WO2009142135A1 - 界面活性剤担持用顆粒群 - Google Patents
界面活性剤担持用顆粒群 Download PDFInfo
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- WO2009142135A1 WO2009142135A1 PCT/JP2009/058934 JP2009058934W WO2009142135A1 WO 2009142135 A1 WO2009142135 A1 WO 2009142135A1 JP 2009058934 W JP2009058934 W JP 2009058934W WO 2009142135 A1 WO2009142135 A1 WO 2009142135A1
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- surfactant
- weight
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- detergent
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 description 1
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 a surfactant-supporting granule group and a method for producing the same. Furthermore, the present invention relates to a high bulk density detergent particle group using such a surfactant-carrying granule group and a detergent composition comprising the detergent particle group.
- a production method including a step of supporting a liquid surfactant on a group of granules for supporting a surfactant.
- a group of granules for supporting a surfactant is required to have a high supporting ability for a liquid surfactant. That is, the supporting ability required for the surfactant-supporting granule group is that it can support a large amount of liquid surfactant (supporting capacity) and can be strongly retained inside the granule without causing the liquid surfactant once absorbed (see FIG. It consists of two factors (bearing force).
- the loading capacity is necessary for blending a surfactant in an amount necessary for cleaning performance, and the loading force is used to suppress bleed out of the liquid surfactant, and the flowability of the powder detergent is reduced. And it is important in preventing the liquid surfactant from transferring to the container and its surface.
- the property of quickly absorbing the liquid surfactant (supporting speed) is also required for the surfactant-supporting granules.
- Patent Literature 1 discloses a surfactant-supporting granule group in which a preparation liquid containing a water-soluble polymer and a water-soluble salt is spray-dried.
- spray drying is essential for the production of this granule group, and a production method that does not use spray drying is required from the viewpoint of economy.
- Patent Document 2 discloses a method of drying a composition comprising a hydrated inorganic salt and a polymer organic binder.
- this method is essentially a technique for releasing water of hydration by drying to increase the absorption capacity (corresponding to the loading capacity in the present application), and it is extremely difficult to adjust the loading force and loading speed. Therefore, there is a demand for a surfactant-supporting granule group that is excellent in all of the supporting capacity / supporting force / supporting speed.
- an object of the present invention is to produce a surfactant-supporting granule group excellent in supporting capacity / supporting power / supporting speed of a liquid surfactant composition by a method not using spray drying.
- Another object of the present invention is to provide a high bulk density detergent particle group using the surfactant-carrying granule group and a detergent composition containing the detergent particle group.
- the gist of the present invention is as follows.
- a method for producing a surfactant-supporting granule group having a bulk density of 550 g / l or less comprising the following steps 1 (a) to 2;
- a process for producing a surfactant-supporting granule group having a bulk density of 550 g / l or less comprising the following steps 1 (b) to 2;
- Step 2 Add water or an aqueous binder solution to the mixed powder obtained in Step 1 (b
- the present invention it is possible to obtain a surfactant-supporting granule group excellent in supporting capacity / supporting force / supporting speed of the liquid surfactant composition by a method not using spray drying. Furthermore, by carrying the liquid surfactant composition on the surfactant-carrying granules, it is possible to efficiently obtain detergent particles having good cleaning performance and quality.
- the surfactant-supporting granule is a granule containing at least a powder raw material having an oil absorption capacity of 0.4 ml / g or more excluding clay mineral and water or an aqueous binder solution.
- the aggregate of the granules is called a surfactant-supporting granule group.
- the detergent particles are particles containing a surfactant, a builder, and the like obtained by supporting a surfactant-supporting granule with a liquid surfactant composition, and the detergent particle group means an aggregate thereof.
- the detergent composition contains detergent particles and is optionally added separately from the detergent particles (for example, builder granules, fluorescent dyes, enzymes, fragrances, antifoams, bleaches, bleach activators) Etc.).
- Water-soluble means that the solubility in water at 25 ° C. is 0.5 g / 100 g or more, and water-insoluble means that the solubility in water at 25 ° C. is less than 0.5 g / 100 g.
- the liquid surfactant composition is a composition containing a surfactant that is liquid or pasty when supported on a surfactant-supporting granule group.
- Powder raw material having an oil absorption capacity of 0.4 ml / g or more excluding clay minerals As an essential component in the present invention, a powder raw material having an oil absorption capacity of 0.4 ml / g or more excluding clay minerals can be mentioned.
- the oil absorption capacity is a value determined by the method described in the quality evaluation method described later.
- the powder raw material having an oil absorption capacity of 0.4 ml / g or more excluding clay minerals is an essentially porous substance having fine pores of 10 ⁇ m or less inside the powder, and a surface activity is present in the pores. It is a substance that can carry an agent.
- the upper limit of the oil absorption capacity is not particularly limited, but is preferably 1.0 ml / g or less, for example.
- the average particle size of the powder raw material is preferably 50 to 250 ⁇ m, more preferably 50 to 200 ⁇ m, still more preferably 80 to 200 ⁇ m.
- solubility it is preferably a water-soluble substance.
- powder raw material examples include light ash or soda ash prepared by baking baking soda, mirabilite, porous powder prepared by drying trihydrate of sodium tripolyphosphate. Light ash is particularly preferable from the viewpoint of easy handling and availability.
- the ability to support the surfactant can be further improved by adjusting the temperature during baking baking soda.
- the firing temperature is preferably 120 to 250 ° C, more preferably 150 to 220 ° C, and even more preferably 150 to 200 ° C.
- the content of the powder raw material is preferably 40 to 95% by weight, more preferably 45 to 90% by weight, still more preferably 50 to 85% by weight, in the surfactant-supporting granule group, from the viewpoint of supportability. 50 to 80% by weight is particularly preferred.
- the granule group before the drying step is preferably 25 to 80% by weight, more preferably 30 to 77% by weight, still more preferably 32 to 77% by weight, 32 to 73% by weight is particularly preferred.
- Binder The granule group for supporting a surfactant in the present invention granulates a mixture of powder raw materials by adding water or an aqueous binder solution and using a low shear granulator.
- clay mineral When clay mineral is used, a mixture of the clay mineral and the powder raw material is granulated.
- the caking property generated by partly dissolving the powder raw material in water or the caking property of clay mineral is used for granulation.
- an aqueous binder solution since the caking property due to the binder can be used, granulation becomes easier.
- a drying step when water is used, there is a concern that the particle strength may decrease with drying, but when an aqueous binder solution is used, the effect of the binder can be expected even after drying. Therefore, it is preferable to use a binder aqueous solution.
- the binder is not particularly limited as long as it has an ability to bind the components constituting the particles in the powder raw material and has a property of rapidly dissolving and / or dispersing in water.
- water-soluble cellulose derivatives, saccharides and carboxylic acid polymers are preferred, and acrylic acid-maleic acid copolymer salts and polyacrylates are more preferred.
- the salt is preferably a sodium salt, potassium salt or ammonium salt.
- the weight average molecular weight of the carboxylic acid polymer is preferably 1000 to 100,000, more preferably 2000 to 80000.
- the content of the binder in the surfactant-carrying granule group is preferably 0 to 35% by weight and more preferably 5 to 30% by weight in the surfactant-carrying granule group from the viewpoints of caking property and oil absorption. 8 to 20% by weight is more preferable, and 10 to 20% by weight is particularly preferable. In the case of adjusting to the above composition by the drying step, 0 to 30% by weight is preferable in the granule group before the drying step, more preferably 3 to 25% by weight, still more preferably 5 to 17% by weight, 7 to 17% by weight is particularly preferred.
- the concentration of the aqueous binder solution is not particularly limited, but the particle size at the time of granulation is greatly affected by the volume of the aqueous binder solution, so the concentration may be determined from the required binder amount and the desired granule particle size.
- Clay minerals have a layered structure and can carry a liquid surfactant between the layers. Therefore, by adding clay minerals, it is possible to increase the loading capacity of the liquid surfactant and at the same time improve the loading capacity.
- the particle size of the particles for supporting the surfactant can be controlled by adjusting the amount of the clay mineral.
- a clay mineral may be added as a component for improving the supporting capacity / supporting power.
- clay minerals examples include talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite), vermiculite, mica (phlogopite, biotite, chinwald mica).
- Muscovite paragonite, ceradonite, sea chlorite, etc.
- chlorite (clinochlore, chamosite, nimite, pennite, sudowite, dombasite, etc.)
- brittle mica (clinentite, margarite, etc.)
- sulite serpentine mineral
- kaolin minerals kaolinite, dickite, nacrite, halloysite, etc.
- talc talc
- smectite swellable mica
- vermiculite chrysotile
- kaolin mineral kaolin mineral
- montmorillonite is further preferable in terms of flexibility. These may be used alone or in appropriate combination of two or more.
- Examples of the clay mineral represented by the general formula (I) include “Round rosyl DGA212”, “Round rosyl PR414”, “Round rosyl DG214”, “Round rosyl DGA powder”, “EXM0242”, “Hulasoft” manufactured by Sud Kemi. 1 powder ”,“ Detasoft GIS ”,“ Detasoft GIB ”,“ Detasoft GISW ”manufactured by Raviossa, Pure Bentonite, Standard Bentonite, Premium Bentonite manufactured by CSM, and the like.
- there are granulated granule types added with a binder component which may be added as long as the effects of the present invention are not impaired. .
- the clay minerals listed above are used in the present invention, those in the form of powder are preferable from the viewpoint of granulation, and in the case of a granulated product, it is preferable to crush in advance until a suitable particle size is obtained.
- the crusher that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. These may be a single-stage operation or a multi-stage operation of the same or different pulverizers.
- the average particle size of the clay mineral powder is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less.
- the clay mineral represented by the general formula (I) is composed of a total of alkali metal ions (Na ions, K ions, Li ions) and alkaline earth metal ions (Ca ions, Mg ions).
- the total molar ratio [(Na + K + Li) / (Ca + Mg)] of ions is preferably 1.0 or more, more preferably 1.5 or more, and further preferably 2.0 or more.
- a clay mineral having a high ratio of alkali metal ions it is only necessary to select a production area if it is a natural product, and it can also be prepared by adding an alkali metal salt when producing a clay granulated product. . Moreover, if it is a synthetic product, it can be arbitrarily prepared by a known method.
- the surfactant-supporting granule group in the present invention contains an appropriate amount of water used in the production process.
- the moisture content measured with an infrared moisture meter is preferably smaller from the viewpoint of increasing the carrying capacity of the liquid surfactant composition of the granule group, preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably. Is 5% by weight or less.
- surfactant-carrying granule group in the present invention substances other than those listed in the above 1 to 4 can be appropriately blended as necessary.
- the blending amount of these substances is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less from the viewpoint of supporting ability. Examples of substances that can be blended are shown below.
- the water-soluble chelating agent is not particularly limited as long as it is a substance that retains sequestering ability, but crystalline silicate, tripolyphosphate, orthophosphate, pyrophosphate and the like can be used. Among these, crystalline silicate and tripolyphosphate are preferable.
- the water-insoluble chelating agent preferably has an average particle diameter of 0.1 to 20 ⁇ m from the viewpoint of dispersibility in water. Suitable water-insoluble chelating agents include crystalline aluminosilicates, such as A-type zeolite, P-type zeolite, and X-type zeolite. A-type zeolite is preferred in terms of sequestering ability and economy. .
- a water-soluble inorganic salt in order to increase the ionic strength of the washing liquid and improve the effect of washing sebum dirt.
- the substance is not particularly defined as long as it has good solubility and does not adversely affect the detergency.
- an alkali metal salt having a sulfate group and a sulfite group, an ammonium salt, and the like can be given.
- sodium sulfate, sodium sulfite, or potassium sulfate having a high degree of ion dissociation as an excipient. From the viewpoint of improving the dissolution rate, the combined use with magnesium sulfate is also preferable.
- Water-insoluble excipient No particular limitation is imposed on the substance as long as it has good dispersibility in water and does not adversely affect detergency. Examples thereof include crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, and the like. From the viewpoint of dispersibility in water, the primary particles preferably have an average particle size of 0.1 to 20 ⁇ m.
- Fluorescent dyes, pigments, dyes, etc. are listed.
- the measurement of the average particle diameter of the said component can be measured by the method as described in the measuring method of the physical property mentioned later.
- the surfactant-supporting granule group of the present invention does not include a spray drying step, and at least a step of stirring or mixing powder raw materials having an oil absorption capacity of 0.4 ml / g or more excluding clay minerals, and the obtained mixed powder. It can be prepared by a method including a step of adding water or an aqueous binder solution and granulating with a low shear granulator.
- Step 1 (a) In the step of mixing powder raw materials having an oil absorption capacity of 0.4 ml / g or more excluding clay mineral powder and clay mineral, any method may be used as long as they can be mixed substantially uniformly.
- the low shear granulator used in step 2 may be used for mixing, or may be mixed in advance using another mixer and then transferred to the low shear granulator.
- the other mixer used for powder mixing include a drum mixer, a bread mixer, a ribbon mixer, a nauter mixer, a Shugi mixer, a Redige mixer, and a high speed mixer.
- the content of the clay mineral is preferably 1 to 45% by weight, more preferably 2 to 40% by weight, more preferably 3 to 40% by weight in the surfactant-supporting granule group, from the viewpoint of supporting ability and particle size control. % By weight is more preferred, 3 to 35% by weight is more preferred, and 4 to 30% by weight is particularly preferred.
- it may be dried as desired. However, in the case of adjusting to the above composition by such a drying step, 1 to 40% by weight is preferable in the granule group before the drying step. Is more preferably 35% by weight, more preferably 3-30% by weight, still more preferably 3-25% by weight, and particularly preferably 6-25% by weight.
- the weight ratio of the clay mineral to the powder raw material is preferably 1/1 to 1/30, more preferably 1/1 to 1/20, and particularly preferably 1/2 to 1/20.
- Step 1 (b) In the step of stirring or mixing powder raw materials having an oil absorption capacity of 0.4 ml / g or more excluding clay minerals, any method may be used as long as they can be mixed substantially uniformly.
- the low shear granulator used in Step 2 may be used for mixing, or may be mixed in advance using the above-described mixer and then transferred to the low shear granulator.
- the powder raw material excluding the clay mineral is a powder raw material which does not substantially contain the clay mineral, and may contain 0 to 1.2% by weight of the clay mineral in the powder raw material.
- the clay mineral content is more preferably 0 to 1.0% by weight in the powder raw material, still more preferably 0 to 0.8% by weight, and particularly preferably 0 to 0.6% by weight.
- the clay mineral content is from 0 to 0 in the surfactant-carrying granule group. It is preferably 1% by weight, more preferably 0 to 0.8% by weight, still more preferably 0 to 0.6% by weight, and particularly preferably 0 to 0.5% by weight.
- it may be dried as desired, but in the case of adjusting to the above composition by such a drying step, 0 to 0.9% by weight in the granule group before the drying step is preferable. 0 to 0.7 wt% is more preferable, 0 to 0.5 wt% is still more preferable, and 0 to 0.4 wt% is particularly preferable.
- Process 2 In this step, water or an aqueous binder solution is added to the mixed powder obtained in step 1 (a) or step 1 (b) and granulated by a low shear granulator. In this process, granules having a structure in which powder raw materials are gradually aggregated are generated. Also, step 1 (a) or step 1 (b) and step 2 can be performed simultaneously.
- the low-shear granulator used in this step may be an apparatus that gives strong shear to the granules and does not greatly compact.
- the granule of the present invention is controlled by setting the number of revolutions and the fluid number described below low to suppress the compaction.
- a pan granulator or a drum granulator in which granulation proceeds by rotation of the main body barrel is preferable from the viewpoint of easy granulation and improved carrying ability.
- These apparatuses can be used in both batch and continuous processes. From the viewpoint of powder mixing property and solid-liquid mixing property, it is preferable to provide a baffle plate for assisting mixing in the pan or drum.
- the fluid number of the granulator defined by the following formula is 1.0 or less from the viewpoint of supporting ability, and 0.8 or less. More preferably, 0.6 or less is further preferable, and 0.4 or less is particularly preferable.
- Fluid number: Fr V 2 / (R ⁇ g) V: peripheral speed [m / s] R: radius from the center of rotation to the circumference of the rotating object [m] g: acceleration of gravity [m / s 2 ]
- the fluid number of the granulator is preferably set to 0.005 or more, and more preferably set to 0.01 or more.
- V and R use the value of the main shaft, and a bread granulator or a drum granulator in which granulation proceeds by rotation of the body barrel.
- the values of the body trunk are used for V and R.
- V and R use values of the crushing blade.
- the present invention it is important to obtain granules having a structure in which they are granulated with low shear and gradually aggregated.
- low shear there is a problem that water or an aqueous binder solution is hardly dispersed uniformly. Therefore, it is preferable to uniformly disperse the binder by a liquid addition method.
- a method of uniformly dispersing the binder there is a method of refining the binder using a multi-fluid nozzle such as a 1-fluid nozzle or a 2-fluid nozzle.
- the multi-fluid nozzle is a nozzle that mixes and atomizes a binder and atomizing gas (air, nitrogen, etc.) through an independent channel to the vicinity of the nozzle tip.
- a binder and atomizing gas air, nitrogen, etc.
- a fluid nozzle or the like can be used.
- the mixing part of the binder and atomizing gas may be either an internal mixing type that mixes in the nozzle tip part or an external mixing type that mixes outside the nozzle tip part.
- a multi-fluid nozzle such as a two-fluid nozzle.
- a multi-fluid nozzle for example, a wide-angle round type two-fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd.), a four-fluid nozzle (manufactured by Fujisaki Electric Co., Ltd.), or the like can be used.
- Process 3 This is an optional step of drying the granules obtained in step 2. By removing moisture, voids in the particles are increased, and the carrying capacity can be further improved.
- a drying method that gives as much strong shearing force as possible is preferable.
- the batch type there are a method of drying in an electric dryer or hot air dryer in a container, a method of drying in a batch type fluidized bed, etc., and in a continuous type, a vibrating fluidized bed, a rotary dryer, a steam tube dryer, etc. Etc.
- the drying temperature is preferably 80 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 180 ° C. or higher from the viewpoint of the drying speed.
- 300 degrees C or less is preferable, 250 degrees C or less is more preferable, and 220 degrees C or less is especially preferable.
- the surfactant-carrying granule group in the present invention is a granule group having a structure in which at least a powder raw material having an oil absorption capacity of 0.4 ml / g or more excluding clay mineral is gradually aggregated. Therefore, it has two supporting sites: (1) a large gap between powder raw materials, and (2) a small gap (for example, a gap of 10 ⁇ m or less) in the powder raw material. Of these, both (1) and (2) have a significant effect on the loading capacity and loading force, and (1) has a significant effect on the loading speed, and the surfactant having the desired loading capacity can be adjusted by adjusting these two loading sites. A group of supporting granules can be obtained.
- liquid surfactant composition when a clay mineral is blended, the liquid surfactant composition can be supported between the layers, so that the supporting ability is expected to be improved.
- the bulk density of the particles for supporting a surfactant of the present invention is 550 g from the viewpoint of securing the loading capacity of the liquid surfactant composition and from the viewpoint of securing a high bulk density after loading the liquid surfactant composition. / L or less, preferably 400 to 550 g / L, more preferably 400 to 500 g / L.
- the relatively low bulk density of the supporting granules of the present invention is considered to be achieved by granulating with the low shear granulator described above.
- the average particle size of the supporting granule group from the viewpoint of powderiness and solubility when the detergent composition containing the detergent particle group in which the liquid surfactant composition is supported on the surfactant supporting granule group is used.
- the diameter is preferably 140 to 600 ⁇ m, more preferably 200 to 500 ⁇ m, still more preferably 200 to 400 ⁇ m.
- the oil-absorbing ability of the liquid surfactant composition in the surfactant-supporting granule group is preferably 0.4 ml / g or more, more preferably from the viewpoint of increasing the allowable range of the liquid surfactant composition content. It is 45 ml / g or more, particularly preferably 0.5 ml / g or more. It is considered that the relatively high oil absorption capacity of the supporting granules of the present invention is achieved by granulating with the low shear granulator described above.
- the amount of water measured by the infrared moisture meter of the granules for supporting the surfactant is preferably smaller from the viewpoint of increasing the carrying capacity of the liquid surfactant composition of the granules, preferably 15% by weight or less, more preferably Is 10% by weight or less, more preferably 5% by weight or less.
- the specific composition of the surfactant-supporting granule group of the present invention is, for example, 40 to 95 powder raw materials having a bulk density of 550 g / l or less and an oil absorption capacity of 0.4 ml / g or more excluding clay minerals.
- Examples include a composition of 0 wt%, 0 to 45 wt% of clay mineral powder, 0 to 35 wt% of binder, and 0 to 15 wt% of water.
- the bulk density, average particle size, oil absorption capacity and water content of the liquid surfactant composition can be measured by the methods described in the physical property measurement method described later.
- the detergent particle group of the present invention is a surfactant-supporting granule group according to the present invention (that is, the surfactant-supporting granule group obtained by the production method of the present invention and the above-described surfactant-supporting granule group of the present invention).
- a surfactant-supporting granule group according to the present invention that is, the surfactant-supporting granule group obtained by the production method of the present invention and the above-described surfactant-supporting granule group of the present invention.
- this detergent particle group in this detergent particle group, as long as it contains the surfactant-supporting granule group according to the present invention, it may not be alone, and it should be used together with the surfactant-supporting granule group by spray drying or other methods. You can also. When used in combination, the mixture of the granule group according to the present invention and the granule group by spray drying or other methods can be handled as the surfactant-supporting granule group.
- an anionic surfactant and a nonionic surfactant can be used alone, but it is more preferable to use a mixture of both.
- a nonionic surfactant having a melting point of 30 ° C. or lower a water-soluble nonionic organic substance having a melting point of 45 to 100 ° C. and a molecular weight of 1,000 to 30,000 has an effect of increasing the melting point of the surfactant.
- a compound hereinafter referred to as a melting point increasing agent
- an aqueous solution thereof a compound (hereinafter referred to as a melting point increasing agent) or an aqueous solution thereof together.
- melting point raising agent examples include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic-type nonionic surfactant. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose. Further, from the viewpoint of improving the dispersibility of the detergent particles in low-temperature water, an anionic surfactant such as an alkylbenzene sulfonate can be preferably added to the detergent particles in an amount of 5 to 25% by weight.
- the surfactant composition for example, one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.
- anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid salt or ester thereof, alkyl or alkenyl ether carboxylate, amino acid type surfactant And N-acylamino acid type surfactants.
- linear alkylbenzene sulfonates, alkyl sulfates or alkyl ether sulfates are preferable, and as counter ions, alkali metals such as sodium and potassium, and amines such as monoethanolamine and diethanolamine are preferable.
- a fatty acid salt can be used in combination.
- nonionic surfactant examples include polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl or alkenyl phenyl ether, polyoxyethylene polyoxypropylene alkyl or alkenyl ether, and polyoxyethylene polyoxypropylene glycol represented by trademark Pluronic , Polyoxyethylene alkylamine, higher fatty acid alkanolamide, alkyl glucoside, alkyl glucose amide, alkyl amine oxide and the like. Among them, those having high hydrophilicity and those having a low liquid crystal forming ability when mixed with water or those that do not produce liquid crystal are preferable, and polyoxyalkylene alkyl or alkenyl ether is particularly preferable.
- EO ethylene oxide
- PO propylene oxide
- PO propylene oxide
- R represents a hydrocarbon group, preferably an alkyl group or an alkenyl group
- EO represents an oxyethylene group
- PO represents an oxypropylene group
- X, Y, and Z each represent an average number of moles added.
- the most preferable average added mole number relationship is X> 0, Z> 0, X + Y +
- cationic surfactant examples include quaternary ammonium salts such as alkyltrimethylammonium salts.
- amphoteric surfactants examples include carbobetaine type and sulfobetaine type.
- the amount of the anionic surfactant in the surfactant composition is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 parts by weight based on 100 parts by weight of the nonionic surfactant. ⁇ 180 parts by weight.
- the blending amount of the nonionic surfactant melting point increasing agent is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the nonionic surfactant.
- the composition has a temperature at which the viscosity of the composition is preferably 10 Pa ⁇ s or less, more preferably 5 Pa ⁇ s or less, particularly preferably 2 Pa ⁇ s or less at a temperature equal to or higher than the pour point of the composition.
- the penetration hardness of the composition is preferably 10 kPa or more, more preferably 30 kPa or more, particularly preferably 50 kPa or more. Suitable because the composition and the detergent particles can be easily handled and the nonionic surfactant can be prevented from smearing during storage of the detergent particles. It is.
- the physical property value of the surfactant composition can be measured by the following method.
- the pour point can be measured by the method of JIS K 2269.
- the melting point is measured by using “Mettler FP81” (manufactured by Mettler Instrument AG) of FP800 thermosystem at a heating rate of 0.2 ° C./min.
- Viscosity was measured using a B type viscometer (“DVM-B type” manufactured by TOKYO KEIKI), rotor No. 3. Measured under conditions of 60 r / min. If the measured value under these conditions exceeds 2 Pa ⁇ s and measurement is impossible, the rotor no. 3. Measured under conditions of 3 and 12 r / min.
- the penetration hardness was measured using a rheometer (“NRM-3002D”, manufactured by Fudo Kogyo Co., Ltd.) and a circular adapter (No. 3, 8 ⁇ ) with a diameter of 8 mm and a bottom area of 0.5 cm 2 . It is the value which divided
- the addition amount of the surfactant composition is preferably in the range of 10 to 100 parts by weight and in the range of 20 to 80 parts by weight with respect to 100 parts by weight of the surfactant-supporting granules from the viewpoint of detergency and solubility. Is more preferable, and the range of 30 to 60 parts by weight is particularly preferable.
- a powder raw material other than the powder raw material may be added if desired, and the addition amount is based on 100 parts by weight of the granule group. 0 to 150 parts by weight is preferable.
- the powder raw material include crystalline silicates such as aluminosilicate and prefeed (manufactured by Tokuyama Siltech Co., Ltd.).
- the bulk density is preferably 500 to 1000 g / L, more preferably 600 to 1000 g / L, and particularly preferably 650 to 900 g / L.
- the average particle diameter is preferably 150 to 500 ⁇ m, more preferably 180 to 400 ⁇ m.
- the said bulk density and an average particle diameter can be measured by the method as described in the measuring method of the below-mentioned physical property.
- a suitable production method for obtaining the detergent particle group includes the following step (I), and may further include step (II) as necessary.
- Step (I) Examples of the method for supporting the surfactant composition on the supporting granule group include a method of mixing the supporting granule group and the surfactant composition using a batch type or continuous mixer.
- the charging method to the mixer is as follows: (1) First, the support granule group is charged into the mixer, and then the surfactant composition is added all at once. (2) The mixer Repeatedly add the supporting granule group and surfactant composition little by little. (3) After charging a part of the supporting granule group into the mixer, the remaining supporting granule group and surfactant composition It is possible to take a method such as repeatedly adding a small amount of the product.
- surfactant compositions those that exist in the form of a solid or paste even when the temperature is raised to a practical temperature range, for example, 50 to 90 ° C., are preliminarily added to the low-viscosity non-ion.
- a surfactant or nonionic surfactant aqueous solution or water is dispersed or dissolved to prepare a surfactant composition mixed solution or aqueous solution, which is added to the supporting granules in the form of the mixed solution or aqueous solution. It ’s fine.
- a surfactant composition existing in a solid or paste form can be easily added to the supporting granules.
- the mixing ratio of the surfactant composition having low viscosity or water and the surfactant composition in the form of solid or paste is preferably within a viscosity range in which the resulting mixed solution or aqueous solution can be sprayed.
- Examples of the method for producing the mixed liquid include a method in which a surfactant having a low viscosity or a solid surfactant composition is added to water and mixing, or a surfactant in a surfactant having low viscosity or in water.
- a surfactant composition mixture by neutralizing an acid precursor of, for example, an anionic surfactant acid precursor with an alkali agent (for example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution) It may be.
- the acid of the anionic surfactant is added before the surfactant composition, simultaneously with the addition of the surfactant composition, during the addition of the surfactant composition, or after the addition of the surfactant composition. It is also possible to add a precursor. By adding an acid precursor of an anionic surfactant, it is possible to increase the amount of the surfactant, to support the supporting granule group, to control the supporting ability, and to prevent the nonionic surfactant in the detergent particle group from bleeding out. In addition, physical properties such as fluidity and quality can be improved.
- Examples of the acid precursor of the anionic surfactant that can be used in the present invention include alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid, alkyl or alkenyl sulfuric acid, ⁇ -olefin sulfonic acid, ⁇ -sulfonated fatty acid, alkyl Or an alkenyl ether carboxylic acid, a fatty acid, etc. are mentioned. It is particularly preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.
- the amount of the anionic surfactant acid precursor used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the supporting granules. More preferred is 1 to 5 parts by weight.
- the method for adding the acid precursor of the anionic surfactant it is preferable to spray the liquid that is liquid at room temperature, and the liquid that is solid at room temperature may be added as a powder or melted. You may supply after spraying. However, when adding with a powder, it is preferable to raise the temperature of the detergent particle group in a mixer to the temperature which a powder fuse
- preferable mixing apparatuses include the following.
- the following (1) to (3) are preferable.
- Henschel mixer manufactured by Mitsui Miike Chemical Co., Ltd.
- high speed mixer manufactured by Fukae Kogyo Co., Ltd.
- vertical granulator manufactured by Paulek, Inc.
- Redige mixer manufactured by Matsuzaka Giken Co., Ltd.
- Proshear mixer manufactured by Taiheiyo Kiko Co., Ltd.
- the mixing device described in Japanese Patent Application Laid-Open No. 10-296064 and the mixing device described in Japanese Patent Application Laid-Open No. 10-296065 can regulate the moisture content and temperature of the mixture by aeration, and can suppress the collapse of the particles for supporting the surfactant.
- a mixing device such as a Nauter mixer, SV mixer, or ribbon mixer capable of mixing powder and liquid without giving a strong shearing force is preferable from the viewpoint that the disintegration of the surfactant-carrying granule group can be suppressed.
- the supporting granule group and the surfactant composition may be mixed using a continuous apparatus.
- the continuous apparatus include a flexographic type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.), and the like.
- a water-soluble nonionic organic substance having a melting point of 45 to 100 ° C. and a molecular weight of 1,000 to 30,000 has an effect of increasing the melting point of the surfactant.
- a compound (hereinafter referred to as a melting point increasing agent) or an aqueous solution thereof is added before the addition of the surfactant composition, simultaneously with the addition of the surfactant composition, during the addition of the surfactant composition, or after the addition of the surfactant composition. Or it is preferable to mix and add to surfactant composition beforehand.
- melting point raising agents the same thing as what was illustrated in the melting point raising agent of the composition of the above-mentioned detergent particle group can be used.
- the amount of the melting point raising agent used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and most preferably 1 to 3 parts by weight with respect to 100 parts by weight of the supporting granule group. This range is preferable from the viewpoint of suppression of aggregation between detergent particles contained in the detergent particle group, high-speed solubility, and suppression of spotting and caking properties.
- melting point increasing agent As a method for adding the melting point increasing agent, mixing with a surfactant in advance by an arbitrary method, or adding a melting point increasing agent after the addition of the surfactant is effective for the detergent particles to cause stains and caking properties. It is advantageous for suppression.
- the temperature in the mixer in this step is higher than the pour point of the surfactant composition and mixed.
- the pour point of the surfactant composition is measured by the method defined in JIS K 2269.
- the temperature to be raised may be higher than the pour point of the surfactant composition added to promote the loading of the surfactant composition.
- a temperature up to 50 ° C. higher than the pour point is preferable, and a temperature higher by 10 ° C. to 30 ° C. than the pour point is more preferable.
- the temperature is raised to a temperature at which the acid precursor of the anionic surfactant can react and mixing is performed.
- the batch mixing time for obtaining a suitable detergent particle group and the average residence time in continuous mixing are preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.
- a surfactant aqueous solution or a water-soluble nonionic organic compound aqueous solution may have a step of drying excess water during and / or after mixing.
- a powdery surfactant and / or a powder builder before, simultaneously with, during or after the addition of the surfactant composition.
- a powder builder By adding a powder builder, the particle diameter of the detergent particles can be controlled, and the cleaning power can be improved.
- an acid precursor of an anionic surfactant is added, it is effective from the viewpoint of accelerating the neutralization reaction to add an alkaline powder builder before adding the acid precursor.
- the term “powder builder” as used herein means a powder detergency enhancer other than a surfactant.
- a base that exhibits sequestering ability such as zeolite and citrate, and sodium carbonate.
- a base exhibiting alkaline ability such as potassium carbonate
- a base having both sequestering ability and alkaline ability such as crystalline silicate, and other bases such as sodium sulfate that enhance ionic strength.
- the crystalline silicate JP-A-5-279013, column 3, line 17 (especially, it is preferably crystallized by firing at 500 to 1000 ° C.), JP-A-7-89712.
- the crystalline silicate described in column 2, line 45, JP-A-60-227895, page 2, lower right column, line 18 (particularly silicates in Table 2 are preferred) is preferably used as a powder builder. it can.
- the alkali metal silicate having SiO 2 / M 2 O (where M represents an alkali metal) is preferably 0.5 to 3.2, more preferably 1.5 to 2.6. Used.
- the amount of the powder builder used is preferably 0.5 to 12 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the supporting granule group.
- the detergent powder builder has good solubility in this range.
- step (II) for modifying the surface of the detergent particles after the step (I).
- Process (II) in order to modify the particle surface of the detergent particle group on which the surfactant is supported in the step (I), the form at the time of addition is as follows: (1) fine powder, (2) liquid One or more steps (II) of adding various surface coating agents may be performed.
- step (II) is preferably, for example, a mixer equipped with both a stirring blade and a crushing blade among the mixers exemplified in step (I).
- Each surface coating agent will be described below.
- the fine powder preferably has an average primary particle size of 10 ⁇ m or less, more preferably 0.1 to 10 ⁇ m. When the average particle size is within this range, the coverage of the detergent particle group on the particle surface is improved, which is preferable from the viewpoint of improving the fluidity and caking resistance of the detergent particle group.
- the average particle diameter of the fine powder is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba Seisakusho) or a measurement by microscopic observation. Further, it is preferable from the viewpoint of detergency that the fine powder has a high ion exchange ability and a high alkali ability.
- the fine powder is preferably an aluminosilicate and may be crystalline or amorphous.
- fine powders such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and crystalline silicate are also preferable.
- a metal soap having an average primary particle size of 0.1 to 10 ⁇ m, a powdered surfactant (such as an alkyl sulfate) and a water-soluble organic salt can be used in the same manner.
- crystalline silicate it is preferable to use it by mixing with fine powder other than crystalline silicate for the purpose of preventing deterioration due to moisture absorption or aggregation of crystalline silicate due to carbon dioxide.
- the amount of fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 20 parts by weight with respect to 100 parts by weight of the detergent particles. When the amount of the fine powder used is within this range, the fluidity is improved and the consumer feels good.
- Liquid substance As a liquid substance, a water-soluble polymer, a fatty acid, etc. are mentioned, It can add in aqueous solution or a molten state.
- water-soluble polymer examples include carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, a polycarboxylic acid salt such as a copolymer of acrylic acid and maleic acid or a salt thereof, and the like.
- the amount of the water-soluble polymer used is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight with respect to 100 parts by weight of the detergent particles. When the amount of the water-soluble polymer used is within this range, a detergent particle group exhibiting good solubility, good fluidity, and caking resistance can be obtained.
- (2-2) Fatty acid examples include fatty acids having 10 to 22 carbon atoms.
- the amount of the fatty acid used is preferably 0.5 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight based on 100 parts by weight of the detergent particles. In the case of a solid at room temperature, it is preferable to spray and supply after heating to a temperature showing fluidity.
- the detergent composition in the present invention is a composition comprising the above-described detergent particle group, and further contains detergent components (for example, builder granules, fluorescent dyes, enzymes, perfumes, odorants, etc.) separately added to the detergent particle group.
- detergent components for example, builder granules, fluorescent dyes, enzymes, perfumes, odorants, etc.
- the content of the detergent particles in the detergent composition is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, 80% by weight or more, 100% by weight or less from the viewpoint of detergency. Is particularly preferred.
- the content of detergent components other than the detergent particle group in the detergent composition is preferably 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less, and particularly preferably 20% by weight or less.
- the method for producing the detergent composition is not particularly limited, and examples thereof include a method of mixing the detergent particle group and a separately added detergent component. Since the detergent composition thus obtained contains detergent particles with a large carrying capacity of a surfactant, a sufficient cleaning effect can be exhibited even with a small amount.
- the use of such a detergent composition is not particularly limited as long as it is a use using a powder detergent, and examples thereof include a powder detergent for clothing and a detergent for automatic tableware.
- Average particle diameter was measured by the following two methods. (1) For those with an average particle size of 80 ⁇ m or more, use a JIS K 8801 standard sieve (mesh 2000 to 125 ⁇ m) for 5 minutes, and then calculate the median diameter from the weight fraction of the sieve mesh size. To do. More specifically, using a 9-stage sieve and a tray with a mesh opening of 125 ⁇ m, 180 ⁇ m, 250 ⁇ m, 355 ⁇ m, 500 ⁇ m, 710 ⁇ m, 1000 ⁇ m, 1400 ⁇ m, and 2000 ⁇ m, the top of the top is stacked in order from the small sieve.
- the moisture content of the granules is measured by the infrared moisture meter method. That is, 3 g of a sample was placed on a sample pan having a known weight, heated at 200 ° C. using an infrared moisture meter (FD-240 manufactured by Kett Science Laboratory Co., Ltd.), and when the weight change disappeared for 30 seconds, drying was completed. It was. Then, the water content is calculated from the weight after drying and the weight before drying.
- FD-240 infrared moisture meter manufactured by Kett Science Laboratory Co., Ltd.
- the flow time is defined as the time required for 100 mL of powder to flow out from the bulk density measurement hopper defined by 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.
- Oil absorption capacity 30-35 g of powder was put into an absorption measuring device (AS410, manufactured by Asahi Research Institute), and the driving blade 200r. p. m. Rotate with.
- a liquid nonion (Emulgen 108 manufactured by Kao Corporation) is dropped at a liquid supply rate of 4 ml / min to determine the point at which the maximum torque is obtained.
- the liquid addition amount at the point where the torque becomes 70% of the point where the maximum torque is reached is divided by the amount of powder input to obtain the oil absorption capacity.
- Particle size distribution As an index of particle size distribution, a detergent particle group that has been passed through a sieve of 1410 ⁇ m is fitted, and the Rosin-Rammler number is calculated and used. The following formula is used to calculate the Rosin-Rammler number.
- n is preferably 1.0 or more, and more preferably 1.5 or more.
- solubility index in the present invention a 60-second dissolution rate of a detergent particle group described below can be used.
- the dissolution rate is preferably 90% or more, and more preferably 95% or more.
- the detergent composition can be evaluated by the same method.
- the dissolution rate of the detergent particle group for 60 seconds is calculated by the following method.
- 1 liter of hard water (Ca / Mg molar ratio 7/3) cooled to 5 ° C. corresponding to a hardness of 71.2 mg CaCO 3 / liter is a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd.) Filled in a 1 liter glass beaker, and kept at a water temperature of 5 ° C.
- stirrer length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) SA ( In the round thin type)
- stirring is performed at a rotational speed (800 rpm) at which the depth of the vortex with respect to the water depth is approximately 1/3.
- the detergent particles which have been reduced and weighed to 1.000 ⁇ 0.0010 g, are added and dispersed in water with stirring, and stirring is continued.
- the detergent particle group dispersion in the beaker is filtered through a standard sieve (diameter: 100 mm) having an opening of 74 ⁇ m as defined in JIS Z 8801, which has a known weight, and the detergent particles in the water state remaining on the sieve are filtered. Collect in an open container with known weight along with sieve. The operation time from the start of filtration until the sieve is collected is 10 ⁇ 2 seconds.
- the collected residue of detergent particles is dried in an electric dryer heated to 105 ° C. for 1 hour, and then cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total weight of the dissolved residue of the dried detergent, the sieve, and the collection container is measured, and the dissolution rate (%) of the detergent particle group is calculated by the equation (1).
- Dissolution rate (%) ⁇ 1 ⁇ (T / S) ⁇ ⁇ 100
- S input weight of detergent particles
- T dry weight of the residue of the detergent particles remaining on the sieve (drying condition: 1 hour at a temperature of 105 ° C. (After holding, hold in a desiccator (25 ° C) containing silica gel for 30 minutes)
- Granule Yield The granule yield in the present invention is determined by the proportion of granules in a specific particle size range among all the granules. For example, the granule yield of 125-1000 ⁇ m indicates the proportion of granules of 125 ⁇ m or more and 1000 ⁇ m or less of all the granules.
- the detergent yield in the present invention refers to the proportion of particles of 1180 ⁇ m or less in the detergent composition obtained by mixing the detergent particle group and a separately added detergent component.
- Light ash 1 average particle size 100 ⁇ m (Oil absorption capacity 0.45ml / g manufactured by Central Glass Co., Ltd.)
- Light ash 2 Average particle size 175 ⁇ m (Oil absorption capacity 0.69ml / g manufactured by Central Glass Co., Ltd.)
- Clay mineral Round rosyl DGA powder (manufactured by Suud Chemi)
- Sodium polyacrylate weight average molecular weight 10,000 (manufactured by Kao Corporation)
- Dens ash average particle size 290 ⁇ m (manufactured by Central Glass Co., Ltd.)
- Sodium sulfate anhydrous neutral sodium sulfate (manufactured by Shikoku Kasei Co., Ltd.)
- the obtained granule group 1 was a granule group having an average particle size of 204 ⁇ m and a bulk density of 490 g / L, and had an oil absorption capacity of 0.52 ml / g.
- the granule yield of 125-1000 ⁇ m was 56%, and the Rosin-Rammler number was 1.0.
- the obtained granule group 2 was a granule group having an average particle size of 320 ⁇ m and a bulk density of 495 g / L, and had an oil absorption capacity of 0.51 ml / g.
- the granule yield of 125-1000 ⁇ m was 56%, and the Rosin-Rammler number was 1.6.
- the resulting granule group 3 was a granule group having an average particle size of 390 ⁇ m and a bulk density of 430 g / L, and had an oil absorption capacity of 0.58 ml / g.
- the granule yield of 125-1000 ⁇ m was 93%, and the Rosin-Rammler number was 2.5.
- Production Example 1 375 parts by weight of water was added to the mixing tank, and 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 fluorescent dye were added and stirred for 10 minutes. 127 parts by weight of sodium carbonate was added, 75 parts by weight of a 40% by weight aqueous sodium polyacrylate solution was added, and the mixture was stirred for 10 minutes to obtain a first preparation liquid. 24 parts by weight of sodium chloride, which is a fine crystal precipitation agent, was added to the first preparation solution and stirred for 10 minutes. Further, 266 parts by weight of zeolite was added and stirred for 30 minutes to obtain a homogeneous second preparation liquid (slurry moisture 42% by weight).
- the second preparation liquid was supplied to a spray drying tower (counterflow type) with a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower.
- the high temperature gas supplied to the spray drying tower was supplied at a temperature of 200 ° C. from the bottom of the tower, and was discharged at 90 ° C. from the top of the tower.
- the water content of the obtained granule group 4 was 4% by weight.
- the obtained granule group was a granule group having an average particle size of 285 ⁇ m and a bulk density of 476 g / L.
- Example 5 100 parts by weight of light ash 1 and 0.6 parts by weight of clay mineral are put into a 70 L drum type granulator ( ⁇ 40 cm ⁇ L60 cm / rotation speed 32 rpm / fluid number 0.23) having a baffle plate. Then, 55.9 parts by weight of 35% sodium polyacrylate aqueous solution was added in 5.5 minutes using a two-fluid nozzle. After the addition, the mixture was granulated for 3 minutes, then discharged from a drum granulator, and dried at 200 ° C. for 3 hours using an electric dryer. The water content after drying was 1.0% by weight.
- the obtained granule group 5 was a granule group having an average particle diameter of 317 ⁇ m and a bulk density of 489 g / L, and had an oil absorption capacity of 0.51 ml / g.
- the granule yield of 125-1000 ⁇ m was 97%, and the Rosin-Rammler number was 2.9.
- Example 6 100 parts by weight of light ash 1 was put into a 70 L drum granulator ( ⁇ 40 cm ⁇ L60 cm / rotation speed 32 rpm / fluid number 0.23) having a baffle plate, and 35% sodium polyacrylate 55.6 parts by weight of the aqueous solution was added using a two-fluid nozzle in 5.5 minutes. After the addition, the mixture was granulated for 3 minutes, then discharged from a drum granulator, and dried at 200 ° C. for 3 hours using an electric dryer. The water content after drying was 0.9% by weight.
- the resulting granule group 6 was a granule group having an average particle size of 328 ⁇ m and a bulk density of 448 g / L, and had an oil absorption capacity of 0.61 ml / g.
- the granule yield of 125-1000 ⁇ m was 95.2%, and the Rosin-Rammler number was 2.5.
- the surfactant composition 50 parts by weight of the surfactant composition was added in 2 minutes, and then stirred for 5 minutes. Furthermore, 6 parts by weight of amorphous aluminosilicate was added, and stirring of the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) was 1 After a minute, the detergent particle group 1 was discharged.
- the obtained detergent particle group 1 had an average particle diameter of 481 ⁇ m, a bulk density of 800 g / L, and a fluidity of 5.8 s.
- detergent particle group 2 was produced by the following method.
- 50 parts by weight of the surfactant-carrying granule group 3 and 50 parts by weight of the surfactant-carrying granule group 4 obtained in a Redige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket) are added.
- stirring of the main shaft stirrring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s
- the resulting detergent particle group 2 had an average particle size of 342 ⁇ m and a bulk density of 807 g / L.
- the dissolution rate was 93% and the fluidity was 6.2 s.
- detergent particle group 3 was produced in the same manner as in Example 8, except that 100 parts by weight of surfactant-carrying granule group 5 was used instead of surfactant-carrying granule group 3.
- the resulting detergent particle group 3 had an average particle size of 356 ⁇ m, a bulk density of 768 g / L, and a fluidity of 6.0 s.
- Example 11 The detergent particle group 4 was discharged in the same manner as in Example 8, except that 100 parts by weight of the surfactant-carrying granule group 6 was used instead of the surfactant-carrying granule group 3.
- the obtained detergent particle group 4 had an average particle diameter of 315 ⁇ m, a bulk density of 808 g / L, and a fluidity of 5.9 s.
- the resulting granule group 9 was a granule group having an average particle size of 352 ⁇ m and a bulk density of 715 g / L, and had an oil absorption capacity of 0.16 ml / g.
- the granule yield of 125-1000 ⁇ m was 92%, and the Rosin-Rammler number was 2.0.
- a 1-fluid nozzle 45.3 parts by weight of 35% sodium polyacrylate aqueous solution was added in 1 minute. After the addition, granulation was performed for 4 minutes, followed by discharging from the granulator and drying at 200 ° C. for 3 hours using an electric dryer. The water content after drying was 1.0% by weight.
- the resulting granule group 10 was a granule group having an average particle size of 362 ⁇ m and a bulk density of 736 g / L, and had an oil absorption capacity of 0.30 ml / g.
- the granule yield of 125-1000 ⁇ m was 55%, and the Rosin-Rammler number was 1.5.
- Comparative Example 3 A detergent particle group 6 was produced in the same manner as in Example 8 except that 100 parts by weight of the surfactant-carrying granule group 10 produced in Comparative Example 2 was used instead of the surfactant-carrying granule group 3.
- the resulting detergent particle group 6 had an average particle size of 876 ⁇ m, a bulk density of 830 g / L, and a fluidity of 6.5 s.
- Comparative Example 4 Detergent particle group 7 was 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 instead of 50 parts by weight of granule group 3 for supporting surfactant.
- the resulting detergent particle group 7 had an average particle size of 424 ⁇ m, a bulk density of 835 g / L, and a fluidity of 6.1 s.
- Example 1 From comparison between Example 1 and Comparative Example 1 and Comparative Example 2, by performing low shear granulation, preferably by performing low shear granulation with a fluid number of 1.0 or less, a desired bulk density, It was revealed that a group of granules with oil-absorbing ability was obtained.
- Example 9 the detergent particle group containing the raw material not granulated in place of the surfactant-carrying granule group of the present invention does not show a good dissolution rate, and The quality was inferior to that containing the supporting granules. This result indicated that granulation by low shear granulation is important for the quality of the detergent particles.
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Abstract
Description
〔1〕 以下の工程1(a)~2を含む嵩密度550g/l以下の界面活性剤担持用顆粒群の製造方法;
工程1(a):粘土鉱物粉末と、粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を混合する工程、及び
工程2:工程1(a)により得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程;
〔2〕 以下の工程1(b)~2を含む嵩密度550g/l以下の界面活性剤担持用顆粒群の製造方法;
工程1(b):粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を混合する工程、及び
工程2:工程1(b)により得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程;
〔3〕 以下の成分を含有する嵩密度550g/l以下の界面活性剤担持用顆粒群;
粘土鉱物を除く吸油能0.4ml/g以上の粉末原料:40~95重量%
粘土鉱物粉末:0~45重量%
バインダー:0~35重量%
水:0~15重量%
〔4〕 前記〔1〕又は〔2〕記載の製造方法により作製される界面活性剤担持用顆粒群又は前記〔3〕記載の界面活性剤担持用顆粒群を含有する顆粒群に界面活性剤組成物を担持させてなる高嵩密度洗剤粒子群;並びに
〔5〕 前記〔4〕記載の洗剤粒子群を含有してなる洗剤組成物;に関するものである。
水溶性とは25℃の水に対する溶解度が0.5g/100g以上であることを意味し、水不溶性とは、25℃の水に対する溶解度が0.5g/100g未満であることを意味する。
1.粘土鉱物を除く吸油能0.4ml/g以上の粉末原料
本発明における必須の成分として、粘土鉱物を除く吸油能0.4ml/g以上の粉末原料が挙げられる。吸油能とは、後述の品質評価方法に記載の方法で決定される値である。粘土鉱物を除く吸油能0.4ml/g以上の吸油能を持つ粉末原料とは、粉末内部に10μm以下の微細な細孔を有する本質的に多孔質な物質であり、その細孔に界面活性剤を担持させることのできる物質である。吸油能の上限は、特に限定されるものでないが、例えば1.0ml/g以下であることが望ましい。
本発明における界面活性剤担持用顆粒群は、水又はバインダー水溶液を添加し、低剪断造粒機を使用することによって、粉末原料の混合物を顆粒化する。粘土鉱物を用いる場合、粘土鉱物と粉末原料との混合物が顆粒化される。水を用いる場合は、粉末原料が一部水に溶解することで生じる粘結性或いは粘土鉱物の粘結性を顆粒化に利用する。バインダー水溶液を用いる場合は、さらにバインダーによる粘結性が利用できるため、顆粒化がより容易になる。
粘土鉱物は層状構造を有しており、その層間に液状界面活性剤を担持することが可能である。その為、粘土鉱物を配合することによって、液状界面活性剤の担持容量を増加させると同時に担持力を向上させることができる。
[Si8(MgaAlb)O20(OH)4]X-・MeX+ (I)
で表される粘土鉱物を、粘土鉱物の主成分とすることが好ましい。ここで、a、b及びxは、0<a≦6、0<b≦4、x=12-2a-3bであり、MeはNa、K、Li、Ca1/2、Mg1/2及びNH4から選ばれる少なくとも1種のイオンである。
本発明における界面活性剤担持用顆粒群は、製造工程で使用される適当量の水分を含有する。赤外線水分計で測定した水分量は、該顆粒群の液状界面活性剤組成物の担持容量を多くする観点から少ない方が好ましく、好ましくは15重量%以下、より好ましくは10重量%以下、更に好ましくは5重量%以下である。
尚、本発明における界面活性剤担持用顆粒群には、上記1~4に挙げた以外の物質であっても、必要に応じて適宜配合することができる。しかし、これらの物質の配合量は担持能の観点から20重量%以下が好ましく、10重量%以下が更に好ましく、5重量%以下が特に好ましい。配合できる物質の例を以下に示す。
金属イオンによる洗浄作用阻害を抑制する為、配合することができる。水溶性キレート剤としては、金属イオン封鎖能を保持する物質であれば特に規定はされないが、結晶性珪酸塩,トリポリリン酸塩,オルトリン酸塩,ピロリン酸塩等が使用可能である。中でも、結晶性珪酸塩及びトリポリリン酸塩が好ましい。水不溶性キレート剤については、水中での分散性の観点から、粒子の平均粒径が0.1~20μmのものが好ましい。好適な水不溶性キレート剤としては、結晶性アルミノ珪酸塩が挙げられ、例えばA型ゼオライト,P型ゼオライト,X型ゼオライト等があるが、金属イオン封鎖能及び経済性の点でA型ゼオライトが好ましい。
洗濯液のイオン強度を高め、皮脂汚れ洗浄等の効果を向上させる為、水溶性無機塩を添加することが好ましい。
溶解性良好で、洗浄力に悪影響を与えない物質であれば特に規定はされない。例えば、硫酸根,亜硫酸根を持つアルカリ金属塩,アンモニウム塩等が挙げられる。
中でも、イオン乖離度の高い硫酸ナトリウム,亜硫酸ナトリウム,硫酸カリウムを賦形剤として使用することが好ましい。又、溶解速度向上の観点からは硫酸マグネシウムとの併用も好ましい。
水中での分散性良好で、洗浄力に悪影響を与えない物質であれば特に規定はされない。例えば結晶性もしくは非晶質のアルミノ珪酸塩や、二酸化珪素、水和珪酸化合物等が挙げられる。水中での分散性の観点から、一次粒子の平均粒径が0.1~20μmのものが好ましい。
蛍光染料、顔料、染料等が挙げられる。
本発明の界面活性剤担持用顆粒群は、噴霧乾燥工程を含まず、少なくとも、粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を撹拌又は混合する工程、及び得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程を含む方法により調製することが出来る。
粘土鉱物粉末と粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を混合する工程においては、それらが実質的に均一に混合できればどのような方法を用いても良い。例えば、工程2で使用する低剪断造粒機を使用して混合しても良いし、予め別の混合機を用いて混合した後、低剪断造粒機へと移送しても良い。粉体混合に使用される該別の混合機としては、例えば、ドラム型ミキサー、パン型ミキサー、リボンミキサー、ナウターミキサー、シュギミキサー、レディゲミキサー、ハイスピードミキサー等が挙げられる。
粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を撹拌又は混合する工程においては、それらが実質的に均一に混合できればどのような方法を用いても良い。例えば、工程2で使用する低剪断造粒機を使用して混合しても良いし、予め上述の混合機を用いて混合した後、低剪断造粒機へと移送しても良い。
工程1(a)又は工程1(b)によって得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程である。この工程において、粉末原料が緩やかに凝集した構造の顆粒を生成する。
又、工程1(a)又は工程1(b)と工程2は同時に行うことも可能である。
V:周速[m/s] R:回転中心から回転物の円周までの半径[m] g:重力加速度[m/s2]
工程2によって得られた顆粒を乾燥する、任意の工程である。水分を除去することにより、粒子内の空隙が増加し、更に担持容量を向上させることができる。
本発明における界面活性剤担持用顆粒群は、少なくとも、粘土鉱物を除く吸油能0.4ml/g以上の粉末原料が緩やかに凝集した構造の顆粒群である。その為、(1)粉末原料間の大きな空隙、(2)粉末原料内の小さな空隙(例えば10μm以下の空隙)の2つの担持サイトを持っている。このうち、担持容量及び担持力には(1)、(2)の双方が、担持速度には(1)が大きく影響し、この2つの担持サイトの調整により所望の担持能を持つ界面活性剤担持用顆粒群を得ることができる。
本発明の洗剤粒子群は、本発明による界面活性剤担持用顆粒群(即ち、本発明の製造方法により得られた界面活性剤担持用顆粒群及び上記の本発明の界面活性剤担持用顆粒群)に界面活性剤組成物を担持させてなる高嵩密度洗剤粒子群である。
R-O-(EO)X-(PO)Y-(EO)Z-H
〔式中、Rは炭化水素基、好ましくはアルキル基又はアルケニル基、EOはオキシエチレン基、POはオキシプロピレン基、X、Y及びZはそれぞれ平均付加モル数を表す。〕
で表されるものであり、その中でも最も好ましい平均付加モル数の関係に関しては、X>0、Z>0、X+Y+Z=6~14であり、X+Z=5~12であり、Y=1~4である。
両性界面活性剤としては、カルボベタイン型のもの、スルホベタイン型のもの等が例示される。
嵩密度は、好ましくは500~1000g/L、より好ましくは600~1000g/L、特に好ましくは650~900g/Lである。平均粒径は、好ましくは150~500μm、より好ましくは180~400μmである。
尚、前記嵩密度、平均粒径は、後述の物性の測定方法に記載の方法で測定することができる。
洗剤粒子群を得る好適な製法は、以下の工程(I)を含んでなり、更に必要に応じて工程(II)を含んでもよい。
工程(I):界面活性剤組成物が液状又はペースト状の条件下にて、該界面活性剤組成物を本発明の製法で得られた界面活性剤担持用顆粒群を含む顆粒群と混合する工程。
工程(II):工程(I)で得られた混合物と表面被覆剤とを混合し、得られる洗剤粒子群の表面を該表面被覆剤で被覆する工程。但し、工程(II)は解砕が同時に進行していてもよい。
担持用顆粒群へ界面活性剤組成物を担持させる方法としては、例えば、回分式や連続式の混合機を用いて、担持用顆粒群と界面活性剤組成物とを混合する方法が挙げられる。ここで、回分式で行う場合に、混合機への仕込み方法としては、(1)混合機に先ず担持用顆粒群を仕込んだ後、界面活性剤組成物を一気に添加する、(2)混合機に担持用顆粒群と、界面活性剤組成物を少量ずつ添加するのを繰り返す、(3)担持用顆粒群の一部を混合機に仕込んだ後、残りの担持用顆粒群と界面活性剤組成物とを少量ずつ添加するのを繰り返す等の方法をとることができる。
本発明においては、工程(I)により界面活性剤が担持された洗剤粒子群の粒子表面を改質するために、添加時の形態として以下の(1)微粉体、(2)液状物のような種々の表面被覆剤を添加する工程(II)を一工程以上行ってもよい。
微粉体としては、その一次粒子の平均粒径が10μm以下であることが好ましく、0.1~10μmであることがより好ましい。平均粒径がこの範囲において、洗剤粒子群の粒子表面の被覆率が向上し、洗剤粒子群の流動性と耐ケーキング性の向上の観点から好適である。当該微粉体の平均粒径は、光散乱を利用した方法、例えばパーティクルアナライザー(堀場製作所製)、又は顕微鏡観察による測定等で測定される。又、該微粉体が高いイオン交換能や高いアルカリ能を有していることが洗浄力の観点から好ましい。
液状物としては、水溶性ポリマーや脂肪酸等が挙げられ、水溶液や溶融状態で添加することができる。
水溶性ポリマーとしては、カルボキシメチルセルロース、ポリエチレングリコール、ポリアクリル酸ナトリウム、アクリル酸とマレイン酸の共重合体又はその塩等のポリカルボン酸塩等が挙げられる。当該水溶性ポリマーの使用量としては、洗剤粒子群100重量部に対して0.5~10重量部が好ましく、1~8重量部がより好ましく、2~6重量部が特に好ましい。当該水溶性ポリマーの使用量はこの範囲において、良好な溶解性、良好な流動性、耐ケーキング性を示す洗剤粒子群を得ることができる。
脂肪酸としては、例えば、炭素数10~22の脂肪酸等が挙げられる。当該脂肪酸の使用量としては、洗剤粒子群100重量部に対して0.5~5重量部が好ましく、0.5~3重量部が特に好ましい。常温で固体のものの場合は、流動性を示す温度まで加温した後に、噴霧して供給することが好ましい。
本発明における洗剤組成物は、上述の洗剤粒子群を含有してなる組成物であり、さらに該洗剤粒子群以外に別途添加された洗剤成分(例えば、ビルダー顆粒、蛍光染料、酵素、香料、消泡剤、漂白剤、漂白活性化剤等)を含有してなる組成物である。
洗剤組成物の製法は、特に限定はなく、例えば、前記洗剤粒子群及び別途添加された洗剤成分を混合する方法が挙げられる。このようにして得られた洗剤組成物は、界面活性剤の担持容量の多い洗剤粒子を含有しているため、少量でも十分な洗浄効果を発現しうるものである。かかる洗剤組成物の用途としては粉末洗剤を用いる用途であれば特に限定はないが、例えば、衣料用粉末洗剤、自動食器用洗剤等が挙げられる。
1.嵩密度
嵩密度は、JIS K 3362により規定された方法で測定する。
平均粒径については、以下の2つの方法により測定した。
(1)平均粒径が80μm以上のものについては、JIS K 8801の標準篩(目開き2000~125μm)を用いて5分間振動させた後、篩目のサイズによる重量分率からメジアン径を算出する。より詳細には、目開き125μm、180μm、250μm、355μm、500μm、710μm、1000μm、1400μm、2000μmの9段の篩と受け皿を用いて、受け皿上に目開きの小さな篩から順に積み重ね、最上部の2000μmの篩の上から100gの粒子を添加し、蓋をしてロータップ型ふるい振とう機(HEIKO製作所製、タッピング156回/分、ローリング:290回/分)に取り付け、5分間振動させたあと、それぞれの篩及び受け皿上に残留した該粒子の重量を測定し、各篩上の該粒子の重量割合(%)を算出した。受け皿から順に目開きの小さな篩上の該粒子の重量割合を積算していき合計が50%となる粒径を平均粒径とした。
顆粒群の水分測定は赤外線水分計法により行う。即ち、試料3gを重量既知の試料皿にはかり採り、赤外線水分計(ケット科学研究所(株)製FD-240)を用いて200℃で加熱し、30秒間重量変化がなくなった時点を乾燥終了とした。そして、乾燥後の重量と乾燥前重量から水分量を算出する。
流動時間は、JIS K 3362により規定された嵩密度測定用のホッパーから、100mLの粉末が流出するのに要する時間とする。流動時間として10秒以下が好ましく、8秒以下がより好ましく、7秒以下が更に好ましい。
1.吸油能
吸収量測定器((株)あさひ総研製S410)に粉末を30~35g投入し、駆動羽根200r.p.m.で回転させる。ここに液状のノニオン(花王(株)製エマルゲン108)を液供給速度4ml/minで滴下し、最大トルクとなる点を見極める。この最大トルクとなる点の70%のトルクとなる点での液添加量を粉末投入量で除算し、吸油能とした。
粒度分布の指標としては1410μmの篩を通過させた洗剤粒子群をフィッティングし、Rosin-Rammler数を算出して用いる。Rosin-Rammler数の算出には以下の式を用いる。
R(Dp) :粒径Dpμm以上の粉体の累積率[%]
Dp :粒径[μm]
De :平均粒径[μm]
n :Rosin-Rammler数
本発明における溶解性の指標としては、以下に説明する洗剤粒子群の60秒間溶解率を用いることができる。溶解率は90%以上が好ましく、95%以上がより好ましい。尚、洗剤組成物についても同様の方法で評価可能である。
硬度が71.2mgCaCO3/リットルに相当する5℃に冷却した1リットルの硬水(Ca/Mgモル比7/3)を1リットルビーカー(内径105mm、高さ150mmの円筒型、例えば岩城硝子社製1リットルガラスビーカー)の中に満たし、5℃の水温をウォーターバスにて一定に保った状態で、攪拌子(長さ35mm、直径8mm、例えば型式:ADVANTEC社製、テフロン(登録商標)SA(丸型細型))にて水深に対する渦巻きの深さが略1/3となる回転数(800r.p.m.)で攪拌する。1.0000±0.0010gとなるように縮分・秤量した洗剤粒子群を攪拌下に水中に投入・分散させ攪拌を続ける。投入から60秒後にビーカー中の洗剤粒子群分散液を、重量既知のJIS Z 8801に規定の目開き74μmの標準篩(直径100mm)で濾過し、篩上に残留した含水状態の洗剤粒子群を篩と共に重量既知の開放容器に回収する。尚、濾過開始から篩を回収するまでの操作時間を10±2秒とする。回収した洗剤粒子群の溶残物を105℃に加熱した電気乾燥機にて1時間乾燥し、その後、シリカゲルを入れたデシケーター(25℃)内で30分間保持して冷却する。冷却後、乾燥した洗剤の溶残物と篩と回収容器の合計の重量を測定し、式(1)によって洗剤粒子群の溶解率(%)を算出する。
S:洗剤粒子群の投入重量(g)
T:上記攪拌条件にて得られた水溶液を上記篩に供したときに、篩上の残存する洗剤粒子群の溶残物の乾燥重量(g)(乾燥条件:105℃の温度下に1時間保持した後、シリカゲルを入れたデシケーター(25℃)内で30分間保持する)
本発明における顆粒収率とは、全顆粒のうち特定粒径範囲の顆粒の割合によって決定される。例えば、125-1000μmの顆粒収率とは、全顆粒のうち125μm以上1000μm以下の顆粒の割合を示す。
本発明における洗剤収率とは、前記洗剤粒子群及び別途添加された洗剤成分を混合して得られた洗剤組成物中、1180μm以下の粒子の割合を示す。
ライト灰1:平均粒径100μm
(セントラル硝子(株)製 吸油能0.45ml/g)
ライト灰2:平均粒径175μm
(セントラル硝子(株)製 吸油能0.69ml/g)
粘土鉱物:ラウンドロジルDGAパウダー(ズード・ケミ社製)
ポリアクリル酸ナトリウム:重量平均分子量1万(花王(株)製)
デンス灰:平均粒径290μm(セントラル硝子(株)製)
硫酸ナトリウム:無水中性芒硝(四国化成(株)製)
粘土鉱物2.1kgとライト灰1の4.9kg(粘土鉱物/粉末原料=3/7)を邪魔板を有した70Lドラム型造粒機(φ40cm×L60cm/回転数32r.p.m./フルード数0.23)中で混合した。2分間混合した後、水2.5kgを1流体ノズル(スプレーイングシステムスジャパン(株)製:バインダー噴霧圧0.4MPa)を用いて、3分間で添加した。添加後、3分間顆粒化を行った後、ドラム型造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は1.1重量%であった。
粘土鉱物2.1kgとライト灰1の4.2kg(粘土鉱物/粉末原料=1/2)を邪魔板を有した70Lドラム型造粒機(φ40cm×L60cm/回転数32r.p.m./フルード数0.23)中で混合した。2分間混合した後、25%ポリアクリル酸ナトリウム水溶液3.8kgを2流体ノズル(スプレーイングシステムスジャパン(株)製:バインダー噴霧圧0.15MPa/微粒化用Air噴霧圧0.3MPa)を用いて、5分間で添加した。添加後、3分間顆粒化を行った後、ドラム型造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は1.3重量%であった。
粘土鉱物2.1kgとライト灰2の4.2kg(粘土鉱物/粉末原料=1/2)を邪魔板を有した70Lドラム型造粒機(φ40cm×L60cm/回転数32r.p.m./フルード数0.23)中で混合した。2分間混合した後、25%ポリアクリル酸ナトリウム水溶液3.8kgを2流体ノズルを用いて、5分間で添加した。添加後、3分間顆粒化を行った後、ドラム型造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は0.9重量%であった。
混合槽に水375重量部を入れ、水温が35℃に達した後に、硫酸ナトリウム127重量部、亜硫酸ナトリウム5重量部、蛍光染料1重量部を添加して10分間攪拌した。炭酸ナトリウム127重量部を添加し、40重量%ポリアクリル酸ナトリウム水溶液75重量部を添加し10分間攪拌して第1調製液とした。微細結晶析出剤である塩化ナトリウム24重量部を第1調製液に添加し、10分間攪拌した。更にゼオライト266重量部を添加し、30分間攪拌して均質な第2調製液を得た(スラリー水分42重量%)。
ライト灰1の100重量部と粘土鉱物0.6重量部を邪魔板を有した70Lドラム型造粒機(φ40cm×L60cm/回転数32r.p.m./フルード数0.23)中に投入し、35%ポリアクリル酸ナトリウム水溶液55.9重量部を2流体ノズルを用いて、5.5分間で添加した。添加後、3分間顆粒化を行った後、ドラム型造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は1.0重量%であった。
ライト灰1の100重量部を邪魔板を有した70Lドラム型造粒機(φ40cm×L60cm/回転数32r.p.m./フルード数0.23)中に投入し、35%ポリアクリル酸ナトリウム水溶液55.6重量部を2流体ノズルを用いて、5.5分間で添加した。添加後、3分間顆粒化を行った後、ドラム型造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は0.9重量%であった。
界面活性剤組成物(ポリオキシエチレンアルキルエーテル/ポリエチレングリコール/アルキルベンゼンスルホン酸ナトリウム/水=42/8/42/8(重量比))を80℃にした。次に、レディゲミキサー(松坂技研(株)製、容量130L、ジャケット付)に、得られた界面活性剤担持用顆粒群3を100重量部投入し、主軸(攪拌翼、回転数:60rpm、周速:1.6m/s)の攪拌を開始した。尚、ジャケットに80℃の温水を10L/分で流した。そこに、上記界面活性剤組成物50重量部を2分間で投入し、その後5分間攪拌を行った。更に、6重量部の無定形アルミノ珪酸塩を投入し、主軸(回転数:120rpm、周速:3.1m/s)とチョッパー(回転数:3600rpm、周速:28m/s)の攪拌を1分間行い、洗剤粒子群1を排出した。
実施例3にて製造した界面活性剤担持用顆粒群3と、製造例1の噴霧乾燥による界面活性剤担持用顆粒群4を用いて次に示す方法で洗剤粒子群2を製造した。
次に、界面活性剤担持用顆粒群3に代えて界面活性剤担持用顆粒群5を100重量部用いた他は実施例8と同様にして洗剤粒子群3を製造した。
得られた洗剤粒子群3は、平均粒径356μm、嵩密度768g/L、流動性6.0sであった。
界面活性剤担持用顆粒群3に代えて界面活性剤担持用顆粒群6を100重量部用いた他は実施例8と同様にして洗剤粒子群4を排出した。
得られた洗剤粒子群4は、平均粒径315μm、嵩密度808g/L、流動性5.9sであった。
粘土鉱物1.5kgとライト灰1の3.5kg(粘土鉱物/粉末原料=3/7)をインテンシブミキサー(アイリッヒ社製02VAC;パン回転数44r.p.m.;解砕翼回転数1650r.p.m./フルード数213)で混合した。2分間混合した後、水1.25kgを1流体ノズルを用いて、1分間で添加した。添加後、3分間顆粒化を行った後、インテンシブミキサーから排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は1.0重量%であった。
ライト灰1の100重量部と粘土鉱物42.9重量部(粘土鉱物/粉末原料=3/7)10Lハイスピードミキサー(深江パウテック(株)製;アジテータ回転数200r.p.m./フルード数8.94;解砕翼回転数3600r.p.m./フルード数398)で混合した。35%ポリアクリル酸ナトリウム水溶液45.3重量部を1流体ノズルを用いて、1分間で添加した。添加後、4分間顆粒化を行った後、造粒機から排出し、電気乾燥機を用いて200℃で3時間乾燥を行った。乾燥後の水分は1.0重量%であった。
界面活性剤担持用顆粒群3の代わりに比較例2で製造した界面活性剤担持用顆粒群10の100重量部を用いて、実施例8と同様にして洗剤粒子群6を製造した。
界面活性剤担持用顆粒群3の50重量部に代えてライト灰1を35重量部、粘土鉱物を15重量部とした他は実施例9と同様の方法で洗剤粒子群7を製造した。
Claims (10)
- 以下の工程1(a)~2を含む嵩密度550g/l以下の界面活性剤担持用顆粒群の製造方法;
工程1(a):粘土鉱物粉末と、粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を混合する工程、及び
工程2:工程1(a)により得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程。 - 以下の工程1(b)~2を含む嵩密度550g/l以下の界面活性剤担持用顆粒群の製造方法;
工程1(b):粘土鉱物を除く吸油能0.4ml/g以上の粉末原料を混合する工程、及び
工程2:工程1(b)により得られた混合粉末に水又はバインダー水溶液を添加し、低剪断造粒機によって顆粒化する工程。 - 低剪断造粒機のフルード数が1.0以下である請求項1又は2に記載の製造方法。
- 更に、工程3を含む請求項1~3いずれか記載の製造方法;
工程3:工程2によって得られた顆粒を乾燥する工程。 - 水又はバインダー水溶液を多流体ノズルを用いて添加する請求項1~4いずれか記載の製造方法。
- 多流体ノズルが2流体ノズルである請求項5記載の製造方法。
- 粉末原料がライト灰を含む請求項1~6いずれか記載の製造方法。
- 以下の成分を含有する嵩密度550g/l以下の界面活性剤担持用顆粒群。
粘土鉱物を除く吸油能0.4ml/g以上の粉末原料:40~95重量%
粘土鉱物粉末:0~45重量%
バインダー:0~35重量%
水:0~15重量% - 請求項1~7いずれか記載の製造方法により作製される界面活性剤担持用顆粒群又は請求項8記載の界面活性剤担持用顆粒群を含有する顆粒群に界面活性剤組成物を担持させてなる高嵩密度洗剤粒子群。
- 請求項9記載の洗剤粒子群を含有してなる洗剤組成物。
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CN200980114826.8A CN102015992B (zh) | 2008-05-19 | 2009-05-13 | 表面活性剂担载用颗粒群 |
AU2009250634A AU2009250634B2 (en) | 2008-05-19 | 2009-05-13 | Surfactant-supporting granule cluster |
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---|---|---|---|---|
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WO2012067227A1 (ja) * | 2010-11-19 | 2012-05-24 | 花王株式会社 | 洗剤粒子群の製造方法 |
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JP2014015536A (ja) * | 2012-07-09 | 2014-01-30 | Kao Corp | 洗剤粒子の製造方法 |
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Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60227895A (ja) | 1984-04-11 | 1985-11-13 | ヘキスト・アクチエンゲゼルシヤフト | 結晶性層状ケイ酸ナトリウムを含有する水軟化剤 |
JPH05279013A (ja) | 1991-12-29 | 1993-10-26 | Kao Corp | 合成無機ビルダー |
JPH0789712A (ja) | 1993-06-26 | 1995-04-04 | Kao Corp | 合成無機ビルダー及び洗浄剤組成物 |
WO1995026394A1 (fr) * | 1994-03-28 | 1995-10-05 | Kao Corporation | Procede de production de particules detergentes a densite apparente elevee |
WO1998010052A1 (fr) * | 1996-09-06 | 1998-03-12 | Kao Corporation | Particules detergentes, procede pour preparer ces particules et composition detergente presentant une masse volumique apparente importante |
JPH10176200A (ja) * | 1996-12-18 | 1998-06-30 | Kao Corp | ノニオン洗剤粒子の製造方法 |
JPH10296064A (ja) | 1997-04-28 | 1998-11-10 | Kao Corp | 混合装置 |
JPH10296065A (ja) | 1997-04-28 | 1998-11-10 | Kao Corp | 混合方法および混合装置 |
JP2000503055A (ja) * | 1996-01-09 | 2000-03-14 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | 粒状洗剤/洗浄剤またはその成分の製造法 |
JP2000186300A (ja) * | 1998-10-16 | 2000-07-04 | Kao Corp | 単核性洗剤粒子群の製法 |
JP2001081499A (ja) * | 1999-09-17 | 2001-03-27 | Lion Corp | 粒状洗剤組成物の製造方法 |
JP2002541267A (ja) | 1999-04-02 | 2002-12-03 | ロディア・シミ | 実質上又は完全に水溶性の鉱物性塩を基材とする組成物、該塩を含有する処方物及びそれらの製造法 |
JP2004176055A (ja) * | 2002-11-15 | 2004-06-24 | Lion Corp | 粒状洗剤の製造方法 |
JP2004244644A (ja) | 1999-06-14 | 2004-09-02 | Kao Corp | 界面活性剤担持用顆粒群 |
JP2005154648A (ja) * | 2003-11-27 | 2005-06-16 | Lion Corp | 粒状洗剤組成物の製造方法 |
JP2006057001A (ja) * | 2004-08-20 | 2006-03-02 | Kao Corp | 洗浄用組成物 |
JP2006291070A (ja) * | 2005-04-12 | 2006-10-26 | Kao Corp | 高嵩密度洗浄剤組成物の製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69922783T2 (de) * | 1998-10-16 | 2005-12-08 | Kao Corp. | Verfahren zur herstellung von detergentteilchen |
KR100434923B1 (ko) * | 1999-06-14 | 2004-06-09 | 카오카부시키가이샤 | 계면활성제 지지용 과립군 및 그의 제법 |
DE102005012638A1 (de) * | 2005-03-18 | 2006-09-21 | Süd-Chemie AG | Granulate aus natürlichen Schichtmineralien und Verfahren zu deren Herstellung |
-
2009
- 2009-05-13 CN CN200980114826.8A patent/CN102015992B/zh active Active
- 2009-05-13 AU AU2009250634A patent/AU2009250634B2/en not_active Ceased
- 2009-05-13 JP JP2009116683A patent/JP5525755B2/ja active Active
- 2009-05-13 EP EP09750497A patent/EP2277985A4/en not_active Withdrawn
- 2009-05-13 WO PCT/JP2009/058934 patent/WO2009142135A1/ja active Application Filing
- 2009-05-19 TW TW98116580A patent/TWI441917B/zh not_active IP Right Cessation
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60227895A (ja) | 1984-04-11 | 1985-11-13 | ヘキスト・アクチエンゲゼルシヤフト | 結晶性層状ケイ酸ナトリウムを含有する水軟化剤 |
JPH05279013A (ja) | 1991-12-29 | 1993-10-26 | Kao Corp | 合成無機ビルダー |
JPH0789712A (ja) | 1993-06-26 | 1995-04-04 | Kao Corp | 合成無機ビルダー及び洗浄剤組成物 |
WO1995026394A1 (fr) * | 1994-03-28 | 1995-10-05 | Kao Corporation | Procede de production de particules detergentes a densite apparente elevee |
JP2000503055A (ja) * | 1996-01-09 | 2000-03-14 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | 粒状洗剤/洗浄剤またはその成分の製造法 |
WO1998010052A1 (fr) * | 1996-09-06 | 1998-03-12 | Kao Corporation | Particules detergentes, procede pour preparer ces particules et composition detergente presentant une masse volumique apparente importante |
JPH10176200A (ja) * | 1996-12-18 | 1998-06-30 | Kao Corp | ノニオン洗剤粒子の製造方法 |
JPH10296064A (ja) | 1997-04-28 | 1998-11-10 | Kao Corp | 混合装置 |
JPH10296065A (ja) | 1997-04-28 | 1998-11-10 | Kao Corp | 混合方法および混合装置 |
JP2000186300A (ja) * | 1998-10-16 | 2000-07-04 | Kao Corp | 単核性洗剤粒子群の製法 |
JP2002541267A (ja) | 1999-04-02 | 2002-12-03 | ロディア・シミ | 実質上又は完全に水溶性の鉱物性塩を基材とする組成物、該塩を含有する処方物及びそれらの製造法 |
JP2004244644A (ja) | 1999-06-14 | 2004-09-02 | Kao Corp | 界面活性剤担持用顆粒群 |
JP2001081499A (ja) * | 1999-09-17 | 2001-03-27 | Lion Corp | 粒状洗剤組成物の製造方法 |
JP2004176055A (ja) * | 2002-11-15 | 2004-06-24 | Lion Corp | 粒状洗剤の製造方法 |
JP2005154648A (ja) * | 2003-11-27 | 2005-06-16 | Lion Corp | 粒状洗剤組成物の製造方法 |
JP2006057001A (ja) * | 2004-08-20 | 2006-03-02 | Kao Corp | 洗浄用組成物 |
JP2006291070A (ja) * | 2005-04-12 | 2006-10-26 | Kao Corp | 高嵩密度洗浄剤組成物の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2277985A4 * |
Cited By (11)
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JP2011026583A (ja) * | 2009-06-30 | 2011-02-10 | Kao Corp | 高嵩密度洗剤粒子群の製造方法 |
CN102459555A (zh) * | 2009-06-30 | 2012-05-16 | 花王株式会社 | 高体积密度洗涤剂粒子群的制造方法 |
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WO2011062235A1 (ja) * | 2009-11-18 | 2011-05-26 | 花王株式会社 | 界面活性剤担持用顆粒群の製造方法 |
AU2010320063B2 (en) * | 2009-11-18 | 2014-11-13 | Kao Corporation | Method for producing surfactant-supporting granule cluster |
CN102686716A (zh) * | 2009-12-17 | 2012-09-19 | 花王株式会社 | 洗涤剂粒子群的制造方法 |
WO2012067227A1 (ja) * | 2010-11-19 | 2012-05-24 | 花王株式会社 | 洗剤粒子群の製造方法 |
CN103228776A (zh) * | 2010-11-19 | 2013-07-31 | 花王株式会社 | 洗涤剂颗粒群的制造方法 |
CN103228776B (zh) * | 2010-11-19 | 2014-11-19 | 花王株式会社 | 洗涤剂颗粒群的制造方法 |
JP2014015536A (ja) * | 2012-07-09 | 2014-01-30 | Kao Corp | 洗剤粒子の製造方法 |
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JP5525755B2 (ja) | 2014-06-18 |
TW201000626A (en) | 2010-01-01 |
EP2277985A1 (en) | 2011-01-26 |
CN102015992A (zh) | 2011-04-13 |
CN102015992B (zh) | 2012-07-11 |
JP2010001460A (ja) | 2010-01-07 |
AU2009250634A1 (en) | 2009-11-26 |
AU2009250634B2 (en) | 2012-11-29 |
EP2277985A4 (en) | 2012-11-28 |
TWI441917B (zh) | 2014-06-21 |
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