KR101793279B1 - Granular detergent composition - Google Patents
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- KR101793279B1 KR101793279B1 KR1020110016892A KR20110016892A KR101793279B1 KR 101793279 B1 KR101793279 B1 KR 101793279B1 KR 1020110016892 A KR1020110016892 A KR 1020110016892A KR 20110016892 A KR20110016892 A KR 20110016892A KR 101793279 B1 KR101793279 B1 KR 101793279B1
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Abstract
(A): a granular material comprising granules composed of particles of sodium hydrogencarbonate or particles of potassium hydrogencarbonate, at least one selected from the components (B): (B) and (C): zeolite and clay mineral Granular detergent composition.
Description
The present invention relates to a granular detergent composition. The present application claims priority based on Japanese Patent Application No. 2010-049617 filed on March 5, 2010, the contents of which are incorporated herein by reference.
The granular detergent composition usually contains a surfactant for the purpose of improving the cleaning performance and imparting various other performances.
In recent years, a detergent having a low surfactant concentration (less than 30% by mass) has become mainstream, because the change in the washing condition and the consciousness about the environmental load increase. At the time of reducing the concentration of the surfactant, maintenance and improvement of the cleaning power are promoted by increasing the amount of the inorganic builder and the like. As the inorganic builder, carbonates of an alkali metal (sodium carbonate, potassium carbonate, etc.) and hydrogen carbonate (sodium hydrogencarbonate, potassium hydrogen carbonate, etc.) are suitably used from the viewpoint of cost and detergency.
Granular detergent compositions, in particular granular detergent compositions used as medical detergents, are prepared by spray drying from aqueous slurries containing surfactants, inorganic builders and the like, and detergents consisting of spray dried particles having pores inside the particles are used come.
Since the spray dried particles have a large volume, the volume used for one cleaning was large. In recent years, a granular detergent composition having a high bulk density, so-called compact detergent, has become mainstream.
Conventionally, as a method for producing a granular detergent composition having a high bulk density, there has been known a method of preparing a slurry containing a surfactant and an inorganic builder, spray-drying the slurry, drying the spray-dried particles obtained by blending the other components with a kneader (For example, Japanese Patent Application Laid-Open No. 2001-3258). The detergent composition thus obtained has a high bulk density.
(Prior art document)
[Patent Literature]
Patent Document 1: JP-A-64-6095
However, the granular detergent composition is required to further reduce the amount of the surfactant. In the invention of Patent Document 1, when sodium carbonate or potassium carbonate is simply increased, the detergent composition tends to solidify. Further, when sodium hydrogen carbonate or potassium hydrogencarbonate was used as the inorganic builder, the detergent composition immediately after preparation did not exhibit solidification, but the solidification progressed with time.
Therefore, the object of the present invention is to provide a granular detergent composition which is hardly solidified even when sodium hydrogencarbonate or potassium hydrogencarbonate is increased.
The granular detergent composition of the present invention is a granular detergent composition comprising (A) component: particles of sodium hydrogencarbonate or potassium hydrogencarbonate, (B) component: binder, (C) component: zeolite and clay (Granulated product) obtained by granulating one kind of the granulated product.
It is preferable that the granulated product is coated with the component (B) and the component (C), and the component (A) is preferably a particle of sodium hydrogencarbonate.
According to the granular detergent composition of the present invention, even when sodium hydrogencarbonate or potassium hydrogencarbonate is increased, the prevention of solidification can be achieved.
(Granular detergent composition)
The granular detergent composition of the present invention is a granular detergent composition comprising (A) component: particles of sodium hydrogencarbonate or particles of potassium hydrogencarbonate, (B) component: binder, (C) component: zeolite and clay mineral And a granulated product obtained by assembling.
The average particle diameter of the granular detergent composition is not particularly limited, but is preferably 200 to 1500 占 퐉, more preferably 250 to 1000 占 퐉. When the average particle diameter is 200 mu m or more, dusting during use is suppressed. On the other hand, when the average particle diameter is 1500 탆 or less, the solubility in water is improved. The average particle diameter of such particles is a value calculated from the particle size distribution by dividing by the mesh according to the test of particles described in Japan Pharmacopoeia.
The average particle size was measured using a nine-step mesh having mesh sizes of 1680 탆, 1410 탆, 1190 탆, 1000 탆, 710 탆, 500 탆, 350 탆, 250 탆, and 149 탆, ). ≪ / RTI > In the classifying operation, a sample having a small eye size and a large eye size were laminated in order on a receiving plate, and a sample of 100 g / sample was placed on the top of a 1680 탆 sieve at the top. Then, the sample was put on a lid, Manufactured by Tosho Corporation, tapping: 156 times / minute, and rolling: 290 times / minute) and vibrated for 10 minutes. Thereafter, the sample remaining on each of the sieve and the receiving tray is collected every sieve, and the mass of the sample is measured. The eye size of the first sieve having the accumulated mass frequency of 50% or more is defined as " a 占 퐉 ", and the eye size of the sieve of one step larger than a 탆 is defined as " b Mu m ". Further, the integrated value of the mass frequency from the receiving plate to the a mu m sieve is defined as "c%", and the mass frequency of the sphere of a mu m is defined as "d%". Then, the average particle size (mass 50%) is determined by the following formula (1), and this is referred to as the average particle size of the sample.
The bulk density of the granular detergent composition is preferably 0.3 kg / dm3 or more, more preferably 0.5 to 1.2 kg / dm3, and still more preferably 0.6 to 1.1 kg / dm3. When the bulk density is 0.3 kg / dm3 or more, the space (storage place) necessary for storing the granular detergent composition can be further reduced. On the other hand, if the bulk density is 1.2 kg / dm 3 or less, the solubility of the granular detergent composition in water becomes good.
The " bulk density (small density) " indicates a value measured in accordance with JIS K3362-1998.
The water content of the granular detergent composition is not particularly limited, but is preferably from 4 to 10 mass%, more preferably from 5 to 9 mass%, still more preferably from 6 to 8 mass% from the viewpoints of solubility and storage stability. In the present specification, the "moisture content" is a value measured by an infrared moisture meter (manufactured by Katsuto Science Laboratory Co., Ltd.) of 5 g and a sample surface temperature of 130 ° C. for 20 minutes.
≪ Aggregates (Granules) >
The granulated product of the present invention is a granulated product of the component (A), the component (B), and the component (C). Examples of the granulated product include mixed particles in which the components (A) to (C) are almost uniformly dispersed, and coated particles in which the component (A) is coated with the component (B) Among them, coated particles are preferable. With the coated particles, it is possible to further improve the effect of preventing solidification of the granular detergent composition during storage of the granular detergent composition.
Examples of the coated particles include a mixture of a component (B) and a component (C) on the surface of the component (A); A first coating layer formed by coating the component (A) with the component (B), and a second coating layer formed by coating the first coating layer with the component (C); A first coating layer in which the component (A) is coated with the component (C), and a second coating layer in which the first coating layer is coated with the component (B). The coated particles preferably cover at least 70% of the surface area thereof, more preferably at least 90%, and even more preferably 100% of the surface area of the coated particles according to the components (B) and (C).
The ratio of the coated area to the surface area of the component (A) (coating ratio) can be determined, for example, by using a microscope (Handi Scope TM manufactured by Nippco Optical Instrument Co., Ltd.), a scanning electron microscope (SUPER SCANSS-550, manufactured by Shimadzu Corporation) and observed by image processing or the like.
The average particle diameter of the granules is not particularly limited, but is, for example, 200 to 1500 占 퐉. The average particle diameter of the granules can be determined in the same manner as the average particle diameter of the granular detergent composition described above.
Component (A)
The component (A) is a particle of sodium hydrogencarbonate or a particle of potassium hydrogencarbonate. Among them, particles of sodium hydrogencarbonate are inexpensive and excellent in solubility, while tend to accelerate the solidification of the granular detergent composition over time. Therefore, the effect of the present invention is remarkable in a granular detergent composition in which the component (A) is made of particles of sodium hydrogencarbonate.
The particle diameter of the component (A) is not particularly limited, but is preferably 10 to 1000 占 퐉, more preferably 50 to 500 占 퐉, for example. When the particle diameter of the component (A) is 10 占 퐉 or more, dusting of the granular detergent composition during the production process is suppressed, and assembly of the granulation process described below is easy. When the particle diameter of the component (A) is 1000 탆 or less, solubility in water is good at the time of use. The average particle diameter of the component (A) can be obtained by the same method as in the granular detergent composition described above. When the particle diameter is less than 149 占 퐉, the value measured by a laser light scattering method (for example, particle size distribution measuring apparatus (LDSA-3400A (17ch), manufactured by the same computer application Co., Ltd.) It is a median diameter.
The blending amount of the component (A) in the granular detergent composition is not particularly limited, but is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, and still more preferably from 5 to 15 mass%. When the blending amount of the component (A) is 1% by mass or more, the function as the inorganic builder is sufficiently exhibited, and when it is 30% by mass or less, deterioration of the washing power is less likely to occur. In addition, the granular detergent composition tends to be solidified as the blending amount of the component (A) increases. Therefore, the effect of the present invention is remarkable in a granular detergent composition having a large amount of component (A).
≪ Component (B) >
The component (B) is a binder. The binder can be determined in consideration of the kind of the component (A), the kind of the component (C), the production conditions and the like. For example, an anionic surfactant or its acid precursor, A water-soluble polymer, and an aqueous solution thereof. Among them, a nonionic surfactant or an aqueous solution thereof is preferable.
Examples of the anionic surfactant or its acid precursor used in the component (B) include a linear alkylbenzene sulfonic acid salt having an alkyl group of 8 to 18 carbon atoms and a higher fatty acid salt having an alkyl group of 8 to 20 carbon atoms; Or one or more alkyls selected from ethylene oxide (hereinafter may be abbreviated as EO), propylene oxide (hereinafter may be abbreviated as PO) and butylene oxide (hereinafter abbreviated as BO) (Or alkenyl) ether sulfate having a straight chain or branched chain alkyl (or alkenyl) group having 10 to 20 carbon atoms in which an average of 0.5 to 10 moles of a phenylene oxide is added.
Examples of the nonionic surfactant used as the component (B) include polyoxyalkylene alkyl (or alkenyl) ether, polyoxyalkylene alkyl (or alkenyl) phenyl ether; Or a fatty acid methyl ester alkoxylate to which EO or PO is added to a fatty acid methyl ester.
As the polyoxyalkylene alkyl (or alkenyl) ether used as the component (B), at least one alkylene oxide selected from EO, PO and BO is preferably added to a saturated or unsaturated alcohol having 8 to 40 carbon atoms Among them, EO and PO are preferably added alone or in admixture thereof. In addition, the average addition mole number of the alkylene oxide is preferably 3 to 35 mols, and more preferably 5 to 30 mols.
As the polyoxyalkylene alkyl (or alkenyl) phenyl ether to be used as the component (B), one having at least one alkylene oxide selected from EO, PO and BO added to an alkylphenol or alkenylphenol having 8 to 12 carbon atoms Among them, EO or PO alone or a mixture thereof is more preferable. In addition, the average addition mole number of alkylene oxide is preferably 5 to 25 moles, more preferably 8 to 20 moles.
As the fatty acid methyl ester alkoxylate to which EO or PO is added to the fatty acid methyl ester used as the component (B), saturated or unsaturated fatty acid methyl esters having an average carbon number of 8 to 40, EO or PO are added singly or in combination . In addition, the average addition mole number of the alkylene oxide is preferably 5 to 30 moles.
(Having a weight average molecular weight of 200 to 20,000), a polyethylene glycol fatty acid ester (the number of carbon atoms of the fatty acid group is 8 to 22, the degree of polymerization of ethylene glycol (average of EO (Number of carbon atoms in the fatty acid group is 8 to 22), polyacrylic acid salt (the weight average molecular weight is in the range of 5 to 25), decaglycerol fatty acid ester (the fatty acid group has 8 to 22 carbon atoms), sorbitan fatty acid ester 1000 to 100000), acrylic acid maleic acid copolymer (weight average molecular weight is 1000 to 100000), and salts thereof.
The blending amount of the component (B) in the granular detergent composition can be determined in consideration of the kinds and blending ratios of the components (A) and (C), and is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass %, More preferably from 0.3 to 3% by mass. When the blending amount of the component (B) in the granular detergent composition is less than 0.1% by mass, the granulation is liable to be insufficient, while when it exceeds 10% by mass, there is a fear that the core product is generated and adhered to the granulating device.
≪ Component (C) >
(C) is at least one member selected from zeolite and clay minerals. As the component (C), a mixture of zeolite and clay mineral is preferable, and a mixture of zeolite and bentnite is more preferable, and a mixture of zeolite A and bentite is more preferable. When a mixture of zeolite and clay mineral is used as the component (C), the mass ratio expressed by clay mineral / zeolite is preferably 0.5 to 2. Within this range, it is possible to further improve the anti-solidifying effect of the granular detergent composition.
The average particle diameter of the component (C) can be determined in consideration of, for example, the average particle diameter of the component (A), and is preferably, for example, 1 to 20 탆. The average particle diameter of the component (C) is a value measured by a laser light scattering method (for example, a particle size distribution measuring apparatus (LDSA-3400A (17 ch), manufactured by the same computer applications Co., Ltd.) It is a median diameter.
As the zeolite of the component (C), any of the A-type zeolite, the P-type zeolite and the X-type zeolite can be used.
As the clay mineral of the component (C), those belonging to the smectite group (group) and having a crystal structure of a dioctahedral laurate type three-layer structure or a trioctahedral laurate type three-layer structure can be preferably used. Such clay minerals have a layered structure with wall cleavage. Clay minerals have the property of preserving a nonionic surfactant in clay mineral by forming chemical adsorption by hydrogen bonding between the crystal layers. Further, the clay mineral has a property of expanding as it stores a nonionic surfactant therein.
Specific examples of such clay minerals include clay minerals having a dioctahedral laurate type three-layer structure, montmorillonite (oil absorption: 50 ml / 100 g, bulk density: 0.3 kg / dm 3), nontronite (Volume of oil: 40 ml / 100 g, bulk density: 0.5 kg / dm 3), beellite (oil absorption: 62 ml / 100 g, bulk density: 0.55 kg / dm 3), pyrophyllite Bulk density: 0.63 kg / dm 3). (Cumulative amount of oil: 73 ml / 100 g, bulk density: 0.15 kg / dm 3), hectorite (oil absorption: 72 ml / 100 g, bulk density: 0.7 kg / d Dm 3), stevensite (oil absorption: 30 ml / 100 g, bulk density: 1.2 kg / dm 3), talc (oil absorption: 70 ml / 100 g, bulk density: 0.1 kg / dm 3). These clay minerals are not particularly limited, although they are both natural ones and artificially hydrothermally synthesized clay minerals. Such clay minerals have a peak derived from the diffusion of the clay layer detected at 10 to 20 angstroms by X-ray analysis and a peak derived from a three-layer structure of clay detected at 4 to 5 angstroms by X-ray analysis , And can be used without limitation. In addition, clay minerals in particular contain a large amount of impurities such as quartz, cristobalite, calcite, and opal feldspar in the case of natural products, and many of these impurities are not suitable for the present invention. Therefore, in the present invention, clay minerals having a purity of at least 60% by mass, more preferably at least 70% by mass, and the best 100% by mass are used. Particularly preferred clay minerals include Na type montmorillonite, Ca type montmorillonite, activated bentonite (Na / Ca type montmorillonite), Na type hectorite, and Ca type hectorite.
The blending amount of the component (C) in the granular detergent composition can be determined in consideration of the kind of the component (A) or the component (B), the average particle size of the component (A), and the like. By mass, more preferably from 1 to 5% by mass, and further preferably from 1 to 3% by mass. When the blending amount of the component (C) in the granular detergent composition is less than 1% by mass, it is difficult to obtain the effect of preventing the granulation deterioration of the granular detergent composition by blending the component (C), and when it exceeds 10% by mass, There is a risk of damage. In addition, within the above range, the component (A) can be satisfactorily coated when the granulated product is formed into coated particles.
≪ Surfactant particles >
The granular detergent composition of the present invention may contain detergent components such as surfactants and builders in addition to the granules. Surfactant particles other than granules (hereinafter sometimes referred to simply as surfactant particles) may be blended . By blending the surfactant particles, the cleaning effect of the granular detergent composition can be improved. The surfactant particles may be incorporated in the granular detergent composition independently from the granules, or may be contained in the granules. It is preferable that the surfactant particles and the granules are independently blended from the viewpoint of improving the effect of preventing granulation deterioration of the granular detergent composition.
The average particle diameter of the surfactant particles is preferably 200 to 1500 占 퐉, more preferably 250 to 1000 占 퐉, and particularly preferably 300 to 700 占 퐉. When the average particle diameter is within the above range, the solubility is excellent. The average particle diameter of the surfactant particles can be measured by the same method as the average particle diameter of the granular detergent composition.
The water content of the surfactant particles is preferably from 4 to 10 mass%, more preferably from 5 to 9 mass%, and still more preferably from 5.5 to 8.5 mass%, from the viewpoint of both solubility and storage stability.
The blending amount of the surfactant particles in the granular detergent composition is preferably 60 mass% or more, more preferably 70 mass% or more, and further preferably 80 mass% or more. If it is less than 60% by mass, there is a possibility that the cleaning effect can not be improved. On the other hand, the blending amount of the surfactant particles in the granular detergent composition is preferably less than 99% by mass. When the amount is 99% by mass or more, the amount of the particles of sodium hydrogencarbonate or potassium hydrogen carbonate is small, so that it is difficult to sufficiently exhibit the function as a builder.
As the surfactant, any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants may be used in addition to the component (B), or a combination of two or more thereof may be used . When the surfactant particles include the following surfactants, the total amount of the surfactants in the surfactant particles is preferably 10 to 90% by mass, and more preferably 15 to 80% by mass.
«Anionic surfactants»
Examples of the anionic surfactant to be incorporated in the surfactant particles include the following.
(1) Methyl, ethyl or propyl ester salts of saturated or unsaturated? -Sulfo fatty acids having 8 to 20 carbon atoms.
(2) Alkali metal salts or alkaline earth metal salts of higher fatty acids having an average carbon number of fatty acids of 10 to 20.
(3) A linear or branched alkylbenzenesulfonic acid salt (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(4) an alkanesulfonic acid salt having 10 to 20 carbon atoms.
(5)? -Olefin sulfonic acid salts (AOS) having 10 to 20 carbon atoms.
(6) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(7) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and propylene oxide (molar ratio: EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether sulfates (AES) having straight or branched chain alkyl (or alkenyl) groups.
(8) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and propylene oxide (molar ratio: EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) phenyl ether sulfates having straight or branched chain alkyl (or alkenyl) groups.
(9) an alkylene oxide having 2 to 4 carbon atoms or an ethylene oxide and propylene oxide (molar ratio: EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Alkyl (or alkenyl) ether carboxylates with straight or branched chain alkyl (or alkenyl) groups.
(10) An alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(11) long-chain monoalkyl, dialkyl or cesium alkyl phosphates having an alkyl group having from 10 to 22 carbon atoms.
(12) A polyoxyethylene monoalkyl, dialkyl or cesium alkyl phosphate having an alkyl group having from 10 to 22 carbon atoms.
These anionic surfactants can be used as a salt with an alkali metal such as sodium or potassium, an amine salt or an ammonium salt. These anionic surfactants may be used alone or in combination of two or more.
«Nonionic surfactant»
Examples of nonionic surfactants to be incorporated into the surfactant particles include the following.
(1) an average of 3 to 30 mol, preferably 5 to 20 mol, more preferably 10 to 18 mol, of an alkylene oxide having 2 to 4 carbon atoms in an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, The added polyoxyalkylene alkyl (or alkenyl) ether. Among them, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are suitable. Examples of the aliphatic alcohol used herein include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether to which ethylene oxide is added to an alkyl (or alkenyl) phenol having carbon atoms (8) to (12).
(3) Fatty acid alkyl ester alkoxylates represented by the following general formula (I) wherein an alkylene oxide is added between ester bonds of long chain fatty acid alkyl esters.
R 1 CO (OA) m OR 2 ... (I)
[In the formula (I), R 1 CO represents a fatty acid residue (residue) having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OA represents an addition unit of an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide; m represents an average addition mole number of alkylene oxide, and is generally a number of 3 to 30, preferably 5 to 20; R 2 represents a lower alkyl (having 1 to 4 carbon atoms) alkyl group having 1 to 3 carbon atoms which may have a substituent]
(4) The polyoxyethylene sorbitan fatty acid ester wherein the number of carbon atoms in the fatty acid group is (8) to (24).
(5) Polyoxyethylene sorbit fatty acid esters such as hexa stearic acid POE sorbitol, tetrastearic acid POE sorbitol, tetra oleic acid POE sorbitol, and monolauric acid POE sorbitol.
(6) Polyoxyethylene fatty acid esters in which the number of carbon atoms in the fatty acid group is (12) to (18).
(7) Polyoxyethylene hardened castor oil.
(8) The glycerin fatty acid ester wherein the number of carbon atoms in the fatty acid group is (14) to (22).
«Cationic surfactant»
Examples of the cationic surfactant to be incorporated in the surfactant particles include the following.
(1) Di long chain alkyl long chain alkyl type quaternary ammonium salt.
(2) Mono long-chain alkyltri-short chain alkyl-type quaternary ammonium salt.
(3) Tree long long chain alkyl mono short chain alkyl type quaternary ammonium salt.
The term "long chain alkyl" refers to an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms. The above "short-chain alkyl" includes a substituent such as a phenyl group, a benzyl group, a hydroxyl group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; Benzyl group; A hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; A polyoxyalkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms is suitable.
«Amphoteric surfactant»
Examples of the amphoteric surfactant include imidazoline amphoteric surfactants and amide betaine amphoteric surfactants. Specifically, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine having an alkyl group of carbon numbers (12) to (18), and lauric acid amide propyl betaine, have.
&Quot; Other components in the surfactant particles "
The surfactant particles may be mixed with a cleansing builder, a fluorescent whitening agent, a polymer, an enzyme stabilizer, an anti-caking agent, a reducing agent, a metal ion capturing agent, a pH adjusting agent and the like.
Examples of the cleaning builder include an inorganic builder and an organic builder.
Examples of the inorganic builder include alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal sulfites such as sodium sulfite and potassium sulfite; (For example, a crystalline alkali metal silicate such as "Na-SKS-6" (δ-Na 2 O 揃 2SiO 2 ) manufactured by Kurarianto Japan Co., Ltd.); Amorphous alkali metal silicates; Sulfates such as sodium sulfate and potassium sulfate; Alkali metal chlorides such as sodium chloride and potassium chloride; Phosphates such as aldophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, and phytic acid salts; A complex of crystalline aluminosilicate, amorphous aluminosilicate, sodium carbonate and amorphous alkali metal silicate (for example, NABION 15 (trade name) manufactured by Rhodia).
Examples of the organic builder include aminocarboxylic acid salts such as nitrilotriacetic acid salt, ethylenediaminetetraacetic acid salt,? -Alanine diacetate salt, aspartic acid diacetate salt, methylglycine diacetate salt and iminodiacetic acid salt; Hydroxyaminocarboxylic acid salts such as serindiacetic acid salt, hydroxyiminodiacetic acid salt, hydroxyethylethylenediamine triacetate and dihydroxyethyl glycine salt; Hydroxycarboxylic acid salts such as hydroxyacetic acid salts, tartaric acid salts, citric acid salts and gluconic acid salts; A cyclocarboxylic acid salt such as a pyromellitic acid salt, a benzopolycarboxylic acid salt, and a cyclopentanetetracarboxylic acid salt; Ether carboxylate such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono or disuccinate; Polyacrylates; Salts of acrylic acid-allyl alcohol copolymers; Salts of acrylic acid-maleic acid copolymer; Salts of polyacetal carboxylic acid such as polyglyoxylic acid; Salts of acrylic acid polymers or copolymers, such as hydroxy acrylic acid polymers, polysaccharides-acrylic acid copolymers; Salts of polymers or copolymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, and aspartic acid; Polysaccharide oxides such as starch, cellulose, amylose, and pectin; Polysaccharide derivatives such as carboxymethylcellulose, and the like.
Among the above-mentioned cleansing builders, the detergency and the contamination dispersibility in the washing liquid are improved. Therefore, it is preferable to use a citrate, an aminocarboxylate, a hydroxyaminocarboxylate, a polyacrylate, a salt of an acrylic acid- It is preferable to use an organic builder such as a salt and an inorganic builder such as zeolite in combination.
The content of the cleansing builder in the surfactant particles is preferably from 10 to 80 mass%, more preferably from 20 to 75 mass%, from the viewpoint of giving sufficient cleaning performance.
&Quot; Method for producing surfactant particles "
The method for producing the surfactant particles can be produced by a known production method. For example, a surfactant or an optional ingredient may be dispersed and dissolved in water, followed by spray drying to obtain powdery surfactant particles. For example, it is also possible to provide a surfactant or an optional component to an apparatus such as a nailing / extrusion, a stirring assembly, a rolling assembly and the like to perform a blade, an assembly, a compression molding and the like, Lt; / RTI > surfactant particles can be obtained.
≪ Other components in granular detergent composition >
The particulate detergent composition of the present invention may be blended with other components (optional components of detergent) in addition to the granules containing the components (A) to (C) described above and the surfactant particles. The detergent optional component may be mixed with the granular detergent composition by powder mixing together with the granules containing the components (A) to (C) and the surfactant particles.
As the detergent-optional components, those conventionally used for detergent compositions for medical use can be cited, and for example, bleaching agents such as percarbonate and perborate; Bleaching activators such as alkanoyloxybenzenesulfonic acid salts; Bleaching activation catalyst; Enzyme assembly; Cationic surfactants; Amphoteric surfactants; Carbonates such as sodium carbonate and calcium carbonate; Silicates such as amorphous silica, calcium silicate and magnesium silicate; Citric acid or its salts; A heavy chain or long chain fatty acid or a salt thereof; Heavy metal chelating agents such as sodium sulfate, sodium chloride, 1-hydroxyethane-1,1-diphosphonic acid / salt; Clay mineral assemblage; Fluorescent brightener; Ultraviolet absorber; Antioxidants; Antimicrobial agents; Ultramarine blue, etc., dyes and the like.
(Method for producing granular detergent composition)
The method for producing the granular detergent composition of the present invention is not particularly limited as long as granules containing the components (A) to (C) can be obtained.
For example, there can be mentioned a method of assembling (B) components while flowing the surfactant particles, (A) component and (C) component in a granulating device (hereinafter, sometimes referred to as batch assembling method). As the batch assembly method, conventionally known methods can be used, and examples thereof include a stirring assembly method, a fluidized bed assembly method, and a motorized assembly method.
The method of adding the component (B) can be determined according to the kind of the component (B) and the like. For example, the addition method by dropping or spraying may be mentioned. In order to add the component (B) by spraying, it is preferable to adjust the viscosity as heating or an aqueous solution so as to be capable of being atomized.
(B) component is preferably heated to room temperature (e.g., 20 캜) to 95 캜. When the temperature is less than room temperature, the component (B) becomes insufficient in fineness, and when it exceeds 95 ° C, the viscosity is excessively lowered, resulting in a higher spraying pressure.
When the component (B) is added as an aqueous solution, the content of the component (B) in the aqueous solution is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 85% . When the content of the component (B) in the aqueous solution is small, the amount of the aqueous solution to be added is increased. With this increase in the amount, the water content of the granular product is increased and the granulating detergent composition may have a deterioration effect.
After the granulation, drying may be performed arbitrarily, or a sizing treatment may be suitably performed to adjust the particle size distribution.
In the batch assembly method, the mass ratio represented by the surfactant particle / (A) / (B) / (C) is preferably 100/1 to 30 / 0.1 to 10/1 to 10, And more preferably from 20 / 0.2 to 5/1 to 5.
For example, the component (A) and the component (C) may be added while the components (A) and (C) (Hereinafter may be referred to as a sole assembly method) is obtained by obtaining a granular product in which the component (A) is coated particles coated with the component (B) and the component (C), and the obtained granular product and the surfactant particles are mixed to obtain a granular detergent composition .
Examples of the single-component granulation method include a method of producing mixed granules or coated granules by an agitation granulation method, a fluidized bed granulation method, or a motorized granulation method. Above all, as the above-mentioned single assembly method, a stirring assembly method is preferable.
The method of adding the component (B) is the same as the above-described batch assembly method.
In the above-mentioned stand-alone assembly method, the mass ratio represented by the component (A) / (B) / (C) is preferably 1 to 30 / 0.1 to 10/1 to 10, more preferably 3 to 20 / 0.2 to 5/1 To 5 is more preferable.
The mixed particles and the coated particles can be divided by adjusting the particle diameter of the particle diameter of the component (A) and the particle diameter of the component (C), the blending ratio of the components (A) to (C) . For example, coated particles can be obtained by assembling the component (A) having an average particle size of 200 to 400 占 퐉 and the component (C) having an average particle size of 10 to 30 占 퐉 by a stirring granulation method, a fluidized bed granulation method, . Alternatively, mixed particles can be obtained by mixing the component (A) having an average particle size of 10 to 30 μm and the component (C) having an average particle size of 10 to 30 μm by a stirring granulation method, a fluidized bed granulation method, or a motorized granulation method.
The discrimination of the mixed particles or the coated particles can be performed by cutting the granule, observing the cut surface with an SEM (scanning electron microscope), and analyzing the element with EDX (energy dispersive X-ray analyzer). When the component (A) is present in the inside of the granule and the surface is covered with the component (C), it can be confirmed that it is a coated particle. When the component (C) .
In addition, it is possible to distinguish the mixed particles or the coated particles by coloring the cut surface of the granule with an oil-soluble red pigment component such as oil red. When the cut surface is colored, the component (B) is colored and the component (A) is not colored. Therefore, when the cut section is observed with a stereoscopic microscope and the interior of the mixture is not colored and the surface is colored, it can be confirmed that it is a coated particle. When the interior of the granule is colored, it can be confirmed that it is a mixed particle.
In the component (A), it is known that a small amount of anhydrous carbonate (sodium carbonate, potassium carbonate) present on the surface forms a double salt with the component (A). When the composite salt is formed, cross-linking between the particles is caused to solidify the granular detergent composition. In addition, in an environment of high temperature and humidity, sodium cesium sulfate or sodium carbonate is produced from sodium hydrogencarbonate, and potassium carbonate is produced from potassium hydrogencarbonate. By using sodium sesquic acid, sodium carbonate or potassium carbonate, the granular detergent composition tends to solidify during storage.
According to the present invention, by assembling the components (A) to (C), the exposed area of the component (A) is reduced and the formation of the double salt is suppressed, and the component (A) Or the generation of potassium carbonate can be suppressed. As a result, solidification of the granular detergent composition can be suppressed. Particularly, when the product is packed in a paper (paper) container, a high bulk density is obtained during transportation, and even if storage is carried out for a long period of time under high temperature and high humidity conditions, The solidification is suppressed.
[Example]
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The compositions in Tables 1 and 2 are expressed as% by mass converted to pure unless otherwise specified, and the compositions in Tables 3 to 5 are the same as those used in Examples 1 to 3, Expressed in mass% of the particles.
(Raw materials used)
The raw materials used in the respective Examples and Comparative Examples are shown below.
≪ Component (A) >
A-1: Sodium hydrogencarbonate, average particle diameter 10 m, manufactured by Kanto Kagaku Co., Ltd.
A-2: eco blast EB-60 (trade name), average particle diameter 0.3 mm, manufactured by Asahi Glass Co., Ltd.
≪ Component (B) >
B-1: A nonionic surfactant having an average of 15 moles of ethylene oxide added, ECOROL26 (trade name, an alcohol having an alkyl group of 12 to 16 carbon atoms, manufactured by ECOGREEN), 90 wt%
≪ Component (C) >
C-1: Bentnite powder, RanDo grade DGA powder (trade name), average particle diameter 20 μm, Na / Ca mass ratio = 2.73,
C-2: Type A zeolite, average particle diameter 3 탆, net fraction 80 mass%, manufactured by Mizusawa Chemical Co.,
<Raw Material of Surfactant Particles>
Sulfo-fatty acid alkyl ester salt-containing paste: (paste composition) C16 / C18 = 8/2, the active ingredient = 63 mass%, the nonionic surfactant = 16 mass% Impurity = 8 mass%, water = 13 mass%
LAS-K is a linear alkyl benzene sulfonic acid (the number of carbon atoms of the straight chain alkyl group is 10 to 14) (Liphon LH-200, trade name, manufactured by Lion Corporation, mg) = 180.0)] was neutralized with a 48% by mass potassium hydroxide solution in a slurry for preparing spray-dried particles. Lion Co., Ltd. (the blending amount in the table indicates the mass% as LAS-K)
Nonionic surfactant: same as B-1 above
AOS-K: potassium alpha -olefin sulfonate having an alkyl group having 14 to 18 carbon atoms, pure; 53% by mass, manufactured by Lion Corporation
A type zeolite: Same as the above C-2
Acrylic acid / maleic acid copolymer salt: Aquaric TL-400, 40% by mass aqueous solution of aqueous solution, Nippon Catalyst Co., Ltd.
· Sodium carbonate: Grain ash, made by Soda Ash Japan Co., Ltd.
Potassium carbonate: Potassium carbonate (powder), manufactured by Asahi Glass Co., Ltd.
Sodium sulfate: Neutral anhydrous sodium A0, manufactured by Shikoku Hoso Co., Ltd.
Sodium silicate: sodium silicate 2, pure; 40 mass%, SiO2 / Na2O ratio (molar ratio) = 2.5, manufactured by Fuji Chemical Co.,
C14 = 0.4% by mass, C16 = 29.2% by mass, C18F0 (stearic acid) = 40% by mass, C18F1 (oleic acid) = 56.8 mass%, C18F2 (linoleic acid) = 1.2 mass%, molecular weight: 289)
Sodium percarbonate: SPC-D, average particle diameter 750 μm, bulk density 0.85 kg / dm 3, manufactured by Mitsubishi Chemical Corporation
Surfactant particles C: MIZULAN (alpha -sulfo fatty acid alkyl ester salt powder), Fatty acids chain carbon number: C16 / C18 = 8/2 (mass ratio), active ingredient = 75 mass%, zeolite 12 mass% Particle diameter 500 mu m, Lion eco-chemical injection
(Evaluation of solidification)
A sheet made of three layers of coated ball paper (basis weight: 350 g / m 2), wax sand paper (basis weight: 30 g / m 2) and kraft pulp paper (basis weight: 70 g / A box having a width of 9.3 cm and a height of 18.5 cm was produced. 1.1 kg of each granular detergent composition of each example was placed in this box and dropped from the height of 10 cm 10 times to increase the contact points of the particles. Thereafter, the box containing the granular detergent composition was stored for 14 days in a constant temperature and humidity room at 45 ° C, 85% RH (Relative humidity) for 8 hours and repeatedly operated at 25 ° C and 65% RH for 16 hours. Thereafter, the box taken out from the constant temperature and humidity chamber was left for 6 hours at 20 DEG C and 60% RH, and the granular detergent composition in the middle was quietly transferred onto a sieve having an eye size of 5 mm. The upper article is gently rocked 10 times to the left and right, and then the mass of the residue on the body and the mass passing through the body is obtained. The solidification rate is calculated from the following formula (2), and the product having a solidification rate of 5% Respectively.
(%) = (Mass of granular detergent composition on the body) 占 (mass of granular detergent composition on the body) + (mass of granular detergent composition passed through the sieve)} x 100 (2)
(Preparation Example 1) Preparation of surfactant particles (A)
According to the composition shown in Table 1, each component except 2 mass% of the zeolite A was put into a reactor equipped with a stirrer and a jacket, and dissolved and dispersed in water (jacket temperature 75 캜) to prepare a slurry having a solid content concentration of 60 mass% .
Subsequently, this slurry was spray-dried using a countercurrent drying tower under the following conditions, and a part (2 mass%) of the A type zeolite was introduced as spray-dried particle coat-coating from the lower part of the spray drying tower, .
· Spray dryer: countercurrent type, tower diameter 2.0m, effective distance 5.0m
· Atomization system: Pressurized nozzle system
· Spraying pressure: 30㎏ / ㎠
· Hot air inlet temperature: 250 ° C
· Hot air outlet temperature: 100 ℃
The spray-dried particles thus obtained had an average particle size of 300 μm, a bulk density of 0.3 kg / dm 3, and a water content of 5% by mass.
73.8 parts by mass of the obtained spray-dried particles, 17 parts by mass of an? -Sulfo fatty acid alkyl ester salt-containing paste, 1.4 parts by mass of a nonionic surfactant and 1.3 parts by mass of water were melt-kneaded with a continuous kneader (KRC-S4 type, manufactured by Kurimoto Ironworks Co., Ltd.) (The number of revolutions of the kneader: 135 rpm; jacket temperature: jacket inlet: 5 DEG C, outlet: 25 DEG C (cooled by jacket cooling)) to prepare dough pieces. The temperature of the resulting dough was 55 占 15 占 폚.
Subsequently, the resultant dough was placed in a Pelitter double (EXD-100 model, manufactured by Fuji Powder Co., Ltd.), extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm and cut 5 m / s), and a pellet-shaped molded body (diameter: about 10 mm, length: 70 mm or less (practically 5 mm or more)).
To 93.5 parts by mass of this pellet-shaped molded article, 6.5 parts by mass of zeolite A as a grinding aid was added and pulverized using Fitzmill (DKA-6 type, manufactured by Hosokawa Micron Co., Ltd.) Particles were obtained. The milling conditions were as follows. The obtained powder had a temperature of 30 占 占 폚, an average particle size of 350 占 퐉, an amount of particles having a particle size of 150 占 퐉 or less of 10% by mass as a whole, and a bulk density of 0.85 kg / dm3.
· Air temperature: 15 ± 3 ℃
· Air volume (ratio of air / solid): 2.8 ± 0.25㎥ / kg
· Screen diameter: 6 mm, 4 mm, 2 mm
· Crusher rotation speed: 100% = 4700 rpm (peripheral speed: about 60 m / s)
· Processing speed: 230 kg / hr
(Preparation Example 2) Preparation of surfactant particles (B)
According to the composition shown in Table 2, each component except 2 mass% of the zeolite A was put into a reactor equipped with a stirrer and a jacket, and dissolved and dispersed in water (jacket temperature 75 캜) to prepare a slurry having a solid content concentration of 60 mass% .
Subsequently, this slurry was spray-dried using a countercurrent drying tower under the following conditions, and a part (2 mass%) of the A type zeolite was introduced as spray-dried particle coat-coating from the bottom of the spray drying tower, .
· Spray dryer: countercurrent type, top diameter 2.0m, effective length 5.0m
· Atomization system: Pressurized nozzle system
· Spraying pressure: 30㎏ / ㎠
· Hot air inlet temperature: 250 ° C
· Hot air outlet temperature: 100 ℃
The obtained spray-dried particles had an average particle size of 280 μm, a bulk density of 0.28 kg / dm 3, and a water content of 5% by mass.
85.8 parts by mass of the obtained spray dried particles, 6.6 parts by mass of a nonionic surfactant and 0.9 parts by mass of water were kneaded with a continuous kneader (KRC-S4 type, manufactured by Kurimoto Ironworks Co., Ltd.) (kneader rotation speed: 135 rpm; jacket temperature: jacket inlet 5 ° C and outlet 25 ° C (cooled by passing through a jacket)) to prepare a dough product. The temperature of the resulting dough was 55 占 15 占 폚.
Subsequently, the resultant dough was placed in a Pelitter double (EXD-100 model, manufactured by Fuji Powder Co., Ltd.), extruded from a die having a hole diameter of 10 mm and a thickness of 10 mm and cut 5 m / s), a pellet-shaped formed body (diameter of about 10 mm, length of not more than 70 mm (practically not less than 5 mm)) was obtained.
6.7 parts by mass of zeolite A as a grinding assistant was added to 93.3 parts by mass of the pellet-shaped molded product, and the mixture was pulverized using Fitz mill (DKA-6 type, manufactured by Hosokawa Micron Co., Ltd.) Particles were obtained. The milling conditions were as follows. The obtained powder had a temperature of 30 占 占 폚, an average particle size of 400 占 퐉, an amount of particles having a particle size of 150 占 퐉 or less of 8% by mass as a whole, and a bulk density of 0.82 kg / dm3.
· Air temperature: 15 ± 3 ℃
· Amount of blowing air (ratio of air / air ratio): 2.8 ± 0.25㎥ / kg
· Screen diameter: 6 mm, 4 mm, 2 mm
· Crusher rotation speed: 100% = 4700 rpm (peripheral speed: about 60 m / s)
· Processing speed: 230 kg / hr
(Examples 1 to 6, 13 to 14 and Comparative Examples 1 to 3)
According to the composition shown in Table 3, a granular detergent composition was prepared by the following batch assembly method. For the preparation of the granular detergent composition, a vessel rotary type cylindrical mixer was used. The container rotary type cylindrical mixer was a container having a diameter of 0.7 m, a length of 1.4 m, an inclination angle of 3.0 °, a height of 0.15 m at the outlet opening (weir), a bladed wing of 0.1 m in height and 1.4 m in length, It is a specification attached with 4 pieces per °. In addition, the number of revolutions of the inner mixing blades was adjusted so that the Frud factor (Fr) = 0.2. The frust number Fr in the container rotary type cylindrical mixer can be expressed by the following equation (3).
Fr = V 2 / (R x g) ... (3)
(3) where V represents the peripheral velocity (m / s) of the outermost periphery in the vessel rotating type cylindrical mixer; R represents the radius (m) from the center of rotation of the outermost periphery in the vessel rotating cylindrical mixer; g represents the gravitational acceleration (m / s 2 )
First, the surfactant particles, the component (A) and the component (C) were charged into a container rotating cylindrical mixer of the above specification at a rate of 15 kg / min. Subsequently, the group of particles fluidized by rotating the vessel was sprayed with the component (B) previously adjusted to 75 캜. The spraying of the component (B) was carried out by using a park air nozzle (K008, manufactured by IKEUCHI CORPORATION) with a spraying pressure of 0.30 to 0.50 MPa and a predetermined flow rate and a droplet diameter (150 mu m). The spraying of the component (B) was carried out within a range of 2/3 from the top in the region where the particle group spread along the rotational direction. When component (B) was sprayed, the average temperature of the group of particles was 35 占 폚. The granular detergent composition thus obtained was evaluated for solidifying properties, and the results are shown in Table 3. [
(Examples 7 to 11 and Comparative Example 4)
According to the composition shown in Table 4, the granulated product was obtained by the following single granulation method, and the obtained granulated product and the surfactant particle (A) were mixed to prepare a granular detergent composition.
First, the component (A) was charged into a Redgee mixer (M20 type, Matsubo Co., Ltd.) having a plow-blade shovel and a clearance of 5 mm between the shovel and the wall surface (charging rate: 30% by volume) Stirring was started at 200 rpm of the main shaft (chopper stopped). Ten minutes after the start of the stirring, the component (B) was added between 30 seconds, and then the component (C) was added and assembled. Thus, a granulated product as a coated particle was obtained.
Then, according to the composition shown in Table 4, the resulting granules and the surfactant particles (A) were mixed in a container rotating cylindrical mixer to obtain a granular detergent composition. The granular detergent composition thus obtained was evaluated for solidification properties, and the results are shown in Table 4. < tb > < TABLE >
With regard to the assembled product in each example, the granulated product is cut, SEM observation of the cut surface thereof, and elemental analysis in EDX show that the surface of component (A) is covered with component (C) Respectively.
In addition, in each example, the cut surfaces of the assembled mixture were colored with oil red and observed under a stereomicroscope, whereby the granules of Examples 7 to 11 exhibited a state in which the surface of component (A) was covered with component (B) Respectively.
(Example 12)
A granulated product was obtained in the same manner as in Example 8 except that the component (A) was A-1 and the chopper was rotated at 1000 rpm.
Subsequently, according to the composition of Table 4, the obtained granules and the surfactant particles (A) were mixed in a container rotating cylindrical mixer to obtain a granular detergent composition. The granular detergent composition thus obtained was evaluated for solidification properties, and the results are shown in Table 4. < tb > < TABLE >
The obtained granules were subjected to SEM observation of cut surfaces, elemental analysis in EDX, and stereomicroscopic observation in the same manner as in Examples 7 to 11 to obtain mixed particles substantially uniformly dispersed in the components (A) to (C) Respectively.
(Example 13)
A granular detergent composition was obtained by the same batch assembling method as in Example 1 except that the surfactant particle (A) was used as the surfactant particle (B) and the composition in Table 5 was used. The resulting granular detergent composition was evaluated for solidification properties, and the results thereof are shown in Table 5. < tb > < TABLE >
(Example 14)
A granular detergent composition was obtained by the same batch assembling method as in Example 1 except that the surfactant particles (A) were surfactant particles (B and C) and the composition of Table 5 was used. The resulting granular detergent composition was evaluated for solidification properties, and the results thereof are shown in Table 5. < tb > < TABLE >
As shown in Tables 3 and 5, in each of Examples 1 to 6 and 13 to 14 to which the present invention was applied, the degree of solidification was 4.8% or less. Examples 2 to 4 in which zeolite (C-1) and bentonite (C-2) were used in combination as component (C) were higher than those of Examples 5 to 6 using either C-1 or C-2. The recurrence rate was low.
On the other hand, in Comparative Examples 1 to 3 in which neither the component (B) nor the component (C) was added, the solidification rate was 5.4% or more.
As shown in Table 4, in all of Examples 7 to 12 to which the present invention was applied, the solidification ratio was 2.7% or less. In addition, in Examples 7 to 11, the surface of the component (A) is completely covered with the component (B) and the component (C) which are mixed together. Examples 7 to 9 and 12, in which C-1 and C-2 were used in combination as the component (C), were lower in hardening rate than Examples 10 to 11 using either C-1 or C-2.
In Example 12 in which the granulated particles were mixed particles, in Comparative Examples 3 and 8 having the same composition of the component (B) and the component (C), the higher rate But it was higher than that of Example 8 as the coated particles.
On the other hand, in Comparative Example 4 in which component (B) was not blended, the degree of solidification was 5.2%.
Claims (4)
Wherein the blending amount of the component (A) in the 100 mass% of the granules is 80 mass% or more,
Wherein the amount of the component (A) is 5 to 30 mass%, the amount of the component (B) is 0.1 to 5 mass%, the amount of the component (C) is 1 to 5 mass% . ≪ / RTI >
The granular detergent composition according to any one of claims 1 to 3, wherein the granules are coated with the component (A) and the component (B).
Wherein the component (A) is a particle of sodium hydrogencarbonate.
Wherein the component (C) is a clay mineral and a zeolite, and the mass ratio of the clay mineral / zeolite is 0.5 to 2.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001152198A (en) | 1999-11-25 | 2001-06-05 | Kao Corp | High bulk density detergent |
| JP2001172691A (en) | 1999-12-15 | 2001-06-26 | Lion Corp | Granular nonionic detergent composition |
| JP2008050411A (en) | 2006-08-22 | 2008-03-06 | Diversey Ip Internatl Bv | Granular detergent composition for clothing, and method for producing the composition, and method for using the composition |
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| JPS5921360B2 (en) * | 1976-07-31 | 1984-05-19 | ライオン株式会社 | Modification method of granular detergent |
| JPS6320397A (en) * | 1986-07-14 | 1988-01-28 | 日本パ−オキサイド株式会社 | Granule based on sodium hydrogen carbonate |
| JP3183737B2 (en) * | 1992-12-01 | 2001-07-09 | ライオン株式会社 | Method for producing high bulk density detergent composition |
| JPH10180081A (en) * | 1996-12-25 | 1998-07-07 | Asahi Glass Co Ltd | Production of alkali metal hydrogencarbonate granule |
| JP5466359B2 (en) * | 2007-10-29 | 2014-04-09 | 花王株式会社 | Detergent particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001152198A (en) | 1999-11-25 | 2001-06-05 | Kao Corp | High bulk density detergent |
| JP2001172691A (en) | 1999-12-15 | 2001-06-26 | Lion Corp | Granular nonionic detergent composition |
| JP2008050411A (en) | 2006-08-22 | 2008-03-06 | Diversey Ip Internatl Bv | Granular detergent composition for clothing, and method for producing the composition, and method for using the composition |
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