WO2006043662A1 - Amylase-containing granular detergent composition - Google Patents

Amylase-containing granular detergent composition Download PDF

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Publication number
WO2006043662A1
WO2006043662A1 PCT/JP2005/019394 JP2005019394W WO2006043662A1 WO 2006043662 A1 WO2006043662 A1 WO 2006043662A1 JP 2005019394 W JP2005019394 W JP 2005019394W WO 2006043662 A1 WO2006043662 A1 WO 2006043662A1
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Prior art keywords
water
particles
soluble
surfactant
mass
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PCT/JP2005/019394
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French (fr)
Japanese (ja)
Inventor
Mizue Chiba
Katsuya Nagayasu
Yasushi Hirata
Satoru Nagata
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Lion Corporation
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Application filed by Lion Corporation filed Critical Lion Corporation
Priority to TW094136460A priority Critical patent/TWI287573B/en
Publication of WO2006043662A1 publication Critical patent/WO2006043662A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • Amylase-containing granular detergent composition
  • the present invention relates to a granular detergent composition used for textile products such as clothing, and more particularly to a granular detergent composition containing a specific amylase having a high effect of spilling dirt.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-95996
  • Patent Document 2 Japanese Patent Publication No. 11-507989
  • an object of the present invention is to provide a granular detergent composition that is highly effective in removing spilled dirt even in normal washing using a washing machine.
  • the present inventors have used the above-mentioned object by combining a specific amylase with surface-treated water-soluble alkali inorganic compound particles and surfactant-containing particles.
  • the present invention has been found to be able to be achieved. That is, the present invention provides a granular detergent composition characterized by containing the following components: (A) an amylase having a viscosity reduction rate calculated by the following formula (1) of 40% or more,
  • a water-soluble alkaline inorganic compound is surface-treated with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound, and the content of the water-soluble alkaline compound is 50 to 98% by mass.
  • Viscosity reduction rate (%) x 0 0 ( 1 )
  • the present invention by using a specific amylase having a high activity and a combination of alkali builder-containing particles and surfactant-containing particles whose surface area is coated in a certain range, Effectively and easily removed. According to the present invention, it is also possible to remove spilled dirt without damaging clothes or the like.
  • the composition of the present invention is also excellent in solubility in water.
  • the component (A) of the present invention is an amylase having a viscosity reduction rate calculated by the above formula (1) of 40% or more.
  • corn starch manufactured by Kanto Chemical Co., Inc. 25g was added to 475g of 90 ⁇ 2 ° C alkali (sodium carbonate 4000ppm) aqueous solution, stirred and dissolved at 90 ⁇ 2 ° C for 1 hour, then 5 ° C Cool for 12 hours. Then, it is allowed to stand at room temperature. After the temperature of the solution becomes equal to room temperature, the temperature is adjusted to 25 ° C.
  • alkali sodium carbonate 4000ppm
  • Amylase satisfying the specific viscosity reduction rate can be appropriately selected by a simple screening method using the above-described commercially available apparatus (CJV5000 manufactured by A & D Co., Ltd.).
  • amylases examples include amylase that hydrolyzes 1,4 bonds such as starch, glycogen and the like, ⁇ -amylase, dialcarcase, darcoamylase, and starch glucoside.
  • amylases include amylase that hydrolyzes 1,4 bonds such as starch, glycogen and the like, ⁇ -amylase, dialcarcase, darcoamylase, and starch glucoside.
  • Examples include dalcore amylase, pullulanase, isoamylase, amiguchi 1,6-dalcositase ⁇ 4-hyglucanotransferase, origo 1,6-dalcosidase, etc. that hydrolyze 1, 6 bonds.
  • the enzyme is not particularly limited as long as it is an enzyme that hydrolyzes starch, and can be used alone or in combination of two or more.
  • amylases that can be used in the present invention are given below. However, the following examples do not limit the present invention.
  • Examples of commercially available enzymes that can be obtained include the following. Termamyl, Dyamyl, Stainzyme, Promozyme 200L (above, Novozymes), Maxamy 1 (Geneencore), Amano Pharmaceutical's pullulanase ama DB-250, Pullulanase derived from Aerobacter aerogenes ATCC9621 (crude or crystallized product released by Seikagaku Corporation).
  • amylase described in the patent publication examples include the following.
  • amylases can be used alone or in combination of two or more. When two or more types are used in combination, even if the viscosity reduction rate for each amylase is less than 40%, if the viscosity reduction rate when used in combination is 40% or more, the (v) component of the present invention Power S to use.
  • the component (ii) of the present invention an amylase having a viscosity reduction rate of 70% or more is preferable, and an amylase having 80% or more is more preferable. It is not bound by any theory, but when the viscosity reduction rate of amylase is 40% or more, the adhesion between clothes and dirt can be weakened, so it has a high removal effect against spilled dirt.
  • the viscosity reduction rate of amylase can be increased by selecting an amylase having a high viscosity reduction effect or by selecting an amylase mutated to increase the viscosity reduction effect.
  • the amylases described in the above patent publications (21) to (33) are preferred. More particularly, stinzym is preferable.
  • Amylase is preferably used as a granulated product with stabilizers, fillers, extenders, brighteners, binders, coating agents, and the like, based on ordinary granulation methods. This is because of excellent stability and solubility in water. From the viewpoint of stability and solubility in water, it is desirable that the average particle size measured by the method described in the examples described later is 200 to 700 ⁇ m. In addition, when two or more kinds of enzymes are granulated, they may be granulated separately, or the enzymes may be mixed to form the same granulated product.
  • the amount of amylase in the enzyme granulated product is about 0.1 to 10% by mass as the enzyme protein, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. It is.
  • methods for granulating enzyme-containing particles JP-A-53-6484, JP-A-60-262900, JP-A-62-257990, JP-A-1-112983, JP-T-3- Examples include the methods described in Japanese Patent No. 503775, Japanese Patent Publication No. 4-503369, Japanese Patent Laid-Open No. 2000-178593.
  • (A) amylase is an enzyme tag based on the total amount of the composition.
  • the amount of the protein is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, particularly preferably 0.003% by mass or more, preferably 0.05% by mass or less, more preferably 0.00%. It is preferably contained in an amount of 03% by mass or less, particularly preferably 0.02% by mass or less. When the amount is less than 001% by mass, the effect of the present invention may be reduced. When the amount is more than 0.05% by mass, the effect may reach a peak.
  • the amount of enzyme protein in the detergent composition is determined by obtaining a crude enzyme by a separation means such as a salting-out method, a precipitation method, or an ultrafiltration method, if necessary, followed by purification and crystallization by a known method. It is possible to stain the band formed by force- or SDS-polyacrylamide gel electrophoresis by a known staining method and compare the degree of staining with a known enzyme purified product.
  • a separation means such as a salting-out method, a precipitation method, or an ultrafiltration method
  • the component (B) of the present invention is a surfactant-containing particle containing 10 to 50% by mass of a surfactant.
  • surfactant used in the surfactant-containing particles examples include an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. These may be used alone or in combination of two or more. They can be used in appropriate combinations.
  • the surfactant in the surfactant-containing particles is preferably a combination of an anionic surfactant and a nonionic surfactant, which is preferably an anionic surfactant and a nonionic surfactant, from the viewpoint of cleaning performance.
  • a nonionic surfactant which is preferably an anionic surfactant and a nonionic surfactant, from the viewpoint of cleaning performance.
  • the mass ratio of the anionic surfactant and the nonionic surfactant is 0.1 to: 10 is preferable, 0.2 to 8 is more preferable, and 0.3 to 7 is more preferable.
  • anionic surfactant various anionic surfactants that are not particularly limited can be used as long as they are conventionally used in detergents. For example, the following can be mentioned.
  • LAS Linear or branched alkylbenzene sulfonate
  • AS C10-20 alkyl sulfate
  • AOS ⁇ -Olefin sulfonate
  • Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms
  • a saturated or unsaturated ⁇ -sulfo fatty acid ( ⁇ -SF) salt having 8 to 20 carbon atoms or a methyl anionic surfactant thereof is an alkali metal salt of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or Potassium salts, etc.), AOS, a-SF, or alkali metal salts (eg, sodium or potassium salts) of methyl, ethinole or propyl esters thereof, alkali metal salts of AES (eg, sodium or potassium salts), higher grades Fatty acid metal salts (for example, sodium or potassium salts) are preferred.
  • LAS linear alkylbenzene sulfonic acid
  • AOS for example, sodium or Potassium salts, etc.
  • AOS alkali metal salts of methyl, ethinole or propyl esters thereof
  • alkali metal salts of AES eg, sodium or potassium salts
  • higher grades Fatty acid metal salts
  • nonionic surfactant examples include the following.
  • polyoxyethylene alkyl (or alkeninole) ether, polyoxyester Tylene polyoxypropylene alkyl (or alkenyl) ether is preferred.
  • the aliphatic alcohols used here include primary alcohols and secondary alcohols.
  • the alkyl group may have a branched chain.
  • a primary alcohol is preferable.
  • fatty acid alkyl ester alkoxylates represented by the following general formula (I)
  • R1C0 represents a fatty acid residue having 6 to 22, preferably 8 to 18 carbon atoms
  • OA represents 2 to 4, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide.
  • N represents an addition unit of alkylene oxide
  • n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20.
  • R2 has a substituent of 1 to 3 carbon atoms. It may be a lower (C1-4) alkyl group.
  • the nonionic surfactant (1) described above is preferred, and an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 12 to 16 carbon atoms.
  • An added polyoxyalkylene alkyl (or alkenyl) ether is preferred.
  • the HLB of the nonionic surfactant in the present invention is a value determined by Griffin's method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Yonsho Co., Ltd., 1991). Year, page 234).
  • the melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Measuring Method of Melting Point and Melting Range of Chemical Products”.
  • Examples of the cationic surfactant include the following.
  • the above long chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and the short chain alkyl is 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, a benzyl group, 2 to 4 carbon atoms, Preferably it represents 2-3 hydroxyalkyl groups or polyoxyalkylene groups.
  • amphoteric surfactants examples include amphoteric surfactants such as imidazolines and amide betaines.
  • the amount of the surfactant is (B) 10 to 50% by mass in the surfactant-containing particles. Preferably, it is 15 to 40% by mass. If it exceeds 50% by mass, the fluidity may be inferior, and if it is less than 10% by mass, the solubility may be inferior.
  • the (B) surfactant-containing particles are preferably contained in an amount of 50 to 94% by mass, more preferably 75 to 90% by mass or more based on the total amount of the composition. preferable.
  • the amount is less than 50% by mass, the cleaning performance may be deteriorated.
  • the amount is more than 94% by mass, the effects of the present invention may be reduced due to lack of other components.
  • the (B) surfactant-containing particles of the present invention can contain any of the following optional components in addition to the above essential components. Note that inorganic compounds and water-soluble polymer compounds are listed in duplicate. Each of these optional components can be used alone or in combination of two or more.
  • Cleaning builder examples of the cleaning builder compounded in the surfactant-containing particles include inorganic and organic builders.
  • inorganic builder examples include sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, non-crystalline layered sodium silicate, etc., neutral salts, sodium sulfate, etc. Salts, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytate, and the following general formula (II)
  • M is an alkali metal atom such as sodium or potassium
  • xl, yl and wl are the number of moles of each component, and in general, xl is 0.7 to 1.5: yl is 0.5. (Numbers from 8 to 6, wl represents any positive number.)
  • M is an alkali metal atom such as sodium or potassium
  • x2, y2 and w2 indicate the number of moles of each component, and are generally white birch, ⁇ 2 ⁇ or 0.7-7: 1: 2, y2i 1. 6 to 2.8, w2i 0 or ⁇ indicates any positive number.
  • M is an alkali metal atom such as sodium or potassium
  • x3, y3, z3, and w3 are monole numbers of each component, and are generally white birch, ⁇ 3 ⁇ or 0.2-2: 1.1, y3i 0.2 to 4.0, ⁇ 3 ⁇ , 0.001 to 0.8, and w3 is 0 or any positive number.
  • Amorphous aluminosilicate represented by the following.
  • inorganic builders sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate and sodium aluminosilicate are preferred.
  • the compounding amount of the inorganic builder in the surfactant-containing particles is 10 to 80% by mass, preferably 20 to 70% by mass, more preferably 30 to 60% by mass. If the amount of inorganic builder is too small, fluidity may deteriorate, and if it is too large, dust generation may occur.
  • Examples of the organic builder include an organic high molecular builder and an organic low molecular builder.
  • Examples of organic polymer builders include acrylic acid polymer compounds, polyacetal carboxylates, cellulose polymer compounds, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, and other heavy polymers. Examples thereof include a polymer and a copolymer.
  • Acrylic acid polymers and acrylic acid Z maleic acid copolymers are preferred as the acrylic acid polymer compounds. Particularly, a salt of acrylic acid Z maleic acid copolymer having a weight average molecular weight of 1,000 to 80,000. A salt of an acrylic acid polymer is preferred.
  • polyacetal carbonate examples include polyacetal carboxyl such as polyglyoxynolic acid having a weight average molecular weight of 800 to 1,000,000, preferably 5,000 to 200,000 described in JP-A-54-52196. Acid salts are preferred.
  • cellulose polymer compound carboxymethyl cellulose (CMC) is preferable.
  • the weight average molecular weight of the water-soluble polymer compound is preferably 1,000,000 to: 1,000,000 force S, more preferably 1,000 to 100,000 force s.
  • the organic polymer builder can be used alone or in combination of two or more.
  • Organic low molecular weight builders include, for example, nitrite triacetate, ethylenediaminetetraacetate, ⁇ -alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate and other aminocarboxylates; serine diacetate Hydroxyaminocarboxylates such as salts, hydroxyiminodisuccinate, hydroxyethylethylenediamin triacetate, dihydroxyethyldaricine; hydroxyacetates, tartrate, citrate, darconate, etc.
  • Hydroxycarboxylates such as pyromellitic acid salts, benzopolycarboxylic acid salts, cyclopentanetetracarboxylic acid salts; carboxymethyl tartronate, ruboxymethyloxysuccinate, oxydisuccinate, Ether carbonates such as tartaric acid mono- or disuccinate Phosphate salts, and the like.
  • citrates aminocarboxylates, hydroxyaminocarboxylates, and hydroxyiminodisuccinates are preferred.
  • the compounding amount of the organic builder in the surfactant-containing particles is 0.:! To 20% by mass, preferably 0.5% to: 15% by mass, more preferably 1 to 10% by mass. . Formulation of organic builder If the amount is too small, the effect of improving the cleaning performance may not be obtained. If the amount is too large, the solubility of the (B) surfactant-containing particles themselves may be deteriorated.
  • citrate aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer, polyacetal
  • organic builder such as carboxylate
  • inorganic builder such as zeolite
  • Examples of the dissolution accelerator blended in the surfactant-containing particles include inorganic ammonium salts such as carbonated ammonium, ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, sodium xylenesulfonate, Water-soluble benzenesulfonate, sodium benzoate, sodium benzenesulfonate, sodium salt sodium salt, citrate, D-gnolecose, urea, sucrose, etc. Substances. Of these, potassium carbonate is particularly preferred from the viewpoint of the balance between the improvement in solubility and the cost that potassium carbonate and sodium chloride are preferred.
  • inorganic ammonium salts such as carbonated ammonium, ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, sodium xylenesulfonate, Water-soluble benzenesulfonate, sodium benzoate, sodium benzenesulfonate
  • the blending amount thereof is preferably (B) surfactant-containing particles in terms of solubility improvement effect: (!) To 15% by mass, more preferably 2 to: 12% by mass, and even more preferably. Is 5 to 10 mass%.
  • the blending amount is preferably (B) in the surfactant-containing particles from the viewpoint of improving the solubility:! -10 mass%, more preferably 2-8 mass%, Preferably it is 3-7 mass%.
  • Swellable water-insoluble substances such as powdered cellulose, crystalline cellulose, bentonite, etc.
  • Fluorescent agent bis (triazinylaminostilbene) disulfonic acid derivative (Tinopearl AM S-GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X], etc.
  • Antistatic agent dialkyl type quaternary ammonium salt and other cationic surfactants
  • Anti-staining agent cellulose derivatives such as carboxymethyl cellulose,
  • Reducing agent sodium sulfite, potassium sulfite, etc.
  • Bleach activation catalyst especially copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum, etc.
  • Cobalt is formed through atoms, oxygen atoms, and the like, and as the transition metal contained, cobalt, manganese, etc. are preferred, and manganese is particularly preferred.
  • the average particle diameter of the (B) surfactant-containing particles is preferably 200 to: 1,500 zm, more preferably 250 to 1,000 zm, and even more preferably 300 to 700 ⁇ m.
  • the bulk density is preferably ⁇ or 0.4 to: 1.2 g / mL, more preferably f to 0.5 to 1. Og / mL.
  • the water content of the (B) surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and further preferably 5 to 8% by mass from the viewpoints of solubility and storage stability.
  • the surfactant-containing particles can be obtained by the following granulation method.
  • the raw powder and binder components (surfactant, water, liquid polymer component, etc.) are kneaded * Extruded granulation method after kneading and then extruding and granulating, the resulting solid detergent after kneading Smashing and granulating the powder, crushing granulation method, stirring granulation method in which the binder component is added to the raw material powder and stirring and stirring with a stirring blade, the binder component is sprayed while rolling the raw material powder Examples thereof include a rolling granulation method for granulation, and a fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder. Specific apparatuses and conditions that can be used in these granulation methods are as described in JP-A-2003-105400, JP-A-2003-238998, edited by Japan Powder Technology Association, and the first edition of
  • the surface-treated water-soluble alkali-inorganic compound particles and (B) the surfactant-containing particles are preferably organic or Surface treatment with inorganic fine powder is preferred.
  • These fine powders are not particularly limited as long as they have a primary particle size of 30 zm or less, preferably 0.1 to 10 zm, but examples include normal temperature solid surfactants and long-chain fatty acid alkaline earths.
  • the amount of the fine powder is preferably 0.1 to 10% by mass in the granular granular detergent composition, more preferably 0.3 to 5% by mass, It is preferably 0.5 to 3% by mass.
  • the water-soluble alkaline inorganic compound of the particles is one or more selected from sodium carbonate or potassium carbonate, and the water-soluble polymer compound is a vinyl polymer compound, a polysaccharide or a derivative thereof, and a polyester compound. 1 or 2 or more types selected from molecular compounds,
  • the amount of the poorly water-soluble compound in the particles is less than 10% by mass, and
  • the surfactant in the surfactant-containing particles The amount is 10-40% by mass. Use of such a combination is preferable because dispersibility at a low water temperature can be greatly improved.
  • the component (C) of the present invention is obtained by subjecting a water-soluble alkaline inorganic compound as a core to a surface treatment with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound, and the content of the water-soluble alkaline inorganic compound.
  • the surface-treated water-soluble alkali-inorganic compound particles having an amount of 50 to 98% by mass.
  • Component (C) uses a water-soluble alkali-inorganic compound as core particles (hereinafter referred to as water-soluble alkali-inorganic compound core particles) from the viewpoint of low-temperature solubility, and the water-soluble alkali-inorganic compound core particles are used as the first surface treatment agent.
  • water-soluble alkali-inorganic compound core particles that can be obtained by surface-treating with an organic or inorganic water-soluble polymer compound as the second surface treatment agent and surface-treating with a poorly water-soluble compound as the second surface treatment agent. I prefer it,
  • the water-soluble alkali-inorganic compound core particles that can be used in the present invention are water-soluble alkali-inorganic compound particles having a solubility in water at 5 ° C of not less than lgZlOOg, preferably not less than 2 gZl00 g, more preferably not less than 3 gZlO Og. Say.
  • Such water-soluble alkali-inorganic compound particles are not particularly limited, and can be used singly or in appropriate combination of two or more.
  • the pH of a saturated aqueous solution at 5 ° C is 8 or higher, preferably the pH of a saturated aqueous solution at 5 ° C is 9 or higher, more preferably, the pH of a saturated aqueous solution at 5 ° C is 10 or higher.
  • Sexual power Re-inorganic compounds are preferred.
  • water-soluble alkali inorganic compound particles include those generally used as an alkali cleaning builder.
  • Specific examples include carbonates, bicarbonates and sesquicarbonates, sulfites, phosphates and polycondensed phosphates, silicates and the like.
  • sodium carbonate, potassium carbonate, sodium tripolyphosphate, and the like are more preferable, such as carbonates and polycondensed phosphates.
  • complex salts with other salts can also be suitably used.
  • burkeite which is a complex salt of sodium carbonate and sodium sulfate
  • the water-soluble alkali inorganic compound can be used alone or in combination of two or more.
  • the water-soluble alkali-inorganic compound core particles can be obtained by a conventional method, and the average particle diameter thereof is preferably 100 to 1500 ⁇ , more preferably f to 200 to 1000 ⁇ .
  • the average particle size is less than lOO x m, the surface treatment with the water-soluble polymer compound may be difficult, and when it exceeds 1500 ⁇ m, the solubility of the water-soluble alkaline inorganic compound may be lowered.
  • commercially available particles can be used as appropriate.
  • an average particle diameter is based on the measuring method as described in the Example mentioned later.
  • water-soluble alkali-inorganic compounds there are various grades of commercially available water-soluble alkali-inorganic compounds, but the use of the present invention is not limited thereto.
  • water-soluble alkaline inorganic compounds containing impurities mixed in the manufacturing process, storage stabilizers for stabilizing the quality, and antioxidants are also included in the scope of the present invention.
  • the organic water-soluble polymer compound which is the second surface treatment agent used for the surface treatment of the water-soluble alkali inorganic compound, is not less than 0.1 lg, preferably not less than 0.2 g, with respect to water lOOg at 40 ° C. Preferably, it is a polymer compound that is uniformly mixed with water at a concentration of 2 g or more.
  • Such an organic water-soluble polymer compound is not particularly limited and may be used alone or in appropriate combination of two or more.
  • organic water-soluble polymer compound examples include natural polymer compounds, semi-synthetic polymer compounds, and synthetic polymer compounds.
  • vinyl polymer compounds, polysaccharides, polyether polymer compounds, polyester polymer compounds, peptide polymers Compounds, polyurethane, and derivatives thereof can be used.
  • bull polymer compound examples include a bull polycarboxylate (acrylic polymer compound), a bull polysulfonate, a polybure pyridine salt, and a polyburimidazol salt.
  • polysaccharide various natural or synthetic polysaccharides can be used.
  • polyester polymer compounds include copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units. Examples of these include commercially available Texcare4291 (manufactured by Clariant), TexcareSRN-300 (manufactured by Clariant), and the like.
  • peptide polymer compound or derivatives thereof include gelatin, casein, albumin, collagen, polyglutamate, polyaspartate, polylysine, polyarginine, and derivatives thereof.
  • polyurethane examples include water-soluble polyurethane.
  • Other water-soluble polymer compounds such as polyethylene glycol can also be used.
  • the initial stage of contacting with water in a state where the water-soluble alkali inorganic compound core particles containing bicarbonate are surface-treated with the water-soluble organic polymer compound are preferred.
  • the water-soluble organic polymer compound having such characteristics include those having hydrophilic functional groups such as anionicity, amphotericity, and nonionicity.
  • Examples of the water-soluble organic polymer compound having an anionic group include a polymer compound having a carboxyl group and a sulfo group, and a water-soluble polysaccharide having an anionic group.
  • Examples of the water-soluble organic polymer compound having a carboxynole group include polymerization of monomers such as acrylic acid, maleic acid, itaconic acid, aconitic acid, methacrylic acid, fumaric acid, 2-hydroxyataryl acid, and citraconic acid.
  • bulle polycarboxylic acids (salts) such as a copolymer of these monomers and other bulle monomers and salts thereof.
  • water-soluble polymer compounds having a sulfo group examples include For example, monomers obtained by polymerizing monomers such as acrylamide propane sulfonic acid, methacrylamide propane sulfonic acid, and styrene sulfonic acid, and salts thereof, copolymers of these polymers with other vinyl polymers, salts thereof, and the like. Biel type polysulfonic acid (salt) etc. are mentioned.
  • water-soluble polysaccharide having an anionic group examples include polyuronic acid salt, alginic acid salt, polyaspartic acid salt, force laganinan, hyaluronic acid salt, chondroitin sulfate, carboxymethyl cellulose and the like.
  • amphoteric water-soluble polymer compound examples include a copolymer of a vinyl monomer having an anionic group and a bur monomer having a cationic group, a carboxybetaine group or a sulfobetaine group.
  • examples thereof include bur-based amphoteric polymers, and specifically include acrylic acid / dimethylaminoethyl methacrylic acid copolymer, acrylic acid / jetylaminoethyl methacrylic acid copolymer, and the like.
  • Nonionic water-soluble polymer compounds include, for example, synthetic polymer compounds such as polyacrylamide, polybutanol, polybutyrrolidone, polyvinylethyl ether, polyethylene glycol, and many other compounds such as hydroxyethyl cellulose, guar gum, dextran, and pullulan. Examples include sugars.
  • polyacrylates acrylic acid / maleic acid copolymer salts, acrylic acid / itaconic acid copolymer salts, alkyl acrylate copolymer salts, and derivatives thereof are most suitable.
  • the weight average molecular weight of the organic water-soluble polymer compound of the present invention is 500 or more, preferably 1,000 to 1,000,000, more preferably ⁇ 1,000 to 200,000.
  • the average molecular weight of polyethylene glycol in the present invention is the average molecular weight described in the Cosmetic Raw Material Standard (2nd edition comment).
  • the weight average molecular weight of the organic water-soluble polymer compound in the present invention is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance.
  • the method for surface-treating the water-soluble alkali inorganic compound with the organic water-soluble polymer compound is not particularly limited. Examples thereof include a method of adding, mixing or coating an organic water-soluble polymer compound to a water-soluble alkali inorganic compound.
  • an organic water-soluble high molecular compound as an aqueous solution for the surface treatment.
  • This aqueous solution is preferably added dropwise or sprayed to the water-soluble alkali inorganic compound in a stirred-fluidized state.
  • the inorganic water-soluble polymer compound is a compound that is uniformly mixed with water at 40 ° C. at a concentration of 0.1 lg or more, preferably 0.2 g or more, more preferably 2 g or more with respect to 100 g of water.
  • Such inorganic water-soluble polymer compound is not particularly limited, and can be used alone or in appropriate combination of two or more.
  • the inorganic water-soluble polymer compound those obtained by subjecting a solution containing a metal alkoxide precursor compound to hydrolysis and polycondensation reaction are preferred, and silicates are particularly preferred.
  • Silicates have long been blended in sarcophagus and have been known as water glass and can be classified according to their anionic form based on their structure (Friedrich Liebau, "Strucctural Chemistry of Silicates p72, 3 ⁇ 4prmg er — Verlag, 1985 Strike Details can be classified by the number of cross-linked oxygen atoms (Si—O—Si) bonded to Si, corresponding to the cross-linked oxygen number forces S4, 3, 2, 1, 0, respectively. It is classified into Q4, Q3, Q2, Ql, and Q0 units (Y. Tsunawaki, N. Iwamoto, T. Hatton and A. Mitsuoishi, J. Non—Cry st. Solids, vol44, p369 (1981)).
  • Silicates contain Q2 units and / or Q3 units from the standpoint of sufficient treatment effects, and Si02 / M20 mole ratio (where M is an alkali metal) is 1.6 to 4, more preferably sodium silicate, more preferably alkali metal silicate having 2 to 3.5.
  • the method for surface-treating the water-soluble alkali-inorganic compound core particles with the inorganic water-soluble polymer compound is not particularly limited. Examples thereof include a method of adding, mixing or coating an inorganic water-soluble polymer compound to water-soluble alkali inorganic compound core particles. It is preferable to use the organic water-soluble polymer compound as an aqueous solution for the surface treatment. This The aqueous solution is preferably added dropwise or sprayed to the water-soluble alkali inorganic compound core particles in a stirred and fluidized state.
  • the poorly water-soluble compound used in the present invention is a compound having a solubility in water at 20 ° C of less than 2 gZl00 g, preferably less than lgZlOOg, more preferably less than 0. Ig / lOOg, and has a water repellency at the initial stage of contact with water. Some are preferable.
  • an organic compound having a melting point of 200 ° C. or less, preferably 0 to 160 ° C., more preferably 20 to 80 ° C., and still more preferably 40 to 60 ° C. is suitable.
  • the poorly water-soluble compounds can be used singly or in appropriate combination of two or more.
  • Examples of the poorly water-soluble compounds include higher fatty acids, dicarboxylic acids, higher alcohols, HLB5 or less, preferably 3 or less higher alcohols or alkylene oxide adducts of higher fatty acids, higher fatty acid esters, higher fatty acid glycerides, and the like.
  • the higher alcohol those having 12 to 22 carbon atoms, more preferably those having a carbon chain length of 14 to 18 carbon atoms, specifically, dodecanol, tetradecanol, hexadecanol, and the like. Octadecanol and the like.
  • a product with an alkylene oxide of a higher alcohol or higher fatty acid having an HLB of 5 or less, preferably 3 or less a 1 to 3 mol ethylene oxide adduct of an alcohol or a fatty acid having 16 to 22 carbon atoms is suitable.
  • Examples include 1 mol ethylene oxide adduct of hexade strength norm, 3 mol ethylene oxide adduct of octadecanol, 1 mol ethylene oxide adduct of palmitic acid, and the like.
  • the higher fatty acid ester methyl ester or ethyl ester such as palmitic acid, myristic acid, stearic acid, arachidic acid, and behenic acid are preferable.
  • As the high-grade fatty acid glyceride mono-, di- or tridalylide such as lauric acid, palmitic acid and stearic acid are suitable.
  • anionic surfactant acid precursor can be used as an anionic surfactant acid precursor. It can be used suitably.
  • Acid precursors for the anionic surfactants include saturated or unsaturated fatty acids (average carbon chain length 8-22), linear or branched alkyl (average carbon chain length 8: 18), benzenesulfonic acid, long chain alkyl (Average carbon chain length 10-20) sulfonic acid, long chain olefin (average carbon chain length 10-20) sulfonic acid, long chain monoalkyl (average carbon chain length 10-20) sulfate ester, polyoxyethylene ( Average degree of polymerization:!
  • Long chain alkyl (average carbon chain length 10 to 20) ether sulfate, polyoxyethylene (average degree of polymerization 3 to 30) alkyl (average carbon chain length 6 to 12) phenyl ether sulfate
  • Examples include monosulfo fatty acids (average carbon chain length of 8 to 22), long-chain monoalkyl, dialkyl or sesquialkyl phosphate, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
  • the anionic surfactant acid precursor is more preferably one having a carbon chain length of 8 to 18 carbon atoms, which is preferable for saturated or unsaturated fatty acids (average carbon chain length of 8 to 22).
  • saturated fatty acids such as force puric acid, lauric acid, myristic acid and palmitic acid, and unsaturated fatty acids such as oleic acid.
  • lauric acid is more preferable from the viewpoint of storage stability, in consideration of manufacturability of saturated fatty acids having 12 to 18 carbon atoms.
  • the method for surface-treating the water-soluble alkali-inorganic compound core particles surface-treated with the first surface-treating agent with the poorly water-soluble compound is not particularly limited.
  • a method of adding, mixing, or coating a poorly water-soluble compound to the surface-treated water-soluble alkali inorganic compound core particles A method in which a poorly water-soluble compound is melted to form a liquid, and this liquid is dropped or sprayed onto the surface-treated water-soluble alkali-inorganic compound core particles in a fluidized state.
  • the water-soluble inorganic compound is preferably used in an amount of 50 to 98 mass% in the surface-treated water-soluble inorganic compound particles, more preferably 70 to 95 mass%. If the amount of water-soluble alkali inorganic compound is less than 50% by mass, it may be insufficient as an alkali agent. On the other hand, if it exceeds 98%, the amount of the treatment agent may be too small and sufficient surface treatment may not be possible. .
  • the organic water-soluble polymer compound is preferably used in an amount of from 0.:! To 10% by mass, particularly from 0.5 to 8% by mass, based on the water-soluble alkali-inorganic compound core particles. 0. Less than 1% by mass, surface The treatment effect may not be obtained, and if it exceeds 10% by mass, the amount of the water-soluble alkaline inorganic compound may be too small.
  • the inorganic water-soluble polymer compound is preferably used in an amount of 1 to 30% by mass, particularly 10 to 28% by mass, based on the surface-treated water-soluble alkali inorganic compound particles. If it is less than 1% by mass, the effect of the surface treatment may not be obtained. If it exceeds 30% by mass, the compounding amount of the inorganic compound may be too small.
  • the poorly water-soluble compound is preferably used in an amount of 0.:! To 10% by mass, particularly 2 to 8% by mass, based on the surface-treated water-soluble alkaline inorganic compound core particles. If the amount is less than 1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the water-soluble alkaline inorganic compound may be too small.
  • the surface-treated water-soluble alkali inorganic compound particles are preferably contained in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the composition. Is preferred. Within such a range, dispersibility at low water temperatures can be greatly improved, which is preferable.
  • the blending ratio of (C) surface-treated water-soluble alkali inorganic compound particles and (B) surfactant-containing particles is (C) particles / (B) particles (mass ratio), preferably 5 / 95-50 / 50 It is preferably 10/90 to 25/75. If the mass ratio exceeds 50/50, the cleaning performance may decrease.
  • the surface-treated water-soluble alkali-inorganic compound particles of the present invention are obtained by treating the water-soluble alkali-inorganic compound core particles with an organic or inorganic water-soluble polymer compound, and further treating the treated surface with a poorly water-soluble compound.
  • the surface of the present invention refers to the surface of primary particles of water-soluble alkali inorganic compound particles or a group of water-soluble alkali inorganic compound particles that are granulated to form about 2 to 30 primary particles. (Including secondary particles or agglomerated particles).
  • the depth of the minute concave portion on the surface is 0.01 to 50 zm.
  • the water-soluble polymer compound and the poorly water-soluble compound are formed on the surface of the water-soluble alkali-inorganic compound core particles. May form a layer, and a poorly water-soluble compound may be present in the outer layer portion or may be in a randomly mixed state. From the viewpoints of solubility and storage stability, it is preferable that more water-insoluble compounds are present in the outermost layer of the surface-treated water-soluble alkali inorganic compound particles than water-soluble polymer compounds. From the viewpoint of manufacturability, it is preferable that more water-soluble polymer compound is present near the surface of the water-soluble alkali-inorganic compound core particles than the poorly water-soluble compound.
  • a particularly preferred structure of the surface-treated water-soluble alkali-inorganic compound particles is a first surface treatment comprising water-soluble alkali-inorganic compound core particles and a water-soluble polymer compound formed on a part or the entire surface of the particle surface. And a second surface treatment portion containing a poorly water-soluble compound formed on a part or the entire surface of the first surface treatment portion.
  • the poorly water-soluble compound is an acid precursor of an anionic surfactant such as a higher fatty acid
  • the water-soluble alkali inorganic salt is usually eluted by the water-soluble polymer aqueous solution in the first surface treatment portion, and the particle surface becomes alkaline. Therefore, the added acid precursor of the anionic surfactant is neutralized on the particle surface. If the amount of the anionic surfactant acid precursor to be added is relatively large, the neutralization reaction does not occur partially, and it may remain in the form of an acid precursor.
  • the neutralization state of the acid precursor of the anionic surfactant can also be examined by differential scanning calorimetry or the like.
  • the acid precursor of the anionic surfactant may be completely neutralized or partially neutralized on the particle surface, it depends on the acid precursor of the anionic surfactant and / or a salt thereof.
  • the second surface treatment portion is formed, in any case, the surface treatment water-soluble alkali inorganic compound particles in the present invention can be suitably used.
  • the first surface treatment section and the second surface treatment section include other components such as a binder, a dispersant, a solubilizer, a pH adjuster, and a poorly water-soluble compound as long as the effects of the present invention are not impaired.
  • Various additives such as an external surfactant are included as appropriate.
  • the content of the surface-treated water-soluble alkali inorganic compound particles is preferably less than 10% by mass, more preferably 5% by mass or less, and even more preferably 1% by mass or less. Fatty acids and the like that are blended as poorly water-soluble compounds are not included in the blending amount of the surfactant in the surface-treated water-soluble alcoholic inorganic compound particles.
  • the physical properties of the (C) surface-treated water-soluble alkali inorganic compound particles of the present invention are not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to : 1.4 g / mL, more preferably 0.6-: 1.3 g / mL. If the bulk density is too small or too large, it may be easily classified when mixed with other particles.
  • the average particle size is preferably f to 200 to 2,000 zm, more preferably f to 300 to 1,500 ⁇ m, and particularly (preferably f to 300 to 500 zm.
  • the average particle size is less than 200 xm. In this case, the specific surface area is too large, and the enzyme activity lowering suppression effect may not be obtained.
  • the angle of repose is preferably 70 ° or less, more preferably 50 ° or less, and if the angle of repose exceeds 70, the handleability of the particles may deteriorate.
  • the particle diameter and bulk density are measured by the measurement method described in the Examples, and the angle of repose is measured by using a turntable type angle of repose measuring instrument manufactured by Tsutsui Rika Instruments Co., Ltd.
  • the water content in the surface-treated water-soluble alkali inorganic compound particles is preferably 8% by mass or less, more preferably 7% by mass or less, and particularly preferably 6% by mass or less.
  • the water content in the present invention is measured by the heat loss method specified in JISK3362-1998.
  • the method for producing surface-treated water-soluble alkali-inorganic compound particles of the present invention includes the following first step and second step.
  • 1st step Adding water-soluble polymer compound aqueous solution to water-soluble alkali-inorganic compound core particles and surface-treating water-soluble alkali-inorganic compound core particles with water-soluble polymer compound 2nd step: Processing in 1st step Adding a poorly water-soluble compound to the water-soluble alkali-inorganic compound core particles, and subjecting the particles to a surface treatment.
  • a water-soluble polymer compound aqueous solution is added to the water-soluble alkali-inorganic compound core particles, and the water-soluble alkali-inorganic compound core particles are surface-treated with the water-soluble polymer compound. It is a process.
  • the water-soluble alkali-inorganic compound core particles are filled in a granulation / coating (coating) apparatus, which will be described later, and a water-soluble polymer compound aqueous solution is added thereto for surface treatment.
  • the water-soluble polymer compound aqueous solution is usually 0.:! To 90% by mass, preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass.
  • An organic water-soluble polymer compound having a viscosity is preferably 0.001 to 100 Pa ⁇ s, more preferably 0.005 to 50 Pa ′s.
  • An aqueous solution is recommended.
  • an inorganic water-soluble polymer compound usually:! To 60% by mass, preferably 5 to 55% by mass, and more preferably 10 to 50% by mass, an inorganic water-soluble polymer compound. It is preferable to drop or spray the water-soluble polymer compound aqueous solution to the water-soluble alkali inorganic compound core particles in a fluidized state.
  • the second step is a step of surface-treating the particles by adding a poorly water-soluble compound to the water-soluble alkali-inorganic compound core particles treated in the first step.
  • the water-soluble alkali-inorganic compound core particles treated in the first step are filled in a granulating / coating apparatus described later, and a poorly water-soluble compound is added thereto for surface treatment.
  • a method in which a poorly water-soluble compound is melted to form a liquid, and this liquid is dropped or sprayed onto the water-soluble alkali-inorganic compound core particles surface-treated in the first step in a stirred and fluidized state is preferred. .
  • examples of the method for specifically granulating and coating the water-soluble alkali inorganic compound core particles include the following methods.
  • Fluidizing water-soluble alkali inorganic compound core particles examples thereof include a fluidized bed granulation method in which a treatment agent or the like is sprayed and granulated.
  • the first step and the second step may be performed by the same granulation and coating method and apparatus, or a plurality of granulation and coating methods and apparatuses may be combined.
  • each method, a manufacturing apparatus, conditions, etc. are demonstrated.
  • the apparatus has a structure in which a stirring shaft provided with a stirring blade is provided in the center and a clearance is formed between the stirring blade and the vessel wall when the stirring blade rotates.
  • the clearance is preferably l-30mm, more preferably 3-10mm.
  • the mixer may be overpowered by the adhesion layer. If it exceeds 30 mm, the compaction efficiency decreases, so the particle size distribution becomes broader, and the granulation time becomes longer, which may reduce productivity.
  • Examples of the agitation granulator having such a structure include, for example, Henshi Kogyo Mixer (Mitsui Miike Chemical Co., Ltd.), High Speed Mixer (Fukae Kogyo Co., Ltd.), and Vertical Granulator (Corporation) And a device such as Norec).
  • a mixer of a horizontal type mixing tank having a stirring shaft at the center of a cylinder and mixing the powder by attaching a stirring blade to this shaft.
  • a mixer for example, Lady Gemixer (manufactured by Matsubo Co., Ltd.) and a professional share-one mixer (manufactured by Taiheiyo Machine Co., Ltd.) are used.
  • Preferable granulation conditions in the stirring granulation method are shown below.
  • the fluid number defined by the following formula is preferably 1 to 16 and more preferably 2 to 9. If the Froude number is less than 1, surface treatment may be insufficient due to insufficient fluidization. On the other hand, if it exceeds 16, the shearing force on the particles becomes too strong, and the surface treatment part may be broken.
  • the agitation granulator used is equipped with a chopper that rotates at a high speed in order to promote compaction of the granulated product and coarse powder crushing.
  • the rotation speed of the chopper is preferably such that the surface treatment portion is not broken.
  • the tipper speed (circumferential speed) is preferably 30 m / s or less, more preferably 0 to 20 m / s or less.
  • the granulation time in batch granulation and the average residence time in continuous granulation are preferably from 0.5 to 20 minutes. preferable. If the granulation time (average residence time) is less than 0.5 minutes, the time is too short and it becomes difficult to control granulation to obtain a suitable average particle size and bulk density, and the particle size distribution becomes broad. There is a case. If it exceeds 20 minutes, the time may be too long and productivity may decrease.
  • the mixing rate (feeding amount) of water-soluble alkali inorganic compound core particles in the granulator is preferably 70% by volume or less of the total internal volume of the mixer. 40% by volume is more preferred. If the filling rate (preparation amount) exceeds 70% by volume, the mixing efficiency in the mixer may decrease, and granulation may not be performed properly.
  • the treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is preferably added dropwise or sprayed to the particles in the stirring / fluid state.
  • agitation is started and granulation / coating operation is also possible.
  • it is preferably added dropwise or sprayed onto the particles in the stirred and flowing state.
  • the drum-type granulator includes horizontal cylindrical granulators, conical drum granulators described in the first edition of the granulation handbook, edited by Japan Powder Industrial Technology Association, multi-stage conical drum granulators, agitation Examples thereof include a drum type granulator with blades.
  • the treatment time in the batch system and the average residence time defined by the following formula in the continuous system are preferably 5 to 120 force S, more preferably 10 to 90 minutes, and still more preferably 10 to 40 minutes.
  • the time is less than 5 minutes, a high bulk density may not be obtained.
  • productivity may be reduced or particles may be collapsed.
  • Tm (m / Q) X 60
  • Tm Average residence time (min)
  • the fluid number defined by the following formula is 0.01-0.8.
  • the number of funades is more preferably 0.05 to 0.7 force S, and more preferably 0.:! To 0.65. If the fanolade number is less than 0.01, uniform and high bulk density particles may not be obtained. On the other hand, if it exceeds 0.8, the particles are scattered in the case of a drum type mixer. Normal shear mixing may not occur.
  • V Peripheral speed (mZs) at the outermost circumference of the rotating container
  • R Radius from the rotation center on the outermost periphery of the container rotating mixer (m)
  • the volume filling rate defined by the following formula is 15 to 50% by volume.
  • the volume filling rate is more preferably 20 to 45% by volume, and further preferably 25 to 40% by volume. If the volume filling rate is less than 15% by volume, the productivity may be poor, whereas if it exceeds 50% by volume, good shear mixing may not occur.
  • volume filling factor (A) (M / p) / VX 100
  • M Amount of water-soluble alkali-inorganic compound core particles charged into the container rotating mixer (g)
  • P Bulk density of water-soluble alkali-inorganic compound core particles (g / U
  • V Volume of container rotation type mixer (L)
  • a treatment agent such as a water-soluble polymer aqueous solution or a poorly water-soluble compound is added by spraying to particles in a rolling-fluid state.
  • agitation is started and granulation / coating operation is possible.
  • it is dripped or sprayed on the agitated / flowing particles. It is preferable to add.
  • any type of fluidized bed granulator composed of a fluidized bed body, current plate, air blower, intake filter, air heater and cooler, spray device, dust collector, etc. can be used.
  • batch-type fluidized bed granulators top spray type, side spray type, bottom spray type, etc.
  • spouted fluidized bed granulators jet fluidized bed granulators, etc.
  • Fluidized bed granulators, semi-continuous fluidized bed granulators disersed plate reverse discharge type, bottom discharge type, side wall discharge type, etc.
  • Continuous fluidized bed granulators horizontal multi-chamber type, cylindrical type, etc. are suitable.
  • the average thickness of the raw material powder layer at the time of standing is preferably about 50 to 500 mm.
  • air is sent to the fluidized bed to fluidize the powder, and then spraying of a treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is started.
  • a treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is started.
  • a treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is started.
  • the spray nozzle it is also preferable to use a two-fluid nozzle in addition to a normal pressure nozzle in order to improve the spray-like body.
  • the average droplet diameter at this time is preferably about 5 to 500 / im.
  • granulation progresses and the particle size increases, so granulation is performed while adjusting the wind speed to maintain the fluidized state.
  • the wind speed is adjusted in the range of 0.2 to 4.
  • Om / s and the wind temperature is 5 to 70 ° C, preferably 7 to 65 ° C. It is preferable to manufacture the fine particles adhering to the bag filter while periodically dropping them with pulsed air.
  • the temperature of the surface-treated water-soluble alkali-inorganic compound particles immediately after the end of the second step is equal to or higher than the melting point of the anionic surfactant acid precursor.
  • the temperature of the water-soluble alkali-inorganic compound core particles treated in the first step is preferable that the temperature of the particles is equal to or higher than the melting point of the poorly water-soluble compound.
  • the temperature of the water-soluble alkali inorganic compound core particles treated in the first step is lower than the melting point of the hardly water-soluble compound.
  • the temperature of the surface-treated water-soluble alkali inorganic compound particles after completion of the surface treatment with the poorly water-soluble compound is equal to or higher than the melting point of the hardly water-soluble compound.
  • the surface-treated water-soluble alkali-inorganic compound particles obtained by the above method may be further surface-treated with an organic or inorganic fine powder.
  • the fine powder for further surface treatment of the surface-treated water-soluble alkali inorganic compound particles include normal temperature solid surfactants, long-chain fatty acid salts, aluminosilicates, oil-absorbing carriers, clay minerals, and the like.
  • the surfactant examples include an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
  • Long-chain fatty acid salts include alkali and non-alkali metal long-chain fatty acid salts, A-type, A-type, P-type, X-type as aluminosilicates, silica, silicate compounds, and spherical porous water as oil-absorbing carriers
  • the clay mineral such as amorphous silicic acid, include montmorillonite, nontronite, gnodelite, pyrophyllite, sabonite, hectorite, stevensite, and talc. These may be used alone or in combination of two or more.
  • Non-alkali metal long-chain fatty acid salts, talc, and aluminosilicates are preferred.
  • Non-alkali metal long-chain fatty acid salts and talc are water-repellent, preventing aggregation of water-soluble alkali inorganic compounds, and aluminosilicates are widely used as Ca capture builders and are mixed when used alone for surface treatment. It serves as a surface treatment agent for detergent particles.
  • the particle diameter of these fine powders is preferably 1/10 or less, more preferably 1/5 or less of the average particle diameter of the surface-treated water-soluble alkali inorganic compound particles. Further, the blending amount of the fine powder is preferably 0 to 10% by mass, more preferably 1 to 8% by mass with respect to the surface-treated water-soluble alkali inorganic compound particles.
  • the surface-treated water-soluble alkali-inorganic compound particles obtained by the above-described method can be classified as required, and only the surface-treated water-soluble alkali-inorganic compound particles having a desired particle size can be used.
  • the classifier a generally known classifier or any other classifier can be used, and a sieve can be particularly preferably used. Of these, a gyro sieve, a flat sieve and a vibrating sieve are suitable.
  • a gyro-type sieve is a sieve that gives a horizontal circular motion to a slightly inclined plane sieve.
  • a plane sieve is a sieve that gives a reciprocating motion to a slightly inclined plane sieve substantially parallel to the surface.
  • a vibrating sieve is a sieve that gives rapid vibration in a direction substantially perpendicular to the sieve surface. It is preferable that the time for sieving is 5 seconds or more. In order to improve the sieving efficiency, it is also preferable to use a tapping ball. Specific examples of such a sieve include a gyro shifter (manufactured by Tokuju Kogakusho Co., Ltd.), a roteckus screener (manufactured by Seishin Enterprise Co., Ltd.), a Dalton vibrating sieve (manufactured by Dalton Co., Ltd.), and the like.
  • the vibration by the sieve is preferably given by 60 to 3,000 times / minute, preferably 100 to 2,500 times / minute, more preferably 150 to 2,000 times / minute. If the frequency of the sieve is less than 60 times / minute, the classification effect may deteriorate, while if it exceeds 3,000 times Z, the dust generation may increase.
  • the fine powder is again charged into the granulator together with the water-soluble alkali inorganic compound core particles and subjected to the granulation and coating operation.
  • the coarse powder is pulverized to the same particle size as that of the water-soluble alkali-inorganic compound before the granulation / coating operation, and then charged again into the granulator together with the water-soluble alkali-inorganic compound core particles. It is suitable to use for coating operation.
  • the powder grinder for pulverizing the coarse powder a model having a classification screen and a rotating blade is preferable.
  • powder mills examples include Fitzmill (manufactured by Hosokawa Micron Corporation), New Speed Mill (manufactured by Seida Okada), and Feather Mill (manufactured by Hosokawa Micron Corporation).
  • Fitzmill manufactured by Hosokawa Micron Corporation
  • New Speed Mill manufactured by Seida Okada
  • Feather Mill manufactured by Hosokawa Micron Corporation
  • it can be pulverized while cooling by flowing cold air into the pulverizer. It is also possible to classify the cold air and the powdered product with a cyclone, and then classify the fine powder.
  • the particle size distribution becomes sharper by multistage grinding.
  • the tip peripheral speed of the powder mill blade is preferably 15 to 90 m / s, more preferably 20 to 80 m / s, and even more preferably 25 to 70 m / s. If the tip peripheral speed is less than 15 m / s, the crushing ability may be insufficient, and if it exceed
  • the third step the surface of the second step
  • the third step it is preferable to include a step of suppressing hydrated crystal growth on the surface of the water-soluble alkali-inorganic compound core particles after the treatment.
  • the smoothness of the surface shape of the surface-treated water-soluble alkali inorganic compound particles should be maintained.
  • hydrated crystals grow, water-soluble alkaline inorganic compound core particles Many irregularities are generated on the surface of the child, the bulk density is lowered, and the angle of repose is increased. In some cases, the hydrated crystals break through the surface treatment, and the hydrated crystals protruding from the nearby surface-treated water-soluble alkali-inorganic compound particles may condense, resulting in strong hydration and consolidation.
  • Examples of the method for suppressing hydrated crystals include [1] a method of cooling the surface-treated particles after the second step, and [2] a method of drying the surface-treated particles after the second step. Among these, from the viewpoint of maintaining good solubility, [1] a cooling method is preferable.
  • the method of cooling the surface-treated particles after the second step is that the surface-treated water-soluble alcoholic inorganic compound particles can be cooled to 30 ° C or lower, preferably 25 ° C or lower. It is not particularly limited.
  • the cooling rate is preferably 5 ° C / hr or more, more preferably 10 ° C / hr or more.
  • the cooling apparatus can be classified into those that cool using a cooled heat transfer surface and those that use airflow.
  • a torus disk manufactured by Hosokawa Micron Co., Ltd.
  • a fright dust status manufactured by Nisshin Engineering Co., Ltd.
  • a fluidized bed can be used as a cooling device by using an air flow.
  • Specific examples of use of the equipment include the Glatt-POWREX series of batch fluidized bed granulators (manufactured by Paulex Co., Ltd.), the flow coater series (manufactured by Dai j11 Hara Manufacturing Co., Ltd.), and the continuous fluidized bed granulator MIXGRAD series (manufactured by Okawara Manufacturing Co., Ltd.).
  • a fluidized bed In view of the possibility that the surface-treated water-soluble alkali-inorganic compound particles are peeled off or broken, it is preferable to use a fluidized bed.
  • the method for drying the surface-treated particles after the second step is not particularly limited as long as the surface-treated water-soluble alcoholic inorganic compound particles can be dried.
  • a similar apparatus used in the above method [1] is obtained by setting the temperature of a heat medium such as a transmission surface or an air flow to 50 to 300 ° C, preferably 60 to 250 ° C. The method of using and drying is mentioned.
  • the granular detergent composition of the present invention can contain components usually contained in a detergent composition for textiles such as clothing as long as the effects of the present invention are not hindered.
  • Specific examples of such components include other enzymes such as protease, bleach particles, bleach activator particles, fragrances, dyes and the like.
  • An optional component similar to the optional component that may be blended in the aforementioned (B) surfactant-containing particles can be included.
  • protease is not particularly limited as long as it is usually used in detergents.
  • Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promelin, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, etc. Is given.
  • protease used in the present invention examples include JP-A 51-8401, JP-A 46-43 551, JP-A 46-42, JP-A ⁇ 9-591, JP-A ⁇ 4- JP 48-2794, JP 50-16435, JP 53-18594, JP 55-46 711, JP 57-42310, JP 58-16200, JP Kaisho 56-24512, JP-A 47-1832, JP-A 52-35758, JP-A 50-34633, JP-B 46-41 596, JP-A 58-134990, JP-A JP 55-14086, JP 51-82833, JP 51-125407, JP 55-39794, JP 46-1840, JP 46-23989, JP 58- Those described in Japanese Patent No.
  • the protease with the detergent composition lg of the present invention from 350 PU to 20,000 PU. More preferably, it is 1,000 PU to: 15,000 PU, and particularly preferably 3,500 PU to: 10,000 PU. Proteases with such a range of activity are preferred because they produce synergistic effects when combined with amylase and increase the cleaning effect against spilled dirt.
  • a normal granulation method such as a granulation method described in JP-A-60-262900 is used. Based on the granulation method, it can be granulated with stabilizers, fillers, extenders, brighteners, binders and coating agents.
  • the amount of protease in the enzyme granulated product is about 0.1 to 10% by mass as the amount of enzyme protein, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. % Is preferred.
  • they may be granulated separately, or the enzymes may be mixed to form the same granulated product.
  • the above examples are not intended to limit the present invention. According to this method, the activity of sabinase 12T, a protease-containing granule from Novozymes, was 700,000 proteaase unit (PU) Zg.
  • Proteases to meet this enzyme activity, 0 in the composition as enzyme protein amount.
  • Amylase protease and the component (A) in the detergent composition is 0.1 as the total amount of enzyme protein amount 006-0. 6 mass 0/0, be especially 0.02 to 0.4 mass 0/0 compounded I like it. If protease and amylase are used in such amounts, the cleaning effect on spilled dirt increases, which is preferable.
  • the ratio of the amount of protease and amylase of component (A) is the mass ratio of the amount of enzyme protein, and protease Z amylase is 1Z5 or more to less than 5Z2, more preferably 1/2 or more to less than 2/1. It is preferable that Protease and Amyler in this ratio It is preferable to use zeta because the cleaning effect against spilled dirt increases.
  • the average particle size is desirably 200 to 700 / im from the viewpoint of stability and solubility.
  • Enzymes which are enzymes that inherently perform enzyme action during the washing process
  • Enzymes include hydrase, oxidoreductases, lyases, transferases, and isomerases from the reactivity of the enzymes.
  • any can be applied to the present invention.
  • Particularly preferred are esterase, lipase, nuclease, cellulase and pectinase.
  • esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase.
  • lipase include commercially available lipases such as ribolase, ribolase ultra, lipex (manufactured by Novozymes), and liposome (manufactured by Showa Denko KK).
  • cellulases include commercially available cellzymes (manufactured by Novozymes), KAC500 (manufactured by Kao Corporation), and cellulases described in claim 4 of JP-A-63-264699. As an enzyme, it is possible to use one or a combination of two or more thereof as appropriate.
  • the enzyme is preferably granulated as a separate stable particle and used in a dry-blended state with a detergent dough (particle).
  • a method for granulating the enzyme-containing particle JP-A-53-6484 JP-A-60-262900, JP-A-62-257990, JP-A-1112983, JP-T 3-503775, JP-A-4 503369, JP-A 2000-178593 Examples include the method described in the publication.
  • the average particle size of the enzyme-containing particles is preferably 200-1, OOO xm, more preferably 300 to 700 ⁇ , from the viewpoint of solubility and storage stability.
  • the bleaching particles are made of hydrogen peroxide or a peroxide that generates hydrogen peroxide when dissolved in water, and usually one or both of sodium percarbonate and sodium perborate are used. In particular, sodium percarbonate is preferred from the viewpoint of stability over time.
  • the chemical compound is used in a form that has been subjected to a treatment such as coating in order to prevent the surface of the particles made of the peroxide from decomposing due to the contact of moisture or other detergent components.
  • Various types of oxygen-based bleaching agents in the form of particles having been coated have been proposed. For example, bleaching particles described in Japanese Patent No. 2918991 can be mentioned.
  • This whitening agent particle is a granulated product obtained by spraying and drying sodium borate particles in a fluidized state separately with an aqueous boric acid solution and an aqueous solution of alkali metal silicate.
  • a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent.
  • the average particle diameter of the coated sodium percarbonate particles is preferably 100 to 2, OOO xm force S, more preferably 200 to 1,000 ⁇ m, even more preferably, from the viewpoint of stability and solubility of the sodium percarbonate particles. Is 300 to 800 zm, and SPC-D manufactured by Mitsubishi Gas Chemical Co., Ltd. can be mentioned as such.
  • the blending amount when the bleaching agent particles are included is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass based on the total amount of the granular detergent composition from the viewpoint of bleaching performance and efficiency.
  • the bleach activator in the bleach activator particles is tetraacetyl ethylenediamine, alkanoyloxybenzene sulfonic acid having 8 to 12 carbon atoms, alkanoyl benzoic acid having 8 to 12 carbon atoms or a salt thereof.
  • alkanoyloxybenzene sulfonic acid having 8 to 12 carbon atoms
  • alkanoyl benzoic acid having 8 to 12 carbon atoms or a salt thereof.
  • 4-decanoyloxybenzoic acid sodium 4-decanoyloxybenzenesulfonate, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred.
  • Bleaching activity ⁇ simultaneous' J is a whitening activator and olefin in a solid binder material heated at room temperature such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000 Surfactant powders such as sulfonates, alkylbenzene sulfonates, alkyl sulfonates, etc.
  • the blending amount of the bleach activator in the granulated product is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the blending amount is out of this range, it may be difficult to obtain a sufficient granulated effect.
  • the blending amount of the binder substance is 0.5 to 30% by mass in the granulated product, preferably 1 to 20% by mass, more preferably 5 to 20% by mass, and the blending amount of the surfactant powder. Is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass in the granulated product.
  • the average particle size of the bleach activator particles is preferably 200 to 1,500 zm, more preferably f to 300 to 1,000 zm from the viewpoint of solubility and storage stability.
  • the blending amount is preferably 0.3: to 15% by mass, particularly preferably 0.3 to 10% by mass, based on the total amount of the granular detergent composition.
  • (C) Surface-treated water-soluble alkali inorganic compound particles, (B) surfactant-containing particles, enzyme-containing particles, bleaching agent particles, and bleaching activator particles are used after the surface is colored with a dye or pigment. I can do it. At this time, dyes and pigments used for coloring should be those that do not stain clothes. Examples of such dyes and pigments include ultramarine, coranyldarin CG-130 (CI number: 74260), food dye red No. 102, and acid dye Acid Yellow 141.
  • These dyes and pigments are made into an aqueous solution or dispersion, and then the particles are stirred and rolled in the same agitation granulator or tumbling granulator as the granulating apparatus for (B) surfactant-containing particles.
  • it can color by adding.
  • the particles can be colored by spraying the aqueous solution or dispersion on the particles while the particles are transported by a belt conveyor.
  • the coloring amount is preferably 0.001 to 1% by mass with respect to the particles to be colored.
  • the fragrance may be mixed with either (C) surface-treated water-soluble alkali inorganic compound particles or (B) surfactant-containing particles, and then mixed.
  • the fragrance used components described in JP-A-2002-146399 and JP-A-2003-89800 can be used.
  • the fragrance is a mixture comprising a fragrance component, a solvent, a fragrance stabilizer, and the like.
  • blending of perfume The amount is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass.
  • flavor is not limited to the fragrance
  • the granular detergent composition of the present invention can be produced by mixing the components (A) to (C).
  • dry mixing is preferably used. Any mixer may be used as long as various particles can be sufficiently mixed.
  • a horizontal cylinder type, double cone type, V type, rotation / revolution type, or the like can be suitably used.
  • a horizontal cylindrical type or a double cone type is used, and mixing is performed at a temperature of 0 to 50 ° C. and an Fr number of 0.01 to 0.2 (the calculation formula is as described above).
  • the order of addition of various particles and other components is not particularly limited.
  • the ratio (Zl) Z (B1) of the average particle diameter of the surface-treated water-soluble alkali inorganic compound particles and the surfactant-containing particles is preferable. Or 0.5 to 2, more preferably 0.5 to 1.5, and even more preferably 0.6 to 1.3.
  • _tt (Z2) / (B2) of the bulk density of the surface-treated surface-treated water-soluble alkali inorganic compound particles and the surfactant-containing particles is preferably 0.5 to 2, more preferably 0.6 to 1 .5, and more preferably 0.7-7:!
  • the physical property value of the granular detergent composition of the present invention is not particularly limited, but the water content is preferably 10% by mass or less, more preferably 4 to 4% from the viewpoint of solubility and storage stability. It is 9 mass%, More preferably, it is 5-8 mass%.
  • the bulk density is usually 0.3 g / mL or more, preferably 0.5 to: 1.2 g / mL, more preferably 0.6 to: 1. lg / mL.
  • the average particle diameter is preferably 200 to 1,500 111, more preferably 250 to 1,000 ⁇ m, and even more preferably 280 to 700 ⁇ m. When the average particle size is less than 200 ⁇ m, dust is likely to be generated and the handling property may be deteriorated.
  • the fluidity of the granular detergent composition is preferably 60 ° or less, particularly 50 ° or less as the angle of repose. Furthermore, after storage (when the moisture permeability is high in a paper container or when stored in a container for a long time, etc.), the fluidity is preferably 60 ° or less, more preferably 50 ° or less as the angle of repose. From the point of view, it is preferable.
  • the granular detergent composition of the present invention can be filled into a suitable container to form a granular detergent article in a container.
  • the container material has a water vapor transmission rate of 30gZm2 '24 hours (in terms of storage stability) 40g, 90% RH) or less is preferred 25g / m2 '24 hours (40 ° C, 90% RH) or less is more preferred. These can be achieved by a combination of general packaging materials and changes in thickness.
  • the moisture permeability in the present invention is measured by the method specified in JIS Z0208-1976.
  • the granular detergent composition of the present invention can be used as a compression molding detergent such as a tablet detergent or a pricket detergent after being further mixed with a disintegrant and then compression molded.
  • composition of the present invention include the following:
  • the surfactant content is 20 to 40% by mass, and as the surfactant, LAS having an alkyl group having 10 to 14 carbon atoms, higher fatty acid having 10 to 20 carbon atoms, 12 to 28 carbon atoms -SF and an interface containing at least one selected from the group consisting of polyoxyalkylene alkyl ethers obtained by adding 5 to 20 moles of ethylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms on average.
  • Activator-containing particles 75-90% by weight, and
  • (C) Sodium carbonate is used as the core particle of the water-soluble alkali-inorganic compound, and the polyacrylic acid salt, acrylic acid / maleic acid copolymer salt, acrylic acid / itaconic acid copolymer salt, and alkyl acrylate are used as the first surface treatment agent. It can be obtained by surface-treating using one selected from the group consisting of copolymer salts, and surface-treating the obtained particles with a saturated fatty acid having 12 to 18 carbon atoms as a second surface-treating agent. Surface-treated water-soluble alkaline inorganic compound particles: 10-20% by mass
  • the viscosity reduction rate was calculated according to the above-described formula (1).
  • surfactant-containing particles bl were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this was added _SF_Na, a surfactant excluding the nonionic surfactant, and PEG # 6000, and the mixture was stirred for 10 minutes. Subsequently, MA1 (acrylic acid Z maleic acid copolymer sodium salt) and a fluorescent agent were added. After stirring for another 10 minutes, a part of the powder A-type zeolite (except for 2.0% equivalent amount (vs.
  • a water slurry of _SF_Na obtained by sulfonating and neutralizing the fatty acid ester of the raw material (water concentration 25%) is mixed with a part of nonionic surfactant (2% of _SF_Na). 5%) was added, and the mixture was concentrated under reduced pressure with a thin-film dryer until the moisture content became 11% to obtain a mixed concentrate of a-SF-Na and a nonionic surfactant.
  • This surfactant-containing kneaded material is extruded with a pelleter double (Nippadar Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm and cut with a cutter (cutter peripheral speed is 5 m / s) )
  • a pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
  • Surfactant-containing particles b2 were obtained in the same manner as the method for preparing the surfactant-containing particles bl. With respect to the obtained surfactant-containing particles bl and b2, the average particle diameter and bulk density were measured by the methods described later. The results are also shown in Table 1.
  • the detergent compositions shown in Table 2 were prepared by the following procedure.
  • This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C, reduced for 2 hours) is 3%, the bulk density is 0.50 g / mL, and the average particle size Gave 250 m spray-dried particles.
  • a nonionic surfactant and a ionic surfactant were added under mixing at 80 ° C. to prepare a surfactant composition having a water content of 10% by mass.
  • the average particle diameter and bulk density were measured by the method described later.
  • a water-soluble inorganic compound is loaded into a professional share-one mixer (Daiheiyo Co., Ltd.) equipped with a blade-shaped excavator with a shovel-wall clearance of 5 mm. and (filling rate 30% by volume), and stirring was started at spindle 150 r P m. (chopper rpm: 1015Rpm, blade tip speed (peripheral speed):.
  • the obtained particles are packed into a fluidized bed (Glatt_POWREX, model number FD_WRT_20, manufactured by Paulex Co., Ltd.). After filling, 15 ° C air (air) is sent into the fluidized bed to cool the particles. To obtain particles cooled to 20 ° C. The wind speed in the fluidized bed was adjusted in the range of 0.2 to 10. Om / s while confirming the fluidization state. The obtained particles were classified using a sieve having a mesh opening of 2,000 ⁇ m to obtain surface-treated water-soluble alkaline inorganic compound particles that passed through a sieve having a mesh opening of 2,000 ⁇ . With respect to the obtained surface-treated alkali inorganic compound particles al, a2, and a3, the average particle diameter and bulk density were measured by the methods described later. The results are also shown in Table 3.
  • the mixed particles were obtained by modification.
  • the particles are transferred on a belt conveyor at a speed of 0.5 mZs (surfactant-containing particle layer on belt conveyor is 30 mm high and layer width is 300 mm).
  • a 20% aqueous dispersion of the dye was sprayed on the surface to obtain a granular detergent composition having the composition shown in Tables 4 and 5.
  • R is a reflectance measured using a color meter ⁇ -9000 made by Nippon Denshoku. The reflectance was measured using a 460 nm filter. The washing rate was evaluated based on the average value of 10 test cloths.
  • Each sampnore and its combination (tread, 1, 680 zm, 1, 410 xm, 1, 190 zm, 1,000 Atm, 710 xm, 500 xm, 350 xm, 250 xm, 149 xm, 9
  • the classification was performed using a plate and a tray, and the classification was carried out in the order of a sieve with a small opening and a sieve with a large opening, and lOOgZ times from the top of the top 1 680 xm sieve.
  • the bulk density was measured according to JIS K3362-1998.
  • MA1 Acrylic / maleic acid copolymer sodium salt, Aquaric TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
  • PEG # 6000 Polyethylene glycol manufactured by Lion Co., Ltd., trade name PEG # 6000M • PA: Sodium polyacrylate, trade name Socaran PA30 (BASF)
  • Type A zeolite Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure)
  • LAS -K Linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Laipon LH-200 (manufactured by Lion Corporation) LAS—96% pure) 48% hydroxylated during preparation of surfactant composition Neutralize with aqueous potassium).
  • the compounding amounts in Table 1 indicate mass% as LAS-K.
  • LAS-Na Linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Laipon LH—20 0 (manufactured by Lion Corporation) LAS _H pure 96%) 48% hydroxylated during preparation of surfactant composition Neutralize with aqueous sodium).
  • the blending amount in Table 2 indicates mass% as LAS_Na.
  • AOS—K Potassium monoolefin sulfonate having an alkyl group with 14 to 18 carbon atoms (manufactured by Lion Corporation)
  • Nonionic surfactant A EC ⁇ R ⁇ L26 (ECOGREEN Co., Ltd., 12 to 16 alcohols with 16 alkyl groups) ethylene oxide average 15 mol adduct (pure 90%)
  • Nonionic surfactant B ECOROL26 (ECOGREEN Co., Ltd., an alcohol with 12 to 16 carbon atoms) An average of 6 moles of ethylene oxide adduct (pure 90%)
  • Dye B Pigment Green 7 (Daiichi Seika Kogyo)
  • 'Dye C Containing monomers of acrylonitrile / styrene / acrylic acid, into spherical resin particles with an average particle size of 0.35 xm obtained by radical emulsion polymerization in an aqueous dispersion, about 1% of resin content An aqueous dispersion of pink fluorescent pigment obtained by adding CI BASIC RED-1 to the polymer resin suspension and heat-treating it.
  • Amylase A Stinzym 12T (manufactured by Novozymes)
  • Amylase B Termaminole 120T (Novozymes)
  • Amylase C Deyuramil 120T (Novozymes)
  • FIG. 1 is a graph showing changes in viscosity over time for three types of amylases (Termamyl, Deyuramil, and Stinzym).

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Abstract

Disclosed is a granular detergent composition containing the following components: (A) an amylase having a viscosity reduction rate of not less than 40% which is calculated by the formula (1) below; (B) surfactant-containing particles containing 10-50% by mass of a surfactant; and (C) surface-treated water-soluble alkaline inorganic compound particles obtained by surface-treating a water-soluble alkaline inorganic compound with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound wherein the water-soluble alkaline inorganic compound content is 50-98% by mass. This granular detergent composition exhibits high performance in removing food stains even in normal washing using a washing machine.

Description

明 細 書  Specification
アミラーゼ含有粒状洗剤組成物  Amylase-containing granular detergent composition
技術分野  Technical field
[0001] 本発明は、衣類等の繊維製品に用いる粒状洗剤組成物に関し、詳しくは、食べこ ぼし汚れ効果の高い特定のアミラーゼを含有する粒状洗剤組成物に関する。  TECHNICAL FIELD [0001] The present invention relates to a granular detergent composition used for textile products such as clothing, and more particularly to a granular detergent composition containing a specific amylase having a high effect of spilling dirt.
背景技術  Background art
[0002] 食事中に食べ物を衣類等に落としてしまうことにより生じる食べこぼし汚れは、色素 や油脂成分等の種々の成分によって発生するため、洗濯機を用いて行う通常の洗 濯によって除去することは困難である。このため、高濃度の洗濯液を汚れに塗布して 、予め洗濯する等の前処理が必要であった。  [0002] Since food spillage stains caused by dropping food into clothing during meals are generated by various components such as pigments and oils and fats, they must be removed by ordinary washing using a washing machine. It is difficult. For this reason, a pretreatment such as applying a high-concentration washing liquid to the soil and washing in advance is necessary.
従って、このような前処理をしなくても食べこぼし汚れを効果的に除去できる粒状洗 剤組成物が望まれていた。  Therefore, there has been a demand for a granular detergent composition that can effectively remove spilled dirt without such pretreatment.
これまでに、アミラーゼと特定の構造を有する漂白活性化剤とを併有する漂白洗浄 剤組成物やアミラーゼと特定のビルダーとを併有する洗剤組成物（特許文献 1、 2)が 知られているが、食べこぼし汚れに対して満足な洗浄効果が得られなかった。  So far, there have been known a bleaching detergent composition containing both amylase and a bleach activator having a specific structure, and a detergent composition containing both amylase and a specific builder (Patent Documents 1 and 2). A satisfactory cleaning effect against spilled dirt was not obtained.
[0003] 特許文献 1 :特開平 10— 95996号公報  Patent Document 1: Japanese Patent Laid-Open No. 10-95996
特許文献 2：特表平 11 - 507989号公報  Patent Document 2: Japanese Patent Publication No. 11-507989
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明は、上記事情に鑑み、洗濯機を用いる通常の洗濯においても食べこぼし汚 れ除去に効果の高い粒状洗剤組成物を提供することを目的とする。 [0004] In view of the above circumstances, an object of the present invention is to provide a granular detergent composition that is highly effective in removing spilled dirt even in normal washing using a washing machine.
課題を解決するための手段  Means for solving the problem
[0005] 本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、特定のアミラーゼと 、表面処理した水溶性アルカリ無機化合物粒子及び界面活性剤含有粒子とを併用 することにより上記目的を達成しうることを見出し、本発明を完成することに至った。す なわち、本発明は、以下の成分を含有することを特徴とする粒状洗剤組成物を提供 する： (A)以下の式（1)により算出される粘度低減率が 40%以上であるアミラーゼ、[0005] As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the above-mentioned object by combining a specific amylase with surface-treated water-soluble alkali inorganic compound particles and surfactant-containing particles. The present invention has been found to be able to be achieved. That is, the present invention provides a granular detergent composition characterized by containing the following components: (A) an amylase having a viscosity reduction rate calculated by the following formula (1) of 40% or more,
(B) 10〜50質量％の界面活性剤を含有する界面活性剤含有粒子、及び (B) a surfactant-containing particle containing 10 to 50% by mass of a surfactant, and
(C)水溶性アルカリ無機化合物を、有機又は無機水溶性高分子化合物と水難溶性 化合物とで表面処理してなり、水溶性アル力リ無機化合物の含有量が 50〜 98質量 %である、  (C) A water-soluble alkaline inorganic compound is surface-treated with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound, and the content of the water-soluble alkaline compound is 50 to 98% by mass.
表面処理した水溶性アル力リ無機化合物粒子。  Surface-treated water-soluble alcoholic inorganic compound particles.
[0006] [数 1] [0006] [Equation 1]
(初期粘度） 一 （6 0分後の粘度） (Initial viscosity) I (Viscosity after 60 minutes)
粘度低減率 （％) = x 0 0 ( 1 ) Viscosity reduction rate (%) = x 0 0 ( 1 )
(初期粘度） 発明の効果  (Initial viscosity) Effect of the invention
[0007] 本発明において、活性の高い特定のアミラーゼを使用し、かつその表面積が一定 範囲被覆処理されているアルカリビルダー含有粒子と界面活性剤含有粒子とを併用 することにより、食べこぼし汚れを、効果的に、簡便に除去することができる。本発明 によればまた、衣類等に損傷を与えることなく食べこぼし汚れを除去することができる 。本発明の組成物はまた、水への溶解性に優れる。  [0007] In the present invention, by using a specific amylase having a high activity and a combination of alkali builder-containing particles and surfactant-containing particles whose surface area is coated in a certain range, Effectively and easily removed. According to the present invention, it is also possible to remove spilled dirt without damaging clothes or the like. The composition of the present invention is also excellent in solubility in water.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] (A)成分 [0008] Component (A)
本発明の (A)成分は、上述した式（1)により算出される粘度低減率が 40%以上で あるアミラーゼである。  The component (A) of the present invention is an amylase having a viscosity reduction rate calculated by the above formula (1) of 40% or more.
詳細には、とうもろこし澱粉（関東化学 (株)製） 25gを 90± 2°Cのアルカリ（炭酸ナト リウム 4000ppm)水溶液 475gに添加、 1時間 90± 2°Cで攪拌溶解した後、 5°Cにて 12時間冷却する。その後、室温にて放置し、該溶液の温度が室温と等しくなつた後、 25°Cに調温する。次いで、 25°Cに調温した該溶液 40gの粘度 (mPa' s)を振動式粘 度計 (株式会社エー ·アンド ·ディ製 CJV5000、振動子の材質：ステンレス鋼 SUS30 4— CSP— H、振動子の形状及び大きさ：円盤状、 t (厚さ） =0. lmm、 φ (直径） = 13mm)にて測定し、初期粘度とする（測定条件:設定振幅値 50mV、振動周波数: 3 0Hz、試料量: 40g (5%水溶液として）、測定温度：25°C)。その後初期粘度を測定 したデンプン水溶液 40gに対してアミラーゼを酵素タンパク量として 0. 004mgを素 早く添加'撹拌し、添加後 10秒後に粘度を初期粘度と同様に測定し、その後 25°Cで 調温する。次いで 10分後、 30分後、 60分後に粘度を初期粘度と同様に測定する。 得られた初期粘度と 60分後の粘度の値を上述の式（1)に代入することにより、粘度 低減率（％)を算出すること力できる。 Specifically, corn starch (manufactured by Kanto Chemical Co., Inc.) 25g was added to 475g of 90 ± 2 ° C alkali (sodium carbonate 4000ppm) aqueous solution, stirred and dissolved at 90 ± 2 ° C for 1 hour, then 5 ° C Cool for 12 hours. Then, it is allowed to stand at room temperature. After the temperature of the solution becomes equal to room temperature, the temperature is adjusted to 25 ° C. Next, the viscosity (mPa's) of 40 g of the solution adjusted to 25 ° C was measured using a vibratory viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS30 4—CSP—H, The shape and size of the vibrator: disk shape, measured at t (thickness) = 0.1 mm, φ (diameter) = 13 mm) and set as initial viscosity (measurement condition: set amplitude value 50 mV, vibration frequency: 3 0Hz, sample amount: 40g (as 5% aqueous solution), measuring temperature: 25 ° C). Then measure the initial viscosity Add 0.004 mg of amylase as enzyme protein to 40 g of the starch aqueous solution quickly and stir. After 10 seconds, add the viscosity, measure the viscosity in the same way as the initial viscosity, and adjust the temperature at 25 ° C. Then, after 10 minutes, 30 minutes and 60 minutes, the viscosity is measured in the same manner as the initial viscosity. By substituting the obtained initial viscosity and the viscosity value after 60 minutes into the above formula (1), it is possible to calculate the viscosity reduction rate (%).
上記特定の粘度低減率を満足するアミラーゼは、上述した市販の装置 (株式会社 エー ·アンド ·ディ製 CJV5000)を用レ、た簡便なスクリーニング法により、適宜選択す ること力 Sできる。  Amylase satisfying the specific viscosity reduction rate can be appropriately selected by a simple screening method using the above-described commercially available apparatus (CJV5000 manufactured by A & D Co., Ltd.).
[0009] 本発明で使用できるアミラーゼとしては、デンプンゃグリコーゲンなどのひ一1 , 4結 合を加水分解するひ一アミラーゼ、 β—アミラーゼ、 ひ一ダルコシターゼ、ダルコアミ ラーゼとデンプンゃグリコーゲンなどのひ一 1 , 6結合を加水分解するダルコアミラー ゼ、プルラナーゼ、イソアミラーゼ、アミ口一1 , 6ダルコシターゼ Ζ4—ひグルカノトラ ンスフェラーゼ、ォリゴー 1 , 6—ダルコシターゼなどが含まれる。でんぷんを加水分 解する酵素であれば特に限定されず、 1種類または 2種類以上を組み合わせて使用 できる。  [0009] Examples of amylases that can be used in the present invention include amylase that hydrolyzes 1,4 bonds such as starch, glycogen and the like, β-amylase, dialcarcase, darcoamylase, and starch glucoside. Examples include dalcore amylase, pullulanase, isoamylase, amiguchi 1,6-dalcositase Ζ4-hyglucanotransferase, origo 1,6-dalcosidase, etc. that hydrolyze 1, 6 bonds. The enzyme is not particularly limited as long as it is an enzyme that hydrolyzes starch, and can be used alone or in combination of two or more.
本発明で使用できるアミラーゼを以下に例示する。し力しながら、以下の例示は本 発明を限定するものではない。入手可能な市販酵素としては、以下の物が例示され る。ターマミノレ（Termamyl)、ァユラミノレ (Duramyl)、ステインサィム (Stainzyme)、 プロモザィム（Promozyme) 200L (以上、ノボザィムズ社製）、マキサミル（Maxamy 1) (ジヱネンコア社製）、天野製薬社のプルラナーゼアマ入 DB— 250、 Aerobacter aerogenes ATCC9621由来のプルラナーゼ（クルードまたは結晶化品が生化学 工業社より発売)。  Examples of amylases that can be used in the present invention are given below. However, the following examples do not limit the present invention. Examples of commercially available enzymes that can be obtained include the following. Termamyl, Dyamyl, Stainzyme, Promozyme 200L (above, Novozymes), Maxamy 1 (Geneencore), Amano Pharmaceutical's pullulanase ama DB-250, Pullulanase derived from Aerobacter aerogenes ATCC9621 (crude or crystallized product released by Seikagaku Corporation).
[0010] 上記アミラーゼの他、特許掲載公報に記載のアミラーゼとして、以下のものが例示 される。  [0010] In addition to the amylase described above, examples of the amylase described in the patent publication include the following.
(1)特開昭 48— 91271号公報記載のバチルス属起源のアルカリアミラーゼ  (1) Alkaline amylase of the genus Bacillus described in JP-A-48-91271
(2)特開昭 61— 209588号公報記載のストレプトマイセス属起源のアルカリアミラー ゼ  (2) Alkaline amylase of the genus Streptomyces described in JP-A-61-209588
(3)特開昭 62— 208278号公報記載のバチルス属起源のアルカリアミラーゼ (4)特開平 2— 49584号公報記載のバチルス属起源のアルカリアミラーゼ (3) Alkaline amylase of the genus Bacillus described in JP-A-62-208278 (4) Alkaline amylase of the genus Bacillus described in JP-A-2-49584
(5)特開平 3— 87176号公報記載のバチルス属起源のアルカリプノレラナ一ゼ (5) Alkaline punorellanase of the genus Bacillus described in JP-A-3-87176
(6)特開平 3— 87177号公報記載のバチルス属起源のアルカリプノレラナ一ゼ(6) Alkaline Pnoleranase derived from the genus Bacillus described in JP-A-3-87177
(7)特開平 3 _ 103177号公報記載のバチルス属起源のアミラーゼ (7) Amylase of the genus Bacillus described in JP-A-3-103177
(8)特開平 3 _ 108482号公報記載のバチルス属起源のアルカリアミラーゼ (8) Alkaline amylase of the genus Bacillus described in JP-A-3-108482
(9)特開平 4_ 23983号公報記載のバチルス属起源のアルカリアミラーゼ (9) Alkaline amylase of the genus Bacillus described in JP-A-4-23983
(10)特開平 4_ 58885号公報記載のバチルス属起源のアルカリアミラーゼ  (10) Alkaline amylase of the genus Bacillus described in JP-A-4-58885
[0011] (11)特開平 4— 211369号公報記載のナトロノコッカス属起源のアルカリアミラー ゼ [0011] (11) Alkaline amylase of the genus Natronococcus described in JP-A-4-211369
(12)特表平 4— 500756号公報記載のバチルス属起源のひ—アミラーゼ  (12) Hyoamylase of the genus Bacillus described in Japanese Patent Publication No. 4-500756
(13)特開平 6 _ 14775号公報記載のバチルス属起源のアルカリイソアミラーゼ (13) Alkaline isoamylase of the genus Bacillus described in JP-A-6-14775
(14)特開平 8— 56662号公報記載のバチルス属起源のアルカリアミラーゼ(14) Alkaline amylase of the genus Bacillus described in JP-A-8-56662
(15)特開平 9— 206073号公報記載のバチルス属起源のアルカリ α—アミラーゼ(15) Alkaline α-amylase of the genus Bacillus described in JP-A-9-206073
(16)特表平 10— 504197号公報記載の α—アミラーゼ変異体 (16) α-Amylase variant described in JP-T-10-504197
(17)特開 2000— 023665号公報記載のアルカリアミラーゼ  (17) Alkaline amylase described in JP-A-2000-0223665
(18)特開 2000— 023666号公報記載のアルカリアミラーゼ  (18) Alkaline amylase described in JP-A-2000-023666
(19)特開 2000— 023667号公報記載のアルカリアミラーゼ  (19) Alkaline amylase described in JP 2000-023667 A
(20)特開 2002— 112792号公報記載の変異 α—アミラーゼ  (20) Mutant α-amylase described in JP-A-2002-112792
[0012] (21)特表平 4— 503757号公報記載のピロコッカス属起源の α—アミラーゼ  [21] (21) α-Amylase of the genus Pyrococcus described in JP-T-4-503757
(22)特表平 8— 500243号公報記載のバチルス属起源の α—アミラーゼ  (22) α-amylase of the genus Bacillus described in JP-T 8-500243
(23)特表平 8— 504586号公報記載のバチルス属又はァスパラギルス属起源の α アミラーゼ  (23) α-amylase of the genus Bacillus or Asparagillus described in JP-T 8-504586
(24)特表平 8— 506731号公報記載のピロコッカス属等起源のデンプン分解酵素 (24) Starch-degrading enzyme of the genus Pyrococcus described in JP-T-8-506731
(25)特表平 9— 503916号公報記載のバチルス属起源のひ—アミラーゼ (25) A amylase of the genus Bacillus described in JP-T 9-503916
(26)特表平 9 - 510617号公報記載のバチルス属起源のひ -アミラーゼ  (26) Saccharomyces-amylase of the genus Bacillus described in JP-T 9-510617
(27)特表 2001— 520006号公報記載のひ一アミラーゼ変異体  (27) One amylase variant described in JP-T-2001-520006
(28)特表 2001 _ 521739号公報記載のひ—アミラーゼ変異体 (29)特表 2002— 504323号公報記載のアルカリ性バチルスアミラーゼ (28) A amylase variant described in JP 2001-521739 A (29) Alkaline Bacillus amylase described in JP-T-2002-504323
(30)特表 2002— 530072号公報記載の α—アミラーゼ変異体  (30) α-Amylase mutant described in JP-T 2002-530072
(31)特表 2002— 540785号公報記載の α—アミラーゼ変異体  (31) α-Amylase variant described in JP-T-2002-540785
(32)特表 2003— 507059号公報記載のアルカリバチルスアミラーゼ  (32) Alkaline Bacillus amylase described in JP-T-2003-507059
(33)特表 2004— 508815号公報記載のひ—アミラーゼ突然変異体  (33) A amylase mutant described in JP 2004-508815 A
これらのアミラーゼは単独で使用することもできるし、 2種以上を併用することもでき る。 2種以上を併用する場合、個々のアミラーゼについての粘度低減率が 40%未満 であっても、併用したときの粘度低減率が 40%以上であるならば、本発明の (Α)成 分として使用すること力 Sできる。本発明の (Α)成分としては、粘度低減率が 70%以上 のアミラーゼが好ましぐ 80%以上のアミラーゼがより好ましい。如何なる理論にも拘 束されるものではなレ、が、アミラーゼの粘度低減率が 40%以上であると、衣類と汚れ の付着力を弱めることができるので、食べこぼし汚れに対して高い除去効果を発揮 するものと考えられる。粘度低減効果の高い起源のアミラーゼを選定するカ あるい は粘度低減効果が高くなるように変異させたアミラーゼを選定することにより、アミラー ゼの粘度低減率を上昇させることができる。特に、上記特許掲載公報（21)〜（33)に 記載のアミラーゼが好ましい。更に特に、スティンザィムが好ましい。  These amylases can be used alone or in combination of two or more. When two or more types are used in combination, even if the viscosity reduction rate for each amylase is less than 40%, if the viscosity reduction rate when used in combination is 40% or more, the (v) component of the present invention Power S to use. As the component (ii) of the present invention, an amylase having a viscosity reduction rate of 70% or more is preferable, and an amylase having 80% or more is more preferable. It is not bound by any theory, but when the viscosity reduction rate of amylase is 40% or more, the adhesion between clothes and dirt can be weakened, so it has a high removal effect against spilled dirt. It is considered that The viscosity reduction rate of amylase can be increased by selecting an amylase having a high viscosity reduction effect or by selecting an amylase mutated to increase the viscosity reduction effect. In particular, the amylases described in the above patent publications (21) to (33) are preferred. More particularly, stinzym is preferable.
アミラーゼは、通常の造粒法に基づき、安定剤、フィラー、増量剤、増白剤、バイン ダー及びコーティング剤等との造粒物として使用するのが好ましい。安定性及び水 への溶解性に優れるためである。安定性及び水への溶解性の面から、後述する実施 例に記載の方法で測定される平均粒子径が 200〜700 μ mであるのが望ましい。な お、 2種以上の酵素の造粒に際しては別々に造粒してもよいし、酵素を混合し、同一 造粒物としてもよい。通常、酵素造粒物中のアミラーゼの配合量としては、酵素タンパ ク量として 0. 1〜： 10質量％程度であり、好ましくは 0. 5〜5質量％、より好ましくは 1 〜3質量％である。酵素含有粒子の造粒方法としては、特開昭 53— 6484号公報、 特開昭 60— 262900号公報、特開昭 62— 257990号公報、特開平 1— 112983号 公報、特表平 3— 503775号公報、特表平 4— 503369号公報、特開 2000— 1785 93号公報記載の方法等が挙げられる。  Amylase is preferably used as a granulated product with stabilizers, fillers, extenders, brighteners, binders, coating agents, and the like, based on ordinary granulation methods. This is because of excellent stability and solubility in water. From the viewpoint of stability and solubility in water, it is desirable that the average particle size measured by the method described in the examples described later is 200 to 700 μm. In addition, when two or more kinds of enzymes are granulated, they may be granulated separately, or the enzymes may be mixed to form the same granulated product. Usually, the amount of amylase in the enzyme granulated product is about 0.1 to 10% by mass as the enzyme protein, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. It is. As methods for granulating enzyme-containing particles, JP-A-53-6484, JP-A-60-262900, JP-A-62-257990, JP-A-1-112983, JP-T-3- Examples include the methods described in Japanese Patent No. 503775, Japanese Patent Publication No. 4-503369, Japanese Patent Laid-Open No. 2000-178593.
本発明の組成物において、 （A)アミラーゼは、組成物の全量を基準として、酵素タ ンパク量として好ましくは 0. 001質量％以上、より好ましくは 0. 002質量％以上、特 に好ましくは 0. 003質量％以上であって、好ましくは 0. 05質量％以下、より好ましく は 0. 03質量％以下、特に好ましくは 0. 02質量％以下の量で含まれるのが好ましい 。 0. 001質量％より少ない場合には本発明の効果が小さくなる場合があり、 0. 05質 量％より多い場合には効果が頭打ちとなってしまう場合がある。 In the composition of the present invention, (A) amylase is an enzyme tag based on the total amount of the composition. The amount of the protein is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, particularly preferably 0.003% by mass or more, preferably 0.05% by mass or less, more preferably 0.00%. It is preferably contained in an amount of 03% by mass or less, particularly preferably 0.02% by mass or less. When the amount is less than 001% by mass, the effect of the present invention may be reduced. When the amount is more than 0.05% by mass, the effect may reach a peak.
なお、洗浄剤組成物中の酵素タンパク量の定量は、必要に応じて塩析法、沈殿法 、限外濾過法等の分離手段により粗酵素を得た後、公知の方法により精製結晶化す る力 \あるいは SDS—ポリアクリルアミドゲル電気泳動で形成されるバンドを公知の染 色法によって染色し、染色の程度を既知の酵素精製品と比較することにより可能であ る。  The amount of enzyme protein in the detergent composition is determined by obtaining a crude enzyme by a separation means such as a salting-out method, a precipitation method, or an ultrafiltration method, if necessary, followed by purification and crystallization by a known method. It is possible to stain the band formed by force- or SDS-polyacrylamide gel electrophoresis by a known staining method and compare the degree of staining with a known enzyme purified product.
[0014] (B)成分  [0014] Component (B)
本発明の（B)成分は、 10〜50質量％の界面活性剤を含有する界面活性剤含有 粒子である。  The component (B) of the present invention is a surfactant-containing particle containing 10 to 50% by mass of a surfactant.
<界面活性剤 >  <Surfactant>
界面活性剤含有粒子に用いられる界面活性剤としては、ァニオン界面活性剤、ノ 二オン界面活性剤、カチオン界面活性剤及び両性界面活性剤が挙げられ、これらを 1種単独で又は 2種以上を適宜組み合わせて用いることができる。  Examples of the surfactant used in the surfactant-containing particles include an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. These may be used alone or in combination of two or more. They can be used in appropriate combinations.
(B)界面活性剤含有粒子中の界面活性剤は、洗浄性能の点から、ァニオン界面活 性剤とノニオン界面活性剤が好ましぐァニオン界面活性剤とノニオン界面活性剤と の併用がより好ましい。ァニオン界面活性剤とノニオン界面活性剤を併用する場合に は、ァニオン界面活性剤とノニオン界面活性剤の配合量の質量比（ァニオン界面活 性剤/ノニオン界面活性剤）が、 0. 1〜： 10が好ましく、 0. 2〜8がより好ましく、 0. 3 〜7がさらに好ましい。  (B) The surfactant in the surfactant-containing particles is preferably a combination of an anionic surfactant and a nonionic surfactant, which is preferably an anionic surfactant and a nonionic surfactant, from the viewpoint of cleaning performance. . When an anionic surfactant and a nonionic surfactant are used in combination, the mass ratio of the anionic surfactant and the nonionic surfactant (anionic surfactant / nonionic surfactant) is 0.1 to: 10 is preferable, 0.2 to 8 is more preferable, and 0.3 to 7 is more preferable.
[0015] ァニオン界面活性剤としては、従来より洗剤において使用されるものであれば、特 に限定されるものではなぐ各種のァニオン界面活性剤を使用することができる。例 えば、以下のものを挙げることができる。  [0015] As the anionic surfactant, various anionic surfactants that are not particularly limited can be used as long as they are conventionally used in detergents. For example, the following can be mentioned.
(1)炭素数 8〜18のアルキル基を有する直鎖又は分岐鎖のアルキルベンゼンスルホ ン酸塩（LAS) (2)炭素数 10〜 20のアルキル硫酸塩 (AS )又はアルケニル硫酸塩 (1) Linear or branched alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms (2) C10-20 alkyl sulfate (AS) or alkenyl sulfate
(3)炭素数 10〜20の α—ォレフインスルホン酸塩 (AOS)  (3) α-Olefin sulfonate (AOS) with 10 to 20 carbon atoms
(4)炭素数 10〜 20のアルカンスルホン酸塩  (4) C10-20 alkane sulfonate
(5)炭素数 10〜20の直鎖又は分岐鎖のアルキル基もしくはアルケニル基を有し、平 均付加モル数が 10モル以下のエチレンオキサイド、プロピレンオキサイド、ブチレン オキサイド又はそれらの混合物を付加したアルキルエーテル硫酸塩 (AES)又はァ ノレケニノレエーテノレ硫酸塩  (5) Alkyl having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of ethylene oxide, propylene oxide, butylene oxide or a mixture thereof of 10 moles or less Ether Sulfate (AES) or Anolekeninoreethenole Sulfate
[0016] (6)炭素数 10〜20の直鎖又は分岐鎖のアルキル基もしくはアルケニル基を有し、平 均付加モル数が 10モル以下のエチレンオキサイド、プロピレンオキサイド、ブチレン オキサイド又はそれらの混合物を付加したアルキルエーテルカルボン酸塩又はアル ケニノレエーテノレ力ノレボン酸塩  (6) An ethylene oxide, propylene oxide, butylene oxide or a mixture thereof having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average addition mole number of 10 mol or less. Added alkyl ether carboxylate or alkenino ethenore force nore bonate
(7)炭素数 10〜20のアルキルグリセリルエーテルスルホン酸等のアルキル多価アル コールエーテル硫酸塩  (7) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms
(8)炭素数 10〜20の高級脂肪酸塩  (8) C10-20 higher fatty acid salt
(9)炭素数 8〜20の飽和又は不飽和 α—スルホ脂肪酸（ α— SF)塩又はそのメチル ァニオン界面活性剤としては、直鎖アルキルベンゼンスルホン酸（LAS)のアルカリ 金属塩 (例えば、ナトリウム又はカリウム塩等）、 AOS、 a— SF又はそのメチル、ェチ ノレもしくはプロピルエステルのアルカリ金属塩 (例えば、ナトリウム又はカリウム塩等）、 AESのアルカリ金属塩 (例えば、ナトリウム又はカリウム塩等）、高級脂肪酸のアル力 リ金属塩 (例えば、ナトリウム又はカリウム塩等）が好ましい。このうち、炭素数 10〜： 14 のアルキル基を有する LAS、炭素数 10〜20の高級脂肪酸塩及び炭素数 12〜18 のひ 一SFが好ましい。  (9) A saturated or unsaturated α-sulfo fatty acid (α-SF) salt having 8 to 20 carbon atoms or a methyl anionic surfactant thereof is an alkali metal salt of linear alkylbenzene sulfonic acid (LAS) (for example, sodium or Potassium salts, etc.), AOS, a-SF, or alkali metal salts (eg, sodium or potassium salts) of methyl, ethinole or propyl esters thereof, alkali metal salts of AES (eg, sodium or potassium salts), higher grades Fatty acid metal salts (for example, sodium or potassium salts) are preferred. Among these, LAS having an alkyl group having 10 to 14 carbon atoms, a higher fatty acid salt having 10 to 20 carbon atoms, and one SF having 12 to 18 carbon atoms are preferable.
[0017] ノニオン界面活性剤としては、例えば、以下のものを挙げることができる。 [0017] Examples of the nonionic surfactant include the following.
(1)炭素数 6〜22、好ましくは 8〜： 18の脂肪族アルコールに炭素数 2〜4のアルキレ ンオキサイドを平均 3〜 30モル、好ましくは 5〜 20モル付加したポリオキシアルキレン ァノレキノレ（又はアルケニノレ）エーテル  (1) A polyoxyalkylene anolenole (or an average of 3 to 30 mol, preferably 5 to 20 mol) of an alkylene oxide having 2 to 4 carbon atoms added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Alkeninole) ether
この中でも、ポリオキシエチレンアルキル（又はアルケニノレ）エーテル、ポリオキシェ チレンポリオキシプロピレンアルキル（又はアルケニル）エーテルが好適である。ここ で使用される脂肪族アルコールとしては、第 1級アルコール、第 2級アルコールが挙 げられる。また、そのアルキル基は、分岐鎖を有していてもよい。脂肪族アルコールと しては、第 1級アルコールが好ましい。 Among these, polyoxyethylene alkyl (or alkeninole) ether, polyoxyester Tylene polyoxypropylene alkyl (or alkenyl) ether is preferred. The aliphatic alcohols used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2)ポリオキシエチレンアルキル（又はアルケニノレ）フエニルエーテノレ  (2) Polyoxyethylene alkyl (or alkeninole) phenyl etherol
(3)長鎖脂肪酸アルキルエステルのエステル結合間にアルキレンオキサイドが付加 した  (3) Alkylene oxide added between ester bonds of long-chain fatty acid alkyl ester
、例えば下記一般式 (I)で表される脂肪酸アルキルエステルアルコキシレート  For example, fatty acid alkyl ester alkoxylates represented by the following general formula (I)
RICO (OA) nOR2 (I)  RICO (OA) nOR2 (I)
(式中、 R1C〇は、炭素数 6〜22、好ましくは 8〜： 18の脂肪酸残基を示し、 OAは、ェ チレンオキサイド、プロピレンオキサイド等の炭素数 2〜4、好ましくは 2〜3のアルキ レンオキサイドの付加単位を示し、 nはアルキレンオキサイドの平均付加モル数を示 し、一般に 3〜30、好ましくは 5〜20の数である。 R2は炭素数 1〜3の置換基を有し てもよい低級 (炭素数 1〜4)アルキル基を示す。） (In the formula, R1C0 represents a fatty acid residue having 6 to 22, preferably 8 to 18 carbon atoms, and OA represents 2 to 4, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. N represents an addition unit of alkylene oxide, n represents the average number of moles of alkylene oxide added, and is generally a number of 3 to 30, preferably 5 to 20. R2 has a substituent of 1 to 3 carbon atoms. It may be a lower (C1-4) alkyl group.)
(4)ポリオキシエチレンソルビタン脂肪酸エステル  (4) Polyoxyethylene sorbitan fatty acid ester
(5)ポリオキシエチレンソルビット脂肪酸エステル  (5) Polyoxyethylene sorbite fatty acid ester
(6)ポリオキシエチレン脂肪酸エステル  (6) Polyoxyethylene fatty acid ester
(7)ポリオキシエチレン硬化ヒマシ油  (7) Polyoxyethylene hydrogenated castor oil
(8)グリセリン脂肪酸エステル  (8) Glycerin fatty acid ester
上記のノニオン界面活性剤の中でも、上述した（1)のノニオン界面活性剤が好まし ぐ特に、炭素数 12〜： 16の脂肪族アルコールに炭素数 2〜4のアルキレンオキサイド を平均 5〜20モル付加したポリオキシアルキレンアルキル（又はァルケニル）エーテ ルが好ましレ、。融点が 50°C以下で HLBが 9〜： 16のポリオキシエチレンアルキル（又 はァルケニル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキル（又はァ ルケニル)エーテル、脂肪酸メチルエステルにエチレンオキサイドが付加した脂肪酸 メチルエステルエトキシレート、脂肪酸メチルエステルにエチレンオキサイドとプロピレ ンオキサイドが付加した脂肪酸メチルエステルエトキシプロポキシレート等が好適に 用いられる。また、これらのノニオン界面活性剤は 1種単独で又は 2種以上を適宜組 み合わせて用いることができる。 Among the nonionic surfactants described above, the nonionic surfactant (1) described above is preferred, and an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 12 to 16 carbon atoms. An added polyoxyalkylene alkyl (or alkenyl) ether is preferred. Melting point of 50 ° C or less and HLB 9 ~: 16 Polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, fatty acid methyl ester with fatty acid methyl ester Ester ethoxylate, fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to fatty acid methyl ester, and the like are preferably used. These nonionic surfactants may be used alone or in combination of two or more. They can be used together.
なお、本発明におけるノニオン界面活性剤の HLBとは、 Griffinの方法により求め られた値である（吉田、進藤、大垣、山中共編、「新版界面活性剤ハンドブック」、ェ 業図書株式会社、 1991年、第 234頁参照）。また、本発明における融点とは、 JIS K0064— 1992「化学製品の融点及び溶融範囲測定方法」に記載されている融点 測定法によって測定された値である。  The HLB of the nonionic surfactant in the present invention is a value determined by Griffin's method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Yonsho Co., Ltd., 1991). Year, page 234). The melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Measuring Method of Melting Point and Melting Range of Chemical Products”.
[0019] カチオン界面活性剤としては、例えば、以下のものを挙げることができる。 [0019] Examples of the cationic surfactant include the following.
( 1 )ジ長鎖アルキルジ短鎖アルキル型 4級アンモニゥム塩  (1) Di long chain alkyl di short chain alkyl type quaternary ammonium salt
(2)モノ長鎖アルキルトリ短鎖アルキル型 4級アンモニゥム塩  (2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt
(3)トリ長鎖アルキルモノ短鎖アルキル型 4級アンモニゥム塩  (3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt
(上記長鎖アルキルは炭素数 12〜26、好ましくは 14〜18のアルキル基、短鎖アル キルは炭素数 1〜4、好ましくは 1〜2のアルキル基、ベンジル基、炭素数 2〜4、好ま しくは 2〜3のヒドロキシアルキル基、又はポリオキシアルキレン基を示す。）  (The above long chain alkyl is an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms, and the short chain alkyl is 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, a benzyl group, 2 to 4 carbon atoms, Preferably it represents 2-3 hydroxyalkyl groups or polyoxyalkylene groups.)
両性界面活性剤としては、イミダゾリン系や、アミドべタイン系等の両性界面活性剤 を挙げることができる。  Examples of amphoteric surfactants include amphoteric surfactants such as imidazolines and amide betaines.
[0020] 界面活性剤の配合量は、（C)表面処理水溶性アルカリ無機化合物粒子との混合 による溶解性や流動性の観点から、 (B)界面活性剤含有粒子中に 10〜50質量％、 好ましくは 15〜40質量％である。 50質量％を超えて配合すると流動性が劣る場合 があり、 10質量％未満であると溶解性が劣る場合がある。  [0020] From the viewpoint of solubility and fluidity when mixed with (C) surface-treated water-soluble alkali-inorganic compound particles, the amount of the surfactant is (B) 10 to 50% by mass in the surfactant-containing particles. Preferably, it is 15 to 40% by mass. If it exceeds 50% by mass, the fluidity may be inferior, and if it is less than 10% by mass, the solubility may be inferior.
本発明の組成物において、 （B)界面活性剤含有粒子は、組成物の全量を基準とし て、好ましくは 50〜94質量％、より好ましくは 75〜90質量％以上の量で含まれるの が好ましい。 50質量％より少ない場合には洗浄性能が低下する場合があり、 94質量 %より多い場合には、他の成分が不足して本発明の効果が小さくなる場合がある。  In the composition of the present invention, the (B) surfactant-containing particles are preferably contained in an amount of 50 to 94% by mass, more preferably 75 to 90% by mass or more based on the total amount of the composition. preferable. When the amount is less than 50% by mass, the cleaning performance may be deteriorated. When the amount is more than 94% by mass, the effects of the present invention may be reduced due to lack of other components.
[0021] 本発明の（B)界面活性剤含有粒子は、上記必須成分のほかに下記に示す任意成 分も含有すること力 Sできる。なお、無機化合物や水溶性高分子化合物は重複して記 載される。これら任意成分は、各々 1種単独で又は 2種以上を適宜組み合わせて用 レ、ることができる。  [0021] The (B) surfactant-containing particles of the present invention can contain any of the following optional components in addition to the above essential components. Note that inorganic compounds and water-soluble polymer compounds are listed in duplicate. Each of these optional components can be used alone or in combination of two or more.
[0022] (1)洗浄ビルダー (B)界面活性剤含有粒子中に配合される洗浄ビルダーとしては、無機及び有機ビ ルダ一が挙げられる。 [0022] (1) Cleaning builder (B) Examples of the cleaning builder compounded in the surfactant-containing particles include inorganic and organic builders.
(1 1)無機ビルダー (1 1) Inorganic builder
無機ビルダーとしては、例えば炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、亜 硫酸ナトリウム、セスキ炭酸ナトリウム、珪酸ナトリウム、結晶性層状珪酸ナトリウム、非 結晶性層状珪酸ナトリウム等のアルカリ性塩、硫酸ナトリウム等の中性塩、オルソリン 酸塩、ピロリン酸塩、トリポリリン酸塩、メタリン酸塩、へキサメタリン酸塩、フィチン酸塩 等のリン酸塩、下記一般式 (II)  Examples of the inorganic builder include sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, non-crystalline layered sodium silicate, etc., neutral salts, sodium sulfate, etc. Salts, orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phosphates such as phytate, and the following general formula (II)
xl (M20) -A1203 -yl (Si02) -wl (H20) (II)  xl (M20) -A1203 -yl (Si02) -wl (H20) (II)
(式中、 Mはナトリウム、カリウム等のアルカリ金属原子、 xl、 yl及び wlは各成分のモ ル数を示し、一般的には、 xlは 0. 7〜： 1. 5、ylは 0. 8〜6の数、 wlは任意の正数を 示す。） (In the formula, M is an alkali metal atom such as sodium or potassium, xl, yl and wl are the number of moles of each component, and in general, xl is 0.7 to 1.5: yl is 0.5. (Numbers from 8 to 6, wl represents any positive number.)
で表される結晶性アルミノ珪酸塩、下記一般式 (111)、 (IV) A crystalline aluminosilicate represented by the following general formula (111), (IV)
x2 (M20) · A1203 'y2 (Si〇2) · w2 (H20) (III)  x2 (M20) A1203 'y2 (Si02) w2 (H20) (III)
(式中、 Mはナトリウム、カリウム等のアルカリ金属原子、 x2、 y2及び w2は各成分のモ ノレ数を示し、一般白勺に ίま、 χ2ίま 0. 7〜： 1. 2、y2iま 1. 6〜2. 8、 w2iま 0又 ίま任意の正 数を示す。 ) (In the formula, M is an alkali metal atom such as sodium or potassium, x2, y2 and w2 indicate the number of moles of each component, and are generally white birch, χ2ί or 0.7-7: 1: 2, y2i 1. 6 to 2.8, w2i 0 or ί indicates any positive number.
x3 (M2〇） -A1203 -y3 (Si02) · ζ3 (Ρ205) -w3 (H20)  x3 (M20) -A1203 -y3 (Si02) · ζ3 (Ρ205) -w3 (H20)
(IV)  (IV)
(式中、 Mはナトリウム、カリウム等のアルカリ金属原子、 x3、 y3、 z3及び w3は各成分 のモノレ数を示し、一般白勺に ίま、 χ3ίま 0. 2〜： 1. 1、 y3iま 0. 2〜4. 0、 ζ3ίま 0. 001〜0 . 8、 w3は 0又は任意の正数を示す。）  (In the formula, M is an alkali metal atom such as sodium or potassium, x3, y3, z3, and w3 are monole numbers of each component, and are generally white birch, χ3ί or 0.2-2: 1.1, y3i 0.2 to 4.0, ζ3ί, 0.001 to 0.8, and w3 is 0 or any positive number.)
で表される無定形アルミノ珪酸塩等が挙げられる。無機ビルダーの中では、炭酸ナト リウム、炭酸カリウム、珪酸ナトリウム、トリポリリン酸ナトリウム、アルミノ珪酸ナトリウムが 好ましい。 Amorphous aluminosilicate represented by the following. Among inorganic builders, sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate and sodium aluminosilicate are preferred.
(B)界面活性剤含有粒子中の無機ビルダーの配合量は、 10〜80質量％、好まし くは 20〜70質量％、より好ましくは 30〜60質量％である。無機ビルダーの配合量が 少なすぎると流動性が劣化する場合があり、多すぎると粉の発塵が起こる場合がある (1 2)有機ビルダー (B) The compounding amount of the inorganic builder in the surfactant-containing particles is 10 to 80% by mass, preferably 20 to 70% by mass, more preferably 30 to 60% by mass. If the amount of inorganic builder is too small, fluidity may deteriorate, and if it is too large, dust generation may occur. (1 2) Organic builder
有機ビルダーとしては、有機高分子系ビルダーと有機低分子系ビルダーが挙げら れる。有機高分子系ビルダーとしては、アクリル酸系高分子化合物、ポリアセタール カルボン酸塩、セルロース系高分子化合物、ィタコン酸、フマル酸、テトラメチレン— 1 , 2 _ジカルボン酸、コハク酸、ァスパラギン酸等の重合体又は共重合体が挙げら れる。アクリル酸系高分子化合物としては、アクリル酸重合体、アクリル酸 Zマレイン 酸共重合体が好ましぐ特に、重量平均分子量が 1 , 000-80, 000のアクリル酸 Z マレイン酸共重合体の塩、アクリル酸重合体の塩が好適である。ポリアセタールカル ボン酸塩としては、特開昭 54— 52196号公報に記載の重量平均分子量が 800〜1 , 000, 000、好ましくは 5， 000〜200, 000のポリグリオキシノレ酸等のポリアセター ルカルボン酸塩が好適である。セルロース系高分子化合物としては、カルボキシメチ ルセルロース（CMC)が好ましい。水溶性高分子化合物の重量平均分子量は 1 , 00 0〜： 1 , 000, 000力 S好ましく、 1, 000〜100, 000力 sより好ましレヽ。有機高分子系ビ ルダ一は 1種単独で又は 2種以上を適宜組み合わせて用いることができる。  Examples of the organic builder include an organic high molecular builder and an organic low molecular builder. Examples of organic polymer builders include acrylic acid polymer compounds, polyacetal carboxylates, cellulose polymer compounds, itaconic acid, fumaric acid, tetramethylene-1,2-dicarboxylic acid, succinic acid, aspartic acid, and other heavy polymers. Examples thereof include a polymer and a copolymer. Acrylic acid polymers and acrylic acid Z maleic acid copolymers are preferred as the acrylic acid polymer compounds. Particularly, a salt of acrylic acid Z maleic acid copolymer having a weight average molecular weight of 1,000 to 80,000. A salt of an acrylic acid polymer is preferred. Examples of the polyacetal carbonate include polyacetal carboxyl such as polyglyoxynolic acid having a weight average molecular weight of 800 to 1,000,000, preferably 5,000 to 200,000 described in JP-A-54-52196. Acid salts are preferred. As the cellulose polymer compound, carboxymethyl cellulose (CMC) is preferable. The weight average molecular weight of the water-soluble polymer compound is preferably 1,000,000 to: 1,000,000 force S, more preferably 1,000 to 100,000 force s. The organic polymer builder can be used alone or in combination of two or more.
有機低分子系ビルダーとしては、例えば二トリ口トリ酢酸塩、エチレンジアミンテトラ 酢酸塩、 βーァラニンジ酢酸塩、ァスパラギン酸ジ酢酸塩、メチルグリシンジ酢酸塩、 イミノジコハク酸塩等のアミノカルボン酸塩；セリンジ酢酸塩、ヒドロキシイミノジコハク 酸塩、ヒドロキシェチルエチレンジァミン三酢酸塩、ジヒドロキシェチルダリシン塩等の ヒドロキシァミノカルボン酸塩；ヒドロキシ酢酸塩、酒石酸塩、クェン酸塩、ダルコン酸 塩等のヒドロキシカルボン酸塩；ピロメリット酸塩、ベンゾポリカルボン酸塩、シクロペン タンテトラカルボン酸塩等のシクロカルボン酸塩；カルボキシメチルタルトロネート、力 ルボキシメチルォキシサクシネート、ォキシジサクシネート、酒石酸モノ又はジサクシ ネート等のエーテルカルボン酸塩等が挙げられる。  Organic low molecular weight builders include, for example, nitrite triacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, iminodisuccinate and other aminocarboxylates; serine diacetate Hydroxyaminocarboxylates such as salts, hydroxyiminodisuccinate, hydroxyethylethylenediamin triacetate, dihydroxyethyldaricine; hydroxyacetates, tartrate, citrate, darconate, etc. Hydroxycarboxylates; cyclocarboxylates such as pyromellitic acid salts, benzopolycarboxylic acid salts, cyclopentanetetracarboxylic acid salts; carboxymethyl tartronate, ruboxymethyloxysuccinate, oxydisuccinate, Ether carbonates such as tartaric acid mono- or disuccinate Phosphate salts, and the like.
これらの有機低分子系ビルダーの中では、クェン酸塩、アミノカルボン酸塩、ヒドロ キシァミノカルボン酸塩、ヒドロキシイミノジコハク酸塩が好ましレ、。  Among these organic low molecular weight builders, citrates, aminocarboxylates, hydroxyaminocarboxylates, and hydroxyiminodisuccinates are preferred.
(Β)界面活性剤含有粒子中の有機ビルダーの配合量は、 0.：!〜 20質量％、好ま しくは 0. 5%〜： 15質量％、より好ましくは 1〜： 10質量％である。有機ビルダーの配合 量が少なすぎると、洗浄性能の向上効果が得られない場合があり、多すぎると (B)界 面活性剤含有粒子そのものの溶解性が劣化してしまう場合がある。 (Ii) The compounding amount of the organic builder in the surfactant-containing particles is 0.:! To 20% by mass, preferably 0.5% to: 15% by mass, more preferably 1 to 10% by mass. . Formulation of organic builder If the amount is too small, the effect of improving the cleaning performance may not be obtained. If the amount is too large, the solubility of the (B) surfactant-containing particles themselves may be deteriorated.
また、洗浄力、洗濯液中での汚れ分散性を改善する目的から、クェン酸塩、アミノカ ルボン酸塩、ヒドロキシァミノカルボン酸塩、ポリアクリル酸塩、アクリル酸—マレイン酸 共重合体、ポリアセタールカルボン酸塩等の有機ビルダーとゼォライト等の無機ビル ダ一とを併用するのが好ましい。  In addition, for the purpose of improving detergency and soil dispersibility in washing liquid, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid copolymer, polyacetal It is preferable to use an organic builder such as carboxylate in combination with an inorganic builder such as zeolite.
[0024] (2)溶解促進剤  [0024] (2) Dissolution promoter
(B)界面活性剤含有粒子中に配合される溶解促進剤としては、例えば、炭酸力リウ ムゃ、硫酸アンモニゥム、塩化アンモニゥム等の無機アンモニゥム塩、 p—トルエンス ルホン酸ナトリウム、キシレンスルホン酸ナトリウム、キュメンスルホン酸ナトリウム等の 炭素数 1〜5の短鎖アルキルを有するベンゼンスルホン酸塩、安息香酸ナトリウム、ベ ンゼンスルホン酸ナトリウム、塩ィ匕ナトリウム、クェン酸、 D—グノレコース、尿素、蔗糖 等の水溶性物質が挙げられる。このうち、炭酸カリウム、塩化ナトリウムが好ましぐ溶 解性向上効果とコストのバランスから、特に炭酸カリウムが好ましい。  (B) Examples of the dissolution accelerator blended in the surfactant-containing particles include inorganic ammonium salts such as carbonated ammonium, ammonium sulfate and ammonium chloride, sodium p-toluenesulfonate, sodium xylenesulfonate, Water-soluble benzenesulfonate, sodium benzoate, sodium benzenesulfonate, sodium salt sodium salt, citrate, D-gnolecose, urea, sucrose, etc. Substances. Of these, potassium carbonate is particularly preferred from the viewpoint of the balance between the improvement in solubility and the cost that potassium carbonate and sodium chloride are preferred.
炭酸カリウムを配合する場合、その配合量は溶解性向上効果の点から、（B)界面 活性剤含有粒子中に好ましくは:!〜 15質量％、より好ましくは 2〜： 12質量％、さらに 好ましくは 5〜： 10質量％である。塩ィ匕ナトリウムを配合する場合、その配合量は溶解 性向上効果の点から、（B)界面活性剤含有粒子中に好ましくは:!〜 10質量％、より 好ましくは 2〜8質量％、さらに好ましくは 3〜7質量％である。  When potassium carbonate is blended, the blending amount thereof is preferably (B) surfactant-containing particles in terms of solubility improvement effect: (!) To 15% by mass, more preferably 2 to: 12% by mass, and even more preferably. Is 5 to 10 mass%. In the case of blending sodium salt sodium, the blending amount is preferably (B) in the surfactant-containing particles from the viewpoint of improving the solubility:! -10 mass%, more preferably 2-8 mass%, Preferably it is 3-7 mass%.
[0025] (3)膨潤性水不溶性物質、例えば粉末セルロース、結晶性セルロース、ベントナイト 等、  (3) Swellable water-insoluble substances such as powdered cellulose, crystalline cellulose, bentonite, etc.
(4)蛍光剤：ビス（トリアジニルアミノスチルベン）ジスルホン酸誘導体（チノパール AM S -GX)、ビス（スルホスチリル）ビフエニル塩 [チノパール CBS—X]等、  (4) Fluorescent agent: bis (triazinylaminostilbene) disulfonic acid derivative (Tinopearl AM S-GX), bis (sulfostyryl) biphenyl salt [Tinopearl CBS-X], etc.
(5)帯電防止剤：ジアルキル型 4級アンモニゥム塩等のカチオン界面活性剤等、 (5) Antistatic agent: dialkyl type quaternary ammonium salt and other cationic surfactants,
(6)再汚染防止剤：カルボキシメチルセルロース等のセルロース誘導体等、 (6) Anti-staining agent: cellulose derivatives such as carboxymethyl cellulose,
(7)増量剤:硫酸ナトリウム、硫酸カリウム等、  (7) Bulking agent: sodium sulfate, potassium sulfate, etc.
(8)還元剤：亜硫酸ナトリウム、亜硫酸カリウム等、  (8) Reducing agent: sodium sulfite, potassium sulfite, etc.
(9)香料 (10)色素 (9) Fragrance (10) Dye
(11)漂白活性化触媒、特に、銅、鉄、マンガン、ニッケル、コバルト、クロム、バナジ ゥム、ルテニウム、ロジウム、パラジウム、レニウム、タングステン、モリブデン等の遷移 金属原子と配位子とが、窒素原子や酸素原子等を介して錯体を形成するものであつ て、含まれる遷移金属としては、コバルト、マンガン等が好ましぐ特にマンガンが好ま しい。  (11) Bleach activation catalyst, especially copper, iron, manganese, nickel, cobalt, chromium, vanadium, ruthenium, rhodium, palladium, rhenium, tungsten, molybdenum, etc. Cobalt is formed through atoms, oxygen atoms, and the like, and as the transition metal contained, cobalt, manganese, etc. are preferred, and manganese is particularly preferred.
[0026] (B)界面活性剤含有粒子の平均粒子径は好ましくは 200〜： 1， 500 z m、より好ま しくは 250〜1， 000 z m、さらに好ましくは 300〜700 μ mである。また、嵩密度は好 ましく ίま 0. 4〜： 1. 2g/mL,より好ましく fま 0. 5〜： 1. Og/mLである。  [0026] The average particle diameter of the (B) surfactant-containing particles is preferably 200 to: 1,500 zm, more preferably 250 to 1,000 zm, and even more preferably 300 to 700 μm. The bulk density is preferably ί or 0.4 to: 1.2 g / mL, more preferably f to 0.5 to 1. Og / mL.
(B)界面活性剤含有粒子の水分量は溶解性と保存安定性の点から好ましくは 4〜 10質量％、より好ましくは 5〜9質量％、さらに好ましくは 5〜8質量％である。  The water content of the (B) surfactant-containing particles is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and further preferably 5 to 8% by mass from the viewpoints of solubility and storage stability.
[0027] (B)界面活性剤含有粒子は、以下の造粒方法によって得ることができる。原料粉末 及びバインダー成分 (界面活性剤、水、液体高分子成分等)を捏和 *混練した後、押 し出して造粒する押し出し造粒法、捏和'混練した後、得られた固形洗剤を破砕して 造粒する捏和'破砕造粒法、原料粉末にバインダー成分を添加し撹拌羽根で撹拌し て造粒する撹拌造粒法、原料粉末を転動させつつバインダー成分を噴霧して造粒 する転動造粒法、原料粉末を流動化させつつ、液体バインダーを噴霧し造粒する流 動層造粒法等が挙げられる。これら造粒方法で使用可能な具体的装置や条件等は 特開 2003— 105400号公報、特開 2003— 238998号公報、 日本粉体技術協会編 及び造粒ハンドブック第一版等に記載の通りである。  [0027] (B) The surfactant-containing particles can be obtained by the following granulation method. The raw powder and binder components (surfactant, water, liquid polymer component, etc.) are kneaded * Extruded granulation method after kneading and then extruding and granulating, the resulting solid detergent after kneading Smashing and granulating the powder, crushing granulation method, stirring granulation method in which the binder component is added to the raw material powder and stirring and stirring with a stirring blade, the binder component is sprayed while rolling the raw material powder Examples thereof include a rolling granulation method for granulation, and a fluidized bed granulation method in which a liquid binder is sprayed and granulated while fluidizing the raw material powder. Specific apparatuses and conditions that can be used in these granulation methods are as described in JP-A-2003-105400, JP-A-2003-238998, edited by Japan Powder Technology Association, and the first edition of the granulation handbook. is there.
[0028] 貯蔵時の固化（ケーキング）を防止する観点から、（C)表面処理水溶性アルカリ無 機化合物粒子と (B)界面活性剤含有粒子のレ、ずれか一方、好ましくは両方を有機 又は無機の微粉体で表面処理することが好ましレ、。これら微粉体としては 1次粒子径 30 z m以下、好ましくは 0. 1〜： 10 z mの微粉体であれば特に限定されないが、例と しては常温固体の界面活性剤、長鎖脂肪酸アルカリ土類金属塩、アルミノ珪酸塩、 シリカ、粘土鉱物等が挙げられる。このうちアルミノ珪酸塩が好ましい。  [0028] From the standpoint of preventing solidification (caking) during storage, (C) the surface-treated water-soluble alkali-inorganic compound particles and (B) the surfactant-containing particles are preferably organic or Surface treatment with inorganic fine powder is preferred. These fine powders are not particularly limited as long as they have a primary particle size of 30 zm or less, preferably 0.1 to 10 zm, but examples include normal temperature solid surfactants and long-chain fatty acid alkaline earths. Metal salts, aluminosilicates, silica, clay minerals and the like. Of these, aluminosilicate is preferred.
(C)粒子及び/又は (B)粒子を微粉体で表面処理する場合、微粉体の量は、粒状 粒状洗剤組成物中好ましくは 0. 1〜： 10質量％、より好ましくは 0. 3〜5質量％、さら に好ましくは 0. 5〜3質量％である。 When (C) particles and / or (B) particles are surface-treated with a fine powder, the amount of the fine powder is preferably 0.1 to 10% by mass in the granular granular detergent composition, more preferably 0.3 to 5% by mass, It is preferably 0.5 to 3% by mass.
[0029] 本発明においては、特に下記条件を満たす (C)表面処理水溶性アルカリ無機化合 物粒子及び (B)界面活性剤含有粒子の組み合わせが好ましレ、。  In the present invention, a combination of (C) surface-treated water-soluble alkali inorganic compound particles and (B) surfactant-containing particles satisfying the following conditions is particularly preferred.
(C)粒子の水溶性アルカリ無機化合物が、炭酸ナトリウム又は炭酸カリウムから選ば れる 1種又は 2種以上であり、水溶性高分子化合物がビニル系高分子化合物、多糖 類又はその誘導体及びポリエステル系高分子化合物から選ばれる 1種又は 2種以上 であり、（C)粒子中の水難溶性化合物の配合量が 10質量％未満であり、かつ（B)界 面活性剤含有粒子中の界面活性剤配合量が 10〜40質量％である。このような組み 合わせを用いると、低水温中での分散性が大きく改善できるので好ましい。  (C) The water-soluble alkaline inorganic compound of the particles is one or more selected from sodium carbonate or potassium carbonate, and the water-soluble polymer compound is a vinyl polymer compound, a polysaccharide or a derivative thereof, and a polyester compound. 1 or 2 or more types selected from molecular compounds, (C) The amount of the poorly water-soluble compound in the particles is less than 10% by mass, and (B) The surfactant in the surfactant-containing particles The amount is 10-40% by mass. Use of such a combination is preferable because dispersibility at a low water temperature can be greatly improved.
[0030] (C)成分  [0030] Component (C)
本発明の（C)成分は、核となる水溶性アルカリ無機化合物を、有機又は無機水溶 性高分子化合物と水難溶性化合物とで表面処理してなり、水溶性アル力リ無機化合 物の含有量が 50〜98質量％である、表面処理した水溶性アルカリ無機化合物粒子 である。  The component (C) of the present invention is obtained by subjecting a water-soluble alkaline inorganic compound as a core to a surface treatment with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound, and the content of the water-soluble alkaline inorganic compound. The surface-treated water-soluble alkali-inorganic compound particles having an amount of 50 to 98% by mass.
(C)成分は低温溶解性の点から、水溶性アルカリ無機化合物を核粒子 (以下、水 溶性アルカリ無機化合物核粒子と記す）として使用し、水溶性アルカリ無機化合物核 粒子を第 1表面処理剤として有機又は無機水溶性高分子化合物で表面処理し、得 られた粒子をさらに第 2表面処理剤として水難溶性化合物で表面処理することにより 得ることができる表面処理した水溶性アルカリ無機化合物粒子であることが好ましレ、  Component (C) uses a water-soluble alkali-inorganic compound as core particles (hereinafter referred to as water-soluble alkali-inorganic compound core particles) from the viewpoint of low-temperature solubility, and the water-soluble alkali-inorganic compound core particles are used as the first surface treatment agent. Surface-treated water-soluble alkali-inorganic compound particles that can be obtained by surface-treating with an organic or inorganic water-soluble polymer compound as the second surface treatment agent and surface-treating with a poorly water-soluble compound as the second surface treatment agent. I prefer it,
<水溶性アルカリ無機化合物核粒子 > <Water-soluble alkali inorganic compound core particles>
本発明におレ、て使用できる水溶性アルカリ無機化合物核粒子とは、 5°Cにおける 水への溶解度が lgZlOOg以上、好ましくは 2gZl00g以上、より好ましくは 3gZlO Og以上の水溶性アルカリ無機化合物粒子をいう。このような水溶性アルカリ無機化合 物粒子であれば、特に限定されず、 1種単独で又は 2種以上を適宜組み合わせて用 レ、ることができる。  The water-soluble alkali-inorganic compound core particles that can be used in the present invention are water-soluble alkali-inorganic compound particles having a solubility in water at 5 ° C of not less than lgZlOOg, preferably not less than 2 gZl00 g, more preferably not less than 3 gZlO Og. Say. Such water-soluble alkali-inorganic compound particles are not particularly limited, and can be used singly or in appropriate combination of two or more.
洗浄性能寄与の点から、 5°Cの飽和水溶液の pHが 8以上、好ましくは 5°Cの飽和水 溶液の pHが 9以上、より好ましくは 5°Cの飽和水溶液の pHが 10以上の水溶性アル力 リ無機化合物が好適である。 From the viewpoint of contribution to cleaning performance, the pH of a saturated aqueous solution at 5 ° C is 8 or higher, preferably the pH of a saturated aqueous solution at 5 ° C is 9 or higher, more preferably, the pH of a saturated aqueous solution at 5 ° C is 10 or higher. Sexual power Re-inorganic compounds are preferred.
このような水溶性アルカリ無機化合物粒子としては、一般にアルカリ洗浄ビルダー として用いられているものが挙げられる。具体的には、炭酸塩類、重炭酸塩類及びセ スキ炭酸塩類、亜硫酸塩類、リン酸塩及び重縮合リン酸塩類、珪酸塩類等が挙げら れる。この中でも、炭酸塩類、重縮合リン酸塩類等がさらに好ましぐ炭酸ナトリウム、 炭酸カリウム、トリポリリン酸ナトリウム等が特に好ましい。  Examples of such water-soluble alkali inorganic compound particles include those generally used as an alkali cleaning builder. Specific examples include carbonates, bicarbonates and sesquicarbonates, sulfites, phosphates and polycondensed phosphates, silicates and the like. Of these, sodium carbonate, potassium carbonate, sodium tripolyphosphate, and the like are more preferable, such as carbonates and polycondensed phosphates.
また、他の塩類との複合塩も好適に用いることができ、例えば、炭酸ナトリウムと硫 酸ナトリウムの複合塩であるバーケアイト等はその代表的な例である。水溶性アルカリ 無機化合物は 1種単独で又は 2種以上を適宜組み合わせて用いることができる。  In addition, complex salts with other salts can also be suitably used. For example, burkeite, which is a complex salt of sodium carbonate and sodium sulfate, is a typical example. The water-soluble alkali inorganic compound can be used alone or in combination of two or more.
[0031] 水溶性アルカリ無機化合物核粒子は常法により得ることができ、その平均粒子径は 、 100〜1500 μ πιカ好ましく、より好ましく fま、 200〜1000 μ πιである。平均粒子径 力 lOO x m未満では、水溶性高分子化合物による表面処理が困難となる場合があり , 1500 μ mを超えると水溶性アルカリ無機化合物の溶解性が低下する場合がある。 このような水溶性アルカリ無機化合物粒子は、市販のものを適宜用いることができる。 なお、平均粒子径は後述する実施例に記載の測定法による。  [0031] The water-soluble alkali-inorganic compound core particles can be obtained by a conventional method, and the average particle diameter thereof is preferably 100 to 1500 μπι, more preferably f to 200 to 1000 μπι. When the average particle size is less than lOO x m, the surface treatment with the water-soluble polymer compound may be difficult, and when it exceeds 1500 μm, the solubility of the water-soluble alkaline inorganic compound may be lowered. As such water-soluble alkali inorganic compound particles, commercially available particles can be used as appropriate. In addition, an average particle diameter is based on the measuring method as described in the Example mentioned later.
市販で入手可能な水溶性アルカリ無機化合物には様々なグレードのものがあるが 、本発明の利用を限定するものではない。例えば、製造工程で混入する不純物や品 質安定化の為の保存安定剤や酸化防止剤を含む水溶性アルカリ無機化合物も本発 明の範囲に含まれる。  There are various grades of commercially available water-soluble alkali-inorganic compounds, but the use of the present invention is not limited thereto. For example, water-soluble alkaline inorganic compounds containing impurities mixed in the manufacturing process, storage stabilizers for stabilizing the quality, and antioxidants are also included in the scope of the present invention.
[0032] <有機水溶性高分子化合物 >  [0032] <Organic water-soluble polymer compound>
上記水溶性アルカリ無機化合物の表面処理に用いる第 2表面処理剤である有機水 溶性高分子化合物は、 40°Cにおいて水 lOOgに対しては 0. lg以上、好ましくは 0. 2 g以上、より好ましくは 2g以上の濃度で水と均一に混和する高分子化合物である。こ のような有機水溶性高分子化合物であれば特に限定されず、 1種単独で又は 2種以 上を適宜組み合わせて用いることができる。  The organic water-soluble polymer compound, which is the second surface treatment agent used for the surface treatment of the water-soluble alkali inorganic compound, is not less than 0.1 lg, preferably not less than 0.2 g, with respect to water lOOg at 40 ° C. Preferably, it is a polymer compound that is uniformly mixed with water at a concentration of 2 g or more. Such an organic water-soluble polymer compound is not particularly limited and may be used alone or in appropriate combination of two or more.
有機水溶性高分子化合物としては、天然高分子化合物、半合成高分子化合物及 び合成高分子化合物等が挙げられる。具体的にはビニル系高分子化合物、多糖類 、ポリエーテル系高分子化合物、ポリエステル系高分子化合物、ペプチド系高分子 化合物、ポリウレタン、及びそれらの誘導体等を用いることができる。この中でも、ビニ ル系高分子化合物、多糖類、その誘導体及びポリエステル系高分子化合物から選 ばれる 1種を単独で又は 2種以上を適宜組み合わせて用いることが好ましい。 Examples of the organic water-soluble polymer compound include natural polymer compounds, semi-synthetic polymer compounds, and synthetic polymer compounds. Specifically, vinyl polymer compounds, polysaccharides, polyether polymer compounds, polyester polymer compounds, peptide polymers Compounds, polyurethane, and derivatives thereof can be used. Among these, it is preferable to use one kind selected from vinyl polymer compounds, polysaccharides, derivatives thereof and polyester polymer compounds alone or in combination of two or more.
ビュル系高分子化合物としては、例えば、ビュル系ポリカルボン酸塩類（アクリル酸 系高分子化合物）、ビュル系ポリスルホン酸塩、ポリビュルピリジン塩、ポリビュルイミ ダゾリゥム塩等が挙げられる。多糖類としては、各種天然又は合成多糖類を用いるこ とができる。  Examples of the bull polymer compound include a bull polycarboxylate (acrylic polymer compound), a bull polysulfonate, a polybure pyridine salt, and a polyburimidazol salt. As the polysaccharide, various natural or synthetic polysaccharides can be used.
[0033] ポリエステル系高分子化合物としては、例えば、テレフタル酸とエチレングリコール 及び/又はプロピレングリコール単位とのコポリマー又はターポリマー等が挙げられ る。これらの例としては、市販品の Texcare4291 (クラリアント社製）、 TexcareSRN - 300 (クラリアント社製）等が挙げられる。  [0033] Examples of polyester polymer compounds include copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units. Examples of these include commercially available Texcare4291 (manufactured by Clariant), TexcareSRN-300 (manufactured by Clariant), and the like.
ペプチド系高分子化合物又はその誘導体の具体例としては、ゼラチン、カゼイン、 アルブミン、コラーゲン、ポリグルタミン酸塩、ポリアスパラギン酸塩、ポリリジン、ポリア ルギニン及びこれらの誘導体等が挙げられる。  Specific examples of the peptide polymer compound or derivatives thereof include gelatin, casein, albumin, collagen, polyglutamate, polyaspartate, polylysine, polyarginine, and derivatives thereof.
ポリウレタンとしては、例えば、水溶性ポリウレタン等が挙げられる。また、ポリエチレ ングリコール等のその他の水溶性高分子化合物も用いることができる。  Examples of the polyurethane include water-soluble polyurethane. Other water-soluble polymer compounds such as polyethylene glycol can also be used.
特に、水溶性アルカリ無機化合物が水和しやすくなるという点から、重炭酸塩を含 む水溶性アルカリ無機化合物核粒子を水溶性有機高分子化合物で表面処理した状 態下、水と接する初期段階において浸水作用を発揮するものが好適である。このよう な特性を有する水溶性有機高分子化合物としては、ァニオン性、両性、ノニオン性等 の親水性官能基を有するものが挙げられる。  In particular, since the water-soluble alkali inorganic compound is easily hydrated, the initial stage of contacting with water in a state where the water-soluble alkali inorganic compound core particles containing bicarbonate are surface-treated with the water-soluble organic polymer compound. Those exhibiting a water immersion effect are preferred. Examples of the water-soluble organic polymer compound having such characteristics include those having hydrophilic functional groups such as anionicity, amphotericity, and nonionicity.
[0034] ァニオン性基を有する水溶性有機高分子化合物としては、例えば、カルボキシル 基、スルホ基を有する高分子化合物、ァニオン性基を有する水溶性多糖類が挙げら れる。カルボキシノレ基を有する水溶性有機高分子化合物としては、例えば、アクリル 酸、マレイン酸、ィタコン酸、アコニット酸、メタクリル酸、フマル酸、 2—ヒドロキシアタリ ル酸、シトラコン酸等のモノマーを重合させてなるポリマー及びその塩、並びにこれら のモノマーとその他のビュル系モノマーとの共重合体及びその塩等のビュル系ポリ カルボン酸 (塩）が挙げられる。スルホ基を有する水溶性高分子化合物としては、例 えば、アクリルアミドプロパンスルホン酸、メタクリルアミドプロパンスルホン酸、スチレ ンスルホン酸等のモノマーを重合してなるモノマー及びその塩、並びにこれらのポリ マーとその他のビニル系ポリマーとの共重合体及びその塩等のビエル系ポリスルホン 酸 (塩)等が挙げられる。ァニオン性基を有する水溶性多糖類としては、例えば、ポリ ゥロン酸塩、アルギン酸塩、ポリアスパラギン酸塩、力ラゲ一ナン、ヒアルロン酸塩、コ ンドロイチン硫酸塩、カルボキシメチルセルロース等が挙げられる。 [0034] Examples of the water-soluble organic polymer compound having an anionic group include a polymer compound having a carboxyl group and a sulfo group, and a water-soluble polysaccharide having an anionic group. Examples of the water-soluble organic polymer compound having a carboxynole group include polymerization of monomers such as acrylic acid, maleic acid, itaconic acid, aconitic acid, methacrylic acid, fumaric acid, 2-hydroxyataryl acid, and citraconic acid. And bulle polycarboxylic acids (salts) such as a copolymer of these monomers and other bulle monomers and salts thereof. Examples of water-soluble polymer compounds having a sulfo group include For example, monomers obtained by polymerizing monomers such as acrylamide propane sulfonic acid, methacrylamide propane sulfonic acid, and styrene sulfonic acid, and salts thereof, copolymers of these polymers with other vinyl polymers, salts thereof, and the like. Biel type polysulfonic acid (salt) etc. are mentioned. Examples of the water-soluble polysaccharide having an anionic group include polyuronic acid salt, alginic acid salt, polyaspartic acid salt, force laganinan, hyaluronic acid salt, chondroitin sulfate, carboxymethyl cellulose and the like.
[0035] 両性水溶性高分子化合物としては、例えば、ァニオン性基を有するビニル系単量 体とカチオン性基を有するビュル系単量体との共重合体、カルボキシベタイン基又 はスルホベタイン基を有するビュル系の両性高分子が挙げられ、具体的には、アタリ ル酸/ジメチルアミノエチルメタクリル酸共重合体、アクリル酸/ジェチルアミノエチ ノレメタクリル酸共重合体等が挙げられる。  [0035] Examples of the amphoteric water-soluble polymer compound include a copolymer of a vinyl monomer having an anionic group and a bur monomer having a cationic group, a carboxybetaine group or a sulfobetaine group. Examples thereof include bur-based amphoteric polymers, and specifically include acrylic acid / dimethylaminoethyl methacrylic acid copolymer, acrylic acid / jetylaminoethyl methacrylic acid copolymer, and the like.
ノニオン性水溶性高分子化合物としては、例えば、ポリアクリルアミド、ポリビュルァ ノレコール、ポリビュルピロリドン、ポリビニルェチルエーテル、ポリエチレングリコール 等の合成高分子化合物、ヒドロキシェチルセルロース、グァーガム、デキストラン、プ ルラン等の多糖類が挙げられる。  Nonionic water-soluble polymer compounds include, for example, synthetic polymer compounds such as polyacrylamide, polybutanol, polybutyrrolidone, polyvinylethyl ether, polyethylene glycol, and many other compounds such as hydroxyethyl cellulose, guar gum, dextran, and pullulan. Examples include sugars.
[0036] これらの中でも、水と接する初期段階における浸水作用に優れ、水に溶解又は分 散する際に発熱する化合物が好ましい。この点を考慮すると、カルボキシル基又はス ルホ基を有するビニル系ポリマーを用いることが好ましぐ特に、単位質量当たりのァ 二オン性基含量の高いビニル系ポリカルボン酸類が好適である。  [0036] Among these, compounds that are excellent in water immersion in the initial stage of contact with water and that generate heat when dissolved or dispersed in water are preferable. In view of this point, it is preferable to use a vinyl polymer having a carboxyl group or a sulfo group, and vinyl polycarboxylic acids having a high anionic group content per unit mass are particularly preferable.
具体的には、ポリアクリル酸塩、アクリル酸/マレイン酸共重合体塩、アクリル酸/ィ タコン酸共重合体塩、アクリル酸アルキル共重合体塩、及びこれらの誘導体等が最 適である。  Specifically, polyacrylates, acrylic acid / maleic acid copolymer salts, acrylic acid / itaconic acid copolymer salts, alkyl acrylate copolymer salts, and derivatives thereof are most suitable.
本発明の有機水溶性高分子化合物の重量平均分子量は 500以上であり、好ましく は 1， 000〜1， 000, 000、より好まし <は 1， 000〜200, 000である。なお、本発明 におけるポリエチレングリコールの平均分子量は、化粧品原料基準（第 2版注解)記 載の平均分子量を示す。また、本発明における有機水溶性高分子化合物の重量平 均分子量は、ポリエチレングリコールを標準物質とするゲルパーミエーシヨンクロマト グラフィ一による測定値である。 有機水溶性高分子化合物で水溶性アルカリ無機化合物を表面処理する方法とし ては、特に限定されるものではない。例えば、水溶性アルカリ無機化合物に有機水 溶性高分子化合物を添加、混合又は被覆する方法等が挙げられる。有機水溶性高 分子化合物を、水溶液として表面処理に用いることが好適である。この水溶液を、撹 拌-流動化状態の水溶性アルカリ無機化合物に滴下又はスプレー添加することが好 ましい。 The weight average molecular weight of the organic water-soluble polymer compound of the present invention is 500 or more, preferably 1,000 to 1,000,000, more preferably <1,000 to 200,000. The average molecular weight of polyethylene glycol in the present invention is the average molecular weight described in the Cosmetic Raw Material Standard (2nd edition comment). The weight average molecular weight of the organic water-soluble polymer compound in the present invention is a value measured by gel permeation chromatography using polyethylene glycol as a standard substance. The method for surface-treating the water-soluble alkali inorganic compound with the organic water-soluble polymer compound is not particularly limited. Examples thereof include a method of adding, mixing or coating an organic water-soluble polymer compound to a water-soluble alkali inorganic compound. It is preferable to use an organic water-soluble high molecular compound as an aqueous solution for the surface treatment. This aqueous solution is preferably added dropwise or sprayed to the water-soluble alkali inorganic compound in a stirred-fluidized state.
[0037] ぐ無機水溶性高分子化合物 >  [0037] Inorganic water-soluble polymer compound>
一方、無機水溶性高分子化合物は、 40°Cにおいて水 100gに対して 0. lg以上、 好ましくは 0. 2g以上、より好ましくは 2g以上の濃度で水と均一に混和する化合物で ある。このような無機水溶性高分子化合物であれば特に限定されず、 1種単独で又 は 2種以上を適宜組み合わせて用いることができる。無機水溶性高分子化合物とし ては、金属アルコキシドの前駆体化合物を含む溶液を加水分解 '縮重合反応するこ とによつて得られるものが好ましく、特に珪酸塩が好ましレ、。  On the other hand, the inorganic water-soluble polymer compound is a compound that is uniformly mixed with water at 40 ° C. at a concentration of 0.1 lg or more, preferably 0.2 g or more, more preferably 2 g or more with respect to 100 g of water. Such inorganic water-soluble polymer compound is not particularly limited, and can be used alone or in appropriate combination of two or more. As the inorganic water-soluble polymer compound, those obtained by subjecting a solution containing a metal alkoxide precursor compound to hydrolysis and polycondensation reaction are preferred, and silicates are particularly preferred.
珪酸塩は古くから石鹼に配合され、水ガラスとして知られており、その構造に基づき 、陰イオンの形による分類に従って分類することができる（Friedrich Liebau, "Str uctural Chemistry of Silicates p72, ¾prmg er— Verlag , 1985年 打 詳細には、 Siに結合する酸素の架橋酸素数（Si— O— Si)で分類でき、その架橋酸 素数力 S4、 3、 2、 1、 0に対応して、それぞれ Q4、 Q3、 Q2、 Ql、 Q0ユニットに分類さ れる (Y. Tsunawaki, N. Iwamoto, T. Hatton and A. Mitsuoishi, J. Non— Cry st. Solids, vol44, p369 (1981) )。  Silicates have long been blended in sarcophagus and have been known as water glass and can be classified according to their anionic form based on their structure (Friedrich Liebau, "Strucctural Chemistry of Silicates p72, ¾prmg er — Verlag, 1985 Strike Details can be classified by the number of cross-linked oxygen atoms (Si—O—Si) bonded to Si, corresponding to the cross-linked oxygen number forces S4, 3, 2, 1, 0, respectively. It is classified into Q4, Q3, Q2, Ql, and Q0 units (Y. Tsunawaki, N. Iwamoto, T. Hatton and A. Mitsuoishi, J. Non—Cry st. Solids, vol44, p369 (1981)).
珪酸塩としては、処理効果を充分に発揮する点から、 Q2ユニット及び/又は Q3ュ ニットを含み、 Si〇2/M2〇モル比（ここで、 Mはアルカリ金属を示す）が 1. 6〜4、好 ましくは 2〜3. 5を有するアルカリ金属珪酸塩が好ましぐ珪酸ナトリウムがより好まし レ、。  Silicates contain Q2 units and / or Q3 units from the standpoint of sufficient treatment effects, and Si02 / M20 mole ratio (where M is an alkali metal) is 1.6 to 4, more preferably sodium silicate, more preferably alkali metal silicate having 2 to 3.5.
[0038] 無機水溶性高分子化合物で水溶性アルカリ無機化合物核粒子を表面処理する方 法としては、特に限定されるものではない。例えば、水溶性アルカリ無機化合物核粒 子に無機水溶性高分子化合物を添加、混合又は被覆する方法等が挙げられる。無 機水溶性高分子化合物を、水溶液として表面処理に用いることが好適である。この 水溶液を、撹拌 ·流動化状態の水溶性アルカリ無機化合物核粒子に滴下又はスプレ 一添加することが好ましい。 [0038] The method for surface-treating the water-soluble alkali-inorganic compound core particles with the inorganic water-soluble polymer compound is not particularly limited. Examples thereof include a method of adding, mixing or coating an inorganic water-soluble polymer compound to water-soluble alkali inorganic compound core particles. It is preferable to use the organic water-soluble polymer compound as an aqueous solution for the surface treatment. this The aqueous solution is preferably added dropwise or sprayed to the water-soluble alkali inorganic compound core particles in a stirred and fluidized state.
[0039] <水難溶性化合物 >  [0039] <Slightly water-soluble compound>
本発明で用いる水難溶性化合物は、 20°Cにおける水への溶解度が 2gZl00g未 満、好ましくは lgZlOOg未満、より好ましくは 0. Ig/lOOg未満の化合物で、水と接 する初期段階で撥水作用のあるものが好ましい。また、 200°C以下、好ましくは 0〜1 60°C、より好ましくは 20〜80°C、さらに好ましくは 40〜60°Cの融点を有する有機化 合物が好適である。水難溶性化合物は 1種単独で又は 2種以上を適宜組み合わせ て用いることができる。  The poorly water-soluble compound used in the present invention is a compound having a solubility in water at 20 ° C of less than 2 gZl00 g, preferably less than lgZlOOg, more preferably less than 0. Ig / lOOg, and has a water repellency at the initial stage of contact with water. Some are preferable. In addition, an organic compound having a melting point of 200 ° C. or less, preferably 0 to 160 ° C., more preferably 20 to 80 ° C., and still more preferably 40 to 60 ° C. is suitable. The poorly water-soluble compounds can be used singly or in appropriate combination of two or more.
水難溶性化合物としては、例えば、高級脂肪酸、ジカルボン酸、高級アルコール、 HLB5以下、好ましくは 3以下の高級アルコール又は高級脂肪酸のアルキレンォキ サイド付加物、高級脂肪酸エステル、高級脂肪酸のグリセライド等が挙げられる。  Examples of the poorly water-soluble compounds include higher fatty acids, dicarboxylic acids, higher alcohols, HLB5 or less, preferably 3 or less higher alcohols or alkylene oxide adducts of higher fatty acids, higher fatty acid esters, higher fatty acid glycerides, and the like.
[0040] 高級アルコールとしては、炭素数 12〜22が好ましぐより好ましくは炭素数 14〜： 18 の炭素鎖長を有するものであり、具体的には、ドデカノール、テトラデカノール、へキ サデカノール、ォクタデカノール等が挙げられる。 HLB5以下、好ましくは 3以下の高 級アルコール又は高級脂肪酸のアルキレンオキサイド付カ卩物としては、炭素数 16〜 22のアルコール又は脂肪酸の 1〜3モルエチレンオキサイド付加体が好適であり、具 体的には、へキサデ力ノールの 1モルエチレンォキシド付加体、ォクタデカノールの 3 モルエチレンォキシド付加体、パルチミン酸の 1モルエチレンォキシド付加体等が挙 げられる。高級脂肪酸エステルとしては、パルミチン酸、ミリスチン酸、ステアリン酸、 ァラキジン酸、ベヘン酸等のメチルエステル又はェチルエステル等が好適である。高 級脂肪酸のグリセライドとしては、ラウリン酸、パルミチン酸、ステアリン酸等のモノ、ジ 又はトリダリセライドが好適である。  [0040] As the higher alcohol, those having 12 to 22 carbon atoms, more preferably those having a carbon chain length of 14 to 18 carbon atoms, specifically, dodecanol, tetradecanol, hexadecanol, and the like. Octadecanol and the like. As a product with an alkylene oxide of a higher alcohol or higher fatty acid having an HLB of 5 or less, preferably 3 or less, a 1 to 3 mol ethylene oxide adduct of an alcohol or a fatty acid having 16 to 22 carbon atoms is suitable. Examples include 1 mol ethylene oxide adduct of hexade strength norm, 3 mol ethylene oxide adduct of octadecanol, 1 mol ethylene oxide adduct of palmitic acid, and the like. As the higher fatty acid ester, methyl ester or ethyl ester such as palmitic acid, myristic acid, stearic acid, arachidic acid, and behenic acid are preferable. As the high-grade fatty acid glyceride, mono-, di- or tridalylide such as lauric acid, palmitic acid and stearic acid are suitable.
[0041] また、初期の湿潤時には吸熱して水溶性アルカリ無機化合物の発熱を制御し、洗 濯すると徐々に水溶性アルカリ無機化合物との中和反応等により水溶性となるという 点から、水難溶性化合物として、ァニオン界面活性剤酸前駆体を用いることが好まし レ、。 [0041] In addition, it absorbs heat during initial wetting to control the heat generation of the water-soluble alkali-inorganic compound, and when washed, it gradually becomes water-soluble due to a neutralization reaction with the water-soluble alkali-inorganic compound. It is preferable to use an anionic surfactant acid precursor as the compound.
ァニオン界面活性剤酸前駆体としては、任意のァニオン界面活性剤の酸前駆体を 好適に用いることができる。ァニオン界面活性剤の酸前駆体としては、飽和又は不飽 和脂肪酸 (平均炭素鎖長 8〜22)、直鎖又は分岐鎖アルキル (平均炭素鎖長 8〜： 18 )ベンゼンスルホン酸、長鎖アルキル（平均炭素鎖長 10〜 20)スルホン酸、長鎖ォレ フィン（平均炭素鎖長 10〜 20)スルホン酸、長鎖モノアルキル（平均炭素鎖長 10〜 2 0)硫酸エステル、ポリオキシエチレン（平均重合度：!〜 10)長鎖アルキル（平均炭素 鎖長 10〜20)エーテル硫酸エステル、ポリオキシエチレン（平均重合度 3〜30)アル キル（平均炭素鎖長 6〜 12)フヱニルエーテル硫酸エステル、 ひ一スルホ脂肪酸（平 均炭素鎖長 8〜22)、長鎖モノアルキル、ジアルキル又はセスキアルキルリン酸、ポリ ォキシエチレンモノアルキル、ジアルキル又はセスキアルキルリン酸等が挙げられる。 ァニオン界面活性剤酸前駆体としては、飽和又は不飽和脂肪酸 (平均炭素鎖長 8 〜22)が好ましぐ炭素数 8〜： 18の炭素鎖長を有するものがより好ましい。具体的に は、力プリン酸、ラウリン酸、ミリスチン酸、パルミチン酸等の飽和脂肪酸、ォレイン酸 等の不飽和脂肪酸等が挙げられる。この中でも、保存安定性の点から、炭素数 12〜 18の飽和脂肪酸が好ましぐ製造性を考慮すると、ラウリン酸がより好ましい。 Any anionic surfactant acid precursor can be used as an anionic surfactant acid precursor. It can be used suitably. Acid precursors for the anionic surfactants include saturated or unsaturated fatty acids (average carbon chain length 8-22), linear or branched alkyl (average carbon chain length 8: 18), benzenesulfonic acid, long chain alkyl (Average carbon chain length 10-20) sulfonic acid, long chain olefin (average carbon chain length 10-20) sulfonic acid, long chain monoalkyl (average carbon chain length 10-20) sulfate ester, polyoxyethylene ( Average degree of polymerization:! To 10) Long chain alkyl (average carbon chain length 10 to 20) ether sulfate, polyoxyethylene (average degree of polymerization 3 to 30) alkyl (average carbon chain length 6 to 12) phenyl ether sulfate, Examples include monosulfo fatty acids (average carbon chain length of 8 to 22), long-chain monoalkyl, dialkyl or sesquialkyl phosphate, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate. The anionic surfactant acid precursor is more preferably one having a carbon chain length of 8 to 18 carbon atoms, which is preferable for saturated or unsaturated fatty acids (average carbon chain length of 8 to 22). Specific examples include saturated fatty acids such as force puric acid, lauric acid, myristic acid and palmitic acid, and unsaturated fatty acids such as oleic acid. Among these, lauric acid is more preferable from the viewpoint of storage stability, in consideration of manufacturability of saturated fatty acids having 12 to 18 carbon atoms.
[0042] 第 1の表面処理剤で表面処理された水溶性アルカリ無機化合物核粒子を、さらに 水難溶性化合物で表面処理する方法としては、特に限定されるものではない。例え ば、表面処理された水溶性アルカリ無機化合物核粒子に水難溶性化合物を添加、 混合又は被覆する方法等が挙げられる。水難溶性化合物を溶融させて液体状とし、 この液体を、撹拌'流動状態の表面処理された水溶性アルカリ無機化合物核粒子に 滴下する又はスプレー添加する方法が好ましい。  [0042] The method for surface-treating the water-soluble alkali-inorganic compound core particles surface-treated with the first surface-treating agent with the poorly water-soluble compound is not particularly limited. For example, a method of adding, mixing, or coating a poorly water-soluble compound to the surface-treated water-soluble alkali inorganic compound core particles. A method in which a poorly water-soluble compound is melted to form a liquid, and this liquid is dropped or sprayed onto the surface-treated water-soluble alkali-inorganic compound core particles in a fluidized state.
[0043] 本発明の表面処理水溶性アルカリ無機化合物粒子中の各成分の配合量を下記に 示す。  [0043] The blending amount of each component in the surface-treated water-soluble alkali inorganic compound particles of the present invention is shown below.
水溶性アル力リ無機化合物は、表面処理水溶性アル力リ無機化合物粒子中 50〜 9 8質量％用いることが好ましぐ 70〜95質量％がより好ましい。水溶性アルカリ無機 化合物が 50質量％未満ではアルカリ剤として不充分となる場合があり、一方、 98% を超えると処理剤の量が少なくなりすぎ、充分な表面処理ができなレ、場合がある。 有機水溶性高分子化合物は、水溶性アルカリ無機化合物核粒子に対して 0.：!〜 1 0質量％、特に 0. 5〜8質量％で用いることが好ましい。 0. 1質量％未満では、表面 処理の効果が得られない場合があり、 10質量％を超えると、水溶性アルカリ性無機 化合物の配合量が少なくなりすぎる場合がある。 The water-soluble inorganic compound is preferably used in an amount of 50 to 98 mass% in the surface-treated water-soluble inorganic compound particles, more preferably 70 to 95 mass%. If the amount of water-soluble alkali inorganic compound is less than 50% by mass, it may be insufficient as an alkali agent. On the other hand, if it exceeds 98%, the amount of the treatment agent may be too small and sufficient surface treatment may not be possible. . The organic water-soluble polymer compound is preferably used in an amount of from 0.:! To 10% by mass, particularly from 0.5 to 8% by mass, based on the water-soluble alkali-inorganic compound core particles. 0. Less than 1% by mass, surface The treatment effect may not be obtained, and if it exceeds 10% by mass, the amount of the water-soluble alkaline inorganic compound may be too small.
[0044] 無機水溶性高分子化合物は、表面処理水溶性アルカリ無機化合物粒子中に対し て 1〜30質量％、特に 10〜28質量％で用いることが好ましい。 1質量％未満では、 表面処理の効果が得られない場合があり、 30質量％を超えると、無機化合物の配合 量が少なくなりすぎる場合がある。  [0044] The inorganic water-soluble polymer compound is preferably used in an amount of 1 to 30% by mass, particularly 10 to 28% by mass, based on the surface-treated water-soluble alkali inorganic compound particles. If it is less than 1% by mass, the effect of the surface treatment may not be obtained. If it exceeds 30% by mass, the compounding amount of the inorganic compound may be too small.
水難溶性化合物は、表面処理された水溶性アルカリ無機化合物核粒子に対して、 0.：!〜 10質量％、特に 2〜8質量％で用いることが好ましい。 0. 1質量％未満では、 表面処理の効果が得られない場合があり、 10質量％を超えると、水溶性のアルカリ 性無機化合物の配合量が少なくなりすぎる場合がある。  The poorly water-soluble compound is preferably used in an amount of 0.:! To 10% by mass, particularly 2 to 8% by mass, based on the surface-treated water-soluble alkaline inorganic compound core particles. If the amount is less than 1% by mass, the effect of the surface treatment may not be obtained. If the amount exceeds 10% by mass, the amount of the water-soluble alkaline inorganic compound may be too small.
本発明の組成物において、 （C)表面処理した水溶性アルカリ無機化合物粒子は、 組成物の全量を基準として、好ましくは 5〜40質量％、より好ましくは 10〜30質量％ の量で含まれるのが好ましい。このような範囲内にあると、低水温中での分散性が大 きく改善できるので好ましい。  In the composition of the present invention, (C) the surface-treated water-soluble alkali inorganic compound particles are preferably contained in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the composition. Is preferred. Within such a range, dispersibility at low water temperatures can be greatly improved, which is preferable.
(C)表面処理水溶性アルカリ無機化合物粒子と (B)界面活性剤含有粒子の配合 比率は（C)粒子/ (B)粒子（質量比）が、好ましくは 5/95〜50/50、より好ましくは 10/90〜25/75である。質量比が 50/50を超えると洗浄性能が低下する場合が ある。  The blending ratio of (C) surface-treated water-soluble alkali inorganic compound particles and (B) surfactant-containing particles is (C) particles / (B) particles (mass ratio), preferably 5 / 95-50 / 50 It is preferably 10/90 to 25/75. If the mass ratio exceeds 50/50, the cleaning performance may decrease.
[0045] <表面処理水溶性アルカリ無機化合物粒子 >  <Surface treatment water-soluble alkali inorganic compound particles>
本発明の表面処理水溶性アルカリ無機化合物粒子は、水溶性アルカリ無機化合物 核粒子が有機又は無機水溶性高分子化合物で表面処理され、さらにその処理され た表面が水難溶性化合物で処理されてなる。本発明の表面とは、水溶性アルカリ無 機化合物粒子の一次粒子表面又は造粒して 1次粒子が 2〜30個程度固まってひと つになってレ、る水溶性アルカリ無機化合物粒子群（2次粒子又は凝集粒子を含む） の全表面のどちらも含むものである。なお、水溶性アルカリ無機化合物粒子群となつ ている場合、表面の微小凹部の深さは 0. 01〜50 z mである。  The surface-treated water-soluble alkali-inorganic compound particles of the present invention are obtained by treating the water-soluble alkali-inorganic compound core particles with an organic or inorganic water-soluble polymer compound, and further treating the treated surface with a poorly water-soluble compound. The surface of the present invention refers to the surface of primary particles of water-soluble alkali inorganic compound particles or a group of water-soluble alkali inorganic compound particles that are granulated to form about 2 to 30 primary particles. (Including secondary particles or agglomerated particles). In the case of the water-soluble alkali-inorganic compound particle group, the depth of the minute concave portion on the surface is 0.01 to 50 zm.
水溶性アルカリ無機化合物核粒子の表面上における、水溶性高分子化合物と水 難溶性化合物は、水溶性アルカリ無機化合物核粒子の表面に水溶性高分子化合物 が存在して層を形成し、その外層部に水難溶性化合物が存在しても、ランダムに混 在した状態になっていてもよい。溶解性と保存安定性の点から、表面処理水溶性ァ ルカリ無機化合物粒子の最外層に水溶性高分子化合物よりも水難溶性化合物が多 く存在していることが好ましい。また、製造性の点から、水溶性アルカリ無機化合物核 粒子の表面近傍に、水難溶性化合物よりも水溶性高分子化合物が多く存在すること が好ましい。 On the surface of the water-soluble alkali-inorganic compound core particles, the water-soluble polymer compound and the poorly water-soluble compound are formed on the surface of the water-soluble alkali-inorganic compound core particles. May form a layer, and a poorly water-soluble compound may be present in the outer layer portion or may be in a randomly mixed state. From the viewpoints of solubility and storage stability, it is preferable that more water-insoluble compounds are present in the outermost layer of the surface-treated water-soluble alkali inorganic compound particles than water-soluble polymer compounds. From the viewpoint of manufacturability, it is preferable that more water-soluble polymer compound is present near the surface of the water-soluble alkali-inorganic compound core particles than the poorly water-soluble compound.
[0046] 表面処理水溶性アルカリ無機化合物粒子の特に好ましい構造は、水溶性アルカリ 無機化合物核粒子と、この粒子表面上の一部又は全面に形成された水溶性高分子 化合物を含む第 1表面処理部と、第 1表面処理部表面上の一部又は全面に形成さ れた水難溶性化合物を含む第 2表面処理部とを有する構造である。  [0046] A particularly preferred structure of the surface-treated water-soluble alkali-inorganic compound particles is a first surface treatment comprising water-soluble alkali-inorganic compound core particles and a water-soluble polymer compound formed on a part or the entire surface of the particle surface. And a second surface treatment portion containing a poorly water-soluble compound formed on a part or the entire surface of the first surface treatment portion.
水難溶性化合物が高級脂肪酸等のァニオン界面活性剤の酸前駆体である場合は 、通常は第 1表面処理部の水溶性高分子水溶液によって水溶性アルカリ無機塩が 溶出し、粒子表面がアルカリ性となっているため、添加されたァニオン界面活性剤の 酸前駆体は粒子表面で中和される。添加するァニオン界面活性剤の酸前駆体の量 が比較的多い場合は、部分的に中和反応が起こらず、酸前駆体の形で残存すること もあり得る。ァニオン界面活性剤の酸前駆体の中和状態は示差走査熱量測定法 (Di fferential Scanning Calorimetry)等によって調べることも可能である。このよう に、ァニオン界面活性剤の酸前駆体は粒子表面で完全中和される場合も部分中和 される場合もあり得るため、ァニオン界面活性剤の酸前駆体及び/又はその塩によ る第 2表面処理部が形成されるが、いずれの場合も本発明における表面処理水溶性 アルカリ無機化合物粒子として好適に利用可能である。  When the poorly water-soluble compound is an acid precursor of an anionic surfactant such as a higher fatty acid, the water-soluble alkali inorganic salt is usually eluted by the water-soluble polymer aqueous solution in the first surface treatment portion, and the particle surface becomes alkaline. Therefore, the added acid precursor of the anionic surfactant is neutralized on the particle surface. If the amount of the anionic surfactant acid precursor to be added is relatively large, the neutralization reaction does not occur partially, and it may remain in the form of an acid precursor. The neutralization state of the acid precursor of the anionic surfactant can also be examined by differential scanning calorimetry or the like. As described above, since the acid precursor of the anionic surfactant may be completely neutralized or partially neutralized on the particle surface, it depends on the acid precursor of the anionic surfactant and / or a salt thereof. Although the second surface treatment portion is formed, in any case, the surface treatment water-soluble alkali inorganic compound particles in the present invention can be suitably used.
[0047] なお、第 1表面処理部及び第 2表面処理部には他の成分として、本発明の効果を 損なわない範囲で、バインダー、分散剤、可溶化剤、 pH調整剤、水難溶性化合物以 外の界面活性剤等の各種添加剤が適宜含まれてレ、てもよレ、。界面活性剤が含まれ る場合は、表面処理水溶性アルカリ無機化合物粒子中、 10質量％未満が好ましぐ より好ましくは 5質量％以下、さらに好ましくは 1質量％以下である。なお、水難溶性 化合物として配合される脂肪酸等は、表面処理水溶性アル力リ無機化合物粒子中の 界面活性剤の配合量には含まれなレ、。 [0048] 本発明の（C)表面処理水溶性アルカリ無機化合物粒子の物性値は、特に制限さ れるものではないが、嵩密度は、通常、 0. 3g/mL以上、好ましくは 0. 5〜： 1. 4g/ mL、より好ましくは 0. 6〜： 1. 3g/mLである。嵩密度が小さ過ぎても大き過ぎても他 の粒子と混合して使用する際に分級しやすくなる場合がある。また、平均粒子径は、 好ましく fま 200〜2， 000 z m、より好ましく fま 300〜1 , 500 μ m、特 (こ好ましく fま 30 0〜500 z mである。平均粒子径が 200 x m未満になると、比表面積が大き過ぎ、酵 素活性低下抑制効果が得られに《なる可能性があり、一方、 2， 000 x mを超えると 表面処理水溶性アルカリ無機化合物粒子そのものの溶解性が劣化する場合がある。 さらに、安息角は 70° 以下が好ましぐより好ましくは 50° 以下である。安息角が 70 。 を超えると粒子の取扱性が悪化する場合がある。なお、本発明における平均粒子 径、嵩密度の測定は実施例に記載の測定法により、安息角の測定は、筒井理化学 器械 (株)製、ターンテーブル形安息角測定器を用いて測定する。 [0047] The first surface treatment section and the second surface treatment section include other components such as a binder, a dispersant, a solubilizer, a pH adjuster, and a poorly water-soluble compound as long as the effects of the present invention are not impaired. Various additives such as an external surfactant are included as appropriate. In the case where a surfactant is included, the content of the surface-treated water-soluble alkali inorganic compound particles is preferably less than 10% by mass, more preferably 5% by mass or less, and even more preferably 1% by mass or less. Fatty acids and the like that are blended as poorly water-soluble compounds are not included in the blending amount of the surfactant in the surface-treated water-soluble alcoholic inorganic compound particles. [0048] The physical properties of the (C) surface-treated water-soluble alkali inorganic compound particles of the present invention are not particularly limited, but the bulk density is usually 0.3 g / mL or more, preferably 0.5 to : 1.4 g / mL, more preferably 0.6-: 1.3 g / mL. If the bulk density is too small or too large, it may be easily classified when mixed with other particles. The average particle size is preferably f to 200 to 2,000 zm, more preferably f to 300 to 1,500 μm, and particularly (preferably f to 300 to 500 zm. The average particle size is less than 200 xm. In this case, the specific surface area is too large, and the enzyme activity lowering suppression effect may not be obtained. On the other hand, if it exceeds 2,000 xm, the solubility of the surface-treated water-soluble alkali inorganic compound particles themselves deteriorates. Furthermore, the angle of repose is preferably 70 ° or less, more preferably 50 ° or less, and if the angle of repose exceeds 70, the handleability of the particles may deteriorate. The particle diameter and bulk density are measured by the measurement method described in the Examples, and the angle of repose is measured by using a turntable type angle of repose measuring instrument manufactured by Tsutsui Rika Instruments Co., Ltd.
表面処理水溶性アルカリ無機化合物粒子中の水分は、貯蔵中の固化 (ケーキング )を防止する観点から、 8質量％以下が好ましぐさらに 7質量％以下、特に 6質量％ 以下が好ましい。なお、本発明における水分量は JISK3362— 1998に規定された 加熱減量法により測定する。  From the viewpoint of preventing solidification (caking) during storage, the water content in the surface-treated water-soluble alkali inorganic compound particles is preferably 8% by mass or less, more preferably 7% by mass or less, and particularly preferably 6% by mass or less. The water content in the present invention is measured by the heat loss method specified in JISK3362-1998.
[0049] <表面処理水溶性アルカリ無機化合物粒子の製造方法 >  <Method for producing surface-treated water-soluble alkali-inorganic compound particles>
以下、本発明の表面処理水溶性アルカリ無機化合物粒子の製造方法について詳 述する。  Hereinafter, the method for producing the surface-treated water-soluble alkali inorganic compound particles of the present invention will be described in detail.
本発明の表面処理水溶性アルカリ無機化合物粒子の製造方法は、下記第 1工程 及び第 2工程を含むものである。  The method for producing surface-treated water-soluble alkali-inorganic compound particles of the present invention includes the following first step and second step.
第 1工程:水溶性アルカリ無機化合物核粒子に水溶性高分子化合物水溶液を添カロ し、水溶性高分子化合物で水溶性アルカリ無機化合物核粒子を表面処理する工程 第 2工程：第 1工程で処理された水溶性アルカリ無機化合物核粒子に水難溶性化合 物を添加し、前記粒子を表面処理する工程。  1st step: Adding water-soluble polymer compound aqueous solution to water-soluble alkali-inorganic compound core particles and surface-treating water-soluble alkali-inorganic compound core particles with water-soluble polymer compound 2nd step: Processing in 1st step Adding a poorly water-soluble compound to the water-soluble alkali-inorganic compound core particles, and subjecting the particles to a surface treatment.
第 1工程は、水溶性アルカリ無機化合物核粒子に水溶性高分子化合物水溶液を 添加し、水溶性高分子化合物で水溶性アルカリ無機化合物核粒子を表面処理する 工程である。 In the first step, a water-soluble polymer compound aqueous solution is added to the water-soluble alkali-inorganic compound core particles, and the water-soluble alkali-inorganic compound core particles are surface-treated with the water-soluble polymer compound. It is a process.
水溶性アルカリ無機化合物核粒子を、後述する造粒 ·被覆 (コーティング)装置内に 充填し、これに水溶性高分子化合物水溶液を添加し、表面処理を行う。  The water-soluble alkali-inorganic compound core particles are filled in a granulation / coating (coating) apparatus, which will be described later, and a water-soluble polymer compound aqueous solution is added thereto for surface treatment.
[0050] 水溶性高分子化合物水溶液は、有機水溶性高分子化合物の場合、通常 0.：!〜 9 0質量％、好ましくは 0. 5〜80質量％、より好ましくは 1〜60質量％であって、粘度（ ブルックフィールド型粘度計を用いた 25°Cにおける測定値）が、好ましくは 0. 001〜 100Pa . s、より好ましくは 0. 005〜50Pa ' sである有機水溶性高分子化合物水溶液 にするとよい。無機水溶性高分子化合物の場合、通常:!〜 60質量％、好ましくは 5〜 55質量％、より好ましくは 10〜50質量％無機水溶性高分子化合物とするとよい。水 溶性高分子化合物水溶液を、撹拌'流動化状態の水溶性アルカリ無機化合物核粒 子に滴下又はスプレー添加することが好ましレ、。  [0050] In the case of an organic water-soluble polymer compound, the water-soluble polymer compound aqueous solution is usually 0.:! To 90% by mass, preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass. An organic water-soluble polymer compound having a viscosity (measured value at 25 ° C. using a Brookfield viscometer) is preferably 0.001 to 100 Pa · s, more preferably 0.005 to 50 Pa ′s. An aqueous solution is recommended. In the case of an inorganic water-soluble polymer compound, usually:! To 60% by mass, preferably 5 to 55% by mass, and more preferably 10 to 50% by mass, an inorganic water-soluble polymer compound. It is preferable to drop or spray the water-soluble polymer compound aqueous solution to the water-soluble alkali inorganic compound core particles in a fluidized state.
[0051] 第 2工程は、第 1工程で処理された水溶性アルカリ無機化合物核粒子に水難溶性 化合物を添加し、前記粒子を表面処理する工程である。  [0051] The second step is a step of surface-treating the particles by adding a poorly water-soluble compound to the water-soluble alkali-inorganic compound core particles treated in the first step.
第 1工程で処理された水溶性アルカリ無機化合物核粒子を、後述する造粒 ·被覆 装置内に充填し、これに水難溶性化合物を添加して表面処理を行う。水難溶性化合 物は、溶融させて液体状とし、この液体を、撹拌'流動状態の第 1工程で表面処理さ れた水溶性アルカリ無機化合物核粒子に滴下する又はスプレー添加する方法が好 ましい。  The water-soluble alkali-inorganic compound core particles treated in the first step are filled in a granulating / coating apparatus described later, and a poorly water-soluble compound is added thereto for surface treatment. A method in which a poorly water-soluble compound is melted to form a liquid, and this liquid is dropped or sprayed onto the water-soluble alkali-inorganic compound core particles surface-treated in the first step in a stirred and fluidized state is preferred. .
上記第 1及び第 2工程において、水溶性アルカリ無機化合物核粒子を具体的に造 粒 ·被覆する方法としては、以下の方法が挙げられる。 （1) .水溶性アルカリ無機化 合物核粒子に処理剤等 (水溶性高分子化合物、水難溶性化合物)を添加し撹拌羽 根で撹拌して造粒 '被覆する撹拌造粒法、（2) .水溶性アルカリ無機化合物核粒子 を転動させつつ処理剤等を噴霧して造粒'被覆する転動造粒法、 (3) .水溶性アル カリ無機化合物核粒子を流動化させつつ、処理剤等を噴霧し造粒'被覆する流動層 造粒法等が挙げられる。上記第 1工程、及び第 2工程はそれぞれ同一の造粒 '被覆 方法及び装置によってなされてもよいし、複数の造粒 ·被覆方法及び装置を組み合 わせてもよい。以下、それぞれの方法、製造装置、条件等について説明する。  In the first and second steps, examples of the method for specifically granulating and coating the water-soluble alkali inorganic compound core particles include the following methods. (1) .Agitation granulation method in which a processing agent or the like (water-soluble polymer compound, poorly water-soluble compound) is added to the water-soluble alkali inorganic compound core particle, and the mixture is stirred with a stirring blade and granulated. ) Rolling granulation method of spraying treatment agent etc. while rolling water-soluble alkali inorganic compound core particles and coating (3). Fluidizing water-soluble alkali inorganic compound core particles, Examples thereof include a fluidized bed granulation method in which a treatment agent or the like is sprayed and granulated. The first step and the second step may be performed by the same granulation and coating method and apparatus, or a plurality of granulation and coating methods and apparatuses may be combined. Hereinafter, each method, a manufacturing apparatus, conditions, etc. are demonstrated.
[0052] (1) .撹拌造粒法 撹拌造粒法では任意の型式の撹拌造粒装置を使用することができる。その中でも、 撹拌羽根を備えた撹拌軸を内部の中心に有し、撹拌羽根が回転する際に撹拌羽根 と器壁との間にクリアランスを形成する構造の装置であることが好ましい。クリアランス は l〜30mmであるのが好ましぐ 3〜10mmがより好ましレ、。クリアランスが lmm未 満では付着層により混合機が過動力となりやすい場合がある。 30mmを超えると圧密 化の効率が低下するため粒度分布がブロードに、また、造粒時間が長くなり生産性 が低下する場合がある。この様な構造を有する撹拌造粒機としては、例えばへンシ工 ルミキサー（三井三池化工機 (株)製）、ハイスピードミキサー (深江工業 (株)製）、バ 一チカルグラニュレーター（ (株)ノ ゥレック製)等の装置が挙げられる。特に好ましく は横型の混合槽で円筒の中心に撹拌軸を有し、この軸に撹拌羽根を取付けて粉末 の混合を行う形式のミキサーである。このようなミキサーとしては、例えばレーディゲミ キサー（ (株）マツボー製）、プロ一シェア一ミキサー（大平洋機ェ (株)製）である。 撹拌造粒法における好適な造粒条件を以下に示す。 [0052] (1) Stirring granulation method Any type of agitation granulator can be used in the agitation granulation method. Among them, it is preferable that the apparatus has a structure in which a stirring shaft provided with a stirring blade is provided in the center and a clearance is formed between the stirring blade and the vessel wall when the stirring blade rotates. The clearance is preferably l-30mm, more preferably 3-10mm. When the clearance is less than lmm, the mixer may be overpowered by the adhesion layer. If it exceeds 30 mm, the compaction efficiency decreases, so the particle size distribution becomes broader, and the granulation time becomes longer, which may reduce productivity. Examples of the agitation granulator having such a structure include, for example, Henshi Kogyo Mixer (Mitsui Miike Chemical Co., Ltd.), High Speed Mixer (Fukae Kogyo Co., Ltd.), and Vertical Granulator (Corporation) And a device such as Norec). Particularly preferred is a mixer of a horizontal type mixing tank having a stirring shaft at the center of a cylinder and mixing the powder by attaching a stirring blade to this shaft. As such a mixer, for example, Lady Gemixer (manufactured by Matsubo Co., Ltd.) and a professional share-one mixer (manufactured by Taiheiyo Machine Co., Ltd.) are used. Preferable granulation conditions in the stirring granulation method are shown below.
[0053] (i)フルード数 (Fr数） [0053] (i) Fluid number (Fr number)
撹拌造粒法においては、下記式で定義されるフルード数は 1〜： 16であるのが好ま しぐ 2〜9がより好ましい。フルード数が 1未満であると、流動化が不充分であるため 表面処理が不充分となる場合がある。一方、 16を超えると粒子に対するせん断力が 強くなり過ぎ表面処理部に壊れが発生する場合がある。  In the stirring granulation method, the fluid number defined by the following formula is preferably 1 to 16 and more preferably 2 to 9. If the Froude number is less than 1, surface treatment may be insufficient due to insufficient fluidization. On the other hand, if it exceeds 16, the shearing force on the particles becomes too strong, and the surface treatment part may be broken.
Fr=V2/ (R X g)  Fr = V2 / (R X g)
V：撹拌羽根の先端の周速 (m/s)  V: Peripheral speed at the tip of the stirring blade (m / s)
R:撹拌羽根の回転半径 (m)  R: Stirring blade rotation radius (m)
g :重力加速度（mZs2)  g: Gravitational acceleration (mZs2)
(ii)チョッパー回転数  (ii) Chopper rotation speed
撹拌造粒法において、使用される撹拌造粒機には、造粒物の圧密化促進及び粗 粉解砕促進のために、高速で回転するチョッパーが装備されている。チョッパーの回 転速度としては表面処理部の壊れが発生しない程度の回転数が好ましい。チヨッパ 一先端速度（周速）で 30m/s以下が好ましぐ 0〜20m/s以下がより好ましい。  In the agitation granulation method, the agitation granulator used is equipped with a chopper that rotates at a high speed in order to promote compaction of the granulated product and coarse powder crushing. The rotation speed of the chopper is preferably such that the surface treatment portion is not broken. The tipper speed (circumferential speed) is preferably 30 m / s or less, more preferably 0 to 20 m / s or less.
[0054] (iii)造粒時間 撹拌造粒法にぉレ、て、回分式の造粒における造粒時間及び連続式の造粒におけ る平均滞留時間は、 0. 5〜20分が好ましぐ 3〜： 10分がより好ましい。造粒時間（平 均滞留時間）が 0. 5分未満であると、時間が短過ぎて好適な平均粒子径及び嵩密 度を得るための造粒制御が困難となり、粒度分布がブロードになる場合がある。 20分 を超えると時間が長過ぎて生産性が低下する場合がある。 [0054] (iii) Granulation time In the agitation granulation method, the granulation time in batch granulation and the average residence time in continuous granulation are preferably from 0.5 to 20 minutes. preferable. If the granulation time (average residence time) is less than 0.5 minutes, the time is too short and it becomes difficult to control granulation to obtain a suitable average particle size and bulk density, and the particle size distribution becomes broad. There is a case. If it exceeds 20 minutes, the time may be too long and productivity may decrease.
(iv)水溶性アルカリ無機化合物核粒子の充填率 (iv) Packing ratio of water-soluble alkali inorganic compound core particles
撹拌造粒法にぉレ、て、水溶性アルカリ無機化合物核粒子の造粒機への充填率 (仕 込み量）としては、混合機の全内容積の 70容積％以下が好ましぐ 15〜40容積％が より好ましい。充填率 (仕込み量）が、 70容積％を超えると混合機内での混合効率が 低下し、好適に造粒を行うことができない場合がある。  The mixing rate (feeding amount) of water-soluble alkali inorganic compound core particles in the granulator is preferably 70% by volume or less of the total internal volume of the mixer. 40% by volume is more preferred. If the filling rate (preparation amount) exceeds 70% by volume, the mixing efficiency in the mixer may decrease, and granulation may not be performed properly.
(V)処理剤の添加方法 (V) Method of adding treatment agent
撹拌造粒法において、水溶性高分子化合物水溶液、水難溶性化合物等の処理剤 は、好ましくは撹拌 ·流動状態の粒子に対して、滴下もしくは噴霧して添加される。静 置状態にある粒子に処理剤等を滴下もしくは添加した後、撹拌を開始して造粒 ·被覆 操作も可能である。し力しながら、被覆性を高めるためにも、撹拌'流動状態の粒子 に対して滴下もしくは噴霧して添加することが好ましい。  In the stirring granulation method, the treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is preferably added dropwise or sprayed to the particles in the stirring / fluid state. After dropping or adding a treatment agent or the like to the particles in a stationary state, agitation is started and granulation / coating operation is also possible. In order to improve the covering property while applying force, it is preferably added dropwise or sprayed onto the particles in the stirred and flowing state.
(2) .転動造粒法 (2) Rolling granulation method
転動造粒法では任意の型式の転動造粒装置を使用することができる。その中でも ドラム状の円筒が回転して処理するものが好ましぐ特に任意の形状の邪魔板を具 備しているものが好ましい。ドラム型造粒機としては、水平円筒型造粒機、 日本粉体 工業技術協会編、造粒ハンドブック第一版第 1刷記載の円錐ドラム型造粒機、多段 円錐ドラム型造粒機、撹拌羽根付ドラム型造粒機等が挙げられる。  Any type of rolling granulator can be used in the rolling granulation method. Among them, a drum-shaped cylinder rotating and processing is preferable, and a device provided with an arbitrarily shaped baffle plate is particularly preferable. The drum-type granulator includes horizontal cylindrical granulators, conical drum granulators described in the first edition of the granulation handbook, edited by Japan Powder Industrial Technology Association, multi-stage conical drum granulators, agitation Examples thereof include a drum type granulator with blades.
転動造粒法における好適な造粒条件を以下に示す。  Suitable granulation conditions in the rolling granulation method are shown below.
(i)処理時間 (i) Processing time
回分式における処理時間、連続式における以下の式で定義される平均滞留時間 は、 5〜： 120分力 S好ましく、より好ましくは 10〜90分、さらに好ましくは 10〜40分であ る。前記時間が 5分未満であると、高嵩密度にならない場合がある一方、 120分を超 えると生産性の低下又は粒子が崩壊する場合がある。 Tm= (m/Q) X 60 The treatment time in the batch system and the average residence time defined by the following formula in the continuous system are preferably 5 to 120 force S, more preferably 10 to 90 minutes, and still more preferably 10 to 40 minutes. When the time is less than 5 minutes, a high bulk density may not be obtained. On the other hand, when the time exceeds 120 minutes, productivity may be reduced or particles may be collapsed. Tm = (m / Q) X 60
Tm:平均滞留時間（min)  Tm: Average residence time (min)
m ：容器回転型混合機内の粒子滞留量 (kg)  m: Particle retention in the container rotating mixer (kg)
Q ：連続運転における能力（kg/hr)  Q: Capacity in continuous operation (kg / hr)
(ii)フルード数（Fr)  (ii) Fluid number (Fr)
下記式で定義されるフルード数は、 0. 01-0. 8となる条件を選択するのが好まし レヽ。フノレード数は、 0. 05〜0. 7力 Sより好ましく、 0.：!〜 0. 65カさらに好ましレヽ。フノレ ード数が 0. 01未満であると、均一でかつ高嵩密度の粒子が得られない場合がある 一方、 0. 8を超えると、ドラム型混合機の場合には、粒子が飛散し、正常な剪断混合 が起こらない場合がある。  It is preferable to select the condition that the fluid number defined by the following formula is 0.01-0.8. The number of funades is more preferably 0.05 to 0.7 force S, and more preferably 0.:! To 0.65. If the fanolade number is less than 0.01, uniform and high bulk density particles may not be obtained. On the other hand, if it exceeds 0.8, the particles are scattered in the case of a drum type mixer. Normal shear mixing may not occur.
Fr=V2/ (R X g)  Fr = V2 / (R X g)
V：容器回転型混合機最外周の周速 (mZs)  V: Peripheral speed (mZs) at the outermost circumference of the rotating container
R：容器回転型混合機最外周の回転中心からの半径 (m)  R: Radius from the rotation center on the outermost periphery of the container rotating mixer (m)
g :重力加速度（m/s2)  g: Gravitational acceleration (m / s2)
(iii)容積充填率 (A)  (iii) Volume filling rate (A)
下記式で定義される容積充填率が、 15〜50容積％となる条件を選択するのが好 ましい。容積充填率は、より好ましくは 20〜45容積％、さらに好ましくは 25〜40容積 %である。容積充填率が 15容積％未満であると、生産性が悪い場合がある一方、 50 容積％を超えると良好な剪断混合が生じない場合がある。  It is preferable to select a condition in which the volume filling rate defined by the following formula is 15 to 50% by volume. The volume filling rate is more preferably 20 to 45% by volume, and further preferably 25 to 40% by volume. If the volume filling rate is less than 15% by volume, the productivity may be poor, whereas if it exceeds 50% by volume, good shear mixing may not occur.
容積充填率 (A) = (M/ p ) /VX 100  Volume filling factor (A) = (M / p) / VX 100
M：容器回転型混合機への水溶性アルカリ無機化合物核粒子の仕込量 (g) P：水溶性アルカリ無機化合物核粒子の嵩密度 (g/U  M: Amount of water-soluble alkali-inorganic compound core particles charged into the container rotating mixer (g) P: Bulk density of water-soluble alkali-inorganic compound core particles (g / U
V：容器回転型混合機の容積 (L)  V: Volume of container rotation type mixer (L)
(iv)処理剤の添加方法  (iv) Treatment agent addition method
転動造粒法において、水溶性高分子水溶液、水難溶性化合物等の処理剤は、転 動-流動状態の粒子に対して噴霧して添加される。静置状態にある粒子に処理剤等 を滴下もしくは添加した後、撹拌を開始して造粒 ·被覆操作も可能である。し力 なが ら、被覆性を高めるためにも、撹拌 ·流動状態の粒子に対して滴下もしくは噴霧して 添加することが好ましい。 In the rolling granulation method, a treatment agent such as a water-soluble polymer aqueous solution or a poorly water-soluble compound is added by spraying to particles in a rolling-fluid state. After dropping or adding a treatment agent or the like to the particles in a stationary state, agitation is started and granulation / coating operation is possible. However, in order to improve the covering property, it is dripped or sprayed on the agitated / flowing particles. It is preferable to add.
[0057] (3) .流動層造粒法  [0057] (3). Fluidized bed granulation method
流動層造粒法では流動層本体、整流板、送風機、吸気フィルター、エアヒーター及 びクーラー、スプレー装置、集塵装置等で構成された任意の型式の流動層造粒装置 を使用することができる。例えば、 日本粉体技術協会編、造粒ハンドブック第一版第 1刷記載の回分式流動層造粒装置（トップスプレー式、サイドスプレー式、ボトムスプ レー式等)、噴流流動層造粒装置、噴流動層造粒装置、半連続式流動層造粒装置（ 分散板反転排出式、下部排出式、側壁排出式等)連続式流動層造粒装置 (横型多 室型、円筒型等)等が好適に利用できる。具体的装置の利用例としては回分式流動 層造粒装置の Glatt _ POWREXシリーズ [ (株）パゥレックス製]、フローコーターシリ ーズ [ (株)大川原製作所製]、連続式流動層造粒装置の MIXGRADシリーズ [ (株） 大 J 11原製作所製]等が挙げられる。  In the fluidized bed granulation method, any type of fluidized bed granulator composed of a fluidized bed body, current plate, air blower, intake filter, air heater and cooler, spray device, dust collector, etc. can be used. . For example, batch-type fluidized bed granulators (top spray type, side spray type, bottom spray type, etc.), spouted fluidized bed granulators, jet fluidized bed granulators, etc. Fluidized bed granulators, semi-continuous fluidized bed granulators (dispersed plate reverse discharge type, bottom discharge type, side wall discharge type, etc.) Continuous fluidized bed granulators (horizontal multi-chamber type, cylindrical type, etc.) are suitable. Available to: Specific examples of use of the equipment include batch type fluidized bed granulator Glatt _ POWREX series [manufactured by Paulex Co., Ltd.], flow coater series [manufactured by Okawara Seisakusho], and continuous fluidized bed granulator MIXGRAD series [Dai J11 Hara Seisakusho] etc. are listed.
[0058] 流動層造粒法における造粒条件として、静置時の原料粉体層の平均厚さは 50〜5 00mm程度が好ましい。その後、流動層に風を送り、粉体を流動化させた後に水溶 性高分子化合物水溶液、水難溶性化合物等の処理剤の噴霧を開始する。噴霧ノズ ノレとしては、通常の加圧ノズルのほか、噴霧状体を良好にするため、 2流体ノズルを 用いることも好ましい。この時の平均液滴径は 5〜500 /i m程度が好ましい。噴霧が 進むにつれて造粒も進み粒子径が大きくなるため、流動化状態を維持するため風速 を調整しながら造粒を行う。風速は 0. 2〜4. Om/sの範囲で調整を行い、風温度は 5〜70°C、好ましくは 7〜65°Cで行う。バグフィルターに付着した微粒子は定期的に パルスエアーで落としながら製造を行うことが好ましい。  [0058] As granulation conditions in the fluidized bed granulation method, the average thickness of the raw material powder layer at the time of standing is preferably about 50 to 500 mm. Thereafter, air is sent to the fluidized bed to fluidize the powder, and then spraying of a treatment agent such as an aqueous solution of a water-soluble polymer compound or a poorly water-soluble compound is started. As the spray nozzle, it is also preferable to use a two-fluid nozzle in addition to a normal pressure nozzle in order to improve the spray-like body. The average droplet diameter at this time is preferably about 5 to 500 / im. As spraying progresses, granulation progresses and the particle size increases, so granulation is performed while adjusting the wind speed to maintain the fluidized state. The wind speed is adjusted in the range of 0.2 to 4. Om / s, and the wind temperature is 5 to 70 ° C, preferably 7 to 65 ° C. It is preferable to manufacture the fine particles adhering to the bag filter while periodically dropping them with pulsed air.
[0059] 上記表面処理水溶性アルカリ無機化合物粒子の製造方法で製造する場合、第 2 工程終了直後における表面処理水溶性アルカリ無機化合物粒子の温度が、ァニォ ン界面活性剤酸前駆体の融点以上であることが好ましい。特に、第 2工程で水難溶 性化合物を添加する際には、第 1工程で処理された水溶性アルカリ無機化合物核粒 子の温度に留意するとよい。具体的にはこの粒子の温度を水難溶性化合物の融点 以上にすることが好ましい。また、水難溶性化合物を添加する時、第 1工程で処理さ れた水溶性アルカリ無機化合物核粒子の温度が該水難溶性化合物の融点未満であ る場合は、水難溶性化合物による表面処理終了後の表面処理水溶性アルカリ無機 化合物粒子の温度が、水難溶性化合物の融点以上であることが好ましい。これらの 温度が融点未満であると、造粒 ·被覆装置系内において水難溶性化合物の分散性 · 均一性が悪くなり、水難溶性化合物による表面処理が不充分となることがある。 [0059] When the surface-treated water-soluble alkali-inorganic compound particles are produced by the method for producing the surface-treated water-soluble alkali-inorganic compound particles, the temperature of the surface-treated water-soluble alkali-inorganic compound particles immediately after the end of the second step is equal to or higher than the melting point of the anionic surfactant acid precursor. Preferably there is. In particular, when adding a poorly water-soluble compound in the second step, attention should be paid to the temperature of the water-soluble alkali-inorganic compound core particles treated in the first step. Specifically, it is preferable that the temperature of the particles is equal to or higher than the melting point of the poorly water-soluble compound. In addition, when the hardly water-soluble compound is added, the temperature of the water-soluble alkali inorganic compound core particles treated in the first step is lower than the melting point of the hardly water-soluble compound. In this case, it is preferable that the temperature of the surface-treated water-soluble alkali inorganic compound particles after completion of the surface treatment with the poorly water-soluble compound is equal to or higher than the melting point of the hardly water-soluble compound. When these temperatures are lower than the melting point, the dispersibility and uniformity of the poorly water-soluble compound in the granulation / coating apparatus system may be deteriorated, and the surface treatment with the poorly water-soluble compound may be insufficient.
[0060] 上述の方法で得られた表面処理水溶性アルカリ無機化合物粒子を、さらに有機又 は無機の微粉体で表面処理してもよい。表面処理水溶性アルカリ無機化合物粒子を さらに表面処理する微粉体としては、常温固体の界面活性剤、長鎖脂肪酸塩、アル ミノ珪酸塩、吸油性担体、粘土鉱物等が挙げられる。  [0060] The surface-treated water-soluble alkali-inorganic compound particles obtained by the above method may be further surface-treated with an organic or inorganic fine powder. Examples of the fine powder for further surface treatment of the surface-treated water-soluble alkali inorganic compound particles include normal temperature solid surfactants, long-chain fatty acid salts, aluminosilicates, oil-absorbing carriers, clay minerals, and the like.
界面活性剤としては、ァニオン界面活性剤、カチオン界面活性剤、ノニオン界面活 性剤が挙げられる。長鎖脂肪酸塩としてはアルカリ、非アルカリ金属の長鎖脂肪酸塩 、アルミノケィ酸塩としては A型、 P型、 X型等、吸油性担体としてはシリカ、珪酸塩ィ匕 合物、球状多孔質含水非晶質珪酸等、粘土鉱物としてはモンモリロナイト、ノントロナ イト、ノくイデライト、パイロフイライト、サボナイト、ヘクトライト、スチープンサイト、タルク 等が挙げられる。これらは 1種単独で又は 2種以上を適宜組み合わせて用いることが できる。この中でも、非アルカリ金属の長鎖脂肪酸塩、タルク、アルミノケィ酸塩が好 ましレ、。非アルカリ金属の長鎖脂肪酸塩及びタルクは撥水性であるため、水溶性ァ ルカリ無機化合物の凝集を防ぎ、アルミノケィ酸塩は Ca捕捉ビルダーとして汎用され 、単独で表面処理に用いた場合、混合される洗剤粒子の表面の処理剤としての役割 を果たす。  Examples of the surfactant include an anionic surfactant, a cationic surfactant, and a nonionic surfactant. Long-chain fatty acid salts include alkali and non-alkali metal long-chain fatty acid salts, A-type, A-type, P-type, X-type as aluminosilicates, silica, silicate compounds, and spherical porous water as oil-absorbing carriers Examples of the clay mineral, such as amorphous silicic acid, include montmorillonite, nontronite, gnodelite, pyrophyllite, sabonite, hectorite, stevensite, and talc. These may be used alone or in combination of two or more. Of these, non-alkali metal long-chain fatty acid salts, talc, and aluminosilicates are preferred. Non-alkali metal long-chain fatty acid salts and talc are water-repellent, preventing aggregation of water-soluble alkali inorganic compounds, and aluminosilicates are widely used as Ca capture builders and are mixed when used alone for surface treatment. It serves as a surface treatment agent for detergent particles.
これら微粉体の粒子径は、表面処理水溶性アルカリ無機化合物粒子の平均粒子 径に対して 1/5以下の 1次粒子径をもつことが好ましぐより好ましくは 1/10以下で ある。また、微粉体の配合量は表面処理水溶性アルカリ無機化合物粒子に対して、 0 .：!〜 10質量％が好ましぐより好ましくは 1〜8質量％である。  The particle diameter of these fine powders is preferably 1/10 or less, more preferably 1/5 or less of the average particle diameter of the surface-treated water-soluble alkali inorganic compound particles. Further, the blending amount of the fine powder is preferably 0 to 10% by mass, more preferably 1 to 8% by mass with respect to the surface-treated water-soluble alkali inorganic compound particles.
[0061] 上述の方法により得られた表面処理水溶性アルカリ無機化合物粒子は、必要に応 じて分級して所望の粒度の表面処理水溶性アルカリ無機化合物粒子のみ利用する こともできる。分級装置としては、一般に知られたレ、かなる分級装置も用いることがで き、特に篩が好適に利用できる。中でもジャイロ式篩、平面篩及び振動篩が好適であ る。ジャイロ式篩は僅かに傾斜した平面篩に対し、水平な円運動を与える篩である。 平面篩は僅かに傾斜した平面篩に、面にほぼ平行に往復運動を与える篩である。振 動篩は、篩面にほぼ直角方向に急速な振動を与える篩である。篩に供する時間は 5 秒以上とすることが好ましぐまた、ふるい効率を向上させる為にはタッピングボール を用いることも好ましい。このような篩の具体例としては、ジャイロシフター（(株)徳寿 工作所製）、ローテツクススクリーナー（ (株)セイシン企業製）、ダルトン振動ふるい（ ( 株)ダルトン製）等が挙げられる。篩による振動は、好適には 60〜3， 000回/分、好 ましくは 100〜2， 500回/分、さらに好ましくは 150〜2， 000回/分の振動で与免 られる。篩の振動数が 60回/分未満であると、分級効果が悪化する場合がある一方 、 3, 000回 Z分を超えると発塵が増大する場合がある。 [0061] The surface-treated water-soluble alkali-inorganic compound particles obtained by the above-described method can be classified as required, and only the surface-treated water-soluble alkali-inorganic compound particles having a desired particle size can be used. As the classifier, a generally known classifier or any other classifier can be used, and a sieve can be particularly preferably used. Of these, a gyro sieve, a flat sieve and a vibrating sieve are suitable. A gyro-type sieve is a sieve that gives a horizontal circular motion to a slightly inclined plane sieve. A plane sieve is a sieve that gives a reciprocating motion to a slightly inclined plane sieve substantially parallel to the surface. A vibrating sieve is a sieve that gives rapid vibration in a direction substantially perpendicular to the sieve surface. It is preferable that the time for sieving is 5 seconds or more. In order to improve the sieving efficiency, it is also preferable to use a tapping ball. Specific examples of such a sieve include a gyro shifter (manufactured by Tokuju Kogakusho Co., Ltd.), a roteckus screener (manufactured by Seishin Enterprise Co., Ltd.), a Dalton vibrating sieve (manufactured by Dalton Co., Ltd.), and the like. The vibration by the sieve is preferably given by 60 to 3,000 times / minute, preferably 100 to 2,500 times / minute, more preferably 150 to 2,000 times / minute. If the frequency of the sieve is less than 60 times / minute, the classification effect may deteriorate, while if it exceeds 3,000 times Z, the dust generation may increase.
[0062] 分級工程で分離した表面処理水溶性アルカリ無機化合物粒子のうち、微粉につい ては再度水溶性アルカリ無機化合物核粒子と共に造粒機に投入し、造粒 '被覆操作 に供することが好ましい。また、粗粉については粉砕し、造粒'被覆操作前の水溶性 アルカリ無機化合物と同等の粒子径にした後、再度水溶性アルカリ無機化合物核粒 子と共に造粒機に投入し、造粒 ·被覆操作に供することが好適である。この際粗粉を 粉砕する粉碎機としては、分級スクリーンと回転ブレードを持った機種が好ましい。こ のような粉碎機としてはフィッツミル (ホソカワミクロン (株)製）、ニュースピードミル（岡 田精ェ (株)製）、フェザーミル (ホソカワミクロン (株)製）等が挙げられる。また、粉砕 機内に冷風を流し冷却しながら粉碎することもできる。冷風と粉碎品をサイクロンで分 級し、その時微粉を分級することも可能である。さらに、多段粉砕することで、より粒度 分布がシャープになる。粉碎機のブレードの先端周速としては 15〜90m/sが好ま しぐ 20〜80m/sがより好ましぐ 25〜70m/sがさらに好ましレ、。先端周速が 15m /s未満であると粉砕能力が不充分となる場合があり、 90m/sを超えると粉砕されや すくなる場合がある。 [0062] Among the surface-treated water-soluble alkali inorganic compound particles separated in the classification step, it is preferable that the fine powder is again charged into the granulator together with the water-soluble alkali inorganic compound core particles and subjected to the granulation and coating operation. The coarse powder is pulverized to the same particle size as that of the water-soluble alkali-inorganic compound before the granulation / coating operation, and then charged again into the granulator together with the water-soluble alkali-inorganic compound core particles. It is suitable to use for coating operation. At this time, as the powder grinder for pulverizing the coarse powder, a model having a classification screen and a rotating blade is preferable. Examples of such powder mills include Fitzmill (manufactured by Hosokawa Micron Corporation), New Speed Mill (manufactured by Seida Okada), and Feather Mill (manufactured by Hosokawa Micron Corporation). In addition, it can be pulverized while cooling by flowing cold air into the pulverizer. It is also possible to classify the cold air and the powdered product with a cyclone, and then classify the fine powder. Furthermore, the particle size distribution becomes sharper by multistage grinding. The tip peripheral speed of the powder mill blade is preferably 15 to 90 m / s, more preferably 20 to 80 m / s, and even more preferably 25 to 70 m / s. If the tip peripheral speed is less than 15 m / s, the crushing ability may be insufficient, and if it exceeds 90 m / s, crushing may be easily performed.
[0063] 表面処理水溶性アルカリ無機化合物粒子を、高嵩密度にし、安息角を小さくするた めには、上記第 1工程及び第 2工程の表面処理後、第 3工程：第 2工程の表面処理 後の水溶性アルカリ無機化合物核粒子の表面上の水和結晶成長を抑制する工程を 含むことが好ましい。これにより表面処理水溶性アルカリ無機化合物粒子の表面形 状の円滑性を保つとよい。水和結晶が成長すると、水溶性アルカリ無機化合物核粒 子の表面に多数の凹凸が生じて、嵩密度が低下し、安息角も大きくなる。場合によつ ては水和結晶が表面処理を突き破り、近傍の表面処理水溶性アルカリ無機化合物 粒子から突き出た水和結晶同士で凝結し、強固な水和固結となることもある。 [0063] In order to make the surface-treated water-soluble alkali inorganic compound particles have a high bulk density and a small angle of repose, after the surface treatment in the first step and the second step, the third step: the surface of the second step It is preferable to include a step of suppressing hydrated crystal growth on the surface of the water-soluble alkali-inorganic compound core particles after the treatment. Thus, the smoothness of the surface shape of the surface-treated water-soluble alkali inorganic compound particles should be maintained. When hydrated crystals grow, water-soluble alkaline inorganic compound core particles Many irregularities are generated on the surface of the child, the bulk density is lowered, and the angle of repose is increased. In some cases, the hydrated crystals break through the surface treatment, and the hydrated crystals protruding from the nearby surface-treated water-soluble alkali-inorganic compound particles may condense, resulting in strong hydration and consolidation.
水和結晶を抑制する方法としては、 [1]第 2工程後の表面処理された粒子を冷却 する方法、 [2]第 2工程後の表面処理された粒子を乾燥する方法等が挙げられる。こ れらのうちで、溶解性を良好に保つ点から、 [1]冷却する方法が好ましい。  Examples of the method for suppressing hydrated crystals include [1] a method of cooling the surface-treated particles after the second step, and [2] a method of drying the surface-treated particles after the second step. Among these, from the viewpoint of maintaining good solubility, [1] a cooling method is preferable.
[0064] [1]第 2工程後の表面処理された粒子を冷却する方法は、表面処理水溶性アル力 リ無機化合物粒子を 30°C以下、好ましくは 25°C以下まで冷却可能であれば特に限 定されない。冷却速度は 5°C/hr以上とすることが好ましぐ 10°C/hr以上とすること 力はり好ましい。冷却方法及び装置は特に限定されないが、冷却装置としては冷却さ れた伝熱面により冷却を行うものと、気流を用レ、るものに分けられる。例えば、冷却さ れた伝面を用レ、るものとしては、トーラスディスク（ホソカワミクロン (株)製）、フリゴミツ タス（日清エンジニアリング (株)製）等が挙げられる。気流を用いることで冷却を行うも のとしては、流動層が挙げられる。具体的装置の利用例としては回分式流動層造粒 装置の Glatt— POWREXシリーズ（（株）パゥレックス製）、フローコーターシリーズ（（ 株)大 j 11原製作所製）、連続式流動層造粒装置の MIXGRADシリーズ（(株)大川原 製作所製）等が挙げられる。表面処理水溶性アルカリ無機化合物粒子の表面処理部 の剥がれ、壊れの可能性を鑑みると、流動層の利用が好ましい。  [0064] [1] The method of cooling the surface-treated particles after the second step is that the surface-treated water-soluble alcoholic inorganic compound particles can be cooled to 30 ° C or lower, preferably 25 ° C or lower. It is not particularly limited. The cooling rate is preferably 5 ° C / hr or more, more preferably 10 ° C / hr or more. Although the cooling method and apparatus are not particularly limited, the cooling apparatus can be classified into those that cool using a cooled heat transfer surface and those that use airflow. For example, a torus disk (manufactured by Hosokawa Micron Co., Ltd.), a fright dust status (manufactured by Nisshin Engineering Co., Ltd.), etc., can be used as the one using a cooled transmission surface. A fluidized bed can be used as a cooling device by using an air flow. Specific examples of use of the equipment include the Glatt-POWREX series of batch fluidized bed granulators (manufactured by Paulex Co., Ltd.), the flow coater series (manufactured by Dai j11 Hara Manufacturing Co., Ltd.), and the continuous fluidized bed granulator MIXGRAD series (manufactured by Okawara Manufacturing Co., Ltd.). In view of the possibility that the surface-treated water-soluble alkali-inorganic compound particles are peeled off or broken, it is preferable to use a fluidized bed.
[0065] [2]第 2工程後の表面処理された粒子を乾燥する方法は、表面処理水溶性アル力 リ無機化合物粒子を乾燥できれば特に限定されない。具体的には、上記 [1]方法に 用いられる同様の装置を、伝面や気流といった熱媒体の温度を 50〜300°C、好まし くは 60〜250°Cとすることで、乾燥装置として利用し乾燥する方法が挙げられる。  [2] The method for drying the surface-treated particles after the second step is not particularly limited as long as the surface-treated water-soluble alcoholic inorganic compound particles can be dried. Specifically, a similar apparatus used in the above method [1] is obtained by setting the temperature of a heat medium such as a transmission surface or an air flow to 50 to 300 ° C, preferably 60 to 250 ° C. The method of using and drying is mentioned.
[0066] 本発明の粒状洗剤組成物は、通常衣類等の繊維製品用洗剤組成物に含まれてい る成分を、本発明の効果を妨げない範囲で含有することができる。このような成分の 具体例としては、プロテアーゼ等の他の酵素、漂白剤粒子、漂白活性化剤粒子、香 料、色素等があげられる。前述の (B)界面活性剤含有粒子に配合してもよい任意成 分と同様の任意成分を含むことができる。  [0066] The granular detergent composition of the present invention can contain components usually contained in a detergent composition for textiles such as clothing as long as the effects of the present invention are not hindered. Specific examples of such components include other enzymes such as protease, bleach particles, bleach activator particles, fragrances, dyes and the like. An optional component similar to the optional component that may be blended in the aforementioned (B) surfactant-containing particles can be included.
[0067] <プロテア一ゼ> プロテアーゼは、通常洗剤に用いられるものであれば特に限定されない。プロテア ーゼの具体例としては、ペプシン、トリプシン、キモトリブシン、コラーゲナーゼ、ケラチ ナーゼ、エラスターゼ、スプチリシン、 BPN、パパイン、プロメリン、カルボキシぺプチ ターゼ A及び B、アミノぺプチターゼ、ァスパーギロぺプチターゼ A及び B等があげら れる。 [0067] <Protea> The protease is not particularly limited as long as it is usually used in detergents. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promelin, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, etc. Is given.
本発明に使用されるプロテアーゼとしては、特開昭 51— 8401号、特開昭 46— 43 551号、特開昭 46— 42 号、特開昭 δ9— 591 号、特開昭 δ4— 号、特 開昭 48— 2794号、特開昭 50— 16435号、特開昭 53— 18594号、特開昭 55— 46 711号、特開昭 57— 42310号、特開昭 58— 16200号、特開昭 56— 24512号、特 開昭 47— 1832号、特開昭 52— 35758号、特開昭 50— 34633号、特公昭 46— 41 596号、特開昭 58— 134990号、特開昭 55— 14086号、特開昭 51— 82783号、 特開昭 51— 125407号、特開昭 55— 39794号、特開昭 46— 1840号、特開昭 46 — 23989号、特開昭 58— 15282号、特開昭 61— 280278号、特開平 4— 197182 号、特公平 3— 79987号、特開平 5— 25492号などに記載されているものも使用す ること力 Sできる。また、これらの精製分画物は勿論、粗酵素及びそれらの造粒物も当 然使用できる。入手可能な巿販酵素としては、サビナーゼ（Savinase)、アルカラ一 ゼ (Alcalase)、エバラーゼ (Everlase)、カンナーゼ (Kannase)、エスペラーゼ (Es peraze) (ノボザィムズ社製）、 API21 (昭和電工（株）製）、マクサターゼ（Maxtaze) 、マクサカル（Maxacal)、ピュラフヱタト（Purafect)、マクサぺム（ジヱネンコア社製） 、 KAP (花王 (株)製）、特開平 5 - 25492号公報記載のプロテアーゼ K— 14、 K— 1 6等を挙げること力 Sできる。このうち、 1種類又は 2種類以上を組合わせて使用すること あでさる。  Examples of the protease used in the present invention include JP-A 51-8401, JP-A 46-43 551, JP-A 46-42, JP-A δ9-591, JP-A δ4- JP 48-2794, JP 50-16435, JP 53-18594, JP 55-46 711, JP 57-42310, JP 58-16200, JP Kaisho 56-24512, JP-A 47-1832, JP-A 52-35758, JP-A 50-34633, JP-B 46-41 596, JP-A 58-134990, JP-A JP 55-14086, JP 51-82833, JP 51-125407, JP 55-39794, JP 46-1840, JP 46-23989, JP 58- Those described in Japanese Patent No. 15282, Japanese Patent Laid-Open No. 61-280278, Japanese Patent Laid-Open No. 4-197182, Japanese Patent Publication No. 3-79987, Japanese Patent Laid-Open No. 5-25492, etc. can be used. In addition to these purified fractions, crude enzymes and their granulated products can naturally be used. Available commercial enzymes include Savinase, Alcalase, Everlase, Kannase, Esperaze (Novozymes), API21 (Showa Denko) ), Maxataze, Maxacal, Purafect, Maxapem (manufactured by Ginencore), KAP (manufactured by Kao Corporation), protease K-14 described in JP-A-5-25492, K — 1 Ability to raise 6 mag. Of these, use one or a combination of two or more.
本発明では、プロテア一ゼを本発明の洗浄剤組成物 lgに対し、 350PU〜20, 00 0PU酉己合することカ好ましレヽ。より好ましくは、 1， 000PU〜： 15， 000PUであり、特に 好ましくは 3， 500PU〜： 10， 000PUである。このような範囲の活性を有するプロテア ーゼを用いると、アミラーゼと併用したときに相乗的に効果を発揮し、食べこぼし汚れ に対する洗浄効果が高まるので好ましレ、。  In the present invention, it is preferable to combine the protease with the detergent composition lg of the present invention from 350 PU to 20,000 PU. More preferably, it is 1,000 PU to: 15,000 PU, and particularly preferably 3,500 PU to: 10,000 PU. Proteases with such a range of activity are preferred because they produce synergistic effects when combined with amylase and increase the cleaning effect against spilled dirt.
造粒物として用いる場合には、特開昭 60— 262900記載の造粒法など、通常の造 粒法に基づき、安定剤、フィラー、増量剤、増白剤、バインダー及びコーティング剤 等と共に造粒し用いることが出来る。通常、酵素造粒物中にプロテアーゼの配合量と しては、酵素タンパク量として 0. 1〜： 10質量％程度であり、好ましくは 0. 5〜5質量 %、より好ましくは 1〜3質量％であるのが好ましい。 2種以上の酵素の造粒に際して は別々に造粒してもよいし、酵素を混合し、同一造粒物としてもよい。しかしながら、 上述の例示は本発明を限定するものではなレ、。なお、本方法によると、ノボザィムズ 社のプロテアーゼ含有顆粒物であるサビナーゼ 12Tの活性は 700, 000プロテア一 ゼユニット（PU) Zgであった。 In the case of using as a granulated product, a normal granulation method such as a granulation method described in JP-A-60-262900 is used. Based on the granulation method, it can be granulated with stabilizers, fillers, extenders, brighteners, binders and coating agents. Usually, the amount of protease in the enzyme granulated product is about 0.1 to 10% by mass as the amount of enzyme protein, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. % Is preferred. When granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed to form the same granulated product. However, the above examples are not intended to limit the present invention. According to this method, the activity of sabinase 12T, a protease-containing granule from Novozymes, was 700,000 proteaase unit (PU) Zg.
プロテアーゼは、この酵素活性を満たすように、酵素タンパク量として組成物中に 0 . 001〜0. 05質量0 /0、より好ましく fま 0. 002〜0. 03質量0 /0、特 (こ好ましく ίま 0. 00 3〜0. 02質量％の範囲で配合することが好ましい。 0. 001質量％より少ない場合に は本発明の効果が小さくなる場合があり、 0. 05質量％より多い場合には効果が頭打 ちとなつてしまう場合がある。なお、プロテアーゼ活性 (PU)は下記の方法で測定した ものである。 Proteases, to meet this enzyme activity, 0 in the composition as enzyme protein amount. 001 to 0.05 mass 0/0, more preferably f or 0.002 to 0.03 mass 0/0, especially (this It is preferable to blend in the range of 0.003 to 0.02% by mass, if less than 0.001% by mass, the effect of the present invention may be reduced, and more than 0.05% by mass. In some cases, the effect may become a peak, and protease activity (PU) is measured by the following method.
<プロテアーゼ活性の測定方法 >  <Method for measuring protease activity>
反応液（0. 6%ミルクカゼイン (メルク社製）、 10mMホウ酸ナトリウム（ρΗ10· 5) ) に酵素溶液 0. 5mL加え、 35°Cで 10分間反応させ、反応終了液（0. 11Mトリクロ口 酢酸、 0. 22M酢酸ナトリウム、 0. 33M酢酸） 3. 2mLを加え、 35°C10分間放置後、 ろ紙（アドバンテック社 No. 131)でろ過し、ろ液の吸光度 275nmを測定することによ りチロシン濃度を測定した。ミルクカゼイン中のチロシンを 1分間に 1 μ g遊離させる活 性を 1PUとした。 Add 0.5 mL of the enzyme solution to the reaction solution (0.6% milk casein (Merck), 10 mM sodium borate (ρΗ10 · 5)) and react at 35 ° C for 10 minutes to complete the reaction solution (0.1M Trichloro Mouth acetic acid, 0.22M sodium acetate, 0.33M acetic acid) 3. Add 2mL, leave at 35 ° C for 10 minutes, filter through filter paper (Advantech No. 131), and measure the absorbance of the filtrate at 275nm. The tyrosine concentration was measured. The activity to release 1 μg of tyrosine in milk casein per minute was defined as 1 PU.
洗浄剤組成物中にプロテアーゼと (A)成分のアミラーゼは酵素タンパク量の合計 量として 0. 006-0. 6質量0 /0、特に 0. 02〜0. 4質量0 /0配合することが好ましレ、。こ のような量でプロテアーゼとアミラーゼとを用いると、食べこぼし汚れに対する洗浄効 果が増大するので好ましレ、。 Amylase protease and the component (A) in the detergent composition is 0.1 as the total amount of enzyme protein amount 006-0. 6 mass 0/0, be especially 0.02 to 0.4 mass 0/0 compounded I like it. If protease and amylase are used in such amounts, the cleaning effect on spilled dirt increases, which is preferable.
また、プロテアーゼと（A)成分のアミラーゼの配合量の比率は酵素タンパク量の質 量比でプロテアーゼ Zアミラーゼが質量比で 1Z5以上〜 5Z2未満、より好ましくは 、 1/2以上〜 2/1未満であることが好ましい。このような比でプロテアーゼとアミラー ゼとを用いると、食べこぼし汚れに対する洗浄効果が増大するので好ましい。なお、 酵素を造粒物として配合する場合には安定性および溶解性の面から平均粒子径が 2 00〜700 /i mであることが望ましい。 The ratio of the amount of protease and amylase of component (A) is the mass ratio of the amount of enzyme protein, and protease Z amylase is 1Z5 or more to less than 5Z2, more preferably 1/2 or more to less than 2/1. It is preferable that Protease and Amyler in this ratio It is preferable to use zeta because the cleaning effect against spilled dirt increases. When the enzyme is blended as a granulated product, the average particle size is desirably 200 to 700 / im from the viewpoint of stability and solubility.
[0070] <他の酵素 > [0070] <Other enzymes>
現在、衣料用洗剤に用いられている市販の酵素粒子をそのまま使用することができ る。酵素（本来的に酵素作用を洗浄工程中になす酵素である）としては、酵素の反応 性から分類すると、ハイド口ラーゼ類、ォキシドレダクターゼ類、リアーゼ類、トランスフ エラーゼ類及びイソメラーゼ類等を挙げることができるが、本発明にはいずれも適用 できる。特に好ましいのは、エステラーゼ、リパーゼ、ヌクレアーゼ、セルラーゼ及び ぺクチナーゼ等である。  At present, commercially available enzyme particles used in clothing detergents can be used as they are. Enzymes (which are enzymes that inherently perform enzyme action during the washing process) include hydrase, oxidoreductases, lyases, transferases, and isomerases from the reactivity of the enzymes. However, any can be applied to the present invention. Particularly preferred are esterase, lipase, nuclease, cellulase and pectinase.
エステラーゼの具体例としては、ガストリックリパーゼ、バンクレアチックリパーゼ、植 物リパーゼ類、ホスホリパーゼ類、コリンエステラーゼ類及びホスホターゼ類等を挙げ ること力 Sできる。リパーゼの具体例としては、リボラーゼ、リボラーゼウルトラ、ライペック ス（ノボザィムズ社製）、リポサム（昭和電工 (株)製)等の市販のリパーゼを挙げること ができる。また、セルラーゼとしては市販品のセルザィム（ノボザィムズ社製）、 KAC5 00 (花王 (株)製）、特開昭 63— 264699号公報の請求項 4記載のセルラーゼ等を挙 げること力 Sできる。酵素としては、これらを 1種又は 2種以上を適宜組み合わせて用い ること力 Sできる。なお、酵素は別途安定な粒子として造粒したものを、洗剤生地 (粒子 )にドライブレンドした状態で使用すると好適であり、酵素含有粒子の造粒方法として は、特開昭 53— 6484号公報、特開昭 60— 262900号公報、特開昭 62— 257990 号公報、特開平 1 112983号公報、特表平 3— 503775号公報、特表平 4 5033 69号公報、特開 2000— 178593号公報記載の方法等が挙げられる。上記酵素含 有粒子の平均粒子径は、溶解性及び保存安定性の点から、 200-1 , OOO x mが好 ましく、より好ましくは 300〜700 μ πιである。  Specific examples of esterases include gastric lipase, bunkreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase. Specific examples of the lipase include commercially available lipases such as ribolase, ribolase ultra, lipex (manufactured by Novozymes), and liposome (manufactured by Showa Denko KK). Examples of cellulases include commercially available cellzymes (manufactured by Novozymes), KAC500 (manufactured by Kao Corporation), and cellulases described in claim 4 of JP-A-63-264699. As an enzyme, it is possible to use one or a combination of two or more thereof as appropriate. The enzyme is preferably granulated as a separate stable particle and used in a dry-blended state with a detergent dough (particle). As a method for granulating the enzyme-containing particle, JP-A-53-6484 JP-A-60-262900, JP-A-62-257990, JP-A-1112983, JP-T 3-503775, JP-A-4 503369, JP-A 2000-178593 Examples include the method described in the publication. The average particle size of the enzyme-containing particles is preferably 200-1, OOO xm, more preferably 300 to 700 μπι, from the viewpoint of solubility and storage stability.
[0071] <漂白剤粒子 > [0071] <Bleach particles>
漂白剤粒子としては、過酸化水素又は水に溶解したときに過酸化水素を発生する 過酸化物からなり、通常、過炭酸ナトリウム、過ホウ酸ナトリウムの一方あるいは両方 が用いられる。特に、経時安定性の点から過炭酸ナトリウムが好ましい。これらの過酸 化物は、該過酸化物からなる粒子の表面に、水分や他の洗浄剤成分等が接触する ことによって分解が生じるのを防止するために、被覆等の処理を施した形態で用いら れる。被覆が施された粒子形態の酸素系漂白剤は、種々のものが提案されており、 例えば特許第 2918991号公報に記載の漂白剤粒子を挙げることができる。この漂 白剤粒子は、流動状態を保った過炭酸ナトリウム粒子にホウ酸水溶液とケィ酸アル力 リ金属塩水溶液とを別々に噴霧して乾燥してなる造粒物である。上記の他に、従来 知られているキレート剤等の安定化剤を被覆剤と併用してもよい。被覆された過炭酸 ナトリウム粒子の平均粒子径は、過炭酸ナトリウム粒子の安定性及び溶解性の点から 、 100〜2， OOO x m力 S好ましく、より好ましくは 200〜1， 000 μ m、さらに好ましくは 3 00〜800 z mであり、このようなものとして三菱瓦斯化学 (株）製の SPC— Dが挙げら れる。 The bleaching particles are made of hydrogen peroxide or a peroxide that generates hydrogen peroxide when dissolved in water, and usually one or both of sodium percarbonate and sodium perborate are used. In particular, sodium percarbonate is preferred from the viewpoint of stability over time. These peracids The chemical compound is used in a form that has been subjected to a treatment such as coating in order to prevent the surface of the particles made of the peroxide from decomposing due to the contact of moisture or other detergent components. Various types of oxygen-based bleaching agents in the form of particles having been coated have been proposed. For example, bleaching particles described in Japanese Patent No. 2918991 can be mentioned. This whitening agent particle is a granulated product obtained by spraying and drying sodium borate particles in a fluidized state separately with an aqueous boric acid solution and an aqueous solution of alkali metal silicate. In addition to the above, a conventionally known stabilizer such as a chelating agent may be used in combination with the coating agent. The average particle diameter of the coated sodium percarbonate particles is preferably 100 to 2, OOO xm force S, more preferably 200 to 1,000 μm, even more preferably, from the viewpoint of stability and solubility of the sodium percarbonate particles. Is 300 to 800 zm, and SPC-D manufactured by Mitsubishi Gas Chemical Co., Ltd. can be mentioned as such.
漂白剤粒子を含む場合の配合量は、漂白性能と効率の点から、粒状洗剤組成物 全量に対し、好ましくは 0. 5〜30質量％、より好ましくは 1〜20質量％である。  The blending amount when the bleaching agent particles are included is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass based on the total amount of the granular detergent composition from the viewpoint of bleaching performance and efficiency.
<漂白活性化剤粒子 > <Bleaching activator particles>
漂白活性化剤粒子中の漂白活性化剤は、テトラァセチルエチレンジァミン、炭素数 8〜 12のアルカノィルォキシベンゼンスルホン酸、炭素数 8〜 12のアルカノィルォキ シ安息香酸又はそれらの塩が挙げられ、このうち、 4ーデカノィルォキシ安息香酸、 4 ーデカノィルォキシベンゼンスルホン酸ナトリウム、 4ードデカノィルォキシベンゼンス ルホン酸ナトリウム、 4—ノナノィルォキシベンゼンスルホン酸ナトリウムが好ましぐ特 に漂白効果の点から、 4ーデカノィルォキシ安息香酸、 4ーデカノィルォキシベンゼ ンスルホン酸ナトリウム、 4—ノナノィルォキシベンゼンスルホン酸ナトリウムがより好ま しレヽ。漂白活性ィ匕斉 'Jは PEG # 3000〜# 20000、好ましくは PEG # 4000〜# 600 0のポリエチレングリコール等の常温で固体のバインダー物質を加熱溶融した中に漂 白活性化剤とォレフインスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキル硫 酸エステル塩等の界面活性剤の粉末を分散後、押し出して直径 lmm程度のヌード ル状の漂白活性化剤造粒物を製造し、その後長さ 0. 5〜 3mm程度に軽く粉砕して 配合されることが好ましい。界面活性剤の粉末としては、アルキル鎖長 14のひ—ォレ フインスルホン酸塩が好ましレ、。 [0073] 造粒物中の漂白活性化剤の配合量は、好ましくは 30〜95質量％、より好ましくは 5 0〜90質量％である。配合量がこの範囲外では造粒した効果が充分に得られ難くな る場合がある。上記バインダー物質の配合量は、造粒物中に 0. 5〜30質量％、好ま しくは 1〜20質量％、より好ましくは 5〜20質量％であり、上記界面活性剤粉末の配 合量は、造粒物中に好ましくは 0〜50質量％、より好ましくは 3〜40質量％、特に好 ましくは 5〜30質量％である。 The bleach activator in the bleach activator particles is tetraacetyl ethylenediamine, alkanoyloxybenzene sulfonic acid having 8 to 12 carbon atoms, alkanoyl benzoic acid having 8 to 12 carbon atoms or a salt thereof. Of these, 4-decanoyloxybenzoic acid, sodium 4-decanoyloxybenzenesulfonate, sodium 4-dodecanoyloxybenzenesulfonate, and sodium 4-nonanoyloxybenzenesulfonate are preferred. In particular, 4-decanoyloxybenzoic acid, sodium 4-decanoyloxybenzensulfonate, and sodium 4-nonanoyloxybenzenesulfonate are more preferred from the standpoint of the bleaching effect. Bleaching activity 匕 simultaneous' J is a whitening activator and olefin in a solid binder material heated at room temperature such as polyethylene glycol of PEG # 3000 to # 20000, preferably PEG # 4000 to # 6000 Surfactant powders such as sulfonates, alkylbenzene sulfonates, alkyl sulfonates, etc. are dispersed and then extruded to produce noodle bleach activator granules with a diameter of about 1 mm, and then length 0 It is preferable to blend by lightly grinding to about 5 to 3 mm. Preferred surfactant powders are olefin sulfonates with an alkyl chain length of 14. [0073] The blending amount of the bleach activator in the granulated product is preferably 30 to 95% by mass, more preferably 50 to 90% by mass. If the blending amount is out of this range, it may be difficult to obtain a sufficient granulated effect. The blending amount of the binder substance is 0.5 to 30% by mass in the granulated product, preferably 1 to 20% by mass, more preferably 5 to 20% by mass, and the blending amount of the surfactant powder. Is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and particularly preferably 5 to 30% by mass in the granulated product.
漂白活性化剤粒子の平均粒子径は、溶解性及び保存安定性の点から、 200〜： 1， 500 z mカ好ましく、より好ましく fま 300〜1， 000 z mである。  The average particle size of the bleach activator particles is preferably 200 to 1,500 zm, more preferably f to 300 to 1,000 zm from the viewpoint of solubility and storage stability.
漂白活性化剤粒子を含む場合の配合量は、粒状洗剤組成物全量に対し 0. ：!〜 1 5質量％が好ましぐ 0. 3〜： 10質量％が特に好ましい。  When the bleaching activator particles are included, the blending amount is preferably 0.3: to 15% by mass, particularly preferably 0.3 to 10% by mass, based on the total amount of the granular detergent composition.
[0074] <着色剤 >  [0074] <Colorant>
(C)表面処理水溶性アルカリ無機化合物粒子、（B)界面活性剤含有粒子、酵素含 有粒子、漂白剤粒子及び漂白活性化剤粒子等は、表面を染料や顔料で着色してか ら用レ、ること力 Sできる。この際着色に用いる染料、顔料は洗浄時に衣類への染着が 起こらないものを用いる。この様な染料、顔料としては、群青、コラニルダリーン CG— 130 (CIナンバー： 74260)、食用色素赤色 102号、酸性染料アシッドイェロー 141 等が挙げられる。これらの染料、顔料は、水溶液や分散液とした後、（B)界面活性剤 含有粒子の造粒装置と同様な撹拌造粒機や転動造粒機中で上記粒子を撹拌、転 動しながら、添加することで着色することができる。また、上記粒子をベルトコンベアで 移送中に上記水溶液や分散液を上記粒子に噴霧して着色することもできる。着色量 としては、着色する粒子に対し 0. 001〜1質量％が好ましい。  (C) Surface-treated water-soluble alkali inorganic compound particles, (B) surfactant-containing particles, enzyme-containing particles, bleaching agent particles, and bleaching activator particles are used after the surface is colored with a dye or pigment. I can do it. At this time, dyes and pigments used for coloring should be those that do not stain clothes. Examples of such dyes and pigments include ultramarine, coranyldarin CG-130 (CI number: 74260), food dye red No. 102, and acid dye Acid Yellow 141. These dyes and pigments are made into an aqueous solution or dispersion, and then the particles are stirred and rolled in the same agitation granulator or tumbling granulator as the granulating apparatus for (B) surfactant-containing particles. However, it can color by adding. Further, the particles can be colored by spraying the aqueous solution or dispersion on the particles while the particles are transported by a belt conveyor. The coloring amount is preferably 0.001 to 1% by mass with respect to the particles to be colored.
[0075] <香料 > [0075] <fragrance>
また、香料は (C)表面処理水溶性アルカリ無機化合物粒子と (B)界面活性剤含有 粒子のいずれか一方あるいは両方に賦香した後、各粒子を混合してもよぐ（C)表面 処理水溶性アルカリ無機化合物粒子と（B)界面活性剤含有粒子を混合した後、賦 香してもよレ、。用いられる香料としては、特開 2002— 146399号公報ゃ特開 2003 — 89800号公報記載の成分を用いることができる。なお、香料とは、香料成分、溶剤 、香料安定化剤等からなる混合物である。本発明の粒状洗剤組成物中、香料の配合 量は、 0. 001〜10質量％が好ましぐ 0. 01〜5質量％がより好ましい。なお、香料 は実施例の香料に限定されるものではない。 Further, the fragrance may be mixed with either (C) surface-treated water-soluble alkali inorganic compound particles or (B) surfactant-containing particles, and then mixed. (C) Surface treatment After mixing the water-soluble alkali inorganic compound particles and the (B) surfactant-containing particles, they may be scented. As the fragrance used, components described in JP-A-2002-146399 and JP-A-2003-89800 can be used. The fragrance is a mixture comprising a fragrance component, a solvent, a fragrance stabilizer, and the like. In the granular detergent composition of the present invention, blending of perfume The amount is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 5% by mass. In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example.
[0076] 本発明の粒状洗剤組成物は、（A)〜（C)成分を混合することにより製造することが できる。その混合方法としては、乾式混合が好適に用いられる。使用する混合機は、 各種粒子同士が充分に混合できる限りいかなる混合機を用いてもよい。混合機として は、水平円筒型、二重円錐型、 V型、 自転 ·公転型等の混合機が好適に利用できる。 また、撹拌造粒機、転動造粒機を用いてもよい。好ましくは、水平円筒型又は二重円 錐型を用い、温度 0〜50°C、 Fr数 0. 01〜0. 2 (算出式は上述した通り）で混合する 。このとき、各種粒子やそれ以外の成分の添加順序は、特に問わない。  [0076] The granular detergent composition of the present invention can be produced by mixing the components (A) to (C). As the mixing method, dry mixing is preferably used. Any mixer may be used as long as various particles can be sufficiently mixed. As the mixer, a horizontal cylinder type, double cone type, V type, rotation / revolution type, or the like can be suitably used. Moreover, you may use a stirring granulator and a rolling granulator. Preferably, a horizontal cylindrical type or a double cone type is used, and mixing is performed at a temperature of 0 to 50 ° C. and an Fr number of 0.01 to 0.2 (the calculation formula is as described above). At this time, the order of addition of various particles and other components is not particularly limited.
[0077] 粒状洗剤組成物の容器内での分級を防止するために、表面処理水溶性アルカリ 無機化合物粒子と界面活性剤含有粒子の平均粒子径の比 (Zl) Z (B1)は、好まし くは 0. 5〜2、より好ましくは 0. 5〜： 1. 5、さらに好ましくは 0. 6〜： 1. 3である。また、 表面処理表面処理水溶性アルカリ無機化合物粒子と界面活性剤含有粒子の嵩密 度の _tt (Z2) / (B2)は、好ましくは 0. 5〜2、より好ましくは 0. 6〜： 1. 5、さらに好まし くは 0. 7〜： ! · 4である。  [0077] In order to prevent classification of the granular detergent composition in the container, the ratio (Zl) Z (B1) of the average particle diameter of the surface-treated water-soluble alkali inorganic compound particles and the surfactant-containing particles is preferable. Or 0.5 to 2, more preferably 0.5 to 1.5, and even more preferably 0.6 to 1.3. Moreover, _tt (Z2) / (B2) of the bulk density of the surface-treated surface-treated water-soluble alkali inorganic compound particles and the surfactant-containing particles is preferably 0.5 to 2, more preferably 0.6 to 1 .5, and more preferably 0.7-7:!
[0078] 本発明の粒状洗剤組成物の物性値は、特に制限されるものではないが、水分量は 、溶解性と保存安定性の点から、好ましくは 10質量％以下、より好ましくは 4〜9質量 %、さらに好ましくは 5〜8質量％である。嵩密度は、通常 0. 3g/mL以上、好ましく は 0. 5〜： 1. 2g/mL、より好ましくは 0. 6〜： 1. lg/mLである。また、平均粒子径は 、好ましくは 200〜1 , 500 111、ょり好ましくは250〜1 , 000 μ m、さらに好ましくは 2 80-700 μ mである。平均粒子径が 200 μ m未満になると粉塵が発生し易くなつた り、ハンドリング性が悪化する場合があり、一方、 1 , 500 x mを超えると本発明が目 的とする溶解性が得られ難くなる場合がある。さらに、粒状洗剤組成物の流動性は、 安息角として 60° 以下、特に 50° 以下が好ましい。さらに貯蔵後（紙容器等の透湿 性の高レ、容器に長期保存された場合等)も流動性が安息角として好ましくは 60° 以 下、より好ましくは 50° 以下であることが使用性の点から好ましい。  The physical property value of the granular detergent composition of the present invention is not particularly limited, but the water content is preferably 10% by mass or less, more preferably 4 to 4% from the viewpoint of solubility and storage stability. It is 9 mass%, More preferably, it is 5-8 mass%. The bulk density is usually 0.3 g / mL or more, preferably 0.5 to: 1.2 g / mL, more preferably 0.6 to: 1. lg / mL. The average particle diameter is preferably 200 to 1,500 111, more preferably 250 to 1,000 μm, and even more preferably 280 to 700 μm. When the average particle size is less than 200 μm, dust is likely to be generated and the handling property may be deteriorated. On the other hand, when it exceeds 1,500 xm, it is difficult to obtain the intended solubility of the present invention. There is a case. Further, the fluidity of the granular detergent composition is preferably 60 ° or less, particularly 50 ° or less as the angle of repose. Furthermore, after storage (when the moisture permeability is high in a paper container or when stored in a container for a long time, etc.), the fluidity is preferably 60 ° or less, more preferably 50 ° or less as the angle of repose. From the point of view, it is preferable.
[0079] 本発明の粒状洗剤組成物は、適当な容器に充填して容器入り粒状洗剤物品とする ことができる。容器の材料としては、保存安定性の点で透湿度が 30gZm2 ' 24時間（ 40°C、 90%RH)以下が好ましぐ 25g/m2 ' 24時間（40°C、 90%RH)以下がより 好ましレ、。これらは一般的な包装材料の組み合わせや厚みの変化により達成できる 。なお、本発明における透湿度は、 JIS Z0208— 1976に規定された方法で測定す る。本発明の粒状洗剤組成物は、さらに崩壊剤等を混合した後圧縮成形して、タブレ ット洗浄剤やプリケット洗浄剤等の圧縮成形洗浄剤としても利用できる。 [0079] The granular detergent composition of the present invention can be filled into a suitable container to form a granular detergent article in a container. The container material has a water vapor transmission rate of 30gZm2 '24 hours (in terms of storage stability) 40g, 90% RH) or less is preferred 25g / m2 '24 hours (40 ° C, 90% RH) or less is more preferred. These can be achieved by a combination of general packaging materials and changes in thickness. The moisture permeability in the present invention is measured by the method specified in JIS Z0208-1976. The granular detergent composition of the present invention can be used as a compression molding detergent such as a tablet detergent or a pricket detergent after being further mixed with a disintegrant and then compression molded.
[0080] 本発明の組成物の好ましい配合例としては、以下のものがあげられる： [0080] Preferable formulation examples of the composition of the present invention include the following:
(A)上述の式（1)で算出される粘度低減率が 90%以上のアミラーゼ:酵素タンパク 量として 0. 001〜0. 05質量0 /0、 (A) of formula (1) reducing the viscosity ratio calculated by the above-described 90% amylase:. 0. As the enzyme protein amount 001-0 05 mass 0/0,
(B)界面活性剤含有量が 20〜40質量％であり、界面活性剤として、炭素数 10〜1 4のアルキル基を有する LAS、炭素数 10〜20の高級脂肪酸、炭素数 12〜28のひ —SF及び炭素数 12〜： 16の脂肪族アルコールに炭素数 2〜4のエチレンオキサイド を平均 5〜20モル付加物したポリオキシアルキレンアルキルエーテルからなる群から 選ばれる少なくとも 1種を含有する界面活性剤含有粒子： 75〜90質量％、及び  (B) The surfactant content is 20 to 40% by mass, and as the surfactant, LAS having an alkyl group having 10 to 14 carbon atoms, higher fatty acid having 10 to 20 carbon atoms, 12 to 28 carbon atoms -SF and an interface containing at least one selected from the group consisting of polyoxyalkylene alkyl ethers obtained by adding 5 to 20 moles of ethylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 12 to 16 carbon atoms on average. Activator-containing particles: 75-90% by weight, and
(C)水溶性アルカリ無機化合物核粒子として炭酸ナトリウムを用い、第 1表面処理 剤としてポリアクリル酸塩、アクリル酸/マレイン酸共重合体塩、アクリル酸/ィタコン 酸共重合体塩及びアクリル酸アルキル共重合体塩からなる群から選ばれる 1種を用 いて表面処理し、得られた粒子をさらに第 2表面処理剤として炭素数 12〜： 18の飽和 脂肪酸で表面処理することにより得ることが出来る、表面処理した水溶性アルカリ無 機化合物粒子： 10〜20質量％  (C) Sodium carbonate is used as the core particle of the water-soluble alkali-inorganic compound, and the polyacrylic acid salt, acrylic acid / maleic acid copolymer salt, acrylic acid / itaconic acid copolymer salt, and alkyl acrylate are used as the first surface treatment agent. It can be obtained by surface-treating using one selected from the group consisting of copolymer salts, and surface-treating the obtained particles with a saturated fatty acid having 12 to 18 carbon atoms as a second surface-treating agent. Surface-treated water-soluble alkaline inorganic compound particles: 10-20% by mass
を含有する粒状洗剤組成物。  A granular detergent composition containing
更に、酵素タンパク量として 0. 001-0. 05質量％のプロテアーゼ及び、酵素タン パク量として 0. 001-0. 03質量％のリパーゼを含有するのが特に好ましい。  Further, it is particularly preferable to contain 0.001-0.05% by mass of protease as the amount of enzyme protein and 0.001-0.03% by mass of lipase as the amount of enzyme protein.
実施例  Example
[0081] 以下に、実施例及び比較例により本発明をより具体的に説明するが、本発明はこ れらの例によって何ら限定されるものではなレ、。なお、下記の例において特に明記の ない場合の組成は、「％」は質量％、比率は質量比を示し、表中の各成分の量は表 2 の（C)水溶性アルカリ無機化合物含有粒子と表 1の（B)界面活性剤含有粒子の組 成については、純分としての配合量を示し、その他の表は記載成分の配合量で示し た。 [0081] Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples below, unless otherwise specified, “%” indicates mass%, ratio indicates mass ratio, and the amount of each component in the table is (C) water-soluble alkali inorganic compound-containing particles in Table 2. For the composition of (B) surfactant-containing particles in Table 1, the compounding amount as a pure component is shown, and the other tables show the compounding amounts of the described components. It was.
[0082] 1. (A)アミラーゼの粘度低減率の測定  [0082] 1. (A) Measurement of viscosity reduction rate of amylase
とうもろこし澱粉（関東化学 (株)製） 25gを 90土 2°Cのアルカリ（炭酸ナトリウム 4000 ppm)水溶液 475gに添加、 1時間 90土 2°Cで攪拌溶解した後、 5°Cにて 12時間冷 却した。その後、室温にて放置し、該溶液の温度が室温と等しくなつた後、 25°Cに調 温した。次いで、 25°Cに調温した該溶液 40gの粘度を振動式粘度計 (株式会社エー 'アンド 'ディ製 CJV5000、振動子の材質：ステンレス鋼 SUS304_CSP_H、振動 子の形状及び大きさ：円盤状、 t (厚さ） =0. lmm、 φ (直径） = 13mm)にて測定し、 初期粘度とした (測定条件:設定振幅値 50mV、振動周波数: 30Hz、試料量 : 40g ( 5%水溶液として）、測定温度： 25°C)。その後デンプン水溶液 40gに対してアミラー ゼを酵素タンパク量として 0. 004mgを素早く添加'撹拌し、添加後 10秒後に粘度を 初期粘度と同様に測定し、その後 25°Cで調温した。次いで 10分後、 30分後、 60分 後に、粘度を初期粘度と同様に測定した。初期粘度と、 60分後の粘度の値を得た。 次いで、既述の式（1)により、粘度低減率を算出した。  Add corn starch (manufactured by Kanto Chemical Co., Inc.) 25g to 475g of 90 ° C 2 ° C alkaline (sodium carbonate 4000 ppm) solution, stir and dissolve at 90 ° C 2 ° C for 1 hour, then 12 hours at 5 ° C Cooled down. Thereafter, the solution was allowed to stand at room temperature, and after the temperature of the solution became equal to room temperature, the temperature was adjusted to 25 ° C. Next, the viscosity of 40 g of the solution adjusted to 25 ° C. was measured using a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd., vibrator material: stainless steel SUS304_CSP_H, vibrator shape and size: disk shape, t (thickness) = 0. lmm, φ (diameter) = 13mm) and measured as initial viscosity (measurement condition: set amplitude value 50mV, vibration frequency: 30Hz, sample amount: 40g (as 5% aqueous solution) , Measuring temperature: 25 ° C). Thereafter, 0.004 mg of amylase as the amount of enzyme protein was quickly added to 40 g of starch aqueous solution and stirred. After 10 seconds from the addition, the viscosity was measured in the same manner as the initial viscosity, and then the temperature was adjusted at 25 ° C. Then, after 10 minutes, 30 minutes and 60 minutes, the viscosity was measured in the same manner as the initial viscosity. The initial viscosity and the viscosity value after 60 minutes were obtained. Next, the viscosity reduction rate was calculated according to the above-described formula (1).
上記方法により、スティンザィム（ノボザィムズ社製）、ターマミル (ノボザィムズ社製） 及びデユラミル (ノボザィムズ社製）の粘度低減率を測定したところ、それぞれ 91 %、 20%、 23%であった。なお、これらの値は、 3回の実験の平均値である。また、測定 値の振れ幅は、 lOmPa' s程度であった。各酵素について時間と粘度との関係を図 1 に示した。  When the viscosity reduction ratios of Stinzym (manufactured by Novozymes), Termamyl (manufactured by Novozymes) and Deyuramil (manufactured by Novozymes) were measured by the above method, they were 91%, 20% and 23%, respectively. These values are average values of three experiments. The fluctuation range of the measured value was about lOmPa's. Figure 1 shows the relationship between time and viscosity for each enzyme.
[0083] 2. (B)界面活性剤含有粒子の製造  [0083] 2. (B) Production of surfactant-containing particles
2- 1. (B)界面活性剤含有粒子 bl， b2の製造  2- 1. (B) Production of surfactant-containing particles bl, b2
下記表 1に示す組成に従って、以下の手順で界面活性剤含有粒子 blを調製した。 まず、撹拌装置を具備したジャケット付き混合槽に水を入れ、温度を 60°Cに調整した 。これにひ _SF_Naとノニオン界面活性剤を除く界面活性剤、及び PEG # 6000を 添カロし、 10分間撹拌した。続いて MA1 (アクリル酸 Zマレイン酸コポリマーナトリウム 塩）と蛍光剤とを添加した。さらに 10分間撹拌した後、粉末 A型ゼオライトの一部（2. 0%相当量 (対各粒子、以下同じ）の捏和時添加用、 3. 2%相当量の粉砕助剤用を 除く）、炭酸ナトリウム、炭酸カリウム及び亜硫酸ナトリウムを添加した。さらに 20分間 撹拌して水分 38%の噴霧乾燥用スラリーを調製した後、向流式噴霧乾燥塔を用い て熱風温度 280°Cの条件で噴霧乾燥し、平均粒子径 320 /i m、嵩密度 0. 30g/m L、水分 5%の噴霧乾燥粒子を得た。 According to the composition shown in Table 1 below, surfactant-containing particles bl were prepared by the following procedure. First, water was put into a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this was added _SF_Na, a surfactant excluding the nonionic surfactant, and PEG # 6000, and the mixture was stirred for 10 minutes. Subsequently, MA1 (acrylic acid Z maleic acid copolymer sodium salt) and a fluorescent agent were added. After stirring for another 10 minutes, a part of the powder A-type zeolite (except for 2.0% equivalent amount (vs. each particle, the same applies below) during kneading and 3.2% equivalent amount of grinding aid) Sodium carbonate, potassium carbonate and sodium sulfite were added. Another 20 minutes After stirring to prepare a slurry for spray drying with a moisture content of 38%, spray drying is performed using a counter-current spray drying tower at a hot air temperature of 280 ° C. The average particle size is 320 / im, and the bulk density is 0.30g /. Spray dried particles with ml and 5% moisture were obtained.
一方、原料の脂肪酸エステルをスルホン化し、中和して得られたひ _ SF_ Naの水 性スラリー（水分濃度 25%)に、ノニオン界面活性剤の一部（ひ _ SF _ Naに対して 2 5%)を添加し、水分を 1 1 %になるまで薄膜式乾燥機で減圧濃縮して、 a - SF - Na とノニオン界面活性剤の混合濃縮物を得た。  On the other hand, a water slurry of _SF_Na obtained by sulfonating and neutralizing the fatty acid ester of the raw material (water concentration 25%) is mixed with a part of nonionic surfactant (2% of _SF_Na). 5%) was added, and the mixture was concentrated under reduced pressure with a thin-film dryer until the moisture content became 11% to obtain a mixed concentrate of a-SF-Na and a nonionic surfactant.
[0084] 上述の噴霧乾燥粒子、この混合濃縮物、 2. 0%相当量の A型ゼオライト、ノニオン 界面活性剤及び水を連続ニーダー（(株)栗本鐵ェ所製、 KRC— S4型）に投入し、 捏和能力 120kgZ 、温度 60°Cの条件で捏和し、界面活性剤含有混練物を得た。 この界面活性剤含有混練物を穴径 10mmのダイスを具備したペレツターダブル（不 ニパゥダル (株）製、 EXDFJS— 100型）を用いて押し出しつつ、カッターで切断し（ カッター周速は 5m/s)長さ 5〜30mm程度のペレット状界面活性剤含有成型物を 得た。  [0084] The above-mentioned spray-dried particles, this mixed concentrate, 2.0% equivalent of A-type zeolite, nonionic surfactant and water into a continuous kneader (Kurimoto Kyosho Co., Ltd., KRC-S4 type) The resulting mixture was kneaded under the conditions of a kneading capacity of 120 kgZ and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded material is extruded with a pelleter double (Nippadar Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm and cut with a cutter (cutter peripheral speed is 5 m / s) ) A pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
次いで、得られたペレット状界面活性剤含有成型物に粉砕助剤としての粒子状 A 型ゼオライト（平均粒子径 180 /i m)を 3 · 2%相当量添加し、冷風（10°C、 15m/s) 共存下で直列 3段に配置したフィッツミル (ホソカワミクロン (株)製、 DKA—3)を用い て粉砕して（スクリーン穴径： 1段目 /2段目 /3段目 = 12mm/6mm/3mm、回転 数： 1段目 /2段目 /3段目いずれも 4, 700rpm)、界面活性剤含有粒子 blを得た。 界面活性剤含有粒子 b lの調製方法と同様にして、界面活性剤含有粒子 b2を得た。 得られた界面活性剤含有粒子 b l、 b2について、後述の方法で平均粒子径、嵩密度 を測定した。結果を表 1に併記する。  Next, an amount equivalent to 3.2% of particulate A-type zeolite (average particle size 180 / im) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and cold air (10 ° C, 15m / m) was added. s) Grinding using Fitzmill (DKA-3, manufactured by Hosokawa Micron Co., Ltd.) arranged in three stages in series in the coexistence (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, number of rotations: 1st stage / 2nd stage / 3rd stage 4,700rpm), surfactant-containing particles bl were obtained. Surfactant-containing particles b2 were obtained in the same manner as the method for preparing the surfactant-containing particles bl. With respect to the obtained surfactant-containing particles bl and b2, the average particle diameter and bulk density were measured by the methods described later. The results are also shown in Table 1.
[0085] [表 1]
Figure imgf000043_0001
2- 2. (Β)界面活性剤含有粒子 b3の製造 [0085] [Table 1]
Figure imgf000043_0001
2- 2. (iii) Production of surfactant-containing particles b3
表 2に示す洗剤組成について、以下の手順によって調製した。  The detergent compositions shown in Table 2 were prepared by the following procedure.
撹拌装置を具備したジャケット付き混合槽に水を入れ、温度を 50°Cに調整した。こ れに硫酸ナトリウム、蛍光増白剤を添加し、 10分撹拌後、炭酸ナトリウムを添加した 後にアクリル酸系ポリマーを添加し、更に 10分撹拌後、塩化ナトリウム、亜硫酸ナトリ ゥム、粉末ゼォライトの一部を添加した。更に 30分間撹拌して噴霧乾燥用スラリーを 調製した。出来上がった噴霧乾燥用スラリーの温度は 60°Cであった。このスラリーを 、圧力噴霧ノズルを具備した向流式噴霧乾燥装置で噴霧乾燥を行い、揮発分（105 °C、 2時間の減量）が 3%、嵩密度が 0. 50g/mL、平均粒径が 250 mの噴霧乾燥 粒子を得た。  Water was placed in a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 50 ° C. Add sodium sulfate and fluorescent brightener to this, and after stirring for 10 minutes, add sodium carbonate and then add acrylic acid polymer, and after stirring for another 10 minutes, add sodium chloride, sodium sulfite, and powdered zeolite. A portion was added. The mixture was further stirred for 30 minutes to prepare a slurry for spray drying. The temperature of the resulting spray drying slurry was 60 ° C. This slurry is spray-dried in a counter-current spray dryer equipped with a pressure spray nozzle, the volatile content (105 ° C, reduced for 2 hours) is 3%, the bulk density is 0.50 g / mL, and the average particle size Gave 250 m spray-dried particles.
次に、 80°Cで混合下でノニオン界面活性剤、ァ-オン界面活性剤を添加して、含 水量 10質量％の界面活性剤組成物を調製した。  Next, a nonionic surfactant and a ionic surfactant were added under mixing at 80 ° C. to prepare a surfactant composition having a water content of 10% by mass.
次に、レーディゲミキサー M20型 (松坂技研 (株)製）に噴霧乾燥粒子を投入し、主 軸（150rpm)とチョッパー（4000rpm)の撹拌を開始した。ジャケットには 80°Cの温 水を 10LZ分の流量で流した。そこに上記界面活性剤組成物を 2分間で投入し、そ の後に 5分間撹拌した後、層状珪酸塩及び上記粉末ゼォライトの一部（10質量％)を 投入して 2分間の表面被覆処理を行い界面活性剤含有粒子 b3を得た。 Next, spray-dried particles were charged into a Ladige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.), and stirring of the spindle (150 rpm) and chopper (4000 rpm) was started. Hot water at 80 ° C was passed through the jacket at a flow rate of 10LZ. The surfactant composition is added to the mixture in 2 minutes. After stirring for 5 minutes, layered silicate and a part (10% by mass) of the above-mentioned powdered zeolite were added to perform surface coating for 2 minutes to obtain surfactant-containing particles b3.
得られた界面活性剤含有粒子 b3について、後述の方法で平均粒子径、嵩密度を 測定し  For the obtained surfactant-containing particles b3, the average particle diameter and bulk density were measured by the method described later.
た。結果を表 2に併記する。  It was. The results are also shown in Table 2.
[0087] [表 2] [0087] [Table 2]
Figure imgf000044_0001
Figure imgf000044_0001
[0088] 3. (C)表面処理水溶性アルカリ無機化合物粒子調製例 al， a2, a3の製造 [0088] 3. (C) Preparation of surface-treated water-soluble alkali-inorganic compound particles Production of al, a2, and a3
第 1工程  1st process
下記表 3に示す組成成分のうち、水溶性アル力リ無機化合物を鋤刃状ショベルを具 備し、ショベル—壁面間クリアランスが 5mmのプロ一シェア一ミキサー（大平洋機ェ（ 株）に投入し (充填率 30容積％)、主軸 150rPmで撹拌を開始した (チョッパー回転 数：1015rpm、ブレード先端速度 (周速）：6. 9mZs)。撹拌開始後 10秒後に水溶 性高分子化合物水溶液 (濃度は後記の原料欄に記載、以下同じ)を噴霧角 1 15度 の加圧ノズル (フラットノズル)で 180秒噴霧添加し、造粒 '被覆操作を行った。また、 第 1工程で調製された粒子全量に対する水分量が 10質量％を超えていた場合には 、上記装置に熱風を導入して乾燥し、水分量を 10質量％以下に調整した。 [0089] 第 2工程 Of the components shown in Table 3 below, a water-soluble inorganic compound is loaded into a professional share-one mixer (Daiheiyo Co., Ltd.) equipped with a blade-shaped excavator with a shovel-wall clearance of 5 mm. and (filling rate 30% by volume), and stirring was started at spindle 150 r P m. (chopper rpm: 1015Rpm, blade tip speed (peripheral speed):. 6 9mZs) a water-soluble polymer compound solution in 10 seconds after the start of stirring (The concentration is described in the raw material column below, the same shall apply hereinafter) was sprayed for 180 seconds with a pressure nozzle (flat nozzle) with a spray angle of 1 15 degrees, and granulation was performed, and the coating operation was performed. When the water content with respect to the total amount of the particles exceeded 10% by mass, hot air was introduced into the apparatus and dried to adjust the water content to 10% by mass or less. [0089] Second step
弓 1き続きプロ一シェア一ミキサーの撹拌を継続しつつ、表 3に示した水難溶性化合 物を噴霧角 60度の加圧ノズノレ（フルコーンノズル）で 180秒噴霧添カ卩し、被覆操作を 行った。 30秒間撹拌を続け粒子を得た。  Bow 1 While continuing to stir in a professional-share-share mixer, spray the slightly water-soluble compound shown in Table 3 with a pressure nozzle (full cone nozzle) at a spray angle of 60 degrees for 180 seconds, and cover operation Went. Stirring was continued for 30 seconds to obtain particles.
[0090] 第 3工程 [0090] Step 3
次いで、得られた粒子を、流動層（Glatt_POWREX、型番 FD_WRT_ 20、 ( 株)パゥレックス製）に充填し、充填後 15°Cの風（空気）を流動層内に送り、粒子の冷 却操作を行い、 20°Cまで冷却された粒子を得た。流動層内風速は流動化状態を確 認しながら 0. 2〜： 10. Om/sの範囲で調整した。得られた粒子を目開き 2， 000 ^ m の篩を用いて分級し、 目開き 2， 000 μ πιの篩を通過する表面処理水溶性アルカリ無 機化合物粒子を得た。得られた表面処理アルカリ無機化合物粒子 al、 a2、 a3につ いて、後述の方法で平均粒子径、嵩密度を測定した。結果を表 3に併記する。  Next, the obtained particles are packed into a fluidized bed (Glatt_POWREX, model number FD_WRT_20, manufactured by Paulex Co., Ltd.). After filling, 15 ° C air (air) is sent into the fluidized bed to cool the particles. To obtain particles cooled to 20 ° C. The wind speed in the fluidized bed was adjusted in the range of 0.2 to 10. Om / s while confirming the fluidization state. The obtained particles were classified using a sieve having a mesh opening of 2,000 ^ m to obtain surface-treated water-soluble alkaline inorganic compound particles that passed through a sieve having a mesh opening of 2,000 μπιι. With respect to the obtained surface-treated alkali inorganic compound particles al, a2, and a3, the average particle diameter and bulk density were measured by the methods described later. The results are also shown in Table 3.
[0091] [表 3] [0091] [Table 3]
Figure imgf000045_0001
Figure imgf000045_0001
[実施例、比較例]  [Examples and comparative examples]
水平円筒型転動混合機（円筒直径 585mm、円筒長さ 490mm、容器 131. 7Lのド ラム内部壁面に内部壁面とのクリアランス 20mm、高さ 45mmの邪魔板を 2枚有する もの）で、充填率 30容積％、回転数 22rPm、 25°Cの条件で、 （A)成分であるアミラ ーゼを含有する粒子、表 1または表 2に記載の（B)成分である界面活性剤含有粒子 及び表 3に記載の（C)成分である表面処理水溶性アルカリ無機化合物粒子と、必要 により、プロテアーゼを含有する粒子、これらの粒子の表面を被覆するための微粉 A 型ゼオライトを洗剤組成物全量に対して 1. 5%相当量と、その他の任意成分を加え て、 0. 5%相当量のノニオン界面活性剤と香料を噴霧しつつ、 1分間転動し表面改 質して混合粒子群を得た。得られた混合粒子群の一部を着色するために、該粒子群 をベルトコンベアで 0. 5mZsの速度で移送しつつ（ベルトコンベア上の界面活性剤 含有粒子層の高 30mm、層幅 300mm)その表面に色素の 20%水分散液を噴霧し 、表 4および表 5記載の組成の粒状洗剤組成物を得た。 Filling rate with horizontal cylindrical rolling mixer (cylinder diameter 585mm, cylinder length 490mm, container 131.7L with 2 baffle plates with inner wall clearance 20mm and height 45mm on the inner wall) Particles containing (A) amylase as component (A), surfactant-containing particles as component (B) in Table 1 or Table 2 under the conditions of 30% by volume, rotational speed 22r P m, and 25 ° C And surface-treated water-soluble alkali-inorganic compound particles (C) listed in Table 3 and, if necessary, particles containing protease, and fine powder A for coating the surfaces of these particles A 1.5% equivalent of total amount of zeolite and other optional ingredients and 0.5% equivalent of nonionic surfactant and perfume are sprayed on the surface for 1 minute while rolling. The mixed particles were obtained by modification. In order to color a part of the obtained mixed particles, the particles are transferred on a belt conveyor at a speed of 0.5 mZs (surfactant-containing particle layer on belt conveyor is 30 mm high and layer width is 300 mm). A 20% aqueous dispersion of the dye was sprayed on the surface to obtain a granular detergent composition having the composition shown in Tables 4 and 5.
得られた洗剤組成物について、下記方法で食べこぼし汚れに対する洗浄性能、平 均粒子径、嵩密度を評価した。結果を表 4および表 5に併記する。  About the obtained detergent composition, the washing | cleaning performance with respect to spilled food stains, an average particle diameter, and bulk density were evaluated by the following method. The results are shown in Table 4 and Table 5.
[0093] 4.評価方法 [0093] 4. Evaluation method
4一 1.食べこぼし汚れ洗浄性能評価  4 1 1. Eating spilled dirt cleaning performance evaluation
(i)イカ墨汚れ評価布の調製方法  (i) Preparation method of squid ink stain evaluation cloth
60番の綿平織り布を 20cm X 30cmに裁断し、イカ墨のソース (ェム ·シ一'シ一食 品)をステンレスバットに開けた中に約 1時間浸した後、表面に付着した固形物を取り 除いて、喑くした 20°C40%RHの恒温恒湿室で一夜風乾したものをイカ墨汚れ評価 布とした。  Cut 60cm cotton plain weave into 20cm x 30cm, soak in squid ink sauce (em shii's food) in a stainless steel vat for about 1 hour, and then adhere to the surface The squid ink stain evaluation cloth was removed and air-dried overnight in a constant temperature and humidity room at 20 ° C and 40% RH.
(ii)高嵩密度粒状漂白洗浄剤組成物の洗浄性能評価  (ii) Evaluation of cleaning performance of high bulk density granular bleaching detergent composition
米国 Testing社の Terg—〇一 tometerを洗浄試験器として用い、上記のイカ墨汚 れ評価布 5枚とセバム布、洗浄メリヤス布を入れ、表 3に示す粒状洗剤組成物を洗剤 濃度が 0. 067%となるように添カロし、浴比 30倍に合わせて、 120rpm、 20°Cで 10分 間洗浄した。水としては 4° DHのものを用い、洗浄液量は 900mLであり、すすぎは 9 OOmLの水で 3分間洗った。すすいだ後、評価布を乾燥させ、下式によって洗浄率を しプし。  Using a Terg--O-tometer from Testing Corp. in the United States as a cleaning tester, put the above five squid ink stain evaluation cloths, sebum cloth, and cleaning knitted cloth, and the detergent concentration of the granular detergent composition shown in Table 3 is 0. The solution was added to 067% and washed at 120 rpm and 20 ° C for 10 minutes according to the bath ratio of 30 times. The water used was 4 ° DH, the washing volume was 900 mL, and the rinse was washed with 9 OO mL water for 3 minutes. After rinsing, the evaluation cloth is dried, and the cleaning rate is determined by the following formula.
[0094] [数 2]  [0094] [Equation 2]
(汚染布の KZ S ) (洗浄布の K/ S ) (KZ S for contaminated cloth) (K / S for cleaning cloth)
洗浄率 (%) X 1 0 0  Cleaning rate (%) X 1 0 0
(汚染布の K/ S ) (標準白布の KZ s )
Figure imgf000046_0001
(K / S for contaminated cloth) (KZ s for standard white cloth)
Figure imgf000046_0001
K/ S = [0095] 式中、 Rは日本電色製の色彩計∑—9000を用いて測定される反射率である。反 射率は 460nmフィルターを使用して測定した。洗浄率の評価は試験布 10枚の平均 値で行った。 K / S = [0095] In the formula, R is a reflectance measured using a color meter ∑-9000 made by Nippon Denshoku. The reflectance was measured using a 460 nm filter. The washing rate was evaluated based on the average value of 10 test cloths.
4-2.平均粒子径の測定  4-2. Measurement of average particle size
各サンプノレ及びその 合物 (こつレヽて、 目開き 1， 680 zm, 1, 410 xm、 1， 190 zm、 1, 000 Atm, 710 xm、 500 xm、 350 xm、 250 xm、 149 xm、の 9段の f帝 と受け皿を用いて分級操作を行った。分級操作は、受け皿に目開きの小さな篩から 目開きの大きな篩の順に積み重ね、最上部の 1, 680 xmの篩の上から lOOgZ回の ベースサンプノレを入れ、蓋をしてロータップ型篩い振盪機（(株)飯田製作所製、タツ ビング： 156回 Z分、ローリング： 290回 Z分）に取り付け、 10分間振動させた後、そ れぞれの篩及び受け皿上に残留したサンプノレを篩目ごとに回収して、サンプルの質 量を測定した。受け皿と各篩との質量頻度を積算してレ、くと、積算の質量頻度が、 50 %以上となる最初の篩の目開きを a μ mとし、 a μ mよりも一段大きレ、篩の目開きを b /imとし、受け皿から a μΐηの篩までの質量頻度の積算を。％、また a mの篩上の質 量頻度を(1%として、次式により平均粒子径 (重量 50%)を求めた。  Each sampnore and its combination (tread, 1, 680 zm, 1, 410 xm, 1, 190 zm, 1,000 Atm, 710 xm, 500 xm, 350 xm, 250 xm, 149 xm, 9 The classification was performed using a plate and a tray, and the classification was carried out in the order of a sieve with a small opening and a sieve with a large opening, and lOOgZ times from the top of the top 1 680 xm sieve. Put a base sump nore, cover and attach to a low-tap type sieve shaker (manufactured by Iida Manufacturing Co., Ltd., Tabbing: 156 times Z minutes, rolling: 290 times Z minutes), vibrate for 10 minutes, Samples remaining on each sieve and saucer were collected for each sieve, and the mass of the sample was measured.The mass frequency of the saucer and each sieve was integrated, and the accumulated mass frequency was measured. Is 50 μm or more, the opening of the first sieve is a μm, one step larger than a μm, and the opening of the sieve is b / im. The average particle size (weight: 50%) was calculated by the following formula, assuming that the mass frequency up to the sieve of a μΐη is%, and the mass frequency on the sieve of a m is 1%.
[0096] [数 3] [0096] [Equation 3]
(50- (c-d/ (logb-loga) X logb) ) I W (logb-loga)) 平均粒子径 （重量 50%) = 10  (50- (c-d / (logb-loga) X logb)) I W (logb-loga)) Average particle size (weight 50%) = 10
[0097] 4-3.嵩密度の測定 [0097] 4-3. Measurement of bulk density
嵩密度は JIS K3362— 1998に準じて測定した。  The bulk density was measured according to JIS K3362-1998.
[0098] [表 4] [0098] [Table 4]
実施例 比較例 Examples Comparative examples
1 2 3 4 5 1 2 3 1 2 3 4 5 1 2 3
(A) ァミラ-セ" A 0.5 0.4 0.2 0.5 0.5 - - - アミラ-セ'、 B - - - - - - ― 0.5(A) Amirase "A 0.5 0.4 0.2 0.5 0.5---Amirase ', B------― 0.5
(B) 種類 b1 b1 b1 b2 b1 b1 b1 b1 配合量（％) 86.69 76.59 86.69 76.69 87.29 87.19 87.69 87.29(B) Type b1 b1 b1 b2 b1 b1 b1 b1 Compound amount (%) 86.69 76.59 86.69 76.69 87.29 87.19 87.69 87.29
(C) 種類 a2 a2 a1 a2 a1 a1 a3 a1 配合量（％) 10.0 20.0 10.0 20.0 10.0 10.0 10.0 10.0 色素 種類 A B A A A A A A 配合量（％) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 香料 種類 A B A A A A A A 配合量（％) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 その他 フ。口テア-セ A 0.5 - 0.8 0.5 一 0.5 - - の成分 フ。□テア-セ、 'B - 0.4 - - - - - - (%) (C) Type a2 a2 a1 a2 a1 a1 a3 a1 Blending amount (%) 10.0 20.0 10.0 20.0 10.0 10.0 10.0 10.0 Dye type ABAAAAAA Blending amount (%) 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Fragrance Type ABAAAAAA Blending amount (%) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Others Ingredients for mouth tears A 0.5-0.8 0.5 One 0.5-- □ Thea, 'B-0.4-------(%)
フ°1]テア-セ C - 0.1 - - - - - - リハ。 -セ 0.1 0.1 0.1 0.1 一 0.1 0.1 - セルラ-セ" - 0.2 - - - - - - 表面被覆用 A型セ オラ仆 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 噴霧用ノ::オン界面活 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 性剤  [° 1] Thea-C C-0.1------Rehabilitation. -Se 0.1 0.1 0.1 0.1 One 0.1 0.1-Cellular "-0.2------Surface coating Type A Theola 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Spray No :: On-surface activity 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Sex agent
合計量 （％) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 平均粒子 ί圣 [ m] 540 520 540 530 530 540 540 530 嵩密度 [g/m L] 0.86 0.88 0.86 0.86 0.86 0.86 0.86 0.86 洗浄力 72 71 66 72 67 61 56 60  Total amount (%) 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Average particle ί 圣 [m] 540 520 540 530 530 540 540 530 Bulk density [g / m L] 0.86 0.88 0.86 0.86 0.86 0.86 0.86 0.86 Detergency 72 71 66 72 67 61 56 60
[0099] [表 5 ]  [0099] [Table 5]
Figure imgf000048_0001
Figure imgf000048_0001
[0100] 実施例中で用いた原料を下記に示す。  [0100] The raw materials used in the examples are shown below.
差替 え 用 紙（規則 26) [水溶性アルカリ無機化合物] Replacement paper (Rule 26) [Water-soluble alkali inorganic compounds]
•炭酸ナトリウム:粒灰 (旭硝子 (株)製、平均粒子径 320 /i m、嵩密度 1. 07g/mL) •炭酸カリウム:炭酸カリウム (粉末）（旭硝子 (株)製、平均粒子径 490 /i m、嵩密度 1 . 30g/mL)  • Sodium carbonate: Granular ash (Asahi Glass Co., Ltd., average particle size 320 / im, bulk density 1.07g / mL) • Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd., average particle size 490 / im , Bulk density 1.30g / mL)
•亜硫酸ナトリウム：無水亜硫酸曹達 (神州化学 (株)製）  • Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.)
[水溶性高分子化合物] [Water-soluble polymer compound]
•MA1：アクリル酸/マレイン酸コポリマーナトリウム塩、アクアリック TL— 400 (日本 触媒 (株)製）（純分 40%水溶液）  • MA1: Acrylic / maleic acid copolymer sodium salt, Aquaric TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
• PEG # 6000：ライオン（株）製ポリエチレングリコール、商品名 PEG # 6000M •PA :ポリアクリル酸ナトリウム、商品名ソカラン PA30 (BASF)  • PEG # 6000: Polyethylene glycol manufactured by Lion Co., Ltd., trade name PEG # 6000M • PA: Sodium polyacrylate, trade name Socaran PA30 (BASF)
[水難溶性化合物]  [Hydrosoluble compounds]
•ラウリン酸：日本油脂 (株)製、 NAA_ 122、融点 43°C  • Lauric acid: manufactured by Nippon Oil & Fats, NAA_122, melting point 43 ° C
[微粉体] [Fine powder]
• A型ゼオライト：シルトン B (水澤化学 (株)製、純分 80%)  • Type A zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd., 80% pure)
[界面活性剤] [Surfactant]
• a SF— Na :炭素数 14 :炭素数 16 = 18 : 82の α スルホ脂肪酸メチルエステル のナトリウム塩 (ライオン (株)製、 ΑΙ = 70%、残部は未反応脂肪酸メチルエステル、 硫酸ナトリウム、メチルサルフェート、過酸化水素、水等）  • a SF—Na: Sodium salt of α-sulfo fatty acid methyl ester with carbon number 14: carbon number 16 = 18: 82 (manufactured by Lion Co., Ltd., ΑΙ = 70%, the remainder is unreacted fatty acid methyl ester, sodium sulfate, methyl Sulfate, hydrogen peroxide, water, etc.)
• LAS -K :直鎖アルキル（炭素数 10〜 14)ベンゼンスルホン酸（ライポン LH— 200 (ライオン (株)製) LAS— Η純分 96%)を界面活性剤組成物調製時に 48%水酸化 カリウム水溶液で中和する）。表 1中の配合量は、 LAS— Kとしての質量％を示す。 • LAS -K: Linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Laipon LH-200 (manufactured by Lion Corporation) LAS—96% pure) 48% hydroxylated during preparation of surfactant composition Neutralize with aqueous potassium). The compounding amounts in Table 1 indicate mass% as LAS-K.
• LAS - Na：直鎖アルキル（炭素数 10〜 14)ベンゼンスルホン酸（ライポン LH— 20 0 (ライオン (株)製) LAS _H純分 96%)を界面活性剤組成物調製時に 48%水酸化 ナトリウム水溶液で中和する）。表 2中の配合量は、 LAS _Naとしての質量％を示す • LAS-Na: Linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (Laipon LH—20 0 (manufactured by Lion Corporation) LAS _H pure 96%) 48% hydroxylated during preparation of surfactant composition Neutralize with aqueous sodium). The blending amount in Table 2 indicates mass% as LAS_Na.
•AOS— K :炭素数 14〜18のアルキル基をもつひ一ォレフインスルホン酸カリウム（ ライオン (株)製） • AOS—K: Potassium monoolefin sulfonate having an alkyl group with 14 to 18 carbon atoms (manufactured by Lion Corporation)
•石鹼:炭素数 12〜： 18の脂肪酸ナトリウム (ライオン (株)製、純分： 67%、タイター： 4 0〜45。C、脂肪酸組成： C12 : l l . 7%、C14 : 0. 4%、C16 : 29. 2%、C18F0 (ス テアリン酸） : 0. 7%, C18F1 (才レイン酸）： 56. 8%, C18F2 (リノ一ノレ酸）： 1. 2%, 分子量： 289) • Ishizuchi: Fatty acid sodium with 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 4 0-45. C, fatty acid composition: C12: ll. 7%, C14: 0.4%, C16: 29. 2%, C18F0 (stearic acid): 0.7%, C18F1 (year-old carboxylic acid): 56.8%, C18F2 (Linoinolic acid): 1. 2%, molecular weight: 289)
.ノ二オン界面活性剤 A: EC〇R〇L26 (ECOGREEN社製炭素数 12〜： 16のアルキ ル基をもつアルコール）の酸化エチレン平均 15モル付加体（純分 90%)  Nonionic surfactant A: EC ○ R ○ L26 (ECOGREEN Co., Ltd., 12 to 16 alcohols with 16 alkyl groups) ethylene oxide average 15 mol adduct (pure 90%)
•ノニオン界面活性剤 B： ECOROL26 (ECOGREEN社製炭素数 12〜： 16のァノレキ ル基をもつアルコール）の酸化エチレン平均 6モル付加体（純分 90%)  • Nonionic surfactant B: ECOROL26 (ECOGREEN Co., Ltd., an alcohol with 12 to 16 carbon atoms) An average of 6 moles of ethylene oxide adduct (pure 90%)
[色素]  [Dye]
•色素 A：群青（大日精化工業 (株）製、 Ultramarine Blue)  • Dye A: Ultramarine Blue (manufactured by Dainichi Seika Kogyo Co., Ltd.)
•色素 B : Pigment Green 7 (大日精化工業製） • Dye B: Pigment Green 7 (Daiichi Seika Kogyo)
'色素 C :アクリロニトリル/スチレン/アクリル酸を構成モノマーとし、水分散系にお けるラジカル乳化重合にて得られる平均粒子径 0. 35 x mの球状樹脂粒子に、樹脂 分に対して約 1%の C. I. BASIC RED— 1を重合樹脂懸濁液に加え加熱処理して 得られる桃色の蛍光顔料水分散体。  'Dye C: Containing monomers of acrylonitrile / styrene / acrylic acid, into spherical resin particles with an average particle size of 0.35 xm obtained by radical emulsion polymerization in an aqueous dispersion, about 1% of resin content An aqueous dispersion of pink fluorescent pigment obtained by adding CI BASIC RED-1 to the polymer resin suspension and heat-treating it.
[香料] [Fragrance]
•香料 A:特開 2002— 146399号公報 [表 11]〜[表 18]に示す香料組成物 A •香料 B :特開 2002— 146399号公報 [表 11]〜[表 18]に示す香料組成物 B •香料 C：特開 2002— 146399号公報 [表 11 ]〜[表 18]に示す香料組成物 C •香料 D :特開 2002— 146399号公報 [表 11]〜[表 18]に示す香料組成物 D  • Perfume A: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18] • Perfume B: Perfume composition shown in JP-A-2002-146399 [Table 11]-[Table 18] Product B • Fragrance C: Perfume composition C shown in JP-A-2002-146399 [Table 11] to [Table 18] C • Perfume D: Shown in JP-A 2002-146399 [Table 11]-[Table 18] Fragrance composition D
[酵素]  [Enzyme]
•プロテアーゼ A：サビナーゼ 12T (ノボザィムズ製）  • Protease A: Sabinase 12T (Novozymes)
•プロテアーゼ B：エバラーゼ 8T (ノボザィムズ製） • Protease B: Everase 8T (Novozymes)
•プロテアーゼ C：カンナーゼ 24T (ノボザィムズ製） • Protease C: Cannase 24T (Novozymes)
•アミラーゼ A：スティンザィム 12T (ノボザィムズ製） • Amylase A: Stinzym 12T (manufactured by Novozymes)
•アミラーゼ B：ターマミノレ 120T (ノボザィムズ製） • Amylase B: Termaminole 120T (Novozymes)
•アミラーゼ C：デユラミル 120T (ノボザィムズ製） • Amylase C: Deyuramil 120T (Novozymes)
•リパーゼ：ライペックス 50T (ノボザィムズ製） • Lipase: Leipex 50T (Novozymes)
•セルラーゼ：セルザィム 0. 7T (ノボザィムズ製） [その他] • Cellulase: Celzym 0.7T (Novozymes) [Other]
•蛍光剤：チノパール CBS— X (チバスペシャルティケミカルズ） Zチノパール AMS— • Fluorescent agent: Chino Pearl CBS— X (Ciba Specialty Chemicals) Z Chino Pearl AMS—
GX (チバスペシャルティケミカルズ） = 8/2 (質量比）の混合物 Mixture of GX (Ciba Specialty Chemicals) = 8/2 (mass ratio)
'結晶性層状ケィ酸ナトリウム （クラリアントトクャマ社製 SKS— 6)  'Crystalline layered sodium silicate (SKS-6 by Clariant Tokuma)
•硫酸ナトリウム：中性無水芒硝（四国化成工業 (株)製）  • Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.)
'塩化ナトリウム：日精のやき塩 C (日本精塩 (株)製）  'Sodium chloride: Nissei Yaki salt C (manufactured by Nippon Seio Inc.)
図面の簡単な説明 Brief Description of Drawings
[図 1]図 1は、 3種類のアミラーゼ（ターマミル、デユラミル及びスティンザィム）につい て、粘度の経時変化を表すグラフである。 [FIG. 1] FIG. 1 is a graph showing changes in viscosity over time for three types of amylases (Termamyl, Deyuramil, and Stinzym).

Claims

請求の範囲 [1] 以下の成分を含有することを特徴とする粒状洗剤組成物： (A)以下の式（1)により算出される粘度低減率が 40%以上であるアミラーゼ、 (B) 10〜50質量％の界面活性剤を含有する界面活性剤含有粒子、及び (C)水溶性アルカリ無機化合物を、有機又は無機水溶性高分子化合物と水難溶性 化合物とで表面処理してなり、水溶性アル力リ無機化合物の含有量が 50〜 98質量 %である、 表面処理した水溶性アルカリ無機化合物粒子。 Claims [1] A granular detergent composition comprising the following components: (A) an amylase having a viscosity reduction rate calculated by the following formula (1) of 40% or more, (B) 10 Surfactant-containing particles containing ~ 50% by mass of surfactant, and (C) a water-soluble alkali inorganic compound is surface-treated with an organic or inorganic water-soluble polymer compound and a poorly water-soluble compound, and is water-soluble. Surface-treated water-soluble alkali inorganic compound particles having an Al force inorganic compound content of 50 to 98% by mass.
[数 1]  [Number 1]
(初期粘度） 一 （6 0分後の粘度） (Initial viscosity) I (Viscosity after 60 minutes)
粘度低減率 （％) = x 0 0 ί ) Viscosity reduction rate (%) = x 0 0 ί)
(初期粘度）  (Initial viscosity)
[2] (Α)成分のアミラーゼが、 50。/。以上の粘度低減率を有することを特徴とする請求項 [2] (Α) Component amylase is 50. /. The viscosity reduction rate is as described above.
1記載の粒状洗剤組成物。  The granular detergent composition according to 1.
[3] (Α)成分のアミラーゼが、スティンザィム（登録商標）である請求項 2記載の粒状洗 剤組成物。 [3] The granular detergent composition according to claim 2, wherein the amylase as component (ii) is Stinzym (registered trademark).
[4] (Α)成分のアミラーゼ力 組成物の全量を基準として、酵素タンパク量として 0. 00 [4] Amylase power of (Α) component Based on the total amount of the composition, the amount of enzyme protein is 0.00.
1質量％〜0. 05質量％の量で含まれる請求項:!〜 3のいずれか 1項記載の粒状洗 剤組成物。 The granular detergent composition according to any one of claims 1 to 3, wherein the granular detergent composition is contained in an amount of 1% by mass to 0.05% by mass.
[5] (Β)成分の界面活性剤含有粒子に含まれる界面活性剤が、炭素数 8〜： 18のアル キル基を有する直鎖アルキルベンゼンスルホン酸のアルカリ金属塩；炭素数 10〜20 の α—ォレフインスルホン酸のアルカリ金属塩；炭素数 8〜20の飽和又は不飽和 α スルホ脂肪酸又はそのメチル、ェチルもしくはプロピルエステルのアルカリ金属塩； 炭素数 10〜20の直鎖又は分岐鎖のアルキル基を有し、平均付加モル数が 10モル 以下のエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド又はそれらの 混合物を付カ卩したアルキルエーテル硫酸塩のアルカリ金属塩；及び高級脂肪酸のァ ルカリ金属塩からなる群から選ばれるァニオン界面活性剤を含有する請求項 1〜4の レ、ずれか 1項記載の粒状洗剤組成物。 [5] The surfactant contained in the surfactant-containing particles of component (ii) is an alkali metal salt of a linear alkylbenzene sulfonic acid having an alkyl group having 8 to 18 carbon atoms; α having 10 to 20 carbon atoms —Alkenyl metal salt of olefin sulfonic acid; saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms or alkali metal salt of methyl, ethyl or propyl ester thereof; linear or branched alkyl having 10 to 20 carbon atoms And an alkali metal salt of an alkyl ether sulfate with an average added mole number of 10 mol or less of ethylene oxide, propylene oxide, butylene oxide or a mixture thereof; and an alkali metal salt of a higher fatty acid. The granular detergent composition according to claim 1, wherein the granular detergent composition contains an anionic surfactant selected from the group.
[6] (B)成分の界面活性剤含有粒子に含まれる界面活性剤が、炭素数 6〜22の脂肪 族アルコールに炭素数 2〜4のアルキレンオキサイドを平均 3〜30モル付加したポリ ォキシアルキレンアルキル (又はアルケニル）エーテルであるノニオン界面活性剤を 含有する請求項:!〜 5のいずれか 1項記載の粒状洗剤組成物。 [6] The surfactant contained in the surfactant-containing particles of component (B) is a polyoxygen obtained by adding an average of 3 to 30 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms. The granular detergent composition according to any one of claims 5 to 5, comprising a nonionic surfactant which is an alkylene alkyl (or alkenyl) ether.
[7] (B)成分の界面活性剤含有粒子が、組成物の全量を基準として、 50〜94質量％ の量で含まれる請求項 1〜6のいずれ力 4項記載の粒状洗剤組成物。  [7] The granular detergent composition according to any one of claims 1 to 6, wherein the surfactant-containing particles (B) are contained in an amount of 50 to 94% by mass based on the total amount of the composition.
[8] (B)成分の界面活性剤含有粒子が、 200〜： 1 , 500 x mの平均粒子径を有する請 求項:!〜 7のいずれか 1項記載の粒状洗剤組成物。  [8] The granular detergent composition according to any one of claims 7 to 7, wherein the surfactant-containing particles of component (B) have an average particle size of 200 to: 1,500 x m.
[9] (B)成分の界面活性剤含有粒子の水分量力 4〜： 10質量％である請求項 1〜8の レ、ずれか 1項記載の粒状洗剤組成物。  [9] The granular detergent composition according to [1] or [8], wherein the water content of the surfactant-containing particles of the component (B) is 4 to 10% by mass.
[10] (C)成分が、平均粒子径 150〜400 μ mの表面処理した水溶性アルカリ無機化合 物粒子である請求項:!〜 9のいずれか 1項記載の粒状洗剤組成物。  [10] The granular detergent composition according to any one of [9] to [9], wherein the component (C) is a surface-treated water-soluble alkali inorganic compound particle having an average particle diameter of 150 to 400 μm.
[11] (C)成分が、水溶性アルカリ無機化合物核粒子を第 1表面処理剤として有機又は 無機水溶性高分子化合物で表面処理し、得られた粒子をさらに第 2表面処理剤とし て水難溶性化合物で表面処理することにより得ることが出来る表面処理した水溶性 アルカリ無機化合物粒子である、請求項：!〜 10のいずれか 1項記載の粒状洗剤組成 物。  [11] The component (C) is a surface-treated water-soluble alkali-inorganic compound core particle with an organic or inorganic water-soluble polymer compound as a first surface treatment agent, and the obtained particle is further treated with a second surface treatment agent as a second surface treatment agent. The granular detergent composition according to any one of claims 10 to 10, which are surface-treated water-soluble alkali-inorganic compound particles that can be obtained by surface treatment with a soluble compound.
[12] 前記水溶性アルカリ無機化合物核粒子が、炭酸ナトリウム、炭酸カリウム及びトリポ リリン酸ナトリウムからなる群から選ばれる請求項 11記載の粒状洗剤組成物。  12. The granular detergent composition according to claim 11, wherein the water-soluble alkali-inorganic compound core particles are selected from the group consisting of sodium carbonate, potassium carbonate, and sodium tripolyphosphate.
[13] 前記第 1表面処理剤が、ポリアクリル酸塩、アクリル酸/マレイン酸共重合体塩、ァ クリル酸/イタコン酸共重合体塩、アクリル酸アルキル共重合体塩、及びこれらの誘 導体からなる群から選ばれる請求項 11又は 12記載の粒状洗剤組成物。  [13] The first surface treatment agent is a polyacrylate, an acrylic acid / maleic acid copolymer salt, an acrylic acid / itaconic acid copolymer salt, an alkyl acrylate copolymer salt, and derivatives thereof. The granular detergent composition according to claim 11 or 12, which is selected from the group consisting of:
[14] 前記第 2表面処理剤が、平均炭素鎖長 8〜22の飽和又は不飽和脂肪酸である請 求項 11〜： 13のいずれか 1項記載の粒状洗剤組成物。  [14] The granular detergent composition according to any one of claims 11 to 13, wherein the second surface treatment agent is a saturated or unsaturated fatty acid having an average carbon chain length of 8 to 22.
[15] (C)成分が、組成物の全量を基準として、 5〜40質量％の量で含まれる請求項 11 〜 14のいずれか 1項記載の粒状洗剤組成物。  [15] The granular detergent composition according to any one of claims 11 to 14, wherein the component (C) is contained in an amount of 5 to 40% by mass based on the total amount of the composition.
[16] (C)成分の水分量力 8質量％以下である請求項 11〜： 15のいずれ力 4項記載の 粒状洗剤組成物。 [17] 更に、プロテアーゼを含有する請求項：!〜 16いずれか 1項記載の粒状洗剤組成物 [16] The granular detergent composition according to any one of claims 11 to 15, wherein the water content of component (C) is 8% by mass or less. [17] The granular detergent composition according to any one of claims 16 to 16, further comprising a protease.
PCT/JP2005/019394 2004-10-22 2005-10-21 Amylase-containing granular detergent composition WO2006043662A1 (en)

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Citations (6)

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JPH06128599A (en) * 1992-10-15 1994-05-10 Lion Corp Production of high-bulk-density granular detergent
JPH09249684A (en) * 1996-03-14 1997-09-22 Kdk Corp Novel compound for determination of amylase activity and determination of amylase activity
JP2000508914A (en) * 1996-04-30 2000-07-18 ノボ ノルディスク アクティーゼルスカブ α-amylase mutant
JP2002540784A (en) * 1999-03-31 2002-12-03 ノボザイムス アクティーゼルスカブ Polypeptides having alkaline α-amylase activity and nucleic acids encoding them
JP2004210956A (en) * 2002-12-27 2004-07-29 Kao Corp Method for producing detergent particle group
JP2004263057A (en) * 2003-02-28 2004-09-24 Asahi Denka Kogyo Kk Detergent composition for automatic dish washer, and preparation process therefor

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Publication number Priority date Publication date Assignee Title
JPH06128599A (en) * 1992-10-15 1994-05-10 Lion Corp Production of high-bulk-density granular detergent
JPH09249684A (en) * 1996-03-14 1997-09-22 Kdk Corp Novel compound for determination of amylase activity and determination of amylase activity
JP2000508914A (en) * 1996-04-30 2000-07-18 ノボ ノルディスク アクティーゼルスカブ α-amylase mutant
JP2002540784A (en) * 1999-03-31 2002-12-03 ノボザイムス アクティーゼルスカブ Polypeptides having alkaline α-amylase activity and nucleic acids encoding them
JP2004210956A (en) * 2002-12-27 2004-07-29 Kao Corp Method for producing detergent particle group
JP2004263057A (en) * 2003-02-28 2004-09-24 Asahi Denka Kogyo Kk Detergent composition for automatic dish washer, and preparation process therefor

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