WO2012043859A1 - Particules contenant chacune de l'acide (sel) aminocarboxylique, et composition de détergent granulaire - Google Patents

Particules contenant chacune de l'acide (sel) aminocarboxylique, et composition de détergent granulaire Download PDF

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Publication number
WO2012043859A1
WO2012043859A1 PCT/JP2011/072806 JP2011072806W WO2012043859A1 WO 2012043859 A1 WO2012043859 A1 WO 2012043859A1 JP 2011072806 W JP2011072806 W JP 2011072806W WO 2012043859 A1 WO2012043859 A1 WO 2012043859A1
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WIPO (PCT)
Prior art keywords
salt
mass
aminocarboxylic acid
containing particles
component
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PCT/JP2011/072806
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English (en)
Japanese (ja)
Inventor
佑樹 西山
孝太郎 松井
達生 永野
大佑 小林
Original Assignee
ライオン株式会社
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Priority claimed from JP2010224126A external-priority patent/JP2013253118A/ja
Priority claimed from JP2011049624A external-priority patent/JP2013253120A/ja
Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to KR1020137006841A priority Critical patent/KR20130115226A/ko
Publication of WO2012043859A1 publication Critical patent/WO2012043859A1/fr

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • 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
    • 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

Definitions

  • detergent compositions for clothing and the like are required to have a sterilizing effect in addition to a cleaning effect.
  • a composition in which an oxidation catalyst containing a chelating agent having a coordination position of 5 or less and a metal compound and a surfactant are blended has been proposed.
  • the chelating agent aminocarboxylates such as methylglycine diacetate, iminodisuccinate, and hydroxyiminodisuccinate are used (see Patent Document 1).
  • aminocarboxylate itself has a hygroscopic property, it tends to be agglomerated with other detergent raw materials when blended into a granular detergent composition. Therefore, the granular detergent composition containing an aminocarboxylate has a problem that solidification is likely to occur (so-called caking is likely to occur).
  • At least one polyethylene glycol or at least one nonionic surfactant or a mixture thereof, or methyl alcohol glycine diacetate (x) as an aminocarboxylate salt, or polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene glycol And a mixed powder or mixed granule in which a polymer (y) selected from the group consisting of derivatives thereof is used in combination has been proposed (see Patent Document 2).
  • the conventional granulated product of the oxidation catalyst has insufficient solubility in water (particularly solubility in water at a low temperature of about 10 ° C.).
  • a zinc compound (a) and an aminocarboxylic acid or a salt thereof (b) are contained, and the molar ratio represented by (a) / (b) is 0.5-6.
  • Aminocarboxylic acid (salt) -containing particles are contained, and the molar ratio represented by (a) / (b) is 0.5-6.
  • Aminocarboxylic acid (salt) -containing particles are contained, and the molar ratio represented by (a) / (b) is 0.5-6.
  • (2) The aminocarboxylic acid (salt) -containing particles according to (1) above, wherein the zinc compound is a sulfate.
  • aminocarboxylic acid (salt) -containing particles and a granular detergent composition that hardly cause solidification.
  • aminocarboxylic acid (salt) -containing particles means particles containing one or both of aminocarboxylic acid and aminocarboxylic acid salt.
  • melting point refers to a value measured by the melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical products”.
  • the moisture absorption rate of the aminocarboxylic acid (salt) -containing particles is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less. When the moisture absorption is less than or equal to the upper limit, solidification is less likely to occur when blended in a granular detergent composition or the like.
  • the “moisture absorption rate” refers to a value measured by the following procedure. First, the sample is spread on a glass petri dish (inner diameter: 85 mm) so as to have a thickness of 5 mm, and is placed in a thermostat set at a temperature of 45 ° C. and a relative humidity of 80%. Next, at every elapsed time (every 60 minutes), the mass of the glass petri dish with the sample spread is measured in the thermostat and the change with time is recorded. And a moisture absorption rate (mass%) is calculated
  • “sample collection amount”, “sample preparation amount”, and “measurement value” are as follows.
  • the average particle size of the aminocarboxylic acid (salt) -containing particles is usually 150 to 2000 ⁇ m, preferably 200 to 1200 ⁇ m, more preferably 50 to 500 ⁇ m, still more preferably 70 to 350 ⁇ m, and more preferably 80 to 300 ⁇ m. Particularly preferred.
  • the average particle size is equal to or greater than the lower limit, dusting is suppressed when mixing with other detergent raw materials.
  • the solubility to water improves that it is below an upper limit.
  • the “average particle diameter” is measured as a volume-based median diameter by a laser light scattering method using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.).
  • the measurement object is classified using a 9-stage sieve having a mesh opening of 1680 ⁇ m, 1410 ⁇ m, 1190 ⁇ m, 1000 ⁇ m, 710 ⁇ m, 500 ⁇ m, 350 ⁇ m, 250 ⁇ m, and 149 ⁇ m and a tray.
  • the 9-stage sieve is stacked above the pan so that the openings gradually increase, and a sample of 100 g / time is placed on the top of the sieve having the top opening of 1680 ⁇ m.
  • the water content of the aminocarboxylic acid (salt) -containing particles is preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 0.3 to 4% by mass.
  • the moisture content indicates a value measured using an infrared moisture meter (product name: Kett moisture meter, manufactured by Kett Scientific Laboratory).
  • component (a) As the zinc compound (a) (hereinafter also referred to as “component (a)”), since granular detergent compositions and the like are usually used by being put into water, those which are easily dissolved in water are preferable. Includes a water-soluble salt of zinc. Examples of the water-soluble salts include nitrates, sulfates, chlorides, acetates, perchlorates, cyanides, ammonium chlorides, tartrates, gluconates, and hydrates thereof. Can do.
  • zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, zinc chloride ammonium, zinc tartrate, zinc perchlorate, zinc gluconate, etc. are preferable.
  • zinc sulfate is more preferable, and anhydrous zinc sulfate, zinc sulfate monohydrate, and zinc sulfate heptahydrate are particularly preferable.
  • the dehydration / transition temperature of the component (a) exists within the range of temperature conditions during kneading or granulation when producing aminocarboxylic acid (salt) -containing particles. Then, the hardness of the aminocarboxylic acid (salt) -containing particles changes abruptly, making it difficult to obtain a uniform (homogeneous) granulated product. Therefore, as the component (a), the dehydration / transition temperature is preferably outside the range of temperature conditions during kneading or granulation, the low temperature side is 55 ° C. or lower, and the high temperature side is 70 ° C. or higher. More preferably, the low temperature side is 43 to 50 ° C., and the high temperature side is 73 to 280 ° C.
  • Dehydration / transition temperature of component (a) indicates a value observed by transition point measurement by differential scanning calorimetry (DSC).
  • the dehydration / transition temperature is determined by setting the temperature at the peak top of the endothermic peak obtained by DSC.
  • any commercially available heat flow rate type or heat guarantee type may be used.
  • ⁇ -alumina is used as a reference, and a polyhydrate of zinc compound (a) is arranged on the sample side. Measurement temperature range: 0 to 100 ° C., temperature increase rate: 2 ° C./min.
  • the dehydration / transition temperature is the peak top temperature of an endothermic peak of 10 mJ / min or more observed at 20 ° C. or more.
  • the endothermic peak observed on the highest temperature side of 100 ° C. or lower is defined as the dehydration / transition temperature.
  • the dehydration / transition temperature is calculated by changing the measurement temperature range to 0 to 300 ° C. and performing the same measurement.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the content of the component (a) is preferably 10 to 80% by mass, more preferably 20 to 55% by mass in terms of anhydride.
  • the content of the component (a) is equal to or higher than the lower limit, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is further reduced and solidification hardly occurs.
  • it is at most the upper limit value it becomes easy to achieve a blending balance with an aminocarboxylic acid or a salt thereof (b) described later, and the effect of the present invention is improved.
  • the aminocarboxylic acid or its salt (b) includes ethylenediaminetetraacetic acid or its salt, ⁇ -alanine diacetic acid or its salt, the following general formula (b1) or (b2 ) And the like.
  • X 11 to X 14 each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal or a cationic ammonium
  • R represents a hydrogen atom or a hydroxyl group
  • n 1 represents 0 or 1 Represents an integer.
  • A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group or a hydrogen atom
  • X 21 to X 23 each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal or a cation.
  • N 2 represents an integer of 0 to 5.
  • examples of the alkali metal in X 11 to X 14 include sodium and potassium.
  • examples of the alkaline earth metal in X 11 to X 14 include calcium and magnesium. Note that when at least one of X 11 to X 14 is an alkaline earth metal, it corresponds to 1/2 atom.
  • X 11 is calcium
  • —COOX 11 becomes “—COO ⁇ 1/2 (Ca)”.
  • Examples of the cationic ammonium in X 11 to X 14 include alkanolamines such as monoethanolamine and diethanolamine, and specific examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. .
  • the alkanol group preferably has 1 to 3 carbon atoms.
  • X 11 to X 14 are preferably alkali metals.
  • X 11 to X 14 may be the same or different from each other.
  • R may be a hydrogen atom or a hydroxyl group.
  • n 1 is preferably 1.
  • the compound represented by the formula (b1) include iminodisuccinic acid, 3-hydroxy-2,2′-iminodisuccinic acid or a salt thereof, and iminodisuccinic acid or a salt thereof is preferable.
  • the salt include alkali metal salts such as sodium salt and potassium salt, alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt and potassium salt are particularly preferable.
  • the alkyl group in A may be either linear or branched.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 18 carbon atoms.
  • a part of the hydrogen atoms may be substituted with a substituent.
  • the substituent include a sulfo group (—SO 3 H), an amino group (—NH 2 ), a hydroxyl group, and a nitro group (—NO 2 ).
  • A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxyl group, and a hydrogen atom, and a hydrogen atom is particularly preferable.
  • the alkali metal, alkaline earth metal and cationic ammonium in X 21 to X 23 are the same as the alkali metal, alkaline earth metal and cationic ammonium in X 11 to X 14 respectively. Things. Among these, X 21 to X 23 are preferably alkali metals. X 21 to X 23 may be the same or different from each other.
  • n 2 is preferably an integer of 0 to 2, and 1 is particularly preferable.
  • the compound represented by the formula (b2) include, for example, nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethylglutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid or salts thereof.
  • nitrilotriacetic acid, methylglycine diacetic acid or a salt thereof is preferable, and methylglycine diacetic acid or a salt thereof is particularly preferable.
  • the salt include alkali metal salts such as sodium salt and potassium salt, alkanolamine salts such as monoethanolamine salt and diethanolamine salt, and sodium salt and potassium salt are particularly preferable.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the compound represented by the general formula (b1) or (b2) is preferable, and the compound represented by the general formula (b2) is more preferable.
  • the content of the component (b) is preferably 10 to 80% by mass, and more preferably 35 to 75% by mass.
  • the blending effect of the component (b) (the effect of forming a chelate compound by coordination with metal ions) is more easily obtained.
  • it is at most the upper limit value it becomes easy to achieve a blending balance with the component (a), and the effect of the present invention is improved.
  • the component (b) since the hygroscopicity of the aminocarboxylic acid (salt) -containing particles can be kept lower, it is preferable to use those having an average neutralization degree of 80% or more, and 90% or more. It is more preferable to use a thing, and it is especially preferable to use what is 100%.
  • degree of neutralization means the molar fraction of the neutralized carboxylic acid relative to the total carboxylic acid in the molecule. It is 1.0 when all carboxylic acids in the molecule are neutralized, and 0 when all are in acid form (—COOH).
  • “(a) / (b)” indicates the content ratio (molar ratio) of the component (a) to the component (b).
  • the mixing ratio of the component (a) and the component (b) in the aminocarboxylic acid (salt) -containing particles is such that the molar ratio represented by (a) / (b) is 0.5 to 6, Is preferably ⁇ 5.8, more preferably 0.5 ⁇ 5.5.
  • the molar ratio represented by (a) / (b) is equal to or greater than the lower limit, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is reduced, and solidification hardly occurs.
  • the concentration of the component (b) is sufficiently secured.
  • the aminocarboxylic acid (salt) -containing particles may contain other components as needed in addition to the components (a) and (b).
  • Other components include bases such as sodium bicarbonate, sodium hydroxide and potassium hydroxide; crystalline aluminosilicates (A-type zeolite, P-type zeolite, X-type zeolite, etc.), amorphous aluminosilicates, clay minerals ( Coating components such as talc and montmorillonite); binders such as polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol.
  • the content of the base is preferably 0.001 to 10% by mass, more preferably 0.002 to 1% by mass, and further preferably 0.003 to 0.1% by mass.
  • the content of the base is at least the lower limit value
  • the component (b) tends to change to a structure that hardly absorbs moisture.
  • it is below the upper limit, it becomes easy to balance with other blending components, and the concentration of the component (b) is sufficiently secured.
  • the content of the coating component is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.
  • the aminocarboxylic acid (salt) -containing particles are unlikely to be agglomerated and the fluidity is improved.
  • it is below the upper limit it becomes easy to balance with other blending components, and the concentration of the component (b) is sufficiently secured.
  • an organic binder (c) is preferable.
  • the organic binder (c) has a function as a binder, is a solid at room temperature, and is preferably a water-soluble organic compound that melts when heated.
  • a component (c) an organic compound having a melting point of 25 to 100 ° C. is more preferable, an organic compound having a melting point of 25 to 80 ° C. is more preferable, an organic compound having a melting point of 40 to 80 ° C. is particularly preferable, Is most preferably an organic compound having a temperature of 45 to 75 ° C.
  • the component (c) does not include the component (d), the component (e), the component (a), and the component (b) in the present invention.
  • component (c) examples include polyethylene glycol, polypropylene glycol, block polymers of ethylene oxide and propylene oxide, and nonionic surfactants having a melting point of 45 ° C. or higher.
  • polyethylene glycol is preferable, polyethylene glycol having an average molecular weight of 400 to 30000 is more preferable, polyethylene glycol having an average molecular weight of 1000 to 20000 is further preferable, and polyethylene glycol having an average molecular weight of 4000 to 20000 is particularly preferable.
  • “average molecular weight” indicates a value in terms of polyethylene glycol conversion by gel permeation chromatography.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • the content of the binder (c) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 8 to 20% by mass.
  • the content of the binder (c) is 3% by mass or more, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles can be further reduced.
  • fine powder is less likely to be generated during pulverization.
  • the content of the binder (c) is 30% by mass or less, the blending balance of the component (a) and the component (b) is particularly well maintained, and the solubility in water is improved.
  • the aminocarboxylic acid (salt) -containing particles may also contain an anionic surfactant (d) and a nonionic surfactant (e) having a melting point of less than 45 ° C.
  • anionic surfactant (d) examples include linear or branched alkyl (average carbon number 8 to 18) benzene sulfonate, long chain alkyl (average carbon number 10 to 20) sulfonate, long Chain olefin (average carbon number 10-20) sulfonate, long chain monoalkyl (average carbon number 10-20) sulfate ester, polyoxyethylene (average degree of polymerization 1-10) long chain alkyl (average carbon number 10-10) 20) Ether sulfate ester salt, polyoxyethylene (average degree of polymerization 3 to 30) alkyl (average carbon number 6 to 12) phenyl ether sulfate ester salt, ⁇ -sulfo fatty acid ester salt (average carbon number 12 to 20); long chain Monoalkyl, dialkyl or sesquialkyl phosphates; polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates are used
  • the above “long chain” may be linear or branched, and may have a saturated or unsaturated bond.
  • the salt form in the component (d) include alkali metal salts such as sodium and potassium, amine salts, ammonium salts and the like, and alkali metal salts are preferable.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type.
  • the content of the component (d) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and particularly preferably 5 to 15% by mass.
  • the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved.
  • the content of the component (d) is 20% by mass or less, the blending balance of the component (a) and the component (b) is kept good, and the bleaching effect is improved.
  • Nonionic surfactant (e) having a melting point of less than 45 ° C. When the aminocarboxylic acid (salt) -containing particles of the present invention are produced, the component (e) is easily melted by heating and sufficiently mixed with other raw materials. Thereby, kneading
  • the melting point of the component (e) is preferably 43 ° C. or less, more preferably 15 to 41 ° C.
  • Examples of the component (e) include polyethylene glycol addition type nonionic surfactants and polyethylene glycol-polypropylene glycol addition type nonionic surfactants.
  • polyethylene glycol addition type nonionic surfactants are exemplified.
  • 3 to 80 moles (preferably 5 to 50 moles) of ethylene glycol or ethylene oxide are added per 1 mole of aliphatic alcohol having 8 to 20 carbon atoms (preferably 10 to 18 carbon atoms), and the melting point is less than 45 ° C.
  • the component (e) include polyoxyethylene alkyl ethers (preferably having 5 to 15 moles of ethylene glycol or ethylene oxide added thereto and alkyl having 12 to 18 carbon atoms).
  • the component (e) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (e) is preferably 1 to 9% by mass, more preferably 2 to 9% by mass, and further preferably 3 to 8% by mass.
  • the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved.
  • the aminocarboxylic acid (salt) -containing particles when the content of the component (e) is 9% by mass or less, when the aminocarboxylic acid (salt) -containing particles are produced, for example, the extrusion pressure at the time of extrusion from the extruder does not become too low, and the extrudate is maintained. The formability becomes better. And the aminocarboxylic acid (salt) containing particle
  • the aminocarboxylic acid (salt) -containing particles of the present invention it is preferable to blend a polyvalent carboxylic acid as a solubility improver, particularly under the condition that the laundry washing solution exhibits alkalinity.
  • the polyvalent carboxylic acid include succinic acid and citric acid.
  • the content of the polyvalent carboxylic acid is preferably 5% by mass or less, and more preferably 3% by mass or less. If it is 5 mass% or less, it will become easy to take especially the compounding balance with (a) component.
  • the lower limit value is preferably 1% by mass or more because the effect of improving solubility is easily obtained.
  • cationic surfactants amphoteric surfactants, aluminosilicate salts such as zeolite as grinding aids; carbonates such as sodium carbonate and calcium carbonate, amorphous silica; calcium silicate, magnesium silicate, etc.
  • bleaching activators such as organic peracid precursors, 1-hydroxyethane-1,1-diphosphone
  • Examples include heavy metal chelating agents other than the component (b) such as acids or salts thereof, clay minerals, fluorescent brighteners, ultraviolet absorbers, antioxidants, antibacterial agents, and pigments.
  • Specific examples of the medium chain or long chain fatty acid include fatty acids having 8 to 10 carbon atoms in the acyl group as the medium chain fatty acid, and long chain fatty acids having 12 to 18 carbon atoms in the acyl group. Fatty acids are mentioned.
  • the “medium chain or long chain” may be linear or branched, and may have a saturated or unsaturated bond.
  • the content of the medium-chain or long-chain fatty acid is preferably 0.1 to 5% by mass, and more preferably 0.5 to 4% by mass.
  • Organic peracid precursors react with hydrogen peroxide (oxygen-based bleaching component) generated from peroxides such as sodium percarbonate to produce organic peracids with strong bleaching power, thereby bleaching clothing, etc. It is effective.
  • the organic peracid precursor is an unstable component that is likely to deteriorate over time, such as when the oxidation promoting effect is reduced due to the interaction with other components when blended in a granular detergent or a bleaching agent. For this reason, since it is difficult to obtain the effect of blending, it is preferable that the aminocarboxylic acid (salt) -containing particles of the present invention do not contain an organic peracid precursor.
  • flavor, etc. can be mix
  • aminocarboxylic acid (salt) -containing particles zinc compound (a), aminocarboxylic acid or salt thereof (b), organic binder (c), anionic surfactant (d), and melting point of less than 45 ° C.
  • Aminocarboxylic acid (salt) -containing particles containing a nonionic surfactant (e) are preferable.
  • the content of the zinc compound (a) is 10 to 80% by mass, and the aminocarboxylic acid or The content of the salt (b) is more preferably 10 to 80% by mass.
  • the mixing ratio of the anionic surfactant (d) and the zinc compound (a) is preferably 0.05 to 0.44 in terms of mass ratio represented by (d) / (a), and is 0.10. More preferably, it is ⁇ 0.40.
  • (d) / (a) is equal to or higher than the lower limit, the effect of suppressing moisture absorption is easily obtained, and when (d) / (a) is equal to or lower than the upper limit, solubility in water is improved.
  • the blending ratio of the nonionic surfactant (e) having a melting point of less than 45 ° C. and the zinc compound (a) is 0.05 to 0.36 in mass ratio represented by (e) / (a). It is preferably 0.06 to 0.30.
  • (e) / (a) is at least the lower limit, solubility in water is improved, and when (e) / (a) is at most the upper limit, aminocarboxylic acid (salt) -containing particles are produced. In this case, the extrusion pressure at the time of extrusion does not become too low, the shape retention is improved, and the solidification of the granulated product is easily suppressed.
  • the mixing ratio of the aminocarboxylic acid or its salt (b) and the zinc compound (a) is preferably 0.44 to 2.0 in terms of mass ratio represented by (b) / (a). More preferably, it is 48 to 1.9.
  • (b) / (a) is at least the lower limit, when producing aminocarboxylic acid (salt) -containing particles, the extrusion pressure during extrusion does not become too high, and (b) / (a) is the upper limit. If it is less than the value, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is easily suppressed.
  • the blending ratio of the organic binder (c), the anionic surfactant (d) and the nonionic surfactant (e) having a melting point of less than 45 ° C. is (c) / [(d) + (e)] Is preferably 0.7 to 2.0, and more preferably 0.8 to 1.5.
  • (c) / [(d) + (e)] is within the above range, the shape retention of the aminocarboxylic acid (salt) -containing particles is improved while maintaining good solubility in water. Hygroscopicity is easily suppressed.
  • the “mass ratio represented by (e) / (a)” is the content (mass%) of the component (e) relative to the content (mass%) of the ingredient (a) in the aminocarboxylic acid (salt) -containing particles. ) Ratio.
  • the “mass ratio represented by (b) / (a)” is the content (mass%) of the component (b) relative to the content (mass%) of the ingredient (a) in the aminocarboxylic acid (salt) -containing particles. ) Ratio.
  • Mass ratio represented by (c) / [(d) + (e)] is the total content (mass of component (d) and component (e) in the aminocarboxylic acid (salt) -containing particles. %) Of the content (mass%) of the component (c).
  • Method (I) A method of adding (a) component (powder) and mixing after adding water or the like by spraying or the like while mixing component (b).
  • water examples include water and an aqueous solution of the above base.
  • the component (a) is likely to change to a structure in which the component (b) hardly absorbs moisture.
  • the pH of the aqueous solution is preferably 8 to 12, and more preferably 8 to 10.
  • the spray amount of water or the like may be appropriately controlled so as to be within the preferable range of the water content described above, and is 0.2 to 5 masses with respect to 100 mass parts in total of the components (a) and (b).
  • coated component can also be added further.
  • the aminocarboxylic acid (salt) -containing particles are less likely to be agglomerated and the fluidity is improved.
  • a Redige mixer M20 type, manufactured by Matsubo Co., Ltd.
  • a high speed mixer a pro-shear mixer, and the like can be used.
  • the mixing condition is such that the stirring speed is, for example, the rotational speed of the main shaft, preferably 100 to 350 rpm, more preferably 150 to 250 rpm.
  • the temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.
  • Method (II) A method in which component (a), component (b) and water are mixed to prepare a slurry, and the slurry is spray-dried.
  • the spray drying conditions are such that the spray pressure (gauge pressure) is preferably 2 to 4 MPa, more preferably 2.5 to 3 MPa.
  • the gas temperature supplied from the lower part of the spray drying tower is preferably 170 to 300 ° C., more preferably 230 to 270 ° C., and the gas temperature discharged from the top of the spray drying tower is 70 ° C. It is preferably set to ⁇ 125 ° C., more preferably 90 to 110 ° C.
  • Method (III) A method in which the component (a) and the component (b) are mixed and then a liquid binder is added and mixed.
  • the liquid binder the binders exemplified above as other components can be used, and a water-soluble polymer that is solid at room temperature and dissolves when heated is preferable.
  • polyethylene glycol is particularly preferable because it is easy to handle.
  • the polyethylene glycol preferably has an average molecular weight of 1,000 to 20,000, more preferably an average molecular weight of 4,000 to 10,000. When the average molecular weight is not less than the lower limit value, the fluidity becomes better, and when it is not more than the upper limit value, the solubility becomes better.
  • An average molecular weight here shows the average molecular weight described in the cosmetics raw material reference
  • a liquid binder By adding a liquid binder, sufficient shearing force is imparted during stirring, the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is further reduced, and solidification hardly occurs.
  • a mixer used in the method (III) a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.), a high speed mixer, a pro-shear mixer, or the like can be used.
  • the mixing condition is such that the stirring speed is, for example, the rotational speed of the main shaft, preferably 100 to 350 rpm, more preferably 150 to 250 rpm.
  • the temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C.
  • the mixing efficiency is increased. Therefore, it is preferable to perform the crushing operation by rotating the chopper at 1000 to 5000 rpm while rotating the main shaft.
  • components (c), (d), and (e) may be added as appropriate.
  • the components (a) to (e) are kneaded.
  • the method for performing the kneading is not particularly limited, and examples thereof include a method using a conventionally known batch type or continuous type kneader.
  • a horizontal type having a stirring blade that rotates the component (c), the component (d), the component (e), and the component (b) in the vertical direction.
  • the mixture is introduced into a chamber, and a batch type kneader is heated to 40 to 80 ° C. to perform stirring and mixing.
  • a kneaded product is obtained by introducing the component (a) into the horizontal chamber and kneading and kneading.
  • the stirring blade rotates in a direction perpendicular to the horizontal axis of the horizontal chamber, and the rotation speed is preferably about 120 to 360 rpm.
  • stirring blades can be used, and among them, a skid type shovel blade is preferable. It is also preferable to use a chopper blade rotating at 3000 to 6000 rpm together with the stirring blade.
  • a pro shear mixer manufactured by Taiheiyo Kiko Co., Ltd.
  • a ladyge mixer a ribbon mixer, a turbulizer, a pug mixer, a Spartan luzer (above, Fuji Powdal Co., Ltd.); tabletop kneader (Irie Shokai Co., Ltd.) and the like.
  • a continuous kneader for example, a closed consolidation apparatus (preferably a horizontal type) heated to a temperature at which the component (e) melts (preferably 25 to 100 ° C., more preferably 40 to 80 ° C.).
  • a closed consolidation apparatus preferably a horizontal type heated to a temperature at which the component (e) melts (preferably 25 to 100 ° C., more preferably 40 to 80 ° C.).
  • the above-mentioned component (c), component (d), component (e), and component (b) are mixed in advance after powder mixing or while mixing component (a).
  • a powder mixture is prepared by introduction and powder mixing, and a kneaded product is obtained by applying a shearing force to the powder mixture and kneading gently at that temperature.
  • the hermetic consolidation apparatus (preferably a horizontal continuous kneader) is continuously heated to a temperature at which the component (A) and the component (e) are melted, and powder mixed therein (a )
  • the powder mixture of the components is continuously introduced and kneaded and kneaded to obtain a kneaded product.
  • Such kneading and kneading can be performed using a single-screw or twin-screw kneading extruder in addition to the kneader.
  • the continuous kneader used here include a KRC kneader manufactured by Kurimoto Steel Corporation, an extruder manufactured by Nara Machinery, and the like.
  • the method using a continuous kneader is preferable because the hygroscopicity of the finally obtained aminocarboxylic acid (salt) -containing particles can be suppressed and solidification is less likely to occur.
  • the components (c) to (e) and (b) are first mixed with powder, A method in which the component (a) is added and kneaded gently is preferred.
  • the temperature during kneading is preferably in a temperature range that does not include the dehydration / transition temperature of component (a), and is a temperature that is 3 ° C. higher than the melting point of component (e). More preferably, the temperature is 5 to 20 ° C. higher than the melting point of the component (c).
  • the kneading and kneading in the kneading step is preferably performed substantially without adding water.
  • the storage stability of the aminocarboxylic acid (salt) -containing particles is improved.
  • the final content of the aminocarboxylic acid (salt) -containing particles is (a) component 10 to 80% by mass, and (b) component 10 to Each component is blended so as to be 80% by mass.
  • both the component (d) and the component (b) are preferably used as they are because the storage stability of the aminocarboxylic acid (salt) -containing particles is improved.
  • the component (d) is used by mixing with a slight amount of inorganic salt (sodium chloride, sodium sulfate, aluminosilicate, calcium carbonate, etc.) from the viewpoint that the component (d) can be easily powdered. Also good.
  • a powder having an average particle size of 30 to 800 ⁇ m is preferably used, a powder of 50 to 600 ⁇ m is more preferable, and a powder of 60 to 550 ⁇ m is more preferable.
  • A When the average particle diameter of a component is more than a lower limit, the powdering of (a) component itself is suppressed. On the other hand, when the average particle size of the component (a) is not more than the upper limit value, a uniform kneaded product is easily obtained.
  • a powder having an average particle size of 30 to 1500 ⁇ m is preferably used, a powder of 50 to 1300 ⁇ m is more preferable, and a powder of 60 to 1200 ⁇ m is more preferable.
  • the average particle size of the component (b) is equal to or greater than the lower limit, the dusting of the component (b) itself is suppressed, and the caking prevention effect due to hygroscopicity is improved.
  • the average particle size of the component (b) is not more than the upper limit value, a uniform kneaded product is easily obtained.
  • the temperature of the kneaded product after the kneading is preferably 50 to 65 ° C, more preferably 53 to 63 ° C.
  • the temperature of the kneaded product is equal to or higher than the lower limit, a homogeneous kneaded product is formed, the solubility is improved, and the storage stability is also improved.
  • the temperature of the kneaded product is not more than the upper limit value, the shape retention after extrusion granulation is improved and the solubility is also improved.
  • Hardness of the kneaded material indicates a value obtained by converting the hardness of the kneaded material into a load, which is measured using a hard meter (manufactured by Fujiwara Seisakusho).
  • the temperature at the time of kneading and kneading may be adjusted, or the blending amount of the component (e) may be adjusted.
  • the kneaded material obtained in the kneading step is extruded and granulated. Specifically, the kneaded product obtained in the kneading step is put into a uniaxial or biaxial screw kneading extruder to be extruded to form strands such as a cylindrical shape, a prismatic shape, and a triangular shape; a spherical shape, a plate shape, or a noodle shape. Get a granulate. Especially, it is preferable to extrude the kneaded material obtained in the kneading step through a die in order to obtain a desired diameter.
  • the hole diameter of the die is preferably about 0.5 to 1.4 mm, and more preferably about 0.8 to 1.2 mm.
  • the temperature of the extrudate after extrusion granulation is preferably 48 to 70 ° C, more preferably 52 to 67 ° C.
  • the extrusion pressure does not become too high, and the burden (load) on the apparatus is easily reduced.
  • the temperature of the extrudate is equal to or lower than the upper limit value, coalescence of the granulated product is easily suppressed during the granulating (grinding) operation described later.
  • the extrusion power in the extruder when extruding the kneaded product is preferably 4 to 50 kwh / t, more preferably 4.5 to 48 kwh / t, still more preferably 5 to 45 kwh / t, It is particularly preferably 5.5 to 40 kwh / t.
  • the extrusion power is 4 kwh / t or more, the storage stability of the resulting aminocarboxylic acid (salt) -containing particles is improved.
  • the extrusion power is 50 kwh / t or less, the extrudate does not become too hard, and it is difficult for fine powder to be generated during pulverization.
  • the solubility of aminocarboxylic acid (salt) -containing particles in water is improved.
  • the extruder include pelleter double (manufactured by Fuji Paudal Co., Ltd.), twin dome gran (manufactured by Fuji Powdal Co., Ltd.), and multi-gran (manufactured by Dalton Co., Ltd.).
  • a method of attaching a mesh plate to the outlet of the kneaded product in a kneading apparatus and passing the mesh plate to obtain a granulated product can be mentioned.
  • an apparatus applicable to this method for example, Extrude Ohmics manufactured by Hosokawa Micron Corporation can be cited.
  • the rotational speed of the high-speed rotary knife cutter is preferably about 30 to 100 m / s.
  • the pulverizer include a comminator (manufactured by Fuji Powder Co., Ltd.), a Fitzmill (manufactured by Hosokawa Micron Corporation), a speed mill (manufactured by Okada Seiko Co., Ltd.), and the like.
  • the extrudate is preferably made into a granulated product having an average particle size of 200 to 700 ⁇ m, more preferably a granulated product having a particle size of 250 to 450 ⁇ m.
  • the particle diameter of the granulated product is not less than the lower limit, the storage stability of the aminocarboxylic acid (salt) -containing particles is improved.
  • the particle size of the granulated product is not more than the upper limit, the solubility of the aminocarboxylic acid (salt) -containing particles in water is improved.
  • the ratio of the granulated particles having a particle diameter of less than 150 ⁇ m is preferably 14% by mass or less, more preferably 0.2 to 10% by mass with respect to the total aminocarboxylic acid (salt) -containing particles. .
  • the amount is not more than the upper limit, dust generation is less likely to occur, and the fluidity of the aminocarboxylic acid (salt) -containing particles is improved.
  • the method for producing aminocarboxylic acid (salt) -containing particles of the present invention may have other steps other than the kneading step and the granulating step described above. Examples of the other steps include a step of further covering the surface of the granulated product obtained in the granulation step.
  • the method (I), the method (III) or the (IV) is preferable from the viewpoint of energy efficiency related to production.
  • the granular detergent composition of the present invention contains the aminocarboxylic acid (salt) -containing particles of the present invention.
  • the average particle size of the granular detergent composition is preferably 200 to 1500 ⁇ m, more preferably 250 to 1000 ⁇ m, and even more preferably 280 to 500 ⁇ m.
  • production of a fine powder is suppressed as this average particle diameter is more than a lower limit, and the solubility to water improves on the other hand when it is below an upper limit.
  • the bulk density of the granular detergent composition is preferably 0.3 to 1.5 g / mL, more preferably 0.6 to 1.2 g / mL, even more preferably 0.7 to 0.9 g / mL. If the bulk density is equal to or higher than the lower limit value, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is below an upper limit, the solubility in water of a granular detergent composition will become favorable.
  • the bulk density is a value measured by a method according to JIS K3362-1998.
  • the water content of the granular detergent composition is preferably 15% by mass or less, more preferably 2 to 9% by mass, and further preferably 4 to 8% by mass. If this water content is below an upper limit, solidification of a granular detergent composition will become harder to arise.
  • the content of aminocarboxylic acid (salt) -containing particles is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 12% by mass.
  • the detergent raw materials surfactants, peroxides, etc.
  • the amount is not more than the upper limit value, it becomes easy to achieve a blending balance with other detergent raw materials, and a sufficient cleaning effect and the like are easily obtained.
  • detergent raw material other than the aminocarboxylic acid (salt) -containing particles in the granular detergent composition those usually blended in detergent compositions for clothing and the like can be used.
  • Detergent raw materials include, for example, surfactants (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.), inorganic builder, organic builder, alkaline agent, sulfate and other particle strength retaining agents, Bleaching agent such as percarbonate or granulated product thereof, recontamination (deposition) inhibitor, dye, pigment, fragrance, enzyme agent (for example, protease, lipase, cellulase, amylase, etc.), bleach activator or granulated product thereof , Reducing agents such as sulfites and thiosulfates, optical brighteners, ultraviolet absorbers, softeners (such as bentonite), foam control agents (such as silicone), surface modifiers, oil absorbers, antioxidants, Examples include antibacterial
  • the manufacturing method of a granular detergent composition can be manufactured with a well-known manufacturing method. For example, after preparing a slurry by dispersing and dissolving a detergent raw material such as a surfactant, an inorganic builder, an organic builder, or an alkali agent in water, the slurry is spray-dried to obtain spray-dried particles. Next, the spray-dried particles and other detergent raw materials are kneaded, extruded, granulated, or pulverized to obtain a powder. Thereafter, the granular detergent composition can be obtained by mixing the powder, aminocarboxylic acid (salt) -containing particles, and other detergent raw materials.
  • a detergent raw material such as a surfactant, an inorganic builder, an organic builder, or an alkali agent in water
  • the slurry is spray-dried to obtain spray-dried particles.
  • the spray-dried particles and other detergent raw materials are kneaded, extruded, granul
  • the aminocarboxylic acid (salt) -containing particles of the present invention have reduced hygroscopicity. Therefore, even if the granular detergent composition containing the aminocarboxylic acid (salt) -containing particles contains hygroscopic aminocarboxylic acid (salt), solidification hardly occurs.
  • the reason why the granular detergent composition containing the aminocarboxylic acid (salt) -containing particles hardly causes solidification is not clear, but is presumed as follows.
  • the aminocarboxylic acid (salt) -containing particles of the present invention by containing the component (a) and the component (b) in a predetermined molar ratio, the surface vicinity of the component particles (b) Therefore, it is considered that it is less affected by the environment and has a lower hygroscopicity than the case of only the component particles (b). Accordingly, it is considered that the granular detergent composition of the present invention hardly causes solidification and hardly causes so-called caking.
  • the granular detergent composition of the present invention has a sterilizing effect in addition to the cleaning effect.
  • the reason for having such an effect is considered to be that the component (a) and the component (b) form a complex in water, and this complex exhibits a sterilizing effect or a bactericidal effect.
  • ⁇ Measuring method of average particle diameter> (Measuring method 1)
  • the average particle diameter of each particle of Examples A1 to A17, Comparative Examples A1 to A8, and Reference Examples A1 to A4 was measured using a particle size distribution analyzer (LDSA-3400A (17ch), manufactured by Tohnichi Computer Applications Co., Ltd.).
  • the volume-based median diameter was measured by a laser light scattering method.
  • the moisture content is 5 g of sample using an infrared moisture meter (product name: Kett moisture meter manufactured by Kett Science Laboratory Co., Ltd.), when the sample surface temperature is 130 ° C. (when measuring a granular detergent composition). ) Or 170 ° C. (when measuring spray-dried particles), measurement was performed under the conditions of a measurement time of 20 minutes.
  • infrared moisture meter product name: Kett moisture meter manufactured by Kett Science Laboratory Co., Ltd.
  • ⁇ Calculation method of moisture absorption rate (actual measurement)> First, the sample was spread on a glass petri dish (inner diameter 85 mm) so as to have a thickness of 5 mm, and placed in a thermostat set at a temperature of 45 ° C. and a relative humidity of 80%. Next, at every elapsed time (every 60 minutes), the mass of the glass petri dish in which the sample was spread was measured in the thermostat and the change with time was recorded. And the moisture absorption rate (actual measurement) (mass%) was calculated
  • the calculated moisture absorption value (% by mass) was determined by the following formula (2).
  • metal salt means zinc sulfate monohydrate or anhydrous sodium sulfate.
  • MGDA blending amount” and metal salt blending amount are “(b) MGDA” and “(a) zinc sulfate monohydrate” or “anhydrous sodium sulfate” shown in Tables A1 to A4, respectively. Content.
  • the “moisture absorption rate of MGDA alone” is 83.4% by mass (Comparative Example A1).
  • the “moisture absorption rate of the metal salt alone” is 4.7% by mass (reference example A1) when the metal salt is zinc sulfate monohydrate, and 0.5% by mass (reference example A2) when it is anhydrous sodium sulfate. is there.
  • the aminocarboxylic acid (salt) is other than MGDA, the calculation is performed by replacing “MGDA” in the following formula (2) with each aminocarboxylic acid (salt).
  • ⁇ Evaluation method of solidification property of granular detergent composition A three-layer paper in which coated cardboard (basis weight: 350 g / m 2 ), wax sand paper (basis weight: 30 g / m 2 ) and kraft pulp paper (basis weight: 70 g / m 2 ) are laminated in this order. Using this, a box having a bottom surface of 150 mm ⁇ 90 mm and a height of 85 mm was produced. 500 g of the granular detergent composition of each example was placed in this box and placed in a thermostatic bath set at a temperature of 30 ° C. and a relative humidity of 80% for 48 hours.
  • the raw materials used in this example are as follows.
  • Zinc compounds (a) Zinc sulfate monohydrate: manufactured by Shinyo Co., Ltd., trade name “dry zinc sulfate”, average particle size 70 ⁇ m.
  • Component comparison component (a ′) Anhydrous sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”, average particle size 89 ⁇ m.
  • Aminocarboxylic acid or salt thereof (b) MGDA: trisodium methylglycine diacetate, manufactured by BASF, trade name “Trilon M Powder”, coordination position 4, content (pure content) 83% by mass, average particle size 63 ⁇ m.
  • NTA nitrilotriacetic acid trisodium, manufactured by BASF, trade name “Trilon A92R”, pure content 92% by mass, average particle size 63 ⁇ m.
  • IDS tetrasodium iminodisuccinate, manufactured by LANXESS, trade name “Baypure CX100”, pure content 80% by mass, average particle size 100 ⁇ m.
  • Sodium bicarbonate Made by Junsei Chemical Co., Ltd., special grade.
  • Zeolite Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 ⁇ m.
  • Polyethylene glycol manufactured by Lion Corporation, trade name “PEG # 6000P”, average molecular weight 6000, melting point 56-61 ° C.
  • MES paste ⁇ -sulfo fatty acid alkyl ester salt-containing paste
  • Paste composition ⁇ -sulfo fatty acid alkyl ester salt (MES-Na) 63 mass%, nonionic surfactant (polyoxyethylene alkyl ether described later) 16 mass% %, Impurities such as di-salt and methylsulfate 8% by mass, moisture 13% by mass
  • ⁇ -sulfo fatty acid alkyl ester salt fatty acid chain lengths of 16 and 18, carbon numbers of 16 and carbon numbers of 18 Mixing ratio C16 / C18 8/2 (mass ratio).
  • LAS-K linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (LAS-H pure content 96 mass%)] > The compound neutralized with 48 mass% potassium hydroxide aqueous solution at the time of slurry preparation for spray-drying particle preparation.
  • LAS-H linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, Rypon LH-200 (pure content 96% by mass)].
  • Polyoxyethylene alkyl ether ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C.). Pure content 90% by mass, moisture content 10% by mass. Soap: fatty acid sodium having 12 to 18 carbon atoms (C) [manufactured by Lion Corporation, pure content 67% by mass, titer 40 to 45 ° C .; fatty acid composition C12 0.7% by mass, C14 11.4% by mass, C16 29. 2 mass%, C18F0 (stearic acid) 0.7 mass%, C18F1 (oleic acid) 56.8 mass%, C18F2 (linoleic acid) 1.2 mass%; molecular weight 289].
  • C fatty acid sodium having 12 to 18 carbon atoms
  • Zeolite Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 ⁇ m.
  • MA agent acrylic acid-maleic acid copolymer salt, manufactured by Nippon Shokubai Co., Ltd., trade name “AQUALIC TL-400”, pure content 40% by mass.
  • Potassium carbonate Potassium carbonate (powder) (Asahi Glass Co., Ltd.) average particle size 490 ⁇ m, bulk density 1.30 g / cm 3 .
  • Sodium carbonate granular ash (manufactured by Asahi Glass Co., Ltd.) Average particle size 320 ⁇ m, bulk density 1.07 g / cm 3 .
  • Anhydrous sodium sulfate manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”.
  • Sodium percarbonate granulated product manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 ⁇ m.
  • Carboxymethyl cellulose manufactured by Daicel Chemical Industries, Ltd., trade name “CMC Daicel 1190”, mass average molecular weight of about 300,000, and degree of etherification of 0.70.
  • Fluorescent agent Ciba Japan Co., Ltd., trade name “Chino Pearl CBS-X”.
  • Dye 20% by mass aqueous dispersion of ultramarine (made by Dainichi Seika Kogyo Co., Ltd.).
  • Perfume Perfume composition A shown in Tables 11 to 18 described in JP-A-2002-146399.
  • Granulated product of bleach activator mass ratio of OBS12 (sodium 4-dodecanoyloxybenzenesulfonate), PEG6000, AOS (sodium ⁇ -olefinsulfonate having 14 carbon atoms) and A-type zeolite powder 70/20/5/5 granulated product.
  • aminocarboxylic acid (salt) -containing particles ⁇ Production example of aminocarboxylic acid (salt) -containing particles>
  • the aminocarboxylic acid (salt) -containing particles of each example were prepared according to the compositions shown in Tables A1 to A4. In the table, the content of the compounding component indicates a pure equivalent amount.
  • Example A1 A MGDA is introduced at 40 ° C. into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) with a scissors blade-shaped excavator and a clearance between the shovel and the wall surface of 5 mm, and water (MGDA 100 mass) while rotating the spindle at 200 rpm. 1.0 parts by mass) was sprayed. After spraying was completed, zinc sulfate monohydrate was added at 40 ° C., and stirring was performed while the main shaft was rotated at 200 rpm (the chopper was stopped). After 5 minutes from the start of stirring, MGDA-containing particles were obtained.
  • Examples A2, A3 According to the composition shown in Table A1, MGDA-containing particles were obtained in the same manner as in Example A1, except that the blending amounts of zinc sulfate monohydrate and MGDA were changed.
  • Example A4 MGDA-containing particles were obtained in the same manner as in Example A2, except that 1% by mass aqueous sodium hydrogen carbonate (bicarbonate) solution (pH 8.5 / 25 ° C.) was sprayed instead of water.
  • aqueous sodium hydrogen carbonate (bicarbonate) solution pH 8.5 / 25 ° C.
  • Example A5 A spray drying slurry preparation device, that is, a mixing tank having a stirring blade including a stirring blade and a rotating shaft and having a circulation line with a pump, water (36% by mass in the slurry for spray drying), MGDA and zinc sulfate monohydrate A Japanese product was introduced. Thereafter, stirring was continued for 10 minutes, the temperature was adjusted to 75 ° C., and a slurry for spray drying was prepared at a scale of a blending amount of 200 kg / batch. The rotation speed of the stirring blade at this time was set to 60 rpm.
  • the obtained slurry for spray drying is transferred to a spray drying tower, sprayed at a spray pressure of 2.5 MPa (gauge pressure) from a pressure spray nozzle installed near the top of the spray drying tower, and spray-dried particles
  • MGDA-containing particles were obtained.
  • a gas at a temperature of 230 to 270 ° C. is supplied from the lower part of the spray drying tower, and a high temperature gas is supplied to the spray drying tower by discharging from the top of the spray drying tower at a temperature of 90 to 110 ° C. did.
  • the temperature of the supplied high-temperature gas was appropriately adjusted in order to obtain MGDA-containing particles having a desired water content (3% by mass).
  • Example A6 A MGDA was introduced at 40 ° C. into a Redige mixer (M20 type, manufactured by Matsubo Co., Ltd.) equipped with a scissors blade-shaped excavator and the clearance between the shovel and the wall surface was 5 mm, and water was sprayed while rotating the main shaft at 200 rpm. . After spraying is completed, zinc sulfate monohydrate is charged at 40 ° C., stirring is performed while the main shaft is rotated at 200 rpm (the chopper is stopped), and after 5 minutes from the start of stirring, zeolite is charged at 40 ° C. Then, MGDA-containing particles were obtained by stirring (chopper stopped) for 5 minutes while rotating the main shaft at 200 rpm.
  • a Redige mixer M20 type, manufactured by Matsubo Co., Ltd.
  • Example A7 A Rougege mixer (M20 type, manufactured by Matsubo Co., Ltd.) with a scissors blade-shaped excavator and a jacket temperature controlled to 65 ° C. and a clearance between the shovel and the wall surface of 5 mm, MGDA at 60 ° C., and zinc sulfate at 60 ° C. Monohydrate was added and stirred (chopper stopped) while rotating the main shaft at 200 rpm. Five minutes after the start of the stirring, the chopper was rotated at 4000 rpm (the rotational speed of the main shaft was unchanged), and polyethylene glycol at 25 ° C. was added and stirred for 5 minutes to obtain MGDA-containing particles.
  • M20 type manufactured by Matsubo Co., Ltd.
  • Example A8 According to the composition shown in Table A2, NTA-containing particles were obtained in the same manner as in Example A1, except that the amount of zinc sulfate monohydrate was changed and MGDA was changed to a predetermined amount of NTA.
  • Example A9 According to the composition shown in Table A2, IDS-containing particles were obtained in the same manner as in Example A1, except that the blending amount of zinc sulfate monohydrate was changed and MGDA was changed to a predetermined amount of IDS.
  • Example A2 MGDA-containing particles were obtained in the same manner as in Example A1, except that anhydrous sodium sulfate was used instead of zinc sulfate monohydrate.
  • the average particle diameter was measured by the method described above, and the moisture absorption rate (actual measurement) and the calculated moisture absorption rate were calculated. The results are also shown in Tables A1 to A4.
  • the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 according to the present invention have a moisture absorption rate (compared with the aminocarboxylic acid (salt) alone of Comparative Examples A1, A5, and A6). It can be seen that the actual measurement is very low. Further, from the comparison between Examples A1 to A9 and Comparative Examples A2 to A4, the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 have a moisture absorption rate (actual measurement) / calculated moisture absorption rate of 30 to 75%. It can be seen that the moisture absorption rate (actual measurement) is significantly lower than the calculated value of moisture absorption rate. Therefore, it was confirmed that the aminocarboxylic acid (salt) -containing particles of Examples A1 to A9 according to the present invention have low hygroscopicity.
  • Example A10 In accordance with the composition shown in Table A5, each compounding component was put into a reactor having a stirrer and a jacket, dissolved and dispersed in water (jacket temperature of the stirrer 75 ° C.), and spray-dried particles having a solid content concentration of 60% by mass. A slurry for preparation was prepared.
  • this slurry for preparing spray-dried particles is spray-dried using a countercurrent drying tower under the following conditions, and zeolite (obtained spray-dried particles obtained) as a coating for coating the spray-dried particles from the bottom of the spray-drying tower.
  • the spray dried particles were obtained by introducing 1 part by mass to 100 parts by mass.
  • Spray drying conditions ⁇ Spray dryer: counter-current type, tower diameter 2.0m, effective length 5.0m ⁇ Atomization method: Pressurized nozzle method ⁇ Spraying pressure: 30 kg / cm 2 ⁇ Hot air inlet temperature: 250 °C -Hot air outlet temperature: 100 ° C The obtained spray-dried particles had an average particle size of 300 ⁇ m, a bulk density of 0.30 g / mL, and a water content of 5.0% by mass (moisture content measurement conditions: 170 ° C., 20 minutes).
  • the obtained dough-like material is put into a pelleter double (product name: EXD-100 type, manufactured by Fuji Paudal Co., Ltd.) and extruded from a die having a hole diameter of about 10 mm and a thickness of 10 mm and simultaneously cut (perimeter of the cutter of the pelleter).
  • the speed was 5 m / s) to obtain a pellet-shaped formed body (diameter: about 10 mm, length: 70 mm or less (substantially 5 mm or more)).
  • Fitzmill manufactured by Hosokawa Micron Co., Ltd., DKA- was added to 74.8% by mass of the obtained pellet-shaped molded body by adding 5.2% by mass of zeolite as a grinding aid and arranged in three stages in the presence of air blowing. 6 type) to obtain a powder.
  • the grinding conditions were as follows. The temperature of the obtained powder was 30 ⁇ 10 ° C. [Crushing conditions] -Air temperature: 15 ⁇ 3 degreeC. ⁇ Blowing rate (ratio of gas / solid): 2.8 ⁇ 0.25 m 3 / kg. -Screen diameter: 6 mm for the first stage, 4 mm for the second stage, and 2 mm for the third stage. -Crusher rotation speed: 470 rpm (circumferential speed about 60 m / s). Processing speed: 230 g / hr.
  • a horizontal cylindrical rolling drum (diameter 0.70 m, length 1.40 m, inclination angle 3 °, thickness 1 mm ⁇ height 50 mm ⁇ length 350 mm baffle 15 so that the processing speed is 240 kg / hr.
  • Example A1 80.0% by mass of the powder, 1.8% by mass of zeolite, 5.0% by mass of sodium percarbonate granule, 1.0% by mass of carboxymethylcellulose, and MGDA of Example A1
  • 10 mass% of the contained particles are added and mixed, and at the same time, 0.5 mass% of polyoxyethylene alkyl ether is sprayed at a spray pressure of 0.5 to 1.5 MPa using a pressure cone nozzle K series (manufactured by Ikeuchi Co., Ltd.). Sprayed.
  • a granular detergent composition (average particle diameter of 360 ⁇ m, bulk density of 0.85 g / mL) was obtained.
  • the moisture content of the obtained granular detergent composition was 7.0 mass% (measuring conditions of moisture content 130 ° C., 20 minutes).
  • Examples A11 to A17, Comparative Examples A7 to A8 A granular detergent in the same manner as in Example A10 except that the aminocarboxylic acid (salt) -containing particles of Examples A2, A4 to A9 and Comparative Examples A1 to A2 were used instead of the MGDA-containing particles of Example A1.
  • a composition was obtained.
  • Example A10 a granular detergent composition was obtained in the same manner as in Example A10, except that the zinc sulfate monohydrate of Reference Example A1 was used instead of the MGDA-containing particles of Example A1.
  • the average particle diameters of Examples B1 to B10 and Comparative Examples B1 and B2 were measured by the measuring method 2 or a method according to the same among the above-mentioned [Measuring method of average particle diameter].
  • the dehydration / transition temperature was measured in the same manner as described above.
  • the compositions of the aminocarboxylic acid (salt) -containing particles produced by the production methods of each example are shown in Tables B1 to B3.
  • the raw materials used in this example are as follows.
  • Anionic surfactant (d) AOS-Na: ⁇ -olefin sulfonic acid Na salt having 14 to 18 carbon atoms, manufactured by Lion Corporation, trade name “Lipolane PJ-400”, average particle size 200 ⁇ m.
  • AS-Na Alkyl sulfate sodium salt having an alkyl group having 10 to 18 carbon atoms, manufactured by Shin Nippon Rika Co., Ltd., trade name “Sinoline 90TK-T”, average particle size 150 ⁇ m.
  • -Nonionic surfactant having a melting point of less than 45 ° C
  • natural alcohol EO ethylene oxide
  • LMAO-90 pure content 90% by mass
  • POE alkyl ether 9): natural alcohol EO 9 mol adduct having 12 to 16 carbon atoms, manufactured by Lion Co., Ltd., trade name “Leox CL-90”, pure content 100 mass%, melting point 28 ° C.
  • Zinc compounds (a) Zinc sulfate monohydrate: manufactured by Horiike Sangyo Co., Ltd. BR> A trade name “ZNS-13”, average particle size 200 ⁇ m, dehydration and transition temperature 270 ° C.
  • Aminocarboxylic acid or salt thereof (b) MGDA: trisodium methylglycine diacetate, manufactured by BASF Japan Ltd., trade name “Trilon M powder”, average particle size 80 ⁇ m; average neutralization degree 100%.
  • Citric acid Made by Junsei Co., Ltd., reagent grade.
  • composition of granular detergent (blending component blending amount): MES-Na 9.0% by mass, LAS-Na 1.0% by mass, polyoxyethylene alkyl ether 4.0% by mass, soap 5.0% by mass, sodium carbonate balance , Potassium carbonate 4.0% by mass, sodium sulfate 13.0% by mass, zeolite 15.0% by mass, acrylic acid-maleic acid copolymer salt 2.0% by mass, fluorescent brightener 0.1% by mass, water 7. 0% by mass, enzyme 1.0% by mass, sodium percarbonate granulated product 5.0% by mass, bleach activator granulated product 1.0% by mass, aminocarboxylic acid (salt) -containing particles 1.0% by mass
  • Preparation method of granular detergent [Drying process] Polyoxyethylene alkyl ether, MES-Na, part of zeolite (for grinding aid, post-mixing step), enzyme, sodium percarbonate granule, bleach activator granule, amino An aqueous slurry having a solid content of 62% by mass was obtained by stirring a predetermined amount of all the components except the carboxylic acid (salt) -containing particles at a preparation temperature of 80 ° C. for 17 minutes.
  • a part of the zeolite represents 30% by mass of the total amount of the zeolite.
  • the aqueous slurry was spray-dried to prepare spray-dried particles having a water content of 5% by mass.
  • a part of polyoxyethylene alkyl ether, MES-Na, and a small amount (1 part by weight with respect to 100 parts by weight of the spray-dried particles) of tap water (Edogawa, Tokyo) was added to a continuous kneader (KRC-S4 type, manufactured by Kurimoto Seiko Co., Ltd.) and kneaded continuously at a temperature of 55 to 65 ° C.
  • the kneaded material obtained by the kneading kneading was extruded while being continuously fed to a pelleter (made by Fuji Powder, die hole diameter 10 mm ⁇ ) to form a pellet-shaped solid detergent.
  • Fitzmill made by Hosokawa Micron Co., Ltd., DKA-3 type
  • the granulated product was obtained by pulverizing and granulating so that the average particle size was 300 to 500 ⁇ m.
  • the production capacity at this time was set to 180 kg / hr.
  • a part of said polyoxyethylene alkyl ether remove excludes the part used by a post-mixing process, and shows 70 mass% part of polyoxyethylene alkyl ether whole quantity.
  • Post-mixing process The granulated product obtained in the granulation step, the remaining polyoxyethylene alkyl ether (for 30% by mass), the remaining zeolite (for post-mixing step), the enzyme, and the sodium percarbonate granulated product, The bleach activator granulated product and the aminocarboxylic acid (salt) -containing particles are mixed with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, drum inner wall surface of vessel 131.7 L and inner wall surface).
  • the mixture was mixed for 1 minute under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. to produce granular detergents of each example.
  • a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. was produced.
  • only polyoxyethylene alkyl ether (30% by mass) was added using a pressure nozzle while spraying so that the droplet diameter was 40 to 150 ⁇ m.
  • the granular detergents obtained in each example had a bulk density in the range of 0.82 to 0.88 g / cm 3 .
  • MES-Na ⁇ -sulfo fatty acid alkyl ester salt-containing paste
  • paste composition ⁇ -sulfo fatty acid alkyl ester salt (MES-Na) 63% by mass, nonionic surfactant (polyoxyethylene alkyl ether described later) 16% by mass, Impurities such as di-salt and methyl sulfate, 8% by mass, moisture 13% by mass
  • MES-Na ⁇ -sulfo fatty acid alkyl ester salt-containing paste
  • nonionic surfactant polyoxyethylene alkyl ether described later
  • Impurities such as di-salt and methyl sulfate, 8% by mass, moisture 13% by mass
  • Polyoxyethylene alkyl ether ECOROL 26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (melting point: 40 ° C.). Pure content 90% by mass, moisture content 10% by mass.
  • Soap C12-18 fatty acid sodium [manufactured by Lion Corporation, pure mass 67 mass%, titer 40-45 ° C; fatty acid composition C12 0.7 mass%, C14 11.4 mass%, C16 29.2 mass% C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight 289].
  • Sodium carbonate granular ash (manufactured by Asahi Glass Co., Ltd.) Average particle size 320 ⁇ m, bulk density 1.07 g / cm 3 .
  • Potassium carbonate Potassium carbonate (powder) (Asahi Glass Co., Ltd.) average particle size 490 ⁇ m, bulk density 1.30 g / cm 3 .
  • Sodium sulfate manufactured by Shikoku Kasei Co., Ltd., trade name “neutral anhydrous sodium sulfate A0”.
  • Zeolite Type A zeolite, manufactured by Thai silicate, trade name “Zeolite Na-4A”, pure content 80% by mass, average particle size 3 ⁇ m.
  • Acrylic acid-maleic acid copolymer salt sodium salt of a copolymer of acrylic acid and maleic acid, trade name “Socaran CP7”, manufactured by BASF Japan Ltd.
  • Optical brightener Ciba Specialty Chemicals Co., Ltd., trade name “Chino Pearl CBS-X”.
  • Water enzyme Protease (sabinase 12T) / Amylase (Stainzyme 12T) / Lipase (LIPEX100T) / Cellulase (CellClean 4500T) Mixture of.
  • Sodium percarbonate granulated product manufactured by Zhejiang JINKE CHEMICALS, trade name “SPCC”, effective oxygen amount 13.8% by mass, average particle size 870 ⁇ m.
  • Granulated bleach activator OBS12 (sodium 4-dodecanoyloxybenzene sulfonate), PEG-6000, AOS (sodium ⁇ -olefin sulfonate having 14 carbon atoms), and A-type zeolite powder Granulated product having a mass ratio of 70/20/5/5.
  • Aminocarboxylic acid (salt) -containing particles Aminocarboxylic acid (salt) -containing particles of Examples B1 to B10 and Comparative Examples B1 and B2 described later.
  • Aminocarboxylic acid (salt) -containing particles were produced by the following production methods in accordance with the blending components and contents (mass%) of the compositions shown in Tables B1 to B3.
  • the content of the component (a) indicates the amount as a hydrated salt containing water molecules.
  • Other components indicate the amount in terms of pure content.
  • the table shows the temperature (° C.) of the kneaded material obtained in the kneading step, the hardness (g) of the kneaded material, and the kneading power (A) when the kneading was performed.
  • the hardness (g) of the kneaded material was measured using a hard meter (manufactured by Fujiwara Seisakusho) with the temperature measurement for the kneaded material immediately after the kneading step. Die pore diameter (mm ⁇ ), extrusion power (A), extrudate temperature (° C), air current value (A), extrusion power (kwh / t), extrusion time (minutes), extrusion rate (kg) ) Is shown in the table.
  • Example B1 [Kazuwa process] Warm water was circulated in the jacket of an S-1KRC kneader manufactured by Kurimoto Steel Corporation, and the kneader body was heated to 60 ° C. and maintained at that temperature. Subsequently, all components except the component (a) shown in Table B1 were powder-mixed at room temperature, and then the component (a) was mixed to prepare a powder mixture having a total amount of 1.5 kg. This powder mixture was continuously added to the kneader for 15 minutes while continuing the operation, and after the addition, a kneaded product was obtained by performing a kneading kneading operation.
  • Example B2 [Kazuwa process] Hot water was circulated in the jacket of a PNV-5 type table kneader (manufactured by Irie Shokai Co., Ltd.), and the kneader body was heated to 60 ° C. to maintain the temperature. Subsequently, components other than the component (a) in the composition shown in Table B1 were introduced into a horizontal chamber having a stirring blade rotating in the vertical direction. Next, after performing the kneading operation at a rotating speed of the stirring blade of 45 rpm, the component (a) heated to 58 ° C.
  • Examples B3 to B8, B10 to B12 Aminocarboxylic acid (salt) -containing particles were obtained by performing the same operations as in Example B1 according to the compositions and production conditions shown in Tables B1 and B2. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.
  • Example B9 [Kazuwa process] Warm water was circulated in the jacket of the S-1KRC kneader manufactured by Kurimoto Steel Corporation, and the kneader body was heated to 57 ° C. and maintained at that temperature. Next, according to the composition and production conditions shown in Table B2, all the components (a) to (e) were powdered together to prepare a powder mixture of a total amount of 1.5 kg. This powder mixture was continuously charged into the kneader while continuing the operation, and after the charging, a kneading operation was performed to obtain a kneaded product. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components. [Granulation process] The obtained kneaded product was subjected to the same operation as in the granulating step in Example B1 to obtain aminocarboxylic acid (salt) -containing particles.
  • Example B1 According to the composition and production conditions shown in Table B3, the same operations as in Example B9 (powder mixing, kneading kneading, extrusion granulation of all the components (a) to (e) together) Aminocarboxylic acid (salt) -containing particles were obtained. The powder mixture was charged for 15 to 30 minutes per 1.5 kg of the total amount of the components.
  • Dissolution rate (%) (measured value of electrical conductivity / maximum value of electrical conductivity) ⁇ 100
  • the time required for the dissolution rate (%) to be 90% or more was determined as the dissolution time (seconds). Specifically, taking the time (seconds) on the horizontal axis and the electric conductivity value on the vertical axis, the measurement is continued until the electric conductivity is balanced over time, and all the aminocarboxylic acid (salt) -containing particles are dissolved.
  • the hygroscopicity of the aminocarboxylic acid (salt) -containing particles is a characteristic that serves as an indicator of the solidification properties of the aminocarboxylic acid (salt) -containing particles themselves and the solidification properties of the detergent when blended in a detergent.
  • the hygroscopic evaluation of the aminocarboxylic acid (salt) -containing particles was performed as follows.
  • the aminocarboxylic acid (salt) -containing particles (samples) obtained in each example were spread on a glass petri dish (inner diameter 85 mm) to a thickness of 5 mm and placed in a thermostatic chamber set at a temperature of 45 ° C. and a relative humidity of 80%. I put it in. Next, every 60 minutes, the mass of the glass petri dish with the sample spread was measured in the thermostat and the change with time was recorded. And the moisture absorption (mass%) was calculated
  • “measured value”, “sample preparation amount”, and “sample collection amount” are as follows. Measured value: Mass of the glass petri dish with the sample spread, measured after 48 hours in total.
  • Sample charge The mass of a glass petri dish with the sample spread, which is measured after standing for 1 minute at a temperature of 25 ° C. before being placed in a thermostatic bath.
  • Sample collection amount A value obtained by subtracting the mass of the glass petri dish measured after standing for 1 minute at a temperature of 25 ° C. from the sample preparation amount.
  • the hygroscopicity of the aminocarboxylic acid (salt) -containing particles was evaluated according to the following evaluation criteria. Those whose evaluation results were A, B, and C were regarded as acceptable. (Evaluation criteria) A: The moisture absorption rate was less than 5% by mass. B: The moisture absorption was 5% by mass or more and less than 10% by mass. C: The moisture absorption was 10% by mass or more and less than 20% by mass. D: The moisture absorption was 20% by mass or more and less than 40% by mass. E: The moisture absorption was 40% by mass or more.
  • the residual amount of the granular detergent remaining on the sieve was measured, and the solidification property of the detergent was evaluated according to the following evaluation criteria. Those whose evaluation results were A and B were regarded as acceptable. (Evaluation criteria) A: The remaining amount of the granular detergent remaining on the sieve was less than 50 g. B: The remaining amount of the granular detergent remaining on the sieve was 50 g or more and less than 100 g. C: The remaining amount of the granular detergent remaining on the sieve was 100 g or more and less than 300 g. D: The residual amount of the granular detergent remaining on the sieve was 300 g or more.
  • aminocarboxylic acid (salt) -containing particles of the present invention are less likely to solidify and have excellent solubility in water, they can be suitably used as a raw material for detergents.

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Abstract

La présente invention concerne des particules contenant chacune de l'acide (sel) aminocarboxylique, chacune comprenant (a) un composé de zinc et (b) un acide aminocarboxylique ou un sel de celui-ci, et qui sont caractérisées en ce que le rapport (a)/(b) est de 0,5 à 6 en moles.
PCT/JP2011/072806 2010-10-01 2011-10-03 Particules contenant chacune de l'acide (sel) aminocarboxylique, et composition de détergent granulaire WO2012043859A1 (fr)

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JP2010224126A JP2013253118A (ja) 2010-10-01 2010-10-01 アミノカルボン酸（塩）含有粒子及び粒状洗剤組成物
JP2011049624A JP2013253120A (ja) 2011-03-07 2011-03-07 金属硫酸塩造粒物及びその製造方法
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016519186A (ja) * 2013-04-02 2016-06-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 組成物、その製造、及び、食器洗い組成物としての、又は食器洗い組成物を製造するためのその使用方法
EP3755778B1 (fr) 2018-02-23 2022-04-06 Unilever Global IP Limited Procédé de préparation d'une composition solide comprenant de l'aminopolycarboxylate

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JPS5859299A (ja) * 1981-08-08 1983-04-08 ザ・プロクタ−・エンド・ギヤンブル・カンパニ− 洗濯組成物とその製法
JP2006182862A (ja) * 2004-12-27 2006-07-13 Lion Corp 粒状洗剤組成物
WO2010103833A1 (fr) * 2009-03-11 2010-09-16 ライオン株式会社 Composition détergente granulaire
JP2011057745A (ja) * 2009-09-07 2011-03-24 Lion Corp 漂白性組成物および繊維製品の処理方法
WO2011118340A1 (fr) * 2010-03-26 2011-09-29 ライオン株式会社 Substance agglomérée activatrice de blanchiment et procédé pour produire celle-ci

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Publication number Priority date Publication date Assignee Title
JPS5859299A (ja) * 1981-08-08 1983-04-08 ザ・プロクタ−・エンド・ギヤンブル・カンパニ− 洗濯組成物とその製法
JP2006182862A (ja) * 2004-12-27 2006-07-13 Lion Corp 粒状洗剤組成物
WO2010103833A1 (fr) * 2009-03-11 2010-09-16 ライオン株式会社 Composition détergente granulaire
JP2011057745A (ja) * 2009-09-07 2011-03-24 Lion Corp 漂白性組成物および繊維製品の処理方法
WO2011118340A1 (fr) * 2010-03-26 2011-09-29 ライオン株式会社 Substance agglomérée activatrice de blanchiment et procédé pour produire celle-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016519186A (ja) * 2013-04-02 2016-06-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 組成物、その製造、及び、食器洗い組成物としての、又は食器洗い組成物を製造するためのその使用方法
EP3755778B1 (fr) 2018-02-23 2022-04-06 Unilever Global IP Limited Procédé de préparation d'une composition solide comprenant de l'aminopolycarboxylate

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