TW462987B - Method for producing high-bulk density detergent composition - Google Patents

Abstract

The method for producing a high-bulk density detergent composition having a bulk density of 650 g/L or more, including the steps of (a) blending the following components in an agitation granulator: (i) a granular, solid, water-soluble alkali inorganic substance, (ii) a tripolyphosphate having an average particle size of from 1 to 30 μm, and (iii) one or more granular solids other than components (i) and (ii); and (b) adding the liquid acid precursor of an anionic surfactant to the mixture obtainable in Step (a) to neutralize the liquid acid precursor of an anionic surfactant with the alkali inorganic substance while the mixture remains in a particulate form, and granulating the neutralized mixture, to give a granular mixture. In step (a), the granular, solid, water-soluble alkali inorganic substance is used in an amount of equal to or greater than that necessary for neutralizing a liquid acid precursor of an anionic surfactant to be used in step (b).

Description

Printed by employees of the Central Bureau of Standards of the Ministry of Economic Affairs on consumer cooperation 6 2 9 R 7 A7 _ B7 V. Description of the invention (1) Field of the invention The present invention relates to a method for manufacturing a high bulk density detergent composition. More particularly, the present invention relates to a method for manufacturing a high bulk density detergent combination, in which a detergent composition containing particles having small particle size is obtained in a high yield. Discussion of Related Techniques Recently, in the detergent industry, attention has been paid to a method of manufacturing a powdered detergent having a relatively high bulk density, for example, those having a bulk density of 650 g / liter or higher, β containing, for example, alkylbenzenesulfonic acid The powdery detergent of the salt anionic surfactant is prepared by using a base, such as sodium hydroxide, sodium carbonate, etc., to neutralize the liquid acid precursor of the anionic surfactant in situ. For example, Japanese Patent Publication No. 60-72999 and GB-2,166,452B disclose a method comprising blending a detergent sulfonic acid, sodium carbonate, and water with a strong shear device; cooling the generated solid matter to 40 or more Low; finely pulverizing the cooled product; and then forming the fine powder into particles. This method is typical of the conventionally proposed method, in which the neutralization reaction product is a dough piece, which requires a kneading device, such as a kneader, which can supply the very large energy required for the neutralization reaction. The GB-1,369,269 patent discloses a method for manufacturing an anionic detergent, which comprises vigorously mixing the detergent sulfonic acid and sodium carbonate powder by using a mixer equipped with a shear device, such as a Lfi (jige PLOUGH SHARE mixer). In this way, in order to obtain a product in a granular form rather than a dough piece, it is necessary to blow a gas into the two-component mixture described above, so that the reaction material is appropriately flowable and the reaction mixture is blended. In order to perform this treatment, the mixer must be It becomes very complicated. Also, because no water is used to accelerate the neutralization reaction, the reaction proceeds mildly, so that a relatively coarse product is formed. The temperature during the neutralization reaction (C is the domain ^ (Pulmonary epidemic disease in 2 veins) — (Please read the note on 35 'Read Island before filling out this page) Revision 46298 7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention ( 2) It usually also rises to about 85 C. When the temperature during the neutralization reaction rises, it is difficult to add thermally degradable ingredients such as perfumes and volatile ingredients, so it is difficult to contain thermally degradable ingredients in the composition. And the volatile ingredients. Japanese Patent Publication 3-33 199 discloses a method for manufacturing a detergent composition comprising drying and neutralizing the ingredients in a high-speed mixer / granulator at a temperature of 55 C or lower, and then A step of adding a liquid binder for granulation. Japanese Patent Publication No. 4-363398 discloses a method for manufacturing a detergent composition, which comprises drying in a high-speed mixer / granulator at a temperature of 55 C or higher. And ingredients, and then a step of adding a liquid binder for granulation. Japanese Patent Laid-Open No. 3-146599 discloses a method for manufacturing a detergent composition comprising drying a neutralizer in a continuous high-speed mixer; then using a medium-speed mixer Increasing the bulk density; and then cooling and / or drying the high bulk density product to be granulated. The detergent composition obtained by the above method includes particles having a small particle size ^ However, for practical purposes, the Yield of Detergent Composition of Particle Size Particles Needs Improvement "Japanese Patent Unexamined Publication No. 7-503 750 discloses a method of manufacturing detergent particles The acidic anionic surfactant is neutralized in a high shear mixer with a granular neutralizer (sodium carbonate) having a particle size of less than 5 microns in diameter of 50% by volume. However, nothing is disclosed in this announcement Or it is suggested to improve the yield with respect to the composition containing a detergent having a desired particle size. Therefore, it is an object of the present invention to provide a method for manufacturing a bulk density cleaner composition at a high yield, which includes a particle size having a suitably low range. The size of this paper is applicable to the Chinese national standard (CNS} A4 grid (210X: 297 mm) (please read ^^ the private note and then fill out this page) "

46298 7 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) These and other objects of the present invention will be apparent from the following description. SUMMARY OF THE INVENTION The present invention relates to the following: (1) A method for manufacturing a high bulk density detergent composition having a bulk density of 650 g / liter or higher, comprising the steps of: (a) mixing in a stirring granulator Combining the following ingredients: (i) granular, solid, water-soluble qualitative inorganic substances, (ii) tripolyscale salt with an average particle size of 1 to 30 microns, and (iU) —or more ingredients (i ) And granular solids other than (ii), wherein the granular, solid, water-soluble alkaline inorganic substance is equal to or greater than the liquid acid precursor required to neutralize the anionic surfactant in step (b) And (b) adding the liquid acid precursor of the anionic surfactant to the mixture obtained in step (0) to neutralize the liquid acid precursor of the anionic surfactant with a basic inorganic substance at the same time, The mixture is still in a granular form, and the neutralized mixture is granulated to give the granular mixture; (2) The method of the above item ⑴, wherein the high-bulk-density detergent composition produced has a thickness of 1,000 microns or less Average particle size, and 1400 microns The smaller particles have a weight percentage of 55% or higher, where the average particle size is determined by the weight percentage after five minutes according to JIS K 88 (Π vibration standard sieve, depending on the sieve degree); 方法 the above item ⑴ or item ⑺ method, Wherein the granular, solid, water-soluble alkaline inorganic material has an average particle size of 30 microns or more; 方法 The method of the above item ⑴ or item ，, in which the 6-private paper scale is applied in step ⑻ 适用 Chinese national standard (CNS ) I -------- ^ V equipment-\ / _ (谙 9 read the precautions for private information and fill in this page again) Order JB, si. 462987 A7 --------- B7 V. Invention (&Quot; ——-Neutralize and bury gas while blowing into the agitating granulator; (") The method of the above item ⑺ or item ，, wherein a liquid acid precursor of an ionic surfactant is added in step ㈨ Previously, the aqueous test solution was added to the mixture obtained in step (a) and blended in an amount of 0.05 to 0.5 times the amount required to neutralize the liquid acid precursor of the anionic surfactant; (6) the above The method of item (5), wherein the aqueous alkali solution is an aqueous solution of sodium hydroxide; (7) The method of the above item (1) or item (2), further comprising steps: (0) surface modification of the granular mixture obtained in step (15); (8) the method of the above item or item (2), wherein the The agitating granulator is equipped with agitator blades and a tool for decomposition and dispersing; (9) The method of the above item (7), wherein the surface modifier used in the surface modification step is 1 to 30 microns. Crystalline or amorphous alkali metal aluminosilicate with average particle size; and (10) the method of item (1) or item above, wherein in the step-further adding and blending crystals having an average particle size of 1 to 30 microns Or amorphous alkali metal aluminosilicate. Detailed description of the invention 1. Step (a) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Step 11 (a) consists of mixing the granulator with the following ingredients: (i) granular, solid, water-soluble alkaline inorganic Substances, (ii) trimerates having an average particle size of 1 to 30 microns, and (iii) one or more ingredients (i) and granular solids other than (ii), among which granular, solid, water-soluble The basic alkaline inorganic substance is equal to or greater than -7- This paper size applies to Chinese national standards (CNS > A4 specifications (2 丨 0 > < 297 mm) 4 6298 7 A7 B7 V. Description of the invention (Ministry of Economics) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards = the liquid acid foresight and the required amount of granular, solid, water-soluble alkaline inorganic substances in the anionic surfactants of the W can be used as the test in any agent composition Agents, and specific examples include sodium carbonate, sodium hydrogen carbonate, sodium hard acid, carbonic acid, carbonic acid, etc. Among granular water-soluble qualitative inorganic substances, carbon materials are preferred because carbonic acid is used in final cleaning. The detergent composition acts as a detergent binder and hazard agent. Therefore, borrow The addition and blending of a granular, solid, water-soluble qualitative inorganic substance component including carbon and an amount of a liquid acid precursor sufficient to neutralize the anionic surfactant can be advantageously performed. Neutralization reaction. In particular, it is preferable to add a granular, solid, water-soluble qualitative inorganic substance in an amount equal to or greater than that eliminated by neutralization, for example, 1 to 2 ... times the amount required for neutralization. 2 to 10 times the amount required for neutralization, especially 3 to 8 times the amount required for neutralization. The average particle size of granular, solid, water-falling alkaline inorganic substances is also not particularly limited. By yield and storage From the viewpoint of a further increase in stability, the average particle size is preferably 30 μm or more, more preferably 40 to 200 μm, especially 50 to 100 μm. In this specification, granular, solid, The average particle size of the water-soluble alkaline inorganic substance is evaluated based on a volume using a laser scattering particle size distribution analyzer (" LA-5 00 ", manufactured by HORIBA Co., Ltd.). The tripolyphosphate has 1 to 30 micrometers, 5 to 20 microns is preferred, and an average of 6 to 15 microns is more preferred Particle size. Generally, the smaller the average particle size of the tripolyphosphate is, the higher the yield is because it is inhibited by the cohesion t of the neutralized granular mixture. On the other hand, a tripolyphosphate containing particles of small size on an industrial scale is prepared Please note

I Side-by-side Paper Money Shicai Guanjiazhuan (CNS) A4 · (21GX297 male thin 462987 A7 -------- B7 V. Description of the invention (6) Viewpoint of productivity of salt The particle size is preferably 1 μm or more. From the viewpoint of suppressing the cohesion of the neutralized granular mixture, the average particle size is preferably 30 μm or less. In this specification, the average particle size of the trimer acid salt is based on It was evaluated using a volume of a laser scattering particle size distribution analyzer ("LA-5OO :, manufactured by HORIBA Co., Ltd.). The amount of tripolyphosphate is also not particularly limited. The trimelinate is preferably 2 to 50% by weight 'more preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight I is contained in the final detergent composition product. From the viewpoint of suppressing the cohesion of the neutralized granular mixture' three The amount of polyphosphonate is preferably 2% by weight or more. From the standpoint of the degree of freedom of combination to generate a detergent composition, the amount is preferably 50% by weight or less.-Or more granular Specific examples of solid, water-soluble alkaline inorganic substances and granular solids other than trimerates are one or more candidates Fluorescent agents; pigments; anti-redeposition agents, such as sodium salts of polycarboxylate polymers and carboxymethyl cellulose; granular surfactants, such as fatty acids, their salts, linear alkylbenzene sulfonates, alkyl sulfates Ester; spray dry powder, diatomite, calcite, kaolin, bentonite, sodium sulfate, sodium sulfite, etc. granular solids can be used alone or in a combination of two or more. The amount of granular, solid, water-soluble alkaline inorganic substances and particulate solids other than trimeric phosphonates is not particularly limited. The amount of granular solids in the final detergent composition product is preferably 2 to 80% by weight, more preferably 5 to 50% by weight, especially 7 to 20% by weight. Further in step (a), a crystalline or amorphous metal test having an average particle size of from 30 to 30 microns may be added. Chopping acid salt. By adding metal inspection salt -9- This standard is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 46298 7 Printed by A7 B7, Consumer Cooperative of Central Standards Bureau, Ministry of Economic Affairs Invention description (7), can suppress excessive Polymerization, and metal salt stearates can be used as an auxiliary to decompose the cohesive products in the tool of the mixing granulator. The amount of the above alkali metal aluminosilicate is not particularly limited. Alkali metal aluminum The amount of silicate in the final detergent composition product is preferably 1 to 8% by weight, more preferably 2 to 5% by weight, and the above effects can be effectively obtained in this range. In this specification, aluminum The average particle size of the silicate was evaluated based on the volume using a laser scattering particle size distribution analyzer (" LA-500 ", manufactured by HORIBA Co., Ltd.). In step (a), each of the above components was blended using a stirring granulator. The agitation granulator is not particularly limited, and it is preferable that the agitation granulator is equipped with a swinging beam leaf and used for decomposition and dispersion. Here, the beam leaves or devices can be replaced by devices with equivalent functions. Specific examples of the stirring granulator that can be used in the present invention in a batch method include vertical granulation (made by Powrex); South speed mixer (made by Fulcae Powtbc. Kogyo); Lfidige mixer (made by Matsuo Co., Ltd.) ; Mixer with PLOUGH SHARE (made by Pacific Machinery and Engineering Co., Ltd.); Mixer by Gedcke (made by Meiji Machinery Co., Ltd.), etc. Here, a Liidige mixer and a PLOUGH SHARE mixer are preferred. Specific examples of stirring granulators that can be used in the present invention in a continuous process include continuous Ladige mixers (medium speed mixers: those with considerable resistance time); CB recirculators (manufactured by L6dige; high speed mixers: having relatively short Those who fight against time); Vortex (manufactured by Hosokawa Micron); Shugi mixer (manufactured by powrex) * 'flow jet mixer (manufactured by Funken Powtechs), etc. Incidentally, in the present invention, the above mixers can be appropriately used in combination. -10- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1 1 K ^ i In-II! IJN Γ---II (谙 Please read the notes on the back * · .. before filling (This page)

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-IT 462987 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (8) It is also better that the stirring granulator is equipped with an outer sleeve to adjust the inner temperature of the granulator and to blow gas into Mix the nozzles in the granulator. The operating conditions of the mixing granulator in step (a) are not particularly limited ^ For example, the #combination time is preferably within five minutes. The stirring speed of the main spindle and the speed of the dispersing and dispersing tools can be appropriately set depending on the type of mixer used. For example, in the case of a mixer for a batch method, the mixing speed around the main mandrel is preferably 2 to 15 m / sec, and the surrounding speed for dispersing and dispersing is preferably 20 to 60 m / sec. Incidentally, at the time of or after the blending in step (a), and / or as the addition of the liquid acid precursor of the anionic surfactant in step (b), water may be added as a reaction initiator. By adding a reaction initiator, the neutralization reaction can be advantageously accelerated. The amount of water to be added is not particularly limited, and the mixture of water obtained in step (a) based on 100 weight, preferably 0.2 to 3 It is added in an amount of 0'5 to 1.5 parts by weight. From the viewpoint of initiating a neutralization reaction, the amount of water is preferably 0 to 2 parts by weight or more, and from the viewpoint of suppressing the cohesion of the detergent composition, the amount is preferably 3 by weight or less. Incidentally, in the case of the above mixture or the liquid acid precursor of the anionic surfactant, or in the case of using other aqueous solutions, the amount of water to be added may be determined by considering the water content of these ingredients. 2. Step (b) Step (b) includes adding a liquid acid precursor of the anionic surfactant to the mixture obtained in step (a) to separate the anionic surfactant from the liquid acid precursor using a magnetic inorganic substance. The body is neutralized while the mixture remains in a granular form, and the neutralized mixture is granulated to give the granular mixture. At this step -11- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back Φ ·. Before filling this page)

46298 7 A7 B7 V. Description of the invention (in 9 steps, a granular mixture is formed and the resulting granular mixture is used as a high bulk density detergent composition · »The liquid acid precursor of the anionic surfactant refers to the acid form in the liquid state Anionic surfactants, which form salts due to the neutralization reaction. Therefore, the liquid acid precursor of the anionic surfactant can be any known anionic surfactant in acid form without any particular limitation. Specific examples include linear aromatic benzene sulfonic acid (LAS), or-fluorene sulfonic acid (AOS), alkyl sulfuric acid (AS), and internal olefin sulfonic acid, fatty acid ester sulfonic acid, alkyl ether sulfuric acid, dialkyl Lithanoic acid, fatty acids, etc. The liquid acid precursor may be used alone or in a combination of two or more ingredients. The amount of the liquid acid precursor of the anionic surfactant may be appropriately determined according to the composition of the desired detergent composition Setting. The amount of the liquid acid precursor of the anionic surfactant, in the form of the anionic surfactant produced by the neutralization reaction of the final detergent composition product, is preferably 5 to 45% by weight, and more preferably 10 Up to 4 0% by weight. 'Extremely preferably 20 to 40% by weight, more preferably 35% by weight. Incidentally, even if the main surfactant in the detergent composition is supplied in an isolated form, the same can be obtained in the present invention. Printed in step (b), the liquid acid precursor of the anionic surfactant is added to the mixture obtained in step (a), while the mixture is maintained in step (a) Β can be obtained in granular form. In order to maintain the mixture in a granular form, it is desirable to gradually add the liquid acid precursor to the mixture. The time required to add the liquid acid precursor of the anionic surfactant depends on the amount added, so it cannot be generalized In the case of a mixer in a batch method, the time required for the addition is preferably one minute or more, more preferably 1 to 10 minutes, more preferably 2 to 5 minutes. Here, the addition station 12-

This paper is suitable for printing from New Zealand (CNS) A4 ^ J $ r (210X297 ^ JT 462987 A7 B7) Printed by the Shell Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. The description of the invention (10) is preferably one minute or The reason is that, when the addition of the liquid acid precursor of the anionic surfactant is performed in an extremely short time, the temperature rise explained below occurs due to the heat of the rapid neutralization reaction. The liquid acid of the anionic surfactant The precursor can also be added continuously or in separate stages in multiple stages. Most addition devices can also be provided. Incidentally, the anionic boundary. The addition of the liquid acid precursor of the surfactant, in step (b ), The neutralization reaction and granulation occur simultaneously, thereby forming a granular mixture. After the addition of the liquid acid precursor of the anionic surfactant, it is desirable to operate the granulator for another 30 seconds or more, preferably It is one minute or more. Thereby, the additional step 'neutralization reaction can be advantageously completed β. In step (b), it is preferable to perform neutralization while blowing gas into the agitating granulator. Into a mixer granulator, steamable The excess water generated during the neutralization reaction, and the gas is used to cool the product, thus inhibiting the granular product from forming dough pieces. The available gases include N2 gas, air, etc. The amount of air blowing (amount of air flow) is not particularly limited Blowing at a rate of based on 100 parts by weight of the granular product, preferably equal to or greater than 2000 parts by weight per minute, more preferably equal to or greater than 0.02 parts by weight per minute. In step (b) Due to the heat of reaction generated by the neutralization reaction, the temperature of the mixture may rise. Because if the temperature of the mixture rises, it is difficult to add thermally decomposable components such as perfumes and volatile components. The temperature of the mixture in step (b) is maintained at a relatively high temperature. It is preferably 90 ° C or lower, more preferably 80. (: or lower. In order to adjust the temperature of the mixture within the range indicated above, for example, it is desirable to use cold water to pass through the outer shell of the stirring granulator as the above. Gas Blowing Mixer -13- This paper is silky) (please read the back " Note ^ | ^ item and fill in this page)% pack -------- 丨 Order W ------- ---- 4 6298 7 Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Print A7 B7 V. Description of the invention (Alternative method in η. = 发 "'在 步 ⑽b) t' After adding the heart acid material of the active agent, the reactivating surfactant ^ The former amount and the required amount of technology are 5 times the amount of G mixed into the blended silk.… The addition of a specific amount of aqueous test solution to the mixture obtained in step ⑷ becomes desirable because of the composition of the detergent particles that form the detergent composition. The particle size can be small '. Moreover, the bulk density and the acceleration of the neutralization reaction can be increased. The amount of the aqueous test solution is preferably the amount required to neutralize the liquid acid precursor of the anionic surfactant, from 0,05 to G. The amount of .5 times is more preferably an amount of m to 0.45 times, and particularly preferably is an amount of 15 to 0.40 times. From the viewpoint of initiating a neutralization reaction and obtaining a desired effect, the amount of the aqueous test solution is preferably at least OM times greater than the amount required for neutralization, and from the viewpoint of suppressing the cohesion of the detergent composition, this amount is more than It is preferably equal to or less than 0.5 times the amount required for neutralization. Incidentally, the degree of the axial aqueous test solution is not particularly limited. In the case of a low concentration, an excessive amount of water and a special aqueous test solution are supplied to the mixture, making the easy-to-clean detergent composition lack cohesion. Therefore, the concentration of the aqueous alkaline solution is preferably 20 to 50% by weight, and more preferably 30 to 50% by weight. /. The special content is 40 to 50% by weight. The kind of aqueous solution of the alkali that can be used in the present invention is not particularly limited. Specific examples thereof include aqueous sodium hydroxide, aqueous potassium hydroxide, and the like, which are aqueous solutions of strong bases which are liable to cause a neutralization reaction with a liquid osmium precursor of an anionic surfactant. Among them, from the viewpoint of cost reduction, aqueous sodium hydroxide is suitably used. It is also more preferable that the above-mentioned aqueous solution of the base has a pH of 12 or higher. The blending in this step can also be carried out until the aqueous solution of the added alkali is uniform. 14- This paper ruler ^ General purpose is not the national length ^ (CNS) A4 size (21〇x29).

Printed by the Consumer Cooperatives of the Central Bureau of Accreditation of the Ministry of Economic Affairs 4 6298 7 A7 -------- B7 V. Description of the Invention (12) a " ------- The degree of geographical dispersion. Incidentally, the addition of the aqueous test solution can be performed in the following specific examples; Π) the addition can be performed after the treatment of step (a); or (2) the addition can be performed at the same time as step (a). In the case where the addition of the aqueous alkaline solution is performed simultaneously with step (a), the mixture is obtained by using the following step (a ') as a specific example of step (a): U') blended in a stirring granulator The following ingredients: (1) granular, solid, water-soluble alkaline inorganic substance, (Π) tripolyphosphate with an average particle size of 1 to 30 microns, (Π1) — or more ingredients (i) and ( H) other granular solids, and (iv) an aqueous test solution, which is an amount of 0.05 to 0.05 times the amount required to neutralize the liquid acid precursor of the anionic surfactant It is added, wherein the granular, solid, water-soluble alkaline inorganic substance is used in an amount equal to or greater than that required for neutralization of the liquid acid precursor to be used for the anionic surfactant in step (b). In this embodiment, it is important to perform the addition of the aqueous alkali solution before step (b). Therefore, the addition step of the aqueous alkali solution is not necessarily limited to the steps after step (a). More specifically, in a specific embodiment, other detergent ingredients may be blended in a granular, solid, and water-soluble manner. Add alkaline alkaline substance and aqueous alkali solution. This method is very effective when adding ingredients with poor alkali resistance. Incidentally, from the viewpoint of uniformly dispersing the aqueous alkali solution in the mixture, it is preferably the specific example (1), in which the addition of the aqueous solution after the treatment in step (a) is performed. Standard (CNS) from the specification (2 丨 0 > < 297 mm) .1: 1: j I installed -----.- order-: ------ (Please & Read Back®, the Please fill in this page again) 46298 7 A7 ------——___ B7 V. Description of the invention (13) ------ By using the method including the above steps, you can get A high bulk density cleaner composition having a granular mixture of a higher bulk density. The high bulk density cleaner composition obtained by the method of the present invention preferably has the following properties: (1), preferably 650 to 950 grams In this specification, the bulk density is the value evaluated by the method defined in jisk 3362; (2) From each solution rate < From a viewpoint, it is preferable to have a thickness of 1,000 μm or more, more preferably 800 μm or more, more preferably 300 to 800 μm, and particularly preferably 35 to 650 μm. Average particle size; and preferably 55% or higher, more preferably 60% or higher, more preferably 65% or higher, especially 70% or higher, a percentage of particles passing through 1400 microns. In this specification, the average particle size is determined by the weight percentage after five minutes of vibration standard sieve according to JISK8 8 01 depending on the sieve degree, and the percentage of particles passing 1400 microns indicates the portion occupied by particles of 14000 microns or less. (3) Free flow force with a flow time of preferably 8 seconds or less, more preferably 7 seconds or less "In this specification, the free flow force is defined as self-use force in accordance with JIS K 3362 Bulk density measurement The time period required for the discharge funnel to discharge 1000 milliliters of powder. Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperative Press 3. Step (c) The method of the present invention may further include step (c), which is Step of surface modification of granular mixture obtained in step (b) "In order to further improve the free-flowing force and storage stability of the high bulk density detergent composition obtained in the method of the present invention, it is desirable to provide step (C). In particular, it is desirable to provide step (C). In accordance with the measures -16- this paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 male thin) 4 6 2 98 7 A7 -------------- B7 5 2. Description of the invention (M) Adding a specific amount of the following surface modifiers to the stomach while blending the granular mixture obtained by step (b) to complete the surface modification. The surface modifier can be any conventionally known Also, crystalline or amorphous alkali metal aluminosilicate (zeolite), calcite 'diatomaceous earth, silica, etc. can be suitably used. The above aluminosilicate preferably has an average degree of 1 to 30 micrometers, more preferably a fork to a micrometer. The amount of the surface modifier 5F in the final detergent composition product is preferably 2 to 15% by weight, and more preferably 4 to 12% by weight. Incidentally, the surface modifier "average particle size basis" is evaluated using the volume of laser scattering particle size distribution analysis (| "LA-500", manufactured by HORBIA Co., Ltd.). * In the case of adding a surface modifier, The operation time of the agitating granulator is not particularly limited, and the operation time is preferably from 5 minutes to 5 minutes. Incidentally, in the method of the present invention, the composition of the cleaning agent composition which can be obtained from the liquid component is selected. Addition. The addition of the liquid component can be performed in any of steps (a) (b) and (c), for example, it is preferred that the addition of the liquid component is performed before the addition of the surface modifier. Examples include any specific optochemical ingredients commonly used in detergent compositions, which include liquid non-ionic surfactants; water-soluble polycharacters, such as polyethylene glycol, acrylic acid, maleic acid copolymer, and the like; Fatty acid ^ Sealed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The liquid component can be used alone or in a combination of two or more. From the viewpoint of cohesion of the detergent and detergent composition, the amount of the liquid component is preferably Final cleaner 15% by weight or less of the compound product, more preferably 10% by weight or less. In the case where a liquid component is added before the addition of the surface modifier, the operation time of the stirring granulator is not particularly limited. And, the operating time is preferably 0 = to. • 17- This paper size applies the Chinese National Standard {CNS) A4 specification (210X297); 46298 7 A7 B7 V. Description of the invention (15) In the present invention, the following The optional ingredients can also be included in the detergent composition. For example, the optional ingredients include enzymes, perfumes, bleaches, pigments, etc. This optional ingredient can be cleaned by blending with the method of the present invention by using a mixer, such as a rotary mixer. The detergent composition and the selected ingredients are formulated. The high bulk density detergent composition obtained by the method of the present invention can also be used as a component for formulating other detergent compositions. Various specific embodiments of the present invention are as follows. [1]-Kind of manufacture A method for a high bulk density detergent composition having a bulk density of 650 g / liter or higher, comprising the steps of: (a ') blending the following ingredients in a stirring granulator: (0 granular, solid, water-soluble Inorganic inorganic substances, (Π) tripolyphosphates having an average particle size of 1 to 30 microns, (iii) one or more ingredients (i) and granular solids other than (ii), and (iv)-a water-based Alkali solution, this aqueous alkali solution is added in an amount of 0.05 to 0.5 times the amount required to neutralize the liquid acid precursor of the anionic surfactant, and the min. i · — Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Carp, where the granular, solid, water-soluble alkaline inorganic substance is equal to or greater than the liquid acid precursor of the anionic surfactant that will be in step (b) And the required amount are used; and (b) the liquid acid precursor of the anionic surfactant is added to the mixture obtained in step (a) to neutralize the liquid anionic interface active ^ with the alkaline inorganic substance , While the mixture still maintains a granular form, and the neutralized mixture is granulated to give a granular mixture. [2] The method described in item Π], wherein neutralization is performed in step (b), 、 / a uses -18

(cns) J 210X297 mm) 462987 A7 ---------- B7_ V. Description of the invention '' At the same time, the gas is blown into the stirring granulator. [3] The method described in item [2], wherein in step (b) the gas is blown in at a rate of equal to or greater than 0.002 parts by weight based on 100 parts by weight of the granular mixture. [4] described in the item The method of any one of [1] to [3], wherein the amount of the tripolyphosphate is 5 to 50% by weight of the obtained detergent composition. [5] The method described in any one of the items [1] to [3], wherein the tripolyscale salt has an average particle size of 1 to 30 m. [6] The method described in any one of items Π] to [3], wherein the generated high bulk density detergent composition has an average particle size of 1000 microns or less, and the weight percentage of particles of JL 1400 microns or less is 55% or higher, in which the average particle size is determined by the weight percentage after five minutes according to the JIS κ 8801 vibration standard sieve, depending on the sieve degree; [7] The method described in any one of items Π] to [3], its progress -The step comprises the steps: (c) surface modification of the granular mixture obtained in step (b). [8] The method described in item [7], wherein the surface modifier is a crystalline or amorphous alkali metal aluminosilicate. [9] The method described in any one of items [1] to [3] and [8], wherein the stirring granulator is equipped with a stirrer paddle and a prayer device for decomposition and dispersion. By using a tripolyphosphate with an average particle size of 1 to 30 microns and a liquid acid precursor that neutralizes anionic surfactants with granular, solid, water-soluble alkaline inorganic substances in a dressing granulator ' A high bulk density detergent composition having a small particle size can be obtained. -19- This paper size applies to China National Standards (CNS) M specifications (210X297 mm) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives 462987 A7 B7 V. Description of the invention (17) Examples The present invention borrows the following working examples It is explained in further detail, and is not intended to limit the scope of the invention. Example 1 A high speed mixer, 1 Lsdige mixer FKM-130D (made by Matsubo Co., Ltd.) was used to prepare a detergent composition having the composition shown in Table 1 in an amount of 35 kg for each unit. This mixer is equipped with a swing-out blade and a shearing device. This shearing device is equipped with a tool for disintegrating or dispersing. Here, the detergent composition is prepared by the following steps detailed below. Powder bonding includes 7.7 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 microns), 11-94 parts by weight of sodium carbonate (" LIGHT ASH ", manufactured by Central Glass Co., Ltd .: average particle size: 56.1 microns), and 11 parts by weight of the solid content of the fluorescer, at a blade speed of 1 30 rpm (peripheral speed: 3.4 m / s) and a shear force of 2 8 50 rpm (peripheral speed; 27 m / s) Under the condition of the device rotation speed, blend for one minute. Addition water of the base initiator is added to the content of the mixer as a reaction initiator in an amount of 0.2 5 parts by weight, and the blending is performed under the same blending conditions as above. Combine one minute and thirty seconds. When the neutralization mixer is operated under the same conditions as above, 10.92 parts by weight of linear alkylbenzenesulfonic acid (LAS) is added to the content of the mixer in four minutes. At the time of addition The ingredients are cooled by flowing 25ttC water through the jacket of the mixer. At this stage -20- f please read the note of self-interest and fill in this page}

I I i F I 46298 7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ___________ B7 5. Description of the invention (18), the temperature rose to 68.8 ° C. Incidentally, at this stage, the reaction mixture maintained a granular form. Incidentally, the above-mentioned LAS contains 0.16 parts by weight of sulfuric acid. After the addition of LAS, the mixer continued to operate for one minute under the same conditions. At the completion of the neutralization reaction of the addition of the body component and the surface modification, and at the same time when the mixer operates in the same manner as above, the effective amount of the copolymer is 0.18 parts by weight and 40% by weight of acrylic acid is added. An aqueous solution of the copolymer was added to the mixture and mixed for one minute = ten seconds. Then, the resulting 5 kun compound was subjected to surface modification by adding 4, 2 parts by weight of zeolite having an average particle size of 4 m to the mixer as a surface modifier, and operating the mixture for another two minutes to undergo surface modification. Incidentally, the zeolite contains 084 parts by weight of crystal water. The resulting detergent composition particles have the following properties: Percentage of particles passing through 1400 microns: 73.9%; average particle size: 577 microns; volumetric bifurcation: 818 g / liter; and free flow force: 2 seconds. Therefore, the particles show excellent properties. Post-blending A rotary mixer was used to join 0.18 parts by weight of the enzyme granules to the detergent composition 'prepared above and then sprayed 0.07 parts by weight of perfume to give the final powder of the high bulk density detergent composition. Incidentally, the amount of 'sodium carbonate' in this example is 6.7 times the amount required for las neutralization. Example 2 (please read the note of the private note ^ before filling this page) --------: l1T: -------------------- II.j 一—J. -21- This paper size applies to China National Standards (CNS) A4 specifications (210 X 29? Public love) 462987 A7 _ B7 V. Description of the invention (19) Use a similar composition as in Example 1 as in Example i A similar procedure, except that sodium tripolyphosphate with an average particle size of 8.3 microns is used, is administered to the detergent composition. The particles of the detergent composition after the post-blending step have the following properties: Percentage of particles passing through 1400 micrometers; average particle size: 530 micrometers; bulk density: 820 g / liter; and free flow force: 6.0 seconds. Therefore, the particles show excellent properties. Example 3 A similar composition as in Example 1 was performed using a similar composition as in Example 1, except that a LIGHT ASH obtained by pulverizing the light ASH used in Example 1 to an average particle size of 6.9 microns using a hammer mill was used to give a detergent composition . The particles of the detergent composition after the post-blending step have the following properties: Percentage of particles passing through 1400 microns: 60.5%; average particle size: 830 microns; bulk density: 83 1 g / liter; and free flowing force : 7,4 seconds. Therefore, the particles show excellent properties. Example 4 A similar procedure as in Example 1 was performed, except that air was blown into the mixer at a rate of 500 liters / minute, and the air was granulated at a rate of 100 parts by weight based on the neutralization and granulation steps per minute. 0.02 parts by weight was blown in, and the cleaners and compounds shown in Table j were given. 22 · This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 meal) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 462987 A7 __-___ B7_ V. Description of the invention ('— Cleaner combination after the post-blending step The particles have the following properties: Percentage of particles passing through 1400 microns: 76 2%; Average particle size: 542 microns; Bulk density: 83 5 g / liter; and Free-flow force: 5.8 seconds. Therefore, the particles show excellent properties. By Air was blown into the mixer, and the average particle size of the generated particles became smaller than that of the example, thereby improving the bulk density and free-flow force. Example 5 Using a high-speed mixer " Lfidige mixer FKM-1 30D " (Matsubo Co., Ltd.) ) For each unit, prepare a detergent composition with a composition of 35 kg. This mixer is equipped with agitator blades and a shearing device, and this shearing device corresponds to a tool β for decomposition or dispersion. Here, The detergent composition was prepared by the following steps detailed below. The powder blend included 7.7 parts by weight of sodium tripolyphosphate (3but 1 > 1 >; average particle size: 112 microns ), 12.62 parts by weight of sodium carbonate (" LIGHT ASH ", manufactured by Chuanliu Eye Co., Ltd .; average particle size: _ 56.1 microns), and (hli parts by weight of the solid component of the glazing agent, agitator at 130 rpm Blend for one minute under the conditions of the blade rotation speed and the shearing device rotation speed of 2850 rpm. Addition water of the reaction initiator is added to the content of the mixer in an amount of 0.25 parts by weight as the reaction initiator, and as above Under the same blending conditions, the joints are made—minutes and thirty seconds. -23 · This paper size applies to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm). )

The paper size printed by the Central Consumers ’Association of the Ministry of Economic Affairs ’s consumer cooperatives is applicable to China ’s National Standards (CNS) A4 (210X297 mm) 462987 A7 ___B7 V. Description of the invention (21) The neutralizer is operated under the same conditions as above At this time, 1092 parts by weight of linear alkylbenzenesulfonic acid (LAS) was added to the contents of the mixer over four minutes. Upon addition, the ingredients are cooled by passing 2 5 C water through the jacket of the mixer. At this stage, the temperature rose to 61.8C. Incidentally, at this stage, the reaction mixture maintained a granular form. Incidentally, the above-mentioned LAS contains 0.16 parts by weight of sulfuric acid. Air was also blown into the mixer under the same conditions as in Example 4. After the addition of LAS, the mixer continued to operate for one minute under the same conditions. The resulting detergent composition particles have the following properties: Percentage of particles passing through 1400 microns: 84.7%; average particle size: 5 78 microns; bulk density: 6 80 g / liter; and free flow force: 8.3 seconds. Surface modification In addition, the particles of the resulting cleaner composition were subjected to surface modification in the same manner as in Example i. The resulting detergent composition particles have the following properties: Percentage of particles passing through 1400 microns: 90: 1%; Average particle size: 462 microns; Bulk density: 68 gram / liter; and Free flowing force: 6.3 seconds. Therefore, the particles show excellent properties. Incidentally, in this example, the amount of sodium carbonate is 7.0 times the amount required for LAS neutralization. Example 6 -24- * ---- — C'-T Pack-(Please also read the notes on the back f and then fill out this page) Order I4 6298 7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. DESCRIPTION OF THE INVENTION (22 Using a high-speed mixer " Liidige mixer FKM-130D "(manufactured by Matsubo Co., Ltd.), a detergent composition having the composition shown in Table 1 in an amount of 35 kg was prepared for each unit. This mixer is equipped with There are agitator blades and a cutting force device, and this cutting force device corresponds to a tool for separating or dispersing. Here, the detergent composition is prepared by the following steps detailed below. The powder blend includes 7.7 parts by weight of trimer Sodium Phosphate (8-but ???; average particle size: 11.2 microns), 13.74 parts by weight of sodium carbonate (" LIGHT ASH1, manufactured by Central Glass Co., Ltd .; average particle size: 56.1 microns), and 0.11 parts by weight of fluorescent agent The solid content is blended for one minute under the conditions of agitator blade rotation speed of 130 rpm and rotation speed of shear force device of 285 0 rpm. Addition water of reaction initiator is added to the mixer in an amount of 0.25 parts by weight. Content as a reaction initiator ' Blending was performed for one minute and thirty seconds under the same blending conditions as above. When the neutralization mixer was operated under the same conditions as above, 7 · 5 1 parts by weight of linear pyrophenylbenzene acid (LAS) and 0.48 parts by weight Fatty acid, 1.4 parts by weight of non-ionic surfactant is added to the contents of the mixer in four minutes. At the time of addition, the ingredients are cooled by passing 25 eC of water through the jacket of the mixer. At this stage, the temperature rises to 5 9, 5 C. Incidentally, at this stage, the reaction mixture remains in a granular form. Incidentally, the above-mentioned [six to eight containing 011 parts by weight of sulfuric acid. Air was also blown in under the same conditions as in Example 4. In the mixer. After the addition of LAS, the mixer will continue to operate for one minute under the same conditions. -25- This paper applies the Chinese National Standard (CNS) A4 · (-~-(Please read the precautions behind it before filling in (This page)

46298 7 A7 -------- B7 V. Description of the invention (23) _ Surface modification At the completion of the neutralization reaction, the resulting mixture is mixed by adding 4 2 parts by weight of zeolite with an average particle size of 4 microns The device acts as a surface modifier and operates the mixture for another two minutes to undergo surface modification. Incidentally, the stagnant stone contains 0.8 4 parts by weight of crystal water. The resulting cleanser composition particles have the following properties: Percentage of particles passing through I 400 micrometers: 7500/0; average particle size: 6 1 3 micrometers; bulk density: 871 g / liter; and free flowing force: 5.4 seconds. Therefore, the particles show excellent properties. After blending, a rotating mixer was used to blend 0.18 parts by weight of the enzyme granules with the detergent composition prepared above, and then spray-filled 0.07 parts by weight of perfume to give the final powder of the high bulk density detergent composition. Incidentally, In this example, the amount of 'sodium carbonate' is 10.7 times the amount required for neutralization of fatty acids with fatty acids. Comparative Example 1 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Similar steps, except that the detergent composition is administered with an average particle size of 58.4 microns. The detergent composition after the post-blending step has the following properties: Percentage of particles passing 1400 microns: 34 2 < ^ Average particle size: 1213 microns; -26- This paper size applies to Chinese National Standard (CNS) A4 specifications (462987 A7 B7 except five. Description of the invention (24) Bulk density: 712 g / liter; and free flow force: 7.8 seconds. Therefore, the granules have a low bulk density and a poor yield of most of the coarse granules. Comparative Example 2 'A similar composition as in Example 1 was used to perform similar steps as in Example 丨 using 36. The average particle size of 5 micrometers is sodium tripolyphosphate, and =; detergent composition. ° 卞 > The granules of the detergent composition after the green post-blending step have the following properties. Percentage of particles passing 1 400 microns: 5 〇5%; · average particle size: 1087 microns; bulk density: 719 g / liter; and free-flow force: 6.7 seconds. Therefore, the particles have a low bulk density and poor yield of most coarse particles. Comparative Example 3 The similar composition of Example 1 was performed similarly as in Example 1 using sodium tripolyphosphate having an average particle size of 58.4 microns and using a hammer mill to pulverize the LIGHT ASH used in Example 1 to an average of 6.9 microns. LIGHT ASH, and the detergent composition is given. The particles of the detergent composition before the post-clamping step have the following properties. Percentage through 1 400 micron particles ^ 27,6%; average particle size: 1 670 micron; bulk density: 769g / litre; and free-flowing force: 7.0 seconds "Therefore, the granules have a low bulk density and a poor yield of most of the pulling granules. • 27. This paper size is applicable to the Chinese national standard (〇 叫 八 4 秘 (2 敝) 297 males) "" Installation-, F fIs-it read and read notes before filling out this page Incidentally, Table 1 shows the composition of the final powdery product of each of the detergent compositions in the above examples and comparative examples. Tables 2 and 3 also show the properties of the granulated detergent composition. Table 1 Detergent Composition The final powdery product of the product 々_ Composition (% by weight) '' Example i-3 Comparative Example 1-3 Example M Example 5 Example 6 LAS-Na 32,00 32,00 32,00 22,00 皀 0.00 0.00. 〇〇1.50 STPP 22.00 22.00 22.00 22 * 00 zeolite. 12.00 12.00 12-00 12.00 sodium carbonate 28.67 29.32 30.62 35.23, terminal acid oblique 0.68 0.68 0.68 0.tf7 acrylic butadiene acid copolymer 6.0.50 0, 50 0,00 0-00 Non-ionic surfactant. 0-00 0.00 0 * 00 if.oo Fluorescent 0.30 0,30 0.30 0.30 S per 0.5〇0.50 0.00 0.50 Spice '0.20 0.20 0.00 0.20 Water 3.15 2.50 2.40 1.80 -28- This paper size applies to China National Standard (CNS) A4 (210X297) %)

4 62 98 T Α7 Β7 V. Description of the invention (26) Table 2 1 2 3 Example η 5 6 Average particle size of STTP (A m) 11.2 8.3 11.2 11 · 2 11.2 11.2 Average particle size of light ash. * • 1-· * 56,1 56.1 6.9 56.1 56.1 56.1 The amount of air passing through; (L / min,) 0 0 0 500 500 500 Maximum powder yield *; CC) 68.8 69.0 711.7 61.0 61.8 59.5 Final powdery product Average particle size (am) 577 530 830 5U2 578 (ij62) * 613 Percentage (%) through 1400 # m (yield) 73.9 77.0 60.5 76.2 刖 .7 (90.1) * 75.0 丨 Bulk density (g / L ), (g / L) 810 820 83! 835 680 (688) * 871 Free flow force (sec) 6,2 6.0 7.H 5.8 8.3 (6.3) * 5.H After getting sex. (Please also read the precautions before filling out this page) • Packing-'al > Printed by Shelley Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs -29 · This paper size applies to China National Standard (CNS) Μ specifications (210X29? Mm) 4 G 2 98 7 A7 B7 V. Description of the invention (27) Table 3 1 Comparative example 2 3_ STTP average particle size (P Π1) 58.U 36.5 58.U LIGHT ASH average particle size (μm) 56.1 56.1 6.9 Maximum powder temperature 70.7 71.8 75.2 (° C) Average particle size of final powdery product 1213 1087 1670 Percentage of particles passing through 1400〆m (%) (yield) 3M.2 50.5 27.6 Bulk density (g / L) '712 719 769 Free-flowing force (sec) 7.8 6.7 7.0 I; ------- Outfit-(Please read the precautions before filling in this page before filling in this page) s' ding f-? Employees of Central Bureau of Standards, Ministry of Economic Affairs Printed by Consumer Cooperatives -30- This paper size is applicable to China National Building Standard (CNS) A4 (210 X 2.97 mm) Printed by Shellfish Consumer Cooperatives, Central Standards Bureau of the Ministry of Economic Affairs 4 62 98 7 A7 ____B7 V. Description of the invention ( 28) As is apparent from the above results, it was confirmed that the cohesiveness or shape of coarse particles of the detergent composition can be significantly suppressed , Since not directly related to the reaction and tripolyphosphate having an average particle size of 1 to 30 microns. Example 7 A detergent composition having the composition shown in the table! Was prepared in an amount of 35 kg for each unit using a “South Speed Is” Lfidige Mixer FKM-130D ”(Matsubp Co., Ltd.). There are agitator blades and a shearing device, and this shearing device corresponds to a tool for disintegration or dispersion. Here, the 'detergent composition is prepared by the following steps detailed below. The powder bonding includes 5.25 parts by weight of sodium tripolyphosphate (STPP; average particle size: 11.2 microns), 13.82 parts by weight of sodium carbonate (" LIGHT ASH ", manufactured by Central Glass Co., Ltd .; average particle size: 56.1 microns), and 0.088 parts by weight of the solid content of the fluorescer, Blend for one minute under the conditions of 130 rpm (surround speed: 3.4 m / s) agitator blade rotation speed and 2850 rpm (surround speed · 27 m / s) shear device rotation speed. Incidentally, The amount of sodium carbonate is 7.8 times the amount of linear alkylsulfonic acid (LAS) used for neutralization. The addition of aqueous alkali solution is 0.56 parts by weight and 48% by weight of aqueous sodium hydroxide is added to the mixer. Content, and raw The mixture was blended for one minute and thirty seconds under the same blending conditions as above. The dung of aqueous sodium hydroxide was 0.2 times that required for LAS neutralization. When the neutralization mixer was operated under the same conditions as above, 1 1.2 6 parts by weight of linear alkane-31- This paper size applies Chinese National Standard (CNS) A4 specification (2I0X297 mm) (Please read the cautionary notes before completing this page)

46298 7 A7 B7 V. Description of the invention (29 printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, two molecular weights' · 322) were added to the mixer within four minutes: ：： 成 时 'The composition is caused by the water flowing through 2rc through the jacket of the mixer: 2: 二 :: The temperature rises to 72W. At this stage, the reaction mixture maintains a granular form of β. LAS after the addition The mixer is continuously operated for one minute under the same conditions to complete the neutralization reaction and the granulation process. Incidentally, during the treatment of neutralization reaction and granulation, air is blown into the mixer at a rate of 5 cubic meters per minute. The addition of the liquid component is replaced by γ. When the neutralization reaction and the granulation process are completed, and the mixer is operated under the same conditions as above, the effective amount of the copolymer is Gm, and the weight is 40% by weight. The aqueous solution of the acid · maleic acid copolymer was added to the mixture, and mixed for one minute and thirty seconds. Then, the resulting mixture was subjected to surface modification by adding 42 parts by weight of zeolite having an average particle size of 4 m to the mixer as a surface modifier, and operating the mixture for another two minutes to undergo surface modification. Incidentally, the zeolite contains 0.84 parts by weight of crystal water. The resulting detergent composition particles have the following properties: Percentage of particles passing 1440 microns · 76.5%; Average particle size: 578 microns; Bulk density: 772 g / litre; and Free flowing force: 6.4 seconds. Therefore, the particles show excellent properties. After changing. Use a rotating mixer to mix 0'105 parts by weight of enzyme granules with the above preparation. Please read the notes on the back again. 4 pages m binding -32- This paper size applies to China National Standard (CNS) A4 specifications. (2IOX297 male thin 4 6298 7 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (30 cleanser composition 'then spray 0.07 parts by weight of perfume and give a high bulk density cleaner combination The final powder of the material "Example 8 A similar composition as in Example 7 was used to perform similar steps as in Example 7, except that the weight of 48" was changed. The amount of aqueous sodium hydroxide was changed to 0.4 times the amount needed to neutralize LAS. ) And give the detergent composition. The particles of the detergent composition after the wishing-up step have the following properties: Percentage of particles passing 1400 microns: 79.0%. Average particle size: 550 microns; Bulk density: 809 g / Liter and free-flowing force: 6.2 seconds. Therefore, the granules showed excellent properties. Example 9 A similar composition as in Example 7 was used to perform similar steps as in Example 7 except that the reaction was neutralized and granulated. It is omitted to blow air into the mixer during the partial treatment, and the detergent composition is given. The particles of the detergent composition after the post-combination step have the following properties: Percentage of particles passing through 1400 microns: 70, Q%: average particle size : 6 30 micrometers; Bulk density: 761 g / L; and free-flow force: 6.7 seconds. Example 10 A similar composition as in Example 7 was used to perform similar steps as in Example 7 except that 48 «% water reduction was not added. Oxygen material, ㈣yoqing · detergent composition /, .33- This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 0X297 mm)

46298 7 A7 ---- B? V. Description of the invention (31) The particles of the detergent composition after the post-blending step have the following properties: Percentage of particles passing 1400 microns: 59 3%; Average particle size: 790 microns; Volume Density: 678 grams / liter; and free-flowing force: 7.2 seconds. Example 1 1 A similar composition as in Example 7 was used to perform similar steps as in Example 7, except that 0.2 5 parts by weight of water was used instead of 48% by weight. Aqueous sodium hydroxide while administering a detergent composition. The particles of the detergent composition after the post-blending step have the following properties: Percentage of particles passing 1400 microns: 67 5%; Average particle size: 660 microns; Bulk density: 711 g / liter; and Free-flow force: 6.8 seconds. Example 1 2 Similar steps as in Example 7 were performed using a similar composition as in Example 7, except that 48% by weight of aqueous sodium hydroxide was not added and that air was blown into the mixer during the entire treatment of neutralization and granulation After the detergent composition is administered, the particles of the detergent composition after the blending step have the following properties: Percentage of particles suitable for 1400 microns: 5 8 6%; Average particle size: 813 microns; Bulk density: 682 g / Liters; and free-flowing force: 7.9 seconds. -34- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm): '? Race-(Please read the $ item of the back cylinder and fill in this tile) Order the shellfish consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative ^ 6298 7 A7 B7 Five invention instructions (32 Example 1 3 Using a similar composition as in Example 7 and performing similar steps as in Example 7 changed the amount of 48% by weight of aqueous sodium hydroxide to 〖· 96 weight Part (amount 0.7 times the amount required to neutralize the LAS) to give the detergent composition. The particles of the detergent composition after the blending step have the following properties: Percentage of particles passing through 1400 microns: 5,7.0% Average particle size: 950 microns; Bulk density: 721 grams / liter; and Free-flow force: 8.0 seconds. Incidentally, Table 4 shows the final powdery product composition of each detergent composition in the examples. Table 5 also shows the granules The properties of the resulting cleaner composition after the conversion. —————- f Jing Mao read the notes on the back and fill out this page) · 〇 Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs -35. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) Λ 6298 Α7 Β7 V. Description of the invention (33 LASia STPP S abandoned review and release-®τ 蕻 h braid plus turning through 蟠 33 15 3 production 0.7. 0.25 0.3 0.2 2.95 33 15 12 3f 18 0.7 0.70.2U1 0,30.2 3.67 33 1U1 12 35 · 1 0.7 0.7 0.25? 3 0-2 2.75 33 15 12 35 .'55 0.7 S 0.25 0.30,2 2'3 33 15 12 3 卬 Ρ7 0.7 0.25 0.3? 2 2.COU1 Poria rate axe ^ '>-^ 隹 命 # (14: 1: ./ 0 > 10 η (please read the precautions before filling in this page) Printed by Consumer Cooperatives

33 15 12 3505 0-7 0,7 0,25 0.3 0.2 2.CD 33 G; 12 33.25 0.7 P7 0.25 0.3? 2 4.6 This paper size is applicable to China National Standard (CNS) A4 (210X297). 13 13 d 62 98 7 A7 B7 V. Description of the invention (34) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ " 1400 μπ J ^^ " '' ^^ (sec) (L / Ein.) ^^ '^ ^ " ^ *, CC), υ100 578 Ίφ5 772 ϊ 8096.2 7 " 6 · 7 6S 7.2 7116,8 682 7.9 7218.0 79.0 70.0 59'3 67.5 58.6 $ .0 550 63 ° 79〇660

S 950 --------- ry Pack — (Please read the back (Notes of ¾ before filling out this page) 75 500 、 7 79 69 500 9】 0 69 71 82 This paper size applies Chinese national standards ( CNS) A4 specification (2 丨 0 × 297), 5D0 0 500 2 12 13 4 6298 7 A7 ~~ ---- B7 V. Description of the invention (35) ~, cleaning agents prepared in Examples 10 to 13 When the composition was compared to those prepared in Examples i to y, due to the fact that it contained a larger amount of surfactant and a smaller amount of tripolyphosphate with an average particle size of 1 to 30 microns, it showed slightly no! Properties. Examples Each of the detergent compositions prepared in 7 to 9 contains a specific! (Permanent alkali solution, the discovery of the properties of the resulting detergent composition, including the percentage of particles passing through 1400 microns, average particle size, bulk density, and The free-flowing force is remarkably improved. It is also obvious from Examples 7 and 9. Since the air is blown into the mixer during the treatment of neutralization and granulation, the discovery that a detergent composition is formed can be further improved. From the examples 9, Example ι〇, and Example 12 are also obvious, the addition of a specific amount of aqueous alkali solution It further contributes to the improvement of the discovery of the properties of the detergent composition in which air is blown into the mixer. The invention is described in this way, and it can be obviously changed in many ways. This change is not to be regarded as a departure from the spirit and scope of the invention, and All such modifications apparent to those skilled in the art are included in the scope of the patent application below. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1 ^^^ 5 ^ China National Standards (Oyang > 8-4 Specifications) (210 > < 297mm) --------: l7T --------------- ... Jiu / IN (Fill in this page again) 4 I. I ·

Claims (1)

Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 4 6298 7 Patent Application No. 8611U34 Amendment to Chinese Patent Application Park (May 90) VI. Application for Patent Park, Seed K Valley Accumulation Fund Level is 650 g / liter or higher. Method of density cleaner composition 'which includes the steps of: (a) joining the following ingredients in a mixing granulator: (1) granular, solid, water-soluble alkaline inorganic substance, (ii) average particle size of 1 to 30 microns Tripolyphosphate, and (in) one or more granular solids other than ingredients (1) and (ii), wherein the amount of the granular, solid, water-soluble alkaline inorganic substance is equal to or greater than step (b) Neutralize the amount of liquid acid precursor used to neutralize the anionic surfactant; and (b) add the liquid acid precursor of the anionic surfactant to the mixture obtained in step (a) to make the alkaline inorganic The material neutralizes the liquid acid precursor of the anionic surfactant while the mixture still maintains a granular form 'and granulates the neutralized mixture to produce a granular mixture' wherein the content of dipolyphosphate is the final detergent composition 2 to 50% by weight of the product, The amount of liquid acid precursor of an anionic surfactant, the composition of the product to the final detergent and by the reaction of an anionic surfactant in the form of meter is 5 to 45 wt. ° / square. 2. The method according to item 1 of the patent application range, wherein the average bulk size of the obtained high bulk density detergent composition is 1,000 microns or less, and the weight percentage of the particles of 1400 microns or less is 55% or less Higher, in which the average particle size is calculated in accordance with jIS K 8801 standard sieve after five minutes of vibration, based on the weight percentage of the sieved particle size. 3. The method according to item 1 or 2 of the scope of patent application, in which the granular, solid paper size is applicable to Chinese standard (CNS > A4 size (210X297 mm)) (Please read the note on the back before reading) Fill in this page) Order I ** · 462987 A8 B8 C8 D8 π, patent application scope, average particle size of water-soluble alkaline inorganic substance is 30 microns or larger. 4. According to the patent application park No. 丨 or 2 Method, in which the gas is blown into the granulator of step (b) during the neutralization process. 5. The method according to item 1 or 2 of the patent application park, wherein an anion is added in step (b) Before the liquid acid precursor of the anionic surfactant, add an aqueous alkali solution to the mixture obtained in step ⑷ and mix it in an amount of 0.05 to 0.5 required to neutralize the liquid acid precursor of the anionic surfactant. 6. The method according to item 5 of the scope of patent application, wherein the aqueous alkali solution is an aqueous sodium hydroxide solution. 7 'The method according to item 1 or 2 of the scope of patent application, further comprising steps: (c) making step ( b) The obtained granular mixture The surface of the object is modified. 8. The method according to item 1 or 2 of the scope of the patent application, wherein the stirrer granulator is equipped with agitator blades and a tool for decomposition and dispersion. 9. According to the scope of the patent application The method according to item 7, wherein the surface modifier suitable for the surface modification step is a crystalline or amorphous alkali metal aluminosilicate having an average particle size of 1 to 30 microns. 10. The method according to item 1 or 2 of the scope of patent application In which, crystalline or amorphous alkali metal aluminosilicates with an average particle size of 1 to 30 microns are further added and blended in the step. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --------__ '.ί (Please read the notes on the back before filling out this page) Order printed by the Ministry of Economic Affairs Central Consumer Bureau's Consumer Cooperatives Printed by the Central Standards Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 4 6298 7 Patent Application No. 8611U34 Amendment to Chinese Patent Application Park (May 90) VI. Application for Patent Park, Seed K Valley Accumulation Fund Level is 650 g / liter or higher. Method of density cleaner composition 'which includes the steps of: (a) joining the following ingredients in a mixing granulator: (1) granular, solid, water-soluble alkaline inorganic substance, (ii) average particle size of 1 to 30 microns Tripolyphosphate, and (in) one or more granular solids other than ingredients (1) and (ii), wherein the amount of the granular, solid, water-soluble alkaline inorganic substance is equal to or greater than step (b) Neutralize the amount of liquid acid precursor used to neutralize the anionic surfactant; and (b) add the liquid acid precursor of the anionic surfactant to the mixture obtained in step (a) to make the alkaline inorganic The material neutralizes the liquid acid precursor of the anionic surfactant while the mixture still maintains a granular form 'and granulates the neutralized mixture to produce a granular mixture' wherein the content of dipolyphosphate is the final detergent composition 2 to 50% by weight of the product, The amount of liquid acid precursor of an anionic surfactant, the composition of the product to the final detergent and by the reaction of an anionic surfactant in the form of meter is 5 to 45 wt. ° / square. 2. The method according to item 1 of the patent application range, wherein the average bulk size of the obtained high bulk density detergent composition is 1,000 microns or less, and the weight percentage of the particles of 1400 microns or less is 55% or less Higher, in which the average particle size is calculated in accordance with jIS K 8801 standard sieve after five minutes of vibration, based on the weight percentage of the sieved particle size. 3. The method according to item 1 or 2 of the scope of patent application, in which the granular, solid paper size is applicable to Chinese standard (CNS > A4 size (210X297 mm)) (Please read the note on the back before reading) Fill in this page) Order I ** ·