 parts by weight, per part by weight of the nonionic surfactant (10). Within this range, the composition has a viscosity of 1 〇 at a temperature above the pour point of the composition.

The temperature range below Pa's, more preferably below 5 Pa_s, and having a flow point below 2 Pa.s, particularly below the composition, is higher than the nonionic 140448.doc •23·201000626 interface activity In the temperature range of the bright point of the agent, the composition has a hardness of preferably 10 kPa or more, more preferably 30 kPa or more, particularly preferably a temperature range of 5 kPa or more, thereby producing the composition and It is suitable for the rinsing property of the detergent particle group and the bleed-out of the nonionic surfactant when the detergent particle group is stored. The physical property value of the surfactant composition can be determined by the following method. The flow point can be measured by the method of JIS K 2269. Melting point can be obtained with the FP800 Thermo System "Mettler FP81" (Mettler

Manufactured by Instrumente AG) The measurement was carried out at a temperature increase rate of 22 °c/min. The viscosity can be determined by measuring the conditions using a B-type viscometer ("dVM_b type" manufactured by TOKY, KEIKI & Division) and a rotor No. 3, 00 r/min. Further, when the measured value under these conditions exceeds 2 pa.s and cannot be measured, the measurement is carried out under the conditions of the rotor N〇3, 12 r/min. Entering the hardness system is a rheometer ("NRM-3002D", manufactured by Immobility Co., Ltd.) and a circular adapter (N〇3, 8φ) with a diameter of 8 mm and a bottom area of 0.5 cm2. The value obtained by dividing the load at 20 mm/min into the interior of the surfactant composition by 2 除 divided by the bottom area of the circular adapter. From the viewpoint of the cleaning property and the solubility, the amount of the surfactant composition added is preferably in the range of from 10 to 100 parts by weight of the surfactant-supporting particle group, and more preferably in the range of from 10 to 100 parts by weight. It is in the range of 2 〇 to 8 〇 by weight, particularly preferably in the range of 30 to 60 parts by weight. The surfactant composition and the surfactant-supporting particle group are mixed, and the powder raw material other than the powder raw material may be added as an addition amount, compared with 1 part by weight of the particle group. Good is 140448.doc -24- 201000626 〇~150 parts by weight. As the raw material of the powder, for example, a crystalline citrate such as aluminum citrate 'PURIFEED (manufactured by Tokuyama Siltech Co., Ltd.) or the like can be given. Preferred physical properties of the detergent particle group of the present invention are as follows. The bulk density is preferably 500 to 1000 g/1, more preferably 6 〇〇~1 〇〇〇g/b, particularly preferably 650 to 900 g/b, and the average particle size is preferably 15 〇 to 5 〇. 〇μηι 'Better is 1 8 〇 ~ 400 μιη. Further, the bulk density and the average particle diameter can be measured by the method described in the measurement method of the physical property described later. &lt;Preparation method of detergent particle group&gt; A suitable method for obtaining a detergent particle group includes the following step (1), and optionally, step (II). Step (I): the surfactant composition and the particle group containing the surfactant-supporting particle group obtained by the production method of the present invention are carried out under the conditions that the surfactant composition is in the form of a liquid or a slurry. The step of mixing. Step (Π): a step of mixing the mixture obtained in the step (1) with a surface coating agent, and coating the surface of the obtained detergent particle group with the surface coating agent. Among them, the step (11) can also be chopped at the same time. ιStep (I) As a method of supporting the surfactant composition in the supporting particle group, a sample group or a surfactant composition can be used by using a batch type or a continuous type mixer. The method of mixing. Here, in the batch type τ day τ, as a method of input into the mixer, the following method may be employed: (1) first, after loading the particle group for loading in the mixer, and then adding the interface activity 140448 .doc 25- 201000626 agent composition, (2) repeatedly adding the L-root group and the surfactant composition to the mixer device; f3, one part of the supporting particle group is mixed After the machine, 'repeated one point' - the remaining loading particle group and the surfactant composition are added to the sw. :: At the boundary, the active agent composition is heated to a temperature within a practical temperature range, for example, 5 Torr to 9 Å. , _ L also exists as a solid or a slurry::: previously prepared or dissolved in a low viscosity non-ionic interface tongue material surfactant aqueous solution or water to prepare the interface = composition of the mixture The liquid or the aqueous solution may be added to the supporting particle group in 4 of the mixed solution or the aqueous solution. By this method, the surfactant composition in the form of a solid or a slurry can be easily added to the granule group. The mixing ratio of the less viscous surfactant composition or the water and the solid surfactant composition is preferably as long as it is a range in which the obtained mixed liquid or aqueous solution can be sprayed. The method for preparing the above-mentioned mixed liquid can be, for example, a method in which a solid or slurry-like surfactant composition is put into a viscous liquid compared with a surfactant or water, and a method of mixing octagonal and + 1 σ is performed. Or the acid precursor of the surfactant, such as an anion a, is known to be used in a less viscous surfactant or in water with an inerting agent (such as aqueous sodium hydroxide or aqueous potassium hydroxide). The acid is then gamma, and the method of preparing a mixture of surfactant compositions is used. In this step, the surfactant composition and the interface may be added to the "human modified composition", the surfactant is added to the compound, and the residue composition is added. Thereafter, an anionic interface 140448.doc -26-201000626 acid precursor of the active agent is added. By adding an acid precursor of an anionic surfactant, the surfactant can be highly formulated and the particle group for loading can be increased. The storage capacity, the loading capacity control, and the non-ionic surfactant of the detergent particles are inhibited from bleeding and physical properties such as fluidity. The acid precursor which can be used in the anionic surfactant of the present invention is, for example, Examples include alkylbenzenesulfonic acid, alkyl or dilute ether sulfuric acid, alkyl or alkenyl sulfuric acid, α-olefinsulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, fatty acid, etc. From the viewpoint of the fluidity of the detergent particle group, it is particularly preferable to add a fatty acid after adding a surfactant. The amount of the acid precursor of the anionic surfactant is 100 parts by weight relative to the particle group for supporting Preferably, it is 5 to 3 parts by weight, more preferably 1 to 20 parts by weight, especially preferably i~i 〇 by weight, particularly preferably} heavy injury. Also, as an anionic surfactant The method for adding the acid precursor is preferably supplied as a liquid at a normal temperature in the form of a spray, or may be added as a solid at a normal temperature in a powder form, or may be sprayed after being melted. When the addition is carried out, it is preferred to raise the temperature of the detergent particle group in the mixer to a temperature at which the powder is melted. Specific examples of the preferred mixing device include the following devices. The following are the following (1) to (3). There are (1) Henschel mixer (manufactured by Mitsui Koike Chemical Co., Ltd.), high-speed mixer (manufactured by Shenjiang Industrial Co., Ltd.), vertical granulation Machine (POWREX (manufacturing)), l〇DIGE mixer (made by Matsusaka Technik Co., Ltd.), coulter mixer (pi〇ughshare Mixer) (made by Pacific Mechanics Co., Ltd.), 曰本专利特平平1〇_ Mixing device described in 296〇64, 曰本专利Kaiping 1 〇 _296〇 No. 65, published in the Gazette 140448.doc -27- 201000626 Mixing equipment, etc., (2) belt mixer (manufactured by Handan Machinery Industry Co., Ltd.), batch kneading machine (manufacturing), Ribocone (manufactured by Okawara Seisakusho Co., Ltd.), (3) conical spiral mixer (manufactured by HOSOKAWAMICRON Co., Ltd.), SV mixer (manufactured by Shinko Pantec Co., Ltd.), etc. In the mixing device described in Japanese Laid-Open Patent Publication No. Hei 10-296065, the same apparatus can be used to perform the steps described later ( Π) 'So it is better in terms of the simplification of the device. In the mixing device described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is preferred because the disintegration of the particle group for loading is carried out. Further, in terms of suppressing the disintegration of the surfactant-supporting particle group, it is also preferable to use a conical spiral mixer or SV which can mix a powder and a liquid without imparting a strong shearing force. Mixing devices such as mixers and belt mixers. Further, the carrier particle group and the surfactant composition may be mixed using a continuous apparatus. Moreover, as a continuous type apparatus, Flexo Mix type (made by POWREX), TURBULIZER (made by HOSOKAWAMICRON), etc. are mentioned. Further, when a nonionic surfactant is used in this step, it is preferred to be added to the surfactant composition before the addition of the surfactant composition, or to the addition of the surfactant composition, or After the surfactant composition is added, or previously mixed in the surfactant composition, 140448.doc * 28 - 201000626

The melting point for increasing the refining point of the surfactant is ^~(10). c, the molecular weight is! A water-soluble nonionic organic compound (hereinafter referred to as a brightening agent) of 1,000 to 30,000 or an aqueous solution thereof. By adding a melting point-increasing agent, the agglomeration of the detergent particle group and the exudation property of the surfactant in the detergent particle group can be suppressed. Further, as the above-mentioned melting point rising agent, the same melting point lifting agent as that exemplified for the bright point rising agent having the composition of the above-mentioned detergent particle group can be used. The amount of the eluting point increasing agent is preferably from 5 to 8 parts by weight, more preferably from 5 to 5 parts by weight, based on 1 part by weight of the supported particle group, and most preferably from 1 to 3 parts by weight. Parts by weight. The above range is preferable in terms of suppressing aggregation between particles of the detergent particles contained in the detergent particle group, achieving high-speed solubility, and suppressing exudation or agglomeration. As a method of adding a melting point-increasing agent, # is added by mixing with a surfactant in advance, or a method of adding a melting point-increasing agent after adding a surfactant, thereby suppressing the exudation property of the detergent particle group or The agglomeration is more favorable. It is more preferable that the temperature in the mixer of this step is raised to a point above the flow point of the surfactant composition and then mixed. Further, the pour point of the surfactant composition can be measured by the method specified in JIS Κ 2269. Here, the temperature to be heated may be higher than the flow point of the surfactant composition added to promote the loading of the surfactant composition, and if the range is practical, it is preferable to exceed the flow. The point to a temperature higher than the flow point of 50 C is more preferably a temperature higher than the flow point of 1 〇 ° c to 3 〇〇 c. Further, when an acid precursor of an anionic surfactant is added in this step, it is more preferable to raise the temperature to a temperature at which the acid precursor of the anionic surfactant can react and then mix. 140448.doc -29· 201000626 It is better to use a batch mixing time to obtain a suitable detergent particle group and an average residence time in a continuous mixture, preferably 2 minutes, more preferably 2~ 1 minute. When the interface is added, an aqueous solution of a lingual agent or an aqueous solution of a water-soluble nonionic organic compound is used as the surfactant composition, the remaining water may be dried after mixing and/or mixing. The powdered surfactant and/or powder builder may also be added before, during, or after the addition of the surfactant composition. By adding a powder builder, the particle size of the detergent particle group can be controlled, and the cleaning power can be improved. In particular, when an acid precursor of an anionic surfactant is added, it is effective to promote a neutralization reaction by adding a powder builder which exhibits alkalinity before the addition of the acid precursor. In addition, the term "powder builder" as used herein refers to a cleaning power-enhancing sword of a powder other than a surfactant, and the specific one is § means that zeolite, citrate, etc. exhibit metal ion sequestration ability. Also I L... ^ The base of this force, or the base of sodium carbonate, potassium carbonate, etc., which shows the performance of the test. 'Crystal money metal ion sonicity and ability to test the ability to have the base 'other sodium sulfate Such as a base for increasing the ionic strength. Here, as the crystalline powder builder, the following materials can be used as a preferred powder builder: Japanese Patent Laid-Open No. WOU No. 3, line 17 (particularly, it is calcined under the 鸠~(10) generation. For the crystallization of the 曰 曰 专利 专利 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Crystalline sulphuric acid salt described in the lithus acid salt. Here, it is better to use 140 . 〇 · · · 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 140 448 448 The metal is 0.5 to 3.2, preferably 1.5 to 26. The amount of the powder builder used is 0.5 to 12 by weight, based on the weight of the supporting particle group (10). The portion is more preferably Η by weight. When the detergent builder uses the powder builder in the range, the solubility is good, and it is better to add the detergent granule after the step (1). Step (II). Coating 2 Step (II): In the present invention, in order to modify the surface of the particles carrying the interface detergent particle group by the step (1), One yang &lt; The following steps (π) of the various surface coating agents of the following (1) fine powder body 22: 颂 = the surface of the particle group of the detergent particles of the present invention is added to the fluidity of the detergent particle group (4) The shell 1 is stored in the surface modification step. The tendency of the step is therefore better than the illusion illustrated in step (1) ^ ^ . ^ ai with both the stirring wing and the chopping wing ^ The following is a description of the surface coating agent. (1) The fine powder is used as the fine powder. The preferred one is ν b, and the average particle size is 1 ο μπι ” 2°, 1 to 10 μηη. When the particle diameter is within this range, the coating ratio of the surface of the particles of the washing agent particle group is the same as the average particle diameter of the detergent particles by the flowability and blocking resistance of the cleaning group. The micropowder (manufactured by Horiba, Ltd.), which is used in the particle analyzer (4), is measured using a micromirror (nine). 140448.doc •31 - 201000626 又. Also, in terms of cleaning power, The good thing is that the fine powder has a relatively high ion exchange capacity and high ability to test. As the fine powder, aluminosilicate is preferable, and both crystalline and amorphous may be used. In addition to aluminum citrate, sodium sulfate, calcium citrate, oxidized oxidized stone, and oxidized earth are also preferred. a fine powder such as talc, clay, amorphous cerium oxide derivative, or crystalline bismuth. Further, a metal soap having an average particle diameter of primary particles of 0_1 to 10 0 can be used in the same manner. A surfactant such as a powder (for example, an alkyl sulfate or the like) or a water-soluble organic salt. When a crystalline decanoate is used, it is preferable to prevent the aggregation due to moisture absorption or carbon dioxide absorption by the crystalline citrate. The fine powder is mixed and used. The amount of the fine powder to be used is preferably from 0.5 to 40 parts by weight, more preferably from 2 parts by weight to 2 parts by weight, based on the weight of the detergent particles. When the amount of the fine powder used is within this range, the fluidity can be improved and the consumer can feel good. (2) Liquid material The liquid material may, for example, be a water-soluble polymer or a fatty acid, and may be added in a water/cold solution or in a molten state. (2-1) Water-Soluble Polymer As the water-soluble polymer, carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, a copolymer of acrylic acid and maleic acid, or a salt thereof can be mentioned. Salt and so on. The amount of the water-soluble polymer to be used is preferably from 5 to 10 parts by weight, more preferably from 1 to 8 parts by weight, particularly preferably from 2 to 6 parts by weight, per 100 parts by weight of the detergent particles. Share. When the water-soluble polymer is used in the range of 140 448.doc • 32 - 201000626, a detergent particle group exhibiting good solubility, good fluidity, and blocking resistance can be obtained. (2-2) Fatty Acid The fatty acid may, for example, be a fatty acid having 1 to 22 carbon atoms. The amount of use of the fatty acid is preferably from 0.5 to 5 parts by weight, based on the weight of the detergent particles, and is particularly preferably from 0.5 to 3 parts by weight. When it is solid at normal temperature f, it is preferred to carry out the spray supply after heating to a temperature at which fluidity is exhibited. Further, &lt;Detergent Composition&gt; The detergent composition of the present month is a T compound which contains the above-mentioned detergent particle group and further contains a washing component added in addition to the detergent particle group. A composition (for example, builder particles, fluorescent dyes, enzymes, perfumes, antifoaming agents: bleaching agents, bleach activators, etc.). In terms of the first force, the cleaning of the detergent composition card is 50% by weight or more, more preferably 6. Group by weight or more: It is 70 weight. /. The above is less than %. Particularly good 疋 80 weight. Above, just wash the particles other than the detergent particles, the good amount of the m detergent composition contains a good Γ reset below 'better 40% by weight or less, especially good 疋 3〇 It is particularly preferably 2% by weight or less, and particularly preferably 2 parts by weight. &lt;Preparation method of detergent composition&gt; τ. The preparation method of the detergent composition is not particularly limited, and for example, the group of particles can be listed and additionally added. The composition of the washing sword is carried out.: The human method. The m composition thus obtained contains the loading capacity of the surfactant of ~5 square 140448.doc -33 - 201000626 The amount of detergent particles is 'cleaned by... As a result of the detergent composition, it is possible to exhibit a sufficient detergent, and it is necessary to use a powder detergent, an automatic dishwashing detergent, etc. A powder for clothing and a method for measuring physical properties. &lt; 1. Method for determining the bulk density by the method of the bulk density κ 3362. The JIS 2. The average particle diameter and the average particle diameter can be measured by the following two methods: (1) For an average particle diameter of 80 μηι or more, Use a standard sieve of m κ嶋 (mesh 2000~125 (four) to vibrate for 5 minutes) The median diameter is calculated based on the weight fraction of the mesh size. In more detail, the mesh is used as (2), 180 _, 25 〇 _, 355 _, 5 〇〇 _, 71 〇 (four), 1000 μπι, 1400 μηι, 2000 grade sieves and trays are stacked on the tray from the small mesh screen. Add 100 g of particles from the top 2 pm sieve and cover them. Type sieve oscillating machine (manufactured by HEIKO, tapping 156 times/min, rolling: 290 times/min) to 'make it vibrate for 5 minutes, and then the particles remaining on each division and tray The weight is measured, and the weight ratio (%) of the particles on each sieve is calculated. The weight ratio of the particles on the sieve having a smaller mesh is sequentially accumulated from the tray, and the total particle diameter is 50% as the average particle. Further, for those having an average particle diameter of 125 μηι or less, mesh 45 μηι, 63 μm, 90 pm, 125 μπι, 180 μπι, 250 μηι, 355 140448.doc -34-201000626 pm, 500 μm, 710 are used. Ιιη, 1〇〇〇_, 14〇〇_, 2〇〇〇陶之η The sieve and the tray were subjected to the same measurement to calculate the average particle diameter. (2) For the average particle diameter of less than 80 (four), a laser diffraction/scattering particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) was used. The particles were dispersed in a solvent in which the particles were not dissolved, and the median diameter was measured as the average particle diameter. Further, '(7) may be measured for 15 Å or less. 3. Moisture

The moisture measurement of the particle group can be carried out by an infrared moisture meter method. That is, the sample is collected in a sample of known weight, and the sample is collected 3 g' using an infrared moisture meter (Ken Institute of Science and Technology (FD-240 manufactured by Kett Electric Co., Ltd.) to heat 20 (TC) for 3 seconds. The time at which the weight is not changed is regarded as the end of drying, and the amount of water is calculated based on the weight after drying and the weight before drying. 4. The fluidity flow time is 100 mL from the funnel for measuring the bulk density measured by Jis κ 3362. The time required for the powder is preferably 10 seconds or less, more preferably 8 seconds or less, and particularly preferably 7 seconds or less. <Quality evaluation method> 1. Oil absorption capacity in the absorption measuring device (S410 manufactured by Asahisouken Co., Ltd.) was charged with 35 g of powder to rotate the driving blade at 200 rpm. Liquid nonionic (EMULGEN 108 manufactured by Kao) was added dropwise at a liquid supply rate of 4 ml/min. The point at which the maximum torque (t〇rque) is reached. The amount of liquid added at the torque point of 70°/min of the maximum torque of 140448.doc -35- 201000626 is divided by the amount of powder input as the oil absorption capacity. Particle size distribution The Rosin-Rammler number is calculated as an index of the particle size distribution by the detergent particle group passing through a sieve of 1410 μm. The calculation of the Rosin-Rammler number can be performed by the following formula: log(log( 100/R(Dp)))=nlog (Dp/De) R(Dp) : Accumulation rate of powder above the particle size Dp μιη [〇/0]

Dp : particle size [μηι]

De : average particle size [μηι] n : Rosin-Rammler number

The higher the Rosin-Rammler number η, the narrower the particle size distribution. As η, it is preferably 1 or more, more preferably 1.5 or more. 3. Solubility As the solubility index of the present invention, the 60 second dissolution rate of the detergent particle group described below can be used. The dissolution rate is preferably at most 9% by weight, more preferably at least 95%. Further, the detergent composition can also be evaluated by the same method. The 60 second dissolution rate of the detergent particle group was calculated by the following method. Cooling to 5t l hard water (Ca/Mg molar ratio 7/3) with a hardness of 71.2 mg CaC〇3/L is filled with a 1 L beaker (cylinder with an inner diameter of l〇5 mm and a height of 15〇mm, For example, in the 玻璃 [glass beaker) manufactured by Iwate Glass Co., the water is used to keep the water temperature of 5 C in a fixed state, using a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, 140448) .doc -36· 201000626

Tef1〇n (registered trademark) SA (circle t-fine) is stirred at a rotation speed (800 r.p, m.) of approximately 1/3 of the water depth. Under agitation, reduce the amount of detergent particles that have reached 丨.0000 0.001 〇 g and disperse in water and continue to stir. After 6 seconds, the standard sieve (diameter i (10) called the detergent particle group dispersion in the beaker beaker) defined by the weight of the known claw Z 88〇i will remain on the _ The detergent particles in the hydrated state are recovered from the open container of known weight. The operation time from the start of filtration until the recovery of the sieve is i (four) seconds. The electric dryer is heated to 105. The residue of the collected detergent particles is dried for a few hours, and then cooled in a desiccator (25 ° C) (4) to which it is charged for 3 G minutes. After cooling, the dried detergent is cleaned ^ The total weight of the residue, the sieve and the recovery container is measured, and the dissolution rate of the detergent particle group (0/〇) is obtained by the formula (1). Solubility (%) = { 1-(T/S) } X 100 (1) S _ detergent input particle weight (g) T · Dissolving the detergent particle group deposited on the sieve when the aqueous solution obtained under the above stirring conditions is supplied to the sieve Dry weight of the material (8) (dry conditions: after holding at a temperature of 105 ° C for a few hours, in a dryer with a silicone ( 25 C) maintained for 30 minutes) 4. Particle yield The particle yield of the present invention is determined by the ratio of particles of a specific particle size range in all particles. For example, the particle yield of 125_1〇〇〇μηι is protected by eight The proportion of particles in the granules of 125 μm or more and 1 00 μmη or less. 5. Detergent yield 140448.doc -37-201000626 The detergent yield of the present invention means that the above detergent particles are additionally added The ratio of the particles of 118 0 μm or less in the detergent composition obtained by mixing the detergent components. EXAMPLES In the examples, unless otherwise specified, the following raw materials were used. : Average particle size 1 〇〇μηι (Manufactured by CENTRAL GLASS, oil absorption capacity 0.45 ml/g) Light soda ash 2 : Average particle size 1 7 5 μιη (Manufactured by CENTRAL GLASS, oil absorption capacity 0.69 ml/g) Clay mineral: Laundrosil DGA Powder (manufactured by Siid-Chemie) Sodium polyacrylate: Weight average molecular weight 10,000 (manufactured by Kao) Heavy soda ash: average particle size 290 pm (manufactured by CENTRAL GLASS) Sodium sulfate: none Aquatic Glauber's Salt (Four Nations (manufactured by the company) Example 1 In a 70!^ barrel type granulator with a separator ((}) 40 (: 11 ^ 1 ^ 60 (: 111 / speed 3 2 rpm / Phloes number 0.23) Mixed clay mineral 2.1 kg and light soda 1:1 kg (clay mineral/powder raw material = 3/7). After mixing for 2 minutes, use 1 fluid nozzle (Spraying Systems-Japan): adhesive spray pressure 0.4 MPa), adding 2.5 kg of water in 3 minutes. After the addition, the mixture was granulated for 3 minutes, and then discharged from a roll type granulator, and dried at 200 ° C for 3 hours using an electric dryer. The moisture after drying was 1.1% by weight/〇. The obtained particle group 1 was a particle group having an average particle diameter of 204 μm and a bulk density of 490 g/1, and the oil absorption capacity was 0.52 ml/g. Also, the 125-1000 μιη piece 140448.doc -38- 201000626 has a grain yield of 56% and a Rosin-Rammler number of 1.0. Example 2 A clay mineral of 2.1 kg and light soda ash, 4.2 kg (clay mineral/powder material) was mixed in a 70 L-cylinder granulator (φ40 cmxL60 cm/rotation speed 32 rpm·/Pota number 0.23) with a separator. =1/2). After mixing for 2 minutes, use 2 fluid nozzle (Spraying Systems-japan (manufactured by Spraying Systems-japan): binder spray pressure · 15 MPa / micronized air spray pressure 3 Mpa), added in 5 minutes (, 25% polyacrylic acid The sodium aqueous solution was 3.8 kg. After the addition, the pellet was granulated for 3 minutes, and then discharged from a roller type granulator, and dried in an electric dryer at 2 ° C &gt; c for 3 hours. The moisture after drying was 1.3% by weight. The obtained particle group 2 was a particle group having an average particle diameter of 320 μηι and a bulk density of 495, and the oil absorption capacity was 0.51 ml/g. Further, the particle yield of 125-1000 μηι was 56%, and the R〇sin_Rammler number was 丨6. Example 3 Mixing 21 kg of clay mineral with 4.2 kg of light soda ash 2 in a 70 L drum type granulator with Pm plate (φ4〇cmxL6〇cm/rotation speed 32 rpm·/ brown number 0·23) Mineral/powder raw material = 1/2). After mixing for 2 minutes, add 2 8 kg of 25% sodium polyacrylate aqueous solution in 5 minutes using a 2 fluid nozzle. Add 'after' for 3 minutes granulation, from the drum type granulator Discharge, use an electric ' &amp; dryer to dry at 2GG ° C for 3 hours. After drying water It is 0.9% by weight. The obtained particle group 3 series average particle diameter 39〇μπ1, bulk density 43〇g/i, particle group oil absorption month b force is 〇58 ml/ge, and (4) particle yield is 93%, Rosin_Ramm ER number is 2 5. 140448.doc -39- 201000626 Production Example 1 375 parts by weight of water is put into the mixing tank, and after the water temperature reaches 35 〇c, stone 'IL k sodium 127 is added 1 part, sodium sulfite 5 Parts by weight, fluorescent dye, parts by weight, stirred for 10 minutes, 127 parts by weight of sodium carbonate was added, and 75 parts by weight of 4% by weight of sodium polyacrylate aqueous solution was added and stirred for 1 minute to prepare a preparation liquid. 24 parts by weight of sodium hydride of the fine crystal precipitation agent was added to the first preparation liquid, and the mixture was stirred for 0 minutes. Further, the weight portion of the zeolite was added and stirred for 30 minutes to obtain a second preparation slurry having a total weight of 42 parts by weight. %). The second preparation liquid is supplied to the spray drying tower (convection type) by a pump, and is sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle provided near the top of the tower: the high temperature gas supplied to the spray drying tower is from the lower portion of the tower The temperature is 00 C into 4T supply 'from the top of the tower to 9 (rc discharge. The moisture of the obtained particle group 4 is 4% by weight. The obtained particle group average particle size 285 _, volumetric twist 476 g / l The particle group. Example 5 In a 70 L drum type granulator with a separator ((4) cmxL6〇(10)/speed U m/Fulu limb 23), (10) parts by weight and clay stone 〇· 6 parts by weight 'Using a 2-fluid nozzle to add 55.9 parts by weight of the solution of the continent polyacrylic acid = 5 minutes after the addition. After the addition, the particles were granulated after the minute, and the self-rolling: type granulator was discharged, using an electric dryer at 2 〇. 〇.. Dry for 3 hours. The moisture after drying is 1 〇 weight 〇 / 〇., bulk density 489 g / 1 again, 125-1000 particles obtained by the 5 series average particle size 3 i 7 The particle group has an oil absorption capacity of 0.5 1 ml/g. H0448.doc -40- 201000626 The grain yield is 97% and the R〇sin_Rammier number is 2 9. Example 6 In a 70 L drum type granulator (φ4〇cmxL60 cm/rotation speed 32 r_P.m./Fulu number 23.23) with a separator, a light soda iiioo part by weight was used, and 2 fluids were used. The nozzle was added with 55. 6 parts by weight of a 35% sodium polyacrylate aqueous solution in 5.5 minutes. After the addition, after granulation for 3 minutes, it was discharged from the drum type granulator.

It was dried at 200 t for 3 hours using a t-air dryer. The water after drying was divided into 0.9 weight ❶/. . The obtained particle group 6 was a particle group having an average particle diameter of 328 μηη and a bulk density of 448 g/i, and the oil absorption capacity was 〇 61 ml/g. Further, the particle yield of 125_1 〇〇〇 _ was 95.2%, and the number of Rosin-Rammler was 2.5. Example 8 The interface activity #] composition (polyoxyethylene (tetra)/polyethylene glycol/household stupid acid/water=42/8/42/8 (weight ratio)) was adjusted to 8 generations. Then, in the L〇DIGEMixer (manufactured by Matsusaka Technik Co., Ltd., the capacity of 13 〇 [, with a casing), 100 parts of the obtained surfactant-supporting particle group 3 were forked, and the spindle was started (stirring wing, Speed: 6 rpm, peripheral speed: 16 m / s). Further, 8 (r warm water of rc was flowed to the cannula at 1 〇 L/min. 5 parts by weight of the above surfactant composition was added thereto in 2 minutes, and then the mixture was stirred for "weighing." A portion of amorphous aluminosilicate, and into the spindle of d minutes (rotation speed: 12 rpm, peripheral speed: 3" m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28, discharge lotion Particle group 1. The obtained detergent particle group was a mean particle #481 _, a bulk density of 140448.doc -41 · 201000626 800 g / l, and a particle group of 5.8 s fluidity. Example 9 Using Example 3 The surfactant-supporting particle group 3 produced in the surfactant-supporting particle group 3 and the surfactant-supporting particle group 4 obtained by spray drying in the production example i were used to produce the detergent particle group 2 by the method described below. The surfactant composition (polyoxyethylene alkyl ether / polyethylene glycol / sodium alkyl phthalate / water = 42 / 8 / 42 / 8 (weight ratio)) was adjusted to 8 〇 t ^ relay ^ LODIGEMixer (Matsaka Institute (manufacturing), capacity n〇L, set of magical investment = 50 parts by weight of the obtained surfactant to support particle group /, part by weight The surfactant-supporting particle group 4 was started, and the spindle (grating blade, rotation speed: 60 rpm, peripheral speed: i 6 m/s) was started. Then, 8 generations of warm water was flowed to 10 L/min. Casing: 50 parts by weight of the above surfactant composition was put into it for 2 minutes. Then, stirring was carried out for 5 minutes. Further, 6 parts by weight of an amorphous (tetra) acid salt was introduced, and the spindle of the minute was entered (rotation speed: 120 ah, The circumferential speed: 3"m/s) and the chopper (", the peripheral speed of one) (4), the detergent particle group 2 obtained by discharging the cleaning group, the average particle size of 342 (four), the particle group of the surgery / 1. The dissolution rate is 6.2, and the flowability is 6.2. Further, according to Example 1, 100, 100 parts by weight of the surfactant-supporting particle group $ ===supporting particle group 3 is used, and Example _ Detergent Particle Group 3 of the formula. The obtained detergent particle group 3 is an average particle size of 356 _, a bulk density of 140448.doc • 42- 201000626 768 g/i, and a particleivity of 6.0 s. Example 11: (10) parts by weight of the surfactant-supporting particle group 6 was used instead of the interface-supporting particle group 3, and The detergent particle group 4 was discharged in the same manner as in Example 8. The detergent particle group obtained by μη and the bulk density was a particle group having an average particle diameter of 3 ι 5 808 g/I and a fluidity of 5 9 s. example 1

Mixing clay minerals 1.5 kg with light soda ash in a 10,000-mass machine (2 VAC manufactured by EIRICH; disk speed 44 rPm 'cutting speed 165 rpm / Phlud number (1)) (clay mineral/powder raw material = 3/ 7). After mixing for 2 minutes, water i25 kg was added in i minutes using an i fluid nozzle. After the addition, after granulation for 3 minutes, it was discharged from a 10,000-horse machine, and dried in an electric dryer at 2 Torr for 3 hours under TC. The moisture after drying was 丨〇% by weight. The obtained particle group 9-series average granules A particle group with a diameter of 352 μηη and a bulk density of 715 g/1 has an oil absorption capacity of 〇·16 ml/g. Further, the yield of particles of 125-1000 μ„ι is 92%. The R〇sin-Rammler number is 2.0. Comparative Example 2 Mixed in a 1 〇L high-speed mixer (manufactured by Fukae p〇wtec); stirrer speed 2〇〇福禄8 94; shredded wing speed 36〇〇rp m / Phloe number 398) 1 part by weight of light soda ash and 42.9 parts by weight of clay mineral (clay mineral/powder material = 3/7). Using a 1-fluid nozzle, adding 35°/min in 1 minute, 45.3 parts by weight of sodium polyacrylate solution After the addition, it was carried out for 4 minutes. 140448.doc -43- 201000626 After granulation, 'self-granulator discharge' was dried using an electric dryer at 2〇η: hour. The moisture after drying was 10% by weight. The particle group 1 has an average particle size of 362, and the particle group with a bulk density of 73 has an oil absorption capacity of 〇.3〇'. Further, ι2 5_ι 〇〇〇 yield was 55% 'R〇sin-Rammler number was $. Comparative Example 3 ❹ _ parts by weight of the surfactant-supporting particle group produced in Comparative Example 2 _ instead of the surfactant The particle group 3 was planted, and the detergent particle group 6 was produced in the same manner as in Example 8. The obtained detergent particle group 6 was an average particle diameter _, a bulk density of 83 〇 gd, and a fluidity of 6.5 s. In the case of the light soda ash 1 of 35 parts by weight, and the clay mineral is 15 parts by weight, instead of 5 parts by weight of the surfactant-supporting particle group 3, the use and the examples are used. In the same manner, a detergent particle group was produced. The obtained detergent particle group 7 was a particle group having an average particle diameter of 424 (four), a bulk density of 835 gd, and a fluidity of 6.1 s. Further, the conditions of the above examples and the like were obtained. Shown in the following table t. 140448.doc -44- 201000626 Example 6 0.23 〇Τ-Η 1 1 19.5 36.1 1 00 (N 448 95.2 in (N 0.61 Example 11 315 808 ON 92.8 Example 5 0.23 〇1 〇19.6 36.3 3/500 317 489 97.0 〇\ (N 0.51 Example 10 〇\ 356 00 VO Ο 95.5 I 幽1 1 1 1 1 1 1 1 1 1 I Example 9 342 807 (Ν 'Ο 93.0 Example 3 0.23 1 100.0 50.0 22.6 67.9 (N 390 430 93.0 IT) &lt;N 0.58 Example 8 m 〇\ 800 00 64.1 Example 2 0.23 〇1 Distortion 1 50.0 22.6 67.9 (N η ΓΛ 56.0 0.51 1 1 1 1 1 1 Example 1 0.23 〇Η 1 42.9 1 51.0 _1 ζ- m 204 490 56.0 Ο 0.52 1 1 1 1 1 1 Particle group granulator Light soda ash 1 Light soda ash 2 Clay mineral polyacrylic acid clay mineral/powder raw material ratio average particle size [μηι] Bulk density [g/1] Particle yield [%] Rosin-Rammler number [-] Oil absorption capacity [ml/ g] detergent yield [%] average particle size [μηι] bulk density [g/1] fluidity [s] solubility [%] 5 tsu $ W. 洗 detergent particle group property -45- 140448 .doc 201000626 [Table 2] Table 2 Comparative Example 1 Comparative Example 2 - Particle Group Granulator Flow Number 213 8.94 - Composition of Particles for Surfactant Loading (Parts by Weight) Light Pure Test 1 100 100 - Light Soda ash 2 - - - Clay mineral 42.9 42.9 - Sodium polyacrylate - 15.9 - Water 35.7 29.4 - Clay mineral/powder raw material ratio 3/7 3/7 - Particle carrier for surfactant loading Average particle size [μπί] 352 362 - Bulk density [g/1] 715 736 - Particle yield [%] 92 55 - Rosin-Rammler number [_] 2.0 1.5 - Oil absorption capacity [ml/g] 0.16 0.30 - - Comparison Example 3 Comparative Example 4 Detergent Particle Group Physical Detergent Yield [%] - 55 93 Average Particle Size [μπί) - 876 424 Bulk Density [g/1] - 830 835 Fluidity [S] - 6.5 6.1 Dissolution Sex [%] - - 74.5 According to the comparison between Example 1, Comparative Example 1, and Comparative Example 2, it is understood that by performing low shear granulation, it is preferred to carry out low shear granulation having a Phlox number of 1.0 or less. To obtain the desired bulk density and oil absorption capacity of the particle group. Further, according to the second, third, fifth, and sixth embodiments, according to the production method of the present invention, a particle group exhibiting desired physical properties can be obtained regardless of the content of the clay mineral, and it can be seen from Examples 8 to 11 that it is used. The detergent particle group of these particle groups also showed substantially the same physical properties and quality as the particle group which became the corresponding raw material 140448.doc • 46- 201000626. On the other hand, according to Comparative Example 3, when a particle group produced by a high shear mixer, specifically, a mixer having a Phlox number exceeding 〗·〇, is used, it is formed from the viewpoint of quality and productivity. A detergent particle group that is inferior to a detergent particle group using a particle group produced by a low shear mixer.

Further, according to the comparison between Example 9 and Comparative Example 4, it was found that the raw material containing ruthenium non-granular material did not exhibit a good dissolution rate in place of the detergent particle group carrying the (four) particle group of the surfactant of the present invention, and The detergent particle group containing the particle group for loading of the present invention is inferior in quality. According to the results, it is shown that the quality of the detergent particles by the granulation of low shear granulation is industrially usable. According to the present invention, the liquid can be obtained by not drying the method. The surfactant-supporting particle composition is excellent in the load of the surfactant composition and the warpage/loading capacity/loading speed.

140448.doc 47·

Claims (1)

201000626 VII. Patent Application Range: 1. A method for producing a particle group for surfactant loading, which is used for producing a particle carrier particle group having a bulk density of 550 g/1 or less, and includes the following step 1 (a)~2 : Step 1 (a): a step of mixing a clay mineral powder and a powder raw material having a oil absorption capacity of ml/g or more other than the clay mineral; and Step 2: mixing in the step 1 (4) A step of granulating the water or a binder aqueous solution using a low shear granulator is carried out. — 2. A method for producing a particle group for surfactant-supporting, which is used for producing a surfactant-supporting particle having a bulk density of 550 a/Ι or less, and a price of w ^ g/1 or less The group includes the following steps 1 (b) to 2: Step i (b) is a step of mixing powder materials having a water absorption capacity other than clay minerals of 〇4 _ or more; and step 2: obtained by stepping) a step of adding water or a binder = aqueous solution to the mixed powder by granulation using a low shear granulator. 3' A method for producing a particle group for surfactant loading according to claim 1 or 2, wherein low shear The number of plutoniums of the granulator is 1 〇 or less. 4· ^ The manufacturing method of the particle group for surfactant-supporting of claim 1 or 2, 2' and 3, step 3 · The granules obtained in step 2 Step of drying: 5. The method for producing a particle group for surfactant-supporting according to claim 3, which comprises the step of drying the particles obtained in the step 2: 6. The request item 1 or 2 Method for producing particle group for surfactant loading, 140448.doc 201000626 The method uses a multi-fluid nozzle to add water or a binder water lacquer solution. 7) The method for producing a particle group for the surfactant-supporting agent of claim 3 ', the water-based or the binder is added to the nozzle 8. The method for producing a particulate material for surfactant-supporting agent according to claim 4, and the use of water or a binder for water-spraying in the nozzle of the machine body. The particle group is manufactured by a method in which a water or a binder is added to a water-spraying wave by a multi-fluid nozzle. 10. The method for producing a surfactant-supporting particle according to Item 6 ', Φ 诘·§* AU .. The multi-fluid nozzle in the middle is a 2-fluid nozzle—^ θ Μ 'muscle bottle $ ϋ筲〇11. : The manufacturer of the surfactant-supporting particle group of the item 7 is a two-fluid nozzle. In the case of the request item Ru^, the surfactant-supporting particle group is manufactured as a two-fluid nozzle. 13. The surfactant-supporting particle group of the item 9 is manufactured in the middle of the nozzle. 2 fluid nozzle. 14. If the request item] 忐9-Tiangong, Zhizhongshishi surfactant The raw material for the loading of the granules is a light soda ash. 15. The method for producing a particle group for surfactant-supporting agent according to claim 3 is a raw material containing light soda ash. In the case of the ash s, the method for producing the particle group for the ash loading, the n raw material contains the light soda ash. 17. The production of the granules for the powdery agent loading in the interfacial activity of claim 5 A method for producing a particle group for interfacial activity-carrying according to claim 6, wherein the method of the method of the present invention, wherein the method of the present invention comprises: 140448.doc 201000626 Light soda ash. 19. The method of producing a particle group for interfacial M loading according to claim 7, wherein the mastrin starting material comprises light soda ash. 20. If the interface of claim 8 is in the middle of the powder; the method for producing the granules for cultivating J is used, and the raw material of the Ningshu end contains light soda ash. 21. The method of producing a particle group for supporting the interfacial activity of claim 9, wherein the raw material comprises light soda ash. 22. The interface activity of claim 1 is the method of manufacturing the particle group for carrying. 23. In the case of the request item j丨, the method of manufacturing the particle group for carrying the powder, wherein the powder raw material comprises light soda ash. 24. The method of producing a particle group for interfacial activity d of claim 12, wherein the powder material comprises light soda ash. 25. The method of producing a (4) particle group of the surfactant-supporting agent according to claim 13, wherein the powder material comprises light soda ash. A surfactant group-supporting particle group having a bulk density of 55 Å or less 'containing the following components: a powdery material having an oil absorption capacity of 0.4 ml/g or more other than a clay mineral: 40 to 95% by weight of a clay mineral powder: ~45% by weight Adhesive: 〇~35wt% Water: 0~1 5wt%. 27. A high bulk density detergent particle group, wherein the surfactant prepared by the method of any one of the items 1 to 25 is used for the frequency of 140,400.doc 201000626 &lt; The particle group or the particle group of the particle group for surfactant-supporting agent of claim 26 is loaded with a surfactant composition. 2 8. A detergent composition comprising the detergent particle group of claim 27. 140448.doc 201000626 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: (5) If there is a chemical formula in this case, please reveal the best indication of the invention. Chemical formula: (none) 140448.doc