EP1788071B1 - Procede pour la production de particules de detergents a noyau unique - Google Patents

Procede pour la production de particules de detergents a noyau unique Download PDF

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Publication number
EP1788071B1
EP1788071B1 EP05768548.9A EP05768548A EP1788071B1 EP 1788071 B1 EP1788071 B1 EP 1788071B1 EP 05768548 A EP05768548 A EP 05768548A EP 1788071 B1 EP1788071 B1 EP 1788071B1
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EP
European Patent Office
Prior art keywords
detergent particles
particles
weight
surfactant composition
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP05768548.9A
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German (de)
English (en)
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EP1788071A1 (fr
EP1788071A4 (fr
Inventor
Takashi Nakayama
Yoshinobu Imaizumi
Teruo Kubota
Hideichi Nitta
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Kao Corp
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Kao Corp
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Publication of EP1788071A4 publication Critical patent/EP1788071A4/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the present invention relates to a method for producing uni-core detergent particles containing, as an anionic surfactant, a compound represented by any of the formulae (1) to (3): R-O-SO 3 M (1) wherein R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms; and M is an alkali metal atom or an amine, R-O(CH 2 CH 2 O)n-SO 3 M (2) wherein R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms; n is an average number of moles added of from 0.1 to 3.0; and M is an alkali metal atom, or an ammonium or an organic amine, and wherein R is an alkyl group or an alkenyl group having 4 to 22 carbon atoms; M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium; and A is an alkyl group having 1 to 4 carbon atoms, H, or M.
  • One of the methods for producing detergent particles includes a production method including the step of mixing a powdery substance and a liquid surfactant composition.
  • a production method including the step of mixing a powdery substance and a liquid surfactant composition.
  • an anionic surfactant represented by the above-mentioned formula (1) is formulated as a detergent surfactant for the purpose of improvements in high detergent activation ability, re-deposition preventing ability, environmental friendliness, and solvency by a combination of surfactants, and the like.
  • a method for producing a granular detergent composition using a liquid surfactant composition composed of an anionic surfactant represented by the above-mentioned formula (1), a nonionic surfactant, and water (Patent Publication 1); and a production method including the step of formulating an anionic surfactant represented by the above-mentioned formula (1) in a detergent slurry (Patent Publication 2), or the step of adding an anionic surfactant represented by the above-mentioned formula (1) to an intermediate product of the extrusion-molding (Patent Publication 3) are disclosed.
  • Patent Publications 2 and 3 are free from any problems in the aspect of stability of the anionic surfactant represented by the above-mentioned formula (1), the dissolubility yet remains unsatisfied because both of the resulting detergent particles go through the treatment of increasing compactness.
  • Patent Publication 4 discloses a method for producing a granular detergent composition including the steps of oil-absorbing a paste of the anionic surfactant represented by the above-mentioned formula (2) to silica or a silicate, granulating the mixture, and drying the granules.
  • the production method as described above has an advantage that the anionic surfactant can be formulated in a high content.
  • an oil-absorbing carrier such as silica or a silicate is necessary, and further a drying step is necessitated after the granulation step in order to remove water contained in the above-mentioned paste.
  • Patent Publication 5 discloses a method for producing a detergent composition including the step of mixing a surfactant composition containing an anionic surfactant represented by the above-mentioned formula (2), a nonionic surfactant, and water, with an adsorbent powder.
  • a surfactant composition containing an anionic surfactant represented by the above-mentioned formula (2), a nonionic surfactant, and water with an adsorbent powder.
  • a method for producing a high-bulk density detergent composition including the steps of making an anionic surfactant represented by the above-mentioned formula (3) in the form of a powder, powder-blending the anionic surfactant with an alkali builder, concurrently adding a water-containing binder thereto, and granulating the mixture (Patent Publication 6); and a method for producing a high-bulk density detergent including the steps of concentrating an anionic surfactant represented by the above-mentioned formula (3), and directly formulating the concentrate into a kneading step (Patent Publication 7) are disclosed.
  • EP 0 969 082 A1 describes a method for preparing detergent particles comprising a step of preparing a slurry containing a water-insoluble inorganic compound, a water-soluble polymer and a water-soluble salt; a step of spray-drying the slurry to prepare base particles and a step of adding a surfactant to the bases particles.
  • an object of the present invention is to provide a method for producing uni-core detergent particles including the step of formulating the anionic surfactant represented by any of the above-mentioned formulae (1) to (3), in which the method for producing the detergent particles secures the stability of the anionic surfactant represented by the above-mentioned formulae (1) to (3), and provides excellent dissolubility.
  • the gist of the present invention relates to a method for producing uni-core detergent particles having an average particle size of 150 ⁇ m or more and a degree of particle growth of 1.5 or less, including the steps of:
  • the uni-core detergent particles containing an anionic surfactant represented by the above-mentioned formulae (1) to (3) which is generally very low in skin irritability and favorable in biodegradability
  • the uni-core detergent particles having an inhibitory particle growth, and a sharp particle size distribution can be produced in a high yield, without necessitating a drying step for removing the water after the granulation step is exhibited.
  • a detergent which is not only improved in external appearance, but also favorable in free-flowability, and excellent in dissolubility can be obtained.
  • One of the great features of the method for producing uni-core detergent particles of the present invention (hereinafter referred to as the production method of the present invention) resides in that the method, as described above, includes the steps of:
  • the effect that the detergent particles containing the anionic surfactant represented by the above-mentioned formulae (1) to (3), which is generally very low in skin irritability and favorable in biodegradability, the detergent particles having an inhibitory particle growth, and a sharp particle size distribution can be produced, without necessitating a drying step for removing the water after the granulation step is exhibited.
  • a mechanism for exhibiting an effect of not necessitating a drying step for removing the water after the granulation step is considered to be due to the fact that in step B), when the surfactant composition containing an anionic surfactant represented by the formulae (1) to (3) and water contacts with the base particles containing a water-soluble inorganic salt, water in the surfactant composition is taken away by the water-soluble inorganic salt, and the composition of the anionic surfactant represented by the formulae (1) to (3) loses free-flowability, whereby powdering can be carried out without adding the drying step.
  • step A) is a step of preparing a surfactant composition containing a) an anionic surfactant represented by the above-mentioned formulae (1) to (3), and b) water in an amount of from 25 to 65 parts by weight based on 100 parts by weight of the above-mentioned component a).
  • R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms, and preferably 12 to 16 carbon atoms.
  • M is preferably an alkali metal atom such as Na or K, or an amine such as monoethanolamine or diethanolamine, and especially preferably Na or K from the viewpoint of an improvement in detergency of the detergent composition.
  • R is an alkyl group or an alkenyl group having 10 to 18 carbon atoms, and preferably 12 to 16 carbon atoms.
  • the average number of moles added n is from 0.1 to 3.0, and preferably from 0.1 to 2.0.
  • M is preferably an alkali metal atom such as Na or K, an ammonium or an organic amine such as monoethanolamine or diethanolamine, and Na or K is especially preferable from the viewpoint of an improvement in detergency of the detergent composition.
  • R is an alkyl group or an alkenyl group having 4 to 22 carbon atoms
  • M is an alkali metal atom, an alkaline earth metal atom, an alkanolamine or an ammonium
  • A is an alkyl group having 1 to 4 carbon atoms, H, or M.
  • the surfactant composition has a temperature range in which the viscosity of the surfactant composition is 10 Pa ⁇ s or less, and preferably 5 Pa ⁇ s or less in an operable temperature range of the surfactant composition, from the viewpoint of handling in the production. It is preferable that the temperature range as mentioned above exists preferably in a range up to 70°C, and more preferably in a range up to 60°C, from the viewpoint of the stability of the surfactant composition.
  • the viscosity is determined with a coaxial double cylindrical rotary viscometer (manufactured by HAAKE; sensor: SV-DIN) at a shearing rate of 50 l/s.
  • the surfactant composition prepared in step A) greatly varies in viscosity depending on its water content. It is preferable that a surfactant composition having a desired water content, i.e., a desired viscosity is prepared by adjusting with an amount of water of an alkali compound usable in the preparation of the surfactant composition by neutralizing an acid precursor of the component a) with the alkali compound. It is generally known that when the surfactant composition contains the component a) and water in an amount of from 25 to 65 parts by weight (water content of the surfactant composition is from 20 to 40%) based on 100 parts by weight of the component a), the viscosity is lowered, thereby making its handling easy. It is preferable that the water of the surfactant composition is adjusted within this range in the present invention.
  • the adjustment is made so that the degradation is suppressed.
  • the method of adjustment is not particularly limited, and a known method can be used.
  • the method may be carried out by removing heat of neutralization with a heat exchanger or the like using a loop reactor while cautiously temperature-controlling the acid precursor of the component a) and the surfactant composition.
  • a temperature range during production includes a temperature of from 30° to 60°C, and a temperature range for storage after the production includes a temperature of 60°C or less.
  • the surfactant composition may be used by optionally elevating the temperature upon use.
  • the surfactant composition represented by the formula (1) or (2) it is preferable that the surfactant composition has an excess alkalinity from the viewpoint of suppressing the degradation.
  • a pH is preferably from 4 to 9, and a pH is more preferably from 5 to 8.
  • the adjusted surfactant composition may contain an unreacted alcohol or an unreacted polyoxyethylene alkyl ether upon the production of the acid precursor of the component a), sodium sulfate, which is a by-product of the neutralization reaction, or a pH buffering agent, which can be added during the neutralization reaction, a decolorizing agent, or the like.
  • the surfactant composition usable for the present invention may contain a known component ordinarily used in detergents, for example, a surfactant known in the field of laundry detergents; a re-deposition preventing agent such as acrylic acid polymer, acrylic acid-maleic acid copolymer, and carboxymethyl cellulose; a reducing agent such as a sulfite; a fluorescent brightener, or the like.
  • a surfactant known in the field of laundry detergents for example, a surfactant known in the field of laundry detergents; a re-deposition preventing agent such as acrylic acid polymer, acrylic acid-maleic acid copolymer, and carboxymethyl cellulose; a reducing agent such as a sulfite; a fluorescent brightener, or the like.
  • the component a) is contained in an amount within the range of preferably from 5 to 30% by weight, and more preferably from 10 to 30% by weight of the uni-core detergent particles obtainable in the present invention, from the viewpoint of an improvement in detergency.
  • the component b) is water contained in an amount of from 25 to 65 parts by weight, and preferably from 30 to 50 parts by weight of the surfactant composition, based on 100 parts by weight of the above-mentioned component a).
  • step B) is a step of mixing the surfactant composition obtained in step A) and base particles having a supporting ability of 20 mL/100 g or more and containing a water-soluble inorganic salt produced by spray-drying, while substantially maintaining the form of the base particles.
  • step B) by mixing the surfactant composition with the base particles containing the water-soluble inorganic salt to contact with each other, the loss of free-flowability of the surfactant composition exhibited by taking water in the surfactant composition away by the water-soluble inorganic salt can be utilized.
  • the base particles usable in step B) have a supporting ability of 20 mL/100 g or more and contain a water-soluble inorganic salt produced by spray-drying.
  • the above-mentioned base particles are prepared by spray-drying a slurry containing the water-soluble inorganic salt.
  • the water-soluble inorganic salt is not particularly limited.
  • the above-mentioned builders generally used in laundry detergents sodium carbonate, potassium carbonate, sodium sulfate, or the like is preferable.
  • the alkalizing agent may be removed from the base particles when a base material agent or
  • zeolite is used in combination with the above-mentioned water-soluble inorganic salt.
  • water in the base particles after the spray-drying is contained in an amount of preferably 5% by weight or less, and more preferably 3% by weight or less of the base particles, from the viewpoint of increasing an action of water absorption in zeolite.
  • the base particles in which the water-soluble inorganic salt and zeolite, which are preferably contained in the base particles, are formulated in an amount of 60% by weight or more in total are favorable to take away water of the surfactant composition.
  • the conditions upon spray-drying the slurry for preparing the above-mentioned base particles are not particularly limited, and a known method may be used.
  • the physical properties of the base particles used in the present invention are given hereinbelow.
  • the base particles have a supporting ability of 20 mL/100 g or more, and preferably 30 mL/100 g or more. Within this range, the aggregation of the base particles themselves is suppressed, thereby making it favorable to maintain the uni-core owned by the particle in the detergent particles.
  • the determination method for the supporting ability is as follows.
  • a cylindrical mixing vessel of an inner diameter of about 5 cm and a height of about 15 cm which is equipped with agitation impellers in the inner portion thereof is charged with 100 g of a sample.
  • linseed oil is supplied at 25°C into the mixing vessel at a rate of about 10 mL/min.
  • the supporting ability is defined as an amount of linseed oil supplied when the agitation torque reaches the highest level.
  • the base particles have a bulk density of preferably from 200 to 1000 g/L, more preferably from 300 to 1000 g/L, even more preferably from 400 to 1000 g/L, and especially preferably from 500 to 800 g/L.
  • the bulk density is measured by a method according to JIS K 3362.
  • the base particles have an average particle size of preferably from 150 to 500 ⁇ m, and more preferably from 180 to 350 ⁇ m.
  • the average particle size is calculated by vibrating a sample using standard sieves according to JIS Z 8801 (sieve openings of from 2000 to 125 ⁇ m) for 5 minutes, and thereafter determining the median particle size from a weight percentage depending upon the size openings of the sieves.
  • a mixer for mixing the surfactant composition and the base particles usable in step B) is, for example, a mixer equipped with a nozzle for adding the surfactant composition or a jacket for controlling the temperature within a mixer.
  • mixing conditions are selected such that the base particles substantially maintain their shapes, i.e., the base particles do not undergo disintegration.
  • the agitation impellers have a Froude number of preferably from 0.5 to 8, more preferably from 0.5 to 4, and even more preferably from 0.5 to 2, from the viewpoint of the suppression of the disintegration of the water-soluble inorganic salt and mixing efficiency.
  • the agitation impellers have a Froude number of preferably from 0.1 to 4, and more preferably from 0.15 to 2. Also, in a case where the mixing impellers have a ribbon shape, the agitation impellers have a Froude number of preferably from 0.05 to 4, and more preferably from 0.1 to 2.
  • a mixer equipped with agitation impellers and disintegration impellers.
  • the disintegration impellers have been conventionally subjected to high-speed rotation, from the viewpoint of accelerating mixing.
  • the phrase "not to substantially rotate the disintegration impellers" refers to a state where the disintegration impellers are not rotated at all, or the disintegration impellers are rotated within a range such that the base particles do not undergo disintegration, in consideration of shapes, sizes, and the like of the disintegration impellers, for the purpose of preventing the retention of various raw materials near the disintegration impellers.
  • the Froude number is preferably 200 or less, and more preferably 100 or less, and in a case where the disintegration impellers are intermittently rotated, the Froude number is not particularly limited.
  • the mixture can be obtained without substantially undergoing disintegration of the base particles by mixing under the conditions as described above.
  • the phrase "the base particles substantially maintain their shapes, i.e. the base particles do not undergo disintegration" as used herein refers to a state in which 70% by number or more of the base particles in the mixture maintain their shapes.
  • a method for confirmation thereof includes, for example, a method of observing particles obtained after extracting a soluble component from the resulting mixture with an organic solvent.
  • Froude number V 2 / R ⁇ g
  • a powdery raw material other than the base particles can be formulated as desired.
  • the amount of the powdery raw material is preferably 30 parts by weight or less, based on 100 parts by weight of the base particles, from the viewpoint of dissolubility
  • the term "powdery raw material other than the base particles" as used herein means a detergency-fortifying agent or an oil-absorbing agent which is in the form of powder at an ambient temperature.
  • the powdery raw materials include base material agents exhibiting a metal ion capturing ability such as zeolite and citrates; base material agents exhibiting an alkalizing ability such as sodium carbonate and potassium carbonate; base material agents exhibiting both a metal ion capturing ability and an alkalizing ability such as crystalline silicates; amorphous silica and amorphous aluminosilicates exhibiting low metal ion capturing ability but high oil-absorbing ability, and the like.
  • the detergent particles produced according to the present invention contains c) a nonionic surfactant having a melting point of 30°C or less.
  • the component c) is added to the base particles in step B).
  • the component c) is added prior to the surfactant composition prepared in step A), to control the structure of liquid crystals and/or crystals in the surfactant composition, thereby increasing the effect of suppressing the bleed-out of the component c).
  • the component c) has a melting point of 30°C or less, preferably 25°C or less, and more preferably 22°C or less.
  • a polyoxyethylene-polyoxypropylene block polymer such as a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenyl ether, an alkyl(polyoxyalkylene)polyglycoside, a polyoxyalkylene sorbitan fatty acid ester, a polyoxyalkylene glycol fatty acid ester, a polyoxyethylene-polyoxypropylene-polyoxyethylene alkyl ether (hereinafter abbreviated as EPE nonionic), or a polyoxyalkylene alkylol(fatty acid)amide is preferable.
  • an alkylene oxide includes ethylene oxide, propylene oxide, or the like, and is preferably ethylene oxide.
  • a compound in which ethylene oxide and propylene oxide, and further optionally ethylene oxide, are subjected to a block polymerization or a random polymerization to the above alcohol is preferable, from the viewpoint of dissolubility, especially dissolubility in a low temperature.
  • the EPE nonionic is preferable.
  • component c) may be used alone or in admixture of two or more kinds.
  • the nonionic surfactant may be used in the form of an aqueous solution.
  • a melting point of the component c) is determined with Mettler FP81 of FP800 Thermo System (manufactured by Mettler Instrumente AG) at a heating rate of 0.2°C/min.
  • the component c) is contained in an amount within the range of preferably from 1 to 20% by weight, and more preferably from 5 to 15% by weight of the uni-core detergent particles, from the viewpoint of an improvement in the detergency, an improvement in the anti-caking ability, and the suppression of choking upon becoming powdery.
  • the component c) may contain, for example, salts of fatty acids, polyethylene glycols, or the like (a molecular weight of from 3,000 to 30,000) as disclosed in JP-B-3161710 , to prevent the generation of the bleed-out of the component c) and deterioration of the anti-caking ability.
  • These components are formulated in an amount of preferably from 2 to 40 parts by weight, and more preferably from 2 to 30 parts by weight, based on 100 parts by weight of the component c).
  • water contained in the surfactant composition is taken away by the water-soluble inorganic salt, and free-flowability of the surfactant composition is lost, thereby allowing a suppression of the bleed-out of the component c) and an improvement in the anti-caking ability even if the component c) does not contain the above salts of fatty acids, polyethylene glycols, or the like.
  • the above salts of fatty acids, polyethylene glycols, or the like may be contained in order to make the suppression of the bleed-out of the component c) and an improvement in the anti-caking ability more effective.
  • a surfactant which is known in the field of laundry detergents may be added.
  • an acid precursor such as a linear alkylbenzenesulfonic acid
  • a method of adding an acid precursor such as a linear alkylbenzenesulfonic acid prior to the surfactant composition is preferable in order to suppress the disintegration of the surfactant composition.
  • polyethylene glycol (PEG) and/or a fatty acid, and/or soap water is added in an amount of from 1 to 10 parts by weight, based on 100 parts by weight of the base particles to coat the surface of the base particles because the coating improves the anti-caking ability.
  • PEG polyethylene glycol
  • soap water is preferable because the addition allows suppression of the aggregation and an increase in dispersibility, thereby improving dissolubility, upon dissolving the detergent particles.
  • the temperature within a mixer during the mixing is preferably a temperature that allows to efficiently mix the surfactant composition and the base particles while substantially suppressing the disintegration of the base particles.
  • a temperature equal to or higher than a pour point of the surfactant composition to be mixed is preferable, more preferably a temperature higher than the pour point by 10°C or more, and especially preferably a temperature higher than the pour point by 20°C or more.
  • the mixing time is preferably from 2 to 10 minutes or so.
  • the temperature control within the mixer can be carried out by allowing cold water or warm water to flow through a jacket or the like. Therefore, the mixer usable for mixing is preferably a mixer having a construction equipped with a jacket.
  • a method for mixing the surfactant composition and the base particles may be a batch process or a continuous process.
  • the base particles are previously supplied to a mixer, and thereafter the surfactant composition is added thereto.
  • the temperature at which the surfactant composition is fed is preferably 70°C or less, and more preferably 60°C or less, from the viewpoint of the stability of the surfactant composition.
  • the mixer is not particularly limited, as long as a mixer which is generally usable for mixing in a batch process is used.
  • a mixer of which - mixing impellers have a paddle shape (1) a mixer in which blending of powders is carried out by having an agitating shaft in the inner portion of a mixing vessel and attaching agitating impellers on the agitating shaft: for example, Henschel Mixer (manufactured by Mitsui Miike Machinery Co., Ltd.), High-Speed Mixer (manufactured by Fukae Powtec Corp.), Vertical Granulator (manufactured by Powrex Corp.), Lödige Mixer (manufactured by MATSUBO CORPORATION), PLOUGH SHARE Mixer (manufactured by PACIFIC MACHINERY & ENGINEERING Co., LTD.), TSK-MTI Mixer (manufactured by Tsukishima
  • the mixer is not particularly limited, as long as a continuous mixer which is generally used for a continuous mixing is used.
  • the base particles and the surfactant composition may be mixed by using a continuous-type mixer among the above-mentioned mixers.
  • Step C) is a step of surface-modifying the mixture obtained in step B) with a fine powder.
  • the fine powder a fine powder of which primary particles have an average particle size of 20 ⁇ m or less is preferable, from the viewpoint of improving the coating ratio of the powder particles, and improving free-flowability and anti-caking ability of the powder particles.
  • the average particle size is determined by a method utilizing light scattering, for example a particle analyzer (manufactured by HORIBA, LTD.), or by a microscopic observation.
  • an aluminosilicate is desirable, and an inorganic fine powder such as calcium silicate, silicon dioxide, bentonite, sodium tripolyphosphate, talc, clay, an amorphous silica derivative, or a silicate compound such as a crystalline silicate compound, or a metal soap of which primary particles have a size of 20 ⁇ m or less can be used.
  • an inorganic fine powder such as calcium silicate, silicon dioxide, bentonite, sodium tripolyphosphate, talc, clay, an amorphous silica derivative, or a silicate compound such as a crystalline silicate compound, or a metal soap of which primary particles have a size of 20 ⁇ m or less can be used.
  • the fine powder has a high ion exchanging ability and an alkalizing ability, from the viewpoint of detergency.
  • the amount of the fine powder used is preferably from 0.5 to 40 parts by weight, and more preferably from 1 to 30 parts by weight, based on 100 parts by weight of the mixture obtained in step B) from the viewpoint of free-flowability and feel of use.
  • mixing conditions in which the shape of the base particles containing a surfactant composition is substantially maintained may be selected.
  • Preferred mixing conditions are the use of a mixer equipped with both the agitation impellers and the disintegration impellers.
  • the agitation impellers equipped in the mixer have a Froude number of preferably 10 or less, and more preferably 7 or less, from the viewpoint of the suppression of the disintegration of the base particles.
  • the agitation impellers have a Froude number of preferably 2 or more, and even more preferably 3 or more, from the viewpoint of the efficiency of the mixing with the fine powder and the dispersion of the fine powder.
  • the disintegration impellers have a Froude number of preferably 8000 or less, and more preferably 5000 or less, from the viewpoint of the efficiency of mixing with the fine powder and the dispersion of the fine powder.
  • Froude number is within this range, uni-core detergent particles having excellent free-flowability can be obtained.
  • Preferred mixers include mixers equipped with both the agitation impellers and the disintegration impellers among the mixers usable jn step B).
  • the temperature-control of the mixture is facilitated.
  • a non-heat resistant component such as perfume or an enzyme
  • the mixture is temperature-controlled in step C).
  • the temperature can be controlled by setting a jacket temperature or aeration.
  • a preferred embodiment is to add a part of a fine powder at the termination of step B).
  • Uni-core detergent particles are obtained in the manner as described above.
  • the uni-core detergent particles those containing 20 to 80% by weight of the base particles, 5 to 30% by weight of the component a), a modifying agent fine powder, and separately added detergent components (for example, a fluorescer, an enzyme, a perfume, a defoaming agent, a bleaching agent, a bleaching activator, or the like) are preferable.
  • the term "uni-core detergent particle” refers to a detergent composition which is produced in which the base particle is used as a core, which is a detergent particle in which a single detergent particle substantially has one base particle as a core.
  • the degree of particle growth defined by the following formula can be used.
  • the uni-core detergent particles as referred to herein have a degree of particle growth of 1.5 or less, preferably 1.4 or less, and more preferably 1.3 or less. Although its lower limit is not particularly limited, a degree of particle growth of 1.0 or more is preferable.
  • Degree of Particle Growth Average Particle Size of Detergent Particles Obtainable in Step C ) Average Particle Size of Base Particles
  • the uni-core detergent particles have an average particle size of 150 ⁇ m or more, preferably from 150 to 500 ⁇ m, and more preferably from 180 to 350 ⁇ m.
  • the uni-core detergent particles have a bulk density of preferably from 300 to 1000 g/L, more preferably from 500 to 1000 g/L, even more preferably from 600 to 1000 g/L, and especially preferably from 650 to 850 g/L.
  • a method including the step of, for example, adding a surfactant or the like to a spray-dried slurry, thereby lowering a bulk density of a base particle; formulating a powder raw material having a bulk density lower than a base particle as a powder raw material other than the base particle in step B); reducing an amount of a surfactant composition to be mixed with a base particle; or the like can be employed.
  • the uni-core detergent particles have free-flowability, in terms of a flow time, of preferably 10 seconds or shorter, and more preferably 8 seconds or shorter.
  • the flow time refers to a time period required for cascading 100 mL of powder from a hopper used in a measurement of bulk density as defined in JIS K 3362.
  • the yield of the uni-core detergent particles is calculated by dividing the weight of a sample passing through a sieve having an opening of 1180 ⁇ m by the weight of an entire sample.
  • the yield is preferably 90% or more, and more preferably 95% or more.
  • the uni-core detergent particles obtainable by the production method having the constitution as described above have, as mentioned above suppressed particle growth, and sharp particle size distribution, and have improved external appearance and favorable free-flowability, whereby detergent particles having excellent dissolubility can be obtained in a high yield.
  • a 60-seconds dissolution ratio of the detergent particles can be used.
  • the dissolution ratio is preferably 80% or more, and more preferably 90% or more.
  • the 60-seconds dissolution ratio of the detergent particles is calculated by the method described below.
  • a 1-L beaker (a cylindrical form having an inner diameter of 105 mm and a height of 150 mm, for instance, a 1-L beaker manufactured by Iwaki Glass Co., Ltd.) is charged with 1 L of hard water cooled to 5°C and having a water hardness corresponding to 71.2 mg CaCO 3 /L (a molar ratio of Ca/Mg: 7/3).
  • a liquid dispersion of the detergent particles in the beaker is filtered with a standard sieve (diameter: 100 mm) having a sieve-opening of 74 ⁇ m as defined by JIS Z 8801 of a known weight. Thereafter, water-containing detergent particles remaining on the sieve are collected in an open vessel of a known weight together with the sieve.
  • the operation time from the start of filtration to collection of the sieve is set at 10 sec ⁇ 2 sec. The insoluble remnants of the collected detergent particles are dried for one hour in an electric dryer heated to 105°C.
  • Dissolution Ratio % 1 - T / S ⁇ 100 wherein S is a weight (g) of the detergent particles supplied; and T is a dry weight (g) of insoluble remnants of the detergent particles remaining on the sieve when an aqueous solution prepared under the above stirring conditions is filtered with the sieve (drying conditions: maintaining at a temperature of 105°C for 1 hour, and thereafter maintaining for 30 minutes in a desiccator (25°C) containing silica gel).
  • the detergent particles of the present invention are excellent in bleed-out preventing property of a nonionic surfactant.
  • the bleed-out property of a nonionic surfactant will be evaluated as follows.
  • An open-top box having dimensions of 10.2 cm in length, 6.2 cm in width, and 4 cm in height is made out of a filter paper (No. 2, manufactured by ADVANTEC) by stapling the filter paper at four corners. Two lines are previously drawn with an oil-based magic marker to be crossed with each other, along the diagonals of the portion corresponding the bottom of the box.
  • the box is charged with a 200 mL sample, and sealed in an acrylic casing. The sample is allowed to stand in a thermostat at a temperature of 30°C for 7 days, and the bleed-out property of a nonionic surfactant is evaluated.
  • the judgment is made by visually examining the extent of bleeding of the oil-based magic marker drawn on the bottom of the box after discharging the sample.
  • the evaluation was made on 1 to 5 ranks, and the state of each rank is as follows.
  • Base particles used in Reference Examples 1-1, 1-2, 1-4, 1-5 and in Examples 1-3 and 1-6 to 1-8 were produced by the following procedures.
  • the amount 460 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 120 kg of sodium sulfate, 140 kg of sodium carbonate and 5 kg of sodium sulfite were added thereto. After agitating the mixture for 10 minutes, 170 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. After agitating the mixture for additional 10 minutes, 40 kg of sodium chloride and 140 kg of zeolite were added thereto, and the resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 58°C.
  • This slurry was sprayed at a spraying pressure of 25 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 225°C to the bottom of the tower and exhausted at a temperature of 105°C from the top of the tower.
  • the water content of the base particles was 1.6%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 281 ⁇ m, a bulk density of 506 g/L, a free-flowability of 5.8 seconds, and a supporting ability of 45 mL/100 g.
  • Base particles used in Examples 1-10 and in Reference Example 1-9 were produced by the following procedures.
  • the amount 430 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 160 kg of sodium sulfate was added thereto. After agitating the mixture for 5 minutes, 100 kg of sodium silicate (effective ingredient: 40%) and 10 kg of carboxymethyl cellulose were added thereto. After agitating the mixture for 5 minutes, 60 kg of sodium tripolyphosphate and 130 kg of sodium carbonate were added thereto. After agitating the mixture for 15 minutes, 60 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. The resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 60°C.
  • This slurry was sprayed at a spraying pressure of 40 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 235°C to the bottom of the tower and exhausted at a temperature of 115°C from the top of the tower.
  • the water content of the base particles was 2.0%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 203 ⁇ m, a bulk density of 420 g/L, a free-flowability of 6.4 seconds, and a supporting ability of 32 mL/100 g.
  • Base particles used in Reference Example 1-11 were produced by the following procedures. The amount 413 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 135 kg of sodium sulfate was added thereto. After agitating the mixture for 5 minutes, 60 kg of sodium silicate (effective ingredient: 40%) and 12 kg of carboxymethyl cellulose were added thereto. After agitating the mixture for 5 minutes, 50 kg of sodium tripolyphosphate and 150 kg of sodium carbonate were added thereto. After agitating the mixture for 15 minutes, 130 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. After agitating the resulting mixture for additional 10 minutes, 50 kg of sodium chloride was added thereto, and the resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 60°C.
  • This slurry was sprayed at a spraying pressure of 35 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 235°C to the bottom of the tower and exhausted at a temperature of 112°C from the top of the tower.
  • the water content of the base particles was 1.2%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 240 ⁇ m, a bulk density of 374 g/L, a free-flowability of 6.0 seconds, and a supporting ability of 30 mL/100 g.
  • the rotation was temporarily stopped, and 13 parts by weight of a fine powder (zeolite) was supplied thereto.
  • the rotations of the main shaft (rotational speed: 150 r/min, Froude number of agitation impellers: 3.8) and the chopper (rotational speed of chopper: 3600 r/min, Froude number of disintegration impellers: 1010) were carried out for 15 seconds. After the 15 seconds, the rotation of the chopper was stopped, and the rotation only with the main shaft was carried out for additional 30 seconds, and the resulting detergent particles were then discharged.
  • the physical properties of the resulting detergent particles were as listed in Table 2.
  • the component b) in the surfactant composition listed in Table 1 was 39 parts by weight, based on 100 parts by weight of the component a), and the viscosity of the surfactant composition was 4.2 Pa ⁇ s (60°C)
  • Detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2. The physical properties of the resulting detergent particles are shown in Table 2.
  • Example 1-3 as the surfactant composition, the same one as that used in Reference Example 1-1 was used.
  • the components and viscosity are as shown in Table 1.
  • Detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, provided that the polyoxyethylene alkyl ether and the surfactant composition were previously mixed and then added over 2 minutes. The physical properties of the resulting detergent particles are shown in Table 2.
  • the surfactant composition used in Reference Example 1-4 was the same one as that used in Reference Example 1-1.
  • the components and viscosity are as shown in Table 1.
  • Detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, except that the surfactant composition was supplied over 1 minute, and thereafter the polyoxyethylene alkyl ether was supplied over 1 minute.
  • the physical properties of the resulting detergent particles are shown in Table 2.
  • surfactant composition used in Reference Example 1-5 was the same one as that used in Reference Example 1-1.
  • the components and viscosity are as shown in Table 1.
  • Detergent particles were obtained in the same manner as in Example 1-3 with the components listed in Table 2, except for the amounts of the polyoxyethylene alkyl ether and the surfactant composition. The physical properties of the resulting detergent particles are shown in Table 2.
  • surfactant compositions used in Examples 1-6 and 1-7 were the same one as that used in Reference Example 1-1.
  • the components and viscosity are as shown in Table 1.
  • the polyoxyethylene alkyl ether was supplied and the surfactant composition was then supplied in the same manner as in Example 1-3 with the components listed in Table 2, provided that 2.0 parts by weight of polyethylene glycol was previously mixed with the polyoxyethylene alkyl ether, and the mixture was then added. After mixing the components for 4 minutes, 3.6 parts by weight of the fatty acid was added thereto over 1 minute, subsequently mixing was carried out for 1 minute, and the rotations were temporarily stopped. The subsequent procedures were carried out in the same manner as in Example 1-3. The physical properties of the resulting detergent particles are shown in Table 2.
  • Example 1-8 the surfactant composition used in Example 1-8 was the same one as that used in Reference Example 1-1.
  • the components and viscosity are as shown in Table 1.
  • Detergent particles were obtained in the same manner as in Example 1-1 with the components listed in Table 2. The physical properties of the resulting detergent particles are shown in Table 2.
  • Detergent particles were obtained in the same manner as in Example 1-8 with the components listed in Table 2. Here, as a fine powder, sodium tripolyphosphate was used. The physical properties of the resulting detergent particles are shown in Table 2.
  • the powder raw material composed of 100 parts by weight of the base particles previously heated to 50°C was supplied into Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the rotation of a main shaft was started (rotational speed of main shaft: 80 r/min, Froude number of agitation impellers: 1.07).
  • Lödige Mixer manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket
  • Froude number of agitation impellers 1.07
  • hot water at 80°C was allowed to flow through the jacket at 10 L/minute, without rotating a chopper (equipped with disintegration impellers).
  • an average particle size (entire particles) of the detergent particles in addition to an average particle size (entire particles) of the detergent particles, an average particle size, of the detergent particles that passed through the sieve having an opening of 1180 ⁇ m used in the calculation of yield was also listed together.
  • the free-flowability, the bulk density, and the dissolution ratio of the detergent particles, and the bleed-out property of the component c) were determined and/or evaluated using detergent particles which were allowed to pass through the above-mentioned sieve to exclude aggregated or coarse particles.
  • Detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2, using a base particle substitute powder in place of the base particles.
  • a base particle substitute powder a powder produced by dry-blending the components so as to have the ratio of the powder raw material blended in the base particles in a given compositional ratio was used.
  • the physical properties of the resulting detergent particles are shown in Table 2.
  • Detergent particles having excellent free-flowability were obtained in the same manner as in Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1-11 and in Examples 1-3, 1-6, 1-7, 1-8 and 1-10; however, the amount of a modifying agent fine powder (zeolite) which was necessary to obtain a detergent having excellent free-flowability was dramatically increased as compared to those of Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1-11 and in Examples 1-3, 1-6, 1-7, 1-8 and 1-10. Also, the aggregation and formation of coarse particles of the particles took place, thereby dramatically lowering its yield. In addition, its dissolution ratio was lowered. The amount and yield of the fine powder added at this time, and the average particle size, the free-flowability, the bulk density, and the dissolution ratio of the detergent particles are shown in Table 2.
  • the surfactant composition used in Comparative Example 1-1 was the same one as that used in Reference Example 1-1.
  • the components and water content and viscosity are as shown in Table 1.
  • Detergent particles were obtained in the same manner as in Reference Example 1-1 with the components listed in Table 2, using a base particle substitute powder in the same manner as in Comparative Example 1-1.
  • the physical properties of the resulting detergent particles are shown in Table 2.
  • a modifying agent fine powder (zeolite) which was necessary to improve its free-flowability was dramatically increased as compared to those of Reference Examples 1-1, 1-2, 1-4, 1-5, 1-9, 1-11 and in Examples 1-3, 1-6, 1-7, 1-8 and 1-10. Also, the aggregation and formation of coarse particles of the particles took place, thereby dramatically lowering its yield.
  • the amount and yield of the fine powder (zeolite) added at this time, and the average particle size, the free-flowability, the bulk density, and the dissolution ratio of the detergent particles are shown in Table 2.
  • Base particles used in Reference Examples 2-1, 2-2, 2-4, 2-5 and in Examples 2-3 and 2-6 were produced by the following procedures.
  • the amount 460 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 120 kg of sodium sulfate, 140 kg of sodium carbonate and 5 kg of sodium sulfite were added thereto. After agitating the mixture for 10 minutes, 170 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. After agitating the mixture for additional 10 minutes, 40 kg of sodium chloride and 140 kg of zeolite were added thereto, and the resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 58°C.
  • This slurry was sprayed at a spraying pressure of 25 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 225°C to the bottom of the tower and exhausted at a temperature of 105°C from the top of the tower.
  • the water content of the base particles was 1.6%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 281 ⁇ m, a bulk density of 506 g/L, a free-flowability of 5.8 seconds, and a supporting ability of 45 mL/100 g. 45 mL/100 g.
  • Base particles used in Reference Examples 2-7 and in Example 2-8 were produced by the following procedures.
  • the amount 430 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 160 kg of sodium sulfate was added thereto. After agitating the mixture for 5 minutes, 100 kg of sodium silicate (effective ingredient: 40%) and 10 kg of carboxymethyl cellulose were added thereto. After agitating the mixture for 5 minutes, 60 kg of sodium tripolyphosphate and 130 kg of sodium carbonate were added thereto. After agitating the mixture for 15 minutes, 60 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. The resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 60°C.
  • This slurry was sprayed at a spraying pressure of 40 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 235°C to the bottom of the tower and exhausted at a temperature of 115°C from the top of the tower.
  • the water content of the base particles was 2.0%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 203 ⁇ m, a bulk density of 420 g/L, a free-flowability of 6.4 seconds, and a supporting ability of 32 mL/100g.
  • Base particles used in Reference Example 2-9 were produced by the following procedures. The amount 413 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 135 kg of sodium sulfate was added thereto. After agitating the mixture for 5 minutes, 60 kg of sodium silicate (effective ingredient: 40%) and 12 kg of carboxymethyl cellulose were added thereto. After agitating the mixture for 5 minutes, 50 kg of sodium tripolyphosphate and 150 kg of sodium carbonate were added thereto. After agitating the mixture for 15 minutes, 130 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. After agitating the resulting mixture for additional 10 minutes, 50 kg of sodium chloride was added thereto, and the resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 60°C.
  • This slurry was sprayed at a spraying pressure of 35 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 235°C to the bottom of the tower and exhausted at a temperature of 112°C from the top of the tower.
  • the water content of the base particles was 1.2%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 240 ⁇ m, a bulk density of 374 g/L, a free-flowability of 6.0 seconds, and a supporting ability of 30 mL/100 g.
  • the rotation was temporarily stopped, and 42 parts by weight of a fine powder (zeolite) was supplied thereto.
  • the rotations of the main shaft (rotational speed: 150 r/min, Froude number of agitation impellers: 3.8) and the chopper (rotational speed of chopper: 3600 r/min, Froude number of disintegration impellers: 1010) were carried out for 15 seconds. After the 15 seconds, the rotation of the chopper was stopped, and the rotation only with the main shaft was carried out for additional 30 seconds, and the resulting detergent particles were then discharged.
  • the physical properties of the resulting detergent particles were as listed in Table 4.
  • the component b) in the surfactant composition listed in Table 3 was 43 parts by weight, based on 100 parts by weight of the component a), and the viscosity of the surfactant composition was 3.1 Pa ⁇ s (60°C).
  • Detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4. The physical properties of the resulting detergent particles are shown in Table 4.
  • Example 2-3 as the surfactant composition, the same one as that used in Reference Example 2-1 was used.
  • the components and viscosity are as shown in Table 3.
  • Detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4, provided that the polyoxyethylene alkyl ether and the surfactant composition were previously mixed and then added over 2 minutes. The physical properties of the resulting detergent particles are shown in Table 4.
  • the surfactant composition used in Reference Example 2-4 was the same one as that used in Reference Example 2-1.
  • the components and viscosity are as shown in Table 3.
  • Detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4, except that the surfactant composition was supplied over 1 minute, and thereafter the polyoxyethylene alkyl ether was supplied over 1 minute.
  • the physical properties of the resulting detergent particles are shown in Table 4.
  • the surfactant composition used in Reference Example 2-5 was the same one as that used in Reference Example 2-1.
  • the components and viscosity are as shown in Table 3.
  • the polyoxyethylene alkyl ether was supplied and the surfactant composition was then supplied in the same manner as in Example 2-3 with the components listed in Table 4, provided that 2.0 parts by weight of polyethylene glycol was previously mixed with the polyoxyethylene alkyl ether, and the mixture was then added.
  • the physical properties of the resulting detergent particles are shown in Table 4. After mixing the components for 4 minutes, 3.6 parts by weight of the fatty acid was added thereto over 1 minute, subsequently mixing was carried out for 1 minute, and the rotations were temporarily stopped. The subsequent procedures were carried out in the same manner as in Example 2-3.
  • Example 2-6 was the same one as that used in Reference Example 2-1.
  • the components and viscosity are as shown in Table 3.
  • Detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4. The physical properties of the resulting detergent particles are shown in Table 4.
  • Detergent particles were obtained in the same manner as in Example 2-3 with the components listed in Table 4. Here, as a fine powder, sodium tripolyphosphate was used. The physical properties of the resulting detergent particles are shown in Table 4.
  • the powder raw material composed of 100 parts by weight of the base particles previously heated to 50°C was supplied into Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the rotation of a main shaft was started (rotational speed of main shaft: 80 r/min, Froude number of agitation impellers: 1.07).
  • Lödige Mixer manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket
  • Froude number of agitation impellers 1.07
  • hot water at 80°C was allowed to flow through the jacket at 10 L/minute, without rotating a chopper (equipped with disintegration impellers).
  • Detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4, using a base particle substitute powder in place of the base particles.
  • a base particle substitute powder a powder produced by dry-blending the components so as to have the ratio of the powder raw material blended in the base particles in a given compositional ratio was used.
  • the physical properties of the resulting detergent particles are shown in Table 4.
  • Detergent particles having excellent free-flowability were obtained in the same manner as in Reference Examples 2-1, 2-2, 2-4, 2-5, 2-7, 2-9, and in Examples 2-3, 2-6 and 2-8 however, the amount of a modifying agent fine powder (zeolite) which was necessary to obtain a detergent having excellent free-flowability was dramatically increased as compared to those of Reference Examples 2-1, 2-2, 2-4, 2-5, 2-7, 2-9, and in Examples 2-3, 2-6 and 2-8. Also, the aggregation and formation of coarse particles of the particles took place, thereby dramatically lowering its yield. In addition, its dissolution ratio was lowered.
  • zeolite zeolite
  • the surfactant composition used in Comparative Example 2-1 was the same one as that used in Reference Example 2-1.
  • the components and water content and viscosity are as shown in Table 3.
  • Detergent particles were obtained in the same manner as in Reference Example 2-1 with the components listed in Table 4, using a base particle substitute powder in the same manner as in Comparative Example 2-1.
  • the physical properties of the resulting detergent particles are shown in Table 4.
  • the amount of a modifying agent fine powder (zeolite) which was necessary to improve its free-flowability was dramatically increased as compared to those of Reference Examples 2-1, 2-2, 2-4, 2-5, 2-7, 2-9, and in Examples 2-3, 2-6 and 2-8.
  • the surfactant composition used in Comparative Example 2-2 was the same one as that used in Reference Example 2-1.
  • Base particles used in Examples 3-1 and 3-2 were produced by the following procedures.
  • the amount 495 kg of water was added to a 1 m 3 -mixing vessel having agitation impellers. After the water temperature reached 55°C, 218 kg of sodium sulfate was added thereto. After agitating the mixture for 10 minutes, 168 kg of a 40% by weight-aqueous sodium polyacrylate solution was added thereto. After agitating the mixture for additional 10 minutes, 45 kg of sodium chloride and 220 kg of zeolite were added thereto, and the resulting mixture was agitated for 30 minutes, to obtain a homogeneous slurry. The final temperature of this slurry was 58°C.
  • This slurry was sprayed at a spraying pressure of 25 kg/cm 2 from a pressure spray nozzle arranged near the top of a spray-drying tower.
  • a high-temperature gas to be fed to the spray-drying tower was supplied at a temperature of 225°C to the bottom of the tower and exhausted at a temperature of 105°C from the top of the tower.
  • the water content of the base particles was 2.5%.
  • the resulting base particles had physical properties such that the base particles had an average particle size of 192 ⁇ m, a bulk density of 536 g/L, a free-flowability of 5.2 seconds, and a supporting ability of 45 mL/100 g.
  • the components of the surfactant composition used in Examples 3-1 to 3-2 are those as listed in Table 5.
  • the powder raw material composed of 100 parts by weight of the base particles previously heated to 50°C was supplied into Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the rotation of a main shaft was started (rotational speed of main shaft: 80 r/min, Froude number of agitation impellers: 1.07).
  • Lödige Mixer manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket
  • Froude number of agitation impellers 1.07
  • hot water at 80°C was allowed to flow through the jacket at 10 L/minute, without rotating a chopper (equipped with disintegration impellers).
  • Zeolite manufactured by Zeobuilder under the trade name of Zeobuilder (zeolite 4A-type, average particle size 3.5 ⁇ m); and Polyoxyethylene Alkyl Ether: manufactured by Kao Corporation under the trade name of 108KM (average number of moles of ethylene oxide: 8.5, number of carbon atoms of alkyl moiety: 12-14), melting point: 18°C).
  • the powder raw material composed of 100 parts by weight of the base particles previously heated to 50°C was supplied into Lödige Mixer (manufactured by MATSUBO CORPORATION; capacity: 20 L, equipped with a jacket), and the rotation of a main shaft was started (rotational speed of main shaft: 80 r/min, Froude number of agitation impellers: 1.07).
  • hot water at 80°C was allowed to flow through the jacket at 10 L/minute, without rotating a chopper (equipped with disintegration impellers).
  • 34 parts by weight of a surfactant composition at 60°C was supplied over 1 minute, and the components were then mixed for 6 minutes.
  • the rotations were temporarily stopped, and 34 parts by weight of a fine powder (zeolite) was supplied to the mixer.
  • the rotations of the main shaft (rotational speed: 150 r/min, Froude number of agitation impellers: 3.8) and the chopper (rotational speed of chopper: 3600 r/min, Froude number of disintegration impellers: 1010) were carried out for 15 seconds. After the 15 seconds, the rotation of the chopper was stopped, and the rotation only with the main shaft was carried out for additional 30 seconds, and the resulting detergent particles were discharged.
  • the physical properties of the resulting detergent particles were as listed in Table 6.
  • Example 3-2 the surfactant composition used in Example 3-2 was the same one as that used in Example 3-2.
  • the components and water content and viscosity are as shown in Table 5.
  • the uni-core detergent particles of the present invention can be suitably used in, for example, the production of a laundry detergent, a dishwashing detergent, or the like.

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Claims (7)

  1. Procédé de production de particules de détergent à noyau unique présentant une taille moyenne de particules de 150 µm ou plus et un degré de croissance de particules de 1,5 ou moins, comprenant les étapes consistant :
    étape A) à préparer une composition tensioactive comprenant :
    a) un agent tensioactif anionique représenté par l'une des formules suivantes (1) à (3) :

            R-O- SO3M     (1)

    où R est un groupe alkyle ou un groupe alcényle ayant 10 à 18 atomes de carbone ; et M est un atome de métal alcalin ou une amine,

            R-O(CH2CH2O)n-SO3M     (2)

    où R est un groupe alkyle ou un groupe alcényle ayant 10 à 18 atomes de carbone ; n est un nombre moyen de moles ajoutées de 0,1 à 3,0 ; et M est un atome de métal alcalin ou un ammonium ou une amine organique et
    Figure imgb0015
     où R est un groupe alkyle ou un groupe alcényle ayant 4 à 22 atomes de carbone ; M est un atome de métal alcalin, un atome de métal alcalino-terreux, une alkanolamine ou un ammonium ; et A est un groupe alkyle ayant 1 à 4 atomes de carbone, H, ou M, et
    b) de l'eau en une quantité de 25 à 65 parties en poids pour 100 parties en poids dudit composant a) ;
    étape B) à mélanger la composition tensioactive obtenue dans l'étape A) et des particules de base ayant une capacité de tolérance de 20 mL/100 g ou plus et comprenant un sel inorganique soluble dans l'eau produit par séchage par pulvérisation, tout en conservant sensiblement la forme des particules de base ; et
    étape C) à modifier la surface du mélange obtenu dans l'étape B) avec une poudre fine,
    où les particules de détergent comprennent en outre c) un agent tensioactif non ionique présentant un point de fusion de 30°C ou moins dans la plage allant de 1 à 20% en poids des particules de détergent,
    le composant c) étant mélangé avec les particules de base avant la composition tensioactive préparée dans l'étape A).
  2. Procédé de production de particules de détergent à noyau unique selon la revendication 1, où le composant a) est présent en une quantité allant de 5 à 30% en poids des particules de détergent.
  3. Procédé de production de particules de détergent à noyau unique selon la revendication 1 ou 2, où la quantité c) de l'agent tensioactif non ionique présentant un point de fusion de 30°C ou moins dans les particules de détergent est dans la plage allant de 5 à 15% en poids des particules de détergent.
  4. Procédé de production de particules de détergent à noyau unique selon l'une quelconque des revendications 1 à 3, où le sel inorganique soluble dans l'eau est au moins un élément choisi dans le groupe constitué de carbonate de sodium, de carbonate de potassium, et de sulfate de sodium.
  5. Procédé de production de particules de détergent à noyau unique selon l'une quelconque des revendications 1 à 4, où une densité apparente des particules de base est de 200 à 1000 g/L.
  6. Procédé de production de particules de détergent à noyau unique selon l'une quelconque des revendications 1 à 5, où la poudre fine est un aluminosilicate.
  7. Procédé de production de particules de détergent à noyau unique selon l'une quelconque des revendications 1 à 6, où une quantité de la poudre fine est comprise entre 0,5 et 40 parties en poids sur 100 parties en poids du mélange obtenu dans l'étape B).
EP05768548.9A 2004-08-06 2005-08-05 Procede pour la production de particules de detergents a noyau unique Not-in-force EP1788071B1 (fr)

Applications Claiming Priority (3)

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JP2004231510 2004-08-06
JP2004300669 2004-10-14
PCT/JP2005/014453 WO2006013982A1 (fr) 2004-08-06 2005-08-05 Procédé pour la production de particules de détergents à noyau unique

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JP2008101196A (ja) * 2006-09-21 2008-05-01 Kao Corp 洗剤粒子群
EP2450428A4 (fr) * 2009-06-30 2014-12-03 Kao Corp Procédé de production de granulés de détergent d'une masse volumique apparente élevée
EP2502981A4 (fr) * 2009-11-18 2014-07-23 Kao Corp Procédé de production de granules de détergent
WO2011074522A1 (fr) * 2009-12-17 2011-06-23 花王株式会社 Procédé de production de particules de détergent

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CA2027518A1 (fr) * 1990-10-03 1992-04-04 Richard L. Tadsen Methode de preparation de compositions detergentes a haute densite, contenant des particules tensio-actives sensibles au ph
DE4415369C1 (de) * 1994-05-02 1995-08-31 Henkel Kgaa Heterogene Tensidgranulate
WO1999029829A1 (fr) * 1997-12-10 1999-06-17 Kao Corporation Particules detergentes et leur procede de preparation
CN1170921C (zh) * 1999-06-14 2004-10-13 花王株式会社 基本颗粒物和颗粒状洗涤剂
JP3720632B2 (ja) * 1999-06-14 2005-11-30 花王株式会社 ベース顆粒群
JP3352977B2 (ja) * 1999-06-15 2002-12-03 花王株式会社 固形状洗剤
JP3444817B2 (ja) * 1999-06-16 2003-09-08 花王株式会社 洗剤粒子群の製法
JP3828489B2 (ja) * 2002-12-27 2006-10-04 花王株式会社 洗剤粒子群の製造法
JP3897303B2 (ja) * 2003-01-06 2007-03-22 住友ベークライト株式会社 一液型エポキシ樹脂組成物

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WO2006013982A1 (fr) 2006-02-09
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CN101001943A (zh) 2007-07-18
EP1788071A4 (fr) 2009-08-12
CN101001943B (zh) 2010-05-05

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