WO2000077158A1 - Base granulaire et detergent particulaire - Google Patents

Base granulaire et detergent particulaire Download PDF

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Publication number
WO2000077158A1
WO2000077158A1 PCT/JP2000/003813 JP0003813W WO0077158A1 WO 2000077158 A1 WO2000077158 A1 WO 2000077158A1 JP 0003813 W JP0003813 W JP 0003813W WO 0077158 A1 WO0077158 A1 WO 0077158A1
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WO
WIPO (PCT)
Prior art keywords
weight
surfactant
water
base
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2000/003813
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English (en)
Japanese (ja)
Inventor
Yoichi Sugiyama
Hiroshi Kitagaito
Shuji Takana
Hitoshi Takaya
Shu Yamaguchi
Hiroyuki Yamashita
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Kao Corp
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Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to EP00935650A priority Critical patent/EP1104806A4/fr
Priority to JP2000607257A priority patent/JP3912986B2/ja
Publication of WO2000077158A1 publication Critical patent/WO2000077158A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/046—Salts
    • 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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a base particle group for supporting a surfactant (hereinafter, referred to as a base particle group) and a detergent particle group.
  • a base particle group for supporting a surfactant (hereinafter, referred to as a base particle group) and a detergent particle group.
  • a technique in which a part of the existing sodium bicarbonate is decomposed into sodium carbonate during spray drying to release carbon dioxide, thereby expanding the base granules and improving the oil absorbing ability.
  • the base granules “bulge”, which leads to a problem of reduced bulk density and Is left in the detergent, causing a decrease in the alkaline buffer area (pH value) of sodium sodium carbonate, which is used as an alkaline agent, and adversely affecting sebum dirt cleaning performance, etc.
  • the present invention provides a base granule having a sufficient bulk density for use in a compact detergent and further having an extremely large oil absorption capacity, and a single granule comprising a surfactant supported on the base granule.
  • An object of the present invention is to provide a detergent particle group containing a nuclear detergent particle group.
  • a group of base granules having a surfactant content of 0 to 10% by weight obtained by spray drying a slurry containing at least (II) a water-soluble polymer and an alkali metal halide.
  • the weight ratio of the water-soluble polymer and the halogenated alkali metal salt in the base granules constituting the base granule group is 0.1 to 100, the water-soluble polymer halogenated alkali metal salt.
  • Base particles for supporting a surfactant
  • a cleaning builder such as water-soluble polymers, water-soluble salts and water-insoluble inorganic substances.
  • the base granules obtained by spray drying (hereinafter referred to as slurry in the present invention) have an extremely low oil absorption compared to the oil absorption capacity (expected value) estimated from the specific surface area of the base and the pore volume in the base granules. Only the ability was expressed. Then, the present inventors examined the cause, and found that the water-soluble polymer component, which is a component for securing the particle strength of the base granule, tends to be unevenly distributed on the surface of the base granule and its vicinity in the spray drying process. As a result, it was clarified that an amorphous film composed of a water-soluble polymer and a water-soluble salt was formed on the surface of the base granules.
  • the present inventors have found that such base granules have a surface state that is unsuitable for supporting a surfactant, which is an oily substance, and for absorbing oil, so that the base granules can fully exhibit the inherent oil absorbing ability of the base granules. I thought he didn't.
  • the present inventor has further studied the process of spray drying and the base granules. As a result, it was found that a certain substance has the ability to inhibit the formation of a film.
  • the base granule group of the present invention is an aggregate of base granules, and has a surfactant content of 0 to 10% by weight.
  • a slurry containing a surfactant is spray-dried to produce base granules, a film tends to be formed on the surface of the obtained base granules. May decrease.
  • the content of the surfactant in the base particles is smaller, and it is most preferable that the surfactant is substantially free of the surfactant.
  • the content of the surfactant in the base particles is more preferably 0 to 5% by weight, and particularly preferably 0 to 3% by weight.
  • surfactant examples include a surfactant carried on the base particles.
  • the bulk density of the base granules of the present invention a surfactant is supported while maintaining the mononuclear properties of the base granules, and the bulk density required for compact detergents is 400 to 100 gZL.
  • the bulk density required for compact detergents is 400 to 100 gZL.
  • 450-800 gZL is more preferable, and 500-650 gZL is most preferable.
  • the average particle size of the base particles is preferably from 150 to 500 zm, more preferably from 180 to 300 m.
  • the base particles can carry a large amount of a nonionic surfactant having a melting point of 40 ° C. or less, which is effective for sebum stains in a low temperature range.
  • the oil-absorbing ability of such a base particle group by a nonionic surfactant dropping method described below is preferably 0.25 gZg or more, more preferably 0.30 gZg or more, still more preferably 0.35 or more. 40 gZg is most preferred.
  • a film-forming inhibitor is present on the surface of the base granules and / or in the vicinity thereof in terms of the surfactant loading and oil absorption.
  • the presence of a film formation inhibitor on and / or in the vicinity of the base granules can be determined by observing the base granules by scanning electron microscopy (SEM) or energy dispersive X-ray spectroscopy (EDS). You can know.
  • SEM scanning electron microscopy
  • EDS energy dispersive X-ray spectroscopy
  • the presence of the film-forming inhibitor as crystals means that a peak derived from the film-forming inhibitor is detected when powder X-ray diffraction analysis of the base granules is performed.
  • Sodium carbonate, sodium sulfate, and the like which are generally used as water-soluble salts to be combined with detergents, are easily compatible with the water-soluble polymer and tend to partially become amorphous.
  • the halogenated alkali metal salt since the halogenated alkali metal salt has high crystallinity, the halogenated alkali metal salt is crystallized alone and usually exists as crystals in the base granules in the present invention. For this reason, it is preferable to use an alkali metal halide as a film formation inhibitor.
  • the water-soluble polymer as the component (A) is an organic polymer having a solubility in water at 25 ° C of 0.5 gZl 100 g or more and a molecular weight of 1,000 or more, which has improved cleaning performance and / or base granules.
  • at least one selected from the group consisting of carboxylic acid polymers, cell derivatives such as carboxymethyl cellulose, aminocarboxylic acid polymers such as polyglyoxylate and polyaspartate, soluble starch, and saccharides is preferred.
  • Preferred examples are carboxylic acid-based polymers.
  • acrylic acid - maleic acid copolymer salts (N a, K, ⁇ ⁇ 4 , etc.) and polyacrylate (N a, K, ⁇ ⁇ 4 , etc.) are particularly excellent.
  • those having a molecular weight of 1,000 to 100,000 are preferable, those having a molecular weight of 2,000 to 80,000 are more preferable, and those having a molecular weight of 5,000 to 50,000 are particularly preferable.
  • the content of the water-soluble polymer in the base particles is preferably 2 to 20% by weight, more preferably 3 to 17% by weight, and most preferably 4 to 12% by weight. Within this range, the base granules have sufficiently high particle strength, and are also preferable in terms of the solubility of the detergent composition.
  • the component (B) of the film-forming inhibitor is (A) a water-soluble polymer, (C) a water-soluble salt other than the film-forming inhibitor, and, if necessary, (D) a slurry comprising a water-insoluble inorganic substance.
  • a slurry comprising a water-insoluble inorganic substance.
  • the water-soluble salts are those having a solubility in water at 25 ° C. of 0.5 gZ100 or more and a molecular weight of less than 1,000. Water-insoluble substances 25.
  • the solubility of C in water is less than 0.5 gZ100.
  • the film-forming inhibitor has a function of roughening or discontinuous the surface of the dried particles by including it in the slurry. It is a substance that makes it easy to do.
  • the film formation inhibitor is prepared by mixing a slurry composed of the component (A), the component (C) and, if necessary, the component (D) with a far-infrared water meter (for example, EB-340MOC type manufactured by Shimadzu Corporation). )
  • the time required for drying when drying the thin film (3 g of slurry is evenly placed on a sample dish and heated, and the slurry is dried from 50% by weight to 3% by weight to form a thin film). (Drying time) is shorter than that in the case where the film formation inhibitor is not contained, which is confirmed. In drying, it is preferable that the fixed-rate drying period is long and the reduced-rate drying period is short. Further, when the formed thin film is observed by SEM, it is preferable that the surface of the thin film is rough or discontinuous.
  • the film formation inhibitor for example, selected from the group consisting of alkali metal halides such as chloride, bromide, iodide, sodium fluoride, potassium, calcium, and magnesium, and alkaline earth metal salts.
  • alkali metal halides such as chloride, bromide, iodide, sodium fluoride, potassium, calcium, and magnesium
  • alkaline earth metal salts alkali metal halides
  • Chloride is preferable in terms of storage stability of the detergent particles, and an alkali metal salt is preferable because of its effect on cleaning performance, and sodium chloride is particularly preferable from an economic viewpoint.
  • the production method or addition method is not limited, but it is particularly preferable to blend the corresponding halide itself into the slurry.
  • a halogen-containing compound such as hydrochloric acid is mixed with the slurry, and a reaction such as salt exchange is performed in the slurry to finally produce a desired halogen-containing compound in the base granules.
  • the content of the film-forming inhibitor in the base particles is preferably 0.2 to 20% by weight, more preferably 1 to 12% by weight, and more preferably 2 to 12% by weight from the viewpoint of sufficient film-forming inhibiting effect and detergency. 8% by weight is particularly preferred.
  • the weight ratio in the base granules is 100 or less, the formation of a film on the surface of the base granules can be prevented, whereby the oil absorption capacity of the base granules can be improved, which is preferable.
  • the weight ratio is 0.1 or more, it is preferable because the particle strength of the base condyle can be secured to a sufficient degree.
  • alkali metal salts such as a carbonate group, a hydrogen carbonate group, a sulfate group, a sulfite group, a hydrogen sulfate group, a phosphate group, an ammonium salt, or Water-soluble inorganic salts such as amine salts and low-molecular-weight water-soluble organic acid salts such as citrate and fumarate can be mentioned. Among them, salts having a carbonate group, a sulfate group and a sulfite group are preferred.
  • the component (C) may be composed of a single component or a plurality of components.
  • sodium carbonate is an alkaline agent that shows a suitable PH buffer region in the washing liquid.
  • salts having a high degree of dissociation such as sodium sulfate, potassium sulfate, and sodium sulfite, increase the ionic strength of the washing liquid and suitably act on sebum stains and the like.
  • Sulfite groups also reduce hypochlorite ions contained in tap water and have the effect of preventing oxidative degradation of detergent components such as enzymes and fragrances by hypochlorite ions.
  • sodium tripolyphosphate can be used as the component (C).
  • Examples of the low molecular weight water-soluble organic acid salts include carboxylate salts such as citrate and fumarate, but p KC a 2+ is large in expectation of sequestering ability, and / or cation exchange capacity is high. Larger bases are preferred.
  • carboxylate salts such as citrate and fumarate
  • p KC a 2+ is large in expectation of sequestering ability, and / or cation exchange capacity is high. Larger bases are preferred.
  • methyliminodiacetic acid salt, iminodisuccinic acid salt, ethylenediamine disuccinic acid salt, phosphoric acid diacetic acid salt, hydroxyethyliminodiacetic acid salt, 5-alanine diacetate, hydroxyiminodiacetic acid Acid salts, methylglycine diacetate, glutamic acid diacetate, asparagine diacetate, and serine diacetate are preferred.
  • Amorphous silicate has the effect of increasing the granule strength of the supporting granules, but when the aluminosilicate is used as the water-insoluble substance contained in the supporting granules, the amorphous silicate becomes It is preferable that it is not substantially contained in the base granules for support of the present invention, since when formed into a slurry for producing the base granules, agglomerates are formed that become insoluble in water with time. .
  • the content of the water-soluble salts in the base particles is preferably 5 to 75% by weight, more preferably 10 to 70% by weight, and most preferably 20 to 60% by weight. Within these ranges, the base granules have sufficiently high particle strength, and are also preferable in terms of the solubility of the detergent particles.
  • water-insoluble inorganic component (D) component As the water-insoluble inorganic component (D), those having an average primary particle size of 0.1 to 20 m are preferable, and those having a mean particle size of 0.5 to 10 m are more preferable. Examples include crystalline aluminoketes, amorphous aluminogates, silicon dioxide, hydrated silicates, clay compounds such as perlite, bentonite, etc., which promote cleaning performance and the generation of undissolved residues of detergents. For example, crystalline aluminoates are preferred.
  • a type of zeolite A (for example, trade name: “Toyobuilder”; manufactured by Tosohichi Co., Ltd.) suitable as the crystalline aluminogate is also preferable in terms of sequestering ability and economy.
  • the value of the oil absorption capacity of the A-type zeolite according to the JIS K 5101 method is preferably 40 to 5 OmLZ100 g.
  • P type for example, trade name: "Doucil A24", “ZSE064", etc .; all manufactured by Crosfield
  • X type for example, trade name: "Wessalith XD”; manufactured by Degussa Co .; oil absorption capacity 80-100 mL Zl 100 g :
  • hybrid zeolite described in WO 98/42622 pamphlet is also a suitable crystalline aluminogenate.
  • S i 0 2 ZA 1 2 0 3 ( molar ratio) is preferably 5.0 or less More preferably, it is preferably 4.0 or less, more preferably 3.3 or less.
  • the volume of pores having a pore size of 0.05 to 0.5 zm is 0 to 0.5 TmLZg and the volume of 0.5 to 2 ⁇ m having a volume of 0.3 OmLZg or more. Or a plurality of components.
  • the content of the water-insoluble inorganic substance in the base particles is preferably 20 to 90% by weight, more preferably 20 to 75% by weight, and most preferably 25 to 70% by weight. Within this range, a base granule having excellent particle strength and solubility can be obtained. From the viewpoint of the washing performance and the improvement of the oil absorbing portion inside the base granules, the base granules further containing (D) a water-insoluble inorganic substance are preferable.
  • the base granules may contain other components such as surfactants and auxiliary components such as fluorescent dyes, pigments, and dyes suitable for detergent compositions.
  • the moisture content in the base granules is preferably from 1 to 10% by weight, more preferably from 1.5 to 8% by weight, still more preferably from 2 to 6% by weight, most preferably from 2 to 5% by weight, as measured by an infrared moisture meter. New Specific embodiments of the base granules according to the present invention are shown below.
  • Embodiment [1] Surfactant-containing obtained by spray-drying a slurry containing (A) a water-soluble polymer, (B) a film-forming inhibitor and (C) a water-soluble salt other than the film-forming inhibitor. Base granules with an amount of 0 to 10% by weight.
  • Embodiment [2] Base granules having a surfactant content of 0 to 10% by weight, obtained by spray-drying a slurry containing at least (A) a water-soluble polymer and an alkali metal halide. Wherein the weight ratio of the water-soluble polymer to the alkali metal halide in the base granules constituting the base granule group is 0.1 to 100 Base granules.
  • the base granules according to the embodiment [1] are obtained from a slurry containing the components (A) to (C).
  • the base granules according to the embodiment [2] include the component (A) and the component (A).
  • This is an embodiment obtained from a slurry containing at least an alkali metal halide which is a preferred example of the component (B).
  • the slurries in both embodiments may further contain the component (D).
  • the detergent particles in the present invention preferably refer to particles containing a surfactant and a builder, and the detergent particles in the present invention refer to an aggregate thereof.
  • the detergent particles of the invention can take any form of mononuclear detergent particles or polynuclear detergent particles, but are preferably mononuclear detergent particles.
  • the detergent particles are such that 1 to 100 parts by weight of a surfactant is supported with respect to 100 parts by weight of the base granules of the present invention, and the average particle size of the detergent particles is Is 150-750 m and the bulk density is 500 g ZL or more.
  • an anionic surfactant and a nonionic surfactant are preferable.
  • the anionic surfactant and the nonionic surfactant can be used alone, it is more preferable to use them in combination.
  • an amphoteric surfactant or a cationic surfactant can be used in combination depending on the purpose.
  • anionic surfactant such as alkylbenzene sulfonic acid salt is incorporated in the detergent particles in an amount of 5 to 25% by weight, the effect is exhibited in terms of non-paste forming property in water.
  • the average particle size of the detergent particles of the present invention is preferably 150 to 75 zm, more preferably 200 to 450 / m, from the viewpoints of solubility, powder feel and storage stability. 20-350 zm is particularly preferred.
  • the bulk density is preferably 500 to 1200 g ZL, more preferably 600 to 900 g ZL, and 65 0 to 800 gZL is particularly preferred.
  • the detergent composition of the present invention is a composition containing the above-described detergent particles, and further contains a detergent component (for example, builder granules, fluorescent dyes, enzymes, fragrances, and detergents) separately added in addition to the detergent particles.
  • a detergent component for example, builder granules, fluorescent dyes, enzymes, fragrances, and detergents
  • the content of the detergent particles in the detergent composition is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and preferably 80% by weight or more from the viewpoint of detergency. Is particularly preferred.
  • the base granules of the present invention include (A) a water-soluble polymer, (B) a film formation inhibitor, ( C) A slurry containing water-soluble salts other than the film formation inhibitor, wherein the dissolution rate of the component (B) in the slurry is such that the formation of a film on the surface of the obtained base granules is prevented. It can be obtained by a production method having a step of spray-drying a sufficient amount of slurry.
  • a specific example of such a production method includes a production method including the following steps (a) and (b).
  • the base granules according to the embodiment [2] can also be produced according to such a production method.
  • the step (a) is a step of preparing a slurry containing a predetermined component, and the obtained slurry is preferably a non-curable one capable of pumping liquid.
  • the dissolution rate of the film formation inhibitor should be sufficient to prevent film formation on the surface of the resulting base granules.
  • the drying step it is desired that the film formation inhibitor moves to the particle surface with the evaporation of water.
  • the weight ratio of the water-soluble polymer in the slurry to the film-forming inhibitor dissolved in the slurry (water-soluble polymer Z film-forming inhibitor) is preferably 100 or less, and 0.15 to 1: 1.
  • the weight ratio is preferably 100 or less from the viewpoint of suppressing the formation of a film, and the weight ratio is preferably 0.15 or more from the viewpoint of mixing a predetermined amount or more of other components such as a surfactant and a builder.
  • a slurry having a dissolution rate of the film formation inhibitor of preferably 60% by weight or more, more preferably 70% by weight or more, further preferably 85% by weight or more, and particularly preferably 90% by weight or more is prepared. I do.
  • the amount of water in the slurry is preferably 30 to 70% by weight, more preferably 35 to 60% by weight, particularly preferably 40 to 55% by weight, and most preferably 45 to 55% by weight. %.
  • the dissolution rate of the film formation inhibitor in the slurry can be measured by using a combination of known analytical methods. For example, the slurry is filtered under reduced pressure, and the water concentration P (%) in the filtrate is measured with a far-infrared heater type moisture meter (manufactured by Shimadzu Corporation). Further, the concentration S ⁇ %) of the film formation inhibitor in the filtrate is determined by ion chromatography or the like. Let the slurry moisture be Q (%) and the concentration of the film formation inhibitor in the slurry be T (%
  • the dissolution rate of the film formation inhibitor is calculated by the following equation.
  • the dissolution rate shall be 100%.
  • the amount of each component dissolved in the slurry can be appropriately set according to the water content of the slurry, the mixing order of the slurry components, the slurry temperature, and the desired content of each component in the base granule group.
  • the slurry temperature is preferably from 30 to 80 ° C, more preferably from 35 to 75 ° C, in view of the solubility of the water-soluble components (A, B, and C) and the pumpability.
  • the method and order of adding the components can be appropriately changed depending on the situation. For example, add all or almost all of the water to the mixing tank first, and preferably add the other ingredients sequentially or simultaneously, preferably after the water temperature has reached the set temperature, preferably 30-45 ° C. .
  • the usual order of addition is to add the liquid component first, and then add the water-soluble powder material. Also, add small amounts of auxiliary components such as dyes. Finally, a water-insoluble component is added. At this time, the water-insoluble component may be added in two or more portions for the purpose of improving the mixing efficiency.
  • the powder raw materials may be mixed in advance, and the mixture may be added to an aqueous medium.
  • the film formation inhibitor may be added first, last, or dividedly as long as a dissolution rate sufficient to prevent film formation is secured.
  • sodium sulfate and sodium carbonate are blended as the component (C), and a film formation inhibitor and
  • sodium chloride it is preferable to add sodium sulfate, sodium carbonate, and sodium chloride in this order, because the oil absorbing ability of the base granules can be further improved. This is because sodium chloride dissolves in a saturated solution of sodium sulfate and sodium carbonate, and fine crystals of baikite, which is a double salt of sodium sulfate and sodium carbonate, are precipitated. This is because the effect of increasing the number of oil sites is exhibited.
  • the slurry prepared in the step (a) is spray-dried.
  • a counter-current tower is more preferable because the thermal efficiency and the particle strength of the base granules are improved.
  • a pressure spray nozzle is particularly preferable in order to obtain a desired average particle size.
  • the temperature of the gas discharged from the drying tower is preferably 70 to 130, more preferably 80 to 120 ° C, in terms of the thermal efficiency of the drying tower.
  • the air blowing temperature may be appropriately set so that the exhaust air temperature is within the above range.
  • a film-forming inhibitor is added to the slurry, and the slurry is spray-dried, so that the film-forming inhibitor is present on the surface of the resulting base granules and at or near Z, or the film formation is inhibited in the base granules.
  • the agent can be present as crystals You.
  • the detergent particles are produced through the step (C) of supporting a surfactant on the base granules of the present invention.
  • the amount of the surfactant supported on the base particles is preferably 1 to 100 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the base particles, from the viewpoint of exhibiting detergency. It is more preferably 30 parts by weight, more preferably 30 parts to 70 parts by weight, particularly preferably 35 parts to 65 parts by weight.
  • the loading amount of the anionic surfactant is preferably 1 to 60 parts by weight, more preferably 1 to 50 parts by weight, and particularly preferably 3 to 40 parts by weight with respect to 100 parts by weight of the base granules. preferable.
  • the loading amount of the nonionic surfactant is preferably from 1 to 45 parts by weight, more preferably from 1 to 35 parts by weight, and even more preferably from 4 to 25 parts by weight, based on 100 parts by weight of the base particles.
  • an amphoteric surfactant or a cationic surfactant can be used in combination depending on the purpose.
  • the amount of the surfactant carried here means that the amount of the surfactant is not included even if the surfactant is added at the time of preparing the slurry in the step (a).
  • the melting point of the nonionic surfactant is preferably 40 ° C. or lower, more preferably 30 ° C. or lower, particularly preferably 25 ° C. or lower, and particularly preferably 22 ° C. or lower.
  • anionic surfactant examples include a sulfuric acid ester salt of an alcohol having 10 to 18 carbon atoms, a sulfuric acid ester salt of an alkoxylated alcohol having 8 to 20 carbon atoms, and an alkyl (10 to 1 carbon atoms).
  • a sulfuric acid ester salt of an alcohol having 10 to 18 carbon atoms examples include a sulfuric acid ester salt of an alcohol having 10 to 18 carbon atoms, a sulfuric acid ester salt of an alkoxylated alcohol having 8 to 20 carbon atoms, and an alkyl (10 to 1 carbon atoms).
  • a linear alkylbenzene sulfonate having an alkyl chain having 10 to 14 carbon atoms, and more preferably 12 to 14 carbon atoms is preferable.
  • sodium ions and / or potassium ions, monoethanolamine and diethanolamine are particularly preferred.
  • Examples of a method of supporting the surfactant on the base granule include a method of mixing the base granule and the surfactant using a batch type or continuous mixer.
  • the method of charging the mixer is as follows: (1) First, the base granules are charged into the mixer, and then the surfactant is added. (2) The base particles are charged into the mixer. , A small amount of the surfactant is charged little by little, and (3) a part of the base particles is charged into the mixer, and then the remaining base particles and the surfactant are charged little by little. .
  • the surfactant is preferably added in a liquid state, and more preferably, the surfactant in a liquid state is supplied by spraying. According to such an addition method, it is possible to produce the detergent particles while maintaining the mononuclear property of the base granules, which is preferable.
  • the detergent particles of the present invention are preferably mononuclear detergent particles from the viewpoint of solubility.
  • the mononuclear detergent particles in the present invention have a particle growth rate of preferably 1.5 or less, more preferably 1.3 or less.
  • Particle growth rate (average particle size of final detergent particle group) / (average particle size of base particle group)
  • the final detergent particle group is the average particle size of detergent particle group after step (c).
  • Detergent particles obtained by subjecting the particles to a surface modification treatment are Detergent particles obtained by subjecting the particles to a surface modification treatment.
  • Mononuclear particles can be confirmed by at least one of the following methods (e), (d), and ( ⁇ ).
  • ( ⁇ ) method The detergent particles sampled arbitrarily from around the average particle size of the detergent particles are cut off, and the presence or absence and the number of base granules in the detergent particles are observed by SEM to determine the mononuclear properties of the detergent particles. How to check. It can be seen that the detergent particles contained in the detergent particle group of the present invention are mononuclear detergent particles having a base granule as a core.
  • ( ⁇ ) method an organic solvent that does not dissolve the water-soluble polymer in the base granules in the detergent particles (eg, polyacrylate as a water-soluble polymer, anionic surfactant (LAS) as a surfactant in the base granules) Or a non-ionic surfactant can be used to extract the organic solvent solubles in the detergent particles, and then observe the organic solvent insolubles by SEM observation. . That is, when one base particle is present in the organic solvent-insoluble matter obtained by treating one detergent particle with the above organic solvent, it is understood that the detergent particle is a mononuclear detergent particle.
  • LAS anionic surfactant
  • Method A method for confirming the mononuclear properties of detergent particles by detecting the two-dimensional element distribution of the cut surface of the detergent particles embedded in resin by EDS or EPMA.
  • surfactants for example, those which exist in a solid or paste state even when the temperature is raised at 50 to 90 ° C. are prepared by preliminarily preparing a low-viscosity nonionic surfactant
  • a mixed solution or aqueous solution of a surfactant may be prepared by dispersing or dissolving in an aqueous ionic surfactant solution or in water, and may be added to the base particles in the form of the mixed solution or aqueous solution.
  • a surfactant existing in a solid or paste state can be easily added to the base granules, which is advantageous for the production of mononuclear detergent particles.
  • the mixing ratio of the low-viscosity surfactant or water and the solid or paste-like surfactant is preferably within a viscosity range in which the resulting mixed solution or aqueous solution can be sprayed.
  • the method for producing the above mixed solution include a method of adding a low-viscosity surfactant or a solid or base-like surfactant to water and mixing them, or a method of adding a surfactant in a surfactant having low curl or water.
  • An acid precursor of an anionic surfactant for example, an acid precursor of an anionic surfactant is neutralized with an alkaline agent (for example, an aqueous sodium hydroxide solution or an aqueous hydroxide water solution) to prepare a surfactant mixture. Good.
  • an acid precursor of an anionic surfactant before the addition of the surfactant, simultaneously with the addition of the surfactant, during the addition of the surfactant, or after the addition of the surfactant. It is.
  • an anionic surfactant acid precursor By adding an anionic surfactant acid precursor, the surfactant is highly compounded, the oil absorption capacity of the base granules is controlled, and the nonionic surfactant of the detergent particles is prevented from bleeding, and the physical properties such as fluidity. , Improved quality o
  • Examples of the acid precursor of the anionic surfactant which can be used in the present invention include: alkyl benzene sulfonic acid, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, hypoolefin sulfonic acid, and sulfonated fatty acid. And alkyl or alkenyl ether carboxylic acids, fatty acids and the like. It is particularly preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.
  • the amount of the acid precursor of the anionic surfactant used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the base granules. A weight part is more preferable, and 1 to 5 parts by weight is particularly preferable.
  • the amount of the acid precursor used is not included in the amount of the surfactant in the present invention. When the amount of the acid precursor of the anionic surfactant is within this range, the mononuclear properties of the particles in the detergent particle group tend to be maintained, and therefore, good high-speed solubility is exhibited.
  • the liquid precursor at normal temperature is supplied by spraying, and the solid precursor at normal temperature may be added as a powder, It may be supplied after spraying. However, if the powder is added, add the powder in the mixer until the powder melts. It is preferable to raise the temperature of the detergent particles.
  • An apparatus preferably used in the step (C) is an apparatus that is hardly subjected to strong shearing force (hard to disintegrate the base granules) from the viewpoint of producing a detergent particle group containing a large amount of mononuclear detergent particles.
  • a device having good mixing efficiency is preferable from the viewpoint of the dispersion efficiency of the surfactant.
  • Particularly preferred mixers include a horizontal mixing tank having a stirring shaft at the center of the cylinder, and a stirring blade attached to this shaft to mix powders. There is a share mixer and the like. Further, a surfactant may be supported on the base granule group by using a continuous type apparatus of the above mixer.
  • a continuous type mixer other than the above, there are, for example, a flexomics type (manufactured by Baurek Co., Ltd.) and a turbulizer (manufactured by Hosokawa Micron Corporation).
  • a nonionic surfactant In the case where a nonionic surfactant is used in this step, it has a function of increasing the melting point of this surfactant, and has a melting point of 45 to 100 and a water-soluble non-ionicity of 1,000 to 30,000.
  • the melting point enhancer that can be used in the present invention include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic nonionic surfactant.
  • the amount of the melting point increasing agent to be used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, most preferably 1 to 3 parts by weight based on 100 parts by weight of the base granules. This range is preferred from the viewpoints of suppression of aggregation between particles of the detergent particles contained in the detergent particles, rapid dissolution, and suppression of spotting and masking.
  • As a method of adding the melting point increasing agent it is necessary to mix and add a surfactant in advance by any method, or The addition of the melting point increasing agent after the addition of the surfactant is advantageous for suppressing the spotting property and the caking property of the detergent particles.
  • the temperature in the mixer in this step is increased by raising the temperature above the pour point of the surfactant to perform mixing.
  • the pour point of the surfactant is measured by a method specified in JIS K 2269.
  • the temperature for raising the temperature may be higher than the pour point of the surfactant added to promote the loading of the surfactant, but in a practical range, the temperature may exceed the pour point and exceed the pour point.
  • the temperature is preferably up to 50 ° C higher, more preferably 10 to 30 ° C higher than the pour point.
  • the temperature is raised to a temperature at which the acid precursor of the anionic surfactant can react, and mixing is performed.
  • the batch type mixing time for obtaining a suitable detergent particle group and the average residence time in continuous mixing are preferably from 1 to 20 minutes, more preferably from 2 to 10 minutes.
  • a step of drying during and / or after mixing of excess water may be included.
  • the powdered surfactant and Z or the powder builder before adding the surfactant, simultaneously with the addition of the surfactant, during the addition of the surfactant, or after adding the surfactant.
  • the powder builder By adding the powder builder, the particle size of the detergent particles can be controlled, and the detergency can be improved.
  • an acid precursor of an anionic surfactant when added, it is effective to add a powder builder exhibiting an alkaline property before adding the acid precursor from the viewpoint of promoting the neutralization reaction. .
  • binder builder means a powder detergency enhancer other than a surfactant, and specifically, a base having sequestering ability such as zeolite and citrate, and a carbonate.
  • Bases exhibiting alkaline ability such as sodium and potassium carbonate, bases having both sequestering ability and crystallinity ability such as crystalline gaterate, and other bases such as sodium sulfate which enhance ion strength Take action.
  • JP-A-5-279130, column 3, line 17 (Especially, those which are crystallized by firing at 500 to 100 ° C.) are described in JP-A-7-89712, column 2, line 45,
  • the crystalline gay acid salt described in the lower right column, line 18, page 2 (preferably the gay acid salt shown in Table 2) of Japanese Patent Application Laid-Open No. 60-222,795 as a preferred powder builder.
  • the alkali metal silicate having a Si 0 2 ZM 2 ⁇ (where M represents an alkali metal) of 0.5 to 3.2, preferably 1.5 to 2.6 is preferred. More preferably used.
  • the amount of the powder builder to be used is preferably 0.5 to 12 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the base granules.
  • the amount of the detergent powder builder used is within this range, the mononuclear property of the detergent particles contained in the detergent particle group is maintained, good high-speed solubility is obtained, and the control of the particle size is also suitable. Ah .
  • step (c) it is preferable to add a step of surface-modifying the detergent particles after the step (c).
  • the fluidity and non-caking properties of the particles of the detergent tend to be improved. Therefore, it is preferable to provide a surface modification step.
  • the apparatus used in the surface modification step for example, the mixer exemplified in the step (C) is preferable.
  • the surface coating agent will be described below.
  • the average particle size of the primary particles is 10 m or less. And more preferably 0.1 to 10 m.
  • the coverage of the particle surface of the detergent particles is improved, which is preferable from the viewpoint of improving the fluidity and the cake resistance of the detergent particles.
  • the average particle size of the fine powder is measured by a method using light scattering, for example, a particle analyzer (manufactured by HORIBA, Ltd.), or a measurement using a microscope. Further, it is preferable from the viewpoint of washing that the fine powder has high ion exchange ability and high alkali ability.
  • the fine powder is preferably an aluminoate salt, and may be either crystalline or amorphous.
  • fine powders such as sodium sulfate, sodium tripolyphosphate, calcium gayate, silicon dioxide, bentonite, talc, clay, silica compounds such as non-crystalline silica derivatives and crystalline silicate compounds
  • the body is also preferred.
  • metal stones having primary particles of 0.1 to 10 m, powdered surfactants (eg, alkyl sulfates) and water-soluble organic salts can be used in the same manner.
  • the crystalline silicate compound When a crystalline silicate compound is used, it is preferable to use the crystalline silicate compound as a mixture with a fine powder other than the crystalline silicate compound in order to prevent deterioration of the crystalline silicate due to aggregation or the like caused by moisture absorption or carbon dioxide gas.
  • the amount of the fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 20 parts by weight based on 100 parts by weight of the detergent particles.
  • the amount of the fine powder used is in this range, the flowability is improved and a good feeling of use is given to consumers.
  • liquid material examples include an aqueous solution and a melt of a water-soluble polymer or a fatty acid.
  • water-soluble polymer examples include carboxymethylcellulose, polyethylene glycol, polyacrylic acid tuda, a copolymer of acrylic acid and maleic acid, or a salt thereof. And the like.
  • the amount of the water-soluble polymer used is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight, based on 100 parts by weight of the detergent particles.
  • the amount of the water-soluble polymer used in this range is a powder that maintains the mononuclear properties of the detergent particles contained in the detergent particle group, obtains good high-speed solubility, and has good fluidity and anti-caking properties. You can get your body.
  • the fatty acid examples include a fatty acid having 10 to 22 carbon atoms.
  • the amount of the fatty acid to be used is preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the detergent particles.
  • the base granules of the present invention can be suitably used as a raw material for a high bulk density detergent composition.
  • the compaction and granulation treatment is performed without adding the surfactant, if necessary, to the base granules obtained in the step (b) without performing the step (c).
  • the use of the base granules of the present invention is not particularly limited to particles for supporting a surfactant as in step (c).
  • Average particle size Determined using a sieve specified in JISZ8801. For example, the opening is 20000m, 1400zm, 1000m, 7100tz, 500m, 350m, 250m, 180m, 125m m 9-stage sieve and saucer, using a single tap machine (made by HEIKO SEISAKUSHO, tapping: 15 6 times Z minutes, low Ring: 290 times for Z minutes), shake 100 g sample for 10 minutes, sieving, then pan, 125 1m, 180 ⁇ m, 250 ⁇ m, 35 Accumulate the weight frequency on the receiving tray and each sieve in the following order: 5 ⁇ m, 500 / zm, 7100tzm, 10000 / m, 1400 czm, 20000 ⁇ m When the opening of the first sieve at which the cumulative weight frequency is 50% or more is a, and when the opening of the sieve one step larger than a Aim is b ⁇ m, a ⁇ m When the integration of the weight frequency up to the sieve is
  • the sieve used should be adjusted appropriately so that the particle size distribution of the measured powder can be accurately estimated.
  • Particle strength Put 20 g of sample in a cylindrical container with an inner diameter of 3 cm x a height of 8 cm and tap it 30 times (Tsutsui Rikagaku Kikai Co., Ltd., TVP 1 type tapping type dense bulk density measuring instrument, tapping Conditions: Cycle 36 times, free fall from the height of 6 Omm for Z minutes), and measure the sample height (initial sample height) at that time. Thereafter, the entire upper end surface of the sample held in the container is pressurized at a speed of 1 OmmZmin using a pressurizing tester, and a load-displacement curve is obtained. Multiply the slope of the linear part when the displacement rate is 5% or less by the initial sample height and divide by the pressed area to obtain the particle strength.
  • the detergent particles were evaluated by the following test methods.
  • Oily marker bleed width is 2 cm or more
  • Oily marker bleed width is 1 cm or more
  • Oily marker bleed width is 0.5 cm or more
  • the base granules of Example 1 were prepared according to the following procedure.
  • the composition (% by weight) of the base granules is as shown in Table 1.
  • Deionized water was added to the mixing tank with stirring blades, and after the water temperature reached 55, sodium chloride (yakisalt: made by Nippon Salt Co., Ltd.), a film formation inhibitor, was added for 15 minutes. Stirred.
  • sodium sulfate anhydrous neutral sodium sulfate: manufactured by Shikoku Chemicals Co., Ltd.
  • sodium sulfite sodium sulfite: manufactured by Mitsui Toatsu Co., Ltd.
  • fluorescent dye Tinopearl CBS-X: manufactured by Ciba Specialty Chemicals
  • Composition 1 A J a ⁇ 7 0 0 q If) 0 Q
  • Example 11 100 parts by weight of the detergent particle group of Example 1, 3 parts by weight of bleach, 2 parts by weight of bleach activator, 1 part by weight of cellulase and 1 part by weight of protease were mixed to give the detergent composition of Example 11 Obtained.
  • Sodium percarbonate Mitsubishi Gas Chemical Co., Ltd.
  • For cellulase use alkaline cellulase described in Japanese Patent Application Laid-Open No. Hei 6-334641, and for protease, use Alkali Reprotease K-16 described in Japanese Patent Application Laid-Open No. 5-254492. did.
  • Such an enzyme was used as enzyme particles by the following method.
  • Cellulase Crystalline aluminoginate (Toyobuilder, manufactured by Tosoh Corporation) 67 parts by weight, sodium polyacrylate aqueous solution (weight average molecular weight: 20,000, manufactured by Kao Corporation) 11 parts by weight, sugar (maltrich)
  • a slurry having a slurry water content of 55% by weight was prepared from 11 parts by weight of MR-25, manufactured by Showa Sangyo Co., Ltd., 11 parts by weight of cellulase, and water.
  • the slurry was sprayed at a spray pressure of 2.5 MPa using a pressurized spray nozzle.
  • Spray drying with a counter flow type spray-drying tower (diameter 3 m, tower height 1 Om) at an air volume of 100 Om for 3 minutes, air temperature of 150 and slurry spray volume of 200 kg Zh was done.
  • a sieve particles having a size of 140 m or more were removed from the obtained particles to obtain enzyme particles having a water content of 4.1% by weight.
  • Protease Crystalline aluminogate (Toyovirda I, Tosoh Corporation) 5 7 parts by weight, sodium polyacrylate aqueous solution (weight average molecular weight 10,000, manufactured by Kao Corporation) 10 parts by weight, sodium sulfate (anhydrous anhydrous sodium sulfate: manufactured by Shikoku Chemicals Co., Ltd.) 4 parts by weight, sugars (maltrich MR) -25, manufactured by Showa Sangyo Co., Ltd.) 4 parts by weight, polyethylene glycol (K-PEG6000, weight average molecular weight 8500, manufactured by Kao Corporation) 5 parts by weight, 20 parts by weight of protease and slurry from water A slurry having a water content of 50% by weight was prepared. Spray drying was performed under the same conditions as for cellulase. Next, particles of 125 / m or less and particles of 710 m or more were removed using a sieve to obtain enzyme particles having a water content of 3.8% by weight.
  • the base granules of Examples 1 to 10 containing the required amount of sodium chloride or sodium bromide as a film formation inhibitor contain such a component. Not have a high oil absorption capacity. As a result, the caking property and stain removal property of the detergent particles are also suppressed. In Examples 1 to 10, since the content of sodium chloride or sodium bromide was an appropriate amount, the cleaning rate was not affected. In Comparative Example 3 in which the amount of sodium chloride was small relative to the amount of the water-soluble polymer, the oil absorption capacity was low, and the effect of sodium chloride blending was not so apparent.
  • Comparative Example 4 in which the amount of sodium chloride was extremely large relative to the amount of the water-soluble polymer, the oil absorbing ability was high, and the caking property and stain removal were suppressed, but the cleaning performance was significantly reduced.
  • the detergent composition of Example 11 had no problem in caking properties and spotting, and had good cleaning performance.
  • detergent particles in Examples and Comparative Examples each contained a mononuclear detergent particle.
  • the base granules and detergent particles of the present invention obtained by blending the film formation inhibitor into the slurry have excellent solubility, sufficient bulk density, and extremely high oil absorption.
  • the present invention described above there are clearly a large number of those in the range of identity. Such variations are not considered to depart from the spirit and scope of the invention, and all such changes that are obvious to those skilled in the art are included within the scope of the following claims.

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Abstract

L'invention porte sur un détergent ayant un poids volumique apparent, et sur une base granulaire destinée à supporter entre 0 et 10 % en poids d'un tensioactif. Cette base granulaire est obtenue, par exemple, par séchage par atomisation d'une bouillie comprenant (A) un polymère soluble dans l'eau, (B) un inhibiteur de formation de film et (C) un sel soluble dans l'eau autre que l'inhibiteur. L'invention porte également sur un procédé de fabrication de la base granulaire ; sur un détergent liquide comprenant 100 parties en poids de la base granulaire et de 1 à 100 parties en poids d'un tensioactif qu'elle supporte, et a un diamètre particulaire moyen compris entre 150 et 750 νm et un poids volumique apparent égal ou supérieur à 500 g/L. L'invention porte en outre sur une composition détergente comprenant le détergent particulaire. La base granulaire et le détergent particulaire ont une excellente solubilité et un poids volumique apparent suffisant, ainsi qu'une capacité d'absorption de l'huile extrêmement élevée. Ils sont donc efficaces pour former une composition aux propriétés détergentes excellentes, aux capacités d'agglutination et d'exsudation du composant réduites.
PCT/JP2000/003813 1999-06-14 2000-06-13 Base granulaire et detergent particulaire Ceased WO2000077158A1 (fr)

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JP2000607257A JP3912986B2 (ja) 1999-06-14 2000-06-13 ベース顆粒群及び洗剤粒子群

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WO2006013982A1 (fr) * 2004-08-06 2006-02-09 Kao Corporation Procédé pour la production de particules de détergents à noyau unique
WO2009142050A1 (fr) 2008-05-23 2009-11-26 花王株式会社 Particule contenant un alkali

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CN1170921C (zh) 2004-10-13
EP1104806A4 (fr) 2004-07-28
EP1104806A1 (fr) 2001-06-06
JP3912986B2 (ja) 2007-05-09
CN1807568A (zh) 2006-07-26
CN100425684C (zh) 2008-10-15
CN1320157A (zh) 2001-10-31

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