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
  • C11D3/02—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
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
• • 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
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • 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
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • 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
  • C11D3/06—Phosphates, including polyphosphates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates

Definitions

• the present invention relates to particles for supporting a surfactant and a method for producing the particles. Further, the present invention relates to high-density detergent particles in which the particles for supporting a surfactant are used, and a detergent composition containing the detergent particles.
• One method of obtaining a powder detergent is a method including the step of supporting a liquid surfactant on particles for supporting a surfactant.
• the particles for supporting a surfactant are desired to have a high supporting ability of the liquid surfactant.
• the supporting abilities desired for the particles for supporting a surfactant are two factors of being capable of supporting a liquid surfactant in a large amount (supporting capacity), and being capable of firmly holding the liquid surfactant that is once absorbed in an inner portion of the particles without bleeding out (supporting ability).
• the supporting capacity is important from the viewpoint of blending a surfactant in a necessary amount for detergency performance, and the supporting ability is important from the viewpoint of suppressing bleed-out of the liquid surfactant, and from the viewpoint of preventing the free-flowability of a powder detergent from being lowered, caking, or preventing the liquid surfactant from being migrated to a vessel or the surface.
• the particles for supporting a surfactant are desired to have a property of quickly absorbing a liquid surfactant (absorbing rate), from the viewpoint of productivity.
• Patent Publication 1 discloses particles for supporting a surfactant prepared by spray-drying a preparation liquid containing a water-soluble polymer and a water-soluble salt.
• spray-drying is essential, and a method without employing spray-drying is desired, from the viewpoint of economic advantages.
• Patent Publication 2 discloses a method of drying a composition containing a hydrated inorganic salt and a polymeric organic binder.
• this method is a technique essentially for increasing absorption ability (corresponding to supporting capacity in the present invention) by drying the composition to thereby release hydration water, by which the adjustments of supporting ability and absorbing rate are very difficult. For this reason, particles for supporting a surfactant that are excellent in all of the supporting capacity/supporting ability/absorbing rate are in demand.
• an object of the present invention is to produce particles for supporting a surfactant that are excellent in supporting capacity/supporting ability/absorbing rate of a liquid surfactant composition without employing spray-drying.
• an object is to provide high-density detergent particles in which the particles for supporting a surfactant are used, and a detergent composition containing the detergent composition.
• the gist of the present invention relates to:
• the effects that particles for supporting a surfactant having excellent supporting capacity/supporting ability/absorbing rate of a liquid surfactant composition can be contained by a method without employing spray-drying are exhibited. Further, the effects that detergent particles having excellent detergent performance, quality or the like can be efficiently obtained by supporting a liquid surfactant composition on the particles for supporting a surfactant are exhibited.
• a particle for supporting a surfactant refers to a particle containing at least a powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more, and water or an aqueous binder solution.
• a particle for supporting a surfactant is preferably a particle obtained by adding water or an aqueous binder solution to a mixed powder containing a powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more, and forming particles with a low-shearing granulator, and the particle is used for supporting a liquid surfactant composition.
• a collective member of the particle is referred to as particles for supporting a surfactant.
• a detergent particle refers to a particle containing a surfactant, a builder, or the like, in which the surfactant contains a liquid surfactant composition supported by a particle for supporting a surfactant, and detergent particles refer to a collective member of detergent particles.
• a detergent composition means a composition that contains detergent particles and separately added detergent components other than the detergent particles as desired (for example, a builder granule, a fluorescer, an enzyme, a perfume, a defoaming agent, a bleaching agent, a bleaching activator, or the like).
• water solubility means that solubility to water at 25°C is 0.5 g/100 g or more
• water insolubility or being water-insoluble means that solubility to water at 25°C is less than 0.5 g/100 g.
• a liquid surfactant composition refers to a composition containing a surfactant in a liquid state or a paste-like state upon supporting the surfactant on the particles for supporting a surfactant.
• Powder Raw material Excluding Clay Mineral, The Powder Raw Material Having An Oil-Absorbing Ability of 0.4 ml/g or More
• An essential component in the present invention includes a powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more.
• the oil-absorbing ability refers to a value determined by a method described in the Evaluation Methods of Qualities described later.
• the powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more refers to substantially a porous substance having fine micropores having sizes of 10 ⁇ m or less in an inner portion of the powder, the substance capable of supporting a surfactant in the micropores.
• the upper limit of the oil-absorbing ability is not particularly limited, and it is desired that the upper limit is, for example, 1.0 ml/g or less.
• the powder raw material has an average particle size of preferably from 50 to 250 ⁇ m, more preferably from 50 to 200 ⁇ m, and even more preferably from 80 to 200 ⁇ m, from the viewpoint of formation of particles.
• the powder raw material is a water-soluble substance, from the viewpoint of dissolubility.
• the powder raw material include soda light ash or soda ash, prepared by baking sodium bicarbonate, sodium sulfate, a porous powder prepared by drying or a hydrate of sodium tripolyphosphate, and the like. Soda light ash is especially preferred, from the viewpoint of easiness in handling and easy availability.
• a surfactant- supporting ability can be even more improved by adjusting a temperature upon baking the sodium bicarbonate.
• the baking temperature is preferably from 120° to 250°C, preferably from 150° to 220°C, and even more preferably from 150° to 200°C, from the viewpoint of supporting ability.
• the powder raw material is contained in an amount of preferably from 40 to 95% by weight, more preferably from 45 to 90% by weight, even more preferably from 50 to 85% by weight, and especially preferably from 50 to 80% by weight, of the particles for supporting a surfactant, from the viewpoint of supporting ability.
• the powder raw material is contained in an amount of preferably from 25 to 80% by weight, more preferably from 30 to 77% by weight, even preferably from 32 to 77% by weight, and especially preferably from 32 to 73% by weight, of the particles before carrying out the drying step.
• the particles for supporting a surfactant in the present invention are obtained by adding water or an aqueous binder solution to a powder raw material, and forming particles from a mixture of the powder raw material with a low-shearing granulator.
• a clay mineral is used
• a mixture of the clay mineral and the powder raw material is formed into particles.
• a bonding property generated by partially dissolving the powder raw material in water, or a bonding property of a clay mineral is utilized in formation of particles.
• an aqueous binder solution a bonding property ascribed to the binder can be utilized, so that the formation of particles is more facilitated.
• the binder is not particularly limited, so long as the binder has an ability of binding the components constituting the particle in the powder raw material with each other, and has the property of dissolving and/or dispersing in water quickly.
• the binder includes, for example, polyethylene glycols, polypropylene glycols, polyoxyethylene alkyl ethers and derivatives thereof, polyvinyl alcohols and derivatives thereof, water-soluble cellulose derivatives (derivatives thereof including ether compounds, and the like); organic polymers such as carboxylate polymers, starch, and saccharides; inorganic polymers such as amorphous silicate; and the like.
• the water-soluble cellulose derivatives, saccharides, and carboxylate polymers are preferred, and a salt of acrylic acid-maleic acid copolymer and a salt of polyacrylic acid are more preferred, from the viewpoint of bonding property and detergency.
• the salt is preferably a sodium salt, a potassium salt, or an ammonium salt.
• the carboxylate polymer has a weight-average molecular weight of preferably from 1,000 to 100,000, and more preferably from 2,000 to 80,000.
• the binder is contained in the particles for supporting a surfactant in an amount of preferably from 0 to 35% by weight, more preferably from 5 to 30% by weight, even more preferably from 8 to 20% by weight, and especially preferably from 10 to 20% by weight, of the particles for supporting a surfactant, from the viewpoint of bonding property and oil-absorbing ability.
• the binder is contained in an amount of preferably from 0 to 30% by weight, more preferably from 3 to 25% by weight, even preferably from 5 to 17% by weight, and especially preferably from 7 to 17% by weight, of the particles before carrying out the drying step.
• the concentration of the aqueous binder solution is not particularly limited. Since the particle sizes upon formation of particles are greatly affected by the volume of the aqueous binder solution, the concentration may be determined from a necessary amount of the binder and a desired particle size of the particles.
• the clay mineral has a layered structure, and is capable of supporting a liquid surfactant between the layers. Therefore, by blending with a clay mineral, a supporting capacity of a liquid surfactant can be increased, and at the same time a supporting ability can be improved.
• the particle size of the particle for supporting a surfactant can be controlled by adjusting the amount of the clay mineral to be blended.
• the clay mineral may be added as a component for improving a supporting capacity/supporting ability, from the viewpoint of supporting ability and particle size control.
• the clay mineral as mentioned above includes, for example, talc, pyrophyllites, smectites such as saponite, hectorite, sauconite, stevensite, montmorillonite, beidellite and nontronite, vermiculites, micas such as phlogopite, biotite, zinnwaldite, muscovite, paragonite, celadonite and glauconite, chlorites such as clinochlore, chamosite, nimite, pennantite, sudoite and donbassite, brittle micas such as clintonite and margarite, thulite, serpentines such as antigorite, lizardite, chrysotile, amesite, cronstedtite, berthierine, greenalite and garnierite, kaolin minerals such as kaolinite, dickite, nacrite and halloysite, and the like.
• talc py
• talc talc
• smectites swellable micas
• vermiculites vermiculites
• chrysotile the kaolin minerals and the like
• the smectites are more preferable, and the montmorillonite is even more preferable.
• These clay minerals can be used alone or in a combination of two or more kinds.
• Examples of the clay mineral represented by the general formula (I) include “Laundrosil DGA212,” “Laundrosil PR414,” “Laundrosil DGA214,” “Laundrosil DGA Powder,” “EXM0242,” and “HULA SOFT-1 Powder,” manufactured by from Süd-Chemie; “Detersoft GIS”, “Detersoft GIB” and “Detersoft GISW” manufactured by Laviosa; Pure Bentonite, Standard Bentonite, and Premium Bentonite, manufactured by CSM; and the like.
• some of them exist in a particle style in which a binder component is added and formed into particles, and the binder component may be added so long as the effects of the present invention would not be impaired.
• the shape of the clay mineral is preferably in the form of powder, from the viewpoint of formation of particles, and in a case of a granular product, it is preferable that the granular product is disintegrated beforehand to a suitable granularity.
• the pulverizer that can be utilized for disintegration includes impact crushers such as hammer crusher; impact pulverizers such as atomizers and pin mills; shearing rough pulverizers such as flash mills. These pulverizers may be carried out in a single-step operation, or multi-step operations with the same or different pulverizers.
• the clay mineral powder has an average particle size of preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
• the alkali metal ions i.e. a total of Na ions, K ions, and Li ions
• the alkaline earth metal ions i.e. a total of Ca ions and Mg ions
• a molar ratio i.e. [(Na + K + Li)/(Ca + Mg)]
• the producing region may be selected, and in a case where the clay granules are produced, an alkali metal salt can be added to prepare the granules, and a synthetic product can be optionally prepared in any manner by a known method.
• the particles for supporting a surfactant in the present invention contain water in a proper amount that is used in the production steps.
• the amount of water is preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less.
• the particles for supporting a surfactant in the present invention can be properly blended even with a substance other than the 1 to 4 listed above as occasion demands.
• the amount of these substances blended is preferably 20% by weight or less, even more preferably 10% by weight or less, and especially preferably 5% by weight or less, from the viewpoint of supporting ability. Examples of substances that can be blended are given hereinbelow.
• the chelating agent can be blended for the purpose of suppressing the inhibition of detergent action by metal ions.
• a water-soluble chelating agent is not particularly limited, so long as the chelating agent is a substance that holds a metal ion sequestering ability, and a crystalline silicate, a tripolyphosphate, an orthophosphate, a pyrophosphate, or the like can be used. Among them, the crystalline silicate and the tripolyphosphate are preferred.
• a water-insoluble chelating agent is preferably particles that have an average particle size of from 0.1 to 20 ⁇ m, from the viewpoint of dispersibility in water.
• the preferred water-insoluble chelating agent includes crystalline aluminosilicates, including, for example, A-type zeolite, P-type zeolite, X-type zeolite, and the like, and the A-type zeolite is preferred, from the viewpoint of metal ion sequestering ability and economic advantages.
• a water-soluble inorganic salt is added, for the purposes of enhancing an ionic strength of a washing liquid, and improving an effect such as sebum dirt washing.
• the water-soluble inorganic salt is not particularly limited, so long as the inorganic salt is a substance that has excellent solubility and does not give a disadvantageous influence on detergency.
• the water-soluble inorganic salt includes, for example, alkali metal salts, ammonium salts, and the like, each having a sulfate group or a sulfite group.
• sodium sulfate, sodium sulfite, or potassium sulfate, each having a high degree of ionic dissociation is used as an excipient. Also, its combined use with magnesium sulfate is effective from the viewpoint of increasing the dissolution rate.
• the water-insoluble excipient is not particularly limited, so long as the water-insoluble excipient is a substance that has excellent dispersibility in water, and does not have a disadvantageous influence on detergency.
• the water-insoluble excipient includes, for example, crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicic acid compounds, and the like. It is preferable that the water-insoluble excipient has an average primary particle size of from 0.1 to 20 ⁇ m, from the viewpoint of dispersibility in water.
• auxiliary components include fluorescers, pigments, dyes, and the like.
• the average particle size of the above components can be measured in accordance with the methods described in the Measurement Methods of Physical Properties described later.
• the particles for supporting a surfactant of the present invention can be prepared by a method including the steps of stirring or mixing at least a powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more, and adding water or an aqueous binder solution to a mixed powder obtained, and forming particles with a low-shearing granulator, that does not include a spray-drying step.
• any methods may be employed so long as the components can be substantially homogeneously mixed.
• the mixing may be carried out with a low-shearing granulator used in the step 2, or the mixing may be previously carried out using a different mixer, and thereafter transferred to a low-shearing granulator.
• the different mixers to be used in powder mixing includes, for example, rotary mixers, pan mixers, ribbon mixers, Nauta mixers, Shugi Mixers, Lödige mixers, High-Speed Mixers, and the like.
• the clay mineral is contained in an amount of preferably from 1 to 45% by weight, more preferably from 2 to 40% by weight, even more preferably from 3 to 40% by weight, even more preferably from 3 to 35% by weight, and especially preferably from 4 to 30% by weight, of the particles for supporting a surfactant, from the viewpoint of supporting ability and particle size control.
• the particles may be dried as desired, and in a case where the components are adjusted to the above components by the drying step as mentioned above, the clay mineral is contained in an amount of preferably from 1 to 40% by weight, more preferably from 2 to 35% by weight, even more preferably from 3 to 30% by weight, even more preferably from 3 to 25% by weight, and especially preferably from 6 to 25% by weight, of the particles before carrying out the drying step.
• the clay mineral and the powder raw material are in a weight ratio, i.e. clay mineral/powder raw material, of preferably from 1/1 to 1/30, more preferably from 1/1 to 1/20, and especially preferably from 1/2 to 1/20.
• any methods may be employed so long as the components can be substantially homogeneously mixed.
• the mixing may be carried out with a low-shearing granulator used in the step 2, or the mixing may be previously carried out using a different mixer, and thereafter transferred to a low-shearing granulator.
• the powder raw material excluding the clay mineral as used herein refers to a powder raw material that does not substantially contain a clay mineral, and the powder raw material may contain a clay mineral in an amount of from 0 to 1.2% by weight, of the powder raw material.
• the clay mineral is contained in an amount of more preferably from 0 to 1.0% by weight, even more preferably from 0 to 0.8% by weight, and especially preferably from 0 to 0.6% by weight, of the powder raw material.
• the clay mineral is contained in an amount of preferably from 0 to 1% by weight, more preferably from 0 to 0.8% by weight, even more preferably from 0 to 0.6% by weight, and especially preferably from 0 to 0.5% by weight, of the particles for supporting a surfactant, from the viewpoint of hues of the particles supporting a surfactant and the detergent particles containing a surfactant composition supported by the particles.
• the particles may be dried as desired, and in a case where the components are adjusted to the above components by the drying step as described above, the clay mineral is contained in an amount of preferably from 0 to 0.9% by weight, more preferably from 0 to 0.7% by weight, even more preferably from 0 to 0.5% by weight, and especially preferably from 0 to 0.4% by weight, of the particles before carrying out the drying step.
• This step is a step including adding water or an aqueous binder solution to a mixed powder obtained in the step 1(a) or (b), and forming particles with a low-shearing granulator.
• a particle having a structure in which the powder raw material is gradually aggregated is formed.
• the step 1(a) or the step 1(b), and the step 2 can be carried out simultaneously.
• the low-shearing granulator usable in this step may be any apparatus that gives a strong shear to a particle without densifying the particle.
• the granulator can be utilized in the production of the particle of the present invention by setting a rotational speed or a Froude number described below to a low value, thereby controlling densification.
• the low-shearing granulator as used herein encompasses a granulator which can be operated by lowering a shearing force by setting or the like of operating conditions, even if the granulator is capable of giving a high shearing force to a particle.
• a pan type granulator or a rotary granulator in which the formation of particles progresses with the rotation of the body of the granulator, are preferred, from the viewpoint of easiness in formation of particles and improvement in supporting ability.
• These apparatuses can be used in both methods of a batch process and continuous process.
• baffles for assisting mixing in the pan or rotary mixer from the viewpoint of powder miscibility and liquid-solid miscibility.
• the granulator is set to have a Froude number, as defined in the following formula, of preferably 1.0 or less, more preferably 0.8 or less, even more preferably 0.6 or less, and especially preferably 0.4 or less, from the viewpoint of supporting ability.
• Fr V 2 / R ⁇ g , wherein V is a peripheral speed [m/s], R is a radius from the center of rotation to the circumference of a rotated object [m], and g is a gravitational acceleration rate [m/s 2 ].
• the granulator is set to have a Froude number of preferably 0.005 or more, and more preferably set to have the number of 0.01 or more, from the viewpoint of homogeneously adding water or an aqueous binder solution to a mixed powder.
• the values for the main blade are used for V and R in a vertical or horizontal granulator equipped with a main blade and a disintegrating blade, and that the values of the body of the granulator are used for V and R in the pan-type granulator or rotary granulator where the granulation is progressed with the rotations of the body of the granulator, the values for the body of the granulator.
• the values for the disintegration blade are used for V and R in the pan-type granulator equipped with a disintegration blade.
• a binder is homogenously dispersed by a liquid addition method.
• a method of homogeneously dispersing a binder there is a method of forming fine binder using a one-fluid nozzle, or a multi-fluid nozzle such as a two-fluid nozzle.
• the multi-fluid nozzle refers to a nozzle that allows to flow a binder and a gas for formation fine particles, such as the air or nitrogen, in independent pathways, to communicate to a portion in the vicinity of a tip end portion of the nozzle, and mixing and forming particles.
• a two-fluid nozzle, a three-fluid nozzle, a four-fluid nozzle, or the like can be used as the multi-fluid nozzle.
• a mixing portion of the binder and the gas for forming fine particles may be any one of an internal mixing type where the mixing is carried out within a tip end portion of the nozzle, or an external mixing type where the mixing is carried out in the external of a tip end portion of the nozzle.
• a multi-fluid nozzle such as a two-fluid nozzle.
• a multi-fluid nozzle for example, a wide-angled round type two-fluid nozzle (manufactured by Spraying Systems Japan K.K.), or a four-fluid nozzle (manufactured by Fujisaki Denki K.K.), or the like can be used.
• a homogenous dispersion can be achieved even in an aqueous binder solution having a high viscosity, so that particles for supporting a surfactant having an improved yield and a sharp particle size distribution are obtained.
• This step is an optional step including drying the particles obtained in the step 2. By removing water, gaps between the particles are increased, whereby a supporting capacity can be even more improved.
• the drying method includes a method including placing the particles in a vessel, and drying the particles with an electric dryer or a hot air dryer; and a method of drying with a batch-type fluidized bed; or the like.
• the drying method employs a vibration fluidized bed, a rotary dryer, a steam tube dryer, or the like.
• a drying temperature is preferably 80°C or more, more preferably 120°C or more, even more preferably 150°C or more, and especially preferably 180°C or more, from the viewpoint of drying rate.
• a drying temperature is preferably 300°C or less, more preferably 250°C or less, and especially preferably 220°C or less, from the viewpoint of suppressing the degradation of the binder.
• the particles for supporting a surfactant in the present invention are particles having a structure in which at least a powder raw material excluding a clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more, is gradually aggregated. For this reason, the particles have two supporting sites: (1) large gaps between the powder raw materials, and (2) small gaps within the powder raw material (for example, gaps having sizes of 10 ⁇ m or less). Among them, both (1) and (2) greatly influence supporting capacity and supporting ability, and (1) greatly influences absorbing rate. By adjusting the two supporting sites, particles for supporting a surfactant having a desired supporting ability can be obtained.
• a liquid surfactant composition in a case where a clay mineral is blended, a liquid surfactant composition can be supported between the layers, so that improvement in supporting ability can be taken into account.
• the particles for supporting a surfactant of the present invention have a bulk density of 550 g/L or less, preferably from 400 to 550 g/L, and more preferably from 400 to 500 g/L, from the viewpoint of securing supporting capacity of a liquid surfactant composition, and from the viewpoint of securing high bulk density after the liquid surfactant composition is supported. It is considered that a relatively low bulk density of the particles for supports of the present invention is accomplished by formation of particles with a low-shearing granulator mentioned above.
• the particles for supports have an average particle size of preferably from 140 to 600 ⁇ m, more preferably from 200 to 500 ⁇ m, and even more preferably from 200 to 400 ⁇ m, from the viewpoint of powder dust property and dissolubility upon the use of a detergent composition containing detergent particles containing particles for supporting a surfactant and a liquid surfactant composition supported thereto.
• the liquid surfactant composition of the particles for supporting a surfactant has an oil-absorbing ability of preferably 0.4 ml/g or more, even more preferably 0.45 ml/g or more, and especially preferably 0.5 ml/g or more, from the viewpoint of increasing an allowable range of the amount of the liquid surfactant composition blended. It is considered that a relatively high oil-absorbing ability of the particles for supports of the present invention is accomplished by formation of particles with a low-shearing granulator mentioned above.
• the water of the particles for supporting a surfactant as measured with an infrared moisture meter contained in a smaller amount is preferred, and the water is contained in an amount of preferably 15% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, from the viewpoint of increasing supporting capacity of the liquid surfactant composition on the particles.
• Specific components of the particles for supporting a surfactant of the present invention include, for example, components in which the particles have a bulk density of 550 g/l or less, a powder raw material excluding the clay mineral, the powder raw material having an oil-absorbing ability of 0.4 ml/g or more in an amount of from 40 to 95% by weight, a clay mineral powder in an amount of from 0 to 45% by weight, a binder in an amount of from 0 to 35% by weight, and water in an amount of from 0 to 15% by weight.
• the detergent particles of the present invention are high-density detergent particles containing the particles for supporting a surfactant according to the present invention, i.e. the particles for supporting a surfactant obtained by the production method of the present invention, and the particles for supporting a surfactant of the present invention, and a surfactant composition supported thereto.
• the detergent particles need not be used alone, so long as the particles for supporting a surfactant according to the present invention are contained, and can be used together with particles for supporting a surfactant obtained by spray drying or other method.
• a mixture of the particles according to the present invention and the particles obtained by spray drying or other method can be handled as the particles for supporting a surfactant.
• each of an anionic surfactant and a nonionic surfactant can be used alone, and it is more preferable that both the surfactants are used in a mixture.
• a nonionic surfactant having a melting point of 30°C or lower it is preferable to use the nonionic surfactant together with a water-soluble nonionic organic compound having a melting point of from 45° to 100°C and a molecular weight of from 1,000 to 30,000, the water-soluble nonionic organic compound having an action of elevating a melting point of a surfactant (hereinafter referred to as a "melting-point elevating agent"), or an aqueous solution thereof.
• the melting-point elevating agent which can be used in the present invention includes, for example, polyethylene glycols, polypropylene glycols, polyoxyethylene alkyl ethers, Pluronic nonionic surfactants, and the like.
• an amphoteric surfactant or a cationic surfactant can be used together, depending upon the purposes.
• an anionic surfactant such as an alkylbenzenesulfonate can be blended in an amount of preferably from 5 to 25% by weight of the detergent particles, from the viewpoint of improving dispersibility of detergent particles in water at low temperatures.
• the surfactant composition for example, one or more members selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.
• the anionic surfactants are exemplified by alkylbenzenesulfonates; alkyl ether or alkenyl ether sulfates; ⁇ -olefinsulfonates; salts of ⁇ -sulfofatty acids or esters thereof; alkyl ether or alkenyl ether carboxylates, amino acid-type surfactants; N-acyl amino acid-type surfactants, and the like.
• linear alkylbenzenesulfonates, alkyl sulfates or alkyl ether sulfates are preferred.
• the counterions are preferably alkali metals such as sodium and potassium, and amines such as monoethanolamine and diethanolamine.
• a fatty acid salt can be used in together therewith.
• the nonionic surfactants include polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl- or alkenylphenyl ethers, polyoxyethylene- polyoxypropylene alkyl or alkenyl ethers, polyoxyethylene- polyoxypropylene glycols as represented by the trade name "pluronic," polyoxyethylene alkylamines, higher fatty acid alkanolamides, alkyl glucosides, alkyl glucosamides, alkylamine oxides, and the like.
• ethylene oxide hereinafter simply referred to as "EO”
• PO propylene oxide
• the cationic surfactant includes quaternary ammonium salts such as alkyl trimethyl ammonium salts.
• the amphoteric surfactant is exemplified by carbobetain-type and sulfobetain-type surfactants and the like.
• the amount of the anionic surfactant blended in the surfactant composition is preferably from 0 to 300 parts by weight, even more preferably from 20 to 200 parts by weight, and especially preferably from 30 to 180 parts by weight, based on 100 parts by weight of the nonionic surfactant.
• the amount of the melting point-elevating agent of the nonionic surfactant blended is preferably from 1 to 100 parts by weight, and even more preferably from 5 to 50 parts by weight, based on 100 parts by weight of the nonionic surfactant.
• the surfactant composition is preferable, because the composition has a temperature range so that the viscosity of the composition at a temperature of a pour point or higher of the composition is adjusted to preferably 10 Pa•s or less, more preferably 5 Pa•s or less, and especially preferably 2 Pa•s or less, and also has a temperature range so that the penetration hardness of the composition in the temperature range of lower than the pour point of the composition and higher than the melting point of the nonionic surfactant is preferably 10 kPa or more, more preferably 30 kPa or more, and especially preferably 50 kPa or more, whereby the handling property of the composition and the detergent particles during production becomes excellent, and the bleed-out of the nonionic surfactant during storage of the detergent particles can be suppressed.
• the values for the physical properties of the surfactant composition can be determined by the following method.
• the pour point can be measured by the method according to JIS K 2269.
• the melting point is determined by using FP800 Thermosystem "Mettler FP81" (manufactured by Mettler Instrumente AG) and heating at a heating rate of 0.2°C/min.
• the viscosity is obtained by measuring with a B-type viscometer ("DVM-B model" manufactured by TOKYO KEIKI), rotor No. 3 under the condition of 60 r/min.
• DVM-B model manufactured by TOKYO KEIKI
• the viscosity is obtained by measuring with rotor No. 3, under the condition of 12 r/min.
• the penetration hardness is a value obtained by determining a load when an adaptor is penetrated for 20 mm at a penetration rate of 20 mm/min into an inner portion of the surfactant composition by using a rheometer ("NRM-3002D” manufactured by Fudo Kogyo K.K.) and a disc-shaped adaptor (No. 3, 8 ⁇ ) having a diameter of 8 mm and a bottom area of 0.5 cm 2 , and dividing the resulting load by the bottom area of the disc-shaped adaptor.
• the amount of the surfactant composition is preferably in a range of from 10 to 100 parts by weight, more preferably in a range of from 20 to 80 parts by weight, and especially preferably in a range of from 30 to 60 parts by weight, based on 100 parts by weight of the particles for supports, from the viewpoint of the detergency and the dissolubility.
• a powder raw material other than the above powder raw material may be added as desired, and the amount thereof is preferably from 0 to 150 parts by weight, based on 100 parts by weight of the particles.
• the powder raw material includes, for example, aluminosilicates, crystalline silicates such as PREFEED (manufactured by Tokuyama Siltex), and the like.
• the preferred physical properties of the detergent particles according to the present invention are as follows.
• the bulk density is preferably from 500 to 1,000 g/L, more preferably from 600 to 1,000 g/L, and especially preferably from 650 to 900 g/L.
• the average particle size is preferably from 150 to 500 ⁇ m, and more preferably from 180 to 400 ⁇ m.
• the bulk density and the average particle size can be measured in accordance with the Measurement Methods of Physical Properties described later.
• a preferred method for obtaining detergent particles includes the following step (I), and may further include step (II) as occasion demands.
• a method of supporting a surfactant composition in the particles for supports includes, for instance, a process including mixing the particles for supports with a surfactant composition by using a mixer for a batch process or continuous process.
• a process of supplying to a mixer there may be employed such methods as (1) a method including previously supplying particles for supports in a mixer, and thereafter adding thereto a surfactant composition; (2) a method including supplying particles for supports and a surfactant composition in the mixer in small amounts at a time; (3) a method including supplying a part of particles for supports in a mixer, and thereafter supplying the remaining particles for supports and a surfactant composition in the mixer in small amounts at a time, and the like.
• surfactant compositions those which are present as solids or pasty states even if heated within a practical temperature range, for instance, from 50° to 90°C, are previously dispersed or dissolved in a nonionic surfactant having low viscosity, an aqueous solution of a nonionic surfactant, or water, to prepare a liquid mixture or aqueous solution of a surfactant composition, to be added to the particles for supports in the form of a liquid mixture or aqueous solution.
• the mixing ratio of the surfactant composition having a low viscosity or water to the solid or pasty surfactant composition is preferably such that the resulting liquid mixture or aqueous solution has a viscosity range of which is sprayable.
• the method for producing the above liquid mixture includes, for example, a method including supplying a solid or paste-like surfactant composition to a surfactant having a low viscosity or water, and mixing the mixture; or a method for producing a liquid mixture of a surfactant composition including neutralizing an acid precursor of a surfactant, for example, a surfactant having a low viscosity or water or an acid precursor of a surfactant in water, with an alkalizing agent, for instance, an aqueous sodium hydroxide or an aqueous potassium hydroxide, in a surfactant having a low viscosity or water.
• an alkalizing agent for instance, an aqueous sodium hydroxide or an aqueous potassium hydroxide
• an acid precursor of an anionic surfactant can be added before adding a surfactant composition, simultaneously with adding a surfactant composition, in the course of adding a surfactant composition, or after adding a surfactant composition.
• an acid precursor of an anionic surfactant By adding the acid precursor of an anionic surfactant, there can be achieved improvements in properties and quality, such as high concentration of the surfactants, supporting abilities of particles for supports, control for the supporting abilities thereof, and suppression of bleed-out of the nonionic surfactant and the flowability of the resulting detergent particles.
• the acid precursor of an anionic surfactant which can be used in the present invention includes, for example, alkylbenzenesulfonic acids, alkyl ether or alkenyl ether sulfuric acids, alkyl- or alkenylsulfuric acids, ⁇ -olefinsulfonic acids, ⁇ -sulfonated fatty acids, alkyl ether or alkenyl ether carboxylic acids, fatty acids, and the like. It is especially preferable that the fatty acid is added after adding the surfactant, from the viewpoint of improvement in the flowability of the detergent particles.
• the amount of the acid precursor of an anionic surfactant used is preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight, even more preferably from 1 to 10 parts by weight, and especially preferably from 1 to 5 parts by weight, based on 100 parts by weight of the particles for supports.
• the method of adding the acid precursor of an anionic surfactant it is preferable that those in a liquid state at an ordinary temperature are supplied by spraying, and that those in a solid state at an ordinary temperature may be added as a powder, or they may be supplied by spraying after melting the solid.
• the temperature of the detergent particles in the mixer is raised to a temperature at which the powder melts.
• Preferable mixers specifically include as follows.
• those of (1) to (3) are preferable: (1) Henschel Mixer (manufactured by Mitsui Miike Machinery Co., Ltd.); High-Speed Mixer (Fukae Powtec Corp.); Vertical Granulator (manufactured by Powrex Corp.); Lödige Mixer (manufactured by Matsuzaka Giken Co., Ltd.); PLOUGH SHARE Mixer (manufactured by PACIFIC MACHINERY & ENGINEERING Co., LTD.); mixers disclosed in JP-A-Hei 10-296064 , mixers disclosed in JP-A-Hei 10-296065 , and the like; (2) Ribbon Mixer (manufactured by Nichiwa Kikai Kogyo K.K.); Batch Kneader (manufactured by Satake Kagaku Kikai Kogyo K.K.); Ribocone (manufactured
• mixers preferable are Lödige Mixer, PLOUGH SHARE Mixer, and the mixers disclosed in JP-A-Hei 10-296064 , mixers disclosed in JP-A-Hei 10-296065 , and the like. Since step (II) described below can be carried out by the same mixer, these mixers are preferable from the viewpoint of simplification of equipments.
• the mixers disclosed in JP-A-Hei 10-296064 and the mixers disclosed in JP-A-Hei 10-296065 are preferable, because the moisture and temperature of the mixture can be regulated by aeration, whereby the disintegration of the particles for supporting a surfactant can be suppressed.
• mixers such as Nauta Mixer, SV Mixer and Ribbon Mixer, which are capable of mixing powders with liquids without applying a strong shearing force, are preferable from the viewpoint that the disintegration of the particles for supporting a surfactant can be suppressed.
• the particles for supports may be mixed with a surfactant composition by using the above-mentioned continuous process-type mixer.
• the continuous process-type mixer other than those listed above includes Flexo Mix (manufactured by Powrex Corp.), Turbulizer (manufactured by Hosokawa Micron Corporation), and the like.
• a nonionic surfactant when used, it is preferable that a water-soluble nonionic organic compound (hereinafter referred to as "melting point-elevating agent") having a melting point of from 45° to 100°C and a molecular weight of from 1000 to 30000, or an aqueous solution thereof, which has a function of elevating a melting point of this nonionic surfactant, is added before adding a surfactant composition, simultaneously with adding a surfactant composition, in the course of adding a surfactant composition, or after adding a surfactant composition, or previously mixed with a surfactant composition.
• melting point-elevating agent a water-soluble nonionic organic compound having a melting point of from 45° to 100°C and a molecular weight of from 1000 to 30000, or an aqueous solution thereof, which has a function of elevating a melting point of this nonionic surfactant
• the caking property of the detergent particles and the bleed-out property of the surfactants in the detergent particles can be suppressed.
• these melting point-elevating agents the same ones as those exemplified in the melting point-elevating agent in the composition of the detergent particles described above can be used.
• the amount of the melting point-elevating agent used is preferably from 0.5 to 8 parts by weight, more preferably from 0.5 to 5 parts by weight, and most preferably from 1 to 3 parts by weight, based on 100 parts by weight of the particles for supports.
• the above range is preferable from the viewpoint of the suppression of the aggregation between particles, the fast dissolubility, and the suppression of the bleed-out property and the caking property, each property of which is owned by the detergent particle contained in the detergent particles.
• a method of adding the melting point-elevating agent including adding by previously mixing the melting point-elevating agent with a surfactant by an arbitrary process, or a method including adding a surfactant, and thereafter adding the melting point-elevating agent, is advantageous for the suppression of the bleed-out property and the caking property of the detergent particles.
• the temperature within the mixer in this step it is more preferable that mixing is carried out by heating to a temperature equal to or higher than the pour point of the surfactant composition.
• the pour point of the surfactant composition is measured according to the method of JIS K 2269.
• the temperature to be heated may be a temperature higher than the pour point of the surfactant composition added in order to promote the support of the surfactant composition, and the practical temperature range is preferably from a temperature exceeding a pour point to a temperature higher than the pour point by 50°C, more preferably a temperature higher than the pour point by 10° to 30°C.
• an acid precursor of an anionic surfactant it is more preferable to mix the components after heating to a temperature at which the acid precursor of an anionic surfactant can react.
• the mixing time in a batch process and the average residence time in the mixing in a continuous process for obtaining the suitable detergent particles are preferably from 1 to 20 minutes, and more preferably from 2 to 10 minutes.
• a step of drying excess water contents during mixing and/or after mixing may be included.
• a powdery surfactant and/or a powdery builder can also be added before adding a surfactant composition, simultaneously with adding a surfactant composition, in the course of adding a surfactant composition, or after adding a surfactant composition.
• the powdery builder By adding the powdery builder, the particle size of the detergent particles can be controlled, and an improvement in detergency can be achieved.
• the acid precursor of an anionic surfactant it is effective to add a powdery builder showing alkaline property prior to adding the acid precursor, from the viewpoint of accelerating the neutralization reaction.
• the term "powdery builder” mentioned herein refers to an agent for enhancing detergency other than surfactants which is in a powdery form, concretely, including base materials showing metal ion sequestering ability, such as zeolite and citrates; base materials showing alkalizing ability, such as sodium carbonate and potassium carbonate; base materials having both metal ion sequestering ability and alkalizing ability, such as crystalline silicates; other base materials enhancing ionic strength, such as sodium sulfate; and the like.
• crystalline silicates those described in JP-A-Hei 5-279013 , column 3, line 17 (especially, those prepared by a process comprising calcinating and crystallizing at a temperature of from 500° to 1000°C being preferable); JP-A-Hei 7-89712 , column 2, line 45; and JP-A-Sho 60-227895 , page 2, lower right column, line 18 (especially the silicates in Table 2 being preferable) can be used as preferred powdery builders.
• the alkali metal silicates having an SiO 2 /M 2 O ratio, wherein M is an alkali metal, of from 0.5 to 3.2, preferably from 1.5 to 2.6, are more favorably used.
• the amount of the powdery builder used is preferably from 0.5 to 12 parts by weight, more preferably from 1 to 6 parts by weight, based on 100 parts by weight of the particles for supports.
• the amount of the powdery builder for detergents used is in the above range, those having an excellent fast dissolubility are obtained.
• step (I) it is preferable to add a step (II) including surface-modifying the detergent particles.
• the embodiments for addition may include a process comprising one or more steps of the step (II) including adding various surface coating agents such as (1) fine powder, and (2) a liquid material.
• the apparatuses used in the step (II) are preferably those equipped with both agitation blades and disintegration blades among the mixers exemplified in the step (I).
• Each of the surface coating agents will be explained below.
• the average particle size of its primary particle is 10 ⁇ m or less, more preferably from 0.1 to 10 ⁇ m.
• the average particle size of the fine powder can be measured by a method utilizing light scattering by, for instance, a particle analyzer (manufactured by Horiba, LTD.), or it may be measured by a microscopic observation or the like.
• the fine powder has a high ion exchange capacity or a high alkalizing ability from the aspect of detergency.
• the fine powder is desirably aluminosilicates, which may be crystalline or amorphous.
• aluminosilicates fine powders of sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicates, and the like are preferable.
• a metal soap of which primary particles have a size of 0.1 to 10 ⁇ m a powdery surfactant (for instance, an alkyl sulfate, or the like), or a water-soluble organic salt.
• the crystalline silicate when used, it is preferably used in admixture with fine powder other than the crystalline silicate for the purpose of preventing deterioration owing to aggregation of the crystalline silicates by moisture absorption and carbon dioxide absorption, and the like.
• the amount of the fine powder used is preferably from 0.5 to 40 parts by weight, more preferably from 1 to 30 parts by weight, and especially preferably from 2 to 20 parts by weight, based on 100 parts by weight of the detergent particles.
• the amount of the fine powder used is in the above range, the flowability is improved, thereby giving a good sense of feel to consumers.
• the liquid materials include water-soluble polymers, fatty acids, and the like, which may be added in the form of aqueous solutions and molten states.
• the water-soluble polymer includes carboxymethyl celluloses, polyethylene glycols, polycarboxylates such as sodium polyacrylate and copolymers of acrylic acid and maleic acid and salts thereof, and the like.
• the amount of the water-soluble polymer used is preferably from 0.5 to 10 parts by weight, more preferably from 1 to 8 parts by weight, and especially preferably from 2 to 6 parts by weight, based on 100 parts by weight of the detergent particles. When the amount of the water-soluble polymer used is in the above range, the detergent particles exhibiting excellent dissolubility and excellent flowability and anti-caking properties can be obtained.
• the fatty acid includes, for instance, fatty acids having 10 to 22 carbon atoms, and the like.
• the amount of the fatty acid used is preferably from 0.5 to 5 parts by weight, and especially preferably from 0.5 to 3 parts by weight, based on 100 parts by weight of the detergent particles.
• the fatty acid is heated to a temperature exhibiting flowability, and then supplied to the detergent particles by spraying.
• the detergent composition in the present invention is a composition containing the detergent particles described above, and the composition further comprises separately added detergent components other than the detergent particles (for instance, builder particles, fluorescent dyes, enzymes, perfumes, defoaming agents, bleaching agents, bleaching activators, and the like).
• detergent components for instance, builder particles, fluorescent dyes, enzymes, perfumes, defoaming agents, bleaching agents, bleaching activators, and the like.
• the detergent particles are contained in an amount of preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, and especially preferably 80% by weight or more and 100% by weight or less, of the detergent composition, from the viewpoint of detergency.
• the detergent components other than the detergent particles are contained in an amount of preferably 50% by weight or less, more preferably 40% by weight or less, even more preferably 30% by weight or less, and especially preferably 20% by weight or less, of the detergent composition.
• the method for producing a detergent composition is not particularly limited, and an example thereof includes a method of mixing the detergent particles and separately added detergent components. Since the detergent composition obtained in the manner described above contains a detergent particle having a large supporting capacity of the surfactant, sufficient detergent effects can be exhibited even with a small amount.
• the application of such a detergent composition is not particularly limited, as long as it is applied to powder detergent, including, for example, laundry powder detergents, detergents for automatic dishwashers, and the like.
• Average particle sizes are determined in accordance with the following two methods. (1) For those having an average particle size of 80 ⁇ m or more, an average particle size is obtained by vibrating particles for 5 minutes using standard sieves of JIS K 8801 (sieve openings from 2000 to 125 ⁇ m), and calculating a median size from weight percentages according to the sizes of the sieve openings.
• the particles are vibrated for 5 minutes, and the weights of the particles remaining on each of the sieves and the receiving tray are measured, and weight proportions (%) of the particles on each sieve is calculated.
• the weight proportions of the particles in the order beginning from the receiving tray to those sieves having smaller sieve openings are cumulated, and a particle size at which a total is 50% is defined as an average particle size.
• Water content of the particle is measured in accordance with an infrared moisture meter method. Specifically, a 3 g sample is weighed and placed on a weighing dish of a known weight, and the sample is heated at 200°C with an infrared moisture meter (FD-240, manufactured by Kett Kagaku Kenkyujo K.K.). A time point at which there is not weight change for 30 seconds is defined as a termination of drying. Thereafter, a water content is calculated from the weight after drying and the weight before drying.
• FD-240 infrared moisture meter
• a flow time is defined as a time period required for flowing 100 mL of powder from a hopper used in a measurement of bulk density as prescribed in JIS K 3362.
• the flow time is preferably 10 seconds or less, more preferably 8 seconds or less, and even more preferably 7 seconds or less.
• a 30 to 35g powder is supplied into an absorption amount measurement apparatus (S410, manufactured by ASAHISOUKEN, and driving blades are rotated at 200 r.p.m.
• an absorption amount measurement apparatus S410, manufactured by ASAHISOUKEN, and driving blades are rotated at 200 r.p.m.
• a liquid nonionic surfactant (EMULGEN 108, manufactured by Kao Corporation) is added dropwise at a liquid feeding rate of 4 ml/min, and a point that reaches a maximum torque is probed thoroughly.
• the amount of the liquid at a point satisfying 70% of the torque of this maximum torque is divided by an amount of the powder supplied, and the resultant value is defined as an oil-absorbing ability.
• n is preferably 1.0 or more, and more preferably 1.5 or more.
• a 60-seconds dissolution ratio of the detergent particles explained hereinbelow can be used as an index for dissolubility in the present invention.
• the dissolution ratio is preferably 90% or more, and more preferably 95% or more.
• detergent compositions can be evaluated in the same manner.
• the 60-seconds dissolution ratio of the detergent particles is calculated by the method described below.
• a 1-litter beaker (a cylindrical form having an inner diameter of 105 mm and a height of 150 mm, for example, a 1-liter glass beaker manufactured by Iwaki Glass Co., Ltd.) is charged with 1 liter 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 or 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.
• the dried insoluble remnants are cooled by keeping in a desiccator with a silica gel (25°C) for 30 minutes. After cooling the insoluble remnants, a total weight of the dried insoluble remnants of the detergent, the sieve and the collected vessel is measured, and the dissolution ratio (%) of the detergent particles is calculated by the formula (1):
• 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).
• Yield of the particles in the present invention is determined by proportions of the particles having a specified particle size range of the entire particles.
• yield in particles having particle sizes of from 125 to 1000 ⁇ m means proportions of the particles having particle sizes of 125 ⁇ m or more and 1000 ⁇ m or less of the entire particles.
• the yield of detergent in the present invention refers to a proportion of the particles having particle sizes of 1180 ⁇ m or less of a detergent composition obtained by mixing the above detergent particles and separately added detergent components.
• Light Ash 1 Average particle size: 100 ⁇ m (manufactured by Central Glass Co., Ltd., oil-absorbing ability: 0.45 ml/g)
• Light Ash 2 Average particle size: 175 ⁇ m (manufactured by Central Glass Co., Ltd., oil-absorbing ability: 0.69 ml/g)
• Clay Mineral "Laundrosil DGA Powder” manufactured by Süd-Chemie Sodium Polyacrylate: Weight-average molecular weight: 10,000 (manufactured by Kao Corporation)
• Dense Ash Average particle size: 290 ⁇ m, (manufactured by Central Glass Co., Ltd. Sodium Sulfate: Anhydrous neutral sodium sulfate (manufactured by Shikoku Kasei K.K.)
• the resulting particles 1 are particles having an average particle size of 204 ⁇ m, a bulk density of 490 g/L, and an oil-absorbing ability of 0.52 ml/g.
• the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 56%, and a Rosin-Rammler number of 1.0.
• the resulting particles 2 are particles having an average particle size of 320 ⁇ m, a bulk density of 495 g/L, and an oil-absorbing ability of 0.51 ml/g.
• the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 56%, and a Rosin-Rammler number of 1.6.
• the resulting particles 3 are particles having an average particle size of 390 ⁇ m, a bulk density of 430 g/L, and an oil-absorbing ability of 0.58 ml/g.
• the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 93%, and a Rosin-Rammler number of 2.5.
• a mixing vessel was charged with 375 parts by weight of water. After the water temperature reached 35°C, 127 parts by weight of sodium sulfate, 5 parts by weight of sodium sulfite, and 1 part by weight of a fluorescer were added thereto, and the components were stirred for 10 minutes. One-hundred and twenty-seven parts by weight of sodium carbonate were added to the mixture, 75 parts by weight of a 40% by weight aqueous solution of sodium polyacrylate were added to the mixture, and the components were stirred for 10 minutes, to provide a first preparation liquid. A fine crystal precipitating agent sodium chloride was added to the first preparation liquid in an amount of 24 parts by weight, and the mixture was stirred for 10 minutes. Further, 266 parts by weight of zeolite were added thereto, and the mixture stirred for 30 minutes, to provide a homogeneous second preparation liquid (water content of slurry: 42% by weight).
• the second preparation liquid was fed to a spray-drying tower (countercurrent type) with a pump, and sprayed from a pressure spraying nozzle arranged near the top of the tower at a spraying pressure of 2.5 MPa.
• a high-temperature gas to be fed to a spray-drying tower was fed at 200°C from the lower part of the tower, and discharged at 90°C from the top of the tower.
• the resulting particles 4 had a water content of 4% by weight.
• the resulting particles were particles having an average particle size of 285 ⁇ m and a bulk density of 476 g/L.
• the resulting particles 5 are particles having an average particle size of 317 ⁇ m, a bulk density of 489 g/L, and an oil-absorbing ability of 0.51 ml/g.
• the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 97%, and a Rosin-Rammler number of 2.9.
• Light Ash 1 One-hundred parts by weight of Light Ash 1 were supplied into a 70-L rotary granulator ( ⁇ 40 cm ⁇ L 60 cm, rotational speed: 32 r.p.m., Froude number: 0.23) having baffles, and 55.6 parts by weight of a 35% aqueous solution of sodium polyacrylate were added thereto in 5.5 minutes with the two-fluid nozzle. After the addition, the mixture was formed into particles for 3 minutes, and the particles were then discharged from the rotary granulator. The particles were dried at 200°C for 3 hours with an electric dryer. The water content after drying was 0.9% by weight.
• the resulting particles 6 are particles having an average particle size of 328 ⁇ m, a bulk density of 448 g/L, and an oil-absorbing ability of 0.61 ml/g. In addition, the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 95.2%, and a Rosin-Rammler number of 2.5.
• 100 parts by weight of the particles 3 for supporting a surfactant obtained were supplied into a Lödige mixer (manufactured by Matsuzaka Giken, volume: 130 L, equipped with a jacket), and stirring of the main shaft (agitation blade, rotational speed: 60 rpm, peripheral speed: 1.6 m/s) was started.
• agitation blade, rotational speed: 60 rpm, peripheral speed: 1.6 m/s was started.
• a hot water at 80°C was allowed to flow through a jacket at a rate of 10 L/min.
• Detergent Particles 1 obtained had an average particle size of 481 ⁇ m, a bulk density of 800 g/L, and a free flowability of 5.8 s.
• Detergent Particles 2 were produced in accordance with the method shown below using the particles 3 for supporting a surfactant produced in Example 3 and the particles 4 for supporting a surfactant produced by spray-drying of Production Example 1.
• 50 parts by weight of the particles 3 for supporting a surfactant and 50 parts by weight of the particles 4 for supporting a surfactant obtained were supplied into a Lödige mixer (manufactured by Matsuzaka Giken, volume: 130 L, equipped with a jacket), and stirring of the main shaft (agitation blade, rotational speed: 60 rpm, peripheral speed: 1.6 m/s) was started.
• agitation blade, rotational speed: 60 rpm, peripheral speed: 1.6 m/s was started.
• a hot water at 80°C was allowed to flow through a jacket at a rate of 10 L/min.
• Detergent Particles 2 obtained had an average particle size of 342 ⁇ m, a bulk density of 807 g/L, a dissolution ratio of 93%, and a free flowability of 6.2 s.
• Detergent Particles 3 were produced in the same manner as in Example 8 except that 100 parts by weight of the particles 5 for supporting a surfactant were used in place of the particles 3 for supporting a surfactant.
• Detergent Particles 3 obtained had an average particle size of 356 ⁇ m, a bulk density of 768 g/L, and a free flowability of 6.0 s.
• Detergent Particles 4 were produced in the same manner as in Example 8 except that 100 parts by weight of the particles 6 for supporting a surfactant were used in place of the particles 3 for supporting a surfactant.
• Detergent Particles 4 obtained had an average particle size of 315 ⁇ m, a bulk density of 808 g/L, and a free flowability of 5.9 s.
• the resulting particles 9 are particles having an average particle size of 352 ⁇ m, a bulk density of 715 g/L, and an oil-absorbing ability of 0.16 ml/g. In addition, the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 92%, and a Rosin-Rammler number of 2.0.
• the resulting particles 10 are particles having an average particle size of 362 ⁇ m, a bulk density of 736 g/L, and an oil-absorbing ability of 0.30 ml/g.
• the particles had an yield of particles having sizes of from 125 to 1000 ⁇ m of 55%, and a Rosin-Rammler number of 1.5.
• Detergent Particles 6 were produced in the same manner as in Example 8 except that 100 parts by weight of the particles 10 for supporting a surfactant produced in Comparative Example 2 were used in place of the particles 3 for supporting a surfactant..
• Detergent Particles 6 obtained had an average particle size of 876 ⁇ m, a bulk density of 830 g/L, and a free flowability of 6.5 s.
• Detergent Particles 7 were produced in the same manner as in Example 9 except that 35 parts by weight of Light Ash 1 and 15 parts by weight of Clay Mineral were used in place of 50 parts by weight of the particles 3 for supporting a surfactant.
• Detergent Particles 7 obtained had an average particle size of 424 ⁇ m, a bulk density of 835 g/L, and a free flowability of 6.1 s.
• Example 1 It was clarified from the comparison of Example 1 with Comparative Example 1 and Comparative Example 2 that by carrying out a low-shearing granulation, preferably a low-shearing granulation in which a Froude number is 1.0 or less, particles having desired bulk densities and oil-absorbing abilities can be obtained.
• a low-shearing granulation preferably a low-shearing granulation in which a Froude number is 1.0 or less, particles having desired bulk densities and oil-absorbing abilities can be obtained.
• Example 9 the detergent particles containing a raw material that are not formed into particles in place of the particles for supporting a surfactant of the present invention do not show an excellent dissolution ratio, so that they were poorer in quality as compared to those containing the particles for supports of the present invention. It was shown from the results that the formation of particles by low-shearing granulation is important in the qualities of the detergent particles.
• particles for supporting a surfactant having excellent supporting capacity/ supporting ability/absorbing rate of a liquid surfactant composition can be obtained by a method without employing spray-drying.

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