TW401457B - Granulated bleaching activator composition and bleaching detergent composition containing the same - Google Patents

Abstract

A colored granulated bleaching activator is provided which, even when added to a bleaching detergent composition, especially one containing zeolite, does not suffer decomposition of the bleaching activator. A pigment selected between ultramarine blue and cyanine green is used as a colorant for a granulated bleaching activator comprising at least one bleaching activator.

Description

II Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 401457 A7 ^ __ B7 V. Description of the invention (1) [Technical scope of the invention] The present invention relates to a granular bleaching accelerator and the granular bleaching agent Promoter's life white detergent, composition. In more detail, the present invention relates to pigmented granular b white accelerators 'even when added to bleaching detergent compositions containing zeolites' and it does not suffer from decomposition of the granular bleach accelerator, and A granular bleaching detergent composition. [Previous skill] In order to impart a bleaching effect, it is customary to incorporate a bleach into a laundry detergent. From the standpoint of bleaching performance, stability, etc., oxygen-based bleaching is widely used. It releases hydrogen peroxide when it decomposes in water, such as sodium percarbonate and high rot acid sword. Since these oxygen-containing bleaches are inferior to gasified bleaches in bleaching efficacy, they are used in combination with one or more bleaching accelerators to enhance the ΔK white effect. Examples of bleaching accelerators include those produced in washing baths, such as tetraethyl brewed ethylene diamine, tetraethyl brewed sweet moon urine, and glucose pentaacetate, and those produced in the washing bath. , Which are disclosed in Japanese Patent Applications A-59-22999, 8-218096, 6-31 6700, and the like. To improve storage stability, these bleach accelerators are often incorporated in the form of granules from the public's hobby, trying to use pigments or dyes to color these granules. It is disclosed in Japanese Patent A2_258872. A coloring method in which a granular bleaching accelerator is sprayed to stabilize an aqueous solution of a water-soluble dye or an aqueous dispersion of a water-dispersible pigment. However, these bleaching accelerators are blended with 夂 bleaching detergents, especially this ... The Zhang scale is applicable to g) national standard () M specifications (plus public) (Please read the precautions on the back first. /:; ^ " this page) • Install · 401457 A7

This constitutes a problem that is: [the content of the present invention] by which the bleach accelerator is greatly reduced [the content of the present invention] sets a goal to improve the stability of the coloring bleach accelerator. Technology, even in the incorporation of accelerators into bleaching detergent compositions. As a result of extensive research done by the inventors of the present invention, JB. L'-L 'CT is Ci-like. Granulation of the mixture of the agent and specific pigment is achieved. Kind of Kun. And the present invention provides particles of a bleach promoter comprising a pigment selected from ultramarine blue and cyan green and at least one bleach promoter. The present invention further provides a bleach accelerator mixture in the form of granules' comprising a pigment selected from ultramarine blue and cyanine green and at least one bleach accelerator. The composition preferably contains 0.01 to L0% by weight of a pigment and 1.0 to 90% by weight of a bleach accelerator. A preferred embodiment of the composition comprises (d) 0.01 to 1.0 wt% pigment and (c) 10 to 90 wt%, more preferably 0 to 70 wt% bleach accelerator (which It has the formula (j) or (π) as defined below, and additionally contains (a) 0-50% by weight of a thioalkyl sulfate, thioether sulfate or a mixture thereof and (b) 0.5-30% by weight It is selected from a fatty acid, polyethylene oxide, and a mixture thereof. The present invention further provides a method for manufacturing a granular bleaching accelerator, which method comprises combining the component (a) with the component (d) and the wound or all the components (a ) Premixing .. Mix the premix with the rest of the ingredients (a) and (b) to prepare a homogeneous mixture. The degree is based on the CNS standard. 8) Secret (21GX 297 mm) (Please read the note on the back first) (In this page) • Packing, 1T Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives ⑽ 1457 a7 _ _ B7 V. Description of the invention (3) • * and extruding and granulating the mixture to produce 0.5 to 2 The average particle diameter of 5 legs. In a preferred embodiment of the method, the binder of component (b) has a winter melting point of 40 ° C or higher and is added after melting. Furthermore, the present invention provides a bleaching detergent composition, which comprises 0.5 to 10% by weight of the bleach accelerator composition shown above in the form of particles and 0.1 to 20% by weight of sodium perdicarbonate and / or sodium perborate. Furthermore, the present invention provides a bleaching detergent composition comprising (1) 011 to 20% by weight of sodium perdicarbonate and / or sodium perborate, and (2) 15 to 40% by weight of a group selected from the group consisting of benzene and benzene. At least one anionic surfactant of sulfonate 'alkyl sulfate and alkyl ether sulfate, (3) 0.5 to 10% by weight as shown above, comprising (a), (b)' ( c) Bleaching accelerator composition with rhenium and (4) 5 to 40% by weight of stagnation. In addition, the present invention provides a granular bleaching accelerator containing the following ingredients to ((1): printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (a) 0 to 50% by weight selected from alkyl sulfate salts and alkanes At least one kind of sulfate of the salts of the ether ether sulfates, (b) 0.5 to 30% by weight of a binder selected from fatty acids, polyethylene oxide and mixtures thereof, (c) 1.0 to 70% by weight Via a bleach accelerator represented by the following general formula (I) or (II) and (d) 0.001 to 0.1% by weight of a pigment selected between ultramarine blue and cyanine green.

COO

S03Na (l) C—ni ^ n + i.

CmH2m + l— COO

COOH (Π) -6 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (0X 4 7 mm) 4Q " i5f A7 B7 Printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation 5. Printing of the invention (4) [of which n and m each represent a number from 5 to 17]. Furthermore, the present invention provides a bleaching detergent composition, which composition contains 0.5 to 10% by weight of the granular bleaching accelerator of the present invention and 0.1 to 20% by weight of "S". Acid steel and / or high shed acid steel. Moreover, the present invention provides a bleaching detergent admixture, the composition comprising the following components (1) to (4): (1) 0.1 to 20% by weight of (ii) sodium carbonate and / or sodium perborate (2) 15 to 40% by weight of at least one anionic surfactant selected from the group consisting of alkylbenzenesulfonates, alkyl sulfates and fluorenyl ether sulfates; (3) 0.5 to 10% by weight Granular bleach accelerators of the following ingredients (&) to ({1): (a) 0 to 50% by weight of at least one sulfate selected from the group consisting of alkyl sulfate salts and alkyl ether sulfate salts (B) 05 to 30% by weight of a binder selected from fatty acids, polyethylene oxide and mixtures thereof, (c) 丨 · 〇 to 70% by weight via the following general formula (I) or (Π) Representative bleach accelerators and (d) 0.001 to 1% by weight of pigments selected between ultramarine blue and cyan blue. CnH2n + 1 _

COO

S03Na (I)

CmH2m + l— ~ — c〇〇 -o

COOH, (II) [where n and m each represent one of 5 to 17 number]; and (4) 5 to 40 sheets of paper 210X297 mm) 5. Description of the invention (A7 B7 zeolite weight. [ Mode for Carrying Out the Invention] First, the granular bleaching accelerator of the present invention / :: Ming is related to the granular bleaching accelerator, which contains colored particles. The pigment between the ultramarine and the cyan is used as the particle Colorants: Colorants can be used together with other dyes or pigments, but this way: reduce the effect of the present invention. Therefore, the preferred is: actually, no. Among the granular accelerators, selected from The amount of pigment between Qunyin Blue and Cyan Green is 0.0H 0% by weight, and G 0.05 to 7% by weight is required, and 0.05 to 5% by weight: the amount% is preferred.% The granular bleaching promotion of the present invention The agent contains at least one bleaching accelerator. The bleaching accelerator preferably includes at least one member selected from the group consisting of tetraethylammonium ethylenediamine, alkanehydrobenzene sulfonate, and alkoxyoxybenzenecarboxylic acid and salts thereof. The preferred is a bleach accelerator which is promoted to be replaced by the general formula (I) or (II). It is 1 to 90% by weight, 10 to 90% by weight is required, and 30.70% by weight is preferred. The Central Standards Bureau of the Ministry of Economic Affairs *: printed by industrial and consumer cooperatives will preferably be selected from alkyl sulfates Salts and alkyl ether sulfates are incorporated into a granular bleaching accelerator of the present invention. These sulfates are used to improve the solubility of the bleaching accelerator in the washing bath. These sulfates can be incorporated in an amount in the range of 0 to 50% by weight, which is 1 to 45% by weight, preferably .5 to 40% by weight. Particularly preferred including sodium sulfate having 10 to 18 carbon atoms are sodium lauryl sulfate and sodium tetradecyl sulfate. Preferred examples of the alkyl ether sulfide salts include polyoxyethylene methyl ether sulfate Salts 8 This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) 4〇t457 A7 _____________ B7 V. Description of the invention (6) ~ ~ 'Especially sodium salts with 10 to 18 carbon atoms The degree of polymerization of the polyoxyethylene group is 1 to 10, preferably i. Particularly preferred is polyoxyethylene lauryl ether Sodium sulfate (with an average number of ethylene oxide molecules added from 2 to 5) and sodium polyoxyethylene tetradecyl ether sulfate (with an average number of ethylene oxide courtyard molecules added from 2 to 5) When manufacturing the granular bleaching accelerator of the present invention, it is preferred to use a binder selected from polyethylene oxide (also known as polyethylene glycol) and fatty acid. The ethylene oxide has a desired 2,000 to 20,000. An average molecular weight of 〇, preferably from 4,000 / to 10,000, more preferably from 4,000 to 8,000. Fatty acids are intended to have 8 to 20 carbon atoms, preferably 10 to 8 carbon atoms, more preferably丨 2 to 丨 8 carbon atoms and may be in the form of a main sodium or potassium soap. The adhesive is used based on a granular accelerator, and the amount is 0 to 5 to 30% by weight, and is preferably 1 to 20% by weight, and more preferably 5 to 20% by weight. The colored granular bleaching accelerator of the present invention produces the best results when prepared by mixing the above-mentioned ingredients in the proportions described above. This granular accelerator has excellent stability of bleach accelerator, satisfactory solubility of bleach accelerator and sufficient bleaching effect. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Any desired method can be used in the present invention to mix the ingredients together and granulate the mixture. A particularly preferred method involves pre-mixing the bleach accelerator with the colorant and some or all of the anionic surfactant and then adding a binder. Adding a pre-cured binder produces satisfactory results. Bring the adhesive to 40 before adding. It is melted at 100 ° C, and is intended to be 50 ° to 100 ° C ', preferably 50 ° to 90 ° C. These ingredients are mixed under stirring until the mixture becomes homogeneous. Produce the raw mixture with ordinary granulation. The paper size is applicable to China. National Standard (CNS) A4 specification (21 χ 297 mm) 401457 A7 B7 5. Description of the invention (7) --- Granulation mechanism. A preferred method of granulation includes extruding into granules, through which the power compound is intended to be formed into an average granule having a diameter of 500 to 5,000 μm (microns) = diameter, (preferably 500 to 3,000 / im) Of the particles. Another preferred method of granulation includes forming the mixture into tablets using a block machine. Ί For the purpose of improving the stability of the bleach accelerator of the present invention, it is preferable to incorporate an acid agent into the granular accelerator. The acid agent is intended to be composed of at least one organic carboxylic acid selected from the group consisting of succinic acid, fumaric acid, citric acid, glycolic acid, and p-hydroxybenzoic acid. The acid agent is based on the granular accelerator composition and is included in a desired amount of 0 to 20% by weight, preferably from i to 15% by weight, and more preferably from 1 to 10% by weight. The bleaching detergent composition of the present invention is explained as follows. The coloring agent-containing granular bleach accelerator is included in the bleaching detergent composition in an amount of 0.5 to 10% by weight based on the composition. The bleaching detergent composition additionally contains sodium per (di) carbonate and / or sodium perborate, and the amount thereof is preferably 0a to 20% by weight / ° so as to produce a bleached species. Particularly preferred examples of the composition of the bleaching detergent composition include the following: (1) 0.1 to 20% by weight of sodium percarbonate and / or sodium perborate, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (2) 15 to 40% by weight of at least one anionic surfactant selected from the group consisting of alkylbenzenesulfonates, alkyl sulfates and salts of alkyl ether sulfates; (3) 0.5 to 10% by weight. / 〇 The bleaching accelerator of the present invention, and (4) 5 to 40% by weight of zeolite. In the above composition, the inorganic peroxide of the component (1) is preferably high-sodium acid. The content of ingredient (1) is 0.1 to 20% by weight, the meaning is 0.5 to 10% by weight, which is more than -10- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 01457 V. Invention Explanation (8 Α7 Β7 ^ 0.5 to 8 weight!%. When the content of the component ⑴ is within this range, the wide bleaching effect and the satisfactory stability of the bleach accelerator can be satisfied. The component =) can be the main particle In another form, and preferably with a granular detergent base and granular bleaching promotion. The bleaching detergent composition of the present invention is used as a surfactant by using at least one anionic surfactant (ingredient XI) selected from the group consisting of ammonium sulphate, sulphuryl sulfate and sulphuryl sulfates < anionic surfactants (ingredient ⑺). The content of the component (2) is from 5 to = 0 wt./%, preferably from 20 to 40 wt.%. These alkylbenzenesulfonates are intended to have 10 to 20 carbon atoms and are preferably sodium or potassium salts. Alkyl sulfate salts have 8 to 18 carbon atoms, are intended to be 10 to 14 carbon atoms, and are preferably sodium or potassium salts. The salts of sodium alkyl ether sulfate are preferably salts of polyethylene oxide alkyl ether sulfate, and are intended to have 8 to 18 carbon atoms, more preferably 10 to 14 carbon atoms. The average number of ethylene oxide molecules added ranges from 1 to 20, and is intended to be from 0 to 5, preferably from 5 to 5. These salts are preferably sodium or potassium salts. The surfactant (2) is preferably incorporated into the detergent base. Ingredient (3) is the colored granular bleach accelerator of the present invention described above. It is included in an amount of 0.5 to 0% by weight based on the bleaching detergent composition, and is intended to be 0.5 to 8% by weight, preferably 0.5 to 5% by weight. If the content of the component (3) is less than 0.5% by weight, a sufficient bleaching effect cannot be obtained. If it exceeds 10% by weight, it causes trouble, such as agglomeration of the bleaching detergent composition. (The granular bleaching accelerator of ingredient (3) preferably contains the following ingredients 丨 &) to ⑷: ί -11 This paper size applies to Chinese national standards (CNS > Α4 specifications (21〇 > < 297 mm) Please A read it-note _ item

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 ^ 1457 Μ: I. _________B7 V. Description of the Invention (9) " ^ ~ —— ~ (a) 0 to 50% by weight sulfuric acid-based fermented salt and calcined base At least one kind of chain sulfate salt, (b) 0.5 to 30% by weight of an adhesive selected from fatty acids, polyethylene oxide, and mixtures thereof, and 10 to 70% by weight via the general formula ⑴ or (II) Represented by a bleaching accelerator, and (d) 0.01 to 1.0% by weight of a pigment selected from ultramarine blue and cyanine green:

CnH2n + 1——COO ~ ow η—S03Na U)

CmH2m + 1-COO-Q COOH (Liao) [where n and m each represent a number from 5 to 17] The zeolite (ingredient (4)) is included in the above composition. Representative examples of zeolites include zeolites A, Z and P, with zeolite A being particularly preferred. The zeolite has a desired average elementary particle diameter of 0.1 to 10 < m, preferably 0.01 to 5 ". Such zeolite is included in the bleaching detergent composition in an amount of 5 to 40% by weight, preferably 10 to 40% by weight. The zeolite is preferably blended into the detergent base. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In addition to the basic ingredients mentioned above, the ingredients usually added to washing can be blended into the bleaching detergent combination of the present invention In. If necessary, in addition to the anionic surfactant as the main component of the component (2), the surfactant that can be added is a nonionic surfactant, except for the anionic surfactant, the cationic surfactant and the amphoteric other than the component (2). Surfactant. Examples include anionic surfactants, such as olefin sulfonates, and chain acid-12- This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) ^ 1457 V. Description of the invention (10A7 B7 a * & Saturated and unsaturated fatty acid salts, alkyl and alkenyl ether carboxylic acid salts, "contanoic acid fatty acid salts and α-sulfonic acid fatty acid esters; non-ionic interface activities such as' poly Acetyl oxide, polyoxypropylene, copolymers thereof, polyoxyalkylene and alkyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamines and their alkyl oxide adducts, sucrose / fat Acid esters and alkanes, (sugars; amphoteric surfactants such as amine oxides, sulfobetaines and carbonyl betaines; and cationic surfactants such as fourth ammonium salts. Particularly preferred, incorporated herein Among other surfactants, at least one of a non-ionic surfactant and a fatty acid package. More desirable non-ionic surfactants are each having an alkyl or alkenyl group (which contains from 0 to 20 carbon atoms) , Preferably 10 to 18) and in the molecule, There is a polyoxyethylene chain, which has an average degree of condensation of 4 to 20, preferably 4 to 5. A suitable fatty acid soap is sodium or 4A, a saturated or unsaturated fatty acid derived from coconut oil or tallow. Salts and each having 8 to 8 carbon atoms, preferably 10 to 18 carbon atoms. § Except for the main ingredients, 'this surfactant is used in an amount of 0 to 30 weight 0 / 〇 ( Satisfactory results can be obtained when incorporated into the bleaching detergent composition at 1 to 20% by weight. 'In addition to zeolite, a metal deactivator can be incorporated into the present invention if necessary. Examples of the metal passivation agent include the following compounds: 1) Various phosphates such as' orthoscale, pyrogenate, trimerate, metaphosphate, hexapolyphosphate, and phytanate. 2) B Keng-1,1 scaly acid salt, Yikeng-1,1,2-trisalcoic acid salt, ethidium chloride -13- This paper size applies to China National Cockroach Standard (CNS) A4 specification (21 〇X 297 (Mm) (Please read the precautions on the back before filling out this page}. Outfit-Printed by Staff Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 40 1457 A7 B7 V. Description of the invention (11) 1,1-bisphosphonate and its derivatives, ethenyl-1,1,2-tritonate, ethenyl-1,2-dicarboxyl-1 , 2-bisphosphonates and mesylphosphonates. 3) Salts of phosphonic acid such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2 , 3,4-tricarboxylic acid and α-phosphonosuccinic acid. 4) Amino acid salts such as aspartic acid, glutamic acid, and glycine. 5) Amino polyacetic acid salts For example, nitrile triacetate, imine diacetate, ethylenediamine tetraacetate, diethylenetriamine pentaacetate, glycol ether diamine tetraacetate, hydroxyethylimine diacetate, Triethylenetetramine hexaacetate and clomidate. 6) Polyelectrolyte, for example, polyacrylic acid, acrylic acid / maleic acid copolymer, although it is horse's fee 'polymaleic acid, poly-or-acrylic acid, polyacrylic acid and its salts . '7) Salts of organic carboxylic acids such as' diglycolic acid, hydroxydisuccinic acid, carboxymethyl peptone, citric acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid' gluconic acid, hydroxymethyl Tartaric acid and carboxymethyl succinic acid. Metal deactivators other than zeolite may be included in the composition in an amount of 0 to 50% by weight. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs The following ingredients can be blended into the bleaching detergent composition of the present invention as appropriate. Conventionally known ingredients can be incorporated in known amounts. Examples include amidine polymers such as '& methylcellulose, test agents such as metal stearic acid,' such as 'soda ash, and metal salts such as still (Japanese m' · / and 3 dream acid Steel; extenders such as sodium sulfate; dispersants, color shift inhibitors or re-contamination inhibitors, such as ethinyl alcohol> VA) ... 1 乂 cilrolidone (PVP) 'poly) acetophenone and carboxymethyl carbamidine A variety of enzymes such as

401457 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (12) ~~~ Proteases, cellulases, amylases and lipases; enzyme stabilizers such as boron compounds and sodium sulfite; biphenyls and diphenyls Vinyl-type fluorescent dyes; defoamers such as silicone / silica compounds; antioxidants, bluing agents, and aromatics. Specific examples thereof described in Japanese A-8-21 8,093 can be used. When blending the optional ingredients listed on the field, the amount is within the following range: (1) Enzymes such as protease, oryzinase, amylase, and lipase. 0 to 10 weight. /. . (2) Fluorescent dyes, for example, 4,4, -bis (2-sulfophenethylfluorenyl double T salts, 4, bis (triazolyl) stilbene derivatives, and bis (trioxazine) fluorenyl ) Diphenyl ethylene disulfonic acid derivative: 0 to 5% by weight. (3) Alkaline electrolytes such as 'silicic acid', carbonic acid, and salts such as sulfuric acid (preferably sodium salt but salt): 450% by weight ⑷ Recontamination inhibitors such as, for example, polyalcohol, polyvinylacetol, polyvinylpyrrolidone, and carboxymethyl to 2% by weight. ^ "[Effect of the present invention] The present invention can provide a colored granular bleach accelerator, which maintains the stability of the bleach accelerator, even after it is incorporated into the detergent composition, especially those containing stagnant stones, and In addition, it is provided with a bleaching detergent composition. [Examples] The present invention will be described with reference to various examples, such as limiting examples. The invention should not be interpreted in Example 1 < Preparation of hydroxy-colored granular bleach accelerator > The following compounds 1 and 4 were used to prepare the granular bleach accelerator shown in Table _ using the following compounds: and B 0 classics (please read the precautions on this page first)

-1T -15- This paper standard Photographic Standard (CNS) A4 specification (210X297 mm 401457 A7 B7) V. Description of the invention (13 Printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economic Affairs A-1: Laurel (base) sulfuric acid Sodium, Emal 10 powder selected by Kao Corporation. A-2: Polyemulsified Ethyl Sodium Lauryl Sulfate 'selected by Kao Corporation. Emal A 70C. Λ Bl: Polyoxidized Ethylene, with a molecular weight of 8,000, was selected by Aldrich Chemical Co., Ltd. Tetradecanoic acid was selected by Kao Corporation. Lunac MY-98. ) Sodium Tetraethylammonium Ethylene Diamine Nonyloxybenzene Sulfonate Ultramarine Blue, selected by Daiichi Kasei Kogyo Co., Ltd. Blue and green, selected by Dainichiseika Color and Chemical Manufacturing Company. D: 1: Food, Pharmaceutical and cosmetic grade, blue dye # 2 D'-2: phthalocyanine blue B (selected by Tokyo Ink Manufacturing Co., Ltd.) E-1: succinic acid (method 1) component A-1 and A- 2. Ingredients B-1 or B-2, ingredients C-1, C-ί, C-3 or C-2, ingredients D-1 or D-2 and ingredients E-1 are added to a South Speed in such amounts. mixing Medium (FS-GC-10, selected by FukaeKogyo) to produce a total amount of 5,000 grams. The contents were mixed and heated at a jacket temperature of 80 ° C, and the rotation speed of the shaft was 200 rpm And the rotating speed of the granulating blade is 1,500 rpm. When the temperature reaches 70 ° C, the generated powder is sung out. B-2 C-1 C-2 C-3 C-4 D-1 D- 2 (Please read and read the notes on the back first, write this page each time). Binding. Order-16- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 01457 A7 B7 V. Description of the invention ( 14) The obtained mixture is extruded through a sieve having an opening diameter of 800 micrometers using a long extrusion tablet press (selected by Fuji Paudal Co., Ltd., tablet press] 乂 100). The extrudate produced was cooled using a vibration cooler (Vibration / Flow Dryer Type VDF / 6OO selected by Fuji Paudal Co., Ltd.), and then a particle size adjuster (manufactured by Fuji paudai Co., Ltd. (Knife cutter type PL-200) is reduced to a finer size. The particles thus obtained were classified to produce particles 0 having an average particle diameter of 900 micrometers. (Method 2) The components shown in Tables 1 and 2 were removed except for the B_i component or the B- 丨 and b_2 components. The ingredients are mixed in the same manner as in Method 2. When the powder / dish degree reaches 70 ° C, it is added at 70 °. (: Melted ingredients 丨 or melted ingredients B-1 and B-2 at 70 °. The resulting mixture is further mixed under stirring for 30 minutes, and then formed in the same manner as method i (Method 3) The ingredients shown in Tables 1, 2 and Π4 are removed and the ingredients A_2 and B-1 are removed, and the ingredients of B-2 and A-2 are mixed in the same manner as in Method]. When the powder temperature reaches 7CTC, add the component melted at 70 ° C (: the component melted at the time and A-2 or the component melted at 7 ° C B-i, B_2 * A_2. The mixture produced by g is further mixed under stirring. 30 minutes, and then granulated in the same manner as the method. (Method 4) Using the ingredients shown in Tables 1, 2 and n-i, except for the ingredients, prepare a granular bleach accelerator. Separate from this丨 Preparation containing 13% by weight of -17- This paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) {Please read the precautions on the back # 'fill_ 痛 本 育) first. _ Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (15) Composition D'-1 and 5.0% by weight of anhydrous sulfur An aqueous solution of steel. This solution was used to color the granular accelerator via the method described in Example 1 shown in Japanese Patent A2-258872. Table 1 Granular accelerator Z-1 Z- 2 Z-3 Z-4 Z-5 Z-6 Z-7 Z-8 Granulation method Method 1 Method 3 Method 2 Method 1 Method 2 Method 3 Method 2 Method 3 Ingredients (wt%) A-1 20 30 30 20 20 30 30 20 A-2 3 2 2 3 3 2 2 3 B-1 15 12.8 12.8 15 10 7.B 7.8 10 B-2 5 5 5 5 C-1 50 60 50 60 C-2 60 50 60 50 C -3 ·· C-4 D-1 0.2 0.2 0.5 0.2 D-2 0.2 0.2 0.2 0.2 D, -l D, -2 El 1.8 5 5 1.8 1.5 5 5 1.8 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please First read the back, v / notes and write this page) -18- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 '乂 297 mm) 7 5 4 i Β 5. Description of the invention (16) Ministry of Economic Affairs Printed by the Central Standards Bureau's Consumer Cooperatives Table 2 The granular accelerators of the present invention are compared to the granular accelerators. The granular accelerators are: Z-9, Z-10, Z-11, Z-12, Z-1, Z-2, Z- 3 ZZ, -4 Granulation method Method 1 Method 3 Method 1 Method 2 Method 3 Method 2 Method 3 Ingredient (wt%) A- 1 20 30 20 30 30 20 A-2 3 2 3 2 2 3 Β- 1 15 7.8 20 30 12.8 10 30 7.8 Β -2 5 5 5 C- 1 50 60 50 60 C-2 60 50 C-3 75 C-4 65 65 D- 1 0.2 2 D-2 0.2 2 D'- 1 0.2 0.2 D, -2 2 0.2 Ε-1 1.8 5 3 3 5 1.8 3 5 Please • 4 Read the note-19- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 401.45 "? A7 B7 V. Invention Explanation (17) Table II-1 Granular accelerator, granulation method A- 1_ Printed by the Employees' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs

Z-13 Method 1 _20 _3 15 60 0.01 A-2 B- 1_ B-2_ C- 1_ C-2_ C-3_ C-4_ D- 1_ D-2 ___ D 丨 -1_ D1 -2_ E -1

Example 2 < Preparation of bleaching detergent composition > Detergent base A or B was prepared via γ, using sodium perborate, and the method described in Example 2 :: =, 制备, cationic preparation (granular bleach Accelerators! 3 and 4 < Gubai detergent composition and II-2 store the 4 obtained in the conditions y shown in Tables 3, 4 and H-2, and then pass through; -20- This paper size is applicable to China National Standards (CNS) 8-4 specification (2 丨 0'〆297 cm) 40145 ^ Μ Β7 Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Ⅴ. Description of the invention (18) Method for testing bleach accelerators Retention. The results are shown in Tables 3, 4 and II-2. (Detergent Base A) An aqueous phase slurry having a solids content of 60% was prepared from the following compounds: 2 g of straight chain gauge • Hua • benzene Sodium Sulfate, 0.5 仟 g of fired-based sulfuric acid steel (selected by Kao, Emal 10 powder), 0.3 仟 g of polyoxyethylene alkyl ether (selected by Shokubai Kagaku Kogyo Co., Ltd., Emulgen 510L) 0.3 gram acrylic acid / maleic acid copolymer (selected by BASF AG, Sokalan cp-5), · 0.3 gram of fatty acid salt ( Oil, sodium salt), 0.6 g of sodium carbonate, 1.5 g of No. 1 silicate, 1.5 g of zeolite 4A '0. 1 g of PEG (polyethylene glycol with an average molecular weight of 6,000), and Glauber's salt (for equalization). This slurry is spray-dried to make particles, which is treated with a high-speed mixer CFS-GC-10, selected by Fukae Kogyo KK, and then granulated to make a detergent. Binder A. It has an average particle diameter of 400 # m (micrometers) and a bulk density of 750 g / L. (Detergent Base B) An aqueous phase slurry having a solid content of 60% was prepared from the following compounds: 3 shi of sodium linear benzene benzoate, 0.1 shi of propionic acid / maleic acid copolymer (from Selected by BASF AG, Sokalan cp-5), 1.5 shi sodium carbonate, 1 仟 stagnation stone 4 A, 2 仟 sodium tripolyphosphate, 0.1 什 peg (polyethylene glycol with an average molecular weight of 6,000) ) And thenardite (for equilibrium). This polymer was spray-dried to form particles, which was treated with a high-speed mixer (type FS-GC-10, selected by Fukae Kogyo KK · KK.), And then granulated to make a detergent base. Material B, which has an average particle diameter of 400 V m (micrometers) and a bulk density of 750 g / L.丨 -21- (CNS) (210X297 ^) ~~ '~~ (Please read the precautions on the back and write this page first)

, 1T .nn n —. Mi A7 B7 V. Description of the invention (19) (detergent base c). The aqueous phase with a solid content of 60% is made from the following compounds: 2.31 g of straight perylene Acid steel, sulphur-based sulphuric acid steel (selected by Ka. Ling, Emal 1 () powder), 0231 Shig of acrylic / maleic copolymer (selected by BASF AG, % K, JJ Sokalan cp-5) »0.462 g of carbonated fishing, 3.388 g of stagnant stone 4A, thenardite (for balance) and 0.23 g of PEG. This body is spray-dried to form particles, which is processed with a high-speed mixer (FS_GC_10 type, processed by Fukae Kogoy κ κ Corporation), and then granulated to make a washing base c, which has a cut micron Mean particle diameter and bulk density of 750 g / L. ≪ Measurement of foot bleaching accelerator retention > 500 grams of each bleaching detergent composition shown in Tables 3 and 4 was used. Coffee grinder was pulverized And made into powder. Accurately weigh out 丨 grams of each of them and put them into a measuring flask with a milliliter. A solution prepared by dissolving a 0.2 N aqueous solution of hydrochloric acid (its concentration is i% by weight) Add to the powder to adjust the total volume to 100 ml. The resulting solution was stored under the conditions shown in Table 3'4 and Π_2. Before storage and storage :, each solution was used with high-efficiency liquid Chromatographic separation method analysis and use; Calculate bleach accelerant retention. Tenth Ministry of Economic Affairs Central Standards Bureau Employee Co-operative Cooperative Printed bleach accelerant retention (%) After storage, bleach accelerant content ... ....... X 1 0 0 22 bleach accelerators before storage Zhang scale applicable Chinese National Standard (CNS) Α4 Specification (21〇 > < 297 mm) Γ- 5 4 1ο 4

7 B Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (2 () Table 3 The granular accelerator of the present invention 1 2 3 4 5 6 7 8 Bleaching detergent composition (%) Detergent base A 93 90 92 93 Detergent base B 92 93 90 93 Sodium peroxide 5 — < — — < — ^ — Zeolite Z-1 2 Hydrate Z-2 3 Zeolite Z-3 5 Zeolite Z-4 2 Zeolite Z -5 3 Zeolite Z-6 5 Zeolite Z-7 2 Zeolite Z-8 2 Zeolite Z-9-Chronite Z-10 Chronite Z-11 Chronite Z-12 Zeolite Z'-1 Zeolite Z-2 Zeolite Z · -3 Zeolite Z'-4 Storage conditions Storage temperature fc) 40 < — < — < r ~ Shelf life (months) 2 < — < — < —— < — < — < — Bleaching Accelerator Retention 91 98 97 92 96 97 98 97 -23- (Please read the Cautions on the reverse side to complete this page). Loading · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) V. Description of invention (21) A7 B7 Staff of Central Bureau of Standards, Ministry of Economic Affairs Consumption Cooperatives Printed Table 4 Granular Accelerator Comparative Granular Accelerator 9 10 11 12 1 2 3 4 Bleaching and washing strip composition (%) Detergent base A 93 93 93 93 Binder 92 92 90 93 Sodium Peroxide 5 <-<-<-Zeolite Z-1 Zeolite Z-2 Zeolite Z-3 Zeolite Z-4 Zeolite Z-5 Zeolite Z-6 Zeolite Z-7 Hematite Z-8 Zeolite Z-9 2 Hematite Z-10 3 'Hematite Z-11 2 Hematite Z-12 2 Zeolite Z'-l 2 Zeolite Z'-2 5 Zeolite Xi-3 2 Hematite Z · -4 2 Storage conditions Storage temperature (° C) 40 < — < — < — < — Shelf life (months) 2 < —-< — < — < — < — Keep bleach accelerator Sex 85 87 85: 88 76 79 79 75 (please read the precautions on the back first and write this page)-pack ·

'1T -24- This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 V. Description of the invention (22) Table II-2 The granular accelerator of the present invention 13 14 15 16 17 18 19 20 Detergent Base A 95 92 Bleaching Detergent Base B 75 39 90 92 White Detergent Base C 90 90 Washed Peroxide Steel 0.1 20 20 5 5 5 5 5 Polyester Zeolite Z-13 5 Agent Stagnant Stone Z -14 5 group of stagnant stone Z-15 5 41 zeolite Z-16 5 material stagnant stone Z-17 5 (%) stagnant stone Z-18 3 stagnant stone Z-19 3 reserve temperature (° C) 40 <- < — < — ^ — < — Condition reserve period (months) 2 < r— < — < — < — ^ — Retainability of bleach accelerator 88 90 92 91 94 95 93 98 Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives -25- This paper size applies to the Chinese National Standard (CNS) Α4 specification (21 × 297 mm)

Claims (1)

A8 B8 C8 D8 401457 Patent Application No. 87101294 Chinese Patent Application Amendment (June 88) VI. Application 1. A granular bleaching accelerator composition comprising 〇. 〇1 to 丨 〇 by weight A pigment selected between ultramarine monitors and cyanine greens and at least one selected from 1.0 to 90% by weight selected from the group consisting of tetraethylammonium ethylenediamine, alkanoyloxybenzene sulfonate and alkanoyloxybenzenecarboxylic acid and salts thereof Bleach accelerator. 2_ The granular bleach accelerator composition according to item 丨 of the patent application scope, which additionally contains 0 to 50% by weight of at least one sulfate salt selected from alkyl sulfate salts and alkyl ether sulfate salts ( a) and 0.5 to 30% by weight of a binder (b) selected from fatty acids, polyethylene oxides and mixtures thereof. 3_ The granular bleach accelerator composition according to item 2 of the scope of the patent application, wherein I bleach accelerator (c) is represented by the following formula (I) or (II) and is contained at 1.0 to 70% by weight. (Please read the precautions on the back before filling this page) CnH2n + 1 C00 S〇3Na (I) CmH2mn ——COO —— COOH (jj) [where n and m each represent a number from 5 to i7] Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards and Technology of the People's Republic of China 4_ Granular bleach accelerator composition according to item i or item 3 of the scope of patent application, which additionally contains a member selected from the group consisting of succinic acid, maleic acid, fumaric acid, and citric acid , Glycolic acid and at least one acid agent of p-hydroxybenzoic acid. 5. — A method for preparing the granular bleaching promoter in item 3 of the patent scope of Shenqing Patent, which method comprises pre-assigning ingredient (c) and ingredients The remaining ingredients and ingredients are mixed to make the paper. The paper size is applicable to Chinese national standards (CNS> A4 specification (210X297)) A8 B8 C8 D8 401457 Patent Application No. 87101294 Chinese Patent Application Amendment (Month 88) 6 1. Shen 1. A granular bleaching accelerator composition, which comprises 0.001 to 1% by weight of a pigment selected between ultramarine youth and cyanine green and at least 1.0 to 90% by weight selected from tetraethyl Bleaching accelerators of fluorenylethylenediamine, alkoxybenzyl sulfonate and alkoxybenzyl carboxylic acid and their salts. 2_ Granular bleach promoter composition according to item 丨 of the patent application scope In addition, it contains 0 to 50% by weight of at least one sulfate (a) selected from alkyl sulfate salts and alkyl ether sulfates and 0.5 to 30% by weight selected from fatty acids, polyethylene oxide And its mixture (b). 3_ According to the application The granular bleach accelerator composition of the range item 2, wherein I bleach accelerator (c) is represented by the following formula (ii) or (II) and is included in the range of 1.0 to 70% by weight. (Please read the precautions on the back first (Fill in this page again) CnH2n + 1 C00 S〇3Na (I) CmH2mn ——COO —— COOH (jj) [where n and m each represents a number from 5 to i7] Employee Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Print 4_ Granular bleach accelerator composition according to item i or item 3 of the scope of patent application, which additionally contains a member selected from the group consisting of succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid and p-hydroxybenzene At least one acid agent of formic acid. 5.-A method for preparing the granular bleaching promoter in item 3 of the patent claim, which method comprises preparing the component (c) and the component (sentence and part or all of the component a. The paper is prepared by mixing the premix with the remaining ingredients ⑷ and ingredients 适用. The paper size is applicable to Chinese national standards (CNS> A4 specification (210X297)) 401451ί Α8 Β8 C8 D8, the scope of patent application is a homogeneous mixture ', and the mixture Extruded and granulated to produce 0.5 to 2.5 The average particle diameter of nun. According to the method in the scope of patent application No. 5, wherein the binder of component (b) has a melting point of 40 ° C or higher and is added after being melted. 7 · —A kind of bleaching detergent A composition comprising 0.05 to 10% by weight of a granular bleach accelerator composition according to any one of items 1 to 4 of the above-mentioned application patent range and 0_1 to 20% by weight of sodium (di) sodium carbonate and / or high Sodium borate. A bleach strip cleaner composition comprising: (1) 0.1 to 20% by weight of sodium per (di) carbonate and / or sodium perborate, and (2) 15 to 40% by weight of an alkyl group selected from At least one kind of anionic surfactants of benzene sulfonates, alkyl sulfates, and ether ether sulfates. (3) 0.5 to 10% by weight of the granular bleaching accelerator _, and (4) 5 to 40% by weight of zeolite. I -1! Mnnm I. ^ 1 n I ^ ---- (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs __I Μ —-----— .uh ^ i ---- 1 _ -2 This paper size adopts China National Standard (CNS) A4 specification (210X297 mm)